羟基磷灰石对沉积物中重金属释放特性的影响

以羟基磷灰石掺杂前后模拟重金属污染沉积物为研究对象,利用混匀释放实验及化学连续萃取法分析沉积物中重金属的释放特征及形态分布特性,考察了羟基磷灰石对重会属污染沉积物中Cu、zn、Pb、Cd稳定性的影响.结果表明不同来源模拟污染沉积物中松花江沉积物中的重金属最易重新释放,而伊通河沉积物中的重金属释放量最小;同时伊通河沉积物中残渣态重金属的比例较其它沉积物高很多,而可交换态和碳酸盐结合态的重金属比例较其它沉积物低很多,说明同时进入沉积物中的重金属,伊通河沉积物中的重金属相对稳定一些.羟基磷灰石的掺杂不同程度降低了沉积物中重金属的释放能力,促使沉积物中的重金属由较不稳定结合态向较稳定结合态转化,减小了沉积物中重金属的生物可利用性,增强了重金属的稳定性.     

Fractionation analysis of some heavy metals in sediments of the north-western part of the Red Sea,Egypt

Sequential extraction was used to study operationally determined chemical forms (exchangeable, carbonate, reducible metal, oxidisable metal and the residual fractions) of the metals Cd, Cu, Zn and Pb in sediments from 12 sample sites collected from the north-western part of the Red Sea, where improper recreational facilities have resulted in diverse impacts on the coastal environments fronting some of the recreation projects. The results showed that the average percentage of each phase was different among metal types; the residual binding fraction was the most important phase for binding Zn and to a lesser degree Cu. The reducible fraction was the second most important phase for Zn and Cu. For Pb, the fractions bounded to the residual fractions and the reducible phases are equal and exhibited the highest percentages. By contrast, the carbonate fraction was predominant for Cd. The percentages of Cd, Cu, Zn and Pb associated with the carbonate and exchangeable fractions, which are potentially the most harmful to the environment, were calculated and assessed at different sampling sites of the studied sediments. According to the Risk Assessment Code (RAC), the results reveal that Cd is the only metal that poses a high risk to the environment.     

Speciation of Heavy Metals in Floodplain and Flood Sediments: a Reconnaissance Survey of the Aire Valley, West Yorkshire, Great Britain

A five-step sequential extraction technique was used to determine the chemical association of heavy metals (Pb, Zn, Cu and Cd), with major sedimentary phases (exchangeable, surface oxide and carbonate, Fe and Mn oxides, organic and residual metal ions), in samples from floodplain and recent flood sediments of the River Aire, West Yorkshire. Analysis indicates that metals Pb and Zn are primarily associated with the Fe and Mn oxides, Cu with the organic fraction and Cd with exchangeable and surface oxide and carbonate metal ions. Knowledge of the chemical speciation of heavy metals in river sediment, despite the procedure's inherent limitations, facilitates an understanding of their bioavailability, storage and remobilisation in floodplain and river channel environments.     

Heavy metals in albanian coastal sediments

Heavy metals (Fe, Mn, Cr, Ni, Cu, Cd, Pb, Sn) concentration has been determined on 39 coastal sediment samples collected in Albania. The relationship between the heavy metals content and the grain size has been considered. All metals, except Cu and Cd, resulted accumulated in the finest fraction, which constituted up to 95% of most of the considered sediments. A good correlation has been found for Ni, Cr, Fe, Zn, Cu in the entire area, indicating a common origin for these metals in the analyzed sediments. Concentration values fall in the range reported for Dinaric chain derived sediments, revealing, generally, a natural origin of the metal contents. Though in some selected areas such as the Drin and the Skumbin Bay, an antropogenic input of Cr, Fe, Ni and Cu can be observed, as the result of discharging of mines and smelter activities.     

Heavy Metal Pollution in Sediment from the Eastern Adriatic Coast,Croatia

Abstract

Sediment samples were collected from the Adriatic Sea in areas near large coastal towns along the eastern Adriatic coast (Zadar, [Ncirc]ibenik, Split, Plo?e and Dubrovnik).

Considerable quantities of untreated effluents are discharged via freshwater runoff and a variety of industrial waste waters, significantly affecting the quality of marine sediments.

Distribution of some trace metals (Pb, Cu, Ni, Cr, Zn, Mn, Cd, and Al) involved in problems related to metal pollution in Adriatic sediment were examined. Values are expressed as a total concentration of heavy metals of sediment dry weight.

