环境水体中三氟乙酸的存在现状及分析方法的研究

三氟乙酸是一种氟里昂替代品的大气降解产物 ,雨水会将其从空气中去除转移到水体中。三氟乙酸化学性质稳定 ,在自然环境中三氟乙酸易于积累在水体中 ,环境地表水中三氟乙酸浓度可达到 1 0～ 4 0 90 0 ng/L,雨水中 30～ 2 80 ng/L。目前 ,环境水体中关于三氟乙酸的分析方法有 :气相色谱法 ,离子色谱法 ,气相色谱质谱联用。根据各种灵敏度的要求 ,再结合各种不同的前处理方法 ,可对环境水体中三氟乙酸进行分析     

环境水系统中氯氟烃替代品降解产物TFA的测定

三氟乙酸为氯氟烃替代品的降解产物,对植物和土壤微生物群落的生长有一定抑制作用.建立测定TFA质量浓度的实验方法,将样品中的三氟乙酸与甲醇在硫酸溶液中衍生化为三氟乙酸甲酯(MTFA),利用三氟乙酸甲酯的易挥发性,以顶空进样进行富集浓缩.使用质谱定性手段确定出峰时间,再通过电子捕捉检测器ECD对实际样品进行分析.仪器检测限为30μg/L,方法检出限约为30ng/L,加标回收率60%～90%.     

太湖以西常州区域水体中典型PPCPs污染特征

为进一步了解环太湖区域药品及个人护理用品（PPCPs）环境污染现状,于2016年9月对太湖以西常州区域水体中典型PPCPs污染水平进行了调查。利用高效液相色谱-串联质谱（HPLC MS/MS）检测分析了24种PPCPs在常州区域水体中的赋存和空间分布特征。结果表明,常州区域水体中24种目标PPCPs均被检出,PPCPs质量浓度总量范围为51.08～325.79 ng/L,20个监测点位中,红凌桥检出PPCPs总量最高,达325.79 ng/L;水体中优势污染物为双酚A和诺氟沙星,双酚A在黄埝桥检出的质量浓度最高,达158.53 ng/L,其次是新河口和红凌桥,质量浓度分别为65.57和57.86 ng/L;诺氟沙星在红凌桥检出的质量浓度最高,达75.12 ng/L。喹诺酮类抗生素、磺胺类抗生素在常州流域内基本呈均匀分布;激素类、大环内酯抗生素、神经镇痛类和心脏病类药物质量浓度与人口密度大致呈正相关。     

中国北方地区水体中四环素族抗生素残留现状分析

为了更好了解北方市政污水等水体中四环素族抗生素残留现状,采用固相萃取方法对中国北方地区市政污水样品进行富集和净化,以高效液相色谱-串联质谱法分析样品中四环素族抗生素残留量。在调查的13个污水样品中四环素族抗生素普遍检出,且浓度分别达到四环素1114.27ng/L、土霉素2175.65ng/L、金霉素149.09ng/L和强力霉素187.45ng/L。结果表明,在我国近岸污水排放中依然有大量四环素类抗生素存在,应加强对近岸海洋环境中抗生素残留的监测与管理。     

鸭绿江水体中有机磷酸酯阻燃剂的浓度水平及污染特征

于2021年4月对鸭绿江干流及其主要支流水体中14种目标有机磷酸酯(OPEs)的浓度水平及污染特征进行了调查研究。结果表明,鸭绿江中∑OPEs的浓度从上游到下游逐渐升高,质量浓度为11.6~557.0 ng/L,平均质量浓度为202.5 ng/L,处于世界偏低,全国中下水平。鸭绿江水体中ρ(氯代OPEs)>ρ(烷基代OPEs)>ρ(芳基代OPEs)。14种OPEs中,磷酸三(1氯2丙基)酯(TCPP)质量浓度最高,其次是磷酸三(2氯乙基)酯(TCEP),平均占比分别为31.8%和20.9%。鸭绿江上游水体中OPEs的质量浓度为11.6~135.5 ng/L,平均值为52.8 ng/L,质量浓度最高的是烷基代OPEs;下游水体中OPEs的质量浓度为179.1~557.0 ng/L,平均值为382.3 ng/L,质量浓度最高的是氯代OPEs。上游水体中OPEs主要来源于大气沉降、径流携带等环境迁移,下游水体则主要受到丹东市区生活污水和沿江工业园区废水排放的影响。研究可为今后科学评估此类物质的环境风险并采取精准管控措施,提供数据支持和科学依据。     

