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At least 73 records · Page 4

The use of multiple indices of physiological activity to access viability in chlorine disinfected Escherichia coli O157:H7

A suite of fluorescent intracellular stains and probes was used, in conjunction with viable plate counts, to assess the effect of chlorine disinfection on membrane potential (rhodamine 123; Rh123 and bis-(1,3-dibutylbarbituric acid) trimethine oxonol; DiBAC4(3)), membrane integrity (LIVE/DEAD BacLight kit), respiratory activity (5-cyano-2,3-ditolyl tetrazolium chloride; CTC) and substrate responsiveness (direct viable counts; DVC) in the commensal pathogen Escherichia coli O157:H7. After a 5 min exposure to the disinfectant, physiological indices were affected in the following order: viable plate counts > substrate responsiveness > membrane potential > respiratory activity > membrane integrity. In situ assessment of physiological activity by examining multiple targets, as demonstrated in this study, permits a more comprehensive determination of the site and extent of injury in bacterial cells following sublethal disinfection with chlorine. This approach to assessing altered bacterial physiology has application in various fields where detection of stressed bacteria is of interest.

NASA Discipline Environmental Health↗

Nighttime OClO in the Winter Arctic Vortex

We show that a nighttime profile of OClO in the Arctic vortex during the winter of 2000 is overestimated, by nearly a factor of 2, using an isentropic trajectory model constrained by observed profiles of ClOx (ClO + 2 X ClOOCl) and BrO. Calculated abundances of nighttime OClO are shown to be sensitive to the abundance of BrOx (BrO + BrCl), details of the air parcel history during the most recent sunrise/sunset transitions, and the BrCl yield from the reaction BrO + ClO. Many uncertainties are considered, and the discrepancy between measured and modeled nighttime OClO appears to be robust. This discrepancy suggests that production of OClO occurs more slowly than implied by standard photochemistry. If the yield of BrCl from the reaction of BrO + ClO is increased from 7% (JPL 2002 value) to 11% (near the upper limit of the uncertainty), good agreement is found between measured and modeled nighttime OClO. This study highlights the importance of accurate knowledge of BrO + ClO reaction kinetics as well as air parcel trajectories for proper interpretation of nighttime OClO. These factors have a considerably smaller impact on the interpretation of OClO observations obtained during twilight (90(deg) <=SZA <= 92(deg)), when photolytic processes are still active.

chlorine activation↗

Composition measurements of the 1989 Arctic winter stratosphere by airborne infrared solar absorption spectroscopy

The paper reports simultaneous measurements of the stratospheric burdens of H2O, HDO, OCS, CO2, O3, N2O, CO, CH4, CF2Cl2, CFCl3, CHF2Cl, C2H6, HCN, NO, NO2, HNO3, ClNO3, HOCl, HCl, and HF made by the JPL MkIV interferometer on board the NASA DC-8 aircraft during January and early February 1989 as part of the Airborne Arctic Stratosphere Experiment. Data were obtained on 11 flights at altitudes of up to 12 km over a geographic region covering the NE Atlantic Ocean, Iceland, and Greenland. Analyses of the chemically active gases reveal highly perturbed conditions within the vortex. The ClNO3 abundance was chemically enhanced near the edge of the vortex but was then depleted inside. NO2 was severely depleted inside the vortex. In contrast to Antarctica, H2O and HNO3 were both more abundant inside the vortex than outside. It is suggested that although the Arctic vortex did not get cold enough to produce any dehydration, or as vertically extensive denitrification as occurred in Antarctica, nevertheless, enough heterogeneous chemistry occurred to convert over 90 percent of the inorganic chlorine to active forms in the 14- to 27-km altitude range by early February 1989.

Toon, G. C.↗

Rechargeable Al/Cl2 battery with molten AlCl4/-/ electrolyte.

A molten salt system based on Al- and Cl2 carbon electrodes, with an AlCl3 alkali chloride eutectic as electrolyte, offers promise as a rechargeable, high energy density battery which can operate at a relatively low temperature. Electrode kinetic studies showed that the electrode reactions at the Al anode were rapid and that the observed passivation phenomena were due to the formation at the electrode surface of a solid salt layer resulting from concentration changes on anodic or cathodic current flow. It was established that carbon electrodes were intrinsically active for chlorine reduction in AlCl3-alkali chloride melts. By means of a rotating vitreous carbon disk electrode, the kinetic parameters were determined.

