Leaching characteristics of polybrominated diphenyl ethers (PBDEs) from flame-retardant plastics

To investigate the effect of leachant on the leachability of polybrominated diphenyl ethers (PBDEs), we determined the leaching concentrations of PBDEs from flame-retardant plastic samples (TV housings and raw materials before molding processing) that are regarded as a source of PBDEs in landfill sites. The leachants used were distilled water, 20% methanol solution, and dissolved humic solution (DHS) of 1000 mg/l based on organic carbon. The leaching test conditions were a liquid-to-solid ratio of 100:1, and a contact period of five days, with twice-daily agitation in a temperature-controlled room of 30 degrees C without pH or ionic strength control. The leaching concentrations of PBDEs increased with increased content, and were found to be remarkably enhanced when methanol and DHS were used instead of distilled water. The enhancement of leachability in the presence of the latter was attributed to the cosolvency effect, and complex formations between the PBDEs and dissolved humic matter (DHM). PBDE concentrations in the leachate obtained from the leaching test and an actual landfill site revealed a significant presence of congeners below heptabromodiphenyl ethers (H7BDEs), detected in the leachate of the actual landfill, while significant amounts of nonabromodiphenyl ethers (N9BDEs) and decabromodiphenyl ether (D10BDE) were detected in the leachate of the leaching test.     

Contamination status of arsenic and other trace elements in drinking water and residents from Tarkwa, a historic mining township in Ghana

This study was conducted to assess the contamination status of 22 trace elements, especially As in water and residents in Tarkwa, a historic mining town in Ghana. Drinking water and human urine samples were collected from Tarkwa in addition to control samples taken from Accra, the capital of Ghana in March, 2004. Concentrations of As and Mn in some drinking water samples from Tarkwa were found above the WHO drinking water guidelines posing a potential health risk for the people. A potential health risk of As and Mn is a concern for the people consuming the contaminated water in this area. No significant difference of As concentrations in human urine between mining town (Tarkwa) and control site (Accra) was observed. Although As concentrations in drinking water in Tarkwa were low, urinary As levels were comparable to those reported in highly As-affected areas in the world. These results suggest the presence of other sources of As contamination in Ghana. This is the first study on multi-elemental contamination in drinking water and human from a mining town in Ghana.     

Congener profiles of PCB and a proposed new set of indicator congeners

In this study, a new method for calculating total PCB and toxic equivalents (TEQ) of coplanar PCB (Co-PCB) was proposed, called the 'PCB dual method'. This method analysed various kinds of technical PCB, samples contaminated by technical PCB and byproduct PCB. In the PCB dual method, a data set of 15 indicator congeners was utilized for the calculations, having IUPAC nos. #3, #8, #28, #52, #77, #101, #105, #118, #126, #138, #153, #180, #194, #206 and #209. The 15 congener set was chosen from the major congeners, determined by HRGC/HRMS analysis, in 18 technical PCB, Kanechlor, Aroclor, Clophen and Chlorofen, and 20 other samples, such as indoor air, flue gases, emission gases, municipal solid waste (MSW), ash and sealant. To obtain total PCB and TEQ of Co-PCB, the intermediate sum for the concentration of the 15 congeners was multiplied by each multiplication factor. As a result, we obtained the average factor used to calculate total PCB in technical PCB and other samples. For technical PCB, the factor was 3.01, while for indoor air samples, flue and emission gases, MSW, ash and sealants, the factors were 3.92, 4.16, 3.68, 4.52 and 4.77, respectively. Moreover, the factor used to calculate the TEQ of Co-PCB in Kanechlor and other source samples were also obtained. The factors for Kanechlor, indoor air samples and emission gases from a cement plant were in the order of 10(-5), while the factor for flue gases in a MSW incinerator was in the order of 10(-3). These data were valuable for the rough estimation of the TEQ of Co-PCB without separation from other PCB before individual measurements.     

