Atmospheric chemistry of the Z and E isomers of CF3CF=CHF; kinetics, mechanisms, and products of gas-phase reactions with Cl atoms, OH radicals, and O3.

Smog chamber/FTIR techniques were used to study the atmospheric chemistry of the Z and E isomers of CF3CF=CHF, which we refer to as CF3CF=CHF(Z) and CF3CF=CHF(E). The rate constants k(Cl + CF3CF=CHF(Z)) = (4.36 +/- 0.48) x 10-11, k(OH + CF3CF=CHF(Z)) = (1.22 +/- 0.14) x 10-12, and k(O3 + CF3CF=CHF(Z)) = (1.45 +/- 0.15) x 10-21 cm3 molecule-1 s-1 were determined for the Z isomer of CF3CF=CHF in 700 Torr air diluent at 296 +/- 2 K. The rate constants k(Cl + CF3CF=CHF(E)) = (5.00 +/- 0.56) x 10-11, k(OH + CF3CF=CHF(E)) = (2.15 +/- 0.23) x 10-12, and k(O3 + CF3CF=CHF(E)) = (1.98 +/- 0.15) x 10-20 cm3 molecule-1 s-1 were determined for the E isomer of CF3CF=CHF in 700 Torr air diluent at 296 +/- 2 K. Both the Cl-atom and OH-radical-initiated atmospheric oxidation of CF3CF=CHF give CF3C(O)F and HC(O)F in molar yields indistinguishable from 100% for both the Z and E isomer. CF3CF=CHF(Z) has an atmospheric lifetime of approximately 18 days and a global warming potential (100 year time horizon) of approximately 6. CF3CF=CHF(E) has an atmospheric lifetime of approximately 10 days and a global warming potential (100 year time horizon) of approximately 3. CF3CF=CHF has a negligible global warming potential and will not make any significant contribution to radiative forcing of climate change.

Atmospheric chemistry of a model biodiesel fuel, CH3C(O)O(CH2)2OC(O)CH3: kinetics, mechanisms, and products of Cl atom and OH radical initiated oxidation in the presence and absence of NOx.

Relative rate techniques were used to study the kinetics of the reactions of Cl atoms and OH radicals with ethylene glycol diacetate, CH3C(O)O(CH2)2OC(O)CH3, in 700 Torr of N2/O2 diluent at 296 K. The rate constants measured were k(Cl + CH3C(O)O(CH2)2OC(O)CH3) = (5.7 +/- 1.1) x 10(-12) and k(OH + CH3C(O)O(CH2)2OC(O)CH3) = (2.36 +/- 0.34) x 10(-12) cm3 molecule-1 s-1. Product studies of the Cl atom initiated oxidation of ethylene glycol diacetate in the absence of NO in 700 Torr of O2/N2 diluent at 296 K show the primary products to be CH3C(O)OC(O)CH2OC(O)CH3, CH3C(O)OC(O)H, and CH3C(O)OH. Product studies of the Cl atom initiated oxidation of ethylene glycol diacetate in the presence of NO in 700 Torr of O2/N2 diluent at 296 K show the primary products to be CH3C(O)OC(O)H and CH3C(O)OH. The CH3C(O)OCH2O* radical is formed during the Cl atom initiated oxidation of ethylene glycol diacetate, and two loss mechanisms were identified: reaction with O2 to give CH3C(O)OC(O)H and alpha-ester rearrangement to give CH3C(O)OH and HC(O) radicals. The reaction of CH3C(O)OCH2O2* with NO gives chemically activated CH3C(O)OCH2O* radicals which are more likely to undergo decomposition via the alpha-ester rearrangement than CH3C(O)OCH2O* radicals produced in the peroxy radical self-reaction.

Atmospheric chemistry of n-C(x)F(2)(x)(+1)CHO (x = 1, 2, 3, 4): fate of n-C(x)F(2)(x)(+1)C(O) radicals.

Smog chamber/FTIR techniques were used to study the atmospheric fate of n-C(x)F(2)(x)(+1)C(O) (x = 1, 2, 3, 4) radicals in 700 Torr O(2)/N(2) diluent at 298 +/- 3 K. A competition is observed between reaction with O(2) to form n-C(x)()F(2)(x)()(+1)C(O)O(2) radicals and decomposition to form n-C(x)F(2)(x)(+1) radicals and CO. In 700 Torr O(2)/N(2) diluent at 298 +/- 3 K, the rate constant ratio, k(n-C(x)F(2)(x)(+1)C(O) + O(2) --> n-C(x)F(2)(x)(+1)C(O)O(2))/k(n-C(x)F(2)(x)(+1)C(O) --> n-C(x)F(2)(x)(+1) + CO) = (1.30 +/- 0.05) x 10(-17), (1.90 +/- 0.17) x 10(-19), (5.04 +/- 0.40) x 10(-20), and (2.67 +/- 0.42) x 10(-20) cm(3) molecule(-1) for x = 1, 2, 3, 4, respectively. In one atmosphere of air at 298 K, reaction with O(2) accounts for 99%, 50%, 21%, and 12% of the loss of n-C(x)F(2)(x)(+1)C(O) radicals for x = 1, 2, 3, 4, respectively. Results are discussed with respect to the atmospheric chemistry of n-C(x)F(2)(x)(+1)C(O) radicals and their possible role in contributing to the formation of perfluorocarboxylic acids in the environment.

