Environmental Research of the

Federal Ministry of the Environment,

Nature Conservation and Nuclear Safety
- Water Economy -

Research Report 200 24 233

Environmentally compatible cooling water

treatment chemicals

by
Dipl. Geogr./Hyd. Stefan Gartiser
Dipl. Hyd. Elke Urich

Hydrotox GmbH, Freiburg

On behalf of the
Federal Environmental Agency

Berlin, April 2002

 I

Report Cover Sheet

1. Report No. 2. 3.
UBA-FB 200 24 233 Water economy
4. Report Title
Environmentally compatible cooling water treatment chemicals
5. Autor(s) (Family Name(s), First Name(s)) 6. Report Date
Gartiser, Stefan; Urich, Elke
7. Publication Date

8. Performing Organisation(s) (Name, Address) 9. UFOPLAN-No.

Hydrotox GmbH 200 24 233
Boetzinger Str. 29 10. No. of Pages

D-79111 Freiburg 106 + 91 (annex)

11. No. of References
103 + 71 (annex)
12. Sponsoring Agency (Name, Address) 13. No. of Tables
German Federal Environmental Agency 20
Postfach 33 00 22, D-14191 Berlin (Germany) 14. No. of Figures
11
15. Supplementary Notes
This project was commissioned in the form of a grant on the basis of costs as partial
financing to the recipients (Grant Decision Z 1.6-25106/182 of 31.01.00)
In Germany about 32 billion m3/a cooling water are discharged from industrial plants and
the power industry. These are conditioned in part with biocides, scaling and corrosion
inhibitors. Within the research project the significance of cooling water chemicals was
evaluated, identifying the chemicals from product information, calculating their loads from
consumption data of more than 180 cooling plants and investigating the basic characteristic
data needed for an environmental hazard assessment. Additionally, the effects of cooling
water samples and products were determined in biological test systems. Batch tests (shock
treatments) were performed under defined conditions in order to measure the inactivation
of cooling water biocides.
Generally the cooling water samples only showed low ecotoxicity, upon considering the
inactivation of the biocides with time. With systematic backtracking, the genotoxicity of the
cooling water from one company in the umu test could be attributed to one biocide with
isothiazolinones and Bronopol as ingredients. Measurement of the inactivation of biocides,
with the luminescent bacteria toxicity test, revealed a strong correlation with the inoculum
concentration and enabled a better estimation of the importance of the elimination factors
degradation and adsorption. An overall balance sheet of chemical loads confirmed that the
principal amounts came from open recirculation cooling systems, whereas only <10% of the
plants with once-through cooling water used conditioning chemicals at all. The extrapolation
of consumption data for Germany gave total loads of about 4.000 t/a oxidative and 125 t/a
non-oxidative biocides. Additionally inputs of about 1.500-2.200 t/a phosphonic acids, 45-
135 t/a molybdate and 113-216 t/a zinc were calculated. Basic substance data sheets were
documented for all chemicals applied, enabling first assessments of environmental
relevance using several approaches of hazard assessment.
17. Keywords
cooling water, treatment chemicals, biocide, degradation, elimination, phosphonates,
phosphonic acids, polycarboxylates, polycarbonic acids, zinc, bioassay, ecotoxicity, geno-
toxicity, Vibrio fischeri assay, Daphnia test, umu-assay, Ames test, balance, load
18. Price 19. 20.
 II

Contents

0 Summary .............................................................................................. 1

1 Introduction.......................................................................................... 5

2 Current knowledge .............................................................................. 6

2.1 Fundamentals ........................................................................................ 6

2.2 Cooling water flow ................................................................................. 7

2.3 Minimum requirements for cooling water discharges in Germany ......... 9

2.4 General environmental hazards from cooling systems ........................ 10

2.5 Cooling water conditioning................................................................... 12

2.5.1 Dispersants and hardness stabilizers .................................................. 12

2.5.2 Scale inhibitors .................................................................................... 13
2.5.3 Biocides ............................................................................................... 14

3 Goals and investigative strategy ...................................................... 18

4 Methods .............................................................................................. 20

4.1 Laboratory investigations ..................................................................... 20

4.1.1 Cooling water samples ........................................................................ 20

4.1.2 Product investigations.......................................................................... 24
4.1.3 Chemical parameters........................................................................... 24
4.1.4 Fluorescent bacteria test according to DIN 38412-34 and
Nr. 404 of the AbwV............................................................................. 24
4.1.5 Alga test according to DIN 38412-33 and Nr. 403 of the AbwV ........... 25
4.1.6 Daphnia test according to DIN 38412-30 and Nr. 402 of the AbwV ..... 25
4.1.7 Ames test in conformance with DIN 38415-4 ...................................... 25
4.1.8 umu test according to DIN 38415-3 and Nr. 410 of the AbwV ............. 26
4.1.9 Elimination of biocides ......................................................................... 27

4.2 Drawing up an overall balance sheet................................................... 28

4.2.1 Compilation of production information materials .................................. 28

 III

4.2.2 Making a balance sheet of the emissions of cooling water

chemicals............................................................................................. 29

4.3 Literature and database-research........................................................ 33

5 Results................................................................................................ 36

5.1 Cooling water investigations ................................................................ 36

5.2 Product investigations.......................................................................... 38

5.2.1 Eco- and Genotoxicity.......................................................................... 38

5.2.2 Identifying the source of the genotoxicity in plant 6 ............................. 38
5.2.3 Decrease of the biocidal effect in the fluorescent bacteria test ........... 41

5.3 Evaluation of the product information sheets....................................... 52

5.4 Evaluation of the questionnnaires........................................................ 53

5.4.1 Open recirculation cooling systems ..................................................... 54

5.4.2 Once-through cooling systems ............................................................ 56
5.4.3 Closed circulation cooling systems ...................................................... 58
5.4.4 Estimation of the total loads for Germany............................................ 58
5.4.5 Overview and comparison ................................................................... 64

5.5 Elimination of chemicals in cooling systems and sewage plants ......... 70

5.6 Regulatory control of cooling water discharges ................................... 70

5.7 Literature and database research ........................................................ 71

6 Evaluation........................................................................................... 74

6.1 Composition of cooling water............................................................... 74

6.2 Emission route for cooling water chemicals ......................................... 75

6.3 Elimination behavior of cooling water biocides .................................... 75

6.4 Choice of active substances ................................................................ 77

6.4.1 Biocides ............................................................................................... 77

6.4.2 Cooling water conditioners................................................................... 82
 IV

7 Recommendations............................................................................. 89

7.1 Energy conservation measures ........................................................... 89

7.2 Technical solutions .............................................................................. 89

7.3 Process operation ................................................................................ 91

7.4 Evaluation and selection of cooling water chemicals ........................... 93

7.4.1 Water risk classes, the VCI-concept for open cooling systems ........... 93
7.4.2 "Benchmarking"-concept ..................................................................... 94
7.4.3 Plant specific evaluation of cooling water chemicals ........................... 95
7.4.4 TEGEWA-concept for indirect dischargers .......................................... 96
7.4.5 Outlook ................................................................................................ 96

8 Sources............................................................................................... 98

9 Ackknowledgements ....................................................................... 105

List of Tables
Table 1: Cooling water discharge in river basins (1995) [Mio. m 3] .............................. 7
Table 2: River flow volume balance for Germany in 1992 .......................................... 7
Table 3: Ratio of used/discharged cooling water (1995) ............................................. 9
Table 4: Charateristic data for the investigated systems .......................................... 23
Table 5: Determination of the elimination of cooling water biocides ......................... 28
Table 6: Summary of the wastewater investigations ................................................. 37
Table 7: Results of the product investigations .......................................................... 39
Table 8: Source of the genotoxicity in the cooling water from plant 6 ....................... 40
Table 9: Dosing of biocides in the circulation cooling ............................................... 42
Table 10: Experimental overview of the elimination curves of cooling
water biocides ........................................................................................... 43
Table 11: Elimination of BCDMH depending on the inoculum .................................. 50
Table 12: Characteristic data for the cooling systems investigated .......................... 53
Table 13: Total amounts of the investigated chemicals in open circulation
cooling ...................................................................................................... 55
Table 14: Consumption data in plants with flow-through cooling .............................. 57
Table 15: Cooling water use for thermal power plants (1995 ) ................................. 60
 V

Table 16: Concentrations of continuously added conditioners (concentration

in the circulation water in mg/l) ................................................................. 61
Table 17: Chemical usage in open circulation cooling systems in Germany ............ 63
Table 18: Total load of cooling water chemicals in the once-through cooling
of the foodstuffs industry........................................................................... 64
Table 19: Comparison of the estimated consumption data for certain biocides
with data from other countries (data in kg/a on a substance basis) .......... 69
Table 20: Summarized evaluation of the eotoxicity and degradability of cooling
water chemicals ........................................................................................ 73

List of Figures
Figure 1: Investigative strategy ................................................................................. 19
Figure 2: Decrease of the fluorescent bacteria inhibition with isothiazolinone .......... 44
Figure 3: Decrease of the fluorescent bacteria inhibition with QAV .......................... 45
Figure 4: Decrease of the fluorescent bacteria inhibition with DBNPA (10 mg/l) ...... 46
Figure 5: Decrease of the fluorescent bacteria inhibition with DBNPA (48 mg/l) ...... 46
Figure 6: Fluorescent bacteria inhibition with glutardialdehyde (30-160 mg/l) .......... 48
Figure 7: Fluorescent bacteria inhibition with glutardialdehyde (30-1000 mg d.s./l) . 48
Figure 8: Decrease of the fluorescent bacteria inhibition with Bronopol ................... 49
Figure 9: Decrease of the fluorescent bacteria inhibition with BCDMH (4 mg/l) ....... 51
Figure 10: Decrease of the fluorescent bacteria inhibition with BCDMH (37 mg/l) ... 51
Figure 11: Proportion of biocidal active ingredients in 101 products ......................... 52
 VI

Abbreviations
AbwV Wastewater Ordinance
AMPA Aminomethylenephosphonic acid
AOX Adsorbable organic halogens (X = Cl, Br, I)
ATMP Aminotrimethylenephosphonic acid
ATV Abwassertechnische Vereinigung e. V.
BAT Best available techniques
BCDMH 1-Bromo-3-chloro-5,5-dimethylhydantoin
BgVV Bundesinstitut für gesundheitlichen Verbraucherschutz
und Veterinärmedizin
BIG Brandweerinformatiecentrum Gevaarlijke Stoffen
BUA Beratergremium für umweltrelevante Schadstoffe
CAS Chemical Abstracts
CHEMIS Chemical information system of the BgVV
COD Chemical oxygen demand
DBNPA Dibromonitrilopropionamide
DTPMP Dieethylenetriaminepentamethylenephosphonic acid
DOSE Dictionary of Substances and Their Effects
ECDIN Environmental Chemicals Data and Information Network
EnviChem Data Bank of Environmental Properties of Chemicals
EC50 50% effect concentration
EDTA Ethylenediaminetetraacetate
EDTMP Ethylenediaminetetramethylenephosphonic acid
EQS Environmental Quality Standard
EC European Community
GESTIS Gefahrstoffinformationssystem der gewerblichen
Berufsgenossenschaften
GSBL Gemeinsame Stoffdatenbank Bund/Länder
GA Lowest ineffective dilution, alga test = lowest dilution
factor at which inhibition of algal biomass growth is below
20%.
GEA Lowest ineffective dilution, Ames test = lowest dilution
factor at which an induction difference as compared with
negative controls of <80 (TA100) resp. <20
revertants/plate (TA98) is determined.
GEU Lowest ineffective dilution, umu assay = lowest dilution
factor with an induction rate below 1.5.
 VII

GL Lowest ineffective dilution, luminescent bacteria test =

lowest dilution factor at which inhibition of luminescence
is below 20%
GD Lowest ineffective dilution, Daphnia test = lowest dilution
factor at which 90% of Daphnia retain their mobility
HSDB Hazardous Substances Data Bank
HEDP Hydroxyethanediphosphonic acid
IR Induction rate in the Ames and umu tests
IUCLID International Uniform Chemical Information Database
IUPAC International Union of Pure and Applied Chemistry
IPPC directive EC-directive Integrated Pollution Prevention and Control
KBwS Kommission zur Bewertung wassergefährdender Stoffe
LAGA Länderarbeitsgemeinschaft Wasser
LC50 50% lethal concentration
MW Molecular weight
MQ Mean water flow
NTA Nitrilotriacetate
OECD Organisation for Economic Co-operation and
Development
OSPAR Oslo/Paris Convention for the protection of the marine
environment of the Northeast Atlantic
PBTC Phosphonobutanetricarbonic acid
PEC Predicted environmental concentrations
PNEC Predicted no effect concentration
QAV Quarternary ammonium compounds
RTECS Register of Toxic Effects of Chemical Substances
SCAS-Test Semi-continuous activated sludge test
TEGEWA Verband der Textilhilfsmittel-, Lederhilfsmittel,- Gerbstoff-
und Waschrohstoff-Industrie e.V.
VCI Verband der Chemischen Industrie
VGB Technische Vereinigung der Großkraftwerksbetreiber e.V.
WF Growth factor in the umu test
WGK Wassergefährdungsklasse
VwVwS Verwaltungsvorschrift wassergefährdender Stoffe
 1

0 Summary

In power plants and industrial processes non-recoverable heat released during the
use and conversion of energy is removed from the industrial processes by cooling
systems. Water is the most important coolant medium used. In Germany about 27
billion. m3 cooling water (109 m3) are discharged per year from power plants mainly
via once-through cooling systems. To this, about 5 billion m 3 from industrial plants
must be added, of which about 376 million m 3 comes from plants with open
recirculation cooling systems. The water consumption of open recirculation systems
amounts to only 2-5% of that of open cooling systems at equal cooling capacities.
Nevertheless, the water added to the system to compensate the loss of water due to
evaporation or blow down ("make-up water") regularly has to be conditioned with
biocides, scale inhibitors, dispersants and/or corrosion inhibitors, in order to prevent
disturbances of processes by depositions (scaling), corrosion or bio-mass growth
(fouling).

Within the research project the input of cooling water chemicals was evaluated,
identifying the chemicals from product information, calculating their loads from
consumption data of more than 180 cooling plants and investigating the basic
characteristic data needed for an environmental hazard assessment. Additionally, 12
water samples from 7 companies and 11 products have been evaluated in biological
test systems. The elimination of eight cooling water biocides has been determined,
using the luminescent bacteria assay and batch tests with defined inoculum
concentrations (30-1000 mg d.s./l).

Generally, the cooling water samples showed only low ecotoxicity in the algae,
Daphnia and luminescent bacteria assays if the elimination time of the biocides is
considered. With systematic backtracking, the genotoxicity of the cooling water from
one company in the umu-assay could be attributed to one biocide with
isothiazolinones and Bronopol as ingredients. No effects of the water samples have
been detected with the Ames test, although several products proved to be mutagenic
in the Ames test. The elimination of biocides in batch tests, as measured with the
luminescent bacteria toxicity test, showed that isothiazolinones and quarternary
ammonium compounds were better removed with higher inoculum concentration due
 2

to their adsorption to activated sludge. In contrast, the elimination velocity for 2,2-
dibromo-3-nitrilopropionamide (DBNPA) increased with increasing pH. For the
oxidative biocide bromochlorodimethylhydantoin (BCDMH) only a weak dependence
on inoculum concentration was observed, while Bronopol showed a distinct toxicity at
low inoculum concentrations even after 8 days. Therefore, the test conditions for the
determination of elimination curves, which determine the period the circuit must be
closed after a shock treatment with non-oxidizing biocides according to Annex 31 of
the German Waste Water Ordinance, must be clearly defined. Inactivation curves
performed applying the test conditions of the VCI-working group "Biocides in cooling
systems" with high inoculum density (activated sludge with 500 mg d.s./l) favor
elimination by adsorption, and the test design corresponds to an inherent bio-
degradation test. Comparable biomass concentrations normally were not found in
cooling systems. If additional information is required, especially for directly
discharged cooling water, results about ready bio-degradation and/or elimination
curves at lower inoculum concentrations (i.e., 30 mg d.s./l corresponding to the test
conditions of the OECD 301 "Ready bio-degradability" tests) should be demanded.

The overall accounting of chemical loads in a balance sheet confirmed that the
principal amounts came from open recirculation cooling systems, whereas only
<10% of the plants with once-through cooling water used conditioning chemicals at
all. The extrapolation of consumption data for Germany gave total loads of about
4000 t/a oxidative (mainly chlorine, chlorine release agents, BCDMH and hydrogen
peroxide) and 125 t/a non-oxidative biocides (mainly isothiazolinones, DBNPA and
quaternary ammonium compounds). Additionally, inputs of about 1500-2200 t/a
phosphonic acids, 45-135 t/a molybdate and 113-216 t/a zinc were calculated.

The questionnaire for actual cooling systems in operation uncovered distinct

capacities for improvement. In 34 out of 110 facilities with open recirculation cooling
systems ground water was used for cooling purposes, and in 12 cooling systems
drinking water (in three systems more than 100,000 m 3 drinking water per year!).

Divergent from the requirements of Annex 31, biocides were continuously added in
some open recirculation and flow-through cooling systems. Among these was one
 3

power plant using salt water as coolant, as well as plants of the chemical and
foodstuff industries. Of course, for foodstuffs hygiene requirements (product safety)
are more important than the prevention of biofouling in the cooling system.

According to the operators’ statements, the recirculation water of closed cooling

systems is often discharged indirectly via municipal treatment plants and only in
isolated cases directly into the recipient water. No luminescent bacteria test results
were available for two thirds of the cooling systems, although 40% of them directly
discharged the cooling water. Only in some cases did operators indicate that
elimination curves of the biocides used have been submitted. As a rule, only the
period of time for which the circuit must be closed after a treatment with biocides is
documented as specified by the producers of conditioning chemicals. Concrete
examples have also been presented in which the usage of chemicals has been
reduced up to 90% by simple technical or organizational measures (cleaning,
shading of cooling towers from the sun).

Basic substance data sheets were documented for all chemicals applied, based on
extensive literature and data bank/database researches, enabling first assessments
of environmental relevance using several approaches of hazard assessment.

For some chemicals (e.g., butylbenzotriazole, chlorotolyltriazole, tetraalkylphos-

phonium chloride) considerable data gaps exist. With reference to the BREF-
document of the EU-Commission about "the application of best available techniques
to industrial cooling systems", different approaches regarding the selection and
optimizing of cooling water chemicals are described. There is a clear confirmation
that this issue cannot be examined separately from the complex thermodynamic
processes, the water quantity available and the site specific characteristics. A
combination of emission- and water-quality-based criteria is recommended to assess
cooling water chemicals. The advantage of emission-based approaches based on
the classification system of harmful water pollutants according to the European R-
phrases of the dangerous substances directive is that, along with the aquatic
ecotoxicity, other protection areas such as health aspects or soil conservation are
considered. Additionally, insufficient databases were considered for the assessment,
following the precautionary principle. However, in order to draw attention to the loads
emitted, both the consumption amount as well as the elimination in cooling systems
 4

and (for indirectly discharged water) municipal treatment plants should be

emphasized, as described in the TEGEWA-concept for indirect discharges. The
advantage of water-quality based approaches such as the "benchmarking"-concept
based on the predicted environmental and effect concentrations is that the intrinsic
properties of chemicals such as bio-degradability and ecotoxicity are combined and
the site specific characteristics are considered. Nevertheless, this approach focuses
on the environmental quality standards for surface water derived from chemical risk
assessment, and the rule of load minimizing seems to be less important when the
water flow capacity of the recipient water is considered to be sufficient. The
determination of toxicity loads (=effect concentration multiplied by load) is a possible
further development of the "benchmarking"-concept. Prequisites for the assessment
of conditioning cooling chemicals are that chemicals can be identified unambiguously
in product descriptions and that data gaps will be closed.
 5

1 Introduction

In power plants and industrial processes non-recoverable heat released during the
use and conversion of energy is removed from the processes by cooling systems.
Due to its high heat capacity water is the most important coolant medium used. Apart
from surface water from rivers and lakes also sea, ground or drinking water is used
for cooling purposes.

Along with the organic and inorganic constituent compounds of this water, non-
negligible amounts of air pollutants, which might cause scaling, growth of
microorganisms and corrosion, are also washed out by cooling water due to the high
air turnover of cooling towers. Hence, the cooling water often is conditioned with
dispersants, corrosion inhibitors and biocides. As wastewater treatment of cooling
water is usually not applied, these chemicals are discharged with the ”blow down”
into the sewer or (from directly discharging plants) into the receiving water.

Within the project a systematic evaluation of the input of cooling water chemicals into
German surface water was carried out. To accomplish this, the chemicals used were
identified from product information, their loads were calculated from consumption
data of more than 180 cooling plants, and the basic characteritic data needed for an
environmental hazard assessment were compiled. Additionally, the effects of cooling
water samples and products were determined in biological test systems. Batch tests
were performed under defined conditions in order to measure the elimination of
cooling water biocides.
 6

2 Current knowledge

2.1 Fundamentals

Cooling systems can be distinguished as once-through systems, as well as open and

closed recirculation systems, and their combinations (Held and Schnell 2000,
Anonymous 2001c). In once-through cooling systems cooling water is used without
recirculation, i.e., the warmed water is directly discharged into the receiving water.
Often once-through cooling is applied in combination with a cooling tower, where the
cooling water is trickled in order to remove part of the heat via evaporation cooling.
Once-through cooling systems demand a large water supply. For instance, power
stations with a difference between in- and outlet temperature of 10°C consume, as a
rule, about 3.5 m 3 cooling water per 100 MW installed electric capacity (Fichte et al.
2000).

Open recirculating cooling systems are wet cooling circuits open to the air, where the
water used for cooling purposes is cooled down by evaporation. As a first
approximation one can assume that in open recirculating systems 70% of the heat
amount is removed by evaporation. The evaporation loss depends on the cooling
capacity and the climatic conditions. As a rule of thumb it can be assumed that, per
10°C temperature elevation, 1.1% to 1.6% of the circulating water flow evaporates in
Central Europe (Fichte et al. 2000, Sommer 1988). Additionally, droplet losses of
about 0.1% of the circulating water flow are emitted. Hereby, cooling water
ingredients are usually concentrated by a factor of 2-4. The concentration factor is
adjusted via the blow down (draining of cooling water to the recipient water body or
municipal treatment plant). The evaporation losses and the blow down are
compensated by the make-up water. The fresh water supply of open recirculating
systems amounts to only 2-5% of that from once-through cooling systems at equal
cooling capacity.

Besides the above mentioned, there are also closed circuit cooling systems (dry air-
cooling), which are operated without wastewater emissions and are usually applied
at high process temperature levels above 50°C. Hybrid cooling systems combine the
wet and dry cooling principles.
 7

2.2 Cooling water flow

The discharge of cooling water into surface water has substantial significance for
water economy. The water resource balance shows that about 40% of the
precipitation drained off in Germany is used for cooling purposes, whereas significant
differences in the river basins can be observed because of to regional industrial main
areas and the varying water flow of the principal water recipients. For example, the
proportion of cooling water from the total flow of the Elbe and Rhine Rivers is above
60%, while the proportion from the Danube River amounts only to about 10% (Table
1; Table 2).

