再生水中消毒副产物——卤乙酸的测定方法研究

参照美国国家环保局(USEPA)推荐的饮用水卤乙酸类消毒副产物测定方法(Method 552.3),通过优化该方法的预处理条件和改变检测方法,提出了酸化萃取-衍生化-中和萃取-GC-MS测定再生水中卤乙酸含量的分析方法,并分析了北方某市再生水中4种卤乙酸类消毒副产物含量。结果表明,该方法适用于我国再生水水质,能够有效地消除再生水中共存污染物的干扰;其相对标准偏差(n=7)小于10%,方法的精密度较好;检出限与USEPA方法基本一致;样品加标回收率满足USEPA 6251B标准方法中(100±30)%要求;再生水中的卤乙酸比自来水高出几十倍,对环境和人类存在一定的潜在危害。     

Solid phase extraction with pyrenebutyric acid-bonded silica for analysis of polychlorinated biphenyls in sewage water by gas chromatography-mass spectrometry

A solid phase extraction (SPE) method using pyrenebutyric acid-bonded silica (PYB) as sorbent was developed to determine 23 polychlorinated biphenyls (PCBs) in sewage water by gas chromatography-mass spectrometry (GC-MS). Factors were optimized in SPE procedures including elution solvent, pH, and cartridge burden. The recoveries of 23 PCB congeners were 69.44-111.91% under optimized conditions. Comparisons were also conducted among PYB-SPE, C(18)-SPE and United States Environmental Protection Agency 608 (USEPA608) methods in the analysis of PCBs in sewage water samples. The results showed that the performance of PYB-SPE method was similar with USEPA608 method and better than C(18)-SPE method. Both PYB-SPE and USEPA608 methods were then employed to analyze PCBs in real spiked sewage water samples. The recoveries of PCB congeners determined by PYB-SPE method ranged from 70.6% to 92.4% in real spiked sewage water samples which were identified to be in accordance with USEPA608 method. Limits of detection (LOD) were in the range of 0.06-0.22ngL(-1) for PCB congeners. The optimized PYB-SPE method was successfully applied to the determination of PCBs in sewage water samples.     

城市生活污水及二级处理水中手足口病病毒及肠道病毒的赋存状态

手足口病是由多种肠道病毒引起的传染病,其主要病原体有EV71、CVA16及CVA10。为了研究污水处理厂的生活原污水及二级处理水中此类病毒的存活情况,实验利用手足口病3种主要病毒的通用引物对其进行分型检测,同时使用肠道病毒通用引物检测所有肠道病毒,并对常规水质指标进行分析。结果表明,原污水及二级处理水的手足口病病毒阳性率分别为83.3%与36.7%,而肠道病毒阳性率更高达100%及93.3%。说明生活污水中的肠道病毒可以稳定存在,且若未进行有效消毒处理,可能存在于二级处理水中。在3种手足口病主要病毒中,CVA10检出率最高,达45.0%,CVA16及EV71检出率分别为8.3%及10.0%。可推断,CVA10为实验阶段该地区主要的手足口病病毒。通过相关性分析,肠道病毒的存活与水质条件密切相关。     

Biological and chemical tools in the toxicological risk assessment of Jarama River, Madrid, Spain

Four river water samples (R) and three sewage samples (S) were collected at different points in the Jarama River, Spain. Organic concentrates were tested on the RTG-2 in vitro cytotoxicity test and analyzed by HPLC and GC/MS. The cytotoxicity assessment demonstrated a progressive increase in the toxicity of the river water when moving downstream. A wide range, from slightly harmful to highly toxic, was observed for sewage samples. The most toxic samples produced decreases of 95% to 100% in the ATP content, cell viability and cell detachment (a parameter to estimate mortality). The most toxic organic concentrates (the sewage from an urban + industrial effluent collected in Paracuellos, Madrid, Spain, and the river 100 m downstream from the discharge of this effluent) were fractioned by an HPLC system. Each chromatographic peak was collected as a fraction of the whole concentrate. The cytotoxicity of each fraction was also assessed on RTG-2 cells. A toxic peak with a retention time of 38.3 min was detected in both samples; this time belongs to the PAHs retention time interval under our chromatographic conditions. Analytical procedures identified fluorene (0.62 microg/l) and benz(a)anthracene (0.44 microg/l) in the sewage and anthracene (0.40 microg/l) and benz(a)anthracene (0.14 microg/l) in the river water. However, the observed cytotoxicity could not be explained by the PAH concentrations. Five additional toxic peaks were observed in each sample. Results suggest that the combination of HPLC with cost-effective toxicity tests produces a useful tool to define environmental management decisions when the chemical analysis cannot identify the substances responsible for the environmental risk.     

