Determination of the solid-water distribution coefficient (Kd) for pharmaceuticals, estrogens and musk fragrances in digested sludge

This work determined the solid-water distribution coefficient (K(d)) and the organic carbon normalized distribution coefficient (K(oc)) of several pharmaceuticals (carbamazepine, ibuprofen, naproxen, diclofenac, iopromide, sulfamethoxazole and roxithromycin), three estrogens (estrone, 17beta-estradiol and 17alpha-ethinylestradiol) and two musk fragrances (HHCB and AHTN) in digested sludge. These sorption coefficients can be used to evaluate the fate of these substances during sludge treatment, thus avoiding the expensive and time-consuming analysis in the sludge phase. For determining the K(d) and K(oc) values of the target compounds in digested sludge, their concentrations were measured in the aqueous and solid phase of the effluent of an anaerobic digestion pilot plant run at several operational conditions. The results obtained were compared with the values modelled by using simple K(ow) approaches. The resulting log K(d) values ranged between 3.5 and 4.4 for the two musk fragrances (log K(oc) of 4.5-6.0), between 2.1 and 2.9 for estrogens (log K(oc) of 2.9-4.2) and between 0.8 and 1.9 for the remaining pharmaceuticals (log K(oc) of 1.8-3.5). These values are in the same range as those reported in the literature for primary and secondary sludge and no significant influence of the anaerobic digestion operational conditions was observed. For most compounds, the modelled K(oc) were close or within the lower range of the experimentally determined K(oc). Major deviations of the modelled K(oc) values were found for iopromide, sulfamethoxazole and roxithromycin, which were 1-3 orders of magnitude lower than the measured values.     

pH dependence of steroid hormone--organic matter interactions at environmental concentrations

The interaction of estradiol, estrone, progesterone and testosterone with environmentally relevant concentrations of Aldrich humic acid, alginic acid and tannic acid was studied using solid-phase microextraction (SPME). Since bulk organic matter and certain hormones such as estradiol and estrone contain dissociable functional groups, the effect of pH on sorption was investigated as this will influence their fate and bioavailability. For humic acid and tannic acid, sorption was strongest at acidic pH when the bulk organic matter was in a non-dissociated form and decreased when they became partially negatively charged. At acidic and neutral pH the strength of partitioning was influenced by hormone functional groups content, with the strongest sorption observed for progesterone and estrone. At alkaline pH conditions, when the bulk organics were dissociated, sorption decreased considerably (up to a factor of 14), although the non-dissociated hormones testosterone and progesterone indicated greater sorption to humic acid at pH 10 compared to the partially deprotonated estradiol and estrone. This study demonstrates that SPME can be used to assess organic matter sorption behaviour of a selected range of micropollutants and at environmentally relevant organic matter concentrations.     

Distributions of polycyclic aromatic hydrocarbons in surface waters, sediments and soils of Hangzhou City, China

Ten polycyclic aromatic hydrocarbons (PAHs) were simultaneously measured in 17 surface water samples and 11 sediments of four water bodies, and 3 soils near the water-body bank in Hangzhou, China in December 2002. It was observed that the sum of PAHs concentrations ranged from 0.989 to 9.663 microg/L in surface waters, from 132.7 to 7343 ng/g dry weight in sediments, and from 59.71 to 615.8 ng/g dry weight in soils. The composition pattern of PAHs by ring size in water, sediment and soil were surveyed. Three-ring PAHs were dominated in surface waters and soils, meanwhile sediments were mostly dominated by four-ring PAHs. Furthermore, PAHs apparent distribution coefficients (K(d)) and solid f(oc)-normalized K(d) (e.g. K(oc)= K(d) / f(oc)) were calculated. The relationship between logK(oc) and logK(ow) of PAHs for field data on sediments and predicted values were compared. The sources of PAHs in different water bodies were evaluated by comparison of K (oc) values in sediments of the river downstream with that in soils. Hangzhou section of the Great Canal was heavily polluted by PAHs released from industrial wastewater in the past and now PAHs in sediment may serve as sources of PAHs in surface water. PAHs in Qiantang River were contributed from soil runoff. Municipal road runoff was mostly contributed to West Lake PAHs.     

