Electrospray Ionization Fourier Transform Ion Cyclotron Resonance Mass Spectrometry Research Articles

Photolysis of Dissolved Organic Matter over Hematite Nanoplatelets.

Solar photoexcitation of chromophoric groups in dissolved organic matter (DOM), when coupled to photoreduction of ubiquitous Fe(III)-oxide nanoparticles, can significantly accelerate DOM degradation in near-surface terrestrial systems, but the mechanisms of these reactions remain elusive. We examined the photolysis of chromophoric soil DOM coated onto hematite nanoplatelets featuring (001) exposed facets using a combination of molecular spectroscopies and density functional theory (DFT) computations. Reactive oxygen species (ROS) probed by electron paramagnetic resonance (EPR) spectroscopy revealed that both singlet oxygen and superoxide are the predominant ROS responsible for DOM degradation. DFT calculations confirmed that Fe(II) on the hematite (001) surface, created by interfacial electron transfer from photoexcited chromophores in DOM, can reduce dioxygen molecules to superoxide radicals (•O2-) through a one-electron transfer process. 1H nuclear magnetic resonance (NMR) and electrospray ionization Fourier-transform ion cyclotron resonance mass spectrometry (ESI-FTICR-MS) spectroscopies show that the association of DOM with hematite enhances the cleavage of aromatic groups during photodegradation. The findings point to a pivotal role for organic matter at the interface that guides specific ROS generation and the subsequent photodegradation process, as well as the prospect of using ROS signatures as a forensic tool to help interpret more complicated field-relevant systems.

Presence of aromatic-rich organic matter and its characterization in grout materials: Implications for radionuclide immobilization

Grout materials are commonly used to immobilize low-level radioactive waste. Organic moieties can be unintentionally present in common ingredients used to make these grout waste forms, which may result in the formation of organo-radionuclide species. These species can positively or negatively affect the immobilization efficiency. However, the presence of organic carbon compounds is rarely considered in models or characterized chemically. Here, we quantify the organic pool of grout formulations with and without slag, as well as the individual dry ingredients used to make the grout samples (ordinary Portland cement (OPC), slag and fly ash), including total organic carbon (TOC) and black carbon, followed by aromaticity evaluation and molecular characterization via Electro Spray Ionization Fourier-Transform Ion Cyclotron Resonance Mass Spectrometry (ESI-FTICRMS). All dry grout ingredients contained significant amounts of organic carbon, ranging from 550 mg/kg to 6250 mg/kg for the TOC pool, with an averaged abundance of 2933 ± 2537 mg/kg, of which 60 ± 29% was composed of black carbon. The significant abundance of a black carbon pool implies the presence of the aromatic-like compounds, which was further identified by both phosphate buffer-assisted aromaticity evaluation (e.g., >1000 mg-C/kg as aromatic-like carbon in the OPC) and dichloromethane (DCM) extraction with ESI-FTICRMS analysis. Besides aromatic-like compounds, other organic moieties were also detected in the OPC, such as carboxyl-containing aliphatic molecules. While the organic compound only consists of minor fractions of the grout materials investigated, our observations of the presence of various radionuclide-binding organic moieties suggests the potential formation of organo-radionuclides, such as radioiodine, which might be present at lower molar concentrations than TOC. Evaluating the role of organic carbon complexation in controlling the disposed radionuclides, especially for those radionuclides with strong association with organic carbon, has important implications for the long-term immobilization of radioactive waste in grout systems.

Comparison of Sample Preparation Techniques for the (−)ESI-FT-ICR-MS Analysis of Humic and Fulvic Acids

Soil organic matter (SOM) plays a key role in the global carbon and nitrogen cycles. Soil biogeochemistry is regularly studied by extracting the base-soluble fractions of SOM: acid-insoluble humic acid (HA) and acid-soluble fulvic acid (FA). Electrospray ionization-Fourier transform-ion cyclotron resonance-mass spectrometry (ESI-FT-ICR-MS) is commonly utilized for molecularly characterizing these fractions. Different sample preparation techniques exist for the analysis of HA and FA though questions remain regarding data comparability following different preparations. Comparisons of different sample preparation techniques here revealed that the negative-mode ESI-FT-ICR-MS analytical window can be skewed to detect different groups of molecules, with primary differences in oxygenation, aromaticity, and molecular weight. It was also observed that HA and FA from soils versus an aquatic matrix behaved very differently. Thus, we conclude that sample preparation techniques determined to be "most optimal" in our study are in no way universal. We recommend that future studies of HA and FA involve similar comparative studies for determining the most suitable sample preparation technique for their particular type of HA or FA matrices. This will enhance data comparability among different studies and environmental systems and ultimately allow us to better understand the complex composition of environmental matrices.

