Washington Braida

Solubility, Sorption, and Soil Respiration Effects of Tungsten and Tungsten Alloys

This laboratory study addresses issues related to the fate and transport of tungsten and tungsten oxides in the environment (soil-water). Tungsten dioxide and tungsten trioxide were dissolved in aqueous solutions whose pH had been adjusted from 4.0 to 11.0. For initial pH smaller than 10.0, dissolved tungsten concentration remained fairly constant at around 10.0 mg/L for WO2 and increased from 0.3 mg/L to 2.0 mg/L for WO3 with increasing values of initial pH. Large amounts of dissolved tungsten were found when tungsten powder or alloy pieces were exposed to aqueous solutions. The dissolution occurs along depletion in solution pH and dissolved oxygen concentration. Depending upon the alloying elements present, the final dissolved tungsten concentration varied from 70 to 475 mg/L. Reduction in pH, dissolved oxygen depletion, and high levels of dissolved tungsten may be of relevance to environmental forensics. In the presence of alloying elements such as iron, nickel, and cobalt, tungsten strongly sorbed to well-characterized model soils. Sorption of tungsten to illite and montmorillonite clays occurs with an increase in pH and appears to be nonreversible. This behavior may significantly retard tungsten mobility. The mixing of tungsten powder with soils at rates higher than 3% (w/w) resulted in acidification of the soil matrix and had a significant impact on soil microbial community as determined by soil respiration.

Degradation of high energetic and insensitive munitions compounds by Fe/Cu bimetal reduction

A reductive technology based on a completely mixed two-phase reactor (bimetallic particles and aqueous stream) was developed for the treatment of aqueous effluents contaminated with nitramines and nitro-substituted energetic materials. Experimental degradation studies were performed using solutions of three high energetics (RDX, HMX, TNT) and three insensitive-munitions components (NTO, NQ, DNAN). The study shows that, on laboratory scale, these energetic compounds are easily degraded in solution by suspensions of bimetallic particles (Fe/Ni and Fe/Cu) prepared by electro-less deposition. The type of bimetal pair (Fe/Cu or Fe/Ni) does not appear to affect the degradation kinetics of RDX, HMX, and TNT. The degradation of all components followed apparent first-order kinetics. The half-lives of all compounds except NTO were under 10 min. Additional parameters affecting the degradation processes were solids loading and initial pH.

Surface-Enhanced Raman Scattering Spectroscopy of Explosive 2,4-Dinitroanisole using Modified Silver Nanoparticles

2,4-Dinitroanisole (DNAN) is being used as a replacement for 2,4,6-trinitrotoluene (TNT) as a less-sensitive melt-cast medium explosive than TNT. In this paper, we studied the surface-enhanced Raman spectroscopy (SERS) analysis of DNAN using Ag nanoparticles (AgNPs) modified by L-cysteine methyl ester hydrochloride. Due to the formation of a Meisenheimer complex between DNAN and the modifier, the modified AgNPs can detect 20 μg/L (0.2 ng) and 0.1 mg/L (1 ng) DNAN in deionized water and aged tap water, respectively. Three other chemicals (L-cysteine, N-acetyl-L-cysteine, and L-cysteine ethyl ester hydrochloride) were used as AgNPs modifiers to study the mechanism of the SERS of DNAN. It was confirmed that the amino group of L-cysteine methyl ester hydrochloride was the active group and that the methyl ester group significantly contributed to the high SERS sensitivity of DNAN. In order to further test the mechanism of Meisenheimer complex formation, the effect of anions and cations present in natural water on the SERS of DNAN was studied. It was found that CO(3)(2-), Cl(-), and K(+) at 100 mg/L did not negatively affect the SERS of 10 mg/L DNAN, while SO(4)(2-), Na(+), Mg(2+), and Ca(2+) at 100 mg/L significantly quenched the SERS of 10 mg/L DNAN. The negative effect of the bivalent cations could be offset by SO(4)(2-).