Novel polymer monolith microextraction using a poly-(methyl methacrylate-co-ethylene dimethacrylate) monolith and its application to the determination of polychlorinated biphenyls in water samples

A novel and simple method based on polymer monolith microextraction (PMME) coupled to gas chromatography with electron-capture detection (GC-ECD) was developed for the determination of six polychlorinated biphenyls (PCBs) residues in water samples. The proposed method used poly-(methyl methacrylate-co-ethylene dimethacrylate) (MMA-co-EDMA) monolith as extraction media. Several factors affecting experiments such as sample flow rate, sample volume, the type of eluent, eluent volume, eluent flow rate, effect of salt addition and carry over effect were investigated and optimized systematically. The limits of detection (LODs) for six PCBs were 0.028-0.043 ng mL⁻¹ in water samples. The intra-day and inter-day precisions (R.S.D.) were less than 9.2% and 9.6%, respectively. The proposed method was successfully applied to the determination of six PCBs in tap water, lake water and industrial waste water and the trueness has been evaluated by recovery experiments. The obtained relative recoveries were in the range of 63.3-105.6%.     

Fast extraction of polychlorinated dibenzo-p-dioxin and polychlorinated dibenzofuran in sewage sludge and soil samples

The current environmental legislations recommend monitoring chemical contaminants such as polychlorinated dibenzo-p-dioxins and polychlorinated dibenzofurans before the use of sewage sludge on the agricultural land. In this study, a solid–liquid extraction with low-temperature purification (SLE-LTP) was optimized and validated to determine 2,3,7,8-tetrachlorodibenzo-p-dioxin and 2,3,7,8-tetrachlorodibenzofuran in sewage sludge and soil samples. The analyses were performed by gas chromatography-mass spectrometry operating in the selective ion mode (GC-MS-SIM). Acetonitrile:ethyl acetate 6.5:1.5 (v/v) was the best extraction phase, and the recoveries percentages were close to 100%. The linearity was demonstrated in the range of 1.25–25 µg L^?1 of 1.25–20 µg L^?1 for sewage sludge and soil, respectively. Matrix effect was proved for the two compounds and in the two matrices studied. Extraction percentages were between 78 and 109% and relative standard deviations ≤ 19%. The proposed method is faster than methods described in the literature because showed a few steps. The quantification limits (LOQ) in sewage sludge were 6.4 and 32 ng TEQ kg^?1 for 2,3,7,8-TCDF and 2,3,7,8-TCDD, respectively. In soil, LOQs were 0.8 and 8.0 ng TEQ kg^?1 for 2,3,7,8-TCDF and 2,3,7,8-TCDD, respectively. These values are lower than the maximum residue limits established by European Legislation. The method was applied to 22 agricultural soil samples from different Brazilian cities and 2,3,7,8-TCDF was detected in one of these samples.     

