Comprehensive study of Pb (II) speciation in soil by X-ray absorption spectroscopy (XANES and EXAFS) and sequential fractionation

Purpose

The study is aimed at the analysis of the spatial–structural organization of Pb(II) in Chernozem soils and the relationship between the metal ion and the soil components using X-ray absorption spectroscopy and chemical extractive fractionation.

Materials and methods

In a model experiment, soil samples were artificially contaminated with elevated rates of Pb(NO₃)₂ and PbO (2000 and 10,000 mg kg^?1). The samples of mineral phases (bentonite, gibbsite, kaolinite, calcite, and hydromuscovite) were saturated with Pb²⁺ ions. The sequential fractionation of Pb in the soil was conducted by the Tessier method. X-ray absorption near-edge fine structure (XANES) spectra at the Pb L_III-edge (13.040 keV) were obtained on a Rigaku R-XAS Looper spectrometer. Extended X-ray absorption fine structure (EXAFS) L_III-edge Pb was measured at the Structural Materials Science beamline of the Kurchatov Center for Synchrotron Radiation.

Results and discussion

The results of successive extraction showed that Pb is associated with strongly bound organic substances, Fe and Mn (hydr)oxides, and carbonates. An increase in the portion of exchangeable fraction is observed under extreme loads. At the addition of Pb in the form of oxide and nitrate to the soil, the fractional compositions were similar, which indicates the good transformation of PbO in Chernozem. The features of XANES spectra indicate different orbital transitions in the electron shells of Pb²⁺ ions for monoxide (PbO) and soluble salt (Pb(NO₃)₂), which affect the ion properties and determine the individual structure of the coordination sphere. The analysis of XANES revealed that sorption of Pb in the soil samples and in the samples of mineral phases does not change its bond valence.

Conclusions

The increased degree of soil contamination with Pb is accompanied by decreasing the stable connection between metal and soil components. Lead ions in bentonite, kaolinite, hydromuscovite, gibbsite, and calcite are incorporated in the positions of the inner-sphere complex replacing some aluminum ions in the octahedral sites. This results in changes the Pb–O distances in Pb-bearing octahedrons. We may suggest that Pb²⁺ is also sorbed by dimer (Pb–Pb) silicate and/or aluminum groups. The structure of adsorbent surface plays the key role in the sorption of Pb²⁺ by mineral phases.

     

Differentiation between adsorbed and precipitated sulphate in soils and at micro-sites of soil aggregates by sulphur K-edge XANES

To investigate the potential of synchrotron‐based X‐ray Absorption Near‐Edge Structure spectroscopy (XANES) at the sulphur (S) K‐edge for a discrimination of adsorbed and precipitated sulphate in soils and soil particles, XANES spectra of ionic sulphate compounds and Al/Fe hydroxy sulphate minerals were compared with spectra of SO₄^2? adsorbed to ferrihydrite, goethite, haematite, gibbsite or allophane. Ionic sulphate and hydroxy sulphate precipitates had broader white‐lines (WL) at 2482.5 eV (full width at half maximum (FWHM) of edge‐normalized spectra, 2.4–4.2 eV; Al hydroxy sulphates, 3.0 eV) than SO₄^2? adsorbed to Al/Fe oxyhydroxides or allophane (FWHM, 1.8–2.4 eV). The ratio of the white‐line (WL) height to the height of the post‐edge feature at 2499 eV (WL/PEF) was larger for SO₄^2? adsorbed to Al/Fe oxyhydroxides or allophane (8.1–11.9) than for Al/Fe hydroxy sulphates and ionic sulphates (3.9–5.7). The WL/PEF ratio of edge‐normalized S K‐edge XANES spectra can be used to distinguish adsorbed from precipitated SO₄^2? in soils and also at microsites of soil particles. The contribution of adsorbed and precipitated SO₄^2? to the total SO₄^2? pool can be roughly quantified. Adsorbed ester sulphate may result in overestimation of precipitated SO₄^2?. The spectra of most soils could be fitted by linear combination fitting (LCF), yielding a similar partitioning between adsorbed and precipitated SO₄^2? as an evaluation of the WL/PEF ratio. The SO₄^2? pool of German forest soils on silicate parent material in most cases was strongly dominated by adsorbed SO₄^2?; however, in three German forest soils subject to elevated atmospheric S deposition, a considerable portion of the SO₄^2? pool was precipitated SO₄^2?, most likely Al hydroxy sulphate. The same is true for Nicaraguan Eutric and Vitric Andosols subject to high volcanogenic S input. In the subsoil of the Vitric Andosol, adsorbed SO₄^2? and Al hydroxy sulphate coexist on a micron scale.     

