Investigation of adsorption characteristics of four toxic gases (nitric oxide,nitrogen dioxide,sulfur dioxide,and hydrogen chloride) on the inner surface of nickel-coated manganese steel cylinders and aluminum cylinders

To develop standard toxic gas mixtures, it is essential to identify adsorption characteristics of each toxic gas on the inner surface of a gas cylinder. Thus, this study quantified adsorbed amounts of the four toxic gases (nitric oxide [NO], nitrogen dioxide [NO₂], sulfur dioxide [SO₂], and hydrogen chloride [HCl]) on the inner surface of aluminum cylinders and nickel-coated manganese steel cylinders. After eluting adsorbed gases on the inside of cylinders with ultrapure water, a quantitative analysis was performed on an ion chromatograph. To evaluate the reaction characteristics of the toxic gases with cylinder materials, quantitative analyses of nickel (Ni), iron (Fe), and aluminum (Al) were also performed by inductively coupled plasma optical emission spectrometry (ICP-OES). It was found that the amounts of NO, NO₂, and SO₂ adsorbed on the inner surface of aluminum cylinders were less than 1.0% at the level of 100 μmol/mol mixing ratio, whereas the signal for most heavy metal elements were below their respective detection limits. This study found that the amounts of HCl adsorbed on the inner surface of nickel-coated manganese steel cylinders were less than 5% at the level of 100 μmol/mol mixing ratio, whereas Ni (86 μmol) and Fe (28 μmol) were detected in the same cylinders. It was revealed that the adsorption mainly took place via the reaction of HCl with inner surface material of nickel-coated manganese steel cylinders. On the other hand, in the case of aluminum cylinders, the amounts of the adsorption were determined to be less than 1% at the level of HCl 100 μmol/mol mixing ratio, whereas most of Ni, Fe, and Al were detected at levels similar to their limits of detection. As a result, this study found that aluminum cylinders are more suitable for preparing HCl gas mixtures than nickel-coated manganese steel cylinders.

Implications: To develop a standard toxic gas mixture, it is essential to understand the adsorption characteristics of each toxic gas inside a gas cylinder. It was found that the amounts of NO, NO₂, and SO₂ adsorbed inside aluminum cylinders were less than 1.0% at the level of 100 μmol/mol mixing ratio. The amounts of HCl adsorbed inside nickel-coated manganese steel cylinders were less than 5% at the level of 100 μmol/mol mixing ratio, whereas those inside aluminum cylinders were less than 1%, indicating that aluminum cylinders are more suitable for preparing HCl gas mixtures.     

Pattern recognition of the movement tracks of medaka (Oryzias latipes) in response to sub-lethal treatments of an insecticide by using artificial neural networks

Specimens of medaka (Oryzias latipes) were observed continuously through an automatic image recognition system before and after treatments of an anti-cholinesterase insecticide, diazinon (0.1 mg/l), for 4 days in semi-natural conditions (2 days before treatment and 2 days after treatment). The "smooth" pattern was typically shown as a normal movement behavior, while the "shaking" pattern was frequently observed after treatments of diazinon. These smooth and shaking patterns were selected for training with an artificial neural network. Parameters characterizing the movement tracks, such as speed, degree of backward movements, stop duration, turning rate, meander, and maximum distance movements in the y-axis of 1-min duration, were given as input (six nodes) to a multi-layer perceptron with the back propagation algorithm. Binary information for the smooth and shaking patterns was separately given as the matching output (one node), while eight nodes were assigned to a single hidden layer. As new input data were given to the trained network, it was possible to recognize the smooth and shaking patterns of the new input data. Average recognition rates of the smooth pattern decreased significantly while those for the shaking pattern increased to a higher degree after treatments of diazinon. The trained network was able to reveal the difference in the shaking pattern in different light phases before treatments of diazinon. This study demonstrated that artificial neural networks could be useful for detecting the presence of toxic chemicals in the environment by serving as in-situ behavioral monitoring tools.     

Hg reactions in the presence of chlorine species: homogeneous gas phase and heterogeneous gas-solid phase

The kinetics of Hg chlorination (with HCl) was studied using a flow reactor system with an online Hg analyzer, and speciation sampling using a set of impingers. Kinetic parameters, such as reaction order (alpha), overall rate constant (k'), and activation energy (Ea), were estimated based on the simple overall reaction pathway. The reaction order with respect to C(Hg), k', and Ea were found to be 1.55, 5.07 x 10(-2) exp(-1939.68/T) [(microg/m3)(-055)(s)(-1)]. and 16.13 [kJ/ mol], respectively. The effect of chlorine species (HCl, CH2Cl2) on the in situ Hg capture method previously developed (28) was also investigated. The efficiency of capture of Hg by this in situ method was higher than 98% in the presence of chlorine species. Furthermore, under certain conditions, the presence of chlorine enhanced the removal of elemental Hg by additional gas-phase oxidation.     