Table 1: Cooling water discharge in river basins (1995) [Mio. m 3]

coast
and
River basin Donau Rhein Maas Ems Weser Elbe sea Oder sum
Cooling water discharges of mining and
industry 536,7 3.621,7 17,1 34,8 175,9 597,4 16,7 45,5 5.045,9
direct dischargers 500,5 3.527,7 15,1 33,0 156,4 532,8 15,6 45,4 4.826,4
indirect dischargers 36,3 93,9 2,0 1,8 19,6 64,6 1,2 0,1 219,4
Cooling water discharges from power
industry for public supply 1.974,6 12.603,0 n.a. 62,1 4.647,8 7.178,9 880,3 1,0 27.347,7
Source: Statistisches Bundesamt Fachserie 19, Reihe 2.2, 1998
Maas=sum of cooling water of the Rur, Schwalm and Niers Rivers

Table 2: River flow volume balance for Germany in 1992

coast
and
River basin Donau Rhein Maas Ems Weser Elbe sea Oder sum
3
Average runoff into BRD [m /s] 579 1225 253 n. a 2057
3
Average runoff from BRD [m /s] 1346 2043 32 111 347 610 201 11 4701
3
Runoff from area of BRD [m /s] 767 818 32 111 347 357 201 11 2644
Cooling water effluents in total [m3/s] 80 514 1 3 153 247 28 1 1027
Proportion of cooling water from MQ with
runoff into BRD 6% 25% 40% 14% n. a 22%
Proportion of cooling water from MQ from
area of BRD 10% 63% 2% 3% 44% 69% 14% 13% 39%
Source: Statistisches Bundesamt Fachserie 19, Umweltökonomische Gesamtrechnungen, August 1994
3
Statistisches Bundesamt Fachserie 19, Reihe 2.2, 1998, changed to m /s
MQ = Average runoff in 1992 of the respective draining areas of rivers; BRD=Federal Republic of Germany

The power plants for public supply, with 84% of all cooling water discharges, are the
most important dischargers. Only 219 million m 3 cooling water from mostly small
companies were indirectly discharged via municipal sewage treatment plants, so the
cooling water proportion of municipal wastewater amounts to only 2-3 % of the total
by volume. Thus, nearly all the volume of cooling water (>99%) is discharged directly
 8

into the receiving water course. Conequently the chemicals used for cooling water
conditioning immediately enter the receiving water, so that a particular risk potential
might arise, unless the chemicals are inactivated in the cooling system itself.

Considering the different industrial sectors of cooling water dischargers (cf., table 3)
it is evident that, next to the power plants for public supply, in particular the chemical,
mining and metal industries are the principal dischargers of cooling water. From the
proportion of "used" and "discharged" cooling water a "utilization factor" can be
calculated. This factor gives an indication of the importance of open recirculating
cooling systems in the respective industrial sector. (The data on cooling water
utilization also contain the recirculated volume and multiple-shift uses for different
purposes.)
 9

Table 3: Ratio of used/discharged cooling water (1995)

Water used for cooling purposes
Discharged
Water used for cooling water Utilisation factor *)
cooling without treatment
*1000 m3 *1000 m3

Power plants for public supply 61.759.994 27.347.665 2,3

Mining industry 5.616.335 812.998 6,9
Foodstuff and tobacco industries 905.610 161.889 5,6
Textile industry 176.554 145.123 1,2
Leather industry 4.170 317 13,2
Wood manufacturing 41.723 11.609 3,6
Paper and printing industry 683.511 390.528 1,8
Coking plant and petroleum processing 2.415.387 127.419 19,0
Chemical industry 11.333.036 2.488.627 4,6
Rubber ware production 640.606 65.111 9,8

Glass, ceramics and stone commerce 382.479 28.497 13,4

Metal products and manufacturing 5.091.455 616.186 8,3
Engine construction 236.904 26.284 9,0
Production of office machines, electrical
engineering 393.444 59.964 6,6
Vehicle construction 1.143.730 108.069 10,6

Production of furniture etc., recycling 50.581 3.261 15,5

Sum of industrial cooling systems 29.115.525 5.045.882 5,8
Grand total of all cooling systems 90.875.519 32.393.547 2,8
Reference: Statistisches Bundesamt Fachserie 19, Reihe 2.2, 1998
*) The Utilisation factor here refers to the discharged cooling water and not to the make-up water!

2.3 Minimum requirements for cooling water discharges in Germany

In Germany the discharge of cooling water is regulated in Annex 31 of the

Framework regulation for wastewater. Here inter alia the following requirements are
given:

• With the exception of phosphonates and polycarboxylates exclusively complexing

agents which are readily bio-degradable may be used,

• The wastewater must not contain chromium, mercury or organometallic

compounds,

• The concentrations for chlorine, AOX, COD, phosphorus and zinc are limited,
 10

• For fresh water cooling systems a shock treatment with microbicidal substances
is limited to oxidative biocides (chlorine, chlorine dioxide, hydrogen peroxide,
ozone).

• After a shock treatment with a biocidal substance the blow down of recirculating
cooling systems is only allowed if the luminescent bacteria toxicity does not
exceed GL =12 (GL= Lowest ineffective dilution factor, LID).

Annex 31 currently is being revised and will be in force in 2002 (Anonymous 2001). A
background paper (draft of the Bund/Länder GK 21/41 from 17.12.2001) will also be
published in 2002.

In the course of the implementation of the EC-directive 96/61/EC concerning

Integrated Pollution Prevention and Control (IPPC-directive) an extensive "Reference
Document on the Application of Best Available Techniques to Industrial Cooling
Systems" was elaborated, which is available in the internet (http://eippcb.jrc.es). The
aim of the IPPC-directive is to optimize the operation of industrial plants, so that
while considering energy efficiency and waste avoidance no substantial pollution of
the environment will be generated. Hereby measures for the improvement of one
environmental compartment (e.g., water) shall not lead to additional stress of another
compartment (e.g., air). The reference document offers a comprehensive
documentation for the selection of cooling systems, technical descriptions and
potential environmental effects. It is clear that the cooling system cannot be
considered separately from the industrial process and location. By optimizing the
overall process substantial amounts of energy can often be saved. In addition, the
excess energy should be used insofar as possible, for example for hydrothermal
heating projects. Although in the reference document approaches for evaluating the
chemical additives in cooling systems are described (cf., sect. 7.4), until now there
has been no systematic presentation of the basic data required for this, both on the
input side (consumption data), as well as on the material, chemical side
(degradability, ecotoxicity, genotoxicity, bioaccumulation).

2.4 General environmental hazards from cooling systems

In the operation of cooling systems a complex field of tensions between various

usage interests and environmental conflicts arises. The water consumption is highest
 11

for once-through cooling systems and for larger power plants this can exceed several
m3/s. Depending on the mesh width of the inflow rates to the cooling system and the
flow rate, substantial numbers of fish, especially young ones, can be sucked in and
killed (up to 25 fish per 1000 m 3; Anonymous 2000). The temperature increase in the
surface water leads to a reduction of the oxygen solubility in the water together with
an increase in the metabolic activity. Since this can lead to a shift in the species
spectrum in the waters (LAWA 1991), heat load plans have been prepared for the
waters. The EU-Guideline 78/659/EWG specifies for Salmonid and Cyprinid waters,
among other things, the maximal permissible temperature elevations (1.5°C and 3°C)
and maximal temperatures (21.5°C and 28°C, and, during the spawning period of
cold-water fish, for certain waters 10°C; 78/659/EWG 1978).

For cooling towers a large part of the heat burden is released as latent heat
(evaporation) and causes an increase of the air temperature, which can lead to
changes in the local microclimate (VDI 3784: 1986). For large power plants natural-
draft wet cooling towers are used, for which the construction height provides
sufficient force to drive the air current. For ventilator cooling towers the necessary
amounts of air are, in contrast, introduced by forced air blowers, for which electrical
energy must be provided (corresponding to 0.5-2% of the amount of emitted heat
energy, Anonymous 2000). For open recirculation cooling systems the water
consumption is usually reduced by ca. 95%-98% compared to once-through cooling
systems at equal cooling capacity. At the same time, however, the electrical energy
needed for the pumps is increased by ca. 50% thus amounting to ca. 1.5% of the
amount of emitted heat energy. The evaporation losses can be taken to be ca. 0.4-
0.7 l/s per 1000 MW of output electricity (Wunderlich 1978b). This leads to an
increase in the concentration of the constituent compounds in the water, so that
often a purification of the water and/or a conditioning of the cooling water is
necessary, which then requires the addition of chemicals to the receiving waters.

The most urgent goal of the plant management of cooling systems, however, is their
efficiency and protecting the system against depositions (scaling), corrosion and
biomass growth (fouling). The formation of depositions on the cool water side of a
heat exchanger or pipeline interferes with heat transfer and increases the loss of
pressure, so that the performance is substantially reduced. Ultimately, this leads to a
 12

higher water consumption and must be compensated by an increased application of

energy. Thus, a calcium deposit 0.5 mm in thickness reduces heat transfer in
condensers by ca. 20% (Todutza and Steinlein 1990). Corrosion processes not only
damage the system, but also increase the risk of leaks on the production side. In
addition, the corrosion products endanger the waters.

A control of the biomass growth is performed with the additional goal of minimizing
the microbiological risks arising from the cooling plant. It is known, for example, that
thermophilic human pathogens, especially Legionella pneumophilia, which causes a
severe pneumonia (Legionnaire’s disease), can be found in cooling systems (States
et al. 1987, Kusnetsov et al. 1997, Werner and Pietsch 1991, Howland and Pope
1983, Kusnetsov et al. 1993). Guidelines for controlling Legionella in cooling systems
are available (Anonymous 2001a).

2.5 Cooling water conditioning

For the prevention of scaling in recirculation cooling systems, dispersants and

hardness stabilizers are added. In addition, corrosion inhibitors and biocides are
used, whereby there are overlaps between the individual groups (e.g., phosphates
act both as hardness stabilizers and corrosion inhibitors).

2.5.1 Dispersants and hardness stabilizers

The precipitation of salts due to their exceeding their solubility limits is termed
scaling. Of particular interest in cooling systems is the precipitation of calcium
carbonate and calcium phosphate, and to a limited extent also calcium sulfate and
silicates. The hardness of the water can also be reduced by active decalcification
(precipitation with calcium hydroxide). The residual hardness is either removed by
conversion of the carbonate hardness into non-carbonate with acids (primarily
hydrochloric and sulfuric acid) or stabilized through the addition of hardness
stabilizers such as orthophosphate, polyphosphates and phosphonic acids. The
ready hydrolysis of polyphosphates to orthophosphate and the associated danger of
calcium phosphate deposition led to the development of stable phosphonic acids,
which are added in sub-stoichiometric amounts (Andres et al. 1980). The most
important phosphonic acids used in the field of cooling water treatment are aminotri-
methylenephosphonic acid (ATMP), hydroxyethanediphosphonic acid (HEDP) and
 13

phosphonobutanetricarbonic acid (PBTC). Organic polymers based on polyacrylic

acid, polymetacrylic acid, polymaleic acid and polyacrylamide (so-called
polycarboxylates) also have a certain hardness stabilizing effect and are often used
in combination with phosphonic acids.

The calcium carbonate hardness can be stabilized with, e.g., carboxymethylcellulose.

To a limited extent complex formers (NTA) are used; EDTA is however excluded de
facto from use because of its poor degradability.

Further depositions can also be caused by the precipitation of suspended organic

and inorganic particles and iron oxides. To prevent this, dispersants based on the
above mentioned polycarboxylates as well as low-molecular weight anionic acids
(e.g., succinates) are added. These are to be distinguished from natural products,
such as lignins and tannins, and from synthetic polymers of the polyacrylic,
polymetacrylic, and polymaleic acids as well as sulfonates. The transition between
the hardness stabilizers and the dispersants is not clear-cut.

2.5.2 Scale inhibitors

The corrosion of metals is enhanced by the presence of oxygen, salt content

(especially chlorides) and a low pH, but also by deposits. During oxygen corrosion
metal ions are dissolved at the metal surface, which acts as the anode, while in the
cathodic reaction oxygen is reduced to hydroxide ion and a high pH is produced
locally (Anonymous 1991). Of particular importance is microbially induced corrosion,
which is caused by acidic metabolic products as well as the anoxic/anaerobic
conditions within biofilms. Sulfate-reducing bacteria of the genus Desulfovibrio act
corrosively, by reducing the sulfate while forming hydrogen sulfide. These bacteria
are among the most important in cooling systems (Koppensteiner 1973). However,
corrosion can also be induced by sulfur bacteria (Thiobacillus), iron bacteria
(Ferrobacillus, Gallionella) and nitrifying bacteria (Nitrosomonas, Nitrobacter).

Passive (anodal) corrosion inhibitors, such as phosphates, phosphonates, nitrite,

silicates and molybdates form a passive protective layer on the metal surface. The
use of chromate is no longer permitted. In contrast, cathodic inhibitors like zinc or
calcium carbonate, and to a limited extent also orthophosphate, form insoluble
deposits which protect the metal surface by reacting with the corrosive hydroxyl ions.
 14

Especially for copper and copper alloys, 1,2,3-triazoles are used as inhibitors.
Mercaptobenzthiazoles may no longer be used for this purpose according to Annex
31 of the AbwV regulations.

2.5.3 Biocides

The mean temperature in water cooling systems is ca. 35°C and thus lies just below
the temperature optimum of most microorganisms (Mattila-Sandholm and Wirtanen
1992). Biocides are used to control biologically induced deposits and corrosion
processes. For cooling water systems algicides, fungicides and molluscicides are
relevant.

2.5.3.1 Biology in cooling systems

The growth of autotrophic algae is dependent on the presence of mineral nutrients,

carbon dioxide and light energy, while the growth of heterotrophic bacteria requires
organic material, which is composed of dead algae and/or the existing burden of the
water or air. In principle, bio-degradable conditioning agents can also function as a
carbon source. Many bacteria secrete a highly hydrated slime consisting of
polysaccharides, which leads to the formation of biofilms on surfaces (biofouling).
Biofilms decrease heat exchange, promote corrosion and hinder control by means of
biocides. Protozoa such as Ciliates or Amöbae colonize affected cooling towers as
consumers, as do higher organisms such as mussels and snails, which can lead to
serious disturbances.

In once-through cooling systems, because of the short retention time and the
requirement for a rapid elimination, fast-acting oxidative biocides are used; and in
open cooling systems, non-oxidative, more stable organic biocides are called for.

2.5.3.2 Oxidative biocides

The most commonly used oxidative biocide, owing to its effectiveness and low price,
is chlorine or cholorine bleach (sodium hypochlorite). At the pH-values of > 8 typical
for cooling system circulation, there is a reduction of the biocidal effect of the active
substance, hypochlorous acid (HOCl), while hypobromous acid is still effective at pH
9. Hypobromous acid is generally generated on site by adding sodium bromide to
sodium hypochlorite (NaOCl). The use of free halogens as biocides may, depending
 15

on the water composition (e.g., DOC- and ammonium concentration), pH-value and
contact time, lead to the formation of disinfectant by-products such as
trihalomethanes, chloro- and bromoamines as well as absorbable organic halogen
compounds (AOX).

In the purification of drinking water chlorine is replaced in part by chlorine dioxide, in

order to minimize the formation of AOX, especially halogen methanes. Chlorine
dioxide reacts noticably more weakly with complex organic molecules and
ammonium, consequently forming less AOX. Chlorine dioxide is also occasionally
used in the cooling water field, whereby it is usually generated on location through
the reaction of chlorine gas with sodium chlorite (NaClO 2). Organic chlorine and
bromine release agents are used especially in open recirculation cooling systems.
Here, above all, the rapidly hydrolyzing biocide 1-bromo-3-chloro-5,5-
dimethylhydantoin (BCDMH) should be mentioned. Related compounds like 1,3-
dichloro-5,5-dimethylhydantoin or 1,3-dichloro-5-ethyl-5-methylhydantoin are also
occasionally used.

Ozone is a highly effective oxidatively acting biocide. Usually, ozone is continuously

added to the cooling water in very low concentrations of 0.1 to 0.3 mg/l (Wasel-
Nielen and Baresel 1997, Viera et al. 1999). Production is achieved directly on
location using high voltage, In comparison with the other oxidative biocides,
hydrogen peroxide is only effective at higher concentrations (> 15 mg/l; cf., van Donk
and Jenner 1996) and has a short half-life. Rarely, peracetic acid is also used as an
organic oxygen release agent in cooling systems. Under unfavorable conditions,
peracetic acid is corrosive. This chemical is readily bio-degradable.

2.5.3.3 Non-oxidative biocides

Non-oxidative biocides are used nearly exclusively in open recirculation cooling

systems, where the contact time of the cooling water with the biocide suffices for a
satisfactory effect. As a rule, here the biocide is added batchwise in a shock
treatment.

One of the most important non-oxidative cooling water biocides, a mixture consisting
of a chemical belonging to the isothiazolinone family, 5-chlorine-2-methyl-4-
isothiazolin-3-one, together with 2-methyl-4-isothiazolin-3-one, is already effective at
 16

concentrations below 1 mg/l. Isothiazolinones hydrolyze slowly (t 1/2 = 7 d at 30°C and

pH 8) and are not readily bio-degradable. Quarternary ammonium compounds (QAV)
act through their binding to the cell membrane and are also not readily bio-
degradable. During passage through the sewage treatment plant they are largely
eliminated by adsorption on the activated sludge. The most important representative
in the cooling water area is alkyldimethylbenzylammonium chloride.

The addition of dibromonitrilopropionamide (DBNPA) is also widespread in the

treatment of cooling water. This compound hydrolyzes rapidly to the still partially
biocidally active compounds dibromoacetonitrile, dibromoacetamide, monobromo-
nitrilopropionamide and cyanoacetamide. Further members of the organic bromine
compound group include 2-bromo-2-nitropropan-1,3-diol (Bronopol) and beta-bromo-
beta-nitrostyrene.

Glutardialdehyde is also rather frequently used in the cooling water field. The
mechanism of action is based on the denaturation of proteins. Glutardialdehyde is
less toxic for aquatic life forms as compared to the other biocides, and the
concentration added is correspondingly higher. This compound is readily bio-
degradable. Specifically for the control of algal growth additional biocides are used,
such as copper sulfate, as well as photosynthesis inhibitors based on triazine-
derivatives.

To reduce the risk of the appearance of microorganisms resistant to the added

biocides combination products containing several biocides are used.

2.5.3.4 Elimination of the biocidal effects

A basic requirement for cooling water biocides is that their damaging action or
biocidal effects must diminish in a relatively short time, since otherwise there might
be toxic effects on the surface waters, especially after the direct discharge of cooling
water. This calls for a rapid hydrolysis and/or biological degradability of the biocides.
For indirect emissions via municipal sewage treatment plants it has to be proven that
the biological wastewater treatment is not inhibited and that the biocides are retained
in the treatment plant. Preferably, the biocides should be biologically degraded.
While elimination through adsorption on the activated sludge (cf., QAV) protects the
 17

receiving water, this merely shifts the problem, when the collected sludge is spread
on the land for agricultural or forestry use.

The elimination of the biocidal effects can be assayed either in the laboratory or on
site at the actual treatment plant. For the completion of such so-called ”elimination
curves” in the laboratory there are, however, no generally acceptable specifications
to date. Here the manufacturers have proposed static experiments with relatively
high concentrations of activated sludge (0.5 g d.s./l), in order to simulate the
influence of a hypothetical biofilm in the cooling system circulation (Scheidel et al.
1996). Other authors, on the other hand, determine an elimination curve without
adding any inoculum (Gartiser and Scharmann 1993, Gellert and Stommel 1995,
Baltus et al. 1999).
 18

3 Goals and investigative strategy

In accordance with the project description, the following goals have been set:

• Estimation of the emission of cooling water conditioners in flowing surface waters

of the Federal Republic of Germany

• Determination of the introduced cooling water chemicals and investigation with

respect to their ecotoxicity, genotoxicity, bioaccumulation and degradability

• Determination of current practices of the governmental control agencies in the

individual Bundesländer

• Extension of the data status on ecotoxicity, genotoxicity and biological

degradability of the cooling water chemicals in use through measurements of our
own

• Develop suggestions/proposals for the reduction and optimization of the addition

of cooling water chemicals

• Develop a recommendation for the selection of cooling water chemicals based on

the present technical state of the art

The investigative strategy is based on three pillars (see Fig. 1):

• Literature and database research on the active ingredients/substances of the

standard commercially used cooling water conditioners

• Drawing up of an overall accounting balance sheet of the loads and

concentrations of cooling water conditioners in treatment systems

• Direct testing of cooling water samples, products and active ingredients with
respect to their ecotoxicity and genotoxicity, as well as determining the rate of
elimination of biocides (elimination curves)
 19

Research Overall Balance

- Products
- Active substances
- Elimination of biocides
- Ecotoxicity, Biodegradability
Genotoxicity
- Consumption data of plants
- Wastewater concentration
- Total volume loads in BRD
- Total loads of active Subst.

Practice of Comparision of
regulatory data State of the art
control

Elimination of
biocides/
Products

Active substances/
Products

Cooling water

Tests

Figure 1: Investigative strategy

 20

4 Methods

4.1 Laboratory investigations

4.1.1 Cooling water samples

Cooling water samples from 7 treatment plants in Southern and Northern Baden
were investigated. All these plants have open recirculation cooling systems.
Collection of the samples was as qualified test samples direct from the investigated
cooling vessel or from the return flow of the circulation (DIN 38402 1991). The
descriptive data of the investigated cooling water with respect to water consumption
and the products added are presented in Table 4.

a) Plant 1, Electroindustry

The operation of a semi-conductor manufacturer has six cooling towers with a total
cooling capacity of 2.5-3 MW. The cooling tower investigated has a cooling capacity
of 1.2 MW and removes the heat produced by a refrigeration system. As a special
feature, the concentrate of the water treatment (reverse-osmosis system with a
capacity of 700 µS/cm) is used as cooling water. For hardness stabilization and
corrosion inhibition a product based on sodium phosphonates, sodium molybdate,
sodium polycarboxylates and triazoles is added continuously. As a biocide,
isothiazolinone is added in summer as needed. Through regular mechanical cleaning
of the cooling vessel and an adequate shading of the cooling tower the amount of
this chemical added was reduced by more than 90% compared to the previous
years. The yearly consumption of isothiazolinones in the year 2000 was ca. 0.4 kg/a
of active substance. At the time of sampling no biocides were being added.

b) Plant 2, Plastics manufacturing industry

The company manufactures molded plastic parts for the automobile industry and has
several cooling towers with a total capacity of 6700 kW, which are fed with ground
water. As biocide a quarternary ammonium compound is added batchwise as
needed and then the outflow is closed for the next three days. The time of addition is
decided upon by visual examination of the algal growth. In addition, corrosion
 21

inhibitors and hardness stabilizers based on phosphonic acids, zinc chloride and
dispersants are continuously added.

