Monitoring of the three organophosphate esters TBP,TCEP and TBEP in river water and ground water (Oder,Germany)

The behaviour of the three organophosphate esters tributyl phosphate (TBP), tris(2-chloroethyl)phosphate (TCEP) and tris(2-butoxyethyl)phosphate (TBEP) during infiltration of river water to ground water has been investigated. The monitoring site is the Oder River and the adjacent Oderbruch aquifer. From March 2000 to July 2001, 76 ground water samples from monitoring wells located close to the Oder River and nine river water samples were collected. Additionally, influent and effluent samples from local waste water treatment plants, one sample of rain water and samples of roof runoff were collected. All samples were analysed by solid-phase-extraction followed by gas chromatography/mass spectrometry. TBP, TCEP and TBEP were detected at mean values of 622 ng l(-1), 352 ng l(-1), and 2955 ng l(-1), respectively in municipal waste water effluents. This points to a major input of these compounds into the Oder River by municipal waste water discharge. The concentrations of TBP and TBEP decreased downstream the Oder River possibly due to aerobic degradation. TBP, TCEP and TBEP were detected in ground water influenced predominantly by bank-filtered water. This demonstrates a transport of organic compounds by river water infiltration to ground water. TBP, TCEP and TBEP were also detected in rain water precipitation, roof runoff and ground water predominantly influenced by rain water infiltration. This hints to an input of these compounds to ground water by dry and wet deposition after atmospheric transport. Organophosphate esters were also detected in parts of the aquifer at 21 m depth. This demonstrates low anaerobic degradation rates of TBP, TCEP and TBEP.     

基于磁性分离测定水样中的吲哚美辛

免疫磁性微球(SMPPA)应用于水样中吲哚美辛的分离富集,并应用高效液相色谱法对吲哚美辛进行测定。在优化的淋洗和洗脱条件下,70%甲醇和10%甲醇分别作为洗脱液和淋洗液,其回收率能达到90%。选择了湖水、河水、自来水、污水厂进口水以及医院排水为真实样品进行测定,其中湖水、河水、自来水3种真实水样中未能检测出吲哚美辛,污水厂进口水以及医院排水中吲哚美辛的含量分别为0.762、35.4 ng/m L。对这5种水进行加标回收吲哚美辛,加标回收率为92.7%~113%,RSD为1.09%~7.73%。该方法具有简便、快速、特异性等特点,能有效地分离富集水样中的目标物,对其他目标物具有广泛的实际应用价值。     

Patterns and levels of halogenated volatile compounds in Portuguese surface waters

The present study focused on monitoring the concentration of 14 halogenated volatile organic compounds in surface waters, including sea, estuarine, river water and industrial effluents in order to determine the most ubiquitous compounds and their concentration levels, which were used to establish their geographical and temporal distribution. EPA Method 502, based on purge and trap techniques, was used. In this method volatile organic pollutants are extracted (purged) from the water sample by bubbling inert gas through the aqueous sample. Purged sample components are trapped in a cartridge containing the polymeric sorbent Tenax and, thereafter, the cartridge is heated and backflushed with helium to desorb the trapped sample components directly into a gas chromatograph with electron capture detector (GC-ECD). The linearity range of the method varied from 0.1 to 4 microg L(-1) with a limit of detection at the low microg L(-1) level. The present study consisted of a monthly monitoring of 46 points throughout Portugal, during 14 months. Chloroform was found in 50% of the samples analyzed, its presence being correlated to both agricultural and industrial activities. Other compounds detected were tetrachloroethylene, trichloroethylene, carbon tetrachloride and 1,2,4 trichlorobenzene, which were present in 10-20% of the samples at concentrations up to 18 microg L(-1). 1,1,2,2-Tetrachloroethane and its degradation product 1,1,2-trichloroethane were found in 5% of the samples, the levels of the latter being higher than those of the parent compound in most samples. Sporadic high concentrations of some volatile halogenated organic compounds were attributed to local uses as solvents.     

