Kinetics of catalytic oxidation of benzene, n-hexane, and emission gas from a refinery oil/water separator over a chromium oxide catalyst

With the advances made in the past decade, catalytic incineration of volatile organic compounds (VOCs) has become the technology of choice in a wide range of pollution abatement strategies. In this study, a test was undertaken for the catalytic incineration, over a chromium oxide (Cr2O3) catalyst, of n-hexane, benzene, and an emission air/vapor mixture collected from an oil/water separator of a refinery. Reactions were carried out by controlling the feed stream to constant VOC concentrations and temperatures, in the ranges of 1300-14,700 mg/m3 and 240-400 degrees C, respectively. The destruction efficiency for each of the three VOCs as a function of influent gas temperature and empty bed gas residence time was obtained. Results indicate that n-hexane and the oil vapor with a composition of straight- and branch-chain aliphatic hydrocarbons exhibited similar catalytic incineration effects, while benzene required a higher incineration temperature or longer gas retention time to achieve comparable results. In the range of the VOC concentrations studied, at a given gas residence time, increasing the operating temperature of the catalyst bed increased the destruction efficiency. However, the much higher temperatures required for a destruction efficiency of over 99% may be not cost-effective and are not suggested. A first-order kinetics with respect to VOC concentration and an Arrhenius temperature dependence of the kinetic constant appeared to be an adequate representation for the catalytic oxidation of these volatile organics. Activation energy and kinetic constants were estimated for each of the VOCs. Low-temperature destruction of the target volatile organics could be achieved by using the Cr2O3 catalyst.     

Determination of S02 Emission from Oil Combustion Sources by Fuel Analyses and S02/C02 Relations

The current S0₂ emission test methods, based on wet chemistry, are time consuming and costly. Final results depend on at least 10 separate measurements of quantities which may introduce significant errors due to human factors especially under unfavorable field environment. Performance evaluation of several promising S0₂ instrumental methods indicated that results were reliable and reproducible, but instrumental problems still exist. The problems were found to be calibration, mechanical and electronic components, and sample conditioning system. An alternative method proposed requires only two separate analyses: ultimate fuel analysis and stack gas analysis for C0₂. This method can be further simplified with reasonable accuracy by a single measurement of sulfur in the fuel if results are corrected to 12% C0₂. The method can be a useful addition to the current methods, especially if cost and manpower preclude actual stack tests. A test program was conducted at four industrial and utility power plants. Results are presented with discussion to show the application and validity of the simplified method.     

Emission characteristics of PCDD/Fs, PCBs, chlorobenzenes, chlorophenols, and PAHs from polyvinylchloride combustion at various temperatures

The effect of temperature on polyvinylchloride (PVC) combustion using a downstream tubular furnace was investigated for the formation of polycylcic aromatic hydrocarbons (PAHs) and chlorinated compounds. As the temperature increased, higher levels of PAHs were generated. Chlorinated compounds reached a peak at 600 degrees C, with low emissions recorded at 300 and 900 degrees C. There was a close correlation (R2 = 0.97) among polychlorinated biphenyls (PCBs), hexachlorobenzene, pentachlorobenzene, and polychlorinated dibenzo-p-dioxins and polychlorinated dibenzofurans (PCDD/Fs). PAHs at all temperatures were analyzed in the gas phase. PCDD/Fs and PCBs were emitted as a solid phase at 300 and 600 degrees C and as a gas phase at 900 degrees C. For some PAHs, chlorobenzenes, and PCDD/Fs, a mathematical equation between the gas and solid phase and the reciprocal temperature in semilog proportion was derived. The proposed equation, which is log (amount in gas phase/amount in solid phase) = -A/T + B, where T is the temperature of the furnace and A and B are constants, for these species relating their gas/solid distributions showed a good relationship.     

