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1.
In recent years, the relevance of physico-chemical heterogeneity patterns in soils at the micron and submicron scale for the regulation of biogeochemical processes has become increasingly evident. For an organic surface soil horizon from a forested Histosol in Germany, microspatial patterns of element distribution (sulfur, phosphorus, aluminium, silicon) and S speciation were investigated by synchrotron-based X-ray spectromicroscopy. Microspatial patterns of S, P, Al and Si contents in the organic topsoil were assessed for a sample region of 50 μm × 30 μm by spatially resolving μ-XRF. Sulfur speciation at four microsites was investigated by focused X-ray absorption near edge structure (μ-XANES) spectroscopy at the S K-edge. The results show a heterogeneous distribution of the investigated elements on the (sub)micron scale, allowing the identification of diatoms, aluminosilicate mineral particles and sulfide minerals in the organic soil matrix. Evaluation of the S K-edge μ-XANES spectra acquired at four different microsites by linear combination fitting revealed a substantial microspatial heterogeneity of S speciation, characterized by the presence of distinct enrichment zones of inorganic sulfide and zones with dominant organic disulfide S within a few micrometers distance, and coexistence of different S species (e.g. reduced inorganic and organic S compounds) at a spatial scale below the resolution of the instrument (60 nm × 60 nm; X-ray penetration depth: 30 μm).  相似文献   

2.
Biofilm-embedded Mn oxides exert important controls on trace metal cycling in aquatic and soil environments. The speciation and mobility of Zn in particular has been linked to Mn oxides found in streams, wetlands, soils, and aquifers. We investigated the mechanisms of Zn sorption to a biogenic Mn oxide within a biofilm produced by model soil and freshwater MnII-oxidizing bacteria Pseudomonas putida. The biogenic Mn oxide is a c-disordered birnessite with hexagonal layer symmetry. Zinc adsorption isotherm and Zn and Mn K-edge extended X-ray absorption fine structure (EXAFS) spectroscopy experiments were conducted at pH 6.9 to characterize Zn sorption to this biogenic Mn oxide, and to determine whether the bioorganic components of the biofilm affect metal sorption properties. The EXAFS data were analyzed by spectral fitting, principal component analysis, and linear least-squares fitting with reference spectra. Zinc speciation was found to change as Zn loading to the biosorbent [bacterial cells, extracellular polymeric substances (EPS), and biogenic Mn oxide] increased. At low Zn loading (0.13 ± 0.04 mol Zn kg−1 biosorbent), Zn was sorbed to crystallographically well-defined sites on the biogenic oxide layers in tetrahedral coordination to structural O atoms. The fit to the EXAFS spectrum was consistent with Zn sorption above and below the MnIV vacancy sites of the oxide layers. As Zn loading increased to 0.72 ± 0.04 mol Zn kg−1 biosorbent, Zn was also detected in octahedral coordination to these sites. Overall, our results indicate that the biofilm did not intervene in Zn sorption by the Mn-oxide because sorption to the organic material was observed only after all Mn vacancy sites were capped by Zn. The organic functional groups present in the biofilm contributed significantly to Zn removal from solution when Zn concentrations exceeded the sorption capacity of the biooxide. At the highest Zn loading studied, 1.50 ± 0.36 mol Zn kg−1 biosorbent, the proportion of total Zn sorption attributed to bioorganic material was 38 mol%. The maximum Zn loading to the biogenic oxide that we observed was 4.1 mol Zn kg−1 biogenic Mn oxide, corresponding to 0.37 ± 0.02 mol Zn mol−1 Mn. This loading is in excellent agreement with previous estimates of the content of cation vacancies in the biogenic oxide. The results of this study improve our knowledge of Zn speciation in natural systems and are consistent with those of Zn speciation in mineral soil fractions and ferromanganese nodules where the Mn oxides present are possibly biogenic.  相似文献   

