Black carbon estimation in French calcareous soils using chemo‐thermal oxidation method

We studied the black carbon (BC) content of ca. 405 samples from French topsoil and artificial soil and carbonate mixtures. Our protocol involved three main steps: (i) decarbonation by HCl, (ii) elimination of non‐pyrogenic organic carbon in a furnace at 375 °C, and (iii) quantification of residual carbon by CHN analysis. BC content increased for calcareous soils according to their carbonates content. Subsequent analyses confirmed the existence of a methodological artefact for BC determination only in calcareous soils. Decarbonation changes the thermal properties of organic matter, creating more recalcitrant carbon than in the initial sample. Higher CaCO₃ and organic carbon content results in a more pronounced artefact. The reversal of the first two steps of the chemo‐thermal oxidation method (i.e. thermal oxidation before soil decarbonation) eliminates this artefact. Overall, our results suggest that BC content may have been overestimated in a large number of studies on calcareous soils.     

Analysis of polynuclear aromatic and aliphatic components in soil humic acids using ruthenium tetroxide oxidation

Although condensed aromatic components are considered to be one of the major structural units of soil humic acids (HAs) and to be responsible for the dark colour of HAs, their amount and composition remain largely unknown. In ruthenium tetroxide oxidation (RTO), condensed aromatic components are detectable as their degradation products, mainly benzenepolycarboxylic acids (BPCAs). We applied this technique to soil HAs with various degrees of humification (darkening). The yields of water‐ and dichloromethane‐soluble products from HAs upon RTO after methylation ranged from 210 to 430 mg g⁻¹ and 10–40 mg g⁻¹, respectively. Eight kinds of BPCAs with two to six carboxyl groups, and seven kinds of BPCAs with additional side chains (tentative assignment) were obtained as methylated counterparts. The yield of each BPCA and the sum of the yields of BPCAs (12–85 mg g⁻¹ HAs) increased with increasing degree of humification and aromatic C content. The compositions of BPCAs indicated that the degree of condensation was greater in the HAs with greater degrees of humification. The sum of the yields of aliphatic compounds ranged from 0.1 to 6.5 mg g⁻¹, and decreased with increasing degree of humification. The C₁₂ to C₃₀ monocarboxylic acid methyl esters accounted for > 56% of the aliphatic compounds assigned, which may be present mainly as end alkyl groups in the HA molecules. We also obtained the methylated counterparts of C₁₄ to C₂₄ dicarboxylic acids; these were possibly derived from polymethylene bridges between adjacent aromatic rings.     

Aggregate-occluded black carbon in soil

The great stability of black carbon (BC) in soils may not be solely attributable to its refractory structure but also to poor accessibility when physically enveloped by soil particles. Our aim was to elucidate the intensity of physical entrapment of BC within soil aggregates. For this purpose, the A horizon of a forest, and of a grassland soil, and of three soils under tillage, were sampled at the experimental station Rotthalmünster, Germany. Black carbon was assessed in water‐stable aggregates and aggregate‐density fractions using benzene polycarboxylic acids as specific markers. The greatest BC concentrations made up 7.2% of organic carbon and were found in the < 53 μm fraction. The smallest BC concentrations occurred in the large macroaggregate fractions (> 2 mm). This pattern has been sustained even after tillage. The C‐normalized BC concentrations were significantly greater (P < 0.05) in the occluded particulate organic matter (OPOM) fractions than in the free particulate organic matter (FPOM) and the mineral fractions. This enrichment of BC compared with organic carbon in the OPOM fractions amounted to factors of 1.5–2.7. Hence, BC was embedded within microaggregates in preference to other organic carbon compounds. Only 2.5–3.5% of BC was located in the OPOM fraction < 1.6 g cm^?3, but 22–24% in the OPOM fraction with a density of 1.6–2.0 g cm^?3. This suggests that BC possibly acted as a binding agent or was selectively enriched during decomposition of protected SOM, or both. Physical inclusion, particularly within microaggregates, could therefore contribute to the long mean‐residence times of soil‐inherent BC.     

