An evaluation of the OECD 308 water/sediment systems for investigating the biodegradation of pharmaceuticals

In recent times, trace levels of pharmaceuticals detected in wastewater effluents and surface waters have raised the level of attention around the ultimate fate and the potential persistence of pharmaceuticals in the environment. We have seen the European Agency for the Evaluation of Medicines (EMEA) recently include more rigorous environmental fate testing in European Union (EU) Environmental Risk Assessment (ERA) guidance to assess the ultimate fate in water/sediment systems. Yet to date, there is little data available that covers the fate of pharmaceuticals in the water/sediment compartment, and little that assess whether current aerobic and anaerobic methods are appropriate for pharmaceuticals. In this study, the biodegradation profiles of 3 Pfizer products were investigated following the latest ERA guidance and its recommendation for OECD 308 water/sediment biodegradation testing. Experiments included 14C-labeled exemestane, azithromycin, and varenicline representing neutral and cationic pharmaceuticals with average K(oc) values of 3704, 49 400, and 10 483 respectively. Specific HPLC/radioactive monitoring (RAM) methods were used to profile water and sediment samples for biotransformation products. Binding to sediment, as "non-extractables", was considerable for all three pharmaceuticals, though most notable for the cationic pharmaceuticals varenicline and azithromycin ranging from 52% to 94% at study termination, respectively. In general, for all 3 pharmaceuticals studied, the anaerobic conditions demonstrated less biotransformation and mineralization than the aerobic; though their biotransformation profile (number of metabolites) and amount bound to sediment were similar. Based on these findings and our current understanding of anaerobic biodegradation, we would recommend a tiered approach to the OECD 308 water/ sediment test: with default testing just for aerobic conditions; and then if needed, anaerobic testing only for those compounds potentially amenable to typical anaerobic processes. We suggest that as a simulation test would be better suited in later tier testing under EU ERA guidance. Inherent biodegradation or die-away tests seem better suited to derive biodegradation rate constants for subsequent environmental modeling of water and sediment compartments.     

Elucidating the relative roles of ammonia oxidizing and heterotrophic bacteria during the biotransformation of 17α-Ethinylestradiol and Trimethoprim

The biological fate of 17α-ethinylestradiol (EE2; 500 ng/L to 1 mg/L) and trimethoprim (TMP; 1 μg/L to 1 mg/L) was evaluated with flow through reactors containing an ammonia oxidizing bacterial (AOB) culture, two enriched heterotrophic cultures devoid of nitrifier activity, and nitrifying activated sludge (NAS) cultures. AOBs biotransformed EE2 but not TMP, whereas heterotrophs mineralized EE2, biotransformed TMP, and mineralized EE2-derived metabolites generated by AOBs. Kinetic bioassays showed that AOBs biotransformed EE2 five times faster than heterotrophs. The basal expression of heterotrophic dioxygenase enzymes was sufficient to achieve the high degree of transformation observed at EE2 and TMP concentrations ≤ 1 mg/L, and enhanced enzyme expression was not necessary. The importance of AOBs in removing EE2 and TMP was evaluated further by performing NAS experiments at lower feed concentrations (500-1000 ng/L). EE2 removal slowed markedly after AOBs were inhibited, while TMP removal was not affected by AOB inhibition. Two key EE2 metabolites formed by AOB and heterotrophic laboratory-scale chemostats were also found in independent laboratory-scale mixed culture bioreactors; one of these, sulfo-EE2, was largely resistant to further biodegradation. AOBs and heterotrophs may cooperatively enhance the reliability of treatment systems where efficient removal of EE2 is desired.     

Screening of human antibiotic substances and determination of weekly mass flows in five sewage treatment plants in Sweden

