The significance of solid‐state 13C NMR spectroscopy of whole soil in the characterization of humic matter

Abstract

Differences in characteristics of humic matter were investigated by solid‐state CP/MAS ¹³C NMR spectroscopy of whole (nontreated) materials and their extracted humic fractions. Samples used in the analysis were lignite, a commercial humate AG, and the Bh horizons of a Mascotte and a Lawnwood soil. Humic fractions were extracted by the 0.1 M NaOH or Na₄P₂O₇ (pH 9.8) method. The humic (HA) and fulvic acid (FA) obtained were weighed and analysed for total acidity, carboxyl and phenolic‐OH group contents. Whole lignite, humate AG and soil samples, and the HA and FA fractions were analyzed by solid state CP MAS ¹³C NMR and infrared spectroscopy. Carbon, H, and N contents were determined by chemical analysis. NMR spectra of the combined HA+FA extracts resembled the spectra of the whole materials. No additional signals were detected, indicating that alien compounds were not produced during the extraction. The best spectra were obtained with HA samples produced by the NaOH method. These spectra closely resembled those of the untreated materials. Spectral and chemical differences noticed between the HA (or FA) fractions were attributed more to differences in origin than to the extraction procedure. Aliphatic, aromatic and carboxyl groups were the major components of HA from lignite and humate AG. In contrast, HA from the two Haplaquods were characterized by four major components: the aliphatic, polysaccharide, aromatic, and carboxyl groups. Regardless of origin, all the HA fractions contained similar functional groups, as indicated by their close similarities in infrared spectra.     

Quantitative solid-state 13C NMR spectroscopy of organic matter fractions in lowland rice soils

Spin counting on solid‐state ¹³C cross‐polarization (CP) nuclear magnetic resonance (NMR) spectra of two humic fractions isolated from tropical lowland soils showed that only 32–81% of potential ¹³C NMR signal was detected. The observability of ¹³C NMR signal (C_obs) was higher in the mobile humic acid (MHA) than in the calcium humate (CaHA) fraction, and increased with increasing intensity of irrigated rice cropping. NMR observability appeared to be related to the nature of the organic carbon, with phenol‐ and methoxyl‐rich samples having the higher values of C_obs. The Bloch decay (BD) technique provided more quantitatively reliable ¹³C NMR spectra, as evidenced by values of C_obs in the range 91–100% for seven of the eight humic fractions studied. The BD spectra contained considerably more aryl and carbonyl signal, and less O–alkyl and alkyl signal, with the greatest differences between CP and BD spectra observed for the samples with low C_obs(CP). The causes of low CP observability were investigated using the spectral editing technique RESTORE ( RE storation of S pectra via T _CH and T O ne R ho (T_1ρH) E diting). Rapid T_1ρH relaxation was found to be primarily responsible for the under‐representation of carbonyl carbon, whereas inefficient cross‐polarization was primarily responsible for the under‐representation of aryl carbon in CP spectra. Proton NMR relaxation rates T_1H and T_1ρH were found to correlate with other NMR properties and also with cropping management. Non‐uniform rates of T_1H relaxation in two of the CaHA fractions enabled the generation of proton spin relaxation editing subspectra.     

Analysis of sulfur compounds in acid sulfate soils and other recent marine soils

Abstract

A refined scheme for the semi micro chemical analysis of sulfur fractions in soils is presented. Pyrite is analyzed, as iron, after extraction in HNO₃. Non‐pyrite iron is excluded by a pretreatment with HF/H₂SO₄. Water‐soluble sulfate and jarosite [KFe₃(SO₄)₂(OH)₆], the other dominant sulfur fractions in acid sulfate soils, are analyzed turbidimetrically, as sulfate, after successive extractions by EDTA.3Na (water soluble plus exchangeable SO₄) and by hot 4 M HCl (jarosite). These methods are simpler, less bulky and more specific than most existing procedures.

