Electrospray and Photoionization Mass Spectrometry for the Characterization of Organic matter in Natural Waters: A Qualitative Assessment

Fourier-transform ion cyclotron resonance mass spectrometry (MS) has demonstrated potential to revolutionize the fields of limnology and chemical oceanography by identifying the individual molecular components of organic matter in natural waters. The use of MS for this purpose is made possible by the electrospray technique which successfully ionizes polar, nonvolatile organic molecules. Another recently developed ion source, atmospheric pressure photoionization (APPI), extends MS capabilities to less polar molecules. This article presents early results on the application of APPI MS to natural organic matter. We compare APPI MS and electrospray MS data for dissolved organic matter from Lake Drummond (Virginia, USA). Collectively, electrospray and APPI MS identify more than 6000 molecular species to which we assign unique molecular formulas. Fewer than 1000 molecular species are common to both electrospray and APPI mass spectra, indicating that the techniques are highly complementary in the types of molecules they ionize. Access to a broad range of molecules provided by combining APPI and electrospray has prompted a qualitative analysis. The goal is to assess the extent to which molecular MS data correspond with elemental (CHNOS) and structural characteristics determined by combustion elemental analyses and 13C nuclear magnetic resonance (NMR). Because the data obtained by these different methods are not directly comparable, we propose a novel data analysis procedure that facilitates their comparison. The bulk elemental composition calculated from electrospray MS data are in close agreement (±15%) with values determined by combustion elemental analysis. APPI and electrospray MS detect protein contributions in agreement with 13C NMR (6 wt %) but underestimate carbohydrates relative to 13C NMR. Nevertheless, MS results agree with NMR on the relative proportions of noncarbohydrate compounds in the organic matter: lignins \u3e lipids \u3e peptides. Finally, we use a molecular mixing model to simulate a 13C NMR spectrum from the MS datasets. The correspondence of the simulated and measured 13C NMR signals (74%) suggests that, collectively, the molecular species identified by APPI and electrospray MS comprise a large portion of the organic matter in Lake Drummond. These results add credibility to electrospray and APPI MS in limnology and oceanography applications, but further characterization of ion source behavior is fundamental to the accurate interpretation of MS data

Investigation into the role of carboxylic acid and phenolic hydroxyl groups in the plant biostimulant activity of a humic acid purified from an oxidized sub-bituminous coal

IntroductionHumic substances (HS) are increasingly being applied as crop plant biostimulants because they have been shown to increase plant productivity, especially under environmentally stressful conditions. There has been intense interest in elucidating the HS molecular structures responsible for eliciting the plant biostimulant response (PBR). The polar and weakly acidic carboxylic (COOH) and phenolic hydroxyl (ArOH) functional groups play major roles in the acid nature, pH dependent solubilities, conformation, and metal- and salt-binding capabilities of HS. Reports on the role played by these groups in the PBR of HS found growth parameters being both positively and negatively correlated with COOH and ArOH functionalities.Materials and methodsTo investigate the role of COOH and ArOH in HS biostimulant activity we used a humic acid (HA), purified from an oxidized sub bituminous coal to prepare HAs with COOH groups methylated (AHA), ArOH groups acetylated (OHA), and with both COOH and ArOH groups methylated (FHA). The original HA was designated (NHA). The four HAs were subjected to elemental, 13C-NMR, FTIR, and EPR analyses and their antioxidant properties were assessed using the trolox equivalents antioxidant capacity assay (TEAC). 13C-NMR and FTIR analysis revealed significant alkylation/acetylation. To determine the effects of alkylating/acetylating these functional groups on the HA elicited PBR, the HAs were evaluated in a plant bioassay on corn (Zea mays L.) seedling under nutrient and non-nutrient stressed conditions. Treatments consisted of the four HAs applied to the soil surface at a concentration of 80 mg C L−1, in 50 ml DI H2O with the control plants receiving 50ml DI H2O.ResultsThe HA-treated plants, at both fertilization rates, were almost always significantly larger than their respective control plants. However, the differences produced under nutrient stress were always much greater than those produced under nutrient sufficiency, supporting previous reports that HA can reduce the effects of stress on plant growth. In addition, for the most part, the HAs with the alkylated/acetylated groups produced plants equal to or larger than plants treated with NHA.ConclusionThese results suggests that COOH and ArOH groups play a limited or no role in the HA elicited PBR. Alternatively, the HA pro-oxidant to antioxidant ratio may play a role in the magnitude of the biostimulant response

