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.

Chemical functionalities of high and low sulfur Australian coals : a case study using micro attenuated total reflectance–fourier transform infrared (ATR–FTIR) spectrometry

The macerals in bituminous coals with varying organic sulfur content from the Early Permian Greta Coal Measures at three locations (Southland Colliery, Drayton Colliery and the Cranky Corner Basin), in and around the Sydney Basin (Australia), have been studied using light-element electron microprobe (EMP) analysis and micro-ATR–FTIR. Electron microprobe analysis of individual macerals reveals that the vitrinite in both the Cranky Corner Basin and Drayton Colliery (Puxtrees seam) samples have similar carbon contents (ca. 78% C in telocollinite), suggesting that they are of equivalent rank. However, the Cranky Corner coals have anomalously low vitrinite reflectance (down to 0.45%) vs. the Drayton materials (ca. 0.7%). They also have very high organic S content (3–6.5%) and lower O content (ca. 10%) than the equivalent macerals in the Drayton sample (0.7% S and 15.6% O). A study was carried out to investigate the impacts of the high organic S on the functional groups of the macerals in these two otherwise iso-rank, stratigraphically-equivalent seams. An iso-rank low-S coal from the overlying Wittingham Coal Measures near Muswellbrook and coals of slightly higher rank from the Greta Coal Measures at Southland Colliery near Cessnock were also evaluated using the same techniques to extend the data set. Although the telocollinite in the Drayton and Cranky Corner coals have very similar carbon content (ca.78% C), the ATR–FTIR spectra of the vitrinite and inertinite macerals in these respectively low S and high S coals show some distinct differences in IR absorbance from various aliphatic and aromatic functional groups. The differences in absorbance of the aliphatic stretching bands (2800–3000 cm−1) and the aromatic carbon (CC) peak at 1606 cm−1 are very obvious. Compared to that of the Drayton sample (0.7% S and 15% O), the telocollinite of the Cranky Corner coal (6% S and 10% O) clearly shows: (i) less absorbance from OH groups, represented by a broad region around 3553 cm−1, (ii) much stronger aliphatic C–H absorbance (stretching modes around 3000–2800 cm−1 and bending modes around 1442 cm−1) and (iii) less absorbance from aromatic carbon functional groups (peaking at 1606 cm−1). Evaluation of the iso-rank Drayton and Cranky Corner coals shows that: (i) the aliphatic C–H absorbances decrease with increasing oxygen content but increase with increasing organic S content and (ii) the aromatic H to aliphatic H ratio (Har/Hali) for the telocollinite increases with (organic) O%, but decreases progressively with increasing organic S. The high organic S content in the maceral appears to be accompanied by a greater proportion of aliphatic functional groups, possibly as a result of some of the O within maceral ring structures in the high S coal samples being replaced.

Effect of thermal treatment on adsorption-desorption of ammonia and sulfur dioxide on palygorskite : change of surface acid-alkali properties

Thermally activated Palygorskite (Pg) has been found to be a good adsorbent material for ammonia (NH3) and sulfur dioxide (SO2). This research investigated the effect of thermal treatment on pore structure and surface acid-alkali properties of Pg through the adsorption-desorption of NH3 and SO2. The results showed that, up to 200 °C, the adsorption of NH3 on Pg was significantly higher than SO2. This was due to NH3 being adsorbed in the internal surface of Pg and forming hydrogen bonds (H-bonds) with coordinated water. The increase in thermal treatment temp. from 150 to 550 °C, showed a gradual decrease in the no. of surface acid sites, while the no. of surface alk. sites increased from 200 to 400 °C. The change of surface acidity-alk. sites is due to the collapse of internal channels of Pg and desorption of different types of hydroxyls assocd. with the Pg structure.

