Chlorinated naphthalene formation from the oxidation of dichlorophenols

Polychlorinated naphthalenes (PCNs) formed along with dibenzo-p-dioxin and dibenzofuran products in the slow combustion of dichlorophenols (DCPs) at 600 degrees C were identified. Each DCP reactant produced a unique set of PCN products. Major PCN congeners observed in the experiments were consistent with products predicted from a mechanism involving an intermediate formed by ortho-ortho carbon coupling of phenoxy radicals; polychlorinated dibenzofurans (PCDFs) are formed from the same intermediate. Tautomerization of the intermediate and H2O elimination produces PCDFs; alternatively, CO elimination to form dihydrofulvalene and fusion produces naphthalenes. Only trace amounts of tetrachloronaphthalene congeners were formed, suggesting that the preferred PCN formation pathways from chlorinated phenols involve loss of chlorine. 3,4-DCP produced the largest yields of PCDF and PCN products with two or more chlorine substituents. 2,6-DCP did not produce tri- or tetra-chlorinated PCDF or PCN congeners. It did produce 1,8-DCN, however, which could not be explained.     

Ambient air monitoring of PCDD/Fs and co-PCBs in Gyeonggi-do, Korea

We started the monitoring for PCDD/Fs in ambient air and soil in August 2001, and co-PCBs in January 2002. Decreasing of PCDD/Fs and co-PCBs levels in ambient air were observed. The higher PCDD/Fs levels were found in winter and lower in autumn. We found that the industrial incinerators influenced the PCDD/Fs levels in ambient air. In the 2,3,7,8-substituted PCDD/Fs concentration profiles, the three major congeners occupied 67% of the total mass. In case of co-PCBs, PCB#118, #105 and #77 were observed as the main congeners. Five cluster groups discriminated by ratio of four components, O(8)CDD, 1,2,3,4,6,7,8-H(7)CDD, 1,2,3,4,6,7,8-H(7)CDF and O(8)CDF, were obtained from HCA (hierarchical cluster analysis).     

Characterization of PM2.5 aerosols dominated by local pollution and Asian dust observed at an urban site in Korea during aerosol characterization experiments (ACE)--Asia Project

Daily fine particulate matter (PM2.5) samples were collected at Gwangju, Korea, during the Aerosol Characterization Experiments (ACE)-Asia Project to determine the chemical properties of PM2.5 originating from local pollution and Asian dust (AD) storms. During the study period, two significant events occurred on April 10-13 and 24-25, 2001, and a minor event occurred on April 19, 2001. Based on air mass transport pathways identified by back-trajectory calculation, the PM2.5 dataset was classified into three types of aerosol populations: local pollution and two AD aerosol types. The two AD types were transported along different pathways. One originated from Gobi desert area in Mongolia, passing through Hunshandake desert in Northern Inner Mongolia, urban and polluted regions of China (AD1), and the other originated in sandy deserts located in the Northeast Inner Mongolia Plateau and then flowed southward through the Korean peninsula (AD2). During the AD2 event, a smoke plume that originated in North Korea was transported to our study site. Mass balance closures show that crustal materials were the most significant species during both AD events, contributing -48% to the PM2.5 mass; sulfate aerosols (19.1%) and organic matter (OM; 24.6%) were the second greatest contributors during the AD1 and AD2 periods, respectively, indicating that aerosol properties were dependent on the transport pathway. The sulfate concentration constituted only 6.4% (4.5 microg/m3) of the AD2 PM2.5 mass. OM was the major chemical species in the local pollution-dominated PM2.5 aerosols, accounting for 28.7% of the measured PM2.5 mass, followed by sulfate (21.4%), nitrate (15%), ammonium (12.8%), elemental carbon (8.9%), and crustal material (6.5%). Together with substantial enhancement of the crustal elements (Mg, Al, K, Ca, Sc, Ti, Mn, Fe, Sr, Zr, Ba, and Ce), higher concentrations of pollution elements (S, V, Ni, Zn, As, Cd, and Pb) were observed during AD1 and AD2 than during the local pollution period, indicating that, in addition to crustal material, the AD dust storms also had a significant influence on anthropogenic elements.     

Identification and interpretation of representative ozone distributions in association with the sea breeze from different synoptic winds over the coastal urban area in Korea

To aid the studies of long-term impact assessment of cumulative ozone (O3) exposures, the representative 8-hr O3 pollution patterns have been identified over the Greater Seoul Area (GSA) in Korea. Principal component analysis and two-stage clustering techniques were used to identify the representative O3 patterns, and numerical and observational analyses were also used to interpret the identified horizontal distribution patterns. The results yielded three major O3 distribution patterns, and each of the three patterns was found to have strong correlations with local and synoptic meteorological conditions over the GSA. For example, pattern 1, accounting for 46% of O3 concentration distributions, mostly occurred under relatively weak westerly synoptic winds. The predominant features of this pattern were infrequent high O3 levels but a distinct gradient of O3 concentration from the western coastal area to the eastern inland area that was mainly induced by the local sea breeze. Pattern 2, accounting for 31% of O3 concentration distributions, was found with higher O3 levels in the western coastal area but lower in the eastern inland area. This is due to the modified sea breeze under the relatively stronger easterly opposing synoptic wind, affecting the high O3 occurrence in the western coastal area only. However, pattern 3, accounting for 21% of O3 concentration distributions, showed significantly higher O3 concentrations over the whole GSA mainly due to the retarded and slow-moving sea-breeze front under the weak opposing synoptic flow. Modeling study also indicated that local and synoptic meteorological processes play a major role in determining the high O3 concentration distribution patterns over the GSA.     

