HUMUS TYPE DISCRIMINATION FROM MASS SPECTRA BY A SIMPLIFIED STATISTICAL TREATMENT

The calculation of a discriminator between mull and mor humus types from the mass spectra of soil pyrolysis products, described earlier by Bracewell and Robertson (1973), used IIO normalized peak heights; these can be reduced to thirteen and the calculation simplified. Assumption of class for some soils, which was necessary in the previous method of obtaining the pattern classifier, has been obviated by the use of principal components analysis.     

A PYROLYSIS-GAS CHROMATOGRAPHY METHOD FOR DISCRIMINATION OF SOIL HUMUS TYPES

Principles governing the choice of a pyrolysis-gas chromatography method for work on soils and organic macromolecules are reviewed, and the method is applied to the discrimination of mull and mor humus in freely drained soils. Relatively undecomposed surface humus shorizons yield pyrolysis products characteristic of lignin, but these are not present in mineral horizons apart from traces persisting in some podzol A horizons. Mor humus incorporated in A horizons is characterized by a high pyrolysate content of furfurals and phenols whilst mull humus yields proportionately more pyrrole. Humus in B horizons yields a low furfural content with respect to pyrrole and a low content of polar heteroatomic molecules with respect to benzene, toluene, and light molecules of low polarity.     

Chemical characterization and decomposition of organic matter from two contrasting grassland soil profiles

Particle size fractions of soils from the surface 6 cm of two adjacent grassland plots which, as a result of different fertilizer treatments since 1897, have either a mor or a mull humus form were analysed using solid-state ¹³C nuclear magnetic resonance spectroscopy and fractionation of organic N by steam distillation. In the mor humus soil, which had received 180 kg (NH⁴)²SO⁴ ha^?1 annually and was pH 4.3, there was more C and N in the larger particle size fractions than in the mull humus soil (pH 5.8). The NMR spectra of correspondingly sized soil fractions were similar for both soils. The intensities of NMR signals between 0 and 40 ppm (alkyl-C) and between 160 and 200 ppm (carbonyl-C) increased with decreasing particle size. The intensities of the NMR signals between 60 and 90 ppm (0-alkyl-C) and between 90 and 110 ppm (acetal- and ketal-C) decreased with increasing particle size. Comparison of the NMR spectra of the >2000 um fractions from both soils with those of dried grass litter from the same plots indicated the exclusive plant origin of the C in the largest size fraction of the soils. NMR resonances between 40 and 60 ppm were attributed to alkyl-amino-C because their intensities agreed with the amino-N determinations obtained during organic N fractionation. During incubation in soil microcosms, the larger sized fractions decomposed more rapidly than the smaller fractions. However, all the correspondingly sized particle fractions from the two soils decomposed at the same rate except the >2000 pm fractions. The largest size fraction from the mor humus soil decomposed faster than that from the mull humus soil. This difference in decomposition rate could not be attributed to differences in the chemical composition of the >2000 pm fraction.     

Pyrolysis-gas chromatography studies on a climosequence of soils in tussock grasslands,New Zealand

The nature of the organic matter in the A horizons of seven New Zealand soils in tussock grasslands has been shown by pyrolysis-gas chromatography of the whole soils to be strongly influenced by climate. A ratio relating the a abundances of four pyrolysis products varies systematically from 1.20 for a brown-grey earth to 3.82 for a high-country podzolized yellow-brown earth, and shown significant correlations with altitude, precipitation, and mean annual temperature; this is in accord with the concept of the seven soils forming members of a climosequence. Similarities with the mull/mor humus sequence in Scottish soils are also noted.     

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.     

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.     

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.     

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.     

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.     

Distribution pattern of total lipids and lipid fractions in forest humus

Mull, moder, and mor humus profiles were investigated for their total lipid contents and the behaviour of lipid-phosphorus and of five neutral lipid classes identified by HPTLC. The quantitative distribution of total and neutral lipids among the humus types is, besides by natural differences between the various parent litter materials, mainly controlled by soil physicochemical properties. In particular strongly acidic conditions, i.e. conditions corresponding to a reduced biological activity, inhibit significantly the decomposition of lipid compounds in (moder and) mor humus. A feature of the lipid depth functions is the input of microbial and root litter-derived lipid material in the fermentation layers and a considerable lipid accumulation in the A horizons, probably at least partly due to mechanical transport processes. Phospholipids show no distinct variation dependent on the humus type, as far as the organic layers are concerned. But obviously, lipid-P in the mineral, soil is closely correlated with, and therefore is a valuable measure for, the overall biological activity increasing from mor to moder and mull humus.     

