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All sourcesNASA NTRSDOE OSTI
NASA NTRS1999

The Budget and Partitioning of Stratospheric Chlorine During the 1997 Arctic Summer

Volume mixing ratio profiles of HCl, HOCl, ClNO3, CH3Cl, CFC-12, and CFC-11, CCl4, HCFC-22, and CFC-113 were measured simultaneously from 9 to 38 km by the Jet Propulsion Laboratory MkIV Fourier Transform Infrared solar absorption spectrometer during two balloon flights from Fairbanks, Alaska (64.8 N), on May 8 and July 8, 1997. The altitude variation of total organic chlorine (CCl(sub y)), total inorganic chlorine (Cl(sub y)), and the nearly constant value (3.7 +/- 0.2 ppbv) of their sum (Cl(sub TOT)) demonstrates that the stratospheric chlorine species available to react with O3 are supplied by the decomposition of organic chlorinated compounds whose abundances are well quantified. Measured profiles of HCl and ClNO3 agree well with profiles found by photochemical model (differences < 10% for altitudes below 35 km) constrained by various other constituents measured by MkIV. The production of HCl by ClO + OH plays a relatively small role in the partitioning of HCl and ClNO3 for the sampled air masses. However, better agreement with the measured profiles of HCl and ClNO3 is obtained when this source of HCl is included in the model. Both the measured and calculated [ClNO3]/[HCl] ratios exhibit the expected near linear variation with [O3](sup 2)/[CH4] over a broad range of altitudes. MkIV measurements of HCl, ClNO3, and CCl(sub y) agree well with ER-2 in situ observations of these quantities for directly comparable air masses. These results demonstrate good understanding of the budget of stratospheric chlorine and that the partitioning of inorganic chlorine is accurately described by photochemical models that employ JPL97 reaction rates and production of HCl from ClO + OH for the environmental conditions encountered: relatively warm temperatures, long periods of solar illumination, and relatively low aerosol surface areas.

Sen, B.↗
NASA NTRS1999

The Budget and Partitioning of Stratospheric Chlorine During the 1997 Arctic Summer

Volume mixing ratio profiles of HCl, HOCl, ClNO3, CH3Cl, CFC-12, CFC-11, CCl4, HCFC-22, and CFC-113 were measured simultaneously from 9 to 38 km by the Jet Propulsion Laboratory MkIV Fourier Transform Infrared solar absorption spectrometer during two balloon flights from Fairbanks, Alaska (64.8 N), on May 8 and July 8, 1997. The altitude variation of total organic chlorine (CCly) total inorganic chlorine (Cly), and the nearly constant value (3.7 +/- 0.2 ppbv) of their sum (Cl(sub TOT)) demonstrates that the stratospheric chlorine species available to react with O3 are supplied by the decomposition of organic chlorinated compounds whose abundances are well quantified. Measured profiles of HCl and ClNO3 agree well with profiles found by photochemical model (differences < 10% for altitudes below 35 km) constrained by various other constituents measured by MkIV. The production of HCl by ClO + OH plays a relatively small role in the partitioning of HCl and ClNO3 for the sampled air masses. However, better agreement with the measured profiles of HCl and ClNO3 is obtained when this source of HCl is included in the model. Both the measured and calculated [ClNO3]/[HCl] ratios exhibit the expected near linear variation with [O3]2/[CH4] over a broad range of altitudes. MkIV measurements of HCl, ClNO3, and CC1y agree well with ER-2 in situ observations of these quantities for directly comparable air masses. These results demonstrate good understanding of the budget of stratospheric chlorine and that the partitioning of inorganic chlorine is accurately described by photochemical models that employ JPL97 reaction rates and production of HCl from ClO + OH for the environmental conditions encountered: relatively warm temperatures, long periods of solar illumination, and relatively low aerosol surface areas.

Sen, B.↗
NASA NTRS2000

An Examination of the Inorganic Chlorine Budget in the Lower Stratosphere

We use the first simultaneous in situ measurements of ClONO2, ClO, and HCl acquired using the NASA ER-2 aircraft during the Photochemistry of Ozone Loss in the Arctic Region in Summer (POLARIS) mission to test whether these three compounds quantitatively account for total inorganic chlorine (Cly) in the lower stratosphere in 1997. We find (ClO + ClONO2 + HCl)/Cly = 0.92 +/- 0.10, where Cly is inferred from in situ measurements of organic chlorine source gases. These observations are consistent with our current understanding of the budget and partitioning of Cly in the lower stratosphere. We find no evidence in support of missing inorganic chlorine species that compose a significant fraction of Cly. We apply the analysis to earlier ER-2 observations dating from 1991 to investigate possible causes of previously observed discrepancies in the inorganic chlorine budget. Using space shuttle, satellite, balloon, and aircraft measurements in combination with ER-2 data, we find that the discrepancy is unlikely to have been caused by missing chlorine species or an error in the photolysis rate of chlorine nitrate. We also find that HCl/Cly is not significantly controlled by aerosol surface area density in the lower stratosphere.

