The role of biodegradation and photo-oxidation in the transformation of terrigenous organic matter

Microbial and photochemical decomposition are two major processes regulating organic matter (OM) transformation in the global carbon cycle. However, photo-oxidation is not as well understood as biodegradation in terms of its impact on OM alteration in terrigenous environments. We examined microbial and photochemical transformation of OM and lignin derived phenols in two plant litters (corn leaves and pine needles). Plant litter was incubated in the laboratory over 3 months and compositional changes to OM were measured using nuclear magnetic resonance (NMR) and gas chromatography-mass spectrometry. We also examined the susceptibility of soil organic matter (SOM) to ultraviolet (UV) radiation. Solid-state ¹³C NMR spectra showed that O-alkyl type structures (mainly from carbohydrates) decreased during biodegradation and the loss of small carbohydrates and aliphatic molecules was observed by solution-state ¹H NMR spectra of water extractable OM from biodegraded litters. Photochemical products were detected in the aliphatic regions of NaOH extracts from both litter samples by solution-state ¹H NMR. Photo-oxidation also increased the solubility of SOM, which was attributed to the enhanced oxidation of lignin derived phenols and photochemical degradation of macromolecular SOM species (as observed by diffusion edited ¹H NMR). Overall, our data collectively suggests that while biodegradation predominates in litter decomposition, photo-oxidation alters litter OM chemistry and plays a role in destabilizing SOM in soils exposed to UV radiation.     

Characterization and quantification of biomarkers from biomass burning at a recent wildfire site in Northern Alberta,Canada

The composition of organic matter (OM) in pine vegetation and soil samples from a pine forest which was charred by a wildfire was analyzed using solid-state nuclear magnetic resonance (¹³C NMR) and gas chromatography–mass spectrometry (GC–MS) of solvent extracts to study the effects of thermal alteration on soil organic matter (SOM). The NMR data revealed the presence of unaltered biomolecules (cellulose, proteins) and low contents of aromatic C (15%) in the charred pine wood and cones while the charred soil samples exhibited higher contents of aromatic C (39–56%). The solvent extraction of charred and uncharred plant and soil samples yielded diterpenoids, triterpenoids, steroids, a series of aliphatic lipids, phenols and carbohydrates indicating the predominant input of higher plant OM and minor contributions from microorganisms and/or fauna. The lower yield of solvent extractable aliphatic lipids in the charred samples versus the uncharred samples suggests that these compounds are thermally degraded during a wildfire. Molecular markers for the burning of cellulose (levoglucosan, mannosan, galactosan) were detected in all charred samples. The comparison of charred and uncharred samples allowed the identification of unaltered pine derived biomolecules and their thermal alteration products in the charred samples. Terpenoid and steroid biomolecules were in part altered during incomplete combustion to aromatic, unsaturated and polar derivatives (“pyromolecules”) that still retained the characteristic skeleton of their precursors. Since some of the polar degradation products found in the charred soils can be generated either from thermal or microbial degradation, the aromatic and unsaturated hydrocarbon products are preferred as molecular markers for SOM burning. Ratios of biological precursors to aromatic (diterpenoids) or unsaturated products (steroids) indicate that the cyclic lipids in the pine wood and the soil surface horizon were highly altered. In conclusion, the solvent extractable lipids and carbohydrates in charred SOM are valuable, source-specific molecular markers for the burning of plant biomass and for tracing the biogeochemistry of charred residues in soils.     

Effects of soil organic matter composition on unfrozen water content and heterotrophic CO2 production of frozen soils

