ALBERT

Description: Bear Seamount (39° 55'N, 67° 30'W) is an extinct undersea volcano located inside the U.S. Exclusive Economic Zone south of Georges Bank. The fauna associated with the seamount was little known until twenty trawl stations were made 2-7 December 2000, by the NOAA ship Delaware II. The objective of the cruise was to begin to document the biodiversity on and over the seamount, particularly of fishes, cephalopods, and crustaceans. Representatives of most species were preserved as vouchers and for subsequent definitive identification. Preliminary identifications indicate the capture of 115 fish species. Among these were a number of new fish records for the area or rare species, including Acromycter pertubator (Congridae), Alepocephalus bairdii (Alepocephalidae), Mirognathus normani (Alepocephalidae), Bathygadus favosus (Bathygadidae), Nezumia longebarbata (Macrouridae), Gaidropsarus argentatus (Phycidae), and Dibranchus tremendus (Ogcocephalidae). Only two fish species of potential commercial importance were encountered: Coryphaenoides rupestris and Macrourus berglax. Cephalopods comprised 26 species in 15 families, including one new distributional record and several rarelycollected species. The crustacean fauna was diverse with at least 46 species. Totals for other invertebrate species are pending laboratory identification, but number at least 113 species in 10 phyla. This includes a number of new distributional records and a new species of gorgonian.

Description: A new solid-phase scrubber for use in conventional ozone (O3) photometers was investigated as a means of reducing interferences from other UV-absorbing species and water vapor. It was found that when heated to 100–130 °C, a tubular graphite scrubber efficiently removed up to 500 ppb ozone and ozone monitors using the heated graphite scrubber were found to be less susceptible to interferences from water vapor, mercury vapor, and aromatic volatile organic compounds (VOCs) compared to conventional metal oxide scrubbers. Ambient measurements from a graphite scrubber-equipped photometer and a co-located Federal equivalent method (FEM) ozone analyzer showed excellent agreement over 38 days of measurements and indicated no loss in the scrubber's ability to remove ozone when operated at 130 °C. The use of a heated graphite scrubber was found to reduce the interference from mercury vapor to ≤ 3 % of that obtained using a packed-bed Hopcalite scrubber. For a series of substituted aromatic compounds (ranging in volatility and absorption cross section at 253.7 nm), the graphite scrubber was observed to consistently exhibit reduced levels of interference, typically by factors of 2.5 to 20 less than with Hopcalite. Conventional solid-phase scrubbers also exhibited complex VOC adsorption and desorption characteristics that were dependent upon the relative humidity (RH), volatility of the VOC, and the available surface area of the scrubber. This complex behavior involving humidity is avoided by use of a heated graphite scrubber. These results suggest that heated graphite scrubbers could be substituted in most ozone photometers as a means of reducing interferences from other UV-absorbing species found in the atmosphere. This could be particularly important in ozone monitoring for compliance with the United States (U.S.) Clean Air Act or for use in VOC-rich environments such as in smog chambers and monitoring indoor air quality.

Description: We describe and characterize a modular folded tubular photometer for making direct measurements of the concentrations of nitrogen dioxide (NO2) and specify how this method could be extended to measure other pollutants such as sulfur dioxide (SO2), ozone (O3), and black carbon particulate matter. Direct absorbance measurements using this photometer can be made across the spectral range from the ultraviolet (UV) to the near infrared. The absorbance cell makes use of modular components (tubular detection cells and mirror cubes) that allow construction of path lengths of up to 2 m or more while maintaining low cell volumes. The long path lengths and low cell volumes enable sensitive detection of ambient air pollutants down to low part-per-billion levels for gas species and aerosol extinctions down to 1 Mm−1, corresponding to ∼ 0.1 µg m−3 for black carbon particulates. Pressure equalization throughout the stages of the absorbance measurement is shown to be critical to accurate measurements of analyte concentrations. The present paper describes the application of this photometer to direct measurements of nitrogen dioxide (NO2) and the incorporation of design features that also enable measurement of nitric oxide (NO) in the same instrument. Excellent agreement for ambient measurements along an urban roadside was found for both NO2 and NO measured by the folded tubular photometer compared to existing standard techniques. Compared to commonly used methods for measurements of NOx species, the advantages of this approach include (1) an absolute quantification for NO2 based on the Beer–Lambert law, thereby greatly reducing the frequency at which calibrations are required; (2) the direct measurement of NO2 concentration without prior conversion to NO as is required for the commonly used chemiluminescence method; (3) the use of modular components that allow construction of absorbance detection cells of varying lengths for extending the dynamic range of concentrations that can be measured; (4) a more economical instrument than other currently available direct measurement techniques for NO2; and (5) the potential for simultaneous detection of additional species such as SO2, O3, and black carbon in the same instrument. In contrast to other commercially available direct NO2 measurements, such as cavity-attenuated phase-shift spectroscopy (CAPS), the folded tubular photometer also measures NO simultaneously in the same apparatus by quantitatively converting NO to NO2 with ozone, which is then detected by direct absorbance.

