In situ trace metal speciation in a eutrophic lake using the technique of diffusion gradients in thin films (DGT)

We evaluated the application of DGT (diffusion gradients in thin films) as a tool to determine Cu, Zn, Ni, Cd, Pb and Mn concentrations and speciation in a hardwater eutrophic lake. This technique was used in situ during six sampling periods over one year in Lake Greifen. The DGT-labile species of Cu and Ni amounted to 15-25% of the total dissolved concentrations. Speciation by ligand-exchange/DPCSV indicated that Cu and Ni were predominantly organically complexed (>99%). Thus, the DGT-labile species for Cu and Ni were much more abundant than the free ionic and inorganic species determined by ligand-exchange/DPCSV. The results can be explained by incomplete metal exchange of very strong complexes with the chelating resin in the DGT devices, metal exchange of less abundant weaker complexes, and by slow diffusion of exchangeable organic complexes. For Zn (36 to >90% DGT-labile) and Mn (50 to 100% DGT-labile), the results indicated that these metals are less strongly organically complexed. A larger fraction of Zn occurred in DGT-labile species in the hypolimnion than it did in the surface water, probably due to a larger concentration of strong ligands in the productive surface water. DGT-labile Cd- (0.01-0.02 nM) and Pb-species (0.03-0.06 nM) were detected at very low levels. The combination of measurements of dissolved and DGT-labile species showed a decrease of Cu, Zn, Cd and Mn concentration at 2.5 m from June to August, which was probably linked to intensive sedimentation of organic matter during summer stagnation. Mixing and oxygenation of the lake in winter-spring led to an increase in dissolved and DGT-labile Ni, Zn and Cd, whereas Mn decreased in the hypolimnion.     

Copper,zinc, cadmium,nickel, iron and manganese in the Southern Bight of the North Sea

Ni, Cd, Cu, Zn, and Fe were determined in water and suspended matter samples and Mn in suspended matter samples from the Southern Bight region of the North Sea. Four distinct areas, comprising the Rhine estuary, the Dutch coastal waters, the centre of the Bight, and the English coastal water can be distinguished on the basis of the distribution of the trace metals. The total concentrations of all metals were high in the Rhine estuary, decreased in a seaward direction to reach very low values, comparable to continental shelf water, in the centre of the Bight, and increased again towards the English coast. Elevated concentrations of dissolved Cu, Ni, Cd and Zn near the English coast are not only due to river inputs. Over the entire region, the fraction of Cd, Ni and Zn in solution was consistently more important than the fraction in the suspended particulate phase. In contast, the fraction of Fe and Mn in the solid phase was consistently greater than the fraction in solution. Total concentrations of Fe, Mn and Cu are more dictated by the suspended particulate matter concentration than Cd, Ni and Zn.     

Temporal distribution of heavy metal concentrations in oysters Crassostrea rhizophorae from the central Venezuelan coast

The oyster Crassostrea rhizophorae is a bivalve abundant in Venezuelan estuaries and consumed by local populations. No known values have been reported on trace metals in oysters from the central Venezuelan coast. We report the concentrations of Al, Cd, Co, Cr, Cu, Fe, Mn, Ni, Pb, Sr, V and Zn in the soft parts of C. rhizophorae, which were collected bimonthly between March 2008 and March 2009, at two sampling areas from the Central Venezuelan Coast: Buche estuary and Mochima estuary. Our results show that for each metal there is a similar temporal variation pattern. The concentrations of the heavy metals reported in this work are useful as reliable baselines and can be used for comparison in future environment studies. Concentrations in C. rhizophorae from the Buche estuary can be interpreted to be high on a global scale for Cd, Cu, Ni and Mn, indicating atypically raised bioavailabilities.     

