Simultaneous determination of 2-phenylbenzotriazole-type mutagens, PBTA-1 through -8, in river water by liquid chromatography-tandem mass spectrometry

We describe a method for the simultaneous determination of eight kinds of phenylbenzotriazole-type mutagens (PBTA-1, -2, -3, -4, -5, -6, -7 and -8) in river water based on liquid chromatography-tandem mass spectrometry (LC/MS/MS). The application of dopant-assisted atmospheric pressure photoionization (APPI) for the detection of the PBTAs was studied. The APPI technique provided higher PBTA signal intensities than those obtained with an electrospray ionization (ESI) source, and the APPI method was used for the determination of the PBTAs. A solid-phase extraction procedure was used for the extractions of PBTA-1 through -8 from river water. The procedure was rapid and the relative standard deviations were below 15%. The detection limits of PBTA-1 through -8 in river water using the proposed method were found to range from 0.04 to 0.5 ng L(-1) and PBTAs were successfully detected in river water at sub-ng L(-1) levels.     

Regulatory Off-Gas Analysis from the Evaporation of Hanford Simulated Waste Spiked with Organic Compounds

Abstract

After strontium/transuranics removal by precipitation followed by cesium/technetium removal by ion exchange, the remaining low-activity waste in the Hanford River Protection Project Waste Treatment Plant is to be concentrated by evaporation before being mixed with glass formers and vitrified. To provide a technical basis to permit the waste treatment facility, a relatively organic-rich Hanford Tank 241-AN-107 waste simulant was spiked with 14 target volatile, semi-volatile, and pesticide compounds and evaporated under vacuum in a bench-scale natural circulation evaporator fitted with an industrial stack off-gas sampler at the Savannah River National Laboratory. An evaporator material balance for the target organics was calculated by combining liquid stream mass and analytical data with off-gas emissions estimates obtained using U.S. Environmental Protection Agency (EPA) SW-846 Methods. Volatile and light semi-volatile organic compounds (<220 °C BP, >1 mm Hg vapor pressure) in the waste simulant were found to largely exit through the condenser vent, while heavier semi-volatiles and pesticides generally remain in the evaporator concentrate. An OLI Environmental Simulation Program (licensed by OLI Systems, Inc.) evaporator model successfully predicted operating conditions and the experimental distribution of the fed target organics exiting in the concentrate, condensate, and off-gas streams, with the exception of a few semi-volatile and pesticide compounds. Comparison with Henry's Law predictions suggests the OLI Environmental Simulation Program model is constrained by available literature data.     

Blood levels of PCDDs,PCDFs, and coplanar PCBs in Yusho mothers and their descendants: Association with fetal Yusho disease

Maternal exposure to polychlorinated dibenzo-p-dioxins (PCDDs), polychlorinated dibenzofurans (PCDFs), and polychlorinated biphenyls (PCBs) may result in adverse health effects in their children. In Japan in 1968, an accidental human exposure to rice oil contaminated with PCDDs, PCDFs, and PCBs, led to the development of Yusho disease. Yusho mothers delivered descendants with low birth weights and hyperpigmented skin and mucosa, which are characteristic of fetal Yusho disease (FYD). The Yusho cohort was used to evaluate the effect of maternal exposure to PCDDs, PCDFs, and PCBs on the development of FYD. Blood samples, obtained from 64 Yusho mothers (117 descendants: 10 with FYD and 107 without FYD), were analyzed for congeners of seven PCDDs, 10 PCDFs, and four coplanar PCBs. We investigated the association between the maternal estimated blood levels of dioxins at delivery and the risk of fetal Yusho disease. We also studied the differences in dioxin blood levels in 24 mother–descendant pairs (5 with FYD and 19 without FYD). The estimated levels of total PCDD TEQ, total PCDF TEQ, total coplanar PCB TEQ, and total TEQ in the maternal blood at delivery were associated with significantly increased risk of FYD. The odds ratios, which present the risk of FYD for a 10-fold increase in blood dioxin, were largest for 1,2,3,6,7,8-HexaCDD (odds ratio = 28.6, 95% confidence interval = 1.67–489.9, p = 0.02). The levels of 1,2,3,6,7,8-HexaCDD in both the Yusho mothers and their descendants with FYD were higher than the levels in those without FYD. These findings suggest that 1,2,3,6,7,8-HexaCDD is the most important causative congener for the development of FYD.     