Assessment of olive cake as soil amendment for the controlled release of triazine herbicides

Organic matter-rich agricultural by-products are being produced in huge quantities and can be applied to soil as a disposal strategy. The application of two different rates (2 and 8% w/w) of olive cake to a Mediterranean calcareous soil resulted in an increased sorption of four triazine herbicides, which was higher for the more hydrophobic compounds (terbuthylazine and prometryn) and lower for the more polar ones (simazine and cyanazine). However, when the sorption coefficients were normalised to the total soil organic carbon (K(oc)), the results did not significantly differ between simazine and cyanazine which is an indication that the olive cake did not exert different sorption capacity for both compounds. On the contrary, K(oc) values for terbuthylazine and prometryn increased in the amended soils. Our results from experiments using mixtures of several pesticides suggest that competition for sorption sites resulted in a decrease of herbicide sorption. Desorption was hysteretical both for the amended and unamended soils, but the addition of olive cake at the highest dose diminished desorption of most of the herbicides. In conclusion, the addition of olive cake behaves as a promising method for reducing the risk of groundwater pollution by pesticides.     

Fate of natural estrogens in batch mixing experiments using municipal sewage and activated sludge

Since natural estrogens such as 17beta-estradiol (E2) and estrone (E1) are excreted daily by humans, E2 and E1, which are classified as inevitable endocrine-disrupting chemicals, are always present in sewage wastewater. For several years, the monitoring and removal of natural estrogens at sewage treatment plants have been examined by many investigators. However, little is known regarding the exact behavior of estrogens in actual sewage when in contact with activated sludge. In this study, the fate of E2 and E1 as a result of adsorption and decomposition in batch mixing experiments using municipal wastewater and activated sludge collected from an actual municipal sewage treatment plant was investigated. Estrogen concentrations were determined using an enzyme-linked immunosorbent assay (ELISA) kit. E2 and E1 in sewage were removed from the liquid phase in contact with activated sludge, and E2 and E1 adsorbed on the sludge were decomposed in 4h. Significant changes in the adsorption and decomposition of E2 and E1 on the sludge were not observed at low temperatures or when different sludge samples were used such as those acclimatized to low-loading and high-loading conditions. In contrast, the processes leading to the removal of estrogens, such as the adsorption and decomposition of estrogens in contact with activated sludge, were inactivated by sterilizing the sludge. Natural estrogens adsorb onto the activated sludge, and are therefore easy to be biodegraded. In a biological reaction process, therefore, the estrogens will be rapidly removed at the initial stage, when the sewage is satisfactorily mixed with the sludge.     

上海城市污泥中HBCD的浓度及土地施用累积水平

利用索氏提取、凝胶渗透色谱及高效液相色谱/质谱联用方法分析了上海市27个污水处理厂最终污泥中六溴环十二烷(HBCD)的浓度及分布情况。结果表明,污泥中HBCD的浓度范围为0.103～37.220 ng/g干重,平均值为4.700 ng/g干重,与世界其他地区相比,污染水平较低。在其中17个样品中,γ-HBCD是主要成分(44.7%～76.3%),在其他10个样品中,α-HBCD所占比例最高(49.6%～90.6%)。据估算,上海市通过污泥每年排放HBCD的量为1.5 kg。污泥如未经处理直接进行土地施用,土壤中HBCD的残留浓度会高出近似背景区一个数量级。     

An inventory of heavy metals inputs to agricultural soils in England and Wales

An inventory of heavy metal inputs (Zn, Cu, Ni, Pb, Cd, Cr, As and Hg) to agricultural soils in England and Wales in 2000 is presented, accounting for major sources including atmospheric deposition, sewage sludge, livestock manures, inorganic fertilisers and lime, agrochemicals, irrigation water, industrial by-product 'wastes' and composts. Across the whole agricultural land area, atmospheric deposition was the main source of most metals, ranging from 25 to 85% of total inputs. Livestock manures and sewage sludge were also important sources, responsible for an estimated 37-40 and 8-17% of total Zn and Cu inputs, respectively. However, at the individual field scale sewage sludge, livestock manures and industrial wastes could be the major source of many metals where these materials are applied. This work will assist in developing strategies for reducing heavy metal inputs to agricultural land and effectively targeting policies to protect soils from long-term heavy metal accumulation.     

