Heterogeneous uptake of carbonyl sulfide on hematite and hematite-NaCl mixtures

Heterogeneous uptake of carbonyl sulfide (COS) on hematite, NaCl, and a series of hematite-NaCl mixtures was investigated in a static reaction chamber at 298 K using in situ diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS). The adsorbed COS was oxidized on the surface of hematite and hematite-NaClmixtures, forming surface hydrogen thiocarbonate (HSCO2-), carbonate (CO3(2-)), and sulfate (SO4(2-)) species as well as gaseous CO2. The reactivity of hematite-NaCI mixtures was lower than that of hematite alone. No uptake of COS was observed on the pure NaCl sample. For mixtures, the 40% hematite + 60% NaCl sample exhibited the highest reactivity. Preadsorption experiments using CO2 as a probe molecule indicated that about 70% of adsorbed COS was oxidized by surface oxygen ions on hematite. In contrast, the Fe-CIO species formed during the sample preparation procedure is proposed to be the active site on the hematite-NaCI mixtures. A plausible reaction mechanism of the heterogeneous oxidation of COS is proposed, and atmospheric implications based on these results are discussed.     

Simulating the degree of oxidation in atmospheric organic particles

Modeled ratios of organic mass to organic carbon (OM/OC) and oxygen to carbon (n(O)/n(C)) in organic particulate matter are presented across the US for the first time and evaluated extensively against ambient measurements. The base model configuration systematically underestimates OM/OC ratios during winter and summer months. Model performance is greatly improved by applying source-specific OM/OC ratios to the primary organic aerosol (POA) emissions and incorporating a new parametrization to simulate oxidative aging of POA in the atmosphere. These model improvements enable simulation of urban-scale gradients in OM/OC with values in urban areas as much as 0.4 lower than in the surrounding regions. Modeled OM/OC and n(O)/n(C) ratios in January range from 1.4 to 2.0 and 0.2 to 0.6, respectively. In July, modeled OM/OC and n(O)/n(C) ratios range from 1.4 to 2.2 and 0.2 to 0.8, respectively. Improved model performance during winter is attributed entirely to our application of source-specific OM/OC ratios to the inventory. During summer, our treatment of oxidative aging also contributes to improved performance. Advancements described in this paper are codified in the latest public release of the Community Multiscale Air Quality model, CMAQv5.0.     

Supercritical water oxidation of sulfide

Supercritical water oxidation (SCWO) of sulfide wastewater with oxygen as the oxidant was investigated using ammonium sulfide solution as the model waste. The experiments, which were conducted in a bench-scale continuous SCWO installation, indicated that S2- could be completely oxidized to SO4(2-) within the residence time of less than 10 s under the supercritical water conditions at 698.2-773.2 K and 22.0 MPa-30.0 MPa. The reaction pathway of S2- in SCWO was determined to be S2- --> S2O3(2-) --> SO3(2-) --> SO4(2-). The effects of temperature, pressure, and oxygen content on SCWO of S2- were also studied. The kinetic model based on this pathway was established with the reaction rate constants and orders found by fitting the experimental data. The dependence of the rate constants on the temperature can be described with Arrhenius' law. The rate constants are dependent on the density of SCW, and the dependence is logarithmically linear.     

硫氧化细菌的筛选及其脱硫性能研究

从含硫土壤中分离得到一株高效的硫氧化细菌A62.通过间歇性试验对菌株A62的特性进行了研究.结果表明,该菌单个细胞为杆状、革兰氏阴性,好氧菌,且当温度30℃,pH7.5,S2-≤300mg/L时,硫化物的去除率最高达92.6%,它对工业脱硫有一定的应用价值.     

