Removal of Linear and Branched p-Alkylphenols from Aqueous Solution by Combined Use of melB Tyrosinase and Chitosan Beads

In this study, melB tyrosinase was applied for enzymatic removal of linear and branched p-alkylphenols from aqueous solutions. First, systematic studies were carried out to estimate the effects of the process parameters such as the temperature, pH value, and enzyme dose on quinone conversion of p-cresol as a model phenol compound. A variety of p-alkylphenols were removed from aqueous solutions through the tyrosinase-catalyzed quinone conversion and subsequent nonenzymatic adsorption of quinone derivatives on chitosan beads at pH 6.0 and 30 °C under the optimum conditions determined for p-cresol. The % removal values of 98–100 were obtained for p-n-alkylphenols. Branched p-alkylphenols with a weak estrogenic activity containing 4-tert-butylphenol and 4-tert-pentylphenol, which underwent no quinone conversion by commercially available mushroom tyrosinase in the absence of H₂O₂, were also effectively removed by further increasing either the melB tyrosinase concentration or the amount of added chitosan beads. The present technique is much effective in the fact that a series of reactions rapidly progress under mild conditions and the chitosan beads can be readily separated from the reaction medium after the enzymatic treatment.     

α1-Microglobulin levels and correlation with cadmium and other metals in urine of non-smoking women among general populations in Japan

The present study was initiated to examine urinary α₁-microglobulin (α₁-MG-U) levels among non-smoking women in the general population in Japan. A previously established database on spot urine samples from adult woman volunteers in 10 non-polluted areas all over Japan was re-examined. The data examined were on α₁-MG-U, cadmium, calcium, magnesium and zinc levels in urine (Cd-U, Ca-U, Mg-U and Zn-U, respectively), urinary creatinine (CR or cr), urine specific gravity (SG or sg), smoking habits and age. Thus, 8975 never-smoking women were selected for statistical analyses. The grand geometric mean (GM) for α₁-MG-U among the population was 2.1?mg/L or 2.5?mg/g?cr, depending on the correction for urine density. It was 1.1?µg/L or 1.3?µg/g?cr for GM Cd-U. The inter-area difference in α₁-MG-U was <1.5?mg/g?cr or <0.7?mg/L; the area with the highest or lowest GM Cd-U was not always highest or lowest in GM α₁-MG-U. The correlation coefficient (0.53) between log?Cd-U and log?α₁-MG-U (both without urine density correction) became substantially smaller when the analyte levels were corrected for CR (0.25) or SG (0.26). In multiple regression analysis, the power of influence of the five independent variables (log?Cd-U, Ca-U, Mg-U, Zn-U and age) in combination was small (R ²?≦?0.13). In contrast, logistic regression analysis suggested that α₁-MG-U might be elevated as a function of an increase in Cd-U, depending on the cut-off values. Discussion was made on dose (Cd-U_cr) and response (α₁-MG-U_cr) relationship based on information available in literatures to show that the increment in α₁-MG-U_cr per Cd-U_cr was much greater when Cd-U_cr was large, e.g., in excess of 10?µg/g?cr.     

Effect of unburned carbon on lead, zinc, and copper recovery from molten fly ash by chloride-induced volatilization

The present work focuses on investigation of the effective recovery of heavy metals from molten fly ash by applying chloride-induced volatilization. In particular, the effect of unburned carbon on the chloride-induced volatilization of lead, zinc, and copper from model and real molten fly ashes was investigated in the temperature range 873–1173 K under a N₂ atmosphere. As a result, almost 100% of lead and a significant proportion of zinc were volatilized from the real molten fly ash samples at 1173 K. In contrast, for the model fly ash, volatilization ratios of lead and zinc at 1173 K were only 85% and 25%, respectively. Further, the results of X-ray diffraction analysis suggested that PbO in molten fly ash was converted either to Pb₂OCl₂ or Pb by respective chlorination and reduction reactions. Meanwhile ZnO and CuO in the molten fly ash were reduced to Zn and Cu by reaction with unburned carbon. Subsequently, Pb, Zn, and Pb₂OCl₂ were volatilized, but Cu remained in the solid residue. Finally, the volatilization ratio of zinc increased with the addition of carbon, and more than 98% of zinc was volatilized at 1173 K from a fly ash with a carbon content of 20%.     

