Chemical forms of copper and zinc in the surficial sediments of Borollos Lake, Egypt

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Trace metals in bivalve molluscs from Thailand

Capture fisheries and aquaculture provide a large quantity of bivalve molluscs for human consumption in Thailand each year. The existing information on trace elements in these bivalves is fragmentary and contradictory. This paper reports data for eight metals (cadmium, chromium, copper, iron, lead, nickel, mercury and zinc) in the four major species marketed. These are the clam Pahia undulata, the cockle Anadara granosa, the green mussel Perna viridis and the rock oyster Crassostrea commercialis. The bivalves analysed were taken at markets or in the field to cover as many of the major sources as possible. The results indicate no major threat to public health from trace elements in these species from Thailand and lend confidence to the expansion of aquaculture operations. In particular, the levels of lead found in the samples analysed are considerably lower than those previously reported by other authors.     

Distribution and partitioning of trace metals (Cd,Cu, Ni,Pb, Zn) in Galveston Bay waters

The distribution of several trace metals has been studied in the surface waters of Galveston Bay, Texas, in order to assess the impact of complexation with organic and reduced sulfur species on the partitioning of trace metals between particulate and aqueous species. The distribution of trace metals in the filter-passing fraction (<0.45 μm) showed two apparent trends: (1) the carrier phase metals (i.e., Fe and Mn) were largely removed in the Anahuac Channel region, which was dominated by direct Trinity River inputs; (2) the other metals (Cd, Cu, Ni, Pb, and Zn) showed non-conservative mixing behaviour, with mid-salinity maxima, within the estuarine regions of Galveston Bay. The average percentage of metal in the filter-passing fraction, as compared to the total metal load, decreased in that region from 95% to 9% in the order Ni>Cu>Cd>Zn>Pb>Mn>Fe, while an increasing trend was found in the same sequence for the acid-leachable fractions. The average values of K_d1, the particle-water partition coefficient, expressed as the ratio of weak acid-leachable particulate fractions to the filter-passing fractions, increased in the order Ni<Cu<Cd<Zn<Mn<Pb<Fe. This sequence is consistent with the relative importance of particulate transport of these trace metals from estuaries to coastal oceans. The observed decrease of K_d1 of Cu with increasing concentrations of suspended particulate matter (SPM), also called the “particle concentration effect” (PCE), can be eliminated when the free ionic, rather than the total concentration of Cu in the filter-passing fraction is used for calculating this ratio. A particle concentration effect would be expected if the binding of these trace metals by particles is mediated by solution (i.e., filter-passing) phase ligands. Complexation of Cd, Cu, Ni, Pb, and Zn with reduced sulfur species could be one of the causes for the observed linear correlations between metals and reduced sulfur species in both the filter-passing and filter-retained fractions. Significant correlations between Cu in the weak acid-leachable fraction and chlorophyll a (Chl a) concentrations suggest biological mediation of Cu uptake into the particulate fraction.     

Etude du transfert de quelques oligo-éléments métalliques entre le milieu sédimentaire estuarien et les poissons plats ‘mangeurs de sédiments’

In order to study the transfer of trace metals (Cd, Pb, Cu, Zn) between sediments and living organisms, flatfishes (flounder, Platichthys flesus and sole, Solea solea) were collected monthly in the Loire estuary (France) for more than a year. Trace metal concentrations were determined in flatfish digestive contents and tissues. The influence of some ecological factors upon bioaccumulation of trace metals was considered.We consider the benthic way of life not to be responsible for a preferential bioaccumulation of trace metals in flatfishes. Although zinc accumulation in external organs is important, the hypothesis of an uptake via food and sediment cannot be rejected.     

