Professor Megh Mallavarapu

© 2020 Taylor & Francis Group, LLC. Unresolved complex mixtures (UCMs) of hydrocarbons are the pollutants of serious concern commonly occurring in most of the environments contaminated with petroleum hydrocarbons. UCMs constitute a relatively unidentified group of compounds compared to the well-resolved hydrocarbons that could easily be identified by the modern chromatographic methods. UCMs that accumulate in the environment cause several toxicological effects of ecological significance, and indirectly affect the human health. Despite decades-long efforts to provide adequate information in this area of research, the fate and environmental impacts of UCMs of petroleum hydrocarbons are poorly understood. Techniques for extraction and analysis of UCMs in the environment are very important in their identification and quantification. Also, remediation of toxic UCMs of petroleum hydrocarbons is all the more essential. In fact, UCMs are often neglected in the risk assessments due to lack of proper identification methods and toxicity data. This critical review presents an overview of our current knowledge on the environmental occurrence, sources, separation, and identification methods for UCMs. The ecological toxicity of UCMs toward the biota and the strategies for remediation of the environments contaminated with UCMs have also been discussed in detail.

© 2017, Springer-Verlag GmbH Germany. Chromium from tannery waste dump site causes significant environmental pollution affecting surrounding flora and fauna. The primary aims of this study were to survey vegetation, investigate the degree of soil pollution occurring near tannery waste dump site and make a systematic evaluation of soil contamination based on the chromium levels found in plants and earthworms from the impacted areas. This paper presents the pollution load of toxic heavy metals, and especially chromium, in 10 soil samples and 12 species of plants. Soil samples were analysed for heavy metals by using ICP-MS/ICP-OES method. Results indicated that Cr in soils exceeded soil quality guideline limits (SQGL). The total chromium present in the above ground parts of plants ranged from 1.7¿mg¿kg-1 in Casuarina sp.¿to 1007¿mg¿kg-1 in Sonchus asper. The Cr bioaccumulation in Eisenia fetida from tannery waste soil ranged from 5 to 194¿mg¿kg-1. The high enrichment factor of Cr in S. asper and bioaccumulation factor in earthworms indicate that there is a steady increase of toxic chromium risk in this area, which could be correlated with the past dumping activity. Emphasis needs to be put on control measures of pollution and remediation techniques in such areas to achieve an ecologically sustainable industrialisation.

© 2018 Elsevier B.V. Heavier fraction hydrocarbons (C15-C36) formed in soil after biotic and abiotic weatherings of engine oil are the continuing constraints in the bioremediation strategy, and their bioavailability remains a poorly quantified regulatory factor. In a microcosm study, we used two strains of Pseudomonas, P. putida TPHK-1 and P. aeruginosa TPHK-4, in strategies of bioremediation, viz., natural attenuation, biostimulation and bioaugmentation, for removal of weathered total petroleum hydrocarbons (TPHs) in soil contaminated long-term with high concentrations of engine oil (39,000¿41,000 mg TPHs kg-1 soil). Both the bacterial strains exhibited a great potential in remediating weathered hydrocarbons of engine oil. Addition of inorganic fertilizers (NPK), at recommended levels for bioremediation, resulted in significant inhibition in biostimulation/enhanced natural attenuation as well as bioaugmentation. The data on dehydrogenase activity clearly confirmed those of bioremediation strategies used, indicating that this enzyme assay could serve as an indicator of bioremediation potential of oil-contaminated soil. Extraction of TPHs from engine oil-contaminated soil with hydroxypropyl-ß-cyclodextrin (HPCD), but not 1-butanol, was found reliable in predicting the bioavailability of weathered hydrocarbons. Also, 454 pyrosequencing data were in accordance with those of bioremediation strategies used in the present microcosm study, suggesting the possible use of pyrosequencing in designing approaches for bioremediation.

© 2017 Elsevier Ltd Sorption and desorption are critical processes to control the mobility and biotoxicity of cadmium (Cd) in soils. It is known that attendant anion species of heavy metals could affect metal adsorption on soils and might further alter their biotoxicity. However, for Cd, the influence of attendant anions on its sorption in soils and subsequent toxicity on soil enzymes are still unknown. In this work, four Cd compounds with different salt anions (SO42-, NO3-, Cl-, and Ac-) were selected to investigate their impact of on the sorption, soil dehydrogenase activity (DHA) and alkaline phosphatase activity (ALP). Thus, a series of simulated Cd pollution batch experiments including measuring adsorption-desorption behavior of Cd on soils and soil enzyme activities were carried out. Results showed that CdSO4 exhibited highest sorption capacity among the tested soils except in Hunan soil. The Cd sorption with NO3- displayed a similar behavior with Cl- on all tested soils. Compared with soil properties, all four kinds of anions on Cd sorption played a more significant role affecting Cd ecological toxicity to soil DHA and ALP. Cd in acetate or nitrate form appears more sensitive towards DHA than sulphate and chloride, while the later pair is more toxic towards ALP than the former. These results have important implications for evaluation of Cd contamination using soil enzyme as bioindicator.

© 2017 Elsevier B.V. Diesel is an important petroleum product, and a common pollutant in soil caused by leaks and accidental spills. Studies dealing with the ecotoxicity of diesel towards earthworms always relied on growth inhibition endpoint (EC50) values that were determined based on the spiked concentrations (nominal), ignoring the substantial portion of hydrocarbons volatilized from soil. In the present study we used, for the first time, the measured concentrations of total petroleum hydrocarbons (TPHs) from soil-applied diesel to assess earthworm (Eisenia fetida) survival, and the activities of dehydrogenase, urease and nitrification as indicators of soil health. The mortality endpoint (LC50) value for initially measured concentrations after exposure of earthworms to diesel for 28¿days was 916¿±¿10¿mg TPHs kg-1 soil which was equivalent to the nominal (initially added) concentration of 1426¿±¿19¿mg TPHs kg-1 soil. Morphological abnormalities such as clitella swelling and curling were noticed when the measured concentrations of diesel were more than 971¿mg¿kg-1 soil. Significant increases in activities of soil dehydrogenase (38¿58%) as well as urease were observed in the diesel-applied soil. Presence of earthworms further enhanced the activities of these soil enzymes. Nitrification was sensitive to application of diesel to soil, and it was inhibited in a dose-related manner even in the presence of earthworms. The differential response of the toxicity criteria to diesel-contaminated soil observed in the present study clearly warrants more studies involving several soil health parameters to arrive at a generalization of ecotoxicity of an environmental pollutant.

© 2017 This study investigates the effect of contaminant zinc (Zn) on lead (Pb) bioavailability and bioaccessibility in six contrasting soils spiked with 1500 mg Pb/kg and aged 12 months under laboratory conditions. Zn was added to the soils (7500 mgZn/kg soil) and aged for a further two weeks. In vivo studies were conducted using juvenile swine as a surrogate model for young children. Two compartment pharmacokinetic models were used to analyze the biological response produced by Pb oral solution and spiked soils. Absolute and relative bioavailability of Pb in soils (oral dose of 100 µ g Pb/kg body weight/day) were estimated by comparing them with intravenously administered soluble Pb salt (25 µ g Pb/kg/day) and orally administered the same Pb salt [Pb acetate =(CH3COO)2Pb·3H2O] administered to 3 juvenile pigs per treatment. Lead bioaccessibility was calculated using the in vitro RBALP (i.e. relative bioaccessibility leaching procedure) method. The in vitro results of RBALP were compared to in vivo relative Pb bioavailability to ascertain whether the changes in bioaccessibility correlated with the in vivo data. Although the in vivo Pb relative bioavailability (RB) in all soils except in MLA (Mount Lofty Acidic) revealed an increase (18%¿159%) in the presence of Zn, the in vitro RBALP bioaccessibility results indicated otherwise (1%¿38% decrease). In vivo RB of Pb in MLA declined by 37% in the presence of Zn. However, the RBALP in vitro bioaccessible Pb did not correlate with the relative bioavailabilities of Pb in the juvenile swine dosing experiment. Caution is therefore needed when predicting Pb bioavailability/bioaccessibility in the presence of metal mixtures. The literature contains much information on the correlation of metal and metalloid bioaccessibility with their bioavailability. There is, however, a paucity of studies investigating the effects of other metals on Pb and their IVIVC (in vitro and in vivo correlations). The current study addresses this knowledge gap by assessing in vivoand in vitro bioavailability of Pb in the presence of Zn.

