Root uptake of lipophilic zinc-rhamnolipid complexes

This study investigated the formation and plant uptake of lipophilic metal-rhamnolipid complexes. Monorhamnosyl and dirhamnosyl rhamnolipids formed lipophilic complexes with copper (Cu), manganese (Mn), and zinc (Zn). Rhamnolipids significantly increased Zn absorption by Brassica napus var. Pinnacle roots in 65Zn-spiked ice-cold solutions, compared with ZnSO4 alone. Therefore, rhamnolipid appeared to facilitate Zn absorption via a nonmetabolically mediated pathway. Synchrotron XRF and XAS showed that Zn was present in roots as Zn-phytate-like compounds when roots were treated with Zn-free solutions, ZnSO4, or Zn-EDTA. With rhamnolipid application, Zn was predominantly found in roots as the Zn-rhamnolipid complex. When applied to a calcareous soil, rhamnolipids increased dry matter production and Zn concentrations in durum (Triticum durum L. cv. Balcali-2000) and bread wheat (Triticum aestivum L. cv. BDME-10) shoots. Rhamnolipids either increased total plant uptake of Zn from the soil or increased Zn translocation by reducing the prevalence of insoluble Zn-phytate-like compounds in roots

Micro-X-Ray Fluorescence, Micro-X-Ray Absorption Spectroscopy, and Micro-X-Ray Diffraction Investigation of Lead Speciation after the Addition of Different Phosphorus Amendments to a Smelter-Contaminated Soil

Citation: Baker, Lucas R., Gary M. Pierzynski, Ganga M. Hettiarachchi, Kirk G. Scheckel, and Matthew Newville. “Micro-X-Ray Fluorescence, Micro-X-Ray Absorption Spectroscopy, and Micro-X-Ray Diffraction Investigation of Lead Speciation after the Addition of Different Phosphorus Amendments to a Smelter-Contaminated Soil.” Journal of Environmental Quality 43, no. 2 (2014): 488–97. https://doi.org/10.2134/jeq2013.07.0281.The stabilization of Pb on additions of P to contaminated soils and mine spoil materials has been well documented. It is clear from the literature that different P sources result in different efficacies of Pb stabilization in the same contaminated material. We hypothesized that the differences in the efficacy of Pb stabilization in contaminated soils on fluid or granular P amendment addition is due to different P reaction processes in and around fertilizer granules and fluid droplets. We used a combination of several synchrotron-based techniques (i.e., spatially resolved micro-X-ray fluorescence, micro-X-ray absorption near-edge structure spectroscopy, and micro-X-ray diffraction) to speciate Pb at two incubation times in a smelter-contaminated soil on addition of several fluid and granular P amendments. The results indicated that the Pb phosphate mineral plumbogummite was an intermediate phase of pyromorphite formation. Additionally, all fluid and granular P sources were able to induce Pb phosphate formation, but fluid phosphoric acid (PA) was the most effective with time and distance from the treatment. Granular phosphate rock and triple super phosphate (TSP) amendments reacted to generate Pb phosphate minerals, with TSP being more effective at greater distances from the point of application. As a result, PA and TSP were the most effective P amendments at inducing Pb phosphate formation, but caution needs to be exercised when adding large amounts of soluble P to the environment

Silver speciation and release in commercial antimicrobial textiles as influenced by washing

The use of nanoscale Ag in textiles is one the most often mentioned uses of nano-Ag. It has previously been shown that significant amounts of the Ag in the textiles are released upon washing. However, the form of Ag present in the textiles remains largely unknown as product labelling is insufficient. The aim of this study was therefore to investigate the solid phase speciation of Ag in original and washed silver textiles using XANES. The original Ag speciation in the textiles was found to vary greatly between different materials with Ag(0), AgCl, Ag2S, Ag–phosphate, ionic Ag and other species identified. Furthermore, within the same textile a number of different species were found to coexist. This is likely due to a combination of factors such as the synthesis processes at industrial scale and the possible reaction of Ag with atmospheric gases. Washing with two different detergents resulted in marked changes in Ag-speciation. For some textiles the two detergents induced similar transformation, in other textiles they resulted in very different Ag species. This study demonstrates that in functional Ag textiles a variety of different Ag species coexist before and after washing. These results have important implications for the risk assessment of Ag textiles because they show that the metallic Ag is only one of the many silver species that need to be considered

