Binoy Sarkar

Remediation of hexavalent chromium through adsorption by bentonite based Arquad® 2HT-75 organoclays

Unlike hydrophobic organic pollutants, the potential of organoclays to adsorb inorganic ionic contaminants is relatively underexplored. The present study attempts to characterise bentonite (QB) based organoclays synthesised from a commercially available, low-cost alkyl ammonium surfactant Arquad® 2HT-75 (Aq) and test their ability to adsorb hexavalent chromium (Cr (VI)) in aqueous solution. XRD, FTIR and TGA characterisation techniques prove successful modification of the bentonite structure and reveal that higher surfactant loadings gives rise to more ordered surfactant conformation in the organoclays. The zeta potential values indicate that higher surfactant loadings also create positive charges on the organoclay surfaces. Detailed isothermal and kinetic studies show that the organoclays effectively remove hexavalent chromium (Cr (VI)) from aqueous solution by both physical and chemical adsorption processes. Higher surfactant loadings provide better adsorption efficiency. The adsorption performance is reasonably efficient under the levels of pH, temperature, electrolyte concentration and natural organic matter concentration that generally prevail in contaminated soil and water. This study shows that organoclay sorbents offer good potential for remediating Cr (VI) under real environmental conditions.

Bioreactive Organoclay: A New Technology for Environmental Remediation

Organoclays, which are synthesized by introducing organic molecules into the clay structure, have been proven effective for remediation of many contaminants in soil and water. The underlying principle for this is sorption. However, a new remediation approach that combines sorption and biodegradation/biotransformation has evolved in recent years. Contaminants sorbed on organoclays can be successfully degraded or transformed into less toxic forms by specific microorganisms, provided the participating microbes thrive well on the organoclays. Thus, bioreactive organoclays are prepared. The authors present a critical review of the scientific principles and scope of integrating microorganisms with organoclays to develop a new environmental friendly, risk–based, and cost-effective remediation technology. Furthermore, they propose new research directions in the field.

Biochar-induced concomitant decrease in ammonia volatilization and increase in nitrogen use efficiency by wheat

Ammonia (NH3) volatilization is a major nitrogen (N) loss from the soil, especially under tropical conditions, NH3 volatilization results in low N use efficiency by crops. Incubation experiments were conducted using five soils (pH 5.5-9.0), three N sources such as, urea, di-ammonium phosphate (DAP), and poultry manure (PM) and two biochars such as, poultry litter biochar (PL-BC) and macadamia nut shell biochar (MS-BC). Ammonia volatilization was higher at soil with higher pH (pH exceeding 8) due to the increased hydroxyl ions. Among the N sources, urea recorded the highest NH3 volatilization (151.6 mg kg(-1)soil) followed by PM (124.2 mg kg(-1)soil) and DAP (99 mg kg(-1)soil). Ammonia volatilization was reduced by approximately 70% with PL-BC and MS-BC. The decreased NH3 volatilization with biochars is attributed to multiple mechanisms such as NH3 adsorption/immobilization, and nitrification. Moreover, biochar increased wheat dry weight and N uptake as high as by 24.24% and 76.11%, respectively. This study unravels the immense potential of biochar in decreasing N volatilization from soils and simultaneously improving use efficiency by wheat.

Bioremediation of PAHs and VOCs: Advances in clay mineral-microbial interaction.

Bioremediation is an effective strategy for cleaning up organic contaminants, such as polycyclic aromatic hydrocarbons (PAHs) and volatile organic compounds (VOCs). Advanced bioremediation implies that biotic agents are more efficient in degrading the contaminants completely. Bioremediation by microbial degradation is often employed and to make this process efficient, natural and cost-effective materials can serve as supportive matrices. Clay/modified clay minerals are effective adsorbents of PAHs/VOCs, and readily available substrate and habitat for microorganisms in the natural soil and sediment. However, the mechanism underpinning clay-mediated biodegradation of organic compounds is often unclear, and this requires critical investigation. This review describes the role of clay/modified clay minerals in hydrocarbon bioremediation through interaction with microbial agents in specific scenarios. The vision is on a faster, more efficient and cost-effective bioremediation technique using clay-based products. This review also proposes future research directions in the field of clay modulated microbial degradation of hydrocarbons.

