Study on the enhancement of citric acid chemical leaching of contaminated soil by modified nano zero-valent iron.

This study aimed to evaluate the effect of modified nanoscale zero-valent iron (SAS-nZVI) on chemical leaching of lead and cadmium composite contaminated soil by citric acid (CA). The synthesized SAS-nZVI was used as a leaching aid to improve the removal rate of soil heavy metals (HMs) by CA chemical leaching. The effects of various factors such as SAS-nZVI dosage, elution temperature and elution time were studied. At the same time, the effect of chemical leaching on the basic physical and chemical properties of soil and the morphology of HMs was evaluated. The results show that when the SAS-nZVI dosage is 2.0 g/L, the leaching temperature is 25 °C, and the leaching time is 720 min, the maximum removal rates of Pb and Cd in the soil are 77.64% and 97.15% respectively. The experimental results were evaluated using elution and desorption kinetic models (Elovich model, double constant model, diffusion model). The elution and desorption process of Pb and Cd in soil by SAS-nZVI-CA fitted well with the double-constant model, indicating that the desorption kinetic process of Pb and Cd is a heterogeneous diffusion process, and the elution process is controlled by diffusion factors. After leaching with SAS-nZVI-CA, the physical and chemical properties of the soil changed little, the mobility and toxicity of HMs in the soil were reduced, and the HMs content in the leaching waste liquid was reduced. It can be concluded that SAS-nZVI enhances the efficiency of CA in extracting Pb and Cd from soil, minimizes soil damage resulting from chemical leaching technology, and alleviates the challenges associated with treating leaching waste liquid.

Ecological and health risk assessments of heavy metals and their accumulation in a peanut-soil system.

Heavy metals pollution is a notable threat to environment and human health. This study evaluated the potential ecological and health risks of heavy metals (Cu, Cr, Cd, Pb, Zn, Ni, and As) and their accumulation in a peanut-soil system based on 34 soil and peanut kernel paired samples across China. Soil As and Cd posed the greatest pollution risk with 47.1% and 17.6% of soil samples exceeding the risk screen levels, respectively, with 26.5% and 20.6% of the soil sites at relatively strong potential ecological risk level, respectively, and with the geo-accumulation levels at several soil sites in the uncontaminated to moderately contaminated categories. About 35.29% and 2.94% of soil sites were moderately and severely polluted based on Nemerow comprehensive pollution index, respectively, and a total of 32.4% of samples were at moderate ecological hazard level based on comprehensive potential ecological risk index values. The Cd, Cr, Ni, and Cu contents exceeded the standard in 11.76, 8.82, 11.76 and 5.88% of the peanut kernel samples, respectively. Soil metals posed more health risks to children than adults in the order As > Ni > Cr > Cu > Pb > Zn > Cd for non-carcinogenic health risks and Ni > Cr â‰« Cd > As > Pb for carcinogenic health risks. The soil As non-cancer risk index for children was greater than the permitted limits at 14 sites, and soil Ni and Cr posed the greatest carcinogenic risk to adults and children at many soil sites. The metals in peanut did not pose a non-carcinogenic risk according to standard. Peanut kernels had strong enrichment ability for Cd with an average bio-concentration factor (BCF) of 1.62. Soil metals contents and significant soil properties accounted for 35-74% of the variation in the BCF values of metals based on empirical prediction models.

Effects of Ca2+ and Mg2+ on Cu binding in hydrophilic and hydrophobic dissolved organic matter fractions extracted from agricultural soil.

Dissolved organic matter (DOM) has significant effects on soil copper (Cu) bioavailability. However, little is known about Cu interactions and major cation binding toward hydrophilic and hydrophobic DOM components extracted from soil solutions. In this study, we investigated the influence of major cations (Ca2+/Mg2+) on Cu complexing characteristics on different hydrophilic and hydrophobic DOM fractions using absorbance spectroscopy at different Cu2+ concentrations in the absence/presence of Ca2+/Mg2+. Different compositional hydrophobic and hydrophilic DOM fraction proportions occurred at three agricultural soil sites, with the hydrophobic acid (HOA) fraction accounting for the highest proportion. The addition of Cu2+ generated distinct ultraviolet (UV) bands/peaks (processed by differential linear and differential logarithmic transformation) of three hydrophilic DOM fractions, whereas Cu2+ induced less and weak specific peaks in the differential spectra and differential logarithmic of the HOA fractions, indicating hydrophilic DOM fractions tend to have a higher density of Cu2+ complexation sites. In the presence of either Ca2+/Mg2+, increased depression caused by Cu2+ binding on different DOM fractions was observed with increasing 10, 100, and 1000 µM Ca2+/Mg2+ levels, with more significant variations in peaks/banks for hydrophilic base (HIB) and HOA fractions, and less for hydrophilic acid (HIA) and hydrophilic neutral (HIN) fractions. In our study, the spectral parameters ΔS225-275 and ΔS275-325 were successfully used to quantify Cu amounts bonded to HIA and HIB, respectively. They exhibited strong linear relationships with correlation coefficients (R2) of 0.96 for HIA and 0.87 for HIB, respectively. Furthermore, Mg2+ exhibited stronger competition with Cu for HIA and HIB binding sites when compared with Ca2+.

