The arsenic maximum contaminant level (MCL) for drinking water is likely to be lowered sometime in 2001 or 2002. If the MCL is lowered, it is speculated that there will be stricter limits imposed on the disposal and handling of arsenic-containing residuals. The purpose of this study is to determine the properties of drinking water residuals, including the chemical characteristics, the amount of arsenic that leaches in common residual handling and dewatering processes, and the hazardous potential of the residuals. Residual samples were collected from seven utilities with high arsenic concentrations in their raw water. Included in the study were four plants that coagulate with ferric chloride, two with aluminum hydroxide, and one softening plant. The residuals from each facility were acid digested and chemically characterized using ICP-AES to determine the total arsenic, aluminum and iron present. TCLP and California WET were performed to verify if the residuals were hazardous. Simulated lagoons were set up and monitored over a six-month period to determine the amount of arsenic that was leached to the liquid portion over time. Toxicity testing was performed on the residuals at 20% and 100% after two months and six months of storage. Bench-scale sand drying beds were used to dewater residuals, and the leachates were analyzed to determine if arsenic leached from residuals. The residuals were found to contain high levels of arsenic during the chemical characterization. However, all of the facilities passed the current TCLP limit of 5 mg/L. For all residuals, the California WET values were much higher than the TCLP values. In the lagoon study, redox potentials decreased and the arsenic and iron concentrations in the liquid portions increased. In the sand drying beds, very little arsenic leached; arsenic concentrations in the leachate were less than 10 ppb. Lagoon storage may not be a safe alternative for residuals containing arsenic. However, sand drying does not appear to present any threats. There were differences between the toxicity tests performed at 100% solids and 20% solids in the lagoon study. Some of the values increased and others decreased. Additionally, toxicity testing conducted after lagoon aging differed from earlier toxicity testing, due to the changing soluble arsenic. These discrepancies suggest that the test results can be affected by the percent solids and age of the residuals, and specific instructions should be given for consistent residuals testing. / Master of Science

abstract: The volume of end-of-life photovoltaic (PV) modules is increasing as the global PV market increases, and the global PV waste streams are expected to reach 250,000 metric tons by the end of 2020. If the recycling processes are not in place, there would be 60 million tons of end-of-life PV modules lying in the landfills by 2050, that may not become a not-so-sustainable way of sourcing energy since all PV modules could contain certain amount of toxic substances. Currently in the United States, PV modules are categorized as general waste and can be disposed in landfills. However, potential leaching of toxic chemicals and materials, if any, from broken end-of-life modules may pose health or environmental risks. There is no standard procedure to remove samples from PV modules for chemical toxicity testing in the Toxicity Characteristic Leaching Procedure (TCLP) laboratories as per EPA 1311 standard. The main objective of this thesis is to develop an unbiased sampling approach for the TCLP testing of PV modules. The TCLP testing was concentrated only for the laminate part of the modules, as they are already existing recycling technologies for the frame and junction box components of PV modules. Four different sample removal methods have been applied to the laminates of five different module manufacturers: coring approach, cell-cut approach, strip-cut approach, and hybrid approach. These removed samples were sent to two different TCLP laboratories, and TCLP results were tested for repeatability within a lab and reproducibility between the labs. The pros and cons of each sample removal method have been explored and the influence of sample removal methods on the variability of TCLP results has been discussed. To reduce the variability of TCLP results to an acceptable level, additional improvements in the coring approach, the best of the four tested options, are still needed. / Dissertation/Thesis / Masters Thesis Engineering 2018

abstract: Solar photovoltaic (PV) deployment has grown at unprecedented rates since the early 2000s. As the global PV market increases, so will the volume of decommissioned PV panels. Growing PV panel waste presents a new environmental challenge, but also unprecedented opportunities to create value and pursue new economic avenues. Currently, in the United States, there are no regulations for governing the recycling of solar panels and the recycling process varies by the manufacturer. To bring in PV specific recycling regulations, whether the PV panels are toxic to the landfills, is to be determined. Per existing EPA regulations, PV panels are categorized as general waste and are subjected to a toxicity characterization leaching procedure (TCLP) to determine if it contains any toxic metals that can possibly leach into the landfill. In this thesis, a standardized procedure is developed for extracting samples from an end of life PV module. A literature review of the existing regulations in Europe and other countries is done. The sample extraction procedure is tested on a crystalline Si module to validate the method. The extracted samples are sent to an independent TCLP testing lab and the results are obtained. Image processing technique developed at ASU PRL is used to detect the particle size in a broken module and the size of samples sent is confirmed to follow the regulation. / Dissertation/Thesis / Masters Thesis Engineering 2017

