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.     

Dissolved trace metal distributions in Port Jackson estuary (Sydney Harbour), Australia

Concentrations of dissolved metals (Cd, Cu, Ni, Mn and Zn) were determined for summer and winter, under low-flow conditions in Port Jackson, a microtidal, well-mixed estuary in south-east Australia. Mean concentrations of Cd (0.04+/-0.02 microg/l), Ni (0.86+/-0.40 microg/l), Mn (20.0+/-25 microg/l) and Zn (6.47+/-2.0 microg/l) were below water quality guidelines. Concentrations of Cu (1.68+/-0.37 microg/l), however, slightly exceeded recommended values. Dissolved Ni and Mn behaved mostly conservatively, whereas Cd, Cu and Zn showed mid-estuarine maxima. Peaks in Cd, Cu and Zn concentrations were located in the upper estuary, independent of the salinity and suspended particulate matter loading, and were consistent with anthropogenic inputs of metals in the estuary. Concentrations of dissolved Cu were highest in summer, whereas concentrations of Cd, Ni and Mn were significantly lower in summer than winter (P< or =0.05). The increase in temperature and biological activity during summer explained the seasonal variation. The sequence of log K(d) values (20-30 salinity) was Mn>Zn>Cu>Ni. These results give unique information concerning the contemporaneous distribution of dissolved trace metals in the Port Jackson estuary and they provide a data set against which the long-term contamination may be assessed.     

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.     

Cd, Cr, Cu, Ni and Pb in the water column and sediments of the Ob-Irtysh Rivers, Russia

Concentrations of Cd, Cr, Cu, Ni and Pb were determined in filtered water, suspended particulate matter, and bottom sediments from a 2000 km section of the Ob and Irtysh Rivers. Dissolved Cd, Cr, Cu and Ni concentrations are similar to, or higher than, results from other Russian Arctic and large world river-estuaries. Concentrations of Cd, Cr, Cu, Ni and Pb in suspended particulate matter are generally comparable to results from other Russian Arctic and large world rivers and estuaries. Comparison of trace metal ratios in crustal material and suspended particulate matter and bottom sediment suggests that the source of Cr, Cu and Ni is continental weathering. Particulate Cd and Pb are elevated relative to their crustal abundance, suggesting a source of these metals to the Ob-Irtysh in addition to continental weathering.     

Distribution of dissolved and labile particulate trace metals in the overlying bottom water in the vistula river plume (southern Baltic Sea).

Overlying bottom water samples were collected in the Vistula River plume, southern Baltic Sea, (Poland) and analysed for dissolved and labile particulate (1 M HCl extractable) Cu, Pb, Zn, Mn, Fe and Ni, hydrological parameters being measured simultaneously. Particulate organic matter (POM), chlorophyll a and dissolved oxygen are key factors governing the chemical behaviour of the measured metal fractions. For the dissolved Cu, Pb, Zn, Fe and Ni two maxima, in the shallow and in the deeper part of the river plume, were found. In the shallow zone desorption from seaward fluxing metal-rich riverine particles account for markedly increased metal concentrations, as confirmed also by high particulate metal contents. For Pb, atmospheric inputs were also considered to have contributed to the elevated concentrations of dissolved Pb adjacent to the river mouth. In the deep zone desorption from detrital and/or resuspended particles by aerobic decomposition of organic material may be the main mechanism responsible for enrichment of particle-reactive metals (Cu, Pb, Zn) in the overyling bottom waters. The increased concentrations of dissolved Fe may have been due to reductive dissolution of Fe oxyhydroxides within the deep sediments by which dissolved Ni was released to the water. The distribution of Mn was related to dissolved oxygen concentrations, indicating that Mn is released to the water column under oxygen reduced conditions. However, Mn transfer to the dissolved phase from anoxic sediments in deeper part of the Vistula plume was hardly evidenced suggesting that benthic flux of Mn occurs under more severe reductive regime than is consistent with mobilization of Fe. Behaviour of Mn in a shallower part has been presumably affected by release from porewaters and by oxidization into less soluble species resulting in seasonal removal of this metal (e.g. in April) from the dissolved phase. The particulate fractions represented from about 6% (Ni) and 33% (Mn, Zn, Cu) to 80% (Fe) and 89% (Pb) of the total (labile particulate plus dissolved) concentrations. The affinity of the metals for particulate matter decreased in the following order: Pb > Fe > Zn > or = > Cu > Mn > Ni. Significant relationships between particulate Pb-Zn-Cu reflected the affinity of these metals for organic matter, and the significant relationship between Ni-Fe reflected the adsorption of Ni onto Fe-Mn oxyhydroxides. A comparison of metal concentrations with data from other similar areas revealed that the river plume is somewhat contaminated with Cu, Pb and Zn which is in agreement with previous findings on anthropogenic origin of these metals in the Polish zone of southern Baltic Sea.     

