Temporal variability of trace metals in new jersey pinelands streams: relationships to discharge and pH

Dissolved and particulate trace metal (Al, Cd, Cu, Pb, and Zn) concentrations were determined over a 21 month time period at four streamwater sites in the Pinelands (New Jersey, USA), a coastal plain region characterized by low-pH waters and highly weathered soils. Al and Zn were also determined at two sites over a 5 day period following a major precipitation event. In the Batsto River (pH 4.4–6.3), a representative Pinelands stream draining a largely forested watershed moderately impacted by agriculture, discharge-weighted mean concentrations of dissolved metals were (in nM): Al = 4610; Cd = 0.39; Cu = 4.6; Pb = 1.0; and Zn = 149. Dissolved Cd, Cu, and Zn in the undeveloped Bass River (pH 4.1–4.8) are in a similar range, but Pb concentration is 2–3 times greater. Dissolved metals show highly significant positive correlations to discharge, and weaker inverse relationships to pH over both the long- and short-term time series. Overall, seasonal and short-term variability in dissolved metal concentrations is most consistent with control by hydrologic flow path changes during high discharge, when shallow groundwaters mobilize anthropogenic metals stored in near-surface soil horizons and bypass potential metal removal processes in bordering wetlands. The data also suggest that in-stream metal removal driven by summertime biological productivity may further reduce low-discharge metal concentrations, as a secondary effect. For these metals, the particulate fraction is generally minor, and variations in solution/particle partitioning are unimportant to spatial/temporal variations dissolved concentrations, except for Pb. Estimates of atmospheric input can account for riverine fluxes of these metals, and suggest that Zn retention is minimal in this system, while Pb, Cu and Cd are more strongly retained. The positive relationship between discharge and metals concentration, and the unusually high concentrations in Pinelands streams compared to other world rivers, suggest that riverine effects on metals distributions in the estuary and nearby coastal ocean will be measurable and strongly seasonal.     

Temporal transport of major and trace elements in the upper reaches of the Xijiang River,SW China

This study investigated the temporal variations of major and trace element contents and controlling factors in the upper reaches of the Xijiang River, SW China. The results showed the major ions principally derived from the weathering of carbonate and silicate rocks, with a seasonal variation impacted by the monsoonal climate. The contents of dissolved trace elements also varied seasonally in the two main tributaries: the Nanpan and Beipan rivers. Most dissolved trace elements such as Mn, Zn and Pb being affected by anthropogenic contributions displayed a large seasonal variability, from onefold to hundred-fold, while V, Rb and U show a relative stable trend uncorrelated with the different seasons, suggesting a natural origin by rock weathering. Suspended particle matter in the Nanpan and Beipan rivers was depleted in Ca, Mg, Na, K and Sr, but enriched in Al, Fe and Sb compared to the upper crust (UC) values. A binary mixture of silicate-rich and carbonate-rich sources dominates the behavior of elements such as Ca and Sr in riverine sediments, while a third end-member with an anthropogenic signature influenced the content of trace elements like Mn, Sb, Pb, Zn, Cd, Cr and Cu. The enrichments of Sb relative to the UC would be related to the mining activity in the studied area. The study highlights the importance of investigating temporal variations of major and trace element contents of rivers controlled by the monsoon climate and impacted by human activity.     

Distribution of trace elements in waters and sediments of the Seversky Donets transboundary watershed (Kharkiv region,Eastern Ukraine)

This paper reports on the aquatic chemistry of trace elements in terms of spatial and temporal distribution, but also pollution sources in the transboundary watershed of the Seversky Donets River (Ukraine/Russia). Bed sediments and filtered water were collected from the Udy and Lopan Rivers at sites from the river source in the Belgorod region (Russia) to rural and urban areas in the Kharkiv region (Ukraine) in May and August 2009. Priority trace elements (As, Cd, Cr, Cu, Hg, Ni, Pb and Zn), an urban tracer (Ag) and additional metals (Co, Mo, V) and Th were measured in stream water and sediments. The low levels and variability of Th-normalized concentrations indicated the absence of geochemical anomalies in the upstream part of the rivers and suggested that these data represent a regional baseline for trace elements in bed sediments. In contrast, water and sediments within the city of Kharkiv were contaminated by Ag, Pb, Cd, Cu, Cr and Zn, which are mainly attributed to municipal wastewater inputs and urban run-off. Results of the environmental quality assessment showed that element concentrations in the sediments can be considered as potentially toxic to aquatic organisms in sites downstream of the wastewater discharges.     

