Metal binding capacity of northern European surface waters for Cd,Cu, and Pb

Total concentrations of and binding capacities for Cd, Cu, and Pb were measured in selected surface waters from northwestern Europe. Linear multiple regression predictive models explained 97, 93, and 96% of the observed variation in Cd, Cu and Pb binding capacities, respectively. The models constructed used (CO₂^3?) and (SO₂^2?) to predict Cd binding capacity, (OH^?) and (SO₄^2?) to predict Cu binding capacity and (OH^?), (CO₃^2?) and (SO₄^2?) to predict Pb binding capacity. Organic carbon was not significantly correlated with binding capacities for Cd, Cu, and Pb and was unimportant in explaining a significant amount of the variability in binding capacities for the metals of northern European surface waters. Thus, the effects of these organics on trace metal speciation can be ignored and predictive models of trace metal speciation constructed, using inorganic solubility equilibria only. Ratios of total Cd, Cu, and Pb concentrations to their respective binding capacities were much less than unity for all waters studied. Copper exhibited the greatest metal concentrations: binding capacity ratio in all waters investigated.     

Trace metal speciation in sea and pore water of the Gotland Deep,Baltic Sea, 1994

Studies on the speciation (particulate, colloidal, anionic and cationic forms) of trace metals (Cd, Co, Cu, Fe, Mn, Mo, Ni, Pb, Zn) in the water column and in pore waters of the Gotland Deep following the 1993/94 salt-water inflows showed dramatic changes in the total “dissolved” metal concentrations and in the ratios between different metal species in the freshly re-oxygenated waters below 125 m. Changes in concentrations were greatest for those metals for which the solubility differs with the redox state (Fe, Mn, Co) but were also noted for those metals which form insoluble sulphides (Cd, Pb, Cu, Zn) and/or stable complexes with natural ligands (Cu). Pore water data from segmented surface muds (0–200 mm) indicated that significant redox and related metal speciation changes took place in the surface sediments only a few weeks after the inflow of the oxygenated sea water into the Gotland Deep.     

Abundance, Sources and Speciation of Trace Elements in Humus-Rich Streams Affected by Acid Sulphate Soils

The behaviour of trace elements (Al, As, Cd, Co, Cr,Cu, Fe, Mn, Ni, V, Zn) was studied in five humus-richstreams (dissolved organic carbon = 14–40 mg/L)impacted by acid sulphate soils developed in marinesulphide-bearing fine-grained sediments. During heavyrainfalls in autumn, on which the study focusses, themetals Al, Cd, Co, Cu, Mn, Ni and Zn are extensivelyleached from these acidic soils (pH = 2.5–4.5), whileAs, Cr, Fe and V are not leached more strongly fromthis soil type than from areas of till and peat. Aspeciation experiment, based on anion and cationexchange of the stream waters in the field, showedthat (1) the metals Al, Cd, Co, Mn, Ni and Zn aretransported in the streams mainly as inorganiccations, (2) Cu exists mainly in cationic form but isalso to a significant extent associated with dissolvedhumic substances, (3) Fe occurs mainly in the anionicfraction explained by organic coating on colloidal Feoxyhydoxides and (4) the hydrochemistry of As, Cr andV is complex as these elements may exist in severalunquantified anionic fractions and to a minor extentin cationic species/forms. Whereas the proportion ofacid sulphate soils in the catchments had a largeimpact on concentrations levels of several elements inthe stream waters, these soils did not have a largeaffect on the speciation of elements in water.     

生态地球化学土壤样品元素形态分析方法研究

对生态地球化学土壤样品,采用振荡提取法提取样品中离子交换态(包括水溶态)、碳酸盐结合态、腐殖酸结合态、铁锰氧化物结合态、强有机质结合态(包括部分硫化物);采用等离子体发射光谱法测定其中Cd、Co、Cr、Cu、Mn、Mo、Ni、Pb、Zn,原子荧光光谱法测定As、Hg、Sb、Se。方法的质量参数满足生态地球化学土壤样品评价形态分析的需要。     

Speciation and potential remobilization of heavy metals in sediments of the Taihu Lake, China

