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1
Bataille, Clément P., Klervia Jaouen, Stefania Milano, Manuel Trost, Sven Steinbrenner, Éric Crubézy, and Rozenn Colleter. "Triple sulfur-oxygen-strontium isotopes probabilistic geographic assignment of archaeological remains using a novel sulfur isoscape of western Europe." PLOS ONE 16, no. 5 (May 5, 2021): e0250383. http://dx.doi.org/10.1371/journal.pone.0250383.
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Sulfur isotope composition of organic tissues is a commonly used tool for gathering information about provenance and diet in archaeology and paleoecology. However, the lack of maps predicting sulfur isotope variations on the landscape limits the possibility to use this isotopic system in quantitative geographic assignments. We compiled a database of 2,680 sulfur isotope analyses in the collagen of archaeological human and animal teeth from 221 individual locations across Western Europe. We used this isotopic compilation and remote sensing data to apply a multivariate machine-learning regression, and to predict sulfur isotope variations across Western Europe. The resulting model shows that sulfur isotope patterns are highly predictable, with 65% of sulfur isotope variations explained using only 4 variables representing marine sulfate deposition and local geological conditions. We used this novel sulfur isoscape and existing strontium and oxygen isoscapes of Western Europe to apply triple isotopes continuous-surface probabilistic geographic assignments to assess the origin of a series of teeth from local animals and humans from Brittany. We accurately and precisely constrained the origin of these individuals to limited regions of Brittany. This approach is broadly transferable to studies in archaeology and paleoecology as illustrated in a companion paper (Colleter et al. 2021).
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Arneson, Lynne S., Stephen MacAvoy, and Ethan Basset. "Metabolic protein replacement drives tissue turnover in adult mice." Canadian Journal of Zoology 84, no. 7 (July 1, 2006): 992–1002. http://dx.doi.org/10.1139/z06-081.
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Stable isotopes are increasingly being used to examine ecological and physiological questions, such as dietary choices, migration routes and timing, and physiological condition. To address these questions in the field, laboratory experiments must be done to determine diet–tissue discrimination values and turnover rates for stable isotopes in tissues. In this study, we examined the carbon and nitrogen turnover rates of whole blood, skeletal muscle, liver, kidney, heart, and brain, as well as the sulfur turnover rate of whole blood, skeletal muscle, and liver in Mus musculus L., 1758 following a diet change. By examining tissue isotope change in two groups of mice fed different diets, we found that tissues turnover at different rates (in order of fastest to slowest — liver, kidney, heart, brain, whole blood, skeletal muscle), but that carbon, nitrogen, and sulfur isotopes turned over with similar half-lives within a single tissue. By using a diet with different nutrient isotopic values, we also calculated that up to approximately 90%–95% of carbon in newly synthesized tissue was contributed by dietary protein. These results will provide field researchers with additional tissue isotopic half-lives to elucidate dietary history with a greater degree of certainty. The tissue sulfur half-lives provide an extra stable isotope that may be used in situations where carbon and nitrogen values do not differ between old and new nutrient sources.
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Lin, Mang, Xiaolin Zhang, Menghan Li, Yilun Xu, Zhisheng Zhang, Jun Tao, Binbin Su, Lanzhong Liu, Yanan Shen, and Mark H. Thiemens. "Five-S-isotope evidence of two distinct mass-independent sulfur isotope effects and implications for the modern and Archean atmospheres." Proceedings of the National Academy of Sciences 115, no. 34 (August 6, 2018): 8541–46. http://dx.doi.org/10.1073/pnas.1803420115.
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The signature of mass-independent fractionation of quadruple sulfur stable isotopes (S-MIF) in Archean rocks, ice cores, and Martian meteorites provides a unique probe of the oxygen and sulfur cycles in the terrestrial and Martian paleoatmospheres. Its mechanistic origin, however, contains some uncertainties. Even for the modern atmosphere, the primary mechanism responsible for the S-MIF observed in nearly all tropospheric sulfates has not been identified. Here we present high-sensitivity measurements of a fifth sulfur isotope, stratospherically produced radiosulfur, along with all four stable sulfur isotopes in the same sulfate aerosols and a suite of chemical species to define sources and mechanisms on a field observational basis. The five-sulfur-isotope and multiple chemical species analysis approach provides strong evidence that S-MIF signatures in tropospheric sulfates are concomitantly affected by two distinct processes: an altitude-dependent positive 33S anomaly, likely linked to stratospheric SO2 photolysis, and a negative 36S anomaly mainly associated with combustion. Our quadruple stable sulfur isotopic measurements in varying coal samples (formed in the Carboniferous, Permian, and Triassic periods) and in SO2 emitted from combustion display normal 33S and 36S, indicating that the observed negative 36S anomalies originate from a previously unknown S-MIF mechanism during combustion (likely recombination reactions) instead of coal itself. The basic chemical physics of S-MIF in both photolytic and thermal reactions and their interplay, which were not explored together in the past, may be another ingredient for providing deeper understanding of the evolution of Earth’s atmosphere and life’s origin.
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Tian, Jiepeng, Jinhui Wang, Tongliang Tian, Ligong Wang, Yingpeng Wang, Xiaowei Yu, Wen Zhang, Tianlong Ren, and Bin Sun. "In-Situ Geochemical and Rb–Sr Dating Analysis of Sulfides from a Gold Deposit Offshore of Northern Sanshandao, Jiaodong Peninsula, North China: Implications for Gold Mineralization." Minerals 14, no. 5 (April 26, 2024): 456. http://dx.doi.org/10.3390/min14050456.
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The gold deposit offshore of Northern Sanshandao is an ultra-large-scale gold deposit discovered in the Jiaodong ore area in recent years. This deposit is a fractured-zone altered-rock-type gold deposit; however, its ore genesis and precise mineralization processes are still highly controversial. Based on petrographical observation, the trace elements, sulfur isotopes, and rubidium–strontium isotopes of the gold-bearing pyrite were analyzed using LA-MC-ICP-MS to obtain the source of the ore-forming fluids and ore genesis. The results show that Au has a good positive correlation with Ag, As, and Cu. It is speculated that the As in the pyrite of the gold deposit offshore of Northern Sanshandao is in the form of As−, replacing S− and entering the pyrite, causing its lattice defects, and thus promoting the entry of Au+ into the gold-bearing pyrite. The Co/Ni ratios mainly range between 0.1 and 10, indicating that the mineralization process has experienced different forms of hydrothermal evolution and the mixing of different fluids. The results of the in-situ sulfur isotope analysis show that pyrite δ34S in the mineralization period is characterized by a high sulfur value. The authors of this study believe that the initial sulfur isotope composition has mantle-derived components. The large-scale, deep cutting, and high degree of fragmentation in the Sanshandao fault zone are conducive to the interaction between fluids and rocks, as well as the mixing and addition of seawater, resulting in the characteristic high δ34S value. The Sr isotopic compositions indicate a crust–mantle mixing attribute of the mineralized material source. The Rb–Sr isochron age of the pyrite is 118.5 ± 0.65 Ma, which represents the age of gold mineralization. According to the characteristics of the trace elements and sulfur isotopes, it is inferred that the gold deposit minerals offshore of Northern Sanshandao originated from deep magmatic-hydrothermal reservoirs, and the mixing of seawater and Au–As-rich hydrothermal fluids was the formation mechanism of huge amounts of gold precipitation.
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Saitoh, Masafumi, Sami Nabhan, Christophe Thomazo, Nicolas Olivier, Jean-François Moyen, Yuichiro Ueno, and Johanna Marin-Carbonne. "Multiple Sulfur Isotope Records of the 3.22 Ga Moodies Group, Barberton Greenstone Belt." Geosciences 10, no. 4 (April 16, 2020): 145. http://dx.doi.org/10.3390/geosciences10040145.
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The Moodies Group, the uppermost unit in the Barberton Greenstone Belt (BGB) in South Africa, is a ~3.7-km-thick coarse clastic succession accumulated on terrestrial-to-shallow marine settings at around 3.22 Ga. The multiple sulfur isotopic composition of pyrite of Moodies intervals was newly obtained to examine the influence of these depositional settings on the sulfur isotope record. Conglomerate and sandstone rocks were collected from three synclines north of the Inyoka Fault of the central BGB, namely, the Eureka, Dycedale, and Saddleback synclines. The sulfur isotopic composition of pyrite was analyzed by Secondary Ion Mass Spectrometry (SIMS) for 6 samples from the three synclines and by Isotope Ratio Mass Spectrometry (IR-MS) for 17 samples from a stratigraphic section in the Saddleback Syncline. The present results show a signal of mass-independent fractionation of sulfur isotopes (S-MIF), although t-tests statistically demonstrated that the Moodies S-MIF signals (mostly 0‰ < ∆33S < +0.5‰) are significantly small compared to the signal of the older Paleoarchean (3.6–3.2 Ga) records. These peculiar signatures might be related to initial deposition of detrital pyrite of juvenile origin from the surrounding intrusive (tonalite–trondhjemite–granodiorite; TTG) and felsic volcanic rocks, and/or to secondary addition of hydrothermal sulfur during late metasomatism. Moreover, fast accumulation (~0.1–1 mm/year) of the Moodies sediments might have led to a reduced accumulation of sulfur derived from an atmospheric source during their deposition. As a result, the sulfur isotopic composition of the sediments may have become susceptible to the secondary addition of metasomatic sulfur on a mass balance point of view. The sulfur isotopic composition of Moodies pyrite is similar to the composition of sulfides from nearby gold mines. It suggests that, after the Moodies deposition, metasomatic pyrite formation commonly occurred north of the Inyoka Fault in the central BGB at 3.1–3.0 Ga.