3.
Industrialization, urbanization, and agricultural practices are 3 of the most important sources of metal accumulations in soils. Concentrations of Cr, Mn, Ni, Cu, Pb, Zn and Cd were determined in surface soils collected under different land uses, including urban (UR), industrial (IN-1 and IN-2), agricultural (AG), abandoned unused (AB), and natural (NA) sites to examine the influence of anthropogenic activities on metals in soils formed in a typical Mediterranean environment. The highest concentrations of Cr, Cd, and Pb observed in the NW industrial area (IN-2) were 63.7, 3.34 and 2330 mg metal kg−1 soil, for each metal, respectively. The SW industrial area (IN-1) contained the highest Zn content at 135 mg kg−1. However, soils with the highest concentrations of Ni and Cu were located in AG sites at 30.9 and 64.9 mg kg−1 soil, respectively. Sampling locations with the highest concentrations of Mn were identified in AB sites. Using the concentrations of metals at the NA sites as the baseline levels, soils collected from all other land uses in the study area exhibited significantly higher total contents of Zn, Mn, Cr and Ni. Metal enrichment was attributed to fertilizer and pesticide applications, industrial activities, and metal deposition from a high volume of vehicular traffic (for Pb and Cd). High concentrations of Mn in some samples were attributed to parent materials. The study demonstrated that anthropogenic activities associated with various land uses contribute to metal accumulation in soils and indicated a need to closely monitor land management practices to reduce human and ecological risks from environmental pollution.  相似文献   

4.
Temporal variations in the concentration and N isotopic ratios of inorganic N (NH4– and NO3–N) as affected by the soil temperature regime together with the input of bird excreta were analyzed in a sedentary soil under a dense colony (1.6 nests/m2) of breeding Black-tailed Gulls (Laruscrassirostris: a ground-nesting seabird). Surface soil samples were taken monthly from mid-March to late July 2005 from Kabushima Island, Hachinohe, northeastern Japan. The spatial concentration of inorganic N in the soils varied considerably on all sampling dates. There may be a statistically significant trend, showing increased NH4–N content from settlement up to early June when the input of fecal N attains its maximum, and then decreases towards the end of breeding activity (early August). Abundant NO3–N was observed in all soils, particularly in the later stage of breeding (up to 3800 mg-N/kg dry soil), refuting earlier claims that nitrification is unimportant in the soils. δ15N values of NH4 in the soils showed unusually high values up to +51‰, reflecting N isotope fractionation due to volatilization of NH3 during the mineralization. Mean δ15N values of the monthly collected totals of NH4 and NO3 were not significantly different at the 5% level based on ANOVA and significant differences were observed only among the three means of NO3–N collected in mid-March (settlement of colony: δ15N = −0.2 ± 3.5‰) and late July (later stages of breeding: δ15N = +22.1 ± 7.0‰, +23.3 ± 7.8‰) at the 1% and 5% levels by t-test, respectively. Such an observation of significantly increased δ15N values for NO3–N in soils from the fledgling stage indicates the integration of denitrification coupled with nitrification under a limited supply of fecal N.  相似文献   

5.
The influence of soil organisms on metal mobility and bioavailability in soils is not currently fully understood. We conducted experiments to determine whether calcium carbonate granules secreted by the earthworm Lumbricus terrestris could incorporate and immobilise lead in lead- and calcium-amended artificial soils. Soil lead concentrations were up to 2000 mg kg−1 and lead:calcium ratios by mass were 0.5-8. Average granule production rates of 0.39 ± 0.04 mgcalcite earthworm−1 day−1 did not vary with soil lead concentration. The lead:calcium ratio in granules increased significantly with that of the soil (r2 = 0.81, p = 0.015) with lead concentrations in granules reaching 1577 mg kg−1. X-ray diffraction detected calcite and aragonite in the granules with indications that lead was incorporated into the calcite at the surface of the granules. In addition to the presence of calcite and aragonite X-ray absorption spectroscopy indicated that lead was present in the granules mainly as complexes sorbed to the surface but with traces of lead-bearing calcite and cerussite. The impact that lead-incorporation into earthworm calcite granules has on lead mobility at lead-contaminated sites will depend on the fraction of total soil lead that would be otherwise mobile.  相似文献   

