Occurrence, phase distribution, and mass loadings of benzothiazoles in riverine runoff of the Pearl River Delta, China

A set of six benzothiazoles was determined in riverine runoff samples of the Pearl River Delta (PRD) collected monthly from March 2005 to February 2006. The concentrations of total benzothiazoles ranged from 220 to 611 ng/L, with benzothiazole (BT) being the most prominent (82%), followed by 2-methylthiobenzothiazole (MBT),thianaphthene (TN), and triphenylene (TP). The annual fluxes ofTN, BT, MBT, dibenzothiophene (DBT), 2-(4-morpholinyl)benzothiazole (24MoBT), and TP from the PRD to the coastal ocean were 1.94, 65.1, 10.1,0.63, 0.18, and 0.89 tons/yr, summing to yield an annual flux of 79 tons/yr for total benzothiazoles. In the PRD, approximately 1.1 x 10(5) tons of rubber are estimated to be released into the environment each year. This corresponds to the annual fluxes of 13 tons/yr for BT and 0.4 tons/yr for 24MoBT from tire particles. The annual fluxes of BT from scrap tires from Japan, Korea, Brazil, the European Union, the United States, and China were 99, 21, 36, 270, 328, and 120 tons/yr, respectively. The fluxes of 24MoBT from the same countries were 3.0, 0.5, 1.1, 8.4, 10.3, and 3.8 tons/ yr, respectively. These results indicated that tire-wear particles and scrap tires are the dominant sources of benzothiazoles in the environment. By comparison, Asia may be the major contributor to the global input of benzothiazoles from auto tires in the coming years. Overall, the six benzothiazoles under investigation appeared to be suitable tracers of pollutant inputs to surface runoff within the PRD aquatic system. In addition, 24MoBT seemed more appropriate than BT to trace tire rubber residues and therefore can be a good indicator of economic development and urbanization in a specific region.     

Removal of sulfur-organic polar micropollutants in a membrane bioreactor treating industrial wastewater

While membrane bioreactors (MBR) have proven their large potential to remove bulk organic matter from municipal as well as industrial wastewater, their suitability to remove poorly degradable polar wastewater contaminants is yet unknown. However, this is an important aspect for the achievable effluent quality and in terms of wastewater reuse. We have analyzed two classes of polar sulfur-organic compounds, naphthalene sulfonates and benzothiazoles, by liquid chromatography-electrospray ionization-tandem mass spectrometry (LC-ESI-MS) over a period of 3 weeks in the influent and effluent of a full-scale MBR with external ultrafiltration that treats tannery wastewater. While naphthalene monosulfonates were completely removed, total naphthalene disulfonate removal was limited to about 40%, and total benzothiazoles concentration decreased for 87%. Quantitative as well as qualitative data did not indicate an adaptation to or a more complete removal of these polar aromatic compounds by the MBR as compared to literature data on conventional activated sludge treatment. While quality improvements in receiving waters for bulk organic matter are documented and the same can be anticipated for apolar particle-associated contaminants, these data provide no indication that MBR will improve the removal of polar poorly biodegradable organic pollutants.     

Fate, transport, and biodegradation of natural estrogens in the environment and engineered systems

Natural steroidal estrogen hormones, e.g., estrone (E1), 17beta-estradiol (E2), estriol (E3), and 17alpha-estradiol (17alpha), are released by humans and livestock in the environment and are the most potent endocrine disrupters even at nanogram per liter levels. Published studies broadly conclude that conventional wastewater treatment is efficient in the removal of 17beta-estradiol (85-99%), but estrone removal is relatively poor (25-80%). The removal occurs mainly through sorption by sludge and subsequent biodegradation. The long solids retention time in wastewater treatment systems enhances estrogen removal due to longer exposure and the presence of a diverse microbial community, particularly nitrifiers. In spite of the treatment, the effluent from conventional biological wastewater treatment systems still contains estrogenic compounds at a level that may cause disruption of endocrine systems in some species. Advanced wastewater treatment systems such as membrane processes remove the estrogen compounds mainly through physical straining of particle-bound estrogens. Another major source, which accounts for 90% of the estrogen load, is animal manure from concentrated animal-feeding operations (CAFOs). Manure is not required to be treated in the United States as long as it is not discharged directly into water bodies. Thus, there is an urgent need to study the fate of animal-borne estrogens from these facilities into the environment. A number of studies have reported the feminization of male aquatic species in water bodies receiving the effluents from wastewater treatment plants (WWTPs) or surface runoff from fields amended with livestock manure and municipal biosolids. Estrogenicity monitoring studies have been conducted in more than 30 countries, and abundant research articles are now available in refereed journals. This review paper focuses on estrogen contributions by wastewater and livestock manure, their removal rate and mechanisms in an engineered system, and their transport and ultimate fate in an engineered system and the environment. The review aims to advance our understanding of fate, transport, and biodegradation of estrogen compounds and outlines some directions for future research.     

