Chlorinated hydrocarbon insecticides
Friend, M.; Franson, J.C.
1999-01-01
Chlorinated hydrocarbon insecticides (OCs) are diverse synthetic chemicals that belong to several groups, based on chemical structure. DDT is the best known of these insecticides. First synthesized in 1874, DDT remained obscure until its insecticidal properties became known in 1939, a discovery that earned a Nobel Prize in 1948. The means of synthesizing the cyclodiene group, the most toxic of the OCs, was discovered in 1928 and resulted in a Nobel Prize in 1950. The insecticidal properties of cyclodienes, which include aldrin, dieldrin, and endrin (Table 40.1), were discovered about 1945. OCs became widely used in the United States following World War II. Their primary uses included broad spectrum applications for agricultural crops and forestry and, to a lesser extent, human health protection by spraying to destroy mosquitoes and other potential disease carriers. These compounds also became widely used to combat insect carriers of domestic animal diseases.
Comparative toxicity of insecticides to Choristoneura species (Lepidoptera: Tortricidae)
Jacqueline L. Robertson; Nancy L. Gillette; Barbara A. Lucas; Robert M. Russell; N.E. Savin
1978-01-01
Selected carbamate, chlorinated hydrocarbon, organophosphorous, and pyrethroid insecticides were tested on six Choristoneura species: conflictana (Walker), fumiferana (Clemens), lambertiana ponderosana Obraztsov, occidentalis Freeman, pinus Freeman, and...
Western tent caterpillar: Contact toxicity of ten insecticides applied to the larvae
Jacqueline L. Robertson; Nancy L. Gillette
1973-01-01
Ten chemicals representative of four insecticide groups (earbamate, organophosphate, chlorinated hydrocarbon, and pyrethroid) were applied topically to mixed groups of 5th- and 6th-stage larvae of Malaeosoma californicum califomicum (Packard). Only 2&emdash;the pyrethroid NIA 24110 ((5-benzyl-3-furyl) methyl trans-( +)-3-(...
Effectiveness of organo-phosphorus insecticides against houseflies and mosquitos
Lindquist, A. W.
1957-01-01
The paper describes the research being undertaken on organo-phosphorus insecticides for the control of houseflies and mosquitos. The information obtained from laboratory and field tests indicates that these insecticides are at present effective substitutes for DDT and other chlorinated-hydrocarbon insecticides for use against resistant houseflies and culicine mosquitos, but the residual applications are not as long lasting as those of DDT and therefore will probably not be as efficient in anopheline control. PMID:13413645
Neurotoxicoses of small animals
DOE Office of Scientific and Technical Information (OSTI.GOV)
Simpson, S.T.
1976-02-01
Among the great variety of potentially neurotoxic substances are insecticides, rodenticides, herbicides, fungicides, heavy metals, plants, drugs, reptile and insect venoms, industrial chemicals and contaminated foodstuffs. The neurotoxicoses associated with several of these are described. Of the insecticides, organophosphates and chlorinated hydrocarbons are discussed. The heavy metals thallium and lead are discussed along with botulism and polyradiculoneuritis. 22 references.
Davis, Paul W.; Friedhoff, Jacqueline M.; Wedemeyer, Gary A.
1972-01-01
The current widespread presence of chlorinated insecticides, polychlorinated biphenyls (PCB's) and herbicides in world waterways has elicited much interest in the mechanisms of their toxicity in fishes. Inhibition of Na+,K+-activated adenosinetriphosphatase (NaK-ATPase) and Mg++-dependent ATPase (Mg-ATPase) by DDT, endosulfan and dicofol has been demonstrated in gill, brain and kidney microsomes of rainbow trout (1,2). Intestinal and gill ATPases in marine teleosts were recently reported to be sensitive to organochlorines (3). CutkonTp et al (4) noted inhibition of NaK-ATPase and Mg-ATPase in bluegill brain, liver, muscle and kidney by DDT and related chlorinated hydrocarbons. Inhibition of ATPases by PCB's has been recently shown in bluegill kidney, brain and liver (5). In the present study, we have further examined the NaK-ATPase enzyme system in trout gill as a site for the possible toxicity of selected organopolychlors, i.e., chlorinated insecticides, herbicides and PCB's.
Behavioral toxicology, risk assessment, and chlorinated hydrocarbons.
Evangelista de Duffard, A M; Duffard, R
1996-01-01
Behavioral end points are being used with greater frequency in neurotoxicology to detect and characterize the adverse effects of chemicals on the nervous system. Behavioral measures are particularly important for neurotoxicity risk assessment since many known neurotoxicants do not result in neuropathology. The chlorinated hydrocarbon class consists of a wide variety of chemicals including polychlorinated biphenyls, clioquinol, trichloroethylene, hexachlorophene, organochlorine insecticides (DDT, dicofol, chlordecone,dieldrin, and lindane), and phenoxyherbicides. Each of these chemicals has effects on motor, sensory, or cognitive function that are detectable using functional measures such as behavior. Furthermore, there is evidence that if exposure occurs during critical periods of development, many of the chlorinated hydrocarbons are developmental neurotoxicants. Developmental neurotoxicity is frequently expressed as alterations in motor function or cognitive abilities or changes in the ontogeny of sensorimotor reflexes. Neurotoxicity risk assessment should include assessments of the full range of possible neurotoxicological effects, including both structural and functional indicators of neurotoxicity. PMID:9182042
Lindane in forestry: a continuing controversy
Thomas W. Koerber
1976-01-01
Use of the chlorinated hydrocarbon insecticide lindane to control bark beetles is controversial. Differences of opinion persist, even among knowledgeable entomologists, on whether use is justified in view of potentially harmful side effects. Effectiveness of lindane treatments, as employed in preventing tree mortality from bark beetles, is also in question. In seven...
Chemical Control of Cottonwood Insects
F. L. Oliveria; L. P. Abrahamson
1976-01-01
Systemic insecticides provide the safest and most effective chemical control of defoliators, borers, and sapsucking insects of PopuLus sp. Carbamates and organo-phosphate sprays are good contact and stomach poisons for defoliators, adult borers, some miners, and immature borers. In many countries chlorinated hydrocarbons are still being used because they are economical...
Gałgowska, Michalina; Pietrzak-Fiećko, Renata
2017-03-04
The aim of this study was to determine the level of chlorinated hydrocarbon residues in selected edible mushrooms from north-eastern Poland. The experiment was carried out on 45 samples consisting of 15 fruiting bodies each of the following species: Boletus edulis, Imleria badia and Cantharellus cibarius. Dried samples were subjected to extraction of lipids with a Soxhlet and a standard procedure-based on the decomposition of lipids by concentrated sulfuric acid and the release of organic insecticides to the hexane layer-was used to determine chlorinated hydrocarbons. The quantitative determination of DDT, DDE, DDD and γ-HCH were conducted using gas chromatography with electron capture detection (GC-ECD). Chlorinated hydrocarbons were found in all tested samples. The contents of these compounds varied between all three species. Mean content of γ-HCH in B. edulis, I. badia and C. cibarius was: 2.60; 4.83; 7.52 µg kg -1 of lipids, while the content of ΣDDT was: 57.02; 25.20; 127.10 µg kg -1 of lipids, respectively. These results show that mushrooms from the north-eastern part of Poland can be used as potential bio-indicators of environmental contamination with chlorinated hydrocarbons. Moreover, the studied fungi could still be used as food due to the low levels of analyzed organochlorine compounds.
Neonicotinoid insecticides: highlights of a symposium on strategic molecular designs.
Tomizawa, Motohiro; Casida, John E
2011-04-13
Neonicotinoids are the newest of the five major classes of insecticides (the others are chlorinated hydrocarbons, organophosphorus compounds, methylcarbamates, and pyrethroids), and they make up approximately one-fourth of the world insecticide market. Nithiazine was the lead compound from Shell Development Co. in California later optimized by Shinzo Kagabu of Nihon Tokushu Noyaku Seizo to increase the potency and photostability, resulting in imidacloprid and thiacloprid. These discoveries are the basis for the International Award for Research in Agrochemicals of the American Chemical Society presented in 2010 to Professor Shinzo Kagabu. Five other neonicotinoids were added by others for the current set of seven commercial compounds. This symposium considers the progress in discovery and development of novel chemotype nicotinic insecticides with enhanced effectiveness, unique biological properties, and maximal safety. Chemorational approaches considered include physicochemical properties, metabolic activation and detoxification, and chemical and structural biology aspects potentially facilitating receptor structure-guided insecticide design.
Chlordane Contamination of Government Quarters and Personal Property, Webb AFB, Texas
1970-03-12
that chlorinated hydrocarbons do not inhibit cholinesterase as is the case with organophosphate and carbamate insecticides. Symptoms of acute poisoning...cardboard lined conduits within the concrete slab. Subsequent activation of the heating systems resulted in extensive human exposure and gross pesticide...they were considered ul.affected by their exposures to cholinesterase depressants. Such indexes of toxicity are now considered incomplete. 0. Table
The relative toxicities of several pesticides to naiads of three species of stoneflies
Sanders, Herman O.; Cope, Oliver B.
1968-01-01
Static bioassays were conducted to determine the relative acute toxicities of some insecticides, herbicides, fungicides, a defoliant, and a molluscicide to the naiads of three species of stonef!y, Pteronarcys califomica, Pteronarcella badia, and Claassenia sabulosa. Toxic effects were measured by determination of median lethal concn (Lcoo) for 24-, 48-, and 96-hr exposures, at 15.5C. Endrin and dieldrin were the most and DDT the least toxic of the chlorinated hydrocarbon insecticides tested. Parathion was the most toxic organophosphate insecticide to P. califomica naiads, but dursban was the most toxic to P. badia and C. sabulosa naiads. Trichlorofon ( Dipterex) was the least toxic to all three species. P. badia, the species of smallest size, was the species most susceptible to most pesticides, followed in descending order of sensitivity by C. sabulosa and P. califomica. Smaller specimens of P. californica naiads were consistently more susceptible to some insecticides than larger specimens of the same species.
Pesticides data-collection activities of the U.S. Geological Survey in Texas
Manigold, Douglas B.
1974-01-01
In 1965, the U.S. Geological Survey initiated a monthly monitoring program on 3 streams in Texas, screening for 9 of the more commonly used organochlorine insecticides: Aldrin, DDD, DDE , DDT, dieldrin, endrin, heptachlor, heptachlor epoxide, and lindane. Later, the herbicides 2,4-D; 2,4,5-T; and silvex were added. In 1967 a quarterly monitoring program was initiated at 26 sites on the principal streams of the State and a survey of the occurrence of pesticide residues in ground water. By 1970, the Geological Survey had developed methods for measuring pesticide residues in sediment, and in that year, the quarterly analysis of stream-bottom materials at 39 sites was added to the data collection program. Geological Survey pesticide data for 108 sites on nontidal reaches of streams in Texas have been summarized by Rawson (1974). The pesticides studied are widely distributed in surface waters in Texas. The most widely distributed chlorinated-hydrocarbon insecticides were dieldrin at 77 sites, DDT at 67 sites, lindane at 59 sites, and chlordane at 38 sites. The most widely distributed phosphorothioate insecticide was diazinon, which was detected at 80 sites. Small amounts of each of the chlorinated-hydrocarbon herbicides were widely distributed (2,4,5-T at 96 sites, 2,4-D at 78 sites, and Silvex at 47 sites). Although only chlordane, in 2 samples from 1 site exceeded the maximum limit recommended for water to be used for public supply, 1 or more pesticides in at least 1 sample from 57 sites exceeded the maximum environmental level for marine waters recommended by the National Technical Advisory Committee. (Woodard-USGS)
40 CFR 268.40 - Applicability of treatment standards.
Code of Federal Regulations, 2011 CFR
2011-07-01
... chlorinated aliphatic hydrocarbons by free radical catalyzed processes. These chlorinated aliphatic... chlorinated aliphatic hydrocarbons, by free radical catalyzed processes. These chlorinated aliphatic... production of certain chlorinated aliphatic hydrocarbons, by free radical catalyzed processes. These...
40 CFR 268.40 - Applicability of treatment standards.
Code of Federal Regulations, 2010 CFR
2010-07-01
... chlorinated aliphatic hydrocarbons by free radical catalyzed processes. These chlorinated aliphatic... chlorinated aliphatic hydrocarbons, by free radical catalyzed processes. These chlorinated aliphatic... production of certain chlorinated aliphatic hydrocarbons, by free radical catalyzed processes. These...
Fox, Irving
1961-01-01
Failure to control Aëdes aegypti in Puerto Rico has suggested resistance to the insecticides, particularly DDT. A laboratory colony (named Isla Verde strain) was established from material obtained near the International Airport. This strain proved highly resistant to DDT and dieldrin as well as various other insecticides. The scientific and practical significance of this is far-reaching. Heretofore, it was thought that populations of Aëdes aegypti could be resistant to the DDT group of insecticides or to the dieldrin group but not to both, and that one type of resistance involved biochemical, toxicological and genetic characteristics different from the other. This theory must now be modified or even abandoned. From the practical point of view, it is clear that the continued use of DDT or dieldrin for Aëdes aegypti control in Puerto Rico is questionable, for it is not wise to attempt to overcome high resistance by increasing the concentration or rate of application. Further, the situation demonstrated for Puerto Rico may also obtain in other islands of the Caribbean where Aëdes aegypti is known to be DDT-resistant. PMID:13701099
DOE Office of Scientific and Technical Information (OSTI.GOV)
Cin, D.A.; Kroger, M.
Concentrations of the chlorinated hydrocarbon insecticide mirex (C/sub 10/Cl/sub 12/) were determined in brown trout from a defined contaminated area of Spring Creek, Centre County, PA, using electron-capture gas chromatography. Conventional heat treatments, namely, baking, frying, poaching, and baking without skin, did not cause significant decreases of the contaminant. Ultraviolet irradiation led to significant reductions (p < 0.05) in mirex concentration in muscle tissue. Exposures of 24, 48, and 72 hr led to degradations of 30.0%, and 45.6%, respectively, of the initial mirex concentration. Gamma irradiation also led to significant reductions (p < 0.05) in mirex concentration in muscle tissue.more » Following absorption of 1, 3, and 5 Mrad, degradations of 9.8%, 23,1%, and 37.5%, respectively, of the initial mirex concentration were observed.« less
40 CFR 261.31 - Hazardous wastes from non-specific sources.
Code of Federal Regulations, 2011 CFR
2011-07-01
... free radical catalyzed processes. These chlorinated aliphatic hydrocarbons are those having carbon... spent desiccant wastes from the production of certain chlorinated aliphatic hydrocarbons, by free radical catalyzed processes. These chlorinated aliphatic hydrocarbons are those having carbon chain...
40 CFR 261.31 - Hazardous wastes from non-specific sources.
Code of Federal Regulations, 2010 CFR
2010-07-01
... free radical catalyzed processes. These chlorinated aliphatic hydrocarbons are those having carbon... spent desiccant wastes from the production of certain chlorinated aliphatic hydrocarbons, by free radical catalyzed processes. These chlorinated aliphatic hydrocarbons are those having carbon chain...
Wang, Xianli; Kang, Haiyan; Wu, Junfeng
2016-05-01
Given the potential risks of chlorinated polycyclic aromatic hydrocarbons, the analysis of their presence in water is very urgent. We have developed a novel procedure for determining chlorinated polycyclic aromatic hydrocarbons in water based on solid-phase extraction coupled with gas chromatography and mass spectrometry. The extraction parameters of solid-phase extraction were optimized in detail. Under the optimal conditions, the proposed method showed wide linear ranges (1.0-1000 ng/L) with correlation coefficients ranging from 0.9952 to 0.9998. The limits of detection and the limits of quantification were in the range of 0.015-0.591 and 0.045-1.502 ng/L, respectively. Recoveries ranged from 82.5 to 102.6% with relative standard deviations below 9.2%. The obtained method was applied successfully to the determination of chlorinated polycyclic aromatic hydrocarbons in real water samples. Most of the chlorinated polycyclic aromatic hydrocarbons were detected and 1-monochloropyrene was predominant in the studied water samples. This is the first report of chlorinated polycyclic aromatic hydrocarbons in water samples in China. The toxic equivalency quotients of chlorinated polycyclic aromatic hydrocarbons in the studied tap water were 9.95 ng the toxic equivalency quotient m(-3) . 9,10-Dichloroanthracene and 1-monochloropyrene accounted for the majority of the total toxic equivalency quotients of chlorinated polycyclic aromatic hydrocarbons in tap water. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.
Hochreiter, Joseph J.
1982-01-01
This report presents chemical-quality data collected from May 1980 to January 1981 at several locations within the Delaware River estuary and selected New Jersey tributaries. Samples of surface water were analyzed Environmental Protection Agency ' priority pollutants, ' including acid extractable, base/neutral extractable and volatile organic compounds, in addition to selected dissolved inorganic constituents. Surficial bed material at selected locations was examined for trace metals, insecticides, polychlorinated biphenyls, and base/neutral extractable organic compounds. Trace levels (1-50 micrograms per liter) of purgeable organic compounds, particularly those associated with the occurrence of hydrocarbons, were found in about 60% of the water samples taken. DDT, DDD, DDE, PCB 's and chlordane are present in most surficial bed material samples. Diazinon was the only organophosphorous insecticide detected in the study (1.6 micrograms per kilogram at one location). High values for select trace metals in bed material were discovered at two locations. Of the 10 sites sampled, the surficial bed material containing the most contamination was found along one cross section of Raccoon Creek at Bridgeport. An additional analysis of Raccoon Creek revealed bed material containing toluene, oil and grease, and trace quantities of 15 base/neutral extractable organic compounds, including polynuclear aromatic hydrocarbons, phthalate esters, and chlorinated benzenes.
Photo-oxidation method using MoS2 nanocluster materials
Wilcoxon, Jess P.
2001-01-01
A method of photo-oxidizing a hydrocarbon compound is provided by dispersing MoS.sub.2 nanoclusters in a solvent containing a hydrocarbon compound contaminant to form a stable solution mixture and irradiating the mixture to photo-oxide the hydrocarbon compound. Hydrocarbon compounds of interest include aromatic hydrocarbon and chlorinated hydrocarbons. MoS.sub.2 nanoclusters with an average diameter less than approximately 10 nanometers are shown to be effective in decomposing potentially toxic aromatic and chlorinated hydrocarbons, such as phenol, pentachlorophenol, chlorinated biphenols, and chloroform, into relatively non-toxic compounds. The irradiation can occur by exposing the MoS.sub.2 nanoclusters and hydrocarbon compound mixture with visible light. The MoS.sub.2 nanoclusters can be introduced to the toxic hydrocarbons as either a MoS.sub.2 solution or deposited on a support material.
Brock, Robert D.; Murtagh, Lucinda K.
1994-01-01
Twenty-two bottom-sediment samples were collected from Town Lake in Austin, Texas, in 1991 and 1992 and analyzed for chlorinated insecticides by a reconnaissance-quality, electron-capture gas chromatography screening method developed by the U.S. Geological Survey (USGS). Four different chlorinated insecticides (aldrin, chlordane, dieldrin, and p,p'-DDT) and two degradation products of p,p'-DDT (p,p'-DDD and p,p'-DDE) were detected in these samples. The most significant insecticides detected were chlordane, which was detected in 20 of the 22 samples at concentrations that ranged from 26 to 140 micrograms per kilogram, and p,p'-DDT, which was detected in all 22 samples at concen- trations that ranged from 5 to 40 micrograms per kilogram. Degradation products of p,p'-DDT were detected in all 22 samples. Concentrations of p,p'-DDD ranged from not detected to 117 micrograms per kilogram and for p,p'-DDE from 9 to 97 micrograms per kilogram. Of the 22 samples collected, 15 also were analyzed by the standard USGS laboratory analytical method for chlorinated insecticides to determine the comparability of the two methods. Correlation coefficients were calculated for chlordane (0.8662), p,p'-DDT (0.6393), p,p'-DDD (0.9401), p,p'-DDE (0.8595), and dieldrin (0.3819). A paired sign test at the 95 percent confidence level showed no significant difference between the screening method and laboratory analytical method for all detected insecticides except aldrin. P-values were calculated from the data for chlordane (l.0000), p,p'-DDT (0.1796), p,p'-DDD (l,0000), p,p'-DDE (0.1796), and dieldrin (0.2891).
Biotransformation of chlorinated aliphatic hydrocarbons under anaerobic conditions has received considerable attention due to the prevalence of these compounds as groundwater contaminants. However, information concerning the impact of mixtures of chlorinated compounds on their...
PRN 75-5: Unacceptable Use of the Word Chlorine in the Name and Labeling of Pesticides
Use of the word CHLORINE on labels other than in products containing liquified chlorine under pressure has been determined to be in violation of Section 2(q)(l)(A) of the Federal Insecticide, Fungicide, and Rodenticide Act.
Water-quality data for selected stations in the East Everglades, Florida
Waller, Bradley G.
1981-01-01
The results of water-quality samples collected from April 1978 through April 1980 from three canal stations, four marsh stations, and two ground-water stations within the East Everglades, Dade County, Florida, are tabulated in 37 tables. The major categories of parameters analyzed are field measurements, physical characteristics, macronutrients (carbon, nitrogen, and phosphorus), major ions, trace elements, and algae. Chemical data for bulk-precipitation stations within and adjacent to the East Everglades are also given. The parameters analyzed include macronutrients, major ions, and trace elements. The period of record for these stations is October 1977 through April 1980. Bottom material at the canal and marsh stations was collected twice during the investigation. These data include analyses for macronutrients, trace elements, and chlorinated-hydrocarbon insecticides. (USGS)
Knauss, Kevin G.; Copenhaver, Sally C.; Aines, Roger D.
2000-01-01
In situ hydrous pyrolysis/oxidation process is useful for in situ degradation of hydrocarbon water and soil contaminants. Fuel hydrocarbons, chlorinated hydrocarbons, polycyclic aromatic hydrocarbons, petroleum distillates and other organic contaminants present in the soil and water are degraded by the process involving hydrous pyrolysis/oxidation into non-toxic products of the degradation. The process uses heat which is distributed through soils and water, optionally combined with oxygen and/or hydrocarbon degradation catalysts, and is particularly useful for remediation of solvent, fuel or other industrially contaminated sites.
Volatile and organic compositions of sedimentary rocks in Yellowknife Bay, Gale crater, Mars.
Ming, D W; Archer, P D; Glavin, D P; Eigenbrode, J L; Franz, H B; Sutter, B; Brunner, A E; Stern, J C; Freissinet, C; McAdam, A C; Mahaffy, P R; Cabane, M; Coll, P; Campbell, J L; Atreya, S K; Niles, P B; Bell, J F; Bish, D L; Brinckerhoff, W B; Buch, A; Conrad, P G; Des Marais, D J; Ehlmann, B L; Fairén, A G; Farley, K; Flesch, G J; Francois, P; Gellert, R; Grant, J A; Grotzinger, J P; Gupta, S; Herkenhoff, K E; Hurowitz, J A; Leshin, L A; Lewis, K W; McLennan, S M; Miller, K E; Moersch, J; Morris, R V; Navarro-González, R; Pavlov, A A; Perrett, G M; Pradler, I; Squyres, S W; Summons, R E; Steele, A; Stolper, E M; Sumner, D Y; Szopa, C; Teinturier, S; Trainer, M G; Treiman, A H; Vaniman, D T; Vasavada, A R; Webster, C R; Wray, J J; Yingst, R A
2014-01-24
H2O, CO2, SO2, O2, H2, H2S, HCl, chlorinated hydrocarbons, NO, and other trace gases were evolved during pyrolysis of two mudstone samples acquired by the Curiosity rover at Yellowknife Bay within Gale crater, Mars. H2O/OH-bearing phases included 2:1 phyllosilicate(s), bassanite, akaganeite, and amorphous materials. Thermal decomposition of carbonates and combustion of organic materials are candidate sources for the CO2. Concurrent evolution of O2 and chlorinated hydrocarbons suggests the presence of oxychlorine phase(s). Sulfides are likely sources for sulfur-bearing species. Higher abundances of chlorinated hydrocarbons in the mudstone compared with Rocknest windblown materials previously analyzed by Curiosity suggest that indigenous martian or meteoritic organic carbon sources may be preserved in the mudstone; however, the carbon source for the chlorinated hydrocarbons is not definitively of martian origin.
Volatile and organic compositions of sedimentary rocks in Yellowknife Bay, Gale crater, Mars
Ming, D. W.; Archer, P.D.; Glavin, D.P.; Eigenbrode, J.L.; Franz, H.B.; Sutter, B.; Brunner, A.E.; Stern, J.C.; Freissinet, C.; McAdam, A.C.; Mahaffy, P.R.; Cabane, M.; Coll, P.; Campbell, J.L.; Atreya, S.K.; Niles, P.B.; Bell, J.F.; Bish, D.L.; Brinckerhoff, W.B.; Buch, A.; Conrad, P.G.; Des Marais, D.J.; Ehlmann, B.L.; Fairén, A.G.; Farley, K.; Flesch, G.J.; Francois, P.; Gellert, Ralf; Grant, J. A.; Grotzinger, J.P.; Gupta, S.; Herkenhoff, K. E.; Hurowitz, J.A.; Leshin, L.A.; Lewis, K.W.; McLennan, S.M.; Miller, Karl E.; Moersch, J.; Morris, R.V.; Navarro- González, R.; Pavlov, A.A.; Perrett, G.M.; Pradler, I.; Squyres, S. W.; Summons, Roger E.; Steele, A.; Stolper, E.M.; Sumner, D.Y.; Szopa, C.; Teinturier, S.; Trainer, M.G.; Treiman, A.H.; Vaniman, D.T.; Vasavada, A.R.; Webster, C.R.; Wray, J.J.; Yingst, R.A.
2014-01-01
H2O, CO2, SO2, O2, H2, H2S, HCl, chlorinated hydrocarbons, NO, and other trace gases were evolved during pyrolysis of two mudstone samples acquired by the Curiosity rover at Yellowknife Bay within Gale crater, Mars. H2O/OH-bearing phases included 2:1 phyllosilicate(s), bassanite, akaganeite, and amorphous materials. Thermal decomposition of carbonates and combustion of organic materials are candidate sources for the CO2. Concurrent evolution of O2 and chlorinated hydrocarbons suggests the presence of oxychlorine phase(s). Sulfides are likely sources for sulfur-bearing species. Higher abundances of chlorinated hydrocarbons in the mudstone compared with Rocknest windblown materials previously analyzed by Curiosity suggest that indigenous martian or meteoritic organic carbon sources may be preserved in the mudstone; however, the carbon source for the chlorinated hydrocarbons is not definitively of martian origin.
Impact Of Landfill Closure Designs On Long-Term Natural Attenuation Of Chlorinated Hydrocarbons
2002-03-01
chlorinated aliphatic hydrocarbons (CAHs) (i.e., chlorinated solvents) in landfills and landfill- leachate -contaminated groundwater. The project was divided...attenuation rather than expensive leachate collection and treatment systems. At some landfills, surface infiltration may accelerate the leaching of...the “source” and reduce the time required for biological stabilization of the landfilled waste. Recirculation of landfill leachate could also be
RELATIONSHIPS BETWEEN LABORATORY AND PILOT-SCALE COMBUSTION OF SOME CHLORINATED HYDROCARBONS
Factors governing the occurence of trace amounts of residual organic substance emmissions (ROSEs) in full-scale incierators are not fully understood. Pilot-scale spray combustion expereiments involving some liquid chlorinated hydrocarbons (CHCs) and their dilute mixtures with hy...
USE OF SONOCHEMISTRY IN MONITORING CHLORINATED HYDROCARBONS IN WATER
The U.S. Environmental Protection Agency (EPA) has been examining the potential of combining sonication with available measurement technologies for monitoring chlorinated hydrocarbons in water. The chloride ion (C1-) concentration, conductivity, and pH were measured before and af...
Birds and Dutch elm disease control
DeWitt, J.B.
1958-01-01
Brief, factual review of information on effect of DDT and other insecticides on birds. One program for control of elm disease caused 22% decrease in number of adult birds and 56% mortality of nestlings. Quail fed 3 oz. of DDT per ton of food had 16% reduction in young hatched and 500% increase in defective chicks. Quail fed same dosage during winter and breeding seasons had 30% decrease in fertile eggs and 800% increase in defective chicks. More than 90% of their chicks died in first 6 weeks although fed no insecticide. Almost equally bad results came from feeding Pheasants diets with about 1 oz. DDT per ton. Other common insecticides (chlorinated hydrocarbons) also caused lowered chick survival and higher percentages of crippled chicks. From field data we know that 2 lbs. DDT/acre can affect birds and has even worse effects on cold-blooded animals. Efforts to control elm disease have left as much as 196 lbs. DDT/acre in top 3 inches of soil. Earthworms concentrate DDT in their tissues. Thus the treated areas can be traps for birds and other animals. What can be done? 1) In control of elm disease, use minimum effective amount of insecticide; mist blowers use less than sprayers. 2) Avoid applications during migration and nesting seasons. It has been reported that adequate control can be obtained with dormant sprays and that foliar applications may not be required. Tables of this paper show effects of DDT on reproduction of Quail, relative toxicity to quail of 8 insecticides, and amounts of 7 insecticides required to cause 40% or more decrease in Quail reproduction. These comparisons demonstrate that Aldrin, Endrin, and Dieldrin are 20 to 200 times as toxic as DDT and that Heptachlor and Chlordane are only slightly less toxic than Dieldrin. Methoxychlor and Strobane are less toxic to Quail than is DDT.
Transformation of Chlorinated Hydrocarbons on Synthetic Green Rusts
Green rusts (GRs) are layered double hydroxides that contain both ferrous and ferric ions in their structure. GRs can potentially serve as a chemical reductant for degradation of chlorinated hydrocarbons. GRs are found in zerovalent iron based permeable reactive barriers and in c...
TURBULENT FLAME REACTOR STUDIES OF CHLORINATED HYDROCARBON DESTRUCTION EFFICIENCY
Four mixtures of C1 and C2 chlorinated hydrocarbons, diluted in heptane, were burned in a Turbulent Flame Reactor (TFR) under high and low oxygen conditions. Emissions of undestroyed feed, stable organic by-products, carbon monoxide, carbon dioxide and oxyg...
Monitoring the Success of Sediment Remediation at a Site Contaminated with Chlorinated Pesticides, Polynuclear Aromatic Hydrocarbons and Arsenic (Baird & McGuire Superfund Site, Holbrook, MA) Contaminated sediment in the Cochato River adjacent to the Baird & McGuire Superfund Sit...
REFINING FLUORINATED COMPOUNDS
Linch, A.L.
1963-01-01
This invention relates to the method of refining a liquid perfluorinated hydrocarbon oil containing fluorocarbons from 12 to 28 carbon atoms per molecule by distilling between 150 deg C and 300 deg C at 10 mm Hg absolute pressure. The perfluorinated oil is washed with a chlorinated lower aliphatic hydrocarbon, which mairtains a separate liquid phase when mixed with the oil. Impurities detrimental to the stability of the oil are extracted by the chlorinated lower aliphatic hydrocarbon. (AEC)
Chang, H L; Alvarez-Cohen, L
1996-01-01
The microbial degradation of chlorinated and nonchlorinated methanes, ethanes, and ethanes by a mixed methane-oxidizing culture grown under chemostat and batch conditions is evaluated and compared with that by two pure methanotrophic strains: CAC1 (isolated from the mixed culture) and Methylosinus trichosporium OB3b. With the exception of 1,1-dichloroethylene, the transformation capacity (Tc) for each chlorinated aliphatic hydrocarbon was generally found to be in inverse proportion to its chlorine content within each aliphatic group (i.e., methanes, ethanes, and ethenes), whereas similar trends were not observed for degradation rate constants. Tc trends were similar for all methane-oxidizing cultures tested. None of the cultures were able to degrade the fully chlorinated aliphatics such as perchloroethylene and carbon tetrachloride. Of the four cultures tested, the chemostat-grown mixed culture exhibited the highest Tc for trichloroethylene, cis-1,2-dichloroethylene, tetrachloroethane, 1,1,1-trichloroethane, and 1,2-dichloroethane, whereas the pure batch-grown OB3b culture exhibited the highest Tc for all other compounds tested. The product toxicity of chlorinated aliphatic hydrocarbons in a mixture containing multiple compounds was cumulative and predictable when using parameters measured from the degradation of individual compounds. The Tc for each chlorinated aliphatic hydrocarbon in a mixture (Tcmix) and the total Tc for the mixture (sigma Tcmix) are functions of the individual Tc, the initial substrate concentration (S0), and the first-order rate constant (k/Ks) of each compound in the mixture, indicating the importance of identifying the properties and compositions of all potentially degradable compounds in a contaminant mixture. PMID:8795228
The paper discusses simulation of the performance of chlorine-free fluorinated ethers and fluorinated hydrocarbons as potential long-term replacements for CFC-11 and -114. Modeling has been done with in-house refrigeration models based on the Carnahan-Starling-DeSantis Equation o...
NASA Technical Reports Server (NTRS)
Glavin, Daniel P.; Freissinet, Caroline; Miller, Kristen E.; Eigenbrode, Jennifer L.; Brunner, Anna E.; Buch, Arnaud; Sutter, Brad; Archer, P. Douglas, Jr.; Atreya, Sushil K.; Brinckerhoff, William B.;
2013-01-01
A single scoop of the Rocknest aeolian deposit was sieved (less than 150 micrometers), and four separate sample portions, each with a mass of approximately 50 mg, were delivered to individual cups inside the Sample Analysis at Mars (SAM) instrument by the Mars Science Laboratory rover's sample acquisition system. The samples were analyzed separately by the SAM pyrolysis evolved gas and gas chromatograph mass spectrometer analysis modes. Several chlorinated hydrocarbons including chloromethane, dichloromethane, trichloromethane, a chloromethylpropene, and chlorobenzene were identified by SAM above background levels with abundances of approximately 0.01 to 2.3 nmol. The evolution of the chloromethanes observed during pyrolysis is coincident with the increase in O2 released from the Rocknest sample and the decomposition of a product of N-methyl-N-(tert-butyldimethylsilyl)-trifluoroacetamide (MTBSTFA), a chemical whose vapors were released from a derivatization cup inside SAM. The best candidate for the oxychlorine compounds in Rocknest is a hydrated calcium perchlorate (Ca(ClO4)2·nH2O), based on the temperature release of O2 that correlates with the release of the chlorinated hydrocarbons measured by SAM, although other chlorine-bearing phases are being considered. Laboratory analog experiments suggest that the reaction of Martian chlorine from perchlorate decomposition with terrestrial organic carbon from MTBSTFA during pyrolysis can explain the presence of three chloromethanes and a chloromethylpropene detected by SAM. Chlorobenzene may be attributed to reactions of Martian chlorine released during pyrolysis with terrestrial benzene or toluene derived from 2,6-diphenylphenylene oxide (Tenax) on the SAM hydrocarbon trap. At this time we do not have definitive evidence to support a nonterrestrial carbon source for these chlorinated hydrocarbons, nor do we exclude the possibility that future SAM analyses will reveal the presence of organic compounds native to the Martian regolith.
A groundwater treatment technology based on catalytic reductive
dehalogenation has been developed to efficiently destroy chlorinated
hydrocarbons in situ using a reactive well approach. The treatment process
utilizes dissolved H2 as an electron donor, in...
Chlorinated hydrocarbons in lichen and moss samples from the Antarctic Peninsula
DOE Office of Scientific and Technical Information (OSTI.GOV)
Bacci, E.; Calamari, D.; Gaggi, C.
1986-01-01
The concentrations of some chlorinated hydrocarbon residues (HCB, HCH isomers, p,p'DDT and DDE, PCB cogeners) in lichen and moss samples from the Antarctic Peninsula are reported and compared with available data from other parts of the world. The use of these materials as indicators of tropospheric contamination levels in Antarctica is discussed.
Jin, Biao; Haderlein, Stefan B; Rolle, Massimo
2013-02-05
We propose a self-consistent method to predict the evolution of carbon and chlorine isotope ratios during degradation of chlorinated hydrocarbons. The method treats explicitly the cleavage of isotopically different C-Cl bonds and thus considers, simultaneously, combined carbon-chlorine isotopologues. To illustrate the proposed modeling approach we focus on the reductive dehalogenation of chlorinated ethenes. We compare our method with the currently available approach, in which carbon and chlorine isotopologues are treated separately. The new approach provides an accurate description of dual-isotope effects regardless of the extent of the isotope fractionation and physical characteristics of the experimental system. We successfully applied the new approach to published experimental results on dehalogenation of chlorinated ethenes both in well-mixed systems and in situations where mass-transfer limitations control the overall rate of biodegradation. The advantages of our self-consistent dual isotope modeling approach proved to be most evident when isotope fractionation factors of carbon and chlorine differed significantly and for systems with mass-transfer limitations, where both physical and (bio)chemical transformation processes affect the observed isotopic values.
Baker, Angela K.; Sauvage, Carina; Thorenz, Ute R.; van Velthoven, Peter; Oram, David E.; Zahn, Andreas; Brenninkmeijer, Carl A. M.; Williams, Jonathan
2016-01-01
The chlorine radical is a potent atmospheric oxidant, capable of perturbing tropospheric oxidative cycles normally controlled by the hydroxyl radical. Significantly faster reaction rates allow chlorine radicals to expedite oxidation of hydrocarbons, including methane, and in polluted environments, to enhance ozone production. Here we present evidence, from the CARIBIC airborne dataset, for extensive chlorine radical chemistry associated with Asian pollution outflow, from airborne observations made over the Malaysian Peninsula in winter. This region is known for persistent convection that regularly delivers surface air to higher altitudes and serves as a major transport pathway into the stratosphere. Oxidant ratios inferred from hydrocarbon relationships show that chlorine radicals were regionally more important than hydroxyl radicals for alkane oxidation and were also important for methane and alkene oxidation (>10%). Our observations reveal pollution-related chlorine chemistry that is both widespread and recurrent, and has implications for tropospheric oxidizing capacity, stratospheric composition and ozone chemistry. PMID:27845366
Schoof, H. F.; Mathis, Willis; Austin, J. R.
1961-01-01
The appearance of resistance to both dieldrin and DDT in several malaria vectors has intensified investigations on the potential of organophosphorus compounds for residual application. This report describes the final year's activities of a three-year study on malathion. Water-wettable formulations of malathion and of Bayer 29493 were evaluated against DDT/dieldrin-resistant Anopheles albimanus in El Salvador. The results indicate that neither compound at a dosage of 0.5 g/m2 offers any promise as a residual agent. At dosages of 1.0 g/m2 or 2.0 g/m2 the two toxicants gave effective kills (70%-100%) for periods of 21/2-3 months, based on 1-hour exposure to the treated surfaces. Up to 3 months, both compounds gave similar levels of effectiveness on wood, thatch, and mud. On whitewash and plaster surfaces, Bayer 29493 was superior to malathion. The findings indicate that each insecticide has considerable potential value for residual treatment in areas where the malaria vector cannot be killed effectively by either DDT or dieldrin. In such areas, further investigation into their utility as replacements for the chlorinated hydrocarbon insecticides is warranted. ImagesFIG. 1FIG. 2FIG. 3FIG. 4FIG. 5 PMID:13748489
Aerobic microorganism for the degradation of chlorinated aliphatic hydrocarbons
Fliermans, Carl B.
1989-01-01
A chlorinated aliphatic hydrocarbon-degrading microorganism, having American Type Culture Collection accession numbers ATCC 53570 and 53571, in a biologically pure culture aseptically collected from a deep subsurface habitat and enhanced, mineralizes trichloroethylene and tetrachloroethylene to HCl, H.sub.2 O and Co.sub.2 under aerobic conditions stimulated by methane, acetate, methanol, tryptone-yeast extract, propane and propane-methane.
Jesus, João; Frascari, Dario; Pozdniakova, Tatiana; Danko, Anthony S
2016-05-15
This review analyses kinetic studies of aerobic cometabolism (AC) of halogenated aliphatic hydrocarbons (HAHs) from 2001-2015 in order to (i) compare the different kinetic models proposed, (ii) analyse the estimated model parameters with a focus on novel HAHs and the identification of general trends, and (iii) identify further research needs. The results of this analysis show that aerobic cometabolism can degrade a wide range of HAHs, including HAHs that were not previously tested such as chlorinated propanes, highly chlorinated ethanes and brominated methanes and ethanes. The degree of chlorine mineralization was very high for the chlorinated HAHs. Bromine mineralization was not determined for studies with brominated aliphatics. The examined research period led to the identification of novel growth substrates of potentially high interest. Decreasing performance of aerobic cometabolism were found with increasing chlorination, indicating the high potential of aerobic cometabolism in the presence of medium- and low-halogenated HAHs. Further research is needed for the AC of brominated aliphatic hydrocarbons, the potential for biofilm aerobic cometabolism processes, HAH-HAH mutual inhibition and the identification of the enzymes responsible for each aerobic cometabolism process. Lastly, some indications for a possible standardization of future kinetic studies of HAH aerobic cometabolism are provided. Copyright © 2016 Elsevier B.V. All rights reserved.
Process for converting light alkanes to higher hydrocarbons
Noceti, Richard P.; Taylor, Charles E.
1988-01-01
A process is disclosed for the production of aromatic-rich, gasoline boiling range hydrocarbons from the lower alkanes, particularly from methane. The process is carried out in two stages. In the first, alkane is reacted with oxygen and hydrogen chloride over an oxyhydrochlorination catalyst such as copper chloride with minor proportions of potassium chloride and rare earth chloride. This produces an intermediate gaseous mixture containing water and chlorinated alkanes. The chlorinated alkanes are contacted with a crystalline aluminosilicate catalyst in the hydrogen or metal promoted form to produce gasoline range hydrocarbons with a high proportion of aromatics and a small percentage of light hydrocarbons (C.sub.2 -C.sub.4). The light hydrocarbons can be recycled for further processing over the oxyhydrochlorination catalyst.
Chlorinated organic compounds in urban river sediments
DOE Office of Scientific and Technical Information (OSTI.GOV)
Soma, Y.; Shiraishi, H.; Inaba, K.
1995-12-31
Among anthropogenic chemicals, many chlorinated organic compounds have been used as insecticides and detected frequently as contaminants in urban river sediments so far. However, the number and total amount of chemicals produced commercially and used are increasing year by year, though each amount of chemicals is not so high. New types of contaminants in the environment may be detected by the use of newly developed chemicals. Chlorinated organic compounds in the urban river sediments around Tokyo and Kyoto, large cities in Japan, were surveyed and recent trends of contaminants were studied. Contaminants of the river sediments in industrial areas hadmore » a variety, but PCB (polychlorinated biphenyls) was detected in common in industrial areas. Concentration of PCB related well to the number of factories on both sides of rivers, although the use of PCB was stopped 20 years ago. In domestic areas, Triclosan (5-chloro-2-(2,4-dichlorophenoxy)-phenol) and Triclocarban (3,4,4{prime}-trichlorocarbanilide)(both are contained in soap or shampoo for fungicides), p-dichlorobenzene (insecticides for wears) and TCEP(tris-chloroethyl phosphate) were detected. EOX(extracted organic halogen) in the sediments was 5 to 10 times of chlorinated organic compounds detected by GC/MS. Major part of organic halogen was suggested to be included in chlorinated organics formed by bleaching or sterilization.« less
RADIATION DOSIMETER AND DOSIMETRIC METHODS
Taplin, G.V.
1958-10-28
The determination of ionizing radiation by means of single fluid phase chemical dosimeters of the colorimetric type is presented. A single fluid composition is used consisting of a chlorinated hydrocarbon, an acidimetric dye, a normalizer and water. Suitable chlorinated hydrocarbons are carbon tetrachloride, chloroform, trichloroethylene, trichlorethane, ethylene dichioride and tetracbloroethylene. Suitable acidimetric indicator dyes are phenol red, bromcresol purple, and creosol red. Suitable normallzers are resorcinol, geraniol, meta cresol, alpha -tocopberol, and alpha -naphthol.
NASA Astrophysics Data System (ADS)
Chen, Hui-Ming; Wu, Ming-Tsang
2017-01-01
Groundwater pollution from the petrochemical industry causes serious deterioration of soil and groundwater quality and impacts on human health worldwide. However, few studies have examined the effect of residential exposure to petrochemical chlorinated hydrocarbon-contaminated groundwater on renal function impairment in humans. We conducted an ecological study to investigate the two. A polyvinyl chloride (PVC) plant was located in one of the six villages, the study area, in Kaohsiung city of southwestern Taiwan. Based on the direction of groundwater flow and previous groundwater measurements of chlorinated hydrocarbons from Taiwan Environmental Protection Bureau, we divided the six villages into highly-polluted villages, moderately-polluted villages, and a non-polluted village. All inhabitants in those six villages were invited to receive free health examinations between May-June, 2010. In total, 4,432 study subjects ≥18 yrs old were analyzed. Compared to those in the non-polluted village, subjects in highly-polluted villages had 1.89- and 1.46-fold the risk of impaired estimated glomerular filtration rate (eGFR) and proteinuria (95% CI = 1.15-1.85 and 1.09-3.28, respectively) after adjusting for other covariates. Given this relative large sample size, we found that groundwater chlorinated hydrocarbon pollution can cause kidney damage in adults.
Method of degrading pollutants in soil
Hazen, Terry C.; Lopez-De-Victoria, Geralyne
1994-01-01
A method and system for enhancing the motility of microorganisms by placing an effective amount of chlorinated hydrocarbons, preferably chlorinated alkenes, and most preferably trichloroethylene in spaced relation to the microbes so that the surprisingly strong, monomodal, chemotactic response of the chlorinated hydrocarbon on subsurface microbes can draw the microbes away from or towards and into a substance, as desired. In remediation of groundwater pollution, for example, TCE can be injected into the plume to increase the population of microbes at the plume whereby the plume can be more quickly degraded. A TCE-degrading microbe, such as Welchia alkenophilia, can be used to degrade the TCE following the degradation of the original pollutant.
DOE Office of Scientific and Technical Information (OSTI.GOV)
Habermehl, Scott D.
Described methods are useful for depositing a silicon carbide film including Alpha-SiC at low temperatures (e.g., below about 1400.degree. C.), and resulting multi-layer structures and devices. A method includes introducing a chlorinated hydrocarbon gas and a chlorosilicon gas into a reaction chamber, and reacting the chlorinated hydrocarbon gas with the chlorosilicon gas at a temperature of less than about 1400.degree. C. to grow the silicon carbide film. The silicon carbide film so-formed includes Alpha-SiC.
,; Goldberg, E.D.; Butler, P.; Meier, P.; Menzel, D.; Paulik, G.; Risebrough, R.; Stickel, L.F.
1971-01-01
SUMMARY AND RECOMMENDATIONS : The oceans are an ultimate accumulation site for the persistent chlorinated hydrocarbons. As much as 25 percent of the DDT compounds produced to date may have been transferred to the sea. The amount of DDT compounds in the marine biota is estimated to be less than 0.1 percent of total production, yet this amount has produced a demonstrable impact upon the marine environment. Populations of fish-eating birds have experienced reproductive failure and decline. With continued accumulations of persistent chlorinated hydrocarbons in the marine ecosystem, additional species will be threatened. Continued release of these pollutants to the environment can only accelerate the accumulation of unacceptable levels of persistent chlorinated hydrocarbons in the tissues of marine food fish. Certain risks in the utilization of chlorinated hydrocarbons are especially hard to quantify, but they require serious consideration. The rate at which such substances degrade to harmless products in the marine system is unknown; the half-lives of some of the more persistent materials are certainly of the order of years, and perhaps even of decades or centuries. If most of the remaining 75 percent of the persistent chlorinated hydrocarbons is now in reservoirs that will in time transfer their contents to the sea, we may expect an increased level of these substances in marine organisms, despite future improvements of manufacturing practices. In fact, if these compounds degrade with half-lives of decades or longer, there will be no opportunity to redress the consequences. The more the problems are studied, the more unexpected effects are identified. In view of the findings of the past decade, our prediction of the potential hazards of chlorinated hydrocarbons in the marine environment may be vastly underestimated. The Panel makes the following recommendations, which will be developed and expanded in the remainder of the report: ? A massive national effort should be made immediately to effect a drastic reduction of the escape of persistent toxicants into the environment, with the ultimate aim of achieving virtual cessation in the shortest possible time. ? Programs should be designed both to determine the rates of entry of each pollutant into the marine environment and to make base-line determinations of the distribution of the pollutants among the components of that environment, These should be followed by a program of monitoring long-term trends in order to record progress and to document possible disaster. ? The laws relating to the registration of chemical substances and the release of production figures by government should be examined and perhaps revised in light of evidence of environmental deterioration caused by some of these substances.
Kim, Jonggun; Sun, Quancai; Yue, Yiren; Yoon, Kyong Sup; Whang, Kwang-Youn; Marshall Clark, J; Park, Yeonhwa
2016-07-01
4,4'-Dichlorodiphenyltrichloroethane (DDT), a chlorinated hydrocarbon insecticide, was extensively used in the 1940s and 1950s. DDT is mainly metabolically converted into 4,4'-dichlorodiphenyldichloroethylene (DDE). Even though most countries banned DDT in the 1970s, due to the highly lipophilic nature and very stable characteristics, DDT and its metabolites are present ubiquitously in the environment, including food. Recently, there are publications on relationships between exposure to insecticides, including DDT and DDE, and weight gain and altered glucose homeostasis. However, there are limited reports regarding DDT or DDE and adipogenesis, thus we investigated effects of DDT and DDE on adipogenesis using 3T3-L1 adipocytes. Treatment of DDT or DDE resulted in increased lipid accumulation accompanied by increased expression of CCAAT/enhancer-binding protein α (C/EBPα), peroxisome-proliferator activated receptor-γ (PPARγ), fatty acid synthase (FAS), acetyl-CoA carboxylase (ACC), adipose triglyceride lipase, and leptin. Moreover, treatment of DDT or DDE increased protein levels of C/EBPα, PPARγ, AMP-activated protein kinase-α (AMPKα), and ACC, while significant decrease of phosphorylated forms of AMPKα and ACC were observed. These finding suggest that increased lipid accumulation caused by DDT and DDE may mediate AMPKα pathway in 3T3-L1 adipocytes. Copyright © 2016 Elsevier B.V. All rights reserved.
Igbinosa, Etinosa O.; Odjadjare, Emmanuel E.; Chigor, Vincent N.; Igbinosa, Isoken H.; Emoghene, Alexander O.; Ekhaise, Fredrick O.; Igiehon, Nicholas O.; Idemudia, Omoruyi G.
2013-01-01
Chlorophenol compounds and their derivatives are ubiquitous contaminants in the environment. These compounds are used as intermediates in manufacturing agricultural chemicals, pharmaceuticals, biocides, and dyes. Chlorophenols gets into the environment from a variety of sources such as industrial waste, pesticides, and insecticides, or by degradation of complex chlorinated hydrocarbons. Thermal and chemical degradation of chlorophenols leads to the formation of harmful substances which constitute public health problems. These compounds may cause histopathological alterations, genotoxicity, mutagenicity, and carcinogenicity amongst other abnormalities in humans and animals. Furthermore, the recalcitrant nature of chlorophenolic compounds to degradation constitutes an environmental nuisance, and a good understanding of the fate and transport of these compounds and their derivatives is needed for a clearer view of the associated risks and mechanisms of pathogenicity to humans and animals. This review looks at chlorophenols and their derivatives, explores current research on their effects on public health, and proffers measures for mitigation. PMID:23690744
NASA Astrophysics Data System (ADS)
Múčka, V.; Buňata, M.; Čuba, V.; Silber, R.; Juha, L.
2015-07-01
Radiation induced dechlorination of trichloroethylene (TCE) and tetrachloroethylene (PCE) in aqueous solutions containing the active carbon (AC) or cupric oxide (CuO) as the modifiers was studied. The obtained results were compared to the previously studied dechlorination of polychlorinated biphenyls (PCBs). Both modifiers were found to decrease the efficiency of dechlorination. The AC modifier acts mainly via adsorption of the aliphatic (unlike the aromatic) hydrocarbons and the CuO oxide mainly inhibits the mineralization of the perchloroethylene. The results presented in this paper will be also helpful for the studies of the impact of chlorinated hydrocarbons on the membrane permeability of living cells.
The greening of pesticide-environment interactions: some personal observations.
Casida, John E
2012-04-01
Pesticide-environment interactions are bidirectional. The environment alters pesticides by metabolism and photodegradation, and pesticides in turn change the environment through nontarget or secondary effects. Approximately 900 currently used commercial pesticides of widely diverse structures act by nearly a hundred mechanisms to control insects, weeds, and fungi, usually with minimal disruption of nature's equilibrium. Here I consider some aspects of the discovery, development, and use of ecofriendly or green pesticides (i.e., pesticides that are safe, effective, and biodegradable with minimal adverse secondary effects on the environment). Emphasis is given to research in my laboratory. The need for understanding and improving pesticide-environment interactions began with production of the first major insecticide approximately 150 years ago: The arsenical poison Paris Green was green in color but definitely not ecofriendly. Development and use of other pesticides has led to a variety of problems. Topics considered here include the need for high purity [e.g., hexachlorocyclohexane and polychloroborane isomers and 2,4,5-trichlorophenoxyacetic acid (2,4,5-T)], environmental degradation and the bioactivity of resulting photoproducts and metabolites, pesticide photochemistry (including the use of structural optimization, photostabilizers, and photosensitizers to achieve suitable persistence), the presence of multiple active ingredients in botanical insecticides, the need to consider compounds with common mechanisms of action, issues related to primary and secondary targets, and chemically induced or genetically modified changes in plant biochemistry. Many insecticides are bird, fish, and honeybee toxicants, whereas herbicides and fungicides pose fewer environmental problems. Six factors have contributed to the greening of pesticide-environment interactions: advances in pesticide chemistry and toxicology, banning of many chlorinated hydrocarbons, the development of new biochemical targets, increased reliance on genetically modified crops that reduce the amount and variety of pesticides applied, emphasis on biodegradability and environmental protection, and integrated pest- and pesticide-management systems.
Microwave-enhanced chemical processes
Varma, Ravi
1990-01-01
A process for disposal of toxic wastes including chlorinated hydrocarbons, comprising, establishing a bed of non-metallic particulates having a high dielectric loss factor. Effecting intimate contact of the particulates and the toxic wastes at a temperature in excess of about 400.degree. C. in the presence of microwave radiation for a time sufficient to break the hydrocarbon chlorine bonds and provide detoxification values in excess of 80 and further detoxifying the bed followed by additional disposal of toxic wastes.
Method of degrading pollutants in soil
Hazen, T.C.; Lopez-De-Victoria, G.
1994-07-05
Disclosed are a method and system for enhancing the motility of microorganisms. This is accomplished by placing an effective amount of chlorinated hydrocarbons, preferably chlorinated alkenes, and most preferably trichloroethylene in spaced relation to the microbes so that the surprisingly strong, monomodal, chemotactic response of the chlorinated hydrocarbon on subsurface microbes can draw the microbes away from or towards and into a substance, as desired. In remediation of groundwater pollution, for example, TCE can be injected into the plume to increase the population of microbes at the plume whereby the plume can be more quickly degraded. A TCE-degrading microbe, such as Welchia alkenophilia, can be used to degrade the TCE following the degradation of the original pollutant. 5 figures.
Microwave-enhanced chemical processes
Varma, R.
1990-06-19
A process is disclosed for the disposal of toxic wastes including chlorinated hydrocarbons, comprising, establishing a bed of non-metallic particulates having a high dielectric loss factor. Intimate contact of the particulates and the toxic wastes at a temperature in excess of about 400 C in the presence of microwave radiation for a time sufficient breaks the hydrocarbon chlorine bonds. Detoxification values in excess of 80 are provided and further detoxification of the bed is followed by additional disposal of toxic wastes. 1 figure.
U. S. EPA’S APPROACH FOR CHLORINATED SOLVENTS
The approach for chlorinated solvents is similar to the approach for petroleum hydrocarbons. However, there are more mechanisms of removal, including reductive dechlorination (biotic or abiotic), dehydrochloroelimination (abiotic), and hydrolysis (biotic or abiotic). As a resul...
NASA Astrophysics Data System (ADS)
Lu, Rui; Mizaikoff, Boris; Li, Wen-Wei; Qian, Chen; Katzir, Abraham; Raichlin, Yosef; Sheng, Guo-Ping; Yu, Han-Qing
2013-08-01
Chlorinated aliphatic hydrocarbons and chlorinated aromatic hydrocarbons (CHCs) are toxic and carcinogenic contaminants commonly found in environmental samples, and efficient online detection of these contaminants is still challenging at the present stage. Here, we report an advanced Fourier transform infrared spectroscopy-attenuated total reflectance (FTIR-ATR) sensor for in-situ and simultaneous detection of multiple CHCs, including monochlorobenzene, 1,2-dichlorobenzene, 1,3-dichlorobenzene, trichloroethylene, perchloroethylene, and chloroform. The polycrystalline silver halide sensor fiber had a unique integrated planar-cylindric geometry, and was coated with an ethylene/propylene copolymer membrane to act as a solid phase extractor, which greatly amplified the analytical signal and contributed to a higher detection sensitivity compared to the previously reported sensors. This system exhibited a high detection sensitivity towards the CHCs mixture at a wide concentration range of 5~700 ppb. The FTIR-ATR sensor described in this study has a high potential to be utilized as a trace-sensitive on-line device for water contamination monitoring.
Lu, Rui; Mizaikoff, Boris; Li, Wen-Wei; Qian, Chen; Katzir, Abraham; Raichlin, Yosef; Sheng, Guo-Ping; Yu, Han-Qing
2013-01-01
Chlorinated aliphatic hydrocarbons and chlorinated aromatic hydrocarbons (CHCs) are toxic and carcinogenic contaminants commonly found in environmental samples, and efficient online detection of these contaminants is still challenging at the present stage. Here, we report an advanced Fourier transform infrared spectroscopy-attenuated total reflectance (FTIR-ATR) sensor for in-situ and simultaneous detection of multiple CHCs, including monochlorobenzene, 1,2-dichlorobenzene, 1,3-dichlorobenzene, trichloroethylene, perchloroethylene, and chloroform. The polycrystalline silver halide sensor fiber had a unique integrated planar-cylindric geometry, and was coated with an ethylene/propylene copolymer membrane to act as a solid phase extractor, which greatly amplified the analytical signal and contributed to a higher detection sensitivity compared to the previously reported sensors. This system exhibited a high detection sensitivity towards the CHCs mixture at a wide concentration range of 5~700 ppb. The FTIR-ATR sensor described in this study has a high potential to be utilized as a trace-sensitive on-line device for water contamination monitoring. PMID:23982222
Lu, Rui; Mizaikoff, Boris; Li, Wen-Wei; Qian, Chen; Katzir, Abraham; Raichlin, Yosef; Sheng, Guo-Ping; Yu, Han-Qing
2013-01-01
Chlorinated aliphatic hydrocarbons and chlorinated aromatic hydrocarbons (CHCs) are toxic and carcinogenic contaminants commonly found in environmental samples, and efficient online detection of these contaminants is still challenging at the present stage. Here, we report an advanced Fourier transform infrared spectroscopy-attenuated total reflectance (FTIR-ATR) sensor for in-situ and simultaneous detection of multiple CHCs, including monochlorobenzene, 1,2-dichlorobenzene, 1,3-dichlorobenzene, trichloroethylene, perchloroethylene, and chloroform. The polycrystalline silver halide sensor fiber had a unique integrated planar-cylindric geometry, and was coated with an ethylene/propylene copolymer membrane to act as a solid phase extractor, which greatly amplified the analytical signal and contributed to a higher detection sensitivity compared to the previously reported sensors. This system exhibited a high detection sensitivity towards the CHCs mixture at a wide concentration range of 5~700 ppb. The FTIR-ATR sensor described in this study has a high potential to be utilized as a trace-sensitive on-line device for water contamination monitoring.
Taylor, Robert T.; Jackson, Kenneth J.; Duba, Alfred G.; Chen, Ching-I
1998-01-01
An in situ thermally enhanced microbial remediation strategy and a method for the biodegradation of toxic petroleum fuel hydrocarbon and halogenated organic solvent contaminants. The method utilizes nonpathogenic, thermophilic bacteria for the thermal biodegradation of toxic and carcinogenic contaminants, such as benzene, toluene, ethylbenzene and xylenes, from fuel leaks and the chlorinated ethenes, such as trichloroethylene, chlorinated ethanes, such as 1,1,1-trichloroethane, and chlorinated methanes, such as chloroform, from past solvent cleaning practices. The method relies on and takes advantage of the pre-existing heated conditions and the array of delivery/recovery wells that are created and in place following primary subsurface contaminant volatilization efforts via thermal approaches, such as dynamic underground steam-electrical heating.
Taylor, R.T.; Jackson, K.J.; Duba, A.G.; Chen, C.I.
1998-05-19
An in situ thermally enhanced microbial remediation strategy and a method for the biodegradation of toxic petroleum fuel hydrocarbon and halogenated organic solvent contaminants are described. The method utilizes nonpathogenic, thermophilic bacteria for the thermal biodegradation of toxic and carcinogenic contaminants, such as benzene, toluene, ethylbenzene and xylenes, from fuel leaks and the chlorinated ethenes, such as trichloroethylene, chlorinated ethanes, such as 1,1,1-trichloroethane, and chlorinated methanes, such as chloroform, from past solvent cleaning practices. The method relies on and takes advantage of the pre-existing heated conditions and the array of delivery/recovery wells that are created and in place following primary subsurface contaminant volatilization efforts via thermal approaches, such as dynamic underground steam-electrical heating. 21 figs.
Method for removing chlorine compounds from hydrocarbon mixtures
Janoski, Edward J.; Hollstein, Elmer J.
1985-12-31
A process for removing halide ions from a hydrocarbon feedstream containing halogenated hydrocarbons wherein the contaminated feedstock is contacted with a solution of a suitable oxidizing acid containing a lanthanide oxide, the acid being present in a concentration of at least about 50 weight percent for a time sufficient to remove substantially all of the halide ion from the hydrocarbon feedstock.
Method for removing chlorine compounds from hydrocarbon mixtures
Janoski, E.J.; Hollstein, E.J.
1984-09-29
A process for removing halide ions from a hydrocarbon feedstream containing halogenated hydrocarbons wherein the contaminated feedstock is contacted with a solution of a suitable oxidizing acid containing a lanthanide oxide, the acid being present in a concentration of at least about 50 weight percent for a time sufficient to remove substantially all of the halide ion from the hydrocarbon feedstock.
Klavarioti, Maria; Kostarelos, Konstantinos; Pourjabbar, Anahita; Ghandehari, Masoud
2014-05-01
There is an imperative need for a chemical sensor capable of remote, in situ, long-term monitoring of chemical species at sites containing toxic chemical spills, specifically at chemical waste dumps, landfills, and locations with underground storage tanks. In the current research, a series of experiments were conducted measuring the near-infrared optical absorption of alkanes, aromatics, and chlorinated hydrocarbons. A spectral library was then developed to characterize the optical spectra of liquid hydrocarbons. Near-infrared analysis was chosen due to compatibility with optical fibers. The goal was to differentiate between classes of hydrocarbons and to also discriminate between compounds within a class of similar molecular structures. It was observed that unique absorption spectra can be obtained for each hydrocarbon, and this uniqueness can be used to discriminate between hydrocarbons from different families. Statistical analyses, namely, principal component analysis (PCA) and correlation coefficient (Spearman and Pearson methods), were attempted to match absorption spectra from an unknown hydrocarbon with the database with limited success. An algorithm was subsequently written to identify the characteristic peaks of each hydrocarbon that could be used to match data from an unknown chemical species with the database.
Effects of an organophosphorus pesticide on reproduction in the rat.
DOT National Transportation Integrated Search
1970-01-01
The toxic effects of organophosphorus insecticides are commonly ascribed to cholinesterase (CHE) inhibition. A search of the scientific literature revealed the well-established fact that a number of chlorinated pesticides adversely affect reproductio...
IN-PLACE REGENERATION OF GAC USING FENTON'S REAGENTS
This paper evaluates the feasibility of using Fenton’s reagents for in-place recovery of spent granular activated carbon (GAC). Fenton’s reagents are cycled through spent GAC to degrade sorbed chlorinated hydrocarbons with little loss of carbon capacity. Seven chlorinated compou...
Exhaled human breath analysis has become a standard technique for assessing exposure to exogenous volatile organic compounds (VOCs) such as trihalomethanes from water chlorination; aromatics, hydrocarbons, and oxygenates from fuels usage; and various chlorinated solvents from i...
DEMONSTRATION BULLETIN: GRACE DEARBORN INC. DARAMEND™ BIOREMEDIATION TECHNOLOGY
The DARAMEND™ Bioremediation Technology may be applied to the remediation of soils and sediments contaminated by a wide variety of organic contaminants including chlorinated phenols, polynuclear aromatic hydrocarbons (PAHs), and petroleum hydrocarbons. The technology may be ap...
ERIC Educational Resources Information Center
Chian, Edward S. K.; DeWalle, Foppe B.
1978-01-01
Presents water analysis literature for 1978. This review is concerned with organics, and it covers: (1) detergents and surfactants; (2) aliphatic and aromatic hydrocarbons; (3) pesticides and chlorinated hydrocarbons; and (4) naturally occurring organics. A list of 208 references is also presented. (HM)
Gałgowska, Michalina; Pietrzak-Fiećko, Renata; Felkner-Poźniakowska, Barbara
2012-11-01
The aim of the study was to determine the content of chlorinated hydrocarbon residues in edible mushrooms from the north-eastern part of Poland. Material consisted of two species of fungi: Xerocomus mushrooms (Xerocomus badius), Boletus mushrooms (Boletus edulis). The dried samples (cups and cut-up material) were extracted with Soxhlet method in order to obtain lipid substances. In the fat chlorinated hydrocarbons were determined by Ludwicki et al. (1996) method. The separation and quantitative determination of DDT, DDE, DDD and γ-HCH were conducted with the method of gas chromatography using an electron capture detector - ECD. In all tested samples the presence of γ-HCH, DDT and its metabolites (DDE, DDD) was detected. The higher content of γ-HCH was found in Xerocomus mushrooms (average 0.125 μg/kg of mushrooms); in the Boletus mushrooms -0.11 μg/kg of mushrooms. The content of ΣDDT in cups of Xerocomus mushrooms was more than 2-fold higher than in those of Boletus mushrooms (3.78:1.71 mg/kg of mushrooms). The opposite relationship was observed for cut-up material. The higher concentration of ΣDDT was found in Boletus mushrooms (2.26 mg/kg of mushrooms) while in Xerocomus mushrooms this content was 0.91 mg/kg of mushrooms. Despite the fact that chlorinated hydrocarbons were determined in all samples under study, their contents do not exceed acceptable levels indicating that the consumption of mushrooms does not pose a health risk to consumers from the organochlorine compounds. Copyright © 2012 Elsevier Ltd. All rights reserved.
Atmospheric chlorinated polycyclic aromatic hydrocarbons in East Asia.
Kakimoto, Kensaku; Nagayoshi, Haruna; Konishi, Yoshimasa; Kajimura, Keiji; Ohura, Takeshi; Hayakawa, Kazuichi; Toriba, Akira
2014-09-01
This study estimates atmospheric concentrations of chlorinated polycyclic aromatic hydrocarbons (ClPAHs) and polycyclic aromatic hydrocarbons (PAHs) in East Asia using a Gas Chromatograph with High Resolution Mass Spectrometer (GC-HRMS). ClPAHs are ubiquitously generated from PAHs through substitution, and some ClPAHs show higher aryl hydrocarbon receptor (AhR)-mediated activities than their parent PAHs. Atmospheric particles were collected using a high-volume air sampler equipped with a quartz-fiber filter. We determined the ClPAH concentrations of atmospheric particles collected in Japan (Sapporo, Sagamihara, Kanazawa, and Kitakyushu), Korea (Busan), and China (Beijing). The concentrations of ClPAHs were highest in the winter Beijing sample, where the total mean concentration was approximately 15-70 times higher than in the winter samples from Japan and Korea. The concentrations of Σ19ClPAHs and Σ9PAHs were significantly correlated in the Kanazawa and the Busan samples. This indicates that within those cities ClPAHs and PAHs share the same origin, implying direct chlorination of parent PAHs. Toxic equivalent concentrations (TEQs) of the total ClPAHs and PAHs were lowest in Kanazawa in the summer, reaching 1.18 and 2610fg-TEQm(-3) respectively, and highest in Beijing in the winter, reaching 627 and 4240000fg-TEQm(-3) respectively. Copyright © 2014 Elsevier Ltd. All rights reserved.
Lovich, J.; Meyer, K.
2002-01-01
During Late 1970 and early 1971, 229 woodcock (Philohela minor) were collected from 23 Eastern and Midwestern States. Analyses for chlorinated hydrocarbons and mercury in these migratory birds showed generally low levels which are not considered dangerous to human consumers. In this survey, Louisiana woodcock had lower residues of heptachlor epoxide and DDE than those tested in a 1965 survey. PCB levels, however, may have increased. Mirex levels were greatest in Mississipi and Louisiana woodcock. Pooling of birds and averaging of individually analyzed birds did not provide equivalent estimates of equivalent residues; pool values tended to be larger and more variable. Levels of six chlorinated hydrocarbons and mercury were negatively correlated with the latitude of the collection site. However, this relationship seemed weakest for PCB's. Among eight chemical residues, PCB levels were most often correlated with levels of the other seven. Levels of chlorinated hydrocarbons in wings were correlated with levels in breast muscle and in carcass; however, mean levels of certain residues differed significantly among wing, muscle, and carcass even when compared on a lipid basis.
Chlorinated hydrocarbons are ubiquitous ground water contaminants due to their widespread use as organic solvents and cleaners/degreasers. The immiscibility of chlorinated organis with ground water causes them to exists as nonaqueous phase liquids (NAPLs); this results in their o...
Russell, Gary M.; Hanson, Chris E.; Pitt, William A.J.
1978-01-01
Water quality in the Old Plantation Water Control District in Broward County, Florida has been affected by effluent from sewage-treatment plants, agriculture, and storm-water runoff. Effect of effluent from sewage-treatment plants on water quality was evident at 3 sites where concentrations of nutrients and bacteria in the Broward County canals exceeded State standards of 2,400 colonies per 100 milliliters for total coliform bacteria. At 2 of the 3 sites the fecal coliform/fecal streptococcus ratios indicated possible human contamination. The effect of agriculture on water quality was evident where relatively high levels of chlorinated hydrocarbon insecticides had concentrated in the bottom sediments, of the canals. For example, DDD reached levels of 330 micrograms per kilogram at one site. The effects of storm-water runoff on water quality were detected during the wet season when concentrations of several trace elements increased. For example, zinc averaged 30 micrograms per milliliter in the wet season compared with 20 micrograms per milliliter during the dry season. (Woodard-USGS)
Research review. Interactions between environmental chemicals and drug biotransformation in man.
Alvares, A P
1978-01-01
Many factors influence the metabolism of drugs in man. Besides genetic factors, environmental factors may play a significant role in explaining the variation observed in the rates of drug metabolism between different individuals. Intentional or unintentional exposure to environmental chemicals could enhance or inhibit the activity of hepatic mixed function oxidases that metabolise drugs and other foreign chemicals, as well as endogenous substrates such as steroid hormones. A major source of such exposure may be occupational. Exposure to the heavy metal, lead, has been shown to inhibit drug metabolism; whereas intensive exposure to chlorinated insecticides, and other halogenated hydrocarbons such as polychlorinated biphenyls, has been shown to enhance the metabolism of test drugs such as antipyrine and phenylbutazone. An intentional source of exposure to foreign chemicals is cigarette smoke. Cigarette smoke contains polycyclic hydrocarbons, which are known inducers of hepatic mixed function oxidases. A number of studies have shown that cigarette smoking can alter the pharmacological action and/or the metabolism of some drugs. Pharmacokinetic studies have shown that cigarette smoking decreases the bioavailability of phenacetin and increases dosage requirements of theophylline by enhancing their rate of metabolism. Data, which are not very conclusive, indicate that heavy marijuana use may have an inhibitory effect on metabolism of some drugs and an inducing effect on others such as theophylline. Dietary factors may also play a significant role in the regulation of drug metabolism. Charcoal broiling which introduces polycyclic hydrocarbons into foods has been shown to enhance the metabolism of the test drug, antipyrine, and of such commonly used drugs as phenacetin and theophylline. Such intentional or unintentional exposure to environmental chemicals which may alter the rates of drug metabolism in man indicates the importance of individualisation of drug therapy.
Carter, L.F.; Anderholm, S.K.
