Professional Documents
Culture Documents
1523
2008 SETAC
15
ABSTRACT
Triclosan (TCS) is a broad-spectrum antimicrobial used in consumer products including toothpaste and hand soap. After
being used, TCS is washed or rinsed off and residuals that are not biodegraded or otherwise removed during wastewater
treatment can enter the aquatic environment in wastewater effluents and sludges. The environmental exposure and toxicity
of TCS has been the subject of various scientific and regulatory discussions in recent years. There have been a number of
publications in the past 5 y reporting toxicity, fate and transport, and in-stream monitoring data as well as predictions from
aquatic risk assessments. State-of-the-science probabilistic exposure models, including Geography-referenced Regional
Exposure Assessment Tool for European Rivers (GREAT-ER) for European surface waters and Pharmaceutical Assessment and
Transport Evalutation (PhATEe) for US surface waters, have been used to predict in-stream concentrations (PECs). These
models take into account spatial and temporal variability in river flows and wastewater emissions based on empirically
derived estimates of chemical removal in wastewater treatment and in receiving waters. These model simulations (based on
realistic use levels of TCS) have been validated with river monitoring data in areas known to be receiving high wastewater
loads. The results suggest that 90th percentile (low flow) TCS concentrations are less than 200 ng/L for the AireCalder
catchment in the United Kingdom and between 250 ng/L (with in-stream removal) and 850 ng/L (without in-stream removal)
for a range of US surface waters. To better identify the aquatic risk of TCS, a species sensitivity distribution (SSD) was
constructed based on chronic toxicity values, either no observed effect concentrations (NOECs) or various percentile adverse
effect concentrations (EC1025 values) for 14 aquatic species including fish, invertebrates, macrophytes, and algae. The SSD
approach is believed to represent a more realistic threshold of effect than a predicted no effect concentration (PNEC) based
on the data from the single most sensitive species tested. The log-logistic SSD was used to estimate a PNEC, based on an
HC5,50 (the concentration estimated to affect the survival, reproduction and/or growth of 5% of species with a 50%
confidence interval). The PNEC for TCS was 1,550 ng/L. Comparing the SSD-based PNEC with the PECs derived from GREATER and PhATE modeling to simulate in-river conditions in Europe and the United States, the PEC to PNEC ratios are less than
unity suggesting risks to pelagic species are low even under the highest likely exposures which would occur immediately
downstream of wastewater treatment plant (WWTP) discharge points. In-stream sorption, biodegradation, and photodegradation will further reduce pelagic exposures of TCS. Monitoring data in Europe and the United States corroborate the
modeled PEC estimates and reductions in TCS concentrations with distance downstream of WWTP discharges. Environmental metabolites, bioaccumulation, biochemical responses including endocrine-related effects, and community level
effects are far less well studied for this chemical but are addressed in the discussion. The aquatic risk assessment for TCS
should be refined as additional information becomes available.
Keywords: Triclosan
INTRODUCTION
The environmental exposure and toxicity of triclosan
(TCS) has been the subject of various scientific and regulatory
discussions in recent years. These discussions have been
motivated by the proximity of the predicted environmental
concentration (PEC) to the predicted no effect concentration
(PNEC) based on most sensitive species conventional aquatic
risk assessment methods (for example, as described in the EU
* To whom correspondence may be addressed: marie_capdevielle@colpal.com
Published on the Web 9/13/2007.
Original Research
Review
16
METHODS
Toxicity assessment
A single SSD was constructed from published chronic
NOEC and EC1025 values for 14 aquatic species using
methods described in Versteeg et al. (1999). The data were
not adjusted for ionization although, with a pKa of 8.1, some
of the TCS in the aquatic environment is expected to be
ionized. Biological membranes are generally permeable to unionized molecules and relatively impermeable to the ionized
species of molecules (Cohn 1979), thus failure to take the
ionized fraction into account in this toxicity assessment is
believed to be conservative. Consistent with this, Orvos et al.
