Distribution behavior of pyrene to adsorbed humic acids on kaolin

The distribution behavior of pyrene on humic acid (HA)-kaolin complexes, prepared by adsorbing HA on kaolin, was investigated by batch experiments. The distribution coefficient (Kd) of pyrene on the HA-kaolin complex increased with the fraction (f(oc)) of organic carbon adsorbed to the surface of the kaolin. This can be attributed to hydrophobic interactions between pyrene and the adsorbed HAs. The effects of adsorbed HAs were quantitatively evaluated by calculating the distribution coefficient (K(oc)) and affinity constant (K(oc)ads) for pyrene to the adsorbed HAs. A fluorescence quenching method was employed to determine the affinity constant (K(oc)aq) of pyrene to HAs dissolved in an aqueous solution. When the K(oc) values were compared with the K(oc)aq values, the K(oc) values were found to be 4 to 11 times larger than the K(oc)aq values. On the other hand, the K(oc)ads values were 4 to 9 times larger than the K(oc)aq values. These indicate that the affinity for pyrene is enhanced by the adsorption of HAs to kaolin. In addition, the K(oc) values increased with increasing average molecular weights of the HAs. These results demonstrate that HAs, when they are adsorbed to clay minerals, play an important role in the deposition of polycyclic aromatic hydrocarbons (PAHs) in a soil environment.     

Use of additives to enhance the removal of phenols from water treated with horseradish and hydrogen peroxide

Use of additives, such as polyethylene glycol (PEG), selected surfactants, chitosan gel, or activated carbon, has been shown to enhance enzymatic treatment of water polluted with organic compounds. In this study, additives were used to facilitate the removal of 2,4-dichlorophenol (2,4-DCP) from water using minced horseradish (Armoracia rusticana P. Gaertn. et al.) as a carrier of peroxidase activity. The specific objectives of the study were to (i) enhance the pollutant removal activity of minced horseradish by the addition of PEG and other additives (e.g., Tween 20, Triton X-100, and rhamnolipid); (ii) eliminate colored reaction products by the addition of chitosan; and (iii) eliminate color by amending treated water with activated carbon. The disappearance of 2,4-DCP in horseradish-treated water samples amended with PEG or various surfactants (75-90%) was greatly increased over that observed in nonamended samples (29%). The effect of PEG depended on its average molecular weight. As indicated by visible spectrophotometry, enclosing horseradish pieces between two sealed chitosan films completely eliminated colored reaction products; however, the decolorization was accompanied by a reduction in 2,4-DCP removal (from 95 to 60%). On the other hand, commercially available activated carbon completely removed colored reaction products from the treated water without reducing the removal efficiency. Based on the results obtained, it can be concluded that the use of additives may considerably improve the quality of wastewater treated by plant materials.     

Effects of dietary habits and CYP1A1 polymorphisms on blood dioxin concentrations in Japanese men

The major source of dioxin impurities in Japan in the past was agrochemical formulations; more recently, it has been exhaust from waste incinerators. To examine the environmental and genetic factors that influence blood dioxin concentration, we investigated the relationship among dioxin concentrations, dietary habits and cytochorome P450 1A1 (CYP1A1) polymorphisms (MspI type and Ile-Val type) in Japanese fishermen and farmers, including also a group of office workers as controls. The mean dioxin concentrations in the fishermen, the farmers and the controls were 161369, 79079 and 100500 pg/g fat, respectively. The elevated dioxin concentration with polychlorinated dibenzo-p-dioxins, polychlorinated dibenzofurans and coplanar-PCBs found in the fishermen may be due to the frequent consumption of fish; no such relationship was found both in the farmers and the controls. We found that the concentrations of congeners found as impurities in certain chemicals such as those previously used in agriculture showed no significant differences among the three groups; we consider it unlikely that the farmers would be directly exposed to dioxins from such chemicals. Thus, it is probable that the primary route of dioxin exposure in the Japanese population is through the food chain via fish consumption, regardless of occupation. No meaningful relationship between blood dioxin concentration and CYP1A1 polymorphisms was found in this study, although there was a significant difference between the concentration of total non-ortho-PCBs in genotypes A and B. Further studies on more subjects, including those of genotype C, are needed to confirm the relationship between blood dioxin concentrations and MspI polymorphisms.     

Temperature-Electrical Conductivity Relation of Water for Environmental Monitoring and Geophysical Data Inversion

Electrical conductivity (EC) is widely used for monitoring the mixing of fresh water and saline water, separating stream hydrographs, and geophysical mapping of contaminated groundwater. The measured EC values at various temperatures need to be reported as corresponding to a standard temperature because EC is dependent on temperature. An arbitrary constant is commonly used for temperature compensation assuming that EC-temperature relation is linear (for example 2% increase of EC per 1 degrees C). This paper examines the EC-temperature relation of natural waters having vastly different compositions and salinities. EC-temperature relation was slightly nonlinear in a temperature range 0-30 degrees C, but the linear equation approximated the relation reasonably well. The temperature compensation factor corresponding to 25 degrees C ranged between 0.0175 and 0.0198. When the mean value 0.0187 was used, the error of estimating EC at 25 degrees C from EC at 10 degrees C was less than about 2% for all samples tested. Temperature compensation factors vary substantially depending on the choice of standard temperature. Therefore, a care must be taken when standard temperatures different from 25 degrees C are used.     