© 2017, The Author(s). Purpose: The study evaluates and provides an overview of the nutritional importance of 19 selected food wastes as aids in human/livestock/soil/plant health. Methods: Nitric acid-digested extracts of food wastes belonging to four different classes (fruits, vegetables, oilseeds and beverages) were analysed for different elements in an inductively coupled plasma mass spectrometer. Results: Our study recommends spent coffee grounds, tea leaves, radish peel, watermelon rind and pineapple skin that contain substantially high concentrations of essential elements such as N, P, K, S and Fe for their use as: (a) substrates for composting, (b) biofertilizers, (c) soil amendments, and (d) bioadsorbents of toxins. Although these food wastes are rich in essential nutrients, we do not suggest them for the preparation of food supplements as they contain non-essential elements in concentrations beyond the human safety limits. However, food wastes like banana peel, plum pomace and pistachio shell that contain low and permissible concentrations of toxic elements can be recommended as dietary supplements for oral intake in spite of their lesser essential elemental composition than the other residues examined. Conclusions: Our study confirms that food wastes are rich sources of essential nutrients and there is need to harness their real industrial systems.

© 2017 Elsevier Ltd Arsenic (As) and zinc (Zn) are common co-contaminants in mining impacted soils. Their interaction on solubility and toxicity when present concurrently is not well understood in natural systems. The aim of this study was to observe their interaction in solubility (soil-solution), bioaccumulation (shoot uptake) and toxicity to cucumber (Cucumis sativa L) conducting 4 weeks pot study in 5 different soils spiked with As (0, 2, 4, 8 to 1024 mg kg-1) individually and with Zn at two phytotoxic doses. The As pore-water concentration was significantly reduced (df = 289, Adjusted R2 = 0.84, p < 0.01) in the presence of Zn in the whole dataset, whereas Zn and Zn2+ activity in pore-water was reduced significantly only in the two alkaline soils. This outcome may be due to adsorption/surface precipitation or tertiary bridging complexation. No homogenous precipitation of zinc arsenate could be established using electron microscopy, XRD or even equilibrium calculations. For bioaccumulation phase, no significant effect of Zn on As uptake was observed except acidic MG soil whereas, Zn uptake was significantly reduced (p < 0.05) by As in whole dataset. However, an additive response was observed mostly except acidic MG soil. The synergistic response (more than additive) was predominant in this soil for a wide range of inhibition concentration (0¿80%) at both Zn EC10 and EC50 levels. Since additive response is mostly considered in risk assessment for mixtures, precautions should be implemented for assessment of toxicity for As-Zn mixture in acidic soil due to their synergistic response in some soils.

© 2015 Elsevier B.V. Bioelectrochemical remediation (BER) systems such as microbial fuel cells (MFCs) have recently emerged as a green technology for the effective remediation of petroleum hydrocarbon contaminants (PH) coupled with simultaneous energy recovery. Recent research has shown that biofilms previously enriched for substrate degrading bacteria resulted in excellent performance in terms of substrate removal and electricity generation but the effects on hydrocarbon contaminant degradation were not examined. Here we investigate the differences between enriched biofilm anodes and freshly inoculated new anodes in diesel fed single chamber mediatorless microbial fuel cells (DMFC) using various techniques for the enhancement of PH contaminant remediation with concomitant electricity generation. An anodophilic microbial consortium previously selected for over a year through continuous culturing with a diesel concentration of about 800mgl^-1 and which now showed complete removal of this concentration of diesel within 30days was compared to that of a freshly inoculated new anode MFC (showing 83.4% removal of diesel) with a simultaneous power generation of 90.81mW/m² and 15.04mW/m² respectively. The behaviour of pre-cultured anodes at a higher concentration of PH (8000mgl^-1) was also investigated. Scanning electron microscopy observation revealed a thick biofilm covering the pre-cultured anodic electrode but not the anode from the freshly inoculated MFC. High resolution imaging showed the presence of thin 60nm diametre pilus-like projections emanating from the cells. Anodic microbial community profiling confirmed that the selection for diesel degrading exoelectrogenic bacteria had occurred. Identification of a biodegradative gene (alkB) provided strong evidence of the catabolic pathway used for diesel degradation in the DMFCs.

© 2016, Springer Science+Business Media Dordrecht. Microalgae are extensively used in the remediation of heavy metals like iron. However, factors like toxicity, bioavailability and iron speciation play a major role in its removal by microalgae. Thus, in this study, toxicity of three different iron salts (FeSO4, FeCl3 and Fe(NO3)3) was evaluated towards three soil microalgal isolates, Chlorella sp. MM3, Chlamydomonas sp. MM7 and Chlorococcum sp. MM11. Interestingly, all the three iron salts gave different EC50 concentrations; however, ferric nitrate was found to be significantly more toxic followed by ferrous sulphate and ferric chloride. The EC50 analysis revealed that Chlorella sp. was significantly resistant to iron compared to other microalgae. However, almost 900¿µg¿g-1 iron was accumulated by Chlamydomonas sp. grown with 12¿mg¿L-1 ferric nitrate as an iron source when compared to other algae and iron salts. The time-course bioaccumulation confirmed that all the three microalgae adsorb the ferric salts such as ferric nitrate and ferric chloride more rapidly than ferrous salt, whereas intracellular accumulation was found to be rapid for ferrous salts. However, the amount of iron accumulated or adsorbed by algae, irrespective of species, from ferrous sulphate medium is comparatively lower than ferric chloride and ferric nitrate medium. The Fourier transform infrared spectroscopy (FTIR) analysis shows that the oxygen atom and P = O group of polysaccharides present in the cell wall of algae played a major role in the bioaccumulation of iron ions by algae.

© 2016 Springer International Publishing. The efficiency of low-cost, abundantly available local forestry waste, oak (Quercus robur) acorn peel (OP), to remove toxic Cr(VI) from aqueous solutions was studied in a batch system as a function of contact time, adsorbate concentration, adsorbent dosage, and pH. In an equilibrium time of 420 min, the maximum Cr removal by OP at pH 2 and 10 was 100 and 97 %, respectively. The sorption data fitted well with Langmuir adsorption model. Evaluation using Langmuir expression presented a monolayer sorption capacity of 47.39 mg g-1 with an equilibrium sorbent dose of 5 g L-1 and pH 7. Uptake of Cr by OP was described by pseudo-second-order chemisorption model. ICP-OES, LC-ICPMS analysis of the aqueous and solid phases revealed that the mechanism of Cr(VI) removal is by 'integrated adsorption and reduction' mechanism. ESEM-EDX and XRD analysis of OP before and after adsorption also confirmed that both adsorption and reduction of Cr(VI) to less toxic Cr3+ forms followed by complexation onto the adsorbent surface contributed to the removal of Cr(VI). Consistent with batch studies, OP effectively removed (>95 %) Cr from the real water samples collected from lake and sea. The results of this study illustrate that OP could be an economical, green, and effective biomaterial for Cr(VI) removal from natural aquatic ecosystems and industrial effluents.

© 2015 Elsevier Ltd. A mercury resistant bacterial strain, SA2, was isolated from soil contaminated with mercury. The 16S rRNA gene sequence of this isolate showed 99% sequence similarity to the genera Sphingobium and Sphingomonas of a-proteobacteria group. However, the isolate formed a distinct phyletic line with the genus Sphingobium suggesting the strain belongs to Sphingobium sp. Toxicity studies indicated resistance to high levels of mercury with estimated EC50 values 4.5 mg L-1 and 44.15 mg L-1 and MIC values 5.1 mg L-1 and 48.48 mg L-1 in minimal and rich media, respectively. The strain SA2 was able to volatilize mercury by producing mercuric reductase enzyme which makes it potential candidate for remediating mercury. ICP-QQQ-MS analysis of Hg supplemented culture solutions confirmed that almost 79% mercury in the culture suspension was volatilized in 6 h. A very small amount of mercury was observed to accumulate in cell pellets which was also evident according to ESEM-EDX analysis. The mercuric reductase gene merA was amplified and sequenced. The deduced amino acid sequence demonstrated sequence homology with a-proteobacteria and Ascomycota group.

© 2016 Elsevier B.V.. Diversity, distribution and composition of bacterial community of soils contaminated long-term with both polycyclic aromatic hydrocarbons (PAHs) and heavy metals were explored for the first time following 454 pyrosequencing. Strikingly, the complete picture of the Gram positive (+ve) and Gram negative (-ve) bacterial profile obtained in our study illustrates novel postulates that include: (1) Metal-tolerant and PAH-degrading Gram -ves belonging to the class Alphaproteobacteria persist relatively more in the real contaminated sites compared to Gram +ves, (2) Gram +ves are not always resistant to heavy metal toxicity, (3) Stenotrophomonas followed by Burkholderia and Pseudomonas are the dominant genera of PAH degraders with high metabolic activity in long-term contaminated soils, (4) Actinobacteria is the predominant group among the Gram +ves in soils contaminated with high molecular weight PAHs that co-exist with toxic heavy metals like Pb, Cu and Zn, (5) Microbial communities are nutrient-driven in natural environments and (6) Catabolically potential Gram +/-ves with diverse applicability to remediate the real contaminated sites evolve eventually in the historically-polluted soils. Thus, the most promising indigenous Gram +/-ve strains from the long-term contaminated sites with increased catabolic potential, enzymatic activity and metal tolerance need to be harnessed for mixed contaminant cleanups.