Polar pollutants entry into the water cycle by municipal wastewater: a European perspective

The effluents of eight municipal wastewater treatment plants (WWTP) in Western Europe were analyzed by liquid-chromatography-mass spectrometry for the occurrence of 36 polar pollutants, comprising household and industrial chemicals, pharmaceuticals, and personal care products. In a long-term study of the effluents of three WWTP over 10 months, sulfophenyl carboxylates and ethylene diamino tetraacetate (EDTA) were detected above 10 microg/L on average, while benzotriazoles, benzothiazole-2-sulfonate, diclofenac, and carbamazepine showed mean concentrations of 1-10 microg/L, followed by some flame retardants, naphthalene disulfonates, and personal care products in the range of 0.1-1 microg/L. Half of the determined compounds were not significantly removed in tertiary wastewater treatment. By dividing the effluent concentration of a compound by its relative removal in WWTP a water cycle spreading index (WCSI) was calculated for each compound. We propose that this index provides a measure for the potential of a polar compound to spread along a partially closed water cycle after discharge with municipal wastewater and to occur in raw waters used for drinking water production. Polar pollutants in surface water samples of different catchments showed increasing concentration for compounds with increasing WCSI.     

Characterization and fate of N-nitrosodimethylamine precursors in municipal wastewater treatment plants

The potent carcinogen, N-nitrosodimethylamine (NDMA), is produced during disinfection of municipal wastewater effluent from the reaction of monochloramine and organic nitrogen-containing precursors. To delineate the sources and fate of NDMA precursors during municipal wastewater treatment, NDMA formation was measured after extended chloramination of both model precursors and samples from conventional and advanced wastewater treatment plants. Of the model precursors, only dimethylamine, tertiary amines with dimethylamine functional groups, and dimethylamides formed significant NDMA concentrations upon chloramination. In samples from municipal wastewater treatment plants, dissolved NDMA precursors always were present in primary and secondary effluents. Biological treatment effectively removed the known NDMA precursor dimethylamine, lowering its concentration to levels that could not produce significant quantities of NDMA upon chlorine disinfection. However, biological treatment was less effective at removing other dissolved NDMA precursors, even after extended biological treatment. Significant concentrations of particle-associated NDMA precursors only were detected in secondary effluent at treatment plants that recycled water from sludge thickening operations in which dimethylamine-based synthetic polymers were used. Effective strategies for the prevention of NDMA formation during wastewater chlorination include ammonia removal by nitrification to preclude chloramine formation during chlorine disinfection, elimination of dimethylamine-based polymers, and use of filtration and reverse osmosis to remove particle-associated precursors and dissolved precursors, respectively.     

Removal of fragrance materials during U.S. and European wastewater treatment

The concentrations and removals of 16 fragrance materials (EMs) were measured in 17 U.S. and European wastewater treatment plants between 1997 and 2000 and were compared to predicted values. The average FM profile and concentrations in U.S. and European influent were similar. The average FM profile in primary effluent was similar to the average influent profile; however, the concentration of FMs was reduced by 14.6-50.6% in primary effluent. The average FM profile in final effluent was significantly different from the primary effluent profile and was a function of the design of the wastewater treatment plant. In general, the removal of sorptive, nonbiodegradable FMs was correlated with the removal of total suspended solids in the plant, while the removal of nonsorptive, biodegradable FMs was correlated with 5-day Biological Oxidation Demand removal in the plant. The overall plant removal (primary + secondary treatment) of FMs ranged from 87.8 to 99.9% for activated sludge plants, 58.6-99.8% for carousel plants, 88.9-99.9% for oxidation ditch plants, 71.3-98.6% for trickling filter plants, 80.8-99.9% for a rotating biological contactor plant, and 96.7-99.9% for lagoons. The average concentration of FMs in final effluent ranged from the limit of quantitation (1-3 ng/L) to 8 microg/L. Measured FM removal and concentrations were compared to predicted values, which were based on industry volume, per capita water use, octanol-water partition coefficient, and biodegradability.     

