Degradation and fate of 2,4-dinitroanisole (DNAN) and its intermediates treated with Mg/Cu bimetal: Surface examination with XAS, DFT, and LDI-MS.

A novel Mg-based bimetal reagent (Mg/Cu) was used as an enhanced reductive system to degrade insensitive munition 2,4-dinitroanisole (DNAN), a contaminant found in energetic-laden waste. Degradation of DNAN was significantly impacted by dissolved oxygen and studied in anoxic and oxic bimetal systems (i.e., purging with N2, air, or O2 gas). Degradation occurred through sequential nitroreduction: first one nitro group was reduced (ortho or para) to form short-lived intermediates 2-amino-4-nitroanisole or 4-amino-2-nitroanisole (2-ANAN or 4-ANAN), and then subsequent reduction of the other nitro group formed 2,4-diaminoanisole (DAAN). The nitro-amino intermediates demonstrated regioselective reduction in the ortho position to 2-ANAN; Regioselectivity was also impacted by the anoxic/oxic environment. Under O2-purging DNAN degradation rate was slightly enhanced, but most notably O2 significantly accelerated DAAN generation. DAAN also further degraded only in the oxygenated Mg/Cu system. Adsorption of DNAN byproducts to the reagent occurred regardless of anoxic/oxic condition, resulting in a partition of carbon mass between the adsorbed phase (27%-35%) and dissolved phase (59%-72%). Additional surface techniques were applied to investigate contaminant interaction with Cu. Density functional theory (DFT) calculations identified preferential adsorption structures for DNAN on Cu with binding through two O atoms of one or both nitro groups. X-ray absorption spectroscopy (XAS) measurements determined the oxidation state of catalytic metal Cu and formation of a Cu-O-N bond during treatment. Laser desorption ionization mass spectrometry (LDI-MS) measurements also identified intermediate 2-ANAN adsorbed to the bimetal surface.

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.

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.

Evidence for Phytoremediation and Phytoexcretion of NTO from Industrial Wastewater by Vetiver Grass.

The use of insensitive munitions such as 3-nitro-1,2,4-triazol-5-one (NTO) is rapidly increasing and is expected to replace conventional munitions in the near future. Various NTO treatment technologies are being developed for the treatment of wastewater from industrial munition facilities. This is the first study to explore the potential phytoremediation of industrial NTO-wastewater using vetiver grass (Chrysopogon zizanioides L.). Here, we present evidence that vetiver can effectively remove NTO from wastewater, and also translocated NTO from root to shoot. NTO was phytotoxic and resulted in a loss of plant biomass and chlorophyll. The metabolomic analysis showed significant differences between treated and control samples, with the upregulation of specific pathways such as glycerophosphate metabolism and amino acid metabolism, providing a glimpse into the stress alleviation strategy of vetiver. One of the mechanisms of NTO stress reduction was the excretion of solid crystals. Scanning electron microscopy (SEM), electrospray ionization mass spectrometry (ESI-MS), and Fourier-transform infrared spectroscopy (FTIR) analysis confirmed the presence of NTO crystals in the plant exudates. Further characterization of the exudates is in progress to ascertain the purity of these crystals, and if vetiver could be used for phytomining NTO from industrial wastewater.

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.

Unrefined and Milled Ilmenite as a Cost-Effective Photocatalyst for UV-Assisted Destruction and Mineralization of PFAS.

Per- and polyfluoroalkyl substances (PFAS) are fluorinated and refractory pollutants that are ubiquitous in industrial wastewater. Photocatalytic destruction of such pollutants with catalysts such as TiO2 and ZnO is an attractive avenue for removal of PFAS, but refined forms of such photocatalysts are expensive. This study, for the first time, utilized milled unrefined raw mineral ilmenite, coupled to UV-C irradiation to achieve mineralization of the two model PFAS compounds perfluorooctanoic acid (PFOA) and perfluoro octane sulfonic acid (PFOS). Results obtained using a bench-scale photocatalytic reactor system demonstrated rapid removal kinetics of PFAS compounds (>90% removal in less than 10 h) in environmentally-relevant concentrations (200-1000 ppb). Raw ilmenite was reused over three consecutive degradation cycles of PFAS, retaining >80% removal efficiency. Analysis of degradation products indicated defluorination and the presence of shorter-chain PFAS intermediates in the initial samples. End samples indicated the disappearance of short-chain PFAS intermediates and further accumulation of fluoride ions, suggesting that original PFAS compounds underwent mineralization due to an oxygen-radical-based photocatalytic destruction mechanism induced by TiO2 present in ilmenite and UV irradiation. The outcome of this study implies that raw ilmenite coupled to UV-C is suitable for cost-effective reactor operation and efficient photocatalytic destruction of PFAS compounds.