© 2016, Springer Science+Business Media New York. Eisenia fetida is a terrestrial organism, which can be used to diagnose sub-lethal concentrations of PFOA by using molecular biomarkers. In order to identify potential molecular biomarkers, we have exposed E.¿fetida to 10¿mg/kg of PFOA in soil for 8¿months. The mRNA isolation, sequencing, transcriptome assembly followed by differential gene expression studies have revealed that genes that are involved in apoptotic process, reproduction, calcium signalling, neuronal development and lipid metabolism are predominantly affected. Highly specific genes that are altered by PFOA can be further validated and used as biomarker to detect sub-lethal concentrations of PFOA in the soil.

© 2015 Elsevier B.V. Since crude oil contamination is one of the biggest environmental concerns, its removal from contaminated sites is of interest for both researchers and industries. In situ bioremediation is a promising technique for decreasing or even eliminating crude oil and hydrocarbon contamination. However, since these compounds are potentially toxic for many microorganisms, high loads of contamination can inhibit the microbial community and therefore reduce the removal rate. Therefore, any strategy with the ability to increase the microbial population in such circumstances can be of promise in improving the remediation process. In this study, multiwall carbon nanotubes were employed to support microbial growth in sediments contaminated with crude oil. Following spiking of fresh water sediments with different concentrations of crude oil alone and in a mixture with carbon nanotubes for 30. days, the microbial profiles in these sediments were obtained using FLX-pyrosequencing. Next, the ratios of each member of the microbial population in these sediments were compared with those values in the untreated control sediment. This study showed that combination of crude oil and carbon nanotubes can increase the diversity of the total microbial population. Furthermore, these treatments could increase the ratios of several microorganisms that are known to be effective in the degradation of hydrocarbons.

© 2016, Springer-Verlag Berlin Heidelberg. In this study, the influence of soil types on the effect of the commercial form of C-nZVI on tissue concentrations, cellular component, reproduction outcome in Eisenia fetida, and the soil health was investigated. C-nZVI at concentration level of 3¿g¿kg-1 soil showed no effect on the survival of E. fetida in the three soil types. However, varying effects such as concentration-dependent increase in tissue iron concentration, lipid peroxidation, and damage to DNA molecules by C-nZVI were observed. C-nZVI at an exposure concentration of 60¿mg¿kg-1 soil induced oxidative stress in E. fetida. Tissue Fe concentration appeared correlated to the DNA damage. Oxidative stress and DNA damage may explain the toxicity mechanisms of nZVI to E. fetida. [Figure not available: see fulltext.].

© 2016, © Taylor & Francis Group, LLC.Systematic site survey for sample collection and analysis was conducted at a derelict copper (Cu) mine at Kapunda, South Australia. Cu concentrations in the soils at this former mine ranged from 65¿10107¿mg kg-1. The pH and EC varied widely in the 3.9¿8.4 and 152¿7311¿µS ranges, respectively. Nine plant species growing over the copper mine site were selected to screen for metal uptake to determine their suitability for phytoremediation. The Australian native tree species Eucalyptus camaldulensis indicated enrichment factor (EF) of 2.17, 1.89, and 1.30 for Cu, Zn, and Pb, respectively, suggesting that this species of tree can accumulate these metals to some degree. The stress-resistant exotic olive, Olea europaea exhibited EF of = 0.01 for Cu, Cd, and Pb, and 0.29 for Zn, which is characteristic of an excluder plant. Acacia pycnantha, the Australian pioneer legume species with EF 0.03, 0.80, 0.32, and 0.01 for Cu, Zn, Cd, and Pb, respectively, emerged as another strong metal excluder and consequently as an ideal metal stabilizer.

© 2016 American Institute of Chemical Engineers Soils contaminated with crude oil are rich sources of enzymes suitable for both degradation of hydrocarbons through bioremediation processes and improvement of crude oil during its refining steps. Due to the long term selection, crude oil fields are unique environments for the identificati on of microorganisms with the ability to produce these enzymes. In this metagenomic study, based on Hiseq Illumina sequencing of samples obtained from a crude oil field and analysis of data on MG-RAST, Actinomycetales (9.8%) were found to be the dominant microorganisms, followed by Rhizobiales (3.3%). Furthermore, several functional genes were found in this study, mostly belong to Actinobacteria (12.35%), which have a role in the metabolism of aliphatic and aromatic hydrocarbons (2.51%), desulfurization (0.03%), element shortage (5.6%), and resistance to heavy metals (1.1%). This information will be useful for assisting in the application of microorganisms in the removal of hydrocarbon contamination and/or for improving the quality of crude oil. © 2016 American Institute of Chemical Engineers Biotechnol. Prog., 32:638¿648, 2016.

© 2016 Elsevier B.V. The development of highly efficient, eco-friendly and cost-effective remediation technology to remove mixed contaminants is now in progress. Here, agarose-Fe nanoparticles (NPs) hydrogel were produced via two green steps to remove mixed contaminants, specifically trichloroethylene (TCE) and hexavalent chromium (Cr(VI)). Approx. 84.9% of Cr(VI) and 93.8% of TCE were simultaneously removed over 24 h in their co-existing solution, while 94.1% of Cr(VI) and 97.2% of TCE were separately removed by agarose-Fe NPs hydrogel. Scanning Electron Microscopy (SEM) suggested that the macroporosity of agarose-Fe NPs hydrogel facilitated the mass transfer between agarose-Fe NPs hydrogels and mixed contaminants, and that Fe NPs were uniformly immobilized into the hydrogel. X-ray Photoelectron Spectroscopy (XPS) and Fourier Transform Infrared Spectroscopy (FTIR) provided evidence supporting the co-removal mechanism. XPS result indicated that: (1) chemical reduction played a role in the removal of both Cr(VI) and TCE; and (2) iron oxides and Fe(III)-Cr(III) complexes might be formed after reaction. FTIR result showed that some functional groups were involved in the removal process. Moreover, the presence of iron oxides were confirmed by FTIR. Both SEM and XPS results verified that encapsulation could describe such immobilization of Fe NPs using agarose. Finally, the kinetics study supported the removal mechanism. Such encapsulation of Fe NPs via a green strategy is simple, quick, and cost-effective, making in situ remediation of mixed contaminants more favorable.

© 2016, Springer Science+Business Media Dordrecht. The lack of awareness for timely management of the environment surrounding a metal mine site results in several adverse consequences such as rampant business losses, abandoning the bread-earning mining industry, domestic instability and rise in ghost towns, increased environmental pollution, and indirect long-term impacts on the ecosystem. Although several abandoned mine lands (AMLs) exist globally, information on these derelict mines has not been consolidated in the literature. We present here the state-of-the-art on AMLs in major mining countries with emphasis on their impact towards soil health and biodiversity, remediation methods, and laws governing management of mined sites. While reclamation of metalliferous mines by phytoremediation is still a suitable option, there exist several limitations for its implementation. However, many issues of phytoremediation at the derelict mines can be resolved following phytostabilization, a technology that is effective also at the modern operational mine sites. The use of transgenic plant species in phytoremediation of metals in contaminated sites is also gaining momentum. In any case, monitoring and efficacy testing for bioremediation of mined sites is essential. The approaches for reclamation of metalliferous mines such as environmental awareness, effective planning and assessment of pre- and post-mining activities, implementation of regulations, and a safe and good use of phytostabilizers among the native plants for revegetation and ecological restoration are discussed in detail in the present review. We also suggest the use of microbially-enhanced phytoremediation and nanotechnology for efficient reclamation of AMLs, and identify future work warranted in this area of research. Further, we believe that the integration of science of remediation with mining policies and regulations is a reliable option which when executed can virtually balance economic development and environmental destruction for safer future.