Polycyclic musks in the Ruhr catchment area--transport, discharges of waste water, and transformations of HHCB, AHTN and HHCB-lactone

The polycyclic musk fragrance compounds HHCB (1,3,4,6,7,8-hexahydro-4,6,6,7,8,8-hexamethylcyclopenta-(g)-2-benzopyran; trade name, e.g. galaxolide) and AHTN (7-acetyl-1,1,3,4,4,6-hexamethyl-1,2,3,4-tetrahydronaphthalene, trade name, e.g. tonalide) and the transformation product of HHCB (HHCB-lactone) were analysed in surface water samples and sewage treatment plants (STP) effluents in the Ruhr megalopolis. The STPs were the dominant source for these pollutants. In the part of the river where the drinking water is extracted from the river, about 60 ng L(-1) HHCB, 10 ng L(-1) AHTN and 20-30 ng L(-1) HHCB-lactone were found as typical riverine concentrations, while none of the compounds were detected near the spring of the river. On the other hand sewage treatment plant effluents exhibited concentrations up to 600 ng L(-1). The STP's effluent resulted in elevated concentrations in some parts of the river and in the lakes into which they discharge. As some of the plants emit HHCB-lactone with a significantly changed enantiomeric pattern, biotransformation of HHCB to HHCB-lactone occurs in some waste water treatment plants operating with activated sludge. In those parts of the river where no relevant discharges of waste water or fresh water takes place neither the concentration nor the pattern changes significantly. This holds true especially for the HHCB versus HHCB-lactone ratios which indicates degradation less than 15% of the HHCB inventory in the river Ruhr itself. In other rivers, such as the Rhine, higher levels of HHCB-lactone in comparison to HHCB were detected (ratio 1 : 1).     

沙颍河流域抗生素污染特征与生态风险评价

于2018年7月 (丰水期)、11月 (枯水期) 和2019年3月(平水期)对沙颍河流域5种抗生素磺胺吡啶(SPD)、磺胺氯哒嗪(SCP)、磺胺嘧啶(SDZ)、环丙沙星(CIP)和四环素(TCL)的污染状况和空间分布进行了研究,并对其生态风险进行了评价。结果表明,沙颍河流域5种抗生素在丰水期、枯水期和平水期均有检出,丰水期CIP、枯水期SPD和SDZ以及平水期SCP的检出率均>50%,平水期SCP的检出率最高达到70.97%,CIP在丰水期的检出值最高(655 ng/L),5种抗生素累积浓度为：丰水期>平水期>枯水期。对比国内其他地区水体环境,沙颍河流域5种抗生素浓度总体处于一般水平,但丰水期CIP检出浓度较高。相关性分析显示抗生素浓度与水质参数硬度、NH₃-N和电导率显著相关。5种抗生素的水生态风险为：丰水期>枯水期>平水期,其中CIP和TCL均为高风险。提出,应加强监测评估与预警管理,有效控制其水生态风险。     

Nitrosamine occurrence at Korean surface water using an analytical method based on GC/LRMS

The survey of nitrosamine occurrence at Korean surface water of Nakdong river is conducted in this study. For this purpose, the nitrosamine analytical method based on more affordable GC/LRMS (low resolution mass spectrometry) has been developed. According to the study results, six nitrosamine compounds (NDEA as N-nitrosomethylethylamine, NDPA as N-nitrosodi-n-propylamine, NDMA as N-nitrosodimethylamine, NMEA as N-nitrosomethylethylamine, NDBA as N-nitrosodi-n-butylamine, and NDPHA as N-nitrosodiphenylamine) were detected at the Nakdong river. Among these, NDEA and NDPA are the most important compounds in terms of the nitrosamine contamination of the Nakdong river. The detected concentration of NDEA exceeded the CDHCS (California Department of Health Care Services) response level of 100 ng/L at several sites. The detected concentration of NDPA approached the response level (500 ng/L) at a few sites. When all nitrosamine concentrations were summed up, the maximum concentration of 735.7 ng/L was detected at the Nakdong river. An equation describing a decrease in total nitrosamine concentration along downstream sampling sites was proposed in this study. The equation can be used to predict the downstream nitrosamine contamination at the Nakdong river. Among various water quality parameters, T-N showed a good correlation with total nitrosamine concentration.     

