HUMUS TYPE DISCRIMINATION USING PATTERN RECOGNITION OF THE MASS SPECTRA OF VOLATILE PYROLYSIS PRODUCTS

Mull and mor humus can be distinguished in freely drained British surface soils by the pyrolysis products derived from whole soil samples. About i milligram of soil is pyrolysed at 770 °C in a Curie point apparatus and a sample of the volatile decomposition products is allowed to enter a low-resolution mass spectrometer. A numerical value (the ‘Discriminator Value’) which will discriminate between the two humus types is then calculated from the spectrum of each sample. This is performed by multiplying the intensity of each mass peak by a weight factor and then summing the weighted intensities up to mass 110 The weight factors are obtained empirically by taking sets of spectra from clearly distinguished mull and mor samples and applying a computerized learning machine procedure. Once obtained, they are relatively easily applied to spectra from other soils. The method places all samples on a numerical scale on which mull types appear positive up to about 20 × 10⁸ and mor types negative down to about -15 × 10³, intermediate types being recognized in about the middle of the range. It is indicated that the most important pyrolysis products active in the discrimination process are the olefin hydrocarbons, particularly ethylene, which are produced in greater abundance from mor humus.     

Fluoride-induced changes in chemical properties and microbial activity of mull,moder and mor soils

Summary Fluoride-induced changes of chemical properties and microbial activities in humus soils were investigated in 12-week lysimeter experiments. The mull soil showed the highest F-adsorption capacity, in which 94% of the fluoride added was retained after addition of 4.5 mg F/cm² as NaF. The moder and mor soils only adsorbed 52% and 41%, respectively. F-additions induced leaching of organic matter, Fe, Al and P and increases in soil pH in the moder and mor. In contrast no Al, Fe and P was leached from the mull and only minor amounts of organic matter dissolved after a single application of 4.5 mg F/cm². Treatments with NaF up to 3700 mg F/kg did not significantly reduce respiration in any of the humus forms. Dehydrogenase, alkaline phosphatase and arylsulfatase activities as well as nitrification were inhibited at much lower F-additions in the moder and mor soils. A significant decrease in ammonification was observed in the moder. In contrast, microbial processes in the mull soil were not inhibited. This is due to its high adsorption capacity and the relatively low toxicity of F-ions. According to computations using GEOCHEM, the F-ion was the most abundant species in mull lysimeter leachates. Leachates of moder and mor soils contained mainly AIF-complexes (90%–99%). The lack of any effects from NaF treatment on soil respiration is attributed to the observed positive effects, e.g. dissolution of organic matter, desorption of P and increases in soil pH.     

Chemical composition of the organic matter in forest soils: The humus layer

Decomposition and humification were studied within three types of forest humus (mull, moder, and mor) by means of CPMAS ¹³C NMR spectroscopy combined with degradative methods. The NMR data show that O-alkyl carbon decreases in all soils, and alkyl as well as carboxyl carbon increase as depth and decomposition increase; the percentage of aromatic carbon remains constant at about 25%. With increasing depth the amount of carbon that can be identified as belonging to specific compound classes by wet chemical methods decreases from 60% to 40%. Microbial polysaccharides and the proportion of non polysaccharide O-alkyl carbon increase with depth. A selective preservation of recalcitrant, condensed lignin structural units is also observed. In order to relate the spectroscopic and chemical data from investigations of whole soils with studies of humification, samples were fractionated into fulvic acid, humic acid, and humin fractions. The fulvic acid fraction contains large concentrations of carbohydrates irrespective of the soil horizon. The humic acid fraction contains less polysaccharides, but high amounts of alkyl carbon and aromatic structures. The percentage of aromatic carbon existing in the humic acid fraction increases with depth, probably reflecting the amount and degree of oxidative decomposition of lignin. A loss of methoxyl and phenolic groups is evident in the ¹³C NMR spectra of the humic acid fraction. The humin fraction resembles relatively unchanged plant-derived materials as evident from the lignin parameters and carbohydrate contents. All the observed data seem to indicate that humic acids originate form oxidative degradation of humin or plant litter.     