Regional and seasonal characteristics of emission sources of fine airborne particulate matter collected in the center and suburbs of Tokyo, Japan as determined by multielement analysis and source receptor models

Airborne particulate matter, suspected to induce adverse effects on human health, have been one of the most important concerns regarding recent air pollution issues in Japan. To characterize regional and seasonal variations in emission sources of fine airborne particulate matter (d < 2 microm), monthly samples (n = 36 for each site) were collected at urban (Tokyo), suburban (Maebashi), and mountainous (Akagi) sites in Japan from April 2003 to March 2006. Multielement analysis of chemical species (Na, Al, K, Ca, V, Cr, Mn, Fe, Ni, Cu, Zn, As, Sb, and Pb) was performed by inductively coupled plasma-atomic emission spectrometry and inductively coupled plasma-mass spectrometry. The combined source receptor model, which consists of positive matrix factorization and chemical mass balance, determined the contributions of nine emission sources (local and continental soils, road dust, coal and oil combustion, waste incineration, steel industry, brake wear, and diesel exhaust) to the observed elemental concentrations. Large regional differences were identified in the source contributions among the observational sites. Diesel exhaust was identified as the most significant source (70% of identified contributions) at the urban site. Local and continental soils, coal combustion, and diesel exhaust were intricately assigned (20-30% each) to the suburban site. Continental soil was the predominant source (65%) at the mountainous site. Respective significant source contributions dominated the seasonal variations of total elemental concentrations at each site. These results suggest that a better understanding of the regional and seasonal characteristics of impacting emission sources will be important for improving regional environments.     

Body color change and serum steroid hormone levels throughout the process of sex change in the adult wrasse, <Emphasis Type="Italic">Pseudolabrus sieboldi</Emphasis>

Gonadal sex steroid hormones are the principal factors that directly control the gonadal and morphological alterations during sex change in hermaphrodite fish; however, the physiological mechanism of action by which these hormones govern body coloration is poorly understood. The protogynous wrasse Pseudolabrus sieboldi is a good model for understanding the physiological mechanisms of gonadal and body color change during sex change in hermaphrodite fish. To obtain information on the relationship between sex steroids and body color change during the process of gonadal sex change, we analyzed body color, gonadal histology, and serum levels of sex steroids. Body color was analyzed using a quantitative analytical method based on the hue value. Compared to other body parts of the fish, the anal fin changed color the most, becoming increasingly redder in association with gonadal changes that converted ovaries to testes. Levels of serum 11-ketotestosterone (11KT) increased as the gonadal sex change proceeded, whereas no significant change was observed in estradiol-17β (E2) levels. Moreover, we found a significant correlation between the hue value of the anal fin and serum 11KT levels, but not E2 levels. These results suggest that androgen, but not estrogen, plays a principle role in the changes in both gonadal morphology and body color in the transformation from female to male in this species. To our knowledge, this is the first quantitative demonstration of the relationship between body color and serum steroid levels during sex change in fish.     

Dissolution kinetics of high explosives particles in a saturated sandy soil

Solid phase high explosive (HE) residues from munitions detonation may be a persistent source of soil and groundwater contamination at military training ranges. Saturated soil column tests were conducted to observe the dissolution behavior of individual components (RDX, HMX, and TNT) from two HE formulations (Comp B and C4). HE particles dissolved readily, with higher velocities yielding higher dissolution rates, higher mass transfer coefficients, and lower effluent concentrations. Effluent concentrations were below solubility limits for all components at superficial velocities of 10-50 cm day(-1). Under continuous flow at 50 cm day(-1), RDX dissolution rates from Comp B and C4 were 34.6 and 97.6 microg h(-1) cm(-2) (based on initial RDX surface area), respectively, significantly lower than previously reported dissolution rates. Cycling between flow and no-flow conditions had a small effect on the dissolution rates and effluent concentrations; however, TNT dissolution from Comp B was enhanced under intermittent-flow conditions. A model that includes advection, dispersion, and film transfer resistance was developed to estimate the steady-state effluent concentrations.     