Spatial and temporal variability of trace element concentrations in an urban subtropical watershed,Honolulu, Hawaii

Trace metal concentrations in soils and in stream and estuarine sediments from a subtropical urban watershed in Hawaii are presented. The results are placed in the context of historical studies of environmental quality (water, soils, and sediment) in Hawaii to elucidate sources of trace elements and the processes responsible for their distribution. This work builds on earlier studies on sediments of Ala Wai Canal of urban Honolulu by examining spatial and temporal variations in the trace elements throughout the watershed. Natural processes and anthropogenic activity in urban Honolulu contribute to spatial and temporal variations of trace element concentrations throughout the watershed. Enrichment of trace elements in watershed soils result, in some cases, from contributions attributed to the weathering of volcanic rocks, as well as to a more variable anthropogenic input that reflects changes in land use in Honolulu. Varying concentrations of As, Cd, Cu, Pb and Zn in sediments reflect about 60 a of anthropogenic activity in Honolulu. Land use has a strong impact on the spatial distribution and abundance of selected trace elements in soils and stream sediments. As noted in continental US settings, the phasing out of Pb-alkyl fuel additives has decreased Pb inputs to recently deposited estuarine sediments. Yet, a substantial historical anthropogenic Pb inventory remains in soils of the watershed and erosion of surface soils continues to contribute to its enrichment in estuarine sediments. Concentrations of other elements (e.g., Cu, Zn, Cd), however, have not decreased with time, suggesting continued active inputs. Concentrations of Ba, Co, Cr, Ni, V and U, although elevated in some cases, typically reflect greater proportions attributed to natural sources rather than anthropogenic input.     

Hydrological and biogeochemical dynamics of the minor and trace elements in the St. Lawrence River

Surface water samples from the St. Lawrence River were collected in order to study the processes controlling minor and trace elements concentrations (Al, Fe, Mn, Cd, Co, Cu, Ni and Zn), and to construct mass balances allowing estimates of the relative importance of their natural and anthropogenic sources. The two major water inputs, the upper St. Lawrence River, which drains waters originating from the Lake Ontario, and the Ottawa River were collected fortnightly over 18 months. In addition, other tributaries were sampled during the spring floods. The output was monitored near Quebec City at the river mouth weekly between 1995 and 1999. Dissolved metal concentrations in the upper St. Lawrence River carbonated waters were lower than in the acidic waters of the tributaries draining the crystalline rocks of the Canadian shield and the forest cover. Biogeochemical and hydrodynamic processes occurring in Lake Ontario drive the seasonal variations observed in the upper St. Lawrence River. Biogeochemical processes relate to biological uptake, regeneration of organic matter (for Cd and Zn) and oxyhydroxide formation (for Mn and Fe), while hydrodynamic processes mainly concern the seasonal change in vertical stratification (for Cd, Mn, and Zn). In the Ottawa River, the main tributary, oxyhydroxide formation in summer governs seasonal patterns of Al, Fe, Mn, Cd, Co and Zn. The downstream section of the St. Lawrence River is a transit zone in which seasonal variations are mainly driven by the mixing of the different water masses and the large input of suspended particulate matter from erosion. The budget of all dissolved elements, except Fe and Zn, was balanced, as the budget of particulate elements (except Cd and Zn). The main sources of metals to the St. Lawrence River are erosion and inputs from tributaries and Lake Ontario. Direct anthropogenic discharges into the river accounted for less than 5% of the load, except for Cd (10%) and Zn (21%). The fluxes in transfer of dissolved Cd, Co, Cu and Zn species from the river to the lower St. Lawrence estuary were equal to corresponding fluxes calculated for Quebec City since the distributions of dissolved concentrations of these metals versus salinity were conservative. For Fe, the curvature of the dilution line obtained suggests that dissolved species were removed during early mixing.     

