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.     

Physical,chemical and biological behaviour of fumigants on cottonseed

Fumigation is required to protect cottonseed in storage and pre-shipment from insect pests and/or microorganisms. Fumigation of cottonseed with carbon disulphide (CS₂), carbonyl sulphide (COS), ethanedinitrile (C₂N₂), ethyl formate (EF), methyl bromide (MB) and phosphine (PH₃) showed that >85% of the fumigants disappeared within 5?h of exposure. COS maintained >20?mg L^–1 for 24?h. After 1?day of aeration, 75%–85% of the absorbed COS and MB and 20%–40% of the absorbed CS₂, EF and PH₃ were released from treated cottonseed. The fumigant residues were reduced by 80% for COS, 50% for EF or MB and 25% for CS₂ after 1?day of aeration. After 13?days of aeration, fumigant residues were reduced by 95% for MB, 65% for EF, 55% for CS₂ and to natural levels in the COS residue. Carbon disulphide, COS, PH₃, EF and C₂N₂ had no effect on the germination of cottonseed, but germination was reduced to 50% by MB. COS has potential as a fumigant for control of insect pests in cottonseed because it dissipates quickly and does not negatively impact germination. On the other hand, MB appears to strongly absorb and requires an extended period for residues to dissipate, and it negatively impacts germination.     

Formation of secondary inorganic aerosols by power plant emissions exhausted through cooling towers in Saxony

Background, aim, and scope  The fraction of ambient PM₁₀ that is due to the formation of secondary inorganic particulate sulfate and nitrate from the emissions of two large, brown-coal-fired power stations in Saxony (East Germany) is examined. The power stations are equipped with natural-draft cooling towers. The flue gases are directly piped into the cooling towers, thereby receiving an additionally intensified uplift. The exhausted gas-steam mixture contains the gases CO, CO₂, NO, NO₂, and SO₂, the directly emitted primary particles, and additionally, an excess of ‘free’ sulfate ions in water solution, which, after the desulfurization steps, remain non-neutralized by cations. The precursor gases NO₂ and SO₂ are capable of forming nitric and sulfuric acid by several pathways. The acids can be neutralized by ammonia and generate secondary particulate matter by heterogeneous condensation on preexisting particles. Materials and methods  The simulations are performed by a nested and multi-scale application of the online-coupled model system LM-MUSCAT. The Local Model (LM; recently renamed as COSMO) of the German Weather Service performs the meteorological processes, while the Multi-scale Atmospheric Transport Model (MUSCAT) includes the transport, the gas phase chemistry, as well as the aerosol chemistry (thermodynamic ammonium–sulfate–nitrate–water system). The highest horizontal resolution in the inner region of Saxony is 0.7 km. One summer and one winter episode, each realizing 5 weeks of the year 2002, are simulated twice, with the cooling tower emissions switched on and off, respectively. This procedure serves to identify the direct and indirect influences of the single plumes on the formation and distribution of the secondary inorganic aerosols. Results and conclusions  Surface traces of the individual tower plumes can be located and distinguished, especially in the well-mixed boundary layer in daytime. At night, the plumes are decoupled from the surface. In no case does the resulting contribution of the cooling tower emissions to PM₁₀ significantly exceed 15 μgm⁻³ at the surface. These extreme values are obtained in narrow plumes on intensive summer conditions, whereas different situations with lower turbulence (night, winter) remain below this value. About 90% of the PM₁₀ concentrations in the plumes are secondarily formed sulfate, mainly ammonium sulfate, and about 10% originate from the primarily emitted particles. Under the assumptions made, ammonium nitrate plays a rather marginal role. Recommendations and perspectives  The analyzed results depend on the specific emission data of power plants with flue gas emissions piped through the cooling towers. The emitted fraction of ‘free’ sulfate ions remaining in excess after the desulfurization steps plays an important role at the formation of secondary aerosols and therefore has to be measured carefully.     

