Isotope dilution analysis of polychlorinated biphenyls (PCBs) in transformer oil and global commercial PCB formulations by high resolution gas chromatography-high resolution mass spectrometry

Special polychlorinated biphenyls (PCBs) standards (native and isotope labeled) were analyzed by isotope dilution method using HRGC-HRMS. Multiple analysis of special PCBs standards by three different laboratories produced the relative response factors (RRFs) and relative standard deviations (RSDs %) was in the average of 0.979 and 3.86, respectively. Additionally, inter-laboratory analysis of various forms of transformer oil revealed the PCBs concentrations were in the following order; PCBs fortified transformer oil (940-1300 ng/g)>PCB polluted transformer oil (490-680 ng/g)>chemically degraded-transformer oil (480-490 ng/g) and PCBs free oil (ND-17 ng/g). Chemical degradation resulted in an order of magnitude decrease in the PCB concentrations. Specifically, higher chlorinated PCBs degraded into lower chlorinated PCBs. Also, composition of PCBs have been determined in PCB formulations from Japan (Kanechlor), Germany (Clophen), USA (Aroclor), Russia (Sovol) and Poland (Chlorofen). Major PCBs (24-PCB congeners) contributed 54-67%, 55-68%, 16-69%, 71% and 72% in Kanechlor, Clophen, Aroclor, Sovol and Chlorofen, respectively to total PCBs. The homologue pattern of Kanechlor, Aroclor and Clophen in technical fromulation was similar (e.g., Kanechlor-300 resembled to those of Clophen A-30 and Aroclor-1242). Furthermore, congener-specific distributions of major PCBs/dioxin-like PCBs and toxic equivalency quantities (TEQ) were calculated. Based on our tentative assumption calculations, cumulative production of five different technical PCB formulations, WHO-TEQ emission was estimated to be approximately 16.05 tons.     

The influence of paddy soil drying on Tc insolubilization by bacteria

Tc insolubilization in four soils samples was compared by pre-incubating them in both dry and wet states, then measuring Tc concentrations in solution when the samples were saturated with an excess of water spiked with 99Tc. Soils pre-incubated in a dry state showed higher Tc insolubilization than soils incubated in a wet state. To clarify the difference in Tc insolubilization, Eh, bacterial abundances, and bacterial species compositions in the dry and wet ponding water samples were determined. For the wet ponding water samples, Eh values were forced to decrease, but no increase in Tc insolubilization was observed. The dry and wet ponding water samples had similar numbers of bacteria. However, denaturing gradient gel electrophoresis analysis revealed that they had different bacterial species compositions. These results suggested the difference in bacterial species compositions would account for the difference in Tc insolubilization.     

Gasification and smelting system using oxygen blowing for plastic waste including polyvinyl chloride

A new type of waste gasification and smelting system using oxygen blowing based on high-temperature metallurgy, was developed by Sumitomo Metals, Japan. This system can steadily gasify and melt not only municipal waste, but also plastic waste and polyvinyl chloride (PVC) waste by using a top-blow oxygen lance together with sideways-blow oxygen lances. As a result of gasification in the high-temperature reducing atmosphere and rapid gas cooling, dioxin-free, high-calorie purified gas was produced. Ash components in the wastes were smelted in a high-temperature reducing atmosphere, and high-quality slag free of heavy metals was produced. Most of the chlorine in the wastes was converted into hydrogen chloride in the off gas. The hydrogen chloride can be recovered as hydrochloric acid or chlorine, which are recyclable to PVC manufacturing.     

Distribution of polychlorinated biphenyls and chlorinated pesticide residues in trout in the Sierra Nevada

