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.

Assessment of soil washing for heavy metal contaminated paddy soil using FeCl3 washing solutions.

In this study, soil washing is applied for the remediation of heavy-metal (Pb, Cu and Zn) contaminated paddy soil located near an abandoned mine area. FeCl3 washing solutions were used in bench-scale soil washing experiments at concentrations in the range of 0.1 to 1 M. The strong acid, HCl was also used in this study for comparison. The washing process was performed at room temperature, mixing at 200 RPM for 1 h and a liquid to solid ratio of 2. A sequential extraction technique was performed to evaluate the chemical fractions of Pb in the soils. The soil washing effectiveness was evaluated and compared against regulations applicable to residential districts (Korean warning standards). The soil washing results showed that the heavy metal concentrations were reduced with increasing concentrations of FeCl3. Moreover, the lowest heavy metal concentrations were obtained with a 1 M FeCl3 washing solution. In the case of Pb removal, a 0.3 M FeCl3 washing solution was required to comply with the Korean warning standard of 200 mg/kg. The lowest Pb concentration of 117 mg/kg was obtained with 1 M FeCl3. Similar washing results were also obtained with HCl. The initial total concentrations for Cu and Zn were below the Korean warning standards of 150 and 300 mg/kg, respectively. Consequently, the reduction in Cu and Zn from the contaminated paddy soil using FeCl3 washing solutions was rather limited. The sequential extraction results showed that the exchangeable and weak acid-soluble fractions of Pb were significantly reduced upon FeCl3 washing.

Impacts of biochar application on upland agriculture: A review.

Soil degradation has become an emerging global problem limiting sustainable upland crop production. Soil erosion, soil acidity, low fertility, inorganic/organic contamination, and salinization challenge food security and lead to severe economic constraints. Therefore, a new research agenda to develop cost-beneficial amendments for improving upland soil quality and productivity is urgently required. Biochar has been used in recent years to mitigate the problems mentioned above. Application of biochar improves the upland soil quality through significant changes in soil physicochemical and biological properties, thereby substantially increasing crop yield. This review article aims to discuss the effects of biochar on upland soil quality and productivity based on biochar-soil interactions. The yield of various upland crops can be enhanced by biochar-induced increases of nutrient availability and topsoil retention/recovery. Furthermore, biochar can assist in controlling unsuitable soil acidity/alkalinity/salinity and remediating a contaminated soil while increasing the retention of soil organic carbon, water content, and thereby high crop yield. Biochar is strongly recommended as one of the best management practices to meet the challenges of upland agriculture. However, the properties of biochar and soil type should be considered carefully prior to application.

Soil washing of fluorine contaminated soil using various washing solutions.

Bench-scale soil washing experiments were conducted to remove fluoride from contaminated soils. Five washing solutions including hydrochloric acid (HCl), nitric acid (HNO3), sodium hydroxide (NaOH), sulfuric acid (H2SO4) and tartaric acid (C4H6O6) were tested. The concentration of the washing solutions used ranged from 0.1 to 3 M with a liquid to solid ratio of 10. The soil washing results showed that the most effective washing solution for the removal of fluoride from contaminated soils was HCl. The highest fluoride removal results of approximately 97 % from the contaminated soil were obtained using 3 M HCl. The fluoride removal efficiency of the washing solution increases in the following order: C4H6O6 < NaOH < H2SO4 < HNO3 < HCl.

Stabilization of lead and copper contaminated firing range soil using calcined oyster shells and fly ash.

A stabilization/solidification treatment scheme was devised to stabilize Pb and Cu contaminated soil from a firing range using renewable waste resources as additives, namely waste oyster shells (WOS) and fly ash (FA). The WOS, serving as the primary stabilizing agent, was pre-treated at a high temperature to activate quicklime from calcite. Class C FA was used as a secondary additive along with the calcined oyster shells (COS). The effectiveness of the treatment was evaluated by means of the toxicity characteristic leaching procedure (TCLP) and the 0.1 M HCl extraction tests following a curing period of 28 days. The combined treatment with 10 wt% COS and 5 wt% FA cause a significant reduction in Pb (>98 %) and Cu (>96 %) leachability which was indicated by the results from both extraction tests (TCLP and 0.1 M HCl). Scanning electron microscopy-energy dispersive X-ray spectroscopy (SEM-EDX) analyses are used to investigate the mechanism responsible for Pb and Cu stabilization. SEM-EDX results indicate that effective Pb and Cu immobilization using the combined COS-FA treatment is most probably associated with ettringite and pozzolanic reaction products. The treatment results suggest that the combined COS-FA treatment is a cost effective method for the stabilization of firing range soil.

