Occurrence, fate and removal of synthetic oral contraceptives (SOCs) in the natural environment: a review

Synthetic oral contraceptives (SOCs) are a group of compounds with progestagenic and/or androgenic activities, with some also possessing estrogenic activities. Recent research has documented that some of these emerging contaminants have adverse effects on aquatic organisms at very low concentrations. To facilitate the evaluation of their latent risks, published works on their occurrence and fate in the environment are reviewed. Androgenic/progestagenic relative potencies or relative binding affinity of these SOCs as well as their physicochemical properties and toxicity are summarized. Appropriate analytical methods are outlined for various environmental sample types, including methods of sample preparation and limit of detection/quantification (LOD/LOQ). Finally results on their occurrence and fate in wastewater treatment plants (WWTPs) and other environments are critically examined.     

Occurrence of synthetic musks in Korean sewage sludges

Six polycyclic musks (PCMs) and five nitro musks (NMs) were analyzed in dewatered sludge samples from 13 municipal, 4 livestock and 1 pharmaceutical wastewater treatment plants (WWTPs) in South Korea. 1,3,4,6,7,8-Hexahydro-4,6,6,7,8,8-hexamethylcyclopenta-(g)-2-benzopyran (HHCB; Galaxolide^®, Abbalide^®), and 7-acetyl-1,1,3,4,4,6-hexamethyl-1,2,3,4-tetrahydronaphthalene (AHTN; Tonalide^®, Fixolide^®) were the two predominant PCMs in the sludge samples, at concentrations ranging from 0.52 to 82.0 mg/kg dry weight (dw) and 0.12 to 28.8 mg/kg (dw), respectively, suggesting the extensive use of these two PCMs in South Korea. Hierarchical cluster analysis (HCA) revealed the different usage patterns of PCMs between livestock cultivating farm and household. The levels of HHCB and AHTN in the effluent discharged from the WWTPs were lower than the threshold effect levels derived for fish, suggesting low potential risks to aquatic organisms. Nevertheless, the calculated discharge of synthetic musks (SMs) from sludge in each target WWTP ranged from 36 to 10,961 g/d. These results indicate the necessity of conducting monitoring studies in marine ecosystems due to ocean disposal of sludge, particularly focused on the two prevailing PCMs.     

Occurrence and fate of the antidiabetic drug metformin and its metabolite guanylurea in the environment and during drinking water treatment

Metformin, an antidiabetic drug with one of the highest consumption rates of all pharmaceuticals worldwide, is biologically degraded to guanylurea in wastewater treatment plants. Due to high metformin influent concentrations of up to 100 μg/L and its high but incomplete degradation both compounds are released in considerable amounts of up to several tens of μg/L into recipient rivers. This is the first systematic study on their environmental fate and the effectiveness of treatment techniques applied in waterworks to remove metformin and guanylurea from surface water influenced raw waters. The concentrations in surface waters depend strongly on the respective wastewater burden of rivers and creeks and are typically in the range of about 1 μg/L for metformin and several μg/L for guanylurea but can reach elevated average concentrations of more than 3 and 20 μg/L, respectively. Treatment techniques applied in waterworks were investigated by an extended monitoring program in three facilities and accompanied by laboratory-scale batch tests. Flocculation and activated carbon filtration proved to be ineffective for removal of metformin and guanylurea. During ozonation and chlorination experiments with waterworks-relevant ozone and chlorine doses they were partly transformed to yet unknown compounds. The effectiveness of the treatment steps under investigation can be ordered chlorination > ozonation > activated carbon filtration > flocculation. However, most effective for removal of both compounds at the three full-scale waterworks studied proved to be an underground passage (riverbank filtration or artificial groundwater recharge). A biological degradation is most likely as sorption can be neglected. This is based on laboratory batch tests conducted with three different soil materials according to OECD guideline 106. Since such treatment steps were implemented in all three drinking water treatment plants, even traces of metformin and its metabolite guanylurea could not be detected at the end of the treatment trains. Both can only be expected in finished drinking water if surface influenced raw water is used by direct abstraction without underground passage.     