The species of Cu, Pb, Zn, Cd and Cr in sediments of the Taihu Lake, China, have been analyzed using the sequential chemical extraction method. Variations in the chemical fractions of these metals and their geographic distributions have also been studied. For all five metals, the residual fraction is highest but the exchangeable fraction is lowest among all the fractions. Compared to other metals, Cd has the highest percentage in the exchangeable fraction, and Cr is associated mainly with the residual fraction. Cu in the organic fraction and Pb in the Fe-Mn fraction are the important species, whereas the lowest percentages are found for Cd in the organic fraction, Cu in the Fe-Mn oxide fraction and Pb in the carbonate fraction. With respect to spatial differences, the total contents in the non-residual fractions of the metals in bay sediments are found to be higher than those in other sediments. The fractions of Cd, Cu and Cr showed significant variations in different regions. The fractions of Pb and Zn, however, did not show significant variations in spatial distribution, suggesting different amounts and different paths of anthropogenic input for the metals. Comparisons of the metal speciation indicated that Cd might be the most bioavailable metal, followed by Pb.     

太湖沉积物中重金属的地球化学形态及特征分析

用连续提取法分析了太湖沉积物5种重金属的地球化学形态,对地球化学形态的组成和地理特征进行了分析研究.重金属地球化学形态配分的共同特点是可交换态最低,残渣态最高.两种形态中Cd的可交换态最高,Cr的残渣态最高,可交换态最低.Cd的碳酸盐态较高,Cr的最低;Pb、Cd的Fe-Mn氧化态较高,Cu的偏低;Cu的有机态最高,Cd的最低;Zn的地球化学形态比例大都处于中间.地域上变化较大的元素是Cd和Cu,变化不明显的元素有Pb和Zn.化学成分中Fe2O3、MnO与重金属地球化学形态的相关性最好,TOC与Cu的形态相关系数最高.综合对比分析表明,太湖沉积物重金属的生物有效性以Cd为最高,其次为Pb.     

Chemical weathering in the drainage basin of a tropical watershed (Nsimi-Zoetele site, Cameroon) : comparison between organic-poor and organic-rich waters

This study deals with the weathering processes operating at the scale of a small catchment (Nsimi-Zoetele, Cameroon) and is focused on the role of organic colloids on mineral weathering and transport of elements in natural waters. Samples of river, spring and groundwaters from Nsimi-Zoetele were filtered through membranes of decreasing pore size (0.22 μm, 0.025 μm, or: 300,000 Da, 5000 Da) to separate colloidal fractions from the truly dissolved one. Major and trace elements and dissolved organic carbon (DOC) were analysed in each fraction. Two kinds of waters can be distinguished in the catchment: clear and coloured waters. Clear waters exhibit low concentrations of major and trace elements and DOC. Elements are carried in these solutions in a true dissolved form except Al and rare earth elements (REEs). By contrast, the higher abundances of Al, Fe and trace elements in coloured waters are controlled by the colloidal fraction. Thermodynamic equilibrium calculations show that clear waters are in equilibrium with kaolinite and iron oxi-hydroxide which are major minerals in the weathered soil. For coloured waters, the aqueous speciation of Ca, Mg, Cu, Fe, Al, La and Th was calculated taking into account the complexes with humic acids. Speciation calculations for Cu, Fe, Al, La, Th show a strong complexation with humic acids, in good agreement with the results of the filtration experiments. By contrast, although filtration experiments show a strong control of major cations by organic matter (for example 75% for Ca), speciation calculations reveal that their complexes with humic ligands do not exceed a few percent of total dissolved elements. This discrepancy is explained as an artefact induced by the organic colloids and occurring during the filtration procedure. Finally, both filtration experiments and speciation calculations show that organic matter plays an important role in natural DOC-rich waters. Organic acids increase significantly the dissolution rates of silicates and oxi-hydroxides and thus the amounts of solutes and of complexed elements leaving the catchment.     

