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Soils, sediments, freshwaters, and marine waters contain natural organic matter (NOM), an exceedingly complex mixture of organic compounds that collectively exhibit a nearly continuous range of properties (size-reactivity continuum). NOM is composed mainly of carbon, hydrogen, and oxygen, with minor contributions from heteroatoms such as nitrogen, sulfur, and phosphorus. Suwannee River fulvic acid (SuwFA) is a fraction of NOM that is relatively depleted in heteroatoms. Ultrahigh resolution Fourier transform ion cyclotron (FTICR) mass spectra of SuwFA reveal several thousand molecular formulas, corresponding in turn to several hundred thousand distinct chemical environments of carbon even without accountancy of isomers. The mass difference Am among adjoining C,H,O-molecules between and within clusters of nominal mass is inversely related to molecular dissimilarity: any decrease of [DELTA]m imposes an ever growing mandatory difference in molecular composition. Molecular formulas that are expected for likely biochemical precursor molecules are notably absent from these spectra, indicating that SuwFA is the product of diagenetic reactions that have altered the major components of biomass beyond the point of recognition. The degree of complexity of SuwFA can be brought into sharp focus through comparison with the theoretical limits of chemical complexity, as constrained and quantized by the fundamentals of chemical binding. The theoretical C,H,O-compositional space denotes the isomer-filtered complement of the entire, very vast space of molecular structures composed solely of carbon, hydrogen, and oxygen. The molecular formulas within SuwFA occupy a sizable proportion of the theoretical C,H,O-compositional space. A 100 percent coverage of the theoretically feasible C,H,O-compositional space by SuwFA molecules is attained throughout a sizable range of mass and H/C and O/C elemental ratios. The substantial differences between (and complementarity of) the SuwFA molecular formulas that are observed using six different modes of ionization (APCI, APPI, and ESI in positive and negative modus) imply considerable selectivity of the ionization process and suggest that the observed mass spectra represent simplified projections of still more complex mixtures.

The aromatic region of two-dimensional heteronuclear [sup.1]H, [sup.13]C NMR spectra of natural organic matter and related materials (e.g.,[sup.1]H and [sup.13]C chemical shifts ranging from approximately 5 to 10 and 80 to 140 ppm, respectively) is highly complex and difficult to interpret using conventional approaches. In principle, this region of the NMR spectrum should be amenable to detailed analysis, because the effects of many common substituents on the chemical shifts of aromatic carbon and hydrogen are well documented. This paper describes the development of a model for prediction of substitution patterns in aromatic rings by increment analysis (SPARIA). In the forward mode, SPARIA is used to predict the chemical shifts of [sup.1]H and [sup.13]C on aromatic moieties containing every possible combination of eight common substituents that are likely to be representative of substituents on aromatic moieties in natural organic matter. The accuracy of SPARIA in the forward mode is evaluated for 29 aromatic compounds (100 peaks) by comparison of predicted chemical shifts for [sup.1]H and [sup.13]C with experimental values and with predictions of commercially available software for prediction of NMR spectra. The most important development in this paper is the inverse mode that is built into SPARIA. Given chemical shifts for [sup.1]H and [sup.13]C (such as may be obtained from a two-dimensional, heteronuclear NMR spectrum), the inverse mode of SPARIA calculates all possible combinations of the eight selected substituents that yield chemical shifts within a specified window of chemical shift for both [sup.1]H and [sup.13]C. Both the distribution of possible substitution patterns and simple descriptive statistics of the distribution are thus obtained. The inverse mode of SPARIA has been tested on the 29 aromatic compounds (100 peaks) that were used to evaluate its forward mode, and the dependence of the inverse process on the size of the chemical shift window has been evaluated. Finally, the inverse mode of SPARIA has been applied to selected peaks from the two-dimensional heteronuclear HSQC spectrum of a sample of natural organic matter that was isolated by reverse osmosis from the Suwannee River in southeastern Georgia.

The binding of cadmium to Suwannee River natural organic matter (NOM) has been investigated across a broad range of Cd/C ratios (0.00056-0.0056) and pH values (3.5-11) by [sup.113]Cd NMR spectroscopy at two magnetic field strengths ([B.sub.0] = 9.4 and 11.7 T). Caused by the very peculiar and highly complex nature of the Cd-NOM exchanging system, these [sup.113]Cd NMR spectra are characterized by a pH- and concentration-dependent superposition of slow, intermediate, and fast chemical exchange. The complex interplay of solution chemistry and chemical exchange requires a thorough mapping of this Cd-NOM chemically exchanging system through NMR acquisition at two magnetic field strengths and a systematic variation of Cd/C ratios and pH values. The interpretation of [sup.113]Cd NMR spectra is greatly facilitated and constrained by simultaneous measurements of pH and pCd, which allows a model-independent calculation of organically bound [Cd.sup.2+] under all experimental conditions. Within the range of chemical conditions applied in this study, [sup.113]Cd NMR spectrometric evidence is consistent with coordination of cadmium by oxygen, nitrogen, and sulfur ligands in NOM. Under all experimental conditions, cadmium is primarily coordinated to oxygen; however, several lines of evidence point to the participation of nitrogen ligands, even in acidic solutions where nitrogen ligands are primarily bound to protons. Under alkaline conditions, up to one-third of cadmium may be coordinated to nitrogen, and a small, but unquantifiable, percentage of cadmium is coordinated to sulfur ligands, as evidenced by far-low-field [sup.113]Cd NMR resonances.

To study the structure and function of soil organic matter, soil scientists have performed alkali extractions for soil humic acid (HA) and fulvic acid (FA) fractions for more than 200 years. Over the last few decades aquatic scientists have used similar fractions of dissolved organic matter, extracted by resin adsorption followed by alkali desorption. Critics have claimed that alkali‐extractable fractions are laboratory artifacts, hence unsuitable for studying natural organic matter structure and function in field conditions. In response, this review first addresses specific conceptual concerns about humic fractions. Then we discuss several case studies in which HA and FA were extracted from soils, waters, and organic materials to address meaningful problems across diverse research settings. Specifically, one case study demonstrated the importance of humic substances for understanding transport and bioavailability of persistent organic pollutants. An understanding of metal binding sites in FA and HA proved essential to accurately model metal ion behavior in soil and water. In landscape‐based studies, pesticides were preferentially bound to HA, reducing their mobility. Compost maturity and acceptability of other organic waste for land application were well evaluated by properties of HA extracted from these materials. A young humic fraction helped understand N cycling in paddy rice (Oryza sativa L.) soils, leading to improved rice management. The HA and FA fractions accurately represent natural organic matter across multiple environments, source materials, and research objectives. Studying them can help resolve important scientific and practical issues. Core Ideas: Humic substances have long been extracted from soils, waters, and organic materials.Their chemical composition has well represented that of natural organic matter.Compost maturation and composition are well represented by their properties.Soil humic studies elucidated metal and organic xenobiotic binding and nutrient cycling.Their quantities and composition in soil respond to field treatments. [ABSTRACT FROM AUTHOR]