Surrogate formulation and molecular characterization of sulfur species in vacuum residues using APPI and ESI FT-ICR mass spectrometry

Vacuum residues (VR) are the bottom of the barrel products left after vacuum distillation of crude oils. VR are primarily used as feedstock for production of syn-gas and hydrogen via gasification; and heavy fuel oil (HFO) for use as fuel in power generation and shipping. However, VR contain relatively large amounts of sulfur (upto 8% by mass) and require the removal of varying amounts depending on the emission norms (eg. International Maritime Organization 2020 sulfur regulations). Understanding the fuel molecular structure and, in particular, the structure of sulfur species enables the adoption and optimization of suitable desulfurization strategies. In the present work, detailed molecular characterization of the sulfur species in VR was performed using positive ion atmospheric pressure photoionization (APPI) and electrospray ionization (ESI) coupled to Fourier transform ion cyclotron resonance (FT-ICR) mass spectrometry (MS). Ions possessing mass to charge (m/z) in the range of 100 to 1200 were detected using the ultra-high resolution instrument and were resolved into unique chemical formulas (CcHhSsNnOo). The assigned masses were then divided into molecular classes based on the presence of heteroatoms, and plots of carbon number versus double bond equivalency (DBE) were made for each molecular class. The molecular classes were further sub-divided based on the presence of sulfur families like sulfides (Su), thiophenes (Th), benzothiophenes (BT), dibenzothiophenes (DBT) and benzonaphthothiophene (BNT) and their derivatives. A single surrogate molecule that represents the average structure of the VR sample was then designed based on the average molecular parameters (AMP) obtained from APPI and ESI FT-ICR MS. Plausible core skeletal structures of VR were drawn from the average DBE value, and then a symmetrical, alkylated, polyaromatic sulfur heterocycles (PASH) molecule was formulated as the VR surrogate. A number of physical and thermo-chemical properties of the VR surrogate were then predicted using quantitative structure property relationships (QSPR). The VR surrogate proposed here will enable high-fidelity computational studies, including chemical kinetic modeling, property estimation, and emissions modeling.

Application of Hydrochar Altered Soil Microbial Community Composition and the Molecular Structure of Native Soil Organic Carbon in a Paddy Soil.

The benefits and disadvantages of hydrochar incorporation into soil have been heavily researched. However, the effect of hydrochar application on the soil microbial communities and the molecular structure of native soil organic carbon (SOC) has not been thoroughly elucidated. This study conducted an incubation experiment at 25 °C for 135 days using a soil column with 0.5 and 1.5% hydrochar-amended paddy soil to explore the interconnections between changes in soil properties and microbial communities and shifts in native SOC structure using electrospray ionization Fourier transform ion cyclotron resonance mass spectrometry (ESI-FT-ICR-MS) and NMR after hydrochar application. Hydrochar addition decreased the labile SOC fraction by 15.6-33.6% and increased the stable SOC fraction by 10.3-27.0%. These effects were significantly stronger for 1.5% hydrochar-treated soil. Additionally, hydrochar addition induced the native SOC with 1.0-3.0% more carbon and 6.0-13.0% higher molecular weight. The SOC in hydrochar-amended soil contained more aromatic compounds but fewer carbohydrates and lower polarity. This was resulted by a statistically significant reduction in Sphingobacterium, which was active in polycyclic aromatic hydrocarbon degradation, and an increase in Flavobacterium, Anaerolinea, Penicillium, and Acremonium, which were the efficient decomposers of labile SOC. These findings will help elucidate the potential influence of hydrochar on the carbon biogeochemical cycle in the soil.

