Prevalence and associated metabolic factors of nonalcoholic fatty liver disease in the general population from 2014 to 2018 in Japan: A large-scale multicenter retrospective study.

AIM: The prevalence of nonalcoholic fatty liver disease (NAFLD) is increasing worldwide. The aim of this study was to determine the recent prevalence and clinical characteristics of NAFLD in Japan. METHODS: This study initially included 410 061 retrospectively enrolled adults from the medical health checkup registry for metabolic syndrome, chronic kidney disease, and fatty liver in Japan (MIRACLE-J; UMIN-CTR no. UMIN000049419), who were evaluated between 2014 and 2018 at 13 health centers in Japan. Individuals consuming >20 g of alcohol/day or with chronic liver disease were excluded. Fatty liver was diagnosed by ultrasonography. The probability of NAFLD with advanced fibrosis was estimated based on the fibrosis-4 index and NAFLD fibrosis score. RESULTS: A total of 71 254 participants were included in the final analysis. The overall prevalence of NAFLD was 25.8%. There was a significant, twofold difference in NAFLD prevalence between men (37.4%) and women (18.1%). Nonalcoholic fatty liver disease prevalence increased linearly with body mass index, triglycerides, and low-density lipoprotein cholesterol regardless of threshold values, even in the absence of obesity. Among patients with NAFLD, 14% had diabetes mellitus, 31% had hypertension, and 48% had dyslipidemia. The estimated prevalence of NAFLD with advanced fibrosis was 1.7% and 1.0% according to the fibrosis-4 index and NAFLD fibrosis score, respectively. CONCLUSIONS: The prevalence of NAFLD was approximately one-quarter of the general population in Japan. There was a linear relationship between NAFLD prevalence and various metabolic parameters, even in nonobese participants. The prevalence of NAFLD with advanced fibrosis was estimated to be 1%-2%.

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.

Singlet Oxygen Photogeneration in Coastal Seawater: Prospect of Large-Scale Modeling in Seawater Surface and Its Environmental Significance.

Chromophoric-dissolved organic matter (CDOM) acts as the precursor to singlet oxygen (1O2) in natural waters, while water acts as the main scavenger. In this study, we showed that 1O2 in coastal seawater can be successfully predicted from CDOM parameters. The 1O2 steady-state concentration [1O2]ss and photoformation rate (R1O2) varied by a factor of 6 across 13 sampling stations in the Seto Inland Sea, Japan, ranging from 1.2 to 8.2 × 10-14 M and 3.32 to 22.7 × 10-9 M s-1, respectively. Investigation of CDOM optical properties revealed that CDOM abundance measured as the absorption coefficient at 300 nm (a300) had the strongest correlation (r = 0.96, p < 0.001) with [1O2]ss, while parameters indicative of CDOM quality (e.g., spectral slope) did not influence [1O2]ss. A linear relationship between [1O2]ss and a300, normalized to a sunlight intensity of 0.91 kW/m2, was derived as [1O2]ss (10-14 M) = 2.12(a300) + 0.48. This was then used to predict [1O2]ss using a300 values from a subsequent, independent sampling exercise conducted 2 years after the first sampling. There was a good agreement (r = 0.93, p < 0.001) between the predicted values and the experimentally determined values based on a 95% prediction interval plot. Kinetic estimations using [1O2]ss suggest that 1O2 mediates the degradation of tetrabromobisphenol A in surface seawater (t1/2 = 0.63 days) while also contributing to the indirect photolysis of methyl mercury. The findings from this study suggest that large-scale modeling of 1O2 generation in surface seawater from CDOM parameters is possible with useful environmental significance for determining the fate of pollutants.

Temporal trends in organophosphorus pesticides use and concentrations in river water in Japan, and risk assessment.

We reviewed organophosphorus pesticide use in Japan between 1982 and 2016 using data from the National Institute of Environmental Studies. Organophosphorus pesticide concentrations in river water throughout Japan were taken from the literature, and risk assessments were performed for some organophosphorus pesticides based on risk quotients and hazard quotients. Assessments were performed for 20 common pesticides, including insecticides, fungicides, and herbicides. The amounts used decreased in the order: insecticides > herbicides > fungicides. Organophosphorus insecticide and fungicide use have decreased over the last four decades, but organophosphorus herbicide use has increased. During this period, annual organophosphorus pesticide use was the highest for chlorpyrifos (105,263 tons/year) and the lowest for glyphosate-sodium (8 tons/year). The ecotoxicological risk assessment indicated that diazinon and fenitrothion posed strong risks to the Japanese aquatic environment, and chlorpyrifos and malathion have moderate risks. None of the pesticides that were assessed posed significant risks to humans. Continued use of organophosphorus pesticides in Japan may cause strong risks to aquatic environments. These risks should be reassessed periodically.

