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USGS2011

Hapke modeling of Rhea surface properties through Cassini-VIMS spectra

T The surface properties of the icy bodies in the saturnian system have been investigated by means of the Cassini-VIMS (Visual Infrared Mapping Spectrometer) hyperspectral imager which operates in the 0.35–5.1 μm wavelength range. In particular, we have analyzed 111 full disk hyperspectral images of Rhea ranging in solar phase between 0.08° and 109.8°. These data have been previously analyzed by Filacchione et al. (Filacchione, G. et al. [2007]. Icarus 186, 259–290; Filacchione, G. et al. [2010]. Icarus 206, 507–523) to study, adopting various “spectral indicators” (such as spectral slopes, band depth, and continuum level), the relations among various saturnian satellites. As a further step we proceed in this paper to a quantitative evaluation of the physical parameters determining the spectrophotometric properties of Rhea’s surface. To do this we have applied Hapke (Hapke, B. [1993]. Theory of Reflectance and Emittance Spectroscopy, Topics in Remote Sensing: 3. Springer, Berlin) IMSA model (Isotropic Multiple Scattering Approximation) which allow us to model the phase function at VIS–IR (visible–infrared) wavelengths as well as the spectra taking into account various types of mixtures of surface materials. Thanks to this method we have been able to constrain the size of water ice particles covering the surface, the amount of organic contaminants, the large scale surface roughness and the opposition effect surge. From our analysis it appears that wavelength dependent parameters, e.g. opposition surge width ( h ) and single-particle phase function parameters ( b , v ), are strongly correlated to the estimated single-scattering albedo of particles. For Rhea the best fit solution is obtained by assuming: (1) an intraparticle mixture of crystalline water ice and a small amount (0.4%) of Triton tholin; (2) a monodisperse grain size distribution having a particle diameter a m = 38 μm; and (3) a surface roughness parameter value of 33°. The study of phase function shows that both shadow hiding and coherent backscattering contribute to the opposition surge. This study represents the first attempt, in the case of Rhea, to join the spectral and the photometric analysis. The surface model we derived gives a good quantitative description of both spectrum and phase curve of the satellite. The same approach and model, with appropriate modifications, shall be applied to VIMS data of the other icy satellites of Saturn, in order to reveal similarities and differences in the surface characteristics to understand how these bodies interact with their environment.

Icarus↗

USGS2013

Correlating multispectral imaging and compositional data from the Mars Exploration Rovers and implications for Mars Science Laboratory

In an effort to infer compositional information about distant targets based on multispectral imaging data, we investigated methods of relating Mars Exploration Rover (MER) Pancam multispectral remote sensing observations to in situ alpha particle X-ray spectrometer (APXS)-derived elemental abundances and Mössbauer (MB)-derived abundances of Fe-bearing phases at the MER field sites in Gusev crater and Meridiani Planum. The majority of the partial correlation coefficients between these data sets were not statistically significant. Restricting the targets to those that were abraded by the rock abrasion tool (RAT) led to improved Pearson’s correlations, most notably between the red–blue ratio (673 nm/434 nm) and Fe 3+ -bearing phases, but partial correlations were not statistically significant. Partial Least Squares (PLS) calculations relating Pancam 11-color visible to near-IR (VNIR; ∼400–1000 nm) “spectra” to APXS and Mössbauer element or mineral abundances showed generally poor performance, although the presence of compositional outliers led to improved PLS results for data from Meridiani. When the Meridiani PLS model for pyroxene was tested by predicting the pyroxene content of Gusev targets, the results were poor, indicating that the PLS models for Meridiani are not applicable to data from other sites. Soft Independent Modeling of Class Analogy (SIMCA) classification of Gusev crater data showed mixed results. Of the 24 Gusev test regions of interest (ROIs) with known classes, 11 had >30% of the pixels in the ROI classified correctly, while others were mis-classified or unclassified. k-Means clustering of APXS and Mössbauer data was used to assign Meridiani targets to compositional classes. The clustering-derived classes corresponded to meaningful geologic and/or color unit differences, and SIMCA classification using these classes was somewhat successful, with >30% of pixels correctly classified in 9 of the 11 ROIs with known classes. This work shows that the relationship between SWIR multispectral imaging data and APXS- and Mössbauer-derived composition/mineralogy is often weak, a perhaps not entirely unexpected result given the different surface sampling depths of SWIR imaging (uppermost few microns) vs. APXS (tens of μm) and MB measurements (hundreds of μm). Results from the upcoming Mars Science Laboratory (MSL) rover’s ChemCam Laser Induced Breakdown Spectroscopy (LIBS) instrument may show a closer relationship to Mastcam SWIR multispectral observations, however, because the initial laser shots onto a target will analyze only the upper few micrometers of the surface. The clustering and classification methods used in this study can be applied to any data set to formalize the definition of classes and identify targets that do not fit in previously defined classes.

