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Open Access Publications from the University of California

Scholarly Works (8 results)

  • Article
  • Peer Reviewed
Faculty Publications (2009)
The atmospheric methyl bromide (CH3Br) burden has declined in recent years, in response to the phaseout of agricultural and structural fumigation consumption under the amendments to the Montreal Protocol. The timing and magnitude of this decrease represents an opportunity to examine our current understanding of atmospheric CH3Br and its budget, response to the phaseout, and response to interannual variability in biomass burning and global OH. In this study, simulations obtained from a time-dependent global model of atmospheric CH3Br emissions and uptake are compared to observations from the NOAA flask network. The model includes a detailed gridded ocean model coupled to a time-dependant atmospheric 2-box model. The phaseout of CH3Br production for agricultural uses began in 1998, concurrent with the pulse in biomass burning associated with the 1998 El Niño. The combined effects of three factors (biomass burning, global OH, and anthropogenic phaseout) appear to explain most of the observed atmospheric methyl bromide variability over the 1997–2008 period. The global budget remains imbalanced, with a large missing source indicated. The missing source does not exhibit a systematic decline during the phaseout period, and therefore, is not the result of significantly underestimating non-QPS agricultural CH3Br emissions. The model results suggest that the oceans should be less undersaturated than before the phaseout began.
    Cover page: Recent trends in atmospheric methyl bromide: analysis of post-Montreal Protocol variabilityCreative Commons 'BY' version 4.0 license
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    Faculty Publications (2004)
    Measurements of methyl chloride (CH3Cl) in Antarctic polar ice and firn air are used to describe the variability of atmospheric CH3Cl during the past 300 years. Firn air results from South Pole and Siple Dome suggest that the atmospheric abundance of CH3Cl increased by about 10% in the 50 years prior to 1990. Ice core measurements from Siple Dome provide evidence for a cyclic natural variability on the order of 10%, with a period of about 110 years in phase with the 20th century rise inferred from firn air. Thus, the CH3Cl increase measured in firn air may largely be a result of natural processes, which may continue to affect the atmospheric CH3Cl burden during the 21st century.
      Cover page: Atmospheric variability of methyl chloride during the last 300 years from an Antarctic ice core and firn airCreative Commons 'BY' version 4.0 license
      • Article
      • Peer Reviewed
      Faculty Publications (2010)
      Firn-air and ambient air measurements of CHF3 (HFC-23) from three excursions to Antarctica between 2001 and 2009 are used to construct a consistent Southern Hemisphere (SH) atmospheric history. The results show atmospheric mixing ratios of HFC-23 continuing to increase through 2008. Mean global emissions derived from this data for 2006–2008 are 13.5 ± 2 Gg/yr (200 ± 30 × 1012 gCO2-equivalent/yr, or MtCO2-eq./yr), ∼50% higher than the 8.7 ± 1 Gg/yr (130 ± 15 MtCO2-eq./yr) derived for the 1990s. HFC-23 emissions arise primarily from over-fluorination of chloroform during HCFC-22 production. The recent global emission increases are attributed to rapidly increasing HCFC-22 production in developing countries since reported HFC-23 emissions from developed countries decreased over this period. The emissions inferred here for developing countries during 2006–2008 averaged 11 ± 2 Gg/yr HFC-23 (160 ± 30 MtCO2-eq./yr) and are larger than the ∼6 Gg/yr of HFC-23 destroyed in United Nations Framework Convention on Climate Change Clean Development Mechanism projects during 2007 and 2008.
