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USGS2005

X-ray scattering and spectroscopy studies on diesel soot from oxygenated fuel under various engine load conditions

Diesel soot from reference diesel fuel and oxygenated fuel under idle and load engine conditions was investigated with X-ray scattering and X-ray carbon K-edge absorption spectroscopy. Up to five characteristic size ranges were found. Idle soot was generally found to have larger primary particles and aggregates but smaller crystallites, than load soot. Load soot has a higher degree of crystallinity than idle soot. Adding oxygenates to diesel fuel enhanced differences in the characteristics of diesel soot, or even reversed them. Aromaticity of idle soot from oxygenated diesel fuel was significantly larger than from the corresponding load soot. Carbon near-edge X-ray absorption fine structure (NEXAFS) spectroscopy was applied to gather information about the presence of relative amounts of carbon double bonds (CC, CO) and carbon single bonds (C-H, C-OH, COOH). Using scanning X-ray transmission microspectroscopy (STXM), the relative amounts of these carbon bond states were shown to vary spatially over distances approximately 50 to 100 nm. The results from the X-ray techniques are supported by thermo-gravimetry analysis and high-resolution transmission electron microscopy. ?? 2005 Elsevier Ltd. All rights reserved.

Carbon↗

USGS2025

Leveraging airborne imaging spectroscopy and multispectral satellite imagery to map glacial sediment plumes in Kachemak Bay, Alaska

Study Region Kachemak Bay is a fjord-type estuary in the northern Gulf of Alaska. Water quality and habitat characteristics are strongly influenced by freshwater and sediment input from multiple glacierized catchments. Study Focus We present a new method combining imaging spectroscopy from an airborne survey with Landsat and Sentinel-2 imagery to map water surface turbidity originating from glacial runoff based on spectral abundance. We compare the spectral characteristics of turbid glacial water to clear water and generate a high resolution reference map of glacial turbidity in Kachemak Bay. This informs the subsequent analysis of a homogenized, Rayleigh corrected time series of Landsat and Sentinel-2 images and seasonal patterns of turbidity. New Hydrological Insights for the Region Our results provide the most comprehensive data set on water surface turbidity in Kachemak Bay to date and improve understanding of spatial and seasonal variability of glacial turbidity in a data sparse region. July and August have the largest plumes with median sizes around 150 km 2 "> 2 , or around a quarter of Kachemak Bay. Plume sizes typically decrease with decreasing glacier runoff in September and October. We show that imaging spectroscopy aids assessments of turbid water in glacial marine catchments across scales. Leveraging high resolution spectral information allows for water color analyses that are customized to local conditions and catchment characteristics as well as scalable to wider regions.

Alaska↗

USGS2004

Speciation and characterization of arsenic in gold ores and cyanidation tailings using X-ray absorption spectroscopy

The knowledge of mineralogy and molecular structure of As is needed to better understand the stability of As in wastes resulting from processing of gold ores. In this study, optical microscopy, scanning electron microscopy, electron microprobe, X-ray diffraction and X-ray absorption fine structure (XAFS) spectroscopy (including both XANES and EXAFS regimes) were employed to determine the mineralogical composition and local coordination environment of As in gold ores and process tailings from bench-scale tests designed to mimic a common plant practice. Arsenic-bearing minerals identified in the ores and tailings include iron (III) oxyhydroxides, scorodite (FeAsO4??2H2O), ferric arsenates, arseniosiderite (Ca2Fe3 (AsO4)3O2??3H2O), Ca-Fe arsenates, pharmacosiderite (KFe4 (AsO4)3(OH)4??6-7H2O), jarosite (K2Fe6(SO4)4 (OH)12) and arsenopyrite (FeAsS). Iron (III) oxyhydroxides contain variable levels of As from trace to about 22 wt% and Ca up to approximately 9 wt%. Finely ground ore and tailings samples were examined by bulk XAFS and selected mineral grains were analyzed by microfocused XAFS (micro-EXAFS) spectroscopy to reconcile the ambiguities of multiple As sources in the complex bulk EXAFS spectra. XANES spectra indicated that As occurs as As5+in all the samples. Micro-EXAFS spectra of individual iron (III) oxyhydroxide grains with varying As concentrations point to inner-sphere bidentate-binuclear arsenate complexes as the predominant form of As. There are indications for the presence of a second Fe shell corresponding to bidentate-mononuclear arrangement. Iron (III) oxyhydroxides with high As concentrations corresponding to maximum adsorption densities probably occur as nanoparticles. The discovery of Ca atoms around As in iron (III) oxyhydroxides at interatomic distances of 4.14-4.17 A?? and the coordination numbers suggest the formation of arseniosiderite-like nanoclusters by coprecipitation rather than simple adsorption of Ca onto iron (III) oxyhydroxides. Correlation of Ca with As in iron (III) oxyhydroxides as determined by electron microprobe analysis supports the coprecipitate origin for the presence of Ca in iron (III) oxyhydroxides. The samples containing higher abundances of ferric arsenates released higher As concentrations during the cyanidation tests. The presence of highly soluble ferric arsenates and Ca-Fe arsenates, and relatively unstable iron (III) oxyhydroxides with Fe/As molar ratios of less than 4 in the ore and process tailings suggests that not only the tailings in the impoundment will continue to release As, but also there is the potential for mobilization of As from the natural sources such as the unmined ore. ?? 2004 Elsevier Ltd.

