► The review focuses on the Cr speciation, uses, toxicity and remediation aspects. ► Assessed amount of hexavalent Cr in soils/metallurgical/other wastes and sites. ► Chemical and bioremediation processes for Cr(VI) are summarised in detail. ► Strategy for bio-remediation of Cr(VI) in different solid wastes is suggested. ► Capability of microbes for reducing Cr(VI) contamination described. ► Mechanism of microbial reduction of Cr(VI) to Cr(III) is included. Chromium is a highly toxic non-essential metal for microorganisms and plants, and its occurrence is rare in nature. Lower to higher chromium containing effluents and solid wastes released by activities such as mining, metal plating, wood preservation, ink manufacture, dyes, pigments, glass and ceramics, tanning and textile industries, and corrosion inhibitors in cooling water, induce pollution and may cause major health hazards. Besides, natural processes (weathering and biochemical) also contribute to the mobility of chromium which enters in to the soil affecting the plant growth and metabolic functions of the living species. Generally, chemical processes are used for Cr- remediation. However, with the inference derived from the diverse Cr-resistance mechanism displayed by microorganisms and the plants including biosorption, diminished accumulation, precipitation, reduction of Cr(VI) to Cr(III), and chromate efflux, bioremediation is emerging as a potential tool to address the problem of Cr(VI) pollution. This review focuses on the chemistry of chromium, its use, and toxicity and mobility in soil, while assessing its concentration in effluents/wastes which becomes the source of pollution. In order to conserve the environment and resources, the chemical/biological remediation processes for Cr(VI) and their efficiency have been summarised in some detail. The interaction of chromium with various microbial/bacterial strains isolated and their reduction capacity towards Cr(VI) are also discussed.
In this article, the use of low-cost adsorbents for the removal of methylene blue (MB) from solution has been reviewed. Adsorption techniques are widely used to remove certain classes of pollutants from waters, especially those which are not easily biodegradable. The removal of MB, as a pollutant, from waste waters of textile, paper, printing and other industries has been addressed by the researchers. Currently, a combination of biological treatment and adsorption on activated carbon is becoming more common for removal of dyes from wastewater. Although commercial activated carbon is a preferred adsorbent for color removal, its widespread use is restricted due to its relatively high cost which led to the researches on alternative non-conventional and low-cost adsorbents. The purpose of this review article is to organize the scattered available information on various aspects on a wide range of potentially low-cost adsorbents for MB removal. These include agricultural wastes, industrial solid wastes, biomass, clays minerals and zeolites. Agricultural waste materials being highly efficient, low cost and renewable source of biomass can be exploited for MB remediation. It is evident from a literature survey of about 185 recently published papers that low-cost adsorbents have demonstrated outstanding removal capabilities for MB.
A bifunctional photocatalyst-Fe-benzenedicarboxylate (MIL-53(Fe)) has been synthesized successfully via a facile solvothermal method. The resulting MIL-53(Fe) photocatalyst exhibited an excellent visible light ( ≥ 420 nm) photocatalytic activity for the reduction of Cr(VI), the reduction rate have reached about 100% after 40 min of visible light irradiation, which has been more efficient than that of N-doped TiO (85%) under identical experimental conditions. Further experimental results have revealed that the photocatalytic activity of MIL-53(Fe) for the reduction of Cr(VI) can be drastically affected by the pH value of the reaction solution, the hole scavenger and atmosphere. Moreover, MIL-53(Fe) has exhibited considerable photocatalytic activity in the mixed systems (Cr(VI)/dyes). After 6 h of visible light illumination, the reduction ratio of Cr(VI) and the degradation ratio of dyes have been exceed 60% and 80%, respectively. More significantly, the synergistic effect can also be found during the process of photocatalytic treatment of Cr(VI) contained wastewater under the same photocatalytic reaction conditions, which makes it a potential candidate for environmental restoration. Finally, a possible reaction mechanism has also been investigated in detail.
