Effect of Land Use Change on Molecular Composition and Concentration of Organic Matter in an Oxisol.

Land use change from native vegetation to cropping can significantly affect the quantity and quality of soil organic matter (SOM). However, it remains unclear how the chemical composition of SOM is affected by such changes. This study employed a sequential chemical extraction to partition SOM from an Oxisol into several distinct fractions: water-soluble fractions (ultrapure water (W)), organometal complexes (sodium pyrophosphate (PP)), short-range ordered (SRO) oxides (hydroxylamine-HCl (HH)), and well-crystalline oxides (dithionite-HCl (DH)). Coupled with Fourier transform ion cyclotron resonance mass spectrometry (FT-ICR-MS), the impact of land use change on the molecular composition of different OM fractions was investigated. Greater amounts of OM were observed in the PP and HH fractions compared to other fractions, highlighting their importance in SOM stabilization. The composition of different OM fractions varied based on extracted phases, with lignin-like and tannin-like compounds being prevalent in the PP and HH fractions, while aliphatic-like compounds dominated in the DH fraction. Despite changes in the concentration of each OM fraction from native vegetation to cropping, there was little influence of land use change on the molecular composition of OM associated with different mineral phases. No significant selective loss or preservation of organic carbon compounds was observed, indicating the composition of SOM remained unchanged.

Emerging investigator series: microplastic-based leachate formation under UV irradiation: the extent, characteristics, and mechanisms.

Microplastics in the aquatic system are among the many inevitable consequences of plastic pollution, which has cascading environmental and public health impacts. Our study aimed at analyzing surface interactions and leachate production of six microplastics under ultraviolet (UV) irradiation. Leachate production was analyzed for the dissolved organic content (DOC), UV254, and fluorescence through excitation emission (EEM) to determine the kinetics and mechanisms involved in the release of organic matter by UV irradiation. The results suggested there was a clear trend of organic matter being released from the surface of the six microplastics caused by UV irradiation based on DOC, UV254 absorbance, and EEM intensity increasing with time. Polystyrene had the greatest and fastest increase in DOC concentrations, followed by the resin coated polystyrene. Experiments conducted at different temperatures indicated the endothermic nature of these leaching mechanisms. The differences in leachate formation for different polymers were attributed to their chemical makeup and their potency to interact with UV. The aged microplastic samples were analyzed by Fourier-transform infrared spectroscopy (FT-IR), Raman, and X-ray photoelectron spectroscopy (XPS), to determine the surface changes with respect to leachate formation. Results indicated that all microplastics had increasing carbonyl indices when aged by UV with polystyrene being the greatest. These findings affirm that the leachate formation is an interfacial interaction and could be a significant source of organic compound influx to natural waters due to the extremely abundant occurrence of microplastics and their large surface areas.

Snowmelt periods as hot moments for soil N dynamics: a case study in Maine, USA.

The vernal transition represents the seasonal transition to spring, occurring as temperatures rise at the end of winter. With rapid snowmelt, microbial community turnover, and accelerated nutrient cycling, this is a critical but relatively under-studied period of ecosystem function. We conducted a study over two consecutive winters (2015-2016) at the Bear Brook Watershed in Maine to examine how changing winter conditions (warming winters, reduced snow accumulation) altered soil nitrogen availability and stream N export during winter and the vernal transition, and how these patterns were influenced by ecosystem N status (N-enriched vs. N-limited). Of the two study years, 2016 had a warmer winter with substantially less snow accumulation and a discontinuous snowpack-and as a result, had a longer vernal transition and a snowpack that thawed before the vernal transition began. Across both years, snowmelt triggered a transition, signaled by increased ammonium concentrations in soil, decreased soil nitrate concentrations due to flushing by meltwater, and increased stream nitrate exports. Despite the contrasting winter conditions, both years showed similar patterns in N availability and export, differing only in the timing of these transitions. The vernal transition has conventionally been considered a critical period for biogeochemical cycling, because the associated snowmelt event triggers physicochemical and biochemical changes in soil systems. This was consistent with our results in 2015, but our data for 2016 show that this may not always hold true, and instead, that warmer, low-snow winters may demonstrate a temporal asynchrony between snowmelt and the vernal transition. We also show that ecosystem N status is a strong driver of the seasonal N pattern, and the interaction of N status and changing climate must be further investigated to understand ecosystem function under our current predicted trajectory of warming winters, declining snowfall, and winter thaw events.

