Trace metals (Cd,Pb, Cu,Zn and Ni) in sediment of the submarine pit Dragon ear (Soline Bay,Rogoznica, Croatia)

Vertical profiles of trace metal (Cd, Pb, Zn, Cu, Ni) concentrations, organic matter content, carbonate content and granulometric composition were determined in two sediment cores from the submarine pit Dragon Ear (Middle Adriatic). Concentrations of the analyzed metals (Cd: 0.06–0.12 mg kg⁻¹, Pb: 28.5–67.3 mg kg⁻¹, Zn: 17.0-65.4 mg kg⁻¹, Cu: 21.1–51.9 mg kg⁻¹, Ni: 27.8–40.2 mg kg⁻¹) were in usual range for Adriatic carbonate marine sediments. Nevertheless, concentrations of Cu, Zn, and especially Pb in the upper layer of sediments (top 12 cm) were higher than in bottom layer, while Cd and Ni concentration profiles were uniform. Regression analysis and principal component analysis were used to interpret distribution of trace metals, organic matter and carbonate content in sediment cores. Results of both analysis showed that concentrations of all trace metals in the core below the entrance to the pit were significantly positively correlated with organic matter and negatively correlated with carbonate, while in the core more distant from the entrance only Pb showed significant positive correlation with organic matter. Obtained results indicated that, except for lead which was enriched in surface sediment, in the time of sampling (before the building of the nautical marina) investigated area belonged to unpolluted areas.     

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.     

Geochemical fractionation of heavy metals in Chilka Lake (east coast of India)—a tropical coastal lagoon

Chilka lake, the largest coastal lagoon of Asia is one of the most dynamic ecosystems along the Indian coast. Historically the lagoon has undergone a considerable reduction in surface area due, in part, to input from natural processes but mostly due to human activities. The purpose of this investigation is to document the heavy metals' affinity for specific geochemical phases in the recently deposited sediments in the lagoon. Thirty-three samples were collected and analyzed for different geochemical phases of Fe, Mn, Cu, Cr, Ni, Pb, and Zn utilizing a sequential extraction scheme. In the nonlithogenous fraction, the exchangeable fraction was not geochemically significant, having <2% of the total metal concentration for all the elements. However, the carbonate fraction contained the following percentages of the total concentration: <1% Fe, 13% Mn, 6% Cu, 4% Cr, 8% Ni, 13% Pb, and 12% Zn, suggesting the detrital origin of the sediments. Reducible and organic matter-bound fractions were the significant phases in the nonlithogenous fraction, containing 9% Fe, 16% Mn, 15% Cu, 16% Cr, 16% Ni, 14% Pb, and 14% Zn in the former and 4% Fe, 3% Mn, 17% Cu, 3% Cr, 14% Ni, 15% Pb, and 14% Zn in the latter. The phenomenon has been attributed to the scavenging affinity of Fe-Mn oxides and affinity for sorption into organic matter of the lagoon sediments. The lithogenous, residual fraction generally considered as a guide for natural background values was determined to contain 87% Fe, 67% Mn, 61% Cu, 77% Cr, 61.3% Ni, 56% Pb, and 60% Zn of the total concentrations.     

Geochemistry of two sediment cores from the west coast of India

Copper, Pb, Zn, Ni, Co, Mn, AI, Ca, magnetic susceptibility and loss on ignition of sediments from two cores near Mangalore along the western continental shelf of India have been studied. The sediments have high Al and organic matter contents due to the high sedimentation rate and their proximity to river mouths. Down-core variations of elements indicate a decrease of lithogenous component during probably the past few centuries. While abundance of calcareous shells in some zones has lead to the dilution of most of the metals, it appears that Pb and Mn are associated with this phase. Copper, Zn and Fe are associated with organic matter and detrital particles, whereas Ni and Co are predominantly associated with the insoluble fraction. Oxides/hydroxides of Fe and Mn are absent because of the reducing conditions and the high terrigenous influx. Geochemically, Mn and Fe are present in different phases of sediments (in the insoluble fraction and organic matter respectively). The Fe content of one of the cores is positively correlated with magnetic susceptibility.     

