Spatial distribution of soil organic carbon quality descriptors determining factors that affect its sequestration in Northeast Algeria.

Increasing soil organic carbon (SOC) content is crucial for soil fertility, conservation, and combating climate-related issues by sequestering CO2. While existing studies explore the total content of SOC, few of them investigate the factors that favor its sequestration and the impact of land use type and management. This research aims to study the spatial variation of the total content and the quality or maturity (in terms of aromaticity) of the humic acid (HA) fraction, along with the factors that enhance its formation and conservation for a longer time in the soil. In addition, the study tries to evaluate the performance of the Regression Kriging (RK) method in producing interpolation maps that describe the natural variation of the SOC and its quality with the aim of defining and preventing soil degradation. Finally, the study aims to evaluate the impact of the land use type and the importance of dense vegetation in the sequestration of the organic carbon (OC) in the soil. The analysis of the SOC was performed in northeast Algeria's semi-arid climate, examining content, quality, and chemical composition. Using geostatistical methods (RK), SOC is correlated with most related factors, producing detailed interpolation maps. The results showed that the SOC and its HA fraction (both its total content and its degree of transformation or maturity (measured in terms of aromaticity and structural condensation) are highly correlated to the topography of the area (P < 0.05). Results reveal variations in HAs' composition across land covers. Notably, areas subjected to burning exhibited a 21% increase in HA aromaticity compared to forested regions and a 29% increase relative to cultivated areas. The study highlights that soil cover has a substantial influence on the performance of SOC sequestration, the forested areas have a positive impact on the storage of SOC in the form of HA with a more complex chemical composition that suggests increased aromaticity and resilience. As a whole, the results indicate the potential of geostatistical methods to provide valuable information about the factors that influence the current status and evolution of SOC in the study area.

Impact of Biochar Amendment on Soil Properties and Organic Matter Composition in Trace Element-Contaminated Soil.

The application of biochar as an organic amendment in polluted soils can facilitate their recovery by reducing the availability of contaminants. In the present work, the effect of biochar application to acid soils contaminated by heavy metal spillage is studied to assess its effect on the quantity and composition of soil organic matter (SOM), with special attention given to soil humic acids (HAs). This effect is poorly known and of great importance, as HA is one of the most active components of SOM. The field experiment was carried out in 12 field plots of fluvisols, with moderate and high contamination by trace elements (called MAS and AS, respectively), that are located in the Guadiamar Green Corridor (SW Spain), which were amended with 8 Mg·ha-1 of olive pit biochar (OB) and rice husk biochar (RB). The results indicate that 22 months after biochar application, a noticeable increase in soil water holding capacity, total organic carbon content, and soil pH were observed. The amounts of oxidisable carbon (C) and extracted HAs in the soils were not altered due to biochar addition. Thermogravimetric analyses of HAs showed an increase in the abundance of the most thermostable OM fraction of the MAS (375-650 °C), whereas the HAs of AS were enriched in the intermediate fraction (200-375 °C). Spectroscopic and chromatographic analyses indicate that the addition of biochar did not alter the composition of the organic fraction of HAs, while Cu, Fe, and as were considerably accumulated at HAs.

Hydrophobicity of soils affected by fires: An assessment using molecular markers from ultra-high resolution mass spectrometry.

