1

2022-2023 | 2º semester

Engenharia de Sistemas de Tratamento II

Treatment Systems Engineering II
Class TP #2 | 20-Feb-2023
 2
P Date G1 G2 G3 G4 Deliverable

13/02/2023 Presentation of P-lab component

20/02/2023 Preliminary test 1 (work #1)

Activated
P1 27/02/2023
sludge
Jar-test Biodiscs Ion Exchange 2 h class
Activated
P2 06/03/2023
sludge
Jar-test Biodiscs Ion Exchange 2 h class
13/03/2023 Preliminary test 2 (work #1)
Activated Preliminary
P1 20/03/2023 Ion Exchange
sludge
Jar-test Biodiscs
tests 1 and 2
2 h class
Activated
P2 27/03/2023 Ion Exchange
sludge
Jar-test Biodiscs Reports P1 2 h class

03/04/2023 Easter holidays week Reports P2

17/04/2023 Class for calculations and reports, preparing of discussion TP Test 1

08/05/2023 Class for calculations and reports, preparing of discussion

Report "Amigo
15/05/2023 Design exercice Excel
Crítico" P1
Report "Amigo
22/05/2023 Design exercice Excel
Crítico" P2
29/05/2023 Design exercice Excel
Design exercice
05/06/2023 Reports discussion
Excel
 3
Evaluation
35 % of the final grade UC (P laboratorial)
15 % of the final grade UC (Excel - P non-laboratorial)
Component P-laboratorial*:
- 15 % grade report
20 %
- 20 % grade report “Amigo crítico” Report “Amigo
(includes oral discussion) 15 % Crítico” plus
Report test 2 and oral
plus test discussion
1
Component P-non-laboratorial*
15 %
- 15% Excel exercice Exercício
em Excel
*Grade communicated by the teachet to the groups:
-group members distribute the grade between
themselves;
-highest grade – lowest grade < 4
-the group emails their decision to the teacher 50 % of the
UC final
grade
NOTE: The reports include the Preliminary tests 1
and 2 that contribute with 15% to the report grade
 4

Characterization of wastewater
(ww) for designing of treatment
systems

Solids
Carbonaceous matter
Nitrogen
 5

Wastewater characterization
Characterization of the residual water to be
treated is the most critical step in the entire
design process
• Lack of data on residual water to be treated
over- or under-dimensioning
inadequate or inefficient treatment
• Detailed and well-grounded knowledge of
residual water
understanding bulking and foaming problems
and establishing appropriate control measures
 6

Wastewater characterization
- Physical-chemical characteristics important
for design
• Solids
• Carbon compounds (BOD and COD) =
Carbonaceous matter
• Nitrogen compounds
- Relation between parameters
- Determination of key parameters
 7
Solids
Classification of solids in wastewater

Parameter Description
Total solids TS Organic and inorganic; suspended and dissolved;
settleable
1) Suspended TSS Non-filterable organic and inorganic solids
1a) Fixed FSS Mineral compounds not heat oxidizable, which are part of
suspended solids
1b) Volatile VSS Organic compounds, oxidizable by heat, which are part of
suspended solids
2) Dissolved TDS (TS-TSS) Organic and inorganic solids that are filterable. Usually
considered as having a dimension < 10-3 m

2a) Fixed FDS Mineral compounds of dissolved solids

2b) Volatile VDS Organic compounds of dissolved solids
3) Settleable Part of the organic and inorganic solids settling in an hour
in an Imhoff cone. Approximate indication of
sedimentation in a sedimentation tank.
 8
Solids
Relation between solids in a sample of wastewater

Proxy for
biomass
concentration
(X)
 9

Settleable solids

Part of the organic and inorganic solids settling in an hour in an Imhoff cone.
Approximate indication of sedimentation in a sedimentation tank.
 10

Solids
Typical composition of domestic wastewater (Sperling & Chernicharo)

Total solids
(1000 mg/L)

Suspended (TSS) Dissolved (TDS)

(non filterable) (filterable)
(350 mg/L) (650 mg/L)

Fixed (FSS) Volatile (VSS) Fixed (FDS) Volatile (VDS)

(50 mg/L) (300 mg/L) (400 mg/L) (250 mg/L)
 11
Organic constituents

Aggregate organic constituents → comprised of a number of individual

compounds that cannot be or are not distinguished separately

Individual organic compounds → constituents that are determined

individually

Aggregate organic constituents measurement methods:

Gross concentrations → (> 1 mg/L) BOD, COD, TOC
Trace concentrations → (< 1 mg/L) specific methods
 12