6.
Effects of sheet flow rate and slope gradient on sediment load   总被引：2，自引：0，他引：2  
Sheet erosion is known as one of the most important forms of erosion, particularly in agricultural land. The purpose of this study was to investigate the effect of flow rate and slope gradient on runoff and sediment discharges in two different soils. Experiments were conducted using a tilting flume facility with the test area of 0.2?×?1.0 m. Overall, 24 experiments on two soils (clay loam and sandy clay loam textures) including six flow rates (75, 100, 125, 150, 175, and 200 ml/s) and two slope gradients (1.5 and 2 %) were performed. The selected flow rates and flume slopes were generated to simulate sheet erosion. The results showed that for both soils and slopes, unit flow discharge (q) and sediment concentration increased with increasing flow rate; however, the effect of slope gradient on flow discharge depends on soil type. In addition, sandy clay loam exhibited higher values of q and sediment concentration and consequently, it showed greater amounts of sediment load. At the start of event, sediment concentration was high but it decreased to approach a steady state. In addition, the time needed to reach a steady state condition was shorter for sandy clay loam than that for clay loam soil and in lower flow rates than higher flow rates. For each soil and slope, there was a direct relationship between sediment load and flow rate. The result implied that the effect of slope gradient on sediment load was almost greater in sandy clay loam soil than clay loam soil. Moreover, the differences between sediment loads of two soils are enlarged at slope 2 %.  相似文献   

7.
To evaluate muck sediments as a potential soil amendment, total and Mehlich III-extractable concentrations of Cd, Cu, Cr, Ni, Pb, Zn, and Co in 59 muck sediment samples from the St. Lucie Estuary were analyzed. A seven-step chemical fractionation procedure was used to assess the potential mobility of heavy metals. Except for Cd, the average total concentrations of the metals are lower than the reported average concentrations of these elements in municipal composts in the U.S.A. The concentrations were also below critical levels for the safe use of wastes and byproducts in agriculture, as established by the United States Environmental Protection Agency. The Cd, Cu, Cr, Ni, Pb, Zn and Co in the sediments were predominantly associated with silicate minerals in the residual form. Most metals in the muck sediments occur predominantly in weakly mobile or nonbioavailable forms. Use of mucks in neutral pH upland soils should not pose any significant hazards or risk to the environment. However, Cd, Cu, Cr, Ni, Pb, Zn, and Co, especially Zn, Cu, and Pb, could be more readily released from the muck sediments under acidic soil conditions.  相似文献   

8.
In the initial period of mining activities in the Idrija basin (the16th and the first half of the17th centuries), Hg ore processing was performed at various small-scale roasting sites in the woods surrounding Idrija, by roasting ore in earthen vessels. The recovery rate of this method was very low; about half of Hg was lost, causing soil contamination and considerable amounts of waste material that could potentially leach Hg into the surrounding environment. The main aims of present geochemical study were to determine the contents, vertical distribution and speciation of Hg in soils at the roasting site at Frbej?ene trate in order to verify the extreme pollution of ancient Hg ore roasting sites in the Idrija area and to establish their significance in the wider spatial contamination of soils and aquatic systems. Soil sampling was performed at the area of the former roasting site. The organic matter-rich surface soil layer (SOM) and underlying mineral soil were sampled at 63 sampling locations. Mercury speciation was performed using Hg thermo-desorption-AAS to distinguish cinnabar from potentially bioavailable forms. The results indicate extremely high Hg concentrations with a maximum of 37,000 mg/kg in SOM and 19,900 mg/kg in mineral soil. The established Hg median in soil was 370 mg/kg and in SOM 96.3 mg/kg. Spatial distributions of Hg in SOM and soil showed very high Hg contents in the central area and decreased rapidly with distance. The results of Hg thermo-desorption measurements indicated the presence of cinnabar (HgS) and Hg bound to organic or mineral soil matter. A significant portion (35–40%) of Hg in the investigated soil and SOM samples was comprised of non-cinnabar compounds, which are potentially bioavailable. It has been shown that soils contain high amounts of potentially transformable non-cinnabar Hg, which is available for surface leaching and runoff into the surrounding environment. Therefore, contaminated soils and roasted residues at the studied area are important for persistent Hg release into the aquatic ecosystem.  相似文献   

