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1.
Soil organic matter is known to contain a stable fraction with an old radiocarbon age. Size and stabilisation processes leading to the formation of this old soil carbon pool are still unclear. Our study aims to differentiate old organic matter from young and labile carbon compounds in two acid forest soils (dystric cambisol, haplic podzol). To identify such fractions soil samples were exposed to oxidation with Na2S2O8 and to dissolution by hydrofluoric acid (HF). A negative correlation between 14C activity and carbon release after dissolution of the mineral matrix by HF indicates a strong association of stabilised carbon compounds with the mineral phase. A negative correlation between the 14C activity and the relative proportion of carbon resistant to oxidation by Na2S2O8 shows that young carbon is removed preferentially by this treatment. The fraction remaining after oxidation represents a certain stabilised, long residence time carbon pool. This old fraction comprises between 1 and 30% of the total soil organic carbon in the surface horizons, but reaches up to 80% in the sub-surface horizons. Old OC is mainly stabilised by organo-mineral associations with clay minerals and/or iron oxides, whereas intercalation in clay minerals was not found to be important.  相似文献   

2.
Microbial and photochemical decomposition are two major processes regulating organic matter (OM) transformation in the global carbon cycle. However, photo-oxidation is not as well understood as biodegradation in terms of its impact on OM alteration in terrigenous environments. We examined microbial and photochemical transformation of OM and lignin derived phenols in two plant litters (corn leaves and pine needles). Plant litter was incubated in the laboratory over 3 months and compositional changes to OM were measured using nuclear magnetic resonance (NMR) and gas chromatography-mass spectrometry. We also examined the susceptibility of soil organic matter (SOM) to ultraviolet (UV) radiation. Solid-state 13C NMR spectra showed that O-alkyl type structures (mainly from carbohydrates) decreased during biodegradation and the loss of small carbohydrates and aliphatic molecules was observed by solution-state 1H NMR spectra of water extractable OM from biodegraded litters. Photochemical products were detected in the aliphatic regions of NaOH extracts from both litter samples by solution-state 1H NMR. Photo-oxidation also increased the solubility of SOM, which was attributed to the enhanced oxidation of lignin derived phenols and photochemical degradation of macromolecular SOM species (as observed by diffusion edited 1H NMR). Overall, our data collectively suggests that while biodegradation predominates in litter decomposition, photo-oxidation alters litter OM chemistry and plays a role in destabilizing SOM in soils exposed to UV radiation.  相似文献   

3.
Radiocarbon Dating of Soil Organic Matter   总被引:2,自引:0,他引:2  
Radiocarbon ages of soil organic matter are evaluated with a model which incorporates the dynamics of the14C content of soil organic matter. Measured14C ages of soil organic matter or its fractions are always younger than the true ages of soils due to continuous input of organic matter into soils. Differences in soil C dynamics due to climate or soil depth will result in significantly different14C signatures of soil organic matter for soils of the same age. As a result, the deviation of the measured14C age from the true age of soil formation could differ significantly among different soils or soil horizons. Our model calculations also suggest that14C ages of soil organic matter will eventually reach a steady state provided that no climatic or ecological perturbations occur. Once a soil or a soil horizon has reached a steady state,14C dating of soil organic matter will provide no useful information regarding the age of the soil. However, for soils in which steady state has not been reached, it is possible to estimate the age of soil formation by modeling the measured14C contents of soil organic matter. Radiocarbon dating of buried soils could, in general, overestimate the true age of the burial by as much as the steady-state age of the soil or soil horizon.  相似文献   

