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In this research, in order to set up the ultimate approaches to determine the content of chromium(¢¾) in seawater, different pH values, the amount of chelating agent, chelating time and extraction time were investigated in two different solvent extraction systems, APDC-MIBK and Aliquat 336-MIBK. In APDC-MIBK system, the ultimate extracting condition is that 400 mL sample is adjusted to pH 3.0, added 4 % APDC 4 mL to chelate chromium(¢¾) for 60 minutes, and added 20 mL MIBK to partiton into two fractions for 5 minutes. The recovery in APDC-MIBK system is 68 %~ 123 %. The method detection limit is 0.2 ppb. In Aliquat 336-MIBK system, the ultimate extracting condition is that 400 mL sample is adjusted to pH 2.0, added 5 % Aliquat 336 4 mL to chelate chromium(¢¾), added 20 mL MIBK to be shaken for 2 minutes, and partitoned into two fractions for 5 minutes. The recovery in Aliquat 336-MIBK system is 80 %~ 120 %. The method detection limit is 0.1ppb. Although in APDC-MIBK system assorted metals can be extracted at same time, it is steadier in Aliquat 336-MIBK system than APDC-MIBK system. Therefore, it is a feasible extraction method to adopt Aliquat 336-MIBK system to determine the content of chromium(¢¾) in seawater.

It was been reported that untreated wastes from ferrochrome plants release heavy metals including lead, chromium, copper, cadmium, zinc and nickel in the environment. Some of these metals such as hexavalent chromium are potentially toxic and carcinogenic, and can cause a serious threat to human health. The contamination of terrestrial and aquatic ecosystems by hexavalent chromium is worldwide of major environmental concern, especially in South Africa which is the largest producer of chromite and ferrochrome. Therefore, the pre-treatment of these wastes before landfill is of great importance to prevent the contamination of the ecosystems. In the present study, vermiculite, a natural occurring mineral, has been tested for its adsorption effectiveness in removing Cr(VI) from ferrochrome dust leachate. Batch adsorption studies have been carried out to determine the effect of pH, contact time and adsorbent dose on the removal of Cr(VI). The process was found to be highly pH dependent. The optimum conditions for the removal were found to be at pH 1.5, contact time 2 hours and adsorbent dose 10 g.L-1. According to kinetic and isotherm studies, the process is best fitted by the pseudo-second order kinetic model, and to both Langmuir and Freundlich isotherms. The maximum adsorption capacity was found to be 23.25 mg.g-1. Thermodynamic parameters show the spontaneous and endothermic nature of Cr(VI) adsorption onto vermiculite. / Dissertation (MSc)--University of Pretoria, 2011. / Materials Science and Metallurgical Engineering / unrestricted

abstract: Carbon nanomaterials have caught tremendous attention in the last few decades due to their unique physical and chemical properties. Tremendous effort has been made to develop new synthesis techniques for carbon nanomaterials and investigate their properties for different applications. In this work, carbon nanospheres (CNSs), carbon foams (CF), and single-walled carbon nanotubes (SWNTs) were studied for various applications, including water treatment, energy storage, actuators, and sensors. A facile spray pyrolysis synthesis technique was developed to synthesize individual CNSs with specific surface area (SSA) up to 1106 m2/g. The hollow CNSs showed adsorption of up to 300 mg rhodamine B dye per gram carbon, which is more than 15 times higher than that observed for conventional carbon black. They were also evaluated as adsorbents for removal of arsenate and selenate from water and displayed good binding to both species, outperforming