ENDOCRINE DISRUPTORS: RISK ASSESSMENT AND CONSENSUS PLATFORM 417 doi:10.2533/chimia.2008.417 CHIMIA 2008, 62, No. 5
Chimia 62 (2008) 417–423 © Schweizerische Chemische Gesellschaft ISSN 0009–4293
Integrative Risk Assessment of Endocrine Disruptors in Switzerland
René Gälli* and Christian Braun
Abstract: The objective of the project was to develop an environmental fate model for various substances with endocrine-disrupting potential for the Glattal/Greifensee region in Switzerland and to assess the concentration levels. The model provides an estimate of environmental concentrations based on mass flow calculations from the source of the emissions to the final fate in the environmental compartments. Based on the chemical proper- ties of 20 substances studied in the NRP50 program, the estimated quantities of the substances used and their respective applications, the model predicts mass flows on a local level. Taking into account the respective water flows, these mass flows result in predicted environmental concentrations in surface water and groundwater. These concentrations can be interpreted as averaged levels with geographical resolution in the local scenario. The estro- genic equivalent concentration was assessed by estrogenic equivalence factor-weighted addition of the individual substance concentrations for four different toxicological endpoints. From the 20 substances modelled in this project only a few substantially contribute to the overall endocrine disruption potential. For three of the endpoints used the steroid hormones dominate the endocrine potential. Only the application of the yeast estrogen system (YES) assay predicts a dominant endocrine potential for the degradation products of nonylphenol-poly-ethoxylates (NPnEO) in the year 2004, which was expected to decrease significantly in the year 2007 due to new legislation (almost complete application ban of NPnEO-based detergents as of August 2006). On the basis of the model’s geographical resolution it is possible to identify ‘hot spots’ in terms of high endocrine-disruption potential in the modelled region. For the densely populated and industrialised Glattal/Greifensee region sewage treatment plants discharging into relatively small receiving water systems show the highest endocrine disruption potential (estradiol equivalence concentration of up to 2 ng/l for the vitellogenin synthesis induction endpoint). In addition to modelling the status quo with respect to endocrine disruption possible future risk reduction measures have been assessed for one identified hot-spot. Whereas an increase in sludge retention time in the existing STP had a moderate effect on the overall endocrine potential, an additional ozonation step showed significant reduction for most endocrine- disrupting substances. Keywords: Endocrine disruption · Local emissions · Mass flow modelling · Surface water
Introduction In particular chemicals such as endocrine disruptors which exhibit low-dose effects Due to improvements in chemical analyt- demand risk assessment tools that are ics and the resulting lower quantification based on predicted environmental concen- limits for micropollutants a large number trations estimated for realistic local geo- of chemicals have been found in waste- graphical and demographical situations. water, surface waters and groundwater. Thus, the development of multimedia Among the micropollutants detected are movement and fate models goes towards pesticides, biocides, pharmaceuticals, real geographical situations, such as the natural hormones and chemicals from geography-referenced regional exposure various household applications.[1] Trace assessment tool GREATER.[3] This model chemicals in the environment can show however is focused on the system ‘sewer − adverse health effects, such as endocrine sewage treatment plant (STP) − river’ and effects on aquatic organisms. Predictive unlike EUSES cannot simulate different models can be used to predict the local emission scenarios and does not track the environmental concentrations of these final fate including transport of chemicals chemicals and, hence, are valuable tools into environmental compartments other for risk assessments and risk management. than rivers. It is recognized that metabo- * Correspondence: Dr. R. Gälli BMG Engineering AG Today’s standardized models such as the lites formed during biological degradation Ifangstrasse 11 ‘European Union System for the Evalua- should be included in risk assessment ap- CH-8952 Schlieren tion of Substances’ EUSES[2] take this ap- proaches.[4] Lately, multi-species models Tel.: +41 44 732 92 87 Fax: +41 44 732 66 22 proach. However, these models predict av- (Level IV) have been proposed by different E-mail: [email protected] erage concentrations for an entire region. authors[5,6] but are not used on a routine ba- ENDOCRINE DISRUPTORS: RISK ASSESSMENT AND CONSENSUS PLATFORM 418 CHIMIA 2008, 62, No. 5 sis in standard risk assessment procedures for the industry so far.
