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

Laminin and fibronectin in rectal adenocarcinoma: relationship to tumour grade, stage and metastasis.

Using an immunoperoxidase procedure, we have examined the distribution of laminin and fibronectin in normal human large intestinal mucosa and in 50 cases of rectal adenocarcinoma for which extensive clinical follow up was available. In normal tissue, laminin staining was largely restricted to basement membranes, including that underlying the epithelial cells, whereas fibronectin was found in both basement membranes and surrounding connective tissue. In rectal carcinomas, basement membrane-like staining for laminin associated with tumour cells was found in only 27 out of the 50 cases studied. Statistical analysis showed that the presence of laminin-containing basement membranes was correlated with low histological grade (well-differentiated tumours), but not with stage (progression through the bowel wall and the development of lymph node metastases) and, in a highly significant way, with a reduced incidence of distant metastases and increased patient survival. Although fibronectin was found in tumour cell basement membranes where these were present, it was also found in the stroma of all 50 tumours. There was no apparent correlation between the presence of stromal fibronectin and grade, stage or development of metastases. Finally, attention is drawn to some of the technical difficulties in detecting basement membrane antigens in formalin-fixed tissue, the material most frequently available for retrospective study

Diffusion and mixing in gravity-driven dense granular flows

We study the transport properties of particles draining from a silo using imaging and direct particle tracking. The particle displacements show a universal transition from super-diffusion to normal diffusion, as a function of the distance fallen, independent of the flow speed. In the super-diffusive (but sub-ballistic) regime, which occurs before a particle falls through its diameter, the displacements have fat-tailed and anisotropic distributions. In the diffusive regime, we observe very slow cage breaking and Peclet numbers of order 100, contrary to the only previous microscopic model (based on diffusing voids). Overall, our experiments show that diffusion and mixing are dominated by geometry, consistent with fluctuating contact networks but not thermal collisions, as in normal fluids

Chemical NOx budget in the upper troposphere over the tropical South Pacific

The chemical NOx budget in the upper troposphere over the tropical South Pacific is analyzed using aircraft measurements made at 6-12 km altitude in September 1996 during the Global Tropospheric Experiment (GTE) Pacific Exploratory Mission (PEM) Tropics A campaign. Chemical loss and production rates of NOx along the aircraft flight tracks are calculated with a photochemical model constrained by observations. Calculations using a standard chemical mechanism show a large missing source for NOx; chemical loss exceeds chemical production by a factor of 2.4 on average. Similar or greater NOx budget imbalances have been reported in analyses of data from previous field studies. Ammonium aerosol concentrations in PEM-Tropics A generally exceeded sulfate on a charge equivalent basis, and relative humidities were low (median 25% relative to ice). This implies that the aerosol could be dry in which case N2O5 hydrolysis would be suppressed as a sink for NOx. Suppression of N2O5 hydrolysis and adoption of new measurements of the reaction rate constants for NO2 + OH + M and HNO3 + OH reduces the median chemical imbalance in the NOx budget for PEM-Tropics A from 2.4 to 1.9. The remaining imbalance cannot be easily explained from known chemistry or long-range transport of primary NOx and may imply a major gap in our understanding of the chemical cycling of NOx in the free troposphere. Copyright 2000 by the American Geophysical Union

Rapid convective outflow from the U.S. to the upper troposphere over the North Atlantic during the NASA INTEX-NA airborne campaign: flight 13 case study

International audienceA case study of convective outflow from the United States (U.S.) was examined using airborne measurements from NASA DC-8 flight 13 during the Intercontinental Chemical Transport Experiment ? North America (INTEX-NA). Mixing ratios of methane (CH4) and carbon monoxide (CO) at 8?11 km altitude over the North Atlantic were elevated to 1843 ppbv and 134 ppbv respectively, while those of carbon dioxide (CO2) and carbonyl sulfide (COS) were reduced to 372.4 ppmv and 411 pptv respectively. In this region, urban and industrial influence was evidenced by elevated mixing ratios and good linear relationships between urban and industrial tracers compared to North Atlantic background air. Moreover, low mixing ratios and a good correlation between COS and CO2 showed a fingerprint of terrestrial uptake and minimal dilution during rapid transport over a 1?2 day time period. Analysis of synoptic conditions, backward trajectories, and photochemical aging estimates based on C3H8/C2H6 strongly suggested that elevated anthropogenic tracers in the upper troposphere of the flight region were the result of fast transport via convective uplifting of boundary layer air over the southeastern U.S. This mechanism is supported by the similar slopes values of linear correlations between long-lived (months) anthropogenic tracers (e.g., C2Cl4 and CHCl3) from the flight region and the planetary boundary layer in the southeastern U.S. In addition, the aircraft measurements suggest that outflow from the U.S. augmented the entire tropospheric column at mid-latitudes over the North Atlantic. Overall, the flight 13 data demonstrate a pervasive impact of U.S. anthropogenic emissions on the troposphere over the North Atlantic

