土壤中有效态重金属的化学试剂提取法研究进展

土壤重金属污染是国内外关注的热点问题，针对采用全量重金属评价土壤污染存在的问题，本文综述了近年来土壤有效态重金属的化学提取方法研究进展，比较分析了各种单一提取法和影响土壤重金属提取率的因素。在此基础上，评价了各类提取方法的特点及其在应用上的优势和局限，指出了筛选通用提取剂的原则和依据。结合实验初步提出以去离子水作为通用提取剂的可行性及尚需研究解决的问题。     

湘江(衡阳段)河流沉积物中重金属潜在生态风险评价

对湘江（衡阳段）10个断面18个采样点的表层沉积物重金属（Cd、Hg、Pb、As、Cr、Zn、Cu）进行监测和分析，采用Lars Hanson潜在生态危害指数法对各种重金属的生态风险进行评价。结果表明，湘江（衡阳段）表层沉积物中各重金属潜在生态危害系数大小排序为：Cd〉Hg〉Pb〉As〉Cu〉Zn〉Cr。多种重金属的综合潜在生态风险指数RI为913．4，表明湘江（衡阳段）沉积物重金属污染属于很强的生态危害。     

M3法测定土壤有效态Cd、Cr、Pb和Ni

通过M3法对耕地土壤重金属的联合测定,为土壤重金属污染监测应用提供快速联合测定的方法。用M3法测定北方耕地土壤的有效Cd、Cr、Pb和Ni,通过对M3法与其他方法进行有效重金属测定值差异性及其相关性比较,与全量的浸出率分析等探讨M3法对耕地土壤有效重金属测定的特征。结果表明,M3法在《土壤环境质量标准》(GB 15618—1995)的土壤重金属含量范围内可以测定土壤有效态重金属Cd、Cr、Pb和Ni,且呈线性极显著相关。M3法与其他方法有效Cd、Cr、Pb和Ni有较好的相关性,与DTPA法呈极显著相关;与NaNO₃法除有效Pb外,呈极显著和显著相关;与HCl法除褐土和潮土的有效Pb外,也呈极显著和显著相关。M3法的有效态Cd、Cr、Pb和Ni的测定值均为最大。M3法对4种耕地土壤有效Cd、Cr、Pb和Ni的浸出率,因土壤类型不同,有效重金属含量所占比率不同,但利用M3法测定的有效态Cd、Cr、Pb和Ni的浸出率最大。     

土壤中重金属可提取态(氯化钙法)分析质量控制样品的研制

为真实反映土壤中重金属的生态风险和环境效应,全国农用地土壤污染状况详查土壤检测要求测定土壤中重金属可提取态(氯化钙法)指标。针对农用地土壤污染状况详查分析质量控制工作要求,研制了土壤中重金属可提取态(氯化钙法)分析质量控制样品。土壤样品为采自江西省旱地农田的红壤,经除杂、干燥、球磨、筛分(0.250 mm)、混匀等加工处理后装瓶。采用重金属总量和重金属可提取态(氯化钙法)两大类指标评价土壤样品的均匀性,均匀性分析结果同时采用单因素方差分析法(F检验法)和相对标准偏差法(RSD法)评价。结果表明:土壤样品均匀性良好,样品最小取样量为4.0g。8家实验室对土壤中As、Cd、Cr、Cu、Hg、Ni、Pb和Zn等8种元素开展联合定值。标准值为联合定值结果的总平均值(X-),标准值上、下限值分别为(X-+3S)和(X--3S),S为联合测定平均值的标准偏差,低于《全国土壤污染状况详查土壤样品分析测试方法技术规定》中分析方法检出限的元素不做量值评定。As、Cd、Cu、Ni和Zn等5种元素评定了标准值,含量范围为0.190 ～ 13.6 mg/kg。Cr、Pb和Hg等3种元素分析结果低于分析方法检出限,未能定值。研制的土壤分析质量控制样品已应用于土壤详查工作,在保证土壤详查检测结果准确可比等方面发挥了重要作用。     

