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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., (Copyright © 2016 Elsevier Ltd. All rights reserved.)

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.

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., (Copyright © 2013 Elsevier Ltd. All rights reserved.)

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., (Copyright © 2013 Elsevier B.V. All rights reserved.)

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., (Copyright © 2011 Elsevier B.V. All rights reserved.)

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., (Copyright © 2011 Elsevier B.V. All rights reserved.)

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., (Copyright © 2011 Elsevier B.V. All rights reserved.)

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.

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.

Restricted by federal regulations and limited remediation options, buildings contaminated with paint laden with polychlorinated biphenyls (PCBs) have high costs associated with the disposal of hazardous materials. As opposed to current remediation methods which are often destructive and a risk to the surrounding environment, this study suggests a non-metal treatment system (NMTS) and a bimetallic treatment system (BTS) as versatile remediation options for painted industrial structures including concrete buildings, and metal machine parts. In this field study, four areas of a discontinued Department of Defense site were treated and monitored over 3 weeks. PCB levels in paint and treatment system samples were analyzed through gas chromatography/electron capture detection (GC-ECD). PCB concentrations were reduced by 95 percent on painted concrete and by 60–97 percent on painted metal with the majority of the PCB removal occurring within the first week of application. Post treatment laboratory studies including the utilization of an activated metal treatment system (AMTS) further degraded PCBs in BTS and NMTS by up to 82 percent and 99 percent, respectively, indicating that a two-step remediation option is viable. These findings demonstrate that the NMTS and BTS can be an effective, nondestructive, remediation process for large painted structures, allowing for the reuse or sale of remediated materials that otherwise may have been disposed. [ABSTRACT FROM AUTHOR]