On-Site Pilot-Scale Microalgae Cultivation Using Industrial Wastewater for Bioenergy Production: A Case Study towards Circular Bioeconomy.

This case study assesses the valorization of industrial wastewater streams for bioenergy generation in an industrial munition facility. On-site pilot-scale demonstrations were performed to investigate the feasibility of algal growth in the target wastewater on a larger outdoor scale. An exploratory field study followed by an optimized one were carried out using two 1000 L open raceway ponds deployed within a greenhouse at an industrial munition facility. An online system allowed for constant monitoring of operational parameters such as temperature, pH, light intensity, and dissolved oxygen within the ponds. The original algal seed evolved into an open-air resilient consortium of green microalgae and cyanobacteria that were identified and characterized successfully. Weekly measurements of the level of nutrients in pond liquors were performed along with the determination of the algal biomass to quantitatively evaluate growth yields. After harvesting algae from the ponds, the biomass was concentrated and evaluated for oil content and biochemical methane potential (BMP) to provide an estimate of the algae-based energy production. Additionally, the correlation among biomass, culturing conditions, oil content, and BMP was evaluated. The higher average areal biomass productivity achieved during the summer months was 23.9 ± 0.9 g/m2d, with a BMP of 350 scc/gVS. An oil content of 22 wt.% was observed during operation under low nitrogen loads. Furthermore, a technoeconomic analysis and life cycle assessment demonstrated the viability of the proposed wastewater valorization scenario and aided in optimizing process performance towards further scale-up.

Enhanced precipitation of magnesium carbonates using carbonic anhydrase.

Carbonate precipitation, as part of the carbon dioxide (CO2) mineralization process, is generally regarded as a high-temperature, high-pressure, and high-purity CO2 process. Typical conditions consist of temperatures around 120 °C and a pressure of 100 bar of pure CO2, making the process costly. A major challenge facing carbonate precipitation is performing the reaction at low temperatures and low partial pressures of CO2 (pCO2) such as 25 °C and CO2 flue gas concentration. In this work, we investigated the effect of carbonic anhydrase (CA) to favor magnesium (Mg) carbonate precipitation at low temperatures and low pCO2. CA is an enzyme that accelerates CO2 hydration promoting its conversion into HCO3- and then CO32-. This increases supersaturation with respect to Mg-carbonates. A geochemical model was implemented and used to identify supersaturated conditions with respect to Mg-carbonates. Tests were run at 25, 40, and 50 °C and at 1 bar of either pure CO2 or 10 vol% CO2 and 90 vol% N2. The concentration of 10 vol% CO2 was chosen to resemble CO2 concentration in flue gas. In selected tests, the CA enzyme was added directly as bovine CA or through microalgae (Scenedesmus obliquus). Experiments were run for 48 hours; 24 hours to reach equilibrium, then another 24 hours until the supersaturated conditions were established. After 48 hours the experiments were interrupted and the solids were characterized. Results show that the addition of CA, either directly or through Scenedesmus obliquus, enhances Mg-carbonate precipitation. Regardless of the temperature, the precipitates were made entirely of nesquehonite (MgCO3-3H2O) when pure CO2 was used. Otherwise, a solid solution containing brucite (Mg(OH)2) and MgCO3-3H2O was formed. Overall, these findings suggest that CA can promote carbonate precipitation at low temperatures, pressures, and CO2 purity. The enzyme is effective when added directly or supplied through microalgae, opening up the possibility for a CO2 mineralization process to be implemented directly at a combustion plant as a CO2 storage option without preliminary CO2 capture.

Oxidative degradation of nitroguanidine (NQ) by UV-C and oxidants: Hydrogen peroxide, persulfate and peroxymonosulfate.