Organic components in wastewater

Organic components in wastewater
(approximate values)

Proteins Carbohydrates Oils & Fats

Carbonaceous matter: all these account for BOD, COD, TOC

 13
Carbonaceous matter
Definition of terms used in the characterization of the carbonaceous fraction of a wastewater

Component Definition
BOD
BOD Biochemical oxygen demand of 5 days total, BOD5 total
sBOD Biochemical oxygen demand of 5 days soluble, soluble BOD5
uBOD Biochemical oxygen demand ultimate, BOD ultimate

COD
COD Chemical oxygen demand total, CODtotal
bCOD Biodegradable chemical oxygen demand, CODbiodegradable
pCOD Particulate chemical oxygen demand, CODparticulate
sCOD Soluble chemical oxygen demand, CODsoluble
nbCOD Non biodegradable chemical oxygen demand, CODnon biodg
rbCOD Chemical oxygen demand rapidly/biodg, CODrapidly biodg
rbsCOD Rapidly/biodegradable soluble chemical oxygen demand, ...
sbCOD Chemical oxigen demand slowly biodegradable, ...
pbCOD Chemical oxygen demand particulate biodegradable, ...
pnbCOD Chemical oxygen demand particulate non biodegradable, ...
snbCOD Chemical oxygen demand soluble non biodegradable, ...
 14
Carbonaceous matter
BOD: amount of oxygen required for biological oxidation of an organic substrate

Conceptual model

Biological oxidation (catabolism)

organic
matter
Synthesis (anabolism)
biomass

Endogenous respiration
 15
Carbonaceous matter
BOD: amount of oxygen required for biological oxidation of an organic substrate

Conceptual model

Biological oxidation (catabolism)

organic
matter
Synthesis (anabolism)
biomass

Endogenous respiration

uBOD
 16
Carbonaceous matter
COD: amount of oxygen required for chemical oxidation of an organic substrate

COD vs BOD
Cheaper, faster, simplier, replicable

COD not always equals uBOD:

• Many organic substances are difficult to oxidize biologically
• Inorganic substances oxidized by dichromate overestimate COD
• Some substances toxic for microorganisms
 17
Carbonaceous matter
Unlike BOD, not all COD is biodegradable

tCOD COD Total

bCOD COD COD

nbCOD
Biodegradable Non biodegradable
rbCOD sbCOD
Fast Slow Non biodegradable Non biodegradable
(soluble) (particulate) (soluble) (particulate)
nbsCOD nbpCOD

Complex Coloidal

Volatile fatty acids Particulate

 18
Carbonaceous matter
Effects of rbCOD concentration on bioprocess performance

Process Efect of rbCOD

Activated Sludge For plug flow or stage flow aeration zones, a high rbCOD fraction
aeration in the feed will lead to an increase in the oxygen demand in front
of the tank

Biological Nitrogen For the pre-anoxic tank there will be a higher denitrification rate if
Removal the fraction of rbCOD in the feed is higher. It may result in a
smaller volume of the anoxic tank

Biological Phosphorus Higher concentration of rbCOD in feed results in greater amount

removal of biological phosphorus removal.

Activated sludge Higher fraction of rbCOD in the feed provides more COD for the
selectors floc-forming bacteria in the selector. It can greatly improve the
SVI.
 19
Carbonaceous matter

To determine the bCOD, BOD data is required.

• CODb BODU
 because not all bCOD is
BOD BOD
oxidized in the BOD test. Some
bCOD is transformed into cell mass.

BODU CODb
• For domestic ww with = 1,5 BOD
=1,6 to 1,7
BOD
 20
Carbonaceous matter
For a long-term incubation:
𝑏𝐶𝑂𝐷 = 𝑢𝐵𝑂𝐷 + 1.42 × 𝑓𝑑 × 𝑌𝐻 × 𝑏𝐶𝑂𝐷
fd = fraction of cell mass
remaining as debris, g/g

YH = coefficient of synthesis
yield for heterotrophic
𝑏𝐶𝑂𝐷 𝑢𝐵𝑂𝐷ൗ
𝐵𝑂𝐷 bacteria, g VSS/g COD
= consumed
𝐵𝑂𝐷 1.0 − 1.42 × 𝑓𝑑 × 𝑌𝐻

Example: Using typical values ​for domestic wastewater

(uBOD/BOD = 1,5 ; fd = 0,15 e YH = 0,4)
bCOD/BOD = 1.64
 21
Carbonaceous matter
Typical uBOD/BOD5 and COD/BOD5 ranges

Ratio

The COD/BOD5 ratio varies as the effluent passes through the various
treatment steps. The COD/BOD5 ratio tends to increase due to the
progressive reduction of the biodegradable fraction, keeping the inert
fraction. The final effluent from the biological treatment generally has a
COD/BOD5 ratio above 3.
 22
Carbonaceous matter
Keep in mind!