Phosphorus speciation in cultivated organic soils revealed by P K‐edge XANES spectroscopy

Cultivated organic soils make a significant contribution to phosphorus (P) leaching losses from agricultural land, despite occupying a small proportion of cultivated area. However, less is known about P mobilisation processes and the P forms present in peat soils compared with mineral soils. In this study, P forms and their distribution with depth were investigated in two cultivated Histosol profiles, using a combination of wet chemical extraction and P K‐edge X‐ray absorption near‐edge structure (XANES) spectroscopy. Both profiles had elevated P content in the topsoil, amounting to around 40 mmol kg^?1, and P speciation in both profiles was strongly dominated by organic P. Topsoils were particularly rich in organic P (P‐org), with relative proportions of up to 80%. Inorganic P in the profiles was almost exclusively adsorbed to surface reactive aluminium (Al) and iron (Fe) minerals. In one of the pro‐files, small contributions of Ca‐phosphates were detected. A commonly used P saturation index (PSI) based on ammonium‐oxalate extraction indicated a low to moderate risk of P leaching from both profiles. However, the capacity of soil Al and Fe to retain P in organic soils could be reduced by high competition from organic compounds for sorption sites. This is not directly accounted for in PSI and similar indices. Accumulation of P‐org in the topsoil may be attributable by microbial peat decomposition and transformation of mineral fertiliser P by both microbiota and crops. Moreover, high carbon–phosphorus ratio in the surface peat material in both profiles suggests reduced net mineralisation of P‐org in the two soils. However, advancing microbial peat decomposition will eventually lead to complete loss of peat horizons and to mineralisation of P‐org. Hence, P‐org in both profiles represents a huge potentially mobilised P pool.     

Soil sulphur speciation in two glacier forefield soil chronosequences assessed by S K‐edge XANES spectroscopy

In regions with little atmospheric input of sulphur (S) and S‐poor parent material, the bio‐availability of S, which is dependent on its speciation, may limit ecosystem production and succession. In our study, soil S speciation in two glacier forefield soil chronosequences (Hailuogou Glacier, Gongga Shan, China; Damma Glacier, Swiss Alps) was investigated for the first time. Different S species were quantified by synchrotron‐based X‐ray absorption near‐edge structure (XANES) spectroscopy at the S K‐edge. Both chronosequences show similar patterns and pedogenetic trends of their topsoil S status. Topsoil concentrations of total S were correlated with the concentrations of organic carbon and pedogenic Fe/Al oxyhydroxides. Both moraine materials contained inorganic sulphides, which in the topsoil were oxidized within 30 (Hailuogou) or 75 years (Damma) of soil development after deglaciation. About 50% of total S in the fresh moraine material at Hailuogou and 75% of that in the 15 year‐old soil at Damma was organically‐bound. During initial soil development, the contribution of organic S to total S increased at the expense of inorganic sulphide and sulphate, resulting in organic S percentages > 90% of total topsoil S after 30 (Hailuogou) and 75 (Damma) years of pedogenesis. Organic S compounds with electronic oxidation states of the S atom > + 1.5 (sulphoxides, sulphones, sulphonates and ester sulphates) dominated the organic S pool in all soils. Hence, microbial degradation of non‐sulphide organic S (sulphonates and ester sulphates) is probably important to mitigate S scarcity caused by limited availability of SO₄^2?‐S in these soils. Changes in topsoil S speciation during initial stages of pedogenesis and ecosystem succession in glacier forefields under a cool, humid climate appear to be governed by combined effects of mineral weathering (oxidation of inorganic sulphides and formation of S‐adsorbing sesquioxides), accumulation and microbial turnover of soil organic matter and the type of vegetation succession.     