Introduction of elemental sulfur analysis permits estimation of organic sulfur fraction as well. Sums of individual sulfur fractions agree well with separate total sulfur determinations.

The proposed analysis of pyrite permits also distinction of the components Fe₂O₃, FeO and FeS₂ in soils and rocks².     

Soil organic matter stabilization in acidic forest soils is preferential and soil type-specific

Minerals with large specific surface areas promote the stabilization of soil organic matter (SOM). We analysed three acidic soils (dystric, skeletic Leptic Cambisol; dystric, laxic Leptic Cambisol; skeletic Leptic Entic Podzol) under Norway spruce (Picea abies) forest with different mineral compositions to determine the effects of soil type on carbon (C) stabilization in soil. The relationship between the amount and chemical composition of soil organic matter (SOM), clay content, oxalate‐extractable Fe and Al (Fe_o; Al_o), and dithionite‐extractable Fe (Fe_d) before and after treatment with 10% hydrofluoric acid (HF) in topsoil and subsoil horizons was analysed. Radiocarbon age, ¹³C CPMAS NMR spectra, lignin phenol content and neutral sugar content in the soils before and after HF‐treatment were determined and compared for bulk soil samples and particle size separates. Changes in the chemical composition of SOM after HF‐treatment were small for the A‐horizons. In contrast, for B‐horizons, HF‐soluble (mineral‐associated) and HF‐resistant (non‐mineral‐associated) SOM showed systematic differences in functional C groups. The non‐mineral associated SOM in the B‐horizons was significantly depleted in microbially‐derived sugars, and the contribution of O/N‐alkyl C to total organic C was less after HF‐treatment. The radiocarbon age of the mineral‐associated SOM was younger than that of the HF‐resistant SOM in subsoil horizons with small amounts of oxalate‐extractable Al and Fe. However, in horizons with large amounts of oxalate‐extractable Al and Fe the HF‐soluble SOM was considerably older than the HF‐resistant SOM. In acid subsoils a specific fraction of the organic C pool (O/N‐alkyl C; microbially‐derived sugars) is preferentially stabilized by association with Fe and Al minerals. Stabilization of SOM with the mineral matrix in soils with large amounts of oxalate‐extractable Al_o and Fe_o results in a particularly stable and relatively old C pool, which is potentially stable for thousands of years.     

Effect of artificial irrigation,acid precipitation and liming on the microbial activity in soil of a spruce forest

Summary The effects of irrigation, acid precipitation and liming on the bioactivity in a spruce forest soil were measured with different tests. Except for the iron reduction test and the FDA hydrolysis, the highest activities were measured in the upper horizons and mostly decreased gradually in the deeper ones. The determination of heat output and respiration without additional energy supply and ATP measurement gave similar results: acid precipitation inhibits the bioactivity in O₁ and O_f1, layers; lime stimulated it mostly in O_f2 horizons. Except for the results of ATP measurement, in O_f2 horizons the influence of lime exceeded that of acid irrigation. The results obtained from respiration and microcalorimetric measurements after the introduction of an energy supply were similar: Humidity, derived either from acid precipitation or from irrigation, stimulated the activity as well as lime, clearly in O_f2, to a smaller extent also in deeper horizons. The bioactivity in Oft increased significantly in the plots in the order: control, plot with acid irrigation, plot with normal irrigation, limed plot, limed plot with acid irrigation, and limed plot with normal irrigation. The difference between irrigated and acid-irrigated plots is due to the inhibitive effects of protons and SO ₄ ^2– . The FDA hydrolysis test showed a clear stimulative effect of humidity in O_f horizons of non-limed plots. With the iron reduction test, stimulation in acid-irrigated and inhibition in limed samples was demonstrated. The maximum bioactivity measured with this method was localized in deeper horizons.     