由河流流速、COD浓度估计河流COD衰减系数的经验模型

本文在综合分析影响河流ＣＯＤ衰减系数的各要素和系统调查相关资料的基础上,采用逐步回归分析方法得到了一个由河流流速、ＣＯＤ浓度估计河流ＣＯＤ衰减系数的经验模型,并通过方差分析检验了模型的可靠性。该经验模型简便,易于操作,既可应用于现有的河流水体,也可与水质模型相结合应用于变化后的河流水体,具有较强的应用性。     

Transportation and fate of cationic surfactant in river water

The degradation, sorption, transportation and material balance of cationic surfactants discharged from domestic waste into river water was studied. Ion-pair solid-phase extraction behavior showed that the sorption of cationic surfactants as an ion-pair with anionic surfactant onto river sediment was so strong that little cationic surfactant was found in the bulk water. Cationic surfactant was found in river sediment at more than 500 times higher concentration than that in the bulk water. The degradation of the cationic surfactant was very slow in river water and much slower in the sediment. A material balance of cationic surfactant was estimated for a river running through Toyama City by measuring the flow rate and the concentration of cationic surfactant in the water at several points. It was found that more than 30% of cationic surfactant introduced to the river was lost during the river running through ca. 3 km in 3 h. This reduction probably comes from a quick transfer of the cationic surfactant from river water to sediment and water weed by means of adsorption or precipitation with suspending solids.     

A long-term survey of heavy metals and specific organic compounds in biofilms, sediments, and surface water in a heavily affected river in the Czech Republic

To assess the long-term anthropogenic load of the Bílina River (Czech Republic), the concentrations of heavy metals and specific organic compounds in different river ecosystem matrices (water, biofilms, and sediments) were determined. Although the current concentrations of pollutants in surface water are low, frequently below the limits of the quantitative analytical methods used, the river ecosystem is still heavily loaded by anthropogenic pollution, mainly from the chemical and mining industries. This was demonstrated by analyzing biofilms and sediments. These matrices are more accurate representatives of the actual situation in the river and do not depend on hydrological conditions or random variability in water quality. The results indicate that the middle and the lower parts of the river are heavily polluted by mercury, arsenic, vanadium, polychlorinated biphenyls, hexachlorobenzene, and dichloro-diphenyl-trichloroethane. As a tributary of the Elbe River, the Bílina River represents a significant risk for the development of quality in this major European river.     

Sensitivity Analysis and Water Quality Modeling of a Tidal River Using a Modified Streeter–Phelps Equation with HEC-RAS-Calculated Hydraulic Characteristics

A modified Streeter–Phelps equation and the Hydrological Engineering Centers River Analysis System (HEC-RAS) were combined to assess water quality of the Tan-Sui River and its tributaries. The Tan-Sui River is the main source of water supply for northern Taiwan, and the water quality of its stream is significantly affected by tides. In this study, HEC-RAS was employed to assess the impact of tides on water quality and to calculate reoxygenation coefficients. The modified Streeter–Phelps equation was used to calculate water quality in terms of contaminant degradation and reoxygenation. Biochemical oxygen demand (BOD) and ammonia nitrogen (NH₃–N), the most important identified sources of water pollution in the rivers investigated, were evaluated. Dissolved oxygen (DO) was also simulated, since it is often used as a staple of water quality. Results showed that employing HEC-RAS for hydraulic calculations improves the modified Streeter–Phelps simulation. In river sections without tidal influence, water quality was sensitive to the BOD and NH₃–N degradation constants. Downstream of Chin-Mei Creek, while the BOD degradation constant decreased by 80%, BOD and DO concentrations increased from 7.1?mg/L to 10.7?mg/L and 5.0?mg/L to 7.2?mg/L, respectively, indicating that water quality was not as sensitive to variations of the BOD degradation constant as expected. The concentrations of DO and BOD at the river mouth had a significant impact on water quality for the tidal sections of the investigated rivers due to mixing of tidal and river waters. The BOD and NH₃–N degradation constants in the tidal sections had little impact on water quality simulations. This study demonstrated the innovative combination of the modified Streeter–Phelps equation and HEC-RAS to assess the impact of tidal variation and to simulate the water quality of a tidal river when available data is rather limited.     