Ion exchange synthesis of copper-based hydroxyapatite for the catalytic degradation of phenol.

Hydroxyapatite (HAP) is a material renowned for its exceptional capabilities in adsorbing and exchanging heavy metal ions, making it a widely employed substance within the environmental domain. This study aims to present a novel material, namely copper-HAP (Cu-HAP), which was synthesized via an ion exchange method. The resulting material underwent comprehensive characterization using scanning electron microscopy, X-ray diffraction, Fourier-transform infrared spectroscopy, and Brunauer-Emmett-Teller (BET) analysis. Subsequently, based on the principle of the Fenton-like oxidation reaction, the material was used for the degradation of phenol. The outcomes of the investigation revealed that the optimal preparation conditions for the catalyst were achieved at a temperature of 40 °C, a pH value of 5, and a relative dosage of Cu-HAP at 100 mg/g. Under the reaction conditions of a catalyst dosage of 2 g/L, a 30% hydrogen peroxide concentration of 30 mM, a phenol concentration of 20 mg/L, a pH value of 6, a temperature of 40 °C, and the degradation rate of phenol impressively reached 98.12%. Furthermore, the degradation rate remained at 42.31% even after five consecutive cycles, indicating the promising potential of Cu-HAP in the treatment of recalcitrant organic compounds within this field.

Study on the migration behaviour of heavy metals at the improved mine soil-plant rhizosphere interface.

With the increasing shortage of land resources and the aggravation of soil pollution in mining areas, the remediation of soil in abandoned mining areas has gradually attracted people's attention. The remediation of heavy metal contaminated soil in mining areas is the key to reduce the harm of heavy metals to the environment and human health. In this study, municipal sludge and phytoremediation technology were combined to investigate the migration and transformation of heavy metals at the soil-plant interface in improved mining areas through indoor pot experiments. The results showed that heavy metals in non-rhizosphere soil entered the rhizosphere environment with the growth of plants, leading to the increase of heavy metal content in rhizosphere soil. The cumulative amounts of Cu, Zn, Pb and Cd were 1299.32, 832.10, 347.89 and 71.34 mg/kg, respectively. The content of oxidized Cu and Zn decreased with increasing planting days, while the oxidized Pb and Cd showed an increasing trend. Under acidic conditions, H+ is easy to compete with heavy metal ions for exchangeable positions in the clay mineral layer, so that the reducible heavy metals are easy to be converted into exchangeable states. In this paper, the effects of various factors on the distribution of heavy metals were discussed by adjusting soil pH, adding humic acid and root exudates, so as to analyse the migration and transformation mechanism of heavy metals at the soil-plant interface, and provide a reliable theoretical basis for soil remediation in mining areas.

Effective adsorption of bisphenol A from aqueous solution using phosphoric acid-assisted hydrochar.

Sycamore leaf biochar (PSAC) was prepared by a two-step phosphoric acid-assisted hydrothermal carbonization combined with a short-time activation method. The characterization results showed that the introduction of phosphoric acid molecules and thermal activation resulted in a substantial increase in the specific surface area (994.21 m2/g) and microporous capacity (0.307 cm3/g) of PSAC. The batch adsorption results showed that the adsorption process of PSAC on bisphenol A (BPA) was best described by the pseudo-second-order kinetic model and Sips isothermal model, with a maximum adsorption capacity of 247.42 mg/g. The adsorption of BPA onto PSAC was determined to be a spontaneous endothermic process. The equilibrium adsorption capacity of PSAC exhibited an upward trend with increasing initial BPA concentration and temperature while decreasing with higher adsorbent dosage and pH value. Coexisting cations and humic acids in water have little impact on the adsorption performance of PSAC for BPA. The adsorption mechanism of BPA by PSAC was mainly governed by pore filling and hydrogen bonding interactions, π-π interactions, and intraparticle diffusion. Furthermore, PSAC demonstrated good reusability by its sustained adsorption capacity of BPA, which remained at 82.6% of the initial adsorption capacity even after four adsorption-desorption cycles. These findings highlight the potential of utilizing low-cost sycamore leaf biochar as an effective adsorbent for the removal of the endocrine disruptor BPA.