Litter decomposition and humification in acidic forest soils studied by chemical degradation,IR and NMR spectroscopy and pyrolysis field ionization mass spectrometry

Two forest soils (Typic Dystrochrept, Entic Haplorthod) with mor and moder were investigated by chemical degradation, IR and CPMAS ¹³C NMR spectroscopy and pyrolysis (Py) field ionization (FI) mass spectrometry (MS). Chemical analyses show that during litter decomposition, humification, and podzolisation, cellulose and lignin structures decrease considerably, whereas no distinct changes were found for the hemicellulose and protein fractions. These results are consistent with current hypotheses on the conversion of plant residues to stable humic substances, but the sum of chemically identified organic soil components of the litter layers only accounts for 40–50% of total organic carbon. The amounts of different carbon types were estimated by the integration of CPMAS ¹³C NMR spectra. For the L layers this calculation assigns 56–58% as O-alkyl-C, 20–22% as alkyl-C, 14–16% as aryl-C, and 6–8% as carboxyl-C. With increasing soil depth O-alkyl-C (with polysaccharides as main source) decrease to 31–42%, aliphatic C increases to 36–43%, and aryl- and carboxyl-C show no distinct changes. The hypothesis of an increasing aromaticity during humification in soils therefore is questionable. Data from Py-FIMS confirm and extend the results' of chemical methods as well as IR and ¹³C NMR spectroscopy. In particular, the Fi mass spectra of the generated pyrolysates show that the increase in polymethylene carbon during the biodegradation and humification of beech and spruce litter is partly due to an increase of saturated fatty acids. This means, Py-FIMS is able to describe the structure of wet-chemically unaccounted, individual humus constituents and thus improves the knowledge about the genesis of humic substances.     

Cyanidadsorption an Sesquioxiden,Tonmineralen und Huminstoffen

Cyanide adsorption on sesquioxides, clay-minerals and humic substances The adsorption of cyanide (KCN) on sesquioxides, clay minerals, and humic substances at different pH-values was studied. Moreover we looked for the CN-adsorption on L-layers of the humus forms mull, moder and mor. Cyanide was only adsorbed by humic acid. The amount of CN adsorbed increased with increasing pH of the reaction solution. IR-spectroscopic investigations of CN treated humic acids revealed that the cyanide was adsorbed at low pH (<7) as HCN-molecules by formation of hydrogen bonds with COOH-, COH-, OH- and NH₂-groups of the humic acid. At pH > 7 the cyanide was mainly adsorbed as CN^? by charge transfer with acceptor-molecules such as chinones. The cyanide adsorption of L-layers of humus forms decreased in the order mor > mull > moder. It is surmised that the HCN-molecules were not only adsorbed by humic acids in these layers but also by oxidation products of lignin, pectin, protein, cellulose, and carbon-hydrates of fulvic acids. Solutions of K₂HPO₄ did not desorb cyanides from humic acids to any great extent.     

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.     

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.     

Selenitadsorption an Waldhumusformen

Adsorption of selenite on different types of forest humus In the present investigation the adsorption of selenite selenium on L-, O-, and A-horizons of the humus forms mull, moder, and mor was studied. Selenite adsorption decreased in the order mull > moder > mor. The organic layers adsorbed nearly the same amount of selenium as the underlying A-horizons. Among the L- and O-layers selenadsorption increased with increasing pH. Amounts of organic carbon, “free” oxides did not influence the adsorption capacity. The Freundlich equation was valid to describe selenite adsorption of all layers under investigation. Additionally the Langmuir equation fitted the adsorption curves of the mull soil and the moder L-horizon. Adsorption experiments using perfusion apparatuses showed microorganismus to incorporate high amounts of selenite under natural conditions.     

Characteristics of soil organic matter in temperate soils by Curie point pyrolysis-mass spectrometry.