Individual and combined effects of fluoranthene, phenanthrene, mannitol and sulfuric acid on marigold (Calendula officinalis).

A study was conducted to characterize marigold stress response to polycyclic aromatic hydrocarbons (PAHs) (oxidative stress inducers) with and without sulfuric acid (S.Acid; pH 3) (acid-stress inducer), and to evaluate reactive oxygen species (ROS) scavenging activity of mannitol (Mann). Marigold (Calendula officinalis) seedlings were grown in a greenhouse and fumigated with fluoranthene (FLU), phenanthrene (PHE), Mann, and S.Acid individually and in various combinations for 40 days. Various physiological and biochemical parameters among others were analyzed using standard methods. The results revealed that fumigation of FLU induced oxidative stress to the plants via ROS generation leading to negative effects on photosynthesis at near saturating irradiance (Amax), stomatal conductance (Gs), internal carbon dioxide concentration (Ci), leaf water relations and chlorophyll pigments. Significant per cent inhibition of Amax (54%), Gs (86%) and Ci (32%), as well as per cent reductions in chlorophyll a (Chl.a) (33%), Chl.b (34%), and total chlorophyll (Tot. Chl) (48%) contents were recorded in FLU fumigated treatment in comparison to control. Combination of Mann with FLU scavenged the generated ROS and substantially lowered the oxidative stress on the plants hence all the measured parameters were not significantly different from control. PHE fumigation had varied effects on marigold plants and was not as deleterious as FLU. Combined fumigation of S.Acid with both the PAHs had significant negative effect on leaf water relations, and positive effect on fresh and turgid weight of the plants but had no effect on the other measured parameters. The lowest proline contents and highest catalase and ascorbate peroxidase activities in FLU fumigated plants further confirmed that oxidative stress was imposed via the generation of ROS. From the results, it is evident that Mann could be an efficient scavenger of ROS-generated by FLU in the marigold plants. We recommend Mann to be widely used for the protection of higher plants from FLU-generated stress in the urban areas.

Evaluation of Levels, Sources and Health Hazards of Road-Dust Associated Toxic Metals in Jalalabad and Kabul Cities, Afghanistan.

This study was designed to investigate selected road-dust associated heavy metals, their relations with natural and anthropogenic sources, and potential human and environmental health risks. For this purpose, 42 and 36 road-dusts samples were collected from Jalalabad and Kabul cities (Afghanistan), respectively. The following elements were found in descending concentrations: Mn, Zn, Pb, Ni, Cu, Cr, Co, and Cd in Jalalabad; and Mn, Zn, Ni, Cu, Cr, Pb, Co, and Cd in Kabul. Except for Ni, all the elemental contents were less than the Canadian permissible limits in residential/parkland soils. Principle Component Analysis and enrichment of Cd, Cu, Ni, Pb, and Zn pointed to anthropogenic sources, whereas Co, Cr, and Mn indicated crustal inputs. Broadly, Cd monomial risk index ([Formula: see text]) was considerable; however, one site each in both cities showed high risk ([Formula: see text] ≥ 350). The potential ecological risk (RI) is mostly low; however, at some sites, the risk was considerable. Ingestion appeared to be the main exposure route (99%) for heavy metals and contributed > 90% to noncancerous (all residents), as well as 92% (children) and 75-89% (adults) cancerous risks. The noncancerous risks of all metals and their integrated risks for all residents were within acceptable levels. Moreover, potential cancer risks in children from Ni and Cr were slightly higher than the US-EPA safe levels but were within acceptable levels for adults. This study found higher risks to children and therefore recommends proper management and ways to control metals pollution load in these areas to decrease human health and RIs.

Spatio-temporal variations of selected pesticide residues in the Kurose River in Higashi-Hiroshima city, Japan.