High-field NMR spectra of Murchison meteorite methanolic extracts revealed primarily aliphatic extraterrestrial organic matter (EOM) with near statistical branching of commonly C3-5 units separated by heteroatoms and aromatic units. The ratios of CC H, OC H and Csp2 H units were 89 : 8 : 3, whereas carbon-based aliphatic chain termination was in the order methyl > COOH > CH(CH3)COOH. Aliphatic methine carbon was abundant, but its weak NMR signatures were primarily deduced from JRES (J-resolved) NMR spectra. Carbon NMR spectra were dominated by methylene and methyl carbon; strong apodization revealed methine carbon, of which about 20% was aromatic. Extrapolation provided 5-7% aromatic carbon present in Murchison soluble EOM. Compositional heterogeneity in Murchison methanolic extracts was visible in NMR and Fourier transform ion cyclotron (FTICR) mass spectra obtained from a few cubic millimeters of solid Murchison meteorite; increasing sample size enhanced uniformity of NMR spectra. Intrinsic chemical diversity and pH-dependent chemical shift variance contributed to the disparity of NMR spectra. FTICR mass spectra provided distinct clustering of CHO/CHOS and CHNO/CHNOS molecular series and confirmed the prevalence of aliphatic/alicyclic (73%) over single aromatic (21%) and polyaromatic (6%) molecular compositions, suggesting extensive aliphatic substitution of aromatic units as proposed by NMR. Murchison soluble EOM molecules feature a center with enhanced aromatic and heteroatom content, which provides rather diffuse and weak NMR signatures resulting from a huge overall chemical diversity. The periphery of Murchison EOM molecules comprises flexible branched aliphatic chains and aliphatic carboxylic acids. These project on narrow ranges of chemical shift, facilitating observation in one-dimensional and two-dimensional NMR spectra. The conformational entropy provided by these flexible surface moieties facilitates the solubility of EOM. Copyright © 2015 John Wiley & Sons, Ltd. [ABSTRACT FROM AUTHOR]

Wetlands provide quintessential ecosystem services such as maintenance of water quality, water supply and biodiversity, among others; however, wetlands are also among the most threatened ecosystems worldwide. They are usually characterized by high levels of natural dissolved organic matter (DOM), representing a critical component in wetland biogeochemistry. This study describes the first detailed, comparative, molecular characterization of DOM in sub-tropical, pulsed, wetlands, namely the Everglades (USA), the Pantanal (Brazil) and the Okavango Delta (Botswana), using optical properties, high field nuclear magnetic resonance (NMR) and ultrahigh resolution mass spectrometry (FT-ICRMS), and compares compositional features to variations in organic matter sources and flooding characteristics (i.e. differences in hydroperiod). While optical properties showed both similarities and differences between these ecosystems, these differences were mainly based on the degree of aromaticity of the DOM. Analogies were such that an established excitation emission matrix fluorescence parallel factor analysis (EEM-PARAFAC) model for the Everglades was perfectly applicable to the other two wetlands. High-field (500 and 800 MHz) NMR spectra with cryogenic detection provided exceptional coverage and chemical description of wetland solid phase extracted (SPE) DOM. Area-normalized ¹H NMR spectra of selected samples revealed clear distinctions of samples along with pronounced congruence within the three pairs of wetland DOM. Within sample pairs (long vs. short hydroperiod sites), internal differences mainly referred to intensity variations (denoting variable abundance) rather than to alterations of NMR resonances positioning (denoting diversity of molecules). The relative disparity was largest between the Everglades long and short hydroperiod samples, whereas Pantanal and Okavango samples were more alike among themselves. Otherwise, molecular divergence was most obvious in the case of unsaturated protons (δH > 5 ppm). The larger discrimination observed between ¹H NMR spectra of DOM from different wetlands in comparison with the intrinsic variance among DOM within each wetland readily suggests the presence of an individual molecular signature, characteristic of each particular wetland. 2-D NMR spectroscopy for a particular sample revealed a large richness of aliphatic and unsaturated substructures, likely derived from microbial sources such as periphyton in the Everglades. In contrast, the chemical diversity of aromatic wetland DOM likely originates from a combination of higher plant sources, progressive microbial and photochemical oxidation, and contributions from combustion-derived products (e.g. black carbon). In addition, FT-ICRMS spectra allowed far-reaching classifications of wetland DOM. While DOM of both Okavango and Pantanal showed near 57 ± 2% CHO, 8 ± 2% CHOS, 33 ± 2 CHNO, and<1% CHNOS molecules, the mass spectra of Everglades samples were fundamentally different compared to those as well as among long and short hydroperiod samples, as they were markedly enriched in CHOS and CHNOS at the expense of CHO and CHNO compounds. Here, four groups of CHOS molecules were differentiated as (a) saturated sulfolipids, (b) unsaturated sulfolipids, (c) molecularly diverse DOM-type CHOS molecules, (d) and particularly enriched in the Everglades short hydroperiod site, a large set of aromatic and oxygen-deficient "black sulphur" compounds. The significantly higher proportion of CHOS compounds in general for the Everglades samples is likely the result of higher inputs of agriculture-derived and sea spray derived sulphate to this wetland compared to the others. Although wetland DOM samples were found to share many molecular features, each sample was unique in its composition, which reflected specific environmental drivers and/or specific biogeochemical processes. [ABSTRACT FROM AUTHOR]

Introduction: The surface and possible sub-surface materials of the asteroid Ryugu were recovered during the two touch-down sampling by the Hayabusa2 spacecraft. Here we present the first results on the solvent soluble organic matter (SOM) of the surface sample (A0106) using ultrahigh-resolution Fourier transform ion cyclotron resonance mass spectroscopy (FTICR/MS) complemented with high field nuclear magnetic resonance spectroscopy (NMR) [1-3]. The goals of the SOM analysis using ultrahigh resolution mass spectrometry and NMR-spectroscopy were (i) to profile organic compounds with the elements C, H, N, O, S, Mg from the Ryugu samples, (ii) to compare these organic signatures to the state of the art in knowledge of meteoritic soluble organic matter, and (iii) to evaluate possible alteration processes that may have occurred on the parent body (temperature and shock stresses, water alteration) leading to organic matter preservation or specific transformations (i.e. organosulfurs, organomagnesiums). The samples A0106 (first touchdown) was sequentially extracted in the Hayabusa2-initial-analysis SOM team with various apolar to polar solvents and demonstrate a never seen molecular complexity and diversity. Results and Discussion: We confirm herewith the close similarity and the possible comparison of the solvent extracts with meteoritic material to the Hayabusa2 return samples. We analyzed the sequential hexane, dichloromethane (DCM), methanol, and water extracts of A0106 with NMR and with ESI- and APPI-FTICR/MS systematically for both negative and positive ions. The hundred thousands of signals obtained were filtered, converted and conservatively cumulative assigned into more than 25,000 elementary compositions consisting of carbon (C), hydrogen (H), nitrogen (N), oxygen (O) and/or sulfur (S). Organomagnesium compounds (CHOMg, CHOSMg) were not found and this reflects the low temperature processes on the parent body [5, 6]. As shown for carbonaceous chondrites previously, our results confirm that the extraterrestrial chemical diversity is much higher compared to terrestrial biological and the biogeochemical spaces and consists in a regular continuum (i) of small to macromolecules and (ii) of carbon oxidation states from apolar (CH, polycyclic aromatic hydrocarbons and branched aliphatics as analyzed with APPI) to polar small molecules (CHO) with increasing functionalized groups with varying oxygen and heteroatom contents (CHN, CHS, CHNO, CHOS); these lead to the observed differential solvent type solubility observed in the sequential extraction and with the diverse ionization methods. Combining the sequential solvent extraction of increasing polarity with the various ionization sources prior FTICR/MS showed evidences of multiple chemosynthesis pathways in describing the mass ranges, the carbon oxidation state distribution, and heteroatom contributions to the assembly of multiple complex molecules. Compared to SOM of meteorites these specific profiles of sample A0106 reflect cold hydrothermalism involved on the parent body [5, 6]. We also confirm the importance of chemical processes involving specific nitrogen and sulfur chemistry. We also revealed specific known molecular targets such as PAHs and alkylated N-containing heterocyclic compounds and alkylpyridine homologues (CnH2n-4N+) such as described on the sample with DESI/HRMS [7] and as described with Murchison meteorite previously [4]. Conclusions: Ryugu sample A0106 showed extreme chemical diversity and complexity, close to low temperature water altered meteoritic materials. These samples present a unique opportunity of having a direct and low invasive insight into the complex organic diversity present on 162173 Ryugu. [ABSTRACT FROM AUTHOR]