Geochimica et Cosmochimica Acta↗

USGS2009

Determination of diffusion coefficients of hydrogen in fused silica between 296 and 523 K by Raman spectroscopy and application of fused silica capillaries in studying redox reactions

Diffusion coefficients ( D ) of hydrogen in fused silica capillaries (FSC) were determined between 296 and 523 K by Raman spectroscopy using CO 2 as an internal standard. FSC capsules (3.25 × 10 −4 m OD, 9.9 × 10 −5 m ID, and ∼0.01 m long) containing CO 2 and H 2 were prepared and the initial relative concentrations of hydrogen in these capsules were derived from the Raman peak-height ratios between H 2 (near 587 cm −1 ) and CO 2 (near 1387 cm −1 ). The sample capsules were then heated at a fixed temperature ( T ) at one atmosphere to let H 2 diffuse out of the capsule, and the changes of hydrogen concentration were monitored by Raman spectroscopy after quench. This process was repeated using different heating durations at 296 (room T ), 323, 375, 430, 473, and 523 K; the same sample capsule was used repeatedly at each temperature. The values of D (in m 2 s −1 ) in FSC were obtained by fitting the observed changes of hydrogen concentration in the FSC capsule to an equation based on Fick’s law. Our D values are in good agreement with the more recent of the two previously reported experimental data sets, and both can be represented by: ln D = - ( 16.471 ± 0.035 ) - 44589 ± 139 RT ( R 2 = 0.99991 ) "> lnD=-(16.471±0.035)-44589±139RT(R2=0.99991) where R is the gas constant (8.3145 J/mol K), T in Kelvin, and errors at 1 σ level. The slope corresponds to an activation energy of 44.59 ± 0.14 kJ/mol. The D in FSC determined at 296 K is about an order of magnitude higher than that in platinum at 723 K, indicating that FSC is a suitable membrane for hydrogen at temperature between 673 K and room temperature, and has a great potential for studying redox reactions at these temperatures, especially for systems containing organic material and/or sulphur.

Geochimica et Cosmochimica Acta↗

USGS2016

Novel insights from NMR spectroscopy into seasonal changes in the composition of dissolved organic matter exported to the Bering Sea by the Yukon River

