Beryllium 7 and Lead 210 in the western hemisphere Arctic atmosphere: Observations from three recent aircraft-based sampling programs

Concentrations of the natural radionuclides 7Be and 210Pb were determined in aerosol samples collected in the western hemisphere Arctic during the recent NOAA Arctic Gas and Aerosol Sampling Program (AGASP 3) and NASA Global Tropospheric Experiment/Arctic Boundary Layer Expeditions (GTE/ABLE 3A and ABLE 3B) missions. Beryllium 7 showed a free tropospheric concentration maximum between 4 and 5 km in the summer of 1990. Previous 7Be data obtained in the late 1950s and early 1960s also indicated a similar vertical distribution of 7Be near 70°N. Injection of stratospheric air through tropopause folds associated with the Arctic jet near 70°N appears to explain the presence of a layer of air near 4–5 km in the high Arctic free troposphere with elevated 7Be concentrations. The vertical distribution of 210Pb showed a distinct difference between the high-Arctic and sub-Arctic in the summer of 1988. At latitudes greater than 65°N, 210Pb concentrations at 3–6 km were elevated compared to those below 1 km. The reverse of this trend was observed near 60°N. These same vertical distributions were also apparent in aerosol SO42−, determined in separate aerosol samples collected on the same flights (Talbot et al., this issue). The results for 210Pb suggest that some of the difference between the summer troposphere in the high- and sub-Arctic is also due to enhanced stratosphere-troposphere exchange in the vicinity of the Arctic jet. These observations, and other findings from ABLE 3A presented in this issue, suggest that for some species the stratosphere may be a principal source influencing their distribution in the Arctic summer troposphere. For example, intrusions of stratospheric air constitute the dominant source term for tropospheric budgets of 7Be and ozone, and may be important in the 210Pb, SO42−, and NOybudgets. Further investigation, including determination of detailed 7Be and 210Pb distributions, is needed to quantify the stratospheric impact on the chemistry of the Arctic troposphere during the summer

Aerosol major ion record at Mount Washington

This study examined the seasonal cycles and regional-scale meteorological controls on the chemical properties of bulk aerosols collected from 1999 to 2004 at Mount Washington, the highest peak in the northeastern United States. The concentrations of NH4+ and SO42− peaked during summer months. The pattern for aerosol NO3− was more complicated with relatively high median concentrations characterizing spring and summer months, but with major elevated events occurring during fall, winter, and spring. The seasonal relationship between NH4+ and SO42− indicated that during warmer months a mixture of (NH4)2SO4 and NH4HSO4 was present, while it was mainly the latter in winter. More acidity and higher concentrations of the major species were generally associated with winds from the southwest and west sectors. The highest (≥95th percentile) concentrations of SO42− and NH4+ were associated with air mass transport from major upwind source regions in the Midwest and along the eastern seaboard. The ionic composition and seasonal cycle observed at Mount Washington were similar to those measured at other northeastern sites, but the range and average concentrations were much lower. These differences were exaggerated during wintertime. Included in this paper are several Eulerian case studies of SO2 conversion to SO42− during transit from Whiteface Mountain, New York, to Mount Washington. The calculations suggest a gas-phase SO2 oxidation rate of ∼1–2% per hour and demonstrate the possibility of using these two sites to investigate the chemical evolution of air masses as they move from Midwestern source regions to northern New England

Large-scale distributions of tropospheric nitric, formic, and acetic acids over the western Pacific basin during wintertime

