黄河宁夏段水体重金属时空分布特征及健康风险评价

通过2019—2020年在黄河宁夏段布设12个采样点监测各季节水体中Cu、Zn、Cd、Hg 4种重金属的质量浓度,分析重金属污染状况和来源,并评价对人体的健康风险。结果表明：黄河宁夏段水体4种重金属质量浓度由高到低为Zn＞Cu＞Cd＞Hg,除了Hg质量浓度有超过Ⅱ类标准限值外,其余重金属均未超标。4种重金属春、夏、秋的浓度高于冬季,Zn浓度分布差异最大。4种重金属对人体产生的总健康风险最大值成人为3.76×10-6 a-1,儿童为4.40×10-6 a-1,远低于最大可接受水平1×10-4 a -1 ,Cd为主要贡献因子。水体中Cu、Cd、Hg可能来源于工农业生产和降雨稀释,Zn可能来源于旅游交通运输和土壤淋溶。     

望虞河西岸九里河中四种除草剂的污染现状

基于气相色谱-质谱联用(GC-MS)法结合固相萃取(SPE)前处理技术,建立了水中4种除草剂氯草定、阿特拉津、乙草胺和异丙甲草胺残留的分析方法,于2018年春(4、5月)、秋(9、10月)和冬(1、3月)季对太湖流域望虞河西岸九里河水体中4种除草剂的污染现状进行调查分析。结果表明,4种除草剂的加标回收率为71. 2%～108%,RSD均10%,方法检出限为3. 5～6. 0 ng/L。九里河水体中氯草定、阿特拉津、乙草胺和异丙甲草胺4种除草剂质量浓度分别为未检出～0. 025 7,0. 019 1～1. 19,未检出～0. 026 0和未检出～0. 094 3μg/L。4种除草剂中阿特拉津最高值接近《地表水环境质量标准》(GB 3838—2002)限值,其他3种其值较低,氯草定首次在太湖流域水体中检出。     

武汉市巡司河中抗生素分布特征及生态风险评价

采用大体积直接进样—超高效液相色谱串联质谱法分析武汉市巡司河中45种抗生素的存在水平，评估其可能存在的生态风险。在巡司河布设6个采样点，于2022年12月—2023年5月进行采样并分析。结果显示，6个采样点共检出27种抗生素，检出最大质量浓度为874.2 ng/L；其中，氧氟沙星、左氧氟沙星检出率均为100%。监测期间，12月抗生素平均质量浓度最高（101.05 ng/L），4月最低（25.87 ng/L）。6个点位中，点位S3与S5抗生素平均质量浓度高于其他点位，分别为1 721.20和1 734.07 ng/L；点位S4是巡司河与长江的交汇处，抗生素平均质量浓度最低（94.54 ng/L）。利用风险商值法对巡司河中抗生素生态风险开展评价，结果表明：氧氟沙星、罗红霉素和克拉霉素呈现出较高风险，左氧氟沙星、林可霉素和莫西沙星在大多数点位处于中等风险，其余几种抗生素风险较低。     

基于QuEChERS提取法优化的液相色谱-串联质谱法测定水中多种除草剂

基于Qu ECh ERS提取方法,用液相色谱-串联质谱法测定水中14种常见除草剂,通过优化样品前处理条件,使14种除草剂在0.005 mg/L~0.500 mg/L范围内线性良好,相关系数均0.99,方法检出限为0.005 mg/L。空白水样3个质量浓度水平的加标回收率为74.5%~109%,5次测定结果的RSD为3.9%~11.4%。将该方法用于测定长江流域3个重点城市的水体,结果为未检出。     

集中式饮用水源地邻苯二甲酸酯类物质分布特征与健康风险评估

以某地区7个集中式饮用水源地为研究对象,采用固相萃取气相色谱-质谱法(SPE-GC-MS)对水体中16种邻苯二甲酸酯的分布特征和溯源进行了研究,并利用健康风险评估模型对水体PAEs进行了健康风险评价。结果表明:邻苯二甲酸二正丁酯、邻苯二甲酸二(2-乙基己基)酯、邻苯二甲酸二异丁酯和邻苯二甲酸二正辛酯在所有PAEs同系物中含量丰富,而所有样品均无邻苯二甲酸二(2-甲氧基)乙酯和邻苯二甲酸二戊酯的检出;二水厂和亨达水务断面Σ_(16)PAEs浓度最高,四水厂和五水厂断面Σ_(16)PAEs浓度最低;水体12种PAEs共提出3个主成分,揭示了91%的影响因子;层次聚类分析表明:7个采样断面聚为2类,分别代表了内河和长江水体。水体中PAEs的致癌风险值和非致癌风险值均远低于参考值,说明研究水体PAEs不会对居民构成致癌风险或其他明显的健康风险,但需加强该地区PAEs使用的规范与监管,强化末端处理,以规避风险。     

