Behavior of Glyphosate in Wastewater Treatment Plants.

The herbicide glyphosate is frequently detected in surface waters and its occurrence is linked to agricultural as well as urban uses. Elevated concentrations downstream of wastewater treatment plants (WWTPs) suggest that municipal wastewater is an important source of glyphosate in surface waters. We therefore conducted a study at a typical municipal WWTP in Switzerland to characterize the seasonality of glyphosate occurrence, the removal efficiency, and the processes involved in glyphosate removal. Glyphosate was present in raw (mechanically treated) wastewater during the whole study period (April to November). A lab incubation experiment with activated sludge indicated negligible degradation of glyphosate. Lack of degradation combined with strong adsorption lead to substantial enrichment of the compound in the sludge. Due to this enrichment and the long residence time of activated sludge (several days, compared to hours for wastewater itself), concentrations in treated wastewater show comparatively little variation, whereas concentrations in raw wastewater may fluctuate considerably. Overall removal efficiencies were in the range of 71-96%. This behavior could be described qualitatively using a numerical model that included input of glyphosate via raw wastewater, adsorption to activated sludge, and export via treated wastewater and excess sludge, but excluded degradation processes.

Identification of groundwater pollution sources in a landfill site using artificial sweeteners, multivariate analysis and transport modeling.

In this study, sources of groundwater pollution in a landfill site were identified, using artificial sweeteners as chemical tracers, multivariate statistical analysis and a quantitative analysis of the groundwater flow system through particle tracking and transport modeling. The study area, located in northern Italy, hosts an older unlined landfill and a newer lined municipal solid waste landfill placed downstream of the former. Groundwater, surface water, treated wastewater, and leachate samples were collected in March 2017 for analysis of the artificial sweeteners saccharin, cyclamate, acesulfame and sucralose together with major cations and anions, inorganic nitrogen compounds, total phosphorus, COD and some further parameters. The interpretation of the results suggests that two main leachate leaks/spills are affecting the study area. The first one concerns leachate probably spilling out of the leachate collection system serving the younger lined landfill, the other one involves leachate from the older unlined landfill that also seems to affect an area downstream of the lined landfill. Direct leachate leaks from the lined landfill seem unlikely, although they cannot be definitively excluded. This work underlines the importance of a multi-methods approach, which integrates here chemical tracers, multivariate analysis and transport modeling, for assessing groundwater pollution sources generated from complex landfill sites, where multiple and different sources may exist. In particular, this work highlights how artificial sweeteners can be used for tracing leachate plumes from landfills. The methodology applied in this study can have a broad applicability also in other polluted landfill sites worldwide.

Behavior of the Chiral Herbicide Imazamox in Soils: pH-Dependent, Enantioselective Degradation, Formation and Degradation of Several Chiral Metabolites.

Many pesticides show a pronounced biphasic degradation in soil, typically with a faster initial phase, followed by a slower decline. For chiral compounds, a biphasic decline of the total concentration may result from enantioselective degradation. In this study with the chiral herbicide imazamox, biphasic degradation was observed in most of the 18 soils investigated. In neutral soils, degradation was, in fact, enantioselective with faster degradation of (+)-imazamox. In slightly acidic soils, differences between enantiomers were not pronounced, and in strongly acidic soils, degradation was again enantioselective, but with reversed preference. Additional experiments with pure enantiomers indicated no interconversion. Enantioselective degradation thus contributed to the biphasic decline of the total concentration in certain soils. However, this was not the only factor since degradation of the individual enantiomers was biphasic in itself. In addition to the observed correlation between enantioselectivity and pH, degradation was generally faster in neutral than in acidic soils with half-lives ranging from only 2 to >120 days. Half-lives were also determined for two known metabolites and a further chiral metabolite, the structure of which was characterized by high resolution tandem mass spectrometry. As for the parent compound, half-lives of the metabolites varied considerably in the different soils.

Behavior of the Chiral Herbicide Imazamox in Soils: Enantiomer Composition Differentiates between Biodegradation and Photodegradation.

