Estrogen equivalent concentration of 13 branched para-nonylphenols in three technical mixtures by isomer-specific determination using their synthetic standards in SIM mode with GC-MS and two new diasteromeric isomers

Thirteen isomers of branched para-nonylphenols (para-NP) in three technical mixtures were isomer-specifically determined using their synthesized standards by SIM of structurally specific ions, m/z 135, 149 or 163 with GC–MS. Of the 13 isomers, four isomers, 4-(2,4-dimethylheptan-4-yl)phenol, 4-(4-methyloctan-4-yl)phenol, 4-(3-ethyl-2-methylhexan-2-yl)phenol (3E22NP) and 4-(2,3-dimethylheptan-2-yl)phenol synthesized for their determinations were first used as standard substances. The 13 isomers in the technical mixtures individually occurred at mass percent portion of more than 2%. The total mass percent portions in the mixtures from Tokyo Chemical Industry (TCI), Aldrich, and Fluka covered with 89 ± 2%, 75 ± 4% and 77 ± 2%, respectively. The abundance of 4-(3,6-dimethylheptan-3-yl)phenol in the three mixtures was the largest with 11.1 ± 2% to 9.9 ± 0.3%, while that of 4-(2-methyloctan-2-yl)phenol was the smallest with 2.9 ± 0.3% to 3.0 ± 0.2%. Additionally, structures of four new isomers of more than 1% portion present in a technical mixture were elucidated as two pairs of diastereomeric isomers: two types of 4-(3,4-dimethylheptan-4-yl)phenol (344NP) and those of 4-(3,4-dimethylheptan-3-yl)phenol (343NP). By estrogenic assay of 13 isomers with yeast estrogen screen system, the activity of 3E22NP was the highest, while that of 4-(3-methyloctan-3-yl)phenol was the least. Their relative activities to that of 3E22NP were individually calculated. Estrogenic equivalent concentrations of the three technical mixtures were predictively evaluated. The ratio of the EEC to the conventional concentration, total mass percent portions of the 13 isomers in technical mixtures were 0.208 for TCI, 0.206 for Aldrich and 0.205 for Fluka. The predicted estrogenic activity of measured concentration of para-NP in technical mixtures was approximately 5-fold greater than the measured estrogen agonist activity.     

Development and application of kinetic model on biological anoxic/aerobic filter

An up-flow biological anoxic filter (BANF) has been developed to achieve high removal performance of suspended solids and BOD removal as well as nitrogen. With a view to understand treatment mechanisms, we developed a filtration model that incorporates filtration, deposit scoring and biological reactions simultaneously. The biological reactions consist of four types of reaction; dissolution of organic particles; utilization of dissolved organic matter; denitrification; and self-degradation of bacteria. Whereas the reactor is generally assumed to be a plug flow reactor in the filtration model, it is assumed a continuous-flow stirred tank reactor (CSTR) in the model of biological reactions. The hydrodynamics is supposed that the filter bottom (the portion sludge settled) is a CSTR and the filter bed (the portion filled with filter media) consists of number of CSTR of equal size arranged in series. The model obtained in this study was verified and simulated using experimental results taken from a pilot-scale plant and predicted the experimental data well, applying to design and operate BANF.     

Relationship of PCDD/Fs congener profiles between beef and raw milk in South Korea

The relationship between profiles of residual PCDD/Fs in beef and raw milk was examined by measuring concentrations and detected frequencies. Unrelated samples of beef and raw milk were collected from nine regions in South Korea. Congener-specific profiles of PCDD/Fs in beef and raw milk were very similar. PCDFs, particularly 2,3,4,7,8-PeCDF, 1,2,3,4,7,8-HxCDF, 1,2,3,6,7,8-HxCDF, and 2,3,4,6,7,8-HxCDF, were dominant congeners in both beef and raw milk suggesting that sources of contamination may not significantly differ nationwide. The profiles of PCDD/Fs in domestic beef and raw milk in this study were closer to the profiles of emission from metal industries although Korea imports over 75% of feedingstuffs. The ratios of PCDF/PCDD in TEQ concentration were more than 5 and 15 in beef and raw milk, respectively. The mean concentrations of PCDD/Fs in 60 samples of beef and 60 samples of raw milk were 0.80 pg WHO-TEQ/g fat and 0.65 pg WHO-TEQ/g fat, respectively. The residual profiles of PCDD/Fs in raw milk resembled that in beef although the congener profiles might change throughout the food chain. This indicated that monitoring of dioxins in milk could provide information for contamination of milk itself or other associated food.     

Oxidation of elemental mercury using atmospheric pressure non-thermal plasma

The oxidation of gas phase elemental mercury (Hg0) by atmospheric pressure non-thermal plasma has been investigated at room temperature, employing both dielectric barrier discharge (DBD) of the gas mixture of Hg0 and injection of ozone (O3) into the gas mixture of Hg0. Results have shown that the oxidative efficiencies of Hg0 by DBD and the injection of O3 are 59% and 93%, respectively, with energy consumption of 23.7 J L(-1). This combined approach has indicated that O3 plays a decisive role in the oxidation of gas phase Hg0. Also the oxidation of Hg0 by injecting O3 into the gas mixture of Hg0 proceeds with better efficiency than DBD of the gas mixture of Hg0. These results have been explained by the incorporation of the competitive reaction pathways between the formation of HgO by O3 and the decomposition of HgO back to Hg0 in the plasma environment.     

