Heavy metals in the hydrological cycle: Trends and explanation

This paper reviews the major sources and transport characteristics of heavy metals in the hydrological cycle. It is demonstrated that heavy metal releases to the environment have changed from 19th and early 20th century production-related activities to consumption-oriented factors in more recent times. The relative roles of particle size, sorption and desorption processes, partitioning and the chemical speciation of heavy metals on fine sediments are identified to understand the likely fate of heavy metals released into fluvial systems. It is argued that the spatial and temporal distribution of heavy metals in the river corridor depends not only on an understanding of metal solubility and speciation, but also on an understanding of sediment dynamics which control, for example, floodplain alluviation and the accumulation of metals in the bottom sediments of contaminated rivers, lakes and reservoirs. Existing long- and short-term records are examined to identify the current state of knowledge about the factors which affect heavy metal releases into aquatic environments. With limited exceptions, it is shown that few long-term studies of trends in heavy metal transport are available although, for some major rivers, limited data on trends in metal concentration exists. Palaeolimnological reconstruction techniques, based on an analysis of lake and reservoir sediments, are identified as a possible means of supplementing monitored records of heavy metal transport. Although numerous studies have suggested that trends in atmospheric contamination, mining and urbanization may be identified in the bottom sediment record, other research has shown that the radionuclide-based chronology and the heavy metal distribution within the sediment are more likely to be a function of post-depositional remobilization than the history of metal loading to the basin. Despite these limitations, it is shown that the incorporation of reservoir bottom sediment analysis into a heavy metal research programme, based in river corridors of Midland England, provides an opportunity to identify and quantify the relative contribution of point and non-point contributions to the heavy metal budget and to relate trends in metal contamination to specific periods of catchment disturbance.     

Influence of mangrove reforestation on heavy metal accumulation and speciation in intertidal sediments

To investigate the influence of mangrove reforestation on heavy metal accumulation and speciation in intertidal sediments, core sediments from a restored mangrove forest and adjacent mud flat in Yifeng Estuary (southeastern China) were analyzed. The chemical speciation of heavy metals (Pb, Zn, Cu, Cr and Ni) was determined according to a sequential extraction procedure. Special attention was paid to the upper 20 cm of sediment, in which metal accumulation was enhanced and speciation was obviously modified. Mangrove reforestation decreased the concentrations of all metals in the acid-soluble fraction and increased metal concentrations in the oxidizable fraction. Increased Pb, Zn and Cu concentrations and decreased Ni and Cr concentrations were observed in the reducible fraction. These results suggest that mangrove reforestation facilitated the accumulation of heavy metals in the upper sediment layers but decreased their bioavailability and mobility.     

Heavy metal contamination and ecological risk in Spartina alterniflora marsh in intertidal sediments of Bohai Bay,China

To investigate the effects of Spartina alterniflora on heavy metals pollution of intertidal sediments, sediment cores of a S. alterniflora salt marsh and a mudflat in Bohai Bay, China were analyzed. The results showed that S. alterniflora caused higher total C and P, but lower bulk density and electrical conductivity. The levels of Cd, Cu and Pb were higher in S. alterniflora sediment. Both Cd and Zn were higher than the probable effect level at both sites, indicating their toxicological importance. The geo-accumulation and potential ecological risk indexes revealed higher metal contamination in S. alterniflora sediment. Multivariate analysis implied that anthropogenic activities altered mobility and bioavailability of heavy metals. The percentage of mobile heavy metals was higher in S. alterniflora sediment, indicating improvement of conversion from the immobilized fraction to the mobilized fraction. These findings indicate that S. alterniflora may facilitate accumulation of heavy metals and increase their bioavailability and mobility.     

