Influence of acidification on the optical properties and molecular composition of dissolved organic matter

Acidification is a common method for preserving dissolved organic matter (DOM) in natural water samples until sophisticated laboratory analyses can be performed. However, little is known about the effects of this practice on the composition and optical properties of DOM. In this study, the effects of acidification on DOM in porewater samples collected from the RL IV bog system of the Glacial Lake Agassiz Peatlands in northern Minnesota were characterized. Molecular composition was determined by ultrahigh resolution mass spectrometry and optical properties by UV absorption and three-dimensional fluorescence spectroscopy. Excitation–emission matrix fluorescence spectroscopy results indicate that the fluorescence properties of the peatland porewater DOM were sensitive to pH and that the observed changes were fluorophore dependent. Ultrahigh resolution Fourier transform ion cyclotron resonance mass spectrometry revealed the appearance of newly formed, oxygen-rich compounds upon acidification. The extent to which these oxygen-rich compounds were formed was also dependent on the composition of the DOM.     

Chemical structure of soil organic matter

Journal of Thermal Analysis and Calorimetry - Selective preservation belongs among the important stabilization mechanisms of soil organic matter (SOM). Conceptually, it is based on non-covalent...     

Influence of heteroatom pre-selection on the molecular formula assignment of soil organic matter components determined by ultrahigh resolution mass spectrometry

Soil organic matter (SOM) is involved in many important ecosystem processes. Ultrahigh resolution mass spectrometry has become a powerful technique in the chemical characterization of SOM, allowing assignment of elemental formulae for thousands of peaks resolved in a typical mass spectrum. We investigated how the addition of N, S, and P heteroatoms in the formula calculation stage of the mass spectra processing workflow affected the formula assignments of mass spectra peaks. Dissolved organic matter extracted from plant biomass and soil as well as the soil humic acid fraction was studied. We show that the addition of S and P into the molecular formula calculation increased peak assignments on average by 17.3 % and 10.7 %, respectively, over the assignments based on the CHON elements frequently reported by SOM researchers using ultrahigh resolution mass spectrometry. The organic matter chemical characteristics as represented by van Krevelen diagrams were appreciably affected by differences in the heteroatom pre-selection for the three organic matter samples investigated, especially so for the wheat-derived dissolved organic matter. These results show that inclusion of both S and P heteroatoms into the formula calculation step, which is not routinely done, is important to obtain a more chemically complete interpretation of the ultrahigh resolution mass spectra of SOM.     

Hyphenation of a carbon analyzer to photo-ionization mass spectrometry to unravel the organic composition of particulate matter on a molecular level

The carbonaceous fraction of airborne particulate matter (PM) is of increasing interest due to the adverse health effects they are linked to. Its analytical ascertainment on a molecular level is still challenging. Hence, analysis of carbonaceous fractions is often carried out by determining bulk parameters such as the overall content of organic compounds (OC) and elemental carbon (EC) as well as the total carbon content, TC (sum of OC and EC), however, no information about the individual substances or substance classes, of which the single fractions consist can be obtained. In this work, a carbon analyzer and a photo-ionization time-of-flight mass spectrometer (PI-TOF-MS) were hyphenated to investigate individual compounds especially from the OC fractions. The carbon analyzer enables the stepwise heating of particle samples and provides the bulk parameters. With the PI-TOF-MS, it is possible to detect the organic compounds released during the single-temperature steps due to soft ionization and fast detection of the molecular ions. The hyphenation was designed, built up, characterized by standard substances, and applied to several kinds of samples, such as ambient aerosol, gasoline, and diesel emission as well as wood combustion emission samples. The ambient filter sample showed a strong impact of wood combustion markers. This was revealed by comparison to the product pattern of the similar analysis of pure cellulose and lignin and the wood combustion PM. At higher temperatures (450 °C), a shift to smaller molecules occurred due to the thermal decomposition of larger structures of oligomeric or polymeric nature comparable to lignocelluloses and similar oxygenated humic-like substances. Finally, particulate matter from gasoline and diesel containing 10% biodiesel vehicle exhaust has been analyzed. Gasoline-derived PM exhibited large polycyclic aromatic hydrocarbons, whereas diesel PM showed a much higher total organic content. The detected pattern revealed a strong influence of the biodiesel content on the nature of the particulate organic material.     

