Identification of surfactant degradation products as toxic organic compounds present in sewage sludge

A cost-effective strategy combining chemical analysis and bioassays for the identification of polar toxic compounds in sewage sludge is reported. ToxAlert 100 bioluminescence inhibition assay was used in combination with chemical analysis involving extraction, clean-up, chromatographic separation and mass spectrometry detection. This methodology was applied to real samples of sludge from three wastewater treatment plants (WWTP) located in Catalonia (Spain) during a 3 month period. In the first step, sewage sludge was lyophilized, treated by sonication with a mixture of methanol and chloroform and finally cleaned up using a sequential solid phase extraction (SSPE) with an octadecylsilica cartridge (C18) in series with a polymeric Lichrolut EN cartridge (Lic EN). In the second step, the toxicity of each fraction of the sludge sample was investigated using the ToxAlert 100. The unequivocal identification and quantification of polar organic cytotoxic substances present in the fractionated extracts were determined by liquid chromatography-mass spectrometry (LC-MS). Major toxic compounds identified were: non-ionic polyethoxylated surfactants (nonylphenol polyethoxylates, alcohol polyethoxylates), their intermediates (polyethylene glycol polyethoxylated, nonylphenol carboxylates and polyethoxylated alcohol carboxylates), linear alkylbenzenesulfonates and heavy metals. The toxic response (in terms of bioluminescence inhibition using ToxAlert 100), defined by the 50% effective concentration (EC50), and the toxicity units (TU) for every standard non-ionic surfactant were calculated. The results provided the identification of polar cytotoxic compounds as well as the evaluation of their contribution to the total toxicity observed in sewage sludge.     

Screening and quantification of emerging contaminants in Periyar River,Kerala (India) by using high-resolution mass spectrometry (LC-Q-ToF-MS)

The presence of emerging contaminants (ECs) in different aquatic systems may contribute to hazardous effects on aquatic organisms and subsequently on human health. In the present work, liquid chromatography coupled to a quadrupole time of flight mass spectrometer (LC-Q-ToF-MS) was used to identify and quantify a series of ECs in Periyar River in Aluva region, Kerala, India. The water samples were pre concentrated using solid-phase extraction (SPE) prior to analysis. The compounds were probed in both positive and negative ionization mode using electro spray ionization (ESI). Method validations were performed for linearity, limit of detection (LOD), limit of quantification (LOQ), accuracy, and precision (intraday and inter day). The ECs were quantified using standard calibration curve. The identified nine ECs include pharmaceuticals, personal care products, steroids, surfactants, and phthalate. A relatively high concentration was observed in the case of 2-dodecyl benzene sulfonic acid (1012 ng/l) and low concentration was observed for lignocaine (4.3 ng/l; since this is below LOQ, the value is only approximate). In addition, we have identified another 28 organic compounds using the technique of non-target analysis out of which seven compounds fall in the category of surfactants. Being the first report on ECs in Periyar River, the data is very important as this river is one of the biggest and important rivers of Kerala having several purification units for drinking water in the province.     

水中多种酚类化合物同步提取方法研究

对水中14种酚类化合物的液液萃取过程进行研究,选取不同萃取溶剂体系、水样pH和盐析条件等多个对萃取效率有决定性影响的参数进行优化。通过上述条件的优化选择,实现了同步对包括低沸点的苯酚、一氯代酚及较难提取的甲基酚和硝基酚等14种不同类型酚类化合物最优的萃取,提取效率达到75.2%~110.3%。     

Simplified determination of lipophilic metabolites of nonylphenol ethoxylates: method development and application in aqueous samples from Buenos Aires, Argentina

In the present work we have developed an analytical methodology for the determination of nonylphenol (NP) and nonylphenol mono- and di-ethoxylates (NP1EO and NP2EO) in water samples. The applicability of this methodology was proved by means of the analysis of environmentally relevant aqueous samples from Buenos Aires. This constitutes a starting point for a rigorous assessment of the incidence of NPnEO surfactants in Argentina, as only very few, qualitative or semi-quantitative data on the occurrence of these compounds in local systems were available up to this time. Enrichment of the analytes was carried out by solid-phase extraction on a C-18 sorbent, followed by elution with ethyl acetate. Normal-phase high performance liquid chromatography on an amino-silica column and fluorescence detection at excitation-emission wavelengths of 230-300 nm were employed for separation and quantification of the analytes. Confirmation of peak assignment in selected real samples was performed by off-line coupling HPLC with GC-MS analysis. A non-polar GC capillary column was used, and a characteristic peak pattern was obtained for the alkyl chain isomers of each ethoxylated homologue and NP. GC-MS analyses yielded in all cases purity levels higher than 80% for the HPLC collected fractions. The elevated concentrations found for the estrogenic metabolites of NPnEO are in accordance with an unrestricted use of this class of non-ionic surfactants in the country.     