Soil water repellency (SWR) is a physical property due to a complex interaction of factors (e.g., fire, soil organic matter, soil texture) that reduces the soil water infiltration capacity. Traditionally, SWR is attributed to the accumulation and redistribution of hydrophobic compounds within soil profile. To obtain further insight into chemical compounds, which could be associated with SWR, a study was done on coarse (1-2 mm) and fine (< 0.05 mm) granulometric fractions of burned and unburned sandy soils under two Mediterranean vegetation biomes from Doñana National Park (Spain). The water drop penetration time (WDPT) test was used to assess the SWR. The molecular composition of extracted humic substances from the soil organic matter (SOM) was determined by Fourier transform ion cyclotron resonance mass spectrometry (FT-ICR/MS). Partial least squares (PLS) regressions showed that the SWR can be predicted (P = 0.006) solely based on the abundances of approximately 1200 common compounds determined by FT-ICR/MS. This model confirmed the significant correlation between a specific SOM molecular composition and the SWR. The comparative analysis revealed that the SWR in the burned samples was significantly (P < 0.05) related to the abundance of aromatic and condensed compounds, while in the unburned samples there was a significant influence of aromatic hydrocarbons and lignin compounds. In the fine fraction, lipid compounds were significantly associated with the SWR. Contrastingly, the coarse fraction did not show any correlation. Alternatively, soils with a high SWR were significantly related to the presence of lipids and lignin. This analysis showed that combining FT-ICR/MS molecular characterizations with statistical treatments is a powerful approach for exploratory analysis suggesting that the structural features associated with SWR in the studied soils are different depending on the types of vegetation or the soil physical fractions with different particle size.

Fire effects on C and H isotopic composition in plant biomass and soil: Bulk and particle size fractions.

This work studies carbon (C) and hydrogen (H) isotope composition of plant biomass and soil organic matter (SOM) in an attempt to assess both, changes exerted by fire and possible inputs of charred materials to the soil after a wildfire. Isotope composition of bulk soil, soil particle size fractions and biomass of the dominant standing vegetation in the area (Quercus suber) from Doñana National Park (SW-Spain) were studied by isotope ratio mass spectrometry (IRMS). SOM C isotope composition indicates the occurrence of two SOM pools with different degree of alteration. Coarse soil fractions (>0.5 mm) were found 13C depleted with δ13C values close to those in leaf biomass, pointing to a predominance of poorly transformed SOM. Conversely, fine fractions (<0.1 mm) were found enriched in 13C as corresponds to a more humified SOM. The fire produced no changes in this trend, although a consistent 13C enrichment (c. 1‰) was observed in all soil fractions with decreasing size. Concerning H isotopes, the coarse fractions (>0.5 mm) displayed significant lower δ2H values than the intermediate and fine ones (<0.5 mm), again similar to those in leaf biomass (c. -80‰), whereas the fine fractions were found deuterium (2H)-enriched with significant higher δ2H values (c. 50‰), suggesting physical speciation of H depending on soil particle size. The fire produced a significant 2H depletion (Δ2H c. -10‰) in the finer fractions (<0.1 mm). The study of stable isotope analysis added new information and complements the results obtained by other proxies to better understand the effect of fire on SOM.

Effect of a wildfire and of post-fire restoration actions in the organic matter structure in soil fractions.

The impact of wildfires and of restoration actions on soil organic matter (SOM) content and structure was studied in a soil under pine (Pinus pinea) from Doñana National Park (SW Spain). Samples were collected from burnt areas before (B) and after post-fire restoration (BR) and compared with an unburnt (UB) site. Analytical pyrolysis (Py-GC/MS) was used to investigate SOM molecular composition in whole soil samples and in coarse (CF) and fine (FF) fractions. The results were interpreted using a van Krevelen graphical-statistical method. Highest total organic carbon (TOC) was found in UB soil and no differences were found between B and BR soils. The CF had the highest TOC values and FF presented differences among the three scenarios. Respect to SOM structure, the B soil was depleted in lignin and enriched in unspecific aromatics and polycyclic aromatic hydrocarbons, and in all scenarios, CF SOM consisted mainly of lignocellulose derived compounds and fatty acids. In general, FF SOM was found more altered than CF. High contribution of unspecific aromatic compounds and polycyclic aromatic hydrocarbons was observed in B-FF whereas BR-FF samples comprised considerable proportions of compounds from labile biomass, possibly due to soil mixing during rehabilitation actions. The fire caused a defunctionalisation of lignin-derived phenolics and the formation of pyrogenic compounds. The van Krevelen diagram was found useful to-at first sight-differentiate between chemical processes caused by fire and of the rehabilitation actions. Fire exerted SOM demethoxylation, dealkylation and dehydration. Our results indicate that soil management actions after the fire lead to an increase in aromaticity corresponding to the accumulation of lignin and polycyclic aromatic compounds. This suggests additional inputs from charred lignocellulosic biomass, including black carbon, that was incorporated into the soil during rehabilitation practices.

