COS,CS2 and SO2 in aluminium smelter exhaust

Measurements of carbonyl sulfide (COS) and carbondisulfide (CS₂) were carried out on samples drawn from a smoke stack of an aluminium smelter. Volume mixing ratios of 6 ppm COS and 0.1 ppm CS₂ were measured for gases from the electrolysis unit that had previously passed an Al₂O₃ fluid bed reactor and electrostatic precipitators. Specific emissions of 1.6 kg COS and 0.03 kg CS₂ per ton of primary aluminium were found. Extrapolating from this particular smelter’s conditions to a world mix specific COS emissions of about 4 kg/t(Al) are calculated resulting in emissions of annually 0.08 Tg COS into the atmosphere due to electrolytic aluminium production in 1995. Besides the photochemical conversion of anthropogenic CS₂ aluminium production is established to be the second major industrial source of COS probably exceeding automotive tire wear’s and coal combustion’s contributions.     

Carbon disulphide production in laboratory cultures of marine phytoplankton

Carbon disulphide (CS₂) data were collected from axenic monocultures of six species of marine phytoplankton. The tested species included Chaetoceros calcitrans, Phaeodactylum tricornutum, Phaeocystis sp., Porphyridium purpureum, Synechococcus sp. and Isochrysis sp. For a period of between two weeks and forty days, substantial accumulation of CS₂ was found in the cultures of C. calcitrans, P. tricornutum and Phaeocystis sp., whereas the change of CS₂ concentration in the remaining cultures was insignificant. C. calcitrans had a potential for CS₂ production about 10 times higher than P. tricornutum or Phaeocystis sp. The formation of the compound was strongly dependent on the physiological state of the cultured species. More investigation is needed to elucidate the mechanisms responsible for the formation of this sulphur compound in these cultures.     

Dissipation and residues of dimethyl disulfide in tomatoes and soil under greenhouse and open field conditions

Abstract

Tomatoes have been widely planted in greenhouses and fields in China. Soil-borne diseases are more harmful to tomatoes than other types of diseases. Dimethyl disulfide (DMDS) was used as a novel fumigant instead of methyl bromide to control soil-borne diseases. To assess the safety of DMDS for use on tomatoes, its dissipation and terminal residues were investigated at three different locations under greenhouse and open field conditions. The QuEChERS method was simplified using gas chromatography with mass spectrometry detection and combined with liquid-liquid extraction purification to allow determination of DMDS levels in both the tomatoes and the soil. The average recovery of the method was between 85.3 and 98.6%, with the relative standard deviation (RSD) ranging from to 1.9–10.3%. The dissipation and terminal residues of DMDS in the tomatoes and the soil were analyzed using the method, the results of which showed that the half-life of DMDS ranged from 0.3–6.5 d in the soil at three different locations. The terminal residues of DMDS in the tomatoes and the soil were not detected. This study provided data that the Chinese government can use to support appropriate and safe guidance for the use of DMDS on agriculture.     

H4SiW12O40/TiO2/beads光催化降解亚甲基蓝的研究

以钛酸四丁酯为原料,空心微珠为载体,采用溶胶凝胶法制备TiO₂/beads光催化剂载体,然后浸渍法制备出H₄SiW₁₂O₄₀/TiO₂/beads表面负载修饰型复合光催化剂,并运用SEM、XRD、FT-IR和DRS对催化剂进行表征和分析。研究了H₄SiW₁₂O₄₀/TiO₂/beads对亚甲基蓝降解的光催化活性,考察了光强度、pH值、曝气量、底物浓度和催化剂用量等对催化效率的影响。实验结果表明,在中性条件下,H₄SiW₁₂O₄₀/TiO₂/beads催化剂的投加量为0.25 g/L,浓度为7.5 mg/L的亚甲基蓝溶液在250 W的紫外灯和600 W的可见光灯下光照60 min降解率分别可达到94.5%和55%。     

Effects of soil fumigants on methanotrophic activity

Negative impacts on methane (CH₄) oxidation capacity have already been observed for a variety of agronomic practices, but the effect of soil fumigation on CH₄ oxidation has not been investigated. Fumigation is a common practice in agricultural crop and nursery seedling protection. Soils from various agricultural experiment stations, forest nurseries, and a landfill were evaluated for effects of 1,3-dichloropropene (1,3-D), methyl isothiocyanate (MITC), and chloropicrin (CP) on CH₄ oxidation capacities. All three fumigants significantly reduced CH₄ oxidation rates in historically non-fumigated soils (>50%). 1,3-D enhanced CH₄ oxidation in 3 out of 5 previously fumigated soils and MITC increased CH₄ oxidation rates in all historically MITC-fumigated soils compared to controls. CP universally decreased oxidation capacity regardless of fumigation history. These results support the conclusion that CH₄ oxidation effects are fumigant specific and that prior fumigation history plays a vital role in determining the impact on CH₄ oxidizer community functionality, which may have implications on the global CH₄ cycle.     

