Aerosol properties, in-canopy gradients, turbulent fluxes and VOC concentrations at a pristine forest site in Amazonia

Aerosol physical and chemical properties were measured in a forest site in central Amazonia (Cuieiras reservation, 2.61S; 60.21W) during the dry season of 2004 (Aug-Oct). Aerosol light scattering and absorption, mass concentration, elemental composition and size distributions were measured at three tower levels (Ground: 2 m; Canopy: 28 m, and Top: 40 m). For the first time, simultaneous eddy covariance fluxes of fine mode particles and volatile organic compounds (VOC) were measured above the Amazonian forest canopy. Aerosol fluxes were measured by eddy covariance using a Condensation Particle Counter (CPC) and a sonic anemometer. VOC fluxes were measured by disjunct eddy covariance using a Proton Transfer Reaction Mass Spectrometer (PTR-MS). At nighttime, a strong vertical gradient of phosphorus and potassium in the aerosol coarse mode was observed, with higher concentrations at Ground level. This suggests a source of primary biogenic particles below the canopy. Equivalent black carbon measurements indicate the presence of light-absorbing aerosols from biogenic origin. Aerosol number size distributions typically consisted of superimposed Aitken (76 nm) and accumulation modes (144 nm), without clear events of new particle formation. Isoprene and monoterpene fluxes reached respectively 7.4 and 0.82 mg m(-2) s(-1) around noon. An average fine particle flux of 0.05 +/- 0.10 10(6) m(-2) s(-1) was calculated, denoting an equilibrium between emission and deposition fluxes of fine mode particles at daytime. No significant correlations were found between VOC and fine mode aerosol concentrations or fluxes. (C) 2009 Elsevier Ltd. All rights reserved.

Disjunct eddy covariance measurements of volatile organic compound fluxes using proton transfer reaction mass spectrometry

Volatile organic compounds (VOCs) are emitted into the atmosphere from natural and anthropogenic sources, vegetation being the dominant source on a global scale. Some of these reactive compounds are deemed major contributors or inhibitors to aerosol particle formation and growth, thus making VOC measurements essential for current climate change research. This thesis discusses ecosystem scale VOC fluxes measured above a boreal Scots pine dominated forest in southern Finland. The flux measurements were performed using the micrometeorological disjunct eddy covariance (DEC) method combined with proton transfer reaction mass spectrometry (PTR-MS), which is an online technique for measuring VOC concentrations. The measurement, calibration, and calculation procedures developed in this work proved to be well suited to long-term VOC concentration and flux measurements with PTR-MS. A new averaging approach based on running averaged covariance functions improved the determination of the lag time between wind and concentration measurements, which is a common challenge in DEC when measuring fluxes near the detection limit. The ecosystem scale emissions of methanol, acetaldehyde, and acetone were substantial. These three oxygenated VOCs made up about half of the total emissions, with the rest comprised of monoterpenes. Contrary to the traditional assumption that monoterpene emissions from Scots pine originate mainly as evaporation from specialized storage pools, the DEC measurements indicated a significant contribution from de novo biosynthesis to the ecosystem scale monoterpene emissions. This thesis offers practical guidelines for long-term DEC measurements with PTR-MS. In particular, the new averaging approach to the lag time determination seems useful in the automation of DEC flux calculations. Seasonal variation in the monoterpene biosynthesis and the detailed structure of a revised hybrid algorithm, describing both de novo and pool emissions, should be determined in further studies to improve biological realism in the modelling of monoterpene emissions from Scots pine forests. The increasing number of DEC measurements of oxygenated VOCs will probably enable better estimates of the role of these compounds in plant physiology and tropospheric chemistry. Keywords: disjunct eddy covariance, lag time determination, long-term flux measurements, proton transfer reaction mass spectrometry, Scots pine forests, volatile organic compounds

Greenhouse Gas Fluxes in Tropical and Temperae Agriculture: The Need for a Full-Cost Accounting of Global Warming Potentials

Agriculture's contribution to radiative forcing is principally through its historical release of carbon in soil and vegetation to the atmosphere and through its contemporary release of nitrous oxide (N2O) and methane (CHM4). The sequestration of soil carbon in soils now depleted in soil organic matter is a well-known strategy for mitigating the buildup of CO2 in the atmosphere. Less well-recognized are other mitigation potentials. A full-cost accounting of the effects of agriculture on greenhouse gas emissions is necessary to quantify the relative importance of all mitigation options. Such an analysis shows nitrogen fertilizer, agricultural liming, fuel use, N2O emissions, and CH4 fluxes to have additional significant potential for mitigation. By evaluating all sources in terms of their global warming potential it becomes possible to directly evaluate greenhouse policy options for agriculture. A comparison of temperate and tropical systems illustrates some of these options.