Spatial distribution of some trace metal values in sediments and correlation of results for grain size effect were examined. the trace elements in marine sediments generally remain in the fine grained fraction, often in the silt-clay fraction. Higher values of heavy metals in some areas (Split, Sibenik) could be attributed to anthropogenic effects, i.e. to land-based activities. the main cause of higher values of some metals at open sea sites and in some coastal areas are probably caused naturally by sedimentation processes in those areas. Our results show that the sediments undoubtedly play a key role in determining the transport and ultimate fate of contaminants.     

广州城市水体沉积物中重金属形态分布研究

选取广州城市水体中的４ 个污染沉积物样品,采用连续提取法研究沉积物中重金属元素（ Ｐｂ 、 Ｚｎ 、 Ｃｕ 、 Ｎｉ 、 Ｃｒ 、 Ｍｎ） 的形态分布,结果表明：重金属元素主要以残渣态、有机结合态和氧化铁结合态存在,其中 Ｐｂ 、 Ｎｉ、 Ｍｎ 以残渣态和氧化铁结合为主, Ｚｎ 以残渣态和有机结合态为主, Ｃｕ 以有机态和氧化铁结合态为主, Ｃｒ 以氧化铁结合态为主。沉积物中固相组分对重金属的富集能力为：无定型氧化锰＞ ＞ 碳酸盐＞ 氧化铁＞ 有机质,而富集量则是后两者大于前两者。     

贵阳市冬季PM_(2.5)中典型重金属元素的化学形态分析与健康风险评价

为了更准确地研究重金属的生物有效性和对环境与人体的潜在生态危害,采用改进BCR法分析了贵阳市冬季PM_(2.5)中Cu、Mn、Co、Cd、Pb这5种重金属元素的化学形态,并评价了它们的生物有效性和健康风险。结果表明:不同重金属元素形态分布存在差异,Cu主要是弱酸溶态,其次是可氧化态;Mn主要是弱酸溶态,其次是残渣态;Co没有检测出可还原态,而在其他3种形态分布比较平均;Pb和Cd绝大部分都是弱酸溶态。生物有效性系数(K)分析结果表明:重金属生物有效性强弱顺序为CdPbMnCuCo,其中Cd和Pb的K0.8,属于生物可利用性元素;Mn、Cu、Co的K值在0.4~0.7之间,属于潜在生物可利用性元素。健康风险评价表明:成人的致癌风险比儿童大,尤其Cd对成年人存在潜在的致癌风险,且成年男性高于成年女性;Mn存在潜在非致癌风险,且对儿童的风险最大。     

填埋场内重金属总量及其形态分布对迁移性的影响

以杭州市天子岭填埋场为例,对不同深度填埋层中的重金属总量、重金属迁移率和重金属形态分布进行了研究．结果表明,尽管填埋层中的重金属总量是土壤背景值的数十倍,超出土壤环境质量标准,但是重金属的迁移率却很低．另外,重金属迁移率与可交换态含量相关;Cd,Cu,Pb,Cr,Ni和Zn在填埋层中均以残渣态为主,填埋场中重金属都得到了有效固定,迁移性很差;各元素的易还原态与难还原态是重金属除残渣态之外主要的结合态(除Cr),铁锰氧化物循环是控制填埋场中重金属转化行为的主要机制之一;Cu的酸可溶态与易还原态具有较好的相关性,说明cu这两种形态的转化行为相似．     

Effect of acid rain on the fractionation of heavy metals and major elements in contaminated soils

Acid rain is a serious environmental problem worldwide. In the present study, we investigated the effect of acid rain (1:1 equivalent basis H₂SO₄:HNO₃) at pH values of 2.0, 4.0 and 7.0 on the fractionation of heavy metals (Cd, Cu, Fe, Mn, Ni, Pb and Zn) and major elements (K, Na, Ca, and Mg) in contaminated calcareous soils over a 2084 h period. Heavy metals and major elements in soil samples were fractionated before and after 2084 h kinetic release using a sequential extraction procedure. Before kinetic studies the predominant fractions of K, Na, Ca, Mg, Cd and Ni were mainly associated with carbonate fraction (CARB), whereas Fe, Mn and Zn were associated with the Fe–Mn oxide fraction (Fe–Mn oxide). The highest percentage of Pb and Cu were found in the exchangeable (EXC) and organic matter (OM) fractions, respectively. After kinetic study using different simulated acid rain solutions, the major fractions of heavy metals (expect of Cu) and Na was the same as before release. Upon the application of different acid rain solutions, K and Mg were found dominantly in Fe–Mn oxide fraction, whereas Ca was in the EXC fraction. The results provide valuable information regarding metal mobility and indicated that speciation of metals (Cu and Zn) and major elements in contaminated calcareous soils can be affected by acid rain.     