Nagasaki sediments reveal that long-term fate of plutonium is controlled by select organic matter moieties

Forecasting the long-term fate of plutonium (Pu) is becoming increasingly important as more worldwide military and nuclear-power waste is being generated. Nagasaki sediments containing bomb-derived Pu that was deposited in 1945 provided a unique opportunity to explore the long-term geochemical behavior of Pu. Through a combination of selective extractions and molecular characterization via electrospray ionization Fourier-transform ion cyclotron resonance mass spectrometry (ESI-FTICRMS), we determined that 55 ± 3% of the bomb-derived 239,240Pu was preferentially associated with more persistent organic matter compounds in Nagasaki sediments, particularly those natural organic matter (NOM) stabilized by Fe oxides (NOMFe-oxide). Other organic matter compounds served as a secondary sink of these bomb-derived 239,240Pu (31 ± 2% on average), and <20% of the 239,240Pu was immobilized by inorganic mineral particles. In a narrow, 239,240Pu-enriched layer of only 9-cm depth (total core depth was 600 cm), N-containing carboxyl aliphatic and/or alicyclic molecules (CCAM) in NOMFe-oxide and other NOM fractions immobilized the majority of 239,240Pu. Among the cluster of N-containing CCAM moieties, hydroxamate siderophores, the strongest known Pu chelators in nature, were further detected in these “aged” Nagasaki bomb residue-containing sediments. While present long-term disposal and environmental remediation modeling assume that solubility limits and sorption to mineral surfaces control Pu subsurface mobility, our observations suggest that NOM, which is present in essentially all subsurface systems, undoubtedly plays an important role in sequestrering Pu. Ignoring the role of NOM in controlling Pu fate and transport is not justified in most environmental systems.

A Novel Natural Influenza A H1N1 Virus Neuraminidase Inhibitory Peptide Derived from Cod Skin Hydrolysates and Its Antiviral Mechanism.

In this paper, a novel natural influenza A H1N1 virus neuraminidase (NA) inhibitory peptide derived from cod skin hydrolysates was purified and its antiviral mechanism was explored. From the hydrolysates, novel efficient NA-inhibitory peptides were purified by a sequential approach utilizing an ultrafiltration membrane (5000 Da), sephadex G-15 gel column and reverse-phase high-performance liquid chromatography (RP-HPLC). The amino acid sequence of the pure peptide was determined by electrospray ionization Fourier transform ion cyclotron resonance mass spectrometry (ESI-FTICR-MS) was PGEKGPSGEAGTAGPPGTPGPQGL, with a molecular weight of 2163 Da. The analysis of the Lineweacer–Burk model indicated that the peptide was a competitive NA inhibitor with Ki of 0.29 mM and could directly bind free enzymes. In addition, docking studies suggested that hydrogen binding might be the driving force for the binding affinity of PGEKGPSGEAGTAGPPGTPGPQGL to NA. The cytopathic effect reduction assay showed that the peptide PGEKGPSGEAGTAGPPGTPGPQGL protected Madin–Darby canine kidney (MDCK) cells from viral infection and reduced the viral production in a dose-dependent manner. The EC50 value was 471 ± 12 μg/mL against H1N1. Time-course analysis showed that PGEKGPSGEAGTAGPPGTPGPQGL inhibited influenza virus in the early stage of the infectious cycle. The virus titers assay indicated that the NA-inhibitory peptide PGEKGPSGEAGTAGPPGTPGPQGL could directly affect the virus toxicity and adsorption by host cells, further proving that the peptide had an anti-viral effect with multiple target sites. The activity of NA-inhibitory peptide was almost inactivated during the simulated in vitro gastrointestinal digestion, suggesting that oral administration is not recommended. The peptide PGEKGPSGEAGTAGPPGTPGPQGL acts as a neuraminidase blocker to inhibit influenza A virus in MDCK cells. Thus, the peptide PGEKGPSGEAGTAGPPGTPGPQGL has potential utility in the treatment of the influenza virus infection.

