Source Identification Analysis of Lead in the Blood of Japanese Children by Stable Isotope Analysis.

Considering the negative effect of lead (Pb) on children's neurodevelopment, Pb exposure should be minimized to the lowest extent possible, though the blood Pb (BPb) concentrations in Japanese children are among the lowest in the world. To identify the sources of Pb in blood, isotope ratios (IRs: 207Pb/206Pb and 208Pb/206Pb) of Pb (PbIR) in whole blood from eight Japanese children were measured by multi-collector ICP mass spectrometry. Further, samples of house dust, soil, duplicate diet, and tobacco, collected from home environments, were also measured and were compared with PbIR of blood case by case. The relative contribution of Pb in the home environment to BPb were estimated by linear programming (finding an optimal solution which satisfy the combination of IRs and intakes from various sources) when appropriate. Source apportionment for three children could be estimated, and contributions of diet, soil, and house dust were 19-34%, 0-55%, and 20-76%, respectively. PbIR for the remaining five children also suggested that non-dietary sources also contributed to Pb exposure, though quantitative contributions could not be estimated. Non-dietary sources such as soil, house dust, and passive tobacco smoke are also important contributors to Pb exposure for Japanese children based on PbIR results.

Three decades of environmental specimen banking at the National Institute for Environmental Studies, Japan.

After two decades operation of the initial environmental specimen banking, a new program, Environmental Time Capsule Program, started in 2002 as a government-supported long-term program to construct a firm scientific basis for various environmental research studies. The program consists of long-term environmental specimen banking activity and specimen collection of endangered wildlife and is based on cryogenic sample preservation facility called Environmental Time Capsule building, which completed construction in 2004. After 9 years of extensive research, research focuses have been selected and the program was reorganized to the environmental sample collection part and endangered wildlife collection part in 2011. Due to huge environmental disaster caused by the Great East Japan earthquake and the tsunami as well as subsequent nuclear power plant accident at Fukushima, a new sampling and monitoring program started at affected areas in collaboration with the reorganized environmental sample collection and archiving program. Outlines of the quality assurance and quality control (QA/QC) activities in the program and future perspective under related international activities, particularly Stockholm Convention, are reported.

Removal of heavy metal cations by biogenic magnetite nanoparticles produced in Fe(III)-reducing microbial enrichment cultures.

The biogenic magnetite nanoparticles presented here had a high capacity of adsorbing metal cations, which was approximately 30- to 40-fold greater than commercially available magnetite. These results suggest the potential application of microbial magnetite formation in the removal of toxic metal cations from water.

Fungal mn oxides supporting Mn(II) oxidase activity as effective Mn(II) sequestering materials.

We examined the Mn(II)-oxidizing ability of the biogenic Mn oxide (BMO) formed in cultures ofa Mn(II)-oxidizing fungus, Acremonium strictum strain KR21-2. The newly formed BMO effectively sequestered dissolved Mn(II) mainly by oxidizing Mn(II) to insoluble Mn under air-equilibrated conditions, and this ability lasted for at least 8 days. Deaerating the BMOs, poisoning them with NaN3, or heating them all readily weakened their Mn(II) oxidation ability, indicating the involvement of enzymatic Mn(II) oxidation. There was no Mn(II)-oxidizing ability observed for mycelia cultivated without Mn(II) or for residual mycelia after the BMO phase was dissolved, suggesting the need for the oxide phase. A sodium dodecyl sulphate-polyacrylamide gel electrophoresis assay demonstrated that the oxide phase embeds the Mn(II) oxidase and thereby maintains the enzymatic activity in BMOs. Freezing at -80 degrees C preserved the Mn(II)-oxidizing ability in BMOs for at least 4 weeks, while lyophilization caused a complete loss of this ability. Based on these results, we propose that fungal Mn oxides supporting Mn(II) oxidase activity are an effective Mn(II)-sequestering material capable of oxidizing Mn(II) continuously from solutions containing no additional nutrients to maintain biological activity.

Isotope ratio analysis of lead in blood and environmental samples by multi-collector inductively coupled plasma mass spectrometry.

It is widely recognized that lead (Pb) affects children's cognitive function, even at relatively low blood lead levels (<10 µg dL(-1)). The determination of the source of Pb in children is essential for effective risk management. The use of multi-collector ICPMS (MC-ICPMS) for isotope ratio measurements of Pb in environmental and biological samples was examined for this purpose. MC-ICPMS with an instrumental mass fractionation correction by Tl allowed accurate isotope ratio measurements of the Pb isotopic reference material NIST SRM 981. However, the presence of matrix elements (Al, Ca, Fe and Na) at more than 10 mg kg(-1) in the sample solution significantly deteriorated the accuracy. The separation of Pb from the matrix is necessary for accurate measurements of the isotope ratio of Pb in environmental and biological samples. Bromide-complexation, followed by anion exchange was found to be satisfactory in terms of the recovery of Pb (90 to 104%) and the efficiency of matrix separation. The procedure was applied to a preliminary source analysis of Pb in the blood of Japanese children, and a significant contribution of indoor dust was demonstrated.

