Enhancement of Detoxification of Petroleum Hydrocarbons and Heavy Metals in Oil-Contaminated Soil by Using Glycine-ß-Cyclodextrin.

Soil contamination with petroleum hydrocarbons and heavy metals is a widespread environmental problem. In recent years, cyclodextrin has attracted research interest because of its special hole structure that can form inclusion complexes with certain small molecules. However, the solubility of ß-cyclodextrin (ß-CD) in water is low and it crystallizes easily, leading to its low utilization in practice. In this experiment, we connected ß-CD with glycine under alkaline conditions to prepare glycine-ß-cyclodextrin (G-ß-CD), which is water soluble, has stronger coordinating ability with heavy metals, and is more suitable for treating oil-contaminated soil. The results show that G-ß-CD provides better desorption of petroleum hydrocarbons and heavy metals in soils with low organic matter content (1%) and NaNO3 of 0.25 mol/L at 70 g/L G-ß-CD under mildly acidic (pH 5⁻6) conditions. The results indicate that petroleum hydrocarbons and heavy metals were removed simultaneously by means of pretreatment with G-ß-CD, and the results can provide a theoretical basis for remediation of petroleum-contaminated soil.

Influence of immobilization on phenanthrene degradation by Bacillus sp. P1 in the presence of Cd(II).

Suspended microbes gradually lost advantages in practical applications of PAHs and heavy metals bioremediation. Therefore this study investigated the effect of immobilization on phenanthrene degradation by Bacillus sp. P1 in the presence of different Cd(II) concentrations. Condensed Bacillus sp. P1 was immobilized with polyvinyl alcohol and sodium alginate and PVA-SA-cell cryogel beads were prepared. The results indicated that the use of gel beads increased the number of adsorption sites thus accelerating phenanthrene degradation. In addition, changes in detoxification indices, including superoxide dismutase (SOD), catalase (CAT) and glutathione (GSH), were determined to elucidate the immobilization mechanisms related to cells protection from Cd(II) when degrading phenanthrene. By protecting the gel membrane, oxidative damage was minimized, while SOD activity increased from 55.72 to 81.33 U/mgprot as Cd(II) increased from 0 to 200 mg/L but later dropped to 44.29 U/mgprot as Cd(II) increased to 300 mg/L for the non-immobilized system. On the other hand, the SOD activity kept increasing from 52.23 to 473.35 U/mgprot for the immobilized system exposed to Cd(II) concentration between 0 and 300 mg/L. For CAT and GSH, immobilization only slowed down the depletion process without any change on the variation trends. The changes in surface properties and physiological responses of microbes caused the differences of immobilization effect on phenanthrene biodegradation in the presence of Cd(II), which is a novel finding.

The effect of several activated biochars on Cd immobilization and microbial community composition during in-situ remediation of heavy metal contaminated sediment.

Chemical activation and microwave assisted activation were adopted to modify biochar. Activated biochars were characterized by SEM, BET, FTIR, XRD and XPS. Raw biochar, activated biochars and commercial activated carbon were compared as remediation strategies for sediment from the Xiangjiang River containing 14.70 mg/kg Cd. After the treatment by activated biochar, the overlying water and pore water concentration of Cd decreased by 71% and 49%, respectively. And the threat of heavy metal along with bioavailability of Cd was depressed. Moreover, the immobilsation of Cd in sediment was related to BET surface area and the content of oxygen containing functional groups of activated biochars. Furthermore, a PCR-DGGE-based experiment was performed for the detection of microbial community. The indigenous microbial community was affected and new microbial community appeared after treat by activated biochar. Activated biochar can be used as an inexpensive and efficient in situ remediation material of sediment containing metal.

Comprehensive Adsorption Studies of Doxycycline and Ciprofloxacin Antibiotics by Biochars Prepared at Different Temperatures.

This paper comparatively investigated the removal efficiency and mechanisms of rice straw biochars prepared under three pyrolytic temperatures for two kinds of tetracycline and quinolone antibiotics (doxycycline and ciprofloxacin). The influencing factors of antibiotic adsorption (including biochar dosage, pH, background electrolytes, humic acid, initial antibiotics concentration, contact time, and temperature) were comprehensively studied. The results suggest that biochars produced at high-temperature [i.e., 700°C (BC700)], have higher adsorption capacity for the two antibiotics than low-temperature (i.e., 300-500°C) biochars (BC300 and BC500). Higher surface area gives rise to greater volume of micropores and mesopores, and higher graphitic surfaces of the BC700 contributed to its higher functionality. The maximum adsorption capacity was found to be in the following order: DOX > CIP. The π-π EDA interaction and hydrogen bonding might be the predominant adsorption mechanisms. Findings in this study highlight the important roles of high-temperature biochars in controlling the contamination of tetracycline and quinolone antibiotics in the environment.