Description: A highly portable ozone (O3) calibration source that can serve as a U.S. EPA level 4 transfer standard for the calibration of ozone analyzers is described and evaluated with respect to analytical figures of merit and effects of ambient pressure and humidity. Reproducible mixing ratios of ozone are produced by the photolysis of oxygen in O3-scrubbed ambient air by UV light at 184.9 nm light from a low-pressure mercury lamp. By maintaining a constant volumetric flow rate (thus constant residence time within the photolysis chamber), the mixing ratio produced is independent of both pressure and temperature and can be varied by varying the lamp intensity. Pulse width modulation of the lamp with feedback from a photodiode monitoring the 253.7 nm emission line is used to maintain target ozone mixing ratios in the range 30–1000 ppb. In order to provide a constant ratio of intensities at 253.7 and 184.9 nm, the photolysis chamber containing the lamp is regulated at a temperature of 40 ∘C. The resulting O3 calibrator has a response time for step changes in output ozone mixing ratio of

Description: Alkenes are reactive hydrocarbons that influence local and regional atmospheric chemistry by playing important roles in the photochemical production of tropospheric ozone and in the formation of secondary organic aerosols. The simplest alkene, ethene (ethylene), is a major plant hormone and ripening agent for agricultural commodities. The group of light alkenes (C2-C4) originates from both biogenic and anthropogenic sources, but their biogenic sources are poorly characterized, with limited field-based flux observations. Here we report net ecosystem fluxes of light alkenes and isoprene from a semiarid ponderosa pine forest in the Rocky Mountains of Colorado, USA using the relaxed eddy accumulation (REA) technique during the summer of 2014. Ethene, propene, butene and isoprene emissions have strong diurnal cycles, with median daytime fluxes of 123, 95, 39 and 17 µg m−2 h−1, respectively. The fluxes were correlated with each other, followed general ecosystem trends of CO2 and water vapor, and showed similar sunlight and temperature response curves as other biogenic VOCs. The May through October flux, based on measurements and modeling, averaged 62, 52, 24 and 18 µg m−2 h−1 for ethene, propene, butene and isoprene, respectively. The light alkenes contribute significantly to the overall biogenic source of reactive hydrocarbons: roughly 18 % of the dominant biogenic VOC, 2-methyl-3-buten-2-ol. The measured ecosystem scale fluxes are 40–80 % larger than estimates used for global emissions models for this type of ecosystem.

Description: Isoprene fluxes vary seasonally with changes in environmental factors (e.g., solar radiation and temperature) and biological factors (e.g., leaf phenology). However, our understanding of the seasonal patterns of isoprene fluxes and the associated mechanistic controls is still limited, especially in Amazonian evergreen forests. In this paper, we aim to connect intensive, field-based measurements of canopy isoprene flux over a central Amazonian evergreen forest site with meteorological observations and with tower-mounted camera leaf phenology to improve our understanding of patterns and causes of isoprene flux seasonality. Our results demonstrate that the highest isoprene emissions are observed during the dry and dry-to-wet transition seasons, whereas the lowest emissions were found during the wet-to-dry transition season. Our results also indicate that light and temperature cannot totally explain isoprene flux seasonality. Instead, the camera-derived leaf area index (LAI) of recently mature leaf age class (e.g., leaf ages of 3–5 months) exhibits the highest correlation with observed isoprene flux seasonality (R2=0.59, p

Description: The concept of disjunct eddy sampling (DES) for use in measuring ecosystem-level micrometeorological fluxes is re-examined. The governing equations are discussed as well as other practical considerations and guidelines concerning this sampling method as it is applied to either the disjunct eddy covariance (DEC) or disjunct eddy accumulation (DEA) techniques. A disjunct eddy sampling system was constructed that could either be combined with relatively slow sensors (response time of 2 to 40 s) to measure fluxes using DEC, or could also be used to accumulate samples in stable reservoirs for later laboratory analysis (DEA technique). Both the DEC and DEA modes of this sampler were tested against conventional eddy covariance (EC) for fluxes of either CO2 (DEC) or isoprene (DEA). Good agreement in both modes was observed relative to the EC systems. However, the uncertainty in a single DEA flux measurement was considerable (~40%) due to both the reduced statistical sampling and the analytical precision of the concentration difference measurements. We have also re-investigated the effects of nonzero mean vertical wind velocity on accumulation techniques as it relates to our DEA measurements. Despite the higher uncertainty, disjunct eddy sampling can provide an alternative technique to eddy covariance for determining ecosystem-level fluxes for species where fast sensors do not currently exist.

