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Microbes (bacteria, phytoplankton) in the ocean are responsible for the copious production of exopolymeric substances (EPS) that include transparent exopolymeric particles. These materials act as a matrix to form marine snow. After the Deepwater Horizon oil spill, marine oil snow (MOS) formed in massive quantities and influenced the fate and transport of oil in the ocean. The processes and pathways of MOS formation require further elucidation to be better understood, in particular we need to better understand how dispersants affect aggregation and degradation of oil. Toward that end, recent work has characterized EPS as a function of microbial community and environmental conditions. We present a conceptual model that incorporates recent findings in our understanding of the driving forces of MOS sedimentation and flocculent accumulation (MOSSFA) including factors that influence the scavenging of oil into MOS and the routes that promote decomposition of the oil post MOS formation. In particular, the model incorporates advances in our understanding of processes that control interactions between oil, dispersant, and EPS in producing either MOS that can sink or dispersed gels promoting microbial degradation of oil compounds. A critical element is the role of protein to carbohydrate ratios (P/C ratios) of EPS in the aggregation process of colloid and particle formation. The P/C ratio of EPS provides a chemical basis for the “stickiness” factor that is used in analytical or numerical simulations of the aggregation process. This factor also provides a relative measure for the strength of attachment of EPS to particle surfaces. Results from recent laboratory experiments demonstrate (i) the rapid formation of microbial assemblages, including their EPS, on oil droplets that is enhanced in the presence of Corexit-dispersed oil, and (ii) the subsequent rapid oil oxidation and microbial degradation in water. These findings, combined with the conceptual model, further improve our understanding of the fate of the sinking MOS (e.g., subsequent sedimentation and preservation/degradation) and expand our ability to predict the behavior and transport of spilled oil in the ocean, and the potential effects of Corexit application, specifically with respect to MOS processes (i.e., formation, fate, and half-lives) and Marine Oil Snow Sedimentation and Flocculent Accumulation.

Marine sinking particulate organic matter (POM), acting as a link between surface primary production and burial of organic matter in marine sediments, undergoes a variety of physical and biochemical alterations on its way to the deep ocean, resulting in an increase in its un-characterizable proportion with diagenesis. Further, the binding ligands in POM for iron, an essential nutrient to marine life and tightly coupled with organic matter, has rarely been studied. In the current study, we employed an approach combining sequential extraction with ultrahigh resolution mass spectrometry (ESI-FTICRMS), in order to explore and unravel the chemical characteristics of organic matter compounds relevant to marine particle flux within the mesopelagic and deep ocean, with a focus on the potential iron-carrying molecules. With increasing depth, POM increases in aliphaticity, and decreases in intensity-normalized O/C ratios, aromatics, and carboxylic-rich alicyclic molecules (CRAM)-like compounds. The potential iron-carrying molecules account for ∼14% of total identified molecules, and appear to have been incorporated into the marine particles via ion complexation, hydrophobic interaction, and/or interlayered “occlusion.” The relative abundance of iron-binding organic molecules in these three operationally-defined categories changes with depth: “surficially-complexed” fraction decreases with depth, the “interlayered-occluded” fraction increases to a comparable extent and “hydrophobic interaction” fraction occurs at all depths. Collectively, the potential iron-carrying organic molecules exhibit a set of unique molecular characteristics: a relatively lower average H/C ratio and a higher O/C ratio compared to bulk POM, a dominance of aromatics, black carbon-like compounds and CRAM-like compounds, and minor amounts of aliphatics. These molecules exhibit partial similar molecular features as precursors formed from photochemical reactions in the surface ocean, but they have been greatly modified by flux processes. Noticeably, a minor fraction of these iron-carrying molecules (

9 páginas.-- 7 figuras.-- 2 tablas.-- 65 referencias.-- Supplementary data related to this article can be found at https://doi.org/10.1016/j.jenvman.2018.07.069., 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., The authors wish to thank MINECO project INTERCARBON (CGL2016-78937-R), and the Department of Chemistry and Biochemistry of the Old Dominion University (Norfolk, VA, USA) that provided access to the analytical facilities of the College of Science Major Instrumentation Cluster (COSMIC). Access to sampling sites and the logistics on-site was provided by project “Soil Carbon Turnover and Fluxes in Mediterranean Natural and Managed Ecosystems” (2017/19). NT Jiménez-Morillo is funded by FPI research grant (BES-2013-062573). N.T. Jiménez-Morillo is thanked for the preparation of the supplementary materials. JM de la Rosa thanks MINECO for funding his “Ramon y Cajal” contract.