Distribution and ecological risk assessment of some heavy metals in coastal surface sediments along the Red Sea,Egypt

The ecological risk assessment for Al,Zn,Cu,Ni,V,Pb,Cd,and Hg in surface sediment collected from the Egyptian Red Sea coast was evaluated using the Geo-accumulation Index(I_(geo)).Sediment Enrichment Factor(SEF) and Potential Ecological Risk Index(PERI) methods.The predominant heavy metal,aluminum,showed high concentrations along both of Aqaba Gulf(4378.8 ± 2554.1 μg/g) and southern part of the Red Sea(2972.8 + 1527.5 μg/g).while it recorded the lowest concentration in Suez Gulf(829.7 ± 398.2 μg/g).The determined heavy metal concentrations had the order of Al Zn -Ni V Pb Cu Cd Hg.The statistical analyses showed some correlations among the heavy metals contents.Several international sediment quality guidelines were used to estimate the quality of the collected sediments.Interestingly,the recorded average heavy metals concentrations were lower than those of the permissible contents for sediment quality guidelines.The Geo-accumulation index calculations(I_(geo)) proved that the investigated region could be classified as an unpolluted area.Sediment Enrichment Factor(K_(SEF)) study showed high values in Suez Gulf region.The single pollution index analysis of heavy metals in the sediments(C~i_f) indicated that Al,Zn,V,and Pb were of natural origin,while Ni,Cd and Hg were seriously affected by human activities.Interestingly,amongst,all the determined heavy metals,Cd and Hg gave moderate ecological risk indicators.     

沉积物金属元素变化的粒度效应--以太湖沉积岩芯为例

水体沉积物中金属元素含量变化除了与人为污染有关之外,在很大程度上受沉积物粒度、矿物组成等沉积物性质的影响．在进行沉积物金属元素研究中,要充分考虑沉积物金属元素含量变化的粒度效应．本文通过对太湖MS岩芯中17种金属元素、沉积物粒度、矿物组成等指标的分析,研究了金属元素变化特征以及与沉积物粒度组成的关系．MS岩芯金属元素变化可分为两类,第一类主要为Al、Fe、K等,该类元素在沉积岩芯中下部含量较高,岩芯上部含量较低;第二类为Na元素,在沉积岩芯中下部含量较低,岩芯上部含量升高．MS岩芯中金属元素与粘土含量之间具有显著相关关系,经沉积物粒度(粘土含量)校正后,沉积岩芯中金属元素含量趋于稳定．因此,沉积物粒度组成(粘土含量)是影响金属元素含量的主要因素,在研究太湖沉积物金属元素变化规律及进行金属污染评价时,应对金属元素含量进行粒度校正．     

Assessment of the bioavailability and toxicity of sediment-associated polycyclic aromatic hydrocarbons and heavy metals applied to Crassostrea gigas embryos and larvae

Sediments represent a vast sink for contaminants in aquatic systems, and may pose a threat to pelagic and benthic organisms. The objective of this research was to determine the bioavailability and toxicity of sediment-associated PAHs and heavy metals, using embryos and larvae of the oyster Crassostrea gigas, exposed to two sediment fractions: the whole sediment and the elutriate. The percentages of abnormal larvae, the contaminant accumulation and, (in the case of metal contamination), the induction of metallothionein in the larvae, were investigated. Sediment-associated PAHs and heavy metals were available for exposure, as indicated by their accumulation in C. gigas larvae and by the abnormalities induced during larval development. The critical body burden of PAHs (Fluo, Pyr, BaA, Triph, Chrys, BbF, BkF, BjK, BeP, BaP, Per, IP, BPer and the DahA) in the larvae was 0.3 micro g g(-1), above which abnormalities were observed. This value corresponds to concentrations observed for most vertebrate and invertebrate species. The bioavailability of PAHs is determined by their solubility; only the soluble fraction of PAHs is accumulated by the embryos. The bioavailability of metals for the larvae is substantiated by MT induction, correlated with cytosolic metal concentrations. MT induction provided a better early-warning response than the embryotoxicity test currently used for evaluating environmental contamination by metals. This study recommends choosing oyster embryos as a particularly sensitive tool for evaluating sediment quality.     