Cancer risk from gaseous carbonyl compounds in indoor environment generated from household coal combustion in Xuanwei,China

Airborne carbonyls were characterized from emitted indoor coal combustion. Samples were collected in Xuanwei (Yunnan Province), a region in China with a high rate of lung cancer. Eleven of 19 types of samples (58%) demonstrated formaldehyde concentrations higher than the World Health Organization exposure limit (a 30-min average of 100 μg m^?3). Different positive significant correlations between glyoxal/methylglyoxal and formaldehyde/acetaldehyde concentrations were observed, suggesting possible different characteristics in emissions between two pairs of carbonyl compounds. A sample in the highest inhalation risk shows 29.2 times higher risk than the lowest sample, suggesting different coal sampling locations could contribute to the variation of inhalation risk. Inhabitants in Xuanwei also tend to spend more time cooking and more days per year indoors than the national average. The calculated cancer risk ranged from 2.2–63 × 10^?5, which shows 13 types of samples at high-risk level. Cumulative effect in combination with different carbonyls could have contributed to the additive actual inhalation cancer risk. There is a need to explicitly address the health effects of environmentally relevant doses, considering life-long exposure in indoor dwellings.     

Utility of stormwater monitoring.

Stormwater runoff is now a major contributor to the pollution of coastal waters in the United States. Public agencies are responding by requiring stormwater monitoring to satisfy the National Pollutant Discharge Elimination System stormwater permit. However, studies to understand the utility of the current programs or to improve their usefulness have not yet been performed. In this paper, we evaluate the land-use-based program, the industrial stormwater permit program, and beach water-quality monitoring in the County of Los Angeles, California, to determine if the results will be helpful to planners and regulators in abating stormwater pollution. The utility of the program has been assessed based on the programs' ability to accurately estimate the emissions for different classes of land use. The land-use program appears successful, while the industrial monitoring program does not. Beach water-quality monitoring suffers from a lack of real-time monitoring techniques. We also provide suggested improvements, such as sampling method and time, and parameter selection.     

Photodegradation of pentachlorophenol and its degradation pathways predicted using density functional theory

The objectives of the present research were (i) to report the mass balance of chlorine during pentachlorophenol (PCP) photodegradation and (ii) to reveal the photodegradation pathway experimentally with a theoretical proof based on the density functional theory (DFT). The chlorine of PCP was completely mineralized to produce chloride ions after 24h of UV irradiation. As intermediates, 2,3,5,6-tetrachlorophenol, 2,3,4,6-tetrachlorophenol and 2,5-dichlorophenol were identified. At least 80% of the chlorine balance during PCP photodegradation was accounted by PCP, these intermediates, and chloride ions. A DFT calculation showed differences in the C-Cl bond dissociation energy level and the positions of respective PCP molecular and the PCP intermediates. The dechlorination intermediates predicted using the calculated C-Cl bond dissociation energy were consistent with those experimentally confirmed, indicating the feasibility of this theoretical method in predicting the dechlorination pathway.     

The effects of perennial ryegrass and alfalfa on microbial abundance and diversity in petroleum contaminated soil

Enhanced rhizosphere degradation uses plants to stimulate the rhizosphere microbial community to degrade organic contaminants. We measured changes in microbial communities caused by the addition of two species of plants in a soil contaminated with 31,000 ppm of total petroleum hydrocarbons. Perennial ryegrass and/or alfalfa increased the number of rhizosphere bacteria in the hydrocarbon-contaminated soil. These plants also increased the number of bacteria capable of petroleum degradation as estimated by the most probable number (MPN) method. Eco-Biolog plates did not detect changes in metabolic diversity between bulk and rhizosphere samples but denaturing gradient gel electrophoresis (DGGE) analysis of PCR-amplified partial 16S rDNA sequences indicated a shift in the bacterial community in the rhizosphere samples. Dice coefficient matrices derived from DGGE profiles showed similarities between the rhizospheres of alfalfa and perennial ryegrass/alfalfa mixture in the contaminated soil at week seven. Perennial ryegrass and perennial ryegrass/alfalfa mixture caused the greatest change in the rhizosphere bacterial community as determined by DGGE analysis. We concluded that plants altered the microbial population; these changes were plant-specific and could contribute to degradation of petroleum hydrocarbons in contaminated soil.     