Effect of Nb doping on structural, optical and photocatalytic properties of flame-made TiO2 nanopowder

TiO₂:Nb nanopowders within a dopant concentration in the range of 0.1?C15?at.% were prepared by one-step flame spray synthesis. Effect of niobium doping on structural, optical and photocatalytic properties of titanium dioxide nanopowders was studied. Morphology and structure were investigated by means of Brunauer?CEmmett?CTeller isotherm, X-ray diffraction and transmission electron microscopy. Diffuse reflectance and the resulting band gap energy were determined by diffuse reflectance spectroscopy. Photocatalytic activity of the investigated nanopowders was revised for the photodecomposition of methylene blue (MB), methyl orange (MO) and 4-chlorophenol under UVA and VIS light irradiation. Commercial TiO₂-P25 nanopowder was used as a reference. The specific surface area of the powders was ranging from 42.9?m²/g for TiO₂:0.1?at.% Nb to 90.0?m²/g for TiO₂:15?at.% Nb. TiO₂:Nb particles were nanosized, spherically shaped and polycrystalline. Anatase was the predominant phase in all samples. The anatase-related transition was at 3.31?eV and rutile-related one at 3.14?eV. TiO₂:Nb nanopowders exhibited additional absorption in the visible range. In comparison to TiO₂-P25, improved photocatalytic activity of TiO₂:Nb was observed for the degradation of MB and MO under both UVA and VIS irradiation, where low doping level (Nb?<?1?at.%) was the most effective. Niobium doping affected structural, optical and photocatalytic properties of TiO₂. Low dopant level enhanced photocatalytic performance under UVA and VIS irradiation. Therefore, TiO₂:Nb (Nb?<?1?at.%) can be proposed as an efficient selective solar light photocatalyst.     

Phosphine migration at the water-air interface in Lake Taihu, China

The diurnal atmospheric phosphine (PH₃) concentrations and fluxes at the water-air interface in Lake Taihu were reported. The results showed that the PH₃ flux at the water-air interface ranged from −69.9 ± 29.7 to 121 ± 42 ng m⁻² h⁻¹, with a mean flux of 14.4 ± 22.5 ng m⁻² h⁻¹. The fluxes were both negative and positive during the diurnal period, indicating that the lake can act as a sink and a source of PH₃. In addition, the PH₃ fluxes were positively correlated with water temperature, total soluble phosphorus and soluble reactive phosphorus, while they were negatively correlated with water redox potential. A similar diurnal variation curve of atmospheric PH₃ concentrations was observed during all four seasons, with the maximum level occurring in early morning and the minimum appearing around midday. These findings suggest that light plays an important role in the elimination of atmospheric PH₃. A significant positive correlation was also found between air temperature and atmospheric PH₃ concentration. The mean flux of PH₃ in Lake Taihu was higher than in other reported wetlands, with an estimated annual emission of PH₃ to the atmosphere of 2.94 × 10⁵ g y⁻¹.     

A novel BiVO4-GO-TiO2-PANI composite for upgraded photocatalytic performance under visible light and its non-toxicity

A novel non-toxic hybrid BiVO₄-GO-TiO₂-polyaniline (PANI) (BVGT-PANI) composite with superior photocatalysis was successfully prepared via a one-pot hydrothermal reaction. The structural and morphological characterizations of the synthesized compounds were analyzed by a series of techniques. We found excellent photocatalytic efficiencies for methylene blue (MB) and phenol degradation under visible light irradiation after adhering the PANI to the photocatalyst. The degradation rates of MB and phenol reach up to approximately 85% and 80%, respectively, after 3 h of irradiation. For photodegradation MB, BVGTA exhibit the highest k_app rate constant of about 1.06?×?10^?2 min^?1, which is about 1.63-fold faster than BVG and 2.94-fold faster than BVGT. For photodegradation of phenol, BVGTA exhibits the highest k_app rate constant, of about 8.86?×?10^?3min^?1, which is about 1.2-fold faster than BVG and 1.96-fold faster than BVGT. Furthermore, vitro toxicity test against Bacillus subtilis and Staphylococcus aureus demonstrated that the nanophotocatalyst is non-toxic.