Adsorption of Organic Acids and Phosphate to an Iron (Oxyhydr)oxide Mineral: A Combined Experimental and Density Functional Theory Study.

The interaction of soil organic matter with mineral surfaces is a critical reaction involved in many ecosystem services, including stabilization of organic matter in the terrestrial carbon pool and bioavailability of plant nutrients. Using model organic acids typically present in soil solutions, this study couples laboratory adsorption studies with density functional theory (DFT) to provide physical insights into the nature of the chemical bonding between carboxylate functional groups and a model FeOOH cluster. Topological determination of electron density at bond critical points using quantum theory of atoms in molecules (QTAIM) analysis revealed that the presence of multiple bonding paths between the organic acid and the FeOOH cluster is essential in determining the competitive adsorption of organic acids and phosphate for FeOOH surface adsorption sites. The electron density and Laplacian parameter values from QTAIM indicated that the primary carboxylate-FeOOH bond was more ionic than covalent in nature. The experimental and computational results provide molecular-level evidence of the important role of electrostatic forces in the bonding between carboxylic acids and Fe-hydroxides. This knowledge may assist in the formulation of management studies to meet the challenges of maintaining ecosystems services in the face of a changing climate.

Direct Evidence for Temporal Molecular Fractionation of Dissolved Organic Matter at the Iron Oxyhydroxide Interface.

While the importance of organic matter adsorption onto reactive iron-bearing mineral surfaces to carbon stabilization in soils and sediments has been well-established, fundamental understanding of how compounds assemble at the mineral interface remains elusive. Organic matter is thought to layer sequentially onto the mineral surface, forming molecular architecture stratified by bond strength and compound polarity. However, prominent complexation models lack experimental backing, despite the role of such architecture in fractionated, compound-dependent persistence of organic matter and modulating future perturbations in mineral stabilization capacity. Here, we use kinetic assays and ultrahigh resolution Fourier transform ion cyclotron resonance mass spectrometry under high temporal frequency to directly detect the molecular partitioning of organic matter onto an iron oxyhydroxide during adsorption. We observed three sequential intervals of discrete molecular composition throughout the adsorption reaction, in which rapid primary adsorption of aromatic compounds was followed by secondary lignin-like and tertiary aliphatic compounds. These findings, paired with observed differential fractionation along formulas nitrogen and oxygen content and decreasing selective sorption with reaction time, support "zonal" assembly models. This work presents direct detection of sequential molecular assembly of organic matter at the mineral interface, an important yet abstruse regulator of carbon stabilization and composition across temporal and spatial scales.

Soil Chemistry and the One Health Initiative: Introduction to the Special Section.

Population growth and technical and social changes have always exerted pressure on environmental quality. However, we are experiencing unprecedented change in the rate and scale of human impacts on the environment. The One Health Initiative recognizes that improving the quality of life for humans and other animal species requires a holistic and integrated framework to seek multidisciplinary solutions to global environmental quality challenges. This special section is designed to elucidate the connections among soil health, environmental quality, food safety and security, and human health. Soil chemistry is defined as the field of soil science that deals with the chemical constituents, properties, and reactions of soils. Soil chemistry plays a central role in food production and the protection of human health. Chemical reactions between nutrients or contaminants and soil solids, and the composition of the soil solution and the atmosphere, influence crop growth as well as the quality of our food, air, and water. This collection of nine papers brings together studies that highlight how soil chemical constituents, properties, and reactions can be examined or managed using a multidisciplinary approach to move toward a more efficient, sustainable, nutrient-rich, and low-contaminant food production system that affords protection of soil, water, and human and animal health. We believe that studies such as these are needed to maintain and enhance environmental quality through interdisciplinary scientific approaches for human, animal, and environmental health outcomes.