Effective immobilization of bisphenol A utilizing activated biochar incorporated into soil: combined with batch adsorption and fixed-bed column studies.

This study presented the mixture of biochar and soil for removal of bisphenol A (BPA) to assess environmental remediation ability. Using phoenix tree leaves as biomass and phosphoric acid as activator, after one-step hydrothermal and short-term activation, the eventual solid product was phosphoric acid hydrothermal activated carbon (HPC). The characterizations showed that HPC had the high specific surface (994.21 m2·g-1), and large unsaturated esters and hydroxyl groups. The saturated adsorption capacities of batch and column adsorption for the addition of 0.5% HPC to soil were 0.790 mg·g-1 and 67.23 mg·kg-1, while to the natural soil were 0.236 mg·g-1 and 8.75 mg·kg-1, respectively. The adsorption kinetics and thermodynamic analysis indicated that the adsorption process utilizing HPC incorporated into soil was a chemical reaction rate-controlled, physical-dominated multilayer adsorption, and spontaneous endothermic. Also, batch adsorption experiments and analysis were performed under different pH levels, HPC contents, organic acid concentrations, and cationic strengths. Successively, fixed-bed column experiments were carried out with and without the HPC; the results showed that the wide mass transfer zone led to the effective fixation of BPA, and the organic acid had no obvious effect on the fixation of BPA when the 1.0% HPC mixed with soil. Finally, through characterizations and data analysis, the enhanced adsorption of BPA by HPC mixed with soil mainly relied on π-π interaction, hydrogen bonding, followed by electrostatic attraction and pore filling.

Degradation of 2,4-DCP by immobilized laccase on modified biochar carrier.

Rape straw was used as the raw material for the biochar in this study, which was then changed using acid, alkali, and magnetic techniques. The laccase was attached using the adsorptions-crosslinking process, and the three modified biochars served as the carriers. The ideal circumstances for laccase immobilization were explored, and both biochar and immobilized laccase's characteristics were examined. The removal of 2,4-dichlorophenol (2,4-DCP) by immobilized laccase from modified biochar and its degradation products were researched. The main conclusions are as follows: the optimal concentration of glutaraldehyde (GLU) was 4%, and the pH was four, and the enzyme dosage was 1.75 mg/mL for the immobilized laccase of acid-modified biochar (SBC@LAC). The optimal concentration of GLU was 5%; the pH was four, and the enzyme dosage was 2 mg/mL for immobilized laccase from alkali-modified biochar (JBC@LAC). The optimal concentration of GLU was 5%; the pH was four, and the enzyme dosage was 1.75 mg/mL for immobilized laccase from magnetically modified biochar (CBC@LAC). SEM images could show the changes in the surface morphology of biochar caused by three modification methods. The BET results demonstrated that acid and magnetic modification increased the specific surface area of biochar, and alkali modification mainly expanded the pore size of biochar. FT-IR and XRD showed that modification and laccase loading had little effect on the structure of biochar. The stability of immobilized laccase was better than that of free laccase in acid-base, heat, and storage. Among the three modified biochar immobilized laccases, JBC@LAC showed the best acid-base stability and thermal stability, and the relative enzyme activity changed the least when pH and temperature conditions changed. The storage stability of SBC@LAC is the best. After 30 days of storage, the relative enzyme activity is still 83%. The removal rates of 2,4-DCP were 57, 99, and 63%, respectively, by SBC@LAC, JBC@LAC, and CBC@LAC. After five reuses, the removal rates of 2,4-DCP by SBC@LAC, JBC@LAC and CBC@LAC were 26, 42, and 27%, respectively. The intermediate products of 2,4-DCP degradation by immobilized laccase were p-phenol, p-benzoquinone and maleic acid.