电子垃圾回收地得克隆的污染水平及分布特征

对浙江某电子垃圾回收地水体、沉积物、土壤以及大气中得克隆（DP）的污染水平及分布特征进行了调查。结果表明，水、沉积物、土壤和大气样品中均检测出了 DP，分别为0．843～1．56 ng/L，0．185～7．03 ng/g干重，0．115～26．4 ng/g干重和11．2 pg/m3；该区域 DP分布特征表明电子垃圾的拆解和焚烧是环境中 DP的重要来源。     

固相萃取-电感耦合等离子体质谱测定自然水体痕量钍和铀

自然水体中Th和U的浓度极低，尤其Th的浓度单位仅为ng/L,定量测试非常困难。该研究建立了一种NOBIAS PA1螯合树脂萃取结合电感耦合等离子体质谱(ICP-MS)同时测定自然水体中痕量Th和U的分析方法。该方法首先使用UV/H₂O₂法消解水样30 min,去除水体中的有机物，然后在pH=3.00±0.05条件下，将水样以2 mL/min流速通过树脂对Th和U进行富集，使用NH₄AC-HAC溶液去除树脂上吸附的盐类，最后用1 mol/L超纯硝酸对样品进行洗脱，用ICP-MS测试。分析结果显示：Th和U的流程空白值分别为0.47、0.22 ng/L,检出限分别为2.9、2.3 ng/L,测定下限分别为11.46、9.11 ng/L。将该方法应用于不同有机物浓度的咸水和淡水中，结果显示：Th和U的回收率分别为97%～104%和98%～103%,相对标准偏差分别为3%～6%和1%～3%。说明该方法具有较高的回收率、精密度和准确度，适用于自然界各种不同水体中Th和U的定量分析。     

吹扫捕集-GC/MS-SIM法测定海水中挥发性有机污染物

采用吹扫捕集 -GC/MS -SIM法测定水中挥发性有机物 ,具有定量准确、操作简便等特点 ,检测限可达ng/L级 ,适合环境水中低浓度挥发性有机物的测定。测定实际海水样品 ,其浓度范围在 0 4ng/L～ 1 0 0 0ng/L之间。     

杭州贴沙河微囊藻毒素污染特征及健康风险评价

在2014年9月杭州贴沙河出现蓝藻异常增殖期间,利用固相萃取-液质联用法对水体中胞外微囊藻毒素(EMC)和总微囊藻毒素(TMC)进行监测。共检出以MC-LR为主的8种微囊藻毒素(MC)单体,TMC总的质量浓度为63.9 ng/L~1 090 ng/L,其中MC-LR质量浓度为31.6 ng/L~472 ng/L,毒性等效MC-LR浓度为51.8 ng/L~862 ng/L,检出的MC-LR浓度值均低于限值标准。采用USEPA推荐模型对水体中MC污染的健康风险进行评价。各批次水样中MC-LR的非致癌健康风险指数(HI)为0.03~0.39,毒性等效MC-LR的HI介于0.04和0.72之间,均低于基准值,说明贴沙河作为饮用水水源尚无明显的健康风险。     

中国表层水体沉积物中多环芳烃源解析及评价

采用索氏提取气相色谱-质谱法测定中国6个重点水体表层沉积物中16种多环芳烃的含量。各化合物含量范围分别为长江6.20~163 ng/g、淮河7.90~249 ng/g、海河12.1~401 ng/g、松花江5.75~152 ng/g、太湖29.1~2 810 ng/g和滇池19.1~795ng/g；16种多环芳烃的总量分别为：长江1 147 ng/g、淮河1 723 ng/g、海河2 595 ng/g、松花江793 ng/g、太湖12472 ng/g、滇池3 714 ng/g，属中等污染水平。利用特征分子比值法分析结果表明6条水体表层沉积物中PAHs均可能以燃料（包括柴油、汽油、煤、木材）燃烧以及焦化污染为主。淮河和滇池还可能存在轻微石油泄漏污染。利用沉积物质量基准法（SQGs）和沉积物质量标准法分别对6条水体表层沉积物中多环芳烃的风险评估表明严重的多环芳烃生态风险在这些水体表层沉积物中不存在，但长江、淮河、松花江、海河均可能存在一定的潜在风险，负面生物毒性效应会偶尔发生，风险主要来源于荧蒽和菲。太湖和滇池水体中存在的潜在多环芳烃风险种类较多，风险主要来源于菲、荧蒽、芘、苯并（a）蒽、苊和蒽，对水生生物毒性效应较高，有必要进行更深入细致的调查研究高风险区域底栖生物的受损状况、污染来源和途径，以制定合理的污染控制对策。     