Comparison of free tropospheric western Pacific air mass classification schemes for the PEM-West A experiment

During September/October 1991, NASA's Global Tropospheric Experiment (GTE) conducted an airborne field measurement program (PEM-West A) in the troposphere over the western Pacific Ocean. In this paper we describe and use the relative abundance of the combustion products C2H2 and CO to classify air masses encountered during PEM-West A based on the degree that these tracers were processed by the combined effects of photochemical reactions and dynamical mixing (termed the degree of atmospheric processing). A large number of trace compounds (e.g., C2H6, C3H8, C6H6, NOy, and O3) are found to be well correlated with the degree of atmospheric processing that is reflected by changes in the ratio of C2H2/CO over the range of values from ∼0.3 to 2.0 (parts per trillion volume) C2H2/ (parts per billion volume) CO. This C2H2/CO-based classification scheme is compared to model simulations and to two independent classification schemes based on air mass back-trajectory analyses and lidar profiles of O3 and aerosols. In general, these schemes agree well, and in combination they suggest that the functional dependence that other observed species exhibit with respect to the C2H2/CO atmospheric processing scale can be used to study the origin, sources, and sinks of trace species and to derive several important findings. First, the degree of atmospheric processing is found to be dominated by dilution associated with atmospheric mixing, which is found to primarily occur through the vertical mixing of relatively recent emissions of surface layer trace species. Photochemical reactions play their major role by influencing the background concentrations of trace species that are entrained during the mixing (i.e., dilution) process. Second, a significant noncontinental source(s) of NO (and NOx) in the free troposphere is evident. In particular, the enhanced NO mixing ratios that were observed in convected air masses are attributed to either emissions from lightning or the rapid recycling of NOy compounds. Third, nonsoluble trace species emitted in the continental boundary layer, such as CO and hydrocarbons, are vertically transported to the upper troposphere as efficiently as they are to the midtroposphere. In addition, the mixing ratios of CO and hydrocarbons in the upper troposphere over the western Pacific may reflect a significant contribution from northern hemisphere land areas other than Asia. Finally, we believe that these results can be valuable for the quantitative evaluation of the vertical transport processes that are usually parameterized in models. Copyright 1996 by the American Geophysical Union

Continental outflow from the US to the upper troposphere over the North Atlantic during the NASA INTEX-NA Airborne Campaign

A case of continental outflow from the United States (US) was examined using airborne measurements from NASA DC-8 flight 13 during the Intercontinental Chemical Transport Experiment – North America (INTEX-NA). Mixing ratios of methane (CH<sub>4</sub>) and carbon monoxide (CO) at 8–11 km altitude over the North Atlantic were elevated to 1843 ppbv and 134 ppbv respectively, while those of carbon dioxide (CO<sub>2</sub>) and carbonyl sulfide (COS) were reduced to 372.4 ppmv and 411 pptv respectively. In this region, urban and industrial influences were evidenced by elevated mixing ratios and good linear relationships between urban and industrial tracers compared to North Atlantic background air. Moreover, low mixing ratios and a good correlation between COS and CO<sub>2</sub> showed a fingerprint of terrestrial uptake and minimal dilution during rapid transport over a 1–2 day time period. Analysis of synoptic conditions, backward trajectories, and photochemical aging estimates based on C<sub>3</sub>H<sub>8</sub>/C<sub>2</sub>H<sub>6</sub> strongly suggested that elevated anthropogenic tracers in the upper troposphere of the flight region were the result of transport via convection and warm conveyor belt (WCB) uplifting of boundary layer air over the southeastern US. This mechanism is supported by the similar slope values of linear correlations between long-lived (months) anthropogenic tracers (e.g., C<sub>2</sub>Cl<sub>4</sub> and CHCl<sub>3</sub>) from the flight region and the planetary boundary layer in the southeastern US. In addition, the aircraft measurements suggest that outflow from the US augmented the entire tropospheric column at mid-latitudes over the North Atlantic. Overall, the flight 13 data demonstrate a pervasive impact of US anthropogenic emissions on the troposphere over the North Atlantic

