Photodegradation of surfactants. XV: Formation of SO4 ions in the photooxidation of sulfur-containing surfactants

Three types of surfactants and related reference compounds containing sulfonate (-SO₃Na), sulfate (-OSO₃Na) or thioether carboxylate (-S-Cn-COOK) group were photodecomposed in an aqueous heterogeneous dispersion system. The photomineralization to SO₄²⁻ions was examined for the surfactants with different chemical structures. The photocatalytic activities of TiO₂ and ZnO were compared for the sulfonates of dodecylbenzene sulfonate (DBS) and polystyrene sulfonate (PSS), the sulfates of sodium dodecyl sulfate (SDS), and the potassium salts of S-dodecylthioglycol acid (TGA), S-dodecylthiopropionic acid (TPA) and S-dodecylthiomalic acid (TMA). ZnO catalyst exhibited higher activity in the formation of SO₄²⁻ion than TiO₂ catalyst.     

Possible change in Asian dust source suggested by atmospheric anthropogenic radionuclides during the 2000s

Decades-long monitoring of anthropogenic radionuclides in the atmospheric deposition in Tsukuba, Japan suggests not only the substantial impacts of the Asian dust (Kosa) on the deposition but also the possible change of the Kosa source region, especially during springs of the 2000s. In order to know more about such change, 4 single wet deposition events occurred in the spring of 2007 were scrutinized. The largest anthropogenic radionuclides wet deposition was supplied by the April 2–4 event. It brought several tens % of the monthly depositions (April 2007) of the dust (residue) mass (4.5 g m^?2) and anthropogenic radionulides (⁹⁰Sr: 16, ¹³⁷Cs: 97 and Pu: 3 mBq m^?2). None of the events observed fulfilled both criteria of the specific activities and ⁹⁰Sr/¹³⁷Cs activity ratio to the Tsukuba soil; they did not exhibit local soil dust signature. The Kosa events in fact have extensive impacts on the atmospheric environment over Japan in spring season. Considering the elevated specific activities as well as greater ¹³⁷Cs/⁹⁰Sr activity ratio in the deposited dust, it is hypothesized that the dust source areas in Asian continent would be shifting from the arid zone to the desert-steppe zone suffering from desertification during the 2000s. This type of the Kosa may be called as the ‘new-regime Kosa’. Chemical observation in the far downwind region of the Kosa dust could allow us to know possible shift in the source regions.     

Estimation of contribution from non-point sources to perfluorinated surfactants in a river by using boron as a wastewater tracer

The contribution of non-point sources to perfluorinated surfactants (PFSs) in a river was evaluated by estimating their fluxes and by using boron (B) as a tracer. The utility of PFSs/B as an indicator for evaluating the impact of non-point sources was demonstrated. River water samples were collected from the Iruma River, upstream of the intake of drinking water treatment plants in Tokyo, during dry weather and wet weather, and 13 PFSs, dissolved organic carbon (DOC), total nitrogen (TN), and B were analyzed. Perfluorohexane sulfonate (PFHxS), perfluorooctane sulfonate (PFOS), perfluoroheptanoate (PFHpA), perfluorooctanoate (PFOA), perfluorononanoate (PFNA), perfluorodecanoate (PFDA), perfluoroundecanoate (PFUA), and perfluorododecanoate (PFDoDA) were detected on all sampling dates. The concentrations and fluxes of perfluorocarboxylates (PFCAs, e.g. PFOA and PFNA) were higher during wet weather, but those of perfluoroalkyl sulfonates (PFASs, e.g. PFHxS and PFOS) were not. The wet/dry ratios of PFSs/B (ratios of PFSs/B during wet weather to those during dry weather) agreed well with those of PFS fluxes (ratios of PFS fluxes during wet weather to those during dry weather), indicating that PFSs/B is useful for evaluating the contribution from non-point sources to PFSs in rivers. The wet/dry ratios of PFOA and PFNA were higher than those of other PFSs, DOC, and TN, showing that non-point sources contributed greatly to PFOA and PFNA in the water. This is the first study to use B as a wastewater tracer to estimate the contribution of non-point sources to PFSs in a river.     

