Determination of Total Sulfur in Agricultural Samples by High-Resolution Continuum Source Flame Molecular Absorption Spectrometry

Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)

(Table 1) Sulfur isotopes, total sulfur, and degree of oxidation of basalt samples from DSDP Hole 69-504B and 70-504B

About 150 basalt samples from Hole 504B, near the Costa Rica Rift were analyzed for sulfur content and sulfur-isotope composition. The basement in Hole 504B can be divided into an upper part, which has oxidative alteration (274.5-550 m below sea floor), and a lower part, which has nonoxidative alteration (550-835 m below sea floor) (the interval from 540 to 585 meters actually is transitional). This division is reflected in both the sulfur content and the sulfurisotope composition. Oxidative alteration of basalts by sea water at low temperatures has resulted in a depletion in sulfur in the upper part of the hole (mostly less than 600 ppm S) as compared to fresh sulfur-saturated oceanic tholeiites (900-1200 ppm S). High amounts of sulfur in the lower part of the hole are a result of precipitation of secondary pyrite under non-oxidative or weakly oxidative conditions from solutions which dissolved igneous sulfides. The average sulfur-isotope composition of the primary igneous sulfides is d34S = -0.01 per mil, which is close to the assumed mantle sulfur composition (d34S = 0 per mil. Pyrite and sulfate sulfur extracted together in a separate preparation step (as "pyrite-sulfate" sulfur) indicate addition of sea-water sulfate to the upper part of the basalts. The d34S of secondary pyrite isolated by hand-picking varies between -8.0 and +5.8 per mil; the "pyrite-sulfate" sulfur (d34S = -4.8 to +10.5 per mil), as well as that of the isolated pyrite, may have originated in the precipitation of pyrite from solutions containing sulfur from the dissolution of igneous sulfides, but addition of sulfur transported by hydrothermal solutions cannot be excluded.

(Table 1) Sulfur isotopes, total sulfur, and degree of oxidation of basalt samples from DSDP Holes 69-504B and 70-504B

Whole-rock basalt samples from the upper half of Deep Sea Drilling Project Hole 504B have oxygen-isotope compositions typical of mid-ocean-ridge basalts which have experienced a moderate degree of low-temperature alteration by sea water. By contrast, d18O values in the lower half of the hole correspond to basalts which have experienced almost no detectable oxygen-isotope alteration. These observations suggest that the overall water/rock ratio was lower in the lower half of the drilled crust. A correlation between d18O values and 87Sr/86Sr ratios suggests that the water/rock ratio, rather than temperature variation, was the main factor determining basalt d18O values. Hydrogen-isotope data appear to be consistent with a low water/rock ratio in the lower part of the crust.

Multiple sulfur isotope analyses support a magmatic model for the volcanogenic massive sulfide deposits of the Teutonic Bore volcanic complex, Yilgarn Craton, Western Australia

We report sensitive high mass resolution ion microprobe, stable isotopes (SHRIMP SI) multiple sulfur isotope analyses (32S, 33S, 34S) to constrain the sources of sulfur in three Archean VMS deposits—Teutonic Bore, Bentley, and Jaguar—from the Teutonic Bore volcanic complex of the Yilgarn Craton, Western Australia, together with sedimentary pyrites from associated black shales and interpillow pyrites. The pyrites from VMS mineralization are dominated by mantle sulfur but include a small amount of slightly negative mass-independent fractionation (MIF) anomalies, whereas sulfur from the pyrites in the sedimentary rocks has pronounced positive MIF, with ∆33S values that lie between 0.19 and 6.20‰ (with one outlier at −1.62‰). The wall rocks to the mineralization include sedimentary rocks that have contributed no detectable positive MIF sulfur to the VMS deposits, which is difficult to reconcile with the leaching model for the formation of these deposits. The sulfur isotope data are best explained by mixing between sulfur derived from a magmatic-hydrothermal fluid and seawater sulfur as represented by the interpillow pyrites. The massive sulfide lens pyrites have a weighted mean ∆33S value of −0.27 ± 0.05‰ (MSWD = 1.6) nearly identical with −0.31 ± 0.08‰ (MSWD = 2.4) for pyrites from the stringer zone, which requires mixing to have occurred below the sea floor. We employed a two-component mixing model to estimate the contribution of seawater sulfur to the total sulfur budget of the two Teutonic Bore volcanic complex VMS deposits. The results are 15 to 18% for both Teutonic Bore and Bentley, much higher than the 3% obtained by Jamieson et al. (2013) for the giant Kidd Creek deposit. Similar calculations, carried out for other Neoarchean VMS deposits give value between 2% and 30%, which are similar to modern hydrothermal VMS deposits. We suggest that multiple sulfur isotope analyses may be used to predict the size of Archean VMS deposits and to provide a vector to ore deposit but further studies are needed to test these suggestions.

