This study explores the possible application of a biodegradable plant based surfactant, obtained from Sapindus mukorossi, for washing low levels of arsenic (As) from an iron (Fe) rich soil. Natural association of As(V) with Fe(III) makes the process difficult. Soapnut solution was compared to anionic surfactant sodium dodecyl sulfate (SDS) in down-flow and a newly introduced suction mode for soil column washing. It was observed that soapnut attained up to 86% efficiency with respect to SDS in removing As. Full factorial design of experiment revealed a very good fit of data. The suction mode generated up to 83 kPa pressure inside column whilst down-flow mode generated a much higher pressure of 214 kPa, thus making the suction mode more efficient. Micellar solubilisation was found to be responsible for As desorption from the soil and it followed 1st order kinetics. Desorption rate coefficient of suction mode was found to be in the range of 0.005 to 0.01, much higher than down-flow mode values. Analysis of the FT-IR data suggested that the soapnut solution did not interact chemically with As, offering an option for reusing the surfactant. Soapnut can be considered as a soil washing agent for removing As even from soil with high Fe content.
Speciation of arsenic and selenium was carried out on water samples taken from rivers used as water intake points in the vicinity of landfill areas used for land-based waste disposal system. Leachates from these landfill areas may contaminate the river water through underground seepage or overflowing, especially after a heavy downpour. Preconcentration of the chemical species was done using a mixture of ammonium pyrrolidinethiocarbamate-chloroform (APDTC-CHCl3). Because only the reduced forms of both arsenic and selenium species could be extracted by the preconcentrating mixture, suitable reducing agents such as 25% sodium thiosulfate for As(III) and 6M HCl for Se(IV) were used throughout the studies. Care was taken to exclude the interfering elements such as the alkali and alkali earth metals from the inorganic arsenic and selenium species by introducing 12% EDTA solution as the masking agent. The extracted mixture was irradiated in a thermal neutron flux of 4 x 10(12)/cm/s from a TRIGA Mk.II reactor at the Malaysia Institute of Nuclear Technology Research (MINT). Gamma rays of 559 keV and 297 keV from 76As and 75Se, respectively, were used in the quantitative determination of the inorganic species. Mixed standards of As(III) and Se(IV) used in the percentage efficiency procedure were prepared from salts of Analar grade. The water quality evaluation was viewed from the ratio of the inorganic species present.
An isotopic dilution assay was developed to measure radiolabile As concentration in a diverse range of soils (pH 3.30-7.62; % C = 1.00-6.55). Soils amended with 50 mg of As kg(-1) (as Na2HAsO4 x 7H2O) were incubated for over 800 d in an aerated "microcosm" experiment. After 818 d, radiolabile As ranged from 27 to 57% of total applied As and showed a pH-dependent increase above pH 6. The radiolabile assay was also applied to three sets of soils historically contaminated with sewage sludge or mine-spoil. Results reflected the various geochemical forms in which the arsenic was present. On soils from a sewage disposal facility, radiolabile arsenate ranged from 3 to 60% of total As; mean lability was lower than in the equivalent pH range of the microcosm soils, suggesting occlusion of As into calcium phosphate compounds in the sludge-amended soils. In soils from mining areas in the U.K. and Malaysia, radiolabile As accounted for 0.44-19% of total As. The lowest levels of lability were associated with extremely large As concentrations, up to 17,000 mg kg(-1), from arsenopyrite. Soil pore water was extracted from the microcosm experiment and speciated using "GEOCHEM". The solid<==>solution equilibria of As in the microcosm soils was described by a simple model based on competition between HAsO4(2-) and HPO4(2-) for "labile" adsorption sites.
In an effort to seek a new technical platform for disposal of drinking water treatment sludge (DWTS: alum sludge), pyrolysis of DWTS was mainly investigated in this study. To establish a more sustainable thermolytic platform for DWTS, this study particularly employed CO2 as reactive gas medium. Thus, this study laid great emphasis on elucidating the mechanistic roles of CO2 during the thermolysis of DWTS. A series of the TGA tests of DWTS in CO2 in reference to N2 revealed no occurrence of the heterogeneous reaction between CO2 and the sample surface of DWTS. As such, at the temperature regime before initiating the Boudouard reaction (i.e., ≥700 °C), the mass decay patterns of DWTS in N2 and CO2 were nearly identical. However, the gaseous effluents from lab-scale pyrolysis of DWTS in CO2 in reference to N2 were different. In sum, the homogeneous reactions between CO2 and volatile matters (VMs) evolved from the thermolysis of DWTS led to the enhanced generation of CO. Also, CO2 suppressed dehydrogenation of VMs. Such the genuine mechanistic roles of CO2 in the thermolysis of DWTS subsequently led to the compositional modifications of the chemical species in pyrolytic oil. Furthermore, the biochar composite was obtained as byproduct of pyrolysis of DWTS. Considering that the high content of Al2O3 and Fe-species in the biochar composite imparts a strong affinity for As(V), the practical use of the biochar composite as a sorptive material for arsenic (V) was evaluated at the fundamental levels. This work reported that adsorption of As(V) onto the biochar composite followed the pseudo-second order model and the Freundlich isotherm model.