Performance of magnetic graphene oxide/diethylenetriaminepentaacetic acid nanocomposite for the tetracycline and ciprofloxacin adsorption in single and binary systems.

Adsorption of tetracycline (TC) and ciprofloxacin (CIP) in single and binary systems by diethylenetriaminepentaacetic acid-functionalized magnetic graphene oxide (DDMGO) was explored. DDMGO were characterized by scanning electron microscopy (SEM), transmission electron microscopy (TEM), X-ray diffraction (XRD), Fourier transform infrared spectroscopy (FTIR), X-ray photoelectron spectroscopy (XPS) and zeta potential measurements. The adsorption kinetics and equilibrium data of single antibiotic were well fitted by pseudo-second-order and Freundlich isotherm models, respectively. Negative ΔGo values hinted the spontaneous nature of TC and CIP sorption. Moreover, the ΔHo was positive for TC removal and negative for CIP removal, indicating that TC adsorption was endothermic and CIP adsorption was exothermic. Various experimental conditions (pH, ionic strength and foreign ions) presented an important influence on TC and CIP removal. In binary systems, TC sorption onto DDMGO exhibited stronger inhibition effect by the coexisting competitive antibiotics than that for CIP. The reusability experiment revealed that the DDMGO had an excellent regeneration performance in single and binary systems. TC and CIP removal mechanism on DDMGO was mainly dependent on π-π interaction, hydrogen bonds and amidation reaction. Besides, TC and CIP uptake could also be explained by cation-π and electrostatic interaction, respectively. These findings showed that DDMGO was an efficient and reusable adsorbent for antibiotics elimination.

Adsorption of emerging contaminant metformin using graphene oxide.

The occurrence of emerging contaminants in our water resources poses potential threats to the livings. Due to the poor treatment in wastewater management, treatment technologies are needed to effectively remove these products for living organism safety. In this study, Graphene oxide (GO) was tested for the first time for its capacity to remove a kind of emerging wastewater contaminants, metformin. The research was conducted by using a series of systematic adsorption and kinetic experiments. The results indicated that GO could rapidly and efficiently reduce the concentration of metformin, which could provide a solution in handling this problem. The uptake of metformin on the graphene oxide was strongly dependent on temperature, pH, ionic strength, and background electrolyte. The adsorption kinetic experiments revealed that almost 80% removal of metformin was achieved within 20 min for all the doses studied, corresponding to the relatively high k1 (0.232 min-1) and k2 (0.007 g mg-1 min-1) values in the kinetic models. It indicated that the highest adsorption capacity in the investigated range (qm) of GO for metformin was at pH 6.0 and 288 K. Thermodynamic study indicated that the adsorption was a spontaneous (ΔG0 < 0) and exothermic (ΔH0 < 0) process. The adsorption of metformin increased when the pH values changed from 4.0 to 6.0, and decreased adsorption were observed at pH 6.0-11.0. GO still exhibited excellent adsorption capacity after several desorption/adsorption cycles. Besides, both so-called π-π interactions and hydrogen bonds might be mainly responsible for the adsorption of metformin onto GO.

Facile synthesis of Cu(II) impregnated biochar with enhanced adsorption activity for the removal of doxycycline hydrochloride from water.

In this study, the effect factors and mechanisms of doxycycline hydrochloride (DOX) adsorption on copper nitrate modified biochar (Cu-BC) was investigated. Cu-BC absorbent was synthesized through calcination of peanut shells biomass at 450°C and then impregnation with copper nitrate. The Cu-BC has exhibited excellent sorption efficiency about 93.22% of doxycycline hydrochloride from aqueous solution, which was double higher than that of the unmodified biochar. The experimental results suggest that the adsorption efficiency of DOX on the Cu-BC is dominated by the strong complexation, electrostatic interactions between DOX molecules and the Cu-BC samples. Comprehensively considering the cost, efficiency and the application to realistic water, the Cu-BC hold the significant potential for enhancing the effectiveness to remove DOX from water.