Polycyclic aromatic hydrocarbons in different forest soils: Mineral horizons

The objective of this study was to assess the behavior of PAH in mineral soil horizons of different forest soils (Allersdorf, All: Inceptisol, mull humus type; Geisberg, Geis: Entisol, mull; Hohe Matzen, HoM: Spodosol, mor). At the mor site, the highest PAH loading was observed in the forest floor (HoM L to Oh, ΣX 20 PAH: 829 g ha^?1), whereas at the mull sites the humified mineral soil horizons were the main sink for PAH (All aAxh, Σ 20 PAH: 522 g ha^?1). In all soils, there was a significant PAH translocation into subsoil horizons (Σ 20 PAH in the subsoil: 76–195 g ha^?1). In order to delineate possible transport mechanisms, double-logarithmic relationships were established between the translocation of the distinct PAH from the surface soil to the subsoil and the PAH's K_ow values. The data suggested that transport of low-molecular PAH into the subsoil was primarily a function of the water solubility of each compound. In the biologically active All and Geis soils, high-molecular PAH were translocated independently from their K_ow value, and particle-bound transport probably by soil burrowing animals was assumed to control translocation of the penta- and hexacyclic PAH. In contrast, at HoM transfer of high-molecular PAH increased with increasing hydrophobicity, suggesting dissolved organic matter (DOM)-mediated transport of PAH. Fractionation of soil into a floatable fraction and into sand- (20–2000 μm), silt- (2–20 μm), coarse clay- (0.2–2 μm), and fine claysized (< 0.2 μm) separates revealed that more than 80% of the PAH loading could be assigned to silt- and coarse clay-sized separates, irrespective of the soil's texture (loamy sand to silty clay loam). Silt generally showed the highest C_org?related PAH concentrations. PAH profiles (relative proportion of each PAH on the sum of 20 PAH) revealed increasing proportions of high-molecular, more refractory PAH from the floatables and the sand-sized separates to the finer particles, corresponding with an increasing degree of SOM alteration in the same direction. At HoM, depth gradients of high-molecular PAH suggested co-transport of penta- and hexacyclic PAH with DOM and subsequent co-sorption selectively to the silt- and coarse-clay sized separates of the Bsh horizon.     

Über Sorption und Wirkung von Blei auf die biologische Aktivität terrestrischer Humusformen

Lead sorption and effect of lead pollution on biological activity of different types of humus forms Effects of Pb(NO₃)₂ on biological activity (e. g. respiration and enzyme activity) of mull, moder and mor soils were investigated under controlled laboratory conditions. Lead sorption capacity of investigated humus forms decreased in the order mull > moder > mor. Soil respiration was inhibited after addition of 10 mg Pb/g soil at lead concentrations > 1 μg Pb/ml of soil solutions of the mor and moder profiles. Highly significant positive regression coefficients were obtained for decreases in soil respiration and decreases in dehydrogenase-, phosphatase- and arylsulfatase activities of O-horizons. It is assumed that minor enzymatic acitivities after lead addition result from its effect on enzyme producing organisms. After additions of 200 mg Pb/g soil biological activities of investigated humus layers were also affected by a marked increase of acidity of soil solutions. This ?secondary”? effect was also obtained using Ca(NO₃)₂ in pollution experiments.     

A re‐evaluation of the enriched labile soil organic matter fraction

Identifying ‘functional' pools of soil organic matter and understanding their response to tillage remains elusive. We have studied the effect of tillage on the enriched labile fraction, thought to derive from microbes and having an intermediate turnover time. Four soils, each under three regimes, long‐term arable use without tillage (NT), long‐term arable under conventional tillage (CT), and native vegetation (NV), were separated into four aggregate size classes. Particle size fractions of macro‐ (250–2000 μm) and microaggregates (53–250 μm) were isolated by sonication and sieving. Subsequently, densiometric and chemical analyses were made on fine‐silt‐sized (2–20 μm) particles to isolate and identify the enriched labile fraction. Across soils, the amounts of C and N in the particle size fractions were highly variable and were strongly influenced by mineralogy, specifically by the contents of Fe and Al oxides. This evidence indicates that the fractionation procedure cannot be standardized across soils. In one soil, C associated with fine‐silt‐sized particles derived from macroaggregates was 567 g C m^?2 under NV, 541 g C m^?2 under NT, and 135 g C m^?2 under CT, whereas C associated with fine‐silt‐sized particles derived from microaggregates was 552, 1018, 1302 g C m^?2 in NV, NT and CT, respectively. These and other data indicate that carbon associated with fine‐silt‐sized particles is not significantly affected by tillage. Its location is simply shifted from macroaggregates to microaggregates with increasing tillage intensity. Natural abundance ¹³C analyses indicated that the enriched labile fraction was the oldest fraction isolated from both macro‐ and microaggregates. We conclude that the enriched labile fraction is a ‘passive' pool of soil organic matter in the soil and is not derived from microbes nor sensitive to cultivation.     

