Application of chemometrics methods for the estimation of heavy metals contamination in river sediments

The concentration and speciation of six heavy metals in sediments of eight sampling sites of Haihe River were investigated. The metals, namely Cd, Cu, Co, Ni, Mn and Pb were considered. By using sequential extraction(SE), the total metals were divided into five fractions: exchangeable, carbonate bound, iron/manganese oxide bound, sulfides and organic matter fraction and residual fraction. A multivariate statistical approach( principal component analysis, PCA) was used to evaluate the contamination of heavy metals by the total levels and chemical forms, respectively. The results showed that the total metals concentration(TMC) could not provide sufficient and accurate information because the mobility, bioavailabllity and toxicity of metals depend not only on their total concentration but also on the physicochemical form in which they occur.     

Catchment soils as a factor of trace metal accumulation in sediments of the reservoir Klingenberg (eastern Ore Mountains, Germany)

The release and accumulation dynamics of trace metals in soils and aquatic sediments were exemplarily investigated in the catchment area of the Reservoir Klingenberg(Germany). Catchment soils were examined for mobilizable and total concentrations of arsenic(As), cadmium(Cd), chrome(Cr), iron(Fe), manganese(Mn), nickel(Ni), lead(Pb),and zinc(Zn) and compared with trace metal quantities accumulated in riverbed and reservoir sediments. The comparison of all samples showed relatively small variations of Cr(7.96–46.0 mg/kg), Fe(7.79–40.4 g/kg), and Ni(6.06–56.5 mg/kg), while stronger differences were found for As(11.2–164 mg/kg), Cd(0.14–30.5 mg/kg), Mn(0.08–1.84 g/kg), Pb(20.7–183 mg/kg), and Zn(69.1–916 mg/kg). The catchment soils were slightly enriched by Cd, Pb, and Zn. Especially Cd and Zn were characterized by large mobilizable proportions.The mean trace metal concentrations in riverbed sediments were higher than in catchment soils, while reservoir sediments accumulated the highest amounts of the analyzed elements. The enrichment of trace metals in reservoir sediments was generally determined by the sedimentation of fine particles, while the distribution of As, Fe, and Mn was additionally impacted by redox conditions. For Cd and Zn, which in comparison were most enriched in riverbed and reservoir sediments, a significant release from soils by leaching processes was observed. The accumulation of As and Pb in reservoir sediments was influenced to a greater extent by soil erosion and by anthropogenic or chalcogen sources in the catchment.     

The role of arbuscular mycorrhiza on change of heavy metal speciation in rhizosphere of maize in wastewater irrigated agriculture soil

To understand the roles of mycorrhiza in metal speciation in the rhizosphere and the impact on increasing host plant tolerance against excessive heavy metals in soil, maize ( Zea mays L. ) inoculated with arbuscular mycorrhizal fungus ( Glomus mosseae) was cultivated in heavy metal contaminated soil. Speciations of copper, zinc and lead in the soil were analyzed with the technique of sequential extraction. The results showed that, in comparison to the bolked soil, the exchangeable copper increased from 26% to 43% in non-infected and AM-infected rhizoshpere respectively; while other speciation (organic, carbonate and Fe-Mn oxide copper) remained constant and the organic bound zinc and lead also increased but the exchangeable zinc and lead were undetectable. The organic bound copper, zinc end lead were higher by 15%, 40% and 20%, respectively, in the rhizosphere of arbuscular mycorrhiza infected maize in comparison to the non-infected maize. The results might indicate that mycorrhiza could protect its host plants from the phytotoxicity of excessive copper, zinc and lead by changing the speciation from bio-available to the non-bio-available form. The fact that copper and zinc accumulation in the roots and shoots of mycorrhia infected plants were significantly lower than those in the non-infected plants might also suggest that mycorrhiza efficiently restricted excessive copper and zinc absorptions into the host plants. Compared to the non-infected seedlings, the lead content of infected seedlings was 60% higher in shoots. This might illustrate that mycorrhiza have a different mechanism for protecting its host from excessive lead phytotoxicity by chelating lead in the shoots.     