Seasonal and monthly variations of columnar aerosol optical properties over east Asia determined from multi-year MODIS,LIDAR, and AERONET Sun/sky radiometer measurements

Multi-year records of MODIS, micro-pulse lidar (MPL), and aerosol robotic network (AERONET) Sun/sky radiometer measurements were analyzed to investigate the seasonal, monthly and geographical variations of columnar aerosol optical properties over east Asia. Similar features of monthly and seasonal variations were found among the measurements, though the observational methodology and periods are not coincident. Seasonal and monthly cycles of MODIS-derived aerosol optical depth (AOD) over east Asia showed a maximum in spring and a minimum in autumn and winter. Aerosol vertical extinction profiles measured by MPL also showed elevated aerosol loads in the middle troposphere during the spring season. Seasonal and spatial distributions were related to the dust and anthropogenic emissions in spring, but modified by precipitation in July–August and regional atmospheric dispersion in September–February. All of the AERONET Sun/sky radiometers utilized in this study showed the same seasonal and monthly variations of MODIS-derived AOD. Interestingly, we found a peak of monthly mean AOD over industrialized coastal regions of China and the Yellow Sea, the Korean Peninsula, and Japan, in June from both MODIS and AERONET Sun/sky radiometer measurements. Especially, the maximum monthly mean AOD in June is more evident at the AERONET urban sites (Beijing and Gwangju). This AOD June maximum is attributable to the relative contribution of various processes such as stagnant synoptic meteorological patterns, secondary aerosol formation, hygroscopic growth of hydrophilic aerosols due to enhanced relative humidity, and smoke aerosols by regional biomass burning.     

Emission profiles of polychlorinated dibenzodioxins, polychlorinated dibenzofurans (PCDD/Fs), dioxin-like PCBs and hexachlorobenzene (HCB) from secondary metallurgy industries in Portugal

This paper reports, for the first time, a study of dioxin emissions from 10 siderurgies and metallurgies, secondary copper, aluminum and lead metallurgies, in Portugal. The study reports the emission factors and total emission amounts of PCDD/Fs, dioxin-like PCBs and hexachlorobenzene (HCB). The congener patterns were characterized and are discussed. The results showed that the total amount of PCDFs is higher than PCDDs in flue gas of each industrial unit. The toxic equivalent emission factors of pollutants emitted are 3098-3338 ngI-TEQt(-1) for PCDD/Fs and 597-659 ng I-TEQt(-1) for dioxin-like PCBs in siderurgies production (total estimated emission amounts released to atmosphere of 3.9-4.5 g I-TEQyr(-1)), 50-152 ng I-TEQt(-1) for PCDD/Fs and 24-121 ng I-TEQt(-1) for dioxin-like PCBs in ferrous foundries production (total estimated emission amounts released to atmosphere of 0.0010-0.0016 g I-TEQyr(-1)) and 5.8-5715 ng I-TEQt(-1) for PCDD/Fs and 0.49-259 ng I-TEQt(-1) for dioxin-like PCBs in non-ferrous foundries production (total estimated emission amounts released to atmosphere of 0.00014-0.12 g I-TEQyr(-1)). The HCB emission from siderurgies production is 0.94-3.2 mg t(-1) (total estimated emission amounts released 0.94-3.8 g yr(-1)), being much smaller, residual, in the emissions of the other types of plants (0.0012-0.026 mg t(-1) production and total estimated emission amounts released to atmosphere of 0.013-1.7 mg yr(-1)).     

Assessment of the emission of PCDD/Fs and dioxin-like PCBs from an industrial area over a nearby town using a selective wind direction sampling device

The development of new sampling devices or strategies to assess the concentration of persistent organic pollutants (POPs) in the environment has increased in the last two decades. In this study, a selective sampling device was used to evaluate the impact of potential local sources of polychlorinated dibenzo-p-dioxin and dibenzofuran (PCDD/Fs) and dioxin-like polychlorinated biphenyl (dl-PCBs) emissions on the ambient air levels of such compounds in a town near an important industrial estate. Average concentrations of target compounds of up to 2.5 times for PCDD/Fs and 2 times for dl-PCBs were found to come from the industrial state confirming this area as the main responsible for the majority of such compounds reaching the town.This finding was supported by a PCDD/F and dl-PCB sample profile analysis and a principal component analysis (PCA), which established a direct link between the dioxin-like compounds found in the samples collected in the town and their source.     