Biochar as potential sustainable precursors for activated carbon production: Multiple applications in environmental protection and energy storage.

There is a growing interest of the scientific community on production of activated carbon using biochar as potential sustainable precursors pyrolyzed from biomass wastes. Physical activation and chemical activation are the main methods applied in the activation process. These methods could have significantly beneficial effects on biochar chemical/physical properties, which make it suitable for multiple applications including water pollution treatment, CO2 capture, and energy storage. The feedstock with different compositions, pyrolysis conditions and activation parameters of biochar have significant influences on the properties of resultant activated carbon. Compared with traditional activated carbon, activated biochar appears to be a new potential cost-effective and environmentally-friendly carbon materials with great application prospect in many fields. This review not only summarizes information from the current analysis of activated biochar and their multiple applications for further optimization and understanding, but also offers new directions for development of activated biochar.

Tetracycline absorbed onto nitrilotriacetic acid-functionalized magnetic graphene oxide: Influencing factors and uptake mechanism.

A novel magnetic nanomaterial was synthesized by grafting nitrilotriacetic acid to magnetic graphene oxide (NDMGO), which was applied as an adsorbent for removing tetracycline (TC) from aqueous solutions. The nanomaterial was characterized using TG-DTA, SEM, TEM, XRD, VSM, XPS, Raman, BET surface area and zeta potential measurements. Several experimental conditions (solution pH, adsorption time, temperature, ionic strength and foreign ions) affecting the adsorption process were investigated. The results showed that the TC adsorption capacity could be affected by solution pH. The adsorption capacity of TC increased rapidly in the initial 20min and finally reached equilibrium was about 600min. The pseudo-second-order kinetics provided the better correlation for the experiment data. Various thermodynamic parameters indicated that the adsorption was a spontaneous and endothermic process. The presence of NaCl and background electrolytes in the solution had a slight influence on TC adsorption. Hydrogen bonds, amidation reaction, π-π and cation-π interaction between NDMGO and TC could be used to explain the adsorption mechanism. The regeneration experiment demonstrated that this nanomaterial possessed an excellent regeneration performance. Based on the experimental results and comparative analysis with other adsorbents, the NDMGO was a high-efficiency and reusable adsorbent for TC pollution control.

Bioremediation mechanisms of combined pollution of PAHs and heavy metals by bacteria and fungi: A mini review.

In recent years, knowledge in regard to bioremediation of combined pollution of polycyclic aromatic hydrocarbons (PAHs) and heavy metals by bacteria and fungi has been widely developed. This paper reviews the species of bacteria and fungi which can tackle with various types of PAHs and heavy metals entering into environment simultaneously or successively. Microbial activity, pollutants bioavailability and environmental factors (e.g. pH, temperature, low molecular weight organic acids and humic acids) can all affect the bioremediation of PAHs and heavy metals. Moreover, this paper summarizes the remediation mechanisms of PAHs and heavy metals by microbes via elucidating the interaction mechanisms of heavy metals with heavy metals, PAHs/PAHs metabolites with PAHs and PAHs with heavy metals. Based on the above reviews, this paper also discusses the potential research needs for this field.

Biochar pyrolyzed from MgAl-layered double hydroxides pre-coated ramie biomass (Boehmeria nivea (L.) Gaud.): Characterization and application for crystal violet removal.

A novel biochar/MgAl-layered double hydroxides composite (CB-LDH) was prepared for the removal of crystal violet from aqueous solution by pyrolyzing MgAl-LDH pre-coated ramie stem (Boehmeria nivea (L.) Gaud.). Pyrolysis played dual role for both converting biomass into biochar and calcining MgAl-LDH during the pyrolysis process. Scanning electron microscopy (SEM), transmission electron microscopy (TEM), energy-dispersive X-ray analysis (EDS), X-ray photoelectron spectroscopy (XPS), Fourier transform infrared (FTIR) and zeta potential analysis were used to characterize the CB-LDH. The results of characterization suggested that the calcined LDH was successfully synthesized and coated on biochar. The resulted CB-LDH had higher total pore volume and more functional groups than the pristine biochar. Adsorption experimental data fitted well with the pseudo-second order kinetics model and the Freundlich isotherm model. The rate-controlled step was controlled by film-diffusion initially and then followed by intra-particle diffusion. Thermodynamic analysis showed that the adsorption of crystal violet was a spontaneous and endothermic process. The higher pH and temperature of the solution enhanced the adsorption performance. CB-LDH could also have excellent ability for the removal of crystal violet from the actual industrial wastewater and groundwater with high ionic strength. LDH adsorption, electrostatic attraction, pore-filling, π-π interaction and hydrogen bond might be the main mechanisms for crystal violet adsorption on CB-LDH. The results of this study indicated that CB-LDH is a sustainable and green adsorbent with high performance for crystal violet contaminated wastewater treatment and groundwater remediation.