Toxicities and risk assessment of heavy metals in sediments of Taihu Lake, China, based on sediment quality guidelines

The occurrence, toxicities, and ecological risks of five heavy metals(Pb, Cu, Cd, Zn and Ni) in the sediment of Taihu Lake were investigated in this study. To evaluate the toxicities caused by the heavy metals, the toxicities induced by organic contaminants and ammonia in the sediments were screened out with activated carbon and zeolite. The toxicities of heavy metals in sediments were tested with benthic invertebrates(tubificid and chironomid).The correlations between toxicity of sediment and the sediment quality guidelines(SQGs)derived previously were evaluated. There were significant correlations(p 0.0001) between the observed toxicities and the total risk quotients of the heavy metals based on SQGs,indicating that threshold effect level(TEL) and probable effect level(PEL) were reliable to predict the toxicities of heavy metals in the sediments of Taihu Lake. By contrast, the method based on acid volatile sulfides(AVS) and simultaneously extracted metals(SEM),such as ∑SEM/AVS and ∑SEM-AVS, did not show correlations with the toxicities. Moreover,the predictive ability of SQGs was confirmed by a total predicting accuracy of 77%. Ecological risk assessment based on TELs and PELs showed that the contaminations of Pb, Cu, Cd and Zn in the sediments of Taihu Lake were at relatively low or medium levels. The risks caused by heavy metals in the sediments of northern bay of the lake, which received more wastewater discharge from upper stream, were higher than other area of the lake.     

Heavy metals in maternal and cord blood in Beijing and their efficiency of placental transfer

This study aimed to determine the effect of exposure to heavy metals in pregnant women in Beijing, China. We also evaluated the association of these heavy metals with birth weight and length of newborns. We measured the levels of 10 heavy metals,including lead(Pb), titanium(Ti), manganese(Mn), nickel(Ni), cadmium(Cd), chromium(Cr), antimony(Sb), stannum(Sn), vanadium(V), and arsenic(As), in 156 maternal and cord blood pairs. An inductively coupled plasma mass spectrometry method was used for measurement. Pb, As, Ti, Mn, and Sb showed high detection rates( 50%) in both maternal and cord blood. Fourteen(9%) mothers had blood Pb levels greater than the United States Center for Disease Control allowable threshold limit for children(50 μg/L).In prenatal exposure to these heavy metals, there was no significant association between any heavy metal and birth weight/length. Moreover, we estimated the placental transfer efficiency of each heavy metal, and the median placental transfer efficiency ranged from 49.6%(Ni) to 194%(Mn)(except for Cd and Sn). The level and detection rate of Cd in maternal blood were much higher than that in cord blood, which suggested that Cd had difficulty in passing the placental barrier. Prospective research should focus on the source and risk of heavy metals in non-occupationally exposed pregnant women in Beijing.     

Application of ultrasonic to speciation analysis of heavy metals in soil

In order to reduce the operation time and improve the extraction efficiency, ultrasonic energy by means of ultrasonic bath was used to the modified Tessier sequential extraction for speciation analysis of heavy metals in soil. Extractable contents of Cu, Fe, Mn, Ni,Pb and Zn were measured by atomic absorption spectroscopy(hAS). The merit of the ultrasonic extraction (UE) applied to the modified Tessier method is not only that the operation time for the first 4 fractions was reduced from ca. 18 h to 8 h, comparing with conventional extraction(CE), but also the extraction efficiency was higher. The results for both of UE and CE were consistent. The extractable Cu, Ni and Zn in the sample No. 1 were mainly associated with the third fraction (Fe-Mn oxides fraction), and fourth fraction (organic matter fraction) in the sample No.2. The extractable Fe and Mn were all mainly associated with the third fraction, and Pb the fourth fraction in both of the samples. The effects of concentration of hydroxylamine chloride on the capability for the extraction of studied metals were also studied.     