9.
Indigofera melanadenia and Tephrosia longipes plant species, collected from Cu–Ni mining area, were evaluated for accumulation of Cu and Ni. The total and bioavailable concentrations of Cu and Ni in the host soils were also determined. Flame Atomic Absorption Spectrometry was used for all metal determinations. The total and bioavailable concentrations of Cu in the soils were in the range 900–9000 μg/g and 200–2000 μg/g respectively. For Ni, the total and bioavailable concentrations were in the range 900–2000 μg/g and ∼ 40–100 μg/g respectively. The concentrations of Cu and Ni in the leaves of I. melanadenia were higher than in the roots with a range 80–130 μg/g in the leaves and 20–80 μg/g in the roots for Cu and a range of 150–200 μg/g in the leaves and 20–60 μg/g in the roots for Ni. Concentration of Cu in T. longipes was in the range of 37–240 μg/g and 150–200 μg/g in the leaves and roots respectively while the concentration of Ni was 80–140 μg/g in the leaves and 25–100 μg/g in the roots. Results indicate that both species have a potential for accumulating Cu and Ni. Translocation factor, a ratio of shoots to roots metal concentration, was used to evaluate the translocation properties of the plants from roots to shoots. Translocation factors of the plants were ≥ 1 suggesting efficient translocation of metals from roots to shoots.  相似文献   

10.
Over the last years a novel group of branched glycerol dialkyl glycerol tetraether (GDGT) membrane lipids has been discovered in peat bogs and soils. They consist of components with 4-6 methyl groups attached to the n-alkyl chains and 0 to 2 cyclopentyl moieties in the alkyl chain. These branched membrane lipids are produced by an as yet unknown group of anaerobic soil bacteria. In this study we analysed the branched membrane lipid content of 134 soil samples from 90 globally distributed locations to study the environmental factors controlling the relative distribution of the different branched GDGT isomers. Our results show that the relative amount of cyclopentyl moieties, expressed in the cyclisation ratio of branched tetraethers (CBT), is primarily related to the pH of the soil (R2 = 0.70) and not to temperature (R2 = 0.03). The relative amount of methyl branches, expressed in the methylation index of branched tetraethers (MBT), is positively correlated with the annual mean air temperature (MAT) (R2 = 0.62) and, to a lesser extent, negatively correlated with the pH of the soil (R2 = 0.37). If both parameters are combined, however, it appears that the variation in the MBT is largely explained by both MAT and pH (R2 = 0.82). These results suggest that the relative distribution of soil-derived GDGT membrane lipids can be used in palaeoenvironmental studies to estimate past annual MAT and soil pH.  相似文献   

11.
Vanadium adsorption by soils representing different soil types from Germany has been studied. For 30 soils ‘Freundlich’ type sorption isotherms have been deduced from laboratory vanadium(V) adsorption experiments. The native adsorbed vanadium quantity of a soil (S0) and the Freundlich parameters m and log k have been determined by non linear regression of the experimental data to the Freundlich model. Pronounced differences in vanadium adsorption of different soils exist and could be quantified. The vanadium adsorption data could be generalized by grouping the soils into four classes according to their vanadium adsorption properties. For each class (sandy soils, top soils, sub soils with pH < 5.5, and sub soils with pH > 5.5) mean Freundlich parameters m and log k have been calculated to be 0.59, 0.72, 0.52, 0.57 and 2.55, 2.89, 4.29, 3.41, respectively. These parameters can be used to estimate vanadium sorption properties of soils for which no vanadium sorption experiments are available. Aqua regia soluble vanadium contents of the studied soils (range 1.7–143 mg/kg; median 32 mg/kg) and leached vanadium concentrations from experiments without vanadium addition (range 0.08–37 µg/l; median 2.1 µg/l) are also given.  相似文献   