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。     

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。     

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。     

太湖主要入湖河流多溴联苯醚和有机磷阻燃剂污染与风险评价

为了解多溴联苯醚（PBDEs）和有机磷阻燃剂（OPFRs）在太湖3条主要入湖河流（太滆运河、太滆南运河和漕桥河）中的污染现状，采集其水体和沉积物样品，利用GC-MS/MS和LC-MS/MS技术对介质中13种PBDEs同族体和9种OPFRs进行分析。结果表明，所有水样品中均检出OPFRs，其总质量浓度为165～504 ng/L，其中三（1-氯-2丙基）磷酸酯（TCPP）为最主要污染物，最高值为160 ng/L；PBDEs在所有沉积物样品中均有检出，总质量比为16.7～765 ng/g。沉积物中PBDEs和OPFRs存在显著的正相关性（p＜0.01），说明这2种化合物的污染来源和环境归趋可能相类似。水中OPFRs基于无效应浓度（PNEC）的风险评价显示，部分化合物对藻类、蚤类和鱼类具有中等生态风险。指出，随着PBDEs的禁用，以及潜在的生物累积效应，OPFRs的环境污染须引起进一步的关注。     

辽宁省生态清洁小流域抗生素监测及生态风险评估

于2021年10月对辽宁省生态清洁小流域抗生素的赋存浓度、分布特征进行了调查。采用风险商值法对小流域的抗生素生态风险进行评价。结果表明,辽宁省生态清洁小流域中8种抗生素均有不同程度检出,检出总质量浓度范围为0013～0.313 μg/L,平均值为0.072 μg/L;小流域中抗生素质量浓度均低于我国大部分河流和流域。不同类型抗生素空间分布规律差异明显,检测出的抗生素中,质量浓度最高的是罗红霉素（ROX）,检出率最高的是磺胺甲噁唑（SMX）;各监测点位抗生素组分的占比排序为：SMX＞ROX＞替米考星（TIC）＞氟苯尼考（FFC）;抗生素主要来源是畜禽养殖和生活污水。生态风险评价结果显示,ROX、脱水红霉素（ERY-H₂O）、诺氟沙星（NOR）和SMX存在高风险,其余种类呈现中、低风险。生态清洁小流域水体中暴露出的抗生素生态风险不容忽视,亟待进一步探究环境风险并采取有效的防治措施。     

珠三角典型河道49种抗生素污染现状及风险评估

为评估抗生素在珠三角地表水中的生态及健康风险,在石岐河布设20个监测点位,分别采集丰水期和枯水期样品,用固相萃取/超高效液相色谱-质谱法对4大类共49种抗生素进行检测。结果显示,在丰水期和枯水期样品中共检出抗生素30种,检出种类和抗生素总浓度都呈现出枯水期明显大于丰水期的现象。从总量上看,喹诺酮类是影响石岐河生态环境安全的主要抗生素类别。石岐河抗生素浓度在枯水期主要受污水处理设施出水的影响,在丰水期主要受沿岸养殖业排水的影响。采用风险熵法对生态风险进行评估,发现枯水期生态风险高于丰水期,头孢匹啉、克林霉素、诺氟沙星3种抗生素处于高生态风险级别,罗红霉素、磺胺二甲异恶唑和奥索利酸3种抗生素处于中等生态风险级别,另有4种抗生素处于低生态风险级别,应引起重视。采用健康风险评价模型对人群健康风险进行评价,发现石岐河抗生素致癌风险和非致癌风险皆处于可接受的健康风险范围内。     