© 2015 Elsevier Ltd. An arsenic hyper-tolerant diazotrophic bacterium was isolated from a heavy metal contaminated soil. The pure isolate MM-17 was identified as Azospirillum sp. based on phylogenetic analysis of 16S rRNA. The strain oxidized 100 µM As(III) to As(V) in both culture media (minimal salts) and real groundwater within 8 and 10 h, respectively. The oxidation of As(III) by this strain was observed within the pH range 5-10 with the best performance at pH 7-8. As(III) oxidation was found to be independent of cell growth which implies the oxidation enzymes are constitutively expressed. The whole cell kinetic study highlighted a lower value of kinetic constant, Ks as 32.9 µM As(III), which indicates that the strain MM-17 has greater affinity for As(III). The gene sequence of the large subunit of arsenite oxidase of MM-17 showed 99 and 72% similarity to the large subunit of arsenite oxidase of Stenotrophomonas sp. MM-7 and Sinorhizobium sp. M14, respectively. Sphaeroplasts experiments suggest that arsenite oxidase is a membrane associated protein in MM-17.

© 2015 Springer International Publishing Switzerland. Treatability studies in real contaminated soils are essential to predict the feasibility of microbial consortium augmentation for field-scale bioremediation of contaminated sites. In this study, the biodegradation of a mixture of seven PAHs in a manufactured gas plant (MGP) soil contaminated with 3967 mg kg-1 of total PAHs using novel acid-, metal-tolerant, N-fixing, P-solubilizing, and biosurfactant-producing LMW and HMW PAH-degrading bacterial combinations as inoculums was compared in slurry- and solid-phase microcosms over natural attenuation. Bioaugmentation of 5 % of bacterial consortia A and N in slurry- and solid-phase systems enhanced 4.6-5.7 and 9.3-10.7 % of total PAH degradation, respectively, over natural attenuation. Occurrence of 62.7-88 % of PAH biodegradation during natural attenuation in soil and slurry illustrated the accelerated rate of intrinsic metabolic activity of the autochthonous microbial community in the selected MGP soil. Monitoring of the total microbial activity and population of PAH degraders revealed that the observed biodegradation trend in MGP soil resulted from microbial mineralization. In the slurry, higher biodegradation rate constant (k) and lower half-life values (t 1/2) was observed during bioaugmentation with consortium N, highlighting the use of bioaugmentation in bioslurries/bioreactor to achieve rapid and efficient bioremediation compared to that of a static solid system. In general, natural attenuation was on par with bioaugmentation. Hence, depending on the type of soil, natural attenuation might outweigh bioaugmentation and a careful investigation using laboratory treatability studies are highly recommended before the upscale of a developed bioremediation strategy to field level.

© 2015 Elsevier B.V. To reduce cost and enhance reactivity, bimetallic Fe/Pd nanoparticles (NPs) were firstly synthesized using grape leaf aqueous extract to remove Orange II. Green synthesized bimetallic Fe/Pd NPs (98.0%) demonstrated a far higher ability to remove Orange II in 12h compared to Fe NPs (16.0%). Meanwhile, all precursors, e.g., grape leaf extract, Fe2+ and Pd2+, had no obvious effect on removing Orange II since less than 2.0% was removed. Kinetics study revealed that the removal rate fitted well to the pseudo-first-order reduction and pseudo-second-order adsorption model, meaning that removing Orange II via Fe/Pd NPs involved both adsorption and catalytic reduction. The remarkable stability of Fe/Pd NPs showed the potential application for removing azo dyes. Furthermore, Scanning Electron Microscopy (SEM) and Fourier Transform Infrared Spectroscopy (FTIR) confirmed the changes in Fe/Pd NPs before and after reaction with Orange II. High Performance Liquid Chromatography-Mass Spectrum (HPLC-MS) identified the degraded products in the removal of Orange II, and finally a removal mechanism was proposed. This one-step strategy using grape leaf aqueous extract to synthesize Fe/Pd NPs is simple, cost-effective and environmentally benign, making possible the large-scale production of Fe/Pd NPs for field remediation.

© 2016 The Royal Society of Chemistry. We demonstrated SERS (surface-enhanced Raman scattering) detection of fluorosurfactants (FSs), which are commonly formulated in aqueous firefighting foams (AFFFs), by increasing their loading affinity and boosting their Raman activity. In order to increase FS's loading affinity, we introduced a cationic dye (ethyl violet or methyl blue) into the aqueous incubation solution to co-precipitate the FS onto the SERS substrate surface by forming an immiscible ion-pair (dye-FS). In the meantime, the Raman signal intensity was boosted due to the much higher Raman activity of the dye than that of FS. We compared two kinds of SERS substrate, patterned silver (Ag) surface and graphene oxide (GO) membrane, and noted the former (dye-FS-Ag) enhanced the Raman signal whilst the latter (dye-FS-GO) increased the loading affinity of the ion-pair due to the hydrophobic surface. We thus introduced silver nanoparticles (AgNPs) into the incubation solution (as well as dye) to co-precipitate FS onto the GO surface via an assembly of dye-FS-AgNP-GO. Using this assembly, we successfully detected FSs including pentadecafluorooctanoic acid (PFOA), perfluorooctanesulfonic acid (PFOS), and 1H,1H,2H,2H-perfluorooctanesulfonic acid (6:2FTS), with a limit-of-detection (LOD) of ~50 ppb (~120 nM) for PFOA.

© 2016, Springer Science+Business Media New York. We exposed the microalgal strain, Chlorella sp. MM3, to unused or used engine oil, or their water accommodated fractions (WAFs) to determine growth inhibition and response of antioxidant enzymes. Oil type and oil concentration greatly affected the microalgal growth. Used oil at 0.04¿% (0.4¿g L-1) resulted in 50¿% inhibition in algal growth, measured in terms of chlorophyll-a, while the corresponding concentration of unused oil was nontoxic. Similarly, used oil WAF showed significant toxicity to the algal growth at 10¿% level, whereas WAF from unused oil was nontoxic even at 100¿% concentration. Peroxidase enzyme in the microalga significantly increased with used oil at concentrations above 0.04¿g L-1 whereas the induction of superoxide dismutase and catalase was apparent only at 0.06¿g L-1. Activities of the antioxidant enzymes increased significantly when the microalga was exposed to 75 and 100¿% WAF obtained from used oil. The used oil toxicity on microalga could be due to the presence of toxic soluble mono- and polyaromatic compounds, heavy metals, and other compounds attained by the oil during its use in the motor engines.

© 2016 Worldwide a multitude of firefighting compounds are currently used for the mitigation and protection of man-made structures and forests alike from fire damages. Among the class of firefighting agents, Class B firefighting foams are generally used to control fires generated from hydrocarbon liquids. In the present study, we assessed the cyto- and genotoxicity of two widely used class B firefighting foam concentrates, Tridol-S 3% and Tridol-S 6% to Alliumcepa through chromosomal aberration and comet assay using root meristem cells. A. cepa root tips were exposed to Tridol-S 3% and Tridol-S 6% with six different concentrations (0%, 0.005%, 0.01%, 0.02%, 0.03%, 0.04% and 0.05%) for 24 h. Cytogenetic effect endpoints such as mitotic index, and chromosomal aberrations were observed. Chromosomal aberrations in the control (untreated onion root tips) was negligible with the mitotic index (MI) value of 79.6%, while the MI significantly decreased in all the test concentrations of firefighting compounds. Genotoxicity assessment through comet assay also revealed that both the products were genotoxic with a significant increase in per cent tail DNA and olive tail moment. Among the test compounds, Tridol-S 3% was more toxic than Tridol-S 6%. To our knowledge, this is the first study on the cyto- and genotoxic effects of class B firefighting foams to A. cepa root meristem cells. This study also suggests that the toxicological studies using A. cepa root meristem cells can be employed for evaluating the toxicological impacts of firefighting foams in the environment.

© 2016 Elsevier B.V. A mercury resistant bacterial strain SE1 isolated from contaminated soil was identified as Pseudoxanthomonas based on 16s rRNA sequencing. The Hg resistance was examined in both nutrient-rich media as well as low nutrient media and expressed as EC50 and MIC values. Estimated EC50 and MIC values in nutrient-rich media and low nutrient media had the following respective recordings ¿ 22.6 mg L-1; 23.1 mg L-1 and 1.4 mg L-1 and 1.7 mg L-1. The isolate was able to volatilize inorganic mercury demonstrated by a modified photographic film experiment and subsequently revealed its ability to remove mercury from the solution. The ICP-QQQ-MS analysis of SE1 inoculated solution showed almost 60% of 1.5 mg L-1 mercury was volatilized in 6 h and almost 40% were accumulated in cell pellets. The mercuric reductase gene merA was identified in the genome of isolate SE1 and sequenced. The deduced amino acid sequence of merA gene indicated a sequence homology with different organisms from the alpha proteobacteria group and eukaryotic fungi. merA encoded enzyme mercuric reductase activity was evident in the crude protein of the isolate. The isolate's ability to resist Hg, it's Hg volatilization potential and the presence of merA gene and mercuric reductase enzyme demonstrates the potential application of this strain in mercury bioremediation.