12.
《Applied Geochemistry》2003,18(11):1723-1731
The mobility and bioavailability of heavy metals depends on the metal retention capacity of soil and also on the geochemical phases with which metals are associated. Laboratory batch experiments were carried out to study the sorption and distribution of Cd, Ni and Pb in 3 soils differing in their physicochemical properties from India: Oxyaquic Haplustalf (SL1), Typic Haplustalf (SL2) and Typic Haplustert (SL3). The heavy metal adsorption was studied by isotherms and the distribution coefficient (KD) for each metal was obtained from the linear regressions of the concentration of metal remaining in equilibrium solution and the amount adsorbed. In general, the sorption capacity for all the metals decreased in the order: SL3>SL2>SL1. Among metals, the sorption capacity in all the soils decreased in the order: Pb>>Ni>Cd. Distribution of sorbed metals at various equilibrating concentrations was studied by sequential extraction. Results showed significant differences in the distribution of metals in these soils. At higher additions (such as 200 μM l−1) most of the metals were extracted in their more mobile fractions, exchangeable and/or inorganic in contrast to their original partitioning in soils, where they were preferentially associated with the less mobile residual fraction. Largest percentages of metals extracted in the exchangeable fraction corresponded to those soil–metal systems with smaller KD values, e.g. Cd, Ni and Pb in SL1 and Cd and Ni in SL2. In neutral and alkaline soils (SL2, pH=7.1, and SL3, pH=8.6) Pb was predominantly extracted from the inorganic fractions and this corresponded to higher KD values for Pb in these soils. The predominance of metals associated with the exchangeable fraction together with low KD values indicates higher mobility of metals retained in the acidic soil (SL1, pH=5.2) compared with the others.  相似文献   

13.
By using accelerator mass spectrometry, we measured 10Be (T1/2 = 1.5 Ma) concentrations in nine Ivory Coast (IVC) tektites, in six soil samples collected near the Bosumtwi impact crater, the likely source region, and in a depth profile taken through a 23 g moldavite. In the core of the moldavite sample we also measured an upper limit on the 36Cl (T1/2 = 0.3 My) concentration. The average 10Be concentration in IVC tektites of (22 ± 11) × 106 atom/g exceeds reasonable limits for a meteoritic component or cosmic-ray production in situ after tektite formation. The 10Be must be meteoric, which implies that IVC tektites formed from soils or sediments. Corrected to the time of formation (ToF) 1.07 Ma ago and for a small in situ component, the average 10Be concentration of (35 ± 7) × 106 atom/g (1 − σ mean) is considerably lower than those of contemporary Bosumtwi soils, ∼250 × 106 atom/g, or of Australasian tektites at their ToF, 0.8 Ma B.P. near Lake Bosumtwi today the soil column is only ∼1 m thick. If the landscape was similar 1.07 Ma ago, then the total thickness of the tektite formation zone probably did not exceed 10 m. With increasing depth below the surface of the moldavite, the 10Be concentrations decrease rapidly owing to the presence of a surface component, probably of recent origin. The main interior mass of the sample contains ∼0.8 × 106 atom 10Be/g and fewer than 0.1 × 106 atom 36Cl/g, little of which can be meteoritic. Although not definitive, consideration of several possible cosmic-ray exposure histories suggests that about half the interior 10Be has a meteoric origin, which if corrected to the time of formation yields a concentration compatible with those measured in typical contemporary soils. The observations are consistent with the formation of three of the four main tektite groups from surface soils or sediments.  相似文献   

