Raman Spectra and Cross Sections of Ammonia, Chlorine, Hydrogen Sulfide, Phosgene, and Sulfur Dioxide Toxic Gases in the Fingerprint Region 400-1400 cm-1

DTIC Science & Technology

2016-02-11

AIP ADVANCES 6, 025310 (2016) Raman spectra and cross sections of ammonia , chlorine, hydrogen sulfide, phosgene, and sulfur dioxide toxic gases in...Received 10 December 2015; accepted 3 February 2016; published online 11 February 2016) Raman spectra of ammonia (NH3), chlorine (Cl2), hydrogen...and cross sections of ammonia (NH3), chlorine (Cl2), hydrogen sulfide (H2S), phosgene (CCl2O), and sulfur dioxide (SO2) toxic gases in the fingerprint

Cutaneous exposure to vesicant phosgene oxime: Acute effects on the skin and systemic toxicity

DOE Office of Scientific and Technical Information (OSTI.GOV)

Tewari-Singh, Neera, E-mail: Neera.tewari-singh@uc

Phosgene Oxime (CX), an urticant or nettle agent categorized as a vesicant, is a potential chemical warfare and terrorist weapon. Its exposure can result in widespread and devastating effects including high mortality due to its fast penetration and ability to cause immediate severe cutaneous injury. It is one of the least studied chemical warfare agents with no effective therapy available. Thus, our goal was to examine the acute effects of CX following its cutaneous exposure in SKH-1 hairless mice to help establish a relevant injury model. Results from our study show that topical cutaneous exposure to CX vapor causes blanchingmore » of exposed skin with an erythematous ring, necrosis, edema, mild urticaria and erythema within minutes after exposure out to 8 h post-exposure. These clinical skin manifestations were accompanied with increases in skin thickness, apoptotic cell death, mast cell degranulation, myeloperoxidase activity indicating neutrophil infiltration, p53 phosphorylation and accumulation, and an increase in COX-2 and TNFα levels. Topical CX-exposure also resulted in the dilatation of the peripheral vessels with a robust increase in RBCs in vessels of the liver, spleen, kidney, lungs and heart tissues. These events could cause a drop in blood pressure leading to shock, hypoxia and death. Together, this is the first report on effects of CX cutaneous exposure, which could help design further comprehensive studies evaluating the acute and chronic skin injuries from CX topical exposure and elucidate the related mechanism of action to aid in the identification of therapeutic targets and mitigation of injury. - Highlights: • Phosgene oxime cutaneous exposure causes skin blanching, edema and urticaria. • Penetration of phosgene oxime causes dilation of vasculature in internal organs. • Mast cells could play an important role in phosgene oxime-induced skin injury. • Phosgene oxime could induce low blood pressure and hypoxia leading to mortality. • Data is significant for developing a phosgene oxime-induced skin injury model.« less

Phosgene

Integrated Risk Information System (IRIS)

Phosgene ; CASRN 75 - 44 - 5 Human health assessment information on a chemical substance is included in the IRIS database only after a comprehensive review of toxicity data , as outlined in the IRIS assessment development process . Sections I ( Health Hazard Assessments for Noncarcinogenic Effects )

Phosgene exposure: a case of accidental industrial exposure.

PubMed

Hardison, Lewis S; Wright, Edward; Pizon, Anthony F

2014-03-01

Phosgene is a rare exposure with strong clinical implications. We report a phosgene exposure that resulted in the patient's death. A 58 year-old man arrived to the emergency department 1 hour after exposure to phosgene with complaints of a sore throat. Initial vital signs were blood pressure 175/118 mmHg, heart rate 98/min, respirations 12/min, and oxygen saturation of 93% on room air. Physical exam revealed few scattered rhonchi, without signs of distress. Initial arterial blood gases (ABG's) revealed pH 7.42, pCO2 43 mmHg, pO2 68 mmHg, HCO3 27 meq/L, and oxygen saturation of 93% on room air. Initial chest x-ray 2 hours after the exposure demonstrated clear lung fields. Approximately 2.5 hours after the exposure, he began complaining of dyspnea, restlessness and his oxygen saturation dropped below 90%. He received nebulized albuterol, 1 gram intravenous methylprednisolone, and 100 % oxygen via face mask. Minimal improvement was noted and he was intubated. The post intubation chest x-ray, 3.5 hours after the exposure, revealed diffuse alveolar infiltrates. Acetylcysteine, terbutaline, and IV steroids were administered without improvement. The patient died 30 hours after exposure. There are many misunderstandings concerning phosgene due to its rare presentation. Traditional treatment modalities are often unproven in human trials and were unsuccessful in this case. This case highlights the significant toxicity that results from phosgene exposure and the challenges of the limited treatment modalities. There is concern for the use of this agent in chemical terrorism.

COLCHICINE DECREASES AIRWAY HYPERACTIVITY AFTER PHOSGENE EXPOSURE

EPA Science Inventory

Phosgene (COCl(2)) exposure affects an influx of inflammatory cells into the lung, which can be reduced in an animal model by pretreatment with colchicine. Inflammation in the respiratory tract can be associated with an increase in airway hyperreactivity. We tested the hypotheses...

AN "INJURY-TIME INTEGRAL" MODEL FOR RELATING ACUTE TO CHRONIC INJURY TO PHOSGENE

EPA Science Inventory

ABSTRACT
The present study compares acute and subchronic episodic exposures to phosgene to test the applicability of the "concentration x time" (C x T) product as a measure of exposure dose, and to relate acute toxicity and adaptive responses to chronic toxicity. Rats (m...

PHOSGENE AS AN EXAMPLE OF THE C X T TOXICITY PRINCIPLE: THE ROLE OF ADAPTATION

EPA Science Inventory

Phosgene as an example of the C x T toxicity principle: the role of adaptation

Name/Title : Dr. Gary E. Hatch
Organization: Pulmonary Toxicology Branch, Experimental Toxicology Division, NHEERL, EPA, RTP
Mailing Address: Mail Drop 82, US EPA, Res. Tri. Park, NC 27...

3. Photocopy of photograph, U.S. Army, ca. 1943 (original print ...

Library of Congress Historic Buildings Survey, Historic Engineering Record, Historic Landscapes Survey

3. Photocopy of photograph, U.S. Army, ca. 1943 (original print located at Rocky Mountain Arsenal, Commerce City, Colorado). R.M.A. - 331 - PHOSGENE FILLING PLANT LOOKING S.W. - Rocky Mountain Arsenal, Phosgene Filling & Storage Building, 1170 feet South of December Seventh Avenue; 230 feet West of D Street, Commerce City, Adams County, CO

2. Photocopy of photograph, U.S. Army, ca. 1943 (original print ...

Library of Congress Historic Buildings Survey, Historic Engineering Record, Historic Landscapes Survey

2. Photocopy of photograph, U.S. Army, ca. 1943 (original print located at Rocky Mountain Arsenal, Commerce City, Colorado). R.M.A. - 331 - PHOSGENE FILLING PLANT LOOKING N.E. - Rocky Mountain Arsenal, Phosgene Filling & Storage Building, 1170 feet South of December Seventh Avenue; 230 feet West of D Street, Commerce City, Adams County, CO

ACE-FTS and MIPAS observations of phosgene (COCl2) and comparisons with SLIMCAT chemical transport model calculations

NASA Astrophysics Data System (ADS)

Harrison, Jeremy; Chipperfield, Martyn; Moore, David; Boone, Christopher; Bernath, Peter; Hossaini, Ryan

2017-04-01

The majority of chlorine in the atmosphere has arisen from anthropogenic emissions of 'organic' species such as chlorofluorocarbons (CFCs) and hydrochlorofluorocarbons (HCFCs). Due to their long lifetimes, many of these species reach the stratosphere where they break down, liberating chlorine which catalyses the destruction of ozone. The principal degradation products of Cl-containing organic species are carbonyl chloride (phosgene, COCl2), carbonyl chloride fluoride (COClF), and hydrogen chloride (HCl). Of these, phosgene is probably the most notorious, having been used as a chemical weapon in World War I. In the lower stratosphere, where the phosgene mixing ratios peak, the principal sources are the photolysis of carbon tetrachloride (CCl4) and, to a lesser extent, methyl chloroform (CH3CCl3). Smaller contributions arise from very short-lived substances such as CH2Cl2, CHCl3 and C2Cl4. Due to the success of the Montreal Protocol in phasing out the use of CCl4 and CH3CCl3, the abundance of phosgene continues to fall. Observing and understanding phosgene in the stratosphere helps us better understand the chlorine budget, and particularly the atmospheric removal of CCl4, which has attracted particular interest recently on account of the inconsistency between observations of its abundance and estimated sources and sinks. This work presents global distributions and trends of COCl2 using data from two satellite limb instruments: the Atmospheric Chemistry Experiment Fourier transform spectrometer (ACE-FTS), and the Michelson Interferometer for Passive Atmospheric Sounding (MIPAS). The ACE-FTS instrument, on board the SCISAT satellite, has been recording solar occultation spectra through the Earth's atmosphere since 2004 and continues to take measurements with only minor loss in performance. ACE-FTS time series are available for a range of chlorine 'source' gases, including CCl3F (CFC-11), CCl2F2 (CFC-12), CHF2Cl (HCFC-22) and CCl4, and the chlorine 'product' gases COCl2, COClF and HCl. The MIPAS instrument, onboard ENVISAT (ENVIronmental SATellite), recorded atmospheric limb emissions spectra between 2002 and 2012, with time series available for the key Cl-containing species except HCl. ACE-FTS and MIPAS phosgene observations are compared with the output of SLIMCAT, a state-of-the-art offline three-dimensional chemical transport model (CTM), which contains a detailed treatment of stratospheric chemistry, including the major species in the Ox, NOy, HOx, Fy, Cly, and Bry chemical families.

Phosgene- and chlorine-induced acute lung injury in rats: comparison of cardiopulmonary function and biomarkers in exhaled breath.

PubMed

Luo, Sa; Trübel, Hubert; Wang, Chen; Pauluhn, Jürgen

2014-12-04

This study compares changes in cardiopulmonary function, selected endpoints in exhaled breath, blood, and bronchoalveolar lavage fluid (BAL) following a single, high-level 30-min nose-only exposure of rats to chlorine and phosgene gas. The time-course of lung injury was systematically examined up to 1-day post-exposure with the objective to identify early diagnostic biomarkers suitable to guide countermeasures to accidental exposures. Chlorine, due to its water solubility, penetrates the lung concentration-dependently whereas the poorly water-soluble phosgene reaches the alveolar region without any appreciable extent of airway injury. Cardiopulmonary endpoints were continually recorded by telemetry and barometric plethysmography for 20h. At several time points blood was collected to evaluate evidence of hemoconcentration, changes in hemostasis, and osteopontin. One day post-exposure, protein, osteopontin, and cytodifferentials were determined in BAL. Nitric oxide (eNO) and eCO2 were non-invasively examined in exhaled breath 5 and 24h post-exposure. Chlorine-exposed rats elaborated a reflexively-induced decreased respiratory rate and bradycardia whereas phosgene-exposed rats developed minimal changes in lung function but a similar magnitude of bradycardia. Despite similar initial changes in cardiac function, the phosgene-exposed rats showed different time-course changes of hemoconcentration and lung weights as compared to chlorine-exposed rats. eNO/eCO2 ratios were most affected in chlorine-exposed rats in the absence of any marked time-related changes. This outcome appears to demonstrate that nociceptive reflexes with changes in cardiopulmonary function resemble typical patterns of mixed airway-alveolar irritation in chlorine-exposed rats and alveolar irritation in phosgene-exposed rats. The degree and time-course of pulmonary injury was reflected best by eNO/eCO2 ratios, hemoconcentration, and protein in BAL. Increased fibrin in blood occurred only in chlorine-exposed rats 1-day post-exposure. Hence, the analysis of NO and CO2 in exhaled breath, including endpoints in blood mirroring changes in the peripheral to pulmonary fluid distribution, seem to be sensitive diagnostic endpoints readily available for early prognostic assessment of severity of injury and efficacy of any chosen countermeasure. Copyright © 2014 Elsevier Ireland Ltd. All rights reserved.

Emergency and Continuous Exposure Limits for Selected Airborne Contaminants. Volume 2

DTIC Science & Technology

1984-10-01

21, fluorocarbon 113, fluorocarbon 114, isopropyl alcohol, phosgene, sodium hydroxide, sulfur dioxide, vinylidene chloride . xylene. b. Identlflers/Open...fluorocarbon 114, isopropyl alcohol, phosgene, sodium hydroxide, sulfur dioxide, vinylidene chloride , xylene. c. COSATI Field/Group 1I. Availability Statement...Hydroxide 87 Sulfur Dioxide 95 Vinylidene Chloride 103 Xylene 113 -" , 0°. •. .. : V.•. ., , • .’’-.’ .’.’ INTRODUCTION The National Research Council’s

Effect of Dietary Treatment with n-Propyl Gallate or Vitamin E on the Survival of Mice Exposed to Phosgene

DTIC Science & Technology

2001-01-01

2000 Accepted 16 September 2000 34 A. M. SCIUTO AND T. S. MORAN and glutathione reductase.10 n-Propyl gallate protects against CCl4 -induced liver ...Ugazio G. Biochemical aspects of the protec- tive action of propyl gallate on liver injury in rats poisoned Published in 2001 by John Wiley & Sons, Ltd...Phosgene, widely used in industrial processes, can cause life-threatening pulmonary edema and acute lung injury . One mechanism of protection against

Dissociative adsorption of CCl 4 on the Fe 3O 4(1 1 1)-(2×2) selvedge of α-Fe 2O 3(0 0 0 1)

NASA Astrophysics Data System (ADS)

Adib, K.; Mullins, D. R.; Totir, G.; Camillone, N.; Fitts, J. P.; Rim, K. T.; Flynn, G. W.; Osgood, R. M.

2003-02-01

The surface reactions of CCl 4 with the Fe 3O 4(1 1 1)-(2×2) selvedge of naturally occurring α-Fe 2O 3(0 0 0 1) single-crystals have been investigated using synchrotron X-ray photoelectron spectroscopy (XPS) and temperature-programmed desorption (TPD). CCl 4 was found to dissociate on the Fe 3O 4 surface at 100 K producing chemisorbed Cl and adsorbed CCl 2. TPD shows that the large majority of the dissociatively adsorbed CCl 2 fragments extract lattice oxygen and desorb as phosgene at >275 K. However, the XPS spectra show no evidence for the formation of surface-bound phosgene, at 100 K, indicating that its formation involves two steps. The first step, dissociation, is spontaneous at 100 K, whereas the second, oxygen atom abstraction to form phosgene, requires thermal excitation. Cl chemisorption yielded two separate species, the mono- and dichloride terminations of surface iron sites. The identification of these two surface terminations is based on the coverage dependence and the surface temperature history of their Cl 2p 3/2 peak intensity. For example, heating to >450 K allows the monochloride to transform into iron dichloride, indicating Cl adatom mobility at these temperatures.

Phosgene

MedlinePlus

... Cyanogen chloride (CK) Digitalis Case Definition: Digitalis Poisoning Ethylene glycol Fentanyls and other opioids Case Definition: Opioids ( ... Thallium Toxic alcohols Case Definition: Toxic Alcohol Poisoning Ethylene glycol Trichothecene Case Definition: Trichothecene Mycotoxin Poisoning Unidentified ...

Method for near-real-time continuous air monitoring of phosgene, hydrogen cyanide, and cyanogen chloride

NASA Astrophysics Data System (ADS)

Lattin, Frank G.; Paul, Donald G.

1996-11-01

A sorbent-based gas chromatographic method provides continuous quantitative measurement of phosgene, hydrogen cyanide, and cyanogen chloride in ambient air. These compounds are subject to workplace exposure limits as well as regulation under terms of the Chemical Arms Treaty and Title III of the 1990 Clean Air Act amendments. The method was developed for on-sit use in a mobile laboratory during remediation operations. Incorporated into the method are automated multi-level calibrations at time weighted average concentrations, or lower. Gaseous standards are prepared in fused silica lined air sampling canisters, then transferred to the analytical system through dynamic spiking. Precision and accuracy studies performed to validate the method are described. Also described are system deactivation and passivation techniques critical to optimum method performance.

An 'injury-time integral' model for extrapolating from acute to chronic effects of phosgene.

