Cases of dioxin pollution where the dioxin levels are over the environmental quality standard have been found in many places in Japan. For the establishment of their remediation plans, polluters should be identified and the source apportionments among polluters should to be carried out. In this paper, the authors applied Positive Matrix Factorization (PMF), one of new receptor models, to an actual river sediment pollution case and discussed the obtained results.
First, the authors mixed four known source profiles of dioxins by Monte Carlo simulation and produced pseudo environmental pollution data. Then PMF was applied to the dataset to see if the original source profiles could be extracted and also to see what kind of data transformation was appropriate to compare the source profiles extracted by PMF with the original source profiles. Then, PMF was applied to the actual dioxin pollution case in Furuayase River, Saitama Prefecture (Dataset: 40 congeners X200 samples). The results showed that 5 factors were contributing to the pollution. Those were identified as incineration, PCB formulation, chloronitrophen (CNP) and pentachlorophenol (PCP) derived dioxins in addition to one unknown source that had lower-chlorinated dibenzofurans in high concentration and dioxin-like PCBs in lower concentration as its characteristic congeners. The ratio of contributions from PCB formulation and from unknown source, however, were uniform for the highly contaminated area and varied for lower contaminated area, indicating that these two sources might have come from a same source in highly contaminated area.
The current study showed that PMF could be successfully applied to a river sediment dioxin pollution case, however, careful interpretation of PMF results was necessary.

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The content of hazardous substances restricted by the European Union directive on the restriction of the use of certain hazardous substances in electrical and electronic equipment 2002/95/EC (RoHS directive) in various consumer products including electrical and electronic equipments (EEE), household products, recycled products etc. were analyzed by using a handheld X-ray fluorescence (XRF) analyzer. Among 358 products investigated, one third failed RoHS compliance for Br when assuming all Br derived from polybrominated biphenyls and/or polybrominated diphenyl ethers (PBDEs), and all passed the RoHS threshold for Hg levels. About half of EEE examined contained more than 0.1 wt% of Br with the maximum concentration of approximately 20 wt% in rear casing of a computer monitor, indicating some sort of brominated flame retardants (BFRs) were intentionally added. From the XRF analysis of chassis of televisions (TV) and personal computer (PC) monitors, it was revealed that the percentage of products which exceeded Br thresholds in liquid crystal display TVs and PC monitors were less than those in cathode-ray tube TVs and PC monitors, suggesting the shift of type of flame retardants used over time. As use of PBDEs was restricted by RoHS directive in 2006, the consumer-electronics makers started using alternative flame retardants including novel non-PBDE BFRs and phosphorus flame retardants as well.

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Micelles, consisting of an anionic surfactant (sodium linear alkylbenzene sulfonate) and a fatty acid released from a fat (linoleic acid), were separated from an aqueous phase using the natural clay mineral, allophane, based on its ion exchange characteristics. The adsorption process of these compounds by the allophane was determined by a UV spectroscopic analysis and by adding anthracene to the micelles as a molecule probe. The fluorescence measurement of anthracene made the study of the adsorption process easier. Furthermore, the fluorescence spectroscopic analysis using pyrene as a polarity probe revealed that the pyrene molecules existed in the lipophilic alkyl moiety of the anionic surfactant and fatty acid adsorbed on the allophane. This result indicated that these compounds were effectively adsorbed on the allophane, thus keeping their micelle form stable.

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Polycyclic aromatic hydrocarbons (PAHs) and dioxins have several toxic properties, including mutagenicity, carcinogenicity and reproductive toxicity. PAHs mainly originate from the burning of petroleum and coal, while dioxins originate mainly from waste incineration and agrochemicals. Both PAHs and dioxins have aryl hydrocarbon receptor (AhR) binding activity which is related to toxicity of PAHs and dioxins.
In this study, we evaluated AhR binding activity of airborne particles collected in Beijing, China and Kanazawa, Japan by DR-CALUX and the contribution of PAHs and dioxins to this activity. AhR binding activity of airborne particles in Beijing (1,200 ng • m^-3) was four hundred times higher than in Kanazawa (2.7 ng • m^-3). The composition of PAHs didn′t show large difference in Beijing and Kanazawa. The contribution of the PAHs to CALUX-TEQ was higher than dioxins and especially high in Kanazawa (10.4 %). These results suggest that PAHs show large contribution to the toxicity of airborne particles, and other kinds of PAH and PAH related compounds will also contribute to that toxicity. The difference of concentration and composition of these compounds result in the different level of toxicity of airborne particles in each city.

