A presença de fármacos em águas superficiais, subterrâneas, solo e efluentes tem gerado preocupações no que diz respeito à ineficiência dos tratamentos convencionais e os riscos ambientais associados ao descarte inadequado destes micropoluentes emergentes. Diante disto, o objetivo deste trabalho foi avaliar a adsorção e a dessorção de ácido acetilsalicílico (AAS) em solução aquosa em carvão ativado de babaçu in natura (CAB) e funcionalizado quimicamente com HNO3 (CAA). Foram determinados aos adsorventes os teores de cinzas, umidade e de material volátil, granulometria, análise elementar, aspectos morfológicos dos adsorventes, por meio de microscopia eletrônica de varredura (MEV), pH no ponto de carga zero (pHPCZ), características da superfície dos adsorventes por meio de adsorção/dessorção de N2 e os grupos funcionais por espectroscopia na região no infravermelho (FTIR) e método de Boehm. Ensaios cinéticos, de equilíbrio e termodinâmicos foram conduzidos para a adsorção e dessorção em batelada. Ensaios em coluna de leito fixo foram conduzidos preliminarmente. Os resultados dos ensaios cinéticos de adsorção e dessorção foram ajustados aos modelos de pseudo-primeira e pseudo-segunda ordem e os resultados de equilíbrio de adsorção aos modelos matemáticos de Langmuir e Freundlich e de dessorção ao modelo de Langmuir-Freundlich. Aos resultados termodinâmicos de adsorção e dessorção foram determinados os valores de ΔG º, ΔH º e ΔS º. Os adsorventes apresentaram características microporosas, com valores de pHPCZ de 6,4 para CAB e 4,5 para CAA que interferem diretamente na adsorção. Os dados da cinética de adsorção foram melhor ajustados ao modelo de pseudo-segunda ordem e os do equilíbrio de adsorção ao modelo de Langmuir. Os resultados do ΔG º e ΔH º resultaram negativos e o do ΔSº positivo nas temperaturas de 25 ºC, 45 ºC e 55 ºC, indicando que o processo é exotérmico e espontâneo. O aumento da temperatura favoreceu a adsorção com o CAB, e reduziu a capacidade adsortiva do CAA. Em pH ácido a quantidade máxima adsorvida do AAS foi de 119,80 mg g -1 para CAB e 115,08 mg g -1 para CAA. Nos ensaios de dessorção os melhores resultados foram observados com o CAB em pHPCZ = 6,4. Os resultados cinéticos tiveram melhor ajuste ao modelo de pseudo-primeira ordem. As isotermas de dessorção ajustadas ao modelo de Langmuir-Freundlich. Adicionalmente, com os ciclos foram obtidos os percentuais médios de adsorção e dessorção de 92% e 75% no CAB e de 72% e 10% no CAA, respectivamente. O conjunto de dados de pH e temperatura avaliados nos ensaios em coluna de leito fixo determinaram que a reação de adsorção é melhor definida em pH 2,0 e temperatura de 40 ºC. / The presence of drugs in surface water, groundwater, soil and effluents has raised concerns regarding the inefficiency of conventional treatments and the environmental risks associated with the inappropriate disposal of these emerging micropollutants. The objective of this work was to evaluate the adsorption and desorption of acetylsalicylic acid (AAS) in aqueous solution of in natura activated babassu carbon (CAB) and chemically functionalized with HNO3 (CAA). The ash adsorbents, moisture and volatile matter, granulometry, elemental analysis, morphological aspects of the adsorbents were determined by scanning electron microscopy (SEM), pH at the zero load point (pHPCZ), surface characteristics of the adsorbents. adsorbents by adsorption/desorption of N2 and functional groups by infrared spectroscopy (FTIR) and Boehm method. Kinetic, equilibrium and thermodynamic tests were conducted for batch adsorption and desorption. Preliminary tests were conducted in a fixed bed column. The adsorption and desorption kinetics results were adjusted to the pseudofirst and pseudo-second order models and the adsorption equilibrium results to the Langmuir and Freundlich mathematical models. The values of ΔG º, ΔH º and ΔS º were determined for the thermodynamic adsorption and desorption results. The desorption equilibrium results were fitted to the Langmuir-Freundlich model. The adsorbents presented microporous characteristics, with values of pHPCZ of 6.4 for CAB and 4,5 for CAA that interfere directly in the adsorption. Adsorption was favored at acidic pH in both adsorbents. The adsorption kinetics data were better fitted to the pseudo second order model and those of the adsorption equilibrium to the Langmuir model, indicating the influence of the chemisorption on the adsorption. The results of ΔGº and ΔHº were negative and that of ΔSº positive at temperatures of 25 ºC, 45 ºC and 55 ºC, indicating the influence of the chemisorption in the process that is exothermic and spontaneous. The increase in temperature favored the adsorption with the CAB, and reduced the adsorptive capacity of the CAA. At acid pH the maximum adsorbed amount of ASA was 119.80 mg g -1 for CAB and 115.08 mg g -1 for CAA. In the desorption experiments the best results were observed with the CAB at pHPCZ = 6.4. The kinetic results had better fit to the pseudo first order model. Desorption isotherms fitted to the Langmuir-Freundlich model indicated affinity between the CAB, ASA and the chosen regenerant. Additionally, the average adsorption and desorption percentages of 92% and 75% in CAB and 72% and 10% in CAA, respectively, were obtained with the cycles. The set of pH and temperature data evaluated in the fixed bed column assays determined that the adsorption reaction is best defined at pH 2.0 and temperature of 40 ºC.