Atmospheric chemistry of 4:2 fluorotelomer alcohol (n-C4F9CH2CH2OH): products and mechanism of Cl atom initiated oxidation in the presence of NOx.

Smog chamber/FTIR techniques were used to study the Cl atom initiated oxidation of 4:2 fluorotelomer alcohol (C(4)F(9)CH(2)CH(2)OH, 4:2 FTOH) in the presence of NO(x) in 700 Torr of N(2)/O(2) diluent at 296 K. Chemical activation effects play an important role in the atmospheric chemistry of the peroxy, and possibly the alkoxy, radicals derived from 4:2 FTOH. Cl atoms react with C(4)F(9)CH(2)CH(2)OH to give C(4)F(9)CH(2)C(*)HOH radicals which add O(2) to give chemically activated alpha-hydroxyperoxy radicals, [C(4)F(9)CH(2)C(OO(*))HOH]*. In 700 Torr of N(2)/O(2) at 296 K, approximately 50% of the [C(4)F(9)CH(2)C(OO(*))HOH]* radicals decompose "promptly" to give HO(2) radicals and C(4)F(9)CH(2)CHO, the remaining [C(4)F(9)CH(2)C(OO(*))HOH]* radicals undergo collisional deactivation to give thermalized peroxy radicals, C(4)F(9)CH(2)C(OO(*))HOH. Decomposition to HO(2) and C(4)F(9)CH(2)CHO is the dominant atmospheric fate of the thermalized peroxy radicals. In the presence of excess NO, the thermalized peroxy radicals react to give C(4)F(9)CH(2)C(O(*))HOH radicals which then decompose at a rate >2.5 x 10(6) s(-1) to give HC(O)OH and the alkyl radical C(4)F(9)CH(2)(*). The primary products of 4:2 FTOH oxidation in the presence of excess NO(x) are C(4)F(9)CH(2)CHO, C(4)F(9)CHO, and HCOOH. Secondary products include C(4)F(9)CH(2)C(O)O(2)NO(2), C(4)F(9)C(O)O(2)NO(2), and COF(2). In contrast to experiments conducted in the absence of NO(x), there was no evidence (<2% yield) for the formation of the perfluorinated acid C(4)F(9)C(O)OH. The results are discussed with regard to the atmospheric chemistry of fluorotelomer alcohols.

The formation of reactive oxygen species catalyzed by neutral, aqueous extracts of NIST ambient particulate matter and diesel engine particles.

It is important to characterize the chemical properties of particulate matter in order to understand how low doses, inhaled by a susceptible population, might cause human health effects. The formation of reactive oxygen species catalyzed by neutral, aqueous extracts of two ambient particulate samples, National Institute of Standards & Technology (NIST) Standard Reference Materials (SRM) 1648 and 1649, and two diesel particulate samples, NIST SRM 1650 and SRM 2975, were measured. The formation of reactive oxygen species was estimated by measuring the formation of malondialdehyde from 2-deoxyribose in the presence of ascorbic acid; H2O2 was not added to this assay. SRM 1649, ambient particulate matter collected from Washington, DC, generated the most malondialdehyde, while SRM 2975, diesel particulate matter collected from a forklift, yielded the least amount. Desferrioxamine inhibited the formation of malondialdehyde from the particulate samples providing additional data to support the observation that transition metals were involved in the generation of reactive oxygen species. Six transition metal sulfates (iron sulfate, copper sulfate, vanadyl sulfate, cobalt sulfate, nickel sulfate, and zinc sulfate) were assayed for their ability to generate reactive oxygen species under the same conditions used for the particulate samples in order to facilitate comparisons between particles and these transition metals. The concentration of transition metals was measured in aqueous extracts of these particulate samples using ion-coupled plasma mass spectrometry (ICP-MS) analysis. There was qualitative agreement between the concentrations of Fe, Cu, and V and the amount of malondialdehyde produced from extracts of these particulate samples. These data suggest that transition metals can be dissolved from particles in neutral, aqueous solutions and that these metals are capable of catalyzing the formation of reactive oxygen species.