Seasonal (spring freshet, summer–autumn, and winter) variability in the chemical composition of dissolved organic matter (DOM) from the Yukon River was determined using advanced one- and two-dimensional (2D) solid-state NMR spectroscopy, coupled with isotopic measurements and UV–visible spectroscopy. Analyses were performed on two major DOM fractions, the hydrophobic organic acid (HPOA) and transphilic organic acid (TPIA) fractions obtained using XAD resins. Together these two fractions comprised 64–74% of the total DOM. Carboxyl-rich alicyclic molecules (CRAM) accounted for the majority of carbon atoms in the HPOA (63–77%) and TPIA (54–78%) samples, and more so in winter and summer than in spring samples. 2D and selective NMR data revealed association of abundant nonprotonated O-alkyl and quaternary alkyl C (OC np , OC np O and C q , 13–17% of HPOA and 15–20% of TPIA) and isolated O–CH structures with CRAM, which were not recognized in previous studies. Spectral editing and 2D NMR allowed for the discrimination of carbohydrate-like O-alkyl C from non-carbohydrate O-alkyl C. Whereas two spring freshet TPIA samples contained carbohydrate clusters such as carboxylated carbohydrates (16% and 26%), TPIA samples from other seasons or HPOA samples mostly had small amounts (<8%) of sugar rings dispersed in a nonpolar alkyl environment. Though nonprotonated aromatic C represented the largest fraction of aromatic C in all HPOA/TPIA isolates, only a small fraction (&sim;5% in HPOA and 3% in TPIA) was possibly associated with dissolved black carbon. Our results imply a relatively stable portion of DOM exported by the Yukon River across different seasons, due to the predominance of CRAM and their associated nonprotonated C–O and O–C–O structures, and elevated reactivity (bio- and photo-lability) of spring DOM due to the presence of terrestrial inputs enriched in carbohydrates and aromatic structures.

Alaska, Yukon↗

USGS2017

Solid-phase arsenic speciation in aquifer sediments: A micro-X-ray absorption spectroscopy approach for quantifying trace-level speciation

e of this research is to identify the solid-phase sources and geochemical mechanisms of release of As in aquifers of the Des Moines Lobe glacial advance. The overarching concept is that conditions present at the aquifer-aquitard interfaces promote a suite of geochemical reactions leading to mineral alteration and release of As to groundwater. A microprobe X-ray absorption spectroscopy (lXAS) approach is developed and applied to rotosonic drill core samples to identify the solid-phase speciation of As in aquifer, aquitard, and aquifer-aquitard interface sediments. This approach addresses the low solid-phase As concentrations, as well as the fine-scale physical and chemical heterogeneity of the sediments. The spectroscopy data are analyzed using novel cosine-distance and correlation-distance hierarchical clustering for Fe 1s and As 1s lXAS datasets. The solid-phase Fe and As speciation is then interpreted using sediment and well-water chemical data to propose solid-phase As reservoirs and release mechanisms. The results confirm that in two of the three locations studied, the glacial sediment forming the aquitard is the source of As to the aquifer sediments. The results are consistent with three different As release mechanisms: (1) desorption from Fe (oxyhydr)oxides, (2) reductive dissolution of Fe (oxyhydr)oxides, and (3) oxidative dissolution of Fe sulfides. The findings confirm that glacial sediments at the interface between aquifer and aquitard are geochemically active zones for As. The diversity of As release mechanisms is consistent with the geographic heterogeneity observed in the distribution of elevated-As wells.

Geochimica et Cosmochimica Acta↗

USGS2002

Surface complexation and precipitate geometry for aqueous Zn(II) sorption on ferrihydrite I: X-ray absorption extended fine structure spectroscopy analysis

“Two-line” ferrihydrite samples precipitated and then exposed to a range of aqueous Zn solutions (10 −5 to 10 −3 M), and also coprecipitated in similar Zn solutions (pH 6.5), have been examined by Zn and Fe K-edge X-ray absorption spectroscopy. Typical Zn complexes on the surface have Zn-O distances of 1.97(.02) Å and coordination numbers of about 4.0(0.5), consistent with tetrahedral oxygen coordination. This contrasts with Zn-O distances of 2.11(.02) Å and coordination numbers of 6 to 7 in the aqueous Zn solutions used in sample preparation. X-ray absorption extended fine structure spectroscopy (EXAFS) fits to the second shell of cation neighbors indicate as many as 4 Zn-Fe neighbors at 3.44(.04) Å in coprecipitated samples, and about two Zn-Fe neighbors at the same distance in adsorptionsamples. In both sets of samples, the fitted coordination number of second shell cations decreases as sorption density increases, indicating changes in the number and type of available complexing sites or the onset of competitive precipitation processes. Comparison of our results with the possible geometries for surface complexes and precipitates suggests that the Zn sorption complexes are inner sphere and at lowest adsorption densities are bidentate, sharing apical oxygens with adjacent edge-sharing Fe(O,OH) 6 octahedra. Coprecipitation samples have complexes with similar geometry, but these are polydentate, sharing apices with more than two adjacent edge-sharing Fe(O,OH) 6 polyhedra. The results are inconsistent with Zn entering the ferrihydrite structure (i.e., solid solution formation) or formation of other Zn-Fe precipitates. The fitted Zn-Fe coordination numbers drop with increasing Zn density with a minimum of about 0.8(.2) at Zn/(Zn + Fe) of 0.08 or more. This change appears to be attributable to the onset of precipitation of zinc hydroxide polymers with mainly tetrahedral Zn coordination. At the highest loadings studied, the nature of the complexes changes further, and a second type of precipitate forms. This has a structure based on a brucite layer topology, with mainly octahedral Zn coordination. Amorphous zinc hydroxide samples prepared for comparison had a closely similar local structure. Analysis of the Fe K-edge EXAFS is consistent with surface complexation reactions and surface precipitation at high Zn loadings with little or no Fe-Zn solid solution formation. The formation of Zn-containing precipitates at solution conditions two or more orders of magnitude below their solubility limit is compared with other sorption and spectroscopic studies that describe similar behavior.

