Electroplating wastewater treatment by in-situ formation of organic anions and inorganic anions intercalated layered double hydroxides.

The electroplating wastewater containing various metal ions was treated by adding sodium dodecyl benzene sulfonate (SDBS) and regulating pH value, and the resulting precipitates were characterized by X-ray diffraction (XRD). The results showed that organic anions intercalated layered double hydroxides (OLDHs) and inorganic anions intercalated layered double hydroxides (ILDHs) were in-situ formed to remove heavy metals during the treatment process. In order to reveal the formation mechanism of the precipitates, SDB- intercalated Ni-Fe OLDHs, NO3- intercalated Ni-Fe ILDHs and Fe3+-DBS complexes were synthsized by co-precipitation at various pH values for comparison. These samples were characterized by XRD, Fourier Transform infrared (FTIR), element analysis as well as the aqueous residual concentrations of Ni2+ and Fe3+ were detected. The results showed that OLDHs with good crystal structures can be formed as pH≤7, while ILDHs began to form at pH = 8. When pH < 7, complexes of Fe3+ and organic anions with the ordered layered structure were formed firstly, and then with increase in pH value, Ni2+ inserted into the solid complex and the OLDHs began to form. However, Ni-Fe ILDHs were not formed when pH ≤ 7. The Ksp (Solubility Product Constant) of OLDHs was calculated to be 3.24 × 10-19 and that of ILDHs was 2.98 × 10-18 at pH = 8, which suggested that OLDHs might be easier to form than ILDHs. The formation process of ILDHs and OLDHs were also simulated through MINTEQ software, and the simulation output verified that OLDHs could be easier to form than ILDHs at pH ≤ 7. Information from this study provides a theoretical basis for effective in-situ formation of OLDHs in wastewater treatment.

Adsorption characteristics of assembled and unassembled Ni/Cr layered double hydroxides towards methyl orange.

The lamella aggregation state of layered double hydroxides (LDHs) may affect their sorption capacity for organic compounds. The dried LDH samples (Ni/Cr LDH-FA-D and Ni/Cr LDH-H2O-D) and the undried samples (Ni/Cr LDH-FA-W and Ni/Cr LDH-H2O-W) were flexibly prepared by a co-precipitation method in formamide (FA) and water, respectively. The results of X-ray diffraction (XRD) and transmission electron microscope (TEM) showed that the undried LDHs were unassembled, which had no the stacking layers but had a pseudohexagonal nanosheet lamella structure. And the unassembled LDH layers can be assembled again during the dry process. Ni/Cr LDH-FA-W and Ni/Cr LDH-H2O-W showed much greater adsorption capacities towards methyl orange (MO) than Ni/Cr LDH-FA-D and Ni/Cr LDH-H2O-D, as well as shorter time to reach equilibrium. The maximum adsorption capacity of MO could be calculated to 806 mg/g and 740 mg/g for Ni/Cr LDH-FA-W and Ni/Cr LDH-H2O-W by Langmuir-type simulation. The greater adsorption capacities of unassembled LDH could be attributed to the loosen structure and much more exposed adsorption sites. It could be concluded that unassembled LDHs were an effective and conducive preparation pathway for the exploration of the adsorption sites of LDHs.

Behavior of fast and slow phosphorus release from sewage sludge-derived biochar amended with CaO.

The pyrolyzation of sewage sludge (SS) could efficiently transform inherent phosphorus (P) into bioavailable phosphate forms, which endows SS-derived biochar (SSB) the potential as a soil fertilizer. However, the details about the release behavior of P in SSB have not been systematically investigated. This study evaluated the fast and slow P releasing behaviors from SSB and CaO-amended SSB prepared under different pyrolysis temperature. The higher pyrolysis temperature and CaO addition could enhance the conversion of non-apatite inorganic phosphorus (NAIP) into more bioavailable apatite inorganic phosphorous (AP). Acidic and alkaline conditions were favorable for the fast release of P from SSB. Higher ionic strength condition gave greater releasing amounts of TP and the SO42- facilitating a rapid release of TP than those for Cl- and NO3-. SSBs with CaO addition showed a much slower TP release than those without CaO both in fast release (24 h, with CaO: 0.05~0.4 mg TP g-1 SSB, e.g., without CaO 0.5~5 mg TP g-1 SSB) and slow release tests (21 days, with CaO: 1.2~4.1 mg TP g-1 SSB, e.g., without CaO 1.8~5.7 mg TP g-1 SSB). Ortho-P release was more remarkable for the SSB amended with CaO (~54% of TP), which was likely due to the formation of orthophosphate. The results of this study suggested that SSB prepared by high pyrolysis temperature and CaO addition had high potential as a slow P-releasing fertilizer for the soil.