1997-01-01
The occurrence and distribution of contaminants in aquatic systems are major components of the National Water-Quality Assessment (NAWQA) Program. Bed-sediment samples were collected at 18 sites in the Rio Grande Valley study unit between September 1992 and March 1993 to characterize the geographic distribution of organic compounds, including chlorinated insecticides, polychlorinated biphenyls (PCB's), and other chlorinated hydrocarbons, and also trace elements. Two-millimeter-size- fraction sediment was analyzed for organic compounds and less than 63-micron-size-fraction sediment was analyzed for trace elements. Concentrations of p,p'-DDE were detected in 33 percent of the bed-sediment samples. With the exception of DDT-related compounds, no other organochlorine insecticides or polychlorinated biphenyls were detected in samples of bed sediment. Whole-body fish samples were collected at 11 of the bed- sediment sites and analyzed for organic compounds. Organic compounds were reported more frequently in samples of fish, and more types of organic compounds were found in whole-body fish samples than in bed-sediment samples. Concentrations of p,p'-DDE were detected in 91 percent of whole-body fish samples. Polychlorinated biphenyls, cis-chlordane, trans-chlordane, trans- nonachlor, and hexachlorobenzene were other organic compounds detected in whole-body samples of fish from at least one site. Because of the extent of mineralized areas in the Rio Grande Basin arsenic, cadmium, copper, lead, mercury, selenium, and zinc concentrations in bed-sediment samples could represent natural conditions at most sites. However, a combination of natural conditions and human activities appears to be associated with elevated trace-element concentrations in the bed-sediment sample from the site Rio Grande near Creede, Colorado, because this sample exceeded the background trace-element concentrations calculated for this study. Fish-liver samples were collected at 12 of the bed-sediment sites and analyzed for trace elements. Certain trace elements were detected at higher concentrations in fish-liver samples than in bed-sediment samples from the same site. Both bed-sediment and fish-tissue samples are necessary for a complete environmental assessment of the occurrence and distribution of trace elements.
Long term impact of anthropogenic emissions of halogenated hydrocarbons on stratospheric ozone level
NASA Technical Reports Server (NTRS)
1977-01-01
Reaction kinetics are studied for stratospheric chlorine atoms, OH initiated degradation of carbon-chlorine compounds, the chemical decomposition of stratospheric HCl and ClONO2. A photochemical study is made of the decomposition of O3 over the wavelength range 2935 to 3165 deg A.
Barra, Paula; Etcheverry, Miriam; Nesci, Andrea
2015-01-01
Entomopathogenic fungi can regulate insect populations. They have extracellular enzymes that degrade cuticle components, mainly hydrocarbons, used as an energy source. The increase in insecticidal activity of fungi in a medium supplemented with cuticular hydrocarbons was assayed and the hydrolytic enzyme profiles of two strains of Purpureocillium lilacinum were evaluated. A spore suspension of P. lilacinum was inoculated in Petri plates with different values (0.99–0.97–0.95) of water activity (Aw) using the substrates gelatin, starch and tween-20. Growth rate on the different substrates and the enzymatic activity index for proteases, amylases and lipases at different incubation times, pH and Aw, was evaluated. Moreover, the insecticidal efficiency of strains grown in media supplemented with n-hexadecane and n-octacosane was analyzed. LT50 was calculated against adults of Tribolium confusum and showed that mortality increased about 15% when the strains grew in amended culture medium. High amylolytic activity was detected, but proteases were the main enzymes produced. Optimal protease production was observed in a range of acid and alkaline pH and lower Aw. The greatest growth rate was obtained in presence of gelatin. Lipase and amylase production was detected in small amounts. Fungal growth in media with hydrocarbon mixtures increased the pathogenicity of the two strains of P. lilacinum, with the strain JQ926223 being more virulent. The information obtained is important for achieving both an increase in insecticidal capacity and an understanding of physiological adaptation of the fungus. PMID:26463076
Barra, Paula; Etcheverry, Miriam; Nesci, Andrea
2015-03-18
Entomopathogenic fungi can regulate insect populations. They have extracellular enzymes that degrade cuticle components, mainly hydrocarbons, used as an energy source. The increase in insecticidal activity of fungi in a medium supplemented with cuticular hydrocarbons was assayed and the hydrolytic enzyme profiles of two strains of Purpureocillium lilacinum were evaluated. A spore suspension of P. lilacinum was inoculated in Petri plates with different values (0.99-0.97-0.95) of water activity (Aw) using the substrates gelatin, starch and tween-20. Growth rate on the different substrates and the enzymatic activity index for proteases, amylases and lipases at different incubation times, pH and Aw, was evaluated. Moreover, the insecticidal efficiency of strains grown in media supplemented with n-hexadecane and n-octacosane was analyzed. LT50 was calculated against adults of Tribolium confusum and showed that mortality increased about 15% when the strains grew in amended culture medium. High amylolytic activity was detected, but proteases were the main enzymes produced. Optimal protease production was observed in a range of acid and alkaline pH and lower Aw. The greatest growth rate was obtained in presence of gelatin. Lipase and amylase production was detected in small amounts. Fungal growth in media with hydrocarbon mixtures increased the pathogenicity of the two strains of P. lilacinum, with the strain JQ926223 being more virulent. The information obtained is important for achieving both an increase in insecticidal capacity and an understanding of physiological adaptation of the fungus.
Poster, Dianne L; Kucklick, John R; Schantz, Michele M; Porter, Barbara J; Leigh, Stefan D; Wise, Stephen A
2003-01-01
The concentrations of a wide range of polychlorinated biphenyl congeners (PCBs) and chlorinated pesticides in a fish tissue Standard Reference Material (SRM) have been determined using multiple methods of analysis. This material, SRM 1946, Lake Superior Fish Tissue, was recently issued by the National Institute of Standards and Technology (NIST) and complements a suite of marine environmental natural-matrix SRMs that are currently available from NIST for the determination of organic contaminants such as aliphatic hydrocarbons, polycyclic aromatic hydrocarbons (PAHs), PCBs, and chlorinated pesticides. SRM 1946 is a fresh tissue homogenate (frozen) prepared from filleted adult lake trout (Salvelinus namaycush namaycush) collected from the Apostle Islands region of Lake Superior. SRM 1946 has certified and reference concentrations for PCB congeners, including the three non- ortho PCB congeners, and chlorinated pesticides. Certified concentrations are available for 30 PCB congeners and 15 chlorinated pesticides. Reference concentrations are available for 12 PCB congeners and 2 chlorinated pesticides. In addition, SRM 1946 is characterized for additional chemical constituents and properties: fatty acids, extractable fat, methylmercury, total mercury, selected trace elements, proximates, and caloric content. The characterization of chlorinated compounds is described in this paper with an emphasis on the approach used for the certification of the concentrations of PCB congeners and chlorinated pesticides. The PCB congener and chlorinated pesticide data are also compared to concentrations in other marine natural-matrix reference materials available from NIST (fish oil, mussel tissue, whale blubber, and a second fresh frozen fish tissue homogenate prepared from filleted adult lake trout collected from Lake Michigan) and from other organizations such as the National Research Council Canada (ground whole carp), the International Atomic Energy Agency (fish homogenate), and the European Commission Joint Research Centre [fish oils (cod and mackerel) and mussel tissue].
The Greening of Pesticide–Environment Interactions: Some Personal Observations
2012-01-01
Background: Pesticide–environment interactions are bidirectional. The environment alters pesticides by metabolism and photodegradation, and pesticides in turn change the environment through nontarget or secondary effects. Objectives: Approximately 900 currently used commercial pesticides of widely diverse structures act by nearly a hundred mechanisms to control insects, weeds, and fungi, usually with minimal disruption of nature’s equilibrium. Here I consider some aspects of the discovery, development, and use of ecofriendly or green pesticides (i.e., pesticides that are safe, effective, and biodegradable with minimal adverse secondary effects on the environment). Emphasis is given to research in my laboratory. Discussion: The need for understanding and improving pesticide–environment interactions began with production of the first major insecticide approximately 150 years ago: The arsenical poison Paris Green was green in color but definitely not ecofriendly. Development and use of other pesticides has led to a variety of problems. Topics considered here include the need for high purity [e.g., hexachlorocyclohexane and polychloroborane isomers and 2,4,5-trichlorophenoxyacetic acid (2,4,5-T)], environmental degradation and the bioactivity of resulting photoproducts and metabolites, pesticide photochemistry (including the use of structural optimization, photostabilizers, and photosensitizers to achieve suitable persistence), the presence of multiple active ingredients in botanical insecticides, the need to consider compounds with common mechanisms of action, issues related to primary and secondary targets, and chemically induced or genetically modified changes in plant biochemistry. Many insecticides are bird, fish, and honeybee toxicants, whereas herbicides and fungicides pose fewer environmental problems. Conclusion: Six factors have contributed to the greening of pesticide–environment interactions: advances in pesticide chemistry and toxicology, banning of many chlorinated hydrocarbons, the development of new biochemical targets, increased reliance on genetically modified crops that reduce the amount and variety of pesticides applied, emphasis on biodegradability and environmental protection, and integrated pest- and pesticide-management systems. PMID:22472325
Loblolly pine (Pinus taeda) was combusted at different charge sizes, fuel moisture, and chlorine content to determine the effect on emissions of polychlorinated dibenzo-p-dioxins and polychlorinated diberizofurans (PCDDslFs) as well as co-pollutants CO, PM, and total hydrocarbons...
NASA Astrophysics Data System (ADS)
Lamont-Friedrich, Stephanie J.; Michl, Thomas D.; Giles, Carla; Griesser, Hans J.; Coad, Bryan R.
2016-07-01
The attachment of pathogenic fungal cells onto materials surfaces, which is often followed by biofilm formation, causes adverse consequences in a wide range of areas. Here we have investigated the ability of thin film coatings from chlorinated molecules to deter fungal colonization of solid materials by contact killing of fungal cells reaching the surface of the coating. Coatings were deposited onto various substrate materials via plasma polymerization, which is a substrate-independent process widely used for industrial coating applications, using 1,1,2-trichloroethane as the process vapour. XPS surface analysis showed that the coatings were characterized by a highly chlorinated hydrocarbon polymer nature, with only a very small amount of oxygen incorporated. The activity of these coatings against human fungal pathogens was quantified using a recently developed, modified yeast assay and excellent antifungal activity was observed against Candida albicans and Candida glabrata. Plasma polymer surface coatings derived from chlorinated hydrocarbon molecules may therefore offer a promising solution to preventing yeast and mould biofilm formation on materials surfaces, for applications such as air conditioners, biomedical devices, food processing equipment, and others.
Sludge incineration tests on circulating fluidised bed furnace.
Lotito, V; Mininni, G; Di Pinto, A C; Spinosa, L
2001-01-01
Results of sludge incineration tests on a demonstrative fluidised bed furnace are reported and discussed. They show that particulate, heavy metals and acidic compounds in the emissions can be easily controlled both when sludge is spiked with chlorinated hydrocarbons up to a chlorine concentration in the feed of 5%, and when the afterburner is switched off. As for organic micropollutants, polynuclear aromatic hydrocarbons (PAH) were much lower than the Italian limits of 10 microg/m3 (no limits are at present considered in the European Directives). Dioxins (PCDDs) and furans (PCDFs) in some tests exceeded the limit of 0.1 ng/m3 (TE) but the concentrations in the fly ashes were much lower, thus evidencing a possible presence of contaminants in gas phase. PAHs and PCDD/PCDFs were not depending on the afterburning operation, the presence of organic chlorine in the feed sludge and the copper addition to sewage sludge.
BIOTRANSFORMATION OF MONOAROMATIC AND CHLORINATED HYDROCARBONS AT AN AVIATION GASOLINE SPILL SITE
A shallow water table aquifer under the U.S. Coast Guard Air Station at Traverse City, MI, has acclimated to the aerobic and anaerobic transformation of monoaromatic hydrocarbons (BTX) released from an aviation gasoline spill. The aquifer also exhibits reductive dechlorination of...
Heterogenous photocatalysis with TiO2 has been extensively investigated as a method to oxidize organic pollutants in water and air, including phenols, chlorinated hydrocarbons, and other hydrocarbons. In addition, the use of titanium dioxide as a photocatalyst has also been demon...
1979-12-01
Nitrates Sulfur dioxide Xylene Nitrites Oxides of nitrogen Mercaptans "Red Water" Carbon monoxide Chlorine Acids: Ketones Fluorine Hydrochloric Esters...Trichloroethylene Varnishes Methylchloroform Undercoatings Mineral spirits Liquid styrene Naphtha Adhesives Halgenated hydrocarbons Nonmethane hydrocarbons
Using Iron to Treat Chlorohydrocarbon-Contaminated Soil
NASA Technical Reports Server (NTRS)
Hitchens, G. Duncan; Hodko, Dalibor; Kim, Heekyung; Rogers, Tom; Singh, Waheguru Pal; Giletto, Anthony; Cisar, Alan
2004-01-01
A method of in situ remediation of soil contaminated with chlorinated hydrocarbon solvents involves injection of nanometer-size iron particles. The present method exploits a combination of prompt chemical remediation followed by longer-term enhanced bioremediation and, optionally, is practiced in conjunction with the method of bioremediation described earlier. Newly injected iron particles chemically reduce chlorinated hydrocarbons upon contact. Thereafter, in the presence of groundwater, the particles slowly corrode via chemical reactions that effect sustained release of dissolved hydrogen. The hydrogen serves as an electron donor, increasing the metabolic activity of the anaerobic bacteria and thereby sustaining bioremediation at a rate higher than the natural rate.
A palladium-on-zeolite catalyst has been optimized for treating groundwater contaminated with halogenated hydrocarbon compounds (HHCs) by hydrodechlorination with dissolved hydrogen. Aqueous sulfite was used as the model poison and the dechlorination of 1,2-di...
A palladium-on-zeolite catalyst has been optimized for treating groundwater contaminated with halogenated hydrocarbon compounds (HHCs) by hydrodechlorination with dissolved hydrogen. Aqueous sulfite was used as the model poison and the dechlorination of 1,2-di...
1990-01-01
herbicides, insecticides, and fungicides is dependent upon both biotic and abiotic reactions, and the rate of these reactions determines the required...The most commonly isolated I hydrocarbon degrading fungi in decreasing order include: Trichoderma , i Penicillium, Aspergillus, and Mortierella (Dragun
The central Asian Republic of Tajikistan has been an area of extensive historical agricultural pesticide use as well as large scale burials of obsolete banned chlorinated insecticides. The current investigation was a four year study of legacy organochlorine pesticides in surface ...
Friend, M.; Franson, J.C.
1999-01-01
Polychlorinated biphenyls (PCBs) are industrial compounds with multiple industrial and commercial uses (Table 41.1). PCBs are chemically inert and stable when heated. These properties contribute greatly to PCBs having become environmental contaminants. The chemical inertness and heat stability properties that make PCBs desirable for industry also protect them from destruction when the products in which they are used are discarded. These same properties also enable PCB residues to persist in the environment for long periods of time and to be transported worldwide when contaminated particulate matter travels through waters, precipitation, wind, and other physical forces.PCBs have a physical structure similar to DDT, and, like DDT, they are classified as aromatic hydrocarbons which contain one or more benzene rings. The presence of chlorine results in DDT, PCBs, and other compounds with similar structures commonly being referred to as chlorinated hydrocarbons. The toxicity of these compounds is associated with the amount of chlorine they contain. The trade name of Aroclor® for PCBs that were produced by a manufacturer in the United States contains a numerical designation that specifies the amount of chlorine present in a particular formulation. For example, Aroclor® 1221 contains 21 percent chlorine while Aroclor® 1254 contains 54 percent chlorine. The first two digits designate the number of carbons in the formulation. The chemical structure of PCBs results in the possibility of many different forms or isomers, (more commonly called congeners) of these compounds. PCBs in other countries have different trade names than Aroclor® (Table 41.2).
2006-05-01
Polycyclic Aromatic Hydrocarbons and Petroleum to Marine Invertebrate Larvae and Juveniles,” Environ. Toxicol. Chem., vol. 16, pp. 2190–2199...aromatic hydrocarbons , polychlorinated biphenyls, and chlorinated pesticides. Seventeen plume mapping surveys, including an on-site floating bioassay...Non-point Source NS&T National Status and Trends PAH Polynuclear Aromatic Hydrocarbon PCB Polychlorinated Biphenyl PMSD Percent
Insect P450 inhibitors and insecticides: challenges and opportunities.
Feyereisen, René
2015-06-01
P450 enzymes are encoded by a large number of genes in insects, often over a hundred. They play important roles in insecticide metabolism and resistance, and growing numbers of P450 enzymes are now known to catalyse important physiological reactions, such as hormone metabolism or cuticular hydrocarbon synthesis. Ways to inhibit P450 enzymes specifically or less specifically are well understood, as P450 inhibitors are found as drugs, as fungicides, as plant growth regulators and as insecticide synergists. Yet there are no P450 inhibitors as insecticides on the market. As new modes of action are constantly needed to support insecticide resistance management, P450 inhibitors should be considered because of their high potential for insect selectivity, their well-known mechanisms of action and the increasing ease of rational design and testing. © 2014 Society of Chemical Industry.
Lee, L; Chung, C; Ma, Y; Wang, G; Chen, P; Hwang, Y; Wang, J
2003-01-01
Aims: To investigate the association between cancer mortality risk and exposure to chlorinated hydrocarbons in groundwater of a downstream community near a contaminated site. Methods: Death certificates inclusive for the years 1966–97 were collected from two villages in the vicinity of an electronics factory operated between 1970 and 1992. These two villages were classified into the downstream (exposed) village and the upstream (unexposed) according to groundwater flow direction. Exposure classification was validated by the contaminant levels in 49 residential wells measured with gas chromatography/mass spectrometry. Mortality odds ratios (MORs) for cancer were calculated with cardiovascular-cerebrovascular diseases as the reference diseases. Multiple logistic regressions were performed to estimate the effects of exposure and period after adjustment for age. Results: Increased MORs were observed among males for all cancer, and liver cancer for the periods after 10 years of latency, namely, 1980–89, and 1990–97. Adjusted MOR for male liver cancer was 2.57 (95% confidence interval 1.21 to 5.46) with a significant linear trend for the period effect. Conclusion: The results suggest a link between exposure to chlorinated hydrocarbons and male liver cancer risk. However, the conclusion is limited by lack of individual information on groundwater exposure and potential confounding factors. PMID:12709523
McIntosh, Grant J; Russell, Douglas K
2013-05-23
Analogues of important aromatic growth mechanisms in hydrocarbon pyrolysis and combustion systems are extended to chlorinated systems. We consider the addition of C2Cl2 to both C4Cl3 and C4Cl5 radicals at the M06-2X/6-311+G(3df,3p)//B3LYP/6-31G(d) level of theory, and we demonstrate that these reaction systems have much in common with those of nonchlorinated species. In particular, we find that these radicals appear to lead preferentially to fulvenes, and not to the observed aromatic products, as is found in nonchlorinated systems. We have therefore also considered nonradical C4/C2 channels by way of Diels-Alder cyclization of C4Cl4/C2Cl2 and C4H2Cl2/C2HCl pairs to describe aromatic formation. While the latter pair readily leads to the formation of partially chlorinated benzenes, the fully chlorinated congeners are sterically prohibited from ring closing directly; this leads to a series of novel rearrangement processes which predict the formation of hexachloro-1,5-diene-3-yne, in addition to hexachlorobenzene, in good agreement with experiment. This suggests, for the first time, that facile nonradical routes to aromatic formation are operative in partially and fully chlorinated pyrolysis and combustion systems.
Effects of land use on surface-water quality in the East Everglades, Dade County, Florida
Waller, Bradley G.
1982-01-01
Water-quality characteristics were determined at five developed areas in the East Everglades, Dade County, Florida, during the 1978 wet season (June through October). These areas are designated as: Coopertown; Chekika Hammock State Park; residential area; rock-plowed tomato field; and Cracker Jack Slough agricultural area. Data from the developed areas were compared with data from four baseline sites in undeveloped areas to determine the effects of land use on the surface-water quality. The rock-plowed tomato field was the only area where surface-water quality was affected. Water quality at this field is affected by agricultural activities and chemical applications as indicated by increased concentrations of orthophosphate, organic nitrogen, organic carbon, copper, manganese, mercury, and potassium. The remaining four areas of land use had water-quality characteristics typical of baseline sites in nearby Northeast Shark River Slough or Taylor Slough. Chemical analyses of soil indicated chlorinated-hydrocarbon insecticide residues at Coopertown and the two agricultural areas, Cracker Jack Slough and the rock-plowed tomato field. Trace elements in concentrations greater than base level occurred at both agricultural areas (manganese), Chekika Hammock State Park (manganese), and at Coopertown (lead and zinc). (USGS)
Waller, Bradley G.
1982-01-01
The U.S. Geological Survey has collected water-quality data in the Everglades National Park since 1959. Major ions, macronutrients, trace elements, and pesticides are the primary chemical groups analyzed. The period of record and frequency of sampling vary for each chemical group, with the longest record for the major ions and the shortest for the macronutrients. Within the park there are three major drainageways: Big Cypress Swamp, Shark River Slough, and Taylor Slough. Each drainageway exhibits unique hydrologic conditions, yet there is a high degree of homogeneity in water-quality characteristics among these areas. Seasonal changes in major-ion, trace-element, and macronutrient concentrations are marked in the shallow marsh. Concentrations generally increase in the dry season due to evapotranspiration, changes in chemical equilibria, and precipitation. Water-management practices in south Florida have changed the water quality in the Shark River Slough. Most major-ion, dissolved-solid, and iron concentrations and color levels have steadily increased since 1963. The water quality in the other two drainageways has not changed since sampling began. Chlorinated-hydrocarbon insecticide residues in bottom material were found in low concentration at every sampling station in the park. (USGS)
Avian endocrine responses to environmental pollutants
Rattner, B.A.; Eroschenko, V.P.; Fox, G.A.; Fry, D.M.; Gorsline, J.
1984-01-01
Many environmental contaminants are hazardous to populations of wild birds. Chlorinated hydrocarbon pesticides and industrial pollutants are thought to be responsible for population declines of several species of predatory birds through eggshell thinning. Studies have demonstrated that these contaminants have estrogenic potency and may affect the functioning of the gonadal and thyroidal endocrine subsystems. Petroleum crude oil exerts toxicity externally, by oiling of plumage, and internally, by way of ingestion of oil while feeding or preening. Extensive ultrastructural damage to the inner zone of the adrenal, diminished adrenal responsiveness to adrenocorticotrophic hormone, and reduced corticosterone secretion rate suggest that low levels of plasma corticosterone reflect a direct effect of petroleum on the adrenal gland. Suppressive effects of oil on the ovary and decreases in circulating prolactin have been associated with impaired reproductive function. Large-scale field studies of free-living seabirds have confirmed some of the inhibitory effects of oil on reproduction that have been observed in laboratory studies. Organophosphorus insecticides, representing the most widely used class of pesticides in North America, have been shown to impair reproductive function, possibly by altering secretion of luteinizing hormone and progesterone. Relevant areas of future research on the effects of contaminants on avian endocrine function are discussed.
Li, Tiejun; Guo, Yuanming; Hu, Hongmei; Zhang, Xiaoning; Jin, Yanjian; Zhang, Xiaojun; Zhang, Yurong
2016-01-01
A simple, efficient, solvent-free, and commercial readily available approach for determination of five volatile chlorinated hydrocarbons in water samples using the static headspace sampling and gas chromatography with electron capture detection has been described. The proposed static headspace sampling method was initially optimized and the optimum experimental conditions found were 10 mL water sample containing 20% w/v sodium chloride placed in a 20 mL vial and stirred at 50ºC for 20 min. The linearity of the method was in the range of 1.2-240 μg/L for dichloromethane, 0.2-40 μg/L for trichloromethane, 0.005-1 μg/L for perchloromethane, 0.025-5 μg/L for trichloroethylene, and 0.01-2 μg/L for perchloroethylene, with coefficients of determination ranging between 0.9979 and 0.9990. The limits of detection were in the low μg/L level, ranging between 0.001 and 0.3 μg/L. The relative recoveries of spiked five volatile chlorinated hydrocarbons with external calibration method at different concentration levels in pure, tap, sea water of Jiaojiang Estuary, and sea water of waters of Xiaomendao were in the range of 91-116, 96-105, 86-112, and 80-111%, respectively, and with relative standard deviations of 1.9-3.6, 2.3-3.5, 1.5-2.7, and 2.3-3.7% (n = 5), respectively. The performance of the proposed method was compared with traditional liquid-liquid extraction on the real water samples (i.e., pure, tap, and sea water, etc.) and comparable efficiencies were obtained. It is concluded that this method can be successfully applied for the determination of volatile chlorinated hydrocarbons in different water samples. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.
Environmental availability of chlorinated organics, explosives, and metals in soils
DOE Office of Scientific and Technical Information (OSTI.GOV)
Anderson, W.C.; Loehr, R.C.; Smith, B.P.
1999-08-01
Environmental availability is key to defining the extent of remediation required. Nationally recognized experts summarize what is known about the environmental availability of chlorinated organics (Perry McCarty), explosives (Judith Pennington), and metals (Rufus Chaney). It also summarizes the current use of environmental availability to set cleanup goals for petroleum hydrocarbons and identifies essential research needed to expand the knowledge base for environmental availability.
Use of On-Site GC/MS Analysis to Distinguish Between Vapor Intrusion and Indoor Sources of VOCs
2013-11-01
Toxaphene, Volatile Organics, Acid Extractables, Benzidines, Phthalates, Nitrosamines, Nitroaromatics & Cyclic Ketones , PAHs, Haloethers, Chlorinated...SW 8270), Nitrosamines (SW 8270), Nitroaromatics & Cyclic Ketones (SW 8270), PAHs (SW 8270), Haloethers (SW 8270), Chlorinated Hydrocarbons (SW 8270...alpha-BHC, beta-BHC, gamma-BHC, delta-BHC, Dieldrin, DDD, DDE, DDT,Endosulfan I, Endosulfan II, Endosulfan sulfate, Endrin, Endrin Aldehyde
DOE Office of Scientific and Technical Information (OSTI.GOV)
Bishop, C.A.; Lean, D.R.S.; Carey, J.H.
1995-03-01
To assess intra-clutch variation in contaminant concentrations in eggs, and to investigate the dynamics of chlorinated hydrocarbon accumulation in embryos of the common snapping turtle (Chelydra serpentina), concentrations of p,p{prime}-DDE, hexachlorobenzene, trans-nonachlor, cis-chlordane, and six PCB congeners were measured in eggs, embryos, and hatchlings. Samples were collected from Cootes Paradise, a wetland at the western end of Lake Ontario, Ontario, Canada. The intra-clutch variation in chlorinated hydrocarbon concentrations within four snapping turtle clutches was determined by analyzing the first, last, and middle five eggs oviposited in the nest. The first five eggs had the highest mean concentrations of all chlorinatedmore » hydrocarbons, wet weight, and egg diameter. On a lipid weight basis, the first five eggs contained the highest concentration of all compounds except total PCBs and cis-chlordane. The concentration of cis-chlordane was the only parameter measured that was significantly different among the three sets of eggs. At hatching, snapping turtles without yolk sacs contained from 55.2 to 90.5% of the absolute amount of organochlorine compounds measured in the egg at oviposition. Eighteen days after hatching, the body burden of PCBs and pesticides decreased to 45.3 to 62.2% of that in the fresh egg. The accumulation of organochlorine chemicals in embryonic turtles peaked at or just before hatching and then declined thereafter, which is consistent with trends reported in developing sea turtles, fish, and birds.« less
Katz, Brian G.; Mallard, Gail E.
1980-01-01
In late 1980, approximately 4 million gallons per day of highly treated wastewater will be used to recharge the groundwater reservoir in central Nassau County through a system of 10 recharge basins and 5 shallow injection wells. To evaluate the impact of large-scale recharge with reclaimed water on groundwater quality, the U.S. Geological Survey has collected hydrologic and water-quality data from a 1-square-mile area around the recharge site to provide a basis for future comparison. Extensive chemical and microbiological analyses are being made on samples from 48 wells screened in the upper glacial (water-table) aquifer and the upper part of the underlying Magothy (public-supply) aquifer. Preliminary results indicate that water from the upper glacial aquifer contains significant concentrations of nitrate and low-molecular-weight chlorinated hydrocarbons and detectable concentrations of organochlorine insecticides and polychlorinated biphenyls. At present, no fecal contamination is evident in either aquifer in the area studied. In the few samples containing fecal indicator bacteria, the numbers were low. Nonpoint sources provide significant loads of organic and inorganic compounds; major sources include cesspool and septic-tank effluent, cesspool and septic-tank cleaners and other over-the-counter domestic organic solvents, fertilizers, insecticides for termite and other pest control, and stormwater runoff to recharge basins. The water-table aquifer is composed mainly of stratified, well-sorted sand and gravel and, as a result, is highly permeable. In the 1-square-mile area studied, some contaminants seem to have traveled 200 feet downward to the bottom of the water-table aquifer and into the upper part of the public-supply aquifer. (USGS)
Abdel-Sattar, Essam; Zaitoun, Ahmed A; Farag, Mohamed A; Gayed, Sabah H El; Harraz, Fathalla M H
2010-02-01
Fruit and leaf essential oils of Schinus molle showed insect repellent and insecticidal activity against Trogoderma granarium and Tribolium castaneum. In these oils, 65 components were identified by GC-MS analysis. Hydrocarbons dominated the oil composition with monoterpenes occurring in the largest amounts in fruits and leaves, 80.43 and 74.84%, respectively. p-Cymene was identified as a major component in both oils. The high yield and efficacy of S. molle essential oil against T. granarium and T. castaneum suggest that it may provide leads for active insecticidal agents.
Wilson, Jennifer T.; Van Metre, Peter C.; Werth, Charles J.; Yang, Yanning
2006-01-01
A previous study by the U.S. Geological Survey of impaired water bodies in Fort Worth, Texas, reported elevated but variable concentrations of particle-associated contaminants (PACs) comprising chlorinated hydrocarbons, polycyclic aromatic hydrocarbons, and trace elements in suspended and bed sediment of lakes and streams affected by urban land use. The U.S. Geological Survey, in cooperation with the City of Fort Worth, collected additional samples during October 2004 to investigate sources of PACs in the watersheds of two impaired lakes: Lake Como and Fosdic Lake. Source materials and aquatic sediment were sampled and analyzed for PACs. Source materials sampled consisted of street dust and soil from areas with residential and commercial land use and parking lot dust from sealed and unsealed parking lots. Aquatic sediment sampled consisted of bottom-sediment cores from the two lakes and suspended and streambed sediment from the influent stream of each lake. Samples were analyzed for chlorinated hydrocarbons (organochlorine pesticides and polychlorinated biphenyls), polycyclic aromatic hydrocarbons, major and trace elements, organic carbon, grain size, and radionuclides.
Persistent Organic Pollutants in Serum and Several Different Fat Compartments in Humans
2011-01-01
vena cava; A: aorta; P: pancreas; K: kidney; L: liver; S: stomach and spleen; C: colon; U: uterus; B: bladder; P: prostate. flame retardants , and...such as dioxins/furans, polychlori- nated biphenyls (PCBs), chlorinated pesticides, brominated Report Documentation Page Form ApprovedOMB No. 0704...perfluorinated compounds. Because of chlorine, bromine , or fluoride groups on the hydrocarbon rings or chains, these substances are resistant to degradation
Cesh, Lillian S; Williams, Tony D; Garcelon, David K; Elliott, John E
2008-10-01
Patterns and trends of chlorinated hydrocarbons were assessed in bald eagle nestling plasma from sites along the west coast of North America. Eagle plasma was sampled from four areas in southwestern British Columbia (BC), a reference site in northern BC, and from Santa Catalina Island, off the coast of California. Sites were chosen to reflect variation in contaminant exposure due to differing recent and/or historic anthropogenic activities. Santa Catalina Island had significantly greater mean concentrations of p,p'-DDE, 41.3 microg/kg wet weight (ww), than other sites, and Nanaimo/Crofton, BC had the greatest mean concentration of total PCBs, 28.9 microg/kg ww. Contaminant levels measured in 2003 in BC were compared to levels measured in 1993; over that ten year span, concentrations and patterns of chlorinated hydrocarbons have not significantly changed. There were no significant differences in levels of p,p'-DDE or hexachlorobenzene between 1993 and 2003, but significant decreases were found for trans-nonachlor and PCBs at BC sites. Levels of total PCBs and trans-nonachlor in the central Fraser Valley and Nanaimo/Crofton area have significantly decreased. Mean concentrations of p,p'-DDE measured in bald eagle nestling plasma samples in 2003 exceeded published criteria for effects on bald eagle reproduction at Santa Catalina Island and Barkley Sound, more than 30 years since heavy usage restrictions were imposed.
Mai, Bi-Xian; Fu, Jia-Mo; Sheng, Guo-Ying; Kang, Yue-Hui; Lin, Zheng; Zhang, Gan; Min, Yu-Shuan; Zeng, Eddy Y
2002-01-01
Spatial distribution of chlorinated hydrocarbons [chlorinated pesticides (CPs) and polychlorinated biphenyls (PCBs)] and polycyclic aromatic hydrocarbons (PAHs) was measured in riverine and estuarine sediment samples from Pearl River Delta, China, collected in 1997. Concentrations of CPs of the riverine sediment samples range from 12 to 158 ng/g, dry weight, while those of PCBs range from 11 to 486 ng/g. The CPs concentrations of the estuarine sediment samples are in the range 6-1658 ng/g, while concentrations of PCBs are in the range 10-339 ng/g. Total PAH concentration ranges from 1168 to 21,329 ng/g in the riverine sediment samples, whereas the PAH concentration ranges from 323 to 14,812 ng/g in the sediment samples of the Estuary. Sediment samples of the Zhujiang River and Macao harbor around the Estuary show the highest concentrations of CPs, PCBs, and PAHs. Possible factors affecting the distribution patterns are also discussed based on the usage history of the chemicals, hydrologic condition, and land erosion due to urbanization processes. The composition of PAHs is investigated and used to assess petrogenic, combustion and naturally derived PAHs of the sediment samples of the Pearl River Delta. In addition, the concentrations of a number of organic compounds of the Pearl River Delta samples indicate that sediments of the Zhujiang river and Macao harbor are most likely to pose biological impairment.
DOE Office of Scientific and Technical Information (OSTI.GOV)
Poster, D.L.; Schantz, M.M.; Parris, R.M.
1995-12-31
Standard reference materials (SRMs) are certified reference materials issued by the National Institute of Standards and Technology (NIST). Natural matrix environmental sample SRMs have been developed the Analytical Chemistry Division to assist in validating measurements for organic contaminants in the environment. Many of these are well characterized for contaminants such as polychlorinated biphenyls (PCBs), chlorinated pesticides, and polycyclic aromatic hydrocarbons (PAHs). SRM 1649, Organics in Urban Dust, is currently available with certified concentrations for 5 PAHs but because of the widespread use of this material in air pollution monitoring programs and to expand the usefulness of this material, the authorsmore » are further characterizing the material for a larger number of PAHs as well as PCBs and chlorinated pesticides. They will also soon issue a diesel particulate extract (SRM 1975) that is well characterized for PAHS, including many nitrogen substituted compounds. In addition to natural matrix materials, solutions useful for calibrating chromatographic detector response factors and retention times, and spiking sample blanks for determination of analyte recoveries, are also available. Solution SRMs currently available contain PCS congeners, chlorinated pesticides, and PAHs. New solution SRMs in preparation will contain additional chlorinated pesticides, PCB congeners (e.g., non-ortho substituted chlorobiphenyls), and perdeuterated PAHs. Recent SRM work will be presented with particular attention on the methods used for determining organic contaminant concentrations in the urban dust material and in the diesel particulate extract.« less
Reductive Degradation: Versatile, Low Cost.
ERIC Educational Resources Information Center
Water and Sewage Works, 1979
1979-01-01
This article discusses the use of reductive degradation as an economical and effective treatment of chlorinated hydrocarbons. Comparisons with activated carbon treatment show lower capital equipment and treatment costs. (CS)
The Influence of Nitrogen Oxides on Chlorine Chemistry in Barrow, Alaska
NASA Astrophysics Data System (ADS)
McNamara, S. M.; Raso, A. R. W.; Wang, S.; Thanekar, S.; Fuentes, J. D.; Shepson, P. B.; Pratt, K.
2016-12-01
Active chlorine chemistry in the springtime Arctic boundary layer impacts the fate of atmospheric pollutants and greenhouse gases. Recent field studies have reported high amounts of molecular chlorine (Cl2), up to 400 parts per trillion (ppt), as well as the presence of chlorinated hydrocarbon oxidation products. However, our knowledge of Arctic chlorine chemistry is limited by a paucity of observations. The presence of nitrogen oxides (NOx) may influence the chlorine chemistry in this region. Here, we report chemical ionization mass spectrometry measurements of Cl2, chlorine monoxide (ClO), nitryl chloride (ClNO2), and dinitrogen pentoxide (N2O5), and NOx measurements at Barrow, AK during March-May 2016. To our knowledge, these data represent the first observations of ClNO2 in the Arctic. While the main source of NOx in a pristine Arctic environment is irradiated snow surfaces, anthropogenic sources can significantly enhance local NOx concentrations. The role of NOx in the activation and temporal trends of the reactive chlorine species are examined using a 0-D photochemical model. The prevalence of chlorine chemistry under elevated nitrogen oxide conditions may have significant impacts on the atmospheric composition in an increasingly polluted Arctic.
Tillner, Jocelyn; Hollard, Caroline; Bach, Cristina; Rosin, Christophe; Munoz, Jean-François; Dauchy, Xavier
2013-11-08
In this study, an automated method for the simultaneous determination of polycyclic aromatic hydrocarbons (PAHs) and their chlorination by-products in drinking water was developed based on online solid-phase microextraction-gas chromatography-mass spectrometry. The main focus was the optimisation of the solid-phase microextraction step. The influence of the agitation rate, type of fibre, desorption time, extraction time, extraction temperature, desorption temperature, and solvent addition was examined. The method was developed and validated using a mixture of 17 PAHs, 11 potential chlorination by-products (chlorinated and oxidised PAHs) and 6 deuterated standards. The limit of quantification was 10 ng/L for all target compounds. The validated method was used to analyse drinking water samples from three different drinking water distribution networks and the presumably coal tar-based pipe coatings of two pipe sections. A number of PAHs were detected in all three networks although individual compositions varied. Several PAH chlorination by-products (anthraquinone, fluorenone, cyclopenta[d,e,f]phenanthrenone, 3-chlorofluoranthene, and 1-chloropyrene) were also found, their presence correlating closely with that of their respective parent compounds. Their concentrations were always below 100 ng/L. In the coatings, all PAHs targeted were detected although concentrations varied between the two coatings (76-12,635 mg/kg and 12-6295 mg/kg, respectively). A number of chlorination by-products (anthraquinone, fluorenone, cyclopenta[d,e,f]phenanthrenone, 3-chlorofluoranthene, and 1-chloropyrene) were also detected (from 40 to 985 mg/kg), suggesting that the reaction of PAHs with disinfectant agents takes place in the coatings and not in the water phase after migration. Copyright © 2013 Elsevier B.V. All rights reserved.
Bright, D A; Healey, N
2003-01-01
This study examines the potential for environmental risks due to organic contaminants at sewage sludge application sites, and documents metals and various potential organic contaminants (volatile organics, chlorinated pesticides, PCBs, dioxins/furans, extractable petroleum hydrocarbons, PAHs, phenols, and others) in current production biosolids from five wastewater treatment plants (WWTPs) within the Greater Vancouver Regional District (GVRD). There has been greater focus in Europe, North America and elsewhere on metals accumulation in biosolids-amended soil than on organic substances, with the exception of polychlorinated dibenzo-p-dioxins and polychlorinated dibenzofurans. Another objective, therefore, was to evaluate the extent to which management of biosolids re-use based on metal/metalloid levels coincidentally minimizes environmental risks from organic contaminants. Historical-use contaminants such as chlorophenols, PCBs, and chlorinated pesticides were not detected at environmentally relevant concentrations in any of the 36 fresh biosolids samples, and appear to have virtually eliminated from sanitary collection system inputs. The few organic contaminants found in freshly produced biosolids samples that exhibited high concentrations relative to British Columbia and Canadian soil quality benchmarks included p-cresol, phenol, phenanthrene, pyrene, naphthalene, and heavy extractable petroleum hydrocarbons (HEPHs--nCl9-C34 effective carbon chain length). It was concluded that, with the exception of these petroleum hydrocarbon constituents or their microbial metabolites, the mixing of biosolids with uncontaminated soils during land application and based on the known metal concentrations in biosolids from the Greater Vancouver WWTPs investigated provides adequate protection against the environmental risks associated with organic substances such as dioxins and furans, phthalate esters, or volatile organics. Unlike many other organic contaminants, the concentrations of petroleum hydrocarbon derived substances in biosolids has not decreased within the last decade or more in the WWTPs studied, and--unlike persistent chlorinated compounds--the associated PAHs and other hydrocarbon constituents merit careful consideration, especially in the context of repeated land-application of biosolid.
Quigley, W W; Ecker, S T; Vahey, P G; Synovec, R E
1999-10-01
The development of liquid chromatography with a commercially available cyano propyl stationary phase and a 100% water mobile phase is reported. Separations were performed at ambient temperature, simplifying instrumental requirements. Excellent separation efficiency using a water mobile phase was achieved, for example N=18 800, or 75 200 m(-1), was obtained for resorcinol, at a retention factor of k'=4.88 (retention time of 9.55 min at 1 ml min(-1) for a 25 cmx4.6 mm i.d. column, packed with 5 mum diameter particles with the cyano propyl stationary phase). A separation via reversed phase liquid chromatography (RP-LC) with a 100% water mobile phase of six phenols and related compounds was compared to a separation of the same compounds by traditional RP-LC, using octadecylsilane (ODS), i.e. C18, bound to silica and an aqueous mobile phase modified with acetonitrile. Nearly identical analysis time was achieved for the separation of six phenols and related compounds using the cyano propyl stationary phase with a 100% water mobile phase, as compared to traditional RP-LC requiring a relatively large fraction of organic solvent modifier in the mobile phase (25% acetonitrile:75% water). Additional understanding of the retention mechanism with the 100% water mobile phase was obtained by relating measured retention factors of aliphatic alcohols, phenols and related compounds, and chlorinated hydrocarbons to their octanol:water partition coefficients. The retention mechanism is found to be consistent with a RP-LC mechanism coupled with an additional retention effect due to residual hydroxyl groups on the cyano propyl stationary phase. Advantages due to a 100% water mobile phase for the chemical analysis of alcohol mixtures and chlorinated hydrocarbons are reported. By placing an absorbance detector in-series and preceding a novel drop interface to a flame ionization detector (FID), selective detection of a separated mixture of phenols and related compounds and aliphatic alcohols is achieved. The compound class of aliphatic alcohols is selectively and sensitively detected by the drop interface/FID, and the phenols and related compounds are selectively and sensitively detected by absorbance detection at 200 nm. The separation and detection of chlorinated hydrocarbons in a water sample matrix further illustrated the advantages of this methodology. The sensitivity and selectivity of the FID signal for the chlorinated hydrocarbons are significantly better than absorbance detection, even at 200 nm. This methodology is well suited to continuous and automated monitoring of water samples. The applicability of samples initially in an organic solvent matrix is explored, since an organic sample matrix may effect retention and efficiency. Separations in acetonitrile and isopropyl alcohol sample matrices compared well to separations with a water sample matrix.
1990-11-01
agents has been associated with the occurrence of liver neoplasia in laboratory rodents (Reddy and Lalwani, 1983). Additionally, some chlorinated ...hepatocarcinogenicity. Toxicol. Appl. Pharmacol. 92:103-112. Goldsworthy, T.L. and J.A. Popp. 1987. Chlorinated hydrocarbon-induced peroxisome enzyme... atmosphere containing 5% ± 1.5% CO2. Laboratory cultures were checked periodically for karyotype stability and for the absence of mycoplasma
Bioremediation and phytoremediation: Chlorinated and recalcitrant compounds
DOE Office of Scientific and Technical Information (OSTI.GOV)
NONE
1998-12-31
Bioremediation and phytoremediation have progressed, especially with regard to the treatment of hydrocarbon-contaminated sites. Sites contaminated with chlorinated and recalcitrant compounds have proven more resistant to these approaches, but exciting progress is being made both in the laboratory and in the field. This book brings together the latest breakthrough thinking and results in bioremediation, with chapters on cometabolic processes, aerobic and anaerobic mechanisms, biological reductive dechlorination processes, bioaugmentation, biomonitoring, and phytoremediation of recalcitrant organic compounds.
7 CFR 94.102 - Analyses available.
Code of Federal Regulations, 2014 CFR
2014-01-01
..., chlorinated hydrocarbon and fumigant residues, dextrin, heavy and light filth, glucose, glycerol and gums. In addition, egg products can be analyzed for high sucrose content, pH, heavy metals and minerals, monosodium...
7 CFR 94.102 - Analyses available.
Code of Federal Regulations, 2011 CFR
2011-01-01
..., chlorinated hydrocarbon and fumigant residues, dextrin, heavy and light filth, glucose, glycerol and gums. In addition, egg products can be analyzed for high sucrose content, pH, heavy metals and minerals, monosodium...
7 CFR 94.102 - Analyses available.
Code of Federal Regulations, 2013 CFR
2013-01-01
..., chlorinated hydrocarbon and fumigant residues, dextrin, heavy and light filth, glucose, glycerol and gums. In addition, egg products can be analyzed for high sucrose content, pH, heavy metals and minerals, monosodium...
7 CFR 94.102 - Analyses available.
Code of Federal Regulations, 2012 CFR
2012-01-01
..., chlorinated hydrocarbon and fumigant residues, dextrin, heavy and light filth, glucose, glycerol and gums. In addition, egg products can be analyzed for high sucrose content, pH, heavy metals and minerals, monosodium...
DOE Office of Scientific and Technical Information (OSTI.GOV)
Wrobel, Michael Hubert, E-mail: m.wrobel@pan.olszt
The aim of the study was to investigate the effect of chlordane, heptachlor and mirex, on hormonal regulation of the force of myometrial contractions. Myometrial, endometrial, granulosa and luteal cells as well as strips of myometrium from non-pregnant cows were incubated with three insecticides at environmentally relevant doses (0.1, 1 or 10 ng/ml). None of the insecticides affected the viability of studied cells. Chlordane stimulated, while heptachlor and mirex inhibited, secretion of testosterone and estradiol from granulosa cells as well as secretion of progesterone from luteal cells, respectively. Secretion of oxytocin (OT) from granulosa cells was increased after incubation withmore » all studied insecticides. Only mirex stimulated OT secretion from luteal cells, while heptachlor inhibited this effect. None of them affected synthesis of OT in luteal cells and prostaglandins (PGF2 and PGE2) secretion from uterine cells, except PGE2 secretion from endometrial cells was decreased when the cells were incubated with 0.1 ng/ml of chlordane. Basal and OT-stimulated myometrial contractions were increased by mirex and decreased by heptachlor. The data show that the insecticides altered secretory function of ovarian cells. Heptachlor and mirex affected also myometrial contractions in vitro, but uterine secretion of prostaglandins were not involved in the mechanism of that adverse effect of insecticides. The data indicate on potential of these insecticides to disturb fertilisation, blastocyst implantation or even the length of gestation. - Highlights: • The studied insecticides affected steroids and oxytocin secretion from ovaries. • Mirex stimulated bovine myometrial contractions. • Heptachlor inhibited bovine myometrial contractions. • Prostaglandins are not involved in adverse effect of the insecticides on uterine contractions.« less
Catalytic Destruction of Chlorinated Volatile Organic Compounds
1993-08-01
Figure 1. The glass reactor passed through two furnaces. Both the furnaces were Lindberg 55035 hinged tube type. The top furnace served the purpose...10. HC1 Scrubber 10 11 12 11 13 11. Thermocouples 12. Manometer Tap 13. Glass Wool Figure 1. Schematic of the Reactor were used to check the...In the case of catalyst pellets, a thin layer of glass wool was used to hold the bed in place. The chlorinated hydrocarbon feed was introduced into
2016-07-01
petroleum hydrocarbon fuels due to higher densities, lower viscosities , and increased weathering (mass depletion) of residual chlorinated solvent DNAPL...generally classified as stratified layers of fine sand and silt with few clay layers. A silt layer was penetrated consistently at a depth of about 45...e.g., stiff clays ) there is potential for the thickness of the dye interaction zone to increase to approximately 1-2 mm. Intuition suggests that this
2004-03-01
al. (1985) reported that the capability for central nervous system depression and liver or kidney injury increases with degree of chlorination...skin irritation, and potential liver or kidney damage (Hathaway et al., 1996). The risk for exposure to groundwater contaminated with a CAH 13 is...oxidative metabolites have caused liver and lung tumors in mice, though it appears that direct extrapolation from rodent data would overstate human TCE
1988-05-01
include poly- chlorinated biphenyls (PCBs) and related chlorinated pesticides of similar polarity in addition to the petroleum hydrocarbons . The...Ui It tILL (JV: FIELD VERIFICATION PROGRAM (AQUATIC DISPOSAL).’Wh TECHNICAL REPORT D-87-6 COMPARISON OF FIELD AND LABORATORY BIOACCUMULATION OF...Laboratory Bioaccumulation of Organic and Inorganic Contaminants from Black Rock Harbor Dredged Material 12 PERSONAL AUTHOR(S) Lake, James L.; Galloway
Pereira, W.E.; Hostettler, F.D.; Rapp, J.B.
1996-01-01
The distribution and fate of chlorinated pesticides, biomarkers, and polycyclic aromatic hydrocarbons (PAHs) in surficial sediments along a contamination gradient in the Lauritzen Canal and Richmond Harbor in San Francisco Bay was investigated. Compounds were identified and quantified using gas chromatography-ion trap mass spectrometry. Biomarkers and PAHs were derived primarily from weathered petroleum. DDT was reductively dechlorinated under anoxic conditions to DDD and several minor degradation products, DDMU, DDMS, and DDNU. Under aerobic conditions, DDT was dehydrochlorinated to DDE and DBP. Aerobic degradation of DDT was diminished or inhibited in zones of high concentration, and increased significantly in zones of lower concentration: Other chlorinated pesticides identified in sediment included dieldrin and chlordane isomers. Multivariate analysis of the distributions of the DDTs suggested that there are probably two sources of DDD. In addition, DDE and DDMU are probably formed by similar mechanisms, i.e. dehydrochlorination. A steep concentration gradient existed from the Canal to the Outer Richmond Harbor, but higher levels of DDD than those found in the remainder of the Bay indicated that these contaminants are transported on particulates and colloidal organic matter from this source into San Francisco Bay. Chlorinated pesticides and PAHs may pose a potential problem to biota in San Francisco Bay.
Xu, Jie; Pu, Yuan; Yang, Xiao Jin; Wan, Pingyu; Wang, Rong; Song, Peng; Fisher, Adrian
2017-09-05
Water contamination with chlorinated hydrocarbons such as chloroform (CHCl 3 ), carbon tetrachloride (CCl 4 ) and trichloroethylene (TCE) is one of the major public health concerns. In this study, we explored the use of aluminum-iron alloys particles in millimeter scale for rapid removal of CHCl 3 , CCl 4 and TCE from water. Three types of Al-Fe alloy particles containing 10, 20 and 58 wt% of Fe (termed as Al-Fe10, Al-Fe20 and Al-Fe58) were prepared and characterized by electrochemical polarization, X-ray diffraction and energy dispersive spectrometer. For concentrations of 30-180 μg/L CHCl 3 , CCl 4 and TCE, a removal efficiency of 45-64% was achieved in a hydraulic contact time of less than 3 min through a column packed with 0.8-2 mm diameter of Al-Fe alloy particles. The concentration of Al and Fe ions released into water was less than 0.15 and 0.05 mg/L, respectively. Alloying Al with Fe enhances reactivity towards chlorinated hydrocarbons' degradation and the enhancement is likely the consequence of galvanic effects between different phases (Al, Fe and intermetallic Al-Fe compounds such as Al 13 Fe 4 , Fe 3 Al and FeAl 2 ) and catalytic role of these intermetallic Al-Fe compounds. The results demonstrate that the use of Al-Fe alloy particles offers a viable and green option for chlorinated hydrocarbons' removal in water treatment.
Occupational exposures and pancreatic cancer: a meta-analysis
Ojajarvi, I; Partanen, T.; Ahlbom, A.; Boffetta, P.; Hakulinen, T.; Jourenkova, N.; Kauppinen, T.; Kogevinas, M.; Porta, M.; Vainio, H.; Weiderpass, E.; Wesseling, C.
2000-01-01
OBJECTIVES—Consolidation of epidemiological data on pancreatic cancer and worksite exposures. METHODS—Publications during 1969-98 were surveyed. Studies without verified exposures were excluded. Meta-analyses were conducted on data from 92 studies covering 161 populations, with results for 23 agents or groups of agents. With a standard format, five epidemiologists extracted risk estimates and variables of the structure and quality of each study. The extracted data were centrally checked. Random meta-models were applied. RESULTS—Based on 20 populations, exposure to chlorinated hydrocarbon (CHC) solvents and related compounds was associated with a meta-risk ratio (MRR) of 1.4 (95% confidence interval (95% CI) 1.0 to 1.8). Nickel and nickel compounds were considered in four populations (1.9; 1.2 to 3.2). Excesses were found also for chromium and chromium compounds (1.4; 0.9 to 2.3), polycyclic aromatic hydrocarbons (PAHs) (1.5; 0.9 to 2.5), organochlorine insecticides (1.5; 0.6 to 3.7), silica dust (1.4; 0.9 to 2.0), and aliphatic and alicyclic hydrocarbon solvents (1.3; 0.8 to 2.8). Evidence on pancreatic carcinogenicity was weak or non-positive for the following agents: acrylonitrile (1.1; 0.0 to 6.2); arsenic (1.0; 0.6 to 1.5); asbestos (1.1; 0.9 to 1.5); diesel engine exhaust (1.0; 0.9 to 1.3); electromagnetic fields (1.1; 0.8 to 1.4); formaldehyde (0.8; 0.5 to 1.0); flour dust (1.1; 0.3 to 3.2); cadmium and cadmium compounds (0.7; 0.4 to 1.4); gasoline (1.0; 0.8 to 1.2); herbicides (1.0; 0.8 to 1.3); iron and iron compounds (1.3; 0.7 to 2.5); lead and lead compounds (1.1; 0.8 to 1.5); man-made vitreous fibres (1.0; 0.6 to 1.6); oil mist (0.9; 0.8 to 1.0); and wood dust (1.1; 0.9 to 2.5). The occupational aetiological fraction of pancreatic cancer was estimated at 12%. In a subpopulation exposed to CHC solvents and related compounds, it was 29%; to chromium and chromium compounds, 23%; to nickel and nickel compounds, 47%; to insecticides, 33%; and to PAHs, 33%. CONCLUSION—Occupational exposures may increase risk of pancreatic cancer. High quality studies are called for on interactions between occupational, environmental, and lifestyle factors as well as interactions between genes and the environment. Keywords: pancreatic cancer; occupational exposure; meta-analysis PMID:10769297
Iron-carbon composites for the remediation of chlorinated hydrocarbons
NASA Astrophysics Data System (ADS)
Sunkara, Bhanu Kiran
This research is focused on engineering submicron spherical carbon particles as effective carriers/supports for nanoscale zerovalent iron (NZVI) particles to address the in situ remediation of soil and groundwater chlorinated contaminants. Chlorinated hydrocarbons such as trichloroethylene (TCE) and tetrachloroethylene (PCE) form a class of dense non-aqueous phase liquid (DNAPL) toxic contaminants in soil and groundwater. The in situ injection of NZVI particles to reduce DNAPLs is a potentially simple, cost-effective, and environmentally benign technology that has become a preferred method in the remediation of these compounds. However, unsupported NZVI particles exhibit ferromagnetism leading to particle aggregation and loss in mobility through the subsurface. This work demonstrates two approaches to prepare carbon supported NZVI (iron-carbon composites) particles. The objective is to establish these iron-carbon composites as extremely useful materials for the environmental remediation of chlorinated hydrocarbons and suitable materials for the in situ injection technology. This research also demonstrates that it is possible to vary the placement of iron nanoparticles either on the external surface or within the interior of carbon microspheres using a one-step aerosol-based process. The simple process of modifying iron placement has significant potential applications in heterogeneous catalysis as both the iron and carbon are widely used catalysts and catalyst supports. Furthermore, the aerosol-based process is applied to prepare new class of supported catalytic materials such as carbon-supported palladium nanoparticles for ex situ remediation of contaminated water. The iron-carbon composites developed in this research have multiple functionalities (a) they are reactive and function effectively in reductive dehalogenation (b) they are highly adsorptive thereby bringing the chlorinated compound to the proximity of the reactive sites and also serving as adsorption materials for decontamination (c) they are of the optimal size for transport through sediments (d) they have amphiphilic chemical functionalities that help stabilize them when they reach the DNAPL target zones. Finally, the iron-carbon composite microspheres prepared through aerosol-based process can used for in situ injection technology as the process is conductive to scale-up and the materials are environmentally benign.
METHODS AND ANALYSES FOR IMPLEMENTING NATURAL ATTENUATION PROTOCOLS
Technical protocols for evaluating natural attenuation at petroleum hydrocarbon and chlorinated solvent contaminated sites specify the analysis of electron acceptors and metabolic by-products for identifying and quantifying natural attenuation processes. However, these protocols ...
Balabanidou, Vasileia; Kampouraki, Anastasia; MacLean, Marina; Blomquist, Gary J; Tittiger, Claus; Juárez, M Patricia; Mijailovsky, Sergio J; Chalepakis, George; Anthousi, Amalia; Lynd, Amy; Antoine, Sanou; Hemingway, Janet; Ranson, Hilary; Lycett, Gareth J; Vontas, John
2016-08-16
The role of cuticle changes in insecticide resistance in the major malaria vector Anopheles gambiae was assessed. The rate of internalization of (14)C deltamethrin was significantly slower in a resistant strain than in a susceptible strain. Topical application of an acetone insecticide formulation to circumvent lipid-based uptake barriers decreased the resistance ratio by ∼50%. Cuticle analysis by electron microscopy and characterization of lipid extracts indicated that resistant mosquitoes had a thicker epicuticular layer and a significant increase in cuticular hydrocarbon (CHC) content (∼29%). However, the CHC profile and relative distribution were similar in resistant and susceptible insects. The cellular localization and in vitro activity of two P450 enzymes, CYP4G16 and CYP4G17, whose genes are frequently overexpressed in resistant Anopheles mosquitoes, were analyzed. These enzymes are potential orthologs of the CYP4G1/2 enzymes that catalyze the final step of CHC biosynthesis in Drosophila and Musca domestica, respectively. Immunostaining indicated that both CYP4G16 and CYP4G17 are highly abundant in oenocytes, the insect cell type thought to secrete hydrocarbons. However, an intriguing difference was indicated; CYP4G17 occurs throughout the cell, as expected for a microsomal P450, but CYP4G16 localizes to the periphery of the cell and lies on the cytoplasmic side of the cell membrane, a unique position for a P450 enzyme. CYP4G16 and CYP4G17 were functionally expressed in insect cells. CYP4G16 produced hydrocarbons from a C18 aldehyde substrate and thus has bona fide decarbonylase activity similar to that of dmCYP4G1/2. The data support the hypothesis that the coevolution of multiple mechanisms, including cuticular barriers, has occurred in highly pyrethroid-resistant An gambiae.
Balabanidou, Vasileia; Kampouraki, Anastasia; MacLean, Marina; Blomquist, Gary J.; Tittiger, Claus; Juárez, M. Patricia; Mijailovsky, Sergio J.; Chalepakis, George; Anthousi, Amalia; Lynd, Amy; Antoine, Sanou; Hemingway, Janet; Ranson, Hilary; Lycett, Gareth J.; Vontas, John
2016-01-01
The role of cuticle changes in insecticide resistance in the major malaria vector Anopheles gambiae was assessed. The rate of internalization of 14C deltamethrin was significantly slower in a resistant strain than in a susceptible strain. Topical application of an acetone insecticide formulation to circumvent lipid-based uptake barriers decreased the resistance ratio by ∼50%. Cuticle analysis by electron microscopy and characterization of lipid extracts indicated that resistant mosquitoes had a thicker epicuticular layer and a significant increase in cuticular hydrocarbon (CHC) content (∼29%). However, the CHC profile and relative distribution were similar in resistant and susceptible insects. The cellular localization and in vitro activity of two P450 enzymes, CYP4G16 and CYP4G17, whose genes are frequently overexpressed in resistant Anopheles mosquitoes, were analyzed. These enzymes are potential orthologs of the CYP4G1/2 enzymes that catalyze the final step of CHC biosynthesis in Drosophila and Musca domestica, respectively. Immunostaining indicated that both CYP4G16 and CYP4G17 are highly abundant in oenocytes, the insect cell type thought to secrete hydrocarbons. However, an intriguing difference was indicated; CYP4G17 occurs throughout the cell, as expected for a microsomal P450, but CYP4G16 localizes to the periphery of the cell and lies on the cytoplasmic side of the cell membrane, a unique position for a P450 enzyme. CYP4G16 and CYP4G17 were functionally expressed in insect cells. CYP4G16 produced hydrocarbons from a C18 aldehyde substrate and thus has bona fide decarbonylase activity similar to that of dmCYP4G1/2. The data support the hypothesis that the coevolution of multiple mechanisms, including cuticular barriers, has occurred in highly pyrethroid-resistant An. gambiae. PMID:27439866
Poupardin, Rodolphe; Reynaud, Stéphane; Strode, Clare; Ranson, Hilary; Vontas, John; David, Jean-Philippe
2008-05-01
The effect of exposure of Aedes aegypti larvae to sub-lethal doses of the pyrethroid insecticide permethrin, the organophosphate temephos, the herbicide atrazine, the polycyclic aromatic hydrocarbon fluoranthene and the heavy metal copper on their subsequent tolerance to insecticides, detoxification enzyme activities and expression of detoxification genes was investigated. Bioassays revealed a moderate increase in larval tolerance to permethrin following exposure to fluoranthene and copper while larval tolerance to temephos increased moderately after exposure to atrazine, copper and permethrin. Cytochrome P450 monooxygenases activities were induced in larvae exposed to permethrin, fluoranthene and copper while glutathione S-transferase activities were induced after exposure to fluoranthene and repressed after exposure to copper. Microarray screening of the expression patterns of all detoxification genes following exposure to each xenobiotic with the Aedes Detox Chip identified multiple genes induced by xenobiotics and insecticides. Further expression studies using real-time quantitative PCR confirmed the induction of multiple CYP genes and one carboxylesterase gene by insecticides and xenobiotics. Overall, this study reveals the potential of xenobiotics found in polluted mosquito breeding sites to affect their tolerance to insecticides, possibly through the cross-induction of particular detoxification genes. Molecular mechanisms involved and impact on mosquito control strategies are discussed.
A large atomic chlorine source inferred from mid-continental reactive nitrogen chemistry.
Thornton, Joel A; Kercher, James P; Riedel, Theran P; Wagner, Nicholas L; Cozic, Julie; Holloway, John S; Dubé, William P; Wolfe, Glenn M; Quinn, Patricia K; Middlebrook, Ann M; Alexander, Becky; Brown, Steven S
2010-03-11
Halogen atoms and oxides are highly reactive and can profoundly affect atmospheric composition. Chlorine atoms can decrease the lifetimes of gaseous elemental mercury and hydrocarbons such as the greenhouse gas methane. Chlorine atoms also influence cycles that catalytically destroy or produce tropospheric ozone, a greenhouse gas potentially toxic to plant and animal life. Conversion of inorganic chloride into gaseous chlorine atom precursors within the troposphere is generally considered a coastal or marine air phenomenon. Here we report mid-continental observations of the chlorine atom precursor nitryl chloride at a distance of 1,400 km from the nearest coastline. We observe persistent and significant nitryl chloride production relative to the consumption of its nitrogen oxide precursors. Comparison of these findings to model predictions based on aerosol and precipitation composition data from long-term monitoring networks suggests nitryl chloride production in the contiguous USA alone is at a level similar to previous global estimates for coastal and marine regions. We also suggest that a significant fraction of tropospheric chlorine atoms may arise directly from anthropogenic pollutants.
MNA of Metals and In Situ Bioremediation
Monitored Natural Attenuation (MNA) is a frequently applied remediation option for organic contaminants in groundwater, especially fuel hydrocarbons and chlorinated compounds. Current lines of research examine whether or not MNA is more broadly applicable to inorganic contaminan...
MOLECULAR BASIS OF BIODEGRADATION OF CHLOROAROMATIC COMPOUNDS
Chlorinated aromatic hydrocarbons are widely used in industry and agriculture, and comprise the bulk of environmental pollutants. Although simple aromatic compounds are biodegradable by a variety of degradative pathways, their halogenated counterparts are more resistant to bacter...
TREATING CHLORINATED WASTES WITH THE KPEG PROCESS
The two reports summarized here describe development of the alkali metal (polyethylene gylycolate (APEG) chemical technology to dechlorinate hazardous hydrocarbons in soils and its application at four demonstration sites: field-scale application to contaminated soils on the isla...
Protocol for Enhanced in situ Bioremediation Using Emulsified Edible Oil
2006-05-01
of molecular hydrogen include natural organic matter, fuel hydrocarbons, landfill leachate , or added organic substrates. Hydrogen is generated by... Phytoremediation of Chlorinated and Recalcitrant Compounds, p. 47-53. APPENDIX A SUBSTRATE CALCULATIONS Excel spreadsheets are
DOE Office of Scientific and Technical Information (OSTI.GOV)
NONE
1996-01-16
The Petro-Processors of Louisiana, Inc. (PPI) site, located in East Baton Rouge Parish, Louisiana, operated two waste disposal facilities: the Brooklawn area and the Scenic Highway area. Both areas contain chlorinated aromatic hydrocarbons and chlorinated hydrocarbons. Contaminants have been detected in samples from soil, groundwater, surface water, and air at the Brooklawn area and in soil, groundwater, and air at the Scenic Highway area. The site is considered a public health hazard because of risks to human health from past, present, and future exposure to hazardous substances. Exposure pathways of public health concern are: ingestion of contaminated fish, potential ingestionmore » of contaminated groundwater and wildlife, dermal contact with contaminated sediments, inhalation of airborne volatile contaminants prior to and during remedial activities, and dermal contact and incidental ingestion of contaminated soils.« less
Bioconcentration of chlorinated hydrocarbons from sediment by oligochaetes
DOE Office of Scientific and Technical Information (OSTI.GOV)
Connell, D.W.; Bowman, M.; Hawker, D.W.
1988-12-01
Previously published data on the accumulation of 15 chlorinated hydrocarbons from sediment by oligochaetes have been interpreted on the basis of bioconcentration from interstitial water. Calculation of the interstitial water concentration allowed determination of uptake and clearance rate constants together with bioconcentration factors (KB) for these compounds. These three factors each exhibited a systematic relationship to the octanol/water partition coefficient (KOW). The log KB versus log KOW relationship was roughly linear over the log KOW range from 4.4 to 6.4 and displayed an increasing nonlinear deviation for log KOW values greater than 6.4. These relationships are qualitatively similar to thosemore » established for other aquatic organisms where bioconcentration from water was the mechanism involved. This suggests that interstitial water may be the phase from which lipophilic compounds in sediment are bioconcentrated by oligochaetes. An expression relating the bioconcentration factor to the biotic concentration and various sediment characteristics has also been developed.« less
NASA Astrophysics Data System (ADS)
Contamination of U.S. coastal areas may be decreasing as a result of environmental regulations that have banned or curtailed toxic chemicals, concludes a report by the National Oceanic and Atmospheric Administration. The report, “Recent Trends in Coastal Environmental Quality: Results from the Mussel Watch Project,” presents results of analyzing chemical concentrations found in mussel and oyster tissues collected every year since 1986.These mollusks are collected once a year at more than 240 sites nationwide and analyzed for over 70 polycyclic aromatic hydrocarbons, polychlorinated biphenyls, chlorinated pesticides, butyltins, and toxic trace elements such as copper, cadmium, and lead. The report states that from 1986 to 1993 there were many more decreases than increases in chemical concentrations in coastal regions. These decreasing trends were not unexpected; all of the monitored chlorinated hydrocarbons have been banned for use in the United States, and tributyltin has been banned as a biocide on recreational boats.
Blondeel, Evelyne; Depuydt, Veerle; Cornelis, Jasper; Chys, Michael; Verliefde, Arne; Van Hulle, Stijin Wim Henk
2015-01-01
Pilot-scale optimisation of different possible physical-chemical water treatment techniques was performed on the wastewater originating from three different recovery and recycling companies in order to select a (combination of) technique(s) for further full-scale implementation. This implementation is necessary to reduce the concentration of both common pollutants (such as COD, nutrients and suspended solids) and potentially toxic metals, polyaromatic hydrocarbons and poly-chlorinated biphenyls frequently below the discharge limits. The pilot-scale tests (at 250 L h(-1) scale) demonstrate that sand anthracite filtration or coagulation/flocculation are interesting as first treatment techniques with removal efficiencies of about 19% to 66% (sand anthracite filtration), respectively 18% to 60% (coagulation/flocculation) for the above mentioned pollutants (metals, polyaromatic hydrocarbons and poly chlorinated biphenyls). If a second treatment step is required, the implementation of an activated carbon filter is recommended (about 46% to 86% additional removal is obtained).
Onodera, Sukeo
2010-09-01
This paper reviews the formation mechanism and chemical safety of nonintentional chemical substances (NICS) present in chlorine-treated water containing organic contaminants. Undesirable compounds, i.e., NICS, may be formed under certain conditions when chlorine reacts with organic matter. The rate and extent of chlorine consumption with organics are strongly dependent on their chemical structures, particularly whether double bonds or sulfur and nitrogen atoms occur in the molecules. Organothiophosphorus pesticides (P=S type) are easily oxidized to their phosphorus compounds (P=O type) in chlorinated water containing HOCl as little as 0.5 mg/l, resulting in an increase in cholinesterase-inhibitory activity. Chlorination of phenols in water also produces a series of highly chlorinated compounds, including chlorophenols, chloroquinones, chlorinated carboxylic acids, and polychlorinated phenoxyphenols (PCPPs). In some of these chloroquinones, 2,6-dichloroalkylsemiquinones exhibit a strong mutagenic response as do positive controls used in the Ames test. 2-phenoxyphenols in these PCPPs are particularly interesting, as they are present in the chlorine-treated phenol solution and they are also precursors (predioxins) of the highly toxic chlorinated dioxins. Polynuclear aromatic hydrocarbons (PAHs) were found to undergo chemical changes due to hypochlorite reactions to give chloro-substituted PAHs, oxygenated (quinones) and hydroxylated (phenols) compounds, but they exhibit a lower mutagenic response. In addition, field work was performed in river water and drinking water to obtain information on chemical distribution and their safety, and the results are compared with those obtained in the model chlorination experiments.
NASA Technical Reports Server (NTRS)
Glavin, Daniel P.; Freissinet, Caroline; Miller, Kristen E.; Eigenbrode, Jennifer L.; Brunner, Anna E.; Buch, Arnaud; Sutter, Brad; Archer, P. Douglas, Jr.; Atreya, Sushil K.; Brinckerhoff, William B.;
2013-01-01
Four individual sample portions from a single scoop of the Rocknest aeolian deposit were sieved ( 150 m) and delivered to the Sample Analysis at Mars (SAM) instrument by the Mars Science Laboratory rover's sample acquisition system. The samples were analyzed separately by the SAM pyrolysis evolved gas and gas chromatography mass spectrometry analysis modes. Several chlorinated hydrocarbons including chloromethane, dichloromethane, trichloromethane, a chloromethylpropene, and chlorobenzene were identified by SAM above background levels with abundances of 0.01 to 2.3 nanomole.The evolution of the chloromethanes observed during pyrolysis is coincident with the increase in O2 released from the Rocknest sample and the decomposition of a product of N-methyl-N- (tert-butyldimethylsilyl)trifluoroacetamide (MTBSTFA), a chemical that leaked from a derivatization cup inside SAM.The best candidate for the oxychloride phase in Rocknest is a hydrated calcium perchlorate (Ca(ClO4)2nH2O), based on the temperature release of O2 that correlates with the release of the chlorinated species measured by SAM, although other chlorine bearing phases are being considered. Laboratory pyrolysis experiments suggest that reaction of martian chlorine with organic carbon from MTBSTFA can explain the presence of the chloromethanes and a chloromethylpropene also detected by SAM.However, we cannot exclude the possibility that traces of organic carbon of either martian or exogenous origin contributed to some of the chloromethanes measured by SAM. Although the alteration history and exposure age of the Rocknest deposit is unknown, it is possible that oxidative degradation of complex organic matter by ionizing radiation or other chemical processes in Rocknest has occurred.
[Combined use of active chlorine and coagulants for drinking water purification and disinfection].
Rakhmanin, Iu A; Zholdakova, Z I; Poliakova, E E; Kir'ianova, L F; Miasnikov, I N; Tul'skaia, E A; Artemova, T Z; Ivanova, L V; Dmitrieva, R A; Doskina, T V
2004-01-01
The authors made an experimental study of the efficiency of water purification procedures based on the combined use of active chlorine and coagulants and hygienically evaluated the procedures. The study included the evaluation of water disinfection with various coagulants and active chlorine; the investigation of the processes of production of deleterious organic chlorine compounds; the assessment of the quality of water after its treatment. The coagulants representing aluminum polyoxychloride: RAX-10 (AQUA-AURATE 10) and RAX-18 (AQUA-AURATE 18), and aluminum sulfate, technically pure grade were tested. The treatment of river water with the coagulants RAX-10 and RAX-18, followed by precipitation, filtration, and chlorination under laboratory conditions, was shown to result in water disinfection to the levels complying with the requirements described in SanPiN 2.1.4.1074-01. RAX-18 showed the best disinfecting activity against total and heat-tolerant coliform bacteria, but also to the highly chlorine-resistant microrganisms--the spores of sulfite-reducing Clostridia, phages, and viruses. Since the coagulants have an increased sorptive capacity relative to humus and other organic substances, substitution of primary chlorination for coagulant treatment may induce a reduction in the risk of formation of oncogenically and mutagenically hazardous chlorinated hydrocarbons.