Geochimica et Cosmochimica Acta↗

USGS2017

Real-time specific surface area measurements via laser-induced breakdown spectroscopy

From healthcare to cosmetics to environmental science, the specific surface area (SSA) of micro- and mesoporous materials or products can greatly affect their chemical and physical properties. SSA results are also widely used to examine source rocks in conventional and unconventional petroleum resource plays. Despite its importance, current methods to measure SSA are often cumbersome, time-consuming, or require cryogenic consumables (e.g., liquid nitrogen). These methods are not amenable to high-throughput environments, have stringent sample preparation requirements, and are not practical for use in the field. We present a new application of laser-induced breakdown spectroscopy for rapid measurement of SSA. This study evaluates geological samples, specifically organic-rich oil shales, but the approach is expected to be applicable to many other types of materials. The method uses optical emission spectroscopy to examine laser-generated plasma and quantify the amount of argon adsorbed to a sample during an inert gas purge. The technique can accommodate a wide range of sample sizes and geometries and has the potential for field use. These advantages for SSA measurement combined with the simultaneous acquisition of composition information make this a promising new approach for characterizing geologic samples and other materials.

Energy and Fuels↗

USGS2009

Characterization of Mars' seasonal caps using neutron spectroscopy

Mars' seasonal caps are characterized during Mars years 26 and 27 (April 2002 to January 2006) using data acquired by the 2001 Mars Odyssey Neutron Spectrometer. Time-dependent maps of the column abundance of seasonal CO 2 surface ice poleward of 60?? latitude in both hemispheres are determined from spatially deconvolved, epithermal neutron counting data. Sources of systematic error are analyzed, including spatial blurring by the spectrometer's broad footprint and the seasonal variations in the abundance of noncondensable gas at high southern latitudes, which are found to be consistent with results reported by Sprague et al. (2004, 2007). Corrections for spatial blurring are found to be important during the recession, when the column abundance of seasonal CO 2 ice has the largest latitude gradient. The measured distribution and inventory of seasonal CO 2 ice is compared to simulations by a general circulation model (GCM) calibrated using Viking lander pressure data, cap edge functions determined by thermal emission spectroscopy, and other nuclear spectroscopy data sets. On the basis of the amount of CO 2 cycled through the caps during years 26 and 27, the gross polar energy balance has not changed significantly since Viking. The distribution of seasonal CO 2 ice is longitudinally asymmetric: in the north, deposition rates of CO 2 ice are elevated in Acidalia, which is exposed to katabatic winds from Chasma Borealis; in the south, CO 2 deposition is highest near the residual cap. During southern recession, CO 2 ice is present longer than calculated by the GCM, which has implications for the local polar energy balance. Copyright 2009 by the American Geophysical Union.

Journal of Geophysical Research E: Planets↗

USGS2024

Identification of kaolins and associated minerals in altered volcanic rocks by infrared spectroscopy

Mid-infrared spectroscopy (2.5-50 /µm) has been extensively used to identify and characterize clays and associated minerals in rocks and soils, with particular emphasis on the 3-, 10-, and 20-/µm regions (Farmer and Russell, 1967; Farmer, 1968; White, 1971; Van der Marel and Beutelspacher, 1976). However, application of mid-infrared spectroscopy in remote-sensing activities has been restricted because the spectral information occurs only as a small perturbation to the emitted radiation from the earth's surface, and much of that which is especially relevant to clays (e.g., the 3.0-µm region) is obscured by atmospheric absorption.