Several recent studies have highlighted the importance of soil organic matter (SOM) mineralization at high latitudes during winter for ecosystem carbon (C) balances, and the ability of the soil to retain unfrozen water at sub-zero temperatures has been shown to be a major determinant of C mineralization rates. Further, SOM is believed to strongly influence the liquid water contents in frozen surface layers of boreal forest soils and tundra, but the mechanisms and specific factors involved are currently unknown. Here we evaluate the effects of the chemical composition of SOM on the amount of unfrozen water, the pore size equivalents in which unfrozen water can exist, and the microbial heterotrophic activity at sub-zero temperatures in boreal forest soils. To do this, we have characterized the chemical composition of SOM in forest soil samples (surface O-horizons) using solid state CP-MAS (cross polarization magic angle spinning) NMR spectroscopy. The acquired information was then used to elucidate the extent to which different fractions of SOM can explain the observed variations in unfrozen water content, pore size equivalents, and biogenic CO₂ production rates in the examined soil samples under frozen conditions (−4 °C). The data evaluation was done by the use of principal component analysis (PCA) and projections to latent structures by means of partial least square (PLS). We conclude that aromatic, O-aromatic, methoxy/N-alkyl and alkyl C are the major SOM components affecting frozen boreal forest soil’s ability to retain unfrozen water and sustain heterotrophic activity (95% confidence level). Our results reveal that solid carbohydrates have a significant negative impact (95% confidence level) on CO₂ production in frozen boreal spruce forest soils, in contrast to the positive effects of carbohydrate polymers during unfrozen conditions. We conclude that the hierarchy of environmental factors controlling SOM mineralization changes as soils freeze. The effect of SOM composition on pore size distribution and unfrozen water content has a superior influence on SOM mineralization and hence on heterotrophic CO₂ production of frozen soils.     

Characteristics and distributions of humic acids in two soil profiles of the southwest China Karst area

Characteristics and distributions of humic acid (HA) and soil organic matter (SOM) in a yellow soil profile and a limestone soil profile of the southwest China Karst area were systematically investigated to reveal their evolutions in different soils of the study area. The results showed that characteristics and distribution of SOM along the two soil profiles were notably different. Total organic carbon (TOC) contents of soil samples decreased just slightly along the limestone soil profile but sharply along the yellow soil profile. TOCs of the limestone soils were significantly higher than those of the corresponding yellow soils, and C/N ratios of SOMs showed a similar variation trend to that of TOCs, indicating that SOM can be better conserved in the limestone soil than in the yellow soil. The soil humic acids were exhaustively extracted and further fractionated according to their apparent molecular weights using ultrafiltration techniques to explore underlying conservation mechanisms. The result showed that C/N ratios of HAs from different limestone soil layers were relatively stable and that large molecular HA fractions predominated the bulk HA of the top soil, indicating that HA in the limestone profile was protected while bio and chemical degradations were retarded. Combined with organic elements contents and mineral contents of two soils, we concluded that high calcium contents in limestone soils may play a key role in SOM conservation by forming complexation compounds with HAs or/and enclosing SOMs with hypergene CaCO₃ precipitation.     

Molecular level analysis of long term vegetative shifts and relationships to soil organic matter composition

Soil organic matter (SOM) is one of the earth’s largest reservoirs of actively cycled carbon and plays a critical role in various ecosystem functions. In this study, mineral soils with the same parent material and of similar approximate age were sampled from the same climatic region in Halsey, Nebraska to determine the relationship between overlying vegetation inputs to SOM composition using complementary molecular level methods (biomarker analyses and solid state ¹³C nuclear magnetic resonance (NMR) spectroscopy). Soil samples were collected from a native prairie and cedar and pine sites planted on the native prairie. Free and bound lipids isolated from the pine soil were more enriched in aliphatic and cutin-derived compounds than the other two soils. Cinnamyl type lignin-derived phenols were more abundant in the grassland soil than in the pine and cedar soils. Acid to aldehyde ratios (Ad/Al) for vanillyl and syringyl type phenols were higher for the pine soil indicating a more advanced stage of lignin oxidation (also observed by ¹³C NMR) in the soil that has also been reported to have accelerated carbon loss. In agreement with the more abundant aliphatic lipids and cutin-derived compounds, solid state ¹³C NMR results also indicated that the SOM of the pine soil may have received more aliphatic carbon inputs or may have lost other components during enhanced decomposition. The observed relationship between vegetation and SOM composition may have important implications for global carbon cycling as some structures (e.g. aliphatics) are hypothesized to be more recalcitrant compared to others and their accumulation in soils may enhance below ground carbon storage.     