4.
A variety of approaches have previously been developed to estimate the fraction of terrestrial or marine organic carbon present in aquatic sediments. The task of quantifying each component is especially important for the Arctic due to the regions’ sensitivity to global climate change and the potential for enhanced terrestrial organic carbon inputs with continued Arctic warming to alter carbon sequestration. Yet it is unclear how each approach compares in defining organic carbon sources in sediments as well as their impact on regional or pan-Arctic carbon budgets. Here, we investigated multiple methods: (1) two end-member mixing models utilizing bulk stable carbon isotopes; (2) the relationship between long-chain n-alkanes and organic carbon (ALKOC); (3) principal components analysis (PCA) combined with scaling of a large suite of lipid biomarkers; and (4) ratios of branched and isoprenoid glycerol dialkyl glycerol tetraether lipids (the BIT index) to calculate the fraction of terrestrial organic matter components preserved in Arctic marine sediments.Estimated terrestrial organic carbon content among approaches showed considerable variation for identical sediment samples. For a majority of the samples, the BIT index resulted in the lowest estimates for terrestrial organic carbon, corroborating recent suggestions that this proxy may represent a distinct fraction of terrestrial organic matter; i.e., peat or soil organic matter, as opposed to markers such as n-alkanes or long-chain fatty acids which measure higher plant wax inputs. Because of the patchy inputs of n-alkanes to this region from coastal erosion in the western Arctic, the ALKOC approach was not as effective as when applied to river-dominated margins found in the eastern Arctic. The difficulties in constraining a marine δ13C end-member limit the applicability of stable isotope mixing models in polar regions. Estimates of terrestrial organic carbon using the lipid-based PCA method and the bulk δ13C mixing model approach varied drastically at each site, suggesting that organic matter fractions such as amino acids or carbohydrates may affect bulk organic matter composition in a manner that is not captured in the lipid-based analysis. Overall, terrestrial organic matter inputs to the Chukchi and western Beaufort Seas using the average of the methods at each site ranged from 11% to 44%, indicating that land-derived organic matter plays a substantial role in carbon dynamics in the western Arctic Ocean.  相似文献   

5.
Considerable fractions of the Hg content of lake and river systems in Scandinavia are discharged from the soil of the catchments. An important soil type in Scandinavia is the iron–humus podzol. The sorption characteristics of this soil type for inorganic Hg(II) and monomethyl mercury were investigated by batch experiments. The solubility of Hg2+ and CH3Hg+ in the soil horizons containing organic matter increases with increasing pH of the soil solution by favoring the formation of solute organic matter–mercury complexes. While the solubility of Hg2+ is strongly dependent on complexation to dissolved organic matter, the solubility of CH3Hg+ is more dependent on ion exchange. The concentration of solute inorganic Hg(II) increased with increasing temperature probably because of an increase in the concentration of dissolved organic carbon. There was no effect of temperature on the concentration of solute CH3Hg+. At pH values where inorganic mercury–hydroxo complexes are formed, inorganic Hg(II) is efficiently sorbed to the metal oxides of the mineral soil. The soil–water distributions of inorganic Hg(II) in the different soil horizons were described by Freundlich isotherms or linear isotherms for common and contaminated mercury contents in the soils.  相似文献   

6.
《Applied Geochemistry》1999,14(3):365-385
The abundance and chemical/mineralogical form of 226Ra, 238U and 232Th were determined on samples of soil and associated vegetation at 12 sites in the eastern United States. Progressive, selective chemical extraction plus size fractionation determined the abundance and radiometric equilibrium condition of these nuclides in 6 operationally defined soil fractions: exchangeable cations, organic matter, “free” Fe-oxides, sand, silt, and clay.In soils, profile-averaged 226Ra/238U activity ratios (AR) are within 10% of unity for most sites, implying little fractionation of U and Ra when the entire soil profile is considered. However, 226Ra greatly exceeds 238U activity in most surface soil (AR up to 1.8, av 1.22), in vegetation (AR up to 65, av. 2.8), in the exchangeable+organic fraction (AR up to 30, av. 13), in some soil Fe oxides (AR up to 3.5, av. 0.83) and in the C horizons of deeply weathered soils (AR up to 1.5).A major factor in Ra behavior is uptake by vegetation, which concentrates Ra>U and moves Ra from deeper soil to surface soil. Vegetation is capable of creating the observed Ra excess in typical surface soil horizons (AR up to 1.8, av. 1.22) in about 1000 a. Of the total Ra in an average A horizon, 42% occurs as exchangeable ions and in organic matter, but only 6–8% of the parent U and Th occur in these soil forms. In contrast, U is slightly enriched relative to Ra in Fe-oxides of A horizons, implying rapid chemical partition of vegetation-cycled U and Ra.In deeper horizons, transfer by vegetation and/or direct chemical partitioning of Ra into organic and exchangeable forms provides a source for unsupported 226Ra in Ra-rich organic matter, and leaves all soil minerals Ra-poor (AR=0.73). Organic matter evidently has a strong affinity for Ra.The phenomena discussed above are relevant to evaluation of indoor Rn hazard, and behavior of Ra at sites affected by radioactive waste disposal, phosphate tailings, Ra-rich brine, and uraniferous fertilizer.  相似文献   