17
Samples were analyzed at the Environment Agency Nottingham laboratory by GC-MS and following the method
described by McAvoy et al. (2002) but substituting acylation
in place of silylation for TCS derivatization. The sampling
dates were 10, 11, and 18 February; 3 and 17 March; and 5
April 2005. Standard laboratory procedures were followed
(e.g., glass bottles, 4 8C storage in the dark, less than 10-d
holding times, blanks and blank spiked analytical quality
control samples). The recoveries were greater than 90% and
the reported limit of quantification was 5 ng/L.
For the application of GREAT-ER to the AireCalder, the
following assumptions were made: a use rate of 1 g TCS per
capita per year, a uniform distribution of WWTP removal
rates with a range of 90% to 98%, and 1st order kinetics for instream removal of TCS with a rate constant of 0.21/h
corresponding to a half-life of 3.3 h. The in-stream removal
rate was derived from a monitoring study employing dyetracing conducted by Sabaliunas et al. (2003) in the Mag
Brook, a tributary of the river Calder. Sorption, biodegradation, and photodegradation all contributed to the losses of
TCS in the field. This value (i.e., half-life of 3.3 h) is
considered to be characteristic of relatively small and shallow
streams of Northern Europe and its use here is reasonable
since it was estimated in the same catchment as the one
discussed. However, the actual rate constant for TCS will
probably vary significantly in space (particularly with river
depth; Boeije et al. 2000) and seasonally (e.g., with temperature). It should be noted that the rate constant assumed here
refers to primary degradation (i.e., disappearance of the
parent molecule) rather than to complete mineralization.
North America
For modeling river water exposure to TCS in North
America, the Pharmaceutical Assessment and Transport
Evalutation (PhATEe) model was applied. PhATE uses a
mass balance approach to estimate PECs in 11 catchments
selected to be representative of the range of hydrologic
regions in the United States (Anderson et al. 2004). These
catchments range widely in size and include between 19 and
more than 1,100 WWTPs as point sources of TCS. The recent
paper by Anderson et al. (2004) includes the results of TCS
simulations using PhATE. The key input parameters for TCS
were 600,000 kg/y annual use; no loss prior to entering
wastewater treatment; WWTP removal of 32% for primary
treatment only, 90% for primary plus secondary treatment,
and 95% for tertiary treatment. In-stream losses of TCS in the
evaluations were assumed to take place with a rate constant of
0.23/d (corresponding to a half-life of approximately 3 d), or
zero. The 0.23/d value was taken from a laboratory
mineralization study reported by Federle and Schwab
(2003) which is likely to be conservative with respect to
TCS degradation in the field. Biodegradation in vitro is often
limited by poor contact with fixed-film microbial biomass.
Furthermore, complete mineralization in the laboratory will
necessarily take longer than primary conversion of parent
TCS to resulting metabolites (Struijs and van den Berg 1995).
Better agreement between modeled and measured data was
obtained with an in-stream loss of zero. This may be due to
the fact that the measured results were from samples taken
close to sewage outfalls, while the PhATE model calculates
concentrations at the end of river segments.
In addition to their modeling efforts, Anderson and
colleagues (2004) reported some model corroboration using
18
19
Species
Durationa
Endpoint
Referenceb
Comment
156
NOEC
9 d ph
290
IC25
21 d
Value
(lg/L)
Fish
Oryzias latipes
Fish
O. latipes
Fish
Danio rerio
10 d ph
200
NOEC
Not reported
Fish
D. rerio
14 d ph
160
IC25
Fish
Oncorhynchus mykiss
61 d ph
34.1
NOEC
Invertebrate
Brachionus calyciflorus
2d
50
NOEC
Not reported
Invertebrate
Ceriodaphnia dubia
7d
182
NOEC
Invertebrate
C. dubia
7d
NOEC
Invertebrate
C. dubia
7d
NOEC
Not reported
Invertebrate
C. dubia
7d
170
IC25
Invertebrate
Daphnia magna
21 d
40
NOEC
Invertebrate
Chironomus tentans
10 d
80
NOEC
Invertebrate
Hyalella azteca
10 d
50
EC10
Algae
Selenastrum
capricornutum
4d
2.44
EC25
Biomass
Algae
S. capricornutum
4d
2.6
NOEC
Not reported
Algae
S. capricornutum
4d
3.4
IC25
growth
Algae
Scenedesmus
subspicatus
4d
0.69
NOEC
Biomass
Algae
S. subspicatus
3d
0.53
NOEC
Nominal, growth
Algae
Skeletonema
4d
EC20
Biomass
Algae
Anabaena
4d
0.67
EC25
Biomass
Algae
Anabaena
4d
0.97
EC10
Biomass
Algae
Navicula
4d
10.7
EC20
Biomass
Macrophyte
Lemna
10 d
62.5
EC20
Biomass
66
ph posthatch.