Black carbon in the zonal steppe soils of Russia

Black Mollisols are typically rich in charred organic matter, however, little is known about the zonal distribution of black C (BC) in steppe soils. In this study, we used benzene polycarboxylic acids (BPCA) as specific markers for BC in particle‐size fractions of depth profiles in several zonal soils (Greyzem, Phaeozem, Chernozem, Kastanozem) of the Russian steppe. In addition, liquid‐state ¹³C‐NMR spectra were obtained on the alkaline‐soluble soil organic matter (SOM). The results showed that both the content and depth distribution of BC varies in the different soil types; the concentration of BC in the bulk top soils being closely related to the aromaticity of the SOM (r² = 0.98 for the native topsoils, 0.83 for top‐ and subsurface soils). Especially the Chernozems were rich in aromatic SOM, which partly contained more than 17% BC of total C, most of which being allocated in the mineral fractions. Long‐term arable cropping did not reduce the BC contents of the surface soil, though it did promote the enrichment of BC in the silt fractions. The same shift was detected as soil depth increased. We conclude that BC is not fully inert in these soils, but apparently can be preserved in the silt as decomposition of SOM increased, i.e., it accumulates exactly in that fraction, which has been formerly assigned to contain old, aromatic C.     

The involvement of iron and aluminum in the bonding of phosphorus to soil humic acid

Abstract

With a peat soil similar amounts of phosphorus (P) were coprecipitated with humic acid from alkali extracts over a limited range of strongly acidic pH, whereas with a mineral soil the amount was pH dependent. The difference between the two soils relates to the much greater total amounts of inorganic P and aluminum (Al) present in the extract of the mineral soil. In this acid mineral soil, Al rather than iron (Fe) may be involved in the formation of metal bridges in humic acid‐metal‐inorganic P complexes. Neither Al or Fe were implicated in binding of organic P to humic acid. The P species observed in humic acids was dependent on the pH at which they were precipitated from the alkali extracts. In the peat soil the inorganic P was an order of magnitude lower than the organic P.     

Mobilization of Zn upon waterlogging riparian Spodosols is related to reductive dissolution of Fe minerals

Contaminated riparian soils can release metals to surface water. Periodic waterlogging affects metal mobility but the processes and soil factors governing net trends are not well understood. Experiments were combined with geochemical modelling to identify processes explaining the dynamics of zinc (Zn) in contaminated soils following waterlogging. Samples were collected from 12 Spodosols near streams in a metal‐contaminated area and four similar but uncontaminated soils were sampled in a reference area. Air‐dried samples were submerged and incubated under N₂. The soil redox potential decreased from 470 mV initially to approximately 30 mV over 2 months. The pore‐water Zn concentrations surprisingly increased over the same period by, on average, a factor of 18 (range 0.6–80; immobilization in one soil only) despite an increase in pH of 1.8 units, on average. Dissolved organic matter (DOM) in the soil solution increased during waterlogging but the observed increase in Zn solubility could not be explained by increased complexation with DOM, because the estimated Zn²⁺ activity also increased by a factor of 18 on average (range 0.2–82). Speciation modelling suggests that Zn mobilization during waterlogging results from Fe²⁺ displacing sorbed Zn²⁺ from particulate organic matter and from dissolution of Zn‐bearing Fe/Mn oxyhydroxides. This hypothesis is supported by the significant positive correlation (r = 0.87, n = 13) between the factor change in pore‐water Zn concentration and the ratio of dithionite‐extractable Fe to organic carbon content. These results show that Fe dynamics are important for predicting the fate of trace metals in anoxic soils.     

Effect of land developmental process on soil solution chemistry in acid sulfate soils distributed in the Mekong Delta,Vietnam