© 2016 Elsevier B.V. Dearth of high molecular weight contaminant degradation, pH tolerance and growth limiting nutrient assimilation potentials of the selected microorganisms are some of the prime factors reasonable for the failures in field-scale bioremediation of PAHs contaminated soils. Hence an effort was made in this study for the first time to identify HMW PAHs degrading, N-fixing and P-solubilizing bacteria with pH tolerance from long-term manufactured gas plant site soils. Four distinct strains that could degrade both LMW and HMW PAHs were identified. Among the isolates, Stenotrophomonas (MTS-2) followed by Citrobacter (MTS-3) and Pseudomonas (MTS-1) were furthermost effective in the degradation of HMW PAHs either as individual or in the presence of co-substrate (LMW PAHs). MTS-1, 2 and 3 (co)degraded model LMW PAHs, Phe (100% of 150 mg L-1) and HMW PAHs Pyr (100% of 150 mg L-1) or BaP (90¿100% of 50 mg L-1) in 3, 12¿15 and 30 days, respectively and recorded the least half-life time (t1/2) and highest biodegradation rate constants (k). One of the significant findings is the diazotrophic P-solubilization ability, acid and alkali tolerance (optimum pH=5.0¿8.0) of the HMW PAHs degrading Pseudomonas strain MTS-1. Stenotrophomonas (MTS-2) was also found to be superior as it could solubilize P and tolerate acidic condition (optimum pH=5.0¿7.5) during HMW PAHs degradation. Further, our study is the first evidence of diazotrophic P solubilization potential of Agrobacterium (MTS-4) and P-solubilizing capacity of Citrobacter (MTS-3) during bioremediation. Thus, the results of this study demonstrate the promising use of the newly identified PAH degraders, notably MTS-1, 2 and 3 either as individuals or as consortia as an excellent candidate in the bioremediation or phytoremediation of PAHs contaminated soils.

© 2016, Springer Science+Business Media Dordrecht. A new green microalgal species was isolated, identified and investigated for its biomass production and nutrient removal efficiency in dairy and winery wastewater in this study. The 18S rRNA-based phylogenetic analysis revealed that this new strain is a Diplosphaera sp. and was designated strain MM1. The growth of this strain was evaluated in different diluted dairy and winery wastewaters. The highest algal biomass production (up to 2.3¿g¿L-1) was obtained in dairy wastewater (D3; dairy wastewater 1:2 deionised water) after 14¿days of culture. However, for winery wastewater, the highest algal biomass production (up to 1.46¿g¿L-1) was obtained in wastewater combination W2 (winery wastewater 1:1 deionised water) after 14¿days of culture. Turbid dairy wastewater with high concentration of nitrogen and phosphorous slowed down the initial growth of the alga. However, at the end of day 14, biomass production was nearly twofold higher than that of winery wastewater. The findings from both types of wastewater suggest that Diplosphaera sp. MM1 has potential for its application in generating biomass with simultaneous remediation of nutrient-rich wastewater.

© 2016 Elsevier Inc. The presence of sulphur-substituted hydrocarbons in fossil fuels are one of main reasons for the release of sulfur oxides into the environment. Dibenzothiophenes (DBT) are organic sulfur-containing molecules in crude oil, which have the potential for biological oxidation, with the sulphur being removed through an enzymatic cleavage of the C. S bonds. Therefore, finding new strains that can desulfurize this compound has recently become a point of interest. In this study, three new genes involved in the bacterial desulfurization of Dibenzothiophene, which were sequenced in the course of a metagenomic study, were isolated by PCR amplification in the laboratory. The activities of these genes were then analysed following insertion into an expression vector and cloning in Escherichia coli DH5a cells. Based on the results, all three genes were actively expressed and their products could act on their corresponding substrates.

© 2016 The Institution of Chemical Engineers. The present study describes for the first time the utilization of dried twigs of Melaleuca diosmifolia, fallen off from the plant, to detoxify and remove hexavalent chromium or Cr(VI) from aqueous systems. Initial characterization by gas chromatography revealed that the selected biomaterial is one of the natural sources of eucalyptol. It constituted high concentrations of reducing compounds (iron, phenols and flavonoids). Batch studies revealed that the biosorbent (5 g L-1) was able to remove 97-99.9% of 250 mg L-1 Cr(VI) at wide-ranging pH (2-10) and temperature (24-48 °C). Adsorption kinetics was well described using the pseudo-second-order kinetic model, while the equilibrium adsorption data were interpreted in terms of the Langmuir isotherm model. The monolayer adsorption capacity was 62.5 mg g-1. Both inductively coupled plasma optical emission spectrometry and liquid chromatography analyses of the aqueous and solid phases revealed that the mechanism of Cr(VI) removal was 'adsorption-coupled reduction'. Scanning electron microscope, infrared spectroscopy and X-ray diffraction analyses of the biosorbent before and after adsorption also confirmed that both adsorption and reduction of Cr(VI) to Cr(III) followed by complexation onto functional groups of the active surface contributed to the removal of Cr(VI) from aqueous solution. The selected biomaterial effectively (99.9%) removed Cr(VI) in lake and sea water samples, highlighting its potential for remediating Cr(VI) in real environmental conditions.

© 2015 Elsevier Ltd. Barite contamination of soil commonly occurs from either barite mining or explorative drilling operations. This work reported in vitro data for barite contaminated soils using the physiologically based extraction test (PBET) methodology. The existence of barite in plant tissue and the possibility of 'biomineralised' zones was also investigated using Scanning Electron Microscopy. Soils with low barium (Ba) concentrations showed a higher proportion of Ba extractability than barite rich samples. Barium uptake to spinach from soil was different between short term spiking studies and field weathered soils. Furthermore, Ba crystals were not evident in spinach tissue or acid digest solutions grown in barium nitrate spiked soils despite high accumulation. Barite was found in the plant digest solutions from barite contaminated soils only. Results indicate that under the conservative assumptions made, a child would need to consume extreme quantities of soil over an extended period to cause chronic health problems.

© 2015 Elsevier Ltd. Recent decades have seen a growing popularity of in vitro bioaccessibility being utilised as a screening tool in human health risk assessment. However the existing bioaccessibility studies only focus on single contaminant. Considering human are likely to ingest multi-contaminants, these contaminants could interact within human gastrointestinal tract which may lead to an increase or decrease in bioaccessibility. In this study, seven different types of soil were spiked with arsenic (As) or cadmium (Cd) and aged for one year. The effects of soil properties on the bioaccessibility were examined. Moreover, the interaction between As and Cd in simulated human digestive system was studied by mixing As-spiked soil with Cd-spiked soil of the same type during bioaccessibility test. Results shows the bioaccessibility of As ranged from 40 ± 2.8 to 95 ± 1.3% in the gastric phase and 16 ± 2.0 to 96 ± 0.8% in the intestinal phase whilst a significant difference was observed between Cd gastric bioaccessibility (72 ± 4.3 to 99 ± 0.8%) and intestinal bioaccessibility (6.2 ± 0.3 to 45 ± 2.7%). Organic carbon, iron oxide and aluminium oxide were key parameters influencing the bioaccessibility of As (gastric and intestinal phases) and Cd (intestinal phase). No interactions between As and Cd during bioaccessibility test were observed in any soils, which indicates As and Cd may age independently and did not interact while being solubilised during bioaccessibility test. Thus additive effect may be proposed when estimating the bioaccessibility of mixtures of independently-aged As and Cd in soils.

© 2016, Islamic Azad University (IAU). Four bacterial strains, capable of degrading diesel oil, n-alkanes or hexadecane, were isolated from soils contaminated with petroleum oil and identified. Strains of Pseudomonas sp., Pseudomonas putida TPHK-1 and Pseudomonas aeruginosa TPHK-4, were more efficient in degrading high concentrations of the hydrocarbons than the other two strains, Stenotrophomonas maltophilia TPHK-2 and Acenitobacter sp. TPHK-3. P. putida TPHK-1 exhibited tolerance to very high concentrations of heavy metals such as cadmium, lead, zinc and copper. The innate ability of P. putida TPHK-1, as evidenced by the amplified genes alkB1 and alkB2 that encode alkane hydroxylases, and cat12o and cat23o coding for catechol dioxygenase, in degrading diesel oil in the presence of heavy metals is far greater than that of the strains reported in the literature. Heavy metal tolerance coupled with rapid degradation of hydrocarbons, even at high concentrations, suggests that P. putida TPHK-1 has a great potential in remediating soils contaminated with mixtures of hydrocarbons and heavy metals.

