Competitive adsorption of nitrate, phosphate, and sulfate on amine-modified wheat straw: In-situ infrared spectroscopic and density functional theory study.

Amine-modified wheat straw (AMWS) has already been reported as a promising adsorbent for nitrate (NO3) removal due to its cost-effectiveness and high efficiency. However, the NO3 removal mechanism has not been well understood, especially in the presence of co-existing ions. Here, the effect of co-existing anions on NO3 removal by AMWS was investigated and the underlying mechanisms were revealed using a combination of in-situ infrared (IR) spectroscopy and computational modeling. The in-situ IR results indicated that NO3, sulfate (SO4), and phosphate (PO4) are all adsorbed as outer-sphere complexes on AMWS. The two-dimensional-correlation spectroscopy analysis implied the adsorption sequence of SO4 > PO4 > NO3. The adsorption energies obtained from density functional theory calculation range from -0.24 to 0.51 eV (-23.2 to 49.2 kJ/mol), confirming that these anions adsorb on AMWS as outer-sphere complexes. For the first time, this study provides direct spectroscopic evidence of the outer-sphere adsorption of NO3 on AMWS, as well as identifies the adsorption sequence, confirmed by computational modeling. The competitive mechanism of NO3, SO4, and PO4 revealed in this study is helpful to understand and predict the applications of AMWS.

MIR31HG polymorphisms are related to steroid-induced osteonecrosis of femoral head among Chinese Han population.

BACKGROUNDS: MIR31 host gene (MIR31HG) polymorphisms play important roles in the occurrence of osteonecrosis. However, the association of MIR31HG polymorphisms with the risk of steroid-induced osteonecrosis of the femoral head (SONFH) remains unclear. In this study, we aimed to investigate the correlation between MIR31HG polymorphisms and SONFH susceptibility in the Chinese Han population. METHODS: A total of 708 volunteers were recruited to detect the effect of seven single nucleotide polymorphisms (SNPs) in the MIR31HG gene on SONFH risk in the Chinese Han population. Genotyping of MIR31HG polymorphisms was performed using the Agena MassARRAY platform. The odds ratio (OR) and 95% confidence interval (95% CI) were used to evaluate the correlation between MIR31HG polymorphisms and SONFH risk using logistic regression model. RESULTS: According to the results of genetic model, rs10965059 in MIR31HG was significantly correlated with the susceptibility to SONFH (OR = 0.56, p = 0.002). Interestingly, the stratified analysis showed that rs10965059 was associated with the reduced risk of SONFH in subjects aged > 40 years (OR = 0.30, p < 0.001) and male populations (OR = 0.35, p < 0 .001). Moreover, rs10965059 was associated with the reduced risk of bilateral SONFH (OR = 0.50, p = 0.002). Finally, multi-factor dimension reduction (MDR) results showed that the combination of rs1332184, rs72703442, rs2025327, rs55683539, rs2181559, rs10965059 and rs10965064 was the best model for predicting SONFH occurrence (p < 0.0001). CONCLUSION: The study indicated that rs10965059 could be involved in SONFH occurrence in the Chinese Han population, which might provide clues for investigating the role of MIR31HG in the pathogenesis of SONFH.

Release of Pb adsorbed on graphene oxide surfaces under conditions of Shewanella putrefaciens metabolism.

In this study, Pb(II) was used as a target heavy metal pollutant, and the metabolism of Shewanella putrefaciens (S. putrefaciens) was applied to achieve reducing conditions to study the effect of microbial reduction on lead that was preadsorbed on graphene oxide (GO) surfaces. The results showed that GO was transformed to its reduced form (r-GO) by bacteria, and this process induced the release of Pb(II) adsorbed on the GO surfaces. After 72 hr of exposure in an S. putrefaciens system, 5.76% of the total adsorbed Pb(II) was stably dispersed in solution in the form of a Pb(II)-extracellular polymer substance (EPS) complex, while another portion of Pb(II) released from GO-Pb(II) was observed as lead phosphate hydroxide (Pb10(PO4)6(OH)2) precipitates or adsorbed species on the surface of the cell. Additionally, increasing pH induced the stripping of oxidative debris (OD) and elevated the content of dispersible Pb(II) in aqueous solution under the conditions of S. putrefaciens metabolism. These research results provide valuable information regarding the migration of heavy metals adsorbed on GO under reducing conditions due to microbial metabolism.