Heavy metal partitioning in river sediments severely polluted by acid mine drainage in the Iberian Pyrite Belt

This study provides a geochemical partitioning pattern of Fe, Mn and potentially toxic trace elements (As, Cd, Cr, Cu, Ni, Pb, Zn) in sediments historically contaminated with acid mine drainage, as determined by using a 4-step sequential extraction scheme. At the upperstream, the sediments occur as ochreous precipitates consisting of amorphous or poorly crystalline oxy-hydroxides of Fe, and locally jarosite, whereas the estuarine sediments are composed mainly of detrital quartz, illite, kaolinite, feldspars, carbonates and heavy minerals, with minor authigenic phases (gypsum, vivianite, halite, pyrite). The sediments are severely contaminated with As, Cd, Cu, Pb and Zn, especially in the vicinity of the mining pollution sources and some sites of the estuary, where the metal concentrations are several orders of magnitude above background levels. Although a significant proportion of Zn, Cd and Cu is present in a readily soluble form, the majority of heavy metals are bonded to reducible phases, suggesting that Fe oxy-hydroxides have a dominant role in the metal accumulation. In the estuary, the sediments are potentially less reactive than in the riverine environment, because relevant concentrations of heavy metals are immobilised in the crystalline structure of minerals.     

Assessing the current state of the Gironde Estuary by mapping priority contaminant distribution and risk potential in surface sediment

Based on high spatial resolution monitoring, the first spatial distribution maps for the eight trace elements identified as priority contaminants in aquatic systems (i.e. As, Cd, Cr, Cu, Hg, Ni, Pb and Zn) in surface sediments of the Gironde Estuary (SW France) are presented. This large European fluvial–estuarine system is known for important historical multi-element (mainly Cd, Zn, Cu and Pb) pollution by former mining and mineral processing activation in the Riou-Mort watershed located 350 km upstream the estuary. As a consequence, oyster production in the estuary is prohibited, and Cd concentrations in oysters from the Marennes-Oléron area are close to consumption thresholds. Surface sediment samples were analysed for grain size, particulate organic C and trace element concentrations. Determination of trace elements was carried out by ICP-MS for As, Cd, Cr, Cu, Ni, Pb, Th and Zn, and by CV-AAS for Hg. Total and potentially released trace element stocks in the surface sediment were evaluated by using concentrations in the estuary and in selected sediment core. Assuming that sediment resuspension affects mainly the uppermost sediment layer, the total trace element stocks in the studied 0–10 cm depth range may represent the equivalent of one (Cd) to eight (As, Cr) times the annual fluvial trace element inputs into the estuary. Comparing total trace element concentrations in surface sediment with: (i) data on the regional geochemical baseline to evaluate the potentially remobilised fraction and (ii) the potentially bioavailable fraction aimed at establishing a first spatially resolved risk assessment of the trace element “cocktail” present in these sediments at the estuary scale. After correction for grain size effects by Th normalisation, potentially highly toxic metals such as Cd and Hg showed the highest enrichment factors. From ecotoxicological indices, areas were identified and quantified where trace element levels and mobility may bear a risk to benthic organisms. The GIS-based spatial distribution of ecotoxicological indices for the trace element “cocktail” suggests that ∼95% of the surface sediment are ‘Low–Medium’-priority zones, highlighting the need for further impact studies. The produced maps of trace element distributions and associated risk potentials are likely to be a useful tool to authorities in charge of sustainable estuarine management, e.g. for the optimisation of dredging activities or development of the estuarine infrastructure.     

