Calibration of remotely sensed, coarse resolution NDVI to CO2 fluxes in a sagebrush-steppe ecosystem

The net ecosystem exchange (NEE) of carbon flux can be partitioned into gross primary productivity (GPP) and respiration (R). The contribution of remote sensing and modeling holds the potential to predict these components and map them spatially and temporally. This has obvious utility to quantify carbon sink and source relationships and to identify improved land management strategies for optimizing carbon sequestration. The objective of our study was to evaluate prediction of 14-day average daytime CO₂ fluxes (F_day) and nighttime CO₂ fluxes (R_n) using remote sensing and other data. F_day and R_n were measured with a Bowen ratio-energy balance (BREB) technique in a sagebrush (Artemisia spp.)-steppe ecosystem in northeast Idaho, USA, during 1996-1999. Micrometeorological variables aggregated across 14-day periods and time-integrated Advanced Very High Resolution Radiometer (AVHRR) Normalized Difference Vegetation Index (iNDVI) were determined during four growing seasons (1996-1999) and used to predict F_day and R_n. We found that iNDVI was a strong predictor of F_day (R²=0.79, n=66, P<0.0001). Inclusion of evapotranspiration in the predictive equation led to improved predictions of F_day (R²=0.82, n=66, P<0.0001). Crossvalidation indicated that regression tree predictions of F_day were prone to overfitting and that linear regression models were more robust. Multiple regression and regression tree models predicted R_n quite well (R²=0.75-0.77, n=66) with the regression tree model being slightly more robust in crossvalidation. Temporal mapping of F_day and R_n is possible with these techniques and would allow the assessment of NEE in sagebrush-steppe ecosystems. Simulations of periodic F_day measurements, as might be provided by a mobile flux tower, indicated that such measurements could be used in combination with iNDVI to accurately predict F_day. These periodic measurements could maximize the utility of expensive flux towers for evaluating various carbon management strategies, carbon certification, and validation and calibration of carbon flux models.     

Parallel adjustments in vegetation greenness and ecosystem CO2 exchange in response to drought in a Southern California chaparral ecosystem

Some form of the light use efficiency (LUE) model is used in most models of ecosystem carbon exchange based on remote sensing. The strong relationship between the normalized difference vegetation index (NDVI) and light absorbed by green vegetation make models based on LUE attractive in the remote sensing context. However, estimation of LUE has proven problematic since it varies with vegetation type and environmental conditions. Here we propose that LUE may in fact be correlated with vegetation greenness (measured either as NDVI at constant solar elevation angle, or a red edge chlorophyll index), making separate estimates of LUE unnecessary, at least for some vegetation types. To test this, we installed an automated tram system for measurement of spectral reflectance in the footprint of an eddy covariance flux system in the Southern California chaparral. This allowed us to match the spatial and temporal scales of the reflectance and flux measurements and thus to make direct comparisons over time scales ranging from minutes to years. The 3-year period of this study included both “normal” precipitation years and an extreme drought in 2002. In this sparse chaparral vegetation, diurnal and seasonal changes in solar angle resulted in large variation in NDVI independent of the actual quantity of green vegetation. In fact, one would come to entirely different conclusions about seasonal changes in vegetation greenness depending on whether NDVI at noon or NDVI at constant solar elevation angle were used. Although chaparral vegetation is generally considered “evergreen”, we found that the majority of the shrubs were actually semi-deciduous, leading to large seasonal changes in NDVI at constant solar elevation angle. LUE was correlated with both greenness indices at the seasonal timescale across all years. In contrast, the relationship between LUE and PRI was inconsistent. PRI was well correlated with LUE during the “normal” years but this relationship changed dramatically during the extreme drought. Contrary to expectations, none of the spectral reflectance indices showed consistent relationships with CO₂ flux or LUE over the diurnal time-course, possibly because of confounding effects of sun angle and stand structure on reflectance. These results suggest that greenness indices can be used to directly estimate CO₂ exchange at weekly timescales in this chaparral ecosystem, even in the face of changes in LUE. Greenness indices are unlikely to be as good predictors of CO₂ exchange in dense evergreen vegetation as they were in the sparse, semi-deciduous chaparral. However, since relatively few ecosystems are entirely evergreen at large spatial scales or over long time spans due to disturbance, these relationships need to be examined across a wider range of vegetation types.     

