Unveiling carcinogenic pollutant levels in environmental water samples through facile fabrication of gold nanoparticles on sulfur-doped graphitic carbon nitride.

Extensive utilization of pesticides and herbicides to boost agricultural production increased the environmental health risks, which can be mitigate with the aid of highly sensitive detection systems. In this study, an electrochemical sensor for monitoring the carcinogenic pesticides in the environmental samples has been developed based on sulfur-doped graphitic-carbon nitride-gold nanoparticles (SCN-AuNPs) nanohybrid. Thermal polycondensation of melamine with thiourea followed by solvent exfoliation via ultrasonication leads to SCN formation and electroless deposition of AuNPs on SCN leads to SCN-AuNPs nanohybrid synthesis. The chemical composition, S-doping, and the morphology of the nanohybrid were confirmed by various microscopic and spectroscopic tools. The as-synthesized nanohybrid was fabricated with glassy carbon (GC) electrode for determining the carcinogenic hydrazine (HZ) and atrazine (ATZ) in field water samples. The present sensor exhibited superior electrocatalytic activity than GC/SCN and GC/AuNPs electrodes due to the synergism between SCN and AuNPs and the amperometric studies showed the good linear range of detection of 20 nM-0.5 mM and 500 nM-0.5 mM with the limit of detection of 0.22 and 69 nM (S/N = 3) and excellent sensitivity of 1173.5 and 13.96 µA mM-1 cm-2 towards HZ and ATZ, respectively. Ultimately, the present sensor is exploited in environmental samples for monitoring HZ and ATZ and the obtained results are validated with high-performance liquid chromatography (HPLC) technique. The excellent recovery percentage and close agreement with the results of HPLC analysis proved the practicability of the present sensor. In addition, the as-prepared materials were utilized for the photocatalytic degradation of ATZ and the SCN-AuNPs nanohybrid exhibited higher photocatalytic activity with the removal efficiency of 93.6% at 90 min. Finally, the degradation mechanism was investigated and discussed.

Estimating airborne trichloramine levels in indoor swimming pools using the well-mixed box model.

Exposure to airborne disinfection by-products, especially trichloramine (TCA), could cause various occupational health effects in indoor swimming pools. However, TCA concentration measurements involve specialized analysis conducted in specific laboratories, which can result in significant costs and time constraints. As an alternative, modeling techniques for estimating exposures are promising in addressing these challenges. This study aims to predict airborne TCA concentrations in indoor swimming pools using a mathematical model, the well-mixed box model, found in the IHMOD tool, freely available on the American Industrial Hygiene Association website. The model's predictions are compared with TCA concentrations measured during various bather load scenarios. The research involved conducting 2-hr successive workplace measurements over 16- to 18-hr periods in four indoor swimming pools in Quebec, Canada. TCA concentrations were estimated using the well-mixed box model, assuming a homogeneous mixing of air within the swimming pool environment. A novel approach was developed to estimate the TCA generation rate from swimming pool water, incorporating the number of swimmers in the model. Average measured concentrations of TCA were 0.24, 0.26, 0.14, and 0.34 mg/m3 for swimming pools 1, 2, 3, and 4, respectively. The ratio of these measured average concentrations to their corresponding predicted values ranged from 0.51 to 1.30, 0.67 to 1.04, 0.57 to 1.14, and 0.68 to 1.49 for the respective swimming pools. In a worst-case scenario simulating the swimming pool at full capacity (maximum bathers allowed), TCA concentrations were estimated as 0.23, 0.36, 0.14, and 0.37 mg/m3 for swimming pools 1, 2, 3, and 4. Recalculated concentrations by adjusting the number of swimmers so as not to exceed the recommended occupational limit concentration of 0.35 mg/m3 gives a maximum number of swimmers of 63 and 335 instead of currently 80 and 424 for swimming pools 2 and 4, respectively. Similarly, for swimming pools 1 and 3, the maximum number of swimmers could be 173 and 398 (instead of the current 160 and 225, respectively). These results demonstrated that the model could be used to estimate and anticipate airborne TCA levels in indoor swimming pools across various scenarios.

Root exudation of carbon and nitrogen compounds varies over the day-night cycle in pea: The role of diurnal changes in internal pools.

