The degree of trace metal pyritization in subtidal sediments of a mariculture area: application to the assessment of toxic risk

Four 2–3 m sediment cores were taken at the sites on the periphery of mussel raft concentrations in the subtidal zone of the inner Ría de Vigo (Galicia, NW Spain) with a view to evaluate the potential risk to mariculture from sediment-borne trace elements (As, Cd, Cr, Cu, Mn, Ni, Pb and Zn). The distribution of each of these elements in reactive, organic, pyrite and silicate-bound fractions was determined at 64 samples, and these data were used to calculate the degree of trace metal pyritization (DTMP) of each metal/metalloid. In the top 10–20 cm, relatively oxic conditions led to As, Cd, Cu, Pb and Zn having large reactive fractions due to their association with Fe and Mn oxyhydroxides. At lower levels, anoxic conditions favoured by intense diagenesis led to the precipitation of trace metals and metalloids as sulphides, with or without association with pyrite. Particularly large pyrite fractions in the 20–100 cm layer are attributed to the organic matter of this layer being more marine in origin than that of deeper sediments. DTMP was greatest for Cu and As, and least for Pb, Zn and Cr. The risk of trace element toxicity in the event of disturbances instituting oxic conditions in these sediments is discussed.     

Scavenging of heavy metals from particulates by brown seaweed

Concentrations of Cu, As, Pb, Zn and Ag (but not Cd, Co, Fe, Mn and Hg) in the tissues of benthic algae (Fucus vesiculosus) correlate significantly with concentrations in sediment. Metals which complex most strongly with algal tissues show the strongest correlations of algal tissue and sediment. Scavenging these metals from particulates may be an important source of uptake by the algae. If so, concentrations of Cu, As, Pb, Zn and Ag in algal tissues may not be good indicators of concentrations of these metals in solution.     

The Apure River: geochemistry of major and selected trace elements in an Orinoco River tributary coming from the Andes,Venezuela

The analysis of physicochemical variables and selected dissolved elements was performed on the Apure River waters for 15 months. The variables pH, alkalinity, dissolved O₂, conductivity and Na, Ca, Mg and Cd concentrations showed maximum values during low water, whereas K, Si, Fe, Al, Mn, Zn, Cu, Cr and dissolved organic carbon (DOC) showed maximum concentrations during rising and high water. Five important factors were found to control the amount and temporal variability of the dissolved elements: lithology, hydrology, vegetation–floodplain processes, redox conditions and organic complexation. Weathering of silicates, carbonates and evaporites in the Andes provides most of the proportion of Na, Ca, Mg and HCO₃^? to waters. The temporal variability of these ions is controlled by a dilution process. Although Si can be taken up by the biomass, Si and K can be leached from the floodplain by weathering of clays. Microbial decay of the submerged plants in the floodplain during the inundation periods provides DOC and K to river waters and changes the redox conditions in water. The changing redox conditions control the solubility of Mn, Zn and Fe. Dissolved Mn is a function of pH‐dependent redox process, whereas Zn solubility is controlled by scavenging of Zn during the oxidation of Mn²⁺ to MnO₂. Positive relationships between Al, Fe, Cu, Cr and DOC suggest that these elements are complexed by organic colloids generated in the floodplain. Moreover, the binding capacity of Fe with DOC increases under reducing conditions. Although Cd seems to be provided by weathering in the Andes, several processes can affect the mobility of Cd during transport. Copyright © 2010 John Wiley & Sons, Ltd.     

Temporal variability of selected dissolved elements in the lower Orinoco River,Venezuela

Monthly analyses of pH, conductance, alkalinity, total suspended solids, dissolved major cations (Na, K, Ca and Mg), and selected dissolved trace elements (Fe, Al, Mn, Cu, Zn and Cr) were conducted on waters of the lower Orinoco River from February 2004 to May 2006. The data show strong seasonal variability. Major cations had maximum concentrations at low water, and were correlated with pH, conductance and alkalinity because of the tributaries coming from the Andean zones, where the weathering of evaporites and carbonate shales controls water chemistry. K concentrations did not show any relation with evaporite weathering, probably because large amounts of K come from the Guayana Shield rivers as a consequence of feldspar weathering. The concentrations of dissolved Fe, Mn and Cu were highest during the high water stage. Concentrations of the elements K, Cr, Zn and Cu are correlated with each other but not with dissolved Fe and Al, which probably are complexed with humic and fulvic substances. Mn concentrations did not show relationships with other variables. Inter‐annual variability of dissolved elements is explained by temporal changes in precipitation. Copyright © 2008 John Wiley & Sons, Ltd.     