Adsorption and Molecular Fractionation of Dissolved Organic Matter on Iron-Bearing Mineral Matrices of Varying Crystallinity.

Iron (Fe)-bearing mineral phases contribute disproportionately to adsorption of soil organic matter (SOM) due to their elevated chemical reactivity and specific surface area (SSA). However, the spectrum of Fe solid-phase speciation present in oxidation-reduction-active soils challenges analysis of SOM-mineral interactions and may induce differential molecular fractionation of dissolved organic matter (DOM). This work used paired selective dissolution experiments and batch sorption of postextraction residues to (1) quantify the contributions of Fe-bearing minerals of varying crystallinity to DOM sorption, and (2) characterize molecular fractionation using Fourier transform ion cyclotron resonance mass spectrometry (FT-ICR-MS). A substantial proportion of soil SSA was derived from extracted Fe-bearing phases, and FT-ICR-MS analysis of extracted DOM revealed distinct chemical signatures across Fe-OM associations. Sorbed carbon (C) was highly correlated with Fe concentrations, suggesting that Fe-bearing phases are strong drivers of sorption in these soils. Molecular fractionation was observed across treatments, particularly those dominated by short-range-order (SRO) mineral phases, which preferentially adsorbed aromatic and lignin-like formulas, and higher-crystallinity phases, associated with aliphatic DOM. These findings suggest Fe speciation-mediated complexation acts as a physicochemical filter of DOM moving through the critical zone, an important observation as predicted changes in precipitation may dynamically alter Fe crystallinity and C stability.

Higher Molecular Mass Organic Matter Molecules Compete with Orthophosphate for Adsorption to Iron (Oxy)hydroxide.

The competition between orthophosphate and water-extractable organic matter (WEOM) for adsorption to iron (oxy)hydroxide mineral surfaces is an important factor in determining the plant bioavailability of P in soils. Chemical force spectroscopy was used to determine the binding force between orthophosphate and iron (oxy)hydroxide that was coated onto atomic force microscopy (AFM) tips and adsorbed with WEOM. The force measurements were conducted at pH 4.65 and 0.02 M ionic strength which are representative of typical acid soil solutions. The chemical composition of the WEOM was determined by ultrahigh resolution electrospray ionization Fourier transform ion cyclotron mass spectrometry. The results indicate a correlation between aromatic WEOM molecules that are greater than 600 Da and the reduced binding force of orthophosphate to WEOM-adsorbed iron (oxy)hydroxide AFM tips suggesting that the molecular mass of aromatic WEOM molecules plays a critical role in regulating the WEOM-P interactions with surface functional groups of minerals. Based on the results of this study, we show the importance of obtaining a detailed, molecular-scale understanding of soil processes that can help develop better management strategies to reduce waste of limited P resources and adverse environmental impacts. Specifically, soil amendments with greater content of high molecular mass aromatic components may positively affect dissolved P use efficiency in soils by maintaining P in soil solution.

Comparative study of organic matter chemical characterization using negative and positive mode electrospray ionization ultrahigh-resolution mass spectrometry.