Dissolved trace element cycles in the San Francisco Bay estuary

Dissolved trace element (copper, nickel, cadmium, zinc, cobalt, and iron) concentrations were measured in surface water samples collected from 27 stations in the San Francisco Bay and Sacramento—San Joaquin Delta during April, August and December of 1989. The trace element distributions were relatively similar for all three sampling periods, and evidenced two distinct biogeochemical regimes within the estuarine system. The two regimes were comprised of relatively typical trace element gradients in the northern reach and anthropogenically perturbed gradients in the southern reach of the estuary. These dichotomous trace element distributions were consistent with previous reports on the distributions of nutrients and some other constituents within the estuary.In the northern reach, trace element and dissolved phosphate concentrations were non-conservative. Simple estuarine mixing models indicated substantial internal sources of dissolved copper (46–150%), nickel (250–500%) and cadmium (630–780%) relative to riverine inputs in April and August, and sizable internal sinks for dissolved cobalt (> 99%) and iron (> 70%) during the same periods. Dissolved zinc fluxes varied temporally, with a relatively large (135%) internal source in April and a relatively small (29%) internal sink in August.Concentrations of many trace elements (copper, nickel, cadmium, zinc, and cobalt) in the southern reach were anomalously high relative to concentrations at comparable salinities in the northern reach. Mass balance calculations indicated that those excesses were primarily due to anthropogenic inputs (waste-water discharges and urban runoff) and diagenetic remobilization from benthic sediments. The magnitude of these excesses was amplified by the long hydraulic residence time of dissolved constituents within the South Bay.The influence of other factors was evident throughout the system. Notably, upwelling appeared to elevate substantially dissolved cadmium concentrations at the mouth of the estuary and authigenic flocculation appeared to dominate the cycling of dissolved iron in both the northern and southern reaches of the system. Biological scavenging, geochemical scavenging and diagenic remobilization were also found to be important in different parts of the estuary. Additional complementary information is required to quantify accurately these processes.     

Trace metal-binding proteins in marine molluscs and crustaceans

Some marine invertebrates, such as the American oyster, Crassostrea virginica, the blue crab, callinectes sapidus and the American lobster, Homarusamericanus, concentrate trace metals in their tissues. The occurrence of metallothionein, a low molecular weight, sulfur-containing metal-binding protein, has been correlated with elevated levels of trace metals in these organisms. It is our hypothesis that, whilst metallothioneins are involved in the sequestration of elevated levels of trace metals, they primarily function in regulating normal metal metabolism. In this paper we describe recent field and laboratory experiments designed to examine how oysters, blue crabs and lobsters manage accumulated cadmium, copper and zinc. The possible rôles of metallothionein, as well as the tissue distribution of metals, are emphasized. Metallothioneins were found in all animals we examined; concentrations of metallothioneins and the the amount of bound trace metals are related to time of exposure. We have also demonstrated that the laboratory developed metallothionein models for blue crabs and lobsters may be useful in predicting the partitioning of trace metals in animals living in environments polluted with trace metals.     

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.     

Cadmium-binding proteins in the blue crab, callinectes sapidus: laboratory-field comparison

The blue crab, Callinectes sapidus, is distributed along the east coast of the United States from Cape Cod, Mass., through the Gulf of Mexico, including both relatively unpolluted coastal areas and estuaries contaminated with trace metals. Cadmium is of particular concern because it is concentrated in the digestive glands of blue crabs and can be passed on to consumer organisms. Tissue concentrations and partitioning of trace metals from crabs exposed in the laboratory to 10 ppb dissolved cadmium for 40 days were compared with blue crabs collected from two locations on the Hudson River, NY, Foundry Cove and Haverstraw Bay, Foundry Cove and Haverstraw Bay, both of which have elevated trace metal levels relative to estuarine areas near Beaufort, NC. Crab digestive glands, gills and muscle were removed and analyzed for total cadmium, copper, zinc and nickel concentrations using acid digestion and atomic absorption spectrophotometry, and metal-binding (metallothionein-like) proteins were determined by gel-filtration chromatography. In crabs exposed to cadmium in the laboratory, the cytosolic partitioning was similar to previous investigations at our laboratory where higher levels of cadmium (100 ppb) and shorter exposure times (14 days) were used. The similarity in cadmium partitioning from these two separate experiments indicates dose independence. In crabs from polluted environments the digestive glands contained the highest concentrations of trace metals. Chromatograms of the cytosol from the digestive glands and gills from both field and laboratory exposed crabs showed similar distributions of cadmium, copper and zinc. The gills of both field and laboratory-exposed crabs had metal-binding proteins that contained mostly cadmium, and the digestive glands had metallothionein-like proteins that contained cadmium, copper and zinc. Estimated molecular weights for these proteins were similar to the metallothioneins found in other crustaceans and mammals.     