Bonne, G. P.↗
NASA NTRS1996

Balloon observations of organic and inorganic chlorine in the stratosphere: the role of HClO4 production on sulfate aerosols

Simultaneous observations of stratospheric organic and inorganic chlorine were made in September 1993 out of Fort Sumner, New Mexico, using JPL balloon-borne MkIV interferometer. Between 15 and 20 km, a significant fraction (20-60%) of the inorganic chlorine could not be accounted for by the sum of measured HCl, ClONO2, and HOCl. Laboratory measurements of the reaction of ClO radicals on sulfuric acid solutions have indicated that, along with HCl, small amounts of perchloric acid, HClO4, were formed. Very little is known about the fate of HClO4 in the stratosphere and we use a photochemical box model to determine the impact of this new species on the partitioning of inorganic chlorine in the stratosphere. Assuming that HClO4 is photochemically stable, it is shown that in the enhanced aerosol loading conditions resulting from Mt. Pinatubo's eruption, HClO4 could represent a significant reservoir of chlorine in the lower stratosphere, sequestering up to 0.2 ppbv (or 50%) of the total inorganic chlorine at 16 km. The occurrence of this new species could bring to closure the inorganic chlorine budget deficiency made apparent by recent ER-2 aircraft in situ measurements of HCl.

unmanned↗
NASA NTRS2012

Ozone Temperature Correlations in the Upper Stratosphere as a Measure of Chlorine Content

We use data from the Nimbus-7 Limb Infrared Monitor of the Stratosphere (LIMS) for the 1978-1979 period together with data from the Upper Atmosphere Research Satellite Microwave Limb Sounder (UARS MLS) for the years 1993 to 1999, the Aura MLS for the years 2004 to 2011, and the Aura High Resolution Infrared Limb Sounder (HIRDLS) for the years 2005 to 2007 to examine ozone-temperature correlations in the upper stratosphere. Our model simulations indicate that the sensitivity coefficient of the ozone response to temperature (Delta ln(O3)/Delta.(l/T)) decreases as chlorine has increased in the stratosphere and should increase in the future as chlorine decreases. The data are in agreement with our simulation of the past. We also find that the sensitivity coefficient does not change in a constant-chlorine simulation. Thus the change in the sensitivity coefficient depends on the change in chlorine, but not on the change in greenhouse gases. We suggest that these and future data can be used to track the impact of chlorine added to the stratosphere and also to track the recovery of the stratosphere as chlorine is removed under the provisions of the Montreal Protocol.

Stolarski, Richard S.↗
NASA NTRS2013

Evidence for Perchlorates and the Origin of Chlorinated Hydrocarbons Detected by SAM at the Rocknest Aeolian Deposit in Gale Crater

A single scoop of the Rocknest aeolian deposit was sieved (less than 150 micrometers), and four separate sample portions, each with a mass of approximately 50 mg, were delivered to individual cups inside the Sample Analysis at Mars (SAM) instrument by the Mars Science Laboratory rover's sample acquisition system. The samples were analyzed separately by the SAM pyrolysis evolved gas and gas chromatograph mass spectrometer analysis modes. Several chlorinated hydrocarbons including chloromethane, dichloromethane, trichloromethane, a chloromethylpropene, and chlorobenzene were identified by SAM above background levels with abundances of approximately 0.01 to 2.3 nmol. The evolution of the chloromethanes observed during pyrolysis is coincident with the increase in O2 released from the Rocknest sample and the decomposition of a product of N-methyl-N-(tert-butyldimethylsilyl)-trifluoroacetamide (MTBSTFA), a chemical whose vapors were released from a derivatization cup inside SAM. The best candidate for the oxychlorine compounds in Rocknest is a hydrated calcium perchlorate (Ca(ClO4)2·nH2O), based on the temperature release of O2 that correlates with the release of the chlorinated hydrocarbons measured by SAM, although other chlorine-bearing phases are being considered. Laboratory analog experiments suggest that the reaction of Martian chlorine from perchlorate decomposition with terrestrial organic carbon from MTBSTFA during pyrolysis can explain the presence of three chloromethanes and a chloromethylpropene detected by SAM. Chlorobenzene may be attributed to reactions of Martian chlorine released during pyrolysis with terrestrial benzene or toluene derived from 2,6-diphenylphenylene oxide (Tenax) on the SAM hydrocarbon trap. At this time we do not have definitive evidence to support a nonterrestrial carbon source for these chlorinated hydrocarbons, nor do we exclude the possibility that future SAM analyses will reveal the presence of organic compounds native to the Martian regolith.