The distribution of minor elements among the components of a soil developed in loess

This previously described buried soil, developed in uniform parent material, was used to study the relative movements of elements and other soil components down the profile. Samples from all horizons were treated with hydrogen peroxide and ammonium oxalate, under ultra-violet light, to remove organic matter and sesquioxides, and the residues were subdivided into six particle size fractions.Downward movement of clay (< 0.5 μm) was accompanied by movement of extractable Al₂O₃ and Fe₂O₃, thus identifying these as part of the mobile fraction. The less close relationship of extractable Fe₂O₃ to the clay suggested that it also occurred partly in coarser aggregates. Proportions of minor elements extracted varied from < 1% for Sr to nearly complete extraction of Co, Cu and Mo in some horizons. The extractable fractions of most minor elements throughout the profile behaved more like Fe₂O₃ than Al₂O₃. In the extraction residues, nearly all elements were enriched in the clay fractions relative to the coarser fractions; this being greatest for V and Fe.     

MODELLING LEACHING OF INORGANIC Hg(II) IN A SCANDINAVIAN IRON-HUMUS PODZOL - VALIDATION AND LONG-TERM LEACHING UNDER VARIOUS DEPOSITION RATES

Increasing mercury contents are reported from freshwater systems and fish in northern Europe and North America. Mercury input from soils is a major source with the leaching being affected by increased atmospheric mercury deposition compared to pre-industrial times and by other environmental conditions such as acid rain. The results of a mathematical model-calculation of vertical inorganic Hg(II) leaching in a Scandinavian iron-humus podzol under different atmospheric input rates of mercury are presented. Leaching under background rain conditions was calculated to be considerably stronger than under acid rain conditions. Increasing fractions of deposited soluble or solute atmospheric mercury were leached from the O _f(h)-horizon with decreasing soil content of soluble mercury under acid rain conditions; this effect was less pronounced under background rain conditions. The steady state concentrations of soluble mercury of the upper soil horizons were calculated and compared with the actual concentrations of total (= soluble + insoluble mercury) and extractable (= estimate of soluble) mercury measured in these horizons. The results indicate that even if the deposition of airborne mercury to soil is strongly reduced, the total mercury content of the soil decreases only slowly. It may take decades or even centuries before a new steady state concentration of total mercury is established in the soil. The decrease of the mercury concentration in the O _f(h)-horizon is probably largely dependent on the turnover of organic matter, binding most of the deposited airborne mercury in an insoluble form. Hence, present day mercury leaching is likely to be dominated by mercury deposited during former times and temporarily retained in an insoluble form in the organic matter.     

Location and chemical composition of stabilized organic carbon in topsoil and subsoil horizons of two acid forest soils

The ¹⁴C age of soil organic matter is known to increase with soil depth. Therefore, the aim of this study was to examine the stabilization of carbon compounds in the entire soil profile using particle size fractionation to distinguish SOM pools with different turnover rates. Samples were taken from a Dystric Cambisol and a Haplic Podzol under forest, which are representative soil types under humid climate conditions. The conceptual approach included the analyses of particle size fractions of all mineral soil horizons for elemental composition and chemical structure of the organic matter by ¹³C cross-polarization magic angle spinning nuclear magnetic resonance (CPMAS NMR) spectroscopy. The contribution of phenols and hydroxyalkanoic acids, which represent recalcitrant plant litter compounds, was analyzed after CuO oxidation.In the Dystric Cambisol, the highest carbon concentration as well as the highest percentage of total organic carbon are found in the <6.3 μm fractions of the B and C horizons. In the Haplic Podzol, carbon distribution among the particle size fractions of the Bh and Bvs horizons is influenced by the adsorption of dissolved organic matter. A relationship between the carbon enrichment in fractions <6.3 μm and the ¹⁴C activity of the bulk soil indicates that stabilization of SOM occurs in fine particle size fractions of both soils. ¹³C CPMAS NMR spectroscopy shows that a high concentration of alkyl carbon is present in the fine particle size fractions of the B horizons of the Dystric Cambisol. Decreasing contribution of O-alkyl and aromatic carbon with particle size as well as soil depth indicates that these compounds are not stabilized in the Dystric Cambisol. These results are in accordance with data obtained by wet chemical analyses showing that cutin/suberin-derived hydroxyalkanoic acids are preserved in the fine particle size fractions of the B horizons. The organic matter composition in particle size fractions of the top- and subsoil horizons of the Haplic Podzol shows that this soil is acting like a chromatographic system preserving insoluble alkyl carbon in the fine particle size fractions of the A horizon. Small molecules, most probably organic acids, dominate in the fine particle size fractions of the C horizons, where they are stabilized in clay-sized fractions most likely due to the interaction with the mineral phase. The characterization of lignin-derived phenols indicated, in accordance with the NMR measurements, that these compounds are not stabilized in the mineral soil horizons.     