北方某水库表层沉积物重金属的赋存形态及其环境影响因子分析

为了解北方某水库重金属污染状况,采用BCR连续提取法对该水库表层沉积物中Cu、Pb、Zn、Cd的赋存形态进行了分析,对其含量及空间分布进行了研究,结合重金属总量讨论了各元素的潜在环境风险。结果表明,该水库表层沉积物中Cu、Pb、Zn、Cd的平均质量比分别为65.20 mg/kg、36.69 mg/kg、137.5 mg/kg、2.38 mg/kg,与该地区土壤元素背景值、该地区水系沉积物平均值及全国水系沉积物平均值相比,4种重金属元素均有一定程度的累积,其中Cd累积最为严重。形态分析结果表明,Cd主要以醋酸可提取态及可还原态存在,具有很高的环境风险;Pb主要以极高比例的可还原态存在,潜在风险较高;Zn和Cu存在较大比例的酸可提取态及可还原态,也具有一定程度的潜在风险。各元素生物有效性即可提取态含量排序为:Cd>Cu>Pb>Zn。     

微波消解法测定铅锌冶炼厂废旧除尘布袋及其飞灰中重金属的应用研究

以广东某铅锌冶炼厂的废旧除尘布袋及其布袋上的飞灰为实验材料,以HNO3-H2O2-HF对布袋及飞灰进行微波全量消解,采用BCR三步浸提法提取飞灰中Cu、Zn、Pb、Cr、Ni、Cd 6种重金属,并利用火焰原子吸收仪器检测布袋及飞灰中6种重金属的含量及飞灰中各形态含量。结果表明,铅锌冶炼厂废旧布袋和飞灰中重金属含量较高,远大于《国家土壤环境质量标准》(GB 15168—1995)三级标准值。不同重金属在飞灰中的形态分布差异较大,Ni主要以残渣态和酸可交换态为主,Cu和Pb以残渣态为主,Zn的4种形态分布都较均匀,Cd、Zn潜在的迁移性最强。     

基于重金属有效态的农田土壤重金属污染评价研究

目前农田土壤重金属污染评价以重金属全量为依据,而评价农田土壤重金属污染影响时主要考虑农产品安全从而保障人体健康,农作物对重金属的吸收积累量则取决于土壤中有效态重金属含量。在阐述土壤重金属有效态定义的基础上,综合分析了土壤重金属有效态的影响因素及其与土壤中重金属全量和农作物中重金属含量的相关性,概括了土壤重金属有效态在土壤重金属污染评价中的应用,以期提出建立以土壤重金属有效态含量为基础、结合土壤重金属全量及作物中吸收的重金属含量的土壤重金属污染评价体系。     

湘江长沙段沉积物重金属污染状况及潜在生态风险评价

根据重金属环境化学行为的特点，应用沉积学原理，对湘江长沙段5个代表性断面10个采样点的表层沉积物中重金属（Hg、CA、As、Pb、Cu、Cr、Zn）进行监测和分析，采用Lars Hakanson潜在生态危害指数法对各种重金属的生态风险进行了评价。结果表明：按当地最高背景值为参比值计算，湘江长沙段表层沉积物中各种重金属潜在生态危害系数大小排序为Cd〉Hg〉As〉Pb〉Cu〉Cr〉Zn，多种重金属的潜在生态风险综合指数为560．8，表明湘江长沙段沉积物重金属污染属于强生态危害。     

南京市大气PM2.5中重金属分布特征及化学形态分析

于2017年1、4、7、10月在南京市主城区采集了大气PM2.5样品,用BCR法对PM_(2.5)中重金属进行连续提取,采用电感耦合等离子体-质谱法进行测定,分析重金属在颗粒物中不同形态和分布特征。结果表明,PM_(2.5)中9种重金属质量比排序为:Fe Zn Pb Mn Cu Cr As Ni Cd。Zn、Pb、Cd、Cu、Mn、As主要分布在弱酸提取态; Ni在弱酸提取态、可氧化态和残渣态中分布较均匀,占比26%～37%;而Fe、Cr主要以残渣态存在,分布比例分别为71%和54%。PM_(2.5)中Zn的生物有效性系数 0.8,属生物可利用性元素,表明其在环境中迁移能力最强,其余8种重金属生物有效性系数为0.2～0.8。     

南京市某垃圾填埋场重金属污染现状调查

对南京市某垃圾填埋场的垃圾、土壤、植物、炉渣等样品中Cu、Pb、Cr、Zn、Cd、Hg、As、Sb、Mn重金属含量进行分析。结果表明，垃圾填埋场的填埋土中Cu、Zn、As3种重金属含量分别高出自然土壤背景值86％、250％，300％。潜在生态危害指数法评价的污染状况为：Cd、As〉Hg〉Cu〉Pb〉Cr、Zn；Cd和As的毒性贡献较大，存在极高的潜在生态风险。     