Though pyrogenic carbon (pyC) has been assumed to be predominantly stable, degradation and transfers of pyC between various pools have been found to influence its cycling and longevity in the environment. Dissolution via leaching may be the main control on loss processes such as microbial or abiotic oxidation, mineral sorption, or export to aquatic systems. Yet, little is known of the controls on pyrogenic dissolved organic matter (pyDOM) generation or composition. Here, the yield and composition of pyDOM generated through batch leaching of a thermal series of oak and grass biochars, as well as several non-pyrogenic reference materials, was compared to that of their parent solids. Over 17 daily leaching cycles, biochars made from oak at 250 to 650° C released decreasing amounts of C on both a weight (16.9 to 0.3%, respectively) and C yield basis (7.4 to 0.2% C, respectively). Aryl-C represented an estimated 32 to 82% of C in the parent solids (identified by 13C-NMR), but only 7 to 38% in the leachates (identified by 1H-NMR), though both increased with pyrolysis temperature. PyC, often operationally defined as condensed aromatic carbon (ConAC), was quantified using the benzenepolycarboxylic acid (BPCA) method. Tri- and tetra-carboxylated BPCAs were formed from non-pyrogenic reference materials, thus, only penta- and hexa-carboxylated BPCAs were used to derive a BPCA-C to ConAC conversion factor of 7.04. ConAC made up 24 to 57% of the pyrogenic solid C (excluding the 250 °C biochar), but only about 9 to 23% of their respective leachates’ DOC, though both proportions generally increased with pyrolysis temperature. Weighted BPCA compound distributions, or the BPCA Aromatic Condensation (BACon) Index, indicate that ConAC cluster size increased in pyrogenic solids but not in leachates. Additional evidence presented suggests that both aromatic cluster size and O-containing functional group contents in the pyrogenic solid control pyC solubility. Overall, pyDOM was found to be compositionally dissimilar from its parent chars and contained a complex mixture of organic compound groups. Thus, it is expected that estimates of dissolved pyC production and export, made only by detection of ConAC, are too low by factors of 4 to 11.

Glycerol dialkyl glycerol tetraethers (GDGTs) are membrane-spanning lipids from Bacteria and Archaea that are ubiquitous in a range of natural archives and especially abundant in peat. Previous work demonstrated that the distribution of bacterial branched GDGTs (brGDGTs) in mineral soils is correlated to environmental factors such as mean annual air temperature (MAAT) and soil pH. However, the influence of these parameters on brGDGT distributions in peat is largely unknown. Here we investigate the distribution of brGDGTs in 470 samples from 96 peatlands around the world with a broad mean annual air temperature (-8 to 27 degrees C) and pH (3-8) range and present the first peat-specific brGDGT-based temperature and pH calibrations. Our results demonstrate that the degree of cyclisation of brGDGTs in peat is positively correlated with pH, pH = 2.49 x CBTpeat + 8.07 (n = 51, R-2 = 0.58, RMSE = 0.8) and the degree of methylation of brGDGTs is positively correlated with MAAT, MAAT(peat) (degrees C) = 52.18 x MBT'(5me) - 23.05 (n = 96, R-2 = 0.76, RMSE = 4.7 degrees C). These peat-specific calibrations are distinct from the available mineral soil calibrations. In light of the error in the temperature calibration (similar to 4.7 degrees C), we urge caution in any application to reconstruct late Holocene climate variability, where the climatic signals are relatively small, and the duration of excursions could be brief. Instead, these proxies are well-suited to reconstruct large amplitude, longer-term shifts in climate such as deglacial transitions. Indeed, when applied to a peat deposit spanning the late glacial period (similar to 15.2 kyr), we demonstrate that MAAT(peat) yields absolute temperatures and relative temperature changes that are consistent with those from other proxies. In addition, the application of MAAT(peat) to fossil peat (i.e. lignites) has the potential to reconstruct terrestrial climate during the Cenozoic. We conclude that there is clear potential to use brGDGTs in peats and lignites to reconstruct past terrestrial climate. (C) 2017 The Authors. Published by Elsevier Ltd.