Clays and Clay Minerals↗

USGS2017

Aerodynamic roughness length estimation with lidar and imaging spectroscopy in a shrub-dominated dryland

The aerodynamic roughness length (Z 0 m ) serves an important role in the flux exchange between the land surface and atmosphere. In this study, airborne lidar ( ALS ), terrestrial lidar ( TLS ), and imaging spectroscopy data were integrated to develop and test two approaches to estimate Z 0 m over a shrub dominated dryland study area in south-central Idaho, USA. Sensitivity of the two parameterization methods to estimate Z 0 m was analyzed. The comparison of eddy covariance-derived Z 0 m and remote sensing-derived Z 0 m showed that the accuracy of the estimated Z 0 m heavily depends on the estimation model and the representation of shrub (e.g., Artemisia tridentata subsp. wyomingensis) height in the models. The geometrical method (RA1994) led to 9 percent (~0.5 cm) and 25% (~1.1 cm) errors at site 1 and site 2, respectively, which performed better than the height variability-based method (MR1994) with bias error of 20 percent and 48 percent at site 1 and site 2, respectively. The RA1994 model resulted in a larger range of Z 0 m than the MR1994 method. We also found that the mean, median and 75th percentiles of heights (H75) from ALS provides the best Z 0 m estimates in the MR1994 model, while the mean, median, and MLD (Median Absolute Deviation from Median Height), as well as AAD (Mean Absolute Deviation from Mean Height) heights from ALS provides the best Z 0 m estimates in the RA1994 model. In addition, the fractional cover of shrub and grass, distinguished with ALS and imaging spectroscopy data, provided the opportunity to estimate the frontal area index at the pixel-level to assess the influence of grass and shrub on Z 0 m estimates in the RA1994 method. Results indicate that grass had little effect on Z 0 m in the RA1994 method. The Z 0 m estimations were tightly coupled with vegetation height and its local variance for the shrubs. Overall, the results demonstrate that the use of height and fractional cover from remote sensing data are promising for estimating Z 0 m , and thus refining land surface models at regional scales in semiarid shrublands.

Photogrammetric Engineering and Remote Sensing↗

USGS2005

Reconnaissance gas measurements on the East Rift Zone of Kilauea Volcano, Hawai'i by Fourier transform infrared spectroscopy

We report the results of a set of measurements of volcanic gases on two small ground level plumes in the vicinity of Pu`u `O`o cone on the middle East Rift Zone (ERZ) of Kilauea volcano, Hawai`i on 15 June 2001 using open-path Fourier transform infrared (FTIR) spectroscopy. The work was carried out as a reconnaissance survey to assess the monitoring and research value of FTIR measurements at this volcano. Despite representing emissions of residual volatiles from lava that has undergone prior degassing, the plumes contained detectable amounts of CO2, CO, SO2, HCl, HF and SiF4. Various processes, including subsurface cooling, condensation of water in the atmospheric plume, oxidation, dissolution in water, and reactions with wall rocks at plume vents affect the abundance of these gases. Low concentrations of volcanic CO2 measured against a high ambient background are not well constrained by FTIR spectroscopy. Although there appear to be some differences between these gases and Pu`u `O`o source gases, ratios of HCl/SO2, HF/SO2 and CO/SO2 determined by FTIR measurements of these two small plumes compare reasonably well with earlier published analyses of ERZ vent samples. The measurements yielded emission rate estimates of 4, 11 and 4 t d-1

Hawaii↗

USGS2018

Application of imaging spectroscopy for mineral exploration in Alaska: A study over porphyry Cu deposits in the eastern Alaska Range

