Passive sampling: A cost-effective method for understanding antibiotic fate,behaviour and impact

The occurrence of antibiotics in the environment has raised much concern in recent years. Understanding their release, fate and behaviour in the environment is vital to assess potential risks. In this study, a novel passive water sampler – diffusion gradients in thin-films for organics (o-DGT) – was employed to assess the occurrence and removal of antibiotics in two waste water treatment plants (WWTPs) — one in China and the other in the United Kingdom (UK). Of the targeted compounds, 11 of 19 were detected in the Chinese WWTP (ND—200 ng/L) and 10 of 40 were found in the UK plant (ND—1380 ng/L). Florfenicol, lincomycin, ofloxacin and roxithromycin were most abundant in the Chinese WWTP (influent), while anhydrous erythromycin, ciprofloxacin, trimethoprim, ofloxacin and sulfapyridine were the most abundant in the UK influent samples. Estimated Chinese and UK consumption data are used to interpret the results. Neither of the WWTPs was very effective at removing antibiotics: ~ 40–50% (overall) was removed by the two plants, with the rest being discharged into the receiving rivers. This is the first study using o-DGT to assess the occurrence and removal of antibiotics in WWTPs. o-DGT is a useful, cost-effective tool to assess WWTP performance and can highlight the effectiveness of treatment steps, which can be applied to wastewater based epidemiology studies.     

Occurrence of sulfonamide residues along the Ebro River basin: removal in wastewater treatment plants and environmental impact assessment

Sulfonamides (SAs) have become one of the antibiotic families most frequently found in all kind of environmental waters. In the present work, the presence of 16 SAs and one of their acetylated metabolites in different water matrices of the Ebro River basin has been evaluated during two different sampling campaigns carried out in 2007 and 2008. Influent and effluent samples from seven wastewater treatment plants (WWTPs), together with a total of 28 river water samples were analyzed by on-line solid phase extraction-liquid chromathography-tandem mass spectrometry (on-line SPE-LC-MS/MS). Sulfamethoxazole and sulfapyridine were the SAs most frequently detected in WWTPs (96-100%), showing also the highest concentrations, ranging from 27.2 ng L(-1) to 596 ng L(-1) for sulfamethoxazole and from 3.7 ng L(-1) to 227 ng L(-1) for sulfapyridine. Sulfamethoxazole was also the SA most frequently detected in surface waters (85% of the samples) at concentrations between 11 ng L(-1) and 112 ng L(-1). In order to assess the effectiveness of the wastewater treatment in degrading SAs, removal efficiencies in the seven WWTPs were calculated for each individual SA (ranging from 4% to 100%) and correlated to the corresponding hydraulic retention times or residence times of the SAs in the plants. SAs half-lives were also estimated, ranging from to 2.5 hours (sulfadimethoxine) to 128 h (sulfamethazine). The contribution of the WWTPs to the presence of SAs depends on both the load of SAs discharging on the surface water from the WWTP effluent but also on the flow of the receiving waters in the discharge sites and the dilution exerted; WWTP4 exerts the highest pressure on the receiving water course. Finally, the potential environmental risk posed by SAs was evaluated calculating the hazard quotients (HQ) to different non-target organisms in effluent and river water. The degree of susceptibility resulted in algae>daphnia>fish. Sulfamethoxazole was the only SA posing a risk to algae in effluent water, with an HQ>7.     