Thallium and co-genetic trace elements in hydrothermal Fe-Mn deposits of Central Spain.

Thallium (Tl) is a hazardous trace metal that can harm human and environmental health. Tl pollution can result from the mining and smelting of Tl-bearing minerals, but also the natural weathering of Tl-bearing sulfide minerals may induce Tl release to the environment. In this study, hydrothermal deposits hosted in dolostone rocks sited along fossil thermal springs in the Lodares region (Soria province, central Spain) were studied. In this hydrothermal mineralization zone, Tl association with primary minerals, identified Tl-bearing secondary products resulting from natural weathering of primary minerals, as well as the dispersion from its natural source along a seasonal small streambed were explored. Samples were analyzed by chemical, microscopic and spectroscopic techniques and epithermal pyrite, sphalerite, galena and barite and secondary gypsum, jarosite, scorodite, anglesite, goethite, epsomite and elemental sulfur produced by both inorganic and bacterial processes were found. The highest Tl contents were found in hydrothermal pyrite (188 mg kg-1), jarosite (142 mg kg-1), Mn-oxides (27 mg kg-1) or kerogen (13 mg kg-1). Feldspar was identified by electron probe microanalysis as potential host phase of Tl. XANES results confirmed the association of Tl(I) with metal sulfides in pyrite-rich samples and highlighted the role of jarosite-like minerals for Tl(I) sequestration upon pyrite oxidation, even in carbonate-rich samples at near-neutral pH. In addition to micaceous minerals, jarosite-group minerals and K-feldspars may contribute to the natural attenuation of Tl in soils and sediments.

Quantitative forecasting black (pyrogenic) carbon in soils by chemometric analysis of infrared spectra.

A detailed and global quantitative assessment of the distribution of pyrogenic carbon (PyC) in soils remains unaccounted due to the current lack of unbiased methods for its routine quantification in environmental samples. Conventional oxidation with potassium dichromate has been reported as a useful approach for the determination of recalcitrant C in soils. However, its inaccuracy due to the presence of residual non-polar but still non-PyC requires additional analysis by 13C solid-state nuclear magnetic resonance (NMR) spectroscopy, which is expensive and time consuming. The goal of this work is to examine the possibility of applying infrared (IR) spectroscopy as a potential alternative. Different soil type samples (paddy soil, Histic Humaquept, Leptosol and Cambisol) have been used. The soils were digested with potassium dichromate to determine the PyC content in environmental samples. Partial Least Squares (PLS) regression was used to build calibration models to predict PyC from IR spectra. A set of artificially produced samples rich in PyC was used as reference to observe in detail the IR bands derived from aromatic structures resistant to dichromate oxidation, representing black carbon. The results showed successful PLS forecasting of PyC in the different samples by using spectra in the 1800-400 cm-1 range. This lead to significant (P < 0.05) cross-validation coefficients for PyC, determined as the aryl C content of the oxidized residue. The Variable Importance for Projection (VIP) traces for the corresponding PLS regression models plotted in the whole IR range indicates the extent to which each IR band contributes to explain the aryl C and PyC contents. In fact, forecasting PyC in soils requires information from several IR regions. In addition to the expected IR bands corresponding to aryl C, other bands are informing about the patterns of oxygen-containing functional groups and the mineralogical composition characteristic of the soils with greater black carbon storage capacity. The VIP traces of the charred biomass samples confirm that aromatic bands (1620 and 1510 cm-1) are the most important in the prediction model for PyC-rich samples. These facts suggest that the mid-IR spectroscopy could be a potential tool to estimate the black carbon.

Chemometric assessment of soil organic matter storage and quality from humic acid infrared spectra.