b
1 Ishibashi et al. 2004; 2 Tatarazako et al. 2004; 3 Ferrari et al. 2002; 4 Orvos et al. 2002; 5 Dussault et al. 2004.
Risk assessment
The chronic PNEC derived from the SSD and based on
toxicity data for 14 aquatic species is 1,550 ng/L TCS. In
comparison, predicted 90th percentile concentrations based
on a state-of-the science exposure estimation model (GREATER) for a worst-case catchment in the United Kingdom,
suggest that concentrations rarely exceed 200 ng/L TCS and
this might occur in a limited number of locations (e.g.,
immediately downstream of significant WWTP effluents). For
North America, PhATE model predictions suggest that TCS
concentrations as high as 850 ng/L may occur (without instream removal and 250 ng/L with in-stream removal). Both
of these PECs represent 90th percentile (low-flow) simulations. However, in all cases, the PEC to PNEC ratios are less
than unity suggesting risks to sensitive aquatic species are low
even under the highest likely exposures which would occur
20
Species
Duration (d)
Value (lg/L)
Endpoint
Referencea
Fish
Oryzias latipes
399
LC50
Fish
Pimephales promelas
260
LC50
Fish
Lepomis macrochirus
440
LC50
Invertebrate
Daphnia magna
343.8
EC50
Invertebrate
Ceriodaphnia dubia
184.7
EC50
Invertebrate
Chironomus tentans
10
3,000
LC50
Invertebrate
Hyalella azteca
10
1,000
LC50
Algae
Selenastrum capricornutum
4.46
EC50
Algae
Scenedesmus subspicatus
1.4
EC50
Algae
Skeletonema
EC50
Algae
Anabaena
1.6
EC50
Algae
Navicula
19.1
EC50
Macrophyte
Lemna
10
62.5
EC50
66
Figure 1. Species sensitivity distribution. The log-logistic nonlinear regression of chronic aquatic toxicity data. Upper and lower confidence limits are shown with
dashed lines. The resulting HC5,50 value, below which 5% (a 0.05 cumulative probability) of the species responses (no observed effect concentrations [NOECs] or
various percentile adverse effect concentrations [ECx]) occur taking into account a 50% confidence interval, is 1.55 lg/L as shown in red on the x-axis.
21
Figure 2. Simulated 90th percentile triclosan (TCS) concentrations in the UK AireCalder catchment using Geography-referenced Regional Exposure
Assessment Tool for European Rivers (GREAT-ER) simulation model along with direct comparison of modeled and measured (in blue) TCS levels in the same river
reach (upper right insert).
Figure 3. The cumulative probability distribution of all triclosan concentrations in US surface waters reported by the US Geological Survey and predicted
environmental concentration (PECs) generated by Pharmaceutical Assessment and Transport Evalutation (PhATETM) for all model segments. Detected triclosan
shown as solid triangles m and nondetects as open triangles D. Model results are shown based on zero in-stream removal. Reproduced with permission,
Copyright 2004, American Chemical Society (Anderson et al. 2004).