Sulfur speciation in well‐aerated and wetland soils in a forested catchment assessed by sulfur K‐edge X‐ray absorption near‐edge spectroscopy (XANES)

In forested catchments, retention and remobilization of S in soils and wetlands regulate soil and water acidification. The prediction of long‐term S budgets of forest ecosystems under changing environmental conditions requires a precise quantification of all relevant soil S pools, comprising S species with different remobilization potential. In this study, the S speciation in topsoil horizons of a soil toposequence with different groundwater influence and oxygen availability was assessed by synchrotron‐based X‐ray absorption near‐edge spectroscopy (XANES). Our investigation was conducted on organic (O, H) and mineral topsoil (A, AE) horizons of a Cambisol–Stagnosol–Histosol catena. We studied the influence of topography (i.e., degree of groundwater influence) and oxygen availability on the S speciation. Soil sampling and pretreatment were conducted under anoxic conditions. With increasing groundwater influence and decreasing oxygen availability in the sequence Cambisol–Stagnosol–Histosol, the C : S ratio in the humic topsoil decreased, indicating an enrichment of soil organic matter in S. Moreover, the contribution of reduced S species (inorganic and organic sulfides, thiols) increased systematically at the expense of intermediate S species (sulfoxide, sulfite, sulfone, sulfonate) and oxidized S species (ester sulfate, SO ). These results support the concept of different S‐retention processes for soils with different oxygen availability. Sulfur contents and speciation in two water‐logged Histosols subject to permanently anoxic and temporarily oxic conditions, respectively, were very different. In the anoxic Histosol, reduced S accounted for 57% to 67% of total S; in the temporarily oxic Histosol, reduced S was only 43% to 54% of total S. Again, the extent of S accumulation and the contribution of reduced S forms to total S closely reflected the degree of O₂ availability. Our study shows that XANES is a powerful tool to elucidate key patterns of the biogeochemical S cycling in oxic and anoxic soil environments. In contrast to traditional wet‐chemical methods, it particularly allows to distinguish organic S compounds in much more detail. It can be used to elucidate microbial S‐metabolism pathways in soils with different oxygen availability by combining soil inventories and repeated analyses of a sample in different stages of field or laboratory incubation experiments under controlled boundary conditions and also to study (sub)microspatial patterns of S speciation in aggregated soils.     

Sulphur speciation and turnover in soils: evidence from sulphur K-edge XANES spectroscopy and isotope dilution studies

Sulphur K-edge X-ray absorption near edge structure (XANES) spectroscopy was used to quantify S species in humic substance extracts from ten soils from the UK, China and New Zealand, which differ in land use and agricultural management. XANES spectroscopy showed the presence of most reduced (sulphides, disulphides, thiols and thiophenes), intermediate (sulphoxides and sulphonates) and highly oxidised S (ester sulphates) forms, with the three groups representing 14-32%, 33-50% and 22-53% of the organic S in the humic substance extracts, respectively. Land use had a profound influence on the relative proportions of S species. Well-drained arable soils generally had a higher proportion of organic S present in the most oxidised form than the grassland soils collected nearby, whereas paddy soils showed a more reduced profile due to episodic flooding. In the Broadbalk Classical Experiment at Rothamsted, reversion of an arable system to grassland or woodland in the 1880s resulted in an increase of the most reduced and intermediate S species at the expense of the most oxidised S species. Long-term applications of farmyard manure to an arable plot also shifted S species from the most oxidised to the intermediate and the most reduced species. Sulphur immobilisation and gross mineralisation were determined in seven soils using the ³⁵S isotope dilution method. Gross mineralisation during a 53-day incubation correlated more closely with the amounts of the most reduced and intermediate S species than with the most oxidised S species, suggesting that the former (C-bonded S) were the main source of organic S for mineralisation in the short-term.     

