Partitioning of heavy metals into mineral and organic fractions in a sediment core sample from Osaka Bay

Partitioning of copper, zinc, iron and manganese into oxide, sulfide, organic and silicate fractions has been determined with a selective chemical leaching technique on sediment samples from a core collected in Osaka Bay. The samples have been dated by the²¹⁰Pb method. Most of the copper and zinc in the polluted surface sediment layer are contained in both oxide and sulfide fractions. This suggests that the transformation of oxides and hydroxides to sulfides under anoxic conditions within the sediment is significant for the fixation of copper and zinc discharged through human activities into the sediment. Manganese is apparently enriched in oxide and hydroxide fractions of the surface layer due to the post-depositional migration of manganese within the sediment. The copper, zinc and manganese contents of the 30 % H₂O₂ soluble fraction (mostly organic fraction) decrease with depth in the sediment core, and correlate significantly with the organic carbon content. The heavy metal (Cu, Zn, Fe and Mn) contents of the silicate fraction, without exchangeable sites, are almost constant with depth.     

Metal-organic complexes in seawater pumped up from under the ground

Metal-organic complexes of transition elements removed by Amberlite XAD-2 resin from seawater pumped up from under the ground were determined. The proportions of iron, copper and zinc retained on the resin to dissolved forms of these metals were about 70, 40 and 5%, respectively, while manganese, cobalt and nickel were not retained on the resin. These results suggest that although iron may be retained in colloidal form, a significant fraction of copper is present in some organic form(s).     

Organic complexation and its control of the dissolved concentrations of copper and zinc in the Scheldt estuary

Cathodic stripping voltammetry (CSV) is used to determine total (after UV-irradiation) and labile dissolved metal concentrations as well as complexing ligand concentrations in samples from the river Scheldt estuary. It was found that even at high added concentrations of catechol (1 m for copper and 0·4 m for iron) and of APDC (1 m for zinc) only part of the dissolved metal was labile (5–58% for copper, 34–69% for zinc, 10–38% for iron); this discrepancy could be explained by the low solubility of iron which is largely present as colloidal material, and by competition for dissolved copper and zinc by organic complexing ligands. Ligand concentrations varied between 28 and 206 n for copper and between 22 and 220 n for zinc; part of the copper complexing ligands could be sub-divided into strong complexing sites with concentrations between 23 and 121 n and weaker sites with concentrations between 44 and 131 n . Values for conditional stability constants varied between (logK′ values) 13·0 and 14·8 for strong and between 11·5 and 12·1 for weaker copper complexing ligands, whereas for zinc the values were between 8·6 and 10·6. The average products of ligand concentrations and conditional stability constants (a-coefficients) were 6 × 10² for zinc and 6 × 10⁶ for copper.The dissolved zinc concentration was found to co-vary with the zinc complexing ligand concentration throughout the estuary. It is argued that the zinc concentration is regulated, in this estuary at least, by interactions with dissolved organic complexing ligands. A similar relationship was apparent between the dissolved copper and the strong copper complexing ligand concentration. The total copper complexing ligand concentrations were much greater than the dissolved copper concentrations, suggesting that only strongly complexed copper is kept in solution.These results provide evidence for the first time that interactions of copper and zinc with dissolved organic complexing ligands determine the geochemical pathway of these metals.     

Heavy metals in some New Zealand commercial sea fishes

To establish a base line against which future pollution may be measured, eight common commercial species of New Zealand sea fish were analysed for cadmium, chromium, copper, iron, lead, manganese, nickel, and zinc. One sample of edible muscle tissue was analysed for each of 70 samples of each species. The internal organs of up to five specimens of each species were also analysed. The fish studied were: kahawai, Arripis trutta, trevally, Caranx lutescens, tarakihi, Cheilodactylis macropterus, snapper, Chrysophrys auratus, moki, Latridopsis ciliaris, hapuku, Polyprion oxygeneios, kingfish, Seriola grandis and gurnard, Trigla kumu.