Anthropogenic influence on the degradation of an urban lake - The Pampulha reservoir in Belo Horizonte, Minas Gerais, Brazil

The artificial reservoir Lagoa da Pampulha in central Brazil has been increasingly affected by sediment deposition and pollution from urban and industrial sources. This study investigates water chemistry and heavy metal concentrations and their fractionation in the lake sediment using ICP-OES, ICP-MS, and XRD analyses. Fractionation analysis was done by sequential extraction under inert gas as well as after oxidation. The lake exhibits a permanent stratification with an oxygen-free hypolimnion below 2 m depth. Nutrient concentrations are enriched for phosphorous components (SRP, PO₄). In the sediment it was not possible to detect oxygen. Carbon, sulfur, and most of the analyzed heavy metals are enriched in the top sediment layer with a pronounced downward decrease, indicating the presence of an anthropogenic influence. Statistical analysis, including correlations and a Principal Component Analysis (PCA) of depth-related total concentration data, helps to distinguish presumably anthropogenic heavy metals from geogenic components. Some samples with high element concentrations in the sediment also show elevated concentrations in their pore water. Analyses of element distribution between sediment and pore water suggest a strong bonding of heavy metals to the anoxic sediment. The trend towards elevated solubility in the pore water of oxidized samples is clear for most of the analyzed elements. Fractionation analysis reveals characteristic associations of selected elements to specific mineral bonding forms. In addition, it indicates that the behavior of heavy metals in the sediment is strongly influenced by organic substances. These substances provide buffering against oxidation, acidification, and metal release. The high nutrient loading causes reducing conditions in the lake sediment. These conditions trigger the accumulation of sediments rich in S²⁻, which stabilizes the fixation of heavy elements. In the future, care must be taken to reduce the supply of contaminants and to prevent the release of heavy metals from sediments dredged for remediation purposes.     

Heavy metals in Chukchi Sea sediments as compared to selected circum-arctic shelves

Surficial sediments from 31 stations on the northeastern Chukchi Sea, Alaskan Arctic were analysed by AAS and ICP-AES for Si, Al, Fe, Mn, Cu, Cr, Co, Zn, Ni and V. The metal concentrations are related to the sediment granulometry and show no correlations with organic carbon. Presumably all the heavy metals, except Cr and Co, are either adsorbed on clays and/or coprecipitated with ferrimanganic hydroxide. Cobalt is partitioned in an unknown mineral phase within the sand fraction.

Comparison of the heavy metal concentrations in muds of the Chukchi Sea with those of the high arctic shelves of Russia, East Greenland and the Beaufort Sea shows relatively lower levels of most metals in the Chukchi. Presumably these disparities are related to regional differences in sediment chemistries inherited from natural terrigenous sources rather than to any enhanced pollution in the non-Chukchi areas.

It is suggested that the concentrations and accumulation rates of the heavy metals reported here can serve as reliable baselines to monitor metal pollution in the Chukchi Sea.     

Indicators of sediment and biotic mercury contamination in a southern New England estuary

Total mercury (Hg) and methylmercury (MeHg) were analyzed in near surface sediments (0-2 cm) and biota (zooplankton, macro-invertebrates, finfish) collected from Narragansett Bay (Rhode Island/Massachusetts, USA) and adjacent embayments and tidal rivers. Spatial patterns in sediment contamination were governed by the high affinity of Hg for total organic carbon (TOC). Sediment MeHg and percent MeHg were also inversely related to summer bottom water dissolved oxygen (DO) concentrations, presumably due to the increased activity of methylating bacteria. For biota, Hg accumulation was influenced by inter-specific habitat preferences and trophic structure, and sediments with high TOC and percent silt-clay composition limited mercury bioavailability. Moreover, hypoxic bottom water limited Hg bioaccumulation, which is possibly mediated by a reduction in biotic foraging, and thus, dietary uptake of mercury. Finally, most biota demonstrated a significant positive relationship between tissue and TOC-normalized sediment Hg, but relationships were much weaker or absent for sediment MeHg. These results have important implications for the utility of estuarine biota as subjects for mercury monitoring programs.     