Speciation of sulphur in soils and soil particles by X-ray spectromicroscopy

Current wet chemical methods for the speciation of sulphur (S) in soils are inaccurate and do not allow one to assess the S speciation of individual soil particles and colloids. X-ray microscopy and Near Edge X-ray Absorption Fine structure Spectroscopy (NEXAFS) can be used to study individual species of S at the K-adsorption edge. We have used these techniques to identify and quantify S species in bulk soil, soil particles and colloids from Oh and Bh horizons of two forested Podzols. The partitioning of soil sulphur as determined on bulk samples of the Oh horizons by X-ray spectromicroscopy agreed fairly well with the results of a conventional S speciation for the soil at Schluchsee, and reasonably well for that at Rotherdbach. The NEXAFS analyses on individual soil particles revealed that they are richer in reduced organic sulphur than the bulk soil for the Schluchsee Oh and richer in sulphate for Rotherdbach Oh. The techniques can be used reliably to separate and quantify sulphur species with different oxidation states in the soil. The combination of X-ray transmission and sulphur fluorescence images with unfocused and focused NEXAFS spectra at the K-adsorption edge of sulphur at specific microsites allowed us to compare the distribution of S species in bulk soil with that of distinct soil particles and soil colloids. Moreover, we can use it to assess the spatial distribution of different S species on soil particles on a scale of a few hundred nanometres.     

Sulfur K-edge XANES spectroscopy reveals differences in sulfur speciation of bulk soils, humic acid, fulvic acid, and particle size separates

X-ray absorption near edge structure (XANES) spectra at the sulfur (S) K-edge (E=2472 eV) were compared for bulk soil material, humic and fulvic acid fractions, and different particle size separates from Ah horizons of two arable Luvisols, from an O and a Bs horizon of a Podzol under Norway spruce forest, and from an H horizon of a Histosol (peat bog). In the bulk soil samples, the contribution of reduced organic S (organic mono- and disulfides) to total sulfur increased from 27% to 52%, and the contribution of ester sulfate and SO₄²⁻-S decreased from 39% to 14% of total S in the following order: arable Luvisols Ah—forested Podzol O—Histosol H. This sequence reflects the increasing organic carbon content and the decreasing O₂ availability in that order. Neither sulfonate nor inorganic sulfide was detected in any of the bulk soil samples. For all samples except the Podzol Bs, the XANES spectra of the bulk soils differed considerably from the spectra of the humic and acid fractions of the respective soils, with the latter containing less reduced S (16-44% of total S) and more oxidized S (sulfone S: 19-35%; ester sulfate S: 14-38% of total S). Also the S speciation of most particle size fractions extracted from the Ah horizon of the Viehhausen Luvisol and the Bs horizon of the Podzol was different from that of the bulk soil. For both soils, the contribution of oxidized S species to total S increased and the contribution of sulfoxides and organic mono- and disulfides decreased with decreasing particle size. Thus, sulfur K-edge XANES spectra of alkaline soil extracts, including humic and fulvic acids or of particle size separates are not representative for the S speciation of the original soil sample they are derived from. The differences can be attributed to (i) artificial changes of the sulfur speciation during alkaline extraction (conversion of reduced S into oxidized S, loss of SO₄²⁻ during purification of the extracts by dialysis) or particle size separation (carry-over of water-soluble S, such as SO₄²⁻), but also to (ii) preferential enrichment of oxidized S in hydrophilic water-soluble soil organic matter (ester sulfate) and in the clay fraction of soils (ester sulfate, adsorbed SO₄²⁻).     

Applications of hierarchical cluster analysis (CLA) and principal component analysis (PCA) in feed structure and feed molecular chemistry research, using synchrotron-based Fourier transform infrared (FTIR) microspectroscopy

Synchrotron technology based Fourier transform infrared microspectroscopy (S-FTIR) is a recently emerging bioanalytical microprobe capable of exploring the molecular chemistry within microstructures of feed tissues at a cellular or subcellular level. To date there has been very little application of hierarchical cluster analysis (CLA) and principal component analysis (PCA) to the study of feed inherent microstructures and feed molecular chemistry between feeds and/or between different structures within a feed, in relation to feed quality and nutrient availability using S-FTIR. In this paper, multivariate statistical methods--CLA and PCA--were used to analyze synchrotron-based FTIR individual spectra obtained from feed inherent microstructures within intact tissues by using the S-FTIR as a novel approach. The S-FTIR spectral data of three feed inherent structures (strucutre 1, feed pericarp; structure 2, feed aleurone; structure 3, feed endosperm) and different varieties of feeds within cellular dimensions were collected at the National Synchrotron Light Source (NSLS) at Brookhaven National Laboratory (BNL), U.S. Department of Energy (NSLS-BNL, New York). Both PCA and CLA methods gave satisfactory analytical results and are conclusive in showing that they can discriminate and classify inherent structures and molecular chemistry between and among the feed tissues. They also can be used to identify whether differences exist between the varieties. These statistical analyses place synchrotron-based FTIR microspectroscopy at the forefront of those new potential techniques that could be used in rapid, nondestructive, and noninvasive screening of feed intrinsic microstructures and feed molecular chemistry in relation to the quality and nutritive value of feeds.     

