Residual organic fluorinated compounds from thermal treatment of PFOA,PFHxA and PFOS adsorbed onto granular activated carbon (GAC)

Perfluorooctanoic acid (PFOA), perfluorohexanoic acid (PFHxA) and perfluorooctane sulfonate (PFOS) adsorbed onto granular activated carbon (GAC) were thermally treated in N₂ gas stream. The purpose was to assess the fate of perfluoroalkyl and polyfluoroalkyl substances (PFASs) during thermal regeneration of GAC, which had been used for water treatment. Mineralized F, residual PFASs including short-chained species, and volatile organic fluorine (VOF) were determined. In a temperature condition of 700 °C, VOF were 13.2, 4.8, and 5.9 % as for PFOA, PFHxA, and PFOS. However, the VOF decreased to 0.1 %, if the GAC and off-gas were kept at 1000 °C. No PFASs remained in GAC at 700–1000 °C; at the same time, short-chained PFASs were slightly detected in the aqueous trapping of off-gas at 800 and 900 °C conditions. The destruction of PFASs on GAC could be perfect if the temperature is higher than 700 °C; however, the process is competitive against volatile escape from GAC. Destruction in gaseous phase needs a temperature as high as 1000 °C. Destruction of PFASs on the surface of GAC, volatile escape from the site, and thermolysis in gas phase should be considered, as to thermal regeneration of GAC.     

Molecular size as a limiting characteristic for bioconcentration in fish

The relationships between the bioconcentration factor (BCF) of chemicals in fish and their size, as characterized by molecular weight (MW), effective cross sectional diameter (Deff), and maximum diameter (Dmax) have been investigated using an experimental data set of 737 new and 441 existing chemicals monitored by the Japanese Chemical Substances Control Law (CSCL). Substances with BCF > or = 5000 (very high bioconcentration potential) typically have MW < 550, Deff < 1.1 nm and Dmax < 2.0 nm, respectively and the substances with BCF > or = 1000 (high bioconcentration potential) have MW < 550, Deff < 1.4 nm and Dmax < 2.9 nm, respectively Therefore, the previously suggested threshold values for Deff (0.95 nm) and Dmax (1.5 nm) used for discriminating between bioconcentrative and non-bioconcentrative substances were found to be somewhat small. We found that many substances with BCF > or = 1000 and Dmax > or = 1.5 nm have Deff < 0.95 nm.     

Degradation of monofluorophenols in water irradiated with gaseous plasma

Decomposition of aqueous monofluorophenols (MFPs) was investigated by contact glow discharge electrolysis (CGDE). During CGDE, both MFPs and the corresponding total organic carbon (TOC) in water were consumed smoothly, suggesting that carbon atoms of benzene nucleus could be eventually mineralized to inorganic carbon (IC). And all the fluorine atoms in the MFPs were equally converted to fluoride ions. Based on the primary intermediates from each starting materials, it showed that aromatic hydroxylation preferentially occurred at the para-or ortho-position to the phenolic OH group of each MFPs. The disappearance of both MFPs and TOC followed the first-order rate law. The apparent rate constants for the decay of MFPs were independent from the pK_a values of MFPs.     

Exhaustive breakdown of aqueous monochlorophenols by contact glow discharge electrolysis

The aqueous monochlorophenols were degraded by contact glow discharge electrolysis (CGDE), in which plasma was generated in a localized zone between an electrolytic solution and an anode. With the decay of monochlorophenols, the amount of total organic carbon (TOC) also decreased smoothly, indicating that carbon atoms of benzene nucleus could be eventually converted to inorganic carbons. Meanwhile, it was also clarified that chlorine atoms in the organics were liberated as chloride ions. In addition, it was revealed that the disappearance of monochlorophenols obeyed the first-order rate law, depending on the isomeric structures.     

Investigation of perfluoroalkyl carboxylic and sulfonic acids in leachates from industrial and municipal solid waste landfills,and their treated waters and effluents from their closest leachate treatment plants

Journal of Material Cycles and Waste Management - Per- and polyfluoroalkyl substances (PFASs) are used in products, such as aqueous film-forming foam and fluorochemical surfactants, because of...     

Arsenic,selenium, and chromium speciation in fly ash

Journal of Material Cycles and Waste Management - Arsenic (As), selenium (Se), and chromium (Cr) are harmful to humans at certain concentrations, and can possibly be eluted from coal ash (fly ash)...     

Estimation of mechanical dispersion and dispersivity in a soil-gas system by column experiments and the dusty gas model

In a previous study, column experiments were carried out with Toyoura sand (permeability 2.05×10(-11)m(2)) and Toyoura sand mixed with bentonite (permeability 9.96×10(-13)m(2)) to obtain the molecular diffusion coefficient, the Knudsen diffusion coefficient, the tortuosity for the molecular diffusion coefficient, and the mechanical dispersion coefficient of soil-gas systems. In this study, we conducted column experiments with field soil (permeability 2.0×10(-13)m(2)) and showed that the above parameters can be obtained for both less-permeable and more-permeable soils by using the proposed method for obtaining the parameters and performing column experiments. We then estimated dispersivity from the mechanical dispersion coefficients obtained by the column experiments. We found that the dispersivity depended on the mole fraction of the tracer gas and could be represented by a quadratic equation.     