Icarus↗

USGS2015

ChemCam results from the Shaler outcrop in Gale crater, Mars

The ChemCam campaign at the fluvial sedimentary outcrop “Shaler” resulted in observations of 28 non-soil targets, 26 of which included active laser induced breakdown spectroscopy (LIBS), and all of which included Remote Micro-Imager (RMI) images. The Shaler outcrop can be divided into seven facies based on grain size, texture, color, resistance to erosion, and sedimentary structures. The ChemCam observations cover Facies 3 through 7. For all targets, the majority of the grains were below the limit of the RMI resolution, but many targets had a portion of resolvable grains coarser than &sim;0.5 mm. The Shaler facies show significant scatter in LIBS spectra and compositions from point to point, but several key compositional trends are apparent, most notably in the average K 2 O content of the observed facies. Facies 3 is lower in K 2 O than the other facies and is similar in composition to the “snake,” a clastic dike that occurs lower in the Yellowknife Bay stratigraphic section. Facies 7 is enriched in K 2 O relative to the other facies and shows some compositional and textural similarities to float rocks near Yellowknife Bay. The remaining facies (4, 5, and 6) are similar in composition to the Sheepbed and Gillespie Lake members, although the Shaler facies have slightly elevated K 2 O and FeO T . Several analysis points within Shaler suggest the presence of feldspars, though these points have excess FeO T which suggests the presence of Fe oxide cement or inclusions. The majority of LIBS analyses have compositions which indicate that they are mixtures of pyroxene and feldspar. The Shaler feldspathic compositions are more alkaline than typical feldspars from shergottites, suggesting an alkaline basaltic source region, particularly for the K 2 O-enriched Facies 7. Apart from possible iron-oxide cement, there is little evidence for chemical alteration at Shaler, although calcium-sulfate veins comparable to those observed lower in the stratigraphic section are present. The differing compositions, and inferred provenances at Shaler, suggest compositionally heterogeneous terrain in the Gale crater rim and surroundings, and intermittent periods of deposition.

Icarus↗

USGS2014

Spectroscopic remote sensing of plant stress at leaf and canopy levels using the chlorophyll 680 nm absorption feature with continuum removal

This paper explores the use of spectral feature analysis to detect plant stress in visible/near infrared wavelengths. A time series of close range leaf and canopy reflectance data of two plant species grown in hydrocarbon-contaminated soil was acquired with a portable spectrometer. The ProSpecTIR-VS airborne imaging spectrometer was used to obtain far range hyperspectral remote sensing data over the field experiment. Parameters describing the chlorophyll 680 nm absorption feature (depth, width, and area) were derived using continuum removal applied to the spectra. A new index, the Plant Stress Detection Index (PSDI), was calculated using continuum-removed values near the chlorophyll feature centre (680 nm) and on the green-edge (560 and 575 nm). Chlorophyll feature’s depth, width and area, the PSDI and a narrow-band normalised difference vegetation index were evaluated for their ability to detect stressed plants. The objective was to analyse how the parameters/indices were affected by increasing degrees of plant stress and to examine their utility as plant stress indicators at the remote sensing level (e.g. airborne sensor). For leaf data, PSDI and the chlorophyll feature area revealed the highest percentage (67–70%) of stressed plants. The PSDI also proved to be the best constraint for detecting the stress in hydrocarbon-impacted plants with field canopy spectra and airborne imaging spectroscopy data. This was particularly true using thresholds based on the ASD canopy data and considering the combination of higher percentage of stressed plants detected (across the thresholds) and fewer false-positives.