We report here measurements of the acidic gases nitric (HNO3), formic (HCOOH), and acetic (CH3COOH) over the western Pacific basin during the February-March 1994 Pacific Exploratory Mission-West (PEM-West B). These data were obtained aboard the NASA DC-8 research aircraft as it flew missions in the altitude range of 0.3–12.5 km over equatorial regions near Guam and then further westward encompassing the entire Pacific Rim arc. Aged marine air over the equatorial Pacific generally exhibited mixing ratios of acidic gases \u3c100 parts per trillion by volume (pptv). Near the Asian continent, discrete plumes encountered below 6 km altitude contained up to 8 parts per billion by volume (ppbv) HNO3 and 10 ppbv HCOOH and CH3COOH. Overall there was a general correlation between mixing ratios of acidic gases with those of CO, C2H2, and C2Cl4, indicative of emissions from combustion and industrial sources. The latitudinal distributions of HNO3 and CO showed that the largest mixing ratios were centered around 15°N, while HCOOH, CH3COOH, and C2Cl4 peaked at 25°N. The mixing ratios of HCOOH and CH3COOH were highly correlated (r2 = 0.87) below 6 km altitude, with a slope (0.89) characteristic of the nongrowing season at midlatitudes in the northern hemisphere. Above 6 km altitude, HCOOH and CH3COOH were marginally correlated (r2 = 0.50), and plumes well defined by CO, C2H2, and C2Cl4 were depleted in acidic gases, most likely due to scavenging during vertical transport of air masses through convective cloud systems over the Asian continent. In stratospheric air masses, HNO3 mixing ratios were several parts per billion by volume (ppbv), yielding relationships with O3 and N2O consistent with those previously reported for NOy

Chemical and physical properties of bulk aerosols within four sectors observed during TRACE-P

Chemical and physical aerosol data collected on the DC-8 during TRACE-P were grouped into four sectors based on back trajectories. The four sectors represent long-range transport from the west (WSW), regional circulation over the western Pacific and Southeast Asia (SE Asia), polluted transport from northern Asia with substantial sea salt at low altitudes (NNW) and a substantial amount of dust (Channel). WSW has generally low mixing ratios at both middle and high altitudes, with the bulk of the aerosol mass due to non-sea-salt water-soluble inorganic species. Low altitude SE Asia also has low mean mixing ratios in general, with the majority of the aerosol mass comprised of non-sea-salts, however, soot is also relatively important in this region. NNW had the highest mean sea salt mixing ratios, with the aerosol mass at low altitudes (\u3c2 km) evenly divided between sea salts, non-sea-salts, and dust. The highest mean mixing ratios of water-soluble ions and soot were observed at the lowest altitudes (\u3c2 km) in the Channel sector. The bulk of the aerosol mass exported from Asia emanates from Channel at both low and midaltitudes, due to the prevalence of dust compared to other sectors. Number densities show enhanced fine particles for Channel and NNW, while their volume distributions are enhanced due to sea salt and dust. Low-altitude Channel exhibits the highest condensation nuclei (CN) number densities along with enhanced scattering coefficients, compared to the other sectors. At midaltitudes (2–7 km), low mean CN number densities coupled with a high proportion of nonvolatile particles (≥65%) observed in polluted sectors (Channel and NNW) are attributed to wet scavenging which removes hygroscopic CN particles. Low single scatter albedo in SE Asia reflects enhanced soot

Species-specific responses to landscape features shaped genomic structure within Alaska galliformes

Aim: Connectivity is vital to the resiliency of populations to environmental change and stochastic events, especially for cold-adapted species as Arctic and alpine tundra habitats retract as the climate warms. We examined the influence of past and current landscapes on genomic connectivity in cold-adapted galliformes as a critical first step to assess the vulnerability of Alaska ptarmigan and grouse to environmental change. We hypothesize that the mosaic of physical features and habitat within Alaska promoted the formation of genetic structure across species. Location: Alaska, United States of America. Taxa: Ptarmigan and Grouse (Galliformes: Tetraoninae). Methods: We collected double digest restriction-site- associated DNA sequence data from six ptarmigan and grouse species (N = 13–145/ species) sampled across multiple ecosystems up to ~10 degrees of latitude. Spatial genomic structure was analysed using methods that reflect different temporal scales: (1) principal components analysis to identify major trends in the distribution of genomic variation; (2) maximum likelihood clustering analyses to test for the presence of multiple genomic groupings; (3) shared co-ancestry analyses to assess contemporary relationships and (4) effective migration surfaces to identify regions that deviate from a null model of isolation by distance. Results: Levels of genomic structure varied across species (ΦST =0.009–0.042). Three general patterns of structure emerged: (1) east-west partition located near the Yukon-Tanana uplands; (2) north-south split coinciding with the Alaska Range and (3) northern group near the Brooks Range. Species-specific patterns were observed; not all landscape features were barriers to gene flow for all ptarmigan and grouse and temporal contrasts were detected at the Brooks Range. Main conclusions: Within Alaska galliformes, patterns of genomic structure coincide with physiographic features and highlight the importance of physical and ecological barriers in shaping how genomic diversity is arrayed across the landscape. Lack of concordance in spatial patterns indicates that species behaviour and habitat affinities play key roles in driving the contrasting patterns of genomic structure