Rhizodeposition is the export of organic compounds from plant roots to the soil. Carbon allocation towards rhizodeposition has to be balanced with allocation for other physiological functions, which depend on both newly assimilated and stored nonstructural carbohydrate (NSC). To test whether the exudation of primary metabolites scales with plant NSC status, we studied diurnal dynamics of NSC and amino acid (AA) pools and fluxes within the plant and the rhizosphere. These diurnal dynamics were measured in the field and under hydroponic-controlled conditions. Further, C-limiting treatments offered further insight into the regulation of rhizodeposition. The exudation of primary metabolites fluctuated diurnally. The diurnal dynamics of soluble sugars (SS) and AA concentrations in tissues coincided with exudate pool fluctuations in the rhizosphere. SS and AA pools in the rhizosphere increased with NSC and AA pools in the roots. C starvation treatments offset the balance of exudates: AA exudate content in the rhizosphere significantly decreased while SS exudate content remained stable. Our results suggest that rhizodeposition is to some extent controlled by plant C:N status. We propose that SS exudation is less controlled than AA exudation because N assimilation depends on controlled C supply while SS exudation relies to a greater extent on passive diffusion mechanisms.

Aqueous-Phase Reactions of Anthropogenic Emissions Lead to the High Chemodiversity of Atmospheric Nitrogen-Containing Compounds during the Haze Event.

Nitrogen-containing organic compounds (NOCs), a type of important reactive-nitrogen species, are abundant in organic aerosols in haze events observed in Northern China. However, due to the complex nature of NOCs, the sources, formation, and influencing factors are still ambiguous. Here, the molecular composition of organic matters (OMs) in hourly PM2.5 samples collected during a haze event in Northern China was characterized using Fourier transform ion cyclotron resonance mass spectrometry (FT-ICR MS). We found that CHON compounds (formulas containing C, H, O, and N atoms) dominated the OM fractions during the haze and showed high chemodiversity and transformability. Relying on the newly developed revised-workflow and oxidation-hydrolyzation knowledge for CHON compounds, 64% of the major aromatic CHON compounds (>80%) could be derived from the oxidization or hydrolyzation processes. Results from FT-ICR MS data analysis further showed that the aerosol liquid water (ALW)-involved aqueous-phase reactions are important for the molecular distribution of aromatic-CHON compounds besides the coal combustion, and the ALW-involved aromatic-CHON compound formation during daytime and nighttime was different. Our results improve the understanding of molecular composition, sources, and potential formation of CHON compounds, which can help to advance the understanding for the formation, evolution, and control of haze.

Molecular Characterization of Nitrogen-Containing Compounds in Humic-like Substances Emitted from Biomass Burning and Coal Combustion.

N-containing organic compounds (NOCs) in humic-like substances (HULIS) emitted from biomass burning (BB) and coal combustion (CC) were characterized by ultrahigh-resolution mass spectrometry in the positive electrospray ionization mode. Our results indicate that NOCs include CHON+ and CHN+ groups, which are detected as a substantial fraction in both BB- and CC-derived HULIS, and suggest that not only BB but also CC is the potential important source of NOCs in the atmosphere. The CHON+ compounds mainly consist of reduced nitrogen compounds with other oxygenated functional groups, and straw- and coal-smoke HULIS exhibit a lower degree of oxidation than pine-smoke HULIS. In addition, the NOCs with higher N atoms (N2 and/or N3) generally bear higher modified aromaticity index (AImod) values and are mainly contained in BB HULIS, especially in straw-smoke HULIS, whereas the NOCs with a lower N atom (N1) always have relatively lower AImod values and are the dominant NOCs in CC HULIS. These findings imply that the primary emission from CC may be a significant source of N1 compounds, whereas high N number (e.g., N2-3) compounds could be associated with burning of biomass materials. Further study is warranted to distinguish the NOCs from more sources.

Metabolomic profiling of Dezhou donkey seminal plasma related to freezability.

