城市河流重金属元素对降雨径流的动态响应

以海口市美舍河市区河段为研究对象,于2020年雨季分别采集降雨径流以及降雨径流汇入后的河流瞬时水样,测定并分析主要重金属元素的浓度及其变化规律,探讨其对降雨径流的动态响应。研究结果表明：降雨径流对河流可溶态污染元素质量浓度的贡献不突出,对可溶态锌（Zn）、砷（As）、镉（Cd）、硒（Se）具有一定稀释作用,排水口下游 3 m处是可溶态铬(Cr）、锰（Mn）、钴（Co）对降雨径流响应最显著区域;降雨径流对各悬浮态元素质量浓度贡献较大,排水口下游7 m处是绝大多数悬浮态元素对降〖JP〗雨径流响应最显著区域;Mn、Zn、Cr、镍（Ni）、As、Co、Cd 7种元素的总质量浓度对降雨径流的动态响应表现为先上升后下降。其中,排水口下游3 m处是Cr、As总质量浓度对降雨径流响应最显著区段,排水口下游7 m处是Mn、Co、Ni、Zn及Cd总质量浓度对降雨径流响应最显著区段。降雨径流对河流主要污染元素年输入总量估算结果表明,海口市建成区降雨径流向美舍河等受纳水体直接年输入量最大的是Mn和Zn,其次是Cr、As、Ni,Se与Cd的年输入量最小。     

《地下水管理条例》实施后的金属指标检测样品采集及前处理规范性分析

《地下水管理条例》自2021年12月1日起施行,但是由于《地下水质量标准》(GB/T 14848—2017)未明确其中的金属指标是检测可溶态含量还是总量,导致各检测机构在检测过程中的采样和前处理环节存在较多不确定之处。梳理了国内外地下水监测相关标准和规范,并进行了实验比对,经分析得出以下结论:铜、铅、锌、铁、锰的可溶态含量和总量检测结果存在明显差异,其中,铁和铅检测结果的差异最明显,铁和锰检测结果的差异会影响地下水质量类别判定。《地下水质量标准》中的金属指标应检测可溶态,包括汞、砷和硒。充分洗井后采集的地下水样品存在一定的浑浊度是合理的。完成采集的地下水金属指标检测样品中不应包含沉淀相。测定地下水可溶态汞、砷和硒时,如采用原子荧光法,则需对样品进行消解;如采用电感耦合等离子体质谱法,则无需对样品进行消解。在此基础上,对地下水采样及前处理关键环节和地下水检测管理工作提出了相关建议。     

运城市区秋冬季大气PM2.5中重金属污染特征及健康风险评估

为了解山西省运城市大气细颗粒物（PM_2.5）中重金属的污染特征和来源及其健康风险,于2020年10月15日—2021年2月14日对运城市大气PM_2.5样品进行连续采集,使用微波消解-电感耦合等离子质谱法（ICP-MS）分析了样品中的铬（Cr）、锰（Mn）、镍（Ni）、铜（Cu）、锌（Zn）、砷（As）、镉（Cd）和铅（Pb）等8种重金属元素的质量浓度。结果表明,采样期间,ρ（PM_2.5）平均值为78.96μg/m³,采暖季ρ（PM_2.5）为（79.84±43.79）μg/m³,高于非采暖季（76.54±23.97）μg/m³,采暖季和非采暖季ρ（PM_2.5）均值均超过《环境空气质量标准》（GB 3095—2012）中的二级标准。富集因子法分析表明,Ni、Cu、Zn、As、Cd和Pb的富集因子均高于10,其中Cd元素的富集因子平均值达到1.089,表明受人为污染影响严重。主成分分析结果表明,运城市区秋冬季大气中重金属主要有3个来源,分别为混合燃烧源、机动车尾气源、工业排放源。健康风险评价结果显示,经手口摄入暴露强度最大,呼吸吸入暴露强度最小,皮肤接触暴露强度居中;儿童在3种暴露途径的总暴露剂量高于成人,儿童重金属暴露风险高于成人。各途径的非致癌风险强度叠加值＜1,表明非致癌风险较小;但As、Pb的非致癌风险相对较高。4种重金属的呼吸吸入途径致癌风险程度排序为：As＞Cr＞Cd＞Ni,单种重金属的致癌风险（TR）值以及重金属的总致癌风险（R）值均＜10^-6,表明本研究中重金属不具有致癌风险。     