Holleck, G. L.↗

Calculations of ozone destruction during the 1988/89 Arctic winter

Calculations of ozone depletion during the 1988/89 Arctic winter using a Lagrangian coupled photochemical-microphysical model are presented. Abundances of ClO in excess of 1 ppbv were observed at the end of the Airborne Arctic Stratospheric Expedition on February 10, 1989. These are shown to be consistent with the removal of more than 90 percent of the reactive nitrogen and the conversion of more than 80 percent of reservoir chlorine to active forms. This chemical state implies that ozone losses of more than 20 ppbv/day can be sustained in heavily denitrified air throughout much of February according to current photochemistry. As much as 74 percent of the loss is calculated to be due to ClO dimer photolysis. Following the warming of the vortex in mid-February 1989, ozone loss through ClO dimer photolysis becomes less effective as the rate of thermal decomposition of the ClO dimer increases. Thus, model results suggest that thermal decomposition of the dimer plays an important role in limiting ozone loss in the Arctic spring.

Mckenna, D. S.↗

Heterogeneous Chemistry Related to Stratospheric Aircraft

Emissions from stratospheric aircraft that may directly or indirectly affect ozone include NO(y), H2O, soot and sulfuric acid. To fully assess the impact of such emissions, it is necessary to have a full understanding of both the homogeneous and heterogeneous transformations that may occur in the stratosphere. Heterogeneous reactions on stratospheric particles play a key role in partitioning ozone-destroying species between their active and reservoir forms. In particular, heterogeneous reactions tend to activate odd chlorine while deactivating odd nitrogen. Accurate modeling of the net atmospheric effects of stratospheric aircraft requires a thorough understanding of the competing effects of this activation/deactivation. In addition, a full understanding of the potential aircraft impacts requires that the abundance, composition and formation mechanisms of the particles themselves be established. Over the last three years with support from the High Speed Research Program, we have performed laboratory experiments to determine the chemical composition, formation mechanism, and reactivity of stratospheric aerosols.

Tolbert, Margaret A.↗

Simulating Observed Ozone Loss in the Northern Hemisphere Winter

Ozone amounts observed at high Northern latitudes in late winter and early spring have been relatively very low in four of the last six years. On the face of it, this decline appears similar to that observed in the Antarctic in the mid-1980s in spite of the fact that the abundance of stratospheric chlorine is currently steady or decreasing. In order to predict the extent to which this change represents a trend, and to understand what combination of factors produces the low ozone, we need to accurately simulate these observations with models. In this presentation, we focus on the winter of 1999-2000, which exhibited some of the lowest ozone ever recorded in the Northern hemisphere. It also contained the largest-ever assembled set of atmospheric measurements and modeling activities in the SAGE III Ozone Loss and Validation Experiment/Third European Stratospheric Experiment on Ozone (SOLVE/THESEO). We use SOLVE/THESEO observations in comparison with the Goddard 3-D global model of stratospheric chemistry and transport to explore the model's capability to simulate the evolution of ozone and other species through the winter. We will discuss advective transport and mixing, chlorine activation, and denitrification, which are key processes to accurately simulating wintertime ozone. Preliminary results show that, although the model tracer transport and chlorine activation compare relatively well with observations, the magnitude of observed ozone loss is difficult to achieve in the model. Calculated ozone loss is sensitive to denitrification, which presents a major challenge to parameterization in a global model. Simulation requirements and uncertainties will be evaluated.

Kawa, S. R.↗

Sulfur, Chlorine, and Flourine Degassing and Atmospheric Loading by the 1783 - 1784 AD Laki (Skaftar Fires) Eruption in Iceland

The 1783-1784 Laki tholeiitic basalt fissure eruption in Iceland was one of the greatest atmospheric pollution events of the past 250 years, with widespread effects in the northern hemisphere. The degassing history and volatile budget of this event are determined by measurements of pre-eruption and residual contents of sulfur, chlorine, and fluorine in the products of all phases of the eruption. In fissure eruptions such as Laki, degassing occurs in two stages: by explosive activity or lava fountaining at the vents, and from the lava as it flows away from the vents. Using the measured sulfur concentrations in glass inclusions in phenocrysts and in groundmass glasses of quenched eruption products, we calculate that the total accumulative atmospheric mass loading of sulfur dioxide was 122 Mt over a period of 8 months. This volatile release is sufficient to have generated approximately 250 Mt of H2SO4 aerosols, an amount which agrees with an independent estimate of the Laki aerosol yield based on atmospheric turbidity measurements. Most of this volatile mass (approximately 60 wt.%) was released during the first 1.5 months of activity. The measured chlorine and fluorine concentrations in the samples indicate that the atmospheric loading of hydrochloric acid and hydrofluoric acid was approximately 7.0 and 15.0 Mt, respectively. Furthermore, approximately 75% of the volatile mass dissolved by the Laki magma was released at the vents and carried by eruption columns to altitudes between 6 and 13 km. The high degree of degassing at the vents is attributed to development of a separated two-phase flow in the upper magma conduit, and implies that high-discharge basaltic eruptions such as Laki are able to loft huge quantities of gas to altitudes where the resulting aerosols can reside for months, or even 1-2 years. The atmospheric volatile contribution due to subsequent degassing of the Laki lava flow is only 18 wt.% of the total dissolved in the magma, and these emissions were confined to the lowest regions of the troposhere and therefore important only over Iceland. This study indicates that determination of the amount of sulfur degassed from the Laki magma batch by measurements of sulfur in the volcanic products (the petrologic method) yields a result which is sufficient to account for the mass of aerosols estimated by other methods.

