Most components of petroleum oily sludge (POS) are toxic, mutagenic and cancer-causing. Often bioremediation using microorganisms is hindered by the toxicity of POS. Under this circumstance, phytoremediation is the main option as it can overcome the toxicity of POS. Cajanus cajan a legume plant, was evaluated as a phyto-remediating agent for petroleum oily sludge-spiked soil. Culture dependent and independent methods were used to determine the rhizosphere microorganisms' composition. Degradation rates were estimated gravimetrically. The population of total heterotrophic bacteria (THRB) was significantly higher in the uncontaminated soil compared to the contaminated rhizosphere soil with C. cajan, but the population of hydrocarbon-utilizing bacteria (HUB) was higher in the contaminated rhizosphere soil. The results show that for 1 to 3% oily sludge concentrations, an increase in microbial counts for all treatments from day 0 to 90 d was observed with the contaminated rhizosphere CR showing the highest significant increase (p soil. The PCoA plot revealed community-level differences between the contaminated non-rhizosphere control and contaminated rhizosphere microbiota. The PCoA differentiated the two treatments based on the presence or absence of plant. The composition and taxonomic analysis of microbiota-amplified sequences were categorized into eight phyla for the contaminated non-rhizosphere and ten phyla for the contaminated rhizosphere. The overall bacterial composition of the two treatments varied, as the distribution shows a similar variation between the two treatments in the phylum distribution. The percentage removal of total petroleum hydrocarbon (TPH) after 90 days of treatments with 1, 2, 3, 4, and 5% (w/w) of POS were 92, 90, 89, 68.3 and 47.3%, respectively, indicating removal inhibition at higher POS concentrations. As the search for more eco-friendly and sustainable remediating green plant continues, C. cajan shows great potential in reclaiming POS contaminated soil. Our findings will provide solutions to POS polluted soils and subsequent re-vegetation.
In phytoremediation of co-contaminated soil, the simultaneous and efficient remediation of multiple pollutants is a major challenge rather than the removal of pollutants. A laboratory-scale experiment was conducted to investigate the effect of 5% addition of each of three different organic waste amendments (tea leaves, soy cake, and potato skin) to enhance the phytoaccumulation of lead (60 mg kg(-1)) and diesel fuel (25,000 mg kg(-1)) in co-contaminated soil by Dracaena reflexa Lam for a period of 180 day. The highest rate of oil degradation was recorded in co-contaminated soil planted with D. reflexa and amended with soy cake (75%), followed by potato skin (52.8%) and tea leaves (50.6%). Although plants did not accumulate hydrocarbon from the contaminated soil, significant bioaccumulation of lead in the roots and stems of D. reflexa was observed. At the end of 180 days, 16.7 and 9.8 mg kg(-1) of lead in the stems and roots of D. reflexa were recorded, respectively, for the treatment with tea leaves. These findings demonstrate the potential of organic waste amendments in enhancing phytoremediation of oil and bioaccumulation of lead.
Terrestrial plants as potential phytoremediators for remediation of surface soil contaminated with toxic metals have gained attention in clean-up technologies. The potential of kenaf (Hibiscus cannabinus L.) to offer a cost-effective mechanism to remediate Fe and As from landfill leachate-contaminated soil was investigated. Pot experiment employing soil polluted with treatments of Jeram landfill leachate was conducted for 120 days. Plants were harvested after 8th, 12th, and 16th weeks of growth. Accumulation of Fe and As was assessed based on Bioconcentration Factor and Translocation Factor. Results showed sequestration of 0.06-0.58 mg As and 66.82-461.71 mg Fe per g plant dry weight in kenaf root, which implies that kenaf root can be an bioavailable sink for toxic metals. Insignificant amount of Fe and As was observed in the aerial plant parts (< 12% of total bioavailable metals). The ability of kenaf to tolerate these metals and avoid phytotoxicity could be attributed to the stabilization of the metals in the roots and hence reduction of toxic metal mobility (TF < 1). With the application of leachate, kenaf was also found to have higher biomass and subsequently recorded 11% higher bioaccumulation capacity, indicating its suitability for phytoextraction of leachate contaminated sites.