Partitioning of heavy metals in the surface sediments of Quanzhou Bay wetland and its availability to Suaeda australis

In order to investigate distributions of heavy metal pollution in Quanzhou Bay wetland, the total concentration and chemical partitioning of a number of heavy metals （Cu, Zn, Cd, Pb, Cr, Hg） in sediments of three sampling sites of Quanzhou Bay wetland and their availability to Suaeda australis were analyzed. The Geoaccumulation Index （Igeo） values reveal that the sediments of three sampling sites may all be considered as moderately contaminated for Pb and Zn, and all sediments might be strongly contaminated with cadmium. The partitioning analyses revealed the measured heavy metals in three sites are bound to the exchangeable fraction at lower concentrations. The measured metals in a considerable amount are bound to the reducible and oxidizable fractions, and a high proportion of the measured heavy metals were distributed in the residual fraction in the sediment samples. The concentrations of Cd in each chemical phase extracted from the sediments are above natural global background levels and should be further investigated because of its toxicity. Suaeda australis has different accumulation abilities for the measured heavy metals. For the root and stem, the bioaccumulation ability assessed by bioaccumulation factor （BAF） for the measured heavy metals follows the decreasing order as： Cu〉Cr〉 Zn〉Cd, Pb, Hg. In the leaf, stronger bioaccumulation ability for Hg is exhibited. The heavy metal concentrations in Suaeda australis roots have positive correlations with their available fractions, while the exchangeable fraction of Cu and Cd might have be more important to both mature plant roots and seedling roots uptake than other fractions; as for Cr, the oxidizable fraction might make a greater contribution to the plant root uptake; as for Zn, the reducible fraction might make so contribution ; and for Pb, the oxidizable fraction might make a significant contribution to the mature plant root uptake, however, the exchangeable fraction might have a significant contribution to the seedling root uptake.     

Speciation and fractionation of heavy metals in soil experimentally contaminated with Pb,Cd, Cu and Zn together and effects on soil negative surface charge

Speciation and fractionation of heavy metals in soil subsamples experimentally loaded with Pb, Cd, Cu and Zn in orthogonal design was investigated by sequential extraction, and operationally defined as water-soluble and exchangeable(SE), weakly specific adsorbed( WSA),Fe and Mn oxides-bound(OX) and organic-bound( ORG). The results showed that fractions of heavy metals in the soil subsamples depended on their speciation. About 90% of Cd and 75% of Zn existed in soil subsamples in the SE fraction. Lead and Cu existed in soil subsamples as SE, WSA and OX fractions simultaneously, although SE was still the major fraction. Organic-bound heavy metals were not clearly apparent in all the soil subsamples. The concentration of some heavy metal fractions in soil subsamples showed the good correlation with ionic impulsion of soil, especially for the SE fraction. Continuous saturation of soil subsamples with 0.20 mol/L NH4CI, which is the first step for determination of the negative surface charge of soil by the ion retention method, resulted in desorption of certain heavy metals from the soil. It was found that the percentage desorption of heavy metals from soil subsamples depended greatly on pH, the composition and original heavy metal content of the soil subsamples. However, most of the heavy metals in the soil subsamples were still be retained after multiple saturation. Compared with the parent soil, the negative surface charge of soil subsamples loaded with heavy metals did not show difference significantly from that of the parent one by statistical analysis. Heavy metals existed in the soil subsamples mainly as exchangeable and precipitated simultaneously.     