Although, none of the edible parts of the fish appeared to have trace element levels likely to be a public health problem (cadmium 0.002–0.02 ppm, chromium 0.01–0.04 ppm, copper 0.04–0.95 ppm, iron 0.9–13.5 ppm, lead ‘ 0.14–0.95 ppm, manganese 0.04–2.00 ppm, nickel 0.01–0.08 ppm, zinc 2.0–36.0 ppm), some of the organs (particularly the liver) had relatively high concentrations of elements such as cadmium (up to 54 ppm). Only if some industry were to seek to exploit internal organs of fish for human consumption would such levels become important. There was some evidence for a relationship between trace element concentrations and fish size for copper in kingfish and snapper, iron in hapuku, manganese in gurnard, and for zinc in kingfish and tarakihi. Some element pairs such as copper and zinc, iron and manganese, appeared to have concentrations which were mutually related. It was assumed that the elemental concentrations reported represent natural levels and are not the result of significant man‐made pollution because there are no major industries or large urban centres adjacent to the fishing grounds.     

An experimental study on the speciation of dissolved zinc,cadmium, lead and copper in river rhine and north sea water,by differential pulsed anodic stripping voltammetry

Dissolved electroactive concentrations of zinc, cadmium, lead and copper in river Rhine and North Sea samples have been measured at natural and lower pH values by differential pulsed anodic stripping voltammetry using a Kemula-type hanging mercury drop electrode. Average concentrations detected in North Sea samples at salinities $\text{? 32‰ S}$ and their range are (in μgl^?1): 3.9 (2.0–7.5) for zinc, 0.23 (0.13–0.31) for cadmium, 0.3 (0.1–0.6) for lead and 0.3 (0.25–0.60) for copper (pH 8.1). The APDC-MIBK extracting/concentrating method, followed by AAS measurement applied to the same samples, resulted in 3.9 (2.0–7.5) for zinc, 0.11 (0.01–0.27) for cadmium, 0.5 (0.2–0.9) for lead and 1.6 (0.7–3.2) for copper. A fraction of the electroactive concentrations at pH 2.7 (6.1 for Zn) is electroactive at pH 8.1. The fractions are 100% for Cd, 20% for Cu, 13% for Pb and 40% for Zn. The remaining fractions are partly composed of organically bound species in solution. The low value for lead may be caused by the presence of particulate lead that is dissolved at low pH.Ionic copper and lead species, added separately to seawater at pH 8.1 are removed from the electroactive form, and taken up in (organic) complexes in the same ratio (at least for copper) as the species already present. Added ionic zinc is not removed within the time scale of the measurements (30 min). North Sea water at the natural pH has a complexing capacity, probably due to the presence of dissolved organic compounds, in a concentration equivalent to 3.10^?7M copper. The complexing capacity is zero at pH 2.7. The usual method of standard addition for the determination of electroactive copper and lead concentrations may lead to erroneous results in samples where complexation of this type occurs.     

The incorporation of minor transition metals into marine manganese nodules

The mechanisms of incorporation of minor transition metals into marine manganese nodules are discussed on the basis of differential chemical leaching.A small portion of iron and manganese in deep-sea nodules was dissolved in dilute acetic acid. Hydrogenous cobalt and nickel in nodules were also slightly leached with the acid solution, while 50–60 % of hydrogenous copper and zinc were leached. This difference suggests that the greater parts of hydrogenous cobalt and nickel are present in the lattices of manganese oxide phases, while the major parts of hydrogenous copper and zinc are present in the sorption sites of manganese oxide phases.The enrichment of minor transition metals in manganese nodules may be controlled by their substitution for manganese atoms in manganese oxide lattices after their sorption on manganese oxide phases.     