The aim of this study was to quantify the influence of the two main categories of factors determining the yield and properties of biochar, i.e., feedstock properties and production conditions, here represented by the highest treatment temperature (HTT). To achieve this, a wide range of production temperatures (200–650 °C) and an extensive set of diverse feedstock ( = 12) were used to calculate the sensitivity. The quantitative evaluation was based on statistical analysis of coefficients of variation, and thus derived indices representing the extent of influence of the two factors, i.e., a feedstock-depended heterogeneity ( ) and a temperature-depended heterogeneity ( ). The results showed that both feedstock properties and production conditions are important for determining the yield and properties of biochar, but their respective influence changes with the property or set of properties of interest. The biochar parameters most affected by feedstock properties were e.g., total organic carbon, fixed carbon, and mineral elements of biochar. On the other hand, biochar surface area and pH was mainly influenced by highest treatment temperature. Biochar recalcitrance was mainly determined by production temperature, while the potential total C sequestration (product of recalcitrance and pyrolysis carbon yield) depended more on feedstock. Overall, the work sheds some light on the relative importance of different biochar production process parameters on the final biochar product, which is an important step towards “designed” biochar.
Cylindrical bonds representative diagram of alumina-coated MWCNTs. ▶ Comparing with uncoated-MWCNTs, alumina-coated MWCNTs has higher adsorption capacity toward lead. ▶ In the fixed bed mode, the percentage of lead removal increases by decreasing the flow rate. ▶ The lead removal increases when the bed thickness increases. Alumina-coated multi-wall carbon nanotubes were synthesized and characterized by scanning electron microscopy, X-ray diffraction, and FTIR. They were used as an adsorbent for the removal of lead ions from aqueous solutions in two modes, batch and fixed bed. In the batch mode, experiments were carried out to investigate the effect of contact time, agitation speed, adsorbent dosage and solution pH on the removal of lead. The coated nanotubes exhibit better removal ability over uncoated. For fixed-bed columns, thickness of the layer and flow rate were investigated. Increasing the thickness and decreasing the flow rate enhanced the removal of lead. The prepared adsorbent displayed the main advantage of separation convenience when a fixed-bed column was used compared to the batch adsorption treatment.
Nano zerovalent iron (nZVI) is an effective adsorbent for removing various organic and inorganic contaminants. In this study, nZVI particles were used to investigate the removal of Cd in the concentration range of 25–450 mg L . The effect of temperature on kinetics and equilibrium of cadmium sorption on nZVI particles was thoroughly examined. Consistent with an endothermic reaction, an increase in the temperature resulted in increasing cadmium adsorption rate. The adsorption kinetics well fitted using a pseudo second-order kinetic model. The calculated activation energy for adsorption was 54.8 kJ mol , indicating the adsorption process to be chemisorption. The intraparticle diffusion model described that the intraparticle diffusion was not the only rate-limiting step. The adsorption isotherm data could be well described by the Langmuir as well as Temkin equations. The maximum adsorption capacity of nZVI for Cd was found to be 769.2 mg g at 297 K. Thermodynamic parameters (i.e., change in the free energy (Δ ), the enthalpy (Δ ), and the entropy (Δ )) were also evaluated. The overall adsorption process was endothermic and spontaneous in nature. EDX analysis indicated the presence of cadmium ions on the nZVI surface. These results suggest that nZVI could be employed as an efficient adsorbent for the removal of cadmium from contaminated water sources.
Lead (Pb) is one of the most toxic heavy metals that pose a direct threat to organisms and it can not been degraded through microbial activities or chemical reaction. Bioavaibility and eco-toxicity of Pb which mostly depend on Pb chemical speciation play an important role in the remediation of Pb-contaminated soils. Phosphate (P) amendments which could transfer Pb from unstable fraction to stable fraction are commonly used to immobilize Pb in soils and have been extensively studied by researchers during decades. Based on the previous study, it can be concluded that three principal mechanisms may be responsible for P-induced Pb immobilization: 1) the precipitation of Pb-phosphates, including direct precipitation, ion-exchange (or substitution) effect and liming effect; 2) the adsorption of Pb, including the direct adsorption and the adsorption of Pb to iron (hydr)oxides; 3) the rhizosphere effect, including acidification effect and mycorrhizae effect. In this review, these mechanisms have been completely discussed and the internal relationships among them were summarized to give a better understanding of P-induced Pb immobilization in soils and promote the development of P-based remediation technology.