7.
The solubility of aluminium (Al) in many acidic soils is controlled by complexation reactions with soil organic matter. In such soils, Al solubility is theoretically a function of the pool size of “active” Al, i.e., the total amount of Al that equilibrates with the soil solution within a defined period of time. To date, no reliable measurements of “active” Al in soil materials exist. In this study, we determined the isotopically exchangeable pool of Al (EAl) as an operationally defined assessment of “active” Al in acidic mineral soils. The suitability of CuCl2 and pyrophosphate (Na4P2O7) as extractants for “active” Al was also evaluated. Eleven samples, mostly from spodic B horizons, were spiked with carrier-free 26Al and equilibrated for different time periods (1-756 h). The size of the Al pool with which the 26Al tracer exchanged increased with time during the whole experimental period. Thus, contact time between solid and solution phases needs to be defined when assessing the “active” Al pool. Values of EAl obtained after 1 to 5 d of equilibration were equal to the amount of CuCl2 extractable Al, but considerably smaller than the Na4P2O7-extractable pool. Equilibration times greater than 5 d resulted in CuCl2 extractable Al concentrations that under-estimated the “active” Al pool. Three of the investigated samples were rich in imogolite-type materials (ITM). In these samples, 30-50 % of the added 26Al rapidly became associated with soil constituents in forms that could not be extracted by Na4P2O7, indicating that a part of ITM may be in a dynamic state.  相似文献   

8.
Aluminium smelters are major sources of F emission to the environment. We studied, in laboratory experiments, the sorption and desorption of fluoride on organic and mineral horizons of soils located within 2 km from one of these factories, situated in the northern coast of Galicia (NW Spain). The soils, developed from granite, are acid (pH H2O 3.9–5.5), rich in organic matter (4–16 % C in the A horizon) and most A horizons have high Al saturation in the exchange complex. All samples showed a notable F sorption, between 1,066 and 1,589 mg kg?1, after adding 200 mg F L?1, which accounts for 53–80 % of F added. The sorption was slightly higher in the A horizons than in the respective organic horizons (differences of up to 194 mg kg?1). The fluoride sorption upon addition of 200 mg F L?1 correlated significantly (p < 0.05) with soil pH in water (r = ?0.77), iron extracted by acid ammonium oxalate (r = 0.68), aluminium plus iron extracted by acid ammonium oxalate (r = 0.63), exchange aluminium (r = 0.52) and clay percentage in soil (r = 0.76). The F sorption fitted to both Langmuir and Freundlich models. Desorbed F accounted for only 12–22 % of sorbed fluoride and correlated (p < 0.05) negatively with non-crystalline (extracted by acid ammonium oxalate) Fe (r = ?0.51) and clay content (r = ?0.74) and positively with organic matter (r = 0.69) and with the effective cation exchange capacity of the soil (r = 0.50).  相似文献   