Twelve antibiotic substances for human use, including trimethoprim and representatives of the fluoroquinolone (FQ), sulfonamide (SA), penicillin (PE), cephalosporin (CE), nitroimidazole (NI), tetracycline (TC), and macrolide (MA) groups, were subjected to a screening study at five Swedish sewage treatment plants (STPs) during one week in 2002 and one week in 2003. The analytes were extracted from raw sewage water, final effluent, and sludge by solid-phase extraction (SPE) or liquid-solid extraction (as appropriate) and then identified and quantified by liquid chromatography/tandem mass spectrometry. The mostfrequently detected antibiotics in the matrices considered in this study were norfloxacin, ofloxacin, ciprofloxacin, trimethoprim, sulfamethoxazole, and doxycycline. The other analytes were only detected in a few samples. Analysis of the weekly mass flows through each STP showed that FQs were partly eliminated from the water during sewage water treatment and the highest amounts of these substances were found in sludge. Sulfamethoxazole and trimethoprim were mainly found in raw sewage water and final effluent, but these substances had balancing mass flows, indicating that they too can withstand sewage water treatment. The mass flow patterns for doxycycline were more complex, with high amounts occurring in sludge in some cases, suggesting thatthe behavior of this analyte may be more strongly influenced by the treatment process and other variables at individual STPs. The environmental load (the sum of the amounts in the final effluent and sludge) normalized to the number of inhabitants in the catchment area of each investigated STP compared with theoretical predictions based on consumption data (in parentheses) showed good correlations: norfloxacin, 0.8 (0.9); ofloxacin, 0.3 (0.2); ciprofloxacin, 1.3 (3.5); sulfamethoxazole, 0.2 (0.4); trimethoprim, 1.1 (1.0); and doxycycline, 0.7 (0.4) mg per person per week. The results show that reasonably accurate predictions of environmental load of these antibiotics can be time-effectively derived from consumption data without additional measurements.     

Behavior of fluoroquinolones and trimethoprim during mechanical, chemical, and active sludge treatment of sewage water and digestion of sludge

The behavior and fate of three fluoroquinolones (norfloxacin, ofloxacin, and ciprofloxacin), one sulfonamide (sulfamethoxazole), and trimethoprim were investigated at a sewage treatment plant in Ume?, Sweden, in 2004. This plant uses conventional mechanical, chemical, and activated sludge methods to treat the sewage water and digest the sludge; the dewatered digested sludge is pelleted (dry weight > 90% of total weight). Raw sewage water and particles as well as effluents and sludge from specific treatment areas within the plant were sampled. In addition to quantifying the antibiotics within the plant, we characterized the sample matrixes to facilitate evaluation of the results. Of the five substances examined, only norfloxacin, ciprofloxacin, and trimethoprim were present in concentrations higher than their limits of quantification. Norfloxacin and ciprofloxacin sorbed to sludge in a manner that was independent of changes in pH during sewage treatment, and more than 70% of the total amount of these compounds passing through the plant was ultimately found in the digested sludge. The results suggest that fluoroquinolones undergo thermal degradation during pelleting, but more studies are needed to confirm this. Trimethoprim was found in the final effluent at approximately the same concentration and mass flow as in the raw sewage, and could not be quantified in any solid sample. Predicted environmental concentrations, based on consumption data for Ume? municipality, correlated well with the results obtained, especially when the predicted concentrations were corrected to account for the amount of each active substance excreted in urine. The results obtained were compared to those of previous studies of these three substances' behavior and fate and were found to be similar, although some of the other plants studied employed the various treatment steps in different orders.     

Enhanced biodegradation of iopromide and trimethoprim in nitrifying activated sludge

Iopromide (an X-ray contrast agent) and trimethoprim (an antibacterial drug) are frequently detected pharmaceuticals in effluents of wastewater treatment plants (WWTPs) and in surface waters due to their persistence and high usage. Laboratory-scale experiments showed that a significantly higher removal rate in nitrifying activated sludge as compared to conventional activated sludge was observed for both iopromide and trimethoprim. When the activity of the nitrifying bacteria was inhibited, the percent removal of iopromide decreased from 97 to 86% while trimethoprim removal decreased from 70 to 25%. The metabolite of iopromide identified when nitrification was not inhibited was a dehydroxylated iopromide at the two side chains. However, when the nitrifying bacteria were inhibited the metabolite identified was a carboxylate, formed during the oxidation of the primary alcohol on the side chain of iopromide. These results suggest that the nitrifying bacteria are important in the observed biodegradation of iopromide in the activated sludge with higher solid retention time (SRT). Results from the laboratory-scale study were corroborated by the observed removal efficiencies in a full-scale municipal WWTP, which showed that iopromide (ranging from 0.10 to 0.27 microg/L) and trimethoprim (ranging from 0.0.08 to 0.53 microg/L) were removed more effectively in the nitrifying activate sludge which has a higher SRT (49 days) than in the conventional activated sludge (SRT of 6 days). In nitrifying activated sludge, the percent removal of iopromide in the WWTP reached 61%, while in conventional activated sludge, average removal was negligible. For trimethoprim, removal was limited to about 1% in the conventional activated sludge, while in the nitrifying activated sludge, the removal was increased to 50%.     

