A study on emission of phthalate esters from plastic materials using a passive flux sampler

Phthalate esters are used as plasticizer in many plastics, and several studies have shown their toxicity. Phthalate esters are gradually emitted over time, and so it is conceivable that they pose a significant health risk. This study aims to investigate the temperature dependence of the emissions of various phthalate esters and to estimate the health risks of these emissions at various temperatures. A passive-type sampler was developed to measure the flux of phthalate esters from the surface of plastic materials. With this sampler, we examined three widely used plastic materials: synthetic leather, wallpaper and vinyl flooring. The observed maximum emissions of diethyl phthalate, dibutyl phthalate, and diethylhexyl phthalate (DEHP) from these materials at 20°C were 0.89, 0.77, and 14 μg m⁻² h⁻¹, respectively. Emissions at 80°C were 2.8, 4.5×10², and 1.5×10³ μg m⁻² h⁻¹, respectively. The results showed this temperature dependence is determined primarily by the type of phthalate ester and less so by the type of material. The estimation from the results of temperature dependence indicated the concentration of DEHP in a vehicle left out in the sunshine during the day can exceed the recommended levels of Japan Ministry of Health, Labour and Welfare.     

Thermodynamic investigation of the effect of oxygen and hydrogen chloride potential upon generation and decomposition behavior of dioxins

The thermodynamic equilibrium of the C‐H‐O‐Cl system has been calculated to elucidate the generation and decomposition behavior of dioxins, and is discussed from the viewpoint of the oxygen and hydrogen chloride potential. The dioxins behavior is greatly dependent on the oxygen potential, i.e. higher temperature and oxygen potential lead to the complete decomposition of dioxins, while low hydrogen chloride potential under insufficient oxygen condition leads to an increase of multi‐chlorine displacement of dioxins.     

Chronic kidney diseases of uncertain etiology (CKDue) in Sri Lanka: geographic distribution and environmental implications

The increase in the number of chronic kidney disease (CKD) patients from the north central region of Sri Lanka has become a environmental health issue of national concern. Unlike in other countries where long-standing diabetes and hypertension are the leading causes of renal diseases, the majority of CKD patients from this part of Sri Lanka do not show any identifiable cause. As the disease is restricted to a remarkably specific geographical terrain, particularly in the north central dry zone of the country, multidisciplinary in-depth research studies are required to identify possible etiologies and risk factors. During this study, population screening in the prevalent region and outside the region, analysis of geoenvironmental and biochemical samples were carried out. Population screening that was carried out using a multistage sampling technique indicated that the point prevalence of CKD with uncertain etiology is about 2–3% among those above 18 years of age. Drinking water collected from high-prevalent and non-endemic regions was analyzed for their trace and ultratrace element contents, including the nephrotoxic heavy metals Cd and U using ICP-MS. The results indicate that the affected regions contain moderate to high levels of fluoride. The Cd contents in drinking water, rice from affected regions and urine from symptomatic and non-symptomatic patients were much lower indicating that Cd is not a contributing factor for CKD with uncertain etiology in Sri Lanka. Although no single geochemical parameter could be clearly and directly related to the CKD etiology on the basis of the elements determined during this study, it is very likely that the unique hydrogeochemistry of the drinking water is closely associated with the incidence of the disease.     

Field validation of an active sampling cartridge as a passive sampler for long-term carbonyl monitoring

A carbonyl sampler originally designed for the active sampling method (Sep-Pak XPoSure) was used for long-term passive sampling, and its applicability as a passive sampler was examined through field experiments. The uptake rates of passive sampling were determined experimentally from collocated passive and active samplings for various sampling periods. The obtained uptake rates of formaldehyde, acetaldehyde, and acetone were 1.48, 1.23, and 1.08 mL/min, respectively. These uptake rates were consistent for a wide range of the sampling term (12 hr-2 weeks). Uptake rates of each carbonyl were proportional to the diffusion coefficients of each. Therefore, the ratios of diffusion coefficients were used to calculate the uptake rates of carbonyls for which the rates were not determined experimentally. Lower limits of determination were 2.16-17.5 microg/m3 for 2-week sampling. It was confirmed that 2-week monitoring of carbonyl concentrations up to 118-229 microg/m3 was possible. Relative standard deviations of the passive method generated from the repeatability test were 2-12.3% error for five samplings, and the recovery efficiencies were larger than 90%. Thus, the passive sampler was found to be highly suitable for long-term monitoring of carbonyl compounds.     