Algal uptake of hydrophobic and hydrophilic dissolved organic nitrogen in effluent from biological nutrient removal municipal wastewater treatment systems

Dissolved organic nitrogen (DON) accounts for a large fraction of the total nitrogen discharged to surface waters by municipal wastewater treatment plants designed for biological nutrient removal (BNR). Previous research indicates that some but not all of the DON in wastewater effluent is available to bacteria and algae over time scales that are relevant to rivers and estuaries. To separate bioavailable DON from nitrate and less reactive DON species, an XAD-8 resin coupled with an anion exchange treatment was employed prior to chemical analysis and algal bioassays. Analysis of effluent samples from a range of municipal BNR plants (total DON concentrations ranging from 0.7 to 1.8 mg N/L) employing a range of technologies indicated that hydrophilic DON, which typically accounted for approximately 80% of the total DON, stimulated algal growth, whereas hydrophobic DON, which accounted for the remaining DON, remained at nearly constant concentrations and had little or no effect on algal growth during a 14-day incubation period. The hydrophobic DON exhibits characteristics of humic substances, and is likely to persist for long periods in the aquatic environment. The distinct differences between these two classes of DON may provide a basis for considering them separately in water quality models and effluent discharge regulations.     

Triclosan: occurrence and fate of a widely used biocide in the aquatic environment: field measurements in wastewater treatment plants,surface waters,and lake sediments

Triclosan is used as an antimicrobial agent in a wide range of medical and consumer care products. To investigate the occurrence and fate of triclosan in the aquatic environment, analytical methods for the quantification of triclosan in surface water and wastewater, sludge, and sediment were developed. Furthermore, the fate of triclosan in a wastewater treatment plant (biological degradation, 79%; sorption to sludge, 15%; input into the receiving surface water, 6%) was measured during a field study. Despite the high overall removal rate, the concentration in the wastewater effluents were in the range of 42-213 ng/L leading to concentrations of 11-98 ng/L in the receiving rivers. Moreover, a high removal rate of 0.03 d(-1) for triclosan in the epilimnion of the lake Greifensee was observed. This is due to photochemical degradation. The measured vertical concentration profile of triclosan in a lake sediment core of lake Greifensee reflects its increased use over 30 years. As the measured concentrations in surface waters are in the range of the predicted no effect concentration of 50 ng/L, more measurements and a detailed investigation of the degradation processes are needed.     

Discharge of three benzotriazole corrosion inhibitors with municipal wastewater and improvements by membrane bioreactor treatment and ozonation

A set of three benzotriazole corrosion inhibitors was analyzed by liquid chromatography-mass spectrometry in wastewaters and in a partially closed water cycle in the Berlin region. Benzotriazole (BTri) and two isomers of tolyltriazole (TTri) were determined in untreated municipal wastewater with mean dissolved concentrations of 12 microg/L (BTri), 2.1 microg/L (4-TTri), and 1.3 microg/L (5-TTri). Removal in conventional activated sludge (CAS) municipal wastewater treatment ranged from 37% for BTri to insignificant removal for 4-TTri. In laboratory batch tests 5-TTri was mineralized completely and 4-TTri was mineralized to only 25%. This different behavior of the three benzotriazoles was confirmed by following the triazoles through a partially closed water cycle, into bank filtrate used for drinking water production, where BTri (0.1 microg/L) and 4-TTri (0.03 microg/ L) but no 5-TTri were detected after a travel time of several months. The environmental half-life appears to increase from 5-TTri over BTri to 4-TTri. Treatment of municipal wastewater by a lab-scale membrane bioreactor (MBR) instead of CAS improved the removal of BTri and 5-TTri but could not avoid their discharge. Almost complete removal was achieved by ozonation of the treatment plant effluent with 1 mg O3/mg DOC.     