PAHs are aromatic hydrocarbons with two or more fused benzene rings with natural as well as anthropogenic sources. They are widely distributed environmental contaminants that have detrimental biological effects, toxicity, mutagenecity and carcinogenicity. Due to their ubiquitous occurrence, recalcitrance, bioaccumulation potential and carcinogenic activity, the PAHs have gathered significant environmental concern. Although PAH may undergo adsorption, volatilization, photolysis, and chemical degradation, microbial degradation is the major degradation process. PAH degradation depends on the environmental conditions, number and type of the microorganisms, nature and chemical structure of the chemical compound being degraded. They are biodegraded/biotransformed into less complex metabolites, and through mineralization into inorganic minerals, H O, CO (aerobic) or CH (anaerobic) and rate of biodegradation depends on pH, temperature, oxygen, microbial population, degree of acclimation, accessibility of nutrients, chemical structure of the compound, cellular transport properties, and chemical partitioning in growth medium. A number of bacterial species are known to degrade PAHs and most of them are isolated from contaminated soil or sediments. , , spp., spp., spp., spp. are some of the commonly studied PAH-degrading bacteria. Lignolytic fungi too have the property of PAH degradation. , , and are the common PAH-degrading fungi. Enzymes involved in the degradation of PAHs are oxygenase, dehydrogenase and lignolytic enzymes. Fungal lignolytic enzymes are lignin peroxidase, laccase, and manganese peroxidase. They are extracellular and catalyze radical formation by oxidation to destabilize bonds in a molecule. The biodegradation of PAHs has been observed under both aerobic and anaerobic conditions and the rate can be enhanced by physical/chemical pretreatment of contaminated soil. Addition of biosurfactant-producing bacteria and light oils can increase the bioavailability of PAHs and metabolic potential of the bacterial community. The supplementation of contaminated soils with compost materials can also enhance biodegradation without long-term accumulation of extractable polar and more available intermediates. Wetlands, too, have found an application in PAH removal from wastewater. The intensive biological activities in such an ecosystem lead to a high rate of autotrophic and heterotrophic processes. Aquatic weeds spp. and have been used in horizontal–vertical macrophyte based wetlands to treat PAHs. An integrated approach of physical, chemical, and biological degradation may be adopted to get synergistically enhanced removal rates and to treat/remediate the contaminated sites in an ecologically favorable process.
The reduced graphene oxide-supported nanoscale zero-valent iron (nZVI/rGO) composites were synthesized by chemical deposition method and were characterized by SEM, high resolution TEM, Raman and potentiometric acid-base titrations. The characteristic results showed that the nZVI nanoparticles can be uniformly dispersed on the surface of rGO. The removal of U(VI) on nZVI/rGO composites as a function of contact time, pH and U(VI) initial concentration was investigated by batch technique. The removal kinetics of U(VI) on nZVI and nZVI/rGO were well simulated by a pseudo-first-order kinetic model and pseudo-second-order kinetic model, respectively. The presence of rGO on nZVI nanoparticles increased the reaction rate and removal capacity of U(VI) significantly, which was attributed to the chemisorbed OH groups of rGO and the massive enrichment of Fe on rGO surface by XPS analysis. The XRD analysis revealed that the presence of rGO retarded the transformation of iron corrosion products from magnetite/maghemite to lepidocrocite. According to the fitting of EXAFS spectra, the U C (at ∼2.9 Å) and U Fe (at ∼3.2 Å) shells were observed, indicating the formation of inner-sphere surface complexes on nZVI/rGO composites. Therefore, the nZVI/rGO composites can be suitable as efficient materials for the in-situ remediation of uranium-contaminated groundwater in the environmental pollution management.