Spatial distribution and quantification of endocrine-disrupting chemicals in Sado River estuary, Portugal

The important Portuguese Sado River estuary has never been investigated for the presence of potentially endocrine-disrupting chemicals (EDCs), such as natural estrogens (estradiol, estrone), pharmaceutical estrogens (17α-ethynylestradiol), phytoestrogens (daidzein, genistein and biochanin A), or industrial chemicals (4-octylphenol, 4-nonylphenol, and bisphenol A). Thus, the main objective of this study was to evaluate their presence at 13 sampling points distributed between both the industrial and the natural reserve areas of the estuary, zones 1 and 2, respectively. For that, water samples collected in summer and winter were processed by solid phase extraction and analyzed by high-performance liquid chromatography with photodiode array detection and gas chromatography–mass spectroscopy. Results showed that estrone, ethynylestradiol, all the aforementioned phytoestrogens as well as bisphenol A and 4-octylphenol were found in zone 1. In zone 2, neither estrogens nor 4-OP were found. However, in the same zone, daidzein (500 ng/L) and genistein (320 ng/L) attained their highest levels in summer, whereas biochanin A peaked in winter (170 ng/L). Furthermore, bisphenol A was also found in some areas of zone 2, but showed similar concentrations in both surveys (about 220 ng/L). This study demonstrated that the Sado River estuary had low EDCs levels, suggesting that the Sado’s high hydrodynamic activity may be involved in the dilution of local pollution. It was suggested that at the current levels of concentrations, all assayed EDCs are unlikely to individually cause endocrine disruption in local animals. However, under a continuous exposure scenario, an additive and/or synergistic action of the estrogenic chemicals load can not be excluded, and so, continuous monitoring is advisable.     

Simultaneous quantitative monitoring of four indicator contaminants of emerging concern (CEC) in different water sources of Central India using SPE/LC-(ESI)MS-MS

Environmental occurrence of CECs poses a great threat to both aquatic life and human health. The aim of this study was to optimize and validate SPE/LC-(ESI)MS-MS method for simultaneous quantitative monitoring of two sub-classes of CECs (pharmaceuticals and hormones) and to estimate the concentrations of select CECs in environmental water samples. For all the tested analytes, recoveries in laboratory reagent water were greater than 81%. Average percent (relative standard deviation) RSD of the analytes in recovery, repeatability, and reproducibility experiments were ≤?10%. Determination coefficients (r²) of primidone, diclofenac, testosterone, and progesterone were estimated to be 0.9979, 0.9972, 0.9968, and 0.9962, respectively. Limits of detection (LOD) for primidone, diclofenac, testosterone, and progesterone were 4.63 ng/L, 5.36 ng/L, 0.55 ng/L, and 0.88 ng/L, respectively. Limits of quantification (LOQ) for primidone, diclofenac, testosterone, and progesterone were 14.72 ng/L, 17.06 ng/L, 1.766 ng/L, and 2.813 ng/L, respectively. Average recoveries in environmental water and wastewater samples were greater than 74% and RSD were ≤?7%. Trace levels (68.33–125.70 ng/L) of primidone were detected in four environmental water samples, whereas diclofenac was not detected in any of the tested sample. Trace levels of progesterone were observed in two environmental samples (16.64 –203.73 ng/L), whereas testosterone was detected in STP inlet sample (178.16 ng/L).     

北京某污水处理厂出水中药物和个人护理品的污染现状

通过两次采集北京某大型污水处理厂的水样,采用HPLC-MS技术对水样中的10种PPCPs进行分析.结果显示,进水口水样中PPCPs浓度为7122.92ng/L,其中咖啡因的检出浓度最高(4490.54ng/L),污水处理厂对咖啡因的去除率大于90％(浓度为78.01ng/L).与文献报道值比较发现,该污水处理厂出水水样中PPCPs的浓度与其他国家报道的浓度基本上处于同一数量级,但污水中PPCPs的去除率都普遍低于国际水平.因此,需加强对污水处理厂水样中PPCPs的监测,完善污水处理的工艺.     