Determination of antibiotic compounds in water by on-line SPE-LC/MSD

This study attempts to provide an improved approach for the analysis of antibiotics, which normally exist at low concentration in complex matrices such as receiving streams of wastewater treatment plant discharge. The analytical method developed in this study combines an existing pretreatment technique of solid-phase extraction (SPE) with liquid chromatography mass spectrometry (LC/MSD) through on-line connection. The on-line connection suppressed the target loss by keeping the cartridge from drying, which resulted in improvement of the recovery and saving of the analytical time. For the on-line solid-phase extraction of 10 ml water samples, recoveries were between 74.3% and 116.5% and average LOQ was 0.11 microg l(-1) for the sulfonamide antibiotics (SA) and 0.09 microg l(-1) for the tetracycline antibiotics (TA). Application of the developed method for the analysis of fourteen antibiotics revealed that several antibiotics were detected at concentrations above the LOQ in ARW. Treated and untreated sewage and agricultural wastewater were mostly responsible for the antibiotics contamination of the river. Antibiotics were detected at much higher concentrations in the agricultural wastewater sample than in the sewage sample, implying substantial use of antibiotics in the agricultural industry. Wastewater treatment was generally effective in separation of the antibiotics tested in this study. The extent of the treatment depended on the type of antibiotics. Hydrophobic antibiotics were more effectively separated from the solution than hydrophilic antibiotics.     

固相微萃取-气相色谱法测定饮用水及其水源水中的氯酚

利用固相微萃取(SPME)-气相色谱法(GC)联用技术测定饮用水及其水源水中的氯酚．优化萃取温度、萃取平衡时间、酸度、离子强度等实验条件．所建方法简便、精确,自来水和太湖水中均检测到氯酚。     

Studies on thio-substituted polyurethane foam (T-PUF) as a new efficient separation medium for the removal of inorganic/organic mercury from industrial effluents and solid wastes

Novel thio-substituted flexible polyurethane foam (T-PUF) was synthesised by addition polymerisation of mercaptan with the precursors of an open-cell polyurethane foam, which can be used as a highly selective sorbent for inorganic and organic mercury from complex matrices. The percentage extraction of inorganic mercury was studied at different flow-rates, over a wide pH range at different concentrations ranging from 1 ppm, to 100 ppm. The break-through capacity and total capacity of unmodified and thio-foams were determined for inorganic and organic mercurials. The absorption efficiency of thio-foam was far superior to other sorbent media, such as activated carbon, polymeric ion-exchange resins and reagent-loaded polyurethane foams. It was observed that even at the 1000 ppm level, divalent ions like Cu, Mg, Ca, Zn do not appreciably influence the per cent extraction of inorganic mercury at the 10 ppm level. These matrix levels are the most concentrated ones which are likely to occur, both in local sewage and effluent waters. Further, the efficiency of this foam was sufficiently high at 10-100 ppm levels of Hg, even from 5-10 litres of effluent volumes using 50 g of thio-foam packed into different columns in series. Thio-foams were found to possess excellent abilities to remove and recover mercury even at low levels from industrial effluents and brine mud of chlor-alkali industry after pre-acid extraction. This makes it a highly efficient sorbent for possible application in effluent treatment. Model schemes for the removal and recovery of mercury from industrial effluents and municipal sewage (100-1000 litre) by a dynamic method are proposed and the costs incurred in a full-scale application method are indicated to show that the use of thio-foam could be commercially attractive.     

An ultrasonic assisted extraction method to release heavy metals from untreated sewage sludge samples

A rapid ultrasound accelerated sequential extraction procedure has been used to develop sequential extraction proposed by BCR protocol (the community Bureau of Reference now the European Union "Measurement and Testing Programme"). The effects of the ultrasonic treatment on the extraction of Cu, Cd, Cr, Pb, Ni and Zn from untreated sewage sludge collected from industrial site of Hyderabad city (Pakistan) were compared with those obtained from conventional sequentional extraction procedure of modified BCR protocol. In BCR method, each extraction steps takes 10h, where as with the use of compromise sonication conditions in ultrasonic bath, steps 1-3 of the sequential extraction (excluding the hydrogen peroxide digestion in step 3, which was not performed with sonication) could be completed in 30, 30 and 30 min, respectively. Extractable Cd, Cr, Pb and Ni contents were obtained by both comparable methodologies were measured by electrothermal atomic absorption spectrometry (ETAAS), while for Cu and Zn Flame atomic absorption spectrometry (FAAS) was used. The validations of both methods were compared by the analysis of certified reference material of soil amended with sewage sludge (BCR 483). According to statistical evaluation of the results, the proposed accelerated extraction method is valid alternative to conventional shaking with much shorter extraction time with p value <0.05. The overall metal recoveries in steps 1-3 (excluding residual step) were 95-100% of those obtained with the conventional BCR protocol, except for Cu extracted (91.6%) as related to indicative values of Cu in BCR 483 obtained in 1-3 steps. The results of the partitioning study of untreated industrial waste water sewage sludge, indicate that more easily mobilized forms (acid exchangeable) were predominant for Cd and Zn, in contrast, the largest amount of Pb and Cr was associated with the iron/manganese oxide and organic matter/sulphide fractions.     