     

Performance Characterization and Optimization of the AgNO3-Filter/FMA Fluorimetric Method for Atmospheric H2S Measurements

This sensitive, albeit precarious, method for measuring ppb-ppt (V/V) concentrations of H₂S was examined for various sources of potential error within the procedure. Filter preparation, filter storage, filter extraction, fluorimetric reagent stabilities, matrix differences between standards and samples, and possible interferences from other sulfur-containing compounds were separately studied for their effects on the analytical performance of the method. The overall method showed no Interference from SO₂, CS₂, COS, CH₃SH, CH₃SCH₃, and SO₄ ^-2. To minimize bias and obtain a reliable estimate of precision, the method should be calibrated with H₂S standards rather than liquid bisulfide standards. The measurement precision is a function of the quantity of H₂S collected as Ag₂S and/or AgSH on the impregnated filters. Because of the method’s linear dynamic range, sufficient air should be sampled to achieve filter loadings of 15 to 35 ng S/filter. A quality control method based on fluorescein mercuric acetate (FMA) is presented that ensures data quality while reducing the otherwise frequent need for fluori-metric calibration.     

Intercomparison of two techniques for the preparation of gaseous sulfur calibration standards in the low to sub-ppb range

Calibration gas standards for H₂S, CH₃SH, CS₂ and SO₂, independently prepared by two separate research groups from the University of Idaho Department of Chemistry and the NOAA Aeronomy Laboratory, were directly intercompared using a gas chromatographic-flame photometric measurement procedure for all four species and a fluorimetric measurement procedure for H₂S. The NOAA gas standard system used gravimetrically-calibrated ‘low loss’ permeation tubes in conjunction with a three-stage dynamic dilution system. The University of Idaho (UI) system used single-stage dilution of the effluent from ‘ultra-low loss’ permeation tubes, which were calibrated by a metal foil collection/flash desorption/flame photometric detection procedure using aqueous sulfate standards. Comparative measurements between UI and NOAA gas standards in the 1–2 ppbv range showed differences no greater than 12 % for CS₂, SO₂ and CH₃SH, and 21 % for H₂S.     

Determination of propineb and its metabolites propylenethiourea and propylenediamine in banana and soil using gas chromatography with flame photometric detection and LC–MS/MS analysis

A sensitive and specific method for the determination of propineb and its metabolites, propylenethiourea (PTU) and propylenediamine (PDA), using gas chromatography with flame photometric detection (GC-FPD) and LC–MS/MS was developed and validated. Propineb and its metabolite residue dynamics in supervised field trials under Good Agricultural Practice (GAP) conditions in banana and soil were studied. Recovery of propineb (as CS₂), PDA and PTU ranged from 75.3 to 115.4% with RSD (n = 5) of 1.3–11.1%. The limit of quantification (LOQ) of CS₂, PDA and PTU ranged from 0.005 to 0.01 mg kg^?1, and the limit of detection (LOD) ranged from 0.0015 to 0.0033 mg kg^?1. Dissipation experiments showed that the half-life of propineb in banana and soil ranged from 4.4 to 13.3 days. PTU was found in banana with a half-life of 31.5–69.3 days, while levels of PDA were less than 0.01 mg kg^?1 in banana and soil. It has been suggested that PTU is the major metabolite of propineb in banana. The method was demonstrated to be reliable and sensitive for the routine monitoring of propineb and its metabolites in banana and soil. It also serves as a reference for the detection and monitoring of dithiocarbamates (DTCs) residues and the evaluation of their metabolic pathway.     

Free atmospheric phosphine concentrations and fluxes in different wetland ecosystems, China

Atmospheric phosphine (PH₃) fluxes from typical types of wetlands and PH₃ concentrations in adjacent atmospheric air were measured. The seasonal distribution of PH₃ in marsh and paddy fields were observed. Positive PH₃ fluxes are significantly related to high air temperature (summer season) and increased vegetation. It is concluded that vegetation speeds up the liberation of PH₃ from soils, while water coverage might function as a diffusion barrier from soils or sediments to the atmosphere. The concentrations of atmospheric PH₃ (ng m⁻³) above different wetlands decrease in the order of paddy fields (51.8 ± 3.1) > marsh (46.5 ± 20.5) > lake (37.0 ± 22.7) > coastal wetland (1.71 ± 0.73). Highest atmospheric PH₃ levels in marsh are found in summer. In paddy fields, atmospheric PH₃ concentrations in flourishing stages are higher than those in slowly growing stages.     

