Contaminated soil organic matter from the Rocky Flats Environmental Technology Site (RFETS) has been previously shown to accumulate plutonium (Pu) in a colloidal subfraction and is hypothesized to contain cutin-like chemical structures cross-linked with hydroxamate functionality. The present study further characterizes this high Pu affinity subfraction using electrospray ionization Fourier transform ion cyclotron resonance mass spectrometry (ESI-FTICRMS) and discovers additional substructural components. The Pu-enriched fraction was extracted and purified through a series of ultrafiltration and isoelectric focusing (IEF) electrophoresis steps. Predominantly low H/C and high double-bond equivalence (DBE) aromatic and condensed aromatic molecular formulas were detected, 66% of which are included in a COO Kendrick mass defect (KMD) homologous series. This suggests the existence of polycarboxylated aromatic and condensed aromatic formulas, with CHON-type COO KMD formulas relatively more abundant in the purified subfraction where Pu had been observed than in the crude soil fractions which had successively lower Pu concentrations. Nitrogen contents increased with the progression of purification (bulk soil → crude colloid → IEF colloid) and coincided with the trend of Pu concentration; thus, we propose that these nitrogen and carboxyl functionalities of aromatic compounds may also impart significant Pu chelation character to the colloid.

•Alicyclic carboxylic acids found as an important constituent of soil humic acid.•Hydroxy, methyl and olefinic groups observed 2–3 bonds from carboxylic acid group.•Findings consistent with alicyclic carboxylic acid formation from lignin.•Lignin proposed to be a source of these molecules in soil humic acid.It has been well accepted that humic acids in soils comprise both aromatic and aliphatic structural units that harbor mainly oxygenated functional groups such as carboxylic acids, aldehydes, ketones, and hydroxyl groups. Recent mass spectral data obtained from electrospray ionization-Fourier transform ion cyclotron resonance mass spectrometry (ESI-FTICRMS) suggest that the main functional groups in humic acids are carboxylic acids bound to both alicyclic and condensed aromatic molecules. It was suggested that these structural entities originate from oxidation of lignin. To provide additional support, detailed structural characteristics were obtained here using several multi-dimensional nuclear magnetic resonance (NMR) techniques to observe the molecular connectivity of humic acid components, with a focus on carboxylic acids in particular. The humic acid sample examined had been shown to exhibit structural characteristics similar to a larger set of soil humic acids. In this study, many carboxylic acid resonances were found to correlate with protons that could be assigned to aliphatic and alicyclic chemical shift regions. Functional groups with heteroatoms such as alcohols, some olefins and an assortment of methyl groups were found to correlate within 2–3 bonds of carboxylic acid groups. The collection of structural components and their proximity to a variety of carboxylic groups supports the occurrence of carboxylated alicyclic molecules as important elements of the aliphatic portion of soil humic acids and a pathway from lignin is consistent with recent findings.

•Molecular characterization of HPLC fractionated lignin presented.•Hydroxyl radical treatment shown to significantly alter lignin fractions.•Polar components of dissolved lignin responsible for new compounds formed.Reactive oxygen species (ROS) are thought to play an important, although poorly understood, role in modifying the composition of terrigenous-derived dissolved organic matter (tDOM) upon export to aquatic systems. Of the dominant ROS in natural systems, OH has been shown to substantially modify lignin under laboratory conditions, simulating processes responsible for transformation of DOM in natural waters. Utilizing high performance liquid chromatography (HPLC) in conjunction with ultrahigh resolution mass spectrometry, we examined HPLC fractionated lignin extracts in an effort to establish which fractionated components of the lignin extract were (i) most susceptible to attack by OH and (ii) most likely to be responsible for compounds observed in the DOM. The results indicate that the most polar components of the lignin extract, representing tDOM, could be responsible for a large portion of newly generated formulas observed within DOM in natural waters. This suggests that partially oxidized lignin may be readily altered to compounds observed in DOM which are not typically associated with terrigenous OM, such as alicyclic and condensed aromatic-like compounds.

In the following study, we addressed the effects of photoirradiation on the turnover of dissolved organic nitrogen (DON) from both natural and anthropogenic sources at the molecular level. Analysis of long-term photoirradiated samples via Fourier-transform ion cyclotron resonance mass spectrometry (FT-ICR-MS) identified both the photolabile and the photoproduced DON from both natural and anthropogenic sources. Although photoproduction of DON was prominent with natural dissolved organic matter (DOM) sources, even in a low nitrogen environment, the anthropogenic source shows a shift from photobleaching to photohumification denoted by an increase in the average molecular weight (MW) and the double bound equivalent (DBE) after 25 days of a continuous exposure to UV light, implying condensation of low MW molecules (LMW) to form high MW (HMW) molecules. Furthermore, the sharp increase in N/C molar ratio, in the anthropogenic source, substantiates the photoinduced dissolved inorganic nitrogen (DIN) incorporation hypothesis. Hence, our findings suggest that anthropogenic input will drive substantial variation in riverine DOM and, thus, estuarine optics and photochemistry and bioavailability. Furthermore, we validate that photochemistry is one of the main processes that shapes the DON quality in aquatic systems regardless of its original source.