Formation of carbonyl sulfide by the reaction of carbon monoxide and inorganic polysulfides

OCS formation by the reaction of inorganic polysulfides with carbon monoxide, which are both abundant in natural aquatic systems, was studied as a model abiotic route for OCS formation in the dark. The net OCS accumulation rate was a function of a bimolecular formation reaction and simultaneous OCS hydrolysis kinetics. The reaction of polysulfides with CO in the dark was found to be first order with respect to CO concentration and first order with respect to the molar sum of the polysulfide species generated by the disproportionation of the dissolved polysulfide precursors. The pH dependence of the OCS production rate was controlled by the pH-dependent disproportionation of polysulfide precursors. Lower temperatures, intermediate redox potentials, and moderately basic pH conditions increase the steady-state concentration of OCS. The speciation of polysulfides in aqueous solutions is still disputed. Some authors claim that hexasulfide is one of the dominant species while others believe that pentasulfide is the largest sulfide species in aqueous systems. Despite the disagreement between different models for speciation of polysulfides, the proposed rate law agreed very well with the thermodynamic data based on four and on five polysulfide species, with only minor differences in the preexponential kinetic coefficients.     

Evaluation of S-residues in grains and grain fractions fumigated with S-labelled carbonyl sulfide

³⁵S-labelled carbonyl sulfide (CO³⁵S) was used to measure the amount of sorbed ³⁵S residues and converted ³⁵S residues in grains and grain fractions after fumigation with CO³⁵S. Hard wheat, soft wheat, paddy rice, brown rice, polished rice, sorghum, maize, canola, barley, oats and peas were exposed for 4 days to 50 mg L⁻¹ of CO³⁵S with a total radioactivity of 20 mCi. After exposure, the samples were aired. The levels of ³⁵S residues varied with extraction solvent, e.g. 0.003–0.02 mg (COS equivalents) kg⁻¹ (grain) in chloroform extractions and 0.09–0.38 mg kg⁻¹ in water extractions. More than 90% of ³⁵S (COS equivalents) residues were in the water extractions. The total radioactivity determined by scanning radiation images (fluorescent image) of extractions and sectioned commodities ranged from 0.1 to 0.4 mg kg⁻¹. The radiation image shows that more than 90% of ³⁵S residues were located or distributed in the embryo, testa, pericarp and husk, and that the ³⁵S was still slowly desorbing from grains after 2 days aeration.     

Effect of oxidation catalysts on diesel soot particles

The effect of a conventional oxidation catalyst and a novel particle oxidation catalyst (POC) on diesel particles is studied using identical methodology. Regulated particulate matter emission measurement is followed by analyzing soluble organic fraction. In addition, size distributions are measured using a partial flow sampling system with a thermodenuder as an option. A parallel ELPI-SMPS method is used to study the particle effective density and, further, the mass. Tests are conducted using a heavy duty diesel engine with a very low sulfur fuel. A decrease in particle mass was observed when using a catalyst. When using a conventional catalyst the decrease was attributed to the decrease of soluble organic fraction, while using POC the nonsoluble fraction was also found to decrease, by 8-38%. This observation is confirmed by particle number measurement, and POC was found to decrease the dry particle number concentration measured downstream of a thermodenuder by 13-28%. Further particle structure analysis indicated lower density values when using conventional catalyst or POC. The physical size of the particles was not changed noticeably over either catalyst--implying the soluble organic fraction was condensed onto the soot, filling the voids in the porous structure of soot agglomerates, when no catalyst is used.     

Fumigation with carbonyl sulfide: a model for the interaction of concentration, time and temperature