Use of compound-specific stable carbon isotope analyses to demonstrate anaerobic biodegradation of MTBE in groundwater at a gasoline release site

Currently it is unclear if natural attenuation is an appropriate remedial approach for groundwater impacted by methyl tertiary butyl ether (MTBE). Site-characterization data at most gasoline release sites are adequate to evaluate attenuation in MTBE concentrations over time or distance. But, demonstrating natural biodegradation of MTBE requires laboratory microcosm studies, which could be expensive and time-consuming. Recently, compound-specific carbon isotope ratio analyses (13C/12C expressed in delta13C notation) have been used to demonstrate aerobic biodegradation of MTBE in laboratory incubations. This study explored the potential of this approach to distinguish MTBE biodegradation from other abiotic processes in an anaerobic groundwater plume that showed extensive decrease in MTBE concentrations. To our knowledge, this is the first study to use delta13C of MTBE data in groundwater and laboratory microcosms to demonstrate anaerobic biodegradation of MTBE. The delta13C of MTBE in monitoring wells increased by up to 31 per thousand (-25.5 per thousand to +5.5 per thousand) along with a 40-fold decrease in MTBE concentrations. Anaerobic incubations in laboratory microcosms indicated up to 20-fold reduction in MTBE concentrations with a corresponding increase in delta13C of MTBE of up to 33.4 per thousand (-28.7 per thousand to +4.7 per thousand) in live microcosms. Little enrichment was observed in autoclaved controls. These results demonstrate that anaerobic biodegradation was the dominant natural attenuation mechanism for MTBE at this site. The estimated isotopic enrichment factors (epsilon(field) = -8.10 per thousand and epsilon(lab) = -9.16 per thousand) were considerably larger than the range (-1.4 per thousand to -2.4 per thousand) previously reported for aerobic biodegradation of MTBE in laboratory incubations. These observations strongly suggest that delta13C of MTBE could be potentially useful as an "indicator" of in-situ MTBE biodegradation.     

Fate of alkylphenolic compounds during activated sludge treatment: impact of loading and organic composition

The impact of loading and organic composition on the fate of alkylphenolic compounds in the activated sludge plant (ASP) has been studied. Three ASP designs comprising carbonaceous, carbonaceous/nitrification, and carbonaceous/nitrification/denitrification treatment were examined to demonstrate the impact of increasing levels of process complexity and to incorporate a spectrum of loading conditions. Based on mass balance, overall biodegradation efficiencies for nonylphenol ethoxylates (NPEOs), short chain carboxylates (NP(1-3)EC) and nonylphenol (NP) were 37%, 59%, and 27% for the carbonaceous, carbonaceous/nitrification, and carbonaceous/nitrification/denitrification ASP, respectively. The presence of a rich community of ammonia oxidizing bacteria does not necessarily facilitate effective alkylphenolic compound degradation. However, a clear correlation between alkylphenolic compound loading and long chain ethoxylate compound biodegradation was determined at the three ASPs, indicating that at higher initial alkylphenolic compound concentrations (or load), greater ethoxylate biotransformation can occur. In addition, the impact of settled sewage organic composition on alkylphenolic compound removal was evaluated. A correlation between the ratio of chemical oxygen demand (COD) to alkylphenolic compound concentration and biomass activity was determined, demonstrating the inhibiting effect of bulk organic matter on alkylphenol polyethoxylate transformation activity. At all three ASPs the biodegradation pathway proposed involves the preferential biodegradation of the amphiphilic ethoxylated compounds, after which the preferential attack of the lipophilic akylphenol moiety occurs. The extent of ethoxylate biodegradation is driven by the initial alkylphenolic compound concentration and the proportion of COD constituted by the alkylphenol polyethoxylates (APEOs) and their metabolites relative to the bulk organic concentration of the sewage composed of proteins, acids, fats, and polysaccharides. Secondary effluents from this study are characterized by low bulk organic concentrations and comparatively high micropollutant concentrations. Based on the biodegradation mechanism proposed in this study, application of high rate tertiary biological treatment processes to secondary effluents characterized by low bulk organic concentrations and comparatively high APEO concentrations is predicted to provide a sustainable solution to micropollutant removal.     