Dynamics of dissolved major (Na,K, Ca,Mg, and Si) and trace (Al,Fe, Mn,Zn, Cu,and Cr) elements along the lower Orinoco River

This study addresses the changes in dissolved major and trace element concentrations along the Orinoco River, including the mixing zone between the Orinoco and Apure Rivers. Water samples from the Apure and Orinoco Rivers were collected monthly in four sectors over a period of 15 months. Auxiliary parameters (pH, dissolved oxygen, conductivity, and temperature), total suspended sediments, dissolved organic carbon (DOC), and major (Na, K, Ca, Mg, and Si) and trace (Al, Fe, Mn, Zn, Cu, and Cr) element concentrations were measured in all sectors. The relative contribution of both rivers after the Apure–Orinoco confluence was determined using Ca as a tracer. Moreover, a mixing model was developed to determine whether dissolved species exhibit a conservative behavior during mixing. The results indicate that DOC is removed from waters during the Apure–Orinoco mixing, probably due to absorption of DOC on mineral phases supplied by the Apure River. Dissolved Na, Ca, and Mg behave conservatively during the mixing processes, and their concentrations are controlled by a dilution process. The anomaly in the temporal pattern of K in the Orinoco is caused by the input of biogenic K originating from the Apure River during the high‐water stage. The loss of dissolved Si during the low‐water stage can be explained by the uptake of Si by diatoms. Dissolved Mn, Zn, Al, and Fe showed a non‐conservative behavior during the Apure–Orinoco mixing. The removal of Mn and Zn from the dissolved phase can be explained by the formation of Mn‐oxyhydroxides and the scavenging of Zn onto Mn oxides. Dissolved Fe is controlled by redox processes, although the removals of Fe and Al due to the preferential adsorption of large organometallic complexes by mineral surfaces after the Apure–Orinoco confluence can affect the mobility of both elements during transport. The conservative behavior shown by Cu and Cr can be related to the tendency of both elements to be complexed with small organic colloids, which are not preferentially adsorbed by clays.     

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.     

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.     

Interpretation of metal profiles in a sediment core from lake geneva: metal mobility or pollution

The transition elements Mn, Fe, Co, Zn, Cu and Cr together with Pb and P were determined in three sequential extractions of sediment and in the pore water of a 35-cm sediment core from Lake Geneva. A high percentage of the mobile Mn, Fe, P, Co, Pb and Zn was extracted in the first (inorganic) fraction, whereas the mobile Cu and Cr were mostly found in the second (organic and sulfide) fraction. Mn was subject to recycling with solubilization from the surface sediment to the oxic bottom water where it was precipitated. Highly enriched Co and P values were observed in the top few mm of the sediment resulting from post depositional solubilization with upward migration and precipitation with oxi-hydroxides at the sediment surface. The slower increase of Cu, Zn and Pb concentrations towards the sediment/water interface are the result of an increase of anthropogenic sources over the past decades. A further increase in Pb in the first cm of the core is believed to be related to the freshly precipitated Mn oxi-hydroxides.     

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.     

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.     

On the speciation of metals in the water column of a polluted estuary

The dissolved (<0.40 γm) fraction of water samples from Newark Bay, New Jersey was analysed for Zn, Cu and Pb content by differential pulse anodic stripping polarographic techniques. In the dissolved fraction, non-labile forms of Zn, Cu and Pb exist as shown by differential pulse anodic stripping voltammetry analysis on acidified samples and acidified-UV irradiated samples. The particulate fraction (>;0.40 μm) contains metals in the form of sulphides (Fe, Zn, Cu, Mn), oxides and oxyhydroxides (Si, Al, Fe, Cu, Ni, Sn), phosphate (Ca, Ce, La), clay minerals (Fe, Zn, Cu, Ti) and carbonaceous material (Fe, Cu, Zn) as demonstrated by X-ray microanalysis. The solid phases are likely present in colloidal form in the dissolved fraction of the water column as well. The forms of the metals in the water column are partially due to the resuspension of bottom sediments by dredging and natural processes, to sewage outfall and to natural geochemical processes.     

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.     

Reconstructing the iron cycle from the horizontal distribution of metals in the sediment of Baldeggersee

In Baldeggersee, the distributions of solid phase Fe, Mn, V, Cr, As and Mo were determined in different sediment strata, deposited under various deep-water oxygen conditions. Iron concentrations are correlated with water depth when an anoxic sediment is in contact with an oxic water column. Benthic redox gradients trigger iron transport towards the deepest site (geochemical focusing) and loss of iron from the shallower parts through the outflow. Fe cycling in the lake is inhibited by oxygen penetration into the sediment. Vanadium and arsenic can be used as tracers for the internal Fe cycle. Their distribution patterns are highly correlated with iron. In case of a stable oxycline in the deep water, Mo is enriched in the sediment and correlates with Mn. The horizontal distribution patterns of Fe, V, As and the correlation of Fe and Mn with trace metals are promising proxy indicators for the reconstruction of deep-water oxygen conditions during deposition.     

