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All sourcesNASA NTRSDOE OSTI
NASA NTRS2006

The Ability of AMSTAR Dechlorination Solution to Remove and Degrade PCBs from Contaminated Surfaces

Polychlorinated biphenyls (PCBs) are a group of synthetic aromatic compounds with the general formula C12H(10-x)Cl(-x) that were historically used in industrial paints, caulking material and adhesives, as their properties enhanced structural integrity, reduced flammability and boosted antifungal properties. Although the United States Environmental Protection Agency (USEPA) has banned the manufacture of PCBs since 1979, they have been found in at least 500 of the 1,598 National Priorities List (Superfund) sites identified by the USEPA. Prior to the US EPA's ban on PCB production, PCBs were commonly used as additives in paints and asphalt-based adhesives that were subsequently applied to a variety of structures. Government facilities constructed as early as 1930 utilized PCB-containing binders or PCB-containing paints, which are now leaching into the environment and posing ecological and worker health concerns. In 2006, a commercially available product known as AMSTAR Dechlorination Solution was tested at NASA's Kennedy Space Center for its ability to remove and degrade PCBs from structural materials. This evaluation was requested by the Environmental Security Technology Certification Program (ESTCP) evaluating the ability of NASA's Bimetallic Treatment System (BTS) to remove and degrade PCBs from structural materials. The results of the laboratory testing are to be used to determine if a side-by-side field-scale test comparing BTS to AMSTAR was warranted. A recommended sampling and analysis testing program was submitted to ESTCP that included triplicate screening of AMSTAR's PCB dechlorination capabilities on a variety of surfaces including glass, bare metal, and painted metal coupons. The test procedures, analytical techniques and results obtained are presented in this interim report to ESTCP.

Quinn, Jacqueline E.↗
NASA NTRS2001

Effects of Potassium Permanganate Oxidation on Subsurface Microbial Activity

In situ chemical oxidation has the potential for degrading large quantities of organic contaminants and can be more effective and timely than traditional ex situ treatment methods. However, there is a need to better characterize the potential effects of this treatment on natural processes. This study focuses on potential inhibition to anaerobic dechlorination of trichloroethene (TCE) in soils from a large manufacturing facility as a result of in situ oxidation using potassium permanganate (KMn04)Previous microcosm studies established that natural attenuation occurs on-site and that it is enhanced by the addition of ethanol to the system. A potential remediation scheme for the site involves the use of potassium permanganate to reduce levels of TCE in heavily contaminated areas, then to inject ethanol into the system to "neutralize" excess oxidant and enhance microbial degradation. However, it is currently unknown whether the exposure of indigenous microbial populations to potassium permanganate may adversely affect biological reductive dechlorination by these microorganisms. Consequently, additional microcosm studies were conducted to evaluate this remediation scheme and assess the effect of potassium permanganate addition on biological reductive dechlorination of TCE. Samples of subsurface soil and groundwater were collected from a TCE-impacted area of the site. A portion of the soil was pretreated with nutrients and ethanol to stimulate microbial activity, while the remainder of the soil was left unamended. Soil/groundwater microcosms were prepared in sealed vials using the nutrient-amended and unamended soils, and the effects of potassium permanganate addition were evaluated using two permanganate concentrations (0.8 and 2.4 percent) and two contact times (1 and 3 weeks). TCE was then re-added to each microcosm and TCE and dichloroethene (DCE) concentrations were monitored to determine the degree to which microbial dechlorination occurred following chemical oxidation. Evidence of microbial degradation was generally detected within four weeks after TCE addition. Increases in DCE concentrations were consistent with decreases in TCE. The concentration of TCE in the nutrient-amended samples exposed to 2.4% KMnO4 for one week degraded somewhat more slowly than the samples exposed to the 0.8% KMnO4. The rates of degradation did not correlate with the length of KMn04 exposure for the nutrient-amended microcosms. Microbial degradation of TCE in the unamended microcosms was generally similar to that observed in the nutrient-amended microcosms. One treatment condition (unamended, one week exposure, 2.4% KMnO4) was exposed to elevated levels of ethanol and showed little evidence of degradation. It is suspected that the high levels of ethanol were toxic to the microorganisms. The results of the study indicate that exposure of indigenous soil and groundwater microbial populations to KMnO4 at concentrations of 0.8 to 2.4% do not impair the ability of the microbial populations to dechlorinate TCE. Consequently, the combination of chemical oxidation followed by enhanced biological reductive dechlorination appears to be a viable remedial strategy for highly-impacted subsurface areas of the site.

