Yukikazu Hattori

A sensitive, selective and rapid analytical method was developed for the determination of 4, 6-dinitro-o-cresol (DNOC) and 2, 6-dinitro-p-cresol (DNPC) in environmental water samples by liquid chromatography/tandem mass spectrometry (LC/MS/MS). Trace amounts of DNOC and DNPC in water samples adjusted to pH3 were collected on an Autoprep PS-Liq@ cartridge (PS-Liq cartridge) at flow rate of a 50ml · min^-1 and then eluted with 5ml of acetonitrile. The targets were separated with a reversed-phase column (ODS-3, 2.1 mm x 150mm, and 5μm) and measured by mass spectrometry operated in the electrospray ionization (ESI)-negative mode. The method detection limit (MDL) was 0.24ng · l^-1 for DNOC and 0.49ng · l^-1 for DNPC. The method was then applied to the environmental water samples from Osaka Prefecture. The concentrations of DNOC were 2.1∼74ng · l^-1 and those of DNPC were n.d.∼43ng · l^-1.

Measurement of acrolein and other aldehydes in ambient air was carried out at the Research Institute of Environment, Agriculture, and Fisheries in Osaka city from May 11 to 19 in 2007. The aldehydes were collected as their derivatives of O-(4-cyanoethoxbenzyl) hydroxylamine (CNET), and determined by liquid chromatography/tandem-mass spectrometry (LC/MS/MS). The concentrations of acrolein, 0.04∼0.49μg/m³, showed the positive correlations with nitrogen monoxide (NO), nitrogen dioxide (NO₂), nitrogen oxides (NO_x), carbon monoxide (CO), and non-methane hydrocarbons (NMHC). On the other hand, it showed the negative correlation with oxidant (O_x). These results suggested that acrolein exhausted from motor vehicles, increased in the morning and midnight, and was easily decomposed under sunlight by photochemical reaction.<BR> Formaldehyde showed a different behavior from acrolein. It showed the positive correlation with oxidant (O_x) generated with the photochemical reaction, and thus increased in the daytime.

A sensitive and selective method was developed for the determination of acrolein in ambient air by using liquid chromatography/tandem-mass spectrometry (LC/MS/MS). Air was sampled by passing through an O-(4-cyano-2-ethoxbenzyl) hydroxylamine (CNET) cartridge for 2∼24 hrs at a constant flow rate (200 mL/min). The acrolein-CNET derivative eluted from the cartridge with acetonitrile was separated by a reversed phase liquid chromatography and determined by LC/MS/MS in turbo spray ionization (ESI) positive mode. The collection efficiency of acrolein on a CNET cartridge was more than 99 %. The method detection limit was 0.4 ng/m³ in case of sampling volume of 0.3 m³ and relative standard deviation of repeated analysis was 5.0 %. Recoveries of acrolein on CNET cartridges under the condition of the relative humidity of 30∼87 % at the temperature of 25∼35 °C were 82∼92 %. In a refrigerator, acrolein-CNET derivative was stable for about 5 days on the cartridge, and that in the solution eluted with acetonitrile was stable for one month.<BR>This method was applied to the determination of ambient acrolein concentration for every 2∼3 hrs during one day. The concentrations of acrolein observed were in the range of 69∼288 ng/m³.

Changes of water temperature in Lake Biwa and the atmospheric factors that can affect the water temperature were analyzed. The water temperatures of effluent from sewage plants were found to increase, but it did not affect the annual mean temperatures of the lake surface water. The change pattern of surface water temperatures in summer resembles the change pattern of the number of hot days with temperatures exceeding 25°C. On the other hand, the change pattern of the water temperatures in winter resembles the change pattern of the number of cold days with temperatures dropping below 0°C. These results show that the water temperatures of Lake Biwa conspicuously increased in the past 30 years, and it was caused mainly by increasing atmospheric temperatures. It is suggested that the increase in the annual mean temperature of the deep water is affected by the absence of a decrease in the water temperatures in winter, and the increase in the annual mean temperature of surface water is affected by the increase in the water temperatures in summer.