Nitroguanidine (NQ), a component used in insensitive munitions formulations, has high solubility which often leads to highly contaminated wastewater streams. In this work, batch experiments were conducted to investigate and compare the NQ degradation by UV-based advanced oxidation processes (AOPs); hydrogen peroxide (H2O2), persulfate (PS) and peroxymonosulfate (PMS) were selected as oxidants. A preliminary evaluation of AOPs kinetics, byproducts, and potential degradation pathways were carried out and compared to NQ degradation by direct UV-C photolysis. The effects of oxidant dosage, NQ concentrations and pH were evaluated by determining the respective kinetic constants of degradation. Among the treatments applied, UV/PS showed to be a promising and effective alternative leading to faster rates of degradation respect to both oxidant dosage (25 mM) and initial NQ concentrations (≤24 mM). Nevertheless, the degradation rate of NQ by UV/PS appeared to be affected strongly by the initial pH compared to UV/H2O2 and UV/PMS, with the lowest rate overall at pH ≥ 8.0. In addition, the main byproducts from NQ degradation, guanidine and cyanamide, showed to be involved in further degradation steps only with UV/PS and UV/PMS suggesting higher degradation effectiveness of these oxidants compared UV/H2O2 and UV alone.

Tungsten speciation and toxicity: acute toxicity of mono- and poly-tungstates to fish.

Tungsten is a widely used transition metal for which very limited information on environmental and toxicological effects is available. Of particular interest is the lack of information linking tungsten speciation and environmental effects. Tungsten anions may polymerize (depending upon concentration, pH, and aquatic geochemistry) in aquatic and soil systems. However, to this date, of all soluble tungstate species only monotungstates have been scrutinized to a fair extent in toxicological studies. The objective of this work is a comparative assessment of the acute toxicity of monotungstates (sodium tungstate, Na(2)WO(4)) and polytungstates (sodium metatungstate, 3Na(2)WO(4).9WO(3)) to Poecilia reticulate. The experiments have been performed according to the OEDC protocols 203 and 204. LD50 values for 1-14 days show that sodium metatungstate is significantly more toxic to fish than sodium tungstate. Based on LD50 (0.86-3.88gL(-1) or 4.67-21.1x10(-3)molNa(2)WO(4)L(-1)), sodium tungstate may be classified as a chemical of low toxicity to fish. Sodium metatungstate caused similar fish mortality to sodium tungstate when it was introduced in 55-80 times lower concentrations (in terms of molL(-1)) than sodium tungstate. LD50 values for sodium metatungstate range from 0.13 to 0.85gWL(-1) or 5.69 to 38.71x10(-5)mol 3Na(2)WO(4).9WO(3)L(-1). Based on these values sodium metatungstate can be classified as a moderate toxic agent to fish.

Identifying the existence and molecular structure of the dissolved HCO3-Ca-As(V) complex in water.

Calcium (Ca2+) and bicarbonate (HCO3-) ions co-exist with arsenic (As) in natural water systems, while Ca-based materials such as lime and cement are widely used to immobilize As(V) in contaminated solids. In this paper, a new dissolved ternary complex, HCO3-Ca-As(V), was discovered and its molecular structure was identified. The results from the batch experiments showed that adding As(V) to the solutions containing Ca2+ and HCO3- increased the dissolved Ca concentration from 4.8 to 73.2 mg/L at pH 11. Both infrared and X-ray absorption spectroscopy indicated the presence of dissolved HCO3-Ca-As(V) complex. Based on the quantitative geometric information obtained from the spectroscopic results, the molecule of (OH)OC-O-(OH2)4Ca-O2-As(OH)2 was identified by the density functional theory (DFT) calculation. Although Ca2+ and As(V) can form complex without HCO3-, the presence of HCO3- further enhanced the stability of the dissolved Ca complex, as evidenced by the lower binding energy (BE) of HCO3-Ca-As(V) (-329.1959 kJ/mol) than Ca-As(V) (4.7171 kJ/mol). The discovery of dissolved HCO3-Ca-As(V) complex is important for understanding the mobility of As(V) in natural water, and the possible release of As(V) in contaminated solids treated with Ca-based materials.

Lead immobilization by phosphate in the presence of iron oxides: Adsorption versus precipitation.