•Degradation of lignin by HO investigated.•Formation of condensed aromatic compounds from lignin proposed.•Formation of alicyclic compounds from lignin proposed.•Potential impact of lignin in humification discussed.Exposure of lignin-derived organic matter (OM) to hydroxyl radicals originating from Fenton type reactions generates condensed aromatic and alicyclic aliphatic compounds, as shown using ultrahigh resolution mass spectrometry. Although condensed aromatic compounds are common in soil and dissolved OM, their presence has been attributed largely to combustion. A non-pyrogenic route for the formation of condensed aromatic compounds from lignin is suggested here, specifically that hydroxyl radical-initiated oxidation of lignin is capable of producing black carbon-like condensed aromatic compounds. Alicyclic aliphatic compounds are also produced, likely as part of a concerted process involving ring opening, polymerization and/or cyclization and hydrogen abstraction. Hydroxyl radicals associated with lignin degradation are produced through photochemistry in aqueous systems and enzymatic microbial processes in soil.

•Investigation into the thermal maturation of algae and algaenan.•Hydrous pyrolysis of algaenan produces a hydrocarbon based oil.•GC × GC–TOFMS analysis of nonpolar fraction of algae and algaenan biofuels.Algae are regarded as the form of biomass most likely to provide sufficient quantities of fuels without impacting our food supplies. Studies investigating the potential of hydrothermal treatment of algae to produce biofuels show that, in many instances, the produced oils do not resemble crude oils and have a high heteroatom content. In this study, Scenedesmus spp. algae and isolated algaenan, a type of biopolymeric cell wall in certain algae and an important precursor to some kerogens, are subjected to hydrous pyrolysis in efforts to mimic the thermal maturation occurring in sediments as a proxy for biofuels production. Our study shows that algaenan can be subjected to hydrous pyrolysis to yield a hydrocarbon rich mixture that resembles many fossil fuel crude oils. More importantly, separation of the algaenan prior to the hydrothermal treatment can yield a paraffin rich crude requiring little additional processing to attempt to reproduce the geological process that gave us crude oils from ancient Type I kerogen. Although it requires algaenan isolation as a prerequisite, this could be a first step in the direction of producing oils without need for further upgrading. Whole algae, however, yield additional oxygenated products derived from oxygenated biopolymers even though the paraffins derived from algaenan dominate.

•Method for examining sediments with FT-ICR-MS investigated.•Five extraction solvents compared using NMR and FT-ICR-MS.•Pyridine was the optimal extraction solvent.•Method effective for molecular characterisation of organic rich and poor sediments.Fourier transform ion cyclotron resonance mass spectrometry (FTICRMS) can begin to tease apart the molecular character of sedimentary organic matter (SOM). We therefore tested five different solvents (aqueous base, CHCl3, MeOH, pyridine and water) for their ability to extract a representative fraction from two organic rich lacustrine sediments, Mangrove Lake, Bermuda (MLB) and Mud Lake, Florida (MLF). Following comparison using liquid state nuclear magnetic resonance spectroscopy (NMR) and negative ion mode electrospray ionization mass spectrometry (FTICRMS) we found that pyridine was the optimal solvent, extracting a more diverse (10–100× greater integration for carbonyl, amide and amine groups) and a larger number of peaks on average (1375–1450 vs. 380–1450). Comparison of the pyridine extracts between MLB, MLF and two organic poor sediments from the Mississippi River Delta and Bayou Grande (Pensacola, FL) showed that only 4.9% of the molecular formulae were common to all four and that unique formulae made up the highest proportion of the assignments. The use of pyridine for extracting immature (Holocene) SOM for FTICRMS analysis can therefore be widely applied to immature sediments and produce representative spectra.

Photochemical processing of dissolved organic matter (DOM) in natural waters can alter its composition and structure, supply particulate organic matter (POM) to sediments, and deliver modified terrestrial DOM to the ocean. Our studies show that terrestrial DOM exposed to simulated sunlight is altered to produce POM with a markedly different molecular composition enriched with newly formed aliphatic and condensed aromatic molecules. This process is closely tied to the chemistry of iron, which primarily exists as dissolved Fe(II) and Fe(III)–organic complexes in initial DOM and photochemically matures to Fe(III) oxyhydroxides before coprecipitating out with POM. The newly formed condensed aromatic compounds resemble black carbon, which until now was thought to be produced by only combustion. These new molecules contribute a pool of Fe-rich, aliphatic, and black carbon-like organic matter to sediments as the terrestrial DOM is transported through rivers. We estimate that the annual global flux of this photoproduced black carbon, most of which may be preserved in sediments, is nearly equivalent to the estimated flux of dissolved black carbon to the ocean from all other sources.

