Determination of PCDD/Fs and dioxin-like PCBs in fish oils for feed ingredients by congener-specific chemical analysis and CALUX bioassay

The present research was intended to determine the suitability of the CALUX assay as a screening method for dioxins in fish oil used as a feed ingredient in Japan. Alteration of TEQ in fish oil according to newly proposed toxic equivalency factors (TEF) is also discussed. In the analysis, polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/Fs) and dioxin-like polychlorinated biphenyls (DL-PCBs) in 41 fish oil samples were determined by using high-resolution gas chromatography/high-resolution mass spectrometry (HRGC/HRMS) and CALUX bioassay. The mean TEQ values derived from 1998 WHO-TEF of PCDD/Fs and DL-PCBs were 2.6 and 9.9 pg g(-1) (ww), respectively. The levels of TEQ derived from the recently re-evaluated 2005 WHO-TEF were slightly lower than those of the former in both groups. Notably, the contribution of mono-ortho DL-PCBs to total 2005 WHO-TEQ was considerably decreased compared to the case of 1998 WHO-TEQ, resulting from the reduction in its TEF values, while the non-ortho DL-PCBs contribution was increased. The mean TEQ determined by CALUX assay for PCDD/Fs was approximately three times higher, whereas DL-PCBs was approximately two times lower than WHO-TEQ determined by HRGC/HRMS; the sum of PCDD/Fs and DL-PCBs was very similar by both methods. The correlation coefficients of TEQ between the CALUX assay and HRGC/HRMS analysis were 0.84, 0.89, and 0.90 for PCDD/Fs, DL-PCBs, and the sum, respectively. These results suggest that the CALUX assay is a very useful method for the screening of dioxin-related compounds in fish oils.     

In vitro evaluation of atmospheric particulate matter and sedimentation particles using yeast bioassay system.

Little information on the evaluation of airborne particulate matter (APM) and sedimentation particles from subway stations is available. The thermal metamorphism of train wheels generating toxic particles in subway stations is a possibility. In this study, the toxicity and physiological effects of particles from subway stations were evaluated using a yeast bioassay system. Estrogenic and antiestrogenic activities of APM in APM extracts from subway stations were determined. No estrogenic activity was found in the APM fractions and their S9-activated APM samples. Sedimentation dust samples also showed no estrogen activity. In contrast, extracts from sedimentation dust samples showed antiestrogen activity. Marked yeast toxicity was observed in the samples extracted from sedimentation dust. Potent yeast toxicity was also found in the S9-activated extracts from sedimentation dust. The results suggest that sedimentation dust from a semiclosed area of a subway system has antiestrogen activity, although both the origin and generation system of this activity are uncertain. These pollutants in sedimentation dust may change to a more toxic form in vivo by S9 activation.     

Fertilization success and sexual behavior in male medaka, Oryzias latipes, exposed to tributyltin

We evaluated the effects of tributyltin (TBT), polychlorinated biphenyls (PCBs), and a mixture of TBT and PCBs on reproduction, gonadal histology, and sexual behavior in Japanese medaka (Oryzias latipes). We administered TBT (1 microg g(-1) body weight [b.w.] daily), PCBs (1 microg g(-1) b.w. daily), or both to medaka for 3 weeks. We assessed reproductive success during week 3 and the sexual behavior of male medaka after the exposure period. Fertilization success was significantly decreased in groups that received TBT. The profiles of fertility developed a bimodal distribution in the TBT and TBT+PCBs groups, and the numbers of males that performed "following" and "dancing" were significantly decreased in the TBT+PCBs group. The frequency of "dancing" also decreased after treatment with TBT, whereas fish that received PCBs only showed no difference in sexual behavior. Testes that had oocytes showed normal spermatogenesis, even though two of the five males treated with TBT+PCBs had some indication of testis-ova, which did not occur in any other group. Our results indicate that TBT, but not PCBs, affects sexual behavior and reproduction in medaka.     

Chlorophyll and suspended sediment mapping to the Caribbean Sea from rivers in the capital city of the Dominican Republic using ALOS AVNIR-2 data

This study aims to study the distribution of contaminants in rivers that flow into the Caribbean Sea using chlorophyll-a (Chl-a) and suspended sediment (SS) as markers and ALOS AVNIR-2 satellite sensor data. The Haina River (HN) and Ozama and Isabela Rivers (OZ-IS) that flow through the city of Santo Domingo, the capital of the Dominican Republic, were chosen. First, in situ spectral reflectance/Chl-a and SS datasets obtained from these rivers were acquired in March 2011 (case A: with no rain influence) and June 2011 (case B: with rain influence), and the estimation algorithm of Chl-a and SS using AVNIR-2 data was developed from the datasets. Moreover, the developed algorithm was applied to AVNIR-2 data in November 2010 for case A and August 2010 for case B. Results revealed that for Chl-a and SS estimations under cases A and B conditions, the reflectance ratio of AVNIR-2 band 4 and band 3 (AV4/AV3) and the reflectance of AVNIR-2 band 4 (AV4) were effective. The Chl-a and SS mapping results obtained using AVNIR-2 data corresponded with the field survey results. Finally, an outline of the distribution of contaminants at the mouth of the river that flows into the Caribbean Sea was obtained for both rivers in cases A and B.     