Phosphorus speciation and bioavailability of sewage sludge derived biochar amended with CaO.

In this study, biochar samples were prepared from the co-pyrolysis of sewage sludge (SS) and CaO to explore the transformation of P speciation in sample. The potential of these biochar as a fertilizer to promote the growth of the plant was also evaluated. The result indicated that CaO addition can greatly facilitate the conversion of non-apatite inorganic phosphorus (NAIP) to apatite inorganic phosphorus (AP, mainly Ca3(PO4)2 and Ca3Mg3(PO4)4). The addition of 10% CaO in feedstock is sufficient to convert SS inherent P into more bioavailable AP. Under such a dosage, AP content in biochar increased by 21.2-33.6% in contrast to CaO free sample at pyrolysis temperature of 500-800 °C, and water-soluble phosphorus (WSP) content decreased to less than 1% of TP. The addition of CaO can also apparently reduce Zn, Mn leaching from biochar. Additionally, hydroponics assay showed that CaO amended SS biochar can promote the growth of rice seedling. The results of this study indicate that preparing CaO amended SS biochar is a technically feasible strategy to utilize P resource in SS.

Formation, characteristics, and applications of environmentally persistent free radicals in biochars: A review.

Due to abundant biomass and eco-friendliness, biochar is exemplified as one of the most promising candidates to mediate the degradation of environmental contaminants. Recently, environmentally persistent free radicals (EPFRs) have been detected in biochars, which can activate S2O82- or H2O2 to generate reactive oxygen species for effective degradation of organic and inorganic contaminants. Comprehending the formation mechanisms of EPFRs in biochars and their interactions with contaminants is indispensable to further develop their environmental applications, e.g., direct and indirect EPFR-mediated removal of organics/inorganics by biochars. With reference to the information of EPFRs in environmental matrices, this article critically reviews the formation mechanisms, characteristics, interactions, and environmental applications of EPFRs in biochars. Synthesis conditions and loading of metals/organics are considered as key parameters controlling their concentrations, types, and activities. This review provides new and important insights into the fate and emerging applications of surface-bound EPFRs in biochars.

Transformation of functional groups and environmentally persistent free radicals in hydrothermal carbonisation of lignin.

In this study, lignin was selected as the main component of waste biomass to synthesise carbonaceous adsorbents with environmentally persistent free radicals (EPFRs) through hydrothermal carbonisation (HTC) under different conditions. The HTC method with Fe(III) doping was superior for promoting dehydration and decarboxylation of lignin hydrochar than that with HTC Cu(II) doping. The deconstruction of oxygen-containing groups of lignin was reduced while esterification was enhanced by Fe(III). The Fe(III) addition was conducive to the formation of EPFRs as carbon-centred radicals with an adjacent oxygen atom and oxygen-centred radicals. A comparison of lignin with cellulose and d-xylose suggests that the formed EPFRs on lignin hydrochar were derived from their phenolic hydroxyl groups. A high removal efficiency of bisphenol A by lignin hydrochar was observed owing to oxygen-centred radicals, which activated H2O2 to produce OH. These results will facilitate the design and application of novel hydrochar materials with EPFRs.

Lignin valorization for the production of renewable chemicals: State-of-the-art review and future prospects.

