There are numerous reports on poly-β-hydroxybutyrate (PHB) depolymerases produced by various microorganisms isolated from various habitats, however, reports on PHB depolymerase production by an isolate from plastic rich sites scares. Although PHB has attracted commercial significance, the inefficient production and recovery methods, inefficient purification of PHB depolymerase and lack of ample knowledge on PHB degradation by PHB depolymerase have hampered its large scale commercialization. Therefore, to ensure the biodegradability of biopolymers, it becomes imperative to study the purification of the biodegrading enzyme system. We report the production, purification, and characterization of extracellular PHB depolymerase from Stenotrophomonas sp. RZS7 isolated from a dumping yard rich in plastic waste. The isolate produced extracellular PHB depolymerase in the mineral salt medium (MSM) at 30°C during 4 days of incubation under shaking. The enzyme was purified by three methods namely ammonium salt precipitation, column chromatography, and solvent purification. Among these purification methods, the enzyme was best purified by column chromatography on the Octyl-Sepharose CL-4B column giving optimum yield (0.7993 Umg-1mL-1). The molecular weight of purified PHB depolymerase was 40 kDa. Studies on the assessment of biodegradation of PHB in liquid culture medium and under natural soil conditions confirmed PHB biodegradation potential of Stenotrophomonas sp. RZS7. The results obtained in Fourier-Transform Infrared (FTIR) analysis, High-Performance Liquid Chromatography (HPLC) study and Gas Chromatography Mass-Spectrometry (GC-MS) analysis confirmed the biodegradation of PHB in liquid medium by Stenotrophomonas sp. RZS7. Changes in surface morphology of PHB film in soil burial as observed in Field Emission Scanning Electron Microscopy (FESEM) analysis confirmed the biodegradation of PHB under natural soil environment. The isolate was capable of degrading PHB and it resulted in 87.74% biodegradation. A higher rate of degradation under the natural soil condition is the result of the activity of soil microbes that complemented the biodegradation of PHB by Stenotrophomonas sp. RZS7.
Polycyclic aromatic hydrocarbons (PAHs) in soil have been recognised as a serious health and environmental issue due to their carcinogenic, mutagenic and teratogenic properties. One of the commonly employed soil remediation techniques to clean up such contamination is soil washing or solvent extraction. The main factor which governs the efficiency of this process is the solubility of PAHs in the extraction agent. Past field-scale soil washing treatments for PAH-contaminated soil have mainly employed organic solvents or water which is either toxic and costly or inefficient in removing higher molecular weight PAHs. Thus, the present article aims to provide a review and discussion of the alternative extraction agents that have been studied, including surfactants, biosurfactants, microemulsions, natural surfactants, cyclodextrins, vegetable oil and solution with solid phase particles. These extraction agents have been found to remove PAHs from soil at percentages ranging from 47 to 100% for various PAHs.
This paper aims to review the applications of Fenton based treatments specifically for polycyclic aromatic hydrocarbons-contaminated soils. An overview of the background and principles of Fenton treatment catalysed by both homogenous (conventional and modified Fenton) and heterogeneous (Fenton-like) catalysts is firstly presented. Laboratory and field soil remediation studies are then discussed in terms of efficiency, kinetics and associated factors. Four main scopes of integrated Fenton treatments, i.e. physical-Fenton, biological-Fenton, electro-Fenton and photo-Fenton are also reviewed in this paper. For each of these integrated remediation technologies, the theoretical background and mechanisms are detailed alongside with achievable removal efficiencies for polycyclic aromatic hydrocarbons in contaminated soils compared to sole Fenton treatment. Finally, the environmental impacts of Fenton based soil treatments are documented and discussed.