Environmental geochemistry of technetium

Technetium-99 (⁹⁹Tc) is a radioactive isotope with a half-life of 2.13 × 10⁵ year. ⁹⁹Tc is a major radionuclide contaminant of concern for the world. Therefore, detailed understanding of ⁹⁹Tc environmental chemistry is important for protecting human and ecological health. Here, we review the aqueous geochemistry of ⁹⁹Tc, focusing on chemical properties and behavior of ⁹⁹Tc in the hydrosphere and pedosphere. We describe the general chemistry of Tc including coordination chemistry, isotope chemistry and solid-state chemistry. Then we present anthropogenic and indigenous sources of ⁹⁹Tc and their environmental distribution. We also discuss the radiotoxicity of ⁹⁹Tc and the use of ⁹⁹Tc for medical purpose. Tc biogeochemistry is described through sorption and desorption reactions at the mineral–water interface, thermodynamic of surface complexation, abiotic and biotic redox reaction of Tc(VII). Finally, we summarize the ⁹⁹Tc remediation technologies including cement waste forms, natural remediation, vitrification, nuclear waste transmutation.     

Fungal levels in houses in the Fukushima Daiichi Nuclear Power Plant evacuation zone after the Great East Japan Earthquake

Residences located within 20 km of the damaged Fukushima Daiichi Nuclear Power Plant were evacuated shortly after the Great East Japan Earthquake. The levels of airborne and surface fungi were measured in six houses in the evacuation zone in August 2012 and February 2013. Airborne fungal levels in all of the houses in the summer were higher than the environmental standard levels for residential houses published in Architectural Institute of Japan (>1000 colony-forming units [CFU]/m³). In two houses whose residents rarely returned to visit, fungal levels were extremely high (>52,000 CFU/m³). Although fungal levels in the winter were much lower than those in the summer, they were still higher than environmental standard levels in several houses. Indoor fungal levels were significantly inversely related to the frequency with which residents returned, but they were not correlated with the air exchange rates, temperature, humidity, or radiation levels. Cladosporium spp. and Penicillium spp. were detected in every house. Aspergillus section Circumdati (Aspergillus ochraceus group) was also detected in several houses. These fungi produced ochratoxin A and ochratoxin B, which have nephrotoxic and carcinogenic potential. The present study suggests that further monitoring of fungal levels is necessary in houses in the Fukushima Daiichi Nuclear Power Plant evacuation zone, and that some houses may require fungal disinfection.

Implications: The results suggest that residents’ health could be at risk owing to the high levels of airborne fungi and toxic fungi Aspergillus section Circumdati. Therefore, monitoring and decontamination/disinfection of fungi are strongly recommended before residents are allowed to return permanently to their homes. In addition, returning to home with a certain frequency and adequate ventilation are necessary during similar situations, e.g., when residents cannot stay in their homes for a long period, because fungal levels in houses in the Fukushima Daiichi Nuclear Power Plant evacuation zone were inversely correlated with the frequency with which residents returned to visit their houses.     

两性修饰磁化炭对紫色土吸附菲的增强作用

为了验证两性修饰磁化炭材料对紫色土吸附菲的增强作用,采用共沉淀负载Fe_3O_4法和湿法有机负载分别制备了磁化炭(MC)和不同十二烷基二甲基甜菜碱(BS-12)修饰比例的两性修饰磁化炭(BS+MC),将其以1%的质量比加入到紫色土(PS)中,分别形成PS_(MC)和PS_(BS+MC)混合样品,批处理法研究各混合样品对菲的等温吸附和热力学特征,并对比了不同温度、离子强度和pH值对菲吸附的影响。结果表明:(1) MC和BS-MC材料的添加均增强了PS对菲的吸附能力,菲吸附量呈现PS_(200BS+MC)> PS_(150BS+MC)> PS_(100BS+MC)> PS_C> PS_(MC)> PS_(50BS+MC)> PS_(25BS+MC)> PS的趋势,PS_(BS+MC)对菲的吸附量随着添加材料上BS-12修饰比例的增加而增加。(2)菲在各供试土样上的吸附均表现为增温负效应(物理吸附),溶液pH值变化仅对PS_(150BS+MC)和PS_(200BS+MC)吸附菲有显著影响。离子强度增大不利于各供试土样对菲的吸附。(3) Henry模型适用于描述菲在供试土样上的等温吸附,且该过程呈现自发的、焓减和熵增的特征。从PS_C到PS_(MC)再到PS_(BS+MC),吸附过程呈现自发性、放热量和混乱度均增大的特征。     