Specifics of the elemental composition of waters in environments with operating mining and ore-processing plants in the Kola North

The paper presents data on the specifics of the distributions of chemical elements in natural waters of the Kola North depending on the landscape–geochemical characteristics of the water catchment areas and aerotechnogenic pollution. The territory is subdivided into seven zones with different dominant rock types and typical landscapes. Lakes in the Kola region generally contain elevated concentrations of Cu, Ni, Co, Cr, V, Mo, U, Sb, Bi, Al, Fe, Mn, Sr, Li, Rb, Pb, Zn, Cd, La, and Ce. The waters of lakes in the influence zones of Cu–Ni mines are enriched in La, Ce, Sm, Gd, Pr, and Nd. In waterlogged landscapes, waters are enriched in certain trace elements because of their migration with humic acids. Technogenic acidic precipitation is proved to result in leaching of several elements, first of all Cd, Zn, and As (as well as other elements contained in rocks composing the water catchment areas) and their transfer into the waters.     

Distribution of dissolved organic carbon and metal-binding capacity among ultrafilterable fractions isolated from selected surface waters of the southeastern United States

The binding capacities of surface waters for Cd, Cu, and Pb were determined for eight water samples representing four rivers and two swamps from Florida and Georgia in the southeastern United States The binding capacity ranges were CdBC=0 04 to 0 79 μg atm/L, CuBC=1 0 to 5 4 μg atm/L, and PbBC=5 0 to 17 8 μg atm/L Binding capacity values from the southeastern United States are shown to be in good agreement with values reported from the northeastern part of the country and northern Europe The CdBC was due primarily to inorganic ligand binding, while PbBC was predominantly a result of organic matter The CuBC was due to a complex function of both organic and inorganic binding Significant portions of the CuBC and PbBC could be removed from the waters by ultrafiltration of particles between 0·45 μm and 52 Å in diameter Ultrafiltration, even to removing particles > 13 Å diameter, did not affect the CdBC Distributional studies of the dissolved organic carbon in these systems reveal that significant fractions of the DOC are present in the ultrafilterable fraction which contains significant portions of the CuBC and PbBC     

恬矿库周围土壤中重金属存在形态特征研究

通过对大冶铜绿山铜铁矿尾矿库周围土壤中重金属形态分析实验,研究了重金属各种形态在土壤中的分布特征。由对比实验可知,尾矿库周围土壤中Ｃｕ、Ｐｂ、Ｚｎ、Ｃｄ等重金属含量都显著地高于对照样品,书经受到重金属的严重污染。土壤中重金属形态分布征为：ｗ（Ｃｒ、Ｚｎ、Ｆｅ）;可变换态〈碳酸盐态〈有机态〈铁锰氧化态〈残渣态;ｗ（Ｃｕ、Ｐｂ）：可变换态〈碳酸盐态〈有机态〈残渣态〈铁锰氧化态;ｗ（Ｃｄ）：残渣态,有机     

Trace metal behaviour in riverine sediments: Role of organic matter and sulfides

Three sediment cores were collected in the Scheldt, Lys and Spiere canals, which drain a highly populated and industrialized area in Western Europe. The speciation and the distribution of trace metals in pore waters and sediment particles were assessed through a combination of computational and experimental techniques. The concentrations of dissolved major and trace elements (anions, cations, sulfides, dissolved organic C, Cd, Co, Fe, Mn, Ni, Pb and Zn) were used to calculate the thermodynamic equilibrium speciation in pore waters and to evaluate the saturation of minerals (Visual Minteq software). A sequential extraction procedure was applied on anoxic sediment particles in order to assess the main host phases of trace elements. Manganese was the most labile metal in pore waters and was mainly associated with carbonates in particles. In contrast, a weak affinity of Cd, Co, Ni, Pb and Zn with carbonates was established because: (1) a systematic under-saturation was noticed in pore waters and (2) less than 10% of these elements were extracted in the exchangeable and carbonate sedimentary fraction. In the studied anoxic sediments, the mobility and the lability of trace metals, apart from Mn, seemed to be controlled through the competition between sulfidic and organic ligands. In particular, the necessity of taking into account organic matter in the modelling of thermodynamic equilibrium was demonstrated for Cd, Ni, Zn and Pb, the latter element exhibiting the strongest affinity with humic substances. Consequently, dissolved organic matter could favour the stabilization of trace metals in the liquid phase. Conversely, sulfide minerals played a key role in the scavenging of trace metals in sediment particles. Finally, similar trace metal lability rankings were obtained for the liquid and solid phases.     