High-performance, non-target, high-resolution organic structural spectroscopy was applied to solid phase extracted marine dissolved organic matter (SPE-DOM) isolated from four different depths in the open South Atlantic Ocean off the Angola coast (3° E, 18° S; Angola Basin) and provided molecular level information with extraordinary coverage and resolution. Sampling was performed at depths of 5 m (Angola Current; near-surface photic zone), 48 m (Angola Current; fluorescence maximum), 200 m (still above Antarctic Intermediate Water, AAIW; upper mesopelagic zone) and 5446 m (North Atlantic Deep Water, NADW; abyssopelagic, ∼30 m above seafloor) and produced SPE-DOM with near 40 % carbon yield and beneficial nuclear magnetic resonance (NMR) relaxation properties, a crucial prerequisite for the acquisition of NMR spectra with excellent resolution. ¹H and 13C NMR spectra of all four marine SPE-DOM showed smooth bulk envelopes, reflecting intrinsic averaging from massive signal overlap, with a few percent of visibly resolved signatures and variable abundances for all major chemical environments. The abundance of singly oxygenated aliphat-ics and acetate derivatives in ¹H NMR spectra declined from surface to deep marine SPE-DOM, whereas C-based aliphat-ics and carboxyl-rich alicyclic molecules (CRAM) increased in abundance. Surface SPE-DOM contained fewer methyl esters than all other samples, likely a consequence of direct exposure to sunlight. Integration of 13C NMR spectra revealed continual increase of carboxylic acids and ketones from surface to depth, reflecting a progressive oxygenation, with concomitant decline of carbohydrate-related substructures. Aliphatic branching increased with depth, whereas the fraction of oxygenated aliphatics declined for methine, methy-lene and methyl carbon. Lipids in the oldest SPE-DOM at 5446 m showed a larger share of ethyl groups and methylene carbon than observed in the other samples. Two-dimensional NMR spectra showed exceptional resolution and depicted resolved molecular signatures in excess of a certain minimum abundance. Classical methyl groups terminating aliphatic chains represented ∼15 % of total methyl in all samples investigated. A noticeable fraction of methyl (∼2 %) was bound to olefinic carbon. Methyl ethers were abundant in surface marine SPE-DOM, and the chemical diversity of carbohydrates was larger than that of freshwater and soil DOM. In all samples, we identified sp²-hybridized carbon chemical environments with discrimination of isolated and conjugated olefins and α,β-unsaturated double bonds. Olefinic proton and carbon atoms were more abundant than aromatic ones; olefinic unsaturation in marine SPE-DOM will be more directly traceable to ultimate biogenic precursors than aromatic unsaturation. The abundance of furan, pyrrol and thiophene derivatives was marginal, whereas benzene derivatives, phenols and six-membered nitrogen heterocycles were prominent; a yet unassigned set of six-membered N-heterocycles with likely more than one single nitrogen occurred in all samples. Various key polycyclic aromatic hydrocarbon substructures suggested the presence of thermogenic organic matter at all water depths. Progressive NMR cross-peak attenuation from surface to deep marine SPE-DOM was particularly strong in COSY NMR spectra and indicated a continual disappearance of biosignatures as well as entropy gain from an ever increased molecular diversity. Nevertheless, a specific near-seafloor SPE-DOM signature of unsaturated molecules recognized in both NMR and Fourier transform ion cyclotron mass spectrometry (FTICR/MS) possibly originated from sediment leaching. The conformity of key NMR and FTICR/MS signatures suggested the presence of a large set of identical molecules throughout the entire ocean column even though the investigated water masses belonged to different oceanic regimes and currents. FTICR/MS showed abundant CHO, CHNO, CHOS and CHNOS molecular series with slightly increasing numbers of mass peaks and average mass from surface to bottom SPEDOM. The proportion of CHO and CHNO negative ions increased from surface to depth, whereas CHOS and especially CHNOS molecular series markedly declined. While certain rather aliphatic CHOS and CHNOS ions were observed solely in the surface, deep marine SPE-DOM was enriched in unique unsaturated and rather oxygenated CHO and CHNO molecular series. With the exception of abyssopelagic SPEDOM at 5446 m, which showed a peculiar CHOS chemistry of unsaturated carbon and reduced sulphur (black sulphur), CHO and CHNO molecular series contributed ∼87% to total positive electrospray ionization FTICR mass peak integral, with a near constant ratio of CHNO/CHO molecular compositions near 1.13±0.05. In case of all four marine SPE-DOM, remarkably disparate average elemental compositions as determined from either MS and NMR spectra were observed, caused by a pronounced ionization selectivity in electrospray ionization FTICR/MS. The study demonstrates that the exhaustive characterization of complex unknowns in marine DOM will enable a meaningful classification of individual marine biogeosignatures. Future in-depth functional biodiversity studies with a clear understanding of DOM structure and function might eventually lead to a novel, unified perception of biodiversity and biogeochemistry. [ABSTRACT FROM AUTHOR]

Atmospheric aerosols impose direct and indirect effects on the climate system, for example, by absorption of radiation in relation to cloud droplets size, on chemical and organic composition and cloud dynamics. The first step in the formation of Organic primary aerosols, i.e. the transfer of dissolved organic matter from the marine surface into the atmosphere, was studied. We present a molecular level description of this phenomenon using the high resolution analytical tools of Fourier transform ion cyclotron resonance mass spectrometry (FT-ICR MS) and nuclear magnetic resonance spectroscopy (NMR). Our experiments confirm the chemoselective transfer of natural organic molecules, especially of aliphatic compounds from the surface water into the atmosphere via bubble bursting processes. Transfer from marine surface water to the atmosphere involves a chemical gradient governed by the physicochemical properties of the involved molecules when comparing elemental compositions and differentiating CHO, CHNO, CHOS and CHNOS bearing compounds. Typical chemical fingerprints of compounds enriched in the aerosol phase were CHO and CHOS molecular series, smaller molecules of higher aliphaticity and lower oxygen content, and typical surfactants. A nontargeted metabolomics analysis demonstrated that many of these molecules corresponded to homologous series of oxo-, hydroxy-, methoxy-, branched fatty acids and mono-, diand tricarboxylic acids as well as monoterpenes and sugars. These surface active biomolecules were preferentially transferred from surface water into the atmosphere via bubble bursting processes to form a significant fraction of primary organic aerosols. This way of sea spray production leaves a selective biological signature of the surface water in the corresponding aerosol that may be transported into higher altitudes up to the lower atmosphere, thus contributing to the formation of secondary organic aerosol on a global scale or transported laterally with possible deposition in the context of global biogeocycling. [ABSTRACT FROM AUTHOR]

