Dynamics and Mass Balance of Polycyclic Aromatic Hydrocarbons in and Around the Seto Inland Sea, Japan.

Polycyclic aromatic hydrocarbons (PAHs) were analyzed to elucidate the distribution, ecological risk, pathways, and fluxes of these pollutants in and around the Seto Inland Sea, an industrialized coastal region of Japan. High molecular weight PAHs (5-6 rings) were primarily found in regions close to the bay estuaries, and their proportions decreased at distances further from the estuaries (offshore areas), where low molecular weight PAHs (2-4 rings) were more ubiquitous. Screening-level risk assessments revealed that the PAHs found in the sediments should have no adverse effects on benthic communities. A mass balance for PAHs in the Seto Inland Sea, calculated based on data collected in the field and published literature findings, showed the PAH flux into the Seto Inland Sea from atmospheric deposition were ca. 6 times higher than that from riverine inflows. Comparison of the amount of the PAH mass flux between the Seto Inland Sea and the sea of the Europe and Asian countries indicated that the Seto Inland Sea is less polluted than the Gulf of Lion, the Mediterranean Sea, and the Bohai Sea, China and more polluted than the Yellow Sea. This paper is the first to determine the fluxes of PAHs in the coastal region of Japan.

Characterization of Chromophoric Water-Soluble Organic Matter in Urban, Forest, and Marine Aerosols by HR-ToF-AMS Analysis and Excitation-Emission Matrix Spectroscopy.

Chromophoric water-soluble organic matter in atmospheric aerosols potentially plays an important role in aqueous reactions and light absorption by organics. The fluorescence and chemical-structural characteristics of the chromophoric water-soluble organic matter in submicron aerosols collected in urban, forest, and marine environments (Nagoya, Kii Peninsula, and the tropical Eastern Pacific) were investigated using excitation-emission matrices (EEMs) and a high-resolution aerosol mass spectrometer. A total of three types of water-soluble chromophores, two with fluorescence characteristics similar to those of humiclike substances (HULIS-1 and HULIS-2) and one with fluorescence characteristics similar to those of protein compounds (PLOM), were identified in atmospheric aerosols by parallel factor analysis (PARAFAC) for EEMs. We found that the chromophore components of HULIS-1 and -2 were associated with highly and less-oxygenated structures, respectively, which may provide a clue to understanding the chemical formation or loss of organic chromophores in atmospheric aerosols. Whereas HULIS-1 was ubiquitous in water-soluble chromophores over different environments, HULIS-2 was abundant only in terrestrial aerosols, and PLOM was abundant in marine aerosols. These findings are useful for further studies regarding the classification and source identification of chromophores in atmospheric aerosols.

Photodegradation of the insecticide fipronil in aquatic environments: photo-dechlorination processes and products.

Fipronil (FIP) is a phenylpyrazole insecticide that, along with neonicotinoid insecticides, is regularly used worldwide. Photodegradation of FIP in aqueous systems is thought mainly to involve the reaction of desulfinylation to give fipronil desulfinyl (FIP-desulfinyl); however, little is known about further degradation reactions. We investigated FIP photodegradation by analyzing photodegradation products by liquid chromatography and liquid chromatography high-resolution tandem mass spectrometry using an Orbitrap instrument. A wide range of products, including dechlorinated compounds, was detected, and the structures were identified. FIP-desulfinyl has previously been found to be an important and persistent FIP photodegradation product; however, we also found that FIP-desulfinyl was photochemically decomposed to a didechlorinated product via a monodechlorinated product. The main photodegradation pathway was probably similar to that of ethiprole, which has a similar skeleton. The photodegradation rate constant was 22.6 times lower for FIP-desulfinyl (0.00372 min-1) than FIP (0.0839 min-1). The photodegradation rate constant was lower for the newly found didechlorinated product (0.001 min-1 or below) than FIP-desulfinyl, suggesting that the product is persistent in aquatic environments and could be an important indicator of long-term FIP contamination.

Distribution and phylogeny of mercury methylation, demethylation, and reduction genes in the Seto Inland Sea of Japan.