PubMed

Hatch, G; Kodavanti, U; Crissman, K; Slade, R; Costa, D

2001-06-01

The present study compares acute and subchronic episodic exposures to phosgene to test the applicability of the 'concentrationxtime' (CxT) product as a measure of exposure dose, and to relate acute toxicity and adaptive responses to chronic toxicity. Rats (male Fischer 344) were exposed (six hours/day) to air or 0.1, 0.2, 0.5 and 1.0 ppm of phosgene one time or on a repeated regimen for up to 12 weeks as follows: 0.1 ppm (five days/week), 0.2 ppm (five days/week), 0.5 ppm (two days/week), or 1.0 ppm (one day/week) (note that the CxT for the three highest exposures was the same). Animals were sacrificed at 4, 8, and 12 weeks during the exposure and after four weeks recovery. Bronchoalveolar lavage (BAL) was performed 18 hours after the last exposure for each time period and the BAL supernatant assayed for protein. Elevated BAL fluid protein was defined as 'acute injury', diminished response after repeated exposure was defined as 'adaptation', and increased lung hydroxyproline or trichrome staining for collagen was defined as 'chronic injury'. Results indicated that exposures that cause maximal chronic injury involve high exposure concentrations and longer times between exposures, not high CxT products. A conceptual model is presented that explains the lack of CxT correlation by the fact that adaptation reduces an 'injury-time integral' as phosgene exposure is lengthened from acute to subchronic. At high exposure concentrations, the adaptive response appears to be overwhelmed, causing a continued injury-time integral, which appears to be related to appearance of chronic injury. The adaptive response is predicted to disappear if the time between exposures is lengthened, leading to a continued high injury-time integral and chronic injury. It has generally been assumed that long, continuous exposures of rodents is a conservative approach for detecting possible chronic effects. The present study suggests that such an approach my not be conservative, but might actually mask effects that could occur under intermittent exposure conditions.

Exposure-Relevant Ozone Chemistry in Occupied Spaces

DOE Office of Scientific and Technical Information (OSTI.GOV)

Coleman, Beverly Kaye

2009-04-01

Ozone, an ambient pollutant, is transformed into other airborne pollutants in the indoor environment. In this dissertation, the type and amount of byproducts that result from ozone reactions with common indoor surfaces, surface residues, and vapors were determined, pollutant concentrations were related to occupant exposure, and frameworks were developed to predict byproduct concentrations under various indoor conditions. In Chapter 2, an analysis is presented of secondary organic aerosol formation from the reaction of ozone with gas-phase, terpene-containing consumer products in small chamber experiments under conditions relevant for residential and commercial buildings. The full particle size distribution was continuously monitored, andmore » ultrafine and fine particle concentrations were in the range of 10 to>300 mu g m -3. Particle nucleation and growth dynamics were characterized.Chapter 3 presents an investigation of ozone reactions with aircraft cabin surfaces including carpet, seat fabric, plastics, and laundered and worn clothing fabric. Small chamber experiments were used to determine ozone deposition velocities, ozone reaction probabilities, byproduct emission rates, and byproduct yields for each surface category. The most commonly detected byproducts included C1?C10 saturated aldehydes and skin oil oxidation products. For all materials, emission rates were higher with ozone than without. Experimental results were used to predict byproduct exposure in the cabin and compare to other environments. Byproduct levels are predicted to be similar to ozone levels in the cabin, which have been found to be tens to low hundreds of ppb in the absence of an ozone converter. In Chapter 4, a model is presented that predicts ozone uptake by and byproduct emission from residual chemicals on surfaces. The effects of input parameters (residue surface concentration, ozone concentration, reactivity of the residue and the surface, near-surface airflow conditions, and byproduct yield) were explored. In Chapter 5, the reaction of ozone with permethrin, a residual insecticide used in aircraft cabins, to form phosgene is investigated. A derivatization technique was developed to detect phosgene at low levels, and chamber experiments were conducted with permethrin-coated cabin materials. It was determined that phosgene formation, if it occurs in the aircraft cabin, is not likely to exceed the relevant, health-based phosgene exposure guidelines.« less

INHALATION EXPOSURE-RESPONSE ASSESSMENTS FOR FIVE CHEMICALS

EPA Science Inventory

Inhalation exposure-response assessments for five chemicals (acrolein, ethylene oxide, hexachlorocyclopentadiene, hydrogen sulfide, and phosgene) for less-than-lifetime durations are being developed to inform the development of the Inhalation Exposure-Response Analysis Methodolog...

First infrared high resolution analysis of the ν5 band of phosgene 37Cl2CO

NASA Astrophysics Data System (ADS)

Flaud, J.-M.; Kwabia Tchana, F.; Perrin, A.; Manceron, L.; Ndao, M.

2018-06-01

A Fourier transform spectrum of phosgene (Cl2CO) has been recorded in the 11.8 μm spectral region at low temperature and at a resolution of 0.00102 cm-1 using a Bruker IFS125HR spectrometer coupled to synchrotron radiation leading to the observation of the ν5 vibrational band of the isotopologue 37Cl2CO. The corresponding upper state rovibrational levels were fit using a Watson-type Hamiltonian. In this way it was possible to reproduce the upper state rovibrational levels almost to within the experimental uncertainty i.e. ∼0.50 × 10-3 cm-1. Very accurate rotational and centrifugal distortion constants were derived from the fit together with the following band center: ν0 (ν5,37Cl2CO) = 848.970769 (20) cm-1.

Pulmonary biochemical effects of inhaled phosgene in rats.

PubMed

Franch, S; Hatch, G E

1986-01-01

Three exposure regimens were used to study the time course of indicators of lung damage and recovery response to single or repeated exposures to phosgene (COCl2). Rats were sacrificed immediately or throughout a 38-d recovery period after inhalation of 1 ppm COCl2 for 4 h, at intervals during a 7-h exposure to 1 ppm phosgene, or at several time points throughout a 17-d exposure to 0.125 and 0.25 ppm COCl2 (4 h/d, 5 d/wk) and during a 21-d recovery period. Regimen 1 revealed significantly elevated lung wet weight, lung nonprotein sulfhydryl (NPSH) content, and glucose-6-phosphate dehydrogenase (G6PD) activity that stayed elevated for up to 14 d. A significant decrease in body weight and food intake was observed 1 d after exposure. Regimen 2 caused a slight depression in NPSH content but did not affect G6PD activity. Regimen 3 animals showed sustained elevations in lung wet weight, NPSH content, and G6PD activity after 7 d of exposure. No significant changes in these endpoints were observed for the 0.125 ppm COCl2 group. No consistent elevation in hydroxyproline content was seen at either exposure concentration. Light microscopic examination of lung tissue exposed to 0.25 ppm COCl2 for 17 d revealed moderate multifocal accumulation of mononuclear cells in the centriacinar region. In summary, exposure to COCl2 caused changes similar in most ways to those observed for other lower-respiratory-tract irritants.

40 CFR Table 7 to Subpart Hhhhh of... - Partially Soluble Hazardous Air Pollutants

Code of Federal Regulations, 2012 CFR

2012-07-01

.... Methyl methacrylate 80626 42. Methyl-t-butyl ether 1634044 43. Methylene chloride 75092 44. N-hexane 110543 45. N,N-dimethylaniline 121697 46. Naphthalene 91203 47. Phosgene 75445 48. Propionaldehyde 123386...

40 CFR Table 7 to Subpart Hhhhh of... - Partially Soluble Hazardous Air Pollutants

Code of Federal Regulations, 2011 CFR

2011-07-01

.... Methyl methacrylate 80626 42. Methyl-t-butyl ether 1634044 43. Methylene chloride 75092 44. N-hexane 110543 45. N,N-dimethylaniline 121697 46. Naphthalene 91203 47. Phosgene 75445 48. Propionaldehyde 123386...

40 CFR Table 8 to Subpart Ffff of... - Partially Soluble Hazardous Air Pollutants

Code of Federal Regulations, 2013 CFR

2013-07-01

.... Methyl methacrylate 80626 41. Methyl-t-butyl ether 1634044 42. Methylene chloride 75092 43. N-hexane 110543 44. N,N-dimethylaniline 121697 45. Naphthalene 91203 46. Phosgene 75445 47. Propionaldehyde 123386...

40 CFR Table 8 to Subpart Ffff of... - Partially Soluble Hazardous Air Pollutants

Code of Federal Regulations, 2014 CFR

2014-07-01

.... Methyl methacrylate 80626 41. Methyl-t-butyl ether 1634044 42. Methylene chloride 75092 43. N-hexane 110543 44. N,N-dimethylaniline 121697 45. Naphthalene 91203 46. Phosgene 75445 47. Propionaldehyde 123386...

40 CFR Table 7 to Subpart Hhhhh of... - Partially Soluble Hazardous Air Pollutants

Code of Federal Regulations, 2014 CFR

2014-07-01

.... Methyl methacrylate 80626 42. Methyl-t-butyl ether 1634044 43. Methylene chloride 75092 44. N-hexane 110543 45. N,N-dimethylaniline 121697 46. Naphthalene 91203 47. Phosgene 75445 48. Propionaldehyde 123386...

40 CFR Table 7 to Subpart Hhhhh of... - Partially Soluble Hazardous Air Pollutants

Code of Federal Regulations, 2010 CFR

2010-07-01

.... Methyl methacrylate 80626 42. Methyl-t-butyl ether 1634044 43. Methylene chloride 75092 44. N-hexane 110543 45. N,N-dimethylaniline 121697 46. Naphthalene 91203 47. Phosgene 75445 48. Propionaldehyde 123386...

40 CFR Table 7 to Subpart Hhhhh of... - Partially Soluble Hazardous Air Pollutants

Code of Federal Regulations, 2013 CFR

2013-07-01

.... Methyl methacrylate 80626 42. Methyl-t-butyl ether 1634044 43. Methylene chloride 75092 44. N-hexane 110543 45. N,N-dimethylaniline 121697 46. Naphthalene 91203 47. Phosgene 75445 48. Propionaldehyde 123386...

Science, Law, and the Pursuit of Knowledge: Should Unethical Research Be Considered for Scientific Knowledge?

ERIC Educational Resources Information Center

Moore, Randy

2002-01-01

Describes similarities and differences between science and law in terms of truth, validity of facts, objectives, and research designs. Discusses ethical issues in teaching science and law and presents two case studies, Nazi hypothermia research and phosgene. (KHR)

2006, REMOTE SENSING AND GIS IN THE REMEDIATION OF CHEMICAL WEAPONS CONTAMINATION IN AN URBAN LANDSCAPE

EPA Science Inventory

This presentation will document the use of historical imagery, GIS, photogrammetry and hyperspectral remote sensing in locating and removing chemical weapons such as Mustard Gas, Phosgene, Ricin, and Lewisite from the environment and establishing a risk assessment methodology for...

Electrochemical systems and methods using metal halide to form products

DOE Office of Scientific and Technical Information (OSTI.GOV)

Albrecht, Thomas A.; Solas, Dennis; Leclerc, Margarete K.

There are provided electrochemical methods and systems to form one or more organic compounds or enantiomers thereof selected from the group consisting of substituted or unsubstituted dioxane, substituted or unsubstituted dioxolane, dichloroethylether, dichloromethyl methyl ether, dichloroethyl methyl ether, chloroform, carbon tetrachloride, phosgene, and combinations thereof.

LOCATING BURIED WW1 MUNITIONS WITH REMOTE SENSING AND GIS

EPA Science Inventory

During World War I, The American University in Washington D.C. was used by the U.S. Army as an experiment station for the development and testing of a variety of battlefield munitions including chemical weapons such as Mustard Gas, Phosgene, Ricin and Lewisite. After the end of t...

REMOTE SENSING IN DETECTING BURIED MUNITIONS FROM WORLD WAR I

EPA Science Inventory

During World War I, The American University in Washington D.C. was used by the U.S. Army as an experiment station for the development and testing of a variety of battlefield munitions including chemical weapons such as Mustard Gas, Phosgene, Ricin and Lewisite, among othe...

LOCATING BURIED WORLD WAR I MUNITIONS WITH REMOTE SENSING AND GIS

EPA Science Inventory

During World War I, the American University in Washington, D.C. was used by the U.S. Army as an experiment station for the development and testing of a variety of battlefield munitons including chemcial weapons such as Mustard Gas, Phosgene, Ricin and Lewisite. After the end of ...

Real World of Industrial Chemistry: Organic Chemicals from Carbon Monoxide.

ERIC Educational Resources Information Center

Kolb, Kenneth E.; Kolb, Doris

1983-01-01

Carbon Monoxide obtained from coal may serve as the source for a wide variety of organic compounds. Several of these compounds are discussed, including phosgene, benzaldehyde, methanol, formic acid and its derivatives, oxo aldehydes, acrylic acids, and others. Commercial reactions of carbon monoxide are highlighted in a table. (JN)

Management of phosgene-induced acute lung injury.

PubMed

Grainge, Christopher; Rice, Paul

2010-07-01

Phosgene is a substance of immense importance in the chemical industry. Because of its widespread industrial use, there is potential for small-scale exposures within the workplace, large-scale accidental release, or even deliberate release into a built-up area. This review aims to examine all published studies concerning potential treatments for phosgene-induced acute lung injury and incorporate them into up-to-date clinical guidance. In addition, it aims to contrast the approaches when dealing with small numbers of patients known to be exposed (possibly with dose information) with the presentation of a large and heterogeneous population of casualties following a significant industrial accident or deliberate release; no published guidelines have specifically addressed this second problem. PubMed and Embase were searched for all available years till April 2010 and 584 papers were identified and considered. Because of the nature of the injury, there have been no human trials of patients exposed to phosgene. Multiple small and large animal studies have been performed to examine potential treatments of phosgene-induced acute lung injury, but many of these used isolated organ models, pretreatment regimens, or clinically improbable doses. Recent studies in large animals using both realistic time frames and dosing regimens have improved our knowledge, but clinical guidance remains based on incomplete data. Management of a small-scale, confirmed exposure. In the circumstance of a small-scale, confirmed industrial release where a few individuals are exposed and present rapidly, an intravenous bolus of high-dose corticosteroid (e.g., methylprednisolone 1 g) should be considered, although there are no experimental data to support this recommendation. The evidence is that there is no benefit from nebulized steroid even when administered 1 h after exposure, or methylprednisolone if administered intravenously ≥6 h after exposure. Consideration should also be given to administration of nebulized acetylcysteine 1-2 g, though there is no substantive evidence of benefit outside a small animal, isolated lung model and there is a possibility of adverse effects. If the oxygen saturation falls below 94%, patients should receive the lowest concentration of supplemental oxygen to maintain their SaO(2) in the normal range. Once patients require oxygen, nebulized β-agonists [e.g., salbutamol (albuterol) 5 mg by nebulizer every 4 h] may reduce lung inflammation if administered within 1 h of exposure. Elective intubation should be considered early using an ARDSnet protective ventilation strategy. Management of a large-scale, non-confirmed exposure. In the circumstances of a large-scale industrial or urban release, not all patients presenting will have been exposed and health services are likely to be highly stretched. In this situation, patients should not be treated immediately as there is no evidence that delaying therapy causes harm, rather they should be rested and observed with regular physical examination and measurement of peripheral oxygen saturations. Once a patient's oxygen saturation falls below 94%, treatment with the lowest concentration of oxygen required to maintain their oxygen saturations in the normal range should be started. Once oxygen has been started, nebulized β-agonists [e.g., salbutamol (albuterol) 5 mg by nebulizer every 4 h] may reduce lung inflammation if administered within 1 h of exposure, though delayed administration which is likely following a large-scale release has not been tested formally. There is no benefit from nebulized steroid even when administered 1 h after exposure, or high-dose corticosteroid if administered intravenously ≥6 h after exposure. Although there are no experimental data to support this recommendation, an intravenous bolus of high-dose corticosteroid (e.g., methylprednisolone 1 g) may be considered if presentation is <6 h and resources allow. Depending on the numbers of casualties presenting, invasive ventilation should be initiated either electively once symptoms present (especially where there is a short latent period, indicating likelihood of more significant injury), or delayed until required. Ventilation should be with high positive end expiratory pressure, ARDSnet recommended ventilation. The mechanisms underlying the phosgene-induced acute lung injury are not well understood. Future experimental work should ensure that potential treatments are tested in a large animal model using realistic dosing regimens and clinically relevant timings, such as those that might be found in a mass casualty situation.