Constraints on the age and dilution of Pacific Exploratory Mission-Tropics biomass burning plumes from the natural radionuclide tracer 210Pb

During the NASA Global Troposphere Experiment Pacific Exploratory Mission-Tropics (PEM-Tropics) airborne sampling campaign we found unexpectedly high concentrations of aerosol-associated 210Pb throughout the free troposphere over the South Pacific. Because of the remoteness of the study region, we expected specific activities to be generally less than 35 μBq m−3 but found an average in the free troposphere of 107 μBq m−3. This average was elevated by a large number of very active (up to 405 μBq m−3) samples that were associated with biomass burning plumes encountered on nearly every PEM-Tropics flight in the southern hemisphere. We use a simple aging and dilution model, which assumes that 222Rn and primary combustion products are pumped into the free troposphere in wet convective systems over fire regions (most likely in Africa), to explain the elevated 210Pb activities. This model reproduces the observed 210Pb activities very well, and predicts the ratios of four hydrocarbon species (emitted by combustion) to CO to better than 20% in most cases. Plume ages calculated by the model depend strongly on the assumed 222Rn activities in the initial plume, but using values plausible for continental boundary layer air yields ages that are consistent with travel times from Africa to the South Pacific calculated with a back trajectory model. The model also shows that despite being easily recognized through the large enhancements of biomass burning tracers, these plumes must have entrained large fractions of the surrounding ambient air during transport

A comparison of GC-FID and PTR-MS toluene measurements in ambient air under conditions of enhanced monoterpene loading

Toluene was measured using both a gas chromatographic system (GC), with a flame ionization detector (FID), and a proton transfer reaction-mass spectrometer (PTR-MS) at the AIRMAP atmospheric monitoring station Thompson Farm (THF) in rural Durham, NH during the summer of 2004. Simultaneous measurements of monoterpenes, including alpha- and beta-pinene, camphene, Delta(3)-carene, and d-limonene, by GC-FID demonstrated large enhancements in monoterpene mixing ratios relative to toluene, with median and maximum enhancement ratios of similar to 2 and similar to 30, respectively. A detailed comparison between the GC-FID and PTR-MS toluene measurements was conducted to test the specificity of PTR-MS for atmospheric toluene measurements under conditions often dominated by biogenic emissions. We derived quantitative estimates of potential interferences in the PTR-MS toluene measurements related to sampling and analysis of monoterpenes, including fragmentation of the monoterpenes and some of their primary carbonyl oxidation products via reactions with H(3)O(+), O(2)(+) and NO(+) in the PTR-MS drift tube. The PTR-MS and GC-FID toluene measurements were in good quantitative agreement and the two systems tracked one another well from the instrumental limits of detection to maximum mixing ratios of similar to 0.5 ppbv. A correlation plot of the PTR-MS versus GC-FID toluene measurements was described by the least squares regression equation y=(1.13 +/- 0.02)x-(0.008 +/- 0.003) ppbv, suggesting a small similar to 13% positive bias in the PTR-MS measurements. The bias corresponded with a similar to 0.055 ppbv difference at the highest measured toluene level. The two systems agreed quantitatively within the combined 1 sigma measurement precisions for 60% of the measurements. Discrepancies in the measured mixing ratios were not well correlated with enhancements in the monoterpenes. Better quantitative agreement between the two systems was obtained by correcting the PTR-MS measurements for contributions from monoterpene fragmentation in the PTR-MS drift tube; however, the improvement was minor (\u3c10%). Interferences in the PTRMS measurements from fragmentation of the monoterpene oxidation products pinonaldehyde, caronaldehyde and alpha-pinene oxide were also likely negligible. A relatively large and variable toluene background in the PTR-MS instrument likely drove the measurement bias; however, the precise contribution was difficult to accurately quantify and thus was not corrected for in this analysis. The results from THF suggest that toluene can be reliably quantified by PTR-MS using our operating conditions (drift tube pressure, temperature and voltage of 2.0 mbar, 45 degrees C and 600V, respectively) under the ambient compositions probed. This work extends the range of field conditions under which PTR-MS validation studies have been conducted