Mercury (Hg) adversely affects human and environmental health. To evaluate the mercury (Hg) speciation (methylation, demethylation, and reduction) of microorganisms in coastal seawater, we analyzed the microbial functional gene sets involved in Hg methylation (hgcA and hgcB), demethylation (merB), and reduction (merA) using a metagenomic approach in the eastern and western parts (the Kii and Bungo channels, respectively) of the Seto Inland Sea (SIS) of Japan. We determined the concentration of dissolved total mercury (dTHg) and methylated mercury (dMeHg) in seawater. The metagenomic analysis detected hgcAB, merA, and merB in both channels, whereas the phylogenies of these genes differed between them. A correlation between Hg concentration (both dTHg and dMeHg) and the relative abundance of each gene was not observed. Our data suggests that microbial Hg methylation and demethylation could occur in the SIS and there could be a distinct microbial Hg speciation process between the Kii and Bungo channels.

Asian dust-deposition flux to the subarctic Pacific estimated using single quartz particles.

Iron availability limits marine ecosystem activities in large areas of the ocean. However, the sources and seasonal supply of iron, critically important for controlling surface ocean biogeochemistry and carbon cycling, are poorly understood. The western subarctic Pacific is a high-nutrient and low-chlorophyll region, and despite high concentrations of macronutrients, iron limits phytoplankton production in summer. Here, we determine the seasonal deposition flux of Asian dust using scanning electron microscope-cathodoluminescence analysis of single quartz particles derived from the western subarctic Pacific during 2003-2022 to trace provenance. We found a high (up to 6.9 mg m-2 day-1) deposition flux of Asian dust in May, June, and early July, with an annual average of 1.0 ± 0.2 mg m-2 day-1. The supply of dissolved-iron flux calculated from Asian dust was 0.9 ± 0.3 µg m-2 day-1 during the high productivity season (April-July), which is approximately half that from the deeper part of the ocean, calculated from vertical profiles of dissolved iron. Our study provides a reliable approach for estimating iron supply from dust to the surface ocean that may be critical for sustaining biological productivity under future ocean stratification, which suppresses nutrient supply from the subsurface ocean.

Wetting properties of fresh urban soot particles: Evaluation based on critical supersaturation and observation of surface trace materials.

Soot particles strongly absorb solar radiation and contribute to global warming. Also, wetting properties of soot at emission can affect its lifetime. We investigated surface conditions related to wetting and hydrophobic properties of fresh soot using data from measurements taken in Tokyo. A cloud condensation nuclei (CCN) counter was used to clarify surface conditions of particles composed mainly of water-insoluble (WI) materials: total and active particles as CCN around critical supersaturation (Sc) of 203-nm-diameter WI particles. Averaged number fractions of inactivated particles as CCN at 1.05% supersaturation (SS), which is Sc of hydrophilic WI particles, were estimated as 1.4%. Number fractions of inactive particles changed less at 1.78%SS during rush hour and increased at 0.89%SS, implying that most of the WI particles included small amounts of water-soluble (WS) materials rather than being completely hydrophobic. Based on transmission electron microscope (TEM) analysis of samples collected during rush hour, 69% of the mostly bare soot particles had Na or K small domains that are regarded as originating in fossil fuels. Based on water dialysis analysis results, some Na and K on soot were WS. Combination results with CCN measurements suggest that these WS materials decrease the Sc of soot. Moreover, the morphological structure of sulfate covering Na and K domains on the soot surface implicates pre-existing sodium and potassium compounds on soot as a trigger of soot aging. However, inactive particles at Sc at poor-hydrophilic particles and soot particles composed solely of WI materials on TEM samples were also found, although they were minor. Such particles, which are unfavorable for obtaining a wettable surface, might retain non-hygroscopicity for a longer period in the atmosphere. Evaluation of long-range soot transport can benefit from consideration of slight and inhomogeneous differences of chemical compounds on soot that occur along with their emission.

Migration of terephthalate from scraps of poly(ethylene terephthalate) (PET) in water and artificial seawater.