Equilibria of weak acids and organic Al complexes explain activity of H+ and Al3+ in a salt extract of exchangeable cations

Two sequential extractions with unbuffered 0.1 m BaCl₂ were done to study the release of salt-exchangeable H⁺ and Al from mineral horizons of five Podzols and a Cambisol. Released Al was found to have a charge close to 3+ in all horizons and in both extractions. This finding was supported by the near-equality of the titrated exchangeable acidity (EA_T) and the sum of exchangeable acids (EA = H_e + 3Al_e, calculated from the pH and Al concentration of the extract). The ratio between EA of the second and the first extraction was over 0.50 in the Bs2 and C horizons and smaller in the other horizons. H⁺ was assumed to be in equilibrium with weak acid groups, and the modified Henderson–Hasselbach equation, pK_HH = pH ? n log (α/(1 ? α)), was used to explain pH of the extract. The degree of dissociation (α) was calculated as the ratio between effective and potential cation exchange capacity. Value of the empirical constant n was found to be near unity in most horizons. When the monoprotic acid dissociation was assumed in all horizons, pK_HH had the same value in both extractions. For Al³⁺, two equilibrium models were evaluated, describing (i) complexation reactions of Al³⁺ with soil organic matter, and (ii) equilibrium with Al(OH)₃. Apparent equilibrium constants were written as (i) pK_o = xpH ? pAl³⁺, and (ii) log Q_gibbs= log Al³⁺ ? 3log H^+. The two extractions gave an average reaction stoichiometry x close to 2 in all horizons. Results suggest that an equilibrium with organic Al complexes can be used to express dissolved Al³⁺, aluminium being apparently bound to bidentate sites. The value of log Q_gibbs was below the solubility of gibbsite (log K_gibbs = 8.04) in many horizons. In addition, log Q_gibbs of the second extraction was greater than that of the first extraction in all horizons except the C horizon. This indicates that equilibrium with Al(OH)₃ cannot explain dissolved Al³⁺ in the soils. We propose that the models of pK_HH and pK_o can be used to simulate exchangeable H⁺ and Al³⁺ in soil acidification models.     