Contamination status of persistent organochlorines in human breast milk from Japan: recent levels and temporal trend

Contamination levels of persistent organochlorines (OCs) such as polychlorinated dibenzo-p-dioxins (PCDDs), dibenzofurans (PCDFs), biphenyls (PCBs), dichlorodiphenyltrichloroethane and its metabolites (DDTs), hexachlorocyclohexane isomers (HCHs), hexachlorobenzene (HCB), and chlordane compounds (CHLs) was examined in human breast milk collected during 2001-2004 from Fukuoka prefecture in Japan. The concentrations of OCs such as dioxins and related compounds, DDTs, CHLs and HCB in human breast milk from primiparae were comparable to or slightly higher than the data obtained during 1998, indicating that the levels of these contaminants in Japanese human breast milk have not decreased since 1998 and Japanese are continuously exposed to these chemicals, presumably via fish intake. In addition, OC levels in human breast milk from primiparae were significantly higher than those from multiparae, implying elimination of OCs via lactation. Furthermore, significant positive correlations were observed between levels of OCs in human breast milk and the age of primiparae. These results indicate that the mothers with higher age may transfer higher amounts of OCs to the first infant than to the infants born afterwards through breast-feeding, and hence the first born children might be at higher risk by OCs.     

Human milk survey for dioxins in the general population in Japan

BACKGROUND: Much attention has been paid to the level of dioxins in breast milk in Japan but few large-scale studies have been conducted on the subject. METHODS: From 1997 to 2002, we collected 839 samples of breast milk from primiparas residing throughout Japan. Starting in 1999, breast milk was also collected from secundiparas. Seven isomers of polychlorinated dibenzo-p-dioxins (PCDDs), 10 of polychlorinated dibenzofurans (PCDFs), 4 of coplanar polychlorinated biphenyls (Co-PCBs) and 8 of mono-orthochlorinated polychlorinated biphenyls (mono-ortho PCBs) were analyzed by employing gas chromatography and mass spectrometry. A correlation between the level of dioxins in human milk and the age of the mothers was noted for the primiparas and the secundiparas; and the levels were compared between the first and the second deliveries. Grouped by parity and prefecture in each year, observations were also made on the trends in these levels. Dioxin levels are shown by using geometric means because their distributions were skewed to the left. RESULTS: The sum of PCDDs and PCDFs, Co-PCBs, mono-ortho PCBs, and total dioxins in the breast milk of primiparas were 13.9, 5.4, 3.4, and 22.7 pg TEQ/g fat, respectively. In the samples obtained from secundiparas, these levels were 63-68 percents of those taken from the primiparas. The correlation coefficients between the PCDDs/DFs, Co-PCBs, mono-ortho PCBs, and total dioxins and the age of the primiparas were 0.19, 0.17, 0.36, and 0.24, respectively. All these correlations were statistically significant (p < 0.001). The positive correlations between these contaminants and the age of the secundiparas were also examined. The total dioxins as well as PCDDs/DFs, Co-PCBs, and mono-ortho PCBs in the breast milk of the primiparas declined significantly between 1998 and 2002 (regression coefficients: -0.04, -0.05, -0.03, and -0.03, respectively). However, no significant decline in these levels was observed when sorted by prefectures. CONCLUSIONS: Much attention should be paid to the age and parity of nursing mothers when investigating the relationship between the level of dioxins in breast milk and the body burden of infants.     

Scenario Formation of Energy Demand and CO_2 Emissions for Sustainable China

Co-integration theory has been employed in this paper and Granger causes are found between urbanization rate and GDP, between capital stock and GDP. Scenario analysis of GDP is performed using the GDP model established in the paper. The energy consumptions in Germany, Japan and other developed countries are analyzed and compared with the energy consumption in China. Environmental friendly scenario of energy demand and CO2 emissions for sustainable China has been formed based on the results of comparison. Under environmental friendly scenario, the primary energy consumption will be 4.31 billion ton coal equivalence （tee） and CO2 emissions will be 1.854 billion t-c in 2050; energy per capital will be 3.06 tee that is 1.8 times of energy consumed in 2005 in China and 51% of consumed energy per capital in Japan in 2003. In 2050, the energy requirement of unit GDP will be 20% lower than that of Germany in 2003, but will be still 37% higher than that in Japan in 2003. It is certain that to fulfill the environmental friendly Scenario of energy demand and CO2 emissions is a difficult task and it needs long term efforts of the whole society, not only in production sectors but also in service and household sectors,     

Formation of mutagens by photochemical reaction of biphenyl in nitrate aqueous solution

Biphenyl was found to be converted to mutagenic compounds by UV irradiation with a high-pressure mercury lamp in nitrate aqueous solution under neutral conditions. The mutagenicity of the reaction mixture increased in proportion to the nitrate ion concentration. The most mutagenic product was dinitro dihydroxy biphenyl, and the main products in this reaction were 2-hydroxy-3-nitrobiphenyl and 4-hydroxy-3-nitrobiphenyl.