A gas chromatography-mass spectrometric (GC/MS) method has been developed for determination of chloroethylene (CE) in exhaust gas. Exhaust gas was sampled at 2-5l/min into a polyethylene bag covered with aluminium film and a Tedlaru^® bag.
0.25ml volume of the sample was injected into capillary GC/MS by using a sample loop valve-system. The detection limits and the relative standard deviations of determined values were 0.27ppm and 5.77%, respectively. CE was stable for at least 7 days in both bags. This method was successfully applied to determine CE in exhaust gases from chemical plants.

View full abstract

Extractable organic halogens (EOX: Cl, Br and I) in soil and sediment samples collected in northern Poland were analysed by instrumental neutron activation technique. The concentrations of EOX were as follows; extractable organic chlorine (EOCl) > extractable organic bromine (EOBr) > extractable organic iodine (EOI) . Organohalogens, which are defined as EOX, were found to be widely distributed in soils and sediments of northern Poland. EOX concentrations in sediment samples were higher than those in soil samples.
Known organochlorine compounds in EOCl were quantified to reveal the content of unknown organochlorine compounds. The results showed that a large part of EOCl was occupied by unidentified compounds. A good statistical correlation was observed between the concentrations of PCBs and unknown EOCl, suggesting that most constituents of unknown fraction in EOCl have been originated from human activities and distributed as PCBs contamination.

View full abstract

The chlorination by-products from a chlorinated culture of Microcystis aeruginosa strain TAC51 were identified and their mutagenicities were studied. A hypochlorite solution was added to the culture of TAC51 until about 0.5 mg/l of free chlorine was detected, and the mixture was stood for 60 min at the room temperature. Low molecular weight organic chlorine compounds such as chloroform, bromodichloromethane, chloral hydrate, dichloroacetonitrile, formaldehyde and isopropyl sulfonyl chloride were detected in the chlorinated culture at, ag/l levels. An AED-GC analysis detected 55 peaks, and showed 7 chlorinated substances and 7 oxidized substances which were produced by chlorination of the culture. Twenty-two compounds, including seven aliphatic hydrocarbons (e.g., hexadecane, heptadecane, methyl heptadecanes, eicosane), five fatty acids (e.g., tetradecanoic acid, hexadecanoic acid) and phytol were identified or characterized to be present in the chlorinated culture. Mutagencity assays of the chlorinated culture using Salmonella typhimurium TA100 without S9 mix showed to be mutagenic with a dose response relationship from 10.6 to 42.4 ml /plate. The mutagenicity of TA100 without S9 mix obtained by strain TAC51 is similar to the mutagenicity of tap water supplied in Japan. We found that the culture containing metabolites from M. aeruginosa strain TAC51 produced oxidized and chlorinated substances and mutagenic substances by chlorination.

View full abstract

A high performance liquid chromatographic analysis for the simultaneous determination of ammonia, nitrite, nitrate and other anion compounds in the environmental samples has been developed.
The method is based on the separation of nitrite, nitrate and sulfate from cation using anion exchange column for ion chromatograph, and detection of ammonia by indophenol reaction.
In the flow pathway of HPLC carrier, anion compounds are detected by conductivity detector, and postcolumn derivatization using spectrophotometric detector at 640 nm of wave length was determined ammonia.
An ammonia can be detected selectivity in water at 0.01 ppm concentration.
It was appllied determining of chloride, nitrite, nitrate, sulfate and ammonia in the environmental water samples such as lake, river, wastewater plant and rain by this method.

View full abstract

Some of chlorinated o-benzoquinones (o-BQs) have been shown to be mutagenic in Ames Salmonella assays. However, no study has been reported on the quantitative estimate of such compounds in aqueous solution. These mutagenic chemicals present in chlorine-treated aqueous solutions of mono- and dihydric phenols were, therefore, quantitatively determined by GC-MS as their phenazine derivatives.
Chlorination of aqueous catechol solution was shown to produce a series of chlorinated compounds, including Chloro-o-BQs, and Chloro-hydroxy-o-BQ, in addition to o-BQ. No Chloro-o-BQs were found to be present in chlorine-treated resolcinol and hydroquinone solutions. After treatment with chlorine of aqueous chlorophenol solutions, dichloro-o-BQs were detected in these solutions. Production of chloro-o-BQs in water is dependent on the equivalents of chlorine per mole of compound, the reaction pH and the presence of lignin or humic acid. These results show that treatment with chlorine of water and wastewater contaminated with phenolic compounds leads to the production of mutagenic chlorinated o-BQs.