Environmental exposure and risk assessment of fluoroquinolone antibacterial agents in wastewater and river water of the Glatt Valley Watershed,Switzerland

The mass flows of fluoroquinolone antibacterial agents (FQs) were investigated in the aqueous compartments of the Glatt Valley Watershed, a densely populated region in Switzerland. The major human-use FQs consumed in Switzerland, ciprofloxacin (CIP) and norfloxacin (NOR), were determined in municipal wastewater effluents and in the receiving surface water, the Glatt River. Individual concentrations in raw sewage and in final wastewater effluents ranged from 255 to 568 ng/L and from 36 to 106 ng/L, respectively. In the Glatt River, the FQs were present at concentrations below 19 ng/L. The removal of FQs from the water stream during wastewater treatment was between 79 and 87%. During the studied summer period, FQs in the dissolved fraction were significantly reduced downstream in the Glatt River (15-20 h residence time) (66% for CIP and 48% for NOR). Thus, after wastewater treatment, transport in rivers causes an additional decrease of residual levels of FQs in the aquatic environment. Refined predicted environmental concentrations for the study area compare favorably with the measured environmental concentrations (MEC) obtained in the monitoring study. Total measured FQ concentrations occurring in the examined aquatic compartments of the Glatt Valley Watershed were related to acute ecotoxicity data from the literature. The risk quotients obtained (MEC/PNEC < 1) following the recommendations of the European guidelines or draft documents suggest a low probability for adverse effects of the occurring FQs, either on microbial activity in WWTPs or on algae, daphnia, and fish in surface waters.     

Caffeine,an anthropogenic marker for wastewater comtamination of surface waters

The suitability of caffeine as a chemical marker for surface water pollution by domestic wastewaters was assessed in this study. Caffeine concentrations in influents and effluents of Swiss wastewater treatment plants (WWTPs, 7-73 and 0.03-9.5 microg/L, respectively) indicated an efficient elimination of 81-99.9%. Corresponding loads in untreated wastewater showed small variations when normalized forthe population discharging to the WWTPs (15.8 +/- 3.8 mg person(-1) d(-1)), reflecting a rather constant consumption. WWTP effluent loads were considerably lower (0.06 +/- 0.03 mg person(-1) d(-1)), apart from installations with low sludge age (< or = 5 d, loads up to 4.4 mg person(-1) d(-1)). Despite the efficient removal in most WWTPs, caffeine was ubiquitously found in Swiss lakes and rivers (6-250 ng/ L), except for remote mountain lakes (<2 ng/L; analytical procedure for wastewater and natural waters: SPE, GC-MS-SIM or GC-MS-MS-MRM, internal standard 13C3-labeled caffeine). Caffeine concentrations in lakes correlated with the anthropogenic burden by domestic wastewaters, demonstrating the suitability of caffeine as a marker. A mass balance for Greifensee revealed that approximately 1-4% of the wastewaters had been discharged without treatment, presumably on rainy days when the capacity of WWTPs had been exceeded. For Zürichsee, it could be shown that the monthly inputs of caffeine correlated with precipitation data. The depth- and seasonal-dependent concentrations in this lake were adequately rationalized by a numerical model considering flushing, biodegradation, and indirect photodegradation via HO. radicals as elimination processes and caffeine inputs as fitting variables.     

Quantifying diffuse and point inputs of perfluoroalkyl acids in a nonindustrial river catchment

Recently, the role of diffuse inputs of perfluoroalkyl acids (PFAAs) into surface waters has been investigated. It has been observed that river loads increased during rain and that street runoff contained considerable loads of PFAAs. This study aims at quantifying these diffuse inputs and identifying the initial sources in a small nonindustrial river catchment. The river was sampled in three distinct subcatchments (rural, urban, and wastewater treatment plant) at high temporal resolution during two rain events and samples were analyzed for perfluorocarboxylates and perfluorosulfonates. Additionally, rain, stormwater runoff, wastewater effluent, and drinking water were sampled. PFAA concentrations in river water were all low (e.g., < 10 ng/L for perfluorooctanoate, PFOA), but increased during rainfall. PFAA concentrations and water discharge data were integrated into a mass balance assessment that shows that 30-60% of PFAA loads can be attributed to diffuse inputs. Rain contributed 10-50% of the overall loads, mobilization of dry deposition and outdoor release of PFAA from products with 20-60%. We estimated that within a year 2.5-5 g of PFOA originating from rain and surface runoff are emitted into this small catchment (6 km(2), 12,500 persons).     