Non target high resolution organic structural spectroscopy of marine dissolved organic matter (DOM) isolated on 27 November 2008 by means of solid phase extraction (SPE) from four different depths in the South Atlantic Ocean off the Angola coast (3.1° E; -17.7° S; Angola basin) provided molecular level information of complex unknowns with unprecedented coverage and resolution. The sampling was intended to represent major characteristic oceanic regimes of general significance: 5m (FISH; near surface photic zone), 48m (FMAX; fluorescence maximum), 200m (upper mesopelagic zone) and 5446m (30m above ground). 800MHz proton (¹H) nuclear magnetic resonance (NMR) ¹H NMR, spectra were least affected by fast and differential transverse NMR relaxation and produced at first similar looking, rather smooth bulk NMR envelopes reflecting intrinsic averaging from massive signal overlap. Visibly resolved NMR signatures were most abundant in surface DOM but contributed at most a few percent to the total ¹H NMR integral and were mainly limited to unsaturated and singly oxygenated carbon chemical environments. The relative abundance and variance of resolved signatures between samples was maximal in the aromatic region; in particular, the aromatic resolved NMR signature of the deep ocean sample at 5446m was considerably different from that of all other samples. When scaled to equal total NMR integral, ¹H NMR spectra of the four marine DOM samples revealed considerable variance in abundance for all major chemical environments across the entire range of chemical shift. Abundance of singly oxygenated CH units and acetate derivatives declined from surface to depth whereas aliphatics and carboxyl-rich alicyclic molecules (CRAM) derived molecules increased in abundance. Surface DOM contained a remarkably lesser abundance of methyl esters than all other marine DOM, likely a consequence of photodegradation from direct exposure to sunlight. All DOM showed similar overall 13C NMR resonance envelopes typical of an intricate mixture of natural organic matter with noticeable peaks of anomerics and C-aromatics carbon whereas oxygenated aromatics and ketones were of too low abundance to result in noticeable humps at the S/N ratio provided. Integration according to major substructure regimes revealed continual increase of carboxylic acids and ketones from surface to deep marine DOM, reflecting a progressive oxygenation of marine DOM, with concomitant decline of carbohydrate-related substructures. Isolation of marine DOM by means of SPE likely discriminated against carbohydrates but produced materials with beneficial NMR relaxation properties: a substantial fraction of dissolved organic molecules present allowed the acquisition of two-dimensional NMR spectra with exceptional resolution. JRES, COSY and HMBC NMR spectra were capable to depict resolved molecular signatures of compounds exceeding a certain minimum abundance. Here, JRES spectra suffered from limited resolution whereas HMBC spectra were constrained because of limited S/N ratio. Hence, COSY NMR spectra appeared best suited to depict organic complexity in marine DOM. The intensity and number of COSY cross peaks was found maximal for sample FMAX and conformed to about 1500 molecules recognizable in variable abundance. Surface DOM (FISH) produced a slightly (~25 %) lesser number of cross peaks with remarkable positional accordance to FMAX (~80% conforming COSY cross peaks were found in FISH and FMAX). With increasing water depth, progressive attenuation of COSY cross peaks was caused by fast transverse NMR relaxation of yet unknown origin. However, most of the faint COSY cross peak positions of deep water DOM conformed to those observed in the surface DOM, suggesting the presence of a numerous set of identical molecules throughout the entire ocean column even if the investigated water masses belonged to different oceanic regimes and currents. Aliphatic chemical environments of methylene (CH2) and methyl (CH3) in marine DOM were nicely discriminated in DEPT HSQC NMR spectra. Classical methyl groups terminating aliphatic chains represented only ~15% of total methyl in all marine DOM investigated. Chemical shift anisotropy from carbonyl derivatives (i.e. most likely carboxylic acids) displaced aliphatic methyl ¹H NMR resonances up toδH ~1.6 ppm, indicative of alicyclic geometry which furnishes more numerous short range connectivities for any given atom pairs. A noticeable fraction of methyl (~2 %) was bound to olefinic carbon. The comparatively large abundance of methyl ethers in surface marine DOM contrasted with DOM of freshwater and soil origin. The chemical diversity of carbohydrates as indicated by H2CO-groups (δC ~62±2 ppm) and anomerics (δC ~102±7 ppm) exceeded that of freshwater and soil DOM considerably. HSQC NMR spectra were best suited to identify chemical environments of methin carbon (CH) and enabled discrimination of olefinic and aromatic cross peaks (δC > 110 ppm) and those of doubly oxygenated carbon (δC < 110 ppm). The abundance of olefinic protons exceeded that of aromatic protons; comparison of relative HSQC cross peak integrals indicated larger abundance of olefinic carbon than aromatic carbon in all marine DOM as well. A considerable fraction of olefins seemed isolated and likely sterically constrained as judged from small nJHH couplings associated with those olefins. High S/N ratio and fair resolution of TOCSY and HSQC cross peaks enabled unprecedented depiction of sp²-hybridized carbon chemical environments in marine DOM with discrimination of isolated and conjugated olefins as well as α, β-unsaturated double bonds. However, contributions from five-membered heterocycles (furan, pyrrol and thiophene derivatives) even if very unlikely from given elemental C/N and C/S ratios and upfield proton NMR chemical shift (δH <6.5 ppm) could not yet been ruled out entirely. In addition to classical aromatic DOM, like benzene derivatives and phenols, six-membered nitrogen heterocycles were found prominent contributors to the downfield region of proton chemical shift (δH > 8 ppm). Specifically, a rather confined HSQC cross peak at δH/δC =8.2/164 ppm indicated a limited set of nitrogen heterocycles with several nitrogen atoms in analogy to RNA derivatives present in all four marine DOM. Appreciable amounts of extended HSQC and TOCSY cross peaks derived from various key polycyclic aromatic hydrocarbon substructures suggested the presence of previously proposed but NMR invisible thermogenic organic matter (TMOC) in marine DOM at all water depths. Eventually, olefinic unsaturation in marine DOM will be more directly traceable to ultimate biogenic precursors than aromatic unsaturation of which a substantial fraction originates from an aged material which from the beginning was subjected to complex and less specific biogeochemical reactions like thermal decomposition. The variance in molecular mass as indicated from Fourier transform ion cyclotron resonance (FTICR) mass spectra was limited and could not satisfactorily explain the observed disparity in NMR transverse relaxation of the four marine DOM samples. Likewise, the presence of metal ions in isolated marine DOM remained near constant or declined from surface to depth for important paramagnetic ions like Mn, Cr, Fe, Co, Ni and Cu. Iron in particular, a strong complexing paramagnetic ion, was found most abundant by a considerable margin in surface (FISH) marine DOM for which well resolved COSY cross peaks were observed. Hence, facile relationships between metal content of isolated DOM (which does not reflect authentic marine DOM metal content) and transverse NMR relaxation were not observed. High field (12 T) negative electrospray ionization FTICR mass spectra showed at first view rather conforming mass spectra for all four DOM samples with abundant CHO, CHNO, CHOS and CHNOS molecular series with slightly increasing numbers of mass peaks from surface to bottom DOM and similar fractions (~50 %) of assigned molecular compositions throughout all DOM samples. The average mass increased from surface to bottom DOM by about 10 Dalton. The limited variance of FTICR mass spectra probably resulted from a rather inherent conformity of marine DOM at the mandatory level of intrinsic averaging provided by FTICR mass spectrometry, when many isomers unavoidably project on single nominal mass peaks. In addition, averaging from ion suppression added to the accordance observed. The proportion of CHO and CHNO molecular series increased from surface to depth whereas CHOS and especially CHNOS molecular series markedly declined. The abundance of certain aromatic CHOS compounds declined with water depth. For future studies, COSY NMR spectra appear best suited to assess organic molecular complexity of marine DOM and to define individual DOM molecules of yet unknown structure and function. Non-target organic structural spectroscopy at the level demonstrated here covered nearly all carbon present in marine DOM. The exhaustive characterization of complex unknowns in marine DOM will reveal a meaningful assessment of individual marine biogeo-signatures which carry the holistic memory of the oceanic water masses (Koch et al., 2011). [ABSTRACT FROM AUTHOR]