This series of papers examines some significant differences in the constitution of organic matter found amongst major soil groups and their genetic and morphological horizons, as determined by the dynamic pyrolysis-mass spectrometry of whole soil samples. Multivariate methods of data analysis identify groups of co-variant mass ions which successfully partition samples in terms of the above soil categories, and correlate with other major properties such as humification and hydromorphism. This first study covers the A horizons from a group of 22 Scottish soils chosen from the major temperate soil groups including brown forest soils, podzols, and noncalcareous, peaty and humic gleys (phaeozems, cambisols, podzols and gleysols). The principal components analysis of 52 mass ion intensities was found to partition the soils successfully in terms of two main factors which represented 62% of the total statistical variance. The first factor was found to correspond closely to the extent of hydromorphism, being high for highly gleyed A horizons, and depended chiefly on the presence of aromatic hydrocarbon ions. The second factor corresponded to the extent of mull humus formation, being high for brown forest soils (phaeozems, cambisols) and low for podzols, and depended chiefly on the abundance of polypeptide products relative to polysaccharide products. This second factor was evidently a more comprehensive expression of a humification factor found in previous studies. The relationships of these factors with C and N content and with base status properties were examined.     

Community structures of Collembola in sugar maple forests: relations to humus type and seasonal trends

Community structures of Collembola and their seasonal fluctuations were studied in eight southern Quebec sugar maple (Acer saccharum Marsh.) forests growing on mull, moder and mor humus types. Endogeic species were extracted from soil cores using Berlese-Tullgren funnels while epigeic species were collected using pit-light traps (Luminoc®). Comparisons of species presence, abundance, and dominance among sites and seasons were done using Sorensen's similarity coefficients and CANOCO. A total of 92 species from 7 families and 35 genera were identified. Species dominance and community structure differed according to humus types. Two groups of endogeic species were identified. The mor/mor-moder type group included Folsomia penicula, Hypogastrura (Ceratophysella) spp. Que., Micrisotoma achromata, Onychiurus (Protaphorura)? parvicornis, Onychiurus (Onychiurus) sp. A Que. And Onychiurus (Onychiurus) sp. B Que. The mull/mull-moder type group included Isotoma (Desoria) notabilis, Tullbergia (Tullbergia) silvicola, Tullbergia (Tullbergia) clavata, and Pseudosinella alba. Such clear humus type relationships were not found among the epigeic species, but important seasonal changes in community structures were found for these species. Spring species were Sminthurinus (Katiannina) macgillivrayi, Hypogastrura (Ceratophysella) maheuxi, Hypogastrura (Hypogastrura) sp. A Que. and Sminthurinus (Sminthurinus) latimaculosus. Tomocerus (Pogonognathellus) flavescens, Sminthurinus (Sminthurinus) henshawi, and Orchesella hexfasciata appeared in the summer samples while Dicyrtoma (Dicyrtoma) aurata was found only in fall samples where it was dominant in most sites along with either Sminthurides (Sminthurides) lepus or Sminthurinus (Sminthurinus) quadrimaculatus. No strong seasonal trends were found among the dominant endogeic species.     

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.     

Dynamics of organic matter in soils of temperate regions: Its action on pedogenesis

The author studies the reciprocal action of the organic and inorganic components during the process of humification in temperate climates. In an Atlantic climate, three main types of organo-mineral complexes occur: humus—CaCO₃ in rendzina soils, humus-allophane in andosols and humus-iron in brown acid soils. These complexes differ in their properties, both biologically (ability to withstand biodegradation) and chemically (ability to withstand extractants).The humus-swelling clay complex, occurring in fluctuating pedoclimates, shows a high degree of polymerization of organic matter (maturation).The temperate humus forms are classified with regard to the kind and degree of transformation of the fresh organic matter: (1) little-transformed humus (e.g., calcic mull and moder); (2) strongly transformed humified humus (e.g., acid mull, andosol); (3) very much transformed, mature humus type (e.g., Vertisol, chernozem).     

A mathematical model of energy budgets of forest humus of the mull,moder and mor types in Poland

A mathematical solution is proposed of the long-discussed problem of accumulation and decomposition of forest humus, and a generalized form of a dynamic mathematical model of energy budgets of a forest humus layer with any number of subhorizons differing in degree of decomposition is presented. Methods of taking measurements of the relevant parameters for the model are also indicated.The model in question has been applied in analysing the results of detailed studies of energy budgets of forest-floor layers in examples of three climax forest ecosystems with three different types of forest humus (mull, moder, mor).