Rowland, Martin A.↗
NASA NTRS1996

Biodegradation of Trihalomethanes and Other Halogenated Aliphatic Compounds

The biological dehalogenation of common water pollutants such as trichloromethane (chloroform) and other halogenated aliphatic compounds was the subject of this project. Samples from diverse water environments such as from groundwater contaminated with halogenated compounds and wastewaters from regional treatment plants were studied to identify conditions that favor certain dehalogenation reactions over others. Gene probe analyses of DNA extracted from the dichlormethane-degrading wastewater indicated the presence of the gene coding for dichloromethane dehalogenase, indicating the genetic basis for the dechlorination activity observed. These studies indicate that methanogenic bacteria are the organisms responsible for the chloroform dechlorination. Dechlorination of a common chlorofluorocarbon (CFC-11) was identified in samples taken from a regional aquifer contaminated with halogenated aliphatic compounds.

HALOGENATED ALIPHATC HYDROCARBONS↗
NASA NTRS1978

Coal desulfurization process

A method for chlorinolysis of coal is an organic solvent at a moderate temperautre and atmospheric pressure has been proven to be effective in removing sulfur, particularly the organic sulfur, from coal. Chlorine gas is bubbled through a slurry of moist coal in chlorinated solvent. The chlorinated coal is separated, hydrolyzed and the dechlorinated. Preliminary results of treating a high sulfutr (4.77%S) bituminous coal show that up to 70% organic sulfur, 90% hyritic sulfur and 76% total sulfur can be removed. The treated coal is dechlorinated by heating at 500 C. The presence of moisture helps to remove organic sulfur.

Hsu, G. C.↗
NASA NTRS2013

Preparation of a Bimetal Using Mechanical Alloying for Environmental or Industrial Use

Following the 1976 Toxic Substances Control Act ban on their manufacture, PCBs remain an environmental threat. PCBs are known to bio-accumulate and concentrate in fatty tissues. Further complications arise from the potential for contamination of commercial mixtures with other more toxic chlorinated compounds such as polychlorinated dibenzodioxins (PCDDs) and polychlorinated dibenzofurans (PCDFs). Until recently, only one option was available for the treatment of PCB-contaminated materials: incineration. This may prove to be more detrimental to the environment than the PCBs themselves due to the potential for formation of PCDDs. Metals have been used for the past ten years for the remediation of halogenated solvents and other contaminants in the environment; however, zero-valent metals alone do not possess the activity required to dehalogenate PCBs. Palladium has been shown to act as an excellent catalyst for the dechlorination of PCBs with active metals. This invention is a method for the production of a palladium/magnesium bimetal capable of dechlorinating PCBs using mechanical milling/mechanical alloying. Other base metals and catalysts may also be alloyed together (e.g., nickel or zinc) to create a similarly functioning catalyst system. Several bimetal catalyst systems currently can be used for processes such as hydrogen peroxide synthesis, oxidation of ethane, selective oxidation, hydrogenation, and production of syngas for further conversion to clean fuels. The processes for making these bimetal catalysts often involve vapor deposition. This technology provides an alternative to vapor deposition that may provide equally active catalysts. A hydrogenation catalyst including a base material coated with a catalytic metal is made using mechanical milling techniques. The hydrogenation catalysts are used as an excellent catalyst for the dehalogenation of contaminated compounds and the remediation of other industrial compounds. The mechanical milling technique is simpler and cheaper than previously used methods for producing hydrogenation catalysts. Preferably, the hydrogenation catalyst is a bimetallic particle formed from a zero-valent iron or zero-valent magnesium particle coated with palladium that is impregnated onto a high-surface-area graphite support. The zero-valent metal particles should be microscale or nanoscale zero-valent magnesium or zero-valent iron particles. Other zero-valent metal particles and combinations may be used. Additionally, the base material may be selected from a variety of minerals including, but not limited to, alumina and zeolites. The catalytic metal is preferably selected from the group consisting of noble metals and transition metals, preferably palladium. The mechanical milling process includes milling the base material with a catalytic metal impregnated into a high-surface-area support to form the hydrogenation catalyst. In a preferred mechanical milling process, a zero-valent metal particle is provided as the base material, preferably having a particle size of less than about 10 microns, preferably 0.1 to 10 microns or smaller, prior to milling. The catalytic metal is supported on a conductive carbon support structure prior to milling. For example, palladium may be impregnated on a graphite support. Other support structures such as semiconductive metal oxides may also be used.

