Distribution and enrichment of heavy metals in a sediment core from the Pearl River Estuary

A sediment core collected from coastal zone near the Qiao Island in the Pearl River Estuary was analyzed for total metal concentrations, chemical partitioning, and physico-chemical properties. Three vertical distribution patterns of the heavy metals in the sediment core were identified, respectively. The dominant binding phases for Cu, Pb, Cr, and Zn were the residual and Fe/Mn oxides fractions. Cd in all sediments was mainly associated with exchangeable fraction. Influences of total organic carbon content and cation exchange capacity on the total concentrations and fractions of almost all the metals were not evident, whereas sand content might play an important role in the distributions of residual phases of Cr, Cu, Pb, and Zn. In addition, sediment pH had also an important influence on the Fe/Mn oxides, organic/sulfide and residual fractions of Cr, Cu, and Zn. Contamination assessment on the heavy metals in the sediment core adopting Index of Geoaccumulation showed that Cr, V, Be, Se, Sn, and Tl were unpolluted, while Cu, Ni, Pb, Zn, Cd, and Co were polluted in different degrees throughout the core. It was remarkable that the various pollution levels of the metals from moderate (for Cu, Pb, and Zn) to strong (for Cd) were observed in the top 45 cm of the profiles. The relative decrease of the residual fraction in the upper 45 cm of the core is striking, especially for Zn and Cu, and, also for Pb, and Cr. The change in fraction distribution in the upper 45 cm, which is very much contrasting to the one at larger depths, confirms that the residual fraction is related to the natural origin of these metals, whereas in the upper part, the non-residual fractions (mainly the Fe/Mn oxides fraction) are increased due to pollution in the last decade. The possible sources for Cu, Pb, Zn, and Cd contaminations were attributed to the increasing municipal and industrial wastewater discharges, agricultural runoff, atmospheric inputs, and runoff from upstream mining or smelting activities, which may be associated with an accelerating growth of economy in the Pearl River Delta region in the past decade.     

Distribution and immobilization of heavy metals in Pliocene aquifer sediments in Wadi El Natrun depression, Western Desert

The Pliocene aquifer receives inflow of Miocene and Pleistocene aquifer waters in Wadi El Natrun depression. The aquifer also receives inflow from the agricultural activity and septic tanks. Nine sediment samples were collected from the Pliocene aquifer in Wadi E1 Natrun. Heavy metal (Cu, Sr, Zn, Mn, Fe, Al, Ba, Cr, Ni, V, Cd, Co, Mo, and Pb) concentrations of Pliocene aquifer sediments were investigated in bulk, sand, and mud fractions. The determination of extractable trace metals (Cu, Zn, Fe, Mn, and Pb) in Pliocene aquifer sediments using sequential extraction procedure (four steps) has been performed in order to study environmental pathways (e.g., mobility of metals, bounding states). These employ a series of successively stronger chemical leaching reagents which nominally target the different compositional fractions. By analyzing the liquid leachates and the residual solid components, it is possible to determine not only the type and concentration of metals retained in each phase but also their potential ecological significance. Cu, Sr, Zn, Mn, Fe, and Al concentrations are higher in finer sediments than in coarser sediments, while Ba, Cr, Ni, V, Cd, Co, Mo, and Pb are enriched in the coarser fraction. The differences in relative concentrations are attributed to intense anthropogenic inputs from different sources. Heavy metal concentrations are higher than global average concentrations in sandstone, USEPA guidelines, and other local and international aquifer sediments. The order of trace elements in the bulk Pliocene aquifer sediments, from high to low concentrations, is Fe?>?Al?>?Mn?>?Cr?>?Zn?>?Cu?>?Ni?>?V?>?Sr?>?Ba?>?Pb?>?Mo?>?Cd?>?Co. The Pliocene aquifer sediments are highly contaminated for most toxic metals, except Pb and Co which have moderate contamination. The active soluble (F0) and exchangeable (F1) phases are represented by high concentrations of Cu, Zn, Fe, and Mn and relatively higher concentrations of Pb and Cd. This may be due to the increase of silt and clay fractions (mud) in sediments, which act as an adsorbent, retaining metals through ion exchange and other processes. The order of mobility of heavy metals in this phase is found to be Pb?>?Cd?>?Zn?>?Cu?>?Fe?>?Mn. The values of the active phase of most heavy metals are relatively high, indicating that Pliocene sediments are potentially a major sink for heavy metals characterized by high mobility and bioavailability. Fe–Mn oxyhydroxide phase is the most important fraction among labile fractions and represents 22% for Cd, 20% for Fe, 11% for Zn, 8% for Cu, 5% for Pb, and 3% for Mn. The organic matter-bound fraction contains 80% of Mn, 72% of Cu, 68% of Zn, 60% of Fe, 35% of Pb, and 30% of Cd (as mean). Summarizing the sequential extraction, a very good immobilization of the heavy metals by the organic matter-bound fraction is followed by the carbonate-exchangeable-bound fraction. The mobility of the Cd metal in the active and Fe–Mn oxyhydroxide phases is the highest, while the Mn metal had the lowest mobility.     

