Comparative study for the removal and destruction of pentachlorophenol using activated magnesium treatment systems.

Chlorophenols are highly toxic, environmentally-persistent compounds which have been classified as probable human carcinogens by the United States Environmental Protection Agency. Due to the high toxicity of these compounds, it is necessary to treat water and soils with concentrations of chlorophenols above the detection limit set by regulatory agencies. The aim of this work is to demonstrate the capabilities of using ball-milled magnesium for the dechlorination of PCP. Comparison of dechlorination processes were performed in an attempt to determine the most effective system for degradation of PCP to phenol. Three systems with powerful capabilities of treatment were studied: ball-milled zero-valent magnesium (ZVMg), ball-milled zero-valent magnesium carbon (ZVMg/C), and ball-milled zero-valent magnesium with palladium (ZVMg/Pd). In addition to measuring PCP disappearance, all byproducts were identified and quantified for each degradation system. The results of these studies indicate that all three of the systems degrade PCP within 30 min. The most rapid and complete PCP dechlorination is achieved using ball-milled Mg/Pd and a matrix consisting of at least 0.02 g Mg0/mL ethanol, and 10 µL acetic acid/mL ethanol, in which case 20 ng/µL of PCP was dechlorinated to chlorophenols in approximately 15 min with complete dechlorination achieved in six days. Carbon mass balances of 90.16% for Mg, 94.76% (Mg/C) and 97.05% (Mg/Pd) verify dechlorination was responsible for declining concentrations of PCP. The reactions of PCP degradation and phenol formation were found to follow pseudo-first order kinetics for all systems. Further work will consist of optimization and development of field-scale applications.

Application of a magnesium/co-solvent system for the degradation of polycyclic aromatic hydrocarbons and their oxygenated derivatives in a spiked soil.

This study evaluates the capability, efficacy and practicality of a combined approach based on solvent extraction and chemical reduction to simultaneously degrade polycyclic aromatic hydrocarbons (PAHs) and their oxygenated derivatives (OPAHs) in spiked soil. The spiked soil was washed using a composite organic solvent consisting of ethanol and ethyl lactate (1:1, v/v) and then degradation of the extracted contaminants using zero-valent magnesium. The extraction conditions were optimized at 25 °C with solvent-soil ratio of 2:1 (v/w) and the ensuing degradation efficiency ranged from 79% to 88% for the OPAHs, and 66% to 87% for the PAHs after 24 h of reaction at pH of 6.1. The reductive degradation of the spiked contaminants followed pseudo-first-order kinetics; however, comparing the kinetic results of this study to soil-free studies, the degradation rates are significantly reduced. It can be inferred that extracted organic or inorganic components from the soil medium hinder the degradation process, possibly by reducing the reactivity of the activated metal. Furthermore, to our understanding, this study is the first report on the simultaneous degradation of these priority pollutants and their oxygenated derivatives. The experimental results encourage the application of this magnesium/co-solvent system for future pilot-scale remediation studies.

Reductive degradation of oxygenated polycyclic aromatic hydrocarbons using an activated magnesium/co-solvent system.

This study evaluates the capability of zero-valent magnesium and a protic co-solvent to promote the degradation of oxygenated polycyclic aromatic hydrocarbons compounds, specifically 9-fluorenone, 9,10-anthraquinone, 7,12-benz(a)anthraquionone, and 7H-benz(de)anthracene-7-one. At room temperature conditions, greater than 86% degradation efficiency is observed after 24h of reaction time for a mixture containing 0.05 g of magnesium and four selected oxygenated aromatic hydrocarbons with 250 mg L(-1) concentrations. It is noted that glacial acetic acid is needed as an activator for the degradation reaction to proceed. It is also presumed that the acid removes oxide and hydroxide species from the magnesium surface. With the GC-MS analysis of the reaction products, possible reductive pathways are suggested. Furthermore, this study is the first report on the degradation of these emerging contaminants and it is proposed that the magnesium-powder/protic-solvent system is a promising low-cost reagent and may allow for the future development of an economic and environmentally-friendly remediation application.

Multivariate evaluation and optimization of an activated-magnesium/co-solvent system for the reductive degradation of polycyclic aromatic hydrocarbons.

The present study evaluates the capability of an activated-magnesium metal and protic co-solvents to promote the reductive degradation of three different polycyclic aromatic hydrocarbons, specifically pyrene, benzo[k]fluoranthene and benzo[g,h,i]perylene. Multivariate analyses demonstrated that the kinetics of degradation was affected by several experimental factors such as magnesium loading, acid addition and solubility of the compounds. It was determined that an acid activator is needed for the degradation reaction to proceed and it is also noted that the use of a 1:1 ethanol/ethyl lactate co-solvent is ideal for the complete dissolution of all three compounds with concentrations varying from 200 to 275mgL(-1). The experimental results also indicate that, at room temperature conditions, only 0.05-0.1g of magnesium is required in order to achieve greater than 93% degradation efficiency after 24h of reaction. This methodology is attractive and may allow for the development of an economic and environmentally friendly field application for the remediation of other polycyclic aromatic hydrocarbons.

