Tropospheric ozonesonde profiles at long-term U.S. monitoring sites: 2. Links between Trinidad Head, CA, profile clusters and inland surface ozone measurements.

Much attention has been focused on the transport of ozone (O3) to the Western U.S., particularly given the latest revision of the National Ambient Air Quality Standard (NAAQS) to 70 parts per billion by volume (ppbv) of O3. This makes defining a "background" O3 amount essential so that the effects of stratosphere-to-troposphere exchange and pollution transport to this region can be quantified. To evaluate free-tropospheric and surface O3 in the Western U.S., we use self-organizing maps to cluster 18 years of ozonesonde profiles (940 samples) from Trinidad Head, CA. Two of nine O3 mixing ratio profile clusters exhibit thin laminae of high O3 above Trinidad Head. A third, consisting of background (~20 - 40 ppbv) O3, occurs in ~10% of profiles. The high O3 layers are located between 1 and 4 km amsl, and reside above a subsidence inversion associated with a northern location of the semi-permanent Pacific subtropical high. Several ancillary data sets are examined to identify the high O3 sources (reanalyses, trajectories, remotely-sensed carbon monoxide), but distinguishing chemical and stratospheric influences of the elevated O3 is difficult. There is marked and long-lasting impact of the elevated tropospheric O3 on high-altitude surface O3 monitors at Lassen Volcanic and Yosemite National Parks, and Truckee, CA. Days corresponding to the high O3 clusters exhibit hourly surface O3 anomalies of +5 - 10 ppbv compared to a climatology; the anomalies can last up to four days. The profile and surface O3 links demonstrate the importance of regular ozonesonde profiling at Trinidad Head.

Recent divergences in stratospheric water vapor measurements by frost point hygrometers and the Aura Microwave Limb Sounder.

Balloon-borne frost point hygrometers (FPs) and the Aura Microwave Limb Sounder (MLS) provide high-quality vertical profile measurements of water vapor in the upper troposphere and lower stratosphere (UTLS). A previous comparison of stratospheric water vapor measurements by FPs and MLS over three sites - Boulder, Colorado (40.0° N); Hilo, Hawaii (19.7° N); and Lauder, New Zealand (45.0° S) - from August 2004 through December 2012 not only demonstrated agreement better than 1% between 68 and 26 hPa but also exposed statistically significant biases of 2 to 10% at 83 and 100 hPa (Hurst et al., 2014). A simple linear regression analysis of the FP-MLS differences revealed no significant long-term drifts between the two instruments. Here we extend the drift comparison to mid-2015 and add two FP sites - Lindenberg, Germany (52.2° N), and San José, Costa Rica (10.0° N) - that employ FPs of different manufacture and calibration for their water vapor soundings. The extended comparison period reveals that stratospheric FP and MLS measurements over four of the five sites have diverged at rates of 0.03 to 0.07 ppmv year-1 (0.6 to 1.5% year-1) from ~2010 to mid-2015. These rates are similar in magnitude to the 30-year (1980-2010) average growth rate of stratospheric water vapor (~ 1% year-1) measured by FPs over Boulder (Hurst et al., 2011). By mid-2015, the FP-MLS differences at some sites were large enough to exceed the combined accuracy estimates of the FP and MLS measurements.

Advancements, measurement uncertainties, and recent comparisons of the NOAA frost point hygrometer.

The NOAA frost point hygrometer (FPH) is a balloon-borne instrument flown monthly at three sites to measure water vapor profiles up to 28 km. The FPH record from Boulder, Colorado, is the longest continuous stratospheric water vapor record. The instrument has an uncertainty in the stratosphere that is < 6 % and up to 12 % in the troposphere. A digital microcontroller version of the instrument improved upon the older versions in 2008 with sunlight filtering, better frost control, and resistance to radio frequency interference (RFI). A new thermistor calibration technique was implemented in 2014, decreasing the uncertainty in the thermistor calibration fit to less than 0.01 °C over the full range of frost - or dew point temperatures (-93 to +20 °C) measured during a profile. Results from multiple water vapor intercomparisons are presented, including the excellent agreement between the NOAA FPH and the direct tunable diode laser absorption spectrometer (dTDLAS) MC-PicT-1.4 during AquaVIT-2 chamber experiments over 6 days that provides confidence in the accuracy of the FPH measurements. Dual instrument flights with two FPHs or an FPH and a cryogenic frost point hygrometer (CFH) also show good agreement when launched on the same balloon. The results from these comparisons demonstrate the high level of accuracy of the NOAA FPH.

