The paper presents a technique for measuring the concentration of 13CH4 in natural methane using Raman spectroscopy. The peak positions and the relative scattering cross-sections of the Q-branches for the most intense vibrational bands of 13CH4 are determined. Features of the 13CH4/12CH4 ratio measurement methods using Q-branches of the ν1 and ν3 bands were considered. It was shown that the 13CH4/12CH4 ratio can be determined by simulation of the ν3 bands of these molecules without the use of experimental spectra. In our experiments the measurement error of δ13C value was 10 ‰ using the 100-s exposure spectrum at a gas pressure close to 1 atm recorded on the developed Raman spectrometer. In addition, the Raman spectra of alkanes (up to n-hexane) in the range of 2850-3050 cm-1 at a resolution of 0.4 cm-1 are presented, and their integrated intensities in the ranges of the characteristic bands of 13CH4 and 12CH4 are provided. The data obtained make it possible to expand the capabilities of Raman gas analyzers in the mud gas logging industry.

The increasing environmental abundance of reactive N (\'Nr\') entails many adverse effects for society such as soil degradation and eutrophication. In addressing the global surplus of N, there is a pressing need to quantify local sources and dynamics of Nr. Although quantified as an important anthropogenic source of Nr, the spatiotemporal patterns of ammonia (\'NH3\') emitted by dairy farming and its resulting pressure on local surface waters lacks quantification. Quantification could optimize farm management with minimized losses of valuable nitrogen and protection of freshwater ecology. This study aimed to unravel spatiotemporal dynamics of ammonia nitrogen emitted by a dairy farm in the atmospheric and aquatic geo-ecosphere. Atmospheric NH3 and aqueous ammonium (\'NH4+\') were determined over time, together with meteorological variables. Aquatic biomonitors (periphyton and phytoplankton) were employed to monitor the spatial impacts of cattle-stable emitted NH3. Atmospheric NH3 on the farm was significantly regulated by wind, sharply declining over increasing distances from the stable (average decrease in the dominant wind direction from 55.5 μg/m3 at 20 m to 5.8 μg/m3 at 500 m, in the other wind directions values decreased from 38.3 μg/m3 to 6.0 μg/m3). This was also reflected in local surface water concentrations of NH4+, with average concentrations decreasing from 37.0 mg [NH4+-N]/L at 65 m to 4.8 mg [NH4+-N]/L in the dominant wind direction, and from 1.2 to 0.7 in other directions. Periphyton biomass, total N (\"TN\") and δ15N all significantly reflected spatiotemporal dynamics of atmospheric NH3 and aqueous NH4+, as did phytoplankton TN. The cattle stable significantly influenced local water quality through atmospheric spreading of NH3, and both aquatic biomonitors were influenced by and reflected dairy farm emitted NH3 with a sharp dilution over distance. This study strongly underlines the importance of atmospheric transport of dairy farm emitted NH3 and its effects on local water quality.

Biological nitrogen fixation (BNF) provides a globally important input of nitrogen (N); its quantification is critical but technically challenging. Leaf reflectance spectroscopy offers a more rapid approach than traditional techniques to measure plant N concentration ([N]) and isotopes (δ15N). Here we present a novel method for rapidly and inexpensively quantifying BNF using optical spectroscopy. We measured plant [N], δ15N, and the amount of N derived from atmospheric fixation (Ndfa) following the standard traditional methodology using isotope ratio mass spectrometry (IRMS) from tissues grown under controlled conditions and taken from field experiments. Using the same tissues, we predicted the same three parameters using optical spectroscopy. By comparing the optical spectroscopy-derived results with traditional measurements (i.e. IRMS), the amount of Ndfa predicted by optical spectroscopy was highly comparable to IRMS-based quantification, with R2 being 0.90 (slope=0.90) and 0.94 (slope=1.02) (root mean square error for predicting legume δ15N was 0.38 and 0.43) for legumes grown in glasshouse and field, respectively. This novel application of optical spectroscopy facilitates BNF studies because it is rapid, scalable, low cost, and complementary to existing technologies. Moreover, the proposed method successfully captures the dynamic response of BNF to climate changes such as warming and drought.

The aim of this paper was to characterise the isotopic composition of oral squamous cell carcinoma (OSCC) specimens of different areas of the oral cavity. Secondly, we assessed whether there was a correlation between clinical stages of OSCC and isotopic abundance. The IRMS procedure was performed on 124 samples derived from 31 patients with OSCC of 15 N and 13 C to assess the isotopic composition. From each individual, four samples from the tumour, two from the margins, and two samples of healthy oral mucous membranes were derived. The two samples from the tumour and two samples from the margin were additionally subjected to histopathological assessment. Then, statistical analysis was conducted. Tumour infiltration tissues of the lower lip were characterised by higher mean δ13C values compared to samples derived from cancers of the other oral cavity regions (-23.82 ± 1.21 vs. -22.67 ± 1.35); (p = 0.04). The mean percentage of nitrogen content in tumour tissues was statistically higher in patients with the most advanced cancers (11.89 ± 0.03%) versus the group of patients with II and III stage cancers (11.12 ± 0.02%); (p = 0.04). In patients at stage IV, the mean δ13C value in the cancer samples equalled -22.69 ± 1.42 and was lower than that in patients at less severe clinical stages (p = 0.04). Lower lip cancer tissues differed in the isotopic abundance of carbon in comparison with tissues derived from the group of combined samples from other locations. Values of δ13C observed in specimens derived from lower lip cancers were similar to those observed in healthy oral mucous membranes. Cancer tissues obtained from patients in the last stage of OSCC had a different isotopic composition in comparison with those obtained from earlier stages. To confirm these observations, further research on larger groups of patients is needed.