Multivariate statistical techniques for evaluating and identifying the environmental significance of heavy metal contamination in sediments of the Yangtze River, China

The concentrations of heavy metals (Cr, Co, Ni, Cu, Zn, Pb, Cd, As, Hg, and Fe) in sediments of the Yangtze River, China, were investigated to evaluate levels of contamination and their potential sources. The lowest heavy metal concentrations were found in the source regions of the river basin. Relatively high concentrations of metals, except Cr, were found in the Sichuan Basin, and the highest concentrations were in the Xiangjiang and Shun’anhe rivers. All concentrations, except Ni, were higher than global averages. Principal component analysis and hierarchical cluster analysis showed that Zn, Pb, As, Hg, and Cd were derived mainly from the exploitation of various multi-metal minerals, industrial wastewater, and domestic sewage. Cu, Co, and Fe were derived mainly from natural weathering (erosion). Cr and Ni were derived mainly from agricultural activities, municipal and industrial wastewater. Sediment pollution was assessed using the geoaccumulation index (I _geo) and enrichment factor (EF). Among the ten heavy metals assessed, Cd and Pb had the highest I _geo values, followed by Cu, As, Zn, and Hg. The I _geo values of Fe, Cr, Co, and Ni were <0 in all sediments. EF provided similar information to I _geo: no enrichment was found for Cr, Co, and Ni. Cu, Zn, As, and Hg were relatively enriched at some sites while Cd and Pb showed significant enrichment.     

Heavy metal distribution in sediments from Calabar River, southeastern Nigeria

The concentration and areal distribution of selected metals (Pb, Zn, Cu, Cd, Ni, Fe, and Cr) in the sediments of the Calabar River were studied to determine the extent of anthropogenic input and to estimate the effects of dumping industrial waste materials into the river. The concentrations of Pb, Zn, and Cu indicate relatively moderate pollution mainly on the left-hand side of the river while Ni, Cr, Co, Cd, and Fe levels are below values found to have adverse effects on the lives of marine biota. High metal contents are found close to industrial establishments and so enhanced metal concentrations are related to industrial sewage and metal leaching from garbage and solid waste dumps.     

Impact of sewage and mining activities on distribution of heavy metals in the water-soil-vegetation system