Assessment of Potentially Toxic Elements Pollution and Human Health Risks in Polluted Farmland Soils around Distinct Mining Areas in China-A Case Study of Chengchao and Tonglushan.

This research study investigates the extent of heavy metal pollution and pollution trends in agricultural soil in mining areas during different time periods. A total of 125 soil samples were collected from two mining areas in China, the Chengchao iron mine and Tonglushan ancient copper mine. The samples were analyzed for various potentially toxic elements (PTEs). The index of geoaccumulation (Igeo), pollution index (Pi), potential ecological risk index (Eri), and hazard index (HI) were calculated to evaluate the pollution status of PTEs in the farmland around the two mining areas. The sources of PTEs were inferred by pollution distribution, and the pollution conditions of the two mining areas were compared. The results showed that the pollution of ancient copper mines was relatively severe. The main pollution elements were Cu, Cd, and As, and their average Pi values were 3.76, 4.12, and 1.84, respectively. These PTEs mainly came from mining and transportation. There are no particularly polluted elements in the Chengchao iron mine and the average Pi of all PTEs were classified as light pollution and had a wide range of sources. The findings suggest that the ancient copper mine, due to outdated mining techniques and insufficient mine restoration efforts, resulted in the spread and accumulation of PTEs in the soil over an extended period, making the farmland soil around the ancient copper mine more polluted compared to the Chengchao iron mine. In the two mining areas, there is no risk of cancer for adults and children. However, the RI values of Cr in adults and children are higher than 10-4, which indicates that the carcinogenic risk of Cr in these soils is very high. The non-carcinogenic effects of PTEs on the human body in the soil of ancient copper mine are also higher than that of the Chengchao iron mine.

Identification and hazard analysis of heavy metal sources in agricultural soils in ancient mining areas: A quantitative method based on the receptor model and risk assessment.

Industry in ancient mining areas caused significant heavy metal pollution (HMP) in agricultural soils. This study measured the hazards of specific sources of heavy metals (HMs) in an ancient mining areas agricultural soil. Firstly, we identified the major pollution sources based on the PMF model. Then, the proposed single-factor pollution load index (SPLIzone) and ecological load index (SELIzone) analyzed the integrated pollution and ecological risks of various elements. Finally, the source-specific soil contamination levels and ecological risks were quantified by combining the source assignment and single-factor assessment processes. SPLIzone and SELIzone showed that Cu and Cd were the most contaminated elements. Five factors were determined as the major sources of HMs, including mining, natural, smelting industry, agricultural and traffic sources. The mining sources contributed the most soil contamination (33.73%). However, the largest contributor to ecological risk was the smelting industrial (42.18%). Lower soil contamination may contain higher ecological risk. Smelting industrial and traffic are the most critical sources that need to be controlled at present. This study proposes a quantitative method for assessing the hazards of HM sources, which provides a beneficial reference for the study and management of HMP.

Study on the removal of Pb(II) from water by coated sulfur-modified nanoscale zero-valent iron.

Being prepared by a liquid-phase reduction method, sulfur-modified nanoscale zero-valent iron (S-nZVI) was then coated with sodium alginate (SA) to form gel beads (SAS-nZVI) which are capable of removing Pb(II) from water. SAS-nZVI was characterized by SEM, EDS, FTIR, XRD, and BET, and its removal effect on Pb(II) in water, including the effects of pH, adsorbent dosage, shaking time, and initial concentration of lead, was also studied. The results demonstrated that the maximum removal efficiency of Pb(II) by SAS-nZVI was 97.89%, and the maximum uptake was 246.40 mg/g. In the Pb(II) removal behavior study, the pseudo-second-order kinetic model and the Langmuir isotherm model were found to fit the adsorption process well. SAS-nZVI was easier to recycle from the reaction system, and the removal efficiency of SAS-nZVI to Pb(II) in water was still able to reach 82.75% after five cycles. Therefore, this study suggests that SAS-nZVI has a high removal capacity for Pb(II) and great potential in water pollution treatment.

Assessment soil cadmium and copper toxicity on barley growth and the influencing soil properties in subtropical agricultural soils.