•A broad range of oceanic DOM, isolated by RO/ED, was analyzed by FTICR-MS.•A high percentage of molecular signatures were common to all samples.•Pacific and Atlantic surface waters were enriched in high H/C molecular formulas.•North Pacific deep waters were enriched in high O/C molecular formulas.•North Pacific subtropical gyre waters were enriched in photo-refractory DOM.A high-recovery technique of dissolved organic matter (DOM) isolation – reverse osmosis coupled with electrodialysis (RO/ED) – was used to isolate DOM from the North Atlantic Senegal-Mauritanian upwelling area surface water (5 m), North Atlantic oxygen minimum water (415 m) and deep water (3000 m), North Pacific subtropical gyre surface water (5 m), and North Pacific intermediate water (674 m) and deep water (3500 m). Samples were characterized by ultrahigh resolution Fourier transform ion cyclotron resonance mass spectrometry with electrospray ionization (ESI FTICR-MS). RO/ED isolated DOM samples share a significant number of common formulas accounting for 54–79% of formulas in each sample. Total dissolved carbohydrate (TCHO) concentrations in RO/ED isolated DOM were specifically measured using a colorimetric method, and were found to have higher contribution to DOC than estimated by FTICR-MS data. Percentages of TCHO-C in DOC are in the range of 3.7–19.6% in all samples, with the North Pacific deep (3500 m) water having the lowest % and the North Atlantic upwelling core surface water having the highest %. Principal component analysis (PCA) using the relative magnitudes of MS peaks facilitated identification of specific peaks that are enriched in different samples. Peaks enriched in surface samples have higher H/C values than peaks enriched in deep samples, in both the North Atlantic DOM and the North Pacific DOM. This enrichment pattern is likely due to the selective photo-degradation of aromatic compounds and the bio-production of aliphatic and carbohydrate-like compounds in surface waters, and the selective bio-degradation of aliphatic and carbohydrate-like compounds with increasing depth. In further support of a photo-degraded signature for DOM in surface waters, photo-resistant and photo-produced molecular formulas were present in the highest numbers in the surface North Pacific subtropical gyre DOM. Peaks enriched in the North Pacific intermediate and deep DOM have significantly higher O/C values than the North Atlantic oxygen minimum layer and deep DOM, for both CHO formula compounds and CHON formula compounds. This difference in O/C values observed for the deep Pacific vs. Atlantic suggests oxidation of DOM, possibly via microbial activity during the ageing of DOM or the preferential remineralization of DOM from sinking particles at depth in the Pacific.

•Algaenan structure changes with different isolation procedures.•High temperature treatments destroy algaenan crystallinity.•Base treatment in presence of alcohol transesterifies ester linkages of algaenan.The isolation of algaenan from its parent algae is the first step employed in the effort to characterize it. Three different protocols are the most followed in the isolation of algaenan. Because different structures have been proposed for algaenan from the same parent algae but isolated using different isolation protocols, we examined the possible effects the isolation procedure has on the algaenan chemistry. Our results indicate that the three different commonly used procedures have an impact on the structure of the recovered algaenan, because they involve different chemical treatments of varying strengths for the removal of non-algaenan components. The modifications to the overall similar dominant aliphatic composition include the formation of esters through transesterification, inclusion of proteins, destruction of crystallinity and hydrolysis of esters.

Artificial maturation techniques, such as hydrothermal liquefaction (HTL), have demonstrated the ability to generate petroleum-like products, termed bio-oils, from feedstocks including manure, algae and agricultural wastes; however, the oxygen, nitrogen, and sulfur content of bio-oils often requires upgrading. The objective of this study was to utilize HTL on a low rank coal to produce a high quality crude oil sample that can be used as a transportation fuel. Coal from the Wyodak-Anderson coal seam was selected for HTL due to its predominant aliphatic character and low heteroatom content. HTL was performed at 360 °C for 72 h. The untreated coal, spent solid, and expelled oil were analyzed using several advance analytical techniques including solid-state 13C NMR, two-dimensional gas chromatography–mass spectrometry and electrospray ionization-Fourier transform ion cyclotron resonance-mass spectrometry to achieve a comprehensive molecular characterization. Solid-state 13C NMR analyses of the untreated and spent coal estimate that 22% of the untreated coal, mostly the aliphatic portion, is lost as expelled hydrocarbon products. The expelled oil exhibits molecular characteristics similar to high quality crude oils, including low heteroatom content, n-alkanes ranging from C9–C32, and other desirable crude oil components such as cycloalkanes, alkyl benzenes and naphthalenes. It is suggested here that upon thermal maturation of the coal, preserved ester bonds in refractory biopolymers present in the coal are being cracked to yield fatty acids, which upon heating undergo decarboxylation, and finally random cleavage of C–C bonds to yield the lower molecular weight n-alkanes. Our results confirm that HTL is an effective technique for the production of a high quality crude oil from a low rank coal.

