Multiple sulfur isotopes fractionations associated with abiotic sulfur transformations in Yellowstone National Park geothermal springs

Background: The paper presents a quantification of main (hydrogen sulfide and sulfate), as well as of intermediate sulfur species (zero-valent sulfur (ZVS), thiosulfate, sulfite, thiocyanate) in the Yellowstone National Park (YNP) hydrothermal springs and pools. We combined these measurements with the measurements of quadruple sulfur isotope composition of sulfate, hydrogen sulfide and zero-valent sulfur. The main goal of this research is to understand multiple sulfur isotope fractionation in the system, which is dominated by complex, mostly abiotic, sulfur cycling. Results: Water samples from six springs and pools in the Yellowstone National Park were characterized by pH, chloride to sulfate ratios, sulfide and intermediate sulfur species concentrations. Concentrations of sulfate in pools indicate either oxidation of sulfide by mixing of deep parent water with shallow oxic water, or surface oxidation of sulfide with atmospheric oxygen. Thiosulfate concentrations are low (<6 mu mol L-1) in the pools with low pH due to fast disproportionation of thiosulfate. In the pools with higher pH, the concentration of thiosulfate varies, depending on different geochemical pathways of thiosulfate formation. The delta S-34 values of sulfate in four systems were close to those calculated using a mixing line of the model based on dilution and boiling of a deep hot parent water body. In two pools delta S-34 values of sulfate varied significantly from the values calculated from this model. Sulfur isotope fractionation between ZVS and hydrogen sulfide was close to zero at pH < 4. At higher pH zero-valent sulfur is slightly heavier than hydrogen sulfide due to equilibration in the rhombic sulfur-polysulfide - hydrogen sulfide system. Triple sulfur isotope (S-32, S-33, S-34) fractionation patterns in waters of hydrothermal pools are more consistent with redox processes involving intermediate sulfur species than with bacterial sulfate reduction. Small but resolved differences in Delta S-33 among species and between pools are observed. Conclusions: The variation of sulfate isotopic composition, the origin of differences in isotopic composition of sulfide and zero-valent sulfur, as well as differences in Delta S-33 of sulfide and sulfate are likely due to a complex network of abiotic redox reactions, including disproportionation pathways

Hydrogen Cyanide Accumulation and Transformations in Non-polluted Salt Marsh Sediments

While cyanide is known to be produced by many organisms, including plants, bacteria, algae, fungi and some animals, it is generally thought that high levels of cyanide in aquatic systems require anthropogenic sources. Here, we report accumulation of relatively high levels of cyanide in non-polluted salt marsh sediments (up to 230 μmol kg[superscript −1]). Concentrations of free cyanide up to 1.92 μmol L[superscript −1], which are toxic to aquatic life, were detected in the pore-waters. Concentration of total (free and complexed) cyanide in the pore-waters was up to 6.94 μmol L[superscript −1]. Free cyanide, which is released to the marsh sediments, is attributed to processes associated with decomposition of cord grass, Spartina alterniflora, roots and possibly from other sources. This cyanide is rapidly complexed with iron and adsorbed on sedimentary organic matter. The ultimate cyanide sink is, however, associated with formation of thiocyanate by reaction with products of sulfide oxidation by Fe(III) minerals, especially polysulfides. The formation of thiocyanate by this pathway detoxifies two poisonous compounds, polysulfides and hydrogen cyanide, preventing release of free hydrogen cyanide from salt marsh sediments into overlying water or air

Hydrogen Cyanide Accumulation and Transformations in Non-polluted Salt Marsh Sediments

While cyanide is known to be produced by many organisms, including plants, bacteria, algae, fungi and some animals, it is generally thought that high levels of cyanide in aquatic systems require anthropogenic sources. Here, we report accumulation of relatively high levels of cyanide in non-polluted salt marsh sediments (up to 230 mu mol kg(-1)). Concentrations of free cyanide up to 1.92 mu mol L-1, which are toxic to aquatic life, were detected in the pore-waters. Concentration of total (free and complexed) cyanide in the pore-waters was up to 6.94 mu mol L-1. Free cyanide, which is released to the marsh sediments, is attributed to processes associated with decomposition of cord grass, Spartina alterniflora, roots and possibly from other sources. This cyanide is rapidly complexed with iron and adsorbed on sedimentary organic matter. The ultimate cyanide sink is, however, associated with formation of thiocyanate by reaction with products of sulfide oxidation by Fe(III) minerals, especially polysulfides. The formation of thiocyanate by this pathway detoxifies two poisonous compounds, polysulfides and hydrogen cyanide, preventing release of free hydrogen cyanide from salt marsh sediments into overlying water or air