Aromaticity and degree of aromatic condensation of char

The aromatic carbon structure is a defining property of chars and is often expressed with the help of two concepts: (i) aromaticity and (ii) degree of aromatic condensation. The varying extent of these two features is assumed to largely determine the relatively high persistence of charred material in the environment and is thus of interest for e.g. biochar characterization or carbon cycle studies. Consequently, a variety of methods has been used to assess the aromatic structure of chars, which has led to interesting insights but has complicated the comparison of data acquired with different methods. We therefore used a suite of seven methods (elemental analysis, MIR spectroscopy, NEXAFS spectroscopy, 13C NMR spectroscopy, BPCA analysis, lipid analysis and helium pycnometry) and compared 13 measurements from them using a diverse sample set of 38 laboratory chars. Our results demonstrate that most of the measurements could be categorized either into those which assess aromaticity or those which assess the degree of aromatic condensation. A variety of measurements, including relatively inexpensive and simple ones, reproducibly captured the two aromatic features in question, and data from different methods could therefore be compared. Moreover, general patterns between the two aromatic features and the pyrolysis conditions were revealed, supporting reconstruction of the highest heat treatment temperature (HTT) of char

Aromaticity and degree of aromatic condensation of char

The aromatic carbon structure is a defining property of chars and is often expressed with the help of two concepts: (i) aromaticity and (ii) degree of aromatic condensation. The varying extent of these two features is assumed to largely determine the relatively high persistence of charred material in the environment and is thus of interest for, e.g., biochar characterization or carbon cycle studies. Consequently, a variety of methods has been used to assess the aromatic structure of chars, which has led to interesting insights but has complicated the comparison of data acquired with different methods. We therefore used a suite of seven methods (elemental analysis, MIR spectroscopy, NEXAFS spectroscopy, ¹³C NMR spectroscopy, BPCA analysis, lipid analysis and helium pycnometry) and compared 13 measurements from them using a diverse sample set of 38 laboratory chars. Our results demonstrate that most of the measurements could be categorized either into those which assess aromaticity or those which assess the degree of aromatic condensation. A variety of measurements, including relatively inexpensive and simple ones, reproducibly captured the two aromatic features in question, and data from different methods could therefore be compared. Moreover, general patterns between the two aromatic features and the pyrolysis conditions were revealed, supporting reconstruction of the highest heat treatment temperature (HTT) of char.Keywords: Aromaticity, Stability, Aromatic condensation, Pyrolysis, Char, Biochar, Pyrogenic organic matter, Heat treatment temperatur

Biochar Volatile Matter and Feedstock Effects on Soil Nitrogen Mineralization and Soil Fungal Colonization

Biochar has important biogeochemical functions in soil—first as a means to sequester carbon, and second as a soil conditioner to potentially enhance soil quality and fertility. Volatile matter (VM) content is a property of biochar that describes its degree of thermal alteration, which can have a direct influence on carbon and nitrogen dynamics in soil. In this study, we characterized the VM in biochars derived from two locally sourced feedstocks (corncob and kiawe wood) and evaluated the relationship of VM content to nitrogen transformations and culturable fungal biomass. Using 13C nuclear magnetic resonance (NMR) spectroscopy, we found that the VM content of biochar primarily consisted of alkyl (5.1–10.1%), oxygen-substituted alkyl (2.2–6.7%), and phenolic carbon (9.4–11.6%). In a series of laboratory incubations, we demonstrated that corncob biochars with high VM (23%) content provide a source of bioavailable carbon that appeared to support enhanced viable, culturable fungi (up to 8 fold increase) and cause nitrogen immobilization in the short-term. Corncob biochar with bioavailable VM was nitrogen-limited, and the addition of nitrogen fertilizer resulted in a four-fold increase in total hydrolytic enzyme activity and the abundance of culturable fungal colonies. In contrast, kiawe biochar with an equivalent VM content differed substantially in its composition and effect on these same biological parameters. Therefore, the rapid measurement of VM content is too coarse to differentiate chemical composition and to predict the behavior of biochars across feedstocks and production methods

Plant species, not climate, controls aboveground biomass O2:CO2 exchange ratios in deciduous and coniferous ecosystems