Occurrence of naproxen,ibuprofen, and diclofenac residues in wastewater and river water of KwaZulu-Natal Province in South Africa

The present paper reports a detailed study that is based on the monitoring of naproxen, ibuprofen, and diclofenac in Mbokodweni River and wastewater treatment plants (WWTPs) located around the city of Durban in KwaZulu-Natal Province of South Africa. Target compounds were extracted from water samples using a multi-template molecularly imprinted solid-phase extraction prior to separation and quantification on a high-performance liquid chromatography equipped with photo diode array detector. The analytical method yielded the detection limits of 0.15, 1.00, and 0.63 μg/L for naproxen, ibuprofen, and diclofenac, respectively. Solid-phase extraction method was evaluated for its performance using deionized water samples that were spiked with 5 and 50 μg/L of target compounds. Recoveries were greater than 80% for all target compounds with RSD values in the range of 4.1 to 10%. Target compounds were detected in most wastewater and river water samples with ibuprofen being the most frequently detected pharmaceutical. Maximum concentrations detected in river water for naproxen, ibuprofen, and diclofenac were 6.84, 19.2, and 9.69 μg/L, respectively. The concentrations of target compounds found in effluent and river water samples compared well with some studies. The analytical method employed in this work is fast, selective, sensitive, and affordable; therefore, it can be used routinely to evaluate the occurrence of acidic pharmaceuticals in South African water resources.     

Emission of volatile organic sulfur compounds from a heavily polluted river in Guangzhou, South China

Emissions of five volatile organic sulfur compounds (VOSCs), including methanethiol, carbonyl sulfide, dimethyl sulfide, carbon disulfide, and dimethyl disulfide, from a heavily polluted river, Shijing River in Guangzhou of South China, was studied. The results showed that the amounts of all VOSCs emitted from the river increased from downstream to upstream along the river with increasing magnitude of water pollution. The emission of carbonyl sulfide was the highest among the target analytes, ranging from 23.8 microg m(-2) h(-1) to 42.6 microg m(-2) h(-1) at the water surface of Shijin River. The concentration levels of VOSCs on the riverbank were lower than those at the water surface either in Shijing River or in Liuxi River. However, the contribution of dimethyl disulfide to the total VOSCs on the riverbank was higher than that at the water surface in most sampling sites, indicating that there might be a point source of dimethyl disulfide on the riverbank besides diffusion from water surface. The 24-h semi-continuous monitoring data revealed that the emissions of VOSCs at the water surface peaked at 9:00 and 21:00, which was consistent with the water quality variability in Shijin River caused by daily tidal variation.     

区域水环境监测网络优化及评价考核方法研究

科学合理地布设水质监测断面是全面准确获取水环境质量监测数据的前提条件。利用研究区域现有断面2014年的监测数据,结合水资源调度方式和水环境功能区划要求,划分为五大片区并采用聚类分析方法进行断面优化,通过F检验和t检验表明优化前后断面无显著差异。同时,提出了一种综合的水环境质量考核办法——区域水环境综合评价考核指标,该指标包括骨干河道、乡村河道两类考核断面,采用综合水质评价与单因子评价相结合的方法,设置适当的权重系数,评价结果较为全面、客观地反映区域水环境质量状况,基本满足对区域水环境质量考核评价的管理需求。     