Reduction of benzo[a]pyrene with acid-activated magnesium metal in ethanol: a possible application for environmental remediation.

Persistent organic pollutants (POPs) are a well-known threat to the environment. Substances such as polycyclic aromatic hydrocarbons (PAHs) in contaminated soils and sediments can have severe and long-term effects on human and environmental health. There is an urgent need for the development of safe technologies for their effective degradation. Here we present a new technique using ball-milled magnesium powder and ethanol solvent as a convenient electron transfer/proton source for the partial reduction of PAHs under ambient conditions. The rates of degradation were determined while evaluating the influences of acetic acid and type of ball-milled magnesium added to the reaction mixture. The results of these triplicate studies indicate that with the use of acetic acid as an activator and ball-milled magnesium carbon (Mg/C), this reducing system (Mg-EtOH) is able to achieve a 94% conversion of 250 µg/mL of toxic benzo[a]pyrene into a mixture of less toxic and partially hydrogenated polycyclic compounds within 24h. This methodology can be used as a combined process involving ethanol washing followed by reduction reaction and it can also be considered as an easy handling and efficient alternative process to the catalytic hydrogenation of PAHs.

The use of mechanical alloying for the preparation of palladized magnesium bimetallic particles for the remediation of PCBs.

The kinetic rate of dechlorination of a polychlorinated biphenyl (PCB-151) by mechanically alloyed Mg/Pd was studied for optimization of the bimetallic system. Bimetal production was first carried out in a small-scale environment using a SPEX 8000M high-energy ball mill with 4-µm-magnesium and palladium impregnated on graphite, with optimized parameters including milling time and Pd-loading. A 5.57-g sample of bimetal containing 0.1257% Pd and ball milled for 3 min resulted in a degradation rate of 0.00176 min(-1)g(-1) catalyst as the most reactive bimetal. The process was then scaled-up, using a Red Devil 5400 Twin-Arm Paint Shaker, fitted with custom plates to hold milling canisters. Optimization parameters tested included milling time, number of ball bearings used, Pd-loading, and total bimetal mass milled. An 85-g sample of bimetal containing 0.1059% Pd and ball-milled for 23 min with 16 ball bearings yielded the most reactive bimetal with a degradation rate of 0.00122 min(-1)g(-1) catalyst. Further testing showed adsorption did not hinder extraction efficiency and that dechlorination products were only seen when using the bimetallic system, as opposed to any of its single components. The bimetallic system was also tested for its ability to degrade a second PCB congener, PCB-45, and a PCB mixture (Arochlor 1254); both contaminants were seen to degrade successfully.

Dechlorination of polychlorinated biphenyls using magnesium and acidified alcohols.

Polychlorinated biphenyls (PCBs) were widely used in industry until their regulation in the 1970s. However, due to their inherent stability, they are still a widespread environmental contaminant. A novel method of degradation of PCBs (via hydrodehalogenation) has been observed using magnesium powder, a carboxylic acid, and alcohol solvents and is described in this paper. The rates of degradation were determined while varying the type of acid (formic, acetic, propionic, butyric, valeric, benzoic, ascorbic, and phosphoric), the amount of magnesium from 0.05 to 0.25 g, the amount of acetic acid from 0.5 to 50 µL and the concentration of PCB-151 from 0.1 to 50 µg/mL, as well as the alcohol solvent (methanol, ethanol, propanol, butanol, octanol, and decanol). The results of these studies indicate that the most rapid PCB dechlorination is achieved using a matrix consisting of at least 0.02 g Mg/mL ethanol, and 10 µL acetic acid/mL ethanol in which case 50 ng/µL of PCB-151 is dechlorinated in approximately 40 min.

Mechanism of the degradation of individual PCB congeners using mechanically alloyed Mg/Pd in methanol.

Polychlorinated biphenyls (PCBs) are a continuing concern in the environment, although legislation restricting the production and use of PCBs was introduced more than 30 years ago. The combination of zero-valent metals and hydrogenation catalysts has been proven effective in the remediation of PCBs, although the exact mechanism of degradation is not known as of yet. The use of mechanically alloyed zero-valent magnesium and palladium (on graphite) has shown great success in the dechlorination of PCBs. Knowing the mechanism for this dechlorination would be helpful in optimizing the bimetallic Mg/Pd for use in the field. A variety of experiments have been performed on a single PCB congener (PCB-151, 2,2',3,5,5',6-polychlorobiphenyl) in an attempt to determine the mechanism by which the degradation occurs. The studies are carried out in methanol to mimic the solvent system which will be used in field applications. Results of these studies have suggested three possible mechanisms, all of which include the removal of the chlorine atom by a hydrogen as the rate-limiting step, varying only in the exact nature of the hydrogen species (radical, hydride, or "hydride-like" radical). BRIEF: A series of studies has suggested three possible mechanistic pathways for the degradation of PCBs in methanol by Mg/Pd.