Soil temperature estimation at different depths, using remotely-sensed data

Soil temperatures at different depths down the soil profile are important agro-meteorological indicators which are necessary for ecological modeling and precision agricultural activities. In this paper, using time series of soil temperature (ST) measured at different depths (0, 5, 10, 20, and 40 cm) at agro-meteorological stations in northern China as reference data, ST was estimated from land surface temperature (LST) and normalized difference vegetation index (NDVI) derived from AQUA/TERRA MODIS data, and solar declination (Ds) in univariate and multivariate linear regression models. Results showed that when daytime LST is used as predictor, the coefficient of determination (R2) values decrease from the 0 cm layer to the 40 cm layer. Additionally, with the use of nighttime LST as predictor, the R2 values were relatively higher at 5, 10 and 15 cm depths than those at 0, 20 and 40 cm depths. It is further observed that the multiple linear regression models for soil temperature estimation outperform the univariate linear regression models based on the root mean squared errors (RMSEs) and R2. These results have demonstrated the potential of MODIS data in tandem with the Ds parameter for soil temperature estimation at the upper layers of the soil profile where plant roots grow in. To the best of our knowledge, this is the first attempt at the synergistic use of LST, NDVI and Ds for soil temperature estimation at different depths of the upper layers of the soil profile, representing a significant contribution to soil remote sensing

Antibiotic use among hospitalised patients in Sierra Leone: a national point prevalence survey using the WHO survey methodology

Objective Inappropriate use of antibiotics is a major driver of antibiotic resistance. A few studies conducted in Africa have documented that about half of hospitalised patients who receive antibiotics should not have received them. A few hospital-based studies that have been conducted in Sierra Leone have documented a high usage of antibiotics in hospitals. Therefore, we conducted a nationwide point prevalence survey on antibiotic use among hospitalised patients in Sierra Leone.Design We conducted a hospital-based, cross-sectional survey on the use of antibiotics using the WHO point prevalence survey methodology.Setting The study was conducted in 26 public and private hospitals that are providing inpatient healthcare services.Participants All patients admitted to paediatric and adult inpatient wards before or at 08:00 on the survey date were enrolled.Outcome measures Prevalence of antibiotic use, antibiotics Access, Watch and Reserve (AWaRe) categorisation, indication for antibiotic use prevalence and proportion of bacteria culture done.Results Of the 1198 patient records reviewed, 883 (73.7%, 95% CI 71.1% to 76.2%) were on antibiotics. Antibiotic use was highest in the paediatric wards (306, 85.7%), followed by medical wards (158, 71.2%), surgical wards (146, 69.5%), mixed wards (97, 68.8%) and lowest in the obstetrics and gynaecology wards (176, 65.7%). The most widely prescribed antibiotics were metronidazole (404, 22.2%), ceftriaxone (373, 20.5%), ampicillin (337, 18.5%), gentamicin (221, 12.1%) and amoxicillin (90, 5.0%). Blood culture was only done for one patient and antibiotic treatments were given empirically. The most common indication for antibiotic use was community-acquired infection (484, 51.9%) followed by surgical prophylaxis (222, 23.8%).Conclusion There was high usage of antibiotics in hospitals in Sierra Leone as the majority of patients admitted received an antibiotic. This has the potential to increase the burden of antibiotic resistance in the country. We, therefore, recommend the establishment of hospital antimicrobial stewardship programmes according to the WHO core components

Performance prediction and validation of equilibrium modeling for gasification of cashew nut shell char

Cashew nut shell, a waste product obtained during deshelling of cashew kernels, had in the past been deemed unfit as a fuel for gasification owing to its high occluded oil content. The oil, a source of natural phenol, oozes upon gasification, thereby clogging the gasifier throat, downstream equipment and associated utilities with oil, resulting in ineffective gasification and premature failure of utilities due to its corrosive characteristics. To overcome this drawback, the cashew shells were de-oiled by charring in closed chambers and were subsequently gasified in an autothermal downdraft gasifier. Equilibrium modeling was carried out to predict the producer gas composition under varying performance influencing parameters, viz., equivalence ratio (ER), reaction temperature (RT) and moisture content (MC). The results were compared with the experimental output and are presented in this paper. The model is quite satisfactory with the experimental outcome at the ER applicable to gasification systems, i.e., 0.15 to 0.30. The results show that the mole fraction of (i) H2, CO and CH4 decreases while (N2 + H2O) and CO2 increases with ER, (ii) H2 and CO increases while CH4, (N2 + H2O) and CO2 decreases with reaction temperature, (iii) H2, CH4, CO2 and (N2 + H2O) increases while CO decreases with moisture content. However at an equivalence ratio less than 0.15, the model predicts an unrealistic composition and is observed to be non valid below this ER