Rush-hour aromatic and chlorinated hydrocarbons in selected subway stations of Shanghai, China.
Zhang, Yanli; Li, Chunlei; Wang, Xinming; Guo, Hai; Feng, Yanli; Chen, Jianmin
2012-01-01
Air samples were collected simultaneously at platform, mezzanine and outdoor in five typical stations of subway system in Shanghai, China using stainless steel canisters and analyzed by gas chromatography-mass selective detector (GC-MSD) after cryogenic preconcentration. Benzene, toluene, ethylbenzene and xylenes (BTEX) at the platforms and mezzanines inside the stations averaged (10.3 +/- 2.1), (38.7 +/- 9.0), (19.4 +/- 10.1) and (30.0 +/- 11.1) microg/m3, respectively; while trichloroethylene (TrCE), tetrachloroethylene (TeCE) and para-dichlorobenzene (pDCB), vinyl chloride and carbon tetrachloride were the most abundant chlorinated hydrocarbons inside the stations with average levels of (3.6 +/- 1.3), (1.3 +/- 0.5), (4.1 +/- 1.1), (2.2 +/- 1.1) and (1.2 +/- 0.3) microg/m3, respectively. Mean levels of major aromatic and chlorinated hydrocarbons were higher indoor (platforms and mezzanines) than outdoor with average indoor/outdoor (I/O) ratios of 1.1-9.5, whereas no significant indoor/outdoor differences were found except for benzene and TrCE. The highly significant mutual correlations (p < 0.01) for BTEX between indoor and outdoor and their significant correlation (p < 0.05) with methyl tert-butyl ether (MTBE), a marker of traffic-related emission without other indoor and outdoor sources, indicated that BTEX were introduced into the subway stations from indoor/outdoor air exchange and traffic emission should be their dominant source. TrCE and pDCB were mainly from indoor emission and TeCE might have both indoor emission sources and contribution from outdoor air, especially in the mezzanines.
McKinney, J D
1989-01-01
Molecular/theoretical modeling studies have revealed that thyroid hormones and toxic chlorinated aromatic hydrocarbons of environmental significance (for which dioxin or TCDD is the prototype) have similar structural properties that could be important in molecular recognition in biochemical systems. These molecular properties include a somewhat rigid, sterically accessible and polarizable aromatic ring and size-limited, hydrophobic lateral substituents, usually contained in opposite adjoining rings of a diphenyl compound. These molecular properties define the primary binding groups thought to be important in molecular recognition of both types of structures in biochemical systems. Similar molecular reactivities are supported by the demonstration of effective specific binding of thyroid hormones and chlorinated aromatic hydrocarbons with four different proteins, enzymes, or receptor preparations that are known or suspected to be involved in the expression of thyroid hormone activity. These binding interactions represent both aromatic-aromatic (stacking) and molecular cleft-type recognition processes. A multiple protein or multifunctional receptor-ligand binding mechanism model is proposed as a way of visualizing the details and possible role of both the stacking and cleft type molecular recognition factors in the expression of biological activity. The model suggests a means by which hormone-responsive effector-linked sites (possible protein-protein-DNA complexes) can maintain highly structurally specific control of hormone action. Finally, the model also provides a theoretical basis for the design and conduct of further biological experimentation on the molecular mechanism(s) of action of toxic chlorinated aromatic hydrocarbons and thyroid hormones. Images FIGURE 3. A FIGURE 3. B FIGURE 3. C FIGURE 3. D PMID:2551666
Contaminants evaluation of Marais des Cygnes National Wildlife Refuge in Kansas and Missouri, USA
NASA Astrophysics Data System (ADS)
Allen, George T.; Nash, Tom J.; Janes, David E.
1995-05-01
At the new Marais des Cygnes National Wildlife Refuge in Linn County, Kansas, and Bates County, Missouri, USA, we evaluated long-lived contaminants before acquisition of the land for the refuge. We sampled sediments at 16 locations and fish at seven locations. The samples were analyzed for metals and for chlorinated hydrocarbon compounds. Selected sediment samples also were analyzed for aliphatic hydrocarbons. Arsenic concentrations in sediment samples from six locations were elevated compared to US norms, but arsenic was not detected in any fish composite. Mercury concentrations in largemouth bass from two locations were comparable to the 85th percentile concentrations in nationwide fish collections. Most sediment concentrations of other metals were unlikely to have detrimental effects on biota. No chlorinated hydrocarbons were detected in any sediment sample. Chlordane compound concentrations in fish composites from two sites at the eastern end of the sampling area were 0.127 and 0.228 μg/g wet weight, respectively, which are high enough to cause concern. Most aliphatic hydrocarbons detected were found at low concentrations and probably were natural in origin. We concluded that there are no serious contaminants concerns within the project area, but past use of arsenical pesticides may mean a legacy of elevated soil arsenic levels in parts of the area and some use of banned pesticides such as chlordane and DDT likely is still occurring near the refuge.
Klarich, Kathryn L.; Pflug, Nicholas C.; DeWald, Eden M.; Hladik, Michelle L.; Kolpin, Dana W.; Cwiertny, David M.; LeFevre, Gergory H.
2017-01-01
Neonicotinoid insecticides are widespread in surface waters across the agriculturally-intensive Midwestern US. We report for the first time the presence of three neonicotinoids in finished drinking water and demonstrate their general persistence during conventional water treatment. Periodic tap water grab samples were collected at the University of Iowa over seven weeks in 2016 (May-July) after maize/soy planting. Clothianidin, imidacloprid, and thiamethoxam were ubiquitously detected in finished water samples and ranged from 0.24-57.3 ng/L. Samples collected along the University of Iowa treatment train indicate no apparent removal of clothianidin and imidacloprid, with modest thiamethoxam removal (~50%). In contrast, the concentrations of all neonicotinoids were substantially lower in the Iowa City treatment facility finished water using granular activated carbon (GAC) filtration. Batch experiments investigated potential losses. Thiamethoxam losses are due to base-catalyzed hydrolysis at high pH conditions during lime softening. GAC rapidly and nearly completely removed all three neonicotinoids. Clothianidin is susceptible to reaction with free chlorine and may undergo at least partial transformation during chlorination. Our work provides new insights into the persistence of neonicotinoids and their potential for transformation during water treatment and distribution, while also identifying GAC as an effective management tool to lower neonicotinoid concentrations in finished drinking water.
Problems in aerial application. I, Some biochemical effects of lindane and dieldrin on vertebrates.
DOT National Transportation Integrated Search
1962-05-01
Chronic exposure to the chlorinated hydrocarbon, lindane, elicited alterations in several biochemical values of rat tissues. These included ribonucleic acid quantities, water content, and the cytochrome oxidase activity of heart sarcosomes. The chlor...
MASS BALANCE ANALYSIS FOR MICROBIAL DECHLORINATION OF TETRACHLOROETHENE
Contamination of subsurface environments by chlorinated aliphatic solvents and petroleum hydrocarbons is a significant public health concern because groundwater is one of the major drinking water resources in the United States. Biotic and abiotic techniques have been widely exam...
Fries, Elke; Sieg, Karsten; Püttmann, Wilhelm; Jaeschke, Wolfgang; Winterhalter, Richard; Williams, Jonathan; Moortgat, Geert K
2008-03-01
Benzene, alkylated benzenes, chlorinated hydrocarbons and monoterpenes were measured in snow/ice collected directly in-cloud at Jungfraujoch (3580 m asl) in February and March 2005 and 2006 during the CLoud and Aerosol Characterization Experiments CLACE 4 and CLACE 5. Melted snow/ice samples were analyzed by headspace-solid-phase-dynamic-extraction (HS-SPDE) followed by gas chromatography/mass spectrometry (GC/MS). Generally, there was a tendency in the results that higher concentrations were found after longer precipitation-free periods, suggesting that higher concentrations in snow/ice may be caused by the washout effect of precipitation. High concentration variations in snow/ice samples taken at the same time at the same place highlight the heterogeneous nature of snow/ice. Air concentrations calculated by scavenging ratios and measured snow/ice values markedly exceed the typically reported concentrations of benzene and alkylbenzenes in air (Li Y, Campana M, Reimann S, Schaub KS, Staehlin J, Peter T. Hydrocarbon concentrations at the alpine mountain sites Jungfraujoch and Arosa. Atmos Environ 2005;39:1113-27). This argues for an efficient snow/ice scavenging of those compounds from the atmosphere during precipitation formation.
Zhuang, An-Xiang; Zhang, Yi-Xi; Zhang, Hui; Liu, Ze-Wen
2016-10-01
Neonicotinoids, such as imidacloprid, are key insecticides extensively used for control of Nilaparvata lugens. However, imidacloprid resistance has been reported in many Asian countries in recent years. To understand the roles of the chlorine atom of pyridyl group on insecticidal activity and resistance, the atom was removed to generate an imidacloprid analogue DC-Imi (DesChlorine Imidacloprid). DC-Imi showed significantly higher toxicity than imidacloprid in the susceptible strain of N. lugens, but had medium level cross-resistance in an imidacloprid-resistant strain. In Xenopus oocyte expressed nicotinic acetylcholine receptors (nAChRs) Nlα1/rβ2, the inward currents evoked by DC-Imi were detected and could be blocked by typical nAChRs antagonist dihydro-β-erythroidine (DHβE), which demonstrated that DC-Imi acted as an agonist on insect nAChRs. The efficacy of DC-Imi on Nlα1/rβ2 was 1.8-fold higher than that of imidacloprid. In addition, the influence of an imidacloprid resistance associated mutation (Y151S) on agonist potencies was evaluated. Compared with the wild-type receptor, the mutation reduced maximal inward current of DC-Imi to 55.6% and increased half maximal effective concentration (EC50 ) to 3.53-fold. Compared with imidacloprid (increasing EC50 to 2.38-fold of wild-type receptor), Y151S mutation decreased DC-Imi potency more significantly. The results indicated that the selective and possibly high toxicities could be achieved through the modification of 6-chloro-3-pyridyl group in imidacloprid and other neonicotinoids. © 2015 Institute of Zoology, Chinese Academy of Sciences.
PHYTOREMEDIATION: AN ECOLOGICAL SOLUTION TO ORGANIC CHEMICAL CONTAMINATION
Phytoremediation is a promising new technology that uses plants to degrade, assimilate, metabolize, or detoxify metals, hydrocarbons, pesticides, and chlorinated solvents. In this review, in situ, in vivo and in vitro methods of application are described for remediation of these ...
Paint removal activities in Germany
NASA Astrophysics Data System (ADS)
Holbein, R.; Arnolds-Mayer, G.
1993-03-01
To replace paint removing chemicals containing chlorinated hydrocarbons several alternative paint stripping methods have been developed or are under study in Germany: high pressure water stripping; plastic media blasting; use of alcalic and acid activated softeners; CO2 pellet blasting; and laser application.
Diagnosis & Treatment of Poisoning by Pesticides.
ERIC Educational Resources Information Center
Environmental Protection Agency, Washington, DC. Office of Pesticide Programs.
This report succinctly discusses the steps necessary to diagnose and treat poisoning from pesticides, especially organophosphates, carbamates and chlorinated hydrocarbons. Immediate and continuing steps in the care of poisoning victims are outlined with supportive information on where to locate emergency assistance. (CS)
Mininni, Giuseppe; Sbrilli, Andrea; Guerriero, Ettore; Rotatori, Mauro
2004-03-01
The factors affecting polychlorinated dibenzo-p-dioxins (PCDD) and polychlorinated dibenzofurans (PCDF) formation were studied in sewage sludge incineration tests carried out on a demonstrative plant. The plant includes a circulating fluidised bed furnace (FBF) and a rotary kiln furnace (RKF), operating alternatively. During the tests sewage sludge was spiked with chlorinated hydrocarbons and the operating parameters of the afterburning chamber were varied. PCDD/F were sampled in each test before the bag filter, thus collecting the above contaminants before abatement systems. From the tests it appeared that PCDD/F were always produced in more abundance in the tests carried out by FBF than by RKF. The higher PCDD/F concentrations in the tests by FBF were reached when sewage sludge was spiked with a high dosage of a surrogate organic mixture of chlorinated hydrocarbons and when the afterburning chamber was used only as transit equipment with the burner off. The distribution of the different PCDD/F homologues was compared. P5CDFs were generally the prevalent fraction, with very few exceptions for the tests by RKF at high temperature of the afterburning chamber. As for FBF tests, it was found that the PCDD/F homologue profile depends on the afterburning chamber temperature.
Shahraki, Hassan; Tabrizchi, Mahmoud; Farrokhpor, Hossein
2018-05-26
The ionization source is an essential component of most explosive detectors based on negative ion mobility spectrometry. Conventional ion sources suffer from such inherent limitations as special safety regulations on radioactive sources or generating interfering ions (for non-radioactive sources) such as corona discharge operating in the air. In this study, a new negative ion source is introduced for ion mobility spectrometry that is based on thermal ionization and operates in the air, applicable to explosives detection. Our system consists of a heating filament powered by an isolated power supply connected to negative high voltage. The ionization is assisted by doping chlorinated compounds in the gas phase using chlorinated hydrocarbons in contact with the heating element to yield Cl - reactant ions. Several chlorinated hydrocarbons are evaluated as the reagent chemicals for providing Cl- reactant ions, of which CCl 4 is identified as the best ionizing reagent. The ion source is evaluated by recording the ion mobility spectra of common explosives, including TNT, RDX, and PETN in the air. A detection limit of 150 pg is obtained for TNT. Compared to other ionization sources, the new source is found to be low-cost, simple, and long-lived, making it suited to portable explosives detection devices. Copyright © 2018 Elsevier B.V. All rights reserved.
NASA Astrophysics Data System (ADS)
Lawrence, Adrian; Stuart, Marianne; Cheney, Colin; Jones, Neil; Moss, Richard
2006-12-01
Contaminant migration behaviour in the unsaturated zone of a fractured porous aquifer is discussed in the context of a study site in Cheshire, UK. The site is situated on gently dipping sandstones, adjacent to a linear lagoon historically used to dispose of industrial wastes containing chlorinated solvents. Two cores of more than 100 m length were recovered and measurements of chlorinated hydrocarbons (CHCs), inorganic chemistry, lithology, fracturing and aquifer properties were made. The results show that selecting an appropriate vertical sampling density is crucial both to providing an understanding of contaminant pathways and distinguishing whether CHCs are present in the aqueous or non-aqueous phase. The spacing of such sampling should be on a similar scale to the heterogeneity that controls water and contaminant movement. For some sections of the Permo-Triassic aquifer, significant changes in lithology and permeability occur over vertical distances of less than 1 m and samples need to be collected at this interval, otherwise considerable resolution is lost, potentially leading to erroneous interpretation of data. At this site, although CHC concentrations were high, the consistent ratio of the two main components of the plume (tetrachloroethene and trichloroethene) provided evidence of movement in the aqueous phase rather than in dense non-aqueous phase liquid (DNAPL).
IRIS Toxicological Review and Summary Documents for Carbon Tetrachloride (Peer Review Plan)
Carbon tetrachloride is a volatile haloalkane with a wide range of industrial and chemical applications. It is produced commercially from chlorination of a variety of low molecular weight hydrocarbons such as carbon disulfide, methanol, methane, propane, and ethylene dichloride....
DEMONSTRATION BULLETIN: GAS-PHASE CHEMICAL REDUCTION - ECO LOGIC INTERNATIONAL, INC.
The patented Eco Logic Process employs a gas-phase reduction reaction of hydrogen with organic and chlorinated organic compounds at elevated temperatures to convert aqueous and oily hazardous contaminants into a hydrocarbon-rich gas product. After passing through a scrubber, the ...
Three transects along a groundwater/surface water interface were characterized for spatial distributions of chlorinated aliphatic hydrocarbons and geochemical conditions to evaluate the natural bioremediation potential of this environmental system. Partly on the basis of ground p...
Pesticides: Environmentalists Seek New Victory in a Frustrating War
ERIC Educational Resources Information Center
Carter, Luther
1973-01-01
Describes the continuing efforts of environmentalists to eliminate the use of chlorinated hydrocarbons as pesticides, and in particular discusses the opposing positions taken by the Environmental Defense Fund and the Shell Chemical Company on the use of aldrin and dieldrin. (JR)
Identification of Polymers in University Class Experiments.
ERIC Educational Resources Information Center
Bowen, Humphry J. M.
1990-01-01
The apparatus, reagents, preliminary classification, nomenclature, acquisition, and procedures used in the identification of synthetic polymers are described. Specific tests for the identification of the presence of hydrocarbons, chlorine, fluorine, sulfur, and nitrogen and the absence of halogens and sulfur are discussed. (CW)
NASA Technical Reports Server (NTRS)
Glavin, Daniel P.; Freissinet, Caroline; Eigenbrode, J.; Miller, K.; Martin, M.; Summons, R.; Steele, A.; Franz, H.; Archer, D.; Brinkerhoff, W.;
2014-01-01
The Sample Analysis at Mars (SAM) instrument on the Curiosity rover is designed to determine the inventory of organic and inorganic volatiles thermally evolved from solid samples using a combination of evolved gas analysis (EGA), gas chromatography mass spectrometry (GCMS), and tunable laser spectroscopy. The first solid samples analyzed by SAM, a scoop of windblown dust and sand at Rocknest (RN), revealed chlorinated hydrocarbons derived primarily from reactions between a martian oxychlorine phase (e.g. perchlorate) and terrestrial carbon from N-methyl-N-(tert-butyldimethylsilyl)-trifluoroacetamide (MTBSTFA) vapor present in the SAM instrument background. Chlorobenzene (CBZ) was also identified by SAM GCMS at RN at trace levels (approx.0.007 nmol) and was attributed to the reaction of chlorine with the Tenax polymers used in the hydrocarbon traps. After the RN analyses, Curiosity traveled to Yellowknife Bay and drilled two separate holes designated John Klein (JK) and Cumberland (CB). Analyses of JK and CB by both SAM and the CheMin x-ray diffraction instrument revealed a mudstone consisting of approx.20 wt% smectite clays, which on Earth are known to aid the concentration and preservation of organic matter. In addition, higher abundances and a more diverse suite of chlorinated hydrocarbons in CB compared to RN suggests that martian or meteoritic organic sources may be preserved in the mudstone. Here we discuss the SAM EGA and GCMS measurements of volatiles released from the Sheepbed mudstone. We focus primarily on the elevated CBZ detections at CB and laboratory analog experiments conducted to help determine if CBZ is derived from primarily terrestrial, martian, or a combination of sources.
Martin, Pamela A; De Solla, Shane R; Ewins, Peter
2003-01-01
Populations of osprey (Pandion haliaetus) in the Great Lakes basin declined dramatically during the 1950s-1970s due largely to adverse effects of persistent chlorinated hydrocarbons, ingested in their fish prey, on eggshell thickness and adult survival. Nevertheless, these contaminants were not measured in osprey tissues during the decades of decline on the Canadian Great Lakes. Between 1991 and 1995, we monitored recovering osprey populations on the Great Lakes, including Georgian Bay and the St. Marys River area on Lake Huron and the St. Lawrence Islands National Park, as well as at two inland sites within the basin. Current OC levels, even from the most contaminated lakes, were typically lower than those associated with reproductive effects. DDE levels in fresh eggs averaged 1.2-2.9 microg/g, well below the 4.2 microg/g level associated with significant eggshell thinning and shell breakage. Nevertheless, a proportion of eggs from all study areas did exceed this level. PCB levels in eggs seldom exceeded 5 microg/g except in one lake of high breeding density in the Kawartha Lakes inland study area, where the mean sum PCB level was 7.1 microg/g and the maximum concentration measured was 26.5 microg/g. On average, mean reproductive output (0.78-2.75 young per occupied nest) of breeding populations in Great Lakes basin study areas exceeded the threshold of 0.8 young thought necessary to maintain stable populations. We concluded that, although eggs and especially nestling plasma, are useful in reflecting local contaminant levels, ospreys are relatively insensitive, at least at the population level, to health effects of current levels of chlorinated hydrocarbons on the Canadian Great Lakes.
DOE Office of Scientific and Technical Information (OSTI.GOV)
Casida, J.E.; Lawrence, L.J.
1985-09-01
(/sup 35/S)t-Butylbicyclophosphorothionate or (/sup 35/S)TBPS is an improved radioligand for the picrotoxinin binding site in rat brain synaptic membranes. The toxic isomers of the hexachlorocyclohexanes, polychlorobornanes, and chlorinated cyclodienes displace (/sup 35/S)TBPS with a stereospecificity and potency generally correlated with their mammalian toxicity. In a few cases this correlation is improved by correction for metabolic activation or detoxification on using a coupled brain receptor/liver microsomal oxidase system. The alpha-cyano-3-phenoxybenzyl pyrethroids, although less potent, inhibit (/sup 35/S)TBPS binding in a stereospecific manner correlated with their toxicity. Scatchard analyses indicate that these three classes of polychlorocycloalkane insecticides act at the TBPS bindingmore » site within the gamma-aminobutyric acid (GABA) receptor-ionophore complex whereas the alpha-cyano pyrethroids interact with a closely associated site. These insecticides and TBPS analogs may serve as useful probes further to elucidate the topography of the TBPS binding site and its relationship to the chloride channel. 46 references.« less
THE BUBBLE STRIPPING METHOD FOR DETERMINING DISSOLVED HYDROGEN (H2) IN WELL WATER
The Bubble Strip Method was developed for determining concentrations of dissolved H2 in ground water (1). This information canaid in assessing the viability of employing the strategyof monitored natural attenuation (MNA) to restore sites contaminated with chlorinated hydrocarbon...
DEVELOPMENT OF BIOPLUME 4 MODEL FOR FUELS AND CHLORINATED SOLVENT BIODEGRADATION
The Bioplume model has been in development and use for modeling biodegradation and natural attenuation since the late 1980s. Bioplume 1 focused on aerobic biodegradation of BTEX. Bioplume II simulated oxygen and hydrocarbons and simulated biodegradation using an instantaneous r...
DOT National Transportation Integrated Search
1963-03-01
In a search for an explanation of an earlier finding that dieldrin decreased the rate of methionine uptake by cardiac muscle, chickens and rats were exposed to this compound and the substrate-linked phosphorylation phenomenon was studied during the a...
DEVELOPMENT OF BIOPLUME4 MODEL FOR FUELS AND CHLORINATED SOLVENT BIODEGRADATION
The Bioplume model has been in development and use for modeling biodegradation and natural attenuation since the late 80's. Bioplume I focused on aerobic biodegradation of BTEX. Bioplume II simulated oxygen and hydrocarbons and simulated biodegradation using an instantaneous re...
BIOAUGMENTATION OF FE(0) FOR REMEDIATION OF CHLORINATED ALIPHATIC HYDROCARBONS. (R825549C053)
The perspectives, information and conclusions conveyed in research project abstracts, progress reports, final reports, journal abstracts and journal publications convey the viewpoints of the principal investigator and may not represent the views and policies of ORD and EPA. Concl...
BIOAUGMENTATION OF FE(0) FOR REMEDIATION OF CHLORINATED ALIPHATIC HYDROCARBONS. (R825549C044)
The perspectives, information and conclusions conveyed in research project abstracts, progress reports, final reports, journal abstracts and journal publications convey the viewpoints of the principal investigator and may not represent the views and policies of ORD and EPA. Concl...
RECOVERY OF METAL VALUES FROM AQUEOUS SOLUTIONS BY SOLVENT EXTRACTION
Moore, R.L.
1959-09-01
An organic solvent mixure is described for extracting actinides from aqueous solutions; the solvent mixture consists of from 10 to 25% by volume of tributyl phosphate and the remainder a chlorine-fluorine-substituted saturated hydrocarbon having two carbon atoms in the molecule.
DOE Office of Scientific and Technical Information (OSTI.GOV)
Strand, Stuart E.
2002-06-01
Several varieties of transgenic poplar containing cytochrome P-450 2E1 have been constructed and are undergoing tests. Strategies for improving public acceptance and safety of transgenic poplar for chlorinated hydrocarbon phytoremediation are being developed. We have discovered a unique rhizobium species that lives within the stems of poplar and we are investigating whether this bacterium contributes nitrogen fixed from the air to the plant and whether this endophyte could be used to introduce genes into poplar. Studies of the production of chloride ion from TCE have shown that our present P-450 constructs did not produce chloride more rapidly than wild typemore » plants. Follow-up studies will determine if there are other rate limiting downstream steps in TCE metabolism in plants. Studies of the metabolism of carbon tetrachloride in poplar cells have provided evidence that the native plant metabolism is due to the activity of oxidative enzymes similar to the mammalian cytochrome P-450 2E1.« less
The perspectives, information and conclusions conveyed in research project abstracts, progress reports, final reports, journal abstracts and journal publications convey the viewpoints of the principal investigator and may not represent the views and policies of ORD and EPA. Concl...
The perspectives, information and conclusions conveyed in research project abstracts, progress reports, final reports, journal abstracts and journal publications convey the viewpoints of the principal investigator and may not represent the views and policies of ORD and EPA. Concl...
Corrosion of aluminum alloys by chlorinated hydrocarbon/methanol mixtures
NASA Technical Reports Server (NTRS)
De Forest, W. S.
1967-01-01
Laboratory investigations show that water-free mixtures of Freon MF /trichlorofluoromethane/ and methanol vigorously attack aluminum alloys which contain significant amounts of copper. Freon MF alone did not attack the aluminum alloys at room temperature. Pure methanol had only a slight corrosive effect on the alloy.
Installation Restoration Program Records Search for Alaska DEW Line Stations
1982-06-01
Chlorinate hydrocarbons Radar components Calgon corrosion inhibitor 55 gallon drums (empty) Lye Lime Corrosives Antifreeze Paper Wood Plastics AVGAS...Factor Subsoare A I Persistence Vcor * Subaccro a C. Appl~y "yicaJ. state =iLtipiisr Sub•coce 3 X Physical State Mltipler - Waste Caracteristics
Pesch, B; Haerting, J; Ranft, U; Klimpel, A; Oelschlägel, B; Schill, W
2000-04-01
This multicentre population-based case-control study was conducted to estimate the urothelial cancer risk for occupational exposure to aromatic amines, polycyclic aromatic hydrocarbons (PAH), and chlorinated hydrocarbons besides other suspected risk factors. In a population-based multicentre study, 1035 incident urothelial cancer cases and 4298 controls matched for region, sex, and age were interviewed between 1991 and 1995 for their occupational history and lifestyle habits. Exposure to the agents under study was self-assessed as well as expert-rated with two job-exposure matrices and a job task-exposure matrix. Conditional logistic regression was used to calculate smoking adjusted odds ratios (OR) and to control for study centre and age. Urothelial cancer risk following exposure to aromatic amines was only slightly elevated. Among males, substantial exposures to PAH as well as to chlorinated solvents and their corresponding occupational settings were associated with significantly elevated risks after adjustment for smoking (PAH exposure, assessed with a job-exposure matrix: OR = 1.6, 95% CI: 1.1-2.3, exposure to chlorinated solvents, assessed with a job task-exposure matrix: OR = 1.8, 95% CI: 1.2-2.6). Metal degreasing showed an elevated urothelial cancer risk among males (OR = 2.3, 95% CI: 1.4-3.8). In females also, exposure to chlorinated solvents indicated a urothelial cancer risk. Because of small numbers the risk evaluation for females should be treated with caution. Occupational exposure to aromatic amines could not be shown to be as strong a risk factor for urothelial carcinomas as in the past. A possible explanation for this finding is the reduction in exposure over the last 50 years. Our results strengthen the evidence that PAH may have a carcinogenic potential for the urothelium. Furthermore, our results indicate a urothelial cancer risk for the use of chlorinated solvents.
Benelli, Giovanni; Pavela, Roman; Rakotosaona, Rianasoambolanoro; Randrianarivo, Emmanuel; Nicoletti, Marcello; Maggi, Filippo
2017-11-03
Helichrysum faradifani (Asteraceae) is a perennial shrub growing in rocky and sandy places of Madagascar. The plant is used in the Malagasy traditional medicine as a wound-healing agent, disinfectant and for the treatment of syphilis, diarrhea, cough and headache. In the present work, we analysed the chemical composition of the essential oil distilled from the aerial parts of H. faradifani by GC-MS and evaluated its insecticidal activity against 2nd, 3rd and 4th instar larvae of the lymphatic filariasis vector Culex quinquefasciatus by acute toxicity assays. The most sensitive were 2nd instar (LC 50 = 85.7 μL L -1 ) larvae. For the 3rd and 4th instar larvae, the estimated LC 50 were 156.8 and 134.1 μL L -1 , respectively. Monoterpene hydrocarbons (51.6%) were the major fraction of the essential oil, with the bicyclic α-fenchene (35.6%) as the predominant component. Sesquiterpene hydrocarbons (34.0%) were the second major group characterising the oil, with γ-curcumene (17.7%) as the most abundant component.
Foster, G.D.; Miller, C.V.; Huff, T.B.; Roberts, E.
2003-01-01
Concentrations of current-use pesticides, polycyclic aromatic hydrocarbons (PAHs), polychlorinated biphenyls (PCBs), and organochlorine (OC) insecticides were determined above the reach of tide in the Chesterville Branch and Nanticoke River on the eastern shore of Chesapeake Bay during base-flow and storm-flow hydrologic regimes to evaluate mass transport to Chesapeake Bay. The two rivers monitored showed relatively high concentrations of atrazine, simazine, alachlor, and metolachlor in comparison to previously investigated western shore tributaries, and reflected the predominant agricultural land use in the eastern shore watersheds. The four current use pesticides showed the greatest seasonal contribution to annual loadings to tidal waters of Chesapeake Bay from the two rivers, and the relative order of annual loadings for the other contaminant classes was PAHs > PCBs > OC insecticides. Annual loadings normalized to the landscape areas of selected Chesapeake Bay watersheds showed correlations to identifiable source areas, with the highest pesticide yields (g/km2/yr) occurring in eastern shore agricultural landscapes, and the highest PAH yields derived from urban regions.
Recovery of copper from PVC multiwire cable waste by steam gasification.
Zabłocka-Malicka, Monika; Rutkowski, Piotr; Szczepaniak, Włodzimierz
2015-12-01
Screened multiwire, PVC insulated tinned copper cable was gasified with steam at high temperature (HTSG) under atmospheric pressure for recovery of cooper. Gases from the process were additionally equilibrated at 850°C on the bed of calcined clay granules and more than 98% of C+H content in the cable was transformed to non-condensing species. Granules prepared from local clay were generally resistant for chlorination, there was also almost no deposition of metals, Cu and Sn, on the catalytic bed. It was found that 28% of chlorine reacted to form CaCl2, 71% was retained in aqueous condensate and only 0.6% was absorbed in alkaline scrubber. More than 99% of calcium existed in the process solid residue as a mixture of calcium chloride and calcium oxide/hydroxide. PVC and other hydrocarbon constituents were completely removed from the cable sample. Copper was preserved in original form and volatilization of copper species appeared insignificant. Tin was alloying with copper and its volatilization was less than 1%. Fractionation and speciation of metals, chlorine and calcium were discussed on the basis of equilibrium model calculated with HSC Chemistry software. High temperature steam gasification prevents direct use of the air and steam/water is in the process simultaneously gaseous carrier and reagent, which may be recycled together with hydrocarbon condensates. Copyright © 2015 Elsevier Ltd. All rights reserved.
BioTrol, Inc., developed a two-stage, methanotrophic, bioreactor system for remediation of water contaminated with trichloroethylene (TCE) and other chlorinated, volatile, aliphatic hydrocarbons. The first stage was a suspended-growth culture vessel with a bubbleless methane tran...
Risk management of petroleum vapor intrusion has been a daunting and challenging task for the Underground Storage Tank Program. Because chlorinated solvents do not degrade in soil gas, techniques that focus on their properties and behavior can produce useful estimates. However, t...
Extended characterization of M-Area settling basin and vicinity. Technical data summary. Revision
DOE Office of Scientific and Technical Information (OSTI.GOV)
Pickett, J B
1985-10-01
The Savannah River Plant M-Area settling basin, an unlined surface impoundment, has received process effluents from the M-Area fuel and target fabrication facilities since 1958. The waste effluents have contained metal degreasing agents (chlorinated hydrocarbons), acids, caustics, and heavy metals. Data analyses are provided.
The perspectives, information and conclusions conveyed in research project abstracts, progress reports, final reports, journal abstracts and journal publications convey the viewpoints of the principal investigator and may not represent the views and policies of ORD and EPA. Concl...
The perspectives, information and conclusions conveyed in research project abstracts, progress reports, final reports, journal abstracts and journal publications convey the viewpoints of the principal investigator and may not represent the views and policies of ORD and EPA. Concl...
Czech, K; Słomkiewicz, P M
2013-05-03
Inverse gas chromatographic methods of isotherm determination peak maximum (PM) and peak division (PD) were compared. These methods were applied to determine adsorption isotherms of dichloroethylene, trichloroethylene and tetrachloroethylene on acid-activated halloysite and adsorption enthalpy. Copyright © 2013 Elsevier B.V. All rights reserved.
ON THE RELATIONSHIP BETWEEN CO, POHC, AND PIC EMISSIONS FROM A SIMULATED HAZARDOUS WASTE INCINERATOR
Measurements conducted on full-scale hazardous waste incinerators have occasionally shown a relationship between carbon monoxide (CO) emissions and emissions of toxic organic compounds. In this study, four mixtures of chlorinated C1 and C2 hydrocarbons were diluted in commercial...
Decontamination of PCBs-containing soil using subcritical water extraction process.
Islam, Mohammad Nazrul; Park, Jeong-Hun; Shin, Moon-Su; Park, Ha-Seung
2014-08-01
Polychlorinated biphenyls (PCBs) are one of the excision compounds listed at the Stockholm convention in 2001. Although their use has been heavily restricted, PCBs can be found in some specific site-contaminated soils. Either removal or destruction is required prior to disposal. The subcritical water extraction (SCWE) of organic hazardous compounds from contaminated soils is a promising technique for hazardous waste contaminated-site cleanup. In this study, the removal of PCBs by the SCWE process was investigated. The effects of temperature and treatment time on removal efficiency have been determined. In the SCWE experiments, a removal percentage of 99.7% was obtained after 1h of treatment at 250°C. The mass removal efficiency of low-chlorinated species was higher than high-chlorinated congeners at lower temperatures, but it was oppositely observed at higher temperatures because the lower chlorinated congeners are formed by dechlorination of higher chlorinated congeners. Gas chromatography/mass spectrometry analysis confirmed that the PCBs underwent partial degradation. Several degradation products including mono- and di-chlorinated biphenyls, oxygen-containing aromatic compounds, and small-size hydrocarbons were identified in the effluent water, which were not initially present in the contaminated soil. Copyright © 2014 Elsevier Ltd. All rights reserved.
Risk of liver cancer and exposure to organic solvents and gasoline vapors among Finnish workers.
Lindbohm, Marja-Liisa; Sallmén, Markku; Kyyrönen, Pentti; Kauppinen, Timo; Pukkala, Eero
2009-06-15
We investigated the association between exposure to various groups of solvents and gasoline vapors and liver cancer. A cohort of economically active Finns born between 1906 and 1945 was followed up during the period 1971-1995. The incident cases of primary liver cancer (n = 2474) were identified in a record linkage with the Finnish Cancer Registry. Occupations from the 1970 census were converted to exposures using a job-exposure matrix. Cumulative exposure was calculated as the product of estimated prevalence, level and duration of exposure, and we used Poisson regression to calculate the relative risks (RR). Among the occupations entailing exposure to organic solvents, an elevated liver cancer incidence was observed in male printers, and varnishers and lacquerers. Among men, the risk was increased in the highest exposure category of aromatic hydrocarbons [RR 1.77, 95% confidence interval (CI) 1.30-2.40], aliphatic/alicyclic hydrocarbons (RR 1.47, 95% CI 0.99-2.18), chlorinated hydrocarbons (RR 2.65, 95% CI 1.38-5.11) and "other solvents" (RR 2.14, 95% CI 1.23-3.71). Among women, the risk was increased for the group "other solvents" that includes mainly alcohols, ketones, esters and glycol ethers (RR 2.73, 95% CI 1.21-6.16). Our finding of an increased risk among workers exposed to chlorinated hydrocarbons is in line with several earlier studies on trichloroethylene. The results also suggest a link between exposure to other types of solvents and the risk of liver cancer. The possibility that alcohol consumption contributes to the observed risks cannot be totally excluded. Copyright 2008 UICC.
Volatile organic compounds in a multi-storey shopping mall in guangzhou, South China
NASA Astrophysics Data System (ADS)
Tang, Jianhui; Chan, C. Y.; Wang, Xinming; Chan, L. Y.; Sheng, Guoying; Fu, Jiamo
Volatile organic compounds (VOCs) specified in the USEPA TO-14 list were analysed in microenvironments of a multi-storey shopping mall in Guangzhou city, South China. The microenvironments studied include both indoor (department store, supermarket, fast-food court, electronic games room, children's playground, gallery and book store) and outdoor ones (rooftop and ground level entrance). The characteristics and concentration of VOCs varied widely in differing microenvironments. The average concentrations of the total VOCs in the indoor microenvironments ranged from 178.5 to 457.7 μg m -3 with a maximum of 596.8 μg m -3. The fast-food court and a leather products department store had the highest concentrations of benzene, toluene, ethylbenzene, xylenes and chlorinated hydrocarbons. A high level of 1,4-dichlorobenzene was found in all indoor microenvironments with an average of 12.3 μg m -3 and a maximum of 44.3 μg m -3. The ratios of average indoor to outdoor concentrations (I/O ratio) in all indoor microenvironments fell between 1 and 3, except an average of 24.6 and a maximum of 77.8 in the fashion department store for 1,4-dichlorobenzene. Indoor emission sources of monocyclic aromatic hydrocarbons in the shopping mall might include cooking stoves, leather products and building materials. Chlorinated hydrocarbons, however, were possibly connected with their use as cleaning agents or deodorizers.
In accord with the research objectives, this project achieved the following major results:
The perspectives, information and conclusions conveyed in research project abstracts, progress reports, final reports, journal abstracts and journal publications convey the viewpoints of the principal investigator and may not represent the views and policies of ORD and EPA. Concl...
The perspectives, information and conclusions conveyed in research project abstracts, progress reports, final reports, journal abstracts and journal publications convey the viewpoints of the principal investigator and may not represent the views and policies of ORD and EPA. Concl...
The perspectives, information and conclusions conveyed in research project abstracts, progress reports, final reports, journal abstracts and journal publications convey the viewpoints of the principal investigator and may not represent the views and policies of ORD and EPA. Concl...
DOE Office of Scientific and Technical Information (OSTI.GOV)
Kendall, R.J.
1982-08-01
Wildlife toxicology may be defined as the study of the effects of environmental contaminants on wildlife species, as related to their wellbeing, general health, and reproduction. Results of studies with pesticides, heavy metals, and chlorinated hydrocarbons are examined. Integrated field and laboratory studies using selected model species might lead to ways of quantifying the adverse effects of chemical contaminants. (KRM)
NASA Astrophysics Data System (ADS)
Bohinc, R.; Žitnik, M.; Bučar, K.; Kavčič, M.; Carniato, S.; Journel, L.; Guillemin, R.; Marchenko, T.; Kawerk, E.; Simon, M.; Cao, W.
2016-04-01
We present a theoretical and experimental study of resonant inelastic x-ray scattering on a large group of chlorinated hydrocarbons: CH3Cl, CH2Cl2, CHCl3, CCl4, CH3CH2Cl, ClCH2CH2Cl, CH3CHCl2, CH3CCl3, C2H2Cl2-iso, C2H2Cl2-cis, C2H2Cl2-trans, and C6H5Cl. Differences in structural and dynamical properties of the molecules generated by diverse chemical environments are observed in the measured Cl(Kα) spectral maps as well as in the Cl(K) total fluorescence yield spectra. The energy position, relative intensity, and the width of the Franck-Condon distribution of low-lying σ∗ and π∗ resonances are extracted by a fitting procedure taking into account the experimental broadening. The theoretical values obtained with the transition potential and Δ Kohn-Sham methods are in good agreement with the experimental parameters indicating subtle differences due to variations in the molecular structure.
Bohinc, R; Žitnik, M; Bučar, K; Kavčič, M; Carniato, S; Journel, L; Guillemin, R; Marchenko, T; Kawerk, E; Simon, M; Cao, W
2016-04-07
We present a theoretical and experimental study of resonant inelastic x-ray scattering on a large group of chlorinated hydrocarbons: CH3Cl, CH2Cl2, CHCl3, CCl4, CH3CH2Cl, ClCH2CH2Cl, CH3CHCl2, CH3CCl3, C2H2Cl2-iso, C2H2Cl2-cis, C2H2Cl2-trans, and C6H5Cl. Differences in structural and dynamical properties of the molecules generated by diverse chemical environments are observed in the measured Cl(K(α)) spectral maps as well as in the Cl(K) total fluorescence yield spectra. The energy position, relative intensity, and the width of the Franck-Condon distribution of low-lying σ* and π* resonances are extracted by a fitting procedure taking into account the experimental broadening. The theoretical values obtained with the transition potential and Δ Kohn-Sham methods are in good agreement with the experimental parameters indicating subtle differences due to variations in the molecular structure.
Guan, Xiangyu; Liu, Fei; Xie, Yuxuan; Zhu, Lingling; Han, Bin
2013-08-01
Pollution of groundwater with chlorinated aliphatic hydrocarbons (CAHs) is a serious environmental problem which is threatening human health. Microorganisms are the major participants in degrading these contaminants. Here, groundwater contaminated for a decade with CAHs was investigated. Numerical simulation and field measurements were used to track and forecast the migration and transformation of the pollutants. The diversity, abundance, and possible activity of groundwater microbial communities at CAH-polluted sites were characterized by molecular approaches. The number of microorganisms was between 5.65E+05 and 1.49E+08 16S rRNA gene clone numbers per liter according to quantitative real-time PCR analysis. In 16S rRNA gene clone libraries constructed from samples along the groundwater flow, eight phyla were detected, and Proteobacteria were dominant (72.8 %). The microbial communities varied with the composition and concentration of pollutants. Meanwhile, toluene monooxygenases and methane monooxygenases capable of degradation of PCE and TCE were detected, demonstrating the major mechanism for PCE and TCE degradation and possibility for in situ remediation by addition of oxygen in this study.
High energy chemical laser system
Gregg, D.W.; Pearson, R.K.
1975-12-23
A high energy chemical laser system is described wherein explosive gaseous mixtures of a reducing agent providing hydrogen isotopes and interhalogen compounds are uniformly ignited by means of an electrical discharge, flash- photolysis or an electron beam. The resulting chemical explosion pumps a lasing chemical species, hydrogen fluoride or deuterium fluoride which is formed in the chemical reaction. The generated lasing pulse has light frequencies in the 3- micron range. Suitable interhalogen compounds include bromine trifluoride (BrF$sub 3$), bromine pentafluoride (BrF$sub 5$), chlorine monofluoride (ClF), chlorine trifluoride (ClF$sub 3$), chlorine pentafluoride (ClF$sub 5$), iodine pentafluoride (IF$sub 5$), and iodine heptafluoride (IF$sub 7$); and suitable reducing agents include hydrogen (H$sub 2$), hydrocarbons such as methane (CH$sub 4$), deuterium (D$sub 2$), and diborane (B$sub 2$H$sub 6$), as well as combinations of the gaseous compound and/or molecular mixtures of the reducing agent.
Legeay, Samuel; Billat, Pierre-André; Clere, Nicolas; Nesslany, Fabrice; Bristeau, Sébastien; Faure, Sébastien; Mouvet, Christophe
2018-05-01
Chlordecone (CLD) is a chlorinated hydrocarbon insecticide, now classified as a persistent organic pollutant. Several studies have previously reported that chronic exposure to CLD leads to hepatotoxicity, neurotoxicity, raises early child development and pregnancy complications, and increases the risk of liver and prostate cancer. In situ chemical reduction (ISCR) has been identified as a possible way for the remediation of soils contaminated by CLD. In the present study, the objectives were (i) to evaluate the genotoxicity and the mutagenicity of two CLD metabolites formed by ISCR, CLD-5a-hydro, or CLD-5-hydro (5a- or 5- according to CAS nomenclature; CLD-1Cl) and tri-hydroCLD (CLD-3Cl), and (ii) to explore the angiogenic properties of these molecules. Mutagenicity and genotoxicity were investigated using the Ames's technique on Salmonella typhimurium and the in vitro micronucleus micromethod with TK6 human lymphoblastoid cells. The proangiogenic properties were evaluated on the in vitro capillary network formation of human primary endothelial cells. Like CLD, the dechlorinated derivatives of CLD studied were devoid of genotoxic and mutagenic activity. In the assay targeting angiogenic properties, significantly lower microvessel lengths formed by endothelial cells were observed for the CLD-3Cl-treated cells compared to the CLD-treated cells for two of the three tested concentrations. These results suggest that dechlorinated CLD derivatives are devoid of mutagenicity and genotoxicity and have lower proangiogenic properties than CLD.
Nishimura, Chiya; Horii, Yuichi; Tanaka, Shuhei; Asante, Kwadwo Ansong; Ballesteros, Florencio; Viet, Pham Hung; Itai, Takaaki; Takigami, Hidetaka; Tanabe, Shinsuke; Fujimori, Takashi
2017-06-01
We conducted this study to assess the occurrence, profiles, and toxicity of chlorinated polycyclic aromatic hydrocarbons (Cl-PAHs) and brominated polycyclic aromatic hydrocarbons (Br-PAHs) in e-waste open burning soils (EOBS). In this study, concentrations of 15 PAHs, 26 Cl-PAHs and 14 Br-PAHs were analyzed in EOBS samples. We found that e-waste open burning is an important emission source of Cl-PAHs and Br-PAHs as well as PAHs. Concentrations of total Cl-PAHs and Br-PAHs in e-waste open burning soil samples ranged from 21 to 2800 ng/g and from 5.8 to 520 ng/g, respectively. Compared with previous studies, the mean of total Cl-PAH concentrations of the EOBS samples in this study was higher than that of electronic shredder waste, that of bottom ash, and comparable to fly ash from waste incinerators in Korea and Japan. The mean of total Br-PAH concentrations of the EOBS samples was generally three to four orders of magnitude higher than those in incinerator bottom ash and comparable to incinerator fly ash, although the number of Br-PAH congeners measured differed among studies. We also found that the Cl-PAH and Br-PAH profiles were similar among all e-waste open burning soil samples but differed from those in waste incinerator fly ash. The profiles and principal component analysis results suggested a unique mechanism of Cl-PAH and Br-PAH formation in EOBS. In addition, the Cl-PAHs and Br-PAHs showed high toxicities equivalent to PCDD/Fs measured in same EOBS samples when calculated based on their relative potencies to benzo[a]pyrene. Along with chlorinated and brominated dioxins and PAHs, Cl-PAHs and Br-PAHs are important environmental pollutants to investigate in EOBS. Copyright © 2016 Elsevier Ltd. All rights reserved.
NASA Technical Reports Server (NTRS)
Glavin, Daniel; Freissinet, Caroline; Mahaffy, Paul; Miller, Kristen; Eigenbrode, Jennifer; Summons, Roger; Archer, Douglas, Jr.; Brunner, Anna; Martin, Mildred; Buch, Arrnaud;
2014-01-01
One of the key objectives of the Mars Science Laboratory rover and the Sample Analysis at Mars (SAM) instrument suite is to determine the inventory of organic and inorganic volatiles in the atmosphere and surface regolith and rocks to help assess the habitability potential of Gale Crater. The SAM instrument on the Curiosity rover can detect volatile organic compounds thermally evolved from solid samples using a combination of evolved gas analysis (EGA) and gas chromatography mass spectrometry (GCMS) (Mahaffy et al. 2012). The first solid samples analyzed by SAM, a scoop of windblown dust and sand at Rocknest, revealed several chloromethanes and a C4-chlorinated hydrocarbon derived primarily from reactions between a martian oxychlorine phase (e.g. perchlorate) and terrestrial carbon from N-methyl-N-(tertbutyldimethylsilyl)- trifluoroacetamide (MTBSTFA) vapor present in the SAM instrument background (Glavin et al. 2013). After the analyses at Rocknest, Curiosity traveled to Yellowknife Bay and drilled two separate holes in a fluvio-lacustrine sediment (the Sheepbed unit) designated John Klein and Cumberland. Analyses of the drilled materials by both SAM and the CheMin X-Ray Diffraction instrument revealed a mudstone consisting of 20 wt% smectite clays (Ming et al. 2013; Vaniman et al. 2013), which on Earth are known to aid the concentration and preservation of organic matter. Oxychlorine compounds were also detected in the Sheepbed mudstone during pyrolysis; however, in contrast to Rocknest, much higher levels of chloromethanes were released from the Sheepbed materials, suggesting an additional, possibly martian source of organic carbon (Ming et al. 2013). In addition, elevated abundances of chlorobenzene and a more diverse suite of chlorinated alkanes including dichloropropane and dichlorobutane detected in Cumberland compared to Rocknest suggest that martian or meteoritic organic carbon sources may be preserved in the mudstone (Freissinet et al. 2013). Chloromethane and dichloromethane were also identified after thermal volatilization of the surface soils by the GCMS instruments at the Viking landing sites, although no other chlorinated hydrocarbons were reported (Biemann et al. 1977). Here we focus on the origin of the chlorinated hydrocarbons detected in the Sheepbed mudstone by SAM and the implications for the preservation of organic matter in near-surface materials on Mars.
Trends in chlorinated hydrocarbon levels in Hudson River basin sediments.
Bopp, R F; Chillrud, S N; Shuster, E L; Simpson, H J; Estabrooks, F D
1998-08-01
Analysis of sections from dated sediment cores were used to establish geographic distributions and temporal trends of chlorinated hydrocarbon contaminant levels in sediments from natural waters of the Hudson River basin. Radiometric dating was based primarily on the depth distribution of 137(Cs) in the cores and on the occurrence of detectable levels of 7(Be) in surface sediment samples. Eighteen sampling sites included several along the main stem of the Hudson, its major tributaries, and components of the New York/New Jersey (NY/NJ) harbor complex. Drinking-water reservoirs were sampled to place upper limits on atmospheric inputs. Core sections were analyzed for polychlorinated biphenyls (PCBs), 1,1,1-trichloro-2,2-bis(p-chlorophenyl) ethane (DDT)-derived compounds, chlordane, and dioxins. Sediment concentrations of most contaminants at most sites have decreased significantly since the mid-1960s. The data provide a basinwide perspective on major point-source inputs of PCBs to the upper Hudson River and of 2,3,7,8-tetrachlorodibenzo-p-dioxin and DDT to the lower Passaic River. Evidence was found for significant but poorly characterized sources of PCBs and chlordane to the western NY/NJ harbor, and of highly chlorinated dioxins to the upstream sites on the main stem of the Hudson. The results indicate that analysis of dated sediment samples is a most effective and efficient monitoring tool for the study of large-scale geographic and temporal trends in levels of particle-associated contaminants.
Heemken, O P; Theobald, N; Wenclawiak, B W
1997-06-01
The methods of accelerated solvent extraction (ASE) and supercritical fluid extraction (SFE) of polycyclic aromatic hydrocarbons (PAHs), aliphatic hydrocarbons, and chlorinated hydrocarbons from marine samples were investigated. The results of extractions of a certified sediment and four samples of suspended particulate matter (SPM) were compared to classical Soxhlet (SOX), ultrasonication (USE), and methanolic saponification extraction (MSE) methods. The recovery data, including precision and systematic deviations of each method, were evaluated statistically. It was found that recoveries and precision of ASE and SFE compared well with the other methods investigated. Using SFE, the average recoveries of PAHs in three different samples ranged from 96 to 105%, for ASE the recoveries were in the range of 97-108% compared to the reference methods. Compared to the certified values of sediment HS-6, the average recoveries of SFE and ASE were 87 and 88%, most compounds being within the limits of confidence. Also, for alkanes the average recoveries by SFE and ASE were equal to the results obtained by SOX, USE, and MSE. In the case of SFE, the recoveries were in the range 93-115%, and ASE achieved recoveries of 94-107% as compared to the other methods. For ASE and SFE, the influence of water on the extraction efficiency was examined. While the natural water content of the SPM sample (56 wt %) led to insufficient recoveries in ASE and SFE, quantitative extractions were achieved in SFE after addition of anhydrous sodium sulfate to the sample. Finally, ASE was applied to SPM-loaded filter candles whereby a mixture of n-hexane/acetone as extraction solvent allowed the simultaneous determination of PAHs, alkanes, and chlorinated hydrocarbons.
Determination of volatile organic hydrocarbons in water samples by solid-phase dynamic extraction.
Jochmann, Maik A; Yuan, Xue; Schmidt, Torsten C
2007-03-01
In the present study a headspace solid-phase dynamic extraction method coupled to gas chromatography-mass spectrometry (HS-SPDE-GC/MS) for the trace determination of volatile halogenated hydrocarbons and benzene from groundwater samples was developed and evaluated. As target compounds, benzene as well as 11 chlorinated and brominated hydrocarbons (vinyl chloride, dichloromethane, cis-1,2-dichloroethylene, trans-1,2-dichloroethylene, carbon tetrachloride, chloroform, trichloroethylene, tetrachloroethylene, bromoform) of environmental and toxicological concern were included in this study. The analytes were extracted using a SPDE needle device, coated with a poly(dimethylsiloxane) with 10% embedded activated carbon phase (50-microm film thickness and 56-mm film length) and were analyzed by GC/MS in full-scan mode. Parameters that affect the extraction yield such as extraction and desorption temperature, salting-out, extraction and desorption flow rate, extraction volume and desorption volume, the number of extraction cycles, and the pre-desorption time have been evaluated and optimized. The linearity of the HS-SPDE-GC/MS method was established over several orders of magnitude. Method detection limits (MDLs) for the compounds investigated ranged between 12 ng/L for cis-dichloroethylene and trans-dichloroethylene and 870 ng/L for vinyl chloride. The method was thoroughly validated, and the precision at two concentration levels (0.1 mg/L and a concentration 5 times above the MDL) was between 3.1 and 16% for the analytes investigated. SPDE provides high sensitivity, short sample preparation and extraction times and a high sample throughput because of full automation. Finally, the applicability to real environmental samples is shown exemplarily for various groundwater samples from a former waste-oil recycling facility. Groundwater from the site showed a complex contamination with chlorinated volatile organic compounds and aromatic hydrocarbons.
NASA Technical Reports Server (NTRS)
1998-01-01
As a result of SBIR (Small Business Innovative Research) work for Johnson Space Center, KSE, Inc., developed a photocatalytic Adsorption-Integrated-Reaction (AIR) air purification process originally used for air revitalization in life support systems during extended space operations. A unit has been purchased by a commercial customer for control of emissions of airborne chlorinated hydrocarbons at a Superfund site.
Soil was taken from the top 10 cm of a soil column that removed halogenated aliphatic hydrocarbons in the presence of natural gas. This soil was used as an enrichment inoculum to determine that the removals seen in the soil column were in fact of a microbiological nature. Methane...
Na/NH3 reductions have been used to dehalogenate polychlorinated biphenyls (PCBs), chlorinated aliphatic hydrocarbons (CAHs) and pesticides at diffusion controlled rates at room temperature in model compound studies in both dry NH3 and when water was adde...
The Examination of the Link between Pesticides in Food and Learning Disorders in Children.
ERIC Educational Resources Information Center
Raby, Sue Ellen
The relationship between pesticides in food and the occurrence of attention deficit disorder (ADD) and attention deficit hyperactivity disorder (ADHD) in school age children is considered. Pesticides include chlorinated hydrocarbons and organic phosphates that are commonly present in fruits and vegetables, which are a large part of the diet of…
Push-Pull Tests for Evaluating the Aerobic Cometabolism of Chlorinated Aliphatic Hydrocarbons
2006-09-01
Z39-18 i COST & PERFORMANCE REPORT ESTCP Project: ER-9921 TABLE OF CONTENTS Page 1.0 EXECUTIVE SUMMARY...31 iv ACRONYMS AND ABBREVIATIONS ACFEE Air Force Center for Environmental Excellence Br bromine BTEX benzene...ESTCP Environmental Security Technology Certification Program FID flame ionization detector GC gas chromatography HP Hewlett-Packard IC
2006-09-01
Std Z39-18 i COST & PERFORMANCE REPORT ESTCP Project: ER-9921 TABLE OF CONTENTS Page 1.0 EXECUTIVE SUMMARY...31 iv ACRONYMS AND ABBREVIATIONS ACFEE Air Force Center for Environmental Excellence Br bromine BTEX...Agency ESTCP Environmental Security Technology Certification Program FID flame ionization detector GC gas chromatography HP Hewlett-Packard
Van Metre, P.C.; Mahler, B.J.
2005-01-01
A shift in national policy toward stronger environmental protection began in the United States in about 1970. Conversely, urban land use, population, energy consumption, and vehicle use have increased greatly since then. To assess the effects of these changes on water quality, the U.S. Geological Survey used sediment cores to reconstruct water-quality histories for38 urban and reference lakes across the United States. Cores were age-dated, and concentration profiles of polycyclic aromatic hydrocarbons (PAHs) and chlorinated hydrocarbons were tested statistically. Significant trends in total DDT, p,p???-DDE, and total PCBs were all downward. Trends in chlordane were split evenly between upward and downward, and trends in PAHs were mostly upward. Significant trends did not occur in about one-half of cases tested. Concentrations of p,p???-DDE, p,p???-DDD, and PCBs were about one-half as likely to exceed the probable effect concentration (PEC), a sediment quality guideline, in sediments deposited in the 1990s as in 1965-1975, whereas PAHs were twice as likely to exceed the PEC in the more recently deposited sediments. Concentrations of all contaminants evaluated correlated strongly with urban land use. Upward trends in PAH concentrations, the strong association of PAH with urban settings, and rapid urbanization occurring in the United States suggest that PAHs could surpass chlorinated hydrocarbons in the threat they pose to aquatic biota in urban streams and lakes.
2002-12-19
High -Density Polyethylene HFCS High Fructose Corn Syrup HRC Hydrogen Release Compound HAS Hollow Stem...subsurface injection of a soluble electron donor solution (typically comprised of a carbohydrate such as molasses, whey, high fructose corn syrup (HFCS...whey, high fructose corn syrup (HFCS), glucose, lactate, butyrate, benzoate). Other approaches to enhanced anaerobic bioremediation exist, but
Blondeel, E; Chys, M; Depuydt, V; Folens, K; Du Laing, G; Verliefde, A; Van Hulle, S W H
2014-12-01
Scrap material recovery and recycling companies are confronted with waste water that has a highly fluctuating flow rate and composition. Common pollutants, such as COD, nutrients and suspended solids, potentially toxic metals, polyaromatic hydrocarbons and poly chlorinated biphenyls can exceed the discharge limits. An analysis of the leaching behaviour of different scrap materials and scrap yard sweepings was performed at full-scale, pilot-scale and lab-scale in order to find possible preventive solutions for this waste water problem. The results of these leaching tests (with concentrations that frequently exceeded the Flemish discharge limits) showed the importance of regular sweeping campaigns at the company, leak proof or covered storage of specific scrap materials and oil/water separation on particular leachates. The particulate versus dissolved fraction was also studied for the pollutants. For example, up to 98% of the polyaromatic hydrocarbons, poly chlorinated biphenyls and some metals were in the particulate form. This confirms the (potential) applicability of sedimentation and filtration techniques for the treatment of the majority of the leachates, and as such the rainwater run-off as a whole. Copyright © 2014 Elsevier Ltd. All rights reserved.
DOE Office of Scientific and Technical Information (OSTI.GOV)
Kostamo, A.; Medvedev, N.; Pellinen, J.
2000-04-01
Organochlorine compounds in blubber samples of the ringed seal (Phoca hispida saimensis, P. H. ladogensis, and P. h. hispida) were analyzed in order to estimate the state of pollution in three different water areas in Northeast Europe, namely, Lake Saimaa in Finland, Lake Lodoga, and the White Sea in Russia. Geographic differences in concentrations and in relative concentrations of tri- and tetrachlorocymenes, hexachlorobenzene, {alpha}-HCH, {beta}-HCH, {gamma}-HCH (Lindane), seven polychlorinated biphenyl (PCB) congeners, and p,p{prime}-DDT and its metabolites in ringed seals were compared. Concentrations of chlorinated hydrocarbons varied between the water areas. The highest concentrations were found in Saimaa ringed seals,more » followed by Lodaga ringed seals, and the lowest concentrations were detected in ringed seals from the White Sea. Extractable organic halogen (EOX) concentrations in blubber were also analyzed. The concentrations showed a geographic trend similar to those for the individual compounds identified. In Lakes Ladoga and Saimaa, the concentrations of EOX and chlorinated hydrocarbons in the blubber were dependent on the age and sex of the seals, but no such relationship was observed in samples from the White Sea.« less
DOE Office of Scientific and Technical Information (OSTI.GOV)
Umezu, Toyoshi, E-mail: umechan2@nies.go.jp; Shibata, Yasuyuki, E-mail: yshibata@nies.go.jp
2014-09-01
The present study aimed to clarify whether dose–response profiles of acute behavioral effects of 1,2-dichloroethane (DCE), 1,1,1-trichloroethane (TCE), trichloroethylene (TRIC), and tetrachloroethylene (PERC) differ. A test battery involving 6 behavioral endpoints was applied to evaluate the effects of DCE, TCE, TRIC, and PERC in male ICR strain mice under the same experimental conditions. The behavioral effect dose–response profiles of these compounds differed. Regression analysis was used to evaluate the relationship between the dose–response profiles and structural and physical properties of the compounds. Dose–response profile differences correlated significantly with differences in specific structural and physical properties. These results suggest that differencesmore » in specific structural and physical properties of DCE, TCE, TRIC, and PERC are responsible for differences in behavioral effects that lead to a variety of dose–response profiles. - Highlights: • We examine effects of 4 chlorinated hydrocarbons on 6 behavioral endpoints in mice. • The behavioral effect dose–response profiles for the 4 compounds are different. • We utilize regression analysis to clarify probable causes of the different profiles. • The compound's physicochemical properties probably produce the different profiles.« less
NASA Astrophysics Data System (ADS)
Semprini, Lewis; Kitanidis, Peter K.; Kampbell, Don H.; Wilson, John T.
1995-04-01
We estimated the distribution of chlorinated aliphatic hydrocarbons (CAHs) from groundwater samples collected along three transects in a sand aquifer. Trichloroethylene (TCE) leaked and contaminated the aquifer probably more than a decade before we collected the measurements. The data show significant concentrations of TCE, cis-l,2-dichloroethylene (c-DCE), vinyl chloride (VC), and ethene. We attributed DCE, VC, and ethene to the reductive dehalogenation of TCE. The CAH concentrations varied significantly with depth and correlate with sulfate and methane concentrations. Anoxic aquifer conditions exist with methane present at relatively high concentrations at depth. High concentrations of TCE correspond with the absence of methane or low methane concentrations, whereas products of TCE dehalogenation are associated with higher methane concentrations and low sulfate concentrations. Indications are that the dechlorination of TCE and DCE to VC and ethene is associated with sulfate reduction and active methanogenesis. TCE dechlorination to DCE is likely occurring under the less reducing conditions of sulfate reduction, with further reductions to VC and ethene occurring under methanogenic conditions. We estimated that about 20% of TCE has dechlorinated to ethene. The analysis of the data enhanced our knowledge of natural in situ transformation and transport processes of CAHs.
Accumulation and diagenesis of chlorinated hydrocarbons in lacustrine sediments
Elsenreich, S.J.; Capel, P.D.; Robbins, J.A.; Bourbonniere, R.
1989-01-01
Two sediment cores were taken from the Rochester Basin of eastern Lake Ontario and analyzed for the radionuclides 210Pb and 137Cs and several high molecular weight chlorinated hydrocarbons (CHs). The two sites are geographically proximate but differ in sedimentation rate, permitting sedimentation-dependent processes to be factored out. The 210Pb chronology showed a mixed depth of 3-5 cm and an intrinsic time resolution of 11-14 years. Vertically integrated numbers of deposit-feeding oligochaete worms and burrowing organisms are insufficient to homogenize the sediment on the time scale of CH inputs, which are non steady state. U.S. production and sales of polychlorinated biphenyls (PCBs), DDT, Mirex, and hexachlorobenzene (HCB), as determinants of the shape of the input function, adequately predict the overall shape and, in many cases, details in the sedimentary profile. Sediment focusing factors (FF) inferred from 137Cs and 210Pb inventories averaged 1.17 and 1.74 for cores E-30 and G-32, respectively. This permitted CH accumulation rates to be corrected for focusing. Apparent molecular diffusion coefficients modeled for many of the CHs were about (1-3) ?? 10-9 cm2/s.
Trends in chlorinated hydrocarbon levels in Hudson River basin sediments.
Bopp, R F; Chillrud, S N; Shuster, E L; Simpson, H J; Estabrooks, F D
1998-01-01
Analysis of sections from dated sediment cores were used to establish geographic distributions and temporal trends of chlorinated hydrocarbon contaminant levels in sediments from natural waters of the Hudson River basin. Radiometric dating was based primarily on the depth distribution of 137(Cs) in the cores and on the occurrence of detectable levels of 7(Be) in surface sediment samples. Eighteen sampling sites included several along the main stem of the Hudson, its major tributaries, and components of the New York/New Jersey (NY/NJ) harbor complex. Drinking-water reservoirs were sampled to place upper limits on atmospheric inputs. Core sections were analyzed for polychlorinated biphenyls (PCBs), 1,1,1-trichloro-2,2-bis(p-chlorophenyl) ethane (DDT)-derived compounds, chlordane, and dioxins. Sediment concentrations of most contaminants at most sites have decreased significantly since the mid-1960s. The data provide a basinwide perspective on major point-source inputs of PCBs to the upper Hudson River and of 2,3,7,8-tetrachlorodibenzo-p-dioxin and DDT to the lower Passaic River. Evidence was found for significant but poorly characterized sources of PCBs and chlordane to the western NY/NJ harbor, and of highly chlorinated dioxins to the upstream sites on the main stem of the Hudson. The results indicate that analysis of dated sediment samples is a most effective and efficient monitoring tool for the study of large-scale geographic and temporal trends in levels of particle-associated contaminants. Images Figure 1 Figure 3 Figure 4 Figure 5 Figure 6 Figure 7 PMID:9703496
Diurnal variability of chlorinated polycyclic aromatic hydrocarbons in urban air, Japan
NASA Astrophysics Data System (ADS)
Ohura, Takeshi; Horii, Yuichi; Kojima, Mitsuhiro; Kamiya, Yuta
2013-12-01
Concentrations of 3- to 5-ring chlorinated polycyclic aromatic hydrocarbons (ClPAHs) and corresponding PAHs were quantified in 3-h integrated air samples, taken serially over 3-day periods in December 2009 (winter) and August 2010 (summer) in the urban area of Shizuoka, Japan. Twenty species of targeted ClPAHs were detected in both gas and particle phases throughout each campaign. Mean concentrations of total ClPAHs in the winter and summer campaigns were 133 ± 53 pg m-3 and 32 ± 27 pg m-3, respectively. Throughout the campaigns, diurnal variations of total ClPAHs concentrations did not have periodic fluctuation such as decreasing in daytime and increasing in nighttime, observed in PAHs. However, the mean concentrations of particulate ClPAHs trended to be slightly higher in nighttime than in daytime, but not for gaseous ClPAHs. Significant correlations were observed between the concentrations of total ClPAHs and total PAHs in particulate phase, but not in gaseous phase. In addition, for particulate phase, there were significant correlations between the concentrations of individual ClPAHs and corresponding parent PAHs, nitrate, and chlorine in summer, but not in winter. Considering these behaviors of ClPAHs in the air, the emission sources could have features of as follows: (i) specific emission sources emitted both ClPAHs and PAHs in particulate phase could be present in the area; (ii) particulate ClPAHs could be more strongly influenced by local sources and photochemical reactions rather than by transboundary air pollution; (iii) the possible sources could be combustion processes included biomass and fossil fuels.
Organic molecules in the Sheepbed Mudstone, Gale Crater, Mars
Freissinet, C; Glavin, D P; Mahaffy, P R; Miller, K E; Eigenbrode, J L; Summons, R E; Brunner, A E; Buch, A; Szopa, C; Archer, P D; Franz, H B; Atreya, S K; Brinckerhoff, W B; Cabane, M; Coll, P; Conrad, P G; Des Marais, D J; Dworkin, J P; Fairén, A G; François, P; Grotzinger, J P; Kashyap, S; ten Kate, I L; Leshin, L A; Malespin, C A; Martin, M G; Martin-Torres, F J; McAdam, A C; Ming, D W; Navarro-González, R; Pavlov, A A; Prats, B D; Squyres, S W; Steele, A; Stern, J C; Sumner, D Y; Sutter, B; Zorzano, M-P
2015-01-01
The Sample Analysis at Mars (SAM) instrument on board the Mars Science Laboratory Curiosity rover is designed to conduct inorganic and organic chemical analyses of the atmosphere and the surface regolith and rocks to help evaluate the past and present habitability potential of Mars at Gale Crater. Central to this task is the development of an inventory of any organic molecules present to elucidate processes associated with their origin, diagenesis, concentration, and long-term preservation. This will guide the future search for biosignatures. Here we report the definitive identification of chlorobenzene (150–300 parts per billion by weight (ppbw)) and C2 to C4 dichloroalkanes (up to 70 ppbw) with the SAM gas chromatograph mass spectrometer (GCMS) and detection of chlorobenzene in the direct evolved gas analysis (EGA) mode, in multiple portions of the fines from the Cumberland drill hole in the Sheepbed mudstone at Yellowknife Bay. When combined with GCMS and EGA data from multiple scooped and drilled samples, blank runs, and supporting laboratory analog studies, the elevated levels of chlorobenzene and the dichloroalkanes cannot be solely explained by instrument background sources known to be present in SAM. We conclude that these chlorinated hydrocarbons are the reaction products of Martian chlorine and organic carbon derived from Martian sources (e.g., igneous, hydrothermal, atmospheric, or biological) or exogenous sources such as meteorites, comets, or interplanetary dust particles. Key Points First in situ evidence of nonterrestrial organics in Martian surface sediments Chlorinated hydrocarbons identified in the Sheepbed mudstone by SAM Organics preserved in sample exposed to ionizing radiation and oxidative condition PMID:26690960
Organic molecules in the Sheepbed Mudstone, Gale Crater, Mars.
Freissinet, C; Glavin, D P; Mahaffy, P R; Miller, K E; Eigenbrode, J L; Summons, R E; Brunner, A E; Buch, A; Szopa, C; Archer, P D; Franz, H B; Atreya, S K; Brinckerhoff, W B; Cabane, M; Coll, P; Conrad, P G; Des Marais, D J; Dworkin, J P; Fairén, A G; François, P; Grotzinger, J P; Kashyap, S; Ten Kate, I L; Leshin, L A; Malespin, C A; Martin, M G; Martin-Torres, F J; McAdam, A C; Ming, D W; Navarro-González, R; Pavlov, A A; Prats, B D; Squyres, S W; Steele, A; Stern, J C; Sumner, D Y; Sutter, B; Zorzano, M-P
2015-03-01
The Sample Analysis at Mars (SAM) instrument on board the Mars Science Laboratory Curiosity rover is designed to conduct inorganic and organic chemical analyses of the atmosphere and the surface regolith and rocks to help evaluate the past and present habitability potential of Mars at Gale Crater. Central to this task is the development of an inventory of any organic molecules present to elucidate processes associated with their origin, diagenesis, concentration, and long-term preservation. This will guide the future search for biosignatures. Here we report the definitive identification of chlorobenzene (150-300 parts per billion by weight (ppbw)) and C 2 to C 4 dichloroalkanes (up to 70 ppbw) with the SAM gas chromatograph mass spectrometer (GCMS) and detection of chlorobenzene in the direct evolved gas analysis (EGA) mode, in multiple portions of the fines from the Cumberland drill hole in the Sheepbed mudstone at Yellowknife Bay. When combined with GCMS and EGA data from multiple scooped and drilled samples, blank runs, and supporting laboratory analog studies, the elevated levels of chlorobenzene and the dichloroalkanes cannot be solely explained by instrument background sources known to be present in SAM. We conclude that these chlorinated hydrocarbons are the reaction products of Martian chlorine and organic carbon derived from Martian sources (e.g., igneous, hydrothermal, atmospheric, or biological) or exogenous sources such as meteorites, comets, or interplanetary dust particles. First in situ evidence of nonterrestrial organics in Martian surface sediments Chlorinated hydrocarbons identified in the Sheepbed mudstone by SAM Organics preserved in sample exposed to ionizing radiation and oxidative condition.
Chemical fate and genotoxic risk associated with hypochlorite treatment of nicotine.