Mercury (Hg) emissions from forest fires, especially tropical forests such as the Amazonian forest, were shown to contribute significantly to the atmospheric mercury budget, but new methods are still necessary to improve the traceability and to reduce the great uncertainties related to this emission source. Recent studies have shown that the combustion process can result in Hg stable isotope fractionation that allows tracking coal combustion Hg emissions, as influenced by different factors such as combustion temperature. The main goal of the present study was, therefore, to investigate for the first time the potential of Hg stable isotopes to trace forest fire Hg emissions and pathways. More specifically, small-scale and a large scale prescribed forest fire experiments were conducted in the Brazilian Amazonian forest to study the impact of fire severity on Hg isotopic composition of litter, soil, and ash samples and associated Hg isotope fractionation pathways. In the small-scale experiment, no difference was found in the mercury isotopic composition of the samples collected before and after burning. In contrast, the larger-scale experiment resulted in significant mass dependent fractionation (MDF δ202Hg) in soils and ash suggesting that higher combustion temperature influence Hg isotopic fractionation with the emission of lighter Hg isotopes to the atmosphere and enrichment with heavier Hg in ashes. As for coal combustion, mass independent fractionation was not observed. To our knowledge, these results are the first to highlight the potential of forest fires to cause Hg isotopic fractionation, depending on the fire severity. The results also allowed to establish an isotopic fingerprint for tropical forest fire Hg emissions that corresponds to a mixture of litter and soil Hg isotopic composition (resulting atmospheric δ202Hg, Δ200Hg and Δ199Hg were -1.79 ± 0.24‰, -0.05 ± 0.04‰ and -0.45 ± 0.12‰, respectively).

Stable isotope ratios and trace elements are well-established tools that act as signatures of the product\'s environmental conditions and agricultural processes; but they involve time, money, and environmentally destructive chemicals. In this study, we tested for the first time the potential of near-infrared reflectance spectroscopy (NIR) to estimate/predict isotope and elemental compositions for the origin verification of coffee. Green coffee samples from two continents, 4 countries, and 10 regions were analysed for five isotope ratios (δ13C, δ15N, δ18O, δ2H, and δ34S) and 41 trace elements. NIR (1100-2400 nm) calibrations were developed using pre-processing with extended multiplicative scatter correction (EMSC) and mean centering and partial-least squares regression (PLS-R). Five elements (Mn, Mo, Rb, B, La) and three isotope ratios (δ13C, δ18O, δ2H) were moderately to well predicted by NIR (R2: 0.69 to 0.93). NIR indirectly measured these parameters by association with organic compounds in coffee. These parameters were related to altitude, temperature and rainfall differences across countries and regions and were previously found to be origin discriminators for coffee.

Water pollution is a worldwide concern that has growing severe in developed and developing nations. Increasing groundwater pollution threatening both the physical and environmental health of billions of people as well as economic progress. Consequently, hydrogeochemistry, water quality and potential health risk assessment is crucial for water resource management. The study area comprises Jamuna Floodplain (Holocene deposit) area in the west and the Madhupur tract (Pleistocene deposit) area in the eastern part. Total 39 groundwater samples were collected from the study area and were analyzed for physicochemical parameters, hydrogeochemical, trace metals, and isotopic composition. The water types are mainly Ca-HCO3- to Na-HCO3- types. The isotopic compositions (δ18O‰ and δ2H‰) analysis traces the recent recharge in Floodplain area from rainwater and no recent recharge in Madhupur tract. The concentration of NO3-, As, Cr, Ni, Pb, Fe, and Mn in shallow and intermediate aquifer at the Floodplain area exceed the WHO-2011 permissible limit and is lower at deep Holocene and Madhupur tract aquifer. The integrated weighted water quality index (IWQI) exposed groundwater from shallow and intermediate aquifer are unsuitable for drinking and deep Holocene aquifer and Madhupur tract are suitable for drinking purposes. PCA analysis confirmed that anthropogenic activity is dominant in shallow and intermediate aquifers. The non-carcinogenic and carcinogenic risk for adults and children is due to oral and dermal exposure. The non-carcinogenic risk evaluation revealed that the mean hazard index (HI) values range from 0.009742 to 16.37 for adults and 0.0124-20.83 for children, respectively, and most groundwater samples from shallow and intermediate aquifers exceed the permissible limit (HI>1). The carcinogenic risk ranges from 2.71 × 10-6-0.014 for adults and 3.44 × 10-6-0.017 for children via oral consumption and 7.09 × 10-11-1.18 × 10-6 for adults and 1.25 × 10-10-2.09 × 10-6 for children via dermal exposure. Spatial distribution shows the presence of trace metal and associated health risk is high in shallow and intermediate aquifer (Holocene) than in the deep (Holocene) Madhupur tract (Pleistocene). The study implies that effective water management will ensure safe drinking water for the future generation of people.