Ultra-high resolution mass spectrometry of physical speciation patterns of organic matter in fire-affected soils

Fire is one of the most important modulating factors of the environment and the forest inducing chemical and biological changes on the most reactive soil component, the soil organic matter (SOM). Assuming the complex composition of the SOM, we used an ultra-high resolution mass spectrometry analysis technique to assess the chemical composition and fire-induced alterations in soil particle size fractions (coarse and fine) from a sandy soil in a Mediterranean oak forest at Doñana National Park (Southwest Spain). Electrospray ionization-Fourier transform ion cyclotron resonance mass spectrometry (ESI-FTICRMS) showed that the coarse fraction of soils not affected by fires consisted mainly of polyphenolic compounds consistent with little-transformed SOM and fresh biomass, whereas the fine fraction was enriched in protein and lipid like homologues suggesting microbially reworked SOM. In fire-affected SOM, the coarse fraction contained a high proportion of aromatic compounds, consistent with inputs of charred litter or in situ chemical transformation of the SOM. Analysis of the fine fraction revealed two differentiated chemical families pointing to the existence of two carbon pools; a native microbial-derived moiety composed of lipids and polypeptide compounds, and a secondary, pyrogenic or thermally-altered moiety rich in aromatic compounds. This work represents the first application of ultra-high resolution mass spectrometry to study the chemical composition of SOM in different particle size fractions.

Investigating organic matter properties affecting the binding behavior of heavy metals in the rhizosphere of wetlands

Soil organic matter (SOM) is a crucial factor affecting the immobilization of heavy metal in wetlands. Recent studies have shown that the rhizosphere SOM has great ability to immobilize heavy metals. However, there existed few works on studying molecular characteristics of SOM to explore the mechanisms. Electrospray ionization–Fourier transform ion cyclotron resonance–mass spectrometry (ESI-FTICR-MS) combined with FTIR spectroscopy were applied to investigate the characteristics of SOM in rhizosphere and nonrhizosphere samples and to find out what characteristics the rhizosphere SOM embodies conducive to metal binding in this paper. The rhizosphere contained higher C, P, Mn, and other metal concentrations. The adsorption of Cr on rhizosphere SOM was greater than that on nonrhizosphere SOM. Compared to nonrhizosphere SOM, rhizosphere SOM contained less saturated and more oxidized compounds, greater overall molecular weights (MW), more condensed aromatic structures (56.59% VS 51.56% by peak intensity), less carboxylate and N-containing COO functional groups (25.98% VS 56.63% by peak intensity), more hydrophilicity, and the latter four are conducive to metal binding. This study showed that the rhizosphere SOM had unique compositional and structural characteristics. These results provided evidence for the phytoremediation technologies of heavy metal contaminated wetlands.

Molecular signatures of dissolved organic matter in a tropical karst system

Karst areas are widespread landforms present on all continents, formed by the dissolution of carbonate or evaporite host rock. Little is known about the composition and nature of dissolved organic matter (DOM) as it moves through karst systems, although karst DOM has been recognized as important for a range of natural processes. Microbial communities living in karst systems are some of the most diverse and intriguing on the planet, and their metabolism and life cycle can give clues related to the development of a host of different life forms. Karst areas are also of interest due to their mostly subterranean hydrology, and the repercussions of these processes on local carbon cycles.We illustrate some of the processes acting on DOM in karst waters through the analysis of soil, drip and cave pool waters at the tropical site of Yok Balum Cave, in southern Belize. Water samples were analyzed using ultra-high resolution electrospray ionization Fourier transform ion cyclotron resonance mass spectrometry (ESI-FT-ICR-MS), a technique that enables the resolution of single molecular formulae within a DOM spectrum. We perform multivariate statistics to detect trends in the data and identify provenance of detected molecular components. In addition to karst waters, four aliquots of a powdered stalagmite sample from the same cave system are analyzed. Our results show a clear gradient between the soil and the cave system. We hypothesize that both sorption on mineral surfaces and microbial reworking are responsible for the observed trend in DOM composition. The stalagmite extracts show an anomalous DOM pattern, which may be due to a variety of factors, including microbial activity on the stalagmite surface and different affinities of compounds to incorporation in the carbonate. The goal of this study was to follow the molecular transformations of DOM on its journey from the surface to the cave, and to provide a molecular basis for the establishment of stalagmite DOM proxies in karst systems.

Alicyclic carboxylic acids in soil humic acid as detected with ultrahigh resolution mass spectrometry and multi-dimensional NMR

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.

Substructural Components of Organic Colloids from a Pu-Polluted Soil with Implications for Pu Mobilization.