Analysis of sulfur-containing compounds in crude oils by comprehensive two-dimensional gas chromatography with sulfur chemiluminescence detection

This paper reports an analytical method for separating, identifying, and quantifying sulfur-containing compounds in crude oil fraction (IBP-360degreesC) samples based on comprehensive two-dimensional gas chromatography coupled with a sulfur chemiluminescence detector. Various sulfur-containing compounds and their groups were analyzed with one direct injection. 3620 peaks were detected including 1722 thiols/thioethers/ disulfides/1-ring thiophenes, 953 benzothiophenes, 704 dibenzothiophenes, and 241 benzonaphthothiophenes. The target sulfur compounds and their groups were identified based on the group separation feature and structured retention of comprehensive two-dimensional gas chromatography as well as standard substances. The quantitative analysis of major sulfur-containing compounds and total sulfur was based on the linear response of the sulfur chemiluminescence detector using the internal standard method. The sulfur contents of target sulfur compounds and their groups in 4 crude oil fractions were also determined. The recoveries for standard sulfur-containing compounds were in the range of 90-102%. The quantitative result of total sulfur in the Oman crude oil fraction sample was compared with those from ASTM D 4294 standard method (total S by X-ray fluorescence spectrometry), the relative deviation (RD%) was 4.2% and the precision of the method satisfactory.

Determination of sulfur-containing compounds in diesel oils by comprehensive two-dimensional gas chromatography with a sulfur chemiluminescence detector

This article reports an analytical method for separating, identifying and quantitating sulfur-containing compounds and their groups in diesel oils (170-400degreesC) using comprehensive two-dimensional gas chromatography coupled with a sulfur chemiluminescence detector. The identification of target compounds and their groups was based on standard substances, the group separation feature and the-effect of comprehensive two-dimensional gas chromatography. The quantitative analysis on major sulfur compounds and total sulfur was carried out based on the linear response of sulfur chemiluminescence detector and the internal standards method. The results of total sulfur determination in the samples were compared with those from ASTM D 4294 standard method, the R.S.D. percentage were <6.02%, correctness of this method can meet the industrial requirement. To the end, the method developed was used to investigate the sulfur-containing compounds in different diesel oils, the result shows that the distribution of sulfur-containing compounds in diesel oils from different process units are apparently different. The sulfur compounds in fluid catalytic cracking (FCC), residuum fluid catalytic cracking (RFCC) diesel oils mainly exist in the form of alkyl-substituted dibenzothiophenes that add up to about 40-50% of the total sulfur, while this number is only 6-8 and 20-28% in visbreaking (VB) and delayed-coking (DC) diesel oils, respectively. (C) 2003 Elsevier B.V. All rights reserved.

Distribution of organic and reduced sulfur forms in marsh soils of coastal Louisiana

Soil samples from a Louisiana Barataria Basin brackish marshes were fractionated into acid-volatile sulfides (AVS), HCl-soluble sulfur, elemental sulfur, pyrite sulfur, ester-sulfate sulfur, and carbon-bonded sulfur. Inorganic sulfur composed 13% of total sulfur in brackish marsh soil with HCl-soluble sulfur representing 63–92% of the inorganic sulfur fraction. AVS represented less than 1% of the total sulfur pool. Pyrite sulfur and elemental sulfur together accounted for 8–33% of the inorganic sulfur pool. Organic sulfur, in the forms of ester-sulfate sulfur and carbon-bonded sulfur, was the most dominant pool representing the majority of total sulfur in brackish marsh. Results were compared to values reported for fresh and salt marshes. Reported inorganic sulfur fractions were greater in adjacent marshes, constituting 24% of total sulfur in salt marsh, and 22% in freshwater marshes. Along a salinity gradient, HCl-soluble sulfur represented 78–86% of the inorganic sulfur fraction in fresh, brackish, and salt marsh. Organic sulfur in the forms of ester-sulfate sulfur and carbon-bonded sulfur was the major constituent (76–87%) of total sulfur in all marshes. Reduced sulfur species, except elemental sulfur, increased seaward along the salinity gradient. Accumulation of reduced sulfur forms through sedimentation processes was significant in marsh energy flow in fresh, brackish and salt marshes.