Nitrogen pools and fluxes in grassland soils sequestering carbon

Carbon sequestration in agricultural, forest, and grassland soils has been promoted as a means by which substantial amounts of CO2 may be removed from the atmosphere, but few studies have evaluated the associated impacts on changes in soil N or net global warming potential (GWP). The purpose of this research was to ( 1) review the literature to examine how changes in grassland management that affect soil C also impact soil N, ( 2) assess the impact of different types of grassland management on changes in soil N and rates of change, and (3) evaluate changes in N2O fluxes from differently managed grassland ecosystems to assess net impacts on GWP. Soil C and N stocks either both increased or both decreased for most studies. Soil C and N sequestration were tightly linked, resulting in little change in C: N ratios with changes in management. Within grazing treatments N2O made a minor contribution to GWP (0.1-4%), but increases in N2O fluxes offset significant portions of C sequestration gains due to fertilization (10-125%) and conversion (average = 27%). Results from this work demonstrate that even when improved management practices result in considerable rates of C and N sequestration, changes in N2O fluxes can offset a substantial portion of gains by C sequestration. Even for cases in which C sequestration rates are not entirely offset by increases in N2O fluxes, small increases in N2O fluxes can substantially reduce C sequestration benefits. Conversely, reduction of N2O fluxes in grassland soils brought about by changes in management represents an opportunity to reduce the contribution of grasslands to net greenhouse gas forcing.

Carbon pools and fluxes along an environmental gradient in northern Arizona

Carbon pools and fluxes were quantified along an environmental gradient in northern Arizona. Data are presented on vegetation, litter, and soil C pools and soil CO2 fluxes from ecosystems ranging from shrub-steppe through woodlands to coniferous forest and the ecotones in between. Carbon pool sizes and fluxes in these semiarid ecosystems vary with temperature and precipitation and are strongly influenced by canopy cover. Ecosystem respiration is approximately 50 percent greater in the more mesic, forest environment than in the dry shrub-steppe environment. Soil respiration rates within a site vary seasonally with temperature but appear to be constrained by low soil moisture during dry summer months, when approximately 75% of total annual soil respiration occurs. Total annual amount of CO2 respired across all sites is positively correlated with annual precipitation and negatively correlated with temperature. Results suggest that changes in the amount and periodicity of precipitation will have a greater effect on C pools and fluxes than will changes in temperature :in the semiarid Southwestern United States.

Implications of patterns of carbon pools and fluxes across a semiarid environmental gradient

Landscape scale environmental gradients present variable spatial patterns and ecological processes caused by climate, topography and soil characteristics and, as such, offer candidate sites to study environmental change. Data are presented on the spatial pattern of dominant species, biomass, and carbon pools and the temporal pattern of fluxes across a transitional zone shifting from Great Basin Desert scrub, up through pinyon-juniper woodlands and into ponderosa pine forest and the ecotones between each vegetation type. The mean annual temperature (MAT) difference across the gradient is approximately 3 degrees C from bottom to top (MAT 8.5-5.5) and annual precipitation averages from 320 to 530 mm/yr, respectively. The stems of the dominant woody vegetation approach a random spatial pattern across the entire gradient, while the canopy cover shows a clustered pattern. The size of the clusters increases with elevation according to available soil moisture which in turn affects available nutrient resources. The total density of woody species declines with increasing soil moisture along the gl-adient, but total biomass increases. Belowground carbon and nutrient pools change from a heterogenous to a homogenous distribution on either side of the woodlands. Although temperature controls the: seasonal patterns of carbon efflux from the soils, soil moisture appears to be the primary driving variable, but response differs underneath the different dominant species, Similarly, decomposition of dominant litter occurs faster-at the cooler and more moist sites, but differs within sites due to litter quality of the different species. The spatial pattern of these communities provides information on the direction of future changes, The ecological processes that we documented are not statistically different in the ecotones as compared to the: adjoining communities, but are different at sites above the woodland than those below the woodland. We speculate that an increase in MAT will have a major impact on C pools and C sequestering and release processes in these semiarid landscapes. However, the impact will be primarily related to moisture availability rather than direct effects of an increase in temperature. (C) 1998 Elsevier Science B.V.

How can soil monitoring networks be used to improve predictions of organic carbon pool dynamics and CO2 fluxes in agricultural soils?