Abstract

Water-soluble ionic substances in acid sulfate soils are likely to be strong controls for crop production and to have impacts on aquatic ecosystems. In dry seasons, in particular, oxidation of the soil surface followed by acidification probably produces lots of acids and soluble metals. To estimate acid and metal loads from acid sulfate soils to aquatic environments, we determined the composition of water-soluble ions from soils distributed in the Mekong Delta, Vietnam. At the end of the dry season, soils were taken from each soil horizon in two soil profiles on the delta under different land developmental processes. Water-soluble ions were extracted using both distilled water and artificially synthesized irrigation water (pH 6.3) adjusted to the same ionic strength and pH as the field canal water. The relationship between extracted basic cations in both extracts showed high linear correlation, indicating a similar extraction mechanism between both extractants. Higher ionic strength in the artificial irrigation water may not have any advantages for extraction by ion exchange and, thus, properties of extracts are likely to depend on the soil properties. The older the soil parent material, the larger the rates of soluble Al and Fe and the lower the pH. Progressive weathering of the soil on the older delta has already discharged greater amounts of bases, probably for compensation of acids, and the soil has started to release exchangeable Al sorbed onto negative-charge colloids and Fe from decomposed oxides. The soil profile of the older delta released relatively greater concentrations of Al with a lower content of base cations, where the annual averaged rice yield was half that of another site. Soluble metals and acids at both sites appear to accumulate in the upper horizons above the low permeable layer, which is probably widely distributed in the Mekong Delta.     

Release of Inorganic Phosphorus from Soils by Low‐Molecular‐Weight Organic Acids

Abstract

Low‐molecular‐weight (LMW) organic acids are found in soils. They originate from the activities of various microorganisms in soils or may be exuded from the roots of living plants. Several of those organic acids are capable of forming stable organo‐metal complexes with various metal ions found in soil solutions. As a result, these processes may lead to the release of inorganic phosphorus (P) associated with aluminum (Al), iron (Fe), and calcium (Ca) in soil minerals. The release of P from soils by LMW organic acids may be important to the P nutrition of plants. Studies on the release of P from soils by a variety of LMW organic acids showed that, in general, the di‐ and tricarboxylic acids were the most effective in releasing P from two Iowa soils, whereas the monocarboxylic, phenolic, and mineral acids released similar amounts of P. Oxalic, malonic, citric, and, in some cases, malic and tartaric acids were the most effective in releasing inorganic P from the two surface soils studied. There was an inverse relationship between the amounts of P released from soils and the pK_a values of the organic acids. The amounts of P released from soils were significantly correlated with the published stability constants for the formation of organic complexes of Al, Fe, or Ca (log K_Al, log K_Fe, or log K_Ca values). In general, the aliphatic acids containing α‐caboxyl and β‐hydroxyl functional groups or phenolic acids containing ortho‐hydroxyl groups were more effective in causing the release of P from soils than similar organic acids having other functional group combinations.     

A critical examination of some common field tests to assess the acid-sulphate condition in soils

Acid‐sulphate soils are of major environmental concern in many wetlands. Severe acidification episodes have occurred worldwide because of the oxidation of iron sulphides to sulphuric acid by human activities, and diverse techniques have been set up to determine the presence of acid‐sulphate soils. This paper evaluates the usefulness of four common easy‐to‐apply field survey tests for potential acid‐sulphate diagnosis in some Histosols and Entisols in wetlands: incomplete oxidation by fast air‐drying, incubation, fast oxidation with hydrogen peroxide, and the indirect determination of sulphide with lead acetate. Samples of 227 surface‐organic and underlying mineral soils of poorly drained Histosols and Entisols of the Orinoco river delta plain were tested. Results showed that for highly organic samples the interpretation of results obtained from the acid‐sulphate soil tests may be misleading, because they cannot be unambiguously related to the production of sulphuric acid derived from pyrite oxidation. Mineral samples yielded more reliable results. The incomplete oxidation by fast air‐drying test did not induce significant acidification either in organic or in mineral samples; the final pH values were dependent on the original pH values. The fast oxidation with hydrogen peroxide test was effective with mineral samples. During the incubation test, the slower rate of pH decrease and the final values obtained with the organic samples suggested retardation in the rate and amount of acid generation by pyrite oxidation because of the concurrent oxygen consumption by organic matter and bacterial activity. The indirect determination of sulphide with lead acetate yielded only qualitative results in organic samples, but worked well in mineral samples, indicating a higher content of pyrite intermediates. Effective estimation of the actual presence and potential for acidification of soil is important, in order to avoid excessive or inappropriate amelioration techniques to prevent acid production.     