Comparison of Pb and Cd adsorption to the surface coatings and surficial sediments collected in Xianghai Wetland

Surface coatings and surficial sediments were obtained in four natural waters in Xianghai Wetland in China to study the role of surface coatings and surficial sediments in controlling the transporting and cycling of heavy metals in aquatic environments. Pb and Cd adsorption to the surface coatings and surficial sediments were measured under controlled laboratory conditions(mineral salts solution with defined speciation, ionic strength 0.0.5 mol/L, 25℃ and pH 6.0 for surface coatings: and 0.00.5 mol/L CaCl2 solution, 25℃ and pH 6.0 for surficial sediments). The Langmuir adsorption isotherm was applied to estimate equilibrium coefficients of Pb and Cd adsorption to the surface coatings and surficial sediments, and the component analyses of surface coatings and surficial sediments were also carried out.Correlation analyses between the maximum adsorption of Pb and Cd (Гmax) and the components in the surface coatings and surficial sediments suggested that there was a statistically significant trend for Pb and Cd adsorption(Гmax) to the surface coatings to increase with increasing in contents of Fe and Mn oxides in the surface coatings and surficial sediments. And the metal adsorption abilities of surface coatings were much stronger than those of surficial sediments, highlighting that in the same water, i.e. at the same pH and initial metal concentrations, the metals(such as lead and cadmium) in supernatant were feasible to be adsorbed by surface coatings than surficial sediments. The more importance of surface coatings than surficial sediments for adsorbing and cycling of heavy metals in aquatic environments was evidenced.     

Distribution and relationship between antimicrobial resistance genes and heavy metals in surface sediments of Taihu Lake, China

Heavy metals, pharmaceuticals, and other wastes released into the environment can significantly influence environmental antibiotic resistance. We investigated the occurrence of 22 antimicrobial resistance genes(ARGs) and 10 heavy metal concentrations, and the relationship between ARGs and heavy metals in surface sediment from seven sites of Lake Taihu. The results showed significant correlations(p 0.05) between sediment ARG levels,especially for tetracycline and sulfonamides(e.g., tet(A), tet(D), tet(E), tet(O), sul1, sul2 and int-1) and specific heavy metals(Fe, Mn, Cr, Cu, Zn, among others) in the Lake. In the surface sediments, heavy metals showed an interaction with resistance genes, but the strength of interaction was diminished with increasing depth. For most of the heavy metals, the concentration of elements in the top sediments was higher than that in other depths.Tetracycline resistance genes(tet(A), tet(B), tet(D), tet(E) and tet(O), β-lactam resistance genes(SHV, TEM, CTX, OXA and OXY) and sulfonamide resistance genes(sulA, sul1, sul2, sul3 and int-1) were detected. They showed a trend which inferred a statistically significant increase followed by decreases in the relative abundance of these ARGs(normalized to 16 S rRNA genes) with increasing depth. This study revealed that tet(A), tet(O), TEM, OXY, int-1, sul1 and sul3 were widespread in surface sediments with high abundance, indicating that these genes deserve more attention in future work.     

重金属元素BCR提取法及在太湖沉积物研究中的应用

采用BCR提取法,HCl—HNO3-HF消化法和ICP—AES仪器测定了西太湖沉积岩芯中Cu,Fe,Mn,Ni,Pb和Zn6种重金属元素不同形态的质量分数。结果表明：采用BCR方法对太湖沉积物重金属元素形态进行提取,提取结果具有较高的精度和稳定性;受元素地球化学性质及沉积物理化性质的影响,Cu,Fe,Ni和Zn以残渣态为主;Mn以可交换态及碳酸盐结合态为主;Pb的有机物及硫化物结合态,Fe／Mn氧化物结合态以及残渣态的质量分数基本一致;重金属元素Fe／Mn氧化物结合态的质量分数与可还原态Mn质量分数有较好的正相关性,有机物及硫化物结合态的质量分数与有机质质量分数相关性较好。     

某铜矿区土壤重金属污染状况研究

通过对某铜矿区土壤重金属含量及化学形态分布进行分析,探讨了采矿过程中的重金属在土壤中的积累特征。结果表明,该矿区的Cu、Zn、Pb、Cd、Ni在土壤中的积累程度相当高。各采样点的重金属综合污染递减顺序依次为:堆浸泥>最后沉淀池>堆浸矿>堆浸土>金矿排污口污泥>原生土壤>铜矿区下游江边土壤。堆浸矿土壤的重金属以残渣态、水溶态、有机质硫化态这三种组分为主,而堆浸泥土壤则以Fe-Mn氧化物结合态为主。     