Sonoelectrochemical and sonochemical effects of cavitation: correlation with interfacial cavitation induced by 20 kHz ultrasound.

Sonoelectrochemical measurements at macro-electrodes under extreme conditions with a very short distance between ultrasonic horn tip and electrode and different ultrasound intensity levels are shown to result in violent cavitation detected in form of current peaks superimposed on the average limiting current. Analysis of the current data obtained for the oxidation of ferrocene in dimethylformamide (0.1 M NBu4PF6) at a 4 mm diameter Pt disc electrode and for the reduction of Ru(NH3)6(3+) in aqueous 0.1 M KCl at a 6 mm diameter Pt disc electrode consistently indicate a change of the physicochemical nature of sonoelectrochemical processes under extreme conditions. The sonoelectrochemical measurement of the rate constant for the carbon bromide bond cleavage of a 3-bromobenzophenone radical anion electrogenerated at a glassy carbon electrode in dimethylformamide solution in the presence of power ultrasound is shown to yield evidence for a breakdown of the conventional mass transport model of a planar diffusion layer under extreme conditions. The change can be correlated to the number of current data points deviating more than 10% from the mean of the current due to violent cavitation processes superimposed onto the average limiting current. Further, a study of the sonochemical destruction of aqueous dilute cyanide solution (in 0.1 M NaOH) demonstrates a correlation between the electrochemically detected cavitation violence and the sonochemical activity. Factors that govern the violence of interfacial cavitation appear to be directly proportional to the factors that make cavitation in the bulk solution chemically efficient.

Why has it proved so difficult to match drug abuse patients to appropriate treatment?

Why has it proved so difficult to match drug abuse patients to appropriate treatment? In seeking answers to this dilemma, attention is directed to the conceptual, semantic, substantive, methodological, political and cultural issues which need to be resolved. In particular, the lack of knowledge about the treatment domain as well as the corresponding dearth of instruments to measure program characteristics and the delivery of treatment services is noted. Although the importance of demographic and cultural determinants of both patient and treatment characteristics seems evident, numerous conceptual issues persist. Is matching patients to treatment and rehabilitation a one-time event or a process? Is matching a simplistic concept? It is suggested that the principal questions to be resolved about matching drug abuse patients to treatment and rehabilitation are conceptual, or theoretical.

Detection of oxidative mutagens in an urban air-particulate extract: a preliminary study.

The Ames assays strains TA98 and TA100 have been useful in characterizing complex mixtures from organic solvent extracts of particles from diesel-powered vehicles, ambient air, and other sources. In this paper we report preliminary experiments using TA102, a bacterial strain that detects compounds that can oxidize DNA, to characterize the mutagenicity of an ambient air sample collected in Ann Arbor, MI. Four sets of ambient air filters were collected in duplicate over a period of several days. The mutagenicities of methylene chloride extracts of these filters were compared using strains TA98, TA100 and TA102. The concentration-mutagenicity data for TA98 and TA100 were linear over the concentration range 0-200 micrograms extract/plate. The mutagenicity of the extracts using TA102 was much lower than the other two strains and was non-linear over the concentration range tested. These results suggest that it would be difficult to use TA102 to identify the oxidative mutagens present in an ambient air particulate extract.

Solvent extraction efficiencies of mutagenic components from diesel particles.

In order to determine the efficiency of organic solvent extractions of fresh diesel-engine exhaust particles a series of Soxhlet extractions were set up using single and sequential extractions of fresh diesel particles with solvents of increasing polarities. Single extractions were carried out with methylene chloride, methanol, acetone and acetonitrile. A single filter was sequentially extracted with methylene chloride followed by methanol, acetone and acetonitrile. Methylene chloride extracted the most mutagenicity relative to the other three solvents. In addition, methylene chloride extracted 97% of the total extracted mutagenicity from a sequential series of extractions. Therefore, we conclude that of the solvents tested methylene chloride extracts the highest proportion of mutagens from fresh diesel exhaust and little mutagenicity is lost using methylene chloride as the only extraction solvent.

Followup study of possible HIV seropositivity among abusers of parenteral drugs in 1971-72.

Serum specimens obtained from a nationwide sample of parenteral drug abusers (PDAs) during the period 1971-72 had previously been screened for human immunodeficiency virus (HIV) antibodies. Some specimens were considered to be positive to both ELISA and Western blot (WB) analysis. These findings have been a topic of controversy, since HIV was not thought to have penetrated at-risk populations at such an early date. This study was a followup of those PDAs with apparent seropositivity to WB analysis. Of 10 persons followed, only one death (in 1985) was documented, and postmortem findings were inconsistent with HIV infection. Eight of the remaining PDAs were traced and found to be alive and well in 1989. Fresh specimens were obtained from the two persons with the strongest 1971-72 WB staining and were found to be both ELISA and WB negative on retesting. Their T-cell parameters were within normal limits. We concluded that the earlier WB results were most likely false positives and that definitive evidence of HIV infection in the U.S. addict population as early as 1971-72 is still lacking.