Changes in the microbial community of an arable soil caused by long-term metal contamination

The effects of past applications of farmyard manure (FYM, applied from 1942 to 1967), metal‐contaminated sewage sludge (applied from 1942 to 1961) and mineral fertilizer (NPK, applied from 1942 until now) on the microbial biomass and community structure in a sandy loam, arable soil from the Woburn Market Garden Experiment, UK, were investigated in 1998. Concentrations of Cu, Ni and Zn in soils which previously received sewage sludge were less than current European Union (EU) limits, but the soil Cd concentration was more than twice the permitted limit. Organic‐C concentration in the FYM‐treated soil and contaminated soils was about twice that of NPK‐treated soil. The initial microbial biomass‐C and estimates of total bacterial numbers by acridine orange direct count were significantly (P < 0.05) greater in the FYM‐treated soil compared with the NPK‐treated and the most contaminated soils. Total phospholipid fatty acid (PLFA) concentration (another measure of biomass) was significantly greater in the FYM‐treated soil compared with either the low or high metal‐contaminated soils, both of which contained similar PLFA concentrations. In the metal‐contaminated soils, in contrast, fluorescent Pseudomonas counts, as a percentage of total plate counts, were at least 1.5 times greater than in the uncontaminated soils. The concentrations of these microbial parameters were significantly (P < 0.05) less in the NPK soil than in all the other treatments. Biomass‐C as a percentage of organic‐C was also significantly (P < 0.05) greater in the uncontaminated soils compared with the metal‐contaminated soils. Biomass specific respiration rates in the metal‐contaminated soils were c. 1.5 times those in the FYM‐treated soil. In the metal‐contaminated soils, the concentration of mono‐unsaturated and hydroxy‐fatty acids (derived from phospholipids), and lipopolysaccharide hydroxy‐fatty acids (all indicative of Gram‐negative bacteria) were significantly (P < 0.05) greater than branched fatty acids (indicative of Gram‐positive bacteria). Furthermore, Gram‐negative counts were 62–68% greater than Gram‐positive counts in the metal‐contaminated soils. Branched fatty acid concentration was significantly (P < 0.05) greater in the FYM‐treated soil than in the metal‐contaminated soils. Gram‐positive counts were also 63% greater than Gram‐negative counts in the FYM‐treated soil. We found that effects of the relatively small heavy metal concentration caused measurable decreases in soil microbial biomass‐C concentrations, acridine orange direct counts and Gram‐positive counts. There were also increases in biomass specific respiration rates, and the microbial community had changed substantially, nearly 40 years after the metal inputs ceased. We conclude that, at the very least, the current EU permitted limits for heavy metals in agricultural soils should not be relaxed.     

Proton interactions with soil organic matter: the importance of aggregation and the weak acids of humin

Samples of three organic‐rich soils (ombrotrophic peat, podzol H‐horizon, humic ranker) were extensively washed with dilute nitric acid, dialysed against deionised water, and then subjected to acid‐base titrations over the pH range 3–10, in 0.3–300 mm NaNO₃, and with soil concentrations in the range 2–150 g l^?1. The results for the three soils were quantitatively similar. Comparison of the titration data with previously published results for humic acids isolated from the same soils showed the soil organic matter to have a greater ionic strength dependency of proton binding and to possess relatively greater buffering capacity at high pH, attributable to weak acid groups (c. 2–5 mmol g^–1) in the humin fraction of the soils. To describe the soil titration data quantitatively, we modified Humic Ion‐Binding Model VI‐FD, which utilizes a fixed Donnan volume to describe counterion accumulation, by increasing the content of weak acid groups. When artefacts in pH measurement caused by the suspension effect were taken into account, the resulting Model VI‐FD2 provided good or fair simulations of all the titration data. The results suggest that soil structure, specifically aggregation, plays a significant role in cation binding by organic soils in situ. The lack of dependence of the titration results on soil suspension concentration suggests that the findings can be applied to soils in situ.     