The oxidative ratio (OR) is the O2:CO2 ratio associated with photosynthesis, respiration, and other ecosystem gas exchange processes and can be reported on the scale of an individual leaf, an ecosystem, up to the entire terrestrial biosphere. The OR of the terrestrial biosphere is used to partition anthropogenic CO2 between oceanic and terrestrial carbon sinks, and the ease of measurement of this property on smaller scales suggests its potential for other uses. However, controls on the natural variation of OR are not understood in either organic matter pools or fluxes, and this lack of basic information limits the use of the tracer. Here we assess the annual variability of the OR of photosynthesis over ~decade for two temperate forests, one coniferous and one deciduous, and show that the photosynthetic OR signature is strongly dominated by plant species. We determined the OR of this flux by measuring the OR of carbon pools that close on annual or shorter timescales (leaves and individual tree rings), via solid‐state 13C NMR spectroscopy and elemental analysis. Leaf litter OR is different between coniferous and deciduous forests, but tree bole OR is constant between species. There was no significant change in leaf litter OR with time, nor any correlations between leaf litter OR and temperature or precipitation. During this time growing season precipitation varied by 95% from the time period average, and growing season temperature by 22%, demonstrating that on the decadal scale photosynthetic OR is invariant over significant shifts in these climate parameters

KeiluweitMarcoCropSoilSciAromaticityDegreeAromatic.pdf

The aromatic carbon structure is a defining property of chars and is often expressed with the help of two concepts: (i) aromaticity and (ii) degree of aromatic condensation. The varying extent of these two features is assumed to largely determine the relatively high persistence of charred material in the environment and is thus of interest for, e.g., biochar characterization or carbon cycle studies. Consequently, a variety of methods has been used to assess the aromatic structure of chars, which has led to interesting insights but has complicated the comparison of data acquired with different methods. We therefore used a suite of seven methods (elemental analysis, MIR spectroscopy, NEXAFS spectroscopy, ¹³C NMR spectroscopy, BPCA analysis, lipid analysis and helium pycnometry) and compared 13 measurements from them using a diverse sample set of 38 laboratory chars. Our results demonstrate that most of the measurements could be categorized either into those which assess aromaticity or those which assess the degree of aromatic condensation. A variety of measurements, including relatively inexpensive and simple ones, reproducibly captured the two aromatic features in question, and data from different methods could therefore be compared. Moreover, general patterns between the two aromatic features and the pyrolysis conditions were revealed, supporting reconstruction of the highest heat treatment temperature (HTT) of char.Keywords: Aromaticity, Heat treatment temperature, Pyrogenic organic matter, Biochar, Aromatic condensation, Pyrolysis, Stability, CharKeywords: Aromaticity, Heat treatment temperature, Pyrogenic organic matter, Biochar, Aromatic condensation, Pyrolysis, Stability, Cha

KeiluweitMarcoCropSoilSciAromaticityDegreeAromatic_SupplementaryData.pdf

The aromatic carbon structure is a defining property of chars and is often expressed with the help of two concepts: (i) aromaticity and (ii) degree of aromatic condensation. The varying extent of these two features is assumed to largely determine the relatively high persistence of charred material in the environment and is thus of interest for, e.g., biochar characterization or carbon cycle studies. Consequently, a variety of methods has been used to assess the aromatic structure of chars, which has led to interesting insights but has complicated the comparison of data acquired with different methods. We therefore used a suite of seven methods (elemental analysis, MIR spectroscopy, NEXAFS spectroscopy, ¹³C NMR spectroscopy, BPCA analysis, lipid analysis and helium pycnometry) and compared 13 measurements from them using a diverse sample set of 38 laboratory chars. Our results demonstrate that most of the measurements could be categorized either into those which assess aromaticity or those which assess the degree of aromatic condensation. A variety of measurements, including relatively inexpensive and simple ones, reproducibly captured the two aromatic features in question, and data from different methods could therefore be compared. Moreover, general patterns between the two aromatic features and the pyrolysis conditions were revealed, supporting reconstruction of the highest heat treatment temperature (HTT) of char.Keywords: Stability, Char, Aromaticity, Pyrolysis, Heat treatment temperature, Aromatic condensation, Pyrogenic organic matter, BiocharKeywords: Stability, Char, Aromaticity, Pyrolysis, Heat treatment temperature, Aromatic condensation, Pyrogenic organic matter, Biocha