PhD (Environmental Sciences) / Department of Ecology and Resource Management / The presence of arsenic in groundwater has drawn worldwide attention from researchers and public health officials due to its effects on human health such as, cancer, skin thickening, neurological disorders, muscular weakness, loss of appetite and nausea. World Health Organisation (WHO) has set the limit of 10 μg/L for arsenic in drinking water in trying to reduce the effects of arsenic. This was further adopted by South African National Standard (SANS). The present study aims at evaluating arsenic concentration in selected groundwater sources around Greater Giyani Municipality in Limpopo Province and further synthesize clay based adsorbents for arsenic removal using Fe3+ and Mn2+ oxides and hexadecylammonium bromide (HDTMA-Br) cationic surfactant as modifying agents. The first section of the work presented the hydrogeochemical characteristics of groundwater in the Greater Giyani Municipality. The results showed that the pH of the samples ranges from neutral to weakly alkaline. The dominance of major anionic and cationic species was found to be in the order: HCO3 ->Cl->SO4 2->NO3 - and Na+>Mg2+>Ca2+>K+>Si4+, respectively. Hydrogeochemical facies identified in the study area include CaHCO3 (90%) and mixed CaNaHCO3 (10%) which shows the dominance of water-rock interaction. About 60% of the tested samples contains arsenic concentration above 10 μg/L as recommended by SANS and WHO. Concentration of arsenic was found to be ranging between 0.1 to 172.53 μg/L with the average of 32.21 μg/L. In the second part of this work, arsenic removal efficiency of locally available smectite rich and kaolin clay was evaluated. Results showed that the percentage As(V) removal by kaolin clay was optimum at pH 2 while the percentage As(III) removal was greater than 60% at pH 2 to 12. For smectite rich clay soils, the percentage of As(III) and As(V) removal was found to be optimum at pH between 6 and 8. The adsorption isotherm data for As(III) and As(V) removal by both clays fitted better to Freundlich isotherm. Adsorption of both species of arsenic onto the clay mineral occurred via electrostatic attraction and ion exchange mechanisms. Both clay soils could be regenerated twice using Na2CO3 as a regenerant. Kaolin clay showed a better performance and was selected for further modification. In the third section of this work, Fe-Mn bimetal oxide modified kaolin clay was successfully synthesized by precipitating Fe3+ and Mn2+ metal oxides to the interlayer surface of kaolin clay. Modification of kaolin clay increased the surface area from 19.2 m2/g to 29.8 m2/g and further v decreased the pore diameter from 9.54 to 8.5 nm. The adsorption data fitted to the pseudo second order of reaction kinetics indicating that adsorption of As(III) and As(V) occurred via chemisorption. The adsorption isotherm data was described by Langmuir isotherm models showing a maximum As(III) and As(V) adsorption capacities of 2.16 and 1.56 mg/g, respectively at a temperature of 289 K. Synthesized adsorbent was successfully reused for 6 adsorptiondesorption cycles using K2SO4 as a regenerant. Column experiments showed that maximum breakthrough volume of ≈2 L could be treated after 6 hours using 5 g adsorbent dosage. Furthermore, the concentration of Fe and Mn were within the WHO permissible limit. In the fourth part of the work kaolin clay was functionalized with hexadecyltrimethylamonium bromide (HDTMA-Br) cationic surfactant and its application in arsenic removal from groundwater was investigated. The results revealed that adsorption of As(III) and As(V) is optimum at pH range 4-8. The maximum As(III) and As(V) adsorption capacities were found 2.33 and 2.88 mg/g, respectively after 60 min contact time. Pseudo first order model of reaction kinetics described the adsorption data for As(V) better while pseudo second order model described As(III) adsorption data. The adsorption isotherm data for As(III) and As(V) fitted well to Langmuir model indicating that adsorption of both species occurred on a mono-layered surface. Adsorption thermodynamics model revealed that adsorption of As(III) and As(V) was spontaneous and exothermic. The As(III)/As(V) adsorption mechanism was ascribed to electrostatic attraction and ion exchange. The regeneration study showed that synthesized adsorbent can be used