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1.
J Phys Chem A ; 112(5): 934-41, 2008 Feb 07.
Article in English | MEDLINE | ID: mdl-18186620

ABSTRACT

Vibronic optical emissions from CS(A1pi --> X1sigma+) and CS(a3pi --> X1sigma+) transitions have been identified from dissociative recombination (DR) of CS2(+) and HCS2(+) plasmas. All of the spectra were taken in flowing afterglow plasmas using an optical monochromator in the UV-visible wavelength region of 180-800 nm. For the CS(A --> X) and CS(a --> X) emissions, the relative vibrational distributions have been calculated for v' < 5 and v' < 3 in both types of plasmas for the CS(A) and CS(a) states, respectively. Both recombining plasmas show a population inversion from the v' = 0 to v' = 1 level of the CS(A) state, similar to other observations of the CS(A) state populations, which were generated using two other energetic processes. The possibility of spectroscopic cascading is addressed, such that transitions from upper level electronic states into the CS(A) and CS(a) states would affect the relative vibrational distribution, and there is no spectroscopic evidence supporting the cascading effect. Additionally, excited-state transitions from neutral sulfur (S(5S(2)0 --> 3P(2)) and S(5S(2)0 --> 3P(1))) and the products of ion-molecule reactions (CS(B1sigma+ --> A1pi), CS(+)(B2sigma+ --> A2pi(i)), and CS2(+) (A2pi(u) --> X2pi(g))) have been observed and are discussed.

2.
J Phys Chem A ; 111(29): 6760-5, 2007 Jul 26.
Article in English | MEDLINE | ID: mdl-17542564

ABSTRACT

A remeasurement of the product distribution from dissociative electron-ion recombination (DR) of N2H+ has been made using a new technique. The technique employs electron impact to ionize the neutral products prior to detection by a quadrupole mass analyzer. Two experimental approaches, both using pulsed gas techniques, isolate and quantify the DR products. In one approach, an electron-attaching gas is pulsed into a flowing afterglow to transiently quench DR. Results from this approach give an upper limit of 5% for the NH+N product channel. In the second approach, the reagent gas N2 is pulsed. The absolute percentages of products were monitored versus initial N2 concentration. Results from this approach also give an upper limit of 5% for NH+N production. This establishes that N2+H is the dominant channel, being at least between 95 and 100%, and that there is no significant NH production contrary to a recent storage ring measurement that yielded 64% NH+N and 36% N2+H. Possible reasons for this dramatic difference are discussed.

3.
Arch Environ Contam Toxicol ; 37(1): 125-34, 1999 Jul.
Article in English | MEDLINE | ID: mdl-10341050

ABSTRACT

Pilot whales strand periodically along the U.S. coast, and these strandings offer an opportunity for the collection of tissues for biomonitoring of contaminant exposure in cetaceans, as well as for specimen archiving. Concentrations of organochlorine (OC) contaminants (e.g., PCB congeners, pesticides, DDTs) were measured in tissue samples from pilot whales that stranded in 1986 and 1990 along the Massachusetts coast. Adult and fetal samples of blubber, liver, brain, and kidney were collected, as well as ovaries from mature female whales. Many of the OCs found in maternal tissues were detected in corresponding fetal tissues indicating maternal transfer of OCs to the fetus. The concentrations of individual OCs in tissues varied considerably among the animals. Statistically significant differences were found between females and males for the concentrations of certain analytes (e.g., SigmaPCBs, p,p'-DDE) and these differences may be partially due to contaminants being transferred by the female whales during gestation and lactation. The concentrations of OCs in different tissues were similar when based on total lipid weight, except for the brain, which contained the lowest lipid-normalized OC concentrations. The low concentrations in brain may be related to the disparate lipid compositions in this tissue as well as the presence of the blood-brain barrier. The availability of data on these archived and biomonitoring samples provides a baseline for future retrospective studies.


Subject(s)
Hydrocarbons, Chlorinated/metabolism , Whales/metabolism , Animals , Female , Hydrocarbons, Chlorinated/analysis , Lipids/analysis , Male , Massachusetts , Pregnancy
4.
Nat Toxins ; 6(3-4): 113-26, 1998.
Article in English | MEDLINE | ID: mdl-10223627