Determination of fecal contamination indicator sterols in an Australian water supply system

This paper reports a reconnaissance survey of the concentrations of sterol compounds (as indicators of fecal contamination) in a large water supply system in southeast Australia comprising a network of rivers, channels, and drains. Levels of coprostanol and cholestanol were determined in surface water and bottom sediment using gas chromatography–mass spectrometry analysis across 17 strategic sampling sites and over 12 months. Clear differences in the levels of fecal contamination were observed among sites. Four sites routinely contained high levels of the fecal indicator sterols indicated from surface water and sediment sample analysis. Coprostanol concentrations at each location varied from 0 ng/L at the reference site to 11,327 ng/L in a surface water sample of a drain directly downstream of a knackery. The majority of the sites contained coprostanol in the range of 500 to 800 ng/L. Since no fecal-associated sterol compounds were detected at the external reference sites, these were assumed to be free from fecal contamination. Sewage water discharge and/or substantial water runoff maybe the principal factors contributing to fecal contamination of the supply drains and channels.     

Total and methyl mercury in the water,sediment, and fishes of Vembanad,a tropical backwater system in India

Mercury contamination in the water bodies of developing countries is a serious concern due to its toxicity, persistence, and bioaccumulation. Vembanad, a tropical backwater lake situated at the southwest coast of India, is the largest Ramsar site in southern India. The lake supports thousands of people directly and indirectly through its resources and ecosystem services. It is highly polluted with toxic pollutants such as heavy metals, as it receives effluent discharges from Kerala’s major industrial zone. In the present study, water, pore water, sediment, and fish samples collected from Vembanad Lake were analysed for total mercury (THg) and methyl mercury (MHg) contents. The maximum concentrations of THg and MHg in surface water samples were31.8 and 0.21 ng/L, respectively, and those in bottom water samples were 206 and 1.22 ng/L, respectively. Maximum concentration of THg in surface sediment was observed during monsoon season (2850 ng/g) followed by that in the pre-monsoon season (2730 ng/g) and the post-monsoon season (2140 ng/g). The highest sediment concentration of MHg (202.02 ng/g) was obtained during monsoon season. The spatial variation in the mercury contamination clearly indicates that the industrial discharge into the Periyar River is a major reason for pollution in the lake. The mercury pollution was found to be much higher in Vembanad Lake than in other wetlands in India. The bioaccumulation was high in carnivorous fishes, followed by benthic carnivores. The THg limit in fish for human consumption (0.5 mg/kg dry wt.) was exceeded for all fish species, except for Glossogobius guiris and Synaptura orientalis. The concentration of THg was five times higher in Megalops cyprinoides and four times higher in Gazza minuta. Significant variation was observed among species with different habits and habitats. Overall, risk assessment factors showed that the mercury levels in the edible fishes of Vembanad Lake can pose serious health impacts to the human population.     

Contamination by perfluorinated compounds in water near waste recycling and disposal sites in Vietnam

There are very few reports on the contamination by perfluorinated chemicals (PFCs) in the environment of developing countries, especially regarding their emission from waste recycling and disposal sites. This is the first study on the occurrence of a wide range of PFCs (17 compounds) in ambient water in Vietnam, including samples collected from a municipal dumping site (MD), an e-waste recycling site (ER), a battery recycling site (BR) and a rural control site. The highest PFC concentration was found in a leachate sample from MD (360 ng/L). The PFC concentrations in ER and BR (mean, 57 and 16 ng/L, respectively) were also significantly higher than those detected in the rural control site (mean, 9.4 ng/L), suggesting that municipal solid waste and waste electrical and electronic equipment are potential contamination sources of PFCs in Vietnam. In general, the most abundant PFCs were perfluorooctanoic acid (PFOA), perfluorononanoic acid (PFNA), and perfluoroundecanoic acid (PFUDA; <1.4–100, <1.2–100, and <0.5–20 ng/L, respectively). Interestingly, there were specific PFC profiles: perfluoroheptanoic acid and perfluorohexanoic acid (88 and 77 ng/L, respectively) were almost as abundant as PFOA in MD leachate (100 ng/L), whereas PFNA was prevalent in ER and BR (mean, 17 and 6.2 ng/L, respectively) and PFUDA was the most abundant in municipal wastewater (mean, 5.6 ng/L), indicating differences in PFC contents in different waste materials.     