The concentration of Cu(II), Pb(II) and Zn(II) from aqueous solutions by particulate algal matter

Experimental studies of the reactions of Cu(II), Pb(II), and Zn(II) in aqueous solutions with organic matter derived from fresh samples of the green filamentous algae Ulothrix spp. and the green unicellular algae Chlamydomonas spp. and Chlorella vulgaris show that, under suitable conditions, a significant proportion of the metals is removed from solution by sorption onto the particulate organic matter of the algal suspension.The metal sorption is strongly suppressed by H⁺ but is only marginally influenced by the proportion of whole cells in the suspension and by complexing of metals in solution by the soluble organic matter. The presence of relatively small amounts of the cations Na⁺ and Mg²⁺ in solution reduces the sorption of Zn(II) to near zero, but Pb(II) and Cu(II) sorption occurs to an appreciable extent even in strong brines. This may be a means for the selective precipitation of Pb(II) from brines rich in Pb(II) and Zn(II).Metal “saturation” values indicate that particulate algal matter of the type used in these experiments could sorb sufficient quantities of metal to form an ore deposit if a weight of organic matter of similar order of magnitude to that of the inorganic sediments in the deposits was available. However, the metal sorption is an equilibrium reaction, and the experimentally determined “enrichment factors” suggest that the “saturation” values could be approached only in solutions whose metal contents were initially at least two orders of magnitude above those of normal seawater.     

Geochemical dispersion of heavy metals via organic complexing: A laboratory study of copper,lead, zinc,and nickel behaviour at a simulated sediment-water boundary

Data are presented in this study from laboratory model experiments describing the behaviour of Cu, Pb, Zn and Ni at a simulated sediment-water boundary. The interactions involved are sorption by kaolin and by bentonite, organic complexing in solution by fulvic acid and by humic acid, carbonate reactions, hydrolysis, and desorption of the cations from a clay-bound phase and from their metal hydroxides by the organic acids. The organic acids increase the solubility of Cu, Zn and Ni in the presence of clay. The Pb solubility is variable and can even decrease, particularly at acidic pH, with organic complexing likely due to colloidal coagulation. Both Zn and Ni are influenced by hydrolysis at basic pH. When carbonate was added to the metal-organic acid-clay mixtures, a further decrease in solubility was observed for Ni and, to a lesser extent, for Zn. The organic acids prove capable of remobilizing Cu, Pb, Zn and Ni from the solid phases examined. However, there is a general kinetic hindrance to the desorption particularly at basic pH. Copper desorption appears to be the most kinetically hindered. Conclusions pertinent to the geochemical dispersion of these metals are drawn.     

Partitioning of heavy metals in surface Black Sea sediments

Bulk heavy metal (Fe, Mn, Co, Cr, Ni, Cu, Zn and Pb) distributions and their chemical partitioning, together with TOC and carbonate data, were studied in oxic to anoxic surface sediments (0–2 cm) obtained at 18 stations throughout the Black Sea. TOC and carbonate contents, and available hydrographic data, indicate biogenic organic matter produced in shallower waters is transported and buried in the deeper waters of the Black Sea. Bulk metal concentrations measured in the sediments can be related to their geochemical cycles and the geology of the surrounding Black Sea region. Somewhat high Cr and Ni contents in the sediments are interpreted to reflect, in part, the weathering of basic-ultrabasic rocks on the Turkish mainland. Maximum carbonate-free levels of Mn (4347 ppm), Ni (355 ppm) and Co (64 ppm) obtained for sediment from the shallow-water station (102 m) probably result from redox cycling at the socalled ‘Mn pump zone’ where scavenging-precipitation processes of Mn prevail. Chemical partitioning of the heavy metals revealed that Cu, Cr and Fe seem to be significantly bound to the detrital phases whereas carbonate phases tend to hold considerable amounts of Mn and Pb. The sequential extraction procedures used in this study also show that the metals Fe, Co, Ni, Cu, Zn and Pb associated with the ‘oxidizable phases’ are in far greater concentrations than the occurrences of these metals with detrital and carbonate phases. These results are in good agreement with the recent studies on suspended matter and thermodynamic calculations which have revealed that organic compounds and sulfides are the major metal carriers in the anoxic Black Sea basin, whereas Fe-Mn oxyhydroxides can also be important phases of other metals, especially at oxic sites. This study shows that, if used with a suitable combination of the various sequential extraction techniques, metal partitioning can provide important information on the varying geological sources and modes of occurrence and distribution of heavy metals in sediments, as well as, on the physical and chemical conditions prevailing in an anoxic marine environment.     