commercial activated carbons for arsenate removal in pH > 8. When evaluated as supercapacitor electrode materials, specific capacitances of up to 112 F/g at a current density of 0.1 A/g were observed. When used as Li-ion battery anode materials, the CNSs achieved a discharge capacity of 270 mAh/g at a current density of 372 mA/g (1C), which is 4-fold higher than that of commercial graphite anode. Carbon foams were synthesized using direct pyrolysis and had SSA up to 2340 m2/g. When used as supercapacitor electrode materials, a specific capacitance up to 280 F/g was achieved at current density of 0.1 A/g and remained as high as 207 F/g, even at a high current density of 10 A/g. A printed walking robot was made from common plastic films and coatings of SWNTs. The solid-state thermal bimorph actuators were multifunctional energy transducers powered by heat, light, or electricity. The actuators were also investigated for photo/thermal detection. Electrochemical actuators based on MnO2 were also studied for potential underwater applications. SWNTs were also used to fabricate printable electrodes for trace Cr(VI) detection, which displayed sensitivity up to 500 nA/ppb for Cr(VI). The limit of detection was shown to be as low as 5 ppb. A flow detection system based on CNT/printed electrodes was also demonstrated. / Dissertation/Thesis / Doctoral Dissertation Materials Science and Engineering 2015

An innovative sampling technique employing extractant impregnated membranes is presented for the selective sorption and stabilization of specific oxidation states of chromium. Polymer-based selective ion traps employing the extractants tricaprylmethylammonium chloride (Aliquat-336) and di-(2-ethylhexyl) phosphoric acid (DEHPA) were used for the selective removal and enrichment of the anionic forms of Cr(VI) and cationic forms of Cr(III), respectively. Results show Aliquat-336 and DEHPA effectively remove Cr(VI) and Cr(III) from aqueous solutions. Extraction efficiency is independent of source concentration from 1-50 ppm but is dependent upon time, pH of the source, ionic strength, extractant concentration, composition of source phase, and choice of stripping agent and stripping agent concentration. Optimum conditions for Cr(VI) and Cr(III) were determined to be 1 v/v% Aliquat-336 and 30 v/v% DEHPA; an extraction time of at least 3-5 days; source phase pH between 3-5; and 1 M NaOH/ 0.5 M HNO3 as stripping agent for Cr(VI) and Cr(III) species, respectively. Batch extraction efficiencies of 97 +/- 3 % were obtained for the optimal conditions. Inductively Coupled Plasma Atomic Emission Spectrometry (ICP-AES) was used for total chromium determination. UV-VIS spectrometry was used for Cr(VI) determination. Scanning Electron Microscopy revealed the physical structure of the polymeric supports and subsequent impregnation was evidenced by the SEM images. X-ray photoelectron spectroscopic results provided the elemental composition of the Versapor-450 membrane to be 71. 5% C, 7.0% O, 9.5% Cl and 12.0% N. The Whatman PP membrane was and 100.0 % C. Elemental composition of 1 v/v% Aliquat-336 on Versapor-450 and Whatman PP membrane was 92.3% C, 0.8% O, 3.6% N, and 3.3% Cl and 94.3% C, 3.3% N, and 2.4% Cl, respectively. Elemental composition of 30 v/v% DEHPA on Versapor-450 and Whatman PP membranes were 78.8% C, 3.4% P, 17.8% O and 76.3% C, 19.3% O, 4.4% P, respectively. Column studies under simulated groundwater conditions utilizing the extractant impregnated membranes showed no statistical difference in Cr(VI) recoveries from those obtained in batch experiments. Cr(III) extraction revealed a statistical difference in analyte recovery vs. batch experiments. This is attributed to the lowered pH and cationic interferences present in simulated groundwater. / Ph. D.