Selected chemical contaminants in surface sediments of Commencement Bay and the Tacoma Waterways, Washington, USA

Eight metals, 21 organic priority pollutants, and 11 other contaminants and contaminant-related sediment characteristics were measured in surface sediments (upper 2 cm) at 21 locations in Commencement Bay and the Tacoma Waterways, Washington. Summary statistics were calculated and statistical approaches (analysis of variance, multiple comparisons tests, cluster analysis and principal component analysis) were applied to subsets of the data to classify sediment contamination. Overall sediment contamination was highest in the Sitcum, City and Hylebos Waterways, intermediate in Commencement Bay, at the entrances to the Tacoma Waterways and in the outer reaches of the Blair and Hylebos Waterways, and lowest at the Blair Waterway turning basin, the mouth of the Puyallup River and at a reference site near Browns Point. High concentrations of some contaminants appeared to be related to proximity to sources of contaminants. Depositional vectors, and chemical adsorption processes may also influence the spatial distribution of sediment contamination in the study area.Results of simple and partial correlation analyses indicate that arsenic, iron and manganese may be more closely associated with the clay fraction, while cadmium, copper and polynuclear aromatic hydrocarbons may be more closely associated with the total organic carbon content of sediments. We were unable to discriminate statistically between the affinity of chromium, lead, zinc and phthalates with the % clay or the total organic carbon content of sediments.     

Trace metal concentrations in brown seaweeds, Cardigan Bay, Wales

Concentrations of zinc, cadmium, copper, manganese, iron, cobalt, nickel and molybdenum are examined in brown algae, Fucus serratus and F. vesiculosus, from Cardigan Bay, Irish Sea, Great Britain. In both species a seasonal variation in metal content was observed. Zinc, cadmium, copper, iron nickel and cobalt concentrations were highest in the spring and lowest in the autumn, probably reflecting levels of metabolic activity and climatic factors. All the studied elements, except nickel, reached highest concentrations in harbour specimens from Aberystwyth and Aberaeron where rivers draining mineralized areas enter the sea. Outside harbours, marked regional variations were observed in most of the studied elements. Zinc values were highest in the Aberystwyth area while copper and manganese were highest in the northeast part of the bay.Trace-element concentrations varied among different species from the same locality and also varied according to position on the shore.Marine algae may be used to monitor coastal-water trace-metal concentrations, provided a careful sampling procedure is adopted.     

Metal concentrations in the shell of Bathymodiolus azoricus from contrasting hydrothermal vent fields on the Mid-Atlantic Ridge

Specimens of Bathymodiolus azoricus were sampled along the Mid-Atlantic Ridge at the Menez Gwen, Lucky Strike and Rainbow hydrothermal fields. Individual shells (n = 51), through the weight range 0.62 to 15.70 g, were analyzed for their magnesium, strontium, iron, manganese, copper, zinc and cadmium concentrations. Amongst the marine molluscs the shell of B. azoricus is confirmed as being particularly impoverished in strontium (mean 943 microg g(-1)). Trace metal concentrations in the shells decreased in the order Fe> Mn> Zn> Cu> Cd. Despite originating from trace metal rich environments mean concentrations were low (37.9, 13.2, 10.7, 1.1 and 0.7 microg g(-1), respectively). Irrespective of geographical origin magnesium, strontium and copper concentrations were primarily dictated by shell weight. In contrast cadmium concentrations were elevated in shells from the Rainbow field and ambient seawater chemistry imparted site specific chemical fingerprints to the shells with respect to the iron to manganese ratio.     

基于PXRF的西南印度洋脊硫化物表层沉积物地球化学找矿研究

海底热液喷发形成的热液羽状流中富含成矿物质,并沉淀在距离热液喷口不等的范围内。对西南印度洋中脊热液喷口附近、距离喷口中等距离、远离喷口的六个表层沉积物样品开展了不同粒度沉积物的便携式XRF（PXRF）分析。结果表明,PXRF可以有效获得的洋中脊钙质沉积物中成矿元素的富集特征。>40目的沉积物样品具有较高的Cu、Zn、Fe、Mn等元素含量,40目以下沉积物中则相对稳定,可能与粗粒沉积物中玄武岩碎屑/玻璃含量较高有关,与镜下鉴定结果一致。以热液喷口为中心,表层沉积物中表现出Cu、Zn、As、Fe、Mn的元素分带,靠近喷口的沉积物中具有较高的成矿元素的含量,并具有较高的Cu/Fe、Zn/Fe比值或者Cu/Mn与Zn/Mn比值。上述结论表明,洋中脊沉积物中成矿元素的含量主要受与喷口的距离的影响,而与粒度的关系不大,洋中脊沉积物地球化学找矿应采用40目以下粒径沉积物作为分析样品。通过PXRF获得的Cu、Zn、As、Fe、Mn等元素含量及其比值特征可以作为海底多金属硫化物沉积物地球化学找矿的指标,该方法满足快速有效识别洋中脊沉积物中地球化学异常的要求。     