Relationship between dietary exposure and serum perfluorochemical (PFC) levels—A case study

Daily dietary intake of perfluorinated chemicals (PFCs) in relation to serum levels was assessed by determination of nine PFCs including perfluorooctane sulfonate (PFOS) and perfluorooctanoic acid (PFOA) in matched daily diet duplicates and serum samples. Diet and serum were collected in year 2004 from 20 women in Osaka and Miyagi, Japan. Only PFOS and PFOA were detected in the diet samples and no significant difference between cities was seen. After adjusted by water content, diet concentration of PFOA was significantly higher in Osaka. The median daily intake calculated using the measured diet concentrations was 1.47 ng PFOS/kg b.w. and 1.28 ng PFOA/kg b.w. for Osaka, and 1.08 ng PFOS/kg b.w. and 0.72 ng PFOA/kg b.w. for Miyagi. A significant difference between cities was seen for the serum concentrations with median of 31 ng/mL PFOS and PFOA in Osaka, compared to 14 ng/mL PFOS and 4.6 ng/mL PFOA in Miyagi. Carboxylates such as perfluorononanoic acid (PFNA) and perfluoroundecanoic acid (PFUnDA) were also detected in serum at median levels 6.9 ng/mL and 3.2 ng/mL (Osaka), and 2.8 ng/mL and 5.1 ng/mL (Miyagi). Based on one-compartment model under steady state, dietary intake of PFOS and PFOA accounted for only 22.4% and 23.7% of serum levels in Osaka females, and in contrast 92.5% and 110.6% in Miyagi females, respectively.     

Hydrostatic pressure-induced apoptosis on nauplii of Calanus sinicus

The effect of hydrostatic pressure on embryonic development of the calanoid copepod Calanus sinicus was studied. Differences of pressure effect among blastomere stages, 1-cell, 2-cell, 4-cell, 8-cell, 16-cell, blastula and limb-bud stage, were examined under two pressurizing conditions, abruptly (10 atm/min) and gradually (0.1 atm/min) increasing. Egg hatching success, deformity frequency and apoptotic cell degradation of hatched nauplii were examined. Egg hatching success rate was not significantly different between blastomere stages, and also between pressurizing conditions. Deformity frequencies of hatched nauplii were low in the early 1-cell and 2-cell stages, and high in the later blastula and limb-bud stages, in both abrupt and gradual pressurizing conditions. On the other hand, in regard to difference in pressurizing conditions, deformity frequency in gradual pressurizing was significantly higher than that in abrupt pressurizing rate. Gradual pressure increase seems to be more harmful to C. sinicus eggs than abrupt pressure change. Apoptosis induced in nauplii by hydrostatic pressure was detected for the first time in marine zooplankton. The embryos of C. sinicus are sensitive to pressure variations, that is, these embryos are supposed to sink to deeper waters, incurring greater risk of having deformities. In the field, C. sinicus ascend to the surface and spawn at night. By looking from this upward behavior, eggs are spawned at lower pressure and warmer temperature. Probably, the harmless low pressure and warm temperature lead eggs to hatch early and to recruit successfully.     

Hydrostatic pressure-induced apoptosis on nauplii of Calanus sinicus

The effect of hydrostatic pressure on embryonic development of the calanoid copepod Calanus sinicus was studied. Differences of pressure effect among blastomere stages, 1-cell, 2-cell, 4-cell, 8-cell, 16-cell, blastula and limb-bud stage, were examined under two pressurizing conditions, abruptly (10 atm/min) and gradually (0.1 atm/min) increasing. Egg hatching success, deformity frequency and apoptotic cell degradation of hatched nauplii were examined. Egg hatching success rate was not significantly different between blastomere stages, and also between pressurizing conditions. Deformity frequencies of hatched nauplii were low in the early 1-cell and 2-cell stages, and high in the later blastula and limb-bud stages, in both abrupt and gradual pressurizing conditions. On the other hand, in regard to difference in pressurizing conditions, deformity frequency in gradual pressurizing was significantly higher than that in abrupt pressurizing rate. Gradual pressure increase seems to be more harmful to C. sinicus eggs than abrupt pressure change. Apoptosis induced in nauplii by hydrostatic pressure was detected for the first time in marine zooplankton. The embryos of C. sinicus are sensitive to pressure variations, that is, these embryos are supposed to sink to deeper waters, incurring greater risk of having deformities. In the field, C. sinicus ascend to the surface and spawn at night. By looking from this upward behavior, eggs are spawned at lower pressure and warmer temperature. Probably, the harmless low pressure and warm temperature lead eggs to hatch early and to recruit successfully.     

