Possible involvement of frontier (π) electrons in the metabolism of poly-chlorinated biphenyls (PCBs)

The electron density, at each carbon atom, of the highest occupied π orbital of thirteen polychlorinated biphenyl (PCB) and one polychlorinated dibenzofuran (PCDF) molecules were calculated and the result was compared with their in vitro and/or in vivo metabolism. We noted that 1. the carbon position at which the frontier electron density was highest was most readily hydroxylated or sulfonated, 2. if the carbon with the highest frontier (π) electrons was occupied by chlorine, either a replacement occurred or the carbon with the next highest electron density was activated for metabolism, 3. due to steric hinderance ‘ortho’ carbons in PCBs were least preferred for such reactions inspite of possessing favorable electron density, 4. this was applicable to both phenobarbitol (PB) - type and 3-methyl cholanthrene (3 MC) - type PCB inducers. Frontier (π) electron density could be an easy guide for understanding the metabolic products of persistent and toxic environmental pollutants in vitro or in vivo and in understanding their environmental fate.     

Dependence of mechanochemically induced decomposition of mono-chlorobiphenyl on the occurrence of radicals

Mechanochemically induced dechlorination of mono-chlorobiphenyl (BP-Cl) on the surfaces of metal oxides was compared with that on metal hydroxides, using the three metals of Mg, Al, and La as examples. The metal oxides, such as gamma-alumina (gamma-Al2O3), magnesium oxide (MgO) and lanthanum oxide (La2O3) showed an efficient ability to dechlorinate the BP-Cl; however, BP-Cl remained in the ground samples when the hydroxides were used. From the product analysis using gas chromatography/mass spectrometry (GC/MS) and electron spin resonance (ESR) measurements, it was confirmed that the charge transfer from the O2- site on the surface of the oxide additives due to the intense grinding has plays a significant role in the decomposition of the chlorinated compound. Based on the observed dependence of the dechlorination on the radical occurrence, some practical methods were proposed to improve the destruction efficiency of the chlorinated organic compounds.     

Chlorinated persistent organic pollutants in black-tailed gulls (Larus crassirostris) from Hokkaido, Japan

Concentrations and patterns of several chlorinated persistent organic pollutants (POPs) including polychlorinated dibenzo-p-dioxins (PCDDs), dibenzofurans (PCDFs) and biphenyls (PCBs) and DDTs, HCHs, CHLs and HCB were determined in black-tailed gulls (Larus crassirostris) from breeding grounds in Hokkaido, Japan. Subcutaneous fat of five adult gulls was analyzed, which had different concentrations of target compounds, whereas gull eggs contained similar concentrations of target compounds. Similar congener profiles were found between adult gulls and eggs. The concentrations of non-ortho PCBs varied from 3.4 to 13.5 ng/g lipid weight (lw) in the fat of black-tailed gulls and from 2.4 to 7.4 ng/g lw in their eggs. 2,3,7,8-PCDD/Fs occurred at relatively lower concentrations than non-ortho PCB congeners in both adult gulls and eggs. The total TEQs (toxic equivalents, PCDD/Fs+ non-ortho PCB) ranged from 0.26 to 1.0 ng/g lw in adult gulls and ranged from 0.19 to 0.58 ng/g lw in eggs.     

mRNA expression of a cadmium-responsive gene is a sensitive biomarker of cadmium exposure in the soil collembolan Folsomia candida

The gene expression of environmental organisms is useful as a biomarker of environmental pollution. One of its advantages is high sensitivity. We identified the cDNA of a novel cadmium-responsive gene in the soil collembolan Folsomia candida. The deduced protein, designated “metallothionein-like motif containing protein” (MTC), was cysteine-rich and contained a metallothionein-like motif with similarity to metallothionein, but had a much longer sequence than metallothionein and contained repeated sequences of amino acids. Expression of MTC mRNA was sensitively induced by cadmium exposure at 0.3 mg/kg of dry food, a concentration at which toxic effects are not observed, but expression was not affected by γ-ray exposure (an inducer of oxidative stress). These findings suggest that MTC is involved in cadmium-binding processes rather than in oxidative-stress responses. In conclusion, we suggest that gene expression of MTC may be a candidate biomarker for detecting low levels of cadmium contamination in soil.     

Isomer‐specific determination and toxic evaluation of potentially hazardous coplanar PCBs,dibenzofurans and dioxins in the tissues of “Yusho” PCB poisoning victim and in the causal oil

In the light of new discoveries on the extremely toxic non‐ortho coplanar 3,3’,4,4'‐tetra‐ (T₄CB), 3,3’,4,4’,5‐penta‐(P₅CB) and 3,3'4,4’,5,5'‐hexachlorobiphenyl (H₆CB) and their mono‐ and di‐ortho analogs, tissue samples of a Yusho poisoning victim and Yusho causal oils were subjected to a thorough congener/isomer‐specific investigation for polychlorinated biphenyls (PCBs), polychlorinated dibenzofurans (PCDFs), polychlorinated dibenzo‐p‐dioxins (PCDDs). Among the many PCB congeners detected in Yusho oil, non‐ortho coplanar T₄CB constituted 3.1%, P₅CB‐0.17% and H₆CB‐0.0072% in total PCBs. Their concentrations in liver and adipose tissue were 130–700 (T₄CB), 54–720 (P₅CB) and 50–380 (H₆CB) pg/g on wet weight basis. The observed concentrations in adipose tissue were two to four fold higher than that detected in unexposed individuals. Among the PCDFs identified, toxic 2,3,7,8‐substituted isomers including 2,3,4,7,8‐P₅CDF were the dominant ones. Tetra‐ through hepta‐CDDs were detected in the oil, whereas octa‐CDD was the dominant isomer in the patient. A comparison with KC‐400 revealed enrichment of coplanar PCBs in Yusho oil along with toxic PCDFs. Enrichment was highest for 3,3'4,4'5,5'‐H₆CB followed by 3,3’,4,4'5‐P₅CB. A comparative toxic evaluation of these chemical groups in Yusho patient's adipose tissue based on “2,3,7,8‐T₄CDD Toxic Equivalent Analysis” revealed accountable toxic contribution from coplanar PCBs. This analysis also confirmed that 2,3,4,7,8‐P₅CDF was the principal causative agent in Yusho poisoning.     