Determination of trace triazine and chloroacetamide herbicides in tile-fed drainage ditch water using solid-phase microextraction coupled with GC-MS

Solid-phase microextraction coupled with gas chromatography-mass spectrometry (SPME-GC-MS) was used to analyze two triazine (atrazine and simazine) and three chloroacetamide herbicides (acetochlor, alachlor, and metolachlor) in water samples from a midwest US agricultural drainage ditch for two growing seasons. The effects of salt concentration, sample volume, extraction time, and injection time on extraction efficiency using a 100-mum polydimethylsiloxane-coated fiber were investigated. By optimizing these parameters, ditch water detection limits of 0.5 microgL(-1) simazine and 0.25 microgL(-1) atrazine, acetochlor, alachlor, and metolachlor were achieved. The optimum salt concentration was found to be 83% NaCl, while sample volume (10 or 20 mL) negligibly affected analyte peak areas. The optimum extraction time was 40 min, and the optimum injection time was 15 min. Results indicated that atrazine levels in the ditch water exceeded the US maximum contaminant level for drinking water 12% of the time, and atrazine was the most frequently detected among studied analytes.     

Determination of phenols and pharmaceuticals in municipal wastewaters from Polish treatment plants by ultrasound-assisted emulsification–microextraction followed by GC–MS

A method combining ultrasound-assisted emulsification–microextraction (USAEME) with gas chromatography–mass spectrometry (GC–MS) was developed for simultaneous determination of four acidic pharmaceuticals, ibuprofen, naproxen, ketoprofen, and diclofenac, as well as four phenols, 4-octylphenol, 4-n-nonylphenol, bisphenol A, and triclosan in municipal wastewaters. Conditions of extraction and simultaneous derivatization were optimized with respect to such aspects as type and volume of extraction solvent, volume of derivatization reagent, kind and amount of buffering salt, location of the test tube in the ultrasonic bath, and extraction time. The average correlation coefficient of the calibration curves was 0.9946. The LOD/(LOQ) values in influent and effluent wastewater were in the range of 0.002–0.121/(0.005–0.403) μg L^?1 and 0.002–0.828/(0.006–2.758) μg L^?1, respectively. Quantitative recoveries (≥94 %) and satisfactory precision (average RSD 8.2 %) were obtained. The optimized USAEME/GC–MS method was applied for determination of the considered pharmaceuticals and phenols in influents and treated effluents from nine Polish municipal wastewater treatment plants. The average concentration of acidic pharmaceuticals in influent and effluent wastewater were in the range of 0.06–551.96 μg L^?1 and 0.01–22.61 μg L^?1, respectively, while for phenols were in the range of 0.03–102.54 μg L^?1 and 0.02–10.84 μg L^?1, respectively. The removal efficiencies of the target compounds during purification process were between 84 and 99 %.     

Pressurised liquid-liquid extraction. An approach to the removal of inorganic non-metal species from used industrial oils

Modified pressurised hot water is used for the development of a high pressure liquid-liquid extraction method for the decontamination of used industrial oils from inorganic non-metal species (chlorine, fluorine and sulphur). The oils were subjected to dynamic extraction with water modified with 5% v/v HNO3 at 200 degrees C as extractant. Under these working conditions the analytes were transferred to the aqueous phase. Spontaneous separation of the two immiscible liquid phases (the used oil and extract) takes place in the collection flask after extraction. The treated and untreated oil samples were oxidised and the chloride, fluoride and sulphate thus formed were determined by ion-chromatography. The method was applied to four oil samples from different locations in Spain. A residence time of approximately =10 min provided oil samples from which 88.3%, 89.4% and 89.4% of chloride, fluoride and sulphate, respectively, have been removed with respect to the initial concentration of each analyte in the oil. The repeatability, expressed as relative standard deviation (RSD), was of 11.9%, 13.7% and 7.2% for Cl(-), F(-) and SO4(2-), respectively; whilst the within-laboratory reproducibility yielded RSDs of 6.2%, 7.9% and 6.2% for the same analytes. The proposed approach has proved to be efficient, simple, easily transferable to industrial scale, cheap, fast and environmentally friendly.     