The chemical characterization of dissolved organic matter (DOM) is critical for understanding carbon sequestration processes in soils. This work evaluated the use of electrospray ionization in both negative ion mode (ESI-) and positive ion mode (ESI+) for the characterization of DOM extracted from nine terrestrial sources using Fourier transform ion cyclotron mass spectrometry (FT-ICR-MS). The compositing of the peaks from ESI- to ESI+ modes increased the total assigned formulas from 23 to 63 % as compared to the traditional use of ESI- alone for DOM characterization. In general, there was a preferential increase in the number of assignments for the aliphatic and carbohydrate-like DOM components in the ESI+ mode. The soil-extracted DOM specifically exhibited greater increases in the aliphatic and carbohydrate-like DOM components with the combined use of ESI- and ESI+ modes likely due to the greater presence of aromatic DOM molecules that suppressed the ionization of these entities in ESI- mode. On the basis of these findings, we show that improved characterization of DOM is possible through the combined use of ESI- and ESI+ modes for FT-ICR-MS analysis, especially for samples rich in condensed aromatic and aromatic molecules.

Chemical Force Spectroscopy Evidence Supporting the Layer-by-Layer Model of Organic Matter Binding to Iron (oxy)Hydroxide Mineral Surfaces.

The adsorption of dissolved organic matter (DOM) to metal (oxy)hydroxide mineral surfaces is a critical step for C sequestration in soils. Although equilibrium studies have described some of the factors controlling this process, the molecular-scale description of the adsorption process has been more limited. Chemical force spectroscopy revealed differing adhesion strengths of DOM extracted from three soils and a reference peat soil material to an iron (oxy)hydroxide mineral surface. The DOM was characterized using ultrahigh-resolution negative ion mode electrospray ionization Fourier Transform ion cyclotron resonance mass spectrometry. The results indicate that carboxyl-rich aromatic and N-containing aliphatic molecules of DOM are correlated with high adhesion forces. Increasing molecular mass was shown to decrease the adhesion force between the mineral surface and the DOM. Kendrick mass defect analysis suggests that mechanisms involving two carboxyl groups result in the most stable bond to the mineral surface. We conceptualize these results using a layer-by-layer "onion" model of organic matter stabilization on soil mineral surfaces.

Molecular composition and biodegradability of soil organic matter: a case study comparing two new England forest types.

Soil organic matter (SOM) is involved in many important soil processes such as carbon sequestration and the solubility of plant nutrients and metals. Ultrahigh resolution mass spectrometry was used to determine the influence of forest vegetation type and soil depth on the molecular composition of the water-extractable organic matter (WEOM) fraction. Contrasting the upper 0-5 cm with the 25-50 cm B horizon depth increment, the relative abundance of lipids and carbohydrates significantly increased, whereas condensed aromatics and tannins significantly decreased for the deciduous stand WEOM. No significant abundance changes were found for the coniferous stand DOM. Kendrick mass defect analysis showed that the WEOM of the 25-50 cm B horizon was depleted in oxygen-rich and higher mass components as compared to the 0-5 cm B horizon WEOM, suggesting that higher mass WEOM components with oxygen-containing functionality show greater reactivity in abiotic and/or biotic reactions. Furthermore, using an inoculated 14-day laboratory incubation study and multivariate ordination methods, we identified the WEOM components with H:C > 1.2 and O:C > 0.5 as being correlated most strongly with biodegradability. Our findings highlight the importance of understanding soil depth differences for various forest types in the chemical composition of SOM and the processes governing SOM production and transformations to fully understand the ecological implications of changes in forest composition and function in a changing climate.

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.

Fourier transform infrared and fluorescence spectral features of organic matter in conventional and organic dairy manure.

Organic dairy production has exhibited potential for growth in the United States dairy sector. However, little information is available on whether there is any difference in manure composition and quality between organic (OD) and conventional (CD) dairy manure even though the composition and quality are important parameters with respect to availability, utilization, and cycling of manure nutrients and environmental impact evaluation. We comparatively characterized whole and water-extracted materials of 15 OD and seven CD dairy manure samples by Fourier transform infrared (FT-IR) and fluorescence spectroscopies. Fourier transform infrared features of manure organic matter varied mainly in the 1650 to 1550 cm range, reflecting the presence of different N compounds in these manure samples. Fluorescence data revealed five fluorophore components present in the water-extracted organic matter from the manures. We found no clearly distinct value ranges in whole and water-extractable organic matter between the two types of dairy manure with respect to C and N contents and FT-IR and fluorescence spectral features. However, based on the average values, we observed general pattern differences on the effect of organic farming on the manure composition: OD contained less soluble C and N compounds on dry weight basis but more hydrophobic aliphatic groups in whole manure. The soluble organic matter in OD samples contained more stable humic- and lignin-related components and less amino/protein N-related components based on their spectroscopic features. These differences might be attributed to more forage feedstuffs in organic dairy farming management and more protein additives in conventional dairy feedstuffs. Information from this work may be useful in aiding organic dairy farmers in making manure management decisions.