Lignin is an abundant biomass resource in aromatic structure with a low price in market, which can serve as renewable precursors of value-added products. However, valorization rate of annually produced lignin is less than 2%, suggesting the need for technological advancement to capitalize lignin as a versatile feedstock. In recent years, efficient utilization of lignin has attracted wide attention. This paper summarizes the research advances in the utilization of lignin resources (mainly in the last three years), with a particular emphasis on two major approaches of lignin utilization: catalytic degradation into aromatics and thermochemical treatment for carbon material production. Hydrogenolysis, direct pyrolysis, hydrothermal liquefaction, and hydrothermal carbonization of lignin are discussed in detail. Based on this critical review, future research directions and development prospects are proposed for sustainable and cost-effective lignin valorization.

Electroplating sludge derived zinc-ferrite catalyst for the efficient photo-Fenton degradation of dye.

A zinc-dominant ferrite catalyst for efficient degradation of organic dye was prepared by the calcination of electroplating sludge (ES). Characterizations indicated that zinc ferrite (ZnFe2O4) coexisted with Fe2O3 structure was the predominant phase in the calcined electroplating sludge (CES). CES displayed a high decolorization ratio (88.3%) of methylene blue (MB) in the presence of H2O2 combined with UV irradiation. The high efficiency could be ascribed to the photocatalytic process induced by ZnFe2O4 and the photo-Fenton dye degradation by ferrous content, and a small amount of Al and Mg in the sludge might also contribute to the catalysis. Moreover, the degradation capability of dye by CES was supported by the synthetic ZnFe2O4 with different Zn to Fe molar ratio (n(Zn): n(Fe)), as 84.81%-86.83% of dye was removed with n(Zn): n(Fe) ranged from 1:0.5 to 1:3. All synthetic ferrite samples in the simulation achieved adjacent equilibrium decolorization ratio, the flexible proportioning of divalent metal ions (M2+) to trivalent metal ions (M3+) applied in the synthesis indicated that the catalyst has a high availability. Therefore, an efficacious catalyst for the degradation of dye can potentially be derived from heavy metal-containing ES, it's a novel approach for the reutilization of ES.

Advanced treatment of stabilized landfill leachate after biochemical process with hydrocalumite chloride (Ca/Al-Cl LDH).

This study investigated the effectiveness of Ca/Al-Cl LDH for the treatment of stabilized landfill leachate. Experiments were performed including different dosage of Ca/Al-Cl LDH and comparison with different reagents, such as CaCl2 and AlCl3. As a result, Ca/Al-Cl LDH efficiently removed organic matters in stabilized landfill leachate with the maximum removal (59.41% COD, 62.06% DOC and 70.56% UV254) at the dose of 30g/L. According to UV254 and EEM, it is remarkable that the formation of Ca/Al-LDH has a greater beneficial to organic removal than other reagents, especially for fulvic acid-like and humic acid-like compounds. Moreover, the removal of fulvic acid-like compounds was much better than humic acid-like compounds. The previous compounds had more carboxylic groups, thus had a better removal selectivity.

Combined (1)H NMR and LSER study for the compound-specific interactions between organic contaminants and organobentonites.

The compound-specific mechanisms for the sorption of organic contaminants onto cetyltrimethylammonium-saturated bentonite (i.e., CTMA-Bentonite) in water were evaluated by (1)H NMR study and Linear Solvation Energy Relationship (LSER) approach. In (1)H NMR study, comparing with pure CTMAB, the up-field shifts of hydrogen peaks for CH2N(+) and CH3N(+) of CTMA(+) in CTMAB-aromatics (1-naphtylamine, aniline and phenol) mixtures are much greater than that in CTMAB-aliphatics (cyclohexanone and cyclohexanol) mixtures. Meanwhile, the peak position of hydrogen on amino- and hydroxyl-groups of aromatic compounds also changes greatly. (1)H NMR data demonstrated the strong molecular interaction between the positive ammonium group of CTMA(+) and the delocalized π-systems of aromatic solutes, whereas the interactions of CTMA(+) with aliphatic compounds having electron-donating groups (such as cyclohexanol and cyclohexanone) or aromatic ring substituted by electron-withdrawing groups (i.e., nitrobenzene) or nonpolar aromatic compounds with single phenyl ring (i.e., toluene) are weak. The derived LSER equation was obtained by a multiple regression of the solid-water sorption coefficients (Kd) of 16 probe solutes upon their solvation parameters, and demonstrates aromatics sorption onto CTMA-Bentonite is concurrently governed by the π-/n-electron pair donor-accepter interaction and the cavity/dispersion interaction, while the predominant mechanism for aliphatic compounds is the cavity/dispersion interaction, consisting with the (1)H NMR results.