Donkeys are indispensable livestock in China because they have transport function and medicinal value. With the popularization of artificial insemination on donkeys, semen cryopreservation technology has gradually become a research hotspot. Seminal plasma is a necessary medium for transporting sperm and provides energy and nutrition for sperm. Seminal plasma metabolites play an important role in the process of sperm freezing, and also have an important impact on sperm motility and fertilization rate after freezing and thawing. In this study, liquid chromatography-tandem mass spectrometry (LC-MS/MS) analysis was used to compare the metabolic characteristics of seminal plasma of high freezability (HF) and low freezability (LF) male donkeys. We identified 672 metabolites from donkey seminal plasma, of which 33 metabolites were significantly different between the two groups. Metabolites were identified and categorized according to their major chemical classes, including homogeneous non-metal compounds, nucleosides, nucleotides, and analogues, organosulphur compounds, phenylpropanoids and polyketide, organoheterocyclic compounds, organic oxygen compounds, benzenoids, organic acids and derivatives, lipids and lipid-like molecules, organooxygen compounds, alkaloids and derivatives, organic nitrogen compounds. The results showed that the contents of phosphatidylcholine, piceatannol and enkephalin in donkey semen of HF group were significantly higher than those of LF group (p < .05), while the contents of taurocholic and lysophosphatidic acid were significantly lower than those of LF group (p < .05). The different metabolites were mainly related to sperm biological pathway response and oxidative stress. These metabolites may be considered as candidate biomarkers for different fertility in jacks.

Nitrogenous Compounds from the Antarctic Fungus Pseudogymnoascus sp. HSX2#-11.

The species Pseudogymnoascus is known as a psychrophilic pathogenic fungus which is ubiquitously distributed in Antarctica. While the studies of its secondary metabolites are infrequent. Systematic research of the metabolites of the Antarctic fungus Pseudogymnoascus sp. HSX2#-11 led to the isolation of one new pyridine derivative, 4-(2-methoxycarbonyl-ethyl)-pyridine-2-carboxylic acid methyl ester (1), together with one pyrimidine, thymine (2), and eight diketopiperazines, cyclo-(dehydroAla-l-Val) (3), cyclo-(dehydroAla-l-Ile) (4), cyclo-(dehydroAla-l-Leu) (5), cyclo-(dehydroAla-l-Phe) (6), cyclo-(l-Val-l-Phe) (7), cyclo-(l-Leu-l-Phe) (8), cyclo-(l-Trp-l-Ile) (9) and cyclo-(l-Trp-l-Phe) (10). The structures of these compounds were established by extensive spectroscopic investigation, as well as by detailed comparison with literature data. This is the first report to discover pyridine, pyrimidine and diketopiperazines from the genus of Pseudogymnoascus.

Occupational exposure to trichloramine and trihalomethanes: adverse health effects among personnel in habilitation and rehabilitation swimming pools.

Personnel in swimming pool facilities typically experience ocular, nasal, and respiratory symptoms due to water chlorination and consequent exposure to disinfection by-products in the air. The aim of the study was to investigate exposure to trichloramine and trihalomethanes (chloroform, bromodichloromethane, dibromochloromethane, and bromoform) from the perspective of adverse health effects on the personnel at Swedish habilitation and rehabilitation swimming pools. The study included 10 habilitation and rehabilitation swimming pool facilities in nine Swedish cities. The study population comprised 24 exposed swimming pool workers and 50 unexposed office workers. Personal and stationary measurements of trichloramine and trihalomethanes in air were performed at all the facilities. Questionnaires were distributed to exposed workers and referents. Spirometry, fraction of exhaled nitric oxide (FENO), and peak expiratory flow (PEF) were measured. Personal and stationary measurements yielded trichloramine levels of 1-76 µg/m3 (average: 19 µg/m3) and 1-140 µg/m3 (average: 23 µg/m3), respectively. A slightly higher, but not significant, prevalence of reported eye- and throat-related symptoms occurred among the exposed workers than among the referents. A significantly increased risk of at least one ocular symptom was attributed to trichloramine exposure above the median (20 µg/m3). Lung function (FVC and FEV1) was in the normal range according to the Swedish reference materials, and no significant change in lung function before and after shift could be established between the groups. Average FENO values were in the normal range in both groups, but the difference in the values between the exposed workers and referents showed a significant increase after shift. Hourly registered PEF values during the day of the investigation did not show any unusual individual variability. In conclusion, the increased risk of developing at least one ocular symptom at personal trichloramine concentrations over 20 µg/m3 combined with an increase in the difference in FENO during the work shift of the exposed workers should not be neglected as an increased risk of respiratory inflammation in the habilitation and rehabilitation swimming pool environment.