Pathways and products of the degradation of PCBs by the sodium dispersion method

Nine polychlorinated biphenyl (PCB) congeners (2-chlorobiphenyl, 3-chlorobiphenyl, 4-chlorobiphenyl, 2,3,4-trichlorobiphenyl, 2,2',5,5'-tetrachlorobiphenyl, 2,3',4,4',5-pentachlorobiphenyl, 3,3',4,4',5-pentachlorobiphenyl, 2,2',4,4',5,5'-hexachlorobiphenyl, and decachlorobiphenyl) were dechlorinated by the sodium dispersion method (SD) at low temperature (60 degrees C). The dechlorination of 4-chlorobiphenyl was the fastest among the three monochlorobiphenyls. As for the other six congeners, we investigated the major dechlorination pathways. Although reaction selectivity was not very sensitive to the position of the chlorine substituent, the chlorines at the para position were slightly easier to dechlorinate than those at the ortho or meta positions. The decomposition rate increased with the total numbers of chlorine substituents. A chlorine situated between two other chlorines showed a high reactivity. When the numbers of chlorines on each of the phenyl rings were different, the reactions occurred on the more substituted ring. In the degradation of 4-chlorobiphenyl at elevated temperature (160 degrees C), we investigated the structures of the polymerized products and whether all the organic chlorinated compounds degraded finally or not. As for the dimers, p-quarterphenyl (QP) and m,p-QP were detected but not o-QP, m-QP, o,p-QP, o,m-QP, or the mono- to tetra-chlorinated QPs. Compounds with a molecular weight of 534.4183 or 758.6713 were detected. They were considered to have C40H54 or C56H86 as their molecular formula. The compounds were most probably the polymerized products resulting from coupling of hexadecane or two hexadecanes and two phenylcyclohexadienes. It was thought the dechlorination and the polymerization were the main reactions. All of many detected compounds were hydrocarbons without chlorines, and no peaks originating from organic chlorinated compounds were observed by mass spectroscopic (MS) methods.     

Strong adsorption of DNA molecules on humic acids

Analysing soil microbial communities is often hampered by DNA adsorption on soil organic compounds such as humic acids. However the role of humic acids in DNA adsorption and stability in soils remains controversial. To characterize DNA–humic acid interactions, we studied DNA adsorption on two commercially available humic acids and a soil humic acid extracted from an Andosol. Desorption of the adsorbed DNA using 4 different solutions—distilled water, 0.1 M NaCl, 0.1 M sodium phosphate buffer (pH 6.0), and 1% sodium dodecyl sulfate solution—was also studied to understand the mechanism of DNA adsorption on humic acids. Here, we show that humic acids play an important role in DNA adsorption to soils. DNA molecules were adsorbed on the humic acids, with adsorption increasing proportionally with the DNA concentrations in the solution. The adsorption on all humic acid samples was fitted with Freundlich equation, and the parameters obtained from the equation indicated a high affinity between the humic acids and DNA molecules. The total amount of DNA desorbed by the 4 solutions was less than 2% of the total DNA adsorbed on all the humic acids. The results demonstrate that DNA molecules are able to bind strongly to humic acids by ligand binding, hydrophobic interaction, aggregation, or precipitation.     

Use of two population metrics clarifies biodiversity dynamics in large-scale monitoring: the case of trees in Japanese old-growth forests

An alkaline comet assay and a micronucleus test were carried out on erythrocytes of the European chub, Squalius cephalus L., collected in spring and autumn in 2005 and 2006 at three sampling sites in River Sava, near Zagreb, Croatia. The results of comet assay showed the lowest genotoxic influence at the least polluted site, while higher DNA damage was observed at the polluted sites. Although the basal levels of DNA damage were elevated, a clear gradation of DNA damage was found due to pollution intensity in all sampling periods. The lowest cytogenetic damage as revealed by the micronucleus test (MNT) was observed as well at the least polluted site. High variations in MN frequency were observed between sampling periods, although the number of micronucleated erythrocytes was consistently the highest one at the polluted site. The comet assay as a biomarker of genotoxic effect exhibited higher sensitivity in discriminating the genotoxic capacity of studied polluted sites while the MNT was less sensitive. However, both tests should be used together in biomonitoring studies because they can reveal different aspects of DNA damage; comet assay, the early event of genotoxic exposure, and MNT, its final result as a mutagenic potential.     