The first sample collection on 19.07.00 took place two months after a shock
treatment with biocides, and the second and third samples were taken either directly
after the biocide was added and after an elimination time of three days resp. Besides
the cooling water, the wastewater produced from the released steam, to which
hydrazine was added, was also examined.

c) Plant 3, Plastics manufacturing industry

The plant manufactures PVC-foils and has a cooling tower with a capacity of 2.3-9.2
MW. Ca. 250 m3 of completely desalted cooling water are added weekly. In the non-
shaded cooling tower problems with algae arise. In this event, a "heterocyclic
sulfur/nitrogen-compound" (Isothiazolinone) is added batchwise in a shock treatment
(total load 0.8 kg/a active ingredient).

d) Plant 4, Plastics industry

The plant of a manufacturer of adhesive foils has four cooling towers, whose function
is to thermally reclaim solvents from activated charcoal filters. About four times a
year a preparation based on isothiazolinones is added batchwise (ca. 30 liters of
product/a). After a retention time of 24 h according to statements from the operator,
the GL-value is ascertained to be below 12. As hardness stabilizers polycarboxylates
and phosphonocarboxylates are added continuously. At the time of the collection of
the first sample, there was no addition of biocide, and the second sample was taken
24 h after a biocide treatment just after the outflow was reopened.

e) Plant 5, Plastics manufacturing industry

The plant manufactures foamed polystyrene- and polypropylene-packaging and has

three cooling towers. For the foaming of the plastics 10-12 t/h of desalted boiler
feeder water (steam) is needed. The boiler feeder water is treated with a corrective
material and the condensed steam (condensate) enters the open cooling system
during the production process. Thereby solid materials from the production process
are also carried over and are removed from the cooling water circulation with bag
filters (towel filters). These filters are cleaned daily. Twice weekly 60 liters of a
 22

biocidal product based on hydrogen peroxide and quarternary ammonium

compounds are added. The cooling water sample was taken in the filter outflow 7 h
after a batch treatment.

f) Plant 6, Chemical industry

The plant has two cooling water systems, which were both sampled. The plant
cicrculation (KW1) has four forced-aeration cooling towers and is operated with a low
compression ratio of 1.1. The second circulation (KW2) handles the central cooling
system and is run at a high cycle of concentration of 3.0. Both circulations are
treated continuously with the biocide 1-bromo-3-chloro-5,5-dimethylhydantoin. As
needed, a product based on 2-bromo-2-nitropropan-1,3-diol and isothiazolinones is
added. For corrosion inhibition phosphonic acids and tolyltriazole are continuously
added.

g) Plant 7, Chemical industry

This pharmaceuticals producing operation set up a new cooling system for the
expansion of the refrigeration plant. A portion of the drinking water needed for
feeding this system is completely desalted by an ion-exchanger. The cooling water is
treated twice weekly for several h with the biocide 1-bromo-3-chloro-5,5-
dimethylhydantoin. To inhibit corrosion phosphonic acids and triazoles are added
continuously. The sample was collected 24 h after the last biocide treatment after
opening the outflow.
 23

Table 4: Charateristic data for the investigated systems

Firm Water consumption Principle Products
Active Active Active Active
ingredient 1 ingredient 2 ingredient 3 ingredient 4
3 3
Branch [kW] [m /a [m / Concen Pro- Bioci Pro- Dis Co Load Conc. Loa Conc. Load
] (a*KW)] tration ducts de- duct cha nc. [kg] [%] d [%] [kg]
ratio additi [kg/a] rge [%] [kg]
on

Nr. 1 2.500 14.402 5,8 RO OK Biocide 1 10 KA CMI 2,4 0,2 MI 2,4 0,2
Electro- TW Product S 457 Triazoles 2,5 11,4 NaOH 2,5 11,4 Phosphonate Na.molybdate
industry Product 90 HCl 21,0 18,9 (without conc.)
Nr. 2 6.700 1.761 0,3 G OK Biocide 3 S 660 KA QAV
Plastics manufacturing 1,8 Product 2250 HEDP 15,1 339,8 ATMP 20,1 452,3 Polyoxy- 10,1 227,3 Zinc chloride
carbonacid (without conc.)
Product 4145 HCl 30,0 1243,4 HEDP 9,9 1,4-Butindiol 9,9 410,3
Nr. 3 3.000 13.000 4,3 VE OK Biocide 4 S 40 KA CMI 0,9 0,4 MI 0,9 0,4
Plastics manufacturing ? PO43- 24 Ortho- 100,0 24,0
phosphate
Nr. 4 18.710 23.579 1,3 G OK Product 900 O Poly- Phosphon-
carbonates carbonate
Foil production 3,0 Biocide 2 S 30 CMI/MI
Nr. 5 4.000 2.600 TW OK Biocide 5 S 6240 KA H2O2 QAV
Plastics manufacturing NaOH 3120 NaOH 25,0 780,0
Product 1200 Polyethoxylate Non-ion.
Tenside
Nr. 6 Chemical Industry 7020 NaOH 3,5 245,7 Tolyltriazole 3,0 210,6 Phosphonic 7,5 526,5
acid
Circulation 6.300 720.000 114, G OK/1,1 1600 Phosphonic
1 3 acids
Biocide 6 K 644 O and BCDMH 25,1 161,6
Biocide 7 S 125 KA Bronopol 9,0 11,3 MI 1,8 2,3 CMI 1,8 2,3
NaOCl 2000 Sodium- 13,0 260,0
hypochlorite
Circulation 43.500 120.000 G OK/3,0 Product 7350 NaOH 3,5 257,3 Tolyltriazole 3,0 220,5 Phosphonic 7,5 551,3
2 acid
Product 1000 Phosphonic
acids
Biocide 6 K 2323 KA BCDMH 25,1 583,1
Biocide 7 S 25 Bronopol 9,0 2,3 MI 1,8 0,5 CMI 1,8
Nr. 7 6.000 58.000 9,7 TW OK Product Planning KA Polycarbonic 17,5 Phosphonic 6,3 Triazole 2,5
acid acid
Chemical Industry max. 4.0 Biocide 8 S stage BCDMH 75,0
Water consumption: G=Ground water; RO=Reverse osmosis; VE=completely desalted water; TW=Drinking water; Biocide added: K= continuous; S=Batch treatment; Source: O=surface water; KA=municipal water
purification plant; ingredients: CMI: 5-chloro-2-methyl-2H-isothiazolin-3-one; MI: 2-methyl-2H-isothiazolin-3-one; BCDMH: 1-bromo-3-chloro-5,5-dimethylhydantoin; Bronopol: 2-bromo-2-nitropropan-1,3-diol; HEDP: 1-
Hydroxyethan-1,1-diphosphonic acid; ATMP: Aminotrimethylphosphonic acid
 24

4.1.2 Product investigations

Altogether five biocides and one corrosion inhibitor were tested. All of these active
substances are used in the plants investigated. They were tested with respect to
their mutagenicity, genotoxicity and ecotoxicity. At a later time four more products as
well as the biocide Bronopol were investigated in the umu test, in order to to
determine the source of the genotoxicity in the wastewater of one plant by systematic
"backtracking". An additional emphasis was the determination of the elimination
behavior of the most important biocides applied in the cooling water field, using the
fluorescent bacteria test (cf., sect. 4.1.9).

4.1.3 Chemical parameters

pH-value: pH 196 pH-meter from WTW GmbH in Weilheim.

Conductivity: Measuring instrument pH-LF 3001 from Neukumelektronik GmbH in

Straubenhardt.

CSB: Round cuvette test (Dr. Lange Co.): Two-hour oxidation with potassium
dichromate, sulfuric acid, silver- and mercury sulfate at 148 °C in conformance with
DIN 38409 H41.

Chlorine (free and total): Round cuvette test (Dr. Lange Co.): reaction with diphenyl-
p-phenylendiamine (DPD) witih the formation of a colored substance; total chlorine
determined after addition of potassium iodide.

4.1.4 Fluorescent bacteria test according to DIN 38412-34 and Nr. 404 of the
AbwV

The toxicity of wastewater contaminants is detected on the marine bacteria of the

species Vibrio fischeri, which show a natural light production (bioluminescence) that
is closely coupled with their metabolic activity. The decrease of the light intensity
provides a quantitative measure of the toxic effect on the bacteria. The test is
performed with the LUMIS-tox system of the company Dr. Lange, Düsseldorf. The
lyophilized bacteria of the strain Vibrio fischeri NRRL-B-11177 were obtained from
the same company (LCK 482). The wastewater samples were tested without further
pre-treatment after salinizing with sufficient sodium chloride to give a 2% solution
 25

and adjusting the pH-value to 7.0 +/- 0.2. The test result is given as the least
stepwise dilution (GL-value), for which the light emission is inhibited less than 20%.

4.1.5 Alga test according to DIN 38412-33 and Nr. 403 of the AbwV

The chronic inhibitory effect of the cooling water samples on the growth of
Scenedesmus subspicatus, a planktonic fresh-water alga, was determined. For this
purpose, a dilution series of the cooling water sample was made, without any further
preparation, but adding an algal nutrient solution inoculated with a defined algae
suspension (corresponding to 10 4 cells/ml) and incubating under defined light and
temperature conditions. After 72 h, the number of cells was determined
microscopically as a measure for the biomass. The result given is the least dilution
step (GA-value), after which the measured inhibitory effect on biomass production is
less than 20%.

4.1.6 Daphnia test according to DIN 38412-30 and Nr. 402 of the AbwV

The acute toxic effect of wastewater on Daphnia magna STRAUS (Crustacea, clone
5 of the German Federal Health Agency) was determined. The value measured is
the dilution factor G D beyond which no acute toxicity for Daphnia is detected within
24 h. The GD-value corresponds to the least dilution factor by which a wastewater
sample must be diluted in order for 90% of the Daphnia to maintain their ability to
swim. The pH-value of the sample was adjusted with hydrochloric acid or sodium
hydroxide solution to 7.0 – 7.5. No other pre-treatment was performed.

4.1.7 Ames test in conformance with DIN 38415-4

The Ames test is a bacterial mutagenicity test with Salmonella typhimurium. The
Salmonella-bacterial strains used are deficient mutants, which are unable to grow in
histidine-free medium. These histidine-requiring mutants can back-mutate (reversion)
and then are able to form colonies on minimal-agar plates. Each of the Salmonella-
strains has a specific spontaneous mutation rate. The number of back-mutated
bacteria (revertants) above this level provides a measure of the mutagenic potential
of a substance or a sample. Certain mutagens in higher organisms are first activated
by being metabolized (promutagens) or are thereby inactivated. Therefore, to the
bacterial system the needed enzymes are added in the form of rat liver extract S9
 26

(Moltox Co.). The test version used is based on a simplified version of the OECD-
Guideline 471 with the test strains TA98 and TA100. The strain TA98 detects
frameshift mutagens; strain TA100 in contrast is for base pair substitution mutagens
(point mutations). The cooling water samples were sterilized over a membrane filter
(0.45 µm). Up to 1 ml of cooling water per Petri dish could be added. Because of the
substantial effort involved, the samples were initially investigated in the Screening-
Test at only one test concentration. A sample is then classified as mutagenic
according to DIN 38415-4 if in one of the strains with or without S9 an induction
difference compared to the control (solvent alone) of 80 (for TA100) or 20 revertants
(for TA98) is induced and a dose-effect relationship is found. The G EA-value
corresponds to the last dilution step at which the induction difference established for
that strain is not exceeded. Since the wastewater sample in the test is diluted by a
factor of 3 with medium/inoculum, the lowest possible G EA-value = 3 (non-
mutagenic). The number of revertants of the negative controls should be: for TA100
in the range of 80-180 and for TA98 in the range of 15-40 revertants per plate.

In testing substances or products a sample was evaluated as being mutagenic in

accordance with the relevant OECD-guideline if the induction rate (ratio of the
number of revertants in the test plates to the negative controls) exceeded a factor of
2 and a dose-effect relationship existed.

4.1.8 umu test according to DIN 38415-3 and Nr. 410 of the AbwV

The umu test is a genotoxicity test with the gene-technologically modified bacterium
Salmonella typhimurium strain TA1535/pSK 1002. The bacteria are exposed to
various concentrations of the cooling water. Here gene toxins induce the so-called
umuC-gene, which belongs to the SOS-repair system of the cell and which acts to
prevent damage to bacterial genetic material. Through the coupling of the umuC-
gene promoter with the lacZ-gene for ß-galactosidase the activation of the umuC-
gene can be indirectly measured spectrophotometrically at 420 nm through the
formation of a colored product from the ß-galactosidase substrate o-nitrophenyl-
galactopyranoside (ONPG). The induction rate (IR) corresponds to the increase of
the extinction at 420 nm relative to the negative control. In calculating the induction
rates one must take into account the growth factor, which is determined
turbidometrically from the optical density at 600 nm. An inhibition of bacterial growth
 27

is expressed as a reduced growth factor ("Wachstumsfaktor" or WF) compared to the

controls. For growth factors below 0.5 (50% growth inhibition) the results are not
evaluated. The result given is the smallest dilution step G (G EU-value), at which an
induction rate < 1.5 is measured. If a different induction rate is seen upon addition of
S9, the higher of the two values is taken (=G EU-value).

4.1.9 Elimination of biocides

Until now there have been no generally accepted specifications for a procedure to
determine elimination curves in the laboratory. On the part of the producing
companies there have been proposals for static experiments with a relatively high
concentration of activated sludge (0.5 g d.s./l), in order to simulate the influence of a
hypothetical biofilm in the cooling circulation (Scheidel et al. 1996). However, at an
UBA-Workshop on the present project the consensus was arrived at that such high
biomass concentrations in cooling circulation are not usual (cf., table 5, (Gartiser and
Urich 2001).

In order to determine the effect of the inoculum concentration on the elimination

behavior of biocides, various inocula were introduced. As a test-system the Zahn-
Wellens test according to DIN EN 29888 or Nr. 408 of the AbwV was
correspondingly adapted. The tests with activated sludge were supplemented with an
inorganic nutrient solution according to DIN EN 29888; all tests were continuously
stirred and aerated with an aquarium pump.
 28

Table 5: Determination of the elimination of cooling water biocides

Inoculum Concentration Comments

Activated sludge 1 g d.s./l Upper conc. Zahn-Wellens test

" 0.5 g d.s./l Proposal by VCI AG

"Microbiocides in Annex 31"

" 0.2 g d.s.//l Lower conc. Zahn-Wellens test

" 0.03 g d.s./l OECD 301 A, B, C and F

"ready bio-degradation"

Outflow final- - Model for microbiologically active

clarifier inoculum with low d.s.-content

Tap water - predominantly abiotic hydrolysis

The starting concentrations of the biocides were selected on the basis of various
information provided on the effective concentrations of the active ingredients in the
cooling water (Baltus and Berbee 1996; Anonymous 1994, Fielden and Iddon 1997)
and in part reduced further according to updated information from the manufacturers
(Klautke 2001) (Table 9). As the end point, after filtration through a folded paper filter
a bacterial fluorescence toxicity test was performed at dilution step 12 (based on
Annex 31 to the AbwV). For low toxicity, dilution step 2 was also tested.

4.2 Drawing up an overall balance sheet

4.2.1 Compilation of production information materials

Letters were sent to a total of more than 100 firms in the chemical industry that also
offer product groups used in the cooling water field (including algicides, antifouling
agents, bactericides, corrosion inhibitors, dispersants, biocides, inhibitors, and water
chemicals). Addresses were obtained in some cases from the relevant handbooks
but also to a large extent through information provided by the operators of the
cooling plants. Altogether, 49 firms replied that they were not engaged in the cooling
water field. Product information was sent by 22 firms. These materials were of
 29

varying quality (from safety data sheets with little useful information to detailed
product descriptions with ecological evaluations). In order to learn more about the
substances in the products investigated in the context of preparing the balance (cf.,
sect. 4.2.2) the operators of ca. 50 cooling plants were requested to provide the
corresponding safety data sheets. In this way information on 418 products from 35
manufacturers was obtained and evaluated. The active substances documented in
these materials served as the basis for our literature- and database-research (cf., sect.
4.3).

4.2.2 Making a balance sheet of the emissions of cooling water chemicals

The yearly emissions of cooling-water chemicals by the firms considered in the

cooling water sampling were determined on site. In order to extend the data base a
questionnaire was prepared for the operators of the cooling plants, including
questions about the cooling system used, the cooling capacity, the source of the
water, the annual consumption of cooling water chemicals (on a product basis), the
mode of addition of biocides and the parameters controlled. Initially, this was sent to
all business-controlling governmental agencies in Baden-Württemberg and then to
the environmental agencies in all the Bundesländer (usually to the Environmental
Ministry). After the questionnaires had been passed on to the local sub-authorities
and/or the operators of the cooling plants, they were then returned to us either
directly or through the authorities. In some cases, Hydrotox was also provided by the
authorities with lists of addresses of operators of cooling plants, and we then
contacted them directly. Ultimately, 182 questionnaires from 176 operators were
evaluated. Because of incorrect or incomplete data, ca. 1/3 of the firms had to be
contacted again by telephone or by e-mail. In most cases, we ultimately succeeded
in obtaining consistent data sets.

We did not ask about and consequently did not make any systematic balance sheet
for chemicals added in treating the water (decarbonizing, flocculation, production of
VE-water, regeneration of the ion-exchanger). Nonetheless, such consumption data
were provided by some of the operators and were evaluated.

Based on the annual consumption data for cooling water conditioners (on a product-
basis) and the recipes for preparation in product information sheets, the loads of
 30

defined ingredients and chemicals could be estimated. In cases where only an order
of magnitude of the substance concentrations was documented, the following
procedure was followed. Where “less than” or “more than” was given, the next lower
or higher concentration after the decimal was used for the balance. Where
concentration ranges were given, the mean was used. Example:

Given in the production information Assumed for the balance

< 10% 9.9%

> 10% 10.1%

10% - 20% 15%

When no concentration was given, and only the product group was listed in the
product information, typical concentrations from the literature or the available additive
concentrations and product recipes were used. For example, for quarternary
ammonium compounds and polycarboxylates no concentration could be obtained
from the product information sheets.

All data were subjected to a plausibility control. Thereby the annual water
consumption per installed kW of cooling capacity was calculated as a basic
parameter and the following classification was made:

Cooling system spec. water consumption [m 3/(kW*a)]

Once-through cooling system 100 - 1000

Open recirculation cooling system 1 - 100

Closed cooling system 0-1

Deviations from this rule of thumb classification indicated incorrect data or special
features such as the use of hybrid cooling towers, a limited running time during the
year or the like. In addition, the calculated concentrations of introduced substances
in the wastewater of the individual plants were compared with the concentrations to
be added as given in the literature (Anonymous 1994, Baltus and Berbee 1996,
Fielden and Iddon 1997). For implausible concentrations the operators of the plants
were contacted.
 31

Estimating the annual loads for Germany:

In order to calculate to an order of magnitude the total consumption of cooling water

chemicals for Germany the questionnaires of the 176 plants were evaluated in
separate categories of once-through, open recirculation, and closed cooling systems.
The addition of chemicals in closed cooling systems was assumed to be irrelevant
for the wastewater since the amounts added at the time of initial filling can only with
some reservation be assigned to any year’s consumption (instead usually being
disposed of as a concentrate in the garbage when the water is changed). Because of
fundamental differences between industrial cooling systems and power plants (cf.,
sect. 5.4.4.1), the two categories were calculated separately. For the remaining
cooling plants the percentage of plants that used a particular substance or a
substance group was determined. Then the means and medians of the
concentrations (on a substance basis rather than a product basis) were calculated
from the annual water- and substance-consumption. Here the relationship of the
amounts consumed to the added water volumes is a parameter which makes it
possible to take into account the temporal components. (In principle, the substance
consumption could also be derived from the wastewater volumes, but usually these
were not known). For substances which were not continuously added, the calculated
mean concentration generally lies well below the actual concentrations in practice.
However, in individual cases, such as the shock treatment by batchwise addition of
oxidative biocides to the circulation water, higher concentrations could also be
calculated when the system volume is larger than the added water volume (cf., sect.
5.4.5). The estimation of the total loads of the non-continuously added chemicals
(biocides) for Germany was then obtained from the following formula:

Fx = Concx * AX * Qx / 1000

where

Fx Substance load [kg/a]

Concx Median of the balance concentration [mg/l]

Ax Relative proportion of the plants that use the substance

 32

(e.g., 0.01 represents 1%)

Qx Water consumption for cooling purposes [m 3/a]

x Cooling principle (x = D for flow-through cooling and x = OK for open

circulation cooling)

This estimation is based on simplifying assumptions, which are briefly explained

below:

• The classification of the plants as once-through, open recirculation, and closed

cooling systems is not always unequivocal. There are substantial overlaps so as
to give more of a continuum.

• The estimation of the total loads from the proportion of the plants that use this
substance, based on the available data set provided by the operators, assumes
that the specific consumption values are independent of the size of the cooling
plant. This is only true to a certain extent. Thus, for example, larger plants tend to
use oxidative and smaller plants non-oxidative biocides. However, because of the
limited database at hand, a further sub-classification into various size classes,
going beyond the separate consideration of industrial cooling and power plants,
was not deemed appropriate.

• In general, it can be assumed that in the various industry branches, different

requirements are placed on cooling water conditioning. Thus in the foodstuffs
industry, because of hygiene requirements, a tendency to higher consumption
amounts for biocides compared to other branches can be observed. However, the
limited database does not permit a separate consideration of each branch.

Although we asked the manufacturing firms to calculate the total loads on the basis
of their product sales for cooling water conditioners in combination with the
preparation recipes and the individual share of the market, we did not succeed in
obtaining the desired results (Gartiser and Urich 2001).

For continuously added conditioners (phosphonates, polycarboxylates) instead of the

balance sheet values, the concentrations to be added in normal practice, as provided
by industry, were used (cf., table 16). The annual loads of auxilliary additives (N-
 33

methyl-2-pyrrolidone, alcohols) as well as inorganic pH-regulators and flocculation

agents such as Fe(III)Cl3 for additional water treatment were not calculated for the
Federal Republic of Germany, because the consumption in the plants was not
systematically determined.

4.3 Literature and database-research

The cooling water chemicals for which literature- and database-research was to be
performed were determined on the basis of the product information. We did not
consider chemicals for water treatment (inorganic acids and bases, salts for
regeneration of the ion-exchanger) as well as auxilliary additives, e.g., solubilizing
aids such as alcohols, which have no specific biocidal, dispersive or corrosion
inhibiting effect. With the help of the following data banks/collections and databases,
research was carried out on the individual substances:

Substance data collections and fact databases

• Roth: Wassergefährdende Stoffe, ecomed-Verlag, Landsberg

• Verschueren: Handbook of Environmental Data on Organic Chemicals, van

Nostrand Reinhold (1996)

• Kommission zur Bewertung wassergefährdender Stoffe (KBwS): Dokumentation

wassergefährdender Stoffe, Hirzel-Verlag, Stuttgart

• Merck Index 12th Ed. (1996)

• Ash: Handbook of Water Treatment Chemicals, Gower House (1996)

• Paulus: Microbicides for the Protection of Materials, Chapman & Hall (1993)

• Rossmoore: Handbook of Biocide and Preservative Use, Chapman & Hall (1995)

• Chemfinder, ECDIN and other Internet-Databases

• Dictionary of Substances and Their Effects (DOSE)

• International Uniform Chemical Information Database (IUCLID)

• Hazardous Substances Data Bank (HSDB)

• Data Bank of Environmental Properties of Chemicals (EnviChem)

• Register of Toxic Effects of Chemical Substances (RTECS)

 34

• Gefahrstoffinformationssystem der gewerblichen Berufsgenossenschaften

(GESTIS)

• PhysProp and Biolog/Biodeg (On-Line Databases of the Syracuse Research

Cooperation, SRC, http://esc.syrres.com)

Literature databases

• Biological Abstracts

• Current Contents

• MEDLINE

The hazard risk statements (R-Phrases) in the dangerous substance regulations

were researched in the GESTIS database. Here, in addition to the official
classification according to Annex I of the Guideline 67/548/EWG, are also found self-
evaluations by the producers (http://www.hvbg.de/d/bia/fac/zesp/zesp.htm). We went
beyond this information and performed – with varied success – additional internet-
searches of the databases of the U.S. Environmental Protection Agency (EPA), the
U.S. National Institutes of Health (NIH) and the National Library of Medicine
(including the database GENE-TOX). The available data were compared with the
internal substance-database shared by Bund/Länder (GSBL), which includes the
UBA-Neustoffdatenbank for new substances, the databases of the KBwS
(RIGOLETTO), the BgVV Chemis and BIG of the Feuerwehrinformationszentrum in
Geel (Belgium). Additional information so obtained substantially extended our
database.