Speciation of heavy metals in Albanian coastal sediments

This article presents results on heavy metal (Fe, Mn, Cr, Ni, Cu, Cd, Pb and Zn) speciation in the coastal sediments of Albania. Sediment samples were collected within the framework of the activities of the Interreg Italia–Albania Project, carried out in the Southern Adriatic Sea in 2000–01. This study shows that Albanian coastal sediments are highly influenced by river input, as the decreasing concentrations from coast to offshore confirm. Pb represents an exception of the general trend; meteoric inputs are prevalent for this metal. Ni, Cr, Fe, Zn and Cu correlate significantly and positively in the entire area, indicating a common origin for these metals in the analyzed sediments. All metals result mostly associated to the most refractory phases, which constitute up to 80% of the total concentration. Nevertheless a recent input of Cr, Ni, Cu and Mn can be observed, as the result of mining and industrial activities, in some selected areas, such as the Drin Bay and Durres. Their high concentration in the bioavailable phase can determine toxic effect upon biota.     

宝鸡城市街尘、土壤及河流沉积物重金属形态迁移特征

在宝鸡城市街尘、土壤及河流沉积物基本理化性质和重金属元素含量分析的基础上,重点研究了重金属元素在街尘、土壤及河流沉积物中的赋存形态和迁移特征.结果表明:在街尘中Cu主要以可氧化态和残余态形式存在,Pb主要以可还原态和可氧化态形式存在,Zn和Cd主要以乙酸可提取态形式存在,Mn、Fe、Co、Ni和Cr主要以残余态形式存在...     

Geochemical forms of trace metals in mangrove sediments—Red Sea (Egypt)

Seven sediment samples from mangrove sediments of the Red Sea were taken in order to evaluate the possible contamination of the sediments by trace metals (iron (Fe), manganese (Mn), zinc (Zn), copper (Cu), lead (Pb) and cadmium (Cd)). Sequential extraction techniques were performed to study the different geochemical forms of these metals. X-ray diffraction analysis has been performed to correlate the mineralogical composition with the geochemical forms of the studied elements. The results of Fe and Mn contents indicate that they are in large part from lithogenous origin. The elevated concentrations are associated with the residual form ranged from 70 to 93% for Fe and 46 to 70% for Mn. The percentage of Zn, Cu, Cd and Pb in the non-residual form was much greater than that of the residual fractions. This reflects the high mobility and bioavailability of these metals in mangrove sediments of the Red Sea. X-ray diffraction analysis revealed the presence of silicate components including quartz, feldspars and clay minerals in some locality. Non-silicate components recorded in the study area as calcite as well as, Mg-calcite. Quantitatively both components i.e. silicate and carbonate varied according to their source material.     

Geochemical forms of trace metals in mangrove sediments—Red Sea (Egypt)

Seven sediment samples from mangrove sediments of the Red Sea were taken in order to evaluate the possible contamination of the sediments by trace metals (iron (Fe), manganese (Mn), zinc (Zn), copper (Cu), lead (Pb) and cadmium (Cd)). Sequential extraction techniques were performed to study the different geochemical forms of these metals. X-ray diffraction analysis has been performed to correlate the mineralogical composition with the geochemical forms of the studied elements. The results of Fe and Mn contents indicate that they are in large part from lithogenous origin. The elevated concentrations are associated with the residual form ranged from 70 to 93% for Fe and 46 to 70% for Mn. The percentage of Zn, Cu, Cd and Pb in the non-residual form was much greater than that of the residual fractions. This reflects the high mobility and bioavailability of these metals in mangrove sediments of the Red Sea. X-ray diffraction analysis revealed the presence of silicate components including quartz, feldspars and clay minerals in some locality. Non-silicate components recorded in the study area as calcite as well as, Mg-calcite. Quantitatively both components i.e. silicate and carbonate varied according to their source material.     