View full abstract

This study aiming at elucidating the photolysis pathways of PCBs by UV irradiation was designed to explore the photolytic characteristics of several PCBs including 2, 4, 4'-TriCB, 2, 2', 5-TriCB and 2, 2', 5, 5'-TetraCB in alkaline 2-propanol solution and to define their respective photolysis pathways. The results show that the chlorine atom at the ortho- position tends to be released more readily than those at the para- or at the meta- position during photochemical process and that the reductive dechlorination pathways in alkaline alcohol do not alter with the changes in UV wavelength and reaction solvents, whereas the PCB isomers are significantly affected by chlorine substitution position and greatly differ in their rates of photolysis.

View full abstract

In the current investigation of the environmental water pollution by chemical compounds, some kinds of pesticide were detected from well water located in golf links. Among the pesticides detected from well water, terbucarb (2, 6-ditert-butyl-p-tolyl methyl carbamate) was detected from 60% of the samples. To clarify the cause of high detection ratio of terbucarb, the behavior of 5 kinds of pesticide in some soils was examined using column system.
As a result, it was clarified that the mobility of terbucarb in fairway soil was almost same as that of simazine, but in masa (soil of weathered granite) the mobile velocity of terbucarb was faster than that of simazine. This seems to be the reason why terbucarb is frequently detected in the well water.

View full abstract

An analytical method of vinylchloride (VC) and chloroethane (CA), i. e., degradation products of tetrachloroethylene (PCE), trichloroethylene (TCE) and 1, 1, 1-trichloroethane (TCA) in groundwater, was studied using a headspace/gas chromatography mass spectrometry (HS/GC/MS)
In order to analyze VC and CA, the GC column oven was kept at an initial temperature of -20°C for 2min to separate VOC peak and methanol peak, then ramped at a rate of 10°C /min to 200°C. The mass spectra were measured in the mass range 35-200 amu to avoid background noise. VC and CA were detected in the groundwater contaminated by cis-1, 2-dichloroethylene (cis-1, 2-DCE) . VC was detected more frequently in shallower wells (6 samples) than in deeper wells (6 samples) .
In the case of soil core samples contaminated by PCE, concentration of PCE, TCE and cis-1, 2-DCE were higher in the clay layer and the silt layer than in the sand layer. PCE concentration in the upper clay layer was higher than in the lower silt layer, but cis-1, 2-DCE concentration was almost equal between the two layers. The behavior of cis-1, 2-DCE in soil was different from that of PCE.
The results suggested that cis-1, 2-DCE in the upper clay layer transfered easily to the lower silt layer than PCE, and that the biodegradation of PCE proceeded in subsurface soil including organic carbon.

View full abstract

It is well known that Salmonella typhimurium TA102 is a useful tester strain in detecting mutagenicity of chemicals which are not or weakly detected by the other tester strains in Ames test. However, this strain gives higher spontaneous revertant colonies, and somewhat large difference of mutagenicity among laboratories. As a part of studies in getting a reliable test protocol for this strain in preincubation method, we studied the effect of growth culture conditions on the mutagenicity of bleomycin and methyl methanesulfonate in the absence of S9 mix and 2-aminoanthracene in the presence of S9 mix.
Highest mutagenicity for these chemicals was observed in the test using 6 hour cultured strain, although 9-16 hour cultured strains have usually been used in Ames test. The mutagenicity was 4 and 12 times higher than those by 9 hour and 16 hour cultured strains for bleomycin, and 2 and 4 times higher than 9 hour and 16 hour cultured strains for methyl methanesulfonate. The mutagenicity of 2-aminoanthracene was nearly same with that by 9 hour cultured strain and slightly higher than that by 16 hour cultured strain. On 6 hour cultured strain, mutagenicity of bleomycin was affected by the interval from the end of growth culture to the beginning of the test, but mutagenicities of methyl methanesulfonate and 2-aminoanthracene were not.
These results suggest that mutagenicity test using Salmonella typhimurium TA102 should be done quickly using strain obtained by growing culture for 6 hour.