Interactions between tree seedling roots and humus forms in the control of soil C and N cycling

The hypothesis that roots enhance soil-N turnover in humified soil organic matter (SOM) (mull) but not in lignified SOM (mor) was tested in a study involving the growth of eight species of tree seedlings on the two contrasting humus forms. After 12 and 22 weeks of seedling growth, soil-CO₂ efflux was measured with (1) growing seedlings, and after 22 weeks, with (2) roots only, shoots excised, and (3) with roots removed and soils amended with different rates of glucose. Indices of C-flux and of soil available-C were derived and compared to plant-N uptake, extractable soil mineral-N, anaerobically mineralized soil-N, N bioavailability to Agrostis grass following harvest of seedlings, and to seedling fine root C-chemistry. Significant soil x species interactions were found for total soil-CO₂ efflux, root-dependent CO₂, soil available-C and microbial biomass. In all cases, roots were important contributors to C-cycling in the mull soil but not in the mor soil. C was more limiting in the mor than in the mull microbial community. Plant-N uptake and the mineral-N pool was greater in the mor soil, reflecting that soil's higher specific N-supplying capacity (N-mineralized:CO₂). Seedlings decreased the mineral-N pool in both soils, but the presence of roots increased N-mineralization in the mull soil and decreased N-mineralization in the mor soil. Significant positive relationships were observed in the mull soil only between soil respiration and plant N uptake at mid-season, and between soil respiration and N-mineralization at late-season. Birch root activity in the mull soil was greater than that of all other seedlings and this observation is discussed with respect to the autecology of birch. Soil respiration correlated with the non-polar extract content but not the lignin:N ratio of fine roots. Results suggest that root-released C in mull SOM is sufficient to relieve energy limitation to soil microbes and allow them to access appreciable amounts of soil-N, whereas ligninolytic activity, which may ultimately control soil-N turnover in mor SOM, is not increased by rhizodeposition.     

Humus forms and metal pollution in soil

Smelters in northern France are a serious source of soil pollution by heavy metals. We have studied a poplar plantation downwind of an active zinc smelter. Three humus profiles were sampled at increasing distance from the smelter, and the thickness of topsoil horizons was measured along a transect. We analysed the vertical distribution of humus components and plant debris to assess the impact of heavy metal pollution on the humus forms and on soil faunal activity. We compared horizons within a profile, humus profiles between them, and traced the recent history of the site. Near the smelter, poplar trees are stunted or dead and the humus form is a mor, with a well‐developed holorganic OM horizon. Here faunal activity is inhibited, so there is little faecal deposition and humification of plant litter. At the distant site poplar grows well and faunal activity is intense, so there are skeletonized leaves and many organo–mineral earthworm and millipede faecal pellets. The humus form is a mull, with a well‐developed hemorganic A horizon. The passage from mor to mull along the transect was abrupt, mor turning to mull at 250 m from the smelter, though there was a progressive decrease in heavy metal deposition. This indicates that there was a threshold (estimated to be 20 000 mg Zn kg^?1) in the resilience of the soil foodweb.     