Temporal and spatial patterns of trace elements in the Patuxent River: A whole watershed approach

Trace element distributions, partitioning, and speciation were examined at 15 sites in the Patuxent River watershed from May 1995 through October 1997 to determine possible sources of trace elements to the river and estuary, to examine the relationship of the trace element discharges to freshwater discharges as well as to land use and geographic region, to validate previous estimates of loadings to the river, and to provide baseline data for trace elements in the Patuxent River watershed and estuary. Six freshwater sites were examined, representing different basins and geographic provinces, and nine sites along the estuarine salinity gradient. Subregions within the watershed varied considerably in concentrations and areal yields for some elements. Concentrations of As, Cd, Ni, Pb, and Zn were elevated in the Coastal Plain sites compared to the Piedmont sites, while Cu and Hg were more evenly distributed. Cadmium, Cu, Hg, Ni, Pb, and Zn showed overall positive correlations with river flow while As and methylHg (meHg) showed negative correlations with river flow. Concentrations of trace elements in the estuarine portion of the river were generally low, and consistent with mixing between Patuxent River water with elevated concentrations and the lower concentrations of the Chesapeake Bay. Interesting features included a local Cd maximum in the low salinity region of the estuary, probably caused by desorption from suspended sediments, and a significant input of water containing high As concentrations from the Chesapeake Bay and from As being released from bottom sediments in summer. Comparisons between the estimated annual flux of trace elements and the estimates of suspected source terms (atmospheric deposition, urban runoff, and known point sources) suggest that, except for Hg, direct atmospheric deposition is small compared to fluvial loads. Current estimates of trace element inputs from point sources or from urban runoff are inadequate for comparison with other sources, because of inappropriate techniques and/or unacceptably high detection limits. A complete examination of trace element dynamics in the Patuxent River (and in other coastal systems) will require better data for these potential sources.     

Endmember analysis of heavy-metal pollution in surficial sediments from the Gulf of Gdansk and the southern Baltic Sea off Poland

Thirty one bulk (<2 mm) samples of surficial sediments from the Gulf of Gdansk and the Southern Baltic Sea off Poland were analyzed for 20 elements and the resulting compositional dataset was subjected to endmember analysis. The compositions of 4 endmember estimates were constructed and the abundances of these endmembers were calculated for each sample. Copper, Zn and Ag appear on one endmember and Cd and Pb on another. This suggests that Cu, Zn and Ag are introduced into the Gulf of Gdansk principally from the Vistula River whereas Cd and Pb are introduced as a result of atmospheric and riverine transport of these elements. The dual source of Cd and Pb into the Gulf of Gdansk may explain the complex interelement relationships displayoed by these elements in the sediments from this region.     

Geochemical variations of major and trace elements in recent sediments,off the Gulf of Mannar,the southeast coast of India

The Gulf of Mannar along the Tuticorin coast is a coral base of the southeast coast of India. To obtain a preliminary view of its environmental conditions, geochemical distribution of major elements (Si, Al, Fe, Ca, Mg, Na, K, P), trace elements (Mn, Cr, Cu, Ni, Co, Pb, Zn, Cd) and acid leachable elements (Fe, Mn, Cr, Cu, Ni, Co, Pb, Zn, Cd) were analyzed in surface sediment samples from two seasons. Geochemical fractionation confirmed the lithogenic origin of metals, which were mainly associated with the detrital phase. The sediments in the gulf are sandy with abundant calcareous debris, which controls the distribution of total and acid leachable elements. Enrichment factors relative to crust vary by a magnitude of two to three and the presence of trace metals indicates the input of Cr, Pb, Cd, Cu and Zn in both forms through industrial activities. Factor analysis supports the above observation with higher loadings on acid leachable elements and its association with CaCO₃. The increase in concentration of trace metals (Cr, Pb, Cd, Cu, Co, Ni, Zn) along the Gulf of Mannar indicates that the area has been contaminated by the input from riverine sources and the industries nearby. The present study indicates that other sources should be evaluated in the long-term monitoring program.     