•We investigated the molecular composition of marine SOM undergoing early diagenesis.•Early diagenesis impacts primarily the O/C atomic ratio and the IO.•Protein and carbohydrate are preferentially degraded.•Calculated diagenesis rates are extremely slow.•These processes result in a significant decrease of the TOC.Although rates and mechanisms of early diagenesis have been well studied, the effects of microbial metabolism on the molecular composition of the sedimentary organic matter (SOM) over long periods of time need more investigation. In this study, we characterize the early diagenesis of marine SOM from organic rich sediments of the Ocean Drilling Program site 1082 located off Namibia, in the vicinity of the Benguela coastal upwelling system. We used both Fourier transform infrared spectroscopy (FTIR) and nuclear magnetic resonance spectroscopy (13C NMR) to assess the quantitative partitioning of the organic carbon into major compound classes (aliphatic, aromatic, ester, carboxylic, amide and carbons from carbohydrates). Then, we calculate the SOM composition in the main biomolecules (proteins, carbohydrates, lipids and lignin) on the basis of previous 13C NMR based estimates of the molecular composition of the organic mixtures. Results show that the SOM is still labile at 7 m below the seafloor (mbsf) and composed of about 25% proteins and 15% carbohydrates. With increasing depth, the protein content exponentially decreases to 13% at 367 mbsf, whereas the carbohydrate content decreases linearly to 11%. The lignin and lipid content consistently represent around 10% and 40% of the SOM, respectively, and show an increase with depth, due mostly to selective enrichment as the more labile components are lost by degradation. Thus, these components of the SOM are considered refractory at the depth scale considered. The calculated remineralization rates are extremely slow ranging from 5.6 mol C m−3 ky−1 at the top of the core to 0.2 mol C m−3 ky−1 according to the organic carbon flux to the seafloor. Knowing the labile carbon losses, we propose a method to calculate the initial TOC before the diagenesis took place.

•Using two dimensional correlation spectroscopy analysis (2D correlations) to study the dynamic of DOM.•Using the multi probes 2D correlations techniques gives more insight on the dynamics of DOM.•Six different compounds classes of DOM identified along salinity transect.Dissolved organic matter (DOM) is the most reactive organic carbon pool in earth. However, the heterogeneity of this organic mixture makes it difficult to investigate its dynamics under different external perturbations. In this review, we present the potential of using the two dimensional correlation spectroscopy analysis (2D correlations) as a tool to study the dynamic of DOM. We demonstrate the application of the 2D correlation analysis on high molecular weight DOM (HMW-DOM) with the salinity as perturbation parameter. We used four different chemical probes: Carbon nuclear magnetic resonance spectroscopy (13C NMR), Fourier transform infrared spectroscopy (FTIR), proton nuclear magnetic resonance spectroscopy (1H NMR) and Fourier transform ion cyclotron resonance mass spectrometry (FTICR-MS).Download high-res image (129KB)Download full-size image

The reaction of peptides with chemicals already present in natural waters (such as polycyclic aromatic hydrocarbons) is one method that has been suggested to preserve peptides for the longer term. In this study we test whether the reaction of tetrapeptides with a model quinone can help stabilise the peptide in one polluted riverine system, Elizabeth River in Virginia, USA. We found that there is almost no difference in rate constants between the peptide and its quinone adduct (e.g. 6.62 versus 6.86 per day for AVFA and its respective adduct). However, when monitoring the removal of the adduct from natural water, we identified two new compounds that are formed as a result of its decomposition. Using tandem mass spectrometry we identified potential structures and mechanisms for the formation of these new compounds. These new compounds are more recalcitrant than their parent peptide–quinone adduct, since they remain in solution for 3–10 times longer. Based on our findings we postulate that the reaction of peptides with quinones can help preserve sections of the original peptide following an initial rearrangement of the original adduct, potentially explaining why seemingly labile peptides are observed in most natural waters.