太湖近代沉积物中重金属元素的累积

利用210Pb、137Cs定年技术,对来自太湖不同生态和沉积特征的三个湖区的沉积物柱状样品进行了定年,用ICP—AES分析了沉积物中重金属等元素的含量,分析了太湖沉积物中重金属的累积特征及其成因.污染较重、蓝藻水华暴发频繁的梅梁湾沉积物中的重金属含量在近25年来逐年增加;太湖上游风浪较大的夹浦湖区表层10cm沉积速率大、粒度粗,除表层1cm外,1—10cm沉积物中各种重金属含量都较低,且层间变化剧烈;下游湖区正逐渐草型化的胥口湾除表层3cm外,沉积物中重金属的含量自底层向表层大致呈不断下降的趋势.研究表明,不同年代的太湖沉积物中重金属含量差异很大,明显大于不同湖区间沉积物重金属平均含量间的差异.水动力作用引起的沉积物粒度分异很可能是影响沉积物中重金属积累的一个重要因素.总体上太湖沉积物中重金属的污染比较轻微,但已经有一定程度的Cd污染,梅梁湾沉积物中自上世纪70年代开始明显积累Cd,其他重金属元素的积累也逐渐增加,值得关注.     

Sediment geochemistry of the urban Lake Paulo Gorski

The objective of this study was to evaluate the concentration and distribution of heavy metals in the sediments of Paulo Gorski Lake, as well as the metals’ bioavailability and potential ecological risk, and to define the anthropogenic and natural heavy metal contributions to the lake. The chemical elements calcium (Ca), cadmium (Cd), cobalt (Co), chromium (Cr), copper (Cu), iron (Fe), potassium (K), magnesium (Mg), manganese (Mn), sodium (Na), nickel (Ni), lead (Pb), and zinc (Zn) were quantified by flame atomic absorption spectrophotometry with two extraction methods to quantify the bioavailable and non-bioavailable fractions. The data were evaluated using multivariate statistics and sediment quality indices. All sediment collection points (S1, S2, S3, S4 and S5) are different in terms of the concentration of heavy metals, except for S4 and S5, which were statistically equal. The bioavailable fraction of the elements in the sediment follows the sequence Pb>Cu>Mn>Zn>Ni>Cr>phosphorus (P) for all points. The elements Co, Cr, Pb, and Zn showed moderate to considerable contamination at all points. Only points S3 and S5 had moderate ecological risk. Urbanization has been affecting Paulo Gorski Lake via the input of chemical elements, especially Co and Pb. The points most affected by heavy metal contamination are S3 and S5 when the sedimentological sensitivity factor is considered. The lake has high hydrodynamics, causing some of the contaminants that enter the system to leave it, leading to potential negative impacts downstream.     

太湖流域滆湖底泥重金属赋存特征及其生物有效性

为了探讨太湖流域滆湖底泥重金属(Cd、Cr、Cu、Zn、Ni和Pb)的赋存特征及其生物有效性,对底泥重金属总量、形态以及生物富集量进行了分析.结果表明,6种重金属含量的空间分布表现为北部湖区最高,其次为南部湖区,中部湖区最低,重金属Ni、Cu、Zn和Pb含量显著高于沉积物背景值,分别是背景值的4.77、3.89、2.96和2.76倍,重金属总量与沉积物中的黏土成分含量具有显著相关性.采用三级四部提取法对重金属形态进行分析表明,6种重金属的生物有效态(弱酸结合态、可还原态和可氧化态之和)含量顺序为CdCuZnPbNiCr,其中Cd、Cu、Zn和Pb的生物有效态含量分别占总量的84.15%、78.47%、76.50%和64.29%.Cu和Zn在铜锈环棱螺中富集含量要显著高于其他金属元素.相关性分析表明,6种重金属中仅Cr和Pb的生物富集量与有效态含量具有显著相关性,这表明,重金属在生物体内的富集不仅与有效态含量有关,还与底泥重金属总量有关.因此,评价滆湖重金属的生态风险时需要综合考虑重金属的总量及生物有效态含量.     