Ultrahigh resolution mass spectrometry and indicator species analysis to identify marker components of soil- and plant biomass- derived organic matter fractions.

The chemical properties of organic matter affect important soil processes such as speciation, solubilization, and transport of plant nutrients and metals. This work uses ultrahigh resolution electrospray ionization Fourier transform ion cyclotron resonance mass spectrometry to determine the molecular composition of three organic matter fractions of soils and aqueous extracts of crop biomass. Comparison of the van Krevelen plots allowed tracking the changes in organic matter with increasing humification. Aqueous plant biomass extracts contain a diverse mixture of lipids, proteins, and lignins. Soil aqueous extracts were marked by increases in lignin and carbohydrate components and decrease in the protein component as compared to the plant extract. Refractory humic acid fractions were marked by decrease in the lignin component and increases in the lipid and condensed aromatic components. The multivariate indicator species analysis was used to identify marker components of the four organic matter types investigated. The plant extract group had 772 marker components compared to 237 for soil aqueous extract, 92 for mobile humic acid, and 418 for calcium humic acid. This study demonstrates that ultrahigh resolution mass spectrometry and multivariate methods can be used to identify marker components to gain a molecular-scale description and understanding of C dynamics.

Evaluation of D-dimer during pregnancy.

AIM: The purpose of the present study was to elucidate the change of D-dimer and the possibility of deep vein thrombosis screening by D-dimer during pregnancy. METHODS: One thousand, one hundred and thirty-one pregnant women were enrolled in the study from April 2006 to March 2007. D-dimer was measured by latex immunoassay at 6 to 14 and 30 to 36 weeks of gestation, respectively, and the veins of the lower extremities were examined by ultrasound at 30 to 36 weeks of gestation. RESULTS: The mean and standard error of D-dimer was 1.1 +/- 1.0 microg/mL in the first trimester and 2.2 +/- 1.1 microg/mL in the third trimester, and both values were significantly higher than adult values. In addition, D-dimer significantly increased during pregnancy. D-dimer was not significantly different between singleton and twin pregnancies in the first trimester, but in the third trimester, the values of twin pregnancies were higher than singleton pregnancies (2.2 +/- 1.6 vs 3.7 +/- 2.5 microg/mL). The mean value of D-dimer of ultrasonographically positive women was 2.6 +/- 2.0 microg/mL, which was significantly higher than the value for negative woman during the third trimester (2.2 +/- 1.6 microg/mL). The positive predictive value was 7.4% and negative predictive value was 95.5% for ultrasonographically positive women when D-dimer was set at 3.2 microg/mL. CONCLUSION: We clearly found a change of D-dimer during pregnancy. When D-dimer was higher than 3.2 microg/mL, the percentage of ultrasonographically positive women was high. We propose that women with D-dimer higher than 3.2 microg/mL are closely monitored for prevention of pulmonary thromboembolism.

[Analysis of demeton-S-methyl, oxydemeton-methyl and demeton-S-methylsulfone in agricultural products by LC-MS].