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Miller, J. J., G. J. Beke, S. Pawluk, and H. R. Krouse. "Sulfur and oxygen isotopic composition of sulfates at two saline sites in southern Alberta." Canadian Journal of Soil Science 73, no. 4 (November 1, 1993): 633–37. http://dx.doi.org/10.4141/cjss93-061.
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Possible sources of SO4 in soil, drift and bedrock at two saline sites in southern Alberta were investigated using sulfur and oxygen isotope analyses. Slight differences (0.6–5.2 per mil) between δ34S values of SO4 and insoluble S in the geologic material were attributed to kinetic fractionation during oxidation of organic S. Negative δ18O values of SO4 in the shallow (<6 m) bedrock, drift and soil reflected oxidation of reduced S. In contrast, positive δ18O values in the deep (>6 m) bedrock indicated sulfate reduction. The exact source of SO4 could not be determined in this preliminary study. The isotope approach, however, shows promise and warrants more detailed study. Key words: Salinization, sulfates, sulfur isotopes, oxygen isotopes
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Rossete, Alexssandra Luiza Rodrigues Molina, Josiane Meire Toloti Carneiro, Carlos Roberto Sant Ana Filho, and José Albertino Bendassolli. "Isotope determination of sulfur by mass spectrometry in soil samples." Revista Brasileira de Ciência do Solo 36, no. 6 (December 2012): 1787–93. http://dx.doi.org/10.1590/s0100-06832012000600012.
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Sulphur plays an essential role in plants and is one of the main nutrients in several metabolic processes. It has four stable isotopes (32S, 33S, 34S, and 36S) with a natural abundance of 95.00, 0.76, 4.22, and 0.014 in atom %, respectively. A method for isotopic determination of S by isotope-ratio mass spectrometry (IRMS) in soil samples is proposed. The procedure involves the oxidation of organic S to sulphate (S-SO4(2-)), which was determined by dry combustion with alkaline oxidizing agents. The total S-SO4(2-) concentration was determined by turbidimetry and the results showed that the conversion process was adequate. To produce gaseous SO2 gas, BaSO4 was thermally decomposed in a vacuum system at 900 ºC in the presence of NaPO3. The isotope determination of S (atom % 34S atoms) was carried out by isotope ratio mass spectrometry (IRMS). In this work, the labeled material (K2(34)SO4) was used to validate the method of isotopic determination of S; the results were precise and accurate, showing the viability of the proposed method.
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Tarboush, Rania A., Stephen E. MacAvoy, Stephen A. Macko, and Victoria Connaughton. "Contribution of catabolic tissue replacement to the turnover of stable isotopes in Danio rerio." Canadian Journal of Zoology 84, no. 10 (October 2006): 1453–60. http://dx.doi.org/10.1139/z06-136.
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Stable isotopes of carbon, nitrogen, and sulfur in organisms can trace nutrient sources and determine trophic interactions. However, time is required for an organism to reflect the isotopic composition of its diet. The rate at which an organism incorporates the isotopic signature of its food has a growth (k) component and a metabolic tissue replacement (m) component. This study shows that metabolic tissue replacement accounts for between 68% and 80% of the observed changes in isotopic signature in zebra danio ( Danio rerio (Hamilton, 1822)) muscle following a dietary shift, with the remainder owing to growth of new tissue. The half-lives of carbon, nitrogen, and sulfur were ~53, ~147 and ~58 days, respectively. This indicates that a significant period of isotopic disequilibria exists before zebra danio resemble dietary isotopic composition. These results show that catabolic replacement of tissue, as well as growth, must be taken into account when predicting the rate of isotope incorporation in warm-water fish. When using isotopic ratios to decipher food webs and trophic interactions, researchers should be aware that the often held assumption of isotopic equilibrium between diet and consumer may be violated.
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Sim, Min Sub, Shuhei Ono, and Tanja Bosak. "Effects of Iron and Nitrogen Limitation on Sulfur Isotope Fractionation during Microbial Sulfate Reduction." Applied and Environmental Microbiology 78, no. 23 (September 21, 2012): 8368–76. http://dx.doi.org/10.1128/aem.01842-12.
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ABSTRACTSulfate-reducing microbes utilize sulfate as an electron acceptor and produce sulfide that is depleted in heavy isotopes of sulfur relative to sulfate. Thus, the distribution of sulfur isotopes in sediments can trace microbial sulfate reduction (MSR), and it also has the potential to reflect the physiology of sulfate-reducing microbes. This study investigates the relationship between the availability of iron and reduced nitrogen and the magnitude of S-isotope fractionation during MSR by a marine sulfate-reducing bacterium, DMSS-1, aDesulfovibriospecies, isolated from salt marsh in Cape Cod, MA. Submicromolar levels of iron increase sulfur isotope fractionation by about 50% relative to iron-replete cultures of DMSS-1. Iron-limited cultures also exhibit decreased cytochromec-to-total protein ratios and cell-specific sulfate reduction rates (csSRR), implying changes in the electron transport chain that couples carbon and sulfur metabolisms. When DMSS-1 fixes nitrogen in ammonium-deficient medium, it also produces larger fractionation, but it occurs at faster csSRRs than in the ammonium-replete control cultures. The energy and reducing power required for nitrogen fixation may be responsible for the reverse trend between S-isotope fractionation and csSRR in this case. Iron deficiency and nitrogen fixation by sulfate-reducing microbes may lead to the large observed S-isotope effects in some euxinic basins and various anoxic sediments.
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Pellerin, André, Luke Anderson-Trocmé, Lyle G. Whyte, Grant M. Zane, Judy D. Wall, and Boswell A. Wing. "Sulfur Isotope Fractionation during the Evolutionary Adaptation of a Sulfate-Reducing Bacterium." Applied and Environmental Microbiology 81, no. 8 (February 6, 2015): 2676–89. http://dx.doi.org/10.1128/aem.03476-14.
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ABSTRACTDissimilatory sulfate reduction is a microbial catabolic pathway that preferentially processes less massive sulfur isotopes relative to their heavier counterparts. This sulfur isotope fractionation is recorded in ancient sedimentary rocks and generally is considered to reflect a phenotypic response to environmental variations rather than to evolutionary adaptation. Modern sulfate-reducing microorganisms isolated from similar environments can exhibit a wide range of sulfur isotope fractionations, suggesting that adaptive processes influence the sulfur isotope phenotype. To date, the relationship between evolutionary adaptation and isotopic phenotypes has not been explored. We addressed this by studying the covariation of fitness, sulfur isotope fractionation, and growth characteristics inDesulfovibrio vulgarisHildenborough in a microbial evolution experiment. After 560 generations, the mean fitness of the evolved lineages relative to the starting isogenic population had increased by ∼17%. After 927 generations, the mean fitness relative to the initial ancestral population had increased by ∼20%. Growth rate in exponential phase increased during the course of the experiment, suggesting that this was a primary influence behind the fitness increases. Consistent changes were observed within different selection intervals between fractionation and fitness. Fitness changes were associated with changes in exponential growth rate but changes in fractionation were not. Instead, they appeared to be a response to changes in the parameters that govern growth rate: yield and cell-specific sulfate respiration rate. We hypothesize that cell-specific sulfate respiration rate, in particular, provides a bridge that allows physiological controls on fractionation to cross over to the adaptive realm.
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Davidson, Chen, Alon Amrani, and Alon Angert. "Tropospheric carbonyl sulfide mass balance based on direct measurements of sulfur isotopes." Proceedings of the National Academy of Sciences 118, no. 6 (February 5, 2021): e2020060118. http://dx.doi.org/10.1073/pnas.2020060118.
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Robust estimates for the rates and trends in terrestrial gross primary production (GPP; plant CO2 uptake) are needed. Carbonyl sulfide (COS) is the major long-lived sulfur-bearing gas in the atmosphere and a promising proxy for GPP. Large uncertainties in estimating the relative magnitude of the COS sources and sinks limit this approach. Sulfur isotope measurements (34S/32S; δ34S) have been suggested as a useful tool to constrain COS sources. Yet such measurements are currently scarce for the atmosphere and absent for the marine source and the plant sink, which are two main fluxes. Here we present sulfur isotopes measurements of marine and atmospheric COS, and of plant-uptake fractionation experiments. These measurements resulted in a complete data-based tropospheric COS isotopic mass balance, which allows improved partition of the sources. We found an isotopic (δ34S ± SE) value of 13.9 ± 0.1‰ for the troposphere, with an isotopic seasonal cycle driven by plant uptake. This seasonality agrees with a fractionation of −1.9 ± 0.3‰ which we measured in plant-chamber experiments. Air samples with strong anthropogenic influence indicated an anthropogenic COS isotopic value of 8 ± 1‰. Samples of seawater-equilibrated-air indicate that the marine COS source has an isotopic value of 14.7 ± 1‰. Using our data-based mass balance, we constrained the relative contribution of the two main tropospheric COS sources resulting in 40 ± 17% for the anthropogenic source and 60 ± 20% for the oceanic source. This constraint is important for a better understanding of the global COS budget and its improved use for GPP determination.