This study investigated spatio-temporal variations of selected pesticide residues in the Kurose River in Higashi-Hiroshima city (Hiroshima Prefecture), Japan. Water samples were collected from the river at seven sites every month for 1 year (March 2016 to February 2017). Pesticide residues were extracted from the samples by a solid phase extraction using Sep Pack C18 cartridges. Once extracted, the samples were analyzed for cyanazine, simetryn, fenarimol, isoprothiolane, and diazinon using a reversed-phase high-performance liquid chromatography ultraviolet visible (HPLC-UV Vis) system. The limits of detection were 3.60, 4.10, 2.80, 6.50, and 7.30 ng L-1 for cyanazine, simetryn, fenarimol, isoprothiolane, and diazinon, respectively. Good recovery rates (88%-102%), and mean percent relative standard deviation range (1.00%-5.70%) (n = 6) were obtained with a spiking at 0.20 µg L-1. The maximum concentrations of 282, 391, 60, 1086, and 1194 ng L-1 were obtained for cyanazine, simetryn, isoprothiolane, fenarimol, and diazinon, respectively. Cyanazine was the most frequently detected pesticide (64% of the samples, n = 84), followed by simetryn (58%), and then diazinon (57%). The highest and lowest pesticide concentrations were measured during the periods May-June, and January-February, respectively. Principal component analysis revealed three principal components in which the pesticides were linked to dissolved organic matter and total suspended solids. The major water quality parameters (electrical conductivity, pH, Na+, K+, Mg2+, Ca2+, NH4+, NO3-, Cl-, SO42-, NO2-, and temperature) showed no clear trends for these pesticides. The presence of simetryn and isoprothiolane was largely attributed to rice paddy farms, whereas diazinon was associated mostly with vegetable farms and orchards. The diazinon and isoprothiolane patterns were consistent with their use of controlling insects and fungi in the prefecture. The maximum diazinon concentration detected was higher than the human safe level specified by the European Union (100 ng L-1) in Council Directive 98/83/EC. This is of concern because of the bioconcentration potential of these residues in fish and other marine animals consumed by humans.

Concentrations of polycyclic aromatic hydrocarbons: Their potential health risks and sources at three non-urban sites in Japan.

This investigation was undertaken to monitor particulate polycyclic aromatic hydrocarbons (PAHs) concentrations in order to determine their emission sources and potential human health risks in remote and rural areas of Japan. Seventeen PAHs in aerosol samples collected in remote (Kamihaya), coastal (Hiki) and inland (Higashi-Hiroshima) areas of Japan during 2013-2014 were analyzed using gas chromatography/mass spectrometry. Total PAH (Σ17PAH) concentrations in aerosol samples were in the range of 0.08-6.51 ng m(-3), 0.09-4.74 ng m(-3), and 0.21-6.53 ng m(-3) at Kamihaya, Hiki, and Higashi-Hiroshima sites, with mean concentrations of 1.63, 1.18, and 2.43 ng m(-3), respectively. Significant seasonal variation in concentrations occurred at Hiki and Higashi-Hiroshima, while no significant variation occurred at Kamihaya. Ambient air temperature greatly affected PAH concentrations in Higashi-Hiroshima, but had only moderate effects in Kamihaya and Hiki. Wind direction also influenced the concentrations of PAHs. Vehicle exhaust, industrial emissions, biomass combustion, and domestic heating and cooking were identified as the main PAH emission sources using principal component analysis. Backward trajectory calculations showed that domestically generated PAHs were significant in Kamihaya and Hiki, while in Higashi-Hiroshima concentrations were mainly influenced by long-range transport. The incremental lifetime lung cancer risk had values of 3.38 × 10(-5) and 1.84 × 10(-5) at Higashi-Hiroshima and Hiki, which are greater than the US EPA acceptable level (10(-6)). Typically, 5-6-ring PAHs contributed 95% to this overall health risk, of which benzo(a)pyrene was the largest contributor, followed by dibenz(a,h)anthracene at both residential sites. Clearly, stricter guidelines for PAHs need to be implemented at these sites to protect the population.

Simultaneous photoinduced generation of Fe(2+) and H2O2 in rivers: An indicator for photo-Fenton reaction.