Abatement of aqueous anionic contaminants by thermo-responsive nanocomposites: (poly(N-isopropylacrylamide))-co-silylanized magnesium/aluminun layered double hydroxides.

A series of novel thermo-responsive composite sorbents, were prepared by free-radical co-polymerization of N-isopropylacrylamide (NIPAm) and the silylanized Mg/Al layered double hydroxides (SiLDHs), named as PNIPAm-co-SiLDHs. For keeping the high affinity of Mg/Al layered double hydroxides towards anions, the layered structure of LDHs was assumed to be reserved in PNIPAm-co-SiLDHs by the silanization of the wet LDH plates as evidenced by the X-ray powder diffraction. The sorption capacity of PNIPAm-co-SiLDH (13.5 mg/g) for Orange-II from water was found to be seven times higher than that of PNIPAm (2.0mg/g), and the sorption capacities of arsenate onto PNIPAm-co-SiLDH are also greater than that onto PNIPAm, for both As(III) and As(V). These sorption results suggest that reserved LDH structure played a significant role in enhancing the sorption capacities. NO3(-) intercalated LDHs composite showed the stronger sorption capacity for Orange-II than that of CO3(2-). After sorption, the PNIPAm-co-SiLDH may be removed from water because of its gel-like nature, and may be easily regenerated contributing to the accelerated desorption of anionic contaminants from PNIPAm-co-SiLDHs by the unique phase-transfer feature through slightly heating (to 40 °C). These recyclable and regeneratable properties of thermo-responsive nanocomposites facilitate its potential application in the in-situ remediation of organic and inorganic anions from contaminated water.

Quick and efficient co-treatment of Zn(2+)/Ni(2+) and CN(-) via the formation of Ni(CN)4(2-) intercalated larger ZnAl-LDH crystals.

The wide use of metal electroplating involving CN(-) necessitates the cost-effective treatment of both CN and metals (Zn, Cu, Ni etc.). In this research, we developed a novel strategy - Ni(2+)-assisted layered double hydroxide (LDH) precipitation - to simultaneously remove aqueous CN and Zn/Ni metals. The strategy is to convert CN(-)/Zn(CN)4(2-) to Ni(CN)4(2-) first, and then to quickly precipitate Ni(CN)4(2-)/CN(-) into LDH crystals. The conversion has been clearly evidenced by the change of CN characteristic FTIR bands of Zn-CN solution before and after adding Ni(NO3)2. The intercalation and efficient removal of CN have also been confirmed through the formation of LDH crystals XRD and SEM. In particular, a set of optimized experimental factors has been obtained by investigating their effects on CN removal efficiency in the simulated tests. Remarkably, over 95% CN were removed with high removal efficiencies of metals. Our results thus suggest that the current strategy is a quick, efficient and promising way to simultaneously treat both Ni and metals/CN rich electroplating wastewaters.

Decomposition of potent greenhouse gas sulfur hexafluoride (SF6) by Kirschsteinite-dominant stainless steel slag.

In this investigation, kirschsteinite-dominant stainless steel slag (SSS) has been found to decompose sulfur hexafluoride (SF6) with the activity higher than pure metal oxides, such as Fe2O3 and CaO. SSS is mainly made up of CaO·FeO·SiO2(CFS)/MgO·FeO·MnO(RO) phase conglomeration. The SF6 decomposition reaction with SSS at 500-700 °C generated solid MF2/MF3 and gaseous SiF4, SO2/SO3 as well as HF. When 10 wt % of SSS was replaced by Fe2O3 or CaO, the SF6 decomposition amount decreased from 21.0 to 15.2 or 15.0 mg/g at 600 °C. The advantage of SSS over Fe2O3 or CaO in the SF6 decomposition is related to its own special microstructure and composition. The dispersion of each oxide component in SSS reduces the sintering of freshly formed MF2/MF3, which is severe in the case of pure metal oxides and inhibits the continuous reaction of inner components. Moreover, SiO2 in SSS reacts with SF6 and evolves as gaseous SiF4, which leaves SSS with voids and consequently exposes inner oxides for further reactions. In addition, we have found that oxygen significantly inhibited the SF6 decomposition with SSS while H2O did not, which could be explained in terms of reaction pathways. This research thus demonstrates that waste material SSS could be potentially an effective removal reagent of greenhouse gas SF6.