Influence of biomass combustion emissions on the distribution of acidic trace gases over the southern Pacific basin during austral springtime

This paper describes the large-scale distributions of HNO3, HCOOH, and CH3COOH over the central and South Pacific basins during the Pacific Exploratory Mission-Tropics (PEM-Tropics) in austral springtime. Because of the remoteness of this region from continental areas, low part per trillion by volume (pptv) mixing ratios of acidic gases were anticipated to be pervasive over the South Pacific basin. However, at altitudes of 2–12 km over the South Pacific, air parcels were encountered frequently with significantly enhanced mixing ratios (up to 1200 pptv) of acidic gases. Most of these air parcels were centered in the 3–7 km altitude range and occurred within the 15°−65°S latitudinal band. The acidic gases exhibited an overall general correlation with CH3Cl, PAN, and O3, suggestive of photochemical and biomass burning sources. There was no correlation or trend of acidic gases with common industrial tracer compounds (e.g., C2Cl4 or CH3CCl3). The combustion emissions sampled over the South Pacific basin were relatively aged exhibiting C2H2/CO ratios in the range of 0.2–2.2 pptv/ppbv. The relationships between acidic gases and this ratio were similar to what was observed in aged air parcels (i.e., \u3e3–5 days since they were over a continental area) over the western North Pacific during the Pacific Exploratory Mission-West Phases A and B (PEM-West A and B). In the South Pacific marine boundary layer a median C2H2/CO ratio of 0.6 suggested that this region was generally not influenced by direct inputs of biomass combustion emissions. Here we observed the lowest mixing ratios of acidic gases, with median values of 14 pptv for HNO3, 19 pptv for HCOOH, and 18 pptv for CH3COOH. These values were coincident with low mixing ratios of NOx(\u3c10 pptv), CO (≈50 parts per billion by volume (ppbv)), O3 (\u3c 20 ppbv), and long-lived hydrocarbons (e.g., C2H6 \u3c300 pptv). Overall, the PEM-Tropics data suggest an important influence of aged biomass combustion emissions on the distributions of acidic gases over the South Pacific basin in austral springtime

Reactive nitrogen in Asian continental outflow over the western Pacific: Results from the NASA Transport and Chemical Evolution over the Pacific (TRACE-P) airborne mission

We present here results for reactive nitrogen species measured aboard the NASA DC-8 aircraft during the Transport and Chemical Evolution over the Pacific (TRACE-P) mission. The large-scale distributions total reactive nitrogen (NOy,sum = NO + NO2 + HNO3 + PAN + C1–C5alkyl nitrates) and O3 and CO were better defined in the boundary layer with significant degradation of the relationships as altitude increased. Typically, NOy,sum was enhanced over background levels of ∼260 pptv by 20-to-30-fold. The ratio C2H2/CO had values of 1–4 at altitudes up to 10 km and as far eastward as 150°E, implying significant vertical mixing of air parcels followed by rapid advection across the Pacific. Analysis air parcels originating from five principal Asian source regions showed that HNO3 and PAN dominated NOy,sum. Correlations of NOy,sum with C2Cl4 (urban tracer) were not well defined in any of the source regions, and they were only slightly better with CH3Cl (biomass tracer). Air parcels over the western Pacific contained a complex mixture of emission sources that are not easily resolvable as shown by analysis of the Shanghai mega-city plume. It contained an intricate mixture of pollution emissions and exhibited the highest mixing ratios of NOy,sum species observed during TRACE-P. Comparison of tropospheric chemistry between the earlier PEM-West B mission and the recent TRACE-P data showed that in the boundary layer significant increases in the mixing ratios of NOy,sum species have occurred, but the middle and upper troposphere seems to have been affected minimally by increasing emissions on the Asian continent over the last 7 years