Lead removal from water using organic acrylic amine fiber (AAF) and inorganic-organic P-AAF, fixed bed filtration and surface-induced precipitation.

Granular porous sorbents were normally used for heavy metals removal from water. To search for the new commercial sorbent and treatment strategy, an organic acrylic amine fiber (AAF) and phosphorus loading inorganic-organic AAF (P-AAF) were prepared and used for lead (Pb) removal from water. A new strategy of inorganic-organic coupling technology was proposed for Pb removal, based on the hypothesis of surface-induced precipitation mechanism. The AAF showed a Pb adsorption capacity of 417 mg/g from the Langmuir fitting, while the column filtration technology was further applied to measure the adsorption edge and applications. Effects of different initial Pb concentrations, hydraulic retention time, and co-existing P were considered in the filtration experiments. The presence of 0.8 mg/L P in water significantly improved the Pb breakthrough point from 15,000 to 41,000 bed volumes of water spiked with 85 µg/L Pb, while the P-AAF fixed bed showed better removal of Pb than AAF SEM/EDX and XRD spectra were employed for determining the surface functional groups and the formation of surface-induced precipitation of pyromorphite (Pb5(PO4)3OH) on AAF. This study verified the application of AAF sorbent for Pb removal and the enhanced effect of coating P on AAF, thus improved our fundamental understanding and application of the surface chemistry process of Pb with P.

Mechanistic Study of Pb(II) Removal by TiO2 and Effect of PO4.

As a commercial adsorbent, TiO2 shows a high adsorption capacity for lead (Pb(II)). However, the molecular structure of Pb(II) adsorption on TiO2 is still unknown. Meanwhile, as a widely used corrosion inhibitor, phosphate (PO4) is usually added into drinking water, and its influential mechanism on Pb(II) removal by TiO2 remains unknown. Here, the mechanisms of Pb(II) adsorption on TiO2 and the effect of PO4 were systematically investigated using a combination of spectroscopic analyses and surface complexation modeling. The adsorption structure of Pb(II) on TiO2 was revealed as a tridentate mononuclear configuration by the extended X-ray absorption fine structure (EXAFS) analysis. In the presence of 0.1-5 mg/L PO4, Pb(II) was removed mainly by adsorption on TiO2 rather than precipitation. Ternary complexation between Pb(II) and PO4 on TiO2 surfaces was found based on EXAFS and in situ Fourier transform infrared characterizations. These complexation structures were used to build a surface complexation model to accurately simulate and predict Pb(II) removal under different conditions. This study provides essential information about the mechanisms of Pb(II) removal by TiO2 and develops a model to predict adsorption behaviors, especially in the presence of PO4.

Adsorption and recovery of phosphate from water by amine fiber, effects of co-existing ions and column filtration.

A weak-base adsorption fiber, acrylic amine fiber (AAF), was prepared for removal and recovery of phosphate from water. The adsorption properties of the AAF for phosphate and effects of co-existing ions were investigated using batch and column filtration experiments, scanning electron microscope, and Fourier transform infrared techniques. Experimental results showed that AAF had a high phosphate adsorption capacity of 119 mg/g at pH 7.0. The effects of calcium, sulfate, carbonate, nitrate, and fluoride showed that sulfate and calcium inhibited phosphate adsorption. However, AAF showed higher binding affinity toward phosphate than sulfate. Column filtration results showed that AAF could filter 1420 bed volumes of tap water containing 1.0 mg-P/L of phosphate. The saturated AAF could be regenerated using 0.5 mol/L hydrochloric acid solution and reused. After desorption, phosphate was recovered through precipitation of hydroxyapatite (Ca5(PO4)3OH). The easy of regeneration, good adsorption performance, and the fiber morphology of AAF make it an attractive alternative for phosphate recovery from multiple water sources.

Mechanistic Study of Lead Adsorption on Activated Carbon.