The new fumigant carbonyl sulfide offers an alternative to both methyl bromide and phosphine as a grain fumigant. Separate mathematical models for levels of kill, based on quantitative toxicological studies were developed for adults and eggs of the rice weevil Sitophilus oryzae (L.). These models suggest that fumigation exposure times for carbonyl sulfide will be a compromise between those of methyl bromide (typically 24 h) and phosphine (7–10 d) to achieve a very high kill of all developmental stages. S. oryzae eggs were more difficult to kill with carbonyl sulfide fumigation than the adults. At 30°C, a 25 g m⁻³ fumigation killed 99.9% of adults in less than 1 d, but took 4 d to kill the same percentage of eggs. Models were generated to describe the mortality of adults at 10, 15, 20, 25 and 30°C. From these models it is predicted that fumigation with carbonyl sulfide for 1–2 d at 30 g m⁻³ will kill 99.9% of adults. Furthermore the models illustrate that fumigations with concentrations below 10 g m⁻³ are unlikely to kill all adult S. oryzae. Significant variation was observed in the response of eggs to the fumigant over the temperature range of 10 to 30°C. Models were generated to describe the mortality of eggs at 10, 15, 20, 25 and 30°C. As the temperature was reduced below 25°C, the time taken to achieve an effective fumigation increased. Extrapolating from the models, a 25 g m⁻³ fumigation to control 99.9% of S. oryzae eggs will take 95 h (4 d) at 30°C, 77 h (3.2 d) at 25°C, 120 h (5 d) at 20°C, 174 h (7.5 d) at 15°C and about 290 h (11 d) at 10°C. The role of temperature in the time taken to kill eggs with carbonyl sulfide cannot be ignored. In order to achieve the desired level of kill of all developmental stages, the fumigation rates need to be set according to the most difficult life stage to kill, in this instance, the egg stage.     

Protective role of vacuum vs. atmospheric frying on PUFA balance and lipid oxidation

The effect of vacuum frying processing on proximate composition, fatty acid profile, oxidative status and sensorial properties of fish patties, was evaluated as compared with conventional (atmospheric) frying.Vacuum frying procedure was carried out at 80 mmHg (water boiling point: 42 °C) and oil temperature (107 °C) determined to obtain an equivalent thermal driving force (Δ65 °C) of that of the atmospheric frying conditions used (165 °C). Frying times of 2, 4, 6, 8 and 10 min were investigated.Vacuum frying significantly prevented degradation of EPA (Eicosapentaenoic acid) and DHA (Docosahexaenoic acid), reducing the polyene index and maintaining a lower ω6/ω3 fatty acid ratio in samples, while no significant differences with conventional frying in total oil content were observed. The use of vacuum also reduced formation of peroxides and carbonyl derivatives. Tocopherol levels decreased in all samples regardless of the frying conditions used, although vacuum-fried samples maintained higher tocopherol levels after processing. These samples also showed higher lightness and lower a* and b* values, which can be associated to lower non-enzymatic browning levels.These results support the applicability of vacuum frying technology for fish patties, since it prevents colour changes, improves juiciness and reduces oxidation when compared to conventionally (atmospheric) fried counterparts.Industrial relevanceConsumers are increasingly aware of the link between food and health, maintaining a high demand for healthy products. In this regard, consumption of fatty fish, with healthy properties widely known, is lower than recommended by health authorities, especially in children. Novel processing technologies focused on increasing the appealing of products based on fatty fish can help in ameliorating this deficient consumption. Vacuum frying is a promising way of obtaining attractive products, due to some product modification after the deep-fat frying process, and yet retaining natural colour, juiciness and healthy properties to a high extent. Vacuum frying allows reducing ω3 fatty acids and tocopherol degradation, differentiating fish products so obtained, which can be launched into the market and benefit from this technology. Compared to conventional frying, the results are better nutritional and sensory properties in a final product.     

