Production and characterization of KOH-activated carbon derived from polychlorinated biphenyl residue generated by the sodium dispersion process

Polychlorinated biphenyl (PCB) residues from the sodium dispersion (SD) process were employed as the raw materials for the production of activated carbon using KOH activation. The pore properties, such as the specific surface area and pore size distribution, were characterized using the Barrett–Joyner–Halenda method and the Horvath–Kawazoe method based on the N₂ adsorption isotherm at 77 K. The activated carbon produced showed similar adsorption capacities and specific surface areas to the commercially available product. The effects of the activation conditions on the porosity of the activated carbon produced were studied. The most significant factor affecting the specific surface proved to be the activation temperature. The activated carbon produced from PCB residues from the high-temperature (423–443 K) SD process had a binary pore size distribution well developed in the 4 nm region and in the micropore region. The pore structure of the carbon produced from PCB residues from the low-temperature (333–393 K) SD process had a wide range of micropores and mesopores.     

Measurement of total OH reactivity by laser-induced pump and probe technique—comprehensive observations in the urban atmosphere of Tokyo

Total OH reactivity was observed by use of the laser-induced pump and probe technique, and the urban air quality in Tokyo was diagnosed comprehensively. The concentrations of NO_x, CO, O₃, non-methane hydrocarbons (NMHCs) and oxygenated volatile organic compounds (OVOCs) were observed simultaneously. The observations were conducted in July and August 2003, and in January, February, May, and November 2004. Generally, the observed OH reactivity was higher than the calculated values derived using the observed concentrations of the trace species. The differences between the observed and calculated values in summer, spring, and autumn were approximately 30%. However, the difference in winter was smaller than those in the other seasons. In addition, while the differences observed in summer, spring, and autumn correlated with the total reactivity of the OVOCs (Σ_i k_OVOCi[OVOC_i](s⁻¹), k_i is rate constant of its compounds with OH), the correlations were not confirmed in the case of winter because atmospheric oxidation was less active and OVOCs levels were low in winter. These results suggest that the secondary products of the photochemical reactions in the atmosphere would be a missing sink for the OH loss process in the urban area.     

Contamination status and accumulation features of persistent organochlorines in pet dogs and cats from Japan

Concentrations of persistent organochlorines (OCs) such as polychlorinated dibenzo-p-dioxin (PCDDs), dibenzofurans (PCDFs), biphenyls, dichlorodiphenyltrichloroethane and their metabolites (DDTs), hexachlorocyclohexane isomers, hexachlorobenzene, and chlordane compounds were determined in genital organs of pet dogs and cats and pet foods from Japan. Levels of OCs in dogs were relatively lower than those in cats, while residue levels in their diets were almost similar, implying that accumulation and elimination mechanisms of these contaminants are different between dogs and cats. When bioconcentration factors (BCFs) were estimated from concentrations of OCs in dogs, cats, and their diets, BCFs of all the OCs except PCDD/DFs exceeded 1.0 in cats. On the other hand, in all the dogs, BCFs of DDTs were below 1.0, suggesting that dogs do not bioconcentrate DDTs. Furthermore, BCFs of all the OCs except PCDD/DFs in dogs were notably lower than those in cats, suggesting that dogs have higher metabolic and elimination capacity for these contaminants than cats. When residue levels of OCs in livers, adipose tissue, and genital organs of two pet dogs were examined, hepatic sequestration of PCDD/DFs and oxychlordane was observed.     

Toxicity evaluation of new antifouling compounds using suspension-cultured fish cells

A simple, rapid toxicity test was developed using the suspension-cultured fish cell line CHSE-sp derived from chinook salmon Oncorhynchus tshawytscha embryos in order to assess the toxicity of new marine antifouling compounds. The compounds tested were copper pyrithione, Diuron, Irgarol 1051, KH101, Sea-Nine 211, and zinc pyrithione, all of which have been nominated in Japan as possible replacements for organotin compounds. The in vitro acute toxicity (24-h EC50) of the six compounds to these fish cells was evaluated using the dye Alamar Blue to determine cell viability, and then correlated with the results of in vivo chronic toxicities (28-day LC50) to juvenile rainbow trout Oncorhynchus mykiss. The suspension-cultured fish cells were found to be suitable for the screening of such chemicals before performing an in vivo test. The toxicities of the test compounds obtained from both tests, shown in decreasing order, were as follows: copper pyrithione > zinc pyrithione > KH101 > or = Sea-Nine 211 > Diuron > Irgarol 1051. The herbicides Diuron and Irgarol 1051 showed the least toxicity, while the pyrithiones had the greatest toxicity.     

Congener-specific analysis of polychlorinated biphenyl in human blood from Japanese

Polychlorinated biphenyl (PCB) congeners were analyzed by high resolution gas chromatography/high resolution mass spectrometry (HRGC/HRMS) of whole blood samples taken from 24 healthy adult Japanese volunteers (12 males and 12 females; age range 25–46 years). On average, 95 PCB congeners were detected in whole blood samples. The mean of total PCB concentration in whole blood was 771.9 pg g^–1 whole blood (139.6 ng per g-lipid). Congener-specific analysis identified the predominant PCB congeners as #153 (22.2), #180 (11.6), #138 (8.4), #182/187 (6.6), #118 (5.6), #163/164 (5.0), #99 (3.9), #74 (3.6), #146 (3.3), #170 (3.0) and #156 (2.2), representing 75.6 of all PCBs detected in the human blood samples. Among the predominant PCB congeners, #153, #180, #138, #187 #118, #99 and #74 had chlorine as the substituent at the 2-, 4- and 5- positions of the phenyl-ring. In human blood in Japanese individuals, it is assumed that these congeners would be characteristic of the entire population, based on the relation between PCB ingestion and metabolism. Measuring 209 PCB congeners has the advantage of providing detailed information regarding the congener distribution within the blood samples, which can be compared to congener patterns in other matrices. Congener-specific analysis of 209 PCB congeners is especially useful in evaluating human exposure to PCBs.     