© 2016 Elsevier Ltd An isolate of Cupriavidus (strain MTS-7) was identified from a long-term PAHs and heavy metals mixed contaminated soil with the potential to biodegrade both LMW and HMW PAHs with added unique traits of acid and alkali tolerance, heavy metal tolerance, self-nutrient assimilation by N fixation and P solubilization. This strain completely degraded the model 3 (150¿mg¿L-1 Phe), 4 (150¿mg¿L-1 Pyr) and 5 (50¿mg¿L-1 BaP) ring PAHs in 4, 20 and 30 days, respectively. It could mineralize 90¿100% of PAHs (200¿mg¿L-1 of Phe and Pyr) within 15 days across pH ranging from 5 to 8 and even in the presence of toxic metal contaminations. During biodegradation, the minimum inhibitory concentrations were 5 (Cu2+) and 3 (Cd2+, Pb2+, Zn2+) mg L-1 of the potentially bioavailable metal ions and over 17¿mg¿L-1 metal levels was lethal for the microbe. Further, it could fix 217¿274¿µg¿mL-1 of N and solubilize 79¿135¿µg¿mL-1 of P while PAHs degradation. MTS-7 as a superior candidate could be thus used in the enhanced bioaugmentation and/or phytoremediation of long-term mixed contaminated sites.

© 2016 Elsevier Ltd We reported the Australian golden wattle as a copper stabilizer in abandoned copper mine soils earlier. Here we investigate to confirm this plant's suitability to grow on metal contaminated mine soils based on stress indication. The seeds of Acacia pycnantha collected from mining area were germinated after heat and no heat treatment on two types of irrigation. The daily irrigated and heat treated seeds gave up to 85% germination on sandy soil. The A. pycnantha was grown under greenhouse condition in six different soils collected from abandoned copper mine at Kapunda in South Australia. Among the six soil samples, soil-1 with the highest copper concentration produced 2.05 mmol g-1 tissue of proline. Proline expression was prominent in more saline soils (1, 5 and 6) having electrical conductivity (EC) 1184, 1364 and 1256 µS, respectively. Chlorophyll a, b and carotenoid levels in plants showed a gradually decreasing trend in all the soils as experiment progressed. The plants grown on soil sample-1, containing 4083 ± 103 mg kg-1 of copper resulted in 18 ± 2 mg kg-1 accumulation in its leaf. The calcium accumulation was significant up to 11648 ± 1209 mg kg-1 in leaf. Although pore water samples showed higher Cu concentration in soils, an increased mobility of arsenic and lead was observed in all the soil samples. Our experiment points out the need for proper monitoring of revegetation processes to avoid revegetation and reclamation failure.

© 2016, Springer International Publishing Switzerland. Perfluorooctanoic acid (PFOA) is a widespread persistent organic contaminant in the environment that has recently raised much of regulatory and public concern. Therefore, assessment of its ecological risk is a top priority research. Hence, this study investigated the toxicity of PFOA to beneficial microbial processes in the soil such as activities of dehydrogenase, urease and potential nitrification in addition to earthworm survival, weight loss and PFOA bioaccumulation in two contrasting soils. In general, PFOA caused inhibition of all the measured microbial processes in a dose-dependent manner and the inhibition was higher in Williamtown (WT) soil than Edinburgh (EB) soil. Thus, WT soil being sandy in nature with low clay content showed higher PFOA bioavailability and hence showed higher toxicity. There was no mortality in earthworms exposed up to 100¿mg PFOA/kilogram soil in both the soils; however, there was a significant weight loss from 25¿mg/kg onwards. This study clearly demonstrates that soil contamination of PFOA can lead to adverse effects on soil health.

© 2016, Springer Science+Business Media New York. Crude oil spills resulting from excavation, transportation and downstream processes can cause intensive damage to living organisms and result in changes in the microbial population of that environment. In this study, we used a pyrosequencing analysis to investigate changes in the microbial population of soils contaminated with crude oil. Crude oil contamination in soil resulted in the creation of a more homogenous population of microorganisms dominated by members of the Actinomycetales, Clostridiales and Bacillales (all belonging to Gram-positive bacteria) as well as Flavobacteriales, Pseudomonadales, Burkholderiales, Rhizobiales and Sphingomonadales (all belonging to Gram-negative bacteria). These changes in the biodiversity decreased the ratios of chemoheterotrophic bacteria at higher concentrations of crude oil contamination, with these being replaced by photoheterotrophic bacteria, mainly Rhodospirillales. Several of the dominant microbial orders in the crude oil contaminated soils are able to degrade crude oil hydrocarbons and therefore are potentially useful for remediation of crude oil in contaminated sites.

© 2016 Elsevier Ltd. Background: There are many uncertainties concerning variations in benzo[a]pyrene (B[a]P) soil guidelines protecting human health based on carcinogenic data obtained in animal studies. Although swine is recognised as being much more representative of the human child in terms of body size, gut physiology and genetic profile the rat/mice model is commonly used in practice. Objectives: We compare B[a]P bioavailability using a rat model to that estimated in a swine model, to investigate the correlation between these two animal models. This may help reduce uncertainty in applying bioavailability to human health risk assessment. Methods: Twelve spiked soil samples and a spiked silica sand (reference material) were dosed to rats in parallel with a swine study. B[a]P bioavailability was estimated by the area under the plasma B[a]P concentration-time curve (AUC) and faecal excretion as well in the rats. Direct comparison between the two animal models was made for: firstly, relative bioavailability (RB) using AUC assay; and secondly, the two assays in the rat model. Results: Both AUC and faecal excretion assays showed linear dose-response for the reference material. However, absolute bioavailability was significantly higher when using faecal excretion assay (p < 0.001). In aged soils faecal excretion estimated based on solvent extraction was not accurate due to the form of non-extractable fraction through ageing. A significant correlation existed between the two models using RB for soil samples (RBrat = 0.26RBswine + 17.3, R2 = 0.70, p < 0.001), despite the regression slope coefficient revealing that the rat model would underestimate RB by about one quarter compared to using swine. Conclusions: In the comparison employed in this study, an interspecies difference of four in RB using AUC assay was identified between the rat and swine models regarding pharmacokinetic differences, which supported the body weight scaling method recommended by US EPA. Future research should focus on the carcinogenic competency (pharmacodynamics) used in experiment animals and humans.

© 2016 Elsevier Inc. The leaf litters of tree species, Acacia pycnantha (Ap) and Eucalyptus camaldulensis (Ec), predominantly growing at an abandoned copper (Cu) mine and mine soils including controls, were assessed for determining the metal toxicity and bioavailability using earthworm species Eisenia fetida, in a microcosm. Significant reduction in body weight as well as mortality were observed when the worms were introduced into mine soil or its combination with mine Ap litter. Virtually, there were no juveniles when the worms were fed on substratum that contained mine soil or mine leaf litter. The extent of bioaccumulation was dependent on water-soluble fraction of a metal in soil. The accumulation of cadmium, lead and copper in worm tissue was significantly more in treatments that received mine soil with or without mine leaf litter. However, the tissue concentration of zinc did not differ much in earthworms irrespective of its exposure to control or contaminated samples. Mine leaf litter from Ec, a known Cu hyperaccumulator, was more hospitable to earthworm survival and juvenile than that of Ap litter. Validation of the data on bioaccumulation of metals indicated that the mine leaf litter significantly contributed to metal bioavailability. However, it was primarily the metal concentration in mine soil that was responsible for earthworm toxicity and bioavailability. Our data also indicate that detrivores like earthworm is greatly responsible for heavy metal transfer from mines into the ecosystem.

© 2015, Springer-Verlag Berlin Heidelberg. In this study, the toxicity, biotransformation and bioaccumulation of arsenite and arsenate in a soil microalga, Chlorella sp., were investigated using different phosphate levels. The results indicated that arsenate was highly toxic than arsenite to the alga, and the phosphate limitation in growth media greatly enhanced arsenate toxicity. The uptake of arsenate in algal cells was more than that of arsenite, and the predominant species in the growth media was arsenate after 8¿days of exposure to arsenite or arsenate, indicating arsenite oxidation by this microalga. Arsenate reduction was also observed when the alga was incubated in a phosphate-limiting growth medium. Similar to the process of biotransformation, the alga accumulated more arsenic when it was exposed to arsenate and preferably more in a phosphate-limiting condition. Although phosphate significantly influences the biotransformation and bioaccumulation of arsenic, the oxidizing ability and higher accumulation capacity of this alga have great potential for its application in arsenic bioremediation.