9.
A depth- and particle size-specific analysis of soil organic carbon (SOC) and its isotopic composition was undertaken to investigate the effects of soil texture (or particle size) on the depth profile of stable carbon isotopic composition of SOC (δ13CSOC) in two tropical soils. Depth-specific samples from two soil profiles of markedly different texture (coarse grained and fine grained) were separated into particle size classes and analyzed for the (mass/mass) concentration of SOC (C) and δ13CSOC. Within 1 m of the soil surface, δ13CSOC in the coarse-textured soil increases by 1.3 to 1.6‰, while δ13CSOC from the fine-textured soil increase by as much as 3.8 to 5.5‰. This increasing depth trend in the coarse-textured soil is approximately linear with respect to normalized C, while the increase in the fine-textured soil follows a logarithmic function with respect to normalized C. A model of Rayleigh distillation describing isotope fractionation during decomposition of soil organic matter (SOM) accounts for the depth profile of δ13CSOC in the fine-textured soil, but does not account for the depth profile observed in the coarse-textured soil despite their similar climate, vegetation, and topographic position. These results suggest that kinetic fractionation during humification of SOM leads to preferential accumulation of 13C in association with fine mineral particles, or aggregates of fine mineral particles in fine-textured soils. In contrast, the coarse-textured soil shows very little applicability of the Rayleigh distillation model. Rather, the depth profile of δ13CSOC in the coarse-textured soil can be accounted for by mixing of soil carbon with different isotopic ratios.  相似文献   

10.
High concentrations of metals in organic matter can inhibit decomposition and limit nutrient availability in ecosystems, but the long-term fate of metals bound to forest litter is poorly understood. Controlled experiments indicate that during the first few years of litter decay, Al, Fe, Pb, and other metals that form stable complexes with organic matter are naturally enriched by several hundred percent as carbon is oxidized. The transformation of fresh litter to humus takes decades, however, such that current datasets describing the accumulation and release of metals in decomposing organic matter are timescale limited. Here we use atmospheric 210Pb to quantify the fate of metals in canopy-derived litter during burial and decay in coniferous forests in New England and Norway where decomposition rates are slow and physical soil mixing is minimal. We measure 210Pb inventories in the O horizon and mineral soil and calculate a 60-630 year timescale for the production of mobile organo-metallic colloids from the decomposition of fresh forest detritus. This production rate is slowest at our highest elevation (∼1000 m) and highest latitude sites (>63°N) where decomposition rates are expected to be low.We calculate soil layer ages by assuming a constant supply of atmospheric 210Pb and find that they are consistent with the distribution of geochemical tracers from weapons fallout, air pollution, and a direct 207Pb application at one site. By quantifying a gradient of organic matter ages with depth in the O horizon, we describe the accumulation and loss of metals in the soil profile as organic matter transforms from fresh litter to humus. While decomposition experiments predict that Al and Fe concentrations increase during the initial few years of decay, we show here that these metals continue to accumulate in humus for decades, and that enrichment occurs at a rate higher than can be explained by quantitative retention during decomposition alone. Acid extractable Al and Fe concentrations are higher in the humus layer of the O horizon than in the mineral soil immediately beneath this layer: it is therefore unlikely that physical soil mixing introduces significant Al and Fe to humus. This continuous enrichment of Al and Fe over time may best be explained by the recent suggestion that metals are mined from deeper horizons and brought into the O horizon via mycorrhizal plants. In sharp contrast to Al and Fe, we find that Mn concentrations in decomposing litter layers decrease exponentially with age, presumably because of leaching or rapid uptake, which may explain the low levels of acid extractable Mn in the mineral soil. This study quantifies how metals are enriched and lost in decomposing organic matter over a longer timescale than previous studies have been able to characterize. We also put new limits on the rate at which metals in litter become mobile organo-metallic complexes that can migrate to deeper soil horizons or surface waters.  相似文献   