Colloidal gas aphron dispersions (CGAs) can be described as a system of microbubbles suspended homogenously in a liquid matrix. This work examines the performance of CGAs in comparison to surfactant solutions for washing low levels of arsenic from an iron rich soil. Sodium Dodecyl Sulfate (SDS) and saponin, a biodegradable surfactant, obtained from Sapindus mukorossi or soapnut fruit were used for generating CGAs and solutions for soil washing. Column washing experiments were performed in down-flow and up flow modes at a soil pH of 5 and 6 using varying concentration of SDS and soapnut solutions as well as CGAs. Soapnut CGAs removed more than 70% arsenic while SDS CGAs removed up to 55% arsenic from the soil columns in the soil pH range of 5-6. CGAs and solutions showed comparable performances in all the cases. CGAs were more economical since it contains 35% of air by volume, thereby requiring less surfactant. Micellar solubilization and low pH of soapnut facilitated arsenic desorption from soil column. FT-IR analysis of effluent suggested that soapnut solution did not interact chemically with arsenic thereby facilitating the recovery of soapnut solution by precipitating the arsenic. Damage to soil was minimal arsenic confirmed by metal dissolution from soil surface and SEM micrograph.
The potential of three submerged aquatic plant species (Cabomba piauhyensis, Egeria densa, and Hydrilla verticillata) to be used for As, Al, and Zn phytoremediation was tested. The plants were exposed for 14 days under hydroponic conditions to mine waste water effluents in order to assess the suitability of the aquatic plants to remediate elevated multi-metals concentrations in mine waste water. The results show that the E. densa and H. verticillata are able to accumulate high amount of arsenic (95.2%) and zinc (93.7%) and resulted in a decrease of arsenic and zinc in the ambient water. On the other hand, C. piauhyensis shows remarkable aluminium accumulation in plant biomass (83.8%) compared to the other tested plants. The ability of these plants to accumulate the studied metals and survive throughout the experiment demonstrates the potential of these plants to remediate metal enriched water especially for mine drainage effluent. Among the three tested aquatic plants, H. verticillata was found to be the most applicable (84.5%) and suitable plant species to phytoremediate elevated metals and metalloid in mine related waste water.
Effects of biological activated carbon (BAC), biological aerated filter (BAF), alum coagulation and Moringa oleifera coagulation were investigated to remove iron and arsenic contaminants from drinking water. At an initial dose of 5 mg/L, the removal efficiency for arsenic and iron was 63% and 58% respectively using alum, and 47% and 41% respectively using Moringa oleifera. The removal of both contaminants increased with the increase in coagulant dose and decrease in pH. Biological processes were more effective in removing these contaminants than coagulation. Compared to BAF, BAC gave greater removal of both arsenic and iron, removing 85% and 74%, respectively. Longer contact time for both processes could reduce the greater concentration of arsenic and iron contaminants. The addition of coagulation (at 5 mg/L dosage) and a biological process (with 15 or 60 min contact time) could significantly increase removal efficiency, and the maximum removal was observed for the combination of alum and BAC treatment (60 min contact time), with 100% and 98.56% for arsenic and iron respectively. The reduction efficiency of arsenic and iron reduced with the increase in the concentration of dissolved organics in the feedwater due to the adsorption competition between organic molecules and heavy metals.
Certain arsenic and selenium compounds show a remarkable mutual cancelation of toxicities, where a lethal dose of one can be voided by an equimolar and otherwise lethal dose of the other. It is now well established that the molecular basis of this antagonism is the formation and biliary excretion of seleno bis-(S-glutathionyl) arsinium anion [(GS)2AsSe](-). Previous work has definitively demonstrated the presence of [(GS)2AsSe](-) in rabbit bile, but only in the presence of other arsenic and selenium species. Rabbits have a gall bladder, which concentrates bile and lowers its pH; it seems likely that this may be responsible for the breakdown of biliary [(GS)2AsSe](-). Since rats have no gall bladder, the bile proceeds directly through the bile duct from the hepatobiliary tree. In the present work we have shown that the primary product of biliary co-excretion of arsenic and selenium in rats is [(GS)2AsSe](-), with essentially 100% of the arsenic and selenium present as this species. The chemical plausibility of the X-ray absorption spectroscopy-derived structural conclusions of this novel arsenic and selenium co-excretion product is supported by density functional theory calculations. These results establish the biomolecular basis to further explore the use of selenium dietary supplements as a possible palliative for chronic low-level arsenic poisoning of human populations.