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A comprehensive analytical method for semi-volatile organic compounds (SVOCs) in water samples by a combination of solid-phase extraction (SPE) and the automated identification and quantification system for gas chromatography-mass spectrometry database (AIQS-DB) has been developed. In the examinations of method development, 202 model compounds (MCs) that represent SVOCs that can be measured with GC-MS were used. Two SPE cartridges of hydrophilic functional group introduced styrenedivinylbenzene (SDB) polymer and activated carbon were selected as a best SPE combination and pH 7.0 was selected as the optimum extraction pH. In the reagent water recovery test (0.1 μg/L), the SPE method showed 96 % of the average recovery for 193 MCs, and that was comparable to 94 % of the average recovery shown by liquid-liquid extraction with dichloromethane (DCM-LLE). The method detection limit of the developed SPE method was 0.029 μg/L in average. In the recovery tests (0.1 μg/L) using seawater, river water and a sewage treatment facility effluent, the SPE method was able to extract 184 MCs (51 classes. logP_ow -0.65-15.07, b.p. 145-536 °C) with 90% of the average recovery except for high polar substances such as aromatic amines. To confirm the recoveries of such low recovery compounds, 17 surrogates were employed. Finally the combination of the SPE method and AIQS-DB was applied to real samples and the results were compared with those by the combination of DCM-LLE and AIQS-DB. As a result, the developed method detected 39 substances with a wide-range physico-chemical properties (logP_ow -0.07-14.6, b.p. 176-404 °C) which were the same as those by DCM-LLE. The detected concentrations by the both methods were almost the same except for sterols, bisphenol A and aniline that were highly extracted by DCM-LLE. From these results,it was demonstrated that SVOCs comprised of a wide range of volatility and polarity were able to be simultaneously extracted and determined by the combination of the developed SPE method and AIQS-DB.

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A liquid chromatography/tandem mass spectrometric (LC/MS/MS) procedure for the determination of fungicide1,1′-[iminodi (octamethylene)]di-guanidine (iminoctadine) in water samples has been developed. A direct derivatization of iminoctadine in watetr samples with benzoyl chloride (C₆H₅COCl) was applied to the procedure for the quantitative detection, in order to prevent the loss of iminoctadine in analytical processes because of the absorption activities. Iminoctadines in a water sample were treated with C₆H₅COCl to form the benzoate derivative, and then the derivative was extracted into dichloromethane. The extract was cleaned up using a florisil cartridge column, and the eluate was exchanged to acetonitrile. The derivative of iminoctadine in acetonitrile solution was determined by LC/MS/MS. The method detection limit for iminoctadine was 0.22 ng/L and the mean recoveries in water samples ranged from 80 to 101 % (c.v. 4.0-8.9 %). It was found that this method enables the reliable determination of iminoctadine residues in water samples at ppt level and is superior in sensitivity and reliability to the HPLC postcolumn derivatization fluorescence detection method which is the official analytical method for iminoctadine in Japan.
Moreover, to clear the behavior of iminoctadine in aquatic environment, a river water sample was fractionated into hydrophobic and hydrophilic fractions, and recovery tests of iminoctadine added to the fractions were conducted using this determination method. The results showed that the behavior of iminoctadine in aquatic environment is affected not only by suspended substances but by aquatic fumic substances of humic and fulvic acids. Some of iminoctadine in aquatic environment are likely incorporated into aquatic fumic substances by hydrogen bond or combining with them to form amides.

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Persistent organochlorine pesticides (OCPs), dichlorodiphenyltrichloroethane and its metabolites (DDTs), chlordane and related compounds (CHLs), heptachlor and its metabolites (HPCs), aldrin, dieldrin and endrin (DRNs), hexachlorobenzene(HCB), mirex and isomers of hexachlorocyclohexane (HCHs), in the muscles of crucian carp that were collected from 14 rivers and lakes throughout Japan during 2003-2005 were determined. OCPs were detected in all samples and the total concentrations ranged from 0.98 to 18 ng/g wet wt. or 120 to 1,600 ng/g lipid wt. Highest concentrations of OCPs were found in large cities, followed by small cities, agricultural areas and remote areas. CHLs and DDTs were the predominant compounds at almost all sites. Biota-sediment accumulation factors (BSAFs) of OCPs for crucian carp were calculated using the concentrations in sediment samples taken from the same locations as crucian carps. The obtained BSAFs of OCPs were higher than PCDDs and PCDFs, and comparable to dioxin-like PCBs. Maternal transfer rates of crucian carps in the spawning season were 21-37% comparable to or higher than those of dioxins.