The photo-Fenton reaction is a key source of the highly reactive hydroxyl radical (HO) that is produced by the reaction of simultaneous photo-induced generation of Fe(2)(+)-dissolved organic matter (DOM) with H2O2 in sunlit surface waters as well as in the treatment of organic pollutants in the advanced oxidation processes (AOPs). Concentrations of both H2O2 and Fe(2)(+)-DOM were dependent on time and total solar intensity flux, and their levels were highest in the diurnal samples collected at noon compared with the samples collected during the period before sunrise and after sunset. H2O2 and Fe(2)(+)-DOM concentrations during monthly readings were also found higher in comparison with the diurnal samples, shortly before sunrise or after sunset. A π-electron bonding system is formed between Fe and the functional groups in DOM (Fe-DOM), through electron donation from the functional groups of DOM to an empty d-orbital of Fe. The π-electron is loosely bound and is highly susceptible to a rapid excitation upon light exposure that will provide better understanding of the formation of aqueous electrons, superoxide radical anions, H2O2 and finally, photo-Fenton reactions, too. Our results imply that simultaneous generation of H2O2 and Fe(2)(+)-DOM upon sunlight exposure during the daytime is most likely to be the key photo-Fenton reaction pathway, taking place in surface waters.

Recessive inheritance of population-specific intronic LINE-1 insertion causes a rotor syndrome phenotype.

Sequences of long-interspersed elements (LINE-1, L1) make up ∼17% of the human genome. De novo insertions of retrotransposition-active L1s can result in genetic diseases. It has been recently shown that the homozygous inactivation of two adjacent genes SLCO1B1 and SLCO1B3 encoding organic anion transporting polypeptides OATP1B1 and OATP1B3 causes a benign recessive disease presenting with conjugated hyperbilirubinemia, Rotor syndrome. Here, we examined SLCO1B1 and SLCO1B3 genes in six Japanese diagnosed with Rotor syndrome on the basis of laboratory data and laparoscopy. All six Japanese patients were homozygous for the c.1738C>T nonsense mutation in SLCO1B1 and homozygous for the insertion of a ∼6.1-kbp L1 retrotransposon in intron 5 of SLCO1B3, which altogether make up a Japanese-specific haplotype. RNA analysis revealed that the L1 insertion induced deleterious splicing resulting in SLCO1B3 transcripts lacking exon 5 or exons 5-7 and containing premature stop codons. The expression of OATP1B1 and OATP1B3 proteins was not detected in liver tissues. This is the first documented case of a population-specific polymorphic intronic L1 transposon insertion contributing to molecular etiology of recessive genetic disease. Since L1 activity in human genomes is currently seen as a major source of individual genetic variation, further investigations are warranted to determine whether this phenomenon results in other autosomal-recessive diseases.

Novel Fluorometric Method for the Determination of Production Rate and Steady-State Concentration of Photochemically Generated Superoxide Radical in Seawater Using 3',6'-(Diphenylphosphinyl)fluorescein.

Superoxide radical (O2(•-)) is an important reactive oxygen species in seawater. Measurements of its production rates and steady-state concentrations generated by photochemical processes have been a Herculean task over the years. In this study, a probe - 3'6'-(diphenylphosphinyl)fluorescein (PF-1) - was used to trap photochemically generated O2(•-) in seawater, thereby yielding fluorescein. The fluorescein produced was measured by an isocratic fluorescence HPLC at excitation/emission wavelengths of 490/513 nm, respectively. The reaction rate constant of PF-1 with O2(•-) (kPF-1) was pH-dependent: (3.2-23.5) × 10(7) M(-1) s(-1) at pHTOT 7.65-8.50. By applying appropriate equations, both the production rate and the steady-state concentration of O2(•-) generated by photochemical reactions in the seawater were quantified. Under the optimized experimental conditions, fluorescein standards (3-50 nM) exhibited linearity in the seawater by HPLC. The photoformation of fluorescein, due to the reaction of PF-1 with the O2(•-) photochemically produced in the seawater, was linear within the 20 min irradiation. The detection limit of the fluorescein photoformation rate was 0.03 pM s(-1), defined as 3σ of the lowest standard fluorescein concentration per 20 min irradiation. Using this value, the yield of fluorescein, and the fraction of O2(•-) that reacted with PF-1 in the seawater, the detection limit of the O2(•-) photoformation rate was 1.78 pM s(-1). Superoxide measurements using the proposed method were relatively unaffected by the potential interfering species in seawater. Application of the proposed method to ten (10) seawater samples from the Seto Inland Sea, Japan, resulted in measured O2(•-) photoformation rates of 3.1-8.5 nM s(-1), with steady-state concentrations ranging (0.06-0.3) × 10(-10) M. The method is simple, requires no technical sample preparation, and can be used to analyze a large number of samples.