A preliminary listing of the results of our research was distributed to participating

firms in preparation for the UBA-Workshop on the present project with the request
that they fill in any gaps in the data (Gartiser and Urich 2001). As a result, the data
pool was enlarged further. Whenever there were no citable published data available,
the product-specific entries on the safety data sheets of the manufacturers were
taken into account after consulting with them. The research results are presented in
the Annex to this report. It remains to be noted that it was not the aim of this report to
carry out a comprehensive and complete evaluation of all substances in the sense of
a “Risk Assessment” in accordance with the laws on chemicals or biocide-
 35

regulations. Consequently, as a standard for the selection of substance data we

relied on the wastewater relevance of the data. In addition, we looked at the oral
toxicity for mammals and the risk statements (R-Phrases), which are the prerequisite
for classification in water-hazard classes (Anonymous 2000). Those organisms that
are of importance in governmental control and are included in the list of parameters
of the wastewater regulations were given a higher significance. Hereby it was sought
to make a comparison possible with the practical investigations on wastewater
sidestreams, products and active ingredients.
 36

5 Results

5.1 Cooling water investigations

The results of the investigated wastewater samples are presented in Table 6. A total
of 12 cooling water samples and one condensate from steam production were
tested. The pH of the cooling water samples lay between 7.9 and 9.5; the
conductivity was between 121 µs/cm (for VE-water in plant 2) and 10,130 µS/cm (for
the concentrate of the reverse-osmosis system in plant 1).

The ecotoxicity of the cooling water samples in the algae, fluorescent bacteria and
Daphnia tests was in most cases low (G A/L/D -values from 1 to 3). After a shock-
treatment with quarternary ammonium compounds (plant 2) and isothiazolinones
(plant 6), values up to a dilution factor of G L=196 were determined. However, after
the elimination times of 1 to 3 days typically observed in practice, the ecotoxicity in
the cooling water of plants 4, 7 and 2 was completely eliminated. In the cooling water
of plant 5, 7 hours after the addition of QAV and hydrogen peroxide a slightly
elevated ecotoxicity was measured, but this can be largely attributed to the input of
solid materials during production. Also in the case of the continuous addition of
bromochlorodimethylhydantoin, no ecotoxicity of the cooling water was observed. In
the Ames test (screening) there was no mutagenic effect. However, one cooling
water sample was toxic after a shock treatment with isothiazolinones (plant 6). The
same sample turned out to be the only one that was genotoxic in the umu test
(GEU=6).
 37

Table 6: Summary of the wastewater investigations

Nr. 1 Nr. 2 Nr. 3 Nr. 4 Nr. 5 Nr. 6 Nr. 7

Electro Plastic Plastic film Plastic Chemical
Plastic manufacturing Chemical industry
Company No./ Branch industry manufacturing manufacturing manufacturing industry
KW after Blow-down
Steam
KW KW biocide shock after inacti- KW KW KW KW KW 1 KW 2 KW2 KW
condensate
dosage vation period

24 h after BCDMH,
BCDMH,
shock Bronopol,
(Bronopol,
Biocide (Isothia- (Isothia- (Isothia- treatment shock- Isothia-
(QAV) QAV H2O2/QAV Isothia- BCDMH
(shock treatment) zolinone) zolinones) zolinones) with dosage with zolinones
zolinones),
Isothiazolino Isothia-
NaOCl
nes zolinones

Sampling 27.06.00 19.07.00 11.10.00 14.10.00 19.07.00 19.07.00 12.07.00 17.07.01 27.07.00 11.12.00 11.12.00 16.07.01 17.07.01
pH pH 9,5 8,7 8,60 9,00 7,6 8,1 8,8 8,6 8,7 8,3 7,9 7,8 9,0
Conductivity µS/cm 10130 1640 2160 121 31600 130 720 831 240 735 2170 2220 1620
1721 302 (unfilt.)
COD mg/l 52 24 67 50 (filtered) 17 14 11 138 (filtered) <15 138 55 23
Ames test TA98 - S9 IF 1,0 1,0 1,1 1,0 0,9 1,0 0,8 1,1 0,9 0,86 tox. 0,87 1,01
Ames test TA98 + S9 IF 1,0 1,3 1,0 0,7 1,0 1,2 1,0 0,8 1,0 0,87 1,04 0,95 0,93
Ames test TA100 - S9 IF 1,1 1,1 0,8 1,1 1,1 1,1 1,0 1,1 1,1 1,12 tox. 1,09 1,09
Ames test TA100 + S9 IF 1,0 0,9 0,9 1,1 1,1 1,0 0,9 1,0 0,7 0,92 1,07 1,14 1,1

umu test - S9 GEU 1,5 3 tox. 1,5 1,5 1,5 1,5 1,5 1,5 1,5 6 1,5 1,5
umu test + S9 GEU 1,5 1,5 tox. 1,5 1,5 1,5 1,5 1,5 1,5 1,5 6 1,5 1,5
Algae toxicity GA 2 2 192 2 4 2 2 1 32 (unfilt.) 3 64 2 1
Luminescent bacteria
toxicity GL 2 2 48 2 2 2 2 2 4 2 192 2 2
384 (unfilt.)
Daphnia toxicity (24 h) GD 2 1 96 1 4 1 1 1 2 (filtered) 1 24 1 1
IF: Induction factor
KW: Cooling water
 38

5.2 Product investigations

5.2.1 Eco- and Genotoxicity

The results on the mutagenicity, genotoxicity and ecotoxicity of the products used in
the plants are presented in Table 7. Biocidal product 1, based on isothiazolinone,
was found to be mutagenic or genotoxic in the Ames- and umu tests. The maximal
induction factor was determined to be 11.1 (TA100). Biocidal product 2, based on a
not further specified "heterocyclic sulfur/nitrogen compound," had a similar action
spectrum and consequently is presumably also assignable to the isothiazolinone
group. Biocidal product 3 also showed an increase in the induction factor in TA98
and in the umu test, although such an effect is not known for the group of the
quarternary ammonium compounds (cf., annex); presumably, another component of
this product is responsible. The effective concentrations (EC 50) in the fluorescent
bacteria and Daphnia tests lie roughly in the range from 1 to 34 µl/l; the corrosion
inhibitor used in plant 1 turned out to be only slightly ecotoxic.

5.2.2 Identifying the source of the genotoxicity in plant 6

In the cooling water of circulation #2 of plant 6 a genotoxic effect was obtained in the
umu test. At the time the sample was taken the cooling water was being continuously
treated with 1-bromo-3-chloro-5,5-dimethylhydantoin (BCDMH) as well as with two
additional products containing tolyltriazole, phosphonic acid and
nonylphenolethoxylate. On the day of sampling there had been an additional shock
treatment with a combination preparation based on 2-bromo-2-nitropropan-1,3-diol
(Bronopol) and isothiazolinone (5 liters to a 50 m 3 system volume). In order to assign
the cause of the genotoxic effect, all these products were investigated in the umu
test. Since no umu test results were available for Bronopol, it was also tested as the
pure substance (Fluka-Chemika 17728). The results are shown in Table 8.
 39

Table 7: Results of the product investigations

Luminescent
Ames test TA98 Ames test TA100 umu test Daphnia test
Usage in Active Dosage bacteria test
Name
plant No. substance µl/l Maximum IF Maximum IF Maximum IF EC10 EC50 EC10 EC50
-S9 + S9 -S9 + S9 -S9 + S9 [µl/l] [µl/l] [µl/l] [µl/l]

Biocide 1 1 Isothiazolinone 200-500 1,6 1,4 11,1 1,7 3,2 2,0 1,15 3,74

(20 µl/Pl) (20 µl/Pl) (20 µl/Pl) (4 µl/Pl) (42 µl/Pl) (42 µl/Pl)

Corrosion 100-200
1 NaOH, Triazoles 1,2 1,7 1,5 1,3 1,0 1,5 100-500 500-1000
inhibitor 1 makeup water
(80 µl/Pl) (20 µl/Pl) (500 µl/Pl) (160 µl/Pl (333 µl/Pl)

Heterocyclic 100 shock

Biocide 2 4 1,3 1,9 10,1 1,5 2,9 2,9 0,6 2,3 1,6 5
sulfur/nitrogen dosage
compound
(20 µl/Pl) (20 µl/Pl) (20 µl/Pl) (4 µl/Pl) (21 µl/Pl) (42 µl/Pl)

Biocide 3 2 QAV 10-100 1,4 2,1 1,0 1,1 0,9 1,8 1,3 2,8 0,1 0,6

(100 µl/Pl) (100 µl/Pl) (5,2 µl/Pl) (42 µl/Pl)

Biocide 4 3 not known 100-250 1,5 1,7 1,4 1,0 1,6 1,3 5,8 29,5 0,2 34

(20 µl/Pl) (10 µl/Pl) (20 µl/Pl) (333 µl/Pl) (21 µl/Pl)

Biocide 5 5 H2O2, QAV 100-200 1,6 1,8 1,2 1,0 1,6 1,6 0,6 2,5 0,8 1,8

(20 µl/Pl) (5 µl/Pl) (5 µl/Pl) (21 µl/Pl) (333 µl/Pl)

IF: Induction factor
 40

Table 8: Source of the genotoxicity in the cooling water from plant 6

Induction-
Concen- factor IF Dilution factor G (- S9) Dilution factor G (+ S9)
Product Active substance
tration Growth-rate
WR 1,5 3 6 12 24 48 96 192 1,5 3 6 12 24 48 96 192
1-Bromo-3-chloro-
Biocide 6 50 mg/l IF 0,53 0,54 0,78 0,77 1,00 1,00 1,11 0,96 0,69 0,87 0,93 0,85 0,84 1,05 0,96 0,90
5,5-dimethyl-
hydantoin
WR 1,38 1,35 1,23 1,24 0,95 1,04 0,91 1,12 1,13 1,01 1,01 1,04 1,05 0,97 0,92 0,93

Solubility aid Nonylphenol- 50 µl/l IF 0,84 0,77 1,03 0,94 0,93 0,82 0,85 1,00 0,76 0,83 0,82 0,98 0,78
ethoxylate
for biocides WR Turbidity 1,17 1,24 0,89 1,04 1,06 1,00 1,01 1,00 1,19 1,13 1,07 0,98 1,05
Corrosion
Tolyltriazole
inhibitor 2 200 µl/l IF 0,71 0,80 0,86 0,80 0,72 0,73 0,78 0,75 0,73 0,78 0,93 0,94 0,79 0,80 0,66 0,79

Phosphonic acid
WR 1,21 1,23 1,21 1,16 1,10 1,00 0,98 1,01 1,00 1,03 0,99 0,94 1,07 1,03 1,01 1,04
2-Bromo-2-
nitropropan-1,3-
Biocide 7 diol (Bronopol) 100 µl/l IF 2,09 1,12 1,18 1,19 1,11 1,03 0,94 0,83 2,05 1,21 1,11 1,05 1,09 0,93 1,10 1,06
2-Methyl-4-
isothiazolin-3-one WR 0,50 0,73 0,78 0,85 0,94 1,05 0,89 0,92 0,55 0,79 0,94 0,96 1,02 1,03 0,89 0,96
5-Chloro-2-methyl-
4-isothiazolin-3-
one
Commercial
2-Bromo-2-
chemical 20 mg/l IF tox. tox. 2,63 1,78 1,35 1,04 1,24 1,02 tox. 2,20 1,53 1,26 1,13 1,05 1,09 1,06
nitropropan-1,3-
diol (Bronopol)
WR 0,15 0,39 0,58 0,87 0,99 0,98 0,88 0,93 0,39 0,73 0,88 0,97 1,01 1,01 0,99 0,94
 41

It turned out that neither the biocide 1-bromo-3-chloro-5,5-dimethylhydantoin, the

corrosion inhibitor, nor the solubilizing agent could explain the observed gentoxic
effects. But biocide 7 proved to be weakly genotoxic, whereby the maximal induction
factor of 2.0 was accompanied by a strong decrease in the growth factor (growth
factor >0.5). From the product testing it is known that the isothiazolinones 2-methyl-
4-isothiazolin-3-one and 5-chloro-2-methyl-4-isothiazolin-3-one are genotoxic (cf.,
sect. 5.2.1). However, here induction factors up to 3.2 were determined. The
substance testing of Bronopol yielded the result that this non-oxidative biocide also
induced a weak effect in the umu test (up to an induction factor of 2.6), whereby also
here the toxic effect must be taken into account in explaining the result.

Thus, the genotoxic effect in circulation #2 of plant 6 is with high probability due to
biocide 7, whereby the effect could be explained by both isothiazolinone as well as
Bronopol.

5.2.3 Decrease of the biocidal effect in the fluorescent bacteria test

5.2.3.1 Starting concentration

According to Annex 31 of the wastewater regulations, after a shock treatment with

biocides the outflow may only be opened when for fluorescent bacteria toxicity the
dilution step GL=12 is not exceeded. Since until now no generally accepted standard
procedure was available for the determination of the elimination behavior of cooling
water biocides in a batch experiment, various conditions with respect to the starting
and inoculum concentration were simulated (cf., sect. 4.1.9). Our aim was to
determine the influence of the biomass on the elimination factors degradation and
adsorption.

The starting concentration of the biocides was chosen based on the effective
concentrations to be added according to values in the literature and manufacturers’
recommendations (cf., table 9).
 42

Table 9: Dosing of biocides in the circulation cooling

Active substance Concentration of active substance
[mg/l]
Reference 1) 2) 3) 4)
Oxidative biocides
Chlorine 5) 0,1 - 0,2 0,1 - 0,2
Sodium hypochlorite 1-5 1-5
1-Bromo-3-chloro-5,5-
2-7 0,2 - 5 0,2 - 5 1-4
dimethylhydantoin
Ozone 0,015 - 0,2 0,015 - 0,2 0,02 - 0,2 0,1 - 0,2
Hydrogen peroxide - 1-5 1-5 >50
Non-oxidative biocides
Glutardialdehyde 25 - 50 11 - 200 1 - 50 25 - 50
2,2-Dibromo-3-
4 - 10 1 - 50 1 - 50 4 - 10
nitrilopropionamide
2-Bromo-2-nitropropan-1,3- 200 - 1500
1 - 25 1 - 25 (?)
1 - 25
diol (Bronopol)
ß-Bromo-ß-nitrostyrene 1-5 4 - 20 1-5
Isothiazolinone 1-5 1 - 30 1 - 30 1-2
Methylenebisthiocyanate 2-6 0,8 - 5 0,75 - 5 2-6
Quarternary ammonium
3 - 50 5 - 40 6 - 10 3 - 15
compounds
1)
Baltus and Berbee: Het gebruik van biociden in recirculatiekoelsysteme. RIZA, 1996
2)
Consultants in Environmental Sciences: Biocides in Cooling Water Systems, April 1994
3)
Fielden and Iddon: Use Category Document - Water Treatment Chemicals, Env.Agency, 1997
4)
Personal communication Dr. Klautke, BetzDearborn GmbH, from 06.07.01
5)
Required concentration without consideration of chlorine depletion

An overview of the experiments carried out and the most important results can be
found in Table 10. In Figures 2-10 the elimination curves are presented.
 43

Table 10: Experimental overview of the elimination curves of cooling water

biocides
Concentration
Time until < 20% inhibition at
active cf., Figure
dilution factor G12
substance
mg/l 0,5 g TS/l 30 mg TS/l No.
Non-oxidative biocides
100 µl/l
(used 2d >7d 2
Isothiazolinones concentration)
50 µl/l
Quarternary ammonium (used 3h 3h not shown
compounds concentration)
Quarternary ammonium 100 µl/l
compounds with hydrogen (used 3h 3h not shown
peroxide concentration)
Alkyldimethyl-
10 2d 3d 3
benzylammonium chloride

2,2-Dibromo-3- 10 48 h 48 h 4
nitrilopropionamide (DBNPA)
48 7d >14 d 5
Glutardialdehyde 30 3d 6
60 3d
120 6d
160 7d 7d 7
2-Bromo-2-nitro-propan-1,3-
35 4d >8 d 10
diol (Bronopol)
oxidative biocides
1-Bromo-3-chloro-5,5-
4 1 h (G2) 1 h (G2) 8
dimethylhydantoin
37 44 h (G2) 44 h (G2) 9
TS: dry solids

5.2.3.2 Non-oxidative biocides

Isothiazolinones

The biocide based on isothiazolinones (biocide 2) was tested at the concentration to

be used according to the manufacturer’s recommendation. There is a clearly
discernible dependence on the density of the inoculum. While the fluorescent
bacteria toxicity at the highest inoculum concentration was already completely
reduced within one day, at the lowest concentration (post-settling outflow of a
municipal sewage treatment plant) no elimination was observed even after 7 days
(Figure 2). In a Daphnia test performed in parallel the product showed a similar
elimination behavior at a dilution step of 12 (data not shown). Adsorption is a
particularly important elimination factor here.
 44

100

90
Isothiazolinone,
Starting concentration 100 µl product/l
Inhibition at dilution factor 12 [%]

80

70
TS: Dry solids;
Nachklärung: Outflow final clarifier
60

50

40

30
1000 mg TS/l
20 500 mg TS/l
200 mg TS/l
10 30 mg TS/l
Nachklärung
0
0 20 40 60 80 100 120 140 160 180

Time [h]

Figure 2: Decrease of the fluorescent bacteria inhibition with isothiazolinone

Quarternary ammonium compounds

Two products with quarternary ammonium compounds (biocide 3 and biocide 4 as a
combination product with hydrogen peroxide) were tested at the concentration
recommended by the manufacturer. However, already at 3 h after the beginning of
the test both products showed no further fluorescent bacteria toxicity (cf., table 10).
Another product was tested at a defined concentration of 10 mg alkyl dimethylbenzyl
ammonium chloride. Depending on the inoculum concentration, 2 typical curves were
obtained. Above 200 mg d.s./l a 70% decrease in the fluorescent bacteria inhibition
was already achieved 3 h after test begin, while in contrast, the time for a decrease
at 30 mg d.s./l and in the outflow of the final-clarifier increased to 3 days (Figure 3).
As a first approximation, biological de

gradation and the adsorption of the quarternary ammonium chloride can be regarded
as equally important elimination factors.
 45

100

90 Alkyldimethylbenzylammonium chloride,
Starting concentration 10 mg/l
Inhibition at dilution factor 12 [%]

80

70
TS: Dry solids;
Nachklärung: Outflow final clarifier
60
1000 mg TS/l
50 500 mg TS/l
200 mg TS/l
40 30 mg TS/l
Nachklärung
30

20

10

0
0 10 20 30 40 50 60 70 80 90 100

Time [h]

Figure 3: Decrease of the fluorescent bacteria inhibition with QAV

Dibromo-nitrilopropionamide (DBNPA)

The biocide dibromo-nitrilopropionamide was investigated at two different

concentrations. At a concentration of 10 mg/l the fluorescent bacteria inhibition for all
inoculum concentrations decreased rapidly within 3 h, but then more slowly
thereafter. The threshhold of 20% inhibition was already reached after only 1 h in the
experiment with the final-clarifier water. In contrast, in the tests with activated sludge
up to 48 h were required (Figure 4). This difference is even more striking with the
higher starting concentration of 48 mg/l; here the fluorescent bacteria inhibition in the
final-clarifier water was completely eliminated within 24 h, while in tests with
activated sludge at higher concentrations up to 14 days were required (Figure 5).
The grounds for this can be found in the pH-dependence of the rate of hydrolysis of
the compound. It is known that DBNPA is hydrolyzed substantially faster in the
alkaline range than under neutral conditions. While the pH-value in the experiments
with final-clarifier water lay between 7.6 and 8.2, in the tests with activated sludge a
pH of 7.4 to 7.6 was measured (data not shown).
 46

100

90 2,2-Dibromo-3-nitrilopropionamide (DBNPA),
Starting concentration 10 mg/l
Inhibition at dilution factor 12 [%]

80

70
TS: Dry solids;
Nachklärung: Outflow final clarifier
60
1000 mg TS/l
50 500 mg TS/l
200 mg TS/l
40 30 mg TS/l
Nachklärung
30

20

10

0
0 10 20 30 40 50 60

Time [h]

Figure 4: Decrease of the fluorescent bacteria inhibition with DBNPA (10 mg/l)

100

90 2,2-Dibromo-3-nitrilopropionamide (DBNPA),
Starting concentration 48 mg/l
Inhibition at dilution factor 12 [%]

80 TS: Dry solids;

Nachklärung: Outflow final clarifier
70
1000 mg TS/l
60 500 mg TS/l
200 mg TS/l
50 30 mg TS/l
Nachklärung
40

30

20

10

0
0 50 100 150 200 250 300 350 400

Time [h]

Figure 5: Decrease of the fluorescent bacteria inhibition with DBNPA (48 mg/l)
 47

Glutaraldehyde

Initially the influence of the glutaraldehyde concentration was investigated at a

constant inoculum-content (30 mg d.s./l activated sludge). While the fluorescent
bacteria inhibition at concentrations below 60 mg/l glutaraldehyde was fully
eliminated within 3 days (Figure 6), the lag-phase at higher concentrations increased
to 6 (at 120 mg/l) or 7 days (at 160 mg/l). In a second experiment the influence of the
inoculum concentration at a constant concentration (160 mg/l) of glutraldehyde was
determined. As was later noticed, this concentration was given in only 1 of 4
reference sources (Table 9). In the final-clarifier the fluorescent bacteria inhibition at
this glutaraldeheyde concentration had not decreased after 7 days. At the highest
inoculum concentration of 1 g d.s./l, in contrast, the inhibitory effect was completely
eliminated after 3 days (Figure 7).
 48

100

Glutardialdehyde; inoculum:
90
activated sludge 30 mg dry solids/l
Inhibition at dilution factor 12 [%]

80

70

60 160 mg/l
120 mg/l
50
60 mg/l
30 mg/l
40

30

20

10

0
0 20 40 60 80 100 120 140 160 180

Time [h]

Figure 6: Fluorescent bacteria inhibition with glutardialdehyde (30-160 mg/l)

100

Glutardialdehyde,
90
Starting concentration 160 mg/l
Inhibition at dilution factor 12 [%]

80

70
1000 mg TS/l
60 500 mg TS/l
200 mg TS/l
30 mg TS/l
50
Nachklärung

40

30 TS: Dry solids;

Nachklärung: Outflow final clarifier
20

10

0
0 20 40 60 80 100 120 140 160 180

Time [h]

Figure 7: Fluorescent bacteria inhibition with glutardialdehyde (30-1000 mg

d.s./l)
 49

Bromonitropropandiol (Bronopol)

The formaldehyde releasing biocide 2-bromo-2-nitro-propan-1,3-diol was

investigated at a concentration of 25 mg/l. The results showed a strict dependence of
the elimination behavior on the inoculum density. At an inoculum concentration of 1 g
d.s./l the fluorescent bacteria inhibition was largely eliminated wilthin 1 day, while at
30 mg d.s./l or in the outflow of the final-clarifier the inhibitory effect remained stable
even after 8 days.