Simultaneous determination of atmospheric sulfur and nitrogen oxides using a battery-operated portable filter pack sampler

We developed a method to analyze atmospheric SO(x) (particulate SO(4)(2-)+ gaseous SO(2)) and NO(x) (NO + NO(2)) simultaneously using a battery-operated portable filter pack sampler. NO(x) determination using a filter pack method is new. SO(x) and NO(x) were collected on a Na(2)CO(3) filter and PTIO (2-phenyl-4,4,5,5-tetramethylimidazoline-3-oxide-1-oxyl) + TEA (triethanolamine) filters (6 piled sheets), respectively. Aqueous solutions were then used to extract pollutants trapped by the filters and the resulting extracts were pre-cleaned (e.g. elimination of PTIO) and analyzed for sulfate and nitrite by ion chromatography. Recoveries of SO(2) and NO(x) from standard pollutant gases and consistency of the field data with those from other instrumental methods were examined to evaluate our method. SO(x) and NO(x) could be analyzed accurately with determination limits of 0.2 ppbv and 1.0 ppbv (as daily average concentrations), respectively. The sampler can determine SO(x) and NO(x) concentrations at mountainous or remote sites without needing an electric power supply.     

Degradation of a Terephthalate-containing Polyester by Thermophilic Actinomycetes and <Emphasis Type="Italic">Bacillus</Emphasis> Species Derived from Composts

We intended to find thermophilic degraders of terephthalate-containing Biomax^® films. Films in mesh bags were buried in composts (inside temperature: approximately 55–60 °C), resulting in the degradation of them in 2 weeks. Fluorescent microscopy of films recovered from composts showed that microorganisms gradually covered the surface of a film during composting. DGGE analysis of microorganisms on the composted film indicated the presence of Bacillus species as main species (approximately 80% of microbial flora) and actinomycetes (approximately 10–20%) as the second major flora. Isolation of Biomax^®-utilizing bacteria was focused on these two genera: two actinomycetes and one Bacillus species were isolated as pure best degraders from the composted polymer films, which were fragmented into small pieces. All the strains were thermophilic and identified, based on their 16S rDNA analyses. Degradation of polymer films was confirmed by (1) accelerated fragmentation of films in composts, compared with a control (no inoculum) and resultant decrease in molecular weights, (2) growth in a powdered Biomax^® medium, compared with a control without powdered Biomax^®, and (3) production of terephthalate in a powdered Biomax^® medium. In this way, we concluded that these bacteria were useful for degradation of thermostable Biomax^® products.     

Effect of ZnCl<Subscript>2</Subscript> impregnation ratio on pore structure of activated carbons prepared from cattle manure compost: application of N<Subscript>2</Subscript> adsorption-desorption isotherms

Activated carbons were prepared from cattle manure compost (CMC) by ZnCl₂ activation with various ZnCl₂/CMC mass ratios. Based on the N₂ adsorption-desorption isotherms, mathematical models including the Dubinin-Radushkevich (DR) equation, the α_s plot, and the Horvath-Kawazoe method were used to analyze the pore structural characteristics of the prepared activated carbons. It was found that for carbons possessing both micro-and mesopores, the DR method provided a more accurate estimation than the α_s method for the extent of microporosity. The effect of the ZnCl₂ impregnation ratio on the pore structure was discussed using the DR method. The results revealed that pore evolution involved three distinct regions with increases in the amount of impregnated ZnCl₂: raising the ZnCl₂/CMC mass ratio from 0.00 to 0.50 resulted in a 19-fold increase in micropore volume (V_me ^D) but caused no change in the mesopore volume (V_me ^D); increasing the ZnCl₂/CMC mass ratio from 0.50 to 1.00 led to an increment in V_mi ^D of about 50% and in V_me ^D of 170%; while raising the ratio from 1.50 to 2.50 caused a slight decrease in V_mi ^D but a 200% increment in the value of V_me ^D.     

Coagulation characteristics of humic acid modified with glucosamine or taurine

To suppress the coagulation of humic acid (HA) in aqueous solutions, HA was modified with hydrophilic amines, such as glucosamine or taurine. These amines were attached to carboxyl groups in HA via amide bond formation. The degree of modification (R(m)) was estimated to be 21-38%. Infrared spectra of the modified HAs were also consistent with the presence of amide bonds. Acid-base titration showed that the average acid-dissociation constant (pK(app)) of the HA samples was increased by the modification. The Ca(2+) binding capacity of HA decreased with an increase in R(m) value. Critical pH or Ca(2+) concentration, at which HA coagulation occurs, was increased as the result of the modification. These critical points for taurine-HA were higher than those for glucosamine-HA. This is mainly due to electrostatic repulsion by sulfonate groups in taurine. These results indicate that the coagulation of HA is suppressed by modifying the molecules with glucosamine or taurine.