Water-stable aggregates, glomalin-related soil protein, and carbohydrates in a chronosequence of sandy hydromorphic soils

The conversion of pasture to cropland leads to a decline of aggregation in topsoils and to a decrease of aggregate-binding agents such as carbohydrates and glomalin-related soil protein (GRSP). Till now, studies on soil aggregation focused either on carbohydrates or on GRSP as a binding agent in aggregates. In this study we analyse the development of the relationship between carbohydrates, GRSP, TOC and aggregate-stability following land-use change. Furthermore, we discuss the contents of carbohydrates, GRSP and TOC in each of the aggregate fractions. For these purposes, a chronosequence of sites, which were converted from pasture to cropland at different periods in history, was established. To get further insight into the impact of different types of land-use, also soils under forest, either afforested or permanent, were studied. The mean-weight diameter (MWD) of water-stable aggregates, the carbohydrate, and the GRSP content were determined in 49 soils. It was found that the MWD of the water-stable aggregates decreased monoexponentially (R² = 0.66) by 66% during the first 46 years after conversion of the soils from pasture to cropland. During the same period, the carbohydrate content decreased very rapidly after the land use change by 64% and the GRSP content decreased more slowly by 57%. The MWD of the forest soils were in the same range as those of the permanent pasture soils although they exhibit significantly higher TOC contents, which indicate that other stabilization mechanisms are dominant in forest soils, less important in the chronosequence soils. TOC, carbohydrates and the GRSP contents were sigmoidally correlated with the MWD. Among the four water-stable aggregate fractions TOC and carbohydrates exhibited high contents in the macroaggregates and were less present in the microaggregates. GRSP, in contrast, was more equally distributed among the four water-stable aggregate fractions.     

Rapid and sensitive determination of microbial activity in soils and in soil aggregates by dimethylsulfoxide reduction

Summary Based on the reduction of dimethylusulfoxide (DMSO) to dimethylsulfide (DMS) by microorganisms, a simple, rapid, sensitive and inexpensive method for the determination of microbial activity in soil samples was developed. When DMSO was added to samples, DMS appeared immediately in the gas phase, which was quantitatively analyzed by gas chromatography. The DMS liberation rate was constant for several hours. The reaction immediately starts and its linearity indicate that neither the physiological state nor the number of organisms were changed by the assay. DMSO reduction is widespread among microorganisms; out of 144 strains tested (both fungi and bacteria) only 5 were unable to carry out this reaction. The reaction in soil samples was strongly inhibited by toluene, cyanide, azide, or by fumigation, but was considerably stimulated by glucose. These findings demonstrate that the reaction was due to the activity of microorganisms. The DMSO reduction in different soil samples was significantly correlated with arginine ammonification and heat output (r>0.9). A good correlation was observed with the organic-matter content (r = 0.74), but not with microbial numbers, clay content, or the pH of the soil. Standard deviations of less than 10% were routinely found. Furthermore, the method is sufficiently sensitive to allow measurements of activity in very small samples (< 0.1 g). For example, a microbial activity profile can be established for a single soil aggregate, revealing marked differences in activity on the outside and in the interior.     

X-ray radiometric determination of lanthanides (praseodymium,neodymium, and samarium) in soils

A procedure of the modified energy-dispersive X-ray fluorescence method (X-ray radiometric analysis using a ²⁴¹Am radionuclide source) was developed for the identification of praseodymium, neodymium, and samarium. The procedure is based on the exclusion of the disturbing effect of barium and lanthanum on the lines of praseodymium and neodymium, as well as the effect of lanthanum and cerium on the lines of samarium. On the basis of the new method, data were obtained on the geochemistry of three lanthanides in soils of the northern taiga. Praseodymium and neodymium were detected by the X-ray radiometric method even in podzols depleted of heavy metals. The method can detect samarium at the levels of the soil clarke and higher. Positive samarium (or, wider, rare-earth) anomalies can be expected in the soils located not far from the deposits of apatite-nephelines, loparites, and phosphorites and in the soils developed on alkaline granites and carbonate weathering crusts.     