11.
Biodiversity loss, climate change, and increased freshwater consumption are some of the main environmental problems on Earth. Mountain ecosystems can reduce these threats by providing several positive influences, such as the maintenance of biodiversity, water regulation, and carbon storage, amongst others. The knowledge of the history of these environments and their response to climate change is very important for management, conservation, and environmental monitoring programs. The genesis of the soil organic matter of the current upper montane vegetation remains unclear and seems to be quite variable depending on location. Some upper montane sites in the very extensive coastal Sea Mountain Range present considerable organic matter from the late Pleistocene and other from only the Holocene. Our study was carried out on three soil profiles (two cores in grassland and one in forest) on the Caratuva Peak of the Serra do Ibitiraquire (a sub-range of Sea Mountain Range – Serra do Mar) in Southern Brazil. The δ13C isotopic analyses of organic matter in soil horizons were conducted to detect whether C3 or C4 plants dominated the past communities. Complementarily, we performed a pollen analysis and 14C dating of the humin fraction to obtain the age of the studied horizons. Except for a short and probably drier period (between 6000 and 4500 cal yr BP), C3 plants, including ombrophilous grasses and trees, have dominated the highlands of the Caratuva Peak (Pico Caratuva), as well as the other uppermost summits of the Serra do Ibitiraquire, since around 9000 cal yr BP. The Caratuva region represents a landscape of high altitude grasslands (campos de altitude altomontanos or campos altomontanos) and upper montane rain/cloud forests with soils that most likely contain some organic matter from the late Pleistocene, as has been reported in Southern and Southeastern Brazil for other sites. However, our results indicate that the studied deposits (near the summit) are from the early to late Holocene, when somewhat wetter and warmer conditions (since around 9000 cal yr BP) enabled a stronger colonization of the ridge of Pico Caratuva by mainly C3 plants, especially grassland species. However, at the same time, even near the summit, the soil core from the forest site already presented the current physiognomy (or a shrubby/elfin or successional forest), indicating that the colonization of the neighboring uppermost saddles and valleys were probably populated mainly by upper montane forest species.  相似文献   

12.
Organic material in metal contaminated soils around an abandoned magnetite mine–smelter complex in the critical Highlands watershed protects the groundwater and surface water from contamination. Metals in these waters were consistently below local and national water standards. Two groups of soil types cover the area: (1) Group A disturbed metal-rich soils, and (2) Group B undisturbed organic soils. Chromium and nickel were more elevated than other metals with Cr more widespread than Ni. In Group A, Cr correlated strongly with sesquioxides in the lower horizons (Fe2O3: r = 0.74, p < 0.025; Al2O3: r = 0.92, p < 0.005). In Group B, Cr correlated strongly (r = 0.96, p < 0.005) with soil organic matter (SOM) in the O-horizons. Ni–Cr (Group A: 52 and 70% in O- and lower horizons, respectively; Group B: ~100% in both horizons) and V–Cr correlations (78% only in Group A lower horizons) suggest similar retention mechanisms for these elements. Average soil \textpH\textCaCl2 {\text{pH}}_{{{\text{CaCl}}_{2} }} for both groups ranged between 3.65 and 5.91, suggesting that soil acidity is determined by organic acids and solubility of Al3+ releasing H+ ions. SOM and sesquioxides contribute significantly to creating naturally occurring filtration systems, removing metals, and protecting water quality. High Ca, Fe, and Ti in Group A soils suggest slag and ash were mixed into the soils. Some low-Cr sources include magnetite, slag, and ash (100, 100 and 200 mg/kg, respectively). Constant ZrO 2 :TiO 2 ratios in the lower soils indicate soil formation from breakdown of underlying tailing rocks, contributing Cr to these layers.  相似文献   

13.
During the past 50 years, the amount of agricultural fertilizer used in Northern China increased from about 7.5 kg ha?1 in the 1950s to approximately 348 kg ha?1 in the 1990s. Given that little is known about the effects of nitrogen fertilization on soil labile carbon fraction in Northern China, this paper evaluated such effects in terms of microbial biomass and dissolved organic carbon in the Sanjiang Plain located in Northeast China. Soils with different cultivation time and undisturbed marsh with Deyeuxia angustifolia were selected to study the effects of nitrogen fertilization on the soil labile organic fractions microbial C (biomass C, microbial quotient, and basal respiration) and to estimate the contributions of nitrogen input on the dynamics of soil labile carbon. Continuous nitrogen application decreased total organic and dissolved organic carbon concentrations significantly, leading to the lack of carbon source for microbes. Therefore, continuous nitrogen fertilizer application induced negative effects on measured soil microbiological properties. However, a moderate nitrogen application rate (60 kg N ha?1) stimulated soil microbial activity in the short term (about 2 months), whereas a high nitrogen application rate (150 kg N ha?1) inhibited measured soil microbiological properties in the same period.  相似文献   