PRESENTED 03/01/2006: 2006 REMOTE SENSING AND GIS IN THE REMEDIATION OF CHEMICAL WEAPONS CONTAMINATION IN AN URBAN LANDSCAPE

EPA Science Inventory

During World War 1, The American University in Washington, DC was used by the U.S. Army as an experiment station for the development and testing of a variety of battlefield munitions including chemical weapons such as Mustard Gas, Phosgene, Ricin and Lewisite

Development and validation of a sensitive thermal desorption-gas chromatography-mass spectrometry (TD-GC-MS) method for the determination of phosgene in air samples.

PubMed

Juillet, Y; Dubois, C; Bintein, F; Dissard, J; Bossée, A

2014-08-01

A new rapid, sensitive and reliable method was developed for the determination of phosgene in air samples using thermal desorption (TD) followed by gas chromatography-mass spectrometry (GC-MS). The method is based on a fast (10 min) active sampling of only 1 L of air onto a Tenax® GR tube doped with 0.5 mL of derivatizing mixture containing dimercaptotoluene and triethylamine in hexane solution. Validation of the TD-GC-MS method showed a low limit of detection (40 ppbv), acceptable repeatability, intermediate fidelity (relative standard deviation within 12 %) and excellent accuracy (>95%). Linearity was demonstrated for two concentration ranges (0.04 to 2.5 ppmv and 2.5 to 10 ppmv) owing to variation of derivatization recovery between low and high concentration levels. Due to its simple on-site implementation and its close similarity with recommended operating procedure (ROP) for chemical warfare agents vapour sampling, the method is particularly useful in the process of verification of the Chemical Weapons Convention.

Genotoxicity surveillance programme in workers dismantling World War I chemical ammunition.

PubMed

Mateuca, R A; Carton, C; Roelants, M; Roesems, S; Lison, D; Kirsch-Volders, M

2010-06-01

To evaluate the effectiveness of personal protective measures in a dismantling plant for chemical weapons from World War I of the Belgian Defence. Seventeen NIOSH level B-equipped plant workers exposed to arsenic trichloride (AsCl(3)) in combination with phosgene or hydrogen cyanide (HCN) were compared to 24 NIOSH level C-protected field workers occasionally exposed to genotoxic chemicals (including AsCl(3)-phosgene/HCN) when collecting chemical ammunition, and 19 matched referents. Chromosomal aberrations (CA), micronuclei (MNCB and MNMC), sister chromatid exchanges (SCE) and high frequency cells (HFC) were analysed in peripheral blood lymphocytes. Urinary arsenic levels and genetic polymorphisms in major DNA repair enzymes (hOGG1(326), XRCC1(399), XRCC3(241)) were also assessed. SCE and HFC levels were significantly higher in plant-exposed versus referent subjects, but MNCB and MNMC were not different. MNCB, SCE and HFC levels were significantly higher and MNMC levels significantly lower in field-exposed workers versus referents. AsCl(3) exposure was not correlated with genotoxicity biomarkers. Protective measures for plant-exposed workers appear adequate, but protection for field-exposed individuals could be improved.

THE ROLE OF REMOTE SENSING IN IDENTIFYING BURIED WORLD WAR 1 MUNITIONS AT THE AMERICAN UNIVERSITY, WASHINGTON, D.C.

EPA Science Inventory

During World War 1, The American University in Washington D.C. was used by the U.S. Army as an experiment station for the development and testing of a variety of battlefield munitions including chemical weapons such as Mustard Gas, Phosgene, Ricin and Lewisite, among others. Afte...

THE ROLE OF REMOTE SENSING IN IDENTIFYING BURIED WORLD WAR I MUNITIONS AT THE AMERICAN UNIVERSITY, WASHINGTON, D.C.

EPA Science Inventory

During World War 1, The American University in Washington D.C. was used by the U.S. Army as an experiment station for the development and testing of a variety of battlefield munitions including chemical weapons such as Mustard Gas, Phosgene, Ricin and Lewisite, among others. Afte...

SEPARATION OF URANIUM AND PLUTONIUM OXIDES

DOEpatents

Benedict, G.E.; Lyon, W.L.

1961-12-01

ABS>A method of separating a mixture of UO/sub 2/ and PuO/sub 2/ is given which comprises immersing the mixture in a fused NaCl-KCl bath, chlorinating with chlorine or phosgene, and preferentially electrolytically or chemically reducing the UO/sub 2/Cl/sub 2/ so produced to UO/sub 2/ and filtering it out. (AEC)

REMOTE SENSING AND GIS IN THE REMEDIATION OF CHEMICAL WEAPONS CONTAMINATION IN AN URBAN LANDSCAPE

EPA Science Inventory

During World War I, The American University in Washington D.C. was used by the U.S. Army as an experiment station for the development and testing of a variety of battlefield munitions including chemical weapons such as Mustard Gas, Phosgene, Ricin and Lewisite. After the end of t...

THE ROLE OF REMOTE SENSING AND GIS IN IDENTIFYING BURIED WORLD WAR I MUNITIONS AT THE AMERICAN UNIVERSITY, WASHINGTON, DC

EPA Science Inventory

During World War 1, The American University in Washington D.C. was used by the U.S. Army as an experiment station for the development and testing of a variety of battlefield munitions including chemical weapons such as Mustard Gas, Phosgene, Ricin and Lewisite, among others. Afte...

THE ROLE OF HISTORICAL AERIAL PHOTOGRAPHS IN THE REMEDIATION OF WWI CHEMICAL CONTAMINATION IN THE SPRING VALLEY SUPERFUND SITE, WASHINGTON, DC

EPA Science Inventory

During World War 1, The American University in Washington D.C. was used by the U.S. Army as an experiment station for the development and testing of a variety of battlefield munitions including chemical weapons such as Mustard Gas, Phosgene, Ricin and Lewisite, among others. Afte...

THE ROLE OF THE REMOTE SENSING IN IDENTIFYING BURIED WORLD WAR I MUNITIONS AT THE AMERICAN UNIVERSITY, WASHINGTON, D.C.

EPA Science Inventory

During World War 1, The American University in Washington D.C. was used by the U.S. Army as an experiment station for the development and testing of a variety of battlefield munitions including chemical weapons such as Mustard Gas, Phosgene, Ricin and Lewisite, among othe...

Antidotes and treatments for chemical warfare/terrorism agents: an evidence-based review.

PubMed

Rodgers, G C; Condurache, C T

2010-09-01

This article reviews the evidence supporting the efficacy of antidotes used or recommended for the potential chemical warfare agents of most concern. Chemical warfare agents considered include cyanide, vesicants, pulmonary irritants such as chlorine and phosgene, and nerve agents. The strength of evidence for most antidotes is weak, highlighting the need for additional research in this area.

THER ROLE OF REMOTE SENSING AND GIS IN IDENTIFYING AND REMOVING BURIED WORLD WAR I MUNITIONS AT THE AMERICAN UNIVERSITY, WASHINGTON, DC

EPA Science Inventory

During World War I, The American University in Washington D.C. was used by the U.S. Am1y as an experiment station for the development and testing of a variety of battlefield munitions including chemical weapons such as Mustard Gas, Phosgene, Ricin and Lewisite, among others. Afte...

Simple, Rapid, and Highly Sensitive Detection of Diphosgene and Triphosgene by Spectrophotometric Methods

PubMed Central

Joy, Abraham; Anim-Danso, Emmanuel; Kohn, Joachim

2009-01-01

Methods for the detection and estimation of diphosgene and triphosgene are described. These compounds are widely used phosgene precursors which produce an intensely colored purple pentamethine oxonol dye when reacted with 1,3-dimethylbarbituric acid (DBA) and pyridine (or a pyridine derivative). Two quantitative methods are described, based on either UV absorbance or fluorescence of the oxonol dye. Detection limits are ~ 4 µmol/L by UV and <0.4 µmol/L by fluorescence. The third method is a test strip for the simple and rapid detection and semi-quantitative estimation of diphosgene and triphosgene, using a filter paper embedded with dimethylbarbituric acid and poly(4-vinylpyridine). Addition of a test solution to the paper causes a color change from white to light blue at low concentrations and to pink at higher concentrations of triphosgene. The test strip is useful for quick on-site detection of triphosgene and diphosgene in reaction mixtures. The test strip is easy to perform and provides clear signal readouts indicative of the presence of phosgene precursors. The utility of this method was demonstrated by the qualitative determination of residual triphosgene during the production of poly(Bisphenol A carbonate). PMID:19782219

PREPARATION OF ACTINIDE-ALUMINUM ALLOYS

DOEpatents

Moore, R.H.

1962-09-01

BS>A process is given for preparing alloys of aluminum with plutonium, uranium, and/or thorium by chlorinating actinide oxide dissolved in molten alkali metal chloride with hydrochloric acid, chlorine, and/or phosgene, adding aluminum metal, and passing air and/or water vapor through the mass. Actinide metal is formed and alloyed with the aluminum. After cooling to solidification, the alloy is separated from the salt. (AEC)

URANIUM SEPARATION PROCESS

DOEpatents

Lyon, W.L.

1962-04-17

A method of separating uranium oxides from PuO/sub 2/, ThO/sub 2/, and other actinide oxides is described. The oxide mixture is suspended in a fused salt melt and a chlorinating agent such as chlorine gas or phosgene is sparged through the suspension. Uranium oxides are selectively chlorinated and dissolve in the melt, which may then be filtered to remove the unchlorinated oxides of the other actinides. (AEC)

Toxic Industrial Chemicals: A Future Weapons of Mass Destruction Threat

DTIC Science & Technology

2002-05-31

1937 by Dr. Gerhard Schrader, a chemist conducting insecticide research with organophosphates (Stockholm International Peace Research Institute 1971...International Peace Research Institute 1971 and 1973). Phosgene oxime is known as “ nettle gas,” so named because of its property of intensely irritating...as a WMD. Common TICs Effects of CW Agents Organophosphate Insecticide Nerve Dimethyl Sulfate Blister Methyl Isocyanate Blood Anhydrous Ammonia

Methodology Report for Phosgene Model (CGModel)

DTIC Science & Technology

2012-01-01

by hydrolysis and acylation reactions, causing irritation and damaging of pulmonary tissue membranes leading to respiratory failure and eventually...literature search: pulmonary edema. 23 Data. from literature search: pulmonary edema. 24 Data from literature search: dyspnea . . . . . . . 2-5 Data...example, "exposures to 2 ppm for 80 minutes will not cause any irritation but result in pulmonary oedema some 12- 16 hours later" [20. p.l50]. This

Why the United States Underestimated the Soviet BW Threat

DTIC Science & Technology

2006-09-01

air sampling.2 For example, the nuclear power plant at Yongbyon in the Democratic People’s Republic of Korea was detected operating shortly after it...Cirincione, Wolfsthal, and Rajkumar, Deadly Arsenals, 435-437. 3 short amount of time. Chemical weapons plants also have large footprints that can...chemical processing plant for industry or agriculture is possible. For example, phosgene was a chemical weapon used extensively in World War I. This

An Approach to the Management of Hazardous Materials.

DTIC Science & Technology

1981-09-01

fluoride carbon disulfide carbon monoxide hydrochloric acid hydrogen sulfide acetone cyanohydrin phosgene Group XII: Poison B - Meeflaneous a) Gases...b) Liquids sulfur dioxide bromine chlorine boron trifluoride Group XIII: Poison C Group XIV: Poison D Liquid Gas tetraethyl lead fluorine Group XV...with a high and o Nitric acid leaks from a 5,000 gallon storage tank In a growing concentration of electronics industries. Over plant one night and

Acute lung injury following refrigeration coil deicing.

PubMed

McKeown, Nathanael J; Burton, Brent T

2012-03-01

We report a case of a worker who developed ALI requiring mechanical ventilatory support after attempting to melt ice condensate by applying the flame of an oxy-acetylene torch to refrigeration coils charged with a halocarbon refrigerant in a closed environment. A discussion of possible etiologies are discussed, including phosgene, carbonyl fluoride, and nitrogen oxides. Primary prevention with adequate respiratory protection is recommended whenever deicing is performed in a closed space environment.

Reactive formulations for a neutralization of toxic industrial chemicals

DOEpatents

Tucker, Mark D [Albuqueruqe, NM; Betty, Rita G [Rio Rancho, NM

2006-10-24

Decontamination formulations for neutralization of toxic industrial chemicals, and methods of making and using same. The formulations are effective for neutralizing malathion, hydrogen cyanide, sodium cyanide, butyl isocyanate, carbon disulfide, phosgene gas, capsaicin in commercial pepper spray, chlorine gas, anhydrous ammonia gas; and may be effective at neutralizing hydrogen sulfide, sulfur dioxide, formaldehyde, ethylene oxide, methyl bromide, boron trichloride, fluorine, tetraethyl pyrophosphate, phosphorous trichloride, arsine, and tungsten hexafluoride.

Environmental Statement. Disposition of Orange Herbicide by Incineration

DTIC Science & Technology

1974-11-01

and will follow all applicable maritime regulations. The vessel has operated for about two years without encountering a situation which required... hypochlorous acid , chlorous acid , chloric acid , perchloric acid , chlorine hydrate, and phosgene. All of these compounds are highly corrosive and toxic...effluent gas stack were operated isokinetically. The system used to sample for TCDD and the butyl esters and acids (of 2,4-D and 2,4,5-T) was not

Characterization of Chemical Weapons Convention Schedule 3 Compounds by Quantitative 13C NMR Spectroscopy

DTIC Science & Technology

2007-11-01

or other pesticides, or as fumigants for rodent extermination. Additionally, they all are used as a raw material for the synthesis of other chemicals...pressure/ vacuum valve NMR sample tubes (Catalog number 528- PV-9), were purchased from Wilmad-Labglass (Buena, NJ). 2.2 Sample Preparation Hydrogen...cyanide, cyanogen chloride, and phosgene were prepared for NMR spectroscopy by condensing their respective gases into pressure/ vacuum valve NMR sample

A Review of the Literature on the Applications of CW Agents with Recommendations of Further Research on Thickened GD

DTIC Science & Technology

1975-12-01

be effective not only in GD but also in VX, although as much as 30% is needed to form a gel. Wills cites the polymethacrylates : the methyl and ethyl...percutaneous toxicity of additives. Horton et al showed that a 50/50 mixture of GB with hexafluoroglutaric acid , phosgene oxime, or xylene is signifi- cantly...amounts of certain products of the decomposition of the agent, viz pinacolyl hydrogen methylphosphonate and methylphosphonic acid , as much as 40 weeks

Minimum Lethal Concentrations, Symptomatology, and Pathology of Phosgene

DTIC Science & Technology

1923-09-15

svewd 1007 6.s5 besovared 740 9.17 Died after 42owl* 1101 Ve" t a4 j AT sv.on U24,3.5 gel 6 8 J965 50 9.17 " 4 74 1106 3.1" JAeovered 1120 10.15 of...be bUeo-tW4. ASAa tW beg dIeS in @,owm) nai oinuliomme When AoP omie for three of four Am" the Linseehe In 1W eyes mind aso ftontiy beso smo-Peu

Sulfur Mustard- and Phosgene- Increased IL-8 in Human Small Airway Cell Cultures: Implications for Medical Countermeasures Against Inhalation Toxicity

DTIC Science & Technology

2005-10-01

TOXICITY Fred M. Cowan, William J . Smith, Ted S. Moran, Michelle M. Parris, Adetunji B. Williams and Alfred M. Sciuto U.S. Army Medical Research...toxicity in rodents (reviewed, 5) and some efficacy in the MEVM (personal communication, Dr. William J . Smith, USAMRICD, APG Md). Ibuprofen (62, 125...and inflammatory response in the toxicity of nerve and blister chemical warfare agents: implications for multi-threat medical countermeasures. J

Development of portable mass spectrometer with electron cyclotron resonance ion source for detection of chemical warfare agents in air.

