Carbonaceous and inorganic composition in long-range transported aerosols over northern Japan: Implication for aging of water-soluble organic fraction

To better understand the influence of sources and atmospheric processing on aerosol chemical composition, we collected atmospheric particles in Sapporo, northern Japan during spring and early summer 2005 under the air mass transport conditions from Siberia, China and surrounding seas. The aerosols were analyzed for inorganic ions, organic carbon (OC), elemental carbon (EC), water-soluble organic carbon (WSOC), and the major water-soluble organic compound classes (i.e., dicarboxylic acids and sugars). SO₄^2? is the most abundant inorganic constituent (average 44% of the identified inorganic ion mass) followed by NH₄⁺ (21%) and NO₃^? (13%). Concentrations of OC, EC, and WSOC ranged from 2.0–16, 0.24–2.9, and 0.80–7.9 μg m^?3 with a mean of 7.4, 1.0, and 3.1 μg m^?3, respectively. High OC/EC ratios (range: 3.6–19, mean: 8.7) were obtained, however WSOC/OC ratios (0.23–0.69, 0.44) do not show any significant diurnal changes. These results suggest that the Sapporo aerosols were already aged, but were not seriously affected by local photochemical processes. Identified water-soluble organic compounds (diacids + sugars) account for <10% of WSOC. Based on some marker species and air mass back trajectory analyses, and using stable carbon isotopic compositions of shorter-chain diacids (i.e., C₂–C₄) as photochemical aging factor of organic aerosols, the present study suggests that a fraction of WSOC in OC is most likely influenced by aerosol aging, although the OC loading in aerosols may be more influenced by their sources and source regions.     

Evaluating the fish safety level of river water and wastewater with a larval medaka assay

A larval medaka (Oryzias latipes) assay was proposed to evaluate the fish safety level of river waters and wastewaters. Organic toxicants were 10-100 times concentrated with adsorption cartridges from 4 l of river water or 1-10 times concentrated from 400 ml of wastewater. Toxicity of these concentrated solutions was determined by exposing 48-72 h post-hatch age larvae for 48 h. The method effectively revealed a variation of the median lethal concentration ratio (LCR50) from 13 to >100 in 125 river water samples, and from <1 to >10 in five typical wastewater samples. Ayase River, which takes water mostly from agricultural or household discharge, showed significantly (P<0.001) lower LCR50 than Sagami River that takes natural water as the source. Safety Levels in both Sagami River and Ayase River were influenced by the irrigation activity, LCR50 at some sites showing a seasonal-specific decrease in winter. Pollution from pulp and paper industries contributed to the low LCR50 in several tributaries of Ayase River. Required little manpower in sampling, pretreatment and testing, the proposed larval medaka assay was proved as an efficient tool for screening those high risk sites for priority management.     

Seasonal change of PCDDs/PCDFs/DL-PCBs in the water of Ayase River, Japan: pollution sources and their contributions to TEQ

In Japan, Ayase River is one of the most polluted rivers by PCDDs, PCDFs and dioxin-like PCBs, which are referred to as dioxins in this paper. The water samples of the river were collected once per month for a year, and dioxins were analyzed to examine the dioxin sources and their contributions to toxic equivalent (TEQ). The WHO-2006 TEQs ranged from 0.26 to 7.0 pg-TEQ L⁻¹ and the average was 2.7 pg-TEQ L⁻¹; eight of 12 samples exceeded the environmental quality standard in Japan (1.0 pg-TEQ L⁻¹). The TEQ value was high during the irrigation period from May to August. The most part of the dioxins in the river water existed in suspended solids (SS) and it seemed that the river received water with highly-dioxin-contaminated SS in the irrigation period. The homologue profiles of the water samples suggested that the dioxins were influenced by pentachlorophenol (PCP) and chlornitrofen (CNP) formulations which were widely used as herbicides for the paddy fields in Japan. According to TEQ apportionment estimated by using indicative congeners, the TEQ was mainly contributed by PCP. Moreover, it was also shown that the TEQ contributions of PCP and CNP formulations increased along with the increase of the total TEQ and the TEQ contribution was dominated by these herbicides during the irrigation period. Therefore, it was concluded that the herbicides-originated dioxins run off from the paddy fields into the river during the irrigation period and increased the dioxins level in the river water. The result from the principal component analysis was consistent with these conclusions.     

Polychlorinated dibenzo-p-dioxins, dibenzofurans, and dioxin-like polychlorinated biphenyls in rice straw smoke and their origins in Japan

Polychlorinated dibenzo-p-dioxins (PCDDs), polychlorinated dibenzofurans (PCDFs), and dioxin-like polychlorinated biphenyls (DL-PCBs) contained in the smoke generated from rice straw burning in post-harvest paddy fields in Japan were analyzed to determine their congener profiles. Both the apportionment of toxic equivalent (TEQ) by using indicative congeners and the comparison of the homolog profiles showed that the PCDDs/PCDFs/DL-PCBs present in the rice-straw smoke were greatly influenced by those present as impurities in pentachlorophenol (PCP) and chlornitrofen (CNP, 4-nitrophenyl-2,4,6-trichlorophenyl ether) formulations that had been widely used as herbicides in paddy fields in Japan. Further, in order to investigate the effects of paddy-field soil on the PCDDs/PCDFs/DL-PCBs present in rice-straw smoke, PCDD/PCDF/DL-PCB homolog profiles of rice straw, rice-straw smoke and paddy-field soil were compared. Rice-straw smoke was generated by burning rice straw on a stainless-steel tray in a laboratory. The results suggested that the herbicides-originated PCDDs/PCDFs/DL-PCBs and the atmospheric PCDDs/PCDFs/DL-PCBs contributed predominantly to the presence of PCDDs/PCDFs/DL-PCBs in the rice-straw smoke while the contribution of PCDDs/PCDFs/DL-PCBs formed during rice straw burning was relatively minimal. The major sources of the PCDDs/PCDFs/DL-PCBs found in the rice-straw smoke were attributed primarily to the paddy-field soil adhered to the rice straw surface and secondarily to the air taken by the rice straw. The principal component analysis supported these conclusions. It is concluded that rice straw burning at paddy fields acts as a driving force in the transfer of PCDDs/PCDFs/DL-PCBs from paddy-field soil to the atmosphere.     