Seasonal variation in the occurrence of pharmaceuticals in effluents from a sewage treatment plant and in the recipient water

The occurrence of five pharmaceuticals (ibuprofen, naproxen, ketoprofen, diclofenac, and bezafibrate) in the influent and effluent water of a sewage treatment plant (STP) in the recipient river water and in a drinking water treatment plant (DWTP) located downstream from the STP was followed during three seasons: winter, spring, and summer. In the STP, the elimination of the pharmaceuticals decreased significantly (an average of 25% compared to spring and summer) in wintertime leading to increased concentrations of pharmaceuticals in the effluent water. The total concentration of all the studied pharmaceuticals in the effluent water was 3-5 times higher in wintertime (about 2500 ng L(-1)) than during the other seasons (about 500-900 ng L(-1)). Accordingly, the highest concentrations (up to 129 ng L(-1)) in the recipient river were measured in the wintertime. Pharmaceuticals were carried longer distances downstream from the STP when the river was covered by ice and snow. During a drastic increase in water flow rate (i.e., during snowmelting), a fast transportation of the pharmaceuticals was observed. The DWTP located downstream from the STP produced water that contained about 8 ng L(-1) of ibuprofen and ketoprofen in the winter sample, whereas in spring and summer the studied pharmaceuticals could not be detected in the drinking water. The results show that cold seasons in boreal areas can severely increase the environmental risk of pharmaceuticals and the risk for contamination of drinking water.     

Elimination of selected acidic pharmaceuticals from municipal wastewater by an activated sludge system and membrane bioreactors

The elimination of six acidic pharmaceuticals (clofibric acid, diclofenac, ibuprofen, ketoprofen, mefenamic acid, and naproxen) in a real wastewater treatment plant (WWTP) using an activated sludge system and membrane bioreactors (MBRs) was investigated by using a gas chromatography/mass spectrometry (GC/MS) system for measurement of the compounds. Limited information is available for some of the tested pharmaceuticals at present. Solid retention times (SRTs) of the WWTP and the two MBRs were 7, 15, and 65 days, respectively. The elimination rates varied from compound to compound. The MBRs exhibited greater elimination rates for the examined pharmaceuticals than did the real plant. Dependency of the elimination rates of the pharmaceuticals on SRTs was obvious; the MBR operated with a longer SRT of 65 days clearly showed better performance than did the MBR with a shorter SRT of 15 days. The difference between the two MBRs was particularly significant in terms of elimination of ketoprofen and diclofenac. Measurements of the amounts of adsorbed pharmaceuticals on the sludge and aerobic batch elimination experiments were carried out to investigate the elimination pathways of the pharmaceuticals. Results of the batch elimination tests revealed that the sludges in the MBRs had large specific sorption capacities mainly due to their large specific surface areas. Despite the sorption capacities of sludges, the main mechanism of elimination of the pharmaceuticals in the investigated processes was found to be biodegradation. Biodegradation of diclofenac, which has been believed to be refractory to biodegradation, seemed to occur very slowly.     

Impact of bioavailability restrictions on microbially induced stable isotope fractionation. 2. Experimental evidence