南通地区酸性降水的特征

①空间分布特征：有明显区域差异。近海地区ｐＨ均值６．５１～６．１２,酸雨频率２．５％～５．９％。市区ｐＨ均值＜５．１,最低值为３．６６,频率为４４．１％～５０．６％。②时间分布特征：从６县（市）属镇的ｐＨ均值,１９９１～１９９５年逐年下降,１９９５～１９９７年逐年上升。③季、月变化：降水酸度为春季＞冬季＞秋季＞夏季,３月份酸雨频率最高（７０％）,ｐＨ均值为４．７７。酸性降水的季节变化与两广地区类似。④化学特征：降水中阴离子以ＳＯ２－４占绝对优势,占阴离子总含量的８０％,ＳＯ２－４与ＮＯ－３的比值…     

贵州煤矿区表层水-沉积物重金属分布特征及来源分析——以新寨河为例

为探索贵州煤矿区表层水-沉积物中重金属的分布特征及来源,科学制定环境保护与污染治理措施,以新寨河为研究对象,在11个样点共采集66个表层水体和沉积物样品,通过对Cd、Pb、Cr、Zn、Cu、As、Hg、Fe、Mn等9种重金属元素进行分析,揭示其在新寨河的空间分布特征。同时,利用多指数法开展了有毒重金属元素污染状况评价,通过相关性分析和主成分分析解析了重金属的来源。结果表明,新寨河流域表层水体中,Fe、Mn点位超标率达100%。表层水中重金属元素的平均含量排序为Fe＞Mn＞Zn＞Cu＞Cr＞As＞Cd＞Pb＞Hg,而沉积物中重金属元素的平均含量排序则是Fe＞Mn＞Zn＞Cr＞Cu＞As＞Pb＞Cd＞Hg,表明新寨河表层水体和沉积物中重金属元素的空间分布存在一定差异。各重金属元素的内梅罗综合污染指数介于0.59~1.13之间,表明新寨河表层水体中重金属的污染程度达到轻微污染水平。单种重金属元素的潜在生态危害系数计算结果显示,90.91%和9.09%的沉积物样点分别被归类为轻微风险和中等风险。所有样点沉积物的潜在生态危害指数介于14.57~120.55之间(均值为72.08),表明新寨河沉积物的潜在生态风险较低。Cu、As在多个样点存在污染现象,需予以重点监控管理。新寨河流域重金属的来源可分为三大类:Cd、Pb、Cr、Zn、Cu为第一类,对应地表径流源;As、Fe、Mn为第二类,对应煤矿开采源;Hg为第三类,对应复合源。     

不同材料复合添加对土壤铬形态的影响

以铬污染黄壤为研究对象,选择有机材料（泥炭）、pH值调节剂（沸石）、生物炭（鸡粪）3种不同种类的土壤重金属污染改良剂,采用正交试验L9（34）设计和室内盆栽试验,考察不同复合材料组对土壤中重金属铬形态、pH值、有机质含量的影响。结果表明：沸石的添加提高了土壤pH值、有机质含量,增加了土壤可还原态、可氧化态铬含量;鸡粪的添加通过提高土壤pH值从而增加土壤可还原态铬的含量;泥炭的添加提高了土壤有机质含量、土壤可氧化态铬含量,降低了土壤可交换态铬含量。     

剩余污泥中重金属形态分析研究

采集徐州市和淮北市三处污水处理厂的剩余污泥,通过室内实验测试,研究污泥中的重金属含量和形态分布特征.结果表明:污泥中不同重金属元素的含量存在差异,Zn的浓度最高.某些重金属元素超出国家农用标准数倍.连续提取的形态分布表明:Cu、Zn、Pb和Cr主要分布在稳定态,生物有效性较差,而Cd的主要分布在不稳定性态,生物有效性强,对环境的危害大.     