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.     

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 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.     

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.     

Variable influence of the atmospheric flux on the trace metal chemistry of oceanic suspended matter

The particulate concentrations of 17 trace metals, Al, Sc, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Se, Ag, Sb, Au, Hg, Pb and Th have been measured in the marine atmosphere (58 samples) and in the deep waters (35 samples) of the Tropical North Atlantic. For oceanic suspended matter, our results are similar to those in samples from the Atlantic and the Pacific Oceans collected during the GEOSECS Program. Based on these results, we have made a flux balance for the mixed layer between input via the atmosphere and removal through small and large particles. These data show that the primary flux of suspended aluminosilicates in the Tropical North Atlantic is attributable to the atmospheric input. Elements Sc, Th, Fe, V, Mn, Co and Cr show high correlation with Al in the marine atmosphere. Of these elements, Fe, Mn, V, Co and Cr are influenced by additional processes such as biological, in the marine environment. For elements Ni, Cu, Zn, Se, Ag, Sb, Au, Hg and Pb, we observe high enrichments (relative to average crustal material) in the marine atmosphere which may be due, at least partially, to the influence of anthropogenic sources. These metals also show similar enrichments in deep ocean suspended matter. Model calculations indicate that the atmospheric flux may not control the deep ocean particulate chemistry of Ni, Cu, Zn, Ag, Sb, Au and Hg. Hence it is likely that, for these elements, the enrichment in the ocean is due to processes within the marine regime, for example their involvement in the biological cycle of the ocean. For Se and Pb, the atmospheric source looks to be the dominant contribution to their particulate concentration in seawater. In the deep North Atlantic, particulate Pb appears to be mostly of anthropogenic origin, which is not the case for Se.     

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.     

An assessment of metal contamination in mangrove sediments and leaves from Punta Mala Bay, Pacific Panama

Due to the growing rate of urbanisation in many tropical coastal areas, there continues to be an increasing concern in relation to the impact of anthropogenic activities on mangrove forests. Punta Mala Bay is located on the Pacific coast of Panama and suffers from intense anthropogenic activities that are potentially harmful to the remaining mangrove forests. Field observations reveal that the mangrove stand within Punta Mala Bay receives high inputs of untreated domestic sewage, storm water run-off and a range of diffuse inputs from shipping activities. Results from analysis of eight metals (Mn, Cu, Zn, Ni, Pb, Fe, Cr, Cd) showed that Fe, Zn and Pb were in concentrations high enough to conclude moderate to serious contamination within the bay, and thus pose the most threat to the regeneration and growth of the mangrove. However, previous biological surveys indicate ongoing mangrove regeneration and domination of stand structure by Laguncularia racemosa, together with high numbers of seedlings and saplings.     

Accumulation of Heavy Metals by Amur Bay Sediments (the Sea of Japan) under the Effect of Biochemical Factors

Water Resources - The average concentrations of elements Fe, Mn, Zn, Pb, Cu, Cr, V, Co, Cd, Ni, As, and Mo in the subcolloidal fraction of bottom sediments were determined in the northern and...     

Dynamics of particulate major and trace elements in the lower reaches of the Daugava River and adjacent area of the Gulf of Riga (Baltic Sea)

Suspended particulate matter (SPM) was collected in the freshwater-seawater mixing zone in the lower reaches of the Daugava River (Latvia) and adjacent marine area, during five cruises in 1998-2001. The study focused on biogeochemical phase exchange processes. SPM in the freshwater was found to be mainly allochthonous with a high content of organic matter, Mn and sorbed phosphate. Property-salinity plots suggested flocculation of humic-Fe complexes across the salinity gradient. The variability of sorbed phosphate was related to particulate Fe, although no dependence on pH and ionic strength was observed. The Mn contents of SPM mainly follow conservative mixing, but there are also indications of interface exchange of Mn in the mixing zone. The geochemical behaviour of particulate Al appears to differ from that of Fe. In early spring, trace element contents in SPM (Cr, Ni, Cu, Zn, Cd, Pb) correlate tightly with particulate organic matter, whose distribution is linked to phytoplankton distributions.     