Improved retention of imidacloprid (Confidor) in soils by adding vermicompost from spent grape marc

Batch sorption experiments of the insecticide imidacloprid by ten widely different Spanish soils were carried out. The sorption was studied for the active ingredient and its registered formulation Confidor. The temperature effect was studied at 15 degrees C and 25 degrees C. The addition of a vermicompost from spent grape marc (natural and ground), containing 344 g kg(-1) organic carbon, on the sorption of imidacloprid by two selected soils, a sandy loam and a silty clay loam, having organic carbon content of 3.6 g kg(-1) and 9.3 g kg(-1), respectively, was evaluated. Prior to the addition of this vermicompost, desorption isotherms with both selected soils, were also performed. The apparent hysteresis index (AHI) parameter was used to quantify sorption-desorption hysteresis. Sorption coefficients, K(d) and K(f), for the active ingredient and Confidor(R) in the different soils were similar. Sorption decreased with increasing temperature, this fact has special interest in greenhouse systems. A significant correlation (R(2)=0.965; P<0.01) between K(f) values and the organic carbon (OC) content was found, but some soils showed higher sorption coefficients than that expected from their OC values. The normalized sorption coefficients with the soil organic carbon content (K(oc)) were dispersed and low, implying that other characteristics of soils could contribute to the retention capacity as well. The spent grape marc vermicompost was an effective sorbent of this insecticide (K(f)=149). The sorption of imidacloprid increased significantly in soils amended with this vermicompost. The most pronounced effect was found in the sandy loam soil with low OC content, where the addition of 5% and 10% of vermicompost increased K(f) values by 8- and 15-fold, respectively. Soil desorption of imidacloprid was slower for the soil with the higher OC and clay content.     

Distribution of estrogens, 17beta-estradiol and estrone, in Canadian municipal wastewater treatment plants

The distribution of female hormones, 17beta-estradiol and estrone, was determined in effluents of 18 selected municipal treatment plants across Canada. Replicate 24-h composite samples were collected from the influent and final effluent of each treatment plant, and the removal efficiency compared to the operational characteristics of the plants. In conventional activated sludge and lagoon treatment systems, the mean concentrations of 17beta-estradiol and estrone in influent were 15.6 ng/l (range 2.4-26 ng/l) and 49 ng/l (19-78 ng/l). In final effluents, the mean concentrations of both 17beta-estradiol and estrone were reduced to 1.8 ng/l (0.2-14.7 ng/l) and 17 ng/l (1-96 ng/l), respectively. 17beta-estradiol was removed effectively, >75% and as high as 98%, in most of the conventional mechanical treatment systems with secondary treatment. The removal of estrone was much more complex with removal varying from 98% to situations where the concentrations in the effluent were elevated above that detected in the influent. The estrogenicity, measured using a transfected estrogen receptor in yeast (YES) assay, was also variable, ranging from high removal to elevations of estrogenicity in final effluent. Although the apparent removals were not statistically correlated with either hydraulic (HRT) or solid (SRT) retention times, plants or lagoons with high SRT were very effective at reducing the levels of hormones. Well-operated plants that achieved nitrification also tended to have higher removal of hormones than those that did not nitrify. Laboratory aerobic reactor experiments confirmed the rapid removal of 17beta-estradiol, estrone, and estrogenicity when exposed to sewage slurries.     

ASSESSMENT OF THE APPLICATION OF TREATED WASTEWATER AND SEWAGE SLUDGE IN PRODUCTIVE AGRICULTURE: A CASE STUDY FROM NORTHERN JORDAN

With the rapid expansion of development in Jordan, more water resources are being consumed and, consequently, incremental quantities of wastewater and sewage sludge are being generated from wastewater treatment plants. These quantities will end up in streams, open ponds or one of the other environmental media, which can cause adverse impacts on human health and the environment. In the mean while, a country like Jordan faces a remarkable shortage of fresh water resources and poor soil. The best way to mitigate the adverse impacts and compensate the water budget and enrich the poor soil is through the proper utilization and management of treated wastewater and sewage sludge in the agricultural sector. One of the main obstacles to this is public rejection of this solution, largely due to lack of information.
The purpose of this paper was to examine the acceptability to the Jordanian farmers of the utilization of reclaimed wastewater and treated sewage sludge in their irrigation activities. The scope of this study considered two potential areas at the northern part of the country, where a representative sample of local farmers were interviewed. The results were very encouraging and positive signs of acceptability were shown at all levels. These results were analyzed and documented and the recommendations are developed at the end of this paper.     