sample analysis at mars↗
NASA NTRS2006

Temporal Decrease in Upper Atmospheric Chlorine

We report a steady decrease in the upper stratospheric and lower mesospheric abundances of hydrogen chloride (HCl) from August 2004 through January 2006, as measured by the Microwave Limb Sounder (MLS) aboard the Aura satellite. For 60(deg)S to 60(deg)N zonal means, the average yearly change in the 0.7 to 0.1 hPa (approx.50 to 65 km) region is -27 +/- 3 pptv/year, or -0.78 +/- 0.08 percent/year. This is consistent with surface abundance decrease rates (about 6 to 7 years earlier) in chlorine source gases. The MLS data confirm that international agreements to reduce global emissions of ozone-depleting industrial gases are leading to global decreases in the total gaseous chlorine burden. Tracking stratospheric HCl variations on a seasonal basis is now possible with MLS data. Inferred stratospheric total chlorine (CITOT) has a value of 3.60 ppbv at the beginning of 2006, with a (2-sigma) accuracy estimate of 7%; the stratospheric chlorine loading has decreased by about 43 pptv in the 18-month period studied here. We discuss the MLS HCl measurements in the context of other satellite-based HCl data, as well as expectations from surface chlorine data. A mean age of air of approx. 5.5 years and an age spectrum width of 2 years or less provide a fairly good fit to the ensemble of measurements.

chlorine↗
NASA NTRS1978

Summary of airborne chlorine and hydrogen chloride gas measurements for August 20 and September 5, 1977 Voyager launches at Air Force Eastern Test Range, Florida

Airborne chlorine and hydrogen chloride measurements were made in the tropospheric ground cloud following the Voyager launches of August 20 and September 5, 1977. The maximum observed hydrogen chloride concentration for both launches was about 25 to 30 parts per million (ppm) occurring typically 2 to 6 minutes after launch. By completion of the sampling mission (1-1/2 hours for August, 4-1/2 hours for September), the maximum in-cloud concentration decayed to about 1 to 2 ppm. Maximum observed chlorine concentrations were about 40 to 55 parts per billion (ppb) about 2 to 8 minutes after launch; by about 15 minutes after launch, chlorine concentrations were less than 10 ppb (detection limit). In-cloud chlorine concentrations were well below 1 percent of hydrogen chloride concentrations. The appendix of the report discusses the chlorine instrument and the laboratory evaluation of the detector.

Gregory, G. L.↗
NASA NTRS1978

The reaction Cl + H2CO yields HCl + HCO: Decreased sensitivity of stratospheric ozone to chlorine perturbations

The absolute rate constant for the reaction Cl + H2CO yields HCl + HCO was determined by the flash-photolysis resonance fluorescence method to be 7.5 plus or minus 0.9 (2 sigma) times 10 to the minus 11th power cu cm/molecule sec at 298 K and to have a negligible temperature dependence. This rate which is more than 2000 times faster than the rate of Cl + CH4 indicates that formaldehyde (H2CO) will compete significantly with methane (CH4) for the conversion of active chlorine in the stratosphere to the inactive reservoir HCl. Chlorine will thus be a less efficient destroyer of stratosphere ozone than previously believed. Ambient stratospheric ozone will depend less on the ambient chlorine amount and the predicted response to chlorine perturbations will be lessened. One-dimensional eddy-diffusion photochemical model calculations indicate a factor of 1.1 less sensitivity to chlorine than recently reported. For a steady-state CFM release at 1975 rates (750,000 tons/year) the eventual ozone depletion is now calculated to be 14%.