Chemical characteristics and risk assessment of typical municipal solid waste incineration (MSWI) fly ash in China.

The release of heavy metals in municipal solid waste incineration (MSWI) fly ash has become a worrying issue while fly ash is utilized or landfilled. This work investigated the potential mobility of heavy metals in the fly ashes from 15 typical MSWI plants in Chinese mainland by the characterization of distribution, chemical speciation and leaching behavior of heavy metals. The results showed that total content of heavy metals decreased in the order Zn>Pb>Cu>Cr>Ni>Cd in samples. The toxicity characteristics leaching procedure (TCLP) of fly ash indicated that the amount of leached Cd in 67% of samples exceeded the regulated limit. Also, the excess amount of leached Zn and Pb was observed in 40% and 53% of samples, respectively. The chemical speciation analysis revealed that this excess of heavy metal leached in TCLP was contributed to the high content of acid soluble fraction (F1) and reducible fraction (F2) of heavy metal. Moreover, the great positive relevance between leaching behavior of heavy metals and F1 fraction was supported by principal component analysis (PCA). Risk assessment code (RAC) results suggested that Cd and Pb showed a very high risk class to the environment.

Mechanism of interaction of hydrocalumites (Ca/Al-LDH) with methyl orange and acidic scarlet GR.

The development of new materials for water purification is of universal importance. Among these types of materials are layered double hydroxides (LDHs). Non-ionic materials pose a significant problem as pollutants. The interaction of methyl orange (MO) and acidic scarlet GR (GR) adsorption on hydrocalumite (Ca/Al-LDH-Cl) was studied by X-ray diffraction (XRD), infrared spectroscopy (MIR), scanning electron microscope (SEM), and near-infrared spectroscopy (NIR). The XRD results revealed that the basal spacing of Ca/Al-LDH-MO was expanded to 2.45 nm, and the MO molecules were intercalated with a interpenetrating bilayer model in the gallery of LDH, with 49° tilting angle. Yet, Ca/Al-LDH-GR was kept the same d-value as Ca/Al-LDH-Cl. The NIR spectrum for Ca/Al-LDH-MO showed a prominent band around 5994 cm(-1), assigned to the combination result of the NH stretching vibrations, which was considered as a mark to assess MO(-) ion intercalation into Ca/Al-LDH-Cl interlayers. From SEM images, the particle morphology of Ca/Al-LDH-MO mainly changed to irregular platelets, with a "honey-comb" like structure. Yet, the Ca/Al-LDH-GR maintained regular hexagon platelets, which was similar to that of Ca/Al-LDH-Cl. All results indicated that MO(-) ion was intercalated into Ca/Al-LDH-Cl interlayers, and acidic scarlet GR was only adsorbed upon Ca/Al-LDH-Cl surfaces.

Effective adsorption of sodium dodecylsulfate (SDS) by hydrocalumite (CaAl-LDH-Cl) induced by self-dissolution and re-precipitation mechanism.

