Degradation kinetics of hexachlorobenzene over zero-valent magnesium/graphite in protic solvent system and modeling of degradation pathways using density functional theory.

Hexachlorobenzene (HCB), like many chlorinated organic compounds, has accumulated in the environment from agricultural and industrial activity. Because of its health risks and adverse impact on various ecosystems, remediation of this contaminant is of vital concern. The objective of this study is to evaluate the proficiency of activated magnesium metal in a protic solvent system to accomplish reductive dechlorination of HCB. Experimental results were compared with those predicted by quantum chemical calculations based on Density Functional Theory (DFT). Multivariate analysis detected complete degradation of HCB within 30 min at room temperature, the reaction having a rate constant of 0.222 min-1. Dechlorination was hypothesized to proceed via an ionic mechanism; the main dechlorination pathways of HCB in 1:1 ethanol:ethyl lactate were HCB → PCBz → 1,2,4,5-TCB; 1,2,3,5-TCB → 1,2,4-TriCB; 1,3,5-TriCB → 1,4-DiCB; 1,3-DiCB. The direct relationship between the decreasing number of Cl substituents and dechlorination reaction kinetics agrees with the ΔG values predicted by the computational model. This methodology shows promise for the development of a practical and sustainable field application for the remediation of other chlorinated aromatic compounds.

Mechanistic and computational studies of PCB 151 dechlorination by zero valent magnesium for field remediation optimization.

Polychlorinated biphenyls (PCBs) are banned in the U.S. but are persistent in the environment; current regulations provide an urgent need to remediate PCBs in a cost-effective way. In prior work, a novel method of degradation of PCBs via hydrodehalogenation with ball milled zero-valent magnesium and activated carbon showed promising results even with water present in the system. In this research, a detailed study of the byproducts formed in the dechlorination process for PCB 151 (used as an example of hexa-chlorinated PCB) and a study of the mechanism involved in this reaction via density functional theory (DFT) computations are presented. It was demonstrated that these reactions are exothermic and involved two transition states, the formation of the ionic transition state being the rate limiting step of the reaction. The torsion angle of the PCB congeners was also shown to be an extremely important factor to be able to use activated carbon as part of the remediation process.

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.

Case study of a non-destructive treatment method for the remediation of military structures containing polychlorinated biphenyl contaminated paint.

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.

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.

Laboratory evaluation of a prospective remediation method for PCB-contaminated paint.

BACKGROUND: Paint laden with polychlorinated biphenyls (PCBs) often acts as a point source for environmental contamination. It is advantageous to address contaminated paint before the PCBs transport to surrounding media; however, current disposal methods of painted material introduce a variety of complications. Previous work demonstrates that PCBs can be broken down at ambient temperatures and pressures through a degradation process involving magnesium metal and acidified ethanol. This report is an extension of that work by describing the development of a delivery system for said reaction in preparation for a field test. Two treatment options including the Activated Metal Treatment System (AMTS) and the Non-Metal Treatment System (NMTS) remove and degrade PCBs from painted surfaces. FINDINGS: AMTS decreased the Aroclor® concentration of a solution by more than 97% within 120 minutes and the Aroclor® concentration of industrial paint chips by up to 98% over three weeks. After removing up to 76% of PCBs on a painted surface after seven days, NMTS also removed trace amounts of PCBs in the paint's concrete substrate. The evaporation rate of the solvent (ethanol) from the treatment system was reduced when the application area was increased. The solvent system's ability to remove more than 90% of PCBs was maintained after losing 36% of its mass to solvent evaporation. CONCLUSIONS: The delivery systems, AMTS and NMTS, are able to support the hydrodechlorination reaction necessary for PCB degradation and are therefore attractive options for further studies regarding the remediation of contaminated painted surfaces.

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.