Phosphine in the marine atmosphere along a hemispheric course from China to Antarctica

The gas phosphine (PH₃) is a part of an atmospheric link of the phosphorus cycle on earth. Previous research reported the terrestrial lower tropospheric PH₃ at night in the 1 ng m⁻³ range in remote areas, with the peak of 100 ng m⁻³ in populated areas, and at daytime even lower concentrations in the pg m⁻³ range. The data of the global marine atmospheric PH₃ are still very sparse.This study presents surprisingly high concentrations of PH₃ in the order of 0.1–1 μg m⁻³ in many of 32 samples of the marine atmosphere in the latitudinal range from 30°N to 65°S (the cruise of research ship Xuelong from Shanghai Harbor, China, to Antarctica). The highest concentrations were measured near coastal areas of Eastern Asia and Western Australia. A significant correlation exists between marine atmospheric PH₃ concentration and air temperature at 22:00 (local time). PH₃ concentrations at different latitudes strongly decline with daylight intensity according to a logarithmic relationship. These surprisingly high concentrations of the readily oxidizable PH₃ in the air indicate hitherto unknown but important PH₃ emission sources in marine environment. More work is necessary to evaluate the sources of atmospheric PH₃ from marine biosphere.     

Removal of SO2 From Flue Gases Using Carbon at Elevated Temperatures

The interaction of a typical flue gas with active charcoal and bituminous coal char at temperatures between 600 and 800°C and atmospheric pressure has been studied. The SO₂ in the flue gas interacts with the carbon to form primarily H₂S, COS, and a carbon-sulfur surface complex. H₂S and COS break through the carbon bed much in advance of SO₂. At 800°C, sulfur retention on the bed exceeds at least 11% before SO₂ breakthrough occurs. The reaction of H₂S and COS with O₂ over active charcoal at 100–140°C to produce sulfur, which deposits on the carbon, has also been studied and found to be feasible. As a result of this study, a new process is outlined for the removal of SO₂ from flue gas, with the ultimate conversion     

pH-gradient real-time aeration control for nitritation community selection in a non-porous hollow fiber membrane biofilm reactor (MBfR) with dilute wastewater

Nitritation (ammonium to nitrite) as a pre-treatment of Anammox (anaerobic ammonium oxidation) is a key step for an energy-efficient nitrogen-removal alternative from dilute wastewaters, e.g. anaerobically-treated sewage, with which limited study has achieved sustainable nitritation at ambient temperature and short hydraulic retention times. To this end, pH-gradient real-time aeration control in an oxygen-based membrane biofilm reactor was observed at 20 °C in the sequencing batch mode. An optimum oxygen supply via diffusion for ammonium-oxidizing bacteria (AOB) was established, but nitrite-oxidizing bacteria (NOB) could be inhibited. The system achieved nitrite accumulation efficiencies varying from 88% to 94% with the aeration control. Mass balance and rate performance analyses indicate that this aeration control is able to supply an oxygen rate of 1.5 mol O₂ mol^?1 ammonium fed, the benchmark oxygenation rate based on stoichiometry for nitritation community selection. Microbial analyses confirmed AOB prevalence with NOB inhibition under this aeration control.     

Formation of shaped barium sulfate-dye hybrids: waste dye utilization for eco-friendly treatment of wastewater

Purpose

Owing to the present complexity and difficulty of concentrated dye wastewater treatment, this work aimed to synthesize a reproducible waste-sorbing material for the treatment of wastewater by forming the dye-conjugating complex hybrid.

Methods

The inorganic/organic hybridization was applied to prepare the objective material by immobilizing waster dye-Mordant blue 9 (MB) with barium sulfate (BaSO₄). The composition and pattern of the formed material were determined by spectrometry and characterized by SEM and XRD, and their formation process was clarified. The adsorption of cationic dye-basic blue BO (BB) and copper ion was investigated..