We report the migration of terephthalate and some low molecular weight organic compounds from poly(ethylene terephthalate) (PET) scraps in Milli-Q water and artificial seawater (ASW). The photochemical processes and the subsequent dark reactions were investigated using PET scraps obtained from postconsumer bottles of commercial non­carbonated mineral water. Concentrations of terephthalate exponentially increased with irradiation time, reaching approximately 6-8 µmol L-1 in ASW after 80 h irradiation. The photochemical migrations of compounds related to terephthalate were also observed. Concentrations of terephthalate and related compounds reached higher concentrations in ASW than in Milli-Q water. After 80 h irradiation, two dark experiments were conducted: one on the solutions after irradiation without PET scraps, and the other on photochemically damaged PET scraps. In ASW in the dark without PET scraps, the terephthalate concentration increased, and concentrations of other compounds related to terephthalate also changed. The results suggested that terephthalate was generated by hydrolytic reaction in dark ASW from the scission products of PET which were generated during the irradiation of PET scraps. Photochemically damaged PET scraps released terephthalate and related compounds in the dark. The half-life of the photo-irradiated PET scraps in the dark is approximately 205 years. Our results show that PET bottles in marine environments can continuously release terephthalate and other low molecular weight organic compounds during the day at the sunny surface, at the dark ocean floor, and during the night.

Optical properties of dissolved organic matter in Japanese rivers and contributions to photoformation of reactive oxygen species.

The optical properties of dissolved organic matter (DOM) from five rivers (Kokubu, Kurose, Ohta, Yamato, and Yodo) in Japan were investigated and contributions of DOM to photoformation of three reactive oxygen species (ROS) (hydroxyl radicals (OH), nitric oxide radicals (NO), and singlet oxygen (1O2)) were assessed. The lowest and highest mean dissolved organic carbon concentrations were for the Ohta River (0.95 (mg C) L-1) and Yamato River (2.85 (mg C) L-1), respectively, and the concentrations correlated with some optical parameters. Absorption ratios (e.g., the E2:E3 and A280/A350 ratios) and the spectral slope S275-295 indicated that DOM from the Yodo and Kokubu rivers had the lowest and highest molecular weights, respectively. PARAFAC models and DOM excitation-emission matrices were used to assess the sources and fates of DOM in the rivers. The PARAFAC model indicated that the main types of fluorescent DOM in the rivers were terrestrial humic-like (TH-L) and tryptophan-like (TP-L) substances. The Kokubu River contained other compounds such as fluorescent whitening agents, autochthonous humic-like substances, and extracellular polymeric substances. Statistically significant relationships between the dissolved organic carbon and TH-L, TP-L, and extracellular polymeric substance concentrations suggested that TH-L, TP-L, and extracellular polymeric substances are important contributors to total DOM in the rivers. TH-L and TP-L substances strongly contribute to ROS photoformation, but TH-L substances play roles in both ROS generation and scavenging. Comprehensive models for estimating the photoformation rates of different ROS (in M s-1) were established by integrating the contributions of the relevant major and minor sources. Examples are ROH (10-12) = 21.0 [NO2-]_µM + 0.460 [TH-L]_QSU + 10.9, RNO (10-12) = 67.9 [NO2-]_µM + 35.2 [a300]_m-1 - 2.51 [TH-L]_QSU - 0.765 [TP-L]_QSU - 8.14, and R1O2 (10-9) = 3.81 [a300]_m-1 - 0.101 [TP-L]_QSU + 11.1.

Comparison of characteristics of suicide attempters with schizophrenia spectrum disorders and those with mood disorders in Japan.

Suicidality in patients with schizophrenia is high. To clarify the characteristics of suicidal behavior in patients with schizophrenia, we investigated suicide attempters with schizophrenia spectrum disorders in comparison with patients with mood disorders. One hundred patients with schizophrenia spectrum disorders and 155 patients with mood disorders admitted to an emergency department after a suicide attempt were interviewed in detail on items concerning 1) demographic characteristics, 2) previous suicidal behavior, and 3) index suicidal behavior. Differences between the two groups were subsequently analyzed. Patients with schizophrenia spectrum disorders showed a lower incidence of previous deliberate self-harm, and a higher incidence of a subsequent suicide attempt more than 1 year after the previous suicide attempt as well as a higher lethality of index suicide attempt compared to patients with mood disorders. Furthermore, the most common motive for making a suicide attempt in patients with schizophrenia spectrum disorders was having a mental problem. This study revealed the factors associated with suicide attempts among Japanese patients with schizophrenia spectrum disorders, and the nature of these factors makes it difficult to predict future attempts. This makes clear the importance of continuous long-term follow-up with careful attention to the mental symptoms and psychological burden for such patients.