Activated carbon (AC) is a carbonaceous material broadly applied in filters to remove lead (Pb(II)) from drinking water through adsorption. However, the chemical interactions between Pb(II) and the reactive sites on AC or other carbonaceous materials are not well understood, yet. The understanding of the mechanism of Pb(II) adsorption onto AC would allow to optimally design AC-based materials even in the presence of a complex liquid phase. Here, the interaction between Pb(II) and functional groups on AC was investigated at the molecular scale to help identifying the chemical reactions at the solid-liquid interface. Spectroscopic analyses and chemical quantum calculations were performed and indicated the formation of monodentate mononuclear Pb(II)-phenol and bidentate mononuclear Pb(II)-carboxyl complexes on AC. Competitive adsorption behavior was observed between Pb(II) and calcium (Ca(II)) because of their similar adsorption configurations on AC. In contrast, anions, including sulfate and phosphate, were observed to enhance Pb(II) adsorption on AC by forming ternary complexes. On the basis of these observations, a new surface complexation model of Pb(II) adsorption onto AC was formulated and validated with batch tests. Overall, this work presents a new set of chemical reactions at the solid-liquid interface between Pb(II) and AC under various conditions of interest for the application of AC or other carbonaceous materials in water treatment.

Competing Interactions of As Adsorption and Fe(III) Polymerization during Ferric Coprecipitation Treatment.

This study revealed the effect of As on the formation and dissolution of iron (hydr)oxides and its further impact on the As removal efficacy of FeCl3 treatment. Adding 6.7 mg/L FeCl3 into 325 µg/L As solution (coprecipitation) resulted in more As removal (99% As(V) and 75% As(III)) at 2 min than adding As into aged FeCl3 solution (preaged, 52-87% As(V) and 7-42% As(III)) at pH 7. However, soluble As gradually increased in the coprecipitation system and decreased in the preaged system to give similar concentrations during 800 h aging. The particle size of the iron (hydr)oxides increased more slowly in the coprecipitation than in the preaged systems. These results suggest the rapid adsorption of As on Fe polymer during the initial polymerization process, which delays the growth of iron (hydr)oxides. Thermodynamically, quantum chemical calculations implied that iron ions adsorption on iron (hydr)oxide polymer was more stable than As adsorption, which is the main driving force for the As release during aging process. This study improved our understanding of the kinetic and thermodynamic processes of As adsorption and iron (hydr)oxide precipitation in the coprecipitation treatment of As, and the potential for As release during aging of sludge generated in the treatment.

Effect of phosphate releasing in activated sludge on phosphorus removal from municipal wastewater.

Aluminum and ferric salts are commonly used in municipal wastewater treatment plants (WWPTs) for phosphorus (P) removal. In this study, on-site jar tests were conducted to determine the removal of different P species from the fresh samples in the presence and absence of activated sludge (AS) with different doses of alum, poly-aluminum chloride, and ferric chloride at different pH. The soluble P (SP) concentration in the samples was about 0.63mg/L. When the mixed liquor containing AS was treated with 8mg/L of Al, SP could be reduced to 0.13mg/L, while it was reduced to 0.16mg/L with only 1mg/L of Al after sedimentation removal of AS from sample. Chemical analysis determined that AS contained 59.8mg-P/g-TSS and 43.8mg-Al/g-TSS and most of the P was associated with the aluminum hydroxide. We discovered that the phosphate in the AS could readily be released from it, which was mainly responsible for ineffective removal of P to low levels in mixed liquor even with very high alum dose. This study provides new insight into the behavior and fate of P in the wastewater treatment plants that use alum to enhance P removal in the final effluent.

Effect of Arsenic on the Formation and Adsorption Property of Ferric Hydroxide Precipitates in ZVI Treatment.