Imazamox is a chiral herbicide that, in laboratory experiments in the dark, exhibits pronounced enantioselective biodegradation in certain soils. Imazamox also shows rapid photodegradation. However, which processes are predominant in the field is not clear. We conducted a set of soil incubation experiments under natural sunlight (and corresponding dark controls), using enantioselective LC-MS/MS analysis as a probe to distinguish biodegradation and photodegradation. Under dark conditions, imazamox was degraded enantioselectively. In contrast, degradation was nonenantioselective and 2× faster when the soil was exposed to sunlight, suggesting that biodegradation (in the dark) and photodegradation (under sunlight) were the predominant degradation processes. We also investigated the effectiveness of strategies that were proposed to exclude photodegradation in field studies, covering of soil with sand or irrigation after herbicide application. The sand cover did not prevent photodegradation. On the contrary, degradation was 10× faster than in the dark and nonenantioselective. Computer simulations supported the explanation that imazamox was transported upward by capillary flow due to evaporation onto the sand surface, where it was rapidly photodegraded. Irrigation postponed but not completely prevented photodegradation. For mobile substances susceptible to photodegradation, upward transport to the soil surface thus needs to be considered when deriving rates for biodegradation from field studies.

Seasonal Dynamics of Glyphosate and AMPA in Lake Greifensee: Rapid Microbial Degradation in the Epilimnion During Summer.

Occurrence and fate of glyphosate, a widely used herbicide, and its main metabolite AMPA was investigated in Lake Greifensee, Switzerland. Monthly vertical concentration profiles in the lake showed an increase of glyphosate concentrations in the epilimnion from 15 ng/L in March to 145 ng/L in July, followed by a sharp decline to <5 ng/L in August. A similar pattern was observed for AMPA. Concentrations of glyphosate and AMPA in the two main tributaries generally were much higher than in the lake. Simulations using a numerical lake model indicated that a substantial amount of glyphosate and AMPA dissipated in the epilimnion, mainly in July and August, with half-lives of only ≈2-4 days which is ≫100 times faster than in the preceding months. Fast dissipation coincided with high water temperatures and phytoplankton densities, and low phosphate concentrations. This indicates that glyphosate might have been used as an alternative phosphorus source by bacterio- and phytoplankton. Metagenomic analysis of lake water revealed the presence of organisms known to be capable of degrading glyphosate and AMPA.

Occurrence of the herbicide glyphosate and its metabolite AMPA in surface waters in Switzerland determined with on-line solid phase extraction LC-MS/MS.

Glyphosate is currently one of the most important herbicides worldwide. Its unique properties provide for a wide range of uses in agriculture but also in non-agricultural areas. At the same time, its zwitterionic nature prevents the inclusion in multi-residue analytical methods for environmental monitoring. Consequently, despite its extensive use, data on occurrence of glyphosate in the aquatic environment is still scarce. Based on existing methods, we developed a simplified procedure for the determination of glyphosate and its main metabolite aminomethylphosphonic acid (AMPA) in water samples using derivatization with fluorenylmethyl chloroformate FMOC-Cl, combined with on-line solid phase extraction and liquid chromatography-tandem mass spectrometry (LC-MS/MS) detection. This method was extensively tested on over 1000 samples of surface water, groundwater, and treated wastewater and proved to be simple, sensitive, and reliable. Limits of quantification of 0.005 µg/L were routinely achieved. Glyphosate and AMPA were detected in the vast majority of stream water samples in the area of Zurich, Switzerland, with median concentrations of 0.11 and 0.20 µg/L and 95th percentile concentrations of 2.1 and 2.6 µg/L, respectively. Stream water data and data from treated wastewater indicated that non-agricultural uses may significantly contribute to the overall loads of glyphosate and AMPA in surface waters. In the investigated groundwater samples, selected specifically because they had shown presence of other herbicides in previous monitoring programs, glyphosate and AMPA were generally not detected, except for two monitoring sites in Karst aquifers, indicating that these compounds show much less tendency for leaching.