As a commonly used corrosion inhibitor, phosphate (PO4) has a complicated effect on the fate and transport of lead (Pb) in drinking water systems. While the formation of pyromorphite has been recognized to be the major driving force of the Pb immobilization mechanism, the role of adsorption on iron oxides is still not clear. This study aims to clarify the contributions of adsorption and precipitation to Pb removal in a system containing both iron oxides and PO4. A combination of batch experiments, X-ray absorption spectroscopy, infrared spectroscopy, and electron spectroscopy was employed to distinguish the adsorbed and precipitated Pb species. The results indicated that the adsorption of Pb on iron oxides still occurred even when the solution was supersaturated to pyromorphite (i.e., 5 mg/L P with 0.1-30 mg/L Pb in 0.01 M NaCl solution at neutral pH). In the tap water containing 0.92 mg/L P and 1 mg/L Pb, adsorption on iron oxides contributed more (62-67%) than precipitation (33-38%) in terms of Pb removal. Surprisingly, the pre-formed pyromorphite is transformed to adsorbed species after mixing with iron oxides in water for 24 h. The illustration of this transformation is important to understand the immobilization mechanisms and transport behaviors of Pb in drinking water systems after the utilization of PO4.

Facilitated transport of nTiO2-kaolin aggregates by bacteria and phosphate in water-saturated quartz sand.

The soil major component of clay plays an important role in governing the fate and transport of engineered nanomaterials (e.g., the most commonly used titanium dioxide nanoparticles; nTiO2) in the subsurface environments via forming nTiO2-clay aggregates. This research is designed to unravel the interplay of naturally-occurring bacteria (Escherichia coli) and phosphate on the transport and retention of nTiO2-kaolin aggregates in water-saturated porous media. Our results showed that nTiO2-nTiO2 homoaggregates and nTiO2-kaolin heteroaggregates dominated in the nTiO2-kaolin nanoaggregate suspension. Transport of nTiO2-kaolin aggregates was enhanced with the copresence of E. coli and phosphate, particularly at the low pH of 6.0. This effect is due to the greater adsorption of phosphate and thus the greater enhancement in repulsive interaction energies between aggregates and sand grains at pH 6.0 (vs. pH 9.0). The charged "soft layer" of E. coli cell surfaces changed the aggregation state and the heterogeneous distribution of nTiO2-kaolin aggregates, and subsequently stabilized the nTiO2-nTiO2 homoaggregates and nTiO2-kaolin heteroaggregates via TEM-EDX measurements and promoted the physical segregation between the aggregates (separation distance = 0.486 vs. 0.614 µm without vs. with the presence of E. coli) via 2D/3D AFM identifications, both of which caused greater mobility of nTiO2-kaolin aggregates with the presence of E. coli. Nonetheless, transport of nTiO2-kaolin aggregates was lower with the copresence of E. coli and phosphate vs. the singular presence of phosphate due to the competitive adsorption of less negatively charged E. coli (vs. phosphate) onto the aggregates. Taken altogether, our findings furnish new insights into better understanding the fate, transport, and potential risks of nTiO2 in real environmental settings (soil and sediment aquifer) where clay, bacteria, and phosphate ubiquitously cooccur.

The use of ultra high-performance liquid chromatography for studying hydrolysis kinetics of CL-20 and related energetic compounds.

Ultra high-performance liquid chromatography (UHPLC) utilizes columns packed with sub-2-mum stationary-phase particles and allows operation with pressures of up to 15,000 psi to yield increased resolution, speed, and sensitivity versus conventional HPLC. This promising new technology was used for the analysis of energetic compounds (RDX, HMX and CL-20) and a selective method was developed on an Acquity UPLC. A fast UHPLC method was applied to determine alkaline hydrolysis reaction kinetics of major energetic compounds. Activation energies of alkaline hydrolysis reaction for CL-20, RDX and HMX were comparable to those in literature, however they were determined in a shorter amount of time due to the speed of analysis of the chromatographic method. The use of liophilic salts (KPF(6)) as mobile-phase additives for the enhancement of separation selectivity of energetic compounds was demonstrated.

Removal of arsenic using functionalized cellulose nanofibrils from aqueous solutions.