Results

The hybrid of MB alone into growing BaSO₄ formed the pineapple-like particles while that of the MB/BB-conjugating complex was the rhombus material. The adsorption of BB on the MB–BaSO₄ hybrid was probably attributed to ion-pair equilibrium and that of Cu²⁺ may result from the complexation. The treatment of dye and heavy metal wastewaters indicated that the MB hybrid material removed 99.8% BB and 97% Cu²⁺ and the dye-conjugating hybrid with growing BaSO₄ 100% MB, 99.5% BB, and 44% Cu²⁺.

Conclusion

The waste MB–BaSO₄ hybrid material is efficient to treat cationic dye and Cu²⁺ wastewater. The dye-conjugating hybridization method is the first to be advanced for in situ wastewater treatment, and it showed a combined effect for the removal of both organic dyes and heavy metals.     

Removal of carbon disulfide via coupled reactions on a bi-functional catalyst: Experimental and modeling results

A mathematical model describing the rate of carbon disulfide (CS₂) removal due to coupled reactions has been developed. Kinetic studies were carried out in a fixed bed reactor under atmospheric pressure and a range of temperatures (85–125 °C). The effects of flow rate, CS₂ inlet concentration, temperature and relative humidity were analyzed. A kinetic model based on axial dispersion, external and internal mass-transfer resistances, as well as effects of S deposition on the inner-face of the catalyst was in agreement with the CS₂ experimental breakthrough curves. The mathematical model can be used for process design and scale up of similar systems.     

In vitro methylation of DNA by the fumigant methyl bromide

Abstract

Investigations have shown that the physical state of the DNA strongly influences the pattern of methylation observed when DNA or a substance containing DNA is treated with the fumigant methyl bromide. 1‐Methyl‐adenine and 7‐methylguanine were identified, after hydrolysis, as the major methylated bases of DNA which had been treated in the solid state. 3‐Methylcytosine, 3‐methyladenine and 7‐methyladenine were found as minor products. The overall methylation pattern was similar to that observed earlier for DNA of maize and wheat which had been fumigated. In contrast, when buffer solutions of DNA were treated with methyl bromide, the N‐7 position of guanine was the major site and the N‐3 position of adenine was the second most important site of methylation. This result corresponds to that previously observed in similar studies with buffer solutions of DNA and other methylating agents.     

Carbonyl Sulfide Removal with Compost and Wood Chip Biofilters,and in the Presence of Hydrogen Sulfide

Abstract

Carbonyl sulfide (COS) is an odor-causing compound and hazardous air pollutant emitted frequently from wastewater treatment facilities and chemical and primary metals industries. This study examined the effectiveness of biofiltration in removing COS. Specific objectives were to compare COS removal efficiency for various biofilter media; to determine whether hydrogen sulfide (H₂S), which is frequently produced along with COS under anaerobic conditions, adversely impacts COS removal; and to determine the maximum elimination capacity of COS for use in biofilter design. Three laboratory-scale polyvinyl chlo-ride biofilter columns were filled with up to 28 in. of biofilter media (aged compost, fresh compost, wood chips, or a compost/wood chip mixture). Inlet COS ranged from 5 to 46 parts per million (ppm) (0.10–9.0 g/m³fihr). Compost and the compost/wood chip mixture produced higher COS removal efficiencies than wood chips alone. The compost and compost/wood chip mixture had a shorter stabilization times compared with wood chips alone. Fresh versus aged compost did not impact COS removal efficiency. The presence of H₂S did not adversely impact COS removal for the concentration ratios tested. The maximum elimination capacity is at least 9 g/m³·hr for COS with compost media.     

Aluminium production as a source of atmospheric carbonyl sulfide (COS)

Carbonyl sulfide is found as a major sulfur compound in anodic gases of commercial aluminium electrolysis. Recent spectroscopic measurements on industrial aluminium smelters found typical CO/COS ratios between 80 and 200. This results in specific COS emissions of between 1 and 7 kg/t(Al) if all COS is released into the atmosphere. In 1993 aluminium production would have been responsible for between 0.02 and 0.14 Tg of COS emissions. Currently, aluminium production does not seem to influence the total atmospheric COS budget to an extent beyond its natural variability. If recent growth rates of global aluminium production are sustained, however, COS emissions would quadruple until 2030. Together with increasing aircraft emissions into the stratosphere, an increase of the sulfate background aerosol is to be expected that could significantly enhance ozone depletion. The use of inert anodes is recommended to reduce aluminium production emissions of COS and CF₄, C₂F₆, CO₂, and CO at the same time.