ABSTRACT

A bloom of the pennate diatom Pseudo-nitzschia, several species of which are associated with the production of the potent excitotoxin domoic acid, was observed in a Puget Sound, Washington embayment in July and August of 1997. Penn Cove, which receives nutrients from the nearby Skagit River and abundant sunshine during summer months due to its location in the rain shadow of the Olympic Mountains, is the home of a commercial mussel farm which supplies shellfish to many coastal areas of the USA. Levels of domoic acid in mussels increased to 3 ppm on 6 and 10 July, corresponding to the observation of a brown algal bloom in Penn Cove. Four species of Pseudo-nitzschia (P. pungens, P. multiseries, P. australis, and P. pseudodelicatissima) were present in our samples from the cove, corresponding to levels of domoic acid in seawater ranging from 0.1-0.8 mirog l(-1) as measured by a receptor binding assay. The highest Pseudo-nitzschia concentration during the time of our sampling was 13 million cells per liter on 28 July. The bloom of Pseudo-nitzschia occurred after a period of strong discharge from the Skagit River and rain accompanied by elevated south and southeasterly winds. Stratification of the cove, providing optimal bloom conditions, was facilitated by weak winds, sunshine, and a freshwater lens at the mouth of the cove. The position of the Pseudo-nitzschia bloom was influenced by buoyancy fronts caused by exchange of water within the cove with that of Saratoga Passage. The decay of this bloom in Penn Cove was accompanied by decreasing nitrate levels at all measured depths. These and future observations aid in the development of a model for prediction of toxic bloom events in the shallow embayments of Puget Sound.


Subject(s)
Diatoms , Eutrophication , Kainic Acid/analogs & derivatives , Neuromuscular Depolarizing Agents/analysis , Forecasting , Kainic Acid/analysis , Marine Toxins/analysis , Nitrates/analysis , Rain , Seasons , Shellfish , Washington
5.
Arch Environ Contam Toxicol ; 33(4): 388-400, 1997 Nov.
Article in English | MEDLINE | ID: mdl-9419257

ABSTRACT

Bioaccumulation of chlorinated hydrocarbons (CHs) from field-contaminated sediments by two infaunal invertebrates, Rhepoxynius abronius (a non-deposit feeding amphipod) and Armandia brevis (a nonselective, deposit-feeding polychaete), was examined and species responses were compared. Sediments were selected over a large geographical area of the Hudson-Raritan estuary to assess the potential for bioaccumulation from a typical urban estuary. Unlike polycyclic aromatic hydrocarbons (PAHs) from these sediments, concentrations of CHs in interstitial water (IW) indicated that partition coefficients (Koc) were generally as expected, especially when based on predicted, nonsorbed, interstitial water CH concentrations (IWfree). Correlations between amphipod and polychaete tissue residues revealed that these species were responding similarly to a gradient of CH concentrations in sediment. While tissue residues and BAFloc (lipid/organic carbon normalized bioaccumulation factor) values for the trichlorobiphenyls were similar for both species, accumulation in the polychaete was three to 10 times higher for the more hydrophobic PCBs, which was attributed to differences in the route of exposure. A negative correlation between the bioaccumulation factor (BAF) and total organic carbon (TOC) was found for both species, which was expected according to equilibrium partitioning theory. Because it was assumed that the amphipod was not feeding in these tests and the polychaete was ingesting sediment, comparison of their tissue residues and bioaccumulation factors was useful for highlighting the importance of sediment ingestion, especially for short-term, nonequilibrium exposures. These results may also help elucidate the limitations associated with assessing bioaccumulation and the resultant toxic response in standard 10-day toxicity tests with similar invertebrates.


Subject(s)
Environmental Monitoring/methods , Hydrocarbons, Chlorinated/metabolism , Invertebrates/metabolism , Polychaeta/metabolism , Soil Pollutants/metabolism , Animals , Tissue Distribution
6.
Astrophys J ; 312(1): 351-7, 1987 Jan 01.
Article in English | MEDLINE | ID: mdl-11539738

ABSTRACT

Laboratory measurements and calculations have been performed to determine the abundance ratio of the deuterated ethynyl radical (CCD) to the normal radical (CCH) which can be achieved in dense interstellar clouds via isotopic fractionation in the C2H2+ (HD) = C2HD+ (H2) system of reactions. According to this limited treatment, the CCD/CCH abundance ratio which can be attained is in the range 0.02-0.03 for the Orion molecular cloud and 0.01-0.02 for TMC-1. These ranges of numbers are in reasonable agreement with the observed values in Orion and TMC-1. However, the analysis of the CCD/CCH abundance ratio is complicated via the presence of competing fractionation mechanisms, especially in the low-temperature source TMC-1.


Subject(s)
Acetylene/chemistry , Extraterrestrial Environment , Gases/analysis , Hydrocarbons/chemistry , Carbon/chemistry , Chemical Fractionation , Free Radicals , Ions , Models, Chemical , Oxygen/chemistry
7.
Am J Occup Ther ; 35(5): 328-31, 1981 May.
Article in English | MEDLINE | ID: mdl-7246713

ABSTRACT

The Career Mobility Program provides an opportunity for certified occupational therapy assistants to become occupational therapists, registered. Data were complied about the 43 therapists who completed the program during its first 5 1/2 years. Performance on the certification examination and the candidates' educational and employment backgrounds were studied. The advantages and disadvantages of participating in the program were gathered via follow-up questionnaires. More than 70 percent of 26 reported career advancement.


Subject(s)
Career Mobility , Certification/standards , Occupational Therapy/standards , Follow-Up Studies , Humans , Internship, Nonmedical/standards
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