Lead Speciation and Bioavailability in Apatite-Amended Sediments

The in situ sequestration of lead (Pb) in sediment with a phosphate amendment was investigated by Pb speciation and bioavailability. Sediment Pb in preamendment samples was identified as galena (PbS) with trace amounts of absorbed Pb. Sediment exposed to atmospheric conditions underwent conversion to hydrocerussite and anglesite. Sediments mixed with apatite exhibited limited conversion to pyromorphite, the hypothesized end product. Conversion of PbS to pyromorphite is inhibited under reducing conditions, and pyromorphite formation appears limited to reaction with pore water Pb and PbS oxidation products. Porewater Pb values were decreased by 94% or more when sediment was amended with apatite. The acute toxicity of the sediment Pb was evaluated with Hyalella azteca and bioaccumulation of Pb with Lumbriculus variegatus. The growth of H. azteca may be mildly inhibited in contaminated sediment, with apatite-amended sediments exhibiting on average a higher growth weight by approximately 20%. The bioaccumulation of Pb in L. variegatus tissue decreased with increased phosphate loading in contaminated sediment. The study indicates limited effectiveness of apatite in sequestering Pb if present as PbS under reducing conditions, but sequestration of porewater Pb and stabilization of near-surface sediment may be a feasible and alternative approach to decreasing potential toxicity of Pb

Bioaccessibility Tests Accurately Estimate Bioavailability Of Lead To Quail

Hazards of soil-borne lead (Pb) to wild birds may be more accurately quantified if the bioavailability of that Pb is known. To better understand the bioavailability of Pb to birds, the authors measured blood Pb concentrations in Japanese quail (Coturnix japonica) fed diets containing Pb-contaminated soils. Relative bioavailabilities were expressed by comparison with blood Pb concentrations in quail fed a Pb acetate reference diet. Diets containing soil from 5 Pb-contaminated Superfund sites had relative bioavailabilities from 33% to 63%, with a mean of approximately 50%. Treatment of 2 of the soils with phosphorus (P) significantly reduced the bioavailability of Pb. Bioaccessibility of Pb in the test soils was then measured in 6 in vitro tests and regressed on bioavailability: the relative bioavailability leaching procedure at pH 1.5, the same test conducted at pH 2.5, the Ohio State University in vitro gastrointestinal method, the urban soil bioaccessible lead test, the modified physiologically based extraction test, and the waterfowl physiologically based extraction test. All regressions had positive slopes. Based on criteria of slope and coefficient of determination, the relative bioavailability leaching procedure at pH 2.5 and Ohio State University in vitro gastrointestinal tests performed very well. Speciation by X-ray absorption spectroscopy demonstrated that, on average, most of the Pb in the sampled soils was sorbed to minerals (30%), bound to organic matter (24%), or present as Pb sulfate (18%). Additional Pb was associated with P (chloropyromorphite, hydroxypyromorphite, and tertiary Pb phosphate) and with Pb carbonates, leadhillite (a lead sulfate carbonate hydroxide), and Pb sulfide. The formation of chloropyromorphite reduced the bioavailability of Pb, and the amendment of Pb-contaminated soils with P may be a thermodynamically favored means to sequester Pb

Reactive gaseous mercury is generated from chloralkali factories resulting in extreme concentrations of mercury in hair of workers

Part of this research was undertaken on the XAS and XFM beamlines at the Australian Synchrotron, Victoria, Australia. The authors thank UNEP Chemicals for financial support of this study as part of the project: Management of Mercury and Mercury containing waste.Peer reviewedPublisher PD

In vivo formation of natural HgSe nanoparticles in the liver and brain of pilot whales

Acknowledgments Z.G. thanks to the College of Physical Sciences at University of Aberdeen and Chevron USA for the provided studentship. P.M.K. is the recipient of an Australian Research Council Future Fellowship (FT120100277). Parts of this research were undertaken on the XFM beamline at the Australian Synchrotron, Victoria, Australia. The assistance of Daryl Howard (XFM beamline, Australian Synchrotron) is acknowledged. Although EPA contributed to this article, the research presented was not performed by or funded by EPA and was not subject to EPA's quality system requirements. Consequently, the views, interpretations, and conclusions expressed in this article are solely those of the authors and do not necessarily reflect or represent EPA's views or policies. MRCAT operations are supported by the Department of Energy and the MRCAT member institutions. This research used resources of the Advanced Photon Source, a U.S. Department of Energy (DOE) Office of Science User Facility operated for the DOE Office of Science by Argonne National Laboratory under Contract No. DE-AC02-06CH11357. The authors declare no competing financial interests. F.L.R. and A.B. acknowledge Scottish Marine Animal Stranding Scheme and Marine Scotland for funding. Author Contributions E.M.K and J.F. designed the experiments. Z.G. measured total Hg and conducted Hg speciation. Total Se was determined by A.R. and Z.G. M.M.L. performed Se speciation and 2D imaging by LA-ICP-MS was done by D.S.U. XANES was performed by K.S. and XRF by E.L. and P.M.K. Samples were obtained by E.M.K. through A.B. and age determination was done by F.R. spICP-MS was performed by E.H.L., K.L., G.W. and Z.G. The manuscript was written by Z.G. and all authors discussed the results and commented on the manuscript.Peer reviewedPublisher PD