Detection of dicofol and related pesticides in human breast milk from China, Korea and Japan

Previously, we demonstrated that the concentrations of DDTs were greater in breast milk collected from Chinese mothers than from Japanese and Korean mothers. To investigate dicofol as a possible source of the DDTs in human breast milk, we collected breast milk samples from 2007 to 2009 in China (Beijing), Korea (Seoul, Busan) and Japan (Sendai, Takarazuka and Takayama). Using these breast milk samples, we quantified the concentrations of dichlorobenzophenone, a pyrolysis product of dicofol (simply referred to as dicofol hereafter), dichlorodiphenyltrichloroethane and its metabolites (DDTs) using GC-MS. Overall, 12 of 14 pooled breast milk samples from 210 mothers contained detectable levels of dicofol (>0.1 ng g⁻¹ lipid). The geometric mean concentration of dicofol in the Japanese breast milk samples was 0.3 ng g⁻¹ lipid and significantly lower than that in Chinese (9.6 ng g⁻¹ lipid) or Korean breast milk samples (1.9 ng g⁻¹ lipid) (p < 0.05 for each). Furthermore, the ΣDDT levels in breast milk from China were 10-fold higher than those from Korea and Japan. The present results strongly suggest the presence of extensive emission sources of both dicofol and DDTs in China. However, exposure to dicofol cannot explain the large exposure of Chinese mothers to DDTs because of the trace levels of dicofol in the ΣDDTs. In the present study, dicofol was confirmed to be detectable in human breast milk. This is the first report to identify dicofol in human samples.     

Biohydrogen using leachate from an industrial waste landfill as inoculum

Since hydrogen is a renewable energy source, biohydrogen has been researched in recent years. However, data on hydrogen fermentation by a leachate from a waste landfill as inoculum are scarce. We investigated hydrogen production using a leachate from an industrial waste landfill in Kanagawa Prefecture. The results showed no methane gas production, and the leachate was a suitable inoculum for hydrogen fermentation. The maximum H₂ yield was 2.67 mol of H₂ per mol of carbohydrate added, obtained at 30°C and an initial pH of 7. The acetate and butyrate production was significant when the H₂ yield was higher. Oxidation–reduction potential analysis of the culture suggested that hydrogen-producing bacteria in the leachate were facultative anaerobic. Scanning electron microscope observations revealed that the hydrogen-producing bacteria comprised bacilli about 2 μm in length.     

Direct determination of neonicotinoid insecticides in an analytically challenging crop such as Chinese chives using selective ELISAs

ABSTRACT

Easy-to-use commercial kit-based enzyme-linked immunosorbent assays (ELISAs) have been used to detect neonicotinoid dinotefuran, clothianidin and imidacloprid in Chinese chives, which are considered a troublesome matrix for chromatographic techniques. Based on their high water solubility, water was used as an extractant. Matrix interference could be avoided substantially just diluting sample extracts. Average recoveries of insecticides from spiked samples were 85–113%, with relative standard deviation of <15%. The concentrations of insecticides detected from the spiked samples with the proposed ELISA methods correlated well with those by the reference high-performance liquid chromatography (HPLC) method. The residues analyzed by the ELISA methods were consistently 1.24 times that found by the HPLC method, attributable to loss of analyte during sample clean-up for HPLC analyses. It was revealed that the ELISA methods can be applied easily to pesticide residue analysis in troublesome matrix such as Chinese chives.     

Correlation of low-volatile organic chlorine (LVOCl) and PCDD/Fs in various municipal waste incinerators (MWIs)

Medium- and low-volatile organic chlorine (M/LVOCl) and PCDD/Fs in flue gas from various municipal waste incinerators (MWIs) were monitored. The sample for M/LVOCl was collected in an adsorption tube which was thermally desorbed and the amount of chlorine was measured by atomic emission spectrometry (AES) detection using radiofrequency helium plasma. The helium plasma excited chlorine having an optical emission line of 837.6 nm was monitored. The MVOCl and LVOCl were organic chlorine groups whose boiling points (bp) ranged from 70-120 degrees C and 170-270 degrees C, respectively. The compounds having bp 120-170 degrees C were distributed in two tubes. LVOCl correlated well with PCDD/Fs (ng/Nm3, r=0.81) in a wide range of 0.01-100 ng/Nm3 of PCDD/Fs, while the correlation of LVOCl vs. TEQ was less related (r=0.69). These results agreed with the fact that LVOCl monitored the amount of organic chlorine without molecular structure information, which is critical to toxicity. Since the bp of LVOCl was not identical with that of PCDD/Fs, the regression was effected by the conditions of the gas treatment devices. Because most data of 2001 were collected just after the installation of PCDD/Fs in MWIs, the regression of 2001 was slightly different from that of 2002-2003. Eliminating these initial unsteady data, the regression of LVOCl vs. PCDD/Fs became better, giving r= 0.86. Besides having PCDD/Fs as surrogates, M/LVOCl is valuable as a versatile element-selective organic chlorine monitor to improve thermal process control.     