Dissolved trace elements in the Mississippi River: Seasonal,interannual, and decadal variability

A monthly trace element sampling of the lower Mississippi River, utilizing ultra-clean methods, was conducted from October 1991 to December 1993. Dissolved concentrations were determined for Fe, Mn, Zn, Ph, V, Mo, U, Cu, Ni, Cd, Rb, and Ba. The results show significant seasonal dissolved concentration changes for a number of elements. Specifically, dissolved Mn and Fe are found to increase rapidly in the fall and then decrease in the spring. Zn and Pb follow a similar seasonal trend, though with lower percentage concentration changes. V, Mo, and U follow an opposite seasonal trend to Mn and Fe. The data do not allow a complete determination of the causes of this variability. However, changes in the adsorption process do not appear to play an important role. Hydrologic factors are also of minimal importance for most elements, with the probable exception of Ba and U. I suggest here that redox processes, occurring both in-stream and in source regions, play an important role in determining seasonal variations in dissolved trace elements.No evidence was found of significant dissolved trace element concentration changes over the past decade and interannual variability in mean concentrations was generally small. The time series also encompassed a period of extreme flooding in the U.S. Midwest. However, the flooding did not significantly influence dissolved trace element concentrations in the lower Mississippi River.     

Biogeochemistry of trace metals (Mn, Sr, Rb, Ba, Cu, Zn, Pb and Cd) in a river-wetland-lake system (Balaton Region, Hungary)

Mn, Sr, Ba, Rb, Cu, Zn, Pb and Cd concentrations have been measured seasonally in the water and deposited sediments of the system comprising: Zala river (main input) — Lakes Kis-Balaton 1 and 2 (small artificial lakes created in a former bay of Lake Balaton) — Keszthely bay (hypertrophic part of Lake Balaton). The concentrations of the trace elements together with pH, alkalinity, dissolved cations (Ca²⁺, Mg²⁺, Na⁺, and K⁺), dissolved inorganic ligands (Cl^–, SO₄ ^2–), particulate Al, Ca, inorganic and organic carbon are used to assess the contamination of the study area and biogeochemical processes controlling trace element concentrations. Thermodynamic speciation calculations have also been utilized to enhance our understanding of the system. In the sediments Rb, Ba, Cu and Zn concentrations were mainly controlled by the abundance of the aluminosilicate fraction. Strontium was mainly associated with the calcium carbonate fraction. The aluminosilicate fraction constitutes a major sink for Mn and Cd but the concentration of these elements are also strongly related to calcite precipitation. The main processes that control the dissolved distribution of trace elements in the Balaton system were: solid phase formation (carbonate) for Mn; coprecipitation with calcite for Sr, Ba, Rb and possibly Mn and Cd; adsorption/desorption processes (pH dependent) for Zn and Pb; solubilization of Mn and precipitation of Cd and Cu in reed covered wetland areas where anoxic conditions were probably existing during the warm season. A preliminary budget of atmospheric and river input to Lake Balaton has also been outlined. Although Lake Balaton, is subjected to anthropogenic inputs mainly from agricultural and domestic activities, their impact on trace element concentrations in the Balaton system is very limited due to the efficiency of removal processes (i.e. adsorption and co-precipitation) and to high sedimentation rates and strong sediment re-suspension. Anthropogenic inputs are only detected for Pb.     

Spatio-temporal trends of heavy metals and source apportionment in Tolo Harbour,Hong Kong