Baseline levels of heavy metals in the waters and sediments of Baffin Bay

Baseline levels of a number of trace metals have been determined in samples of water and sediment from Baffin Bay. Concentrations of Cr, Mn, Fe, Ni, Cu and Cd in the waters of Baffin Bay are generally lower than those observed in eastern Canadian coastal waters, levels being close to reported open ocean concentrations. Nearshore sediment samples, analysed for Cr, V, Mn, Ni, Co, Cu, Zn, Hg and Pb, display comparable concentrations to unpolluted muds in eastern Canadian coastal regions. Concentrations of these elements in the deep sediments of central Baffin Bay closely resemble levels in Atlantic Ocean deep-sea clays.     

Dissolved and particulate trace metals in a Scottish sea loch: an example of a pristine environment?

In the near pristine environment of a silled fjord on the west coast of Scotland samples were taken for the determination of dissolved and particulate trace metals (Fe, Mn, Cu, Ni, Cd, Zn and Pb), together with nutrient and hydrographic data, during 19 surveys carried out over a year. An indication of the pristine nature of the environment are the low concentrations of dissolved silicon, phosphate and nitrate which are considerably lower than those of coastal waters which are subject to larger anthropogenic burdens. Distributions of dissolved Cu, Ni and Cd were found to broadly reflect conservative mixing of freshwater and seawater with both end members having similar concentrations. The concentration of dissolved Cu and Ni in seawater entering upper Loch Linnhe (Cu 0.28 μg l⁻¹; Ni 0.26 μg l⁻¹) was consistent with the 1:1 conservative mix of Irish Sea water and North Atlantic surface water predicted from radio-caesium tracer experiments (Mackay & Baxter, 1985). Atmospheric input of trace metals to upper Loch Linnhe appeared to be a relatively minor term in the mass balance relative to fluvial inputs. Values of distribution coefficients Kd were similar to those previously reported for the coastal environment. Iron showed the strongest affinity for the suspended sediments; with particulate percentages of the total load usually greater than 80%. Lead and Mn showed a similar strong affinity to the particle phase. For Cu, Ni and Zn the mass of the element in the dissolved phase was generally greater than that in the particulate fraction. Cadmium, was least associated with the particles, with typically greater than 90% existing in the dissolved phase.     

Heavy metals contamination levels at the Coast of Aliağa (Turkey) ship recycling zone

Alia?a Bay is one of the most important maritime zones of Turkey where shipping activity, shipbreaking industry, steel works and petrochemical complexes exist together. Concentrations of heavy metals and organic carbon in sediment of the Alia?a Bay were investigated to evaluate an environmental risk assessment from metals contamination in 2009-2010. Comparison of the metal concentrations with average shale and Mediterranean background levels revealed that most of the samples from the Alia?a were polluted with Hg, Cd, Pb, Cr, Cu, Zn, Mn and Ni. It was found that Hg, Pb, Cu, Zn and Ni levels in Alia?a Bay exceeded the PEL values. Sediments, contaminated with Pb, Cr, Cu, Zn and Ni were considered as heavily polluted per the SQG.     

Dissolved and particulate trace metal fluxes through the central English Channel, and the influence of coastal gyres

Measurements of dissolved Cd, Co, Cu, Mn, Ni, Pb, and Zn have been made on a seasonal basis at five stations on a north–south transect across the central English Channel between Cherbourg and the Isle of Wight. Vertical and horizontal distributions of dissolved Cd, Pb, Cu and Zn are relatively uniform except for sampling sites near the English coast. Dissolved Mn and Co show increased concentrations in the English coastal waters, and for Mn the seasonal trend in concentration follows the pattern seen in the Strait of Dover with higher values in the late summer. Ni and Cu are higher in concentration on the English side, which reflects mainly riverine sources. Measurements were also made of particulate forms of the metals above plus particulate Al, Ca, Fe, Mg, Sr and Ti. Water column concentrations of particulate metals broadly follow the distribution of suspended particulate matter, with highest concentrations near the UK coast. Trace metal concentrations have been integrated with modelled data on fluxes of water to provide estimates of fluxes for these elements into the eastern Channel, and an initial comparison is made with data for fluxes of metals through the Strait of Dover obtained during an earlier study. A major influence on the fluxes of particulate metals through the Isle of Wight-Cherbourg transect is the gyre system to the South east to the Isle of Wight, which has important east to west as well as west to east transport components. For those elements where the dissolved form of the metal dominates, the large flow of water in the central Channel waters leads to major fluxes of the metals towards the east and the Strait of Dover. However, the high suspended particulate matter loadings in the coastal waters and impact of the gyre system lead to net east to west fluxes of particulate Al, Fe, Mn and Ti. Comparison of these fluxes with data on the net west to east transport of these materials through the Strait of Dover infers that there must be a significant supply of these particulate metals to the eastern Channel.     

