Cadmium Release from a Reprocessing Electrorefiner
The possible biological consequences of a release
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The possible biological consequences of a release
Novel Fe3O4 at TiO2 magnetic nanoparticles were prepared and developed for a new nanoparticle-based immunosensor for electrochemical quantification of organophosphorylated butyrylcholinesterase (BChE) in plasma, a specific biomarker of exposure to organophosphorus (OP) agents. The Fe3O4 at TiO2 nanoparticles were synthesized by hydrolysis of tetrabutyltitanate on the surface of Fe3O4 magnetic nanospheres, and characterized by attenuated total reflection Fourier-transform infrared spectra, transmission electron microscope and X-ray diffraction. The functional Fe3O4 at TiO2 nanoparticles were performed as capture antibody to selectively enrich phosphorylated moiety instead of phosphoserine antibody in the traditional sandwich immunoassays. The secondary recognition was served by quantum dots (QDs)-tagged anti-BChE antibody (QDs-anti-BChE). With the help of a magnet, the resulting sandwich-like complex, Fe3O4 at TiO2/OP-BChE/QDs-anti-BChE, was easily isolated from sample solutions and the released cadmium ions were detected on a disposable screen-printed electrode (SPE). The binding affinities were investigated by both surface plasmon resonance (SPR) and square wave voltammetry (SWV). This method not only avoids the drawback of unavailability of commercial OP-specific antibody but also amplifies detection signal by QDs-tags together with easy separation of samples by magnetic forces. The proposed immunosensor yields a linear response over a broad OP-BChE concentrations range from 0.02 to 10 nM, with detection limit of 0.01 nM. Moreover, the disposable nanoparticle-based immunosensor has been validated with human plasma samples. It offers a new method for rapid, sensitive, selective and inexpensive screening/evaluating exposure to OP pesticides.
(Part of the data collected for this work and discussed in this report was subject to data quality and bias issues. All the affected tests have subsequently been repeated, as directed by the Waste Treatment Plant Project, and new statistical analyses have been performed on the revised data set. A subsequently-issued report supercedes this report and describes the revised data, together with the revised composition-property models (Kot et al. 2004). The reader should refer to the new report for discussion of the revised data set and composition-property (TCLP cadmium release) models. None of the data for the spike glasses, designed for Case 1 and Case 2 COPCs testing, were affected by this issue.)
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An electrochemically-assisted wastewater treatment using Faradaic materials offers a promising technique for the selective removal of hazardous substances. Here, we demonstrate the reversible capture and release of cadmium ions in aqueous solutions, using a redox-active metal-organic framework (MOF) electrode. As-synthesized copper-based MOF (Cu-MOF-74; copper 2,5-dihydroxyterephthalate) is a highly attractive candidate for Faradaic electrosorption due to its large surface area, water stability, and redox-active metal nodes. Our work demonstrates the reversible capture and release of Cd 2+ ions assisted by the electrochemical redox reaction of Cu 2+ /Cu + within the MOF structure. Combined material characterization and electrosorption tests were carried out to determine the operational conditions for maximizing adsorption capacity, energy efficiency, and material stability, thus leading to excellent electrosorption (>100 mg g -1 ) and regeneration efficiency (>90%). This study demonstrates the feasibility of leveraging MOFs containing redox-active metal nodes for the selective separation of toxic cations, and paves the way for promising future applications of these 3-D porous structures for wastewater treatment and environmental remediation.