Active and passive organic matter fractions in Mediterranean forest soils

Soil organic carbon (C) is a complex set of pools, and to understand its dynamics it is necessary to know which of these pools are active at a given moment, and which act as passive, due to either physical protection or biochemical recalcitrance, or both. This matter has been studied mainly in agricultural soils. For forest soils, especially in Mediterranean areas, there is a data gap that needs to be filled. Therefore, we studied three profiles in Catalonia (NE Spain) over marl and under Pinus halepensis stands. Soil horizons were incubated under optimal conditions for 45 days. The respiration rate on day 45 was taken as basal respiration rate (BR_R). The following fractions were quantified: (1) soluble C, (2) microbial C, both corrected (MC_C) and uncorrected (MC_UC) (i.e., applying or not a correction factor to account for the non-extractable microbial carbon), (3) C in size fractions, isolated by ultrasonic dispersion and sieving plus sedimentation, and (4) labile and recalcitrant C, quantified by acid hydrolysis, applied to both the whole soil horizons and the size fractions. The basal respiration rate (BR_R) correlated best with the sum soluble + MC_UC, which altogether seem the best estimator of the active C pool. The correlation between BR_R and MC_C was worse, thus suggesting that not all microbial C should be included in the active pool. The correlation of BR_R with the C associated to coarse fractions (>50 μm) was positive, whereas that\with C associated to fine fractions (<20 μm) was negative. The correlations were lower than those obtained with the soluble + MC_UC, thus suggesting that the coarse organic fractions are probably the main source of active C, but not active C itself. Alone, the pools obtained by acid hydrolysis (labile and recalcitrant) correlated poorly with BR_R, but the combination of size fractionation with acid hydrolysis resulted in some of the best predictors of microbial activity. Hydrolyzable polyphenolic compounds inhibited microbial activity. Unhydrolyzable C associated to fine fractions (<20 μm) seemed the most stable of all the C pools studied. By contrast the unhydrolyzable part was apparently as unstable as the hydrolyzable part in the coarse organic debris. Overall, our results point to a hierarchy of constraints: both the physical protection and the biochemical quality affect microbial activity, but the physical protection goes first. In the profiles studied, C did not appear to be more stable in deep horizons than in surface horizons.     

Acid and mineral components determining the exchangeable acidity in mineral horizons of taiga soils of the Komi Republic

Analysis of acid components in soil-KCl suspension filtrates from the mineral horizons was performed on the basis of analytical data reported between 1958 and 2003, including the data on more than 60 soil profiles (about 300 horizons) from the taiga zone of the Komi Republic. It was shown that the acid ions Al³⁺, H⁺ (exchangeable hydrogen), and Fe³⁺ and the basic ion H₃SiO ₄ ^? are the main components determining the pH of filtrates. Groups of horizons with the predominance of specific ions were separated.     

Stoffbilanzierung in einer Pseudogley-Parabraunerde aus Löß unter Anwendung der IR-Phasenanalyse

Material balance in an aquic Hapludalf from loess by means of IR-phase analysis Grain size fractions of an aquic Hapludalf from loess near Göttingen were examined mineralogically and chemically. On the base of actual mineral composition (mode) by means of infrared spectroscopy weathering balances were made up. The results reveal a strong illite/mica loss of about 80 kg/m², which is due to decomposition in the A-horizon, and which is not compensated by a slight gain in the B-horizon. The mineral balance of the total profile yields a clay degradation of 44 kg/m². Furthermore, in the A-horizon the chemical balance gives evidence of considerable mobilizations and substantial losses mainly of SiO₂, Al₂O₃, MgO and K₂O combined in silicates. Depending on soil horizons and grain sizes the illites have K-contents varying from 4 to 8% K₂O. Al₂O₃ and MgO also show distinct variations. Both components are correlated negatively and decrease (Al₂O₃) respectively increase (MgO) from the top to the bottom.     

IMOGOLITE AND PROTO-IMOGOLITE ALLOPHANE IN SPODIC HORIZONS: EVIDENCE FOR A MOBILE ALUMINIUM SILICATE COMPLEX IN PODZOL FORMATION

Examination by infrared spectroscopy and electron microscopy of the fine clays (<0.5 μm) dispersed at pH 3.5 from H₂O₂-treated soil indicates that imogolite and proto-imogolite allophanes are concentrated in podzolic B₂ and B₃ horizons, and make up at least 6 percent of one B₂ horizon soil, which contains virtually no layer silicate clays. It is argued here that imogolite-type components are the principal source of extractable aluminium and silicon in such horizons, that they may act as cementing agents in indurated horizons, and that proto-imogolite, a soluble aluminium-silicate complex, is the predominant mobile form in which aluminium is transported to B₂ and lower horizons of podzols. Comparison of the amounts of aluminium extracted by acetic acid with those extracted by EDTA indicates that extractable aluminium in Bhg, Bh, and organic-rich A₂ horizons is present principally in organic complexes. It is proposed that the aluminium fulvates concentrated in these horizons are formed in situ.     