Space-time variations of river water chemistry in RF southern Far East

Concentrations and seasonal variations of water chemistry, including dissolved and particulate forms of Fe, Mn, Zn, Cu, Pb, Cd, and Ni in rivers of Primorskii Krai are determined. It is shown that, unlike the macrocomposition, the effect of hydrological regime on the concentration of dissolved metal forms is controversial and depends on anthropogenic load, watershed landscapes, and pH variations. Elevated concentrations of dissolved metal forms are recorded in the beginning of spring flood and during low-water period. Beyond the limits of local impact of wastewater, the concentrations of dissolved forms of Cu, Zn, Ni, Pb, and Cd in river waters of the region insignificantly differ from the clearest rivers of the World.     

Assessment of Urban Source Metal Levels in Influent,Effluent, and Sludge of Two Municipal Biological Nutrient Removal Wastewater Treatment Plants of Bursa,an Industrial City in Turkey

Removal of Al, As, Cd, total Cr (Tot. Cr), Cu, Total Fe (Tot. Fe), Mn, Ni, Pb, Sb, Sn, and Zn from urban effluent by wastewater treatment plants (WWTPs) operated under five‐stage Bardenpho® process were investigated and water soluble metals in the dewatered sludge were quantified. Samples were collected from two WWTPs on a weekly basis over an approximately 2.5‐year time span. Tot. Fe and Al were the most abundant, As, Pb, Ni, Cu, and Cd were the least abundant metals in the influents of both WWTPs. Removal efficiencies above 75% were achieved for Tot. Cr, Tot. Fe, Al, and Cu, whereas, no significant removal was observed for As, Cd, Pb, Sb, and Sn. Removal of Tot. Cr, Cu, Tot. Fe, Zn, Al, Mn, and Ni were influenced by influent suspended solids concentrations, and of Tot. Cr, Zn, and Cd were influenced by their initial content in the influent. Zn removal efficiency of biological nutrient removal (BNR) system in this study was higher and Cd removal efficiency was lower than that of conventional activated sludge reported in the literature. No remarkable difference for metals such as Cu, Mn, Ni, and Pb was observed between the removal efficiencies of conventional system and BNR system.     

Metal speciation and environmental impact on sandy beaches due to El Salvador copper mine, Chile

Several coastal rocky shores in northern Chile have been affected by the discharges of copper mine tailings. The present study aims to analyze the chemical speciation of heavy metals in relation to the diversity of sessile species in the rocky intertidal benthic community on the northern Chilean coast, which is influenced by the presence of copper mine tailings. In particular, the chemical forms of Cd, Cu, Fe, Mn, Ni, Pb and Zn in beach sediment samples collected in the area influenced by El Salvador mine tailings were studied using a sequential chemical extraction method. In general, all the elements present a maximum concentration in the area near the actual discharge point (Caleta Palito). With regard to Cu and Mn, the concentrations range between 7.2-985 and 746-22,739 microg/g respectively, being lower than background levels only in the control site of Caleta Zenteno. Moreover, the correlation coefficients highlight that Fe, Mn and Ni correlate significantly and positively in the studied area, showing a possible common, natural origin, whilst Cu shows a negative correlation with Fe, Mn and Ni. It could be possible that Cu has an anthropogenic origin, coming from mining activity in the area. Cd, Fe, Mn, Ni, Pb and Zn are mostly associated with the residual phase, whilst Cu presents a different speciation pattern, as resulted from selective extractions. In fact, Cu is highly associated with organic and exchangeable phases in contaminated localities, whilst it is mainly bound to the residual phase in control sites. Moreover, our results, compared to local biological diversity, showed that those sites characterized by the highest metal concentrations in bioavailable phase had the lowest biodiversity.     