Stereoselective Metabolism of the Sterol Biosynthesis Inhibitor Fungicides Fenpropidin, Fenpropimorph, and Spiroxamine in Grapes, Sugar Beets, and Wheat.

Metabolism of chiral pesticides in crops is typically studied using achiral analytical methods and, consequently, the stereoisomer composition of residues is unknown. In this study, we developed an enantioselective GC-MS/MS method to quantify residues of the fungicides fenpropidin, fenpropimorph, and spiroxamine in plant matrices. In field trials, the fungicides were applied to grapevines, sugar beets, or wheat. Fenpropidin was metabolized with no or only weak enantioselectivity. For fenpropimorph, slightly enantioselective metabolism was observed in wheat but more pronounced in sugar beets. This enantioselectivity was due to different rates of metabolism and not due to interconversion of enantiomers. The four stereoisomers of spiroxamine were also metabolized at different rates, but selectivity was only found between diastereomers and not between enantiomers. trans-Spiroxamine was preferentially degraded in grapes and cis-spiroxamine in wheat. These findings may affect the consumer dietary risk assessment because toxicological end points were determined using racemic test substances.

Time-dependent sorption of two novel fungicides in soils within a regulatory framework.

BACKGROUND: Convincing experimental evidence suggests increased sorption of pesticides on soil over time, which, so far, has not been considered in the regulatory assessment of leaching to groundwater. Recently, Beulke and van Beinum (2012) proposed a guidance on how to conduct, analyse and use time-dependent sorption studies in pesticide registration. The applicability of the recommended experimental set-up and fitting procedure was examined for two fungicides, penflufen and fluxapyroxad, in four soils during a 170 day incubation experiment. RESULTS: The apparent distribution coefficient increased by a factor of 2.5-4.5 for penflufen and by a factor of 2.5-2.8 for fluxapyroxad. The recommended two-site, one-rate sorption model adequately described measurements of total mass and liquid phase concentration in the calcium chloride suspension and the calculated apparent distribution coefficient, passing all prescribed quality criteria for model fit and parameter reliability. CONCLUSION: The guidance is technically mature regarding the experimental set-up and parameterisation of the sorption model for the two moderately mobile and relatively persistent fungicides under investigation. These parameters can be used for transport modelling in soil, thereby recognising the existence of the experimentally observed, but in the regulatory leaching assessment of pesticides not yet routinely considered phenomenon of time-dependent sorption. © 2016 Society of Chemical Industry.

Environmental behavior of the chiral herbicide haloxyfop. 2. Unchanged enantiomer composition in blackgrass (Alopecurus myosuroides) and garden cress (Lepidium sativum).

Haloxyfop-methyl is a chiral herbicide against grasses in dicotyledonous crops. In plants and soil, haloxyfop-methyl is rapidly hydrolyzed to haloxyfop-acid, whose R-enantiomer carries the actual herbicidal activity. In soil, S-haloxyfop-acid is converted within less than 1 day and almost completely into R-haloxyfop-acid. In this study, we investigated the possible interconversion of the enantiomers of haloxyfop-methyl and haloxyfop-acid in blackgrass and garden cress. Racemic or enantiopure haloxyfop-methyl was applied to the leaves of plants grown in agar. The metabolism was followed during 4 days using enantioselective GC-MS. In contrast to soils, no interconversion was observed in plants, and metabolism was nonenantioselective. These findings are consistent with the fact that after pre-emergence application to soil and uptake by roots, the observed herbicidal effect is basically independent of the enantiomer composition of the applied substance, whereas after postemergence application, the efficacy clearly is different for the two enantiomers.

Environmental behavior of the chiral herbicide haloxyfop. 1. Rapid and preferential interconversion of the enantiomers in soil.