The primary goal of the testing described in this report was to collect data to demonstrate compliance of the immobilized high-level waste (IHLW) glasses with delisting requirements. The collected data will be used to support a petition to delist the IHLW glasses destined for the national disposal facility. The Delisting Data Quality Objectives (DQO) (Cook and Blumenkranz 2003) identified a list of (16) inorganic constituents of potential concern (COPCs) and their associated limits for delisting. These COPCs can be divided into three groups, Cases 1, 2, and 3, based on their Toxicity Characteristic Leaching Procedure (TCLP) responses versus their respective delisting limits. To briefly summarize, Case 1 COPCs are those that, when loaded at their highest expected concentration in Waste Treatment Plant (WTP) glasses, are not expected to leach at their respective delisting limits when the glasses are exposed to the TCLP. Case 2 COPCs may reach the delisting limits in TCLP leachates of WTP glasses if loaded to concentrations near their maximum expected concentrations in glass. Finally, Case 3 COPCs are components that are likely to be present in concentrations sufficient to exceed their respective delisting limits in TCLP leachates of some possible glasses. The test objective was to show that, for (i) the expected range of inorganic contents in the waste feed to the Hanford WTP high level waste (HLW) vitrification facility, (ii) the expected range of glass product compositions, and (iii) the Case 1 and Case 2 COPCs identified by the DQO, the IHLW glasses meet all the relevant requirements for delisting. For Case 3 COPCs (i.e., Cd), the testing was to demonstrate the relationship between glass composition and TCLP cadmium (Cd) release, and then employ the results to develop TCLP-composition response models. During WTP operations, TCLP-composition models can be used to predict, within the required statistical uncertainties, TCLP responses of IHLW production glasses that are within the compositional region used to develop the model.
Abstract The sequestration of carbon dioxide (CO2) in deep underground reservoirs has been identified as an important strategy to decrease atmospheric CO2 levels and mitigate global warming, but potential risks on overlying aquifers currently lack a complete evaluation. In addition to CO2, other gases such as methane (CH4) may be present in storage reservoirs. This paper explores for the first time the combined effect of leaking CO2 and CH4 gasses on the fate of major, minor and trace elements in an aquifer overlying a potential sequestration site. Emphasis is placed on the fate of arsenic (As) and cadmium (Cd) released from the sediments or present as soluble constituents in the leaking brine. Results from macroscopic batch and column experiments show that the presence of CH4 (at a concentration of 1 % in the mixture CO2/CH4) does not have a significant effect on solution pH or the concentrations of most major elements (such as Ca, Ba, and Mg). However, the concentrations of Mn, Mo, Si and Na are inconsistently affected by the presence of CH4 (i.e., in at least one sediment tested in this study). Cd is not released from the sediments and spiked Cd is mostly removed from the aqueous phase most likely via adsorption. The fate of sediment associated As [mainly sorbed arsenite or As(III) in minerals] and spiked As [i.e., As5+] is complex. Possible mechanisms that control the As behavior in this system are discussed in this paper. Results are significant for CO2 sequestration risk evaluation and site selection and demonstrate the importance of evaluating reservoir brine and gas stream composition during site selection to ensure the safest site is being chosen.
Climate change and metals independently stress soil microbiomes, but their combined effects remain unresolved. Here we show that future climate affects soil cadmium through altered soil microbiome and nutrient cycles, with soil pH as critical factor. In soils with pH<7 and during summer temperatures, future climate increased porewater cadmium, shifting total and potentially active taxonomic microbiome structures. Microbial ammonium oxidation released protons liberating cadmium through cation exchange from mineral surfaces. When porewater cadmium levels became toxic to non-cadmium-tolerant bacteria, microbial activity, and nutrient cycling decreased, reducing carbon and nitrogen emissions. In contrast, pH>7 soil show no climate impacts on cadmium mobilization, though imprints on microbiome structure were apparent. Subsequent nutrient cycling increased under future climate, stimulating soil respiration and nitrous oxide release. These findings underscore complex interactions between climate change and soil contaminants affecting the soil microbiome and its activity and highlights potential impacts on crop production, groundwater quality, and climate feedback.
Statolith formation in Cnidaria was reviewed with an emphasis on Aurelia statoliths. The review provides information on the chemical composition, mechanisms of initiation of mineralization, and effects of environmental factors on Cnidarian statolith formation. Environmental factors discussed included modified sea water ingredients, X-irradiation, clinostat rotation, and petroleum oil ingredients. A detailed account of the effects of cadmium on mineralization and demineralization of Aurelia statoliths is given. Cadmium at dosages of 2 to 4 micromoles significantly reduces statolith numbers in developing ephyrae. At a dosage of 3 micromoles, cadmium accelerates statolith loss in unfed ephyrae studied at 4 and 8 days following ephyrae release from strobilae. Cadmium, therefore, is shown to reduce statolith numbers in developing ephyrae and to cause greater reduction of statolith numbers in unfed ephyrae after 4 and 8 days than occurred in controls. Supplementation of Cd(2+)-containing artificial sea water (ASW) with calcium (3X and 5X ASW calcium content) results in higher numbers of statoliths at day 4 as compared with cadmium-treated ephyrae. At 8 days only the 5X calcium supplemented ASW is effective in enhancing statolith numbers in Cd(2+)-treated ephyrae. These results suggest that cadmium competes in some manner with calcium at the mineralizing sites of Aurelia.