Quantitative determination of fluorinated alkyl substances by large-volume-injection liquid chromatography tandem mass spectrometry-characterization of municipal wastewaters

A quantitative method was developed for the determination of fluorinated alkyl substances in municipal wastewater influents and effluents. The method consisted of centrifugation followed by large-volume injection (500 microL) of the supernatant onto a liquid chromatograph with a reverse-phase column and detection by electrospray ionization and tandem mass spectrometry. The fluorinated analytes studied include perfluoroalkyl sulfonates, fluorotelomer sulfonates, perfluorocarboxylates, and select fluorinated alkyl sulfonamides. Recoveries of the fluorinated analytes from wastewater treatment plant (WWTP) raw influents and final effluent were in the ranges of 82-100% and 86-100%, respectively. The lower limit of quantitation was 0.5 ng/L depending on the analyte. The method was applied to flow-proportional composites of raw influent and final effluent collected over a 24 h period from 10 WWTPs nationwide. Fluorinated alkyl substances were observed in wastewater at all treatment plants, and each plant exhibited unique distributions of fluorinated alkyl substances despite similarities in treatment processes. In 9 out of the 10 plants sampled, at least one class of fluorinated alkyl substances exhibited increased concentrations in the effluent as compared to the influent concentrations. In some instances, decreases in certain fluorinated analyte concentrations were observed and attributed to sorption to sludge.     

Combined sewer overflows: an environmental source of hormones and wastewater micropollutants

Data were collected at a wastewater treatment plant (WWTP) in Burlington, Vermont, USA, (serving 30,000 people) to assess the relative contribution of CSO (combined sewer overflow) bypass flows and treated wastewater effluent to the load of steroid hormones and other wastewater micropollutants (WMPs) from a WWTP to a lake. Flow-weighted composite samples were collected over a 13 month period at this WWTP from CSO bypass flows or plant influent flows (n = 28) and treated effluent discharges (n = 22). Although CSO discharges represent 10% of the total annual water discharge (CSO plus treated plant effluent discharges) from the WWTP, CSO discharges contribute 40-90% of the annual load for hormones and WMPs with high (>90%) wastewater treatment removal efficiency. By contrast, compounds with low removal efficiencies (<90%) have less than 10% of annual load contributed by CSO discharges. Concentrations of estrogens, androgens, and WMPs generally are 10 times higher in CSO discharges compared to treated wastewater discharges. Compound concentrations in samples of CSO discharges generally decrease with increasing flow because of wastewater dilution by rainfall runoff. By contrast, concentrations of hormones and many WMPs in samples from treated discharges can increase with increasing flow due to decreasing removal efficiency.     

Use of the chiral pharmaceutical propranolol to identify sewage discharges into surface waters

The discharge of relatively small volumes of untreated sewage is a source of wastewater-derived contaminants in surface waters that is often ignored because it is difficult to discriminate from wastewater effluent. To identify raw sewage discharges, we analyzed the two enantiomers of the popular chiral pharmaceutical, propranolol, after derivitization to convert the enantiomers to diastereomers. The enantiomeric fraction (the ratio of the concentration of one of its isomers to the total concentration) of propranolol in the influent of five wastewater treatment plants was 0.50 +/- 0.02, while after secondary treatment it was 0.42 or less. In a laboratory study designed to simulate an activated sludge municipal wastewater treatment system, the enantiomeric fraction of propranolol decreased from 0.5 to 0.43 as the compound underwent biotransformation. In a similar system designed to simulate an effluent-dominanted surface water, the enantiomeric fraction of propranolol remained constant as it underwent biotransformation. Analysis of samples from surface waters with known or suspected discharges of untreated sewage contained propranolol with an enantiomeric fraction of approximately 0.50 whereas surface waters with large discharges of wastewater effluent contained propranolol with enantiomeric fractions similar to those observed in wastewater effluent. Measurement of enantiomers of propranolol may be useful in detecting and documenting contaminants related to leaking sewers and combined sewer overflows.     