This research project aimed at evaluating four internationally accepted leachate extraction tests to determine their applicability on sewage sludge samples. Furthermore, the present analytical method to determine the leachable fraction of sludge for compliance to South African sludge legislation was evaluated. Leaching tests are done on sludge samples to determine element mobility. This is important since land application of sewage sludge is an accepted and regulated sludge management practice. A literature survey was done to evaluate the mobility over time of metals originating from sludge-amended soils. Mobility is initially due to the organic content of the soil and after organic matter decomposition, it is dependant on the inorganic content. Mobile metals in sludge-amended soil can cause potential environmental risks like groundwater contamination and metal accumulation in soil. Metal accumulation can further lead to increased plant uptake of metals. To determine the partitioning or fractionation of metals found in sludge-amended soil, selective sequential extractions and single extractions can be used. Since South African sludge legislation specifies a single extraction procedure, four were selected for comparative studies. The selected procedures were the USA Environmental Protection Agency (EPA) Toxicity Characteristic Leaching Procedure (TCLP) the Australian Standard Bottle leaching Test (AS 4439.3) the Nederlands Normalisatie-Insitiuut availability test (NEN 7341) and the Deutches Institut für Normung water leachability test (DIN 38 414-S4). A variation of the TCLP is specified for use in South Africa. Three sewage sludge sample lots were collected. The first consisted of 24 sub-samples that were collected from 24 different wastewater treatment works on the East Rand. Both leachable (TCLP) and total (aqua regia) extraction was done on these samples for Cd, Co, Cr, Cu, Hg, Mo, Ni, Pb, Zn, Se, B and Fe. A relationship between the leachable and total extractions was found for Co and Pb but could not be tested by literature values due to a variation in the sample preparation. The TCLP leachates were also analysed by Atomic Absorption and Inductively Coupled Plasma techniques to compare the applicability of the two. It was found that both techniques are acceptable for leachate analysis. The second sample lot collected from a single wastewater treatment plant was used to determine the leachable effect of the difference between the South African adapted TCLP and the USA EPA procedure as well as the NEN procedure. The EPA specifies all samples be extracted on an “as is” basis while the South African adaptation specifies dry samples. It was found that no element was comparative between dry and wet sample for both extraction procedures. It was observed that wet extractions yield generally higher values than dry extractions. A third sample lot was collected two months after the second sample lot at the same wastewater treatment works. It was used to compare the four extraction procedures. From this it was found that the DIN yielded the highest results for the specified elements. This procedure could not be recommended since the experimental difficulties and the duration of the test make it an unsuitable regulatory compliance tests protocol. / Dissertation (MSc (Environmental Technology))--University of Pretoria, 2006. / Chemical Engineering / unrestricted

>Magister Scientiae - MSc / Fly ash is the most abundant of the waste materials generated from coal combustion in coal-fired power stations. South Africa uses more than 100 million tonnes of low grade bituminous coal annually to produce cheap electricity thereby generating huge amounts of fly ash each year. The disposal of fly ash has been a major concern to the world because of its potential environmental impact due to the possible leaching of the toxic elements contained in fly ash. This study centres on the chemical characterization and leaching behaviour of the fly ashes generated from SASOL Synfuels and ESKOM power station at Secunda and Tutuka in South Africa respectively. The aim is to understand the composition of the fly ashes and to determine the leachability of species from the ashes in order to predict the environmental effect of the different ash handling system of the coalfired stations (wet disposal system in Secunda and dry disposal system in Tutuka). Several leaching methods were employed in this study in order to develop a methodology for evaluating and modelling ash system and were able to discriminate between ash types and model ash handling system. Fly ashes from the two South African coal-fired stations were subjected to total acid-digestion and XRF analyses in order to determine the total amounts of major and minor species contained in the fly ashes. The total acid-digestion test and the XRF analysis revealed that the major species such as Al, Si, Ca, Na, Mg, K, Sr, Ba and S04, and minor species such as Fe, Ti, V, Mn, Cr, Ni and Cu were present in both fly ashes in fairly similar concentrations. The mineralogical characterization by XRD of Secunda and Tutuka fly ashes revealed mullite and quartz as the major mineral phases with minor peaks of CaO and calcite. Several leaching tests and different leaching conditions were employed in this study in order to develop a standardized replicable methodology for environmental impact assessment and for modelling the impact of different ash handling scenarios. The fly ashes were exposed to these