高黎贡山土壤腐殖质特性与团聚体数量特征研究

采用野外调查与室内分析结合的方法,研究高黎贡山土壤腐殖质特性与团聚体数量特征,对进一步了解高黎贡山生态系统中土壤特征,降低土壤侵蚀,减少水土流失提供科学依据。结果表明:土壤腐殖质的组成具有明显地带性特征,有机质、腐殖酸含量、胡/富(HA/FA)随海拔高度的降低呈先上升后下降的趋势,A1层胡敏酸(HA)、富里酸(FA)含量分布规律为暗棕壤棕壤棕色针叶林土亚高山草甸土黄棕壤黄壤黄红壤。A2层腐殖酸、FA变化趋势为暗棕壤棕壤棕色针叶林土黄棕壤黄壤亚高山草甸土黄红壤。A1层HA、FA分子复杂程度、化学稳定性比A2层强。1～0.5mm和0.25mm粒径的团聚体含量占绝大多数,约占60%～70%。随着海拔高度的降低,粗粒减少,细粒增多。土壤团聚体服从对数正态分布,其几何平均直径与几何标准差、土壤可蚀性K值之间存在负相关关系,土壤可蚀性K值与几何标准差存在正相关关系,同时土壤也具有一定的分形特性。其中亚高山草甸土几何平均直径(Dg)、平均重量直径(MWD)值最大,几何标准差(δg)、可蚀性K值、分形维数(CFD)值最小,土壤结构稳定性和抗蚀能力相对较强。胡敏酸含量是影响土壤可蚀性的重要因素。     

Alterations of soil aggregates and intra-aggregate organic carbon fractions after soil conversion from paddy soils to upland soils: Distribution, mineralization and driving mechanism

Investigating the impacts of soil conversion on soil organic carbon(OC) content and its fractions within soil aggregates is essential for defining better strategies to improve soil structure and OC sequestration in terrestrial ecosystems. However, the consequences of soil conversion from paddy soil to upland soil for soil aggregates and intra-aggregate OC pools are poorly understood. Therefore, the objective of this study was to quantify the effects of soil conversion on soil aggregate and intra...     

Sulphur speciation and biogeochemical cycling in long-term arable cropping of subtropical soils: evidence from wet-chemical reduction and S K-edge XANES spectroscopy

Agriculture has claimed a large share of terrestrial environments in the tropics and subtropics through cultivation of native grasslands or forests. The impact of this anthropogenic change on speciation, dynamics, and ecological significance of sulphur (S) compounds is still poorly understood. We combined degradative wet-chemical reduction and S K-edge X-ray absorption near edge structure (XANES) spectroscopy techniques to evaluate the impact of long-term agricultural management of native grassland soils in South African Highveld on the amount, form and dynamics of S species. Sulphur XANES in the humic substances extracted by 0.1 m NaOH/0.4 m NaF solution showed the presence of strongly reduced (polysulphides, disulphides, thiols, monosulphides and thiophenes), intermediate (sulphoxides and sulphonates) and strongly oxidized (ester sulphates) organic-S. It showed that strongly oxidized-S is the predominant form (39–54%) of the total organic-S in the humic substances, and organic-S in the intermediate oxidation state represented 30–37% (78–93% of which was attributed to sulphonates). The strongly reduced organic-S comprised only 17–24% of the total organic-S. We did not find a close correlation between the results of a degradative wet-chemical procedure and XANES spectroscopy conducted in both the bulk soils (ester SO₄-S from XANES versus HI-fractionation, r = 0.27; P < 0.05) and the humic substance extracts (ester SO₄-S from XANES versus HI-fractionation, r= 0.39; P < 0.05). The ratio of reduced-S to strongly oxidized-S (R-S/O-S) in the humic substances decreased from 0.61 to 0.21, while the ratio of intermediate-S to strongly oxidized-S (I-S/O-S) declined from 0.93 to 0.61 after 90 years of arable cropping of the native grassland soils. Hence, there was a shift in oxidation state towards strongly oxidized-S (+6) and, thereby, a change in the relative proportion of the organic-S moieties associated with each oxidation state following cultivation of the native grassland soils. Therefore, we conclude that changes in land-use practice brought about not only quantitative change but also altered the composition of organic-S functional groups in these native subtropical grassland soils.     