Fluorochemical mass flows in a municipal wastewater treatment facility

Fluorochemicals have widespread applications and are released into municipal wastewater treatment plants via domestic wastewater. A field study was conducted at a full-scale municipal wastewater treatment plant to determine the mass flows of selected fluorochemicals. Flow-proportional, 24 h samples of raw influent, primary effluent, trickling filter effluent, secondary effluent, and final effluent and grab samples of primary, thickened, activated, and anaerobically digested sludge were collected over 10 days and analyzed by liquid chromatography electrospray-ionization tandem mass spectrometry. Significant decreases in the mass flows of perfluorohexane sulfonate and perfluorodecanoate occurred during trickling filtration and primary clarification, while activated sludge treatment decreased the mass flow of perfluorohexanoate. Mass flows of the 6:2 fluorotelomer sulfonate and perfluorooctanoate were unchanged as a result of wastewater treatment, which indicates that conventional wastewater treatment is not effective for removal of these compounds. A net increase in the mass flows for perfluorooctane and perfluorodecane sulfonates occurred from trickling filtration and activated sludge treatment. Mass flows for perfluoroalkylsulfonamides and perfluorononanoate also increased during activated sludge treatment and are attributed to degradation of precursor molecules.     

Partitioning, persistence, and accumulation in digested sludge of the topical antiseptic triclocarban during wastewater treatment

The topical antiseptic agent triclocarban (TCC) is a common additive in many antimicrobial household consumables, including soaps and other personal care products. Long-term usage of the mass-produced compound and a lack of understanding of its fate during sewage treatment motivated the present mass balance analysis conducted at a typical U.S. activated sludge wastewater treatment plant featuring a design capacity of 680 million liters per day. Using automated samplers and grab sampling, the mass of TCC contained in influent, effluent, and digested sludge was monitored by isotope dilution liquid chromatography (tandem) mass spectrometry. The average mass of TCC (mean +/- standard deviation) entering and exiting the plant in influent (6.1 +/- 2.0 microg/L) and effluent (0.17 +/- 0.03 microg/ L) was 3737 +/- 694 and 127 +/- 6 g/d, respectively, indicating an aqueous-phase removal efficiency of 97 +/- 1%. Tertiary treatment by chlorination and sand filtration provided no detectable benefit to the overall removal. Due to strong sorption of TCC to wastewater particulate matter (78 +/- 11% sorbed), the majority of the TCC mass was sequestered into sludge in the primary and secondary clarifiers of the plant. Anaerobic digestion for 19 days did not promote TCC transformation, resulting in an accumulation of the antiseptic compound in dewatered, digested municipal sludge to levels of 51 +/- 15 mg/kg dry weight (2815 +/- 917 g/d). In addition to the biocide mass passing through the plant contained in the effluent (3 +/- 1%), 76 +/- 30% of the TCC input entering the plant underwent no net transformation and instead partitioned into and accumulated in municipal sludge. Based on the rate of beneficial reuse of sludge produced by this facility (95%), which exceeds the national average (63%), study results suggest that approximately three-quarters of the mass of TCC disposed of by consumers in the sewershed of the plant ultimately is released into the environment by application of municipal sludge (biosolids) on land used in part for agriculture.     

Occurrence and fate of carbamazepine,clofibric acid,diclofenac, ibuprofen,ketoprofen, and naproxen in surface waters