Effects of diesel/biodiesel blends on regulated and unregulated pollutants from a passenger vehicle operated over the European and the Athens driving cycles

This paper presents the regulated and unregulated exhaust emissions of a diesel passenger vehicle, operated with low sulphur automotive diesel and soy methyl ester blends. Emission and fuel consumption measurements were conducted under real driving conditions (Athens Driving Cycle, ADC) and compared with those of a modified New European Driving Cycle (NEDC) using a chassis dynamometer. A Euro II compliant diesel vehicle was used in this study, equipped with an indirect injection diesel engine, fuelled with diesel fuel and biodiesel blends at proportions of 5, 10, and 20% respectively. Unregulated emissions of 11 polycyclic aromatic hydrocarbons (PAHs), 5 nitro-PAHs, 13 carbonyl compounds (CBCs) and the soluble organic fraction (SOF) of the particulate matter were measured. Qualitative hydrocarbon analysis was also performed on the SOF. Regulated emissions of NO_x, CO, HC, CO₂, and PM were also measured over the two test cycles. It was established that some of the emissions measured over the (hot-start) NEDC differed from the real-world cycle. Significant differences were also observed in the vehicle's fuel consumption between the two test cycles. The addition of biodiesel reduced the regulated emissions of CO, HC and PM, while an increase in NO_x was observed over the ADC. Carbonyl emissions, PAHs and nitro-PAHs were reduced with the addition of biodiesel over both driving cycles.     

Removal of heavy metal ions from wastewater by a novel HEA/AMPS copolymer hydrogel: preparation, characterization, and mechanism

This study aims to synthesize 2-hydroxyethyl acrylate (HEA) and 2-acrylamido-2-methylpropane sulfonic (AMPS) acid-based hydrogels by gamma radiation and to investigate their swelling behavior and heavy metal ion adsorption capabilities. The copolymer hydrogels prepared were characterized via scanning electron microscopy, Fourier transformed infrared spectra, thermal gravimetric analysis, and X-ray photoelectron spectroscopy. The research showed that the copolymer hydrogel was beneficial for permeation due to its porous structure. In addition, the experimental group A-2-d [70 % water volume ratio and (n (AMPS)/n (HEA))?=?1:1] was an optimal adsorbent. The optimal pH was 6.0 and the optimal temperature was 15 °C. Pb²⁺, Cd²⁺, Cu²⁺, and Fe³+ achieved adsorption equilibriums within 24 h, whereas Cr³⁺ reached equilibrium in 5 h. Pb²+, Cd²⁺, Cr³⁺, and Fe³⁺ maximum load capacity was 1,000 mg L^?1, whereas the Cu²⁺ maximum capacity was 500 mg L^?1. The priority order in the multicomponent adsorption was Cr³⁺>Fe³⁺>Cu²⁺>Cd²⁺>Pb²⁺. The adsorption process of the HEA/AMPS copolymer hydrogel for the heavy metal ions was mainly due to chemisorption, and was only partly due to physisorption, according to the pseudo-second-order equation and Langmuir adsorption isotherm analyses. The HEA/AMPS copolymer hydrogel was confirmed to be an effective adsorbent for heavy metal ion adsorption.     

Study of PCDD/Fs distribution in fly ash,ash deposits,and bottom ash from a medical waste incinerator in China

Over the past decades in China, the number of medical waste incinerators (MWIs) has been rising rapidly, causing emissions of polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/Fs). In this study, samples of fly ash, ash deposits, and bottom ash from typical MWIs were analyzed for PCDD/Fs and their distribution characteristics. Results showed international toxic equivalent (I-TEQ) values in the range of 6.9–67 ng I-TEQ/g in fly ash and ash deposits, whereas the concentration in bottom ash was extremely low (only 1.33 pg I-TEQ/g), yet the generation of PCDD/Fs was mostly de novo synthesis in fly ash and ash deposits according to the ratio of PCDFs to PCDDs; the major distribution differences of PCDD/Fs in fly ash was manifested by the content of toxic furan 2,3,7,8-TCDF, but other toxic PCDD/Fs showed similar distribution. Other findings are that 2,3,4,7,8-PeCDF had the most contribution to TEQ concentration, and that the most abundant toxic furan congener is 1,2,3,4,6,7,8-HpCDF. Correlation analysis showed that there was no significant correlation between PCDD/Fs concentration and several other physical and chemical parameters.