A sampler has been fabricated to facilitate the in-situ speciation of Cr. Teflon® was selected as the material for the samplers because of its inert chemical nature. The design of the sampler is based on the Supported Liquid Membrane (SLM) extraction technique, which utilizes charged organic carrier molecules loaded onto a polymeric (Teflon®) support membrane and the principles of electrostatics to selectively transport Cr ions through an ion-pairing mechanism. Cr ions in the feed solution that have an opposite charge from the carrier molecule form an ion-pair with the carrier and are transported through the membrane and deposited into a second aqueous phase referred to as the acceptor phase. A counter-ion from the acceptor phase is exchanged for the Cr ion to complete the extraction process. Since the acceptor phase is contained in a Teflon® bottle, the SLM sampler is capable of speciation and storage of Cr ions, which is a major advantage over current speciation techniques. A food coloring test was used to check the samplers for leaks. A plastic barrier was used in place of the polymeric membrane and the acceptor phase bottle was filled with DI water. The sampler was submerged in a beaker containing food coloring and DI water. The bottle contents were checked for the presence of food coloring using UV-vis spectroscopy. The sampler was determined to be leak-free if the bottle did not contain food coloring. All systems prepared were validated upon the initial test and required no further manipulation to ensure structural soundness. The SLM extraction technique involves two liquid-liquid extractions (LLEs). Before the samplers could be evaluated for their performance and stability in Cr speciation applications, liquid-liquid extraction studies were conducted on both systems (Cr (III) and Cr (VI)) to determine the optimal operating parameters (carrier concentration, decanol concentration, and acceptor phase concentration) of the SLM system. The selectivity of each system was also evaluated to validate proper SLM function. The performance of the samplers was evaluated in a series of tank studies that focused on the uptake of Cr into the acceptor phase as well as the depletion of Cr ion from this phase. The goal of the performance studies was to determine the mechanical and chemical stability of the SLM samplers. As part of the validation process, selectivity studies and studies without the carrier molecule were conducted to ensure that the systems were functioning according to SLM theory. Tank studies that simulated natural sampling condition were also conducted. The results of the tests conducted in the laboratory indicate that the SLM samplers are a stable, reliable, and viable method for Cr speciation. Future directions of this project will include the incorporation of the SLM sampler into the existing Multi-layer Sampler (MLS) technology as well as the analysis of the stability and performance of the incorporated systems in the ""in-situ speciation application. / Ph. D.

Ces travaux de thèse ont débuté par la présentation des propriétés physico-chimiques du chrome, ses principaux domaines d'application. On a aussi indiqué les problèmes posés et les risques associés à l'emploi des dérivés chromiques qui s'expriment essentiellement au niveau cutané, respiratoire et même immunologique. Ensuite, on a cité les différents procédés d'élimination tels que les procédés membranaires, procédés chimiques, procédés biologiques et procédés physiques en précisant les avantages et inconvénients de chacun de ces procédés. Après, on a présenté le procédé d'adsorption sur alumine activée, en rappelant brièvement les différents adsorbants utilisés ainsi que les modèles thermodynamiques et cinétiques utilisés pour décrire ce phénomène. Enfin, on a rappelé quelques généralités sur les membranes échangeuses d'ions et sur le procédé de dialyse ionique croisée. Dans une seconde étape, on a étudié la validation de la technique analytique selon la norme Française XPT 90-120, ensuite une étude préliminaire de l'influence des différents paramètres selon le plan d'expérimentation factorielle afin de montrer l'influence de chaque paramètre indépendamment et leurs dépendances aussi. Ces facteurs sont les suivants : pH, quantité de l'adsorbant, concentration du métal initial et de la température. Cette étude a porté sur l'effet du pH mais aussi l'effet de la masse de l'alumine activée et l'effet de la concentration initiale du chrome afin d'optimiser ces paramètres, les résultats expérimentaux ont montré que l'adsorption du chrome dépend essentiellement du pH et de la concentration du chrome initiale. Dans les conditions optimales, les taux d'élimination du chrome VI peuvent attendre 98 % pour une concentration initiale de 10 mg/L en chrome. Les résultats expérimentaux ont été appliqués aux modèles de Freundlich, Langmuir, Dubinin-Redushkevich et Temkin. Des études cinétique et thermodynamiques suivront pour déterminer l'ordre de la réaction d'adsorption des métaux lourds et nature exothermique du mécanisme. La troisième partie a porté sur la Dialyse Ionique Croisée, dans un premier temps on a développé une étude préliminaire de l'influence des différents paramètres selon le plan d'expérimentation effectué afin d'identifier et d'évaluer l'influence de chaque paramètre sur les taux d'élimination de l'ion métallique. Ces facteurs sont la concentration initiale de l'ion métallique, la concentration initiale de l'ion de substitution, le type de la membrane et l'agitation magnétique. Cette démarche est nécessaire afin de fixer les paramètres optimaux et évaluer leurs interactions mutuelles. Cette étude a permis de montrer que le type de membrane échangeuse d'anions est le plus important paramètre influant sur l'élimination du chrome et ceci peut s'expliquer par les valeurs élevées de la capacité d'échange et de la teneur