We studied the simultaneous determination of demeton-S-methyl, oxydemeton-methyl, and their oxide demeton-S-methylsulfone, in agricultural products by liquid chromatography coupled with mass spectrometry (LC-MS). The sample homogenized with antioxidants L-ascorbic acid and butylhydroxytoluene was extracted with acetone. An aliquot of the crude extract was reextracted with ethyl acetate by using an EXtrelut column. After hexane/acetonitrile partitioning lipid-rich samples such as cereals, the extract was cleaned up on a PSA column or tandem graphitized carbon/PSA column, and determined by ESI-SIM mode LC-MS. Average recoveries (n=5) of compounds from ten kinds of samples fortified at the analyte concentration of 0.05 microg/g were from 73.8% to 102.5%, and the relative standard deviations were

[Study on the method of setting limits for pesticides residues under the positive list system based on the data for pesticide residues in vegetables and fruits collected in Aichi Prefecture (Fiscal Years 2001-2005)].

Based on the data for pesticide residues in vegetables and fruits collected in Aichi prefecture (fiscal years 2001-2005), we selected groups of foods and pesticides that would allow efficient and effective inspection under the positive list system. Statistical analyses were done to examine the rates of detection of pesticides and the numbers of kinds of pesticides detected in samples of domestic vegetables, domestic fruits, imported vegetables, and imported fruits. The rate of detection of pesticides has decreased gradually in domestic vegetables. The number of different kinds of pesticides detected in each sample was significant higher in domestic fruits. Data for previous years were reassessed in terms of the present maximum residue limits (MRL), and classified as relative value to the MRL. The proportion of pesticides detected at levels that exceeded the MRLs showed a decreasing tendency. In addition, we were able to identify combinations of pesticides and agricultural commodities in which the MRLs were more likely to be exceeded.

[Multiresidue analysis of pesticides in agricultural products by GC/MS coupled with database software].

We evaluated a multiresidue method for determination of pesticides in agricultural products by SCAN mode GC/MS coupled with three kinds of database for 253 pesticides: relative retention time, mass spectra and calibration curve (SCAN method). Twenty-six pesticides, a total of 131 pesticides were detected in samples by the SCAN method. The detection results agreed closely with those of the SIM mode GC/MS method using calibration standards (SIM method). The ratios of the SCAN method to the SIM method ranged from 0.3 to 3.1 with SD values of 0.63. It was judged that the SCAN method could be applied to the screening analysis of pesticide residues in agricultural products, provided that the sample preparation method makes it possible to effectively remove sample matrixes with minimal loss of analytes.

Parallel factor analysis of excitation-emission matrix fluorescence spectra of water soluble soil organic matter as basis for the determination of conditional metal binding parameters.

Organic matter-metal complexes in soil solution and aquatic systems are involved in important environmental and ecological processes such as plant nutrient availability and the solubilization and transport of metals. Our work presented here extends the use of fluorescence spectrometry for determining conditional stability constants for such complexes. We combine the use of excitation-emission matrix (EEM) fluorescence spectrometry and parallel factor analysis (PARAFAC) to determine the stability constants of the chemically meaningful components modeled by PARAFAC. Water-soluble organic matter (WSOM) from O-horizon soils of deciduous and coniferous forest stands were extracted and titrated at pH = 4.7 with iron(lll) (Fe) and aluminum (Al) which are important metals in acid soil systems. The EEM spectra were then recorded and PARAFAC analysis showed that the WSOM contained three humic-substance-like components. Fe titration led to fluorescence quenching of the three components, while Al titration enhanced fluorescence for two components and quenched one of the components. The average Ryan-Weber stability constants at pH 4.7 ranged from log K of 4.28 to 4.91 for Fe and 4.84 to 5.96 for Al. The conditional stability constants were similar for Fe binding for deciduous and coniferous stand-derived WSOM, while they were stronger for Al binding with coniferous stand-derived WSOM. This difference in binding strengths for Al may affect the chemical behavior of Al in soil and aquatic systems. Determining the individual binding parameters of organic matter components with metals represents a significant advance over current approaches that utilize fluorescence quenching at a single excitation-emission wavelength pair to characterize organic matter-metal interactions.