22
CONCLUSIONS
This pelagic aquatic risk assessment for TCS combined a
more sophisticated toxicity (PNEC) methodology with a
probabilistic exposure (PEC) assessment. Based on the PNEC
derived using a species sensitivity distribution and the PECs
derived from GREAT-ER and PhATE modeling to simulate
in-river conditions in Europe and the United States, the PEC
to PNEC ratios are less than unity suggesting risks to sensitive
aquatic species are low even under the highest likely
exposures that would occur immediately downstream of
WWTP discharge points. In reality, in-stream sorption,
biodegradation, and photodegradation of TCS will tend to
reduce pelagic exposures further. Monitoring data in Europe
and the United States corroborate the modeled PEC
estimates as well as expected reductions in TCS concentrations with increasing distance downstream of WWTP
discharges. Environmental metabolites, bioaccumulation,
biochemical responses including endocrine-related effects,
and community level effects are far less well studied and the
aquatic risk assessment for TCS should be continuously
refined as additional information becomes available.
REFERENCES
Adolfsson-Erici M, Pettersson M, Parkkonen J, Sturve J. 2002. Triclosan, a
commonly used bactericide found in human milk and in the aquatic
environment in Sweden. Chemosphere 46:14851489.
Anderson PD, DAco VJ, Shanahan P, Chapra SC, Buzby ME, Cunningham VL,
Duplessie BM, Hayes EP, Mastrocco FJ, Parke NJ, Rader JC, Samuelian JH,
Schwab BW. 2004. Screening analysis of human pharmaceutical compounds
in U.S. surface waters. Environ Sci Technol 38:838849.
Aranami K, Readman J. 2007. Photolytic degradation of triclosan in freshwater
and seawater. Chemosphere 66:10521056.
Bester K. 2003. Triclosan in a sewage treatment processbalances and
monitoring data. Water Res 37:38913896.
Bester K. 2005. Fate of triclosan and triclosan-methyl in sewage treatment plants
and surface waters. Arch Environ Contam Toxicol 49:917.
Boeije GM, Wagner J-O, Koormann F, Vanrolleghem PA, Schowanek DR, Feijtel TCJ.
2000. New PEC definitions for river basins applicable to GIS-based environmental exposure assessment. Chemosphere 40:255265.
Canesi L, Ciacci C, Lorusso LC, Betti M, Gallo G, Pojana G, Marcomini A. 2007.
Effects of triclosan on Mytilus galloprovincialis hemocyte function and
digestive gland enzyme activities: Possible modes of action on non target
organisms. Comp Biochem Physiol Chem Toxicol Pharmacol 145:464472.
Cohn VH. 1979. Transmembrane movement of drug molecules. In: La Du BN,
Mandel HG, Way EL, editors. Fundamentals of drug metabolism and drug
disposition. New York (NY): Robert E. Krieger. p 316.
Coogan MA, Edziyie RE, LaPoint TW, Venables BJ. 2007. Algal bioaccumulation of
triclocarban, triclosan and methyl-triclosan in a North Texas wastewater
treatment plant receiving stream. Chemosphere 67:19111918.
Dayan A. 2007. Risk assessment of triclosan (Irgasant) in human breast milk. Food
Chem Toxicol 45:125129.
Dussault E, Solomon K, Sibley P. 2004. Aquatic toxicity of carbamazepine,
atorvastatin and triclosan to benthic invertebrates [poster]. In: Society of
Environmental Toxicology and Chemistry (SETAC) 25th Annual Meeting; 2004
Nov 1418; Portland, OR. Pensacola (FL): SETAC. Poster IP006.
[EC] European Commission. 2000. IUCLID Dataset on 2,4-dichlorophenol: CAS No.
120-83-2, February 18, European Chemicals Bureau. European Commission.
58 p.
[EC] European Commission. 2003. Technical guidance document on risk assessment in support of Directive 93/67/EEC (new notified substances) and
Regulation 1488/94 (existing substances). European Chemicals Bureau
Institute for Health and Consumer Protection. Part II. 328 p.
23