Organische Stoffgruppen im Mullhumus nicht kultivierter Böden mit besonderer Berücksichtigung der Stickstoff-Fraktionen

Fractions of organic components in mull humus of non cultivated soil profiles with special reference to various nitrogen fractions Different fractions of organic components were studied by horizons in four mull humus profiles, differing in genesis and ecology. Two of the soils were located in unmanaged grassland (Rendoll and Entisol) and two under deciduous hardwood (Eutrochept and Fluvaquent). In the grassland soils characteristic F-mull developed, but in the woodland soils L – and wet mull occurred respectively. Water soluble-, hemicellulose-, cellulose sugars and lignin derivates decreased with increasing soil depth. In contrast, amino sugars, proteins, lipids and unknown nitrogen containing fractions increased. Essential changes of those fractions happened in the organic-mineral horizons. Some clear differences among the profiles were recorded, depending on litter type, the genesis and soil water regime. At least 41% (Rendoll) to at most 50% (Fluvaquent) of the organic substance were extractable and identified. Amounts and distribution of the different organic fractions in the litter layers depend on the chemical composition of the litter. Hydrolysable unknown N, non hydrolysable and pseudo amide N increased from the litter to the mineral horizons in the Eutrochrept from 34 to 44 and in the Rendoll from 27 to 49% of total N, but in the Entisol these fractions are decreasing from 52 to 43% of total N. No change was observed in the Fluvaquent. In contrast, amino acid-, amino sugar – and true amide N decreased in most cases from the litter to the mineral horizons. Inorganic bound N, nearly exclusive fixed NH₄⁺-N, reached not more than 5% of total nitrogen.     

Fertilization effects on organic matter in physically fractionated soils as studied by 13C NMR: Results from two long-term field experiments

^l3C–nuclear magnetic resonance (NMR) spectra taken using magic–angle spinning (MAS), cross polarization (CP) and with total suppression of side bands (TOSS) are reported for soils from two long–term field experiments. One set of soils was from the Broadbalk Experiment at Rothamsted, UK (monoculture of winter wheat since 1843) and the other was from the Lermarken site of the Askov Long–Term Experiment on Animal Manure and Mineral Fertilizers (arable rotation since 1894). At both sites soil samples were taken from three fertilizer treatments: nil, inorganic fertilizers, animal manure. Spectra were obtained from whole soil samples and from the size fractions clay (<2 μrn), silt (2–20 μm) and, in some cases, sand (20–2000 μm). Comparison of the total strengths of the ¹³C–NMR signal for each size separate in relation to its total organic C content shows that clay, particularly, contains large percentages of C not detected by NMR because of the large magnetic susceptibilities of the soil minerals. It is proposed that the observed signals come from the more labile pools of soil organic matter (SOM), on the presumption that these pools are less closely associated with soil minerals and iron oxides and are likely to be less protected from microbial or enzymic decomposition. For both Rothamsted and Askov, functional groups in the 45–110 ppm region (N– and O–alkyls) dominate in the spectra for whole soils, with aromatics (110–160 ppm) and alkyls (0–45 ppm) signals being the next prominent. In the Askov whole soil samples ¹³C–NMR revealed no differences between nil, inorganic fertilizer and animal manure treatments but in the Rothamsted whole soil there were some small differences. Clay and silt fractions from Askov contain more alkyls and less aromatics than those from Rothamsted. For both sites clay in enriched in alkyls and depleted in aromatics relative to silt. Clay from Askov, but not Rothamsted, contains more N–alkyls (45–65 ppm) and less acetals (90–110 ppm) than silt. O–alkyls (65–90 ppm) account for more than 20% of the total signal in clay and silt from both sites. Fertilization regimes have not significantly affected the chemical composition of SOM associated with clay– and silt–sized fractions in the soils at either site. We conclude that the chemical composition of SOM is determined primarily by the interaction between the organisms responsible for decomposition and the mineral soil matrix rather than the nature of substrate input.     

Characterization of cultivation effects on soil organic matter

Humus properties in various Ap horizons from field plots, that have been cultivated in long-term experiments under different management conditions, were investigated by pyrolysis-field ionization mass spectrometry (Py-FIMS) and ¹³C-NMR spectroscopy. The results of Py-FIMS were evaluated by correlation and principal component analysis from reproducible data sets of bulk soil samples and extracted humic substances, and allowed a distinct discrimination on the basis of humus quality and composition. The chemical subunits suitable for discrimination are the major plant constituents carbohydrates, lignin, and proteinaceous materials as well as their humification products. The contribution of these compound classes to soil organic matter decreased with the intensity of management. CPMAS and solution ¹³C NMR spectra of soils and humic substances demonstrated that with more intense management, both the intensities of the phenolic region (140–160 ppm) and the aromatic region (110–140 ppm) decreased. The combination of both independent methods MS and NMR, together with microbiological and biochemical data, yields the general result that intensive soil management leads to a less active humus.     