Near-infrared spectroscopy for analysis of chemical and microbiological properties of forest soil organic horizons in a heavy-metal-polluted area

In industrial areas, heavy metals may accumulate in forest soil organic horizons, affecting soil microorganisms and causing changes in the chemical composition of the accumulated organic matter. The objectives of this study were to test the ability of near-infrared spectroscopy (NIRS) to detect heavy metal effects on the chemical composition of forest soil O horizons and to test whether NIRS may be used to quantitatively determine total and exchangeable concentrations of Zn and Pb (Zn_t, Pb_t, Zn_ex, Pb_ex) and other chemical and microbial properties in forest soil O horizons polluted with heavy metals. The samples of O horizons (n = 79) were analyzed for organic C (C_org), total N and S (N_t, S_t), Zn_t, Pb_t, Zn_ex, Pb_ex, basal respiration (BR), microbial biomass (C_mic) and C_mic-to-C_org ratio. Spectra of the samples were recorded in the Vis-NIR range (400–2,500 nm). To detect heavy-metal-induced changes in the chemical composition of O horizons principal components (PC1–PC7) based on the spectral data were regressed against Zn_t + Pb_t values. A modified partial least squares method was used to develop calibration models for prediction of various chemical and microbial properties of the samples from their spectra. Regression analysis revealed a significant relationship between PC3 and PC5 (r = −0.27 and −0.34, respectively) and Zn_t + Pb_t values, indicating an effect of heavy metal pollution on the spectral properties of the O horizons and thus on their chemical composition. For quantitative estimations, the best calibration model was obtained for C_org-to-N_t ratio (r = 0.98). The models for C_org, N_t, and microbial properties were satisfactory but less accurate. NIRS failed to accurately predict S_t, C_org-to-S_t, Zn_t, Pb_t, Zn_ex, and Pb_ex.     

Apparent cation-exchange equilibria in podzolic forest soils

The Gaines–Thomas selectivity coefficient, K, was used to express the relation between the cations in solution and the cations in exchange sites in podzolic forest soils. Soil solution was obtained by centrifuging a fresh bulked soil sample. Exchangeable cations HX, AlX, CaX, MgX and KX and effective cation-exchange capacity, CEC_e, were determined with 0.1 m BaCl₂. Apparent values of K indicated a preference of Ca²⁺ over Mg²⁺ and over Al³⁺ in O, A and B horizons (log K_Al–Ca < 0 and log K_Mg–Ca < 0), whereas log K_K–Ca and log K_H–Ca exceeded zero. The horizons were similar with respect to log K_H–Ca, and the differences in log K_Mg–Ca were small. Log K_K–Ca and log K_Al–Ca increased in the horizons in the order O < A < B. Log K_Al–Ca was not significantly correlated with the fraction AlX/CEC_e. Log K_Mg–Ca was positively correlated with the fractions HX/CEC_e and AlX/CEC_e, and negatively correlated with log (CaX/MgX). The selectivity coefficient of binary cation exchange seemed to be applicable to in situ soil solutions. However, the fraction of each cation on exchange sites should be based on the CEC_e rather than on the sum of the two cations. The latter, also, seemed to be acceptable in cases of exchangeable cations with a large relative content in soil, e.g. in Al³⁺–Ca²⁺ exchange in A and B horizons, and in H⁺–Ca²⁺ exchange in O and A horizons.     