© 2015 Elsevier Ltd. 'Biochar' represents an emerging technology that is increasingly being recognized for its potential role in carbon sequestration, reducing greenhouse gas emissions, waste management, renewable energy, soil improvement, crop productivity enhancement and environmental remediation. Published reviews have so far focused mainly on the above listed agronomic and environmental benefits of applying biochar, yet paid little or no attention to its harmful effects on the ecological system. This review highlights a balanced overview of the advantages and disadvantages of the pyrolysis process of biochar production, end-product quality and the benefits versus drawbacks of biochar on: (a) soil geochemistry and albedo, (b) microflora and fauna, (c) agrochemicals, (d) greenhouse gas efflux, (e) nutrients, (f) crop yield, and (g) contaminants (organic and inorganic). Future research should focus more on the unintended long-term consequences of biochar on biological organisms and their processes in the soil.

© 2015 Elsevier B.V. Arsenic (As) is a mobile and ecotoxic metalloid that is of serious concern to the environment. In this study, As phytotoxicity was studied using a dose-response approach for seven contrasting soils considering 3 end-points (shoot biomass, root elongation and chlorophyll content) and focusing on predictors of toxicity. Root elongation study was carried out for 4days using both Cucumis sativus L. (cucumber) and Triticum aestivum L. (wheat) and shoot end-points with a 4week a pot study using cucumber only. Root elongation of cucumber was a substantially less sensitive indicator to As than data from the 4weeks pot study. Effective concentrations (50%)(EC50) from cucumber root elongation studies were overall 1.6 times higher than the 4week shoot data. Cucumber was however considerably more sensitive to wheat. Given the large discrepancy in phytotoxicity end points for 7 soils, root elongation data for ecotoxicological assessment should be treated with some caution. Arsenic phytotoxicity was strongly related to the sorption constants of each of the seven soils in our study. Both root elongation and shoot data were related strongly to Freundlich partitioning constants (Kf) (L/kg). Wheat and cucumber root elongation had R2 values 0.90 and 0.91 respectively, while cucumber shoot data was 0.79. The Kf values were related to soil pH and also EC50 data and, thus, shows that As phytotoxicity in our study was primarily controlled by sorption reactions. The rate of As bioaccumulation to cucumber shoots depended heavily on the soil under consideration. Chlorophyll and carotenoid content of cucumber shoots increased with As content in 3 soils and decreased in other soils.

© 2016 Elsevier B.V. The sorption behavior of cadmium (Cd(II)) and zinc (Zn(II)) on two virgin soils with different pH levels was studied using single metal and competitive dual metal systems. In the single metal system, Zn exhibited a greater affinity for the alkaline soil, as indicated by the Langmuir constant (KL = 8.85 L/kg) compared with Cd (KL = 1.79 L/kg). However, much less sorption of both Zn (KL = 0.19 L/kg) and Cd (KL = 0.07 L/kg) was observed in the acidic soil. The competitive sorption data were modeled using two-metal Freundlich and Langmuir functions. The competition for metal sorption occurred in the alkaline soil only at a higher concentration of the competing metals, whereas the effect was significant even at lower concentrations in the acidic soil. The cumulative amount of both metals sorbed in the soil was similar to that of single metal systems in the studied concentration range, demonstrating that the number of sites available for sorption remained constant irrespective of the competition. This study indicated that Cd might be more mobile in a mixed-metal system than in a single-metal scenario and thus poses a serious ecotoxicological threat. This study is important for assessing the risks and developing management strategies for multiple heavy metal contaminated soils.

© 2015 Elsevier Ltd. Field-scale bioremediation of PAHs contaminated soils have proved to be difficult and challenging due to inhibited growth of PAH degrading microbes. In this study, for the first time mixed bacterial cultures designated as consortia-A and N were developed using elite metal or acid tolerant, N-fixing, P-solubilizing and biosurfactant producing PAH degraders enriched from manufactured gas plant sites. The two consortia could degrade both LMW and HMW PAHs. Kinetic studies of PAH degradation by the consortia showed the highest biodegradation rate constants (k = 0.027-0.61 day-1) and lowest half-life time (t1/2 = 1-26 days) values reported to date in liquid cultures and highlighted the use of consortium-A for the remediation of acidic soils due to its tolerance up to pH 5. Furthermore, bioaugmentation of these consortia has proven to be effective in degradation of LMW (>95%) and HMW (90%) PAHs from spiked soil slurries. Amendment of consortia-A and N exhibited 10.7 and 44.3% more total PAHs degradation, respectively than natural attenuation in 60 days even from the real long-term mixed contaminated soils. Thus the results of this study demonstrate the great potential of these novel bacterial consortia, particularly consortium-N for use in field-scale bioremediation of PAHs in long-term mixed contaminated neutral soils.

© 2016 The Korean Society of Industrial and Engineering Chemistry.The potential of dried twigs of Melaleuca diosmifolia as a novel biosorbent for removing three cationic dyes, methylene blue (MB), acridine orange (AO) and malachite green (MG), and an anionic dye, eriochrome black T (EB) was evaluated in a batch adsorption process. Notably, the biosorbent removed 77-99% of both cationic and anionic dyes in a wide ranging pH of 2-10, and the reactions were endothermic. The dye adsorption equilibria were rapidly attained within 3 h. The monolayer adsorption capacity of the sorbent added at 5 g L-1 was 119.05, 126.8, 116.28 and 94.34 mg g-1 for MB, AO, MG and EB, respectively. The water extract obtained from the plant material induced fast decolourization of both categories of dyes followed by gradual flocculation, indicating its potential as a natural coagulant. Gas chromatographic analysis also indicated that the main electrostatic attraction between 1,8-cineole, 1-p-methene-8-thiol and furfural compounds of the biomaterial, and dye molecules resulted in the formation of initial supramolecular complexes which further progressed into strong aggregates, leading to precipitation of dye-biomaterial complexes. Subsequently, the overall complex mechanism of dye removal was confirmed to be a combined process of adsorption and coagulation. Consistent with the batch studies, using selected plant material in real environmental water samples also resulted in effective dye removal, highlighting its potential for use in wastewater treatment.

© 2015 Elsevier B.V. All rights reserved. The green synthesis of functional iron nanoparticles (Fe NPs) by tea extracts was used as a catalyst for the Fenton-like oxidation of malachite green (MG), where more than 85% of MG was removed. The new findings are that the removal of MG by Fe NPs was based on the adsorption of MG onto iron oxide and degradation of MG by iron nanoparticles. This was confirmed by adsorption and degradation kinetics, indicating that: firstly, the adsorption kinetics follows the pseudo-first-order model; and secondly, degradation kinetics fitted well to the pseudo-second-order model. Morphology, size and changes in the Fe NPs surface were characterized using SEM, XRD, and FTIR techniques, showing that Fe<inf>2</inf>O<inf>3</inf> and Fe<inf>3</inf>O<inf>4</inf> was formed and green tea extract contained a high concentration of caffeine/polyphenols. It acted as both reducing and capping agents in the synthesis of Fe NPs. To further confirm the removal mechanism of MG by the functional Fe NPs, the degraded products were identified by FTIR and GC-MS analysis. Finally the mechanism of Fenton-like oxidation of MG based on both adsorption and degradation was proposed.

© The Royal Society of Chemistry 2015. Electronic dialogue between proteins is expected to be a key component of charge transport at the microbe-mineral interface (MMI) and requires complex structures. Microbial nanofilaments are one such structure produced in energetically engineered environments. These nanostructures consist of natural protein electronic conduits which can target the microbe-mineral interface and facilitate charge transport over a distance. Nanofilaments are phylogenetically diverse inducible extracellular appendages, and have the potential to serve as organic electronic conductors. However, recent investigations on such microbial nanofilaments have been confined to a few bacterial genera such as Geobacter, Shewanella and Synechocystis. Here, we report the evidence for longitudinal electron transport through inducible nanofilaments produced by another genus, the metabolically versatile photosynthetic, iron(iii) respiring bacterium Rhodopseudomonas palustris strain RP2, in photic, iron(iii) oxide-rich environments. In contrast, chemosynthetic dark-grown anoxic cells are weak in their ability to reduce ferric-oxide and no longer produce extracellular structures. Independent evaluation techniques illustrate the induction of extracellular filaments and their electrical properties. Scanning probe and nanofabricated electrode measurements provide conclusive evidence for the occurrence of direct charge transfer along the length and radius of nanofilaments from strain RP2. These findings not only expand our knowledge of the range of bacteria known to produce nanofilaments but also provide further research opportunities in the field of bionanotechnology, sustainable remediation (bioelectrochemical remediation systems) in contaminated sites (petroleum hydrocarbons) and MMI process at photic environments.