高效液相色谱-串联质谱法同时测定地表水中33种药物

采用固相萃取-高效液相色谱-串联质谱法(SPE-HPLC-MS/MS)建立了地表水中25种抗生素类药物和8种非抗生素类药物的分析方法。通过重点优化质谱参数、色谱条件、样品pH、洗脱溶剂组成及用量等确定了最佳分析条件。水样经过滤、固相萃取柱富集净化后,选择Shim-pack XR-ODS为色谱柱,以乙腈和0.2%甲酸-2 mmol/L乙酸铵-水溶液为流动相进行梯度洗脱,采用电喷雾电离源,在多反应监测模式下(MRM)分析测定,内标法定量。33种药物的仪器定量限为0.012～4.68 ng/L,方法检出限为0.011～7.60 ng/L,地表水加标回收率为53.7%～122%,相对标准偏差为1.22%～32.1%(n=6)。方法成功应用于北京市凉水河12个地表水样分析,共检出32种药物,检出质量浓度为未检出～239 ng/L。利托那韦(RTV)作为新型冠状病毒诊疗方案中推荐的药物在凉水河检出率为100%。     

Industrial effluent quality, pollution monitoring and environmental management

Royal Commission Environmental Control Department (RC-ECD) at Yanbu industrial city in Kingdom of Saudi Arabia has established a well-defined monitoring program to control the pollution from industrial effluents. The quality of effluent from each facility is monitored round the clock. Different strategic measures have been taken by the RC-ECD to implement the zero discharge policy of RC. Industries are required to pre-treat the effluent to conform pretreatment standards before discharging to central biological treatment plant. Industries are not allowed to discharge any treated or untreated effluent in open channels. After treatment, reclaimed water must have to comply with direct discharge standards before discharge to the sea. Data of industrial wastewater collected from five major industries and central industrial wastewater treatment plant (IWTP) is summarized in this report. During 5-year period, 3,705 samples were collected and analyzed for 43,436 parameters. There were 1,377 violations from pretreatment standards from all the industries. Overall violation percentage was 3.17%. Maximum violations were recorded from one of the petrochemical plants. The results show no significant pollution due to heavy metals. Almost all heavy metals were within RC pretreatment standards. High COD and TOC indicates that major pollution was due to hydrocarbons. Typical compounds identified by GC-MS were branched alkanes, branched alkenes, aliphatic ketones, substituted thiophenes, substituted phenols, aromatics and aromatic alcohols. Quality of treated water was also in compliance with RC direct discharge standards. In order to achieve the zero discharge goal, further studies and measures are in progress.     

Monitoring of the ecotoxicological hazard potential by polar organic micropollutants in sewage treatment plants and surface waters using a mode-of-action based test battery

We propose and evaluate a mode-of-action based test battery of low-complexity and in-vitro bioassays that can be used as a routine monitoring tool for sewage treatment efficiency and water quality assessment. The test battery comprises five bioassays covering five different modes of toxic action. The bioluminescence inhibition test with Vibrio fischeri and a growth rate inhibition test with the green algae Pseudokirchneriella subcapitata are measures of non-specific integrative effects. A second endpoint in the algae test, the specific inhibition of the efficiency of photosynthesis, gives an account of the presence of herbicides. An enzymatic assay covers an important aspect of insecticidal activity, the inhibition of the acetylcholine esterase activity. Estrogenic effects are assessed with the yeast estrogen screen (YES) and genotoxicity with the umuC test. Three field studies, each lasting six to seven consecutive days, were undertaken at a sewage treatment plant (STP) in Switzerland. Samples were collected in summer and late autumn, under dry and rainy conditions. None of the bioassays gave positive results with raw water in whole effluent toxicity testing. Therefore, water samples from various sites during wastewater treatment and from surface water were enriched with solid-phase extraction. The focus was on non-volatile compounds of average to moderate hydrophobicity, a range that includes most pesticides, biocides and pharmaceuticals. Various polar solid phases were evaluated for their extraction efficiency, disturbance by matrix components and overall performance. We finally selected a mixture of a polymeric sorbent and a C18-sorbent, Lichrolut EN and RP-18 or, alternatively, Empore SDB-RPS disks. All bioassays gave clear and robust responses with the SPE extracts. With the bioassay data the treatment efficiency of the STP can be assessed with respect to different modes of toxic action and accordingly different groups of micropollutants. Furthermore, the data allowed for a comparison between the effluent and the receiving river. In all bioassays the primary effluent had a strong effect and this effect was reduced after passing the STP. Treatment efficiency was high (typically over 90%) but varied from bioassay to bioassay, which is expected because each bioassay detects different types of micropollutants and therefore we cannot expect a common answer.     

