Environmental Fate, Recovery and Microbial Toxicity of the Semiconductor Materials GaAs, CdTe and CdSe

摘要

Gallium arsenide (GaAs), cadmium selenide (CdSe), and cadmium telluride (CdTe) are semiconductor materials with remarkable opto-electronic properties that make them suitable for a wide variety of applications including, light emitting diodes (LEDs), mobile phones, tablets, and solar panels. Due to the growing demand and the short lifespan of these electronic devices, a remarkable amount of electronic waste (e-waste) has been produced in the last decades. An important fate of e-waste is landfill disposal; therefore, there is an increasing concern about the release of toxic elements into the landfill environment and the potential risks for human health and the environment. Among the elements constituting GaAs, CdTe, and CdSe, tellurium (Te) has gained increasing attention in recent years. Tellurium is a scarce element on the earth’s crust, and a shortage in its supply might compromise the development of new advanced technology, particularly in the energy and defense fields. For these reasons, the US Department of Energy and the European Union regard Te as a critical element, and have urged the need to develop efficient and cost-effective processes to recover Te from waste streams. This thesis dissertation explored different aspects related to the fate and impact of the widely used semiconductor materials, GaAs, CdSe and CdTe in municipal mixed solid waste (MSW) landfills. Furthermore, it investigated the removal of the Te oxyanions, tellurite (Teᴵⱽ, TeO₃²⁻) and tellurate (Teⱽᴵ, TeO₄²⁻), from aqueous streams and the recovery of this strategic metalloid as biogenic, elemental tellurite (Te⁰) nanoparticles (NPs). In the first part this work, the dissolution of GaAs was evaluated under a range of redox conditions, pH levels, ionic strength, and the presence of organic constituents commonly found in landfills. Our results indicated that aerobic conditions and mildly alkaline pH conditions favor the dissolution and release of high levels of soluble arsenic (As) and gallium (Ga) to the synthetic leaching solutions. The rate of As and Ga dissolution in long-term exposure experiments was initially constant but later progressively decreased due to the formation of a passivating layer on the surface of GaAs. The leaching behavior of CdSe and CdTe was also investigated under different pH and redox conditions in solutions simulating landfill leachates. CdTe and CdSe were subjected to two different standardized leaching tests, the federal Toxicity Characteristic Leaching Procedure (TCLP) and the California Waste Extraction Test (WET). CdTe showed a very high leaching potential in both tests and the concentrations of Cd released were 1500- and 260-times higher than the regulatory limit (1 mg Cd L⁻¹), respectively. In contrast, CdSe was relatively stable and dissolved selenium (Se) in both leaching tests was below the regulatory threshold (1 mg Se L⁻¹). Tests performed under different pH and redox conditions confirmed a marked enhancement in CdTe and CdSe dissolution both under acidic pH and aerobic conditions, which is consistent with thermodynamic predictions. Due to the high leaching potential observed for CdTe in the previous batch experiments, leaching studies were designed to investigate the potential release of soluble Cd and Te from a commercially available CdTe thin-film solar panel under different chemical and biogeochemical conditions commonly found in landfills. The solar panel was subjected to two standardized batch leaching tests (i.e., TCLP and WET), and to a continuous column test designed to investigate the dissolution of CdTe under conditions simulating the acidic- and the methanogenic circumneutral phases of a MSW landfill. A negligible amount of Cd and Te was measured in the synthetic leachate of both batch tests. On the other hand, a significant amount of Cd and Te was released from the panel to the synthetic leachate of the column simulating an acid landfill after 30 days (73% and 21% of the total Cd and Te, respectively). In contrast, the amount of Cd or Te detected in the effluent of the column operated at circumneutral pH values was negligible. The marked difference in the leaching behavior of CdTe in both columns is related to the different aqueous pH and redox conditions promoted by the microbial communities in the columns. The microbial toxicity of the soluble species that can be released from CdTe and CdSe was also assessed as a part of this work. The toxicity of cadmium (Cdᴵᴵ), selenite (Seᴵⱽ), selenate (Seⱽᴵ), Teᴵⱽ, and Teⱽᴵ was evaluated in bioassays with different microbial targets, including acetoclastic and hydrogenotrophic methanogenic populations in a mixed microbial culture, similar to those involved in the stabilization of organic waste stabilization in a landfill, and the bioluminescent marine bacterium, u1d434u1d459u1d456u1d456u1d463u1d456u1d44fu1d45fu1d456u1d45c u1d453u1d456u1d460u1d450ℎu1d452u1d45fu1d456 (Microtox® test). The acetoclastic methanogens were most sensitive to the presence of the various soluble species, with the toxicity decreasing in the following order: Cdᴵᴵ, Teᴵⱽ, Teⱽᴵ, Seᴵⱽ, while Seⱽᴵ was only toxic at non-environmentally relevant concentration. Hydrogenotrophic methanogens were highly inhibited by Cdᴵᴵ and Seᴵⱽ, but Teᴵⱽ and Teⱽᴵ only had a moderate toxic impact. The bacterium u1d434. u1d453u1d456u1d460u1d450ℎu1d452u1d45fu1d456 was very sensitive to inhibition by Cdᴵᴵ and Seᴵⱽ, and Teᴵⱽ. In the last part of this work, the potential recovery of insoluble, elemental Te⁰ NPs from aqueous solutions containing soluble Teᴵⱽ or Teⱽᴵ was investigated in batch- and continuous flow bioreactors inoculated with a methanogenic granular mixed culture. In the batch experiments, the capacity of the culture to catalyze the reduction of the Te oxyanions and to produce Te⁰ NPs internally and externally to the cells was demonstrated. The granular sludge was found to contain enough endogenous substrates to provide the electron equivalents required to reduce both Te oxyanions and the reduction rates were only modestly increased by an exogenous electron-donor (e-donor) such as H₂. The effect of several redox mediators (RM), namely, anthraquinone-2,6-disulfonate (AQDS), hydroxocobalamin, riboflavin, and lawsone, was also tested. Riboflavin and lawsone caused a remarkable increase of the rate of Teᴵⱽ and Teⱽᴵ reduction, respectively, and also enhanced the fraction of Te recovered as extracellular Te⁰ NPs. The morphology and localization of the Te⁰ NPs were also impacted by the presence of a particular RM and e-donor in the system, suggesting that NP production can be tailored for a particular application. Finally, the feasibility of utilizing upflow anaerobic sludge bed (UASB) bioreactors to reduce Teᴵⱽ oxyanions to non-toxic Te⁰ NPs was also investigated. Two reactors were supplied with ethanol as the external e-donor source to promote the biological reduction of Teᴵⱽ. Riboflavin, a redox mediator, was supplied to one of the reactors to enhance Teᴵⱽ bioreduction. Continuous formation of Te⁰ NPs using an UASB was found to be feasible and remarkably improved by addition of riboflavin at the low Teᴵⱽ:riboflavin molar ratio of 4:1. This flavonoid enhanced the conversion rate of Teᴵⱽ and reduced the toxic impact of Teᴵⱽ towards the methanogenic consortium. Overall, the evidence found in this work indicates that recycling of decommissioned devices containing GaAs, CdTe, or CdSe is desirable to prevent the potential environmental release of toxic metals and metalloids in MSW landfills, but also to allow the recovery of critical resources. Microbial processes offer potential for the removal and recovery of soluble metals and metalloid ions leached from decommissioned semiconductor materials. In particular, this study demonstrated the feasibility of utilizing continuous UASB bioreactors for the removal of Teᴵⱽ from aqueous streams and the recovery of this valuable metalloid as biogenic Te⁰ NPs.