Quinn, Jacqueline↗
NASA NTRS1977

Coal desulfurization by low-temperature chlorinolysis

Among the three principal methods for precombustion desulfurization of coal, which include physical depyriting, chemical desulfurization, and coal conversion to low-sulfur liquid and gaseous fuels, the potential of chemical methods looks promising in terms of both total sulfur removal and processing cost. The principal chemical methods for coal desulfurization involve treatment with either oxidizing agents or basic media at elevated temperature and pressure. A description is given of some recent experimental results which show the feasibility of removing sulfur, particularly organic sulfur, from high-sulfur coals by a simple method of low-temperature chlorinolysis followed by hydrolysis and dechlorination. The chemical feasibility of sulfur removal by chlorinolysis rather than the detailed engineering process is emphasized.

Hsu, G. C.↗
NASA NTRS1982

Coal desulfurization by aqueous chlorination

A method of desulfurizing coal is described in which chlorine gas is bubbled through an aqueous slurry of coal at low temperature below 130 degrees C., and at ambient pressure. Chlorinolysis converts both inorganic and organic sulfur components of coal into water soluble compounds which enter the aqueous suspending media. The media is separated after chlorinolysis and the coal dechlorinated at a temperature of from 300 C to 500 C to form a non-caking, low-sulfur coal product.

Kalvinskas, J. J.↗
NASA NTRS1983

Hydrodesulfurization of chlorinized coal

A method of desulfurization is described in which high sulfur coals are desulfurized by low temperature chlorinolysis of coal in liquid media, preferably water, followed by hydrodesulfurization at a temperature above 500 C. The coals are desulfurized to an extent of up to 90% by weight and simultaneously dechlorinated to a chlorine content below 0.1% by weight. The product coals have lower volatiles loss, lower oxygen and nitrogen content and higher fixed carbon than raw coals treated with hydrogen under the same conditions. Heating the chlorinated coal to a temperature above 500 C. in inert gas such as nitrogen results in significantly less desulfurization.

Kalvinskas, J. J.↗
NASA NTRS1983

Fluidized bed coal desulfurization

Laboratory scale experiments were conducted on two high volatile bituminous coals in a bench scale batch fluidized bed reactor. Chemical pretreatment and posttreatment of coals were tried as a means of enhancing desulfurization. Sequential chlorination and dechlorination cum hydrodesulfurization under modest conditions relative to the water slurry process were found to result in substantial sulfur reductions of about 80%. Sulfur forms as well as proximate and ultimate analyses of the processed coals are included. These studies indicate that a fluidized bed reactor process has considerable potential for being developed into a simple and economic process for coal desulfurization.

Ravindram, M.↗
NASA NTRS1985

Fluidized bed desulfurization

High sulfur content carbonaceous material, such as coal is desulfurized by continuous fluidized suspension in a reactor with chlorine gas, inert dechlorinating gas and hydrogen gas. A source of chlorine gas, a source of inert gas and a source of hydrogen gas are connected to the bottom inlet through a manifold and a heater. A flow controler operates servos in a manner to continuously and sequentially suspend coal in the three gases. The sulfur content is reduced at least 50% by the treatment.