The use of peepers to sample pore water in acid sulphate soils

Serious environmental impacts of acidic drainage from acid sulphate soils in coastal areas are the result of the interactions between the hydrologic cycle, land use and drainage management, and pore water chemistry. In this study, in situ , diffusion-controlled dialysis profile samplers, or peepers, were used to examine pore water chemistry of acid sulphate soils in a coastal, sugarcane-producing area in Eastern Australia. The peepers sampled pore water at 20-mm intervals over a 1.0-m length, permitting excellent resolution of the sharp transitions in pore water chemistry that occur around a soil profile's iron sulphide oxidation front. Comparison of peeper profiles with soil water profiles extracted from soil samples by centrifuging, illustrated the advantages of peepers over conventional soil water sampling techniques in unconsolidated, sulphidic soils. For conventional sampling, the low permeability, gel-like, unoxidized soil samples had to be frozen then thawed before water could be extracted by centrifuging. Peeper profiles of species not involved in redox reactions agreed well with those from centrifuged soil extracts. Redox sensitive species, however, were in poorer agreement because of the lengthy soil sample preparation and extraction procedures required for extraction by centrifuging. The approximately 6-day equilibration time required for peeper sampling allows them to follow monthly or seasonal changes in pore water chemistry in acid sulphate soils due to variations in climate, and land use and management.     

Comparative evaluation of residual and total metal analyses in polluted soils

Abstract

Two digestion procedures, employing aqua regia‐HF (ARHF) and HNO₃‐HCIO4‐HF (HHH), were used to analyze residual metals (following a chemical fractionation scheme) and total metal content of two soils, one moderately polluted by municipal sludge applications and the other a grossly‐contaminated sample (20.8% Pb) from a battery recycling site. Although commonly used in sequential extraction analyses, the ARHF method solubilized only 53% (significant at p = 0.05) of the HHH‐determined residual Pb in the battery soil. For the sludge‐amended soil, residual Cd, Pb, and Zn were not statistically different by the two methods. For the battery soil, a single ARHF extraction also underestimated total Pb and Cu relative to HHH, but both methods gave statistically‐similar total Cd, Cu, Pb, and Zn for the sludge‐amended soil. As the sample metal concentration increased, the ability of ARHF to solubilize HHH‐equivalent metal quantities generally decreased. Since the degree of contamination is often unknown for environmental samples, the HHH method is more reliable for assessing residual and total metals in polluted soils     

Influence of Soil Chemical Properties on Adsorption and Oxidation of Phenolic Acids in Soil Suspension

Relationships between abiotic oxidation and adsorption of phenolic acids added to soils and soil chemical properties were investigated by using 32 soil samples and ferulic, vanillic, and p-hydroxybenzoic acids. Soil properties studied were as follows: (as adsorption factors) contents of acid oxalate extractable Al (Alo), Fe (Feo), dithionite-citrate-bicarbonate (DCB) extractable Fe (Fed), total carbon and clay, and (as oxidation factors) level of soil oxidative activity (Cr oxidation) determined by the amount of Cr(VI) converted from Cr(III) added to soils. Soil samples were divided into 3 types based on chemical properties: Andosols A (A horizon of Andosols), Andosols B (B horizon of Andosols and light-colored Andosols), and non-Andosols.

The recovery of all phenolic acids (RPA) was negatively correlated with the total carbon and Feo contents in Andosols A and B, respectively, which suggested adsorption onto soil organic matter in Andosols A and onto Feo in Andosols B. It was considered that almost no oxidation of phenolic acids occurred in Andosols A, because a very small amount of Cr(VI) was obtained. The recovery of ferulic acid (RFA) and vanillic acid (RVA), however, was negatively correlated with Cr oxidation in non-Andosols, suggesting that these phenolic acids were oxidized, while almost all of the p-hydroxybenzoic acid was recovered.

These results were also supported by the comparison between RFA and recovery of dissolved organic carbon (RTOC). RFA was very similar to RTOC in Andosols A and B, which indicated that adsorption occurred, whereas RFA was lower than RTOC in the non-Andosols that showed a high level of Cr oxidation, indicating that oxidation took place. Manganese dissolution which occurred when phenolic acids were added to soils was also examined.     