Measurement of total body water (TBW) and total energy expenditure (TEE) using stable isotopes

Understanding the relationship between diet, physical activity and health in humans requires accurate measurement of body composition and daily energy expenditure. Stable isotopes provide a means of measuring total body water and daily energy expenditure under free-living conditions. While the use of isotope ratio mass spectrometry (IRMS) for the analysis of 2H (Deuterium) and 18O (Oxygen-18) is well established in the field of human energy metabolism research, numerous questions remain regarding the factors which influence analytical and measurement error using this methodology. This thesis was comprised of four studies with the following emphases. The aim of Study 1 was to determine the analytical and measurement error of the IRMS with regard to sample handling under certain conditions. Study 2 involved the comparison of TEE (Total daily energy expenditure) using two commonly employed equations. Further, saliva and urine samples, collected at different times, were used to determine if clinically significant differences would occur. Study 3 was undertaken to determine the appropriate collection times for TBW estimates and derived body composition values. Finally, Study 4, a single case study to investigate if TEE measures are affected when the human condition changes due to altered exercise and water intake. The aim of Study 1 was to validate laboratory approaches to measure isotopic enrichment to ensure accurate (to international standards), precise (reproducibility of three replicate samples) and linear (isotope ratio was constant over the expected concentration range) results. This established the machine variability for the IRMS equipment in use at Queensland University for both TBW and TEE. Using either 0.4mL or 0.5mL sample volumes for both oxygen-18 and deuterium were statistically acceptable (p>0.05) and showed a within analytical variance of 5.8 Delta VSOW units for deuterium, 0.41 Delta VSOW units for oxygen-18. This variance was used as “within analytical noise” to determine sample deviations. It was also found that there was no influence of equilibration time on oxygen-18 or deuterium values when comparing the minimum (oxygen-18: 24hr; deuterium: 3 days) and maximum (oxygen-18: and deuterium: 14 days) equilibration times. With regard to preparation using the vacuum line, any order of preparation is suitable as the TEE values fall within 8% of each other regardless of preparation order. An 8% variation is acceptable for the TEE values due to biological and technical errors (Schoeller, 1988). However, for the automated line, deuterium must be assessed first followed by oxygen-18 as the automated machine line does not evacuate tubes but merely refills them with an injection of gas for a predetermined time. Any fractionation (which may occur for both isotopes), would cause a slight elevation in the values and hence a lower TEE. The purpose of the second and third study was to investigate the use of IRMS to measure the TEE and TBW of and to validate the current IRMS practices in use with regard to sample collection times of urine and saliva, the use of two TEE equations from different research centers and the body composition values derived from these TEE and TBW values. Following the collection of a fasting baseline urine and saliva sample, 10 people (8 women, 2 men) were dosed with a doubly labeled water does comprised of 1.25g 10% oxygen-18 and 0.1 g 100% deuterium/kg body weight. The samples were collected hourly for 12 hrs on the first day and then morning, midday, and evening samples were collected for the next 14 days. The samples were analyzed using an isotope ratio mass spectrometer. For the TBW, time to equilibration was determined using three commonly employed data analysis approaches. Isotopic equilibration was reached in 90% of the sample by hour 6, and in 100% of the sample by hour 7. With regard to the TBW estimations, the optimal time for urine collection was found to be between hours 4 and 10 as to where there was no significant difference between values. In contrast, statistically significant differences in TBW estimations were found between hours 1-3 and from 11-12 when compared with hours 4-10. Most of the individuals in this study were in equilibrium after 7 hours. The TEE equations of Prof Dale Scholler (Chicago, USA, IAEA) and Prof K.Westerterp were compared with that of Prof. Andrew Coward (Dunn Nutrition Centre). When comparing values derived from samples collected in the morning and evening there was no effect of time or equation on resulting TEE values. The fourth study was a pilot study (n=1) to test the variability in TEE as a result of manipulations in fluid consumption and level of physical activity; the magnitude of change which may be expected in a sedentary adult. Physical activity levels were manipulated by increasing the number of steps per day to mimic the increases that may result when a sedentary individual commences an activity program. The study was comprised of three sub-studies completed on the same individual over a period of 8 months. There were no significant changes in TBW across all studies, even though the elimination rates changed with the supplemented water intake and additional physical activity. The extra activity may not have sufficiently strenuous enough and the water intake high enough to cause a significant change in the TBW and hence the CO2 production and TEE values. The TEE values measured show good agreement based on the estimated values calculated on an RMR of 1455 kcal/day, a DIT of 10% of TEE and activity based on measured steps. The covariance values tracked when plotting the residuals were found to be representative of “well-behaved” data and are indicative of the analytical accuracy. The ratio and product plots were found to reflect the water turnover and CO2 production and thus could, with further investigation, be employed to identify the changes in physical activity.