Objectives
The objective of this project was to develop a predictive model for concentra- tions of a wide range of substances with endocrine-disrupting potential. A model for the Glattal/Greifensee region capable of as- sessing the risks associated with nonylphe- nol polyethoxylates and their degradation products which had been developed during an earlier stage of NRP50[7] was further de- veloped. Fig. 1. Mass fl ow scheme of substances for each catchment area (STP) in the model for the most relevant pathways. Transfer and degradation/formation is calculated inside the compartments Material and Methods (boxes).
Model Structure and Capabilities The model is set up as a geographical region that is divided into sub-regions de- fined by the catchment area of the respec- tive sewage treatment plant (STP). The model calculation starts by distributing the emissions between the five environmental compartments air, wastewater treatment, surface water, soil/groundwater, and solid wastes (Fig. 1). The model processes and visualizes mass flows at various levels of detail ( e.g. region, district, STP, activated sludge reactor, biodegradation processes). This provides insight into possible hot spots with high endocrine potency, and in turn, may lead to ideas for further measures which had not previously been considered as a result of the information gained about the concentrations within the individual compartments.
Characterization of the Region Glattal/Greifensee Fig. 2. Geographical representation of the Glatt/Greifensee catchment The region Glattal/Greifensee, located area. The blue line shows the magnitude of surface water fl ows in the near Zurich, Switzerland, was chosen for region (maximum is 8.64 m 3 /s in river Glatt before entering the river Rhine). its good availability of data, the dense pop- Boxes represent the 17 STP catchments in the region. ulation and the high rate of industrializa- tion, leading to high emissions. Since the 17 STPs was supplied by the environmen- Finally, the concentration in each sur- receiving waters upstream of Lake Grei- tal authorities (AWEL, Kt. Zürich). Data face water body is calculated from the fensee are small and the river Glatt is only include estimations of removal efficiency initial level of pollution upstream, the cal- medium-sized, rather high concentrations for characteristic parameters (BSB5, CSB, culated mass added in the catchment area, of pollutants are expected. Furthermore, NH4-N, and P). and the average water flow for the section. this region has a set of wastewater treatment These concentrations can be interpreted as plants ranging from very small and basic Movement and Fate of Chemicals average levels with geographical resolution (ARA Glattfelden/Rheinsfelden, popu- Based on the chemical properties of the in the local scenario. lation equivalent of 1’250) to relatively substances, the estimated quantities used, Modelling the fate of organic com- large plants with state-of-the-art equipment and the applications, the model predicts the pounds in the environment has at least two (ARA Dübendorf, ARA Uster, population movement and fate of the chemicals based levels of complexity: (a) the degradation equivalent of >50’000). All this made the on mass flows on a local level. All the neces- (mineralization) of substances in different region a good test case for the validation of sary calculations (degradation of parent com- compartments (STP, surface water, soil) the model. pounds and formation of metabolites, sorp- and (b) the formation of toxic metabolites Data on geography and hydrology was tion, volatilization, etc.) are performed for due to the degradation of substances. taken from public sources, e.g. Bundesamt the five compartments, resulting in new mass For instance, the degradation of atrazine für Statistik and Statistisches Amt Kt. ZH flows to the connected compartments or to leads to formation of the toxic metabolite (population, agriculture, industry). The the model’s boundaries (sediment, soil, solid desethyl-atrazine that is subsequently de- modelled region with the network of sur- wastes). The mass flows in surface water are graded in the environment. A more com- face waters is shown in Fig. 2. Data on the passed on to the next catchment area. plex example is the formation of degrada- ENDOCRINE DISRUPTORS: RISK ASSESSMENT AND CONSENSUS PLATFORM 419 CHIMIA 2008, 62, No. 5 tion products such as nonylphenol from nonylphenolethoxylate: in our model this transformation involves six degradation constants for each environmental compart- ment and six fractions of formation.