Dechlorination comparison of mono-substituted PCBs with Mg/Pd in different solvent systems.

It is widely recognized that polychlorinated biphenyls (PCBs) are a dangerous environmental pollutant. Even though the use and production of PCBs have been restricted, heavy industrial use has made them a wide-spread environmental issue today. Dehalogenation using zero-valent metals has been a promising avenue of research for the remediation of chlorinated compounds and other contaminants that are present in the environment. However, zero-valent metals by themselves have shown little capability of dechlorinating polychlorinated biphenyls (PCBs). Mechanically alloying the metal with a catalyst, such as palladium, creates a bimetallic system capable of dechlorinating PCBs very rapidly to biphenyl. This study primarily aims to evaluate the effects of solvent specificity on the kinetics of mono-substituted PCBs, in an attempt to determine the mechanism of degradation. Rate constants and final byproducts were determined for the contaminant systems in both water and methanol, and significant differences in the relative rates of reaction were observed between the two solvents.

Analysis of triacetone triperoxide by gas chromatography/mass spectrometry and gas chromatography/tandem mass spectrometry by electron and chemical ionization.

The explosive triacetone triperoxide (TATP) has been analyzed by gas chromatography/mass spectrometry (GC/MS) and sub-nanogram detection limits are reported by ammonia positive ion chemical ionization (PICI), electron ionization (EI) and methane negative ion chemical ionization (NICI). Analysis by methane PICI and ammonia NICI gave detection limits in the low nanogram range. Analyses were carried out on (linear) quadrupole and ion trap instruments. Analysis of TATP by PICI using ammonia reagent gas is the preferred analytical method, producing low limits of detection as well as an abundant (greater than 60% of base peak) diagnostic adduct ion at m/z 240 corresponding to [TATP + NH4]+. Isolation of the [TATP + NH4]+ ion with subsequent collision-induced dissociation (CID) produces extremely low abundance product ions at m/z values greater than 60, and the m/z 223 ion corresponding to [TATP + H]+ was not observed. Density functional theory (DFT) calculations at the B88LYP/DVZP level indicate that dissociation of the complex to form NH4+ and TATP occurs at energies lower than peroxide bond dissociation, while protonation of TATP leads to cleavage of the ring structure. These results provide a method for pico-gram detection levels of TATP using commercial instrumentation commonly available in forensic laboratories. As a point of comparison, a detection limit of 15 ng was obtained by flame ionization detection.

Control of Nitrogen Oxide Emissions by Hydrogen Peroxide-Enhanced Gas-Phase Oxidation Of Nitric Oxide.

Nitrogen oxides (NOX) and sulfur oxides (SOX) are criteria air pollutants, emitted in large quantities from fossil-fueled electric power plants. Emissions of SOX are currently being reduced significantly in many places by wet scrubbing of the exhaust or flue gases, but most of the NOX in the flue gases is NO, which is so insoluble that it is virtually impossible to scrub. Consequently, NOX control is mostly achieved by using combustion modifications to limit the formation of NOX, or by using chemical reduction techniques to reduce NOX to N2. Low NOX burners are relatively inexpensive but can only achieve about 50% reduction in NOX emissions; selective catalytic reduction (SCR) can achieve high reductions but is very expensive. The removal of NOX in wet scrubbers could be greatly enhanced by gas-phase oxidation of the NO to NO2, HNO2, and HNO3 (the acid gases are much more soluble in water than NO). This oxidation is accomplished by injecting liquid hydrogen peroxide into the flue gas; the H2O2 vaporizes and dissociates into hydroxyl radicals. The active OH radicals then oxidize the NO and NO2. This NOX control technique might prove economically feasible at power plants with existing SO2 scrubbers. The higher chemical costs for H2O2 would be balanced by the investment cost savings, compared with an alternative such as SCR. The oxidation of NOX by using hydrogen peroxide has been demonstrated in a laboratory quartz tube reactor. NO conversions of 97% and 75% were achieved at hydrogen peroxide/NO mole ratios of 2.6 and 1.6, respectively. The reactor conditions (500 °C, a pressure of one atmosphere, and 0.7 seconds residence time) are representative of flue gas conditions for a variety of combustion sources. The oxidized NOX species were removed by caustic water scrubbing.