Global tropospheric chemistry: Chemical fluexes in the global atmosphere

In October 1987, NSF, NASA, and NOAA jointly sponsored a workshop at Columbia University to assess the experimental tools and analysis procedures in use and under development to measure and understand gas and particle fluxes across this critical air-surface boundary. Results are presented for that workshop. It is published to summarize the present understanding of the various measurement techniques that are available, identify promising new technological developments for improved measurements, and stimulate thinking about this important measurement challenge

Measurement and modelling of ammonia emissions from an anaerobic digestion plant

Anaerobic digestion (AD) is becoming increasingly popular for treating organic waste. The methane produced can be burned to generate electricity, and the digestate, which is rich in mineral nitrogen, can be used as a fertiliser. The storage and processing of large volumes of organic wastes through AD has been identified as a significant source of NH3 emissions, however only one study has previously quantified the totality NH3 emissions that arise in situ at an AD plant. In this study the emissions from an AD plant was estimated through the integration of supportive methodologies involving passive and continuous air NH3 sampling, atmospheric dispersion modelling and the application of published emission factors (EFs) and empirical models within the literature. Two dispersion models (ADMS and a Lagrangian stochastic model) were applied to produce robust emission estimates. The Lagrangian stochastic model (Windtrax) was used for inverse dispersion modelling to back-calculate the total emission rate from the point of continuous measurement. Back-calculated emission rates and literature EFs were applied to the ADMS model to make predictions of air NH3 concentrations. Predicted concentrations were verified against weekly passive (CEH ALPHA) NH3 measurements, where measured concentrations were well described by the numerical model framework using the emission rate estimated by inverse dispersion modelling. EFs that were applied from the literature required adjustment to fit the measured concentrations, however after sensible adjustment an excellent match of observed and predicted concentrations was achieved. Total emissions from the AD plant was estimated to be 16.8 μg s-1 ± 1.8 mg s-1. This is significantly higher than the back-calculated estimate (10.3 ± 1.1 mgs-1), due to a more realistic treatment of the source area. The storage of solid digestate and the aerobic treatment of liquid effluents were the most significant sources of NH3. The representativeness of the existing EF estimated for AD plants is evaluated through application to the present case study and comparing with NH3 measurements and estimated emission rates. The existing AD EF considerably overestimated observed concentrations by an average factor of 54. The applicability of calculated EFs to other AD plants is discussed

The Holy Grail: A road map for unlocking the climate record stored within Mars' polar layered deposits

In its polar layered deposits (PLD), Mars possesses a record of its recent climate, analogous to terrestrial ice sheets containing climate records on Earth. Each PLD is greater than 2 ​km thick and contains thousands of layers, each containing information on the climatic and atmospheric state during its deposition, creating a climate archive. With detailed measurements of layer composition, it may be possible to extract age, accumulation rates, atmospheric conditions, and surface activity at the time of deposition, among other important parameters; gaining the information would allow us to “read” the climate record. Because Mars has fewer complicating factors than Earth (e.g. oceans, biology, and human-modified climate), the planet offers a unique opportunity to study the history of a terrestrial planet’s climate, which in turn can teach us about our own planet and the thousands of terrestrial exoplanets waiting to be discovered. During a two-part workshop, the Keck Institute for Space Studies (KISS) hosted 38 Mars scientists and engineers who focused on determining the measurements needed to extract the climate record contained in the PLD. The group converged on four fundamental questions that must be answered with the goal of interpreting the climate record and finding its history based on the climate drivers. The group then proposed numerous measurements in order to answer these questions and detailed a sequence of missions and architecture to complete the measurements. In all, several missions are required, including an orbiter that can characterize the present climate and volatile reservoirs; a static reconnaissance lander capable of characterizing near surface atmospheric processes, annual accumulation, surface properties, and layer formation mechanism in the upper 50 ​cm of the PLD; a network of SmallSat landers focused on meteorology for ground truth of the low-altitude orbiter data; and finally, a second landed platform to access ~500 ​m of layers to measure layer variability through time. This mission architecture, with two landers, would meet the science goals and is designed to save costs compared to a single very capable landed mission. The rationale for this plan is presented below. In this paper we discuss numerous aspects, including our motivation, background of polar science, the climate science that drives polar layer formation, modeling of the atmosphere and climate to create hypotheses for what the layers mean, and terrestrial analogs to climatological studies. Finally, we present a list of measurements and missions required to answer the four major questions and read the climate record. 1. What are present and past fluxes of volatiles, dust, and other materials into and out of the polar regions? 2. How do orbital forcing and exchange with other reservoirs affect those fluxes? 3. What chemical and physical processes form and modify layers? 4. What is the timespan, completeness, and temporal resolution of the climate history recorded in the PLD

Contemporary geomorphological activity throughout the proglacial area of an alpine catchment

Quantification of contemporary geomorphological activity is a fundamental prerequisite for predicting the effects of future earth surface process and landscape development changes. However, there is a lack of high-resolution spatial and temporal data on geomorphological activity within alpine catchments, which are especially sensitive to climate change, human impacts and which are amongst the most dynamic landscapes on Earth. This study used data from repeated laser scanning to identify and quantify the distribution of contemporary sediment sources and the intensity of geomorphological activity within the lower part of a glaciated alpine catchment; Ödenwinkelkees, central Austria. Spatially, geomorphological activity was discriminated by substrate class. Activity decreased in both areal extent and intensity with distance from the glacier, becoming progressively more restricted to the fluvially-dominated valley floor. Temporally, geomorphological activity was identified on annual, seasonal, weekly and daily timescales. Activity became more extensive with increasing study duration but more intense over shorter timescales, thereby demonstrating the importance of temporary storage of sediment within the catchment. The mean volume of material moved within the proglacial zone was 4400m.yr, which suggests a net surface lowering of 34mm.yr in this part of the catchment. We extrapolate a minimum of 4.8mm.yr net surface lowering across the whole catchment. These surface lowering values are approximately twice those calculated elsewhere from contemporary measurements of suspended sediment flux, and of rates calculated from the geological record, perhaps because we measure total geomorphological activity within the catchment rather than overall efflux of material. Repeated geomorphological surveying therefore appears to mitigate the problems of hydrological studies underestimating sediment fluxes on decadal-annual time-scales. Further development of the approach outlined in this study will enable the quantification of geomorphological activity, alpine terrain stability and persistence of landforms