Measurement of manganese, zinc and cadmium complexation in seawater using Chelex ion exchange equilibria

Equilibria between Chelex 100* and manganese, zinc and cadmium ions were used to determine the complexation of these trace metals in 36‰ Gulf Stream seawater at 25°C and pH 8.2. The method utilized radiotracers (⁵⁴Mn, ⁶⁵Zn, and ¹⁰⁹Cd) to quantify trace metal adsorption from trace metal-amended seawater and from seawater containing a series of ethylenediaminetetracetate (EDTA)—metal ion buffers. Results were consistent with Chelex adsorption of both trace metal ions and trace metal—EDTA chelates. Equilibrium models fitted to the data were used to establish conditional stability constants for Chelex adsorption of manganese, zinc and cadmium ions and for adsorption of EDTA-chelates. These models also yielded ratios of free metal ions to total dissolved trace metal concentrations in seawater: 10^−0.1 for manganese, 10^−0.2 for zinc, and 10^−1.5 for cadmium. Independent measurements with a cadmium ion-selective electrode also yielded a free: total cadmium ratio of 10^−1.5.     

鱼类的痕量矿物质研究进展

鱼类生命的全过程均需要矿物质，这些矿物质主要由无机元素构成。鱼类通过饲料和周围的水体获得矿物质。矿物质参与鱼类细胞和组织的代谢，并在骨骼的形成、胶体系统的维持、酸碱平衡的调节以及激素和酶等重要的生物化合物中发挥重要作用。如果鱼类缺乏矿物质，便能够引起生化、结构和功能上的病症。 迄今，一些痕量矿物质在吸收、生物利用和自身功能等方面的生理作用尚待进一步研究。尽管鱼类对这些痕量矿物质的需求量很低，但这些矿物质却是鱼类正常生长所必需的(表1)。如果鱼类过量地消化、吸收了这些矿物质，可能会产生毒副作用。因此，鱼类需要通过吸收、储存和排泄使体内各种痕量金属的含量维持一种微妙的平衡。     

Dissolved iron and zinc in Sagami Bay and the Izu-Ogasawara Trench

Using a clean seawater sampling system for trace metals onboard the R. V. Shinsei-Maru, newly launched in 2013, we investigated the vertical distributions of dissolved iron and zinc in Sagami Bay and the Izu-Ogasawara Trench. We applied appropriate clean sampling and filtering processes for trace metals, so that uncontaminated seawater samples were successfully collected. The distribution of zinc in the trench area was similar to that of silicate and the same as that previously reported in the subtropical North Pacific. There were spatial variations in the iron (Fe) distribution in the trench areas. We used previously reported information about biogeochemical cycling in the trench area, and found that Fe has a residence time of 29 years in the water column. The short residence time of Fe (29 years) corresponds to the vertical variations of dissolved Fe in the water column.     

Relationships between physiological stress and trace toxic substances in the bay mussel, Mytilus edulis, from San Francisco bay,California

Resident populations of Mytilus edulis from Tomales and San Francisco Bay, California, were measured for scope of growth, a physiological integration of the energy consumed by individual animals (feeding rate and assimilation efficiency) less the energy lost in metabolic processes (oxygen consumption and ammonia excretion). Scope for growth of mussels was significantly correlated (p≤ 0·05) with feeding rates. There was a significant decline in the scope for growth between the Golden Gate, at the bay's entrance and RedwoodCity in south San Francisco Bay. The scope for growth in resident M. edulis was significantly negatively correlated (p≤ 0·05) with increased environmental concentrations (from transplanted M. californianus body burden data) of the following trace elements and higher molecular weight chlorinated organic compounds: Cr, Cu, Hg (p ≤ 0·01) and Ag, Al, Zn, total chlordanes, and dieldrin. Scope for growth was significantly correlated (p ≤0·05) with body condition index (dry body weight1shell length).     

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.     