Thermodynamic modeling of heavy metal forms in bottom sediments: By the example of the Ivankovsky Reservoir

The technique of thermodynamic modeling for interactions in system “pore water-solid phase of bottom sediments” is suggested (including dissolved and sorbed forms of heavy metals). The main sorbent phases (clay minerals, iron and manganese hydroxides, and organic matter) are presented as multi-component ideal solid solutions. The capacities of sorbing phases are calculated according to the results of selective extraction by the Tessier scheme supplemented with determination macro-cations. The selectivity constants and free energy of metal bonding (Fe, Mn, Zn, Cu, Ni, Pb, Co, and Cd) with sorbing phases are calculated for bottom sediments of various compositions within the Ivankovsky Reservoir and the estimation of their natural variations is given.     

Spatial trends in the geochemical composition of sediments in the Panuco River discharge area, Gulf of Mexico.

Major and trace elements, organic matter, carbonates, loss of ignition, grain size, gravel, sand, silt, clay, and qualitative mineralogical composition were determined on surficial marine sediments sampled during the stormy (February), dry (May), and rainy (September) seasons in the coastal area adjacent to Panuco River discharges into the Gulf of Mexico. The sediments supplied by the river move in a north-east direction, and are deposited in the north-east extreme of the studied area. Terrigenous sediments show a strong association of Al₂O₃ with Fe₂O₃, Na₂O, K₂O, P₂O₅, Rb, Cu, Zn, organic matter, clay, and grain size (Mz). Mineralogical analysis shows that they are formed by quartz, kaolinite, montmorillonite, illite-montmorillonite and biotite. The highest metal concentration of Cu (25 mg/kg), Zn (155 mg/kg), Pb (50 mg/kg) and organic matter (1.26%) was observed in the sampling points located very close to the river mouth. A statistical analysis was done with the information contained in the variables. Five significant factors explain 77% of the total variance: factor 1 is due to sediments from a terrigenous source, factor 2 corresponds to sediments from a biogenous source, factor 3 is associated to sediments with heavy minerals, factor 4 is due to Co concentration, and factor 5 is due to Ni concentration. The sediments supplied from the river had a short-term local impact on the sediment distribution, as observed by the carbonate and heavy mineral concentration of the sediments.     

Enriched stable carbon isotopes in the pore waters of carbonate sediments dominated by seagrasses: Evidence for coupled carbonate dissolution and reprecipitation