Trace element content of seagrasses in the Leschenault Estuary,Western Australia

Estuarine environments are particularly vulnerable to human impacts. In this study, trace elements in Ruppia megacarpa, Halophila ovalis, sediment and porewater were analysed to assess the potential contamination of the Leschenault Estuary, Western Australia, from a primarily agricultural drain. Sediment concentrations of Cd, Cu, Mn, and Ni and were highest nearest the drain while Al, As, Cr, Fe and Zn and were highest further from the drain. H. ovalis showed greater accumulation of Fe, Al, and As than R. megacarpa. Concentrations of Fe, Al, As, and Ni were generally higher in below-ground plant parts than above, suggesting uptake of these trace elements via the sediment-route pathway. This study suggested that the drain was a source of Cu and Mn, with these elements entering the estuary through water inflows. As and Fe, were highest furthest from the drain suggesting input of trace elements from sources other than the drain under study.     

Seasonal distribution of trace metals in suspended particulate and bottom sediments of four microtidal river estuaries,west coast of India

ABSTRACT

The seasonal distribution of metals (V, Cr, Co, Cu, Ni, Zn, Pb, Mn, Fe, Al and Ti) in suspended and bottom sediments of four minor estuaries (Terekhol, Chapora, Sal and Talpona rivers) of Goa, India was investigated to understand the metal distribution process in the estuarine region. The highest particulate-metal concentrations were found in low-salinity regions of all the estuaries, in the wet season (e.g. in the Terekhol River, the averages in ppm were Co: 53, Ni: 197, Cu: 208, Zn: 212 and Pb: 65) compared to the dry season averages (Co: 27, Ni: 76, Cu: 105, Zn: 164 and Pb: 13 ppm). The estuarine-mixing diagrams showed non-conservative behaviour in both seasons. The Sal River had the highest particulate-metal concentration (Co: 106, Ni: 300 and Zn: 323 ppm), suggesting an anthropogenic input. The enrichment factor for suspended matter was higher than bottom sediments with extremely high enrichment for Mn (>10). The Geo-accumulation index displayed unpolluted to polluted class for all metals. The study highlights the important role played by small estuaries in seasonal metal release and accumulation along the coastal region.     

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.     

Assessment of heavy metal pollution from the sediment of Tupilipalem Coast,southeast coast of India

Sediment from twelve stations was sampled from the Tupilipalem Coast, southeast coast of India, and the presence of a set of heavy metals was established including iron (Fe), manganese (Mn), chromium (Cr), copper (Cu), nickel (Ni), lead (Pb), zinc (Zn) and cadmium (Cd). The heavy metals were assessed by factor analysis, the results of which showed positive and/or negative correlations among Fe, Mn, Cr, Cu, Ni, Pb, Zn, and Cd. Factor analysis also indicated that heavy metals in the sediments of the study area have different natural and anthropogenic sources. Similarly, a sediment pollution assessment was done using the Geoaccumulation Index (Igeo), Enrichment Factor (EF), and Pollution Load Index (PLI). The Geoaccumulation Index indicated that the surface sediment of the Tupilipalem Coast was extremely contaminated with Fe, Mn, Cr, Cu, Ni, Pb, and Zn. The calculation of enrichment factors showed a significant enrichment with respect to Pb, Zn, and Cd and a moderate enrichment with Cr, Cu, and Ni. The falling trend of average contents’ enrichment factors is Cd> Pb> Zn> Cu> Cr> Ni> Mn> Fe. The PLI values of the Cd show higher (>1) values due to the influence of distinct external sources like agricultural runoff, industrial activities, and other anthropogenic inputs. Ninety two percent of heavy metals under study showed the highest concentrations at station TP-5 where the Buckingham Canal and other agricultural and aquacultural effluents connect with the Bay of Bengal. This location is the second inlet which is periodically closed and it seemed that these parts of the study area are heavily affected by anthropogenic pollution.