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Canfield, D. E. "Biogeochemistry of Sulfur Isotopes." Reviews in Mineralogy and Geochemistry 43, no. 1 (January 1, 2001): 607–36. http://dx.doi.org/10.2138/gsrmg.43.1.607.
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Guibourdenche, Laetitia. "Deciphering sulfur cycling with multiple sulfur isotopes." Nature Reviews Earth & Environment 3, no. 3 (February 21, 2022): 163. http://dx.doi.org/10.1038/s43017-022-00273-0.
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Cornwell, Jeffrey C., J. C. Stevenson, and C. Neill. "Biogeochemieal origin of δ34S isotopic signatures in a prairie marsh." Canadian Journal of Fisheries and Aquatic Sciences 52, no. 8 (August 1, 1995): 1816–20. http://dx.doi.org/10.1139/f95-174.
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Sulfur isotope ratios were determined in a prairie marsh at Delta, Manitoba, Canada, to determine whether organic matter produced in the marsh had distinctive isotopic signatures. High sulfate levels in sediments from the Delta Marsh arise from high salt concentrations in soils. Sulfate reduction is the major anaerobic metabolic pathway in this sediment system and sulfate diffused into sediment both from deeper soil horizons and from overlying water. Surface water δ34S-SO42− values of 15 ± 1‰ increased to a maximum of almost 40‰ in deeper sediment horizons, in marked contrast to sediment pore water δ34S-H2S values of 2 ± 4‰. The high degree of discrimination between δ34S in sulfate and in hydrogen sulfide is similar to that found in brackish and marine ecosystems. Emergent macrophytes such as phragmites and cattail had isotopic signatures similar to reduced sulfur in this system. The data from this study suggest that in some nontidal wetland ecosystems, sulfur isotopes may be useful in determining producer–consumer relationships in a manner similar to their application in marine ecosystems.
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Goryachev, N. A., A. V. Ignatiev, T. A. Velivetskaya, A. E. Budyak, and Yu I. Tarasova. "Experience in applying a local analysis an sulfur isotopes in the ore sulfides of the largest deposits of Bodaibinsky Synclinoria (Eastern Siberia)." Доклады Академии наук 484, no. 4 (May 5, 2019): 460–63. http://dx.doi.org/10.31857/s0869-56524844460-463.
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The experience of LA—ICP determining of the isotopic composition of sulfur pyrite and arsenopyrite of gold deposits of the Baikal-patomsky plateau is considered. The technique is characterized. It is shown that all the studied samples have values δ34S and δ33S strictly corresponding to the law of mass-dependent fractionation of sulfur isotopes. A regular alleviation of the isotopic composition of sulfur of pyrite as its crystals grow for Sukhoi Log and the isotopic homogeneity of pyrite and pyrrhotite of the Golets Vysokhashiy deposit are established. It is concluded that the possible role of metamorphism of the Mamsko-Oronsky belt in the formation of isotopic homogeneity of ore sulfides.
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Balter, Vincent, Andre Nogueira da Costa, Victor Paky Bondanese, Klervia Jaouen, Aline Lamboux, Suleeporn Sangrajrang, Nicolas Vincent, et al. "Natural variations of copper and sulfur stable isotopes in blood of hepatocellular carcinoma patients." Proceedings of the National Academy of Sciences 112, no. 4 (January 12, 2015): 982–85. http://dx.doi.org/10.1073/pnas.1415151112.
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The widespread hypoxic conditions of the tumor microenvironment can impair the metabolism of bioessential elements such as copper and sulfur, notably by changing their redox state and, as a consequence, their ability to bind specific molecules. Because competing redox state is known to drive isotopic fractionation, we have used here the stable isotope compositions of copper (65Cu/63Cu) and sulfur (34S/32S) in the blood of patients with hepatocellular carcinoma (HCC) as a tool to explore the cancer-driven copper and sulfur imbalances. We report that copper is 63Cu-enriched by ∼0.4‰ and sulfur is 32S-enriched by ∼1.5‰ in the blood of patients compared with that of control subjects. As expected, HCC patients have more copper in red blood cells and serum compared with control subjects. However, the isotopic signature of this blood extra copper burden is not in favor of a dietary origin but rather suggests a reallocation in the body of copper bound to cysteine-rich proteins such as metallothioneins. The magnitude of the sulfur isotope effect is similar in red blood cells and serum of HCC patients, implying that sulfur fractionation is systemic. The 32S-enrichment of sulfur in the blood of HCC patients is compatible with the notion that sulfur partly originates from tumor-derived sulfides. The measurement of natural variations of stable isotope compositions, using techniques developed in the field of Earth sciences, can provide new means to detect and quantify cancer metabolic changes and provide insights into underlying mechanisms.
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Madej, Adam, Ewa Forma, Michał Golberg, Rafał Kamiński, Piotr Paneth, Józef Kobos, Waldemar Różański, and Marek Lipiński. "13C Natural Isotope Abundance in Urothelium as a New Marker in the Follow-Up of Patients with Bladder Cancer." Cancers 14, no. 10 (May 13, 2022): 2423. http://dx.doi.org/10.3390/cancers14102423.
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Bladder cancer (BC) is the most common urological malignancy and has a high incidence of recurrence. BC cells alter their nutrient uptake and metabolic pathways in order to continue the production of sufficient levels of ATP and metabolic intermediates for proliferation and survival. Changes in metabolic pathways regarding the rate of the enzymatic reaction and transport lead to differences in the content of natural isotopes (13C, 15N, 34S) between normal and cancerous tissues. The assessment of the stable isotopes of carbon, nitrogen, and sulfur in normal urothelium and bladder cancer samples was performed using Isotope Ratio Mass Spectrometry (IRMS). The natural abundance of 15N and 13C was decreased in bladder cancer samples when compared to normal urothelium. No significant correlation was observed in BC specimens depending on the tumor grade and stage. Samples derived from bladder tumors and normal urothelium had a different pattern of 15N and 13C isotope abundance. Decreased 13C natural isotopes in the normal urothelium of BC patients were significantly associated with a shorter DFS. Our results suggest that isotopic analysis of normal urothelium of BC patients can be used to predict bladder cancer recurrence.
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Smit, Karen V., Steven B. Shirey, Erik H. Hauri, and Richard A. Stern. "Sulfur isotopes in diamonds reveal differences in continent construction." Science 364, no. 6438 (April 25, 2019): 383–85. http://dx.doi.org/10.1126/science.aaw9548.
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Neoproterozoic West African diamonds contain sulfide inclusions with mass-independently fractionated (MIF) sulfur isotopes that trace Archean surficial signatures into the mantle. Two episodes of subduction are recorded in these West African sulfide inclusions: thickening of the continental lithosphere through horizontal processes around 3 billion years ago and reworking and diamond growth around 650 million years ago. We find that the sulfur isotope record in worldwide diamond inclusions is consistent with changes in tectonic processes that formed the continental lithosphere in the Archean. Slave craton diamonds that formed 3.5 billion years ago do not contain any MIF sulfur. Younger diamonds from the Kaapvaal, Zimbabwe, and West African cratons do contain MIF sulfur, which suggests craton construction by advective thickening of mantle lithosphere through conventional subduction-style horizontal tectonics.
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Merrett, Deborah C., Christina Cheung, Christopher Meiklejohn, and Michael P. Richards. "Stable isotope analysis of human bone from Ganj Dareh, Iran, ca. 10,100 calBP." PLOS ONE 16, no. 3 (March 2, 2021): e0247569. http://dx.doi.org/10.1371/journal.pone.0247569.
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We report here on stable carbon, nitrogen, and sulfur isotope values from bone collagen of human (n = 20) and faunal (n = 11) remains from the Early Neolithic site of Ganj Dareh, Iran, dating to ca. 10,100 cal. BP. Our focus explores how isotope values of human bone vary by age and sex, and evaluates dietary practices at this site. It also provides a baseline for future studies of subsistence in the early Holocene Central Zagros Mountains, from the site with the first evidence for human ovicaprid management in the Near East. Human remains include individuals of all age groups for dietary reconstruction, as well two Ottoman intrusive burials for temporal and cultural comparison. All analyzed individuals exhibited δ13C and δ15N values consistent with a diet based heavily on C3 terrestrial sources. There is no statistically significant difference between the isotopic compositions of the two sexes, though males appear to show larger variations compared to females. Interesting patterns in the isotopic compositions of the subadults suggested weaning children may be fed with supplements with distinctive δ13C values. Significant difference in sulfur isotope values between humans and fauna could be the earliest evidence of transhumance and could identify one older adult male as a possible transhumant shepherd. Both Ottoman individuals had distinctively different δ13C, δ15N, and δ34S values compared to the Neolithic individuals. This is the first large scale analysis of human stable isotopes from the eastern end of the early Holocene Fertile Crescent. It provides a baseline for future intersite exploration of stable isotopes and insight into the lifeways, health, and processes of neolithisation associated with the origins of goat domestication at Ganj Dareh and the surrounding Central Zagros.