Zarrelli, Armando; DellaGreca, Marina; Parolisi, Alice; Iesce, Maria Rosaria; Cermola, Flavio; Temussi, Fabio; Isidori, Marina; Lavorgna, Margherita; Passananti, Monica; Previtera, Lucio
2012-06-01
Nicotine, the main alkaloid of tobacco, is a non- prescription drug to which all members of a tobacco-smoking society are exposed either through direct smoke inhalation or through second-hand passive 'smoking'. Nicotine is also commercially available in some pharmaceutical products and is used worldwide as a botanical insecticide in agriculture. Nicotine dynamics in indoor and outdoor environments as well as the human excretions and the manufacturing process are responsible for its entry in the environment through municipal and industrial wastewater discharges. The presence of nicotine in surface and ground waters points out that it survives a conventional treatment process and persists in potable-water supplies. Complete removal of nicotine is instead reported when additional chlorination steps are used. In this paper a simulation of STP chlorination of nicotine and a genotoxic evaluation of its main degradation products are reported. Under laboratory conditions removal of nicotine seems not to be due to mineralization but to transformation in oxidized and chlorinated products. The by-products have been isolated after fractionation by diverse chromatographic procedures and their structures determined using mass spectrometry and (1)H and (13)C NMR spectroscopy. Preliminary genotoxic SOS Chromotests with Escherichia coli PQ37 evidence no toxicity of the products. Copyright © 2012 Elsevier B.V. All rights reserved.
NASA Astrophysics Data System (ADS)
Piosik, Emilia; Synak, Anna; Martyński, Tomasz
2018-01-01
The influence of chlorine atoms in the bay positions of the perylene-3,4,9,10-tetracarboxylic acids with the different alkyl chains length on their spectral properties in monomolecular films has been studied. The chlorinated (PCln) and for comparison non-chlorinated (Pn) perylene derivatives were deposited onto quartz plates using a Langmuir-Blodgett (LB) technique. The absorption spectra showed that the PCln and Pn dyes form in monolayers the I- and J-type aggregates, respectively. In turn, their steady-state and time-resolved emission spectra revealed presence of two emitter types, which we assigned to monomers and excimers. The luminescence lifetimes of the PCln monomers and excimers determined with a time-correlated single photon counting method (TCSPC) are significantly shorter than these obtained for the same emitter types in the Pn monolayers. In the case of the chlorinated dyes, the contribution of the monomer emission dominates over the excimer emission and is almost independent from the alkyl chain length. By contrast, the share of the Pn monomer emission increases strongly with a number of carbon atoms in their hydrocarbon chains. The luminescence quantum yields (LQY) of the Pn and PCln monolayers measured in an integrating sphere are in the range of 0.06-0.11. The presented results reveal that the PCln dyes exhibit lower tendency for aggregation than the non-chlorinated derivatives. It can be explained by limited intermolecular interaction between neighbouring PCln molecules caused by deformation of the perylene core as a result of strongly electronegative chlorine atoms in the bay positions of these dyes. Moreover, the strong influence of the alkyl chain length on the Pn aggregation contrary to the case of the PCln derivatives was observed.
Rajasekharan, Vishnu V; Clark, Brandi N; Boonsalee, Sansanee; Switzer, Jay A
2007-06-15
The commonly used disinfectants in drinking water are free chlorine (in the form of HOCl/OCl-) and monochloramine (NH2Cl). While free chlorine reacts with natural organic matter in water to produce chlorinated hydrocarbon byproducts, there is also concern that NH2Cl may react with Pbto produce soluble Pb(II) products--leading to elevated Pb levels in drinking water. In this study, electrochemical methods are used to compare the thermodynamics and kinetics of the reduction of these two disinfectants. The standard reduction potential for NH2Cl/Cl- was estimated to be +1.45 V in acidic media and +0.74 V in alkaline media versus NHE using thermodynamic cycles. The kinetics of electroreduction of the two disinfectants was studied using an Au rotating disk electrode. The exchange current densities estimated from Koutecky-Levich plots were 8.2 x 10(-5) and 4.1 x 10(-5) A/cm2, and by low overpotential experiments were 7.5 +/- 0.3 x 10(-5) and 3.7 +/- 0.4 x 10(-5) A/cm2 for free chlorine and NH2Cl, respectively. The rate constantforthe electrochemical reduction of free chlorine at equilibrium is approximately twice as large as that for the reduction of NH2Cl. Equilibrium potential measurements show that free chlorine will oxidize Pb to PbO2 above pH 1.7, whereas NH2Cl will oxidize Pb to PbO2 only above about pH 9.5, if the total dissolved inorganic carbon (DIC) is 18 ppm. Hence, NH2Cl is not capable of producing a passivating PbO2 layer on Pb, and could lead to elevated levels of dissolved Pb in drinking water.
NASA Astrophysics Data System (ADS)
Hannus, I.; Kropok, Zs.; Halász, J.
2007-05-01
Some of the chlorinated organic compounds are widely used commercially, because of their advantageous chemical/physical properties or having toxicity for pestiferous living substances. However, emitted into the atmosphere they are responsible for diminishing the ozone layer in the stratosphere. Therefore, a lot of effort is devoted in finding proper solutions to decompose these chemicals in environmentally friendly ways. Platinum on different carriers play very important role in catalytic hydrodechlorination of these compounds. We have found that Pt-containing Y-FAU zeolite is an active catalyst in the hydrodechlorination of trichloroethene. IR spectroscopic experiments showed that the final products are ethane and HCl, and the hydrogen/reactant ratio exerts large influence on the rate of the hydrodechlorination reaction.
NASA Technical Reports Server (NTRS)
Colombo, G. V.; Putnam, D. F.
1977-01-01
The effluent gas stream from an electrolytic urine pretreatment process was analyzed by gas chromatography-mass spectroscopy and wet chemical methods to determine its composition. The major constituents were identified as: hydrogen, carbon dioxide, oxygen, nitrogen, water vapor, and chlorine. The trace impurities were chlorinated light hydrocarbons, and a number of other organic impurities in the low ppm range. Several methods of removing all of the undesirable gases to levels acceptable for return to a space cabin atmosphere were investigated experimentally. A subsystem concept comprised of the following sequential unit processes and operations was successfully demonstrated: (1) raw urine scrubbing, (2) silica gel sorption, (3) dilution with cabin air, and (4) catalytic oxidation.
McCarthy, Kathleen A.; Lilly, Michael R.; Braddock, Joan F.; Hinzman, Larry D.
1998-01-01
Natural attenuation processes include biological degradation, by which microorganisms break down contaminants into simpler product compounds; adsorption of contaminants to soil particles, which decreases the mass of contaminants dissolved in ground water; and dispersion, which decreases dissolved contaminant concentrations through dilution. The primary objectives of this study are to (1) assess the degree to which such natural processes are attenuating chlorinated-hydrocarbon contamination in ground water, and (2) evaluate the effects of ground-water/surface-water interactions on natural-attenuation processes in the area of the former East and West Quartermasters Fueling Systems for Fort Wainwright, Alaska. The study will include investigations of the hydrologic, geochemical, and microbiological processes occurring at this site that influence the transport and fate of chlorinated hydrocarbons in ground water. To accomplish these objectives, a data-collection program has been initiated that includes measurements of water-table elevations and the stage of the Chena River; measurements of vertical temperature profiles within the subsurface; characterization of moisture distribution and movement in the unsaturated zone; collection of ground-water samples for determination of both organic and inorganic chemical constituents; and collection of ground-water samples for enumeration of microorganisms and determination of their potential to mineralize contaminants. We will use results from the data-collection program described above to refine our conceptual model of hydrology and contaminant attenuation at this site. Measurements of water-table elevations and river stage will help us to understand the magnitude and direction of ground-water flow and how changes in the stage of the Chena River affect ground-water flow. Because ambient ground water and surface water typically have different temperature characteristics, temperature monitoring will likely provide further insight into ground-water/surface-water interactions in the subsurface. Characterization of the unsaturated zone will improve our understanding of interactions among ground water, the unsaturated zone, and the atmosphere. The interactions likely of importance to this study include the migration of water, dissolved contaminants, nutrients, and gases (oxygen, carbon dioxide, and methane) between the saturated and unsaturated zones. We will use the results of ground-water chemical analyses to determine the spatial and temporal distribution of (1) chlorinated-hydrocarbon contaminants and their degradation products, (2) oxidation-reduction indicators, (3) nutrients, and (4) major ground-water ions. These water-quality data will provide insight into ground-water flow directions, interactions between ground water and surface water, attenuation of contaminant concentrations caused by dispersion, and intrinsic microbiological processes. Microbiological analyses will indicate whether microorganisms at the site are capable of degrading the contaminants of interest, and will allow us to estimate their potential to attenuate existing contamination. Physical and chemical data interpreted as part of the analysis of ground water and surface water mixing will improve our understanding of the relationship between water quality and contaminant source mixing.
Kumar, Sunil; Park, Jiyeong; Kim, Eunseong; Na, Jahyun; Chun, Yong Shik; Kwon, Hyeok; Kim, Wook; Kim, Yonggyun
2015-10-01
A novel fumigant, chlorine dioxide (ClO2) is a commercial bleaching and disinfection agent. Recent study indicates its insecticidal activity. However, its mode of action to kill insects is yet to be understood. This study set up a hypothesis that an oxidative stress induced by ClO2 is a main factor to kill insects. The Indian meal moth, Plodia interpunctella, is a lepidopteran insect pest infesting various stored grains. Larvae of P. interpunctella were highly susceptible to ClO2 gas, which exhibited an acute toxicity. Physiological damages by ClO2 were observed in hemocytes. At high doses, the larvae of P. interpunctella suffered significant reduction of total hemocytes. At low doses, ClO2 impaired hemocyte behaviors. The cytotoxicity of ClO2 was further analyzed using two insect cell lines, where Sf9 cells were more susceptible to ClO2 than High Five cells. The cells treated with ClO2 produced reactive oxygen species (ROS). The produced ROS amounts increased with an increase of the treated ClO2 amount. However, the addition of an antioxidant, vitamin E, significantly attenuated the cytotoxicity of ClO2 in a dose-dependent manner. To support the oxidative stress induced by ClO2, two antioxidant genes (superoxide dismutase (SOD) and thioredoxin-peroxidase (Tpx)) were identified from P. interpunctella EST library using ortholog sequences of Bombyx mori. Both SOD and Tpx were expressed in larvae of P. interpunctella especially under oxidative stress induced by bacterial challenge. Exposure to ClO2 gas significantly induced the gene expression of both SOD and Tpx. RNA interference of SOD or Tpx using specific double stranded RNAs significantly enhanced the lethality of P. interpunctella to ClO2 gas treatment as well as to the bacterial challenge. These results suggest that ClO2 induces the production of insecticidal ROS, which results in a fatal oxidative stress in P. interpunctella. Copyright © 2015 Elsevier Inc. All rights reserved.
Emamectin benzoate: new insecticide against Helicoverpa armigera.
Fanigliulo, A; Sacchetti, M
2008-01-01
Emamectin benzoate is a new insecticide of Syngenta Crop Protection, with a new mechanism of action and a strong activity against Lepidoptera as well as with and a high selectivity on useful organisms. This molecule acts if swallowed and has some contact action. It penetrates leaf tissues (translaminar activity) and forms a reservoir within the leaf. The mechanism of action is unique in the panorama of insecticides. In facts, it inhibits muscle contraction, causing a continuous flow of chlorine ions in the GABA and H-Glutamate receptor sites. During 2006 and 2007, experimentation was performed by the Bioagritest test facility, according to EPPO guidelines and Principles of Good Experimental Practice (GEP), aiming at establishing the biological efficacy and the selectivity of Emamectin benzoate on industry tomato against Helicoverpa armigera (Lepidoptera: Noctuidoe). The study was performed in Tursi-Policoro (Matera), southern Italy. Experimental design consisted in random blocks, in 4 repetitions. A dosage of 1.5 Kg/ha of the formulate was compared with two commercial formulates: Spinosad 0.2 kg/ha (Laser, Dow Agrosciences Italia) and Indoxacarb 0.125 kg/ha (Steward EC insecticide, Dupont). Three foliage applications were applied every 8 days. The severity of damage induced by H. armigera was evaluated on fruits. Eventual phytotoxic effects were also evaluated. Climatic conditions were optimal for Lepidoptera development, so that the percentage of fruits attacked in 2007 at the first scouting was 68.28%. Emamectin benzoate has shown, in two years of testing, a high control of H. armigera if compared with the standards Indoxacarb and Spinosad. No effect of phytotoxicity was noticed on fruits.
Vacuum-based surface modification of organic and metallic substrates
NASA Astrophysics Data System (ADS)
Torres, Jessica
Surface physico-chemical properties play an important role in the development and performance of materials in different applications. Consequently, understanding the chemical and physical processes involved during surface modification strategies is of great scientific and technological importance. This dissertation presents results from the surface modification of polymers, organic films and metallic substrates with reactive species, with the intent of simulating important modification processes and elucidating surface property changes of materials under different environments. The reactions of thermally evaporated copper and titanium with halogenated polytetrafluoroethylene (PTFE) and polyvinyl chloride (PVC) are used to contrast the interaction of metals with polymers. Results indicate that reactive metallization is thermodynamically favored when the metal-halogen bond strength is greater than the carbon-halogen bond strength. X-ray post-metallization treatment results in an increase in metal-halide bond formation due to the production of volatile halogen species in the polymer that react with the metallic overlayer. The reactions of atomic oxygen (AO) and atomic chlorine with polyethylene (PE) and self-assembled monolayers (SAMs) films were followed to ascertain the role of radical species during plasma-induced polymer surface modification. The reactions of AO with X-ray modified SAMs are initially the dominated by the incorporation of new oxygen containing functionality at the vacuum/film interface, leading to the production of volatile carbon containing species such as CO2 that erodes the hydrocarbon film. The reaction of atomic chlorine species with hydrocarbon SAMs, reveals that chlorination introduces C-Cl and C-Cl2 functionalities without erosion. A comparison of the reactions of AO and atomic chlorine with PE reveal a maximum incorporation of the corresponding C-O and C-Cl functionalities at the polymer surface. A novel method to prepare phosphorous-containing polymer surfaces through ion implantation of trimethyl phosphine onto PE is presented. Air exposure of the resulting P-implanted PE leads to the surface selective oxidation of phosphorous moieties. P-containing hydrocarbon films are used to model the surface chemical changes of P-containing polymers exposed to AO. Results indicate that oxidized phosphorous species protect the film from AO-induced erosion. The low temperature (<150 K) oxidation of nitrided iron surfaces exposed to oxygen reveal the formation of iron oxynitride (FexNyO z, nitrosonium ions (NO+) as well as nitrite/nitrito and nitrate type species. The production of nitrite/nitrito and nitrate species is taken as evidence for the existence of oxygen insertion chemistry into the iron nitride lattice under these low temperature oxidation conditions. Upon annealing the oxidized iron nitride surface, nitrogen desorbs exclusively as nitric oxide (NO).
Environmental impact of pesticides in Egypt.
Mansour, Sameeh A
2008-01-01
The first use of petroleum-derived pesticides in Egyptian agriculture was initiated in 1950. Early applications consisted of distributing insecticidal dusts containing DDT/BHC/S onto cotton fields. This practice was followed by use of toxaphene until 1961. Carbamates, organophosphates, and synthetic pyrethroids were subsequently used, mainly for applications to cotton. In addition to the use of about 1 million metric tons (t) of pesticides in the agricultural sector over a 50-yr period, specific health and environmental problems are documented in this review. Major problems represented and discussed in this review are human poisoning, incidental toxicity to farm animals, insect pest resistance, destruction of beneficial parasites and predators, contamination of food by pesticide residues, and pollution of environmental ecosystems. Several reports reveal that chlorinated hydrocarbon pesticide residues are still detectable in several environmental compartments; however, these residues are in decline. Since 1990, there is a growing movement toward reduced consumption of traditional pesticides and a tendency to expand use of biopesticides, including "Bt," and plant incorporated protectants (PIPs). On the other hand, DDT and lindane were used for indoor and hygienic purposes as early as 1952. Presently, indoor use of pesticides for pest control is widespread in Egypt. Accurate information concerning the types and amounts of Egyptian household pesticide use, or numbers of poisoning or contamination incidents, is unavailable. Generally, use of indoor pesticides is inadequately managed. The results of a survey of Egyptian farmers' attitudes toward pesticides and their behavior in using them garnered new insights as to how pesticides should be better controlled and regulated in Egypt.
Nerve membrane ion channels as the target site of environmental toxicants
DOE Office of Scientific and Technical Information (OSTI.GOV)
Narahashi, T.
1987-04-01
There are many environmentally important chemicals which exhibit potent effects on the nervous system. Since nerve excitation takes place in a fraction of a second, electrophysiological methods provide the authors with the most straightforward approach to the study of the mechanisms of action of environmental toxicants on the nervous system. Aquatic animals such as crayfish, lobster, squid, and marine snails represent extremely useful materials for such electrophysiological studies, because much of the authors knowledge of nerve excitation is derived from those animals. Nerve excitation takes place as a result of opening and closing of ion channels of the membrane. Thesemore » functions are independent of metabolic energy, and can be measured most effectively by voltage clamp techniques as applied to the giant axons of the crayfish and the squid. Patch clamp techniques developed during the past 10 years have added a new dimension to the electrophysiological investigation. These techniques allow them to measure the activity of individual ion channels, thereby making it possible to analyze the interaction of toxic molecules directly with single ion channels. Examples are given summarizing electrophysiological studies of environmental neurotoxicants. The abdominal nerve cords and neuromuscular preparations isolated from the crayfish are convenient materials for bioassay of certain environmental toxicants such as pyrethroids, chlorinated hydrocarbons, and other insecticides. Only a small fraction of the flux through the sodium channel, less than 1%, must be modified by pyrethroids for the animal to develop symptoms of poisoning. Such a toxicological application from channel to animal is important is understanding the potent toxic effect.« less
Smith, James A.; Witkowski, Patrick J.; Fusillo, Thomas V.
1987-01-01
This report reviews the occurrence and distribution of manmade organic compounds in the surface waters of the United States. On the basis of their aqueous solubilities, nonionic organic compounds partition themselves between water, dissolved organic matter, particulate organic matter, and the lipid reservoirs of aquatic organisms. Ionized organic compounds can be absorbed to sediments, thereby reducing their aqueous concentrations. Transformation processes of photolysis, hydrolysis, biodegradation, and volatilization can attenuate organic compounds, and attenuation rate commonly follow a first-order kinetic process. Eight groups of manmade organic compounds are discussed: 1. Polychlorinated biphenyls and organochlorine insecticides, 2. Carbamate and organophosphorus insecticides, 3. Herbicides, 4. Phenols, 5. Halogenated aliphatic and monocyclic aromatic hydrocarbons, 6. Phthalate esters, 7. Polychlorinated dibenzo-p-dioxins, and 8. Polycyclic aromatic hydrocarbons. For each compound group, data pertaining to use, production, and properties are presented and discussed. Processes that influence that the environmental fate of each group, as determined primarily through laboratory studies, are reviewed, and important fate processes are identified. Environmental concentrations of compounds from each group in water, biota, and sediment are given to demonstrate representative values for comparison to concentrations determined during ongoing research. Finally, where sufficient data exist, regional and temporal contamination trends in the United States are discussed.
Smith, James A.; Witkowski, P.J.; Fusillo, Thomas V.
1988-01-01
This report reviews the occurrence and distribution of manmade organic compounds in the surface waters of the United States. On the basis of their aqueous solubilities, nonionic organic compounds partition themselves among water, dissolved organic matter, particulate organic matter, and the lipid reservoirs of aquatic organisms. Ionized organic compounds can be adsorbed to sediments, thereby reducing their aqueous concentrations. Transformation processes of photolysis, hydrolysis, biodegradation, and volatilization can attenuate organic compounds, and attenuation rates commonly follow a first-order kinetic process. Eight groups of manmade organic compounds are discussed: 1. Polychlorinated biphenyls and organochlorine insecticides, 2. Carbamate and organophosphorus insecticides, 3. Herbicides, 4. Phenols, 5. Halogenated aliphatic and monocyclic aromatic hydrocarbons, 6. Phthalate esters, 7. Polychlorinated dibenzo-p-dioxins, and 8. Polycyclic aromatic hydrocarbons. For each compound group, data pertaining to use, production, and properties are presented and discussed. Processes that influence the environmental fate of each group, as determined primarily through laboratory studies, are reviewed, and important fate processes are identified. Environmental concentrations of compounds from each group in water, biota, and sediment are given to demonstrate representative values for comparison with concentrations determined during ongoing research. Finally, where data are sufficient, regional and temporal contamination trends in the United States are discussed.
Xin, Shanzhi; Gao, Wei; Wang, Yawei; Jiang, Guibin
2017-10-01
Chlorinated paraffins (CPs) generally function as flame retardants and plasticizers in various materials. They are most likely to be processed by thermal processes during the entire life cycle. However, data on the formation and emission of CPs during thermal processes are still not fully understood. In this study, we simulated industrial thermal processes to investigate the emission of medium-chain chlorinated paraffins (MCCPs) and short-chain chlorinated paraffins (SCCPs) using commercial CP52 as the feedstock. We found that CP52 decomposed very easily at 210-320 °C. The decomposition of CPs generated large quantities of MCCPs and SCCPs. These remained in the residue at low temperature (∼200 °C) and were gradually released into the gas phase at higher temperatures. MCCPs and SCCPs were not detected in either the residue or the gas phase when the temperature exceeded 400 °C. However, considerable concentrations of aromatic and chlorinated aromatic hydrocarbons (Cl-PAHs) were identified in the gas phase, and they were formed as the amount of SCCPs and MCCPs decreased. Cl-PAHs were dominated by low-chlorinated chlorobenzenes, polychlorinated biphenyls, and polychlorinated naphthalenes. Oxygen promoted the release and decomposition of SCCPs in the gas phase. The results of the present study revealed the release of MCCPs and SCCPs and their synergistic emission with Cl-PAHs when CPs were subjected to heat. This work may also provide data for developing multiple techniques to control the emission of CPs and Cl-PAHs. Copyright © 2017 Elsevier Ltd. All rights reserved.
1990-10-01
adsorption/incineration * Membrane vapor separation/condensation * Supercritical fluid oxidation • UV/ozone destruction * Molten salt combustion process...separation/ separate air stream contaminants 9 Oxygenated solvents condensation * Chlorinated hydrocarbons Supercritical fluid * Technology utilizing high...testing or full-scale unit capacity; they are: * Supercritical fluid oxidation • UV/ozone destruction * Molten salt incineration * Infrared incineration
Identifying and Determining Halocarbons in Water Using Headspace Gas Chromatography.
1981-10-01
chromatography Halogenated hydrocarbons , / Wastewater 26. T -ACT C’Cth.I .- ,,ee .- ,ncee, ,Id ntify y block number) --/,*Since the discovery that...USING HEADSPACE GAS CHROMATOGRAPHY Daniel C. Leggett INTRODUCTION Chlorination is a well-established method of disinfecting water for drinking and of... disinfecting municipal wastewater prior to disposal. The recent discovery that persistent chloro-organic molecules are formed in this processi 5 has
Blake, Donald [University of California, Irvine, Irvine, CA (USA)
2013-09-01
Whole-air samples are collected in conditioned, evacuated, 2-L stainless steel canisters; each canister is filled to ambient pressure over a period of about 1 minute (approximately 20 seconds to 2 minutes). These canisters are returned to the University of California at Irvine for chromatographic analysis.
Tenbus, Frederick J.; Fleck, William B.
2001-01-01
Military activity at Graces Quarters, a former open-air chemical-agent facility at Aberdeen Proving Ground, Maryland, has resulted in ground-water contamination by chlorinated hydrocarbons. As part of a ground-water remediation feasibility study, a three-dimensional model was constructed to simulate transport of four chlorinated hydrocarbons (1,1,2,2-tetrachloroethane, trichloroethene, carbon tetrachloride, and chloroform) that are components of a contaminant plume in the surficial and middle aquifers underlying the east-central part of Graces Quarters. The model was calibrated to steady-state hydraulic head at 58 observation wells and to the concentration of 1,1,2,2-tetrachloroethane in 58 observation wells and 101direct-push probe samples from the mid-1990s. Simulations using the same basic model with minor adjustments were then run for each of the other plume constituents. The error statistics between the simulated and measured concentrations of each of the constituents compared favorably to the error statisticst,1,2,2-tetrachloroethane calibration. Model simulations were used in conjunction with contaminant concentration data to examine the sources and degradation of the plume constituents. It was determined from this that mixed contaminant sources with no ambient degradation was the best approach for simulating multi-species solute transport at the site. Forward simulations were run to show potential solute transport 30 years and 100 years into the future with and without source removal. Although forward simulations are subject to uncertainty, they can be useful for illustrating various aspects of the conceptual model and its implementation. The forward simulation with no source removal indicates that contaminants would spread throughout various parts of the surficial and middle aquifers, with the100-year simulation showing potential discharge areas in either the marshes at the end of the Graces Quarters peninsula or just offshore in the estuaries. The simulation with source removal indicates that if the modeling assumptions are reasonable and ground-water cleanup within30 years is important, source removal alone is not a sufficient remedy, and cleanup might not even occur within 100 years.
Sankoda, Kenshi; Nomiyama, Kei; Yonehara, Takayuki; Kuribayashi, Tomonori; Shinohara, Ryota
2012-07-01
This study investigated environmental distributions and production mechanisms of chlorinated polycyclic aromatic hydrocarbons (Cl-PAHs) in the sediments from some tidal flats located in Asia. Cl-PAHs were found in sediments taken from Arao tidal flat, Kikuchigawa River and Shirakawa River. The range of ∑Cl-PAHs was from 25.5 to 483 pg g(-1) for Kikuchigawa River and Arao tidal flat, respectively. Concentrations of PAHs and Cl-PAHs showed no significant correlations (r=0.134). This result suggests that the origins of these compounds differ. In the identified Cl-PAH isomers, the most abundant Cl-PAH isomer was 9,10-dichloroanthracene (9,10-di-Cl-ANT) in the three sites. In general, concentrations of Cl-ANTs in the coastal environment are about 3-5 orders of magnitude lower than those of anthracene (ANT). However, concentration ratios between Cl-ANTs and ANT (Cl-ANTs/ANT) in the sediments ranged from 4.1% to 24.6%. This result indicated that Cl-PAHs were not generated under industrial processes but the high concentration ratios have resulted from the contribution of photochemical production of Cl-ANTs in the sediments because ANT is known to have high photochemical reactivity. For examining this phenomenon, ANT adsorbed onto glass beads was irradiated with UV under the mimicked field conditions of tidal flats. As a result, it was noticed that, while chlorinated derivatives were negligible in a light-controlled group, production of 2-Cl-ANT, 9-Cl-ANT and 9,10-diCl-ANT on the irradiated surface were found in this study. These results suggest that photochemical reaction of PAHs can be a potential source of the occurrence of Cl-PAHs in the coastal environment. Copyright © 2012 Elsevier Ltd. All rights reserved.
Díez, C; Martínez, O; Calvo, L F; Cara, J; Morán, A
2004-01-01
A study was made of the pyrolysis of tyre particles, with the aim of determining the possibilities of using the products resulting from the process as fuel. Three final temperatures were used, determined from thermogravimetric data. The design of the experiment was a horizontal oven containing a reactor into which particles of the original tyre were placed. After the process, a solid fraction (char) remained in the reactor, while the gases generated went through a set of scrubbers where most of the condensable fraction (oils) was retained. Finally, once free of this fraction, the gases were collected in glass ampoules. Solid and liquids fractions were subjected to thermogravimetric analyses in order to study their combustibility. The gas fraction was analysed by means of gas chromatography to establish the content of CO, CO2, H2 and hydrocarbons present in the samples (mainly components of gases produced in the pyrolysis process). A special study was made of the sulphur and chlorine content of all the fractions, as the presence of these elements could be problematic if the products are used as fuel. Tyre pyrolysis engenders a solid carbon residue that concentrates sulphur and chorine, with a relatively high calorific value, although not so high as that of the original tyre. The liquid fraction produced by the process has a high calorific value, which rises with the final temperature, up to 40 MJ/kg. The chlorine content of this fraction is negligible. Over 95% of the gas fraction, regardless of the final temperature, is composed of hydrocarbons of a low molecular weight and hydrogen, this fraction also appearing to be free of chlorine.
Jin, Rong; Liu, Guorui; Zheng, Minghui; Fiedler, Heidelore; Jiang, Xiaoxu; Yang, Lili; Wu, Xiaolin; Xu, Yang
2017-08-04
Isotopic dilution gas chromatography combined with high resolution mass spectrometry (GC/HRMS) has overwhelming advantages with respect to the accuracy of congener-specific ultratrace analysis of complex persistent organic pollutants (POPs) in environmental matrices. However, an isotopic dilution GC/HRMS method for analysis of chlorinated and brominated polycyclic aromatic hydrocarbons (Cl-PAHs and Br-PAHs) using 13 C-labelled congeners as internal standards has not been established. In this study, a method for identification and quantification of 38 congeners of Cl-PAHs and Br-PAHs in atmosphere and stack gas samples from waste incinerators was developed using the isotopic dilution GC/HRMS technique. The instrumental detection limits of the GC/HRMS method ranged from 0.2pg to 1.8pg for Cl-PAH congeners, and 0.7pg to 2.7pg for Br-PAH congeners, which were about three orders of magnitude lower than those of the GC/quadrupole MS method. This new method developed was also the first to enable determination of Cl-PAH and Br-PAH homologs comprising congeners with the same molecular skeleton and chlorine or bromine substitution numbers. Among the detected congeners, seven Cl-PAH congeners and thirteen Br-PAH congeners that were abundant in the atmosphere and stack gases released from waste incinerators were firstly detected in real samples and reported using the established isotopic dilution GC/HRMS method. The developed isotopic dilution GC/HRMS is significant and needed for better studying the environmental behavior and health risk of Cl-PAHs and Br-PAHs. Copyright © 2017 Elsevier B.V. All rights reserved.
Computation of porosity redistribution resulting from thermal convection in slanted porous layers
NASA Astrophysics Data System (ADS)
Gouze, Phillippe; Coudrain-Ribstein, Anne; Bernard, Dominique
1994-01-01
Unlike fluid displacement due to regional hydraulic head, thermoconvetive motions are generally slow. The thermal impacts of such movements are very weak, whereas their chemical impacts may be significant because of their cumulated effects over geologic time. For nonhorizontal thick sedimentary reservoirs, the fluid velocity due to thermal convection can be accurately approximated by an explicit function of the dip of the reservior, the permeability and the difference in thermal conductivity between the aquifer and the confining beds. The latter parameter controls the rotation direction of the flow and, for clastic reservoirs bounded by impervious clayey media, fluid moves up the slope along the caprock layer. As the fluid velocity is small, the major rock-forming minerals control the fluid composition by thermodynamic equilibrium. Thus, whereas the volume of redistributed mineral depends on the volume of water circulated, the localization of porosity enhancement is strongly controlled by the reservoir mineralogy. With realistic values of permeability and layer thickness, several per cent of secondary porosity per million years can be created or lost at shallow depth (less than 2 km), depending on the chlorinity, the set of representative minerals and the temperature. In sandstone resevoirs and high-chlorinity calcarenite resoervoirs, the porosity decreases under the caprock where hydrocarbons can accumulate. In chlorinity calcarenite resevoirs, the porosity decreases under the caprock where hydrocarbons can accumulate. In chloride-depleted carbonate aquifers, the simulataneous control by carbonates, silica and aluminosilicates can produce a decrease of porosity above the bedrock and an enhancement of porosity under the caprock. However, computations show that the quality of the upper part of the reservoir is mainly reduced by the precipitation of silica and clays.
Elliott, J.E.; Henny, Charles J.; Harris, M.L.; Wilson, L.K.; Norstrom, R.J.
1999-01-01
We investigated chlorinated hydrocarbon contaminants in aquatic mustelid species on the Fraser and Columbia Rivers of northwestern North America. Carcasses of river otter (Lutra canadensis) (N=24) and mink (Mustela vison) (N=34) were obtained from commercial trappers during the winters of 1990-91 and 1991a??92. Pooled liver samples were analyzed for organochlorine pesticides, polychlorinated biphenyls (PCBs), including non-ortho congeners, polychlorinated dibenzo-p-dioxins (PCDDs) and dibenzofurans (PCDFs). Most samples contained detectable concentrations of DDE, PCBs, although there was substantial variability in patterns and trends among neighboring samples. Concentrations of DDE were in some mink and several otter samples from the lower Columbia River elevated (to 4700 g/kg wet weight); excluding one mink sample from the Wenatchee area, mean DDE levels generally decreased between 1978a??79 and 1990a??92. PCBs were present in all samples. PCB concentrations in otter livers collected from the lower Columbia were ten-fold lower than measured a decade previously; nevertheless, a sample taken near Portland had a mean concentration of 1500 g/kg, within a range of concentrations associated with reproductive effects in captive mink. Concentrations of 2,3,7,8-TCDD and TCDF were generally below detection limits, except for one otter collected near a pulp mill at Castlegar, on the upper Columbia, with 11 ng TCDD/kg in liver. Elevated concentrations of higher chlorinated PCDD/Fs, probably resulting from use of chlorophenolic wood preservatives, were found in both species; one otter sample from the lower Columbia had 2200 ng OCDD/kg. International TCDD toxic equivalent levels in mink (31 ng/kg) and otter (93 ng/kg) from the lower Columbia River approached toxicity thresholds for effects on reproduction in ranch mink.
The use of gamma radiation for removal of pesticides from waste water
NASA Astrophysics Data System (ADS)
Dessouki, A. M.; Aly, H. F.; Sokker, H. H.
1999-01-01
In the present study, a try was made to explain the degradation kinetics due to irradiation of aqueous solutions of some active ingredient pesticides. These pesticides are as follows: one type of triazine herbicide Ametryn and one type of carbamate insecticide (Applaud) and two types of chlorinated organic pesticides, Aldrin and Chlorothalonil. Factors affecting the radiolysis of these pesticides such as the pesticide concentration, irradiation dose, dose rate and pH of the solutions were studied. Ametryn, Applaud, Chlorothalonil and Aldrin insecticides were degraded by γ-radiation and in the case of the chlorinated pesticides hydrochloric acid was detected. The pH effect has proved to vary according to the type of the pesticide and little degradation was observed in allkaline medium, while more degradation of the pesticides in the neutral medium was observed depending on the type of pesticide and on its chemical structure. However, the degradation in the acid medium was even higher. A drop in pH was observed and may be attributed to the degradation of the pesticide molecules to lower molecular weight compounds, such as organic acids. A combined treatment of gamma irradiation and conventional methods was applied and the effect of different additives such as nitrogen and oxygen showed that nitrogen did not enhance the degradation, while an enhancement in the degradation process was observed when oxygen was added. Experiments on the adsorption of these pesticides on certain polymeric materials and on Granular Activated Carbon (GAC), showed that GAC has the highest adsorption capacity. It may be concluded that the radiation degradation followed by adsorption of the toxic pesticide pollutants and their removal from wastewater down to concentrations not exceeding the maximum permissible concentration (MPC), according to international standards, proved to be better than the conventional methods of purification.
A kinetics investigation of several reactions involving chlorine containing compounds
NASA Technical Reports Server (NTRS)
Davis, D. D.
1978-01-01
The technique of flash photolysis-resonance fluorescence was utilized to study nine reactions of stratospheric importance. The tropospheric degradation reactions of seven halogenated hydrocarbons were studied to assess their possible influx into the stratosphere. There are reactions of either Cl, OH, or O(3P) species with hydrogenated species, O3 or chlorinated compounds. Apart from the kinetic measurements, the quantum yield for the production of O(1D) from O3 in the crucial wavelength region of 293 to 316.5 nm was studied by utilizing a narrow wavelength laser as the photolysis source. The product formation was monitored by measuring the fluorescence of NO2 formed through O(1D) reaction with N2O followed by NO reaction with O3 to give NO2.
Population kinetics on K alpha lines of partially ionized Cl atoms.
Kawamura, Tohru; Nishimura, Hiroaki; Koike, Fumihiro; Ochi, Yoshihiro; Matsui, Ryoji; Miao, Wen Yong; Okihara, Shinichiro; Sakabe, Shuji; Uschmann, Ingo; Förster, Eckhart; Mima, Kunioki
2002-07-01
A population kinetics code was developed to analyze K alpha emission from partially ionized chlorine atoms in hydrocarbon plasmas. Atomic processes are solved under collisional-radiative equilibrium for two-temperature plasmas. It is shown that the fast electrons dominantly contribute to ionize the K-shell bound electrons (i.e., inner-shell ionization) and the cold electrons to the outer-shell bound ones. Ratios of K alpha lines of partially ionized atoms are presented as a function of cold-electron temperature. The model was validated by observation of the K alpha lines from a chlorinated plastic target irradiated with 1 TW Ti:sapphire laser pulses at 1.5 x 10(17) W/cm(2), inferring a plasma temperature of about 100 eV on the target surface.
NASA Technical Reports Server (NTRS)
Miyoshi, K.; Shigaki, H.; Buckley, D. H.
1982-01-01
X-ray photoelectron spectroscopy analyses and hardness experiments were conducted with cleaved magnesium oxide /001/ surfaces. The magnesium oxide bulk crystals were cleaved into specimens along the /001/ surface, and indentations were made on the cleaved surface in laboratory air, in nitrogen gas, or in degassed mineral oil with and without an additive while not exposing specimen surface to any other environment. The various additives examined contained sulfur, phosphorus, chlorine, or oleic acid. The sulfur-containing additive exhibited the highest hardness and smallest dislocation patterns evidencing plastic deformation; the chlorine-containing additive exhibited the lowest hardness and largest dislocation patterns evidencing plastic deformation. Hydrocarbon and chloride (MgCl2) films formed on the magnesium oxide surface. A chloride film was responsible for the lowest measured hardness.
DOE Office of Scientific and Technical Information (OSTI.GOV)
Carlberg, G.E.; Ofstad, E.B.; Drangsholt, H.
1983-01-01
Moss and lichen samples from eleven remote sites from all parts of Norway were analyzed for persistent chlorinated hydrocarbons. The highest and lowest concentration levels were found in the most southwesterly and northerly locations, respectively. Moss and lichen samples from one site were also analyzed for other organic micropollutants. They were found to contain alkanes, mostly of biogenic origin, PAH and phthalates.
Solid state synthesis of poly(dichlorophosphazene)
Allen, Christopher W.; Hneihen, Azzam S.; Peterson, Eric S.
2001-01-01
A method for making poly(dichlorophosphazene) using solid state reactants is disclosed and described. The present invention improves upon previous methods by removing the need for chlorinated hydrocarbon solvents, eliminating complicated equipment and simplifying the overall process by providing a "single pot" two step reaction sequence. This may be accomplished by the condensation reaction of raw materials in the melt phase of the reactants and in the absence of an environmentally damaging solvent.
Report for Full-Scale Mulch Wall Treatment of Chlorinated Hydrocarbon-Impacted Groundwater
2004-04-13
7.1 Direction of Groundwater Flow Through the Test Area Static water level measurements were taken every quarter after the installation of the...volatile organic compounds, alternate electron acceptors/byproducts and water quality parameters. Potentiometric surface maps showed the groundwater ... groundwater and surface water restrictions 10 Established clear zone (3000 ft by 3000 ft) Building 301 CEA Previously installed soil boring MW-19I 19
Infrared detection of chlorinated hydrocarbons in water at ppb levels of concentrations.
Roy, Gilles; Mielczarski, Jerzy A
2002-04-01
Infrared sensor, based on attenuated total reflection phenomenon, for the detection of chlorinated hydrocarbons (CHCs) represents a big advantage compared to chromatographic and mass spectroscopic techniques since it is a one step detector. Pre-concentration and separation take place in the polymer film with simultaneous identification of pollutants by the infrared beam. The analysis is rapid, sample does not require any initial preparation, and can be easily performed in the field. The main default of the latest version of the sensor was a low sensibility (above 1 ppm) compared to the threshold levels of the contaminants. In the present work, it is documented that the response dynamics of the optical sensor and its sensitivity depend strongly on the diffusion of pollutants through a boundary layer formed between polymer film and the monitored solution and in the polymer film. The reduction of thickness of the boundary layer through a controlled high flow rate, and the optimization of thickness (volume) of polymer films result in a tremendous improvement of the response dynamics. It is demonstrated that the sensor can detect simultaneously six CHCs: monochlorobenzene, 1,2-dichlorobenzene, 1,2,4-trichlorobenzene, chloroform, trichloroethylene, and perchloroethylene in their mixture with a sensitivity as low as a few ppb. This level of detection opens up numerous applications for the optical sensor.
Cardarelli, Ettore; Di Filippo, Gerardina
2009-09-01
Resistivity and induced polarization surveying were originally developed for mineral exploration but are now finding new applications in the field of environmental and engineering geophysics. The present article reports the results of a geophysical survey performed with the aim of identifying a plume of chlorinated hydrocarbons in sedimentary formations of the Pandania plain. The tested site is characterized by three sand and gravel aquifers containing a quantity of clay particles which influence the overall bulk resistivity and chargeability. According to data obtained using shallow boreholes, mainly dense non-aqueous phase liquids were found as contaminants in the first and second aquifer. The aforementioned geo-electrical methods were applied in both two- and three-dimensional approaches. Steel and copper electrodes were used in the process of field data acquisition and the results of the survey were compared. The geophysical survey revealed some anomalies that could be explained by the presence of dense non-aqueous phase liquids in the soil medium. The concept of normalized chargeability facilitates the interpretation of detected induced polarization anomalies. The shape of the plume was inferred from maps of resistivity and chargeability to a depth of 25 m below the surface of the ground.
Landmeyer, James E.
2001-01-01
At contaminated groundwater sites, poplar trees can be used to affect ground-water levels, flow directions, and ultimately total groundwater and contaminant flux to areas downgradient of the trees. The magnitude of the hydrologic changes can be monitored using fundamental concepts of groundwater hydrology, in addition to plant physiology-based approaches, and can be viewed as being almost independent of the contaminant released. The affect of poplar trees on the fate of groundwater contaminants, however, is contaminant dependent. Some petroleum hydrocarbons or chlorinated solvents may be mineralized or transformed to innocuous compounds by rhizospheric bacteria associated with the tree roots, mineralized or transformed by plant tissues in the transpiration stream or leaves after uptake, or passively volatilized and rapidly dispersed or oxidized in the atmosphere. These processes also can be monitored using a combination of physiological- or geochemical-based field or laboratory approaches. When combined, such hydrologic and contaminant monitoring approaches can result in a more accurate assessment of the use of poplar trees to meet regulatory goals at contaminated groundwater sites, verify that these goals continue to be met in the future, and ultimately lead to a consensus on how the performance of plant-based remedial strategies (phytoremediation) is to be assessed.
Lacorte, S; Quintana, J; Tauler, R; Ventura, F; Tovar-Sánchez, A; Duarte, C M
2009-12-04
This study presents the optimization and application of an analytical method based on the use of stir bar sorptive extraction (SBSE) gas chromatography coupled to mass spectrometry (GC-MS) for the ultra-trace analysis of POPs (Persistent Organic Pollutants) in Arctic ice. In a first step, the mass-spectrometry conditions were optimized to quantify 48 compounds (polycyclic aromatic hydrocarbons, brominated diphenyl ethers, chlorinated biphenyls, and organochlorinated pesticides) at the low pg/L level. In a second step, the performance of this analytical method was evaluated to determine POPs in Arctic cores collected during an oceanographic campaign. Using a calibration range from 1 to 1800 pg/L and by adjusting acquisition parameters, limits of detection at the 0.1-99 and 102-891 pg/L for organohalogenated compounds and polycyclic aromatic hydrocarbons, respectively, were obtained by extracting 200 mL of unfiltered ice water. alpha-hexachlorocyclohexane, DDTs, chlorinated biphenyl congeners 28, 101 and 118 and brominated diphenyl ethers congeners 47 and 99 were detected in ice cores at levels between 0.5 to 258 pg/L. We emphasise the advantages and disadvantages of in situ SBSE in comparison with traditional extraction techniques used to analyze POPs in ice.
Contaminated environments in the subsurface and bioremediation: organic contaminants.
Holliger, C; Gaspard, S; Glod, G; Heijman, C; Schumacher, W; Schwarzenbach, R P; Vazquez, F
1997-07-01
Due to leakages, spills, improper disposal and accidents during transport, organic compounds have become subsurface contaminants that threaten important drinking water resources. One strategy to remediate such polluted subsurface environments is to make use of the degradative capacity of bacteria. It is often sufficient to supply the subsurface with nutrients such as nitrogen and phosphorus, and aerobic treatments are still dominating. However, anaerobic processes have advantages such as low biomass production and good electron acceptor availability, and they are sometimes the only possible solution. This review will focus on three important groups of environmental organic contaminants: hydrocarbons, chlorinated and nitroaromatic compounds. Whereas hydrocarbons are oxidized and completely mineralized under anaerobic conditions in the presence of electron acceptors such as nitrate, iron, sulfate and carbon dioxide, chlorinated and nitroaromatic compounds are reductively transformed. For the aerobic often persistent polychlorinated compounds, reductive dechlorination leads to harmless products or to compounds that are aerobically degradable. The nitroaromatic compounds are first reductively transformed to the corresponding amines and can subsequently be bound to the humic fraction in an aerobic process. Such new findings and developments give hope that in the near future contaminated aquifers can efficiently be remediated, a prerequisite for a sustainable use of the precious-subsurface drinking water resources.
Zhu, Dongqiang; Pignatello, Joseph J
2005-11-15
A LFER of the type in the title is applied to sorption of numerous compounds to polyethylene and three soils for which sorption to natural organic matter (NOM) is presumed dominant. It provides fractional contributions to the Gibbs free energy of sorption corresponding to hydrophobic effects, dipolar/polarizability (D/P) effects in excess of the reference state, and the sum of possible specific forces such as H-bonding and pi-pi electron donor-acceptor (pi-pi EDA) interactions in excess of the reference state. Minimal inputs are the isotherm, the n-hexadecane-water partition coefficient and the Abraham pi parameter representing D/P effects. Sorption of all compounds to polyethylene can be described by considering only hydrophobic effects. Sorption of a calibration set of apolar compounds (aromatic and aliphatic hydrocarbons and chlorinated hydrocarbons) to the natural sorbents is well-described by a combination of hydrophobic and D/P effects. For the apolar set, D/P contributes approximately 15-40% (2-8% for cyclohexane) of sorption free energy. D/P effects increase with the degree of chlorination for aliphatic compounds. For aromatic compounds D/P effects increase with fused ring size but do not vary with degree of chlorination and chlorine substitution pattern. H-bonding contributes substantially to sorption of alcohols, and similarly for 2-nonanol and 2,4-dichlorophenol (33-44%). pi-pi EDA forces contribute to phenanthrene sorption in one case. The effects of concentration, sorbent aromaticity (literature NMR), and sorbent polarity [(O + N)/C] on hydrophobic and D/P contributions for all compounds indicate that (a) molecules fill sites of progressively greater hydrophilic character; (b) the energy penalty for cavity formation in the solid decreases with concentration due to plasticization and greater intermolecular contact; (c) sorbent aromatic content more than sorbent polarity controls D/P interactions. Basing free energy on an inert electrostatic chemical environment afforded by n-hexadecane permits evaluation of direct electrostatic forces in NOM that contribute to sorption.
Hamonts, Kelly; Kuhn, Thomas; Vos, Johan; Maesen, Miranda; Kalka, Harald; Smidt, Hauke; Springael, Dirk; Meckenstock, Rainer U; Dejonghe, Winnie
2012-04-15
Chlorinated aliphatic hydrocarbons (CAHs) often discharge into rivers as contaminated groundwater baseflow. Biotransformation, sorption and dilution of CAHs in the impacted river sediments have been reported to reduce discharge, but the effect of temporal variations in environmental conditions on the occurrence and extent of those processes in river sediments is largely unknown. We monitored the reduction of CAH discharge into the Zenne River during a 21-month period. Despite a relatively stable influx of CAHs from the groundwater, the total reduction in CAH discharge from 120 to 20 cm depth in the river sediments, on average 74 ± 21%, showed moderate to large temporal variations, depending on the riverbed location. High organic carbon and anaerobic conditions in the river sediments allowed microbial reductive dechlorination of both chlorinated ethenes and chlorinated ethanes. δ(13)C values of the CAHs showed that this biotransformation was remarkably stable over time, despite fluctuating pore water temperatures. Daughter products of the CAHs, however, were not detected in stoichiometric amounts and suggested the co-occurrence of a physical process reducing the concentrations of CAHs in the riverbed. This process was the main process causing temporal variations in natural attenuation of the CAHs and was most likely dilution by surface water-mixing. However, higher spatial resolution monitoring of flow transients in the riverbed is required to prove dilution contributions due to dynamic surface water-groundwater flow exchanges. δ(13)C values and a site-specific isotope enrichment factor for reductive dechlorination of the main groundwater pollutant vinyl chloride (VC) allowed assessment of changes over time in the extent of both biotransformation and dilution of VC for different scenarios in which those processes either occurred consecutively or simultaneously between 120 and 20 cm depth in the riverbed. The extent of reductive dechlorination of VC ranged from 27 to 89% and differed spatially but was remarkably stable over time, whereas the extent of VC reduction by dilution ranged from 6 to 94%, showed large temporal variations, and was often the main process contributing to the reduction of VC discharge into the river. Copyright © 2012 Elsevier Ltd. All rights reserved.
NASA Astrophysics Data System (ADS)
Buch, Arnaud; Belmahdi, Imene; Szopa, Cyril; Freissinet, Caroline; Glavin, Daniel P.; Eigenbrode, Jennifer; Summons, Roger; Miller, Kristen; Coll, Patrice; cabane, Michel; Navarro-Gonzalez, Rafael; Stern, Jennifer; Coscia, David; Teinturier, Samuel; Bonnet, Jean-Yves; Dequaire, Tristan; Mahaffy, Paul; MSL Science Team
2016-10-01
Sample Analysis at Mars (SAM) is one of the instruments of the MSL mission. Three analytical devices are onboard SAM: the Tunable Laser Spectrometer (TLS), the Gas Chromatography (GC) and the Mass Spectrometer (MS). To adapt the nature of a sample to the analytical devices used on SAM, a sample preparation and gas processing system is implemented with (a) a pyrolysis system, (b) wet chemistry: MTBSTFA and TMAH (c) the hydrocarbon trap (silica beads, Tenax® TA and Carbosieve G) which is employed to concentrate volatiles released from the sample prior to GC-MS analysis [1].Volatile compounds and abundant chlorinated hydrocarbons have been detected with SAM when analyzing samples collected in several sites explored by Curiosity rover. Some volatile compounds (chlorinated and non-chlorinated) come from the degradation of the MTBSTFA under high temperature or by the reaction of Martian oxychlorine compounds (present in the samples) with terrestrial carbon coming from the derivatization agent (MTBSTFA) used in SAM [2,3]. But other chlorinated compounds do not follow this pathway. For example, Chlorobenzene has been detected by SAM but it cannot be formed by the reaction of MTBSTFA and perchlorates. Then, two other reaction pathways for chlorobenzene were therefore proposed: (1) reactions between the volatile thermal degradation products of perchlorates (e.g. O2, Cl2 and HCl) and Tenax® and (2) the interaction of perchlorates (T>200°C) with organic material from Mars's soil such as benzenecarboxylates. However, even if major part of the chlorobenzene detected has been identified as Martian origin [4] it is important to list all the potential byproducts able to be released from the Tenax®.Thus, this study inventory all the possible compounds which are originated from Tenax®, MTBSTFA and their interaction with perchlorate.References: [1] Buch, A. et al. (2009) J chrom. A, 43, 143-151. [2] Glavin, D., A. et al. (2013), LPSC. [3] Eigenbrode, J. et al. (2013), LPSC. [4] Freissinet, C. et al., JGR (2015)
NASA Technical Reports Server (NTRS)
Skinner, S. Ballou
1991-01-01
Chlorofluorocarbons (CFC's) in the atmosphere are believed to present a major environmental problem because they are able to interact with and deplete the ozone layer. NASA has been mandated to replace chlorinated solvents in precision cleaning, cleanliness verification, and degreasing of aerospace fluid systems hardware and ground support equipment. KSC has a CFC phase-out plan which provides for the elimination of over 90 percent of the CFC and halon use by 1995. The Materials Science Laboratory and KSC is evaluating four analytical methods for the determination of nonvolatile residues removal by water: (1) infrared analyses using an attenuated total reflectance; (2) surface tension analyses, (3) total organic content analyses, and (4) turbidity analyses. This research project examined the ultrasonic-turbidity responses for 22 hydrocarbons in an effect to determine: (1) if ultrasonics in heated water (70 C) will clean hydrocarbons (oils, greases, gels, and fluids) from aerospace hardware; (2) if the cleaning process by ultrasonics will simultaneously emulsify the removed hydrocarbons in the water; and (3) if a turbidimeter can be used successfully as an analytical instrument for quantifying the removal of hydrocarbons. Sixteen of the 22 hydrocarbons tested showed that ultrasonics would remove it at least 90 percent of the contaminated hydrocarbon from the hardware in 10 minutes or less giving a good ultrasonic-turbidity response. Six hydrocarbons had a lower percentage removal, a slower removal rate, and a marginal ultrasonic-turbidity response.
Occurrence of Organic Contaminants in Lower Reaches of River Ganges, India
NASA Astrophysics Data System (ADS)
Dutta Gupta, S.; Bhattacharya, A.; Mukherjee, A.; Bhattacharya, J.
2016-12-01
The Gangetic plain of eastern India has been long known as the "bread basket" of the Indian subcontinent. However, indiscriminate use of pesticides in the agricultural fields is to increase crop production. These resulted to increased vulnerability of pesticide pollution of the hydrological systems of the area, potentially exposing to significant human health consequences. Our present study delineate pesticides occurrence in lower Ganges in West Bengal. The major organic contaminants regularly detected in the studied reaches of the Ganges belong to wide range of herbicides and insecticides, which especially include organochlorides and organophosphates such as Aldrin, Alachlor, Lindane, Malathion, Chlorpyrifos and Methyl parathion. Results show Alachlor and Malathion were the most abundant organic contaminant in the river. Among the other pesticides, one of the most venomous substances, Malathion has been noticed from the last year insecticide screening study. The mean concentration of river water Malathion was found to be 5 times higher than the maximum concentration limit (MCL). Presence of Malathion or its derivative Malaoxon in river water is suspected to be caused by agricultural run-off and it showed a good correlation with river water chlorine concentrations.
Shelton, Keith L.
2009-01-01
Rationale Because the toxicity of many inhalants precludes evaluation in humans, drug discrimination, an animal model of subjective effects, can be used to gain insights on their poorly understood abuse-related effects. Objectives The purpose of the present study was to train a prototypic inhalant that has known abuse liability, 1,1,1-trichloroethane (TCE), as a discriminative stimulus in mice and compare it to other classes of inhalants. Methods Eight B6SJLF1/J mice were trained to discriminate 10 min of exposure to 12000 ppm inhaled TCE vapor from air and seven mice were trained to discriminate 4000 ppm TCE from air. Tests were then conducted to characterize the discriminative stimulus of TCE and to compare it to representative aromatic and chlorinated hydrocarbon vapors, volatile halogenated anesthetics as well as an odorant compound. Results Only the 12000 ppm TCE versus air discrimination group exhibited sufficient discrimination accuracy for substitution testing. TCE vapor concentration- and exposure time-dependently substituted for the 12000 ppm TCE vapor training stimulus. Full substitution was produced by trichloroethylene, toluene, enflurane and sevoflurane. Varying degrees of partial substitution were produced by the other volatile test compounds. The odorant, 2-butanol, did not produce any substitution for TCE. Conclusions The discriminative stimulus effects of TCE are shared fully or partially by chlorinated and aromatic hydrocarbons as well as by halogenated volatile anesthetics. However, these compounds can be differentiated from TCE both quantitatively and qualitatively. It appears that the degree of similarity is not solely a function of chemical classification but may also be dependent upon the neurochemical effects of the individual compounds. PMID:18972104
2003-04-04
processes in the subsurface. This substrate is typically molasses although these substrates can include high fructose corn syrup , whey, etc. (Suthersan...typically comprised of a carbohydrate such as molasses, whey, high fructose corn syrup , lactate, butyrate, or benzoate). Through periodic subsurface...this purpose; other carbohydrates such as high fructose corn syrup and whey can also be effective. This approach has been accepted by regulators and
Organic Molecules in the Sheepbed Mudstone, Gale Crater, Mars
NASA Technical Reports Server (NTRS)
Freissinet, C.; Glavin, D. P.; Mahaffy, P. R.; Miller, K. E.; Eigenbrode, J. L.; Summons, R. E.; Brunner, A. E.; Buch, A.; Szopa, C.; Archer, P. D.;
2014-01-01
The Sample Analysis at Mars (SAM) instrument on the Curiosity rover is designed to determine the inventory of organic and inorganic volatiles thermally released from solid samples using a combination of evolved gas analysis (EGA), gas chromatography mass spectrometry (GCMS), and tunable laser spectroscopy. Here we report on various chlorinated hydrocarbons (chloromethanes, chlorobenzene and dichloroalkanes) detected at elevated levels above instrument background at the Cumberland (CB) drill site, and discuss their possible sources.
Impact of Landfill Closure Designs on Long-Term Natural Attenuation of Chlorinated Hydrocarbons
2008-10-01
Parsons, 2004). The bioreactor provides a source of leachable organic material for the CAH-contaminated aquifer, which is used by native microorganisms ...bioreactor concept is not new. “Bioreactor” is a generic term for a system that degrades contaminants using microorganisms . Bioreactors have been used in a...of CAHs (USEPA, 1998) and using prior experience monitoring enhanced bioremediation sites. The bioreactor was sampled to monitor the chemical and
de Mora, Stephen; Tolosa, Imma; Fowler, Scott W; Villeneuve, Jean-Pierre; Cassi, Roberto; Cattini, Chantal
2010-12-01
The composition and spatial distribution of various petroleum hydrocarbons (PHs), comprising both aliphatic and polycyclic aromatic hydrocarbons (PAHs), and selected chlorinated pesticides and PCBs were measured in biota and coastal sediments from seven countries in the Persian Gulf and the Gulf of Oman (Bahrain, Iran, Kuwait, Oman, Qatar, Saudi Arabia and the United Arab Emirates). Evidence of extensive marine contamination with respect to organochlorinated compounds and PHs was not observed. Only one site, namely the BAPCO oil refinery in Bahrain, was considered to be chronically contaminated. Comparison of the results from this survey for Σ DDTs and Σ PCBs in rock oysters from the Gulf of Oman with similar measurements made at the same locations over the past two decades indicates a temporal trend of overall decreasing Σ PCB concentrations in oysters, whereas Σ DDTs levels have little changed during that period. Copyright © 2010 Elsevier Ltd. All rights reserved.
Preparation of B-trichloroborazine
NASA Technical Reports Server (NTRS)
Riccitiello, Salvatore R.; Hsu, Ming-Ta S.; Chen, Timothy S.
1987-01-01
The present invention relates to a method of preparing B-trichloroborazine. Generally, the method includes the combination of gaseous boron trichloride in an anhydrous aprotic organic solvent followed by addition of excess gaseous ammonia at ambient temperature or below. The reaction mixture is heated to about 100 to 140 C followed by cooling, removal of the solid ammonium chloride at ambient temperature, distillation of the solvent under vacuum if necessary at a temperature of up to about 112 C, and recovery of the B-trichloroborazine. Solvents include toluene, benzene, xylene, chlorinated hydrocarbons, chlorinated aromatic compounds, or mixtures thereof. Toluene is a preferred solvent. The process provides a convenient synthesis of a material which often decomposes on standing. B-trichloroborazine is useful in a number of chemical reactions, and particularly in the formation of high temperature inorganic polymers and polymer precursors.
Performance of PAHs emission from bituminous coal combustion.
Yan, Jian-Hua; You, Xiao-Fang; Li, Xiao-Dong; Ni, Ming-Jiang; Yin, Xue-Feng; Cen, Ke-Fa
2004-12-01
Carcinogenic and mutagenic polycyclic aromatic hydrocarbons (PAHs) generated in coal combustion have caused great environmental health concern. Seventeen PAHs (16 high priority PAHs recommended by USEPA plus Benzo[e]pyrene) present in five raw bituminous coals and released during bituminous coal combustion were studied. The effects of combustion temperature, gas atmosphere, and chlorine content of raw coal on PAHs formation were investigated. Two additives (copper and cupric oxide) were added when the coal was burned. The results indicated that significant quantities of PAHs were produced from incomplete combustion of coal pyrolysis products at high temperature, and that temperature is an important causative factor of PAHs formation. PAHs concentrations decrease with the increase of chlorine content in oxygen or in nitrogen atmosphere. Copper and cupric oxide additives can promote PAHs formation (especially the multi-ring PAHs) during coal combustion.
Giesy, J.P.; Verbrugge, D.A.; Othoudt, R. A.; Bowerman, W.W.; Mora, M.A.; Jones, P.D.; Newsted, J.L.; Vandervoort, C.; Heaton, S. N.; Aulerich, R.J.; Bursian, S.J.; Ludwig, J. P.; Ludwig, M.; Dawson, G. A.; Kubiak, T.J.; Best, D. A.; Tillitt, D. E.
1994-01-01
Fishes of the Great Lakes contain hazardous chemicals such as synthetic halogenated hydrocarbons and metals. These fish can move from the lakes into the Great Lakes tributaries of Michigan. In doing so, they transport concentrationsof contaminants which may represent a risk to wildlife. Concentrations of mercury (Hg), total polychlorinated biphenyls (PCBs), 2,3,7,8-tetrachlorodibenzo-p-dioxin equivalents (TCDD-EQ), total DDT complex, aldrin, endrin, dieldrin, heptachlor, heptachlor epoxide, lindane, hexachlorobenzene, cis-chlordane, oxychlordane, endosulfan-I, methoxychlor, trans-chlordane, and trans-nonachlor were determined in composite samples of fishes from above and below Michigan hydroelectric dams, which separate the fishes which have access to the Great Lakes from fishes that do not. Mean concentrations of total PCBs, TCDD-EQ, DDT, and most of the other pesticides were greater in composite samples of six species of fishes from below than above the dams on the Au Sable, Manistee, and Muskegon Rivers. Concentrations of mercury, were the same or greater above the dams than below. However, this difference was statistically significant only on the Au Sable. Mercury concentrations ranged from less than 0.05 mg/kg to 0.73 mg Hg/kg, ww. Total concentrations of PCBs ranged from 0.02 to 1.7 mg/kg, ww. Concentrations of 2,3,7,8-tetrachlordibenzo-p-dioxin equivalents varied among fishes and locations. The concentrations of TCDD-EQ ranged from 2.4 to 71 μg/kg, ww, with concentrations in carp being the greatest. Concentrations of TCDD-EQ were greater than the concentrations which would be expected to occur, due solely to the presence of polychlorinated dibenzo-p-dioxins (PCDD), polychlorinated dibenzofurans (PCDF), and technical mixtures of PCBs.
Reif, Andrew G.; Sloto, Ronald A.
1997-01-01
The Schuylkill River flows through Valley Forge National Historical Park in Lower Providence and West Norriton Townships in Montgomery County, Pa. The concentration of selected metals, pesticides, semivolatile organic compounds, and total carbon in stream-bottom sediments from Valley Forge National Historical Park were determined for samples collected once at 12 sites in and around the Schuylkill River.Relatively low concentrations of arsenic, chromium, copper, and lead were detected in all samples. The concentrations of these metals are similar to concentrations in other stream-bottom sediment samples collected in the region. The concentrations of iron, manganese, and zinc were elevated in samples from four sites in the Schuylkill River, and the concentration of mercury was elevated in a sample from an impoundment along the river.The organophosphorus insecticide diazinon was detected in relatively low concentrations in half of the 12 samples analyzed. The organo-chlorine insecticide DDE was detected in all 12 samples analyzed; dieldrin was detected in 10 samples, chlordane, DDD, and DDT were detected in 9 samples, and heptachlor epoxide was detected in one sample. The concentrations of organo-chlorine and organophosphorus insecticides were relatively low and similar to concentrations in samples collected in the region.Detectable concentrations of 17 semivolatile organic compounds were measured in the 12 samples analyzed. The most commonly detected compounds were fluoranthene, phenanthrene, and pyrene. The maximum concentration detected was 4,800 micrograms per kilogram of phenanthrene. The highest concentrations of compounds were detected in Lamb Run, a small tributary to the Schuylkill River with headwaters in an industrial corporate center. The concentration of compounds in the Schuylkill River below Lamb Run is higher than the Schuylkill River above Lamb Run, indicating that sediment from Lamb Run is increasing the concentration of semivolatile organic compounds in sediment from the Schuylkill River. Concentrations of semivolatile organic compounds are lower in sediment from the Schuylkill River below Myer's Run than above Myer's Run because of the addition of relatively clean sediment from Myer's Run. Samples collected from the floodplain, impounding basin, and wetland along the Schuylkill River contained the lowest concen-trations of semivolatile organic compounds.Detectable concentrations of polychlorinated biphenyls (PCB's) were measured in 11 of the 12 samples analyzed. The maximum PCB concentration was 37 micrograms per kilogram. Sediment samples from Lamb Run contained the highest concentrations of semivolatile organic compounds and PCB's.
Yager, R.M.; Bilotta, S.E.; Mann, C.L.; Madsen, E.L.
1997-01-01
A combination of hydrogeological, geochemical, and microbiological methods was used to document the biotransformation of trichloroethene (TCE) to ethene, a completely dechlorinated and environmentally benign compound, by naturally occurring microorganisms within a fractured dolomite aquifer. Analyses of groundwater samples showed that three microbially produced TCE breakdown products (cis-1,2-dichloroethene, vinyl chloride, and ethene) were present in the contaminant plume. Hydrogen (H2) concentrations in groundwater indicated that iron reduction was the predominant terminal electron-accepting process in the most contaminated geologic zone of the site. Laboratory microcosms prepared with groundwater demonstrated complete sequential dechlorination of TCE to ethene. Microcosm assays also revealed that reductive dechlorination activity was present in waters from the center but not from the periphery of the contaminant plume. This dechlorination activity indicated that naturally occurring microorganisms have adapted to utilize chlorinated ethenes and suggested that dehalorespiring rather than cometabolic, microbial processes were the cause of the dechlorination. The addition of pulverized dolomite to microcosms enhanced the rate of reductive dechlorination, suggesting that hydrocarbons in the dolomite aquifer may serve as electron donors to drive microbially mediated reductive dechlorination reactions. Biodegradation of the chlorinated ethenes appears to contribute significantly to decontamination of the site.A combination of hydrogeological, geochemical, and microbiological methods was used to document the biotransformation of trichloroethene (TCE) to ethene, a completely dechlorinated and environmentally benign compound, by naturally occurring microorganisms within a fractured dolomite aquifer. Analyses of groundwater samples showed that three microbially produced TCE breakdown products (cis-1,2-dichloroethene, vinyl chloride, and ethene) were present in the contaminant plume. Hydrogen (H2) concentrations in groundwater indicated that iron reduction was the predominant terminal electron-accepting process in the most contaminated geologic zone of the site. Laboratory microcosms prepared with groundwater demonstrated complete sequential dechlorination of TCE to ethene. Microcosm assays also revealed that reductive dechlorination activity was present in waters from the center but not from the periphery of the contaminant plume. This dechlorination activity indicated that naturally occurring microorganisms have adapted to utilize chlorinated ethenes and suggested that dehalorespiring rather than cometabolic, microbial processes were the cause of the dechlorination. The addition of pulverized dolomite to microcosms enhanced the rate of reductive dechlorination, suggesting that hydrocarbons in the dolomite aquifer may serve as electron donors to drive microbially mediated reductive dechlorination reactions. Biodegradation of the chlorinated ethenes appears to contribute significantly to decontamination of the site.
Owolabi, Moses S; Padilla-Camberos, Eduardo; Ogundajo, Akintayo L; Ogunwande, Isiaka A; Flamini, Guido; Yusuff, Olaniyi K; Allen, Kirk; Flores-Fernandez, Karen Isabel; Flores-Fernandez, Jose Miguel
2014-01-01
Insecticidal activity of essential oil extracted from Morinda lucida was tested on pulse beetle Callosobruchus maculatus, which is a pest that causes serious damage to several pulses. The insecticidal activity was compared with two pesticides, Phostoxin and Primo-ban-20. 120 mixed sex adult C. maculatus were introduced, along with 30 g of cowpeas. Four concentrations (0.40, 0.20, 0.10, and 0.05 μg/mL) of the M. lucida essential oil, Phostoxin, and Primo-ban-20 were tested. Essential oil chemical composition was analyzed by GC-MS. M. lucida essential oil showed a high toxicological effect, producing 100% mortality after 72 hours at a dose of 0.20 μg/mL. M. lucida essential oil had a potent insecticidal activity (LC90 = 0.629 μg/mL) compared to both pesticides, Phostoxin (LC90 = 0.652 μg/mL) and Primo-ban-20 (LC90 = 0.726 μg/mL), at 24 h. The main compounds of the essential oil were the oxygenated monoterpenoids, 1,8-cineole (43.4%), and α-terpinyl acetate (14.5%), and the monoterpene hydrocarbons, mostly sabinene (8.2%) and β-pinene (4.0%). Results clearly indicate that M. lucida essential oil can be used as an effective alternative for pulse beetle C. maculatus control, and it could be tested against other pulse beetles affecting Asia and Africa and throughout the world, thereby reducing use of synthetic pesticides.
Dominierende Prozesse bei der thermischen In-situ-Sanierung (TISS) kontaminierter Geringleiter
NASA Astrophysics Data System (ADS)
Hiester, Uwe; Bieber, Laura
2017-09-01
Contaminants such as chlorinated, aromatic or polycyclic aromatic hydrocarbons (CHC, BTEX, PAH) or mineral oil hydrocarbons (TPH) constitute a prevalent threat to water resources. The significant storage capacity of low permeable soils (aquitards) leads to their long-term contamination. In situ thermal remediation (ISTR) proved to work successfully in treating these soils. Thus, the area of ISTR application grew continuously over the past 10 years. The dominating processes during the remediation can vary considerably, depending on hydrogeological and geological boundary conditions and the contamination itself. This article summarizes the application for in-situ thermal remediation (ISTR) in low permeable soils and aquitards for soil and groundwater treatment. Dominating remediation processes during volatile organic compound (VOC) and residual oil phase recovery are presented. The processes are illustrated by project examples.
2004-12-17
other substrates can also be used, including high fructose corn syrup , whey, etc. Through this subsurface molasses injection, the existing aerobic or...is not the only carbohydrate material that can be used for this purpose; other carbohydrates such as high fructose corn syrup and whey can also be... fructose corn syrup , lactate, butyrate, or benzoate). Through periodic subsurface substrate injection, the ERD technology alters existing aerobic or mildly
Anaerobic Degradation of C1 and C2 Chlorinated Hydrocarbons
1985-12-01
two substrates, chloroform (CF) and dichloromethane (DCH), degradative pathways were examined through use of radioisotopes . An aqueous stock solution...sealed with a TeflonTH-lined rubber septum and aluminum crimp cap, and stored in a refrigerator when " not in use. In the case of DCM, the radioisotope was...sealed LSV, which was then shaken to dissolve the radioisotope . Another 0.5 mL headspace samp]e from the serum bottle was injected into the GC, for
1987-04-01
biological effects (benthic community structure, bioaccumulation , fish histopathology) indi- cators were used along with historical data to iden...chlorinated pesticides, plasticizers (pthalates), and poly- nuclear aromatic hydrocarbons (PAH)]. Over 425 point and nonpoint discharges have been identified...collected sediments (i.e., amphipod blo- assays as a lethal indicator and oyster larvae bioassays as a sublethal Indi- cator), bioaccumulation of
Bioenvironmental Engineer’s Guide to TVA-1000B Toxic Vapor Analyzer
2014-01-01
chemicals including aromatics, unsaturated chlorinated hydrocarbons, aldehydes , ketones , ethylene oxide, hydrogen sulfide, and glycol ether solvents. The...Dimethoxyethane 9.65 Diethyl ketone 9.32 Ethyl amine 8.86 1,1-Dimethylhydrazine 7.28 Diethyl sulfide 8.43 Ethyl benzene 8.76 1,2-Dibromoethene 9.45...Chemical IP (eV) Chemical IP (eV) Chemical IP (eV) Freon 13 (chlorotrifluoromethane) 12.91 Isobutyric acid 10.02 Methyl butyl ketone 9.34
Kamiya, Yuta; Iijima, Akihiro; Ikemori, Fumikazu; Okuda, Tomoaki; Ohura, Takeshi
2016-01-01
Chlorinated polycyclic aromatic hydrocarbons (ClPAHs) are novel species of environmental contaminants whose possible sources remain unclear. The occurrence of ClPAHs within total suspended particles (TSP) is compared with weekly air samples at two sites of differing characteristics (industrial and residential) in the megacity of Nagoya, Japan. Samples were collected over 12 months during 2011–2012. All 24 species of targeted ClPAHs were detected at both industrial and residential sites, where mean concentrations of total ClPAHs in TSP were 20.7 and 14.1 pg/m3, respectively. High concentrations at the industrial site were frequently observed during winter, suggesting potent seasonal ClPAH sources there. Positive matrix factorization modeling of particulate ClPAH source identification and apportioning were conducted for datasets including ClPAHs, PAHs, elements and ions, plus elemental carbons in TSP. Eight factors were identified as possible ClPAH sources, with estimates that the dominant one was a specific source of ClPAH emission (31%), followed by traffic (23%), photodegradable and semi-volatile species (18%), long-range transport (11%), and industry and oil combustion (10%). Source contributions of ClPAHs differed substantially from those of PAHs. This suggests specific and/or potent ClPAH sources in the local area, and that the production mechanisms between ClPAHs and PAHs are substantially different. PMID:27922081
DOE Office of Scientific and Technical Information (OSTI.GOV)
Wallace, L.A.; Pellizzari, E.; Hartwell, T.
