Polychlorinated dibenzo-p-dioxins and related compounds in breast milk of Japanese primiparas and multiparas

We analyzed polychlorinated dibenzo-p-dioxins and related compounds in the breast milk of primiparas and multiparas, and estimated the levels transferred to newborns by breast milk in Western Japan. 2,3,7,8-TeCDD equivalents (TEQ) of the chemicals in primiparas decreased slightly from 1994 to 1996. In particular, decreases of the TEQs of total PCDDs and total coplanar PCBs were higher than that of total PCDFs. In 2,3,7,8-TeCDD, 1,2,3,7,8-PeCDD, 1,2,3,6,7,8-HxCDD, 1,2,3,7,8,9-HxCDD, 2,3,4,7,8-PeCDF, 1,2,3,6,7,8-HxCDF, 3,3',4,4',5-PeCB and 3,3',4,4',5,5'-HxCB concentrations, those in the breast milk of multiparas were significantly lower than those in the breast milk of primiparas (p < 0.05, lipid basis). Based on the assumption that newborns ingest 120 g of breast milk per kg body weight per day, the amounts converted to TEQ values were 121 pg/kg/day (primiparas) and 97.2 pg/kg/day (multiparas).     

Recent trend of polychlorinated dibenzo-p-dioxins and their related compounds in the blood and sebum of Yusho and Yu Cheng patients

We investigated the levels of polychlorinated dibenzo-p-dioxins (PCDDs) and their related compounds in blood and sebum from Yusho and Yu-Cheng patients and findings compared with those of normal subjects. Concentrations of these compounds in blood and sebum still were obviously reflected the chemical concentration in the causal rice oil ingested 17 or 26 years since the outbreak. In addition, sebum form the body surface was the most useful sample for monitoring the amount of chemicals contaminating the human body.     

Measurement and modeling of oxidation rate of hydrogen isotopic gases by soil

Measurements of oxidation rate of hydrogen isotopic gases by soil were made to model HT oxidation rate by soil. Soil was sampled at a cultivated farmland and laboratory measurements of the oxidation rate of H(2) and D(2) gases simulating HT gas were carried out under controlled conditions of soil. The oxidation rate increased with increase of H(2) or D(2) concentration in air and nearly saturated at high concentration. The oxidation rate was low under extremely dry and wet soil conditions and was the highest at soil water content of 8-14 w/w%. The oxidation rate increased exponentially with increasing soil temperature and was the highest at 46 degrees C. Michaelis constant K(m) increased exponentially with increasing soil temperature. Oxidation rate of H(2) was generally higher than that of D(2), while K(m) of H(2) was generally lower than that of D(2). From these results, oxidation rate of HT was modeled as a product of the functions that represent dependency on each soil factor.     

Odd-numbered perfluorocarboxylates predominate over perfluorooctanoic acid in serum samples from Japan, Korea and Vietnam

Perfluorooctanoic acid (PFOA) has recently attracted attention as a potential health risk following environmental contamination. However, information detailing exposure to perfluorinated carboxylic acids (PFCAs) other than PFOA is limited. We measured the concentrations of PFCAs (from perfluorohexanoic acid to perfluorotetradecanoic acid) in serum samples obtained from patients in Japan (Sendai, Takayama, Kyoto and Osaka) between 2002 and 2009, Korea (Busan and Seoul) between 1994 and 2008 and Vietnam (Hanoi) in 2007/2008. Total PFCA levels (geometric mean) were increased from 8.9 ng mL(-1) to 10.3 ng mL(-1) in Japan; from 7.0 ng mL(-1) to 9.2 ng mL(-1) in Korea; and were estimated at 4.7 ng mL(-1) in Vietnam. PFCAs of greater length than PFOA were significantly increased in Sendai, Takayama and Kyoto, Japan, and levels of long-chain PFCAs exceeded PFOA levels in serum. Among these PFCAs, perfluoroundecanoic acid (PFUnDA) was the predominant component (28.5%), followed by perfluorononanoic acid (PFNA 17.5%), perfluorodecanoic acid (PFDA 7.9%), perfluorotridecanoic acid (PFTrDA 6.1%) and perfluorododecanoic acid (PFDoDA 1.8%). Odd-numbered PFCAs (PFNA, PFUnDA and PFTrDA) were also observed in Korea and Vietnam and their presence increased significantly in Korea between 1994 and 2007/2008. The proportion of long-chain PFCAs in serum was relatively high compared to reports in Western countries. Further investigations into the sources and exposure routes are needed to predict the future trajectory of these serum PFCA levels.     