Chemicals Included in the Model The model contains data on 20 sub- stances: Steroidhormones:17β -estradiol(E2),es- trone (E1), estriol (E3), 17α -ethynylestradiol (EE2) Pesticides: atrazine and desetyhlatra- zine Plastics monomer: bisphenol A (BPA) Polybrominated flame retardants (PBDE): decaBDE, octaBDE, pentaBDE, tetrabromobisphenol A UV filters: 4-methylbenzylidene cam- phor (4-MBC), benzophenone-3 (BP-3), ethyhexyl methoxycinnamate (EHMC) Detergents: nonylphenol polyethoxy- late (NPnEO) with its degradation products Fig. 3. Histogram showing the distribution of the mass fl ow of Bisphenol A in the receiving water. The inset shows the convergence of the distribution’s mean value and standard deviation while nonylphenol-di-ethoxylate (NP2EO), non- increasing the number of runs. ylphenol-di-carboxylate (NP2EC), non- ylphenolethoxylate (NP1EO), nonylphe- nolcarboxylate (NP1EC), and nonylphenol surface waters a so-called estradiol equiva- the overall error. Fig. 3 shows the resulting (NP) lent concentration (EEQ) can be calculated distribution of mass flows of bisphenol A in The physicochemical and eco-toxicity the receiving water downstream of an STP. using estradiol equivalence factors ( EEFi data was either taken from literature or [13] = EC50(Estradiol)/EC50(substancei ) ). calculated with the help of estimation pro- Scenarios Calculated EC50 values of endocrine disruption exist grams.[8] Where applicable, i.e. where suffi- for different endpoints, in its current state, Two scenarios have been calculated for cient data was available, harmonized values the model calculates EEQs for MCF-7 cell the Glattal/Greifensee: in 2004 and 2007 were used.[9] The data was revised by mem- proliferation (EEQ1), YES assay (EEQ2), with reduced NPnEO emissions due to new bers of other NRP50 projects. ER-CALUX (EEQ3), and Vitellogenin syn- legislationasofAugust2006.NPnEO-based Emission data was deduced from indus- detergents are only to be used in closed thesis (EEQ4). Since not all EC50 values are try sources ( e.g . amount produced or pro- known for each substance and each end- systems and are not allowed in wastewa- cessed), literature, and in cooperation with point, the individual EEQs are not readily ter streams. In this scenario the emissions other NRP50 projects. Transfer coefficients comparable and should be regarded as indi- are reduced to 1% of the 2004 emissions to (fraction of emissions entering a specific account for any residual amounts of these cators. EC50 data on the different endpoints compartment) were taken either from lit- was taken from literature.[13,14] compounds still used in ‘normal’ applica- erature ( e.g. risk assessment for BPA,[10] tions. studies on atrazine,[11] cooperation partners Sensitivity and Uncertainty To assess the effect of different modes (PBDEs:[12]), or were estimated due to the Analyses of operation for a single STP, two addi- simplicity of the potential pathways, e.g. The modelled concentration of a sub- tional scenarios were set up for STP Egg: steroid hormones are always discharged stance depends on roughly 50 parameters increased sludge retention time and adding into the sewer system. (emission data, substance data, geographi- an ozonation treatment step. The local emissions are calculated from cal data, and hydrological data). Sensitivity the Swiss grand total consumption per sub- analyses were performed to assess the level stance and year multiplied either by the of influence of every single parameter on Results population share in the STP catchment area the calculated result. Sensitivity varies with (‘per capita’ − substances like steroid hor- the substance properties: NP concentrations Comparison of Model Results with mones) or by industrial share ( e.g. NPnEO) are highly sensitive to the degradation and Measured Data or by the share of agricultural land in the formation constants of the precursor sub- Estimated mass flows and expected con- STP catchment area (atrazine). The local stances, whereas the most sensitive param- centrations for surface waters for the vari- emission value is multiplied with the trans- eters for i.e. the concentration of the steroid ous chemicals were compared to measured fer coefficient for the respective compart- hormones are the respective emissions. values from the same region. Comparisons ment, which leads to local environmental To assess the model’s uncertainty with were made for the 2004 emission scenario. emissions to air, wastewater, surface water, respect to the calculated mass flows we The course of nonylphenol concen- soil, and solid waste of the substance. performed uncertainty analyses for differ- trations as modelled and measured in the ent substances. For these analyses we made river Glatt downstream of Lake Greifen- Estrogenic Equivalent assumptions for the shape of the distribu- see is shown in Fig. 4. The measurement Concentration (EEQ) tion of every input parameter and subse- campaign was carried out in 2003 (June, The EEQ can be assessed by estrogen quently ran simulations with parameter August, and October by Voutsa et al.[15]), equivalence factor-weighted addition of values randomly picked from these distri- before the application ban of the parent the calculated individual substance con- butions. From the resulting distribution of substance NPnEO. The modelled concen- centrations. From the concentrations in the surface water concentrations we deduce trations are within the predicted uncertainty ENDOCRINE DISRUPTORS: RISK ASSESSMENT AND CONSENSUS PLATFORM 420 CHIMIA 2008, 62, No. 5
as the model emissions take the form of 250 MeasurementsPH EBRO ( D .Voutsaetal. 2003) an average atrazine mass flow throughout
Model,scenario2004 the year. For nonylphenol the model predicts 200 concentrations that are in the range of the measured concentrations in 2003, but the concentrations of the precursor substances 150 are much higher (our emission scenario is
L still before the complete ban of NPEOs,
ng/ August 2006). This must be due to incor- ng/l 100 rect values of fractions of formation, and moreover, the degradation constant of NP must have been overestimated.