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Pasquier, Virgil, Pierre Sansjofre, Marina Rabineau, Sidonie Revillon, Jennifer Houghton, and David A. Fike. "Pyrite sulfur isotopes reveal glacial−interglacial environmental changes." Proceedings of the National Academy of Sciences 114, no. 23 (May 22, 2017): 5941–45. http://dx.doi.org/10.1073/pnas.1618245114.
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The sulfur biogeochemical cycle plays a key role in regulating Earth’s surface redox through diverse abiotic and biological reactions that have distinctive stable isotopic fractionations. As such, variations in the sulfur isotopic composition (δ34S) of sedimentary sulfate and sulfide phases over Earth history can be used to infer substantive changes to the Earth’s surface environment, including the rise of atmospheric oxygen. Such inferences assume that individual δ34S records reflect temporal changes in the global sulfur cycle; this assumption may be well grounded for sulfate-bearing minerals but is less well established for pyrite-based records. Here, we investigate alternative controls on the sedimentary sulfur isotopic composition of marine pyrite by examining a 300-m drill core of Mediterranean sediments deposited over the past 500,000 y and spanning the last five glacial−interglacial periods. Because this interval is far shorter than the residence time of marine sulfate, any change in the sulfur isotopic record preserved in pyrite (δ34Spyr) necessarily corresponds to local environmental changes. The stratigraphic variations (>76‰) in the isotopic data reported here are among the largest ever observed in pyrite, and are in phase with glacial−interglacial sea level and temperature changes. In this case, the dominant control appears to be glacial−interglacial variations in sedimentation rates. These results suggest that there exist important but previously overlooked depositional controls on sedimentary sulfur isotope records, especially associated with intervals of substantial sea level change. This work provides an important perspective on the origin of variability in such records and suggests meaningful paleoenvironmental information can be derived from pyrite δ34S records.
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Prichko, T. G., U. F. Yakuba, and M. V. Karpushina. "Study of the possibility of using data on the content of stable isotopes of magnesium to predict the region of apple production." Agrarian science, no. 2 (March 5, 2023): 95–99. http://dx.doi.org/10.32634/0869-8155-2023-367-2-95-99.
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Relevance. Reliable criteria for determining the region of origin of fruit products attract the constant attention of researchers in various countries. A number of approaches aimed at solving this problem are already known, and some progress has been made in interpreting experimental data for fruits on the content of stable isotopes of hydrogen, carbon, oxygen, nitrogen, and sulfur. It is possible that information about the fractionation of stable isotopes of magnesium will allow us to obtain equally important and reliable information to achieve the same goals.Methods. A mass spectrometer with inductively coupled plasma, standard samples of stable isotopes of magnesium produced in Russia were used to perform the work. The total concentration of magnesium cations was determined by atomic absorption in the flame and on the capillary electrophoresis system.Results. During the research, the mass and percentage ratio of three stable isotopes (24Mg, 25Mg, 26Mg) in the studied samples of apples grown in different soil and climatic zones was established. The data obtained reflect the relative prevalence of isotopes of this element, expressed in the ratio of the least common isotope to the most common. The deviation of the isotopic composition of Mg prototypes from the conventional standard was determined, significant deviations were obtained for the magnetic isotope 25Mg and non-magnetic 26Mg. The initial data on the fractionation of stable isotopes of magnesium in raw materials growing in different regions were obtained, with the aim of possible subsequent use as indicators in biochemical and physiological studies. A combination of the obtained information on Mg isotopes is assumed, taking into account the content of isotopes of other metals, which will make it possible to specify the region of growth of raw materials with greater reliability.
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Ebert, Claire E., Asta J. Rand, Kirsten Green-Mink, Julie A. Hoggarth, Carolyn Freiwald, Jaime J. Awe, Willa R. Trask, et al. "Sulfur isotopes as a proxy for human diet and mobility from the preclassic through colonial periods in the Eastern Maya lowlands." PLOS ONE 16, no. 8 (August 12, 2021): e0254992. http://dx.doi.org/10.1371/journal.pone.0254992.
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Maya archaeologists have long been interested in understanding ancient diets because they provide information about broad-scale economic and societal transformations. Though paleodietary studies have primarily relied on stable carbon (δ13C) and nitrogen (δ15N) isotopic analyses of human bone collagen to document the types of food people consumed, stable sulfur (δ34S) isotope analysis can potentially provide valuable data to identify terrestrial, freshwater, or marine/coastal food sources, as well as determine human mobility and migration patterns. Here we assess applications of δ34S for investigating Maya diet and migration through stable isotope analyses of human bone collagen (δ13C, δ15N, and δ34S) from 114 individuals from 12 sites in the Eastern Maya lowlands, temporally spanning from the Late Preclassic (300 BCE—300 CE) through Colonial periods (1520–1800 CE). Results document a diet dominated by maize and other terrestrial resources, consistent with expectations for this inland region. Because δ34S values reflect local geology, our analyses also identified recent migrants to the Eastern lowlands who had non-local δ34S signatures. When combined with other indicators of mobility (e.g., strontium isotopes), sulfur isotopic data provide a powerful tool to investigate movement across a person’s lifespan. This study represents the largest examination of archaeological human δ34S isotope values for the Maya lowlands and provides a foundation for novel insights into both subsistence practices and migration.
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Cheltsov, A. N., N. S. Babaev, L. Yu Sosnin, Yu D. Shipilov, A. V. Bespalov, P. V. Mochalov, and V. K. Khamylov. "Centrifugal enrichment of sulfur isotopes." Journal of Radioanalytical and Nuclear Chemistry 299, no. 2 (July 19, 2013): 989–93. http://dx.doi.org/10.1007/s10967-013-2650-4.
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Zheng, Y. F. "Sulfur isotopes in the mantle." Naturwissenschaften 79, no. 11 (November 1992): 511–12. http://dx.doi.org/10.1007/bf01135769.
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Zhang, Songsong, Xiaoyong Yang, and Lei Liu. "Evolution, Magmatic Source and Metallogenesis of A-Type Granites in the Fanchang Volcanic Basin, Middle and Lower Yangtze Metallogenic Belt: A Review." Minerals 13, no. 4 (April 18, 2023): 571. http://dx.doi.org/10.3390/min13040571.
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The Fanchang volcanic basin (FVB) is located in the Middle and Lower Yangtze Metallogenic Belt (MLYMB) between the ore districts of Ningwu and Tongling. The existing ore deposits in the FVB are relatively small in scale and related to late Mesozoic A-type granites. In this paper, the crystallization age, major and trace element composition, and Sr-Nd and Hf isotope compositions of the A-type granites are summarized from the literature; in addition, the magnetite composition, H and O isotopes of fluid inclusions, and sulfur isotope composition of metal sulfides in some typical ore deposits in the FVB are also summarized to give insights into the petrogenesis and mineralization of the A-type granites intruding into the FVB. The results show that: (1) Orthopyroxene, plagioclase, K-feldspar, and biotite are the main fractionating minerals controlling the evolution of the magmas of A-type granites in the FVB and other areas in the MLYMB. (2) The whole-rock Sr-Nd and zircon Hf isotopic characteristics show that the source of A-type granite magma is complex and includes the enriched mantle, lower crust, and upper crust, probably with stronger participation of Archaean–Paleoproterozoic crustal materials in the FVB granites than in other regions of the MLYMB. (3) The ores in the FVB are dominated by skarn and hydrothermal deposits. H and O isotopes of fluid inclusions indicate that ore-forming fluids have been derived from mixtures of magmatic hydrothermal fluid, meteoric waters, and deep brine related to gypsum layers. S isotopes of metal sulfides indicate that the sulfur may be a mixture of magmatically derived sulfur and sulfur originating from the Triassic gypsum-bearing layers. The deposit and ore characteristics of the main deposits in the FVB are also illustrated, and the evaluation of metal resources indicates that the skarn and hydrothermal iron–zinc ores in the FVB also have potential as sources of Cd, Ga, and Se. In addition, in terms of the oxygen fugacity, rock type, and geochemical characteristics of magmatic rocks, the metallogenic characteristics and potential of the A-type granites in the FVB are evaluated. It is considered that in addition to the dominant constituents of iron and zinc and the minor constituents listed above, the FVB could have the potential for providing copper, gold, molybdenum, uranium, and other metals as well.
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Harris, E., B. Sinha, P. Hoppe, J. N. Crowley, S. Ono, and S. Foley. "Sulfur isotope fractionation during oxidation of sulfur dioxide: gas-phase oxidation by OH radicals and aqueous oxidation by H<sub>2</sub>O<sub>2</sub>, O<sub>3</sub> and iron catalysis." Atmospheric Chemistry and Physics 12, no. 1 (January 6, 2012): 407–23. http://dx.doi.org/10.5194/acp-12-407-2012.