汕头湾表层沉积物重金属元素含量和分布特征研究

于2002年9月在汕头湾采集了13个表层沉积物样品,测定了它们的细粒级组分、总有机质、铝、铁、锰、铜、锌、铅、镉、铬、镍、钴的含量,对其分布特征及其彼此之间相关性进行了分析,并以南海陆架区重金属含量为背景值计算了汕头湾表层沉积物重金属元素的富集系数,结果表明,铁、锰、铜、锌、铅、镉、铬、镍、钴的含量范围分别为2.91%~3.94%,427.85~810.96,24.43~79.49,84.83~248.50,35.56~50.25,0.30~1.75,36.11~74.22,16.99~31.69,8.22~10.87 mg/kg,其分布由汕头湾上游的榕江口至湾口呈波浪状递减(锰除外)。汕头湾表层沉积物中各重金属的富集系数均大于1,其中富集系数从大到小的重金属元素是铜、镉、铅、锌、镍、铬和锰。人为排污、水动力作用、黏土含量、盐度是多数重金属元素分布特征的控制因素。锰的分布特征更多地取决于汕头湾水域的氧化还原条件。     

Seasonal metal remobilization in the sediments of Great Bay,New Hampshire

Concentrations of dissolved iron, manganese, molybdenum, copper, and organic carbon (DOC) were measured in the pore waters from surficial sediments of a temperate estuary to delineate seasonal metal remobilization from 1978 through 1980. Iron and DOC data were collected for 31 months and covaried inversely and exponentially. Iron dissolution occurred during the spring and during periods of active bioturbation with concentrations as high as 18 mg 1^?1. Iron values were low during winter due to oxidation to ferric oxides. The lack of active bioturbation during the summer of 1978 allowed for the nearly complete removal of iron as a monosulfide precipitate. However, bioturbation resumed during the summer of 1979 and 1980 and dissolved iron concentrations as high as 10 mg 1^?1 were observed at those times. The iron and DOC data were a qualitative measure of bioturbation activity. Dissolved manganese, molybdenum, and copper data were collected for 18 months during 1978 and 1979. All three metals displayed spring maxima covariate with iron, suggesting that they behaved chemically like iron and/or were associated with iron- or manganese-rich phases during this time of the year. In general, manganese and molybdenum varied temporally with iron while copper concentrations mimicked iron variations only during the spring.     

渤海中部表层沉积物中重金属赋存相态及来源

近年来由于环渤海经济圈的快速发展,渤海接受了来自周边河流、沿岸排污及海上油气开采所产生的大量的重金属等污染物质,使得渤海的生态环境系统面临前所未有的压力。本文采用电感耦合等离子质谱仪（ICP-MS）对采自渤海中部的25个表层沉积物样品中的Cu、Co、Ni、Zn、Pb、Cr、Cd等重金属元素的含量和赋存相态进行了分析,探讨了重金属分布规律、污染状况及来源。研究结果表明,Cu、Co、Ni、Zn、Cr在渤海湾的近岸区域和渤海中部泥质区有较高的含量,而Pb和Cd则在整个研究区的含量都较高;表层沉积物中Cu、Co、Ni、Zn、Cr主要以残渣态形式存在,而Pb和Cd则具有较高的非残渣态含量;生态风险评价结果表明该区表层沉积物未受到Co、Ni、Cr的污染,Cu、Zn、Pb和Cd则为未污染-中等程度污染。重金属元素Co、Ni、Cr以自然来源为主,在沉积物中的分布主要受沉积物物质组成的影响,而Cu、Zn、Pb,尤其是Cd,则受到了人类活动的显著影响。黄河沉积物是研究区表层沉积物中重金属的主要来源,影响范围涵盖了本区大部分区域,但在研究区的北端受到滦河来源物质的影响,渤海湾和研究区中部则受到海河物质和大气沉降来源重金属的一定影响。     