Haloxyfop-methyl is a chiral herbicide that was first introduced as racemate and later replaced by "haloxyfop-P-methyl", mainly consisting of the R-enantiomer, which carries the herbicidal activity. We studied the ester cleavage of haloxyfop-methyl and further degradation and chiral inversion of the acid enantiomers in three different soils using enantioselective gas chromatography-mass spectrometry. Our results confirm the rapid ester hydrolysis of haloxyfop-methyl with half-lives of a few hours and indicate that hydrolysis is weakly enantioselective. Further degradation of haloxyfop was slower with half-lives of several days. In all three soils, S-haloxyfop was rapidly converted to R-haloxyfop. In sterile soil, no degradation and no inversion were observed, indicating that both processes are biologically mediated. In soil where 50% of the water had been replaced by deuterium oxide, significant H-D exchange in haloxyfop was observed, pointing to a reaction mechanism involving abstraction of the proton at the chiral center of the molecule.

Online solid phase extraction LC-MS/MS method for the analysis of succinate dehydrogenase inhibitor fungicides and its applicability to surface water samples.

A sensitive and selective analytical method, based on online solid phase extraction coupled to LC-MS/MS, was developed and validated to determine traces of several recently introduced fungicides in surface water and wastewater. The list of target analytes included eight succinate dehydrogenase inhibitors (bixafen, boscalid, fluopyram, flutolanil, fluxapyroxad, isopyrazam, penflufen, and penthiopyrad), and two other fungicides with different modes of action, fenpyrazamine and fluopicolide. Detection and quantification limits in various matrices were in the range of 0.1 to 2 and 0.5 to 10 ng/L, respectively. Moderate signal suppression was observed in surface water (≤15%) and wastewater (≤25%) and was well compensated by the selected internal standard. The intra- and inter-day precisions were generally <10 and <20%, respectively. The applicability of the method was demonstrated in a study on the occurrence of fungicides in the river Glatt, Switzerland, that drains a catchment area of 419 km(2) with a substantial proportion of agricultural land. Of the studied compounds, only boscalid and fluopicolide were detected in flow-proportional weekly composite samples, generally at low concentrations up to 15 and 5 ng/L, respectively. While fluopicolide was detected in only 30% of the samples above the LOD of 0.5 ng/L, boscalid was detected in all samples analyzed between March and October 2012.

The chiral herbicide beflubutamid (II): Enantioselective degradation and enantiomerization in soil, and formation/degradation of chiral metabolites.

Beflubutamid is a chiral soil herbicide currently marketed as racemate against dicotyledonous weeds in cereals. Biotests have shown that (-)-beflubutamid is at least 1000× more active than (+)-beflubutamid. Potential substitution of the racemate by (-)-beflubutamid should therefore be further considered. Here, we investigated the degradation behavior in soils and formation and degradation of two chiral metabolites. Laboratory incubation experiments were performed with an alkaline and an acidic soil. The compounds were analyzed by enantioselective GC-MS. Degradation rate constants were determined by kinetic modeling. In the alkaline soil, degradation of beflubutamid was slightly enantioselective, with slower degradation of the herbicidally active (-)-enantiomer. In the acidic soil, however, both enantiomers were degraded at similar rates. In contrast, degradation of a phenoxybutanamide metabolite was highly enantioselective. Chiral stability of beflubutamid and its metabolites was studied in separate incubations with the pure enantiomers in the same soils. In these experiments, (-)-beflubutamid was not converted to the nonactive (+)-enantiomer and vice versa. Significant enantiomerization was, however, observed for the major metabolite, a phenoxybutanoic acid. With regard to biological activity and behavior in soils, enantiopure (-)-beflubutamid definitively has the potential to substitute for the racemic herbicide.

The chiral herbicide beflubutamid (I): Isolation of pure enantiomers by HPLC, herbicidal activity of enantiomers, and analysis by enantioselective GC-MS.