Occurrence of filamentous fungi and yeasts in three different drinking water sources

In order to determine the occurrence of fungi in different drinking water sources and capture variability in terms of matrix composition and seasonal effects, surface water, spring water, and groundwater samples were collected in numerous sampling events. The occurrence and significance of fungi detected in the different water sources are reported and discussed in terms of colony-forming units per millilitre and by the identification of the most frequently detected isolates, at the species level, based on morphology and other phenotypic characters. All the samples were also analyzed in terms of total coliforms and Escherichia coli that are widely monitored bacteria considered as microbiology indicators of water quality. All the groundwater samples showed significantly lower levels of total coliforms, E. coli, and fungi compared to the surface and spring water samples. No significant correlations were found between the levels of fungi detected in all the matrices and the physico-chemical parameters and bacteria regularly monitored by drinking water utilities. Fifty-two fungi isolates were identified in this study, most of which have never been described to occur in water sources. The results obtained show that fungi occur widely in drinking water sources and that further studies should be conducted to address their biodegradation potential as well as if the drinking water treatment processes currently used are effective in removing these organisms and the potential secondary metabolites produced.     

Occurrence and fate of antibiotics in the Seine River in various hydrological conditions

Occurrence and fate of 17 antibiotics were investigated in the aqueous phase of river water under different hydrological conditions at 5 sampling locations in the Seine River inner estuary. The target analytes belonged to 4 groups: quinolones, sulfonamides, nitro-imidazoles and diaminopyrimidines. This six-month survey (from January to June 2006) showed that different compounds were occurring at individual concentrations reaching 544 ng L(-)(1) (sulfamethoxazole). All 17 compounds were detected at least once in the survey. Sulfamethoxazole was detected in every sample, and showed the highest concentrations. Norfloxacin and flumequine were found to be the most ubiquitous quinolones, with detection frequencies of 33 and 75% respectively at the most contaminated site (Poses). Investigations concerning the origins of this contamination were made by means of a longitudinal profile along the Seine River between Paris and Poses. It showed large inputs of norfloxacin, ofloxacin, trimethoprim and sulfamethoxazole from wastewater treatment plants, with an increase in norfloxacin and sulfamethoxazole concentrations of 84% and 70% respectively, both reaching 155 ng L(-)(1) in the river, downstream from a wastewater outlet. The detected compounds showed different dissipation patterns and behaviours under different hydrological conditions. Higher inputs of norfloxacin were found in low flow conditions, which were rapidly attenuated along the stream. In contrast, sulfamethoxazole inputs were increasing in high flow conditions, and dissipation of this compound was found to be slow. Similar behaviour was observed for the synergist trimethoprim. Flumequine was also frequently detected and its input increased during flood events.     

Impacts of emerging organic contaminants on freshwater resources: review of recent occurrences, sources, fate and effects

Rapid urbanization and frequent disposal of wastewater to surface water cause widespread contamination of freshwater supplies with emerging contaminants, such as pharmaceuticals, insecticides, surfactants, endocrine disruptors, including hormones. Although these organic contaminants may be present at trace levels, their adverse effects on aquatic life, animals and even humans are a growing concern. Numerous studies have been published on the occurrence and fate of emerging organic contaminants in different parts of the world, spanning a wide range of sources and aquatic environments including freshwater catchments, effluent wastewater streams, lakes, rivers, reservoirs, estuaries and marine waters. This paper reviews recent studies on the occurrence and fate of frequently detected pharmaceuticals and hormones and identifies areas that merit further research.     