Testing benthic foraminiferal distributions as a contemporary quantitative approach to biomonitoring estuarine heavy metal pollution

Biomonitoring of estuarine pollution is the subject of active research, and benthic foraminifera are an attractive group to use for these purposes due to their ubiquitous presence in saline water and wide diversity. Here, we describe a case study of biomonitoring using benthic foraminifera in the French Mediterranean lagoon, Bages-Sigean lagoon. In this case, the major pollutants of interest are heavy metals in the sediment, particularly contaminated by Cu and Cd derived from industrial and agricultural sources. The foraminiferal assemblages of the Bages-Sigean lagoon are typical of normal paralic environments, but unusually almost completely lack agglutinated forms. The density of benthic foraminifera was shown to be more influenced by the sediment characteristics rather than heavy metal pollution. However, the relative abundance of Quinqueloculina bicostata was shown to increase in the most polluted areas and we propose that this taxon may be used as an indicator of heavy metal pollution.     

Sedimentary Records of Evolution of Heavy Metals in Songhua Lake,Northeast China

In this paper, the vertical variations of heavy metal elements (including Cd, Cr, Cu, Hg, Mn, Ni, Pb, and Zn) in the sediments of Songhua Lake are analyzed using sediment cores. A 70‐year evolutionary history of these heavy metal elements in Songhua Lake is described and the sources of the heavy metals in the sediments are investigated by evaluating the pollution characteristics of the metals in terms of their enrichment coefficients and geoaccumulation indexes. The results indicate that Cr, Cu, Mn, Ni, Pb, and Zn in the sediments originated mainly from basin erosion and were transported to the lake by rivers. Cd and Hg in the sediments also originated from basin erosion that occurred prior to the mid‐1990s, and these sediments have since been overlaid by artificial pollution. The distribution of heavy metals in the sediments of Songhua Lake is influenced by many factors, including sediment composition, the relative importance of fluvial input, and artificial pollution.     

Geochemical features of the silt sediment of the Novosibirsk Reservoir

Earlier data on heavy metal concentrations in bottom sediments of the Novosibirsk Reservoir are supplemented by new geochemical characteristics of fine silt sediment in the near-dam part of the reservoir with the list of chemical elements extended to 55. After the beginning of the Ob’s runoff regulation by HPP dam, a new geochemical type of sediment started forming in the new reservoir. This type of sediment features higher concentrations of chemical elements (including heavy metals), reaching the values typical of Baikal silt recorded in the central hollow of the lake.     

Biomonitoring of heavy metal availability in the marine environment

Biomonitors can be used to establish geographical and/or temporal variations in the bioavailabilities of heavy metals in the marine environment, offering time-integrated measures of those portions of the total ambient metal load that are of direct ecotoxicological relevance. Heavy metal biomonitors need to conform to certain required characteristics, not least being metal accumulators. Use of a suite of biomonitors allows recognition of the presence and relative magnitude of different metal sources. For example, a macrophytic alga responds essentially to dissolved metal sources only, a suspension feeder like a mussel responds to metal sources in dissolved and suspended phases, and a deposit feeder responds to metal available in the sediment. Examples are given of suitable heavy metal biomonitors in the coastal waters of Europe, New Zealand, Hong Kong and China. It is not valid to compare absolute accumulated metal concentrations in biomonitors interspecifically, although interspecific comparisions of rank orders do allow cross correlations of relative bioavailabilities of heavy metals to different biomonitors at the same sites. There is a need to identify widespread cosmopolitan biomonitors to allow intra-specific comparisons of bioavailabilities between geographical areas. Such cosmopolitan biomonitors may include the alga Ulva lactuca, mussels of the genera Mytilus and Perna, the oysters Ostrea and Crassostrea, barnacles like Balanus amphitrite and Tetraclita squamosa, and the talitrid amphipod Platorchestia platensis. A major caveat in the use of such cosmopolitan biomonitors remains the need for reliable, specific taxonomic identification.     