Iron and organo-bentonite for the reduction and sorption of trichloroethylene

Hybrid barriers using dechlorination and immobilization were studied to remove trichloroethylene (TCE) in this study. Hybrid barriers of iron filings and organo (hexadecyltrimethylammonium, HDTMA)-bentonite were simulated in columns to assess the performance of the hybrid barriers. TCE reduction rate for the mixture of zero valent iron (ZVI) and HDTMA-bentonite was approximately seven times higher than that for ZVI, suggesting the reduction of TCE was accelerated when HDTMA-bentonite was mixed with ZVI. For the column of two separate layers of iron and HDTMA-bentonite, TCE reduction rate was nearly similar to that for ZVI alone, but the partition coefficient (Kd) was 4.5 times higher than that for ZVI only. TCE was immobilized in the first layer with HDTMA-bentonite due to sorption, and then dechlorinated in the second layer with iron filings due to reduction. The HDTMA-bentonite and minimally-desorbed HDTMA from the organo-bentonite are believed to contribute the increase in TCE concentration on iron surface so that more TCE could be available for reduction. Therefore, the incorporation of HDTMA-bentonite into ZVI not only can effectively retard the transport of chlorinated organic contaminants from landfill leachate or oil shock in subsurface environment, also can expedite the reduction rate of TCE.     

Bioregeneration of powdered activated carbon in the treatment of alkyl-substituted phenolic compounds in simultaneous adsorption and biodegradation processes

The role of bioregeneration process in renewing the adsorbent surface for further adsorption of organics during simultaneous adsorption and biodegradation processes has been well recognized. The extent of bioregeneration of powdered activated carbon (PAC) as an adsorbent loaded with phenol, p-methylphenol, p-ethylphenol and p-isopropylphenol, respectively, in the simultaneous adsorption and biodegradation processes were quantitatively determined using oxygen uptake as a measure of substrate consumption. Bioregeneration phenomenon was also evaluated in the simultaneous adsorption and biodegradation processes under sequencing batch reactor (SBR) operation to treat synthetic wastewater containing 1200 mg l(-1) phenol and p-methylphenol, respectively. The SBR systems were operated with FILL, REACT, SETTLE, DRAW and IDLE periods in the ratio of 4:6:1:0.75:0.25 for a cycle time of 12 h. The results show that the percentage of desorption from loaded PAC decreased in the order phenol>p-methylphenol>p-ethylphenol>p-isopropylphenol. For the treatment of phenol and p-methylphenol in the SBR reactors, respectively, the simultaneous adsorption and biodegradation processes were able to produce a consistent effluent quality of COD < or = 100 mg l(-1) when the applied PAC dosage was 0.115 and 0.143 g PAC per cycle, respectively. When no further PAC was added, the treatment performance deteriorated to that of the case without PAC addition after 68 and 48 cycles of SBR operation, respectively, for phenol and p-methylphenol. This observation is consistent with the greater extent of bioregeneration for phenol-loaded PAC as compared to p-methylphenol-loaded PAC.     

Local circulation and aerosol water-soluble ions--a case study in Taiwan during Mei-yu season

The Mei-yu (plum rain) season is a short but important period when the weather changes from spring to summer in Taiwan. In this study, size-segregated aerosols were collected alternately at 5 sampling sites in northwestern Taiwan from June 16 to 24, 1994. For the first time in Taiwan, this study revealed the aerosol mass spectra and water-soluble ions in the Mei-yu season. For all samples, a bi-modal aerosol mass spectra was found with modal diameters at 3.2 and 0.32 microm, respectively. The aerosol samples were able to be divided into different groups to show their mass and ion spectra according to the calculated 5-hr backward air trajectory. The utilization of enrichment factors showed that aerosol Cl-, Na+, and Mg2+ for all sizes, and super-micron SO4(2-) were related to the sea. Both the scheme of "chlorine loss" (Ohta and Okita, 1990) and a multivariate analysis (Thurston and Spengler, 1985) for categorizing water-soluble ions showed that sea-salts were major contributors in the prevalence of a sea breeze. In contrast, the secondary salts were significant for land breeze and a mix of land-sea breeze. In conclusion, the influence of local circulation on the distribution of aerosol mass and ionic species was found to be prominent.