A pilot study to test methods of estimating personal exposures to toxic substances and corresponding body burdens was carried out between July and December 1980. Individual exposures to about a dozen volatile organic compounds in air and drinking water were measured for volunteers in New Jersey and North Carolina. Breath samples were also collected from all subjects. About 230 personal air samples, 170 drinking water samples, 66 breath samples, and 4 food samples (16 composites) were analyzed for the target chemicals. Ten compounds were present in air and eight were transmitted mainly through that medium. Chloroform and bromodichloromethane were predominantlymore » transmitted through water and beverages. Food appeared to be a miner route of exposure, except possibly for trichloroethylene in margarine. Seven compounds were present in more than half of the breath samples. Diurnal and seasonal variations were noted in air and water concentrations of some compounds. Some, but not all, of the potentially occupationally exposed individuals had significantly higher workplace exposures to several chemicals. Distributions of air exposures were closer to log normal than normal for most chemicals. Several chemicals were highly correlated with each other in personal air samples, indicating possible common sources of exposures. Compounds detected included benzene, chlorinated aromatic hydrocarbons, chlorinated aliphatic hydrocarbons, halogens and vinyl chloride.« less
Ma, Yan; Shi, Yi; Hou, Deyi; Zhang, Xi; Chen, Jiaqi; Wang, Zhifen; Xu, Zhu; Li, Fasheng; Du, Xiaoming
2017-04-01
Mechanical soil aeration is a simple, effective, and low-cost soil remediation technology that is suitable for sites contaminated with volatile chlorinated hydrocarbons (VCHs). Conventionally, this technique is used to treat the mixed soil of a site without considering the diversity and treatability of different soils within the site. A laboratory test was conducted to evaluate the effectiveness of mechanical soil aeration for remediating soils of different textures (silty, clayey, and sandy soils) along a vertical profile at an abandoned chloro-alkali chemical site in China. The collected soils were artificially contaminated with chloroform (TCM) and trichloroethylene (TCE). Mechanical soil aeration was effective for remediating VCHs (removal efficiency >98%). The volatilization process was described by an exponential kinetic function. In the early stage of treatment (0-7hr), rapid contaminant volatilization followed a pseudo-first order kinetic model. VCH concentrations decreased to low levels and showed a tailing phenomenon with very slow contaminant release after 8hr. Compared with silty and sandy soils, clayey soil has high organic-matter content, a large specific surface area, a high clay fraction, and a complex pore structure. These characteristics substantially influenced the removal process, making it less efficient, more time consuming, and consequently more expensive. Our findings provide a potential basis for optimizing soil remediation strategy in a cost-effective manner. Copyright © 2016. Published by Elsevier B.V.
Li, Ning; Du, Jian; Yang, Jing; Fan, Qiang; Tian, Wen
2017-11-01
A gas standard mixture containing 22 chlorinated hydrocarbons in high purity nitrogen was prepared using a two-step weighing method and a gasifying apparatus developed in-house. The concentration of each component was determined using a gas chromatograph with flame ionization detection (GC/FID). Linear regression analysis of every component was performed using the gas standard mixture with concentrations ranging from 1 to 10 μmol/mol, showing the complete gasification of volatile organic compound (VOCs) species in a selected cylinder. Repeatability was also examined to ensure the reliability of the preparation method. In addition, no significant difference was observed between domestic treated and imported treated cylinders, which were conducive to reduction of the cost of raw materials. Moreover, the results of stability testing at different pressures and long-term stability tests indicated that the gas standard at 1 μmol/mol level with relative expanded uncertainties of 5% was stable above 2 MPa for a minimum of 12 months. Finally, a quantity comparison was conducted between the gas standard and a commercial gas standard from Scott Specialty Gases (now Air Liquide America Specialty Gases). The excellent agreement of every species suggested the favorable accuracy of our gas standard. Therefore, this reference material can be applied to routine observation of VOCs and for other purposes.
Wang, Feidi; Zhang, Haijun; Geng, Ningbo; Ren, Xiaoqian; Zhang, Baoqin; Gong, Yufeng; Chen, Jiping
2018-03-01
The combined toxicity of mixed chemicals is usually evaluated according to several specific endpoints, and other potentially toxic effects are disregarded. In this study, we provided a metabolomics strategy to achieve a comprehensive understanding of toxicological interactions between mixed chemicals on metabolism. The metabolic changes were quantified by a pseudotargeted analysis, and the types of combined effects were quantitatively discriminated according to the calculation of metabolic effect level index (MELI). The metabolomics strategy was used to assess the combined effects of polycyclic aromatic hydrocarbons (PAHs) and short-chain chlorinated paraffins (SCCPs) on the metabolism of human hepatoma HepG2 cells. Our data suggested that exposure to a combination of PAHs and SCCPs at human internal exposure levels could result in an additive effect on the overall metabolism, whereas diverse joint effects were observed on various metabolic pathways. The combined exposure could induce a synergistic up-regulation of phospholipid metabolism, an additive up-regulation of fatty acid metabolism, an additive down-regulation of tricarboxylic acid cycle and glycolysis, and an antagonistic effect on purine metabolism. SCCPs in the mixture acted as the primary driver for the acceleration of phospholipid and fatty acid metabolism. Lipid metabolism disorder caused by exposure to a combination of PAHs and SCCPs should be an important concern for human health. Copyright © 2017 Elsevier Ltd. All rights reserved.
Hamonts, Kelly; Ryngaert, Annemie; Smidt, Hauke; Springael, Dirk; Dejonghe, Winnie
2014-03-01
Chlorinated aliphatic hydrocarbons (CAHs) often discharge into rivers as contaminated groundwater baseflow. As biotransformation of CAHs in the impacted river sediments might be an effective remediation strategy, we investigated the determinants of the microbial community structure of eutrophic, CAH-polluted sediments of the Zenne River. Based on PCR-DGGE analysis, a high diversity of Bacteria, sulfate-reducing bacteria, Geobacteraceae, methanogenic archaea, and CAH-respiring Dehalococcoides was found. Depth in the riverbed, organic carbon content, CAH content and texture of the sediment, pore water temperature and conductivity, and concentrations of toluene and methane significantly contributed to the variance in the microbial community structure. On a meter scale, CAH concentrations alone explained only 6% of the variance in the Dehalococcoides and sulfate-reducing communities. On a cm-scale, however, CAHs explained 14.5-35% of the variation in DGGE profiles of Geobacteraceae, methanogens, sulfate-reducing bacteria, and Bacteria, while organic carbon content explained 2-14%. Neither the presence of the CAH reductive dehalogenase genes tceA, bvcA, and vcrA, nor the community structure of the targeted groups significantly differed between riverbed locations showing either no attenuation or reductive dechlorination, indicating that the microbial community composition was not a limiting factor for biotransformation in the Zenne sediments. © 2013 Federation of European Microbiological Societies. Published by John Wiley & Sons Ltd. All rights reserved.
Bobo, Linda L.; Renn, Danny E.
1980-01-01
Water type in the 241-square mile Porter County watershed in Indiana, was calcium bicarbonate or mixed calcium bicarbonate and calcium sulfate. Concentrations of dissolved chemical constituents in surface water and contents of chlorinated hydrocarbons in streambed samples in the watershed were generally less than water-quality alert limits set by the U.S. Environmental Protection Agency, except in Crooked Creek. During sampling, this stream was affected by sewage, chlorinated hydrocarbons, and two chemical spills. Ranges of on-site field measurements were: specific conductance, from 102 to 1,060 micromhos per centimeter at 25 Celcius; water temperature, from 7.0 to 31.8 Celsius; pH, from 6.8 to 8.9; dissolved oxygen, from 2.5 to 14.9 milligrams per liter and from 27 to 148% saturation; and instantaneous discharge from 0 to 101 cubic feet per second. Concentrations of most dissolved-inorganic constituents (heavy metals and major ions) and dissolved solids did not vary significantly from one sampling period to the next at each site. Dissolved constituents whose concentrations varied significantly were iron, manganese, organic carbon, ammonia, nitrate plus nitrite, organic nitrogen, Kjeldahl nitrogen, and phosphorus. Concentrations of dissolved manganese, organic carbon, dissolved nitrite plus nitrate, and suspended sediment varied seasonally at most sites. Populations and identification of bacteria, phytoplankton, periphyton, and benthic invertebrates indicate a well-balanced environment at most sites, except in Crooked Creek.
Ma, Yan; Du, Xiaoming; Shi, Yi; Xu, Zhu; Fang, Jidun; Li, Zheng; Li, Fasheng
2015-02-01
Mechanical soil aeration has long been regarded as an effective ex-situ remediation technique and as suitable for remediation of large-scale sites contaminated by volatile organic compounds (VOCs) at low cost. However, it has been reported that the removal efficiency of VOCs from soil is relatively low in the late stages of remediation, in association with tailing. Tailing may extend the remediation time required; moreover, it typically results in the presence of contaminants residues at levels far exceeding regulations. In this context, the present study aimed to discuss the tailing that occurs during the process of remediation of soils contaminated artificially with volatile chlorinated hydrocarbons (VCHs) and to assess possible quicklime-enhanced removal mechanisms. The results revealed the following conclusions. First, temperature and aeration rate can be important controls on both the timing of appearance of tailing and the levels of residual contaminants. Furthermore, the addition of quicklime to soil during tailing can reduce the residual concentrations rapidly to below the remedial target values required for site remediation. Finally, mechanical soil aeration can be enhanced using quicklime, which can improve the volatilization of VCHs via increasing soil temperature, reducing soil moisture, and enhancing soil permeability. Our findings give a basic understanding to the elimination of the tailing in the application of mechanical soil aeration, particularly for VOCs-contaminated soils. Copyright © 2014 Elsevier Ltd. All rights reserved.
Kidney cancer and hydrocarbon exposures among petroleum refinery workers.
Poole, C; Dreyer, N A; Satterfield, M H; Levin, L; Rothman, K J
1993-12-01
To evaluate the hypothesis of increased kidney cancer risk after exposure to hydrocarbons, especially those present in gasoline, we conducted a case-control study in a cohort of approximately 100,000 male refinery workers from five petroleum companies. A review of 18,323 death certificates identified 102 kidney cancer cases, to each of whom four controls were matched by refinery location and decade of birth. Work histories, containing an average of 15.7 job assignments per subject, were found for 98% of the cases and 94% of the controls. To each job, industrial hygienists assigned semiquantitative ratings for the intensity and frequency of exposures to three hydrocarbon categories: nonaromatic liquid gasoline distillates, aromatic hydrocarbons, and the more volatile hydrocarbons. Ratings of "present" or "absent" were assigned for seven additional exposures: higher boiling hydrocarbons, polynuclear aromatic hydrocarbons, asbestos, chlorinated solvents, ionizing radiation, and lead. Each exposure had either no association or a weak association with kidney cancer. For the hydrocarbon category of principal a priori interest, the nonaromatic liquid gasoline distillates, the estimated relative risk (RR) for any exposure above refinery background was 1.0 (95% confidence interval [CI] 0.5-1.9). Analyses of cumulative exposures and of exposures in varying time periods before kidney cancer occurrence also produced null or near-null results. In an analysis of the longest job held by each subject (average duration 9.2 years or 40% of the refinery work history), three groups appeared to be at increased risk: laborers (RR = 1.9, 95% CI 1.0-3.9); workers in receipt, storage, and movements (RR = 2.5, 95% CI 0.9-6.6); and unit cleaners (RR = 2.3, 95% CI 0.5-9.9).
NASA Astrophysics Data System (ADS)
de Oliveira, Diogo N.; de Menezes, Maico; Catharino, Rodrigo R.
2015-04-01
In the late years, much attention has been brought to the scientific community regarding the safety of sucralose and its industrial applications. Although it is the most used artificial sweetener in foods and pharmaceuticals, many questions still arise on its potential to form chlorinated byproducts in high temperatures, as demonstrated by several recent studies. In the present contribution, we use a combination of differential scanning calorimetry and thermogravimetric analysis coupled with infrared spectroscopy (DSC/TGA/IR), Hot-stage microscopy (HSM) and high-resolution mass spectrometry (HRMS) on samples submitted to water bath at mild temperatures to evaluate a broad spectrum of hazardous compounds formed in the degradation of this product. TGA/IR has revealed that there is effective decomposition in form of CO2 along with the formation of hydrogen chloride and other minor compounds. HSM results have provided accurate information, where the melting of the crystals was observed, followed by decomposition. Chlorinated derivatives, including polychlorinated aromatic hydrocarbons (PCAHs) were also confirmed by HRMS. These findings not only corroborate the suspected instability of sucralose to high temperatures, but also indicate that even exposed to mild conditions the formation of hazardous polychlorinated compounds is observed.
McGuire, Jennifer T.; Smith, Erik W.; Long, David T.; Hyndman, David W.; Haack, Sheridan K.; Klug, Michael J.; Velbel, Michael A.
2000-01-01
A fundamental issue in aquifer biogeochemistry is the means by which solute transport, geochemical processes, and microbiological activity combine to produce spatial and temporal variations in redox zonation. In this paper, we describe the temporal variability of TEAP conditions in shallow groundwater contaminated with both waste fuel and chlorinated solvents. TEAP parameters (including methane, dissolved iron, and dissolved hydrogen) were measured to characterize the contaminant plume over a 3-year period. We observed that concentrations of TEAP parameters changed on different time scales and appear to be related, in part, to recharge events. Changes in all TEAP parameters were observed on short time scales (months), and over a longer 3-year period. The results indicate that (1) interpretations of TEAP conditions in aquifers contaminated with a variety of organic chemicals, such as those with petroleum hydrocarbons and chlorinated solvents, must consider additional hydrogen-consuming reactions (e.g., dehalogenation); (2) interpretations must consider the roles of both in situ (at the sampling point) biogeochemical and solute transport processes; and (3) determinations of microbial communities are often necessary to confirm the interpretations made from geochemical and hydrogeological measurements on these processes.
de Oliveira, Diogo N; de Menezes, Maico; Catharino, Rodrigo R
2015-04-15
In the late years, much attention has been brought to the scientific community regarding the safety of sucralose and its industrial applications. Although it is the most used artificial sweetener in foods and pharmaceuticals, many questions still arise on its potential to form chlorinated byproducts in high temperatures, as demonstrated by several recent studies. In the present contribution, we use a combination of differential scanning calorimetry and thermogravimetric analysis coupled with infrared spectroscopy (DSC/TGA/IR), Hot-stage microscopy (HSM) and high-resolution mass spectrometry (HRMS) on samples submitted to water bath at mild temperatures to evaluate a broad spectrum of hazardous compounds formed in the degradation of this product. TGA/IR has revealed that there is effective decomposition in form of CO2 along with the formation of hydrogen chloride and other minor compounds. HSM results have provided accurate information, where the melting of the crystals was observed, followed by decomposition. Chlorinated derivatives, including polychlorinated aromatic hydrocarbons (PCAHs) were also confirmed by HRMS. These findings not only corroborate the suspected instability of sucralose to high temperatures, but also indicate that even exposed to mild conditions the formation of hazardous polychlorinated compounds is observed.
de Oliveira, Diogo N.; de Menezes, Maico; Catharino, Rodrigo R.
2015-01-01
In the late years, much attention has been brought to the scientific community regarding the safety of sucralose and its industrial applications. Although it is the most used artificial sweetener in foods and pharmaceuticals, many questions still arise on its potential to form chlorinated byproducts in high temperatures, as demonstrated by several recent studies. In the present contribution, we use a combination of differential scanning calorimetry and thermogravimetric analysis coupled with infrared spectroscopy (DSC/TGA/IR), Hot-stage microscopy (HSM) and high-resolution mass spectrometry (HRMS) on samples submitted to water bath at mild temperatures to evaluate a broad spectrum of hazardous compounds formed in the degradation of this product. TGA/IR has revealed that there is effective decomposition in form of CO2 along with the formation of hydrogen chloride and other minor compounds. HSM results have provided accurate information, where the melting of the crystals was observed, followed by decomposition. Chlorinated derivatives, including polychlorinated aromatic hydrocarbons (PCAHs) were also confirmed by HRMS. These findings not only corroborate the suspected instability of sucralose to high temperatures, but also indicate that even exposed to mild conditions the formation of hazardous polychlorinated compounds is observed. PMID:25873245
Natural attenuation software (NAS): Assessing remedial strategies and estimating timeframes
Mendez, E.; Widdowson, M.; Chapelle, F.; Casey, C.
2005-01-01
Natural Attenuation Software (NAS) is a screening tool to estimate remediation timeframes for monitored natural attenuation (MNA) and to assist in decision-making on the level of source zone treatment in conjunction with MNA using site-specific remediation objectives. Natural attenuation processes that NAS models include are advection, dispersion, sorption, non-aqueous phase liquid (NAPL) dissolution, and biodegradation of either petroleum hydrocarbons or chlorinated ethylenes. Newly-implemented enhancements to NAS designed to maximize the utility of NAS for site managers were observed. NAS has expanded source contaminant specification options to include chlorinated ethanes and chlorinated methanes, and to allow for the analysis of any other user-defined contaminants that may be subject to microbially-mediated transformations (heavy metals, radioisotopes, etc.). Included is the capability to model co-mingled plumes, with constituents from multiple contaminant categories. To enable comparison of remediation timeframe estimates between MNA and specific engineered remedial actions , NAS was modified to incorporate an estimation technique for timeframes associated with pump-and-treat remediation technology for comparison to MNA. This is an abstract of a paper presented at the 8th International In Situ and On-Site Bioremediation Symposium (Baltimore, MD 6/6-9/2005).
Lazareva, Svetlana; Ismagilov, Zinfer; Kuznetsov, Vadim; Shikina, Nadezhda; Kerzhentsev, Mikhail
2018-02-05
Huge amounts of nuclear waste, including depleted uranium, significantly contribute to the adverse environmental situation throughout the world. An approach to the effective use of uranium oxides in catalysts for the deep oxidation of chlorine-containing hydrocarbons is suggested. Investigation of the catalytic activity of the synthesized supported uranium oxide catalysts doped with Cr, Mn and Co transition metals in the chlorobenzene oxidation showed that these catalysts are comparable with conventional commercial ones. Physicochemical properties of the catalysts were studied by X-ray diffraction, temperature-programmed reduction with hydrogen (H 2 -TPR), and Fourier transform infrared spectroscopy. The higher activity of Mn- and Co-containing uranium oxide catalysts in the H 2 -TPR and oxidation of chlorobenzene in comparison with non-uranium catalysts may be related to the formation of a new disperse phase represented by uranates. The study of chlorobenzene adsorption revealed that the surface oxygen is involved in the catalytic process.
DOE Office of Scientific and Technical Information (OSTI.GOV)
Field, E.A.; Sleet, R.B.; Price, C.J.
Hexachloro-1,3-butadiene (HCBD) is an agricultural and industrial chemical and by-product which has been identified as a neprhotoxin in both humans and laboratory animals. It is used industrially to recover chlorine-containing gas, as a fluid for gyroscopes and in the production of lubricants and rubber. HCBD is also a by-product of chlorinated hydrocarbon production. Agriculturally, it is used as a fumigant on grapes. HCBD contamination has been detected in air, water and soil surrounding chemical manufacturing plants and toxic waste landfills and in food and beverages. The current study was undertaken to examine peri-/postnatal development of the rat during maternal exposuremore » to HCBD in the diet during late gestation and lactation with particular attention to structural and functional renal endpoints.« less
Pollutant emissions during the pyrolysis and combustion of flexible polyurethane foam.
Garrido, María A; Font, Rafael; Conesa, Juan A
2016-06-01
Thermal decomposition of flexible polyurethane foam (FPUF) was studied under nitrogen and air atmospheres at 550°C and 850°C using a laboratory scale reactor to analyse the evolved products. Ammonia, hydrogen cyanide and nitrile compounds were obtained in high yields in pyrolysis at the lower temperature, whereas at 850°C polycyclic aromatic hydrocarbons (PAHs) and other semivolatile compounds, especially compounds containing nitrogen (benzonitrile, aniline, quinolone and indene) were the most abundant products. Different behaviour was observed in the evolution of polychlorodibenzo-p-dioxins and furans (PCDD/Fs) at 550°C and 850°C. At 550°C, the less chlorinated congeners, mainly PCDF, were more abundant. Contrarily, at 850°C the most chlorinated PCDD were dominant. In addition, the total yields of PCDD/Fs in the pyrolysis and combustion runs at 850°C were low and quite similar. Copyright © 2016 Elsevier Ltd. All rights reserved.
Puri, S; Chickos, J S; Welsh, W J
2001-04-01
The vaporization enthalpies of 16 polychlorinated biphenyls have been determined by correlation gas chromatography. This study was prompted by the realization that the vaporization enthalpy of the standard compounds used in previous studies, octadecane and eicosane, were values measured at 340 and 362 K, respectively, rather than at 298 K. Adjustment to 298 K amounts to a 7-8 kJ/mol increment in the values. With the inclusion of this adjustment, vaporization enthalpies evaluated by correlation gas chromatography are in good agreement with the values determined previously in the literature. The present results are based on the vaporization enthalpies of several standards whose values are well established in the literature. The standards include a variety of n-alkanes and various chlorinated hydrocarbons. The vaporization enthalpies of PCBs increased with the number of chlorine atoms and were found to be larger for meta- and para-substituted polychlorinated biphenyls.
NASA Astrophysics Data System (ADS)
Skubal, Karen L.; Barcelona, Michael J.; Adriaens, Peter
2001-05-01
Field biogeochemical characterization and laboratory microcosm studies were performed to assess the potential for future biotransformation of trichloroethylene (TCE) and toluene in a plume containing petroleum hydrocarbons and chlorinated solvents at the former Wurtsmith Air Force Base in Oscoda, MI. In situ terminal electron accepting processes (TEAPs), contaminant composition and microbial phylogeny were studied at a plume transect 100 m downgradient of the source. The presence of reduced electron acceptors, relevant microbial communities, and elevated dissolved methane and carbon dioxide concentrations at the transect, as well as downgradient accumulation of BTEX metabolites and dechlorination products, indicated that past or current reductive dechlorination at the transect was likely driven by BTEX biodegradation in the methanogenic zone. However, TCE and toluene mineralization in sediment-groundwater microcosms without added electron acceptors did not exceed 5% during 300 days of incubation and was nearly invariant with original sediment TEAP, even following amendments of nitrogen and phosphorus. Mineralization rates were on the order of 0.0015-0.03 μmol/g day. After 8 months, microcosms showed evidence of methanogenesis, but CH 4 and CO 2 production arose from the degradation of contaminants other than toluene. Cis-dichloroethylene was observed in only one methanogenic microcosm after more than 500 days. It appears likely that spatially and temporally dynamic redox zonation at the plume transect will prevent future sustained reductive dehalogenation of highly chlorinated solvents, for during the course of a year, the predominant TEAP at the highly contaminated water table shifted from methanogenesis to iron- and sulfate-reduction. It is recommended that biotransformation studies combine considerations of long-term, spatially relevant changes in redox zonation with laboratory-scale studies of electron donor utilization and cometabolic substrate transformation to yield a more accurate assessment of natural bioattenuation of specific pollutants in aquifers contaminated by undefined organic waste mixtures.
NASA Astrophysics Data System (ADS)
Rodriguez, L. E.; Abbott, D. H.; Breger, D.
2011-12-01
Analysis using light microscopy, analytical scanning electron microscopy, and measurements of the magnetic susceptibility of five sediment cores (MD 28-MD 32) from the Gulf of Carpentaria have revealed that each has had an impact layer less than a centimeter (10s to 100s of micrometers) thick prior to bioturbation. The present stratigraphic thickness of the impact layer (result of bioturbation) within every core was determined based on whether or not we had observed at least one of the following impact ejecta: FeNiCrCl (a recent discovery), metallic spherules (some of which consisted of Fe and Ni), or chlorinated hydrocarbon; the highest peak of magnetic susceptibility correlated with the highest concentration of impact ejecta. We used modeling of the magnetic susceptibility of a hematite-calcium carbonate mixture to constrain the minimum thickness of the impact ejecta layer (prior to bioturbation). Until recently we had been unaware that the red, glassy, semi-spherules we found within the impact layer were in fact FeNiCrCl. Nickel is not abundant within the Earth's crust, thus it is highly likely that these fragments are cometary debris from an impact event within the Gulf of Carpentaria. Furthermore, SEM analysis has confirmed that the chlorinated hydrocarbon was not PVC contamination from the coring process; with such high levels of chlorine the results strongly suggest that the material was a by product of a marine water impact event. In addition, by using impact modeling we deduced that the observed impact ejecta layer could not have been transported via an impact generated tsunami. The model also predicts that the layer could have been produced by a cometary impact event (average velocity 51 km/s) that would have produced the 12 km crater at the site of the Tabban crater candidate.
Metal loaded zeolitic media for the storage and oxidative destruction of chlorinated VOCs
NASA Astrophysics Data System (ADS)
Chintawar, Prashant Shiodas
Industrial solvents such as trichloroethylene (TCE), perchloroethylene (PCE), etc. are suspected carcinogens and are linked to atmospheric and groundwater pollution. Therefore, the destruction and/or safe disposal of these chlorinated volatile organic compounds (CVOCs) is an immediate national need. The objective of this dissertation was to study transition metal (TM) loaded zeolites for adsorption (storage) and subsequent catalytic destruction of CVOCs present in humid air streams. In this study, zeolite Y, ZSM-5 and ETS-10 were modified by introduction of a TM cation to make them suitable as dual function sorbent/catalyst (S/C) media. In order to develop these S/C media, five investigations were carried out. In the first investigation, the activity and selectivity of three catalysts viz., Cr-Y, Co-Y, Co/Alsb2Osb3, was compared for the destruction of CVOCs. Cr-Y was the most promising catalyst with its activity decreasing with an increase in the chlorine content of the CVOC molecule. In the second investigation, in order to elucidate the pathways involved in the destruction of CVOCs, in situ FT-IR studies were carried out on active Cr-Y surfaces at 25, 100 (or 130) and 300sp°C which showed that CVOC destruction proceeded through the formation of oxygenated intermediates (carbonyl, carboxylate, etc.). These investigations showed the necessity of chromium for destruction of CVOCs. However, chromium residues in the spent catalysts are an environmental concern. Therefore, in the third investigation, attempts were made to stabilize low levels of chromium on ZSM-5 zeolites. Thus, Cr-ZSM-5 media of varying SiOsb2/Alsb2Osb3 ratio were evaluated for sorption and destruction of TCE. This investigation led to the development of a Cr-ZSM-5 (SiOsb2/Alsb2Osb3=80,\\ {˜}0.5 wt% chromium) as an efficient S/C medium for TCE destruction. In the fourth investigation, deactivation experiments were carried out on four Cr-ZSM-5 catalysts. Under the conditions used, all the catalysts lost destruction activity and selectivity which was found to be related to the catalyst and CVOC composition. The deactivation was caused by the loss and migration of exchanged chromium cations from the straight channels of ZSM-5. Since the loss of exchanged chromium cations from Cr-ZSM-5 catalyst during CVOC destruction was inevitable, an attempt was made to introduce chromium in the framework of ETS-10 in the final investigation. The resulting Cr-ETS-10 and Cr-ZSM-5 S/C media were then used to evaluate the effect of CVOC chlorine content by determining adsorptivity and reactivity of aliphatic and aromatic hydrocarbons and their chlorinated counterparts. Chlorination was found to increase the hydrocarbon adsorptivity on both S/C media. Characterization of the Cr-ETS-10 revealed that chromium had been introduced into the framework of ETS-10.
Odabasi, Mustafa
2008-03-01
Sodium hypochlorite (NaOCl) and many organic chemicals contained in household cleaning products may react to generate halogenated volatile organic compounds (VOCs). Halogenated VOC emissions from eight different chlorine bleach containing household products (pure and diluted) were investigated by headspace experiments. Chloroform and carbon tetrachloride were the leading compounds along with several halogenated compounds in the headspace of chlorine bleach products. One of the most surprising results was the presence of carbon tetrachloride (a probable human carcinogen and a powerful greenhouse gas that was banned for household use by the U.S. Food and Drug Administration) in very high concentrations (up to 101 mg m(-3)). By mixing surfactants or soap with NaOCl, it was shown that the formation of carbon tetrachloride and several other halogenated VOCs is possible. In addition to quantitatively determined halogenated VOCs (n = 15), several nitrogen-containing (n = 4), chlorinated (n = 10), oxygenated compounds (n = 22), and hydrocarbons (n = 14) were identified in the headspace of bleach products. Among these, 1,1-dichlorobutane and 2-chloro-2-nitropropane were the most abundant chlorinated VOCs, whereas trichloronitromethane and hexachloroethane were the most frequently detected ones. Indoor air halogenated VOC concentrations resulting from the use of four selected household products were also measured before, during, and 30 min after bathroom, kitchen, and floor cleaning applications. Chloroform (2.9-24.6 microg m(-3)) and carbon tetrachloride (0.25-459 microg m(-3)) concentrations significantly increased during the use of bleach containing products. During/ before concentration ratios ranged between 8 and 52 (25 +/- 14, average +/- SD) for chloroform and 1-1170 (146 +/- 367, average +/- SD) for carbon tetrachloride, respectively. These results indicated that the bleach use can be important in terms of inhalation exposure to carbon tetrachloride, chloroform and several other halogenated VOCs.
Stewart, Donald J.; Stein, Roy A.
1974-01-01
Short-term fate of dietary dieldrin in the digestive tract of fishes is poorly known. Studies of the uptake, distribution, and elimination of chlorinated hydrocarbons have suggested that uptake or degradation is rapid in the intestine (GROSS 1969; MACEK et al. 1970; GRZENDA et al. 1970, 1971). The present study was designed to determine the short-term fate of a single oral dose of dieldrin in the digestive tract of lake trout (Salvelinus namaycush).
Chemistry and photochemistry of low-volatility organic chemicals on environmental surfaces
DOE Office of Scientific and Technical Information (OSTI.GOV)
Miller, G.C.; Hebert, V.R.; Zepp, R.G.
Hydrophobic organic xenobiotics such as polychlorinated dibenzodioxins and polycyclic aromatic hydrocarbons have strong tendencies to sorb on environmental surfaces. This paper summarizes a workshop in which scientists and modelers assembled to discuss nonbiological processes that affect sorption to soil or sediment surfaces and on atmospheric particles. The 20 scientists discussed a variety of topics with a major emphasis on the fate of chlorinated dioxins. The topics include transformation processes, mobility of organic pollutants, fate of organics, and evaluative fate models.
Conversion from solvent rinsable fluxes to aqueous rinsable fluxes for hot oil solder leveling
NASA Astrophysics Data System (ADS)
1992-03-01
A water rinsable flux was evaluated for hot oil solder leveling of printed wiring boards. The previously used rosin-activated flux required a solvent containing a chlorinated hydrocarbon for removing the flux residues after soldering. The water rinsable flux requires hot water or a solution of hot detergent for removing flux residues after smoldering. The water rinsable flux produced an acceptable soldered surface. Flux residues were removed by either hot water (120 F) or a solution of hot detergent (120 F).
1997-10-01
and xylene (BTEX) in the shallow groundwater system at the site. Dissolved chlorinated aliphatic hydrocarbons (CAHs) also are present in the shallow...micrograms per liter (gg/L)], RNA with LTM I should be used to complement the ROD-mandated bioventing and air sparging systems . 0 When bioventing and...The ROD identifies benzene as the primary contaminant of concern (COC) for FT-i and specifies the use of air sparging in the remediation system
Phytoremediation and innovative strategies for specialized remedial actions
DOE Office of Scientific and Technical Information (OSTI.GOV)
Alleman, B.C.; Leeson, A.
1999-01-01
Phytoremediation is a site remediation strategy whose time seems to have come in the past few years, with field implementations taking place in a host of applications. From laboratory studies on plant uptake to full-scale phytoremediation treatment strategies, this volume covers the use of plants to treat contaminants such as hydrocarbons, metals, pesticides, perchlorate, and chlorinated solvents. In addition to the phytoremediation studies, this volume also covers specialized remediation approaches such as sequential anaerobic/aerobic in situ treatment, membrane bioreactors, and Fenton's reagent oxidation.
Phytoremediation and innovative strategies for specialized remedial actions
DOE Office of Scientific and Technical Information (OSTI.GOV)
Alleman, B.C.; Leeson, A.
1999-11-01
Phytoremediation is a site remediation strategy whose time seems to have come in the past few years, with field implementations taking place in a host of applications. From laboratory studies on plant uptake to full-scale phytoremediation treatment strategies, this volume covers the use of plants to treat contaminants such as hydrocarbons, metals, pesticides, perchlorate, and chlorinated solvents. In addition to the phytoremediation studies, this volume also covers specialized remediation approaches such as sequential anaerobic/aerobic in situ treatment, membrane bioreactors, and Fenton`s reagent oxidation.
Phytoremediation and innovative strategies for specialized remedial applications
DOE Office of Scientific and Technical Information (OSTI.GOV)
Alleman, B.C.; Leeson, A.
1999-10-01
Phytoremediation is a site remediation strategy whose time seems to have come in the past few years, with field implementations taking place in a host of applications. From laboratory studies on plant uptake to full-scale phytoremediation treatment strategies, this volume covers the use of plants to treat contaminants such as hydrocarbons, metals, pesticides, perchlorate, and chlorinated solvents. In addition to the phytoremediation studies, this volume also covers specialized remediation approaches such as sequential anaerobic/aerobic in situ treatment, membrane bioreactors, and Fenton`s reagent oxidation.
Volatile halogenated hydrocarbons in foods
DOE Office of Scientific and Technical Information (OSTI.GOV)
Miyahara, Makoto; Toyoda, Masatake; Saito, Yukio
1995-02-01
Volatile halogenated organic compounds were determined in foods. Statistical treatment of the data for 13 sampled from 20 families living in suburban Tokyo (Saitama prefecture) indicated that the foods were contaminated by water pollution and/or substances introduced by the process of food production. Butter and margarine were contaminated by chlorinated ethylene, ethane, and related compounds released by dry cleaning and other operations. Soybean sprouts and tofu (soybean curd) contained chloroform and related trihalomethanes absorbed during the production process. 27 refs., 6 figs., 5 tabs.
Jerry Lee Michael
2003-01-01
The impact of forestry herbicides on ecosystems, terrestrial and aquatic, is a subject which has received much attention. That attention increased with the publication of Rachel Carson's book Silent Spring in 1962. At that time, several chlorinated hydrocarbons were in wide spread use in the US and around the world, the most well known of which...
1979-08-01
eating contaminated fish and birds. Oil on feathers of birds carried to their eggs can kill the embryos. Heavier petroleum products, if spilled, would...result in death or sickness. Petroleum products on shore or in the water can get on bird feathers. Birds in the water lose both insulation and buoyancy...lake basin did not find detectable levels of hazardous substances such as arsenic, phenols, mercury, PCB’s and other chlorinated hydrocarbons . The
Flow-through Fourier transform infrared sensor for total hydrocarbons determination in water.
Pérez-Palacios, David; Armenta, Sergio; Lendl, Bernhard
2009-09-01
A new flow-through Fourier transform infrared (FT-IR) sensor for oil in water analysis based on solid-phase spectroscopy on octadecyl (C18) silica particles has been developed. The C18 non-polar sorbent is placed inside the sensor and is able to retain hydrocarbons from water samples. The system does not require the use of chlorinated solvents, reducing the environmental impact, and the minimal sample handling stages serve to ensure sample integrity whilst reducing exposure of the analyst to any toxic hydrocarbons present within the samples. Fourier transform infrared (FT-IR) spectra were recorded by co-adding 32 scans at a resolution of 4 cm(-1) and the band located at 1462 cm(-1) due to the CH(2) bending was integrated from 1475 to 1450 cm(-1) using a baseline correction established between 1485 and 1440 cm(-1) using the areas as analytical signal. The technique, which provides a limit of detection (LOD) of 22 mg L(-1) and a precision expressed as relative standard deviation (RSD) lower than 5%, is considerably rapid and allows for a high level of automation.
Sevimoğlu, Orhan; Tansel, Berrin
2013-01-01
Performances of gas engines operated with landfill gas (LFG) are affected by the impurities in the LFG, reducing the economic viability of energy recovery. The purpose of this study was to characterize the trace compounds in the LFG at the Odayeri Landfill, Istanbul, Turkey which is used for energy recovery. Composite gas samples were collected and analyzed for trace compounds (hydrocarbons, siloxanes, and volatile halogenated hydrocarbons) over a 3-year period. Trace compounds entering the gas engines, their impact on the engine performance were evaluated. The operational problems included deposit formation in the combustion chamber, turbocharger, and intercooler of engine before the scheduled maintenance times. High levels of hydrogen sulfide, as well as chlorinated and fluorinated compounds cause corrosion of the engine parts and decrease life of the engine oils. Persistence of siloxanes results in deposit formation, increasing engine maintenance costs. Pretreatment of LFG is necessary to protect the engines at the waste-to-energy facilities with persistence levels of siloxanes and volatile halogenated hydrocarbons. Copyright © 2012 Elsevier Ltd. All rights reserved.
Gold-Bouchot, G; Ceja-Moreno, V; Chan-Cocom, E; Zapata-Perez, O
2014-01-01
In October 2007, a light crude oil spill took place in the off shore Kab121 oil well, 32 km north of the mouth of the Grijalva River, Tabasco, Mexico. In order to estimate the possible effects of oil spill on the biota in the area surrounding the spilled well, the level of different fractions of petroleum hydrocarbons were measured in fish, as well as the concentration of some chlorinated hydrocarbons and PCBs. The organisms examined were cat fish (Ariopsis felis), in addition fluorescent aromatic compounds in bile, the contaminants above mentioned and their relationship with cyotochrome P-450 and Ethoxyresorufin-O-deethylase, Glutathion-S-Transferase and catalase activities in liver were determined. The concentration of most pollutants were low, except PAHs. Spatial distribution of these compounds, as well as most biomarkers, reflected the highest exposure of fish to pollutants in the area adjacent to well, as well as in the proximity of rivers. The profile of exposure to this environment was chronic in nature and not temporary.
APPLICATION, PERFORMANCE, AND COSTS OF ...
A critical review of biological treatment processes for remediation of contaminated soils is presented. The focus of the review is on documented cost and performance of biological treatment technologies demonstrated at full- or field-scale. Some of the data were generated by the U.S. Environmental Protection Agency's (EPA's) Bioremediation in the Field Program, jointly supported by EPA's Office of Research and Development, EPA's Office of Solid Waste and Emergency Waste, and the EPA Regions through the Superfund Innovative Technology Evaluation Program (SITE) Program. Military sites proved to be another fertile data source. Technologies reviewed in this report include both ex-situ processes, (land treatment, biopile/biocell treatment, composting, and bioslurry reactor treatment) and in-situ alternatives (conventional bioventing, enhanced or cometabolic bioventing, anaerobic bioventing, bioslurping, phytoremediation, and natural attenuation). Targeted soil contaminants at the documented sites were primarily organic chemicals, including BTEX, petroleum hydrocarbons, polycyclic aromatic hydrocarbons (PAHs), chlorinated aliphatic hydrocarbons (CAHs), organic solvents, polychlorinated biphenyls (PCBs), pesticides, dioxin, and energetics. The advantages, limitations, and major cost drivers for each technology are discussed. Box and whisker plots are used to summarize before and after concentrations of important contaminant groups for those technologies consider
Owolabi, Moses S.; Ogundajo, Akintayo L.; Ogunwande, Isiaka A.; Yusuff, Olaniyi K.; Flores-Fernandez, Karen Isabel; Flores-Fernandez, Jose Miguel
2014-01-01
Insecticidal activity of essential oil extracted from Morinda lucida was tested on pulse beetle Callosobruchus maculatus, which is a pest that causes serious damage to several pulses. The insecticidal activity was compared with two pesticides, Phostoxin and Primo-ban-20. 120 mixed sex adult C. maculatus were introduced, along with 30 g of cowpeas. Four concentrations (0.40, 0.20, 0.10, and 0.05 μg/mL) of the M. lucida essential oil, Phostoxin, and Primo-ban-20 were tested. Essential oil chemical composition was analyzed by GC-MS. M. lucida essential oil showed a high toxicological effect, producing 100% mortality after 72 hours at a dose of 0.20 μg/mL. M. lucida essential oil had a potent insecticidal activity (LC90 = 0.629 μg/mL) compared to both pesticides, Phostoxin (LC90 = 0.652 μg/mL) and Primo-ban-20 (LC90 = 0.726 μg/mL), at 24 h. The main compounds of the essential oil were the oxygenated monoterpenoids, 1,8-cineole (43.4%), and α-terpinyl acetate (14.5%), and the monoterpene hydrocarbons, mostly sabinene (8.2%) and β-pinene (4.0%). Results clearly indicate that M. lucida essential oil can be used as an effective alternative for pulse beetle C. maculatus control, and it could be tested against other pulse beetles affecting Asia and Africa and throughout the world, thereby reducing use of synthetic pesticides. PMID:25143991
Process for functionalizing alkanes
Bergman, Robert G.; Janowicz, Andrew H.; Periana, Roy A.
1988-01-01
Process for functionalizing saturated hydrocarbons comprising: (a) reacting said saturated hydrocarbons of the formula: R.sub.1 H wherein H represents a hydrogen atom; and R.sub.1 represents a saturated hydrocarbon radical, with a metal complex of the formula: CpRh[P(R.sub.2).sub.3 ]H.sub.2 wherein Cp represents a cyclopentadienyl or alkylcyclopentadienyl radical; Rh represents a rhodium atom; P represents a phosphorus atom; R.sub.2 represents a hydrocarbon radical; H represents a hydrogen atom, in the presence of ultraviolet radiation to form a hydridoalkyl complex of the formula: CpRh[P(R.sub.2).sub.3 ](R.sub.1)H (b) reacting said hydridoalkyl complex with an organic halogenating agent such as a tetrahalomethane or a haloform of the formulas: CX'X''X'''X'''' or CHX'X''X''' wherein X', X'', X'", X"" represent halogens selected from bromine, iodine or chlorine atom, at a temperature in the range of about -60.degree. to -17.degree. C. to form the corresponding haloalkyl complex of step (a) having the formula: CpRhPMe.sub.3 RX; and, (c) reacting said haloalkyl complex formed in (b) with halogen (X.sub.2) at a temperature in the range of about -60.degree. to 25.degree. C. (i.e., ambient) to form a functional haloalkyl compound.
Long-chain (C19-C29) 1-chloro-n-alkanes in leaf waxes of halophytes of the Chenopodiaceae.
Grossi, Vincent; Raphel, Danielle
2003-07-01
The hydrocarbon fraction of leaf waxes of three halophytes of the Chenopodiaceae common to Mediterranean salt marshes (Suaeda vera, Sarcocornia fruticosa and Halimione portulacoides) revealed the presence of a minor series of odd and even chains 1-chloro-n-alkanes ranging from C(19) to C(29). The identification of these new chlorinated plant constituents was based on a combination of mass spectrometry data with selective chlorine detection (CPG-AED) and was confirmed by comparison with authentic standards. The qualitative and quantitative distributions of these 1-chloro-n-alkanes varied inter-specifically. Homologues with an odd carbon-chain were predominant in all species but maximised at C(25) and C(27) in S. vera and S. fruticosa, and at C(27) and C(29) in H. portulacoides. Remarkably, 1-chloro-nonacosane was an abundant homologue only in this latter species. Leaves of S. vera contained 4 to 7 times more of total chloroalkanes than leaves of the other two species. These compounds accounted for 10, 4 and 1% of the hydrocarbon fraction of leaf waxes of S. vera, S. fruticosa and H. portulacoides, respectively. Attempts to link the occurrence of these chloroalkanes with other classes of leaf waxes (n-alkenes, n-aldehydes and n-alcohols) did not allowed a clear precursor-product relationship to be established. The biological functions as well as the mode of synthesis of alkylchlorides in (halophyte) plants remain unknown but undoubtedly deserve further attention.
Ma, Yan; Dong, Binbin; He, Xiaosong; Shi, Yi; Xu, Mingyue; He, Xuwen; Du, Xiaoming; Li, Fasheng
2017-04-01
Mechanical soil aeration is used for soil remediation at sites contaminated by volatile organic compounds. However, the effectiveness of the method is limited by low soil temperature, high soil moisture, and high soil viscosity. Combined with mechanical soil aeration, quicklime has a practical application value related to reinforcement remediation and to its action in the remediation of soil contaminated with volatile organic compounds. In this study, the target pollutant was trichloroethylene, which is a volatile chlorinated hydrocarbon pollutant commonly found in contaminated soils. A restoration experiment was carried out, using a set of mechanical soil-aeration simulation tests, by adding quicklime (mass ratios of 3, 10, and 20%) to the contaminated soil. The results clearly indicate that quicklime changed the physical properties of the soil, which affected the environmental behaviour of trichloroethylene in the soil. The addition of CaO increased soil temperature and reduced soil moisture to improve the mass transfer of trichloroethylene. In addition, it improved the macroporous cumulative pore volume and average pore size, which increased soil permeability. As soil pH increased, the clay mineral content in the soils decreased, the cation exchange capacity and the redox potential decreased, and the removal of trichloroethylene from the soil was enhanced to a certain extent. After the addition of quicklime, the functional group COO of soil organic matter could interact with calcium ions, which increased soil polarity and promoted the removal of trichloroethylene. Copyright © 2017 Elsevier Ltd. All rights reserved.
Polycyclic aromatic hydrocarbon (PAH) emissions from a coal-fired pilot FBC system.
Liu, K; Han, W; Pan, W P; Riley, J T
2001-06-29
Due to the extensive amount of data suggesting the hazards of these compounds, 16 polycyclic aromatic hydrocarbons (PAHs) are on the Environmental Protection Agency (EPA) Priority Pollutant List. Emissions of these PAHs in the flue gas from the combustion of four coals were measured during four 1000h combustion runs using the 0.1MW heat-input (MWth) bench-scale fluidized bed combustor (FBC). An on-line sampling system was designed for the 16 PAHs, which consisted of a glass wool filter, condenser, glass fiber filter, Teflon filter, and a Tenax trap. The filters and Tenax were extracted by methylene chloride and hexane, respectively, followed by GC/MS analysis using the selective ion monitoring (SIM) mode. In this project, the effects of operating parameters, limestone addition, chlorine content in the coal, and Ca/S molar ratio on the emissions of PAHs were studied. The results indicated that the emissions of PAHs in an FBC system are primarily dependent on the combustion temperature and excess air ratio. The injection of secondary air with high velocity in the freeboard effectively reduces PAH emissions. The addition of extra limestone can promote the formation of PAHs in the FBC system. Chlorine in the coal can possibly lead to large benzene ring PAH formation during combustion. The total PAH emission increases with an increase in the sulfur content of coal. Incomplete combustion results in PAHs with four or more benzene rings. High efficiency combustion results in PAHs with two or three benzene rings.
Jin, Rong; Zheng, Minghui; Yang, Hongbo; Yang, Lili; Wu, Xiaolin; Xu, Yang; Liu, Guorui
2017-12-01
Chlorinated and brominated polycyclic aromatic hydrocarbons (Cl/Br-PAHs) are emerging semi-volatile organic pollutants in haze-associated particulate matter (PM). Their gas-particle phase partitioning and distribution among PM fractions have not been clarified. Clarification would increase understanding of atmospheric behavior and health risks of Cl/Br-PAHs. In this study, samples of the gas phase and 4 PM phases (aerodynamic diameters (d ae ) > 10 μm, 2.5-10 μm, 1.0-2.5 μm, and <1.0 μm) were collected simultaneously during haze events in Beijing and analyzed. Normalized histogram distribution indicated that the Cl/Br-PAHs tended to adhere to fine particles. Over 80% of the Cl-PAHs and 70% of the Br-PAHs were associated with fine PM (d ae < 2.5 μm). The gas-particle phase partitioning and PM distribution of Cl/Br-PAHs when heating of buildings was required, which was associated with haze events, were obviously different from those when heating was not required. The relationship between the logarithmic geometric mean diameters of the Cl/Br-PAH congeners and reciprocal of the temperature (1/T) suggested that low air temperatures during the heating period could lead to high proportions of Cl/Br-PAHs in the fine particles. Increased coal burning during the heating period also contributed to high Cl/Br-PAH loads in the fine particles. Copyright © 2017 Elsevier Ltd. All rights reserved.
Dojka, Michael A.; Hugenholtz, Philip; Haack, Sheridan K.; Pace, Norman R.
1998-01-01
A culture-independent molecular phylogenetic approach was used to survey constituents of microbial communities associated with an aquifer contaminated with hydrocarbons (mainly jet fuel) and chlorinated solvents undergoing intrinsic bioremediation. Samples were obtained from three redox zones: methanogenic, methanogenic-sulfate reducing, and iron or sulfate reducing. Small-subunit rRNA genes were amplified directly from aquifer material DNA by PCR with universally conserved or Bacteria- or Archaea-specific primers and were cloned. A total of 812 clones were screened by restriction fragment length polymorphisms (RFLP), approximately 50% of which were unique. All RFLP types that occurred more than once in the libraries, as well as many of the unique types, were sequenced. A total of 104 (94 bacterial and 10 archaeal) sequence types were determined. Of the 94 bacterial sequence types, 10 have no phylogenetic association with known taxonomic divisions and are phylogenetically grouped in six novel division level groups (candidate divisions WS1 to WS6); 21 belong to four recently described candidate divisions with no cultivated representatives (OP5, OP8, OP10, and OP11); and 63 are phylogenetically associated with 10 well-recognized divisions. The physiology of two particularly abundant sequence types obtained from the methanogenic zone could be inferred from their phylogenetic association with groups of microorganisms with a consistent phenotype. One of these sequence types is associated with the genus Syntrophus; Syntrophus spp. produce energy from the anaerobic oxidation of organic acids, with the production of acetate and hydrogen. The organism represented by the other sequence type is closely related to Methanosaeta spp., which are known to be capable of energy generation only through aceticlastic methanogenesis. We hypothesize, therefore, that the terminal step of hydrocarbon degradation in the methanogenic zone of the aquifer is aceticlastic methanogenesis and that the microorganisms represented by these two sequence types occur in syntrophic association. PMID:9758812
Dojka, M.A.; Hugenholtz, P.; Haack, S.K.; Pace, N.R.
1998-01-01
A culture-independent molecular phylogenetic approach was used to survey constituents of microbial communities associated with an aquifer contaminated with hydrocarbons (mainly jet fuel) and chlorinated solvents undergoing intrinsic bioremediation. Samples were obtained from three redox zones: methanogenic, methanogenic-sulfate reducing, and iron or sulfate reducing. Small-subunit rRNA genes were amplified directly from aquifer material DNA by PCR with universally conserved or Bacteria- or Archaea-specific primers and were cloned. A total of 812 clones were screened by restriction fragment length polymorphisms (RFLP), approximately 50% of which were unique. All RFLP types that occurred more than once in the libraries, as well as many of the unique types, were sequenced. A total of 104 (94 bacterial and 10 archaeal) sequence types were determined. Of the 94 bacterial sequence types, 10 have no phylogenetic association with known taxonomic divisions and are phylogenetically grouped in six novel division level groups (candidate divisions WS1 to WS6); 21 belong to four recently described candidate divisions with no cultivated representatives (OPS, OP8, OP10, and OP11); and 63 are phylogenetically associated with 10 well-recognized divisions. The physiology of two particularly abundant sequence types obtained from the methanogenic zone could be inferred from their phylogenetic association with groups of microorganisms with a consistent phenotype. One of these sequence types is associated with the genus Syntrophus; Syntrophus spp. produce energy from the anaerobic oxidation of organic acids, with the production of acetate and hydrogen. The organism represented by the other sequence type is closely related to Methanosaeta spp., which are known to be capable of energy generation only through aceticlastic methanogenesis. We hypothesize, therefore, that the terminal step of hydrocarbon degradation in the methanogenic zone of the aquifer is aceticlastic methanogenesis and that the microorganisms represented by these two sequence types occur in syntrophic association.
UV light and urban pollution: bad cocktail for mosquitoes?
Tetreau, Guillaume; Chandor-Proust, Alexia; Faucon, Frédéric; Stalinski, Renaud; Akhouayri, Idir; Prud'homme, Sophie M; Régent-Kloeckner, Myriam; Raveton, Muriel; Reynaud, Stéphane
2014-01-01
Mosquito breeding sites consist of water pools, which can either be large open areas or highly covered ponds with vegetation, thus with different light exposures combined with the presence in water of xenobiotics including polycyclic aromatic hydrocarbons (PAHs) generated by urban pollution. UV light and PAHs are abiotic factors known to both affect the mosquito insecticide resistance status. Nonetheless, their potential combined effects on the mosquito physiology have never been investigated. The present article aims at describing the effects of UV exposure alongside water contamination with two major PAH pollutants (fluoranthene and benzo[a]pyrene) on a laboratory population of the yellow fever mosquito Aedes aegypti. To evaluate the effects of PAH exposure and low energetic UV (UV-A) irradiation on mosquitoes, different parameters were measured including: (1) The PAH localization and its impact on cell mortality by fluorescent microscopy; (2) The detoxification capacities (cytochrome P450, glutathione-S-transferase, esterase); (3) The responses to oxidative stress (Reactive Oxygen Species-ROS) and (4) The tolerance of mosquito larvae to a bioinsecticide (Bacillus thuringiensis subsp. israelensis-Bti) and to five chemical insecticides (DDT, imidacloprid, permethrin, propoxur and temephos). Contrasting effects regarding mosquito cell mortality, detoxification and oxidative stress were observed as being dependent on the pollutant considered, despite the fact that the two PAHs belong to the same family. Moreover, UV is able to modify pollutant effects on mosquitoes, including tolerance to three insecticides (imidacloprid, propoxur and temephos), cell damage and response to oxidative stress. Taken together, our results suggest that UV and pollution, individually or in combination, are abiotic parameters that can affect the physiology and insecticide tolerance of mosquitoes; but the complexity of their direct effect and of their interaction will require further investigation to know in which condition they can affect the efficacy of insecticide-based vector control strategies in the field. Published by Elsevier B.V.
Research by the U.S. Geological Survey on organic materials in water
Baker, Robert Andrew
1976-01-01
The U.S. Geological Survey has responsibility for investigating the Nation's water resources for source, availability, quantity, and quality. This paper describes the Geological Survey's research on organic substances in water and fluvial sediments. Results and ongoing studies are examined. Typical research includes: Separation, concentration, and chromatographic identification of volatile acids; free-flow electrophoresis fractionation of natural organic materials; identification of chlorinated insecticides in suspended sediments and bottom materials; fate of organics following underground disposal; determination of humic and fulvic acid stability constants and characterizations; identification of low-molecular weight chloroorganic constituents in water; PCB (polychlorinated biphenyl compound) distribution in aquatic environments; dissolved organic carbon in ground water; and improvement in separation and concentration schemes prior to analyses.
DOE Office of Scientific and Technical Information (OSTI.GOV)
Wade, T.L.; Velinsky, D.J.; Reinharz, E.
1994-06-01
Concentrations of aliphatic, aromatic, and chlorinated hydrocarbons were determined from 33 surface-sediment samples taken from the Tidal Basin, Washington Ship Channel, and the Anacostia and Potomac rivers in Washington, D.C. In conjunction with these samples, selected storm sewers and outfalls also were sampled to help elucidate general sources of contamination to the area. All of the sediments contained detectable concentrations of aliphatic and aromatic hydrocarbons, DDT (total dichlorodiphenytrichloroethande), DDE (dichlorodiphenyldichloroethene), DDD (dichlorodiphenyldichloroethane), PCBx (total polychlorinated biphenyls) and total chlordanes (oxy-, {alpha}-, and {gamma}-chlordane and cis + trans-nonachlor). Sediment concentrations of most contaminants were highest in the Anacostia River just downstreammore » of the Washington Navy Yard, except for total chlordane, which appeared to have upstream sources in addition to storm and combined sewer runoff. This area has the highest number of storm and combined sewer outfalls in the river. Potomac River stations had lower concentrations than other stations. Polycyclic aromatic hydrocarbons, saturated hydrocarbons, and the unresolved complex mixture (UCM) distributions reflect mixtures of combustion products and direct discharges of petroleum products. Sources of PCBs appear to be related to specific outfalls, while hydrocarbon inputs, especially PAHs, are diffuse, and may be related to street runoff. This study indicates that in large urban areas, nonpoint sources deliver substantial amounts of contaminants to ecosystems through storm and combined sewer systems, and control of these inputs must be addressed. 33 refs., 6 figs., 3 tabs.« less
Vorkamp, Katrin; Rigét, Frank F; Bossi, Rossana; Sonne, Christian; Dietz, Rune
2017-11-01
Besides globally banned "legacy" persistent organic pollutants, other compounds might be present in Arctic wildlife, for which regulation was introduced recently (the insecticide endosulfan), is considered (short-chain chlorinated paraffins, SCCPs) or does not exist (octachlorostyrene, OCS, a byproduct of manufacturing and combustion processes involving chlorine). The purpose of this study was to analyze the time trend of endosulfan (1986-2012) in ringed seals and to address the levels of SCCPs and OCS in wildlife species from Greenland (black guillemot, glaucous gull, ringed seal, polar bear), while taking a critical standpoint to analytical methods typically applied. The metabolite endosulfan sulfate was the only endosulfan compound consistently above detection limits, with a median concentration of 0.23 ng/g lipid weight (lw) and a significant annual decrease of -5.6%. The low-resolution mass spectrometry (LRMS) method appeared accurate and sufficiently precise; however, the gel permeation chromatography had to balance lipid removal and analyte loss. SCCPs and OCS were present in all samples. OCS median concentrations were between 2.8 (ringed seal blubber) and 29 (glaucous gull liver) ng/g lw, determined by a straightforward dual column electron capture detection method. SCCPs were analyzed by LRMS, following removal of potential interferences, and had median concentrations of several 100 ng/g wet weight. While the method showed good precision and recovery rates as well as acceptable accuracy in control samples, the Greenland samples had high concentrations in an Arctic context, possibly indicating limited selectivity of the LRMS method.
IRIS Toxicological Review and Summary Documents for ...
Carbon tetrachloride is a volatile haloalkane with a wide range of industrial and chemical applications. It is produced commercially from chlorination of a variety of low molecular weight hydrocarbons such as carbon disulfide, methanol, methane, propane, and ethylene dichloride. It is also produced by thermal chlorination in the production of tetrachloroethylene. Major uses of carbon tetrachloride have been in the recovery of tin from tin plating waste, in formulation of petrol additives and refrigerants, in metal degreasing and agricultural fumigants, in chlorination of organic compounds, in the production of semiconductors, in the reduction of fire hazard, as a solvent for rubber cement, and as a catalyst in polymer technology. Its production has been decreasing and it is no longer permitted in products intended for home use. Despite this ban, carbon tetrachloride has been detected at 314 hazardous waste sites. EPA's assessment of noncancer health effects and carcinogenic potential of carbon tetrachloride was last prepared and added to the IRIS database in 1991. The IRIS program is preparing an assessment that will incorporate health effects information available for carbon tetrachloride, and current risk assessment methods. The IRIS assessment for carbon tetrachloride will consist of a Toxicological Review and IRIS Summary. The Toxicological Review is a critical review of the physiochemical and toxicokinetic properties of a chemical, and its toxicity
Laroo, Christopher A; Schenk, Charles R; Sanchez, L James; McDonald, Joseph
2011-08-01
Exhaust emissions of 17 2,3,7,8-substituted chlorinated dibenzo-p-dioxin/furan (CDD/F) congeners, tetra-octa CDD/F homologues, 12 2005 WHO chlorinated biphenyls (CB) congeners, mono-nona CB homologues, and 19 polycyclic aromatic hydrocarbons (PAHs) from a model year 2008 Cummins ISB engine were investigated. Testing included configurations composed of different combinations of aftertreatment including a diesel oxidation catalyst (DOC), catalyzed diesel particulate filter (CDPF), copper zeolite urea selective catalytic reduction (SCR), iron zeolite SCR, and ammonia slip catalyst. Results were compared to a baseline engine out configuration. Testing included the use of fuel that contained the maximum expected chlorine (Cl) concentration of U.S. highway diesel fuel and a Cl level 1.5 orders of magnitude above. Results indicate there is no risk for an increase in polychlorinated dibenzo-p-dioxin/furan and polychlorinated biphenyl emissions from modern diesel engines with catalyzed aftertreatment when compared to engine out emissions for configurations tested in this program. These results, along with PAH results, compare well with similar results from modern diesel engines in the literature. The results further indicate that polychlorinated dibenzo-p-dioxin/furan emissions from modern diesel engines both with and without aftertreatment are below historical values reported in the literature as well as the current inventory value.
NASA Astrophysics Data System (ADS)
Kamgang-Youbi, G.; Poizot, K.; Lemont, F.
2012-12-01
The performance of a plasma reactor for the degradation of chlorinated hydrocarbon waste is reported. Chloroform was used as a target for a recently patented destruction process based using an inductive plasma torch. Liquid waste was directly injected axially into the argon plasma with a supplied power of ~4 kW in the presence of oxygen as oxidant and carrier gas. Decomposition was performed at CHCl3 feed rates up to 400 g·h-1 with different oxygen/waste molar ratios, chloroform destruction was obtained with at least 99% efficiency and the energy efficiency reached 100 g·kWh-1. The conversion end products were identified and assayed by online FTIR spectroscopy (CO2, HCl and H2O) and redox titration (Cl2). Considering phosgene as representative of toxic compounds, only very small quantities of toxics were released (< 1 g·h-1) even with high waste feed rates. The experimental results were very close to the equilibrium composition predicted by thermodynamic calculations. At the bottom of the reactor, the chlorinated acids were successfully trapped in a scrubber and transformed into mineral salts, hence, only CO2 and H2O have been found in the final off-gases composition.
Thermal decomposition of electronic wastes: Mobile phone case and other parts
DOE Office of Scientific and Technical Information (OSTI.GOV)
Molto, Julia, E-mail: julia.molto@ua.es; Egea, Silvia; Conesa, Juan Antonio
Highlights: > Pyrolysis and combustion of different parts of mobile phones produce important quantities of CO and CO{sub 2}. > Naphthalene is the most abundant PAH obtained in the thermal treatment of mobile phones. > Higher combustion temperature increases the chlorinated species evolved. - Abstract: Pyrolysis and combustion runs at 850 {sup o}C in a horizontal laboratory furnace were carried out on different parts of a mobile phone (printed circuit board, mobile case and a mixture of both materials). The analyses of the carbon oxides, light hydrocarbons, polycyclic aromatic hydrocarbons (PAHs), polychlorodibenzo-p-dioxin, polychlorodibenzofurans (PCDD/Fs), and dioxin-like PCBs are shown. Regardingmore » semivolatile compounds, phenol, styrene, and its derivatives had the highest yields. In nearly all the runs the same PAHs were identified, naphthalene being the most common component obtained. Combustion of the printed circuit board produced the highest emission factor of PCDD/Fs, possibly due to the high copper content.« less
Degradation of halogenated aliphatic compounds by Xanthobacter autotrophicus GJ10.
Janssen, D B; Scheper, A; Dijkhuizen, L; Witholt, B
1985-01-01
A bacterium that is able to utilize a number of halogenated short-chain hydrocarbons and halogenated carboxylic acids as sole carbon source for growth was identified as a strain of Xanthobacter autotrophicus. The organism constitutively produces two different dehalogenases. One enzyme is specific for halogenated alkanes, whereas the other, which is more heat stable and has a higher pH optimum, is specific for halogenated carboxylic acids. Haloalkanes were hydrolyzed in cell extracts to produce alcohols and halide ions, and a route for the metabolism of 1,2-dichlorethane is proposed. Both dehalogenases show a broad substrate specificity, allowing the degradation of bromine- and chlorine-substituted organic compounds. The results show that X. autotrophicus may play a role in the degradation of organochlorine compounds and that hydrolytic dehalogenases may be involved in the microbial metabolism of short-chain halogenated hydrocarbons in microorganisms. Images PMID:3994371
Ethylene/acrylic elastomers (EAE): sealing application candidates for the automotive industry
DOE Office of Scientific and Technical Information (OSTI.GOV)
Carr, J.; Ginn, A.
1979-01-01
EAE, based on experimental elastomers developed by Du Pont and called ''Vamac'' (formerly ''MPE''), are ethylene/methyl acrylate copolymers compounded with appropriate plasticizers, fillers, and other additives. They function satisfactorily at -54/sup 0/ to +177/sup 0/C and have excellent tensile strength, elongation, and resistance to compression set, corrosion, tear, and weathering. They show good resistance to automatic transmission fluids, engine oil, some gear lubricants and hydrocarbon greases, water, engine coolants, and dilute acids and bases, but should not be used with gasoline, concentrated acids, high-pressure steam, automotive brake fluids, phosphate ester-based hydraulic fluids, diester-based synthetic lubricants, or chlorinated hydrocarbons. They needmore » no solid-lubricant or antiwear additives, but special mold-release preparations are necessary. They should be useful as seals for the transmission front pump, the clutch, and the engine front crankshaft and possibly for other sealing and nonseal applications (e.g., spark-plug boots).« less
2007-03-01
subsurface. The substrate is typically molasses, but other substrates can be used, including high fructose corn syrup , whey, etc. Through subsurface...solution, typically consisting of a carbohydrate such as molasses, whey, high fructose corn syrup , lactate, butyrate, or benzoate. The technology alters...lb of PCE Treated Molasses 0.20 – 0.35 0.16 Sugar ( corn syrup ) 0.25 – 0.30 0.4 Sodium Lactate 1.25 – 1.46 NA Whey (powdered, dry) 1.17 NA Whey
Verreault, Jonathan; Muir, Derek C G; Norstrom, Ross J; Stirling, Ian; Fisk, Aaron T; Gabrielsen, Geir W; Derocher, Andrew E; Evans, Thomas J; Dietz, Rune; Sonne, Christian; Sandala, Gregory M; Gebbink, Wouter; Riget, Frank F; Born, Erik W; Taylor, Mitch K; Nagy, John; Letcher, Robert J
2005-12-01
A suite of chlorinated hydrocarbon contaminants (CHCs) including organochlorine pesticides (OCPs) and by-products, polychlorinated biphenyls (PCBs), and methyl sulfone (MeSO2) PCB and p,p'-dichlorodiphenyldichloroethylene (p,p'-DDE) metabolites were determined in adipose tissue of 107 adult and sub-adult polar bears, almost exclusively females, sampled between 1996 and 2002 from populations spanning Arctic and Subarctic regions of Alaska, Canada, East Greenland, and Svalbard. The East Greenland and Svalbard populations of polar bears were distinguished by higher proportions of dichlorodiphenyldichloroethane (DDT)-related compounds, nonachlors, oxychlordane, and higher-chlorinated and persistent PCB congeners (hepta- to nona-chlorinated). Conversely, Alaska, the westernmost population of the North American Arctic, was characterized by higher proportions of relatively volatile compounds such as hexachlorocyclohexanes (HCHs) and pentachlorobenzene (PnCBz), lower-chlorinated PCB congeners (tri- to penta-chlorinated), and lower proportions of oxychlordane. Geometric mean (GM) with 95% confidence limits (CL) SigmaHCH concentrations were highest in Alaska male polar bear fat samples (GM 593; CL 363-909 ng g-1 lipid weight), SigmaDDT concentration were highest in East Greenland female samples (GM 309; CL 249-490 ng g-1 l.w.), and Sigma42PCB (GM 5972; CL 4637-9129 ng g-1 l.w.) and SigmaMeSO2-PCB (GM 198; CL 162-279 ng g-1 l.w.) concentrations were highest in female samples collected from Svalbard. The distribution of Sigma-chlordane-related compounds (SigmaCHL), SigmaCBz, mirex, and dieldrin was relatively uniform among the populations of polar bears investigated. The present 1996-2002 data of female polar bear fat samples was compared to spatial assessments of female polar bear fat samples collected between 1989 and 1993 from comparable populations. The two-point temporal comparisons showed a general decrease for age-adjusted mean concentrations of SigmaCHL, p,p'-DDE, Sigma42PCB, SigmaMeSO2-PCB and 3-MeSO2-p,p'-DDE over a period of approximately 10 years. However, concentrations of dieldrin were comparatively unchanged. Comparisons of present 2001-2002 concentrations in fat of female polar bears from Western Hudson Bay showed great consistency with temporal trends (1991-1999) previously reported for the same region, i.e. the apparent non-decreasing trend of SigmaCHL, beta-HCH, SigmaHCH and dieldrin, and the apparent declining trend for SigmaPCB. However, present concentrations of alpha-HCH and SigmaCBz were elevated, and SigmaDDT was notably lower in Western Hudson Bay samples compared to the last measurements in fat samples collected in 1999, which was not in accord with reported temporal trends for this region. As a result of their relatively high degree of contamination, East Greenland and Svalbard polar bears are at higher health risk of contaminant exposure among Arctic and Subarctic populations. In addition to continued biomonitoring, further research on health and population status is needed to evaluate the impact from chronic exposure of polar bear populations to CHCs and their metabolites.
Mahl, Magnus; Shoyama, Kazutaka; Rühe, Jessica; Grande, Vincenzo; Würthner, Frank
2018-04-24
Herein we report a palladium-catalyzed annulation reaction consisting of a Suzuki-Miyaura cross-coupling and a C-H arylation cascade for the synthesis of tetrachlorinated polycyclic aromatic dicarboximides (PADIs). This convergent synthetic route afforded a broad series of hitherto unknown electron-deficient PADIs under optimized reaction conditions by coupling of a dibromo-tetrachloro-perylene dicarboximide with different polycyclic aromatic hydrocarbon (PAH) boronic acid pinacol esters in up to 89% yields. The new PADI compounds show broad absorption in the visible range and some of them emit in the near-infrared (NIR) region. Cyclic and square wave voltammetric studies revealed that these tetrachlorinated PADIs are more electron-deficient than a non-chlorinated reference compound and they possess lower lying frontier orbitals. Thus, the newly synthesized electron-poor PADIs are potential n-type semiconductors. Moreover, these chlorinated PADIs are interesting building blocks for the construction of large π-extended arrays by metal-mediated coupling reactions. © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.
NASA Technical Reports Server (NTRS)
Sutter, B.; Archer, D.; Ming, D.; Eigenbrode, J. L.; Franz, H.; Glavin, D. P.; McAdam, A.; Mahaffy, P.; Stern, J.; Navarro-Gonzalex, R.;
2013-01-01
The Sample Analysis at Mars (SAM) instrument onboard the Curiosity rover detected an O2 gas release from the Rocknest eolain bedform (Fig. 1). The detection of perchlorate (ClO4-) by the Mars Phoenix Lander s Wet Chemistry Laboratory (WCL) [1] suggests that perchlorate is a possible candidate for evolved O2 release detected by SAM. The perchlorate would also serve as a source of chlorine in the chlorinated hydrocarbons detected by the SAM quadrupole mass spectrometer (QMS) and gas chromatography/mass spectrometer (GCMS) [2,3]. Chlorates (ClO3-) [4,5] and/or superoxides [6] may also be sources of evolved O2 from the Rocknest materials. The work objectives are to 1) evaluate the O2 release temperatures from Rocknest materials, 2) compare these O2 release temperatures with a series of perchlorates and chlorates, and 3) evaluate superoxide O2- sources and possible perchlorate interactions with other Rocknest phases during QMS analysis.
Natural attenuation of chlorinated hydrocarbons in a freshwater wetland
Lora, Michelle M.; Olsen, Lisa D.; Smith, Barrett L.; Alleman, Bruce C.; Leeson, Andrea
1997-01-01
Natural attenuation of chlorinated volatile organic compounds (VOC's) occurs as ground water discharges from a sand aquifer to a freshwater wetland at Aberdeen Proving Ground, Md. Field and laboratory results indicate that biotransformation in the anaerobic wetland sediments is an important attenuation process. Relatively high concentrations of the parent compounds trichloroethylene (TCE) and 1,1,2,2-tetrachloroethane (PCA) and low or undetectable concentrations of daughter products were measured in the aquifer. In contrast, relatively high concentrations of the daughter products cis- and trans-1,2-dichloroethylene (12DCE); vinyl chloride (VC); 1,1,2-trichloroethane (112TCA); and 1,2-dichloroethane (12DCA) were measured in ground water in the wetland sediments, although total VOC concentrations decreased upward from about 1 mu mol/L (micromoles per liter) at the base of the wetland sediments to less than 0.2 near the surface. Microcosm experiments showed that 12DCE and VC are produced from anaerobic degradation of both TCE and PCA; PCA degradation also produced 112TCA and 12DCA.