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Abstract. The oxidation of SO2 to sulfate is a key reaction in determining the role of sulfate in the environment through its effect on aerosol size distribution and composition. Sulfur isotope analysis has been used to investigate sources and chemical processes of sulfur dioxide and sulfate in the atmosphere, however interpretation of measured sulfur isotope ratios is challenging due to a lack of reliable information on the isotopic fractionation involved in major transformation pathways. This paper presents laboratory measurements of the fractionation factors for the major atmospheric oxidation reactions for SO2: Gas-phase oxidation by OH radicals, and aqueous oxidation by H2O2, O3 and a radical chain reaction initiated by iron. The measured fractionation factor for 34S/32S during the gas-phase reaction is αOH = (1.0089±0.0007)−((4±5)×10−5) T(°C). The measured fractionation factor for 34S/32S during aqueous oxidation by H2O2 or O3 is αaq = (1.0167±0.0019)−((8.7±3.5) ×10−5)T(°C). The observed fractionation during oxidation by H2O2 and O3 appeared to be controlled primarily by protonation and acid-base equilibria of S(IV) in solution, which is the reason that there is no significant difference between the fractionation produced by the two oxidants within the experimental error. The isotopic fractionation factor from a radical chain reaction in solution catalysed by iron is αFe = (0.9894±0.0043) at 19 °C for 34S/32S. Fractionation was mass-dependent with regards to 33S/32S for all the reactions investigated. The radical chain reaction mechanism was the only measured reaction that had a faster rate for the light isotopes. The results presented in this study will be particularly useful to determine the importance of the transition metal-catalysed oxidation pathway compared to other oxidation pathways, but other main oxidation pathways can not be distinguished based on stable sulfur isotope measurements alone.
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Borzenko, Svetlana. "Geochemical transformations of sulfur in salt lakes (Transbaikalia)." E3S Web of Conferences 411 (2023): 02009. http://dx.doi.org/10.1051/e3sconf/202341102009.
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The water column in brackish and saline lakes hosts various forms of sulfur including sulfide (hydrosulfide), elemental, thiosulfate, and sulfate sulfur. The unequal distribution of these reduced sulfur species indicates the presence of two opposing processes - sulfate reduction and oxidation of newly formed hydrogen sulfide. The scale of these processes varies among lakes, resulting in differing proportions of reduced sulfur forms. The bacterial reduction of sulfate ions is confirmed by a significant separation of sulfur isotopes into sulfide and sulfate ions, with the lighter isotope accumulating in the former and heavier isotope in the latter. In most soda, chloride, brackish, and salt lakes, sulfate reduction is the principal process responsible for relatively low sulfate ion content. Additionally, the presence of an oxidizing environment and sulfides in host rocks provide additional sources for sulfates, leading to the formation of sulfate-type lakes. The formation of specific types and subtypes of brackish and salt lakes is determined by processes such as water evaporation, dissolution of aluminosilicates, sulfate reduction, and oxidation of sulfides. The dominance of these processes contributes to the geochemical diversity of lakes.
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Bontognali, Tomaso R. R., Alex L. Sessions, Abigail C. Allwood, Woodward W. Fischer, John P. Grotzinger, Roger E. Summons, and John M. Eiler. "Sulfur isotopes of organic matter preserved in 3.45-billion-year-old stromatolites reveal microbial metabolism." Proceedings of the National Academy of Sciences 109, no. 38 (September 4, 2012): 15146–51. http://dx.doi.org/10.1073/pnas.1207491109.
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The 3.45-billion-year-old Strelley Pool Formation of Western Australia preserves stromatolites that are considered among the oldest evidence for life on Earth. In places of exceptional preservation, these stromatolites contain laminae rich in organic carbon, interpreted as the fossil remains of ancient microbial mats. To better understand the biogeochemistry of these rocks, we performed microscale in situ sulfur isotope measurements of the preserved organic sulfur, including both Δ33S and . This approach allows us to tie physiological inference from isotope ratios directly to fossil biomass, providing a means to understand sulfur metabolism that is complimentary to, and independent from, inorganic proxies (e.g., pyrite). Δ33S values of the kerogen reveal mass-anomalous fractionations expected of the Archean sulfur cycle, whereas values show large fractionations at very small spatial scales, including values below -15‰. We interpret these isotopic patterns as recording the process of sulfurization of organic matter by H2S in heterogeneous mat pore-waters influenced by respiratory S metabolism. Positive Δ33S anomalies suggest that disproportionation of elemental sulfur would have been a prominent microbial process in these communities.
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Khuong, Hung The, Ta Dinh Tung, Do Quoc Binh, Pham Nhu Sang, Nguyen Thi Cuc, Nguyen Thi Hoang Linh, and Quach Duc Tin. "Sulfur and lead isotope geochemical characteristics of Pb-Zn deposits in the Khau Loc zone, northeastern Vietnam, and their significance." Geology, Geophysics and Environment 47, no. 3 (December 1, 2021): 143–57. http://dx.doi.org/10.7494/geol.2021.47.3.143.
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In northeastern Vietnam, the Khau Loc zone is considered to have high potential for lead-zinc mineralization. The lead isotope data for 18 galena samples and 18 ones of δ34S isotope data (including galena and pyrite samples) were collected from lead-zinc ore deposits in some areas in the Khau Loc zone, including Phia Dam, Khuoi Man, Ban Lin, Lung Dam, and Ta Pan. These were employed to investigate the sulfur and lead isotope geochemical characteristics of Pb-Zn deposits and their significance in this study. The samples were analyzed using the LA-ICP-MS to show that the Pb isotopic ratios of 206Pb/204Pb, 207Pb/204Pb, and 208Pb/204Pb in the galena samples range from 17.8908 to 18.6012, 15.5794 to 16.1025, 38.4420 to 39.2118, with the average values of 18.296, 15.749, and 38.812, respectively. The pyrite and galena samples had the δ34S isotope, ranging from 9.0 to 15.106. The sulfur isotope systematics implies that most of the lead-zinc ore formations originated from marine sedimentary evaporation deposits and magmatic intrusion-volcanic eruption sources rich in silica. The distribution of lead isotopic ratios had a well-defined cluster for each deposit, indicating the formation of lead-zinc deposits and lower crust and orogen trends. In addition, these findings of lead isotopic ratios and δ 34S isotopes proved that the Khau Loc zone is an activated structure with continuous growth in continental crust thickness during the early Proterozoic and Cenozoic periods. Furthermore, the study results also presented the evolution of material sources involved in the formation of lead-zinc ores in the Khau Loc zone.
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Velojic, Milos, Dejan Prelevic, and Rade Jelenkovic. "The origin of lead and sulphur in Tulare ore field, Lece magmatic complex, SE Serbia." Annales g?ologiques de la Peninsule balkanique 79, no. 2 (2018): 19–28. http://dx.doi.org/10.2298/gabp1802019v.
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Lece magmatic complex in SE Serbia, part of the Serbo-Macedonian Metallogenic Province, is one of the most promising zones for lead, zinc and precious metals for the country. This complex was formed as a result of the post-collisional magmatic activity that lasted from Oligocene to Miocene. This study brings new lead and sulphur isotope data with an aim to constrain the origin of mineralizing fluids and to estimate the temperature of their formation. Galena from the Bakrenjaca locality shows high 207Pb/204Pb values implying that the lead was dominantly derived from the upper continental crustal geochemical reservoir which was probably recycled within the mantle and erupted during Tertiary post-collisional magmatism. Sulfur isotope composition of galena, sphalerite and pyrite show overlapping ?34S values in the range between 0 and 3? indicating a mantle origin of sulphur. Sulfur isotopes were also used to estimate the temperature under which the minerals were deposited forming a complex of veins. The calculated temperature is around 350?C. Since this temperature is too high for epithermal deposits, it is probable that the associated minerals weren?t deposited in isotopic equilibrium and other methods should be conducted for more precise temperature evaluation.
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Sela-Adler, Michal, Ward Said-Ahmad, Orit Sivan, Werner Eckert, Ronald P. Kiene, and Alon Amrani. "Isotopic evidence for the origin of dimethylsulfide and dimethylsulfoniopropionate-like compounds in a warm, monomictic freshwater lake." Environmental Chemistry 13, no. 2 (2016): 340. http://dx.doi.org/10.1071/en15042.