The chemical composition of organic aerosols in the atmosphere is strongly influenced by human emissions. The effect these have on the environment, human health, and climate change is determined by the molecular nature of these chemical species. The complexity of organic aerosol samples limits the ability to study the chemical composition, and therefore the associated properties and the impacts they have. Many studies have addressed the water-soluble fraction of organic aerosols and have had much success in identifying specific molecular formulas for thousands of compounds present. However, little attention is given to the water-insoluble portion, which can contain most of the fossil material that is emitted through human activity. Here we compare the organic aerosols present in water extracts and organic solvent extracts (pyridine and acetonitrile) of an ambient aerosol sample collected in a rural location that is impacted by natural and anthropogenic emission sources. A semiquantitative method was developed using proton nuclear magnetic resonance spectroscopy to determine that the amount of organic matter extracted by pyridine is comparable to that of water. Electrospray ionization Fourier transform ion cyclotron resonance mass spectra show that pyridine extracts a molecularly unique fraction of organic matter compared to water or acetonitrile, which extract chemically similar organic matter components. The molecular formulas unique to pyridine were less polar, more aliphatic, and reveal formulas containing sulfur to be an important component of insoluble aerosol organic matter.

The shape of pulverized bituminous coal particles (vitrinites) was determined by optical and laser light scattering. Vitrain samples were collected from obvious tree remains located in the ceilings of two Appalachian coal mines. Wet sieving produced narrow size cuts. The particles were determined to be oblong or blocky in shape, with average length-to-width ratio of 1.7 and sphericity of 0.78. They were analogous in shape to a square ended, rectangular “house brick”. The two bituminous coals and different size cuts of each coal had essentially the same shape parameters. Characteristic heating times and terminal velocities were higher by 22 and 20%, respectively compared to spherical particles.

Organic aerosols (OA) are universally regarded as an important component of the atmosphere that have far-ranging impacts on climate forcing and human health. Many of these impacts are related to OA molecular characteristics. Despite the acknowledged importance, current uncertainties related to the source apportionment of molecular properties and environmental impacts make it difficult to confidently predict the net impacts of OA. Here we evaluate the specific molecular compounds as well as bulk structural properties of total suspended particulates in ambient OA collected from key emission sources (marine, biomass burning, and urban) using ultrahigh resolution mass spectrometry (UHR-MS) and proton nuclear magnetic resonance spectroscopy (1H NMR). UHR-MS and 1H NMR show that OA within each source is structurally diverse, and the molecular characteristics are described in detail. Principal component analysis (PCA) revealed that (1) aromatic nitrogen species are distinguishing components for these biomass burning aerosols; (2) these urban aerosols are distinguished by having formulas with high O/C ratios and lesser aromatic and condensed aromatic formulas; and (3) these marine aerosols are distinguished by lipid-like compounds of likely marine biological origin. This study provides a unique qualitative approach for enhancing the chemical characterization of OA necessary for molecular source apportionment.

Electrospray ionization Fourier transform ion cyclotron resonance mass spectrometry (ESI-FTICR-MS) has proven to be a powerful technique revealing complexity and diversity of natural DOM molecules, but its application to DOM analysis in grazing-impacted agricultural systems remains scarce. In the present study, we presented a case study of using ESI-FTICR-MS in analyzing DOM from four headwater streams draining forest- or pasture-dominated watersheds in Virginia, USA. In all samples, most formulas were CHO compounds (71.8–87.9%), with other molecular series (CHOS, CHON, CHONS, and CHOP (N, S)) accounting for only minor fractions. All samples were dominated by molecules falling in the lignin-like region (H/C = 0.7–1.5, O/C = 0.1–0.67), suggesting the predominance of allochthonous, terrestrial plant-derived DOM. Relative to the two pasture streams, DOM formulas in the two forest streams were more similar, based on Jaccard similarity coefficients and nonmetric multidimensional scaling calculated from Bray-Curtis distance. Formulas from the pasture streams were characterized by lower proportions of aromatic formulas and lower unsaturation, suggesting that the allochthonous versus autochthonous contributions of organic matter to streams were modified by pasture land use. The number of condensed aromatic structures (CAS) was higher for the forest streams, which is possibly due to the controlled burning in the forest-dominated watersheds and suggests that black carbon was mobilized from soils to streams. During 15-day biodegradation experiments, DOM from the two pasture streams was altered to a greater extent than DOM from the forest streams, with formulas with H/C and O/C ranges similar to protein (H/C = 1.5–2.2, O/C = 0.3–0.67), lipid (H/C = 1.5–2.0, O/C = 0–0.3), and unsaturated hydrocarbon (H/C = 0.7–1.5, O/C = 0–0.1) being the most bioreactive groups. Aromatic compound formulas including CAS were preferentially removed during combined light+bacterial incubations, supporting the contention that black carbon is labile to light alterations. Collectively, our data demonstrate that headwater DOM composition contains integrative information on watershed sources and processes, and the application of ESI-FTICR-MS technique offers additional insights into compound composition and reactivity unrevealed by fluorescence and stable carbon isotopic measurements.