The knowledge of biogeochemical mechanisms involved in soil organic carbon (SOC) storage is crucial to control its release to the atmosphere. In particular, the chemical composition of soil organic matter (SOM) plays an important role in the performance of the C storage and resilience in soils. The structural information provided by infrared spectroscopy (IR) of soil humic acid (HA) was used in the assessment of the C storage potential of 35 Spanish soils. Partial least squares (PLS) regression using the intensities of the points of the IR spectra of the HAs (4000-400 cm-1) as descriptors shows that a relationship exists between IR spectral pattern and the SOC content. This was also the case for E4 (humification index based on HA optical density at 465 nm). In addition, the chemical characteristics of the HAs correlated with the SOC levels were identified from digital data treatments of the IR spectra. Additional application of principal component analysis (PCA) and multidimensional scaling (MDS) suggested that bands assigned to carboxyl and amide structures were characteristic in HAs from soils with low C content, whereas HA spectra from soils with high C levels showed a conspicuous band pattern suggesting structural units of lignin from slightly transformed plant residues. The spectral profiles were analyzed in detail by an approach based on digital subtraction of IR spectra obtained by averaging those from HAs extracted from soils in the upper and lower quartiles of the SOC distribution. The results showed that significant relationships exist between the molecular composition of HAs and SOC levels and E4 values in a way in which aromatic, carboxyl and amide groups were predominant in HAs from soils with low SOC content, whereas lignin-derived structures were more characteristic of HAs from soils with high SOC content.

Mulching-induced preservation of soil organic matter quality in a burnt eucalypt plantation in central Portugal.

Mulching has amply proven its effectiveness to mitigate post-fire soil erosion but its impacts on soil organic matter (SOM) quality and quantity continue poorly studied. The present study addressed this knowledge gap for a eucalypt plantation in central Portugal that had been burnt and, immediately after the wildfire, mulched with 13.6 Mg ha-1 of eucalypt logging residues some five years before. This was done by performing a range of analytical techniques (elemental and isotope analyses, analytical pyrolysis and 13C NMR spectroscopy) not only on the bulk soil samples but also on their humic acids (HAs) and free organic matter (FOM) fractions. While mulching reduced soil and SOM losses with 91 and 93%, respectively, it also improved SOM quality of the topsoil, in particular in terms of HAs and FOM. At 0-4 cm depth, both HAs and FOM contents were roughly twice as high in the mulched plots as in the control plots. The effects of mulching on the molecular composition of HAs and FOM fractions, however, varied markedly. Analytical pyrolysis (Py-GC/MS) revealed that mulching had led to a noticeable accumulation of labile, aliphatic SOM constituents such as carbohydrate-derived and alkyl compounds (fatty acids and n-alkanes) but that it hardly affected the composition of HAs. Even so, solid-state 13C NMR spectroscopy showed that mulching had resulted in a relative increase in aryl C in the FOM fraction, suggesting an enhanced preservation of the pyrogenic OM. Overall, the combined use of a range of analytical techniques allowed to conclude that, five years after their application, the forest logging residues had led to a greater preservation of the fire-derived pyrogenic OM (mainly aromatic compounds) in the topsoil as well as to higher contents of SOM's most labile molecular constituents (mainly carbohydrates and n-alkyl compounds). The former reflected the reduced erosion rates, while the latter was probably due to a combination of reduced erosion rates with the additional input of fresh organic matter.

Soil Perturbation in Mediterranean Ecosystems Reflected by Differences in Free-Lipid Biomarker Assemblages.