Use of Energy Scenarios in Addressing the CO2 Question

A reference scenario for CO₂ emissions was developed using a model of world energy supply and demand. In the reference scenario, world GNP and world energy demand increase at average rates of 2.1 percent per year and 1.5 percent per year, respectively during the period 1975-2100. The corresponding annual CO₂ emissions rise to a maximum of 16 gigatons of carbon around 2050 and then decline as a result of a transition to nonfossil fuel energy systems. A modified scenario for high CO₂ emissions was obtained by assuming an abundant supply of low cost coal, thus eliminating the transition. A low case was developed in which the low cost of alternative energy (i.e., solar, nuclear) induces an earlier shift away from fossil fuels.

Annual emissions of the three scenarios were used as input to a global carbon cycle model and the CO₂ buildup in the atmosphere during the period 1980-2100 was determined by the model. All three scenarios showed continuous rises in atmospheric CO₂ concentration. The reference scenario reached 775 ppm by 2100. The high CO₂ case resulted in concentrations of over 1040 ppm, and for the low case the 2100 concentration was just under 700 ppm. If the climate theory is correct, even 700 ppm is sufficient to give significant climate warming, but by experiencing the change gradually over a century, adaptation may not be painful. An early transition to nonfossil fuel supplies makes the problem less severe but does not eliminate it.     

Free Enterprise and Air Pollution Control

Abstract

Title III of the 1990 Clean Air Act Amendments designated methanol as a pollutant to be regulated. The U.S. Environmental Protection Agency (EPA), through a contract with Research Triangle Institute, has developed a method for measuring methanol emissions from stationary sources. The methanol sampling train (MST) consists of a glass-lined heated probe, two condensate knockout traps, and three sorbent cartridges packed with Anasorb® 747. Samples are desorbed with a 1:1 mixture of carbon disulfide (CS₂) and N, N-dimethylformamide (DMF). Condensate water and CS₂/ DMF samples are analyzed by gas chromatography with flame ionization detection. The MST has a practical quantitation limit of approximately 3 ppm for a 20-L sample. Samples were shown to be stable for at least two weeks after collection.

Field tests of the MST and the National Council of the Paper Industry for Air and Stream Improvement (NCASI) methanol sampling method were conducted at two pulp and paper mills. Sampling and analysis procedures followed EPA Method 301 requirements.

The sampling location for the first field test was the inlet vent to a softwood bleach plant scrubber, where the methanol concentration was approximately 30 ppm. The mean recovery of spike was 108.3% for the MST method and 81.6% for the NCASI method. Although neither method showed significant bias at the 95% confidence level, the betweenmethods bias was significantly different.

A second field test was conducted at a vent from a black liquor oxidation tank where the methanol concentration was approximately 350 ppm. Mean spike recoveries were 96.6 and 94.2% for the MST and NCASI methods, respectively. The biases of the two methods and the between-methods bias were not significantly different for the second field test.     

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.     

Ambient and Source SO2 Detector Based on a Fluorescence Method

The principle of this detector is based on the measurement of the intensity of the ultraviolet fluorescence of SO₂ produced by absorption of the Zn 2138 Å or Cd 2288 Å line. The fluorescence intensity was found to be linear from 0.1 to 500 ppm of SO₂ in air with the Zn lamp and from 0.1 to 1600 ppm with the Cd lamp. The detection limit at present is about 20 ppb. There is no detectable interference from O₃, H₂S, NO₂, CO₂, CO, or H₂, although the presence of a large concentration of CS₂ (500 times as much as SO₂) NO (500 times) or C₂H₄ (4000 times) interferes with the measurement. The presence of 2% H₂0 reduces the signal by 25%, while up to 1 % CH₄ has almost no effect.     

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.     

N2O Emissions at Solid Waste Disposal Sites in Osaka City

Nitrous oxide (N₂O) is a trace gas contributing to stratospheric ozone depletion and global warming. Although a large quantity of information exists about N₂O emissions from various ecosystems, this study was initiated to demonstrate the features of N₂O emissions from sea-based waste disposal sites in Osaka City in relation to CH₄ emissions.

Average N₂O emissions at an active landfill (S-Site) were several times higher than those at a closed landfill (N Site). Average CH₄ emissions were also much greater at the S-Site. Regarding the nature of N₂O emissions, remarkable emissions often were observed with aerobic waste layers at the N-Site, suggesting almost inversely related N₂O emissions with CH₄ production at the N-Site. However, at the S-Site a few exceptionally high N₂O emissions were noted in cases of high CH₄ emissions.     