We have developed a theoretical approach for evaluating the maturation of kerogen-like material, involving molecular dynamic reactive modelling with a reactive force field to simulate thermal stress. Morwell Brown Coal was selected to study the thermal evolution of terrestrial organic matter (OM). To achieve this, a structural model is first constructed on the basis of literature models and analytical characterization of our samples using modern 1and 2D nuclear magnetic resonance (NMR) spectroscopy, Fourier transform infrared (FTIR) spectroscopy and elemental analysis. Then, artificial maturation of the coal is performed at low conversion in order to obtain quantitative and qualitative detailed evidence for the structural evolution of the kerogen upon maturation. The chemical changes include defunctionalization of carboxyl, carbonyl and methoxy functional groups, coupled with an increase in cross linking in the residual matured kerogen. Gaseous and liquid hydrocarbons, essentially CH4, C4H8 and C14+ hydrocarbons, are generated in low amount, merely via cleavage of the lignin side chain.

Seeking to quantify the amount of refractory organic matter (ROM), which includes black carbon-like material (BC), in marine sediments, we have applied a two-step procedure that consists of a chemical oxidation with sodium chlorite of the demineralized sediments followed by integration of the aromatic C region in the remaining residues by solid-state 13C nuclear magnetic resonance (NMR) spectroscopy. The efficacy for lignin removal was tested by analytical pyrolysis in the presence of tetramethyl ammonium hydroxide (TMAH). Riverine, estuarine and offshore marine sediment samples were collected from the southwest Atlantic coast of Spain, a site of geological and environmental interest. Measured contents of BC-like material ranged between 3.0 and 45.7% of the total organic carbon. Greater relative BC contents were found in riverine sediments close to urban areas, which show an elevated input of anthropogenic organic material. The contents of BC-like material in offshore marine sediments (5.5–6.1%) were similar to those previously reported for these kinds of samples. However, NMR and pyrolysis-GC/MS of the isolated ROM reveals that abundant refractory aliphatic organic material remains in most of the marine samples after chlorite oxidation. We suggest that this pool of aliphatic carbon may play an important role as a stable carbon pool within the global C cycle., The Spanish Ministry of Education provided financial support for this research (fellowship BES-2003-1900 and project CGL2006-12730-C03-C01)., 9 páginas, 3 figuras, 6 tablas, 38 referencias.-- cmartin@irnase.csic.es

7 páginas, 5 figuras, 37 referencias., Using solid-state cross-polarization-magic-angle-spinning (CPMAS) 13C and 15N nuclear magnetic resonance (NMR) and 2-D double cross polarization (DCP) MAS 15N 13C NMR techniques, microbially degraded Botryococcus braunii was analyzed to study the chemical nature of organic nitrogen in the algal residue. The amide linkage, as found in protein, was observed as the major nitrogen component in 201-day-old degraded algae. No significant amount of heterocyclic nitrogen, or evidence for melanoidin products, was found. The results strongly suggest that proteinaceous material can survive early diagenesis and be preserved via its encapsulation by refractory, macromolecular, organic matter., Financial support for this work was provided by the National Science Foundation (OCE-9711596 to PGH and OCE-9907069 to HRH), the donors of the Petroleum Research Fund of the American Chemical Society (HRH), and the Ohio State University through a Graduate Student Award to X. Zang.

Este trabajo constituye el Capítulo 5 del libro.-- El DOI del volumen 651 es: 10.1021/bk-1996-0651., Nuclear magnetic resonance (NMR) spectroscopy has been used to characterize soil organic matter and study soil humification processes for nearly two decades, but only recently it has been considered a valuable analytical method in modern soil science. Technological and theoretical advances in the early development of NMR resulted in increased sensitivity and resolution of the NMR spectra of humic materials in soils. In turn, the increased utility of NMR led to the widespread initial use of this technique which is documented in the scientific literature by numerous NMR studies to obtain structural information on soil organic matter. Since those early applications spanning the 1970's and 1980's, a general hiatus has limited new developments in the field of soil science and the technique became routine in its application. Recently, some new applications involving isotope labeling combined with both 13C and 15N NMR has renewed interest in NMR as the premier technique for modern soil science research. This article reviews these recent developments.