An examination of the toxic properties of water extracts in the vicinity of an oil sand extraction site

The industrial extraction of oil sands (OS) in northern Alberta, Canada, has raised concerns about the quality of the Athabasca River. The purpose of this study was to examine the toxic properties of various water extracts on Oncorhynchus mykiss trout hepatocytes. The water samples were fractionated on a reverse-phase C(18) cartridge and the levels of light-, medium- and heavy-weight polycyclic aromatic hydrocarbons (PAHs) were determined by fluorescence spectroscopy. Primary cultures of trout hepatocytes were exposed for 48 h at 15 °C to increasing concentrations of the C(18) extract corresponding to 0.02, 0.1, 0.5 and 2.5X concentrations from upstream/downstream sites in the Athabasca River, lake and groundwater samples, OS tailings and interceptor well-water samples. Changes in cell viability, phase I and phase II biotransformation enzymes (cytochrome P4501A and glutathione S-transferase activities), oxidative damage (lipid peroxidation LPO) and genotoxicity (single and double DNA strand breaks) were monitored in post-exposure cells. The water samples decreased cell viability and increased all the above endpoints at thresholds of between 0.02 and 0.1X the water concentration. The most responsive biomarker was DNA damage but it also offered the least discrimination among sites. LPO was higher at sites downstream of the industrial operations compared to upstream sites. A decision tree analysis was performed to formulate a set of rules by which to identify the distinctive properties of each type of water samples. The analysis revealed that OS tailings and interceptor waters were characterized by an increased concentration in light PAHs (>42 μg L(-1)) and this fraction represented more than 85% of the total PAHs. These samples also inhibited GST activity, which could compromise the elimination of genotoxic PAHs present in the system. An analysis of groundwater samples revealed a contamination pattern similar to that for OS tailings. There is a need for more research into specific biomarkers of toxicity from OS tailings compounds such as naphthenic acids, light PAHs among others, which are a characteristic fingerprint of OS extraction activities.     

Impact of wastewater treatment plant discharge of lidocaine, tramadol, venlafaxine and their metabolites on the quality of surface waters and groundwater

The presence of the anesthetic lidocaine (LDC), the analgesic tramadol (TRA), the antidepressant venlafaxine (VEN) and the metabolites O-desmethyltramadol (ODT) and O-desmethylvenlafaxine (ODV) was investigated in wastewater treatment plant (WWTP) effluents, in surface waters and in groundwater. The analytes were detected in all effluent samples and in only 64% of the surface water samples. The mean concentrations of the analytes in effluent samples from WWTPs with wastewater from only households and hospitals were 107 (LDC), 757 (TRA), 122 (ODT), 160 (VEN) and 637 ng L(-1) (ODV), while the mean concentrations in effluents from WWTPs treating additionally wastewater from pharmaceutical industries as indirect dischargers were for some pharmaceuticals clearly higher. WWTP effluents were identified as important sources of the analyzed pharmaceuticals and their metabolites in surface waters. The concentrations of the compounds found in surface waters ranged from 相似文献   

Solid-phase extraction followed by liquid chromatography-time-of-flight-mass spectrometry to evaluate pharmaceuticals in effluents. A pilot monitoring study