Impact of sewage sludge conditioning and dewatering on the fate of nonylphenol in sludge-amended soils

The fate of (14)C-labelled p353-nonylphenol (NP) in soils amended with differently treated sludges originating from the same precursor sludge was assessed. The effects of commonly applied conditioning and dewatering techniques were investigated. Nonylphenol was degraded considerably faster in soils amended with liquid sludge, while a significant portion of it remained intact and extractable by organic solvents when sludge had been centrifuged before soil amendment. Mineralization was reduced or even inhibited when freeze-thaw or lime conditioning was applied, respectively. Flocculation by an acrylamide-based cationic polymer led to the formation of a nitro-addition product of nonylphenol in soil, as well to decreased mineralization rates after prolonged incubation times. Possible mechanisms underlying the observations are suggested and discussed.     

Occurrence and behaviour of linear alkylbenzenesulphonates, nonylphenol, nonylphenol mono- and nonylphenol diethoxylates in sewage and sewage sludge treatment

The fluxes of linear alkylbenzenesulphonates (LAS), nonylphenol (NP), nonylphenol monoethoxylate (NP1EO) and nonylphenol diethoxylate (NP2EO) through sewage and sludge treatment of 29 Swiss sewage treatment plants were investigated. Reversed-phase high-performance liquid chromatography (HPLC) was used to determine LAS. Normal-phase HPLC was employed to measure NP, NP1EO and NP2EO which are metabolites of the nonionic surfactants of the nonylphenol polyethoxylate type (NPnEO). Quantitative determinations were performed of raw sewage, primary and secondary effluents and of sewage sludge. Under normal conditions of sewage and sludge treatment, LAS were efficiently removed from the raw wastewater (> 99% w/w) and were partly transferred to the sewage sludge (15–20% w/w). About 50% (molar base) of NPnEO in the sewage were transformed to NP and accumulated in the digested sludge. Large variations existed among different sewage treatment plants. It was estimated that 1.0 g m⁻² y⁻¹ of LAS and 0.3 g m⁻² y⁻¹ of NP are applied with sewage sludge to Swiss soils.     

Estimating sludge loadings to land based on trace metal sorption in soil: effect of dissolved organo-metallic complexes

This paper describes the results of research examining the effect of dissolved organo-metallic complexes of copper (Cu) and zinc (Zn) from sewage sludge leachate on sorption by a humic-gley soil A-horizon, and the influence of such complexes on resultant sludge loading estimates. Sorption was described with Linear, Freundlich or Langmuir equations, and compared between a sample of sludge leachate (containing 97.4% of Cu and 63.2% of Zn as dissolved organo-metallic complexes) and a reference solution (which mimicked the leachate, except for a lack of dissolved organic material). This comparison revealed that dissolved organo-metallic complexes significantly depressed Cu and Zn sorption in the study soil. The isotherm equations were then used to estimate sludge-derived Cu and Zn loadings to soil in order to result in an "allowable" output concentration from the soil solution to the surrounding environment. These loadings, together with soil bulk density and "availability" of sludge Cu and Zn, were incorporated in a preliminary model to estimate sludge application rates which are acceptable in terms of off-site movement of these metals through leaching losses. In the absence of dissolved organo-metallic complexes (sorption from the reference solution), levels of Cu and Zn sorption in the study soil indicated a sludge application rate of approximately 3500 kg/ha. However, when Cu and Zn sorption from the sludge leachate with dissolved organo-metallic complexes was considered, calculated loading rates were reduced to approximately 690 kg-sludge/ha. This suggests that for sludge loading estimates based on soil sorption characteristics to be relevant to environmental protection, the sorption depressing effect of dissolved organo-metallic complexes should be quantitatively considered.     

Behaviour and occurrence of estrogens in municipal sewage treatment plants--II. Aerobic batch experiments with activated sludge