Five out of seven marine microalgal species investigated were found to biosynthesize nonhydrolysable, mainly aliphatic, biomacromolecules (algaenans). The molecular structure of the algaenan isolated from the microalga Nannochloropsis salina of the class Eustigmatophyceae was determined by solid state 13 C NMR spectroscopy, Curie point pyrolysis-gas chromatography-mass spectrometry, and chemical degradations with HI and RuO 4 . The structure is predominantly composed of C 28 -C 34 linear chains linked by ether bridges. The algaenan isolated from a second eustigmatophyte ( Nannochloropsis sp.) was structurally similar. Algaenans isolated from two chlorophytes also possess a strongly aliphatic nature, as revealed by the dominance of alkenes/alkanes in their pyrolysates. Accordingly, we propose that the aliphatic character of numerous Recent and ancient marine kerogens reflects selectively preserved algaenans and that these algaenans may act as a source of n -alkanes in marine crude oils.

High‐resolution mass spectrometry (HRMS) has become a vital tool for dissolved organic matter (DOM) characterization. The upward trend in HRMS analysis of DOM presents challenges in data comparison and interpretation among laboratories operating instruments with differing performance and user operating conditions. It is therefore essential that the community establishes metric ranges and compositional trends for data comparison with reference samples so that data can be robustly compared among research groups. To this end, four identically prepared DOM samples were each measured by 16 laboratories, using 17 commercially purchased instruments, using positive‐ion and negative‐ion mode electrospray ionization (ESI) HRMS analyses. The instruments identified ~1000 common ions in both negative‐ and positive‐ion modes over a wide range of m/z values and chemical space, as determined by van Krevelen diagrams. Calculated metrics of abundance‐weighted average indices (H/C, O/C, aromaticity, and m/z) of the commonly detected ions showed that hydrogen saturation and aromaticity were consistent for each reference sample across the instruments, while average mass and oxygenation were more affected by differences in instrument type and settings. In this paper we present 32 metric values for future benchmarking. The metric values were obtained for the four different parameters from four samples in two ionization modes and can be used in future work to evaluate the performance of HRMS instruments Research Funding: Beatriu de Pinos. Grant Number: 2016‐00215 Division of Chemical, Bioengineering, Environmental, and Transport Systems. Grant Number: 1802388 Engineering and Physical Sciences Research Council. Grant Number: EP/L015307/1 French National FT‐ICR network. Grant Number: FR 3624 CNRS H2020 European Research Council. Grant Number: ERC‐STG 716196 H2020 Marie Skłodowska‐Curie Actions. Grant Number: CHROME‐839709 National Science Foundation. Grant Number: AGS‐1531454 Newton Fund. Grant Number: 275910721 NIH. Grant Number: S10OD018475 Vetenskapsrådet. Grant Number: 2018‐04618

Humic substances are ubiquitous in the environment, complex mixtures, and known to be beneficial to plant growth. To better understand and identify components responsible for plant growth stimulation, a terrestrial aquatic DOM sample was fractionated according to pH and polarity, obtaining acid-soluble and acid-insoluble portions, as well as acid-soluble hydrophobic and hydrophilic fractions using C18. The various fractions were characterized then evaluated for their biological effects on plant growth using bioassays with corn at two carbon rates. Approximately 43% and 57% of the carbon, and 31% and 69% of the iron, was found in the acid-insoluble and acid-soluble fractions, respectively. Upon separating the acid-soluble portion using C18 extraction, about 64% and 36% of the carbon (and 96% and 4% of the iron) was present in the hydrophilic and hydrophobic fractions, respectively. The acid-insoluble portion was more aromatic and less oxygenated than the acid-soluble fraction. The hydrophilic filtrate was oxygen-rich and contained mostly tannin-like molecules, while the hydrophobic retentate was more aromatic and lignin-like. During bioassay testing, it was found that more hydrophilic samples (those that are more oxygenated) yielded the highest response for shoot measurements. For root measurements, the lower DOC rate (0.01 mg/L C) gave better results than the higher DOC rate (0.1 mg/L C). Also, the hydrophobic, less oxygenated acid-insoluble sample performed better than the more hydrophilic acid-soluble portion. The polarity fractions at the lower carbon application showed that larger root systems occurred when there was more hydrophobic C18 retentate material present. The opposite was true for the root system at the higher carbon application, where larger roots existed when more hydrophilic C18 filtrate material was present. Compositional differences were found when comparing the acid-soluble versus acid-insoluble portions and the hydrophobic versus hydrophilic C18 fractions, and activity with respect to plant stimulation was discerned. While a carbon rate affect was observed during foliar application to corn plants (with the lower carbon rate generally yielding the best biological stimulation), the various observed trends indicate that plant response is due to not only the amount of carbon present but also the type of carbon.