Characterization of soil organic carbon in drained thaw-lake basins of Arctic Alaska using NMR and FTIR photoacoustic spectroscopy

Arctic soils contain a large fraction of Earth’s stored carbon. Temperature increases in the Arctic may enhance decomposition of this stored carbon, shifting the role of Arctic soils from a net sink to a new source of atmospheric CO₂. Predicting the impact of Arctic warming on soil carbon reserves requires knowledge of the composition of the stored organic matter. Here, we employ solid state ¹³C nuclear magnetic resonance (NMR) spectroscopy and Fourier transform infrared-photoacoustic spectroscopy (FTIR-PAS) to investigate the chemical composition of soil organic matter collected from drained thaw-lake basins ranging in age from 0 to 5500 years before present (y BP). The ¹³C NMR and FTIR-PAS data were largely congruent. Surface horizons contain relatively large amounts of O-alkyl carbon, suggesting that the soil organic matter is rich in labile constituents. Soil organic matter decreases with depth with the relative amounts of O-alkyl carbon decreasing and aromatic carbon increasing. These data indicate that lower horizons are in a more advanced stage of decomposition than upper horizons. Nonetheless, a substantial fraction of carbon in lower horizons, even for ancient thaw-lake basins (2000-5500 y BP), is present as O-alkyl carbon reflecting the preservation of intrinsically labile organic matter constituents. Climate change-induced increases in the depth of the soil active layer are expected to accelerate the depletion of this carbon.     

Quantitative C NMR of whole and fractionated Iowa Mollisols for assessment of organic matter composition

Both the concentrations and the stocks of soil organic carbon vary across the landscape. Do the amounts of recalcitrant components of soil organic matter (SOM) vary with landscape position? To address this question, we studied four Mollisols in central Iowa, two developed in till and two developed in loess. Two of the soils were well drained and two were poorly drained. We collected surface-horizon samples and studied organic matter in the particulate organic matter (POM) fraction, the clay fractions, and the whole, unfractionated samples. We treated the soil samples with 5 M HF at ambient temperature or at 60 °C for 30 min to concentrate the SOM. To assess the composition of the SOM, we used solid-state nuclear magnetic resonance (NMR) spectroscopy, in particular, quantitative ¹³C DP/MAS (direct-polarization/magic-angle spinning), with and without recoupled dipolar dephasing. Spin counting by correlation of the integral NMR intensity with the C concentration by elemental analysis showed that NMR was ?85% quantitative for the majority of the samples studied. For untreated whole-soil samples with <2.5 wt.% C, which is considerably less than in most previous quantitative NMR analyses of SOM, useful spectra that reflected ?65% of all C were obtained. The NMR analyses allowed us to conclude (1) that the HF treatment (with or without heat) had low impact on the organic C composition in the samples, except for protonating carboxylate anions to carboxylic acids, (2) that most organic C was observable by NMR even in untreated soil materials, (3) that esters were likely to compose only a minor fraction of SOM in these Mollisols, and (4) that the aromatic components of SOM were enriched to ∼53% in the poorly drained soils, compared with ∼48% in the well drained soils; in plant tissue and particulate organic matter (POM) the aromaticities were ∼18% and ∼32%, respectively. Nonpolar, nonprotonated aromatic C, interpreted as a proxy for charcoal C, dominated the aromatic C in all soil samples, composing 69-78% of aromatic C and 27-36% of total organic C in the whole-soil and clay-fraction samples.     

Fate of microbial biomass-derived amino acids in soil and their contribution to soil organic matter

Soil organic matter (SOM) is important for soil fertility and for the global C cycle. Previous studies have shown that during SOM formation no new compound classes are formed and that it consists basically of plant- and microorganism-derived materials. However, little data on the contribution from microbial sources are available. Therefore, we investigated previously in a model study the fate of C from ¹³C-labelled Gram-negative bacteria in soil (Kindler, R., Miltner, A. Richnow, H.H., Kästner, M., 2006. Fate of gram negative bacterial biomass in soil – mineralization and contribution to SOM. Soil Biology and Biochemistry 38, 2860–2870) and showed that 44% of the bulk ¹³C remained in the soil. Here we present the corresponding data on the fate of amino acids hydrolysed from proteins, which are the most abundant components of microbial biomass. After 224 days incubation, the label in the total amino acids in the soil amended with ¹³C-labelled cells decreased only to >95%. The total amino acids therefore clearly showed a lower turnover than the bulk ¹³C and a surprisingly stable concentration. Proteins therefore have to be considered as being stabilised in soil in dead, non-extractable biomass or cell fragments by known general stabilisation mechanisms. The label in the amino acids in a fraction highly enriched in living microbial biomass decreased to a greater extent, i.e. to 25% of the initially added amount. The amino acids removed from this fraction were redistributed via the microbial food web to non-living SOM. All amino acids in the microbial biomass were degraded at similar rates without a change in isotopic signature. The nuclear magnetic resonance (NMR) spectra of the soils were very similar and indicate that the residues of the degraded microbial biomass were very similar to those of the SOM and are a significant source for the formation of the SOM.     