Environmental information provided by free lipids in soil samples collected from control and disturbed plots (Madrid, Spain) was assessed by comparing molecular assemblages of terpenoids and distribution patterns of alkanes and fatty acids (FAs) analyzed by gas chromatography-mass spectrometry (GC-MS). Wildfires in pine forests led to increased proportions of retene, dehydroabietin, and simonellite. Friedo-oleananes were characteristic in soils under angiosperms, and norambreinolide-type diterpenes were characteristic in soils encroached by Cistus bushes. Steroids were major compounds in pastured sites. Enhanced Shannon's lipid biodiversity index in disturbed soils compared with in control soils suggested patterns of recent lipids overlapping a preserved original lipid signature. The extent of the environmental impacts was illustrated as Euclidean distances between paired control and disturbed sites calculated using the compounds in alkyl homologous series as descriptors. As expected, reforestation, bush encroachment, wildfires, and cultivation were reflected by changes in the molecular record of lipids in soils.

Ultra-high resolution mass spectrometry of physical speciation patterns of organic matter in fire-affected soils.

Fire is one of the most important modulating factors of the environment and the forest inducing chemical and biological changes on the most reactive soil component, the soil organic matter (SOM). Assuming the complex composition of the SOM, we used an ultra-high resolution mass spectrometry analysis technique to assess the chemical composition and fire-induced alterations in soil particle size fractions (coarse and fine) from a sandy soil in a Mediterranean oak forest at Doñana National Park (Southwest Spain). Electrospray ionization-Fourier transform ion cyclotron resonance mass spectrometry (ESI-FTICRMS) showed that the coarse fraction of soils not affected by fires consisted mainly of polyphenolic compounds consistent with little-transformed SOM and fresh biomass, whereas the fine fraction was enriched in protein and lipid like homologues suggesting microbially reworked SOM. In fire-affected SOM, the coarse fraction contained a high proportion of aromatic compounds, consistent with inputs of charred litter or in situ chemical transformation of the SOM. Analysis of the fine fraction revealed two differentiated chemical families pointing to the existence of two carbon pools; a native microbial-derived moiety composed of lipids and polypeptide compounds, and a secondary, pyrogenic or thermally-altered moiety rich in aromatic compounds. This work represents the first application of ultra-high resolution mass spectrometry to study the chemical composition of SOM in different particle size fractions.

Graphical statistical approach to soil organic matter resilience using analytical pyrolysis data.

Pyrolysis-gas chromatography-mass spectrometry (Py-GC-MS) of humic acids (HAs) from 30 agricultural soils from a volcanic island (Tenerife, Spain) was used to discern the molecular characteristics of soil organic matter (SOM) associated to resilience. For faster perceptual identification of the results, the yields of the pyrolysis products in the form of surface density plots were compared in an update of the Van Krevelen graphical statistical method. This approach, with respect to data reduction and visualization, was also used to collectively represent statistical indices that were obtained after simple and partial least squares (PLS) regression. The resulting plots illustrate different SOM structural domains (for example, carbohydrate- and lignin-derived and condensed lipid). The content of SOM and total mineralization coefficient (TMC) values can be well estimated from the relative abundance of 57 major pyrolysis compounds: SOM content and composition parallels the accumulation of lignin- and carbohydrate-derived structures (lignocellulosic material) and the depletion of condensed polyalkyl structures. In other words, in the volcanic ash soils that were studied, we found that the higher the amount of SOM, the lower its quality in terms of resilience. Although no cause-and-effect is inferred from this fact, it is evident that the resistance to biodegradation of the SOM is related to its molecular composition.

The diversity of methoxyphenols released by pyrolysis-gas chromatography as predictor of soil carbon storage.