Calculation of environmental concentration and comparison of output for existing chemicals using regional multimedia modeling

The environmental fate of 40 existing chemicals is discussed using the EUSES multimedia distribution and risk assessment model with site-specific parameter setting in an urban area of Japan including a highly industrial region. There has been a strong need to assess the environmental fate of a huge number of existing chemicals. Data on the emission amounts of chemicals are essential for such prediction, and PRTR surveys may yield this data. The study delivered the following results: (1) Volatile compounds with large amounts of emission showed higher predicted concentrations in air, and the concentrations of several compounds agreed well with averaged monitoring data within an order of magnitude. (2) A close relationship was found between the concentration of water and that of sediment, suggesting that the fate of chemicals in sediment essentially depended on the water environment. (3) A group of volatile solvents had high mass distribution ratio to air. Some compounds having high solubility in water were also included in that group due to the high ratio of air emission. Highly hydrophobic compounds with logK(OW) larger than 6.0 showed a high distribution ratio to soil and sediment. (4) Volatile compounds were mostly taken through air. The exposure through fish is a dominant pathway for highly hydrophobic compounds. (5) Exposure ratio could be gathered from physicochemical properties. The exposure from fish intake was roughly estimated by logK(OW), whereas exposure from air and water intake was difficult to estimate simply by vapor pressure and solubility in water, respectively.     

Emission and fate assessment of methyl tertiary butyl ether in the Boston area airshed using a simple multimedia box model: comparison with urban air measurements

Expected urban air concentrations of the gasoline additive methyl tertiary butyl ether (MTBE) were calculated using volatile emissions estimates and screening transport models, and these predictions were compared with Boston, MA, area urban air measurements. The total volatile flux of MTBE into the Boston primary metropolitan statistical area (PMSA) airshed was calculated based on estimated automobile nontailpipe emissions and the Universal Quasi-Chemical Functional-Group Activity Coefficient computed abundance of MTBE in gasoline vapor. The fate of MTBE in the Boston PMSA was assessed using both the European Union System for the Evaluation of Substances, which is a steady-state multimedia box model, and a simple airshed box model. Both models were parameterized based on the meteorological conditions observed during air sampling in the Boston area. Measured average urban air concentrations of 0.1 and 1 microg/m3 MTBE during February and September of 2000, respectively, were comparable to corresponding model predictions of 0.3 and 1 microg/m3 and could be essentially explained from estimated temperature-dependent volatile emissions rates, observed average wind speed (the airshed flushing rate), and reaction with ambient tropospheric hydroxyl radical (*OH), within model uncertainty. These findings support the proposition that one can estimate gasoline component source fluxes and use simple multimedia models to screen the potential impact of future proposed gasoline additives on urban airsheds.     

Formation characteristics of polychlorinated dibenzo-p-dioxins, polychlorinated dibenzofurans, and coplanar PCBs in fly ash from a gasification–melting process of municipal solid waste

PCDDs/DF and Co-PCB (dioxin) formations were studied with ash from a newly developed gasification and melting process for municipal solid waste. Ash samples were heated in a laboratory-scale fixed-bed reactor. Emphasis was placed on the effects of the type and composition of ash, temperatures, gas residence time, and gaseous organic precursors. Investigations using macroscopic and homologue distribution analyses led to the following conclusion. The ash from the gasification–melting process had the ability to generate dioxins in flue gas. A possible carbon source is unburned carbon in the ash samples, although this was very low (less than 0.01%). An experimental result that the level of dioxins generated from preheated fly ash obtained from a conventional incinerator was much lower than that from nonheated fly ash supported this conclusion. Dioxin concentrations obviously showed temperature dependence and peaked at 350°C. Dioxins formed in a gasification–melting process ash were readily desorbed from the surface, probably because of the low carbon content of the ash. There was no experimental evidence that gaseous organic precursors fed to the reactor generated dioxins. Therefore, an organic precursor was not essential for the formation of dioxins. A good linear relationship obtained between PCDDs/DFs and gas residence time also supported the assumption. Received: February 14, 2000 / Accepted: June 30, 2000     