Aerobic batch experiments containing a diluted slurry of activated sludge from a real sewage treatment plant (STP) near Frankfurt/Main were undertaken, in order to investigate the persistence of natural estrogens and contraceptives under aerobic conditions. The batch experiments showed that while in contact with activated sludge the natural estrogen 17 beta-estradiol was oxidized to estrone, which was further eliminated in the batch experiments in an approximate linear time dependence. Further degradation products of estrone were not observed. 16 alpha-hydroxyestrone was rapidly eliminated, again without detection of further degradation products. The contraceptive 17 alpha-ethinylestradiol was principally persistent under the selected aerobic conditions, whereas mestranol was rapidly eliminated and small portions of 17 alpha-ethinylestradiol were formed by demethylation. Additionally, two glucuronides of 17 beta-estradiol (17 beta-estradiol-17-glucuronide and 17 beta-estradiol-3-glucuronide) were cleaved in contact with the diluted activated sludge solution and thus 17 beta-estradiol was released. The glucuronidase activity of the activated sludge was further confirmed by the cleavage of 4-methylumbelliferyl-beta-D-glucuronide (MUF-beta-glucuronide) in a solution of a activated sludge slurry and Milli-Q-water (1:100, v/v). The turnover rate obtained was approximately steady state, with a turnover rate of 0.1 mumol/l for the released MUF. Hence, it is very likely that the glucuronic acid moiety of 17 beta-estradiol glucuronides and other estrogen glucuronides become cleaved in a real municipal STP, so that the concentrations of the free estrogens increase.     

Fate and removal of selected endocrine‐disrupting compounds in sewage using activated sludge treatment

The variation and fate of four endocrine‐disrupting compounds (EDCs) composed of 4‐n‐nonylphenol (4‐n‐NP), bisphenol A (BPA), 17β‐estradiol (E2) and 17α‐ethinylestradiol (EE2) were investigated along treatment units in a sewage treatment plant (STP), China with anaerobic, anoxic and aerobic activated sludge processes. The mean concentrations were 64.8 ng/L (E2), 115.3 ng/L (4‐n‐NP), 171.5 ng/L (EE2), and 920.7 ng/L (BPA) in the influents, and 22.8 ng/L (E2), 50.9 ng/L (4‐n‐NP), 49.9 ng/L (EE2), and 84.3 ng/L (BPA) in the effluents. The biological treatment was more effective in removing NP, BPA and E2 from the aqueous phase than the primary treatment, while the latter could effectively remove EE2. Their possible removal mechanisms during the biological treatment with activated sludge were further explored through spiked batch experiments under three oxygen‐supplying conditions (anaerobic, anoxic and aerobic). The batch experiments showed that 4‐n‐NP, E2 and BPA were removed from the aqueous phase through biodegradation. The combination of sludge sorption and biodegradation accounted for the removal of EE2. Anoxic activated sludge showed the most rapid degradation of 4‐n‐NP, while E2 could be removed most effectively by aerobic activated sludge, and sludge sorption had a remarkable effect on its removal within the initial 15 min of the experiments under three oxygen‐supplying conditions.     

Atrazine sorption on surface soils: time-dependent phase distribution and apparent desorption hysteresis

Non-equilibrium sorption-desorption behavior of atrazine was studied on two surface soils. Impact of sorption contact time was evaluated by interpreting temporal variations in Freundlich sorption isotherm parameters n(t) and K(F)(t) obtained from the phase distribution relationships. The extent of sorption linearity was very similar (n approximately 0.90) for the two soils at all sorption contact times. K(F)(t) increased with contact time and stabilized upon reaching apparent equilibrium. K(F) for woodland soil was significantly higher than that for agricultural soil. The Apparent Hysteresis Index (AHI) parameter was used to quantify sorption-desorption hysteresis arising from non-equilibrium sorption. AHI was a function of the sorption contact time and correlated well with K(F)(t). The woodland soil sorbed more herbicide due to its higher organic matter content. However, a larger fraction of the herbicide sorbed to this soil was released rapidly (within 24 h) following sorptive uptake. The differences in sorption-desorption behavior of atrazine in the two soils appear to be related to variations in the type and location of organic matter in the two soils. The parameters K(F)(t) and AHI(t) consistently demonstrated the effects that arise when batch systems are not brought to equilibrium during sorption studies.     

Laboratory tests on the impact of superabsorbent polymers on transformation and sorption of xenobiotics in soil taking 14C-imazalil as an example