Greenhouse gas emissions from dairy open lot and manure stockpile in northern China: A case study

The open lots and manure stockpiles of dairy farm are major sources of greenhouse gas (GHG) emissions in typical dairy cow housing and manure management system in China. GHG (CO₂, CH₄ and N₂O) emissions from the ground level of brick-paved open lots and uncovered manure stockpiles were estimated according to the field measurements of a typical dairy farm in Beijing by closed chambers in four consecutive seasons. Location variation and manure removal strategy impacts were assessed on GHG emissions from the open lots. Estimated CO₂, CH₄ and N₂O emissions from the ground level of the open lots were 137.5±64.7 kg hd^-1 yr^-1, 0.45±0.21 kg hd^-1 yr^-1 and 0.13±0.08 kg hd^-1 yr^-1, respectively. There were remarkable location variations of GHG emissions from different zones (cubicle zone vs. aisle zone) of the open lot. However, the emissions from the whole open lot were less affected by the locations. After manure removal, lower CH₄ but higher N₂O emitted from the open lot. Estimated CO₂, CH₄ and N₂O emissions from stockpile with a stacking height of 55±12 cm were 858.9±375.8 kg hd^-1 yr^-1, 8.5±5.4 kg hd^-1 yr^-1 and 2.3±1.1 kg hd^-1 yr^-1, respectively. In situ storage duration, which estimated by manure volatile solid contents (VS), would affect GHG emissions from stockpiles. Much higher N₂O was emitted from stockpiles in summer due to longer manure storage.

Implications: This study deals with greenhouse gas (GHG) emissions from open lots and stockpiles. It’s an increasing area of concern in some livestock producing countries. The Intergovernmental Panel on Climate Change (IPCC) methodology is commonly used for estimation of national GHG emission inventories. There is a shortage of on-farm information to evaluate the accuracy of these equations and default emission factors. This work provides valuable information for improving accounting practices within China or for similar manure management practice in other countries.     

Measuring and modeling nitrous oxide and methane emissions from beef cattle feedlot manure management: First assessments under Brazilian condition

Intensive beef production has increased during recent decades in Brazil and may substantially increase both methane (CH₄) and nitrous oxide (N₂O) emissions from manure management. However, the quantification of these gases and methods for extrapolating them are scarce in Brazil. A case study examines CH₄ and N₂O emissions from one typical beef cattle feedlot manure management continuum in Brazil and the applicability of Manure-DNDC model in predicting these emissions for better understand fluxes and mitigation options. Measurements track CH₄ and N₂O emissions from manure excreted in one housing floor holding 21 animals for 78 days, stockpiled for 73 days and field spread (360 kg N ha^?1). We found total emissions (CH₄ + N₂O) of 0.19 ± 0.10 kg CO₂eq per kg of animal live weight gain; mostly coming from field application (73%), followed housing (25%) and storage (2%). The Manure-DNDC simulations were generally within the statistical deviation ranges of the field data, differing in ?28% in total emission. Large uncertainties in measurements showed the model was more accurate estimating the magnitude of gases emissions than replicate results at daily basis. Modeled results suggested increasing the frequency of manure removal from housing, splitting the field application and adopting no-tillage system is the most efficient management for reducing emissions from manure (up to about 75%). Since this work consists in the first assessment under Brazilian conditions, more and continuous field measurements are required for decreasing uncertainties and improving model validations. However, this paper reports promising results and scientific perceptions for the design of further integrated work on farm-scale measurements and Manure-DNDC model development for Brazilian conditions.     