A level change in mutagenicity of Japanese tap water over the past 12 yr

A relative comparison study of mutagenicity in Japanese tap water was conducted for 1993 and 2005 surveys. It intended to assess the effects of advanced water treatment installations to water works, improvement of raw water quality and improvement of residual HOCl concentration controlling. Sampling points (taps) were the same in both surveys. The results of 245 samples obtained by the Ames Salmonella mutagenicity test (Ames test) were analyzed. The Ames tests were conducted by using Salmonella typhimurium TA98 and TA100 strains with and without exogenous activation (S9). With the exception of TA100-S9, the other conditions needed no discussion as a factor in the mutagenicity level change. The average mutagenicity in 1993 and 2005 under the conditions of TA100-S9 were 2600 and 1100 net revertant L⁻¹, respectively. This indicated that the mutagenicity level of Japanese tap water decreased during the 12-yr period. Particularly a remarkable decrease in mutagenicity was observed in the water works where the advanced water treatments were installed during the 12-yr period. The advanced water treatments were effective in decreasing the mutagenicity of tap water. Mutagenicity also decreased in the water works with conventional water treatments; the improvement of residual HOCl concentration controlling was also considered to be effective in decreasing the mutagenicity of tap water.     

Occurrence of polycyclic aromatic hydrocarbons in sewage sludge and their contribution to its toxicity in the toxalert 100 bioassay.

The contribution of polycyclic aromatic hydrocarbons (PAH) present in sewage sludge samples to toxicity was investigated. Chemical analysis using gas chromatography mass spectrometry (GC-MS) and the ToxAlert 100 bioassay, based on the inhibition to Vibrio fischeri, were applied to sludge extracts after purification by column chromatography. The levels of the 16 US EPA PAH analyzed in the sewage sludge samples varied from 17 to 2,030 microg kg(-1). In all samples examined phenanthrene was the most prominent compound. The toxicity data obtained by ToxAlert 100 can be explained by the levels and composition of the different PAH in sewage sludge samples. The present approach can contribute to evaluate the toxicity of sewage sludge.     

Effect of ozonization in degradation of trifluralin residues in aqueous and food matrices

Abstract

This study investigates the oxidation of trifluralin residues during ozonation in aqueous and food matrices (tomato). Domestic ozonation equipment with average production of 23.9?mg O₃ L^?1 h^?1 was used in the tests. Modern chromatographic systems (SPME-GC-IT/MS/MS and QuEChERS-GC-IT/MS/MS) were applied for extraction and detection of trifluralin residue in fortified samples of ultrapure water, tap water, superficial water and tomato fruit. The samples were submitted to the ozonation process during 0, 5, 10 and 20?min. Treatment at 5?min was able to degrade 71.5% of herbicide trifluralin in surface water. The removal (%) in ultrapure water reached 83.4% after 20?min of ozonation. The degradation of trifluralin in fortified tomato samples (0.025–0.1?mg kg^?1) were conducted with ozonation at 20?min, and it ranged from 84.4 to 92.7%. After treatment, levels of trifluralin in tomato remained within the established MRLs to EU, USEPA and ANVISA (Brazil). The data provided evidence that ozone is effective for removing trace trifluralin from water and foods.     