different leaf leachant of different pHs on the leachability of species from the fly ashes. To achieve this, DIN-S4, TCLP and ANC tests were employed. The natural pH of the fly ash leachates were very high ranging between 12.56 and 13.08. The DIN-S4 leaching test revealed that the easily soluble species of the fly ashes include Ca, Mg, Na, K and S04 and various toxic elements. The leachates from the TCLP test recorded higher concentrations of Ca, Mg, Na, K and S04 which was attributed to the slight decrease in the pH due to the addition of a acidic leachant with a pH of 2.88. Comparison of the amount leached (DIN-S4) from the fly ashes with the total concentrations of each of the components of the fly ashes (determined by the total acid-digestion), the percentage of each of the readily soluble species ranged from 15-24.23% for Ca, 0.23-0.45% for K, 0.58-0.82% for Na, 0.0047-0.007% for Mg, 0.96-3.33% for Ba and 0.012-1.51 % for S04 per dry mass of each component in the fly ash. The ANC test revealed the effect of a leachant of specified pH on the release of species from the fly ashes with concentrations of the major and minor species leached out of the fly ashes found to be higher than the concentrations released into the leachates when DIN-S4 and TCLP test were considered at specific pH and showed the pH dependence of the solubility and release of species. These tests also showed the effect of the liquid to solid ratio upon leachability of species. In addition to the batch leaching tests mentioned above, dissolution kinetics and up-flow percolation tests were carried out on the fly ashes to determine the leaching behaviours of the fly ashes over time and the factors controlling the release of species from the fly ashes in the long term. The dissolution kinetics test was done for an extended period of 60 days with recycle of the leachant and the up-flow percolation test was carried out with constant leachant renewal until a liquid/solid ratio of 20 was attained (:::::;9d0ays). The geochemical computer code PHREEQC and MINTEQ database was used for geochemical modelling of the leachates at various reaction times and LIS ratios. The geochemical modelling results revealed that the release of the species from the fly ashes is controlled by the solubility of mineral phases in many case except for Na. The release of Ca, S04, Mg, Ba and Sr in the leachates of the fly ashes were predicted to be controlled by portlandite, gypsum, brucite, barite and celestite respectively while birnessite, magnetite, BaCr04, CaMo04 and Ba(As04h were predicted to be the mineral phases controlling the release of Mn, Fe, Cr, Mo and As respectively. The pH of the leachates plays a significant role in the leaching of both major and minor species from the fly ashes. The concentrations of species leached into solution at low pH (ANC and TCLP) were higher than the concentrations released at high pH (DIN-S4, dissolution kinetics and up-flow percolation tests). The amounts of the toxic elements such as As, Se, Cd, Cr and Pb that leached out of the fly ashes when in contact with demineralized water (DIN-S4) were very low and below the target water quality range (TWQR) of South African Department of Water Affairs and Forestry (DWAF), but the amounts of As and Se leached out by acidic leachant applied in the TCLP test and at lower pH ranging between 8 and 10 the case of the ANC test were slightly higher than the TWQR, which is an indication that the pH of the leaching solution and the contact time playa significant role on the leaching of species out of the fly ashes. This study revealed that the leaching of species from the fly ashes depends on various factors which include: physical and chemical characteristics and mineralogical composition of the fly ashes, the total concentrations of species in the ash, the rate of flow through the ash system and more importantly the pH of the leachant to which the ash system is exposed to. The results of different experiments and analysis carried out on the two South African fly ashes (Secunda and Tutuka fly ashes) showed that, despite the high concentrations of soluble species or leachable elements in the fly ashes, the leaching of major, minor and trace elements into the soils and the groundwater could be minimized if certain conditions such as avoiding acidic precipitation that could reduce the pH of the ash system are adhered to. The leaching trends of the species and the geochemical modelling data also showed that the formation of secondary mineral phases could reduce the release of toxic elements, the release of which would require aggressive low pH leachants, high flow rate, high recharge and long-term leaching for the dissolution of the formed mineral phases. In conclusion, the combination of the leaching tests employed in this study gives information on the leaching behaviour of the Secunda and Tutuka fly ashes and the factors controlling the leaching of the elements from the fly ashes. This study has been able to show that elements are leached out of the fly ashes at both alkaline and acidic pH. It is also revealed in the study that the disposal techniques employed by the coal-fired stations which were simulated by using the dissolution kinetics and up-flow percolation tests are adequate methods for modelling of the ash disposal scenario. These two methods show that the dry disposal system at Tutuka will encourage equilibration of the ash/water system thereby facilitating the precipitation of mineral phases that could control the release of both major and minor species from the fly ash, whereas the wet ashing system at Secunda may expose the ash to sufficient flow to rapidly leach species out into the environment.