Barnacles as biomonitors of trace metal availabilities in Hong Kong coastal waters: changes in space and time

The use of selected organisms as biomonitors of trace metal bioavailabilities allows comparisons to be made over space and time. The concentrations of 11 trace metals (arsenic, cadmium, chromium, cobalt, copper, iron, lead, manganese, nickel, silver, zinc) were measured in the bodies of two barnacle species, Balanus amphitrite and Tetraclita squamosa, from up to 18 littoral sites from Hong Kong coastal waters in April 1998. These data provide evidence on the geographical variation in metal bioavailabilities at this time, and are compared selectively against historical data sets for 1986 and 1989. Geographical variation in bioavailabilities is clear for several metals, with hotspots for arsenic, copper, nickel and silver at Chai Wan Kok, and for lead in Junk Bay. Victoria Harbour sites head the rankings for silver and arsenic, and Tolo Harbour sites exhibit relatively elevated cobalt, manganese and zinc. Many bioavailabilities of trace metals to barnacles are lower in Hong Kong coastal waters in 1998 than in 1986. The two barnacle species are widespread and the extensive data set presented is a benchmark which can be compared to the results of similar biomonitoring programmes elsewhere in the Indo-Pacific and beyond.     

Assessment of copper,cadmium and zinc remobilization in Mediterranean marine coastal sediments

The remobilization of copper, cadmium and zinc in sediments of three selected coastal microenvironments of the Aegean Sea (Eastern Mediterranean) is assessed. Various analytical methods and techniques were employed providing concentrations, profiles and forms of metals and organic matter in sediments and pore waters.     

Grain size, geochemistry, magnetic susceptibility: Proxies in identifying sources and factors controlling distribution of metals in a tropical estuary, India

The aim of this study is to understand the various sources and factors controlling the abundance and distribution of the metals through the analyses of selected metals (iron, manganese, chromium, copper, zinc and cobalt), sand, silt, clay, organic carbon and magnetic susceptibility of the surface sediments of Zuari estuary in three different seasons. Total suspended matter (TSM) concentration and salinity of near surface and bottom waters were also measured. The study undertaken for three seasons, based on 18 selected stations all along the estuary, indicated that the concentration of most of the metals were comparatively higher during pre-monsoon than in monsoon and post-monsoon seasons. Further, along the length of the estuary, high concentrations were observed at lower middle and lower estuary and also at few stations at the upstream end. Salinity, distribution of TSM, size of the sediment, organic matter, geomorphological setup, fresh water input from land and release of industrial waste within the estuary played a role in distribution and concentration of metals. Magnetic measurements indicated the dominance of haematite like minerals and helped in understanding the source and depositional processes.     

The chemical composition and nickel,cobalt, copper,zinc and lead contents of Nanao Bay sediments

The contents of major and some of the minor elements, nickel, cobalt, copper, zinc and lead were studied on sediments collected from three inlets of Nanao Bay located at eastern side of Noto Peninsula. Little variation was found on the average contents of silicon, iron, titanium, aluminum, manganese, magnesium and potassium among the sediments of West, South and North Bays in Nanao Bay. Whereas significant difference was found on the contents of calcium, chlorine, sulfur and nitrogen among sediments of three bays.As to the minor elements, the average contents of nickel (20±5 ppm), cobalt (5±1 ppm), copper (18±5 ppm) and lead (17±8 ppm) are relatively low but zinc content is high in these sediments comparing with those of coastal deposit around Japan Island. From the results obtained here, it became clear that no environmental contamination of nickel, cobalt, copper and lead, and a little organic pollution were found in Nanao Bay sediments.     