Permanganate oxidation of methylated and non-methylated aquatic humus in Norway

The chemical composition of aquatic humus was investigated by permanganate oxidation. Both methylated and non-methylated samples were investigated and the results compared with those of different soil humic fractions investigated earlier.The total amount of oxidation products identified from the methylated sample was 2%, and from the non-methylated sample 0.9%. The composition of the oxidation products from methylated aquatic humus was 42% benzenecarboxylic acid methyl esters (8 different compounds), 43% methoxy-benzenecarboxylic acid methyl esters (12 compounds), 10% dimethoxy-benzenecarboxylic acid methyl esters (4 compounds), and 5% of 1, 2, 3-propanetricarboxylic acid trimethyl ester. The unmethylated aquatic humus yielded 84% benzenecarboxylic acid methyl ester (7 compounds), 7% methoxy-benzenecarboxylic acid methyl esters (2 compounds), and 9% of 1, 2, 3-propanetricarboxylic acid trimethyl ester. Three diazines isolated from methylated material were believed to be artefacts from diazomethane treatment. Two of the diazines have earlier been found by oxidation of methylated soil samples, the third, C₁₀H₁₂N₂O₆, is an oxidation product of methylated aquatic humus only.Oxidation of aquatic humus yielded more benzenecarboxylic acids and methoxy-benzenecarboxylic acids than soil humic fractions, and less dimethoxy-benzenecarboxylic acids. No aliphatic dicarboxylic acids were detected among the oxidation products of the aquatic humus.The compounds identified are mainly the same as those found by oxidation of different soil humic fractions, although their yields clearly demonstrated that the aquatic humus differed in composition from the soil fractions.     

Sorption and leaching behaviour of polar aromatic acids in agricultural soils by batch and column leaching tests

Aromatic acids can reach the soil from direct anthropogenic activities or, indirectly, from the degradation of many aromatic compounds, such as pesticides or polycyclic aromatic hydrocarbons. Because of the anionic character of aromatic acids at the pH of most soil and sediment environments, they are expected to move rapidly through the soil profile and to pose a great risk of ground water contamination. We designed batch and column leaching tests to characterize the behaviour of three aromatic acids differing in their chemical structures, picloram (4‐amino‐3,5,6‐trichloropicolinic acid), phthalic acid (2,2‐benzenedicarboxylic acid), and salicylic acid (2‐hydroxybenzoic acid), in four European soils with different physicochemical characteristics. Batch experiments revealed that the persistence of the three acids in soil:water suspensions decreased in the order: picloram ? phthalic acid > salicylic acid, and their dissipation curves were relatively independent of soil type. Sorption by the soils, their clay‐size fractions and model sorbents indicated much greater affinity of soil constituents for salicylic acid than for picloram or phthalic acid, most likely due to the ability of salicylic acid to form bidentate complexes with positively charged soil components. The extent of leaching of the aromatic acids in hand‐packed soil columns decreased in the order: picloram (90–96%) > phthalic acid (25–90%) > salicylic acid (0–37%), which was consistent with the sorption and persistence results of the batch tests. The organic C content, the amount of small‐size pores, and the initial concentration of aromatic acid in soil appeared to be important factors influencing the leaching patterns of phthalic acid and salicylic acid in the soils studied, but did not greatly influence the leaching pattern of picloram. Sorption and leaching of polar aromatic acids in soil can therefore vary considerably depending on the structural characteristics of the aromatic acid or soil type.     

Tea Plantation–Induced Activation of Soil Heavy Metals

Abstract

The accumulation of heavy metals in tea leaves is of concern because of its impact on tea quality. This study characterized long‐term changes of soil properties and heavy‐metal fractions in tea gardens and their effect on the uptake of metals from soils by the plants. Soil and tea leaf samples were collected from five plantations with a history of 2–70 years in Jinghua, Zhejiang Province, southeast China. The six chemical fractions (water‐soluble, exchangeable, carbonate‐bound, organic‐matterbound, oxide‐bound, and residual forms) of cadmium (Cd), chromium (Cr), copper (Cu), iron (Fe), nickel (Ni), manganese (Mn), lead (Pb), and zinc (Zn) in the soils were characterized. Dissolved organic‐matter accumulation in the soils and effects of low‐molecular‐weight organic acids on solubility of soil heavy metals were also tested. Long‐term tea plantation use resulted in accumulation of dissolved organic matter, decrease of soil pH, and elevation of water‐soluble and exchangeable metal fractions, thereby increasing metal contents in leaves. The influence was more significant when soil pH was less than 4.4. The results indicated that both acidification and accumulation of dissolved organic matter induced by tea plantations were also important causes of increased accumulation of the metals in the tea leaves. This was particularly true for the soils polluted with low concentration of heavy metals, because availability of the metals in these soils was mainly controlled by pH and dissolved organic matter.     