Suitability of extractants for predicting available sulfur in natural grassland in the Inner Mongolia steppe of China

It was the objective of this study to compare the suitability of different extractants for predicting the availability of sulfur (S) in natural grassland in a sulfur response trial on three different soil types in the Inner Mongolia steppe of China. For soil analysis, seven different extractants have been employed. The inorganic SO4-S concentration was determined by ion chromatography. Additionally, in the Ca(H-2-PO4)(2) extract the total soluble S was determined employing turbidimetry. Weak salt solutions (0.15% CaCl2, Ca(H2PO4)(2), and KH2PO4) extracted similar amounts Of SO4-S. Extraction with 0.025 M KCl provided the lowest SO4-S values. Deionized water dissolved significantly more SO4-S in the control plots than most weak salt extractants. The concentration of soluble organic S decreased in the control plots after 100 days of plant growth, indicating that the organic S pool contributed significantly to the S nutrition of the forage crops. Significant relationships among the SO4-S in the soil determined in different extracts and crop yield, sulfur content in the forage, and total sulfur uptake were only found for the Ca(H2PO4)(2) extract. In general, the correlation coefficients proved to be unsatisfactory for field experimentation.

Sulfur concentrations and isotopic composition of serpentinized oceanic peridotites

The mineralogy, contents, and isotopic compositions of sulfur in oceanic serpentinites reflect variations in temperatures and fluid fluxes. Serpentinization of <1 Ma peridotites at Hess Deep occurred at high temperatures (200°-400°C) and low water/rock ratios. Oxidation of ferrous iron to magnetite maintained low fO2 and produced a reduced, low-sulfur assemblage including NiFe alloy. Small amounts of sulfate reduction by thermophilic microbes occurred as the system cooled, producing low-delta34S sulfide (1.5? to -23.7?). In contrast, serpentinization of Iberian Margin peridotites occurred at low temperatures(~20°-200°C) and high water/rock ratios. Complete serpentinization and consumption of ferrous iron allowed evolution to higher fO2. Microbial reduction of seawater sulfate resulted in addition of low-delta34S sulfide (~15 to ~43?) and formation of higher-sulfur assemblages that include valleriite and pyrite. The high SO4/total S ratio of Hess Deep serpentinites (0.89) results in an increase of total sulfur and high delta34S of total sulfur (mean ~8?). In contrast, Iberian Margin serpentinites gained large amounts of 34S-poor sulfide (mean total S = 3800 ppm), and the high sulfide/total S ratio (0.61) results in a net decrease in delta34S of total sulfur (mean ~ -5?). Thus serpentinization is a net sink for seawater sulfur, but the amount fixed and its isotopic composition vary significantly. Serpentinization may result in uptake of 0.4-14 * 10**12 g S/yr from the oceans, comparable to isotopic exchange in mafic rocks of seafloor hydrothermal systems and approaching global fluxes of riverine sulfate input and sedimentary sulfide output.

Contencentrations of reduced inorganic sulfur forms in Mediterranean Sea waters

The first data on content of inorganic reduced sulfur compounds [H2S, S°, S2O3(2-), SO3(2-)] were obtained at two stations in the northeastern Levant Sea (Mediterranean Basin). With lower detection limit for the mentioned sulfur forms of 30 nM, sulfide forms were not found, while thiosulfate concentration varied from 178 to 890 nM (from 24 to 78 % of total reduced S), and S° varied from 156 to 1090 nM. Vertical distribution of these compounds showed irregular character; correlation between total reduced S maxima, fluorescence, and increase of nutrient element content near the lower pycnocline boundary was observed. The maximum total sulfur concentration in the surface layer was likely due an anthropogenic influence. The ''starting'' mechanism that controls appearance and distribution of sulfur compounds in oxygen-containing water is the process of bacterial sulfate reduction in micropatches of fresh organic detritus. Reduced sulfur forms participate further in a series of chemical and biochemical processes. Contribution of hydrolysis of organic sulfur-containing compounds is insignificant for the region in study.