Paulinia↗

USGS2025

Reaction kinetics and accelerant effects of sulfides in early mature hydrocarbon generation using hydrous pyrolysis

Hydrocarbon generation in organic-rich sediments is influenced by the molecular organic composition and relative abundance of associated minerals. Certain mineral-derived elements act as catalysts and reaction intermediaries, facilitating early-stage hydrocarbon formation in potential source rocks. This study investigated the role of sulfur contributed from pyrite as an accelerant in thermal reaction, focusing on its effects on early maturation and consequent hydrocarbon generation from gilsonite (low-sulfur solid petroleum). Hydrous pyrolysis (HP) experiments were conducted on mixtures of gilsonite and pyrite in varying ratios (1:0.1, 1:0.5, 1:1, 1:2, and 1:10 w/w gilsonite:pyrite) at 320, 350, and 370 °C for 72 h. Untreated and thermally altered residues were analyzed using solid bitumen reflectance (BR o , %), total organic carbon (TOC) content, programmed temperature pyrolysis, scanning electron microscopy with energy-dispersive spectroscopy (SEM-EDS), and X-ray diffraction (XRD) to evaluate the potential accelerant role of pyritic sulfur in hydrocarbon formation. The results show HP residues at 320 and 350 °C with greater pyrite concentrations had higher BR o , while reflectance values were similar in the 370 °C residues, regardless of pyrite concentration, suggesting enhanced reaction at lower thermal conditions. Increasing pyrite content systematically decreased hydrogen index (HI) values while increasing the transformation ratio (TR) and production index (PI), indicating enhanced conversion of organic matter to hydrocarbons with increasing pyrite concentrations. Gas yields increased with pyrite addition, particularly at 350 °C, confirming secondary cracking effects. However, gas production stabilized or declined at higher pyrite loadings (1:10), suggesting alternative reaction pathways such as coke formation. Our data indicate the presence of pyrite lowers the activation energy for thermal cracking, shifting peak experimental hydrocarbon generation temperatures downward by 20–30 °C, with the most pronounced accelerant effects observed at moderate pyrite concentrations (1:0.5 and 1:1). The thermodynamic framework reveals that pyrite stability is influenced by experimental conditions, with pyrrhotite formation favored in the presence of gilsonite due to reduced oxygen fugacity. Pyrite transformation to pyrrhotite, as observed through XRD, SEM-EDS, and predicted by thermodynamic data, further supports the accelerant role of S, as pyrrhotite exhibits a higher hydrogen transfer potential, promoting early oil generation. These findings highlight the importance of pyrite in modulating hydrocarbon generation pathways in organic-rich systems.

Journal of Analytical and Applied Pyrolysis↗

USGS2004

EXAFS study of mercury(II) sorption to Fe- and Al-(hydr)oxides - II. Effects of chloride and sulfate