Atmospheric aerosols impose direct and indirect effects on the climate system, for example, by adsorption of radiation in relation to cloud droplets size, on chemical and organic composition and cloud dynamics. The first step in the formation of primary marine aerosols, i.e., the transfer of dissolved organic matter from the marine surface into the atmosphere was studied, and we present a molecular level description of this phenomenon using high resolution analytical tools (Fourier transform ion cyclotron resonance = FT-ICR MS and NMR). We could experimentally confirm the chemo-selective transfer of natural organic molecules, especially of aliphatic compounds from the sur face water into the atmosphere via bubble bursting processes. Transfer from marine surface water to the atmosphere involves a chemical gradient governed by the physicochemical properties of the involved molecules when comparing elemental compositions and differentiating CHO, CHNO, CHOS and CHNOS bearing compounds. Typical chemical fingerprints of concentrated compounds were CHO and CHOS type of molecules, smaller molecules of higher aliphaticity and lower oxygen content and typical surfactants. A non-targeted mass spectrometric analysis of the samples showed that many of these molecules correspond to homologous series of oxo-, hydroxyl-, methoxy-, branched fatty acids and mono-, di- and tricarboxylic acids as well as monoterpenes and sugars. These surface active biomolecules were preferentially transferred from surface water into the atmosphere via bubble bursting processes to form a significant fraction of primary organic aerosols. This way of production of sea spray leaves a specific biological signature of the surface water in the corresponding lower atmosphere that can be transported laterally in the context of global cycling. [ABSTRACT FROM AUTHOR]

The binding of cadmium to Suwannee River natural organic matter (NOM) has been investigated across a broad range of Cd/C ratios (0.00056-0.0056) and pH values (3.5-11) by 113Cd NMR spectroscopy at two magnetic field strengths (B0 = 9.4 and 11.7 1). Caused by the very peculiar and highly complex nature of the Cd- NOM exchanging system, these 113Cd NMR spectra are characterized by a pH- and concentration-dependent superposition of slow, intermediate, and fast chemical exchange. The complex interplay of solution chemistry and chemical exchange requires a thorough mapping of this Cd-NOM chemically exchanging system through NMR acquisition at two magnetic field strengths and a systematic variation of Cd/C ratios and pH values. The interpretation of 113Cd NMR spectra is greatly facilitated and constrained by simultaneous measurements of pH and pCd, which allows a model-independent calculation of organically bound Cd2+ under all experimental conditions. Within the range of chemical conditions applied in this study, 113Cd NMR spectrometric evidence is consistent with coordination of cadmium by oxygen, nitrogen, and sulfur ligands in NOM. Under all experimental conditions, cadmium is primarily coordinated to oxygen; however, several lines of evidence point to the participation of nitrogen ligands, even in acidic solutions where nitrogen ligands are primarily bound to protons. Under alkaline conditions, up to one-third of cadmium may be coordinated to nitrogen, and a small, but unquantifiable, percentage of cadmium is coordinated to sulfur ligands, as evidenced by far-low-field 113Cd NMR resonances. [ABSTRACT FROM AUTHOR]

Investigates the transformation of aquatic humic substances (HS) by autochthonois microorganisms. Loss of aromaticity and aliphatic carbon in HS; Cometabolic degradation of HS; Formations of HS in the microbial cultures.

Nuclear magnetic resonance (NMR) resonance integrals obtained from one‐dimensional NMR spectra provide semiquantitative contents of humic constituents with limited resolution in structural detail. When supplemented by connectivity information available from homo‐ and heteronuclear two‐dimensional NMR spectra a more reliable assignment of humic substructures becomes available. This is demonstrated with a comparative one‐ and two‐dimensional NMR analysis of a fulvic and a humic acid obtained from Eriophorum peat. An example of a detailed analysis of the proton chemical shift region normally attributed to carbohydrates shows substantial contributions from amino acids, amino and desoxy sugars, and highly oxidized aliphatic chains of intermediate length. The very good resolution of structural detail by a combined analysis of all NMR spectra shows that the effect of the fractionation procedure on the composition and chemical structure of humic materials is very significant. The comparison of the partial structures comprising humic acid (HA) and fulvic acid (FA) of the peat humic materials studied indicates that FA is diagenetically downstream of HA, favoring the biopolymer degradation (BD) model of humification. [ABSTRACT FROM AUTHOR]

Examines the use of the capillary electrophoresis (CE) in the evaluation of the influence of tetrahydroxyborate ions on the electrophoretic mobility of humic acids. Consistency of the capillary electrophoresis instrumentation; Acquisition of the B nuclear magnetic resonance (NMR) spectra; Analysis of the complexation of borate ions and humic acid fractions.

Dissolved organic matter (DOM) is one of the most complex, dynamic and abundant sources of organic carbon, but its chemical reactivity remains uncertain 1-3 . Greater insights into DOM structural features could facilitate understanding its synthesis, turnover and processing in the global carbon cycle 4,5 . Here we use complementary multiplicity-edited 13 C nuclear magnetic resonance (NMR) spectra to quantify key substructures assembling the carbon skeletons of DOM from four main Amazon rivers and two mid-size Swedish boreal lakes. We find that one type of reaction mechanism, oxidative dearomatization (ODA), widely used in organic synthetic chemistry to create natural product scaffolds 6-10 , is probably a key driver for generating structural diversity during processing of DOM that are rich in suitable polyphenolic precursor molecules. Our data suggest a high abundance of tetrahedral quaternary carbons bound to one oxygen and three carbon atoms (OC q C 3 units). These units are rare in common biomolecules but could be readily produced by ODA of lignin-derived and tannin-derived polyphenols. Tautomerization of (poly)phenols by ODA creates non-planar cyclohexadienones, which are subject to immediate and parallel cycloadditions. This combination leads to a proliferation of structural diversity of DOM compounds from early stages of DOM processing, with an increase in oxygenated aliphatic structures. Overall, we propose that ODA is a key reaction mechanism for complexity acceleration in the processing of DOM molecules, creation of new oxygenated aliphatic molecules and that it could be prevalent in nature., (© 2024. The Author(s).)