Studies of the δ¹³C of pore water dissolved inorganic carbon (δ¹³C-DIC) were carried out in shallow water carbonate sediments of the Great Bahamas Bank (GBB) to further examine sediment-seagrass relationships and to more quantitatively describe the couplings between organic matter remineralization and sediment carbonate diagenesis. At all sites studied δ¹³C-DIC provided evidence for the dissolution of sediment carbonate mediated by metabolic CO₂ (i.e., CO₂ produced during sediment organic matter remineralization); these observations are also consistent with pore water profiles of alkalinity, total DIC and Ca²⁺ at these sites. In bare oolitic sands, isotope mass balance further indicates that the sediment organic matter undergoing remineralization is a mixture of water column detritus and seagrass material; in sediments with intermediate seagrass densities, seagrass derived material appears to be the predominant source of organic matter undergoing remineralization. However, in sediments with high seagrass densities, the pore water δ¹³C-DIC data cannot be simply explained by dissolution of sediment carbonate mediated by metabolic CO₂, regardless of the organic matter type. Rather, these results suggest that dissolution of metastable carbonate phases occurs in conjunction with reprecipitation of more stable carbonate phases. Simple closed system calculations support this suggestion, and are broadly consistent with results from more eutrophic Florida Bay sediments, where evidence of this type of carbonate dissolution/reprecipitation has also been observed. In conjunction with our previous work in the Bahamas, these observations provide further evidence for the important role that seagrasses play in mediating early diagenetic processes in tropical shallow water carbonate sediments. At the same time, when these results are compared with results from other terrigenous coastal sediments, as well as supralysoclinal carbonate-rich deep-sea sediments, they suggest that carbonate dissolution/reprecipitation may be more important than previously thought, in general, in the early diagenesis of marine sediments.     

Distribution of heavy metals in the clastic fine-grained sediments of Gavkhuni playa lake (Southeast of Isfahan,Iran)

The sedimentary basin of Gavkhuni playa lake includes two sedimentary environments of delta and playa lake. These environments consist of mud, sand and salt flats. There are potentials for concentration of heavy metals in the fine-grained sediments (silt and clay) of the playa due to existence of Pb/Zn ore deposits, industrial and agricultural regions in the water catchment of Zayandehrud River terminating to this area. In order to study the concentration of heavy metals and the controlling factors on their distribution in the fine-grained sediments, 13 samples were taken from the muddy facies and concentration of the heavy metals were determined. The results showed that the heavy metal concentrations range in the sediments (in ppm) are Mn (395.5–1,040), Sr (100.4–725.76), Pb (14.66–91.06), Zn (23.59–80.9), Ni (37–73.66), Cu (13.83–29.83), Co (5.73–13.78), Ag (3.03–4.76) and Cd (2.3–5.5) in their order of abundances. The concentration of Ag is noticeable in the sediments relative to the average concentration of this element in mud sediments. The amounts of Pb and Zn are relatively high in all the samples in comparison with the other elements. The concentration of Ni is relatively high in the oxidized samples. The distribution of Pb is directly related to organic matter content of the sediments. The concentrations of Zn, Sr, Cu, Co and Cd in the samples of the playa are lower than those in the delta. The amount of illite is another factor influencing Zn and Pb concentrations. Sr is more concentrated in the sediments with the high content of calcium carbonate. The distribution pattern of Cu, Co, Pb and Mn resembles to that of the clay content of the sediments. The clay content shows positive correlations with Co, Cu and Mn concentrations and negative correlation with Ag. The Sr and Ag concentrations are positively correlated with the amount of CaCO₃. The amounts of Co, Cu, Ni and Mn show negative correlations with the calcium carbonate content. Pb and Co are noticeably correlated with Mn.     

黄河包头段不同粒级沉积物中重金属形态分布特征

以黄河包头段为研究对象,探讨了该河段不同粒级沉积物中重金属的形态分布特征,并估算了各粒级沉积物对各形态重金属的贡献率。结果表明,铁锰氧化物结合态是黄河干流各粒级沉积物中Cu、Pb和Zn非稳定态的主导形态;总体上,黄河干支流沉积物中3种重金属各形态含量均随粒级增大而减小,表现明显的粒度效应;重金属形态分布的粒度效应是沉积...     