中国部分城市污泥中矿质元素形态与生物可利用性研究

近年来随着城市污水处理厂数目迅速增加,低成本、高效率的污泥农用受到越来越多的关注。研究从北到南的五家污水处理厂消化污泥中矿质元素的含量和形态分布,为污泥资源化的合理利用提供科学参考。结果表明：消化污泥总体呈高有机质、高氮磷、低K、高矿质元素营养的相似性,但其理化性质如阳离子交换容量(CEC)、pH等差异较大,对矿质元素的形态分布与生物可利用性有明显的影响。同种元素在不同污泥中含量的差异较大,相差数倍,甚至十倍以上。污泥中不同元素含量明显不同,Fe的浓度最高,次之是Mg、Zn、B的浓度最低。连续提取研究表明,污泥pH对污泥中矿质元素的形态分布有明显影响,酸性污泥(厦门污水处理厂)中各矿质元素酸溶／交换态百分率明显高于其他污泥。Cu主要分布在氧化态;Zn的三态分布百分率均在10％以上;Mg、Mn的酸溶／交换态含量较高;Fe主要分布在残渣态;B氧化态和还原态的百分率较高。建议在全国范围内进行一次污水处理厂污泥品质调查,为污泥合理农用提供科学依据。     

Development of an in-line system for the analysis of 4,4'-DDT in water

An in-line system for trace persistent organic pollutants (POPs) in water was developed by using a laboratory-made hollow fiber membrane (HFM) unit connected with a high-resolution gas chromatograph-mass spectrometer (HRGC-MS). The semivolatile organic compound, 4,4'-Dichlorodiphenyl trichloroethane (4,4'-DDT), was chosen as a representative of a persistent organic compound. The synthetic water contaminated with 4,4'-DDT was passed through the HFM unit, the extraction occurred by the analyte pervaporated and permeated, then stripped into HRGC-MS. Several factors were investigated for the high extraction efficiency. The best performance was obtained at sample and stripping gas flow rates of 6 and 9 mLmin-1, respectively, and desorption temperature of 60 degrees C. At this temperature, the diffusion rate was enhanced by 15 times over 25 degrees C. A wide linear dynamic range was obtained, i.e., 0.10-1.0 mgL-1, with a limit of detection (LOD) of 90 microgL-1. The extraction efficiency of 4,4'-DDT in real water samples was in the range of 83-94%. Real water samples were analyzed and 0.6 microgL-1 of 4,4'-DDT was found in unregistered bottled water and 7.0 microgL-1 in tap water.     

Polycyclic aromatic hydrocarbons in sewage,mussels and tap water

Polycyclic aromatic hydrocarbons (PAH) have been determined in sewage discharge, mussels and tap water by glass capillary gas chromatography. Up to 30 PAH compounds have been identified. The concentration levels are low, respectively 0.8 – 7.7μg/1, 0.5–1.1 μg/g and 0.002 – 0.2μg/1 of sum PAH have been determined in sewage discharge, mussels and tap water. The accumulation rate in mussels seems to be rather slow at the ambient water concentrations.     

Easy and fast extraction methods to determine organochlorine pesticides in sewage sludge,soil, and water samples based at low temperature

Organochlorine pesticides present in sewage sludge can contaminate soil and water when they are used as either fertilizer or agricultural soil conditioner. In this study, the technique solid–liquid extraction with low temperature purification was optimized and validated for determination of ten organochlorine pesticides in sewage sludge and soil samples. Liquid–liquid extraction with low temperature purification was also validated for the same compounds in water. Analyses were performed by gas chromatography-mass spectrometry operating in the selective ion monitoring mode. After optimization, the methods showed recoveries between 70% and 115% with relative standard deviation lower than 13% for all target analytes in the three matrices. The linearity was demonstrated in the range of 20 to 70 µg L^?1, 0.5 to 60 µg L^?1, and 3 to 13 µg L^?1, for sludge, soil, and acetonitrile, respectively. The limit of quantification ranged between 2 and 40 µg kg^?1, 1 and 6 µg kg^?1, and 0.5 µg L^?1 for sludge, soil, and water, respectively. The methods were used in the study of pesticide lixiviation carried out in a poly vinyl chlorine column filled with soil, which had its surface layer mixed with sludge. The results showed that pesticides are not leached into soil, part of them is adsorbed by the sewage sludge (4–40%), and most pesticides are lost by volatilization.