Polycyclic aromatic hydrocarbons (PAHs) contain ≲20% of the carbon in the interstellar medium. They are potentially produced in circumstellar environments (at temperatures ≳1000 kelvin), by reactions within cold (~10 kelvin) interstellar clouds, or by processing of carbon-rich dust grains. We report isotopic properties of PAHs extracted from samples of the asteroid Ryugu and the meteorite Murchison. The doubly- 13 C substituted compositions (Δ2× 13 C values) of the PAHs naphthalene, fluoranthene, and pyrene are 9 to 51‰ higher than values expected for a stochastic distribution of isotopes. The Δ2× 13 C values are higher than expected if the PAHs formed in a circumstellar environment, but consistent with formation in the interstellar medium. By contrast, the PAHs phenanthrene and anthracene in Ryugu samples have Δ2× 13 C values consistent with formation by higher-temperature reactions.

Effluent organic matter (EfOM) discharged from wastewater treatment plants (WWTPs) carry substantial risks to river ecosystems. The fate and role of EfOM in the receiving water is affected by its exposure to sunlight and microbial processes, but the extent of these processes remains unclear. In this study, three-phase sequence of irradiation and microbial incubation with EfOM were conducted to compare the behavior of EfOM with that of natural organic matter in receiving rivers (RNOM). The dissolved organic carbon (DOC) in EfOM was degraded by 23% after three sequential phases, while that in RNOM was degraded by 19%. In the first phase, the irradiation of EfOM stimulated microbial respiration and growth by producing easily metabolizable less aromatic lignin-type molecules, leading to a 21% increase in biodegradation. Conversely, the irradiation of RNOM removed biodegradable lignin-type molecules, causing a 50% decreased in biodegradation. The second and third irradiation phases of EfOM and RNOM produced biodegradable lignin-type molecules, making their molecular compositions increasingly similar. The acute toxicity of EfOM decreased by 55%, and differences in microbial species composition between EfOM and RNOM waters decreased by 82% after the three-phase sequence. These findings can improve understanding of the fate of EfOM discharged into receiving rivers., Competing Interests: Declaration of Competing Interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2023 Elsevier B.V. All rights reserved.)

The sample from the near-Earth carbonaceous asteroid (162173) Ryugu is analyzed in the context of carbonaceous meteorites soluble organic matter. The analysis of soluble molecules of samples collected by the Hayabusa2 spacecraft shines light on an extremely high molecular diversity on the C-type asteroid. Sequential solvent extracts of increasing polarity of Ryugu samples are analyzed using mass spectrometry with complementary ionization methods and structural information confirmed by nuclear magnetic resonance spectroscopy. Here we show a continuum in the molecular size and polarity, and no organomagnesium molecules are detected, reflecting a low temperature and water-rich environment on the parent body approving earlier mineralogical and chemical data. High abundance of sulfidic and nitrogen rich compounds as well as high abundance of ammonium ions confirm the water processing. Polycyclic aromatic hydrocarbons are also detected in a structural continuum of carbon saturations and oxidations, implying multiple origins of the observed organic complexity, thus involving generic processes such as earlier carbonization and serpentinization with successive low temperature aqueous alteration., (© 2023. Springer Nature Limited.)

Natural organic matter (NOM) is critical for the biogeochemical cycles of energy and many elements in terrestrial and aquatic ecosystems, and protonation-active functional groups in NOM molecules, notably carboxylic and phenolic groups often mediate these critical environmental functions. Molecular heterogeneity, polydispersity and dynamic behavior of NOM complicate achieving an unambiguous description of its molecular properties and reactivity. This study demonstrates that differential ultraviolet-visible (UV/VIS) absorbance spectra (DAS) of NOM acquired at varying pH values exhibit several distinct features associated with the deprotonation of NOM molecules, independent of the environmental provenance of NOM (e.g., surface water, seawater, sediment, and wastewater). The protonation-active functionalities that contribute to the Gaussian distribution bands present in the DAS were identified here by comparing characteristic properties of the bands with the stoichiometries of NOM molecules ascertained by Ultrahigh-Resolution Fourier-Transform Ion Cyclotron Resonance Mass Spectrometry (FT-ICR-MS). The protonation-active individual chromophores universally present in NOM molecules were identified by a genetic molecular network analysis. The observed DAS features were closely modeled via superimposing DAS spectra of 51 individual protonation-active chromophores. Molecular orbital theory was applied to further interpret the deprotonation of these chromophores, their molecular structure, electron distribution, and electron transitions measured using DAS. The high sensitivity and easy implementation of the DAS approach allows using it as a powerful tool to quantify the molecular properties and reactivity of NOM at environmental concentrations., Competing Interests: Declaration of Competing Interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2023 Elsevier Ltd. All rights reserved.)

Samples from the carbonaceous asteroid (162173) Ryugu provide information on the chemical evolution of organic molecules in the early solar system. Here we show the element partitioning of the major component ions by sequential extractions of salts, carbonates, and phyllosilicate-bearing fractions to reveal primordial brine composition of the primitive asteroid. Sodium is the dominant electrolyte of the salt fraction extract. Anions and NH 4 + are more abundant in the salt fraction than in the carbonate and phyllosilicate fractions, with molar concentrations in the order SO 4 2-  > Cl -  > S 2 O 3 2-  -polythionic acids (n < 6), C 3 -alkylsulfonates, alkylthiosulfonates, hydroxyalkylsulfonates, and hydroxyalkylthiosulfonates (n < 7). The sulfur-bearing soluble compounds may have driven the molecular evolution of prebiotic organic material transforming simple organic molecules into hydrophilic, amphiphilic, and refractory S allotropes.-  > NH 4 + . The salt fraction extracts contain anionic soluble sulfur-bearing species such as S n -polythionic acids (n < 6), C n -alkylsulfonates, alkylthiosulfonates, hydroxyalkylsulfonates, and hydroxyalkylthiosulfonates (n < 7). The sulfur-bearing soluble compounds may have driven the molecular evolution of prebiotic organic material transforming simple organic molecules into hydrophilic, amphiphilic, and refractory S allotropes., (© 2023. Springer Nature Limited.)

Background: Growing up on traditional European or US Amish dairy farms in close contact with cows and hay protects children against asthma, and airway administration of extracts from dust collected from cowsheds of those farms prevents allergic asthma in mice., Objectives: This study sought to begin identifying farm-derived asthma-protective agents., Methods: Our work unfolded along 2 unbiased and independent but complementary discovery paths. Dust extracts (DEs) from protective and nonprotective farms (European and Amish cowsheds vs European sheep sheds) were analyzed by comparative nuclear magnetic resonance profiling and differential proteomics. Bioactivity-guided size fractionation focused on protective Amish cowshed DEs. Multiple in vitro and in vivo functional assays were used in both paths. Some of the proteins thus identified were characterized by in-solution and in-gel sodium dodecyl sulfate-polyacrylamide gel electrophoresis enzymatic digestion/peptide mapping followed by liquid chromatography/mass spectrometry. The cargo carried by these proteins was analyzed by untargeted liquid chromatography-high-resolution mass spectrometry., Results: Twelve carrier proteins of animal and plant origin, including the bovine lipocalins Bos d 2 and odorant binding protein, were enriched in DEs from protective European cowsheds. A potent asthma-protective fraction of Amish cowshed DEs (≈0.5% of the total carbon content of unfractionated extracts) contained 7 animal and plant proteins, including Bos d 2 and odorant binding protein loaded with fatty acid metabolites from plants, bacteria, and fungi., Conclusions: Animals and plants from traditional farms produce proteins that transport hydrophobic microbial and plant metabolites. When delivered to mucosal surfaces, these agents might regulate airway responses., (Copyright © 2023 The Authors. Published by Elsevier Inc. All rights reserved.)