Relating NDVI to ecosystem CO2 exchange patterns in response to season length and soil warming manipulations in arctic Alaska

Climate change in the Arctic will differentially affect physiological rates, leaf phenology, and species composition of tundra, resulting in changing patterns and magnitudes of ecosystem CO₂ flux. The normalized difference vegetation index (NDVI) provides a potential means to infer changes in CO₂ flux, but whether relationships developed between NDVI and flux components can be generalized across the entire growing season and in response to changes induced by climate warming is uncertain. To investigate how well such changes might be assessed using multispectral digital images, ecosystem CO₂ fluxes and NDVI were compared throughout the 2002 growing season on experimental plots with increased growing season length and soil temperature at Toolik Lake, Alaska. Season length was increased by snow removal early in the season and soil temperatures were increased using heating cables. Carbon dioxide fluxes were measured using static chamber techniques and corresponding NDVI images were taken with an agricultural digital camera. The seasonal patterns of NDVI in all treatments showed an increase to a peak in early August followed by an abrupt decline, with the snow removal plots phenologically advanced compared to the controls. Net ecosystem production (NEP) showed uptake of CO₂ early in the season leveling out to a slight loss of CO₂ at peak season for both control and extended season plots. Gross primary productivity (GPP) closely followed the pattern of NDVI and the pattern of ecosystem respiration (R_e) mirrored that of GPP. NDVI was significantly correlated to GPP and ecosystem respiration (R² = 0.50 and 0.36 respectively) across plots, dates, and treatments combined. However, most of the covariation was across dates. After accounting for seasonal variation, NDVI never accounted for more than 25% of the remaining variation in flux measures. Analysis of covariance showed that a given NDVI value corresponded to different flux rates on different dates and to different R_e among treatments after correcting for date. The slopes of the NDVI-GPP and NDVI-Re relationships were much steeper across dates than across plots. These plot-scale results suggest that NDVI alone is not sufficient to estimate carbon flux rate responses to climate change across space or years.     

Development of SAW-based multi-gas sensor for simultaneous detection of CO2 and NO2

A 440 MHz wireless and passive surface acoustic wave (SAW)-based multi-gas sensor integrated with a temperature sensor was developed on a 41° YX LiNbO₃ piezoelectric substrate for the simultaneous detection of CO₂, NO₂, and temperature. The developed sensor was composed of a SAW reflective delay lines structured by an interdigital transducer (IDT), ten reflectors, a CO₂ sensitive film (Teflon AF 2400), and a NO₂ sensitive film (indium tin oxide). Teflon AF 2400 was used for the CO₂ sensitive film because it provides a high CO₂ solubility, with good permeability and selectivity. For the NO₂ sensitive film, indium tin oxide (ITO) was used. Coupling of mode (COM) modeling was conducted to determine the optimal device parameters prior to fabrication. Using the parameters determined by the simulation results, the device was fabricated and then wirelessly measured using a network analyzer. The measured reflective coefficient S₁₁ in the time domain showed high signal/noise (S/N) ratio, small signal attenuation, and few spurious peaks. The time positions of the reflection peaks were well matched with the predicted values from the simulation. High sensitivity and selectivity were observed at each target gas testing. The obtained sensitivity was 2.12°/ppm for CO₂ and 51.5°/ppm for NO₂, respectively. With the integrated temperature sensor, temperature compensation was also performed during gas sensitivity evaluation process.     

Electrical response of Sm2O3-doped SnO2 to C2H2 and effect of humidity interference

Pure and Sm₂O₃-doped SnO₂ are prepared through a sol–gel method and characterized by X-ray diffraction (XRD) and transmission electron microscopy (TEM). The sensor based on 6 wt% Sm₂O₃-doped SnO₂ displays superior response at an operating temperature of 180 °C, and the response magnitude to 1000 ppm C₂H₂ can reach 63.8, which is 16.8 times larger than that of pure SnO₂. This sensor also shows high sensitivity under various humidity conditions. These results make our product be a good candidate in fabricating C₂H₂ sensors.     

The effect of La2CuO4 sensing electrode thickness on a potentiometric NOx sensor response

In order to further understand the different contributions to NO_x sensing mechanism as well as the importance of electrode geometry, solid state potentiometric sensors with varying La₂CuO₄ sensing electrode thicknesses were studied. These sensors (with a Pt counter electrode) showed a dependence of NO₂ sensitivity which decreased with increasing thickness in the temperature range of 550-650 °C. They also showed NO sensitivity that was independent of thickness at 400 °C and 600 °C, but varied at temperatures between. This behavior was attributed to multiple mechanistic contributions explained by Differential Electrode Equilibria.     