Nitroaromatic detection and infrared communication from wild-type plants using plant nanobionics.

Plant nanobionics aims to embed non-native functions to plants by interfacing them with specifically designed nanoparticles. Here, we demonstrate that living spinach plants (Spinacia oleracea) can be engineered to serve as self-powered pre-concentrators and autosamplers of analytes in ambient groundwater and as infrared communication platforms that can send information to a smartphone. The plants employ a pair of near-infrared fluorescent nanosensors-single-walled carbon nanotubes (SWCNTs) conjugated to the peptide Bombolitin II to recognize nitroaromatics via infrared fluorescent emission, and polyvinyl-alcohol functionalized SWCNTs that act as an invariant reference signal-embedded within the plant leaf mesophyll. As contaminant nitroaromatics are transported up the roots and stem into leaf tissues, they accumulate in the mesophyll, resulting in relative changes in emission intensity. The real-time monitoring of embedded SWCNT sensors also allows residence times in the roots, stems and leaves to be estimated, calculated to be 8.3 min (combined residence times of root and stem) and 1.9 min mm-1 leaf, respectively. These results demonstrate the ability of living, wild-type plants to function as chemical monitors of groundwater and communication devices to external electronics at standoff distances.

Evaluation of needle trap micro-extraction and solid-phase micro-extraction: Obtaining comprehensive information on volatile emissions from in vitro cultures.

Volatile organic compounds (VOCs) emitted from in vitro cultures may reveal information on species and metabolism. Owing to low nmol L-1 concentration ranges, pre-concentration techniques are required for gas chromatography-mass spectrometry (GC-MS) based analyses. This study was intended to compare the efficiency of established micro-extraction techniques - solid-phase micro-extraction (SPME) and needle-trap micro-extraction (NTME) - for the analysis of complex VOC patterns. For SPME, a 75 µm Carboxen®/polydimethylsiloxane fiber was used. The NTME needle was packed with divinylbenzene, Carbopack X and Carboxen 1000. The headspace was sampled bi-directionally. Seventy-two VOCs were calibrated by reference standard mixtures in the range of 0.041-62.24 nmol L-1 by means of GC-MS. Both pre-concentration methods were applied to profile VOCs from cultures of Mycobacterium avium ssp. paratuberculosis. Limits of detection ranged from 0.004 to 3.93 nmol L-1 (median = 0.030 nmol L-1 ) for NTME and from 0.001 to 5.684 nmol L-1 (median = 0.043 nmol L-1 ) for SPME. NTME showed advantages in assessing polar compounds such as alcohols. SPME showed advantages in reproducibility but disadvantages in sensitivity for N-containing compounds. Micro-extraction techniques such as SPME and NTME are well suited for trace VOC profiling over cultures if the limitations of each technique is taken into account.

The investigation of the bio-oil produced by hydrothermal liquefaction of Spirulina platensis using ultrahigh resolution Fourier transform ion cyclotron resonance mass spectrometry.

We report the investigation of the hydrothermal liquefaction products of the Spirulina platensis microalgae by using the Fourier transform ion cyclotron resonance mass spectrometry. The hydrothermal liquefaction produced two fractions: one with boiling temperature below 300℃ and the dense residue that remained in the reactor. It was observed that N2 and N classes of compounds that dominate in the positive ESI Fourier transform ion cyclotron resonance spectra for both fractions, and that the light fraction is considerably more saturated then the heavy one. The performed hydrogen/deuterium exchange reaction indicated the presence of the onium compounds in the bio-oil.

Formation and control of nitrogenous DBPs from Western Australian source waters: Investigating the impacts of high nitrogen and bromide concentrations.

