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Biases in Total Precipitable Water Vapor Climatologies from Atmospheric Infrared Sounder and Advanced Microwave Scanning Radiometer

We examine differences in total precipitable water vapor (PWV) from the Atmospheric Infrared Sounder (AIRS) and the Advanced Microwave Scanning Radiometer (AMSR-E) experiments sharing the Aqua spacecraft platform. Both systems provide estimates of PWV over water surfaces. We compare AIRS and AMSR-E PWV to constrain AIRS retrieval uncertainties as functions of AIRS retrieved infrared cloud fraction. PWV differences between the two instruments vary only weakly with infrared cloud fraction up to about 70%. Maps of AIRS-AMSR-E PWV differences vary with location and season. Observational biases, when both instruments observe identical scenes, are generally less than 5%. Exceptions are in cold air outbreaks where AIRS is biased moist by 10-20% or 10-60% (depending on retrieval processing) and at high latitudes in winter where AIRS is dry by 5-10%. Sampling biases, from different sampling characteristics of AIRS and AMSR-E, vary in sign and magnitude. AIRS sampling is dry by up to 30% in most high-latitude regions but moist by 5-15% in subtropical stratus cloud belts. Over the northwest Pacific, AIRS samples conditions more moist than AMSR-E by a much as 60%. We hypothesize that both wet and dry sampling biases are due to the effects of clouds on the AIRS retrieval methodology. The sign and magnitude of these biases depend upon the types of cloud present and on the relationship between clouds and PWV. These results for PWV imply that climatologies of height-resolved water vapor from AIRS must take into consideration local meteorological processes affecting AIRS sampling.

Atmospheric Infrared Sounder (AIRS)↗

Soyuz 7 Return Samples: Assessment of Air Quality Aboard the International Space Station

The toxicological assessments of one grab sample canister (GSC), 6 dual sorbent tubes (DSTs), and 20 formaldehyde badges returned aboard Soyuz 7 are reported. Analytical methods have not changed from earlier reports. Surrogate standard recoveries from the GSC were 84-89%. The recoveries of the less volatile surrogates from the DSTs were 87 to 112%; however, 13C-acetone was only recovered at 53-59%. Formaldehyde recoveries from 2 lab controls were 87 and 95%; trip controls were not returned to ground.

James, John T.↗

STS 117 Return Samples: Assessment of Air Quality aboard the Shuttle (STS-117) and International Space Station

The toxicological assessments of 2 grab sample canisters (GSCs) and one pair of formaldehyde badges from the Shuttle are reported. Analytical methods have not changed from earlier reports. The recoveries of the 3 surrogates (C-13-acetone, fluorobenzene, and chlorobenzene) from the 2 GSCs averaged 109, 95, and 97%, respectively. Three formaldehyde controls averaged 93% recovery. The Shuttle atmosphere was acceptable for human respiration.

James, John T.↗

STS 118 Return Samples: Assessment of Air Quality aboard the Shuttle (STS-118) and International Space Station

The toxicological assessments of 2 grab sample canisters (GSCs) and one pair of formaldehyde badges from the Shuttle are reported. Analytical methods have not changed from earlier reports. The recoveries of the 3 surrogates (C-13-acetone, fluorobenzene, and chlorobenzene) from the 2 GSCs averaged 120, 117, and 122 %, respectively. Three formaldehyde controls averaged 98% recovery. The Shuttle atmosphere was acceptable for human respiration. The toxicological assessment of 8 GSCs and 6 pairs of formaldehyde badges from the ISS is shown. The recoveries of the 3 standards (as listed above) from the GSCs averaged 99, 99 and 99%, respectively. Three formaldehyde control badges averaged 98% recovery. Based on these limited samples, the ISS atmosphere is acceptable for human respiration. The alcohol levels were well controlled throughout the period of sampling.

James, John T.↗

Hygrometer for Detecting Water in Partially Enclosed Volumes

A portable hygrometer has been devised to implement a pre-existing technique for detecting water trapped in partially enclosed volumes that may be difficult to reach and cannot be examined directly. The technique is based on the fact that eventually the air in such a volume becomes saturated or nearly so. The technique is straightforward: One measures the relative humidity and temperature of both the ambient air and a sample of air from the enclosed volume. If the relative humidity of the sample is significantly greater than that of the ambient air and/or if the sample is at or close to the dew point, then it can be concluded that water is trapped in the volume. Of course, the success of this technique depends on the existence of an access hole through which one can withdraw some air from the enclosed volume.

