The association between clustering based on composition of volatile organic compound in indoor air and building-related symptoms.

Volatile organic compounds (VOCs) have been suspected to cause building-related symptoms (BRSs). Although some studies investigated the association between BRSs and VOCs in indoor air, those results were inconsistent. This study investigated the contamination status of VOCs in the indoor air of 154 houses in Japan. Additionally, these samples were grouped by hierarchical clustering analysis based on the VOC composition, and the relationship between a VOC cluster and the BRSs was investigated. The median concentration of the sum of VOCs (ΣVOCs) was 140 µg m-3 (range: 18-3500 µg m-3). The levels of acetaldehyde in four samples and p-dichlorobenzene in one sample exceeded the guideline value. As a result of the hierarchical clustering analysis, the samples in this study were divided into six characteristic clusters based on the VOC composition. The ΣVOCs in cluster 1 were significantly lower than those in other clusters. In cluster 2, acyclic and aromatic hydrocarbons were dominant. Cluster 3 had a relatively high proportion of limonene. In cluster 4, the concentrations and composition ratios of α-pinene were higher than those of other clusters. In cluster 5, p-dichlorobenzene accounted for 42 %-72 % of the total VOCs. Cluster 6 had a relatively high proportion of decamethyl cyclopentasiloxane. This clustering likely depended on the construction of houses and lifestyles. As a result of logistic regression analysis, cluster 5 was associated with the cough symptoms of the BRSs. The results of the present study suggest that investigating the association between VOCs and BRSs is necessary to consider not only total concentrations such as TVOC and ΣVOCs but also VOC composition.

Determination of brominated flame retardants including polybrominated diphenyl ethers, pentabromoethylbenzene, hexabromobiphenyl, and decabromodiphenyl ethane in sediment samples: Validation of a rapid and efficient clean-up method and application to a sediment core from Lake Biwa, Japan.

The development of rapid and efficient analytical method for the determination of legacy and current-use brominated flame retardants (BFRs) has been performed due to environmental concern related to these pollutants. In the present study, we used an automated clean-up device equipped with pre-packed micro-column sets (containing sulfuric acid impregnated silica gel and silver-modified alumina) to develop an effective purification method for polybrominated diphenyl ethers (PBDEs), pentabromoethylbenzene, hexabromobiphenyl, and decabromodiphenyl ethane (DBDPE) in sediment extracts. Matrix-spiked sediments (n = 6) and the Standard Reference Material® 1944 samples (n = 6) were tested. Our method showed acceptable accuracy, repeatability, and sensitivity for almost all the target compounds with reduced processing time, labor requirement, and solvent amounts as compared to conventional clean-up method (e.g., sulfuric acid treatment and self-packed chromatographic columns). The validated method was applied to sediment core samples (n = 16) collected in 2019 from Lake Biwa, the largest lake in Japan. PBDEs were detected in sediment samples of 0-13 cm depth (dated between 1990 and 2019) at relatively low concentrations (median 5.7; range 2.6-9.4 ng/g dry weight). PBDE profiles were dominated by BDE-209, which accounted for 91 ± 10% of total PBDEs. Among other BFRs, only DBDPE was found in sediment layers of 0-9 cm depth (deposited between 2005 and 2019). DBDPE concentrations ranged from 0.43 to 1.6 (median 0.71) ng/g and showed increasing trend toward shallower depths.

Comparison of the enzymatic digestibility of physically and chemically pretreated selected line of diploid-Miscanthus sinensis Shiozuka and triploid-M.×giganteus.

The diploid Miscanthus sinensis "Shiozuka" which was selected as a high-biomass producing line, and the triploid M. × giganteus (M×G) were treated by ball milling (physical treatment) and alkaline hydrogen peroxide treatment (AHP; chemical treatment), and their structural sugar compositions and enzymatic digestibility were compared. The structural sugar content of Shiozuka was moderate and lower than that of M×G. The Klason lignin content of Shiozuka was also lower than that of M×G. However, Shiozuka was sensitive to ball milling and AHP treatment; ball milled and AHP-treated Shiozuka had higher enzymatic digestibility than ball milled and AHP-treated M×G. Shiozuka would be promising feedstock to obtain fermentable sugars with low energy consumption. Finally, enzymes for the hydrolysis of chemically treated Miscanthus were isolated from Trichoderma reesei ATCC 66589 and Penicillium pinophilum. The sugar yield could be increased by enzymatic hydrolysis of AHP-treated samples with NaOH and H2O2 and the isolated enzymes.