Thermal decomposition of selected chlorinated hydrocarbons during gas combustion in fluidized bed
2013-01-01
Background The process of thermal decomposition of dichloromethane (DCM) and chlorobenzene (MCB) during the combustion in an inert, bubbling fluidized bed, supported by LPG as auxiliary fuel, have been studied. The concentration profiles of C6H5CI, CH2Cl2, CO2, CO, NOx, COCl2, CHCl3, CH3Cl, C2H2, C6H6, CH4 in the flue gases were specified versus mean bed temperature. Results The role of preheating of gaseous mixture in fluidized bed prior to its ignition inside bubbles was identified as important factor for increase the degree of conversion of DCM and MCB in low bed temperature, in comparison to similar process in the tubular reactor. Conclusions Taking into account possible combustion mechanisms, it was identified that autoignition in bubbles rather than flame propagation between bubbles is needed to achieve complete destruction of DCM and MCB. These condition occurs above 900°C causing the degree of conversion of chlorine compounds of 92-100%. PMID:23289764
Oxidative decomposition of aromatic hydrocarbons by electron beam irradiation
NASA Astrophysics Data System (ADS)
Han, Do-Hung; Stuchinskaya, Tatiana; Won, Yang-Soo; Park, Wan-Sik; Lim, Jae-Kyong
2003-05-01
Decomposition of aromatic volatile organic compounds (VOCs) under electron beam irradiation was studied in order to examine the kinetics of the process, to characterize the reaction product distribution and to develop a process of waste gas control technology. Toluene, ethylbenzene, o-, m-, p-xylenes and chlorobenzene were used as target materials. The experiments were carried out at doses ranging from 0.5 to 10 kGy, using a flow reactor utilized under electron beam irradiation. Maximum degrees of decomposition carried out at 10 kGy in air environment were 55-65% for “non-chlorinated” aromatic VOC and 85% for chlorobenzene. It was found that a combination of aromatic pollutants with chlorobenzene would considerably increase the degradation value up to nearly 50% compared to the same compounds in the absence of chlorine groups. Based on our experimental observation, the degradation mechanism of the aromatic compounds combined with chloro-compound suggests that a chlorine radical, formed from EB irradiation, induces a chain reaction, resulting in an accelerating oxidative destruction of aromatic VOCs.
Greis, Tillman; Helmholz, Kathrin; Schöniger, Hans Matthias; Haarstrick, Andreas
2012-06-01
In this study, a 3D urban groundwater model is presented which serves for calculation of multispecies contaminant transport in the subsurface on the regional scale. The total model consists of two submodels, the groundwater flow and reactive transport model, and is validated against field data. The model equations are solved applying finite element method. A sensitivity analysis is carried out to perform parameter identification of flow, transport and reaction processes. Coming from the latter, stochastic variation of flow, transport, and reaction input parameters and Monte Carlo simulation are used in calculating probabilities of pollutant occurrence in the domain. These probabilities could be part of determining future spots of contamination and their measure of damages. Application and validation is exemplarily shown for a contaminated site in Braunschweig (Germany), where a vast plume of chlorinated ethenes pollutes the groundwater. With respect to field application, the methods used for modelling reveal feasible and helpful tools to assess natural attenuation (MNA) and the risk that might be reduced by remediation actions.
Thermal decomposition of selected chlorinated hydrocarbons during gas combustion in fluidized bed.
Olek, Malgorzata; Baron, Jerzy; Zukowski, Witold
2013-01-06
The process of thermal decomposition of dichloromethane (DCM) and chlorobenzene (MCB) during the combustion in an inert, bubbling fluidized bed, supported by LPG as auxiliary fuel, have been studied. The concentration profiles of C6H5CI, CH2Cl2, CO2, CO, NOx, COCl2, CHCl3, CH3Cl, C2H2, C6H6, CH4 in the flue gases were specified versus mean bed temperature. The role of preheating of gaseous mixture in fluidized bed prior to its ignition inside bubbles was identified as important factor for increase the degree of conversion of DCM and MCB in low bed temperature, in comparison to similar process in the tubular reactor. Taking into account possible combustion mechanisms, it was identified that autoignition in bubbles rather than flame propagation between bubbles is needed to achieve complete destruction of DCM and MCB. These condition occurs above 900°C causing the degree of conversion of chlorine compounds of 92-100%.
Han, D M; Tong, X X; Jin, M G; Hepburn, Emily; Tong, C S; Song, X F
2013-04-01
This paper investigates the organic pollution status of shallow aquifer sediments and groundwater around Zhoukou landfill. Chlorinated aliphatic hydrocarbons, monocylic aromatic hydrocarbons, halogenated aromatic hydrocarbons, organochlorine pesticides and other pesticides, and polycyclic aromatic hydrocarbons (PAHs) have been detected in some water samples. Among the detected eleven PAHs, phenanthrene, fluorine, and fluoranthene are the three dominant in most of the groundwater samples. Analysis of groundwater samples around the landfill revealed concentrations of PAHs ranging from not detected to 2.19 μg/L. The results show that sediments below the waste dump were low in pollution, and the shallow aquifer, at a depth of 18-30 m, was heavily contaminated, particularly during the wet season. An oval-shaped pollution halo has formed, spanning 3 km from west to east and 2 km from south to north, and mainly occurs in groundwater depths of 2-4 m. For PAH source identification, both diagnostic ratios of selected PAHs and principal component analysis were studied, suggesting mixed sources of pyro- and petrogenic derived PAHs in the Zhoukou landfill. Groundwater table fluctuations play an important role in the distribution of organic pollutants within the shallow aquifer. A conceptual model of leachate migration in the Quaternary aquifers surrounding the Zhoukou landfill has been developed to describe the contamination processes based on the major contaminant (PAHs). The groundwater zone contaminated by leachate has been identified surrounding the landfill.
Nocturnal chlorine radical reservoir species at noon during CalNex-LA 2010
NASA Astrophysics Data System (ADS)
Mielke, L. H.; Griffith, S. M.; Hansen, R. F.; Dusanter, S.; Stevens, P. S.; Flynn, J. H.; Grossberg, N.; Lefer, B. L.; Veres, P. R.; Roberts, J. M.; Gilman, J. B.; Kuster, W. C.; Young, C. J.; Washenfelder, R. A.; Cochran, A. K.; Osthoff, H. D.
2011-12-01
While the role of the hydroxyl radical (OH) in the oxidation of volatile organic compounds (VOCs) is relatively well understood and recognized, less attention has been paid to Cl as an oxidant even though Cl is more reactive towards VOCs than OH. In the troposphere, mixing ratios of chlorine atoms are quite low (103 - 105 atoms cm-3), making them difficult to quantify directly in the atmosphere. The presence of chlorine atoms has been inferred only indirectly using hydrocarbon ratios, but this approach works well only in very remote environments. In polluted coastal urban areas such as Los Angeles, modeling studies have indicated that Cl radical initiated chemistry can have a significant impact on ozone formation. Here, chlorine atoms are produced by reaction of OH with hydrochloric acid and by photolysis of photolabile chlorine containing species, such as the nocturnally formed nitryl chloride (ClNO2) and molecular chlorine (Cl2). In this presentation, measurements of ClNO2 and Cl2 mixing ratios using chemical ionization mass spectrometry (CIMS) at the Calnex-LA campaign ground site between May 15, and June 15, 2010 are presented with a focus on their daytime abundances and photolysis to produce Cl atoms. Photolysis of ClNO2 in the morning (7 am to 10 am) produced Cl atoms at a median rate of 6.1×105 atoms cm-3 s-1. Daytime ClNO2 was observed with a median mixing ratio of 14 parts-per-trillion by volume (pptv). Assuming a steady state between ClNO2 photolysis and its formation via the reaction of Cl atom with NO2, we calculate a median Cl atom concentration of up to 1×105 atoms cm-3, approximately 3% of that of OH, which was quantified by laser induced fluorescence. Implications of Cl on the oxidation of VOCs in the Los Angeles area will be discussed. For example, methane is oxidized by Cl at a relative rate of up to half that of OH under the conditions outlined above.
Process for functionalizing alkanes
Bergman, Robert G.; Janowicz, Andrew H.; Periana-Pillai, Roy A.
1985-01-01
Process for functionalizing saturated hydrocarbons selectively in the terminal position comprising: (a) reacting said saturated hydrocarbons of the formula: RH where: H represents a hydrogen atom, and R represents a saturated hydrocarbon radical, with a metal complex of the formula: CpRhPMe.sub.3 H.sub.2 where: Cp represents a pentamethylated cyclopentadienyl radical, Rh represents a rhodium atom, P represents a phosphorous atom, Me represents a methyl group, H represents a hydrogen atom, in the presence of ultraviolet radiation at a temperature maintained at about -60.degree. to -17.degree. C. to form a hydridoalkyl complex of the formula: CpRhPMe.sub.3 RH (b) reacting said hydridoalkyl complex with a haloform of the formula: CHX.sub.3 where: X represents a bromine, iodine or chlorine atom, at a temperature in the range of about -60.degree. to -17.degree. C. to form the corresponding haloalkyl complex of step (a) having the formula: CpRhPMe.sub.3 RX; and, (c) reacting said haloalkyl complex formed in (b) with halogen (X.sub.2) at a temperature in the range of about -60.degree. to 25.degree. C. (i.e. ambient) to form a functional haloalkyl compound.
Yang, Jie; Meng, Liang; Guo, Lin
2018-02-01
Chlorinated solvents in groundwater pose threats to human health and the environment due to their carcinogenesis and bioaccumulation. These problems are often more severe in developing countries such as China. Thus, methods for chlorinated solvent-contaminated groundwater remediation are urgently needed. This study presents a technique of in situ remediation via the direct-push amendment injection that enhances the reductive dechlorination of chlorinated solvents in groundwater in the low-permeability aquifer. A field-based pilot test and a following real-world, full-scale application were conducted at an active manufacturing facility in Shanghai, China. The chlorinated solvents found at the clay till site included 1,1,1-trichloroethane (1,1,1-TCA), 1,1-dichloroethane (1,1-DCA), 1,1-dichloroethylene (1,1-DCE), vinyl chloride (VC), and chloroethane (CA). A commercially available amendment (EHC ® , Peroxychem, Philadelphia, PA) combining zero-valent iron and organic carbon was used to treat the above pollutants. Pilot test results showed that direct-push EHC injection efficiently facilitated the in situ reductive remediation of groundwater contaminated with chlorinated solvents. The mean removal rates of 1,1,1-TCA, 1,1-DCA, and 1,1-DCE at 270 days post-injection were 99.6, 99.3, and 73.3%, respectively, which were obviously higher than those of VC and CA (42.3 and 37.1%, respectively). Clear decreases in oxidation-reduction potential and dissolved oxygen concentration, and increases in Fe 2+ and total organic carbon concentration, were also observed during the monitoring period. These indicate that EHC promotes the anaerobic degradation of chlorinated hydrocarbons primarily via long-term biological reductive dechlorination, with instant chemical reductive dechlorination acting as a secondary pathway. The optimal effective time of EHC injection was 0-90 days, and its radius of influence was 1.5 m. In full-scale application, the maximum concentrations of 1,1,1-TCA and 1,1-DCA in the contaminate plume fell below the relevant Dutch Intervention Values at 180 days post-injection. Moreover, the dynamics of the target pollutant concentrations mirrored those of the pilot test. Thus, we have demonstrated that the direct-push injection of EHC successfully leads to the remediation of chlorinated solvent-contaminated groundwater in a real-world scenario. The parameters determined by this study (e.g., effectiveness, injection amount, injection depth, injection pressures, and radius of influence) are applicable to other low-permeability contaminated sites where in situ remediation by enhanced reductive dechlorination is required.
Biological Chlorine Cycling in Arctic Peat Soils
NASA Astrophysics Data System (ADS)
Zlamal, J. E.; Raab, T. K.; Lipson, D.
2014-12-01
Soils of the Arctic tundra near Barrow, Alaska are waterlogged and anoxic throughout most of the profile due to underlying permafrost. Microbial communities in these soils are adapted for the dominant anaerobic conditions and are capable of a surprising diversity of metabolic pathways. Anaerobic respiration in this environment warrants further study, particularly in the realm of electron cycling involving chlorine, which preliminary data suggest may play an important role in arctic anaerobic soil respiration. For decades, Cl was rarely studied outside of the context of solvent-contaminated sites due to the widely held belief that it is an inert element. However, Cl has increasingly become recognized as a metabolic player in microbial communities and soil cycling processes. Organic chlorinated compounds (Clorg) can be made by various organisms and used metabolically by others, such as serving as electron acceptors for microbes performing organohalide respiration. Sequencing our arctic soil samples has uncovered multiple genera of microorganisms capable of participating in many Cl-cycling processes including organohalide respiration, chlorinated hydrocarbon degradation, and perchlorate reduction. Metagenomic analysis of these soils has revealed genes for key enzymes of Cl-related metabolic processes such as dehalogenases and haloperoxidases, and close matches to genomes of known organohalide respiring microorganisms from the Dehalococcoides, Dechloromonas, Carboxydothermus, and Anaeromyxobacter genera. A TOX-100 Chlorine Analyzer was used to quantify total Cl in arctic soils, and these data were examined further to separate levels of inorganic Cl compounds and Clorg. Levels of Clorg increased with soil organic matter content, although total Cl levels lack this trend. X-ray Absorption Near Edge Structure (XANES) was used to provide information on the structure of Clorg in arctic soils, showing great diversity with Cl bound to both aromatic and alkyl groups. Incubations were conducted in the laboratory providing arctic soils with Clorg, and measurements taken to assess rates of organohalide respiration show an increase in chloride production due to microbial activity. Investigating these soils with diverse techniques affirms the importance of Cl-cycling in a pristine arctic tundra ecosystem.
Harding, L E; Harris, M L; Stephen, C R; Elliott, J E
1999-02-01
We assessed chlorinated hydrocarbon contamination of mink and river otters on the Columbia and Fraser River systems of northwestern North America, in relation to morphological measures of condition. We obtained carcasses of mink and river otters from commercial trappers during the winters 1994-1995 and 1995-1996. Necropsies included evaluation of the following biological parameters: sex, body mass and length, age, thymus, heart, liver, lung, spleen, pancreas, kidney, gonad, omentum, adrenal gland and baculum masses, baculum length, and stomach contents. Livers were analyzed, individually or in pools, for residues of organochlorine (OC) pesticides, polychlorinated biphenyls (PCBs), dibenzo-p-dioxins, and dibenzofurans. Contaminant levels were relatively low compared to those documented in other North American populations, although they ranged higher than those detected during an earlier survey (1990-1992) of these regional populations. Body condition varied slightly among collection regions, but showed no relationship with contaminant burden. Mink from the upper Fraser River had less fat stores and also had some of the lowest OC contamination levels observed. Similarly, a few individuals with enlarged livers and kidneys had low contaminant levels. Although a few individual animals with gross abnormalities of reproductive systems did not show high levels of contamination, there was a significant negative correlation between total PCB concentrations (as Aroclor 1260) and baculum length in juvenile mink (r = 0.707; p = 0.033; n = 8). The association of juvenile baculum length with eventual reproductive success is unknown, but further characterization of reproductive organ morphology and relationship to contaminants should be undertaken in a larger subset of these populations.
Velimirovic, Milica; Larsson, Per-Olof; Simons, Queenie; Bastiaens, Leen
2013-11-01
Zerovalent iron (ZVI) abiotically degrades several chlorinated aliphatic hydrocarbons (CAHs) via reductive dechlorination, which offers perspectives for in situ groundwater remediation applications. The difference in reactivity between ZVI particles is often linked with their specific surface area. However, other parameters may influence the reactivity as well. Earlier, we reported for a set of microscale zerovalent iron (mZVI) particles the disappearance kinetic of different CAHs which were collected under consistent experimental conditions. In the present study, these kinetic data were correlated with the carbon, oxygen and sulfur content of mZVI particles. It was confirmed that not only the specific surface area affects the disappearance kinetic of CAHs, but also the chemical composition of the mZVI particles. The chemical composition, in addition, influences CAHs removal mechanism inducing sorption onto mZVI particles instead of dechlorination. Generally, high disappearance kinetic of CAHs was observed for particles containing less oxygen. A high carbon content, on the other hand, induced nonreactive sorption of the contaminants on the mZVI particles. To obtain efficient remediation of CAHs by mZVI particles, this study suggested that the carbon and oxygen content should not exceed 0.5% and 1% respectively. Finally, the efficiency of the mZVI particles may be improved to some extent by enriching them with sulfur. However, the impact of sulfur content on the reactivity of mZVI particles is less pronounced than that of the carbon and oxygen content. Copyright © 2013 Elsevier Ltd. All rights reserved.
Atmospheric reactivity of alcohols, thiols and fluoroalcohols with chlorine atoms
NASA Astrophysics Data System (ADS)
Garzon Ruiz, Andres
Alcohols, thiols and fluoroalcohols are volatile organic compounds (VOCs) which are emitted to the atmosphere from both natural (vegetation, oceans, volcanoes, etc.) and anthropogenic sources (fuels, solvents, wastewater, incinerators, refrigerants, etc.). These pollutants can be eliminated from the troposphere by deposition on the terrestrial surface, direct photolysis or reaction with different tropospheric oxidants. Reactions of VOCs with tropospheric oxidants are involved in the well-known atmospheric phenomenon of photochemical smog or the production of tropospheric ozone. The oxidation of these VOCs in the troposphere is mainly initiated by reaction with OH radicals during the daytime and with NO radicals at night. However, in recent years, the oxidation by chlorine atoms (Cl) has gained great importance in the study of atmospheric reactions because they may exert some influence in the boundary layer, particularly in marine and coastal environments. In general, Cl atoms are much more reactive species than OH and NO; radicals and therefore low concentrations of Cl may compete with OH and NO3 in hydrocarbon oxidation processes. The main source of tropospheric Cl atoms is believed to be the photolysis of chlorine-containing molecules generated by heterogeneous reactions of sea salt aerosols. It has also been proposed that Cl atoms, produced in the photolysis of Cl2 emitted from industrial processes, may enhance hydrocarbon oxidation rates and ozone production in urban environments. In this work, a kinetic, theoretical and mechanistic study of the reaction of several alcohols, thiols, and fluoroalcohols with Cl atoms has been carried out. Pulsed laser photolysis-fluorescence resonance (PLP-RF) technique was used for the kinetic study as a function of temperature and pressure. An environmental chamber-Fourier transform infrared (FTIR) system was also employed in the kinetic studies. Tropospheric lifetimes of these pollutants were estimated using obtained kinetic data. Products of these reactions were determined by FTIR and derivatization with 2,4-dinitrophenylhydrazine and HPLC analysis. Finally, in order to determine the main reaction pathways a theoretical study at QCISD(T)/6-311G**//MP2(Full)(6-311C** level was performed for each reaction.
Persistent Organic Pollutants in Dust From Older Homes: Learning From Lead
Metayer, Catherine; Ward, Mary H.; Colt, Joanne S.; Gunier, Robert B.; Deziel, Nicole C.; Rappaport, Stephen M.; Buffler, Patricia A.
2014-01-01
Objectives. We aimed to (1) evaluate the relation between home age and concentrations of multiple chemical contaminants in settled dust and (2) discuss the feasibility of using lead hazard controls to reduce children’s exposure to persistent organic pollutants. Methods. As part of the California Childhood Leukemia Study, from 2001 to 2007, we used a high-volume small surface sampler and household vacuum cleaners to collect dust samples from 583 homes and analyzed the samples for 94 chemicals with gas chromatography–mass spectrometry and inductively coupled plasma mass spectrometry. We evaluated relations between chemical concentrations in dust and home age with Spearman rank correlation coefficients. Results. Dust concentrations of lead, polychlorinated biphenyls, organochlorine insecticides, and polycyclic aromatic hydrocarbons were correlated with home age (ρ > 0.2; P < .001), whereas concentrations of pyrethroid insecticides and polybrominated diphenyl ethers were not. Conclusions. Dust in older homes contains higher levels of multiple, persistent chemicals than does dust in newer homes. Further development of strategies to reduce chemical exposures for children living in older homes is warranted. PMID:24832145
Šyc, Michal; Horák, Jiří; Hopan, František; Krpec, Kamil; Tomšej, Tomáš; Ocelka, Tomáš; Pekárek, Vladimír
2011-11-01
This study reports on the first complex data set of emission factors (EFs) of selected pollutants from combustion of five fuel types (lignite, bituminous coal, spruce, beech, and maize) in six different domestic heating appliances of various combustion designs. The effect of fuel as well as the effect of boiler type was studied. In total, 46 combustion runs were performed, during which numerous EFs were measured, including the EFs of particulate matter (PM), carbon monoxide, polyaromatic hydrocarbons (PAH), hexachlorobenzene (HxCBz), polychlorinated dibenzo-p-dioxins and furans (PCDD/F), etc. The highest EFs of nonchlorinated pollutants were measured for old-type boilers with over-fire and under-fire designs and with manual stoking and natural draft. Emissions of the above-mentioned pollutants from modern-type boilers (automatic, downdraft) were 10 times lower or more. The decisive factor for emission rate of nonchlorinated pollutants was the type of appliance; the type of fuel plays only a minor role. Emissions of chlorinated pollutants were proportional mainly to the chlorine content in fuel, but the type of appliance also influenced the rate of emissions significantly. Surprisingly, higher EFs of PCDD/F from combustion of chlorinated bituminous coal were observed for modern-type boilers (downdraft, automatic) than for old-type ones. On the other hand, when bituminous coal was burned, higher emissions of HxCBz were found for old-type boilers than for modern-type ones.
Sercu, Bram; Jones, Antony D G; Wu, Cindy H; Escobar, Mauricio H; Serlin, Carol L; Knapp, Timothy A; Andersen, Gary L; Holden, Patricia A
2013-01-01
In situ chemical oxidation with permanganate has become an accepted remedial treatment for groundwater contaminated with chlorinated solvents. This study focuses on the immediate and short-term effects of sodium permanganate (NaMnO(4)) on the indigenous subsurface microbial community composition in groundwater impacted by trichloroethylene (TCE). Planktonic and biofilm microbial communities were studied using groundwater grab samples and reticulated vitreous carbon passive samplers, respectively. Microbial community composition was analyzed by terminal restriction fragment length polymorphism and a high-density phylogenetic microarray (PhyloChip). Significant reductions in microbial diversity and biomass were shown during NaMnO(4) exposure, followed by recovery within several weeks after the oxidant concentrations decreased to <1 mg/L. Bray-Curtis similarities and nonmetric multidimensional scaling showed that microbial community composition before and after NaMnO(4) was similar, when taking into account the natural variation of the microbial communities. Also, 16S rRNA genes of two reductive dechlorinators (Desulfuromonas spp. and Sulfurospirillum spp.) and diverse taxa capable of cometabolic TCE oxidation were detected in similar quantities by PhyloChip across all monitoring wells, irrespective of NaMnO(4) exposure and TCE concentrations. However, minimal biodegradation of TCE was observed in this study, based on oxidized conditions, concentration patterns of chlorinated and nonchlorinated hydrocarbons, geochemistry, and spatiotemporal distribution of TCE-degrading bacteria.
NASA Technical Reports Server (NTRS)
Sutter, B.; Archer, D. P.; Ming, D. W.; Niles, P. B.; Eigenbrode, J. L.; Franz, H.; Glavin, D. P.; McAdam, A. C.; Mahaffy, P; Stern, J. C.;
2014-01-01
The Sample Analysis at Mars (SAM) instrument onboard the Curiosity rover detect-ed O2 and HCl gas releases from the Rocknest (RN) eolian bedform and the John Klein (JK) and Cumberland (CB) drill hole materials in Gale Crater. Chlorinated hydrocarbons have also been detected by the SAM quadrupole mass spectrometer (QMS) and gas chromatography/mass spectrometer (GCMS). These detections along with the detection of perchlorate (ClO4-) by the Mars Phoenix Lander’s Wet Chemistry Laboratory (WCL) suggesting perchlorate is a possible candidate for evolved O2 and chlorine species. Laboratory thermal analysis of perchlorates has yet to provide an unequivocal temperature match to the SAM O2 and HCl release data. Iron mineralogy found in the Rocknest materials when mixed with Ca-perchlorate does cause O2 release temperatures to be closer match to the SAM O2 release data but more work is required in evaluating the catalytic effects of Fe mineralogy on perchlorate decomposition. Chlorates (ClO3-) are relevant Mars materials and potential O2 and Cl sources. The objective of this work is to evaluate the thermal decomposition of select chlorate (ClO3-) salts as possible sources of the O2 and HCl releases in the Gale Crater materials.
Kinetics and Near-Infrared Spectroscopy of Organic Peroxy Radicals
NASA Astrophysics Data System (ADS)
Smarte, M. D.; Okumura, M.
2016-12-01
Organic peroxy radicals are important intermediates in atmospheric chemistry with fates that control the rate of radical propagation in an oxidation mechanism. Laboratory methods for detecting peroxy radicals are essential to measuring precise rate constants that constrain these fates. In this work, we discuss the use of near-infrared cavity ringdown spectroscopy to detect organic peroxy radicals for the purpose of laboratory kinetics measurements. We focus on chlorine-substituted peroxy radicals generated in the oxidation of alkenes by chlorine, a minor tropospheric oxidant found in marine and coastal regions. Previous kinetics experiments on peroxy radicals have largely used UV absorption spectroscopy via the dissociative B-X transition. However, the spectra produced are featureless and exhibit substantial overlap; determining the concentration profile of an individual peroxy radical can be an arduous task. In our work, we probe the forbidden peroxy radical A-X transition in the near-infrared. While this approach requires overcoming small cross sections ( 10-21 cm2), the A state is bound and leads to structured absorption spectra that may be useful in constraining the kinetics of mixtures of organic peroxy radicals formed in the oxidation of complex hydrocarbons. Only a few kinetics studies utilizing the A-X transition exist in the literature and they are focused on small, unsubstituted species. This presentation explores the ability of the A-X transition to unravel the kinetics of more complex peroxy radicals in laboratory experiments using several example systems: (1) Determining rate constants for the self and cross reactions of β-chloroethylperoxy and HO2. (2) Detecting the second generation of peroxy radicals formed from alkoxy radical decomposition in the chlorine-initiated oxidation of 2-butene. (3) Observing different rates of reactivity with NO across the pool of peroxy radical isomers formed in the chlorine-initiated oxidation of isoprene.
Effects of DDT on bobwhite quail adrenal gland
Lehman, J.W.; Peterle, T.J.; Mulls, C.M.
1974-01-01
A wide range of responses to sublethal levels of DDT exist, many of which are species specific and vary within each species depending upon age, sex, and physiological state. Sublethal levels of DDT do cause an increase in the adrenal cortical tissue of bobwhite quail, which may cause increased secretion of corticosteroids, and in turn affect reproduction. A delicate homeostatic balance exists within the avian endocrine system which may be disturbed by feeding sublethal levels of chlorinated hydrocarbon pesticides. This adverse effect on the endocrine system may cause subtle reproductive failures which go unnoticed until the population is greatly reduced.
Design of a vehicle based system to prevent ozone loss
NASA Technical Reports Server (NTRS)
Lynn, Sean R.; Bunker, Deborah; Hesbach, Thomas D., Jr.; Howerton, Everett B.; Hreinsson, G.; Mistr, E. Kirk; Palmer, Matthew E.; Rogers, Claiborne; Tischler, Dayna S.; Wrona, Daniel J.
1993-01-01
Reduced quantities of ozone in the atmosphere allow greater levels of ultraviolet light (UV) radiation to reach the earth's surface. This is known to cause skin cancer and mutations. Chlorine liberated from Chlorofluorocarbons (CFC's) and natural sources initiate the destruction of stratospheric ozone through a free radical chain reaction. The project goals are to understand the processes which contribute to stratospheric ozone loss, examine ways to prevent ozone loss, and design a vehicle-based system to carry out the prevention scheme. The 1992/1993 design objectives were to accomplish the first two goals and define the requirements for an implementation vehicle to be designed in detail starting next year. Many different ozone intervention schemes have been proposed though few have been researched and none have been tested. A scheme proposed by R.J. Cicerone, Scott Elliot and R.P.Turco late in 1991 was selected because of its research support and economic feasibility. This scheme uses hydrocarbon injected into the Antarctic ozone hole to form stable compounds with free chlorine, thus reducing ozone depletion. Because most polar ozone depletion takes place during a 3-4 week period each year, the hydrocarbon must be injected during this time window. A study of the hydrocarbon injection requirements determined that 100 aircraft traveling Mach 2.4 at a maximum altitude of 66,000 ft. would provide the most economic approach to preventing ozone loss. Each aircraft would require an 8,000 nm. range and be able to carry 35,000 lbs. of propane. The propane would be stored in a three-tank high pressure system. Missions would be based from airport regions located in South America and Australia. To best provide the requirements of mission analysis, an aircraft with L/D(sub cruise) = 10.5, SFC = 0.65 (the faculty advisor suggested that this number is too low) and a 250,000 lb TOGW was selected as a baseline. Modularity and multi-role functionality were selected to be key design features. Modularity provides ease of turnaround for the down-time critical mission. Multi-role functionality allows the aircraft to be used beyond its design mission, perhaps as an High Speed Civil Transport (HSCT) or for high altitude research.
Two Catalysts for Selective Oxidation of Contaminant Gases
NASA Technical Reports Server (NTRS)
Wright, John D.
2011-01-01
Two catalysts for the selective oxidation of trace amounts of contaminant gases in air have been developed for use aboard the International Space Station. These catalysts might also be useful for reducing concentrations of fumes in terrestrial industrial facilities especially facilities that use halocarbons as solvents, refrigerant liquids, and foaming agents, as well as facilities that generate or utilize ammonia. The first catalyst is of the supported-precious-metal type. This catalyst is highly active for the oxidation of halocarbons, hydrocarbons, and oxygenates at low concentrations in air. This catalyst is more active for the oxidation of hydrocarbons and halocarbons than are competing catalysts developed in recent years. This catalyst completely converts these airborne contaminant gases to carbon dioxide, water, and mineral acids that can be easily removed from the air, and does not make any chlorine gas in the process. The catalyst is thermally stable and is not poisoned by chlorine or fluorine atoms produced on its surface during the destruction of a halocarbon. In addition, the catalyst can selectively oxidize ammonia to nitrogen at a temperature between 200 and 260 C, without making nitrogen oxides, which are toxic. The temperature of 260 C is higher than the operational temperature of any other precious-metal catalyst that can selectively oxidize ammonia. The purpose of the platinum in this catalyst is to oxidize hydrocarbons and to ensure that the oxidation of halocarbons goes to completion. However, the platinum exhibits little or no activity for initiating the destruction of halocarbons. Instead, the attack on the halocarbons is initiated by the support. The support also provides a high surface area for exposure of the platinum. Moreover, the support resists deactivation or destruction by halogens released during the destruction of halocarbons. The second catalyst is of the supported- metal-oxide type. This catalyst can selectively oxidize ammonia to nitrogen at temperatures up to 400 C, without producing nitrogen oxides. This catalyst converts ammonia completely to nitrogen, even when the concentration of ammonia is very low. No other catalyst is known to oxidize ammonia selectively at such a high temperature and low concentration. Both the metal oxide and the support contribute to the activity and selectivity of this catalyst.
NASA Technical Reports Server (NTRS)
Baedecker, M. J.; Ikan, R.; Ishiwatari, R.; Kaplan, I. R.
1977-01-01
The fate of naturally occurring lipids and pigments in a marine sediment exposed to elevated temperatures was studied. Samples of a young marine sediment from Tanner Basin, California, were heated to a series of temperatures (65-200 C) for varying periods of time (7-64 days). The sediment was analyzed prior to and after heating for pigments, isoprenoid compounds, alcohols, fatty acids, and hydrocarbons. Structural changes caused by heating unextractable organic material (kerogen) were also studied, and the significance of the results for understanding petroleum genesis is considered. Among other results, fatty acids and hydrocarbons increased in abundance although there appeared to be no obvious precursor-to-product relationship via simple decarboxylation reactions. Chlorins were partially converted into porphyrins. The phytyl side chain of pheophytin was initially preserved intact by reduction of the phytyl double bond, but later converted to a variety of isoprenoid compounds including alkanes. Thermal grafting of components onto kerogen occurred as well as structural changes caused by heat.
NASA Technical Reports Server (NTRS)
Stern, J. C.; McAdam, A. C.; Archer, P. D., Jr.; Bower, H.; Buch, A.; Eigenbrode, J.; Freissinet, C.; Franz, H. B.; Glavin, D.; Jones, J. H.;
2013-01-01
The Sample Analysis at Mars (SAM) Instrument Suite on the Mars Science Laboratory (MSL) Rover Curiosity made its first solid sample evolved gas analysis of unconsolidated material at aeolian bedform Rocknest in Gale Crater. The magnitude of O2 evolved in each run as well as the chlorinated hydrocarbons detected by SAM gas chromatograph/ mass spectrometer (GCMS) [1] suggest a chlorinated oxidant such as perchlorate in Rocknest materials [2]. Perchlorate induced combustion of organics present in the sample would contribute to the CO2 volatile inventory, possibly overlapping with CO2 from inorganic sources. The resulting carbon and oxygen isotopic composition of CO2 sent to the Tunable Laser Spectrometer (TLS) for analysis would represent mixed sources. This work was undertaken to better understand a) how well the carbon isotopic composition ( 13C) of CO2 from partially combusted products represents their source and b) how the 13C of combusted products can be deconvolved from other carbon sources such as thermal decomposition of carbonate.
NASA Technical Reports Server (NTRS)
Shmalzer, Paul A.; Hensley, Melissa A.; Mota, Mario; Hall, Carlton R.; Dunlevy, Colleen A.
2000-01-01
This study documented background chemical composition of soils, groundwater, surface; water, and sediments of Kennedy Space Center. Two hundred soil samples were collected, 20 each in 10 soil classes. Fifty-one groundwater wells were installed in 4 subaquifers of the Surficial Aquifer and sampled; there were 24 shallow, 16 intermediate, and 11 deep wells. Forty surface water and sediment samples were collected in major watershed basins. All samples were away from sites of known contamination. Samples were analyzed for organochlorine pesticides, aroclors, chlorinated herbicides, polycyclic aromatic hydrocarbons (PAH), total metals, and other parameters. All aroclors (6) were below detection in all media. Some organochlorine pesticides were detected at very low frequencies in soil, sediment, and surface water. Chlorinated herbicides were detected at very low frequencies in soil and sediments. PAH occurred in low frequencies in soiL, shallow groundwater, surface water, and sediments. Concentrations of some metals differed among soil classes, with subaquifers and depths, and among watershed basins for surface water but not sediments. Most of the variation in metal concentrations was natural, but agriculture had increased Cr, Cu, Mn, and Zn.
PCB intake from sport fishing along the Northern Illinois shore of Lake Michigan
DOE Office of Scientific and Technical Information (OSTI.GOV)
Pellettieri, M.B.; Hallenbeck, W.H.; Brenniman, G.R.
1996-12-31
Polychlorinated biphenyls (PCBs) are chlorinated hydrocarbons with an empirical formula of C{sub 12}H{sub 10-x}Cl{sub x}. The biphenyl can have from one to 10 chlorine substitutions resulting in 209 theoretical congeners. Commercial formulations of PCBs are complex mixtures of congeners; 125 congeners have been identified in commercial formulations. PCBs have entered the aquatic environment by industrial discharge, airborne deposition, and release from sediments. The most likely route of non-occupational human exposure to PCBs is from consumption of contaminated fish. PCBs are considered to be the most important contaminants in fish from the Great Lakes. Hence, in 1993 the Great Lakes Fishmore » and Advisory Task Force developed a fish consumption advisory for the Great Lakes which incorporated a Health Protection Value (HPV) of 3.5 {mu}g of PCBs/day. This study combines the creel species, weight, and length distribution data with PCB monitoring data to quantitate the theoretical intake of PCBs by sport fishermen in the Chicago area. 6 refs., 3 tabs.« less
Complete dechlorination of DDE/DDD using magnesium/palladium system.
Gautam, Sumit Kumar; Suresh, Sumathi
2007-04-01
Kinetic studies on the dechlorination of 1,1-dichloro-2,2 bis (4,-chlorophenyl) ethane (DDD) and 1,1,dichloro-2,2 bis (4,-chlorophenyl) ethylene (DDE) in 0.05% biosurfactant revealed that the reaction follows second-order kinetics. The rate of reaction was dependent on the presence of acid, initial concentrations of the target compound, and zerovalent magnesium/tetravalent palladium. Gas chromatography-mass spectrometry analyses of DDE dechlorination revealed the formation of a completely dechlorinated hydrocarbon skeleton, with diphenylethane as the end product, thereby implying the removal of all four chlorine atoms of DDE. In the case of DDD, we identified two partially dechlorinated intermediates [namely, 1,1-dichloro-2, 2 bis (phenyl) ethane and 1, chloro-2, 2 bis (phenyl) ethane] and diphenylethane as the end product. On the basis of products formed from DDD dehalogenation, we propose the removal of aryl chlorine atoms as a first step. Our investigation reveals that biosurfactant may be an attractive solubilizing agent for DDT and its residues. The magnesium/palladium system is a promising option because of its high reactivity and ability to achieve complete dechlorination of DDE and DDD.
Tsai, Wen-Tien
2017-09-21
Among the halogenated hydrocarbons, chloromethanes (i.e., methyl chloride, CH₃Cl; methylene chloride, CH₂Cl₂; chloroform, CHCl₃; and carbon tetrachloride, CCl₄) play a vital role due to their extensive uses as solvents and chemical intermediates. This article aims to review their main chemical/physical properties and commercial/industrial uses, as well as the environment and health hazards posed by them and their toxic decomposition products. The environmental properties (including atmospheric lifetime, radiative efficiency, ozone depletion potential, global warming potential, photochemical ozone creation potential, and surface mixing ratio) of these chlorinated methanes are also reviewed. In addition, this paper further discusses their atmospheric fates and human health implications because they are apt to reside in the lower atmosphere when released into the environment. According to the atmospheric degradation mechanism, their toxic degradation products in the troposphere include hydrogen chloride (HCl), carbon monoxide (CO), chlorine (Cl₂), formyl chloride (HCOCl), carbonyl chloride (COCl₂), and hydrogen peroxide (H₂O₂). Among them, COCl₂ (also called phosgene) is a powerful irritating gas, which is easily hydrolyzed or thermally decomposed to form hydrogen chloride.
DOE Office of Scientific and Technical Information (OSTI.GOV)
Not Available
The Texarkana Wood Preserving Company (TWPC) is a National Priorities List site located in northeastern Texas, at the southern extremity of the City of Texarkana in Bowie County. The TWPC site has been used for various lumber-related activities since the early 1900s and for creosoting operations since the early 1950s. Contaminated soils, groundwater, surface water, and surface water sediments have been detected on and off of the TWPC site. The primary contaminants of concern are polycyclic aromatic hydrocarbons, pentachlorophenol, chlorinated dibenzodioxins and chlorinated dibenzofurans. The population at greatest risk of exposure to these contaminants are on-site workers engaged in remedialmore » activities. There are currently no residences or businesses located immediately adjacent to the site and no documentation that contaminated groundwater is being used for potable purposes. The Texarkana Wood Preserving Company site has been evaluated by the Agency for Toxic Substances and Disease Registry (ATSDR) Health Activities Recommendation Panel (HARP) for appropriate follow-up with respect to health activities.« less
SMM mesospheric ozone measurements
NASA Technical Reports Server (NTRS)
Aikin, A. C.
1990-01-01
The main objective was to understand the secular and seasonal behavior of ozone in the lower mesosphere, 50 to 70 km. This altitude region is important in understanding the factors which determine ozone behavior. A secondary objective is the study of stratospheric ozone in the polar regions. Use is made of results from the SBUV satellite borne instrument. In the Arctic the interaction between chlorine compounds and low molecular weight hydrocarbons is studied. More than 30,000 profiles were obtained using the UVSP instrument on the SMM spacecraft. Several orbits of ozone data per day were obtained allowing study of the current rise in solar activity from the minimum until the present. Analysis of Nimbus 7 SBUV data in Antarctic spring indicates that ozone is depleted within the polar vortex relative to ozone outside the vortex. This depletion confirms the picture of ozone loss at altitudes where polar stratospheric clouds exist. In addition, there is ozone loss above the cloud level indicating that there is another mechanism in addition to ozone loss initiated by heterogeneous chlorine reactions on cloud particles.
Xu, Hui; Xiao, Xiao; Zhao, Xue-Fei; Guo, Yong; Yao, Xiao-Jun
2011-07-01
Twenty-one 4α-acyloxy-2-chloropodophyllotoxin derivatives (5a-u), whose C-4 spatial configuration was mainly stereocontrolled by the configuration of C-2 chlorine atom, were unexpectedly prepared by the reaction of 2-chloropodophyllotoxin with carboxylic acids in the presence of BF(3)·Et(2)O. Compared with ordinary esterifications of carboxylic acids mediated by the condensation agent, for example, N,N'-diisopropylcarbodiimide (DIC), the present method made the procedure for the preparation of 4α-acyloxy-2-chloropodophyllotoxins more convenient, practical and easy. Meanwhile, the insecticidal activity of compounds 5a-u was preliminarily evaluated against the pre-third-instar larvae of Mythimna separata Walker in vivo at the concentration of 1mg/mL. Copyright © 2011 Elsevier Ltd. All rights reserved.
In situ bioremediation of petroleum hydrocarbons and chlorinated hydrocarbons: Three case studies
DOE Office of Scientific and Technical Information (OSTI.GOV)
Bost, R.C.; Perry, R.G.; Barber, T.
1997-06-01
In situ biodegradation of organic contaminants is one of the most cost-effective means of site remediation. This method has proven successful in soils, ground water, and slurries. Bacteria capable of degrading organic contaminants within an aquifer include many species from a wide spectrum of genera, e.g. Pseudomonas, Corynebacterium, Bacillus, etc. In most cases, a mixture of bacterial strains is required to completely oxidize a complex organic contaminant. Each strain of an organism may target a specific compound, working together with other organisms to ultimately degrade each intermediate until complete degradation, also known as mineralization, occurs. One or more of themore » following mechanisms are utilized by bacteria for organic chemical degradation: (1) aerobic, (2) anaerobic, and (3) co-metabolic. During aerobic oxidation of organic chemicals, bacteria utilize the pollutant as an electron and hydrogen source and oxygen acts as the electron and hydrogen acceptor, resulting in water. As the bacterial enzymes cleave the compound, oxidized products are produced along with energy for the reaction to proceed. This is the most rapid and widely utilized mechanism. Dehalogenation occurs under aerobic, or perhaps more often, under anoxic conditions. This process occurs in the presence of alternate electron acceptors and replaces chlorine with hydrogen. The mechanism of co-metabolism can be aerobic or anaerobic, but is more often aerobic. This process requires a separate energy source for the bacterial cell because the pollutant is not utilized as an energy source. The role of bioremediation in site remediation is demonstrated below by three case studies: (1) a refinery, (2) a municipal landfill and (3) a pesticide formulation plant.« less
Hunt, James; Birch, Gavin; Warne, Michael St J
2010-05-01
Groundwater contaminated with volatile chlorinated hydrocarbons (VCHs) was identified as discharging to Penrhyn Estuary, an intertidal embayment of Botany Bay, New South Wales, Australia. A screening-level hazard assessment of surface water in Penrhyn Estuary identified an unacceptable hazard to marine organisms posed by VCHs. Given the limitations of hazard assessments, the present study conducted a higher-tier, quantitative probabilistic risk assessment using the joint probability curve (JPC) method that accounted for variability in exposure and toxicity profiles to quantify risk (delta). Risk was assessed for 24 scenarios, including four areas of the estuary based on three exposure scenarios (low tide, high tide, and both low and high tides) and two toxicity scenarios (chronic no-observed-effect concentrations [NOEC] and 50% effect concentrations [EC50]). Risk (delta) was greater at low tide than at high tide and varied throughout the tidal cycle. Spatial distributions of risk in the estuary were similar using both NOEC and EC50 data. The exposure scenario including data combined from both tides was considered the most accurate representation of the ecological risk in the estuary. When assessing risk using data across both tides, the greatest risk was identified in the Springvale tributary (delta=25%)-closest to the source area-followed by the inner estuary (delta=4%) and the Floodvale tributary (delta=2%), with the lowest risk in the outer estuary (delta=0.1%), farthest from the source area. Going from the screening level ecological risk assessment (ERA) to the probabilistic ERA changed the risk from unacceptable to acceptable in 50% of exposure scenarios in two of the four areas within the estuary. The probabilistic ERA provided a more realistic assessment of risk than the screening-level hazard assessment. Copyright (c) 2010 SETAC.
Venkatesan, M.I.; De Leon, R. P.; VanGeen, A.; Luoma, S.N.
1999-01-01
Sediment cores of known chronology from Richardson and San Pablo Bays in San Francisco Bay, CA, were analyzed for a suite of chlorinated hydrocarbon pesticides and polychlorinated biphenyls to reconstruct a historic record of inputs. Total DDTs (DDT = 2,4'- and 4,4'-dichlorodiphenyltrichloroethane and the metabolites, 2,4'- and 4,4'-DDE, -DDD) range in concentration from 4-21 ng/g and constitute a major fraction (> 84%) of the total pesticides in the top 70 cm of Richardson Bay sediment. A subsurface maximum corresponds to a peak deposition date of 1969-1974. The first measurable DDT levels are found in sediment deposited in the late 1930's. The higher DDT inventory in the San Pablo relative to the Richardson Bay core probably reflects the greater proximity of San Pablo Bay to agricultural activities in the watershed of the Sacramento and San Joaquin rivers. Total polychlorinated biphenyls (PCBs) occur at comparable levels in the two Bays (< 1-34 ng/g). PCBs are first detected in sediment deposited during the 1930's in Richardson Bay, about a decade earlier than the onset of detectable levels of DDTs. PCB inventories in San Pablo Bay are about a factor of four higher in the last four decades than in Richardson Bay, suggesting a distribution of inputs not as strongly weighed towards the upper reaches of the estuary as DDTs. The shallower subsurface maximum in PCBs compared to DDT in the San Pablo Bay core is consistent with the imposition of drastic source control measures four these constituents in 1970 and 1977 respectively. The observed decline in DDT and PCB levels towards the surface of both cores is consistent with a dramatic drop in the input of these pollutants once the effect of sediment resuspension and mixing is taken into account.
Nuhu, Abdulmumin A; Basheer, Chanbasha; Abu-Thabit, Nedal Y; Alhooshani, Khalid; Al-Arfaj, Abdul Rahman
2011-12-15
In this study, functionalized polysulfone membrane has been utilized as a sorbent for the extraction of chlorinated hydrocarbons (CHCs) in water samples. Two different functionalized polysulfones (i) phosphonic acid functionalized polysulfone (PPSU-A) with different forms (cross-linked and non cross-linked) membranes and (ii) phosphonic ester functionalized polysulfone (PPSU-E) with different forms (cross-linked and non cross-linked) were evaluated for the extraction of CHCs in water. A 10 ml of spiked water sample was extracted with 50mg piece of the functionalized membrane. After extraction, the membrane was desorbed by organic solvent and the extract was analyzed by gas chromatography-mass spectrometry. Eight CHCs, 1,3,5-trichlorobenzene (1,3,5-TCB), 1,2,3-trichlorobenzene (1,2,3-TCB), 1,1,2,3,4,4-hexachloro-1,3-butadiene (HCBD), 1,2,4-trichloro-3-methylbenzene (TCMB), 1,2,3,4-tetrachlorobenzene (1,2,3,4-TeCB), 1,2,4,5-tetrachlorobenzene (1,2,4,5-TeCB), pentachlorobenzene (PeCB) and hexachlorobenzene (HCB) were used as model compounds. Experimental parameters such as extraction time, desorption time, types of polymer membrane as well the nature of desorption solvent were optimized. Using optimum extraction conditions calibration curves were linear with coefficients of determination between 0.9954 and 0.9999 over wide range of concentrations (0.05-100 μgl(-1)). The method detection limits (at a signal-to-noise ratio of 3) were in the range of 0.4-3.9 ng l(-1). The proposed method was evaluated for the determination of CHCs in drinking water samples. Copyright © 2011 Elsevier B.V. All rights reserved.
NASA Astrophysics Data System (ADS)
Stephens, C. R.; Helmig, D.; Evans, J.; Hueber, J.; Park, J.; Boylan, P.
2013-12-01
Emissions of non-methane hydrocarbons (NMHC) are primarily linked to anthropogenic fossil fuel activities, such as oil and natural gas extraction and distribution, and are important tropospheric ozone precursors. The Uintah Basin, Utah, is a region of heavy oil and natural gas development where high winter-time ozone production events have been observed during strong inversions when there is snow cover present. In the winters of 2012 and 2013, we conducted measurements of methane and NMHC during the Uintah Basin Winter Ozone Study. NMHC were monitored along a vertical gradient up to 150 m using a flux tower and tethered balloon. In 2013, measurements of NMHC were also conducted from within the snowpack. In 2012, no high ozone events were observed. In contrast, during the 2013 study, several periods of high ozone occurred concurrently with strong increases in ambient NMHC. Here, we present vertical profile measurements of C2-C5 alkanes, benzene and toluene comparing 2012 and 2013. Data from 2013 show strong vertical gradients with build-up of NMHC and ozone near the surface during inversion events, with wash out of both ozone and ozone precursors during low pressure front passage from the west. The NOAA/INSTAAR global flask network provides a useful comparison for expected regional background values of NMHC, and we find up to a 570-fold enhancement in Uintah, providing evidence for the importance of local emissions sources. Investigation of NMHC ratios reveals distinctly different values in the ambient air and within the snowpack, suggesting active radical chemistry occurring in the snow. Analysis of butane and pentane isomer ratios points towards the presence of chlorine radicals, indicating that the snow may serve as a reactive chlorine reservoir that may enhance ozone production chemistry.
Pierro, Lucia; Matturro, Bruna; Rossetti, Simona; Sagliaschi, Marco; Sucato, Salvatore; Alesi, Eduard; Bartsch, Ernst; Arjmand, Firoozeh; Papini, Marco Petrangeli
2017-07-25
A pilot-scale study aiming to evaluate the potential use of poly-3-hydroxy-butyrate (PHB) as an electron donor source for in situ bioremediation of chlorinated hydrocarbons in groundwater was conducted. Compared with commercially available electron donors, PHB offers a restricted fermentation pathway (i.e., through acetic acid and molecular hydrogen) by avoiding the formation of any residual carbon that could potentially spoil groundwater quality. The pilot study was carried out at an industrial site in Italy, heavily contaminated by different chlorinated aliphatic hydrocarbons (CAHs). Prior to field testing, PHB was experimentally verified as a suitable electron donor for biological reductive dechlorination processes at the investigated site by microcosm studies carried out on site aquifer material and measuring the quantitative transformation of detected CAHs to ethene. Owing to the complex geological characteristics of the aquifer, the use of a groundwater circulation well (GCW) was identified as a potential strategy to enable effective delivery and distribution of electron donors in less permeable layers and to mobilise contaminants. A 3-screened, 30-m-deep GCW coupled with an external treatment unit was installed at the site. The effect of PHB fermentation products on the in situ reductive dechlorination processes were evaluated by quantitative real-time polymerase chain reaction (qPCR). The results from the first 4 months of operation clearly demonstrated that the PHB fermentation products were effectively delivered to the aquifer and positively influenced the biological dechlorination activity. Indeed, an increased abundance of Dehalococcoides mccartyi (up to 6.6 fold) and reduced CAH concentrations at the installed monitoring wells were observed. Copyright © 2016 Elsevier B.V. All rights reserved.
Chemical compatibility screening test results
DOE Office of Scientific and Technical Information (OSTI.GOV)
Nigrey, P.J.; Dickens, T.G.
1997-12-01
A program for evaluating packaging components that may be used in transporting mixed-waste forms has been developed and the first phase has been completed. This effort involved the screening of ten plastic materials in four simulant mixed-waste types. These plastics were butadiene-acrylonitrile copolymer rubber, cross-linked polyethylene (XLPE), epichlorohydrin rubber, ethylene-propylene rubber (EPDM), fluorocarbon (Viton or Kel-F), polytetrafluoroethylene, high-density polyethylene (HDPE), isobutylene-isoprene copolymer rubber (butyl), polypropylene, and styrene-butadiene rubber (SBR). The selected simulant mixed wastes were (1) an aqueous alkaline mixture of sodium nitrate and sodium nitrite; (2) a chlorinated hydrocarbon mixture; (3) a simulant liquid scintillation fluid; and (4) amore » mixture of ketones. The testing protocol involved exposing the respective materials to 286,000 rads of gamma radiation followed by 14-day exposures to the waste types at 60{degrees}C. The seal materials were tested using vapor transport rate (VTR) measurements while the liner materials were tested using specific gravity as a metric. For these tests, a screening criterion of 0.9 g/hr/m{sup 2} for VTR and a specific gravity change of 10% was used. Based on this work, it was concluded that while all seal materials passed exposure to the aqueous simulant mixed waste, EPDM and SBR had the lowest VTRs. In the chlorinated hydrocarbon simulant mixed waste, only Viton passed the screening tests. In both the simulant scintillation fluid mixed waste and the ketone mixture simulant mixed waste, none of the seal materials met the screening criteria. For specific gravity testing of liner materials, the data showed that while all materials with the exception of polypropylene passed the screening criteria, Kel-F, HDPE, and XLPE offered the greatest resistance to the combination of radiation and chemicals.« less
Delta 37Cl and Characterisation of Petroleum-gas Reservoirs
NASA Astrophysics Data System (ADS)
Woulé Ebongué, V.; Jendrzejewski, N.; Walgenwitz, F.; Pineau, F.; Javoy, M.
2003-04-01
The geochemical characterisation of formation waters from oil/gas fields is used to detect fluid-flow barriers in reservoirs and to reconstruct the system dynamic. During the progression of the reservoir filling, the aquifer waters are pushed by hydrocarbons toward the reservoir bottom and their compositions evolve due to several parameters such as water-rock interactions, mixing with oil-associated waters, physical processes etc. The chemical and isotopic evolution of these waters is recorded in irreducible waters that have been progressively "fossilised" in the oil/gas column. Residual salts precipitated from these waters were recovered. Chloride being the most important dissolved anion in these waters and not involved in diagenetic reactions, its investigation should give insights into the different transport or mixing processes taking place in the sedimentary basin and point out to the formation waters origins. The first aim of our study was to test the Cl-RSA technique (Chlorine Residual Salts Analysis) based on the well-established Sr-RSA technique. The main studied area is a turbiditic sandstone reservoir located in the Lower Congo basin in Angola. Present-day aquifer waters, irreducible waters from sandstone and shale layers as well as drilling mud and salt dome samples were analysed. Formation waters (aquifer and irreducible trapped in shale) show an overall increase of chlorinity with depth. Their δ37Cl values range from -1.11 ppm to +2.30 ppm ± 0.05 ppm/ SMOC. Most Cl-RSA data as well as the δ37Cl obtained on a set of water samples (from different aquifers in the same area) are lower than -0.13 ppm with lower δ37Cl values at shallower depths. In a δ37Cl versus chlorinity diagram, they are distributed along a large range of chlorinity: 21 to 139 g/l, in two distinct groups. (1) Irreducible waters from one of the wells display a positive correlation between chlorinity and the δ37Cl values. (2) In contrary, the majority of δ37Cl measured on aquifers and on residual salts from a second well are anti-correlated with chlorinity. The preliminary determinations of δ37Cl values of sandstone irreducible waters seem to match the values obtained on irreducible waters trapped in the shale porosity. δ37Cl values and chlorinities are used to identify the contributions of physico-chemical processes such as ion filtration, diffusion or mixing. The chronology of the events and their relative importance are discussed.
DOE Office of Scientific and Technical Information (OSTI.GOV)
Bercovici, B.; Wassermann, M.; Cucos, S.
Polychlorinated biphenyls and some organochlorine insecticides (DDT isomers and their metabolites, indane (..gamma..-BHC), dieldrin, heptachlor epoxide) were assessed in the serum of 17 women with recent missed abortions, 7 women who experienced one or several missed abortions in their past, and 7 women with normal, second trimester pregnancy. Fifty-three percent of the cases of recent missed abortion had PCB serum levels higher than the mean plus two standard deviations of the control group. The mean PCB serum level in women with recent missed abortion and relatively high PCB serum levels was significantly different from that of the control group (103.04more » versus 20.69 ppb,P<0.001). The mean PCB serum level of the former missed abortions group was also significantly different from that of the control group (82.00 versus 20.69 ppb, P<0.001). The quantity of the higher chlorinated biphenyl homologues (penta- and hexachlorobiphenyls) was increased in the high PCB level, missed abortion group and in the former missed abortion group, while the lower chlorinated biphenyl homologues were decreased in these groups in comparsion with the control group. The fact that the former missed abortion group showed increased PCB serum levels similar to those found in the high PCB level, recent missed abortion group confirms the existence of an association between relatively high PCB serum levels and the occurance of missed abortion. (JMT)« less
Hanley, M E; Cruickshanks, K L; Dunn, D; Stewart-Jones, A; Goulson, D
2009-03-01
Houseflies (Musca domestica L.) are a major pest species of livestock units and landfill sites. Insecticide resistance has resulted in an increased emphasis on lure-and-kill control methods, but the success of this approach relies on the effective attraction of houseflies with olfactory or visual stimuli. This study examined the efficacy of olfactory (cuticular hydrocarbons) or visual (colours and groups of flies) attractants in a commercial poultry unit. Despite simulating the cuticular hydrocarbon profiles of male and female houseflies, we found no significant increase in the number of individuals lured to traps and no sex-specific responses were evident. The use of target colours selected to match the three peaks in housefly visual spectral sensitivity yielded no significant increase in the catch rate of traps to which they were applied. This study also demonstrated that male and female flies possess significantly different spectral reflectance (males are brighter at 320-470 nm; females are brighter at 470-670 nm). An experiment incorporating groups of recently killed flies from which cuticular hydrocarbons were either removed by solvent or left intact also failed to show any evidence of olfactory or visual attraction for houseflies of either sex. This study concluded that variations of the most commonly applied methods of luring houseflies to traps in commercial livestock units fail to significantly increase capture rates. These results support commonly observed inconsistencies associated with using olfactory or visual stimuli in lure-and-kill systems, possibly because field conditions lessen the attractant properties observed in laboratory experiments.
Ramaiah, K Pattabhi; Satyasri, D; Sridhar, S; Krishnaiah, A
2013-10-15
Hydrophobic polymer possesses significant potential for selective separation of volatile organic compounds (VOCs) from their aqueous solutions by pervaporation (PV). In the present study mixed matrix hydrophobic membranes of polydimethylsiloxane (PDMS) supported on polyvinylidenefluoride (PVDF) substrate were synthesized by incorporating hydrophobic inorganic ZSM-5 filler. The indigenous membranes were crosslinked with tetraethylorthosilicate (TEOS) for the extraction of volatile chlorinated hydrocarbons such as dichloromethane (DCM), trichloromethane (TCM), 1,2-dichloroethane (DCE), and 1,1,2,2-tetrachloroethane (TeCE), which pose serious environment threat and health hazard. Thermal stability, crosslinking, crystallinity, surface morphology and swelling characteristics of the indigenously developed membranes were determined by TGA, FTIR, XRD, SEM and sorption studies, respectively. Effect of operating parameters such as feed composition and filler concentration on separation performance in terms of flux and selectivity were determined. Flux of DCM, TCM, DCE and TeCE was found to be 0.166, 0.146, 0.141 and 0.06 kg m(-2)h(-1) with selectivity of 541, 1068, 917 and 15,000, respectively, for 20% ZSM-5 filled PDMS membrane for aqueous feeds containing 1.33% (w/v) DCM, 0.8% (w/v) TCM, 0.84% (w/v) DCE and 0.28% (w/v) TeCE in water. The membrane exhibited considerable feasibility for scale-up with significant potential for removal of hazardous chlorinated VOCs from aqueous solutions. Copyright © 2013 Elsevier B.V. All rights reserved.
DOE Office of Scientific and Technical Information (OSTI.GOV)
NONE
1996-05-14
The Tutu Wellfield National Priorities List (NPL) site is in east-central St. Thomas, U.S. Virgin Island. Twenty-two wells in the Turpentine Run Basin contain at minimum a trace of volatile organic contaminants. Volatile and chlorinated hydrocarbons including benzene; toluene; 1,2-trans-dichloroethene (DCE); trichloroethene (TCE); and tetrachloroethene (PCE) were detected in several of the wells. The Agency for Toxic Substances and Disease Registry (ATSDR) has concluded that the Tutu Wellfield National Priorities List (NPL) site, St. Thomas, U.S. Virgin Islands, poses a public health hazard for past, present, and possible future ingestion of contaminated groundwater.
Depth-dependent positron annihilation in different polymers
NASA Astrophysics Data System (ADS)
Yang, J.; Zhang, P.; Cheng, G. D.; Li, D. X.; Wu, H. B.; Li, Z. X.; Cao, X. Z.; Jia, Q. J.; Yu, R. S.; Wang, B. Y.
2013-09-01
Depth-dependent positron annihilation Doppler broadening measurements were conducted for polymers with different chemical compositions. Variations of the S parameter with respect to incident positron energy were observed. For pure hydrocarbons PP, HDPE and oxygen-containing polymer PC, S parameter rises with increasing positron implantation depth. While for PI and fluoropolymers like PTFE, ETFE and PVF, S parameter decreases with higher positron energy. For chlorine-containing polymer PVDC, S parameter remains nearly constant at all incident positron energies. It is suggested that these three variation trends are resulted from a competitive effect between the depth-dependent positronium formation and the influence of highly electronegative atoms on positron annihilation characteristics.
The comparative toxicity of DDT and analogues to susceptible and resistant houseflies and mosquitos*
Metcalf, R. L.; Fukuto, T. R.
1968-01-01
Studies of the comparative toxicity of more than 120 DDT analogues to susceptible and insecticide-resistant houseflies (Musca domestica L.) and mosquitos (Culex fatigans Wiedemann and Anopheles albimanus Wiedemann) have shown that the relative effectiveness of these compounds against DDT-resistant insects is correlated with the susceptibility of the molecule to attack by DDT-ase at the benzylic hydrogen. Compounds highly effective against DDT-resistant flies and mosquitos are produced by blocking this detoxication mechanism by o-chlorination, α-fluorination, and by altering the aliphatic portion of the molecule as in the nitropropyl, neopentyl, dichlorocyclopropyl, and trichlorobenzanilide derivatives. These compounds offer practical possibilities for the control of DDT-resistant insects. The correlation of structure, DDT-like activity, and resistance ratios gives new insight into the mode of action of DDT and the nature of DDT resistance. PMID:4386201
Sharma, Suman; Singh, Partapbir; Raj, Mayil; Chadha, Bhupinder Singh; Saini, Harvinder Singh
2009-11-15
The different isomers of technical-grade hexachlorocyclohexane (t-HCH) including the insecticidal gamma-isomer, commonly known as lindane, have been reported to be toxic, carcinogenic and endocrine disrupters. The spatial arrangements of the chlorine atoms on different isomers and low aqueous phase solubility contribute to their persistence in environment, beta-HCH being the most resistance to transformation. The biosurfactant preparation of Pseudomonas aeruginosa isolate WH-2 was evaluated for its ability to improve the aqueous phase partitioning of different isomers of HCH-muck. Further, the ability of biosurfactant preparation to emulsify HCH and n-hexadecane was checked under different conditions, usually characteristic of sites contaminated with pollutants viz. wide range of pH, temperature, and salinity. The data obtained from this study will be helpful in designing suitable bioremediation strategies for huge stock piles of HCH-muck and sites polluted by reckless use/disposal of HCH-isomers.
Cui, Xinyi; Mayer, Philipp; Gan, Jay
2013-01-01
Many important environmental contaminants are hydrophobic organic contaminants (HOCs), which include PCBs, PAHs, PBDEs, DDT and other chlorinated insecticides, among others. Owing to their strong hydrophobicity, HOCs have their final destination in soil or sediment, where their ecotoxicological effects are closely regulated by sorption and thus bioavailability. The last two decades has seen a dramatic increase in research efforts in developing and applying partitioning based methods and biomimetic extractions for measuring HOC bioavailability. However, the many variations of both analytical methods and associated measurement endpoints are often a source of confusion for users. In this review, we distinguish the most commonly used analytical approaches based on their measurement objectives, and illustrate their practical operational steps, strengths and limitations using simple flowcharts. This review may serve as guidance for new users on the selection and use of established methods, and a reference for experienced investigators to identify potential topics for further research. PMID:23064200
DOE Office of Scientific and Technical Information (OSTI.GOV)
Dawson, Gaynor; McKeon, Tom
Enhanced reductive dechlorination (ERD) has rapidly become a remedy of choice for use on chlorinated solvent contamination when site conditions allow. With this approach, solutions of an organic substrate are injected into the affected aquifer to stimulate biological growth and the resultant production of reducing conditions in the target zone. Under the reducing conditions, hydrogen is produced and ultimately replaces chlorine atoms on the contaminant molecule causing sequential dechlorination. Under suitable conditions the process continues until the parent hydrocarbon precursor is produced, such as the complete dechlorination of trichloroethylene (TCE) to ethene. The process is optimized by use of amore » substrate that maximizes hydrogen production per unit cost. When natural biota are not present to promote the desired degradation, inoculates can be added with the substrate. The in-situ method both reduces cost and accelerates cleanup. Successful applications have been extended from the most common chlorinated compounds perchloroethylene (PCE) and TCE and related products of degradation, to perchlorate, and even explosives such as RDX and trinitrotoluene on which nitrates are attacked in lieu of chloride. In recent work, the process has been further improved through use of beverage industry wastewaters that are available at little or no cost. With material cost removed from the equation, applications can maximize the substrate loading without significantly increasing total cost. The extra substrate loading both accelerates reaction rates and extends the period of time over which reducing conditions are maintained. In some cases, the presence of other organic matter in addition to simple sugars provides for longer performance times of individual injections, thereby working in a fashion similar to emulsified vegetable oil. The paper discusses results of applications at three different sites contaminated with chlorinated ethylenes. The applications have included wastewaters of both natural fruit juices and corn syrup solutions from carbonated beverages. Cost implications include both the reduced cost of substrate and the cost avoidance of needing to pay for treatment of the wastewater. (authors)« less
Nguyen, Thanh H; Cho, Hyun-Hee; Poster, Dianne L; Ball, William P
2007-02-15
Sorption isotherms for five aromatic hydrocarbons were obtained with a natural wood char (NC1) and its residue after solvent extraction (ENC1). Substantial isotherm nonlinearity was observed in all cases. ENC1 showed higher BET surface area, higher nitrogen-accessible micropore volume, and lower mass of extractable organic chemicals, including quantifiable polycyclic aromatic hydrocarbons (PAHs),while the two chars showed identical surface oxygen/ carbon (O/C) ratio. For two chlorinated benzenes that normally condense as liquids at the temperatures used, sorption isotherms with NC1 and ENC1 were found to be statistically identical. For the solid-phase compounds (1,4-dichlorobenzene (1,4-DCB) and two PAHs), sorption was statistically higher with ENC1, thus demonstrating sorption effects due to both (1) authigenic organic content in the sorbentand (2)the sorbate's condensed state. Polanyi-based isotherm modeling, pore size measurements, and comparisons with activated carbon showthe relative importance of adsorptive pore filling and help explain results. With both chars, maximum sorption increased in the order of decreasing molecular diameter: phenanthrene < naphthalene < 1,2-dichlorobenzene/1,2,4-trichlorobenzene < 1,4-DCB. Comparison of 1,4- and 1,2-DCB shows that the critical molecular diameter was apparently more important than the condensed state, suggesting that 1,4-DCB sorbed in the liquid state for ENC1.
Montone, Rosalinda C; Taniguchi, Satie; Colabuono, Fernanda I; Martins, César C; Cipro, Caio Vinícius Z; Barroso, Hileia S; da Silva, Josilene; Bícego, Márcia C; Weber, Rolf R
2016-05-15
Persistent organic pollutants were assessed in fat samples of the Gentoo (Pygoscelis papua), Chinstrap (Pygoscelis antarcticus) and Adélie (Pygoscelis adeliae) penguins collected during the austral summers of 2005/06 and 2006/07 in Admiralty Bay, King George Island, Antarctica. The predominant organic pollutants were PCB (114 to 1115), polycyclic aromatic hydrocarbons (PAHs) (60.1 to 238.7), HCB (<0.3 to 132.2) and BDE-47 (<1.0 to 10.7) in ng g(-1) wet weight. The mean concentrations of the majority of organic pollutants were similar among the three species of penguins. Chicks of all three species showed similar profiles of PCB congeners, with predominance of lower chlorinated compounds. The distribution of PAHs was similar in all birds, with a predominance of naphthalene and alkyl-naphthalene, which are the main constituents of arctic diesel fuel. These data contribute to the monitoring of the continued exposure to organic pollutants in the Antarctic biota. Copyright © 2016 Elsevier Ltd. All rights reserved.
Trace organic compounds in wet atmospheric deposition: an overview
Steinheimer, T.R.; Johnson, S.M.
1987-01-01
An overview of the occurrence of organic compounds in wet atmospheric deposition is given. Multiplicity of sources and problems associated with source identification are discussed. Available literature is reviewed by using citations from Chemical Abstracts and Water Resources Abstracts through June 1985 and includes reports published through December 1984 that summarize current knowledge. Approaches to the chemical determination of organic compounds in precipitation are examined in addition to aspects of sampling protocols. Best methods for sample collection and preparation for instrumental analysis continue to be discussed among various investigators. Automatic wet-deposition-only devices for collection and extraction are preferred. Classes of organic compounds that have been identified in precipitation include a spectrum of compounds with differing properties of acidity or basicity, polarity, and water solubility. Those compounds that have been reported in rainfall, snowfall, and ice include hydrocarbons (both aromatic and nonaromatic), chlorinated derivatives of these hydrocarbons, carbonyl compounds (both acidic and nonacidic), and carboxylic acids and esters. Formic and acetic are the most abundant organic acids present. Cloudwater, fogwater, and mist also have been collected and analyzed for organic composition.
DOE Office of Scientific and Technical Information (OSTI.GOV)
Antrim, Liam D.; Kohn, Nancy P.
Marine sediment remediation at the United Heckathorn Superfund Site was completed in April 1997. Water and mussel tissues were sampled in February 1999 from four stations near Lauritzen Canal in Richmond, California, for Year 2 of post-remediation monitoring of marine areas near the United Heckathorn Site. Dieldrin and dichlorodiphenyl trichloroethane (DDT) were analyzed in water samples, tissue samples from resident mussels, and tissue samples from transplanted mussels deployed for 4 months. Mussel tissues were also analyzed for polychlorinated biphenyls (PCB), which were detected in sediment samples. Chlorinated pesticide concentrations in water samples were similar to preremediation levels and did notmore » meet remediation goals. Biomonitoring results indicated that the bioavailability of chlorinated pesticides has been reduced from preremediation levels both in the dredged area and throughout Richmond Harbor. Total DDT and dieldrin concentrations in mussel tissues were lower than measured levels from preremediation surveys and also lower than Year 1 levels from post-remediation biomonitoring. Sediment analyses showed the presence of elevated DDT, dieldrin, PCB aroclor 1254, and very high levels of polynuclear aromatic hydrocarbons (PAH) in Lauritzen Channel.« less
Schwartz, Ted R.; Tillitt, Donald E.; Feltz, Kevin P.; Peterman, Paul H.
1993-01-01
High resolution capillary gas chromatography (GC) is the best known technique for the separation of complex mixtures; however, no single GC column has yet separated all 209 congeners of polychlorinated biphenyls (PCBs). A number of coeluting PCB congener pairs exist, and even under favorable separation conditions such as with multidimensional GC, assignment of peak identities to known PCB structures is tedious, subject to errors from other contaminants, and requires enrichment to achieve the necessary detection limits for the most toxic PCB congeners. Routine analysis of PCBs is also complicated by coelution with other halogenated hydrocarbons such as naphthalenes, terphenyls, dibenzofurans, and pesticides. Therefore, techniques for class separations of PCBs prior to gas chromatography must be developed. These techniques should separate PCB congeners along lines that have environmental or toxicological significance. The unique ability of activated carbon to separate halogenated aromatics on the basis of molecular planarity and degree of halogenation has been demonstrated. We present a method that uses dispersed carbon on glass fibers and commercially available instrumentation to fractionate and determine mono- and non-o,o′-chlorine substituted PCB congeners in Aroclors and environmental samples.
Tolerance of anaerobic bacteria to chlorinated solvents.
Koenig, Joanna C; Groissmeier, Kathrin D; Manefield, Mike J
2014-01-01
The aim of this research was to evaluate the effects of four chlorinated aliphatic hydrocarbons (CAHs), perchloroethene (PCE), carbon tetrachloride (CT), chloroform (CF) and 1,2-dichloroethane (1,2-DCA), on the growth of eight anaerobic bacteria: four fermentative species (Escherichia coli, Klebsiella sp., Clostridium sp. and Paenibacillus sp.) and four respiring species (Pseudomonas aeruginosa, Geobacter sulfurreducens, Shewanella oneidensis and Desulfovibrio vulgaris). Effective concentrations of solvents which inhibited growth rates by 50% (EC50) were determined. The octanol-water partition coefficient or log Po/w of a CAH proved a generally satisfactory measure of its toxicity. Most species tolerated approximately 3-fold and 10-fold higher concentrations of the two relatively more polar CAHs CF and 1,2-DCA, respectively, than the two relatively less polar compounds PCE and CT. EC50 values correlated well with growth rates observed in solvent-free cultures, with fast-growing organisms displaying higher tolerance levels. Overall, fermentative bacteria were more tolerant to CAHs than respiring species, with iron- and sulfate-reducing bacteria in particular appearing highly sensitive to CAHs. These data extend the current understanding of the impact of CAHs on a range of anaerobic bacteria, which will benefit the field of bioremediation.