Several samples of groundwater and soils and plants have been collected from Sohar (Batina region, NE Oman), which is affected by various activities such as mining, agriculture, and sewage. To characterize quality of groundwater, As and Cu concentrations have been investigated in waters collected from different wells. Comparison of data with local and international standard values revealed that groundwater in Sohar region is characterized by lower concentrations in Cu and As compared with standards. In soils collected from the same area, concentrations of heavy metals have been measured in different fractions in order to investigate the mobility of such elements and risk of vulnerability in this area. A sequential extraction procedure has been applied to surface sediments to determine the partitioning of Zn, Cu, Co, Mn, Fe, Pb, Cr, Cd and Ni among (1) exchangeable and acid-soluble phases, (2) Fe–Mn oxides, (3) organic matter and sulphides and (4) resistant phases. The results showed that the mobile fraction in the sewage area accounts only for 10 % of the total concentration in sediments while in the Cu mining area, the contribution of the mobile fraction may exceed 10 %, especially for Pb, Mn, Cd, Cu and Co. Investigation of concentrations in As and Cu in plants collected from mining and sewage areas revealed an important accumulation of these elements in leaves and may explain enrichment of As in shallow groundwater relative to deep groundwater. This investigation also showed that Cu is more available in sewage area than in mining zone, as opposed to As.     

Speciation and potential remobilization of heavy metals in sediments of the Taihu Lake, China

The species of Cu, Pb, Zn, Cd and Cr in sediments of the Taihu Lake, China, have been analyzed using the sequential chemical extraction method. Variations in the chemical fractions of these metals and their geographic distributions have also been studied. For all five metals, the residual fraction is highest but the exchangeable fraction is lowest among all the fractions. Compared to other metals, Cd has the highest percentage in the exchangeable fraction, and Cr is associated mainly with the residual fraction. Cu in the organic fraction and Pb in the Fe-Mn fraction are the important species, whereas the lowest percentages are found for Cd in the organic fraction, Cu in the Fe-Mn oxide fraction and Pb in the carbonate fraction. With respect to spatial differences, the total contents in the non-residual fractions of the metals in bay sediments are found to be higher than those in other sediments. The fractions of Cd, Cu and Cr showed significant variations in different regions. The fractions of Pb and Zn, however, did not show significant variations in spatial distribution, suggesting different amounts and different paths of anthropogenic input for the metals. Comparisons of the metal speciation indicated that Cd might be the most bioavailable metal, followed by Pb.     

大亚湾表层沉积物重金属元素形态特征、控制因素及风险评价分析

为了解大亚湾表层沉积物中重金属的污染状况,对大亚湾海域23个点位表层沉积物中7种重金属元素（Cr、Ni、Cu、Pb、Zn、Cd、As）的质量分数、形态特征、来源控制因素以及潜在生态风险进行了研究。采用优化BCR提取法分析重金属元素赋存形态,并依据各种重金属元素的形态特征与沉积物基质属性进行了相关因子分析,了解其分布的控制因素。结果表明：大亚湾沉积物重金属元素呈现环带状分布特征,从岸向湾内逐渐减小;重金属元素质量分数的高值区主要分布于大鹏澳、哑铃湾及范和港附近;重金属元素赋存形态中Cr、Ni、Cu、Zn、As主要以残渣态存在,Pb主要以可还原态存在,Cd主要以酸提取态存在;7种重金属元素各自非残渣态所占比率从大到小为Pb(78.83%)、Cd(78.65%)、Cu(48.54%)、Zn(48.10%)、Ni(38.31%)、Cr(28.43%)、As(27.76%),即Pb最高,As最低,表明Pb的迁移性最强;通过因子分析,大亚湾重金属主要为沿岸自然风化产物的输入,其次为工业废水及养殖污水。运用酸提取态风险评估法对重金属元素潜在生态风险进行评价,发现研究区所选重金属元素综合风险评价Cd为高风险,其余重金属为中-低风险等级。     

长江口海域表层沉积物重金属元素赋存形态特征

通过长江河口地区水下表层沉积物样品多种化学元素的赋存形态分析测试数据,综合分析重金属元素的赋存形态特征。研究结果显示：镉、汞、铅残渣态所占比例均小于50%,锌、砷、铬、铜、镍残渣态占比均大于50%;8个元素的残渣态与全量呈显著正相关关系。沉积环境和沉积物粒径对重金属元素赋存形态具有重要影响。沉积物的物质来源、矿物组成特征、水动力作用与沉积物粒度和物理化学条件等是长江口地区表层沉积物重金属元素赋存形态的主要控制因素。     

Evidences for heavy metal contamination in surface sediments of seagrass ecosystem of Lakshadweep archipelago, India