Ethanol-based organosolv treatment with trace hydrochloric acid improves the enzymatic digestibility of Japanese cypress (Chamaecyparis obtusa) by exposing nanofibers on the surface.

The effects of adding trace acids in ethanol based organosolv treatment were investigated to increase the enzymatic digestibility of Japanese cypress. A high glucose yield (60%) in the enzymatic hydrolysis was obtained by treating the sample at 170 °C for 45 min in 50% ethanol liquor containing 0.4% hydrochloric acid. Moreover, the enzymatic digestibility of the treated sample was improved to ∼70% by changing the enzyme from acremonium cellulase to Accellerase1500. Field emission scanning electron microscopy revealed the presence of lignin droplets and partial cellulose nanofibers on the surface of the treated sample. Simultaneous saccharification and fermentation of the treated samples using thermotolerant yeast (Kluyveromyces marxianus NBRC1777) was tested. A high ethanol concentration (22.1 g/L) was achieved using the EtOH50/W50/HCl0.4-treated sample compared with samples from other treatments.

Physicochemical characteristics of carbonaceous adsorbent for dioxin-like polychlorinated biphenyl adsorption.

It has been known that dioxin-like polychlorinated biphenyls (DL-PCBs) are present in almost all types of environments worldwide. Activated carbon treatment has been expected for the removal of DL-PCBs because it is a simple and low-cost removal technology. In the present study, the physicochemical properties of activated carbon were investigated to identify the characteristics of 16 different types of activated carbon on adsorption properties for DL-PCBs. To accomplish this, micropore volume, and pore diameter were calculated by t-plot analysis and the mesopore volume was analyzed by the Barrett-Joyner-Halenda (BJH) method. In addition, the Brunauer-Emmett-Teller (BET) surface area, pH, metal elements, and surface acid functional groups were analyzed. Then, adsorption experiments using DL-PCB in hexane solution were conducted, and the relationship between adsorption and physicochemical properties of activated carbon was investigated. The results showed that activated carbons having a surface area of 700-1200 m(2)g(-1) and micropores with diameters of about 0.7-0.8 nm exhibited high activity for the adsorption of PCBs. The results also clearly showed that the mesopore volume of activated carbon influenced the adsorption rate and the equilibrium adsorption.

Dioxin-like polychlorinated biphenyl adsorbent obtained from enzymatic saccharification residue of lignocellulose.

In this study, the effective utilization of lignocellulose residue as an adsorbent was investigated. Japanese cypress wood flour subjected to hydrothermal pretreatment and ball-mill grinding was saccharified with an enzyme. The residual wood flour was carbonized and activated by physical and chemical activation to produce adsorbents for persistent organic pollutant removal. The adsorption properties were investigated by pore analysis using the N(2) adsorption/desorption isotherm and adsorption tests for dioxin-like polychlorinated biphenyls in a hexane solution. The obtained adsorbents showed high production yields and adsorption properties for dioxin-like polychlorinated biphenyls.

Degradation of methylene blue by radio frequency plasmas in water under ultraviolet irradiation.

The degradation of methylene blue by radio frequency (RF) plasmas in water under ultraviolet (UV) irradiation was studied experimentally. When the methylene blue solution was exposed to RF plasma, UV irradiation from a mercury vapor lamp enhanced degradation significantly. A lamp without power supply also enhanced degradation since weak UV light was emitted weakly from the lamp due to the excitation of mercury vapor by stray RF power. Such an enhancement is explained by the fact that after hydrogen peroxide is produced via the recombination process of OH radicals around the plasma, OH radicals reproduced from hydrogen peroxide via the photolysis process degrade methylene blue.