黄河流域水质和工业污染源研究

为科学评价黄河流域的水质状况及工业企业污染源现状,根据黄河流域2018—2019年地表水和饮用水水源地水质监测数据,建立了综合反映流域水环境质量和可定量分析排名的城市水质指数;利用大数据技术分析工业企业水污染物排放数据,研究建立了企业环境信用动态评价体系。研究结果表明:2018—2019年,黄河流域城市水环境质量得到一定程度的改善,城市地表水环境质量优和良等级数量从17个增加到19个,饮用水水源地优等级城市数量从7个增加到11个;但黄河流域中游地区水污染问题较为严重,需要重点加强水污染控制。水质污染主要以点源工业污染为主,COD和氨氮排放量较多,COD和氨氮年日均排放浓度平均值分别为51.1、3.1 mg/L,工业废水处理率偏低;山西、陕西、河南等"高"风险企业数量较多,分别达到3 047、1 630、1 442家。建议加强黄河流域上下游、左右岸、干支流协同配合,加大水污染防治工作的深度和力度。     

Estrogenic activity profiles and risks in surface waters and sediments of the Pearl River system in South China assessed by chemical analysis and in vitro bioassay

Estrogenic activity risks in the Pearl River system (Liuxi River, Zhujiang River and Shijing River) in South China were assessed by combined chemical analysis and recombinant yeast estrogen screen (YES) bioassay for surface waters and sediments collected in both dry and wet seasons. The xenoestrogens 4-tert-octylphenol, 4-nonylphenol and bisphenol A were detected at almost every sampling site at concentrations of several ng L(-1) (ng g(-1)) to tens of μg L(-1) (μg g(-1)) in surface waters (and sediments). The estrogens estrone and 17β-estradiol were also detected in most of the samples with concentrations from several ng L(-1) (ng g(-1)) to tens of ng L(-1) (ng g(-1)) in surface waters (and sediments). However, synthetic estrogens diethylstilbestrol and 17α-ethinylestradiol were only detected at a few sites. The 17β-estradiol equivalents (EEQ) screened by the YES bioassay were in the range of 0.23-324 ng L(-1) in surface waters and from not detected to 101 ng g(-1) in sediments. Shijing River displayed one to two orders of magnitude higher levels for both measured chemical concentrations and estrogenic activities than the Zhujiang River and the Liuxi River. A risk assessment for the surface waters showed high risks for the downstream reaches of the Liuxi River and the upstream to midstream reaches of the Zhujiang River and the Shijing River. Higher estrogenic risks were observed in the wet season than in the dry season for surface waters, probably due to the input of runoff and direct overflow of small urban streams during heavy rain events. Only small variations in estrogenic risk were found for the sediments between the two seasons, suggesting that sediments are a sink for these estrogenic compounds in the rivers.     

Assessment of pesticide residues in freshwater areas affected by rice paddy effluents in Southern Japan

Pesticide residues in five freshwater areas that are directly affected by rice paddy effluents in southern Japan were measured to determine their maximum concentrations and temporal variations. Water samples were collected every week during the 2005 rice planting season in Kagoshima Prefecture and stations were established in Amori River, Sudo River, Nagaida River (that drains into the bigger Kotsuki River), rice paddy drainage canal, and wastewater reservoir (that collects effluents from rice paddy fields). Of the 14 target pesticides examined, a total of 11 were detected in all stations. Mefenacet, fenobucarb, and flutolanil were the three pesticides with the highest maximum concentrations and were also detected frequently. Analysis of temporal variations of pesticides showed that herbicides had relatively higher concentrations in the earlier stages of the rice planting season, while insecticides and fungicides had relatively higher concentrations at the later stages. There was no significant difference among stations with regards to the temporal patterns of the top three pesticides. The calculated toxic units were less than 1 in all stations, implying low or negligible environmental risk of pesticides detected to freshwater organisms.     

黄河口的水质、底质污染及其变化

分析了2001年在黄河口附近所取的3处水样和3处泥样中污染物的含量,并与历史数据进行了比较.利用<地表水环境质量标准>(GB3838-2002)和美国国家海洋大气管理局(NOAA)水体泥沙质量标准等分别对水体和底泥中的重金属(砷)和氮磷污染进行了评价.认为黄河口的水污染严重,主要污染物为汞和氮;泥沙污染尚不严重,但污染物的增长率高;水体中较高的氮含量和泥沙中氮含量的迅速增高可能会对渤海湾的富营养化情况产生影响.     