Soil contamination by hydrocarbons, especially by used lubricating oil, is a growing problem in developing countries, which poses a serious threat to the environment. Phytoremediation of these contaminated soils offers environmental friendly and a cost effective method for their remediation. Hibiscus cannabinus was studied for the remediation of soil contaminated with 2.5 and 1% used lubricating oil and treated with organic wastes [banana skin (BS), brewery spent grain (BSG) and spent mushroom compost (SMC)] for a period of 90 days under natural conditions. Loss of 86.4 and 91.8% used lubricating oil was recorded in soil contaminated with 2.5 and 1% oil and treated with organic wastes respectively at the end of 90 days. However, 52.5 and 58.9% oil loss was recorded in unamended soil contaminated with 2.5 and 1% oil, respectively. The plant did not accumulate hydrocarbon from the soil but shows appreciable accumulation of Fe and Zn in the root and stem of H. cannabinus at the end of the experiment. The first order kinetic rate of uptake of Fe and Zn in H. cannabinus was higher in organic wastes amendment treatments compared to the unamended treatments, which are extremely low. The results of this study suggest that H. cannabinus has a high potential for remediation of hydrocarbon and heavy metal contaminated soil.
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.
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.
Spent Pleurotus sajor-caju compost mixed with livestock excreta, i.e. cow dung or goat manure, was contaminated with landfill leachate and vermiremediated in 75 days. Results showed an extreme decrease of heavy metals, i.e. Cd, Cr and Pb up to 99.81% removal as effect of vermiconversion process employing epigeic earthworms i.e. Lumbricus rubellus. In addition, there were increments of Cu and Zn from 15.01% to 85.63%, which was expected as non-accumulative in L. rubellus and secreted out as contained in vermicompost. This phenomenon is due to dual effects of heavy metal excretion period and mineralisation. Nonetheless, the increments were 50-fold below the limit set by EU and USA compost limits and the Malaysian Recommended Site Screening Levels for Contaminated Land (SSLs). Moreover, the vermicompost C:N ratio range is 20.65-22.93 and it can be an advantageous tool to revitalise insalubrious soil by acting as soil stabiliser or conditioner.
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 influence of temperature, moisture and organic matter on the persistence of cyfluthrin was determined using three types of Malaysian soils, namely clay, clay loam and sandy clay loam obtained from a tomato farm in Cameron Highlands, Pahang. The persistence of cyfluthrin was observed in the laboratory at two temperature levels of 25 and 35 degreeC and field water capacity of 30 and 80%. Treated soil samples were incubated in a growth chamber for 1, 2, 3, 5, 7, 10, 14, 21 and 28 days. The results from the incubation studies showed that temperature and organic matter content significantly reduced the half-life (t1/2) values of cyfluthrin in the three soil types, but moisture content had very little effect. It was observed that cyfluthrin persisted longer at lower temperature and moisture content and higher organic matter content in all the three soil types. The present study demonstrated that under the tropical conditions of Malaysia, cyfluthrin dissipated rapidly in soils compared to its dissipation in soils of temperate regions, evidently due to high temperature.
Toxic inorganic and organic chemicals are major contributors to environmental contamination and pose major health risks to human population. In this work, Dracaena reflexa and Podocarpus polystachyus were investigated for their potential to remove hydrocarbons from 2.5% and 1% diesel fuel-contaminated soil amended individually with 5% organic wastes (tea leaf, soy cake and potato skin) for a period of 270 days. Loss of 90% and 99% oil was recorded in soil contaminated with 2.5% and 1% oil with soy cake amendment, respectively, compared with 52% and 62% in unamended soil with D. reflexa at the end of 270 days. Similarly, 84% and 91% oil loss was recorded for P. polystachyus amended with organic wastes in 2.5% and 1% oil, respectively. Diesel fuel disappeared more rapidly in the soil amendment with SC than in other organic waste supplementation. It was evident that plants did not accumulate hydrocarbon from the soil, while the number of hydrocarbon-utilizing bacteria was high in the rhizosphere, thus suggesting that the mechanism of the oil degradation was rhizodegradation. The kinetic model result indicated a high rate of degradation in soil amendment with SC at 1% with D. reflexa compared with other treatments. Thus, a positive relationship was observed between diesel hydrocarbon degradation with plant biomass production. Dracaena reflexa with organic wastes amendment has a greater potential of restoring hydrocarbon-contaminated soil compared to P. polystachyus plant.