14.
Changes in surface charge of soil particles that accompany mineral transformations during soil formation were measured for a humid tropical chronosequence in Hawaiian basalt ranging in lava flow age from 0.3 to 4100 kiloyears (ky). Parent mineralogy is dominated by glass, olivine, pyroxene, and feldspar, whereas poorly crystalline (PC) weathering products (allophane, microcrystalline gibbsite, ferrihydrite) accumulate in early to intermediate weathering stages (through 400 ky), and crystalline secondary minerals (kaolinite, gibbsite, goethite) are dominant in the oldest (1400 and 4100 ky) soils. Detailed characterization of the solid phase was accomplished with chemical extractions, X-ray diffraction analysis, and molecular spectroscopy (FTIR and 13C MAS NMR). Simultaneous proton titration and background ion adsorption measurements were made on LiCl saturated soils over a range in pH (2-9) and ionic strength (0.001 and 0.01 M LiCl). Dependence of variable surface charge on solution composition reflects the changing nature of mineral-organic interactions over the course of pedogenesis. Points of zero net proton charge (PZNPC) ranged from 3.4 to 6.2 and 2.0 to 5.8 at 0.001 and 0.01 M ionic strength (I), respectively. Intermediate-aged soils containing the highest mass concentration of humified soil organic matter (SOM) and its complexes with PC minerals gave rise to the steepest charging curves (largest pH dependence) and highest PZNPC values. Surface charge properties of these soils most closely reflected their weakly acidic Al and Fe hydroxide constituents, which is consistent with metal hydroxide saturation of organic functional groups, rather than organic coating of mineral surfaces. Charging curves were less steep and PZNPC values were lower for the older soils, consistent with SOM coating of more crystalline goethite, kaolinite, and gibbsite surfaces in a soil system less impacted by labile Al and Fe.  相似文献   

15.
A peat deposit from the East European Russian Arctic, spanning nearly 10 000 years, was investigated to study soil organic matter degradation using analyses of bulk elemental and stable isotopic compositions and plant macrofossil remains. The peat accumulated initially in a wet fen that was transformed into a peat plateau bog following aggradation of permafrost in the late Holocene (~2500 cal a BP). Total organic carbon and total nitrogen (N) concentrations are higher in the fen peat than in the moss‐dominated bog peat layers. Layers in the sequence that have lower concentrations of total hydrogen (H) are associated with degraded vascular plant residues. C/N and H/C atomic ratios indicate better preservation of organic matter in peat material dominated by bryophytes as opposed to vascular plants. The presence of permafrost in the peat plateau stage and water‐saturated conditions at the bottom of the fen stage appear to lead to better preservation of organic plant material. δ15N values suggest N isotopic fractionation was driven primarily by microbial decomposition whereas differences in δ13C values appear to reflect mainly changes in plant assemblages. Positive shifts in both δ15N and δ13C values coincide with a local change to drier conditions as a result of the onset of permafrost and frost heave of the peat surface. This pattern suggests that permafrost aggradation not only resulted in changes in vegetation but also aerated the underlying fen peat, which enhanced microbial denitrification, causing the observed 15N‐enrichment. Copyright © 2012 John Wiley & Sons, Ltd.  相似文献   