PubMed

Urabe, Tatsuya; Takahashi, Kazuya; Kitagawa, Michiko; Sato, Takafumi; Kondo, Tomohide; Enomoto, Shuichi; Kidera, Masanori; Seto, Yasuo

2014-01-01

A portable mass spectrometer with an electron cyclotron resonance ion source (miniECRIS-MS) was developed. It was used for in situ monitoring of trace amounts of chemical warfare agents (CWAs) in atmospheric air. Instrumental construction and parameters were optimized to realize a fast response, high sensitivity, and a small body size. Three types of CWAs, i.e., phosgene, mustard gas, and hydrogen cyanide were examined to check if the mass spectrometer was able to detect characteristic elements and atomic groups. From the results, it was found that CWAs were effectively ionized in the miniECRIS-MS, and their specific signals could be discerned over the background signals of air. In phosgene, the signals of the 35Cl+ and 37Cl+ ions were clearly observed with high dose-response relationships in the parts-per-billion level, which could lead to the quantitative on-site analysis of CWAs. A parts-per-million level of mustard gas, which was far lower than its lethal dosage (LCt50), was successfully detected with a high signal-stability of the plasma ion source. It was also found that the chemical forms of CWAs ionized in the plasma, i.e., monoatomic ions, fragment ions, and molecular ions, could be detected, thereby enabling the effective identification of the target CWAs. Despite the disadvantages associated with miniaturization, the overall performance (sensitivity and response time) of the miniECRIS-MS in detecting CWAs exceeded those of sector-type ECRIS-MS, showing its potential for on-site detection in the future. Copyright © 2013 Elsevier B.V. All rights reserved.

RADIOLYSIS OF DILUTE SOLUTIONS OF DIPHENYLPICRYLHYDRAZYLE (DPPH) IN ORGANIC SOLVENTS. IV. NATURE OF THE ADDITION PRODUCTS. INTERCEPTION CHEMICAL PROCESSES (in French)

DOE Office of Scientific and Technical Information (OSTI.GOV)

Bouby, L.; Chapiro, A.; Chapiro, E.

1961-04-01

The nature of the addition compounds formed during the irradiation of chloroform and carbon tetrachloride in the presence of DPPH and during the reaction of DPPH with chlorine, hydrochloric acid, and phosgene was studied by chromatography on alumina. The principal fraction, isolated among the products of these different reactions, is constituted by red-orange compound whose spectrum is identical with that of the diphenylpicrylhydrazine DPPH-H. The chromatograms contain "black bodies" which possess in- tense absorption bands at long wave lengths and which are paramagnetic. These "black bodies" which are probably substitute derivatives of DPPH yield by reduction red range substances havingmore » the same spectrum as hydrozine DPPH-H. However on reoxidation, these hydrozines give e "black bodies"; they act then as substituted hydrazines. The "black bodies" can be reduced to two types of compounds: blue-black compounds formed during the irradiation of chloroform or from the action of DPPH on phosgene and brown-black compounds resulting from the radiolysis of CCl/sub 4/ or from the action of DPPH on chlorine. The elementary analysis of this last compound indicates at it contains more than 3 Cl/molecule. It was concluded that the chemical mechanisms of the interception of free radicals by DPPH is in reality more complex than a simple reaction of radical combination. However, the secondary reactions do not appear to perturb in a significant manner the radical yields determined by the DPPH method. (tr-auth)« less

Sensing behavior of a graphene quantum dot phenalenyl towards toxic gases

NASA Astrophysics Data System (ADS)

Sharma, Vaishali; Narayan, Som; Dabhi, Shweta D.; Shinde, Satyam; Jha, Prafulla K.

2018-04-01

In the present work, by studying the interaction of graphene quantum dot (GQD) Phenalenylwith toxic gases hydrogen cyanide (HCN) and phosgene (COCl2) using density functional theory, we are aiming to evaluate the possibility of using GQD phenalenyl in the detection of HCN and COCl2. Owing to strong interactions between HCN/COCl2 and the GQD Phenalenyl, dramatic changes in the electronic properties of the graphene quantum dots together with highest occupied molecular orbitals and lowest unoccupied molecularorbitals (HOMO-LUMO) gap variationsare observed. The findings show that the GQD phenalenyl can be used as chemical nanosensor to detect HCN and COCl2 toxic gases.

Acute nose-only exposure of rats to phosgene. Part II. Concentration x time dependence of changes in bronchoalveolar lavage during a follow-up period of 3 months.

PubMed

Pauluhn, Jürgen

2006-08-01

Groups of young adult male Wistar rats were acutely exposed to phosgene gas for either 30 or 240 min using a directed-flow nose-only mode of exposure. In 30-min exposed rats the concentrations were 0.94, 2.02, 3.89, 7.35, and 15.36 mg/m3, which relate to C x t products of 28.2, 60.6, 116.7, 220.5, and 460.8 mg/m3 x min. In 240-min exposed rats the concentrations were 0.96, 0.387, 0.786, 1.567, and 4.2 mg/m3, which relate C x t products of 47.0, 92.9, 188.6, 376, and 1008 mg/m3 x min. Six rats/group were sacrificed on postexposure days 1, 3, 7, 14, and 84, while the rats of the 1008 mg/m3 x min group where sacrificed on postexposure days 1, 7, 14, and 28. The focus of measurements was directed toward indicators of inflammatory response and increased transmucosal permeability in bronchoalveolar lavage (BAL), including lung weights. Lungs from rats sacrificed at the end of the postexposure period were additionally examined by histopathology. Mortality did not occur at any C x t product. The most pronounced changes were related to C x t-dependent increases in the following markers in BAL: protein, soluble collagen, polymorphonuclear leukocytes (PMN) counts, and alveolar macrophages with foamy appearance. These indicators were maximal on the first postexposure day, while total cell counts and alveolar macrophages containing increased phospholipids reached their climax around post-exposure day 3. At 1008 mg/m3 x min the most sensitive indicators in BAL, that is, protein, PMN, and collagen, resolved within 2 wk, whereas at lower C x t products they reached the level of the control by postexposure day 7. At 1008 mg/m3 x min (day 28), histopathology revealed a minimal to slight hypercellularity in terminal bronchioles with focal peribronchiolar inflammatory infiltrates and focal septal thickening. At lower C x t products (day 84) the rats from all groups were indistinguishable and Sirius red-stained lungs did not provide evidence of late-onset sequelae, such as fibrotic changes or collagen deposition. At similar C x t products the changes in BAL were slightly less pronounced using 30-min exposure periods when compared to 240-min exposure periods. In summary, the phosgene-induced transmucosal permeability caused a C x t-dependent increase of several BAL indicators, of which those of protein, PMN, and soluble collagen were most pronounced. Exposure intensities up to 116.7 mg/m3 x min did not cause changes different from those observed in controls, while at 188.6 mg/m3 x min distinct differences to the control existed. Despite the extensively increased airway permeability, histopathology did not provide evidence of lung tissue remodeling or irreversible sequelae.

Effect of temperature and initial dibutyl sulfide concentration in chloroform on its oxidation rate by ozone.

PubMed

Popiel, Stanisław; Nalepa, Tomasz; Dzierzak, Dorota; Stankiewicz, Romuald; Witkiewicz, Zygfryd

2008-09-15

A scheme of dibutyl sulfide (DBS) oxidation with ozone and generation of transitional products was determined in this study. The main identified intermediate product was dibutyl sulfoxide (DBSO), and the main end product of DBS oxidation was dibutyl sulfone (DBSO2). It was determined that for three temperatures: 0, 10 and 20 degrees C there was certain initial DBS concentration for which half-times observed in experimental conditions were equal and independent from temperature. Generation of phosgene and water as by-products was confirmed for the reaction of DBS with ozone in chloroform. Results of the described study allowed to present generalized mechanism of sulfide oxidation with ozone.

Transesterification of diethyl oxalate with phenol over sol-gel MoO(3)/TiO(2) catalysts.

PubMed

Kotbagi, Trupti; Nguyen, Duy Luan; Lancelot, Christine; Lamonier, Carole; Thavornprasert, Kaew-Arpha; Wenli, Zhu; Capron, Mickaël; Jalowiecki-Duhamel, Louise; Umbarkar, Shubhangi; Dongare, Mohan; Dumeignil, Franck

2012-08-01

The transesterification of diethyl oxalate (DEO) with phenol to form diphenyl oxalate (DPO) has been carried out in the liquid phase over very efficient MoO(3)/TiO(2) solid-acid sol-gel catalysts. A selectivity of 100 % with a remarkable maximum yield of 88 % were obtained, which opens the route to downstream phosgene-free processes for the synthesis of polycarbonates. Interpretation of the results of various acidity measurements (NH(3) and pyridine desorption, methanol oxidation as a probe reaction) allowed us to identify the catalytic sites as Lewis acid sites. Copyright © 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Devices and methods to detect and quantify trace gases

DOEpatents

Allendorf, Mark D.; Robinson, Alex

2016-05-03

Sensing devices based on a surface acoustic wave ("SAW") device coated with an absorbent crystalline or amorphous layer for detecting at least one chemical analyte in a gaseous carrier. Methods for detecting the presence of a chemical analyte in a gaseous carrier using such devices are also disclosed. The sensing devices and methods for their use may be configured for sensing chemical analytes selected from the group consisting of water vapor, carbon dioxide, methanol, ethanol, carbon monoxide, nitric oxide, nitrous oxide, organic amines, organic compounds containing NO.sub.2 groups, halogenated hydrocarbons, acetone, hexane, toluene, isopropanol, alcohols, alkanes, alkenes, benzene, functionalized aromatics, ammonia (NH.sub.3), phosgene (COCl.sub.2), sulfur mustard, nerve agents, sulfur dioxide, tetrahydrofuran (THF) and methyltertbutyl ether (MTBE) and combinations thereof.

Gas sensing properties and in situ diffuse reflectance infrared Fourier transform spectroscopy study of trichloroethylene adsorption and reactions on SnO2 films

NASA Astrophysics Data System (ADS)

Zhang, Zhenxin; Huang, Kaijin; Yuan, Fangli; Xie, Changsheng

2014-05-01

The detection of trichloroethylene has attracted much attention because it has an important effect on human health. The sensitivity of the SnO2 flat-type coplanar gas sensor arrays to 100 ppm trichloroethylene in air was investigated. The adsorption and surface reactions of trichloroethylene were investigated at 100-200 °C by in-situ diffuse reflection Fourier transform infrared spectroscopy (DIRFTS) on SnO2 films. Molecularly adsorbed trichloroethylene, dichloroacetyl chloride (DCAC), phosgene, HCl, CO, H2O, CHCl3, Cl2 and CO2 surface species are formed during trichloroethylene adsorption at 100-200 °C. A possible mechanism of the reaction process is discussed.

Chemical Warfare and Medical Response During World War I

PubMed Central

Fitzgerald, Gerard J.

2008-01-01

The first large-scale use of a traditional weapon of mass destruction (chemical, biological, or nuclear) involved the successful deployment of chemical weapons during World War I (1914–1918). Historians now refer to the Great War as the chemist’s war because of the scientific and engineering mobilization efforts by the major belligerents. The development, production, and deployment of war gases such as chlorine, phosgene, and mustard created a new and complex public health threat that endangered not only soldiers and civilians on the battlefield but also chemical workers on the home front involved in the large-scale manufacturing processes. The story of chemical weapons research and development during that war provides useful insights for current public health practitioners faced with a possible chemical weapons attack against civilian or military populations. PMID:18356568

Emergency management of chemical weapons injuries.

PubMed

Anderson, Peter D

2012-02-01

The potential for chemical weapons to be used in terrorism is a real possibility. Classes of chemical weapons include nerve agents, vesicants (blister agents), choking agents, incapacitating agents, riot control agents, blood agents, and toxic industrial chemicals. The nerve agents work by blocking the actions of acetylcholinesterase leading to a cholinergic syndrome. Nerve agents include sarin, tabun, VX, cyclosarin, and soman. The vesicants include sulfur mustard and lewisite. The vesicants produce blisters and also damage the upper airways. Choking agents include phosgene and chlorine gas. Choking agents cause pulmonary edema. Incapacitating agents include fentanyl and its derivatives and adamsite. Riot control agents include Mace and pepper spray. Blood agents include cyanide. The mechanism of toxicity for cyanide is blocking oxidative phosphorylation. Toxic industrial chemicals include agents such as formaldehyde, hydrofluoric acid, and ammonia.

Chemical warfare and medical response during World War I.

PubMed

Fitzgerald, Gerard J

2008-04-01

The first large-scale use of a traditional weapon of mass destruction (chemical, biological, or nuclear) involved the successful deployment of chemical weapons during World War I (1914-1918). Historians now refer to the Great War as the chemist's war because of the scientific and engineering mobilization efforts by the major belligerents. The development, production, and deployment of war gases such as chlorine, phosgene, and mustard created a new and complex public health threat that endangered not only soldiers and civilians on the battlefield but also chemical workers on the home front involved in the large-scale manufacturing processes. The story of chemical weapons research and development during that war provides useful insights for current public health practitioners faced with a possible chemical weapons attack against civilian or military populations.

Raman spectra and cross sections of ammonia, chlorine, hydrogen sulfide, phosgene, and sulfur dioxide toxic gases in the fingerprint region 400-1400 cm-1

NASA Astrophysics Data System (ADS)

Aggarwal, R. L.; Farrar, L. W.; Di Cecca, S.; Jeys, T. H.

2016-02-01

Raman spectra of ammonia (NH3), chlorine (Cl2), hydrogen sulfide (H2S), phosgene (COCl2), and sulfur dioxide (SO2) toxic gases have been measured in the fingerprint region 400-1400 cm-1. A relatively compact (<2'x2'x2'), sensitive, 532 nm 10 W CW Raman system with double-pass laser and double-sided collection was used for these measurements. Two Raman modes are observed at 934 and 967 cm-1 in NH3. Three Raman modes are observed in Cl2 at 554, 547, and 539 cm-1, which are due to the 35/35 35/37, and 37/37 Cl isotopes, respectively. Raman modes are observed at 870, 570, and 1151 cm-1 in H2S, COCl2, and SO2, respectively. Values of 3.68 ± 0.26x10-32 cm2/sr (3.68 ± 0.26x10-36 m2/sr), 1.37 ± 0.10x10-30 cm2/sr (1.37 ± 0.10x10-34 m2/sr), 3.25 ± 0.23x10-31 cm2/sr (3.25 ± 0.23x10-35 m2/sr), 1.63 ± 0.14x10-30 cm2/sr (1.63 ± 0.14x10-34 m2/sr), and 3.08 ± 0.22x10-30 cm2/sr (and 3.08 ± 0.22x10-34 m2/sr) were determined for the differential Raman cross section of the 967 cm-1 mode of NH3, sum of the 554, 547, and 539 cm-1 modes of Cl2, 870 cm-1 mode of H2S, 570 cm-1 mode of COCl2, and 1151 cm-1 mode of SO2, respectively, using the differential Raman cross section of 3.56 ± 0.14x10-31 cm2/sr (3.56 ± 0.14x10-35 m2/sr) for the 1285 cm-1 mode of CO2 as the reference.

Time-dependent infrared emission following photodissociation of nitromethane and chloropicrin.

PubMed

Wade, Elisabeth A; Reak, Kristina E; Li, Sissi L; Clegg, Samuel M; Zou, Peng; Osborn, David L

2006-04-06

Nitromethane (CH(3)NO(2)) and its chlorinated analogue, chloropicrin (CCl(3)NO(2)), were photolyzed at 193, 248, and 266 nm, and the products were observed by time-dependent Fourier transform infrared emission spectroscopy. At 193 and 248 nm, the primary photodissociation pathway for nitromethane was cleavage of the C-N bond to produce CH(3) + NO(2)(A (2)B(2)). At 266 nm, weak emission was observed following photodissociation of nitromethane, but an infrared spectrum could not be obtained. The photodissociation of chloropicrin at 193 nm produced the analogous product channel CCl(3) + NO(2)(A (2)B(2)) in addition to several other product channels. At 248 and 266 nm, only CCl(3) + NO(2)(A (2)B(2)) was observed. The production of phosgene (CCl(2)O) from chloropicrin photodissociation was not observed in this study.

Hazardous-waste analysis plan for LLNL operations

DOE Office of Scientific and Technical Information (OSTI.GOV)

Roberts, R.S.