Determination of the zinc complexing capacity in seawater by cathodic stripping voltammetry of zinc—APDC complex ions

A novel technique to determine complexing capacities for zinc is presented. The free zinc concentration is determined by cathodic stripping voltammetry preceded by adsorptive collection of complexes of zinc with ammonium pyrrolidine dithiocarbamate (APDC). The reduction peak of zinc is depressed as a result of ligand competition by natural organic material in the sample. Sufficient time is allowed to reach equilibrium between this material and added APDC, and equilibrium is maintained during the measurement. Both electrochemically reversible and irreversible complexes can therefore be investigated. Values for K_ZnAPDC^′ are calibrated against NTA and EDTA in seawater of several salinities; log K_ZnAPDC^′ was found to be 4.40 at 36‰, 4.36 at 24‰, 4.43 at 12‰, and 4.87 at 2.3‰. The ligand concentration and conditional stability constant, K_ZnL^′, for complexing ligands in a sample from the Irish Sea were determined in the presence of 4 × 10^?5 M APDC and with added zinc concentrations between 5 × 10^?9 and 3 × 10^?7 M. The data best fitted a complexation model containing two ligands with concentrations of 2.6 and 6.2 and 10^?8 M, and with values for log K_ZnL^′ of 8.4 and 7.5, respectively. These results are comparable to those obtained with other equilibrium techniques, but the values of the constants are greater than those from ASV measurements.     

Trace metals (Cd, Cr, Cu, Fe, Ni, Pb, and Zn) in feathers of Black-browed Albatross Thalassarche melanophrys attending the Patagonian Shelf

We investigated the concentrations of cadmium, chromium, copper, iron, nickel, lead and zinc among feather tissues in sexes of Black-browed Albatross Thalassarche melanophrys killed in longliners off Argentina in 2005. We found no different metal concentration with sex for cadmium, copper, iron, lead and zinc in feathers of adult birds, though there were significant body-size differences between sexes. However, the concentrations of trace metals differed significantly among the type of feather within individual bird. The mean concentrations of copper, iron, and zinc in breast feathers of T.?melanophrys were lower than those reported for the species from Georgias del Sur/South Georgia, the southern Indian Ocean and for other seabirds' worldwide. While cadmium fall within the known range of concentrations for bird feathers lead were not. Our results may be indicating that level of pollution in Patagonia may not be as negligible as previously thought at least for some trace metals.     

Heavy metals and accumulation rates of sediments in Osaka Bay,the Seto Inland Sea,Japan

The metal load into sediments and the change in the sedimentary environment of Osaka Bay in the Seto Inland Sea have been studied through geochemical analysis of core sediments, using both Pb-210 dating and a selective chemical leaching technique. Analytical results from a 6-m core of sediment show that copper and zinc pollution started in the late 1800's and the present enrichment ratios of copper and zinc, relative to background levels (20 mg kg^–1 for Cu and 94 mg kg^–1 for Zn), are 2.8 and 4.1, respectively. The present anthropogenic copper and zinc loads into Osaka Bay sediments, are 47 and 368 ton yr^–1, while natural copper and zinc loads are 40 and 186 ton yr^–1, respectively. Osaka Bay sediment at the present day is considered to be seriously polluted by zinc, now. The vertical profiles of copper and zinc in four successively separated fractions (10% acetic acid soluble fraction: F-HAC, 0.1M hydrochloric acid-soluble fraction: F-HCl, hydrogen peroxide-soluble fraction: F-H₂O₂ and hydrofluoric acid-soluble fraction: F-HF) from the core sediments indicate that enrichments of copper and zinc in the upper layer of the sediment are dependent on increases in the metal contents of the F-HAC, F-HCl and F-H₂O₂ fractions. Copper in F-HAC, and zinc in F-HAC and F-HCl, seem to be of anthropogenic origin.Results of sequential studies of the whole Seto Inland Sea can be summarized as follows: At the present time, the sedimentary loads of copper and zinc over the whole Seto Inland Sea area are 630 and 3,500 ton yr^–1, respectively, while the natural and anthropogenic loads are 320 and 310 ton yr^–1 for copper and 1,800 and 1,700 ton yr^–1 for zinc, respectively.     

