Yasuyuki Zushi

Existence of nonpoint source of perfluorinated compounds and their loads in the Tsurumi River basin, Japan.

Products containing perfluorinated compounds (PFCs) have been widely used during the last 50 years. As a result, worldwide environmental pollution by PFCs has been reported. The sources of PFC pollution in the aquatic environment have been poorly understood. In this study, river water and sewage treatment plant (STP) effluent were sampled along the stretch of the Tsurumi River and also at a fixed station in the river. The concentrations of perfluorooctanesulfonate (PFOS), perfluorohexanoic acid (PFHxA), perfluoroheptanoic acid (PFHpA), perfluorooctanoic acid (PFOA), perfluorononanoic acid (PFNA) and perfluorodecanoic acid (PFDA) were measured. With an increase in river flow rate, it was observed that the PFC concentrations in the river water at fixed station were remained the same or increased for PFOS (179.9+/-34.4-179.6+/-69.5 ng l(-1)), PFHxA (5.5+/-0.8-9.0+/-2.6 ng l(-1)), PFHpA (3.1+/-0.3-4.4+/-1.0 ng l(-1)), and PFOA (15.9+/-0.3-13.4+/-2.5 ng l(-1)) whereas the concentration of PFNA (38.0+/-3.3-15.4+/-3.0 ng l(-1)) and PFDA (3.9+/-0.3-2.1+/-0.3 ng l(-1)) were decreased. On the other hand, the loads of every PFC increased with an increase in river flow rate. The loads of PFCs in rain runoff were estimated to be 2-11 times greater than those in STP effluents that are discharged into the river. These results indicate the existence of a PFC nonpoint source (NPS) and its impact to the total PFC load of river is significant.

Time trends of perfluorinated compounds from the sediment core of Tokyo Bay, Japan (1950s-2004).

Perfluorinated compounds (PFCs) were detected in sediment core samples collected in Tokyo Bay to reveal their time trends. The core sample deposited during 1950s-2004 was divided into two- to three-year intervals and the concentrations of 24 types of PFCs were determined. Perfluorooctane sulfonate (PFOS) decreased gradually from the early 1990s and its precursor decreased rapidly in the late 1990s, whereas perfluorooctanoic acid (PFOA) increased rapidly. The observed trends were regarded as a reflection of the shift from perfluorooctyl sulfonyl fluoride (PFOSF)-based products to telomer-based products after the phaseout of PFOSF-based products in 2001. The branched isomers of perfluoroundecanoic acid (PFUnDA) and perfluorotridecanoic acid (PFTrDA) were detected in the sample with its ratio of linear-isomer/branched-isomer concentrations decreasing. In this study, we revealed that the sediment core can serve as a tool for reconstructing the past pollution trend of PFCs and can provide interesting evidence concerning their environmental dynamics and time trend.

Spatially detailed survey on pollution by multiple perfluorinated compounds in the Tokyo Bay basin of Japan.

Pollution from 35 perfluorinated compounds (PFCs) in the water of the Tokyo Bay basin was examined. The water in the basin contained relatively high levels of perfluorononanoate (PFNA), perfluorooctanoate (PFOA), and perfluorooctane sulfonate (PFOS) compared to the other PFCs, which were present at concentrations of 20.1 ng/L, 6.7 ng/L, and 5.8 ng/L, respectively. In contrast, the concentrations of their precursors and degradation products were an order of magnitude lower. Sewage treatment plant (STP) effluent in the area also contained high levels of PFNA compared with the river water samples (Mann-Whitney U-test, p<0.0002). From a spatial aspect, increases in PFC pollution levels correlated with increased urbanization in the study area suggested that there are nonpoint source contributors to the PFC pollution in this area. Branched isomers of the PFCs were also quantified. Samples that contained high concentrations of perfluoroalkyl carboxylates (PFCA) showed lower proportions of its branched isomer. This indicates that the branched isomers are more prominent in the area with lower PFC pollution. This analysis was beneficial for estimating the individual contributions of different PFCA production processes. This survey provided new information on the sources, spatial distribution, and behavioral characteristics of PFC pollutants in this area.