Changes in concentrations of hydrophilic organic contaminants and of endocrine-disrupting potential downstream of small communities located adjacent to headwaters

Endocrine-disruptive potential and concentrations of polar organic contaminants were measured in seven headwaters flowing through relatively unpolluted areas of the Czech Republic. Towns with Wastewater Treatment Plant (WWTP) discharges were the first known sources of anthropogenic pollution in the areas. River water was sampled several kilometers upstream (US) and several tens of meters downstream (DS) of the WWTP discharges, by use of Pesticide and Pharmaceutical Polar Organic Integrative Samplers (POCIS-Pest, POCIS-Pharm). Extracts of passive samplers were tested by use of a battery of in vitro bioassays to determine overall non-specific cytotoxicity, endocrine-disruptive (ED) potential and dioxin-like toxicity. The extracts were also used for quantification of polar organics. There was little toxicity to cells caused by most extracts of POCIS. Estrogenicity was detected in all types of samples even though US locations are considered to be background. At US locations, concentrations of estrogen equivalents (EEq) ranged from less than the detection limits (LOD) to 0.5 ng EEq/POCIS. Downstream concentrations of EEqs ranged from less than LOD to 4.8 ng EEq/POCIS. Concentrations of EEq in POCIS extracts from all DS locations were 1 to 14 times greater than those at US locations. Concentrations of EEq measured in extracts of POCIS-Pest and POCIS-Pharm were in a good agreement. Neither antiestrogenic nor anti/androgenic activities were detected. Concentrations of 2,3,7,8-TCDD equivalents (TEq_bio) were detected in both types of POCIS at concentrations ranging from less than the LOD to 0.39 ng TEq_bio/POCIS. Nearly all extracts of POCIS-Pharm contained greater concentrations of TEq_bio activity than extracts of POCIS-Pest. Concentrations of pesticides and pharmaceuticals in extracts of POCIS were generally small at all sampling sites, but levels of some pharmaceuticals were significantly greater in both types of POCIS from DS locations. Chemical analyses along with the results of bioassays documented impacts of small towns with WWTPs on headwaters.     

Assessment of environmental estrogens and the intersex/sex reversal capacity for chinook salmon (Oncorhynchus tshawytscha) in primary and final municipal wastewater effluents

A trickling filter/solid contact (TF/SC) biological secondary treatment plant with chlorine disinfection serving a suburban population of 740,000 was assessed for environmental estrogens. Weekly grab samples were taken at established sampling points and analyzed for various pertinent environmental estrogens including industrial chemicals, and natural and synthetic steroidal estrogens. Additionally, human estrogen receptor (hER) activity and capacity to elicit intersex/sex reversal for the wastewater was monitored using a recombinant yeast assay and whole fish exposures, respectively. hER activity levels varied from 76 to 106 ng/L E2 equivalents in the primary effluent, and were reduced by 25% by biological treatment. For the primary and final effluent no evidence of sex reversal or intersex was apparent in any of the treatment groups (1%, 3%, 10%, or 100%) based on genetic sex determinations and histological examination of the gonads in alevin from 28 d exposed chinook salmon (Oncorhynchus tshawytscha) eggs.     

Triclosan in wastewaters and biosolids from Australian wastewater treatment plants

Triclosan (TCS) is an antimicrobial agent widely used in many personal care products. This study investigated the occurrence of TCS in effluents, biosolids and surface waters, and its fate in wastewater treatment plants (WWTPs). The aqueous concentrations of TCS in nineteen effluents from Australian WWTPs ranged from 23 ng/L to 434 ng/L with a median concentration of 108 ng/L, while its concentrations in nineteen biosolids ranged from 0.09 mg/kg to 16.79 mg/kg on dry weight basis with a median concentration of 2.32 mg/kg. The removal rates for TCS in five selected WWTPs were found to range between 72% and 93%. Biological degradation was believed to be the predominant removal mechanism for TCS in the WWTPs. However, adsorption onto sludge also played a significant role in the removal of TCS in the WWTPs. TCS at concentrations up to 75 ng/L was detected in surface waters (outfall, upstream, and downstream) from five rivers receiving effluent discharge from WWTPs. Preliminary risk assessment based on the worst-case scenario showed that the TCS concentrations in surface waters might lead to risks to aquatic organisms such as algae. Based on the TCS levels in the biosolids, application of biosolids on agricultural land may also cause adverse effects in the soil environment.     