This study was conducted to determine the effects of rice husk ash (RHA) and Fe-coated rice husk ash (Fe-RHA) on the bioavailability and mobility of As, Cd, and Mn in mine tailings. The amendments were added to the tailings at 0, 5, 10, or 20% (w/w) and the mixtures were incubated for 0, 7, 15, 30, 45, and 60 days. The CaCl2 extractable As, Cd, and Mn in the amended tailings were determined at each interval of incubation period. In addition, the tailings mixture was leached with simulated rain water (SRW) every week from 0 day (D 0) until day 60 (D 60). The results showed that both RHA and Fe-RHA application significantly decreased the CaCl2-extractable Cd and Mn but increased that of As in the tailings throughout the incubation period. Consequently, addition of both RHA and Fe-RHA leached out higher amount of As from the tailings but decreased Cd and Mn concentration compared to the controls. The amount of As leached from the Fe-RHA-amended tailings was less than that from RHA-amended tailings. Application of both RHA and Fe-RHA could be an effective way in decreasing the availability of cationic heavy metals (Cd and Mn) in the tailings but these amendments could result in increasing the availability of anionic metalloid (As). Therefore, selection of organic amendments to remediate metal-contaminated tailings must be done with great care because the outcomes might be different among the elements.
To develop a novel granular adsorbent to remove arsenic and antimony from water, calcined Mg/Al-layered double-hydroxide (CLDH)-incorporated polyethersulfone (PES) granular adsorbents (PES-LDH) were prepared using a core-shell method having 25% PES in an N,N-dimethylformamide solution. The PES-LDH displayed a spherical hollow shape having a rough surface and the average particle size of 1-2 mm. On the PES-LDH surface, nanosized CLDH (100-150 nm) was successfully immobilized by consolidation between PES and CLDH. The adsorption of Sb(V) by PES-LDH was found to be more favorable than for As(V), with the maximum adsorption capacity of As(V) and Sb(V) being 7.44 and 22.8 mg/g, respectively. The regeneration results indicated that a 0.5 M NaOH and 5 M NaCl mixed solution achieved an 80% regeneration efficiency in As(V) adsorption and desorption. However, the regeneration efficiency of Sb(V) gradually decreased due to its strong binding affinity, even though the PES-LDH showed much higher Sb(V) adsorption efficiency than As(V). This study suggested that PES-LDH could be a promising granular adsorbent for the remediation of As(V) and Sb(V) contained in wastewater.
β-Cyclodextrin-ionic liquid polymer (CD-ILP) was first synthesized by functionalized β-cyclodextrin (CD) with 1-benzylimidazole (BIM) to form monofunctionalized CD (βCD-BIMOTs) and was further polymerized using a toluene diisocyanate (TDI) linker to form insoluble CD-ILP (βCD-BIMOTs-TDI). The βCD-BIMOTs-TDI polymer was characterized using various tools and the results obtained were compared with those derived from the native β-cyclodextrin polymer (βCD-TDI). The SEM result shows that the presence of ionic liquid (IL) increases the pore size, while the thermo gravimetric analysis (TGA) result shows that the presence of IL increases the stability of the polymer. Meanwhile, Brunauer-Emmett-Teller (BET) results show that βCD-BIMOTs-TDI polymer has 1.254 m(2)/g surface areas and the Barret-Joyner-Halenda (BJH) pore size distribution result reveals that the polymer exhibits macropores with a pore size of 77.66 nm. Preliminary sorption experiments were carried out and the βCD-BIMOTs-TDI polymer shows enhanced sorption capacity and high removal towards phenols and As(V).
Cellulose acetate (CA) and cellulose acetate phthalate (CAP) were used as additives (1 wt%, 3 wt%, and 5 wt%) to prepare polyphenylsulfone (PPSU) hollow fiber membranes. Prepared hollow fiber membranes were characterized by surface morphology using scanning electron microscopy (SEM), surface roughness by atomic force microscopy (AFM), the surface charge of the membrane was analyzed by zeta potential measurement, hydrophilicity by contact angle measurement and the functional groups by fourier transform infrared spectroscopy (FTIR). Fouling resistant nature of the prepared hollow fiber membranes was evaluated by bovine serum albumin (BSA) and molecular weight cutoff was investigated using polyethylene glycol (PEG). By total organic carbon (TOC), the percentage rejection of PEG was found to be 14,489 Da. It was found that the hollow fiber membrane prepared by the addition of 5 wt% of CAP in PPSU confirmed increased arsenic removal from water as compared to hollow fiber membrane prepared by 5 wt% of CA in PPSU. The removal percentages of arsenic with CA-5 and CAP-5 hollow fiber membrane was 34% and 41% with arsenic removal permeability was 44.42 L/m2h bar and 40.11 L/m2h bar respectively. The increased pure water permeability for CA-5 and CAP-5 hollow fiber membrane was 61.47 L/m2h bar and 69.60 L/m2 h bar, respectively.