Hydrocalumite (CaAl-LDH-Cl) was synthesized through a rehydration method involving a freshly prepared tricalcium aluminate (C(3)A) with CaCl(2) solution. To understand the intercalation behavior of sodium dodecylsulfate (SDS) with CaAl-LDH-Cl, X-ray diffraction (XRD), Fourier transform infrared (FTIR), scanning electron microscopy (SEM), transmission electron microscope (TEM), X-ray photoelectron spectroscopy (XPS), inductively coupled plasma-atomic emission spectrometer (ICP), and elemental analysis have been undertaken. The sorption isotherms with SDS reveal that the maximum sorption amount of SDS by CaAl-LDH-Cl could reach 3.67 mmol g(-1). The results revealed that CaAl-LDH-Cl holds a self-dissolution property, about 20-30% of which is dissolved. And the dissolved Ca(2+) and Al(3+) ions are combined with SDS to form CaAl-SDS or Ca-SDS precipitation. It has been highlighted that the composition of resulting products is strongly dependent upon the SDS concentration. With increasing SDS concentrations, the main resulting product changes from CaAl-SDS to Ca-SDS, and the value of interlayer spacing increased to 3.27 nm.

Adsorptive characteristics of the siloxane surfaces of reduced-charge bentonites saturated with tetramethylammonium cation.

To elucidate interactions of neutral organic contaminants (NOCs) with siloxane surfaces (often referred to hydrophobic nanosites)found between cations in 2:1 phyllosilicates, adsorption of aliphatic and aromatic compounds onto both internal and external siloxane surfaces oftetramethylammonium-intercalated bentonite with a cation exchange capacity (CEC) of 108 cmol/kg (108TMA) and its reduced-charge bentonite (CEC = 65 cmol/ kg, 65TMA) were investigated. Reduction of the layer charge and saturation of bentonite interlayers with TMA+ modify the interlayer microenvironments, which dramatically promote adsorption of NOCs. Specific mechanisms (i.e., steric restriction and phenyl-effect) control the adsorption of NOCs onto internal siloxane surfaces of TMA+ -bentonites from water. The adsorption sites of 108TMA can not provide sufficient space to accommodate NOCs, hence hindering adsorption. Adsorption mechanism on 65TMA varies with solute-loadings, from polarity-selective at low loadings to aromaticity-preferable at high loadings. Significant contribution of phenyl-effect between adsorbed-solutes to aromatics adsorption on 65TMA is found. Solvent polarity effect on the aggregation of TMA+ -bentonites and aniline adsorption demonstrated that the contribution of external siloxane surfaces to favor adsorption in n-hexane are actually exploited but generally omitted. These observations provide significant insights into distinguishing different uptake mechanisms as well as the potential means for the rational design of better organic sorbents.

Efficient removal and mechanisms of water soluble aromatic contaminants by a reduced-charge bentonite modified with benzyltrimethylammonium cation.

A novel strategy utilizing the phenyls interaction and the hydrophobic affinity of available siloxane surface in the interlayer of bentonite was proposed to improve the sorption capabilities of organobentonites for water soluble aromatic contaminants. A unique organobentonite (65BTMA) was synthesized by intercalating benzyltrimethylammonium cation (BTMA(+)) into the interlayer of a reduced-charge bentonite with cation exchange capacity (CEC) of 65 cmol kg(-1). Phenol, aniline and toluene were used as model compounds of water soluble aromatic contaminants. Their respective removal efficiencies by 65BTMA were achieved at 83.3%, 89.2% and 97.3% at the initial concentration of 20 mg l(-1). To reveal the sorption mechanism, sorption characteristics of aromatic contaminants to 65BTMA were compared with that of aliphatic contaminants in similar molecular size. And various organobentonites were prepared by combining TMA(+) (tetramethylammonium), BTMA(+), HTMA(+) (heptyltrimethylammonium) and CTMA(+) (cetyltrimethylammonium) with two bentonites (CEC=108 and 65 cmol kg(-1)). To 65BTMA, sorption magnitudes of aromatic contaminants were much greater than that of aliphatic compounds with similar size; and dramatically higher than those to other organobentonites at low pollutant concentrations. These observations revealed that the strong phenyls interactions contributed significantly to sorb the aqueous soluble aromatic contaminants to 65BTMA (>90%), and which favored to design uniquely powerful sorbents.

A facile solid phase synthesis of tetramic acid.

The condensation of N-acylated amino acids with polymer-supported cyclic malonic acid ester was carried out in the presence of DCC/DMAP. The cyclisation of the intermediate resin, by heating in an organic solvent, gave the N-protected tetramic acid derivatives in good yields and high purity.