50 Overview of Modelled Results for the Glattal/Greifensee Region, Scenario 2004 0 Havingvalidatedthecalculatedconcen- at G reifensee before STP afterSTP beforeriver Rhine D übendorf Kloten/Opfikon tration values for surface waters within the directionofflow anticipated errors for the individual sub- stances, we applied the proposed system of estradiol equivalence calculation based Fig. 4. Measured and modelled concentrations of nonylphenol in the river Glatt on the substance concentrations and the re- spective estradiol equivalence factors. Visualization of the calculated EEQs of the model for this substance which is whose emissions data were used is stated. helps to pin-point sections of surface wa- roughly one order of magnitude. Bearing The EEQs cannot be ascribed to a specific ters with potentially high concentrations the results of the sensitivity analyses in year since these are calculated from the in- of endocrine-disrupting compounds. The mind, the pronounced decrease of concen- dividual substance concentrations. modelling shows (Fig. 5), that high con- trations towards the river Rhine might be In general, the model predicts the centrations of endocrine-disrupting com- due to an underestimation of the param- measured environmental concentrations pounds can occur downstream of STPs eters for the formation constants in the in surface waters at least within an order with a low dilution ratio or at STPs receiv- NPnEO … NP degradation formalism. of magnitude of the measured values. For ing wastewaters from regions with high All these parameters were shown to be im- the steroid hormones and bisphenol A the emissions. portant by the NP sensitivity analysis. model makes excellent forecasts; for atra- Two examples for local hot-spots in the The Table summarizes concentration zine and desethylatrazine the modelled region have been identified: The brook Aa measurements in surface water bodies in average concentrations are slightly lower downstream of STP Egg/Oetwil and the the Glattal/Greifensee region. The year than the measured values. This is due to the river Glatt downstream of STP Dübendorf. of measurement is given in parentheses. emission spikes in the summer months, the For the small brook Aa downstream of For the modelled concentrations the year only application period of atrazine, where- STP Egg/Oetwil which treats mainly mu-
Table. Comparison of measured and modelled concentration in the river Glatt. Parameter Locationa ref. measurement modellingb ng/l year ng/l scenario EEQ (YES) Glatt d/s of STP Dübendorf [16] 1.0 ± 0.4 2003 2.6 Glatt d/s of former STP Glatt [17] 8 7 6 5 /L ng 4 Q/ EE EEQ/ng/l 3 EEQ/ng/l 2004 2007 2 1 0 r f f t t n gg to en en a en e E d ot gl l ach ld l d ü fe hal l an endor Kl er B tt fe äl üb n- ed la ns önc F D G ei M fiko Ni h R Op 0eeq lossbyvolatilization 0eeq lossbybiodegr adat io n SW down st rea m 0eeq mass in drinking water 0eeq Plantupt ake Fig. 6 Calculated EEQs in the receiving water downstream of STP Egg G Wdownstrea m 0eeq 314. 5eeq sorbed to sedim ent 0eeq lossfromsewer syst em 0eeq . 0eeq solid waste(incinerati on) Input 0eeq 0eeq So il additional wa ter 0eeq Rheinsfelden formatio nbydegradation of precursors G Wdownstream03 0eeq 765. 5eeq loss byvolatilization 0eeq SW upstream 0eeq loss bybiodegradation 0eeq 984. 2eeq mass in drinkin gwat er 0eeq (brook Aa) when applying different treatment options for the 2007 emission 0eeq Input03 0eeq 0eeq Plantuptake G Wupstream additional wa ter 0eeq 0eeq sorbed to sedim ent format io nbydegradation of precursors 0eeq loss from se we rsys tem 0eeq solid wa ste(incineration) 0eeq G lattfelden 0eeq 046. 7eeq Soil 0eeq G Wupstream03 G latt/ G lattfeld 780. q36ee scenario: sludge age of 12 and 20 days and an additional ozonation step. G Wdownstream01 0eeq loss byvolatilization 0eeq 0eeq loss bybiodegradation St adel 0eeq mass in drinkin gwat er Input 01 0eeq 0eeq Plantuptake additional wa ter 0eeq 0eeq sorbed to sediment formatio nbydegradat ionofprecursors 046. 