We prepared novel Fe O magnetic nanoparticles (MNPs) modified with 3-aminopropyltriethoxysilane (APS) and copolymers of acrylic acid (AA) and crotonic acid (CA). The MNPs were characterized by transmission electron microscopy, X-ray diffraction, infra-red spectra and thermogravimetric analysis. We explored the ability of the MNPs for removing heavy metal ions (Cd , Zn , Pb and Cu ) from aqueous solution. We investigated the adsorption capacity of Fe O @APS@AA-co-CA at different pH in solution and metal ion uptake capacity as a function of contact time and metal ion concentration. Moreover, adsorption isotherms, kinetics and thermodynamics were studied to understand the mechanism of the synthesized MNPs adsorbing metal ions. In addition, we evaluated the effect of background electrolytes on the adsorption. Furthermore, we explored desorption and reuse of MNPs. Fe O @APS@AA-co-CA MNPs are excellent for removal of heavy metal ions such as Cd , Zn , Pb and Cu from aqueous solution. Furthermore, the MNPs could efficiently remove the metal ions with high maximum adsorption capacity at pH 5.5 and could be used as a reusable adsorbent with convenient conditions.
Mesoporous silica SBA-15 supported iron and cobalt (Fe–Co/SBA-15) was prepared and used as catalyst in the ultrasound (US) enhanced heterogeneous activation of peroxymonosulfate (PMS, HSO ) process. The effects of some important reaction parameters on the removal of Orange II by US/Fe–Co/SBA-15/PMS process were investigated. The results indicated that the removal rate of Orange II was not significantly affected by the initial pH, and it increased with the higher PMS concentration, reaction temperature, Fe–Co/SBA-15 dosage and ultrasonic power. Furthermore, sulfate radicals (SO ) were assumed to be the dominating reactive species for the Orange II decolorization. Moreover, the Fe–Co/SBA-15 catalyst showed high activity during the repeated experiments. The intermediate products were identified by GC–MS, thereby a plausible degradation pathway is proposed. In addition, the chemical oxygen demand (COD) removal efficiencies at 2 and 24 h were 56.8% and 80.1%, respectively and the corresponding total organic carbon (TOC) removal efficiencies were 33.8 and 53.3%. Finally, toxicity tests with activated sludge showed that the toxicity of the solution increased during the first stage and then decreased significantly with the progress of the oxidation.
Magnetic iron based materials are generally effective for many catalytic reactions and can be magnetically recovered after application, showing advantages than other metal oxides. In the present work, magnetic MnFe O nanoparticle and MnFe O -reduced graphene oxide (rGO) hybrid were prepared and used as catalysts to activate peroxymonosulfate (PMS) to oxidatively degrade various organic pollutants in water. From a process of chemical deposition and reduction, MnFe O -rGO hybrids were produced with nanosized MnFe O particles (ca. 13.2 nm). It was found that MnFe O or MnFe O -rGO presented high activity in activating PMS to produce sulfate radicals for degradation of organic dyes (Methyl violet, Methyl orange, Methylene blue, Orange II and Rhodamine B) and could be separated with a magnet without any loss. The reaction kinetics, effect of different ion species and strength, reaction temperature (25–65 °C), catalytic stability, as well as degradation mechanism were comprehensively studied. The lower activation energy on MnFe O -rGO (25.7 kJ/mol) justify the higher chemical performance than that of MnFe O (31.7 kJ/mol), suggesting that graphene plays a significant role in the enhanced degradation of dyes. More importantly, the as-prepared MnFe O and MnFe O -rGO hybrid exhibited stable performance to remove the organic pollutants in wastewater with easy recycling and good stability by successive degradation experiments.