Factors controlling the degradation of hydrogen peroxide in river water, and the role of riverbed sand.

Diurnal changes of H2O2 in river water during mid-summer were investigated. H2O2 in river water increased with the increase in intensity of solar radiation in the morning, and reached a maximum at 14:00, although solar radiation reached a maximum around 12:00. In the afternoon, a gradual decrease in H2O2 was observed, and H2O2 reached a minimum just before sunrise. Degradation rate constants determined using unfiltered river water samples were 0.081-0.161 h-1, corresponding to a half-life of 4.3-8.5 h. We simulated diurnal changes in H2O2 using a simple formation, accumulation, and degradation model for static water using formation and degradation rate constants. The results of the modeling suggested that in situ degradation rate constants in rivers could be faster than those determined for unfiltered river water samples. Experiments using river sand indicated that riverbed sand could play an important role in H2O2 decay in rivers. We discussed the decomposition process of H2O2 in rivers.

Carbaryl residue concentrations, degradation, and major sinks in the Seto Inland Sea, Japan.

The fate of carbaryl in the Seto Inland Sea (west Japan) was predicted using a mass distribution model using carbaryl concentrations in river and sea water samples, degradation data, and published data. The predicted carbaryl concentrations in water in Kurose River and the Seto Inland Sea were 4.320 and 0.2134 µg/L, respectively, and the predicted concentrations in plankton, fish, and sediment were 0.4140, 2.436, and 1.851 µg/g dry weight, respectively. The carbaryl photodegradation and biodegradation rates were higher for river water (0.330 and 0.029 day-1, respectively) than sea water (0.23 and 0.001 day-1, respectively). The carbaryl photodegradation rates for river and sea water (0.33 and 0.23 day-1, respectively) were higher than the biodegradation rates (0.029 and 0.001 day-1, respectively). The hydrolysis degradation rate for carbaryl in sea water was 0.003 day-1, and the half-life was 231 days. Land (via rivers) was the main source of carbaryl to the Seto Inland Sea. The model confirmed carbaryl is distributed between sediment, plankton, and fish in the Seto Inland Sea. Degradation, loss to the Open Ocean, and sedimentation are the main carbaryl sinks in the Seto Inland Sea, accounting for 43.81, 27.90, and 17.68%, respectively, of total carbaryl inputs. Carbaryl source and sink data produced by the model could help in the management of the negative impacts of carbaryl on aquatic systems and human health.

Heterogeneity and potential aquatic toxicity of hydrogen peroxide concentrations in selected rivers across Japan.

Hydrogen peroxide (H2O2) is a reactive oxygen species formed in natural water. It is reportedly toxic to aquatic organisms with a predicted no-effect concentration (PNEC) of about 380 nM. In this study, a countrywide investigation of H2O2 concentrations in selected rivers across Japan was conducted to identify rivers that pose toxicity concerns. Twelve rivers with a total catchment area of 13,646 km2 were selected from different prefectures. Spatial and temporal variation studies showed that the H2O2 concentrations (avg. 320 nM, n = 111) varied by two orders of magnitude (range 21-2929 nM) across the rivers. The Yamato River in Osaka and Nara prefectures and the Kokubu River in Chiba Prefecture had the highest concentrations at 276-669 nM and 236-2929 nM, respectively. >75% of the data from the two rivers were either close to or exceeded the PNEC. Most of the results for the other rivers were less than the PNEC. There was a clear seasonal variation in the H2O2 concentrations, with the highest values obtained in summer because of high solar irradiation. The H2O2 concentration had the highest positive correlation (r = 0.61, p < 0.01, n = 111) with the product of dissolved organic carbon and solar radiation intensity, which suggests that these two factors in combination are important in determining the H2O2 concentrations in river water. It was also observed that bigger rivers had lower H2O2 concentration and vice-versa. This shows that the size of a river may influence its H2O2 concentration. This study is the first countrywide survey of H2O2 concentrations in different rivers and evaluation of their relationship with the PNEC. The data provide insight on the factors influencing the concentrations of H2O2 in river water.