Tsai, Wen-Tien
2017-01-01
Among the halogenated hydrocarbons, chloromethanes (i.e., methyl chloride, CH3Cl; methylene chloride, CH2Cl2; chloroform, CHCl3; and carbon tetrachloride, CCl4) play a vital role due to their extensive uses as solvents and chemical intermediates. This article aims to review their main chemical/physical properties and commercial/industrial uses, as well as the environment and health hazards posed by them and their toxic decomposition products. The environmental properties (including atmospheric lifetime, radiative efficiency, ozone depletion potential, global warming potential, photochemical ozone creation potential, and surface mixing ratio) of these chlorinated methanes are also reviewed. In addition, this paper further discusses their atmospheric fates and human health implications because they are apt to reside in the lower atmosphere when released into the environment. According to the atmospheric degradation mechanism, their toxic degradation products in the troposphere include hydrogen chloride (HCl), carbon monoxide (CO), chlorine (Cl2), formyl chloride (HCOCl), carbonyl chloride (COCl2), and hydrogen peroxide (H2O2). Among them, COCl2 (also called phosgene) is a powerful irritating gas, which is easily hydrolyzed or thermally decomposed to form hydrogen chloride. PMID:29051455
Tolerance of Anaerobic Bacteria to Chlorinated Solvents
Koenig, Joanna C.; Groissmeier, Kathrin D.; Manefield, Mike J.
2014-01-01
The aim of this research was to evaluate the effects of four chlorinated aliphatic hydrocarbons (CAHs), perchloroethene (PCE), carbon tetrachloride (CT), chloroform (CF) and 1,2-dichloroethane (1,2-DCA), on the growth of eight anaerobic bacteria: four fermentative species (Escherichia coli, Klebsiella sp., Clostridium sp. and Paenibacillus sp.) and four respiring species (Pseudomonas aeruginosa, Geobacter sulfurreducens, Shewanella oneidensis and Desulfovibrio vulgaris). Effective concentrations of solvents which inhibited growth rates by 50% (EC50) were determined. The octanol-water partition coefficient or log Po/w of a CAH proved a generally satisfactory measure of its toxicity. Most species tolerated approximately 3-fold and 10-fold higher concentrations of the two relatively more polar CAHs CF and 1,2-DCA, respectively, than the two relatively less polar compounds PCE and CT. EC50 values correlated well with growth rates observed in solvent-free cultures, with fast-growing organisms displaying higher tolerance levels. Overall, fermentative bacteria were more tolerant to CAHs than respiring species, with iron- and sulfate-reducing bacteria in particular appearing highly sensitive to CAHs. These data extend the current understanding of the impact of CAHs on a range of anaerobic bacteria, which will benefit the field of bioremediation. PMID:24441515
Elder, J.F.; Mattraw, H.C.
1984-01-01
A survey of trace element and synthetic organic compound concentrations in botton materials was conducted on the Apalachichola River in northwest Florida in 1979-80 as part of the Apalachicola River Quality Assessment. Substances analyzed included trace elements (predominantly heavy metals), organochlorine insecticides, organophosphorus insecticides, chlorinated phenoxy-acid herbicides, and polychlorinated biphenyls (PCBs). Three kinds of materials were surveyed: fine-grained sediments, whole-body tissue of the Asiatic clam Corbicula manilensis, and bottom-load organic detritus. No hazardous levels of any of the substances were found. Concentrations in the fine-grained sediments and clams were generally at least ten times lower than maximum limits considered safe for biota of aquatic systems. A comparison of trace-substance data from the Apalachicola River with data from Lake Seminole (upstream) and Apalachicola Bay (downstream) showed lower concentrations in riverine clams. Sediment concentrations in all parts of the system were comparable. Most trace substances in the Apalachicola River enter the river from the upstream part of the basin (the Chattahoochee and Flint Rivers in Georgia and Alabama) and from nonpoint sources throughout the basin. There are no major point discharges along the Apalachicola. Trend analysis was limited by the scope of the study, but did not reveal any spatial or temporal trends in concentrations of any of the substances analyzed. Concentrations of organic compounds and most metals in Corbicula manilensis did not correlate with those in sediments.
Puzyn, T; Haranczyk, M; Suzuki, N; Sakurai, T
2011-02-01
We have estimated degradation half-lives of both brominated and chlorinated dibenzo-p-dioxins (PBDDs and PCDDs), furans (PBDFs and PCDFs), biphenyls (PBBs and PCBs), naphthalenes (PBNs and PCNs), diphenyl ethers (PBDEs and PCDEs) as well as selected unsubstituted polycyclic aromatic hydrocarbons (PAHs) in air, surface water, surface soil, and sediments (in total of 1,431 compounds in four compartments). Next, we compared the persistence between chloro- (relatively well-studied) and bromo- (less studied) analogs. The predictions have been performed based on the quantitative structure-property relationship (QSPR) scheme with use of k-nearest neighbors (kNN) classifier and the semi-quantitative system of persistence classes. The classification models utilized principal components derived from the principal component analysis of a set of 24 constitutional and quantum mechanical descriptors as input variables. Accuracies of classification (based on an external validation) were 86, 85, 87, and 75% for air, surface water, surface soil, and sediments, respectively. The persistence of all chlorinated species increased with increasing halogenation degree. In the case of brominated organic pollutants (Br-OPs), the trend was the same for air and sediments. However, we noticed that the opposite trend for persistence in surface water and soil. The results suggest that, due to high photoreactivity of C-Br chemical bonds, photolytic processes occurring in surface water and soil are able to play significant role in transforming and removing Br-OPs from these compartments. This contribution is the first attempt of classifying together Br-OPs and Cl-OPs according to their persistence, in particular, environmental compartments.
Structures and Nuclear Quadrupole Coupling Tensors of a Series of Chlorine-Containing Hydrocarbons
NASA Astrophysics Data System (ADS)
Dikkumbura, Asela S.; Webster, Erica R.; Dorris, Rachel E.; Peebles, Rebecca A.; Peebles, Sean A.; Seifert, Nathan A.; Pate, Brooks
2016-06-01
Rotational spectra for gauche-1,2-dichloroethane (12DCE), gauche-1-chloro-2-fluoroethane (1C2FE) and both anti- and gauche-2,3-dichloropropene (23DCP) have been observed using chirped-pulse Fourier-transform microwave (FTMW) spectroscopy in the 6-18 GHz region. Although the anti conformers for all three species are predicted to be more stable than the gauche forms, they are nonpolar (12DCE) or nearly nonpolar (predicted dipole components for anti-1C2FE: μ_a = 0.11 D, μ_b = 0.02 D and for anti-23DCP: μ_a = 0.25 D, μ_b = 0.02 D); nevertheless, it was also possible to observe and assign the spectrum of anti-23DCP. Assignments of parent spectra and 37Cl and 13C substituted isotopologues utilized predictions at the MP2/6-311++G(2d,2p) level and Pickett's SPCAT/SPFIT programs. For the weak anti-23DCP spectra, additional measurements also utilized a resonant-cavity FTMW spectrometer. Full chlorine nuclear quadrupole coupling tensors for gauche-12DCE and both anti- and gauche-23DCP have been diagonalized to allow comparison of coupling constants. Kraitchman's equations were used to determine r_s coordinates of isotopically substituted atoms and r_0 structures were also deduced for gauche conformers of 12DCE and 1C2FE. Structural details and chlorine nuclear quadrupole coupling constants of all three molecules will be compared, and effects of differing halogen substitution and carbon chain length on molecular properties will be evaluated.
Sedimentary record of environmental pollution in the Western Baltic Sea
NASA Astrophysics Data System (ADS)
Müller, German; Dominik, J.; Reuther, R.; Malisch, R.; Schulte, E.; Acker, L.; Irion, G.
1980-12-01
The chronological development of environmental pollution in the Western Baltic Sea for the past hundred years was investigated in dated sediment cores. An artificial radionuclide (137Cs), nutrients, heavy metals, chlorinated hydrocarbons (PCB, DDT, Lindane) and plasticizers (phthalate esters) show characteristic distribution patterns within the various cores. They can be related to the production and use of specific chemicals and goods, to emissions associated with the increased combustion of coal parallel to industrialization and —in the case of 137Cs — to emissions associated with atomic weapons tests in the high atmosphere. Characteristic trends in the general development of pollution may be superimposed by specific emissions from local sources.
Removing environmental organic pollutants with bioremediation and phytoremediation.
Kang, Jun Won
2014-06-01
Hazardous organic pollutants represent a threat to human, animal, and environmental health. If left unmanaged, these pollutants could cause concern. Many researchers have stepped up efforts to find more sustainable and cost-effective alternatives to using hazardous chemicals and treatments to remove existing harmful pollutants. Environmental biotechnology, such as bioremediation and phytoremediation, is a promising field that utilizes natural resources including microbes and plants to eliminate toxic organic contaminants. This technology offers an attractive alternative to other conventional remediation processes because of its relatively low cost and environmentally-friendly method. This review discusses current biological technologies for the removal of organic contaminants, including chlorinated hydrocarbons, focusing on their limitation and recent efforts to correct the drawbacks.
Ma, Jing; Horii, Yuichi; Cheng, Jinping; Wang, Wenhua; Wu, Qian; Ohura, Takeshi; Kannan, Kurunthachalam
2009-02-01
Chlorinated polycyclic aromatic hydrocarbons (CIPAHs) are a class of halogenated contaminants found in the urban atmosphere; they have toxic potential similar to that of dioxins. Information on the sources of CIPAHs is limited. In this study, concentrations of 20 CIPAHs and 16 parent PAHs were measured in electronic wastes, workshop-floor dust, vegetation, and surface soil collected from the vicinity of an electronic waste (e-waste) recycling facility and in surface soil from a chemical industrial complex (comprising a coke-oven plant, a coal-fired power plant, and a chlor-alkali plant), and agricultural areas in central and eastern China. High concentrations of SigmaCIPAHs were found in floor dust (mean, 103 ng/g dry wt), followed in order of decreasing concentration by leaves (87.5 ng/g drywt), electronic shredder waste (59.1 ng/g dry wt), and soil (26.8 ng/g dry wt) from an e-waste recycling facility in Taizhou. The mean concentration of SigmaCIPAHs in soil from the chemical industrial complex (88 ng/g dry wt) was approximately 3-fold higher than the concentration in soil from e-waste recycling facilities. The soils from e-waste sites and industrial areas contained mean concentrations of SigmaCIPAHs 2 to 3 orders of magnitude higher than the concentrations in agricultural soils (ND-0.76 ng/g), suggesting that e-waste recycling and chlorine-chemical industries are potential emission sources of CIPAHs. The profiles of CIPAHs in soil and dust were similar to a profile that has been reported previously for fly ash from municipal solid waste incinerators (6-CIBaP was the predominant compound), but the profiles in vegetation and electronic shredder waste were different from those found in fly ash. Concentrations of 16 parent PAHs were high (150-49,700 ng/g) in samples collected from the e-waste recycling facility. Significant correlation between SigmaCIPAH and SigmaPAH concentrations suggests that direct chlorination of parent PAHs is the major pathway of formation of CIPAHs during e-waste recycling operations. Dioxin-like toxic equivalency quotients (TEQs) for CIPAHs and PAHs in samples were calculated on the basis of relative potencies reported for CIPAHs and PAHs. The highest mean TEQ concentrations of CIPAHs (518 pg-TEQ/g) were found for workshop-floor dust, followed by leaves (361 pg-TEQ/g), electronic shredder waste (308 pg-TEQ/g), soil from the chemical industrial complex (146 pg-TEQ/g), and soil from the sites of the e-waste recycling facility (92.3 pg-TEQ/g). With one exception, the floor dust samples, the TEQ concentrations of CIPAHs found in multiple environmental matrices in this study were higher than the TEQ concentrations of PCDD/Fs in the same samples reported in our earlier study.
Conti, Barbara; Canale, Angelo; Bertoli, Alessandra; Gozzini, Francesca; Pistelli, Luisa
2010-11-01
Laboratory bioassays on insecticidal activity of essential oils (EOs) extracted from six Mediterranean plants (Achillea millefolium, Lavandula angustifolia, Helichrysum italicum, Foeniculum vulgare, Myrtus communis, and Rosmarinus officinalis) were carried out against the larvae of the Culicidae mosquito Aedes albopictus. The chemical composition of the six EOs was also investigated. Results from applications showed that all tested oils had insecticidal activity, with differences in mortality rates as a function of both oil and dosage. At the highest dosage (300 ppm), EOs from H. italicum, A. millefolium, and F. vulgare caused higher mortality than the other three oils, with mortality rates ranging from 98.3% to 100%. M. communis EO induced only 36.7% larval mortality at the highest dosage (300 ppm), a similar value to those recorded at the same dosage by using R. officinalis and L. angustifolia (51.7% and 55%, respectively). Identified compounds ranged from 91% to 99%. The analyzed EOs had higher content of monoterpenoids (80-99%) than sesquiterpenes (1-15%), and they can be categorized into three groups on the basis of their composition. Few EOs showed the hydrocarbon sesquiterpenes, and these volatile compounds were generally predominant in comparison with the oxygenated forms, which were detected in lower quantities only in H. italicum (1.80%) and in M. communis (1%).
Gołebiowski, Marek; Maliński, Edmund; Nawrot, Jan; Szafranek, Janusz; Stepnowski, Piotr
2007-06-01
The Western Flower Thrips Frankliniella occidentalis effectively resists many insecticides, but it can be controlled by the use of bioinsecticides such as entomopathogenic fungi. The epicuticular chemistry of these insects is therefore of great interest, and accordingly, the cuticular lipid composition of F. occidentalis was analysed. It was found that the cuticular lipids of both the adult and larval stages of F. occidentalis consist of two groups of compounds--hydrocarbons and free fatty acids. The same hydrocarbon pattern was found in both adults and larvae, with the exception of n-hentriacontane, which was detected only in adult insects. The following homologous series were identified: n-alkanes from C-25 to C-29 (31) with the marked dominance of odd numbers of carbon atoms, 3-methylalkanes with 26 and 28 carbon atoms, and branched monomethylalkanes (branched at C-9, -11, -13 and -15) with 26, 28 and 30 carbon atoms. The chemical composition of the free fatty acids consists of two homologous series: saturated (C(14:0), C(16:0), C(18:0)) and unsaturated fatty acids (C(16:1) and C(18:1)). This analysis confirmed the lack of potential inhibitors of entomopathogenic fungi in the cuticular lipids of this insect species.
Dietary exposure of mink to carp from Saginaw Bay, Michigan: 2. Hematology and liver pathology
Heaton, S. N.; Bursian, S.J.; Giesy, J.P.; Tillitt, D. E.; Render, J. A.; Jones, P.D.; Verbrugge, D.A.; Kubiak, T.J.; Aulerich, R.J.
1995-01-01
The effects of consumption of environmental contaminants contained in carp (Cyprinus carpio)from Saginaw Bay, Michigan on various hematological parameters and liver integrity of adult female mink (Mustela vison) were determined. Mink were fed diets that contained 0 (control), 10, 20, or 40% carp prior to and throughout the reproductive period (182 days). The diets contained 0.015, 0.72, 1.53, and 2.56 mg polychlorinated biphenyls (PCBs)/kg diet and 1.0, 19, 40, and 81 pg 2,3,7,8-tetrachlorodibenzo-p-dioxin equivalents (TEQs)/g diet, respectively. Mink fed the diets containing carp showed a general dose-dependent occurrence of clinical signs commonly associated with chlorinated hydrocarbon toxicity, including listlessness, nervousness when approached, anorexia, and melena. Erythrocyte counts were less in mink exposed to Saginaw Bay carp than in controls, while the number of white blood cells was greater than in controls. Significant differences (p<0.05) in the concentrations of neutrophils, lymphocytes, monocytes, and eosinophils were also found between the control and carp-fed groups, but are considered to be of limited clinical or biological importance. Hematocrit values for the mink fed the 20 and 40% carp diets were significantly less than those of mink in the control and 10% carp groups. There were no significant differences in hemoglobin concentrations among the groups. Necropsies revealed enlarged yellowish livers in many of the carp-fed mink, especially those fed the 40% carp diet. Liver, spleen, and lung weights of carp-fed mink were significantly greater than those of control mink. Histopathologic examination of the livers revealed various degrees of congestion, hepatocellular fatty changes, and scattered portal lymphocytic infiltration which were most prevalent in mink fed the carp diets. These clinical signs, hematological effects, and histologic alterations are similar to those previously described for chlorinated hydrocarbon toxicoses in mink.
Recent progress on mid-IR sensing with optical fibers
NASA Astrophysics Data System (ADS)
Kellner, Robert A.; Gobel, R.; Goetz, R.; Lendl, B.; Edl-Mizaikoff, B.; Tacke, Maurus; Katzir, Abraham
1995-09-01
Chemical sensors are analytical systems for the evaluation of compound- or ion-specific or - selective signals produced by specific or selective chemical reactions taking place at the interface between the chemically modified sensor surface and the substrate. The well known electrochemical sensing schemes have greatly contributed that sensors are considered now as the 'third supporting pillar of analytical chemistry' besides chromatography and spectroscopy. The aim of this paper is to describe the novel capabilities of chemical modified IR-transparent fibers as chemical IR-sensors for the on-line analysis of chlorinated hydrocarbons and organic compounds in aqueous solutions and gaseous mixtures, glucose, and sucrose in aqueous solution as developed in our laboratory. Moreover, the relative merits of this new method wil be depicted in comparison to other sensing techniques. Optical fiber sensors are novel analysis systems, based on molecular spectroscopy in the UV/VIS/IR-range. They benefit from the tremendous development in the field of optical fibers, an offspring of the telecommunication industry and the electronic revolution during the last few years. With the development of new materials besides the well known quartz fibers for the UV/VIS/NIR-range the optical window for fiber optic sensors was enlarged from 0,2 to 20 micrometers recently. The fiber length was increased recently to up to 2 meters for silver halides and approximately 10 meters for chalcogenides. New applications for environmental, food, and clinical sensing as well as process analysis are the driving force for modern research in IR-optical fiber sensors using mainly sapphire (Al2O3), chalcogenide (As-Se-Te) and silver halide (AgBr/AgCl) fibers and flow injection analysis (FIA) systems. Few representative examples for each of the various optical sensor types will be presented. Particular attention will be given to the use of silver halide fibers for the simultaneous determination of traces of chlorinated hydrocarbons in water and to FIA-systems for the process analysis of beverages.
NASA Astrophysics Data System (ADS)
Schreiter, I. J.; Wefer-Roehl, A.; Graber, E. R.; Schueth, C.
2016-12-01
Biochar (BC) is increasingly deemed a potential sorbent for contaminants in soil and water remediation, and brownfield restoration. In this study, sorption and extraction experiments were performed to assess the potential of three different BCs to sorb and retain the chlorinated hydrocarbons TCE and PCE. BCs studied were produced from wood chips, grain husk, and cattle manure at 450 °C. A commercially available activated carbon (AC) served as a reference. The sorption behaviour was studied in batch experiments in single solute and bi-solute systems. Resulting isotherms were fitted to the Freundlich model. To assess the desorption behaviour, a five step extraction scheme (water at 40°C, water at 80°C, methanol at 50°C, toluene at 50°C, and n-hexane at 50°) was developed utilizing Accelerated Solvent Extraction. Isotherms revealed distinct differences in sorption behaviour depending on BC feedstock. Sorption capacity ranked as follows: wood chip BC > grain husk BC > cattle manure BC for both contaminants. This sequence could be attributable to an increasing specific surface area and a decreasing ash content of the sorbents. It is noteworthy that all three BCs were more effective in adsorbing TCE, which is surprising, given the higher logKOWof PCE. The reverse trend was observed for the AC. In bi-solute experiments, PCE sorbed as good as or stronger than TCE, yet the total mass of sorbed compounds was higher. In contrast, AC showed a significant decrease of TCE sorption. Extraction experiments revealed that for all BCs a large fraction of the contaminants could not be readily desorbed. In all cases, water remobilized < 5 % of the total contaminant mass and up to 70 % could not be extracted by any of the solvents. The findings suggest that BC is a promising sorbent for mixed contaminant systems as it offers a diverse nature of sorption sites and is more effective in long-term stabilization than AC.
NASA Astrophysics Data System (ADS)
Powell, C. L.; Goltz, M. N.; Agrawal, A.
2014-12-01
Chlorinated aliphatic hydrocarbons (CAHs) are common groundwater contaminants that can be removed from the environment by natural attenuation processes. CAH biodegradation can occur in wetland environments by reductive dechlorination as well as oxidation pathways. In particular, CAH oxidation may occur in vegetated wetlands, by microorganisms that are naturally associated with the roots of wetland plants. The main objective of this study was to evaluate the cometabolic degradation kinetics of the CAHs, cis-1,2-dichloroethene (cisDCE), trichloroethene (TCE), and 1,1,1-trichloroethane (1,1,1TCA), by methane-oxidizing bacteria associated with the roots of a typical wetland plant in soil-free system. Laboratory microcosms with washed live roots investigated aerobic, cometabolic degradation of CAHs by the root-associated methane-oxidizing bacteria at initial aqueous [CH4] ~ 1.9 mg L- 1, and initial aqueous [CAH] ~ 150 μg L- 1; cisDCE and TCE (in the presence of 1,1,1TCA) degraded significantly, with a removal efficiency of approximately 90% and 46%, respectively. 1,1,1TCA degradation was not observed in the presence of active methane oxidizers. The pseudo first-order degradation rate-constants of TCE and cisDCE were 0.12 ± 0.01 and 0.59 ± 0.07 d- 1, respectively, which are comparable to published values. However, their biomass-normalized degradation rate constants obtained in this study were significantly smaller than pure-culture studies, yet they were comparable to values reported for biofilm systems. The study suggests that CAH removal in wetland plant roots may be comparable to processes within biofilms. This has led us to speculate that the active biomass may be on the root surface as a biofilm. The cisDCE and TCE mass losses due to methane oxidizers in this study offer insight into the role of shallow, vegetated wetlands as an environmental sink for such xenobiotic compounds.
Powell, C L; Goltz, M N; Agrawal, A
2014-12-01
Chlorinated aliphatic hydrocarbons (CAHs) are common groundwater contaminants that can be removed from the environment by natural attenuation processes. CAH biodegradation can occur in wetland environments by reductive dechlorination as well as oxidation pathways. In particular, CAH oxidation may occur in vegetated wetlands, by microorganisms that are naturally associated with the roots of wetland plants. The main objective of this study was to evaluate the cometabolic degradation kinetics of the CAHs, cis-1,2-dichloroethene (cisDCE), trichloroethene (TCE), and 1,1,1-trichloroethane (1,1,1TCA), by methane-oxidizing bacteria associated with the roots of a typical wetland plant in soil-free system. Laboratory microcosms with washed live roots investigated aerobic, cometabolic degradation of CAHs by the root-associated methane-oxidizing bacteria at initial aqueous [CH4] ~1.9mgL(-1), and initial aqueous [CAH] ~150μgL(-1); cisDCE and TCE (in the presence of 1,1,1TCA) degraded significantly, with a removal efficiency of approximately 90% and 46%, respectively. 1,1,1TCA degradation was not observed in the presence of active methane oxidizers. The pseudo first-order degradation rate-constants of TCE and cisDCE were 0.12±0.01 and 0.59±0.07d(-1), respectively, which are comparable to published values. However, their biomass-normalized degradation rate constants obtained in this study were significantly smaller than pure-culture studies, yet they were comparable to values reported for biofilm systems. The study suggests that CAH removal in wetland plant roots may be comparable to processes within biofilms. This has led us to speculate that the active biomass may be on the root surface as a biofilm. The cisDCE and TCE mass losses due to methane oxidizers in this study offer insight into the role of shallow, vegetated wetlands as an environmental sink for such xenobiotic compounds. Copyright © 2014 Elsevier B.V. All rights reserved.
Trichloroacetic acid in the environment.
McCulloch, A
2002-05-01
Suppositions that the trichloroacetic acid (TCA, CCl3C(O)OH) found in nature was a consequence solely of the use of chlorinated hydrocarbon solvents prompted this critical review of the literature on its environmental fluxes and occurrences. TCA is widely distributed in forest soils (where it was rarely used as an herbicide) and measurements suggest a soil flux of 160 000 tonnes yr(-1) in European forests alone. TCA is also produced during oxidative water treatment and the global flux could amount to 55 000 tonnes yr(-1) (from pulp and paper manufacture, potable water and cooling water treatments). By contrast, the yields of TCA from chlorinated hydrocarbon solvents are small: from tetrachloroethene 13 600 tonnes yr(-1) and from 1,1,1-trichloroethane 4300 tonnes yr(-1) on a global basis, at the atmospheric burdens and removal rates typical of the late 1990s. TCA is ubiquitous in rainwater and snow. Its concentrations are highly variable and the variations cannot be connected with location or date. However, there is no significant difference between the concentrations found in Chile and in eastern Canada (by the same analysts), or between Malawi and western Canada, or between Antarctica and Switzerland, nor any significant difference globally between the concentrations in cloud, rain and snow (although local enhancement in fog water has been shown). TCA is present in old ice and firn. At the deepest levels, the firn was deposited early in the 19th century, well before the possibility of contamination by industrial production of reactive chlorine, implying a non-industrial background. This proposition is supported by plume measurements from pulp mills in Finland. TCA is ubiquitous in soils; concentrations are very variable but there are some indications that soils under coniferous trees contain higher amounts. The concentrations of TCA found in plant tissue are region-specific and may also be plant-specific, to the extent that conifers seem to contain more than other species. TCA is removed from the environment naturally. There is abundant evidence that soil microorganisms dehalogenate TCA and it is lost from within spruce needles with a half-life of 10 days. There is also recent evidence of an abiotic aqueous decarboxylation mechanism with a half-life of 22 days. The supposedly widespread effects of TCA in conifer needles are not shown in controlled experiments. At concentrations in the needles of Scots pine similar to those observed in needles in forest trees, changes consequent on TCA treatment of field laboratory specimens were almost all insignificant.
Fleming, Donald A.; Woskie, Susan R.; Jones, James H.; Silver, Sharon R.; Luo, Lian; Bertke, Stephen J.
2015-01-01
A retrospective exposure assessment was performed for use in a health outcomes study of a facility manufacturing circuit boards, business machines, and other equipment during the years 1969–2002. A matrix was developed identifying chemical use by department-year based on company-provided information. Use of six chemical agents (fiberglass, lead, methylene chloride, methyl chloroform, perchloroethylene, and trichloroethylene) and six chemical classes (acid-base, aromatic hydrocarbons, chlorinated hydrocarbons, other hydrocarbons, chlorofluorocarbons, and metals), and general (including unspecified) chemicals was identified. The matrix also contained an assignment for each department-year categorizing the potential for use of chemicals as negligible, intermittent/incidental, or routine. These department-based exposure matrix data were combined with work history data to provide duration of potential chemical use for workers. Negligible, intermittent/incidental or routine extent-of-chemical-use categories comprised 42.6%, 39.4%, and 17.9%, respectively, of total person-years of employment. Cumulative exposure scores were also developed, representing a relative measure of the cumulative extent of potential exposure to the six chemical agents, six chemical classes, and general (including unspecified) chemicals. Additionally, the study period was divided into manufacturing eras showing trends in chemical use, and showing that process use of trichloroethylene and methylene chloride ended in the mid-1980s and the mid-1990s, respectively. This approach may be useful in other assessments addressing a variety of chemicals, and with data constraints common to retrospective chemical exposure studies. PMID:24224613
Electrolysis-driven bioremediation of crude oil-contaminated marine sediments.
Bellagamba, Marco; Cruz Viggi, Carolina; Ademollo, Nicoletta; Rossetti, Simona; Aulenta, Federico
2017-09-25
Bioremediation is an effective technology to tackle crude oil spill disasters, which takes advantage of the capacity of naturally occurring microorganisms to degrade petroleum hydrocarbons under a range of environmental conditions. The enzymatic process of breaking down oil is usually more rapid in the presence of oxygen. However, in contaminated sediments, oxygen levels are typically too low to sustain the rapid and complete biodegradation of buried hydrocarbons. Here, we explored the possibility to electrochemically manipulate the redox potential of a crude oil-contaminated marine sediment in order to establish, in situ, conditions that are conducive to contaminants biodegradation by autochthonous microbial communities. The proposed approach is based on the exploitation of low-voltage (2V) seawater electrolysis to drive oxygen generation (while minimizing chlorine evolution) on Dimensionally Stable Anodes (DSA) placed within the contaminated sediment. Results, based on a laboratory scale setup with chronically polluted sediments spiked with crude oil, showed an increased redox potential and a decreased pH in the vicinity of the anode of 'electrified' treatments, consistent with the occurrence of oxygen generation. Accordingly, hydrocarbons biodegradation was substantially accelerated (up to 3-times) compared to 'non-electrified' controls, while sulfate reduction was severely inhibited. Intermittent application of electrolysis proved to be an effective strategy to minimize the energy requirements of the process, without adversely affecting degradation performance. Taken as a whole, this study suggests that electrolysis-driven bioremediation could be a sustainable technology for the management of contaminated sediments. Copyright © 2016 Elsevier B.V. All rights reserved.
Puerto Rico - 2002 : field studies to resolve aerosol processes.
DOE Office of Scientific and Technical Information (OSTI.GOV)
Gaffney, J. S.; Marley, N. A.; Ravelo, R.
1999-10-05
A number of questions remain concerning homogeneous aerosol formation by natural organics interacting with anthropogenic pollutants. For example, chlorine has been proposed as a potential oxidant in the troposphere because of its very high reactivity with a wide range of organics (Finlayson-Pitts, 1993). Indeed, sea salt aerosol in the presence of ozone has been shown to produce chlorine atoms in heterogeneous photochemical reactions under laboratory conditions. Whether chlorine can initiate oxidation of natural organics such as monoterpene hydrocarbons and can generate homogeneous nucleation or condensable material that contributes to aerosol loadings needs to be assessed. The nighttime reactions of ozonemore » and nitrate radical can also result in monoterpene reactions that contribute to aerosol mass. We are currently planning field studies in Puerto Rico to assess these aerosol issues and other atmospheric chemistry questions. Puerto Rico has a number of key features that make it very attractive for a field study of this sort. The principal feature is the island's very regular meteorology and its position in the Caribbean Sea relative to the easterly trade winds. This meteorology and the island's rectangular shape (100 x 35 miles) make it highly suitable for simplification of boundary layer conditions. In addition, the long stretch between Puerto Rico and the nearest pollution sources in Africa and southern Europe make the incoming background air relatively clean and constant. Furthermore, Puerto Rico has approximately 3.5 million people with a very well defined source region and a central area of rain forest vegetation. These features make Puerto Rico an ideal locale for assessing aerosol processes. The following sections describe specific areas of atmospheric chemistry that can be explored during the proposed field study.« less
McIntosh, Grant J; Russell, Douglas K
2013-05-23
The mechanism of formation of benzene rings during the pyrolysis of dichloro- and trichloroethylenes has been investigated by the method of laser powered homogeneous pyrolysis coupled with product analysis by gas chromatography. Additionally, selected (co)pyrolyses between the chlorinated ethylenes, CH2Cl2, C4Cl4, C4Cl6, and C2H2 have been performed to explicitly probe the roles of 2C3 and C4/C2 reaction pairs in aromatic growth. The presence of odd-carbon products in neat C4Cl6 pyrolyses indicates that 2C3 processes are operative in these systems; however, comparison with product yields from C2HCl3 suggests that C4/C2 processes dominate most other systems. This is further evidenced by an absence of C3 and other odd-carbon species in (co)pyrolyses with dichloromethane which should seed C3-based growth. The reactions of perchlorinated C4 species C4Cl5, C4Cl3, and C4Cl4 with C2Cl2 were subsequently explored through extensive kinetic simulations of the possible reaction pathways based on previous kinetic models and the exhaustive quantum chemical investigations of our preceding work. The experimental and theoretical results strongly suggest that, at moderate temperatures, aromatic ring formation from chlorinated ethylenes normally follows a Diels-Alder coupling of C4 and C2 molecular units followed by internal shifts; the one exception is the C4Cl4 + C2Cl2 system, where steric factors lead to the formation of nonaromatic products. There is little evidence for radical-based routes in these systems.
Organochlorine pesticides, HCB, and PCBs in human milk in Poland
DOE Office of Scientific and Technical Information (OSTI.GOV)
Czaja, K.; Ludwicki, J.K.; Goralczyk, K.
1997-05-01
Persistent organochlorine compounds were used in agriculture and industry for years. Their ability to accumulate in organisms constituting links of the food chain and a unique chemical stability made them a hazardous environmental contaminants. The metabolism and excretion of chlorinated hydrocarbons is a very slow process. One of the most important means of elimination such compounds from the woman`s body is lactation. Consequently, human milk has occasionally a significant concentration of organochlorine compounds. Such compounds are identified in women`s milk all over the world. The objective of this study was to identify organochlorine pesticides, HCB, and PCBs concentrations in humanmore » milk in Poland by comparing more and less industrialized regions. 15 refs., 3 tabs.« less
Noreña-Barroso, E; Simá-Alvarez, R; Gold-Bouchot, G; Zapata-Pérez, O
2004-02-01
Livers of catfish (Ariopsis assimilis) from the Bay of Chetumal were analyzed for organochlorine compounds and hydrocarbons as part of a study to diagnose the environmental health of the Bay after a catfish mass mortality that occurred in 1996. The presence of histological lesions in several organs of the fish as result of chemical exposure was also evaluated. The concentrations of organic pollutants found in the Bay may be considered high if compared to the levels reported for sites affected by chemical pollution. High prevalences of cellular alteration histopathologies were found in liver, including hepatic tumors. The presence of some lesions may be related statistically to environmental pollution in the Bay, specially with chlorinated compounds.
Biomagnification of bioassay derived 2,3,7,8-tetrachlorodibenzo-p-dioxin equivalents
Jones, P.D.; Ankley, G.T.; Best, D. A.; Crawford, R.; DeGalan, N.; Giesy, J.P.; Kubiak, T.J.; Ludwig, J. P.; Newsted, J.L.; Tillitt, D. E.; Verbrugge, D.A.
1993-01-01
In recent years contamination of the Great Lakes ecosystem with planar chlorinated hydrocarbons (PCHs) has attracted considerable concern due to their known reproductive and teratogenic effects. The H4IIE bioassay has been standardized as a means of measuring the biological potency of a PCH mixture as 2,3,7,8-tetrachloro-p-dibenzodioxin equivalents (TCDD-EQ). Using this bioassay we have investigated the biomagnification of TCDD-EQ in a semi-closed ecosystem. The biomagnification of TCDD-EQ is demonstrated and results indicate that the food chain is the major pathway for TCDD-EQ through this ecosystem. The H4IIE assay system is demonstrated to be a viable integrative measure of the total concentration of TCDD-EQ in different trophic levels.
Vroblesky, Don A.; Lorah, Michelle M.; Oliveros, James P.
1995-01-01
Disposal of munitions and chemical-warfare substances has introduced inorganic and organic contaminants to the ground water, surface water, and bottom sediment at O-Field, in the Edgewood area of Aberdeen Proving Ground, Maryland. Contaminants include chloride, arsenic, transition metals, chlorinated aliphatic hydrocarbons, aromatic compounds, and organosulfur and organophosphorus compounds. The hydrologic effects of several remedial actions were estimated by use of a ground-water-flow model. The remedial actions examined were an impermeable covering, encapsulation, subsurface barriers, a ground-water drain, pumping of wells to manage water levels or to remove contaminated ground water for treatment, and no action.
Bioremediation of contaminated groundwater
Hazen, T.C.; Fliermans, C.B.
1994-01-01
Disclosed is an apparatus and method for in situ remediation of contaminated subsurface soil or groundwater contaminated by chlorinated hydrocarbons. A nutrient fluid (NF) is selected to simulated the growth and reproduction of indigenous subsurface microorganisms capable of degrading the contaminants; an oxygenated fluid (OF) is selected to create an aerobic environment with anaerobic pockets. NF is injected periodically while OF is injected continuously and both are extracted so that both are drawn across the plume. NF stimulates microbial colony growth; withholding it periodically forces the larger, healthy colony of microbes to degrade the contaminants. Treatment is continued until the subsurface concentration of contaminants is acceptable. NF can be methane and OF be air, for stimulating production of methanotrophs to break down chlorohydrocarbons, especially TCE and tetrachloroethylene.
Experimental infrared measurements for hydrocarbon pollutant determination in subterranean waters
NASA Astrophysics Data System (ADS)
Lay-Ekuakille, A.; Palamara, I.; Caratelli, D.; Morabito, F. C.
2013-01-01
Subterranean waters are often polluted by industrial and anthropic effluents that are drained in subsoil. To prevent and control pollution, legislations of different developed countries require an online monitoring measurement, especially for detecting organic solvents (chlorinated and unchlorinated ones). Online measurements include both real-time and no real-time measurements. In general, it is difficult to implement real-time measurements in stricto sensu for online acquisitions on aqueous effluents since they need to be processed by a modeling. This research presents an experimental measurement system based on infrared (IR) spectroscopy for aqueous effluents containing hydrocarbons and capable of displaying excellent values of pollutant concentrations even in instable conditions; the system is able to detect pollutants either in laminar or turbulent flow. The results show the possibility of avoiding the use of "Pitot tube" that is employed to create a stagnation point in order to convert kinetic energy into potential one. This conversion allows the transformation of a turbulent flow in a laminar flow making easy measurement of pollutants included in an aqueous effluent. Obviously, "Pitot tube" is also used for other fluid effluents. The obtained results have been compared with those produced by means of sophisticated IR instrumentation for laboratory applications.
Experimental infrared measurements for hydrocarbon pollutant determination in subterranean waters.
Lay-Ekuakille, A; Palamara, I; Caratelli, D; Morabito, F C
2013-01-01
Subterranean waters are often polluted by industrial and anthropic effluents that are drained in subsoil. To prevent and control pollution, legislations of different developed countries require an online monitoring measurement, especially for detecting organic solvents (chlorinated and unchlorinated ones). Online measurements include both real-time and no real-time measurements. In general, it is difficult to implement real-time measurements in stricto sensu for online acquisitions on aqueous effluents since they need to be processed by a modeling. This research presents an experimental measurement system based on infrared (IR) spectroscopy for aqueous effluents containing hydrocarbons and capable of displaying excellent values of pollutant concentrations even in instable conditions; the system is able to detect pollutants either in laminar or turbulent flow. The results show the possibility of avoiding the use of "Pitot tube" that is employed to create a stagnation point in order to convert kinetic energy into potential one. This conversion allows the transformation of a turbulent flow in a laminar flow making easy measurement of pollutants included in an aqueous effluent. Obviously, "Pitot tube" is also used for other fluid effluents. The obtained results have been compared with those produced by means of sophisticated IR instrumentation for laboratory applications.
Evaluation of various molecular parameters as predictors of bioconcentration in fish
DOE Office of Scientific and Technical Information (OSTI.GOV)
Connell, D.W.; Schueuermann G3
1988-06-01
A reliable set of data on the bioconcentration factors (KB) of a diverse range of compounds in fish was selected from the literature. Using the structures of these compounds, the following molecular parameters were calculated: molecular weight (MW), solvent accessible molecular surface area (SASA), solvent accessible molecular volume (SAV), molar refraction (MR), largest principal moment of inertia (LPMI) and several molecular connectivity indices of the Randic type (1 chi, 2 chi, 3 chi, 1 chi vr, 3 chi c). The relationships between these parameters and log KB were evaluated for all compounds and the following subgroups: chlorinated hydrocarbons (CHC), polyaromaticmore » hydrocarbons (PAH), and CHC and PAH combined. These relationships indicated that SASA, SAV, and MR were good predictors of log KB for the CHC and PAH combined or alone and the other parameters were less satisfactory with these groups. In addition with the CHC, the log of these parameters displayed an improved correlation with log KB due to apparent nonlinearity in the log to linear relationship. Thus, with these groups of compounds, calculated values of SASA, SAV, and MR provide a satisfactory means of estimating log KB without measured data.« less
NASA Astrophysics Data System (ADS)
Higgins, C.
2017-12-01
Poly and perfluoroalkyl substances (PFASs) are constituents in aqueous film-forming foam (AFFF) used to extinguish fuel fires. Substantially elevated PFAS groundwater concentrations have been observed at firefighter protection training areas, where co-contaminants such as chlorinated solvents and fuel hydrocarbons are also commonly present. Research into the fate and transport potential of PFASs at AFFF-impacted sites will be presented, with a particular focus on how co-contaminants and co-contaminant remediation technologies may alter the composition and transport behavior of PFASs at these sites. A detailed analysis of data collected from a U.S. Air Force site (Ellsworth Air Force Base, South Dakota) indicates that that conversion of polyfluoroalkyl chemicals to perfluoroalkyl acids (PFAAs) in situ due to natural and enhanced remediation of petroleum hydrocarbons. In addition, bench-scale studies examining the effects of various chemical oxidants, typically employed via in situ chemical oxidation (ISCO), indicates that oxidation-based remediation technologies have the potential to alter the release and composition of PFASs in AFFF-impacted source zones. Future challenges in addressing PFAS contamination will be discussed, particularly with respect to closing the mass balance on PFAAs and their precursors at AFFF-impacted sites.
Design of a Vehicle-Based Intervention System to Prevent Ozone Loss
NASA Technical Reports Server (NTRS)
Mason, William H.; Kirchbaum, Nathan; Kay, Jacob; Benoliel, Alexander M.; Lynn, Sean R.; Bunker, Deborah; Hesbach, Thomas D., Jr.; Howerton, Everett B.; Hreinsson, Gudbjoern; Mistr, E. Kirk
1993-01-01
Reduced quantities of ozone in the atmosphere allow greater levels of ultraviolet (UV) radiation to reach the earth's surface. The 1992/1993 project goals for the Virginia Tech Senior Design Team were to 1) understand the processes which contribute to stratospheric ozone loss, 2) examine ways to prevent ozone loss, and 3) define the requirements for an implementation vehicle to carry out the prevention scheme. A scheme proposed by R.J. Cicerone, el al late in 1991 was selected because of its supporting research and economic feasibility. This scheme uses hydrocarbon injected into the Antarctic ozone hole to form stable compounds with free chlorine, thus reducing ozone depletion. A study of the hydrocarbon injection requirements determined that 130 aircraft traveling Mach 2.4 at a maximum altitude of 66,000 ft. would provide the most economic approach to preventing ozone loss. Each aircraft would require an 8,000 nm. range and be able to carry 35,000 lbs. of propane. The propane would be stored in a three-tank high pressure system. Modularity and multi-role functionality were selected to be key design features. Missions originate from airports located in South America and Australia.
The role of microbial reductive dechlorination of TCE at a phytoremediation site
Godsy, E.M.; Warren, E.; Paganelli, V.V.
2003-01-01
In April 1996, a phytoremediation field demonstration site at the Naval Air Station, Fort Worth, Texas, was developed to remediate shallow oxic ground water (< 3.7 m deep) contaminated with chlorinated ethenes. Microbial populations were sampled in February and June 1998. The populations under the newly planted cottonwood trees had not yet matured to an anaerobic community that could dechlorinate trichloroethene (TCE) to cis-1,2-dichloroethene (DCE); however, the microbial population under a mature (???22-year-old) cottonwood tree about 30 m southwest of the plantings had a mature anaerobic population capable of dechlorinating TCE to DCE, and DCE to vinyl chloride (VC). Oxygen-free sediment incubations with contaminated groundwater also demonstrated that resident microorganisms were capable of the dechlorination of TCE to DCE. This suggests that a sufficient amount of organic material is present for microbial dechlorination in aquifer microniches where dissolved O2 concentrations are low. Phenol, benzoic acid, acetic acid, and a cyclic hydrocarbon, compounds consistent with the degradation of root exudates and complex aromatic compounds, were identified by gas chromatography/mass spectrometry (GC/MS) in sediment samples under the mature cottonwood tree. Elsewhere at the site, transpiration and degradation by the cottonwood trees appears to be responsible for loss of chlorinated ethenes.
Stackelberg, P.E.; Gibs, J.; Furlong, E.T.; Meyer, M.T.; Zaugg, S.D.; Lippincott, R.L.
2007-01-01
Samples of water and sediment from a conventional drinking-water-treatment (DWT) plant were analyzed for 113 organic compounds (OCs) that included pharmaceuticals, detergent degradates, flame retardants and plasticizers, polycyclic aromatic hydrocarbons (PAHs), fragrances and flavorants, pesticides and an insect repellent, and plant and animal steroids. 45 of these compounds were detected in samples of source water and 34 were detected in samples of settled sludge and (or) filter-backwash sediments. The average percent removal of these compounds was calculated from their average concentration in time-composited water samples collected after clarification, disinfection (chlorination), and granular-activated-carbon (GAC) filtration. In general, GAC filtration accounted for 53% of the removal of these compounds from the aqueous phase; disinfection accounted for 32%, and clarification accounted for 15%. The effectiveness of these treatments varied widely within and among classes of compounds; some hydrophobic compounds were strongly oxidized by free chlorine, and some hydrophilic compounds were partly removed through adsorption processes. The detection of 21 of the compounds in 1 or more samples of finished water, and of 3 to 13 compounds in every finished-water sample, indicates substantial but incomplete degradation or removal of OCs through the conventional DWT process used at this plant. ?? 2007 Elsevier B.V. All rights reserved.
Stackelberg, Paul E; Gibs, Jacob; Furlong, Edward T; Meyer, Michael T; Zaugg, Steven D; Lippincott, R Lee
2007-05-15
Samples of water and sediment from a conventional drinking-water-treatment (DWT) plant were analyzed for 113 organic compounds (OCs) that included pharmaceuticals, detergent degradates, flame retardants and plasticizers, polycyclic aromatic hydrocarbons (PAHs), fragrances and flavorants, pesticides and an insect repellent, and plant and animal steroids. 45 of these compounds were detected in samples of source water and 34 were detected in samples of settled sludge and (or) filter-backwash sediments. The average percent removal of these compounds was calculated from their average concentration in time-composited water samples collected after clarification, disinfection (chlorination), and granular-activated-carbon (GAC) filtration. In general, GAC filtration accounted for 53% of the removal of these compounds from the aqueous phase; disinfection accounted for 32%, and clarification accounted for 15%. The effectiveness of these treatments varied widely within and among classes of compounds; some hydrophobic compounds were strongly oxidized by free chlorine, and some hydrophilic compounds were partly removed through adsorption processes. The detection of 21 of the compounds in 1 or more samples of finished water, and of 3 to 13 compounds in every finished-water sample, indicates substantial but incomplete degradation or removal of OCs through the conventional DWT process used at this plant.
Witt, M.E.; Klecka, G.M.; Lutz, E.J.; Ei, T.A.; Grosso, N.R.; Chapelle, F.H.
2002-01-01
Monitored natural attenuation (MNA) has recently emerged as a viable groundwater remediation technology in the United States. Area 6 at Dover Air Force Base (Dover, DE) was chosen as a test site to examine the potential for MNA of tetrachloroethene (PCE) and trichloroethene (TCE) in groundwater and aquifer sediments. A "lines of evidence" approach was used to document the occurrence of natural attenuation. Chlorinated hydrocarbon and biogeochemical data were used to develop a site-specific conceptual model where both anaerobic and aerobic biological processes are responsible for the destruction of PCE, TCE, and daughter metabolites. An examination of groundwater biogeochemical data showed a region of depleted dissolved oxygen with elevated dissolved methane and hydrogen concentrations. Reductive dechlorination likely dominated in the anaerobic portion of the aquifer where PCE and TCE levels were observed to decrease with a simultaneous increase in cis-1,2-dichloroethene (cis-DCE), vinyl chloride (VC), ethene, and dissolved chloride. Near the anaerobic/aerobic interface, concentrations of cis-DCE and VC decreased to below detection limits, presumably due to aerobic biotransformation processes. Therefore, the contaminant and daughter product plumes present at the site appear to have been naturally attenuated by a combination of active anaerobic and aerobic biotransformation processes. ?? 2002 Elsevier Science B.V. All rights reserved.
Dioxins and polyvinylchloride in combustion and fires.
Zhang, Mengmei; Buekens, Alfons; Jiang, Xuguang; Li, Xiaodong
2015-07-01
This review on polyvinylchloride (PVC) and dioxins collects, collates, and compares data from selected sources on the formation of polychlorinated dibenzofurans (PCDFs) and dibenzo-p-dioxins (PCDDs), or in brief dioxins, in combustion and fires. In professional spheres, the incineration of PVC as part of municipal solid waste is seldom seen as a problem, since deep flue gas cleaning is required anyhow. Conversely, with its high content of chlorine, PVC is frequently branded as a major chlorine donor and spitefully leads to substantial formation of dioxins during poorly controlled or uncontrolled combustion and open fires. Numerous still ill-documented and diverse factors of influence may affect the formation of dioxins during combustion: on the one hand PVC-compounds represent an array of materials with widely different formulations; on the other hand these may all be exposed to fires of different nature and consequences. Hence, attention should be paid to PVC with respect to the ignition and development of fires, as well as attenuating the emission of objectionable compounds, such as carbon monoxide, hydrogen chloride, polycyclic aromatic hydrocarbons, and dioxins. This review summarises available dioxin emissions data, gathers experimental and simulation studies of fires and combustion tests involving PVC, and identifies and analyses the effects of several local factors of influence, affecting the formation of dioxins during PVC combustion. © The Author(s) 2015.
Oxychlorine Species on Mars: The Gale Crater Story
NASA Technical Reports Server (NTRS)
Archer, P. D., Jr.; Ming, D. W.; Sutter, B.; Morris, R. V.; Clark, B. C.; Mahaffy, P. H.; Wray, J. J.; Fairen, A. G.; Gellert, R.; Yen, A. S.;
2015-01-01
Comparing data from the Alpha- Particle X-Ray Spectrometer (APXS) and the Sample Analysis at Mars (SAM) instruments on MSL reveals a strong linear correlation between chlorine and oxygen, further demonstrating the presence of oxychlorine species in Gale Crater and, very likely, globally on Mars. Perchlorate was first discovered on Mars by the Microscopy, Electrochemistry, and Conductivity Analyzer (MECA) instrument on the Phoenix lander in 2008. Current hypotheses suggest that the formation of oxychlorine species such as perchlorate or chlorate is a global process and that these species should be globally distributed on Mars [e.g. 2-4]. To date, the SAM and Chemistry and Mineralogy (CheMin) instruments on MSL have analyzed one scooped sample of aeolian material (Rocknest [RN]), and four drilled samples (John Klein [JK], Cumberland [CB], Windjana [WJ], and Confidence Hills [CH]). The APXS instrument has also investigated the same or very similar samples. Although not definitively identified, oxychlorine species have been proposed to explain releases of O2, HCl, and chlorinated hydrocarbon species detected by evolved gas analysis (EGA) with the SAM instrument. We report a strong linear correlation between wt. % Cl detected by APXS and moles O2 detected by SAM during pyrolysis, indicating the presence of oxychlorine species in Gale Crater.
Cui, Xinyi; Mayer, Philipp; Gan, Jay
2013-01-01
Many important environmental contaminants are hydrophobic organic contaminants (HOCs), which include PCBs, PAHs, PBDEs, DDT and other chlorinated insecticides, among others. Owing to their strong hydrophobicity, HOCs have their final destination in soil or sediment, where their ecotoxicological effects are closely regulated by sorption and thus bioavailability. The last two decades have seen a dramatic increase in research efforts in developing and applying partitioning based methods and biomimetic extractions for measuring HOC bioavailability. However, the many variations of both analytical methods and associated measurement endpoints are often a source of confusion for users. In this review, we distinguish the most commonly used analytical approaches based on their measurement objectives, and illustrate their practical operational steps, strengths and limitations using simple flowcharts. This review may serve as guidance for new users on the selection and use of established methods, and a reference for experienced investigators to identify potential topics for further research. Copyright © 2012 Elsevier Ltd. All rights reserved.
Analysis of Halogen-Mercury Reactions in Flue Gas
DOE Office of Scientific and Technical Information (OSTI.GOV)
Paula Buitrago; Geoffrey Silcox; Constance Senior
2010-01-01
Oxidized mercury species may be formed in combustion systems through gas-phase reactions between elemental mercury and halogens, such as chorine or bromine. This study examines how bromine species affect mercury oxidation in the gas phase and examines the effects of mixtures of bromine and chlorine on extents of oxidation. Experiments were conducted in a bench-scale, laminar flow, methane-fired (300 W), quartz-lined reactor in which gas composition (HCl, HBr, NO{sub x}, SO{sub 2}) and temperature profile were varied. In the experiments, the post-combustion gases were quenched from flame temperatures to about 350 C, and then speciated mercury was measured using amore » wet conditioning system and continuous emissions monitor (CEM). Supporting kinetic calculations were performed and compared with measured levels of oxidation. A significant portion of this report is devoted to sample conditioning as part of the mercury analysis system. In combustion systems with significant amounts of Br{sub 2} in the flue gas, the impinger solutions used to speciate mercury may be biased and care must be taken in interpreting mercury oxidation results. The stannous chloride solution used in the CEM conditioning system to convert all mercury to total mercury did not provide complete conversion of oxidized mercury to elemental, when bromine was added to the combustion system, resulting in a low bias for the total mercury measurement. The use of a hydroxylamine hydrochloride and sodium hydroxide solution instead of stannous chloride showed a significant improvement in the measurement of total mercury. Bromine was shown to be much more effective in the post-flame, homogeneous oxidation of mercury than chlorine, on an equivalent molar basis. Addition of NO to the flame (up to 400 ppmv) had no impact on mercury oxidation by chlorine or bromine. Addition of SO{sub 2} had no effect on mercury oxidation by chlorine at SO{sub 2} concentrations below about 400 ppmv; some increase in mercury oxidation was observed at SO{sub 2} concentrations of 400 ppmv and higher. In contrast, SO{sub 2} concentrations as low as 50 ppmv significantly reduced mercury oxidation by bromine, this reduction could be due to both gas and liquid phase interactions between SO{sub 2} and oxidized mercury species. The simultaneous presence of chlorine and bromine in the flue gas resulted in a slight increase in mercury oxidation above that obtained with bromine alone, the extent of the observed increase is proportional to the chlorine concentration. The results of this study can be used to understand the relative importance of gas-phase mercury oxidation by bromine and chlorine in combustion systems. Two temperature profiles were tested: a low quench (210 K/s) and a high quench (440 K/s). For chlorine the effects of quench rate were slight and hard to characterize with confidence. Oxidation with bromine proved sensitive to quench rate with significantly more oxidation at the lower rate. The data generated in this program are the first homogeneous laboratory-scale data on bromine-induced oxidation of mercury in a combustion system. Five Hg-Cl and three Hg-Br mechanisms, some published and others under development, were evaluated and compared to the new data. The Hg-halogen mechanisms were combined with submechanisms from Reaction Engineering International for NO{sub x}, SO{sub x}, and hydrocarbons. The homogeneous kinetics under-predicted the levels of mercury oxidation observed in full-scale systems. This shortcoming can be corrected by including heterogeneous kinetics in the model calculations.« less
Partition characteristics of polycyclic aromatic hydrocarbons on soils and sediments
Chiou, C.T.; Mcgroddy, S.E.; Kile, D.E.
1998-01-01
The partition behavior was determined for three polycyclic aromatic hydrocarbons (PAHs), i.e., naphthalene, phenanthrene, and pyrene, from water to a range of soil and sediment samples. The measured partition coefficients of the individual PAHs between soil/sediment organic matter (SOM) and water (i.e., K(oc) values) are relatively invariant either for the 'clean' (uncontaminated) soils or for the clean sediments; however, the mean K(oc) values on the sediments are about twice the values on the soils. This disparity is similar to the earlier observation for other nonpolar solutes and reflects the compositional differences between soil and sediment organic matters. No significant differences in K(oc) are observed between a clean coastal marine sediment and freshwater sediments. The coastal sediments that are significantly impacted by organic contaminants exhibit higher K(oc) values. At given K(ow) values (octanol-water), the PAHs exhibit much higher K(oc) values than other relatively nonpolar solutes (e.g., chlorinated hydrocarbons). This effect is shown to result from the enhanced partition of PAHs to SOM rather than from lower K(ow) values of PAHs at given supercooled liquid solute solubilities in water. The enhanced partition of PAHs over other nonpolar solutes in SOM provides an account of the markedly different correlations between log K(oc) and log K(ow) for PAHs and for other nonpolar solutes. The improved partition of PAHs in SOM stems apparently from the enhanced compatibility of their cohesive energy densities with those of the aromatic components in SOM. The approximate aromatic fraction in soil/sediment organic matter has been assessed by solid-state 13C-NMR spectroscopy.The partition behavior was determined for three polycyclic aromatic hydrocarbons (PAHs), i.e., naphthalene, phenanthrene, and pyrene, from water to a range of soil and sediment samples. The measured partition coefficients of the individual PAHs between soil/sediment organic matter (SOM) and water (i.e., Koc values) are relatively invariant either for the `clean' (uncontaminated) soils or for the clean sediments; however, the mean Koc values on the sediments are about twice the values on the soils. This disparity is similar to the earlier observation for other nonpolar solutes and reflects the compositional differences between soil and sediment organic matters. No significant differences in Koc are observed between a clean coastal marine sediment and freshwater sediments. The coastal sediments that are significantly impacted by organic contaminants exhibit higher Koc values. At given Kow values (octanol-water), the PAHs exhibit much higher Koc values than other relatively nonpolar solutes (e.g., chlorinated hydrocarbons). This effect is shown to result from the enhanced partition of PAHs to SOM rather than from lower Kow values of PAHs at given supercooled liquid solute solubilities in water. The enhanced partition of PAHs over other nonpolar solutes in SOM provides an account of the markedly different correlations between log Koc and log Kow for PAHs and for other nonpolar solutes. The improved partition of PAHs in SOM stems apparently from the enhanced compatibility of their cohesive energy densities with those of the aromatic components in SOM. The approximate aromatic fraction in soil/sediment organic matter has been assessed by solid-state 13C-NMR spectroscopy.
NASA Technical Reports Server (NTRS)
Navarro-Gonzalex, Rafael; Sutter, Brad; Archer, Doug; Ming, Doug; Eigenbrode, Jennifer; Franz, Heather; Glavin, Daniel; McAdam, Amy; Stern, Jennifer; McKay, Christopher;
2013-01-01
The first chemical analysis of soluble salts in the soil was carried out by the Phoenix Lander in the Martian Arctic [1]. Surprisingly, chlorine was present as magnesium or calcium perchlorate at 0.4 to 0.6 percent. Additional support for the identification of perchlorate came from the evolved gas analysis which detected the release of molecular oxygen at 350-550C [1]. When Mars-like soils from the Atacama Desert were spiked with magnesium perchlorate (1 percent) and heated using the Viking GC-MS protocol, nearly all the organics were combusted but a small amount was chlorinated, forming chloromethane and dichloromethane [2]. These chlorohydrocarbons were detected by the Viking GC-MS experiments when the Martian soil was analyzed but they were considered to be terrestrial contaminants [3]. Reinterpretation of the Viking results suggests <0.1 percent perchlorate and ppm levels of organic carbon at landing site 1 and 2 [2]. The suggestion of perchlorate in the Viking sites [2] has been challenged on the grounds that the detected compounds (CH3Cl and CH2Cl2) were carried from Earth [4]. Recently the Sample Analysis at Mars (SAM) instrument on board the Mars Science Laboratory (MSL) ran four samples from an aeolian bedform named Rocknest. The samples analyzed were portioned from the fifth scoop at this location. The samples were heated to 835C at 35C/min with a He flow. The SAM QMS detected a major oxygen release (300-500C) [5], coupled with the release of chlorinated hydrocarbons (chloromethane, dichloromethane, trichloromethane, and chloromethylpropene) detected both by SAM QMS and GC-MS derived from known Earth organic contaminants in the instrument [6]. Calcium perchlorate appears to be the best candidate for evolved O2 in the Rocknest samples at this time but other Cl species (e.g., chlorates) are possible and must be evaluated. The potential detection of perchlorates in Rocknest material adds weight to the argument that both Viking Landers measured signatures of perchlorates. Even if the source of the organic carbon detected is still unknown, the chlorine source was likely Martian. Two mechanisms have been hypothesized for the formation of soil perchlorate: (1) Atmospheric oxidation of chlorine; and (2) UV photooxidation of chlorides catalyzed by mineral catalysts [7]. The presence of soil perchlorates in the Martian surface has important implications for the detection of organics [2], carbonates [8] and nitrates [9] by SAM.
NASA Astrophysics Data System (ADS)
Cutshall, N. H.; Gilmore, T.; Looney, B. B.; Vangelas, K. M.; Adams, K. M.; Sink, C. H.
2006-05-01
Like many US industries and businesses, the Department of Energy (DOE) is responsible for remediation and restoration of soils and ground water contaminated with chlorinated ethenes. Monitored Natural Attenuation (MNA) is an attractive remediation approach and is probably the universal end-stage technology for removing such contamination. Since 2003 we have carried out a multifaceted program at the Savannah River Site designed to advance the state of the art for MNA of chlorinated ethenes in soils and groundwater. Three lines of effort were originally planned: 1) Improving the fundamental science for MNA, 2) Promoting better characterization and monitoring (CM) techniques, and 3) Advancing the regulatory aspects of MNA management. A fourth line, developing enhanced attenuation methods based on sustainable natural processes, was added in order to deal with sites where the initial natural attenuation capacity cannot offset contaminant loading rates. These four lines have been pursued in an integrated and mutually supportive fashion. Many DOE site-cleanup program managers view CM as major expenses, especially for natural attenuation where measuring attenuation is complex and the most critical attenuation mechanisms cannot be determined directly. We have reviewed new and developing approaches to CM for potential application in support of natural attenuation of chlorinated hydrocarbons in ground water at DOE sites (Gilmore, Tyler, et al., 2006 WSRC-TR- 2005-00199). Although our project is focused on chlorinated ethenes, many of the concepts and strategies are also applicable to a wider range of contaminants including radionuclides and metals. The greatest savings in CM are likely to come from new management approaches. New approaches can be based, for example, on conceptual models of attenuation capacity, the ability of a formation to reduce risks caused by contaminants. Using the mass balance concept as a guide, the integrated mass flux of contaminant is compared to the attenuation capacity. The mass balance approach is controlled by a combination of boundary conditions (e.g., water inputs and outputs), flow dynamics, and contaminant concentrations. As a result, long term monitoring might be improved while reducing costs by measuring fewer point concentrations and simultaneously adding large-scale measurements of boundary conditions, using weather data, remote sensing of evapotranspiration, stream-flow monitoring, etc. Because there are no specific regulatory drivers for performance-monitoring, regulators are not accustomed to participating in monitoring system design. A partnership with the Interstate Technology Regulatory Council (ITRC) has been formed to promote communication and develop advanced guidance for MNA. Early and continued communication among technology developers, end users, regulators and the public has been essential to this progress.
Amakura, Yoshiaki; Tsutsumi, Tomoaki; Yoshimura, Morio; Nakamura, Masafumi; Handa, Hiroshi; Matsuda, Rieko; Teshima, Reiko; Watanabe, Takahiro
2016-01-01
The purpose of this study was to examine whether a simple bioassay used for the detection of dioxins (DXNs) could be applied to detect trace amounts of harmful DXN-like substances in food products. To identify substances with possible DXN-like activity, we assessed the ability of various compounds in the environment to bind the aryl hydrocarbon receptor (AhR) that binds specifically to DXNs. The compounds tested included 19 polycyclic aromatic hydrocarbons (PAHs), 20 PAH derivatives (nitrated, halogenated, and aminated derivatives), 23 pesticides, six amino acids, and eight amino acid metabolites. The AhR binding activities (AhR activity) of these compounds were measured using the chemical activated luciferase gene expression (CALUX) reporter gene assay system. The majority of the PAHs exhibited marked AhR activity that increased in a concentration-dependent manner. Furthermore, there was a positive link between AhR activity and the number of aromatic rings in the PAH derivatives. Conversely, there appeared to be a negative correlation between AhR activity and the number of chlorine residues present on halogenated PAH derivatives. However, there was no correlation between AhR activity and the number and position of substituents among nitrated and aminated derivatives. Among the pesticides tested, the indole-type compounds carbendazim and thiabendazole showed high levels of activity. Similarly, the indole compound tryptamine was the only amino acid metabolite to induce AhR activity. The results are useful in understanding the identification and characterization of AhR ligands in the CALUX assay. PMID:28231110
Na+, K+-activated-ATPase inhibition in rainbow trout: A site for organochlorine pesticide toxicity?
Davis, Paul W.; Wedemeyer, Gary A.
1971-01-01
1. The Na+, K+-activated, Mg2+-dependent-ATPase enzyme system in a heavy microsomal fraction of rainbow trout (Salmo gairdneri) brain was inhibited in vitro by chlorinated hydrocarbon pesticides.2. T50 (concentration at 50 per cent inhibition) values for dicofol, endosulfan and DDT were 5 × 10−6, 3 × 10−5 and 1 × 10−4 M respectively. Similar inhibition by these pesticides occurred in kidney and gill ATPase preparations.3. An unexpected finding was a failure of the classic inhibitor, ouabain, to block the Na+, K+-activated component of ATPase activity in the gill.4. It is suggested that inhibition of ATPase activity may be a causal factor in the toxic effects of organochlorine pesticides in fishes.
NASA Technical Reports Server (NTRS)
Fewell, L. L.
1976-01-01
Analysis of the volatiles and sublimate produced when para-polyphenylene is pyrolyzed to constant weight under vacuum in the temperature range from 380 to 1000 C indicates that the polymer undergoes thermal degradation in two stages. The first stage involved dehydrohalogenation, which is essentially a curing reaction that produces crosslinking between polyphenylene chains resulting from the loss of chlorine from the polymer in the form of hydrogen chloride. The second stage of the thermal degradation is dehydrogenation because hydrogen is the major volatile species. Increasing amounts of polycyclic aromatic hydrocarbons (phenanthrene and 9, 10 benzphenanthrene) in the sublimate, concomitant with increasing C/H ratios of the polymeric residue with pyrolysis temperature, is consistent with the buildup of polynuclear structures in the polymer matrix.
NASA Astrophysics Data System (ADS)
Kryazhev, Yu. G.; Vorob'ev, M. S.; Koval', N. N.; Trenikhin, M. V.; Solodovnichenko, V. S.; Sulakshin, S. A.; Likholobov, V. A.
2016-10-01
This work shows the possibility in principle of forming hydrocarbon structures in polyvinyl chloride films free of admixtures and polyvinyl chloride films modified with 5-mass % ferrocene via a radiation chemical transformation in the atmosphere with the use of an electron accelerator with a plasma cathode operating in the pulsed-periodic mode maximal electron energy no higher than 160 keV, pulse length of 40 μs, and current density of 5 mA/cm2. According to the results of semiquantitative X-ray microanalysis, an irradiated polyvinyl chloride film free of admixtures contains 92 of carbon, 6 of oxygen, and 2 mass % of chlorine; the irradiated polyvinyl chloride is an amorphous carbon material. A possible mechanism of the phenomenon is discussed.
Hoffman, D.J.; Albers, P.H.
1984-01-01
Results are reported for the embryotoxicity of 42 environmental contaminants applied externally to mallard (Anas platyrhynchos) eggs including crude and refined petroleum, and commercial formulations of herbicides and insecticides. Many of the petroleum pollutants were embryotoxic and moderately teratogenic and had LD50s of 0.3 to 5 ?l per egg (~6?90 ?g/g egg). The most toxic was a commercial oil used for control of road dust followed by South Louisiana crude oil, Kuwait crude, no. 2 fuel oil, bunker C fuel oil, and industrial and automotive waste oil. Prudhoe Bay crude, unused crankcase oil, aviation kerosene, and aliphatic hydrocarbon mixtures were less toxic ( LD50s of 18 to over 75 ? l) and less teratogenic. The LD50s of herbicides and insecticides in aqueous emulsion were measured by egg immersion; the most toxic were paraquat and trifluralin (LD50s of about 1.5 Ibs/A; 1.7 kg/ha). Propanil, bromoxynil with MCPA, methyl diclofop, prometon, endrin, sulprofos, and parathion were toxic (LD50s of 7 to 40 Ibs/A; 7.8?44.8 kg/ha), whereas 2,4-D, glyphosate, atrazine, carbaryl, dalapon, dicamba, methomyl, and phosmet were only slightly toxic or not toxic (LD50s of 178 to over 500 Ibs/A; 199?560 kg/ha). Pesticides in nontoxic oil vehicle applied by microliter pipet were up to 18 times more toxic than when applied in water vehicle, which was probably due to better penetration of the pesticide past the eggshell and its membranes. Teratogenic effects and impaired embryonic growth are reported and results discussed in terms of potential hazard at field levels of application. A discussion is provided on the effects of pollutants on the eggs of other species of birds under laboratory and field conditions.
Study on Sources of Volatile Organic Compounds (CMB) in Pearl River Delta region, China
NASA Astrophysics Data System (ADS)
Liu, Y.; Shao, M.; Lu, S.; Chang, C.; Wang, C. J.; Wang, B.
2007-05-01
The profiles of major Volatile organic compounds (VOCs) sources including vehicle exhaust, gasoline vapor, painting, asphalt, liquefied petroleum gas (LPG), biomass burning and petrochemical industry in Pearl River Delta were experimentally determined. Source samples were taken by using dilution chamber for mobile and stationary sources, laboratory simulation for biomass burning. The concentrations of 108 VOC species of sources were quantified by using canister with pre-concentration-GC/MS system, from which 52 PAMS hydrocarbons and one kind of chlorinated hydrocarbon were deployed to build the source profiles for source apportionment of VOCs. Based the measurement of source profiles, the possible tracers for various emission sources were identified, e.g 2-methylbutane and 1,3-butadiene were the tracers for motor vehicle exhaust, the characteristic compounds of architectural and furnishing coatings are aromatics such as toluene and m/p-xylene; the light hydrocarbons, namely n-butane, trans-2-butene and n-pentane, dominated the composition of gasoline vapor; and the nonane, decane and undecane are found to represent the asphalt emissions etc.. The CMB receptor model was applied to source apportionment of 58 hydrocarbons measured at seven sites during the PRD campaign, 2004. The 12 kinds of VOC sources include gasoline/diesel-powered vehicle exhaust, gasoline/diesel headspace vapor, vehicle evaporative emissions, liquid petroleum gas (LPG) leakage, painting vapors, asphalt emission from paved road, biomass burning, coal burning, chemical industry and petroleum refinery. Vehicle exhaust was the largest sources contributing over half of the ambient VOCs at the three urban sites (GuangZhou, FoShan and ZhongShan). LPG leakage played an important role with the percentage of 8- 16% in most sites in PRD. Contributions from solvents usage were highest at DongGuan, an industrial site. At XinKen, the solvents and coatings had the largest percentage of 31% probably due to the influence of its upwind area of DongGuan. The local biomass burning was also found to be a noticeable source at XK.
Becker, Carol J.
2010-01-01
The U.S. Geological Survey worked in cooperation with the U.S. Environmental Protection Agency and the Kickapoo Tribe of Oklahoma on two separate reconnaissance projects carried out concurrently. Both projects entailed the use of passive samplers as a sampling methodology to investigate the detection of selected organic compounds at stream sites in jurisdictional areas of several tribes in central Oklahoma during January-February 2009. The focus of the project with the U.S. Environmental Protection Agency was the detection of pesticides and pesticide metabolites using Semipermeable Membrane Devices at five stream sites in jurisdictional areas of several tribes. The project with the Kickapoo Tribe of Oklahoma focused on the detection of pesticides, pesticide metabolites, polycyclic aromatic hydrocarbons, polychlorinated biphenyl compounds, and synthetic organic compounds using Semipermeable Membrane Devices and Polar Organic Chemical Integrative Samplers at two stream sites adjacent to the Kickapoo tribal lands. The seven stream sites were located in central Oklahoma on the Cimarron River, Little River, North Canadian River, Deep Fork, and Washita River. Extracts from SPMDs submerged at five stream sites, in cooperation with the U.S. Environmental Protection Agency, were analyzed for 46 pesticides and 6 pesticide metabolites. Dacthal, a pre-emergent herbicide, was detected at all five sites. Pendimethalin, also a pre-emergent, was detected at one site. The insecticides chlorpyrifos and dieldrin were detected at three sites and p,p'-DDE, a metabolite of the insecticide DDT, also was detected at three sites. SPMDs and POCIS were submerged at the upstream edge and downstream edge of the Kickapoo tribal boundaries. Both sites are downstream from the Oklahoma City metropolitan area and multiple municipal wastewater treatment plants. Extracts from the passive samplers were analyzed for 62 pesticides, 10 pesticide metabolites, 3 polychlorinated biphenyl compounds, 35 polycyclic aromatic hydrocarbons, and 49 synthetic organic compounds. Ten pesticides and four pesticide metabolites were detected at the upstream site and seven pesticides and four pesticide metabolites were detected at the downstream site. Pesticides detected at both sites were atrazine, chlorpyrifos, dacthal, dieldrin, metolachlor, pendimethalin, and trans-nonachlor. Additionally at the upstream site, heptachlor, pentachlorophenol, and prometon were detected. The pesticide metabolites p,p'-DDE, cis-chlordane, and trans-chlordane also were detected at both sites. Polychlorinated biphenyl compounds aroclor-1016/1242, aroclor-1254, and aroclor-1260 were detected at both sites. The upstream site had 16 polycyclic aromatic hydrocarbon detections and the downstream site had 8 detections. Because of chromatographic interference during analysis, a positive identification of 17 polycyclic aromatic hydrocarbons could not be made. Consequently, there may have been a greater number of these compounds detected at both sites. A total of 36 synthetic organic compounds were detected at the two sites adjacent to the Kickapoo tribal lands. The upstream site had 21 synthetic organic compound detections: three detergent metabolites, two fecal indicators, three flame retardants, seven industrial compounds, five compounds related to personal care products, and beta-sitosterol, a plant sterol. Fifteen synthetic organic compounds were detected at the downstream site and included: one fecal indicator, three flame retardants, six industrial compounds, and five compounds related to personal care products.