Assessment of pesticide contamination in three Mississippi Delta oxbow lakes using Hyalella azteca

Three oxbow lakes in northwestern Mississippi, USA, an area of intensive agriculture, were assessed for biological impairment from historic and current-use pesticide contamination using the amphipod, Hyalella azteca. Surface water and sediment samples from three sites in each lake were collected from Deep Hollow, Beasley, and Thighman Lakes from September 2000 to February 2001. Samples were analyzed for 17 historic and current-use pesticides and selected metabolites. Ten-day H. azteca survival and growth (as length and dry weight) were measured to determine the degree of biological impairment. Maximum number of detectable pesticides in surface water from Deep Hollow, Beasley and Thighman Lakes was 10, 11, and 17, respectively. Maximum number of detectable pesticides in lake sediments was 17, 17, and 15, respectively. Bioassay results indicated no observable survival effects on H. azteca exposed to surface water or sediment from any lake examined and no growth impairment in animals exposed to lake sediments. However, growth was significantly impaired in surface water exposures from Deep Hollow Lake (2 sites) and Beasley Lake (1 site). Statistically significant relationships between growth impairment (length) and cyanazine, methyl parathion, λ-cyhalothrin, chlorfenapyr, and pp′DDE surface water concentrations in Deep Hollow Lake as well as trifluralin, atrazine, and methyl parathion in Beasley Lake were observed. Although pesticide frequency and concentrations were typically greater in sediment than surface water, bioassay results indicated decreased availability of these pesticides in sediment due to the presence of clay and organic carbon. Growth impairment observed in surface water exposures was likely due to complex interaction of pesticide mixtures that were present.     

Background levels and dietary intake of PCDD/Fs in domestic and imported meat in South Korea

A survey was conducted in South Korea to determine residual levels and dietary intake of polychlorinated dibenzo-p-dioxins (PCDDs) and dibenzofurans (PCDFs) from meat. Altogether 119 domestic and 164 imported samples of beef, pork, and chicken were examined. The mean levels of PCDD/Fs in upper bound were 0.21, 0.22, and 0.04pg WHO-TEQ/g fat for beef, pork, and chicken, respectively. The low level of PCDD/Fs in chicken probably resulted from the low fat content in the samples used. The samples were separated into domestic and imported products in order to investigate the sources of contamination. PCDFs were the more dominant congeners in domestic beef and were similar to those found from emission of incineration. However, the congener profiles of domestic beef and incineration were difficult to compare because the environmental fate and animal metabolism were involved. The upper bound dietary intake of PCDD/Fs from beef, pork and chicken was calculated to be 0.04pg/WHO-TEQ/kgbw/day. The combined consumption of beef, pork, and chicken was found to be 84.8g per day for a person weighing 60kg and represented 5.7% of their total daily food intake.     

Identification of potential biomarkers for diazinon exposure to Japanese Medaka (Oryzias latipes) using annealing control primers

A new differential display-polymerase chain reaction (PCR) method based on annealing control primers was used to screen and identify potential biomarkers from differentially expressed genes (DEGs) in medaka exposed to sub-lethal concentration of diazinon (100 ppb). Among the differentially expressed genes identified, the majority were in functional categories of protein biosynthesis, transport and metabolism according to the gene ontology classification. The differential expression of ribosomal protein genes was quantified by real time PCR. The genes encoding ribosomal proteins including L3 and S17 were selected as potential biomarkers for diazinon exposure in medaka fish.     

Contaminant exposure in terrestrial vertebrates

Here we review mechanisms and factors influencing contaminant exposure among terrestrial vertebrate wildlife. There exists a complex mixture of biotic and abiotic factors that dictate potential for contaminant exposure among terrestrial and semi-terrestrial vertebrates. Chemical fate and transport in the environment determine contaminant bioaccessibility. Species-specific natural history characteristics and behavioral traits then play significant roles in the likelihood that exposure pathways, from source to receptor, are complete. Detailed knowledge of natural history traits of receptors considered in conjunction with the knowledge of contaminant behavior and distribution on a site are critical when assessing and quantifying exposure. We review limitations in our understanding of elements of exposure and the unique aspects of exposure associated with terrestrial and semi-terrestrial taxa. We provide insight on taxa-specific traits that contribute, or limit exposure to, transport phenomenon that influence exposure throughout terrestrial systems, novel contaminants, bioavailability, exposure data analysis, and uncertainty associated with exposure in wildlife risk assessments. Lastly, we identify areas related to exposure among terrestrial and semi-terrestrial organisms that warrant additional research.     

Reductive dechlorination and biodegradation of 2,4,6-trichlorophenol using sequential permeable reactive barriers: laboratory studies

The reductive dechlorination and biodegradation of 2,4,6-trichlorophenol (2,4,6-TCP) was investigated in a laboratory-scale sequential barrier system consisting of a chemical and biological reactive barrier. Palladium coated iron (Pd/Fe) was used as a reactive barrier medium for the chemical degradation of 2,4,6-TCP, and a sand column seeded with anaerobic microbes was used as a biobarrier following the chemical reactive barrier in this study. Only phenol was detected in the effluent from the Pd/Fe column reactor, indicating that the complete dechlorination of 2,4,6-TCP was achieved. The residence time of 30.2-21.2h was required for the complete dechlorination of 2,4,6-TCP of 100 mg l(-1) in the column reactor. The surface area-normalized rate constant (k(SA)) is 3.84 (+/-0.48)x10(-5)lm(-2)h(-1). The reaction rate in the column tests was one order of magnitude slower than that in the batch test. In the operation of the biobarrier, about 100 microM of phenol was completely removed with a residence time of 7-8d. Consequently, the dechlorination prior to biodegradation turns out to increase the overall treatability. Moreover, the sequential permeable reactive barriers, consisting of iron barrier and biobarrier, could be recommended for groundwater contaminated with toxic organic compounds such as chlorophenols.