The Heavy Metals Speciations in Bottom Sediments of Vyshny Volochek Reservoir

The water ecosystem of the Vyshny Volochek Reservoir is characterized based on the study of the distribution of heavy metals speciations in the solid phase and pore waters of bottom sediments. Using the sequential extraction procedure, it is shown that Mn is mainly present in exchangeable and carbonate-bound forms; significant roles for Fe, Zn, Pb, and Co are played by forms that are bound to iron and manganese hydroxides and Cu and Ni are mainly bound to organic matter. Thermodynamic calculations have established the prevailing share of the following forms in pore waters: free ions for Zn, Ni, Co, and Cd, carbonate complexes for Pb, and fulvic complexes for Cu. It has been revealed that the speciation forms of heavy metals in bottom sediments depend on the lithological features and content of organic matter in sediments.     

In situ adsorption of mercury,methylmercury and other elements by iron oxyhydroxides and organic matter in lake sediments

Samples of authigenic material, sediment overlying water and oxic surface sediment (0–0.5-cm depth) from a perennially oxygenated lacustrine basin were analysed to investigate which solid phases are important for binding a suite of trace elements (Ag, As, Ca, Cd, Cu, Hg, In, methylmercury (MeHg), Mg, Mo, Pb, Sb and Zn). The authigenic material, which was collected with inert Teflon sheets deployed for several years across the sediment–water interface, contained mainly poorly crystallized Fe oxyhydroxides and natural organic matter, presumably humic substances derived from the watershed. Manganese oxyhydroxides were not present in the collected authigenic material due to the slightly acidic condition (pH = 5.6) of the lake that prevents the formation and recycling of these compounds. Conditional equilibrium constants for the adsorption of cationic (K_Fe–M) and anionic (K_Fe–A) trace elements onto the authigenic Fe oxyhydroxides were estimated from their concentrations in the authigenic material and in bottom water samples. These field-derived values of K_Fe–M and K_Fe–A were compared with those predicted by the surface complexation model, using laboratory-derived intrinsic adsorption constants and the water composition at the study site. Equilibrium constants (K_POM–M) were also calculated for the adsorption of the cationic trace elements onto the humic substances contained in the diagenetic material. The field-derived values of K_POM–M were compared to those predicted by the speciation code WHAM 6 for the complexation of the trace elements by dissolved humic substances in the lake. Combining the results of the present study with those on the distributions of trace elements in the porewater and solid-phase sediments reported in previous studies at the same site, it was determined whether the trace elements bind preferentially to Fe oxyhydroxides or natural organic matter in oxic sediments. The main inferences are that the anionic trace elements As, Mo and Sb, as well as the cationic metal Pb are preferentially bound to the authigenic Fe oxyhydroxides whereas the other trace elements, and especially Hg and MeHg, are preferentially bound to the humic substances.     

Aquatic geochemistry of small lakes: Effects of environment changes

This paper reports the results of an extensive investigation of water chemistry in the small lakes of European Russia and Western Siberia along a climatic gradient. It was demonstrated that small lakes unaffected by any direct contamination can be used as indicators of natural geochemical conditions of water formation, as well as global and regional fluxes of airborne pollution and climate warming. A novel concept was developed for within- and between-zone variability in water chemistry over vast areas of tundra, taiga, forest, and steppe, and contributions of natural and anthropogenic factors to its formation under present-day conditions were estimated. A proposed predictive scenario showed that climate warming will result in an increase in water salinity in southern regions and ubiquitous phosphorus enrichment in terrestrial waters; the hydrologic and geochemical conditions of water formation in northern Siberia will change significantly in response to permafrost thawing. Zonal features in the development of anthropogenically-induced processes in terrestrial surface waters (acidification, eutrophication, and metal enrichment) were determined. It was demonstrated that, in addition to naturally acidified lakes with high contents of humic acids, acid lakes of anthropogenic origin occur over the whole humid region discussed here, and acidification processes were characterized for each subregion. The trophic status of lakes and limitation of their bioproductivity with respect to nutrients were estimated. The concentrations and distribution of trace elements were analyzed in terrestrial waters from various climatic zones of European Russia and Western Siberia, and the first estimates were obtained for the mean concentrations and coefficients of migration of a wide range of elements in terrestrial freshwaters. We distinguished a group of metal (Mo, As, U, Bi, Sb, Cd, Ag, Se, Re, Pb, Cd, W, etc.) the enrichment of which in natural waters results from their global dispersion in the environment. Experimental results and natural observations are presented on the processes of metal ion complexation with humus substances, and sequences of their increasing activity in competing for organic ligands were derived. Data are presented on the speciation of metals depending on natural water chemistry in the tundra, taiga, and steppe zones. The pioneering investigations on the geochemistry of natural waters allowed us to substantiate new regional norms for water quality.     