Evaluation joint cadmium (Cd) and copper (Cu) phytotoxicity in wide range of subtropical agricultural soils is highly vital for phytoremediation of soils contaminated with Cd and Cu. In this study, barley root elongation assays were performed in 30 representative soils in response to single and combined Cd and Cu inhibition. The single Cd caused nearly 50% inhibition of barley root elongation, and Cu induced more than 50% inhibition in most soils. Mixed Cd + Cu caused significant inhibition on barley growth with average relative root elongation values of 20.0% and 30.4% in soil with a pH < 7 and pH > 7, respectively. An antagonistic interaction was evaluated in combined Cd + Cu toxicity, which was strong in soils containing low soluble Cu and Cd contents. Soil pH was the controlling factor in predicting single and mixed Cd and Cu phytotoxicity, which could explain 44% and 46% variation of single Cd and Cu toxicity, respectively. Soil organic carbon and effective cation exchange capacity were another important factor positively influencing metal toxicity, which further improved empirical prediction models accuracy, with determined coefficient (r2) values of 0.44-0.84. These results provide a theoretical basis for soils Cd and Cu pollution control.

Evaluating Fouling Control and Energy Consumption in a Pilot-Scale, Low-Energy POREFLON Non-Aerated Membrane Bioreactor (LEP-N-MBR) System at Different Frequencies and Amplitudes.

Continual aeration, a fouling control strategy that causes high energy consumption, is the major obstacle in the deployment of membrane bioreactors (MBRs) for wastewater treatment. In recent years, a technology has been developed which adopts mechanical reciprocity for membrane vibration, and it has been proven efficient for membrane scouring, as well as for saving energy: the low-energy POREFLON non-aerated membrane bioreactor (LEP-N-MBR). In this study, a pilot-scale LEP-N-MBR system was designed, established, and operated at various frequencies and amplitudes, and with various membrane models, so as to evaluate energy usage and membrane fouling. The results showed that a slower TMP rise occurred when the frequency and amplitude were set to 0.5 Hz and 10 cm, respectively. Under a suitable frequency and amplitude, the TMP increasing rate of model B (sealed only with epoxy resin) was slower than that of model A (sealed with a combination of polyurethane and epoxy resin). The average specific energy demand (SED) of the LEP-N-MBR was 0.18 kWh·m-3, much lower than the aerated MBR with 0.43 kWh·m-3 (obtained from a previous study), indicating a significant decrease of 59.54% in the SED. However, the uneven distribution of sludge within the membrane tank indicated that the poor hydraulic mixing in the reactor may result in sludge accumulation, which requires further operational optimization. The findings of this pilot-scale study suggest that the LEP-N-MBR system is promising and effective for municipal wastewater treatment with a much lower level of energy usage. More research is needed to further optimize the operation of the LEP-N-MBR for wide application.

A novel carbonized derivative of Fe-Cu bimetallic organic framework (Fe-Cu-MOF@C): preparation and optimization.

A carbon derivative with Fe-Cu bimetallic organic framework (Fe-Cu-MOF@C) was prepared by microwave synthesis and pyrolysis. Using potassium persulfate (PS) as oxidant and 2,4-dichlorophenol (2,4-DCP) as target pollutant, the optimal preparation conditions of Fe-Cu-MOF@C were studied. The factors affecting the synthesis of Fe-Cu-MOF include microwave power, microwave time, microwave temperature, the molar ratio of metal ions to organic ligands, the molar ratio of iron and copper, etc. In addition, the influence of pyrolysis temperature on the performance of Fe-Cu-MOF@C cannot be ignored. The results show that Fe-Cu-MOF@C has the best catalytic performance when the microwave time is 30 min, the microwave power is 600 W, the microwave temperature is 150 °C, the molar ratio of (Fe2+ + Cu2+)/H2BDC is 10:3, the molar ratio of Fe2+/Cu2+ is 10:1, and the pyrolysis temperature is 700 °C. After 90 min of reaction, 2,4-DCP was completely removed. Repeatable experiments show that Fe-Cu-MOF@C has good stability and its service life can be restored by heat treatment. In this study, a heterogeneous catalyst with strong catalytic capacity, high stability and easy recovery was prepared by a simple and efficient process, which is conducive to the development of advanced oxidation technology and the progress of water environmental protection.

Study on the remediation of heavy metal contaminated soils by citric acid and polyepoxysuccinic acid complex leaching.