14.
Aluminium has received great attention in the second half of the 20th century, mainly in the context of the acid rain problem mostly in forest soils. In this research the effect of land use and depth of the groundwater on Al, pH and DOC concentration in groundwater under Dutch sandy soils has been studied. Both pH and DOC concentration play a major role in the speciation of Al in solution. Furthermore, the equilibrium with mineral phases like gibbsite, amorphous Al(OH)3 and imogolite, has been considered. Agricultural and natural land use were expected to have different effects on the pH and DOC concentration, which in turn could influence the total Al concentration and the speciation of Al in groundwater at different depths (phreatic, shallow and deep). An extensive dataset (n = 2181) from the national and some provincial monitoring networks on soil and groundwater quality was used. Land use type and groundwater depth did influence the pH, and Al and DOC concentrations in groundwater samples. The Al concentration ranged from <0.4 μmol L−1 at pH > 7 to 1941 μmol L−1 at pH < 4; highest Al concentrations were found for natural-phreatic groundwater. The DOC concentration decreased and the median pH increased with depth of the groundwater. Natural-phreatic groundwater showed lower pH than the agricultural-phreatic groundwater. Highest DOC concentrations were found for the agricultural-phreatic groundwater, induced by the application of organic fertilizers. Besides inorganic complexation, the NICA-Donnan model was used to calculate Al3+ concentrations for complexation with DOC. Below pH 4.5 groundwater samples were mainly in disequilibrium with a mineral phase. This disequilibrium is considered to be the result of kinetic constraints or equilibrium with organic matter. Log K values were derived by linear regression and were close to theoretical values for Al(OH)3 minerals (e.g. gibbsite or amorphous Al(OH)3), except for natural-phreatic groundwater for which lower log K values were found. Complexation of Al with DOC is shown to be an important factor for the Al concentrations, especially at high DOC concentrations as was found for agricultural-phreatic groundwater.  相似文献   

15.
The soils of the Atacama Desert in northern Chile have long been known to contain large quantities of unusual salts, yet the processes that form these soils are not yet fully understood. We examined the morphology and geochemistry of soils on post-Miocene fans and stream terraces along a south-to-north (27° to 24° S) rainfall transect that spans the arid to hyperarid transition (21 to ∼2 mm rain y−1). Landform ages are ? 2 My based on cosmogenic radionuclide concentrations in surface boulders, and Ar isotopes in interbedded volcanic ash deposits near the driest site indicate a maximum age of 2.1 My. A chemical mass balance analysis that explicitly accounts for atmospheric additions was used to quantify net changes in mass and volume as a function of rainfall. In the arid (21 mm rain y−1) soil, total mass loss to weathering of silicate alluvium and dust (−1030 kg m−2) is offset by net addition of salts (+170 kg m−2). The most hyperarid soil has accumulated 830 kg m−2 of atmospheric salts (including 260 kg sulfate m−2 and 90 kg chloride m−2), resulting in unusually high volumetric expansion (120%) for a soil of this age. The composition of both airborne particles and atmospheric deposition in passive traps indicates that the geochemistry of the driest soil reflects accumulated atmospheric influxes coupled with limited in-soil chemical transformation and loss. Long-term rates of atmospheric solute addition were derived from the ion inventories in the driest soil, divided by the landform age, and compared to measured contemporary rates. With decreasing rainfall, the soil salt inventories increase, and the retained salts are both more soluble and present at shallower depths. All soils generally exhibit vertical variation in their chemistry, suggesting slow and stochastic downward water movement, and greater climate variability over the past 2 My than is reflected in recent (∼100 y) rainfall averages. The geochemistry of these soils shows that the transition from arid to hyperarid rainfall levels marks a fundamental geochemical threshold: in wetter soils, the rate and character of chemical weathering results in net mass loss and associated volumetric collapse after 105 to 106 years, while continuous accumulation of atmospheric solutes in hyperarid soils over similar timescales results in dramatic volumetric expansion. The specific geochemistry of hyperarid soils is a function of atmospheric sources, and is expected to vary accordingly at other hyperarid sites. This work identifies key processes in hyperarid soil formation that are likely to be independent of location, and suggests that analogous processes may occur on Mars.  相似文献   