Nitrogen distribution and 15N natural abundances in particle size fractions of a long‐term agricultural field experiment

The present study combined a physical fractionation procedure with the determination of the natural abundance of ¹⁵N to investigate the impact of organic manure and mineral fertilizer application, and fallow on changes of N associated with different soil particle size fractions. The long‐term field experiment was conducted since 1956 in Ultuna, Sweden, on an Eutric Cambisol. Nitrogen in bulk soil and in particle size fractions changed significantly since 1956. The N_t concentrations in bulk soil decreased in all treatments not receiving organic materials. Comparing the N contribution of particle‐size fractions to the total N amount revealed the following ranking: silt > clay > fine clay > fine sand > coarse sand. The relative contribution of N in silt sized particles significantly increased from low to high bulk soil N contents, whereas N in clay and fine clay fractions decreased. The C : N ratios of particle size fractions differed considerably more between treatments than C : N ratios in bulk soils. Generally, the C : N ratios decreased from coarse to fine fractions emphasizing the tendency of smaller fractions being more significant as N sink than as C_org sink. ¹⁵N abundances varied more between particle size fractions of single treatments than between bulk soil from differently treated plots. Within treatments we observed differences of up to 7.1 ‰ between particle size fractions. In most cases δ ¹⁵N values increased with decreasing particle sizes. This pattern on average was similar to changes in δ ¹³ C. Our results suggest that silt sized particles acted as medium‐term sink of introduced N and that ¹⁵N abundances in particle size fractions sensitively reflect changes in N status in response to soil management.     

长江三角洲地区土壤环境质量与修复研究 Ⅳ.多环芳烃在土壤不同有机质组分中分配特征的研究

多环芳烃(PAHs)在土壤不同活性有机质库中的分配会影响它们在土壤中的迁移和生物有效性。本研究采用土壤有机无机复合体的分组方法,分离出以游离态有机物质存在的轻组和以有机无机复合体存在的重组,研究了15种美国环境保护署(USEPA)优控的PAHs在土壤轻组和重组以及重组结合态腐殖质不同组分中的分配特征。结果表明,轻组中PAHs总量的含量范围为1.30×104~1.07×105μg kg-1,远远高于PAHs总量的含量为221.7~297.8μg kg-1的重组。土壤中轻组的含量虽然只有0.4%~2.3%,但它结合的PAHs量却占土壤中PAHs总量的31.5%~69.5%。重组中PAHs含量主要分布在紧结态腐殖质中,占重组PAHs总量71.2%~87.2%。结合态腐殖质不同组分中PAHs的含量与它们有机碳的含量呈显著性正相关(p<0.01),紧结态腐殖质对PAHs的富集能力显著高于稳结态和松结态腐殖质。PAHs污染土壤的环境风险可能主要在于轻组结合的PAHs。     

Studies of nitrogen immobilization and mineralization in calcareous soils—II: Mineralization of immobilized nitrogen from soil fractions of different particle size and density

¹⁵NO^?₃ was immobilized in a calcareous sandy soil and a calcareous clay soil each incubated with glucose and wheat straw. Net mineralization of organic-¹⁵N was more rapid in the sandy soil, irrespective of C amendment, and in soils amended with glucose. Intermittent drying and wetting of soils during incubation stimulated mineralization of ¹⁵N-labelled and native soil organic-N in all treatments. The availability (percentage mineralization) of recently-immobilized ¹⁵N consistently exceeded that of the native soil N. Ratios of the availability of labelled and unlabelled N were similar in the sandy and clay soils but varied according to C amendment, drying and wetting cycle and incubation period.Changes in the distribution of immobilized N amongst soil extracts and soil fractions of different particle size and density were determined during periods of net N mineralization. In straw-amended soils, the organic-¹⁵N of a light fraction, sp.gr. < 1.59, decomposed relatively rapidly during the late mineralization period. Decreases of organic ¹⁵N of the fine clay fraction were also recorded. In glucose-amended soils, net N mineralization was accompanied by significant decreases in the concentrations of organic-¹⁵N of the silt and fine clay fractions.Drying and rewetting of soils hastened or magnified changes occurring in the organic-¹⁵N of soil fractions, but qualitatively, the pattern of change was similar to that observed with soils incubated under uniformly-moist conditions.The percentage distribution of labelled and unlabelled N suggested that in the long term, the silt fraction will accumulate an increasing proportion of the more stable nitrogenous residues.     