Economic assessment of batch biodiesel production processes using homogeneous and heterogeneous alkali catalysts.

An economic feasibility study on four batch processes for the production of biodiesel ranging from 1452 tonnes/year (5000 l/day) to 14,520 tonnes/year (50,000 l/day) is conducted. The four processes assessed are the (1) KOH-W process, characterized by a homogeneous KOH catalyst and hot water purification process; (2) KOH-D process, characterized by a homogeneous KOH catalyst and vacuum FAME distillation process; (3) CaO-W process, characterized by a heterogeneous CaO catalyst and hot water purification process; and (4) CaO-D process, characterized by a heterogeneous CaO catalyst and vacuum FAME distillation process. The costs of the waste cooking oil, fixed costs, and manufacturing costs for producing 7260 tonnes/year (25,000 l/day) of biodiesel by means of the four processes are estimated to be $248-256, $194-232, and $584-641 per tonne of biodiesel, respectively. Among the four processes, the manufacturing costs involved in the CaO-W process are the lowest, in the range from 1452 tonnes/year to 14,520 tonnes/year.

Removal of dioxins and dioxin-like PCBs from fish oil by countercurrent supercritical CO2 extraction and activated carbon treatment.

It has been known that fish oils are prone to contamination by polychlorinated dibenzo-p-dioxins (PCDDs), polychlorinated dibenzofurans (PCDFs), and dioxin-like polychlorinated biphenyls (DL-PCBs). In this study, the removal of contaminants from fish oil by countercurrent supercritical CO(2) extraction (CC-SCE) and activated carbon treatment was investigated. Fish oil was treated by CC-SCE at 70 degrees C and 30MPa and with a CO(2)/oil ratio of 72; this resulted in a 93% reduction in the sum of PCDDs, PCDFs and DL-PCBs concentration level by and 85% reduction in toxic equivalency (TEQ). CC-SCE uses 40% less CO(2) and yields 30% more refined oil than semi-batch-type processes. Subsequent treatment by activated carbon reduced the concentration level by 94% and TEQ by 93%. CC-SCE is effective for the removal of DL-PCBs, whereas activated carbon treatment is effective for the removal of PCDD/Fs. These results reveal that the combination of CC-SCE and activated carbon treatment is applicable to the removal of PCDD/Fs and DL-PCBs from fish oil.

Acceleration of catalytic activity of calcium oxide for biodiesel production.

This research was aimed at studying the acceleration of the catalytic activity of calcium oxide (CaO) for developing an effective heterogeneous catalyst for biodiesel production by the transesterification of plant oil with methanol. CaO was activated by pretreatment with methanol and was used for the transesterification reaction. The activation and transesterification reaction conditions were examined. The obtained optimal reaction conditions were 0.1-g CaO, 3.9-g methanol, 15-g rapeseed oil, and 1.5-h activation time at room temperature that provided methyl ester in approximately 90% yield within a reaction time of 3h at 60 degrees C. The activation mechanism was also investigated, and the proposed mechanism is as follows. By pretreatment with methanol, a small amount of CaO gets converted into Ca(OCH(3))(2) that acts as an initiating reagent for the transesterification reaction and produces glycerin as a by-product. Subsequently, a calcium-glycerin complex, formed due to the reaction of CaO with glycerin, functions as the main catalyst and accelerates the transesterification reaction.

Development of supercritical carbon dioxide extraction with a solid phase trap for dioxins in soils and sediments.

A method involving supercritical fluid extraction (SFE) with a solid phase trap containing activated alumina was investigated for the rapid analysis of polychlorinated dibenzo-p-dioxins (PCDDs), polychlorinated dibenzofurans (PCDFs), and dioxin like polychlorinated biphenyls (DL-PCBs) in soils and sediments. The samples were extracted by using supercritical carbon dioxide with water (2% versus CO(2) flow velocity) being used as an entrainer at a pressure of 30 MPa and a temperature of 130 degrees C for 50 min. The extracts were adsorbed on an activated alumina trap that was maintained at a temperature of 150 degrees C, and then, PCDD/DFs and DL-PCBs were eluted with 20 ml of hexane at 60 degrees C. After concentration, they were measured with a high-resolution gas chromatograph interfaced to a high-resolution mass spectrometric detector. The average concentrations of PCDD/DFs and DL-PCBs corresponded to the results obtained by the conventional method, and the reproducibility of this SFE method was below 21% of the relative standard deviations for all samples. The total time required for the analysis of the pretreatment of this method was only 2 h.