Phylogenomics reveals ancient and contemporary gene flow contributing to the evolutionary history of sea ducks (Tribe Mergini)

Insight into complex evolutionary histories continues to build through broad comparative phylogenomic and population genomic studies. In particular, there is a need to understand the extent and scale that gene flow contributes to standing genomic diversity and the role introgression has played in evolutionary processes such as hybrid speciation. Here, we investigate the evolutionary history of the Mergini tribe (sea ducks) by coupling multi-species comparisons with phylogenomic analyses of thousands of nuclear ddRAD-seq loci, including Z-sex chromosome and autosomal linked loci, and the mitogenome assayed across all extant sea duck species in North America. All sea duck species are strongly structured across all sampled marker types (pair-wise species ΦST \u3e 0.2), with clear genetic assignments of individuals to their respective species, and phylogenetic relationships recapitulate known relationships. Despite strong species integrity, we identify at least 18 putative hybrids; with all but one being late generational backcrosses. Most interesting, we provide the first evidence that an ancestral gene flow event between long-tailed ducks (Clangula hyemalis) and true Eiders (Somateria spp.) not only moved genetic material into the former species, but likely generated a novel species — the Steller’s eider (Polysticta stelleri) — via hybrid speciation. Despite generally low contemporary levels of gene flow, we conclude that hybridization has and continues to be an important process that shifts novel genetic variation between species within the tribe Mergini. Finally, we outline methods that permit researchers to contrast genomic patterns of contemporary versus ancestral gene flow when attempting to reconstruct potentially complex evolutionary histories

Are biogenic emissions a significant source of summertime atmospheric toluene in the rural Northeastern United States?

Summertime atmospheric toluene enhancements at Thompson Farm in the rural northeastern United States were unexpected and resulted in a toluene/benzene seasonal pattern that was distinctly different from that of other anthropogenic volatile organic compounds. Consequently, three hydrocarbon sources were investigated for potential contributions to the enhancements during 2004–2006. These included: (1) increased warm season fuel evaporation coupled with changes in reformulated gasoline (RFG) content to meet US EPA summertime volatility standards, (2) local industrial emissions and (3) local vegetative emissions. The contribution of fuel evaporation emission to summer toluene mixing ratios was estimated to range from 16 to 30 pptv d−1, and did not fully account for the observed enhancements (20–50 pptv) in 2004–2006. Static chamber measurements of alfalfa, a crop at Thompson Farm, and dynamic branch enclosure measurements of loblolly pine trees in North Carolina suggested vegetative emissions of 5 and 12 pptv d−1 for crops and coniferous trees, respectively. Toluene emission rates from alfalfa are potentially much larger as these plants were only sampled at the end of the growing season. Measured biogenic fluxes were on the same order of magnitude as the influence from gasoline evaporation and industrial sources (regional industrial emissions estimated at 7 pptv d−1 and indicated that local vegetative emissions make a significant contribution to summertime toluene enhancements. Additional studies are needed to characterize the variability and factors controlling toluene emissions from alfalfa and other vegetation types throughout the growing season