Amino acids in Quaternary soil horizons from southwest Poland

Aminostratigraphy has proved to be a useful approach for dating fossils from the Quaternary. In these studies the amino acids in Quaternary soil formations were determined in an attempt to establish their stratigraphical relationships and relative ages. The sampling sites are in the southwest of Poland, in the Trzebnickie Hills. Three samples of fossil soils and two of recent soils were analysed. The absolute age of the soil samples was estimated by radiocarbon dating. We found that the total amount of amino acids decreased with the increasing age of soil. The smallest amounts of amino acids were found in the oldest fossil soil of Denekamp (Vistulian) age dated 29 600 ± 760 years bp . A sample of recent loess soil contained the most total amino acids, whereas the fossil soil of Lower Atlantic age, dated 3540 ± 230 years bp , was intermediate in respect of the total amount of amino acids, oxidation state and degree of biochemical transformation. Neutral amino acids formed a majority of all the amino acids studied. The method we describe could be useful in relative chronostratigraphical identification of fossil soils.     

Chemical speciation and bioavailability of Cd,Cu, Pb and Zn in Western Balkan soils

Abstract

Three thermal power plants in Serbia, Croatia and Bosnia of the Western Balkan region were expected to be metal polluting sources, and this study was performed to investigate the bioavailability and chemical speciation of trace metals in soils and soil water extracts, respectively. Surface (0–15 cm) soil samples along with maize and grass samples were collected at a gradient from the pollution source. The chemical speciation of metals was conducted using the Windereme Humic Aqueous Model (WHAM)/Model VI for water, whereas the Diffusion Gradient in Thin Films (DGT) technique was used to estimate plant availability. The chemical speciation indicated that more than 99% of all four metals in soil water extracts were complexed to fulvic acid. This is connected to relatively high soil pH (> 6.5) and high contents of soil organic matter in these soils. The accumulation of trace metals by DGT was not correlated to plant uptake. This is connected to the very low partitioning of free ions in solution, but also to the low variation in metal solubility and metal concentration in plant tissue between sites. In spite of active thermal power plants located in the areas, hardly any differences in concentration of soil metals between sites were seen and the partition of metals in soil waters was insignificant. The latter indicates that these soils have a large metal-retaining capacity. The only significant soil chemical variable affecting the variation in metal solubility was the soil pH. In a time with large infrastructure and industrial expansion in these areas, this investigation indicates the importance of protecting these high-quality soils from industrial use and degradation. High industrial activity has so far had insignificant effect on soil quality with respect to bioavailability of trace metals in these soils.     

Pollution induced community tolerance (PICT) and analysis of 16S rRNA genes to evaluate the long-term effects of herbicides on methanotrophic communities in soil

There is an increasing interest in agricultural systems in which the use of herbicides is forbidden. Therefore, soils treated with herbicides atrazine and metolachlor for the last 20 years were compared with soil samples from the same field that had never been treated (control soil). We determined the pollution induced community tolerance (PICT) by evaluating the methane oxidation capacity of soil samples after adding increasing amounts of a methane oxidation inhibitor, 2,4‐dichlorophenoxyacetic acid (2,4‐D). Denaturing gradient gel electrophoresis (DGGE) of 16S rRNA genes assessed whether the soil methanotrophic community differed between the two treatments. Addition of 60 µg 2,4‐D per g soil clearly inhibited methane oxidation in both soils but increased the time needed to oxidize 5% methane in the headspace by 250% for the control soil compared with 175% for the herbicide‐treated soil. This indicates that the soil with a long‐term herbicide history had a greater tolerance to the methane oxidation inhibitor than did the control soil. The DGGE of 16S rRNA genes amplified directly from soil community DNA could also distinguish the two treatments. The banding patterns of the Type I methanotrophs contained fewer bands in the herbicide‐treated soil. It seems that both the PICT approach and DGGE analysis are effective assays to distinguish a long‐term herbicide‐treated soil from an untreated soil.