Effect of Resuspension on the Release of Heavy Metals and Water Chemistry in Anoxic and Oxic Sediments

Two types of river sediments with contrasting characteristics (anoxic or oxic) were resuspended and the release of heavy metals and changes in water chemistry were investigated. During resuspension of the anoxic sediment, the dissolved oxygen (DO) concentration and redox potential of the water layer decreased abruptly within the first 1 min, followed by increases toward the end of the resuspension period. Heavy metals were released rapidly in the first 6 h, probably due to the oxidation of acid volatile sulfide (AVS) of the anoxic sediment, and then the aqueous phase concentrations of the heavy metals decreased due to resorption onto the sediment until the 12‐h point. During resuspension of the oxic sediment, the DO concentration and redox potential remained relatively constant in the oxic ranges. The heavy metals were released from the oxic sediment gradually during a 24‐h resuspension period. The temporal maximum concentrations of Ni, Cu, Zn, and Cd in the aqueous phases in both experiments frequently exceeded the USEPA water quality criteria or the water quality guidelines of Australia and New Zealand. This suggests that a resuspension event could bring about temporal water quality deterioration in the two sediment environments.     

Iron in the southeastern Bering Sea: Elevated leachable particulate Fe in shelf bottom waters as an important source for surface waters

Surface transects and vertical profiles of total and leachable particulate Fe, Mn, Al and P, along with dissolved and soluble Fe were obtained during August 2003 in the southeastern Bering Sea. High concentrations of leachable particulate Fe were observed in the bottom waters over the Bering Sea shelf with an unusually high percentage of the suspended particulate Fe being leachable. Leachable particulate Fe averaged 81% of total particulate Fe, and existed at elevated concentrations that averaged 23 times greater than dissolved Fe in the isolated cool pool waters over the mid shelf where substantial influence of sedimentary denitrification was apparent. The elevated leachable particulate Fe is suggested to be a result of sedimentary Fe reduction in surficial sediments, diffusion of Fe(II) from the sediments to the bottom waters, and subsequent oxidation and precipitation of reduced Fe in the overlying bottom waters. Eddies and meanders of the Bering Slope Current can mix this Fe-rich water into the Green Belt at the outer shelf-break front. Elevated levels of leachable particulate Fe were observed in surface waters near the Pribilof Islands where enhanced vertical mixing exists. Storm events and/or cooling during fall/winter with the resultant destruction of the thermally stratified two-layer system can also mix the subsurface water into surface waters where the elevated leachable particulate Fe is a substantial source of biologically available Fe.     

Trace metal dynamics in the water column and pore waters in a temperate tidal system: response to the fate of algae-derived organic matter

Tidal and seasonal behaviour of the redox-sensitive trace metals Mn, Fe, Mo, U, and V have been investigated in the open-water column and shallow pore waters of the backbarrier tidal flats of the island of Spiekeroog (Southern North Sea) in 2002 and 2007. The purpose was to study the response of trace metal cycles on algae blooms, which are assumed to cause significant changes in the redox state of the entire ecosystem. Trace metal data were complemented by measurements of nutrients and enumeration of algae cells in 2007. Generally, Mn and V show a tidal cyclicity in the water column with maximum values during low tide which is most pronounced in summer due to elevated microbial activity in the sediments. Mo and U behave almost conservatively throughout the year with slightly increasing levels towards high tide. Exceptions are observed for both metals after summer algae blooms. Thus, the seasonal behaviour of the trace metals appear to be significantly influenced by productivity in the water column as the occurrence of algae blooms is associated with an intense release of organic matter (e.g. transparent exopolymer particles, TEP) thereby forming larger organic-rich aggregates. Along with elevated temperatures in summer, the deposition of such aggregates favours microbial activity within the surface sediments and release of DOC, nutrients and trace metals (Mn, Mo and V) during the degradation of the aggregates. Additionally, pronounced reducing conditions lead to the reduction of Mn(IV)-oxides and Fe(III)-(oxihydr)oxides, thereby releasing formerly scavenged compounds as V and phosphate. Therefore, pore-water profiles show significant enrichments in trace metals especially from July to September. Finally, the trace metals are released to the open water column via draining pore waters (esp. Mo, Mn, and V) and/or fixed in the sediment as sulphides (Fe, Mo) and bound to organic matter (U). Non-conservative behaviour of Mo in oxygenated seawater, first observed in the investigation area by Dellwig et al. (Geochim Cosmochim Acta 71:2745–2761, 2007a), was shown to be a recurrent phenomenon which is closely coupled to bacterial activity after the breakdown of algae blooms. In addition to the postulated fixation of Mo in oxygen-depleted micro-zones of the aggregates or by freshly formed organic matter, a direct removal of Mo from the water column by reduced sediment surfaces may also play an important role.     