Youngquist, Robert C.↗

STS 120 Return Samples: Assessment of Air Quality Aboard the Shuttle (STS-120) and International Space Station (10A)

The toxicological assessments of 2 grab sample canisters (GSCs) from the Shuttle are reported. Formaldehyde badges were not used. Analytical methods have not changed from earlier reports. The recoveries of the 3 surrogates (C-13-acetone, fluorobenzene, and chlorobenzene) from the 2 GSCs averaged 111, 82, and 78%, respectively. The Shuttle atmosphere was acceptable for human respiration.

James, John T.↗

STS 119 Return Samples: Assessment of Air Quality aboard the Shuttle (STS-119) and International Space Station (15A)

The toxicological assessments of 2 grab sample canisters (GSCs) from the Shuttle are reported. Analytical methods have not changed from earlier reports. The recoveries of the 3 surrogates (C-13-acetone, fluorobenzene, and chlorobenzene) from the 2 GSCs averaged 106, 106, and 101 %,respectively. Based on the end-of-mission sample, the Shuttle atmosphere was acceptable for human respiration.

James, John T.↗

STS 130 Return Samples: Assessment of Air Quality Aboard the Shuttle (STS-130) and International Space Station (20A)

The toxicological assessments of 3 grab sample canisters (GSCs) from the Shuttle are reported in Table 1. Analytical methods have not changed from earlier reports. The recoveries of the 3 surrogates ( 13C-acetone, fluorobenzene, and chlorobenzene) from the 3 Shuttle GSCs averaged 96, 90, and 85 %, respectively. Based on the end-of-mission sample, the Shuttle atmosphere was acceptable for human respiration.

James, John T.↗

STS 132 Return Samples: Assessment of Air Quality Aboard the Shuttle (STS-132) and International Space Station (ULF4)

The toxicological assessments of 2 grab sample canisters (GSCs) from the Shuttle are reported. Analytical methods have not changed from earlier reports. The recoveries of the 3 surrogates (13C-acetone, fluorobenzene, and chlorobenzene) from the 2 Shuttle GSCs averaged 93, 85%, and 88%, respectively. Based on the end-of-mission sample, the Shuttle atmosphere was acceptable for human respiration. The toxicological assessment of 7 GSCs from the ISS is also shown. The recoveries of the 3 standards (as listed above) from the GSCs averaged 78, 96 and 90%, respectively. Recovery from formaldehyde control badges ranged from 90 to 112%.

James. John T.↗

STS 131 Return Samples: Assessment of Air Quality Aboard the Shuttle (STS-131) and International Space Station (19A)

The toxicological assessments of 1 grab sample canister (GSC) from the Shuttle are reported in Table 1. Analytical methods have not changed from earlier reports. The recoveries of the 3 surrogates (C-13-acetone, fluorobenzene, and chlorobenzene) from the Shuttle GSC were 100%, 93%, and 101%, respectively. Based on the historical experience using end-of-mission samples, the Shuttle atmosphere was acceptable for human respiration.

James, John T.↗

STS 129 Return Samples: Assessment of Air Quality aboard the Shuttle (STS-129) and International Space Station (ULF3)

Reports on the air quality aboard the Space Shuttle (STS-129), and the International Space station (ULF3). NASA analyzed the grab sample canisters (GSCs) and the formaldehyde badges aboard both locations for carbon monoxide levels. The three surrogates: (sup 13)C-acetone, fluorobenzene, and chlorobenzene registered 109, 101, and 109% in the space shuttle and 81, 87, and 55% in the International Space Station (ISS). From these results the atmosphere in both the Space Shuttle and the International Space Station (ISS) was found to be breathable.

James, John T.↗

6S Return Samples: Assessment of Air Quality in the International Space Station (ISS) Based on Solid Sorbent Air Sampler (SSAS) and Formaldehyde Monitoring Kit (FMK) Analyses

