PubMed · 5271417
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P Calmettes. 1970. [Compressors].. https://pubmed.ncbi.nlm.nih.gov/5271417/
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As part of the Atmospheric Exchange Over Lakes and Oceans Study (AEOLOS), air-water exchange fluxes of polychlorinated biphenyls (PCBs) were determined along a transect in the Baltimore Harbor from the Inner Harbor of Baltimore, MD, to the mainstem of the northern Chesapeake Bay to assess the overall contributions of urban source PCBs through air-water exchange and their impacts on coastal waters. Six sites were sampled during three intensive sampling periods in June 1996, February 1997, and July 1997 and at two sites (urban and rural) every ninth day between March 1997 and March 1998 to measure spatial and temporal variability in the PCB air-water exchange fluxes. During the intensive sampling campaigns, net total PCB (t-PCBs) volatilization fluxes ranged between 5 and 2120 ng m(-2) day(-1), varying on both temporal and spatial scales. Volatilization fluxes were highest in February, driven by high winds and elevated dissolved PCB concentrations. Throughout the annual sampling period, t-PCB volatilization fluxes were similar between urban (130 microg m(-2) yr(-1)) and rural (120 microg m(-2) yr(-1)) sites. Approximately 10% of the dissolved t-PCB inventory in the water column in Baltimore Harbor exchanges with the atmosphere each day. From air-water exchange alone, the estimated residence time of dissolved t-PCBs in the harbor is approximately 10 days (estimated hydraulic residence time of water in the harbor is between 7 and 14 days), indicating that air-water exchange is an efficient removal mechanism of t-PCBs from urban coastal waters. Furthermore, the annual flux of t-PCBs volatilizing from Baltimore Harbor is approximately 12% of the gas-phase t-PCB inventory over the water, and at the northern Chesapeake Bay site, the t-PCB flux is approximately 40% of the gas-phase t-PCB inventory. This suggests that air-water exchange of t-PCBs has the potential to be a significant source of PCBs to the rural atmosphere.
The kinetics of amide bond formation in a monolayer film has been studied by proton NMR spectroscopy. Compression of a hexadecyl thioester of N-acetyl glycine (1) and a hexadecyl amide of glycine (2) at the air-water interface produces a single dipeptide product (4) that remains at the surface once formed. Extraction of the reaction mixture from the interface, followed by (1)H NMR spectroscopy, provides quantitative data on the rate of product formation. The kinetics of this reaction was examined as a function of surface pressure, subphase pH, and temperature. The monolayer provides an effective molarity for the reaction of approximately 500 M as compared to the bimolecular reaction of 1 and 4 in chloroform solution. The first-order rate constant for the reaction of 1 and 2 in the monolayer is less than 70-fold slower than k(cat) for condensation of the first amide bond in the enzymatic synthesis of the cyclic antibiotic gramicidin S by gramicidin S synthetase. Activation energies of the reaction were extracted from the temperature dependence of the rate constants of the reaction and are 9.9 +/- 1.0 and 2.1 +/- 0.2 kcal/mol for the chloroform solution and monolayer reactions, respectively. The pK(a) of 2 in the monolayer was estimated to be approximately 0.5 pK(a) units lower than that of related amines in solution. The lower pK(a) at the interface as compared to that in solution may be ascribed to increased electrostatic repulsion at the interface relative to solution. The rate of reaction in the monolayer was also followed by monitoring changes in surface area as a function of time. The rate constant for the reaction of 1 and 4 as determined by changes in surface area differs significantly from the rate determined by NMR. The results indicate that measurements of surface area versus time may yield erroneous rate constants for reactions in monolayers.
A new international Code of Practice for radiotherapy dosimetry co-sponsored by several international organizations has been published by the IAEA, TRS-398. It is based on standards of absorbed dose to water, whereas previous protocols (TRS-381 and TRS-277) were based on air kerma standards. To estimate the changes in beam calibration caused by the introduction of TRS-398, a detailed experimental comparison of the dose determination in reference conditions in high-energy photon and electron beams has been made using the different IAEA protocols. A summary of the formulation and reference conditions in the various Codes of Practice, as well as of their basic data, is presented first. Accurate measurements have been made in 25 photon and electron beams from 10 clinical accelerators using 12 different cylindrical and plane-parallel chambers, and dose ratios under different conditions of TRS-398 to the other protocols determined. A strict step-by-step checklist was followed by the two participating clinical institutions to ascertain that the resulting calculations agreed within tenths of a per cent. The maximum differences found between TRS-398 and the previous Codes of Practice TRS-277 (2nd edn) and TRS-381 are of the order of 1.5-2.0%. TRS-398 yields absorbed doses larger than the previous protocols, around 1.0% for photons (TRS-277) and for electrons (TRS-381 and TRS-277) when plane-parallel chambers are cross-calibrated. For the Markus chamber, results show a very large variation, although a fortuitous cancellation of the old stopping powers with the ND,w/NK ratios makes the overall discrepancy between TRS-398 and TRS-277 in this case smaller than for well-guarded plane-parallel chambers. Chambers of the Roos-type with a 60Co ND,w calibration yield the maximum discrepancy in absorbed dose, which varies between 1.0% and 1.5% for TRS-381 and between 1.5% and 2.0% for TRS-277. Photon beam calibrations using directly measured or calculated TPR20,10 from a percentage dose data at SSD = 100 cm were found to be indistinguishable. Considering that approximately 0.8% of the differences between TRS-398 and the NK-based protocols are caused by the change to the new type of standards, the remaining difference in absolute dose is due either to a close similarity in basic data or to a fortuitous cancellation of the discrepancies in data and type of chamber calibration. It is emphasized that the NK-ND,air and ND,w formalisms have very similar uncertainty when the same criteria are used for both procedures. Arguments are provided in support of the recommendation for a change in reference dosimetry based on standards of absorbed dose to water.