Identification of atmospheric ozone generated from seismic activity during the occurrence of multiple earthquakes across Japan in 2022.

Ground-level atmospheric ozone (tropospheric ozone) is a well-known indicator of photochemical air pollution. Atmospheric ozone may also be an indicator of earthquake generation. Ground-level observations of atmospheric ozone at multiple sites were conducted in this study at the time of multiple earthquake occurrences in Japan in 2022. As the result of this study, ozone peaks of unknown origin were detected during the occurrence of multiple earthquakes across Japan in 2022. The level of these ozone peaks began to increase from a few days to a few hours before each earthquake, reaching a maximum concentration coincident with the time of earthquake generation. 'Unknown ozone' were detected at near earthquake epicentres, except in the case of deep earthquakes. The 'unknown ozone' were also associated with earthquake seismic intensities, which were monitored at seismograph stations in various Japanese cities, towns, and villages. A laboratory experiment by Baragiola et al. (2011) indicated that ppm levels of ozone can be generated in air by the crushing and grinding of terrestrial crustal rocks, generated by exo-electrons emitted by high electric fields, resulting from charge separation during rock fracture. Baragiola et al. (2011) proposed a hypothesis whereby atmospheric ozone could be generated via rock fracturing during the occurrence of earthquakes. This hypothesis could explain the ozone peaks correlating with multiple Japanese earthquakes observed in this study. The significance of atmospheric ozone generated by seismic activity is discussed in terms of it being a possible indicator of earthquake generation and prediction.

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.

Protective and curative effects of foliar-spray Fenton solutions against cucumber (Cucumis sativus, L.) powdery mildew.

Various Fenton solutions have been developed for advanced oxidation processes in wastewater treatment. In this study, conventional Fenton solutions such as hydrogen peroxide (HOOH) + Fe(2+) (Mix 1) or HOOH + Fe(3+) (Mix 2), and a new type of solution, HOOH + Fe(3+) + oxalic acid (Mix 3), were used as foliar sprays against powdery mildew on cucumber caused by Sphaerotheca fuliginea. Three Fenton solutions, plus a fungicide, fenarimol, were used to cure and/or protect the plant from powdery mildew under greenhouse conditions. Determination of the ·OH photoformation rate of these Fenton solutions revealed that Mix 3 had a photoformation rate 3.6 - 4.3 times higher than those of Mix 1 and 2. Application of fenarimol and Mix 3 to each plant once a week for three weeks resulted in high curative effects for already-diseased plants. Double spraying with fenarimol and the Mix 3 solutions 1-7 days before S. fuliginea inoculation resulted in the protective effects continuing for up to 20 days after spraying. When the disease reemerged at 20 days post inoculation, one reapplication of the spray suppressed the disease for another 7 days. Overall, fenarimol and Mix 3 were most effective for both the protection and suppression of the disease. These results implied that Mix 3 had fungicidal effects similar to fenarimol; therefore, the use of a Fenton solution such as Mix 3 may offer new possibilities for disease control.

[A rare case report of incarceration of Lambl's excrescence of aortic valve resulting in myocardial infarction].

We report a rare autopsy case of Lambl's excrescence of the aortic valve resulting in myocardial infarction. A 50-year-old female patient was referred to our hospital, but she died 4 hours after admission due to myocardial infarction. Autopsy disclosed Lambl's excrescence of the aortic valve, which obstructed the main branch of the left coronary artery. Histologically, fibrin thrombus and bacterial flora were found on surface of Lambl's excrescence. Differential diagnosis of infected Lambl's excrescence, so called endocarditis with infected vegetation, and papillary fibroelastomais discussed with a literature review.

Ecotoxicological and human health risk assessment of selected pesticides in Kurose River, Higashi-Hiroshima City (Japan).

