Evaluation of pressurized liquid extraction for determination of organophosphorus and pyrethroid pesticides in soybean

The purpose of this study was to develop an analytical method for the determination of organophosphorus and pyrethroid pesticides in soybean by pressurized liquid extraction (PLE). Two organic solvents, acetone and acetonitrile, were evaluated as extraction solvents. In both cases, the amount of extract was enhanced with increasing extraction temperature. The extracts obtained using acetonitrile were measured by gas chromatography/mass spectrometry after a cleanup process based on the analytical method for the Japanese Positive List System for Agricultural Chemicals Remaining in Foods. The effect of extraction temperature (range: 40– 130°C) on extraction efficiency was evaluated by a recovery study using 21 organophosphorus pesticides and 10 pyrethroid pesticides as target analytes and acetonitrile as the solvent. The results indicated that at 130°C, some organophosphorus pesticides might be degraded, whereas extraction temperatures between 70°C and 100°C were optimal. Next, a prepared sample containing fenitrothion and permethrin was analyzed. Although the sample was not soaked in water prior to analysis, PLE provided analytical results comparable to those obtained by solvent extraction with homogenization. Therefore, PLE is considered a simple and alternative technique for the extraction of organophosphorus and pyrethroid pesticides in soybean.     

Laboratory studies of the diffusive transport of Cs and Co through potential waste repository soils

Tests using reconstituted samples have been performed to assess the diffusive transport of ¹³⁷Cs and ⁶⁰Co through natural regolith materials from a region in South Australia being considered for a radioactive waste repository. A double diffusion cell apparatus made of polycarbonate resin was developed to estimate the effective diffusion (D_e) and sorption coefficients (K_d) that allowed large withdrawals from the source and collector cells and has enabled tests with low concentrations of radioactivity. An alternative to porous stainless steel filter plates has also been used to reduce uncertainty in test interpretation. Analysis of the transient data used a staged method of the Laplace transform to take into consideration the volume of the samples withdrawn from the apparatus during testing. At test completion samples were cut into slices and analysed for radionuclide concentration. Data obtained from the sliced samples confirmed that both numerical and experimental data produced acceptable mass balance. The D_e values obtained in this study were of the order of 10⁻⁶ cm² s⁻¹ for both species, higher than previously published data. The K_d values from the diffusion and batch sorption tests were in reasonable agreement for ¹³⁷Cs, but an order of magnitude different for ⁶⁰Co. The sorption of the latter radionuclide was strongly pH dependent, and this dependency during diffusion tests would benefit from further investigation.     

Evaluation of pressurized liquid extraction for determination of organophosphorus and pyrethroid pesticides in soybean

The purpose of this study was to develop an analytical method for the determination of organophosphorus and pyrethroid pesticides in soybean by pressurized liquid extraction (PLE). Two organic solvents, acetone and acetonitrile, were evaluated as extraction solvents. In both cases, the amount of extract was enhanced with increasing extraction temperature. The extracts obtained using acetonitrile were measured by gas chromatography/mass spectrometry after a cleanup process based on the analytical method for the Japanese Positive List System for Agricultural Chemicals Remaining in Foods. The effect of extraction temperature (range: 40- 130°C) on extraction efficiency was evaluated by a recovery study using 21 organophosphorus pesticides and 10 pyrethroid pesticides as target analytes and acetonitrile as the solvent. The results indicated that at 130°C, some organophosphorus pesticides might be degraded, whereas extraction temperatures between 70°C and 100°C were optimal. Next, a prepared sample containing fenitrothion and permethrin was analyzed. Although the sample was not soaked in water prior to analysis, PLE provided analytical results comparable to those obtained by solvent extraction with homogenization. Therefore, PLE is considered a simple and alternative technique for the extraction of organophosphorus and pyrethroid pesticides in soybean.     