山东南四湖沉积物中汞的污染现状及迁移研究

通过测定南四湖及其入湖河流沉积物中总汞和形态含量,研究南四湖沉积物中汞的污染现状及空间迁移特征.南四湖表层沉积物中总汞含量为0.046 mg·kg-1,明显高于其环境背景值,表明南四湖受到一定程度的汞污染;沉积物中汞的形态主要以残渣态为主,占总汞含量的65.15%,非残渣态占总汞比例相对较小,依次为有机结合态(30.61%)、可提取态(2.93%)、铁锰氧化态(1.31%),其空间变化为独山湖区和昭阳湖区非残渣态汞含量较低,南阳湖区和微山湖区相对较高,具有一定的潜在生态危害;从水平方向来看,南四湖表层沉积物中汞含量具有明显差异,各湖区污染程度不同,汞在水平方向迁移较明显;垂直方向来看,从柱状沉积物底部到顶部汞的含量呈增加趋势,这可能与不同时期社会经济状况有关.     

西南典型碳酸盐岩高地质背景区农田重金属化学形态、影响因素及回归模型

土壤重金属化学形态是决定重金属生物活性和生物毒性的重要因素,是科学评价西南碳酸盐岩高地质背景区土壤重金属生态风险的关键.为了探明碳酸盐岩高地质背景区土壤重金属化学形态分布情况,选择贵州省典型碳酸盐岩分布区,以第二次全国土壤普查图斑为采样单元,在农田中采集土壤表层样品309件,利用改进的Tessier七步顺序提取法,分析了As、Cd、Cu、Hg、Ni、Pb和Zn等7种重金属的水溶态（F1）、离子交换态（F2）、碳酸盐结合态（F3）、弱有机结合态（F4）、铁锰氧化物结合态（F5）、强有机结合态（F6）和残渣态（F7）这7种化学形态.结果发现,土壤中重金属As、Cu、Hg、Ni、Pb和Zn残渣态比例均超过50%,有效组分（F1~F3）比例均小于5%,潜在生物有效组分（F4~F6）比例低于45%,活性较低,生态风险不高.Cd的有效组分和潜在生物有效组分占比分别为55.49%和29.37%,远高于其他重金属,基于土壤重金属形态的生态风险远小于基于土壤总量的生态风险.逐步回归方程可以有效建立Cd、Cu和Pb生物有效组分与影响因素之间的关系.重金属全量和pH值是影响碳酸盐岩高地质背景区土壤重金属化学形态的重要因子,受研究区长期土法炼锌活动和碳酸盐岩风化成土过程中重金属元素倾向于在残渣态中富集的影响,土壤有机质（OM）和氧化物含量对土壤重金属化学形态影响相对较小.     

典型砒霜厂污染场地重金属污染特征及环境风险评价

以某个砒霜厂旧址为研究对象,分析场地的重金属污染特征。结果表明,该场地受到砷、铜、铅、镉和锌等重金属污染,其中,砷污染指标超过评价标准值达7 199倍;基于《展览会用地土壤环境质量评价标准(暂行)》条件下,采用RBCA模型计算砷、镉、铜、锌对人体健康的环境风险,结果表明,该场地砷超过了致癌风险指数标准限值-6(10)及非致癌危害商标准限值(1),说明砷具有很大的环境风险;采用IEUBK模型计算铅对人体的健康风险,结果表明,铅也具有一定的环境风险。因此,该污染场地在开发利用过程中需要对环境风险区域进行治理修复后才能使用。     

环渤海湾诸河口底质现状的调查研究

20 0 1年 6月实地采集了环渤海湾诸河口 19处土样 ,进行了汞、铜、锌、铅、砷、总氮、总磷和有机质含量分析 ,发现环渤海湾诸河口底泥中基本无重金属 (及砷 )污染 ,但与历史资料相比 ,近年来重金属含量普遍增加 ,特别是铅和锌含量增加幅度较大 .大多数河口底泥中的总氮和总磷含量较高 ,尤其是海河口附近的河口总氮和总磷含量高达 0 14%和 0 0 9%,通过与水体的交换 ,将对水体富营养化产生影响 .     