Concentrations and their ratio of (222)Rn decay products in rainwater measured by gamma-ray spectrometry using a low-background Ge detector

The concentrations and the concentration ratios of individual short-lived (222)Rn decay products ((214)Pb and (214)Bi) in rainwater were measured at Kumatori village (34.39 degrees N, 135.35 degrees E, approximately 70 m above sea level) in Osaka, Japan, by gamma-ray spectrometry using a low-background Ge detector. The dependence of the time variations of the concentrations and their ratios on rainfall rate was investigated. It was observed that the concentrations were negatively correlated with the rainfall rate in some rainfall events, and that there was no clear correlation in other rainfall events. The changes in the dependence of the concentration on the rainfall rate occurred after the passage of a cold front during a single rainfall event. The concentration ratios showed a weak negative correlation with the rainfall rate for most of the observed rainfall events. A scavenging model was designed in this study in order to explain the observation results. Based on the relationship between the concentrations of (214)Pb and (214)Bi in the rainwater and the rainfall rate for an individual rainfall event, the increase in the environmental gamma-ray dose rate from (214)Pb and (214)Bi deposited on the ground was calculated, and the calculated increase agreed well with that observed by the in situ measurement on flat ground.     

Deposition processes of ionic constituents to snow cover

Atmospheric deposition is an important removal process of aerosol particles and gases from the atmosphere. To elucidate the relative contributions of wet and dry processes and in-cloud and below-cloud scavenging based on deposition amounts in winter at Mt. Tateyama, central Japan, we obtained daily samples (December, 2006–March, 2007) of size-segregated aerosol particles and precipitation at Senjyugahara (SJ; 475 m a.s.l.) and vertical samples of spring snow cover at Murododaira (MR, 2450 m a.s.l., 13 km distance from SJ) on the western flank of Mt. Tateyama. The NH₄⁺ and nssSO₄^2? in aerosols were mostly found in the fine fraction (<2 μm), although Na⁺, NO₃^?, and nssCa²⁺ were mainly detected in the coarse fraction (>2 μm). Average ionic concentrations (μg g^?1) in precipitation at SJ were higher about 3.8 for Na⁺ and nssCa²⁺, 3.4 for NO₃^?, 3.7 for NH₄⁺, 2.5 for nssSO₄^2? than those at MR, whereas cumulative precipitation amounts at SJ and MR were, respectively, 84 and 175 cm of water equivalent. Wet and dry deposition amounts during the study period were estimated for sites using size-segregated aerosol data, winter averages of HNO₃, NH₃, and SO₂ concentrations, and dry deposition velocities. Particle-dry deposition comprised about 3% (Na⁺) to 11% (NH₄⁺) of the total deposition at MR. The maximum amounts of gas dry deposition were estimated, respectively, as 4, 13, and 3% of the total deposition at MR for NH₄⁺, NO₃^?, and nssSO₄^2?. The relative contributions of below-cloud scavenging (BCS) between MR and SJ were estimated as considering the wet only deposition amount at MR. Higher contributions of BCS were obtained for Na⁺ (56%) and nssCa²⁺ (45%), whereas BCSs for NH₄⁺, NO₃^?, and nssSO₄^2? were lower than 28%. Ionic constituents existing predominantly in the coarse fraction showed a large contribution of BCS.     

Evaluation of chemical stability of heavy metals in industrial waste slag by infrared spectroscopy