Treatment of arsenic by zerovalent iron (ZVI) has been studied extensively. However, the effect of arsenic on the formation of ferric hydroxide precipitates in the ZVI treatment has not been investigated. We discovered that the specific surface area (ca. 187 m2/g) and arsenic content (ca. 67 mg/g) of the suspended solids (As-containing solids) generated in the ZVI treatment of arsenic solutions were much higher than the specific surface area (ca. 37 m2/g) and adsorption capacity (ca.12 mg/g) of the suspended solids (As-free solids) generated in the arsenic-free solutions. Arsenic in the As-containing solids was much more stable than the adsorbed arsenic in As-free solids. XRD, SEM, TEM, and selected area electron diffraction (SAED) analyses showed that the As-containing solids consisted of amorphous nanoparticles, while the As-free solids were composed of micron particles with weak crystallinity. Extended X-ray absorption fine structure (EXAFS) analysis determined that As(V) was adsorbed on the As-containing suspended solids and magnetic solid surfaces through bidentate binuclear complexation; and As(V) formed a mononuclear complex on the As-free suspended solids. The formation of the surface As(V) complexes retarded the bonding of free FeO6 octahedra to the oxygen sites on FeO6 octahedral clusters and prevented the growth of the clusters and their development into 3-dimensional crystalline phases.

Fluoride removal by Al, Ti, and Fe hydroxides and coexisting ion effect.

Batch experiments were conducted to evaluate fluoride removal by Al, Fe, and Ti-based coagulants and adsorbents, as well as the effects of coexisting ions and formation of aluminum-fluoride complexes on fluoride removal by co-precipitation with alum (Al2(SO4)3·18H2O). Aluminum sulfate was more efficient than the other coagulants for fluoride removal in the pH range between 6 and 8. Nano-crystalline TiO2 was more effective for fluoride removal than Al and Fe hydroxides in a pH range of 3-5. Coexisting anions in water decreased the removal of fluoride in the order: phosphate (2.5mg/L)>arsenate (0.1mg/L)>bicarbonate (200mg/L)>sulfate (100mg/L)=nitrate (100mg/L)>silicate (10mg/L) at a pH of 6.0. The effect of silicate became more significant at pH>7.0. Calcium and magnesium improved the removal of fluoride. Zeta-potential measurements determined that the adsorption of fluoride shifted the PZC of Al(OH)3 precipitates from 8.9 to 8.4, indicating the chemical adsorption of fluoride at the surface. The presence of fluoride in solution significantly increased the soluble aluminum concentration at pH<6.5. A Visual MINTEQ modeling study indicated that the increased aluminum solubility was caused by the formation of AlF2+, AlF2+, and AlF3 complexes. The AlFx complexes decreased the removal of fluoride during co-precipitation with aluminum sulfate.

Adsorption of Ca2+ on single layer graphene oxide.

Graphene oxide (GO) holds great promise for a broad array of applications in many fields, but also poses serious potential risks to human health and the environment. In this study, the adsorptive properties of GO toward Ca2+ and Na+ were investigated using batch adsorption experiments, zeta potential measurements, and spectroscopic analysis. When pH increased from 4 to 9, Ca2+ adsorption by GO and the zeta potential of GO increased significantly. Raman spectra suggest that Ca2+ was strongly adsorbed on the GO via -COOCa+ formation. On the other hand, Na+ was adsorbed into the electrical diffuse layer as an inert counterion to increase the diffuse layer zeta potential. While the GO suspension became unstable with increasing pH from 4 to 10 in the presence of Ca2+, it was more stable at higher pH in the NaCl solution. The findings of this research provide insights in the adsorption of Ca2+ on GO and fundamental basis for prediction of its effect on the colloidal stability of GO in the environment.

Decolorization of Methyl Orange by a new clay-supported nanoscale zero-valent iron: Synergetic effect, efficiency optimization and mechanism.