Positive and negative electrospray ionization Fourier transform ion cyclotron resonance mass spectrometry and 1 H NMR revealed major compositional and structural changes of dissolved organic matter (DOM) after mixing two sets of river waters in Amazon confluences: the Solimões and Negro Rivers (S + N) and the Amazon and Tapajós Rivers (A + T). We also studied the effects of water mixing ratios and incubation time on the composition and structure of DOM molecules. NMR spectra demonstrated large-scale structural transformations in the case of S + N mixing, with gain of pure and functionalized aliphatic units and loss of all other structures after 1d incubation. A + T mixing resulted in comparatively minor structural alterations, with a major gain of small aliphatic biomolecular binding motifs. Remarkably, structural alterations from mixing to 1d incubation were in essence reversed from 1d to 5d incubation for both S + N and A + T mixing experiments. Heterotrophic bacterial production (HBP) in endmembers S, N, and S + N mixtures remained near 0.03 μgC L -1 h -1 , whereas HBP in A, T, and A + T were about five times higher. High rates of dark carbon fixation took place at S + N mixing in particular. In-depth biogeochemical characterization revealed major distinctions between DOM biogeochemical changes and temporal evolution at these key confluence sites within the Amazon basin., Competing Interests: The authors declare no competing financial interest., (© 2023 The Authors. Published by American Chemical Society.)

The Hayabusa2 spacecraft collected samples from the surface of the carbonaceous near-Earth asteroid (162173) Ryugu and brought them to Earth. The samples were expected to contain organic molecules, which record processes that occurred in the early Solar System. We analyzed organic molecules extracted from the Ryugu surface samples. We identified a variety of molecules containing the atoms CHNOS, formed by methylation, hydration, hydroxylation, and sulfurization reactions. Amino acids, aliphatic amines, carboxylic acids, polycyclic aromatic hydrocarbons, and nitrogen-heterocyclic compounds were detected, which had properties consistent with an abiotic origin. These compounds likely arose from an aqueous reaction on Ryugu's parent body and are similar to the organics in Ivuna-type meteorites. These molecules can survive on the surfaces of asteroids and be transported throughout the Solar System.

Many essential building blocks of life, including amino acids, sugars, and nucleosides, require aldehydes for prebiotic synthesis. Pathways for their formation under early earth conditions are therefore of great importance. We investigated the formation of aldehydes by an experimental simulation of primordial early earth conditions, in line with the metal-sulfur world theory in an acetylene-containing atmosphere. We describe a pH-driven, intrinsically autoregulatory environment that concentrates acetaldehyde and other higher molecular weight aldehydes. We demonstrate that acetaldehyde is rapidly formed from acetylene over a nickel sulfide catalyst in an aqueous solution, followed by sequential reactions progressively increasing the molecular diversity and complexity of the reaction mixture. Interestingly, through inherent pH changes, the evolution of this complex matrix leads to auto-stabilization of de novo synthesized aldehydes and alters the subsequent synthesis of relevant biomolecules rather than yielding uncontrolled polymerization products. Our results emphasize the impact of progressively generated compounds on the overall reaction conditions and strengthen the role of acetylene in forming essential building blocks that are fundamental for the emergence of terrestrial life., (© 2023. The Author(s).)

Rivers are natural biogeochemical systems shaping the fates of dissolved organic matter (DOM) from leaving soils to reaching the oceans. This study focuses on Amazon basin DOM processing employing negative and positive electrospray ionization Fourier transform ion cyclotron resonance mass spectrometry (ESI[±] FT-ICR MS) and nuclear magnetic resonance spectroscopy (NMR) to reveal effects of major processes on the compositional space and structural characteristics of black, white and clear water systems. These include non-conservative mixing at the confluences of (1) Solimões and the Negro River, (2) the Amazon River and the Madeira River, and (3) in-stream processing of Amazon River DOM between the Madeira River and the Tapajós River. The Negro River (black water) supplies more highly oxygenated and high molecular weight compounds, whereas the Solimões and Madeira Rivers (white water) contribute more CHNO and CHOS molecules to the Amazon River main stem. Aliphatic CHO and abundant CHNO compounds prevail in Tapajos River DOM (clear water), likely originating from primary production. Sorption onto particles and heterotrophic microbial degradation are probably the principal mechanisms for the observed changes in DOM composition in the Amazon River and its tributaries., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2022. Published by Elsevier B.V.)

We report a huge organic diversity in the Tissint Mars meteorite and the sampling of several mineralogical lithologies, which revealed that the organic molecules were nonuniformly distributed in functionality and abundance. The range of organics in Tissint meteorite were abundant C 3-7 aliphatic branched carboxylic acids and aldehydes, olefins, and polyaromatics with and without heteroatoms in a homologous oxidation structural continuum. Organomagnesium compounds were extremely abundant in olivine macrocrystals and in the melt veins, reflecting specific organo-synsthesis processes in close interaction with the magnesium silicates and temperature stresses, as previously observed. The diverse chemistry and abundance in complex molecules reveal heterogeneity in organic speciation within the minerals grown in the martian mantle and crust that may have evolved over geological time.

The current study examines the desiccation-resistant Ramlibacter tataouinensis TTB310 T as a model organism for the production of novel exopolysaccharides and their structural features. This bacterium is able to produce dividing forms of cysts which synthesize cell-bound exopolysaccharide. Initial experiments were conducted on the enrichment of cyst biomass for exopolysaccharide production under batch-fed conditions in a pilot-scale bioreactor, with lactate as the source of carbon and energy. The optimized medium produced significant quantities of exopolysaccharide in a single growth phase, since the production of exopolysaccharide took place during the division of the cysts. The exopolysaccharide layer was extracted from the cysts using a modified trichloroacetic acid method. The biochemical characterization of purified exopolysaccharide was performed by gas chromatography, ultrahigh-resolution mass spectrometry, nuclear magnetic resonance, and Fourier-transform infrared spectrometry. The repeating unit of exopolysaccharide was a decasaccharide consisting of ribose, glucose, rhamnose, galactose, mannose, and glucuronic acid with the ratio 3:2:2:1:1:1, and additional substituents such as acetyl, succinyl, and methyl moieties were also observed as a part of the exopolysaccharide structure. This study contributes to a fundamental understanding of the novel structural features of exopolysaccharide from a dividing form of cysts, and, further, results can be used to study its rheological properties for various industrial applications.