Cellulose nanofibrils (CNF) functionalized by introduction of trimethylammonium chloride were investigated for the uptake of arsenate [As(V)] from aqueous solutions. The modified-CNF was characterized using Energy Dispersive Spectrometry (EDS), argentometric titration, Boehr titration, zeta-potential, Scanning Electron Microscopy (SEM), Fourrier Transform Infrared (FTIR) spectroscopy, Nuclear Magnetic Resonance (NMR) spectroscopy, Brunauer-Emmet-Teller (BET), and Dynamic Light Scattering (DLS). The modified-CNF was effective for As(V) removal from laboratory and field samples. The As(V) adsorption was rapid and equilibrium was attained within two hours. The kinetic data were adequately described by the pseudo-second-order kinetics model suggesting that As(V) adsorption onto modified-CNF involves electrostatic forces and bonds between As(V) and adsorption sites. The adsorption isotherm data were well correlated with model. The modified-CNF exhibited an As(V) adsorption capacity (qe) of approximately 25.5 mg g-1. Competitive adsorption between As(V) and anions including NO2-, NO3-, and SO42- was investigated and the results showed negligible influence on As(V) removal. However, PO43- presence slightly reduced As(V) adsorption. Thermodynamics study showed that the As(V) adsorption onto modified-CNF is temperature dependent and is spontaneous and exothermic. Overall, the results of this study demonstrated that modified-CNF offers a propitious alterative for As(V) removal from water.

Lead and cadmium adsorption by electrospun PVA/PAA nanofibers: Batch, spectroscopic, and modeling study.

Water-stable PVA/PAA nanofibers were fabricated through electrospinning and evaluated for their performance in lead (Pb(II)) and cadmium (Cd(II)) removal from water in a batch experiment. The adsorption mechanism of Pb(II) was explored using the extended X-ray absorption fine structure (EXAFS) spectroscopic analysis. The PVA/PAA nanofibers showed a pH-dependent behavior for heavy metal removal, and its adsorption capacities for Pb(II) and Cd(II) could reach as high as 159 and 102 mg/g, respectively. The calcium ion (Ca(II)) had no effect on Pb(II) removal at pH 5.0 whereas it significantly reduced Cd(II) removal at pH 7.0. The adsorption of Pb(II) and Cd(II) was spontaneous and exothermic in nature with a decrease in randomness. The saturated PVA/PAA nanofibers could be regenerated using acidic solutions for reuse. The Fourier-transform infrared (FTIR) spectroscopic analysis indicated the formation of surface complexes between adsorbed Pb(II) and Cd(II) and carboxyl groups on PVA/PAA nanofibers. Moreover, EXAFS analysis suggested that a Pb(II) cation was chelated with three carboxyl groups on the nanofibers. This molecular-level adsorption structure was successfully implemented into a surface complexation model for the prediction of the macroscopic Pb(II) and Cd(II) adsorption behaviors. The results gained from this study provided complementary information on heavy metal removal by a new generation of adsorbents and improved the fundamental understanding for the removal process.

Evaluation of metal oxides and activated carbon for lead removal: Kinetics, isotherms, column tests, and the role of co-existing ions.

Activated carbon (AC) is commonly used in faucet and pitcher filters for lead (Pb(II)) removal in homes. This study evaluated the Pb(II) removal performance of AC and metal oxides (e.g. Fe(OH)3 and TiO2), as well as the co-existing ions' effect on Pb(II) removal. Results showed that metal oxides had higher adsorption capacity (28.9-51.5 mg/g) than AC (21.2 mg/g). Pb(II) was inner-spherically adsorbed onto both AC and metal oxides surfaces. Among various metal ions, calcium (Ca(II)) demonstrated dramatic effects on Pb(II) removal ability of AC, while it had no effect on Pb(II) adsorption by metal oxides. This difference resulted from the inner- and outer-sphere adsorption of Ca(II) on AC and metal oxides, respectively. The presence of orthophosphate (orth-P) and sulfate enhanced Pb(II) removal by those three adsorbents, whereas carbonate and silicate had negligible effect on Pb(II) adsorption. Interestingly, while the orth-P was usually used as corrosion inhibitor because of the formation of lead-phosphate coprecipitate, we found that the enhanced effect of orth-P on Pb(II) removal was mainly due to the synergistic adsorption. This study provides valuable information for the selection of effective adsorbents for Pb(II) removal and is helpful for understanding the roles of co-existing ions on it.

Particle size and pH effects on remediation of chromite ore processing residue using calcium polysulfide (CaS5).