Abstract As regional and continental carbon balances of terrestrial ecosystems become available, it becomes clear that the soils are the largest source of uncertainty. Repeated inventories of soil organic carbon (SOC) organized in soil monitoring networks (SMN) are being implemented in a number of countries. This paper reviews the concepts and design of SMNs in ten countries, and discusses the contribution of such networks to reducing the uncertainty of soil carbon balances. Some SMNs are designed to estimate country-specific land use or management effects on SOC stocks, while others collect soil carbon and ancillary data to provide a nationally consistent assessment of soil carbon condition across the major land-use/soil type combinations. The former use a single sampling campaign of paired sites, while for the latter both systematic (usually grid based) and stratified repeated sampling campaigns (5–10 years interval) are used with densities of one site per 10–1,040 km². For paired sites, multiple samples at each site are taken in order to allow statistical analysis, while for the single sites, composite samples are taken. In both cases, fixed depth increments together with samples for bulk density and stone content are recommended. Samples should be archived to allow for re-measurement purposes using updated techniques. Information on land management, and where possible, land use history should be systematically recorded for each site. A case study of the agricultural frontier in Brazil is presented in which land use effect factors are calculated in order to quantify the CO2 fluxes from national land use/management conversion matrices. Process-based SOC models can be run for the individual points of the SMN, provided detailed land management records are available. These studies are still rare, as most SMNs have been implemented recently or are in progress. Examples from the USA and Belgium show that uncertainties in SOC change range from 1.6–6.5 Mg C ha−1 for the prediction of SOC stock changes on individual sites to 11.72 Mg C ha−1 or 34% of the median SOC change for soil/land use/climate units. For national SOC monitoring, stratified sampling sites appears to be the most straightforward attribution of SOC values to units with similar soil/land use/climate conditions (i.e. a spatially implicit upscaling approach). Keywords Soil monitoring networks - Soil organic carbon - Modeling - Sampling design

Pyrolysing poultry litter reduces N2O and CO2 fluxes

Application of poultry litter (PL) to soil can lead to substantial nitrous oxide (N2O) emissions due to the co-application of labile carbon (C) and nitrogen (N). Slow pyrolysis of PL to produce biochar may mitigate N2O emissions from this source, whilst still providing agronomic benefits. In a corn crop on ferrosol with similarly matched available N inputs of ca. 116 kg N/ha, PL-biochar plus urea emitted significantly less N2O (1.5 kg N2O-N/ha) compared to raw PL at 4.9 kg N2O-N/ha. Urea amendment without the PL-biochar emitted 1.2 kg N2O-N/ha, and the PL-biochar alone emitted only 0.35 kg N2O-N/ha. Both PL and PL-biochar resulted in similar corn yields and total N uptake which was significantly greater than for urea alone. Using stable isotope methodology, the majority (~ 80%) of N2O emissions were shown to be from non-urea sources. Amendment with raw PL significantly increased C mineralisation and the quantity of permanganate oxidisable organic C. The low molar H/C (0.49) and O/C (0.16) ratios of the PL-biochar suggest its higher stability in soil than raw PL. The PL-biochar also had higher P and K fertiliser value than raw PL. This study suggests that PL-biochar is a valuable soil amendment with the potential to significantly reduce emissions of soil greenhouse gases compared to the raw product. Contrary to other studies, PL-biochar incorporated to 100 mm did not reduce N2O emissions from surface applied urea, which suggests that further field evaluation of biochar impacts, and methods of application of both biochar and fertiliser, are needed.

Uniformity of postprocessing of dense nanotube arrays by neutral and ion fluxes

The advantages of using low-temperature plasma environments for postprocessing of dense nanotube arrays are shown by means of multiscale hybrid numerical simulations. By controlling plasma-extracted ion fluxes and varying the plasma and sheath parameters, one can selectively coat, dope, or functionalize different areas on nanotube surfaces. Conditions of uniform deposition of ion fluxes over the entire nanotube surfaces are obtained for different array densities. The plasma route enables a uniform processing of lateral nanotube surfaces in very dense (with a step-to-height ratio of 1:4) arrays, impossible via the neutral gas process wherein radical penetration into the internanotube gaps is poor. © 2006 American Institute of Physics.

Disentangling fluxes of energy and matter in plasma-surface interactions : effect of process parameters

The possibility to discriminate between the relative importance of the fluxes of energy and matter in plasma-surface interaction is demonstrated by the energy flux measurements in low-temperature plasmas ignited by the radio frequency discharge (power and pressure ranges 50-250 W and 8-11.5 Pa) in Ar, Ar+ H2, and Ar+ H2 + CH4 gas mixtures typically used in nanoscale synthesis and processing of silicon- and carbon-based nanostructures. It is shown that by varying the gas composition and pressure, the discharge power, and the surface bias one can effectively control the surface temperature and the matter supply rates. The experimental findings are explained in terms of the plasma-specific reactions in the plasma bulk and on the surface.