Speciation of heavy metals on suspended sediment under high flow conditions in the River Aire,West Yorkshire,UK

Concentrations of heavy metals (Cd, Cu, Pb and Zn) on suspended sediments during a flood event at Thwaite Mills, River Aire, were analysed using a five step sequential extraction technique to determine their major chemical associations (exchangeable, surface oxide and carbonate, Fe and Mn oxides, organic and residual metal ions). Total metal concentrations were lowest at higher discharges, resulting from dilution by clean sediment. The major transport fractions are the Fe and Mn oxides, which carry 29% of the total metals. Knowledge of the chemical forms of heavy metals on suspended sediment is essential for estimating their biological availability and physicochemical reactivity. © 1998 John Wiley & Sons, Ltd.     

Dissolved trace elements in a nitrogen-polluted river near to the Liaodong Bay in Northeast China

Dissolved trace element concentrations (Ba, Fe, Mn, Si, Sr, and Zn) were investigated in the Haicheng River near to the Liaodong Bay in Northeast China during 2010. Dissolved Ba, Fe, Mn, and Sr showed significant spatial variation, whereas dissolved Fe, Mn, and Zn displayed seasonal variations. Conditions such as water temperature, pH, and dissolved oxygen were found to have an important impact on redox reactions involving dissolved Ba, Fe, and Zn. Dissolved Fe and Mn concentrations were regulated by adsorption or desorption of Fe/Mn oxyhydroxides and the effects of organic carbon complexation on dissolved Ba and Sr were found to be significant. The sources of dissolved trace elements were found to be mainly from domestic sewage, industrial waste, agricultural surface runoff, and natural origin, with estimated seasonal and annual river fluxes established as important inputs of dissolved trace elements from the Haicheng River into the Liaodong Bay or Bohai Sea.     

Phosphorus fractionation and release characteristics of sediment in the Saemangeum Reservoir for seasonal change

Periodical algal blooms result in deposition and release of phosphorus (P) from the sediment into the water. Therefore, during seasonal changes when algal particles begin to settle to the bottom, understanding the behavior and distribution characteristics of the P in sediment is the most important key to manage the water quality of the Saemangeum Reservoir. In this study, the variation of water quality and sediment composition including chlorophyll-a (Chl-a) and P was investigated to determine the interaction between water and sediment. The study focused primarily on algal particle sedimentation that affects the P release and mineralization of sediment. The Chl-a concentration in water showed a sharp decline in October when the algae began to die in the fall, and afterward the concentration of chemical oxygen demand (COD) and total P (TP) in the sediment increased due to the sedimentation of decaying algal particles in November. During the same period of time, the readily bio-available P (RAP) in the sediment showed a drastic increase in the upper region where the Chl-a concentration of water was high. In sequence, the high RAP zone shifted from the upper region to the lower region in the early winter. The RAP shift was considered to be derived from the physical flow of the overlying water from which the decomposing algae settled on the surface of the sediment. The Saemangeum Reservoir was constructed recently; therefore, all the types of inorganic P fractions except soluble reactive phosphorus (SRP) that exist on the bottom surface of the lake and the marsh's sediment layer were not sufficient to significantly influence the overlying water. On the other hand, the released P from the algae was distinct and sensitive to the seasonal change. In conclusion, the algal particle sedimentation was important to control eutrophication rather than P release from the mineralized inorganic P of the sediment surface layer in the Seamangeum Reservoir.     

苏州河网区河道沉积物重金属的污染特征

分析测定了苏州河网区河道底泥十个剖面样点60个样品中Cu、Pb、Zn、Cr、Al、Fe、K、Mn、有机质、TP、TN、粒度、pH及含水量,采用地累积指数、生态风险指数和相关分析等方法研究其重金属污染特征.结果表明:Cu和Zn处于中或中-强度污染,Pb处于无-中污染,没有Cr污染;垂直分布特征显示:Cu和Zn污染逐年变化较为一致,Pb污染有逐年加重趋势;重金属潜在生态风险处于轻微污染状态;相关性分析显示,有机质是影响其分布的重要因素,Mn、Cr、Cu、Zn、Pb五种重金属相关性显著;通过与国内外河流、水库和湖泊沉积物中重金属含量比较,苏州河网区河道重金属的累积受多种因素影响.