Photodegradation of hexachlorobenzene and theoretical prediction of its degradation pathways using quantum chemical calculation

Experimentally determined photodegradation pathways of hexachlorobenzene (HCB), a chlorinated aromatic compound, in hexane, 2-propanol (IPA), and methanol were compared with those predicted by quantum chemical calculation based on density functional theory (DFT), and the adequacy of the prediction method was evaluated. The experimental main degradation pathways of HCB were virtually the same for the three solvents and also agreed with the predicted main degradation pathways. In the DFT method, the main degradation product was the dechlorinated benzene at the position where the C-Cl bond was predicted to have the lowest bond dissociation energy. This result suggested that the photodechlorination pathways of chlorinated aromatic compounds could be predicted by comparing the bond dissociation energies calculated with the DFT method.     

Abiotic reduction of antimony(V) by green rust (Fe(4)(II)Fe(2)(III)(OH)(12)SO(4).3H(2)O)

Green rust (Fe(4)(II)Fe(2)(III)(OH)(12)SO(4).3H(2)O) is an intermediate phase in the formation of iron (oxyhydr)oxides such as goethite, lepidocrocite, and magnetite. It is widely considered that green rust occurs in many soil and sediment systems. Green rust has been shown to reduce sorbed Se(VI), Cr(VI), and U(VI). In addition, it is also reported that green rust does not reduce As(V) to As(III). In this study, we have investigated for the first time the interaction between Sb(V) and green rust using XAFS and HPLC-ICP-MS. Most of the added Sb(V) was adsorbed on green rust, and Sb(III), a reduced form, was observed in both solid and liquid phases. Thus, it was shown that green rust has high affinity for Sb(V), and that Sb(V) was reduced to more toxic Sb(III) by green rust despite the high stability of the Sb(V) species even under reducing condition as reported in previous studies. Therefore, green rust can be one of the most important reducing agents for Sb(V), which can influence the Sb mobility in suboxic environments where green rust is formed.     

Reproduction and recruitment of scleractinian corals in a high-latitude coral community, Amakusa, southwestern Japan

Reproduction and recruitment in high-latitude coral populations in Japan have been little studied. A comprehensive study of the reproduction and early life history was conducted on nine common scleractinian coral species in Amakusa, southwestern Japan (32°N) from 2001 to 2003 including; (1) fecundity (the proportion of colonies with mature eggs), (2) timing and synchrony of spawning, (3) initial larval settlement pattern, (4) recruitment, (5) post-settlement mortality. The fecundity was high (76.7–100%) in six of seven species examined in 2002 and 2003. Annual spawning of the seven species occurred from mid July to August in 2001–2003, when seawater temperature was at the annual maximum. Spawning was highly synchronised among conspecific colonies and species in 2002 and 2003, with five species spawning five to nine nights after the full moon and another two spawning around the new moon. Temporal patterns of larval settlement of three spawning species during the first 10 days after spawning were similar to those of other spawning species from low latitudes. The number of scleractinian recruits on settlement plates, deployed from July to October (the major recruitment period at the study site), was low (2 recruits/m²) for the three consecutive years. Post-settlement mortality of 1–1.5 month old spat of five species ranged between 88 and 100% over 3–10 months in the field, similar to the values reported for both high and low latitude species (>94–99%). Among the key stages examined, the low recruitment rate may be the most important step in limiting successful reproduction and recruitment of these high-latitude scleractinian populations. The low recruitment rate may be attributable to (1) the reduced influx of larval supply from other coral populations, which are smaller and more isolated at high-latitudes and (2) the longer precompetent larval phase of broadcast-spawning corals which results in an increased chance of larvae being dispersed away from parent populations.     

Analysis on the influence of forest soil characteristics on radioactive Cs infiltration and evaluation of residual radioactive Cs on surfaces

We investigated the depth profiles of radioactive Cs, ignition loss, and cation exchange capacity (CEC) in five types of forest soils sampled using scraper plates. We then simulated the monitored depth profiles in a compartment model, taking ignition loss as a parameter based on experimental results showing a positive correlation between ignition loss and the CEC. The calculated values were comparable with the monitored values, though some discrepancy was observed in the middle of the soil layer. Based on decontamination data on the surface dose rate and surface contamination concentration, we newly defined a surface residual index (SRI) to evaluate the residual radioactive Cs on surfaces. The SRI value tended to gradually decrease in forests and unpaved roads and was much smaller in forests and on unpaved roads than on paved roads. The radioactive Cs was assumed to have already infiltrated underground 18 months after the nuclear power plant accident, and the sinking was assumed to be ongoing. The SRI values measured on paved roads suggested that radioactive Cs remained on the surfaces, though a gradual infiltration was observed towards the end of the monitoring term. The SRI value is thought to be effective in grasping the rough condition of residual radioactive Cs quickly at sites of decontamination activity in the field. The SRI value may be serviceable for actual contamination works after further research is done to elucidate points such as the relation between the SRI and the infiltration of radioactive Cs in various types of objects.     