Comparison of the Complexation of Cu and Cd by Humic or Fulvic Acids and by Ligands Observed in Lake Waters

The complexation of Cu and Cd by ligands observed in filtered unfractionated lakewaters is compared to the complexation by humic and fulvic acids. Complexation parameters (conditional stability constants and ligand concentrations) of Suwannee River fulvic acids (FA), purified peat humic acids (HA) and of ligands in lakewater samples have been determined using the same methods (ligand-exchange and CSV (cathodic stripping voltammetry) or ASV (anodic stripping voltammetry)), and the same titration ranges of Cu, Cd and organic carbon concentrations. The performance of the used techniques is first evaluated in FA and HA suspensions, and gives comparable results with the literature values for the same materials, according to published models (5-site model, NICA model) and parameters. Model calculations using the WHAM model for FA and HA (Tipping, 1994) are also presented. The comparison of titrations of FA and HA with Cu and Cd with those of lakewater samples indicates that stronger ligands than FA and HA are present at low concentrations in the lakewaters. Specific strong ligands occur in particular in eutrophic lake waters, whereas in a lake with higher metal concentrations and low biological productivity the ligands more closely match the fulvic acid characteristics.     

Effects of long-term irrigation with treated wastewater. Part II: Role of organic carbon on Cu,Pb and Cr behaviour

The long-term impact of irrigation on a Mediterranean sandy soil irrigated with treated wastewater (TWW) since 1980 was evaluated. The main soil properties (CEC, pH, size distribution, exchangeable cations and chloride, hydraulic conductivity) as well as the organic matter and Cu, Cr and Pb speciation in an irrigated soil and a non-irrigated control soil at various soil depths were monitored and compared during a 2 year experiment. In this second part, we focused on Cu, Cr and Pb behaviour in relation with soil organic carbon (SOC). Soil samples were collected every 3 months during 2 years at the depths 0–20, 20–40 and 40–60 cm and were analysed for exchangeable and total metals, organic carbon content, metal sequential extraction and humic substances – Humic Acids (HA), Fulvic Acids (FA) and Non-Humified Fraction (NHF). Long-term irrigation with a domestic treated wastewater (TWW) may be considered safe with regard to trace metal accumulation in soil. Irrigation lowered the HA and NHF fractions of SOC and made the FA fraction more mobile. Cu bound preferentially to the SOC fraction, Cr was found mainly in the reducible fraction and Pb was bound to all fractions indiscriminately. Cu exhibited a high affinity for the HA fraction, while Pb and Cr had a high affinity for the FA fraction, which indicates a greater mobility of the organically-bound Pb and Cr than of the organically-bound Cu. Evaluation of the potential metal mobility has to take into account not only the usual speciation between labile, reducible and oxidisable fractions, but also the nature of the SOC responsible for the oxidisable fraction.     

Trace metal dynamics in a seasonally anoxic lake

Selected results are presented from a detailed 12-month study of trace metals in a seasonally anoxic lake. Dissolved concentrations of Fe, Mn, organic carbon, Cd, Cu, Pb, Zn, and pH were determined in the water column and the interstitial waters on 39 occasions. Trace metal concentrations remained low throughout the year in both water column and pore waters. There was evidence for some remobilization at the sediment-water interface but sediments deeper than 3 cm acted as a sink throughout the year. Variations in the water concentrations were largely associated with increased loading during periods of heavy rainfall. During the summer, concentrations of Cu and Zn in the waters overlying the sediments were enhanced by release from decomposing algal material. Similarly, enhanced concentrations of Cd, Cu, Pb, and Zn were observed during periods of much reduced mixing during ice-cover. Although there were large seasonal variations in the concentrations of dissolved and particulate Fe and Mn, there were no comparable changes in the concentrations of trace metals.     