滇池沉积物中重金属污染特征及其生态风险评估

采集了滇池北部和中心区域2根柱状沉积物样品,分析其常量元素（Fe、Mn、Al、Ti、Ca、K）、微量元素（Ba、Sr、Cu、Pb、Zn、V、Cd）剖面分布特征,并采用H？kanson潜在生态危害指数法对典型重金属（Cd、Cu、Zn、Pb）进行了污染潜在生态风险评估。结果表明：沉积物中常量元素以Fe2O3、CaO及Al2O3为主,MnO、K2O及TiO2含量较少,变化范围是Fe2O3为8.0～14.9%、MnO为0.1～0.2%、Al2O3为9.0～20.1%、TiO2为1.5%～2.8%、CaO为0.4～21.7%、K2O为1.5～2.0%;微量元素Pb, Cd, Zn, Ba, Cu, Sr 及V含量均较高,变化范围是Pb为73.8～105.3 mg·kg^-1、Cd为1.0～3.4 mg·kg^-1、Zn为123.4～210.6 mg·kg^-1、Ba为264.8～435.7 mg·kg^-1、Cu为77.5～133.5 mg·kg^-1、Sr为34.9～137.5 mg·kg^-1以及V为177.7～284.7 mg·kg^-1。尤其表层0～12 cm内（1950 s以后）,各元素含量值均明显高于12 cm以下各值,20世纪50年代后滇池流域内工农业发展及污染物输入是造成金属元素含量累积的主要因素。沉积物中典型重金属Cu、Zn、Pb、Cd污染潜在生态风险评估结果：Cu、Zn和Pb处于中度污染,且C if 值越接近表层（0～12 cm）其值越高,这表明自1950S后污染程度不断加重,其中 Cd 累积与污染比较严重,分析多种元素的多因子污染参数之和C d表明滇池沉积物中多种元素污染整体处于“较高”污染程度,分析多种元素的潜在生态风险指数RI表明滇池沉积物中重金属潜在生态风险处于“很高”水平。同时,滇池北部沉积物中重金属潜在危害较严重且近年来污染有加重趋势。     

Fractionation of trace metals (Mn,Zn, Cu,Pb) in Red Sea sediments,Gulf of Aden,Yemen

A sequential extraction technique was applied to estimate the chemical association of Mn, Zn, Cu and Pb in five chemical phases (exchangeable, carbonate, Fe–Mn oxides, organic matter and residual) in sediments of the Gulf of Aden, Yemen. The results indicated that a higher level of Mn was associated with the residual fraction (natural sources) than the non-residual fraction (anthropogenic sources). Zn fractionations revealed that it was associated more with Fe–Mn oxides and organic fractions than exchangeable and carbonate fractions. Most of the Cu was present in the residual form (60–72%) except for in the main port area (zone III), where it was associated with the organic phase (77% of the total Cu content, the organic matter content was 5%). Similarly, most Pb was bound in the residual fraction (56–71%) except the main port area where ～ 62% of the total Pb was bound in non-residual fractions. It was also found that the Pb concentration in the exchangeable fraction was very high compared with other metals. The risk assessment code for the metals showed a low risk for Zn and Cu, but low to medium risk for Mn. Fractionation of Pb showed medium risk at most of the regions except at the eastern area, which revealed a high risk for the aquatic environment.     

典型城市污染水体底泥中重金属形态分布和相关性

采用Tessier五步连续提取法,研究了南京市莫愁湖、玄武湖、秦淮河13个底泥样品中的重金属的形态分布情况,分析了重金属浸出量与各形态间的相关性及有机质与有机结合态的相关性,并通过红外谱图分析了有机质与重金属结合的机理.结果表明:底泥中Pb,cu,zh,Ni,Cr主要以有机结合态和残渣态俘在,两种形态的含量占总量70%以上,Zn和Cd的可交换态和碳酸盐结合态含量相列较高,Zn约占20%,Cd约占30%;Zn,Cu,Cd,Ni,Cr的浸出量均与可交换离子态呈现显著的相关性,因此可通过减小可交换离子态含量控制底泥重金属污染的风险性;研究还表明,有机质与有机结合态呈现显著的正相关,因此增加底泥中有机质含量有助于重金属向有_棚结合态转化,有机质与重金属的结合主要是由于其中-些官能团和重金属形成稳定的络合物.     

Trace metal distribution in different chemical fractions of marine sediments along the eastern Aegean shelf

The major objective of this study was to carry out sequential chemical extraction for the partitioning of particulate trace metals in sediment samples, collected along the eastern Aegean shelf during cruises July‐August 1994, in the framework of a National Marine Measurement and Monitoring Programme for the Aegean Sea.

Five metals, Cd, Pb, Cu, Zn and Cr were examined in each of sediment samples. Three chemical fractions of the sediments were separated and concentrations of the trace metals were determined by AAS techniques. The three different leaches used were hydroxylamine hydrochloride‐acetic acid, hydrogen peroxide and nitric‐perchloric acids.

Metals were concentrated mainly in the fraction extracted by nitric‐perchloric acids. Lead in the first fraction were found in the sediments of Northern part of Aegean, where the concentration of organic material was high.