Associations between grab sample and integrated radon measurements in dwellings in Maine and Texas

Radon concentrations were measured in several locations in each of approximately 100 dwellings in central Maine and in Houston, TX. Integrated samples were taken during the heating (or cooling) seasons with commercially available passive alpha track devices, while grab samples were taken at the time of integrated sampler deployment. It was found that both indoor and outdoor measurements in both areas were distributed log normally, and that the geometric mean of indoor measurements in Maine was three times higher than that of corresponding measurements in the Houston area. It was also noted that the mean of the indoor grab sample measurements was not significantly different from the mean of the indoor integrated measurements, and that the degree of correlation between the grab samples and a given indoor integrated sample was nearly as good as between integrated samples taken at different living area locations.     

Occurrence and risk assessment of pharmaceutically active compounds in wastewater treatment plants. A case study: Seville city (Spain)

The occurrence of four anti-inflammatory drugs (diclofenac, ibuprofen, ketoprofen and naproxen), an antiepileptic drug (carbamazepine) and a nervous stimulant (caffeine) in influent and effluent samples from four wastewater treatment plants (WWTPs) in Seville was evaluated. Removal rates in the WWTPs and risk assessment of the pharmaceutically active compounds have been studied. Analytical determination was carried out by high performance liquid chromatography (HPLC) with diode array (DAD) and fluorescence (Fl) detectors after sample clean up and concentration by solid phase extraction. All pharmaceutically active compounds, except diclofenac, were detected not only in wastewater influents but also in wastewater effluents. Mean concentrations of caffeine, carbamazepine, ketoprofen and naproxen ranged between 0.28-11.44 microg l(-1) and 0.21-2.62 microg l(-1) in influent and effluent wastewater, respectively. Ibuprofen was present in the highest concentrations in the range 12.13-373.11 microg l(-1) and 0.78-48.24 microg l(-1) in influent and effluent wastewater, respectively. Removal rates of the pharmaceuticals ranged between 6 and 98%. Risk quotients, expressed as ratios between the measured environmental concentration (MEC) and the predicted no effect concentrations (PNEC) were higher than 1 for ibuprofen and naproxen in influent wastewater and for ibuprofen in effluent wastewater.     

Measurement of flame retardants and triclosan in municipal sewage sludge and biosolids

As polybrominated diphenyl ethers (PBDEs) face increasing restrictions worldwide, several alternate flame retardants are expected to see increased use as replacement compounds in consumer products. Chemical analysis of biosolids collected from wastewater treatment plants (WWTPs) can help determine whether these flame retardants are migrating from the indoor environment to the outdoor environment, where little is known about their ultimate fate and effects. The objective of this study was to measure concentrations of a suite of flame retardants, and the antimicrobial compound triclosan, in opportunistic samples of municipal biosolids and the domestic sludge Standard Reference Material (SRM) 2781. Grab samples of biosolids were collected from two WWTPs in North Carolina and two in California. Biosolids samples were also obtained during three subsequent collection events at one of the North Carolina WWTPs to evaluate fluctuations in contaminant levels within a given facility over a period of three years. The biosolids and SRM 2781 were analyzed for PBDEs, hexabromobenzene (HBB), 1,2-bis(2,4,6-tribromophenoxy)ethane (BTBPE), 2-ethylhexyl 2,3,4,5-tetrabromobenzoate (TBB), di(2-ethylhexyl)-2,3,4,5-tetrabromophthalate (TBPH), the chlorinated flame retardant Dechlorane Plus (syn- and anti-isomers), and the antimicrobial agent 5-chloro-2-(2,4-dichlorophenoxy)phenol (triclosan). PBDEs were detected in every sample analyzed, and ΣPBDE concentrations ranged from 1750 to 6358 ng/g dry weight. Additionally, the PBDE replacement chemicals TBB and TBPH were detected at concentrations ranging from 120 to 3749 ng/g dry weight and from 206 to 1631 ng/g dry weight, respectively. Triclosan concentrations ranged from 490 to 13,866 ng/g dry weight. The detection of these contaminants of emerging concern in biosolids suggests that these chemicals have the potential to migrate out of consumer products and enter the outdoor environment.     