Generating candidate networks for optimization: The CO2 capture and storage optimization problem

We develop a new framework for spatially optimizing infrastructure for CO₂ capture and storage (CCS). CCS is a complex and challenging problem: domestically deploying CCS at a meaningful scale will require linking hundreds of coal-fired power plants with CO₂ sequestration reservoirs through a dedicated and extensive (many tens-of-thousands of miles) CO₂ pipeline network. We introduce a unique method for generating a candidate network from scratch, from which the optimization model selects the optimal set of arcs to form the pipeline network. This new generation method can be applied to any network optimization problem including transmission line, roads, and telecommunication applications. We demonstrate the model and candidate network methodology using a real example of capturing CO₂ from coal-fired power plants in the US Midwest and storing the CO₂ in depleted oil and gas fields. Results illustrate the critical need to balance CCS investments with generating a candidate network of arcs.     

Effect of La2CuO4 electrode area on potentiometric NOx sensor response and its implications on sensing mechanism

The intent of this work is to look at the effects of varying the La₂CuO₄ electrode area and the asymmetry between the sensing and counter electrode in a solid state potentiometric sensor with respect to NO_x sensitivity. NO₂ sensitivity was observed at 500-600 °C with a maximum sensitivity of ∼22 mV/decade [NO₂] observed at 500 °C for the sensor with a La₂CuO₄ electrode area of ∼30 mm². The relationship between NO₂ sensitivity and area is nearly parabolic at 500 °C, decreases linearly with increasing electrode area at 600 °C, and was a mixture of parabolic and linear behavior 550 °C. NO sensitivity varied non-linearly with electrode area with a minima (maximum sensitivity) of ∼−22 mV/decade [NO] at 450 °C for the sensor with a La₂CuO₄ electrode area of 16 mm². The behavior at 400 °C was similar to that of 450 °C, but with smaller sensitivities due to a saturation effect. At 500 °C, NO sensitivity decreases linearly with area.We also used electrochemical impedance spectroscopy (EIS) to investigate the electrochemical processes that are affected when the sensing electrode area is changed. Changes in impedance with exposure to NO_x were attributed to either changes in La₂CuO₄ conductivity due to gas adsorption (high frequency impedance) or electrocatalysis occurring at the electrode/electrolyte interface (total electrode impedance). NO₂ caused a decrease in high frequency impedance while NO caused an increase. In contrast, NO₂ and NO both caused a decrease in the total electrode impedance. The effect of area on both the potentiometric and impedance responses show relationships that can be explained through the mechanistic contributions included in differential electrode equilibria.     

Conduction mechanisms in SnO2 based polycrystalline thick film gas sensors exposed to CO and H2 in different oxygen backgrounds

The conduction mechanism in polycrystalline SnO₂ thick sensing films was modeled and experimentally investigated by means of simultaneous DC electrical resistance and work function changes measurements under CO and H₂ exposure in different oxygen backgrounds. It was shown that, according to the composition of the ambient atmosphere, the conduction changes from the case in which it is controlled by the surface depletion layers to a situation in which the main contribution comes from free charge transport in the surface accumulation layer. This is significant for the interpretation of work function changes measurements results because the relation between the different measured electrical resistance and surface band bending depends on the conduction model. Furthermore, the CO sensing mechanism dependence on the oxygen amount in the ambient was explained.     

Global biomass mapping for an improved understanding of the CO2 balance—the Earth observation mission Carbon-3D

Understanding global climate change and developing strategies for sustainable use of our environmental resources are major scientific and political challenges. In response to an announcement of the German Aerospace Center (DLR) for a national Earth observation (EO) mission, the Friedrich-Schiller University Jena and the JenaOptronik GmbH proposed the EO mission Carbon-3D. The data products of this mission will for the first time accurately estimate aboveground biomass globally, one of the most important parameters of the carbon cycle. Simultaneous acquisition of multiangle optical with Light Detection and Ranging (LIDAR) observations is unprecedented. The optical imager extrapolates the laser-retrieved height profiles to biophysical vegetation maps. This innovative mission will reduce uncertainties about net effects of deforestation and forest regrowth on atmospheric CO₂ concentrations and will also provide key biophysical information for biosphere models.     