Thordarson, T.↗

Detection of Polar Stratospheric Clouds Using AVHRR Imagery

In recent years, the role of PSCs in the ozone depletion process has become better understood. PSCs provide the surfaces upon which heterogeneous reactions take place that affect the gas phase partitioning between active and reservoir chlorine and nitrogen species. Present methods of PSC detection include in situ measurements by lidar and various satellite-borne instruments such as the Stratospheric Aerosol Measurement II (SAM II) on the Nimbus 7 spacecraft, which produced PSC measurements from 1978 to 1994 and several instruments onboard the Upper Atmospheric Research Satellite (UARS) such as the Cryogenic Limb Array Etalon Spectrometer (CLAES) which provided measurements for 1991-1993. All of the PSC-detection methods devised so far have been hampered by incomplete sampling of the places and times in which PSCs are likely to form. There is a need to understand the climatology of PSCS, in particular the timing of their onset and duration, their vertical distribution, geographic extent, annual variability and responses to volcanic aerosol forcing. Poole and Pitts [1994] assembled a PSC climatology based on SAM II data, but this climatology is incomplete, as it is limited to the edge of the polar night due to the limitations of the solar occultation scan geometry. The Advanced Very High Resolution Radiometer (AVHRR) five- channel sensors onboard the NOAA polar-orbiting satellites have been collecting data over the polar regions continuously since 1979. These operational satellites provide unmatched coverage in space and time of both polar regions, but were not designed for the detection of optically-thin PSCS. However, the AVHRR data archive would be an invaluable source for the construction of a long-term climatology of PSCs if techniques can be developed and tested to detect PSCs in AVHRR data. In the last few years, the members of our group at San Francisco State University and NASA Ames Research Center have been engaged in the development of various PSC detection methods using AVHRR data. There is strong evidence that a subset of PSCS, those that are optically thick, can be readily identified in the AVHRR data set. Our group has also made significant progress in the identification of optically thinner PSCs using a variety of techniques.

Garcia, Oswaldo↗

Adaptative Site Management for a 115 Acre Chlorinated Solvent Plume with Two Separate Source Areas at Kennedy Space Center, Florida