We studied the formation of four nitrogenous DBPs (N-DBPs) classes (haloacetonitriles, halonitromethanes, haloacetamides, and N-nitrosamines), as well as trihalomethanes and total organic halogen (TOX), after chlorination or chloramination of source waters. We also evaluated the relative and additive toxicity of N-DBPs and water treatment options for minimisation of N-DBPs. The formation of halonitromethanes, haloacetamides, and N-nitrosamines was higher after chloramination and positively correlated with dissolved organic nitrogen or total nitrogen. N-DBPs were major contributors to the toxicity of both chlorinated and chloraminated waters. The strong correlation between bromide concentration and the overall calculated DBP additive toxicity for both chlorinated and chloraminated source waters demonstrated that formation of brominated haloacetonitriles was the main contributor to toxicity. Ozone-biological activated carbon treatment was not effective in removing N-DBP precursors. The occurrence and formation of N-DBPs should be investigated on a case-by-case basis, especially where advanced water treatment processes are being considered to minimise their formation in drinking waters, and where chloramination is used for final disinfection.

Determination of emerging nitrogenous economic adulterants in milk proteins by high-performance liquid chromatography/compact mass spectrometry.

RATIONALE: Milk-derived ingredients are widely used around the world in the manufacturing of nutritional products. They are prone to economically motivated adulteration with nitrogenous compounds such as melamine and its analogs in order to increase the nitrogen content of these ingredients. The need to rapidly screen milk-derived ingredients to detect adulteration is of paramount public health concern. A liquid chromatography/mass spectrometry (LC/MS)-based method using a single quadrupole mass spectrometer has been developed for the rapid frontline analysis of six nitrogenous protein adulterants, i.e. melamine, ammeline, ammelide, amidinourea, cyromazine and cyanuric acid, in three key milk-derived ingredients, i.e. whole milk powder, nonfat milk powder and whey protein concentrate. METHODS: The sample preparation scheme involves both 'dilute and shoot' as well as solid-phase extraction (SPE)-based methods. The 'dilute and shoot' scheme uses a tenfold dilution of sample with water followed by protein precipitation using 2% formic acid in acetonitrile. The SPE scheme involves tenfold dilution of sample with water, followed by protein precipitation using acetonitrile, and further cleanup through Strata Melamine SPE cartridges. Sample extracts were analyzed by hydrophilic interaction chromatography/single quadrupole mass spectrometry (HILIC/MS) in both positive and negative electrospray ionization mode. Accurate quantitation was achieved using stable isotope labeled internal standards. RESULTS: A multi-day method validation study was conducted using three different milk-derived ingredients. Average accuracies, relative standard deviations (RSD) and method detection limits (MDL) for all analytes in whole milk powder were 65-118%, 7-11% and 0.9-30 mg/kg, using the 'dilute and shoot' extraction procedure. The SPE procedure results were 102-111%, 5-13%, and 0.4-2.5 mg/kg, respectively, for melamine, ammeline, ammelide and cyromazine only. CONCLUSIONS: A rugged and simple to use analytical method to screen for the presence of nitrogenous economic adulterants in milk-derived ingredients has been developed for routine frontline use. Copyright © 2016 John Wiley & Sons, Ltd.

Biodegradability and Molecular Composition of Dissolved Organic Nitrogen in Urban Stormwater Runoff and Outflow Water from a Stormwater Retention Pond.

Dissolved organic nitrogen (DON) can be a significant part of the reactive N in aquatic ecosystems and can accelerate eutrophication and harmful algal blooms. A bioassay method was coupled with Fourier transform ion cyclotron resonance mass spectrometry (FT-ICR-MS) to determine the biodegradability and molecular composition of DON in the urban stormwater runoff and outflow water from an urban stormwater retention pond. The biodegradability of DON increased from 10% in the stormwater runoff to 40% in the pond outflow water and DON was less aromatic and had lower overall molecular weight in the pond outflow water than in the stormwater runoff. More than 1227 N-bearing organic formulas were identified with FT-ICR-MS in the stormwater runoff and pond outflow water, which were only 13% different in runoff and outflow water. These molecular formulas represented a wide range of biomolecules such as lipids, proteins, amino sugars, lignins, and tannins in DON from runoff and pond outflow water. This work implies that the urban infrastructure (i.e., stormwater retention ponds) has the potential to influence biogeochemical processes in downstream water bodies because retention ponds are often a junction between the natural and the built environment.

Bacterial Diversity in Bohai Bay Solar Saltworks, China.