Characteristics of suicide attempters with family history of suicide attempt: a retrospective chart review.

BACKGROUND: Family history of suicide attempt is one of the risks of suicide. We aimed at exploring the characteristics of Japanese suicide attempters with and without a family history of suicide attempt. METHODS: Suicide attempters admitted to an urban emergency department from 2003 to 2008 were interviewed by two attending psychiatrists on items concerning family history of suicide attempt and other sociodemographic and clinical information. Subjects were divided into two groups based on the presence or absence of a family history of suicide attempt, and differences between the two groups were subsequently analyzed. RESULTS: Out of the 469 suicide attempters, 70 (14.9%) had a family history of suicide attempt. A significantly higher rate of suicide motive connected with family relations (odds ratio 2.21, confidence interval 1.18-4.17, p < .05) as well as a significantly higher rate of deliberate self-harm (odds ratio 2.51, confidence interval 1.38-4.57, p < .05) were observed in patients with a family history of suicide compared to those without such history. No significant differences were observed in other items investigated. CONCLUSION: The present study has revealed the characteristics of suicide attempters with a family history of suicide attempt. Further understanding of the situation of such individuals is expected to lead to better treatment provision and outcomes, and family function might be a suitable focus in their treatment.

Corrigendum: Collocated observations of cloud condensation nuclei, particle size distributions, and chemical composition.

This corrects the article DOI: 10.1038/sdata.2017.3.

Collocated observations of cloud condensation nuclei, particle size distributions, and chemical composition.

Cloud condensation nuclei (CCN) number concentrations alongside with submicrometer particle number size distributions and particle chemical composition have been measured at atmospheric observatories of the Aerosols, Clouds, and Trace gases Research InfraStructure (ACTRIS) as well as other international sites over multiple years. Here, harmonized data records from 11 observatories are summarized, spanning 98,677 instrument hours for CCN data, 157,880 for particle number size distributions, and 70,817 for chemical composition data. The observatories represent nine different environments, e.g., Arctic, Atlantic, Pacific and Mediterranean maritime, boreal forest, or high alpine atmospheric conditions. This is a unique collection of aerosol particle properties most relevant for studying aerosol-cloud interactions which constitute the largest uncertainty in anthropogenic radiative forcing of the climate. The dataset is appropriate for comprehensive aerosol characterization (e.g., closure studies of CCN), model-measurement intercomparison and satellite retrieval method evaluation, among others. Data have been acquired and processed following international recommendations for quality assurance and have undergone multiple stages of quality assessment.

Effect of JTT-705 on cholesteryl ester transfer protein and plasma lipid levels in normolipidemic animals.

This study evaluated JTT-705, S-[2-([[1-(2-ethylbutyl)cyclohexyl]carbonyl]amino)phenyl]2-methylpropanethioate, as a cholesteryl ester transfer protein (CETP) inhibitor in several animal species. In vitro, JTT-705 inhibited plasma CETP activities of humans, rabbits, hamsters, cynomolgus monkeys and marmosets with IC(50) values of 5.5, 1.0, 11.7, 2.4 and 6.3 microM, respectively. The thiol form (JTP-25203) also inhibited those activities with IC(50) values of 2.8, 0.44, 0.52, 1.3 and 1.1 microM, respectively. Following oral administration to normolipidemic animals (rabbits, hamsters and marmosets), JTT-705 reduced plasma CETP activity, increased high density lipoprotein cholesterol (HDL-cholesterol), and decreased the ratio of non-HDL-cholesterol to HDL-cholesterol (atherogenic index) in all species. In marmosets, JTT-705 increased slow alpha-migrating lipoprotein (apolipoprotein E-rich HDL) in agarose gel electrophoresis, indicating that HDL metabolism in JTT-705-treated marmosets is similar to that in CETP-deficient humans. These results indicate that JTT-705 can be expected to inhibit plasma CETP activity and improve plasma lipoprotein profiles in a wide range of animal species, including humans.