Comparison of the concentrations of polychlorinated biphenyls and dioxins in mothers affected by the Yusho incident and their children

Accumulated maternal dioxins are passed onto the fetus and neonate via the placenta and maternal milk. In Japan in 1968, an accidental human exposure to rice oil contaminated with polychlorinated biphenyls (PCBs) and other dioxin-related compounds, such as polychlorinated dibenzofurans (PCDFs), led to development of Yusho oil disease. We investigated differences in blood dioxin concentrations in mother-children pairs affected by the Yusho incident. From 2002 to 2008, blood samples were collected from 26 pairs of Yusho mothers and their children (19 mothers, 26 children). Specific congeners of seven polychlorinated dibenzo-p-dioxins (PCDDs), ten PCDFs, and four non-ortho PCBs were analyzed. The children had significantly lower TEQ concentrations of PCDDs, PCDFs, and coplanar PCBs compared to their mothers. The mother-child difference in blood concentrations varied with the congeners; the largest for 2,3,4,7,8-pentaCDF and the smallest for 1,2,3,4,6,7,8-heptaCDD. The level for 2,3,4,7,8-pentaCDF, which characterizes Yusho oil disease, was approximately 17-30 times higher in the mothers than in the general population, whereas there were no significant differences between children in the formula-fed group and the general population. In contrast, the mean level for 2,3,4,7,8-pentaCDF in the breast-fed group was approximately 1.5 times, (range 0.5-6.5 times) higher than that in the general population. Over 30 years after the Yusho incident, the mean blood dioxin levels in the offspring were only a fraction of the levels in their mothers. This is more consistent with exposure via breast milk than via transplacental transfer in the Yusho incident.     

Concentrations of polychlorinated dibenzo-p-dioxins, polychlorinated dibenzofurans, and dioxin-like polychlorinated biphenyls in blood collected from 195 pregnant women in Sapporo City, Japan

We measured the concentrations of polychlorinated dibenzo-p-dioxins (PCDDs), polychlorinated dibenzofurans (PCDFs), non-ortho coplanar polychlorinated biphenyls (non-ortho PCBs), and mono-ortho coplanar polychlorinated biphenyls (mono-ortho PCBs) in blood collected between 2002 and 2004 from 195 pregnant women living in Sapporo City of Hokkaido Prefecture, Japan. The present study is one of the few studies in which PCDDs, PCDFs, and dioxin-like PCBs have been measured in the blood of pregnant women. Of the 195 pregnant women, 101 were primipara (mean: 28.8 years) and 94 were multipara (mean: 32.4 years). The arithmetic mean total TEQ concentrations of PCDDs, PCDFs, non-ortho PCBs, and mono-ortho PCBs of primiparous and multiparous mothers in Sapporo City were 17.4 (median: 15.7) and 14.0 (median: 13.9)pgTEQ/glipid, respectively, and the concentrations were in the range of 6.6-43.4 and 3.4-28.2pgTEQ/glipid, respectively. In regard to the relationship between the total TEQ concentrations of PCDDs, PCDFs, non-ortho PCBs, and mono-ortho PCBs in maternal blood and the number of deliveries or age of primiparous and multiparius mothers, the levels of these dioxin-like compounds tended to decrease with increases in the number of deliveries and significantly increased with increasing maternal age in both groups. Furthermore, significant correlations were observed between the total TEQ concentrations of these dioxin-like compounds and the age of primiparae and multiparae. The total TEQ concentration of PCDDs, PCDFs, non-ortho PCBs, and mono-ortho PCBs measured in 195 pregnant women has decreased compared to past levels in Japan for the last several decades. The results of the present study have indicated that dioxin contamination in the blood of young women in Japan is continuing to decrease.     

Immunologic effects of perinatal exposure to dioxins, PCBs and organochlorine pesticides in Japanese infants

Effects of perinatal exposure to dioxins, PCBs and organochlorine pesticides on lymphocyte subsets were investigated in the peripheral blood from 101 Japanese infants with approximately 10 months of age. Perinatal exposure to these organochlorine compounds were estimated by their contamination levels in the breast milk of the mothers. Lymphocyte subsets such as CD16+, HLA-DR+, CD4+, CD4+8+, CD8+, CD3+ and CD20+ cells in peripheral venous blood were assessed in a subgroup of 92 infants. Greater exposures to HCE, chlordane and dioxins were significantly associated with the increase in the percentages of CD8+ and CD3+ T lymphocytes and CD4+/CD8+ T cell ratios, respectively. In addition, higher HCH exposure was also associated with a decrease in the percentage of HLA-DR+ T lymphocytes. Furthermore effects of dioxins, DDT and PCBs on the percentage of CD16+ T lymphocyte were more pronounced by the combined exposure of dioxins and PCBs or by the combined exposure of DDT and PCBs. Effects of HCE on the percentages of CD8+ T lymphocyte were also more pronounced by the combined exposure of HCE and chlordane. In conclusion, our study suggests that greater exposures to dioxins, PCBs and organochlorine pesticides determined in this study (except dieldrin) influence the immune system of Japanese infant, although the clinical significance of these changes is uncertain.     