Biochar-based nano-composites for the decontamination of wastewater: A review.

Synthesizing biochar-based nano-composites can obtain new composites and combine the advantages of biochar with nano-materials. The resulting composites usually exhibit great improvement in functional groups, pore properties, surface active sites, catalytic degradation ability and easy to separation. These composites have excellent abilities to adsorb a range of contaminants from aqueous solutions. Particularly, catalytic material-coated biochar can exert simultaneous adsorption and catalytic degradation function for organic contaminants removal. Synthesizing biochar-based nano-composites has become an important practice for expanding the environmental applications of biochar and nanotechnology. This paper aims to review and summarize the various synthesis techniques for biochar-based nano-composites and their effects on the decontamination of wastewater. The characteristic and advantages of existing synthesis methods are summarized and discussed. Application of biochar-based nano-composites for different contaminants removal and the underlying mechanisms are reviewed. Furthermore, knowledge gaps that exist in the fabrication and application of biochar-based nano-composites are also identified.

Effects of inorganic electrolyte anions on enrichment of Cu(II) ions with aminated Fe3O4/graphene oxide: Cu(II) speciation prediction and surface charge measurement.

The present work evaluated the effects of six inorganic electrolyte anions on Cu(II) removal using aminated Fe3O4/graphene oxide (AMGO) in single- and multi-ion systems. A 2(6-2) fractional factorial design (FFD) was employed for assessing the effects of multiple anions on the adsorption process. The results indicated that the Cu(II) adsorption was strongly dependent on pH and could be significantly affected by inorganic electrolyte anions due to the changes in Cu(II) speciation and surface charge of AMGO. In the single-ion systems, the presence of monovalent anions (Cl(-), ClO4(-), and NO3(-)) slightly increased the Cu(II) adsorption onto AMGO at low pH, while the Cu(II) adsorption was largely enhanced by the presence of SO4(2-), CO3(2-), and HPO4(2-). Based on the estimates of major effects and interactions from FFD, the factorial effects of the six selected species on Cu(II) adsorption in multi-ion system were in the following sequence: HPO4(2-)>CO3(2-)>Cl(-)>SO4(2-)>NO3(-)=ClO4(-), and the combined factors of AD (Cl(-)×SO4(2-)) and EF (Cl(-)×SO4(2-)) had significant effects on Cu(II) removal.

Effects of background electrolytes and ionic strength on enrichment of Cd(II) ions with magnetic graphene oxide-supported sulfanilic acid.

To elucidate the influence mechanisms of background electrolytes and ionic strength on Cd(II) removal, the adsorption of Cd(II) onto magnetic graphene oxide-supported sulfanilic acid (MGO-SA) in aqueous solutions containing different types and concentrations of background electrolytes was studied. The results indicate that Cd(II) adsorption was strongly dependent on pH and could be strongly affected by background electrolytes and ionic strength. The Cd(II) removal was decreased with the presence of background electrolyte cations (Na(+), K(+), Ca(2+), Mg(2+), Mn(2+), Zn(2+), and Ni(2+)), and the divalent cations exerted more obvious influences on the Cd(II) uptake than the monovalent cations at pH 6. Both Cl(-) and NO3(-) had negative effects on Cd(II) adsorption because they can form water-soluble metal-anion complexes with Cd(II) ions. The presence of 0.01molL(-1) Na3PO4 reduced the removal percentage of Cd(II) at pH<5 but extremely enhanced the Cd(II) removal when the pH>5. The Cd(II) adsorption was sensitive to changes in the concentration of NaCl, NaNO3, NaClO4, and Na3PO4. Besides, the adsorption isotherm of Cd(II) onto MGO-SA could be well described by the Freundlich model and was also influenced by the type of background electrolyte ions and the ionic strength.