COD/BOD5 and uBOD/BOD5 ratios (domestic effluent):

❖ The ratios can not be lower than 1

❖ The ratios increase from the untreated effluent to the

biologically treated effluent

❖ The greater the efficiency, the greater the value of ratio

at the end of the treatment.
 23
Carbonaceous matter
Keep in mind!

► The COD/BOD5 ratio for domestic effluent ranges from 1.7 to 2.4
► The COD/BOD5 ratio indicates the biodegradability of the effluent:

➢ COD / BOD5 low (less than 2.5 or 3.0)

• The biodegradable fraction is high
• Good indication for biological treatment

➢ COD / BOD5 medium (between 2.5 and 4.0)

• The inert (non-biodegradable) fraction is somewhat high
• Treatability studies to verify the applicability of biological treatment

➢ COD/BOD5 high (above 3.5 or 4.0)

• The inert (non-biodegradable) fraction is very high
• Possible indication for physical-chemical treatment
 24
Nitrogen
• Major nutrient for biosphere (also for microorganisms responsible
for biological treatment)
• Building block for protein synthesis
• Insufficient N may require addition to the WW for its treatment
• Complex chemistry: several oxidation states, brought by living
organisms (changes both positive and negative)

NH4+ NO2- NO3-

Organic N + NH4+ + NH3 = Total Kjeldhal Nitrogen (TKN)

 Nitrogen 25

NH4+  NH3 + H+
ammonium ion free ammonia

[ NH 3 ] éëH + ùû
= K a =10-9,25 = 5, 62.10-10
éë NH 4+ ùû

NH3 ,% =
NH3 x100
=
100
=
100
NH3  + NH4  1 + NH4 
+ +
1+ H +

NH3  Ka
 26
100
90
80
70
60
%

50
NH3,%
40
NH4+,%
30
20
10
0
0 5 10 15
pH

NH4+  NH3 + H+
ammonium ion free ammonia

For pH below 7 the equilibrium is shifted to the left and the

ammonium ion predominates; at pH above 7 the equilibrium is shifted
to the right and ammonia predominates. Ammonia is determined by
increasing the pH and using steam to distill it from the solution, the
condensed vapor is then analyzed by collorimetry or other methods.
Nitrogen cycle 27
 28
Nitrogen
N removal from wastewaters

Nitrification
NH4+ + 2HCO3- + 2O2 → NO3- + 2CO2 + 3H2O

Denitrification
C10H19O3N + 10NO3- → 5N2 + 10CO2 + 3H2O + NH3 + 10OH-
 29
Nitrogen
Parameter Description
Nitrogen total Total nitrogen includes organic nitrogen,
ammonia, nitrite and nitrate. It is an
essential nutrient for the growth of
microorganisms in biological treatment of
effluents. Organic nitrogen and ammonia
form Kjeldhal nitrogen (TKN).

Nitrogen Nitrogen in the form of proteins, amino

organic acids and urea.
TKN
Ammonia Produced in the first step of organic
nitrogen decomposition.

Nitrites Intermediate stage in oxidation of

ammonia. Practically absent in raw
effluent.

Nitrates Final product in ammonia oxidation.

Practically absent in raw effluent.
 30
Nitrogen fractions
TKN

N Ammonia N organic

Biodegradable Non biodegradable

nbsON
bsON

Soluble Soluble

Particulate Particulate

bpON nbpON
 31

Nitrogen
Forms present in untreated domestic effluent:

60% to 70%
N ammonia,
Directly available for
NH3 & NH4+
nitrification and cell synthesis
TKN

N organic,
40% to 30%
Total Ammino groups
nitrogen
Nitrates, NO3- , practically nonexistent

Nitrites, NO2- , practically nonexistent

 32

Nitrogen
Distribution of nitrogen in domestic effluent

What matters
determine for WW
treatment?