The total concentrations of Cd, Cu, Zn, Cr were higher in Izmir Bay than the other sampling points. The distribution of Pb concentrations was the highest in Edremit Bay and Izmir Bay.     

城市地表颗粒物重金属分布特征及其影响因素分析

城市地表颗粒物作为重金属的重要载体,严重危害城市人群和水体,已成为城市环境的重要研究对象。阐述了对地表颗粒物重金属的空间、粒径、赋存形态等分布特征及其影响因素进行系统分析的意义。通过对国内不同城市不同功能区的重金属（主要为：Zn、Cu、Cd、Pb）数据进行对比分析,各功能区重金属污染情况为：Cu、Pb：工业区〉商业区〉交通区〉居民区〉休闲区;Zn：工业区〉交通区〉商业区〉居民区〉休闲区;Cd：交通区〉工业区〉商业区〉居民区〉休闲区,同时各功能区中Zn、Pb含量波动性较大。整体上国内工业区、交通区和商业区地表颗粒物重金属污染严重。与我国的土壤重金属背景值相比,4种金属中Cd污染程度最为严重。探讨了与国外部分城市地表颗粒重金属污染特征之间的差异,指出国内城市重金属含量均值整体上低于欧美发达城市,而国内一线城市重金属含量明显偏高。系统分析了颗粒物重金属的粒级效应,赋存形态以及生物有效性。综述了城市交通活动（主要为交通流量、车辆行驶速度、变速频率、车辆类型、道路特征等）、降雨冲刷事件、雨前干燥期、大气风力作用、和其他因素对地表颗粒物重金属分布特征的影响。某种程度上,道路车辆的行驶速度和变速对颗粒物重金属累积的影响作用大于交通流量。不同降雨事件和雨前干燥期对重金属分布特征影响的研究结论不一,但地表颗粒对大气PM2.5重金属贡献较大。今后应在以下方面进一步加强对城市地表颗粒物重金属的研究：建立颗粒物粒径划分标准;加强重金属在降雨冲刷过程变化规律的分析;探讨地表颗粒物与大气颗粒物重金属转换关系;还应开展中小型城市,城乡结合部（城中村）地表颗粒物重金属污染特性研究。     

长江南京段近岸沉积物中重金属富集特征与形态分析

在对长江南京段八卦洲和杨中两个冲积洲近岸沉积物及其优势野生植物中A1、Cu、zn、Cr、Pb、Nj和Cd元素含量分析的基础上,分别考查了这些重金属的富集系数(EF)和生物富集因子(BCF),并采用BCR连续提取法对Cd的赋存形态进行了研究.结果表明,本区域长江近岸沉积物和野生植物中重金属存在不同程度的富集现象,两洲沉积物中Cu、Cr、Pb、Ni、Cd均有富集趋势,各元素EF>1的样品占总样品比例分别为Cu 50%、Cr40%、Pb40%、Ni 40%、Cd20%.而在野生桐蒿和芦蒿两种优势植物中Cd富集显著,其中桐蒿的BCF平均值高达2.57.采用BCR连续提取法对沉积物中Cd进行形态分析,结果显示,沉积物中Cd主要以酸溶/交换态(B1)和可还原态(B2)为主,二者分别为31.7%和45.5%,占到总量的70%以上,B1态远高于一般土壤和沉积物中重金属的分布,表现出很强的迁移性和生物可利用性.新生成沉积物较老沉积物中的B1态有显著增加,反映出沉积物越新,Cd的迁移性越强的趋势.研究结果说明长江城市段近岸沉积物中Cd受近期人为因素影响明显,具有一定的生态风险.     

Heavy metal and nutrient contamination of marine sediments in Hong Kong

A monitoring programme was performed to use marine sediments as an indicator of marine contamination in Hong Kong. A total of 51 samples were collected from eight marine sites and analysed for pH, redox potential, salinity, total‐N, total‐P, total organic carbon, and total Cu, Zn Pb, Cr and Cd. Sites with high industrial or aquacultural activities contained high total organic carbon contents, total‐N and total‐P contents. Sediments from sites with high industrial activities also enriched with heavy metals. Metal speciation results indicate that Cu and Cr existed mainly in the organic fraction, Pb and Zn were distributed approximately equally in both the organic and residual fractions while Cd mainly occurred in the residual fraction. The Cu, Cr and Zn contents were highly correlated with total organic carbon contents. All samples were classified as non‐acid forming according to the net acid generation test and only samples from the industrial site released a high concentration of heavy metals under a complete oxidising condition. The present study reveals that organic and heavy metal pollution is serious in the marine sediments of Hong Kong, and industrial and aquacultural activities are probably the major sources of contamination.