Ravindram, M.↗
NASA NTRS1988

Filter measurements of chemical composition during the airborne Antarctic ozone experiment

During the Airborne Antarctic Ozone Experiment campaign, a filter sampler was flown to measure the bulk composition of aerosol and gas phases. The background sulfate aerosol was measured in regions inside and outside of the chemically perturbed region (CPR) of the polar vortex. The mass ratio of sulfate outside to inside was 2.8. This is indicative of a cleansing mechanism effecting the CPR or of a different air mass inside versus outside. The absolute value of the sulfate mixing ratio shows that the background aerosol has not been influenced by recent volcanic eruptions. The sulfate measured on the ferry flight returning to NASA Ames shows a decrease towards the equator with increasing concentrations in the northern hemisphere. Nitrate in the aerosol phase was observed on two flights. The largest amount of nitrate measured in the aerosol was 44 percent of the total amount of nitrate observed. Other samples on the same flights show no nitrate in the aerosol phase. The presence of nitrate in the aerosol is correlated with the coldest temperatures observed on a given flight. Total nitrate (aerosol plus acidic vapor nitrate) concentrations were observed to increase at flight altitude with increasing latitude north and south of the equator. Total nitrate was lower inside the CPR than outside. Chloride and flouride were not detected in the aerosol phase. From the concentrations of acidic chloride vapor, the ratio of acidic vapor Cl to acidic vapor F and a summing of the individual chloride containing species to yield a total chloride concentration, there is a suggestion that some of the air sampled was dechlorinated. Acidic vapor phase fluoride was observed to increase at flight altitude with increasing latitude both north and south of the equator. The acidic vapor phase fluoride was the only compound measured with the filter technique that exhibited larger concentrations inside the CPR than outside.

Grandrud, B. W.↗
NASA NTRS1988

Heterogeneous physicochemistry of the winter polar stratosphere

Present chemical theories of the Antarctic ozone hole assume that heterogeneous reactions involving polar stratospheric clouds (PSCs) are the precursor of springtime ozone depletions. However, none of the theories quantify the rates of proposed heterogeneous processed, and none utilize the extensive data base on PSC's. Thus, all of the theories must be considered incomplete until the heterogeneous mechanisms are properly defined. A unified treatment developed of the cloud related processes, both physical and chemical, and the importance of these processes using observation data is calibrated. The rates are compared competitive heterogeneous processes to place reasonable limits on critical mechanisms such as the denitrification and dechlorination of the polar winter stratosphere. Among the subjects addressed here are the physical/chemical properties of PSC's including their relevant microphysical, optical and compositional characteristics, mass transfer rates of gaseous constituents to cloud particles, adsorption, accommodation and sticking coefficients on cloud particles, time constants for condensation, absorption and other microphysical processes, effects of solubility and vapor pressure on cloud composition, the statistics of cloud processing of chemically active condensible species, rate limiting steps in heterogeneous chemical reactions, and the nonlinear dependence of ozone loss on physical and chemical parameters.

Turco, R. P.↗
NASA NTRS1992

Measurements and model calculations of HCl column amounts and related parameters over McMurdo during the austral spring in 1989

Solar spectra obtained from a ground-based Fourier transform infrared instrument at McMurdo (Antarctica) in the spring of 1989 have been analyzed to determine total HCl column amounts. A one-dimensional photochemical model was used to simulate the rate of recovery of HCl in the springtime. Low column amounts (about 1 x 10 exp 15 molecules/sq cm) were observed in early September and may be attributed to the heterogeneous conversion of HCl to active chlorine species during the polar night. The rate of recovery of HCl is consistent with its production by chlorine atoms reacting with methane and is dependent on concentrations of active chlorine species and NO molecules in the altitude region from 12 to 22 km. High HCl column amounts (about 7 x 10 exp 15 molecules/sq cm) were observed following recovery in late October, suggesting that the lower stratosphere in the polar region had descended relative to mid-latitudes and that the degree of dechlorination of the transported air was very small.