Determination of lead, cadmium and copper in roadside soil and plants in Elazig, Turkey

The concentrations of lead, cadmium and copper in roadside soil and plants in Elazig, Turkey were investigated. Soil samples were collected at distances of 0, 25 and 50 m from the roadside. The concentrations of lead, cadmium and copper were measured by Flame Atomic Absorption Spectrophotometry (FAAS). A slotted tube atom trap (STAT) was used to increase the sensitivity of lead and cadmium in FAAS. Lead concentrations in soil samples varied from 1.3 to 45 mg kg⁻¹ while mean lead levels in plants ranged from120 ng g⁻¹ for grape in point-4 to 866 ng g⁻¹ for apple leaves in point-2. Lead analyses showed that there was a considerable contamination in both soil and plants affected from traffic intensity. Overall level of Cd in soil samples lies between 78 and 527 ng/g while cadmium concentration in different vegetations varied in the range of 0.8–98.0 ng g⁻¹. Concentrations of copper in soil and plant samples were found in the range of 11.1–27.9 mg kg⁻¹ for soil and 0.8–5.6 mg kg⁻¹ for plants. Standard reference material (SRM) was used to find the accuracy of the results of soil analyses.     

Enrichment and fractionation of heavy metals in bed sediments of River Narmada, India

A metal fractionation study on bed sediments of River Narmada in Central India has been carried out to examine the enrichment and partitioning of different metal species between five geochemical phases (exchangeable fraction, carbonate fraction, Fe/Mn oxide fraction, organic fraction and residual fraction). The river receives toxic substances through a large number of tributaries and drains flowing in the catchment of the river. The toxic substances of particular interest are heavy metals derived from urban runoff as well as municipal sewage and industrial effluents. Heavy metals entering the river get adsorbed onto the suspended sediments, which in due course of time settle down in the bottom of the river. In this study fractionation of metal ions has been carried out with the objective to determine the eco-toxic potential of metal ions. Although, in most cases (except iron) the average trace/heavy metal concentrations in sediments were higher than the standard shale values, the risk assessment code as applied to the present study reveals that only about 1–3% of manganese, <1% of copper, 16–19% of nickel, 4–20% of chromium, 1–4% of lead, 8–13% of cadmium and 1–3% of zinc exist in exchangeable fraction and therefore falls under low to medium risk category. According to the Geo-accumulation Index (GAI), cadmium shows high accumulation in the river sediments, rest of other metals are under unpolluted to moderately polluted class.     

Water-soluble species and heavy metal contamination of the petroleum refinary area,Jordan

The levels of lead, cadmium, copper, zinc, aluminum, chromium, and iron in street dust, soil, and plants in the Jordanian petroleum refinery were determined using flame and graphite-furnace atomic absorption spectrophotometry. Major cations (Li+, Na+, NH4+, K+, Mg2+, and Ca2+) and anions (F-, Cl-, NO3-, SO4(2-), and Br-) were also determined using suppression mode ion chromatography. Generally, higher levels of the heavy metals studied were found in street dust samples than in soil samples. On the other hand, except Cl-, and Li+ ions, other anions and cations showed higher concentrations in soil than in street dust samples. For plant samples, unwashed samples showed higher levels of heavy metals than their washed counterparts, indicating that dust fall is a source of heavy metal contamination.     

Health Risks Associated with Predicted Increase of Cadmium in Cultivated Soils and in the Diet

We have assessed the change of the dietary intake and the potential health risks of cadmium in Finland, assuming that a high level of cadmium in fertilizers (138 mg Cd/kg P) would prevail for the next 100 years. Soil measurements and modelling were used to derive the predicted level of cadmium in foods. In three important cultivars, wheat, potato and sugar beet, the cadmium concentration would increase by 20–35%. Consequently, the average dietary intake of cadmium in Finland would increase from 7.9 to 10.0 μg/day, corresponding with the urinary level of about 0.2 μg/l, a level that has not been associated with effects on the human health. However, in the risk group with 1) high dietary intake of cadmium, 2) elevated gastrointestinal absorption, and 3) tobacco smoking, the estimated urinary level of cadmium would be 2.0 μg/l. Recent epidemiological studies have shown that urinary level of 1–2 μg Cd/l is associated with an increased risk of bone demineralization and fractures, and 2–4 μg Cd/l with pre-clinical kidney damage. People characterized by more than one of the above-mentioned risks factors, may develop the adverse health effects at an old age, when cadmium has accumulated in the body.     