7eeq 0eeq 0eeq loss from sewersystem EEQ1: MCF-7, EEQ2: YES, EEQ3: ER-CALUX, EEQ4: Vitellogenin. 0eeq solid wa ste(incinerat ion) 0eeq Soil 0eeq 0eeq G Wupstreamsw01upstream01 EEQ1 (MCF-7) G Wdownstrea m04 EEQ2 (YE S) lossbyvolatilization 0eeq 0eeq lossbybiodegradation 0eeq 0eeq mass in drinkin gwater 0eeq mass in drinkin gwater B ülach Input04 0eeq Plantuptake 0eeq additional wa ter 0eeq 0eeq sorbed to sedim ent formatio nbydegradation of precursors 0eeq 706. 4eeq lossfromsewer syst em 0eeq 0eeq 0eeq solid wa ste(incineration) EEQ3 ( E R-CALUX) So il 0eeq G latt/ B ülach G Wupstream04 706. 4eeq G Wdownstream05 EEQ4 (Vitellog.) lossbyvolatilization 0eeq 0eeq lossbybiodegradation 0eeq 0eeq mass in drinkin gwater Input 05 0eeq Plantupt ake 0eeq additional wa ter 0eeq sorbed to sedim ent 0eeq formatio nbydegradation of precursors 0eeq lossfromsewer syst em 0eeq 0eeq solid waste(incineration) 0eeq So il 0eeq Niederglatt tribute substantially to the overall EEQ. G Wupstream05 805. 4eeq The estradiol equivalent concentrations of BPA, UV filters, and flame retardants G latt/Nie dergla are at least two orders of magnitude be- Kloten low the main contributors’ concentration 805. 4eeq G Wdownstream06 0eeq loss byvolatilization 0eeq loss bybiodegradation 0eeq 0eeq mass in drinkin gwater 0eeq Plantuptake 0eeq 0eeq G Wupstream08 SW upstream08 Input 06 sorbed to sedim ent 0eeq 0eeq B assersdorf additional wa ter loss from se we rsys tem 0eeq 0eeq 0eeq 0eeq format io nbydegradation of precursors solid wa ste(incineration) value. This might change in situations lossbyvolatilization 0eeq Opfikon 0eeq 0eeq Input08 Soil 0eeq lossbybiodegr adatio n additional wa ter 0eeq 0eeq 0eeq mass in drinking wa ter formatio nbydegradat ion of precursors 0eeq mass in drinking wa ter 0eeq G Wupstream06 0eeq Plantupt ake 748. 5eeq 0eeq sorbed to sedim ent 0eeq lossfromsewer system 0eeq 0eeq solid waste(incinerat ion) 0eeq So il G Wdownstream08 where higher loads of single compounds lossbyvolatilization G latt/Opfi kon 0eeq lossbybiodegr adatio n mass in drinking wa ter Plantupt ake sorbed to sedim ent 0eeq lossfromsewer system G Wdownstrea m are discharged ( e.g. BPA in effluent of an solid waste(incinerat ion) 0eeq 8.745 eeq So il 4.552 eeq C onsumption of C he micals 0eeq D übendorf additional wa ter 0eeq 7.811 eeq formatio nbydegradat ion of precursors 3.259 eeq G latt/ D üb endorf industrial STP). G Wupstream In parallel with the decrease in sur- G Wdownstream09 0eeq 0eeq lossbyvolatilization 0eeq lossbybiodegradation 0eeq mass in drinkin gwater Input09 0eeq Zürich Input09 0eeq 0eeq Plantupt ake additional wa ter 0eeq 0eeq sorbed to sedim ent format io nbydegradation of precursors 0eeq 0eeq lossfromsewer syst em face water concentrations, the concen- 0eeq solid waste(incineration) 0eeq 0eeq So il G Wupstream09 G WupstrSweamup12stream 12 0eeq loss byvolatilization 0eeq 0eeq Pfäffikon 174. 4eeq Uster 0eeq loss bybiodegradation Input12 0eeq 0eeq mass in drinkin gwat er additional water 0eeq 0eeq Plantuptake formatio nbydegradat ion of precursors 0eeq formatio nbydegradat ion of precursors 0eeq trations in other environmental compart- 0eeq sorbed to sedim ent 0eeq loss from se we rsys tem 0eeq solid wa ste(incinerat ion) 0eeq loss byvolatilization 0eeq 0eeq Soil 0eeq loss bybiodegradation F ällanden G Wdownstrea m12 0eeq mass in drinkin gwater G W D ownstrea m10 G lalatttt// F älällalandndenen 0eeq Plantuptake sorbed to sedim ent 0eeq Uster 0eeq 0eeq loss from se we rsys tem 452. 1eeq ments are also expected to decrease. The 0eeq solid wa ste(incineration) Soil 0eeq Input10 0eeq additional wa ter 0eeq G reifensee/Uste 0eeq 504. 4eeq Wetzikon format io nbydegradation of precursors 0eeq G Wdownstream14 G Wupstream10 230. q02ee 0eeq loss byvolatilization 0eeq Maur 501. 2eeq estimated concentration of NP in freshly 0eeq loss bybiodegradation Input 14 0eeq 0eeq mass in drinkin gwat er additional wa ter 0eeq 0eeq Plantuptake 504. 