Photochemical oxidation and dispersion of gaseous sulfur compounds from natural and anthropogenic sources around a coastal location

The photochemical oxidation and dispersion of reduced sulfur compounds (RSCs: H₂S, CH₃SH, DMS, CS₂, and DMDS) emitted from anthropogenic (A) and natural (N) sources were evaluated based on a numerical modeling approach. The anthropogenic emission concentrations of RSCs were measured from several sampling sites at the Donghae landfill (D-LF) (i.e., source type A) in South Korea during a series of field campaigns (May through December 2004). The emissions of natural RSCs in a coastal study area near the D-LF (i.e., source type N) were estimated from sea surface DMS concentrations and transfer velocity during the same study period. These emission data were then used as input to the CALPUFF dispersion model, revised with 34 chemical reactions for RSCs. A significant fraction of sulfur dioxide (SO₂) was produced photochemically during the summer (about 34% of total SO₂ concentrations) followed by fall (21%), spring (15%), and winter (5%). Photochemical production of SO₂ was dominated by H₂S (about 55% of total contributions) and DMS (24%). The largest impact of RSCs from source type A on SO₂ concentrations occurred around the D-LF during summer. The total SO₂ concentrations produced from source type N around the D-LF during the summer (a mean SO₂ concentration of 7.4 ppbv) were significantly higher than those (≤0.3 ppbv) during the other seasons. This may be because of the high RSC and SO₂ emissions and their photochemistry along with the wind convergence.     

Quantifying direct N2O emissions in paddy fields during rice growing season in mainland China: Dependence on water regime

Various water management regimes, such as continuous flooding (F), flooding-midseason drainage-reflooding (F-D-F), and flooding-midseason drainage-reflooding-moist intermittent irrigation, but without water logging (F-D-F-M), are currently practiced in paddy rice production in mainland China. These water regimes have incurred a sensitive change in direct N₂O emission from rice paddy fields. We compiled and statistically analyzed field data on N₂O emission from paddy fields during the rice growing season (71 measurements from 17 field studies) that were published in peer-reviewed Chinese and English journals. Seasonal total N₂O was, on average, equivalent to 0.02% of the nitrogen applied in the continuous flooding rice paddies. Under the water regime of F-D-F or the F-D-F-M, seasonal N₂O emissions increased with N fertilizer applied in rice paddies. An ordinary least square (OLS) linear regression model produced the emission factor (EF) of nitrogen for N₂O averaged 0.42%, but background N₂O emission was not pronounced under the water regime of F-D-F. Under the F-D-F-M water regime, N₂O EF and background emission were estimated to be 0.73% and 0.79 kg N₂O-N ha⁻¹, respectively, during the paddy rice growing season. Based on results of the present study and national rice production data, subsequently, direct N₂O emissions during the rice growing season amounted to 29.0 Gg N₂O-N with the uncertainty of 30.1%, which accounted for 7–11% of the reported estimates of annual total emission from croplands in mainland China. The results of this study suggest that paddy rice relative to upland crop production could have contributed to mitigating N₂O emissions from agriculture in mainland China.     

Occurrence of Carbon Monoxide during Organic Waste Degradation

Abstract

The concentrations of carbon monoxide (CO) and other gases were measured in the emissions from solid waste degradation under aerobic and anaerobic conditions during laboratory and field investigations. The emissions were measured as room temperature headspace gas concentrations in reactors of 1, 30, and 150 L, as well as sucked gas concentrations from windrow composting piles and a biocell, under field conditions. The aerobic composting laboratory experiments consisted of treatments with and without lime. The CO concentrations measured during anaerobic conditions varied from 0 to 3000 ppm, the average being 23 ppm, increasing to 133 ppm when methane (CH₄) concentrations were low. The mean/maximum CO concentrations during the aerobic degradation in the 2-L reactor were 101/194 ppm without lime, 486/2022 ppm with lime, and 275/980 ppm in the 150-L reactors. The presence of CO during the aerobic composting followed a rapid decline in O₂ concentrations Significantly higher CO concentrations were obtained when the aerobic degradation was amended with lime, probably because of a more extreme depletion of oxygen. The mean/maximum CO concentrations under field conditions during aerobic composting were 95/1000 ppm. The CO concentrations from the anaerobic biocell varied from 20 to 160 ppm. The hydrogen sulfide concentrations reached almost 1200 ppm during the anaerobic degradation and 67 ppm during the composting experiments. There is a positive correlation between the CO and hydrogen sulfide concentrations measured during the anaerobic degradation experiments.     

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.     