Degradation activity of Clostridium species DC-1 in the cis-1,2-dichloroethylene contaminated site in the presence of indigenous microorganisms and Escherichia coli

We showed the cis-1,2-dichloroethylene (cis-1,2-DCE) dechlorination ability of Clostridium species DC-1 in association with other bacteria. Result of denaturing gradient gel electrophoresis showed the dominant band pattern of DC-1 during the degradation time of cis-1,2-DCE and dominance of some other Clostridium species. Experiment with addition of Escherichia coli (E. coli) showed that dechlorinating activity of DC-1 was not inhibited by the presence of E. coli. Pour plate experiment with DC-1 and E. coli revealed that the dominance of Clostridium species caused the decrease of E. coli growth in a bioremediation state. This result suggested the possibility of Clostridium species DC-1 as a degrader of cis-1,2-DCE, in a cis-1,2-DCE contaminated site where an indigenous microbial community is present. Experiment conducting with E. coli suggested that the strain in the contaminated site did not inhibit the degradation of cis-1,2-DCE and during the degradation period, rather some other Clostridium species became dominant and the growth of E. coli would be decreased. This finding could be a very positive approach for implementing the dechlorinating bacteria at aliphatic chlorinated component contaminated sites.     

Estimation of internal radiation dose to the adult Asian population from the dietary intakes of two long-lived radionuclides

Daily dietary intakes of two naturally occurring long-lived radionuclides, 232Th and 238U, were estimated for the adult population living in a number of Asian countries, using highly sensitive analytical methods such as instrumental and radiochemical neutron activation analysis (INAA and RNAA), and inductively coupled plasma mass spectrometry (ICP-MS). The Asian countries that participated in the study were Bangladesh (BGD), China (CPR), India (IND), Japan (JPN), Pakistan (PAK), Philippines (PHI), Republic of Korea (ROK) and Vietnam (VIE). Altogether, these countries represent more than 50% of the world population. The median daily intakes of 232Th ranged between 0.6 and 14.4 mBq, the lowest being for Philippines and the highest for Bangladesh, and daily intakes of 238U ranged between 6.7 and 62.5 mBq, lowest and the highest being for India and China, respectively. The Asian median intakes were obtained as 4.2 mBq for 232Th and 12.7 mBq for 238U. Although the Asian intakes were lower than intakes of 12.3 mBq (3.0 ug) 232Th and 23.6 mBq (1.9 ug) 238U proposed by the International Commission on Radiological Protection (ICRP) for the ICRP Reference Man, they were comparable to the global intake values of 4.6 mBq 232Th and 15.6 mBq 238U proposed by the United Nation Scientific Commission on Effects of Radiation (UNSCEAR). The annual committed effective doses to Asian population from the dietary intake of 232Th and 238U were calculated to be 0.34 and 0.20 microSv, respectively, which are three orders of magnitude lower than the global average annual radiation dose of 2400 microSv to man from the natural radiation sources as proposed by UNSCEAR.     

Intercomparison of INAA and ICP-MS results for thorium determination in Pakistani diet

A pilot study on ingestion and organ content of trace elements of importance in radiological protection was to be carried out in Pakistan. Baseline analytical data on daily dietary intake of thorium was to be measured using Instrumental Neutron Activation Analysis (INAA) technique. To determine the accuracy and reliability of our technique, some samples were measured in Pakistan using INAA and in Japan using Inductively Coupled Plasma-Mass Spectrometry. For intercomparison of results overall mean Z-scores were calculated. The results showed validity of our technique. Mean value of 232Th concentration in Pakistani diet samples using INAA technique is 0.0062 +/- 0.0028 microg/g and with ICP-MS technique is 0.0069 +/- 0.0032 microg/g.     

Behavior of a hammerhead ribozyme in aqueous solution at medium to high temperatures

The “RNA world” hypothesis proposes that—early in the evolution of life—RNA molecules played important roles both in information storage and in enzymatic functions. However, this hypothesis seems to be inconsistent with the concept that life may have emerged under hydrothermal conditions since RNA molecules are considered to be labile under such extreme conditions. Presently, the possibility that the last common ancestor of the present organisms was a hyperthermophilic organism which is important to support the hypothesis of the hydrothermal origin of life has been subject of strong discussions. Consequently, it is of importance to study the behavior of RNA molecules under hydrothermal conditions from the viewpoints of stability, catalytic functions, and storage of genetic information of RNA molecules and determination of the upper limit of temperature where life could have emerged. In the present work, self-cleavage of a natural hammerhead ribozyme was examined at temperatures 10–200?°C. Self-cleavage was investigated in the presence of Mg²⁺, which facilitates and accelerates this reaction. Self-cleavage of the hammerhead ribozyme was clearly observed at temperatures up to 60?°C, but at higher temperatures self-cleavage occurs together with hydrolysis and with increasing temperature hydrolysis becomes dominant. The influence of the amount of Mg²⁺ on the reaction rate was also investigated. In addition, we discovered that the reaction proceeds in the presence of high concentrations of monovalent cations (Na⁺ or K⁺), although very slowly. Furthermore, at high temperatures (above 60?°C), monovalent cations protect the ribozyme against degradation.