The toxicological assessments of SSAS and FMK analytical results are reported. Analytical methods have not changed from earlier reports. Surrogate standard recoveries from the SSAS tubes were 66-76% for 13C-acetone, 85-96% for fluorobenzene, and 73-89% for chlorobenzene. Post-flight flows were far below pre-flight flows and an investigation of the problem revealed that the reduced flow was caused by a leak at the interface of the pump inlet tube and the pump head. This resulted in degradation of pump efficiency. Further investigation showed that the problem occurred before the SSAS was operated on orbit and that use of the post-flight flows yielded consistent and useful results. Recoveries from formaldehyde control badges were 86 to 104%. The two general criteria used to assess air quality are the total-non-methane-volatile organic hydrocarbons (NMVOCs) and the total T-value (minus the CO2 and formaldehyde contributions). The T values will not be reported for these data due to the flow anomaly. Control of atmospheric alcohols is important to the water recovery system engineers, hence total alcohols (including acetone) are also shown for each sample. Octafluoropropane (OFP) is not efficiently trapped by the sorbents used in the SSAS. Because formaldehyde is quantified from sorbent badges, its concentration is also listed separately. These five indices of air quality are summarized.

James, John T.↗

Tonopah Test Range Air Monitoring: CY2018 Meteorological, Radiological, and Wind Transported Particulate Observations