GC／MS在水污染事故监测中的应用

用ＧＣ／ＭＳ仪对一起严重的水污染事故水样进行了监测,检出的几十种化合物中,有多种与某化工厂的原料,产品及其中间体相吻合,该厂排放的污水与被污染河水水样有极其相似的指纹特征,迅速地判定了污染事故的责任者。     

Butyltin contamination in sediments and seawater from Kaohsiung Harbor, Taiwan

The distribution of butyltin (BT) compounds in the sediments and seawater, at the river outfalls, fishing ports, shipyards, and industrial zone docks of Kaohsiung Harbor, Taiwan were investigated. Twenty sediment and seawater samples were collected from various locations in the Harbor in 2006 and analyzed for monobutyltin (MBT), dibutyltin (DBT), and tributyltin (TBT). Results showed that the concentration of total BTs varied from 1.5 to 151 ng/g in sediment samples, with TBT being the major component of the sediment samples. This suggests that sediments could be the most possible sink of TBT brought by the sorption mechanism. The concentrations of BTs ranged from 9.7 to 270 ng/L in seawater samples, whereas DBT and MBT, the degradation byproducts of TBT, were mainly the most abundant BT compounds of the seawater samples. This indicates that the abiotic or biotic degradation potential of TBT was significant. Spatially, the highest concentrations of BTs were observed in both water and sediment samples collected from the shipyard and fishing port areas. This indicates that the shipping-related activities (e.g., navigation, ship repair, and ship building) would contribute most of BTs in the environment. Results show that the concentrations of degradation products (DBT and MBT) were related closely to temperature, salinity, dissolved oxygen (DO), and chlorophyll-a of the seawater. This implies that seasonal changes of the water parameters controlled the degradation of TBT in seawater. The observed levels of BT compounds in both seawater and sediments were much higher than those required to induce toxic effects on marine organisms, suggesting that appropriate TBT control strategies should be taken in Kaohsiung Harbor.     

Determination of organophosphorus pesticides and related compounds in water samples by membrane extraction and gas chromatography

A membrane extraction-gas chromatography method was developed fordetermination of organophosphorus pesticides and related compounds including methamidophos, DDVP, dimethoate, methyl parathion, parathion, thiophosphoric acid trimethyl ester, and thiophosphoramidic acid dimethyl ester in water samples. In thismethod, surface-modified acetic cellulose membranes were used to extract the target analytes in water samples, the extracted analytes were back-extracted into a small amount of methanol, andgas chromatography with pulsed flame photometric detector (GC-PFPD) was used to determine the concentrations of targetanalytes in the extracts. The recoveries obtained for thetarget analytes spiked into the water samples ranged from 66to 94%. The method detection limit for each target analyte was 0.05 g L^-1. The method developed in this study had shown the advantages of being cheap, simple, fast, and reliable. It had been used successfully to determine the concentrations of target analytes in river water samples.     

Occurrence of estrogenic chemicals in South Korean surface waters and municipal wastewaters