Perfluoroalkyl compounds in Danish wastewater treatment plants and aquatic environments

This study reports the results of a screening survey of perfluoroalkyl compounds (PFCs) in the Danish environment. The study included point sources (municipal and industrial wastewater treatment plants and landfill sites) and the marine and freshwater environments. Effluent and influent water and sewage sludge were analysed for point sources. Sediment, blue mussels (Mytilus edulis) and liver from plaice (Pleuronectes platessa), flounder (Platichthys flesus) and eel (Anguilla anguilla) were analysed for the freshwater and marine environments. The results obtained show a diffuse PFCs contamination of the Danish environment with concentrations similar to those measured in other countries with the absence of primary contamination sources such as fluorochemical production. PFOS and PFOA were generally the most dominating PFCs measured in both point sources and the aquatic environments. PFCs were found in both inflow and outflow water and sewage sludge from municipal and industrial wastewater treatment plants (WWTPs), indicating that WWTPs can be significant sources to PFCs in the environment. This is also reflected in the locally elevated PFCs concentrations found in fish like eels from shallow freshwater and marine areas. However, the highest PFCs concentrations found in fish in this study was in plaice from the Skagerrak (156 ng/g wet weight PFOS), but it is unknown if this can be related to significant sources in the North Sea region or to differences between species. The concentrations of PFCs were below the detection limit in all analysed freshwater and marine samples of sediment and mussels. Despite the relatively low PFCs concentrations measured in marine fish, the high bioaccumulation potential of PFCs, particularly PFOS, may lead to high concentrations of PFCs in marine mammals as shown by previous investigations.     

Analysis of phytoestrogens,progestogens and estrogens in environmental waters from Rio de Janeiro (Brazil)

The environment is currently exposed to a large variety of man-made chemicals (e.g. for industrial, medicinal use) which have potential adverse effects to its ecological status. In addition, the densely populated areas represent local high emissions of those chemicals leading to more aggravating consequences. Estrogenic compounds that end-up in environmental water directly affect living organisms by interfering with their endocrine metabolism. The assessment of their presence in the environment requires sensitive and selective analytical methods. Nineteen estrogenic compounds belonging to different classes (5 free estrogens, 6 conjugated estrogens, 3 progestogens and 5 phytoestrogens) have been studied. The analytical methodology developed is based on solid phase extraction followed by liquid chromatography tandem mass spectrometry and has been applied to study the occurrence of the above mentioned analytes in environmental waters from the state of Rio de Janeiro (Brazil). Due to insufficient infra-structure in this region, waste waters are released onto the environment without or with incomplete previous treatment. The results show that high levels of the phytoestrogens daidzein, coumestrol and genistein of up to 366 ng/L and progesterone of up to 47 ng/L could be found in river water. Estrogens and their conjugated derivatives were detected in the lower ng/L range up to 7 ng/L. The main estrogens estrone, estradiol and the synthetic ethinyl estradiol could not be detected. The developed method showed overall good performance with recoveries above 80% (with one exception), limits of detection ≤ 2 ng/L, good linearity and reproducibility.     