This study provided a picture of the spatial and temporal distributions of Cr, Co, Ni Cu, Zn, As, Cd and Pb in bottom sediments of Tolo Harbour. The concentrations of the eight heavy metals differed significantly between sites due to the poor tidal flushing in Tolo Harbour. The levels of Cu, Zn, Cd and Pb were generally enriched in sediments from inner Tolo Harbour, while sediments from outer Tolo Harbour (Tolo Channel) had higher levels of Cr, Co and Ni. The redox sensitive element arsenic showed no distinct spatial pattern in Tolo Harbour. The decreasing levels of Cu, Zn, Pb and Cd in sediments with increasing distance from land demonstrated a typical diffusion pattern from land to the direction of sea. Two hot spots of Cu, Zn, Pb and Cd in sediments were located near Tai Po and Sha Tin new town, indicating that Cu, Zn, Pb and Zn were from land-derived sources. The sites with relatively high levels of Cr, Co and Ni in sediments were located in areas close to waste spoil in sea floor. The natural and anthropogenic inputs from Sha Tin and Tai Po to Tolo Harbour were mostly responsible for Cu, Zn, Cd and Pb enrichment in sediments from inner Tolo Harbour. The waste spoil in sea floor was believed to contribute to the Cr, Co and Ni in outer Tolo Harbour. The results of correlation coefficient between the eight heavy metals showed that Cu, Zn, Cd and Pb were strongly positively correlated, and Cr, Co and Ni were also significantly correlated with each other. The best explanation of strong correlation was their similar source. As, however, is not well correlated with the other seven heavy metals. The average concentrations of Cu and Zn displayed general increasing trends from 1978 to 2006 in Tolo Harbour, while the mean levels of Cr and Pb displayed a substantial decrease from 1978 to 1987, then a slight increase after 1987. No distinct temporal trends of the concentrations of Ni and As were observed from 1978 due to the inconsecutive data. On the other hand, the increasing trends of Cr, Cu, Zn, Cd and Pb were observed since 1996.     

Anthropogenic components of heavy metal (Cd,Zn, Cu,Pb) budgets in the Lot-Garonne fluvial system (France)

Heavy metal (Zn, Cd, Cu and Pb) mass balances in the Lot-Garonne fluvial system have been established for 1999 and 2000. The mean annual discharges of these years are close to the mean discharge of the previous decade. The estimated annual dissolved and particulate fluxes in this model watershed integrate daily input from diffuse and point sources, diffusive fluxes at the water/sediment interface, changes in the dissolved-particulate partition and changes in sediment stock. Cadmium, Zn, Cu and Pb entering the Gironde estuary via the Garonne River (11–14 t a⁻¹ of Cd; 1330–1450 t a⁻¹ of Zn; 126–214 t a⁻¹ of Cu and 127–155 t a⁻¹ of Pb) are mainly transported in the particulate phase and the major part (i.e. ∼74 to 96% for Cd, ∼60% for Zn, ∼50 to 60% for Cu and ∼80% for Pb) is transported by the Lot River. The main anthropogenic heavy metal point source is located in a small upstream watershed (Riou-Mort River) accounting for at least 47% (Cd), ∼20% (Zn), ∼4% (Cu) and ∼7 to 9% (Pb) of the total heavy metal inputs into the Garonne River, although it contributes only 1% of the discharge. Mass balances for 1999 suggest that under mean annual hydrologic conditions on the basin scale, the heavy metal budget of the Lot-Garonne fluvial system is balanced and that the stocks of Cd [200 t; Environ. Tech. 16 (1995) 1145] and Zn in the Lot River sediment are constant under mean discharge conditions. Heavy metal input by molecular diffusion at the sediment surface represents an important component of dissolved metal inputs into the system (e.g. 30% for Cu). Except for Cu, these dissolved inputs are totally removed from solution by SPM. Based on the generally constant Zn/Cd (∼50) concentration ratio in sediment cores from the polluted Lot River reaches and the sediment stock of Cd [200 t; Environ. Tech. 16 (1995) 1145], the present day Zn stock in the Lot River sediments has been estimated at about 10,000 t. In addition to the mobilization of river-bed sediment and associated heavy metals by intense floods, local human activities, including river-bed dredging, may strongly modify the heavy metal budget of the river system. In 2000, the dredging-related remobilization of polluted Lot River sediment released 2–6 t Cd. This additional Cd point source was estimated to account for 15–43% of the gross inputs into the Gironde Estuary.     