The present work provides a multi-residue analytical method for determining a selection of 20 pharmaceuticals from diverse therapeutical classes in hospital effluent wastewater. The method is based on the simultaneous extraction of the target compounds by solid phase extraction (SPE), followed by liquid chromatography-time-of-flight-mass spectrometry (LC-TOF-MS) analysis. Using TOF-MS, accurate mass measurements within 2 ppm error were obtained for most of the pharmaceuticals studied. Empirical formula information can be obtained by this method, allowing the unequivocal identification of the target compounds in the samples. Validation studies showed that LC-TOF-MS analysis is a valuable new tool for identification and quantification of pharmaceuticals in wastewater. Recoveries, using Oasis HLB cartridges at pH 7, were higher than 75% for all pharmaceuticals, except for ranitidine, 4-methylaminoantipyrine (4-MAA), cefotaxime and omeprazole, which needed specific pH conditions for their extraction. Linearity of response over two orders of magnitude was demonstrated (r > 0.99). Matrix effects resulting in suppression of the response were observed. For most of the compounds ion suppression was less than 39%, except for metronidazole, carbamazepine 10,11-epoxide, naproxen and erythromycin, where the signal suppression was 42%, 59%, 46% and 95%, respectively. A simple and effective approach to minimize or avoid matrix interferences was the 1 : 4 dilution of the SPE extracts. Method detection limits (MDLs) and quantification limits (MQLs) ranged between 4-115 ng l(-1) and 14-384 ng l(-1), respectively. The precision of the method, calculated as relative standard deviation (RSD), ranged from 1.1-19.8% and 1.7-21.7% for intra- and inter-day, respectively. The developed analytical method was applied to the analysis of hospital effluent wastewater during a survey study. 18 of the 20 pharmaceuticals studied were detected at concentration levels of microg l(-1), reaching in some cases concentrations over 100 microg l(-1), and in the case of the analgesic and antipyretic dipyrone metabolite, higher than 1000 microg l(-1).     

The impact of land use and season on the riverine transport of mercury into the marine coastal zone

In Mediterranean seas and coastal zones, rivers can be the main source of mercury (Hg). Catchment management therefore affects the load of Hg reaching the sea with surface runoff. The major freshwater inflows to the Baltic Sea consist of large rivers. However, their systems are complex and identification of factors affecting the outflow of Hg from its catchments is difficult. For this reason, a study into the impact of watershed land use and season on mercury biogeochemistry and transport in rivers was performed along two small rivers which may be considered typical of the southern Baltic region. Neither of these rivers are currently impacted by industrial effluents, thus allowing assessment of the influence of catchment terrain and season on Hg geochemistry. The study was performed between June 2008 and May 2009 at 13 sampling points situated at different terrain types within the catchments (forest, wetland, agriculture and urban). Hg analyses were conducted by CVAFS. Arable land erosion was found to be an important source of Hg to the aquatic system, similar to urban areas. Furthermore, inflows of untreated storm water discharge resulted in a fivefold increase of Hg concentration in the rivers. The highest Hg concentration in the urban runoff was observed with the greatest amount of precipitation during summer. Moderate rainfalls enhance the inflow of bioavailable dissolved mercury into water bodies. Despite the lack of industrial effluents entering the rivers directly, the sub-catchments with anthropogenic land use were important sources of Hg in the rivers. This was caused by elution of metal, deposited in soils over the past decades, into the rivers. The obtained results are especially important in the light of recent environmental conscience regulations, enforcing the decrease of pollution by Baltic countries.     

石油化工废水中有机组分剖析

采用二氯甲烷液—液萃取预处理水样，气相色谱—质谱联用技术分析了炼油厂生化曝气池进、出水，腈纶厂干法纺丝废水及其经ＳＢＲ小试处理的出水中二氯甲烷可萃取的有机组分，并半定量地评估了生化处理对这些有机组分的去除效果。结果表明，炼油厂生化曝气池对酚类及芳烃类化合物的去除效果较好，而长链脂肪烃的去除率相对较低；腈纶干法纺丝工艺废水中可萃取的有机组分主要为Ｎ，Ｎ二甲基甲酰胺，其相对含量大于９５％（ｍ／ｍ），该废水经ＳＢＲ小试处理后，原水中各种可萃取的有机化合物均得到分解，结构发生了变化，但不能全部彻底地转化为ＣＯ２和水。     

固相萃取-高效液相色谱法测定水中氯酚类化合物

采用固相萃取-高效液相色谱法测定水中7种氯酚类化合物,Waters OASIS WAX柱萃取效率最高,最佳萃取时间和洗脱时间分别为60和5 min。该法的线性范围为1.0~40 mg/L,检出限为0.015~0.5μg/L,精密度为0.558%~2.22%,回收率为83.2%~105%。该法适用于地表水及饮用水中氯酚类化合物的检测。     