Variation of four phosphorus properties in woodland soils

Variation in total, organic and available-P contents and phosphatase activity of P-deficient soils of some English Lake District woodlands of differing vegetative composition were examined in relation to individual woodlands, two depths in the soil profile, mull, moder and mor humus types, and different times of the year. Depth in the soil profile was a more important source of variation in the P properties than different woodlands. Soils in individual woodlands differed in their degree of variability in the four P properties. Available P contents and phosphatase activities were more variable than total and organic P contents. Available-P and organic-P contents and phosphatase activity showed seasonal variation. Seasonal variation in available-P was almost as great as differences in available-P between woodlands. Total and organic-P contents showed similar patterns of variation with respect to individual woodlands, humus type and soil depth. Differences in degree of variation within woodlands and differences in degree and pattern of variation of the four P-properties may need to be taken into account in soil sampling programmes of studies comparing soils under differing vegetation regimes.Different interpretations of the variation in the soil-P properties were obtained by expressing the data respectively in terms of soil weight (g^?1 soil) or soil volume (cm^?1 soil), due to marked variation in bulk-densities of the woodland soils. It is suggested that where soils vary in bulk-density, soil data should be expressed in terms of soil volume.The P-deficiency of the woodland soils is probably associated with the relatively low total P content per unit volume of soil and the high proportion of it which is organically bound.     

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.     

Improvement of 13C and 15N CPMAS NMR spectra of bulk soils, particle size fractions and organic material by treatment with 10% hydrofluoric acid

The small organic matter content of mineral soils makes it difficult to obtain ¹³C and ¹⁵N nuclear magnetic resonance (NMR) spectra with acceptable signal-to-noise ratios. Subjecting such samples to hydrofluoric acid removes mineral matter and leads to a relative increase in organic material. The effect of treatment with 10% hydrofluoric acid on bulk chemical composition and resolution of solid-state ¹³C NMR spectra was investigated with six soils, some associated particle size fractions, plant litter and compost. The treatment enhanced the signal-to-noise ratio of the solid-state ¹³C NMR spectra. The improvement in spectrum quality was greatest in the clay fraction of soil contaminated with coal ash. The removal of paramagnetic compounds associated with the ash may be the main reason for the improvement. Based on total C, total N, C/N ratio and intensity distribution of the solid-state ¹³C NMR spectra, no changes in organic matter composition could be detected, except for a possible loss of carbohydrates. After treatment with HF, solid-state ¹⁵N NMR spectra of particle size fractions were obtained and indicated that the observable nitrogen is present mostly as peptides and free amino groups. Extraction with hydrofluoric acid is recommended as a routine treatment prior to solid-state ¹³C and ¹⁵N NMR on soil containing little C or N and soil samples containing paramagnetic compounds from natural or anthropogenic sources.     

Polycyclic Aromatic Hydrocarbons Content in Contaminated Forest Soils with Different Humus Types

The aim of the study was to determine polycyclic aromatic hydrocarbon (PAH) content in different forest humus types. The investigation was carried out in Chrzanów Forest District in southern Poland. Twenty research plots with different humus types (mor and mull) were selected. The samples for analysis were taken after litter horizons removing from a depth of 0–10 cm (from the Of- and Oh-horizon total or A-horizon). pH, organic carbon and total nitrogen content, base cations, acidity, and heavy metal content were determined. In the natural moisture state, the activity of dehydrogenase was determined. The study included the determination of PAH content. The conducted research confirms strong contamination of study soil by PAHs and heavy metals. Our experiment provided evidence that different forest humus types accumulate different PAH amounts. The highest content of PAHs and heavy metals was recorded in mor humus type. The content of PAHs in forest humus horizon depends on the content and quality of soil organic matter. Weaker degradation of hydrocarbons is associated with lower biological activity of soils. The mull humus type showed lower content of PAHs and at the same time the highest biological activity confirmed by high dehydrogenase activity.     