Our aim was to clarify the chemical bonding type and stability of heavy metals in industrial waste slag (IWS) by using Fourier transform infrared (FT-IR) spectroscopy. The chemical composition of the IWS sample used in this study was an Al/Si ratio of 0.50 with Fe, Pb, and other minor heavy metals present. The IR peak position of the Si-OSi( M) band (M: Al, Pb, or Fe) was lower for IWS (971 cm⁻¹) than for synthetic Si-Al glass with an Al/Si ratio of 0.5 (1029 cm⁻¹). This implies the formation of covalent Si-O-Pb and Si-O-Fe bonds in the IWS, which caused a shift in the peak position toward a lower wavenumber. FT-IR spectra of synthetic Si-Al-Pb and Si-Al-Fe glasses with various Pb/Si and Fe/Si ratios with a constant Al/Si ratio of 0.5 showed that the peak position of the Si-O-Si(M) band continuously shifted toward lower wavenumbers with increasing Pb/Si and Fe/Si ratios. This suggests that covalent Si-O-Pb and Si-O-Fe bonds are formed in IWS. The comparison of peak positions of the Si-O-Si(M) band between IWS and Si-Al-Fe glass indicated that not only Pb but also other minor heavy metals such as Cu and Cr were included by covalent bonds into the structure of IWS. Therefore, we concluded that most of the heavy metals in IWS formed covalent Si-O-M bodings and were chemically stable.     

Polychlorinated dibenzo-p-dioxins and related compounds: The blood levels of young Japanese women

We investigated PCDDs and related compounds in the blood of young Japanese women, approximately 20 years of age, who had not yet had children, and discussed how the TEQ level of PCDDs and related compounds in their blood may affect the next generation. Means of total TEQ levels were 0.063 pg/g for whole blood basis and 21 pg/g for lipid basis. TEQ of PCDDs, PCDFs and coplanar PCBs accounted for about 43, 34 and 23% of the total TEQ in the whole blood basis, respectively. In the lipid basis, their values were about 44, 34 and 22%, respectively. Previously, we investigated PCDDs and related compounds levels in mother's breast milk, lymphocyte subpopulation and thyroid function of their children, and found negative correlations between the TEQ level of PCDDs and related compounds and CD4+/CD8+, and/or the TEQ level of PCDDs and related compounds and the T₄ level in 36 mothers and children. Of these cases, the average age was approximately 28 years. PCDDs and related compounds may be related to immunopathy, such as atopic dermatitis. The effects of PCDDs and related compounds on babies of young Japanese women are important and must be further evaluated.     

Polychlorinated dibenzo-p-dioxins,polychlorinated dibenzofurans and non-ortho,mono-ortho chlorine substituted biphenyls in Japanese human liver and adipose tissue

We measured PCDDs/DFs levels in Japanese human livers and adipose tissues in 1999, and TEQ were calculated with WHO TEF. The mean total levels of PCDDs/DFs in livers and adipose tissues were 57 pg TEQ/g on a lipid basis and 49 pg TEQ/g on a lipid basis, respectively. 1,2,3,6,7,8-HxCDD, 1,2,3,4,6,7,8-HpCDD, OCDD, 2,3,4,7,8-PeCDF, 1,2,3,4,7,8-HxCDF, 1,2,3,6,7,8-HxCDF, 2,3,4,6,7,8-HxCDF, 1,2,3,7,8,9-HxCDF and 1,2,3,4,6,7,8-HpCDF concentrations in livers considerably differed from those in 1989 (p < 0.05). The mean non-ortho-chlorine substituted biphenyls levels showed 20 pg TEQ/g on a lipid basis and 17 pg TEQ/g on a lipid basis in livers and adipose tissues, respectively. In livers, the mean of 3,3',4,4'-TCB concentrations was 131 pg/g on a lipid basis, and 7.7-fold higher than that in 1989. The mean total mono-ortho-chlorine substituted biphenyls level was 13.0 pg TEQ/g on a lipid basis in livers and 21.6 pg TEQ/g on a lipid basis in adipose tissues. 3,3',4,4',5-PeCB and 3,3',4,4',5,5'-HxCB levels decreased in adipose tissues, and 3,3',4,4',5-PeCB level only decreased in livers. PCDDs, PCDFs, and mono- and non-ortho-chlorine substituted biphenyls levels may have decreased in livers and adipose tissues because of a governmental policy on dioxins discharge for the decade. Then, we estimated the correlations of PCDDs, PCDFs and the related compound levels between livers and adipose tissues. The correlative PCDDs congeners may have had a similar behavior to that between liver and adipose tissue. On the contrary, most PCDFs isomers may have different behavior between liver and adipose tissue, while 2',3,4,4',5-PeCB (IUPAC No. 123) may also have a different behavior between liver and adipose tissue.