Historical and geographical aspects of the increasing perfluorooctanoate and perfluorooctane sulfonate contamination in human serum in Japan

Perfluorooctane sulfonate (PFOS) and perfluorooctanoate (PFOA) have recently received attention due to their widespread contamination in the environment, as well as in wildlife and humans. We measured the PFOS and PFOA concentrations in historically recorded human serum samples at an age range between 20 and 59 years collected in Kyoto, 20 persons per each time point (n=100), and also the PFOS and PFOA concentrations in human serum samples at an age range between 20 and 59 years from 10 locations throughout Japan (n=200). The historical samples collected from 1983 to 1999 demonstrated that the PFOA concentrations in males and females from Kyoto have increased 4.4-fold and 4.3-fold at a rate of increase of 0.49 ng/ml/year and 0.42 ng/ml/year, respectively. In contrast, serum concentrations of PFOS reached a plateau in the late 1980s. There are also regional differences in both the PFOS and PFOA serum concentrations. The concentrations in serum [geometric mean (geometric standard deviation)] (ng/ml) in 2003-2004 ranged from 7.6(1.6) in the town of Matsuoka in Fukui prefecture to 27.8(1.6) in Kyoto city, and ranged from 2.3(1.5) in Matsuoka to 14.5(1.3) in Osaka city for PFOS and PFOA, respectively.     

Analysis of biomagnification of persistent organic pollutants in the aquatic food web of the Mekong Delta, South Vietnam using stable carbon and nitrogen isotopes

The present study elucidated the biomagnification profiles of persistent organic pollutants (POPs) through a tropical aquatic food web of Vietnam based on trophic characterization using stable nitrogen analysis. Various biological samples collected from the main stream of the Mekong Delta were provided for the analysis for both POPs, and stable nitrogen and carbon isotope ratios. Of the POPs analyzed, dichlorodiphenyltrichloroethane and its metabolites (DDTs) were the predominant contaminants with concentrations ranging from 0.058 to 12 ng/g wet weight, followed by polychlorinated biphenyls (PCBs) at 0.017-8.9 ng/g, chlordane compounds (CHLs) at 0.0043-0.76 ng/g, tris-4-chlorophenyl methane (TCPMe) at N.D.-0.26 ng/g, hexachlorocyclohexane isomers (HCHs) at N.D.-0.20 ng/g and hexachlorobenzene (HCB) at 0.0021-0.096 ng/g. Significant positive increases of concentrations in DDTs, CHLs, and TCPMe against the stable nitrogen ratio (delta(15)N) were detected, while, concentrations of HCHs and HCB showed no significant increase. The slopes of the regression equations between the log-transformed concentrations of these POPs and delta(15)N were used as indices of biomagnification. The slopes of the POPs for which positive biomagnification was detected ranged from 0.149 to 0.177 on a wet weight basis. The slopes of DDTs and CHLs were less than those reported for a marine food web of the Arctic Ocean, indicating that less biomagnification had occurred in the tropical food web. Of the isomers of CHLs, unlike the studies of the Arctic Ocean, oxychlordane did not undergo significant biomagnification through the food web of the Mekong Delta. This difference is considered to be due to a lack of marine mammals, which might metabolize cis- and trans-chlordane to oxychlordane, in the Mekong Delta ecosystem. The biomagnification profile of TCPMe is reported for the first time in the present study.     

Changes in gonadal development,androgenic gland cell structure,and hemolymph vitellogenin levels during male phase and sex change in laboratory-maintained protandric shrimp, <Emphasis Type="Italic">Pandalus hypsinotus</Emphasis> (Crustacea: Caridea: Pandalidae)