白马湖甲壳动物体内重金属含量调查

对白马湖3种甲壳动物体内的Pb、Cd、Cu、Cr、Zn的含量进行了调查。结果表明,Cu、Zn含量较高;同种重金属元素在不同种类的软体动物体内含量差异较大,富集能力的次序是克氏原敖虾＞日本青沼＞秀丽白虾;Cd 和 Pb 在克氏原螯虾体内的不同器官和组织中富集程度不同,其中以肌肉中含量最低,鳃中的含量居中,虾壳中的含量为最高。     

铅锌冶炼废水处理后沉渣重金属元素特征与环境活性研究

通过扫描电子显微镜与X射线衍射仪分析、BCR法三步连续提取及元素化学分析,对铅锌冶炼废水处理后沉渣中重金属的赋存状态、环境活性进行研究。结果表明,沉渣中主要毒害元素为Zn、Pb、Mn、Cd和Cu,且以非晶态存在,其含量分别为62350、29530、7650、4530和830 mg/kg。渣中Zn和Cd酸可提取态所占比例较大,分别为37.72%和34.44%; Mn的可还原态相对含量很高,达到49.67%;Zn和Pb的可氧化态含量较高,分别占全量的34.16%、34.68%;Pb和Cu的残渣态含量较高,分别占全量的39.72%和61.69%。     

我国土壤中主要元素监测技术及难点

文章梳理了国内外土壤中元素的标准分析方法,对比总结了我国标准方法的特点及与国外标准方法的差异,如我国多为元素全量监测,国外则多为酸可溶态的监测等。剖析了土壤中主要元素分析技术中的样品消解与干扰消除等难点问题,阐述了不同的酸在消解过程中的作用,说明了如何正确控制酸的用量、添加顺序、温度等关键因素,总结了干扰消除的方法等,并初步提出技术发展建议。     

Speciation of metals in bed sediments and water of Qaraaoun Reservoir, Lebanon

Determination of only total element in sediments does not give an accurate estimate of the likely environmental impacts. Speciation study of metals in sediment provides information on the potential availability of metals (toxic) to biota under various environmental conditions. In water, the toxic metal specie is the free hydrated metal ion. The toxicity of metals depends especially on their chemical forms rather than their total metal content. The present study focuses on Qaraaoun Reservoir, Lebanon. Earlier studies focused only on total metal concentrations in sediment and water. The objective of this study was to determine metal speciation (Fe, Cr, Ni, Zn, Cu, Pb, Cd) in the (operationally defined) sediment chemical fractions and metal speciation in reservoir water. This would reflect on metal bioavailability and toxicity. Water samples and bed sediments were collected from nine sites during the dry season and a sequential chemical fraction scheme was applied to the <75-??m sieve sediment fraction. Metal content in each fraction was determined by the FAAS technique. The data showed that the highest percentages of total metal content in sediment fractions were for: Fe in residual followed by reducible, Cr and Ni in residual and in reducible, Cu in organic followed by exchangeable, Zn in residual and in organic, Pb in organic and carbonate, Cd was mainly in carbonate. Total metal content in water was determined by ICP-MS technique and aqueous metal speciation was predicted using AQUACHEM software interfaced to PHREEQC geochemical computer model. The water speciation data predicted that a high percentage of Pb and Ni were present as carbonate complex species and low percentages as free hydrated ions, highest percentage of Zn as carbonate complex species followed by free hydrated ion, highest percentage of Cd as free hydrated ion followed by carbonate complex species. The sensitivity attempt of free hydrated ion of Ni, Zn, Pb, and Cd in reservoir water revealed dependence of Zn and Cd on pH and alkalinity, while Ni and Pb were only dependent on pH.     

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。     

Occurrence of selected antibiotics in Jiulongjiang River in various seasons, South China

The concentrations of six sulfonamides (SAs) and three tetracyclines (TCs) were investigated in Jiulongjiang River during the low water season and the high water season. They were monitored in both surface water and sediment. Total concentrations of all these antibiotics varied from 31 to 25,771 ng g(-1) in sediment samples. In water they ranged from 60 to 2607 ng L(-1) during the low water season and from ND (not detected) to 134 ng L(-1) during the high water season. At the sites nearby breeding farms, chlorotetracycline was found to have the highest concentration of 1036 ng L(-1) in water and 14,666 ng g(-1) in sediments. According to the published data, the concentrations of sulfamethazine, sulfameter and TCs at these sites were higher than that in most rivers. The concentrations during the low water season were tens to hundreds of times higher than that in the high water season. The lower concentrations of TCs in the high water season might result from both dilution and photo-degradation, while dilution and bio-degradation might lead to the lower concentrations of SAs. However, further study is needed to clarify the specific reasons. Concerning the relationship between sediment and water samples, the pseudo-partitioning values of TCs were much higher than SAs. It indicates that the TCs are prone to accumulate in the sediment.     