Optimized NMR spectroscopic strategy to characterize water dynamics in soil samples

¹H wideline NMR spectra of soil samples offer the possibility to analyze soil material based on their proton mobility. Care has to be taken to remove unwanted signal contributions from the probe background. We demonstrate that unstructured wideline spectra can be analyzed quantitatively by a combination of a Gaussian line for rigid and a Lorentzian line for mobile protons. This is used to study effects of hydrogen-bonded water networks upon heat treatment for a series of different soil samples with varying water content as a contribution to study physical aging of soil organic matter (SOM). Results are combined with ¹H projections from ¹³C 2D WISE (wideline separation) experiments representing solely the broad Gaussian line. Furthermore, for the first time applied to soils, ¹H structural information from soil samples is obtained from 2D PMLG phase modulated Lee-Goldburg measurements under magic angle spinning (MAS). Low water contents improve the resolution of main functional groups significantly.     

Al speciation in tropical podzols of the upper Amazon Basin: A solid-state Al MAS and MQMAS NMR study

In the upper Amazon Basin, aluminum previously accumulated in lateritic formations is massively remobilised in soils by podzolization and exported in waters. We have investigated the speciation of aluminum in the clay-size fractions of eight horizons of waterlogged podzols lying in a depression of a plateau. The horizons illustrate the main steps involved in the podzolization of laterites. They belong to eluviated topsoil A horizons and illuviated subsoil Bhs, Bh and 2BCs horizons of weakly and better-expressed podzols located at the margin and centre of the depression. For the first time, aluminum speciation is quantitatively assessed in soils by spectroscopic methods, namely FTIR, ²⁷Al magic angle spinning (MAS) and multiple-quantum magic angle spinning (MQMAS), nuclear magnetic resonance (NMR). The results thus obtained are compared to chemical extraction data.Solid-state ²⁷Al MAS NMR spectra enable to distinguish Al bound to organic compounds from that incorporated in secondary mineral phases detected by FTIR. MQMAS experiments additionally show that both chemical shifts and quadrupolar constants are distributed for Al nuclei linked with organic compounds. Similar amounts of chelated Al are obtained from NMR spectra and chemical extractions. The study enables to highlight three major steps in the fate of aluminum. (i) Aluminum is first released by mineral weathering, feeds complexing sites of organic matter and accumulates in subsurface Bhs horizons of weakly expressed podzols (acidocomplexolysis). (ii) Complexes of aluminum with organic matter (Al-OM) then migrate downwards in sandy horizons of better-expressed podzols and accumulate at depth in less permeable 2BCs horizons. (iii) The minor amounts of aluminum present in the 2BCs horizon of the downslope podzol show that aluminum is eventually exported towards the river network, either complexed with organic matter or as Al³⁺ ions after desorption from organic compounds, due to decreasing pH or biodegradation of organic ligands. The direct spectroscopic determination of Al-speciation during the formation of podzolic soils opens new perspectives to trace metal loads in the rivers of the upper Amazon Basin.     

Loss on ignition and kjeldahl digestion for estimating organic carbon and total nitrogen in estuarine marsh soils: Calibration with dry combustion

Soils (n=250) were collected from ten salt and brackish-water marshes of North Carolina and analyzed for organic matter content by loss on ignition (LOI) and Kjeldahl nitrogen (KN). Total organic carbon and total nitrogen were determined on the same samples using an elemental CHN analyzer. Regression analyses indicated that LOI and KN were excellent estimators of organic C (R²=0.990) and total N(R²=0.986), respectively, in low clay content (0–11%) marsh soils containing a wide range of soil organic C (0.1–28%) and total N (0–1.6%). A quadratic equation best described the relationship between organic C and organic matter (Organic C=0.40 [LOI] +0.0025 [LOI]²) while a linear model accurately described the relationship between total N and Kjeldahl N (Total N=1.048 [KN]?0.010). The proportion of organic C in organic matter (C/OM) increased with increasing soil organic matter content, probably as a result of aging. Young marshes, which are characterized by low soil organic content contain C/OM ratios similar to emergent vegetation (40–45%). In old organic soils (70–80% organic matter), C/OM increased to 57–60% due to accumulation of reduced organic materials.     