The soil aggregates stability index (ASI) and its extreme values

A method for determining maximum–minimum values of the soil aggregates stability index (ASI) is presented. This allows for the calculation of the range of variations of the soil aggregates stability index for destructive changes of soil aggregation and for assuming criterion of the soil aggregation stability evaluation. The data used for the calculations are distributions of soil aggregate frequencies before and after destruction. On the base of the ASI, determined for the tested soil and the range of its possible variations, other indices that characterise the relative nature of aggregate variations have been defined. The presented methodology for the analysis of the soil aggregation stability index has been illustrated for three soils and various methods of water stability determination.     

Reveal protein molecular structural-chemical differences between two types of winterfat (forage) seeds with physiological differences in low temperature tolerance using synchrotron-based Fourier transform infrared microspectroscopy

Winterfat (Krascheninnikovia lanata) (forage seed) is a long-lived native shrub with superior forage quality for livestock and wildlife. The objectives of this study were to use advanced synchrotron technology [S-Fourier transform infrared microspectroscopy (FTIR)] as a novel approach to reveal protein molecular structural-chemical differences in terms of protein secondary structures between the two types of winterfat (forage) seeds, which show physiological differences in low-temperature tolerances. This experiment was performed at beamline U10B at the National Synchrotron Light Source (NSLS) in Brookhaven National Laboratory (BNL), U.S. Department of Energy (NSLS-BNL, New York). The results showed that with the synchrotron analytical technique (S-FTIR), the molecular structural-chemical makeup and characteristics of the winterfat seed tissues could be imaged and revealed. The protein secondary structures differed between the large and the small seed tissues. By using the multicomponent peaks modeling method, the results show that the large seeds contained no significant differences (P > 0.05) in percentage of beta-sheet (average 37.0%) and alpha-helix (average 24.1%). However, the large seeds contained a lower (P < 0.05) percentage of beta-turns (18.1 vs 20.1%) and a lower (P < 0.05) ratio of beta-turns to alpha-helices (0.8 vs 0.9) and beta-turns to beta-sheets (0.5 vs 0.6). Our results demonstrate the potential of highly spatially resolved synchrotron-based FTIR microspectroscopy to reveal differences of structural molecular chemistry and protein secondary structures, which are associated with seed size variation and may affect germination behaviors.     

Organic matter stabilization in soil aggregates and rock fragments as revealed by low-temperature ashing (LTA) oxidation

Low-temperature ashing (LTA), which is able to remove the organic material from mineral grains or aggregates without any disturbance to their physical structure, was used to oxidize the organic matter present into soil aggregates and sandstone- and siltstone-derived rock fragments. The three fractions were characterized for their mineralogy and pores distribution, and treated with LTA apparatus for 24 and 96 h. The losses of C and N were evaluated and the chemical modifications produced by LTA in the extractable organic matter and humin were investigated by chemical and spectroscopic methods. During the LTA treatment, the simplest organic molecules were lost, and the remaining material acquired a higher degree of oxidation, making this heterogeneous mix of fresh, partially and well-humified substances more homogeneous. In the aggregates and in the sandstone rock fragments, the composition of extractable material changed and was enriched in the aromatic component, due also to the contribution of fragments deriving from humin, as the oxidation produced compounds enriched in carboxyl groups and characterized by a higher solubility. This could mean the occurrence of a continuum between humin and extractable organic matter mediated by oxidation processes. In the siltstone rock fragments extractable organic matter and humin underwent lesser severe transformation than those in the sandstone rock fragments and aggregates; the mineralized C and N derived almost entirely from the extractable fraction, whereas humin appeared to be virtually indifferent to the LTA treatment. In fact, although the amount of C lost during the treatment was similar for the three fractions, the siltstone rock fragments lost only 11% of initial humin-C pool, against 30% of the aggregates and 60% of sandstone rock fragments. As the three fractions showed similar mineralogy, the obtained results indicated that the soil fraction richest in micropores exerts a better protection on the organic matter.