Acid waste bentonite is a byproduct from vegetable oil bleaching that is acidic (pH < 3.0) and hydrophobic. These materials are currently disposed of in landfills and could potentially have a negative impact on the effective function of microbes that are intolerant of acidic conditions. A study was undertaken using three different sources of acid waste bentonites, namely soybean oil bentonite (SB), palm oil bentonite (PB), and rice bran oil bentonite (RB). These materials were co-composted with rice husk, rice husk ash, and chicken litter to eliminate their acid reactivity and hydrophobic nature. The organic carbon (OC) content, pH, exchangeable cations, and cation exchange capacity (CEC) of the acid-activated bentonites increased significantly after the co-composting phase. In addition, the hydrophobic nature of these materials as measured using the water drop penetration time (WDPT) decreased from >10 800 s to 16 to 80 s after composting. Furthermore, these composted materials showed positive impacts on soil physical attributes including specific surface area, bulk density, and available water content for crop growth. Highly significant increases in maize biomass (Zea mays L.) production over two consecutive cropping cycles was observed in treatments receiving co-composted bentonite. The study clearly demonstrates the potential for converting an environmentally hazardous material into a high-quality soil conditioner using readily available agricultural byproducts. It is envisaged that the application of these composted acid waste bentonites to degraded soils will increase productivity and on-farm income, thus contributing toward food security and poverty alleviation.
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.
A diesel-degrading bacterium was isolated from a diesel-contaminated site in Selangor, Malaysia. The isolate was tentatively identified as Acinetobacter sp. strain DRY12 based on partial 16S rDNA molecular phylogeny and Biolog GN microplate panels and Microlog database. Optimum growth occurred from 3 to 5% diesel and the strain was able to tolerate as high as 8% diesel. The optimal pH that supported growth of the bacterium was between pH 7.5 to 8.0. The isolate exhibited optimal growth in between 30 and 35 degrees C. The best nitrogen source was potassium nitrate (between 0.6 and 0.9% (w/v)) followed by ammonium chloride, sodium nitrite and ammonium sulphate in descending order. An almost complete removal of diesel components was seen from the reduction in hydrocarbon peaks observed using Solid Phase Microextraction Gas Chromatography analysis after 10 days of incubation. The best growth kinetic model to fit experimental data was the Haldane model of substrate inhibiting growth with a correlation coefficient value of 0.97. The maximum growth rate- micromax was 0.039 hr(-1) while the saturation constant or half velocity constant Ks and inhibition constant Ki, were 0.387% and 4.46%, respectively. MATH assays showed that 75% of the bacterium was found in the hexadecane phase indicating that the bacterium was hydrophobic. The characteristics of this bacterium make it useful for bioremediation works in the Tropics.
The degradation behavior of veterinary antibiotics in soil is commonly studied using the following methods of adding antibiotics to the soil: (i) adding manure collected from animals fed with a diet containing antibiotics, (ii) adding antibiotic-free animal manure spiked with antibiotics and (iii) directly adding antibiotics. No research simultaneously comparing different antibiotic addition methods was found. Oxytetracycline (OTC) was used as a model antibiotic to compare the effect of the three commonly used antibiotic addition methods on OTC degradation behavior in soil. The three treatment methods have similar trends, though OTC degradation half-lives show the following significant differences (P<0.05): manure from swine fed OTC (treatment A)soil. Because the main entry route for veterinary antibiotics into soil is via the manure of animals given with antibiotics, the most appropriate method to study the degradation and ecotoxicity of antibiotic residues in soil may be to use manure from animals that are given a particular antibiotic, rather than by adding it directly to the soil.
This study aims to investigate the impacts of ethyl lactate (EL) based Fenton treatment on soil quality for polycyclic aromatic hydrocarbons (PAHs)-contaminated soils. Accumulation of oxygenated-polycyclic aromatic hydrocarbons (oxy-PAHs) was observed, but quantitative measurement on the most abundant compound 9,10-anthraquinone (ATQ) showed lower accumulation of the compound than that reported for ethanol (ET) based Fenton treatment. In general, as compared to conventional water (CW) based Fenton treatment, the EL based Fenton treatment exerted either a lower or higher negative impact on soil physicochemical properties depending on the property type and shared the main disadvantage of reduced soil pH. For revegetation, EL based Fenton treatment was most appropriately adopted for soil with native pH >/~ 6.2 in order to obtain a final soil pH >/~ 4.9 subject to the soil buffering capacity.