村庄规划建设中水环境的困境与出路

基于一些对农村水环境、水生态的相关研究及山东济南、菏泽等的实地调研,发现这些地区在新农村建设中水环境确实面临诸多困境。现有不少研究已对其提出解决策略,大部分研究偏向从单一角度进行研究寻求解决路径。然而水环境问题涉及多个学科、多个部门、多个产业甚至多个行为主体,需要以综合系统的角度进行分析解决。本文主要针对山东片区乡村水环境出现的现象问题进行探讨,试着从结合公众需求的村域规划、生态价值和合理水面率理论等多个方面探讨走出这一困境的综合策略,以期修复广大农村腹地生态环境,继承中国传统聚落形态特色,提高基层人居住环境质量。     

Occurrence and fate modeling of MTBE and BTEX compounds in a Swiss Lake used as drinking water supply

Emissions of fuel components from boating use on multiple-use lakes and reservoirs are of high concern with regard to the drinking water supply from such water bodies. We report results of a detailed study on the occurrence, sources and fate of aromatic hydrocarbons and methyl tert-butyl ether (MTBE) in a typical holomictic lake, Lake Zurich, that supplies drinking water for the largest Swiss city. Emphasis of the investigation was on the fuel oxygenate MTBE, which was found in concentrations up to 1.4 microg/L in the epilimnion and up to 0.05microg/L in the hypolimnion of the lake. The concentration difference was due to the stratification of the lake during the boating season with very limited water exchange across the thermocline. MTBE and BTEX nearly completely volatilized before vertical lake mixing occurred in winter. Spatial and temporal variations of MTBE concentrations in the lake were observed and successfully predicted using two complementary box models (MASAS Light and Aquasim). The drinking water supply from holomictic lakes is not at risk for the scenarios studied if water is extracted from well below the thermocline. Since emissions of unburned gasoline into such water bodies are caused predominantly by boating activities, restrictions of highly emitting two-stroke engines could substantially reduce the MTBE and BTEX load of the epilimnion during the boating season.     

Occurrence and formation of chloro- and bromo-benzoquinones during drinking water disinfection

Consumption of chlorinated drinking water has shown somewhat consistent association with increased risk of bladder cancer in a series of epidemiological studies, but plausible causative agents have not been identified. Halobenzoquinones (HBQs) have been recently predicted as putative disinfection byproducts (DBPs) that might be of toxicological relevance. This study reports the occurrence frequencies and concentrations of HBQs in plant effluents from nine drinking water treatment plants in the USA and Canada, where four common disinfection methods, chlorination, chloramination, chlorination with chloramination, and ozonation with chloramination, are used. In total, 16 water samples were collected and analyzed for eight HBQs: 2,6-dichloro-1,4-benzoquinone (2,6-DCBQ), 2,6-dibromo-1,4-benzoquinone (2,6-DBBQ), 2,6-dichloro-3-methyl-1,4-benzoquinone (2,6-DC-3-MBQ), 2,3,6-trichloro-1,4-benzoquinone (2,3,6-TriCBQ), 2,5-dibromo-1,4-benzoquinone (2,5-DBBQ), 2,3-dibromo-5,6-dimethyl-1,4-benzoquinone (2,3-DB-5,6-DM-BQ), tetrabromo-1,4-benzoquinone (TetraB-1,4-BQ), and tetrabromo-1,2-benzoquinone (TetraB-1,2-BQ). Of these, 2,6-DCBQ, 2,6-DBBQ, 2,6-DC-3-MBQ and 2,3,6-TriCBQ were detected in 16, 11, 6, and 3 of the 16 samples with the method detection limit (DL) of 1.0, 0.5, 0.9 and 1.5 ng/L, respectively, using a solid phase extraction and high performance liquid chromatography-tandem mass spectrometry method. The concentrations were in the ranges of 4.5-274.5 ng/L for 2,6-DCBQ, below DL to 37.9 ng/L for 2,6-DBBQ, below DL to 6.5 ng/L for 2,6-DC-3-MBQ, and below DL to 9.1 ng/L for 2,3,6-TriCBQ. These authentic samples show DCBQ and DBBQ as the most abundant and frequently detectable HBQs. In addition, laboratory controlled experiments were performed to examine the formation of HBQs and their subsequent stability toward hydrolysis when the disinfectants, chlorine, chloramine, or ozone followed by chloramines, reacted with phenol (a known precursor) under various conditions. The controlled reactions demonstrate that chlorination produces the highest amounts of DCBQ, while pre-ozonation increases the formation of DBBQ in the presence of bromide. At pH < 6.8, 2,6-DCBQ was observed to be stable, but it was easily hydrolyzed to form mostly 3-hydroxyl-2,6-DCBQ at pH 7.6 in drinking water.     