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.

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.

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.

Hexahydro-1,3,5-trinitro-1,3,5-triazine (RDX) reduction by granular zero-valent iron in continuous flow reactor.

Wastewater streams containing hexahydro-1,3,5-trinitro-1,3,5-triazine (RDX) are subject to regulatory discharge regulations that require processing through industrial waste treatment. Thus, the development of easy-to-apply technologies for the treatment of RDX-laden wastewater streams is imperative. In the present study, the reduction of RDX by granular zero valent iron (GZVI) in batch and column experiments was investigated. Preliminary batch tests conducted under both oxic and anoxic conditions showed that after 3.0 h of reaction with GZVI, RDX was mainly converted to formaldehyde (CH2O), nitrate (NO3-), and ammonium (NH4+). Column filtration tests showed that pretreatment of the GZVI media with acid wash and low influent pH (4.0 ± 0.1) achieved 99% removal of RDX up to 5000 bed volume. BOD tests carried out on the post-treatment streams showed increased biodegradability of the treated wastewater, leading to a lower environmental impact for the final waste.

Characterization of Mg-based bimetal treatment of insensitive munition 2,4-dinitroanisole.

The manufacturing of insensitive munition 2,4-dinitroanisole (DNAN) generates waste streams that require treatment. DNAN has been treated previously with zero-valent iron (ZVI) and Fe-based bimetals. Use of Mg-based bimetals offers certain advantages including potential higher reactivity and relative insensitivity to pH conditions. This work reports preliminary findings of DNAN degradation by three Mg-based bimetals: Mg/Cu, Mg/Ni, and Mg/Zn. Treatment of DNAN by all three bimetals is highly effective in aqueous solutions (> 89% removal) and wastewater (> 91% removal) in comparison with treatment solely with zero-valent magnesium (ZVMg; 35% removal). Investigation of reaction byproducts supports a partial degradation pathway involving reduction of the ortho or para nitro to amino group, leading to 2-amino-4-nitroanisole (2-ANAN) and 4-amino-2-nitroanisole (4-ANAN). Further reduction of the second nitro group leads to 2,4-diaminoanisole (DAAN). These byproducts are detected in small quantities in the aqueous phase. Carbon mass balance analysis suggests near-complete closure (91%) with 12.4 and 78.4% of the total organic carbon (TOC) distributed in the aqueous and mineral bimetal phases, respectively. Post-treatment surface mineral phase analysis indicates Mg(OH)2 as the main oxidized species; oxide formation does not appear to impair treatment.

Stabilization of lead (Pb) and zinc (Zn) in contaminated rice paddy soil using starfish: A preliminary study.

Lead (Pb) and zinc (Zn) contaminated rice paddy soil was stabilized using natural (NSF) and calcined starfish (CSF). Contaminated soil was treated with NSF in the range of 0-10 wt% and CSF in the range of 0-5 wt% and cured for 28 days. Toxicity characteristic leaching procedure (TCLP) test was used to evaluate effectiveness of starfish treatment. Scanning electron microscopy-energy dispersive X-ray spectroscopy (SEM-EDX) analyses were conducted to investigate the mechanism responsible for effective immobilization of Pb and Zn. Experimental results suggest that NSF and CSF treatments effectively immobilize Pb and Zn in treated rice paddy soil. TCLP levels for Pb and Zn were reduced with increasing NSF and CSF dosage. Comparison of the two treatment methods reveals that CSF treatment is more effective than NSF treatment. Leachability of the two metals is reduced approximately 58% for Pb and 51% for Zn, upon 10 wt% NSF treatment. More pronounced leachability reductions, 93% for Pb and 76% for Zn, are achieved upon treatment with 5 wt% CSF. Sequential extraction results reveal that NSF and CSF treatments of contaminated soil generated decrease in exchangeable/weak acid Pb and Zn soluble fractions, and increase of residual Pb and Zn fractions. Results for the SEM-EDX sample treated with 5 wt% CSF indicate that effective Pb and Zn immobilization is most probably associated with calcium silicate hydrates (CSHs) and calcium aluminum hydrates (CAHs).