The Influence of a Coal-Fired Power Plant in Turkey on the Chemical Composition of Rain Water in a Certain Region

In this study, the chemical composition of the rainwater in Yatağan, which is a region surrounding a coal power plant was investigated from February to April 2002. Rainwater samples were obtained from Yatağan, located northwest of Muğla City in Turkey. pH values and concentrations of major ions (Ca²⁺, Na⁺, K⁺, , , ) in the rainwater samples were analyzed. The pH varied from 5.1 to 7.9 with an average of 6.7 which was in alkaline range considering 5.6 as the neutral pH of cloud water in equilibrium with atmospheric CO₂. In the total of 30 rain events, only three events were observed with water in the acidic range (<5.6), which occurred after continuous rains. The equivalent concentration of components followed the order: Ca²⁺ > > Na⁺ > > > K⁺ > H⁺. The anion and cation concentrations in the rainwater samples showed a high sulphate concentration (131 μEq/l), as well as high sodium (40 μEq/l) and calcium (298 μEq/l) concentrations. These values indicate that one probable source of the high sodium concentration is fly ash, after the coal burning process and the power plant can be effective on level concentrations in rainwater. In addition, the dust-rich local and surrounding limestone environment might have caused the high concentration of Ca²⁺ in rainwater of the Yatağan Basin. Due to a large contribution of these cations to the sulphate neutralization action, the rainwater of this region displays only a moderate acidity, which does not cause significant environmental impact.     

Assessment of dissolved heavy metal in the Yangtze River estuary and its adjacent sea, China

The purpose of this paper is to determine the concentrations of dissolved heavy metals namely mercury (Hg), lead (Pb), cadmium (Cd), and copper (Cu) and to investigate the relationships between nutrients (nitrate-nitrogen and phosphate) and dissolved heavy metals. For this purpose, the concentrations of dissolved heavy metals were measured through 51 voyages form 1984 to 2006 in the Yangtze river estuary and its adjacent sea. Results analysis showed that dissolved heavy metals were not the main pollutants in the Yangtze river estuary, and the main source of heavy metal contamination was industrial wastewater from terrestrial pollution during the past 20 years. Heavy metal values showed significant abundance in the south branch of the Yangtze River estuary and Hangzhou Bay. In addition, Pb showed negative correlation with nutrients, while the positive correlations between Hg, Cd, and nutrients were shown. The obtained molar ratios, $\Delta \mbox{Cd}/\Delta \mbox{N} = 1.68 \times 10^{-5}$ and $\Delta \mbox{Cd}/\Delta \mbox{P} = 1.66 \times 10^{-4}$ , are close to those in plankton, showing the biogeochemical behavior and process of dissolved cadmium.     

Trace elements and organochlorines in surf scoters from San Francisco Bay, 1985

Surf scoters (Melanitta perspicillata) were collected from 6 locations in San Francisco Bay during January and March 1985. Overall, mean concentrations of cadmium and zinc were higher in livers of scoters from the southern region of the Bay, whereas mean iron and lead were higher in those from the northern Bay region. Mean concentrations of arsenic, copper, lead, zinc, aluminum (January only) and iron (January) also differed among individual locations. Mean concentrations of copper and zinc increased, arsenic decreased, and cadmium remained the same between January and March. Selenium and mercury concentrations in scoter livers were not significantly correlated (P>0.05), but cadmium concentrations in livers and kidneys were positively correlated (P<0.0001), and body weight was negatively related to mercury concentration in the liver (P<0.05). Body weight differed among locations but not between January and March. Body weight was correlated with lipid content (P<0.0001). DDE and PCBs were each detected in 34 of 36 scoter carcasses. DDE increased significantly between January and March at Richmond Harbor, but BCBs did not differ between January and March at the 3 locations that could be tested.     