基于养分指标相关性的土壤有机质预测模型研究

为探究土壤间各养分指标间的相互关系,选取了天津市宁河区不同区域的种植土壤,基于行业标准规定的检测方法,对主要养分指标进行了测定,并研究各指标间的相关性。结果表明,各区域土壤pH值变异系数最小,整体均呈碱性;有机质、全氮及速效钾变异系数属于中等;有效磷的变异系数最高。各研究区域土壤有机质含量与全氮含量呈显著正相关(P<0.01),与pH值呈显著负相关(P<0.01),而与其他指标间不具备普遍且显著的相关性。基于多元线性回归分析建立了土壤有机质与全氮及pH值之间的预测模型,通过模型计算出的预测值与实际测定值的拟合性较好;另取土壤样品进行验证表明,预测模型具有良好的可靠性和准确性。     

Photodegradation of soil organic matter and its effect on gram-negative bacterial growth

To learn more about the role of the reactive oxygen species (ROS) in the production of bioavailable products of the dissolved organic matter, we investigate here the effect of the photolysis (lambda(exc) > 320 nm) of a soil extract (SE) on the growth of bacteria isolated from the same soil as used for obtaining the extract. Comparative experiments with Aldrich humic acid (AHA) as substrate were performed. The photodegradation of the SE was evaluated with different techniques-UV-visible absorption spectroscopy, fluorescence excitation emission matrices (EEM) and Fourier transform infrared spectroscopy (FTIR). Known ROS scavengers were employed to study the effect of photochemically produced ROS on the photodegradation of the substrates. To evaluate the effect of irradiation on the bioavailability of the SE and AHA, photolyzed and nonphotolyzed substrates were added to different culture media and the growth of Pseudomonas sp. isolated from the soil and a strain of Escherichia coli were studied. The different results obtained were assigned to the dissimilar metabolisms of both bacteria.     

Modeling sorption of soil organic matter on mineral surfaces: wood-derived polymers on mica

Molecular mechanics and molecular dynamics calculations were carried out on model organo–mineral composites typical of both paper products and soil. Sorption energy of neutral model linear chains of lignin, carbohydrate, and humic substances on muscovite mica depends on the mutual orientation of organic and mineral components, spatial organization and functionality of the organic chain, and the presence of metal cations. Carbohydrates are characterized by their higher affinity towards the mineral surface than the more flexible helical aromatic polymers. In the model calculations, sorption energies are twice as high. Oxidation of lignin into respective humic acids does not lead to better sorption. Unlike metal cations, water molecules interlacing between organic and mineral surfaces do not act as bridges and sharply decrease sorption energy. Flexible linear polymers may undergo drastic conformational changes when approaching the mineral surface, to ensure a gain in the interaction energy that more than compensates a loss in the conformational energy proper.     

Elucidating molecular level impact of peat fire on soil organic matter by laser desorption ionization Fourier transform ion cyclotron resonance mass spectrometry

Analytical and Bioanalytical Chemistry - In this work, laser desorption ionization coupled with Fourier transform ion cyclotron resonance mass spectrometry (LDI–FTICRMS) was used to...     

Methodological considerations for using thermal analysis in the characterization of soil organic matter

Thermal analysis is primarily used in the field of materials science, but has a long history in the geosciences. Soil organic matter (SOM) has received a great deal of recent scientific interest because of its role in the global carbon cycle. Conventional methods of characterizing SOM quality are unsatisfactory because they do not adequately capture the complete quality continuum that SOM comprises or the various mechanisms that act to stabilize it in the soil matrix. Thermal analysis techniques have the potential to capture this quality continuum, but are dependent on numerous experimental conditions that limit the comparability of results among different studies. Published methodology on thermal analysis of soils and sediments has largely focused on the characterization of the mineral component, while the organic component has received little attention. We tested several experimental conditions for their effects on the exothermic region of curves generated by thermal analysis of easily dispersed soil clay fractions and non-protected light-density particulate organic matter fractions isolated from the surface horizon of a forest soil. Results were found to be highly repeatable but strongly sensitive to crucible material, heating rate, and sample amount, and relatively insensitive to the use of a reference material. Thermal analysis is an important addition to the set of analytical tools used to characterize SOM quality because it provides direct, quantitative information of the energy potentially available for microbial metabolism. However, users will need to balance the needs of specific scientific objectives with the need for standardized methods and comparability between studies.     