Two-dimensional (2D) correlation analysis was applied to 20 Fourier transform ion cyclotron resonance mass spectra (FTICR-MS) of ultrafiltered dissolved organic matter samples from a salinity transect of the lower Chesapeake Bay. We were able to investigate the chemical changes in the dissolved organic matter pool at the molecular level and classify the individual peaks based on their biogeochemical reactivity. The power of this technique is its ability to be used on either the presence/absence of the individual peaks or their normalized magnitudes. The presence or absence of the peaks are utilized to identify the reactivity and correlation between peaks that plot in different regions of the van Krevelen diagram, whereas the normalized magnitudes are used to correlate the changes among individual peaks. One of the promising advantages of 2D correlation of FTICR-MS data is the ability to associate the variations of the individual peaks with the changes in the functional groups that are measured by other spectroscopic techniques. This approach takes us one step further from identifying molecular formulas to proposing chemical structures.

•European-influenced aerosols have higher WSOC/trace metal ratios than North African.•European aerosol WSOM is characterized as more aliphatic and carboxyl-rich.•Aerosol WSOM characteristics may help explain higher fractional Fe and Al solubility.The atmospheric delivery of soluble and bioavailable iron (Fe) is essential for the biogeochemical functioning of many oceanic ecosystems where Fe is a limiting micronutrient for biological production. Aerosol samples associated with air masses characterized as European-influenced, primarily marine (no continental influence within 5 day back trajectories), or North African-influenced were collected along a cruise track in the eastern North Atlantic Ocean during a 2010 US GEOTRACES cruise. Aerosols were analyzed for total and soluble Fe and aluminum (Al) and organic matter (OM) loadings and OM chemical characteristics, to explore potential relationships between aerosol OM and Fe and Al that contribute to higher Fe and Al solubilities in combustion-influenced aerosols. Similar to the results from previous studies, North African-influenced air masses contained higher aerosol Fe (4.7–86 nmol m− 3) and Al (13–240 nmol m− 3) total loadings than European-influenced air masses (Fe: 0.63–2.7 nmol m− 3; Al: 2.5–5.9 nmol m− 3), but Fe and Al relative solubilities were much higher for European (Fe: 2.1–4.6%; Al: 1.9–3.2%) versus North African-influenced aerosols (Fe: 0.22–0.70%; Al: 0.39–1.1%). Water soluble organic carbon (WSOC) to trace metal ratios correlated positively with this trend in Fe and Al relative solubilities, as European-influenced WSOC/trace metal ratios ranged from ~ 2 to 32 while North African-influenced aerosol WSOC/trace metal ratios ranged from 0.04 to 0.51. Aerosols from primarily marine air masses showed the lowest Fe, Al, and OM loadings of all samples and Fe (0.71–2.5%) and Al (0.36–9.2%) solubilities that were variable and did not fit the patterns described for the continentally-influenced samples. Principal component analysis was employed on aerosol water soluble OM (WSOM) solution state 1H nuclear magnetic resonance spectra and revealed the European-influenced aerosol WSOM to be characterized by higher contributions from acetic acid (a common photoproduct of atmospheric OM) and aliphatic hydrogens, while North African-influenced aerosol WSOM was characterized by carbohydrate-like compounds and compounds with unsaturations. The abundance of the acetic acid photoproduct in European-influenced aerosol WSOM suggests this WSOM to be rich in carboxyl groups that are thought to be strong Fe-binding ligands and provides evidence for the potential role of WSOM in maintaining aerosol Fe and Al solubilities.

Suberan is a biopolymer located in the periderm (cork) of above ground parts of plants or the endoderm of roots. It acts as a protective barrier between plants and the environment and is commonly associated with another suberinic biopolymer, suberin. The structure of suberan has not been suggested, but is believed to have structural components similar to suberin. With the use of destructive and non-destructive techniques, including Fourier transform infrared (FTIR) spectroscopy, flash pyrolysis–gas chromatography–mass spectrometry (py–GC–MS), one and two-dimensional high-resolution magic angle spinning (HRMAS) nuclear magnetic resonance (NMR) spectroscopy, the structure of suberan from the Betula nigra bark, is now described. Based on data obtained from B. nigra bark, the non-saponifiable residue, considered to be suberan, is a polymethylenic biopolymer with alkyl chain length consisting mainly of 22 carbons, which is consistent with previous degradative studies. Furthermore, esters, acids and primary alcohols were also observed in suberan, which contribute to a glyceryl structural entity. The long-chain polymethylenic structures demonstrate a high degree of crystallinity, providing a primary structural difference between suberan and suberin.Highlights► A complete structure for suberan has been proposed. ► Structure of suberan assessed from FTIR, py–GC–MS and NMR. ► Suberan is crystalline, whereas suberin is predominantly non-crystalline. ► Suberinic material was subjected to base hydrolysis to isolate suberan.