Chemical forms of some heavy metals in Huanghe River sediments (China) and comparison with data from Rhine River sediments (West Germany)

The chemical forms of Fe, Mn, Zn, Cu, Cr, Pb and Cd in the Huanghe River sediments have been studied by sequential extraction techniques and the comparison with data from the Rhine River sediments has been made. In the Huanghe River sediments the average contents of metals, without exception, are below their respective contents in average shales and very close to their levels in Ca-poor granites. The major portion of metals is combined with the detrital and moderately reducible phases. Both in the Huanghe River and in the Rhine River sediments the distribution ratios of metals between the moderately reducible and the easily reducible phases are generally more than unity. However, the distribution ratios of Mn, Zn and Cd are obviously lower than those of Fe, Cr, Cu and Pb. As a result of contamination, the ratios of Fe, Cr, Cu and Pb show an apparent increase, but no remarkable ratio variation is observed for Mn, Zn and Cd. Metals in the Huanghe River sediments, especially Cu and Zn, show a tendency to be associated with the organic phase. The effect of carbonate on metal association preference seems to be less important than that in the Rhine River although there is higher content of carbonate in the Huanghe River sediments. Cd has a greater percentage of the exchangeable phase, which is similar to the result from the Rhine River sediments.     

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.     

Halogens and noble gases in sedimentary formation waters and Zn–Pb deposits: A case study from the Lennard Shelf,Australia

Halogen ratios (Br/Cl and I/Cl) and concentrations provide important information about how sedimentary formation waters acquire their salinity, but the possible influence of organic Br derived from sedimentary wall-rocks is rarely quantified. Here, it is demonstrated that Br/Cl versus I/Cl mixing diagrams can be used to deconvolve organic Br contributions; that organic matter has a limited range of Br/I ratios; and that organic Br is a more significant component in Zn–Pb deposit ore fluids than previously recognised. The significance of these findings is illustrated for the Lennard Shelf Zn–Pb deposits of Western Australia.Fluid inclusions related to Lennard Shelf Zn–Pb mineralisation have variable salinity and hydrocarbon contents. The halogen data from these fluid inclusions require mixing of three fluid end-members: (1) an evaporated seawater bittern brine (30 wt.% NaCl equiv.) with greater than seawater Br/Cl ratio; (2) a lower salinity pore fluid (?5 wt.% NaCl equiv.) with moderately elevated Br/Cl and I/Cl; and (3) fluids with Br/Cl ratios of ～5 times seawater and extremely elevated I/Cl ratios of ～11,500 times seawater. The first two fluids have ⁴⁰Ar/³⁶Ar of 300–400 and greater than air saturated water ³⁶Ar concentrations that are typical of fluid inclusions related to Zn–Pb mineralisation. The third ‘organic-rich’ fluid has the highest ⁴⁰Ar/³⁶Ar ratio of up to 1500 and a depleted ³⁶Ar concentration.Mineralisation is interpreted to have resulted from mixing of Zn-rich evaporitic brines and H₂S present in hydrocarbons. It is suggested that aqueous fluids acquired organic Br and I from hydrocarbons, and that hydrocarbons exsolving from the aqueous fluid removed noble gases from solution. Interaction of variably saline brines and hydrocarbons could account for the variable Br/Cl and I/Cl composition, and ³⁶Ar concentrations, recorded by Lennard Shelf fluid inclusions. The distinct ⁴⁰Ar/³⁶Ar signature of the fluid with the highest I/Cl ratio suggests the hydrocarbons and brines were sourced independently from different parts of the sedimentary basin. These data indicate the complementary nature of halogen and noble gas analysis and provide new constraints on important mixing processes during sediment-hosted Zn–Pb mineralisation.     