16.
Zinc isotopes have been studied along two smelter-impacted soil profiles sampled near one of the largest Pb and Zn processing plants in Europe located in northern France, about 50 km south of Lille. Mean δ66Zn values along these two soil profiles range from +0.22 ± 0.17‰ (2σ) to +0.34 ± 0.17‰ (2σ) at the lowest horizons and from +0.38 ± 0.45‰ (2σ) to +0.76 ± 0.14‰ (2σ) near the surface. The δ66Zn values in the lowest horizons of the soils are interpreted as being representative of the local geochemical background (mean value +0.31 ± 0.38‰), whereas heavier δ66Zn values near the surface of the two soils are related to anthropogenic Zn. This anthropogenic Zn occurs in the form of franklinite (ZnFe2O4)-bearing slag grains originating from processing wastes at the smelter site and exhibiting δ66Zn values of +0.81 ± 0.20‰ (2σ). The presence of franklinite is indicated by EXAFS analysis of the topsoil samples from both soil profiles as well as by micro-XANES analysis of the surface horizon of a third smelter-impacted soil from a distant site. These results indicate that naturally occurring Zn and smelter-derived Zn exhibit significantly different δ66Zn values, which suggests that zinc isotopes can be used to distinguish between geogenic and anthropogenic sources of Zn in smelter-impacted soils. In addition to a possible influence of additional past sources of light Zn (likely Zn-sulfides and Zn-sulfates directly emitted by the smelter), the light δ66Zn values in the surface horizons compared to smelter-derived slag materials are interpreted as resulting mainly from fractionation processes associated with biotic and/or abiotic pedological processes (Zn-bearing mineral precipitation, Zn complexation by organic matter, and plant uptake of Zn). This conclusion emphasizes the need for additional Zn isotopic studies before being able to use Zn isotopes to trace sources and pathways of this element in surface environments.  相似文献   

17.
Mineral soil horizons (Ae, Bhf1, Bhf2, Bf, BC and C) were carefully collected from two podzolic soil profiles in the Lake Clair watershed (Québec) in order to assess anthropogenic trace metal accumulation. Petrographic and selective analyses were performed to establish the soil mineralogy and properties. Furthermore, a complete sequential extraction procedure has been applied to help understanding the complex chemical speciation of Pb in forest soils. Chemical speciation of Pb showed a strong vertical gradient: 85% of this metal is mainly partitioned in refractory minerals in the C-horizon whereas in the upper Bhf1 and Ae-horizons, less than 50% of Pb is associated with this fraction. In the Ae-horizon, for example, 35%, 30% and 12% of total Pb, respectively, is associated with the exchangeable, labile organic matter and amorphous Fe-Mn oxides fractions. The distribution of Pb and Cr in the studied forest soils mainly reflects progressive contamination of the watershed by anthropogenic atmospheric sources. The anthropogenic source is indicated by elevated Cr and Pb concentrations in the topsoil (Bhf and Ae) horizons and by strong negative correlation between 206Pb/207Pb ratios and total Pb concentrations. According to these isotopic values, penetration of anthropogenic Pb does not exceed 10 cm in both soil profiles. Below this depth, both Pb concentrations and isotopic ratios remain nearly constant and similar to values observed in pre-anthropogenic sediments from Lake Clair. These values are interpreted as the natural geochemical backgrounds of the watershed. Based on that behaviour, calculated anthropogenic Pb net inputs amounted to between 1.24 and 1.8 g/m2.  相似文献   

18.
Taking limestone soil and yellow soil, the two major soil types in karst areas as examples, analyzing stable carbon isotope composition (δ13C value) of soil organic matter (SOM) in bulk soils and particle-size fractions of four soil profiles under three vegetable forms, the following results are reached: in the limestone soil profile, soil organic carbon contents are all above 1.0%, the highest value is 7.1% in the surface soil; however, they are between 0.3% and 4.6% in the three yellow soil profiles. From the surface to the bottom of the soil profiles, the variation of δ13C value of soil organic carbon for limestone soil profile is only between −24.1‰ and −23.0‰, however, it’s between −24.8‰ and −21.1‰ for yellow soil profiles. The variation range of δ13C value of soil organic carbon associated with particle-size separates is slight for limestone soil but is considerable for yellow soil. The contrast research indicates that the changes between the contents and the δ13C value of soil organic carbon with depth are complex. The vertical patterns of stable carbon isotope in soil organic matter have a distinct regional characteristic in karst areas.  相似文献   