Post-depositional redistribution of trace metals in reservoir sediments of a mining/smelting-impacted watershed (the Lot River,SW France)

Mining/smelting wastes and reservoir sediment cores from the Lot River watershed were studied using mineralogical (XRD, SEM–EDS, EMPA) and geochemical (redox dynamics, selective extractions) approaches to characterize the main carrier phases of trace metals. These two approaches permitted determining the role of post-depositional redistribution processes in sediments and their effects on the fate and mobility of trace metals. The mining/smelting wastes showed heterogeneous mineral compositions with highly variable contents of trace metals. The main trace metal-bearing phases include spinels affected by secondary processes, silicates and sulfates. The results indicate a clear change in the chemical partitioning of trace metals between the reservoir sediments upstream and downstream of the mining/smelting activities, with the downstream sediments showing a 2-fold to 5-fold greater contribution of the oxidizable fraction. This increase was ascribed to stronger post-depositional redistribution of trace metals related to intense early diagenetic processes, including dissolution of trace metal-bearing phases and precipitation of authigenic sulfide phases through organic matter (OM) mineralization. This redistribution is due to high inputs (derived from mining/smelting waste weathering) at the water–sediment interface of (i) dissolved SO₄ promoting more efficient OM mineralization, and (ii) highly reactive trace metal-bearing particles. As a result, the main trace metal-bearing phases in the downstream sediments are represented by Zn- and Fe-sulfides, with minor occurrence of detrital zincian spinels, sulfates and Fe-oxyhydroxides. Sequestration of trace metals in sulfides at depth in reservoir sediments does not represent long term sequestration owing to possible resuspension of anoxic sediments by natural (floods) and/or anthropogenic (dredging, dam flush) events that might promote trace metal mobilization through sulfide oxidation. It is estimated that, during a major flood event, about 870 t of Zn, 18 t of Cd, 25 t of Pb and 17 t of Cu could be mobilized from the downstream reservoir sediments along the Lot River by resuspension-induced oxidation of sulfide phases. These amounts are equivalent to 13-fold (Cd), ∼6-fold (Zn), 4-fold (Pb) the mean annual inputs of the respective dissolved trace metals into the Gironde estuary.     

Distribution of selected trace elements in sediments of Pamlico river estuary,north Carolina

Sixty-eight samples of sediment collected on a variably-spaced grid pattern from Pamlico River Estuary of North Carolina were analyzed for As, Cd, Co, Cr, Cu, F, Ni, Pb, U, Zn, clay, and organic matter. The major objectives of the study were to determine background and anomalous levels of trace elements in the sediments, and the effects of human activities on concentration and distribution of trace elements in the sediments. Clay and organic matter are more concentrated near the center of the estuary. This causes the highest concentration of trace elements in the sediments to be located there also owing to their preferential uptake of these elements. Highest trace element concentrations were observed in clay and organic matter near industrial sites, housing developments, and tributary mouths that drain areas of human activity. The apparent increase in trace element contents of fine sediments in Pamlico River Estuary owing to human activities is 4 to 1,750 times normal background levels.     

Using Multivariate Statistical and Geostatistical Methods to Identify Spatial Variability of Trace Elements in Agricultural Soils in Dongguan City,Guangdong,China

Dongguan (东莞) City, located in the Pearl River Delta, South China, is famous for its rapid industrialization in the past 30 years. A total of 90 topsoil samples have been collected from agricultural fields, including vegetable and orchard soils in the city, and eight heavy metals (As, Cu, Cd,Cr, Hg, Ni, Pb, and Zn) and other items (pH values and organic matter) have been analyzed, to evaluate the influence of anthropie activities on the environmental quality of agricultural soils and to identify the spatial distribution of trace elements and possible sources of trace elements. The elements Hg, Pb, and Cd have accumulated remarkably here, incomparison with the soil background content of elements in Guangdong (广东) Province. Pollution is more serious in the western plain and the central region, which are heavily distributed with industries and rivers. Multivariate and geostatistical methods have been applied to differentiate the influences of natural processes and human activities on the pollution of heavy metals in topsoils in the study area. The results of cluster analysis (CA) and factor analysis (FA) show that Ni, Cr, Cu, Zn, and As are grouped in factor F1,Pb in F2, and Cd and Hg in F3, respectively. The spatial pattern of the three factors may be well demonstrated by geostatistical analysis. It is shown that the first factor could be considered as a natural source controlled by parent rocks. The second factor could be referred to as "industrial and traffic pollution sources". The source of the third factor is mainly controlled by long-term anthropic activities ,ad a consequence of agricultural fossil fuel consumption and atmospheric deposition.     