Metal binding by humic acids in recent sediments from the SW Iberian coastal area

The concentrations of Cu, Zn, Cr, Ni, Pb, As, Mn and Co were determined by Inductively Coupled Plasma–Mass Spectrometry both in recent sediments from different locations of the Huelva littoral (SW Iberian Peninsula) and in their humic acid (HA) fractions in order to evaluate distribution and binding capacity of those trace elements to HAs. In addition, elemental composition (C, N, S) and δ¹³C values were determined to appraise the sources of organic matter in the area. This study involved the comparison of selected samples taken from different environments including the estuary of the Guadiana River, the main fluvial system of the region, the Tinto and Odiel estuary system and the proximal shelf. Significant positive correlations were found among Cu, Zn, As and Pb in bulk sediments, suggesting a common origin of all of those elements: the mining activities and pyrite deposits located hinterland. On the other hand, results for Cr, Co and Ni pointed to the basic rocks from the low basin of the Guadiana River as their main source. Elemental (C, N) and isotopic (δ¹³C) composition of sediments indicated a significant contribution of autochthonous plankton in coastal shelf sediments, whereas estuarine and riverine sediments showed a major contribution of terrestrial biomass. Geochemical values for their corresponding HAs suggested a greater terrestrial contribution in the sedimentary OM of the coastal shelf sediments than in bulk sediments, which evidenced the influence of coastal currents and sediment fluxes. Humic acids sequester considerable amounts of Cu and Zn contributing to reduce the bioavailability of these contaminants.     

胶州湾海水痕量金属?溶解有机质分配特征及其影响因素探讨

采集胶州湾表层和底层海水样品,分析了Cu、Cr、Cd、Pb、Ni、Co等痕量金属在海水中的空间分布特征及其在不同分子量溶解有机质中的分配特征,并探讨了痕量金属?溶解有机质分配机理及浮游生物活动与盐度等环境因素对该分配过程的影响。结果表明,胶州湾海水中痕量金属呈近岸浓度较高的分布特征,在湾东北部出现高值区,Cd和Pb还分别在湾口与湾中部出现高值区。胶州湾海水中痕量金属平均有70.1%分配于低分子量(<1 kDa)组分中,其中Cu和Cd低分子量组分所占平均比例分别达79.0%与77.6%,Cr、Ni和Co稍低,分别为71.5%、67.3%及66.9%,Pb则仅为58.2%。海水中的溶解有机碳也以低分子量组分为主,所占比例平均达73.1%,且光谱特征显示低分子量溶解有机质中类腐殖质含量更高,含有丰富的羧基和羟基,金属配合能力较高,导致痕量金属多分配于低分子量溶解有机质中。高分子量溶解有机质(>1 kDa)所占比例与叶绿素a浓度呈显著正相关,表明浮游植物初级生产通过释放高分子量溶解有机质影响海水痕量金属?溶解有机质的分配过程。胶州湾湾顶盐度较低海域痕量金属高分子量组分略高,可能是生物活动及陆源输入(产生更多高分子量溶解有机质)与盐度(低盐有利于高分子量有机质的稳定性)共同作用的结果。     

Impact of diatom growth on trace metal dynamics (Mn,Mo, V,U)

In order to examine the specific role of diatoms in cycling of the trace metals manganese (Mn), molybdenum (Mo), vanadium (V), and uranium (U) Thalassiosira rotula, Skeletonema marinoi, Chaetoceros decipiens, and Rhizosolenia setigera were grown in batch cultures axenically and inoculated with three different bacterial strains isolated from the North Sea. Algal and bacterial growth, concentrations of trace metals and dissolved organic carbon (DOC) were monitored over time and showed that Mn and V were removed from the dissolved phase whereas Mo and U were not. R. setigera and T. rotula exhibited lowest growth and lowest removal whereas S. marinoi grew best and removed highest fractions of Mn and V. The high potential of Mn removal by S. marinoi was also evident from its 7 × higher Mn/P elemental ratio relative to T. rotula. The presence of bacteria modified the timing of the growth of S. marinoi but not directly trace metal removal whereas bacteria enhanced trace metal removal in the cultures of T. rotula and C. decipiens. Modeling of phytoplankton growth, concentrations of Mn and DOC fraction in axenic T. rotula cultures indicated that processes of binding and desorption of Mn to excreted organic components are important to explain the varying proportions of dissolved Mn and thus must be considered as an active component in Mn cycling. The results show distinct differences in the potential of the diatoms in the removal of Mn and V and that bacteria can play an active role in this context. S. marinoi presumably is an important player in Mn and V dynamics in coastal marine systems.