19.
X-ray absorption near-edge structure (XANES) and nuclear magnetic resonance (NMR) spectroscopy were used in combination to characterize organic carbon structures in a series of wetland soils in Saskatchewan, and XANES spectroscopy was also used to examine sulphur speciation in the soils. The organic C contents of most of the wetland soils are consistently higher by a factor of two to five times compared to adjacent well-drained soils. NMR analyses indicate that the organic matter in the wetland soils consists of predominantly aliphatic structures such as carbohydrates and long chain poly(methylene) units which are refractory structures found in plant waxes. The poly(methylene) structures have a significant capacity to sorb nonpolar organic molecules. The phenolic OH and carboxyl group content of the wetland soils studied is an additional significant factor in their sequestering ability for heavy metals or pesticides. Carbon XANES spectroscopy shows that the surface (∼10 nm) layer of particulate organic matter has a structure dominated by aromatic, carbohydrate and carboxylic acid-like material apparently derived from partially degraded lignin and cellulose polymers which are adsorbed onto clay minerals. The aliphatic structures remaining in this surface layer are probably recalcitrant (poly)methylene units. At a depth of ∼100 nm, the aliphatic content significantly increases suggesting the presence of more labile structures. The presence of these more labile aliphatic compounds may be due to slow decomposition rates in the wet, often cool environments present and to the protective action of the more refractory components in the surface ∼10 nm of the organic matter. Drying of the wetlands, either by draining or as a result of climate change, is likely to result in the rapid decomposition of these labile organic structures releasing carbon dioxide. Our data indicate that the preservation of the organic carbon compounds in these soils is a result of their presence as surface adsorbed layers on the soil mineral particles. The soils contain three different classes of sulphur compounds: reduced organic sulphur such as sulphides, low valent oxidized sulphur such as sulphoxides, and high valent oxidized sulphur such as sulphonate and sulphate. Of these, reduced sulphur species constitute between one-third and two-thirds of the total. Sulphonate structures comprise between a fifth and a third of the total. Sulphates exhibit a wide variation in content, and sulphoxides are either not detected or are present to a lesser extent (<5%). Drying of the wetlands would cause oxidation of sulphides to sulphates.  相似文献   

20.
Copper stable isotope ratios are fractionated during various biogeochemical processes and may trace the fate of Cu during long-term pedogenetic processes. We assessed the effects of oxic weathering (formation of Cambisols) and podzolization on Cu isotope ratios (δ65Cu). Two Cambisols (oxic weathered soils without strong vertical translocations of soil constituents) and two Podzols (soils showing vertical translocation of organic matter, Fe and Al) were analyzed for Cu concentrations, partitioning of Cu in seven fractions of a sequential extraction and δ65Cu values in bulk soil. Cu concentrations in the studied soils were low (1.4-27.6 μg g−1) and Cu was mainly associated with strongly bound Fe oxide- and silicate-associated forms. Bulk δ65Cu values varied between −0.57‰ and 0.44‰ in all studied horizons. The O horizons had on average significantly lighter Cu isotope compositions (−0.21‰) than the A horizons (0.13‰) which can either be explained by Cu isotope fractionation during cycling through the plants or deposition of isotopically light Cu from the atmosphere. Oxic weathering without pronounced podzolization in both Cambisols and a weakly developed Podzol (Haplic Podzol 2) caused no significant isotope fractionation in the single profiles, while a slight tendency to lower δ65Cu values with depth was visible in all four profiles. This is the opposite depth distribution of δ65Cu values to that we observed in hydromorphic soils (soils which show indication of redox changes because of the influence of water saturation) in a previous study. In a more pronounced Podzol (Haplic Podzol 1), δ65Cu values and Cu concentrations decreased from Ah to E horizons and increased again deeper in the soil. Humus-rich sections of the Bhs horizon had higher Cu concentrations (2.8 μg g−1) and a higher δ65Cu value (−0.18‰) than oxide-rich sections (1.9 μg g−1, −0.35‰) suggesting Cu translocation between E and B horizons as organo-Cu complexes. The different depth distributions in oxic weathered and hydromorphic soils and the pronounced vertical differences in δ65Cu values in Haplic Podzol 1 indicate a promising potential of δ65Cu values to improve our knowledge of the fate of Cu during long-term pedogenetic processes.  相似文献   

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