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Environmental context The volatile sulfur compound, dimethylsulfide (DMS), plays a major role in the global sulfur cycle by transferring sulfur from aquatic environments to the atmosphere. Compared to marine environments, freshwater environments are under studied with respect to DMS cycling. The goal of this study was to assess the formation pathways of DMS in a freshwater lake using natural stable isotopes of sulfur. Our results provide unique sulfur isotopic evidence for the multiple DMS sources and dynamics that are linked to the various biogeochemical processes that occur in freshwater lake water columns and sediments. Abstract The volatile methylated sulfur compound, dimethylsulfide (DMS), plays a major role in the global sulfur cycle by transferring sulfur from aquatic environments to the atmosphere. The main precursor of DMS in saline environments is dimethylsulfoniopropionate (DMSP), a common osmolyte in algae. The goal of this study was to assess the formation pathways of DMS in the water column and sediments of a monomictic freshwater lake based on seasonal profiles of the concentrations and isotopic signatures of DMS and DMSP. Profiles of DMS in the epilimnion during March and June 2014 in Lake Kinneret showed sulfur isotope (δ34S) values of +15.8±2.0 per mille (‰), which were enriched by up to 4.8 ‰ compared with DMSP δ34S values in the epilimnion at that time. During the stratified period, the δ34S values of DMS in the hypolimnion decreased to –7.0 ‰, close to the δ34S values of coexisting H2S derived from dissimilatory sulfate reduction in the reduced bottom water and sediments. This suggests that H2S was methylated by unknown microbial processes to form DMS. In the hypolimnion during the stratified period DMSP was significantly 34S enriched relative to DMS reflecting its different S source, which was mostly from sulfate assimilation. In the sediments, δ34S values of DMS were depleted by 2–4 ‰ relative to porewater (HCl-extracted) DMSP and enriched relative to H2S. This observation suggests two main formation pathways for DMS in the sediment, one from the degradation of DMSP and one from methylation of H2S. The present study provides isotopic evidence for multiple sources of DMS in stratified water bodies and complex DMSP–DMS dynamics that are linked to the various biogeochemical processes within the sulfur cycle.
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Coplen, Tyler B., and Yesha Shrestha. "Isotope-abundance variations and atomic weights of selected elements: 2016 (IUPAC Technical Report)." Pure and Applied Chemistry 88, no. 12 (December 1, 2016): 1203–24. http://dx.doi.org/10.1515/pac-2016-0302.
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AbstractThere are 63 chemical elements that have two or more isotopes that are used to determine their standard atomic weights. The isotopic abundances and atomic weights of these elements can vary in normal materials due to physical and chemical fractionation processes (not due to radioactive decay). These variations are well known for 12 elements (hydrogen, lithium, boron, carbon, nitrogen, oxygen, magnesium, silicon, sulfur, chlorine, bromine, and thallium), and the standard atomic weight of each of these elements is given by IUPAC as an interval with lower and upper bounds. Graphical plots of selected materials and compounds of each of these elements have been published previously. Herein and at the URL http://dx.doi.org/10.5066/F7GF0RN2, we provide isotopic abundances, isotope-delta values, and atomic weights for each of the upper and lower bounds of these materials and compounds.
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Bin, CUI, ZHAO Lei, ZHAN Zhaoyang, and HE Zhijun. "Mixed Population Screening for Sulfur Isotopes." Acta Geologica Sinica - English Edition 78, no. 2 (September 7, 2010): 568–70. http://dx.doi.org/10.1111/j.1755-6724.2004.tb00168.x.
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Gunnarsson-Robin, Jóhann, Andri Stefánsson, Shuhei Ono, and Peter Torssander. "Sulfur isotopes in Icelandic thermal fluids." Journal of Volcanology and Geothermal Research 346 (October 2017): 161–79. http://dx.doi.org/10.1016/j.jvolgeores.2017.01.021.
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McDermott, Jill M., Shuhei Ono, Margaret K. Tivey, Jeffrey S. Seewald, Wayne C. Shanks, and Andrew R. Solow. "Identification of sulfur sources and isotopic equilibria in submarine hot-springs using multiple sulfur isotopes." Geochimica et Cosmochimica Acta 160 (July 2015): 169–87. http://dx.doi.org/10.1016/j.gca.2015.02.016.
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Watkinson, Charles J., Peter Gasson, Gareth O. Rees, and Markus Boner. "The Development and Use of Isoscapes to Determine the Geographical Origin of Quercus spp. in the United States." Forests 11, no. 8 (August 7, 2020): 862. http://dx.doi.org/10.3390/f11080862.
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The stable isotope ratios of oxygen, hydrogen, carbon and sulfur from extracted wood of 87 samples of oaks from the United States were analysed. Relationships with climate variables and the stable isotope ratios of the 69 training dataset samples were investigated to a monthly resolution using long-term monthly mean climate data from NASA and the University of East Anglia’s Climate Research Unit, in conjunction with forecast data for hydrogen and oxygen isotope ratios in precipitation. These relationships were used to construct model isoscapes for oxygen, hydrogen, carbon and sulfur for US oak with the aim of using them to forecast isotopic patterns in areas that were not sampled and predict values in samples not used to construct the models. The leading predictors for isoscape generation were oxygen isotope ratios in January precipitation for oak oxygen isotope ratios, hydrogen isotope ratios in July precipitation for oak hydrogen isotope ratios, water vapour in April for carbon isotope ratios, and reflected shortwave radiation in March in combination with sulfate concentration in May for oak sulfur isotopes. The generated isoscapes can be used to show regions an unknown sample may have originated from with a resolution dependent on the rarity of the stable isotope signature within the United States. The models were assessed using the data of 18 samples of georeferenced oak. The assessment found that 100% of oxygen, 94% of hydrogen, 78% of carbon, and 94% of sulfur isotope ratios in the 18 test dataset samples fell within two standard deviations of the isoscape models. Using the results of the isoscapes in combination found that there were 4/18 test samples which did not fall within two standard deviations of the four models, this is largely attributed to the lower predictive power of the carbon isoscape model in conjunction with high local variability in carbon isotope ratios in both the test and training data. The method by which this geographic origin method has been developed will be useful to combat illegal logging and to validate legal supply chains for the purpose of good practice due diligence.
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Lin, Y., M. S. Sim, and S. Ono. "Multiple-sulfur isotope effects during photolysis of carbonyl sulfide." Atmospheric Chemistry and Physics Discussions 11, no. 5 (May 9, 2011): 14233–58. http://dx.doi.org/10.5194/acpd-11-14233-2011.
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Abstract. Laboratory experiments were carried out to determine sulfur isotope effects during ultraviolet photolysis of carbonyl sulfide (OCS) to carbon monoxide (CO) and elemental sulfur (S0). The OCS gas at 3.7 to 501 mbar was irradiated with or without a N2 bath gas using a 150 W Xe arc lamp. Sulfur isotope ratios for the product S0 and residual OCS were analyzed by an isotope ratio mass-spectrometer with SF6 as the analyte gas. The isotope effect after correction for the reservoir effects is −6.8 ‰ for the ratio 34S/32S, where product S0 is depleted in heavy isotopes. The magnitude of the overall isotope effect is not sensitive to the addition of N2 but increases to −9.5 ‰ when radiation of λ >285 nm is used. The measured isotope effect reflects that of photolysis as well as the subsequent sulfur abstraction (from OCS) reaction. The magnitude of isotope effects for the abstraction reaction is estimated by transition state theory to be between −18.9 and −3.1 ‰ for 34S which gives the photolysis isotope effect as −10.5 to +5.3 ‰. The measured isotope effects are found to be δ33S/δ34S = 0.534±0.005 and δ36S/δ34S = 1.980±0.021. These values are largely mass-dependent but statistically differ from canonical values for mass-dependent fractionation of 0.515 and 1.90, respectively. The result demonstrates that the OCS photolysis may not produce large isotope effect of more than about 10 \\permil, and can be the major source of background stratospheric sulfate aerosol (SSA) during volcanic quiescence.
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Lin, Y., M. S. Sim, and S. Ono. "Multiple-sulfur isotope effects during photolysis of carbonyl sulfide." Atmospheric Chemistry and Physics 11, no. 19 (October 14, 2011): 10283–92. http://dx.doi.org/10.5194/acp-11-10283-2011.
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Abstract. Laboratory experiments were carried out to determine sulfur isotope effects during ultraviolet photolysis of carbonyl sulfide (OCS) to carbon monoxide (CO) and elemental sulfur (S0). The OCS gas at 3.7 to 501 mbar was irradiated with or without a N2 bath gas using a 150 W Xe arc lamp. Sulfur isotope ratios for the product S0 and residual OCS were analyzed by an isotope ratio mass-spectrometer with SF6 as the analyte gas. The isotope fractionation after correction for the reservoir effects is −6.8‰ for the ratio 34S/32S, where product S0 is depleted in heavy isotopes. The magnitude of the overall isotope effect is not sensitive to the addition of N2 but increases to −9.5‰ when radiation of λ > 285 nm is used. The measured isotope effect reflects that of photolysis as well as the subsequent sulfur abstraction (from OCS) reaction. The magnitude of isotope effects for the abstraction reaction is estimated by transition state theory to be between −18.9 and −3.1‰ for 34S which gives the photolysis isotope effect as −10.5 to +5.3‰. The observed triple isotope coefficients are ln(δ34S + 1)/ln(δ34S + 1) = 0.534 ± 0.005 and ln(δ36S + 1)/ln(δ34S + 1) = 1.980 ± 0.021. These values differ from canonical values for mass-dependent fractionation of 0.515 and 1.90, respectively. The result demonstrates that the OCS photolysis does not produce large isotope effects of more than about 10‰ for 34S/32S, and can be the major source of background stratospheric sulfate aerosol (SSA) during volcanic quiescence.