This study describes a method for evaluating the reproducibility of replicate mass spectra acquired for complex natural organic matter (NOM) samples analyzed by electrospray ionization Fourier transform ion cyclotron resonance mass spectrometry, with regard to both peak detection and peak magnitude. Because studies of NOM characterization utilize not only the emergence and disappearance of peaks but also changes in relative peak magnitude, it is important to establish that the differences between samples are significantly larger than those between sample replicates. Here, a method is developed for correcting strict signal-to-noise thresholds, along with a new scheme for assessing the reproducibility of peak magnitudes. Furthermore, a systematic approach for discerning when the comparison of samples by the presence or absence of peaks is appropriate and when it is necessary to compare based on the relative magnitude of the peaks is presented. A variety of 10 different types of NOM samples are analyzed in duplicate or triplicate instrumental injections or experimental extractions. A framework for these procedures is provided, and acceptable reproducibility levels are recommended.

We apply multivariate statistics to explore the large data sets encountered from Fourier transform ion cyclotron resonance mass spectra of dissolved organic matter (DOM). Molecular formula assignments for the individual constituents of DOM are examined by hierarchal cluster analysis (HCA) and principal component analysis (PCA), to measure the relationships between numerous DOM samples. We compare two approaches: (1) using averages of elemental ratios and double bond equivalents calculated from the formulas, and (2) employing individual formulas and either their presence/absence or relative magnitude in each sample. With approach 2, PCA deciphers which of the thousands of formulas are significant to particular samples, and then a van Krevelen diagram highlights what types of compounds are molecular signatures to the samples. Our dual approach, especially approach 2, allows for complex data sets to be more easily interpreted, aiding in the characterization of DOM from various sources. By applying this methodology, clear trends can be delineated, trends that are not apparent from currently employed methods. Terrestrial DOM contains various lignin-derived compounds, tannins, and condensed aromatics. Marine DOM contains aliphatic compounds with heteroatom functionalities, as well as lignin-like molecules.

Applying two-dimensional correlation spectroscopy to 13C NMR and FTIR spectra of the high molecular-weight dissolved organic matter (HMW-DOM) isolated along an Elizabeth River/Chesapeake Bay salinity transect shows that HMW-DOM consists of three major components that have different biogeochemical reactivities. The first appears to be a heteropolysaccharide (HPS) component and its contribution to carbon increases as we approach the marine offshore. The second appears to be composed of carboxyl-rich compounds (CRC); its carbon percentage decreases. The third component contains the major functional group of amide/amino sugar (AMS) and its carbon percentage stays almost constant along the salinity transect. It seems that the HPS and CRC are present in many aquatic environments at different relative ratios. The 2D-correlation maps reveal that each of these components is composed of dynamic mixtures of compounds that share similar backbone structures but have significant functional group differences. Two-dimensional (2D) correlation spectroscopy is a powerful new biogeochemical tool to track the changes in complex organic matter as a function of space, time, or environmental effects.

A major obstacle for characterizing dissolved organic matter (DOM) with ultrahigh resolution mass spectrometry has been its low concentrations in natural waters. Many previous mass spectrometric studies of both terrestrial and marine DOM typically have isolated and concentrated the DOM using solid phase C18 extraction disks, ultrafiltration, or XAD resins, all of which are known to discriminate against many different classes of compounds. We have, for the first time, developed an approach to directly analyze natural water samples with less than 6 mg/l DOC (dissolved organic carbon), using electrospray ionization Fourier transform ion cyclotron resonance mass spectrometry (ESI-FTICR-MS). We demonstrate the sensitivity and ability of sequential selective ion accumulation (SSIA) to detect the thousands of components in a single freshwater DOM sample without any significant pretreatment. By utilizing SSIA, the baseline noise decreases while signal to noise ratios of the peaks increase, allowing for approximately 40% more formulas to be assigned to peaks in the mass spectra.

•Production of high value methylated derivatives of glycerol is discussed.•Thermally assisted methylation of glycerol using tetramethylammonium hydroxide (TMAH).•TMAH methylation can be performed in flow through reactors with efficient glycerol conversion.A novel method to rapidly methylate glycerol and generate products having greater value has been demonstrated using tetramethylammonium hydroxide (TMAH) thermochemolysis. Through analysis with GC–MS, it is shown that the reaction between TMAH and glycerol at elevated temperatures produces a series of mono, di and tri-methoxylated glycerols with potential applications as organic solvents. While other methylation reactions can only be carried out in batch reactions, thermally assisted methylation using TMAH can be performed in a continuous flow process.