en eau de la membrane AFN. La modélisation du transfert des ions HCrO4- en dialyse ionique croisée a montré la présence de deux phases : la couche limite de diffusion du côté de l'alimentation (solution à traiter contant les ions HCrO4-) et la membrane. En deuxième étape, nous avons effectué une étude du vieillissement des membranes, qui consiste à faire un suivie de l'épaisseur membranaire, de la conductivité membranaire et de leur morphologie par MEB. Nous avons montré que les membranes AMV et AFN se dégradent peu à priori de la même manière. Finalement, nous avons effectué un nouveau montage qui couple les deux procédés et ceci dans le but d'améliorer le taux d'élimination. Ce couplage a permis d'augmenter l'efficacité et la cinétique d'échange de la dialyse, en plus une réduction considérable de la quantité d'alumine activée à régénérer et l'amélioration de la cinétique de transfert transmembranaire / The removal of chromium (VI) from aqueous solutions by activated alumina has been investigated as a function of solution pH, initial chromium concentration, adsorbent dose of activated alumina and temperature. The pH and the adsorbent dose of activated alumina are the most significant parameters affecting chromium (VI) adsorption. The chromium concentrations were analyzed by reaction with 1,5-diphenylcarbazide. This method has been validated according to the French standard XPT-90-210. In order to optimize the effect of the main parameters and their mutual interaction for the adsorption process, a full factor design of the type nk has been used. In this study the removal of chromium (VI) by adsorption on activated alumina was investigated and results were fitted to Langmuir, Freundlich, Dubinin-Redushkevich and Temkin adsorption models, at different temperatures. The constants of each model were evaluated depending on temperature. Thermodynamic parameters for the adsorption system were determined at 10, 25 and 40°C. The obtained values showed that Cr (VI) adsorption is a spontaneous and exothermic process. The kinetic process was evaluated by first–order, second–order and Elovich kinetic models. In second section, the removal of chromium (VI) from aqueous solutions by Donnan dialysis has been investigated. The tows AEMs: Selemion AMV and Neosepta AFN. The amount of chromium removed was determined on the basis of the following parameters: initial chromium concentration, type of anion exchange membranes, co-ion concentration and magnetic stirring. A 24 full factorial design analysis was performed to screen the parameters affecting Cr (VI) removal efficiency were examined. Using the experimental results, a linear mathematical model representing the influence of the different parameters and their interactions was obtained. Analysis of variance (ANOVA), F-test and student's t- test showed that the type of anion exchange membrane is the most significant parameter affecting chromium (VI) removal. The statistical analysis of experimental data assumes that the data come from normal distribution. Then, a modelisation of chromium removal by Donnan dialysis through anion exchange membrane, these results are compared with the theoretical predictions given by the resolution of the corrected Nernst–Planck's equation in the cases of the homogeneous models of ion-exchange membranes. This confrontation confirms the existence of three domains corresponding respectively to a complete diffusion boundary layers (DBLs) control, a mixed control and a complete membrane control of the inter-diffusion process. And finally, the Donnan dialysis and adsorption onto activated alumina has been coupled. The coupling DIC-AAA was successfully achieved with 90% of chromium removed

Chromium is a common groundwater pollutant originating from industrial processes such as metal plating, leather tanning and pigment manufacturing. Permeable reactive barriers (PRBs) have proven to be viable and cost-effective systems for remediation of chromium contaminated groundwater at many sites. The purpose of this research presented in this thesis is to focus on two parameters that affect the performance of PRB on chromium removal, namely the concentration of reactive media and groundwater flux by analyzing the data obtained from laboratory column studies. Laboratory scale columns packed with different amounts of iron powder and quartz sand mixtures were fed with 20 mg/l chromium influent solution under different fluxes. When chromium treatment efficiencies of the columns were compared with respect to iron powder/quartz sand ratio, the amount of iron powder was found to be an important parameter for treatment efficiency of PRBs. The formation of H2 gas and the reddish-brown precipitates throughout the column matrix were observed, suggesting the reductive precipitation reactions. SEM-EDX analysis of the iron surface after the breakthrough illustrated chromium precipitation. In addition to chromium / calcium and significant amount of iron-oxides or -hydroxides was also detected on the iron surfaces. When the same experiments were conducted at higher fluxes, an increase was observed in the treatment efficiency in the column containing 50% iron. This suggested that the precipitates may not be accumulating at higher fluxes which, in turn, create available surface area for reduction. Extraction experiments were also performed to determine the fraction of chromium that adsorbed to ironhydroxides. The analysis showed that chromium was not removed by adsorption to oxyhydroxides and that reduction is the only removal mechanism in the laboratory experiments. The observed rate of Cr(VI) removal was calculated for each reactive mixture which ranged from 48.86 hour-1 to 3804.13 hour-1. These rate constants and complete removal efficiency values were thought to be important design parameters in the field scale permeable reactive barrier applications.

