1H-NMR-based metabolomic study on toxicity of methomyl and methidathion in fish

A ¹H-nuclear magnetic resonance (NMR) spectroscopy with multivariate analysis was applied to detect the toxicity of antiacetylcholinesterase insecticides, methomyl (methyl (1E)-N-(methylcarbamoyloxy)ethanimidothioate) and methidathion (3-(dimethoxyphosphinothioyl sulfanylmethyl)-5-methoxy-1,3,4-thiadiazol-2-one), using zebrafish (Danio rerio) and Chinese bleak (Aphyocypris chinensis). Generally, methomyl and methidathion have been believed not to highly accumulate in fish tissues. However, these pesticides showed their toxicity by altering patterns of whole-body metabolites in neurotransmitter balance, energy metabolism, oxidative stress, and muscle maintenance in low concentrations. We used Pearson correlation analysis to contextualize the metabolic markers in pesticide treated groups. We observed that the positive correlations of choline with acetate and betaine in untreated control were shifted to null correlations showing acetylcholinesterase specific toxicity. This research demonstrated the applicability and potential of NMR metabolomics in detecting toxic effects of insecticide with a modicum of concentrations in aquatic environment.     

Effect of metabolic uncouplers on the performance of toluene-degrading biotrickling filter

Environmental Science and Pollution Research - The biomass control potential of three metabolic uncouplers (carbonyl cyanide-p-trifluoromethoxyphenylhydrazone (FCCP), carbonyl cyanide...     

Trichloroethylene degradation by photocatalysis in annular flow and annulus fluidized bed photoreactors

The effects of trichloroethylene (TCE) gas flow rate, relative humidity, TiO(2) film thickness, and UV light intensity on photodegradation of TCE have been determined in an annular flow type photoreactor. Phosgene and dichloroacetyl chloride formation could be controlled as a function of TCE gas flow rate and photodegradation of TCE decreased with increasing relative humidity. The optimum thickness of TiO(2) film was found to be approximately 5 mum and the photocatalytic reaction rate of TCE increased with square root of UV light intensity. In addition, the effects of the initial TCE concentration, phase holdup ratio of gas and solid phases (epsilon(g)/epsilon(s)), CuO loading on the photodegradation of TCE have been determined in an annulus fluidized bed photoreactor. The TCE photodegradation decreased with increasing the initial TCE concentration. The optimum conditions of the phase holdup ratio (epsilon(g)/epsilon(s)) and CuO wt.% for the maximum photodegradation of TCE was found to be 2.1 and 1.1 wt.%, respectively. Therefore, an annulus fluidized bed photoreactor is an effective tool for TCE degradation over TiO(2)/silica gel with efficient utilization of photon energy.     

Assessment of the photochemistry of OH and NO3 on Jeju Island during the Asian-dust-storm period in the spring of 2001

In this study, we examined the influence of the long-range transport of dust particles and air pollutants on the photochemistry of OH and NO3 on Jeju Island, Korea (33.17 degrees N, 126.10 degrees E) during the Asian-dust-storm (ADS) period of April 2001. Three ADS events were observed during the periods of April 10-12, 13-14, and 25-26. Average concentration levels of daytime OH and nighttime NO3 on Jeju Island during the ADS period were estimated to be about 1x10(6) and 2x10(8) moleculescm(-3) ( approximately 9 pptv), respectively. OH levels during the ADS period were lower than those during the non-Asian-dust-storm (NADS) period by a factor of 1.5. This was likely to result from higher CO levels and the significant loading of dust particles, reducing the photolysis frequencies of ozone. Decreases in NO3 levels during the ADS period was likely to be determined mainly by the enhancement of the N2O5 heterogeneous reaction on dust aerosol surfaces. Averaged over 24 h, the reaction between HO2 and NO was the most important source of OH during the study period, followed by ozone photolysis, which contributed more than 95% of the total source. The reactions with CO, NO2, and non-methane hydrocarbons (NMHCs) during the study period were major sinks for OH. The reaction of N2O5 on aerosol surfaces was a more important sink for nighttime NO3 during the ADS due to the significant loading of dust particles. The reaction of NO3 with NMHCs and the gas-phase reaction of N2O5 with water vapor were both significant loss mechanisms during the study period, especially during the NADS. However, dry deposition of these oxidized nitrogen species and a heterogeneous reaction of NO3 were of no importance.     

