Michio Murakami

International Pellet Watch: Global monitoring of persistent organic pollutants (POPs) in coastal waters. 1. Initial phase data on PCBs, DDTs, and HCHs

Samples of polyethylene pellets were collected at 30 beaches from 17 countries and analyzed for organochlorine compounds. PCB concentrations in the pellets were highest on US coasts, followed by western Europe and Japan, and were lower in tropical Asia, southern Africa and Australia. This spatial pattern reflected regional differences in the usage of PCBs and was positively correlated with data from Mussel Watch, another monitoring approach. DDTs showed high concentrations on the US west coast and in Vietnam. In Vietnam, DDT was predominant over its metabolites (DDE and DDD), suggesting the principal source may be current usage of the pesticide for malaria control. High concentrations of pesticide HCHs were detected in the pellets from southern Africa, suggesting current usage of the pesticides in southern Africa. This study demonstrates the utility and feasibility of the International Pellet Watch approach to monitor POPs at a global scale.

Evaluation of wastewater and street runoff as sources of perfluorinated surfactants (PFSs).

Perfluorinated surfactants (PFSs) in wastewater and street runoff in Japan were measured to determine their pathways of travel and utility as indicators of each to water environments. Among PFS species, perfluorooctanesulfonate (PFOS), perfluorooctanoate (PFOA), and perfluorononanoate (PFNA) were dominant in wastewater. PFS concentrations were higher in secondary effluents than in influents, possibly because of biodegradation of their precursors. This was supported by a significant correlation between concentration increases of PFOA and PFNA. Biodegradation of the same precursors probably produced mainly PFOA and secondarily PFNA. Concentrations of perfluorocarboxylates (PFCAs), especially longer- and even-chain PFCAs, in street runoff were equal to or higher than those in wastewater influents and secondary effluents, but PFOS concentrations were lower in street runoff. This result suggests that street runoff potentially contaminates water environments with PFCAs. In street runoff, perfluorodecanoate (PFDA), perfluoroundecanoate (PFUA), and perfluorododecanoate (PFDDA) were abundant along with PFOA and PFNA. PFS profiles in street runoff were significantly different from those in wastewater samples, suggesting that relative proportions of PFSs can be useful as indicators. Four ratios - PFOA/PFOS, PFNA/PFOS, long-chain/(short-chain+long-chain), and even-chain/(even-chain+odd-chain) - were proposed to evaluate the contributions of PFSs from wastewater and street runoff to water environments.

Sources of sedimentary PAHs in tropical Asian waters: Differentiation between pyrogenic and petrogenic sources by alkyl homolog abundance

We collected surface sediment samples from 174 locations in India, Indonesia, Malaysia, Thailand, Vietnam, Cambodia, Laos, and the Philippines and analyzed them for polycyclic aromatic hydrocarbons (PAHs) and hopanes. PAHs were widely distributed in the sediments, with comparatively higher concentrations in urban areas (Sigma PAHs: approximately 1000 to approximately 100,000 ng/g-dry) than in rural areas ( approximately 10 to approximately 100g-dry), indicating large sources of PAHs in urban areas. To distinguish petrogenic and pyrogenic sources of PAHs, we calculated the ratios of alkyl PAHs to parent PAHs: methylphenanthrenes to phenanthrene (MP/P), methylpyrenes+methylfluoranthenes to pyrene+fluoranthene (MPy/Py), and methylchrysenes+methylbenz[a]anthracenes to chrysene+benz[a]anthracene (MC/C). Analysis of source materials (crude oil, automobile exhaust, and coal and wood combustion products) gave thresholds of MP/P=0.4, MPy/Py=0.5, and MC/C=1.0 for exclusive combustion origin. All the combustion product samples had the ratios of alkyl PAHs to parent PAHs below these threshold values. Contributions of petrogenic and pyrogenic sources to the sedimentary PAHs were uneven among the homologs: the phenanthrene series had a greater petrogenic contribution, whereas the chrysene series had a greater pyrogenic contribution. All the Indian sediments showed a strong pyrogenic signature with MP/P approximately 0.5, MPy/Py approximately 0.1, and MC/C approximately 0.2, together with depletion of hopanes indicating intensive inputs of combustion products of coal and/or wood, probably due to the heavy dependence on these fuels as sources of energy. In contrast, sedimentary PAHs from all other tropical Asian cities were abundant in alkylated PAHs with MP/P approximately 1-4, MPy/Py approximately 0.3-1, and MC/C approximately 0.2-1.0, suggesting a ubiquitous input of petrogenic PAHs. Petrogenic contributions to PAH homologs varied among the countries: largest in Malaysia whereas inferior in Laos. The higher abundance of alkylated PAHs together with constant hopane profiles suggests widespread inputs of automobile-derived petrogenic PAHs to Asian waters.

Assessment of groundwater pollution in Tokyo using PPCPs as sewage markers.