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Serious pollution of the beach environment by plastic marine debris (litter) has been reported around the world. However, these reports are recorded in two types of measurement units: /m and /m². Therefore, we investigated which measurement is the more appropriate unit to measure beach debris. Our analysis is based on our 146 surveys of anthropogenic debris larger than or almost equal to plastic resin pellets from November 2004 to November 2009 at five relatively deserted beaches in Tottori, Japan. A total of 173, 981 fragments and items with a total weight of 433kg were collected. Surprisingly, about ten percent were thermal-fused plastic lumps, presumably due to incomplete burning. The floating marine debris washed up on the beaches normally forms a wrack belt, and the debris in the belt is over half of the total number and weight of the debris from shoreline to upper wrack limit. Since the wrack belts are narrow, the depth of sandy beaches affects neither the wash-up of floating debris nor the formation of debris belts. In fact, the correlation coefficients between the depth of beach and the number and weight of debris are very low (r_n=0.20 and r_w=0.19). The quantity of beach debris is significantly correlated with the length of the beach line because the wrack belt is usually parallel to the shoreline. Since the floating debris is ideally washed up on a one-dimensional intersection between beach and water surfaces,the unit of measure to quantify beach debris ought to be defined by the length of the beach line.

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Diarrhetic shellfish poisoning (DSP) is one of the gastrointestinal illness caused by the consumption of shellfish contaminated with toxigenic dinoflagellates. The main toxins responsible for DSP are Okadaic acid (OA) and its derivatives. Remarkable increase of free fatty acid (FFA) in the hepatopancreas (HP) of scallops during storage in a freezer is occasionally observed and it results in pseudo-positive with the MBA for DSP. In the process of making reference material(RM) for MBA, which is consisted of a set of a vial containing a piece of filter infused with OA and DSP negative slurry of homogenized scallop whole meat (WH), we investigated the concentration of FFA. The determination of OA and FFA concentrations was performed using liquid chromatography with a fluorometric detector for anthryl diazomethane (ADAM) derivatives. In this study FFA composition and toxicity were surveyed in homogenized scallop tissue stored in a freezer at -70°C for 4 months. Most of the samples were nontoxic as determined by mouse bioassay and showed low FFA concentration; one sample showed both toxic and high FFA concentrations. These results suggest that the determination of FFA concentration in scallop tissue by HPLC coupled with the MBA for DSP is important for RM.

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We established an estimation equation for dioxin TEQ (based on the WHO-2006 TEF system) by using the concentrations of indicative congeners. In the equation, total TEQ was evaluated by the sum of the products of each concentration of five indicative congeners (2,3,4,7,8-pentachlorodibenzofuran, 3,3′,4,4′,5-pentachlorobiphenyl (#126), 2,3,3′,4,4′-pentachlorobiphenyl (#105), 1,2,3,4,6,7,8-heptachlorodibenzo-p-dioxin and 1,2,3,7,8-pentachlorodibenzo-p-dioxin) and the corresponding coefficient (0.866, 0.112, 1.11X10^-4, 0.0313 and 1.29, respectively). To evaluate the effectiveness of the equation, analytical data of various environmental samples (ambient air, soil, and river sediment) were applied. As a result, the estimated total TEQ was in good agreement with the actual total TEQ which calculated from 29 TEF congener concentrations: the ratio of the estimated and actual total TEQ was 0.98 with the standard deviation at 0.09. This suggests the equation can assess the validity of dioxin-analytical result by comparing the total TEQ which calculated from 29 TEF congener concentrations with the estimated total TEQ. The equation can be useful for checking the quality of analytical results. We proposed an acceptable range of the ratio of the estimated total TEQ to the 29 TEF congener concentrations based one was 0.76-1.21.

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The production of bio diesel fuel(BDF) has been carried out nationwide as one method of recycling of used cooking oil. In general, the manufacturers of BDF are schools, NPO groups, and small and medium-sized enterprises, etc. However, the quality of BDF is hardly ever reported. Therefore, concentrations of fatty acid methyl ester (FAME), triglyceride, organic acids, methanol and acid number in BDF produced by used cooking oil in Kumamoto district were measured during a three-year period. In this investigation, the measurement methods adopted in the light oil compulsion standard were improved to ensure high precision. The concentrations of organic acids, methanol and acid number were lower than those of the standards. The average concentrations of FAME and triglyceride in BDF were 91.0 % and 2.5 % respectively. However, there were no serious problems due to the use of the BDF as a fuel for a diesel engine. Moreover, questionnaires concerning BDF manufacturing methods were distributed to BDF manufacturers.

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