The microbiota in solar salterns plays an important role in salt production quantitatively and qualitatively. Bohai Bay coast is the major sea salt producing area in China. However, few ecological characterization studies of the Bohai Bay salt ponds, particularly of their microbial diversity, have been conducted. This study investigated the structure and diversity of the bacterial community in Hangu saltworks in response to environmental factors. The brine water was sampled from five selected saltponds within a salinity range of 5.0-19.3% in May, July, and October, 2012. Phylogenetic analysis based on the denaturing gradient gel electrophoresis (DGGE) patterns of the PCR-amplified 16S rRNA gene fragment showed that, rather than pond salinity, especially the month of sampling influenced the structure of the bacterial community in the saltponds, which may be related to the water temperature or other factors fluctuating over the months. Moreover, canonical correspondence analysis of biological and physico-chemical parameters indicated that especially other environmental factors such as nitrogenous and phosphorous nutrient contents and pH structured the microbial community. The relatively high range-weighted richness index and Shannon-Wiener index (H') observed in this study reflect the high level of richness and biodiversity present, though there were substantial fluctuations over the months and salinities of sampling. The fragment of 16S rRNA gene sequence recovered from DGGE bands indicated that the bacterial assemblage in Hangu Saltworks was dominated by members of γ-Proteobacteria (34% of total sequences obtained), followed by Firmicutes (14%) and Bacteroidetes (9%).

Raman spectroscopy as an effective screening method for detecting adulteration of milk with small nitrogen-rich molecules and sucrose.

Adulteration of milk for commercial gain is acknowledged as a serious issue facing the dairy industry. Several analytical techniques can be used to detect adulteration but they often require time-consuming sample preparation, expensive laboratory equipment, and highly skilled personnel. Here we show that Raman spectroscopy provides a simple, selective, and sensitive method for screening milk, specifically for small nitrogen-rich compounds, such as melamine, urea, ammonium sulfate, dicyandiamide, and for sucrose. Univariate and multivariate statistical methods were used to determine limits of detection and quantification from Raman spectra of milk spiked with 50 to 1,000 mg/L of the N-rich compounds and 0.25 to 4% sucrose. Partial least squares (PLS) calibration provided limit of detection minimum thresholds <200mg/L (0.02%) for the 4 N-rich compounds and <0.8% for sucrose, without the need for surface-enhanced Raman spectroscopy. The results show high reproducibility (7% residual standard deviation) and 100% efficiency for screening of milk for these adulterants.

Principles and limitations of stable isotopes in differentiating organic and conventional foodstuffs: 1. Plant products.

Among the lighter elements having two or more stable isotopes (H, C, N, O, S), δ(15)N appears to be the most promising isotopic marker to differentiate plant products from conventional and organic farms. Organic plant products vary within a range of δ(15)N values of +0.3 to +14.6%, while conventional plant products range from negative to positive values, i.e. -4.0 to +8.7%. The main factors affecting δ(15)N signatures of plants are N fertilizers, biological N2 fixation, plant organs and plant age. Correlations between mode of production and δ(13)C (except greenhouse tomatoes warmed with natural gas) or δ(34)S signatures have not been established, and δ(2)H and δ(18)O are unsuitable markers due to the overriding effect of climate on the isotopic composition of plant-available water. Because there is potential overlap between the δ(15)N signatures of organic and conventionally produced plant products, δ(15)N has seldom been used successfully as the sole criterion for differentiation, but when combined with complementary analytical techniques and appropriate statistical tools, the probability of a correct identification increases. The use of organic fertilizers by conventional farmers or the marketing of organic produce as conventional due to market pressures are additional factors confounding correct identification. The robustness of using δ(15)N to differentiate mode of production will depend on the establishment of databases that have been verified for individual plant products.

Isotopic disproportionation during hydrogen isotopic analysis of nitrogen-bearing organic compounds.