For many chiral pesticides, little information is available on the properties and fate of individual stereoisomers. A basic data set would, first of all, include stereoisomer-specific analytical methods and data on the biological activity of stereoisomers. The herbicide beflubutamid, which acts as an inhibitor of carotenoid biosynthesis, is currently marketed as racemate against dicotyledonous weeds in cereals. Here, we present analytical methods for enantiomer separation of beflubutamid and two metabolites based on chiral HPLC. These methods were used to assign the optical rotation and to prepare milligram quantities of the pure enantiomers for further characterization with respect to herbicidal activity. In addition, sensitive analytical methods were developed for enantiomer separation and quantification of beflubutamid and its metabolites at trace level, using chiral GC-MS. In miniaturized biotests with garden cress, (-)-beflubutamid showed at least 1000× higher herbicidal activity (EC50, 0.50 µM) than (+)-beflubutamid, as determined by analysis of chlorophyll a in 5-day-old leaves. The agricultural use of enantiopure (-)-beflubutamid rather than the racemic compound may therefore be advantageous from an environmental perspective. In further biotests, the (+)-enantiomer of the phenoxybutanoic acid metabolite showed effects on root growth, possibly via an auxin-type mode of action, but at 100× higher concentrations than the structurally related herbicide (+)-mecoprop.

Saccharin and other artificial sweeteners in soils: estimated inputs from agriculture and households, degradation, and leaching to groundwater.

Artificial sweeteners are consumed in substantial quantities as sugar substitutes and were previously shown to be ubiquitously present in the aquatic environment. The sweetener saccharin is also registered as additive in piglet feed. Saccharin fed to piglets was largely excreted and, consequently, found in liquid manure at concentrations up to 12 mg/L, where it was stable during 2 months of storage. Saccharin may thus end up in soils in considerable quantities with manure. Furthermore, other studies showed that saccharin is a soil metabolite of certain sulfonylurea herbicides. Sweeteners may also get into soils via irrigation with wastewater-polluted surface water, fertilization with sewage sludge (1-43 µg/L), or through leaky sewers. In soil incubation experiments, cyclamate, saccharin, acesulfame, and sucralose were degraded with half-lives of 0.4-6 d, 3-12 d, 3-49 d, and 8-124 d, respectively. The relative importance of entry pathways to soils was compared and degradation and leaching to groundwater were evaluated with computer simulations. The data suggest that detection of saccharin in groundwater (observed concentrations, up to 0.26 µg/L) is most likely due to application of manure. However, elevated concentrations of acesulfame in groundwater (up to 5 µg/L) may result primarily from infiltration of wastewater-polluted surface water through stream beds.

Composition of aldrin, dieldrin, and photodieldrin enantiomers in technical and environmental samples.

Aldrin and dieldrin belong to the group of polycyclic chlorinated insecticides that are banned under the Stockholm Convention (POP Convention). Despite the fact that the use of these compounds ceased many years ago, aldrin and, in particular, dieldrin are still present in the environment from former applications, leading occasionally to contamination of agricultural produce and food, particularly Cucurbitaceae. These prochiral compounds have a complex stereochemistry. In the environment, aldrin is rapidly converted to its epoxide, dieldrin. Photolysis is one of the environmental transformation processes reported to be important for the compounds, leading to photoproducts such as photoaldrin and photodieldrin. In contrast to the parent compounds, photoaldrin and photodieldrin are chiral and exist as pairs of enantiomers. Although dieldrin and its metabolites have been extensively reviewed, the chirality of many of its metabolites has so far not been considered. In this study, the composition of technical aldrin and dieldrin from the 1950s and their photoproducts was investigated using both non-enantioselective and enantioselective gas chromatography with detection by several mass spectrometric techniques. Full enantiomer resolution of photodieldrin was achieved using a column with a silylated gamma-cyclodextrin as chiral selector. Photoaldrin, however, showed peak broadening, indicating some marginal resolution of the enantiomers. Whereas photodieldrin was formed as a racemate from both aldrin and dieldrin by natural sunlight, the analysis of environmental and biological samples (soil, biota) indicated its presence mostly with enantiomer compositions clearly differing from 1:1. The presence of photodieldrin in soil, treated more than 40 years ago with aldrin or dieldrin, documents that the photoreaction of dieldrin plays some role in the transformation of the compounds in the environment and that enantioselective biological processes are involved in its further transformation. The preliminary data also indicate that photodieldrin probably is not bioaccumulated more than dieldrin.

Hydrophilic anthropogenic markers for quantification of wastewater contamination in ground- and surface waters.