Production of biogenic manganese oxides by repeated-batch cultures of laboratory microcosms.

We investigated the production of manganese (Mn) oxides using repeated-batch bioreactors maintained over long periods under laboratory conditions. Freshwater epilithic biofilms were used as the initial inocula. The bioreactors yielded suspended solids that could remove 0.1 mM dissolved Mn(II) within a few days. Chemical titration, X-ray absorption near-edge structure spectroscopy, and X-ray diffraction analysis revealed that the Mn(II) had been converted to poorly crystallized layer-type Mn(IV) oxides, which were similar to known biogenic Mn oxides from pure bacterial cultures. Spherical or rod-shaped Mn microconcretions occurred in the suspended solids; transmission electron microscopy showed that these structures likely resulted from the microbial activity but not represent living cells. Instead, the presence of encapsulated, sheathed, and hyphal budding cells in the suspended solids indicated that a range of Mn-depositing bacteria contributed to the Mn oxide formation. To our knowledge, our data represent the first observation of production of such Mn oxides in a laboratory microcosm wherein a range of Mn-depositing bacteria coexist. The fact that sorption of trace Zn(II) and Ni(II) ions onto the suspended solids co-occurred with the removal of dissolved Mn(II) emphasizes the important role of Mn-oxidizing microorganisms in the fates of trace or contaminant metals in the aquatic environment.

Sorption of Co(II), Ni(II), and Zn(II) on biogenic manganese oxides produced by a Mn-oxidizing fungus, strain KR21-2.

The characteristics of Co(II), Ni(II), and Zn(II) sorption on freshly produced biogenic Mn oxides by a Mn-oxidizing fungus, strain KR21-2, were investigated. The biogenic Mn oxides showed about 10-fold higher efficiencies for sorbing the metal ions than a synthetic Mn oxide (gamma-MnO2) on the basis of unit weight and unit surface area. The order of sorption efficiency on the biogenic Mn oxides was Co(II) > Zn(II) > Ni(II), while that on the synthetic Mn oxide was Zn(II) > Co(II) > Ni(II). These sorption selectivities were confirmed by both sorption isotherms and competitive sorption experiments. Two-step extraction, using 10mM CuSO4 solution for exchangeable sorbed ions and 10-20mM hydroxylamine hydrochloride for ions bound to reducible Mn oxide phase, showed higher irreversibility of Co(II) and Ni(II) sorption on the biogenic Mn oxides while Zn(II) sorption was mostly reversible (Cu(II)-exchangeable). Sorptions of Co(II), Ni(II), and Zn(II) on the synthetic Mn oxide were, however, found to be mostly reversible. Higher irreversibility of Co(II) and Ni(II) sorption on the biogenic Mn oxides may partly explain higher accumulation of these metal ions in Mn oxide phases in natural environments. The results obtained in this study raise the possibility to applying the biogenic Mn oxide formation to treatment of water contaminated with toxic metal ions.

Interaction of inorganic arsenic with biogenic manganese oxide produced by a Mn-oxidizing fungus, strain KR21-2.

In batch culture experiments we examined oxidation of As(III) and adsorption of As(III/V) by biogenic manganese oxide formed by a manganese oxide-depositing fungus, strain KR21-2. We expected to gain insight into the applicability of Mn-depositing microorganisms for biological treatment of As-contaminated waters. In cultures containing Mn2+ and As(V), the solid Mn phase was rich in bound Mn2+ (molar ratio, approximately 30%) and showed a transiently high accumulation of As(V) during the early stage of manganese oxide formation. As manganese oxide formation progressed, a large proportion of adsorbed As(V) was subsequently released. The high proportion of bound Mn2+ may suppress a charge repulsion between As(V) and the manganese oxide surface, which has structural negative charges, promoting complex formation. In cultures containing Mn2+ and As(III), As(III) started to be oxidized to As(V) after manganese oxide formation was mostly completed. In suspensions of the biogenic manganese oxides with dissolved Mn2+, As(III) oxidation rates decreased with increasing dissolved Mn2+. These results indicate that biogenic manganese oxide with a high proportion of bound Mn2+ oxidizes As(III) less effectively than with a low proportion of bound Mn2+. Coexisting Zn2+, Ni2+, and Co2+ also showed similar effects to different extents. The present study demonstrates characteristic features of oxidation and adsorption of As by biogenic manganese oxides and suggests possibilities of developing a microbial treatment system for water contaminated with As that is suited to the actual situation of contamination.

Surface-analytical studies on environmental and geochemical surface processes.

The surface chemical compositions of solid samples from environmental and geological sources can differ from the bulk or average compositions, because of changes caused by adsorption, dissolution, oxidation, etc. Accordingly, analytical information on surface layers is important for a better understanding of the environmental chemistry involving solid surfaces. The rapid development of surface-analytical techniques has enabled us to probe the surface chemistry of environmental and geological solid samples of complex composition. This article demonstrates some examples of important items of information that can be obtained by applying surface-analytical techniques, such as X-ray photoelectron spectroscopy and secondary ion mass spectrometry, to environmental and geological samples. The surface analysis of fly ashes, soils, sediments and weathered silicate minerals is reviewed.