Stable isotope fractionation analysis (SIFA) of contaminants is an emerging technique to characterize in situ microbial activity. The kinetic isotope effect in microbial degradation reactions, or enzyme catalysis, is caused by the preferential cleavage of bonds containing light rather than heavy isotopes. This leads to a relative enrichment of the heavier isotopes in the residual substrate pool. However, a number of nonisotopically sensitive steps preceding the isotopically sensitive bond cleavage may affect the reaction kinetics of a degradation process, thus reducing the observed (i.e., the macroscopically detectable) isotope fractionation. Low bioavailability of contaminants poses kinetic limitations on the biodegradation process and can significantly reduce the observed kinetic isotope fractionation. Here we present experimental evidence for the influence of bioavailability-limited pollutant biodegradation on observed stable isotope fractionation. Batch laboratory experiments were performed to quantify the toluene hydrogen isotope fractionation of Pseudomonas putida mt-2 (pWWO) subjected to different small concentrations of toluene with and without deuterium label, which corresponded to realistic environmental mass transfer scenarios. Detected isotope fractionations depended significantly on the toluene concentration, hence confirming the influence of substrate mass transfer limitation on observed isotope fractionation, hypothesized by Thullner et al. (Environ. Sci. Technol. 2008, 42,6544-6551). Our results indicate that the bioavailability of a substrate should be considered during quantitative analysis of microbial degradation based on SIFA.     

Volatilization and biodegradation of naphthalene in the vadose zone impacted by phytoremediation

The combined remediation mechanisms of volatilization and biodegradation in the vadose zone were investigated for naphthalene remediation at a creosote-contaminated site where a poplar tree-based phytoremediation system has been installed. Concurrent field and laboratory experiments were conducted to study the transport and biodegradation of naphthalene in the vadose zone. Soil gas sampling showed that more than 90% of the naphthalene vapors were biodegraded aerobically within 5-10 cm above the water table during the summer months. Peak naphthalene soil gas concentrations were observed in the late summer, corresponding with peak naphthalene aqueous concentrations and the minimum saturated zone thickness. An analytical solution was developed for vapor transport where the diffusion coefficient and first-order biodegradation rate vary vertically in two discrete zones. First-order aerobic biodegradation rates in laboratory columns using unsaturated site soil ranged from 5 to 28 days(-1) with a mean rate of 11 days(-1). The observed naphthalene mass flux at the source (3.3-22 microg cm(-2) d(-1)) was enhanced by aerobic biodegradation and was greater than the mean observed flux in the abiotic control column and the maximum theoretical mass flux by factors of 7 and 28, respectively.     

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.     

Oxidation of pharmaceuticals during ozonation of municipal wastewater effluents: a pilot study

To reduce the release of pharmaceuticals and endocrine disruptors into the aquatic environment or to remove them from wastewater intended for direct or indirect reuse, the application of advanced wastewater treatment may be required. In the present study, municipal wastewater effluents were treated with ozone (O3) in a pilot-scale plant consisting of two bubble columns. The investigated effluents, which varied in suspended solids concentrations, comprised an effluent of conventional activated sludge treatment (CAS), the same effluent dosed with 15 mg of TSS L(-1) of activated sludge (CAS + SS), and the effluent of a membrane bioreactor pilot plant (MBR). Selected classes of pharmaceuticals were spiked in the wastewater at realistic levels ranging from 0.5 to 5 microg L(-1). Samples taken at the inlet and the outlet of the pilot plant were analyzed with liquid chromatography (LC)-electrospray tandem mass spectrometry (MS). Macrolide and sulfonamide antibiotics, estrogens, and the acidic pharmaceuticals diclofenac, naproxen, and indomethacin were oxidized by more than 90-99% for O3 doses > or = 2 mg L(-1) in all effluents. X-ray contrast media and a few acidic pharmaceuticals were only partly oxidized, but no significant differences were observed among the three effluents. These results show that many pharmaceuticals present in wastewater can be efficiently oxidized with O3 and that suspended solids have only a minor influence on the oxidation efficiency of nonsorbing micropollutants.     

Occurrence of pharmaceuticals in river water and their elimination in a pilot-scale drinking water treatment plant

The occurrence of four beta blockers, one antiepileptic drug, one lipid regulator, four anti-inflammatories, and three fluoroquinolones was studied in a river receiving sewage effluents. All compounds but two of the fluoroquinolones were observed in the water above their limit of quantification concentrations. The highest concentrations (up to 107 ng L(-1)) of the compounds were measured during the winter months. The river water was passed to a pilot-scale drinking water treatment plant, and the elimination of the pharmaceuticals was followed during the treatment. The processes applied by the plant consisted of ferric salt coagulation, rapid sand filtration, ozonation, two-stage granular activated carbon filtration (GAC), and UV disinfection. Following the coagulation, sedimentation, and rapid sand filtration, the studied pharmaceuticals were found to be eliminated only by an average of 13%. An efficient elimination was found to take place during ozonation at an ozone dose of about 1 mg L(-1) (i.e., 0.2-0.4 mg of O3/ mg of TOC). Following this treatment, the concentrations of the pharmaceuticals dropped to below the quantification limits with the exception of ciprofloxacin. Atenolol, sotalol, and ciprofloxacin, the most hydrophilic of the studied pharmaceuticals, were not fully eliminated during the GAC filtrations. All in all, the treatment train was found to very effectively eliminate the pharmaceuticals from the rawwater. The only compound that was found to pass almost unaffected through all the treatment steps was ciprofloxacin.     