Determination of coastal ground and surface water processes and character by use of hydrochemistry and stable isotopes, Fraser Coast, Queensland

This study was part of an integrated project developed in response to concerns regarding current and future land practices affecting water quality within coastal catchments and adjacent marine environments. Two forested coastal catchments on the Fraser Coast, Australia, were chosen as examples of low-modification areas with similar geomorphological and land-use characteristics to many other coastal zones in southeast Queensland. For this component of the overall project, organic , physico-chemical (Eh, pH and DO), ionic (Fe2+, Fe3+), and isotopic (ä13CDIC, ä15NDIN ä34SSO4) data were used to characterise waters and identify sources and processes contributing to concentrations and form of dissolved Fe, C, N and S within the ground and surface waters of these coastal catchments. Three sites with elevated Fe concentrations are discussed in detail. These included a shallow pool with intermittent interaction with the surface water drainage system, a monitoring well within a semi-confined alluvial aquifer, and a monitoring well within the fresh/saline water mixing zone adjacent to an estuary. Conceptual models of processes occurring in these environments are presented. The primary factors influencing Fe transport were; microbial reduction of Fe3+ oxyhydroxides in groundwaters and in the hyporheic zone of surface drainage systems, organic input available for microbial reduction and Fe3+ complexation, bacterial activity for reduction and oxidation, iron curtain effects where saline/fresh water mixing occurs, and variation in redox conditions with depth in ground and surface water columns. Data indicated that groundwater seepage appears a more likely source of Fe to coastal waters (during periods of low rainfall) via tidal flux. The drainage system is ephemeral and contributes little discharge to marine waters. However, data collected during a high rainfall event indicated considerable Fe loads can be transported to the estuary mouth from the catchment.

Surface sulfur measurements on stratospheric particles

The surface chemistries of three particulate samples collected from the lower stratosphere have been determined using a Scanning Auger Microprobe (SAM). These samples are typical of the most abundant natural and anthropogenic particles observed within the stratosphere in the >2µm diameter size fraction. Successive sputtering and analysis below the first few adsorbed monolayers of all particles shows the presence of a thin <150A) sulphur layer. These sulphur regions probably formed by surface reaction of sulphur-rich aerosols with each particle within the stratosphere. Settling rate calculations show that a typical sphere (10µm diameter) may reside within the aerosol layer for ~20 days and thus, provide a qualitative guide to surface sulphur reaction rates.

Sulfur resistant emissions catalyst

A catalyst comprising one or more complex oxides having a nominal compn. as set out in formula (1): AxB1-y-zMyPzOn (1) wherein A is selected from one or more group III elements including the lanthanide elements or one or more divalent or monovalent cations; B is selected from one or more elements with at. no. 22 to 24, 40 to 42 and 72 to 75; M is selected from one or more elements with at. no. 25 to 30; P is selected from one or more elements with at. no. 44 to 50 and 76 to 83; x is defined as a no. where 0

Ion-molecule reactions of O,S-Dimethyl methylphosphonothioate : Evidence for intramolecular sulfur oxidation during VX perhydrolysis