Impacts of manipulated regime shifts in shallow lake model ecosystems on the fate of hydrophobic organic compounds

Regime shifts in shallow lakes may significantly affect partitioning of sediment-bound hydrophobic organic chemicals (HOCs) such as polychlorobiphenyls (PCB) and polycyclic aromatic hydrocarbons (PAH). In replicated experimental model ecosystems mimicking the alternative stable states ‘macrophyte-dominated’ and ‘suspended solid – phytoplankton dominated’, we tested the effects of macrophytes and benthivorous fish presence on mass distribution and bioaccumulation of hexachlorobenzene, PCBs and PAHs. HOC mass distributions and lipid-normalized concentrations in sediment (Soxhlet- and 6-h Tenax-extractable), suspended solids, macrophytes, periphyton, algae, zooplankton, invertebrates and carp revealed that mobile, i.e. less hydrophobic or less aged HOCs were more susceptible to ecological changes than their sequestered native counterparts. Macrophytes were capable of depleting considerable percentages of the bioavailable, fast desorbing HOC fractions in the sediment upper (bioactive) layer, but did not have a significant diluting effect on lipid-normalized HOC concentrations in carp. Carp structured invertebrate communities through predation and stimulated partitioning of HOCs to other system compartments by resuspending the sediment. These results show that shifts in ecosystem structure have clear effects on fate, risks and natural attenuation of sediment-bound organic contaminants.     

The fate of wastewater-derived NDMA precursors in the aquatic environment

To assess the stability of precursors of the chloramine disinfection byproduct N-nitrosodimethylamine (NDMA) under conditions expected in effluent-dominated surface waters, effluent samples from four municipal wastewater treatment plants were subjected to chlorination and chloramination followed by incubation in the presence of inocula derived from activated sludge. Samples subjected to free chlorine disinfection showed lower initial concentrations of NDMA precursors than those that were not chlorinated or were disinfected with pre-formed chloramines. For chloraminated and control (unchlorinated) treatments, the concentration of NDMA precursors decreased by an average of 24% over the 30-day incubation in samples from three of the four facilities. At the fourth facility, where samples were collected on three different days, NDMA precursor concentrations decreased by approximately 80% in one sample and decreased by less than 20% in the other two samples. In contrast to the low reactivity of the NDMA precursors, NDMA disappeared within 30 days under the conditions employed in these experiments. These results and measurements made in an effluent-dominated river suggest that although NDMA may be removed after wastewater effluent is discharged, wastewater-derived NDMA precursors could persist long enough to form significant concentrations of NDMA in drinking water treatment plants that use water originating from sources that are subjected to wastewater effluent discharges.     

复杂环境下高水位深基坑支护渗漏止水施工技术

某工程项目地处福州闽江北江滨,地下水位高且受闽江水位涨落影响变化极大,因此如何止水成为基坑支护的关键,本文从支护桩的选型进行分析,确定采用冲孔咬合桩加钢筋混凝土内支撑体系,冲孔咬合桩在该体系中既承担围护作用又起到止水作用。同时针对开挖过程中出现的渗漏进行原因分析并采取相应的止水措施。     

Occurrence and fate of corrosion-induced zinc in runoff water from external structures