Distribution and partitioning of major and trace elements in pyrite-bearing sediments of a Mediterranean coastal lagoon

The formation of iron sulphide minerals exerts significant control on the behaviour of trace elements in sediments. In this study, three short sediment cores, retrieved from the remote Antinioti lagoon (N. Kerkyra Island, NW Greece), are investigated concerning the solid phase composition, distribution, and partitioning of major (Al, Fe) and trace elements (Cd, Cu, Mn, Pb, and Zn). According to ²¹⁰Pb, the sediments sampled correspond to depositions of the last 120 years. The high amounts of organic carbon (4.1–27.5%) result in the formation of Fe sulphides, predominantly pyrite, already at the surface sediment layers. Pyrite morphologies include monocrystals, polyframboids, and complex FeS–FeS₂ aggregates. According to synchrotron-generated micro X-ray fluorescence and X-ray absorption near-edge structure spectra, authigenically formed, Mn-containing, Fe(III) oxyhydroxides (goethite type) co-exist with pyrite in the sediments studied. Microscopic techniques evidence the formation of galena, sphalerite and CuS, whereas sequential extractions show that carbonates are important hosts for Mn, Cd, and Zn. However, significant percentages of non-lattice held elements are bound to Fe/Mn oxyhydroxides that resist reductive dissolution (on average 60% of Pb, 46% of Cd, 43% of Zn and 9% of Cu). The partitioning pattern changes drastically in the deeper part of the core that is influenced by freshwater inputs. In these sediments, the post-depositional pyritization mechanism, illustrated by overgrowths of Fe monosulphides on pre-existing pyrite grains, results in relatively high degree of pyritization that reaches 49% for Cd, 66% for Cu, 32% for Zn and 7% for Pb.     

Sources and flux of trace elements in river water collected from the Lake Qinghai catchment,NE Tibetan Plateau

River waters play a significant role in supplying naturally- and anthropogenically-derived materials to Lake Qinghai, northeastern Tibetan Plateau. To define the sources and controlling processes for river water chemistry within the Lake Qinghai catchment, high precision ICP-MS trace element concentrations were measured in water samples collected from the Buha River weekly in 2007, and from other major rivers in the post-monsoon (late October 2006) and monsoon (late July 2007) seasons. The distributions of trace elements vary in time and space with distinct seasonal patterns. The primary flux in the Buha River is higher TDS and dissolved Al, B, Cr, Li, Mo, Rb, Sr and U during springtime than those during other seasons and is attributed to the inputs derived from both rock weathering and atmospheric processes. Among these elements, the fluxes of dissolved Cr, B and Rb are strongly influenced by eolian dust input. The fluxes of dissolved Li, Mo, Sr and U are also influenced by weathering processes, reflecting the sensitivity of chemical weathering to monsoon conditions. The anthropogenic sources appear to be the dominant contribution to potentially harmful metals (Ni, Cu, Co, Zn and Pb), with high fluxes at onset of the main discharge pulses due, at least partially, to a runoff washout effect. For other major rivers, except for Ba, concentrations of trace elements are higher in the monsoon than in the post-monsoon season. A total of 38.5 ± 3.1 tons of potentially harmful elements are transported into the lake annually, despite human activities within the catchment being limited. Nearly all river water samples contain dissolved trace elements below the World Health Organization guidelines for drinking water, with the exception of As and B in the Daotang River water samples collected in late July probably mobilized from underlying lacustrine sediments.