A Review of Molybdenum Adsorption in Soils/Bed Sediments: Speciation, Mechanism, and Model Applications

Mo is an essential trace element for both plants and animals in low concentrations (<5 ppm). However, provoked by uncontrolled industrial waste releases in freshwater or seawater, it is plausible that excessive availability of soluble Mo(VI) would be potentially toxic. In the environment, soluble Mo(VI) is mainly present in anionic forms of molybdate (MoO4 2−) and/or tetrathiomolybdate (MoS4 2−). The fate and transport of soluble Mo(VI) anions in surface and subsurface aquatic environments is typically controlled by adsorption in acidic soils and sediment. As such, the ability of soils/bed sediments to retain Mo(VI) is a key to determine its general mobility in the aquatic environment. This article reviews the sources and distribution of Mo speciation in solution and Mo(VI) anions adsorption mechanisms in soils and bed sediments, and evaluates the surface adsorption complexation models at the solid-water interface to estimate Mo(VI) anions adsorption in these chemical systems. Mo(VI) anions adsorption mechanisms included MoO4 2− and MoS4 2− adsorption by several prevailing adsorbent contents (including clay, Fe, Al oxides, iron sulfide, manganese oxides, and organic matter) of soils and bed sediments, and the influence of the competitive adsorption of other anions (e.g., sulfate, selenate, phosphate, arsenate, silicate, or tungstate). Models to estimate Mo(VI) anions adsorption include the triple layer model (TLM), the diffuse layer model (DLM), the constant capacitance surface complexation model (CCM), and charge distribution multisite complexation model (CD-MUSIC).

Ultrafiltration of ink and latex wastewaters using cellulose membranes

Ultrafiltration (UF) studies were conducted on latex and ink rinse wastewaters to assess the potential of concentrating the wastewater and recovering the permeate for reuse and recycling purposes. The physicochemical characteristics of the ink and latex wastewater suggested that the quality of both wastewaters was strongly dependent on the rinse process. A 4-fold and 7-fold concentration of ink and latex wastewater, respectively, may be achieved depending on the initial physicochemical characteristics of the wastewater. The UF system concentrated the latex wastewater to a total solids (TS) concentration of 275 g/L (approx. 28%) and to 99 g/L (approx. 10%) for ink wastewater. The permeates had turbidities ranging from 0.13 to 0.4 NTU. However, a significant percentage of the TS remained in the permeate of the ink wastewater which may require further treatment before it can be reused. For latex wastewater, it is likely that the retentate can be reused along with the permeate for rinsing purposes. For the ink wastewater, both pore blocking and cake resistance models were able to describe the change in flux with time. However, for the latex wastewater, pore blocking seemed to describe the flux with time data better than the cake resistance models. The fouling coefficient, K, for the pore blocking model was found to be a function of the TS present in the latex wastewater.

Evaluation of the Adsorption of Mono- and Polytungstates onto Different Types of Clay Minerals and Pahokee Peat

Detailed knowledge about the fate and transport of tungsten in soils is critical to understanding and effectively addressing tungsten behavior in the environment. Recent studies have shown that tungsten anions may polymerize (depending upon concentration, pH, and aquatic geochemistry) in aquatic and soil systems. However, to date, of all soluble tungstate species only monotungstates have been scrutinized to a fair extent in adsorption studies. There is a lack of information evaluating adsorption mechanisms of mono- and polytungstates onto clay minerals. The objective of this work is to investigate the adsorption behavior of monotungstates (sodium tungstate, Na2WO4) and polytungstates (sodium metatungstate, 3Na2WO4·9WO3) onto different types of clay minerals (montmorillonite, kaolinite, illite) and an organic adsorbent (Pahokee peat). Batch equilibrium experiments as a function of concentration (adsorption isotherms) and pH (adsorption envelopes) were performed to provide information about mono- and polytungstate adsorption onto clays and Pahokee peat. Adsorption equilibrium data for mono- and polytungstates onto different types of clay minerals and Pahokee peat were modeled with Freundlich and Langmuir isotherms. The adsorption affinity of clays and Pahokee peat for monotungstates follows the order: Pahokee peat>kaolinite>montmorillonite>illite; for polytungstates, the order is as follows: kaolinite>Pahokee peat>montmorillonite>illite. Results of this study suggest that the charges of the clay mineral surface, tungsten species, and solution pH are the main factors controlling tungsten adsorption. Moreover, polymeric tungsten species (i.e., metatungstate) appear to be more mobile in the environment than monomeric tungstate.