The Lawrence Livermore National Laboratory is involved in many facets of research ranging from nuclear weapons research to advanced Biomedical studies. Approximately 80% of all programs at LLNL generate hazardous waste in one form or another. Aside from producing waste from industrial type operations (oils, solvents, bottom sludges, etc.) many unique and toxic wastes are generated such as phosgene, dioxin (TCDD), radioactive wastes and high explosives. One key to any successful waste management program must address the following: proper identification of the waste, safe handling procedures and proper storage containers and areas. This section of the Waste Management Plan willmore » address methodologies used for the Analysis of Hazardous Waste. In addition to the wastes defined in 40 CFR 261, LLNL and Site 300 also generate radioactive waste not specifically covered by RCRA. However, for completeness, the Waste Analysis Plan will address all hazardous waste.« less

Automated parameterization of intermolecular pair potentials using global optimization techniques

NASA Astrophysics Data System (ADS)

Krämer, Andreas; Hülsmann, Marco; Köddermann, Thorsten; Reith, Dirk

2014-12-01

In this work, different global optimization techniques are assessed for the automated development of molecular force fields, as used in molecular dynamics and Monte Carlo simulations. The quest of finding suitable force field parameters is treated as a mathematical minimization problem. Intricate problem characteristics such as extremely costly and even abortive simulations, noisy simulation results, and especially multiple local minima naturally lead to the use of sophisticated global optimization algorithms. Five diverse algorithms (pure random search, recursive random search, CMA-ES, differential evolution, and taboo search) are compared to our own tailor-made solution named CoSMoS. CoSMoS is an automated workflow. It models the parameters' influence on the simulation observables to detect a globally optimal set of parameters. It is shown how and why this approach is superior to other algorithms. Applied to suitable test functions and simulations for phosgene, CoSMoS effectively reduces the number of required simulations and real time for the optimization task.

Quantum yield for carbon monoxide production in the 248 nm photodissociation of carbonyl sulfide (OCS)

NASA Technical Reports Server (NTRS)

Zhao, Z.; Stickel, R. E.; Wine, P. H.

1995-01-01

Tunable diode laser absorption spectroscopy has been coupled with excimer laser flash photolysis to measure the quantum yield for CO production from 248 nm photodissociation of carbonyl sulfide (OCS) relative to the well-known quantum yield for CO production from 248 nm photolysis of phosgene (Cl2CO2). The temporal resolution of the experiments was sufficient to distinguish CO formed directly by photodissociation from that formed by subsequent S((sup 3)P(sub J)) reaction with OCS. Under the experimental conditions employed, CO formation via the fast S((sup 1)D(sub 2)) + OCS reaction was minimal. Measurements at 297K and total pressures from 4 to 100 Torr N2 + N2O show the CO yield to be greater than 0.95 and most likely unity. This result suggests that the contribution of OCS as a precursor to the lower stratospheric sulfate aerosol layer is somewhat larger than previously thought.

Three-Dimensional Printing of Bisphenol A-Free Polycarbonates.

PubMed

Zhu, Wei; Pyo, Sang-Hyun; Wang, Pengrui; You, Shangting; Yu, Claire; Alido, Jeffrey; Liu, Justin; Leong, Yew; Chen, Shaochen

2018-02-14

Polycarbonates are widely used in food packages, drink bottles, and various healthcare products such as dental sealants and tooth coatings. However, bisphenol A (BPA) and phosgene used in the production of commercial polycarbonates pose major concerns to public health safety. Here, we report a green pathway to prepare BPA-free polycarbonates (BFPs) by thermal ring-opening polymerization and photopolymerization. Polycarbonates prepared from two cyclic carbonates in different mole ratios demonstrated tunable mechanical stiffness, excellent thermal stability, and high optical transparency. Three-dimensional (3D) printing of the new BFPs was demonstrated using a two-photon laser direct writing system and a rapid 3D optical projection printer to produce structures possessing complex high-resolution geometries. Seeded C3H10T1/2 cells also showed over 95% viability with potential applications in biological studies. By combining biocompatible BFPs with 3D printing, novel safe and high-performance biomedical devices and healthcare products could be developed with broad long-term benefits to society.

[Use of chemical war gases at the Russian-German front during the First World War].

PubMed

Budko, A A; Ivanovskii, Yu V

2016-02-01

The First World War was notable for the widespread use of machine military hardware and absolutely new type of weapon--chemical weapon. As a result of the first gas attack by chlorine undertaken by the German army against the Russian armies on May, 31st, 1915, heavy poisonings have received 9100 people, 6000 of them died. Chemical attack of Germany against Russia was limited by the use chemical gases of suffocating action: chlorine, bromine,phosgene and diphosgene. It is not known exactly, how many times Germany attacked Russian positions with use of chemical gases. On available data, in the First World War from application by German of the chemical weapon Russia has suffered more, than any other of the at war countries: from five hundred thousand poisoned have died nearby 66,000 people. In turn, having received in the order the chemical weapon of own manufacture, Russian army itself tried to attack in the German armies. It is authentically known only about several cases of application dy Russian of fighting poison gases, and in all cases of loss of germen were insignificant.

Template-assisted formation of microsized nanocrystalline CeO2 tubes and their catalytic performance in the carboxylation of methanol

PubMed Central

Naumann, Meike; Schäfer, Christian; Brandner, Armin; Hofmann, Heiko J; Claus, Peter

2011-01-01

Summary Polymethylmethacrylate (PMMA)/ceria composite fibres were synthesized by using a sequential combination of polymer electrospinning, spray-coating with a sol, and a final calcination step to yield microstructured ceria tubes, which are composed of nanocrystalline ceria particles. The PMMA template is removed from the organic/inorganic hybrid material by radio frequency (rf) plasma etching followed by calcination of the ceramic green-body fibres. Microsized ceria (CeO2) tubes, with a diameter of ca. 0.75 µm, composed of nanocrystalline agglomerated ceria particles were thus obtained. The 1-D ceramic ceria material was characterized by X-ray diffraction, scanning electron microscopy (SEM), high-resolution transmission electron microscopy (HRTEM), UV–vis and photoluminescence spectroscopy (PL), as well as thermogravimetric analysis (TGA). Its catalytic performance was studied in the direct carboxylation of methanol with carbon dioxide leading to dimethyl carbonate [(CH3O)2CO, DMC], which is widely employed as a phosgene and dimethyl sulfate substitute, and as well as a fuel additive. PMID:22259761

Thermal treatment of electronic waste in a fluidised bed and chemical digestion of solid products.

PubMed

Woynarowska, Amelia; Żukowski, Witold; Żelazny, Sylwester

2016-07-01

The article presents the results of e-waste thermal treatment in a fluidised bed reactor and solid products digestion under acidic conditions. During the processes, measurements of carbon monoxide, carbon dioxide, volatile organic compounds, nitrogen oxides, sulphur dioxide, hydrogen chloride, hydrogen bromide, hydrogen cyanide, ammonia, phenol, aliphatic and aromatic hydrocarbons, hydrogen fluoride and phosgene were carried out. Several digestion tests of the solid residue in sulphuric acid (VI) at 25 °C-65 °C, for 55 min-24 h were conducted. In each case, the dilution method was used, i.e. preliminary digestion in concentrated sulphuric acid (VI) (95%) for 40 min, and then dilution to expected concentrations (30%-50%). Most preferred results were obtained using sulphuric acid (VI) with a target concentration of 40% at 65 °C, where the leaching degrees were 76.56% for copper, 71.67% for iron, 91.89% for zinc and 97.40% for tin. The time necessary to effectively carry out the digestion process was 220 min. © The Author(s) 2016.

Growth in stratospheric chlorine from short-lived chemicals not controlled by the Montreal Protocol.

PubMed

Hossaini, R; Chipperfield, M P; Saiz-Lopez, A; Harrison, J J; von Glasow, R; Sommariva, R; Atlas, E; Navarro, M; Montzka, S A; Feng, W; Dhomse, S; Harth, C; Mühle, J; Lunder, C; O'Doherty, S; Young, D; Reimann, S; Vollmer, M K; Krummel, P B; Bernath, P F

2015-06-16

We have developed a chemical mechanism describing the tropospheric degradation of chlorine containing very short-lived substances (VSLS). The scheme was included in a global atmospheric model and used to quantify the stratospheric injection of chlorine from anthropogenic VSLS ( ClyVSLS) between 2005 and 2013. By constraining the model with surface measurements of chloroform (CHCl 3 ), dichloromethane (CH 2 Cl 2 ), tetrachloroethene (C 2 Cl 4 ), trichloroethene (C 2 HCl 3 ), and 1,2-dichloroethane (CH 2 ClCH 2 Cl), we infer a 2013 ClyVSLS mixing ratio of 123 parts per trillion (ppt). Stratospheric injection of source gases dominates this supply, accounting for ∼83% of the total. The remainder comes from VSLS-derived organic products, phosgene (COCl 2 , 7%) and formyl chloride (CHClO, 2%), and also hydrogen chloride (HCl, 8%). Stratospheric ClyVSLS increased by ∼52% between 2005 and 2013, with a mean growth rate of 3.7 ppt Cl/yr. This increase is due to recent and ongoing growth in anthropogenic CH 2 Cl 2 -the most abundant chlorinated VSLS not controlled by the Montreal Protocol.

[Household gas poisonings].

PubMed

Maloca, Ivana; Macan, Jelena; Varnai, Veda Marija; Turk, Rajka

2006-12-01

Exposure to toxic gases which can induce serious health effects, can occur in the working as well as in general environment, including home. The severity of gas poisoning is determined by its physical and chemical characteristics, intensity and duration of exposure, and concomitant diseases and injuries in the poisoned person. Manifestations of gas toxic action involve simple asphyxia, local irritation of respiratory mucosa, systemic toxicity, and a combination of these mechanisms. This article describes the characteristics, modes of exposure and health effects of most common gases causing poisoning at home. These include gas fuels, carbon monoxide, ammonia, chlorine, and fire gases such as nitrogen and sulphur oxides, hydrogen cyanide and phosgene. First aid as well as preventive measures to avoid exposure to toxic gases and prevent fire at home are also given. The Croatian Poison Control Centre gathered data on toxic gas exposures in households between November 2005 and July 2006. During this period 30 persons (3 % of the total number of cases) were exposed to toxic gases at home, including carbon monoxide, irritating vapours from cleaning agents and disinfectants, gas fuels, septic tank gases, tear-gas, and chlorofluorocarbons from refrigerators.

Gas: the greatest terror of the Great War.

PubMed

Padley, A P

2016-07-01

The Great War began just over a century ago and this monumental event changed the world forever. 1915 saw the emergence of gas warfare-the first weapon of mass terror. It is relevant to anaesthetists to reflect on these gases for a number of reasons. Firstly and most importantly we should acknowledge and be aware of the suffering and sacrifice of those soldiers who were injured or killed so that we could enjoy the freedoms we have today. Secondly, it is interesting to consider the overlap between poison gases and anaesthetic gases and vapors, for example that phosgene can be formed by the interaction of chloroform and sunlight. Thirdly the shadow of gas warfare is very long and covers us still. The very agents used in the Great War are still causing death and injury through deployment in conflict areas such as Iraq and Syria. Industrial accidents, train derailments and dumped or buried gas shells are other sources of poison gas hazards. In this age of terrorism, anaesthetists, as front-line resuscitation specialists, may be directly involved in the management of gas casualties or become victims ourselves.

Growth in stratospheric chlorine from short-lived chemicals not controlled by the Montreal Protocol

NASA Astrophysics Data System (ADS)

Hossaini, R.; Chipperfield, M. P.; Saiz-Lopez, A.; Harrison, J. J.; Glasow, R.; Sommariva, R.; Atlas, E.; Navarro, M.; Montzka, S. A.; Feng, W.; Dhomse, S.; Harth, C.; Mühle, J.; Lunder, C.; O'Doherty, S.; Young, D.; Reimann, S.; Vollmer, M. K.; Krummel, P. B.; Bernath, P. F.

2015-06-01

We have developed a chemical mechanism describing the tropospheric degradation of chlorine containing very short-lived substances (VSLS). The scheme was included in a global atmospheric model and used to quantify the stratospheric injection of chlorine from anthropogenic VSLS ( ClyVSLS) between 2005 and 2013. By constraining the model with surface measurements of chloroform (CHCl3), dichloromethane (CH2Cl2), tetrachloroethene (C2Cl4), trichloroethene (C2HCl3), and 1,2-dichloroethane (CH2ClCH2Cl), we infer a 2013 ClyVSLS mixing ratio of 123 parts per trillion (ppt). Stratospheric injection of source gases dominates this supply, accounting for ˜83% of the total. The remainder comes from VSLS-derived organic products, phosgene (COCl2, 7%) and formyl chloride (CHClO, 2%), and also hydrogen chloride (HCl, 8%). Stratospheric ClyVSLS increased by ˜52% between 2005 and 2013, with a mean growth rate of 3.7 ppt Cl/yr. This increase is due to recent and ongoing growth in anthropogenic CH2Cl2—the most abundant chlorinated VSLS not controlled by the Montreal Protocol.

Fate of Chloromethanes in the Atmospheric Environment: Implications for Human Health, Ozone Formation and Depletion, and Global Warming Impacts.

PubMed

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.

History and perspectives of bioanalytical methods for chemical warfare agent detection.

PubMed

Black, Robin M

2010-05-15

This paper provides a short historical overview of the development of bioanalytical methods for chemical warfare (CW) agents and their biological markers of exposure, with a more detailed overview of methods for organophosphorus nerve agents. Bioanalytical methods for unchanged CW agents are used primarily for toxicokinetic/toxicodynamic studies. An important aspect of nerve agent toxicokinetics is the different biological activity and detoxification pathways for enantiomers. CW agents have a relatively short lifetime in the human body, and are hydrolysed, metabolised, or adducted to nucleophilic sites on macromolecules such as proteins and DNA. These provide biological markers of exposure. In the past two decades, metabolites, protein adducts of nerve agents, vesicants and phosgene, and DNA adducts of sulfur and nitrogen mustards, have been identified and characterized. Sensitive analytical methods have been developed for their detection, based mainly on mass spectrometry combined with gas or liquid chromatography. Biological markers for sarin, VX and sulfur mustard have been validated in cases of accidental and deliberate human exposures. The concern for terrorist use of CW agents has stimulated the development of higher throughput analytical methods in support of homeland security. Copyright (c) 2010. Published by Elsevier B.V.

Fate of Chloromethanes in the Atmospheric Environment: Implications for Human Health, Ozone Formation and Depletion, and Global Warming Impacts

PubMed Central

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

Enzyme immobilization techniques on poly(glycidyl methacrylate-co-ethylene dimethacrylate) carrier with penicillin amidase as model.

PubMed

Drobník, J; Saudek, V; Svec, F; Kálal, J; Vojtísek, V; Bárta, M

1979-08-01

Two types of bead-form macroporous carriers based on glycidyl methacrylate with ethylene dimethacrylate copolymers were used for the immobilization of penicillin amidase either directly or after chemical modification. Direct binding through oxirane groups, which is equally efficient at pH 4.2 and 7, is relatively slow and brings about an activity loss at low enzyme concentrations. The most efficient immobilization was achieved on glutaraldehyde-activated amino carrier, irrespective of whether the amino groups were formed by ammonia or 1,6-diaminohexane treatment of the original oxirane carrier. Hydrazine treatment gave lower immobilization yields. The same is true of the azide method independent of the length of the spacer. Most enzyme activity was preserved by coupling the carbodiimide-activated enzyme to the carrier with alkyl or arylamino groups at the end of a longer substituent. Immobilization on diazo-modified carrier gave average results. Rapid immobilization by a lysine-modified phosgene-treated carrier resulted in an activity loss. It is suggested that multipoint and very tight attachment of the enzyme molecule to the matrix decreased the activity. The immobilized activity is quite stable in solution and very stable upon lyophilization with sucrose.

Detecting critical state before phase transition of complex systems by hidden Markov model

NASA Astrophysics Data System (ADS)

Liu, Rui; Chen, Pei; Li, Yongjun; Chen, Luonan

Identifying the critical state or pre-transition state just before the occurrence of a phase transition is a challenging task, because the state of the system may show little apparent change before this critical transition during the gradual parameter variations. Such dynamics of phase transition is generally composed of three stages, i.e., before-transition state, pre-transition state, and after-transition state, which can be considered as three different Markov processes. Thus, based on this dynamical feature, we present a novel computational method, i.e., hidden Markov model (HMM), to detect the switching point of the two Markov processes from the before-transition state (a stationary Markov process) to the pre-transition state (a time-varying Markov process), thereby identifying the pre-transition state or early-warning signals of the phase transition. To validate the effectiveness, we apply this method to detect the signals of the imminent phase transitions of complex systems based on the simulated datasets, and further identify the pre-transition states as well as their critical modules for three real datasets, i.e., the acute lung injury triggered by phosgene inhalation, MCF-7 human breast cancer caused by heregulin, and HCV-induced dysplasia and hepatocellular carcinoma.