Microscopic ion fluxes in plasma-aided nanofabrication of ordered carbon nanotip structures

Three-dimensional topography of microscopic ion fluxes in the reactive hydrocarbon-based plasma-aided nanofabrication of ordered arrays of vertically aligned single-crystalline carbon nanotip microemitter structures is simulated by using a Monte Carlo technique. The individual ion trajectories are computed by integrating the ion equations of motion in the electrostatic field created by a biased nanostructured substrate. It is shown that the ion flux focusing onto carbon nanotips is more efficient under the conditions of low potential drop Us across the near-substrate plasma sheath. Under low- Us conditions, the ion current density onto the surface of individual nanotips is higher for higher-aspect-ratio nanotips and can exceed the mean ion current density onto the entire nanopattern in up to approximately five times. This effect becomes less pronounced with increasing the substrate bias, with the mean relative enhancement of the ion current density ξi not exceeding ∼1.7. The value of ξi is higher in denser plasmas and behaves differently with the electron temperature Te depending on the substrate bias. When the substrate bias is low, ξi decreases with Te, with the opposite tendency under higher- Us conditions. The results are relevant to the plasma-enhanced chemical-vapor deposition of ordered large-area nanopatterns of vertically aligned carbon nanotips, nanofibers, and nanopyramidal microemitter structures for flat-panel display applications. © 2005 American Institute of Physics.

Diagnostics and two-dimensional simulation of low-frequency inductively coupled plasmas with neutral gas heating and electron heat fluxes

This article presents the results on the diagnostics and numerical modeling of low-frequency (∼460 KHz) inductively coupled plasmas generated in a cylindrical metal chamber by an external flat spiral coil. Experimental data on the electron number densities and temperatures, electron energy distribution functions, and optical emission intensities of the abundant plasma species in low/intermediate pressure argon discharges are included. The spatial profiles of the plasma density, electron temperature, and excited argon species are computed, for different rf powers and working gas pressures, using the two-dimensional fluid approach. The model allows one to achieve a reasonable agreement between the computed and experimental data. The effect of the neutral gas temperature on the plasma parameters is also investigated. It is shown that neutral gas heating (at rf powers≥0.55kW) is one of the key factors that control the electron number density and temperature. The dependence of the average rf power loss, per electron-ion pair created, on the working gas pressure shows that the electron heat flux to the walls appears to be a critical factor in the total power loss in the discharge.

Surface fluxes of Si and C adatoms at initial growth stages of SiC quantum dots

Self-assembly of highly stoichiometric SiC quantum dots still remains a major challenge for the gas/plasma-based nanodot synthesis. By means of a multiscale hybrid numerical simulation of the initial stage (0.1-2.5 s into the process) of deposition of SiCSi (100) quantum dot nuclei, it is shown that equal Si and kst atom deposition fluxes result in strong nonstoichiometric nanodot composition due to very different surface fluxes of Si and C adatoms to the quantum dots. At this stage, the surface fluxes of Si and C adatoms to SiC nanodots can be effectively controlled by manipulating the SiC atom influx ratio and the Si (100) surface temperature. It is demonstrated that at a surface temperature of 800 K the surface fluxes can be equalized after only 0.05 s into the process; however, it takes more then 1 s at a surface temperature of 600 K. Based on the results of this study, effective strategies to maintain a stoichiometric ([Si] [C] =1:1) elemental ratio during the initial stages of deposition of SiCSi (100) quantum dot nuclei in a neutral/ionized gas-based process are proposed.

Effective control of ion fluxes over large areas by magnetic fields : from narrow beams to highly uniform fluxes

An effective control of the ion current distribution over large-area (up to 103 cm2) substrates with the magnetic fields of a complex structure by using two additional magnetic coils installed under the substrate exposed to vacuum arc plasmas is demonstrated. When the magnetic field generated by the additional coils is aligned with the direction of the magnetic field generated by the guiding and focusing coils of the vacuum arc source, a narrow ion density distribution with the maximum current density 117 A m-2 is achieved. When one of the additional coils is set to generate the magnetic field of the opposite direction, an area almost uniform over the substrate of 103 cm2 ion current distribution with the mean value of 45 A m-2 is achieved. Our findings suggest that the system with the vacuum arc source and two additional magnetic coils can be effectively used for the effective, high throughput, and highly controllable plasma processing.

Nanostructures of various dimensionalities from plasma and neutral fluxes

A complex multi-scale model and numerical simulations are used to demonstrate, by simulating the development of patterns of nanotips, nanowalls, nanoislands and nanovoids of a characteristic size of 5-100 nm, a greater degree of determinism in the formation of various nanostructures by using the low-density, low-temperature plasma-based processes. It is shown that in the plasma, in contrast to the neutral gas-based processes, one can synthesize nanostructures of various dimensionalities and shapes with a larger surface density, desired geometrical parameters and narrower size distribution functions. This effect is mainly attributed to strong ion focusing by irregular electric fields in the nanopatterns, which effectively redistributes the influxes of plasma-generated building units and thus provides a selective control of their delivery to the growing nanostructures.