Relationship between metal enrichments and a biological adverse effects index in sediments from Todos Santos Bay, northwest coast of Baja California, México

In 1992 and 2004, heavy metals concentrations were measured in surficial sediments from Todos Santos Bay, located in Ensenada, Baja California, Mexico. The aim was to search for relationships between metal enrichment factors and a biological adverse effects index. Unlike Ni, the elements Cd, Cu and Zn showed significant correlations (p<0.05) between enrichment factors and the biological adverse effects index. Cu showed a 0.74:1 relationship, which means that any enrichment above 0.74 could represent biological adverse effects. On the other hand, Cd and Zn enrichments must be >5.5 and >1.5, respectively, in order for the sediments to be considered toxic. In general, data showed that most of the metal concentrations in Todos Santos Bay sediments could not cause adverse effects to biota. Only Ensenada's harbor and the zone next to a dredging dumping site showed metal enrichments that could be toxic.     

Integrative assessment of coastal pollution: Development and evaluation of sediment quality criteria from chemical contamination and ecotoxicological data

Elutriate embryo-larval bioassays with sea-urchins (Paracentrotus lividus) were conducted concurrently with chemical analyses of sediments and biota as part of an integrative assessment of pollution in highly productive coastal regions. High metal contents and organic compounds in sediments and mussels were found in localised areas from the inner part of the estuaries indicating a clear anthropogenic influence. In particular, average maximum concentrations of 2803 mg Cu/kg dw, 776 mg Pb/kg dw, 2.5 mg Hg/kg dw and 5803 μg ∑₇PAHs/kg dw were measured in sediments from the most polluted sites. Significant correlations were observed between sediment chemistry and toxicity bioassays. Moreover, the Mantel test revealed a significant correlation (r_M=0.80; p<0.01) between sediment pollutant concentrations and toxicity data profiles. In addition, sediment quality criteria were used to help in the ecological interpretation of sediment chemistry data and to identify pollutants of concern. The toxicity bioassays identified polluted sites and quantified the level of toxicity, providing a cost-effective tool to complement the routine chemical monitoring currently conducted in European coastal waters with ecologically relevant information. This is in line with the recent European legislation that advocates the use of biological tools with the ultimate aim of protecting marine resources from anthropogenic substances that will affect their sensitive early life stages.     

基于筛分水平浓度法的洞庭湖沉积物质量基准初步分析

基于2013 2015年调查获取的129个洞庭湖表层沉积物和底栖生物的调查数据,应用筛分水平浓度法初步探讨了洞庭湖沉积物几种重金属沉积物质量基准的推荐值.结果表明,洞庭湖沉积物砷(As)、镉(Cd)、铬(Cr)、铜(Cu)、铅(Pb)和锌(Zn)含量均值为17.2、2.63、56.9、32.4、38.4和96.3 mg/kg(DW);筛分水平浓度法获取的洞庭湖沉积物As、Cd、Cr、Cu、Pb和Zn质量基准分别为11.97、1.13、42.03、19.17、23.63和67.54 mg/kg(DW).通过与不同国家及地区指定的重金属质量基准推荐值以及本地区采用其他方法推导的重金属基准推荐值进行比较,推算出本研究获取的6种重金属沉积物质量基准推荐值接近所有数据的中间值.对于洞庭湖流域,不同方法获取的沉积物重金属质量基准具有可比性.然而,鉴于用于推导沉积物质量基准的数据采集涉及的区域较为有限,且除了重金属污染外,影响底栖生物分布的因素较为复杂,导致获取的沉积物重金属质量基准推荐值存在一定的不确定性.