The input-output balance of cadmium in a paddy field of Tokyo

Field monitoring was practiced from 2001 to 2003 to evaluate the input (irrigation, atmospheric deposition, and fertilizer application) and the output (uptake and accumulation into the above-ground biomass of rice plants and leaching) of cadmium (Cd) in a contaminated paddy field in Tokyo. The cadmium concentrations of irrigated water, open-bulk precipitation, soil solution (leaching water), rice plants collected at the harvesting stage and the chemical fertilizer and the cow manure compost applied were determined. The Cd flux of each factor was calculated by multiplying the Cd concentration by the volume or mass of the media. The annual input-output balance of Cd in the paddy field in 2001 and 2002 was estimated to be -5.44 [corrected] g ha(-1) and -2.01 [corrected] g ha(-1), respectively, indicating the loss of Cd from the paddy field, although the losses accounted for only 0.24% [corrected] and 0.089% [corrected] of the total amount of Cd in the ploughed layer soil in 2001 and 2002, respectively. Among the factors involved, the input from fertilizers (including manure compost) and the output due to the uptake by rice plants played a major role in the balance. The former largely depended on the types and amounts of fertilizers applied, and the latter on the water management practices in the paddy field, such as flooding and drainage of the surface water.     

Factors affecting the degradation of amoxicillin in composting toilet

The biological and non-biological factors that affect the degradation of amoxicillin in the composting process of feces have been investigated. The effect of living bacteria and the enzyme (beta-lactamase) on amoxicillin decay was examined, and our results indicated that the biological effects are likely to be negligible. Consequently, the effect of phosphate, ammonia and pH level as non-biological factors was investigated by monitoring the reduction rate of amoxicillin in phosphate and ammonia buffer solutions with several pH levels. Each reduction rate constant was integrated by a simulation model, and the each calculated amoxicillin reduction profile was compared to the reduction profiles of amoxicillin in the composting process of feces. The calculated results corresponded almost exactly to the experimental profiles. We therefore concluded that the degradation of amoxicillin in a toilet matrix was dependent on the concentration of ammonia, phosphate and hydroxyl ion.     

Transfer of symbiotic luminous bacteria from parental Leiognathus nuchalis to their offspring

Juveniles of Leiognathus nuchalis were raised from fertilized eggs for up to 60 d and examined for luminescence activity. Almost all juveniles raised separately from adults failed to produce detectable light. In contrast, a significant percentage (33 to 100%) of the juveniles became luminescent in less than 48 h when they were either kept with adults or inoculated with a homogenate of the adult light organs. The luminescence tended to increase with time after the treatments. These findings suggest that: (1) most of L. nuchalis offspring typically hatch and develop apo-symbiotically and (2) at least 45 d after hatching, juveniles can be infected with symbiotic luminous bacteria from the light organ of adult fish, and thereby gain the ability to produce light. Received: 16 February 1999 / Accepted: 21 September 1999     

Feeding and growth of juvenile stone flounder in estuaries: generality and the importance of sublethal tissue cropping of benthic invertebrates

We investigated the feeding habits and growth of juvenile stone flounder (Platichthys bicoloratus) in several estuarine nurseries in Sendai Bay, Japan. Prey abundance and composition and juvenile diet varied largely among sites. However, polychaete palps (mostly Pseudopolydora kempi) and bivalve siphons (mostly Nuttallia olivacea) were positively selected and frequently consumed by juveniles, indicating the generality of sublethal feeding of juvenile stone flounder in estuarine nurseries. Recent growth rates determined by otolith microstructure analyses were dependent on juvenile body size and water temperature, but independent of juvenile density and food abundance. Growth rates were nearly maximal from March to May, suggesting that food conditions are nearly optimal in these estuarine nurseries. Sublethal tissue cropping of benthic invertebrates is thought to contribute largely to these high growth rates.