The alkaline perhydrolysis of the nerve agent O-ethyl S-[2-(diisopropylamino)ethyl] methylphosphonothioate (VX) was investigated by studying the ion-molecule reactions of HOO(-) with O,S-dimethyl methylphosphonothioate in a modified linear ion-trap mass spectrometer. In addition to simple proton transfer, two other abundant product ions are observed at m/z 125 and 109 corresponding to the S-methyl methylphosphonothioate and methyl methylphosphonate anions, respectively. The structure of these product ions is demonstrated by a combination of collision-induced dissociation and isotope-labeling experiments that also provide evidence for their formation by nucleophilic reaction pathways, namely, (i) S(N)2 at carbon to yield the S-methyl methylphosphonothioate anion and (ii) nucleophilic addition at phosphorus affording a reactive pentavalent intermediate that readily undergoes internal sulfur oxidation and concomitant elimination of CH(3)SOH to yield the methyl methylphosphonate anion. Consistent with previous Solution phase observations of VX perhydrolysis, the toxic P-O cleavage product is not observed in this VX model system and theoretical calculations identify P-O cleavage to be energetically uncompetitive. Conversely, intramolecular sulfur oxidation is calculated to be extremely exothermic and kinetically accessible explaining its competitiveness with the facile gas phase proton transfer process. Elimination of a sulfur moiety deactivates the nerve agent VX and thus the intramolecular sulfur oxidation process reported here is also able to explain the selective perhydrolysis of the nerve agent to relatively nontoxic products.

Sulfur-containing amide-based [2]rotaxanes and molecular shuttles

We report the synthesis, structure and properties of [2]rotaxanes prepared by the assembly of benzylic amide macrocycles around a series of amide and sulfide-/sulfoxide-/sulfone-containing threads. The efficacy of rotaxane formation is related to the hydrogen bond accepting properties of the various sulfur-containing functional groups in the thread, with the highest yields (up to 63% with a rigid vinyl spacer in the template site) obtained for sulfoxide rotaxanes. X-Ray crystallography of a sulfoxide rotaxane, 5, shows that the macrocycle adopts a highly symmetrical chair-like conformation in the solid state, with short hydrogen bonds between the macrocycle isophthalamide NH-protons and the amide carbonyl and sulfoxide S-O of the thread. In contrast, in the X-ray crystal structures of the analogous sulfide (4) and sulfone (6) rotaxanes the macrocycle adopts boat-like conformations with long intercomponent NH…O=SO and NH…S hydrogen bonds (in addition to several intercomponent amide-amide hydrogen bonds). Taking advantage of the different hydrogen bonding modes of the sulfur-based functional groups, a switchable molecular shuttle was prepared in which the oxidation level of sulfur determines the position of the macrocycle on the thread.

Influence of the diesel fuel sulfur content on the formation of nanoparticles

In recent years fine and ultra fine particles emitted from internal combustion engines have attracted an increasing level of attention. This attention has arisen from epidemiological studies conducted by a number of research groups and pointing to the health effects resulting from inhalation of fine particles. Previous studies on the influence of fuel sulfur level on diesel vehicle emissions were mainly concentrated on particle mass emissions. This study aims at investigating the influence of the reduction of diesel fuel sulfur level on the emission and formation of nanoparticles

Environment and productivities in developed and developing countries : the case of carbon dioxide and sulfur dioxide

We propose a productivity index for undesirable outputs such as carbon dioxide (CO2) and sulfur dioxide (SO2) emissions and measure it using data from 51 developed and developing countries over the period 1971-2000. About half of the countries exhibit the productivity growth. The changes in the productivity index are linked with their respective per capita income using a semi-parametric model. Our results show technological catch up of low-income countries. However, overall productivities both of SO2 and CO2 show somewhat different results.

Sulfur dioxide allowances : trading and technological progress

The US Clean Air Act Amendments introduce an emissions trading system to regulate SO2 emissions. This study finds that changes in SO2 emissions prices are related to innovations induced by these amendments. We find that electricity-generating plants are able to increase electricity output and reduce emissions of SO2 and NOx from 1995 to 2007 due to the introduction of the allowance trading system. However, compared to the approximate 8% per year of exogenous technological progress, the induced effect is relatively small, and the contribution of the induced effect to overall technological progress is about 1-2%.