While the occurrence of pharmaceuticals and personal care products (PPCPs) in groundwater has typically been reported in bank filtration sites, irrigated fields, septic tanks, and sewage disposal practices, fewer studies have been conducted in highly urbanized areas, where infiltration of treated or untreated sewage is not supposed to be a source of groundwater recharge. Furthermore, little is known about the occurrence of various kinds of PPCPs in relation to microbial indicators in groundwater from different types of aquifers. Thus, we examined the city-wide occurrence of selected PPCPs (diethyltoluamide, crotamiton, ethenzamide, propyphenazone, carbamazepine, and caffeine) and E. coli in 50 groundwaters from unconfined aquifers (<30 m in depth) and confined aquifers (up to 500 m in depth) in Tokyo, where unintended groundwater contamination could take place due to decrepit sewer networks. PPCPs were detected in unconfined aquifers and springs (23/34 samples, 68%), and in confined aquifers (7/16 samples, 44%). Compared with published results for sewage influents, concentrations of PPCPs, excluding caffeine, were generally 1-2 orders of magnitude lower, while in some samples concentrations were quite comparable. The high occurrence rate of PPCPs, even in confined aquifers, indicated that such aquifers are not always protected from pollution by sewage near the land surface. Among the PPCPs analyzed, carbamazepine and crotamiton were most frequently detected, which would appear to be owing to their high persistence, combined with the high concentration of crotamiton in sewage. Crotamiton was detected in all four E. coli-positive groundwaters, and thus may potentially serve as a precautionary indicator of E. coli contamination. Using carbamazepine as a sewage marker, we estimated that 0.8%-1.7% of the dry-weather flow of sewage was leaking out into the unconfined aquifers.

Multiple evaluations of the removal of pollutants in road runoff by soil infiltration.

Groundwater replenishment by infiltration of road runoff is expected to be a promising option for ensuring a sustainable urban water cycle. In this study, we performed a soil infiltration column test using artificial road runoff equivalent to approximately 11-12 years of rainfall to evaluate the removal of pollutants by using various chemical analyses and bioassay tests. These results indicated that soil infiltration treatment works effectively to remove most of the pollutants such as organic matter (chemical oxygen demand (CODMn) and dissolved organic carbon (DOC)), P species, polycyclic aromatic hydrocarbons (PAHs), numerous heavy metals and oestrogenic activities. Bioassay tests, including algal growth inhibition test, Microtox and mutagen formation potential (MFP) test, also revealed effective removal of toxicities by the soils. However, limited amounts of NO3, Mn, Ni, alkaline earth metals, perfluorooctane sulphonate (PFOS) and perfluorooctane sulphonamide (FOSA) were removed by the soils and they possibly reach the groundwater and cause contamination.

Perfluorinated surfactants (PFSs) in size-fractionated street dust in Tokyo.

We investigated perfluorinated surfactants (PFSs) in size-fractionated street dust to identify their occurrence, contributions from traffic, and potential routes of entry into waters. Street dust was collected from residential areas and heavily trafficked areas in Tokyo and sorted into fine (<63 microm) and coarse fractions (63-2000 microm). Five PFS species were analyzed by liquid chromatography-tandem mass spectrometry: perfluorooctanesulfonate (PFOS), perfluorooctanoate (PFOA), perfluorononanoate (PFNA), perfluorodecanoate (PFDA), and perfluoroundecanoate (PFUA). In fine fractions, PFS contents were significantly higher in heavily trafficked street dust than in residential street dust, but in coarse fractions, no significant differences were observed. Additionally, in heavily trafficked areas, PFS contents were significantly higher in fine fractions than in coarse fractions, but in residential areas, no significant differences were observed. PFS compositions differed between size fractions, not locations, indicating differences in sources between size fractions. Fine particles from traffic contributed to PFSs in street dust. Street dust possibly acts as the origin of PFSs in street runoff and eventually enters waters. This is the first report of PFSs in street dust.

Sorption behavior of heavy metal species by soakaway sediment receiving urban road runoff from residential and heavily trafficked areas.

Groundwater contamination by heavy metals from infiltration facilities receiving road runoff is of potential concern. In this study, sorption tests were conducted to evaluate the influence of the water quality of road runoff, especially dissolved organic matter (DOM), on the sorption of heavy metal species by soakaway sediment. Sequential batch tests were conducted to assess metal sorption by the soakaway sediment receiving road runoff from residential and heavily trafficked areas. Ni was adsorbed by the sediment, indicating that soakaway sediments function to prevent groundwater contamination by Ni. In contrast, Zn was released from the soakaway sediment in sorption tests using heavily trafficked road dust leachates. Ni, Cu, Zn, and dissolved organic carbon concentrations were higher in soakaway sediment leachates obtained by sorption tests using heavily trafficked road dust leachates than those using residential road dust leachates, suggesting traffic activities contaminate these pollutants. A large portion of Zn, released from the soakaway sediment, existed as stable complexes. DOM in road runoff possibly enhances the release of Zn from the sediments within infiltration facilities and might cause groundwater contamination.