抚顺市典型区域土壤重金属污染调查与评价

对抚顺市城区4个典型区域的土壤重金属铜、锌、铅、镉、铬、镍、汞、砷的污染现状进行了调查和分析。结果表明：重金属含量在各典型区域内差异较大,说明点污染源有较大影响;固体废物填埋场及周边地区土壤污染等级为3级轻污染,重污染企业及周边地区和采矿区及周边地区土壤污染等级为2级警戒限,而污灌区及周边地区的土壤污染等级为1级安全;抚顺市城区4个典型区域土壤重金属潜在生态风险均处于低水平。     

巢湖沉积物中重金属的BCR形态分析

以巢湖沉积物为研究对象,利用BCR(European Communities Bureau of Reference)连续提取法分析了沉积物样品中Zn、Cu、Pb、Cd、Mn赋存特征,分为可交换态及碳酸盐结合态、铁锰氧化物结合态、有机物及硫化物结合态和残渣态。结果表明:南淝河入湖区S1采样点五种金属总量都达到最高,兆河入湖区S2采样点金属总量浓度最低。五种金属中锌和锰的质量较高,重金属回收率分别为:锌(93%),铜(92%),铅(90%),镉(92%),锰(93%)。Cu以残渣态为主(54.7%),Zn以铁锰氧化物结合态为主(40.5%),Pb以有机物、硫化物结合态为主(35.3%),Cd和Mn以可交换态及碳酸盐结合态为主,所占比例分布为41.9%、58.6%。研究表明,应用BCR连续提取法有助于确定沉积物中重金属的污染状况和潜在释放能力。     

伊犁河谷典型区域土壤重金属含量状况及评价研究

"十二五"期间自治区加大了对伊犁河谷境内典型生态环境区域集中式饮用水源地土壤、农田、果园、菜地以及昭苏、特克斯和新源三大天然草场土壤汞(Hg)、镉(Cd)、铅(Pb)、砷(As)、铜(Cu)、铬(Cr)、镍(Ni)、锌(Zn)八种重金属元素的监测,通过对上述监测数据的统计分析和评价表明:伊犁河谷典型区域土壤重金属含量均低于《土壤环境质量标准》(GB 15618-1995)(二级、旱地)限值,整体处于清洁安全水平,尚未受到人为显著影响.     

螯合剂复配对实际重金属污染土壤洗脱效率影响及形态变化特征

乙二胺四乙酸二钠(EDTA)是土壤重金属污染洗涤修复中最常用的洗涤剂,然而其难降解性会对环境产生不利影响.而污染场地重金属形态分布对其环境风险至关重要.以某化工场地多种重金属污染土壤为对象,为减少EDTA用量,开展室内振荡实验考察EDTA与EDDS复配对As、Cd、Cu及Pb的洗脱效果和最佳复配比条件下洗涤前后重金属形态变化.结果表明在最优洗脱条件下,As、Cd和Pb去除率在EDTA∶EDDS=7∶3时达到最高,分别为12.67%、38.71%和31.09%;Cu在复配比为9∶1时可达16.91%.洗涤后,As的铁锰氧化态含量升高,会增加一定的环境风险;Cd的形态分布大体与原土一致;Cu和Pb的洗脱主要来自铁锰氧化态,其中Pb的铁锰氧化态洗脱量最大,而有机结合态所占百分比降幅最显著.复配体系不仅对4种重金属的洗脱率有一定提升,洗涤后重金属有效态比例也有所降低,对土壤重金属污染的修复具有指导意义.