Neurotoxic Weapons and Syndromes.

PubMed

Carota, Antonio; Calabrese, Pasquale; Bogousslavsky, Julien

2016-01-01

The modern era of chemical and biological warfare began in World War I with the large-scale production and use of blistering and choking agents (chlorine, phosgene and mustard gases) in the battlefield. International treaties (the 1925 Geneva Protocol, the 1975 Biological and Toxin Weapons Convention and the 1993 Chemical Weapons Convention) banned biological and chemical weapons. However, several countries are probably still engaged in their development. Hence, there is risk of these weapons being used in the future. This chapter will focus on neurotoxic weapons (e.g. nerve agents, chemical and biological neurotoxins, psychostimulants), which act specifically or preeminently on the central nervous system and/or the neuromuscular junction. Deeply affecting the function of the nervous system, these agents either have incapacitating effects or cause clusters of casualties who manifest primary symptoms of encephalopathy, seizures, muscle paralysis and respiratory failure. The neurologist should be prepared both to notice patterns of symptoms and signs that are sufficiently consistent to raise the alarm of neurotoxic attacks and to define specific therapeutic interventions. Additionally, extensive knowledge on neurotoxic syndromes should stimulate scientific research to produce more effective antidotes and antibodies (which are still lacking for most neurotoxic weapons) for rapid administration in aerosolized forms in the case of terrorist or warfare scenarios. © 2016 S. Karger AG, Basel.

Chemical munitions dumped at sea

NASA Astrophysics Data System (ADS)

Edwards, Margo; Bełdowski, Jacek

2016-06-01

Modern chemical warfare is a byproduct of the industrial revolution, which created factories capable of rapidly producing artillery shells that could be filled with toxic chemicals such as chlorine, phosgene and mustard agent. The trench warfare of World War I inaugurated extensive deployments of modern chemical weapons in 1915. Concomitantly, the need arose to dispose of damaged, captured or excess chemical munitions and their constituents. Whereas today chemical warfare agents (CWA) are destroyed via chemical neutralization processes or high-temperature incineration in tandem with environmental monitoring, in the early to middle 20th century the options for CWA disposal were limited to open-air burning, burial and disposal at sea. The latter option was identified as the least likely of the three to impact mankind, and sea dumping of chemical munitions commenced. Eventually, the potential impacts of sea dumping human waste were recognized, and in 1972 an international treaty, the Convention on the Prevention of Marine Pollution by Dumping of Wastes and Other Matter, was developed to protect the marine environment from pollution caused by the dumping of wastes and other matter into the ocean. By the time this treaty, referred to as the London Convention, was signed by a majority of nations, millions of tons of munitions were known to have been disposed throughout the world's oceans.

Efficiency of inductively torch plasma operating at atmospheric pressure on destruction of chlorinated liquid wastes- A path to the treatment of radioactive organic halogen liquid wastes

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.

Chlorobenzene degeradation by non-thermal plasma combined with EG-TiO2/ZnO as a photocatalyst: Effect of photocatalyst on CO2 selectivity and byproducts reduction.

PubMed

Ghorbani Shahna, Farshid; Bahrami, Abdulrahman; Alimohammadi, Iraj; Yarahmadi, Rassuol; Jaleh, Babak; Gandomi, Mastaneh; Ebrahimi, Hossein; Ad-Din Abedi, Kamal

2017-02-15

The non-thermal plasma (NTP) technique, which suffers from low selectivity in complete oxidation of volatile organic compounds to CO 2 and H 2 O, creates unwanted and harmful byproducts. NTP in concert with photocatalyst can resolve this limitation due to additional oxidation. TiO 2 and ZnO nanoparticles were coated on the surface of the expanded graphite and placed downstream of the NTP reactor under UV light. In this study, to compare the performance of NTP and the combined system, chlorobenzene removal, selectivity of CO 2 and byproducts formation were investigated. The results showed that the combined system enhanced both the removal efficiency and CO 2 selectivity. The output gas of the NTP reactor contained chlorobenzene, phosgene, O 3 , NO, NO 2 , CO, CO 2 , HCL and CL. The bulk of these byproducts was oxidized on the surface of the nanocomposite; as a result, the content of the byproducts in the output gas of the combined system decreased dramatically. The removal efficiency and CO 2 selectivity increased by rising the applied voltage and residence time because the collision between active species and pollutant molecules increases. Based on these results, the combined system is preferred due to a higher performance and lower formation of harmful byproducts. Copyright © 2016 Elsevier B.V. All rights reserved.

The Isonzo front in the First World War: glass ampoules found in the vicinity of the village Kred.

PubMed

Krbavcic, Ales

2015-01-01

To identify the contents of ampoules stored items at the WW I Kobarid Museum, Slovenia. Sources and methods: Analysis of ampoules from the Kobarid Museum using pharmacopoeial methods. The contents of the unlabelled ampoules were identified as calcium hypochlorite, a decontaminant for mustard gas (Yperite). The Isonzo front/Soška fronta was opened on May 24 1915 by the Kingdom of Italy according to a secret London Treaty. In exchange for the opening of this front, the Kingdom of Italy would be granted large tracts of territory in the wesster provinces of the Austro-Hungarian Empire and along the Adriatic coast. The ensuing trench-warfare during the eleven Isonzo battles ended with the 12th battle known as the Kobarid/Karfeit/Caporetto break-thru in October 1917. The joint German and Austro-Hungarian forces waged a massive gas-attack with dichloroarsine and phosgene, which was later disclosed as the horrifying overture to the general disordered retreat of the Italian troops to Piave. The possibility of a chemical attack was underestimated by the Italian high command as shown by the ineffective gas-masks issued to the troops. Hovewer, a recent find of ampoules with calcium hypochlorite at the village of Kred, now exhibited at the Kobarid WWI Museum, leads to the conclusion that the Italian IVth army's command, located in Kred, considered decontamination measures against Yperite necessary.

Developing Health-Based Pre-Planning Clearance Goals for Airport Remediation Following Chemical Terrorist Attack: Introduction and Key Assessment Considerations

PubMed Central

Watson, Annetta; Hall, Linda; Raber, Ellen; Hauschild, Veronique D.; Dolislager, Fredrick; Love, Adam H.; Hanna, M. Leslie

2011-01-01

In the event of a chemical terrorist attack on a transportation hub, post-event remediation and restoration activities necessary to attain unrestricted facility reuse and re-entry could require hours to multiple days. While restoration timeframes are dependent on numerous variables, a primary controlling factor is the level of pre-planning and decision-making completed prior to chemical terrorist release. What follows is the first of a two-part analysis identifying key considerations, critical information, and decision criteria to facilitate post-attack and post-decontamination consequence management activities. A conceptual site model and human health-based exposure guidelines are developed and reported as an aid to site-specific pre-planning in the current absence of U.S. state or Federal values designated as compound-specific remediation or re-entry concentrations, and to safely expedite facility recovery to full operational status. Chemicals of concern include chemical warfare nerve and vesicant agents and the toxic industrial compounds phosgene, hydrogen cyanide, and cyanogen chloride. This work has been performed as a national case study conducted in partnership with the Los Angeles International Airport and The Bradley International Terminal. All recommended guidelines have been selected for consistency with airport scenario release parameters of a one-time, short-duration, finite airborne release from a single source followed by compound-specific decontamination. PMID:21390292

Developing Health-Based Pre-Planning Clearance Goals for Airport Remediation Following Chemical Terrorist Attack: Introduction and Key Assessment Considerations.

PubMed

Watson, Annetta; Hall, Linda; Raber, Ellen; Hauschild, Veronique D; Dolislager, Fredrick; Love, Adam H; Hanna, M Leslie

2011-02-13

In the event of a chemical terrorist attack on a transportation hub, post-event remediation and restoration activities necessary to attain unrestricted facility reuse and re-entry could require hours to multiple days. While restoration timeframes are dependent on numerous variables, a primary controlling factor is the level of pre-planning and decision-making completed prior to chemical terrorist release. What follows is the first of a two-part analysis identifying key considerations, critical information, and decision criteria to facilitate post-attack and post-decontamination consequence management activities. A conceptual site model and human health-based exposure guidelines are developed and reported as an aid to site-specific pre-planning in the current absence of U.S. state or Federal values designated as compound-specific remediation or re-entry concentrations, and to safely expedite facility recovery to full operational status. Chemicals of concern include chemical warfare nerve and vesicant agents and the toxic industrial compounds phosgene, hydrogen cyanide, and cyanogen chloride. This work has been performed as a national case study conducted in partnership with the Los Angeles International Airport and The Bradley International Terminal. All recommended guidelines have been selected for consistency with airport scenario release parameters of a one-time, short-duration, finite airborne release from a single source followed by compound-specific decontamination.

An Official American Thoracic Society Workshop Report: Chemical Inhalational Disasters. Biology of Lung Injury, Development of Novel Therapeutics, and Medical Preparedness

PubMed Central

Hoyle, Gary W.; Jordt, Sven-Eric; Jugg, Bronwen J.; Martin, James G.; Matalon, Sadis; Patterson, Steven E.; Prezant, David J.; Sciuto, Alfred M.; Svendsen, Erik R.; White, Carl W.; Veress, Livia A.

2017-01-01

This report is based on the proceedings from the Inhalational Lung Injury Workshop jointly sponsored by the American Thoracic Society (ATS) and the National Institutes of Health (NIH) Countermeasures Against Chemical Threats (CounterACT) program on May 21, 2013, in Philadelphia, Pennsylvania. The CounterACT program facilitates research leading to the development of new and improved medical countermeasures for chemical threat agents. The workshop was initiated by the Terrorism and Inhalational Disasters Section of the Environmental, Occupational, and Population Health Assembly of the ATS. Participants included both domestic and international experts in the field, as well as representatives from U.S. governmental funding agencies. The meeting objectives were to (1) provide a forum to review the evidence supporting current standard medical therapies, (2) present updates on our understanding of the epidemiology and underlying pathophysiology of inhalational lung injuries, (3) discuss innovative investigative approaches to further delineating mechanisms of lung injury and identifying new specific therapeutic targets, (4) present promising novel medical countermeasures, (5) facilitate collaborative research efforts, and (6) identify challenges and future directions in the ongoing development, manufacture, and distribution of effective and specific medical countermeasures. Specific inhalational toxins discussed included irritants/pulmonary toxicants (chlorine gas, bromine, and phosgene), vesicants (sulfur mustard), chemical asphyxiants (cyanide), particulates (World Trade Center dust), and respirable nerve agents. PMID:28418689

Developing health-based pre-planning clearance goals for airport remediation following chemical terrorist attack: Introduction and key assessment considerations

DOE Office of Scientific and Technical Information (OSTI.GOV)

Watson, Annetta Paule; Raber, Ellen; Dolislager, Frederick

2011-01-01

In the event of a chemical terrorist attack on a transportation hub, post-event remediation and restoration activities necessary to attain unrestricted facility re-use and re-entry could require hours to multiple days. While restoration timeframes are dependent on numerous variables, a primary controlling factor is the level of pre-planning and decision-making completed prior to chemical terrorist release. What follows is the first of a two-part analysis identifying key considerations, critical information, and decision criteria to facilitate post-attack and post-decontamination consequence management activities. A conceptual site model and human health-based exposure guidelines are developed and reported as an aid to site-specific pre-planningmore » in the current absence of U.S. state or Federal values designated as compound-specific remediation or re-entry concentrations, and to safely expedite facility recovery to full operational status. Chemicals of concern include chemical warfare nerve and vesicant agents and the toxic industrial compounds phosgene, hydrogen cyanide, and cyanogen chloride. This work has been performed as a national case study conducted in partnership with the Los Angeles International Airport and The Bradley International Terminal. All recommended guidelines have been selected for consistency with airport scenario release parameters of a one-time, short-duration, finite airborne release from a single source followed by compound-specific decontamination.« less

New poly(ester urea) derived from L-leucine: electrospun scaffolds loaded with antibacterial drugs and enzymes.

PubMed

Díaz, Angélica; del Valle, Luis J; Tugushi, David; Katsarava, Ramaz; Puiggalí, Jordi

2015-01-01

Electrospun scaffolds from an amino acid containing poly(ester urea) (PEU) were developed as promising materials in the biomedical field and specifically in tissue engineering applications. The selected poly(ester urea) was obtained with a high yield and molecular weight by reaction of phosgene with a bis(α-aminoacyl)-α,ω-diol-diester monomer. The polymer having L-leucine, 1,6-hexanediol and carbonic acid units had a semicrystalline character and relatively high glass transition and melting temperatures. Furthermore it was highly soluble in most organic solvents, an interesting feature that facilitated the electrospinning process and the effective incorporation of drugs with bactericidal activity (e.g. biguanide derivatives such as clorhexidine and polyhexamethylenebiguanide) and enzymes (e.g. α-chymotrypsin) that accelerated the degradation process. Continuous micro/nanofibers were obtained under a wide range of processing conditions, being diameters of electrospun fibers dependent on the drug and solvent used. Poly(ester urea) samples were degradable in media containing lipases and proteinases but the degradation rate was highly dependent on the surface area, being specifically greater for scaffolds with respect to films. The high hydrophobicity of new scaffolds had repercussions on enzymatic degradability since different weight loss rates were found depending on how samples were exposed to the medium (e.g. forced or non-forced immersion). New scaffolds were biocompatible, as demonstrated by adhesion and proliferation assays performed with fibroblast and epithelial cells. Copyright © 2014 Elsevier B.V. All rights reserved.

Potential health impacts from range fires at Aberdeen Proving Ground, Maryland.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Willians, G.P.; Hermes, A.M.; Policastro, A.J.

1998-03-01

This study uses atmospheric dispersion computer models to evaluate the potential for human health impacts from exposure to contaminants that could be dispersed by fires on the testing ranges at Aberdeen Proving Ground, Maryland. It was designed as a screening study and does not estimate actual human health risks. Considered are five contaminants possibly present in the soil and vegetation from past human activities at APG--lead, arsenic, trichloroethylene (TCE), depleted uranium (DU), and dichlorodiphenyltrichloroethane (DDT); and two chemical warfare agents that could be released from unexploded ordnance rounds heated in a range fire--mustard and phosgene. For comparison, dispersion of twomore » naturally occurring compounds that could be released by burning of uncontaminated vegetation--vinyl acetate and 2-furaldehyde--is also examined. Data from previous studies on soil contamination at APG are used in conjunction with conservative estimates about plant uptake of contaminants, atmospheric conditions, and size and frequency of range fires at APG to estimate dispersion and possible human exposure. The results are compared with US Environmental Protection Agency action levels. The comparisons indicate that for all of the anthropogenic contaminants except arsenic and mustard, exposure levels would be at least an order of magnitude lower than the corresponding action levels. Because of the compoundingly conservative nature of the assumptions made, they conclude that the potential for significant human health risks from range fires is low. The authors recommend that future efforts be directed at fire management and control, rather than at conducting additional studies to more accurately estimate actual human health risk from range fires.« less

Fate of chemical warfare agents and toxic industrial chemicals in landfills.

PubMed

Bartelt-Hunt, Shannon L; Barlaz, Morton A; Knappe, Detlef R U; Kjeldsen, Peter

2006-07-01

One component of preparedness for a chemical attack is planning for the disposal of contaminated debris. To assess the feasibility of contaminated debris disposal in municipal solid waste (MSW) landfills, the fate of selected chemical warfare agents (CWAs) and toxic industrial chemicals (TICs) in MSW landfills was predicted with a mathematical model. Five blister agents [sulfur mustard (HD), nitrogen mustard (HN-2), lewisite (L), ethyldichloroarsine (ED), and phosgene oxime (CX)], eight nerve agents [tabun (GA), sarin (GB), soman (GD), GE, GF, VX, VG, and VM], one riot-control agent [CS], and two TICs [furan and carbon disulfide] were studied. The effects of both infiltration (climate) and contaminant biodegradability on fate predictions were assessed. Model results showed that hydrolysis and gas-phase advection were the principal fate pathways for CWAs and TICs, respectively. Apart from CX and the TICs, none of the investigated compounds was predicted to persist in a landfill for more than 5 years. Climate had little impact on CWA/TIC fate, and biodegradability was only important for compounds with long hydrolysis half-lives. Monte Carlo simulations were performed to assess the influence of uncertainty in model input parameters on CWA/TIC fate predictions. Correlation analyses showed that uncertainty in hydrolysis rate constants was the primary contributor to variance of CWA fate predictions, while uncertainty in the Henry's Law constant and landfill gas-production rate accounted for most of the variance of TIC fate predictions. CWA hydrolysates were more persistent than the parent CWAs, but limited information is available on abiotic or biotic transformation rates for these chemicals.