Liu, X.↗
NASA NTRS2005

Valiant 'Zero-Valent' Effort Restores Contaminated Grounds

Dense non-aqueous phase liquids (DNAPLs) are chemical compounds that can contaminate soil and groundwater to the point of irreparability. These substances are only slightly soluble in water, and are much denser than water. Because of their solubility, DNAPLs form separate liquid phases in groundwater, and because of their density, DNAPLs sink in aquifers instead of floating at the water table, making it extremely difficult to detect their presence. If left untreated in the ground, they can taint fresh water sources. Common DNAPLs include chlorinated hydrocarbon compounds such as carbon tetrachloride, chloroform, tetrachloroethylene, and trichloroethylene. Trichloroethylene was used during the early days of the Space Program, as a solvent for flushing rocket engines, and for metal cleaning and degreasing of equipment, electronics, and heavy machinery. As a result, areas of Cape Canaveral s Launch Complex 34, the site of several historic Saturn rocket launches occurring from 1959 to 1968, were polluted with chlorinated DNAPLs. Through the direction and guidance of Dr. Jacqueline Quinn, an environmental engineer in the Spaceport Engineering and Technology Directorate at NASA s Kennedy Space Center, a biodegradable environmental cleanup technology was developed to reductively dechlorinate DNAPL sources in polluted water at Launch Complex 34. It was important for Kennedy to nip this problem in the bud, in light of the fact that the Space Center is also a National Wildlife Refuge, home to thousands of shorebirds, endangered sea turtles and eagles, manatees, alligators, and diverse habitats that include brackish marshes and salt water estuaries. The success in remediating this historic launch site has led to numerous commercial applications that are restoring the health of our environmental surroundings.

Source record↗
NASA NTRS2023

In Situ Chemical Reduction Interim Measures Work Plan Hot Spot 3 Mobile Launcher Platform Rehabilitation Sites / Vehicle Assembly Building Area (SWMU 056) Kennedy Space Center, Florida

This document presents the design details of an In Situ Chemical Reduction (ISCR) Interim Measures Work Plan for Hot Spot 3 within Mobile Launcher Platform Rehabilitation Sites/Vehicle Assembly Building Area, Solid Waste Management Unit (SWMU) 056 (SWMU 056), located at the John F. Kennedy Space Center, Florida. The interim measures (IM) treatment zone encompasses an area identified as the High Concentration Plume (HCP), which is defined as the area with chlorinated volatile organic compound (CVOC) groundwater concentrations greater than their respective Natural Attenuation Default Concentration (NADC). The objective of the IM is to remove CVOC mass within the treatment area to levels that facilitate a transition to natural attenuation monitoring. The IM design consists of the selected ISCR amendment, Provect-IR, which is a mixture of solid reagents in a single product that promotes enhanced reductive dechlorination and ISCR. ProvectIR includes natural antimethanogenic compounds; multiple hydrophilic, nutrient-rich organic carbon sources; zero valent iron; chemical oxygen scavengers; and vitamin and mineral sources. The proposed treatment area for this IM encompasses less than 1 acre and includes three vertical treatment intervals to reach the NADC plumes that vary per CVOC and depth: 4 to 10 feet below land surface (bls), 10 to 18 feet bls, and 42 to 52 feet bls. The amendment will be distributed through 16 injection points (IP01 through IP16) using dosing rates ranging from 0.4% to 0.6% of soil mass within the treatment interval and a 15% or 20% slurry strength. Dosage rates and slurry strength are based on groundwater geochemistry, soil characteristics, and contaminant concentrations. To aid in the evaluation of the ISCR IM performance, six performance monitoring wells will be installed following injections and sampled semiannually. CVOC parameters will be sampled until concentrations reduce to below their NADC. Underground Injection Control parameters will be sampled until concentrations decrease to background levels or to levels that meet respective groundwater standards. Sampling frequency will be evaluated annually and modified as needed. The path forward for the ISCR IM implementation includes preparing the IM Implementation Work Plan, ISCR injections, monitoring well installation, performance monitoring, and reporting.

Randall K. Sillan↗