A diverse surfactant, including the nonionic Tween 80 and Brij 30, the anionic sodium dodecyl sulphate, the cationic surfactant Tetradecyltrimethylammonium bromide, and biosurfactant Rhamnolipid were investigated under fluorine-enriched medium by Armilaria sp. F022. The cultures were performed at 25 °C in malt extract medium containing 1 % of surfactant and 5 mg/L of fluorene. The results showed among the tested surfactants, Tween-80 harvested the highest cell density and obtained the maximum specific growth rate. This due Tween-80 provide a suitable carbon source for fungi. Fluorane was also successfully eliminated (>95 %) from the cultures within 30 days in all flasks. During the experiment, laccase production was the highest among other enzymes and Armillaria sp. F022-enriched culture containing Non-ionic Tween 80 showed a significant result for laccase activity (1,945 U/L). The increased enzyme activity was resulted by the increased biodegradation activity as results of the addition of suitable surfactants. The biotransformation of fluorene was accelerated by Tween 80 at the concentration level of 10 mg/L. Fluorene was initially oxidized at C-2,3 positions resulting 9-fluorenone. Through oxidative decarboxylation, 9-fluorenone subjected to meta-cleavage to form salicylic acid. One metabolite detected in the end of experiment, was identified as catechol. Armillaria sp. F022 evidently posses efficient, high effective degrader and potential for further application on the enhanced bioremediation technologies for treating fluorene-contaminated soil.
A white-rot fungus of Polyporus sp. S133 was isolated from an oil-polluted soil. The metabolism of pyrene by this fungus was investigated in liquid medium with 5 mg of the compound. Depletion of pyrene was evident during the 30-day growth period and was 21% and 90%, respectively, in cometabolism and metabolism of pyrene alone. Pyrene was absorbed to fungal cells or biodegraded to form simpler structural compounds. Seventy-one percent of eliminated pyrene was transformed by Polyporus sp. S133 into other compounds, whereas only 18% was absorbed in the fungal cell. The effects of pH and temperature on biomass production of Polyporus sp. S133 for pyrene were examined; the properties of laccase and 1,2-dioxygenase produced by Polyporus sp. S133 during pyrene degradation were investigated. The optimal values of pH were 3, 5, and 4 for laccase, 1,2-dioxygenase, and biomass production, respectively, whereas the optimal values of temperature were 25 °C for laccase and 50 °C for 1,2-dioxygenase and biomass production. Under optimal conditions, pyrene was mainly metabolized to 1-hydroxypyrene and gentisic acid. The structure of 1-hydroxypyrene and gentisic acid was determined by gas chromatography-mass spectrometry after identification using thin-layer chromatography.
This work focuses on the remediation of polycyclic aromatic hydrocarbon (PAH)-contaminated soil using modified Fenton (MF) treatment coupled with a novel chelating agent (CA), a more effective technique among currently available technologies. The performance of MF treatment to promote PAH oxidation in artificially contaminated soil was investigated in a packed column with a hydrogen peroxide (H(2)O(2)) delivery system simulating in-situ soil flushing which is more representative of field conditions. The effectiveness of process parameters H(2)O(2)/soil, Fe(3+)/soil, CA/soil weight ratios and reaction time were studied using a 2(4) three level factorial design experiments. An optimised operating condition of the MF treatment was observed at H(2)O(2)/soil 0.05, Fe(3+)/soil 0.025, CA/soil 0.04 and 3h reaction time with 79.42% and 68.08% PAH removals attainable for the upper and lower parts of the soil column respectively. The effects of natural attenuation and biostimulation process as post-treatment in the remediation of the PAH-contaminated soil were also studied. In all cases, 3-aromatic ring PAH (phenanthrene) was more readily degraded than 4-aromatic ring PAH (fluoranthene) regardless of the bioremediation approach. The results revealed that both natural attenuation and biostimulation could offer remarkable enhancement of up to 6.34% and 9.38% in PAH removals respectively after 8 weeks of incubation period. Overall, the results demonstrated that combined inorganic CA-enhanced MF treatment and bioremediation serves as a suitable strategy to enhance soil quality particularly to remediate soils heavily contaminated with mixtures of PAHs.