The aliphatic region of natural organic matter (NOM) can retain polycyclic aromatic hydrocarbons (PAH) due to the presence of non-polar binding sites. Thus NOM may act as a vehicle for entry of PAH into the gastrointestinal system in man and animals. In this study, the release of phenanthrene from the aliphatic NOM surrogates cutin and cutan was measured under simulated human gastrointestinal formulations using three treatments designed to simulate the biological and chemical conditions of the gastrointestinal environment. The three experimental treatments were composed of fecal microorganisms, chyme, and chyme+fecal microorganisms. Water was used as a control treatment. Phenanthrene laden biopolymer and a C18 membrane were immersed in each treatment. Phenanthrene was extracted from each membrane and measured with HPLC. Membrane-associated phenanthrene was taken to represent the fraction that had desorbed from the biopolymer. Cutin was found to yield an average phenanthrene release 55% higher than cutan (94% vs. 39%). A significant decrease (p<0.05) in phenanthrene release was observed in both the chyme and chyme+fecal microorganism treatments as compared to the water treatment (control). The presence of enteric microorganisms did not significantly influence phenanthrene release and did not reduce phenanthrene bioaccessibility in gastrointestinal chyme. Over 80% of the phenanthrene in cutin was recovered in the C18 matrix and its relative amount was uninfluenced by the treatments. For cutan, only 25–50% of the phenanthrene was recovered, suggesting that cutin-associated phenanthrene was more loosely bound. These data demonstrate that the fractions of NOM retained phenanthrene to a varying extent and thus the predictions of phenanthrene bioavailability should also be assessed on the basis of the constituents of the NOM matrix.

Chemical characteristics of dissolved organic matter (DOM) extracted from an ombrotrophic bog in northern Minnesota by two methods – XAD-8 and DEAE-cellulose – were compared using 13C NMR spectroscopy, excitation–emission matrix fluorescence spectroscopy (EEMS), and Fourier transform ion cyclotron resonance mass spectrometry (FT-ICR MS). DOM extracted with XAD-8, a relatively hydrophobic sorbent, had a larger 13C NMR signal in the aromatic carbon region, but DOM extracted by DEAE-cellulose, a weak anion exchanger, had a larger signal in the carboxylic carbon region. DOM extracts prepared by the two methods were similar in their overall chemical characteristics that serve as proxies for organic matter sources. For example, only small differences were observed in the fluorescence index (FI) values of the extracts, and all values were within the range expected for terrestrially-derived DOM. EEMS spectra of both extracts had “humic-like” peak A areas smaller than that of standard reference Suwannee River fulvic acid. Of 2801 distinct chemical formulas assigned during FT-ICR MS analysis of the two extracts, 66% were present in both; 15% were unique to the XAD-8 extract, and 19% were unique to the DEAE-cellulose extract. Van Krevelen plots showed that the DEAE-cellulose extract had more tannin-like and condensed aromatic entities and formulas with higher O/C ratios, whereas the XAD-8 extract had more lignin-like material and formulas with higher H/C ratios. Overall, differences in chemical characteristics of the extracts reflect the mechanisms by which the extractants operate.

Fixed nitrogen (N) plays an integral role in global cycling; while most is recycled to refuel primary productivity, a small fraction escapes to be preserved and stabilised in sediments. Despite decades of research, the functionality and reactivity of this sequestered organic N has been poorly understood. This study was undertaken to shed light on this problem by characterising the bulk sediment organic matter using nuclear magnetic resonance (NMR), followed by molecular level analysis using ultrahigh resolution Fourier transform ion cyclotron resonance mass spectrometry (FT–ICR–MS). We studied two organic-rich anaerobic sediments, one from a freshwater system and another from a marine paralic basin. Mangrove Lake, Bermuda (marine) and Mud Lake, Florida (freshwater) have been shown in past studies to contain high levels of N-containing organic matter. Our resulting multidimensional NMR data suggests the existence of a new type of amide functionality in both these lake sediments, and we investigated this further using FT–ICR–MS and gas chromatography mass spectrometry (GC–MS). FT–ICR–MS confirmed the existence of homologous series of CHNO containing compounds, whose structures are verified using GC–MS as alkyl amides. Model reactions involving naturally occurring esters and ammonia suggest the source of alkyl amides to be amidation of esters with sedimentary ammonia derived from anaerobic degradation of organic matter. This expands upon previous hypotheses for preservation of amide containing compounds that call upon biological/abiological protection of proteins and peptides or the formation of refractory nitrogenous adducts.