This study was carried out to clarify the influence of sewage effluent on the temperature of urban river water. This investigation focused on the river basin of the Yodo River. The annual mean water temperature of the river depended on the annual mean atmospheric temperatures at all monitoring points except the Katsura River (Miyamaebashi) located on the lower reaches of a large-scale sewage treatment plant. The annual mean water temperature of Katsura River (Miyamaebashi) was significantly higher than the annual mean atmospheric temperature and increased by approximately 1.2°C within the period from 1972 to 2001. The increase in the water temperature of the Katsura River (Miyamaebashi) was attributable almost entirely to effluent from the sewage treatment plant. Because the temperature of the effluent from the sewage treatment plant was higher than the river water temperature before the inflow of the effluent, Katsura River water warmed significantly following the inflow of the sewage effluent. Katsura River water temperature after the inflow of sewage effluent increased considerably within the period from 1970 to 2003. The influence of sewage effluent was remarkable in winter in comparison with summer. These results suggest that effluent from sewage treatment plants is one of the factors causing the increase in river water temperature.

Concentrations for polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/PCDFs), and Co-PCBs in river waters and sediments of Kanzaki rivers, in which environmental standards of water and sediment were exceeded, were investigated. Distributions of dioxin concentrations and variations of constituents from upstream to downstream were showed. In sampling point 3, dioxin concentration of water and sediment were high, it is showed that dioxin in sediment were raised up to water layer and then water concentration increased.<BR>Dioxin concentrations in river waters were highest in middle area of Kanzaki river and these concentration became decreased and stable as descending to downstream of the river.<BR>Dioxin concentration constituents in suspended at river waters in middle area of Kanzaki river (around point 3) were beyond 90 % and those in soluble of low chlorinated PCDD/PCDFs and Co-PCBs were about 20 %.<BR>Co-PCBs concentrations in sediment of downstream were higher than those of middle stream by 10 times. Dioxin concentrations in sediment were higher, where ignition loss, water content, and sulfide concentration were higher.

Distributions for polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/PCDFs), and Co-PCBs in river waters and sediments at 36 points in Osaka Prefecture were investigated. Total PCDD/PCDFs concentrations of waters were ranged in 0.076 1.8 pg-TEQ/l (0.50 pg-TEQ/l in average) . Those of sediments were ranged in 0.18-510 pg-TEQ/g (27 pg-TEQ/g in average) . The average constituent ratio of water concentration in TEQ were arranged in a magnitude of PCDDs>PCDFs>Co-PCBs for Yodo rivers and Sensyu rivers, and those were arranged in PCDFs>PCDDs>Co-PCBs for Kanzaki rivers, Neya rivers and Yamato rivers. The ratios in river sediments were in order of PCDDs>PCDFs>Co-PCBs for all of rivers except Sensyu rivers (PCDFs > PCDDs > Co-PCBs) .<BR>Homologue profiles for PCDD/PCDFs in water and sediment from all rivers were similar with each other. TeCDFs through OCDFs and TeCDDs homologues showed larger reagional variation than other homologues in both waters and sediments. Average constituent ratios of Co-PCBs congeners for river waters were in order of #118 (48%) >#105 (22%) >#77 (14%) > #156 (5.5%) and thus congener profiles were observed in all water regions. In addition, the similar profiles were recognized for river sediments.<BR>A principal analysis for PCDD/PCDFs constituent ratios of river waters, sediments, ambient airs (vapor-phase and paraticle-bound), exhaust gases from incinerators and agrochemicals such as PCP and CNP was perfomed. Component 1 was supposed from combustion for positive and from agrochemicals (PCP) for negative, showing to be 38 % in contribution percentage. Component 2 was from particulate matter of PCDD/PCDFs for positive and vapor phase of PCDD/PCDFs for negative, with a contribution of 27 %. Component 3 and component 4 showed contributions of 13 % and 12 %. and the cumulative value of components 1-4 was in 90 %.

Study on the determination of acrylamide in exhaust gas was conducted for two methods. In one method, acrylamide was collected by using Sep-Pak Plus PS-2 cartridge conditioned with methanol and was eluted with methanol. Propionamide was added to the eluate as an internal standard for capillary gas chromatography-mass spectrometry (GC/MS) and gas chromatography -flame thermoionic detection (GC/FTID) . In the other method, acrylamide was collected by bubbling the sample through 20me of water. After dibromination, extraction, dehydrobromination and addition of the internal standard, acrylamide was determined by GC/MS and GC/FTID. The detection limits, the relative standard deviations and the recoveries in the former method were 21.8μg/m³, 3.2-6.6%, 99.8%-102% in the GC/MS, and 89.0μg/m³, 5.3-9.0%, 99.9%-108% in the GC/FTID, respectively. Those in the latter method were 37.3μg/m³, 6.6-7.8%, 88.7%-97.6% in the GC/MS, and 63.7μg/m³, 3.7-9.1%, 79.6%-94.0% in the GC/FTID, respectively. The both methods were successfully applied to determine acrylamide in exhaust gas.