Photocatalytic oxidation of gaseous 2-chloroethyl ethyl sulfide over TiO2

Photocatalytic oxidation of gaseous 2-chloroethyl ethyl sulfide (2-CEES, ClCH2CH2SCH2CH3) over TiO2 illuminated with UV light and maintained at 25 or 80 degrees C in air has been investigated. 2-CEES was found to suffer progressive oxidation to yield ethylene (CH2CH2), chloroethylene (ClCHCH2), ethanol (CH3CH2OH), acetaldehyde (CH3C(O)H), chloroacetaldehyde (ClCH2C(O)H), diethyl disulfide (CH3CH2S2CH2CH3), 2-chloroethyl ethyl disulfide (ClCH2CH2S2CH2CH3), and bis(2-chloroethyl) disulfide (ClCH2CH2S2CH2CH2Cl) as the main primary intermediates, and water (H2O), carbon dioxide (CO2), sulfur dioxide (SO2), surface sulfate ions (SO4(2-)), and hydrogen chloride (HCl) as the final products. Trace concentrations of gaseous 2-chloroethanol (ClCH2CH2OH), ethanesulfonyl chloride (CH3CH2SO2Cl), ethyl thioacetate (CH3CH2SC(O)CH3), and considerable amounts of acetic acid (CH3C(O)OH), crotonaldehyde (CH3CHCHC(O)H), methyl acetate (CH3C(O)OCH3), and methyl formate (CH3OC(O)H) were also detected in the gas phase during the photooxidation conducted at 80 degrees C. Increase in temperature from 25 to 80 degrees C accelerates formation of gaseous ethanol, acetaldehyde, chloroacetaldehyde, diethyl disulfide, 2-chloroethyl ethyl disulfide, and bis(2-chloroethyl) disulfide but suppresses ethylene and chloroethylene production at initial stages of the process. Some aspects of the possible reaction mechanism leading to this wide array of intermediates and final products are discussed.     

Regional modeling of the atmospheric fate and transport of benzene and diesel particles

The Community Multiscale Air Quality model (CMAQ) was modified to simulate the atmospheric fate and transport of benzene and diesel particles. We simulated the July 11-15, 1995 period over a domain covering the eastern United States with a 12-km horizontal resolution and a finer (4 km) resolution over a part of the northeastern United States that includes Washington, DC and New York City. The meteorological fields were obtained from a simulation conducted earlier with the mesoscale model MM5. Gridded emission files for benzene and diesel particles were developed using the SMOKE modeling system. The results of the model simulations showed that benzene concentrations were commensurate with available measurements. Over the 4-km resolution domain, a comparison between simulated and measured 24-h average concentrations showed a fractional error of 0.46, a fractional bias of 0.14, and a coefficient of determination (r2) of 0.25. A comparison between simulated benzene hourly concentrations in New York City and in the Brigantine Wilderness Area, NJ, showed that urban concentrations were greater than the remote area concentrations by a factor of 2-5. The results of the diesel particle simulations showed spatial and temporal patterns that were similar to those obtained for benzene. However, because of the lesser contribution of on-road mobile sources to diesel particle emissions compared to benzene emissions, diesel particle concentrations showed stronger gradients between urban areas and remote areas. A comparison between diesel particle concentrations in New York City and in the Brigantine Wilderness Area, NJ, showed that the urban concentrations were greater than the remote area concentrations by a factor of 2-10. Assuming that diesel particles consist of 50% "elemental" carbon (EC), the simulated EC concentrations were in close agreement (within 10%) with the measured concentration in the urban area (Washington, DC) but were significantly lower than the measured EC concentrations in the remote area (Brigantine Wilderness Area). This result suggests that other sources beside diesel fuel engines contribute to atmospheric EC concentrations and that EC may not be a good surrogate for diesel particles. A comparison of both benzene and diesel particle simulated concentrations between an urban area (New York City) and a remote area (Brigantine Wilderness Area) shows that, at a spatial resolution of 4 km, the regional background may contribute from 10 to 20% to the peak concentrations. These results suggest that the regional background may not be negligible and should be taken into account in urban air toxics studies.     

Determination of kinetics and stoichiometry of chemical sulfide oxidation in wastewater of sewer networks

A method for determination of kinetics and stoichiometry of chemical sulfide oxidation by dissolved oxygen (DO) in wastewater is presented. The method was particularly developed to investigate chemical sulfide oxidation in wastewater of sewer networks at low DO concentrations. The method is based on continuous measurement of the reactants allowing the kinetics to be determined at varying reactant concentrations during the course of the experiment. The kinetics determined was simulated by a rate equation. The precision of the method was assessed in terms of the standard deviation of the kinetic parameters determined in a triplicate experiment. The kinetic parameters determined in 25 experiments on wastewater samples from a single site exhibited good constancy with a variation of the same order of magnitude as the precision of the method. It was found that the stoichiometry of the reaction could be considered constant during the course of the experiments although intermediates accumulated. This was explained by an apparent slow oxidation rate of the intermediates. The method was capable of determining kinetics and stoichiometry of chemical sulfide oxidation at DO concentrations lower than 1 g of O2 m(-3).     