Development of heterogeneous base catalysts for biodiesel production.

Investigations were conducted on heterogeneous base catalysts for the transesterification of oil aimed at effective production of biodiesel. Thirteen different kinds of metal oxides containing calcium, barium, magnesium, or lanthanum were prepared as catalysts. Their catalytic activities were tested for transesterification at 60 degrees C with a 6:1 molar ratio of methanol to oil and a reaction time of 10h. The calcium-containing catalysts - CaTiO3, CaMnO3, Ca2Fe2O5, CaZrO3, and CaO-CeO2 - showed high activities and approximately 90% yields of methyl ester. Furthermore, catalytic durability tests were performed by repeating the transesterification reaction several times with the calcium-containing catalysts recovered from the previous reaction mixture. It was found that CaZrO3 and CaO-CeO2 show high durability and have the potential to be used in biodiesel production processes as heterogeneous base catalysts.

A supercritical carbon dioxide plasma process for preparing tungsten oxide nanowires.

A supercritical carbon dioxide (CO(2)) plasma process for fabricating one-dimensional tungsten oxide nanowires coated with amorphous carbon is presented. High-frequency plasma was generated in supercritical carbon dioxide at 20 MPa by using tungsten electrodes mounted in a supercritical cell, and subsequently an organic solvent was introduced with supercritical carbon dioxide into the plasma. Electron microscopy and Raman spectroscopy investigations of the deposited materials showed the production of tungsten oxide nanowires with or without an outer layer. The nanowires with an outer layer exhibited a coaxial structure with an outer concentric layer of amorphous carbon and an inner layer of tungsten oxide with a thickness and diameter of 20-30 and 10-20 nm, respectively.

Experimental study on the removal of dioxins and coplanar polychlorinated biphenyls (PCBS) from fish oil.

Recently, it has been found that fish oils contain a high proportion of contaminants, namely, polychlorinated dibenzo-p-dioxins (PCDDs), polychlorinated dibenzofurans (PCDFs), and coplanar polychlorinated biphenyls (cPCBs). In this study, the removal of contaminants from fish oil by supercritical CO2 extraction (SCE) and by using adsorbents (0.13 wt % of oil) was investigated. Dioxins and cPCBs were extracted from fish oil by SCE at a temperature of 60 degrees C and a pressure of 28 MPa, and the removal efficiencies for PCDDs and PCDFs were in the range of 15-90% and those for cPCBs were in the range of 70-90%. However, 40% of the oil was extracted simultaneously with contaminants. On the adsorbent treatment, activated carbon showed high efficiency, and the removal efficiencies were >90% for PCDDs and PCDFs, but below 30% for cPCBs. A combination of both of these methods is more effective, and almost 100% of the total toxicity equivalence quantity value could be reduced.

Influence of the characteristics of soil and fly ash on the supercritical carbon dioxide extraction of dioxins.

Several investigations on the extraction of dioxins from soil and fly ash with supercritical fluid have been reported; however, few of them describe the influence of components on the extraction. We extracted dioxins from eight samples with different values of organic carbon content and surface area with supercritical CO(2) at a temperature of 463 K, a pressure of 40 MPa, and using 10% toluene as an entrainer. We researched the influence of the characteristics of soil and fly ash on supercritical CO(2) extraction of dioxins. The results revealed that the extraction efficiencies of PCDD/DFs and PCBs were high for all soil samples, while that of fly ash samples decreased with the increase in organic carbon content and surface area. The extraction efficiencies of dioxins from four standard samples, activated carbon, humic acid, alumina, and florisil, were also examined. The results revealed that the extraction efficiencies were strongly influenced by activated carbon like components present in the samples.