Measurement of estrogenic activity in sediments from Haihe and Dagu River, China

Sediments from two rivers in China, the Haihe and Dagu Rivers, were examined for estrogenic activity using an estrogen receptor (ER)-mediated in vitro bioassay system. ER-active compounds were isolated from sediments by Soxhlet extraction, and the crude extracts were fractionated using a florisil column into three fractions. The estrogenic activity of each extract was detected by measuring luciferase activity in the human breast cancer cell line MCF-7 transfected with a luciferase receptor gene. Significant estrogenic activity was observed in each total extract. The 17beta-estradiol equivalents (E2-EQs) ranged from 8.24 to 95.28 ng E2 g(-1) dw. As a result, the relative estrogenic potencies of three fractions in this study descended in the order of Fraction 3>Fraction 2>Fraction 1. The results of the bioassay analysis indicated the heavy pollution status of these sites with estrogenic contaminants. In this study, five selected chemicals, the natural estrogens 17beta-estradiol (E2) and estrone (E1), and the xeno-estrogens 4-octylphenol (OP), 4-nonylphenol (NP), and Bisphenol A (BPA) were also analyzed using the in vitro bioassay. The estrogenic activity of these chemicals were E2>E1>NP>OP>BPA.     

Development of extraction method of pharmaceuticals and their occurrences found in Japanese wastewater treatment plants

In this study, occurrence of 66 PPCPs (pharmaceuticals and personal care products) in liquid and solid phases of sewage sludge was elucidated. The extraction methods for the PPCPs from sludge were newly developed employing Pressurized Liquid Extraction (PLE) and Ultrasonic Solvent Extraction (USE). As an appropriate method, PLE using water (pH2), PLE using methanol (pH4), and USE using mixture of methanol and water (1/9,v/v, pH11) was found most effective because total recovery of most of the PPCPs indicated 40 to 130%. The developed extraction method with previously developed method for liquid phase analysis was applied to field survey at wastewater treatment plants (WWTPs) in Japan. 56 compounds were detected from the primary sludge and 61 compounds were detected from the excess sludge. The concentration was ranged between several ng/g and several μg/g. Solid-water distribution coefficient (Log K_d) ranged between 0.9 L/kg (Caffeine) and 3.7 L/kg (Levofloxacin) for primary sludge and between 1.4 L/kg (Sulpirid) and 4.3 L/kg (Mefenamic acid) for excess sludge.     

Environmental estrogens in an urban aquatic ecosystem: I. Spatial and temporal occurrence of estrogenic activity in effluent-dominated systems

The present study investigated occurrence of environmental estrogens (EEs) in waterways managed by the Metropolitan Water Reclamation District of Greater Chicago (‘District’) — one of the largest and most complex water districts in the United States. The objectives of the study were: (i) to document spatial and temporal occurrence of EEs in the Chicago Area Waterways (CAWs); (ii) to determine whether water reclamation plant (WRP) effluents contribute to estrogenic pollution of the receiving streams; (iii) to determine whether the mandated water quality monitoring data could be used to predict estrogenic pollution in the receiving streams; and (iv) to determine whether snow melt, storm runoff and combined sewer overflows may also be contributors of estrogenic activity to these systems. The estrogenic potency of the waterways was assessed using a cell-based reporter gene assay. The water quality data was readily available as part of the District's regular monitoring program. Our findings indicate that EEs are commonly found in the CAWs, and that WRP effluents are one of, but not the only important contributor to estrogenic activity. Mean estrogenic activities in CAWs (11 ng estradiol equivalents (EEQs/L)) are well within the values reported for other urban areas and WRP effluents. The estrogenic activity exhibited significant seasonal variation with highest values noted during the spring and summer months. When comparing the mean estrogenic activity of general use waters, secondary contact waters and WRP effluents, we found that general use waters had significantly lower estrogenic activity (ca 5 ng EEQ/L) than the other two matrices (ca 15 and 17 ng EEQ/L respectively). Our analyses indicate that estrogenic activity of the waterways was not reliably associated with mandated water quality parameters, and that such measurements may not be useful for predicting estrogenic activity, especially so in the complex urban systems. One of the prominent findings of this study is that EEs do not follow predictable spatial patterns — many of the upstream sites in the heavily urbanized areas had levels of estrogenic activity comparable to those found in the effluents and downstream locations. Our data suggest that surface runoff and snow melt are estrogenic (0–9 ng EEQ/L), and given that their estrogenic activities are similar to those of their receiving waterways (0–7 ng EEQ/L), we conclude that these non-WRP sources are important contributors to estrogenic activity of the CAWs.     