This study describes the chemical speciation of Pb, Zn, Cu, Cr, As, and Sn in soil of former tin mining catchment. Total five sites were selected for sampling and subsequent subsamples were collected from each site in order to create a composite sample for analysis. Samples were analysed by the sequential extraction procedure using optical emission spectrometry (ICP OES). Small amounts of Cu, Cr, and As retrieved from the exchangeable phase, the ready available for biogeochemical cycles in the ecosystem. Low quantities of Cu and As could be taken up by plants in these kind of acidic soils. Zn not detected in the bioavailable forms while Pb is only present in negligible amounts in very few samples. The absence of mobile forms of Pb eliminates the toxic risk both in the trophic chain and its migration downwards the soil profile. The results also indicate that most of the metals have high abundance in residual fraction indicating lithogenic origin and low bioavailability of the metals in the studied soil. The average potential mobility for the metals giving the following order: Sn > Cu > Zn > Pb > Cr > As.
This study was carried out to determine the sorption-desorption, degradation and leaching of napropamide in selected Malaysian soils. The sorption capacities of the selected Malaysian soils for napropamide were the following in descending order: Linau > Teringkap > Gunung Berinchang > Jambu > Rudua > Baging soil. The results indicate that napropamide degradation decreased with increasing soil sorption capacity. Napropamide was leached out earlier in the Baging soil than the other soils. Overall, the application of napropamide in the selected Malaysian soils would not pose a threat to the environment except in soil with low organic matter and clay content and high hydraulic conductivity, such as the Baging soil.
Solubility data of recalcitrant contaminants in cosolvents is essential to determine their potential applications in enhanced soil remediation. The solubilities of phenanthrene, anthracene, fluoranthene and benzo[a]pyrene in ethyl lactate/water and ethanol/water mixtures were measured using equilibrium techniques. The cosolvency powers derived from solubility data were then applied to the model developed from the solvophobic approach to predict the capability of ethyl lactate and ethanol in enhancing the desorption of contaminants from soils. Both ethyl lactate and ethanol cosolvents were shown to be able to enhance the solubilisation of the tested four polycyclic aromatic hydrocarbons by > 4 orders of magnitude above the levels obtained with water alone. However, ethyl lactate demonstrated a greater capacity to enhance PAH solubility than ethanol. The cosolvency powers of ethyl lactate/water system obtained from the end-to-end slope (sigma) and the end-to-half slope (sigma0.5) of the solubilisation curve were 1.0-1.5 and 2.0-2.9 higher than ethanol/water system respectively. In line with this, ethyl lactate/water was demonstrated to enhance the desorption of contaminants from soil by 20%-37% and 18%-61% higher compared to ethanol/water system in low organic content and high organic content soils respectively, with a 2:1 (V/W) ratio of solution:soil and with cosolvent fraction as low as 0.4. With the exception of benzo[a]pyrene, the experimental desorption results agreed fairly with the predicted values, under an applied solution:soil ratio that was enough to hold the capacity of released contaminants.
Weathered crude oil (WCO) removals in shoreline sediment samples were monitored for 60 days in bioremediation experimentation. Experimental modeling was carried out using statistical design of experiments. At optimum conditions maximum of 83.13, 78.06 and 69.92% WCO removals were observed for 2, 16 and 30 g/kg initial oil concentrations, respectively. Significant variations in the crude oil degradation pattern were observed with respect to oil, nutrient and microorganism contents. Crude oil bioremediation were successfully described by a first-order kinetic model. The study indicated that the rate of hydrocarbon biodegradation increased with decrease of crude oil concentrations.
Acephate is poorly sorbed to soil, thus the risk of leaching to the aquatic environment is high if it is not quickly degraded. The effect of soil moisture, temperature, microbial activity and application rate on acephate degradation has been studied in three Malaysian soils to examine and identify critical variables determining its degradation and mineralization kinetics. First-order kinetics could be used to describe degradation in all cases (r(2)>0.91). Acephate degraded faster in air-dry (t((1/2)) 9-11 d) and field capacity (t((1/2)) 10-16d) soils than in the wet soils (t((1/2)) 32-77 d). The activation energy of degradation was in the range 17-28 kJ mol(-1) and significantly higher for the soil with higher pH and lower clay and iron oxide contents. Soil sterilization caused a 3- to 10-fold decrease in degradation rates compared to non-sterile soils (t((1/2)) 53-116 d) demonstrating that acephate degradation is mainly governed by microbial processes. At 5-fold increase in application rates (25 microg g(-1)), half-life increased slightly (t((1/2)) 13-19 d) or was unaffected. Half-life from acephate mineralization was similar to those from degradation but much longer at the 5-fold increase in acephate application rates (t((1/2)) 41-96 d) demonstrating that degradation of metabolites is rate limiting. Thus, application of acephate should be restricted or avoided during wet seasons with heavy rainfall and flooded soil as in paddy cultivation. Sandy soils with low microbial activity are more prone to acephate leaching than clay soils rich in humic matter.