Distribution of heavy metals in sediment and water of river Gomti

Gomti river receives industrial as well as domestic wastes from various drains of Lucknow city. In the process the water and sediment of the river Gomti get contaminated with heavy metals and other pollutants. In the present study, impacts of domestic/industrial wastes on the water and sediment chemistry of river Gomti with special reference to heavy metals have been investigated in different seasons (summer, winter and rainy). For this, seven sampling sites: Gaughat, Mohan Meakin, Martyrs Memorial, Hanuman Setu, Nishatganj bridge, Pipraghat and Malhaur, in the river Gomti in Lucknow region were identified and samples of water and sediments were collected in all the three seasons. In the collected water and sediment samples, six metals (Cd, Cr, Cu, Ni, Pb, and Zn) were analyzed on ICP-AES (Inductively coupled plasma emission spectroscopy) Labtam Plasmalab 8440. High concentrations of all the metals were noticed in water and sediment in rainy season compared to summer and winter. Because in rainy season runoff from open contaminated sites, agricultural field and industries, directly comes into the river without any treatment. In both the cases, the concentration of zinc was maximum (0.091 g/ml in water and 182.13 g/g in sediment) and the concentration of cadmium (0.001 g/ml in water and 17.26 g/g in sediment) was minimum. Higher concentration of metal in water and sediment during rainy season could be due to the industrial/agricultural/domestic runoff coming into the river.     

Monitoring the impact of urban effluents on mineral contents of water and sediments of four sites of the river Ravi, Lahore

We assessed the impact of urban effluents on the concentrations of selected minerals (Cd, Cr, Cu, Fe, Pb, Zn, Mn, Ni, and Hg) in river Ravi before and after its passage through Lahore city. Water and sediment samples were collected from three lowly to highly polluted downstream sites (Shahdera (B), Sunder (C), and Balloki (D)) alongside the least polluted upstream site (Siphon (A)) during high and low river flow seasons. All the mineral concentrations increased up to site C but stabilized at site D, showing some recovery as compared to the third sampling site. The trend of mean mineral concentration was significantly higher during the low than the high flow season at all the sites. The mean Hg concentrations approached 0.14 and 0.12 mg/l at site A which increased (%) up to 107 and 25 % at site B, 1,700 and 1,317 % at site C, and 1,185 and 1,177 % at site D during low and high river flows, respectively. All mineral concentrations were much higher in the sediment than the water samples. Mean Cd (917 %), Cr (461 %), Cu (300 %), Fe (254 %), Pb (179 %), Zn (170 %), Mn (723 %), Ni (853 %), and Hg (1,699 %) concentrations were higher in riverbed sediments sampled from site C in comparison with the sample collected at site A during low flow season. The domestic and industrial discharges from Lahore city have created undesirable water qualities during the low river flow season. As majority of the mineral levels in the river Ravi were higher than the permissible and safe levels, this is of immediate concern for riverine fish consumers and the users of water for recreation and even irrigation. The use of these waters may pose health risks, and therefore, urgent intervention strategies are needed to minimize river water pollution and its impact on fish-consuming communities of this study area and beyond.     

珠海码头内铜污染现状及生态风险分析

以珠海码头作为调查船舶防污漆使用影响的对象,分析了珠海周边海域码头内表层沉积物与海水中的重金属含量,以Cu元素为讨论重点,对其进行污染程度与潜在生态危害的评估。结果表明,码头内表层沉积物中Cu含量明显高于码头外沉积物,离市区较近的香洲码头和金沙滩码头内沉积物受到中等至较高程度的Cu污染,海岛东澳岛码头海水易流通,因此受污染程度较低。使用Hakanson生态危害指数法对沉积物进行评估的结果为低潜在生态危害,但码头内海水中Cu元素含量已高于生态安全限值。     

An assessment of heavy metal contamination in soils of fresh water aquifer system and evaluation of eco-toxicity by lithogenic implications