The U.S. Geological Survey tested the utility of imaging spectroscopy (also referred to as hyperspectral remote sensing) as an aid to regional mineral exploration efforts in remote parts of Alaska. Airborne imaging spectrometer data were collected in 2014 over unmined porphyry Cu deposits in the eastern Alaska Range using the HyMap™ sensor. Maps of the distributions of predominant minerals, made by matching reflectance signatures in the remotely sensed data to reference spectra in the shortwave infrared region, do not uniquely discriminate individual rock units. However, they do highlight hydrothermal alteration associated with porphyry deposits and prospects hosted mostly within the Nabesna pluton. In and around porphyry Cu deposits at Orange Hill and Bond Creek, unique spectral signatures are related to variations in chlorite and white mica abundance and their chemical composition. This is best revealed in the longer-wavelength 2,200-nm Al-OH absorption feature positions in pixels spectrally dominated by white mica proximal to porphyry deposits. Similar spectral signatures of chlorite and white mica wavelength positions were also recognized away from the porphyry deposits; follow-up sampling identified these satellite areas to also contain Cu-Mo-Au mineralized rock. Our study confirms that airborne imaging spectroscopy has application for regional mineral exploration in exposed mountainous terrain in Alaska.

Alaska↗

USGS2013

Pre-flight calibration and initial data processing for the ChemCam laser-induced breakdown spectroscopy instrument on the Mars Science Laboratory rover

The ChemCam instrument package on the Mars Science Laboratory rover, Curiosity, is the first planetary science instrument to employ laser-induced breakdown spectroscopy (LIBS) to determine the compositions of geological samples on another planet. Pre-processing of the spectra involves subtracting the ambient light background, removing noise, removing the electron continuum, calibrating for the wavelength, correcting for the variable distance to the target, and applying a wavelength-dependent correction for the instrument response. Further processing of the data uses multivariate and univariate comparisons with a LIBS spectral library developed prior to launch as well as comparisons with several on-board standards post-landing. The level-2 data products include semi-quantitative abundances derived from partial least squares regression. A LIBS spectral library was developed using 69 rock standards in the form of pressed powder disks, glasses, and ceramics to minimize heterogeneity on the scale of the observation (350–550 μm dia.). The standards covered typical compositional ranges of igneous materials and also included sulfates, carbonates, and phyllosilicates. The provenance and elemental and mineralogical compositions of these standards are described. Spectral characteristics of this data set are presented, including the size distribution and integrated irradiances of the plasmas, and a proxy for plasma temperature as a function of distance from the instrument. Two laboratory-based clones of ChemCam reside in Los Alamos and Toulouse for the purpose of adding new spectra to the database as the need arises. Sensitivity to differences in wavelength correlation to spectral channels and spectral resolution has been investigated, indicating that spectral registration needs to be within half a pixel and resolution needs to match within 1.5 to 2.6 pixels. Absolute errors are tabulated for derived compositions of each major element in each standard using PLS regression. Sources of errors are investigated and discussed, and methods for improving the analytical accuracy of compositions derived from ChemCam spectra are discussed.

Spectrochimica Acta Part B: Atomic Spectroscopy↗

USGS2017

Improved accuracy in quantitative laser-induced breakdown spectroscopy using sub-models

Accurate quantitative analysis of diverse geologic materials is one of the primary challenges faced by the Laser-Induced Breakdown Spectroscopy (LIBS)-based ChemCam instrument on the Mars Science Laboratory (MSL) rover. The SuperCam instrument on the Mars 2020 rover, as well as other LIBS instruments developed for geochemical analysis on Earth or other planets, will face the same challenge. Consequently, part of the ChemCam science team has focused on the development of improved multivariate analysis calibrations methods. Developing a single regression model capable of accurately determining the composition of very different target materials is difficult because the response of an element’s emission lines in LIBS spectra can vary with the concentration of other elements. We demonstrate a conceptually simple “sub-model” method for improving the accuracy of quantitative LIBS analysis of diverse target materials. The method is based on training several regression models on sets of targets with limited composition ranges and then “blending” these “sub-models” into a single final result. Tests of the sub-model method show improvement in test set root mean squared error of prediction (RMSEP) for almost all cases. The sub-model method, using partial least squares regression (PLS), is being used as part of the current ChemCam quantitative calibration, but the sub-model method is applicable to any multivariate regression method and may yield similar improvements.