This paper comprises data from an extensive cross-disciplinary research project aiming to elucidate the environmental fate of corrosion-induced zinc release from external structures. It includes an exposure assessment that provide long-term runoff rates, concentrations and chemical speciation of zinc, from 14 zinc-based materials exposed during 5 years in Stockholm, Sweden, and an effect assessment including bioavailability and ecotoxicity measurements, both at the immediate release situation and after soil interaction. Runoff rates of total zinc ranged from 0.07 to 2.5 g Znm-2 yr-1 with zinc primarily released as the free ion for all materials investigated. The average effect concentration, causing a 50% growth reduction after 72 h to the green algae Raphidocelis subcapitata, was at the immediate release situation 69 microg ZnL-1. Upon interaction of runoff water with soil, which simulated 18 to 34 years of exposure, the total zinc concentration was significantly reduced, from milligram per litre to microgram per litre levels. Simultaneously, the most bioavailable fraction of zinc in runoff, the hydrated zinc(II)-ion, decreased from more than 95% to about 30%. The major fraction, 98-99%, of the introduced total zinc concentration in the runoff water was retained within the soil. As long as the soil retention capacity was not reached, this resulted in zinc concentrations in the percolate water transported through the soil layer, close to background values and below growth inhibition concentrations for the green algae investigated. Zinc retained in soil was to a large extent (85-99.9%) extractable with EDTA, and available for plant uptake after 5 to 7 months of ageing.     

Distribution and fate of nonylphenol in an aquatic microcosm

An aquatic microcosm consisting of four compartments, namely surface microlayer (SM), water sediment and biota (zebra fish), was developed to investigate the distribution and fate of nonylphenol (NP) in an aquatic environment. Level III and level IV fugacity-based multimedia models were used to calculate the distribution and fate of NP. Data obtained from model calculations were in good agreement with those of the experiments. Results of the model calculations showed that 86.50% of all NP input was removed by advective outflow, while 61.99% of the remainder was distributed to the sediment phase, 34.89% to the water phase, 2.50×10⁻²% to SM and 3.13% to the biotic phase. This finding demonstrates that sediment plays a key role in the fate of NP and acts as a sink in the aquatic environment. Bioconcentration factor (BCF) of NP in the zebra fish was high and varied in different parts of the fish. The highest BCF was 1440 in the viscera. After the uptake experiment, depuration of NP in clean water indicated that, the concentration of residue NP in the zebra fish was still high. This implies that NP in fish can pose a potential threat to human health due to its bioaccumulation in the food chain.     

Persistence of pharmaceuticals and other organic compounds in chlorinated drinking water as a function of time

Ninety eight pharmaceuticals and other organic compounds (POOCs) that were amended to samples of chlorinated drinking-water were extracted and analyzed 1, 3, 6, 8, and 10 days after amendment to determine whether the total chlorine residual reacted with the amended POOCs in drinking water in a time frame similar to the residence time of drinking water in a water distribution system. Results indicated that if all 98 were present in the finished drinking water from a drinking-water treatment plant using free chlorine at 1.2 mg/L as the distribution system disinfectant residual, 52 POOCs would be present in the drinking water after 10 days at approximately the same concentration as in the newly finished drinking water. Concentrations of 16 POOCs would be reduced by 32% to 92%, and 22 POOCs would react completely with residual chlorine within 24 h. Thus, the presence of free chlorine residual is an effective means for transforming some POOCs during distribution.     

给水排水对住宅建筑室内声环境的影响与控制

随着对住宅舒适性的要求越来越高,人们越来越关注住宅建筑室内声环境的质量。在影响室内声环境的多个因素中,给排水系统的影响是较大的。本文从给排水系统方面,分析论述了其对住宅室内声环境产生的影响、产生影响的原因以及噪声控制的方法。     

Norovirus pathway in water environment estimated by genetic analysis of strains from patients of gastroenteritis, sewage, treated wastewater, river water and oysters

In this study, Norovirus (NV) capsid gene was detected from patients of gastroenteritis, domestic sewage, treated wastewater, river water and cultivated oysters in geographically close areas where all of samples were collected. In order to improve recovery efficiency of NVs from oysters, a new method using a spallation apparatus was developed. As a result, 18 of 30 oysters (60%) were positive for NV gene, while 7 of 30 (23%) oysters from the same sampling point were positive with the conventional ultracentrifugal method between November 2003 and February 2004. These results indicate that our new method exhibits the higher efficiency of recovering NVs than the conventional ultracentrifugal method. Six of 8 samples (75%) of river water were positive for NV gene between November 2003 and February 2004. Furthermore, 8 of 9 samples (89%) of treated wastewater and all 9 samples of sewage were positive for NV gene in the same period. These results indicated that treated wastewater would be one of the main sources for NV pollution in this area. The phylogenetic analysis in isolated NV capsid genes was conducted, in which high identities of gene sequences between NVs from patients, domestic sewage, river water and cultivated oysters were observed. These results implied that there would be a geographically associated circulation of NVs between human and cultivated oysters via water environment. It would be important to quantitatively analyze the moving pathway of NVs, which directly link to the development of a new scheme for preventing water environment and cultivated oysters from NV contamination.     