100

90

2-Bromo-2-nitro-propan-1,3-diol (Bronopol),
Inhibition at dilution factor 2 [%]

80
Starting concentration 25 mg/l active substance
70 TS: Dry solids;
Nachklärung: Outflow final clarifier
60

50 1000 mg TS/l
500 mg TS/l
40 200 mg TS/l
30 mg TS/l
30 Nachklärung

20

10

0
0 50 100 150 200 250

Time [h]

Figure 8: Decrease of the fluorescent bacteria inhibition with Bronopol

 50

5.2.3.3 Oxidative biocides

Bromochlorodimethylhydantoin (BCDMH)

Bromochlorodimethylhydantoin is used as a solid granulate with a sidestream water

flow channeled through a filter filled with BCDMH. Because the granulate proved to
be poorly soluble in the mineral salts nutrient solution needed for the Zahn-Wellens
test, the substance was dissolved in tap water. The elimination behavior was
determined for two starting concentrations. Because of the known instability of the
compound, additional total chlorine determinations were carried out. At the required
dilution step 12 there was no detectable fluorescent bacteria inhibition for either
starting concentration, so the undiluted samples (G=2) were investigated. At a
substance-concentration of 4 mg/l (1 mg total chlorine), for all inoculum
concentrations there was no more measurable fluorescent bacteria toxicity after 3 h
(Figure 8). At a substance-concentration of 37 mg/l (10 mg/l total chlorine) already
within the first 6 h a clear dependence of elimination on the inoculum concentration
could be observed. Thereafter, the inhibitory effect for all tests with inoculum lay
between 10 and 30%, while the fluorescent bacteria inhibition in the test with tap
water still lay at 90% even after 45 h (Figure 9). The decrease in the fluorescent
bacteria toxicity accompanied the decrease in the total chlorine concentration (cf.,
table 11).

Table 11: Elimination of BCDMH depending on the inoculum

Free chlorine [mg/l]
500 mg 200 mg 30 mg Outflow final Tap
TS/l TS/l TS/l clarifier water
0h 2,08 0,48 0,17 0,98 4,98
3h 1,11 0,13 0,15 0,49 5,55
20 h 0,12 0,05 0,10 0,30 4,78
44 h 0,11 0,07 0,05 0,04 0,57
Total chlorine [mg/l]
500 mg 200 mg 30 mg Outflow final Tap
TS/l TS/l TS/l clarifier water
0h 4,92 3,81 2,62 4,09 8,30
3h 2,70 2,48 0,82 2,92 8,65
20 h 0,72 0,49 0,17 1,13 6,45
44 h 0,14 0,09 0,07 0,07 0,61
Start concentration 9,9 mg/l total chlorine
 51

100

1-Bromo-3-chloro-5,5-dimethylhydantoin,
90
Starting concentration 1 mg/l total chlorine
Inhibition at dilution factor 2 [%]

80
TS: Dry solids; Nachklärung: Outflow final clarifier; Leitungswasser: Tap water
70

1000 mg/l
60
500 mg TS/l
200 mg TS/l
50
30 mg TS/l
Nachklärung
40
Leitungswasser

30

20

10

0
0 0,5 1 1,5 2 2,5 3 3,5

Time [h]

Figure 9: Decrease of the fluorescent bacteria inhibition with BCDMH (4 mg/l)

120

110 1-Bromo-3-chloro-5,5-dimethylhydantoin,
Starting concentration 9.9 mg/l total chlorine
100
Inhibition at dilution factor 2 [%]

90
TS: Dry solids; Nachklärung: Outflow final clarifier; Leitungswasser: Tap water
80

70 500 mg TS/l
200 mg TS/l
60 30 mg TS/l
Nachklärung
50 Leitungswasser
40

30

20

10

0
0 5 10 15 20 25 30 35 40 45 50

Time [h]

Figure 10: Decrease of the fluorescent bacteria inhibition with BCDMH

(37 mg/l)
 52

5.3 Evaluation of the product information sheets

In the course of the study documentation was compiled for a total of 418 products for
cooling water conditioning from ca. 35 manufacturing firms. A total of 101 products
therefrom contained biocides. The qualitity of the documents ranged from poorly
documented safety data sheets to detailed eco logical evaluations. Very few
elimination curves for cooling water biocides were provided. Since all the leading
producers in the field sent us information, an estimated 80% of the total market has
been surveyed.

In Figure 11 the product groups for the cooling water conditioners are documented.

Not known
3%
Others
3%
Guanidines
3% Chlorine releasers
8%
Quaternary ammonium
compounds
9% Bromine releasers
16%
Organic sulfuric
compounds
8%
Oxygen releasers
8%
Aldehydes
6%
Isothiazolinones
Organic bromine
26%
compounds
10%

Figure 11: Proportion of biocidal active ingredients in 101 products

 53

5.4 Evaluation of the questionnnaires

Altogether 182 questionnaires on the cooling systems of 176 plants were evaluated.
Of these, 110 had open circulation cooling, 48 had once-through cooling, and 24
could be classified as closed-circulation cooling. The most important characteristic
data from the data set are given in Table 12.

Table 12: Characteristic data for the cooling systems investigated

Cooling systems with

Mean specific
Cooling Cooling Water Products Condition- Biocides and
water Biocides
systems capacity consumption used ing conditioning
consumption
3 3
[n] MW [1000 m /a] [m /(kW*a)] [t/a] [n] [n] [n]
Power
10 4.817 40.380 6 83 5 8 4
Open plants
recirculation Industrial
cooling cooling 100 2.051 35.421 20 778 69 72 62
systems

Once-through cooling
48 18.936 5.985.084 501 23 4 4 2
Closed circulation *)
24 198 13 0,6 7 4 16 4
cooling

Sum 182 26.002 6.060.898 891 82 100 72

[n]: Number *) Partly once-only filling not attributable to annual amount

The water consumption for cooling purposes of ca. 6 billion m 3 represents 19% of the
total untreated discharged cooling water (Stat. Bundesamt 1998). Only 76 Mio. m 3
are assigned to open circulation cooling. Overall, it could be established that in most
cases it was not possible to make an unequivocal assignment of the continuously
added substances as well as their concentration ranges from the product
information; often only the substance group was indicated. For the batchwise added
biocides, in contrast, the names of the active substances and their concentration
ranges are better documented, because these are listed as hazardous substances in
the safety information sheets.
 54

5.4.1 Open recirculation cooling systems

In the cooling systems investigated a total of 891 t of cooling water conditioners

(weight on a product basis) was used. This does not include the chemicals used for
treatment of raw water (de-carbonizing, flocculation and pH-adjustment) such as
inorganic acids and bases. For these latter purposes, a total of 53 t of sulfuric acid, 4
t of hydrochloric acid, 0.2 t of sodium hydroxide, 145 t of ferric(III) chloride (weights
of the pure substances) as well as 2 t of organic flocculation aids (weight of the
products) were consumed. The total loads of defined substances which were used in
the 110 plants for open circulation cooling are given in Table 13. Here products were
not considered if they could not be assigned to a group or if the concentrations used
were not given, so the values given are minimal values. For the 10 power plants with
open circulation cooling investigated, no zinc or molybdate was used, in agreement
with Annex 31. Therefore, it seems justified to consider these separately from the
industrial cooling systems.
 55

Table 13: Total amounts of the investigated chemicals in open circulation

cooling

Industrial
cooling Power plants
systems
[t/a] 1) [t/a] 2)
Oxidative biocides
Chlorine 52,3
Sodium hypochlorite 27,7 8,2
Calcium hypochlorite 0,01
Trichlorisocyanuric acid 0,03
Ammonium bromide / sodium
bromide ?
Sodium hypobromite 0,5
1-Bromo-3-chloro-5,5-
dimethylhydantoin 1,6 0,7
Hydrogen peroxide 9,7
Ozone 0,2
Potassium peroxymonobisulfate 0,1
Peracetic acid 0,3
Non oxidative biocides

2,2-Dibromo-3-nitrilopropionamide
2-Bromo-2-nitropropan-1,3-diol 0,1
(Bronopol) 0,01
Isothiazolinones 0,6
S-Triazine ?
Dodecylguanidine hydrochloride
(DGH) 0,01
Methylenebisthiocyanate 0,1

Quaternary ammonium compounds ?

Conditioning chemicals
Phosphonic acids 6,6 1,7
Phosphates 0,7
Triazoles 2,4 ?
Polycarboxylates >7,7 >0,3
Sodium molybdate 1,0
Zinc salts 11,9
Auxiliary additives/water treatment
N-methyl-2-pyrrolidone 0,2
Alcohols 2,4
Fe(III)Cl3 145,2
inorganic lyes 1,6 0,1
inorganic acids 42,2 4,9
1)
100 industrial cooling systems with open recirculation cooling
2)
10 power plants with open recirculation cooling
 56

5.4.2 Once-through cooling systems

The 48 investigated plants with once-through cooling systems include about 20%
each from the branches foodstuffs industry, chemical industry and energy
production, with the remaining plants belonging to the plastics, metal and paper
industries, as well as other areas. Only 6 of the 48 plants used cooling water
conditioners. These plants should be considered separately (see Table 14). In one
food processing plant the canned goods were cooled with water after sterilization. In
order to prevent contamination or corrosion of the cans, fatty alcohol ethoxylates,
sodium ethyl-hexanoate and chlorine in the form of sodium hypochlorite were
continuously added to the cooling water. In another plant manufacturing canned
foodstuffs, corrosion inhibitors (sodium molybdate; alcohol ethoxylates) and
hardness stabilizers (phosphocarbonic acids) were continuously fed into the cooling
water. In one plant, which manufactures packaging materials, the cooling water is
treated with isothiazolinone and phosphonic acids. The provision of cooling waters
here is made more difficult by the very high hardness (25 °dH) and manganese
content.

In one plant of the chemical industry chlorine was continuously added to the cooling
water. Sodium hypochlorite is used in a thermal power plant cooled by sea water. In
one large thermal power plant iron(II) sulfate is used, since in low concentrations
(0.05-1 mg/l) in sea water and brackish water it acts anticorrosively through the
formation of a protective layer of iron hydroxide (Wunderlich 1978a).

All in all, the use and selection of conditioners in plants with once-though water
cooling presents a very heterogeneous picture.
 57

Table 14: Consumption data in plants with flow-through cooling

Nr. Branch Capacity Water consumption Origin of Biocide Product Active ingredient 1 Active ingredient 2 Active ingredient 3 Active ingredient 4
Dis-
water dosage consump- charge
3 3 [kg] [kg] [kg] [kg]
[MW] [1000 m /a] [m /(a*KW)] tion [kg]
Sodium Phosphon-
molybdate Cocoimino- Alkanol- carbonic
37 Foodstuffs ? 17 other Product 1 2.400 KA dihydrate 132,0 propionate 132,0 ethoxylate 132 acids 132
industry none
Sodium 2-
O and Ethoxylated ethylhexano
65 Foodstuffs ? 314 O Product 2 1.300 KA alcohols 258,7 ate 63,7
industry 240 G Product 3 S 502 NaOCl 50,7 NaOH 49,7
Chlorine K 300 Chlorine 300,0
68 Power 3.400 420.000 124 M Sodium S 12.000 M NaOCl 1560,0
plant hypochlorite
Ferrous(II)-
Power
83 plant 1.486 1.040.000 700 (M) sulfate 450.000 O Ferrous(II)sulfate

5-Chlor-2-methyl- 2-Methyl-4-
4-isothiazolin-3- isothiazolin-
120 Bandage 0,2 55 275 G Product 4 K 430 O one 6,5 3-one 2,2
material Butanephos-
phonotricar-
Product 5 1.200 Phosphonic acids bonic acid
134 Chemical ? 7.000 O Chlorine K 4.380 O Chlorine 4380,0
industry
Origin of water: G=ground water; O=surface water; M= marine water; (M)=brackish water
Biocide dosage: K=continuously, S=batchwise (shock) dosing
Discharge: O=surface water; KA=municipal treatment plant; M=sea
 58

5.4.3 Closed circulation cooling systems

The 24 closed circulation cooling systems investigated were mostly small plalnts with
less than 10 MW cooling capacity. In 8 plants the cooling water is not conditioned. In
all, the chemicals added weighed 13 t (on a product basis), but only a small
proportion (< 0.5 t) could be attributed to defined chemicals. A large proportion of the
products consists of not further characterized antifreeze agents. To inhibit corrosion,
molybdate and zinc salts are used, as well as phosphonic acids and triazoles. As
biocides, quarternary ammonium compounds, organobromine compounds and
isothiazolinone are used. The estimation of the total amounts used was made even
more difficult by the fact that in some cases the first filling of the closed systems was
involved and as a rule the circulation water is only changed at intervals of several
years. According to the operators’ responses on the filled out questionnaires, ca. 1/3
of the plants have the cooling water taken away for disposal after use, while 2/3 of
the plants release it into the municipal sewage treatment plants, in individual cases
also over the surface water.

5.4.4 Estimation of the total loads for Germany

5.4.4.1 Water consumption for cooling purposes

In keeping with our originally stated aims, on the basis of the consumption data of
the cooling plants surveyed an overall balance sheet calculation is to be made of the
total annual loads for conditioners (on a substance basis) for Germany as a whole.
Here the water consumption data for cooling purposes collected by the German
Federal Statistics Office is directly applied (Stat. Bundesamt 1998). However, the
Statistics Office does not distinguish between plants with flow-through cooling and
those with open circulation cooling, so that several assumptions must be made.

a) Mining and processing activities

In 1995 376 Mio. m 3 of cooling water were discharged after recirculation cooling and
4.981 Mio. m3 without recirculation cooling (Stat. Bundesamt 1998). While in a first
approximation the discharged amount without recirculation cooling equals the
amount of water used, for the plants with recirculation cooling the evaporation losses
must be considered. For a concentration factor of 3 ca. 1/3 of the make-up water is
re-emitted, while 2/3 evaporates. Thus a total water use for recirculation cooling
 59

plants of 1.1 billion m 3 (109 m3) can be calculated. However, hereby once-through
cooling systems with outflow cooling are included.

An alternative procedure is based on the data given by the Statistics Office for the
total use of cooling waters and the utilization factor for multiple and recirculation use
(Stat. Bundesamt 1998). In calculating the “total use” the recirculation water is
included repeatedly with a factor corresponding to the number of times it recirculates.
"Multiple use" is understood to mean the further use of the cooling waters for other
purposes (e.g., for cleaning). From the total use of the cooling water (29.1 billion m 3)
and the utilization factor of 4.8 (Statistisches Bundesamt, Fachserie 19, Reihe 2.2
(1995), 3.1) it can be calculated that ca. 6 billion m 3 fresh water were used for
cooling purposes in 1995. If one subtracts from this value the amount of water used
only once (i.e., without recirculation cooling), then ca. 1 billion m 3 water were used
for open recirculation cooling and 5 billion m 3 water for once-through circulation
cooling. By and large, these data agree with the rule of thumb numerical
classification given above. Using these values we then performed the calculations to
obtain the overall estimates.

b) Cooling water provision for the thermal power plants for the public power supply

The thermal power plants supplying the public have a special position and are
treated separately by the Federal Statistics Office and also in Annex 31. The
operations of the plants are more uniform in comparison to the industrial cooling
systems. The principal demand for cooling water is for the turbine condensors, and
secondary cooling locations are usually operated in closed systems. For large
cooling systems of modern power plants with condensors made of stainless steel or
titanium the addition of corrosion inhibitors is not necessary. Large cooling towers of
power plants should be so constructed and operated that the regular use of
microbiocides is not necessary (Fichte et al. 2000). The total amount of cooling water
used in 1995 (including multiple use and circulation use) was ca. 61 billion m 3, and
the utilization factor was ca. 2.2 (Stat. Bundesamt 1998). In response to our enquiry,
the Federal Statistics Office provided us with the data for the proportion of multiple
use and circulation use, as this could not be ascertained from the published
information (Mr. Knichel 2001). From the total amount of discharged cooling water,
by subtracting the water used only once, the proportion used for multiple use and
 60

circulation cooling water was calculated in the first approximation to be 4% of the

total discharged cooling water (cf., table 15).

Table 15: Cooling water use for thermal power plants (1995 )

Cooling water
Cooling water used discharged
[1000 m3] [1000 m3] [%]
Multiple use 458.861
1.126.255 4
Circulation use 34.354.663
Single use 26.946.470 26.946.470 96
Sums 61.759.994 28.072.725 100
Sources: (Mr. Knichel 2001); (Stat. Bundesamt 1998)

Based on these considerations, it was assumed for further calculations that 1 billion
m3 cooling water are discharged from open circulation cooling and 27 billion m 3
cooling water from once-through cooling. Assuming a concentration factor of 2, this
represents ca. 2 billion m 3/a of fresh water consumed for open circulation cooling of
power plants.

5.4.4.2 Open circulation cooling

The procedure for calculating the concentrations of chemicals and the proportion
(percentage) of the plants which use a particular chemical or chemical group is
described in Sect. 4.2.3. The total loads are obtained from the total amount of 1
billion m3 cooling water used for mining and processing industries. The thermal
power plants, which use ca. 2 billion m 3 of additional water, were calculated
separately.

Continuously added conditioners

A preliminary version of the balance drawn up from these data was sent to the
participants of the workshop of 18.05.01 for their comments. Several participants
expressed skepticism about the level in the balance for the added concentrations
and loads, especially for the continuously added cooling water conditioners such as
the phosphonates. In response, an accounting for this compound was additionally
undertaken on the basis of the concentrations added in normal practice (cf., table 16)
Since the standard concentrations are based on the circulation water, the estimation
of the total load here is not made on the basis of the fresh water volumes, but rather
 61

on the actually discharged cooling water (376 Mio. m 3 from industrial cooling plants,
1 billion m3 from power plants). The consumption of auxiliary aids (N-methyl-2-
pyrrolidone, alcohols) as well as inorganic pH-regulators and flocculants like
Fe(III)Cl3 was not systematically surveyed and thus not included in the calculation for
total consumption for all of Germany. In the substance group polycarboxylates
several differently named compounds were included (polycarboxylate, polycarbonic
acid, alkylepoxycarboxylate, polyoxycarbonic acid, polymaleic acid, maleic acid/co-
polymer, acrylic acid-co-polymer, acrylic acid-Ter-polymer). The less important low
molecular weight acids were omitted here.

Table 16: Concentrations of continuously added conditioners (concentration in

the circulation water in mg/l)
Industrial cooling- Corrosion Hardness Cooling water
Active substance Power plants 2), 3)
water circulation inhibitors 4) stabilizers/Dispersants 4) 5
)

Phosphonate 3-8 1.5 - 3 5 - 20 2 - 10 6 - 12

(~ ppm P) 6) (~ 0.8 - 2) (~ 0.4 - 0.8) (~ 1.3 - 5) (~ 0.5 - 0.8) (~ 1.5 - 3)

Phosphate 12 - 15 6 5 - 25 7 - 15
n.a.
(~ ppm P) (~ 4 - 5) (~ 2) (~ 1.6 - 8) (~ 2.2 - 4.8)
Polycarboxylates
6 - 12 2-7 - 5 - 20 20 - 50
and Polycarbonic
Zinc 1-3 - 2 - 10 - 3-4

Molybdate 5-7 - 2 - 15 - n.a.

Triazole derivatives 1-2 1-2 1-5 - n. a.

n.a.= no information available; "-" = not used for this purpose

1)
Personal communication from Dr. Klautke, BetzDearborn GmbH , 09.01.02
2)
Personal communication from Dr. Olkis, ONDEO Nalco GmbH, 10.12.01
3)
Personal communication from Dr. Hater, Henkel Surface Technologies, 13.12.02
4)
Fielden et al. (1997)
5)
Wunderlich (1978)
6)
The usual P-content of phosphonates lies between 10 and 30%, due to the substances present in the largest amounts,
HEDP and ATMP, with 30% P-content assumed to be present at an average content of 25%.

Shock treatments by batchwise addition of cooling water biocides

The balance sheet calculations used for continuously added chemicals could not be
applied for the biocides which are usually added batchwise, as this would have led to
a gross overestimation of the loads. In order to take into account the time factor, the
total loads were calculated as described in sect. 4.2.3 from the consumption
numbers and the documented fresh water use.The concentration calculated here
represents a helpful parameter, which does not necessarily correspond to the
concentration in the circulation water (after a shock treatment).
 62

For the biocide groups of quarternary ammonium compounds (QAV), triazine

derivatives and guanidine, no information on concentrations was available for the
products involved. It was assumed that these biocides as well as isothiazolinones
were usually added batchwise at long intervals. The median of the calculated
substance concentration for isothiazolinones is 0.08 mg/l (cf., table 17). To take into
account the higher concentrations used for QAV and triazine derivatives this value
was adjusted upward, to 0.26 mg/l (QAV) and 0.533 mg/l (triazine/guanidine). Here it
was assumed that the effective substance concentrations of isothiazolinones, QAV
and triazine/guanidine correspond to 3, 10 and 20 mg/l (cf., also table 9). In Table 17
the balance of the total amounts of cooling water chemicals in open circulation
systems are presented for Germany, with industrial cooling systems and power
plants given separately. For continuously added conditioners the loads are
calculated in two ways for comparison, from the concentrations usually applied in
practice and from the concentrations inferred from drawing up the balance.
 63

Table 17: Chemical usage in open circulation cooling systems in Germany

Industrial cooling systems Power plants Sum
Median of active Median of
Proportion Proportion
subst. Load active subst. Load Total load
of plants of plants
concentration [t/a] concentration [t/a] [t/a]
[%] [%]
[mg/l] [mg/l]
Oxidative biocides 1)
Chlorine 4,6 4 184 184
Sodium hypochlorite 2,4 11 264 2,05 10 (410) (674)
Calcium hypochlorite 14,6 1 (146) (146)
Trichlorisocyanuric acid 1 1 (10) (10)
Ammonium bromide / sodium
bromide ? 2 ?
Sodium hypobromite 1,1 4 (44) (44)
1-Brom-3-chloro-5,5-
dimethylhydantoin 3,4 11 374 3,64 20 (1456) (1830)
Hydrogen peroxide 23,6 5 (1180) (1180)
Ozone 0,3 1 (3) (3)
Potassium peroxymonobisulfate 1,1 1 (11) (11)
Peracetic acid 5 1 (50) (50)
1)
Non-oxidative biocides

2,2-Dibromo-3-nitrilopropionamide 0,66 3 20 20
2-Bromo-2-nitropropan-1,3-diol
(Bronopol) 0,02 2 0,4 0,4
Isothiazolinones 0,08 26 21 21
S-Triazines 0,53 2 11 0,5 10 (100) (111)
Dodecylguanidine hydrochloride
(DGH) 0,69 1 (7) (7)
Methylenebisthiocyanate 0,08 3 2 2

Quaternary ammonium compounds 0,267 4 11 0,267 10 (53) (64)

Conditioning chemicals, concentrations used in practice 1)
Phosphate 14 8 421 6 0 0 421
Phosphonic acids 6 42 948 2,3 30 690 1638
Triazoles 1,5 22 124 1,5 30 450 574
Polycarboxylates 9 36 1218 4,5 10 (450) (1668)
Molybdate 6 6 135 - - 135
Zinc 2 15 113 - - 113
Conditioning chemicals, balanced concentration 1)
Phosphate 2 8 160 - 0 160
Phosphonic acids 4,6 42 1932 0,4 30 240 2172
Triazoles 1,1 22 242 ? 30 242
Polycarboxylates ? 36 ? ? 10
Molybdate 0,752 6 45 - - 45
Zinc 1,44 15 216 - - 216
3 3
1) With reference to the fresh water consumption (1000 Mill. m for industrial ccoling, 2000 Mill. m for power plants)
3 3
2) With reference to the discharged water (376 Mill. m for industrial systems, 1000 Mill. m for power plants)
Values in brackets are based on unreliable data basis

5.4.4.3 Once-through cooling

The database for an estimation of the total loads of chemicals used in once-through
cooling systems is not adequate for a reliable calculation, because in most plants
conditioners are not used. An extrapolation of total loads from the 6 plants given (cf.,
table 14) is very unreliable, since these represent individual examples.
 64

At best, an evaluation of the foodstuffs industry sector seems permissible, although

even these numbers have only limited validity (Table 18). In the foodstuffs industry,
based on the data documented in Table 3, ca. 3.2% of the cooling water is
consumed in the processing industry. This corresponds to ca 160 Mio. m 3 cooling
water for once-through cooling (3.2% of 5 billion m 3). In one thermal power plant 1.6
t/a active chlorine is added for the treatment of sea water from the Baltic. However,
this value is not representative for once-through water cooled thermal power plants.
According to an estimate made by the Bund/Länder working group on cooling water
ca. 50 t/a of chlorine are used in thermal power plants with once-through cooling
(Piegsa 2001a). Only in one plant of the chemical industry is chlorine continuously
added. In the discharge of this plant, according ot the operator, there is no
detectable chlorine and the AOX-value of ca. 50 µg/l lies substantially below the
threshhold value.