Surface sediments of nine islands of Lakshadweep were evaluated for their heavy metal concentration (Cd, Co, Cr, Cu, Fe, Mn, Ni, Pb and Zn). Sediments of thirteen seagrass and seven non seagrass sites were collected randomly and analysed for heavy metal concentration using Inductively Coupled Plasma Optical Emission Spectrometer. Heavy metals like Cu, Ni and Zn were found in higher concentrations in the seagrass sediments, whereas other heavy metals such as Cd, Co, Cr, Fe, Mn and Pb were higher in non seagrass sediments. Different pollution indices were calculated to evaluate contamination level of all heavy metals in the sediments. Cadmium recorded higher contamination factor (1.733–21.067), enrichment factor (276.10–12,270) and Geo-accumulation Index (0.208–3.811) both in seagrass and nonseagrass sediments. Multivariate statistical analysis such as principal component analysis and cluster analysis coupled together with correlation co-efficient was used to identify the possible sources of heavy metal pollution in the region. Average concentrations of Cd in Lakshadweep islands were slightly higher than effective range, low but still below effective range medium. All other metals were still below these ranges indicating fairly uncontaminated sediment in the region.     

Heavy metals in mangrove sediments of the central Arabian Gulf shoreline,Saudi Arabia

To assess heavy metals in mangrove swamps of Sehat and Tarut coastal areas along the Arabian Gulf, 18 sediment samples were collected for Al, V, Cr, Mn, Cu, Zn, Cd, Pb, Hg, Sr, As, Fe, Co, and Ni analysis. The results indicated that the distribution of some metals was largely controlled by anthropogenic inputs, while others were of terrigenous origin and most strongly associated with distribution of aluminum and total organic carbon in sediments. Mangrove sediments were extremely severe enriched with Sr (EF?=?67.59) and very severe enriched with V, Hg, Cd, Cu, As (EF?=?44.28, 37.45, 35.77, 25.97, and 11.53, respectively). Average values of Sr, V, Hg, Cd, Cu, Ni, As, and Cr were mostly higher than the ones recorded from the Mediterranean Sea, the Red Sea, the Gulf of Aqaba, the Caspian Sea, the Arabian and Oman gulfs, coast of Tanzania, sediment quality guidelines, and the background shale and the earth crust. Landfilling due to coastal infrastructure development around mangrove forests, oil spills and petrochemical and desalination effluents from Al-Jubail industrial city to the north were the anthropogenic activities that further enhanced heavy metals in the studied mangrove sediments.     

Application of multivariate statistical methods to indicate the origin and geochemical behavior of potentially hazardous elements in sediment around the Sarcheshmeh copper mine,SE Iran

Multivariate statistical techniques, i.e., correlation coefficient analysis, principal components analysis (PCA), and hierarchical cluster analysis (CA), were applied to the total and water-soluble concentrations of potentially hazardous metals in sediments associated with the Sarcheshmeh mine, one of the largest Oligo-Miocene porphyry copper deposits in the world. The samples were analyzed for hazardous metal concentration levels by inductively coupled plasma mass spectrometry method. Results indicate that the contaminant metals As, Cd, Cu, Mo, S, Sb, Sn, Se, Pb, and Zn were positively correlated with the total concentrations. These hazardous metals also have strong association in the PCA and CA results. Different anthropic versus natural sources of contaminant metals were distinguished by using CA method. Water-soluble fraction of hazardous metals showed that the hydro-geochemical behavior of these metals in sediments is different considerably. Elements such as Cd, Co, Cr, Cu, Fe, Mn, Ni, S, and Zn are readily water soluble from contaminated samples, especially from evaporative mineral phases, while the release of As, Mo, Sb, and Pb into the water is limited by adsorption processes. Results obtained from the application of multivariate techniques on the water-soluble fraction data set show that the hazardous metals are categorized into three groups including (1) Ni, S, Co, Cu, Cr, and Fe; (2) Se, Mn, Cd, and Zn; and (3) Sb, As, Mo, and Sn. This classification describes the hydro-geochemical behavior of hazardous metals in water–sediment environments of the Sarcheshmeh porphyry copper mine and can be used as a basis in remedial and treatment strategies.     