The variable extent to which environmental factors are involved in soil carbon storage is currently a subject of controversy. In fact, justifying why some soils accumulate more organic matter than others is not trivial. Some abiotic factors such as organo-mineral associations have classically been invoked as the main drivers for soil C stabilization. However, in this research indirect evidences based on correlations between soil C storage and compositional descriptors of the soil organic matter are presented. It is assumed that the intrinsic structure of soil organic matter should have a bearing in the soil carbon storage. This is examined here by focusing on the methoxyphenols released by direct pyrolysis from a wide variety of topsoil samples from continental Mediterranean ecosystems from Spain with different properties and carbon content. Methoxyphenols are typical signature compounds presumptively informing on the occurrence and degree of alteration of lignin in soils. The methoxyphenol assemblages (12 major guaiacyl- and syringyl-type compounds) were analyzed by pyrolysis-gas chromatography-mass spectrometry. The Shannon-Wiener diversity index was chosen to describe the complexity of this phenolic signature. A series of exploratory statistical analyses (simple regression, partial least squares regression, multidimensional scaling) were applied to analyze the relationships existing between chemical and spectroscopic characteristics and the carbon content in the soils. These treatments coincided in pointing out that significant correlations exist between the progressive molecular diversity of the methoxyphenol assemblages and the concentration of organic carbon stored in the corresponding soils. This potential of the diversity in the phenolic signature as a surrogate index of the carbon storage in soils is tentatively interpreted as the accumulation of plant macromolecules altered into microbially reworked structures not readily recognized by soil enzymes. From a quantitative viewpoint, the partial least squares regression models exclusively based on total abundances of the 12 major methoxyphenols were especially successful in forecasting soil carbon storage.

Post-fire recovery of soil organic matter in a Cambisol from typical Mediterranean forest in Southwestern Spain.

Wildfire is a recurrent phenomenon in Mediterranean ecosystems and contributes to soil degradation and desertification, which are partially caused by alterations to soil organic matter (SOM). The SOM composition from a Cambisol under a Mediterranean forest affected by a wildfire is studied in detail in order to assess soil health status and better understand of soil recovery after the fire event. The soil was sampled one month and twenty-five months after the wildfire. A nearby unburnt site was taken as control soil. Soil rehabilitation actions involving heavy machinery to remove burnt vegetation were conducted sixteen months after the wildfire. Immediately after fire the SOM increased in topsoil due to inputs from charred vegetation, whereas a decrease was observed in the underlying soil layer. Twenty-five months after fire soil-pH increased in fire-affected topsoil due to the presence of ashes, a decrease in SOM content was recorded for the burnt topsoil and similar trend was observed for the water holding capacity. The pyro-chromatograms of burned soils revealed the formation of additional aromatic compounds. The thermal cracking of long-chain n-alkanes was also detected. Solid-state 13C NMR spectroscopy supported the increase of aromatic compounds in the fire-affected topsoil due to the accumulation of charcoal, whereas the deeper soil sections were not affected by the fire. Two years later, soil parameters for the unburnt and burnt sites showed comparable values. The reduction of the relative intensity in the aromatic C region of the NMR spectra indicated a decrease in the charcoal content of the topsoil. Due to the negligible slope in the sampling site, the loss of charcoal was explained by the post-fire restoration activity, degradation, leaching of pyrogenic SOM into deeper soil horizons or wind erosion. Our results support that in the Mediterranean region, fire-induced alteration of the SOM is not lasting in the long-term.

Compound-specific stable carbon isotopic signature of carbohydrate pyrolysis products from C3 and C4 plants.

BACKGROUND: Pyrolysis-compound specific isotopic analysis (Py-CSIA: Py-GC-(FID)-C-IRMS) is a relatively novel technique that allows on-line quantification of stable isotope proportions in chromatographically separated products released by pyrolysis. Validation of the Py-CSIA technique is compulsory for molecular traceability in basic and applied research. In this work, commercial sucrose from C4 (sugarcane) and C3 (sugarbeet) photosystem plants and admixtures were studied using analytical pyrolysis (Py-GC/MS), bulk δ(13)C IRMS and δ(13)C Py-CSIA. RESULTS: Major pyrolysis compounds were furfural (F), furfural-5-hydroxymethyl (HMF) and levoglucosan (LV). Bulk and main pyrolysis compound δ(13)C (‰) values were dependent on plant origin: C3 (F, -24.65 ± 0.89; HMF, -22.07 ± 0.41‰; LV, -21.74 ± 0.17‰) and C4 (F, -14.35 ± 0.89‰; HMF, -11.22 ± 0.54‰; LV, -11.44 ± 1.26‰). Significant regressions were obtained for δ(13)C of bulk and pyrolysis compounds in C3 and C4 admixtures. Furfural (F) was found (13)C depleted with respect to bulk and HMF and LV, indicating the incorporation of the light carbon atom in position 6 of carbohydrates in the furan ring after pyrolysis. CONCLUSION: This is the first detailed report on the δ(13)C signature of major pyrolytically generated carbohydrate-derived molecules. The information provided by Py-CSIA is valuable for identifying source marker compounds of use in food science/fraud detection or in environmental research.