Quality improvement of acidic soils by biochar derived from renewable materials.

Biochar derived from waste plant materials and agricultural residues was used to improve the quality of an acidic soil. The acidic soil was treated for 1 month with both soy bean stover-derived biochar and oak-derived biochar in the range of 1 to 5 wt% for pH improvement and exchangeable cation enhancement. Following 1 month of treatment, the soil pH was monitored and exchangeable cations were measured. Moreover, a maize growth experiment was performed for 14 days with selected treated soil samples to confirm the effectiveness of the treatment. The results showed that the pH of the treated acidic soil increased by more than 2 units, and the exchangeable cation values were greatly enhanced upon treatment with 5 wt% of both biochars, after 1 month of curing. Maize growth was superior in the 3 wt% biochar-treated samples compared to the control sample. The presented results demonstrate the effective use of biochar derived from renewable materials such as waste plant materials and agricultural residues for quality improvement of acidic soils.

Assessment of waste oyster shells and coal mine drainage sludge for the stabilization of As-, Pb-, and Cu-contaminated soil.

A novel treatment mix was designed for the simultaneous immobilization of As, Cu, and Pb in contaminated soils using natural (waste oyster shells (WOS)) and industrial (coal mine drainage sludge (CMDS)) waste materials. The treatments were conducted using the standard U.S. sieve size no. 20 (0.85 mm) calcined oyster shells (COS) and CMDS materials with a curing time of 1 and 28 days. The As immobilization treatments were evaluated using the 1-N HCl extraction fluid, whereas the Pb and Cu immobilization treatments were evaluated using the 0.1-N HCl extraction fluid based on the Korean leaching standards. The treatment results showed that the immobilization of As, Cu, and Pb was best achieved using a combination mix of 10 wt% COS and 10 wt% CMDS. This treatment mix was highly effective leading to superior leachability reductions for all three target contaminants (>93 % for As and >99 % for Cu and Pb) for a curing period of 28 days. The X-ray absorption near-edge structure (XANES) results showed that As was present in the form of As(V) in the control sample and that no changes in As speciation were observed following the COS-CMDS treatments. The scanning electron microscopy (SEM)-energy dispersive X-ray spectroscopy (EDX) sample treated with 10 wt% COS and 10 wt% CMDS indicated that As immobilization may be associated with the formation of Ca-As and Fe-As precipitates while Pb and Cu immobilization was most probably linked to calcium silicate hydrates (CSHs) and calcium aluminum hydrates (CAHs).

Effects of tungsten on environmental systems.

Tungsten is a metal with many industrial and military applications, including manufacturing of commercial and military ammunition. Despite its widespread use, the potential environmental effects of tungsten are essentially unknown. This study addresses environmental effects of particulate and soluble forms of tungsten, and to a minor extent certain tungsten alloy components, present in some munitions formulations. Dissolution of tungsten powder significantly acidifies soils. Tungsten powder mixed with soils at rates higher than 1% on a mass basis, trigger changes in soil microbial communities resulting in the death of a substantial portion of the bacterial component and an increase of the fungal biomass. It also induces the death of red worms and plants. These effects appear to be related with the soil acidification occurring during tungsten dissolution. Dissolved tungsten species significantly decrease microbial yields by as much as 38% for a tungsten media concentration of 89 mg l(-1). Soluble tungsten concentrations as low as 10(-5) mg l(-1), cause a decrease in biomass production by 8% which is possibly related to production of stress proteins. Plants and worms take up tungsten ions from soil in significant amounts while an enrichment of tungsten in the plant rhizosphere is observed. These results provide an indication that tungsten compounds may be introduced into the food chain and suggest the possibility of development of phytoremediation-based technologies for the cleanup of tungsten contaminated sites.