Sorption of the fumigant 1,3-dichloropropene on soil

The fumigant 1,3-dichloropropene (1,3-D) is considered a major replacement to methyl bromide, which is to be phased out of use in the United States by 2005. The main purpose of this study was to evaluate soil-water partitioning of 1,3-D in two California agricultural soils (Salinas clay loam and Arlington sandy loam). The partition coefficients (Kd and Kf) were determined by directly measuring the concentration of 1,3-D in the solid phase (Cs) and aqueous phase (Cw) after batch equilibration. In the Salinas clay loam, the Kf of cis-1,3-D in adsorption and desorption isotherms was 0.47 and 0.54, respectively, with respective values of 0.39 and 0.49 for trans-1,3-D. This slight hysteric effect suggests that a different range of forces are involved in the adsorption and desorption process. Since n was near unity in the Freundlich equation, the Freundlich isotherms can also be approximated using the liner isotherm. At 25 degrees C, the Kd of the 1,3-D isomers in both soils ranged from 0.46 to 0.56, and the Koc (organic matter partition coefficient) ranged from 58 to 70. The relatively low Kd values and a Koc that falls within the range of 50-150, suggests that 1,3-D is weakly sorbed and highly mobile in these soils. Understanding the sorption behavior of 1,3-D in soil is important when developing fumigation practices to reduce the movement of 1,3-D to the air and groundwater.     

Leaching of brominated flame retardants in leachate from landfills in Japan

Leachate samples were taken from seven different landfills and concentrations of brominated flame retardants (BFRs), i.e. polybrominated diphenyl ethers (PBDEs) and tetrabromobisphenol A (TBBPA), were quantified. Leaching characteristics of BFRs, especially factors affecting leachability, were clarified to obtain basic information regarding the release of BFRs into the environment. The results obtained for observed levels of the sum of PBDE-47, -99 and -100 were n.d.--4000 pg/l for the raw leachate and n.d. for the treated one, respectively, and those of TBBPA were n.d.--620,000 pg/l for the raw leachate and n.d.--11,000 pg/l for the treated one, respectively. Three sites that not only had crushed material from bulk wastes such as waste electric and electronic equipment, but also were under operation or within a year since closure, indicated a higher concentration of BFRs than the other sites. In particular extremely high concentration of PBDEs was observed at a site with a large amount of organics. Considering the leaching characteristics of BFRs, there exists the possibility that leachability of PBDEs is influenced by the presence of dissolved humic matter (DHM) in the leachate. The high removal efficiency for BFRs in the leachate treatment process was also confirmed.     

Influence of coexisting surface-active agents on leachability of dioxins in raw and treated fly ash from an MSW incinerator

The leaching behavior of dioxins from raw and treated fly ash (FA) under the coexistence of several types of surface-active agents (SAAs) was examined by batch leaching tests to obtain significant information not only for evaluating leachability of dioxins as hydrophobic organic pollutants (HOPs) under the severe environment in which SAAs coexist, but also for evaluating the reduction efficiency of dioxin-leachability from the treated FA. Enhancement of dioxin-leachability by sufficient addition of SAAs was observed in the leaching test, whereas addition of a smaller quantity depressed the leachability. The higher the degree of chlorination in PCDDs/PCDFs homologues, the more effectively the SAAs enhanced the leachability. Moreover, there was a large difference in the potential for leachability enhancement due to each surface activity, based on critical micelle concentration (CMC) of the SAAs although Aldrich humic acid enhanced the leachability at a much lower concentration than CMC. A comparison of the leachability in FA treated by several methods showed a difference in the reduction efficiency of leachability, depending on the adsorption of SAAs by each treated FA.     