Structural characterisation of Arquad® 2HT-75 organobentonites: Surface charge characteristics and environmental application

Organoclays are increasingly being used to remediate both contaminated soils and waste water. The present study was attempted to elucidate the structural evolution of bentonite based organoclays prepared from a commercially available, low-cost alkyl ammonium surfactant Arquad(®) 2HT-75. XRD, FTIR, SEM and zeta potential measurement were used to characterise the organoclays. In particular, the relationship between surface charge characteristics of the organoclays and their ability to remediate organic contaminants such as phenol and p-nitrophenol was investigated. The investigation revealed that the arrangement and conformation of surfactant molecules in the bentonite became more regular, ordered and solid-like as of Arquad(®) 2HT-75 loading increased. This also led to the formation of a positive zeta potential on the surface of organobentonites prepared with 3.57:1 and 4.75:1 surfactant-clay (w/w) ratio. The zeta potential values decreased with increasing pH of the suspension. The adsorption data of phenol and p-nitrophenol were best fitted to Freundlich isotherm model. The adsorption was controlled by multiple mechanisms of partitioning, physico-sorption and chemisorption. The outcomes of this study are useful for the synthesis of low cost organobentonite adsorbents for the remediation of ionisable organic contaminants such as phenol and p-nitrophenol from waste water.

Manganese(II)-catalyzed and clay-minerals-mediated reduction of chromium(VI) by citrate.

Unlike lower valent iron (Fe), the potential role of lower valent manganese (Mn) in the reduction of hexavalent chromium (Cr(VI)) in soil is poorly documented. In this study, we report that citrate along with Mn(II) and clay minerals (montmorillonite and kaolinite) reduce Cr(VI) both in aqueous phase and in the presence of dissolved organic carbon (SDOC) extracted from a forest soil. The reduction was favorable at acidic pH (up to pH 5) and followed the pseudo-first-order kinetic model. The citrate (10 mM) + Mn(II) (182.02 μM) + clay minerals (3% w/v) system in SDOC accounted for complete reduction of Cr(VI) (192.32 μM) in about 72 h at pH 4.9. In this system, citrate was the reductant, Mn(II) was a catalyst, and the clay minerals acted as an accelerator for both the reductant and catalyst. The clay minerals also serve as a sink for Cr(III). This study reveals the underlying mechanism of the Mn(II)-induced reduction of Cr(VI) by organic ligand in the presence of clay minerals under certain environmental conditions.

Heavy metal-immobilizing organoclay facilitates polycyclic aromatic hydrocarbon biodegradation in mixed-contaminated soil.

Soils contaminated with a mixture of heavy metals and polycyclic aromatic hydrocarbons (PAHs) pose toxic metal stress to native PAH-degrading microorganisms. Adsorbents such as clay and modified clay minerals can bind the metal and reduce its toxicity to microorganisms. However, in a mixed-contaminated soil, an adsorption process more specific to the metals without affecting the bioavailability of PAHs is desired for effective degradation. Furthermore, the adsorbent should enhance the viability of PAH-degrading microorganisms. A metal-immobilizing organoclay (Arquad(®) 2HT-75-bentonite treated with palmitic acid) (MIOC) able to reduce metal (cadmium (Cd)) toxicity and enhance PAH (phenanthrene) biodegradation was developed and characterized in this study. The MIOC differed considerably from the parent clay in terms of its ability to reduce metal toxicity (MIOC>unmodified bentonite>Arquad-bentonite). The MIOC variably increased the microbial count (10-43%) as well as activities (respiration 3-44%; enzymatic activities up to 68%), and simultaneously maintained phenanthrene in bioavailable form in a Cd-phenanthrene mixed-contaminated soil over a 21-day incubation period. This study may lead to a new MIOC-assisted bioremediation technique for PAHs in mixed-contaminated soils.