Spectrochimica Acta Part B: Atomic Spectroscopy↗

USGS2006

In situ study of mass transfer in aqueous solutions under high pressures via Raman spectroscopy: A new method for the determination of diffusion coefficients of methane in water near hydrate formation conditions

A new method was developed for in situ study of the diffusive transfer of methane in aqueous solution under high pressures near hydrate formation conditions within an optical capillary cell. Time-dependent Raman spectra of the solution at several different spots along the one-dimensional diffusion path were collected and thus the varying composition profile of the solution was monitored. Diffusion coefficients were estimated by the least squares method based on the variations in methane concentration data in space and time in the cell. The measured diffusion coefficients of methane in water at the liquid (L)-vapor (V) stable region and L-V metastable region are close to previously reported values determined at lower pressure and similar temperature. This in situ monitoring method was demonstrated to be suitable for the study of mass transfer in aqueous solution under high pressure and at various temperature conditions and will be applied to the study of nucleation and dissolution kinetics of methane hydrate in a hydrate-water system where the interaction of methane and water would be more complicated than that presented here for the L-V metastable condition. ?? 2006 Society for Applied Spectroscopy.

Applied Spectroscopy↗

USGS2017

Remote measurement of high preeruptive water vapor emissions at Sabancaya volcano by passive differential optical absorption spectroscopy

Water (H 2 O) is by far the most abundant volcanic volatile species and plays a predominant role in driving volcanic eruptions. However, numerous difficulties associated with making accurate measurements of water vapor in volcanic plumes have limited their use as a diagnostic tool. Here we present the first detection of water vapor in a volcanic plume using passive visible-light differential optical absorption spectroscopy (DOAS). Ultraviolet and visible-light DOAS measurements were made on 21 May 2016 at Sabancaya Volcano, Peru. We find that Sabancaya's plume contained an exceptionally high relative water vapor abundance 6 months prior to its November 2016 eruption. Our measurements yielded average sulfur dioxide (SO 2 ) emission rates of 800–900 t/d, H 2 O emission rates of around 250,000 t/d, and an H 2 O/SO 2 molecular ratio of 1000 which is about an order of magnitude larger than typically found in high-temperature volcanic gases. We attribute the high water vapor emissions to a boiling-off of Sabancaya's hydrothermal system caused by intrusion of magma to shallow depths. This hypothesis is supported by a significant increase in the thermal output of the volcanic edifice detected in infrared satellite imagery leading up to and after our measurements. Though the measurement conditions encountered at Sabancaya were very favorable for our experiment, we show that visible-light DOAS systems could be used to measure water vapor emissions at numerous other high-elevation volcanoes. Such measurements would provide observatories with additional information particularly useful for forecasting eruptions at volcanoes harboring significant hydrothermal systems.

Journal of Geophysical Research B: Solid Earth↗

USGS2023

Evaluation of spectral collection strategies for identification of Dalbergia spp. using handheld laser-induced breakdown spectroscopy

The illegal timber trade has significant impact on the survival of endangered tropical hardwood species like Dalbergia spp. (rosewood), a world-wide protected genus from the Convention on International Trade in Endangered Species of Wild Fauna and Flora (CITES). Due to increased threat to Dalbergia spp., and lack of action to reduce threats, port of entry analysis methods are required to identify Dalbergia spp. Handheld laser-induced breakdown spectroscopy (LIBS) has been shown to be capable of identifying species and establishing provenance of Dalbergia spp. and other tropical hardwoods, but analysis methods for this work have yet to be investigated in detail. The present work investigates five well-known algorithms—partial least squares discriminant analysis (PLS-DA), classification and regression trees (CART), k -nearest neighbor ( k -NN), random forest (RF), and support vector machine (SVM)—two training/test set sampling regimes, and data collection at two signal-to-noise (S/N) ratios to assess the potential for handheld LIBS analyses. Additionally, imbalanced classes are addressed. For this application, SVM and RF yield near identical results (though RF takes nearly 100 longer to compute), while the S/N ratio has a significant effect on model success assuming all else is equal. It was found that forming a training set with replicate low S/N analyses can perform as well as higher precision training sets for true prediction, even if the predicted samples have low signal to noise! This work confirms handheld LIBS analyzers can provide a viable method for classification of hardwood species, even within the same genus.

Journal of Chemometrics↗