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Harris, E., B. Sinha, P. Hoppe, J. N. Crowley, S. Ono, and S. Foley. "Sulfur isotope fractionation during oxidation of sulfur dioxide: gas-phase oxidation by OH radicals and aqueous oxidation by H<sub>2</sub>O<sub>2</sub>, O<sub>3</sub> and iron catalysis." Atmospheric Chemistry and Physics Discussions 11, no. 8 (August 25, 2011): 23959–4002. http://dx.doi.org/10.5194/acpd-11-23959-2011.
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Abstract. The oxidation of SO2 to sulfate is a key reaction in determining the role of sulfate in the environment through its effect on aerosol size distribution and composition. Sulfur isotope analysis has been used to investigate sources and chemistry of sulfur dioxide and sulfate in the atmosphere, however interpretation of measured sulfur isotope ratios is challenging due to a lack of reliable information on the isotopic fractionation involved in major transformation pathways. This paper presents measurements of the fractionation factors for the major atmospheric oxidation reactions for SO2: Gas-phase oxidation by OH radicals, and aqueous oxidation by H2O2, O3 and a radical chain reaction initiated by iron. The measured fractionation factor for 34S/32S during the gas-phase reaction is αOH = (1.0089±0.0007) − ((4±5)×10−5) T(°C). The measured fractionation factor for 34S/32S during aqueous oxidation by H2O2 or O3 is αaq=(1.0167±0.0019) − ((8.7±3.5) ×10−5) T(°C). The observed fractionation during oxidation by H2O2 and O3 appeared to be controlled primarily by protonation and acid-base equilbria of S(IV) in solution, and there was no significant difference between the fractionation produced by the two oxidants within the experimental error. The isotopic fractionation factor from a radical chain reaction in solution catalysed by iron is αFe = (0.989±0.0043) at 19 °C for 34S/32S. Fractionation was mass-dependent with regards to 33S for all the reactions investigated. The radical chain reaction mechanism was the only measured reaction that had a faster rate for the light isotopes, and will be particularly useful to determine the importance of the transition-metal catalysed oxidation pathway.
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Awadh, Salih Muhammad, and Zinah Saleem Al-Ankaz. "SULFUR ISOTOPES GEOCHEMISTRY OF THE BITUMINOUS FATHA EVAPORATES IN FATHA FORMATION, HIT–ABU JIR AREA, WESTERN IRAQ." Iraqi Geological Journal 39-49, no. 2 (December 31, 2016): 34–45. http://dx.doi.org/10.46717/igj.39-49.2.3ms-2016-12-26.
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Fatha Formation (Middle Miocene) in Hit area, western Iraq was targeted for this study. Pure gypsum, bituminous gypsum and native sulfur were investigated for δ34S, FTIR and SEM to define the historical scenario of the paleo-environment and the relationship between sulfur, bitumen and evaporates (gypsum and anhydrite). SEM along with FTIR clarified that the bitumen were injected into the gypsum under high stress generated from the basin hydrodynamic pressure. The pure gypsum samples are enriched in heavy sulfur isotope and characterized by narrow range of δ34S values (22.5 – 23.52 ‰) indicating a primary gypsum formed by direct precipitation from saline without bacterial activity. The lighter sulfur values (14.13 – 14.42 ‰) in the sulfur samples of the Abu-Jir area indicate a bacterial reduction of gypsum into native sulfur. The difference between δ34S values in sulfur deposits in the Abu-Jir area (14.13 – 14.42 ‰) and in the Mishraq Mine (9.51 ‰) is clearly attributed to the remnant of gypsum as impurities within sulfur deposits in the Abu-Jir area. The bitumen sample has depleted in δ34S value (-2.57 ‰), whilst the bituminous gypsum samples have enriched (22.07 – 24.11 ‰). This high variation reflects the highly isotopic fractionation between oxic and anoxic environments.
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Vavilin, Vasily, Lyudmila Lokshina, and Sergey Rytov. "Using kinetic isotope effect to evaluate the significance of the sequential and parallel steps: formation of microbial consortium during reversible anaerobic methane oxidation coupled with sulfate reduction." Water Science and Technology 79, no. 11 (June 1, 2019): 2056–67. http://dx.doi.org/10.2166/wst.2019.201.
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Abstract The purpose of this study was to describe the dynamics of anaerobic oxidation of methane (AOM) coupled with sulfate reduction (SR) using experimental data from a continuous incubation experiments published earlier in order to show that formation of consortia of anaerobic archaea (ANME) and Desulfosarcina-like bacteria (DSS) may have a significant effect on sulfur isotope fractionation. The dynamic simulation of reversible AOM by ANME coupled with SR by DSS was performed. This simulation took into account biomass growth and fractionation of stable isotopes of sulfur. Two kinetic schemes with and without ANME + DSS consortium formation were tested. The respective models were applied at five influent methane concentrations. A good fit to experimental data was obtained only when assuming active ANME and DSS biomass accumulation. The assumption about incorporation of reversibility of anaerobic methane oxidation and sulfate reduction did not improve the model's fit to experimental data. In accordance with both the models, sulfur isotope fractionation was smallest for the highest influent methane concentration. The model considering the formation of consortia of ANME + DSS is proved to be more appropriate.
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Yartsev, E. I., I. V. Vikentyev, and N. I. Eremin. "Isotopic composition and geochemical features of ores of Dzhusa pyrite-polymetallic deposit (South Urals)." Moscow University Bulletin. Series 4. Geology, no. 4 (August 28, 2019): 78–83. http://dx.doi.org/10.33623/0579-9406-2019-4-78-83.
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The sulfur isotopic composition was studied for the main morphological types and generation of sulfides composing the ore of the Dzhusinsky deposit, and the content of trace elements was analyzed using the highly sensitive method of mass spectrometry with inductively coupled plasma and laser sampling (LA-ICP-MS). Both types of studies were performed for ore deposits for the first time. According to the geochemistry of sulfur isotopes, its deep magmatic source was reconstructed, which made a predominant contribution to the ore-forming fluid. Using the modules of the STATISTICA, correlations were calculated and the patterns of distribution of micro impurities in sulfide minerals were revealed.
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Hattori, Shohei, Kazuki Kamezaki, and Naohiro Yoshida. "Constraining the atmospheric OCS budget from sulfur isotopes." Proceedings of the National Academy of Sciences 117, no. 34 (August 5, 2020): 20447–52. http://dx.doi.org/10.1073/pnas.2007260117.
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Carbonyl sulfide (OCS), the most abundant sulfur-containing gas in the atmosphere, is used as a proxy for photosynthesis rate estimation. However, a large missing source of atmospheric OCS has been inferred. Sulfur isotope measurements (34S/32S ratio andδ34S) on OCS are a feasible tool to distinguish OCS sources from oceanic and anthropogenic emissions. Here we present the latitudinal (north–south) observations of OCS concentration andδ34S within Japan. The observedδ34S of OCS of 9.7 to 14.5‰ reflects source and sink effects. Particularly in winter, latitudinal decreases inδ34S values of OCS were found to be correlated with increases in OCS concentrations, resulting an intercept of (4.7 ± 0.8)‰ in the Keeling plot approach. This result implies the transport of anthropogenic OCS emissions from the Asian continent to the western Pacific by the Asian monsoon outflow. The estimated backgroundδ34S of OCS in eastern Asia is consistent with theδ34S of OCS previously reported in Israel and the Canary Islands, suggesting that the backgroundδ34S of OCS in the Northern Hemisphere ranges from 12.0 to 13.5‰. Our constructed sulfur isotopic mass balance of OCS revealed that anthropogenic sources, not merely oceanic sources, account for much of the missing source of atmospheric OCS.
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Jiang, Yongguo, Yinliang Cui, Hongliang Nian, Changhua Yang, Yahui Zhang, Mingyong Liu, Heng Xu, Jinjun Cai, and Hesong Liu. "The Origin of the Caiyuanzi Pb–Zn Deposit in SE Yunnan Province, China: Constraints from In Situ S and Pb Isotopes." Minerals 13, no. 2 (February 8, 2023): 238. http://dx.doi.org/10.3390/min13020238.
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Located at the intersection of the Tethys and Pacific Rim metallogenic belts, the Laojunshan polymetallic metallogenic province in SE Yunnan Province hosts many large-scale W–Sn and Sn–Zn polymetallic deposits. The newly discovered Caiyuanzi medium-sized Pb–Zn deposit is located in the northern part of this province and has eight sulfide ore bodies. All the ore bodies occur in the siliceous rocks of the Lower Devonian Pojiao Formation (D1p). The ore bodies are conformable with stratigraphy and controlled by a lithologic horizon. The sulfide ores have banded or laminated structures. The ore minerals are mainly pyrite, chalcopyrite, sphalerite, and galena. In this study, in situ sulfur and lead isotopes were used to constrain the origin of the Caiyuanzi Pb–Zn deposit. The results show that the in situ δ34S values of pyrite, chalcopyrite, and sphalerite range from 0.1‰ to 6.0‰, with an average of 4.7‰. This δ34S signature reflects the mixing between magmatic-derived and reduced seawater sulfate sulfur. The in situ Pb isotopes characteristics of pyrite, galena, and sphalerite suggest that the sulfur and lead of ore minerals come from the upper crust. Integrating the data obtained from the studies including regional geology, ore geology, and S–Pb isotope geochemistry, we proposed that the Caiyuanzi Pb–Zn deposit is a hydrothermal deposit formed by sedimentary exhalative and magmatic hydrothermal superimposition.