Adjoint inverse modeling of NOx emissions over eastern China using satellite observations of NO2 vertical column densities

A four-dimensional variational data assimilation system for optimization of NO_x emissions (RC4-NO_x) was developed. A parameterized NO_x chemistry scheme was introduced into the RC4-NO_x system, and key parameters such as chemical production and loss terms of NO_x were calculated in advance using the Community Multiscale Air Quality (CMAQ) modeling system. RC4-NO_x was applied to optimize NO_x emissions over eastern China (EC) in July 1996, 1999, and 2002 using Global Ozone Monitoring Experiment (GOME) satellite observations of NO₂ vertical column densities (VCDs) and a priori emissions from the Regional Emission Inventory in Asia (REAS). After assimilation, RC4-NO_x generally reproduced the spatial distribution, regional averaged values, and time evolution of GOME NO₂ VCDs. Over EC, a priori emissions were reduced by 20% in 1996 and by 8% in 1999, whereas a posteriori emissions were almost the same as a priori emissions in 2002. A priori emissions in the Beijing region were reduced by optimization over the whole simulation period. A posteriori emissions over the Yangtze Delta were larger than a priori emissions in 2002, although they were smaller in both 1996 and 1999. As in other areas, a priori emissions over the North China Plain were reduced in 1996; but those over the eastern part of the plain were increased in 1999, and the area of increased emissions moved slightly westward in 2002. In each region, the growth rates of a posteriori emissions during both 1996–1999 and 1999–2002 became generally larger than those of a priori emissions, and the trends of a posteriori emissions became similar to those of GOME NO₂ VCDs. Our inverse modeling analysis indicates that the rate of increase of NO_x emissions over EC from 1996 to 2002 was much larger for a posteriori emissions (49%) than for a priori emissions (19%).     

Degradation of 1,2-dichloroethane from wash water of ion-exchange resin using Fenton’s oxidation

Background, aim, and scope  

Chlorinated volatile organic compounds (CVOCs), widely used in industry as solvents and chemical intermediates in the production of synthetic resins, plastics, and pharmaceuticals, are highly toxic to the environment and public health. Various studies reported that Fenton’s oxidation could degrade a variety of chlorinated VOCs in aqueous solutions. In acidic conditions, ferrous ion catalyzes the decomposition of H₂O₂ to form a powerful ^•OH radical. In this study, wastewater from wash of ion-exchange resin containing typical CVOC, 1,2-dichloroethane, was treated using Fenton’s oxidation. To reduce environmental load and processing costs of wastewater, Fenton process as a simple and efficient treatment method was applied to degrade 1,2-dichloroethane of wash water.     

Soil CO2 fluxes from direct seeding rice fields under two tillage practices in central China

Agricultural practices affect the production and emission of carbon dioxide (CO₂) from paddy soils. It is crucial to understand the effects of tillage and N fertilization on soil CO₂ flux and its influencing factors for a better comprehension of carbon dynamics in subtropical paddy ecosystems. A 2-yr field study was conducted to assess the effects of tillage (conventional tillage [CT] and no-tillage [NT]) and N fertilization (0 and 210 kg N ha^?1) on soil CO₂ fluxes during the 2008 and 2009 rice growing seasons in central China. Treatments were established following a split-plot design of a randomized complete block with tillage practices as the main plot and N fertilizer level as the split-plot treatment. The soil CO₂ fluxes were measured 24 times in 2008 and 17 times in 2009. N fertilization did not affect soil CO₂ emissions while tillage affected soil CO₂ emissions, where NT had similar soil CO₂ emissions to CT in 2008, but in 2009, NT significantly increased soil CO₂ emissions. Cumulative CO₂ emissions were 2079–2245 kg CO₂–C ha^?1 from NT treatments, and 2084–2141 kg CO₂–C ha^?1 from CT treatments in 2008, and were 1257–1401 kg CO₂–C ha^?1 from NT treatments, and 1003–1034 kg CO₂–C ha^?1 from CT treatments in 2009, respectively. Cumulative CO₂ emissions were significantly related to aboveground biomass and soil organic C. Before drainage of paddy fields, soil CO₂ fluxes were significantly related to soil temperature with correlation coefficients (R) of 0.67–0.87 in 2008 and 0.69–0.85 in 2009; moreover, the Q₁₀ values ranged from 1.28 to 1.55 and from 2.10 to 5.21 in 2009, respectively. Our results suggested that NT rice production system appeared to be ineffective in decreasing carbon emission, which suggested that CO₂ emissions from integrated rice-based system should be taken into account to assess effects of tillage.     