A long-term bench scale treatability study was performed to assess the ability to remediate chromite ore processing residue (COPR) using calcium polysulfide (CaS(5)). COPR materials were characterized with respect to particle size, pH, curing period and mineralogy. A stoichiometric ratio of sulfide species to hexavalent chromium (Cr(6+)) of 2 was used for the long-term treatment of COPR. The effectiveness of CaS(5) treatment was assessed using the toxicity characteristic leaching procedure (TCLP), alkaline digestion, and X-ray absorption near edge structure (XANES) analyses. The formation of ettringite, known as a heaving agent, was investigated following the treatment of CaS(5), using X-ray powder diffraction (XRPD) and scanning electron microscopy (SEM) along with an energy dispersive X-ray spectroscopy (EDX). Overall, after a curing period of 18 months, the TCLP total chromium (Cr) and alkaline digestion (Cr(6+)) results obtained from the treatability study showed that the concentrations were lower than 5 mg L(-1) and 9 mg kg(-1), respectively. However, XANES results obtained from samples cured for 18 months showed that all of the treated samples had higher Cr(6+) concentrations than shown using alkaline digestion. The lowest XANES Cr(6+) concentration of 610.2 mg kg(-1) was obtained from the sample with a particle size less than 0.075 mm and a pH value of 9. Particle size reduction prior to the addition of the reductant, along with pH reduction was found to be strongly associated with the treatment performance. Ettringite formation, due to pH increase over time in the samples, where the initial pH was adjusted to 9, was verified by XRPD and SEM-EDX analyses, indicating that a pH less than 9 should be maintained to avoid ettringite formation.

Leaching mechanisms of Cr(VI) from chromite ore processing residue.

Batch leaching tests, qualitative and quantitative x-ray powder diffraction (XRPD) analyses, and geochemical modeling were used to investigate the leaching mechanisms of Cr(VI) from chromite ore processing residue (COPR) samples obtained from an urban area in Hudson County, New Jersey. The pH of the leaching solutions was adjusted to cover a wide range between 1 and 12.5. The concentration levels for total chromium (Cr) and Cr(VI) in the leaching solutions were virtually identical for pH values >5. For pH values <5, the concentration of total Cr exceeded that of Cr(VI) with the difference between the two attributed to Cr(III). Geochemical modeling results indicated that the solubility of Cr(VI) is controlled by Cr(VI)-hydrocalumite and Cr(VI)-ettringite at pH >10.5 and by adsorption at pH <8. However, experimental results suggested that Cr(VI) solubility is controlled partially by Cr(VI)-hydrocalumite at pH >10.5 and by hydrotalcites at pH >8 in addition to adsorption of anionic chromate species onto inherently present metal oxides and hydroxides at pH <8. As pH decreased to <10, most of the Cr(VI) bearing minerals become unstable and their dissolution contributes to the increase in Cr(VI) concentration in the leachate solution. At low pH ( <1.5), Cr(III) solid phases and the oxides responsible for Cr(VI) adsorption dissolve and release Cr(III) and Cr(VI) into solution.

Synergistic effects of phosphorus and humic acid on the transport of anatase titanium dioxide nanoparticles in water-saturated porous media.

The (un)intentional release of titanium dioxide nanoparticles (TiO2 NPs) poses potential risks to the environment and human health. Phosphorus (P) and humic acid (HA) usually coexist in the natural environments. This study aims at investigating the transport and retention behaviors of TiO2 NPs in the single and binary systems of P and HA in water-saturated porous media. The experimental results showed that HA alone favored the transport of TiO2 NPs in sand columns to a greater extent than that of P alone at pH 6.0. Interestingly, the co-presence of P and HA acting in a synergistic fashion enhanced the transport of TiO2 NPs in sand-packed columns more significantly compared to that in the single-presence of P or HA. Particularly, P plays a dominant role in the synergistic effect. This is largely due to the competitive effect between P and HA for the same adsorption sites on the sand surfaces favorable for TiO2 NPs retention. A two-site kinetic attachment model that considers Langmuirian blocking of particles at one site provided a good approximation of TiO2 NPs transport. Modeled first-order attachment coefficient (k2) and the maximum solid-phase retention capacity on site 2 (Smax2) for P or HA alone were larger than those in the co-presence of P and HA, suggesting a less retention degree of TiO2 NPs in the binary system of P and HA. Our findings indicate that the mobility of TiO2 NPs is expected to be appreciable in soil and water environments, where P and HA are rich and always co-present at low pH conditions.