Heavy metals in freshly deposited sediments of the Gomati River (a tributary of the Ganga River): effects of human activities

 The concentrations of various metals (Cr, Cu, Co, Fe, Mn, Ni, Pb, Zn, and Cd) were determined in recently deposited surface sediments of the Gomati River in the Lucknow urban area. Markedly elevated concentrations (milligrams per kilogram) of some of the metals, Cd (0.26–3.62), Cu (33–147), Ni (45–86), Pb (25–77), and Zn (90–389) were observed. Profiles of these metals across the Lucknow urban stretch show a progressive downstream increase due to additions from 4 major drainage networks discharging the urban effluents into the river. The degree of metal contamination is compared with the local background and global standards. The geoaccumulation index order for the river sediments is Cd>Zn>Cu>Cr>Pb. Significant correlations were observed between Cr and Zn, Cr and Cu, Cu and Zn and total sediment carbon with Cr and Zn. This study reveals that the urbanization process is associated with higher concentrations of heavy metals such as Cd, Cu, Cr, Pb, and Zn in the Gomati River sediments. To keep the river clean for the future, it is strongly recommended that urban effluents should not be overlooked before their discharge into the river. Received: 16 February 1996 · Accepted: 29 February 1996     

太湖沉积物中重金属的地球化学形态及特征分析

用连续提取法分析了太湖沉积物5种重金属的地球化学形态,对地球化学形态的组成和地理特征进行了分析研究.重金属地球化学形态配分的共同特点是可交换态最低,残渣态最高.两种形态中Cd的可交换态最高,Cr的残渣态最高,可交换态最低.Cd的碳酸盐态较高,Cr的最低;Pb、Cd的Fe-Mn氧化态较高,Cu的偏低;Cu的有机态最高,Cd的最低;Zn的地球化学形态比例大都处于中间.地域上变化较大的元素是Cd和Cu,变化不明显的元素有Pb和Zn.化学成分中Fe2O3、MnO与重金属地球化学形态的相关性最好,TOC与Cu的形态相关系数最高.综合对比分析表明,太湖沉积物重金属的生物有效性以Cd为最高,其次为Pb.     

Distribution and chemical speciation of heavy metals in the surficial sediments of the Bak?r?ay and Gediz Rivers, Eastern Aegean

The pollution of aquatic ecosystem by heavy metals has assumed serious proportions due to their toxicity and accumulative behaviour. The toxicity and fate of the water borne metal is dependent on its chemical form and therefore quantification of the different forms of metal is more meaningful than the estimation of its total metal concentrations. A five-step sequential extraction procedure was applied for the determination of the distribution of seven elements (Pb, Cr, Cu, Mn, Zn, Ni, Fe) in sediment samples collected from Bakır?ay and Gediz Rivers. According to this study, the results of metals are mostly retained in the residual, oxidizable and reducible fractions. Based on the chemical distribution of metals, we found that Cr, Zn, Cu and Ni are the most non-mobile metals. Pb is the metal that showed the highest percentages in the residual and reducible fractions. Mn is present in the higher percentages in the reducible and carbonate fractions. However, Fe is present in the greatest percentages in the residual fraction, which implies that these metals are strongly linked to the sediments. The risk assessment code as applied to the present study shows that about 12.3–26.9 and 15.7–33.5% of manganese at most of the sites exist in carbonate fraction in the Bakır?ay and Gediz Rivers, respectively. Therefore, Mn comes under the medium risk category in the Bakır?ay and high-risk category in the Gediz River. Speciation pattern of Cu, Zn, Pb, Cr, Ni, Fe shows low to medium risk to aquatic environment health in both rivers.     