Effects of soil pH and organic matter on distribution of thorium fractions in soil contaminated by rare-earth industries

The labilities of thorium fractions including mobility and bioavailability vary significantly with soil properties. The effects of soil pH and soil organic matter on the distribution and transfer of thorium fractions defined by a sequential extraction procedure were investigated. Decrease of soil pH could enhance the phytoavailability and the potential availability of thorium in soil. Increase of organic matter reduced the phytoavailability of thorium, but enhanced the potential availability of it. The reasons why soil pH and soil organic matter affect thorium fractions were discussed, and the behavior of the effects of soil properties on thorium fractions was elucidated. Fourier-transform infrared (FTIR) spectra were employed to reveal the positive relationship between the amounts adsorbed in humic material and/or amorphous oxides and the content of soil organic matter.     

Investigation on the binding of polycyclic aromatic hydrocarbons with soil organic matter: a theoretical approach

Polycyclic aromatic hydrocarbons (PAHs) are ubiquitous contaminants of the terrestrial environment that have been designated as Environmental Protection Agency (EPA) Priority Pollutants. In this study, molecular modeling was used to examine the physical and chemical characteristics of soil organic matter (SOM), fulvic acid (FA) and humic acid (HA), as well as their binding interactions with PAHs. The molecular structures of 18 PAHs were built by using the SYBYL 7.0 program and then fully optimized by a semiempirical (AM1) method. A molecular docking program, AutoDock 3.05, was used to calculate the binding interactions between the PAHs, and three molecular structure models including FA (Buffle's model), HA (Stevenson's model) and SOM (Schulten and Schnitzer's model). The pi-pi interactions and H-bonding interactions were found to play an important role in the intermolecular bonding of the SOM/PAHs complexes. In addition, significant correlations between two chemical properties, boiling point (bp) and octanol/water partition coefficient (Log K(ow)) and final docking energies were observed. The preliminary docking results provided knowledge of the important binding modes to FA, HA and SOM, and thereby to predict the sorption behavior of PAHs and other pollutants.     

Application of scanning calorimetry to estimate soil organic matter loss after fires

The severe heating of soil during wildfires and prescribed burns may result in adverse effects on soil fertility due to organic matter loss. No rapid and reliable procedure exists to evaluate soil organic matter (SOM) losses due to heating. Enthalpy of SOM combustion correlates with organic matter content. Quartz is a ubiquitous mineral in soils and has a remarkably constant composition and reversible α–β phase transition at 575 °C. We suggest that SOM content in heated and unheated soils can be compared using the ratio of SOM combustion enthalpy on heating to the β–α quartz transition enthalpy measured on cooling of the same sample. This eliminates the need to dry and weigh the samples, making possible field applications of the proposed method. The feasibility of using the (ΔH _{comb SOM})/(ΔH _β–α Qz) ratio was established with experiments on soil samples heated in the laboratory and the method was then used for evaluation of SOM loss on two pile burn sites at UC Berkeley’s Blodgett Forest Research Station in Georgetown, California.     

Molecular turnover time of soil organic matter in particle‐size fractions of an arable soil

The composition and molecular residence time of soil organic matter (SOM) in four particle‐size fractions (POM >200 µm, POM 63–200 µm, silt and clay) were determined using Curie‐point pyrolysis/gas chromatography coupled on‐line to mass spectrometry. The fractions were isolated from soils, either continuously with a C₃ wheat (soil ¹³C value = ?26.4‰), or transferred to a C₄ maize (soil ¹³C value = ?20.2‰) cropping system 23 years ago. Pyrograms contained up to 45 different pyrolysis peaks; 37 (ca. 85%) were identifiable compounds. Lignins and carbohydrates dominated the POM fractions, proteins were abundant, but lignin was (nearly) absent in the silt and clay fractions. The mean turnover time (MRT) for the pyrolysis products in particulate organic matter (POM) was generally <15 years (fast C pool) and 20–300 years (medium or slow C pools) in silt and clay fractions. Methylcyclopentenone (carbohydrate) in the clay fraction and benzene (mixed source) in the silt fraction exhibited the longest MRTs, 297 and 159 years, respectively. Plant‐derived organic matter was not stored in soils, but was transformed to microbial remains, mainly in the form of carbohydrates and proteins and held in soil by organo‐mineral interactions. Selective preservation of plant‐derived OM (i.e. lignin) based on chemical recalcitrance was not observed in these arable soils. Association/presence of C with silt or clays in soils clearly increased MRT values, but in an as yet unresolved manner (i.e. ‘truly’ stabilized, or potentially still ‘labile’ but just not accessible C). Copyright © 2009 John Wiley & Sons, Ltd.     