Description: The concept of disjunct eddy sampling (DES) for use in measuring ecosystem-level micrometeorological fluxes is re-examined. The governing equations are discussed as well as other practical considerations and guidelines concerning this sampling method as it is applied to either the disjunct eddy covariance (DEC) or disjunct eddy accumulation (DEA) techniques. A disjunct eddy sampling system was constructed that could either be combined with relatively slow sensors (response time of 2 to 40 s) to measure fluxes using DEC, or could also be used to accumulate samples in stable reservoirs for later laboratory analysis (DEA technique). Both the DEC and DEA modes of this sampler were tested against conventional eddy covariance (EC) for fluxes of either CO2 (DEC) or isoprene (DEA). Good agreement in both modes was observed relative to the EC systems. However, the uncertainty in a single DEA flux measurement was considerable (~40%) due to both the reduced statistical sampling and the analytical precision of the concentration difference measurements. We have also re-investigated the effects of nonzero mean vertical wind velocity on accumulation techniques as it relates to our DEA measurements. Despite the higher uncertainty, disjunct eddy sampling can provide an alternative technique to eddy covariance for determining ecosystem-level fluxes for species where fast sensors do not currently exist.

Description: We present the first eddy covariance flux measurements of volatile organic compounds (VOCs) using a proton-transfer-reaction time-of-flight mass spectrometer (PTR-TOF-MS) above a ponderosa pine forest in Colorado, USA. The high mass resolution of the PTR-TOF-MS enabled the identification of chemical sum formulas. During a 30 day measurement period in August and September 2010, 649 different ion mass peaks were detected in the ambient air mass spectrum (including primary ions and mass calibration compounds). Eddy covariance with the vertical wind speed was calculated for all ion mass peaks. On a typical day, 17 ion mass peaks, including protonated parent compounds, their fragments and isotopes as well as VOC-H+-water clusters, showed a significant flux with daytime average emissions above a reliable flux threshold of 0.1 mg compound m−2 h−1. These ion mass peaks could be assigned to seven compound classes. The main flux contributions during daytime (10:00–18:00 LT) are attributed to the sum of 2-methyl-3-buten-2-ol (MBO) and isoprene (50%), methanol (12%), the sum of acetic acid and glycolaldehyde (10%) and the sum of monoterpenes (10%). The total MBO + isoprene flux was composed of 10% isoprene and 90% MBO. There was good agreement between the light- and temperature dependency of the sum of MBO and isoprene observed for this work and those of earlier studies. The above canopy flux measurements of the sum of MBO and isoprene and the sum of monoterpenes were compared to emissions calculated using the Model of Emissions of Gases and Aerosols from Nature (MEGAN 2.1). The best agreement between MEGAN 2.1 and measurements was reached using emission factors determined from site-specific leaf cuvette measurements. While the modeled and measured MBO + isoprene fluxes agree well, the emissions of the sum of monoterpenes is underestimated by MEGAN 2.1. This is expected as some factors impacting monoterpene emissions, such as physical damage of needles and branches due to storms, are not included in MEGAN 2.1. After a severe hailstorm event, 22 ion mass peaks (attributed to six compound classes plus some unknown compounds) showed an elevated flux for the two following days. The sum of monoterpene emissions was 4–23 times higher compared to emissions prior to the hailstorm while MBO emissions remained unchanged. The monoterpene emission (in mg compound m−2) during this measurement period is underestimated by 40% if the effect of this disturbance source is not considered.

Description: Formation and growth of ultrafine particles is crudely represented in chemistry-climate models, contributing to uncertainties in aerosol composition, size distribution, and aerosol effects on cloud condensation nuclei (CCN) concentrations. Measurements of ultrafine particles, their precursor gases, and meteorological parameters were performed in a ponderosa pine forest in the Colorado Front Range in July–August 2011, and were analyzed to study processes leading to small particle burst events (PBEs) which were characterized by an increase in the number concentrations of ultrafine 4–30 nm diameter size particles. These measurements suggest that PBEs were associated with the arrival at the site of anthropogenic pollution plumes midday to early afternoon. During PBEs, number concentrations of 4–30 nm diameter particles typically exceeded 104 cm−3, and these elevated concentrations coincided with increased SO2 and monoterpene concentrations, and led to a factor-of-2 increase in CCN concentrations at 0.5% supersaturation. The PBEs were simulated using the regional WRF-Chem model, which was extended to account for ultrafine particle sizes starting at 1 nm in diameter, to include an empirical activation nucleation scheme in the planetary boundary layer, and to explicitly simulate the subsequent growth of Aitken particles (10–100 nm) by condensation of organic and inorganic vapors. The updated model reasonably captured measured aerosol number concentrations and size distribution during PBEs, as well as ground-level CCN concentrations. Model results suggest that sulfuric acid originating from anthropogenic SO2 triggered PBEs, and that the condensation of monoterpene oxidation products onto freshly nucleated particles contributes to their growth. The simulated growth rate of ~ 3.4 nm h−1 for 4–40 nm diameter particles was comparable to the measured average value of 2.3 nm h−1. Results also suggest that the presence of PBEs tends to modify the composition of sub-20 nm diameter particles, leading to a higher mass fraction of sulfate aerosols. Sensitivity simulations suggest that the representation of nucleation processes in the model largely influences the predicted number concentrations and thus CCN concentrations. We estimate that nucleation contributes 67% of surface CCN at 0.5% supersaturation in this pine forest environment.