Amelioration of acidic soil using various renewable waste resources.

In this study, improvement of acidic soil with respect to soil pH and exchangeable cations was attempted for sample with an initial pH of approximately 5. Acidic soil was amended with various waste resources in the range of 1 to 5 wt.% including waste oyster shells (WOS), calcined oyster shells (COS), Class C fly ash (FA), and cement kiln dust (CKD) to improve soil pH and exchangeable cations. Upon treatment, the soil pH was monitored for periods up to 3 months. The exchangeable cations were measured after 1 month of curing. After a curing period of 1 month, a maize growth experiment was conducted with selected-treated samples to evaluate the effectiveness of treatment. The treatment results indicate that in order to increase the soil pH to a value of 7, 1 wt.% of WOS, 3 wt.% of FA, and 1 wt.% of CKD are required. In the case of COS, 1 wt.% was more than enough to increase the soil pH value to 7 because of COS's strong alkalinity. Moreover, the soil pH increases after a curing period of 7 days and remains virtually unchanged thereafter up to 1 month of curing. Upon treatment, the summation of cations (Ca, Mg, K, and Na) significantly increased. The growth of maize is superior in the treated samples rather than the untreated one, indicating that the amelioration of acidic soil is beneficial to plant growth, since soil pH was improved and nutrients were replenished.

Assessment of natural and calcined starfish for the amelioration of acidic soil.

Quality improvement of acidic soil (with an initial pH of approximately 4.5) with respect to soil pH, exchangeable cations, organic matter content, and maize growth was attempted using natural (NSF) and calcined starfish (CSF). Acidic soil was amended with NSF and CSF in the range of 1 to 10 wt.% to improve soil pH, organic matter content, and exchangeable cations. Following the treatment, the soil pH was monitored for periods up to 3 months. The exchangeable cations were measured after 1 month of curing. After a curing period of 1 month, the maize growth experiment was performed with selected treated samples to evaluate the effectiveness of the treatment. The results show that 1 wt.% of NSF and CSF (700 and 900 °C) were required to increase the soil pH to a value higher than 7. In the case of CSF (900 °C), 1 wt.% was sufficient to increase the soil pH value to 9 due to the strong alkalinity in the treatment. No significant changes in soil pHs were observed after 7 days of curing and up to 3 months of curing. Upon treatment, the cation exchange capacity values significantly increased as compared to the untreated samples. The organic content of the samples increased upon NSF treatment, but it remains virtually unchanged upon CSF treatment. Maize growth was greater in the treated samples rather than the untreated samples, except for the samples treated with 1 and 3 wt.% CSF (900 °C), where maize growth was limited due to strong alkalinity. This indicates that the amelioration of acidic soil using natural and calcined starfish is beneficial for plant growth as long as the application rate does not produce alkaline conditions outside the optimal pH range for maize growth.

Immobilization of lead in contaminated firing range soil using biochar.

Soybean stover-derived biochar was used to immobilize lead (Pb) in military firing range soil at a mass application rate of 0 to 20 wt.% and a curing period of 7 days. The toxicity characteristic leaching procedure (TCLP) was performed to evaluate the effectiveness of the treatment. The mechanism responsible for Pb immobilization in military firing range soil was evaluated by scanning electron microscopy-energy dispersive x-ray spectroscopy (SEM-EDX) and x-ray absorption fine structure (XAFS) spectroscopy analyses. The treatment results showed that TCLP Pb leachability decreased with increasing biochar content. A reduction of over 90 % in Pb leachability was achieved upon treatment with 20 wt.% soybean stover-derived biochar. SEM-EDX, elemental dot mapping and XAFS results in conjunction with TCLP leachability revealed that effective Pb immobilization was probably associated with the pozzolanic reaction products, chloropyromorphite and Pb-phosphate. The results of this study demonstrated that soybean stover-derived biochar was effective in immobilizing Pb in contaminated firing range soil.