Phytoestrogens and mycoestrogens in surface waters — Their sources,occurrence, and potential contribution to estrogenic activity

This review discusses the potential contribution of phytoestrogens and mycoestrogens to in vitro estrogenic activities occurring in surface waters and in vivo estrogenic effects in fish. Main types, sources, and pathways of entry into aquatic environment of these detected compounds were summarized. Reviewed concentrations of phyto/mycoestrogens in surface waters were mostly undetectable or in low ng/L ranges, but exceeded tens of μg/L for the flavonoids biochanin A, daidzein and genistein at some sites. While a few phytosterols were reported to occur at relatively high concentrations in surface waters, information about their potencies in in vitro systems is very limited, and contradictory in some cases. The relative estrogenic activities of compounds (compared to standard estrogen 17β-estradiol) by various in vitro assays were included, and found to differ by orders of magnitude. These potencies were used to estimate total potential estrogenic activities based on chemical analyses of phyto/mycoestrogens. In vivo effective concentrations of waterborne phyto/mycoestrogens were available only for biochanin A, daidzein, formononetin, genistein, equol, sitosterol, and zearalenone. The lowest observable effect concentrations in vivo were reported for the mycoestrogen zearalenone. This compound and especially its metabolites also elicited the highest in vitro estrogenic potencies. Despite the limited information available, the review documents low contribution of phyto/mycoestrogens to estrogenic activity in vast majority of surface waters, but significant contribution to in vitro responses and potentially also to in vivo effects in areas with high concentrations.     

Natural and synthetic endocrine disrupting compounds (EDCs) in water, sediment and biota of a coastal lagoon

We report a survey on the occurrence and distribution of natural (17beta-estradiol, E2; estrone, E1) and synthetic (nonylphenol, NP; nonylphenol monoethoxylate carboxylate, NP1EC; bisphenol-A, BPA; benzophenone, BP; mestranol, MES; 17alpha-ethinylestradiol, EE2; diethylstilbestrol, DES) endocrine disrupting compounds (EDCs) in water, sediment and biota (Mediterranean mussel, Mytilus galloprovincialis) in the Venice lagoon, a highly urbanized coastal water ecosystem that receives both industrial and municipal wastewater effluents. The survey was preceded by the development of tailor made extraction and clean-up procedures for the simultaneous HPLC-ESI-MS determination of all examined EDCs in sediment and biota samples. Satisfactory extraction performances and method detection limits (MDLs) were obtained for almost all EDCs. Most of the selected compounds were found in water and sediment (concentration range: 2.8-211 ng/L, and 3.1-289 microg/kg, d.w., respectively), while only 17alpha-ethinylestradiol and nonylphenol were recorded in biota samples (conc. range: 7.2-240 ng/g, d.w.). 17beta-estradiol and ethinylestradiol contributed mostly to the water estradiol equivalent concentration (EEQ) (1.1-191 ng/L, average: 25 ng/L), while synthetic EDCs (17alpha-ethinylestradiol, diethylstilbestrol) were mainly responsible of the sediment EEQ (1.1-191 microg/kg, average: 71 microg/kg, d.w.). Whenever diethylstilbestrol was not recorded in the sediment, water EEQs were similar to sediment EEQs. A remarkable increase of nonylphenol was observed in sediments over the last decade.     