In this study, a novel nanoscale zero-valent iron (nZVI) composite material was successfully synthesized using a low-cost natural clay, "Hangjin 2# clay" (HJ clay) as the support and tested for the decolorization of the azo dye Methyl Orange (MO) in aqueous solution by nZVI particles. According to the characterization and MO decolorization experiments, the sample with 5:1 HJ clay-supported nZVI (HJ/nZVI) mass ratio (HJ-nZVI5) showed the best dispersion and reactivity and the highest MO decolorization efficiency. With the same equivalent Fe0 dosage, the HJ-nZVI1 and HJ-nZVI5 samples demonstrated a synergetic effect for the decolorization of MO: their decolorization efficiencies were much higher than that achieved by physical mixing of HJ clay and nZVIs, or the sum of HJ clay and nZVIs alone. The synergetic effect was primarily due to the improved dispersion and more effective utilization of the nZVI particles on/in the composite materials. Higher decolorization efficiency of MO was obtained at larger HJ-nZVI dosage, higher temperature and under N2 atmosphere, while the MO initial concentration and pH were negatively correlated to the efficiency. HJ clay not only works as a carrier for nZVI nanoparticles, but also contributes to the decolorization through an "adsorption-enhanced reduction" mechanism. The high efficiency of HJ-nZVI for decontamination gives it great potential for use in a variety of remediation applications.

Phosphate recovery from anaerobic digester effluents using CaMg(OH)4.

Dolomite lime (DL) (CaMg(OH)4) was used as an economical source of Mg(2+) for the removal and recovery of phosphate from an anaerobic digester effluent of a municipal wastewater treatment plant (MWWTP) wastewater. Batch precipitation results determined that phosphate was effectively reduced from 87 to less than 4mg-P/L when the effluent water was mixed with 0.3g/L of DL. The competitive precipitation mechanisms of different solids in the treatment system consisting of Ca(2+)-Mg(2+)-NH4(+)-PO4(3-)CO3(2-) were determined by comparing model predictions with experimental results. Thermodynamic model calculations indicated that hydroxyapatite (Ca10(PO4)6(OH)2), Ca4H(PO4)3∙3H2O, Ca3(PO4)2(beta), and Ca3(PO4)2(am2) were more stable than struvite (MgNH4PO3∙6H2O) and calcite (CaCO3). However, X-ray diffraction (XRD) analysis determined the formation of struvite and calcite minerals in the treated effluent. Kinetic experimental results showed that most of the phosphate was removed from synthetic effluent containing NH4(+) within 2hr, while only 20% of the PO4(3-) was removed in the absence of NH4(+) after 24hr of treatment. The formation of struvite in the DL-treated effluent was due to the rapid precipitation rate of the mineral. The final pH of the DL-treated effluent significantly influenced the mass ratio of struvite to calcite in the precipitates. Because more calcite was formed when the pH increased from 8.4 to 9.6, a pH range of 8.0-8.5 should be used to produce solid with high PO4(3-) content. This study demonstrated that DL could be used for effective removal of phosphate from the effluent and that resultant precipitates contained high content of phosphate and ammonium.

DDT Vertical Migration and Formation of Accumulation Layer in Pesticide-Producing Sites.

Soil samples were collected at various depths (0.5-21.5 m) from ten boreholes that were drilled with a SH-30 Model Rig, four of which were at a dicofol production site while six were at a dichlorodiphenyltrichloroethane (DDT) production site. In industrial sites, the shallow soils at depths of 0-2 m were mostly backfill soils, which cannot represent the contamination situation of the sites. The contaminated levels in the deep original soil can represent the situation in contaminated sites. All the soil samples investigated at the DDT and dicofol production sites were found to be seriously polluted. The contents of both DDT (0.6-6071 mg/kg) and dicofol (0.5-1440 mg/kg) were much higher at the dicofol production site than at the DDT production site (DDTs, 0.01-664.6 mg/kg; dicofol, <0.1 mg/kg), even in the deep soil. DDTs had a different distribution in the soil of the pesticide production site from that in the soil outside the sites and that in agricultural soils. The results of the investigation revealed that DDTs were easily enriched in cohesive soil and in the bottom zone of aquifers, where the concentration was higher than in above the layers. DDTs were found to be hard to degrade, and their degradation speed was slower than their vertical migration, despite the fact that hydrophobic DDTs did not migrate easily in soils. In the dicofol production site, the value of DDE/DDD cannot indicate the degradation condition of DDTs, nor can the value of (DDE + DDD)/DDT identify how long DDTs have remained in the soil. It is debatable that the half-life of DDT inputted to soils is about 20-30 years, maybe longer than the generally recognized time.

Metals Bioaccumulation Mechanism in Neem Bark.