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.

Isolation and Structural Characterization of Two New Furanoditerpenes from Pterodon emarginatus (Fabaceae)

A furanoditerpene-enriched fraction was obtained from the fruits of Pterodon emarginatus and submitted to semipreparative high performance liquid chromatography (HPLC). Two new furanoditerpenes, 6α,19β-diacetoxy-7β,14β-dihydroxyvouacapan and 6α-acetoxy-7β,14β-dihydroxyvouacapan, in addition to the known compound methyl 6α-acetoxy-7β-hydroxyvouacapan-17β-oate were obtained. Compound structures were determined by 1D and 2D nuclear magnetic resonance (NMR) experiments and electrospray ionization Fourier transform ion cyclotron resonance mass spectrometry (ESI-FTICR-MS). The major compound methyl 6α-acetoxy-7β-hydroxyvouacapan-17β-oate was evaluated against promastigote forms of Leishmania amazonensis and L. braziliensis, presenting the concentration which causes lysis on 50% of parasites IC50 < 30 µg mL-1.

Comparing molecular composition of dissolved organic matter in soil and stream water: Influence of land use and chemical characteristics

Electrospray ionization Fourier transform ion cyclotron resonance mass spectrometry (ESI-FT-ICR-MS) was used to examine the molecular composition of dissolved organic matter (DOM) from soils under different land use regimes and how the DOM composition in the catchment is reflected in adjacent streams. The study was carried out in a small area of the Schwingbach catchment, an anthropogenic-influenced landscape in central Germany. We investigated 30 different soil water samples from 4 sites and different depths (managed meadow (0–5cm, 40–50cm), deciduous forest (0–5cm), mixed-coniferous forest (0–5cm) and agricultural land (0–5cm, 40–50cm)) and 8 stream samples. 6194 molecular formulae and their magnitude-weighted parameters ((O/C)w, (H/C)w, (N/C)w, (AI-mod)w, (DBE/C)w, (DBE/O)w, (DBE-O)w, (C#)w, (MW)w) were used to describe the molecular composition of the samples.The samples can be roughly divided in three groups. Group 1 contains samples from managed meadow 40–50cm and stream water, which are characterized by high saturation compared to samples from group 2 including agricultural samples and samples from the surface meadow (0–5cm), which held more nitrogen containing and aromatic compounds. Samples from both forested sites (group 3) are characterized by higher molecular weight and O/C ratio. Environmental parameters vary between sites and among these parameters pH and nitrate significantly affect chemical composition of DOM. Results indicate that most DOM in streams is of terrestrial origin. However, 120 molecular formulae were detected only in streams and not in any of the soil samples. These compounds share molecular formulae with peptides, unsaturated aliphatics and saturated FA-CHO/FA-CHOX. Compounds only found in soil samples are much more aromatic, have more double bonds and a much lower H/C ratio but higher oxygen content, which indicates the availability of fresh plant material and less microbial processed material compared to stream samples.

Linking molecular size, composition and carbon turnover of extractable soil microbial compounds

Microbial contribution to the maintenance and turnover of soil organic matter is significant. Yet, we do not have a thorough understanding of how biochemical composition of soil microbial biomass is related to carbon turnover and persistence of different microbial components. Using a suite of state-of-the-art analytical techniques, we investigated the molecular characteristics of extractable microbial biomass and linked it to its carbon turnover time. A 13CO2 plant pulse labelling experiment was used to trace plant carbon into rhizosphere soil microbial biomass, which was obtained by chloroform fumigation extraction (CFE). 13C content in molecular size classes of extracted microbial compounds was analysed using size exclusion chromatography (SEC) coupled online to high performance liquid chromatography–isotope ratio mass spectrometry (SEC-HPLC-IRMS). Molecular characterization of microbial compounds was performed using complementary approaches, namely SEC-HPLC coupled to Fourier transform infrared spectroscopy (SEC-HPLC-FTIR) and electrospray ionization Fourier transform ion cyclotron resonance mass spectrometry (ESI-FT-ICR-MS). SEC-HPLC-FTIR suggests that mid to high molecular weight (MW) microbial compounds were richer in aliphatic CH bonds, carbohydrate-like compounds and possibly PO derivatives from phospholipids. On the contrary, the lower size range was characterized by more oxidised compounds with hydroxyl, carbonyl, ether and/or carboxyl groups. ESI-FT-ICR-MS suggests that microbial compounds were largely aliphatic and richer in N than the background detrital material. Both molecular characterization tools suggest that CFE derived microbial biomass was largely lipid, carbohydrate and protein derived. SEC-HPLC-IRMS analysis revealed that 13C enrichment decreased with increasing MW of microbial compounds and the turnover time was deduced as 12.8 ± 0.6, 18.5 ± 0.6 and 22.9 ± 0.7 days for low, mid and high MW size classes, respectively. We conclude that low MW compounds represent the rapidly turned-over metabolite fraction of extractable soil microbial biomass consisting of organic acids, alcohols, amino acids and sugars; whereas, larger structural compounds are part of the cell envelope (likely membrane lipids, proteins or polysaccharides) with a much lower renewal rate. This relation of microbial carbon turnover to its molecular size, structure and composition thus highlights the significance of cellular biochemistry in determining the microbial contribution to soil carbon cycling and specifically soil organic matter formation.