Improved quartz furnace method for chlorine and sulfur determination in municipal solid waste

 A method of determining the chlorine (Cl) and sulfur (S) in municipal solid waste (MSW) was studied. The quartz furnace method was improved in two ways: recovery from ash by hot extraction with dilute nitric acid, and avoidance of the volatilization of alkali (earth) metal chlorides by setting the sample combustion temperature at 600°C. In a comparison with the bomb method, using nine sets of kitchen garbage and waste plastics, the bomb method yielded a 15%–25% lower value than the improved quartz furnace method. Combustion in the bomb was frequently incomplete, resulting in recovery losses of Cl and S. The average kitchen garbage involved 5.2 mg Cl/g, of which at least 24.1% would be converted to HCl. Plastics contained 23 mg Cl/g generating 88.1% HCl on average. In the same way, kitchen garbage contained 3.0 mg S/g, generating 52.3% SO _x , whereas plastics contained 1.1 mg S/g with 55.1% SO _x formation. Received: March 20, 2002 / Accepted: October 13, 2002     

Chlorine promotes antimony volatilization in municipal waste incineration

Antimony volatilization in municipal waste incineration was studied. Two municipal waste samples and antimony(III) oxide (Sb₄O₆) were heated to 500°C and 700°C in an air stream in a quartz furnace. The volatilization of Sb₄O₆ occurred more at 700°C that at 500°C. Conversely, antimony volatilization form municipal waste was stronger at 500°C than at 700°C. This implies that antimony from municipal waste is volatilized as chloride instead of oxide. The chlorine sources for antimony chlorination, a gas-phase reaction involving hydrochloric acid and a solid-phase reaction of inorganic chlorine, e.g., CaCl₂, were compared. Only the solid-phase reaction could offer enough active chlorine to induce chlorination of antimony oxide. Received: July 2, 1998 / Accepted: January 28, 1999     

Online measurements of low-volatile organic chlorine for dioxin monitoring at municipal waste incinerators

In this study, an automatic sampling device and an analysis device have been developed for the measurement of low-volatile organic chlorine (LVOCl) in flue gas. The concentrations of dioxins (polychlorinated dibenzo-p-dioxins, polychlorinated dibenzofurans, and dioxin-like polychlorinated biphenyls) have been estimated by online measurements of LVOCl at a municipal solid waste incinerator (MSWI) using these devices. The LVOCl concentration at the outlet of the selective catalyst reactor (SCR) of the MSWI increased momentarily up to 95 μg Cl m⁻³ during the startup period of the MSWI; subsequently, it gradually decreased to less than 1.0 μg Cl m⁻³ after 50 h from the start of waste feeding. The concentration of toxic equivalent quantity (TEQ)-Dioxins at the SCR outlet had a linear positive relationship with the LVOCl concentrations. Moreover, the level of TEQ-Dioxins concentration can be estimated by using this relationship with LVOCl. From our results, since the LVOCl concentrations in a flue gas can thus be automatically analyzed every hour by online measurements, the operators of an MSWI would be able to monitor approximate TEQ-Dioxin emissions on a daily basis.     

Nervous system disruption and concomitant behavioral abnormality in early hatched pufferfish larvae exposed to heavy oil

BACKGROUND AND OBJECTIVE: Spills of heavy oil (HO) over the oceans have been proven to have an adverse effect on marine life. It has been hypothesized that exposure of early larvae of sinking eggs to HO leads largely to normal morphology, whereas abnormal organization of the developing neural scaffold is likely to be found. HO-induced disruption of the nervous system, which controls animal behavior, may in turn cause abnormalities in the swimming behavior of hatched larvae. To clarify the toxicological effects of HO, we performed exposure experiments and morphological and behavioral analyses in pufferfish (Takifugu rubripes) larvae. EXPERIMENTAL PROCEDURE: Fertilized eggs of pufferfish were exposed to 50?mg/L of HO for 8?days and transferred to fresh seawater before hatching. The hatched larvae were observed for their swimming behavior, morphological appearance, and construction of muscles and nervous system. RESULTS AND DISCUSSION: In HO-exposed larvae, we did not detect any anomaly of body morphology. However, they showed an abnormal swimming pattern and disorganized midbrain, a higher center controlling movement. Our results suggest that HO-exposed fishes suffer developmental disorder of the brain that triggers an abnormal swimming behavior and that HO may be selectively toxic to the brain and cause physical disability throughout the life span of these fishes.     

Comparative study of microbial dechlorination of chlorinated ethenes in an aquifer and a clayey aquitard

In order to determine whether natural attenuation of chlorinated ethenes by microbial activity occurs in aquitards, sediments at a site contaminated with tetrachloroethene were vertically studied by drilling. The distribution of microbes (Dehalococcoides group and anaerobic hydrogen producers) and the ability of the sediments to sustain microbial dechlorination were determined in an aquitard as well as in an aquifer. Close-spaced sampling revealed the existence of large populations of Dehalococcoides and H(2)-producing bacteria, especially in the organic-rich clayey aquitard rather than in the aquifer. The vinyl chloride reductase gene was also detected in the clay layer. Furthermore, incubation experiments indicated that the clay sediment could sustain transformations of tetrachloroethene at least to vinyl chloride. In contrast, no significant transformation was observed in the aquifer sand. Our results indicate that dechlorination of tetrachloroethene by bacteria can take place in an organic-rich clayey aquitard, and that organic-rich clay may also be important in the natural attenuation in an adjacent aquifer, possibly supplying a carbon source or an electron donor.