Temporal variation of Be concentrations in atmosphere for 8 y from 2000 at Yamagata,Japan: solar influence on the Be time series

We have been continuously observing the daily ⁷Be concentrations in surface air at Yamagata, Japan (38.25° N, 140.35° E) since 2000. The yearly profile of the ⁷Be concentration indicates the variation in galactic cosmic rays owing to solar modulation. Over 8 y, the ⁷Be concentration, cosmic neutrons, and number of sunspots varied by 37.4%, 12.2%, and 92.8%, respectively. The influence of precipitation on the ⁷Be variability was approximately 5%. Hence, the yearly ⁷Be concentration was mainly varied by the solar modulation of the ⁷Be production rates. Based on the production rates found in an EXPACS simulation, the observed variability indicates ⁷Be transport from high latitudes. The daily ⁷Be concentrations have two significant periodic components of 19 d and 36 d. The 36-d component implies a relationship between the sun's rotation and the vertical transport of air masses under quiet solar activity.     

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.     

Analysis of adsorption processes of dissolved organic matter (DOM) on ferrihydrite using surrogate organic compounds

Environmental Science and Pollution Research - Ferrihydrite (Fh) has been recently used in water treatment for removing dissolved organic matter (DOM), but its governing interactions with...     

Changes in the quality of chromophoric dissolved organic matter leached from senescent leaf litter during the early decomposition

Chromophoric dissolved organic matter (CDOM) leached from leaf litter is a major source of humus in mineral soil of forest ecosystems. While their functions and refractoriness depend on the physicochemical structure, there is little information on the quality of CDOM, especially for that leached in the very early stages of litter decomposition when a large amount of dissolved organic matter (DOM) is leached. This study aimed to better understand the variations/changes in the composition of CDOM leached from senescent leaf litter from two tree species during the early stage of decomposition. Leaf litter from a conifer tree (Japanese cedar, D. Don) and a deciduous broad-leaved tree (Konara oak, Thunb.) were incubated in columns using simulated rainfall events periodically for a total of 300 d at 20°C. The quality of CDOM was investigated based on the fluorescence properties by using a combination of excitation-emission matrix fluorescence (EEM) and parallel factor analysis (PARAFAC). In addition, the phenolic composition of DOM was investigated at a molecular level by thermally assisted hydrolysis and methylation-gas chromatography-mass spectrometry (THM-GC-MS) in the presence of tetramethylammonium hydroxide (TMAH). The EEM was statistically decomposed into eight fluorescence components (two tannin/peptide-like peaks, one protein-like peak, and five humic-like peaks). A significant contribution of tannin/peptide-like peaks was observed at the beginning of incubation, but these peaks decreased quickly and humic-like peaks increased within 1 mo of incubation. The composition of humic-like peaks was different between tree species and changed over the incubation period. Since tannin-derived phenolic compounds were detected in the DOM collected after 254 d of incubation on THM-GC-MS, it was suggested that tannins partially changed its structure, forming various humic-like peaks during the early decomposition.     

Polyfluorinated telomers in indoor air of Japanese houses

The fluorotelomer alcohols (FTOHs) have been detected in various environmental compartments, including indoor and outdoor air, in North America and Europe. In our previous studies, FTOHs were detected at a relative higher concentration in outdoor air in the Keihan (Kyoto–Osaka, one of the major industrial zones) area, Japan compared to reported data. The exposure level of FTOHs in indoor air in the Keihan area remains unclear. In the present study, indoor air FTOH concentrations were investigated using a passive air sampler containing activated carbon felts. The indoor air sampling was conducted in 49 households of the Keihan area, during winter and summer 2008. Most samples contained 6:2 FTOH, 8:2 FTOH, 10:2 FTOH and 8:2 FTOAc. The median concentration of 8:2 FTOH (5.84 ng m^?3) was highest among fluorotelomers, followed by those of 10:2 FTOH (1.12 ng m^?3), 6:2 FTOH (0.29 ng m^?3), and others. Significant correlations among fluorotelomers were observed in collected samples. The association between housing conditions and 8:2 FTOH concentrations showed that samples collected from bed rooms have higher 8:2 FTOH concentrations than those collected from other locations. In addition, samples collected in winter showed lower levels of 8:2 FTOH than those collected in summer. These findings suggest that 8:2 FTOH is the predominant component among fluorotelomers in indoor air, and that there are emission sources of fluorotelomers in indoor environments of the Keihan area. Further investigations into the origins of fluorotelomers are needed to evaluate indoor contamination with fluorotelomers.     

Detection of Dechlorane Plus and brominated flame retardants in marketed fish in Japan

Fish samples purchased from Japanese markets were analyzed for Dechlorane Plus (DP)(syn-, anti-), polybrominated diphenyl ether (PBDE), and hexabromocyclododecane (HBCD)(α, γ). Twenty fish were analyzed using gas chromatography-mass spectrometry for DP and PBDE, and using liquid chromatography-tandem mass spectrometry for HBCD. DP was detected in 18 samples and ∑DP concentrations were <0.2-14.2 pg g⁻¹ wet wt. Among the DP isomers, anti-DP was the dominant residue observed in this study. PBDE was detected in all samples. Concentrations of ∑PBDE ranged from 2.2 to 878 pg g⁻¹ wet wt. HBCD was detected in 18 samples, and ∑HBCD concentrations were <0.02-21.9 ng g⁻¹ wet wt. In fish landed near the East China Sea and the Sea of Japan, we detected relatively high concentrations of DP, PBDE, and HBCD. These results indicate that the seawaters around East Asia are contaminated with flame retardants. This study demonstrates the presence of DP in fish marketed in Japan for the first time.