Table 18: Total load of cooling water chemicals in the once-through cooling of
the foodstuffs industry
Chemical Proportion of Total load 1)
concentration companies
[mg/l] [%] [t/a]
Sodium molybdate dihydrate 7,8 8 104
Chlorine and chlorine releasers 0,6 8 8
Ethoxylated alcohols 0,5 8 6
Cocoiminopropionate 7,8 8 104
Phosphono-carbonic acids 7,8 8 104
1) 3
Cooling water demand of the branch 160 Mill. m

5.4.5 Overview and comparison

The balance sheet of the chemical usage in open circulation cooling shows a
consumption of ca. 4100 t/a for oxidative and 125 t/a for non-oxidative biocides. For
once-through cooling systems there are, in addition, ca. 50 t of chlorine/chlorine-
releasers. The balance shows chlorine concentrations in 4 plants with open
circulation cooling of ca. 4 to 5 mg/l, substantially higher than the value of 0.2 mg/l
given in Table 9. However, the concentration added depends primarily on the
chlorine removal, and the value of 0.3 mg/l pertains to the targeted residual chlorine
concentration in the circulation water. The balance for the chlorine concentration of
4.6 mg/l was based on data reports from only 3 operators, so these values are quite
 65

possibly non-representative. The sodium hypochlorite-concentration (2.1-2.4 mg/l

active chlorine) was, in contrast, calculated from 10 reports and is thus more valid.
However, more extensive research on the cooling plants in which chlorine was used
revealed that the hydraulic conditions also had to be considered. As examples, 2
cases are described:

In one plant of the chemical industry with 2 open cooling systems (Cycles of concentration 2.5 – 3.0)
3
100 kg of liquid chlorine are added batchwise daily to a total circulating volume of 48.000 m /h and the
outflow is closed for 4 h. The measured chlorine concentration after the shock treatment is 0.3 to 0.8
mg/l. However, if one relates the annual consumption of active chlorine of 30.000 kg/a to the amount of
3
fresh water used of 6.5 Mio. m /a, the hypothetical concentration "in the inflow" is increased to 4.6 mg/l.
The ground for this lies in the fact that the amount of fresh “make-up” water introduced is less than the
system volume (which is not known to the operator).

In another plant, also from the chemical industry, ca. 20 kg of liquid chlorine is automatically added
daily to each of 3 cooling circulation systems (concentration factor 2.0 - 2.5) , until a free chlorine
content in the circulation water of 0.3 mg/l is reached (corresponding to a total amount added of 2.9
3
mg/l of circulation water). The overall system volume is 21.000 m , and the mean amount of make-up
3
water added is 9.378 m /d. From this it can be calculated that the system volume (neglecting the
evaporation) is only exchanged once every 2 days. Thereby the hypothetical chlorine concentration "in
the inflow" increases to 6 mg/l.

Thus for batchwise addition of chemicals to the circulation water when the
consumption is based on the volume of added make-up water, substantially higher
hypothetical concentrations may be calculated than the corresponding applied
concentration.

While the consumption of sodium hypochlorite (including chlorine) in Germany is at

about the same level as in the neighboring European countries, the consumption of
hydrogen peroxide and peroxyacetic acid in Germany is notably higher (cf., table 19,
after Anonymous 2000). However, the loads for Germany have been extrapolated
from only 5 reports on the use of H 2O2 and one mention of the use of peroxyacetic
acid. Hydrogen peroxide is used at high substance concentrations (up to 50 mg/l)
and is frequently added continuously, so the large loads seem plausible at first
inspection. However, the calculated consumption numbers for Germany are probably
too high, since hydrogen peroxide is for the most part used in small to medium-sized
cooling systems. A restriction of its use to selected branches of industry, as
supposed by certain employees of the manufacturers, could not be confirmed.
 66

It was noted by the producers that the loads calculated for BCDMH are also too high,
because this biocide is primarily used in smaller plants. The balance drawn up
revealed that BCDM was used in 13 of 110 plants with open circulation cooling with a
total cooling capacity of 140 MW and a total water consumption of 1.5 Mio m 3. In the
largest plant (chemical industry), comprising 2 cooling towers, for a total capacity of
50 MW and a water consumption of 840,000 m 3, ca. 750 kg/a of BCDMH were
consumed. Both power plants were small thermal power plants, with a cooling
capacity under 25 MW.

The production of sodium hypobromite generally takes place on site, through the
reaction of sodium bromide with sodium hypochlorite. The consumption of sodium
hypochlorite was taken into account in Table 17, but for sodium bromide no
concentration data were available. The total load of sodium hypobromite in the
balance in Table 17 is based on one product based with stabilized sodium
hypobromite. The extrapolation of the consumption data for calcium hypochlorite is
just as inaccurate. Its use (as a solid) in cooling systems is unusual, but is
documented in one actual case.

For non-oxidative biocides the consumption data for quarternary ammonium

compounds, isothiazolinones, dibromonitrilopropionamide and methylene-
(bis)thiocyanate are comparable with the values for England. For some biocides
such as ß-bromo-ß-nitrostyrene or glutardialdehyde no consumption values for
Germany were provided, although products with these active ingredients are on the
market. On the other hand, other biocides such as triazine derivatives, guanidine and
Bronopol, for which relevant loads were determined in this study, were not
investigated in neighboring countries. The total load for triazines was substantially
influenced by its rather untypical use in one of the surveyed power plants, and the
high water consumption of power plants over all, which appears unrealistically high.
In a first approximation, the total consumption should be maximally of the same
order of magnitude as for the other non-oxidative biocides (ca. 10-20 t/a).

For hardness stabilisation and corrosion inhibition ca. 1,600-2,200 t of phosphonic

acids were consumed in open circulation cooling. In an earlier study a consumption
of ca. 3.900 t of phosphonates was reported for Europe (without indicating the year)
for cooling water conditioning (Gledhill and Feijtel 1992, Meerkerk and Puijker 1997).
Horstmann et al. (1986) estimated the phosphonate load from cooling circulation for
 67

Germany (the old Bundesländer) to be 3,400 t/a, assuming for all cooling water
circulation a phosphonate concentration of 5 mg/l and for indirect dischargers a 50%
elimination of the phosphonates (Horstmann and Grohmann 1986). Since in this
estimate the concentration factor was not taken into account, the number was later
corrected to 1,200 t/a (Hässelbarth 1987). The amount of PBTC produced in
Germany is given as 1,000-10,000 t/a, and consumption is estimated to be 500-
1,000 t/a. Of this amount, 40% is used in cooling systems (UNEP 1996). Thus the
total load of phosphonates calculated in this project lies at a realistic level. (The total
consumption of phosphonates in all areas of application for the entire U.S.A. is
estimated to be ca. 20,000 t/a; cf., Nowack and Stone 1999). Knepper et al. (2002)
used the data in the Register for washing detergents and cleaning agents to estimate
the consumption of ATMP, HEDP, EDTMP, PBTC and DTPMP as complex-formers
for this purpose in Germany at 11.100 t/a. For the areas of textile-, leather- and
paper-aids another 472 t/a are used. However, these values are also inaccurate
because they fail to include changes in the formulations to be found in the database
and are probably substantial overestimates (Kleinstück 2002).

Heavy metals used in open circulation cooling include ca. 45-135 t molybdenum in
the form of sodium molybdate and 110-220 t zinc, mostly in the form of zinc chloride.

On the other hand, a survey of the emissions of zinc from the cooling water area for
Nordrhein-Westfalen gave a total load of only 5 t zinc/a from cooling water emissions
for the drainage basins of the Rhine, Lippe and Ruhr Rivers (Piegsa 2001a).

However, there are altogether only very few comparative numbers which could be
used to evaluate the reliability of the balance drawn up. Wunderlich (1978) estimated
the consumption of hardness stabilizers, corrosion inhibitors and dispersents in
cooling water conditioning at 12,000 to 20,000 t/a (on a substance-weight basis). To
this total, the biocides must be added, whereby 95% of the biocides were used in
circulation cooling. The applied biocides included chlorine and inorganic chlorine
compounds (95%), acrolein (1%), quarternary ammonium compounds (2%) and
others (together 2%, Wunderlich 1978a). The estimate was based on the then
available cooling systems (flow-through and open circulation cooling), as well as the
concentration of substances corresponding to the most likely used doses and
procedures (Wunderlich 2002).
 68

In principle the size of the cooling plants could also be considered in estimating total
loads of cooling water conditioners, so as not to overestimate the load of, for
example, biocides like hydrogen peroxide or BCDMH, which are primarily used in
smaller plants. However, data on the size in terms of the water volumes are only
available for the 314 thermal power plants supplying the public (from < 5 Mio m 3/a to
>500 Mio. m3/a; cf., Stat. Bundesamt 1998). So as to preserve the systematic basis
of and the plausibility or validity of the balance, it was consciously decided not to
attempt to include any, at best rather arbitrary, “size factor” in assuming the total
water consumption. In order to introduce such a factor, the da tabase would have to
be substantially enlarged. Instead, doubtful data in the balance data in Table 17 are
suitably marked.
 69

Table 19: Comparison of the estimated consumption data for certain biocides
with data from other countries (data in kg/a on a substance basis)

1) 1) 2)
Active substance UK NL F D
oxidative biocides
Chlorine based Chlorine 184.000
Sodium hypochlorite 731.000 2.100.000 817.000 674.000
Calcium hypochlorite 146.000
Sodium dichlorisocyanuric acid 19.300 10.000
Chlorodioxide 13.000
Bromine based Sodium bromide 356.000
1-Brom-3-chlor-5,5-
dimethylhydantoin (BCDMH) 286.000 1.830.000
Sodium hypobromite 44.000
Ozone 0 3.000
Hydrogen peroxide 910 1.180.000

Potassium peroxymonobisulfate 11.000

Peracetic acid 975 50.000
Total amount of oxidative biocides 1.407.185 2.100.000 817.000 4.132.000
non-oxidative biocides
Dimethylcocobenzyl-ammonium
QAV chloride 23.400
Benzylalkylammonium chloride 21.400
Total amount of QAV 71.152 64.100
5-Chlor-2-methyl-4-isothiazolin-3-
Isothiazolinones on 13.200
Total amount of Isothiazolinones 18.000 2.250 20.800
halogenated Bisphenols
(Dichlorophen, Fentichlor) 12.150
Thiocarbamate 56.800
Others Glutardialdehyde 56.400 15.000
Tetraalkylphosphoniumchloride 9.500
2,2-Dibromo-3-nitrilo-
propionamid 17.200 10.000 19.800
2-Bromo-2-nitropropan-1,3-diol 400
S-Triazine 11.000
Dodecylguanidinehydrochloride 6.900
Methylenbisthiocyanate (MBT) 2.270 2.400
ß-Bromo-ß-nitrostyrene 231
Fatty amines 3) 20.000
Others 4.412

Total amount of non-oxidative biocides 248.115 27.250 20.000 125.400

Reference:
UK, F: IPPC Reference Document on the Application of BAT to Industrial Cooling Systems (11/2000)
NL: IKSR Synthesebericht Antifoulings und Kühlwassersysteme (Entwurf 15.11.2001)
D: This study (F+E 200 24 33, Januar 2001)
1) All cooling water systems
2) Only recirculation cooling systems, NaOCl is indicated as Cl2
3) Consumption of fatty amines in a costal power plant
 70

5.5 Elimination of chemicals in cooling systems and sewage plants

Alongside the intended reaction, the greater part of the biocides and conditioners is
eliminated in the cooling system through hydrolysis, adsorption, biological
degradation or evaporation and is thus not relevant for surface waters. This is
especially true for oxidatively acting biocides, whereby the in part more stable
disinfectant side-products (including trihalomethane, AOX, and bromate) must still be
considered. For the non-oxidatively acting biocides the elimination of fluorescent
bacteria toxicity is used as the criterion for inactivation, whereby the elimination
factors involved can usually not be distinguished.

Organic corrosion inhibitors, dispersents and hardness stabilizers are usually not
developed with ready biological degradability in mind, rather it is intended that they
should be stable in the cooling system. The addition of readily degradable carbon
sources in cooling systems would be counterproductive, since these serve as a
substrate for the formation of biomass. Nonetheless, poorly or non-degradable
compounds undergo some degree of elimination in cooling systems. Thus, for the
phosphonic acid 2-phosphono-1,2,4-butantricarbonic acid (PBTC), for example, it is
reported that in the presence of oxidative biocides (chlorine, bromine, ozone) as well
as through photolysis an average of 20% of the PBTC is degraded after its addition
in cooling systems (BUA 1996).

For indirectly discharged cooling waters the elimination ability of the municipal
sewage plant must also be taken into account, for which some examples are given in
Sect. 6.4.2. In the Annex the substance-specific data are presented for hydrolysis,
adsorption tendency (water solubility, log Pow) as well as for the elimination or
biological degradability. From this information, the behavior in cooling towers and in
municipal sewage plants can be estimated, at least roughly.

5.6 Regulatory control of cooling water discharges

The discharge of cooling water is regarded as wastewater emission and accordingly

regulated through the still valid Annex 31 to the Framework-wastewater-
administrative procedures, which was revised in 2002 and is to be included again as
Annex 31 in the German Wastewater Ordinance (Anonymous 2001). In the course of
surveying the companies (cf., sect. 5.3) the responsible authorities were asked to
provide information on the usual practices in controlling cooling water discharges. Of
 71

special interest here was the experience with the fluorescent bacteria test, since it
has been used since 1994 as the legally established standard test for determining
the outflow shut-off pauses for cooling systems with non-oxidative biocides. The
answers of the representatives of the agencies (as a rule, the local water authorities)
were very non-uniform. In some districts only direct dischargers were considered,
while in others all plants above a certain flow-volume were considered. Data on
fluorescent bacteria toxicity were often only requested for direct dischargers. A
systematic presentation of the experiences and results is not available. In personal
discussions with representatives of the agencies it was reported to us that in general
no significant pollutant loads were expected from cooling water emissions. Moreover,
cooling water discharges were often sampled together with partial flows from other
parts of the commercial operations, so that a separate compilation of the data for
cooling systems would require a rather substantial effort.

In our questionnaire distributed to the plants the persons responsible were also
asked about the measured wastewater parameters (governmental agency control or
their own). Of 156 plants with open circulation cooling or flow-through cooling that
provided the corresponding data, for only 23% were data on fluorescent bacteria
toxicity given. Some based their answers on single measurements taken several
years previously, which were not regularly repeated. And even when only those
cooling systems were considered for which biocides were known to have been used,
a similar picture is seen. For only 1/3 of these cooling plants (n=52) were fluorescent
bacteria-test results available. In 2/3 of the cooling systems with biocide use no
fluorescent bacteria tests were performed, even though 40% of these discharged
directly. Only in isolated cases was it mentioned that elimination curves for the
biocides used were even on hand.

In summary, it can be concluded from these data that there is a notable deficit in the
performance of fluorescent bacteria tests for the evaluation of cooling water
discharges.

5.7 Literature and database research

The results of the research on the environmentally relevant substance properties of

the cooling water chemicals are presented in the Annex. Along with the literature-
and database research the information provided by the producers is documented as
 72

“personal communications”. As a rule, the data provided by the manufacturers could

not be verified from original data.

The comprehensive evaluation of the ecotoxicity and degradability is presented in

Table 20. As expected, the aquatic ecotoxicity of the biocides is quite high, while the
corrosion inhibitors and hardness stabilizers can be described as relatively "non-
toxic". With the exception of glutaraldehyde a ready degradability has not been
shown for any of the organic biocides or conditioners. Only for quarternary
ammonium compounds was a complete degradation reported in several studies
(without respecting the 10-day window). In some cases there are still some
significant data gaps. For some of the applied triazole compounds (e.g.,
butylbenzotriazole, chlorotolyltriazole) and phosphonic acids
(hydroxyphosphonoacetic acid, tetraalkylphosphonium chloride) there are virtually no
data available. For PBTC and ATMP, in contrast, there are extensive substance
dossiers (UNEP 1996, UNEP year not indicated). Also, little is known about several
biocides such as the BCDMH-related 1,3-dichloro-5-ethyl-5-methylhydantoin or the
QAV dimethylcocobenzylammonium chloride.
 73

Table 20: Summarized evaluation of the eotoxicity and degradability of cooling

water chemicals
Daphnia Fish Bacteria Biol.
Degradation
Biocides
Chlorine 3 3 3
Sodium hypochlorite 2 2-3 1-0
BCDMH 3 3 + (DMH)
Ozone 3 3
Hydrogen peroxide 2 1 1-2
Glutardialdehyde 2 2 2 +++
Org. Bromo 2-3 1-3 3 +
compounds
Isothiazolines 3 3 3 +
Org. sufluric 2-3 2-3 +
compounds
QAV 3 1-2 1-3 +-++
Corrosion inhibitors and Hardness stabilizers
Phosphonic acids 0 0 0 +
Triazoles 0 1 0 +
Polycarboxylates 0 0 0 +
Triethanolamine 0 0-1 0 +
Zinc- /copper salts 3 2-3 1
Molybdate 0 0
Silicate 0 0 0

The classification of ecotoxicity was performed following the criteria of the GefahrstoffVO:
Classification Classification LC50 or EC50
number
0 Non-hazardous >100 mg/l
1 Hazardous 10-100 mg/l
2 Toxic 1-10 mg/l
3 Very toxic <1 mg/l

The classification of bio-degradability was made following the criteria:

+++ Readily bio-degradability proven
++ Bio-degradable without 10 days window
+ Poorly bio-degradable or inconsistent results
 74

6 Evaluation

6.1 Composition of cooling water

As a rule no ecotoxicity could be found for the cooling waters investigated. After a
shock treatment with biocides a higher toxicity was measured, but this was
completely eliminated within the prescribed inactivation period. Only in one plant with
continuous addition of biocides (BCDMH) was a high toxicity found after an
additional batch treatment with isothiazolinones. Although the outflow was not closed
during treatment in this case, an indirect discharger was involved, so that no direct
hazard for the surface waters was anticipated.

In Germany the first results on the ecotoxicity of cooling water samples treated with
biocides were presented by Börnert and Hagendorf (1992). For one indirect
discharger the effectiveness of a not further specified biocide was inactivated after 4
h, but for another, also after 4 h, a G L- or GA-value of up to 192 was still measured
(Börnert and Hagendorf 1992). Gellert and Stommel (1995) investigated the cooling
water from 41 production plants and found among plants with flow-through cooling
none exceeding the legally prescribed threshhold valules for fluorescent bacteria
toxicity (GL≤12). For plants with circulation cooling with sodium hypochlorite shock
treatments the fluorescent bacteria toxicity correlated with the chlorine concentration
(up to 2.75 mg/l). The highest toxicity was measured immediately after the treatment
of a circulation water with methylenebisthiocyanate (G L=1024). After 5 days the
fluorescent bacteria toxicity of this biocide was also completely eliminated (Gellert
and Stommel 1995). In the most extensive data collection on the ecotoxicity of
cooling water up to that point, Diehl and Hagendorf (1998) presented 248 test
results. The medians for the Daphnia, fluorescent bacteria and algae toxicity lay at
GD=6, GL=1 and GA=6, the maxima at G D=128, GL=16 and GA=32. In comparison to
the other biotests the fluorescent bacteria test was found to be less sensitive (Diehl
and Hagendorf 1998). In a Dutch study the cooling water from 14 plants was
investigated and a clear relationship was demonstrated between the substance
concentration and the ecotoxicity of cooling water samples. In general, cooling
waters treated with the non-oxidative biocides isothiazolinone, DBNPA, ß-bromo-
nitrostyrene and methylenebisthiocyanate showed higher toxicity (up to a dilution
 75

factor of 769) than those treated with the oxidative biocides sodium hypochlorite and
ozone (< dilution factor of 2; cf., Baltus et al. 1999).

6.2 Emission route for cooling water chemicals

The most important emission route for cooling water chemicals or their reaction-
products (e.g., AOX) is the outflow, or for indirect dischargers the municipal sewage
plant. In open cooling circulations a portion of the oxidative biocides can be stripped
out in the cooling tower (cf., sect. 6.4.1 for the example of chlorine, chlorine dioxide).
In addition, chemicals dissolved in water are emitted in the form of expelled water
droplets (ca. 0.01% of the water flow). Along with the chemicals added for
conditioning, these also contain salts and microorganisms from the cooling waters
(VDI 3784: 1986).

6.3 Elimination behavior of cooling water biocides

Having information on the elimination time, for which period the outflow is to remain
closed after a shock treatment with a non-oxidative biocide, provides an opportunity,
according to Annex 31 of the AbwV regulations, to limit the effort involved in direct
on-site measurements of fluorescent bacteria toxicity. This makes it all the more
important to specify precisely the conditions for performing these tests. The results of
the present study show that predictions about the decline in the biocidal effects
should not be considered separately from the inoculum concentration. At a lower
activated-sludge concentration (30 mg d.s./l) the fluorescent bacteria inhibition from
isothiazolinone and Bronopol was not completely eliminated even after 7 days, while
at the highest concentration (1 g d.s./l) a decrease within 1 day to G L<12 was
observed; here elimination through adsorption played an important role. According to
statements from cooling tower operators and manufacturers of cooling water
conditioners, a closure of the outflow for more than 24 h is usually not practical.