The chemistry of heavy metals in sediments with respect to bio-availability and chemical reactivity is regulated by pH, texture, and organic matter contents of the sediments and specific binding form and coupled reactivity of the metals within. To focus on the metal distribution (Fe, Mn, Pb, Cd, Zn, Co, Cu, and Cr) and behavior in a fresh water aquifer system along with the ecological toxicity parameters, a four-step sequential extraction method was applied on 18 Eastern Ghats’ type sediments from fluorosis-hit Nayagarh district, India. Geo-accumulation index of metals in the sediments indicates that they are practically uncontaminated and/or less contaminated with and Fe, Mn, and Cu; contaminated to moderately contaminated with Pb, Zn, and Cr; and strongly contaminated with Cd. Rather, more than 80 % recovered Cd metal concentration in sediments constitute the labile fractions. Temporal clustering of metal fractions indicates transition metal fraction distribution claiming the sediment pH regulation. Similarly, base metal distribution accounts for organic carbon and soil conductivity due to their greater availability in exchangeable and sulfide fractions. Correlation analysis and factor analysis scores demonstrate lack of inter-relationship between transition group and base metal fractions. High fluoride concentration in ground water is associated with high sodium-bicarbonate-iron affinity with elevated pH values (i.e., >7.0) and high positive factor score with the total iron concentration in ground water.     

菏泽市主要河流中氟的分布及其影响因素

菏泽市地处鲁西南高氟地区,其河流中的高浓度氟化物不仅会通过径流过程影响南四湖水质,还会影响当地水生态平衡及人体健康。通过分析菏泽市主要河流中氟化物的时空分布特征,并结合地下水、土壤及废污水调查结果,探讨了影响河流中氟化物分布的主要因素。结果表明:研究区河流中氟化物的平均浓度在0.98~1.45 mg/L之间,氟化物浓度分布呈现出枯水期＞平水期＞丰水期、下游＞上游、支流＞干流的特征。氟化物浓度较高的河流呈现高pH、低钙的特点,水化学组分以Na-HCO₃型、Na-SO₄型为主。河流中氟化物的浓度主要受蒸发浓缩和岩石风化作用的影响。研究区地下水和土壤中氟化物的背景浓度整体较高。枯水期高氟地下水可能通过直接补给河流对河流水体产生影响,丰水期土壤中的氟也会通过径流过程汇入河流。人类工农业生产过程大量开采利用当地高氟地下水,而高氟废水最终则会进入河流,导致河流中氟化物的含量升高。     

京杭运河常州段泥水界面无机氮交换过程模拟研究

分别在枯水期、平水期、丰水期利用原柱样静态释放实验对京杭运河常州段4个点位的无机氮界面交换过程进行模拟,并借助模拟结果对运河不同形态氮的界面循环过程进行了初步探讨。结果表明,全年NH+4N界面交换特征均表现为底泥向上覆水体释放,平均交换速率比较结果为平水期[182.3mg/(m2·d)]>丰水期[94.0mg/(m2·d)]>枯水期[29.5mg/(m2·d)],而底泥污染严重的下游点位释放通量高于其他断面;丰水期底泥为上覆水NO-3N的源,平水期和丰水期则成汇,且平水期底泥平均吸附速率若为枯水期的6倍;全年NO-2N交换过程表现底泥吸附的特征,枯水期交换速率极低,全年底泥DIN(总无机氮)输入量>输出量,底泥对高浓度上覆水NO-3N的吸附作用可能是底泥污染逐渐加重的原因。     

西南涌流域底泥重金属污染特征及潜在生态危害评价

西南涌流域近年来受到比较严重的污染,为了解受重金属污染状况,对该流域底泥重金属污染水平与特征进行了调查与分析,并在此基础上采用地累积指数法和潜在生态危害指数法对西南涌流域底泥重金属污染程度与生态危害进行了评价。结果表明,西南涌流域底泥已不同程度受到重金属Cu、Zn、Pb、Cd、Cr的污染,与珠三角土壤背景值相比,西南涌流域底泥重金属Cu、Zn、Pb、Cd、Cr分别超标11.38、3.32、1.81、19.45、3.20倍;底泥中的Cu、Zn、Cr、Cd之间呈极显著正相关(r=0.615~0.964)。通过地累积指数法评价表明,西南涌流域底泥中的Cd为偏重污染,Cu、Zn为偏中度污染,Pb为轻度污染,Cr为无污染;潜在生态危害指数法评价结果表明,西南涌流域底泥重金属的潜在生态危害程度总体属中等,主要是由Cd的含量过高引起。