Perfluorooctane sulfonate (PFOS) distribution and effect factors in the water and sediment of the Yellow River Estuary, China

The distribution of perfluorooctane sulfonate (PFOS) was investigated in a total of 15 water and sediment samples from the Yellow River Estuary, China in April 2011. The results indicated that the concentrations of PFOS in the water and sediment samples averaged 157.5 ng/L and 198.8 ng/g and ranged from 82.30 to 261.8 ng/L and 75.48 to 457.0 ng/g, respectively. The concentrations of PFOS in the sediment column increased from 45.32 to 379.98 ng/g with the decrease of the sampling depth, which showed that the increased PFOS pollution in the sediment appeared in this region in over recent years. The distribution coefficient (K _d) of PFOS between water and sediment linearly increased from 0.37 to 4.80 L/g as the salinity (S‰) increased from 0.18 to 4.47. Correlation analysis revealed that K _d was significantly and positively correlated to the contents of total organic carbon and clay of the sediment, and salinity. Therefore, salinity was an important parameter in controlling the sediment–water interactions and the fate or transport of PFOS in the aquatic environment. The results of this study showed that the estuary was an important sink for PFOS and suggested that PFOS might be carried with the river water and transported for long distances before it reached to the sea and largely scavenged to the sediment in the estuaries due to the change in salinity.     

Performance of different composting techniques in reducing oestrogens content in manure from livestock in a Vietnamese setting

Steroid oestrogens (SE) are released by humans and animals into the environment. In the Mekong Delta animal excrement is directly discharged into surface water and can pollute the water. Only a few animal production sites are currently treating the excrement in either biogas plants or vermicomposting systems. The concentration of SE in manures from pigs and cattle was monitored in the Mekong Delta, Vietnam. Fresh cow faeces had an oestrogen concentration of 3.3 ng E2 eq/g dry weight. The SE concentration in effluent from biogas plants fed with animal manures was 341 ng E2 eq/L. Most of the SE were in the solid phase (77.9–98.7%). Vermicomposting reduced SE to 95% of the original input.     

Pollution by oestrogenic endocrine disruptors and β-sitosterol in a south-western European river (Mira,Portugal)

The Mira River is a Portuguese water body widely known for its wilderness and is advertised as one of the less polluted European rivers. On this presumption, the levels of endocrine-disrupting compounds (EDCs) in Mira waters were never measured. However, because environmentalists have claimed that the Mira could be moderately polluted, a range of 17 EDCs were measured not only at the estuary but also along the river. The targeted EDCs included natural and pharmaceutical oestrogens (17β-oestradiol, oestrone and 17α-ethynylestradiol), industrial/household pollutants (octylphenols, nonylphenols and their monoethoxylates and diethoxylates and bisphenol A), phytoestrogens (formononetin, biochanin A, daidzein, genistein) and the phytosterol sitosterol (SITO). For this propose, waters from six sampling sites were taken every 2 months, over a 1-year period (2011), and analysed by gas chromatography–mass spectrometry. Unexpectedly high levels of oestrogens and of industrial/household pollutants were measured at all sampling sites, including those located inside natural protected areas. Indeed, the annual average sum of EDCs was ≈57 ng/L for oestrogens and ≈1.3 μg/L for industrial/household chemicals. In contrast, the global average levels of phytoestrogens (≈140 ng/L) and of SITO (≈295 ng/L) were lower than those reported worldwide. The EDC concentrations were normalised for ethynylestradiol equivalents (EE_2eq). In view of these, the oestrogenic load of the Mira River attained ≈47 ng/L EE_2eq. In addition, phosphates were above legal limits at both spring and summer (>1 mg/L). Overall, data show EDCs at toxicant relevant levels in the Mira and stress the need to monitor rivers that are allegedly less polluted.     

Assessment of organochlorine pesticides and plasticisers in the Selangor River basin and possible pollution sources

A study on the quality of water abstracted for potable use was conducted in the Selangor River basin from November 2008 to July 2009. Seven sampling sites representing the intake points of water treatment plants in the basin were selected to determine the occurrence and level of 15 organochlorine pesticides (OCPs), six phthalate esters (PAEs) and bisphenol A (BPA). Results indicated OCPs were still detected regularly in 66.1 % of the samples with the Σ₁₅OCPs ranging from 0.6–25.2 ng/L. The first data on PAEs contamination in the basin revealed Σ₆PAEs concentrations were between 39.0 and 1,096.6 ng/L with a median concentration of 186.0 ng/L while BPA concentration ranged from <1.2 to 120.0 ng/L. Although di-n-butyl phthalate was detected in all the samples, concentrations of di-ethyl(hexyl)phthalate were higher. Sampling sites located downstream recorded the highest concentrations, together with samples collected during the dry season. Comparison of the detected contaminants with the Department of Environment Water Quality Index (DOE-WQI) showed some agreement between the concentration and the current classification of stream water. While the results suggest that the sites were only slightly polluted and suitable to be used as drinking water source, its presence is cause for concern especially to the fragile firefly “Pteroptyx tener” ecosystem located further downstream.