Hydrophilic, persistent markers are useful to detect, locate, and quantify contamination of natural waters with domestic wastewater. The present study focused on occurrence and fate of seven marker candidates including carbamazepine (CBZ), 10,11-dihydro-10,11-dihydroxycarbamazepine (DiOH-CBZ), primidone (PMD), crotamiton (CTMT), N-acetyl-4-aminoantipyrine (AAA), N-formyl-4-aminoantipyrine (FAA), and benzotriazole (BTri) in wastewater treatment plants (WWTPs), lakes, and groundwater. In WWTPs, concentrations from 0.14 microg/L to several micrograms per liter were observed for all substances, except CTMT, which was detected at lower concentrations. Loads determined in untreated and treated wastewater indicated that removal of the potential markers in WWTPs is negligible; only BTri was partly eliminated (average 33%). In lakes, five compounds, CBZ, DiOH-CBZ, FAA, AAA, and BTri, were consistently detected in concentrations of 2 to 70 ng/L, 3 to 150 ng/L, less than the limit of quantification to 30 ng/L, 2 to 80 ng/L, and 11 to 920 ng/L, respectively. Mean per capita loads in the outflows of the lakes suggested possible dissipation in surface waters, especially of AAA and FAA. Nevertheless, concentrations of CBZ, DiOH-CBZ, and BTri correlated with the actual anthropogenic burden of the lakes by domestic wastewater, indicating that these compounds are suitable for quantification of wastewater contamination in lakes. Marker candidates were also detected in a number of groundwater samples. Carbamazepine concentrations up to 42 ng/L were observed in aquifers with significant infiltration of river water, receiving considerable wastewater discharges from WWTPs. Concentration ratios between compounds indicated some elimination of BTri and DiOH-CBZ during subsurface passage or in groundwater, while CBZ and PMD appeared to be more stable and thus are promising wastewater markers for groundwater. The wastewater burden in groundwater, estimated with the markers CBZ and PMD, reached up to 6%.

Ubiquitous occurrence of the artificial sweetener acesulfame in the aquatic environment: an ideal chemical marker of domestic wastewater in groundwater.

Artificial low-calorie sweeteners are consumed in considerable quantities with food and beverages. After ingestion, some sweeteners pass through the human metabolism largely unaffected, are quantitatively excreted via urine and feces, and thus reach the environment associated with domestic wastewater. Here, we document the widespread occurrence of four sweeteners in the aquatic environment and show that one of these compounds, acesulfame, meets all of the criteria of an ideal marker for the detection of domestic wastewater in natural waters, particularly groundwater. Acesulfame was consistently detected in untreated and treated wastewater (12-46 microg/L), in most surface waters, in 65% of the investigated groundwater samples, and even in several tap water samples (up to 2.6 microg/L) from Switzerland. The sweetener was not eliminated in wastewater treatment plants (WWTPs) and was quite persistent in surface waters, where concentrations increased with population in the catchment area and decreased with water throughflow. The highest concentrations in groundwater, up to 4.7 microg/L, were observed in areas with significant infiltration of river water, where the infiltrating water received considerable discharges from WWTPs. Given the currently achieved detection limit of approximately 0.01 microg/L, it is possible to trace the presence of > or = 0.05% wastewater in groundwater.

Azole fungicides: occurrence and fate in wastewater and surface waters.

The mode of action of azole compounds implies a potential to affect endocrine systems of different organisms and is reason for environmental concern. The occurrence and fate of nine agricultural azole fungicides, some of them also used as biocides, and four azole pharmaceuticals were studied in wastewater treatment plants (WWTPs) and lakes in Switzerland. Two pharmaceuticals (fluconazole, clotrimazole, 10-110 ng L(-1)) and two biocides (propiconazole, tebuconazole, 1-30 ng L(-1)) were consistently observed in WWTP influents. Loads determined in untreated and treated wastewater indicated thatfluconazole, propiconazole, and tebuconazole were largely unaffected by wastewater treatment, but clotrimazole was effectively eliminated (> 80%). Incubation studies with activated sludge showed no degradation for fluconazole and clotrimazole within 24 h, but strong sorption of clotrimazole to activated sludge. Slow degradation and some sorption were observed for tebuconazole and propiconazole (degradation half-lives, 2-3 d). In lakes, fluconazole, propiconazole, and tebuconazole were detected at low nanogram-per-liter levels. Concentrations of the pharmaceutical fluconazole correlated with the expected contamination by domestic wastewater, but not those of the biocides. Per capita loads of propiconazole and tebuconazole in lakes suggested additional inputs; for example, from agricultural use or urban runoff rainwater.