Organo-colloidal control on major- and trace-element partitioning in shallow groundwaters: Confronting ultrafiltration and modelling

Ultrafiltration experiments using new small ultracentifugal filter devices were performed at different pore size cut-offs to allow the study of organo-colloidal control on metal partitioning in water samples. Two shallow, circumneutral pH waters from the Mercy site wetland (western France) were sampled: one dissolved organic carbon (DOC)- and Fe-rich and a second DOC-rich and Fe-poor. Major- and trace-element cations and DOC concentrations were analysed and data treated using an ascendant hierarchical classification method. This reveals the presence of three groups: (i) a “truly” dissolved group (Na, K, Rb, Ca, Mg, Ba, Sr, Si and Ni); (ii) an inorganic colloidal group carrying Fe, Al and Th; and (iii) an organic colloidal group enriched in Cr, Mn, Co, Cu and U. However, REE and V have an ambivalent behaviour, being alternatively in the organic pool and in the inorganic pool depending on sample. Moreover, organic speciation calculation using Model VI were performed on both samples for elements for which binding constants were available (Ca, Mg, Ni, Fe, Al, Th, Cr, Cu, Dy, Eu). Calculation shows relatively the same partitioning of these elements as ultrafiltration does. However, some limitations appear such as (i) a direct use of ultrafiltration results which tends to overestimate the fraction of elements bound to humic material in the inorganic pool as regards to model calculations as well as, (ii) a direct use of speciation calculation results which tends to overestimate the fraction of elements bound to humic material in the organic pool with regard to ultrafiltration results. Beside these limitations, one can consider that both techniques, ultrafiltration and speciation calculation, give complementary information, especially for more complex samples where inorganic and organic colloids compete.     

New operational method of testing colloid complexation with metals in natural waters

A dialysis procedure was used to assess the distribution coefficients of ∼50 major and trace elements (TEs) between colloidal (1 kDa–0.22 μm) and truly dissolved (<1 kDa) phases in Fe- and organic-rich boreal surface waters. These measurements allowed quantification of both TE partitioning coefficients and the proportion of colloidal forms as a function of solution pH (from 3 to 8). Two groups of elements can be distinguished according to their behaviour during dialysis: (i) elements which are strongly associated with colloids and exhibit significant increases of relative proportion of colloidal forms with pH increase (Al, Ba, Cd, Co, Cr, Cu, Fe, Ga, Hf, Mn, Ni, Pb, rare earth elements (REEs), Sr, Th, U, Y, Zn, Zr and dissolved organic C) and (ii) elements that are weakly associated with colloids and whose distribution coefficients between colloidal and truly dissolved phases are not significantly affected by solution pH (As, B, Ca, Cs, Ge, K, Li, Mg, Mo, Na, Nb, Rb, Sb, Si, Sn, Ti, V). Element speciation was assessed using the Visual MINTEQ computer code with an implemented NICA-Donnan humic ion binding model and database. The model reproduces quantitatively the pH-dependence of colloidal form proportion for alkaline-earth (Ba, Ca, Mg, Sr) and most divalent metals (Co, Cd, Mn, Ni, Pb, Zn) implying that the complexation of these metals with low molecular weight organic matter (<1 kDa fraction) is negligible. In contrast, model prediction of colloidal proportion (fraction of 1 kDa–0.22 μm) of Cu²⁺ and all trivalent and tetravalent metals is much higher than that measured in the experiment. This difference may be explained by (i) the presence of strong metal-binding organic ligands in the <1 kDa fraction whose stability constants are several orders of magnitude higher than those of colloidal humic and fulvic acids and/or (ii) coprecipitation of TE with Fe(Al) oxy(hydr)oxides in the colloidal fraction, whose dissolution and aggregation controls the pH-dependent pattern of TE partitioning. Quantitative modeling of metal – organic ligand complexation and empirical distribution coefficients corroborate the existence of two colloidal pools, formerly reported in boreal surface waters: “classic” fulvic or humic acids binding divalent transition metals and alkaline-earth elements and large-size organo-ferric colloids transporting insoluble trivalent and tetravalent elements.