-Free ammonia
-bsON
-bpON
-nbsON
-nbpON

• Oxidized forms are practically non-existent

• Soluble ≈ ammoniacal
• Particulate ≈ organic (mixture of complex compounds, amino acids, amino sugars,
proteins)
 33

Characterization of wastewater
(ww) for designing of treatment
systems

Useful remarks for calculations

 34

Determining of rbCOD by the

filtration method

– Sample of raw waste water decanted

– Sample of aerated wastewater with activated
sludge and decanted
– Coagulation & Filtration

sCOD(raw ww) – sCOD(aerated ww) = rbCOD

 35

Determining of nbVSS
– From COD, sCOD, BOD, sBOD and VSS data
– Assume COD/VSS is equal for both biodegradable and non-
biodegradable VSS

  bpCOD  bpCOD (bCOD

BOD)(BOD - sBOD)
nbVSS = 1 −  VSS =
  pCOD  pCOD COD - sCOD

bpCOD = COD particulate biodegradable, mg/L

pCOD = COD particulate, mg/L
sCOD = COD soluble in the treated effluent, mg/L
 36

Determining of nbVSS
é æ bpCOD öù
nbVSS= ê1- ç ÷úVSS
ë è pCOD øû
Assume that the COD/VSS is the same for biodegradable and non biodegradable VSS

pCOD nbpCOD
=
VSS nbVSS
Assume that the ratio particulate/total is the same for bCOD and BOD

bpCOD pBOD BOD - sBOD

= =
bCOD BOD BOD
bpCOD = (bCOD ) ( BOD - sBOD)
BOD
 37

Determining of nbVSS
Using COD data:

Assume that the COD/VSS is the same for biodegradable and non biodegradable VSS
 38

Determining of nbON
• nbsON cannot be determined directly, but can be estimated from the low
concentration of sON
• nbpON  analysis of influent VSS and nbVSS (previously estimated)
• Fraction o N in VSS:
𝑇𝐾𝑁 − 𝑠𝑂𝑁 − 𝑁𝐻4 𝑎𝑠 𝑁
𝑓𝑁,𝑉𝑆𝑆 =
𝑉𝑆𝑆

𝑛𝑏𝑝𝑂𝑁 = 𝑓𝑁,𝑉𝑆𝑆 × 𝑛𝑏𝑉𝑆𝑆

fN,VSS = nitrogen fraction in VSS, g N /g VSS

TKN = TKN, mg/L
sON = soluble (filtered) organic nitrogen, g/m3
nbpON = non biodegradable particulate organic nitrogen, g/m3
 39
Formulas
I. COD = bCOD + nbCOD
II. bCOD = ~ 1.6 BOD
III. nbCOD = sCODe + nbpCOD
IV. bCOD = sbCOD + rbCOD
V. TKN = NH4-N + ON
VI. ON = bON + nbON
VII. nbON = snbON + pnbON
VIII. nbVSS = [1-bpCOD/pCOD]VSS
IX. bpCOD/pCOD = (bCOD/BOD)(BOD-sBOD)/(COD-sCOD)
X. nbpCOD = tCOD – bCOD – nbsCOD
XI. VSSCOD = (tCOD – sCOD)/VSS
XII. nbVSS = nbCOD/VSSCOD
XIII. fN = (TKN – sON – NH4-N)/VSS
XIV. nbpON = fN nbVSS
 40
Exercise
 41
Exercise

1. bCOD = ~ 1,6 BOD

= 1,6(200 mg/L) = 320 mg/L

2. nbpCOD
nbCOD = COD - bCOD
= (420-320) mg/L = 100 mg/L
nbpCOD = nbCOD – sCODe
= (100-30) mg/L = 70 mg/L
 42
Exercise

3. sbCOD = bCOD – rbCOD

= (320-80) mg/L = 240 mg/L

4. nbVSS
VSSCOD = (tCOD – sCOD)/VSS
= (420-170)/200 = 1.25 g COD /g VSS

nbVSS = nbpCOD / VSSCOD

= 70 / 1.25 = 56 mg/L

5. iTSS = TSS – VSS = 220 – 200 = 20 mg/L

 43
Exercise
6. nbpON
ON content of VSS = fN,VSS
fN,VSS = (TKN – sON – NH4-N)/VSS
= (40 – 1.2 – 26)/200 = 0.064

nbpON = fN,VSS x nbVSS

= 0.064 x 56 = 3.6 mg/L

7. bTKN = TKN – nbpON – sON

= 40 – 3.6 -1.2 = 35.2 mg/L
 44
Homework #1
For the following wastewater sample in the
following table, with values for conventional
wastewater characterization parameters,
determine:

1. the biodegradable COD concentration,

2. the slowly biodegradable COD concentration
3. the non-biodegradable volatile suspended
solids concentration,
4. the inert total suspended solids concentration,
5. the average COD/VSS ratio.

Assume that the treated effluent sCODe equals

30.0 mg/L.