16.
Cadmium (Cd) is a toxic trace element and due to human activities soils and waters are contaminated by Cd both on a local and global scale. It is widely accepted that chemical interactions with functional groups of natural organic matter (NOM) is vital for the bioavailability and mobility of trace elements. In this study the binding strength of cadmium (Cd) to soil organic matter (SOM) was determined in an organic (49% organic C) soil as a function of reaction time, pH and Cd concentration. In experiments conducted at native Cd concentrations in soil (0.23 μg g−1 dry soil), halides (Cl, Br) were used as competing ligands to functional groups in SOM. The concentration of Cd in the aqueous phase was determined by isotope-dilution (ID) inductively-coupled-plasma-mass-spectrometry (ICP-MS), and the activity of Cd2+ was calculated from the well-established Cd-halide constants. At higher Cd loading (500-54,000 μg g−1), the Cd2+ activity was directly determined by an ion-selective electrode (ISE). On the basis of results from extended X-ray absorption fine structure (EXAFS) spectroscopy, a model with one thiolate group (RS−) was used to describe the complexation (Cd2+ + RS− ? CdSR+; log KCdSR) at native Cd concentrations. The concentration of thiols (RSH; 0.047 mol kg−1 C) was independently determined by X-ray absorption near-edge structure (XANES) spectroscopy. Log KCdSR values of 11.2-11.6 (pKa for RSH = 9.96), determined in the pH range 3.1-4.6, compare favorably with stability constants for the association between Cd and well-defined thiolates like glutathione. In the concentration range 500-54,000 μg Cd g−1, a model consisting of one thiolate and one carboxylate (RCOO−) gave the best fit to data, indicating an increasing role for RCOOH groups as RSH groups become saturated. The determined log KCdOOCR of 3.2 (Cd2+ +  RCOO− ? CdOOCR+; log KCdOOCR; pKa for RCOOH = 4.5) is in accordance with stability constants determined for the association between Cd and well-defined carboxylates. Given a concentration of reduced sulfur groups of 0.2% or higher in NOM, we conclude that the complexation to organic RSH groups may control the speciation of Cd in soils, and most likely also in surface waters, with a total concentration less than 5 mg Cd g−1 organic C.  相似文献   

17.
Lake Iso Valkjärvi (southern Finland, Europe) was divided in two with a plastic curtain in 1991. One half was neutralized with CaCO3, and the other acted as a control. Mercury concentrations of perch (Perca fluviatilis) and northern pike (Esox lucius) in the limed and control side of the lake were studied both before and after the treatment. Average Hg concentrations of perch and pike were 0.40 and 1.2 μg g−1 (ww) in the early 1980s and 0.25 and 0.72 μg g−1 (ww) a decade later at the time of liming. Ten years after the liming the Hg concentrations of perch in the limed and control sides of the lake were 0.21 and 0.28 μg g−1 (ww) and those of pike were 0.69 and 0.43 μg g−1 (ww), respectively. Nitrogen isotope ratios (δ15N) for perch in the sampling period 2002–2004 showed wide variation suggesting variable trophic positions for individual fish. Pike formed two groups according to their δ15N-values, suggesting that zoobenthos dominated the diet of pike around 20 cm in length and fish that of the larger pikes. Because the δ15N-values of fish were at similar levels in the limed and control sides of L. Iso Valkjärvi, differences in food web structure cannot account for the different fish Hg concentrations. A more likely explanation is water quality induced differences in the dynamics and bioavailability of Hg, leading to decreased formation of methyl Hg.  相似文献   

18.
This study investigates the potential risks associated with high levels and long term exposure of carbon dioxide (CO2) on the mobility and speciation of exchangeable metals in soils. CO2 incubation batch experiments at high pressure and temperature coupled with geochemical modelling were carried out to elucidate the behaviour and mobilisation of metals and the response of soil chemical parameters as a result of long term CO2 exposure. A t-Student analysis was performed to ascertain whether differences in the mean concentration of exchangeable metals in soils before and after CO2-incubations are attributable to increase of metal molibilisation because of the long term CO2 exposure. The t-Student revealed the CO2 long term incubation was statistically significant (p < 0.05) for the exchangeable concentration of Ni, Zn, and Pb. The CO2-soil incubation induces the acidification of the pore water of soils via CO2 hydrolysis and as a consequence, it increases the exchangeable concentration of Ni, Zn, and Pb in the soils. As, Al, Cr, Cu, and Fe show a different mobilisation pattern depending on the moisture content in soils. Al3+, Fe2+, Cr3+, and Cu2+ as free cations, As as HAsO2, Pb2+and PbHCO3−, Zn2+ and ZnHCO3−, are predicted to be the predominant aqueous complexes in the pore water of the incubated soils.  相似文献   