Stief, L. J.↗
NASA NTRS1990

High temperature reactions of ceramics and metals with chlorine and oxygen

The reactions of chlorine and oxygen with solids are complex and quite dependent on material and reaction conditions. However, there are four reaction schemes that describe many of these reactions. These are direct reaction of chlorine with the oxide layer, penetration of the oxide layer by chlorine, paralinear behavior where oxidation and chlorination are of comparable rates, and finally, gas phase reactions where the volatile chlorides react with oxygen. Examples of chlorine and oxygen reactions with cobalt, nickel, chromium, molybdenum, and silicon carbide illustrate each of these four reaction schemes.

Jacobson, N. S.↗
NASA NTRS1993

Stratospheric chlorine injection by volcanic eruptions - HCl scavenging and implications for ozone

Because the output of volatile chlorine during a major volcanic event can greatly exceed the annual anthropogenic emissions of chlorine to the atmosphere, the fate of volcanic chlorine must be known. Although numerous observations have shown that volcanoes do not significantly contribute to the stratospheric chlorine burden, no quantitative explanation has been published. Hydrogen chloride (HCl) scavenging processes during the early phases of a volcanic eruption are discussed. A plume dynamics and thermodynamics model is used to show that HCl removal in condensed supercooled water can reduce HCl vapor concentrations by up to four orders of magnitude, preventing substantial stratospheric chlorine injection.

Tabazadeh, A.↗
NASA NTRS1994

Application of Chlorine-Assisted Chemical Vapor Deposition of Diamond at Low Temperatures

Low temperature deposition of diamond has been achieved by a chlorine-assisted diamond chemical vapor deposition (CA-CVD) process. This method begins with the thermal dissociation of molecular chlorine into atomic chlorine in a resistively heated graphite furnace at temperatures between 1300 and 1500 deg. C. The atomic chlorine, upon mixing, subsequently reacts with molecular hydrogen and hydrocarbons. The rapid exchange reactions between the atomic chlorine, molecular hydrogen, and hydrocarbons give rise to the atomic hydrogen and carbon precursors required for diamond deposition. Homoepitaxial diamond growth on diamond substrates has been studied over the substrate temperature range of 100-950 C. It was found that the diamond growth rates are approximately 0.2 microns/hr in the temperature range between 102 and 300 C and that the growth rates do not decrease significantly with a decrease in substrate temperature. This is unique because the traditional diamond deposition using H2/CH4 systems usually disappears at substrate temperatures below approx. 500 deg. C. This opens up a possible route to the deposition of diamond on low-melting point materials such as aluminum and its alloys.

Pan, Chenyu↗
NASA NTRS1996

Chlorine Deactivation in the Lower Stratospheric Polar Regions during late Winter: Results from UARS

Recovery from enhanced chlorine conditions in the lower stratospheric polar regions of both hemispheres is investigated using data from the Upper Atmosphere Research Satellite (UARS). Microwave Limb Sounder (MLS) measurements of ClO within the polar vortices are used to infer ClO(sub x) (ClO + 2Cl202) abundances that are then correlated with simultaneous Cryogenic Limb Array Etalon Spectrometer (CLAES) measurements of ClON02 and Halogen Occultation Experiment (HALOE) measurements of HCl obtained starting within 5 days of the end of the MLS and CLAES high-latitude observing periods in each hemisphere. Time series of vortex-averaged mixing ratios are calculated on two potential temperature surfaces (585 K and 465 K) in the lower stratosphere for approximately month-long intervals during late winter: August 17 - September 17, 1992, in the southern hemisphere and February 12 - March 16, 1993, in the northern hemisphere. The observed mixing ratios are adjusted for the effects of vertical transport using diabatic vertical velocities estimated from CLAES tracer data. In the northern hemisphere, the decrease in ClO, is balanced on both surfaces by an increase in ClON02- In the southern hemisphere, continuing polar stratospheric cloud activity prevents ClO from undergoing sustained decline until about September 3. In contrast to the northern hemisphere, there is no significant chemical change in vortex-averaged ClON02 at 465 K, and there is an apparent decrease in ClON02 at 585 K, even after the enhanced ClO abundances have started to recede. Results from the SLIMCAT chemical transport model initialized with UARS data and run with OH + ClO yields HCl + 02 as an 8% channel suggest that the primary recovery product in the south during this time period is not ClON02, but HCl. HALOE HCl mixing ratios are extrapolated back to the time of the MLS and CLAES data. At 585 K, the chlorine budget can be made to balance by extrapolating HCl back to a value of 0.6 parts per billion by volume (ppbv) at the beginning of the study period; at 465 K, the contribution from extrapolated HCl is not sufficient to offset the loss in ClOx, and there is a slight imbalance between the decrease in reactive chlorine and the change in chlorine reservoirs. The difficulty in closing the chlorine budget in the southern hemisphere may arise from complications caused by ongoing activation, incomplete photochemical assumptions, and/or inadequate data quality.