Effect of butylated hydroxytoluene (BHT) on the aerobic biodegradation of a model vegetable oil in aquatic media

Antioxidants added to vegetable oils to prevent lipid oxidation significantly affect their biodegradation in impacted aquatic environments. In this study, the effect of butylated-hydroxytoluene (BHT) on the biodegradation of glyceryl trilinoleate, a model vegetable oil highly susceptible to autoxidation, was determined. Biodegradation experiments were conducted in respirometric microcosms at an oil loading of 333 gal acre(-1) (0.31 L m(-2)) and BHT concentrations ranging from 0 to 800 mg kg(-1) (0, 50, 100, 200, 400, and 800 mg kg(-1)). Competition between polymerization and biodegradation of the oil was observed at all BHT concentrations and was significant in the microcosms not supplemented with the antioxidant. In all microcosms, intractable rigid polymers unavailable for bacterial degradation were formed. Infrared analysis evidenced the advanced stages of the oil autoxidation. After 19 weeks of incubation, only about 41% of the oil was mineralized in the microcosms with no BHT. However, mineralization exceeded 67% in the microcosms with added antioxidant and did not significantly increase with increasing BHT concentrations. Biodegradation rate constants were calculated by nonlinear regression and were not significantly different in the microcosms with added BHT (k = 0.001 h(-1)). Higher k values were measured in the microcosms lacking the antioxidant (k = 0.0023 h(-1)), most likely due to the increased oxygen consumption associated with the autoxidation process in this case. No toxicity was detected in all biotic microcosms at the end of the incubation period, while high toxicity (EC(50) = 4.78%) was measured in the abiotic blanks with no antioxidant and was attributed to the accumulation of autoxidation products.     

Photosensitized oxidation of emerging organic pollutants by tetrakis C₆₀ aminofullerene-derivatized silica under visible light irradiation

We recently reported that C(60) aminofullerenes immobilized on silica support (aminoC(60)/silica) efficiently produce singlet oxygen ((1)O(2)) and inactivate virus and bacteria under visible light irradiation. (1) We herein evaluate this new photocatalyst for oxidative degradation of 11 emerging organic contaminants, including pharmaceuticals such as acetaminophen, carbamazepine, cimetidine, propranolol, ranitidine, sulfisoxazole, and trimethoprim, and endocrine disruptors such as bisphenol A and pentachlorophenol. Tetrakis aminoC(60)/silica degraded pharmaceuticals under visible light irradiation faster than common semiconductor photocatalysts such as platinized WO(3) and carbon-doped TiO(2). Furthermore, aminoC(60)/silica exhibited high target-specificity without significant interference by natural organic matter. AminoC(60)/silica was more efficient than unsupported (water-suspended) C(60) aminofullerene. This was attributed to kinetically enhanced (1)O(2) production after immobilization, which reduces agglomeration of the photocatalyst, and to adsorption of pharmaceuticals onto the silica support, which increases exposure to (1)O(2) near photocatalytic sites. Removal efficiency increased with pH for contaminants with a phenolic moiety, such as bisphenol A and acetaminophen, because the electron-rich phenolates that form at alkaline pH are more vulnerable to singlet oxygenation.     