Arsenic and Mn levels in Isaza (Gymnogobius isaza) during the mass mortality event in Lake Biwa, Japan

The present study measured the concentrations of 25 elements (Li, Mg, V, Cr, Mn, Co, Ni, Cu, Zn, As, Se, Rb, Sr, Mo, Ag, Cd, In, Sn, Sb, Cs, Ba, Hg, Tl, Pb and Bi) in the whole body of Isaza which is an endemic fish species to Lake Biwa, Japan, and compared the values in the specimens from the mass mortality Isaza (MMI) and normal fresh Isaza (NFI). The mean levels of Mn and total As (T-As) were relatively higher in MMI than in NFI. In the T-As, highly toxic inorganic As was detected in MMI. Moreover we found Mn and As concentrations in surface sediment were extremely high and temporally increased. From all these results, we could infer that the dissolution of Mn and As from surface sediment of Lake Biwa might have been one of the cause for the mass mortality of Isaza.     

Evaluation of operational parameters in thermophilic acid fermentation of kitchen waste

In this study, the effect of operational parameters, such as solids retention time (SRT), pH, and substrate total solids (TS) concentration, on acid fermentation efficiency was investigated. From batch tests, it was shown that the appropriate pH range for thermophilic acidogens was around 6–7 and that the optimum pH condition was 6. From the continuous experiment, pH and SRT were shown to be the most important operational parameters for solubilization and organic acid production. In contrast, TS concentration did not show any obvious effect on chromium chemical oxygen demand (CODcr) solubilization when TS was in the range 3.5%–10%. The optimum operational conditions for thermophilic acid fermentation were an SRT of 2 days and a pH of 6. This research was carried as a part of the CREST project of Japan Science and Technology Agency.     

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.     

What Anthropogenic Radionuclides (90Sr and 137Cs in Atmospheric Deposition, Surface Soils and Aeolian Dusts Suggest for Dust Transport over Japan

Currently, atmospheric anthropogenic radionuclides (particulate) are controlled by suspension of the surface dust containing those radionuclides (resuspension). We have found, therefore, that such radionuclides can be used as tracers of the surface dust suspension, transport and its subsequent deposition in distant areas. The ¹³⁷Cs/⁹⁰Sr activity ratios in the atmospheric deposition, without the direct influence of nuclear tests and accidents, at the Meteorological Research Institute (MRI, Tsukuba, Japan) during the 1990s were fairly low (average: 2.1). This value is not in agreement with the ratios in Japanese surface soils (range of averages: 4–7), which had been considered as the primary source of the deposited dust. This suggests that the current atmospheric dust deposition in Japan is a mixture of local and remote components. The remote component could be an aeolian dust that has been transported long distances from arid areas. The major component is most likely to be Asian dust. It was further hypothesized that other remote source may exist beyond the Asian domain, based on accumulated observations and model results. To obtain more information about the dust transport, Sahara dust deposited in Monaco in 2002 and a suspended dust collected in the Taklamakan area in 2001 were analyzed for ⁹⁰Sr and ¹³⁷Cs. The Taklamakan dust exhibited a ¹³⁷Cs/⁹⁰Sr ratio of about 4, which is within the range of atmospheric deposition observed at the MRI, while the Sahara dust exhibited a higher ¹³⁷Cs/⁹⁰Sr ratio (about 13). Although the present Sahara datum was negative for our hypothesis of ‘hyper-range transport’, the seasonal change of the ¹³⁷Cs/⁹⁰Sr ratio in the atmospheric deposition observed at the MRI requires an aeolian dust source having a low ¹³⁷Cs/⁹⁰Sr ratio, other than Asian dust.     