Identification of nonvolatile neutral organic compounds in tap water

Nonvolatile neutral organic compounds in tap water were examined by high-pressure liquid chromatography, infrared spectrometry, ¹H- and ¹³C-FT-NMR, gel permeation chromatography, elementary analysis, and field desorption mass spectrometry. Neutral organic compounds in 10 m³ of tap water were continuously extracted by the Amberlite XAD-2 resin column, and separated into four fractions by silica-gel column chromatography. Removal of volatile compounds in fraction 3 including polar oxygenated compounds was carried out with microdistillation column under high vacuum by using a diffusion pump. Nonvolatile organic compounds isolated from tap water were identified as poly(vinyl acetate) derivatives with molecular weights ranging from 300 to 1300.     

Improved method for the formation of recycled resins from depolymerized products of waste fiber-reinforced plastics: simple and effective purification of recovered monomers by washing with water

The synthesis of recycled plastics from recovered monomeric materials obtained from the depolymerization reaction of fiber-reinforced plastics (FRP) was examined. The depolymerization reaction of FRP in the presence of N,N-dimethylaminopyridine (DMAP) smoothly yielded the corresponding monomers, which mainly consisted of dimethyl phthalates. The polymerization reaction with this monomer failed to form the corresponding unsaturated polyesters due to contamination by N-methyl-4-pyridone, a decomposition product of DMAP. An efficient purification of the recovered monomer was achieved by washing with water, and the purified monomer successfully yielded the corresponding polymers. A hardness test revealed that the polymers were as hard as the polyester made from virgin materials. The present modification provides a practical method for the preparation of recycled plastics from depolymerized plastics.     

Levels and profiles of long-chain perfluorinated carboxylic acids in human breast milk and infant formulas in East Asia

In this study, 90 human breast milk samples collected from Japan, Korea, and China were analyzed for perfluorooctanoic acid (PFOA) (C8), perfluorononanoic acid (PFNA) (C9), perfluorodecanoic acid (PFDA) (C10), perfluoroundecanoic acid (PFUnDA) (C11), perfluorododecanoic acid (PFDoDA) (C12), and perfluorotridecanoic acid (PFTrDA) (C13). In addition, infant formulas (n = 9) obtained from retail stores in China and Japan were analyzed. PFOA was the predominant compound and was detected in more than 60% of samples in all three countries. The PFOA, PFNA, PFDA, and PFUnDA levels in Japan were significantly higher than those in Korea and China (p < 0.05). The PFTrDA level was highest in Korea (p < 0.05). The median PFOA concentrations were 89 pg mL⁻¹ (48% of total perfluorinated carboxylic acids (PFCAs) (C8-C13)) in Japan, 62 pg mL⁻¹ (54%) in Korea, and 51 pg mL⁻¹ (61%) in China. The remaining ∑PFCAs (C9-C13) were 95 pg mL⁻¹ in Japan, 52 pg mL⁻¹ in Korea, and 33 pg mL⁻¹ in China. Among the long-chain PFCAs, odd-numbered PFCAs were more frequently detected than even-numbered PFCAs, except for PFDA in Japan. There were no evident correlations between the mother’s demographic factors and the PFCA concentrations. PFOA, PFNA, and PFDA were frequently detected in both Japan and China, but there were no significant differences between the two countries. The total PFCA concentrations in the infant formulas were lower than those in the breast milk samples in Japan (p < 0.05), but not in China (p > 0.05). In conclusion, various PFCAs were detected in human breast milk samples from East Asian countries.