Assessment of groundwater pollution in Tokyo using PPCPs as sewage markers

While the occurrence of pharmaceuticals and personal care products (PPCPs) in groundwater has typically been reported in bank filtration sites, irrigated fields, septic tanks, and sewage disposal practices, fewer studies have been conducted in highly urbanized areas, where infiltration of treated or untreated sewage is not supposed to be a source of groundwater recharge. Furthermore, little is known about the occurrence of various kinds of PPCPs in relation to microbial indicators in groundwater from different types of aquifers. Thus, we examined the city-wide occurrence of selected PPCPs (diethyltoluamide, crotamiton, ethenzamide, propyphenazone, carbamazepine, and caffeine) and E. coli in 50 groundwaters from unconfined aquifers (<30 m in depth) and confined aquifers (up to 500 m in depth) in Tokyo, where unintended groundwater contamination could take place due to decrepit sewer networks. PPCPs were detected in unconfined aquifers and springs (23/34 samples, 68%), and in confined aquifers (7/16 samples, 44%). Compared with published results for sewage influents, concentrations of PPCPs, excluding caffeine, were generally 1-2 orders of magnitude lower, while in some samples concentrations were quite comparable. The high occurrence rate of PPCPs, even in confined aquifers, indicated that such aquifers are not always protected from pollution by sewage near the land surface. Among the PPCPs analyzed, carbamazepine and crotamiton were most frequently detected, which would appear to be owing to their high persistence, combined with the high concentration of crotamiton in sewage. Crotamiton was detected in all four E. coli-positive groundwaters, and thus may potentially serve as a precautionary indicator of E. coli contamination. Using carbamazepine as a sewage marker, we estimated that 0.8%-1.7% of the dry-weather flow of sewage was leaking out into the unconfined aquifers.     

印染行业各口径数据污染源源强核算分析

通过比对总量减排、环境影响评价、排污许可、环境统计中污染源源强的核算差异,对统一源强核算方法和推进各口径数据衔接提出建议,使排污许可证制度真正成为固定污染源环境管理的核心制度。     

Sorption kinetics and microbial biodegradation activity of hydrophobic chemicals in sewage sludge: model and measurements based on free concentrations

In the current study, a new method is introduced with which the rate-limiting factor of biodegradation processes of hydrophobic chemicals in organic and aqueous systems can be determined. The novelty of this approach lies in the combination of a free concentration-based kinetic model with measurements of both free and total concentrations in time. This model includes microbial biodegradation activity of the chemical in the aqueous phase and chemical sorption kinetics with respect to organic carbon and aqueous phases. The time dependency of free and total concentrations of 7-acetyl-1,1,3,4,4,6-hexamethyltetrahydronaphthalene and 7-acetyl-1,1,3,4,4,6-hexahydro-4,6,6,7,8,8-hexamethylcyclopenta(g)-2-benzopyrane in activated sludge was experimentally determined in vitro. Evaporation losses from the test system were also determined. Least-squares regression to optimize the model parameters resulted in a model that is in accordance with the experimental data. Additionally, the model shows that a comparison between the decrease of free and total chemical concentrations in time, in combination with an independent measurement of the organic carbon/water partition coefficient provides information aboutthe rate-limiting step of the degradation process. This information can be used by sewage treatment plant managers to decide whether the microbial biodegradation activity itself or the desorption from organic carbon to the aqueous phase should be improved.     

Regulatory FOCUS Surface Water Models Fail to Predict Insecticide Concentrations in the Field

The FOrum for the Co-ordination of pesticide fate models and their USe (FOCUS) exposure models are used to predict the frequency and magnitude of pesticide surface water concentrations within the European regulatory risk assessment. The predictions are based on realistic worst-case assumptions that result in predicted environmental concentrations (PEC). Here, we compared for the first time a larger data set of 122 measured field concentrations (MFC) of agricultural insecticides extracted from 22 field studies to respective PECs by using FOCUS steps 1-4. While FOCUS step 1 and 2 PECs generally overpredicted the MFCs, 23% of step 3 and 31% of step 4 standard PECs were exceeded by surface water MFCs, which questions the protectiveness of the FOCUS exposure assessment. Using realistic input parameters, step 3 simulations underpredicted MFCs in surface water and sediment by 43% and 78%, respectively, which indicate that a higher degree of realism even reduces the protectiveness of model results. The ratios between PEC and MFC in surface water were significantly lower for pyrethroids than for organophosphorus or organochlorine insecticides, which suggests that the FOCUS predictions are less protective for hydrophobic insecticides. In conclusion, the FOCUS modeling approach is not protective for insecticide concentrations in the field.