Generation and Detection of Gaseous W12O41-˙ and Other Tungstate Anions by Laser Desorption Ionization Mass Spectrometry

The presence of a peak centered near m/z 2862, observed for the first time for the caged dodecatungstate radical-anion, [W12O41]−·, enables distinguishing WO2 from WO3 by Laser Desorption Ionization mass spectrometry (LDI-MS). In addition to WO2, laser irradiation of dry deposits made from aqueous ammonium paratungstate, and calcium and lead orthotungstate also produce the [W12O41]−·. In contrast, spectra recorded from deposits made from aqueous Na2WO4, sodium metatungstate, and WO3, or non-aqueous calcium and lead orthotungstate, and ammonium paratungstate, failed to show the m/z 2862 peak cluster. These observations support the hypothesis that polycondensation reactions to form [W12O41]−· occur solely in the presence of water. Although dry spots are irradiated for ionization, the solvent used for sample preparation plays an important role on the chemical composition endowed to ions detected. For example, the m/z 2862 peak seen from deposits made from aqueous ammonium paratungstate, and calcium and lead orthotungstate, is absent in the spectra recorded either from pristine deposits or those derived from solutions made with organic solvents such as acetonitrile or ethanol.

Assessing tungsten transport in the vadose zone: From dissolution studies to soil columns

This study investigates the dissolution, sorption, leachability, and plant uptake of tungsten and alloying metals from canister round munitions in the presence of model, well characterized soils. The source of tungsten was canister round munitions, composed mainly of tungsten (95%) with iron and nickel making up the remaining fraction. Three soils were chosen for the lysimeter studies while four model soils were selected for the adsorption studies. Lysimeter soils were representatives of the typical range of soils across the continental USA; muck-peat, clay-loamy and sandy-quartzose soil. Adsorption equilibrium data on the four model soils were modeled with Langmuir and linear isotherms and the model parameters were obtained. The adsorption affinity of soils for tungsten follows the order: Pahokee peat>kaolinite>montmorillonite>illite. A canister round munition dissolution study was also performed. After 24 d, the measured dissolved concentrations were: 61.97, 3.56, 15.83 mg L(-1) for tungsten, iron and nickel, respectively. Lysimeter transport studies show muck peat and sandy quartzose soils having higher tungsten concentration, up to 150 mg kg(-1) in the upper layers of the lysimeters and a sharp decline with depth suggesting strong retardation processes along the soil profile. The concentrations of tungsten, iron and nickel in soil lysimeter effluents were very low in terms of posing any environmental concern; although no regulatory limits have been established for tungsten in natural waters. The substantial uptake of tungsten and nickel by ryegrass after 120 d of exposure to soils containing canister round munition suggests the possibility of tungsten and nickel entering the food chain.

Sustainable municipal solid waste management decision making

Purpose – The purpose of this paper is to assess a comprehensive model that computes a single score in order to evaluate the sustainability of the municipal solid waste management (MSWM) system of a given city. The model was applied to calculate the sustainability index for the MSWM of Istanbul, Turkey as a case study. Design/methodology/approach – Different sustainability indicators (including environmental, economical, and social parameters) along with exergy analysis were integrated to utilize an analytical hierarchy process (AHP) under a life cycle perspective. Findings – The Istanbul case study helped to verify that AHP is an effective and efficient decision-making tool. According to the analysis, the current MSWM system of Istanbul is sustainable, and the sustainability can be improved only by changing the amounts to be treated by the current system without any new technological investments. Research limitations/implications – The Municipal Solid Waste Management Sustainability Index (MSWMSI) in thi...

Degradation of trichloroethylene using iron, bimetals and trimetals

A cold, electrodeless method was used to prepare bimetals (Fe/Cu, Fe/Ni) and trimetals (Fe/Cu/Ni) for the treatment of trichloroethylene (TCE). With Fe/Cu, the degradation of TCE was observed to increase with increasing copper content up to 9.26 % (w/w) with a first-order degradation rate constant approximately 10 times faster than that of zero-valent iron (ZVI) alone. For copper content greater than 9.26 %, the TCE degradation rate decreased. Dechlorinated compounds were initially observed but they were transitory and accounted for no more than 9 % of initial TCE mass on a carbon molar basis. Ethylene was the primary end product of TCE reduction. Similarly for Fe/Ni, increasing rates of degradation were observed with increasing amounts of nickel with a maximum degradation rate constant of about 30 times higher than that of ZVI alone. However, the amount of nickel needed to reach the maximum rate was only 0.25 %. When copper and nickel were plated onto iron, the maximum reaction rate constant was approximately 50 times higher than that of ZVI. The maximum degradation of TCE was observed for a copper and nickel content of 4.17 % and 0.40 %, respectively. The experimental results indicated that TCE degradation was enhanced by more than one order of magnitude when copper and/or nickel was plated onto the zero-valent iron. However, copper or nickel plated onto iron by the elctrodeless process was found to leach out during the reaction which may, in turn, impact the contaminated water.