4eeq formatio nbydegradat ion of precursors 0eeq sorbed to sedim ent 0eeq G Wdownstream11 0eeq loss from se we rsys tem 0eeq lossbyvolatilization solid wa ste(incinerat ion) 0eeq 0eeq Wetzikon 0eeq lossbybiodegradation 0eeq Soil 0eeq 0eeq Input 11 0eeq 0eeq mass in drinkin gwater additional wa ter 0eeq Plantupt ake G WupstrSWeam1upst4 ream 14 0eeq formatio nbydegradat ion of precursors 0eeq formed sediments is reduced by a factor 0eeq sorbed to sedim ent 476. 3eeq 0eeq lossfromsewer syst em A abach/W etziko n 0eeq solid waste(incineration) 0eeq 0eeq So il G Wupstream11 474. 4eeq 0eeq lossbyvolatilization 0eeq lossbybiodegr adatio n mass in drinking wa ter G Wdownstream15 0eeq 974. 1eeq 0eeq Plantupt ake of 100 between 2004 and 2007 (data not 0eeq 0eeq sorbed to sedim ent Mönchaltorf G Wdownstrea m13 0eeq lossfromsewer system 0eeq Hinwil 0eeq Input 15 0eeq Hinwil 0eeq loss byvolatilization 0eeq solid waste(incineration) 0eeq additiona lwater 0eeq 0eeq loss bybiodegradation 0eeq 619. 2eeq So il A a/Mönc haltorf Input 13 0eeq format io nbydegradat ion of precursors 0eeq 0eeq mass in drinkin gwater additional wa ter 0eeq 0eeq Plantuptake G Wdownstrea m17 format io nbydegradation of precursors 0eeq 0eeq sorbed to sedim ent 0eeq loss from se we rsys tem 0eeq 0eeq lossbyvolatilization 0eeq G Wupstream15 072. 3eeq shown). G ossau 0eeq lossbybiodegr adat io n 0eeq solid wa ste(incineration) 0eeq 0eeq 0eeq 0eeq mass in drinking wa ter Soil Input 17 0eeq Plantupt ake additional water 0eeq G WupstrSWeam13upst ream13 0eeq 0eeq sorbed to sedim ent formatio nbydegradat ion of precursors 0eeq 547. eeq 0eeq lossfromsewer syst em solid waste(incinerati on) G Wdownstream16 0eeq 0eeq So il 0eeq 0eeq 0eeq lossbyvolatilization 0eeq 0eeq lossbybiodegr adat io n G WupstrSWeam17upstream17 Input 16 0eeq 0eeq mass in drinking water additional wa ter 0eeq 0eeq Plantupt ake Hinwil formatio nbydegradat ion of precursors 0eeq 0eeq sorbed to sediment lossfromsewer syst em 0eeq 0eeq solid waste(incinerati on) 0eeq So il 0eeq 0eeq G WupstrSWeamups16 tream16 Modelling Risk Reduction E gg Measures for the STP Egg Fig. 5. EEQs in receiving waters of the Glatt/Greifensee catchment area For the STP Egg in the Glattal/Grei- modelled for 2004 and 2007 emission scenarios. fensee region we calculated two additional scenarios for different treatment alterna- tives for the 2007 scenario emissions: nicipal wastewater, the main contribution EEQs in the river Glatt:YES assay activity Increase of sludge retention time from to the EEQ are the steroid hormones. How- (EEQ2) is drastically reduced (by a factor 12 days to 20 days and the addition of an ever, the STP Dübendorf receives a large of 25) and EEQ4 (vitellogenin synthesis) ozonation treatment step. The rainwater portion of industrial wastewater contain- is reduced by a factor of 2. The contribu- bypass was set to an average of 3%. For ing NPnEO which leads to corresponding tion of the NPnEO degradation products all three cases we compare the endocrine high EEQ values in the YES assay activity to the expectedYES assay activity (EEQ2) potential in the receiving water, not in the (EEQ2) from NPnEO. is reduced from 97% in 2004 to 25% in STP effluent. 2007. In general, the pollutant concentra- Comparison of Emission Scenarios This decrease of endocrine activity is tion decreases as sludge retention time is for NPnEO 2004 and 2007 only expected for those endpoints where increased or the ozonation step is imple- Due to the ban of NPnEO we assumed NPnEO or its degradation products show mented. drastically reduced usage and a corre- high activity (YES andVitellogenin, EEQ2 Fig. 6 shows that increasing sludge sponding reduction in emissions (99% and EEQ4). Whereas for MCF-7 and ER- retention time can reduce the EEQ in the reduction), particularly in catchment areas CALUX (EEQ1 and EEQ3) there is hardly receiving water. For the four endpoints with high industrial activities. The reduced any change in the overall endocrine ac- (EEQ1 to EEQ4) the endocrine potential emissions of NPnEO in the Dübendorf re- tivity. In terms of individual compounds is decreased by 30%. Adding