Identifying the nonpoint source of perfluorinated compounds using a geographic information system based approach

Perfluorinated compounds (PFCs) have been detected in a wide range of places. They have also been reported to come from nonpoint sources, but the origin of these sources has not been identified. In the present study, we attempted to characterize the nonpoint source of PFCs in the Hayabuchi River, Japan, which runs through an urban area, using a geographic information system (GIS) and statistical analysis. We also estimated annual PFC loads from nonpoint sources in Japan as a whole, determining a magnitude comparable to that from sewage treatment plants (STPs); the range was a few tons per year for each PFC. Perfluorinated compound pollution in river water was found to increase when the river received drainage from an area with a high proportion of commercial and/or transportation land use. It was also found that more PFCs were discharged from the watersheds where train stations are located. This result could be interpreted as the use of land for commercial and transportation purposes is prevalent in close proximity to train stations, and that the effluents from those areas contain high concentrations of PFCs. These findings suggested that train stations could be indicators of nonpoint sources of PFCs.

First-flush loads of perfluorinated compounds in stormwater runoff from Hayabuchi River basin, Japan served by separated sewerage system

Worldwide environmental pollution by perfluorinated compounds (PFCs) has been reported. PFCs have also been reported to have nonpoint sources (NPSs). A fixed-point hourly monitoring in the river was conducted during a storm event using an automatic sampler to estimate the impact of the first-flush of PFCs from NPS in this study. Perfluorocarboxylates (PFCAs) and perfluoroalkyl sulfonates (PFASs) with different chain lengths were monitored. The concentrations of short- to medium-chain-length PFCAs such as PFHpA, PFOA and PFNA, and PFASs such as PFBS, PFPeS, PFHxS, PFHpS and PFOS showed no marked increase with the storm-runoff event. However, in contrast to this, concentrations of long-chain-length PFCAs such as PFDA and PFUnA increased markedly. The concentrations of PFDA and PFUnA increased 3.4 (1.5-5.0 ng L(-1))- and 2.0 (3.3-6.7 ng L(-1))-fold, respectively. This study demonstrates that large loads of long-chain-length PFCAs are discharged to the Hayabuchi River during the first-flush after the rain event.

Selective extraction of halogenated compounds from data measured by comprehensive multidimensional gas chromatography/high resolution time-of-flight mass spectrometry for non-target analysis of environmental and biological samples.

We developed a method that selectively extracts a subset from comprehensive 2D gas chromatography (GC×GC) and high-resolution time-of-flight mass spectrometry (HRTOFMS) data to detect and identify trace levels of organohalogens. The data were obtained by measuring several environmental and biological samples, namely fly ash, soil, sediment, the atmosphere, and human urine. For global analysis, some samples were measured without purification. By using our novel software, the mass spectra of organochlorines or organobromines were then extracted into a data subset under high mass accuracy conditions that were approximately equivalent to a mass resolution of 6000 for some samples. Mass defect filtering as pre-screening for the data extraction was very effective in removing the mass spectra of hydrocarbons. Those results showed that data obtained with HRTOFMS are valuable for global analysis of organohalogens, and probably of other compounds if specific data extraction methods can be devised.

Rapid automatic identification and quantification of compounds in complex matrices using comprehensive two-dimensional gas chromatography coupled to high resolution time-of-flight mass spectrometry with a peak sentinel tool.

Comprehensive two-dimensional gas chromatography coupled to mass spectrometry (GC×GC-MS) is a powerful tool for comprehensive analysis of organic pollutants. In this study, we developed a powerful analytical method using GC×GC for rapid and accurate identification and quantification of compounds in environmental samples with complex matrices. Specifically, we have developed an automatic peak sentinel tool, T-SEN, with free programming software, R. The tool, which consists of a simple algorithm for on peak finding and peak shape identification, allows rapid screening of target compounds, even for large data sets from GC×GC coupled to high resolution time of flight mass spectrometry (HRTOFMS). The software tool automatically assigns and quantifies compounds that are listed in user databases. T-SEN works on a typical 64 bit workstation, and the reference calculation speed is 10-20 min for approximately 170 compounds for peak finding (five ion count setting) and integration from 1-2GB of sample data acquired by GC×GC-HRTOFMS. We analyzed and quantified 17 PCDD/F congeners and 24 PCB congeners in a crude lake sediment extract by both GC×GC coupled to quadrupole mass spectrometry (qMS) and GC×GC-HRTOFMS with T-SEN. While GC×GC-qMS with T-SEN resulted in false identification and inaccurate quantification, GC×GC-HRTOFMS with T-SEN provided correct identification and accurate quantification of compounds without sample pre-treatment. The differences between the values measured by GC×GC-HRTOFMS with T-SEN and the certified values for the certified reference material ranged from 7.3 to 36.9% for compounds with concentrations above the limit of quantification. False positives/negatives were not observed, except for when co-elution occurred. The technique of GC×GC-HRTOFMS in combination with T-SEN provides rapid and accurate screening and represents a powerful new approach for comprehensive analysis.