江苏扬中长江漫滩沉积物重金属垂向分布特征及其背景值确定方法

对扬中长江漫滩柱状沉积物Cd、Pb、Cu、N i、Cr、Zn重金属垂向变化特征分析,表层20 cm以上,重金属含量普遍较高,表明了人类活动对长江重金属输入量呈现日益增加的趋势。通过重金属与Fe元素作线性回归方程,求得重金属的背景含量。相比而言,表层沉积物重金属含量反映了长江滩涂沉积物已经呈现明显的污染趋势。     

Trends in the solid phase partitioning of metals in the Thames Estuary sediments during recent decades

A sequential extraction method was employed to extract the metals Al, Ag, Cd, Co, Cr, Cu, Pb, Fe, Li, Mn, Ni, and Zn from a 10-m sediment core taken from the Tilbury Basin on the Thames Estuary. Characteristics of the observed metal partitioning distributions were attributed primarily to the composition of the estuarine waters at the time of deposition. For some metals, a decrease in the bulk sediment metal concentrations from a depth of ?6.59 m ODN to the surface was also observed in one of the solid phases. This was the case for Cr, Cu, and Pb extracted from the organic phase and for Zn extracted from the carbonate phase. This decrease in sediment concentrations is thought to reflect reported improvements to water quality in this region of the Thames Estuary in the early 1960s, following updating of major sewage treatment works (STW) approximately 20 km upstream. These findings give an indication of the influence of estuarine inputs from STW on metal partitioning distributions. The order of mobility for the metals of environmental concern was Cd>Ag>Cr>Ni, Zn>Co, Cu, Pb. for Cd and Ag there was a tendency to partition towards the exchangeable phase, both at the surface and at depth, which indicates the potential for long-term leaching of these metals from the sediments.     

Assessment of trace element geochemistry of Hampton Roads harbor and lower Chesapeake Bay area sediments

Acid extractable Cd, Co, Cr, Cu, Fe, Mn, Ni, Pb. and Zn were determined in sediments from the Inner Virginia Shelf, and from shipping channels in the lower Chesapeake Bay and Hampton Roads, Virginia, harbor system. Data were evaluated by a variety of techniques Levels of Cd, Cu, Pb, and Zn exceeded average crustal abundances for most of the study sites. Cumulative frequency curves suggested that there were two major populations for all metals and perhaps a third and smaller, one for Cd, Cr, and Mn Plots of metal vs Fe indicated no anthropogenic inputs of metals for shelf and Chesapeake Bay channel sites, but suggested anthropogenic influences for all metals in several of the inshore sites. Enrichment factor calculations showed enrichment of Cd, Pb, and Zn with respect to average crustal abundances for all sites and of Cu for the industrial harbor system. A recommendation of this study for evaluation of environmental geochemical metals data is to utilize mean concentrations, cumulative frequency plots, and metal vs Fe and/or enrichment factor calculations when evaluating the pollution status of sediments.     

Environmental geochemistry of El Temsah Lake sediments, Suez Canal district, Egypt

The heavy metal contents of Mn, Ni, Cu, Zn, Cr, Co, Pb, Cd, Fe, and V in the surface sediments from five selected sites of El Temsah Lake was determined by graphite furnace atomic absorption spectrophotometer. Geochemical forms of elements were investigated using four-step sequential chemical extraction procedure in order to identify and evaluate the mobility and the availability of trace metals on lake sediments, in comparison with the total element content. The operationally defined host fractions were: (1) exchangeable/bound to carbonate, (2) bound to Fe/Mn oxide, (3) bound to organic matter/sulfides, and (4) acid-soluble residue. The speciation data reveals that metals Zn, Cd, Pb, Ni, Mn, Cu, Cr, Fe, and V are sink primarily in organic and Fe–Mn oxyhydroxides phases. Co is mainly concentrated in the active phase. This is alarming because the element is enriched in Al Sayadin Lagoon which is still the main site of open fishing in Ismailia. Average concentration of the elements is mostly above the geochemical background and pristine values of the present study. There is a difference on the elemental composition of the sediment collected at the western lagoon (Al Sayadin Lagoon), junction, the shoreline shipyard workshops, and eastern beach of the lake. Depending upon the nature of elements and local pollution source, high concentration of Zn, Pb, and Cu are emitted by industrial wastewater flow (shoreline workshops), while sanitary and agricultural wastewater (El Bahtini and El Mahsama Drains) emit Co and Cd in Al Sayadin Lagoon. On the other hand, there is a marked decrease in potentially toxic heavy metal concentrations in the sediments at the most eastern side of the lake, probably due to the successive sediment dredging and improvements in water purification systems for navigation objective. These result show that El Temsah receives concentrations in anthropogenic metals that risk provoking more or less important disruptions, which are harmful and irreversible on the fauna and flora of this lake and on the whole ecobiological equilibrium.     