Relative contribution of foliar and fine root pine litter to the molecular composition of soil organic matter after in situ degradation

The influence of litter quality on soil organic matter (SOM) stabilization rate and pathways remains unclear. We used ¹³C/¹⁵N labeled litter addition and Curie-point pyrolysis gas chromatography–mass spectrometry combustion-isotope ratio mass spectrometry (Py–GC–MS–C–IRMS) to explore the transformation of litter with different composition and decay rate (ponderosa pine needle vs. fine root) to SOM during 18 months in a temperate conifer forest mineral (A horizon) soil. Based on ¹³C Py–GC–MS–C–IRMS the initial litter and bulk soil had ∼1/3 of the total pyrolysis products identified in common. The majority was related either to carbohydrates or was non-specific in origin. In bulk soil, carbohydrates had similar levels of enrichment after needle input and fine root input, while the non-specific products were more enriched after needle input. In the humin SOM fraction (260 yr C turnover time) we found only carbohydrate and alkyl C-derived compounds and greater ¹³C enrichment in the “carbohydrate” pool after fine root decomposition. ¹⁵N Py–GC–MS–C–IRMS of humic substances showed that root litter contributed more than needle litter to the enrichment of specific protein markers during initial decomposition.We found little evidence for the selective preservation of plant compounds considered to be recalcitrant. Our findings suggest an indirect role for decomposing plant material composition, where microbial alteration of fine root litter seems to favor greater initial stabilization of microbially derived C and N in SOM fractions with long mean turnover times, such as humin, compared to needles with a faster decay rate.     

Geochemistry of radium in soils of the Eastern United States

The abundance and chemical/mineralogical form of ²²⁶Ra, ²³⁸U and ²³²Th were determined on samples of soil and associated vegetation at 12 sites in the eastern United States. Progressive, selective chemical extraction plus size fractionation determined the abundance and radiometric equilibrium condition of these nuclides in 6 operationally defined soil fractions: exchangeable cations, organic matter, “free” Fe-oxides, sand, silt, and clay.In soils, profile-averaged ²²⁶Ra/²³⁸U activity ratios (AR) are within 10% of unity for most sites, implying little fractionation of U and Ra when the entire soil profile is considered. However, ²²⁶Ra greatly exceeds ²³⁸U activity in most surface soil (AR up to 1.8, av 1.22), in vegetation (AR up to 65, av. 2.8), in the exchangeable+organic fraction (AR up to 30, av. 13), in some soil Fe oxides (AR up to 3.5, av. 0.83) and in the C horizons of deeply weathered soils (AR up to 1.5).A major factor in Ra behavior is uptake by vegetation, which concentrates Ra>U and moves Ra from deeper soil to surface soil. Vegetation is capable of creating the observed Ra excess in typical surface soil horizons (AR up to 1.8, av. 1.22) in about 1000 a. Of the total Ra in an average A horizon, 42% occurs as exchangeable ions and in organic matter, but only 6–8% of the parent U and Th occur in these soil forms. In contrast, U is slightly enriched relative to Ra in Fe-oxides of A horizons, implying rapid chemical partition of vegetation-cycled U and Ra.In deeper horizons, transfer by vegetation and/or direct chemical partitioning of Ra into organic and exchangeable forms provides a source for unsupported ²²⁶Ra in Ra-rich organic matter, and leaves all soil minerals Ra-poor (AR=0.73). Organic matter evidently has a strong affinity for Ra.The phenomena discussed above are relevant to evaluation of indoor Rn hazard, and behavior of Ra at sites affected by radioactive waste disposal, phosphate tailings, Ra-rich brine, and uraniferous fertilizer.     