In 1963, the U.S. Department of Energy (DOE) (formerly the Atomic Energy Commission [AEC]), implemented Operation Roller Coaster on the Tonopah Test Range (TTR) and an adjacent area of the Nevada Test and Training Range (NTTR) (formerly the Nellis Air Force Range). This operation resulted in radionuclide-contaminated soils at the Double Tracks site and Clean Slate I, II, and III sites. This report documents observations made during ongoing monitoring of radiological, meteorological, and dust conditions at stations installed adjacent to the Clean Slate sites and at the TTR Sandia National Laboratories (SNL) Range Operations Center (ROC). The primary objective of the monitoring effort is to support the DOE Environmental Management Nevada Program (EM NV) in the safe remediation of the environmental legacy of nuclear device development and testing by determining if wind blowing across the Clean Slate sites is transporting particles of radionuclide-contaminated soil beyond the physical and administrative boundaries of the sites, and to provide information for designing long-term monitoring of the sites. The monitoring program in 2018 included five stations. Station 400, located within TTR Area 3 and near the ROC, monitors conditions near the local workforce center. Stations 401 and 403 are located on the northern and southeastern perimeter fence lines, respectively, of the Clean Slate III site. Stations 404 and 405 are along the northern and eastern boundary fence, respectively, at Clean Slate II. The stations are generally downwind of the contaminated areas during either northwesterly or southerly winds, which are the predominant wind directions. The stations—which are similar in design to the Community Environmental Monitoring Program (CEMP) stations operating at locations surrounding the Nevada National Security Site and TTR—include meteorological instruments and continuous-flow, low-volume air samplers. Three pressurized ionization chambers for measuring gamma energy are in use at Stations 400, 401, and 403. Saltation sensors and saltation traps are deployed at the stations adjacent to the Clean Slate sites. Detailed meteorological data are recorded on data loggers, with periodic uploads via a satellite system to the Western Regional Climate Center (WRCC) at Desert Research Institute (DRI), to monitor instrument and site conditions. Air filter samples are collected every two weeks and the deposits in the saltation traps are collected when a sufficient sample mass for analysis has accumulated (generally a six- to eight-month interval). Monitoring at TTR in calendar year (CY) 2018 provided surveillance of both ambient conditions, and ground disturbance associated with remediation activities at Clean Slate II and III. The first half of CY2018 data from Stations 404 and 405 at Clean Slate II were collected during remediation activities at that site, and data collected during the final third of the year at Stations 401 and 403 at Clean Slate III coincided with remediation work at the site. Ambient conditions prevailed at Station 400 throughout the year. Dust transport by suspension and saltation is strongly dependent on wind speed. Concentrations of PM 10 (particulate matter of aerodynamic diameter ≤10 micrometers [μm], a size fraction of small particles that are suspended in the air and can be easily inhaled) remain low until winds exceed approximately 32 kilometers per hour (km/hr) (20 miles per hour [mph]). Saltation particle counts also increase above the same general threshold wind speed. Wind speeds in excess of 32 km/hr (20 mph) occur less than three percent of the time at the sites. Ground disturbing remediation activities were carried out at Clean Slate II from October 31, 2017, until July 26, 2018. Station 404 is located closest to the remediation area and is downwind of the area when winds are from the south. By late November, analysis of dust from the air sampler at Station 404 registered increases in plutonium-239+240 ( 239+240 Pu) concentrations. Peak plutonium concentrations, accompanied by elevated gross alpha concentrations and the detection of americium-241 ( 241 Am) by gamma spectroscopy, occurred between March and May 2018. During spring and early summer of 2018, elevated radionuclide concentrations were also measured in dust collected from the air sampler at Station 405, which is more than twice the distance from the remediation activity as Station 404. A minor but sustained increase in gross alpha concentration of suspended dust collected at Stations 400, 401, and 403 was also observed starting in May 2018 and continuing into August. Stations 401 and 403 are approximately 4.8 to 6.4 km (three to four miles) from Clean Slate II and Station 400 is approximately 13 km (eight miles) from that site. The radionuclide content of material that saltated into the passive Big Spring Number Eight (BSNE) traps during the Clean Slate II remediation period increased in both the traps facing toward and away from the fenced contamination area at Station 404, with the largest increases in concentration (almost five times the previous 239+240 Pu concentration) observed in the traps facing the fenced area. The radionuclide concentration in material in the trap facing away from the fence more than doubled from that measured in 2017. A similar increase was observed for the saltation trap facing away from the fenced area at Station 405, although no increase was observed for material captured in the trap facing the fenced area. Particles ranging in size from 50 to 500 µm generally move by saltation processes and are not expected to significantly contribute to dose for someone breathing in the standard respiratory zone for adult humans (1.5 to 1.7 m [4.9 to 5.6 ft] above ground level) because they are too large to be entrained in the air as suspended dust. Remediation activities at Clean Slate III began on September 5, 2018, and continued until a brief hiatus started on December 20, 2018. Although Station 401 is much closer to the remediation area than Station 403, the first increase in gross alpha and 239+240 Pu concentrations was noted in dust from filters collected at Station 403 in early November 2018. The highest radionuclide concentrations of 2018 at the Clean Slate III stations were recorded in air samples taken from Stations 401 and 403 in late December 2018 and these concentrations were comparable between the two station locations. Gamma rate data measured by the PICs was slightly higher than the annual average at Stations 401 and 403 after remediation activities began, but no single measurement was outside of the range observed in 2018 prior to remediation activities. No increase in radionuclide concentration was observed for the Clean Slate III remediation time period on air filters collected from the other stations. Radiological monitoring at Station 400—which is located at the ROC, and therefore the closest regularly staffed work location to the Clean Slate sites—recorded a higher mean gross alpha activity from dust collected on air sampler filters than in previous years. The individual biweekly air filters yielded measurements of gross alpha that were at or below the mean plus one standard deviation measured in CY2017, except for the period from April 25, 2018, through September 12, 2018. Nonetheless, gamma spectroscopy of all air filters from Station 400 identified only naturally occurring radionuclides, with no detection of americium-241 ( 241 Am) (which is used as an indicator of plutonium-241[ 241 Pu]). Alpha spectroscopy of selected air filters collected at Station 400 did not detect plutonium-238 ( 238 Pu) or 239+240 Pu above the analytical detection limit. Gross beta and gamma exposure rate data were comparable to data from regional CEMP stations. No saltation traps are deployed at Station 400. Considering the ambient monitoring periods during CY2018, the monitoring stations adjacent to the Clean Slate sites recorded above-background 238 Pu and 239+240 Pu concentrations (SNL, 1998; Turner et al., 2003) in samples collected by passive saltation traps and on selected air filters. These observations were consistent with previous years and indicated that radionuclide movement occurred under ambient conditions by processes of both saltation and suspension. The presence of radionuclides in all saltation traps, both upwind and downwind of the fenced contamination areas, was consistent with previous radiological survey results (EG&G, 1979) that show lower concentration radiologically contaminated material dispersed outside the fenced area. Although 239+240 Pu concentrations in the air filter samples were sometimes orders of magnitude higher than background, the concentrations were below risk-based action levels defined for an industrial area worker scenario (U.S. DOE, 2014). The interception of airborne dust with above-background radionuclide concentrations demonstrates that dispersal processes are continuing. Strong winds are the driver for both suspension and saltation of dust and soil. The recorded wind speed and PM10 during remediation activities at Clean Slate II and III identified discrete wind events lasting approximately five to eight hours each, which accounted for the greatest PM 10 concentrations at the monitoring stations. These events captured the effect of winds from the northwest and from the south. The observed differences in dust loading and radionuclide concentrations for the monitoring stations when they were either upwind or downwind of the contamination area identify the remediation area as a source of plutonium contaminated dust. The increase in concentration of radionuclides in airborne dust during the remediation activities, compared with measurements under previous ambient conditions (mean 239+240 Pu concentrations during remediation activities are approximately nine to 40 times higher compared to pre-remediation concentrations, depending on monitoring station), highlights the impact of land disturbance on wind-borne contaminant transport from the Clean Slate test areas. The meteorological and particulate matter monitoring indicated that conditions for wind-borne contaminant movement exist at the Clean Slate sites, and that transport of radionuclide-contaminated soil by both suspension and saltation occurred under ambient conditions and accelerated when the sites were disturbed. The 239+240 Pu alpha spectroscopy results indicated that airborne concentrations during remediation activities ranged from 2 × 10-16 to 380 × 10-16 µCi/ml. These results can be compared to the derived air concentration limit for 239 Pu of 6 × 10-11 µCi/ml for occupational workers contained in Code of Federal Regulations 10 CFR 835, Occupational Radiation Protection. Even though the air sampling results document an increase in concentration during remediation activities, the observed concentrations are less than 0.06 percent of the occupational limit. The Corrective Action Unit (CAU) closure strategy uses a risk-based approach, whereby acceptable contaminant concentrations are determined as a function of anticipated human exposure.