Climate variability modulates western US ozone air quality in spring via deep stratospheric intrusions.

Evidence suggests deep stratospheric intrusions can elevate western US surface ozone to unhealthy levels during spring. These intrusions can be classified as 'exceptional events', which are not counted towards non-attainment determinations. Understanding the factors driving the year-to-year variability of these intrusions is thus relevant for effective implementation of the US ozone air quality standard. Here we use observations and model simulations to link these events to modes of climate variability. We show more frequent late spring stratospheric intrusions when the polar jet meanders towards the western United States, such as occurs following strong La Niña winters (Niño3.4<-1.0 °C). While El Niño leads to enhancements of upper tropospheric ozone, we find this influence does not reach surface air. Fewer and weaker intrusion events follow in the two springs after the 1991 volcanic eruption of Mt. Pinatubo. The linkage between La Niña and western US stratospheric intrusions can be exploited to provide a few months of lead time during which preparations could be made to deploy targeted measurements aimed at identifying these exceptional events.

Validation of Aura Microwave Limb Sounder stratospheric water vapor measurements by the NOAA frost point hygrometer.

Differences between stratospheric water vapor measurements by NOAA frost point hygrometers (FPHs) and the Aura Microwave Limb Sounder (MLS) are evaluated for the period August 2004 through December 2012 at Boulder, Colorado, Hilo, Hawaii, and Lauder, New Zealand. Two groups of MLS profiles coincident with the FPH soundings at each site are identified using unique sets of spatiotemporal criteria. Before evaluating the differences between coincident FPH and MLS profiles, each FPH profile is convolved with the MLS averaging kernels for eight pressure levels from 100 to 26 hPa (~16 to 25 km) to reduce its vertical resolution to that of the MLS water vapor retrievals. The mean FPH - MLS differences at every pressure level (100 to 26 hPa) are well within the combined measurement uncertainties of the two instruments. However, the mean differences at 100 and 83 hPa are statistically significant and negative, ranging from -0.46 ± 0.22 ppmv (-10.3 ± 4.8%) to -0.10 ± 0.05 ppmv (-2.2 ± 1.2%). Mean differences at the six pressure levels from 68 to 26 hPa are on average 0.8% (0.04 ppmv), and only a few are statistically significant. The FPH - MLS differences at each site are examined for temporal trends using weighted linear regression analyses. The vast majority of trends determined here are not statistically significant, and most are smaller than the minimum trends detectable in this analysis. Except at 100 and 83 hPa, the average agreement between MLS retrievals and FPH measurements of stratospheric water vapor is better than 1%.

Establishing policy relevant background (PRB) ozone concentrations in the United States.

Policy Relevant Background (PRB) ozone concentrations are defined by the United States (U.S.) Environmental Protection Agency (EPA) as those concentrations that would occur in the U.S. in the absence of anthropogenic emissions in continental North America (i.e., the U.S, Canada, and Mexico). Estimates of PRB ozone have had an important role historically in the EPA's human health and welfare risk analyses used in establishing National Ambient Air Quality Standards (NAAQS). The margin of safety for the protection of public health in the ozone rulemaking process has been established from human health risks calculated based on PRB ozone estimates. Sensitivity analyses conducted by the EPA have illustrated that changing estimates of PRB ozone concentrations have a progressively greater impact on estimates of mortality risk as more stringent standards are considered. As defined by the EPA, PRB ozone is a model construct, but it is informed by measurements at relatively remote monitoring sites (RRMS). This review examines the current understanding of PRB ozone, based on both model predictions and measurements at RRMS, and provides recommendations for improving the definition and determination of PRB ozone.