Background/Objectives. During Resource Conservation and Recovery Act (RCRA) Facility Investigation (RFI) activities, Geosyntec delineated a chlorinated volatile organic compound (CVOC) plume at the National Aeronautics and Space Administration’s (NASA’s) Vehicle Assembly Building (VAB) area located at KSC, Florida. The RFI activities identified an approximate 115-acre dissolved plume (primarily vinyl chloride) and a trichloroethene (TCE) source area in an active aerospace complex that is surrounded by sensitive wetland/waterbodies. Due to the size of the impacted area, the Corrective Measure Design included a multi-component strategy: (i) address the source area via bioremediation; (ii) protect sensitive wetlands from impacted groundwater discharge via biosparging; and (iii) Long Term Monitoring (LTM) of the remaining dissolved plume. After the Corrective Measures implementation (CMI), NASA and Geosyntec worked with Florida Department of Environmental Protection (FDEP) to implement an adaptive site management for the complex, 115-acre site outside of the traditional RCRA process. The adaptive site management approach relied on performing supplemental assessments and implementing Interim Measures (IMs) to further assess and implement remedies over time while working within site and budget constraints, with an overall goal of achieving enough mass reduction to transition the entire site to LTM and eventually achieve site closure. Approach/Activities. After the biosparge barrier was operational and bioremediation within the source area (referred to as Hot Spot 1) achieved the Corrective Action Objective (CAO), supplemental assessment of the area between Hot Spot 1 and the biosparge barrier was performed. The conceptual site model was updated using the supplemental assessment results and an air sparge system IM was designed to treat an approximate 1.2 acre area (referred to as Hot Spot 2). After installation of the air sparge system, supplemental assessment within the remainder of the 115-acre dissolved plume was performed and a second TCE source area was identified. The TCE source area and associated areas with elevated CVOC concentrations (referred to as Hot Spot 3) were delineated and a bioremediation IM was implemented. Also, the downgradient impacts from Hot Spot 3 were adjacent to a sensitive waterbody, and negotiations with the FDEP allowed the area to be monitored using LTM. Results/Lessons Learned. The performance of supplemental assessment activities and implementation of remedial alternatives as IMs allowed NASA to successfully address groundwater impacts over time, while working within the FDEP regulatory framework. The implementation of the CMI and multiple IMs has achieved the following goals: (i) the biosparge barrier has mitigated the potential discharge of impacted groundwater to an adjacent wetland; (ii) enhanced bioremediation within Hot Spot 1 achieved the CAO within 2 years and transitioned the area into LTM; (iii) operation of an air sparge system within Hot Spot 2 removed TCE as a constituent of concern and contributed to a reduction (approximately 43%) in the impacted groundwater area outside the air sparge treatment area (plume collapse); and (iv) bioremediation within Hot Spot 3 removed approximately 80% of the CVOC mass and contributed to a reduction (approximately 47%) in the impacted groundwater area outside the bioremediation IM treatment area. Overall, the adaptive approach is protecting the sensitive water bodies surrounding the complex site and reducing the area of impacted groundwater, which is moving the entire site towards LTM.

Rebecca C Daprato↗

In situ measurements constraining the role of sulphate aerosols in mid-latitude ozone depletion

In situ measurements of stratospheric sulphate aerosol, reactive nitrogen and chlorine concentrations at middle latitudes confirm the importance of aerosol surface reactions that convert active nitrogen to a less active, reservoir form. This makes mid-latitude stratospheric ozone less vulnerable to active nitrogen and more vulnerable to chlorine species. The effect of aerosol reactions on active nitrogen depends on gas phase reaction rates, so that increases in aerosol concentration following volcanic eruptions will have only a limited effect on ozone depletion at these latitudes.

Fahey, D. W.↗

Heterogeneous processes: Laboratory, field, and modeling studies

The efficiencies of chemical families such as ClO(x) and NO(x) for altering the total abundance and distribution of stratospheric ozone are controlled by a partitioning between reactive (active) and nonreactive (reservoir) compounds within each family. Gas phase thermodynamics, photochemistry, and kinetics would dictate, for example, that only about 1 percent of the chlorine resident in the lower stratosphere would be in the form of active Cl or ClO, the remainder existing in the reservoir compounds HCl and ClONO2. The consistency of this picture was recently challenged by the recognition that important chemical transformations take place on polar regions: the Airborne Antarctic Ozone Experiment (AAOE) and the Airborne Arctic Stratospheric Expedition (AASA). Following the discovery of the Antarctic ozone hole, Solomon et al. suggested that the heterogeneous chemical reaction: ClONO2(g)+HCl(s) yields Cl2(g)+HNO3(s) could play a key role in converting chlorine from inactive forms into a species (Cl2) that would rapidly dissociate in sunlight to liberate atomic chlorine and initiate ozone depletion. The symbols (s) and (g) denote solid phase, or adsorbed onto a solid surface, and gas phase, respectively, and represent the approach by which such a reaction is modeled rather than the microscopic details of the reaction. The reaction was expected to be most important at altitudes where PSC's were most prevalent (10 to 25 km), thereby extending the altitude range over which chlorine compounds can efficiently destroy ozone from the 35 to 45 km region (where concentrations of active chlorine are usually highest) to lower altitudes where the ozone concentration is at its peak. This chapter will briefly review the current state of knowledge of heterogeneous processes in the stratosphere, emphasizing those results obtained since the World Meteorological Organization (WMO) conference. Sections are included on laboratory investigations of heterogeneous reactions, the characteristics and climatology of PSC's, stratospheric sulfate aerosols, and evidence of heterogeneous chemical processing.