Solid-phase micro-extraction (SPME) in the early detection of potentially active volatile compounds from organic wastes used for the management of soil-borne pathogens.

The complex molecular assemblages were analysed in the soil gas phase after applying pine forest wastes (PFW) or sugarbeet vinasses (SBV) for soil-borne crop pests' management. For this purpose, solid-phase micro-extraction (SPME) and gas chromatography (GC) were used coupled with mass spectrometry (MS). The organic wastes were applied either to Calcic Entisol or Haplic Arenosol moistened at field capacity and soil was covered with polyethylene sheet for 28-30 days to retain the volatiles. The PFW-treated soil mainly released volatile terpene hydrocarbons (trans-caryophyllene, beta-myrcene and p-cymene), with alpha-humulene and ethylbenzotriazole prevailing in the untreated soil. After SBV application mainly alkyl compounds and alkylbenzenes were released, whereas cyclohexanone, limonene, butanone, acetic acid, camphor and benzaldehyde occurred in the untreated soil. Compound assemblages also depended on the increasing water saturation in terms of soil depth, with sulphur compounds prevailing in deep horizons. Our results showed that SPME can be directly applied to soils to provide valuable information on volatile products from organic amendments.

Complementary multianalytical approach to study the distinctive structural features of the main humic fractions in solution: gray humic acid, brown humic acid, and fulvic acid.

Previous studies have indicated that the main fractions of humic substances (HS), gray humic acid (GHA), brown humic acid (BHA), and fulvic acid (FA), present different molecular patterns in water solution that are probably associated with specific structural features. However, the techniques used in these previous studies did not permit clarification of the principal qualitative characteristics of these structures. To study more in depth this subject several GHA, BHA, and FA have been analyzed through the complementary use of UV-visible and FTIR spectroscopy, (13)C NMR, thermogravimetry, and pyrolysis GC-MS. The results indicate that the studied humic fractions have different and distinctive structural features. Thus, large and nonpolar structural units (paraffins, olefins, terpenes) and aliphatic structures seem to accumulate in the gray fraction, whereas the smallest and more polar (furfural, phenols) and simpler structural units (sugar- and amino acid-related structures) are present in the fulvic one. BHA has a higher content in polycyclic aromatic moieties, S-containing compounds and aromatic structures, thus suggesting the presence of more condensed aromatic rings. Likewise, differences in both the presence of polar groups and the apparent molecular size explain the pattern of solubility as a function of pH and ionic strength (I) that defines each HS fraction. These results also indicate that the structural differences among the HS fractions are not only quantitative (the presence of the same type of structures differing in size and the concentration of functional groups) but also qualitative, because each fraction presented different and distinctive structural domains. These structural domains explain the molecular patterns associated with each HS fraction. Thus, the presence of smaller and more O-functionalized structural units including aromatic domains in FA explain their tendency to form molecular aggregates (hydrogen bridges, metal bridges, and hydrophobic interactions) in solution. This fact could also explain the presence of molecular aggregates in BHA, although to a lesser extent than in FA. Finally, the dominant aliphatic and less functionalized character of GHA may justify its lower tendency to form aggregates in solution at neutral and alkaline pH. Likewise, the results also indicate that the different structural domains associated with these fractions may be the consequence of diverse biosynthetic pathways involving different precursors.

Bioreactor treatment of municipal solid waste landfill leachates: characterization of organic fractions.