Lake Vida (LV) is located in the McMurdo Dry Valleys (Victoria Valley, East Antarctica) and has no inflows, outflows, or connectivity to the atmosphere due to a thick (16 m), turbid ice surface and cold (<−20 °C) subsurface alluvium surrounding the lake. The liquid portion of LV has a salinity about seven times that of seawater and is entrained in ice and sediment below the ice cap. This subzero (−13.4 °C), anoxic brine supports a microbial community, which has low levels of activity and has been isolated from the atmosphere for at least 2800 14C years before present. The brine has high dissolved organic carbon concentration (DOC; 580 mg-C L−1 or greater); the study of which provides a unique opportunity to better understand biological and/or abiotic processes taking place in an isolated saline ecosystem with no external inputs. We isolated two sub-fractions of LV dissolved organic matter (DOM) by chemical separation using XAD-8 and XAD-4 resins in series. This separation was followed by physical separation using ultrafiltration to isolate a higher molecular weight (HMW) fraction that was retained by the membrane and a salty, dilute low molecular weight fraction. This analytical path resulted in three, low salt sub-fractions and allowed comparison to other Antarctic lake DOM samples isolated using similar procedures. Compared to other Antarctic lakes, a lower portion of the DOC was retained by XAD-8 (∼10% vs. 16–24%) resin, while the portions retained by XAD-4 (∼8%) resin and the 1 kDa ultrafiltration membrane (∼50%) were similar. The 14C radiocarbon ages of the XAD-8 (mean 3940 ybp), XAD-4 (mean 4048 ybp) and HMW (mean 3270 ybp) fractions are all older than the apparent age of ice-cover formation (2800 ybp). Ultrahigh resolution mass spectrometry showed that compounds with two and three nitrogen atoms in the molecular formulas were common in both the LV-XAD8 and LV-XAD4 fractions, consistent with microbial production and processing. The long-term oxidation of LVBr DOM by abiotic oxidants including perchlorate and chlorate may explain the low portion in the XAD8 fraction and the lack of aromatic carbon, as measured by 13C NMR spectroscopy, found for all but the most hydrophobic fraction, LV-XAD8. Overall, the chemical characteristics of Lake Vida brine DOM suggest that legacy DOM sealed and concentrated within the brine has been altered due to a combination of both biological and abiotic chemical reactions.

The incomplete combustion of fossil fuels and biomass has resulted in the global-scale distribution and accumulation of black carbon (BC) in the environment. Recently, the molecular identity of BC in the dissolved phase has been distinguished from that of natural organic matter. However, many of the processes that control BC cycling remain unidentified. We investigate changes in soil charcoal particle morphology and chemical composition using surface area analysis, scanning electron microscopy, energy dispersive X-ray spectroscopy, chemical oxidation, and 13C NMR spectroscopy. A comparison of soil charcoals differing in age by 100 years shows that aged charcoal has lower specific surface areas, higher BC/OC ratios, direct associations with soil minerals and microbial biomass, and a greater abundance of non-aromatic carbon. The water-soluble portion of soil charcoal and dissolved organic matter (DOM) from the watershed were also characterized by electrospray ionization mass spectrometry. Aqueous charcoal extracts are comprised mostly of condensed aromatic ring structures (CARS) which are also present in soil pore, river, and ground water samples. We present indirect evidence and a chemical rationale for a microbial BC dissolution mechanism. Furthermore, the speciation of CARS in the soil solution versus river and ground water provides molecular evidence of reactivity in the dissolved phase. The dissolution and export of soil BC are presently unmeasured fluxes with important implications for the global carbon cycle.

Evidence suggests that reactive oxygen species (ROS) are important in transforming the chemical composition of the large pool of terrestrially-derived dissolved organic matter (DOM) exported from land to water annually. However, due to the challenges inherent in isolating the effects of individual ROS on DOM composition, the role of ROS in the photochemical alteration of DOM remains poorly characterized. In this work, terrestrial DOM was independently exposed to singlet oxygen (1O2), and superoxide (O2- under controlled laboratory conditions). Using ultra-high resolution mass spectrometry to track molecular level alterations of DOM by ROS, these findings suggest exposure to 1O2 (generated using Rose Bengal and visible light) removed formulas with an O/C > 0.3, and primarily resulted in DOM comprised of formulas with higher oxygen content, while O2- exposure (from KO2 in DMSO) removed formulas with O/C < 0.3 and produced aliphatic formulas (H/C > 1.5). Comparison of DOM altered by ROS in this study to riverine and coastal DOM showed that (20–80%) overlap in formulas, providing evidence for the role of ROS in shaping the composition of DOM exported from rivers to oceans.

The reaction of peptides with chemicals already present in natural waters (such as polycyclic aromatic hydrocarbons) is one method that has been suggested to preserve peptides for the longer term. In this study we test whether the reaction of tetrapeptides with a model quinone can help stabilise the peptide in one polluted riverine system, Elizabeth River in Virginia, USA. We found that there is almost no difference in rate constants between the peptide and its quinone adduct (e.g. 6.62 versus 6.86 per day for AVFA and its respective adduct). However, when monitoring the removal of the adduct from natural water, we identified two new compounds that are formed as a result of its decomposition. Using tandem mass spectrometry we identified potential structures and mechanisms for the formation of these new compounds. These new compounds are more recalcitrant than their parent peptide–quinone adduct, since they remain in solution for 3–10 times longer. Based on our findings we postulate that the reaction of peptides with quinones can help preserve sections of the original peptide following an initial rearrangement of the original adduct, potentially explaining why seemingly labile peptides are observed in most natural waters.