Redistribution of particulate organic matter during ultrasonic dispersion of highly weathered soils

The use of ultrasonic energy for the dispersion of aggregates in studies of soil organic matter (SOM) fractionation entails a risk of redistribution of particulate organic matter (POM) to smaller particle‐size fractions. As the mechanical strength of straw also decreases with increasing state of decomposition, it can be expected that not all POM will be redistributed to the same extent during such dispersion. Therefore, we studied the redistribution of POM during ultrasonic dispersion and fractionation as a function of (i) dispersion energy applied and (ii) its state of decomposition. Three soils were dispersed at different ultrasonic energies (750, 1500 and 2250 J g^?1 soil) or with sodium carbonate and were fractionated by particle size. Fraction yields were compared with those obtained with a standard particle‐size analysis. Undecomposed or incubated (for 2, 4 or 6 months) ¹³C‐enriched wheat straw was added to the POM fraction (0.25–2 mm) of one of the soils before dispersion and fractionation. Dispersion with sodium carbonate resulted in the weakest dispersion and affected the chemical properties of the fractions obtained through its high pH and the introduction of carbonate. The mildest ultrasonic dispersion treatment (750 J g^?1) did not result in adequate soil dispersion as too much clay was still recovered in the larger fractions. Ultrasonic dispersion at 1500 J g^?1 soil obtained a nearly complete dispersion down to the clay level (0.002 mm), and it did not have a significant effect on the total amount of carbon and nitrogen in the POM fractions. The 2250 J g^?1 treatment was too destructive for the POM fractions since it redistributed up to 31 and 37%, respectively, of the total amount of carbon and nitrogen in these POM fractions to smaller particle‐size fractions. The amount of ¹³C‐enriched wheat straw that was redistributed to smaller particle‐size fractions during ultrasonic dispersion at 1500 J g^?1 increased with increasing incubation time of this straw. Straw particles incubated for 6 months were completely transferred to smaller particle‐size fractions. Therefore, ultrasonic dispersion resulted in fractionation of POM, leaving only the less decomposed particles in this fraction. The amounts of carbon and nitrogen transferred to the silt and clay fractions were, however, negligible compared with the total amounts of carbon and nitrogen in these fractions. It is concluded that ultrasonic dispersion seriously affects the amount and properties of POM fractions. However, it is still considered as an acceptable and appropriate method for the isolation and study of SOM associated with silt and clay fractions.     

Transformation of organic matter from maize residues into labile and humic fractions of three European soils as revealed by 13C distribution and CPMAS-NMR spectra

The dynamics of incorporation of fresh organic residues into the various fractions of soil organic matter have yet to be clarified in terms of chemical structures and mechanisms involved. We studied by ¹³C‐dilution analysis and CPMAS‐¹³C‐NMR spectroscopy the distribution of organic carbon from mixed or mulched maize residues into specific defined fractions such as carbohydrates and humic fractions isolated by selective extractants in a year‐long incubation of three European soils. The contents of carbohydrates in soil particle size fractions and relative δ¹³C values showed no retention of carbohydrates from maize but rather decomposition of those from native organic matter in the soil. By contrast, CPMAS‐¹³C‐NMR spectra of humic (HA) and fulvic acids (FA) extracted by alkaline solution generally indicated the transfer of maize C (mostly carbohydrates and peptides) into humic materials, whereas spectra of organic matter extracted with an acetone solution (HE) indicated solubilization of an aliphatic‐rich, hydrophobic fraction that seemed not to contain any C from maize. The abundance of ¹³C showed that all humic fractions behaved as a sink for C from maize residues but the FA fraction was related to the turnover of fresh organic matter more than the HA. Removal of hydrophobic components from incubated soils by acetone solution allowed a subsequent extraction of HA and, especially, FA still containing much C from maize. The combination of isotopic measurements and NMR spectra indicated that while hydrophilic compounds from maize were retained in HA and FA, hydrophobic components in the HE fraction had chemical features similar to those of humin. Our results show that the organic compounds released in soils by mineralization of fresh plant residues are stored mainly in the hydrophilic fraction of humic substances which are, in turn, stabilized against microbial degradation by the most hydrophobic humic matter. Our findings suggest that native soil humic substances contribute to the accumulation of new organic matter in soils.