Organochlorine compounds are known to be atmospherically transported to long distances from their original sources. To understand the influence of California's Sierra Nevada range on the air transport and subsequent distribution pattern of some of these residues within the range, we have chosen salmonid fish as an indicator species. Fish were collected from 10 locations throughout the northern and central Sierra Nevada and polychlorinated biphenyl (PCB), toxaphene, chlordane, and DDT [1,1,1-trichloro, 2,2'-bis (p-chlorophenyl) ethane] residues in muscle tissue were analyzed. Rainbow trout (Oncorhynchus mykiss) were found in all sampling locations, and therefore analyses mainly focused on this species. When similar-sized rainbow trout samples from several similar oligotrophic, high-altitude lakes and streams were compared, it became apparent that altitude is one of the factors affecting the residual levels of PCB (r(2) = 0.882), but not for total DDT, toxaphene, or chlordane in trout. Analysis of correlations among these four organochlorine compound residue groups indicated that there are modest correlations in patterns of distribution between chlordane vs. toxaphene (r(2) = 0.345), and chlordane vs. total DDT (r(2) = 0.239), but toxaphene residues are not correlated with PCB or total DDT. In view of significant correlation to the altitude it is concluded that PCB residue in rainbow trout is a good monitoring tool for studying the effect of high-altitude mountain ranges on the long-range transport and distribution of those persistent pollutants.     

Evidence for similarities between cyclodiene type insecticides and picrotoxinin in their action mechanisms

Evidence has been obtained to indicate that cyclodiene-type insecticides, e.g., heptachlor epoxide and gamma-BHC, mimic the action of picrotoxinin. These insecticides inhibit the GABA (gamma-aminobutyric acid)-stimulated chloride uptake in the coxal muscle of the American cockroach, and directly compete against [3H]a-dihydropicrotoxinin for binding in the rat brain synaptosomes. Moreover, several cyclodiene-resistant insect strains are also resistant to picrotoxinin. This cross-resistance is specific to picrotoxinin and does not extend to other neuroexcitants. These insecticides, like picrotoxinin, cause central nerve excitation by stimulating transmitter release. Similarity in molecular structures also has been pointed out. These results indicate that some of the nerve excitation symptoms that insecticides cause are likely due to their interaction with picrotoxinin receptor.     

Novel malonate-type copolymers containing vinyl alcohol blocks as biodegradable segments and their builder performance in detergent formulations

Poly[(disodium methylene malonate)-co-(vinyl alcohol)] [P(DSMM-VA)] and poly[(disodium ethoxymethylene malonate)-co-(vinyl alcohol)] [P(DSEMM-VA)] containing a poly(vinyl alcohol) (PVA) block as a biodegradable segment were prepared and their biodegradability and functionality were evaluated and compared with those of the corresponding fumarate and maleate copolymers. It was found that the 1,1-dicarboxylate-type copolymers, P(DSMM-VA) and P(DSEMM-VA), showed better biodegradability than the corresponding 1,2-dicarboxylate-type copolymers, P(DSF-VA) and P(DSM-VA). This improved biodegradability of P(DSMM-VA) and P(DSEMM-VA) is probably attributable to their more expanded polymer chain in aqueous solution, which will be more accessible to the degrading enzymes. The minimum chain length of the PVA-block, which acts as a biodegradable segment in the polymer chain, is estimated to be 2–3 and 3–4 monomer units for P(DSMM-VA) and P(DSEMM-VA), respectively. On the other hand, the minimum PVA block is about 5 and 7 monomer units for the fumarate and maleate copolymers, respectively. It was confirmed that P(DSMM-VA) showed excellent builder performance compared to the corresponding fumarate copolymer.Paper presented at the Bio/Environmentally Degradable Polymer Society—Second National Meeting, August 19–21, 1993, Chicago, Illinois.     

Motivation of Japanese companies to take environmental action to reduce their greenhouse gas emissions: an econometric analysis

To analyze the motivations of Japanese companies to take environmental actions to reduce their greenhouse gas (GHG) emissions, we used FY2006 research data and questioned Japanese industries regarding their reduction of GHG emissions. Empirical investigations revealed that voluntary targets set by industry organizations, government requirements, and advance responses to possible future regulations can positively influence environmental actions for GHG emission reduction; however, cost reductions and corporate social responsibility fulfillment cannot.