Quantitative and qualitative changes in organic matter were studied at different stages of treatment in a bioreactor designed to process leachates from a municipal solid waste landfill. The particulate matter (PM) and macromolecular fractions of the dissolved organic matter with solubility properties comparable to humic (acid-insoluble) and fulvic (acid-soluble) acid fractions (AI, AS, respectively) from the incoming black liquid, the bioreactor content, and the final processed effluent were isolated, quantified, and characterized by visible and infrared (IR) spectroscopies. The macromolecular signature either aliphatic (glycopeptides, carbohydrates) or aromatic (coinciding with infrared patterns of lignin, tannins etc.) enabled us to characterize the different organic fractions during the course of microbial transformation. The results reveal significant changes in the nitrogen speciation patterns within the different organic fractions isolated from the wastewater. The final increase in the relative proportions of nitrogen in the least aromatic AS fraction during microbial transformation could be related to protein formation inside the bioreactor. After biological treatment and ultrafiltration, the amount of organic matter was reduced by approximately 70%, whereas aromaticity increased in all fractions, indicating preferential elimination of aliphatic wastewater compounds. Most of the remaining fractions at the end of the process consisted of a yellow residue rich in low molecular weight AS fractions.

Multivariate statistical analysis of mass spectra as a tool for the classification of the main humic substances according to their structural and conformational features.

The aim of this work is to explore the suitability of the complementary use of mass spectra and the corresponding statistical analysis (principal components-Pareto analysis (PCA) and discriminant analysis (DA)) of these spectra to differentiate diverse humic samples as a function of their structural and conformational features. To this end, the mass spectra of humic samples belonging to the main humic fraction types (gray humic acid, brown humic acid, and fulvic acid) were obtained by electrospray ionization mass spectrometry (ESI-MS). The results obtained showed that the application of PCA yielded a clear separation between blanks and humic samples. However, a clear differentiation among the humic fraction types was not achieved. The DA of PCA data, however, yielded a clear separation among the humic substances (HS) samples belonging to each HS fraction type considered: gray humic acids, brown humic acids, and fulvic acids. These results showed that the mass spectra of each humic sample include characteristic mass/charge (m/z) distribution values that can be considered as a "fingerprint" representative of its specific structural features. Our results also indicate that, although the m/z values principally corresponded to single-charged ions, we cannot identify these molecular weight distributions with those of humic samples, since sample molecular fragmentation, as well as partial molecular ionization, cannot be ruled out under our experimental and instrumental conditions.

Raw or incubated olive-mill wastes and its biotransformed products as agricultural soil amendments-effect on sorption-desorption of triazine herbicides.

Raw olive-mill waste and soil amendments obtained from their traditional composting or vermicomposting were added, at rates equivalent to 200 Mg ha-1, to a calcareous silty clay loam soil in a laboratory test, in order to improve its fertility and physicochemical characteristics. In particular, the effects on the sorption-desorption processes of four triazine herbicides have been examined. We found that comparatively hydrophobic herbicides terbuthylazine and prometryn increased their retention on amended soil whereas the more polar herbicides simazine and cyanazine were less affected. Soil application of olive cake, without transformation, resulted in the highest herbicide retention. Its relatively high content in aliphatic fractions and lipids could explain the increased herbicide retention through hydrophobic bonding and herbicide diffusion favored by poorly condensed macromolecular structures. On the other hand, the condensed aromatic structure of the compost and vermicompost from olive cake could hinder diffusion processes, resulting in lower herbicide sorption. In fact, the progressive humification in soil of olive-mill solid waste led to a decrease of sorption capacity, which suggested important changes in organic matter quality and interactions during the mineralization process. When soil amended with vermicompost was incubated for different periods of time, the enhanced herbicide sorption capacity persisted for 2 months. Pesticide desorption was reduced by the addition of fresh amendments but was enhanced during the transformation process of amendments in soil. Our results indicate the potential of soil amendments based on olive-mill wastes in the controlled, selective release of triazine herbicides, which varies depending on the maturity achieved by their biological transformation.