Emission of artificial sweeteners,select pharmaceuticals,and personal care products through sewage sludge from wastewater treatment plants in Korea

Concern over the occurrence of artificial sweeteners (ASWs) as well as pharmaceuticals and personal care products (PPCPs) in the environment is growing, due to their high use and potential adverse effects on non-target organisms. The data for this study are drawn from a nationwide survey of ASWs in sewage sludge from 40 representative wastewater treatment plants (WWTPs) that receive domestic (WWTP_D), industrial (WWTP_I), or mixed (domestic plus industrial; WWTP_M) wastewaters in Korea. Five ASWs (concentrations ranged from 7.08 to 5220 ng/g dry weight [dw]) and ten PPCPs (4.95–6930 ng/g dw) were determined in sludge. Aspartame (concentrations ranged from 28.4 to 5220 ng/g dw) was determined for the first time in sewage sludge. The median concentrations of ASWs and PPCPs in sludge from domestic WWTPs were 0.8–2.5 and 1.0–3.4 times, respectively, the concentrations found in WWTPs that receive combined domestic and industrial wastewaters. Among the five ASWs analyzed, the median environmental emission rates of aspartame through domestic WWTPs (both sludge and effluent discharges combined) were calculated to be 417 μg/capita/day, followed by sucralose (117 μg/capita/day), acesulfame (90 μg/capita/day), and saccharin (66 μg/capita/day). The per-capita emission rates of select PPCPs, such as antimicrobials (triclocarban: 158 μg/capita/day) and analgesics (acetaminophen: 59 μg/capita/day), were an order of magnitude higher than those calculated for antimycotic (miconazole) and anthelmintic (thiabendazole) drugs analyzed in this study. Multiple linear regression analysis of measured concentrations of ASWs and PPCPs in sludge revealed that several WWTP parameters, such as treatment capacity, population-served, sludge production rate, and hydraulic retention time could influence the concentrations found in sludge.     

Estrogenic activity in extracts and exudates of cyanobacteria and green algae

Here is presented some of the first information on interactions of compounds produced by cyanobacteria and green algae with estrogen receptor signaling. Estrogenic potency of aqueous extracts and exudates (culture spent media with extracellular products) of seven species of cyanobacteria (10 different laboratory strains) and two algal species were assessed by use of in vitro trans-activation assays. Compounds produced by cyanobacteria and algae, and in particular those excreted from the cells, were estrogenic. Most exudates were estrogenic with potencies expressed at 50% of the maximum response under control of the estrogen receptor ranging from 0.2 to 7.2 ng 17β-estradiol (E₂) equivalents (EEQ)/L. The greatest estrogenic potency was observed for exudates of Microcystis aerigunosa, a common species that forms water blooms. Aqueous extracts of both green algae, but only one species of cyanobacteria (Aphanizomenon gracile) elicited significant estrogenicity with EEQ ranging from 15 to 280 ng 17β-estradiol (E₂)/g dry weight. Scenedesmus quadricauda exudates and extracts of Aphanizomenon flos-aquae were antagonistic to the ER when coexposed to E₂. The EEQ potency was not correlated with concentrations of cyanotoxins, such as microcystin and cylindrospermopsin, which suggests that the EEQ was comprised of other compounds. The study demonstrates some differences between the estrogenic potency of aqueous extracts prepared from the same species, but of different origin, while the effects of exudates were comparable within species. The observed estrogenic potencies are important namely in relation to the possible mass expansion of cyanobacteria and release of the active compounds into surrounding water.     

Fate of Irgarol 1051, diuron and their main metabolites in two UK marine systems after restrictions in antifouling paints

Two major antifouling biocides used worldwide, Irgarol 1051 and diuron, and their degradation products in Shoreham Harbour and Brighton Marina, UK were studied during 2003-2004. The highest concentrations of Irgarol 1051 were 136 and 102 ng L(-1) in water and 40 and 49 ng g(-1) dry weight in sediments for Shoreham Harbour and Brighton Marina, respectively. As the degradation product of Irgarol 1051, M1 was also widespread, with the highest concentration of 59 ng L(-1) in water and 23 ng g(-1) in sediments in Shoreham Harbour, and 37 ng L(-1) in water and 5.6 ng g(-1) in sediments in Brighton Marina. The target compounds showed enhanced concentrations during the boating season (May-July), when boats were being re-painted (January-February), and where the density of pleasure crafts was high. Overall, the concentration of Irgarol 1051 decreased significantly from late 2000 to early 2004, indicating the effectiveness of controlling its concentrations in the marine environment following restricted use. Diuron was only detected in 14% of water samples, and mostly absent from sediment samples.     