Although various single-concentration measurements of pharmaceuticals are available in the literature, detailed information on the variation over time of the concentration and the load in wastewater effluents and rivers and on the fate of these compounds in the aquatic environment are lacking. We measured the concentrations of six pharmaceuticals, carbamazepine, clofibric acid, diclofenac, ibuprofen, ketoprofen, and naproxen, in the effluents of three wastewater treatment plants (WWTPs), in two rivers and in the water column of Lake Greifensee (Switzerland) over a time period of three months. In WWTP effluents, the concentrations reached 0.95 microg/L for carbamazepine, 0.06 microg/L for clofibric acid, 0.99 microg/L for diclofenac, 1.3 microg/L for ibuprofen, 0.18 microg/L for ketoprofen, and 2.6 microg/L for naproxen. The relative importance in terms of loads was carbamazepine, followed by diclofenac, naproxen, ibuprofen, clofibric acid, and ketoprofen. An overall removal rate of all these pharmaceuticals was estimated in surface waters, under real-world conditions (in a lake), using field measurements and modeling. Carbamazepine and clofibric acid were fairly persistent. Phototransformation was identified as the main elimination process of diclofenac in the lake water during the study period. With a relatively high sorption coefficient to particles, ibuprofen might be eliminated by sedimentation. For ketoprofen and naproxen, biodegradation and phototransformation might be elimination processes. For the first time, quantitative data regarding removal rates were determined in surface waters under real-world conditions. All these findings are important data for a risk assessment of these compounds in surface waters.     

Removal of estrogens in municipal wastewater treatment under aerobic and anaerobic conditions: consequences for plant optimization

The removal of estrogens (estrone E1, estradiol E2, and ethinylestradiol EE2) was studied in various municipal wastewater treatment processes equipped for nutrient removal. A biological degradation model is formulated, and kinetic parameters are evaluated with batch experiments under various redox conditions. The resulting model calculations are then compared with sampling campaigns performed on differenttypes of full-scale plant: conventional activated-sludge treatment, a membrane bioreactor, and a fixed-bed reactor. The results show a > 90% removal of all estrogens in the activated sludge processes. (Due to the analytical quantification limit and low influent concentrations, however, this removal efficiency represents only an observable minimum.) The removal efficiencies of 77% and > or = 90% for E1 and E2, respectively, in the fixed-bed reactor represent a good performance in view of the short hydraulic retention time of 35 min. The first-order removal-rate constant in batch experiments observed for E2 varied from 150 to 950 d(-1) for a 1 gSS L(-1) sludge suspension. The removal efficiency of E1 and EE2 clearly depends on the redox conditions, the maximum removal rate occurring under aerobic conditions when E1 was reduced to E2. Sampling campaigns on full-scale plants indicate that the kinetic values identified in batch experiments (without substrate addition) for the natural estrogens may overestimate the actual removal rates. Although this paper does not give direct experimental evidence, it seems that the substrate present in the raw influent competitively inhibits the degradation of E1 and E2. These compounds are therefore removed mainly in activated sludge compartments with low substrate loading. Theoretical evaluation leads us to expect that diffusive mass transfer inside the floc (but not across the laminar boundary layer) appreciably influences the observed degradation rates of E1 and E2, but not of EE2.     

Survey of organic wastewater contaminants in biosolids destined for land application

In this study, the presence, composition, and concentrations of organic wastewater contaminants (OWCs) were determined in solid materials produced during wastewater treatment. This study was undertaken to evaluate the potential of these solids, collectively referred to as biosolids, as a source of OWCs to soil and water in contact with soil. Nine different biosolid products, produced by municipal wastewater treatment plants in seven different states, were analyzed for 87 different OWCs. Fifty-five of the OWCs were detected in at least one biosolid product. The 87 different OWCs represent a diverse cross section of emerging organic contaminants that enter wastewater treatment plants and may be discharged without being completely metabolized or degraded. A minimum of 30 and a maximum of 45 OWCs were detected in any one biosolid. The biosolids used in this study are produced by several production methods, and the plants they originate from have differing population demographics, yet the percent composition of total OWC content, and of the most common OWCs, typically did not vary greatly between the biosolids tested. The summed OWC content ranged from 64 to 1811 mg/kg dry weight. Six biosolids were collected twice, 3-18 months apart, and the total OWC content of each biosolid varied by less than a factor of 2. These results indicate that the biosolids investigated in this study have OWC compositions and concentrations that are more similar than different and that biosolids are highly enriched in OWCs (as mass-normalized concentrations) when compared to effluents or effluent-impacted water. These results demonstrate the need to better describe the composition and fate of OWCs in biosolids since about 50% of biosolids are land applied and thus become a potentially ubiquitous nonpoint source of OWCs into the environment.