In the publication from German et al. (1996) 4 elimination curves for cooling water
biocides in the fluorescent bacteria test are presented. The static experiments were
inoculated with activated sludge from a municipal sewage plant (0.5 g d.s./l), and the
determination of the fluorescent bacteria inhibition was made at a dilution of 12, as in
the present study. Methylenebisthiocyanate (20 mg/l) showed an inhibitory effect of
ca. 80%, which was also not completely eliminated after 24 h. In contrast, a
 76

quarternary ammonium compound, isothiazolinone, and a

dibromonitrilopropionamide-formulation (at product-concentrations of 10, 70 and 100
mg/l) showed inhibitory effects even at the start of only 27% to 50%, so that under
these experimental conditions no effective biocidal effect was detected even by using
individual species such as the fluorescent bacteria. After 2 to 3 h, all 3 compounds
were below the threshold value of 20% inhibitory effect (German et al. 1996).

In a Dutch study the decrease in the fluorescent bacteria inhibition by cooling water
biocides was investigated specifically with regard to hydrolysis as an elimination
factor. Here the surface water used for cooling was tested, without any additional
inoculum, after removing zooplankton by filtration through 25 µm pores. Within 96 h
the fluorescent bacteria inhibition from DBNPA (12.5 mg/l), ß-bromo-ß-nitrostyrene
(2.5 mg/l) and ß-bromo-ß-nitrostyrene/methylenebisthiocyanate (4 and 2.2 mg/l) was
completely inactivated, while for isothiazolinone (1.5 mg/l) and glutardialdehyde (50
mg/l) only minimal elimination was observed (Baltus et al. 1999).

Gartiser and Scharmann (1993) utilized unconditioned cooling water without addition
of any further inoculum to determine the inactivation kinetics of 3 biocides at their
usage concentration. For the biocide based on isothiazolinone the G L-value indeed
decreased within 13 days from G L=128 to GL=16., but did not reach the legally
prescribed threshhold value G L=12. The fluorescent bacteria toxicity of the biocide
based on hydrogen peroxide was completely degraded in 3-6 days. A dye used
against algal growth was already below the threshhold value of GL=12 when tested at
its application concentration (Gartiser and Scharmann 1993).

The question of establishing the experimental conditions for the determination of

"elimination curves" for cooling water still remains open. Elimination curves obtained
under the experimental conditions of the VCI-working group "Biocides in cooling
circulations" with a higher inoculum concentration (activated sludge, 500 mg d.s./l),
favor elimination through adsorption and correspond to the design of an inherent
degradation test. Comparably high biomass concentrations are not normally found in
cooling circulations. The biomass in water channeling systems is sessile, primarily in
the form of biofilms; the microbe count in the water is 10 3 to 104 fold lower. Biofilms
in water-channelling systems seldom exceed a thickness of more than 1 mm and
contain 98% to 99% water. The greater part of their dry mass consists of
extracellular polysaccharides, and only maximally 10% of the dry mass is present in
 77

the form of cells (Cloete and Brözel 1992). A comparative measurement of the
elimination behavior of cooling water biocides in a laboratory test and in real plants is
important, in order to interpret the data correctly. However, here there are scarcely
any published results available. For all such measurements at real plants it is
important that the decrease in the fluorescent bacteria toxicity is not caused by
dilution with added make-up water. Therefore, the outflow must be closed during
such an experimental series. When additional information on the biological
degradability is called for, especially when evaluating direct dischargers, results on
ready biological degradability and/or elimination curves with lower inoculum
concentrations (e.g., 30 mg d.s./l in conformance witih the conditions for the OECD
301 Test of "ready bio-degradability") should be called for.

6.4 Choice of active substances

6.4.1 Biocides

The choice of a biocide depends in part on the organisms whose growth is to be

controlled. Especially for preventing algal growth, copper sulfate, quarternary
ammonium compounds and photosynthesis inhibitors based on triazine derivatives
are used. There are also some contradictory reports on experience concerning the
effect spectrum of cooling water biocides. Thus, for example, it was reported that
glutardialdehyde and quarternary ammonium compounds can only be effectively
used against algae, while isothiazolinones showed the best effect against bacteria.
With methylenebisthiocyanate biofilm formation could not be effectively prevented
(Mattila-Sandholm and Wirtanen 1992). Mussels cannot be effectively combatted in
cooling systems with chlorine-releasers, because they protect themslves by closing
their shells. In these cases non-oxidative biocides such as QAV are used. In one
investigation isothiazolinone but also QAV and thiocarbamate also proved ineffective
against several amoebae isolated from cooling water thought to be causing the
spread of pathogenic Legionella (host organism). On the contrary, a growth-
promoting effect was even observed in some cases (Srikanth and Berk 1993).

In the following, the most important biocides will be described.

 78

Chlorine and sodium hypochlorite

Active chlorine added in the form of chlorine and sodium hypochlorite is the most
important oxidative biocide for cooling plants. For cooling plants that use sea water
as a heat carrier, usually 0.5-1.5 mg/l chlorine is continuously added. In conformance
with the reference document on the IPPC-directive, this is also BAT (Anonymous
2000). Because of the bromides contained in the saltwater, different disinfectant by-
products are produced here than those found for fresh-water chlorination. In a
French study bromoform, dibromoacetonitrile, tribromophenol and dibromoacetic
acid were identified as the main components (Allonier et al. 1999). The VGB-cooling
water guideline recommends a level for continuous addition of 0.1 mg/l free chlorine
(for brackish water) and 0.25 mg/l (for sea water), and for batchwise shock-treatment
chlorination concentrations of 2-3 mg/l free chlorine (Fichte et al. 2000). At the usual
pH-values > 8 in cooling circulation, the biocidal effect of chlorine in the water is
reduced, because the dissociation equilibrium is shifted away from hypochlorous
acid in favor of the less effective hypochlorite-ion (OCI -). In this case it is better to
use the more weakly dissociating hypobromous acid (HOBr), which dominates over
the only weakly microbiocidally acting hypobromite-ion (OBr -) up to pH 9.
Hypobromous acid is, as a rule, generated on site from sodium bromide by adding
sodium hypochlorite (NaOCl). With decreasing pH an increasing proportion of the
hypochlorous acid is stripped out during cooling tower passage (ca. 30-40% at pH 6
and ca. 10% at pH 8.5, Holzwarth et al. 1984, Baltus and Berbee 1996); therefore, it
is recommended to use chlorine-releasing biocides in open circulation cooling in
spite of their lower effectiveness at pH-values above 8 (Anonymous 2000).

Depending on the water composition (including DOC- and ammonium

concentration), pH-value and contact time, the use of free halogens as biocides
leads to the formation of disinfectant by-products such as trihalomethane, chlor- and
bromamine as well as adsorbable organic halogen compounds (AOX).
 79

Chlorine dioxide

In the treatment of drinking water chlorine is in part replaced by chlorine dioxide, in

order to minimize the formation of AOX, especially halogenmethanes. Chlorine
dioxide reacts substantially more weakly with complex organic molecules and
ammonium and thus forms less AOX. Ocasionally, chlorine dioxide is also used in
the cooling water field, whereby it is usually produced on site through the reaction of
chlorine gas with sodium chlorite (NaClO 2). Chlorine dioxide is considerably more
volatile than hypochlorous acid and consequently can be more easily stripped out
from open cooling plants (Anonymous 1991, Groshart and Balk 2000).

BCDMH

Among the organic chlorine- and bromine-releasers, 1-bromo-3-chloro-5,5-

dimethylhydantoin (BCDMH) is preferentially used. Here the actual active compound,
hypobromous or hypochlorous acid, is released after a time delay.

BCDMH hydrolyzes rapidly and because of its limited water solubility it is usually
added over a separate sidestream (over BCDMH filtered cooling water) (van Donk
and Jenner 1996). The organic residue after hydrolysis, 5,5-dimethylhydantoin, is
poorly bio-degradable, but has a weak tendency to adsorption (Anonymous 1994). It
has been reproted that the biocidal effect of 1-bromo-3-chloro-5,5-dimethylhydantoin
is 10 to 20 fold higher than that of chlorine-releasers (Mattila-Sandholm and
Wirtanen 1992). Related compounds such as 1,3-dichloro-5,5-dimethylhydantoin or
1,3-dichloro-5-ethyl-5-methylhydantoin are also occasionally used.

Ozone

Ozone is a highly effective oxidative biocide. While ozone holds a firm position in the
treatment of swimming-pool water, there is little practical epxerience available on the
use of ozone in cooling water treatment (Schmittecker et al. 1997, Schmittecker et al.
1999, Wasel-Nielen and Baresel 1997). In the data we compiled on cooling water
practices (cf., sect. 5.3), there was only one plant that used ozone. In a study of the
Landesanstalt for Environmentschutz Baden-Württemberg the following advantages
of treating cooling water with ozone, as compared to chlorine and non-oxidative
biocides, were listed: effective inhibition of biogrowth, no storage necessary since
 80

ozone is produced on site, no formation of AOX, attainment of the CSB-threshhold,

elevation of the ozone concentration in the air near the ground by maximally 1 µg/m 3
(Schweitzer 1995). The chemical reactions of ozone in water have been described by
Rice and Wilkes (1992). It is reported that ozone decomposes at pH-values above 8
to free hydroxyl radicals. These have a stronger oxidizing effect than ozone itself, but
at the same time they also have a very short half-life of a few micro seconds.
Especially with high concentrations of hydrogen carbonate as a radical-trap, the
disinfectant effect of ozone at pH-values >9 is poor. In the ozonation of bromide-
containing water, the bromide is oxidized to hypobromite-ion (OBr -), which is rapidly
hydrolyzed to the equally biocidal hypobromous acid (HOBr) or to the genotoxic
bromate (BrO3-) ion. As disinfectant by-products compounds such as bromate,
bromoform or monobromoamine are formed, some of which show a genotoxic effect
(Rice and Wilkes 1992, Gunten and Hoigné 1994). Comparative measurements with
the Ames test on the mutagenicity of disinfectant-by-products of ozone, chlorine and
chlorine dioxide in the treatment of drinking water, showed a substantially higher
mutagenicity after disinfection with chlorine. At a dose of 3 mg/l ozone a slight
increase in the mutation rate was found, but at higher ozone concentrations (10 mg/l)
this was eliminated (Kool and Hrubec 1986).

Usually, ozone is added to the cooling water continuously in very low concentrations
of 0.1 to 0.3 mg/l (Wasel-Nielen and Baresel 1997)(Viera et al. 1999). Production
occurs directly on site using high voltage, with an energy expenditure of ca. 10 kWh
per kg ozone. Thus, for cooling systems in energy generation, up to 0.1% of the
energy generated must be used for the production of ozone (Anonymous 2000). Due
to the high oxidative potential of ozone decomposition, when used at high
concentrations, the intermediate hydroxyl radicals formed may attack structures
made of plastic or wood. Organic conditioners, for example dispersents, can also be
degraded by ozone. In order to keep the ozone content low, the cooling water should
have the lowest possible content of organic material.
 81

Hydrogen peroxide

In comparison to the other oxidative biocides, hydrogen peroxide is only effective at

higher concentrations (>15 mg/l; cf., van Donk and Jenner 1996). Reports of lower
effective concentrations were questioned on the part of industry (cf., table 9). Due to
iron- or copper-catalyzed decomposition, it only has a very short half-life. In some
cases, the effectiveness of hydrogen peroxide was improved through the use of
special catalysts.

Rarely, peracetic acid is used as an organic oxygen-releaser in the cooling field. This
compound is readily biologically degradable, but under unfavorable conditions it is
corrosive.

Isothiazolinones

One of the most important non-oxidative cooling water biocides consists of a mixture
of compounds from the isothiazolinone substance group: 5-chloro-2-methyl-4-
isothiazolin-3-one and 2-methyl-4-isothiazolin-3-one. They are already effective in
the concentration range below 1 mg/l. The mechanism of action involves an inhibition
of cellular proteins (Groshart & Balk, 2000). The isothiazolinones hydrolyze slowly
(t1/2 = 7 d at 30°C and pH 8) and are biologically not readily degradable. In
experiments with laboratory sewage treatment plants a limited mineralization of the
compounds (<25%) was demonstarted (Baltus & Berbee, 1996; Krzeminski et al.,
1975). Unpublished test reports from Thor GmbH in simulation tests
(Water/Sediment-test according to BBA IV 5-1) confirm the rapid primary
degradation of the investigated isothiazolinones, but only ca. 10% was mineralized to
14
CO2. Thus, 5-chloro-2-methyl-4-isothiazolin-3-one and 2-methyl-4-isothiazolin-3-
one form stable metabolites, which are to a large part adsorbed in the sediment in
the test system (Schoester 2001).

Isothiazolinones are rapidly bound to biomass. Adsorption and bioaccumula tion in

the biomass are major elimination factors. Investigations with the bacteria
Pseudomonas aeruginosa and P. fluorescens showed that the concentration of 5-
chloro-2-methyl-4-isothiazol-3-one inside the cells was a factor of 400 higher than
outside (Diehl and Chapman 1999).
 82

Quarternary ammonium compounds

Quarternary ammonium compounds (QAV) act by binding to the cell membrane and
are also not readily biologically degradable. In sewage plant passage they are largely
eliminated by adsorption to the activated sludge. With an adapted inoculum or after
longer incubation times, an extensive mineralization of QAV has been reported. The
most important representative in the cooling water field is alkyldimethylbenzyl-
ammonium chloride.

Organic bromine compounds

The non-oxidatively acting dibromonitrilopropionamide (DBNPA) is hydrolyzed rapidly

to the in part still biocidal compounds dibromoacetonitrile, dibromoacetamide,
monobromonitrilopropionamide and cyanoacetamide. Only substance-specific
degradation data are available (Blanchard et al., 1987). The substance itself is
presumably poorly biologically degradable (Groshart & Balk, 2000). Other members
of this group include 2-bromo-2-nitropropan-1,3-diol (Bronopol) and ß-bromo-ß-
nitrostyrene, but no degradation data on these compounds is available. Bronopol is
hydrolyzed slowly (t1/2=14 d at 30°C and pH 8), but in contrast ß-bromo-ß-
nitrostyrene hydroyzes rapidly (t 1/2=20 min at 30°C and pH 8) (Baltus and Berbee
1996).

Glutardialdehyde

Glutardialdehyde is only used occasionally in the cooling water field. The mecha nism
of action is based on the denaturation of proteins. Glutardialdehyde is less toxic for
aquatic living organisms as compared to the other biocides, and the concentration
used is correspondingly higher. The compound is readily bio-degradable.

6.4.2 Cooling water conditioners

Phosphates

Phosphates and polyphosphates have been used for a long time as corrosion
inhhibitors. For very soft waters a cooling water treatment with zinc ions or inorganic
phosphates is often used for steel as a satisfactory protection against corrosion. The
concentration of orthophosphate used to inhibit corrosion is maximally 15 mg/l. This
corresponds to a concentration of phosphorus of ca. 5 mg/l. In the opinion of several
 83

of the manufacturing companies, in the present study the balance sheet loads of
inorganic (poly)phosphates are probably underestimates. However, this could not be
confirmed. Even if the consumption of phosphoric acid is assigned to the phosphates
(as was the case), in comparison to the organic phosphonic acids substantially fewer
plants report the use of inorganic phosphorus compounds. The evaluation of product
information showed that phosphates were primarily used in combination with
phosphonic acids and/or polycarboxylates, as well as with zinc or molybdates. This
explains why the overall balance gave phosphate concentrations lower than would
correspond to the concentration added if used alone. Thus, for example, a good
protective effect was achieved for non-alloy steel in cooling circulations using sodium
polyphosphate as well as sodium polyphosphate or polyacrylate in combination with
zinc sulfate. The exclusive addition of zinc sulfate did not reduce the rate of corrosion
(Naumann and Schimke 1991). Hence, the calculated concentrations (1.8 mg/l) also
are lower than the values that would be necessary for the sole addition of phosphate
(cf., table 16). Of note is the frequent use of inorganic phosphates in the water added
to the heating vessel.

Phosphonic acids

Phosphonic acids are used in very sub-stoichiometric concentrations for hardness-

stabilsation (treshold-effect) and in higher concentrations as corrosion inhibitors.
They are biologically poorly degradable and stable against hydrolysis. In the
concentration range of 5-20 mg/l some phosphonic acids have good properties as
corrosion inhibitors for steel (all-organic operation). In conjunction with zinc, however,
only one-half the phosphonic acid concentration is needed for a corrosion inhibiting
effect.

Under the phosphonic acids which could be unequivocally identified in the product
information provided, the frequency distribution was HEDP >
hydroxyphosphonoacetic acid > PBTC >> ATMP and DTPMP. By and large, this
agrees with the frequency of the surveyed phosphonic acids
(hydroxyphosphonoacetic acid > HEDP >> ATMP = PBTC = DTPMP). However,
owing to the poor documentation, the predominantly consumption numbers for
phosphonic acids could not be assigned to particular substances.
 84

The elimination of PBTC in sewage plants appears to occur, according to laboratory

experiments, 0-60% through adsorption, as well as 60-100% through flocculation (P-
elimination (BUA) 1996). Metzner et al. measured the elimination capacity for HEDP
and ATMP in municipal sewage plants to be ca. 50% (Metzner 1990).

The elimination of some other phosphonates in municipal sewage plants is reported

to be on the order of 50%. Adsorption experiments with radioactively labeled
phosphonic acids at environmentally realistic concentrations showed that 23-70% of
EDTMP and 80-90% of DTPMP was adsorbed to various activated sludges (Gledhill
and Feijtel 1992). In general, phosphonates influenced the phosphate-precipitation,
as the third purification step, since they form complexes with iron(III)-ions. However,
this influence is compensated by the higher concentrations of flocculants (Horstmann
and Grohmann 1986). The dependence on pH-value and the concentration of heavy
metals for the adsorption of phosphonic acids onto clay minerals was investigated by
Nowack et al. (1999). They found that the adsorption decreased substantially above
pH 8. While copper and iron ions only had a limited influence on adsorption, it
increased noticeably in the presence of calcium (Nowack and Stone 1999). In the
outflow of 7 municipal sewage plants with phosphate-precipitation, phosphonate
concentrations were generally below the detectability limit (ca. 2 µg/l). The
elimination in the sewage plant was over 80% (Nowack 1998).

Only a few studies considered the behavior of the metabolites of phosphonic acids.
In a recent Dutch study the in- and outflow-concentrations of aminomethylene-
phosphonic acid (AMPA), a degradation product of ATMP, were determined in 5
municipal sewage plants. In some cases, higher concentrations were measured in
the outflow. (Meerkerk and Puijker 1997). The proportion of the cooling water
conditioners (for direct dischargers) in the total load of AMPA in a part of the
drainage basin of the Maas River was estimated at 28%. The contribution by
municipal sewage plants was in the same range. An additional source for AMPA is
the degradation product of the herbicide Glyphosat (Meerkerk and Puijker 1997).

Nowack et al. (2001) investigated 2 diphosphonates which are formed in the catalytic
degradation of ATMP in the presence of manganese(II)-ions and molecular oxygen.
These compounds were also effectively eliminated in the sewage plant (>80%)
(Nowack 2001).
 85

In the surface water the photodegradation of phosphonic acids surpasses bio logical
degradation by far, especially when they are present in the form of iron complexes
(Gledhill and Feijtel 1992, Steber and Hater 1997). It should be noted, however, that
only the primary degradation of the substances was determined. Several studies
document a substantial photodegradation of phosphonic acids in the presence of
equimolar amounts of iron ions (ca. 44% to 82% at pH 7 in 17 days with natural
sunlight illumination; Gledhill and Feijtel 1992). Unpublished data of the Bayer AG on
the photodegradability of PBTC, HEDP and ATMP at a test concentration of 10 mg/l
in the presence of 0.2 mg/l iron-ions indicate a PBTC-degradation of 53-81% within
24 h, but a negligible degradation of HEDP and ATMP over this time. Without the
addition of the iron-ions no photodegradation of PBTC was detected. The presence
of nitrate also favored photodegradation. Adsorption experiments with radioactively
labeled PBTC (1 mg/l) showed that 95% adsorbed to the activated sludge
(Kleinstück 2001). However, the photolysis of the iron(III) complexes of ATMP and
DTPMP, unlike that of the iron(III)complex of EDTA does not lead to biologically
degradable compounds (Nowack and Baumann 1998). As an additional, relevant
degradation mechanism in natural surface waters, the catalytic oxidation in the
presence of manganese-ions and oxygen has been discussed (Nowack and Stone
2000).

The analytical determination of phosphonic acids and their metabolites in surface

waters has so far been limited by the relatively high detection threshold of ca. 2-13
µg/l with the method of Klinger et al. (1999) and Nowack (2001). However, since it
can be expected that phosphonic acids will be found in surface waters, their
elimination in the treatment of drinking water has been investigated. The results
show that all phosphonates are removed by precipitation with iron(III)- or aluminum-
salts under practically relevant conditions. Using ozone only the nitrogeneous
phosphonic acids are completely converted, whereby the herbicide Glyphosat and its
main degradation product aminomethylphosphonic acid (AMPA) are formed as
oxidation products (Klinger et al. 1998).

Polycarboxylates

Polycarboxylates are generally regarded to include the water-soluble negatively

charged polymers (polyelectrolytes) which are primarily used (alongside zeolites) as
phosphate substitutes in the wash-detergent field. These are homopolymers of
 86

acrylic acid as well as co-polymers of acrylic acid and maleic acid with a mean
molecular weight (MW) of ca. 70,000 (Opgenorth 1992). These are not classified as
defined compounds with their own CAS-numbers, so no direct substance searches
could be carried out, and reference had to be made to more general studies. This
substance group is consequently not included in the Annex.

In Germany ca. 20,000 t/a polycarboxylates are used in wash detergents (Kaiser et
al. 1998). In the cooling water field, hardness stabilizers and dispersants of
polyacrylates, polymethacrylates and polymaleinates, sulfonated copolymers and
polyacrylamides are all grouped together under polycarboxylates (Piegsa 2001b).
Polycarboxylates with MW of 500-20,000 are used in the cooling water field for
hardness stabilizing, and higher molecular forms (up to MW 50,000) as dispersents
(Andres et al. 1980). In the product information these compounds are often listed
under polycarbonic acids. All these compounds are poorly bio-degradable, whereby
a low molecular weight favors degradation. Thus, the copolymer of acrylic acid and
maleic acid at a MW of 70,000 is only degraded 20% after 30-90 days, and at a MW
of 1000 up to 45% (Opgenorth 1992). In municipal sewage plant polycarboxylates
are primarily eliminated through precipitation with calcium and magnesium hardness
and adsorption to the activated sludge, whereby in laboratory experiments (Zahn-
Wellens-test, SCAS-test, laboratory sewage plant) values up to 98% were
determined for higher molecular weight compounds. Below a MW of 10,000 the
adsorption tendency of a copolymer of acrylic acid and maleic acid decreases
substantially (Opgenorth 1992). In a recent study on the degradability of 2
radioactively labeled polycarboxylates based on acrylic and methacrylic acid and
styrol at a MW of 55,000 and 7,000 only negligible mineralization in the CO 2-
evolution-test (OECD 301 B) was measured. In the SCAS-test (semi-continuous
activated sludge test according to OECD 302 A) < 1% of the polycarboxylates was in
the aqueous phase, and the bulk (96-99%) was adsorbed to the activated sludge
(Jop et al. 1997).