Monitoring OH-PCBs in PCB transport worker’s urine as a non-invasive exposure assessment tool

In this study, we analyzed hydroxylated polychlorinated biphenyls (OH-PCBs) in urine of both PCB transport workers and PCB researchers. A method to monitor OH-PCB in urine was developed. Urine was solid-phase extracted with 0.1% ammonia/ methanol (v/v) and glucuronic acid/sulfate conjugates and then decomposed using β-glucuronidase/arylsulfatase. After alkaline digestion/derivatization, the concentration of OH-PCBs was determined by HRGC/HRMS-SIM. In the first sampling campaign, the worker’s OH-PCB levels increased several fold after the PCB waste transportation work, indicating exposure to PCBs. The concentration of OH-PCBs in PCB transport workers’ urine (0.55~11 μg/g creatinine (Cre)) was higher than in PCB researchers’ urine (< 0.20 μg/g Cre). However, also a slight increase of OH-PCBs was observed in the researchers doing the air sampling at PCB storage area. In the second sampling, after recommended PCB exposure reduction measures had been enacted, the worker’s PCB levels did not increase during handling of PCB equipment. This suggests that applied safety measures improved the situation. Hydroxylated trichlorobiphenyls (OH-TrCBs) were identified as a major homolog of OH-PCBs in urine. Also, hydroxylated tetrachlorobiphenyls (OH-TeCBs) to hydroxylated hexachlorobiphenyls (OH-HxCBs) were detected. For the sum of ten selected major indicators, a strong correlation to total OH-PCBs were found and these can possibly be used as non-invasive biomarkers of PCB exposure in workers managing PCB capacitors and transformer oils. We suggest that monitoring of OH-PCBs in PCB management projects could be considered a non-invasive way to detect exposure. It could also be used as a tool to assess and improve PCB management. This is highly relevant considering the fact that in the next 10 years, approx. 14 million tons of PCB waste need to be managed. Also, the selected populations could be screened to assess whether exposure at work, school, or home has taken place.     

Association of serum levels of polychlorinated biphenyls with IL-8 mRNA expression in blood samples from asthmatic and non-asthmatic Japanese children

Background

One of the suggested health outcomes of PCB exposure is childhood asthma.

Objectives

This study was conducted to find health relevant biomarkers providing the molecular epidemiological evidence for the positive relationship between exposure to PCBs and childhood asthma.

Methods

Blood samples from fifteen asthmatic children as well as an equal number of non-asthmatic children (average 2 year old) were collected, and were analyzed for PCBs and their select marker expression by using qRT-PCR.

Results

Among biomarkers examined IL-8 expression was significantly correlated to serum levels of PCB #163 + 164 (P = 0.022), #170 (P = 0.046), #177 (P = 0.022), #178 (P = 0.022) and #180 + 193 (P = 0.046) in a dose-dependent manner, which was found only among asthmatic children. In contrast, COX-2 correlations to individual congener levels were recognized only among control subjects, not among asthmatic subjects.

Conclusion

Serum concentrations of PCB#163 + 164, #170, #177, #178 and #180 + 193 correlate significantly with IL-8 mRNA expressions among asthmatic children.     

Mapping the global supply and demand structure of rice

Rice plays a major role in the global supply and demand for sustainable food production. The constraints of maintaining sustainable rice production are closely linked to the relationship between the distribution patterns of human activity on the planet and economic growth. Global patterns of rice production can be mapped by using various criteria linked to domestic income, population patterns, and associated satellite brightness data of rice-producing regions. Prosperous regions have more electric lighting, and there are documented correlations between gross domestic product (GDP) and nighttime light. We chose to examine global rice production patterns on a geographical basis. For the purposes of this study, each country is considered to be made up of regions, and rice production is discussed in terms of regional distribution. A region is delineated by its administrative boundaries; the number of regions where rice is produced is about 13,839. We used gridded spatial population distribution data overlain by nocturnal light imagery derived from satellite imagery. The resultant relationship revealed a correlation between regional income (nominal values of GDP were used) and rice production in the world. The following criteria were used to examine the supply and demand structure of rice. Global rice consumption = “caloric rice consumption per capita per day” multiplied by “regional population values”. Regional rice yields = “country-based production” divided by “harvested area” (multiple harvests are taken into account). Regional rice production = “regional harvested areas” multiplied by “rice yield values”. We compared regional rice consumption and production values according to these methods. Analysis of the data sets generated a map of rice supply and demand. Inter-regional shipping costs were not accounted for. This map can contribute to the understanding of food security issues in rice-producing regions and to estimating potential population values in such regions.