Ames assay mutagenicity and electronic structure calculations of bromomethylfluoranthenes, chloromethylfluoranthenes, and hydroxymethylfluoranthenes.

The mutagenicities of the five possible isomers of bromomethylfluoranthene, chloromethylfluoranthene, and hydroxymethylfluoranthene were determined in the Ames assay using strains TA100 and TA98 without the addition of rat-liver S9 tissue extract. The mutagenicities of the bromomethyl and chloromethylfluoranthenes ranged from 25 to 6000 rev./nmol. The most mutagenic compound was 8-chloromethylfluoranthene in strain TA98 (6000 rev./nmol). The reactivities of the bromomethylfluoranthenes and the chloromethylfluoranthenes were estimated from electronic structure calculations using the MNDO and the PM3 semi-empirical methods. The bromomethylfluoranthenes showed the smallest differences between the heats of formation of the carbocations and the heats of formation of the parent bromomethyl derivatives. Therefore, the bromomethylfluoranthenes were estimated to be the most reactive of the halomethylfluoranthenes studied. The compound that showed the largest change in heat of formation (the most stable halomethylfluoranthene) going from the halomethylfluoranthene to the carbocation was 2-chloromethylfluoranthene. However, neither the most reactive nor the most stable halomethylfluoranthenes were the most mutagenic in either strain of bacteria. These results are interpreted to suggest that the reactivity of the parent halomethylfluoranthene is not a critical factor in the mechanism by which these compounds are mutagenic, but some other factor, perhaps intercalation, must be a critical step in the mechanism of mutagenesis of these compounds.

A treatment crisis: cocaine use by clients in methadone maintenance programs.

We surveyed 11 methadone maintenance treatment programs in the Baltimore, Maryland, area to examine cocaine use among their 2414 clients and the methods employed to cope with that use. The percent of clients with at least one urine sample positive for cocaine during the month previous to study was 15.7% (379/2414) and ranged from 5.9% to 33.0% among the 11 programs. We determined the programs' use of monitoring strategies, treatment services, and administrative controls. We discuss the policy implications of our findings for methadone maintenance programs' efforts to address cocaine use with particular regard to the epidemic of human immunodeficiency virus (HIV) among intravenous drug users, their sexual partners, and offspring.

MNDO calculations of highly mutagenic (chloromethyl)benzo[a]pyrenes.

(Chloromethyl)benzo[a]pyrenes (ClMeB[a]P) are among the most potent direct-acting mutagens (i.e., not requiring metabolic activation) detected by the Ames assay using strain TA98 and TA100. We wanted to determine if molecular quantum mechanics would yield insights into the reactivity and mutagenicity of these compounds. Calculations using the MNDO semiempirical method (MOPAC program) were carried out on a series of ClMeB[a]P. The experimental rates of solvolysis of ClMeB[a]P in 50% aqueous acetone correlated well (r = -0.95) with the differences between the calculated heats of formation of ClMeB[a]P and those of their respective carbocations, supporting the hypothesis that ClMeB[a]P react via carbocations. None of the calculated parameters correlated with mutagenicity. Thus, the prediction of mutagenicity of ClMeB[a]P in the Ames assay is more complex than the simple formation of carbocation intermediates.

The Lexington addicts, 1971-1972: demographic characteristics, drug use patterns, and selected infectious disease experience.

The demographics, drug habits, and medical complications of a cohort of 1,129 addicts treated at Lexington in the period 1971-1972 were studied. These patients, admitted from 41 different states, had a mean period of addiction of 5.4 years. Over one-third of the sample had engaged in pimping or prostitution, and there were no differences by gender in terms of involvement. Eight-eight percent had shared injection equipment, and surprisingly, 78% admitted to some effort at sterilizing their "works." Hepatitis was the most common associated medical condition: 87% had serologic markers of hepatitis B virus (HBV) infection, 60% had evidence of hepatitis A virus (HAV) exposure, and 47% had abnormal liver function parameters. Gynecomastia was evident in 2% of male subjects. Thirteen percent of the sample had a reactive VDRL assay, but 64% of these were biologically false positive. Subtle abnormalities of immune function were also observed; 18% of the patients had recent unexplained weight loss, 6% had lymphadenopathy, 8% had leukopenia, and 2% had lymphocytopenia. We conclude that both HBV and HAV were important infectious disease risks in these addicts, and that many evidenced deficiencies in immune function well before AIDS became a major public health concern.