Santee, M. L.↗
NASA NTRS2011

Impact of January 2005 Solar Proton Events on Chlorine Species

Sudden changes in stratospheric chlorine species in the polar northern atmosphere, caused by the Solar Proton Events (SPEs) of 17 and 20 January 2005, have been investigated and compared with version 4 of the Whole Atmosphere Community Climate Model (WACCM4). We used Aura Microwave Limb Sounder (MLS) measurements to monitor the variability of ClO, HCl, HOCl and Michelson Interferometer for Passive Atmospheric Sounder (MIPAS) on ENVISAT to retrieve ClONO2. SPE-induced chlorine activation has been identified. HCl decrease occurred at nearly all the investigated altitudes with the lowest values (of less than 0.25 ppbv) on 21 January. HOCl was found to be the main active chlorine species under nighttime conditions (with increases of more than 0.2 ppbv) whereas both HOCL and CLO enhancements (about 0.1 ppbv) have been observed at the polar night terminator. Further, small ClO decreases (of less than 0.1 ppbv) and ClONO2 enhancements (~0.2 ppbv) have been observed at higher latitudes (i.e., at nighttime) roughly above 2hPa. While WACCM4 reproduces most of the SPE-induced variability in the chlorine species fairly well, in some particular regions discrepancies between the modeled and measured temporal evolution of the abundances of chlorine species were found. HOCl changes are modelled very well with respect to both magnitude and geographic distribution. ClO decreases are reproduced at high latitudes, whereas ClO enhancements in the terminator region are underestimated and attributed to background variations. WACCM4 also reproduces the HCl depletion in the mesosphere but it does not show the observed decrease below about 2 hPa. Finally, WACCM4 simulations indicate that the observed ClONO2 increase is dominated by background variability, although SPE-induced production might contribute by 0.1 ppbv.

Damiani, A.↗
NASA NTRS2012

Impact of January 2005 Solar Proton Events on Chlorine Species

Sudden changes in stratospheric chlorine species in the polar northern atmosphere, caused by the Solar Proton Events (SPEs) of 17 and 20 January 2005, have been investigated and compared with version 4 of the Whole Atmosphere Community Climate Model (WACCM4). We used Aura Microwave Limb Sounder (MLS) measurements to monitor the variability of ClO, HCl, HOCl and Michelson Interferometer for Passive Atmospheric Sounder (MIPAS) on ENVISAT to retrieve ClONO2. SPE-induced chlorine activation has been identified. HCl decrease occurred at nearly all the investigated altitudes (i.e., 10-0.5 hPa) with the strongest decrease (of about 0.25 ppbv) on 21 January. HOCl was found to be the main active chlorine species under nighttime conditions (with increases of more than 0.2 ppbv) whereas both HOCl and ClO enhancements (about 0.1 ppbv) have been observed at the polar night terminator. Further, small ClO decreases (of less than 0.1 ppbv) and ClONO2 enhancements (about 0.2 ppbv) have been observed at higher latitudes (i.e., at nighttime) roughly above 2 hPa. While WACCM4 reproduces most of the SPE-induced variability in the chlorine species fairly well, in some particular regions discrepancies between the modeled and measured temporal evolution of the abundances of chlorine species were found. HOCl changes are modelled very well with respect to both magnitude and geographic distribution. ClO decreases are reproduced at high latitudes, whereas ClO enhancements in the terminator region are underestimated and attributed to background variations. WACCM4 also reproduces the HCl depletion in the mesosphere but it does not show the observed decrease below about 2 hPa. Finally, WACCM4 simulations indicate that the observed ClONO2 increase is dominated by background variability, although SPE-induced production might contribute by 0.1 ppbv.