Metals in Sediments of the Upper Laguna Madre

The Laguna Madre system is the largest hypersaline coastal basin in the United States. Surface sediments from 22 Upper Laguna Madre (ULM) sites were analyzed for grain size and metals (Cd, Cu, Ba, Cr, Mn, Ni, Pb, V, Zn, Fe, and Al) to assess the extent of contamination in the area. Sediments were found to consist mainly of sand texture. Clay and silts were minor constituents (<10%) of the sediments. Anomalies in metal concentrations were found at some sites and were related to probable sources, i.e., recreational and industrial activities. Concentrations of metals were normalized to grain size, Al, and Fe to distinguish natural and anthropogenic sources. Most metals showed positive correlations (p < 0.001) with Fe and Al, suggesting a natural variability of metal concentrations in sediments. Concentrations of metals, except Cd and Pb, at most sites were found to be below threshold concentrations thought to produce toxic effects in marine and estuarine organisms.     

Trace metal concentrations in Antarctic sea spiders (Pycnogonida, Pantopoda)

Trace metals were analysed in sea spiders collected on two Polarstern cruises in the Weddell Sea. We found a substantial interspecific heterogeneity of Cd, Cu, Ni, and Zn, indicating varying accumulation strategies and metabolic demands for essential elements. Means and 95%-confidence intervals for all 44 samples analysed are 26+/-7 mg Cd kg(-1), 38+/-22 mg Cu kg(-1), 62+/-13 mg Ni kg(-1) and 990+/-130 mg Zn kg(-1) DW. Only for Pb do we find values less than 1.0 mg kg(-1) for most collectives analysed, in good agreement with other Antarctic arthropods such as crustaceans. Our study provides further evidence for the frequently reported "Cd anomaly" in many polar arthropods. While Cu concentrations in pantopods are within the reported range for Antarctic amphipods and decapods, Ni concentrations are exceptionally high and might be part of predation defence mechanisms. These possibilities should be investigated in more detail in future studies.     

Dissolved and particulate trace metals in meltwater from the Rhône glacier

Glacial meltwater and sediment at the source of the River Rhône have been analyzed to determine: 1. the partitioning of Al, Cd, Co, Cu, Cr. Fe, Mn, Ni, Pb and Zn between the water and particulate phase. 2. the particle size ranges which affect the dissolved trace metal ion composition of the meltwater and 3. the availability (potential release) of the ten trace metal ions from the sediment. Greater than 80% of the total Cd, Cu, Mn, Ni and Zn were found to be in operationally-defined (0.4 μm) dissolved forms. Fe and Al in the meltwater are primarily associated with particles in the size range 0.4–8 μm, while Cd. Cu, Mn, Ni and Zn occur with particles smaller than 0.1 μm. For the sediment, Cu, Ni and Pb were significantly present as exchangeable forms; only Cu, Ni, Pb and Zn were determined as organicallybound forms.     

Spatial and Temporal Distribution of Dust‐Bound Trace Metal Elements around Kuhdasht Watershed Area in Iran