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.<BR>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.

A list of hazardous air pollutants has been newly assigned for emission regulation in amended ordinance of Osaka Prefectural Government.<BR>Measurement methods for listed pollutants in exhaust/flue gas have been developed/selected for the implementation of amended ordinance. Round robin tests for methods evaluation have been performed among many laboratories in Osaka. Most of the methods showed good recovery (higher than 80%) and precision (better than 20%) . After some revision/improvement, methods have been established, and manuals have been prepared.

A new method for the determination of ο-, m-, ρ-chloronitrobenzenes (CNBs) in exhaust gas was developed. The method was applicable to the analysis of CNBs in gas samples containing up to 30% of water. CNBs were collected with SEP PAK^®PS2 cartridge after conditioning with η-hexane. CNBs were eluted with n-hexane and determined by capillary gas chromatography-mass spectrometry (GC/MS) and gas chromatography using flame thermoionic detector (GC/FTID) .<BR>Detection limits, relative standard deviations and recoveries of CNBs were 28.1-46.2 μg/m³, 3.62-8.94%, 85.6.95.0% in GC/MS and 155-200 μg/m³, 3.9-25.4%, 78.7-98.6% in GC/FTID.

A method for the determination of N-methylaniline, N-ethylaniline, ο-anisidine and ρ-anisidine in exhaust gas has been studied. Those compounds were sampled with a SEP-PAK^®C₁₈impregnated with phosphoric acid. Trapped substance were eluted with ethanol, extracted with dichloromethane, transferred into η-hexane and determined by capillary gas chromatography/mass spectrometry (GC/MS) or flame thermoionic detector (GC/FTID) . The most suitable pH on extraction was about 12.0. When water content of exhaust gas is more than 3%, those compounds could be sampled with absorption bottle admitting 1% hydrochloric acid aqueous solution. Detection limits, relative standard deviation and recoveries of this method were 70.8-93.3μg /m³, 6.93-17.4%, 82.3-111% with GC/MS, 45.5-105μg/m³, 2.09-15.9%, 87.3-106% with GC/FTID respectively.

A method for the determination of LAS in environmental water and domestic waste water was developed. This method was not interfered by coexisting substances.<BR>Sample water was passed through SEP-PAK C18 cartridge. The cartridge was washed with methanol/0.1M NaCl (3 : 2) 4ml and distilled water, then LAS was eluted with methanol 4ml.This eluent was determined by high performance liquid chromatography with UV and fluorescence detectors.<BR>When the interfereing peaks were on the chromatogram yet, distilled water was added to the eluent. It was passed throgh SEP-PAK ACCELL QMA anion exchange cartridge again. The cartridge was washed with methanol/0.0025M sodium citrate (1 : 1, pH 5.5) 8ml. LAS was eluted with acetonitorile/0.5M NaCl (1 : 1) 5ml. Then, the eluent was determined with HPLC.<BR>The detection limit of total LAS concentration by the proposed method was 0.1μg·l^-1 when sample volume was 1 liter.<BR>This method was applied to the determinations of LAS concentration in influent and effluent from a domestic waste water treatment plant, river and sea water of Osaka Prefecture. The concentration of LAS in river and sea water ranged from 19 to 1, 400μg·l^-1, and from no detection to 7.2μg·l^-1, respectively.

Environmental fate in river and sea water was studied for 6 organic phosphate esters; tributyl phosphate (TBP), tris (butoxyethyl) phosphate (TBXP), trioctyl phosphate (TOP), tricresyl phosphate (TCP), triphenyl phosphate (TPP), and tris (dichloropropyl) phosphate (CRP). In the river waters, the degradation rates of TPP and TCP, both having phenyl ester groups were faster than those of other phosphate esters. The rates of the phosphate esters having liner alkyl ester groups such as TBP, TBXP, and TOP, were faster as the length of alkyl chain become shorter. The rate of CRP which has chlorine atoms was much slower. The decay characteristics in the polluted sea water was similar to that in the river water. Moreover, the degradation rates in the clean sea water were much slower.