Recovery of coagulant from water supply plant sludge and its effect on clarification

Spent coagulant in water supply plant sludge was extracted with H₂SO₄ and the efficiency of the reused coagulant was studied. The optimum pH values for coagulant extraction and clarification with the reused coagulant were 3.0–4.0 and about 6, respectively. In treating raw influent obtained from a sewage treatment plant and wastewater from a coastal landfill site, the removal of chemical oxygen demand (COD), total nitrogen, and total phosphorous with the recovered coagulant was higher than that with commercial aluminum sulfate or polyaluminum chloride. In addition, the sludge settling properties, the extra sludge mass formation, the supernatant quality, and the cost of reagents were also studied. The coagulant recovered from water supply plant sludge by H₂SO₄ extraction could be successfully reused for the clarification of domestic and food industry wastewaters.     

Estrogen content and relative performance of Japanese and British sewage treatment plants and their potential impact on endocrine disruption.

Both the UK and Japan are densely populated islands with relatively short rivers. Therefore, both countries are likely to be highly exposed to contaminants emanating from their human populations. This review considered how effective the different sewage treatment facilities of the two countries are at removing steroid estrogens from the effluent. The methods of estrogen analysis in sewage effluent, the number and importance of different sewage treatment types, and their apparent effectiveness at removing estrogens were all considered. In both countries, the activated sludge treatment was dominant in terms of people served and water discharged. The analytical techniques used by those studying estrogen concentrations in effluents in both countries were broadly similar. Activated sludge plant (ASP) effluent in the UK typically contained around 2 ng/L estradiol (E2) and 8 ng/L estrone (E1), while Japanese ASPs typically reported E2 as below detection, and 10 ng/L E1 in their effluents. When estrogenic bioassays were used in Japan, they typically record an estrogenic potency of 10 ng/L E2 equivalents. Even taking into account ethinylestradiol (EE2) (not found in Japanese effluents), the overall estrogenicity of British sewage effluents would appear to be the same as that of Japanese sewage effluents (around 10 ng/L E2 equivalents). This suggests that the ASPs serving the large urban communities in Japan and the UK would have effluent of similar estrogenic potencies. Less information is available about the more numerous biological (trickling) filter plants (BFP) in the UK and oxygen ditches (OD) in Japan which tend to serve smaller, more rural communities. The available data would suggest that the BFPs are significantly less efficient than the ODs at removing E1. This would suggest that in similar circumstances, British headwaters (where this sewage treatment plant (STP) type is often found) might be more at risk from endocrine disruption than their Japanese counterparts. Overall, the apparently higher incidence of endocrine disruption in British wild fish than in Japanese wild fish cannot be attributed to differences in the efficiency of their respective STPs.     

A novel extractant for removal of hazardous metals from preservative-treated wood waste

The purpose of this study was to develop a one-step metal extraction process that would effectively remove hazardous elements from wood powder or chips of western hemlock [Tsuga heterophylla (Raf.) Sarg.] treated with chromated copper arsenate (CCA) preservative. In addition, we tested this method for wood treated with other copper-based preservatives such as ammoniacal copper quaternary (ACQ) and copper, boron, and azole (CuAz). A bioxalate solution consisting of 0.125 M oxalic acid adjusted to pH 3.2 with sodium hydroxide was tested for its ability to extract chromium, copper, and arsenic from wood treated with CCA and copper from ACQ, CuAz, or a mixture of CCA-, ACQ-, and CuAz-treated wood in single step. The extraction proceeded efficiently with 6 h of treatment, and was insensitive to the differences in chemical characteristics, including solubility of individual elements. After 6 h of treatment, approximately 90% of chromium, copper, and arsenic were effectively removed from wood treated with CCA or a mixture of CCA, ACQ, and CuAz and 90% of copper from ACQ- and CuAz-treated wood. These results demonstrate that the solvent extraction technique using pH-adjusted bioxalate solution with sodium hydroxide is a promising method for pollution minimization by various types of wastes contaminated with heavy metals and arsenic.