Occurrence and formation potential of N-nitrosodimethylamine in ground water and river water in Tokyo

N-nitrosodimethylamine (NDMA), a disinfection byproduct of water and wastewater treatment processes, is a potent carcinogen. We investigated its occurrence and the potential for its formation by chlorination (NDMA-FP Cl2) and by chloramination (NDMA-FP NH2Cl) in ground water and river water in Tokyo. To characterize NDMA precursors, we revealed their molecular weight distributions in ground water and river water. We collected 23 ground water and 18 river water samples and analyzed NDMA by liquid chromatography-tandem mass spectrometry. NDMA-FP Cl2 was evaluated by chlorinating water samples with free chlorine for 24 h at pH 7.0 while residual free chlorine was kept at 1.0-2.0 mg Cl(2)/L. NDMA-FP NH2Cl was evaluated by dosing water samples with monochloramine at 140 mg Cl(2)/L for 10 days at pH 6.8. NDMA precursors and dissolved organic carbon (DOC) were fractionated by filtration through 30-, 3-, and 0.5 kDa membranes. NDMA concentrations were <0.5-5.2 ng/L (median: 0.9 ng/L) in ground water and <0.5-3.4 ng/L (2.2 ng/L) in river water. NDMA concentrations in ground water were slightly lower than or comparable to those in river water. Concentrations of NDMA-FP Cl2 were not much higher than concentrations of NDMA except in samples containing high concentrations of NH(3) and NDMA precursors. The increased NDMA was possibly caused by reactions between NDMA precursors and monochloramine unintentionally formed by the reaction between free chlorine and NH(3) in the samples. NDMA precursors ranged from 4 to 84 ng-NDMA eq./L in ground water and from 11 to 185 ng-NDMA eq./L in river water. Those in ground water were significantly lower than those in river water, suggesting that NDMA precursors were biodegraded, adsorbed, or volatilized during infiltration. The molecular weight of NDMA precursors in river water was dominant in the <0.5 kDa fraction, followed by 0.5-3 kDa. However, their distribution was inconsistent in ground water: one was dominant in the <0.5 kDa fraction, and the other in 0.5-3 kDa. Molecular weight distributions of NDMA precursors were very different from those of DOC. This is the first study to reveal the widespread occurrence and characterization of NDMA precursors in ground water.

Was the risk from nursing-home evacuation after the Fukushima accident higher than the radiation risk?

After the 2011 accident at the Fukushima Daiichi nuclear power plant, nursing-home residents and staff were evacuated voluntarily from damaged areas to avoid radiation exposure. Unfortunately, the evacuation resulted in increased mortalities among nursing home residents. We assessed the risk trade-off between evacuation and radiation for 191 residents and 184 staff at three nursing homes by using the same detriment indicator, namely loss of life expectancy (LLE), under four scenarios, i.e. “rapid evacuation (in accordance with the actual situation; i.e. evacuation on 22 March),” “deliberate evacuation (i.e. evacuation on 20 June),” “20-mSv exposure,” and “100-mSv exposure.” The LLE from evacuation-related mortality among nursing home residents was assessed with survival probability data from nursing homes in the city of Minamisoma and the city of Soma. The LLE from radiation mortality was calculated from the estimated age-specific mortality rates from leukemia and all solid cancers based on the additional effective doses and the survival probabilities. The total LLE of residents due to evacuation-related risks in rapid evacuation was 11,000 persons-d—much higher than the total LLEs of residents and staff due to radiation in the other scenarios (27, 1100, and 5800 persons-d for deliberate evacuation, 20 mSv-exposure, and 100 mSv-exposure, respectively). The latitude for reducing evacuation risks among nursing home residents is surprisingly large. Evacuation regulation and planning should therefore be well balanced with the trade-offs against radiation risks. This is the first quantitative assessment of the risk trade-off between radiation exposure and evacuation after a nuclear power plant accident.

A GIS-based evaluation of the effect of decontamination on effective doses due to long-term external exposures in Fukushima.

Despite the enormous cost of radiation decontamination, there has been almost no quantitative discussion on how much it would reduce the long-term external radiation exposure in the Evacuation Zone and Planned Evacuation Zone (restricted zone) in Fukushima. The aim of this study is to assess the effectiveness of decontamination and return options and to identify important parameters for estimating the long-term cumulated effective dose (CED) during 15, 30 and 70 year period using data on land-use, population and decontamination in the restricted zone (about 1100 km(2)) in Fukushima. Decontamination of the land is assumed to have a certain efficacy in terms of the reduction of CED. The EeCC (external exposure conversion coefficient) is the parameter having the greatest effect on the percentage of area having CED during the 30 years above 100 m Sv after decontamination, ranging from 13% (EeCC=0.2) to 55% (EeCC=0.6). Therefore, we recommend a detailed investigation of the EeCC in Japan.