Analytical characterisation of nanoscale zero-valent iron: A methodological review.

Zero-valent iron nanoparticles (nZVI) have been widely tested as they are showing significant promise for environmental remediation. However, many recent studies have demonstrated that their mobility and reactivity in subsurface environments are significantly affected by their tendency to aggregate. Both the mobility and reactivity of nZVI mainly depends on properties such as particle size, surface chemistry and bulk composition. In order to ensure efficient remediation, it is crucial to accurately assess and understand the implications of these properties before deploying these materials into contaminated environments. Many analytical techniques are now available to determine these parameters and this paper provides a critical review of their usefulness and limitations for nZVI characterisation. These analytical techniques include microscopy and light scattering techniques for the determination of particle size, size distribution and aggregation state, and X-ray techniques for the characterisation of surface chemistry and bulk composition. Example characterisation data derived from commercial nZVI materials is used to further illustrate method strengths and limitations. Finally, some important challenges with respect to the characterisation of nZVI in groundwater samples are discussed.

Toxicity of organoclays to microbial processes and earthworm survival in soils

Organoclays have wide spread application in environmental remediation and nanocomposites synthesis. Some of the quaternary ammonium compounds (QACs) commonly used to prepare organoclays are toxic to biota. However, information on the toxicity of organoclays is rarely available in the literature. This study assessed the toxicity of three laboratory prepared bentonite organoclays on the soil microbially mediated processes (such as dehydrogenase activity and potential nitrification) and soil inhabiting animals, such as earthworms. Toxicity to both microbial processes and earthworm followed the order: hexadecyltrimethyl ammonium modified bentonite>octadecyltrimethyl ammonium modified bentonite>arquad modified bentonite>unmodified bentonite. The organoclays were able to cause slight improvement (up to 25%) in the potential nitrification in some soils when they were added at low application rates up to 5%, but caused reduction (3-86%) in the dehydrogenase activity in all the soils irrespective of loading rates. The organoclays were extremely toxic to the survival and vigour of the earthworms. The average body weight loss of the worms reached as high as 62% in hexadecyltrimethyl ammonium modified bentonite treated soil even at 1% loading. This study holds utmost importance in assessing the toxicity of organoclays to soil microbially mediated processes and earthworms.

Surface tailored organobentonite enhances bacterial proliferation and phenanthrene biodegradation under cadmium co-contamination.

Co-contamination of soil and water with polycyclic aromatic hydrocarbon (PAH) and heavy metals makes biodegradation of the former extremely challenging. Modified clay-modulated microbial degradation provides a novel insight in addressing this issue. This study was conducted to evaluate the growth and phenanthrene degradation performance of Mycobacterium gilvum VF1 in the presence of a palmitic acid (PA)-grafted Arquad® 2HT-75-based organobentonite in cadmium (Cd)-phenanthrene co-contaminated water. The PA-grafted organobentonite (ABP) adsorbed a slightly greater quantity of Cd than bentonite at up to 30mgL(-1) metal concentration, but its highly negative surface charge imparted by carboxylic groups indicated the potential of being a significantly superior adsorbent of Cd at higher metal concentrations. In systems co-contained with Cd (5 and 10mgL(-1)), the Arquad® 2HT-75-modified bentonite (AB) and PA-grafted organobentonite (ABP) resulted in a significantly higher (72-78%) degradation of phenanthrene than bentonite (62%) by the bacterium. The growth and proliferation of bacteria were supported by ABP which not only eliminated Cd toxicity through adsorption but also created a congenial microenvironment for bacterial survival. The macromolecules produced during ABP-bacteria interaction could form a stable clay-bacterial cluster by overcoming the electrostatic repulsion among individual components. Findings of this study provide new insights for designing clay modulated PAH bioremediation technologies in mixed-contaminated water and soil.