Soil leaching remediation has attracted extensive attention because of its good removal effect, short operation period and stable removal effect of heavy metals. The key to reduce the harm of heavy metal contaminated soil to the environment and human health is to use appropriate leachate to repair heavy metal contaminated soil. In this study, citric acid (CA), iron nitrate (Fe(NO3)3) and polyepoxysuccinic acid (PESA) with different concentrations were used as research reagents to explore the best combination of leaching effects of heavy metals (Cu, Zn, Pb, Cd) in contaminated soil. The effects of concentration of eluent, liquid to solid ratio and leaching time on leaching efficiency of heavy metals and the changes of soil physical and chemical properties before and after leaching were studied. The results showed that 0.5 mol/L CA and 0.05 mol/L PESA were combined according to the volume ratio of 7:3, and the leaching effect was the best when the liquid-solid ratio was 15 and the leaching time was 240 min. Under the optimal leaching condition, the four heavy metals in the soil had significant removal effects, and the removal rates were, respectively, 86.06% Cu, Zn 74.55%, Pb 67.88% and Cd 91.63%. The X-ray spectrum and Fourier infrared spectrum analysis of soil before and after leaching showed that CA-PESA combined leaching had little effect on soil structure change. This study provided theoretical support for the development and application of suitable leaching agents for the remediation of heavy metal-contaminated soil.

Degradation of 2,4-DCP by the immobilized laccase on the carrier of sodium alginate-sodium carboxymethyl cellulose.

In this paper, sodium alginate-sodium carboxymethyl cellulose (SA-CMC) composite material was used as a carrier, and sodium alginate-embedded laccase (Lac@SC) was prepared by traditional embedding method. After that, ethylene glycol diglycidyl ether (EGDE) and glutaraldehyde (GLU) were used as cross-linking agents, two different cross-linking-embedded co-immobilized laccases (Lac@SCG and Lac@SCE) were innovatively prepared, respectively, and then these immobilized laccases were characterized by SEM, FT-IR and XRD, and the stability of the three immobilized laccases was explored. In addition, the effects of different factors on the removal of 2,4-DCP by immobilized laccase were studied, and the degradation kinetic models of three immobilized laccases on 2,4-DCP were summarized, the possible degradation pathways of pollutants were also given. Experimental results showed that compared to free laccase, the pH stability, thermal stability and storage stability of immobilized laccase were greatly improved. These immobilized laccases could maintain high activity at pH3~6, 45~55 °C. Lac@SCG had the best storage stability. After 30 days of storage, the relative enzyme activity was still more than 40%. Lac@SC had good reusability, the relative enzyme activity was still more than 50% after 5 uses. In the degradation of 2,4-DCP, all three immobilized laccases showed good performance, when Lac@SCE was at pH5, 35 °C, 25 h, the removal rate of 2,4-DCP could reach 95.2%; When at 45 °C, Lac@SC had the highest degradation rate which reach to 94%; At 45 °C, the degradation rate of Lac@SCG reached 83.2%.

Adsorption and removal of direct red 31 by Cu-MOF: optimization by response surface.

Cu(PABA) is a Cu-based MOF material assembled from Cu2+ and the organic ligand p-aminobenzoic acid (PABA). Cu (PABA) was synthesized by a solvothermal method, characterized and applied to the adsorption of direct red 31 dye (DR-31). The effects of pH, DR-31 concentration and temperature on the adsorption performance of Cu(PABA) were investigated. The adsorption kinetics were analyzed by pseudo-first-order, pseudo-second-order and intra-particle diffusion models, and the adsorption equilibrium data was fitted by Langmuir and Freundlich isotherm models. The pseudo-first-order kinetics and Langmuir model satisfactorily described the adsorption kinetics and adsorption equilibrium, respectively. The maximum adsorption capacity of Cu(PABA) for DR-31 dye at room temperature was 1,244.8 mg/g, as calculated using the Langmuir adsorption isotherm model. By response surface methodology (RSM), the optimal adsorption was found at pH value of 10.9, DR-31 dye concentration of 216.6 mg/L, and temperature of 27 °C, and the removal rate was as high as 99.4%. Therefore, Cu(PABA) can be used as an efficient adsorbent for removing DR-31 dye from aqueous solution.

Immobilization of laccase on chitosan functionalized halloysite nanotubes for degradation of Bisphenol A in aqueous solution: degradation mechanism and mineralization pathway.