Due to water scarcity, the agricultural production in arid areas is dependent on a sustainable irrigation management. In order to optimize irrigation systems, the application of superabsorbent polymers (SAP) as soil amendments, frequently studied within the last years, may be an appropriate measure to enhance the water holding capacity and the plant-available water in poor arable soils. These persistent polymers are also able to reduce heavy metal and salt stress to crops by accumulating those inorganic compounds. However, the impact of SAP on fate and behavior of organic xenobiotics in soil is unknown. Therefore, transformation and sorption of the model substance ¹⁴C-imazalil were monitored without and with SAP amendment in silty sand and sand soil under laboratory conditions.Within the 100-d incubation period, the transformation of ¹⁴C-imazalil was not substantially affected by the SAP amendment even though the microbial activity increased considerably. In the silty sand soil, extractable residues dropped from 90% to 45% without and from 96% to 46% with SAP amendment. Non-extractable residues continuously increased up to 49% and 35% while mineralization reached 6% and 5%, respectively. In the sand soil, characterized by its lower microbial activity and lower organic carbon content, extractable residues merely dropped from 99% to 81% and from 100% to 85% while non-extractable residues increased from 2% to 14% and 1% to 10%, respectively. Mineralization was lower than 2%. The increased microbial activity, usually promoting transformation processes of xenobiotics, was compensated by the enhanced sorption in the amended soils revealed by the increase of soil/water distribution coefficients (K_d) of 26 to 42 L kg^− 1 for the silty sand and 6 to 25 L kg^− 1 for the sand, respectively.     

Occurrence and removal of pharmaceuticals and endocrine disruptors in South Korean surface, drinking, and waste waters

Liquid chromatography/tandem mass spectrometry (LC-MS/MS) with electrospray ionization (ESI) and atmospheric pressure chemical ionization (APCI) was used to measure the concentrations of 14 pharmaceuticals, 6 hormones, 2 antibiotics, 3 personal care products (PCPs), and 1 flame retardant in surface waters and wastewater treatment plant effluents in South Korea. Tris (2-chloroethyl) phosphate (TCEP), iopromide, naproxen, carbamazepine, and caffeine were quite frequently observed (>80%) in both surface waters and effluents. The analytes of greatest concentration were iopromide, TCEP, sulfamethoxazole, and carbamazepine. However, the primary estrogen hormones, 17alpha-ethynylestradiol and 17beta-estradiol, were rarely detected, while estrone was detected in both surface water and wastewater effluent. The elimination of these chemicals during drinking water and wastewater treatment processes at full- and pilot-scale also was investigated. Conventional drinking water treatment methods were relatively inefficient for contaminant removal, while efficient removal (approximately equal to 99%) was achieved by granular activated carbon (GAC). In wastewater treatment processes, membrane bioreactors (MBR) showed limited target compound removal, but were effective at eliminating hormones and some pharmaceuticals (e.g., acetaminophen, ibuprofen, and caffeine). Membrane filtration processes using reverse osmosis (RO) and nanofiltration (NF) showed excellent removal (>95%) for all target analytes.     

Environmental exposure assessment of ethinyl estradiol (EE) from a combined hormonal vaginal contraceptive ring after disposal; leaching from landfills

In this study an environmental exposure assessment and experiments were carried out to identify the leaching potential of ethinyl estradiol (EE) present in a vaginal contraceptive (NuvaRing) when disposed of in landfills. Landfill material and a sandy soil were used to investigate the mobility of EE. Log K(oc) values determined in the range of 3 to 4 indicate that EE does not have a high mobility in landfills and soils. Column experiments were used to estimate that it takes approximately 40 years before EE leaches from a column of 1 m of landfill material or sandy soil. This column experiment, which was performed with an EE concentration based on worst-case assumptions, demonstrates that the emission of EE from landfills is negligible. Sandy soils below landfills also act as a strong sorbent of EE, thereby further reducing the potential for groundwater contamination.     

Field study using two immunoassays for the determination of estradiol and ethinylestradiol in the aquatic environment

The effluent of four sewage treatment plants (STP) and eight surface water samples from the river Rhine in Germany and two smaller rivers were monitored for the hormones estradiol (E2) and ethinylestradiol (EE2). The studied STPs are using different treatment processes. Two facilities include an activated sludge treatment, one is a constructed wetland, and one is just an aerated lagoon. For analysis of E2 and EE2 in the aquatic environment two immunoassays have been developed allowing a very cost-effective screening for both hormones in environmental samples. Detection limits could be established at 0.05 ng L(-1) for E2 and 0.01 ng L(-1) for EE2, taking a 50-fold enrichment into account. Median concentrations for E2 and EE2 in effluent samples were 12 and 1.8 ng L(-1), in surface water 4.0 and 0.7 ng L(-1), respectively. The highest estrogen concentrations were found in the effluent of the lagoon, equipped with very basic means of wastewater treatment.