Back contacting p-type CdTe has been identified as one of the major areas of loss in CdTe photovoltaic (PV) power conversion efficiency (PCE). In research settings, Au is a common contact material due to its ease of use and decent performance. This work provides a detailed investigation into using gold for back contacting As-doped, CdCl2 treated, polycrystalline CdTe that has been exposed to air after absorber processing, another routine practice. First, X-ray photoemission spectroscopy (XPS) is used to determine the native oxide to be 1.6 nm of CdTeO3 using a combination of angle-resolved XPS and the cadmium modified Auger parameter. During gold metallization of CdTe, oxygen and oxidized tellurium are eliminated from the thin CdTeO3 native oxide. The fate of the released oxygen and possibly cadmium and tellurium are not known, but these reaction byproducts can enter the absorber bulk or grain boundaries, stay at the interface, or dissolve in the Au. Interfacial hole barriers between CdTe and Au are measured for samples with and without the native oxide present prior to metallization. Results show that the thin CdTeO3 alleviates the downward band bending by 40 meV from 470 meV to 430 meV even though it is consumed during interface formation. The implications of these chemical reactions on the device are assessed through photoluminescence (PL) spectroscopy which shows losses in internal open circuit voltage (iVoc) from 820 meV to 795 meV, carrier lifetime from 123 ns to 45 ns, and PL quantum yield from 2.9x10-5 to 1.2x10-5. Modeling time-resolved PL lifetimes demonstrates the back surface recombination velocity due to metallization reduces minority carrier lifetimes. These results identify the native oxide and show that it plays an important role in mediating downward band bending along with how the back interface reaction can negatively impact device-scale parameters and reduce PV PCE.
Back-contacting p-type CdTe has been identified as one of the major areas of loss in CdTe photovoltaic (PV) power conversion efficiency (PCE). In research settings, Au is a common contact material due to its ease of use and decent performance. This work provides a detailed investigation into using gold for back contacting As-doped, CdCl 2 -treated, polycrystalline CdTe that has been exposed to air after absorber processing, another routine practice. First, X-ray photoemission spectroscopy (XPS) is used to determine the native oxide to be 1.6 nm of CdTeO 3 by using a combination of angle-resolved XPS and the cadmium-modified Auger parameter. During gold metallization of CdTe, oxygen and oxidized tellurium are eliminated from the thin CdTeO 3 native oxide. The fates of the released oxygen and possibly cadmium and tellurium are not known, but these reaction byproducts can enter the absorber bulk or grain boundaries, stay at the interface, or dissolve in the Au. Interfacial hole barriers between CdTe and Au are measured for samples with and without the native oxide present prior to metallization. Results show that the thin CdTeO 3 alleviates the downward band bending by 40 meV from 470 to 430 meV even though it is consumed during interface formation. The implications of these chemical reactions on the device are assessed through photoluminescence (PL) spectroscopy, which shows losses in internal open circuit voltage (iVoc) from 820 to 795 meV, carrier lifetime from 123 to 45 ns, and PL quantum yield from 2.9 × 10 −5 to 1.2 × 10 −5 . Modeling timeresolved PL lifetimes demonstrates the back surface recombination velocity due to metallization reduces minority carrier lifetimes. These results identify the native oxide and show that it plays an important role in mediating downward band bending along with how the back interface reaction can negatively impact device-scale parameters and reduce PV PCE.