Recent advances in low-cost particulate matter sensor: calibration and application

Particulate matter (PM) has been monitored routinely due to its negative effects on human health and atmospheric visibility. Standard gravimetric measurements and current commercial instruments for field measurements are still expensive and laborious. The high cost of conventional instruments typically limits the number of monitoring sites, which in turn undermines the accuracy of real-time mapping of sources and hotspots of air pollutants with insufficient spatial resolution. The new trends of PM concentration measurement are personalized portable devices for individual customers and networking of large quantity sensors to meet the demand of Big Data. Therefore, low-cost PM sensors have been studied extensively due to their price advantage and compact size. These sensors have been considered as a good supplement of current monitoring sites for high spatial-temporal PM mapping. However, a large concern is the accuracy of these low-cost PM sensors. Multiple types of low-cost PM sensors and monitors were calibrated against reference instruments. All these units demonstrated high linearity against reference instruments with high R2 values for different types of aerosols over a wide range of concentration levels. The question of whether low-cost PM monitors can be considered as a substituent of conventional instruments was discussed, together with how to qualitatively describe the improvement of data quality due to calibrations. A limitation of these sensors and monitors is that their outputs depended highly on particle composition and size, resulting in as high as 10 times difference in the sensor outputs. Optical characterization of low-cost PM sensors (ensemble measurement) was conducted by combining experimental results with Mie scattering theory. The reasons for their dependence on the PM composition and size distribution were studied. To improve accuracy in estimation of mass concentration, an expression for K as a function of the geometric mean diameter, geometric standard deviation, and refractive index is proposed. To get rid of the influence of the refractive index, we propose a new design of a multi-wavelength sensor with a robust data inversion routine to estimate the PM size distribution and refractive index simultaneously. The utility of the networked system with improved sensitivity was demonstrated by deploying it in a woodworking shop. Data collected by the networked system was utilized to construct spatiotemporal PM concentration distributions using an ordinary Kriging method and an Artificial Neural Network model to elucidate particle generation and ventilation processes. Furthermore, for the outdoor environment, data reported by low-cost sensors were compared against satellite data. The remote sensing data could provide a daily calibration of these low-cost sensors. On the other hand, low-cost PM sensors could provide better accuracy to demonstrate the microenvironment

Measurement of Agriculture-Related Air Pollutant Emissions Using Point and Remote Sensors

Measuring air pollution emissions from agricultural activities is usually difficult because of their large area and variability. Traditional air quality sensors, called point samplers, measure conditions in one location, which may not adequately measure a plume. Remote sensors, instruments that measure pollution along a line rather than at a single point, are better able to measure conditions around large areas. This dissertation reports on four agricultural air emissions studies that used both point and remote sensors for comparison. The methods used to calculate the emissions are based on previous work and are further developed in these studies. In particular, an atmospheric dispersion model was developed and tested that can account for a particle behaving different than the surrounding gas due to gravity and inertia and depositing out of the flow. Particulate matter (PM) emissions values are reported for two agricultural tillage conservation management practices (CMPs)and the corresponding traditional tillage methods in order to determine how well the CMP reduces emissions. In addition, gas-phase ammonia (NH3) emissions for a dairy operation and PM emissions from a feedlot operation are reported. These studies can help us better measure emissions from agricultural operations and understand how much air pollution is being emitted

Dynamic parameter estimation of atomic layer deposition kinetics applied to in situ quartz crystal microbalance diagnostics

This paper presents the elaboration of an experimentally validated model of a continuous cross-flow atomic layer deposition (ALD) reactor with temporally separated precursor pulsing encoded in the Modelica language. For the experimental validation of the model, in situ quartz crystal microbalance (QCM) diagnostics was used to yield submonolayer resolution of mass deposition resulting from thin film growth of ZnO from Zn(C2H5)2 and H2O precursors. The ZnO ALD reaction intrinsic kinetic mechanism that was developed accounted for the temporal evolution of the equilibrium fractional surface concentrations of precursor adducts and their transition states for each half-reaction. This mechanism was incorporated into a rigorous model of reactor transport, which comprises isothermal compressible equations for the conservation of mass, momentum and gas-phase species. The physically based model in this way relates the local partial pressures of precursors to the dynamic composition of the growth surface, and ultimately governs the accumulated mass trajectory at the QCM sensor. Quantitative rate information can then be extracted by means of dynamic parameter estimation. The continuous operation of the reactor is described by limit-cycle dynamic solutions and numerically computed using Radau collocation schemes and solved using CasADi's interface to IPOPT. Model predictions of the transient mass gain per unit area of exposed surface QCM sensor, resolved at a single pulse sequence, were in good agreement with experimental data under a wide range of operating conditions. An important property of the limit-cycle solution procedure is that it enables the systematic approach to analyze the dynamic nature of the growth surface composition as a function of process operating parameters. Especially, the dependency of the film growth rate per limit-cycle on the half-cycle precursor exposure dose and the process temperature was thoroughly assessed and the difference between ALD in saturating and in non-saturating film growth conditions distinguished