Dust, as a source of trace metal elements, affects the health of society. The spatial and temporal concentrations of dust‐bound trace metals (Cd, Pb, Ni, Zn, Cu, and Mn) in Kuhdasht watershed (456 km²), Lorestan Province, Iran, is investigated. Dust is collected using glass traps placed in ten research stations in the region. The spatial and temporal distribution of dust trace metals are plotted using ARC‐GIS. The highest and the lowest concentrations of Zn (9751150 mg kg^?1), Pb (46.352.9 mg kg^?1), and Cd (2.443.30 mg kg^?1) are obtained in winter, of Ni (98110 mg kg^?1) and Cu in autumn (16.053.5 mg kg^?1), and of Mn in summer (385505 mg kg^?1). The spatial concentrations of dust‐bound trace metals indicate all, except Cu, show a decreasing trend from the mountains toward the plains, similar to that of soil and of dust, except for Zn, which shows higher concentrations in dust than in soil. The potential sources of dust‐bound trace metals and their rate of contamination are also investigated using the enrichment and contamination factors. The major sources of Cd and Zn in the dust of watershed are due to anthropogenic activities or from activities outside the borders.     

鄱阳湖流域赣江水系溶解态金属元素空间分布特征及污染来源

于2015年1月和7月在赣江干流和主要支流37个采样点共采集74个水样,分析赣江水系15种溶解态金属元素(Be、Al、V、Mn、Fe、Co、Ni、Cu、As、Mo、Cd、Sb、Tl、Pb、U)的空间分布特征和污染来源的贡献率.结果表明:多数水样的溶解态金属元素浓度符合水质标准,主要的超标元素是Fe,样品超标率为21.60%,其次为As(8.10%)、Mn(4.05%)、Tl(4.05%)和Al(1.35%).Be、Al、V、Fe、Co、Ni、Cu、U浓度在枯水期显著高于丰水期,其他元素差异不显著.依据溶解态金属元素的空间分布特征,赣江流域可分为3个区域:湘水、章水和赣江赣州市段(C1),桃江、袁水和锦江(C2),其他区域(C3);溶解态金属元素水平大小排序为C1C2C3,其中Be、Al、Cu、Mo、Sb、As浓度在C1最高,V、Mn、Fe、Ni、Cd浓度在C2最高.采矿废水、矿渣和农田土壤降雨淋滤、钢铁冶炼废水是赣江溶解金属元素的主要来源;Be、Al、Cu、Pb、U的污染源超过40%来自采矿废水,Cu、As、Mo、Cd的污染源超过35%来自矿渣和农田土壤降雨淋滤,V、Mn、Co、Ni的污染源超过41%来自钢铁冶炼废水.     

The speciation of dissolved copper,cadmium and zinc in Manila Bay,Philippines

At present, there is a very limited information on the levels and distribution of dissolved metals in Manila Bay. In this study, the horizontal and vertical distribution of operationally defined species (labile, bound and total) of dissolved copper (Cu), cadmium (Cd) and zinc (Zn) were determined using differential pulse anodic and cathodic stripping voltammetry in water samples obtained from 18 stations in November 1998. In addition, the 24-h variability in the concentrations of these species at different depths in the water column was determined. These measurements were complemented by the determination of temperature, salinity, dissolved oxygen, chlorophyll a, particulate organic carbon and nutrients. Results showed that more than 50% of total dissolved copper and cadmium were labile while 50% of total dissolved zinc was organically bound. Vertical profiles showed that Cu, Cd and Zn concentrations were generally high at the surface. Zinc and cadmium were characterised by the presence of a mid-depth minimum while copper did not show any clear vertical trend.

Dissolved Cu concentrations during the spatial and diurnal samplings ranged from 0.32 to 6.95 nM and 1.52 to 45.65 nM, respectively. For Cd, the concentrations in 18 stations ranged from 0.05 to 2.92 nM, and from 0.03 to 2.42 nM over a 24-h period. Zn concentrations ranged from 2.48 to 147.43 nM and 2.87 to 88.27 nM during the spatial and diurnal samplings, respectively. The large variation in the concentration of Cu, Cd and Zn in the bay was observed to be associated with the presence of a large vertical density gradient in the water column, which appeared to limit the exchange of materials between the surface and bottom waters. Elevated levels of these metals near point sources suggest anthropogenic inputs in the bay.     