Seasonal variations of monoterpene emissions from Pinus densiflora in East Asia

The emission rates and compositions of monoterpene from Pinus densiflora were investigated in the Gumsung (GM) and Worak (WM) mountains. The standard emission rates (ERs: ERs is the monoterpene emission rate at standard temperature, 30 degrees C) from P. densiflora ranged from 0.817 to 1.704 (mugC/gdw-h). The ERs and beta-values of total monoterpene were measured at the two study sites (GM and WM). In the spring and summer, the ERs were the highest, while relatively low values (<0.058mugC/gdw-h) were measured in the autumn and winter. In GM and WM sites the beta-value obtained for the different seasons ranged from 0.047 to 0.179, with an average of 0.09. The major monoterpene compounds from P. densiflora were alpha-pinene, myrcene, beta-phellandrene, d-limonene and alpha-terpinene. The fractional compositions of individual monoterpene compounds were significantly different between the two test sites in the summer and winter. The ERs of the older group (31-40 years) were higher than those in the younger group (21-30 years). However, the monoterpene compositions were similar between the two age groups.     

Ozonation of pentachlorophenol in unsaturated soils

A heterogeneous model was developed to describe interactions between ozone and hydrophobic organic compounds, exemplified by pentachlorophenol, in highly gas-saturated vadose zones where water moisture was limited to a thin film on soil particle surfaces. The soil was assumed to be free of soil organic matter. The model included a set of transient equations considering diffusion with simultaneous chemical reaction and hydrophobic partitioning. From dimensionless analysis, it was found that the film concentrations of ozone and the hydrophobic organic component were dependent on the Damk?hler numbers. Effects of Damk?hler numbers on the film profiles of components were examined. With the interfacial flux of ozone calculated from film profiles, dimensionless governing equations of ozone transport and contaminant removal across an experimental column were established. These equations were dependent on the Stanton number. One-dimensional column experiments were conducted to test the model. The optimal time for flow rate adjustment during the process was approximated. Finally, effects of ozone velocity and ozone gas concentration on the Stanton number were evaluated.     

Influence of calcium chloride on the thermal behavior of heavy and alkali metals in sewage sludge incineration

In order to separate and reuse heavy and alkali metals from flue gas during sewage sludge incineration, experiments were carried out in a pilot incinerator. The experimental results show that most of the heavy and alkali metals form condensed phase at temperature above 600 degrees C. With the addition of 5% calcium chloride into sewage sludge, the gas/solid transformation temperature of part of the metals (As, Cu, Mg and Na) is evidently decreased due to the formation of chloride, while calcium chloride seems to have no significant influence on Zn and P. Moreover, the mass fractions of some heavy and alkali metals in the collected fly ash are relatively high. For example, the mass fractions for Pb and Cu in the fly ash collected by the filter are 1.19% and 19.7%, respectively, which are well above those in lead and copper ores. In the case of adding 5% calcium chloride, the heavy and alkali metals can be divided into three groups based on their conversion temperature: Group A that includes Na, Zn, K, Mg and P, which are converted into condensed phase above 600 degrees C; Group B that includes Pb and Cu which solidify when the temperature is above 400 degrees C; and Group C that includes As, whose condensation temperature is as low as 300 degrees C.     

Bioleaching of metals from spent lithium ion secondary batteries using Acidithiobacillus ferrooxidans

Bioleaching of spent lithium ion secondary batteries, containing LiCoO2, was attempted in this investigation. The present study was carried out using chemolithotrophic and acidophilic bacteria Acidithiobacillus ferrooxidans, which utilized elemental sulfur and ferrous ion as the energy source to produce metabolites like sulfuric acids and ferric ion in the leaching medium. These metabolites helped dissolve metals from spent batteries. Bio-dissolution of cobalt was found to be faster than lithium. The effect of initial Fe(II) concentration, initial pH and solid/liquid (w/v) ratio during bioleaching of spent battery wastes were studied in detail. Higher Fe(II) concentration showed a decrease in dissolution due co-precipitation of Fe(III) with the metals in the residues. The higher solid/liquid ratio (w/v) also affected the metal dissolution by arresting the cell growth due to increased metal concentration in the waste sample. An EDXA mapping was carried out to compare the solubility of both cobalt and lithium, and the slow dissolution rate was clearly found from the figures.     

Durability of recycled aggregate concrete using pozzolanic materials

In this study, pulverized fuel ash (PFA) and ground granulated blast furnace slag (GGBS) were used to compensate for the loss of strength and durability of concrete containing recycled aggregate. As a result, 30% PFA and 65% GGBS concretes increased the compressive strength to the level of control specimens cast with natural granite gravel, but the tensile strength was still lowered at 28 days. Replacement with PFA and GGBS was effective in raising the resistance to chloride ion penetrability into the concrete body, measured by a rapid chloride ion penetration test based on ASTM C 1202-91. It was found that the corrosion rate of 30% PFA and 65% GGBS concretes was kept at a lower level after corrosion initiation, compared to the control specimens, presumably due to the restriction of oxygen and water access. However, it was less effective in increasing the chloride threshold level for steel corrosion. Hence, it is expected that the corrosion time for 30% PFA and 65% GGBS concrete containing recycled aggregate mostly equates to the corrosion-free life of control specimens.