Monitoring of trace metals and pharmaceuticals as anthropogenic and socio-economic indicators of urban and industrial impact on surface waters

The research focuses on the monitoring of trace metals and pharmaceuticals as potential anthropogenic indicators of industrial and urban influences on surface water. This study includes analysis of tracers use for the indication of water pollution events and discussion of the detection method of these chemicals. The following criteria were proposed for the evaluation of indicators: specificity (physical chemical properties), variability (spatial and temporal), and practicality (capacity of the sampling and analytical techniques). The combination of grab and passive water sampling (i.e., diffusive gradient in the thin film and polar organic chemical integrated samplers) procedure was applied for the determination of dissolved and labile trace metals (Ag, Cd, Cr, Cu, Ni, Pb, and Zn) and pharmaceuticals (carbamazepine, diazepam, paracetamol, caffeine, diclofenac, and ketoprofen). Samples were analyzed using inductively coupled plasma mass spectrometry (MS; trace metals) and liquid chromatography–tandem MS electrospray ionization+/? (pharmaceuticals). Our results demonstrate the distinctive spatial and temporal patterns of trace elements distribution along an urban watercourse. Accordingly, two general groups of trace metals have been discriminated: “stable” (Cd and Cr) and “time varying” (Cu, Zn, Ni, and Pb). The relationship Cd???Cu?>?Ag?>?Cr?≥?Zn was proposed as an anthropogenic signature of the industrial and urban activities pressuring the environment from point sources (municipal wastewaters) and the group Pb–Ni was discussed as a relevant fingerprint of the economic activity (industry and transport) mainly from non-point sources (runoff, atmospheric depositions, etc.). Pharmaceuticals with contrasting hydro-chemical properties of molecules (water solubility, bioaccumulation, persistence during wastewater treatment processes) were discriminated on conservative, labile, and with combined properties in order to provide information on wastewater treatment plant efficiency, punctual events (e.g., accidents on sewage works, runoff), and uncontrolled discharges. Applying mass balance modeling, medicaments were described as relevant socio-economic indicators, which can give a picture of main social aspects of the region.     

Phenolic water pollutants in a Malaysian River basin

Phenolic chemicals with their very low taste and odour thresholds, high persistence and toxicity, are of growing concern as water pollutants. The compounds are known to exist in raw water as well as in treated water. The level of phenolic priority pollutants in water within the catchment area of the Linggi River Treatment Plant in Negeri Sembilan, Malaysia, which includes the Linggi river basin, was monitored. The 4-aminoantipyrin colourimetric method was used to determine total phenols whereas capillary column gas chromatography was used to determine the individual compounds. The results show that at most sampling stations, particularly those within the Seremban municipality, the level of phenols was found to exceed the recommended Malaysian standard of 2.0 g/L^-1 for raw water. This is seen as the direct impact of industrial and urbanization of the area and clearly indicates the unhealthy state of the Linggi river. The results also indicate the need to improve the water quality if the river is going to be used as a source of raw water.     

中国沿海三省主要饮用水源有机物监测

采用固相萃取、吹扫捕集和气相色谱-质谱联用仪(GC-MS)对江苏、浙江、山东省的21个主要地表饮用水源、126份水样中的25种VOCs、38种SVOCs进行定量检测。结果有19种VOCs、10种SVOCs至少在一个水源地多次被检出,其中挥发性氯代烃、苯系物、氯代苯类、酚类、硝基苯类、酞酸酯类、农药为中国或美国环境保护局提出的"水中优先控制污染物",最高检出量为27.79μg/L。三省主要地表水受到有机物轻度污染,水体中VOCs、SVOCs含量尚未超过《地表水环境质量标准》(GB 3838-2002)和《生活饮用水卫生标准》(GB 5749-2006)限值,工业废水排放及农田雨水径流是地表水有机物的重要来源。     

Assessment of priority phenolic compounds in sediments from an extremely polluted coastal wetland (Lake Maryut, Egypt)