Graphical abstract: - Highlights: • CdSe@ZnS nanocomposites were produced by milling. • Negligible cadmium leakage was observed. • No toxicity against living cells was documented. • The material is suitable for biological imaging. - Abstract: CdSe@ZnS nanocomposites have been prepared by a two-step solid state mechanochemical synthesis. CdSe prepared from Cd and Se elements in the first step was mixed with zinc acetate and sodium sulphide in the second step of milling to prepare a CdSe@ZnS nanocomposite. In the third step, the obtained nanocomposite was coated with L-cysteine to prepare a biocompatible system. The crystallite size of the new type of nanocomposite was 20–35 nm for cubic CdSe and 3–8 nm for hexagonal ZnS as calculated from XRD, TEM and SEM data. The synthesised samples show good crystallinity and have been tested for dissolution and cytotoxicity. The dissolution of cadmium from CdSe@ZnS was less than 0.05 μg mL{sup −1}, whereas a value of 0.8 μg mL{sup −1} was measured for CdSe alone. The binding of ZnS with CdSe in the nanocomposite practically eliminated the release of cadmium into solution. As a consequence, a very low cytotoxic activity has been evidenced for CdSe@ZnS. The nanocomposites coated with L-cysteine have a great potential as fluorescent labels in biomedical engineering.
Contamination of soils with heavy metals may pose long-term risk to groundwater quality leading to health implications. Bioavailability of heavy metals, like cadmium (Cd) is strongly affected by sorption and desorption processes. The release of heavy metals from contaminated soils is a major contamination risks to natural waters. The release of Cd from contaminated soils is strongly influenced by its mobility and bioavailability. In this study, the kinetics of Cd desorption from ten samples of contaminated calcareous soils, with widely varying physicochemical properties, were studied using 0.01 M EDTA extraction. The median percentage of Cd released was about 27.7% of the total extractable Cd in the soils. The release of Cd was characterized by an initial fast release rate (of labile fractions) followed by a slower release rate (of less labile fractions) and a model of two first-order reactions adequately describes the observed release of Cd from the studied soil samples. There was positive correlation between the amount of Cd released at first phase of release and Cd in exchangeable fraction, indicating that this fraction of Cd is the main fraction controlling the Cd in the kinetic experiments. There was strongly negative correlation between the amount of Cd released at first and second phases of release and residual fraction, suggesting that this fraction did not contribute in Cd release in the kinetic experiments. The results can be used to provide information for evaluation of Cd potential toxicity and ecological risk from contaminated calcareous soils.
Highlights: • Chemical risks were assessed in the nine cathode ray tube screens recycling facilities. • The main hazardous agents are dust containing lead, cadmium, barium and yttrium. • Exposure and pollutant levels are described for different operations and processes. • All the operations and processes are concerned by significant levels of pollutants. • We suggest recommendations to reduce chemical risk. - Abstract: The Waste Electrical and Electronic Equipment (WEEE) or e-waste recycling sector has grown considerably in the last fifteen years due to the ever shorter life cycles of consumables and an increasingly restrictive policy context. Cathode Ray Tubes (CRTs) from used television and computer screens represent one of the main sources of e-waste. CRTs contain toxic materials such as lead, cadmium, barium, and fluorescent powders which can be released if recycling of CRTs is not appropriate. Exposure to these harmful substances was assessed in nine workshops where CRT screens are treated. Particulate exposure levels were measured using a gravimetric method and metals were analysed by plasma emission spectrometry. The maximum levels of worker exposure were 8.8 mg/m{sup 3}, 1504.3 μg/m{sup 3}, 434.9 μg/m{sup 3}, 576.3 μg/m{sup 3} and 2894.3 μg/m{sup 3} respectively for inhalable dust, barium, cadmium, lead and yttrium. The maximum levels of airborne pollutants in static samples were 39.0 mg/m{sup 3}, 848.2 μg/m{sup 3}, 698.4 μg/m{sup 3}, 549.3 μg/m{sup 3} and 3437.9 μg/m{sup 3} for inhalable dust, barium, cadmium, lead and yttrium. The most harmful operations were identified, and preventive measures for reducing the chemical risk associated with screen recycling were proposed. Workplace measurements were used to define recommendations for reducing the chemical risks in CRT screens recycling facilities and for promoting the design and development of “clean and safe” processes in emerging recycling channels.