Characterization of heteroatom-containing species in the soluble portion from the ethanolysis of the extraction residue from Xinghe lignite by electrospray ionization Fourier transform ion cyclotron resonance mass spectrometry

The extraction residue (ER) from Xinghe lignite was subjected to ethanolysis at 300°C and the yield of ethanol-soluble portion (ESP) is 66.8wt% (daf). The ER was characterized by solid-state 13C nuclear magnetic resonance spectrometry (SS 13C NMRS) and X-ray photoelectron spectrometry (XPS), while non-basic and basic heteroatom-containing species in the ESP were analyzed by negative- and positive-ion electrospray ionization (ESI) Fourier transform ion cyclotron resonance mass spectrometry (FTICRMS), respectively. According to the characterization by SS 13C NMRS, the ER contains 56.6% of aromatic carbon and 37.8% of aliphatic carbon and each aromatic cluster contains 2 aromatic rings on average. The characterization by XPS suggests that OH, pyrrolic nitrogen, thiophene, and sulfoxide are important heteroatom occurrences in the ER. According to the analysis by ESI FTICRMS, the non-basic and basic species distribute in the range of molecular mass from 160 to 450u and 200 to 950u, respectively. The abundant O2 class species among the identified non-basic species could be alkanoic acids, arenediols, and arenoic acids. Non-basic N and NO classes could be pyrroles, indoles, and carbazoles with double bond equivalent (DBE) values from 1 to 16 and carbon numbers (CNs) from 7 to 28. The NOx class species dominate the basic species and span wider DBE values (4–24) and CNs (14–54). Most of these species could be attributed to quinolines (DBE⩾7), acridines (DBE⩾10), and N-heterocyclic aromatics with at least 4 rings like benzoacridine ring (DBE=13). Sulfur in the acidic classes (O3S, S2, and OS2) mainly exists in mercapto group and/or thiophene ring, while the basic OS and O2S classes may have sulfur present in thiophene sulfoxides and thiophene sulfones, respectively.

Use of ESI-FTICR-MS to Characterize Dissolved Organic Matter in Headwater Streams Draining Forest-Dominated and Pasture-Dominated Watersheds.

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

Tracking changes in the optical properties and molecular composition of dissolved organic matter during drinking water production