54 ENVIRONMENTAL SCIENCES↗

Toxicological Assessment of ISS Air Quality: Contingency Sampling - February 2013

Two grab sample containers (GSCs) were collected by crew members onboard ISS in response to a vinegar-like odor in the US Lab. On February 5, the first sample was collected approximately 1 hour after the odor was noted by the crew in the forward portion of the Lab. The second sample was collected on February 22 when a similar odor was noted and localized to the end ports of the microgravity science glovebox (MSG). The crewmember removed a glove from the MSG and collected the GSC inside the glovebox volume. Both samples were returned on SpaceX-2 for ground analysis.

Meyers, Valerie↗

Crystal structure and high-temperature properties of the Ruddlesden–Popper phases Sr{sub 3−x}Y{sub x}(Fe{sub 1.25}Ni{sub 0.75})O{sub 7−δ} (0≤x≤0.75)

Ruddlesden–Popper n=2 member phases Sr{sub 3−x}Y{sub x}Fe{sub 1.25}Ni{sub 0.75}O{sub 7−δ}, 0≤x≤0.75, have been investigated by X-ray and neutron powder diffraction, thermogravimetry and Mössbauer spectroscopy. Both samples as-prepared at 1300 °C under N{sub 2}(g) flow and samples subsequently air-annealed at 900 °C were studied. The as-prepared x=0.75 phase is highly oxygen deficient with δ=1, the O1 atom site being vacant, and the Fe{sup 3+}/Ni{sup 2+} ions having a square pyramidal coordination. For as-prepared phases with lower x values, the Mössbauer spectral data are in good agreement with the presence of both 5- and 4-coordinated Fe{sup 3+} ions, implying in addition a partial occupancy of the O3 atom sites that form the basal plane of the square pyramid. The air-annealed x=0.75 sample has a δ value of 0.61(1) and the structure has Fe/Ni ions in both square pyramids and octahedra. Mössbauer spectroscopy shows the phase to contain only Fe{sup 3+}, implying that all Ni is present as Ni{sup 3+}. Air-annealed phases with lower x values are found to contain both Fe{sup 3+} and Fe{sup 4+}. For both the as-prepared and the air-annealed samples, the Y{sup 3+} cations are found to be mainly located in the perovskite block. The high-temperature thermal expansion of as-prepared and air-annealed x=0.75 phases were investigated by high-temperature X-ray diffraction and dilatometry and the linear thermal expansion coefficient determined to be 14.4 ppm K{sup −1}. Electrical conductivity measurements showed that the air-annealed samples have higher conductivity than the as-prepared ones. - Highlights: • Ruddlesden–Popper, n=2, Sr{sub 3−x}Y{sub x}Fe{sub 1.25}Ni{sub 0.75}O{sub 7−δ}, 0≤x≤0.75, have been synthesised. • The crystal structures of the phases have been determined. • Sr{sub 2.25}Y{sub 0.75}Fe{sub 1.25}Ni{sub 0.75}O{sub 6}, made in N{sub 2}(g) has Fe{sup 3+}/Ni{sup 2+} in square pyramides. • Sr{sub 2.25}Y{sub 0.75}Fe{sub 1.25}Ni{sub 0.75}O{sub 6.4}, made in air has Fe{sup 3+}/Ni{sup 3+} in square pyramides and octahedra. • Air annealed samples have higher electrical conductivity than N{sub 2}(g) annealed.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