Sensory Detection and Responses to Toxic Gases

PubMed Central

Bessac, Bret F.; Jordt, Sven-Eric

2010-01-01

The inhalation of reactive gases and vapors can lead to severe damage of the airways and lung, compromising the function of the respiratory system. Exposures to oxidizing, electrophilic, acidic, or basic gases frequently occur in occupational and ambient environments. Corrosive gases and vapors such as chlorine, phosgene, and chloropicrin were used as warfare agents and in terrorist acts. Chemical airway exposures are detected by the olfactory, gustatory, and nociceptive sensory systems that initiate protective physiological and behavioral responses. This review focuses on the role of airway nociceptive sensory neurons in chemical sensing and discusses the recent discovery of neuronal receptors for reactive chemicals. Using physiological, imaging, and genetic approaches, Transient Receptor Potential (TRP) ion channels in sensory neurons were shown to respond to a wide range of noxious chemical stimuli, initiating pain, respiratory depression, cough, glandular secretions, and other protective responses. TRPA1, a TRP ion channel expressed in chemosensory C-fibers, is activated by almost all oxidizing and electrophilic chemicals, including chlorine, acrolein, tear gas agents, and methyl isocyanate, the highly noxious chemical released in the Bhopal disaster. Chemicals likely activate TRPA1 through covalent protein modification. Animal studies using TRPA1 antagonists or TRPA1-deficient mice confirmed the role of TRPA1 in chemically induced respiratory reflexes, pain, and inflammation in vivo. New research shows that sensory neurons are not merely passive sensors of chemical exposures. Sensory channels such as TRPA1 are essential for maintenance of airway inflammation in asthma and may contribute to the progression of airway injury following high-level chemical exposures. PMID:20601631

[Eustachy Gryszkiewicz-Trochimowski (1888-1971) chemist].

PubMed

Morawski, Bogdan

2011-01-01

Eustachy Gryszkiewicz-Trochimowski was born on April 17, 1888, in Kowle on Volhynia. Having graduated from classical grammar-school in Humań, he began his studies in the Faculty of Mathematics and Natural Science in the University of St. Wlodzimierz in Kiev. His scientific interests in chemistry appeared already during university studies. This fact attracted his teacher's attention--a distinguished organic chemist--professor S. N. Reformatski (1860-1938). The first works he published in the years 1908-1909. In 1910 professor Reformatski appointed him to a post of assistant in laboratory of organic chemistry within Higher Women Classes. In 1913 Gryszkiewicz-Trochimowski was employed as an assistant professor, and as a lecturer in chemistry was appointed to a post of professor in Higher Institute of Trade. After professor Reformatski had retired in 1917, Gryszkiewicz-Trochimowski was appointed to a professorship and took over a chair in Organic Chemistry Department. In 1925, having moved to Poland, he resigned from academic career. Having returned to Poland, he began to work in Research Institute of Chemical Weapons, in which took up systematic and extensive research works over arsenoorganic compounds, and combinations including fluorine. He worked out an original method of producing an unavailable compound of oxym of phosgene, which later was widely used, and also beyond the army. The combination was available just by dint of the method that was introduced by Gryszkiewicz-Trochimowski. In Poland the method of producing oxym of phosgene was concealed, and the compound was produced under a secret name TSD together with sulphuric yperite. Moreover, Gryszkiewicz-Trochimowski took up intensive scientific researches on synthesis of halogen derivatives of aliphatic, and aliphatic and aromatic ketones. In the second half of the 1930s, together with the closest co-workers--doctor Adam Sporzyński and Lieutenant MA Jakub Wnuk--he worked out a new method of synthesis of organic-fluoric combinations. The method was kept in the strictest secrecy and was revealed in 1942 to the English by doctor Sporzyński while visiting Great Britain. The results of the Warsaw research works were laid before professor of the University of Cambridge--H. McCombiem, who presented them as his own discovery, and who took a patent for the method. While doing research works in the Institute, Eustachy Gryszkiewicz-Trochimowski with an approval of army administration since January, 1929, started to work in Industry and Trade Establishments of Chemistry--L. Spiess & Son. Co-operating with the company for 10 years, he elaborated and applied the modified methods of producing many synthetic remedies, and worked out a program of establishment's production that could easily conform with the modern chemical and pharmaceutical factory. The program in the post-war period was continued almost for two decades. Gryszkiewicz-Trochimowski was the only chemist in Poland, who did his research works over synthetic healers. In the period of occupation he worked for a while in the company "Spiess". In 1943 he was informed of the murder in Katyń of his co-worker--captain doctor Wnuk. A perspective of annextion of Polish territories by the Soviets was for him a serious threat and thus he started making attempts at leaving for the west. He left the country under unknown circumstances and found himself in France. After the end of World War II he published a great many of his works that earlier had been kept in secret. In France he was employed in the military scientific and research institution--Centre d'Etudes du Buchet--and was engaged in works over a French program of defence. Having lived to be seventy nine, died on February 25, 1971, in Brazil.

Health-based Provisional Advisory Levels (PALs) for homeland security.

PubMed

Adeshina, Femi; Sonich-Mullin, Cynthia; Ross, Robert H; Wood, Carol S

2009-12-01

The Homeland Security Presidential Directive #8 (HSPD-8) for National Emergency Preparedness was issued to " establish policies to strengthen the preparedness of the United States to prevent and respond to threatened or actual domestic terrorist attacks, major disasters, and other emergencies by requiring a national domestic all- hazards preparedness goal. "In response to HSPD-8 and HSPD-22 (classified) on Domestic Chemical Defense, the US Environmental Protection Agency (US EPA) National Homeland Security Research Center (NHSRC) is developing health-based Provisional Advisory Levels (PALs) for priority chemicals (including chemical warfare agents, pesticides, and toxic industrial chemicals) in air and drinking water. PALs are temporary values that will neither be promulgated, nor be formally issued as regulatory guidance. They are intended to be used at the discretion of risk managers in emergency situations. The PAL Program provides advisory exposure levels for chemical agents to assist in emergency planning and response decision-making, and to aid in making informed risk management decisions for evacuation, temporary re-entry into affected areas, and resumed-use of infrastructure, such as water resources. These risk management decisions may be made at the federal, state, and local levels. Three exposure levels (PAL 1, PAL 2, and PAL 3), distinguished by severity of toxic effects, are developed for 24-hour, 30-day, 90-day, and 2-year durations for potential exposure to drinking water and ambient air by the general public. Developed PALs are evaluated both by a US EPA working group, and an external multidisciplinary panel to ensure scientific credibility and wide acceptance. In this Special Issue publication, we present background information on the PAL program, the methodology used in deriving PALs, and the technical support documents for the derivation of PALs for acrylonitrile, hydrogen sulfide, and phosgene.

High Resolution Thz and FIR Spectroscopy of SOCl_2

NASA Astrophysics Data System (ADS)

Martin-Drumel, M. A.; Cuisset, A.; Sadovskii, D. A.; Mouret, G.; Hindle, F.; Pirali, O.

2013-06-01

Thionyl chloride (SOCl_2) is an extremely powerful oxidant widely used in industrial processes and playing a role in the chemistry of the atmosphere. In addition, it has a molecular configuration similar to that of phosgene (COCl_2), and is therefore of particular interest for security and defense applications. Low resolution vibrational spectra of gas phase SOCl_2 as well as high resolution pure rotational transitions up to 25 GHz have previously been investigated. To date no high resolution data are reported at frequencies higher than 25 GHz. We have investigated the THz absorption spectrum of SOCl_2 in the spectral region 70-650 GHz using a frequency multiplier chain coupled to a 1 m long single path cell containing a pressure of about 15 μbar. At the time of the writing, about 8000 pure rotational transitions of SO^{35}Cl_2 with highest J and K_a values of 110 and 50 respectively have been assigned on the spectrum. We have also recorded the high resolution FIR spectra of SOCl_2 in the spectral range 50-700 wn using synchrotron radiation at the AILES beamline of SOLEIL facility. A White-type cell aligned with an absorption path length of 150 m has been used to record, at a resolution of 0.001 wn, two spectra at pressures of 5 and 56 μbar of SOCl_2. On these spectra all FIR modes of SOCl_2 are observed (ν_2 to ν_6) and present a resolved rotational structure. Their analysis is in progress. T. J. Johnson et al., J. Phys. Chem. A 107, 6183 (2003) D. E. Martz and R. T. Lagemann, J. Chem. Phys. 22,1193 (1954) H. S. P. Müller and M. C. L. Gerry, J. Chem. Soc. Faraday Trans. 90, 3473 (1994)

Morphological and functional differentiation in BE(2)-M17 human neuroblastoma cells by treatment with Trans-retinoic acid

PubMed Central

2013-01-01

Background Immortalized neuronal cell lines can be induced to differentiate into more mature neurons by adding specific compounds or growth factors to the culture medium. This property makes neuronal cell lines attractive as in vitro cell models to study neuronal functions and neurotoxicity. The clonal human neuroblastoma BE(2)-M17 cell line is known to differentiate into a more prominent neuronal cell type by treatment with trans-retinoic acid. However, there is a lack of information on the morphological and functional aspects of these differentiated cells. Results We studied the effects of trans-retinoic acid treatment on (a) some differentiation marker proteins, (b) types of voltage-gated calcium (Ca2+) channels and (c) Ca2+-dependent neurotransmitter ([3H] glycine) release in cultured BE(2)-M17 cells. Cells treated with 10 μM trans-retinoic acid (RA) for 72 hrs exhibited marked changes in morphology to include neurite extensions; presence of P/Q, N and T-type voltage-gated Ca2+ channels; and expression of neuron specific enolase (NSE), synaptosomal-associated protein 25 (SNAP-25), nicotinic acetylcholine receptor α7 (nAChR-α7) and other neuronal markers. Moreover, retinoic acid treated cells had a significant increase in evoked Ca2+-dependent neurotransmitter release capacity. In toxicity studies of the toxic gas, phosgene (CG), that differentiation of M17 cells with RA was required to see the changes in intracellular free Ca2+ concentrations following exposure to CG. Conclusion Taken together, retinoic acid treated cells had improved morphological features as well as neuronal characteristics and functions; thus, these retinoic acid differentiated BE(2)-M17 cells may serve as a better neuronal model to study neurobiology and/or neurotoxicity. PMID:23597229

Morphological and functional differentiation in BE(2)-M17 human neuroblastoma cells by treatment with Trans-retinoic acid.

PubMed

Andres, Devon; Keyser, Brian M; Petrali, John; Benton, Betty; Hubbard, Kyle S; McNutt, Patrick M; Ray, Radharaman

2013-04-18

Immortalized neuronal cell lines can be induced to differentiate into more mature neurons by adding specific compounds or growth factors to the culture medium. This property makes neuronal cell lines attractive as in vitro cell models to study neuronal functions and neurotoxicity. The clonal human neuroblastoma BE(2)-M17 cell line is known to differentiate into a more prominent neuronal cell type by treatment with trans-retinoic acid. However, there is a lack of information on the morphological and functional aspects of these differentiated cells. We studied the effects of trans-retinoic acid treatment on (a) some differentiation marker proteins, (b) types of voltage-gated calcium (Ca2+) channels and (c) Ca2+-dependent neurotransmitter ([3H] glycine) release in cultured BE(2)-M17 cells. Cells treated with 10 μM trans-retinoic acid (RA) for 72 hrs exhibited marked changes in morphology to include neurite extensions; presence of P/Q, N and T-type voltage-gated Ca2+ channels; and expression of neuron specific enolase (NSE), synaptosomal-associated protein 25 (SNAP-25), nicotinic acetylcholine receptor α7 (nAChR-α7) and other neuronal markers. Moreover, retinoic acid treated cells had a significant increase in evoked Ca2+-dependent neurotransmitter release capacity. In toxicity studies of the toxic gas, phosgene (CG), that differentiation of M17 cells with RA was required to see the changes in intracellular free Ca2+ concentrations following exposure to CG. Taken together, retinoic acid treated cells had improved morphological features as well as neuronal characteristics and functions; thus, these retinoic acid differentiated BE(2)-M17 cells may serve as a better neuronal model to study neurobiology and/or neurotoxicity.

Reactive chromophores for sensitive and selective detection of chemical warfare agents and toxic industrial chemicals

NASA Astrophysics Data System (ADS)

Frye-Mason, Greg; Leuschen, Martin; Wald, Lara; Paul, Kateri; Hancock, Lawrence F.

2005-05-01

A reactive chromophore developed at MIT exhibits sensitive and selective detection of surrogates for G-class nerve agents. This reporter acts by reacting with the agent to form an intermediate that goes through an internal cyclization reaction. The reaction locks the molecule into a form that provides a strong fluorescent signal. Using a fluorescent sensor platform, Nomadics has demonstrated rapid and sensitive detection of reactive simulants such as diethyl chloro-phosphate (simulant for sarin, soman, and related agents) and diethyl cyanophosphate (simulant for tabun). Since the unreacted chromophore does not fluoresce at the excitation wavelength used for the cyclized reporter, the onset of fluo-rescence can be easily detected. This fluorescence-based detection method provides very high sensitivity and could enable rapid detection at permissible exposure levels. Tests with potential interferents show that the reporter is very selective, with responses from only a few highly toxic, electrophilic chemicals such as phosgene, thionyl chloride, and strong acids such as HF, HCl, and nitric acid. Dimethyl methyl phosphonate (DMMP), a common and inactive simu-lant for other CW detectors, is not reactive enough to generate a signal. The unique selectivity to chemical reactivity means that a highly toxic and hazardous chemical is present when the reporter responds and illustrates that this sensor can provide very low false alarm rates. Current efforts focus on demonstrating the sensitivity and range of agents and toxic industrial chemicals detected with this reporter as well as developing additional fluorescent reporters for a range of chemical reactivity classes. The goal is to produce a hand-held sensor that can sensitively detect a broad range of chemical warfare agent and toxic industrial chemical threats.

Fast Orthogonal Separation by Superposition of Time of Flight and Field Asymmetric Ion Mobility Spectrometry.

PubMed

Bohnhorst, Alexander; Kirk, Ansgar T; Berger, Marc; Zimmermann, Stefan

2018-01-16

Ion mobility spectrometry is a powerful and low-cost technique for the identification of chemical warfare agents, toxic chemicals, or explosives in air. Drift tube ion mobility spectrometers (DT-IMS) separate ions by the absolute value of their low field ion mobility, while field asymmetric ion mobility spectrometers (FAIMS) separate them by the change of their ion mobility at high fields. However, using one of these devices alone, some common and harmless substances show the same response as the hazardous target substances. In order to increase the selectivity, orthogonal data are required. Thus, in this work, we present for the first time an ambient pressure ion mobility spectrometer which is able to separate ions both by their differential and low field mobility, providing additional information for selectivity enhancement. This novel field asymmetric time of flight ion mobility spectrometer (FAT-IMS) allows high repetition rates and reaches limits of detection in the low ppb range common for DT-IMS. The device consists of a compact 44 mm drift tube with a tritium ionization source and a resolving power of 70. An increased separation of four substances with similar low field ion mobility is shown: phosgene (K 0 = 2.33 cm 2 /(V s)), 1,1,2-trichlorethane (K 0 = 2.31 cm 2 /(V s)), chlorine (K 0 = 2.24 cm 2 /(V s)), and nitrogen dioxide (K 0 = 2.25 cm 2 /(V s)). Furthermore, the behavior and limits of detection for acetonitrile, dimethyl methylphosphonate, diisopropyl methyl phosphonate in positive polarity and carbon dioxide, sulfur dioxide, hydrochloric acid, cyanogen chloride, and hydrogen cyanide in negative polarity are investigated.

Investigations of chemical warfare agents and toxic industrial compounds with proton-transfer-reaction mass spectrometry for a real-time threat monitoring scenario.