The aim of this work was to define the bioaccumulation mechanism of metals onto the non-living biomaterial prepared from an extensively available plant bark biomass of neem (Azadirachta indica). Based on maximum ultimate fixation capacities (mmol/g) of the product, metals ions could be arranged as Hg(2+) < Cd(2+) < Pb(2+) ≅ Cu(2+). Surface properties of the biomaterial were characterized by X-ray photoelectron spectroscopy and X-ray diffraction techniques for their sorption mechanism. Whewellite (C2CaO4 · H2O) was identified in the biomaterial, which indicated that calcium ions are electrovalently bonded with carboxylate ions facilitating the ion exchange mechanism with metal ions. Bioaccumulation of metal ions was also studied by Fourier transform infrared spectroscopy, which indicated the presence of functional groups implicated in adsorbing metal ions. Biomaterial did not adsorb anionic As(III), As(V) and Cr(VI), because of their electrostatic repulsion with carboxylic functional groups. Neem bark can be used as bioindicators, bioaccumulators and biomonitors while determining environmental pressures. Metal bioaccumulative properties and structural investigation of plant bark has potential in providing quantitative information on the metal contamination in the surrounding environment.

SERS detection of arsenic in water: A review.

Arsenic (As) is one of the most toxic contaminants found in the environment. Development of novel detection methods for As species in water with the potential for field use has been an urgent need in recent years. In past decades, surface-enhanced Raman scattering (SERS) has gained a reputation as one of the most sensitive spectroscopic methods for chemical and biomolecular sensing. The SERS technique has emerged as an extremely promising solution for in-situ detection of arsenic species in the field, particularly when coupled with portable/handheld Raman spectrometers. In this article, the recent advances in SERS analysis of arsenic species in water media are reviewed, and the potential of this technique for fast screening and field testing of arsenic-contaminated environmental water samples is discussed. The problems that remain in the field are also discussed and an outlook for the future is featured at the end of the article.

Spectrophotometric analyses of hexahydro-1,3,5-trinitro-1,3,5-triazine (RDX) in water.

A simple and accurate spectrophotometric method for on-site analysis of royal demolition explosive (RDX) in water samples was developed based on the Berthelot reaction. The sensitivity and accuracy of an existing spectrophotometric method was improved by: replacing toxic chemicals with more stable and safer reagents; optimizing the reagent dose and reaction time; improving color stability; and eliminating the interference from inorganic nitrogen compounds in water samples. Cation and anion exchange resin cartridges were developed and used for sample pretreatment to eliminate the effect of ammonia and nitrate on RDX analyses. The detection limit of the method was determined to be 100 µg/L. The method was used successfully for analysis of RDX in untreated industrial wastewater samples. It can be used for on-site monitoring of RDX in wastewater for early detection of chemical spills and failure of wastewater treatment systems.

Bioregeneration of spent anion exchange resin for treatment of nitrate in water.

Anion exchange resin treatment is a commonly used technique for removal of nitrate from water. However, spent anion exchange resins are themselves regenerated using brine solution, which produces spent solution containing a high concentration of nitrate and salt. The present study developed a bioregeneration technique for conversion of nitrate on the spent resins to nitrogen gas while eliminating the use of brine solutions. Batch experiments were conducted to investigate the effect of biomass content, pH, salinity, and molar ratio of exogenous organic carbon to nitrate on the kinetics of bioregeneration. The bioregeneration rate decreased when pH increased from 7 to 10. It increased with increasing microbial concentration from 8.3 to 13.8 g/L as volatile suspended solid (VSS) and with decreasing conductivity of the regeneration suspension from 31 to 9 mS/cm. Spent exchange resins were effectively regenerated within 5 h under the optimal conditions and the regenerated resins could be used repeatedly for filtration removal of nitrate from water. A desorption-denitrification model was developed to describe bioregeneration kinetics. Modeling results indicated that the bioregeneration was through desorption of nitrate from the spent resin and subsequent denitrification of the soluble nitrate. Denitrification was the rate-limiting process. This research demonstrated the feasibility of using a biological process to regenerate nitrate-saturated resins.