Sulfur toxicity and media capacity for H2S removal in biofilters packed with a natural or a commercial granular medium

Two types of media, a natural medium (wood chips) and a commercially engineered medium, were evaluated for sulfur inhibition and capacity for removal of hydrogen sulfide (H2S). Sulfate was added artificially (40, 65, and 100 mg of S/g of medium) to test its effect on removal efficiency and the media. A humidified gas stream of 50 ppm by volume H2S was passed through the media-packed columns, and effluent readings for H2S at the outlet were measured continuously. The overall H2S baseline removal efficiencies of the column packed with natural medium remained >95% over a 2-day period even with the accumulated sulfur species. Added sulfate at a concentration high enough to saturate the biofilter moisture phase did not appear to affect the H2S removal process efficiency. The results of additional experiments with a commercial granular medium also demonstrated that the accumulation of amounts of sulfate sufficient enough to saturate the moisture phase of the medium did not have a significant effect on H2S removal. When the pH of the biofilter medium was lowered to 4, H2S removal efficiency did drop to 36%. This work suggests that sulfate mass transfer through the moisture phase to the biofilm phase does not appear to inhibit H2S removal rates in biofilters. Thus, performance degradation for odor-removing biofilters or H2S breakthrough in field applications is probably caused by other consequences of high H2S loading, such as sulfur precipitation.     

Evidence of immunomodulation in nestling American kestrels (Falco sparverius) exposed to environmentally relevant PBDEs

We investigated whether exposure to environmentally relevant polybrominated diphenyl ethers (PBDEs) causes immunomodulation in captive nestling American kestrels (Falco sparverius). Eggs within each clutch, divided by laying sequence, were injected with safflower oil or penta-BDE congeners-47, -99, -100, and -153 dissolved in safflower oil (18.7 microg sigmaPBDEs/egg) approximating Great Lakes birds. For 29 days, nestlings consumed the same PBDE mixture (15.6+/-0.3 ng/g body weight per day), reaching sigmaPBDE body burden concentrations that were 120x higher in the treatment birds (86.1+/-29.1 ng/g ww) than controls (0.73+/-0.5 ng/g ww). PBDE-exposed birds had a greater PHA response (T-cell-mediated immunity), which was negatively associated with increasing BDE-47 concentrations, but a reduced antibody-mediated response that was positively associated with increasing BDE-183 concentrations. There were also structural changes in the spleen (fewer germinal centers), bursa (reduced apoptosis) and thymus (increased macrophages), and negative associations between the spleen somatic index and sigmaPBDEs, and the bursa somatic index and BDE-47. Immunomodulation from PBDE exposure may be exacerbated in wild birds experiencing greater environmental stresses.     

Factors influencing natural occurrence of fluoride-rich groundwaters: a case study in the southeastern part of the Korean Peninsula

Factors regulating the occurrence of fluoride in groundwater were investigated using natural isotope tracers and geochemical data in the southeastern part of Korea where about 10% of the total public water-supply wells (n=422) inspected in this study had fluoride levels exceeding the drinking water limit of Korea (1.5 mg/l). The F-rich public wells are mostly distributed along the major faults, especially in the terrain of the F-rich granitic rocks. The stable isotope analysis results provide substantial information for the relative ages of groundwaters. It is revealed that the F-rich groundwaters are deeply circulating paleogroundwaters and occur along the faults due to upward flow along the fault plane. While reacting with granitic rocks for a prolonged period, the F concentrations of groundwater are continuously enriched even after the groundwater reaches an equilibrium state with respect to fluorite (CaF2) due to removal of Ca by precipitation of calcite (CaCO3). These observations reflect that rock chemistry, groundwater age, well depth, and geologic structure are the important factors controlling the occurrence of high F groundwaters. However, high F groundwaters are rarely observed in the fault zones where the associated fractures are widely developed. Isotopic signature provides an evidence for deep penetration of recently recharged groundwater into the wide fault zone, indicating that the hydrologic condition of the fault is also an important factor controlling the occurrence of high F groundwaters.