Geochemical features of heavy metals in core sediments of northwestern Taihu Lake, China

Sequential core sediments from northwestern Taihu Lake in China were analyzed for grain size, organic carbon and heavy metal content. The sediments are composed of organic-poor clayey-fine silts. The chemical speciations of Cu, Fe, Mn, Ni, Pb, and Zn were also analyzed using the BCR sequential extraction procedure. Cu, Fe, Ni, and Zn are mainly associated with the residue fraction; Mn is concentrated mainly in exchangeable/carbonate fraction and residue fraction; and Pb mainly in Fe/Mn oxide fraction and organic/sulfide fraction. The exchangeable/carbonate fractions of Cu, Fe, Ni, Zn and Pb are lower. The fractions of Ni, Pb and Zn bound to the Fe/Mn oxide have significant correlations with reducible Mn; the organic/sulfide fractions of Cu, Mn, Ni, Pb, and Zn have significant correlations with TOC. The extractable fractions of Cu, Mn, Ni, Pb, and Zn are high at the top 4 cm of the core sediments as compared to those in the deeper layers, showing the anthropogenic input of heavy metals is due to rapid industrial development. The heavy metal pollution history of the sediments has been recorded since the late 1970s, determined by the result of ^137Cs dating.     

Statistical modeling the effect of sediment physicochemical properties on the concentration of heavy metal (case study: Musa Creek,SW Iran)

Heavy metal accumulation in sediments is important even at low levels due to their irresolvable character and harmful effects. Therefore, contamination of creeks, especially their sediments, is highly important for scientific communities. This study investigates the relationship between heavy metal accumulation and some physicochemical parameters of sediments (pH, EC, calcium carbonate, texture, specific gravity, density, porosity and percentage of organic matter) in a stretch of Musa Creek beaches. The results showed that the studied sediments are extremely salty and have slight variations in terms of pH. Although there are mostly clay-sized sediments in the studied area, their mineralogical composition contains calcite with smaller amounts of dolomite, aragonite and halite minerals. The correlation between each of the parameters and heavy metal concentration was modeled using OLS regression. Cr, Ni, Zn and Pb concentrations are positively correlated with each other and inversely correlated with Cd. The accumulation of heavy metals is directly related to parameters such as EC, organic matter, clay and silt, specific gravity and porosity; it is negatively related to calcium carbonate, sand and density parameters. Owing to slight variations, the pH parameter lacks any significant correlation with heavy metal concentrations.     

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.     

Size and elemental distributions of nano- to micro-particulates in the geochemically-stratified Great Salt Lake

The characterization of trace elements in terms of their apportionment among dissolved, macromolecular, nano- and micro-particulate phases in the water column of the Great Salt Lake carries implications for the potential entry of toxins into the food web of the lake. Samples from the anoxic deep and oxic shallow brine layers of the lake were fractionated using asymmetric flow field-flow fractionation (AF4). The associated trace elements were measured via online collision cell inductively-coupled plasma mass spectrometry (CC-ICP-MS). Results showed that of the total (dissolved + particulate) trace element mass, the percent associated with particulates varied from negligible (e.g. Sb), to greater than 50% (e.g. Al, Fe, Pb). Elements such as Cu, Zn, Mn, Co, Au, Hg, and U were associated with nanoparticles, as well as being present as dissolved species. Particulate-associated trace elements were predominantly associated with particulates larger than 450 nm in size. Among the smaller nanoparticulates (<450 nm), some trace elements (Ni, Zn, Au and Pb) showed higher percent mass (associated with nanoparticles) in the 0.9–7.5 nm size range relative to the 10–250 nm size range. The apparent nanoparticle size distributions were similar between the two brine layers; whereas, important differences in elemental associations to nanoparticles were discerned between the two layers. Elements such as Zn, Cu, Pb and Mo showed increasing signal intensities from oxic shallow to anoxic deep brine, suggesting the formation of sulfide nanoparticles, although this may also reflect association with dissolved organic matter. Aluminum and Fe showed greatly increased concentration with depth and equivalent size distributions that differed from those of Zn, Cu, Pb and Mo. Other elements (e.g. Mn, Ni, and Co) showed no significant change in signal intensity with depth. Arsenic was associated with <2 nm nanoparticles, and showed no increase in concentration with depth, possibly indicating dissolved arsenite. Mercury was associated with <2 nm nanoparticles, and showed greatly increased concentration with depth, possibly indicating association with dissolved organic matter.     

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.