Effects of amine, amine salt and amide on the behaviour of carbon dioxide absorption into calcium hydroxide suspension to precipitate calcium carbonate

The amount of carbon dioxide （CO2） absorption and calcium ion （Ca^2＋） concentration besides the pH of aqueous solution were observed during the COz absorption to precipitate calcium carbonate （CaCO3） from calcium hydroxide （Ca（OH）2）. A reaction rate-limiting effect of an amount of CO2 absorption without any organic additives in the early stage of the precipitation was observed, which was attributed to an interruption effect of bicarbonate ion （HCO3） on the precipitation of CaCO3. The improvement for the reaction rate was achieved not only by amine additives but also by neutral additives such as ε-caprolactam or amine salt. When the hexamethylene diamine was dissolved in the solution, successive change of crystal forms of CaCO3 aragonite to calcite in aqueous suspensions, confirmed by Ca^2＋ concentration change and X-ray diffraction, was concluded that a local environment around the amine group in aqueous solution and an interaction of the diamine with precipitated CaCO3 particles were important factors for these reactions.     

Formation and decomposition of tetrafluoroborate ions in the presence of aluminum

The formation and decomposition of tetrafluoroborate ions (BF₄⁻) in H₃BO₃-Al³⁺-F⁻ solutions were investigated via experiments and thermodynamic calculations. The concentration of the formed BF₄⁻ increased with decreasing pH, raising the total fluoride concentration and lowering the total aluminum ion concentration. Once formed, BF₄⁻ was stable under neutral and alkaline conditions. Fluoride in the form of BF₄⁻ was converted to fluoroaluminate ions by adding an aluminum compound under acidic conditions. A method for removing fluoride in the form of BF₄⁻ is proposed whereby fluoroaluminate ions formed by the reaction of BF₄⁻ with aluminum are decomposed with calcium ions. This process was applied to the treatment of wastewater from flue gas desulfurization plants, and resulted in a satisfying level of reduction in the range of the fluoride emission limit of 8 mg/l.     

Removal of tetrafluoroborate ion from aqueous solution using magnesium-aluminum oxide produced by the thermal decomposition of a hydrotalcite-like compound

Magnesium-aluminum oxide (Mg-Al oxide) prepared by the thermal decomposition of a hydrotalcite-like compound was found to have potential for treating NaBF(4) wastewater. The Mg-Al oxide removed the BF(4)(-) and F(-) and H(3)BO(3) from the NaBF(4) solution. With increasing Mg-Al oxide quantity and time, the BF(4)(-) concentration decreased and the degree of BF(4)(-), F(-), and boron removal increased. The decrease in the BF(4)(-) concentration resulted from uptake by the Mg-Al oxide and not hydrolysis. The Mg-Al oxide took up F(-) from the solution preferentially. The Mg-Al oxide also converted the H(3)BO(3) in the aqueous solution into H(2)BO(3)(-), which it took up.     

Concentrations and accumulation profiles of polychlorinated dibenzo-p-dioxins and dibenzofurans in aquatic tissues, and ambient air from South Korea

Polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDDs/DFs), including 2378-substituted isomers were present in samples of shellfish and fish, and ambient air collected from Masan Bay, and Masan City, South Korea. Total concentrations of PCDDs/DFs in mussel and clam were 750 pg g(-1), lipid weight (lw), and 3418 pg g(-1), lw, respectively. Total concentrations of PCDDs/DFs in mullet, gizzard and flounder were 52, 82, and 122 pg g(-1), lw, respectively. Shellfish tissues contained a greater number of PCDD/DF isomers, contributing greater total concentrations of PCDDs/DFs compared to fish collected from the same locations. The predominance of 2378-substituted PCDDs/DFs in fish is represented in greater total concentrations of 2378-TeCDD equivalents (TEQs), whereas there was very limited occurrence of 2378-substituted isomers in shellfish. TEQ concentrations in samples of mussel and clam were 0.97 and 12 pg g(-1), lw, respectively. Total TEQs in mullet, gizzard and flounder were 12, 22 and 18 pg g(-1), lw, respectively. In fish 2378-substituted PCDDs accounted for 100% of the total concentrations of PCDDs, and 2378-substituted PCDFs accounted from 59% to 73% of the total PCDFs. The 2378-substituted isomers accounted for only 3% of the total PCDDs/DFs in shellfish. Ambient air collected from two sites contained a wide range of isomers of tetra- through heptachlorinated PCDDs/DFs. Even though the total concentration of PCDDs/DFs in ambient air (12.8 pgm(-3)) collected from an industrial area was 2-fold greater than that in air samples (6.3 pgm(-3)) collected from an urban/rural area, total TEQs (0.07 and 0.08 pgm(-3)) there was no statistical difference between the two samples.