Exports of dissolved ammonium (NH4 +) during storm events across multiple catchments in a glaciated forested watershed

Storm event exports of dissolved were explored for multiple events in the Point Peter Brook watershed (PPBW), a glaciated, forested watershed located in Western New York, USA. Investigations were performed across four catchments (1.6–696 ha) with varying topography and the extent of surface-saturated areas. While wetland and riparian waters were important sources of during non-storm periods, throughfall and litter leachate were the dominant contributors of during storm events. Ammonium concentrations in catchment discharge displayed a sinusoidal seasonal pattern with a maximum during early spring (March) and a minimum in late summer (August–September). Storm event concentrations of in streamflow were much greater than baseflow values and showed a consistent temporal pattern with an increase in concentrations on the hydrograph rising limb, a peak at or before the discharge peak, followed by a decline in concentrations. Storm event patterns of DON were similar to while the patterns of differed from for the summer and fall events. The storm event expression of was attributed to throughfall and throughfall-mediated leaching of the litter layer. The reactive behavior of precluded its use in an end member mixing model (EMMA) for predicting streamflow concentrations. While concentrations of in precipitation and streamflow were high for the spring events, exports of in streamflow were highest for the large and intense storm events. Baseflow concentrations increased with the percent wetland/saturated area in the catchment but the same trend did not hold for storm-event concentrations.     

Lead and cadmium concentrations in shorebirds from the Yeongjong Island, Korea

This study presents concentration levels of pollutants (lead, and cadmium) in tissues (livers, kidneys, muscles, and bones) of shorebirds (Kentish Plovers (n = 5), Mongolian Plovers (n = 2), Dunlins (n = 6), Great Knots (n = 10), Terek Sandpipers (n = 10)) from Yeongjong Island, Korea in the East Asian–Australian migration flyways during the autumn migration in 1994–1995. Lead concentrations in livers, in kidneys, in muscles, and in bones were significantly different among shorebird species. Lead concentrations in livers of Kentish Plovers (4.76 ± 2.72 μg/wet g), Mongolian Plovers (2.05 μg/wet g), Dunlins (3.77 ± 1.07 μg/wet g), and Great Knots (4.27 ± 3.19 μg/wet g) were less than the toxic level, and lead concentrations in livers of Terek Sandpipers (1.20 ± 0.94 μg/wet g) were at the background level. Cadmium concentrations in livers, in kidneys, in muscles, and in bones did not vary among shorebirds, and concentrations of cadmium in livers and in kidneys were at background level (respectively, approximate 1 μg/wet g, approximate 2.67 μg/wet g) in all shorebird species. We suggest that interspecific differences of lead and cadmium concentrations were attributed to differences in exposure time and differences of diet, microhabitats in wintering ground. In livers and kidney of shorebirds from Yeongjong Island, lead and cadmium concentrations were higher than other locations previously reported.     

Effects of a constructed wetland and pond system upon shallow groundwater quality

Constructed wetland (CW) and constructed pond (CP) are commonly utilized for removal of excess nutrients and certain pollutants from stormwater. This study characterized shallow groundwater quality for pre- and post-CW and CP system conditions using data from monitoring wells. Results showed that the average concentrations of groundwater phosphorus (P) decreased from pre-CW to post-CW but increased from pre-CP to post-CP. The average concentrations of groundwater total Kjeldahl nitrogen and ammonium ( $ {\mathrm{NH}}{_4^{ + }} $ ) increased from pre-CW (or CP) to post-CW (or CP), whereas the average concentrations of groundwater arsenic (As), chromium, nickel, and zinc (Zn) decreased from pre-CW to post-CW regardless of the well locations. Variations of groundwater cadmium, copper, and Zn concentrations were larger in pre-CP than in post-CP and had a tendency to decrease from pre-CP to post-CP. In general, the average concentrations of groundwater aluminum and manganese decreased and of groundwater calcium, iron, magnesium, and sodium increased from pre-CP to post-CP. The average values of water levels (depth from the ground surface), redox potential, and conductance decreased and of chloride and sulfate ( $ {\mathrm{SO}}{_4^{{ - 2}}} $ ) increased after the wetland and pond were constructed regardless of the well locations. Results further revealed that there were significant differences (α?=?0.05) between the pre- and post-CW (or CP) for redox potential, water level, and As. This study suggests that the CW–CP system had discernible effects on some of the shallow groundwater quality constituents. This information is very useful for fully estimating overall performance of stormwater treatment with the CW–CP system.