It is generally accepted that eutrophic lakes significantly contribute to nitrous oxide (N2O) emissions. However, how these emissions are affected by the formation, disappearance, and mechanisms of algal blooms in these lakes has not been systematically investigated. This study examined and determined the relative contribution of spatiotemporal N2O production pathways in hypereutrophic Lake Taihu. Synchronously, the multi-impacts of algae on N2O production and release potential were measured in the field and in microcosms using isotope ratios of oxygen (δ18O) and bulk nitrogen (δ15N) to N2O and to intramolecular 15N site preference (SP). Results showed that N2O production in Lake Taihu was derived from microbial effects (nitrification and incomplete denitrification) and water air exchanges. N2O production was also affected by the N2O reduction process. The mean dissolved N2O concentrations in the water column during the pre-outbreak, outbreak, and decay stages of algae accumulation were almost the same (0.05 μmol·L-1), which was 2-10 times higher than in lake areas algae was not accumulating. However, except for the central lake area, all surveyed areas (with and without accumulated algae) displayed strong release potential and acted as the emission source because of dissolved N2O supersaturation in the water column. The mean N2O release fluxes during the pre-outbreak, outbreak, and decay stages of algae accumulation areas were 17.95, 26.36, and 79.32 μmol·m-2·d-1, respectively, which were 2.0-7.5 times higher than the values in the non-algae accumulation areas. In addition, the decay and decomposition of algae released large amounts of nutrients and changed the physiochemical properties of the water column. Additionally, the increased algae biomass promoted N2O release and improved the proportion of N2O produced via denitrification process to being 9.8-20.4% microbial-derived N2O. This proportion became higher when the N2O consumption during denitrification was considered as evidenced by isotopic data. However, when the algae biomass was excessive in hypereutrophic state, the algae decomposition also consumed a large amount of oxygen, thus limiting the N2O production due to complete denitrification as well as due to the limited substrate supply of nitrate by nitrification in hypoxic or anoxic conditions. Further, the excessive algae accumulation on the water surface reduced N2O release fluxes via hindering the migration of the dissolved N2O into the atmosphere. These findings provide a new perspective and understanding for accurately evaluating N2O release fluxes driven by algae processes in eutrophic lakes.

Anthropogenic emissions have severely perturbed the marine biogeochemical cycle of lead (Pb). Here, we present new Pb concentration and isotope data for surface seawater from GEOTRACES section GA02, sampled in the western South Atlantic in 2011. The South Atlantic is divided into three hydrographic zones: equatorial (0-20°S), subtropical (20-40°S), and subantarctic (40-60°S). The equatorial zone is dominated by previously deposited Pb transported by surface currents. The subtropical zone largely reflects anthropogenic Pb emissions from South America, whilst the subantarctic zone presents a mixture of South American anthropogenic Pb and natural Pb from Patagonian dust. The mean Pb concentration of 16.7 ± 3.8 pmol/kg is 34 % lower than in the 1990s, mostly driven by changes in the subtropical zone, with the fraction of natural Pb increasing from 24 % to 36 % between 1996 and 2011. Although anthropogenic Pb remains predominant, these findings demonstrate the effectiveness of policies that banned leaded gasoline.

To better understand zinc and copper regulation and their involvement in various biochemical pathways as it relates to autism spectrum disorder (ASD), isotopic composition of serum zinc and copper were evaluated in both healthy children and children with ASD in North America. No significant difference in isotopic composition of serum zinc or copper with respect to healthy controls and ASD children were identified. However, the isotopic composition of serum copper in boys was found to be enriched in 65Cu in comparison to previously published healthy adult copper isotopic composition. Furthermore, in both boys and girls, the average isotopic composition of serum zinc is heavier than previously published healthy adult isotopic zinc composition. There was also a negative association between total zinc concentrations in serum and the zinc isotopic composition of serum in boys. Finally, children with heavier isotopic composition of copper also showed a high degree of variability in their zinc isotopic composition. While numerous studies have measured the isotopic composition of serum zinc and copper in adults, this is one of the first studies which measured the isotopic composition of serum copper and zinc in children, specifically those diagnosed with ASD. The results of this study showed that age and gender specific normal ranges of isotopic composition must be established to effectively use isotopic composition analysis in studying various diseases including ASD.