Absorbance, 3D fluorescence and ultrahigh resolution electrospray ionization Fourier transform ion cyclotron resonance mass spectrometry (ESI-FT-ICR-MS) were used to explain patterns in the removal of chromophoric and fluorescent dissolved organic matter (CDOM and FDOM) at the molecular level during drinking water production at four large drinking water treatment plants in Sweden. When dissolved organic carbon (DOC) removal was low, shifts in the dissolved organic matter (DOM) composition could not be detected with commonly used DOC-normalized parameters (e.g. specific UV254 absorbance – SUVA), but was clearly observed by using differential absorbance and fluorescence or ESI-FT-ICR-MS. In addition, we took a novel approach by identifying how optical parameters were correlated to the elemental composition of DOM by using rank correlation to connect optical properties to chemical formulas assigned to mass peaks from FT-ICR-MS analyses. Coagulation treatment selectively removed FDOM at longer emission wavelengths (450–600 nm), which significantly correlated with chemical formulas containing oxidized carbon (average carbon oxidation state ≥0), low hydrogen to carbon ratios (H/C: average ± SD = 0.83 ± 0.13), and abundant oxygen-containing functional groups (O/C = 0.62 ± 0.10). Slow sand filtration was less efficient in removing DOM, yet selectively targeted FDOM at shorter emission wavelengths (between 300 and 450 nm), which commonly represents algal rather than terrestrial sources. This shorter wavelength FDOM correlated with chemical formulas containing reduced carbon (average carbon oxidation state ≤0), with relatively few carbon-carbon double bonds (H/C = 1.32 ± 0.16) and less oxygen per carbon (O/C = 0.43 ± 0.10) than those removed during coagulation. By coupling optical approaches with FT-ICR-MS to characterize DOM, we were for the first time able to confirm the molecular composition of absorbing and fluorescing DOM selectively targeted during drinking water treatment.

The molecular composition of dissolved organic matter in forest soils as a function of pH and temperature.

We examined the molecular composition of forest soil water during three different seasons at three different sites, using electrospray ionization Fourier transform ion cyclotron resonance mass spectrometry (ESI-FT-ICR-MS). We examined oxic soils and tested the hypothesis that pH and season correlate with the molecular composition of dissolved organic matter (DOM). We used molecular formulae and their relative intensity from ESI-FT-ICR-MS for statistical analysis. Applying unconstrained and constrained ordination methods, we observed that pH, dissolved organic carbon (DOC) concentration and season were the main factors correlating with DOM molecular composition. This result is consistent with a previous study where pH was a main driver of the molecular differences between DOM from oxic rivers and anoxic bog systems in the Yenisei River catchment. At a higher pH, the molecular formulae had a lower degree of unsaturation and oxygenation, lower molecular size and a higher abundance of nitrogen-containing compounds. These characteristics suggest a higher abundance of tannin connected to lower pH that possibly inhibited biological decomposition. Higher biological activity at a higher pH might also be related to the higher abundance of nitrogen-containing compounds. Comparing the seasons, we observed a decrease in unsaturation, molecular diversity and the number of nitrogen-containing compounds in the course of the year from March to November. Temperature possibly inhibited biological degradation during winter, which could cause the accumulation of a more diverse compound spectrum until the temperature increased again. Our findings suggest that the molecular composition of DOM in soil pore waters is dynamic and a function of ecosystem activity, pH and temperature.

Ecosystem‐Specific Composition of Dissolved Organic Matter

We investigated the molecular composition of dissolved organic matter (DOM) from various rivers, bogs and soil sites to test for their ecosystems unique molecular patterns. This information is prerequisite for searching of new marker compounds that might help tracing the fate of ecosystem‐derived organic matter from terrestrial to marine systems. We used electrospray ionization Fourier transform ion cyclotron resonance mass spectrometry (ESI‐FT‐ICR‐MS) to identify the ecosystem‐specific molecular DOM characteristics. We investigated 39 samples and explored their patterns through nonmetric multidimensional scaling (NMDS). Based on the intrasystem similarity, we identified unique molecular formulae for each ecosystem and compared their main characteristics. Our data indicate a pH influence on all samples and possibly a vegetation influence on soil water samples. We interpreted the lack of nitrogen‐containing compounds in the surface water and the lower molecular size in the soil water with higher microbial activity and reworking in soils and the lack of aromatic compounds in surface waters as the result of photo degradation. Our results demonstrate that this approach is suitable for resolving ecosystem‐specific markers; the tannin molecular formulae seemed to be particularly suited markers for forest systems. However, we emphasize that it is necessary to collect a larger number of samples and reasonable environmental parameters to explain the distinctive molecular features and evaluate new markers. Aside from the ecosystem‐specific features, we also found a suite of compounds that were present in all samples, indicating the convergent evolution of terrestrial DOM for a wide gradient of physicochemical and biological features. The molecular formulae of these ubiquitous compounds match those of carboxyl‐rich alicyclic molecules (CRAM), but distinction from lignin is only possible by applying methods that elucidated the molecular structure.