Occurrence,removal and bioaccumulation of steroid estrogens in Dianchi Lake catchment,China

The occurrence, removal and bioaccumulation of steroid estrogens such as the natural estrone (E1), 17β-estradiol (E2) and estriol (E3), as well as the synthetic 17α-ethynylestradiol (EE2) were investigated in Dianchi Lake catchment, China. The results show that traditional secondary treatment processes in eight sewage treatment plants (STPs) of Kunming were not efficient enough to completely remove steroid estrogens, but ultraviolet (UV) photodegradation in advanced treatment displayed more effectively for the removal of the residual compounds. The amount of total steroid estrogens (∑ SEs) discharged to Dianchi Lake catchment by the eight STPs was 35.8 g/day, in which STP-3 was the dominant source, accounting for 50.8%. Because of the pollution input from treated and untreated sewages, estrogens were widely detected in surface water and sediment samples collected from 21 inflow rivers of Dianchi Lake, 10 National Surface Water Quality Monitoring Sites of the lake itself and its unique outflow river, with the mean concentration of ∑ SEs in the range of 5.3–798.2 ng/L (water) and 3.7–202.4 ng/g (dry weight, sediment), 1.5–39.2 ng/L (water) and 2.7–20.9 ng/g (sediment), and 4.2 ng/L (water) and 6.6 ng/g (sediment), respectively. Due to the continuous input of estrogens to Dianchi Lake from STPs and inflow rivers, present estrogen levels in various tissues of wild fish species sampled from the lake (2013) were higher than the values detected in the previous years (2009 and 2010). The bioaccumulation of steroid estrogens in wild fish species from different sampling sites was in the order of STP-5 > Dianchi Lake (2013) > Dianchi Lake (2010) ≈ Dianchi Lake (2009) ≫ field control > laboratory control, which is mainly affected by exposure concentrations. By employing risk quotient (RQ), it is found that eco-toxicological risk of steroid estrogens in Dianchi Lake catchment was in a sequence of 22 rivers > effluents of eight STPs > Dianchi Lake (2013) > Dianchi Lake (2010), and high RQs were found in EE2, which should be controlled preferentially in this catchment.     

PAH mass concentrations measured in PM10 particle fraction

This paper presents daily, monthly and yearly variations of PAH mass concentrations measured in PM(10) particle fraction, collected at one measuring site in Zagreb air between 2001 and 2004, and seasonal differences in PAH mass concentrations in PM(10) samples collected from 21 March 2003 to 20 March 2004. Twenty-four hour samples were taken in the northern residential part of Zagreb using a low-volume (50 m(3)) sampler and glass or quartz filters. The analysis was performed using a high-performance liquid chromatograph (HPLC) and fluorescence detector with changeable excitation and emission wavelength. The annual average mass concentrations over the four-year measuring period for BaP ranged from 1.17 ng/m(3) in 2004 to 1.87 ng/m(3) in 2003 and were below the limit value (2 ng/m(3)) set by the Ordinance on Recommended and Limit Air Quality Values in Croatia. The highest concentrations of all PAHs measured in PM(10) samples collected from 21 March 2003 to 20 March 2004 were found in the winter and the lowest in the summer. Winter average of BaP was 2.94 ng/m(3) and summer average 0.12 ng/m(3). Autumn average was 2.76 ng/m(3) and was very similar to winter concentrations. Spring average of 0.58 ng/m(3) was higher than the summer average (0.12 ng/m(3)). Mass concentrations of all measured PAHs were much higher in the autumn than in the spring. Although annual averages for BaP did not exceed the limit value, autumn and winter BaP mass concentrations did, which calls for measures for reducing PAH emissions in the autumn and winter.