Anthropogenic activities such as industrial processes often produce copious amounts of contaminants that have the potential to negatively impact growth, survival, and reproduction of exposed wildlife. Coal combustion residues (CCRs) represent a major source of pollutants globally, resulting in the release of potentially harmful trace elements such as arsenic (As), cadmium (Cd), and selenium (Se) into the environment. In the United States, CCRs are typically stored in aquatic settling basins that may become attractive nuisances to wildlife. Trace element contaminants, such as CCRs, may pose a threat to biota yet little is known about their sublethal effects on reptiles. To assess the effects of CCR exposure in turtles, we sampled 81 yellow-bellied sliders (Trachemys scripta scripta) in 2014-2015 from CCR-contaminated and uncontaminated reference wetlands located on the Savannah River Site (Aiken, SC, USA). Specific aims were to (1) compare the accumulation of trace elements in T. s. scripta claw and blood samples between reference and CCR-contaminated site types, (2) evaluate potential immunological effects of CCRs via bacterial killing assays and phytohaemagglutinin (PHA) assays, and (3) quantify differences in hemogregarine parasite loads between site types. Claw As, Cd, copper (Cu), and Se (all p ≤ 0.001) and blood As, Cu, Se, and strontium (Sr; p ≤ 0.015) were significantly elevated in turtles from CCR-contaminated wetlands compared to turtles from reference wetlands. Turtles from reference wetlands exhibited lower bacterial killing (p = 0.015) abilities than individuals from contaminated sites but neither PHA responses (p = 0.566) nor parasite loads (p = 0.980) differed by site type. Despite relatively high CCR body burdens, sliders did not exhibit apparent impairment of immunological response or parasite load. Additionally, the high correlation between claw and blood concentrations within individuals suggests that nonlethal tissue sampling may be useful for monitoring CCR exposure in turtles.
End-of-life management is important for addressing large future photovoltaic (PV) waste volumes and conserving raw materials for use in new PV modules. In regions without regulatory mandates for PV recycling, end-of-life PV modules can be disposed in accordance with general waste laws. Given the use of various metals as raw materials in semiconductor compounds and electrical contacts in commercial PV modules, some stakeholders have raised concerns regarding potential environmental impacts if PV modules are subject to improper disposal instead of being recycled or disposed in sanitary landfills, as is required in most world regions. To evaluate these concerns, screening-level risk assessment methods are developed herein that evaluate potential human health risks from groundwater and surface (air, soil, surface water) exposure pathways. The methods estimate potential impacts from disposal of end-of-life (EOL) PV modules in non-sanitary landfills under the following worst-case conditions: no leachate collection or groundwater monitoring, no liner for preventing leachate migration, uncovered waste, and lack of stormwater management. Examining worst-case conditions allows the exploration of maximum potential risk to attempt to ensure disposal does not increase health risk above regulatory thresholds. Specifically, this report presents an analysis of potential human health risks associated with non-sanitary landfill disposal for three PV technologies, focusing on release of the highest-prioritized chemical element for each: lead (Pb) in crystalline-silicon (c-Si) PV modules, cadmium (Cd) in thin film cadmium telluride (CdTe) PV modules, and selenium (Se) in thin film copper indium selenide (CIS) PV modules. The prioritization of these chemical elements for analysis is based on stakeholder interest. Because the methodology is chemical-specific, the risk assessment results for these chemicals cannot be directly generalized to other chemicals, although the risk assessment methodology can be applied to other chemicals. If the chemicals chosen are indeed the ones presenting greatest risk, then the results herein should represent the upper bound of health risk from exposure to a single constituent.
Photovoltaic (PV) modules are designed and tested for long-term durability in harsh outdoor environments, but a small percentage may break during installation or operation. Some industry stakeholders have expressed concerns regarding potential human exposure to hazardous materials should a PV module break in the field. To evaluate these concerns, screening-level risk assessment methods are presented that can estimate emissions that may occur when broken PV modules are exposed to rainwater, estimate the associated chemical concentrations in soil, groundwater and air, and finally compare these exposure-point concentrations to health-protective screening levels based on 1 x 10-6 cancer risk and hazard quotient of 1. The screening-level methods can be used to decide whether further evaluation of potential health risks is warranted. A few example scenarios demonstrate application of the methods. Specifically, this report presents an analysis of potential human health impacts associated with rainwater leaching from broken modules for two PV technologies, focusing on release of the highest-prioritized chemical element for each: lead (Pb) content in crystalline-silicon (c-Si) PV modules and cadmium (Cd) content in thin film cadmium telluride (CdTe) PV modules. The prioritization of these chemical elements for analysis is based on stakeholder interest. Because the methodology is chemical-specific, the risk assessment results for these chemicals cannot be directly generalized to other chemicals, although the risk assessment methodology can be applied to other chemicals.