TMAH-preparative thermochemolysis for the characterization of organic matter in densimetric fractions of a Mediterranean forest soil

Physical protection is one of the most important ways for stabilization of organic carbon in soils, and in order to properly manage soils as a sink for carbon, it is necessary to know how much organic carbon a given soil could protect and to have information on the molecular composition of this protected organic matter in soil. To this end, we studied individual horizons taken from a soil profile under Quercus rotundifolia stands over calcareous parent material. Horizons were subjected to a sequential extraction using solutions of sodium polytungstate (NaPT) of increasing density (1.6, 1.8 and 2.0) to differentiate five fractions: a free light, extractable without sonication, three occluded (extractable by sonication) and a dense (retained in the dense residue, after sonication). The obtained fractions were analyzed by preparative thermochemolysis followed by gas chromatography–mass spectrometry (GC/MS) in order to get some insight on the molecular composition. The total ion chromatograms obtained for the pyrolysates of both of the densimetric fractions show various series of fatty acids (as their methyl esters), n-alkanols (as their methyl ethers), methylated α,ω-diacids, methylated ω-hydroxyacids, various lignous subunits and permethylated deoxy aldonic acids derived from carbohydrates. The comparison of the distributions of the thermochemolysis products shows that organic carbon in the dense fractions of the deepest horizons were more influenced by a microbial reworking than the others dense fractions from the upper horizons. It is also the case for the occluded fraction 1 of the H horizon even the vegetal part of the organic carbon in that occluded fraction appears to have a non-woody origin. On the other hand, the dense fraction of the H horizon is strongly marked by vegetal origin.     

Determination of low molecular weight organic acids in soil solution by HPLC

An HPLC method employing an ion exclusion column was developed for the determination of low molecular weight organic acids in soil solution. The method includes extensive sample pretreatment using ultrafiltration and cation exchange. The method showed linear calibration graphs (r>0.99) and the limits of detection in the range 0.1-26 muM. The recovery of eleven added acids ranged from 89 to 102%. Soil solutions of five horizons of a podzolised soil were analysed. The results showed that these compounds made up 1-3% of the dissolved organic carbon and 0-14% of the acidity. Identification of the major acids was also carried out by capillary zone electrophoresis.     

Pyrolysis—gas chromatography—mass spectrometry of a low organic matter calcareous soil

A modification to the general method of pyrolysis-gas chromatography of soils which improves the reproducibility of the technique is described. It has been applied to the study of a calcareous soil, low in organic matter and varations have been studied in programs from soil at different depths as well as from the corresponding humic acids, fulvic acids and extraction residues.Most of the major peaks have identified by gas chromatography-mass spectrometry: they correspond to those cited in earlier works. Data are presented on the characteristics of the pyrolysis products of this soil in the relation to their probobic origin. The evolution of organic matter through various pyrolysis relations is also discussed.     

Distribution of mercury in soil organic matter fractions obtained by dissolution/precipitation method

Sequential multistep procedure, usually used for the fractionation and characterization of soil organic matter was tested for Hg content in the individual steps and fractions. Under general laboratory conditions serious problems have arosen during the attempt in the Hg mass balance calculation. Several sources of Hg contamination were recognized. The most serious was the background concentration of Hg even in research grade chemicals (what is in general not declared) and laboratory air. The work on operational Hg speciation as non-humic bound, humic acid, fulvic acid bound proceeds from the established status-quo on distribution of mercury of soil organic matter.     

Analysis of soil organic matter biomarkers by sequential chemical degradation and gas chromatography-mass spectrometry

Low molecular weight (LMW) biomarkers can be used to trace the source and stage of soil organic matter. However, methods that selectively isolate these groups of compounds are underdeveloped. In this study, we isolate biomarkers by a successive series of extraction and chemical degradation procedures involving solvent extraction (TSE), base (BHY) and acid hydrolysis (AHY), and CuO oxidation (CUO). GC-MS was used to analyze these fractions and the extraction methods were verified by solid-state 13C NMR spectroscopy. The GC-MS response was high for the BHY products (96%), intermediate for the TSE (30%) and CUO (19%), but very low for the AHY fraction (5%) indicating that the fractions contain polar or high molecular weight compounds. Aliphatic lipids (62%), phenols and benzyls (17%) were the predominant classes, accompanied by minor abundances of mono- and disaccharides, LMW acids, terpenoids, steroids, amino acids, and amino sugars. The TSE and BHY fractions contained mainly aliphatic lipids derived from plant waxes, cutin, and suberin. Lignin-derived phenols are the major products in the CUO fraction, and amino compounds and carbohydrates of various sources were identified in the AHY products. The sequential degradation method is useful for the isolation and identification of apolar, LMW biomarkers in soil.