Urinary concentrations of organophosphorus insecticide metabolites in Japanese workers

A recent development in analytical chemistry has enabled us to monitor systemic organophosphorus insecticide (OP) exposure at individual levels. At present, however, limited data are currently available on urinary OP metabolite levels worldwide. The purpose of this study was to assess urinary dialkylphosphate (DAP) concentrations in Japanese workers. Urine samples were collected in both summer and winter from 339 Japanese adults who worked as food distributors (FDs, n = 164), apple farmers (AFs, n = 147) and pest control operators (PCOs, n = 28). DAPs were measured by gas chromatography-mass spectrometry after derivatization with pentafluorobenzylbromide. Dimethylphosphate (DMP), diethylphosphate (DEP), dimethylthiophosphate (DMTP) and diethylthiophosphate (DETP) were detected in the urine of over 87% of the studied populations in both seasons. The geometric mean values of total DAPs (nmol g⁻¹ creatinine), DMP, DMTP, DEP and DETP (μg g⁻¹ creatinine) in summer and winter were 106.7 and 98.3, 7.0 and 3.8, 3.4 and 4.5, 0.8 and 1.5, and 0.3 and 0.2 for the FDs, 440.8 and 197.7, 33.1 and 10.8, 10.1 and 5.8, 4.2 and 4.7 and 1.6 and 0.8 for the AFs, and 473.4 and 284.6, 28.9 and 22.2, 17.6 and 4.6, 3.5 and 4.4, and 0.5 and 0.6 for the PCOs, respectively, thereby revealing significantly higher concentrations in AFs and PCOs groups than in the FDs in both seasons except for winter DMTP. These DAP concentrations were approximately the same or at lower levels compared with those reported in the previous literature. This is one of the first studies to demonstrate urinary DAP concentrations in Japanese adults.     

Thermal analysis of polyethylene glycol: evolved gas analysis with ion attachment mass spectrometry

The thermal decomposition of polyethylene glycol was investigated by using a technique combining evolved gas analysis (time-resolved pyrolysis) with ion-attachment mass spectrometry. This technique allows the detection of intact pyrolysis products and, therefore, offers the opportunity for direct real-time monitoring of thermal by-products. Unstable products can thus be detected; for instance, many highly reactive organic peroxides, such as CH₃OOH and HOCH₂OOH, were found in this study. Classification analysis revealed 10 major compositional formulas among the product species: C_nH_2n+2O, C_nH_2n+2O₂, C_nH_2n+2O₃, C_nH_2n+2O₄, C_nH_2n+2O₅, C_nH_2n+2O₆, C_nH_2n+2O₇, C_nH_2nO, C_nH_2nO₂, and HO(CH₂CH₂O)_nH ethylene glycol oligomers. The Li⁺ ion adduct mass spectra showed a characteristic profile in terms of both the appearance of unique components and the distribution of pyrolysis products. Among the products of the thermal decomposition of PEG, formaldehyde (HCHO) and organic peroxides were particularly interesting. Formaldehyde, one of the 10 most abundant products, is a known human carcinogen. The detection of peroxides suggests that they may form during the incineration of PEG, which may have important environmental implications. The existence of peroxide products may have implications for chemical evolution in incinerator systems.     

Polychlorinated biphenyl (118) activates osteoclasts and induces bone resorption in goldfish

To analyze the effect of polychlorinated biphenyl (PCB) 118 on fish bone metabolism, we examined osteoclastic and osteoblastic activities, as well as plasma calcium levels, in the scales of PCB (118)-injected goldfish. In addition, effect of PCB (118) on osteoclasts and osteoblasts was investigated in vitro. Immature goldfish, in which the endogenous effects of sex steroids are negligible, were used. PCB (118) was solubilized in dimethyl sulfoxide at a concentration of 10 ppm. At 1 and 2 days after PCB (118) injection (100 ng/g body weight), both osteoclastic and osteoblastic activities, and plasma calcium levels were measured. In an in vitro study, then, both osteoclastic and osteoblastic activities as well as each marker mRNA expression were examined. At 2 days, scale osteoclastic activity in PCB (118)-injected goldfish increased significantly, while osteoblastic activity did not change significantly. Corresponding to osteoclastic activity, plasma calcium levels increased significantly at 2 days after PCB (118) administration. Osteoclastic activation also occurred in the marker enzyme activities and mRNA expressions in vitro. Thus, we conclude that PCB (118) disrupts bone metabolism in goldfish both in vivo and in vitro experiments.