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      Cover page: Recent increases in global HFC-23 emissionsCreative Commons 'BY' version 4.0 license
      • Article
      • Peer Reviewed
      Faculty Publications (2004)
      Carbonyl sulfide (COS) and other trace gases were measured in firn air collected near South Pole (89.98°S) and from air trapped in ice at Siple Dome, Antarctica (81.65°S). The results, when considered with ambient air data and previous ice core measurements, provide further evidence that atmospheric mixing ratios of COS over Antarctica between 1650 and 1850 A.D. were substantially lower than those observed today. Specifically, the results suggest annual mean COS mixing ratios between 300 and 400 pmol mol−1 (ppt) during 1650–1850 A.D. and increases throughout most of the twentieth century. Measurements of COS in modern air and in the upper layers of the firn at South Pole indicate ambient, annual mean mixing ratios between 480 and 490 ppt with substantial seasonal variations. Peak mixing ratios are observed during austral summer in ambient air at South Pole and Cape Grim, Tasmania (40.41°S). Provided COS is not produced or destroyed in firn, these results also suggest that atmospheric COS mixing ratios have decreased 60–90 ppt (10–16%) since the 1980s in high latitudes of the Southern Hemisphere. The history derived for atmospheric mixing ratios of COS in the Southern Hemisphere since 1850 is closely related to historical anthropogenic sulfur emissions. The fraction of anthropogenic sulfur emissions released as COS (directly or indirectly) needed to explain the secular changes in atmospheric COS over this period is 0.3–0.6%.
        Cover page: A 350-year atmospheric history for carbonyl sulfide inferred from Antarctic firn air and air trapped in iceCreative Commons 'BY' version 4.0 license
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        UC Irvine Previously Published Works (2011)
        We sampled interstitial air from the perennial snowpack (firn) at a site near the West Antarctic Ice Sheet Divide (WAIS-D) and analyzed the air samples for a wide variety of gas species and their isotopes. We find limited convective influence (1.4-5.2 m, depending on detection method) in the shallow firn, gravitational enrichment of heavy species throughout the diffusive column in general agreement with theoretical expectations, a similar to 10 m thick lock-in zone beginning at similar to 67 m, and a total firn thickness consistent with predictions of Kaspers et al. (2004). Our modeling work shows that the air has an age spread (spectral width) of 4.8 yr for CO2 at the firn-ice transition. We also find that advection of firn air due to the 22 cm yr(-1) ice-equivalent accumulation rate has a minor impact on firn air composition, causing changes that are comparable to other modeling uncertainties and intrinsic sample variability. Furthermore, estimates of 1 age (the gas age/ice age difference) at WAIS-D appear to be largely unaffected by bubble closure above the lock-in zone. Within the lock-in zone, small gas species and their isotopes show evidence of size-dependent fractionation due to permeation through the ice lattice with a size threshold of 0.36 nm, as at other sites. We also see an unequivocal and unprecedented signal of oxygen isotope fractionation within the lock-in zone, which we interpret as the mass-dependent expression of a size-dependent fractionation process.
          Cover page: Controls on the movement and composition of firn air at the West Antarctic Ice Sheet DivideCreative Commons 'BY' version 4.0 license
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          Faculty Publications (2000)

          A global climatological distribution of tropospheric OH is computed using observed distributions of O3, H2O, NOt (NO2 +NO + 2N2O5 + NO3 + HNO2 +HNO4), CO, hydrocarbons, temperature, and cloud optical depth. Global annual mean OH is 1.16×106 molecules cm−3(integrated with respect to mass of air up to 100 hPa within ±32° latitude and up to 200 hPa outside that region). Mean hemispheric concentrations of OH are nearly equal. While global mean OH increased by 33% compared to that from Spivakovsky et al. [1990], mean loss frequencies of CH3CCl3 and CH4 increased by only 23% because a lower fraction of total OH resides in the lower troposphere in the present distribution. The value for temperature used for determining lifetimes of hydrochlorofluorocarbons (HCFCs) by scaling rate constants [Prather and Spivakovsky, 1990] is revised from 277 K to 272 K. The present distribution of OH is consistent within a few percent with the current budgets of CH3CCl3 and HCFC-22. For CH3CCl3, it results in a lifetime of 4.6 years, including stratospheric and ocean sinks with atmospheric