Most pandalid shrimps show protandric hermaphroditism, and male sexual differentiation is considered to be controlled by the androgenic gland. In the present study, we examined the histology of gonadal development during the male phase and sex change and the involvement of the androgenic gland in regulating male reproduction in laboratory-maintained Pandalus hypsinotus. Juvenile shrimps developed testicular tissues in the peripheral part of gonads during the age of 16–31 months and produced spermatozoa between 34 and 36 months. After reaching sexual maturity, male shrimps exhibited seasonal testicular development: active production of spermatozoa (February–May), disappearance of spermatozoa (spent, April–June), increase of spermatocytes (May–November), appearance of spermatids and spermatozoa in the gonads (November–February). The androgenic gland cells became larger and the rough endoplasmic reticulum in the cytoplasm developed at male sexual maturity. The cell structure shows that the androgenic gland hormone is a peptide. Furthermore, bilateral eyestalk ablation on immature male shrimps induced hypertrophy of the androgenic gland and acceleration of male sexual maturation. These results indicate the involvement of androgenic gland hormone and some eyestalk factor in regulating male sexual maturation. Over a 1-year laboratory-rearing period, some male shrimps (16.7%) changed sex. In transitional shrimps, testicular tissues in the gonads and androgenic glands degenerated; on the other hand, oocytes started yolk protein accumulation and hemolymph vitellogenin levels became high. These results suggest that androgenic gland degeneration is a trigger for sex change and that the vitellogenin level is a useful marker for sex change.     

Participation of the C-type hemolymph lectin in mineralization of the acorn barnacle Megabalanus rosa

BRA-2, a major C-type lectin in the hemolymph of the acorn barnacle Megabalanus rosa was detected in shell-associated proteins. Immobilized BRA-2 promoted CaCO₃ crystallization as determined by an in vitro pH-drift mineralization assay. In nature, calcification occurs as wound repair in M. rosa after breakage of the shell plate. To observe this phenomenon, we inserted a rubber cube inside the mantle cavity of M. rosa through the basal plate, and kept the organisms in a tank for several weeks. The rubber cube was covered first with brownish-colored material, probably a melanin, and then with CaCO₃ 5 weeks after the insertion. In the CaCO₃-associated proteins, BRA-3, a minor component of M. rosa hemolymph lectins, was present in addition to BRA-2. The presence of both the lectins and their ligands on the hemocyte was also observed. These results suggest that the C-type lectins of the M. rosa hemolymph participate in mineralization as well as defense in these organisms.     

Concentrations and composition of PCB congeners in the air around stored used capacitors containing PCB insulator oil in a suburb of Bangkok, Thailand

Accumulation of Zn, Cu, Pb and Cd was studied in snails fed for 120 days on diets contaminated with each metal separately and with all metals mixed together. The concentrations of Zn in food were in the range 39 to 12 200 mg kg(-1), Cu 9-1640 mg kg(-1), Pb 0.4-12 700 mg kg(-1), and Cd 0.16-146 mg kg(-1) on a dry weight basis. At the highest concentrations of all metals the consumption rates decreased significantly. For the remaining concentrations, Zn and Cu were accumulated in soft tissue in proportion to their concentrations in food. The lowest treatments of Pb and Cd did not cause any increase in soft tissue concentrations of these metals but at average treatments, a clear increase was observed. Copper was accumulated especially efficiently, exceeding concentrations in food throughout the whole range of treatments. Except for the lower end of experimental treatments, Zn was accumulated approximately in direct proportion to its concentration in the diet. Lead was the most efficiently regulated metal, with soft tissue concentrations always substantially lower than in food. Approximately 60% of Zn, 90% of Cu, 43% of Pb and 68% of Cd on average was assimilated from food. The assimilation efficiency of food alone was ca 74%. The concentrations of metals in shells increased significantly with exposure, but (with one exception) the concentrations in shells did not exceed 5% of those found in soft tissue. We argue that snails are more important as agents of food-chain transport of Cu and Cd, than of Zn or Pb. Our results indicate also that snails are not able to deposit significant quantities of metals in their shells, at least during the time scale of our laboratory experiment.     

Estimation of sources and inflow of dioxins and polycyclic aromatic hydrocarbons from the sediment core of Lake Suwa, Japan

To elucidate the historical changes in polychlorinated dibenzo-p-dioxin (PCDD), polychlorinated dibenzofuran (PCDF), coplanar polychlorinated biphenyl (co-PCB), and polycyclic aromatic hydrocarbon (PAH) inflows in Lake Suwa, their concentrations in the sediment core were analyzed in 5 cm interval. The maximum concentrations (depth cm) of PCDDs/DFs, co-PCBs, and PAHs were 25.2 ng/g dry (30-35 cm), 19.0 ng/g dry (30-35 cm), and 738, 795 ng/g dry (50-55 cm, 30-35 cm), respectively. Age and sedimentation rate of the sediment were estimated from the vertical changes in apparent density. Deposition rate of dioxins and PAHs were calculated from the concentration and sedimentation rate of the sediment. The results indicate that large amounts of dioxins and PAHs flowed into the lake in flood stage compared to normal stage.