Damiani, A.↗
NASA NTRS2016

The Chlorine Isotopic Composition Of Lunar UrKREEP

Since the long standing paradigm of an anhydrous Moon was challenged there has been a renewed focus on investigating volatiles in a variety of lunar samples. Numerous studies have examined the abundances and isotopic compositions of volatiles in lunar apatite, Ca5(PO4)3(F,Cl,OH). In particular, apatite has been used as a tool for assessing the sources of H2O in the lunar interior. However, current models for the Moon's formation have yet to fully account for its thermal evolution in the presence of H2O and other volatiles. For ex-ample, in the context of the lunar magma ocean (LMO) model, it is anticipated that chlorine (and other volatiles) should have been concentrated in the late-stage LMO residual melts (i.e., the dregs enriched in incompatible elements such as K, REEs (Rare Earth Elements), and P, collectively called KREEP, and in its primitive form - urKREEP, given its incompatibility in mafic minerals like olivine and pyroxene, which were the dominant phases that crystallized early in the cumulate pile of the LMO. When compared to chondritic meteorites and terrestrial rocks, lunar samples have exotic chlorine isotope compositions, which are difficult to explain in light of the abundance and isotopic composition of other volatile species, especially H, and the current estimates for chlorine and H2O in the bulk silicate Moon (BSM). In order to better understand the processes involved in giving rise to the heavy chlorine isotope compositions of lunar samples, we have performed a comprehensive in situ high precision study of chlorine isotopes in lunar apatite from a suite of Apollo samples covering a range of geochemical characteristics and petrologic types.

Barnes, J. J.↗
NASA NTRS2017

Chlorine in Lunar Basalts

In the context of the lunar magma ocean (LMO) model, it is anticipated that chlorine (and other volatiles) should have been concentrated in the late-stage LMO residual melts (i.e., the dregs enriched in incompatible elements such as K, REEs, and P, collectively called KREEP, and in its primitive form - urKREEP, [1]), given its incompatibility in mafic minerals like olivine and pyroxene, which were the dominant phases that crystallized early in the cumulate pile of the LMO (e.g., [2]). When compared to chondritic meteorites and terrestrial rocks (e.g., [3-4]), lunar samples often display heavy chlorine isotope compositions [5-9]. Boyce et al. [8] found a correlation between delta Cl-37 (sub Ap) and bulk-rock incompatible trace elements (ITEs) in lunar basalts, and used this to propose that early degassing of Cl (likely as metal chlorides) from the LMO led to progressive enrichment in remaining LMO melt in Cl-37over Cl-35- the early degassing model. Barnes et al. [9] suggested that relatively late degassing of chlorine from urKREEP (to yield delta Cl-37 (sub urKREEP greater than +25 per mille) followed by variable mixing between KREEPy melts and mantle cumulates (characterized by delta Cl-37~0 per mille) could explain the majority of Cl isotope data from igneous lunar samples. In order to better understand the processes involved in giving rise to the heavy chlorine isotope compositions of lunar samples, we have performed an in situ study of chlorine isotopes and abundances of volatiles in lunar apatite from a diverse suite of lunar basalts spanning a range of geochemical types.

Barnes, J. J.↗
NASA NTRS2013

Evidence for Perchlorates and the Origin of Chlorinated Hydrocarbons Detected by SAM at the Rocknest Aeolian Deposit in Gale Crater

Four individual sample portions from a single scoop of the Rocknest aeolian deposit were sieved ( 150 m) and delivered to the Sample Analysis at Mars (SAM) instrument by the Mars Science Laboratory rover's sample acquisition system. The samples were analyzed separately by the SAM pyrolysis evolved gas and gas chromatography mass spectrometry analysis modes. Several chlorinated hydrocarbons including chloromethane, dichloromethane, trichloromethane, a chloromethylpropene, and chlorobenzene were identified by SAM above background levels with abundances of 0.01 to 2.3 nanomole.The evolution of the chloromethanes observed during pyrolysis is coincident with the increase in O2 released from the Rocknest sample and the decomposition of a product of N-methyl-N- (tert-butyldimethylsilyl)trifluoroacetamide (MTBSTFA), a chemical that leaked from a derivatization cup inside SAM.The best candidate for the oxychloride phase in Rocknest is a hydrated calcium perchlorate (Ca(ClO4)2nH2O), based on the temperature release of O2 that correlates with the release of the chlorinated species measured by SAM, although other chlorine bearing phases are being considered. Laboratory pyrolysis experiments suggest that reaction of martian chlorine with organic carbon from MTBSTFA can explain the presence of the chloromethanes and a chloromethylpropene also detected by SAM.However, we cannot exclude the possibility that traces of organic carbon of either martian or exogenous origin contributed to some of the chloromethanes measured by SAM. Although the alteration history and exposure age of the Rocknest deposit is unknown, it is possible that oxidative degradation of complex organic matter by ionizing radiation or other chemical processes in Rocknest has occurred.

Mars Rover↗