As a hazardous organic chemical raw material, Bisphenol A (BPA) has attracted a great deal of scientific and public attention. In this study, the chitosan functionalized halloysite nanotubes immobilized laccase (lac@CS-HNTs) was prepared by simultaneous adsorption-covalent binding method to remove BPA for the first time. We optimized the preparation of lac@CS-NHTs by controlling one-factor variable method and response surface methodology (RSM). The cubic polynomial regression model via Design-Expert 12 was developed to describe the optimal preparation conditions of immobilized laccase. Under the optimal conditions, lac@CS-NHTs obtained the maximum enzyme activity, and the enzyme loading was as high as 60.10 mg/g. The results of batch removal experiment of BPA showed that under the optimum treatment condition, the BPA removal rate of lac@CS-NHTs, FL and heat-inactivated lac@CS-NHTs was 87.31 %, 60.89 % and 24.54 %, respectively, which indicated that the contribution of biodegradation was greater than adsorption. In addition, the relative activity of lac@CS-NHTs dropped to about 44.24 % after 8 cycles of BPA removal, which demonstrated that lac@CS-NHTs have the potential to reduce costs in practical applications. Finally, the possible degradation mechanism and mineralization pathway of BPA were given via High-performance liquid chromatography (HPLC) analysis and gas chromatography-mass spectrometry (GC-MS) analysis.

Improved stability and promoted activity of laccase by One-Pot encapsulation with Cu (PABA) nanoarchitectonics and its application for removal of Azo dyes.

Immobilization of laccase helps protect the laccase and realizes repeated use. However, excessive encapsulation protection will also limit the release of laccase activity. This work introduces an effective one-pot method encapsulating laccase in the porous material of metal organic framework (MOF) containing specific metal ions, which provided a new way to solve the problem of limited laccase activity. The immobilization process was mathematically modeled. The morphological and encapsulated properties of the prepared materials were confirmed by the characterization results of SEM, FTIR, XRD, TGA, XPS and CLSM. The results showed that laccase was successfully encapsulated, and the Cu (PABA) with Cu2+ as the central structure promoted the laccase activity, the activity of immobilized laccase increased by 1.7 times. The prepared laccase@Cu (PABA) (Lac@Cu (PABA)) showed enhanced stability to extreme pH, high temperature and storage time. More importantly, the Lac@Cu (PABA) exhibited superior reusability, maintaining 70% removal rate of Direct Red 31 (DR31) even after 10 cycles. The dye removal rate of immobilized laccase reached 92% in 6 h under optimal conditions. This research improved the stability of laccase while releasing the activity of laccase, which not only broadened the applicable environment of laccase, but also increased the rate of degradation, and provided a new idea for the clean and efficient treatment of water pollution in textile industry.

The spectral characteristics and cadmium complexation of soil dissolved organic matter in a wide range of forest lands.

The quality and quantity of dissolved organic matter (DOM) greatly controls the fate of heavy metals. The characteristics of DOM and its interaction with metals are essential for the metal ecological risk assessment of soils. In this study, the DOM spectral characteristics of representative forest soils and the complex capacities between fluorescent DOM components and cadmium (Cd) were analyzed. Functional groups, such as carboxylic acids, alcohols and phenols, were determined by FT-IR analysis. Chromophoric DOM, fluorescent DOM and dissolved organic carbon (DOC) concentrations exhibited strong correlations with each other, indicating that variations of DOC could be well explained by Chromophoric DOM or fluorescent DOM due to high correlation coefficients. The spectral slope ratio was in the range of 0.85-5.90, implying an abundance of heavy macromolecular humic acids, peptides, and polycondensates. The absorbance spectral at 254 nm (SUVA254) strongly correlated with SUVA260 (r = 0.992, P < 0.01), indicating that hydrophobicity closely related with aromatic structure, and aromatic groups could be broadly hydrophobic. Fluorescence indices were from 1.62 to 2.21 and biological index values ranged from 0.54 to 1.14, where the DOM was mainly sourced from mixed terrestrial and autogenous inputs in most sites. Four universal fluorescence components were identified and characterized by fluorescence EEM-PARAFAC, including two humic-like (components 1 and 2), one tyrosine-like (components 3) and one fulvic-like (components 4) component. Both components 3 and 4 showed fluorescence quenching with increasing Cd concentrations, while components 1 and 2 had no evident change in fluorescence intensity. The logK3 and logK4 values ranged from 4.41 to 5.29 and 4.71 to 5.54, respectively, with most logK values of component 3 for Cd binding being smaller than that of component 4, thus, indicating that the fulvic acid substances exhibited stronger and more stable interactions with Cd than protein-like components.