Nicotine derivatives in wastewater and surface waters: application as chemical markers for domestic wastewater.

Nicotine is extensively metabolized in the human body to a number of compounds, which may enter natural waters via discharge of domestic wastewater. However, little is known on exposure of and potential effects on the aquatic environment. In this study, two major urinary metabolites, cotinine and 3'-hydroxycotinine, as well as a further tobacco alkaloid, N-formylnornicotine, were measured in wastewater and water from Swiss lakes using an analytical procedure based on SPE and LC-MS/MS SRM with cotinine-d3 as internal standard (LOQs, 1.0-1.5 ng/L). Typical concentrations of cotinine and 3'-hydroxycotinine were approximately 1-10 microg/L in untreated wastewater, but clearly less in treated wastewater (approximately 0.01-0.6 microg/L), corresponding to elimination efficiencies of 90-99%. N-Formylnornicotine, however,was found at similar concentrations in untreated and treated wastewater (0.02-0.15 microg/L). Its apparent persistence during wastewater treatment was further confirmed by incubation experiments with activated sludge. In lakes, cotinine, 3'-hydroxycotinine, and N-formylnornicotine were detected at concentrations up to 15, 80, and 6 ng/L, respectively. Concentrations in lakes correlated with the expected anthropogenic burden by domestic wastewater (ratio population per water throughflow), demonstrating the suitability of these nicotine derivatives as hydrophilic, anthropogenic markers. In small receiving waters with significant wastewater discharges, concentrations of a few hundred ng/L may be expected. Possible ecotoxicological risks associated with such environmental concentrations, can, however, not be assessed at present as data on effects on aquatic organisms are very limited, in particular on long-term effects.

Occurrence and fate of the cytostatic drugs cyclophosphamide and ifosfamide in wastewater and surface waters.

The two oxazaphosphorine compounds cyclophosphamide and ifosfamide are important cytostatic drugs used in the chemotherapy of cancer and in the treatment of autoimmune diseases. Their mechanism of action, involving metabolic activation and unspecific alkylation of nucleophilic compounds, accounts for genotoxic effects described in the literature and is reason for environmental concern. The occurrence and fate of cyclophosphamide and ifosfamide were studied in wastewater treatment plants (WWTPs) and surface waters in Switzerland, using a highly sensitive analytical method based on solid-phase extraction and liquid chromatography tandem mass spectrometry. The compounds were detected in untreated and treated wastewater at concentrations of <0.3-11 ng/L, which corresponded well with concentrations predicted from consumption data and typical renal excretion rates. Weekly loads determined in influent and effluent wastewater were comparable and suggested a high persistence in WWTPs. Furthermore, no degradation was observed in activated sludge incubation experiments within 24 h at concentrations of approximately 100 ng/L. Processes that may be relevant for elimination in natural waterbodies were studied with a set of incubation experiments in the laboratory. After extrapolation to natural conditions in surface waters, a slow dark-chemical degradation (half-lives on the order of years) is the most important transformation process. Degradation by photochemically formed HO* radicals may be of some relevance only in shallow, clear, and nitrate-rich waterbodies but could be further exploited for elimination of these compounds by advanced oxidation processes, i.e., in a treatment of hospital wastewater. In surface waters, concentrations ranged from < or =50 to 170 pg/L and were thus several orders of magnitude lower than the levels at which acute ecotoxicological effects have been reported in the literature (mg/L range). However, due to a lack of studies on chronic effects on aquatic organisms and data on occurrence and effects of metabolites, a final risk assessment cannot be made.