View full abstract

A headspace gas chromatography-mass spectrometric (GC/MS) method was developed to determine concentrations of 53 volatile organic compounds (VOCs) in river water. Effects of vial incubation temperature and incubation time on VOC concentrations (C_G's) in headspace phase in a vial were examined to increase C_G's. A 70°C incubation for 20 min was the recommended condition for the simultaneous determination of the 53 VOCs. C_G's were increased to 120 to 470% by addition of 3.6 g of sodium chloride to 12 ml of a water sample. Recoveries of the VOCs of this method were 90% to 113%. The minimum detectable concentrations ranged from 0.04μg·l^-1 to 0.17μg·l^-1.
This method was applied to the screening of VOCs in river water from 16 rivers in Niigata Prefecture. Benzene, sec-butylbenzene, ethylbenzene, isopropylbenzene, n-propylbenzene, styrene, toluene, 1, 2, 4- and 1, 3, 5-trimethylbenzenes, o-, m- and p-xylenes, 1, 1- and 1, 2-dichloroethanes, cis- and trans-1, 2-dichloroethenes, dichloromethane, 1, 2-dichloropropane, tetrachloroethene, 1, 1, 1- and 1, 1, 2-trichloroethanes, trichloroethene, trichloromethane, chlorobenzene, o-and p-chlorotoluene, and 1, 2-, 1, 3- and 1, 4-dichlorobenzenes were determined from some water samples. Moreover, extra-target VOCs, 2-chloro-1, 3-butadiene, methyl acetate, ethyl acetate and 4-methyl-2-pentanone were also detected.

View full abstract

A method for the analysis of 54 Volatile Organic Compounds (VOCs, EPA method 524.2) in Public water was developed based on a Headspace Cryofocus Gas Chromatography/Mass Spectrometry.
The method detection limits (MDL) ranged from 0.005 to 0.035 μg/l. Most of 54 VOCs's recoveries for river water were above 90%.
The EPICS procedure was employed to determine Henry's constants for 54 VOCs over a temperature range from 25.4 to 60°C, representing a range in dimensionless Henry's constants (Hc) of from 0.014 to 1.339.
The precision achievable with the EPICS procedure deteriorates markedly for compounds with very low Henry's constants (i. e., Hc<0.1) .
The effects of ionic strength on apparent Henry's constants were evaluated for 54 VOCs, with Na₂SO₄ concentration up to 2.82 mol/l . Salting-out coefficient (k) ranged from 0.097 to 0.216 l /mol at 60°C.

View full abstract

For accurate evaluation of human exposure to VOC in the environmental air, concentrations of 5 volatile chemicals (tetrachloroethylene; 1, 1, 1-trichloroethane; trichloroethylene; carbon tetrachloride; chloroform) were measured both in exhaled and inhaled airs by GC/ECD analysis. When a clean air chamber was used to lower VOC concentrations in inhaled air, higher concentrations of exhaled air were observed, suggesting that the desorption of these chemicals from human body occurred. Some technical difficulties encountered during the experiments were discussed.

View full abstract

1, 4-Dioxane has been frequently detected in river water, and particularly in ground water polluted by volatile halogenated hydrocarbons. However conventional determination method was not suitable for analyzing many samples due to the complexities and difficulties in extraction procedures. In this study, the application of solid phase extraction was investigated in order to simplify a preconcentration procedure. Water samples were passed through activated carbon catridge and styrene divinyl benzene polymer cartridge connected in a series, and 1, 4-dioxane on activated carbon cartridge was desorbed with lml of acetone. The desorbed solution was directly subjected to GC/MS without loss of 1, 4-dioxane during con-centration procedure, hence rapid and sensitive determination of 1, 4-dioxane in water sample became possible. Detection limit was 0.1 μg/l . This method was applied to the analysis of real samples, and the results were nd-16 μg/l for river samples from 10 sites in six rivers, 0.3-0.9 μg/l for coastal seawater, nd-79 μg/l for ground water and 0.2-1.5 μg/l for tap water from 6 Cities in Kanagawa Prefecture in Japan from 1995 to 1996. This method was useful to elucidate the sources and diffusion mechanism in an aquatic environment.

View full abstract