Implications: This paper is of interest because it presents the emission performances of PCDD/Fs in ash from medical waste incineration in China. PCDD/F contents in fly ash and ash deposits vary between 6.9 and 67.3 ng I-TEQ/g. However, the concentration in bottom ash was extremely low (only 1.33?×?10^?3 ng I-TEQ/g). The fingerprints of PCDD/Fs in fly ash are almost similar, except for 2,3,7,8-TCDF. There is no marked correlation between PCDD/Fs and other physicochemical properties.

Supplemental Materials: Supplemental materials are available for this paper. Go to the publisher's online edition of the Journal of the Air & Waste Management Association.     

Carbon source/sink function of a subtropical, eutrophic lake determined from an overall mass balance and a gas exchange and carbon burial balance

Although studies on carbon burial in lake sediments have shown that lakes are disproportionately important carbon sinks, many studies on gaseous carbon exchange across the water-air interface have demonstrated that lakes are supersaturated with CO(2) and CH(4) causing a net release of CO(2) and CH(4) to the atmosphere. In order to more accurately estimate the net carbon source/sink function of lake ecosystems, a more comprehensive carbon budget is needed, especially for gaseous carbon exchange across the water-air interface. Using two methods, overall mass balance and gas exchange and carbon burial balance, we assessed the carbon source/sink function of Lake Donghu, a subtropical, eutrophic lake, from April 2003 to March 2004. With the overall mass balance calculations, total carbon input was 14 905 t, total carbon output was 4950 t, and net carbon budget was +9955 t, suggesting that Lake Donghu was a great carbon sink. For the gas exchange and carbon burial balance, gaseous carbon (CO(2) and CH(4)) emission across the water-air interface totaled 752 t while carbon burial in the lake sediment was 9477 t. The ratio of carbon emission into the atmosphere to carbon burial into the sediment was only 0.08. This low ratio indicates that Lake Donghu is a great carbon sink. Results showed good agreement between the two methods with both showing Lake Donghu to be a great carbon sink. This results from the high primary production of Lake Donghu, substantive allochthonous carbon inputs and intensive anthropogenic activity. Gaseous carbon emission accounted for about 15% of the total carbon output, indicating that the total output would be underestimated without including gaseous carbon exchange.     

Comparison of PCDD/PCDF levels in soil, grass, cow''s milk, human blood and spruce needles in an area of PCDD/PCDF contamination through emissions from a metal reclamation plant

When in the vicinity of a metal reclamation plant in Tyrol, Austria, increased PCDD/PCDF levels were found in soil and spruce needles, the extent of grass contamination as well as the PCDD/PCDF content in milk of cows fed with hay from this area was determined. The milk samples showed a significant increase in PCDD/PCDF levels compared to control samples. In a blood sample of a farmer a significant increase in PCDD/PCDF levels was found. Correlations in PCDD/PCDF levels between soil, spruce needles, grass, cow's milk and human blood will be presented.     

Distribution of PCDD/Fs and dioxin-like PCBs in sediment and plants from a contaminated salt marsh (Tejo estuary,Portugal)

Concentrations and profiles of 2,3,7,8-substituted polychlorinated dibenzo-p-dioxins, polychlorinated dibenzofurans (PCDD/Fs) and dioxin-like polychlorinated biphenyls (dl-PCBs) were investigated in sediment and plants collected from a salt marsh in the Tejo estuary, Portugal. The highest PCDD/F and dl-PCB concentrations were detected in uncolonized sediments, averaging 325.25?±?57.55 pg g^?1 dry weight (dw) and 8,146.33?±?2,142.14 pg g^?1 dw, respectively. The plants Sarcocornia perennis and Halimione portulacoides growing in PCDD/F and dl-PCB contaminated sediments accumulated contaminants in roots, stems, and leaves. It was observed that PCDD/F and dl-PCB concentrations in roots were significantly lower in comparison with stems and leaves. In general, concentration of ΣPCDD/Fs and Σdl-PCBs in H. portulacoides tissues were found to be twofold higher than those in S. perennis, indicating a difference in the accumulation capability of both species. Furthermore, congener profiles changed between sediments and plant tissues, reflecting a selective accumulation of low chlorinated PCDD/Fs and non-ortho dl-PCBs in plants.     