Broad scale monitoring of estrogenic compounds was performed at 19 sampling points throughout the Yeongsan and Seomjin river basins and 5 wastewater treatment plants (WWTPs) adjacent to the Gwangju area, Korea, from December 2005 to August 2007. The concentrations of estrogenic compounds, including estrone (E1), 17β-estradiol (E2), 17α-ethynylestradiol (EE2), bisphenol-A, nonylphenol (NP) and 4-octylphenol (OP), in the samples was measured with gas chromatography/mass spectrometry (GC-MS). In addition, the estrogenic activities throughout the river were investigated using the E-screen assay. Of the six estrogenic chemicals, NP (114.6-336.1 ng L(-1)) and EE2 (0.23-1.90 ng L(-1)) were detected at the highest and lowest levels, respectively in both the river waters and the WWTP effluents. Bisphenol-A showed the largest concentration range, from 7.5 to 335 ng L(-1). The concentrations of E1, E2 and octylphenol ranges were 3.6-69.1, 1.2-10.7, and 2.2-16.9 ng L(-1), respectively. According to the calculated estradiol equivalent concentration (EEQ); however, no estrogenic contribution was observed due to the phenolic compounds in the river waters and effluents. E1 and E2 dominated in both the river water and effluent samples, with contributions to the calculated EEQ of over 79 and 77%, respectively. Conversely, EE2 was rarely detected in the river waters (21%) and effluents (0%). The largest contribution of EE2 to the calculated EEQ was 21% in the river water at S-7. The levels of E1, E2, and EE2 were remarkably decreased in the effluents, indicating that the 5 WWTPs did not contribute to the estrogenic effect of the receiving streams. Overall, the WWTPs did not contributed to the estrogenic activity of the receiving waters, but the livestock industry or wildlife may play an important role in the estrogenic contribution to river water.     

Water Environmental Degradation of the Heihe River Basin in Arid Northwestern China

Water environmental degradation is a major issue in the Heihe River Basin belonging to the inland river basin of temperate arid zone in northwestern China. Mankind’s activities, such as dense population and heavy dependence on irrigated agriculture, place immense pressure on available and limited water resources during the last century, especially the recent five decades. An investigation on the water environmental degradation in the Heihe River Basin and analysis of its causation were conducted. The results indicated that water environmental changes in the whole basin were tremendous mostly in the middle reaches, which reflected in surface water runoff change, decline of groundwater table and degeneration of surface water and groundwater quality. Some new forms of management based on traditional and scientific knowledge must be introduced to solve problems of water environmental degradation in the Heihe River Basin.     

Assessment of land cover changes & water quality changes in the Zayandehroud River Basin between 1997–2008

Water quality of rivers is strongly influenced by landscape characteristics of their watershed, including land use /cover types, and their spatial configuration. This research evaluates the effects of land cover changes on the water quality of the Zayandehroud River, which is the most important river in the center of Iran. The main goal of this study was to quantify the change in rangelands, forests, and bare lands in the Zayandehroud river basin, which suffered intense human interference, in a period of 11 years (1997–2008), and to evaluate how landscape patterns (including the number of patches, edge density, percentage of rangelands, forests, and bare lands) influence on the 14 water quality indices (including BOD5, EC, NO3, P, and TDS) measured in 10 stations along the river. Results showed that from 1997 to 2008, bare lands increased from 5.8 to 20 %, while rangelands decreased from 70 to 55 % in the whole basin. The results indicated that water quality was significantly correlated with both the proportions and configuration of rangeland and bare land areas. The total edge (TE) of rangeland area had positive effects on water quality, especially on BOD5 and EC. Percentage of landscape (PLAND) and largest patch index (LPI) metrics of rangeland had positive effect on decreasing nutrient (NO₃, PO₄). The results showed that water quality was more likely degraded when there was high edge density (ED) of bare lands. Results of this study also revealed that degradation of rangeland lead to the degradation of water quality. Finding of this study highlights the importance of rangeland conservation in water quality management at landscape scale.     

江苏省水质全要素代表性监测体系的设计

为了评价并进行城市水环境质量考核排名,介绍了江苏省组织开展涵盖地表水、饮用水、地下水、近岸海域和城市内河5种类型"全要素、代表性"水质监测断面(点位)体系建设工作的情况以及全要素断面设置的基本原则和做法。分苏南、苏北、苏中3个区域,对全省地表水监测代表性进行了量化计算,结果表明,调整后全省水质综合指数极差从41.07降至7.17,标准差从3.16降为0.49;采用德尔斐层次分析法分析,设计了水质代表性指数,含1项一级指标、5项二级指标、12项三级指标,计算表明,调整前全省水质代表性指数得分为69.1分,调整后为88.7分。将调整结果进行论证后再与各市环保主管部门交换意见,取得最终一致后正式实施。