© 2015 Elsevier B.V. 'Green waste' (food, agro-industrial and forest residues) is a renowned valuable resource of polyphenols. Natural polyphenols are relatively efficient in the clean-up of environmental pollutants based on their unique traits of chelation, adsorption, reduction, complexation, nutrient cycling, antibacterial effects and plant growth promotion. These significant traits have found emerging applications in the removal of heavy metals, pathogenic bacteria and dyes from contaminated soil and water through existing bioremedial techniques such as biosorption, phytoextraction and coagulation. Increasingly, polyphenol-rich natural extracts harnessed for green nanoparticle synthesis (production of particles between 1 and 100 nm in size using biological entities such as microorganisms or plant biomass) have found promising use as a remedial agent in the detoxification of toxic pollutants. However, current bioremediation approaches do not sufficiently exploit natural polyphenols, which are abundantly available and are non-toxic. This review examines the extent of natural polyphenol availability in green waste, and provides a critical view on the existing remedial options, knowledge gaps and hence scope for future research. It highlights the use of natural polyphenol-rich green wastes as nanofertilizers, bioamendments, biofilters and bacteriostats. Field application strategies such as microbe-assisted phytoremediation, bioaugmention and biostimulation are also emphasized, showing the multifunctional biotechnological potentials offered by natural polyphenols.

© 2015 Elsevier B.V. Irrespective of the nature of contamination, the use of total contaminant loading as a measure of risk together with conservative policy guidance is proving major stumbling block towards remediation of contaminated sites. The objective of this study was to investigate the use of risk based approach to manage contaminated sites at field scale. This study recognizes the presence of weathered hydrocarbon compounds in long-term total petroleum hydrocarbon (TPH) contaminated soils and that such compounds may not pose risk to local receptors. A multispecies ecotoxicological assessment was used to determine the potential risk from weathered hydrocarbons to the surrounding environment. The ecotoxicity of soil residual TPHs was evaluated using earthworm, water-flea, two native and two non-native Australian plants, and soil microbial activity. Plant germination was 100% in all soils but post germination, seedlings except Ryegrass failed to establish. Earthworm toxicity studies found that there was a negative impact on earthworm reproduction and mortality. Further investigation of the poor plant growth and earthworm mortality revealed that it was due to the elevated salinity that developed due to surface evaporation of the saturated calcium sulphate and not residual soil TPHs. Toxicity assessment of the soil leachate on the aquatic environment showed no effect on the survival of water-flea even though the TPH concentrations in the first year leachate were as high as 1.6 mg TPH L-1. The study concluded that the residual TPHs in soils had little impact on a range of environmental receptors. Assessment of the residual TPH ecotoxicity was complicated by the elevated salinity of stockpile soils which impacted on the earthworm and phytotoxicity assessments. Therefore results of this study suggest that it is paramount to focus beyond target contaminants while implementing risk-based management approach. Indicators for risk based assessment are considered critical for regulatory decision making. The results of this study provide a valuable input in to the risk based management of contaminated sites.

© 2015 SETAC. The present study tested some aqueous film-forming foam (AFFF) products for the presence of or the potential to form 1H,1H,2H,2H-perfluorooctanesulfonic acid (6:2FTS) and 1H,1H,2H,2H-perfluorodecane sulfonic acid (8:2FTS). The results demonstrated the appearance of significant levels of 6:2FTS and 8:2FTS after the oxidization of those AFFFs. The authors concluded that fluorotelomer skeletons exist but are derived from those formulations of AFFFs.

© 2015 The Authors Accumulation and enrichment of heavy metals in the above ground parts of Australian native Acacia pycnantha (Ap) and Eucalyptus camaldulensis (Ec) growing in an abandoned copper mine located in Kapunda, South Australia have been studied. Cu and other metals (Na, Al, K, Ca, Fe, Zn, Cd and Pb) in plants and corresponding soils were analysed to evaluate plant interaction with soils containing heavy metals. As per the total metal analysis of leaf and corresponding soil samples, Ap accumulated 93.6 mg kg-1 of Cu in leaf while the corresponding soil concentration was 1632 mg kg-1. The Ec accumulated 5341 mg kg-1 of Cu in leaf while the concentration of this heavy metal in soil was 65 mg kg-1 in soil. The ESEM spectral analysis also showed a high leaf concentration of Cu in Ec (7%) as against only 0.12% in Ap. The average bioconcentration factor for Cu, Zn, Cd and Pb in Ec was much higher than that of Ap. Similarly, enrichment factor was more in Ec for Cu, Zn and Pb than in Ap. In contrast, translocation factor for only Zn and Cd was high in Ap. This study points out that Ec and Ap have different stabilising potential in remediating heavy metals like Cu in mined soils.

© 2015 Elsevier Inc. Zinc (Zn) is a widespread soil contaminant arising from a numerous anthropogenic sources. However, adequately predicting toxicity of Zn to ecological receptors remains difficult due to the complexity of soil characteristics. In this study, we examined solid-solution partitioning using pore-water data and toxicity of Zn to cucumber (Cucumis sativus L.) in spiked soils. Pore-water effective concentration (ECx, x=10%, 20% and 50% reduction) values were negatively related to pH, indicating lower Zn pore water concentration were needed to cause phytotoxicity at high pH soils. Total dissolved zinc (Zn<inf>pw</inf>) and free zinc (Zn²⁺) in soil-pore water successfully described 78% and 80.3% of the variation in relative growth (%) in the full dataset. When the complete data set was used (10 soils), the estimated EC50<inf>pw</inf> was 450 and 79.2µM for Zn<inf>pw</inf> and Zn²⁺, respectively. Total added Zn, soil pore water pH (pH<inf>pw</inf>) and dissolve organic carbon (DOC) were the best predictors of Zn<inf>pw</inf> and Zn²⁺ in pore-water. The EC10 (total loading) values ranged from 179 to 5214mg/kg, depending on soil type. Only pH measurements in soil were related to ECx total Zn data. The strongest relationship to ECx overall was pH<inf>ca</inf>, although pH<inf>w</inf> and pH<inf>pw</inf> were in general related to Zn ECx. Similarly, when a solution-only model was used to predict Zn in shoot, DOC was negatively related to Zn in shoot, indicating a reduction in uptake/ translocation of Zn from solution with increasing DOC.

© The Royal Society of Chemistry 2015. In this study, we report a facile synthesis of shape controlled three dimensional hydroxyapatite nanostructures (HAp) using a sacrificial thermoplastic polyurethane (TPU) nanofiber template. The TPU nanofibers synthesised using an electrospinning process were used as a template during the HAp synthesis through a precipitation process. Various HAp morphologies including distinctly placed cylindrically porous HAp architecture, coral reef like, tightly packed fibrous sheet like and nanofiber like were synthesised using the TPU nanofiber template. All the synthesised HAp were characterized using appropriate techniques like Fourier transform infrared spectroscopy (FTIR), X-ray diffraction (XRD), field emission scanning electron microscopy (FESEM) attached with selected area electron diffraction (SAED), energy dispersive X-ray spectroscopy (EDS) and X-ray photoelectron spectroscopy (XPS). The morphology, pore arrangement and the particle size of the HAp varied significantly with varying dimensions of the template and the template available per unit area of HAp. Hence, we have achieved four different 3D HAp morphologies using a single type of TPU nanofiber template. The TPU templated HAp nanostructures were more biodegradable than the control HAp.

© 2015 Elsevier B.V. This study introduced a patented novel methodological system for automatically analysis of Fourier Transform Infrared Spectrometer (FTIR) spectrum data located at 'fingerprint' region (wavenumber 670-800 cm-1), to simultaneously determinate multiple petroleum hydrocarbons (PHs) in real mixture samples. This system includes: an object oriented baseline correction; Band decomposition (curve fitting) method with mathematical optimization; and Artificial Neural Network (ANN) for determination, which is suitable for the characteristics of this IR regions, where the spectra are normally with low signal to noise ratio and high density of peaks. BTEX components are potentially lethal carcinogens and contained in many petroleum products. As a case study, six BTEX components were determinate automatically and simultaneously in mixture vapor samples. The robustness of the BTEX determination was validated using real petroleum samples, and the prediction results were compared with gas chromatography-mass spectrometry (GC-MS).

Arsenic contamination of groundwater and surface water is widespread throughout the world. Considering its carcinogenicity and toxicity to human and animal health, remediation of arsenic-contaminated water has become a high priority. There are several physicochemical-based conventional technologies available for removing arsenic from water. However, these technologies possess a number of limitations such as high cost and generation of toxic by-products, etc. Therefore, research on new sustainable and cost-effective arsenic removal technologies for water has recently become an area of intense research activity. Bioremediation technology offers great potential for possible future application in decontamination of pollutants from the natural environment. It is not only environmentally friendly but cost-effective as well. This review focuses on the state-of-art knowledge of currently available arsenic remediation methods, their prospects, and recent advances with particular emphasis on bioremediation strategies. © 2013 Springer Science+Business Media Dordrecht.