Analysis of volatile organic compounds, using the purge and trap injector coupled to a gas chromatograph/ion-trap mass spectrometer: review of the results in Dutch surface water of the Rhine, Meuse, Northern Delta Area and Westerscheldt, over the period 1992-1997

Volatile organic compounds are widely introduced into the Dutch aquatic environment. Liquid-liquid extraction and isolation by means of resins give poor recoveries for volatiles. In this study, a method has been developed to analyse these compounds with a purge and trap injection (PTI) coupled to a chromatograph/ion trap mass spectrometer. Volatile compounds are "purged" from the sample by carrier gas flow and transported through a condenser to a cooled trap. The bulk of liquid matrix is condensed in the condenser, while volatile compounds are left unaffected. The compounds of interest are trapped at a low temperature, by liquid nitrogen in the cooled trap of fused silica. Injection takes place by flash heating of the trap. The detection limits of the volatile compounds are in the range of 0.001-0.04 microgram l-1, in full spectrum mode. In this paper a review of the results in Dutch surface water of the Rhine, Meuse, Northern Delta Area and Westerscheldt, over the period 1992-1997, is presented. For calamities causing high levels of volatiles, the method is very useful. The compounds can be monitored over a certain period. In the Meuse, high levels of volatile organic compounds are observed. Diisopropyl ether at a maximum of 592 micrograms l-1.     

Evolution of tolerance to PCBs and susceptibility to a bacterial pathogen (Vibrio harveyi) in Atlantic killifish (Fundulus heteroclitus) from New Bedford (MA, USA) harbor

A population of the non-migratory estuarine fish Fundulus heteroclitus (Atlantic killifish) resident to New Bedford (NB), Massachusetts, USA, an urban harbor highly contaminated with polychlorinated biphenyls (PCBs), demonstrates recently evolved tolerance to some aspects of PCB toxicity. PCB toxicology, ecological theory, and some precedence supported expectations of increased susceptibility to pathogens in NB killifish. However, laboratory bacterial challenges of the marine pathogen Vibrio harveyi to wild fish throughout the reproductive season and to their mature laboratory-raised progeny demonstrated comparable survival by NB and reference killifish, and improved survival by NB males. These results are inconsistent with hypothesized trade-offs of adaptation, and suggest that evolved tolerance in NB killifish may include mechanisms that minimize the immunosuppressive effects of PCBs. Compensatory strategies of populations persisting in highly contaminated environments provide a unique perspective for understanding the long-term ecological effects of toxic chemicals.     

New cytochrome P450 1B1, 1C1, 2Aa, 2Y3, and 2K genes from Chinese rare minnow (Gobiocypris rarus): Molecular characterization,basal expression and response of rare minnow CYP1s and CYP2s mRNA exposed to the AHR agonist benzo[a]pyrene

Cytochrome P450 (CYP450) genes play an important role in catalyzing oxidative metabolism of toxicants. Recently, CYP1 subfamily were discovered and reported in fish, however, little is known regarding the CYP2 isoforms in fish. In the present study, the cDNA fragments of CYP 1B1 and 1C1 and CYP2Aa, 2Y3, and 2K of rare minnow were cloned and exhibited a high amino acid sequence identity compared with their zebrafish orthologs. Basal expression showed CYP1C1 and CYP 2Aa expression were observed in all eight tissues analyzed (liver, gill, intestine, kidney, spleen, brain, skin, and muscle). CYP 1A, and 1B1 expression was found in all tissues except for muscle and skin. However, CYP 2Y3 was expressed in liver, spleen, intestine and muscle whereas CYP 2 K in liver, kidney and intestine. 4 and 100 μg L⁻¹ Benzo[a]pyrene (BaP) induced patterns showed that CYP 1A, 1B1 and 1C1 expression in liver, gill, and intestine was strongly up-regulated (p < 0.05). Furthermore, CYP 2Y3 was strongly induced in liver from BaP treatments (p < 0.05). The high induction on mRNA level of CYP1s and CYP 2Y3 by BaP could be associated with catalyzing detoxification and indicated that CYP2s may also be potential biomarker to screen AHR agonist. The high responsiveness of CYP1 and 2 genes suggested Chinese rare minnow is feasible to screen and assess pollution with AHR agonist.