This thesis examines the use of electrochemically treated viscose rayon based activated carbon cloth (ACC) for the removal of metal ions from aqueous effluent streams. Two types of treatment were performed: (i) electrochemical oxidation and (ii) electrochemical reduction to enhance cation and anion sorption capacities of the ACC, respectively. Electrochemical oxidation resulted in a loss of 61% BET surface area due to blockage of pores through formation of carboxylic acidic groups but its cation exchange capacity and oxygen content increased by 365% and 121%, respectively. The optimum constant current at which a combination of applied current and oxidation time at any extent of oxidation to produce ACC of maximum cation exchange capacity was found to be 1.1 A, with voltage of 4.2 V and current density of 0.8 mA/m2. Batch sorption experiments showed that the maximum copper and lead sorption capacities for electrochemically oxidised ACC increased 17 and 4 times, respectively, for noncompetitive sorption and 8.8 and 8.6 times, respectively for competitive sorption. Therefore, electrochemically oxidised ACC is an effective adsorbent for treating aqueous solution contaminated with copper/lead in both single component and multi-component systems. Industrial wastewaters are multicomponent systems, therefore, electrochemical oxidation of ACC is an efficient way of enhancing lead and copper ions sorptive capacity for industrial wastewater treatment. Electrochemical reduction resulted in a loss of 28% BET surface area due to formation of ether groups but its anion exchange capacity increased by 292%. The optimum constant current at which a combination of applied current and reduction time at any extent of reduction to produce ACC of maximum anion exchange capacity was found to be 5.5 A, with voltage of 9.8 V and current density of 6.4 mA/m2. Batch sorption experiments showed that the maximum chromium(VI) sorption capacity for electrochemically reduced ACC increased 2.12 times, with highest maximum chromium(VI) sorption capacity of 3.8 mmol/g at solution pH 4. Most industrial wastewaters contaminated with chromium(VI) are highly acidic, therefore, electrochemical reduction of ACC is an efficient way of enhancing chromium(VI) sorptive capacity for industrial wastewater treatment.