for up to 5 times. In the firth part of the work inorgano-organo modified kaolin clay was successfully synthesized through intercalation of Fe3+ and Mn2+ metal oxides and HDTMA-Br surfactant onto the interlayers of the clay mineral. The batch experiments showed that As(III) removal was optimum at pH range of 4-6, while the As(V) removal was optimum at pH range 4-8. The adsorption data for both species of arsenic showed a better fit to pseudo second order of reaction kinetics which suggest that the dominant mechanism of adsorption was chemisorption. The isotherm studies showed better fit to Langmuir isotherm model as compared to Freundlich model. The maximum adsorption capacity As(III) and As(V) at room temperature as determined by Langmuir model were found to be 7.99 mg/g and 7.32 mg/g, respectively. The thermodynamic studies for sorption of As(III) and As(V) showed negative value of ΔGᴼ and ΔHᴼ indicating that adsorption process occurred spontaneously and is exothermic in nature. The regeneration study showed that the vi inorgano-organo modified kaolin clay can be reused for up 7 adsorption-regeneration cycles using 0.01 M HCl as a regenerant. Thomas kinetic model and Yoon-Nelson model showed that the rate of adsorption increases with increasing flow rate and initial concentration and decreases with increasing of the bed mass. In conclusions, adsorbents synthesized from this work showed a better performance as compared to other adsorbents available in the literature. Among the synthesized adsorbents, inorgano-organo modified clay showed highest adsorption capacity as compared to surfactant functionalized and Fe-Mn bimetal oxides modified kaolin clay. However, all adsorbents were recommended for use in arsenic remediation from groundwater. The following recommendations were made following the findings from this study: 1) routine monitoring of arsenic in groundwater of Greater Giyani Municipality, 2) evaluating the possible link between arsenic exposure and arsenic related diseases within Giyani in order to find the extent of the problem in order to establish the population at risk, 3) The toxicity assessment for HDTMA-Br modified kaolin clay should be carried out, 4) Materials developed in the present study should be modeled and tested at the point of use for arsenic removal, and lastly, 5) this study further encourage the development of other arsenic removal materials that can be used at household level. / NRF

Indiana University-Purdue University Indianapolis (IUPUI) / Numerous studies have investigated the fate of pollutants in riparian buffers, but few studies have focused on the control of multiple contaminants simultaneously in riparian zones. To better understand what drives the biogeochemical cycles of multiple contaminants in riparian zones, a 19-month study was conducted in riparian buffers across a range of hydrogeomorphic (HGM) settings in the White River watershed in Indiana. Three research sites [Leary Webber Ditch (LWD), Scott Starling (SS) and White River (WR)] with contrasting hydro-geomorphology were selected. We monitored groundwater table depth, oxidation reduction potential (ORP), dissolved oxygen (DO), dissolved organic carbon (DOC), NO3-, NH4+, soluble reactive phosphorus (SRP), SO42- , total Hg and methylmercury (MeHg). Our results revealed that differences in HGM conditions translated into distinctive site hydrology, but significant differences in site hydrology did not lead to different biogeochemical conditions. Nitrate reduction and sulfate re-oxidation were likely associated with major hydrological events, while sulfate reduction, ammonia and methylmercury production were likely associated with seasonal changes in biogeochemical conditions. Results also suggest that the LWD site was a small sink for nitrate but a source for sulfate and MeHg, the SS site was a small sink for MeHg but had little effect on NO3-, SO42- and SRP, and the WR was an intermediate to a large sink for nitrate, an intermediate sink for SRP, and a small source for MeHg. Land use and point source appears to have played an important role in regulating solute concentrations (NO3-, SRP and THg). Thermodynamic theories probably oversimplify the complex patterns of solute dynamics which, at the sites monitored in the present study, were more strongly impacted by HGM settings, land use, and proximity to a point source.