The aquatic ecotoxicity of polycarboxylates is generally low. The EC 50 for Daphnia,

and fish was > 200 mg/l for the copolymer of acrylic acid and maleic acid with MW=
4500 or 70,000 (Kaiser et al. 1998, Opgenorth 1992). In the activated sludge-
respiration-inhibition test (OECD 209) up to a concentration of 3,200 mg/l no
significant inhibitory effect against the activated sludge could be detected (Jop et al.
 87

1997). Similar data were reported by Guiney et al. (1996). Also the polycarboxylates
used in the wash-detergent field have a low ecotoxicity. A potential to remobilize
heavy metals and for bioaccumulation was not observed (Schöberl and Huber 1988).
Dispersants based on acrylic acid with a MW of 45,000 were weakly ecotoxic in the
activated sludge respiration-inhibition test, fluorescent bacteria test and algae test
with EC50 values <100 mg/l. However, for aquatic crustaceans of the species
Ceriodaphnia dubia chronic effects due to physical damage have been reported, the
NOEC (no effect concentration) here was 1 mg/l (Guiney et al. 1996).

Triazoles

Triazoles are predominantly used as corrosion inhibitors for copper and its alloys.
The most important compounds are benzotriazole and tolyltriazole (Andres et al.
1980). The triazoles generally have low aquatic ecotoxicity. Few data are available
on the degradability or elimination, but triazoles are generally regarded as not readily
degradable. The degradability of tolyltriazoles appears to depend on the position of
the methyl group. While 5-methyl-1H-benzotriazole reported to be degraded in
cooling towers, 4-methyl-1H-benzotriazole is stable (Cornell et al. 2000). These data
agree with the Zahn-Wellens test results (96% elimination for 5-methyl-, 0% for 4-
methyl-1H-benzotriazole; cf., annex). For other compounds there are serious data
gaps as regards the ecotoxicity and eliminability.

Heavy metals

Zinc and molybdenum are also used as corrosion inhibitors in open industrial cooling
circulations. When these heavy metals are indirectly discharged, elimination in the
sewage plant through adsorption should also be taken into account. It is well known
that adsorption to the activated sludge occurs, and consequently threshold limits
have been established according to the sewage-sludge regulations (for removal for
spreading on agriculturally used soils, for zinc 200 mg/kg).

Zinc

According to Annex 31, zinc salts may not be used in open cooling systems of power
plants. The evaluation of the questionnaires confirmed that this restriction was
respected. In industrial cooling systems zinc is often used in combination with
phosphates or phosphonates. In combination with phosphate the pH in the
 88

circulation water is maintained in the neutral range through the addition of mineral
acids, in order to avoid excessive deposition of poorly soluble zinc hydroxides or
calcium phosphate. In contrast, when using phosphonates the addition of acid is not
necessary (Piegsa 2001b).

A balance for the zinc loads in the in- and outflows of municipal sewage plants
revealed that ca. 50% was eliminated with the excess sludge and 50% passed with
the wastewater in the final settling tank (pond) (Kroiss and Zessner 2001). Zinc is an
essential trace element for animals and plants, but in higher concentrations is toxic.
The zinc content in the outflow of industrial cooling circulations is limited to 4 mg/l
according to Annex 31.

Molybdenum

Several manufacturers remarked that molybdate is primarily used in closed systems.

Nonetheless, its use in open systems is documented for 6 plants (from the foodstuffs
industry, automobile industry, chemical industry and one steel plant), so its loads
may not be neglected. The use in open systems also agrees with the producer’s
information for several products. Molybdenum is an essential trace element for plants
and is contained in the enzyme for nitrogen fixation (nitrogenase), as well as in
several animal enzymes. Consequently, small amounts of molybdates are added to
some fertilizers. However, higher concentrations can be toxic for both plants and
grazing animals (Parker 1986). In comparison to zinc salts, the aquatic ecotoxicity of
molybdates is substantially lower. Investigations on the adsorption of molybdates to
activated sludge are not available, but it can be supposed that there is an enrichment
on the activated sludge.
 89

7 Recommendations

Cooling plants are components of complex thermal technical processes and

furthermore are dependent on the available water and the local conditions.
Consequently, an optimization of the cooling and the selection of the conditioners
should always take into account the whole process.

7.1 Energy conservation measures

Cooling plants are used to remove from the industrial process excess heat produced
during the consumption of primary energy. Hence, a rational use of the energy leads
not only to cost savings, it also reduces the emissions of greenhouse-gases and the
effort required of the cooling plants including the amount of chemicals. In optimizing
the process internal measures to save energy should thus have the highest priority.
In addition, the use of the industrial waste heat for thermal energy is by far the most
environmentally friendly system for the provision of low-temperature heating. For this
reason, an increased development of thermal energy production with the utilization of
industrial excess heat is being sponsored (Roth et al. 1996).

7.2 Technical solutions

In the reference document "Industrial cooling systems" the various technical

possibilities for the optimization of cooling plants are comprehensively presented, so
here only the essential elements need to be mentioned. The choice of the cooling
system depends on the local givens, such as, e.g., the capacity of the surface water
to be used. From the questionnaire to the cooling plants it was surprisingly learned
that, in 34 of the 110 surveyed plants with open circulation cooling, ground water was
used for cooling purposes and in 12 plants drinking water. Indeed, in 3 plants more
than 100,000 m 3 drinking water were used annually for cooling. Thus, the water
supply can be a significant cost factor and influence the site selection.

Regarding the choice of basic materials, it seems that because of the complexity of
cooling water systems there is no ideal basic material. Nonetheless, the choice must
be made according to the specific requirements. In the VGB-cooling water guideline
recommendations for basic materials for pipes, heat exchangers and water
 90

chambers are provided with considerations of the water composition (chloride

content).

From the experiences reported by the employees of the plants included in this study,
it became clear that already through simple measures the cost intensive use of
cooling water biocides could be reduced, in some cases by 90%. Thus, for example,
the orientation of the cooling tower with respect to the sun plays a decisive role for
the growth of algae, the primary producer of biomass. Already through the placement
of the cooling tower and/or its subsequent shading, algal growth can be substantially
reduced.

Pre-treatment of cooling water: Through treatment of the added water dispersed

material can be removed by filtration procedures, or the carbonate hardness and/or
the salt content of the added water reduced with an ion-exchanger. Thereby, the
amount chemicals required can be reduced and higher concentration cycle factors
can be adjusted downward. However, in making a comparative evaluation, the
chemicals required for the decarbonization and regeneration of the ion-exchanger
must also be taken into account. Thus, the regeneration requirements for
hydrochloric acid and sodium hydroxide fluctuate between 110% and 250% of the
stochiometrically called for amounts, and for sodium chloride solution (NaCl)
between 150% and 300% (Greiner et al. 1987, Kohler 2000). For power plants,
because of the large demand for water, the treatment of the added water is generally
limited to the primary interfering substances (mechanical prurification by filtration,
decarbonation with sulfuric acid or calcium hydrate) (Fichte et al. 2000).

Side-stream filtration: The addition of chemicals in open circulation cooling can also
be reduced by continuously cleaning a partial-stream using filter technology. Thus
concepts were developed to reduce the potential for biofouling in cooling systems by
removing the nutrient materials. By introducing a reverse-flow washable sand filter
upstream, the formation of the biofilm can be specifically limited to an easily
controllable system and thereby protecting the downstream cooling plant. The
biologically degradable carbon could be reduced in one plant with this technique to
1/4 of the original value. The thickness of the biofilm was corresponding reduced by
90% (Griebe and Flemming 1996). By cleaning just 1-3% of the circulating water
over a continuously operating sand filter the consumption of sodium hypochlorite was
reduced by 70-80% (Daamen et al. 2000). The VGB-cooling water guideline
 91

recommends where appropriate the filtration of a side-stream of up to 5% of the total

flow through the use of gravel-filters (Fichte et al. 2000). According to Kunz (1993)
water circulations “should be regarded as bioreactors in which growth should not
take place". Based on the observation that many organisms protect themselves from
colonization with bacteria by keeping their milieu iron-free, his biotechnological
concept for limiting the biomass growth consists of seeking to specifically reduce the
concentration of iron ions in the cooling system (Kunz 1993).

Water-flow velocity: Periods of standing, stagnation phases and too low flow
velocities are to be avoided, in order to minimize the risk of biomass formation,
corrosion and scaling. In the reference document of the EU on industrial cooling
systems current velocities of 1.8 m/s are described as a BAT-measure to protect
condensers and heat-exchangers (Anonymous 2000). On the other hand,
excessively high flow should also be avoided to prevent possible erosion corrosion
phenomena and the formation of a protective layer. In the VGB-cooling water
guideline a current-flow velocity range of 0.5-3 m/s is recommended (Fichte et al.
2000).

Chemical-free operation: Occasionally, there are reports of attempts to introduce

physical procedures for cooling water treatment. Thus, for example, in laboratory
experiments electrical impulses were successfully used to control salt-water polyps
(Hydrozoa arge) (Abou-Ghazala and Schoenbach 2000). Brief treatments with heat
or microwaves are supposed to control the biology in cooling systems (Anonymous
2001c). However, corresponding descriptions of practical experience here are not
available.

7.3 Process operation

In the course of our visits to the plants, various employees reported to us that the
amounts of chemicals to be added could be substantially reduced by regular
cleaning of the cooling pans and sprinkling structures. It is known that biofilms are
substantially more resistant to biocides than planktonic microorganisms. Moreover,
killing the organisms present does not remove the biofilm itself, so that the possibility
of a rapid recolonization and a continuation of the biofouling exists. Therefore,
attempts are made to remove the dead biofilm with dispersants, but often this only
partially succeeds (MacDonald et al. 2000). Insofar as the formation of biofilms with
 92

acceptable thicknesses cannot be prevented in advance, mechanical cleaning

methods are more effective. The VGB-cooling water guideline recommends the
continuous cleaning of the cooling pipes with beads or brushes. A number of bead-
carriers (sponge, granulate or polishing beads), coated with various materials
(pumice, plastic, natural rubber, corundum), are available on the market (Fichte et al.
2000).

There are also self-cleaning heat-exchangers available on the market in which

particles 1 to 3 mm in diameter are carried with the cooling water current and before
emission are reclaimed, e.g., via hydrocyclones (internal circulation, e.g. Klarex
Technology B.V., the Netherlands). Fully automatic systems for the cleaning of
condensers with compressed air have been developed. Larger surfaces are cleaned
with high-pressure water streams (50-200 bar), and for pipes automatic cleaning
systems are offered (brush-cleaning, sponge-bead-cleaning, swab-cleaning) (Paikert
1986).

Closing the blow-down after a batch treatment with biocides until their demonstrated
inactivation is an important instrument for protecting the sewage plant and the final
tanks. Another advantage of closing the outflow is that the contact time of the
biocides with the cooling water is increased and at the same time also their
effectiveness.

Carefully measuring the added cooling water chemicals to match the amount actually
needed can potentially bring a great savings. For example, quick methods were
developed for surveillance (monitoring) of the microbiological activity of cooling water
samples. One possible measureable endpoint for this is the content of adenosine
triphosphate (ATP) in the cooling water, which can be measured with luciferin as
released light (Marczewski et al. 1995, Hild 2000). In addition, fluorescent bacteria
toxicity is also used to monitor the effect of a present biocide. At G L-values >2 there
was a distinct reduction of the total number of colonies (Schaaf no year given).
Several companies offer measuring instruments for the determination of the
fluorescent bacteria toxicity (e.g., Dr. Lange Lumismini, Merck ToxAlert ®, FH-
Furtwangen, BetzDearborn Bioscan TM). However, based on previous experience,
these techniques are hardly ever applied in practice. Instead, a continuous
conductance measurement in the outflow of open circulation cooling plants is state of
the art in order to permit adjustment of the blow-down and with it the concentration
 93

factor. Moreover, the dosing of the addition of chemicals can be guided by online
measurements. Phosphonic acids can also measured with online phosphate
analyzers (Elfering and Schmitz 1995).

7.4 Evaluation and selection of cooling water chemicals

There are essentially 4 approaches with which the hazard potential from cooling
water chemicals can be evaluated and applied as an instrument for the selection of
an active ingredient. In the reference document of the European Commission 3 of
these are presented in detail, so here only the basic outlines and possible
associations will be mentioned (Anonymous 2000).

7.4.1 Water risk classes, the VCI-concept for open cooling systems

The concept of the Verband der Chemischen Industrie was not developed for the
evaluation of cooling water chemicals, rather for taking measures during possible
leakages with water-hazardous substances. It proposes measures for monitoring and
adjusting fresh-water and open circulation operation, as well as alternatives to once-
through cooling, depending on the water-risk presented by the substances which
could be introduced by leakages of cooling water. The basis is a derivation of water-
hazard classes in conformance with European laws on hazardous substances from
the Risk- or “Gefahren-“Phrases (R-Phrases), which are presented in the
“Verwaltungsvorschrift wassergefährdender Stoffe" from 17 May 1999 (VwVwS) and
expounded by the Commission for the evaluation of water-endangering substances
(Kommission zur Bewertung watergefährdender Stoffe 1999). Here each R-Phrase
relevant for the protectable natural resource aquatic environment in combination with
the protectable natural resources human health and soil protection is assigned a
certain point value. The points for all the R-Phrases given to a particular substance
are added up to give a total number of points. Here data gaps on ecotoxicity,
degradability/bioaccumulation or acute oral/dermal mammalian toxicity are
compensated with additional default assigned values. With this total point value the
water-risk class of a substance in accordance with the VwVwS can be determined.
For prepared mixtures a water-risk class for the product is then generally determined
from the consideration-limits (the sum of proportional values for each of the WGK-
substances present, scaled on a percentage basis corresponding to its proportion in
the mixture) (Annex 4 VwVwS).
 94

The VCI-concept links the total point value with the necessary cooling water safety
measures (Anonymous 2001b, Anonymous 2000, Piegsa 2001b). For substances
with a total point value > 5 (corresponding to WGK 2) depending on the
contingencies of each individual case, measures for the monitoring of once-through
cooling systems should be immediately undertaken and where appropriate the
cooling water should be directed into wastewater treatment facilities (usually
municipal sewage plants). However, the concept is only valid for direct dischargers.

Although the VCI-concept is not intended for the selection of cooling water chemicals
based on environmental aspects, the emission based approach for considering
water-risk classes could be a possible instrument for a comparative evaluation of
cooling water chemicals.

However, since the assignment of water-risk classes especially considers the

accident situation, the concept requires further development, e.g., in order to
relativize the high ecotoxicity of a chemical to a known rapid elimination in cooling
systems or sewage plants. In addition, for mixtures the consideration-limits (the sum
of proportional values for each of the WGK-substances present based on the
composition of the mixture) must be incorporated for the determination of WGK-
classes.

7.4.2 "Benchmarking"-concept

Benchmarking is a continuous process, in which a defining evaluation parameter is

compared with a reference situation (benchmark). Here data from comparable
situations are collected and compared with the target data of the reference situation
in the form of a relative "ranking" so that every participant can recognize "where he
stands", i.e., how far he is from the benchmark. In the reference-document of the EU
"Industrial cooling systems" this instrument was applied to the procedure of risk
evaluation for chemicals usually followed in the EU, as described in the Technical
Guidance Document (Commission 1996). This is based on the ratio of the
environmental concentration to be expected (predicted environmental concentration,
PEC) to the threshold-concentration, below which no effects would be expected
(predicted no effect concentration, PNEC). Here the PEC is calculated from emission
scenarios from the discharged amounts, the elimination factors and the dilution; the
PNEC is generally determined from laboratory ecotoxicity tests assuming certain
 95

safety factors (up to a factor of 1000). In special cases the PNEC is also extended
using model ecosystems as well as field studies. In Annex V of the Water-
Framework-Directive of the EU (2000/60/EG) the procedure for obtaining the PNEC
is to be introduced in order to define the chemical quality standards to be established
by the member states. Here data on persistence and bioaccumulation are to be
considered (environmental quality standards, EQS). The "benchmarking"-concept
only envisages a relative evaluation of the cooling water chemicals, corresponding to
their ratios for PEC/PNEC or PEC/EQS. A conceivable further development of the
concept for the evaluation of substance mixtures exists in the introduction of an
Index-Number (=sum of the PEC/PNEC-ratios of the individual components).

The advantages of this immission-based procedure are that substance-inherent

properties of the chemicals can be used and the local conditions taken into account.
However, the focus is on the aquatic ecotoxicity. Indirect negative effects on humans
are not considered, insofar as there are no official EQS derived from the chemical
evaluations of the EU available. A further disadvantage is that the PEC depends on
the flow of the receiving river, so that there is a tendency to view dilution as solving
the problem ("dilution as solution"), while the real goal of limiting the load recedes
from view. In addition, the additional burden on the receiving river through other
emissions upstream can only be taken into account with great effort. While the
elimination in sewage plants is fully considered, also for adsorptively bound
chemicals, other exposure paths, e.g., through an agricultural utilization of the
activated-sludge ase not considered. The "benchmarking"-concept thus remains only
a promising approach, which still should be further developed.

7.4.3 Plant specific evaluation of cooling water chemicals

The benchmarking-concept was further developed by Baltus et al., among others,

especially to provide an instrument with which the use and selection of cooling water
biocides could be optimized (Baltus and Berbee 1996, van Donk and Jenner 1996,
Baltus et al. 1999). The basis for this is an extension of the benchmarking-concept to
actual cooling plants. While in the benchmark-process the inital pre-selection of the
biocide is made on the basis of relative "rankings", in the optimization phase all
available techniques for process operation, dosing, treatment and control are
considered. Thereafter the local effects on the environment are estimated and
 96

measures for their reduction, for example through treatment of the added water,
dosing, closing the outflow or monitoring, are established.

7.4.4 TEGEWA-concept for indirect dischargers

The TEGEWA, together with the Gesamtverband der Deutschen Textilver-

edelungsindustrie developed an evaluation concept for the classification of textile
treatment aids. Based on their relevance for surface waters and in 1997 in this was
established as a self-commitment to be followed voluntarily (Noll and Reetz 1998).
The basis is a classification of textile additives in 3 classes from slightly to strongly
relevant for emitted water depending on their composition of bio-accumulable
substances (classification in R 53), their toxicity for surface waters (LC 50 Daphnia),
their ready bio-degradability (OECD 301 tests) and their eliminability in sewage
plants (Zahn-Wellens test). Certain problem substances (cancerogenic, genotoxic
and reproduction toxic substances) a priori lead to classification in Class 3, while on
the other hand textile chemicals, which are hazardous to water organisms (R 52) and
are not readily degradable (R 53) are still assigned to Class 1 if substantial
elimination in sewage plants occurs. In its structure the TEGEWA-concept resembles
a classification of water-endangering substances, but it takes into account the
elimination in municipal sewage plants.

7.4.5 Outlook

From the viewpoint of the researcher a combination of an emission-based approach

based on the classification in water-endangering classes or the TEGEWA-concept
with the immission-based "benchmarking"-approach would be a possible instrument
for making a pre-selection of suitable cooling water chemicals. The assignment to
water-endangering classes also includes health aspects, along with aquatic
ecotoxicity. Moreover, any lacking data are compensated by default values following
the precautionary principle. However, in order to place priority attention on the
emitted loads, both the used amounts as well as the elimination in the cooling
system and (for indirect dischargers) in the municipal sewage plant must be more
strongly considered. Thus the TEGEWA-concept tends more to include the
elimination in the wastewater treatment facility. The total load should, however, also
be considered, so that, for example, effective biocides with higher aquatic toxicity but
a lower use concentration are not a priori rated as worse than less effective biocides
 97

with higher loads. The total load is included in the evaluation in the "benchmarking"-
concept, but is also relativized through the dilution in the final settling pond. However,
the goal should be the minimizing principle, in introducing hazardous substances
while at the same time maintaining the goal of environmental quality. In order to
direct the idea of "benchmarking" in this direction, a relative ranking of cooling water
chemicals in the direction of toxicity loads (=effect concentrations x load) should be
possible.

In general, the emission-based wastewater-evaluation is regarded as the stricter,

precautionary principle-bound approach, while the immission-based approach first of
all requires the definition of quality criteria. Of course, there have been attempts to
link the two strategies. Also in the EU-Water Framework guideline the "combined
approach" has elements of emission- (emission controls for prioritary substances)
and immission-based criteria (environmental quality standards), (cf., also Reemtsma
and Klinkow 2001).

More advanced concepts for the evaluation of wastewater inputs on the basis of
ecotoxicity, bioaccumulation, degradability and genotoxicity have been developed by
Reemtsma and Klinkow, among others, and are currently being discussed at the
OSPAR (Reemtsma and Klinkow 2001, Commission 2000).

In order to undertake a qualified evaluation of cooling water chemicals their identity

and properties must be known. In the Annex some essential data regarding
ecotoxicity, genotoxicity and biological degradability, which were obtained in
extensive substance-based searches, are listed together with the R-Phrases and the
physico-chemical properties. It should be emphasized that this data set is only
sufficient to permit an initial estimation of the environmental relevance of cooling
water chemicals to be made and is not sufficient for a complete evaluation in
accordance with chemical laws.

In any case, the optimization of the use of cooling water chemicals must be made
with a consideration of the local conditions and the available techniques for process
management, dosing, treatment and monitoring. The various evaluation strategies
described above can only reflect general basic principles. In order to achieve the
needed linkage of the emission- and immission-based approaches, these strategies
must be further developed.
 98

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9 Ackknowledgements

The successful completion of the F+E-Project was only possible through the
cooperation and assistance of numerous persons, whom we would like to thank here
most sincerely:

• Mr. Mehlhorn, Fachbereichsleiter Abteilung II 3.2 "Stoffhaushalt Gewässer",

Environmentbundesamt and Leiter des IKSR-Expertenkreises "Antifouling and
Kühlwaterkreisläufe" for outstanding support, advice and coordination of the
project,
• Mr. Seelisch, FG II 3.1 "Übergreifende Angelegenheiten Gewässergüte and
Waterwirtschaft", Environmentbundesamt for research in internal data banks,
• The otehr employees of Hydrotox GmbH for conscientious performance of the
tests, especially Mrs. Stiene (Daphnia-, algae-tests), Mrs. Welsch (umu test,
Ames test) as well as Dr. Schnurstein (coordination in the area of mutagenicity),
• Mrs. Knieß for the secretarial work and for correcting the manuscript,
• Mr. Piegsa, Staatliches Environmentamt Herten and Obmann des Bund-/Länder-
Gesprächskreises "Kühlwater",
• The representatives of the agencies of the Länder and Bezirke for their support
with the questionnaire on the use of cooling water chemicals in the operating
facilities,
• Dr. Ungeheuer, TEGEWA, for the organisation of the Workshop,
• The employees of the facilities considered for providing information and samples
and for filling out the questionnaire,
• The representatives of the companies manufacturing conditioners for providing
product information, safety data sheets and additional, in part unpublished
information, especially Dr. Klautke, BetzDearborn GmbH; Dr. Hater, Henkel
Surface Technologies GmbH; Dr. Kleinstück, Bayer AG; Dr. Weindel, BK-Giulini
Chemie GmbH & Co OHG; Dr. Olkis, Fa. ONDEO Nalco Deutschland GmbH; Dr.
Heinl, Drew Ameroid Deutschland GmbH; and Dr. Schoester, Thor GmbH.