Assessing the economic value of urban green spaces in Kuala Lumpur

Environmental Science and Pollution Research - This study assessed the economic value of public urban green spaces (UGSs) in Kuala Lumpur (KL) city by using the hedonic price method (HPM). It...     

Physicochemical properties of selected polybrominated diphenyl ethers and extension of the UNIFAC model to brominated aromatic compounds

The aqueous solubilities (S(w)) at various temperatures from 283 K to 308 K and 1-octanol/water partition coefficients (K(ow)) for four polybrominated diphenyl ethers (PBDEs: 4,4'-dibromodiphenyl ether (BDE-15), 2,2',4,4'-tetrabromodiphenyl ether (BDE-47), 2,2',4,4',5-pentabromodiphenyl ether (BDE-99), and 2,2',4,4',5,5'-hexabromodiphenyl ether (BDE-153)) were measured by the generator column method. The S(w) and K(ow) data revealed the effect of bromine substitution and basic structure on S(w) and K(ow). To estimate the infinite dilution activity coefficients (gamma(i)(w,infinity)) of the PBDEs in water from the S(w) data, enthalpies of fusion and melting points for those compounds were measured with a differential scanning calorimeter. Henry's Law constants (H(w)) of the PBDEs were derived from the determined gamma(i)(w,infinity) and literature vapor pressure data. Some physicochemical characteristics of PBDEs were also suggested by comparing the present property data with that of polychlorinated dibenzo-p-dioxins, brominated phenols and brominated benzenes in past studies. Furthermore, in order to represent different phase equilibria including solubility and partition equilibrium for other brominated aromatic compounds using the UNIFAC model, a pair of UNIFAC group interaction parameters between the bromine and water group were determined from the S(w) and K(ow) data of PBDEs and brominated benzenes. The ability of the determined parameters to represent both properties of brominated aromatics was evaluated.     

Characterization of semi-volatile organic compounds emitted during heating of nitrogen-containing plastics at low temperature

Because of recent volume increases, appropriate management of plastic recycling, which generates various organic compounds, is required to ensure the chemical safety of the processes. The processing temperature and resin type are the important factors determining both the efficiency of the processes and the emission of chemicals. Therefore, we studied the thermal degradation of various plastics at various temperatures from 70 to 300 °C under oxygen-present conditions to identify the semi-volatile organic compounds (SVOCs) emitted and to understand their thermal behaviors. The plastics examined were nitrogen-containing resins, such as polyamide 6, polyurethane, melamine formaldehyde, urea formaldehyde and acrylonitrile-butadiene-styrene. Major commodity plastics were also investigated for comparison. In total, more than 500 SVOCs were detected as emissions from plastics. While various nitrogen-containing SVOCs were detected from nitrogen-containing resins, the major commodity plastics released only these, which possibly were included as additives. These results indicate that the nitrogen atoms in the SVOCs emitted originated from the resins and additives, and not from ambient air at low temperature. As a result of the detection of raw materials, degradation chemicals and by-products of the polymers in the emissions, we found that the variation in chemical species is dependent on the resins. Additives were also emitted from all the resins, meaning that these chemicals were also released to the environment at the temperature examined. In most cases, the numbers and concentrations of SVOCs increased with increasing heating temperature. The variation of thermal behaviors of SVOCs was related to the origins and chemical species of SVOCs.     

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.