RATIONALE: High-precision hydrogen isotope ratio analysis of nitrogen-bearing organic materials using high-temperature conversion (HTC) techniques has proven troublesome in the past. Formation of reaction products other than molecular hydrogen (H(2)) has been suspected as a possible cause of incomplete H(2) yield and hydrogen isotopic fractionation. METHODS: The classical HTC reactor setup and a modified version including elemental chromium, both operated at temperatures in excess of 1400 °C, have been compared using a selection of nitrogen-bearing organic compounds, including caffeine. A focus of the experiments was to avoid or suppress hydrogen cyanide (HCN) formation and to reach quantitative H(2) yields. The technique also was optimized to provide acceptable sample throughput. RESULTS: The classical HTC reaction of a number of selected compounds exhibited H(2) yields from 60 to 90 %. Yields close to 100 % were measured for the experiments with the chromium-enhanced reactor. The δ(2)H values also were substantially different between the two types of experiments. For the majority of the compounds studied, a highly significant relationship was observed between the amount of missing H(2) and the number of nitrogen atoms in the molecules, suggesting the pyrolytic formation of HCN as a byproduct. A similar linear relationship was found between the amount of missing H(2) and the observed hydrogen isotopic result, reflecting isotopic fractionation. CONCLUSIONS: The classical HTC technique to produce H(2) from organic materials using high temperatures in the presence of glassy carbon is not suitable for nitrogen-bearing compounds. Adding chromium to the reaction zone improves the yield to 100 % in most cases. The initial formation of HCN is accompanied by a strong hydrogen isotope effect, with the observed hydrogen isotope results on H(2) being substantially shifted to more negative δ(2)H values. The reaction can be understood as an initial disproportionation leading to H(2) and HCN with the HCN-hydrogen systematically enriched in (2)H by more than 50 ‰. In the reaction of HCN with chromium, H(2) and chromium-containing solid residues are formed quantitatively.

Exploring the complexity of oil sands process-affected water by high efficiency supercritical fluid chromatography/orbitrap mass spectrometry.

RATIONALE: Approximately 1 billion m(3) of oil sands process-affected water (OSPW) is currently stored in tailings ponds in Northern Alberta, Canada. The dissolved organic compounds in OSPW have been termed a supercomplex mixture of bitumen-derived substances and continuing efforts to understand its underlying chemical composition are important for evaluating its environmental hazards. METHODS: Packed column supercritical fluid chromatography (SFC) was applied to OSPW analysis for the first time. By combining four columns in series (each 25 cm × 4.6 mm I.D., 5.0 µm bare silica) approximately 80,000 plates were achieved on a 1 m column. Using a simple fixed restrictor, the SFC eluent was coupled directly to ultrahigh-resolution orbitrap mass spectrometry (SFC/Orbitrap-MS). RESULTS: SFC/Orbitrap-MS, with positive and negative atmospheric pressure chemical ionization (APCI +/-), revealed the partial or full chromatographic separation of isomers for a wide array of chemical species, including naphthenic acids (Cn H2n + Z O2 ) and unknown sulfur- and nitrogen-containing molecules. For smaller compounds (e.g. naphthenic acids where n ≤10), or for larger structurally constrained compounds (e.g. C16 naphthenic acid with 9 double-bond equivalents), apparent baseline resolution of many isomers was possible. Isomer-specific MS/MS experiments furthermore allowed characterization of functional groups in novel species. For example, in APCI+ mode, up to 16 isomers of C6 H11 ON were revealed to have amide and amino functionalities. CONCLUSIONS: This combination of high efficiency chromatography and ultra-high mass resolution detection resulted in a powerful method with capabilities for characterizing or 'fingerprinting' unknown species with little interference. The method has great promise for environmental monitoring and forensics in the oil sands region, as well as for further studies on the composition of dissolved organic compounds in OSPW.

Magnetic graphene composites as both an adsorbent for sample enrichment and a MALDI-TOF MS matrix for the detection of nitropolycyclic aromatic hydrocarbons in PM2.5.

A simple and rapid method that uses synthesized magnetic graphene composites as both an adsorbent for enrichment and as a matrix in MALDI-TOF MS analysis was developed for the detection of nitropolycyclic hydrocarbons (nitro-PAHs) in PM2.5 samples. Three nitro-PAHs were detected down to sub pg µL(-1) levels based on calculations from an instrumental signal-to-noise better than 3, which shows the feasibility of using the new materials in MALDI-TOF MS as a potential powerful analytical approach for the analysis of nitro-PAHs in PM2.5 samples.