This study conducted an integrated approach combining monitoring and risk assessment of pesticides in Kurose River and its catchment area, Japan. Water samples (n = 168) were collected every month for 1 year (March 2016 to February 2017). Pesticides (cyanazine, simetryn, fenarimol, isoprothiolane, and diazinon) were extracted by Sep-Pack C18 cartridges and analyzed using a reversed-phase HPLC-UV system. The pesticides were also determined in non-target organisms Red algae (Audouinella sp.) and diatoms (Cocconeis placentula) from the river. Based on the residual concentrations, an ecotoxicological risk assessment was conducted using the risk quotient (RQ) index. The human health carcinogenic and non-carcinogenic risk assessments were evaluated using hazard quotients (HQ). Results showed that cyanazine was the most commonly detected (64%), followed by simetryn (58%), and diazinon (57%) in all the sample sites (n = 12). Except for isoprothiolane, the pesticides were highest in spring followed by summer, autumn and winter. Based on extreme values (ex), non-acceptable ecotoxicological risk was obtained for diazinon (RQex = 21.317), cyanazine (RQex = 3.129), simetryn (RQex = 8.577) and fenarimol (RQex = 10.855), while that of isoprothiolane (RQex  = 0.013) was negligible. Based on the HQ estimates, all the pesticides were below the threshold value of 1, hence pose no significant health risks to humans. PRACTITIONER POINTS: Pesticides affect non-target organisms in rivers and other aquatic systems Pesticides were frequently detected in spring and summer and accumulated in red algae and diatom The detected pesticides posed high ecotoxicological and human health risks.

Contamination, dynamics, and health risk assessment of pesticides in seawater and marine samples from the Seto Inland Sea, Japan.

We assessed the contamination, dynamics, and health risks of the pesticides cyanazine, simetryn, fenarimol, isoprothiolane, diazinon, irgarol, fenitrothion, and diuron in marine samples (seawater, sediments, plankton, fish, and other edible organisms) at various locations in the Seto Inland Sea in Japan in 2016 and 2017. Pesticide concentrations were highest at sampling sites close to the coastline, and mean concentrations in seawater were slightly higher in surface water than in bottom water. All eight pesticides were detected in plankton. Diazinon concentrations (77-387 ng/g dw) were highest in sediments and cyanazine was the most frequently detected pesticide (88%, n = 17) in sediments. Only cyanazine (2.7-41.9 ng/g dw), simetryn (1.0-34.3 ng/g dw), and diazinon (6.3-308.8 ng/g dw) were detected in fish and other edible marine organisms. Based on the calculated bioconcentration factor, the results showed that plankton, fish, and marine animals bioaccumulated pesticides. The highest hazard quotients were calculated for diazinon in red seabream and greenling, indicating a possible risk to consumers. It is, therefore, imperative to promote strict implementation of pollution control, integrated pest management practices, and policy formulation on pesticides. Usage of diazinon must be controlled and monitored to ensure large residues do not reach aquatic ecosystems and marine coastlines.

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.

Photochemically generated nitric oxide in seawater: The peroxynitrite sink and its implications for daytime air quality.

In this study, we experimentally investigated the magnitude of the peroxynitrite sink: a radical-radical consumption mechanism for photochemically generated nitric oxide (NO) in surface seawater that describes NO reactions with co-generated superoxide (O2-) to yield peroxynitrite (ONOO-). Measurements of photochemically generated NO, O2- and ONOO- were conducted on seawater samples obtained from the Seto Inland Sea, Japan. Nitrite, dissolved organic carbon, chromophoric dissolved organic matter and pH were also measured in the same samples using standard analytical methods. The average photoformation rates of NO, O2- and ONOO- were: 1.78 × 10-12 M s-1, 7.19 × 10-10 M s-1 and 9.0 × 10-10 M s-1, respectively, and the average steady-state concentrations were: 67.28 × 10-12 M, 2.69 × 10-12 M and 2.26 × 10-11 M, respectively. Further evaluation of the experimental data indicated that the existence of ONOO- in seawater strongly depends on, and is limited by, photoformed NO. Seawater alkalinity favored the consumption of photoformed NO· via the peroxynitrite sink. The magnitude of average sinks (%) calculated from kinetic estimates and experimental data were: 0.17% and 0.11%, respectively. These results show that the consumption of photochemically generated NO· via the peroxynitrite sink is not significant in surface seawater. Therefore, we propose that sea-to-air efflux across the marine boundary layer is the major sink of photochemical NO· and can be regarded as a non-anthropogenic contributor to daytime atmospheric NOx concentrations.