Changes in the tissue concentrations and contents of calcium, copper and zinc in the shore crab Carcinus maenas (L.) (Crustacea: Decapoda) during the moult cycle and following copper exposure during ecdysis

The tissue concentrations and contents of calcium, copper and zinc were determined at different stages in the moult cycle of the shore crab Carcinus maenas. The crabs were dissected into the following tissues: the midgut gland, the gill, the ‘rest tissue’ (the latter defined as the left over tissue, i.e. muscles and exoskeleton), and the haemolymph, and analysed as such. One group of crabs was maintained in clean seawater. In these crabs, calcium was lost from haemolymph during premoult and apparently stored in the midgut gland. At ecdysis approximately 90% of the whole body calcium content was lost with the exuviae while the haemolymph calcium content doubled. During early postmoult calcium stored in the midgut gland was used in combination with calcium absorbed from the surrounding seawater for a rapid calcification of the new exoskeleton. Both the copper and zinc concentrations declined in the ‘rest tissue’ compartment during premoult. At ecdysis the haemolymph copper and zinc contents increased 35 and 86%, respectively, from premoult to the newly moult stage. At the same time, however, the copper and zinc haemolymph concentrations decreased. During postmoult, copper (25%) and zinc (45%) were lost from haemolymph and mainly excreted but a minor fraction (5–10%) was stored in the midgut gland.A second group of crabs was maintained in copper-contaminated seawater (0.1 mgl⁻¹) during ecdysis and postmoult. Following exposure of the animals to raised ambient levels of copper, the calcium and zinc contents of the midgut gland were reduced while the copper contents of the midgut gland and most other tissues were increased in comparison to crabs held in clean seawater.     

C18 Sep-Pak Extractable Dissolved Organic Copper Related to Hydrochemistry in the North-west Mediterranean

Extractable organic copper using C18 Sep-Pak cartridges was investigated in seawater after laboratory experiment showed that the (C18 Sep-Pak) cartridges were reliable, in open and coastal waters with normal levels of dissolved organic carbon, for the separation of a specific fraction of organo-copper complexes.Given that the Sep-Pak cartridges retain the hydrophobic fraction of the dissolved organic matter, this extraction technique was applied for studying the characteristics of this particular hydrophobic dissolved organic copper fraction (hDOCu) in the north-western Mediterranean waters. Surface distribution of hDOC is influenced by organic matter input from the river Rhone and its estuary as well as the physical processes affecting the primary productivity such as coastal upwelling. By correlating hDOCu concentrations with total dissolved copper and other hydrochemical data such as salinity and dissolved organic carbon, it was possible to examine the behaviour of hDOCu in the water masses of different sources and ages.Marine organic matter has been shown to have high complexing capacity. Productive superficial and intermediate waters as well as deep waters showed relatively high and comparable complexing capacity indicating that old organic matter may have strong complexing sites.     

Temporal and spatial distribution of dissolved copper, lead, zinc and cadmium in the Changjiang Estuary and its adjacent waters

Heavy metal concentrations were measured in the Changjiang Estuary and its adjacent waters. Results from a systematic survey in April 2002 to March 2003 indicate that the ranges of the concentrations of dissolved copper, lead, zinc and cadmium in the study waters are 1.01 - 6.86, 0. 10 - 0.39,3.17 - 9.12 and 0.011 - 0. 049 μg/dm^3 , respectively. Similar to zinc, the behavior of dissolved copper was essentially conservative, but high scatter has been observed for high salinity samples, which can be attributed to the decomposition or mineralization of organic matter by bacteria. Dissolved lead may have active behavior with an addition at high salinity. Overall concentrations of dissolved cadmium increase with salinity. The mean values of these dissolved metals calculated for the surface waters were higher than those for the middle and bottom ones. External inputs of dissolved heavy metals to the surface waters were the likely explanation for these higher values. The maximum seasonal average values of dissolved copper and zinc were found in summer, reflecting higher amounts of riverine input in this season. In contrast, the maximum seasonal average values of dissolved lead and copper were found in winter and the lowest ones in summer, respectively, which might be asso- ciated with a combination of low concentration with heterogeneous scavenging. Concentrations of these dissolved metals found for the Changjiang Estuary fall in the range observed for the other estuaries but are noticeably higher than those from uncontaminated rivers, except for cadmium. Compared with observations for the Changjiang Estuary in the last two decades, it is clear that the Changjiang estuarine waters has been contaminated with copper, lead, zinc and cadmium during China＇ s industrialization, but concentrations of them have decreased in the last few years.