Lithogenic thallium behavior in soils with different land use

In order to evaluate the effect of different land use on lithogenic Tl geochemistry, two forest and grassland soils developed on an identical Tl-rich substrate were examined. For this purpose a complex soil-plant investigation supplemented by mineralogical methods was performed. The modified BCR sequential extraction combined with X-ray diffraction analysis (XRD) and voltammetry of microparticles (VMP) were performed for a detailed insight on lithogenic Tl speciation and availability in both contrasting soils. It was revealed that soil forming processes like bioturbation and probably dust deposition may influence the increased input of lithogenic Tl into the forest floor. Thallium was predominantly bound within the residual fraction (up to 95%) corresponding to primary silicates (mainly orthoclase and muscovite) and probably secondary illite, which were detected by XRD in all studied horizons. Thus, stable silicates can be thought as the phases controlling the solubility of lithogenic Tl in both the forest and grassland soils. The highest portion (~ 5%) of “labile” Tl was found in the organic horizons of the forest soil indicating a distinct role of forest soil organic matter (SOM) on Tl mobilization and availability. Thallium adsorption was dominated by an identified non-crystalline Mn(III,IV) oxide detected by VMP proving thus its strong affinity for Mn oxides in mineral soils. On the contrary, Tl adsorption by more abundant Fe(III) oxides (goethite and ferrihydrite) was evaluated to be negligible. Organically bound Tl in the forest floor was found to be associated with primary SOM corresponding to the raw and partially decomposed litter of Norway spruce (Picea abies L.). Moreover, a relatively high Tl uptake was recorded by this species. In contrast, lithogenic Tl uptake by common grasses like red clover (Trifolium pratense L.) or timothy grass (Phleum pratense L.) seems to be very low.     

The impact of climate changes during the Holocene on vegetation in northern French Guiana

The impact of climatic changes that occurred during the last glacial maximum and the Holocene on vegetation changes in the Amazon Basin and the Guiana Shield are still widely debated. The aim of our study was to investigate whether major changes in vegetation (i.e. transitions between rainforests and C₄ savannas) occurred in northern French Guiana during the Holocene. We measured variations in the δ¹³C of soil organic matter at eight sites now occupied by forest or savannah. The forest sites were selected to cover two regions (forest refugia and peneplains) which are thought to have experienced different intensities of disturbance during the latest Pleistocene and the Holocene. We found that none of the forest sites underwent major disturbances during the Holocene, i.e. they were not replaced by C₄ savannahs or C₄ forest savannahs for long periods. Our results thus suggest that tropical rainforests in northern French Guiana were resilient to drier climatic conditions during the Holocene. Nevertheless, geographical and vertical variations in the ¹³C of SOM were compatible with minor changes in vegetation, variations in soil processes or in soil physical properties.     

Organic matter quality in reclaimed boreal forest soils following oil sands mining

Following surface mining of the Athabasca Oil Sands deposits in northeastern Alberta, Canada, land reclamation entails the reconstruction of soil-like profiles using salvaged soil materials such as peat and mining by-products. The overall objective of this research was to assess soil organic matter (SOM) quality in different reclamation practices as compared to undisturbed soils found in the region. Soil samples (0–10 cm) were taken from 45 plots selected to represent undisturbed reference ecosites and reclamation treatments. Soil OM pools were isolated using a combination of acid hydrolysis and physical separation techniques. Chemical composition of the low density fractions was characterized using ramped cross polarization (RAMP-CP) ¹³C nuclear magnetic resonance (NMR). Differences between disturbed and undisturbed sites reflected the influence of different botanical inputs (peat vs. forest litter) to SOM composition. Reconstructed soils were characterized by significantly lower alkyl over O-alkyl carbon (ALK/O-ALK) ratios (0.3) than undisturbed sites (0.5). For these reconstructed soils, a significantly higher proportion of soil carbon was present in the sand associated (Heavy sand) pool (49.2 vs. 37.3) and in the acid-unhydrolyzable residue (AUR) fraction (61.3 vs. 54.7). These SOM parameters were significantly related to time since reconstruction, with the AUR (p value = 0.012) and Heavy sand (p value = 0.05) fractions decreasing with time since reconstruction, while the ALK/O-ALK ratio increased (p value = 0.006). These findings suggest that the ALK/O-ALK, AUR, and Heavy sand parameters are suitable indicators for monitoring SOM quality in these reconstructed soils following oil sands mining.     