lifetimes of 43 and 80 years, respectively. For HCFC-22, the lifetime is 11.4 years, allowing for the stratospheric sink with an atmospheric lifetime of 229 years. Corrections suggested by observed levels of CH2Cl2 (annual means) depend strongly on the rate of interhemispheric mixing in the model. An increase in OH in the Northern Hemisphere by 20% combined with a decrease in the southern tropics by 25% is suggested if this rate is at its upper limit consistent with observations of CFCs and 85Kr. For the lower limit, observations of CH2Cl2 imply an increase in OH in the Northern Hemisphere by 35% combined with a decrease in OH in the southern tropics by 60%. However, such large corrections are inconsistent with observations for 14CO in the tropics and for the interhemispheric gradient of CH3CCl3. Industrial sources of CH2Cl2 are sufficient for balancing its budget. The available tests do not establish significant errors in OH except for a possible underestimate in winter in the northern and southern tropics by 15–20% and 10–15%, respectively, and an overestimate in southern extratropics by ∼25%. Observations of seasonal variations of CH3CCl3, CH2Cl2,14CO, and C2H6 offer no evidence for higher levels of OH in the southern than in the northern extratropics. It is expected that in the next few years the latitudinal distribution and annual cycle of CH3CCl3 will be determined primarily by its loss frequency, allowing for additional constraints for OH on scales smaller than global.

            Cover page: Three-dimensional climatological distribution of tropospheric OH: Update and evaluationCreative Commons 'BY' version 4.0 license
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            • Peer Reviewed
            Faculty Publications (2010)
            n this study, we report measurements of CFC-12 (CCl2F2) in firn air and in air extracted from shallow ice cores from three Antarctic sites. The firn air data are consistent with the known atmospheric history of CFC-12. In contrast, some of the ice core samples collected near the firn-ice transition exhibit anomalously high CFC-12 levels. Together, the ice core and firn air data provide evidence for the presence of modern air entrapped in the shallow ice core samples that likely contained open pores at the time of collection. We propose that this is due to closure of the open pores after drilling, entrapping modern air and resulting in elevated CFC-12 mixing ratios. Our results reveal that open porosity can exist below the maximum depth at which firn air samples can be collected, particularly at sites with lower accumulation rates. CFC-12 measurements demonstrate that post-drilling closure of open pores can lead to a change in the composition of bubble air in shallow ice cores through purely physical processes. The results have implications for investigations involving trace gas composition of bubbles in shallow ice cores collected near the firn-ice transition.
              Cover page: Post-coring entrapment of modern air in some shallow ice cores collected near the firn-ice transition: evidence from CFC-12 measurements in Antarctic firn air and ice coresCreative Commons 'BY' version 4.0 license
              • Article
              • Peer Reviewed
              Faculty Publications (2013)
              The International Halocarbons in Air Comparison Experiment (IHALACE) was conducted to document relationships between calibration scales among various laboratories that measure atmospheric greenhouse and ozone depleting gases. Six stainless steel cylinders containing natural and modified natural air samples were circulated among 19 laboratories. Results from this experiment reveal relatively good agreement among commonly used calibration scales for a number of trace gases present in the unpolluted atmosphere at pmol mol−1 (parts per trillion) levels, such as chlorofluorocarbons (CFCs), hydrochlorofluorocarbons (HCFCs), and hydrofluorocarbons (HFCs). Some scale relationships were found to be consistent with those derived from bi-lateral experiments or from analysis of atmospheric data, while others revealed discrepancies. The transfer of calibration scales among laboratories was found to be problematic in many cases, meaning that measurements tied to a common scale may not, in fact, be compatible. These results reveal substantial improvements in calibration over previous comparisons. However there is room for improvement in communication and coordination of calibration activities with respect to the measurement of halogenated and related trace gases.
                Cover page: Results from the International Halocarbons in Air Comparison Experiment (IHALACE)Creative Commons 'BY' version 4.0 license
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