Effects of Long-Term Ungulate Exclusion and Recent Alien Species Control on the Preservation and Restoration of a Hawaiian Tropical Dry Forest

Abstract: Although the destruction of tropical rain forests receives much attention, tropical dry forests are in general far more threatened and endangered. Eliminating grazing ungulates is often considered a key first step toward protecting these ecosystems, but few studies have investigated the long-term effects of this technique. We examined the effects of ungulate exclusion from a 2.3-ha native dry-forest preserve on the island of Hawaii by comparing its present flora to the flora of an adjacent area subjected to continuous grazing since the preserve was fenced over 40 years ago. Relative to this adjacent area, the fenced preserve contained a more diverse flora with substantially greater coverage of native overstory and understory species. Until recently, however, regeneration of native canopy trees within the preserve appears to have been thwarted by a dominant herbaceous cover of alien fountain grass (   Pennisetum setaceum ) and predation by alien rodent species. Our results indicate that although ungulate exclusion may be a necessary and critical first step, it is not sufficient to adequately preserve and maintain Hawaii's remaining tropical dry forest remnants. Our recent efforts to control the dominant alien species within the fenced preserve suggest that this practice may facilitate both the regeneration of native species and the colonization and potential invasion of new alien plants. Comparisons of seedlings of the dominant native canopy tree Diospyros sandwicensis growing in sites both dominated by and free of fountain grass suggested that fountain grass inhibits Diospyros seedling growth and photosynthesis but may increase survival if seedlings are protected from ungulates.     

Urinary 8-hydroxy-2'-deoxyguanosine in inhabitants chronically exposed to arsenic in groundwater in Cambodia

Arsenic concentrations in hair and urine, and urinary levels of 8-hydroxy-2'-deoxyguanosine (8-OHdG), a marker of oxidative DNA damage, were examined for inhabitants of the Mekong Basin in Kratie Province, Cambodia. Also, the arsenic levels of tube-well water were determined. Total arsenic concentrations in tube-well water ranged from <1 to 886 microg L(-1), and 44.8% of these exceeded the WHO drinking water guideline of 10 microg L(-1). Elevated levels of arsenic were observed in the human hair and urine, and also a significant positive correlation was observed between the concentrations in hair and urine. These results suggest that the inhabitants are chronically exposed to arsenic through drinking the tube-well water. Levels of urinary 8-OHdG were higher for the subjects with higher arsenic levels in hair and urine, suggesting that induction of oxidative DNA damage was caused by chronic exposure to arsenic in tube-well water for the inhabitants in Kratie Province. To our knowledge, this is the first report on the oxidative DNA damage caused by chronic exposure to arsenic in groundwater for the inhabitants in Cambodia.     

Degradation pathways of decabromodiphenyl ether during hydrothermal treatment

The hydrothermal degradation pathways of decabromodiphenyl ether during hydrothermal treatment were investigated. After an initial "Heating time", the reaction runs were carried out at constant temperature (heating to 300 degrees C and keeping temperature) and pressure (8MPa) in a SUS316 stainless steel micro autoclave filled with water. Some decomposition of decabromodiphenyl ether was observed over 200 degrees C, and it was decomposed by more than 99% after 10 min at 300 degrees C. The reactivities of bromine on para and meta substituents were relatively high, while its reactivity on ortho bromine was extremely low. The formations of polybrominated dibenzo-p-dioxins and furans (PBDD/DFs) were observed in the early stages of the reactions at around 300 degrees C. The TCDD toxicity equivalency (TCDD-EQs) of the by-products was determined based on relative potencies (REPs EC(5TCDD)) with the Dioxin-Responsive-Chemical Activated Luciferase gene eXpression (DR-CALUX) bioassays technology. These results indicated that the risk of formation of PBDD/DFs in the hydrothermal degradation of deca-BDE was low, and it would be possible to reduce the TCDD-EQs value by adding some catalyst or alkali, or extending processing time.     

Mercury in hair and blood from residents of Phnom Penh (Cambodia) and possible effect on serum hormone levels

High concentration of mercury (Hg) in hair has been reported for Cambodians. To confirm the Hg contamination occurring through intake, Hg concentrations were determined in both hair and blood of residents (n=20) from Phnom Penh, Cambodia. Mercury concentrations in the hair and blood were 0.69-190microg g(-1) dry wt and 5.2-58microg l(-1), respectively, which were lower than those from Hg contaminated or high fish intake regions, but were higher than those from non-contaminated regions. Some female subjects had hair and blood Hg levels exceeding the threshold values for neurotoxic effects. Interestingly, serum estrone and estradiol levels were positively correlated with blood Hg level for both males and females, indicating possible induction of female hormones by Hg exposure in Cambodians.