Influence of the Aznalcóllar mining spill on the vertical distribution of heavy metals in sediments from the Guadalquivir estuary (SW Spain)

The Natural Park of Do?ana and the Guadalquivir estuary were impacted by the release of 6 million cubic meters of acid waste after the mine-tailing spill in Aznalcóllar (Andalusia, SW, Spain). Here is presented the monitoring of the accidental spill on vertical distribution of heavy metals in the estuarine sediments. The total concentration of six metals (Fe, Mn, Zn, Cd, Pb, Cu), their chemical speciation and the organic carbon concentration were analyzed in sediment vertical profiles. The results obtained determine background levels similar to previously reported in the area. The analysis catalogues the impact of the accident on the estuary as acute and mainly associated with high concentrations of Zn and Cd. The recent enrichment in Zn and Cd and their geochemical association with the more mobile fractions of the sediment determine an environmental risk associated with the acute impact and detected in some of the areas of the estuary.     

Distributions and removal fluxes of trace metals in the water column of the Hung-Tsai Trough off southwestern Taiwan

Vertical profiles of dissolved and particulate Mn, Fe, Ni, Cu, Zn, Cd, Pb, and (234)Th were determined in the Hung-Tsai Trough off southwestern Taiwan during 19-23 November, 2004. Except in the case of Cd, the distribution coefficient (K(d)) of the trace elements showed a negative correlation with the suspended particle concentration. Based on the average K(d) values, the general sequence of particle affinities for the eight trace elements is, from highest to lowest, Fe>Mn≈Pb>Zn≈Th>Cd≈Cu≈Ni. The trace metal data was coupled with the particle removal flux estimated from (234)Th/(238)U disequilibrium to investigate metal removal by particle sinking from the euphotic layer. The residence time of trace elements with respect to particle removal from the euphotic layer was estimated. A negative correlation between the residence time and the distribution coefficient for the trace metals was found.     

Fluxes of selected trace metals from the Seine estuary to the eastern English Channel during the period August 1994 to July 1995

Two sampling cruises conducted in the Seine estuary (France) under low-water and flood conditions produced high resolution profiles for dissolved cadmium, lead, copper, zinc and nickel concentrations versus salinity. The distribution of dissolved trace metals differed depending on hydrologic conditions, partly because of the dilution of upstream inputs during flood periods. Daily fluxes of these dissolved trace metals were estimated for the two sampling periods (September 1994 and February 1995) by extrapolating the dilution lines observed in higher salinity waters to salinity=0 and then multiplying the effective freshwater concentrations thus obtained by the corresponding freshwater flow. Several procedures were subsequently applied to deduce each daily flux for the year studied from data for these two periods. A consensus was found among these procedures, allowing the determination of net fluxes of dissolved trace metals with a precision of 20–35%. The net fluxes thus estimated were 4 T yr⁻¹ for Cd, 4 T yr⁻¹ for Pb, 40 T yr⁻¹ for Cu, 130 T yr⁻¹ for Zn and 50 T yr⁻¹ for Ni.     

Distribution of heavy metals in marine bivalves, fish and coastal sediments in the Gulf and Gulf of Oman

An assessment of marine contamination due to heavy metals was made in the Gulf and Gulf of Oman based on marine biota (fish and various bivalves) and coastal sediment collected in Bahrain, Oman, Qatar, and the United Arab Emirates (UAE) during 2000-2001. Sediment metal loadings were generally not remarkable, although hot spots were noted in Bahrain (Cu, Hg, Pb, Zn) and on the east coast of the UAE (As, Co, Cr, Ni). Concentrations of As and Hg were typically low in sediments and the total Hg levels in top predator fish commonly consumed in the region were < 0.5 microg g(-1) and posed no threat to public health. Very high Cd concentrations (up to 195 microg g(-1)) in the liver of some fish from southern Oman may result from food-chain bioaccumulation of elevated Cd levels brought into the productive surface waters by upwelling in the region. Very high As concentrations (up to 156 microg g(-1)) were measured in certain bivalve species from the region. Although not certain, the As is probably derived from natural origins rather than anthropogenic contamination.