Adsorptive conversion of nitrogen dioxide from etching vent gases over activated carbon

Some metal etching operations emit limited flow rates of waste gases with reddish-brown NO₂ fume, which may cause visual and acidic-odor complaints, as well as negative health effects. In this study, tests were performed by passing caustic-treated waste gases vented from Al-etching operations through columns packed either with virgin or regenerated granular activated carbon (GAC) to test their adsorptive conversion performance of NO₂ in the gases. The gases contained 5–55 ppm NO₂ and acetic and nitric acids of below 3 ppm. Exhausted carbon was regenerated by scrubbing it with caustic solution and water, and dried for further adsorption tests. Results indicate that with an (empty bed residence time (EBRT) of 0.15 sec for the gas through the GAC-packed space, around 60% of the influent NO₂ of 54 ppm could be removed, and 47% of the removed NO₂ was converted by and desorbed from the carbon as NO. GAC used in the present study could be regenerated at least twice to restore its capacity for NO₂ adsorption. Within EBRTs of 0.076–0.18 sec, the adsorptive conversion capacity was linearly varied with EBRT. In practice, with an EBRT of 0.20 sec, a conversion capacity of 0.80 kg NO₂ (kg GAC)^?1 with an influent NO₂ of 40 ppm can be used as a basis for system design.

Implications: Some metal etching operations emit waste gases with reddish-brown (yellow when diluted) NO₂ fume which may cause visual and acidic-odor complaints, as well as negative health effects. This study provides a simple process for the adsorptive conversion of NO₂ in caustic-treated waste gases vented from metal-etching operations through a GAC column. With an EBRT of 0.20 sec, a conversion capacity of 0.80 kg NO₂ (kg GAC)^?1 with an influent NO₂ of 40 ppm can be used as a basis for system design. Saturated GAC can be regenerated at least twice by simply scrubbing it with aqueous caustic solution.     

Carbonyl sulfide,dimethyl sulfide and carbon disulfide in the Pearl River Delta of southern China: Impact of anthropogenic and biogenic sources

Reduced sulfur compounds (RSCs) such as carbonyl sulfide (OCS), dimethyl sulfide (DMS) and carbon disulfide (CS₂) impact radiative forcing, ozone depletion, and acid rain. Although Asia is a large source of these compounds, until now a long-term study of their emission patterns has not been carried out. Here we analyze 16 months of RSC data measured at a polluted rural/coastal site in the greater Pearl River Delta (PRD) of southern China. A total of 188 canister air samples were collected from August 2001 to December 2002. The OCS and CS₂ mixing ratios within these samples were higher in autumn/winter and lower in summer due to the influence of Asian monsoon circulations. Comparatively low DMS values observed in this coastal region suggest a relatively low biological productivity during summer months. The springtime OCS levels in the study region (574 ± 40 pptv) were 25% higher than those on other East Asia coasts such Japan, whereas the springtime CS₂ and DMS mixing ratios in the PRD (47 ± 38 pptv and 22 ± 5 pptv, respectively) were 3–30 times lower than elevated values that have been measured elsewhere in East Asia (Japan and Korea) at this time of year. Poor correlations were found among the three RSCs in the whole group of 188 samples, suggesting their complex and variable sources in the region. By means of backward Lagrangian particle release simulations, air samples originating from the inner PRD, urban Hong Kong and South China Sea were identified. The mean mixing ratio of OCS in the inner PRD was significantly higher than that in Hong Kong urban air and South China Sea marine air (p < 0.001), whereas no statistical differences were found for DMS and CS₂ among the three regions (p > 0.05). Using a linear regression method based on correlations with the urban tracer CO, the estimated OCS emission in inner PRD (49.6 ± 4.7 Gg yr^?1) was much higher than that in Hong Kong (0.32 ± 0.05 Gg yr^?1), whereas the estimated CS₂ and DMS emissions in the study region accounted for a very few percentage of the total CS₂ and DMS emission in China. These findings lay the foundation for better understanding sulfur chemistry in the greater PRD region of southern China.