Denk, Michael K; Milutinović, Nicholas S
2018-01-01
The insecticide DDT is an omnipresent environmental contaminant and an ongoing toxicological concern. The recent discovery that methylenetetrahydrofolate (MTHF) models are capable of reducing a range of halocarbons to hydrocarbons under biomimetic conditions has prompted us to investigate the possible role of MTHF in the metabolism of DDT. We now report that the reaction of MTHF models with DDT produces no less than five known in vivo metabolites of DDT, namely DDD, DDE, DDMU, DBP, and DDM. The capability of the MTHF models to produce the full spectrum of known DDT dehalogenation products is strong evidence that the mechanistically obscure metabolism of DDT may involve MTHF. The findings also suggest that DDT should be capable of disrupting folate-dependent pathways. Copyright © 2017 Elsevier Ltd. All rights reserved.
CADDIS Volume 2. Sources, Stressors and Responses: Insecticides
Introduction to the insecticides module, when to list insecticides as a candidate cause, ways to measure insecticides, simple and detailed conceptual diagrams for insecticides, insecticides module references and literature reviews.
CADDIS Volume 2. Sources, Stressors and Responses: Insecticides - Simple Conceptual Diagram
Introduction to the insecticides module, when to list insecticides as a candidate cause, ways to measure insecticides, simple and detailed conceptual diagrams for insecticides, insecticides module references and literature reviews.
CADDIS Volume 2. Sources, Stressors and Responses: Insecticides - Detailed Conceptual Diagram
Introduction to the insecticides module, when to list insecticides as a candidate cause, ways to measure insecticides, simple and detailed conceptual diagrams for insecticides, insecticides module references and literature reviews.
Bryant, Wade L.; Goodbred, Steve L.; Leiker, Thomas L.; Inouye, Laura; Johnson, B. Thomas
2007-01-01
Studies to assess the effects of urbanization on stream ecosystems are being conducted as part of the U.S. Geological Survey’s National Water-Quality Assessment (NAWQA) Program. The overall objectives of these studies are to (1) determine how hydrologic, geomorphic, water quality, habitat, and biological characteristics respond to land-use changes associated with urbanization in specific environmental settings, and (2) compare these responses across environmental settings. As part of an integrated assessment, semipermeable membrane devices (SPMDs) were deployed in streams along a gradient of urban land-use intensity in and around Atlanta, Georgia; Raleigh-Durham, North Carolina; and Denver-Fort Collins, Colorado, in 2003; and Dallas-Fort Worth, Texas; Milwaukee-Green Bay, Wisconsin; and Portland, Oregon, in 2004. Sites were selected to avoid point-source discharge and to minimize natural variability within each of the six metropolitan areas. In addition to standard chemical analysis for hydrophobic organic contaminants, three assays were used to address mixtures and potential toxicity: (1) Fluoroscan provides an estimate of the total concentration of polycyclic aromatic hydrocarbons (PAHs); (2) the P450RGS assay indicates the presence and levels of aryl hydrocarbon receptor agonists; and (3) Microtox® measures toxicological effects on photo-luminescent bacteria.Of the 140 compounds targeted or identified by gas chromatography/mass spectrometry analysis in this study, 67 were not detected. In terms of numbers and types of compounds, the following were detected: 2 wood preservatives, 6 insecticides (parent compounds), 5 herbicides, 22 polycyclic aromatic hydrocarbons, 2 dibenzofurans, 4 polychlorinated biphenyls, 7 compounds associated with fragrances or personal care products, 4 steroids associated with wastewater, 5 polydibromated diphenyl ethers (flame retardants), 3 plasticizers, 3 antimicrobials/disinfectants, and 3 detergent metabolites.Of the 73 compounds detected and three assays utilized, 29 were detected in 25 percent or more of the streams and were strongly related to increases in urban intensity (defined as having a Spearman’s rho > 0.5 with percent urban land cover) in at least one of the six metropolitan areas investigated. These 29 endpoints included 16 PAHs, a wood preservative (pentachloroanisole), 2 insecticides (chlorpyrifos and chlordane), 3 herbicides (benfluralin, trifluralin, and dacthal), a synthetic musk (hexahydrohexamethylcyclopentabenzopyran, HHCB), 2 furans (methyldibenzofuran and benzo[b]naphtho[2,3-d]furan), and a flame retardant (BDE 47). In addition, the number of compounds detected and results of the Fluoroscan and P450RGS assays were strongly related to urban intensity.Average water concentrations estimated from SPMDs were compared to screening benchmarks for the protection of human health and aquatic life; of the 14 compounds with available benchmarks, 3 compounds (anthracene, dieldrin, and diazinon) exceeded those levels in one or more streams. Both dieldrin and anthracene exceeded their respective benchmarks in seven streams, and diazinon in only one stream. There were more exceedances in Milwaukee-Green Bay and Raleigh-Durham than in the other metropolitan areas, and there were no exceedances in Dallas-Fort Worth.The six metropolitan areas studied differed in the number and types of endpoints related to urban intensity, probably from a combination of factors governing source strength, transport, and fate of hydrophobic compounds. The number of endpoints strongly related to urban intensity ranged from 3 in Dallas-Fort Worth and Portland to 21 in Raleigh-Durham. High frequencies of detection and strong correlations with urban land cover for pyrogenic PAHs (such as unsubstituted 4-ringed PAHs) in all six metropolitan areas indicate that these compounds are an important component of urbanization, regardless of location. Pentachloroanisole, dibenzofurans, and petrogenic PAHs (alkylated PAHs and heterocyclic dibenzothiophenes) were frequently detected and strongly related to urban intensity in Atlanta, Raleigh-Durham, Milwaukee-Green Bay, and Denver-Fort Collins. Two insecticides were related to urban intensity: chlorpyrifos in Atlanta, Raleigh-Durham, and Dallas-Fort Worth; and chlordane in Raleigh-Durham. Three herbicides were strongly related to urban intensity: trifluralin in Atlanta and Raleigh-Durham; benfluralin in Atlanta, and dacthal in Denver-Fort Collins. The detection frequencies for most wastewater indicator compounds were too low to establish relations with urban intensity. Of the wastewater compounds analyzed, HHCB in Raleigh-Durham and Denver-Fort Collins, and BDE 47 in Denver-Fort Collins and Dallas-Forth Worth, had the strongest relations with urban intensity.In addition to pyrogenic PAHs, levels of aryl hydrocarbon receptor agonists (as measured by the P450RGS assay) were strongly related to increasing urban intensity in all six metropolitan areas. PAHs were the only group of aryl hydrocarbon agonists consistently detected and related with urban intensity in all six metropolitan areas. It is unknown which compounds in the SPMDs caused the increased response in the P450RGS assay because the SPMDs likely contained many aryl hydrocarbon receptor agonists not quantified by chemical analysis. It is clear that bioavailable, aryl hydrocarbon receptor agonists increase in streams with increasing urban intensity in the basin. Potential toxicity mediated by this metabolic pathway should be considered in integrated assessments of the response of aquatic biota to urbanization.
NASA Astrophysics Data System (ADS)
Badin, Alice; Buttet, Géraldine; Maillard, Julien; Holliger, Christof; Hunkeler, Daniel
2014-05-01
Chlorinated ethenes (CEs) such as tetrachloroethene (PCE) are common persistent groundwater contaminants. Among clean-up strategies applied to sites affected by such pollution, bioremediation has been considered with a growing interest as it represents a cost-effective, environmental friendly approach. This technique however sometimes leads to an incomplete and slow biodegradation of CEs resulting in an accumulation of toxic metabolites. Understanding the reaction mechanisms underlying anaerobic reductive dechlorination would thus help assessing PCE biodegradation in polluted sites. Stable isotope analysis can provide insight into reaction mechanisms. For chlorinated hydrocarbons, carbon (C) and chlorine (Cl) isotope data (δ13C and δ37Cl) tend to show a linear correlation with a slope (m ≡ ɛC/ɛCl) characteristic of the reaction mechanism [1]. This study hence aims at exploring the potential of a dual C-Cl isotope approach in the determination of the reaction mechanisms involved in PCE reductive dechlorination. C and Cl isotope fractionation were investigated during anaerobic PCE dechlorination by two bacterial consortia containing members of the Sulfurospirillum genus. The specificity in these consortia resides in the fact that they each conduct PCE reductive dechlorination catalysed by one different reductive dehalogenase, i.e. PceADCE which yields trichloroethene (TCE) and cis-dichloroethene (cDCE), and PceATCE which yields TCE only. The bulk C isotope enrichment factors were -3.6±0.3 o for PceATCE and -0.7±0.1o for PceADCE. The bulk Cl isotope enrichment factors were -1.3±0.2 o for PceATCE and -0.9±0.1 o for PceADCE. When applying the dual isotope approach, two m values of 2.7±0.1 and 0.7±0.2 were obtained for the reductive dehalogenases PceATCE and PceADCE, respectively. These results suggest that PCE can be degraded according to two different mechanisms. Furthermore, despite their highly similar protein sequences, each reductive dehalogenase seems to catalyse PCE reductive dechlorination according to a different mechanism. In another study, an m value of 2.5±0.8 was found for PCE anaerobic dechlorination by a bacterial consortium dominated by species closely related to Desulfitobacterium aromaticivorans strain UKTL (consortia A) [2]. This value is indistinguishable from the one found for PceATCE within a 95% confidence interval although the reductive dehalogenase protein sequence of consortia A is distinctly different from the sequences of our two cultures. This suggests that the reaction mechanism is not related to the similarities between reductive dehalogenases. References 1. Abe, Y., et al., Carbon and Chlorine Isotope Fractionation during Aerobic Oxidation and Reductive Dechlorination of Vinyl Chloride and cis-1,2-Dichloroethene. Environmental Science & Technology, 2009. 43(1): p. 101-107. 2. Wiegert, C., et al., Carbon and Chlorine Isotope Fractionation During Microbial Degradation of Tetra- and Trichloroethene. Environmental Science & Technology, 2013. 47(12): p. 6449-6456.
Monitoring of the aerobe biodegradation of chlorinated organic solvents by stable isotope analysis
NASA Astrophysics Data System (ADS)
Horváth, Anikó; Futó, István; Palcsu, László
2014-05-01
Our chemical-biological basic research aims to eliminate chlorinated environmental contaminants from aquifers around industrial areas in the frame of research program supported by the European Social Fund (TÁMOP-4.2.2.A-11/1/KONV-2012-0043). The most careful and simplest way includes the in situ biodegradation with the help of cultured and compound specific strains. Numerous members of Pseudomonas bacteria are famous about function of bioremediation. They can metabolism the environmental hazardous chemicals like gas oils, dyes, and organic solvents. Our research based on the Pseudomonas putida F1 strain, because its ability to degrade halogenated hydrocarbons such as trichloroethylene. Several methods were investigated to estimate the rate of biodegradation, such as the measurement of the concentration of the pollutant along the contamination pathway, the microcosm's studies or the compound specific stable isotope analysis. In this area in the Transcarpathian basin we are pioneers in the stable isotope monitoring of biodegradation. The main goal is to find stable isotope fractionation factors by stable isotope analysis, which can help us to estimate the rate and effectiveness of the biodegradation. The subsequent research period includes the investigation of the method, testing its feasibility and adaptation in the environment. Last but not least, the research gives an opportunity to identify the producer of the contaminant based on the stable isotope composition of the contaminant.
DOE Office of Scientific and Technical Information (OSTI.GOV)
Safe, S.; Mason, G.; Keys, B.
1986-01-01
Polychlorinated dibenzofurans (PCDFs) and dibenzo-p-dioxins (PCDDs) elicit a number of common biologic and toxic responses which are triggered by their initial binding to a cytosolic receptor protein. These effects include the induction of several cytochrome P-448 dependent monoxygenases (eg, aryl hydrocarbon hydroxylase, AHH), body weight loss and thymic atrophy. The dose-response effects of selected PCDFs on AHH induction in rat hepatoma H-4-II E cells and cytosolic receptor binding affinities have been determined. The results of these in vivo and in vitro studies demonstrate the remarkable effects of structure on the activity of PCDFs. A systematic study of each of themore » four different position for chlorine substitution in the dibenzofuran ring system showed that the toxic and biologic potencies of these compounds varied with respect to differential chlorine substitution at all four position, i.e. C-3(7) > C-2(8) >C-4(6) > C-1(9). In vitro SARs for PCDDs confirmed the importance of the lateral CI substituents and also showed that 1,2(or 6,7-) substituted PCDDs were more active than the corresponding 1,3-dichloro analogs. In addition, there were significant decreases in activity with increasing non-lateral CI substitution. The SARs for PCDFs were different from the PCDDs and this was directly related to the asymmetric structure of the former group of compounds.« less
DOE Office of Scientific and Technical Information (OSTI.GOV)
Weisbrod, A.V.; Shea, D.; Moore, M.J.
1995-12-31
Populations of many marine organisms in Boston Harbor and Massachusetts Bay have been declining for decades. Overfishing, habitat loss, disease, and exposure to toxic contaminants have been implicated as causative factors for reductions in both commercially important species and endangered marine mammal populations. The purpose of this study was to determine if exposure to organic contaminants could be a factor in the pilot whale population decline and to develop a simple bioaccumulation model to assess the relative importance of the route of uptake and the significance of total elimination. Liver and blubber samples from ten individuals beached in 1991 onmore » Cape Cod, MA were analyzed by gas chromatography/electron capture detection (GC/ECD) and gas chromatography/mass spectrometry (GC/MS) for polychlorinated biphenyls (PCBs), chlorinated pesticides, polycyclic aromatic hydrocarbons (PAHs), and linear alkyl benzenes (LABs). PCBs, DDT, DDE, DDD, and other chlorinated pesticides were identified and found to be high (ppm range) in several individuals. PAHs and LABs were typically below one ppb. Concentrations of these contaminants in the water and food that pilot whales consume were used in a bioaccumulation model. The model predicted lower concentrations in the whale than the authors observed. For all but the least hydrophobic contaminants (e.g., naphthalene) they predict that food (biomagnification) is the dominant route of uptake into the whales.« less
Virulence and antibiotic susceptibility of Aeromonas spp. isolated from drinking water.
Scoaris, Denise de Oliveira; Colacite, Jean; Nakamura, Celso V; Ueda-Nakamura, Tânia; de Abreu Filho, Benício A; Dias Filho, Benedito P
2008-01-01
Aeromonas isolates from tap water, mineral water, and artesian well water were investigated for their ability to produce different potential virulence factors or markers such as hemolysins, cytotoxins, phospholipase, DNase, hydrophobicity and their ability to adhere to epithelial cells and to abiotic surfaces. The susceptibility to antibiotics of Aeromonas isolates was also examined. Majority of the isolates displayed hemolytic activity against sheep erythrocytes, while only 7 of the 23 Aeromonas strains displayed DNase activity and 4 of the 23 Aeromonas strains tested were regarded as positive for phospholipase production. Most of the isolates showed cytotoxic activities in culture filtrate dilutions at titer of 1/8 or lower. No general relation between the strain isolated and the ability to interact with epithelial cells could be established. Using the bacterial adherence to hydrocarbons method, most of the strains were classified as highly hydrophilic. All five Aeromonas jandaei strains isolates, 9 of the 12 Aeromonas sp strains and four of the five Aeromonas hydrophila were multidrug resistant. The most active antimicrobial was ciprofloxacin (susceptible in 100% of the isolates), and the least active antibiotic was ampicillin (resistance in 92% of the isolates). The majority of the isolates tested were not killed by chlorine at 1.2 mg/l. Whether the high tolerance to chlorine of Aeromonas isolates can be linked to greater virulence is not know.
A new sensor for the assessment of personal exposure to volatile organic compounds
NASA Astrophysics Data System (ADS)
Chen, Cheng; Driggs Campbell, Katherine; Negi, Indira; Iglesias, Rodrigo A.; Owens, Patrick; Tao, Nongjian; Tsow, Francis; Forzani, Erica S.
2012-07-01
To improve our understanding of indoor and outdoor personal exposures to common environmental toxicants released into the environment, new technologies that can monitor and quantify the toxicants anytime anywhere are needed. This paper presents a wearable sensor to provide such capabilities. The sensor can communicate with a common smart phone and provides accurate measurement of volatile organic compound concentration at a personal level in real-time, providing environmental toxicants data every three minutes. The sensor has high specificity and sensitivity to aromatic, alkyl, and chlorinated hydrocarbons with a resolution as low as 4 parts-per-billion (ppb), with a detection range of 4 ppb-1000 ppm (parts-per-million). The sensor's performance was validated using Gas Chromatography and Selected Ion Flow Tube - Mass Spectrometry reference methods in a variety of environments and activities with overall accuracy higher than 81% (r2 > 0.9). Field tests examined personal exposure in various scenarios including: indoor and outdoor environments, traffic exposure in different cities which vary from 0 to 50 ppmC (part-per-million carbon from hydrocarbons), and pollutants near the 2010 Deepwater Horizon's oil spill. These field tests not only validated the performance but also demonstrated unprecedented high temporal and spatial toxicant information provided by the new technology.
A New Sensor for the Assessment of Personal Exposure to Volatile Organic Compounds
Chen, Cheng; Campbell, Katherine Driggs; Negi, Indira; Iglesias, Rodrigo A.; Owens, Patrick; Tao, Nongjian; Tsow, Francis; Forzani, Erica
2012-01-01
To improve our understanding of indoor and outdoor personal exposures to common environmental toxicants released into the environment, new technologies that can monitor and quantify the toxicants anytime anywhere are needed. This paper presents a wearable sensor to provide such capabilities. The sensor can communicate with a common smart phone and provides accurate measurement of volatile organic compound concentration at a personal level in real time, providing environmental toxicants data every three minutes. The sensor has high specificity and sensitivity to aromatic, alkyl, and chlorinated hydrocarbons with a resolution as low as 4 parts per billion (ppb), with a detection range of 4 ppb to 1000 ppm (parts per million). The sensor's performance was validated using Gas Chromatography and Selected Ion Flow Tube - Mass Spectrometry reference methods in a variety of environments and activities with overall accuracy higher than 81% (r2 > 0.9). Field tests examined personal exposure in various scenarios including: indoor and outdoor environments, traffic exposure in different cities which vary from 0 to 50 ppmC (part-per-million carbon from hydrocarbons), and pollutants near the 2010 Deepwater Horizon's oil spill. These field tests not only validated the performance but also demonstrated unprecedented high temporal and spatial toxicant information provided by the new technology. PMID:22736952
Kannan, K.; Moon, H.-B.; Yun, S.-H.; Agusa, T.; Thomas, N.J.; Tanabe, S.
2008-01-01
Concentrations of organochlorine pesticides (DDTs, HCHs, and chlordanes), polychlorinated biphenyls (PCBs), polybrominated diphenyl ethers (PBDEs), polycyclic aromatic hydrocarbons (PAHs), perfluorinated compounds (PFCs), and 20 trace elements were determined in livers of 3- to 5-year old stranded sea otters collected from the coastal waters of California, Washington, and Alaska (USA) and from Kamchatka (Russia). Concentrations of organochlorine pesticides, PCBs, and PBDEs were high in sea otters collected from the California coast. Concentrations of DDTs were 10-fold higher in California sea otters than in otters from other locations; PCB concentrations were 5-fold higher, and PBDE concentrations were 2-fold higher, in California sea otters than in otters from other locations. Concentrations of PAHs were higher in sea otters from Prince William Sound than in sea otters from other locations. Concentrations of several trace elements were elevated in sea otters collected from California and Prince William Sound. Elevated concentrations of Mn and Zn in sea otters from California and Prince William Sound were indicative of oxidative stress-related injuries in these two populations. Concentrations of all of the target compounds, including trace elements, that were analyzed in sea otters from Kamchatka were lower than those found from the US coastal locations. ?? The Royal Society of Chemistry.
Control of Pyrethroid-Resistant Chagas Disease Vectors with Entomopathogenic Fungi
Pedrini, Nicolás; Mijailovsky, Sergio J.; Girotti, Juan R.; Stariolo, Raúl; Cardozo, Rubén M.; Gentile, Alberto; Juárez, M. Patricia
2009-01-01
Background Triatoma infestans-mediated transmission of Tripanosoma cruzi, the causative agent of Chagas disease, remains as a major health issue in southern South America. Key factors of T. infestans prevalence in specific areas of the geographic Gran Chaco region—which extends through northern Argentina, Bolivia, and Paraguay—are both recurrent reinfestations after insecticide spraying and emerging pyrethroid-resistance over the past ten years. Among alternative control tools, the pathogenicity of entomopathogenic fungi against triatomines is already known; furthermore, these fungi have the ability to fully degrade hydrocarbons from T. infestans cuticle and to utilize them as fuel and for incorporation into cellular components. Methodology and Findings Here we provide evidence of resistance-related cuticle differences; capillary gas chromatography coupled to mass spectrometry analyses revealed that pyrethroid-resistant bugs have significantly larger amounts of surface hydrocarbons, peaking 56.2±6.4% higher than susceptible specimens. Also, a thicker cuticle was detected by scanning electron microscopy (32.1±5.9 µm and 17.8±5.4 µm for pyrethroid-resistant and pyrethroid-susceptible, respectively). In laboratory bioassays, we showed that the virulence of the entomopathogenic fungi Beauveria bassiana against T. infestans was significantly enhanced after fungal adaptation to grow on a medium containing insect-like hydrocarbons as the carbon source, regardless of bug susceptibility to pyrethroids. We designed an attraction-infection trap based on manipulating T. infestans behavior in order to facilitate close contact with B. bassiana. Field assays performed in rural village houses infested with pyrethroid-resistant insects showed 52.4% bug mortality. Using available mathematical models, we predicted that further fungal applications could eventually halt infection transmission. Conclusions This low cost, low tech, ecologically friendly methodology could help in controlling the spread of pyrethroid-resistant bugs. PMID:19434231
Synergistic degradation of chlorinated hydrocarbons with microorganisms and zero valent iron
NASA Astrophysics Data System (ADS)
Schöftner, Philipp; Summer, Dorothea; Leitner, Simon; Watzinger, Andrea; Wimmer, Bernhard; Reichenauer, Thomas
2016-04-01
Sites contaminated with chlorinated hydrocarbons (CHC) are located mainly within build-up regions. Therefore in most cases only in-situ technologies without excavation of soil material can be used for remediation. This project examines a novel in-situ remediation method, in which the biotic degradation via bacteria is combined with abiotic degradation via zero-valent iron particles (ZVI). ZVI particles are injected into the aquifer where CHC-molecules are reductively dechlorinated. However Fe0 is also oxidized by reaction with water leading to generation of H2 without any CHC degradation. To achieve biotic degradation often strictly anaerobic strains of the bacteria Dehalococcoides are used. These bacteria can dechlorinate CHC by utilizing H2. By combining these processes the H2, produced during the anaerobic corrosion of Fe0, could be used by bacteria for further CHC degradation. Therefore the amount of used Fe0 and as a consequence also remediation costs could be reduced. Additionally the continuous supply of H2 could make the bacterial degradation more controllable. Different Fe0 particles (nano- and micro-scale) were tested for their perchloroethene (PCE) degradation rate and H2 production rate in microcosms. PCE-degradation rate by different bacterial cultures was investigated in the same microcosm system. In course of these experiments the 13C enrichment factors of the PCE degradation of the different particles and cultures were determined to enable the differentiation of biotic and abiotic degradation. Preliminary results showed, that the nano-scale particles reacted faster with PCE and water than their micro-scaled counterparts. The PCE degradation via micro-scaled particles lead to 13C enrichment factors in the range of -3,6 ‰ ± 0,6 to -9,5 ‰ ± 0,2. With one of the examined bacterial cultures a fast reduction of PCE to ethene was observed. Although PCE and TCE were completely degraded by this culture the metabolites DCE and VC could still be detected. Further microcosm experiments will be implemented by the time of the EGU General Assembly 2016. In the framework of these experiments other bacterial cultures and ZVI particles as well as the combination of biotic and abiotic dehalogenation will be investigated.
NASA Astrophysics Data System (ADS)
Rolston, H. M.; Semprini, L.; Thankitkul, S.; Azizian, M.; Hyman, M. R.
2016-12-01
1,4-dioxane (1,4-D) is a frequently observed groundwater contaminant due to its use as a stabilizer in commercial solvent formulations. In situ bioremediation could potentially provide a large cost savings for treatment of mixtures of chlorinated aliphatic hydrocarbons (CAHs) that include 1,4-D. Aerobic cometabolism is a particularly attractive option, as microorganisms can be stimulated in situ using specific primary substrates. Results will be presented that show the model isobutane-metabolizing bacteria, Rhodococcus rhodochrous (ATCC 21198), has the ability to transform 14-D at high rates and transformation capacities to concentrations below the drinking water screening level of 0.67 µg L-1. Resting cell transformation tests showed 1,4-D and a broad range of CAHs can be cometabolized by ATCC 21198. The maximum transformation rate (kmax) and the half-substrate coefficient (Ks) were determined for isobutane (the growth substrate), 1,4-D, 1,1,1-trichloroethane (1,1,1-TCA), 1,1,2-trichloroethane (1,1,2-TCA), 1,1-dichloroethane (1,1-DCA); 1,2-dichloroethane ((1,2-DCA) and 1,1-dichloroethene (1,1-DCE). Of the CAHs tested, 1,1-DCA had the highest kmax, approximately 25% of that for isobutane utilization, while 1,1,1-TCA had the lowest kmax, approximately 2% of isobutane's. 1,4-D was rapidly transformed and had a kmax 25% of that of isobutane. ATCC 21198 effectively transformed mixtures of 1,4-D, 1,1-DCE, 1,2-DCA and 1,1,1-TCA, both in the presence and absence isobutane. Model simulations were performed for the simultaneous cometabolism of 1,4-D and CAH mixtures by ATCC 21198, that included inhibition among the contaminants and isobutane , and terms for a limited transformation capacity. A good match to experimental observations was obtaining using the independently measured rate parameters. Results of model simulations will also be presented using a reactive transport model to evaluate conditions of in situ bioremediation using strain ATCC 21198.
NASA Astrophysics Data System (ADS)
Schreiter, Inga J.; Wefer-Roehl, Annette; Graber, Ellen R.; Schüth, Christoph
2017-04-01
Biochar (BC) is increasingly deemed a potential sorbent for contaminants in soil and water remediation, and brownfield restoration. In this study, sorption and extraction experiments were performed to assess the potential of three different BCs to sorb and retain the chlorinated hydrocarbons trichloroethylene (TCE) and tetrachloroethylene (PCE). BCs studied were produced from wood chips, grain husk, and cattle manure at 450 °C. A commercially available activated carbon (AC) served as a reference. The sorption behaviour was studied in batch experiments in single solute and bi-solute systems. Resulting isotherms were fitted to the Freundlich model. To assess the desorption behaviour, a five-step extraction scheme (water at 40°C, water at 80°C, methanol at 50°C, toluene at 50°C, and n-hexane at 50°) was developed, utilizing Accelerated Solvent Extraction. Isotherms revealed distinct differences in sorption behaviour depending on BC feedstock. Sorption capacity ranked as follows: wood chip BC > grain husk BC > cattle manure BC for both contaminants. This sequence could be attributable to an increasing specific surface area, an increasing amount of carbon, and a decreasing ash content of the sorbents. It is noteworthy that all three BCs were more effective in adsorbing TCE, which is surprising, given the higher logKow of PCE. The reverse was observed for the AC. Here, sorption is purely driven by the hydrophobicity of the compound rather than sorbent properties. In bi-solute experiments, PCE sorbed as good as or stronger than TCE, yet the total mass of sorbed compounds increased slightly. In contrast, AC showed a significant decrease of TCE sorption and no significant changes in the total mass sorbed. Extraction experiments revealed that for all BCs a large fraction of the contaminants could not be readily desorbed. In all cases, water remobilized < 5 % of the total contaminant mass and up to 70 % could not be extracted by any of the solvents. The findings suggest that BC is a promising sorbent for mixed contaminant systems as it offers a diverse nature of sorption sites and is more effective in long-term immobilization than AC.
Woskie, Susan R.; Gore, Rebecca; Sandler, Dale P.; Schmidt, Silke; Kamel, Freya
2017-01-01
Abstract Objective: This paper describes the retrospective exposure assessment conducted to assess occupational exposures for the Genes and Environmental Exposures in Veterans (GENEVA) study, a case–control study investigating the joint contribution of genetics and environmental exposures to the risk of amyotrophic lateral sclerosis (ALS) among military veterans. Methods: Occupational histories for 1597 study participants collected as part of the GENEVA study were the basis for this retrospective exposure assessment. The data set included 15528 jobs held from 1924 to 2010, representing 4539 unique industry and occupation (I&O) combinations. Three industrial hygiene experts were recruited to independently rate occupational exposures to specific agents previously associated with an increased risk of ALS. Utilizing information on industry, job title, tasks performed, and materials used for each job held, raters assigned exposures associated with each I&O for the ‘current time’ defined as the period after 1995 (post-1995). The exposure assessment targeted agents identified as potential occupational risk factors for ALS. Experts rated semi-quantitatively exposure intensity in five exposure categories (0–4) for Group A agents (lead, formaldehyde, hydrocarbon solvents, and chlorinated solvents) and qualitatively as yes/no (1/0) exposed for Group B agents (mercury, selenium, arsenic, polychlorinated biphenyls, electromagnetic field, pesticides, and viral agents). Confidence scores (0–3) were reported for every I&O rated based on raters’ experience with that industry and/or job. Each I&O was assigned an average exposure score of the raters and an alternative exposure rating was developed for each I&O by excluding low confidence (<2) scores before averaging. Exposure reconstruction for jobs held pre-1995 was done by comparing exposure data extracted from the OSHA Chemical Exposure and Health Database (CEHD) during pre-1995 and post-1995. For agents with limited exposure data in the CEHD, pre-1995 exposures were determined based on raters’ judgment. Results: The proportion of I&O combinations determined to be ‘exposed’ ranged from 0.1 to 26% across different agents, with the highest values corresponding to hydrocarbon solvents and the lowest to selenium. Industries with the highest proportion of exposed records include manufacturing, utilities, healthcare, and military with non-combat jobs. Analyses for raters’ reliability showed the best agreement between the raters when rating exposure to viral agents (kappa = 0.67), hydrocarbon solvents (kappa = 0.53), and lead (kappa = 0.50). The proportion of ‘exposed’ I&O combinations increased for hydrocarbon solvents, chlorinated solvents, and pesticides when exposure ratings were adjusted by raters’ confidence. Compared to post-1995, exposures in the earlier period (pre-1995) were deemed higher or the same for most of the agents and lower for formaldehyde and electromagnetic field exposures. Conclusions: Our results indicate that using raters’ confidence assessment in determining exposure scores increases both the proportion of I&O combinations regarded as exposed and the intensity scores, suggesting raters tend to be conservative in their assessment when they lack detailed knowledge of an industry or job. PMID:28355414
NASA Technical Reports Server (NTRS)
Sutter, B.; Heil, E.; Morris, R. V.; Archer, P. D.; Ming, D. W.; Niles, P. B.; Eigenbrode, J. L.; Franz, H.; Freissinet C.; Glavin, D. P.;
2015-01-01
The Sample Analysis at Mars (SAM) instrument onboard the Curiosity rover detected O2 and HCl gas releases from the Rocknest (RN) eolian bedform and the John Klein (JK) and Cumberland (CB) drill hole materials in Gale Crater. Chlorinated hydrocarbons have also been detected by the SAM quadrupole mass spectrometer (QMS) and gas chromatography/mass spectrometer (GCMS). These detections along with the detection of perchlorate (ClO4-) by the Mars Phoenix Lander's Wet Chemistry Laboratory (WCL) suggesting perchlorate is a possible candidate for evolved O2 and chlorine species. Laboratory thermal analysis of individual per-chlorates has yet to provide an unequivocal temperature match to the SAM O2 and HCl release data. These detections along with the detection of perchlorate (ClO4-) by the Mars Phoenix Lander's Wet Chemistry Laboratory suggested perchlorate is a possible candidate for evolved O2 and chlorine species. Laboratory thermal analysis of pure perchlorates has yet to provide an unequivocal temperature match to the SAM O2 and HCl release data. Analog laboratory analysis of iron mineralogy detected in Gale materials that was physically mixed with Ca- and Mg-perchlorate has been shown to catalyze lower O2 release temperatures and approach some SAM O2 release data. Instead of physical mixtures used in previous work, the work presented here utilized perchlorate solutions added to Fe phases. This technique allowed for perchlorate to come in closer contact with the Fe-phase and may more closely mimic Mars conditions where humidity can increase enough to cause deliquescence of the highly hygroscopic perchlorate phases. The objective of this work is to: 1) Utilize a laboratory SAM analog instrument to evaluate the O2 release temperatures from Mg- and Ca-perchlorates solutions applied to Fephases detetected in Gale Crate; and 2) Determine if perchlorate solutions can provide improved matches with the SAM O2 temperature release profiles.
Pittman, Charles U; He, Jinbao
2002-05-03
Na/NH3 reductions have been used to dehalogenate polychlorinated biphenyls (PCBs), chlorinated aliphatic hydrocarbons (CAHs) and pesticides at diffusion controlled rates at room temperature in model compound studies in both dry NH3 and when water was added. The rate ratio of dechlorination (aliphatic and aromatic compounds) versus reaction of the solvated electron with water is very large, allowing wet soils or sludges to be remediated without an unreasonable consumption of sodium. Several soils, purposely contaminated with 1,1,1-trichloroethane, 1-chlorooctane and tetrachloroethylene, were remediated by slurring the soils in NH3 followed by addition of sodium. The consumption of sodium per mole of chlorine removed was examined as a function of both the hazardous substrate's concentration in the soil and the amount of water present. The Na consumption per Cl removed increases as the amount of water increases and as the substrate concentration in soil decreases. However, remediation was still readily accomplished from 5000 to 3000ppm to sub ppm levels of RCl in the presence of substantial amounts of water. PCB- and dioxin-contaminated oils were remediated with Na/NH3 as were PCB-contaminated soils and sludges from contaminated sites. Ca/NH3 treatments also successfully remediated PCB-contaminated clay, sandy and organic soils but laboratory studies demonstrated that Ca was less efficient than Na when substantial amounts of water were present. The advantages of solvated electron reductions using Na/NH3 include: (1) very rapid dehalogenation rates at ambient temperature, (2) soils (even clay soils) break down into particles and slurry nicely in NH3, (3) liquid ammonia handling technology is well known and (4) removal from soils, recovery and recycle of ammonia is easy due to its low boiling point. Finally, dechlorination is extremely fast even for the 'corner' chlorines in the substrate Mirex (structure in Eq. (5)).
NASA Astrophysics Data System (ADS)
Schöftner, Philipp; Summer, Dorothea; Wimmer, Bernhard; Reichenauer, Thomas
2017-04-01
Chlorinated hydrocarbons (CHCs) are especially toxic pollutants which are frequently found at contaminated sites in urban areas which are densely covered with buildings. In specific in such areas, in-situ technologies are favourable since conventional remediation technologies as excavation are often not applicable. This project examines a combination of two in-situ remediation methods, in which the biotic degradation via bacteria (dehalococcoides) is combined with abiotic degradation by zero-valent iron particles (ZVI). ZVI particles are injected into the aquifer where CHC-molecules are reductively dechlorinated. However Fe(0) is also oxidized by reaction with water leading to generation of H2 without any CHC degradation. To achieve biotic degradation often strictly anaerobic strains of the bacteria Dehalococcoides are used. These bacteria can dechlorinate CHC by utilizing H2. By combining these processes the H2, produced during the anaerobic corrosion of Fe(0), could be used by bacteria for further CHC degradation. Different Fe(0) particles (nano- and micro-scale) were combined with microbial dehalogenation for dehalogenation of perchloroethene (PCE) in batch experiments. PCE degradation rates and H2 production rates of the different particles and cultures were determined. Additionally an artificial aquifer (approximately 1.0 x 0.5 x 0.5 metres) was established. This aquifer was spiked with PCE and subsequently treated with Fe(0) particles and microbial. Molasses was added to facilitate microbial dehalogenation. Preliminary results showed that all H2 evolved during oxidation of Fe(0) were used by the associated microbial community. Nevertheless the overall dehalogenation of chlorinated compounds as well as the production of methane was hardly influenced by the addition of Fe(0), at least not over the experimental period of 28 days. Independent if Fe(0) was added or not all chlorinated compounds were dehalogenated whereby ethene and ethane were the only end products.
Altman, Bob; Henson, C.M.; Waite, I.R.
1997-01-01
Aquatic toxicological investigations in the basin have focused primarily on fish. These studies have addressed chlorinated pesticides, polychlorinated biphenyls (PCBs), dioxins and furans, polycyclic aromatic hydrocarbons (PAHs), and trace elements in aquatic tissue, as well as fish health assessments, skeletal abnormalities, and aquatic toxicological responses. Several pesticides exceeded U.S. Environmental Protection Agency and State water-quality criteria for the protection of aquatic life. Elevated PCB, dioxin, and furan concentrations were associated with point sources, such as pulp and paper mills. Elevated concentrations of mercury in aquatic tissue were associated with several reservoirs. Fish health assessments and skeletal abnormality studies detected high levels of abnormalities in fish from the main stem Willamette River. Few investigations have examined aquatic toxicological responses, such as enzyme induction assays, growth assays, and biomarker studies.
Organochlorine pesticides, their toxic effects on living organisms and their fate in the environment
Megha, Pankajshan; Sreedev, Puthur
2016-01-01
Organochlorine (OC) pesticides are synthetic pesticides widely used all over the world. They belong to the group of chlorinated hydrocarbon derivatives, which have vast application in the chemical industry and in agriculture. These compounds are known for their high toxicity, slow degradation and bioaccumulation. Even though many of the compounds which belong to OC were banned in developed countries, the use of these agents has been rising. This concerns particularly abuse of these chemicals which is in practice across the continents. Though pesticides have been developed with the concept of target organism toxicity, often non-target species are affected badly by their application. The purpose of this review is to list the major classes of pesticides, to understand organochlorine pesticides based on their activity and persistence, and also to understand their biochemical toxicity. PMID:28652852
Fathepure, B Z; Tiedje, J M; Boyd, S A
1988-01-01
Hexachlorobenzene was dechlorinated to tri- and dichlorobenzenes in anaerobic sewage sludge. The complete biotransformation of 190 microM hexachlorobenzene (approximately 50 ppm) occurred within 3 weeks. The calculated rate of hexachlorobenzene dechlorination was 13.6 mumol liter-1 day-1. Hexachlorobenzene was dechlorinated via two routes, both involving the sequential removal of chlorine from the aromatic ring. The major route was hexachlorobenzene----pentachlorobenzene----1,2,3,5-tetrachlorobenzene--- -1,3,5- trichlorobenzene. Greater than 90% of the added hexachlorobenzene was recovered as 1,3,5-trichlorobenzene, and there was no evidence for further dechlorination of 1,3,5-trichlorobenzene. The minor route was hexachlorobenzene----pentachlorobenzene----1,2,4,5-tetrachlorobenzene--- -1,2,4- trichlorobenzene----dichlorobenzenes. These results extend reductive dechlorination to poorly water soluble aromatic hydrocarbons which could potentially include other important environmental pollutants like polychlorinated biphenyls. PMID:3355129
Bioconcentration of chlorinated aromatic hydrocarbons in aquatic macrophytes
DOE Office of Scientific and Technical Information (OSTI.GOV)
Gobas, F.A.P.C.; McNeil, E.J.; Lovett-Doust, L.
1991-05-01
This study reports the bioconcentration and the uptake and elimination kinetics of a series of nonreactive, hydrophobic organic substances in the submerged aquatic macrophyte Myriophyllum spicatum. The tested substances represent a wide range of aqueous solubilities and 1-octanol-water partition coefficients (K{sub OW}). The plant-water bioconcentration factor is shown to follow a linear relationship with the octanol-water partition coefficient for all chemicals, including the superhydrophobic chemicals with log K{sub OW} up to 8.3. The uptake and elimination rate constants tend to follow a biphasic relationship with K{sub OW}. A kinetic model is developed for organic chemical bioconcentration is submerged aquatic macrophytemore » species. This model is applied to the Detroit River and Lake St. Clair to illustrate the role of aquatic macrophytes in chemical dynamics in aquatic systems.« less
Modeling the GPR response of leaking, buried pipes
DOE Office of Scientific and Technical Information (OSTI.GOV)
Powers, M.H.; Olhoeft, G.R.
1996-11-01
Using a 2.5D, dispersive, full waveform GPR modeling program that generates complete GPR response profiles in minutes on a Pentium PC, the effects of leaking versus non-leaking buried pipes are examined. The program accounts for the dispersive, lossy nature of subsurface materials to GPR wave propagation, and accepts complex functions of dielectric permittivity and magnetic permeability versus frequency through Cole-Cole parameters fit to laboratory data. Steel and plastic pipes containing a DNAPL chlorinated solvent, an LNAPL hydrocarbon, and natural gas are modeled in a surrounding medium of wet, moist, and dry sand. Leaking fluids are found to be more detectablemore » when the sand around the pipes is fully water saturated. The short runtimes of the modeling program and its execution on a PC make it a useful tool for exploring various subsurface models.« less
Effect of five lubricants on life of AISI 9310 spur gears
NASA Technical Reports Server (NTRS)
Townsend, D. P.; Zaretsky, E. V.
1985-01-01
Spur-gear surface fatigue tests were conducted with five lubricants using a single lot of consumable-electrode vacuum melted (CVM) AISI 9310 spur gears. The lot of gears was divided into five groups, each of which was tested with a different lubricant. The test lubricants are classified as either a synthetic hydrocarbon, mineral oil, or ester-based lubricant. All five lubricants have imilar viscosity and pressure-viscosity coefficients. A pentaerythritol base stock without sufficient antiwear additives produced a surface fatigue life pproximately 22 percent that of the same base stock with chlorine and phosphorus type additives. The presence of sulfur type antiwear additives in the lubricant did not appear to affect the surface fatigue life of the gears tested. No statistical difference in the 10-percent surface fatigue life was produced with four of the five lubricants.
Martin, Kiri E.; Ozsvar, Jazmin
2014-01-01
Monooxygenase (MO) enzymes initiate the aerobic oxidation of alkanes and alkenes in bacteria. A cluster of MO genes (smoXYB1C1Z) of thus-far-unknown function was found previously in the genomes of two Mycobacterium strains (NBB3 and NBB4) which grow on hydrocarbons. The predicted Smo enzymes have only moderate amino acid identity (30 to 60%) to their closest homologs, the soluble methane and butane MOs (sMMO and sBMO), and the smo gene cluster has a different organization from those of sMMO and sBMO. The smoXYB1C1Z genes of NBB4 were cloned into pMycoFos to make pSmo, which was transformed into Mycobacterium smegmatis mc2-155. Cells of mc2-155(pSmo) metabolized C2 to C4 alkanes, alkenes, and chlorinated hydrocarbons. The activities of mc2-155(pSmo) cells were 0.94, 0.57, 0.12, and 0.04 nmol/min/mg of protein with ethene, ethane, propane, and butane as substrates, respectively. The mc2-155(pSmo) cells made epoxides from ethene, propene, and 1-butene, confirming that Smo was an oxygenase. Epoxides were not produced from larger alkenes (1-octene and styrene). Vinyl chloride and 1,2-dichloroethane were biodegraded by cells expressing Smo, with production of inorganic chloride. This study shows that Smo is a functional oxygenase which is active against small hydrocarbons. M. smegmatis mc2-155(pSmo) provides a new model for studying sMMO-like monooxygenases. PMID:25015887
Hohnstock-Ashe, A. M.; Plummer, S.M.; Yager, R.M.; Baveye, P.; Madsen, E.L.
2001-01-01
A recent article presented geochemical and microbial evidence establishing metabolic adaptation to and in-situ reductive dechlorination of trichloroethene (TCE) in a fractured dolomite aquifer. This study was designed to further explore site conditions and microbial populations and to explain previously reported enhancement of reductive dechlorination by the addition of pulverized dolomite to laboratory microcosms. A survey of groundwater geochemical parameters (chlorinated ethenes, ethene, H2, CH4, DIC, DOC, and ??13C values for CH4, DIC, and DOC) indicated that in situ reductive dechlorination was ongoing and that an unidentified pool of organic carbon was contributing, likely via microbial respiration, to the large and relatively light onsite DIC pool. Petroleum hydrocarbons associated with the dolomite rock were analyzed by GC/MS and featured a characteristically low ??13C value. Straight chain hydrocarbons were extracted from the dolomite previously found to stimulate reductive dechlorination; these were particularly depleted in hexadecane (HD). Thus, we hypothesized that HD and related hydrocarbons might be anaerobically respired and serve both as the source of onsite DIC and support reductive dechlorination of TCE. Microcosms amended with pulverized dolomite demonstrated reductive dechlorination, whereas a combusted dolomite amendment did not. HD-amended microcosms were also inactive. Therefore, the stimulatory factor in the pulverized dolomite was heat labile, but that component was not HD. Amplified Ribosomal DNA Restriction Analysis (ARDRA) of the microbial populations in well waters indicated that a relatively low diversity, sulfur-transforming community outside the plume was shifted toward a high diversity community including Dehalococcoides ethenogenes-type microorganisms inside the zone of contamination. These observations illustrate biogeochemical intricacies of in situ reductive dechlorination reactions.
Jia, Jian-li; Li, Guang-he; Zhong, Yi
2004-05-01
By means of the biostimulation and bioaugmentation in the micro-ecological environment of contaminated soil with petrochemical hydrocarbons, the biodegradation rates and mode of the contaminants were significantly improved. Based on the investigations carried out in some oilfields and petrochemical industrial area of Northern China, the relationship between the abiotic factors such as nutrient, pH, contaminants, water content, alkalinity, etc., and microbial activities was interpreted and identified in this paper. The results from the investigations and indoor and in-situ experiments conducted recent years indicated that the soils in the areas, to the extent, have been polluted by the different kinds of organic compounds composed of monoaromatic benzene, PAHs, chlorinated solvent, and alkanes, and the concentrations of the compounds mostly were elevated as compared to the background, with the highest 34,000 mg/kg dry soil. The column chromatography analysis results showed that the alkyl and aromatic compounds were accounted for more than 50% of the total hydrocarbon contents, which was readily degraded by degrading bacteria and improved the degrading microbe activities. The effective nitrogen and phosphorus encountered in the soil was less than 30 mg/kg dry soil and 10 mg/kg dry soil, only about 5% of total contents of them respectively. Based on the stoichiometric calculation and reasonable ratio of carbon to nutrient content regarding the biodegradation of organic compounds, the nutrient levels mainly composed of nitrogen and phosphorus in polluted soil as importantly limiting factors to degrading bacterial growth and activity were insufficient to the biodegradation of petrochemicals, and it is needed to add the nutrient for the bioremediation of contaminated soil. It is undoubted that the optimization of abiotic factors play significant role in increasing the microbial activity and improving the biodegradation rates.
Multiple stressor effects in relation to declining amphibian populations
Linder, Greg L.; Krest, Sherry K.; Sparling, Donald; Little, E.
2003-01-01
Original research discusses the protocols and approaches to studying the effects of multiple environmental stressors on amphibian populations and gives new perspectives on this complicated subject. This new publication integrates a variety of stressors that can act in concert and may ultimately cause a decline in amphibian populations.Sixteen peer-reviewed papers cover:Toxicity Assessment examines methods, which range from long-established laboratory approaches for evaluating adverse chemical effects to amphibians, to methods that link chemicals in surface waters, sediments, and soils with adverse effects observed among amphibians in the field.Field and Laboratory Studies illustrates studies in the evaluation of multiple stressor effects that may lead to declining amphibian populations. A range of laboratory and field studies of chemicals, such as herbicides, insecticides, chlorinated organic compounds, metals, and complex mixtures are also included.Causal Analysis demonstrates the range of tools currently available for evaluating "cause-effect" relationships between environmental stressors and declining amphibian populations.Audience: This new publication is a must-have for scientists and resource management professionals from diverse fields, including ecotoxicology, chemistry, ecology, field biology, conservation biology, and natural resource management.
The impact of insecticides to local honey bee colony Apis cerana indica in laboratory condition
NASA Astrophysics Data System (ADS)
Putra, Ramadhani E.; Permana, Agus D.; Nuriyah, Syayidah
2014-03-01
Heavy use of insecticides considered as one of common practice at local farming systems. Even though many Indonesian researchers had stated the possible detrimental effect of insecticide on agriculture environment and biodiversity, researches on this subject had been neglected. Therefore, our purpose in this research is observing the impact of insecticides usage by farmer to non target organisme like local honey bee (Apis cerana indica), which commonly kept in area near agriculture system. This research consisted of field observations out at Ciburial, Dago Pakar, Bandung and laboratory tests at School of Life Sciences and Technology, Institut Teknologi Bandung. The field observations recorded visited agriculture corps and types of pollen carried by bees to the nest while laboratory test recorderd the effect of common insecticide to mortality and behavior of honey bees. Three types of insecticides used in this research were insecticides A with active agent Chlorantraniliprol 50 g/l, insecticide B with active agent Profenofos 500 g/l, and insecticides C with active agent Chlorantraniliprol 100 g/l and λ-cyhalotrin 50g/l. The results show that during one week visit, wild flower, Wedelia montana, visited by most honey bees with average visit 60 honey bees followed by corn, Zea mays, with 21 honey bees. The most pollen carried by foragers was Wedelia montana, Calliandra callothyrsus, and Zea mays. Preference test show that honeybees tend move to flowers without insecticides as the preference to insecticides A was 12.5%, insecticides B was 0%, and insecticides was C 4.2%. Mortality test showed that insecticides A has LD50 value 0.01 μg/μl, insecticide B 0.31 μg/μl, and insecticides C 0.09 μg/μl which much lower than suggested dosage recommended by insecticides producer. This research conclude that the use of insecticide could lower the pollination service provide by honey bee due to low visitation rate to flowers and mortality of foraging bees.
DOE Office of Scientific and Technical Information (OSTI.GOV)
Golovanova, I.L.; Chuiko, G.M.; Pavlov, D.F.
1994-03-01
Previous research has shown that sublethal concentrations of cadmium, naphthalene and dichlorvos (DDVP) decreased growth rates in bream and Mozambique tilapia. One of the factors known to affect fish growth is the activity of gut digestive enzymes such as of lipases, proteases, carbohydrases. We assumed that toxicant-induced inhibition of the digestive enzyme activity and, consequently, the impaired digestion of food may contribute to the reduction of growth in fish exposed to toxicants. However, the influence of toxicants on digestive enzyme activities is poorly studied. The contribution of toxicant-induced changes of digestive enzymes activity to growth rate retardation in exposed fishmore » remains unknown. The goal of this study was to examine the influence of an organophosphorus insecticide DDVP, a polyaromatic hydrocarbon naphthalene, and a metal cadmium on fish gut carbohydrase (CH) activity. 14 refs., 2 tabs.« less
Pang, Yuan-Ping; Brimijoin, Stephen; Ragsdale, David W; Zhu, Kun Yan; Suranyi, Robert
2012-04-01
Insect pests are responsible for human suffering and financial losses worldwide. New and environmentally safe insecticides are urgently needed to cope with these serious problems. Resistance to current insecticides has resulted in a resurgence of insect pests, and growing concerns about insecticide toxicity to humans discourage the use of insecticides for pest control. The small market for insecticides has hampered insecticide development; however, advances in genomics and structural genomics offer new opportunities to develop insecticides that are less dependent on the insecticide market. This review summarizes the literature data that support the hypothesis that an insect-specific cysteine residue located at the opening of the acetylcholinesterase active site is a promising target site for developing new insecticides with reduced off-target toxicity and low propensity for insect resistance. These data are used to discuss the differences between targeting the insect-specific cysteine residue and targeting the ubiquitous catalytic serine residue of acetylcholinesterase from the perspective of reducing off-target toxicity and insect resistance. Also discussed is the prospect of developing cysteine-targeting anticholinesterases as effective and environmentally safe insecticides for control of disease vectors, crop damage, and residential insect pests within the financial confines of the present insecticide market.
Pang, Yuan-Ping; Brimijoin, Stephen; Ragsdale, David W; Zhu, Kun Yan; Suranyi, Robert
2012-01-01
Insect pests are responsible for human suffering and financial losses worldwide. New and environmentally safe insecticides are urgently needed to cope with these serious problems. Resistance to current insecticides has resulted in a resurgence of insect pests, and growing concerns about insecticide toxicity to humans discourage the use of insecticides for pest control. The small market for insecticides has hampered insecticide development; however, advances in genomics and structural genomics offer new opportunities to develop insecticides that are less dependent on the insecticide market. This review summarizes the literature data that support the hypothesis that an insect-specific cysteine residue located at the opening of the acetylcholinesterase active site is a promising target site for developing new insecticides with reduced off-target toxicity and low propensity for insect resistance. These data are used to discuss the differences between targeting the insect-specific cysteine residue and targeting the ubiquitous catalytic serine residue of acetylcholinesterase from the perspective of reducing off-target toxicity and insect resistance. Also discussed is the prospect of developing cysteine-targeting anticholinesterases as effective and environmentally safe insecticides for control of disease vectors, crop damage, and residential insect pests within the financial confines of the present insecticide market. PMID:22280344
Using degree-days to maximize your pest management tool box
USDA-ARS?s Scientific Manuscript database
Insecticide control is limited by many factors: insecticide coverage, insecticide half-life, insect life stage, and plant growth. Using degree-day models to time insecticide applications accurately is a powerful tactic that increases the efficacy of each insecticide application. Mating disruption op...
Miarinjara, Adélaïde; Boyer, Sébastien
2016-02-01
Plague is a rodent disease transmissible to humans by infected flea bites, and Madagascar is one of the countries with the highest plague incidence in the world. This study reports the susceptibility of the main plague vector Xenopsylla cheopis to 12 different insecticides belonging to 4 insecticide families (carbamates, organophosphates, pyrethroids and organochlorines). Eight populations from different geographical regions of Madagascar previously resistant to deltamethrin were tested with a World Health Organization standard bioassay. Insecticide susceptibility varied amongst populations, but all of them were resistant to six insecticides belonging to pyrethroid and carbamate insecticides (alphacypermethrin, lambdacyhalothrin, etofenprox, deltamethrin, bendiocarb and propoxur). Only one insecticide (dieldrin) was an efficient pulicide for all flea populations. Cross resistances were suspected. This study proposes at least three alternative insecticides (malathion, fenitrothion and cyfluthrin) to replace deltamethrin during plague epidemic responses, but the most efficient insecticide may be different for each population studied. We highlight the importance of continuous insecticide susceptibility surveillance in the areas of high plague risk in Madagascar.
Analysis of Insecticides in Dead Wild Birds in Korea from 2010 to 2013.
Kim, Soohee; Park, Mi-Young; Kim, Hyo-Jin; Shin, Jin Young; Ko, Kyung Yuk; Kim, Dong-Gyu; Kim, MeeKyung; Kang, Hwan-Goo; So, ByungJae; Park, Sung-Won
2016-01-01
Wild birds are exposed to insecticides in a variety of ways, at different dose levels and via multiple routes, including ingestion of contaminated food items, and dermal, inhalation, preening, and embryonic exposure. Most poisoning by insecticides occurs as a result of misuse or accidental exposure, but intentional killing of unwanted animals also occurs. In this study, we investigated insecticides in the gastric contents of dead wild birds that were suspected to have died from insecticide poisoning based on necropsy. The wild birds were found dead in various regions and locations such as in mountains, and agricultural and urban areas. A total of 182 dead wild birds of 27 species were analyzed in this study, and insecticide residue levels were determined in 60.4% of the total samples analyzed. Monocrotophos and phosphamidon were the most common insecticides identified at rates of 50.0% and 30.7% of the insecticide-positive samples, respectively. Other insecticides identified in dead wild birds included organophosphorous, organochlorine and carbamate insecticides. However, there was limited evidence to conclusively establish the cause of death related to insecticides in this study. Nevertheless, considering the level of insecticide exposure, it is speculated that the exposure was mainly a result of accidental or intentional killing, and not from environmental residue.
Huber, Sandra; Warner, Nicholas A; Nygård, Torgeir; Remberger, Mikael; Harju, Mikael; Uggerud, Hilde T; Kaj, Lennart; Hanssen, Linda
2015-06-01
Eggs of 3 seabird species, common eider (Somateria mollisima), European shag (Phalacrocorax aristotelis aristotelis), and European herring gull (Larus argentatus), were surveyed for a broad range of legacy and emerging pollutants to assess chemical mixture exposure profiles of seabirds from the Norwegian marine environment. In total, 201 chemical substances were targeted for analysis ranging from metals, organotin compounds, polycyclic aromatic hydrocarbons (PAHs), polychlorinated biphenyls (PCBs) and associated metabolites, chlorinated paraffins, chlorinated and nonchlorinated organic pesticides, per- and polyfluoroalkyl substances (PFAS), dechlorane plus, octachlorostyrene, brominated flame retardants (BFRs), organophosphorous compounds, brominated and alkyl phenols, cyclic siloxanes, and phthalates. Of the chemicals targeted, 149 substances were found above the detection limits, with metals dominating the contaminant profile and comprising 60% of the total contaminant load. Polychlorinated biphenyls, pesticides, organophosphorous compounds, and PFAS were the dominant contaminant classes of organic pollutants found within the seabird species, with the highest loads occurring in herring gulls, followed by shag, and common eider. New generation pollutants (e.g., PFAS, organophosphorous compounds, and alkylphenols) were detected at similar or higher concentrations than the legacy persistent organic pollutants (POPs). Time trends of reported concentrations of legacy POPs appear to have decreased in recent decades from the Norwegian coastal environment. Concentrations of detected pollutants do not appear to have a negative effect on seabird population development within the sampling area. Additional stress caused by pollutants, however, may affect seabird health more at the individual level. © 2015 SETAC.
Lorah, Michelle M.; Clark, Jeffrey S.
1996-01-01
Chemical manufacturing, munitions filling, and other military-support activities have resulted in the contamination of ground water, surface water, and soil in the Canal Creek area of Aberdeen Proving Ground, Maryland. Chlorinated volatile organic compounds, including 1,1,2,2-tetrachloroethane and trichloroethylene, are widespread ground-water contaminants in two aquifers that are composed of unconsolidated sand and gravel. Distribution and fate of chlorinated organic compounds in the ground water has been affected by the movement and dissolution of solvents in their dense immiscible phase and by microbial degradation under anaerobic conditions. Detection of volatile organic contaminants in adjacent surface water indicates that shallow contaminated ground water discharges to surface water. Semivolatile organic compounds, especially polycyclic aromatic hydrocarbons, are the most prevalent organic contaminants in soils. Various trace elements, such as arsenic, cadmium, lead, and zinc, were found in elevated concentrations in ground water, surface water, and soil. Simulations with a ground-water-flow model and particle tracker postprocessor show that, without remedial pumpage, the contaminants will eventually migrate to Canal Creek and Gunpowder River. Simulations indicate that remedial pumpage of 2.0 million gallons per day from existing wells is needed to capture all particles originating in the contaminant plumes. Simulated pumpage from offsite wells screened in a lower confined aquifer does not affect the flow of contaminated ground water in the Canal Creek area.
Lord, Kevin; Moll, David; Lindsey, John K.; Mahne, Sarah; Raman, Girija; Dugas, Tammy; Cormier, Stephania; Troxlair, Dana; Lomnicki, Slawo; Dellinger, Barry; Varner, Kurt
2011-01-01
Exposure to airborne particles is associated with increased cardiovascular morbidity and mortality. During the combustion of chlorine-containing hazardous materials and fuels, chlorinated hydrocarbons chemisorb to the surface of transition metal-oxide-containing particles, reduce the metal, and form an organic free radical. These radical-particle systems can survive in the environment for days and are called environmentally persistent free radicals (EPFRs). This study determined whether EPFRs could decrease left ventricular function before and after ischemia and reperfusion (I/R) in vivo. Male Brown Norway rats were dosed (8 mg/kg, i.t.) 24 hr prior to testing with particles containing the EPFR of 1, 2-dichlorobenzene (DCB230). DCB230 treatment decreased systolic and diastolic function. DCB230 also produced pulmonary and cardiac inflammation. After ischemia, systolic, but not diastolic function was significantly decreased in DCB230-treated rats. Ventricular function was not affected by I/R in control rats. There was greater oxidative stress in the heart and increased 8-isoprostane (biomarker of oxidative stress) in the plasma of treated vs control rats after I/R. These data demonstrate for the first time that DCB230 can produce inflammation and significantly decrease cardiac function at baseline and after I/R in vivo. Furthermore, these data suggest that EPFRs may be a risk factor for cardiac toxicity in healthy individuals and individuals with ischemic heart disease. Potential mechanisms involving cytokines/chemokines and/or oxidative stress are discussed. PMID:21385100
Yuan, G; Chen, D; Yin, L; Wang, Z; Zhao, L; Wang, J Y
2014-06-01
In this research a gas-liquid fluidized bed reactor was developed for removing chlorine (Cl) from polyvinyl chloride (PVC) to favor its pyrolysis treatment. In order to efficiently remove Cl within a limited time before extensive generation of hydrocarbon products, the gas-liquid fluidized bed reactor was running at 280-320 °C, where hot N2 was used as fluidizing gas to fluidize the molten polymer, letting the molten polymer contact well with N2 to release Cl in form of HCl. Experimental results showed that dechlorination efficiency is mainly temperature dependent and 300 °C is a proper reaction temperature for efficient dechlorination within a limited time duration and for prevention of extensive pyrolysis; under this temperature 99.5% of Cl removal efficiency can be obtained within reaction time around 1 min after melting is completed as the flow rate of N2 gas was set around 0.47-0.85 Nm(3) kg(-1) for the molten PVC. Larger N2 flow rate and additives in PVC would enhance HCl release but did not change the final dechlorination efficiency; and excessive N2 flow rate should be avoided for prevention of polymer entrainment. HCl is emitted from PVC granules or scraps at the mean time they started to melt and the melting stage should be taken into consideration when design the gas-liquid fluidized bed reactor for dechlorination. Copyright © 2013 Elsevier Ltd. All rights reserved.
Simultaneous control of microorganisms and disinfection by-products by sequential chlorination.
Chen, Chao; Zhang, Xiao-Jian; He, Wen-Jie; Han, Hong-Da
2007-04-01
To introduce a new sequential chlorination disinfection process in which short-term free chlorine and chloramine are sequentially added. Pilot tests of this sequential chlorination were carried out in a drinking water plant. The sequential chlorination disinfection process had the same or better efficiency on microbe (including virus) inactivation compared with the free chlorine disinfection process. There seemed to be some synergetic disinfection effect between free chlorine and monochloramine because they attacked different targets. The sequential chlorination disinfection process resulted in 35.7%-77.0% TTHM formation and 36.6%-54.8% THAA5 formation less than the free chlorination process. The poorer the water quality was, the more advantage the sequential chlorination disinfection had over the free chlorination. This process takes advantages of free chlorine's quick inactivation of microorganisms and chloramine's low disinfection by-product (DBP) yield and long-term residual effect, allowing simultaneous control of microbes and DBPs in an effective and economic way.
75 FR 30824 - Methidathion; Cancellation Order for Pesticide Registrations
Federal Register 2010, 2011, 2012, 2013, 2014
2010-06-02
... Chemical Name 100-530 Methidathion Methidathion Technical 10163-236 Supracide 2E Methidathion Insecticide... Supracide 2E Methidathion Insecticide 10163-CA-01-0002 Supracide 2E Methidathion Insecticide 10163-CA-01... Supracide 2E Methidathion Insecticide 10163-CA-04-0023 Supracide 2E Methidathion Insecticide 10163-CO-01...
NASA Astrophysics Data System (ADS)
Xu, Zhiping; Shi, Lina; Jiang, Danping; Cheng, Jiagao; Shao, Xusheng; Li, Zhong
2015-10-01
Incorporating the photoisomerizable azobenzene into imidacloprid produced a photoswitchable insecticidal molecule as the first neonicotinoid example of remote control insecticide performance with spatiotemporal resolution. The designed photoswitchable insecticides showed distinguishable activity against Musca both in vivo and in vitro upon irradiation. Molecular docking study further suggested the binding difference of the two photoisomers. The generation of these photomediated insecticides provides novel insight into the insecticidal activity facilitating further investigation on the functions of insect nicotinic acetylcholine receptors and opens a novel way to control and study insect behavior on insecticide poisoning using light.
Resistance to bio-insecticides or how to enhance their sustainability: a review.
Siegwart, Myriam; Graillot, Benoit; Blachere Lopez, Christine; Besse, Samantha; Bardin, Marc; Nicot, Philippe C; Lopez-Ferber, Miguel
2015-01-01
After more than 70 years of chemical pesticide use, modern agriculture is increasingly using biological control products. Resistances to conventional insecticides are wide spread, while those to bio-insecticides have raised less attention, and resistance management is frequently neglected. However, a good knowledge of the limitations of a new technique often provides greater sustainability. In this review, we compile cases of resistance to widely used bio-insecticides and describe the associated resistance mechanisms. This overview shows that all widely used bio-insecticides ultimately select resistant individuals. For example, at least 27 species of insects have been described as resistant to Bacillus thuringiensis toxins. The resistance mechanisms are at least as diverse as those that are involved in resistance to chemical insecticides, some of them being common to bio-insecticides and chemical insecticides. This analysis highlights the specific properties of bio-insecticides that the scientific community should use to provide a better sustainability of these products.
Yang, Yajun; Dong, Biqin; Xu, Hongxing; Zheng, Xusong; Tian, Junce; Heong, Kongleun; Lu, Zhongxian
2014-08-01
The brown planthopper, Nilaparvata lugens (Stål), is one of the most important insect pests on paddy rice in tropical and temperate Asia. Overuse and misuse of insecticides have resulted in the development of high resistance to many different insecticides in this pest. Studies were conducted to evaluate the change of resistance level to four insecticides over 15 generations without any exposure to insecticides in brown planthopper. After 15 generations' rearing without exposure to insecticide, brown planthopper could reverse the resistance to imidacloprid, chlorpyrifos, fipronil, and fenobucarb. The range and style of resistance reversal of brown planthopper differed when treated with four different insecticides. To monitor potential changes in insect physiological responses, we measured the activity of each of the three selected enzymes, including acetylcholinesterases (AChE), general esterases (EST), and glutathione S-transferases. After multiple generations' rearing without exposure to insecticide, AChE and EST activities of brown planthopper declined with the increased generations, suggesting that the brown planthopper population adjusted activities of EST and AChE to adapt to the non-insecticide environment. These findings suggest that the reducing, temporary stop, or rotation of insecticide application could be incorporated into the brown planthopper management.
Hayat, Khizar; Afzal, Muhammad; Aqueel, Muhammad Anjum; Ali, Sajjad; Saeed, Muhammad Farhan; Khan, Qaiser M; Ashfaq, Muhammad; Damalas, Christos A
2018-09-01
Insecticide exposure can affect honey bees in agro-ecosystems, posing behavioral stresses that can lead to population decline. In this study, insecticide incidence, DNA damage, and antioxidant enzyme activity were studied in Apis florea and A. dorsata honey bee samples collected from insecticide-treated and insecticide-free areas of Punjab, Pakistan. Seven insecticides: chlorpyrifos, dimethoate, imidacloprid, phorate, emamectin, chlorfenapyr, and acetamiprid were detected in seven samples of A. florea and five samples of A. dorsata. In total, 12 samples (22.2%) of honey bees were found positive to insecticide presence out of 54 samples. The most frequently detected insecticide was chlorpyrifos, which was found in four samples (7.4%), with a concentration ranging from 0.01 to 0.05 μg/g and an average concentration 0.03 μg/g. The comet assay or single cell gel electrophoresis assay, a simple way to measure DNA strand breaks in eukaryotic cells, was used to microscopically find damage of DNA at the level of a single cell. Comet tail lengths of DNA in A. florea and A. dorsata samples from insecticide-treated areas were significantly higher (P < 0.05) than samples from insecticide-free areas. The highest comet tail length (19.28 ± 2.67 μm) was observed in DNA of A. dorsata from insecticide-treated areas, while the minimum one (3.18 ± 1.46 μm) was noted in A. dorsata from insecticide-free areas. Catalase (CAT) activity did not vary significantly between honey bee samples from insecticide-treated and insecticide-free areas, while glutathione S-transferase (GST) activity showed a significant reduction in response to insecticide exposure. Significant positive correlations were detected between enzyme activity and insecticide concentration in honey bee species from insecticide-treated areas compared with control groups. Toxicity from pesticide exposure at sub-lethal levels after application or from exposure to pesticide residues should not be underestimated in honey bees, as it may induce physiological impairment that can decline honey bees' health. Copyright © 2018 Elsevier B.V. All rights reserved.
Temporal variability of selected air toxics in the United States
NASA Astrophysics Data System (ADS)
McCarthy, Michael C.; Hafner, Hilary R.; Chinkin, Lyle R.; Charrier, Jessica G.
Ambient measurements of hazardous air pollutants (HAPs, air toxics) collected in the United States from 1990 to 2005 were analyzed for diurnal, seasonal, and/or annual variability and trends. Visual and statistical analyses were used to identify and quantify temporal variations in air toxics at national and regional levels. Sufficient data were available to analyze diurnal variability for 14 air toxics, seasonal variability for 24 air toxics, and annual trends for 26 air toxics. Four diurnal variation patterns were identified and labeled invariant, nighttime peak, morning peak, and daytime peak. Three distinct seasonal patterns were identified and labeled invariant, cool, and warm. Multiple air toxics showed consistent decreasing trends over three trend periods, 1990-2005, 1995-2005, and 2000-2005. Trends appeared to be relatively consistent within chemically similar pollutant groups. Hydrocarbons such as benzene, 1,3-butadiene, styrene, xylene, and toluene decreased by approximately 5% or more per year at more than half of all monitoring sites. Concentrations of carbonyl compounds such as formaldehyde, acetaldehyde, and propionaldehyde were equally likely to have increased or decreased at monitoring sites. Chlorinated volatile organic compounds (VOCs) such as tetrachloroethylene, dichloromethane, and methyl chloroform decreased at more than half of all monitoring sites, but decreases among these species were much more variable than among the hydrocarbons. Lead particles decreased in concentration at most monitoring sites, but trends in other metals were not consistent over time.
Shie, Ruei-Hao; Chan, Chang-Chuan
2013-10-15
The air monitors used by most regulatory authorities are designed to track the daily emissions of conventional pollutants and are not well suited for measuring hazardous air pollutants that are released from accidents such as refinery fires. By applying a wide variety of air-monitoring systems, including on-line Fourier transform infrared spectroscopy, gas chromatography with a flame ionization detector, and off-line gas chromatography-mass spectrometry for measuring hazardous air pollutants during and after a fire at a petrochemical complex in central Taiwan on May 12, 2011, we were able to detect significantly higher levels of combustion-related gaseous and particulate pollutants, refinery-related hydrocarbons, and chlorinated hydrocarbons, such as 1,2-dichloroethane, vinyl chloride monomer, and dichloromethane, inside the complex and 10 km downwind from the fire than those measured during the normal operation periods. Both back trajectories and dispersion models further confirmed that high levels of hazardous air pollutants in the neighboring communities were carried by air mass flown from the 22 plants that were shut down by the fire. This study demonstrates that hazardous air pollutants from industrial accidents can successfully be identified and traced back to their emission sources by applying a timely and comprehensive air-monitoring campaign and back trajectory air flow models. Copyright © 2013 The Authors. Published by Elsevier B.V. All rights reserved.
Two-step chlorination: A new approach to disinfection of a primary sewage effluent.
Li, Yu; Yang, Mengting; Zhang, Xiangru; Jiang, Jingyi; Liu, Jiaqi; Yau, Cie Fu; Graham, Nigel J D; Li, Xiaoyan
2017-01-01
Sewage disinfection aims at inactivating pathogenic microorganisms and preventing the transmission of waterborne diseases. Chlorination is extensively applied for disinfecting sewage effluents. The objective of achieving a disinfection goal and reducing disinfectant consumption and operational costs remains a challenge in sewage treatment. In this study, we have demonstrated that, for the same chlorine dosage, a two-step addition of chlorine (two-step chlorination) was significantly more efficient in disinfecting a primary sewage effluent than a one-step addition of chlorine (one-step chlorination), and shown how the two-step chlorination was optimized with respect to time interval and dosage ratio. Two-step chlorination of the sewage effluent attained its highest disinfection efficiency at a time interval of 19 s and a dosage ratio of 5:1. Compared to one-step chlorination, two-step chlorination enhanced the disinfection efficiency by up to 0.81- or even 1.02-log for two different chlorine doses and contact times. An empirical relationship involving disinfection efficiency, time interval and dosage ratio was obtained by best fitting. Mechanisms (including a higher overall Ct value, an intensive synergistic effect, and a shorter recovery time) were proposed for the higher disinfection efficiency of two-step chlorination in the sewage effluent disinfection. Annual chlorine consumption costs in one-step and two-step chlorination of the primary sewage effluent were estimated. Compared to one-step chlorination, two-step chlorination reduced the cost by up to 16.7%. Copyright © 2016 Elsevier Ltd. All rights reserved.