Development and verification of new evaluation indicators for chemical management in corporations to meet WSSD goals

During the World Summit on Sustainable Development (WSSD), it was agreed that adequate chemical management based on risk assessment should be achieved by 2020. To achieve the WSSD goals, it is important to evaluate and enhance the voluntary activities of corporations because they are the main agents dealing with chemical management. To this end, we developed new evaluation indicators that were combined with the SCP Axes (Science Axis - evaluation of the scientific basis; Capacity Axis - evaluation of the abilities of personnel and organizations; and the Performance Axis - evaluation of results of activities and information disclosure to the community, etc.) and 4 elements (hazard assessment, exposure assessment, risk assessment, and risk management). We administered surveys to Japanese corporations from 2006 to 2008 to verify the developed indicators. The survey results showed that the activities concerning chemical management were very different across corporations for each industry category and that the hazard assessment improved, reflecting a vigorous social movement that included legal obligations. Therefore, the new evaluation indicators possessed high resolution and precisely grasped the changes in corporate activities. We found that these indicators provided an effective way to understand corporate activities designed to meet the goals of the WSSD.     

Estimation and validation of biomass of a mountainous agroecosystem by means of sampling,spectral data and QuickBird satellite image

Biomass estimation in agroecosystems (AESs) is important to understand their role in carbon exchange for a sustainable environment. We used field spectra and sampled biomass of an AES including cultivated and abandoned croplands to develop a simple biomass estimation model. The digital number (DN) of a QuickBird (QB) satellite image was converted to a reflectance factor using the dark object subtraction method and the spectral reflectance of asphalt. The relationship between the reflectance factor of field-based spectra and the QB image obtained in early July 2007 was insignificant in the blue (R ² = 0.15) and green (R ² = 0.18) bands but was significant (p < 0.05) in the red (R ² = 0.57) and near-infrared (NIR, R ² = 0.45) bands in the AES. Better correlations were obtained between field-based and QB-based vegetation indices (VIs). The best correlations were obtained with the normalized difference vegetation index (NDVI) (R ² = 0.97, p < 0.001) and the ratio vegetation index (RVI) (R ² = 0.99, p < 0.001). Biomass was significantly correlated with both field-based NDVI and RVI (R ² = 0.79 and 0.72, respectively, p < 0.001). Although RVI saturated at higher biomass densities (>600 g m^?2), NDVI showed a linear relationship. Other field-based VIs showed poorer correlations with biomass. The model was evaluated by incorporating it into high-resolution QB images to obtain the observed biomass. The relationship between field-estimated and QB-observed biomass appeared to be a one-to-one linear relationship (R ² = 0.79). Thus, models using field spectra and sampled biomass can be applied to QB images for remote estimation of biomass in an AES.     

Hydrodynamic characteristics and related mass-transfer properties in open-channel flows with rectangular embayment zone

Consecutive groynes and embayments form dead water zones, where sedimentation and high concentrations of pollutants are often observed. It is thus very important to understand the mass and momentum exchange between the main channel and side cavities in rivers and hydraulic engineering structures. The spanwise gradient of the streamwise velocity near the junction produces small-scale turbulent vortices because of shear instability. Furthermore, large-scale horizontal circulation is also generated in the cavity zone. These coherent turbulent structures play a significant role in mass and sediment transfer at the boundary between the mainstream and embayment. However, the relation between turbulence and mass transfer is poorly understood. In this study, we performed particle image velocity and laser-induced fluorescence experiments using a laboratory flume, laser light sheets and a high-speed CMOS camera. We examined the exchange properties of a dye as a function of bed configuration and sedimentation effect. Both primary and secondary gyres were observed in the flat bed and downward-sloping bed, whereas the primary gyre was prevalent in the upward-sloping bed. Moreover, the horizontal circulation strongly affected the mass-transfer properties between the mainstream and side cavity.