Synthesis of novel SnO2/ZnSnO3 core-shell microspheres and their gas sensing properities

Large-scale novel core-shell structural SnO₂/ZnSnO₃ microspheres were successfully synthesized by a simple hydrothermal method with the help of the surfactant poly(vinyl pyrrolidone) PVP. The as-synthesized samples were characterized using X-ray powder diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM), and high-resolution transmission electron microscopy (HRTEM). The results indicate that the shell was formed by single crystalline ZnSnO₃ nanorods and the core was formed by aggregated SnO₂ nanoparticles. The effects of PVP and hydrothermal time on the morphology of SnO₂/ZnSnO₃ were investigated. A possible formation mechanism of these hierarchical structures was discussed. Moreover, the sensor performance of the prepared core-shell SnO₂/ZnSnO₃ nanostructures to ethanol was studied. The results indicate that the as-synthesized samples exhibited high response and quick response-recovery to ethanol.     

Synthesis of Bi and Gd doped ZnB2O4 for evaluation as potential materials in luminescent display applications

A series of Bi³⁺ and Gd³⁺ doped ZnB₂O₄ phosphors were synthesized with solid state reaction technique. X-ray diffraction technique was employed to study the structure of prepared samples. Excitation and emission spectra were recorded to investigate the luminescence properties of phosphors. The doping of Bi³⁺ or Gd³⁺ with a small amount (no more than 3 mol%) does not change the structure of prepared samples remarkably. Bi³⁺ in ZnB₂O₄ can emit intense broad-band purplish blue light peaking at 428 nm under the excitation of a broad-band peaking at 329 nm. The optimal doping concentration of Bi³⁺ is experimentally ascertained to be 0.5 mol%. The decay time of Bi³⁺ in ZnB₂O₄ changes from 0.88 to 1.69 ms. Gd³⁺ in ZnB₂O₄ can be excited with 254 nm ultraviolet light and yield intense 312 nm emission. The optimal doping concentration of Gd³⁺ is experimentally ascertained to be 5 mol%. The decay time of Gd³⁺ in ZnB₂O₄ changes from 0.42 to 1.36 ms.     

Nanoplates of α-SnWO4 and SnW3O9 prepared via a facile hydrothermal method and their gas-sensing property

Nanoplates of α-SnWO₄ and SnW₃O₉ were selectively synthesized in large scale via a facile hydrothermal reaction method. The final products obtained were dependent on the reaction pH and the molar ratio of W⁶⁺ to Sn²⁺ in the precursors. The as-prepared nanoplates of α-SnWO₄ and SnW₃O₉ were characterized by X-ray powder diffraction (XRD), N₂-sorption BET surface area, transmission electron microscopy (TEM), high-resolution transmission electron microscopy (HRTEM) and X-ray photoelectron spectroscopy (XPS). The XPS results showed that Sn exists in divalent form (Sn²⁺) in SnW₃O₉ as well as in α-SnWO₄. The gas-sensing performances of the as-prepared α-SnWO₄ and SnW₃O₉ toward H₂S and H₂ were investigated. The hydrothermal prepared α-SnWO₄ showed higher response toward H₂ than that prepared via a solid-state reaction due to the high specific surface area. The gas-sensing property toward H₂S as well as H₂ over SnW₃O₉ was for the first time reported. As compared to α-SnWO₄, SnW₃O₉ exhibits higher response toward H₂S and its higher response can be well explained by the existence of the multivalent W (W⁶⁺/W⁴⁺) in SnW₃O₉.     

Responses of the reflectance indices PRI and NDVI to experimental warming and drought in European shrublands along a north-south climatic gradient

The aim of this study was to evaluate the use of ground-based canopy reflectance measurements to detect changes in physiology and structure of vegetation in response to experimental warming and drought treatment at six European shrublands located along a North-South climatic gradient. We measured canopy reflectance, effective green leaf area index (green LAIe) and chlorophyll fluorescence of dominant species. The treatment effects on green LAIe varied among sites. We calculated three reflectance indices: photochemical reflectance index PRI [531 nm; 570 nm], normalized difference vegetation index NDVI₆₈₀ [780 nm; 680 nm] using red spectral region, and NDVI₅₇₀ [780 nm; 570 nm] using the same green spectral region as PRI. All three reflectance indices were significantly related to green LAIe and were able to detect changes in shrubland vegetation among treatments. In general warming treatment increased PRI and drought treatment reduced NDVI values. The significant treatment effect on photochemical efficiency of plants detected with PRI could not be detected by fluorescence measurements. However, we found canopy level measured PRI to be very sensitive to soil reflectance properties especially in vegetation areas with low green LAIe. As both soil reflectance and LAI varied between northern and southern sites it is problematic to draw universal conclusions of climate-derived changes in all vegetation types based merely on PRI measurements. We propose that canopy level PRI measurements can be more useful in areas of dense vegetation and dark soils.     