• The graphene/Fe O composite was synthesized by conversion of FeCl to Fe O and simultaneous reduction of GO into graphene in ethylene glycol solution. • The adsorption process was characterized by kinetics, isotherm and thermodynamic analysis. • The graphene/Fe O composite could be utilized as a magnetically separable and efficient adsorbent for the environmental cleanup. In this study, we have demonstrated a facile one-step solvothermal method for the synthesis of the graphene nanosheet (GNS)/magnetite (Fe O ) composite. During the solvothermal treatment, conversion of FeCl to Fe O and simultaneous reduction of graphene oxide (GO) into graphene in ethylene glycol solution were achieved. Electron microscopy study suggests the Fe O spheres with a size of about 200 nm are uniformly distributed and firmly anchored on the wrinkled graphene layers with a high density. The resulting GNS/Fe O composite shows extraordinary adsorption capacity and fast adsorption rates for removal of organic dye, methylene blue (MB), in water. The adsorption kinetics, isotherms and thermodynamics were investigated in detail to reveal that the kinetics and equilibrium adsorptions are well-described by pseudo-second-order kinetic and Langmuir isotherm model, respectively. The thermodynamic parameters reveal that the adsorption process is spontaneous and endothermic in nature. This study shows that the as-prepared GNS/Fe O composite could be utilized as an efficient, magnetically separable adsorbent for the environmental cleanup.
In this study, chitosan/polyvinyl alcohol (PVA)/zeolite nanofibrous composite membrane was fabricated via electrospinning. First, crude chitosan was hydrolyzed with NaOH for 24 h. Afterward, hydrolyzed chitosan solution was blended with aqueous PVA solution in different weight ratios. Morphological analysis of chitosan/PVA electrospun nanofiber showed a defect-free nanofiber material with 50:50 weight ratio of chitosan/PVA. Subsequently, 1 wt.% of zeolite was added to this blended solution of 50:50 chitosan/PVA. The resulting nanofiber was characterized with field emission scanning electron microscopy, X-Ray diffraction, Fourier transform infrared spectroscopy, swelling test, and adsorption test. Fine, bead-free nanofiber with homogeneous nanofiber was electrospun. The resulting membrane was stable in distilled water, acidic, and basic media in 20 days. Moreover, the adsorption ability of nanofibrous membrane was studied over Cr (VI), Fe (III), and Ni (II) ions using Langmuir isotherm. Kinetic parameters were estimated using the Lagergren first-order, pseudo-second-order, and intraparticle diffusion kinetic models. Kinetic study showed that adsorption rate was high. However, the resulting nanofiber membrane showed less adsorption capacity at high concentration. The adsorption capacity of nanofiber was unaltered after five recycling runs, which indicated the reusability of chitosan/PVA/zeolite nanofibrous membrane. Therefore, chitosan/PVA/zeolite nanofiber can be a useful material for water treatment at moderate concentration of heavy metals.
This paper presents a review of the main sludge treatment techniques used as a pretreatment to anaerobic digestion. These processes include biological (largely thermal phased anaerobic), thermal hydrolysis, mechanical (such as ultrasound, high pressure and lysis), chemical with oxidation (mainly ozonation), and alkali treatments. The first three are the most widespread. Emphasis is put on their impact on the resulting sludge properties, on the potential biogas (renewable energy) production and on their application at industrial scale. Thermal biological provides a moderate performance increase over mesophilic digestion, with moderate energetic input. Mechanical treatment methods are comparable, and provide moderate performance improvements with moderate electrical input. Thermal hydrolysis provides substantial performance increases, with a substantial consumption of thermal energy. It is likely that low impact pretreatment methods such as mechanical and thermal phased improve speed of degradation, while high impact methods such as thermal hydrolysis or oxidation improve both speed and extent of degradation. While increased nutrient release can be a substantial cost in enhanced sludge destruction, it also offers opportunities to recover nutrients from a concentrated water stream as mineral fertiliser.