For decades Malaysia was the world's largest producer of Sn, but now the vast open cast mining operations have left a legacy of some 100,000 ha of what is effectively wasteland, covered with a mosaic of tailings and lagoons. Few plants naturally recolonise these areas. The demand for such land for both urban expansion and agricultural use has presented an urgent need for better characterisation. This study reports on the formation of artificial soils from alluvial Sn mining waste with a focus on the effects of experimental treatments on soil chemistry. Soil organic matter, clay, and pH were manipulated in a controlled environment. Adding both clay tailings and peat enhanced the cation exchange capacity of sand tailings but also reduced the pH. The addition of peat reduced the extractable levels of some elements but increased the availability of Ca and Mg, thus proving beneficial. The use of clay tailings increased the levels of macro and micronutrients but also released Al, As, La, Pb and U. Additionally, the effects of soil mix and mycorrhizal treatments on growth and foliar chemistry were studied. Two plant species were selected: Panicum milicaeum and Pueraria phaseoloides. Different growth patterns were observed with respect to the additions of peat and clay. The results for mycorrhizal treatment (live inoculum or sterile carrier medium) are more complex, but both resulted in improved growth. The use of mycorrhizal fungi could greatly enhance rehabilitation efforts on sand tailings.
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.
Experiments were conducted to remove heavy metals (Cr, Cd, Pb, Cu and Zn) from urban sewage sludge (SS) amended with spent mushroom compost (SMC) using worms, Lumbricus rubellus, for 105 days, after 21 days of pre-composting. Five combinations of SS/SMC treatments were prepared in triplicate along with a control for each treatment in microcosms. Analysis of the earthworms' multiplication and growth and laboratory analysis were conducted during the tenth and fifteenth week of vermicomposting. Our result showed that the final biomass of earthworms (mg) and final number of earthworms showed significant differences between treatments i.e. F=554.70, P=0.00 and F=729.10, P=0.00 respectively. The heavy metals Cr, Cd and Pb contained in vermicompost were lower than initial concentrations, with 90-98.7 percent removal on week ten. However, concentrations of Cu and Zn, that are considered as micronutrients, were higher than initial concentrations, but they were 10-200-fold lower than the EU and USA biosolid compost limits and Malaysian Recommended Site Screening Levels for Contaminated Land (SSLs). An increment of heavy metals were recorded in vermicompost for all treatments on week fifteen compared to week ten, while concentration of heavy metals in earthworms' tissue were lower compared to vermicompost. Hence, it is suggested that earthworms begin to discharge heavy metals into their surroundings and it was evident that the earthworms' heavy metals excretion period was within the interval of ten to fifteen weeks.
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."
The accumulation and removal efficiency of Fe by Centella asiatica was carried out at various Fe concentrations in soil treatments (0, 50, 100, 150 and 200 mg Fe/kg soil). Iron accumulation in different parts of C. asiatica (leaf, stem and root) was analyzed by atomic absorption spectrophotometer (AAS). Factorial experiment with a completely randomized design and Duncan's test were used for data analyses. The results revealed that C. asiatica have the ability to uptake and accumulate Fe significantly (p soil treatments had significant effect on the total Fe accumulations in C. asiatica (p soil has been evaluated by bioconcentration factor and translocation factor, found to be >1 and <1, respectively, further supporting its metal hyperaccumulator properties.