Distribution and contamination assessment of toxic trace elements in sediment of the Daliao River System, China

The Daliao River System (DRS) is one of the major river systems in the northeastern China and receives substantial discharges from industrial, municipal, and agricultural effluents. In this study, the contents and partition of toxic trace elements in the DRS sediments were evaluated in terms of contamination levels and ecological risks using geoaccumulation index (Igeo), relative enrichment factor (REF), sediment pollution index (SPI), and potential effect concentration quotient (PECQ). Fourteen samples were collected and measured for trace and major elements and sediment properties. The following concentration ranges (mg kg^?1) of toxic trace elements were found: As, 1.6–18.0; Cd 0.1–0.9; Co 3.8–23.4; Cr 12.9–151.6; Cu 4.6–86.1; Hg 0.01–0.35; Ni 8.4–64.4; Pb 11.6–67.1; Sb 0.13–1.77; V 18.5–153.3; and Zn 20.4–211.3. The proportions of soluble and exchangeable trace metals were less than 1 %, while the proportions of trace metals bound to carbonate, amorphous oxides, organic matter, and crystalline oxides were usually each <10 %. However, 28.8 % of Cd, on average, was associated with carbonate. The average proportions of trace metals in the residual fraction ranged 57.3 % for Cd to 85.4 % for Cr, indicating low mobility and bioavailability. Cr, Ni, V, and Co in the sediments mainly originated from natural sources, while Cd, As, Pb, Sb, and Hg partially originated from anthropogenic sources. The Igeo, REF, SPI, and PECQ values of the heavy metals in the sediment were not in agreement with each another. The average REF values of Cd and As were higher than those of the other metals. However, the average PECQ value was higher for Cr and Ni than for the other metals, indicating that these two metals would cause higher adverse biological effects than the other metals. In addition, the sediments located adjacent to cities were more contaminated. Therefore, it is suggested that future management and pollution control within the DRS might focus on As, Cd, Cr, and Ni in the sediments, particularly in the sediments adjacent to cities.     

Heavy metal partitioning in river sediments severely polluted by acid mine drainage in the Iberian Pyrite Belt

This study provides a geochemical partitioning pattern of Fe, Mn and potentially toxic trace elements (As, Cd, Cr, Cu, Ni, Pb, Zn) in sediments historically contaminated with acid mine drainage, as determined by using a 4-step sequential extraction scheme. At the upperstream, the sediments occur as ochreous precipitates consisting of amorphous or poorly crystalline oxy-hydroxides of Fe, and locally jarosite, whereas the estuarine sediments are composed mainly of detrital quartz, illite, kaolinite, feldspars, carbonates and heavy minerals, with minor authigenic phases (gypsum, vivianite, halite, pyrite). The sediments are severely contaminated with As, Cd, Cu, Pb and Zn, especially in the vicinity of the mining pollution sources and some sites of the estuary, where the metal concentrations are several orders of magnitude above background levels. Although a significant proportion of Zn, Cd and Cu is present in a readily soluble form, the majority of heavy metals are bonded to reducible phases, suggesting that Fe oxy-hydroxides have a dominant role in the metal accumulation. In the estuary, the sediments are potentially less reactive than in the riverine environment, because relevant concentrations of heavy metals are immobilised in the crystalline structure of minerals.