This paper presents the findings of a study on solidification/stabilization (S/S) of lead-contaminated soil using ordinary Portland cement (OPC) and rice husk ash (RHA). The effects of varying lead concentrations (in the form of nitrates) in soil samples on the physical properties of their stabilized forms, namely unconfined compressive strength (UCS), setting times of early mixtures and changes in crystalline phases as well as chemical properties such as leachability of lead, pH and alkalinity of leachates are studied. Results have indicated that usage of OPC with RHA as an overall binder system for S/S of lead-contaminated soils is more favorable in reducing the leachability of lead from the treated samples than a binder system with standalone OPC. On the other hand, partial replacement of OPC with RHA in the binder system has reduced the UCS of solidified samples.
Triazine-2-(14)C metsulfuron-methyl is a selective, systemic sulfonylurea herbicide. Degradation studies in soils are essential for the evaluation of the persistence of pesticides and their breakdown products. The purpose of the present study was to investigate the degradation of triazine-2-(14)C metsulfuron-methyl in soil under laboratory conditions. A High Performance Liquid Chromatograph (HPLC) equipped with an UV detector and an on-line radio-chemical detector, plus a Supelco Discovery column (250 x 4.6 mm, 5 μm), and PRP-1 column (305 x 7.0 mm, 10 μm) was used for the HPLC analysis. The radioactivity was determined by a Liquid Scintillation Counter (LSC) in scintillation fluid. The soil used was both sterilized and non-sterilized in order to observe the involvement of soil microbes. The estimated DT50 and DT90 values of metsulfuron-methyl in a non-sterile system were observed to be 13 and 44 days, whereas in sterilized soil, the DT50 and DT90 were 31 and 70 days, respectively. The principal degradation product after 60 days was CO2. The higher cumulative amount of (14)CO2 in (14)C-triazine in the non-sterilized soil compared to that in the sterile system suggests that biological degradation by soil micro-organisms significantly contributes to the dissipation of the compound. The major routes of degradation were O-demethylation, sulfonylurea bridge cleavage and the triazine "ring-opened."
This study was carried out to evaluate the efficiency of Guar gum in removing Persistent Organic Pollutants (POPs), viz. phenol,2,4-bis(1,1-dimethylethyl) and bis(2-ethylhexyl) phthalate (DEHP), from farm effluent. The removal efficiency was compared with alum. The results indicated that 4.0 mg L(-1) of Guar gum at pH 7 could remove 99.70% and 99.99% of phenol,2,4-bis(1,1-dimethylethyl) and DEHP, respectively. Box Behnken design was used for optimization of the operating parameters for optimal POPs removal. Scanning Electron Microscopy (SEM) and Fourier Transform Infrared (FTIR) spectroscopy studies were conducted on the flocs. SEM micrographs showed numerous void spaces in the flocs produced by Guar gum as opposed to those produced by alum. This indicated why Guar gum was more effective in capturing and removal of suspended particles and POPs as compared to alum. FTIR spectra indicated a shift in the bonding of functional groups in the flocs produced by Guar gum as compared to raw Guar gum powder signifying chemical attachment of the organics present in the effluent to the coagulant resulting in their removal. Guar gum is highly recommended as a substitute to chemical coagulant in treating POPs due to its non-toxic and biodegradable characteristics.