Evaluation of the factors affecting direct polarization solid state 31P-NMR spectroscopy of bulk soils

³¹P‐NMR spectroscopy on bulk soils is a powerful tool for the identification of the different phosphorus forms in soils and for the evaluation of the dynamics of soil P. Up to now the majority of the papers dealt with liquid state ³¹P‐NMR spectroscopy on soluble soil organic substances. Only few papers were addressed to the study of the different phosphorus forms directly in bulk soils. In the present paper, some organic and inorganic phosphates of known structures, which are likely to be present in soil systems, were studied by direct polarization (DP) magic angle spinning (MAS) ³¹P‐NMR spectroscopy in order to understand the electronic factors responsible for chemical shifts of the phosphorus (P) nucleus and to serve as guidelines to assign P resonances in soil spectra. Number of hydrating water molecules, type of counter‐cation, degree of covalence, and spatial conformation of P in phosphate structures were found to affect signal positions in ³¹P‐NMR spectra. Both hydrating water and increase in degree of covalence of the X‐O‐P bonds (X=H, Na) enhanced the electronic density (E_D) around P, thereby producing up‐field shifts in ³¹P‐NMR spectra. The exchange of the Na⁺ counter‐cation with NH₄⁺ resulted in an increase of the cation potential (P_C) that is a measure of the cation polarizing power, and induced a down‐field shift of P signals, due to a corresponding reduction in E_D around the P nucleus. Both NMR down‐ and up‐field shifts were observed in organic phosphates, and were dependent on the spatial orientation of the phosphate groups that may have been fixed anisotropically in the solid state. Based on the factors that influence P chemical shifts for standard phosphates, attempts to assign ³¹P‐NMR signals in the spectra of five different unperturbed bulk soils were made.     

Geogenic CO2 affects stabilization of soil organic matter

The soil on mofette sites is affected by ascending geogenic carbon dioxide (CO₂), which partially fills the soil atmosphere. We hypothesized that geogenic CO₂ affects the stabilization of soil organic matter (SOM) at lower partial pressures than had been discussed previously for mofette sites. We studied loamy Ah horizons (n = 22; pH 3.4–4) of the soil along a transect on a grassland mofette site in the northwest Czech Republic with CO₂ partial pressures (p(CO₂)) of up to 0.52. The samples were fractionated by particle size, density and solubility (water‐soluble organic matter (WSOM)), and analysed quantitatively for organic carbon (C) and total nitrogen (N) and qualitatively (¹³C‐NMR spectroscopy). Soil OM with a narrower C:N ratio accumulated in the clay fraction, but at p(CO₂) less than approximately 0.1 the proportion of SOM in the clay fraction relative to total SOM tended to decrease with increasing p(CO₂), whereas that of particulate organic matter (POM) fractions increased with increasing p(CO₂). We attribute the distribution of SOM among the mineral soil and POM to decreased interactions with minerals of the clay fraction. The formation of iron (Fe) hydroxides, which potentially sorb SOM, was not affected negatively by CO₂. The potential reactivity of Fe hydroxides was even positively affected by increased p(CO₂). Export of dissolved SOM into the subsoil might increase at mofette sites because of the large amounts of WSOM and decreasing interactions with minerals of the clay fraction. Therefore, our results show negative effects of CO₂ on SOM stabilization even at moderate p(CO₂).     

Soil microbial biomass and activity: the effect of site characteristics in humid temperate forest ecosystems

Microbial biomass, respiratory activity, and in‐situ substrate decomposition were studied in soils from humid temperate forest ecosystems in SW Germany. The sites cover a wide range of abiotic soil and climatic properties. Microbial biomass and respiration were related to both soil dry mass in individual horizons and to the soil volume in the top 25 cm. Soil microbial properties covered the following ranges: soil microbial biomass: 20 µg C g^–1–8.3 mg C g^–1 and 14–249 g C m^–2, respectively; microbial C–to–total organic C ratio: 0.1%–3.6%; soil respiration: 109–963 mg CO₂‐C m^–2 h^–1; metabolic quotient (qCO₂): 1.4–14.7 mg C (g C_mic)^–1 h^–1; daily in‐situ substrate decomposition rate: 0.17%–2.3%. The main abiotic properties affecting concentrations of microbial biomass differed between forest‐floor/organic horizons and mineral horizons. Whereas microbial biomass decreased with increasing soil moisture and altitude in the forest‐floor/organic horizons, it increased with increasing N_tot content and pH value in the mineral horizons. Quantities of microbial biomass in forest soils appear to be mainly controlled by the quality of the soil organic matter (SOM), i.e., by its C : N ratio, the quantity of N_tot, the soil pH, and also showed an optimum relationship with increasing soil moisture conditions. The ratio of C_mic to C_org was a good indicator of SOM quality. The quality of the SOM (C : N ratio) and soil pH appear to be crucial for the incorporation of C into microbial tissue. The data and functional relations between microbial and abiotic variables from this study provide the basis for a valuation scheme for the function of soils to serve as a habitat for microorganisms.     