Detailed investigation of organic matter components in extracts and drainage waters from a soil under long term cultivation

Aqueous solutions of increasing pH (7.0, 10.6 and 12.6) were used to extract exhaustively the organic matter (OM) from a pelo-stagnogley (heavy clay) soil in long term cultivation. OM yield was 1.7 times greater when the extracts were processed using an XAD-8 and XAD-4 resin-in-tandem procedure than that from the procedure of the International Humic Substances Society (IHSS). The substantial difference can be attributed to the amount retained by the XAD-4 resin, which is lost in the IHSS process. Elemental, δ¹³C, δ¹⁵N, cation exchange capacity, neutral sugars, amino acids and solid state CPMAS ¹³C NMR analyses indicated significant, but rational similarities and differences between the various fractions isolated. There was strong NMR evidence for material derived from lignin in all the humic and fulvic acid isolates. The signals were attenuated in the more transformed/oxidized fractions isolated at lower pH. Novel humic acid fractions enriched in carbohydrate/peptide functionalities were isolated from the more hydrophobic extracts at pH 10.6 and 12.6. Isolates from XAD-4, of microbial origin, were enriched in neutral sugars but not in amino acids, and had minimal aromaticity. Components isolated from the cultivated soil were broadly similar to those from a comparable soil in long term grassland. The compositions of fractions isolated from the drainage water were similar to those extracted from the soil but had higher carboxyl content. The amount and composition of the various organic fractions in grassland and the continuously cropped soil are discussed in terms of their potential to contribute to carbon sequestration by soil under similar management regimes.     

Deforestation modifying terrestrial organic transport in the Rio Tapajós, Brazilian Amazon

The concentration and biomarker compositions of sedimentary organic matter (OM) as well as fine and coarse suspended particles were analysed to identify the impact of deforestation on the transport of terrigenous organic matter (OM) in the Rio Tapajós, a major tributary to the Amazon. Substantial shifts in the concentration and composition of recently deposited sedimentary OM suggest that intensive deforestation over the last few decades has considerably modified the natural inputs of sedimentary materials to the aquatic ecosystems by disrupting the terrigenous fluxes of humus and soil materials from the drainage basin. The observed compositional changes of bulk OM and land derived biomarkers (e.g. lignin) in recent sediments illustrate a sedimentary enrichment in OM from soil horizons that, under normal forest cover, tend to be retained in the drainage basin. On average, the recently accumulated OM is nitrogen-rich ((C/N)a=12–15) and more highly degraded ((Ac/Al)v=0.4–0.6 and DHBA/V=0.15–0.20) than deep materials ((C/N)a=20–30, (Ac/Al)v=0.25–0.4, and DHBA/V=0.05–0.10), showing that this recently accumulated material is more humified than original inputs to the aquatic system, and consistent with increased exportation of fine eroded mineral and organic particles from surface soils along river banks. The present study illustrates the relevance of using OM oxidation products in sediment profiles to evaluate deforestation impacts on aquatic ecosystems and to characterize the nature of eroded soil materials, complementing studies on mineral/metal cycling.     

Stable carbon isotopic composition of soil organic matter in the karst areas of Southwest China

This study dealt with the distribution characteristics of soil organic carbon （SOC） and the variation of stable carbon isotopic composition （δ^13C values） with depth in six soil profiles, including two soil types and three vegetation forms in the karst areas of Southwest China. The δ^13C values of plant-dominant species, leaf litter and soils were measured using the sealed-tube high-temperature combustion method. Soil organic carbon contents of the limestone soil profiles are all above 11.4 g/kg, with the highest value of 71.1 g/kg in the surface soil. However, the contents vary between 2.9 g/kg and 46.0 g/kg in three yellow soil profiles. The difference between the maximum and minimum δ^13C values of soil organic matter （SOM） changes from 2.2‰ to 2.9‰ for the three yellow soil profiles. But it changes from 0.8‰ to 1.6‰ for the limestone soil profiles. The contrast research indicated that there existed significant difference in vertical pattems of organic carbon and δ^13C values of SOM between yellow soil and limestone soil. This difference may reflect site-specific factors, such as soil type, vegetation form, soil pH value, and clay content, etc., which control the contents of different organic components comprising SOM and soil carbon turnover rates in the profiles. The vertical variation patterns of stable carbon isotope in SOM have a distinct regional character in the karst areas.