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Baartman, Sophie L., Maarten C. Krol, Thomas Röckmann, Shohei Hattori, Kazuki Kamezaki, Naohiro Yoshida, and Maria Elena Popa. "A GC-IRMS method for measuring sulfur isotope ratios of carbonyl sulfide from small air samples." Open Research Europe 1 (September 13, 2021): 105. http://dx.doi.org/10.12688/openreseurope.13875.1.
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A new system was developed for measuring sulfur isotopes Δ33S and Δ34S from atmospheric carbonyl sulfide (COS or OCS) on small air samples of several liters, using a pre-concentration and gas chromatography – isotope ratio mass spectrometry (GC-IRMS) method. Measurements of COS isotopes provide a tool for quantifying the COS budget, which will help towards better understanding climate feedback mechanisms. For a 4 liter sample at ambient COS mixing ratio, ~500 parts per trillion (ppt), we obtain a reproducibility error of 2.1 ‰ for Δ33S and 0.4 ‰ for Δ34S. After applying corrections, the uncertainty for an individual ambient air sample measurement is 3.3 ‰ for Δ33S and 0.9 ‰ for Δ34S. The ability to measure small samples allows application to a global-scale sampling program with limited logistical effort. To illustrate the application of this newly developed system, we present a timeseries of ambient air measurements, during the fall and winter of 2020 and 2021 in Utrecht, the Netherlands. The observed background values were Δ33S = 1.0 ± 3.4 ‰ and Δ34S = 15.5 ± 0.8 ‰ (VCDT). The maximum observed COS mixing ratios was 620 ppt, suggesting that the Netherlands receives little COS-containing anthropogenic emissions. We observed a change in COS mixing ratio and sometimes also Δ34S with different air mass origin, as modelled with the Hybrid Single-Particle Lagrangian Integrated Trajectory model (HYSPLIT) backward trajectory analyses. An increasing trend of 40 ppt was observed in the COS mixing ratio between fall and winter, which is consistent with the expected seasonal cycle in the Netherlands. Additionally, we present the results from samples taken inside a highway tunnel in Utrecht to characterize vehicle COS emissions and isotopic composition. The vehicle emissions were small, with a COS/CO2 ratio of 0.4 ppt/ppm; the isotopic signatures are depleted relatively to background atmospheric COS.
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Baartman, Sophie L., Maarten C. Krol, Thomas Röckmann, Shohei Hattori, Kazuki Kamezaki, Naohiro Yoshida, and Maria Elena Popa. "A GC-IRMS method for measuring sulfur isotope ratios of carbonyl sulfide from small air samples." Open Research Europe 1 (March 8, 2022): 105. http://dx.doi.org/10.12688/openreseurope.13875.2.
Full textAbstract:
A new system was developed for measuring sulfur isotopes δ 33S and δ 34S from atmospheric carbonyl sulfide (COS) on small air samples of several liters, using pre-concentration and gas chromatography – isotope ratio mass spectrometry (GC-IRMS). Measurements of COS isotopes provide a tool for quantifying the COS budget, which will help towards better understanding climate feedback mechanisms. For a 4 liter sample at ambient COS mixing ratio, ~500 parts per trillion (ppt), we obtain a reproducibility error of 2.1 ‰ for δ 33S and 0.4 ‰ for δ 34S. After applying corrections, the uncertainty for an individual ambient air sample measurement is 2.5 ‰ for δ 33S and 0.9 ‰ for δ 34S. The ability to measure small samples allows application to a global-scale sampling program with limited logistical effort. To illustrate the application of this newly developed system, we present a timeseries of ambient air measurements, during the fall and winter of 2020 and 2021 in Utrecht, the Netherlands. The observed background values were δ 33S = 1.0 ± 3.4 ‰ and δ 34S = 15.5 ± 0.8 ‰ (VCDT). The maximum observed COS mixing ratios was only 620 ppt. This, in combination with the relatively high δ 34S suggests that the Netherlands receives little COS-containing anthropogenic emissions. We observed a change in COS mixing ratio and δ 34S with different air mass origin, as modelled with HYSPLIT backward trajectory analyses. An increase of 40 ppt in mean COS mixing ratio was observed between fall and winter, which is consistent with the expected seasonal cycle in the Netherlands. Additionally, we present the results of samples from a highway tunnel to characterize vehicle COS emissions and isotopic composition. The vehicle emissions were small, with COS/CO 2 being 0.4 ppt/ppm; the isotopic signatures are depleted relatively to background atmospheric COS.
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Watson, Elizabeth Burke, Alejandro Hinojosa-Corona, Johannes R. Krause, Juan Carlos Herguera, Julianna McDonnell, Karen Raquel Villegas Villegas Manríquez, Michelle E. Gannon, and Andrew B. Gray. "Lagoon Biogeochemical Processing is Reflected in Spatial Patterns of Sediment Stable Isotopic Ratios." Journal of Marine Science and Engineering 8, no. 11 (November 3, 2020): 874. http://dx.doi.org/10.3390/jmse8110874.
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The spatial analysis of biota, particulate organic matter, and sediments for stable isotopes of carbon (δ13C), nitrogen (δ15N), and sulfur (δ34S) have proved useful for identifying patterns in productivity, nutrient pollution, and relationships between biological and physiochemical variables at the local and global scales. Yet such approaches are rarely applied to studies of lagoon or estuarine metabolism. Focusing on Bahía San Quintín, a heterotrophic seagrass-dominated lagoon on the Pacific coast of Baja California, México, we report on spatial patterns in surficial sediment CNS stable isotopic ratios as tracers of lagoon biogeochemical function. Stable nitrogen isotopes highlighted potential spatial variability in the balance between denitrification and nitrogen-fixation within the lagoon and identified an association between elevated δ15N levels and oyster culture, suggesting that oyster presence may be enhancing N2 production. Spatial patterns in δ34S covaried with sediment particle size, underlining the importance of sediment texture in determining the depth of sub-oxic-anoxic redox zones. Sediment carbon stable isotope ratios highlighted the lack of incorporation of seagrass carbon into seagrass meadow sediments, thus emphasizing the importance of phytoplankton or microphytobenthos for carbon accumulation in seagrass meadows. This report highlights the value of sediment isotopic values in corroborating spatial patterns in estuarine metabolism or macronutrient processing identified from chamber or flux-based studies. Stable isotope mapping can provide a useful addition to assessment of estuarine metabolism, or act as a stand-alone tool for generating hypotheses, identifying the influence of spatial gradients, and/or suggesting prime locations for investigation of microbial abundance or function.
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Altwegg, K., H. Balsiger, M. Combi, J. De Keyser, M. N. Drozdovskaya, S. A. Fuselier, T. I. Gombosi, et al. "Molecule-dependent oxygen isotopic ratios in the coma of comet 67P/Churyumov–Gerasimenko." Monthly Notices of the Royal Astronomical Society 498, no. 4 (September 10, 2020): 5855–62. http://dx.doi.org/10.1093/mnras/staa2701.
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ABSTRACT The ratios of the three stable oxygen isotopes 16O, 17O, and 18O on the Earth and, as far as we know in the Solar system, show variations on the order of a few per cent at most, with a few outliers in meteorites. However, in the interstellar medium there are some highly fractionated oxygen isotopic ratios in some specific molecules. The goal of this work is to investigate the oxygen isotopic ratios in different volatile molecules found in the coma of comet 67P/Churyumov–Gerasimenko and compare them with findings from interstellar clouds in order to assess commonalities and differences. To accomplish this goal, we analysed data from the ROSINA instrument on Rosetta during its mission around the comet. 16O/18O ratios could be determined for O2, methanol, formaldehyde, carbonyl sulfide, and sulfur monoxide/dioxide. For O2 the 16O/17O ratio is also available. Some ratios are strongly enriched in the heavy isotopes, especially for sulfur-bearing molecules and formaldehyde, whereas for methanol the ratios are compatible with the ones in the Solar system. O2 falls in-between, but its oxygen isotopic ratios clearly differ from water, which likely rules out an origin of O2 from water, be it by radiolysis, dismutation during sublimation, or the Eley–Rideal process from water ions hitting the nucleus as postulated in the literature.
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Johnston, David T. "Multiple sulfur isotopes and the evolution of Earth's surface sulfur cycle." Earth-Science Reviews 106, no. 1-2 (May 2011): 161–83. http://dx.doi.org/10.1016/j.earscirev.2011.02.003.
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Morgan, Mark D. "Modeling excess sulfur deposition on wetland soils using stable sulfur isotopes." Water, Air, & Soil Pollution 79, no. 1-4 (January 1995): 299–307. http://dx.doi.org/10.1007/bf01100443.
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