Characteristics of and Human Influences on Nitrogen Contamination in Yellow River System, China

Nitrogen (N) contamination in the Yellow River mainstream and its tributaries was studied using data from 1960 to 2000 from 312 monitoring sites in the Yellow River system. Data showed that N concentrations in the Yellow River have increased since 1960, especially after 1990. N concentrations in the Yellow River mainstream increased from the upper reaches (less than 1.0 mg L(-1) for TN and less than 0.10 mg L(-1) for NH4(+)-N) to lower reaches (higher than 4-5 mg L(-1) for TN and higher than 1.0 mg L(-1) for NH4(+)-N). However, the highest N contaminations (50-250 mg L(-1) for TN and 10-20 mg L(-1) for NH4(+)-N) was found in some tributaries, which was attributed as an effect of industrial wastewater and municipal sewage. Nitrogen concentrations from several monitoring sites were positively correlated with several regional socio-economic indices, such as population density, fertilization rates, livestock, industrial input and GDP. Depending on location, seasonal N concentrations contrasted among watersheds. Monitoring stations located in rural and agricultural areas showed higher N concentrations during the flood season while those located in areas with urban and industrial centers showed higher N concentration during the dry season. Mainstream flow and N concentrations showed a strong inverse relationship; with higher N concentrations as the river flow declined. Intensive water extraction for agricultural irrigation and increasing N input to the river from fertilized agricultural fields could explain the increasing N concentrations during extensive droughts.     

基于压力-状态-响应(PSR)模型的黄河流域环境安全评价体系法治化研究

黄河流域环境安全评价包括对水环境质量、水环境健康、水环境风险的综合评估和对环境治理有效性的评价，是监测河流环境安全和支撑环境管理决策的重要技术手段。当前，我国尚未形成全面、有效的黄河流域环境安全评价体系。为此，基于压力-状态-响应(PSR)模型，构建了一套具有法治特色的黄河流域环境安全评价指标体系，并以黄河流域河南段2019年和2020年环境治理工作为例，对模型进行了验证。同时，提出探索赋予河流合法权利，完善以《黄河保护法》为核心的黄河流域环境风险防控法律体系，将适应性治理融入联合执法，建立和完善“河长-警长-检察长”联动机制，建立黄河流域环境风险治理体系和突发环境事件监控预警体系等法治化建议。     

基于多元统计的宁夏典农河水质演替特征探究

宁夏典农河是黄河宁夏段的主要入黄排水沟之一，其水质状况对黄河宁夏-内蒙古段跨省流域水质安全至关重要。选取典农河2011—2020年10个监测点位的16项水质参数，采用综合污染指数(WPI)法，结合相关性分析、主成分分析、聚类分析等分析方法，综合分析该流域水污染特征，并对污染程度进行评估，对污染因子和污染原因进行解析，最终提出管控建议。研究结果表明：2011—2020年，影响典农河水质的主要污染因子为COD_Cr、NH₃-N、TP、TN,对应的年均浓度范围分别为22.3～71.5、0.64～9.09、0.173～0.662、2.89～21.52 mg/L,超标率分别为46%、8%、13%、85%。典农河2011—2020年WPI范围为0.59～1.74,重金属含量一直维持在较低水平。流域TN与TP年均浓度比值范围为20～84,整体呈下降趋势，且各监测点的差异性逐渐减小；BOD₅与COD_Cr浓度比值范围为0.02～0.19,反映出典农河流域水体可生化性较差。各监测断面污染物之间存在较强相关性，其中：流域C...     

Influence of High Levels of Total Suspended Solids on Measurement of Cod and Bod in the Yellow River, China

Using the Yellow River, China, the study explores the problem of the use of COD and BOD₅ as water quality management parameters in the presence of very high levels of suspended sediment (TSS) that characterize this river. Although the amount of natural organic matter per unit of suspended sediment of the Yellow River is not high, the very high concentration of mineral sediment in the Yellow River results in a large concentration of organic matter, which artificially inflates the laboratory values of COD and, as a consequent, leads to greatly exaggerated reports of pollution of the Yellow River. BOD₅ can more accurately reflect the pollution of the Yellow River than COD; however, measured values of BOD under-report the actual values due to settling of the sediment in the incubation chamber resulting in values that are 21.6--38.3% less than the actual values. Therefore corrections are required for laboratory COD and BOD values so that the values are not artifacts of the sediment regime. Our work provides new insight into this phenomenon and demonstrates how correction factors may be determined and used with pollution data. Our work also suggests that the actual pollution levels of the Yellow River are probably not as high as reported by monitoring agencies.