Colloid mobilization is a significant process governing colloid-associated transport of heavy metals in subsurface environments. It has been studied for the last three decades to understand this process. However, colloid mobilization and heavy metal transport in soil solutions have rarely been studied using soils in South Korea. We investigated the colloid mobilization in a variety of flow rates during sampling soil solutions in sand columns. The colloid concentrations were increased at low flow rates and in saturated regimes. Colloid concentrations increased 1000-fold higher at pH 9.2 than at pH 7.3 in the absence of 10 mM NaCl solution. In addition, those were fourfold higher in the absence than in the presence of the NaCl solution at pH 9.2. It was suggested that the mobility of colloids should be enhanced in porous media under the basic conditions and the low ionic strength. In real field soils, the concentrations of As, Cr, and Pb in soil solutions increased with the increase in colloid concentrations at initial momentarily changed soil water pressure, whereas the concentrations of Cd, Cu, Fe, Ni, Al, and Co lagged behind the colloid release. Therefore, physicochemical changes and heavy metal characteristics have important implications for colloid-facilitated transport during sampling soil solutions.
Imidazolinones as a persistent and active herbicides group have potential risks to non-target organisms in the environment. Biochar is a carbon-rich sorbent used as an amendment to change soil properties and its microbial communities effective on pesticides degradation rate. The present study was the first to compare empty fruit bunch (EFB) of oil palm and rice husk (RH) biomasses as biochar feedstock for remediation of imidazolinones-contaminated soils. Degradations of imazapic, imazapyr, and a mixture of them (Onduty®) was investigated in the presence of the optimized biochars in the soil during a 70-days incubation. Based on the results, the polar herbicides were resistant to hydrolysis degradation. Photolysis rates of the herbicides reduced significantly in the presence of the biochars in the soil. EFB biochar had greater effects due to its chemical compositions and surface functional groups. Photo-degradation of imazapyr was more affected by biochars amendment. The imidazolinones bio-degradation, however, accelerated significantly with the presence of EFB and RH biochars in soil with the greater effects of RH biochar. It was concluded that the application of the optimized EFB and RH biochars as an innovative sustainable strategy has the potential to decrease the persistence of the imidazolinones and minimize their environmental hazards.
Deep eutectic solvents (DESs) are a class of green solvents analogous to ionic liquids, but less costly and easier to prepare. The objective of this study is to remove lead (Pb) from a contaminated soil by using polyol based DESs mixed with a natural surfactant saponin for the first time. The DESs used in this study were prepared by mixing a quaternary ammonium salt choline chloride with polyols e.g. glycerol and ethylene glycol. A natural surfactant saponin obtained from soapnut fruit pericarp, was mixed with DESs to boost their efficiency. The DESs on their own did not perform satisfactory due to higher pH; however, they improved the performance of soapnut by up to 100%. Pb removal from contaminated soil using mixture of 40% DES-Gly and 1% saponin and mixture of 10% DES-Gly and 2% saponin were above 72% XRD and SEM studies did not detect any major corrosion in the soil texture. The environmental friendliness of both DESs and saponin and their affordable costs merit thorough investigation of their potential as soil washing agents.
Electrokinetic process has emerged as an important tool for remediating heavy metal-contaminated soil. The process can concentrate heavy metals into smaller soil volume even in the absence of hydraulic flow. This makes it an attractive soil pre-treatment method before other remediation techniques are applied such that the chemical consumption in the latter stage can be reduced. The present study evaluates the feasibility of electrokinetic process in concentrating lead (Pb) and chromium (Cr) in a co-contaminated soil using different types of wetting agents, namely 0.01 M NaNO3, 0.1 M citric acid and 0.1 M EDTA. The data obtained showed that NaNO3 and citric acid resulted in poor Pb electromigration in this study. As for Cr migration, these agents were also found to give lower electromigration rate especially at low pH region as a result of Cr(VI) adsorption and possible reduction into Cr(III). In contrast, EDTA emerged as the best wetting agent in this study as it formed water-soluble anionic complexes with both Pb and Cr. This provided effective one-way electromigration towards the anode for both ions, and they were accumulated into smaller soil volume with an enrichment ratio of 1.55-1.82. A further study on the application of approaching cathode in EDTA test showed that soil alkalisation was achieved, but this did not provide significant enhancement on electromigration for Pb and Cr. Nevertheless, the power consumption for electrokinetic process was decreased by 22.5%.