Acid-volatile sulfide oxidation in coastal flood plain drains: iron-sulfur cycling and effects on water quality

The effect of acid-volatile sulfide (AVS) oxidation on Fe-S cycling and water quality in coastal flood plain drains from acid-sulfate soil landscapes was examined using natural sediments and synthetic iron monosulfide. Oxidation of AVS occurred rapidly (half-time < or = 1 h) and produced elemental sulfur (S8(0)(s)) and iron oxyhydroxide (FeOOH(s)). The initial rapid AVS oxidation process occurred without significant acidification or changes to the aqueous-phase composition. Severe acidification (pH < 4) occurred only once S8(0)(s) began to oxidize to SO4 (within 2-3 days of the initial AVS oxidation). Our results demonstrate, for the first time with natural sediments, a significant pH-buffered (near-neutral) AVS oxidation step with the trigger to acidification being the oxidation of S8(0)(s). Acidification resulted in the pH-dependent release of large amounts of Al, Mn, Ni, and Zn even though the sediment metal content was low.     

Impacts of the Canadian forest fires on atmospheric mercury and carbonaceous particles in Northern New York

The impact of Canadian forest fires in Quebec on May 31, 2010 on PM(2.5), carbonaceous species, and atmospheric mercury species was observed at three rural sites in northern New York. The results were compared with previous studies during a 2002 Quebec forest fire episode. MODIS satellite images showed transport of forest fire smoke from southern Quebec, Canada to northern New York on May 31, 2010. Back-trajectories were consistent with this regional transport. During the forest fire event, as much as an 18-fold increase in PM(2.5) concentration was observed. The concentrations of episode-related OC, EC, BC, UVBC, and their difference (Delta-C), reactive gaseous mercury (RGM), and particle-bound mercury (PBM) were also significantly higher than those under normal conditions, suggesting a high impact of Canadian forest fire emissions on air quality in northern New York. PBM, RGM, and Delta-C are all emitted from forest fires. The correlation coefficient between Delta-C and other carbonaceous species may serve as an indicator of forest fire smoke. Given the marked changes in PBM, it may serve as a more useful tracer of forest fires over distances of several hundred kilometers relative to GEM. However, the Delta-C concentration changes are more readily measured.     

Photochemistry of iron in simulated crustal aerosols with dimethyl sulfide oxidation products

Iron contained in dust-derived aerosol particles deposited into remote oceans is essential for phytoplankton productivity, which controls photosynthesis rate and the uptake and release of climate forcing gases. Understanding chemical mechanisms that control iron bioavailability, that is, its speciation, is therefore crucial for global climate predictions. In the present study, the photoredox chemistry of iron in marine atmospheric aerosol particles was investigated by using ferrihydrite as a surrogate iron phase in the presence of dimethyl sulfide (DMS) derived oxidation products: dimethyl sulfoxide (DMSO), dimethyl sulfone (DMS02), methane sulfinic acid (MSIA), and methane sulfonic acid (MSA). Reactants and products were analyzed with UV-vis absorption spectroscopy, ion chromatography, and a hydrogen peroxide sensitive electrode. Results show that MSIA enhances the photoreductive dissolution of iron in a ligand-to-metal charge transfer reaction producing Fe(II), MSA, and H2O2. The rate law for Fe(II) is close to first order (0.79) with regard to adsorbed MSIA and has an empirical rate constant of 1.4 x 10(-4) s(-1). This mechanism may represent a significant pathway through which iron becomes more bioavailable, and it contributes to models of iron and sulfur chemistries in the marine atmosphere.