Nanoremediation strategies applied to contaminated river sediments can induce changes in the mobility and bioavailability of metals with potential consequences on ecosystem health. In this study, the performance of rhamnolipid (RL) coated nanoscale zero-valent iron (NZVI) in immobilizing cadmium (Cd) and lead (Pb) from contaminated river sediments was investigated. We demonstrated that RNZVI was effective in transforming labile Cd and Pb to stable fraction (the maximum residual percentage of Cd and Pb increased by 56.40% and 43.10% after 42 days of incubation, respectively), with the decrease of the mobility of metals. The increase of pH in NZVI and RNZVI treated sediment samples indicated the related mechanism for Cd and Pb immobilization. The contents of organic matter (OM) were higher than in control, with the initial addition of RL during 7 days incubation, and then the contents gradually decreased and became stable, maybe resulting from the enhancement of the activity of microorganisms and the decomposition of OM. Urease and catalase activities were enhanced with the increase of incubation time, showing certain degrees of recovery in sediment metabolic function. This work provides a new insight into the potential effects of RNZVI applications on the Cd and Pb immobilization in contaminated river sediments.
Dried raw sludge was pyrolyzed at temperatures ranging from 400 to 600 °C at the increase of 50 °C intervals to investigate the influence of pyrolysis temperature on properties and environmental safety of heavy metals in biochar derived from municipal sewage sludge. The sludge biochar yield decreased significantly with increasing pyrolysis temperature but the pH, ash content and specific surface area increased. Conversion of sludge to biochar markedly decreased the H/C and N/C ratios. FT-IR analysis confirmed a dramatic depletion of H and N and a higher degree of aromatic condensation in process of biochar formation at higher temperatures. The total concentrations of Cu, Zn, Pb, Cr, Mn, and Ni increased with conversion of sludge to biochar and increasing pyrolysis temperature. However, using BCR sequential extraction and analysis, it was found that most of the heavy metals existed in the oxizable and residual forms after pyrolysis, especially at 600 °C, resulting in a significant reduction in their bioavailability, leading to a very low environmental risk of the biochar. The present study indicates pyrolysis is a promising sludge treatment method for heavy metals immobilization in biochar, and highlights the potential to minimize the harmful effects of biochar by controlling pyrolysis temperature.
With the increasing worldwide demand for energy, utilization of fossil fuels is increasing proportionally. Additionally, new and unconventional energy sources are also being utilized at an increasing rate day-by-day. These sources, along with some industrial processes, result in the exposal of several sulfur- and nitrogen-containing compounds (SCCs and NCCs, respectively) to the environment, and the exposure is one of the greatest environmental threats in the recent years. Although, several methods were established for the removal of these pollutants during the last few decades, recent advancements in adsorptive desulfurization and denitrogenation (ADS and ADN, respectively) with metal-organic frameworks (MOFs) make this the most promising and remarkable method. Therefore, many research groups are currently involved with ADS and ADN with MOFs, and the results are improving gradually by modifying the MOF adsorbents according to several specific adsorption mechanisms. In this review, ADS and ADN studies are thoroughly discussed for both liquid-phase and gas-phase adsorption. The MOF modification procedures, which are important for improved adsorption, are also described. To improve the knowledge among the scientific community, it is very important to understand the detailed chemistry and mechanism involved in a chemical process, which also creates the possibility and pathway for further developments in research and applications. Therefore, the mechanisms related to the adsorption procedures are also discussed in detail. From this review, it can be expected that the scientific community will obtain an understanding of the current state of ADS and ADN, their importance, and some encouragement and insight to take the research knowledge base to a higher level.
Heavy metal contamination in croplands has been a serious concern because of its high health risk through soil-food chain transfer. A field experiment was conducted in 2010–2012 in a contaminated rice paddy in southern China to determine if bioavailability of soil Cd and Pb could be reduced while grain yield was sustained over 3 years after a single soil amendment of wheat straw biochar. Contaminated biochar particles were separated from the biochar amended soil and microscopically analyzed to help determine where, and how, metals were immobilized with biochar. Biochar soil amendment (BSA) consistently and significantly increased soil pH, total organic carbon and decreased soil extractable Cd and Pb over the 3 year period. While rice plant tissues’ Cd content was significantly reduced, depending on biochar application rate, reduction in plant Pb concentration was found only in root tissue. Analysis of the fresh and contaminated biochar particles indicated that Cd and Pb had probably been bonded with the mineral phases of Al, Fe and P on and around and inside the contaminated biochar particle. Immobilization of the Pb and Cd also occurred to cation exchange on the porous carbon structure.