Poole, Lamont R.↗

General Services Administration Reclamation Yard Solid Waste Management Unit 010: 2022 Groundwater Monitoring Report Kennedy Space Center, Florida

This report presents a summary of the groundwater monitoring activities that occurred in September and October 2022 at General Services Administration Reclamation Yard, Solid Waste Management Unit 010, located at the John F. Kennedy Space Center (KSC), Florida. The site is monitored under KSC’s Resource Conservation and Recovery Act Corrective Action Program. This approach also meets the requirements of Chapter 62-780, Florida Administrative Code. For the purposes of this report, two separate plumes, known as the Polychlorinated Biphenyl (PCB)/Volatile Organic Aromatic (VOA) Plume and the Chlorinated Volatile Organic Compound (VOC) Plume, were identified for this site. The contaminants of concern (COCs) for the PCB/VOA Plume consist of PCBs, 1,2,4-trichlorobenzene, and breakdown products of 1,2,4-trichlorobenzene. The COCs for the Chlorinated VOC Plume were tetrachloroethene, trichloroethene, cis-1,2-dichloroethene, and vinyl chloride. Groundwater monitoring for VOCs in the Chlorinated VOC Plume area was discontinued following the December 2021 annual monitoring event. Annual groundwater monitoring for underground injection control (UIC) parameters continues for both the PCB/VOA Plume and the Chlorinated VOC Plume areas. The activities presented in this report include one field event: September and October 2022, which includes sitewide semi-annual water level measurements of 55 monitoring wells, redevelopment of all monitoring wells listed in the sampling plan, and groundwater sampling of 28 monitoring wells. The sampling and analysis demonstrated that the PCB/VOA plume is not expanding and is significantly reduced compared to before a 2018 source removal interim measure. Recommendations are made for the 2023 groundwater monitoring program.

groundwater↗

Measurement of trace levels of chlorine in the stratosphere

Mathematical models of stratospheric ozone have predicted a reduction in the total ozone due to chlorofluoromethanes released into the atmosphere. Analytical procedures for the collection of air in the stratosphere and for analysis of these air samples for trace levels of chlorine, regardless of the state of chemical composition were developed. Calibration experiments are conducted in order to validate all methods and procedures. Results of neutron activation analysis calibration procedures using standard chlorine gases are included.

Warren, D. C.↗

Can Chlorine Anion Catalyze the Reaction fo HOCl with HCl?

The reaction of HOCl + HCl -> Cl2 + H20 in the presence of Cl has been studied using ab initio methods. This reaction has been shown to have a high activation barrier of 46.5 kcal/mol. The chlorine anion, Cl- is found to catalyze the reaction, viz. two mechanisms. The first involves Cl- interacting through the concerted four-center transition state of the neutral reaction. The other mechanism involves the formation of a HCl-HOCl-Cl- intermediate which dissociates into Cl2 + Cl- + H20. The steps are found to have no barriers. The overall exothermicity is 15.5 kcal/mol.

Richardson, S. L.↗

Episodic total ozone minima and associated effects on heterogeneous chemistry and lower stratospheric transport

Three-dimensional model simulations are used to describe the January 31, 1989 ozone minihole over Stavanger, Norway. This minihole is typical of many transient events in the lower stratosphere that arise because of cyclonic-scale disturbances in the troposphere. Although the ozone reduction is a short-lived reversible dynamical event, through heterogeneous chemical processes there can be a significant transfer of chlorine from reservoir molecules to active radicals. This chemically perturbed air is defined as processed air, and it is found that a single event can produce enough processed air to reduce the HCl in the entire polar vortex. Chemical processing on clouds associated with transient events is shown to be a major source of processed air in the polar vortex in December before background temperatures are cold enough for more uniform heterogeneous conversion.

Rood, Richard B.↗

Column measurements of stratospheric trace species over Are, Sweden in the winter of 1991-1992

Total vertical column amounts of stratospheric HCl, HF, ClONO2 and HNO3 are reported from high resolution infrared solar absorption spectra taken during the European Arctic Stratospheric Ozone Experiment (EASOE) in the winter of 1991-1992. These ground based measurements were made near Are in North Sweden (63.4 deg N, 13.1 deg E) at an altitude of 800 m using a Fourier transform spectrometer and tunable diode laser heterodyne spectrometer. On 9th January 1992 the HCl vertical column dropped to 1.2 x 10(exp 15) molecules/sq cm from a November average of 3.6 x 10(exp 15) molecules/sq cm. The HCl drop occurred at a time when Are was below the polar vortex and the lower stratospheric ClO column above Are was elevated to approximately 2 x 10(exp 15) molecules/sq cm as measured by the Microwave Limb Sounder experiment on the Upper Atmosphere Research Satellite. These measurements indicate conversion of lower stratospheric chlorine from reservoir to chemically active forms.

Bell, W.↗