Radiological maps for fallout 7Be in forest soil horizons in a mountainous area of Turkey

Due to the paucity of data on separate spatial distribution of cosmogenic ⁷Be radionuclide activities in forest soil layers, a spatial study was performed in Mount Ida (Kazdagi)/Edremit, Turkey. In this study, it was aimed to examine the ⁷Be spatial variability and depth distribution in the surface soil layers. The ⁷Be activity concentrations were determined by HPGe gamma spectrometry system and the distributions of ⁷Be activities in the O_L and O_F + O_H horizons throughout the region were mapped separately. Activity concentrations of ⁷Be in O_L horizons and O_F+O_H horizons varied as 35 ± 23–701 ± 40 Bq kg^?1 and 0.96 ± 0.63–197 ± 11 Bq kg^?1, respectively. ⁷Be inventories (0.20 ± 0.06–5.69 ± 0.75 kBq m^?2) in the study area were relatively higher when compared with the other regions of the world. ⁷Be inventories increased with altitude, slope and the thickness of the humus layer in some of the investigated area. Average ⁷Be activity level in deciduous forest stand type was significantly higher than that for coniferous and mixed stand types. Our limited data could not provide a latitudinal distribution pattern of ⁷Be soil inventory or precipitation dependence and further investigation is needed.     

Chemical composition of young and old carbon pools throughout Cambisol and Luvisol profiles under forests

The long-term storage of soil organic matter (SOM) in forest soils is still poorly understood. In this study, particle size fractionation in combination with accelerator mass spectroscopy (AMS) and solid state ¹³C nuclear magnetic resonance (NMR) spectroscopy was applied to investigate organic carbon (OC) stabilisation in Cambisol and Luvisol profiles under spruce (Picea abies) and beech (Fagus sylvatica L.) forests. In most samples, OC was preferentially associated with <2 μm fractions. Throughout soil profiles the contribution of OC in the clay fraction to the total OC increased from 27%-53% in A horizons to 44-86% in E, B and EB horizons. The 200-2000 μm fractions from all sites and all depths showed a percentage of modern C (pmC)>100. They were enriched in ¹⁴C owing to high inputs of recent material from leaves and roots. Clearly less active material was associated with <2 and 2-20 μm fractions. This demonstrated that the particle size fractionation procedure applied to our study was capable to isolate a young OC fraction in all samples. The pmC values were strongly decreasing with depth but the decrease was much more pronounced in the fine fractions. The <2 and 2-20 μm fractions of B, E and EB horizons revealed radiocarbon ages between 512 and 4745 years before present which indicated that the SOM in those horizons was little affected by the recent vegetation. The major components of labile and stable SOM pools in topsoils and subsoils were always O/N-alkyl C (28-53%) and alkyl C (14-48%) compounds. NMR spectra of bulk soils and particle size fractions indicated that high alkyl C and O/N-alkyl C proportions throughout the soil profile are typical of Cambisols and Luvisols which were not subjected to regular burning. A relation between radiocarbon age and chemical composition throughout soil profiles was not observed. This suggests that the long-term stabilisation of SOM is mainly controlled by the existence of various mechanisms of protection offered by the soil matrix and soil minerals but not by the chemical structure of SOM itself.