GIS-based source identification and apportionment of diffuse water pollution: Perfluorinated compound pollution in the Tokyo Bay basin

To efficiently reduce perfluorinated compound (PFC) pollution, it is important to have an understanding of PFC sources and their contribution to the pollution. In this study, source identification of diffuse water pollution by PFCs was conducted using a GIS-based approach. Major components of the source identification were collection of the monitoring data and preparation of the corresponding geographic information that was extracted from a constructed GIS database. The spatially distributed pollution factors were then explored by multiple linear regression analysis, after which they were visually expressed using GIS. Among the 35 PFC homologues measured in a survey of the Tokyo Bay basin, 18 homologues were analyzed. Pollution by perfluorooctane sulfonate (PFOS) was explained well by the percentage of arterial traffic area in the basin, and the 84% variance of the measured PFOS concentration was explained by two geographic variables, arterial traffic area and population. Source apportionment between point and nonpoint sources was conducted based on the results of the analysis. The contribution of PFOS from nonpoint sources was comparable to that from point sources in several major rivers flowing into Tokyo Bay. Source identification and apportionment using the GIS-based approach was shown to be effective, especially for ubiquitous types of pollution, such as PFC pollution.

Survey of perfluoroalkyl acids (PFAAs) and their precursors present in Japanese consumer products

Perfluoroalkyl acids (PFAAs) and their precursors have been used in various consumer products. However, limited information regarding their occurrence and concentration levels in products is available. In this study, we investigated 18 PFAAs and 14 PFAA precursors in various categories of consumer products purchased in Japan. Relatively high total concentrations of PFAAs and their precursors were found in sprays for fabrics and textiles (<limit of quantitation (LOQ)-30000 ng g(-1)) and car wash/coating products (<LOQ-7500 ng g(-1)) compared to other categories, and the similar observation was found in previous studies in Norway and Germany. A precursor of perfluorooctane sulfonic acid (PFOS), N-methyl perfluorooctane sulfonamidoethanol (MeFOSE) was detected in a higher frequency (8%) and in greater concentrations (<LOQ-3600±1800 ng g(-1)) than PFOS (frequency 4%; concentrations<LOQ-59±10 ng g(-1)). These results indicate that careful control of PFOS precursors in consumer products is required. Furthermore, the amount of PFAAs emitted from consumer products may be underestimated if the occurrence of PFAA precursors is not considered. In addition to PFAA precursors, long chain perfluoroalkyl carboxylic acids (PFCAs) (carbon chain length⩾7) were also detected in greater concentrations than short chain PFCAs (⩽6). This result suggests that consumer products are one of the important sources of long-chain PFCAs in the environment.

Spatial distribution and importance of potential perfluoroalkyl acid precursors in urban rivers and sewage treatment plant effluent--case study of Tama River, Japan.

Production and use of perfluorooctane sulfonate (PFOS) is regulated worldwide. However, numerous potential precursors that eventually decompose into PFOS and other perfluoroalkyl acids (PFAAs) such as perfluorooctanoic acid (PFOA) are still being used and have not been studied in detail. Therefore, knowledge about the levels and sources of the precursors is essential. We investigated the total concentration of potential PFAA precursors in the Tama River, which is one of the major rivers flowing into the Tokyo Bay, by converting all the perfluorinated carboxylic acid (PFCA) and perfluoroalkyl sulfonic acid (PFSA) precursors into PFCAs by chemical oxidation. The importance of controlling PFAA precursors was determined by calculating the ratios of PFCAs formed by oxidation to the PFAAs originally present (ΣΔ[PFCAC4-C12]/Σ[PFAAs]before oxidation) (average = 0.28 and 0.69 for main and tributary branch rivers, respectively). Higher total concentrations of Δ[PFCAs] were found in sewage treatment plant (STP) effluents. However, the ratios found in the effluents were lower (average = 0.21) than those found in the river water samples, which implies the decomposition of some precursors into PFAAs during the treatment process. On the other hand, higher ratios were observed in the upstream water samples and the existence of emission sources other than the STP effluents was indicated. This study showed that although the treatment process converting a part of the PFAA precursors into PFAAs, STPs were important sources of precursors to the Tama River. To reduce the levels of PFAAs in the aquatic environment, it is necessary to reduce the emission of the PFAA precursors as well.