Critical thermodynamic evaluation and optimization of the MnO–“ TiO2 ”–“ Ti2O3 ” system

A complete review, critical evaluation, and thermodynamic optimization of the phase equilibrium and thermodynamic properties of the MnO–“ TiO₂”–“ Ti₂O₃” systems at 1 bar pressure are presented. The molten oxide phase was described by the Modified Quasichemical Model. The Gibbs energy of spinel, pyrophanite and pseudobrookite solid solutions were modeled using the Compound Energy Formalism, and rutile solid solution was treated as a simple Henrian solution. Manganosite solid solution was assumed to dissolve both Ti⁴⁺ and Ti³⁺. A set of optimized model parameters for all phases was obtained which reproduces all available reliable thermodynamic and phase equilibrium data within experimental error limits from 25 ^°C to above the liquidus temperatures over the entire composition ranges and in the range of pO₂ from 10⁻²⁰ to 10⁻⁷ bar. Complex phase relationships in these systems have been elucidated, and discrepancies among the data have been resolved. The database of model parameters can be used along with software for Gibbs energy minimization in order to calculate any phase diagram section or thermodynamic properties.     

Synthesis of ZnO nanorods and its application in NO2 sensors

One-dimensional (1D) ZnO nanorods with pencil-like shape and high aspect ratio were successfully synthesized using a cetyltrimethylammonium bromide (CTAB)-assisted hydrothermal process at 90 °C. The surface morphology and structure of nanocrystals were characterized by FE-SEM, XRD and XPS analysis. Experimental results show that the surfactant and base concentration play important roles in the formation and growth orientation of ZnO nanorods. The ZnO nanorods synthesized exhibits high response and selectivity to NO₂, the highest response to 40 ppm NO₂ reached 206 and the selectivity with respect to CO and CH₄ at same concentration reached 10.3 and 30 times, respectively. The effects of synthesis method, surfactant and calcination condition on sensing properties were systematically investigated. The results indicate that the CTAB-assisted low temperature hydrothermal process is a potentially facile method for synthesis of 1D ZnO nanorods and excellent potential candidates as gas sensing materials.     

In2O3 + xBaO (x = 0.5-5 at.%) - A novel material for trace level detection of NOx in the ambient

Indium oxide (In₂O₃) doped with 0.5-5 at.% of Ba was examined for their response towards trace levels of NO_x in the ambient. Crystallographic phase studies, electrical conductivity and sensor studies for NO_x with cross interference for hydrogen, petroleum gas (PG) and ammonia were carried out. Bulk compositions with x ≤ 1 at.% of Ba exhibited high response towards NO_x with extremely low cross interference for hydrogen, PG and ammonia, offering high selectivity. Thin films of 0.5 at.% Ba doped In₂O₃ were deposited using pulsed laser deposition technique using an excimer laser (KrF) operating at a wavelength of (λ) 248 nm with a fluence of ∼3 J/cm² and pulsed at 10 Hz. Thin film sensors exhibited better response towards 3 ppm NO_x quite reliably and reproducibly and offer the potential to develop NO_x sensors (Threshold limit value of NO₂ and NO is 3 and 25 ppm, respectively).     

Growth kinetics of nanograins in SnO2 fibers and size dependent sensing properties

The present study investigates the growth kinetics of SnO₂ nanograins and determines the activation energy and mechanism of the growth in nanofiber form. The activation energy for the growth of the SnO₂ nanograins was estimated to be ∼28.28 kJ/mol, which is an order of magnitude smaller than that of bulk SnO₂. The estimated m value suggests that the growth mechanism of the nanograins is primarily through lattice diffusion in the pore control scheme. Precise control of the calcination temperature and time is necessary to maximize the efficiency of electrospinning-synthesized SnO₂ nanofibers for sensor applications. Importantly, the sensor fabricated with nanofibers of small nanograins showed much better sensing properties to CO and NO₂ comparing with the sensor fabricated with nanofibers of large nanograins. A mechanism to explain this finding is suggested.