(Table 1) Sulfur content and sulfur-isotope ratios at DSDP Leg 82 Holes basalts

The sulfur contents of 21 basalt samples from four DSDP Leg 82 holes were determined and the isotopic compositions of sulfur were measured on 15 of them. Most of the basalts are altered and have sulfur contents of about 100 ppm. Isotopic ratios for sulfate and total sulfur range from +0.7 to +10.5 per mil, indicating almost complete leaching of the igneous sulfide in low-sulfur samples by alteration. Total sulfur content of some samples ranges between 960 and 1170 ppm, somewhat higher than expected for tholeiitic basalts. The isotope ratios of total sulfur in these samples are slightly shifted to values heavier than the generally assumed mantle ratio of zero, and this shift is thought to result from a secondary source of sulfur.

Sulfur in oceans and seas

The book summarizes results of long-term studies of sulfur geochemistry in bottom sediments of seas and oceans. Processes of hydrogen sulfide formation in bacterial reduction of sulfates, its transformation into transient and stable compounds of reduced sulfur in liquid and solid phases of sediments are under consideration. Regularities of distribution of sulfate and reduced sulfur in ocean sediments are shown. Problems of sulfur budget in the modern oceans are discussed.

Sulfur concentrations and isotope ratios in sediments from Kiel Bay, western Baltic Sea

The isotope-ratios of sulfur-components in several sedimentologically different cores of recent marine sediments from Kiel Bay (Baltic Sea) were investigated. In addition, quantitative determinations were made on total sulfur, sulfate, sulfide, chloride, organic carbon, iron and watercontent in the sediment or in the pore-water solution. The investigations gave the following results: 1. The sulfur in the sediment (about 0.3 -2 % of the dry sample) was for the most part introduced into the sediment after sedimentation. This confirms the results of Kaplan et al. (1963, doi:10.1016/0016-7037(63)90074-7). The yield of Sulfur from organic material is very small (in our samples about 5-10% of the total sulfur in the sediment). 2. The sulfur bound in the sediment is taken from the sulfate of the interstitial water. During normal sedimentation, the exchange of sulfate by diffusion significant for changes in the sulfur-content goes down to a sediment depth of 4-6 cm. In this way the sulfate consumed by reduction and formation of sulfide or pyrite is mostly replaced. The uppermost layer of the sediment is an partly open system for the sulfur. The diagenesis of the sulfur is allochemical. 3. The isotope-values of the sediment-sulfur are largely influenced by the sulfur coming into the sediment by diffusion and being bound by bacteriological reduction. Due to the prevailing reduction of 32S and reverse-diffusion of sulfate into the open sea-water, an 32S enrichment takes place in the uppermost layer of the sediment. delta34S-values in the sediment range between -15 and -35 ? while seawater-sulfate has +20 ?. No relationship could be established between sedimentological or chemical changes and isotope-ratios. In the cores, successive sandy and clayly layers showed no change in the delta-values. The sedimentation rate, however, seems to influence isotope-ratios. In one core with low sedimentationrates the delta34S-values varied between -29 and -33 ?, while cores with higher sedimentationrates showed values between -17 and -24 ?. 4. As sediment depth increases, the pore-water sulfate shows decreasing concentrations (in a depth of 30-40 cm we found between 20 and 70 % of the seawater-values), and increasing delta 34S-values (in one case reaching more than +60 ?). The concentration of sulfide in the pore-water increases with sediment-depth (reaching 80 mg S/l in one case). The (delta34S-values of the pore-water-sulfide in all cores show increases paralleling the sulfate sulfur, with a nearly constant delta-distance of 50-60 ? in all cores. This seems to confirm the genetic relationship between the two components.

Pore water and solid phase sulfur, carbon and iron data from samples collected in the Argentine Basin during expedition M78

Sulfur phases in the Argentine Basin.