the ozona- gion result in large reductions in the con- one can deduce that, of the substances tion step reduces all EEQs by at least 70% centrations of NPnEO metabolites and modelled, only the steroid hormones and (EEQ2) compared to the 12 d scenario. It therefore have a pronounced effect on the NPnEO with its degradation products con- was assumed that NPnEO and its degrada- ENDOCRINE DISRUPTORS: RISK ASSESSMENT AND CONSENSUS PLATFORM 422 CHIMIA 2008, 62, No. 5 tion products are reduced by 80%, while to the results of the YES assay the endo- Glattal/Greifensee region or are lo- NP is reduced by 99%. crine potential in the river Glatt after the cated in the catchment area of large Compared to the good elimination in STP Dübendorf has been reduced between surface water systems. Therefore it the STP ( e.g . for E2 the removal rates 2004 and 2007 by a factor of 25 due to the can be concluded that in general a low are: 93% (12 d), 96% (20 d), and 99.8% restrictions in the use of NPnEO. endocrine potential can be expected for (ozonation) respectively), the resulting a large part of Switzerland. EEQs in the receiving water are relatively Glattal/Greifensee Region • Catchment areas with large popula- high. This is due to the residual amount The endocrine disruption potential in tions and STPs discharging to small of pollutants that do not pass the STP but the river Glatt varies from low (outflow of surface waters (hot spots) can lead to are discharged directly into the receiving Lake Greifensee) to high (downstream of endocrine potentials which are in the water, either by rainwater bypass or by STP Dübendorf). Compared to the average order of magnitude of the EC50 values product leaching and surface run-off ( e.g . concentration in the river Glatt at Glatt- for estradiol for the most sensitive end- bisphenol A) and the amount of pollutants felden (before flowing into river Rhine) point used ( e.g. MCF-7). The environ- already present in the receiving water. the highest local concentrations in the mental significance of the individual catchment area are up to about a factor of endpoints is still under discussion. eight higher. These so called hot spots are • In state-of-the-art Swiss STPs most of Conclusions due to STPs discharging into small receiv- the steroid hormones passing through ing waters (STP Egg, STP Bassersdorf). the plant are eliminated (sludge age The model calculations have shown Further reasons for locally higher concen- >10 days). In order to further reduce that it is possible to estimate environmen- trations are high industrial emissions (STP the endocrine potential as well as other tal concentrations and the corresponding Dübendorf) and low removal efficiency micropollutants in STPs additional ecotoxicity for various substances simul- (STP Egg). treatment steps are being assessed by taneously based on a very limited data set. Although the estimated local concen- the federal government (ozonation, ac- The model allows the prediction not only trations are high, they are rather low when tivated carbon). of environmental concentration on a year- compared to published concentrations • In addition organizational measures ly average basis but also the generation of from other countries such as Great Britain such as the combined treatment of predictions for specific environmental sce- or the USA. Williams et al.[19] measured wastewater from different small and narios such as improvement of STP, rain estradiol concentrations of up to 4.3 ng/l ineffective STPs in larger and more events etc. and estrone concentrations of up to 12.2 effective plants or the direction of the The substances modelled in this project ng/l in rivers downstream of STPs, which treated wastewater to larger surface have been thoroughly studied by various are at least a factor of six higher than our waters are possible. research groups and therefore were ideal modelled yearly averages. for the validation of the model. Since the Received: March 22, 2008 substances used represent a wide range