水利工程建设中环境监理工作探究

水利工程建设项目会对生态环境产生重要的影响,针对环境监理的目的和内容,结合万家寨引黄工程中的环境监理工作实际,对当前水利工程建设项目环境监理工作提出几点建议,为进一步完善和推广环境监理和监测机制提供有益的参考。     

Occurrence and fate of bulk organic matter and pharmaceutically active compounds in managed aquifer recharge: a review

Managed aquifer recharge (MAR) is a natural water treatment process that induces surface water to flow in response to a hydraulic gradient through soil/sediment and into a vertical or horizontal well. It is a relatively cost-effective, robust and sustainable technology. Detailed characteristics of bulk organic matter and the occurrence and fate of pharmaceutically active compounds (PhACs) during MAR processes such as bank filtration (BF) and artificial recharge (AR) were reviewed. Understanding the fate of bulk organic matter during BF and AR is an essential step in determining pre- and/or post-treatment requirements. Analysis of organic matter characteristics using a suite of analytical tools suggests that there is a preferential removal of non-humic substances during MAR. Different classes of PhACs were found to behave differently during BF and AR. Antibiotics, non-steroidal anti-inflammatory drugs (NSAIDs), beta blockers, and steroid hormones generally exhibited good removal efficiencies, especially for compounds having hydrophobic-neutral characteristics. However, anticonvulsants showed a persistent behavior during soil passage. There were also some redox-dependent PhACs. For example, X-ray contrast agents measured, as adsorbable organic iodine (AOI), and sulfamethoxazole (an antibiotic) degraded more favorably under anoxic conditions compared to oxic conditions. Phenazone-type pharmaceuticals (NSAIDs) exhibited better removal under oxic conditions. The redox transition from oxic to anoxic conditions during soil passage can enhance the removal of PhACs that are sensitive to redox conditions. In general, BF and AR can be included in a multi-barrier treatment system for the removal of PhACs.     

Occurrence of endocrine disrupting compounds, pharmaceuticals, and personal care products in the Han River (Seoul, South Korea)

The occurrence of 31 selected endocrine disrupting compounds (EDCs) and pharmaceuticals and personal care products (PPCPs) in Korean surface waters was investigated. The area was selected since there is a lack of information in the Seoul area on the suspected contamination of rivers by micropollutants, although over 99% of drinking water is produced from surface waters in this area that has a population of approximately 15 million inhabitants. Samples were collected from upstream/downstream and effluent-dominated creeks along the Han River, Seoul (South Korea) and analyzed by liquid chromatography with tandem mass spectrometry (LC-MS/MS) with electrospray ionization (ESI) and atmospheric pressure chemical ionization (APCI). Most target compounds were detected in both the Han River samples (63%) and the effluent-dominated creek samples (79%). Iopromide, atenolol, TCPP, TECP, musk ketone, naproxen, DEET, carbamazepine, caffeine, and benzophenone were frequently detected in both river and creek samples, although the mean concentrations in effluent-dominated creek samples (102 ng/L-3745 ng/L) were significantly higher than those in river samples (56 ng/L-1013 ng/L). However, the steroid hormones 17β-estradiol, 17α-ethynylestradiol, progesterone, and testosterone, were not detected (< 1 ng/L) in both the river and creek samples. Numerous target compounds (15) were found to be positively correlated (over 0.8) to the conventional water quality parameters (chemical oxygen demand, biochemical oxygen demand, dissolved organic carbon, and ultraviolet absorbance). Results of this study provide increasing evidence that certain EDCs and PPCPs commonly occur in the Han River as the result of wastewater outfalls.