The temporal evolution of molecular compositions and changes in structural features of Hillsboro Canal (Florida, USA) dissolved organic matter (DOM) was studied with an emphasis on nitrogen and sulfur containing molecules, after a 13 day time-series exposure to simulated sunlight. The Hillsboro Canal drains from the ridge and slough wetland environment underlain by peat soils from the northern extent of the Greater Everglades Ecosystem. The Hillsboro Canal-DOM was characterized by combining ultrahigh-resolution mass spectrometry (FT-ICR-MS), high-field nuclear magnetic resonance spectroscopy ( 1 H NMR), size exclusion chromatography (SEC) with UV detection, and ultraviolet/visible (UV/vis) absorbance and excitation emission matrix (EEM) fluorescence spectroscopy. Size exclusion chromatography (SEC) demonstrated progressive depletion of higher mass molecules and a concomitant decrease of absorbance during photo-irradiation. NMR and FT-ICR-MS revealed nonlinear temporal evolution of DOM. In fact, FT-ICR-MS showed an initial depletion of supposedly chromophoric molecules often carrying major unsaturation accompanied by an uneven evolution of numbers of CHO, CHOS and CHNO compounds. While CHNO compounds continually increased throughout the entire photo-exposure time, CHO and CHOS compounds temporarily increased but declined after further light exposure. Progressive loss of highly unsaturated compounds was accompanied by production of low mass CHO and CHNO compounds with high O/C ratios. Area-normalized 1 H NMR spectra of DOM in water and of the water insoluble fraction (~5%) in methanol revealed clear distinctions between irradiated and non-irradiated samples and congruent evolution of DOM structural features during irradiation, with more uniform trends in methanolic-DOM. Photoirradiation caused initial photoproduction of oxygenated aliphatic compounds, continued depletion of phenols and oxygenated aromatics, substantial change from initial natural product derived olefins to photoproduced olefins, and uneven evolution of carboxylated and alkylated benzene derivatives. This study demonstrates longer-term heteroatom-dependent photochemistry of DOM, which will affect the speciation of N and S heteroatoms, their connections to inorganic nutrients, and potentially their bioavailability., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2022. Published by Elsevier B.V.)

Aquifers are important reservoirs for organic carbon. A fundamental understanding of the role of groundwater ecosystems in carbon cycling, however, is still missing. Using sediment flow-through microcosms, long-term (171d) experiments were conducted to test two scenarios. First, aquifer sediment microbial communities received dissolved organic matter (DOM) at low concentration and typical to groundwater in terms of composition (DOM-1x). Second, sediments received an elevated concentration of DOM originating from soil (DOM-5x). Changes in DOM composition were analyzed via NMR and Fourier transform ion cyclotron resonance mass spectrometry (FT-ICR-MS). Carbon production, physiological adaptations and biodiversity of groundwater, and sediment prokaryotic communities were monitored by total cell counts, substrate use arrays, and deep amplicon sequencing. The experiments showed that groundwater microbial communities do not react very fast to the sudden availability of labile organic carbon from soil in terms of carbon degradation and biomass production. It took days to weeks for incoming DOM being efficiently degraded and pronounced cell production occurred. Once conditioned, the DOM-1x supplied sediments mineralized 294(±230) μgC L -1 sed d -1 , 10-times less than the DOM-5x fed sediment communities [2.9(±1.1) mgC L -1 sed d -1 ]. However, the overall biomass carbon production was hardly different in the two treatments with 13.7(±4.8) μgC L -1 sed d -1 and 14.3(±3.5) μgC L -1 sed d -1 , respectively, hinting at a significantly lower carbon use efficiency with higher DOM availability. However, the molecularly more diverse DOM from soil fostered a higher bacterial diversity. Taking the irregular inputs of labile DOM into account, shallow aquifers are assumed to have a low resilience. Lacking a highly active and responsive microbial community, oligotrophic aquifers are at high risk of contamination with organic chemicals., (Copyright © 2020 Hofmann, Uhl, Hertkorn and Griebler.)

Boreal lakes are considered hot spots of dissolved organic matter (DOM) processing within the global carbon cycle. This study has used FT-ICR mass spectrometry and comprehensive data evaluation to assess the molecular differences of SPE-DOM between lake column water SPE-DOM and sedimentary pore water SPE-DOM in 10 Swedish boreal lakes of the Malingsbo area, which were selected for their large diversity of physicochemical and morphological characteristics. While lake column water is well mixed and fairly oxygenated, sedimentary pore water is subject to depletion of oxygen and to confinement of molecules. Robust trends were deduced from molecular compositions present in all compartments and in all 10 lakes ("common compositions") with recognition of relative abundance. Sedimentary pore water SPE-DOM featured higher proportions of heteroatoms N and S, higher average H/C ratios in presence of higher DBE/C ratios, and higher average oxygenation than lake column water SPE-DOM. These trends were observed in all lakes except Ljustjärn, which is a ground water fed kettle lake with an unique lake biogeochemistry. Analogous trends were also observed in case of single or a few lakes and operated also for compounds present solely in either lake column water or sedimentary pore water. Unique compounds detected in either compartments and/or in a few lakes showed higher molecular diversity than the "common compositions". Processing of DOM molecules in sediments included selective preservation for polyphenolic compounds and microbial resynthesis of selected molecules of considerable diversity., (Copyright © 2019. Published by Elsevier Ltd.)

Pseudomonas sp. BGI-2 is a psychrotrophic bacterium isolated from the ice sample collected from Batura glacier, Pakistan. This strain produces highly viscous colonies on agar media supplemented with glucose. In this study, we have optimized growth and production of exopolysaccharide (EPS) by the cold-adapted Pseudomonas sp. BGI-2 using different nutritional and environmental conditions. Pseudomonas sp. BGI-2 is able to grow in a wide range of temperatures (4-35°C), pH (5-11), and salt concentrations (1-5%). Carbon utilization for growth and EPS production was extensively studied and we found that glucose, galactose, mannose, mannitol, and glycerol are the preferable carbon sources. The strain is also able to use sugar waste molasses as a growth substrate, an alternative for the relatively expensive sugars for large scale EPS production. Maximum EPS production was observed at 15°C, pH 6, NaCl (10 g L -1 ), glucose as carbon source (100 g L -1 ), yeast extract as nitrogen source (10 g L -1 ), and glucose/yeast extract ratio (10/1). Under optimized conditions, EPS production was 2.01 g L -1 , which is relatively high for a Pseudomonas species compared to previous studies using the same method for quantification. High-performance anion-exchange chromatography with pulsed amperometric detection (HPAEC-PAD) analysis of EPS revealed glucose, galactose, and glucosamine as the main sugar monomers. Membrane protection assay using human RBCs revealed significant reduction in cell lysis (∼50%) in the presence of EPS, suggesting its role in membrane protection. The EPS (5%) also conferred significant cryoprotection for a mesophilic Escherichia coli k12 which was comparable to glycerol (20%). Also, improvement in lipid peroxidation inhibition ( in vitro ) resulted when lipids from the E. coli was pretreated with EPS. Increased EPS production at low temperatures, freeze thaw tolerance of the EPS producing strain, and increased survivability of E. coli in the presence of EPS as cryoprotective agent supports the hypothesis that EPS production is a strategy for survival in extremely cold environments such as the glacier ice., (Copyright © 2020 Ali, Shah, Hasan, Hertkorn, Gonsior, Sajjad and Chen.)