PubMed

Kassebacher, Thomas; Sulzer, Philipp; Jürschik, Simone; Hartungen, Eugen; Jordan, Alfons; Edtbauer, Achim; Feil, Stefan; Hanel, Gernot; Jaksch, Stefan; Märk, Lukas; Mayhew, Chris A; Märk, Tilmann D

2013-01-30

Security and protection against terrorist attacks are major issues in modern society. One especially challenging task is the monitoring and protection of air conditioning and heating systems of buildings against terrorist attacks with toxic chemicals. As existing technologies have low selectivity, long response times or insufficient sensitivity, there is a need for a novel approach such as we present here. We have analyzed various chemical warfare agents (CWAs) and/or toxic industrial compounds (TICs) and related compounds, namely phosgene, diphosgene, chloroacetone, chloroacetophenone, diisopropylaminoethanol, and triethyl phosphate, utilizing a high-resolution proton-transfer-reaction time-of-flight mass spectrometry (PTR-TOFMS) instrument with the objective of finding key product ions and their intensities, which will allow a low-resolution quadrupole mass spectrometry based PTR-MS system to be used with high confidence in the assignment of threat agents in the atmosphere. We obtained high accuracy PTR-TOFMS mass spectra of the six compounds under study at two different values for the reduced electric field in the drift tube (E/N). From these data we have compiled a table containing product ions, and isotopic and E/N ratios for highly selective threat compound detection with a compact and cost-effective quadrupole-based PTR-MS instrument. Furthermore, using chloroacetophenone (tear gas), we demonstrated that this instrument's response is highly linear in the concentration range of typical Acute Exposure Guideline Levels (AEGLs). On the basis of the presented results it is possible to develop a compact and cost-effective PTR-QMS instrument that monitors air supply systems and triggers an alarm as soon as the presence of a threat agent is detected. We hope that this real-time surveillance device will help to seriously improve safety and security in environments vulnerable to terrorist attacks with toxic chemicals. Copyright © 2012 John Wiley & Sons, Ltd.

Synthesis and pharmacological activity of new carbonyl derivatives of 1-aryl-2-iminoimidazolidine: part 2. Synthesis and pharmacological activity of 1,6-diaryl-5,7(1H)dioxo-2,3-dihydroimidazo[1,2-a][1,3,5]triazines.

PubMed

Matosiuk, Dariusz; Fidecka, Sylwia; Antkiewicz-Michaluk, Lucyna; Lipkowski, Janusz; Dybala, Izabela; Koziol, Anna E

2002-09-01

Synthesis and pharmacological activity of 1,6-diaryl-5,7(1H)dioxo-2,3-dihydroimidazo-[1,2-a][1,3,5]triazines (C) are presented. The title compounds were obtained from 1-arylimidazolinurea derivatives in cyclization reaction with difunctional carbonyl reagents--phosgene (method I) or carbonyldiimidazole (CDI) (method II). Their molecular structures were confirmed by the X-ray analysis of 1-phenyl-6-(4-chlorophenyl)-5,7(1H)-dioxo-2,3-dihydroimidazo[1,2-a][1,3,5]triazine (C2) crystals. Compounds C exhibited significant depressive action on the central nervous system (CNS) of the laboratory animals, correlated with very low acute toxicity (LD(50) > 2000 mg kg(-1) i.p.), and showed antinociceptive activity in behavioural models. Reversion of this effect by small dose of naloxone (5 mg kg(-1)) can suggest opioid-like mechanism of antinociception produced by these and other carbonyl derivatives of 1-aryl-2-iminoimidazolidine. Additionally, an effect on the serotonin neurotransmission pathway was also observed. The receptor mechanism of activity for investigated compounds was confirmed only for the opioid mu receptor in binding affinity assay test. Same tests performed for the serotonin 5-HT(2) and benzodiazepine BZD receptors showed no affinity for tested compounds. The opioid-like and serotonergic activities are similar to these described earlier for chain carbonyl 1-aryl-2-iminoimidazolidine derivatives containing urea moiety, mainly due to similar chemical structure, although compounds C are not able to adopt any of the higher energy conformations of urea derivatives. Rigid location of aromatic ring (Ar') at N6, acting as a spacer blocking any direct access to the carbonyl groups (e.g. through the hydrogen bonding), could be responsible for lack of affinity toward 5-HT(2) expressed in the binding assay test. Copyright 2002 Editions scienctifiques et médicales Elsevier SAS

Identification of chemical warfare agents from vapor samples using a field-portable capillary gas chromatography/membrane-interfaced electron ionization quadrupole mass spectrometry instrument with Tri-Bed concentrator.

PubMed

Nagashima, Hisayuki; Kondo, Tomohide; Nagoya, Tomoki; Ikeda, Toru; Kurimata, Naoko; Unoke, Shohei; Seto, Yasuo

2015-08-07

A field-portable gas chromatograph-mass spectrometer (Hapsite ER system) was evaluated for the detection of chemical warfare agents (CWAs) in the vapor phase. The system consisted of Tri-Bed concentrator gas sampler (trapping time: 3s(-1)min), a nonpolar low thermal-mass capillary gas chromatography column capable of raising temperatures up to 200°C, a hydrophobic membrane-interfaced electron ionization quadrupole mass spectrometer evacuated by a non-evaporative getter pump for data acquisition, and a personal computer for data analysis. Sample vapors containing as little as 22μg sarin (GB), 100μg soman (GD), 210μg tabun (GA), 55μg cyclohexylsarin (GF), 4.8μg sulfur mustard, 390μg nitrogen mustard 1, 140μg of nitrogen mustard 2, 130μg nitrogen mustard 3, 120μg of 2-chloroacetophenone and 990μg of chloropicrin per cubic meter could be confirmed after Tri-Bed micro-concentration (for 1min) and automated AMDIS search within 12min. Using manual deconvolution by background subtraction of neighboring regions on the extracted ion chromatograms, the above-mentioned CWAs could be confirmed at lower concentration levels. The memory effects were also examined and we found that blister agents showed significantly more carry-over than nerve agents. Gasoline vapor was found to interfere with the detection of GB and GD, raising the concentration limits for confirmation in the presence of gasoline by both AMDIS search and manual deconvolution; however, GA and GF were not subject to interference by gasoline. Lewisite 1, and o-chlorobenzylidene malononitrile could also be confirmed by gas chromatography, but it was hard to quantify them. Vapors of phosgene, chlorine, and cyanogen chloride could be confirmed by direct mass spectrometric detection at concentration levels higher than 2, 140, and 10mg/m(3) respectively, by bypassing the micro-concentration trap and gas chromatographic separation. Copyright © 2015 Elsevier B.V. All rights reserved.

CCl 4 chemistry on the reduced selvedge of a α-Fe 2O 3(0 0 0 1) surface: a scanning tunneling microscopy study

NASA Astrophysics Data System (ADS)

Rim, Kwang Taeg; Fitts, Jeffrey P.; Müller, Thomas; Adib, Kaveh; Camillone, Nicholas; Osgood, Richard M.; Joyce, S. A.; Flynn, George W.

2003-09-01

Scanning tunneling microscopy (STM) and low energy electron diffraction (LEED) were used to study the degradation of CCl 4 on the reduced selvedge of a natural single crystal α-Fe 2O 3(0 0 0 1) surface in ultrahigh vacuum. Before exposure to CCl 4, STM images indicate that approximately 85% of the reduced surface exhibits a Fe 3O 4(1 1 1) 2 × 2 termination, while the remaining 15% is terminated by 1 × 1 and superstructure phases. Images obtained after room temperature dosing with CCl 4 and subsequent flashing to 600 K reveal that chlorine atoms are adsorbed only on surface regions with the Fe 3O 4(1 1 1) 2 × 2 termination, not on 1 × 1 and superstructure regions. Chlorine atoms from dissociative adsorption of CCl 4 are observed to occupy two distinct positions located atop lattice protrusions and in threefold oxygen vacancy sites. However, in companion chemical labeling experiments, chlorine atoms provided by room temperature, dissociative Cl 2 adsorption on this surface are found to occupy sites atop lattice protrusions exclusively. The clear dissimilarity in STM feature shape and brightness at the two distinct chlorine adsorption sites arising from CCl 4 dissociation as well as the results of the Cl 2 chemical labeling experiments are best explained via reactions on a Fe 3O 4(1 1 1) 2 × 2 selvedge terminated by a 1/4 monolayer of tetrahedrally coordinated iron atoms. On this surface, adsorption atop an iron atom occurs for both the CCl 4 and Cl 2 dissociative reactions. A second adsorption site, assigned as binding to second layer iron atoms left exposed following surface oxygen atom abstraction resulting in the formation of phosgene (COCl 2), only appears in the case of reaction with CCl 4. The reaction mechanism and active site requirements for CCl 4 degradation on iron oxide surfaces are discussed in light of this evidence and in the context of our previously reported results from Auger electron spectroscopy (AES), LEED, temperature-programmed desorption (TPD), and X-ray photoelectron spectroscopy studies.

Anatomy in the Third Reich - The Anatomical Institute of the Reichsuniversität Strassburg and the deliveries of dead bodies.

PubMed

Toledano, Raphael

2016-05-01

August Hirt (1898-1945) was director of the Institute of Anatomy of the Reichsuniversität Strassburg from November 1941 to November 1944. During this period, he was involved in many criminal activities: mustard gas experiments on prisoners of KL Natzweiler-Struthof, creating a collection of Jewish skeletons by gassing 86 Jews from KL Auschwitz in the Struthof-Natzweiler gas chamber, and involvement in experiments on phosgene gas performed by Otto Bickenbach. Extensive literature exists on these crimes. However, there has been very little work completed on the so-called normal activity of the Institute of Anatomy of which he was head and in particular the question of deliveries of corpses. We estimate that between 244 and 724 bodies were delivered to the Anatomical Institute of the Reichsuniversität Strassburg between 1942 and 1944. In the course of our investigations, we have determined the identity of 232 corpses received between 1942 and 1944, the vast majority of Soviet prisoners of war from two hospitals for prisoners of war (Strassburg and Mutzig). Other sources of dead bodies have been found, such as hospital patients and French citizens who had been executed by shooting. Most of the corpses were used for dissection by medical students, but many anatomical preparations were also made from the bodies. The bodies were buried during and after the war, but the fate of the anatomical and histological specimens is unknown. Newly discovered archival record allowed us to identify and find three jars with tissues from the 86 gassed Jews. These pieces were in the Museum of the Institute of Forensic Medicine of Strasbourg. At this point the following proposals are made: (1) opening of the Medical Faculty of Strasbourg archives, (2) creation of an historical commission, (3) identification and publication of the complete inventory of all preparations at the Strasbourg Anatomical Museum, (4) research of the fate of the dry and wet preparations made under National Socialism, (5) verification of histological slides, embryological specimens and the tissues from the institutes already existing under National Socialism, (6) verification of the pieces of the Museum of Forensic Medicine, (7) publications of these results and information of the press and (8) creation of a memorial for the victims of the NS delivered to the Institute of Anatomy. Copyright © 2016 Elsevier GmbH. All rights reserved.

Aerosol-halogen interaction: Change of physico-chemical properties of SOA by naturally released halogen species

NASA Astrophysics Data System (ADS)

Ofner, J.; Balzer, N.; Buxmann, J.; Grothe, H.; Krüger, H.; Platt, U.; Schmitt-Kopplin, P.; Zetzsch, C.

2011-12-01

Reactive halogen species are released by various sources like photo-activated sea-salt aerosol or salt pans and salt lakes. These heterogeneous release mechanisms have been overlooked so far, although their potential of interaction with organic aerosols like Secondary Organic Aerosol (SOA), Biomass Burning Organic Aerosol (BBOA) or Atmospheric Humic LIke Substances (HULIS) is completely unknown. Such reactions can constitute sources of gaseous organo-halogen compounds or halogenated organic particles in the atmospheric boundary layer. To study the interaction of organic aerosols with reactive halogen species (RHS), SOA was produced from α-pinene, catechol and guaiacol using an aerosol smog-chamber. The model SOAs were characterized in detail using a variety of physico-chemical methods (Ofner et al., 2011). Those aerosols were exposed to molecular halogens in the presence of UV/VIS irradiation and to halogens, released from simulated natural halogen sources like salt pans, in order to study the complex aerosol-halogen interaction. The heterogeneous reaction of RHS with those model aerosols leads to different gaseous species like CO2, CO and small reactive/toxic molecules like phosgene (COCl2). Hydrogen containing groups on the aerosol particles are destroyed to form HCl or HBr, and a significant formation of C-Br bonds could be verified in the particle phase. Carbonyl containing functional groups of the aerosol are strongly affected by the halogenation process. While changes of functional groups and gaseous species were visible using FTIR spectroscopy, optical properties were studied using Diffuse Reflectance UV/VIS spectroscopy. Overall, the optical properties of the processed organic aerosols are significantly changed. While chlorine causes a "bleaching" of the aerosol particles, bromine shifts the maximum of UV/VIS absorption to the red end of the UV/VIS spectrum. Further physico-chemical changes were recognized according to the aerosol size-distributions or the averaged carbon oxidation state (OSc). The heterogeneous reaction of SOA with molecular halogens released from the simulated salt-pan at different simulated environmental conditions leads to changes of several physico-chemical features of the aerosol. However, the halogen release mechanisms are also affected by the presence of organic aerosols. One order of magnitude less BrO was detected by an active Differential Optical Absorption Spectroscopy (DOAS) instrument in the presence of SOA compared to experiments without SOA. This work was supported by the German Research Foundation within the HALOPROC project. Ofner, J., Krüger, H.-U., Grothe, H., Schmitt-Kopplin, P., Whitmore, K., and Zetzsch, C. (2011), Atmos. Chem. Phys., 11, 1-15.

A combined ToF-SIMS and XPS study for the elucidation of the role of water in the performances of a Post-Plasma Process using LaMnO3+δ as catalyst in the total oxidation of trichloroethylene

NASA Astrophysics Data System (ADS)

Nuns, N.; Beaurain, A.; Dinh, M. T. Nguyen; Vandenbroucke, A.; De Geyter, N.; Morent, R.; Leys, C.; Giraudon, J.-M.; Lamonier, J.-F.

2014-11-01

LaMnO3+δ which is an environment-friendly and inexpensive material has been previously used as catalyst in Post-Plasma Catalysis (PPC) in the total oxidation of trichloroethylene (TCE) which is a solvent widely used in dry cleaning and degreasing processes. It has been shown that the process efficiency increases in moist air (RH = 18%).The issue we want to address herein is the effect of water on the location of chlorine at the surface of the catalyst as chlorine is able to alter the catalyst structure, activity and stability. Therefore, a combined Time of Flight-Secondary Ion Mass Spectrometry (ToF-SIMS) and X-ray Photoelectron Spectroscopy (XPS) study has been carried out on the fresh LaMnO3+δ catalyst (LM) and used catalysts after performing PPC with TCE diluted in dry synthetic air (LM0) or with industrial air containing water (LM18; 18 stands for the Relative Humidity) and CO2 (about 560 ppmv) at a temperature of 150 °C. XPS and ToF-SIMS results both show the presence of chlorine on the tested catalysts whose amount increases by exposure of the catalyst to the reactive mixture in dry synthetic air. XPS results reveal that chlorine is present as both chloride ion and covalent chlorine on LM0 while organic chlorinated residues are absent on LM18 catalyst. ToF-SIMS study indicates that lanthanum excess as oxide(hydroxide) partially covering the perovskite mainly transforms into LaOCl and to a minor extent into LaCl3. Extent of Mn chlorination seems to be favored over LM0 having a higher MnClx±/MnOCl± ionic ratio compared to LM18. Furthermore ToF-SIMS clearly identifies C1 chlorinated organic ions, mainly CH2Cl+ and CHCl2-, on LM0 which may contribute to the XPS Cl organic component. From the combined ToF-SIMS and XPS results it is found that water delays the surface degradation extent of the perovskite into related (oxy)(hydroxy)chlorinated inorganic phases by less molecular chlorine and related chlorine species on the catalyst surface. A reaction scheme of Cl removal over LaMnO3+δ emphasing the role of water is given taking into account the detection of ToF-SIMS ions representative of the successive Mn intermediate states. As a consequence water allows tuning the degradation pathways of the main intermediate of the reaction, dichloroacetyl chloride (DCAC), which decomposes to give phosgene, HCCl3 and CCl4 by a successive Cl incorporation over (oxy)(hydroxy)chorinated perovskite or/and Mn species while COx species are likely formed over the perovskite.