Although high concentrations of trace organic pollutants were recorded along the Egyptian Mediterranean Coast and its corresponding coastal wetlands, no published data are available for the levels of phenolic compounds. Thus, this work aimed to investigate the levels of phenolic compounds in sediments of a heavily polluted coastal wetland (Lake Maryut, Egypt). For that purpose, a method was optimized for the extraction and detection of chlorophenols, methylphenols, and nitrophenols in sediments using GC-MS. Sediments were extracted with 0.1 M NaOH/methanol by sonication. Cleanup of sediment extracts using liquid–liquid extraction and SPE was found important to remove most of the interfering co-extracts. The proposed analytical methodology was validated by analysis of matrix spikes. Detection limits were 0.063–0.694 μg/kg dw for sediments. Good recoveries (70–110%) and precision values (RSD?<?20%) were obtained from the fortification experiments at the parts per billion level in sediments. The method was applied to investigate the level of contamination with phenols in 19 sediment samples from Lake Maryut. Results revealed that higher concentrations were observed in the main basin (MB) of Lake Maryut affected by the discharge of effluents from a primary wastewater treatment plant, direct discharge of industrial effluents, domestic wastes, and agricultural effluents from Qalaa Drain (QD). Chlorophenols (CPs) were the major group detected in the lake sediments followed by methylphenols (MPs) and nitrophenols (NPs). CPs were dominated by 2-, 4-, and 3-chlorophenols. Concentrations of CPs were higher at the north and northwestern parts of the MB indicating the influence of industrial effluents discharged into the lake. On the other hand, higher concentrations of NPs were observed at the south and southwestern parts of the MB, which is subjected to the discharge of agricultural and domestic effluents via QD. Results of the risk assessment revealed that phenol, cresols, 2,4-dinitrophenol, 4-NP, 2-CP, 2,3,4,6-tetrachlorophenol and 2,4-dimethylphenol are contaminants of concern and that adverse ecological effects could possibly occur to benthic species from the exposure to these pollutants in Lake Maryut and thus phenols should be included in monitoring and pollution prevention programs in the Egyptian aquatic environment affected by anthropogenic activities.     

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.     

Tracking sewage derived contamination in riverine settings by analysis of synthetic surfactants

A study has been made of the presence and reactivity of the most commonly used surfactants, both anionic (linear alkylbenzene sulfonates, LAS, and alkyl ethoxysulfates, AES) and non-ionic (alcohol polyethoxylates, AEOs, and nonylphenol polyethoxylates, NPEOs), in water and surface sediments from the middle stretch of the Guadalete River in SW Spain (12 stations). Average values were between 0.1 and 3.7 mg kg(-1) in sediment, and between 0.2 and 37 μg L(-1) in water. The sorption of surfactants was dominated by hydrophobic mechanisms, so those homologues having longer alkyl chains (e.g. C(18)AEO) showed higher relative percentages and concentrations in sediments compared with water. Local and sharply higher concentrations of these compounds were observed at three sampling stations (7, 9 and 12), indicating the occurrence of wastewater discharges into the river. By analysing the distributions of different surfactant homologues and their metabolites we were able to distinguish between sewage contamination from sources discharging treated and untreated wastewaters. Upstream (stations 1-2), LAS concentrations were below 30 μg L(-1) and the composition of their degradation intermediates (sulfophenyl carboxylic acids, SPCs) (160 μg L(-1)) was dominated by short-chain homologues (C(6)-C(9)SPCs), indicating that the degradation of this surfactant is at an advanced stage. The highest concentration (487 μg L(-1)) of SPCs was detected near the effluent outlet of a sewage treatment plant (STP) (station 12). Sampling stations (7 and 9) affected by untreated wastewater discharges were the only ones showing the presence of the most reactive and biodegradable SPC isomers and homologues (e.g. C(11)SPC). Here, LAS reached the highest concentration values measured (>2 mg L(-1)), and showed a homologue distribution closer to that of commercial mixtures than LAS found at the other stations.     

乙腈盐析萃取HPLC-PDA同时测定水中11种苯胺类化合物

通过对色谱分析和样品萃取条件的选择和优化，建立了同时分析水中11种苯胺类化合物的HPLC方法。样品经乙腈盐析萃取后直接进样分析，采用 ODS色谱柱，以乙腈-水为流动相进行梯度洗脱，用PDA检测。结果表明，11种苯胺类化合物在0.20~100mg/L范围内其浓度和检测信号呈良好的线性关系，方法检出限为0.002~0.007mg/L，地表水和废水样品加标回收率为81.6%~97.4%，相对标准偏差为1.5%~5.5%。