19.
Heavy metals are governed by parent material of soils and influenced by the soil physicochemical properties and soil and crop management practices. This paper evaluates total heavy metal concentrations in rainfed soils under diverse management practices of tropical India. Vertisols (clayey soils with high shrink/swell capacity) had the highest concentrations of heavy metals. However, chromium (Cr) content was above the threshold value in Aridisol [calcium carbonate (CaCO3)]-containing soils of the arid environments with subsurface horizon development. Concentration increased at lower depths (>30 cm). Basaltic soils showed higher concentrations of nickel (Ni), copper (Cu) and manganese (Mn). Cadmium (Cd), cobalt (Co), Cu and Mn concentrations were higher in soils cultivated to cotton, whereas Cr concentration was above the threshold level of 110 mg kg?1 in food crop cultivated soils. As the specific soil surface is closely related to clay content and clay type, soil’s ability to retain heavy metals is more closely tied to the specific surface than to the soil cation exchange capacity. Higher positive correlations were found between heavy metal concentrations and clay content [Cd(r = 0.85; p ≤ 0.01); Co (r = 0.88; p ≤ 0.05); Ni (r = 0.87; p ≤ 0.01); Co (r = 0.81; p ≤ 0.05); Zn (r = 0.49; p ≤ 0.01); Cr (r = 0.80; p ≤ 0.05); Mn (r = 0.79; p ≤ 0.01)]. The amounts of nitrogen–phosphorus–potassium applied showed a positive correlation with Co and Ni (r = 0.62; p ≤ 0.05). As several soils used for growing food crops are high in Ni, Cr and Mn, the flow of these metals in soil–plant–livestock/human chain needs further attention.  相似文献   

20.
In soils, silicon released by mineral weathering can be retrieved from soil solution through clay formation, Si adsorption onto secondary oxides and plant uptake, thereby impacting the Si-isotopic signature and Ge/Si ratio of dissolved Si (DSi) exported to rivers. Here we use these proxies to study the contribution of biogenic Si (BSi) in a soil-plant system involving basaltic ash soils differing in weathering degree under intensive banana cropping. δ30Si and Ge/Si ratios were determined in bulk soils (<2 mm), sand (50-2000 μm), silt (2-50 μm), amorphous Si (ASi, 2-50 μm) and clay (<2 μm) fractions: δ30Si by MC-ICP-MS Nu Plasma in medium resolution, operating in dry plasma with Mg doping (δ30Si vs. NBS28 ± 0.12‰ ± 2σSD), Ge/Si computed after determination of Ge and Si concentrations by HR-ICP-MS and ICP-AES, respectively. Components of the ASi fraction were quantified by microscopic counting (phytoliths, diatoms, ashes). Compared to fresh ash (δ30Si = −0.38‰; Ge/Si = 2.21 μmol mol−1), soil clay fractions (<2 μm) were enriched in light Si isotopes and Ge: with increasing weathering degree, δ30Si decreased from −1.19 to −2.37‰ and Ge/Si increased from 4.10 to 5.25 μmol mol−1. Sand and silt fractions displayed δ30Si values close to fresh ash (−0.33‰) or higher due to saharian dust quartz deposition, whose contribution was evaluated by isotopic mass balance calculation. Si-isotopic signatures of bulk soils (<2 mm) were strongly governed by the relative proportions of primary and secondary minerals: the bulk soil Si-isotopic budget could be closed indicating that all the phases involved were identified. Microscopic counting highlighted a surface accumulation of banana phytoliths and a stable phytolith pool from previous forested vegetation. δ30Si and Ge/Si values of clay fractions in poorly developed volcanic soils, isotopically heavier and Ge-depleted in surface horizons, support the occurrence of a DSi source from banana phytolith dissolution, available for Si sequestration in clay-sized secondary minerals (clay minerals formation and Si adsorption onto Fe-oxide). In the soil-plant system, δ30Si and Ge/Si are thus highly relevant to trace weathering and input of DSi from phytoliths in secondary minerals, although not quantifying the net input of BSi to DSi.  相似文献   

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