Chromium is used in many processing applications, which has led to the formation of chromium(VI) waste. Cr(VI) is an unstable, mobile carcinogen, which is interchangeable with Cr(III) under certain environmental conditions. Management of this waste, however, is often not considered. Mine under investigation is an example of such historic mismanagement. During the second World War, Cr(VI) waste was transferred to the study site from areas where leather products were made for the war effort. This waste was not managed appropriately in the past and with time Cr(VI) leached into the groundwater and possibly surface water resources. As these water resources are used for domestic and agricultural water supply, this may have serious effects on the human and environmental health in the area. Some of the major Cr(VI) effects on human and animal health include malignant tumours, skin irritation, respiratory and reproductive system damage. Lung cancer is of concern when Cr(VI) is inhaled and stomach tumours occur when this chemical pollutant is ingested. The effects of Cr(VI) on plants include the disruption of shoot and root elongation, and if it accumulates enough within the plant can cause ingested health problems for humans and animals. Water quality guidelines state that the Target Water Quality Range for Cr(VI) in drinking water should not exceed 0.05 mg/L. Prolonged exposure of values higher than this target value has adverse health effects and may result in cancer. The study site has a scarcity in water sources and therefore requires good quality water resources. This study aims to identify and use biomarkers to assist in the hydrological characterization of the mine. Available mitigation options can be implemented once it is known how the water in the area moves and distributes Cr(VI) pollution. A biomarker is an indicator of a biological state, which in turn can be used to assist in characterizing the chemical conditions of the sub-surface. Bacteria can aid as environmental biomarkers as they are sensitive and specific to the environmental conditions in which they flourish. In this way they give a good indication of the environmental condition and any possible pollution. Due to the fact that ground- and surface water are integrated resources, it is likely that if one is impacted by pollution, it will indirectly impact the other one. Therefore, the biomarkers identified can be used to characterize water pollutants that are present in ground- and some surface water resources. A description of the study site is provided, wherein the climate, elevation, geology, land use, geohydrology, hydrochemistry and surface water are documented. These factors help to identify and clarify the sources and pathways that water and the pollution would follow. Ten water samples, from surface and groundwater, were obtained in two separate sampling opportunities. The first analysis of the water samples included the determination of the chemical constituents. Two of these constituents analyzed were the total Cr and individual Cr(VI) levels. Six water samples had excessively high Cr values (exceeding the Water Quality Target Range of drinking water and water agricultural use). These values ranged from 0.1 – 3.9 mg/L. The 6 samples with excessive Cr(VI) values were used for the microbial analyses. The microbial analyses consisted of DAPI (4’,6-diamidino-2-phenylindole ) staining, for cell enumeration, and molecular analyses. The molecular analyses included polymerase chain reaction (PCR), denaturing gradient gel electrophoresis (DGGE) and sequencing applications concluded in the laboratory. Fifteen bands, representing different organisms, were removed from the DGGE polyacrylamide gel and processed for sequencing. The organisms that were present in the sample were uncultured Cyanobacterium, Sediminibacterium salmoneum, uncultured Bacteroidetes bacterium, uncultured betaproteobacterium, uncultured actinobacterium, uncultured Rhodocyclaceae, uncultured Chloroflexi bacterium and uncultured delta-proteobacterium. According to literature most of these organisms may adapt the ability to either reduce Cr(VI) or resist any effect of Cr(VI) in the environment. Two of the bands were highly unidentified organisms, which means that these organisms have not yet been cultured or identified in any sense. The reason for this is that most microorganisms have not yet been documented. This also makes it difficult to identify the exact bacterial strain present within the samples. The deoxyribonucleic acid (DNA) sequences of the different organisms were very different from each other, when compared by a dendrogram. This means that there was a diverse community present within the samples. Electrical conductivity profiles were conducted in the monitoring boreholes to identify possible fracture positions. The total chromium and chromium(VI) levels were documented and compared. Other chemical factors were analysed and those of high value, such as chloride, nitrate and chromium measurements, were used for statistical analyses and comparison with the biomarkers present in the sample. A positive correlation was found between the sample sites and the organisms present within each. It was noted that different communities have different metabolic activities related to susceptibility and will therefore differ under specific environmental conditions. The microorganisms that were present in the 6 water samples all have the ability to either resist or reduce Cr(VI). This means that in Cr(VI) polluted areas they are more likely to flourish than organisms that do not possess this ability. Such susceptible, non-resistant organisms would otherwise occur naturally in a non-polluted environment. From the obtained results it was noted that microorganisms could aid as biomarkers when determining the environmental condition (with respect to Cr(VI) pollution). The bacteria analysed in the samples all indicate a level of chromium pollution, and aided in the determination of pollution sources. These biomarkers can therefore be used to determine the location of other chromium deposits not yet located. / MSc (Environmental Sciences), North-West University, Potchefstroom Campus, 2013