of Relevant Endocrine-disrupting physical-chemical properties and emission Chemicals [1] R. P. Schwarzenbach, B. I. Escher, K. pathways the model is ready to predict the From the 20 substances modelled in Fenner, T. B. Hofstetter, C. A. Johnson, movement and fate of other chemicals this project only a few substantially con- U. von Gunten, B. Wehrli, Science 2006, such as pharmaceuticals, biocides, corro- tribute to the overall endocrine-disruption 313, 1072. sion inhibitors etc. potential. For three of the endpoints used, [2] EUSES 2.0, European Commission, The model can easily be adapted to the steroid hormones dominate the endo- National Institute of Public Health and new geographical areas and a model for crine potential. Only the application of the the Environment (RIVM), Bilthoven, Netherlands, 2004. Switzerland is envisaged, which would in- YES assay predicts a dominant endocrine [3] T. Feijtel, G. Boeije, M. Matthies, A. clude all major STP and surface waters of potential for the degradation products of Young, G. Morris, C. Gandolfi, B. Switzerland. NPnEO in 2004, which decreases signifi- Hansen, K. Fox, M. Holt, V. Koch, R. Since the model has an integrated com- cantly in the year 2007. Schroder, G. Cassani, D. Schowanek, J. pound database new (emerging) chemicals The contribution of substances such as Rosenblom, H. Niessen, Chemosphere can be introduced as they are studied by bisphenol A and the various UV filters to 1997, 34, 2351. the environmental authorities or research the overall endocrine potential is small. [4] A. B. A. Boxall, Environ. Sci. Technol. groups. This provides an overview of the However, it has to be considered that the 2004, 38, 368A. environmental contamination of the sur- endocrine potential for all endpoints is not [5] T. M. Cahill, I. Cousins, D. Mackay, face waters in Switzerland. The model can known for all the substances entering sur- Environ. Toxicol. Chem. 2003, 22, 483. [6] K. Fenner, M. Scheringer, K. serve as an important tool for the manage- face waters. Near major emission sources Hungerbühler, Environ. Sci. Technol. ment of the risk posed by emissions of ( e.g. wastewater of a specific industry) 2000, 34, 3809. chemicals. The models allows risk man- these chemicals may become relevant. [7] M. Schluep, R. Gälli, Swiss National agement options such as local vs. central Science Foundation NRP50 project 03, wastewater treatment, restriction of chem- Attempt to Assess the Situation for Final Report, 2004. icals or organizational changes in the man- the Glattal/Greifensee Region [8] Estimation Programs Interface Suite™ agement of wastewater to be assessed. Based on the modelling results the fol- for Microsoft® Windows, v3.20. United lowing conclusions can be drawn for Swit- States Environmental Protection Agency, General conclusions zerland: USA, 2000. EEQs vary from endpoint to endpoint, • The overall endocrine potential in sur- [9] U.Schenker,M.MacLeod,M.Scheringer, K. Hungerbühler, Environ. Sci. Technol. which is especially critical for NPnEO face water depends mainly on the ef- 2005, 39, 8434. and its degradation products which exhibit ficiency of the corresponding STP and [10] ‘European Union Risk Assessment high activity in the YES assay. However, the dilution ratio of the treated effluent Report, 4,4’-isopropylidenediphenol this result can be used to demonstrate the in the surface water. (bisphenol A)’, Volume 37, Editors: effect of risk reduction measures ( i.e. the • Most areas of Switzerland are less S.J. Munn, R. Allanou, K. Aschberger, restricted use of NPnEO). With respect densely populated compared to the F. Berthault, J. de Bruijn, C. Musset, S. ENDOCRINE DISRUPTORS: RISK ASSESSMENT AND CONSENSUS PLATFORM 423 CHIMIA 2008, 62, No. 5 O’Connor, S. Pakalin, G. Pellegrini, S. Research Report University Tübingen, Scheer, S. Vegro, Luxembourg, Office PUG U 95 004, 1999; h) K. L. Thorpe, for Official Publications of the European R. I. Cummings, T. H. Hutchinson, M. 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