Common complexing ligands such as chloride and sulfate can significantly impact the sorption of Hg(II) to particle surfaces in aqueous environmental systems. To examine the effects of these ligands on Hg(II) sorption to mineral sorbents, macroscopic Hg(II) uptake measurements were conducted at pH 6 and [Hg]i=0.5 mM on goethite (??-FeOOH), ??-alumina (??-Al2O3), and bayerite (??-Al(OH)3) in the presence of chloride or sulfate, and the sorption products were characterized by extended X-ray absorption fine structure (EXAFS) spectroscopy. The presence of chloride resulted in reduced uptake of Hg(II) on all three substrates over the Cl- concentration ([Cl-]) range 10-5 to 10-2 M, lowering Hg surface coverages on goethite, ??-alumina, and bayerite from 0.42 to 0.07 ??mol/m2, 0.06 to 0.006 ??mol/m2, and 0.55 to 0.39 ??mol/m2 ([Cl -]=10-5 to 10-3 M only), respectively. This reduction in Hg(II) uptake is primarily a result of the formation of stable, nonsorbing aqueous HgCl2 complexes in solution, limiting the amount of free Hg(II) available to sorb. At higher [Cl-] beam reduction of Hg(II) to Hg(I) was observed, resulting in the possible formation of aqueous Hg2Cl2 species and the precipitation of calomel, Hg 2Cl2(s). The presence of sulfate caused enhanced Hg(II) uptake over the sulfate concentration ([SO42-]) range 10-5 to 0.9 M, increasing Hg surface coverages on goethite, ??-alumina, and bayerite from 0.39 to 0.45 ??mol/m2, 0.11 to 0.38 ??mol/m2, and 0.36 to 3.33 ??mol/m2, respectively. This effect is likely due to the direct sorption or accumulation of sulfate ions at the substrate interface, effectively reducing the positive surface charge that electrostatically inhibits Hg(II) sorption. Spectroscopic evidence for ternary surface complexation was observed in isolated cases, specifically in the Hg-goethite-sulfate system at high [SO42-] and in the Hg-goethite-chloride system. ?? 2003 Elsevier Inc. All rights reserved.

Journal of Colloid and Interface Science↗

USGS2012

Effects of sulfate ligand on uranyl carbonato surface species on ferrihydrite surfaces

Understanding uranium (U) sorption processes in permeable reactive barriers (PRB) are critical in modeling reactive transport for evaluating PRB performance at the Fry Canyon demonstration site in Utah, USA. To gain insight into the U sequestration mechanism in the amorphous ferric oxyhydroxide (AFO)-coated gravel PRB, U(VI) sorption processes on ferrihydrite surfaces were studied in 0.01 M Na 2 SO 4 solutions to simulate the major chemical composition of U-contaminatedgroundwater (i.e., [SO 4 2- ]~13 mM L -1 ) at the site. Uranyl sorption was greater at pH 7.5 than that at pH 4 in both air- and 2% pCO 2 -equilibrated systems. While there were negligible effects of sulfate ligands on the pH-dependent U(VI) sorption (<24 h) in both systems, X-ray absorption spectroscopy (XAS) analysis showed sulfate ligand associated U(VI) surface species at the ferrihydrite–water interface. In air-equilibrated systems, binary and mono-sulfate U(VI) ternary surface species co-existed at pH 5.43. At pH 6.55–7.83, a mixture of mono-sulfate and bis-carbonato U(VI) ternary surface species became more important. At 2% pCO 2 , there was no contribution of sulfate ligands on the U(VI) ternary surface species. Instead, a mixture of bis-carbonato inner-sphere (38%) and tris-carbonato outer-sphere U(VI) ternary surface species (62%) was found at pH 7.62. The study suggests that the competitive ligand (bicarbonate and sulfate) coordination on U(VI) surface species might be important in evaluating the U solid-state speciation in the AFO PRB at the study site where pCO 2 fluctuates between 1 and 2 pCO 2 %.

Journal of Colloid and Interface Science↗

USGS2021

Hydrocarbons to carboxyl-rich alicyclic molecules: A continuum model to describe biodegradation of petroleum-derived dissolved organic matter in contaminated groundwater plumes

Relationships between dissolved organic matter (DOM) reactivity and chemical composition in a groundwater plume containing petroleum-derived DOM (DOM HC ) were examined by quantitative and qualitative measurements to determine the source and chemical composition of the compounds that persist downgradient. Samples were collected from a transect down the core of the plume in the direction of groundwater flow. An exponential decrease in dissolved organic carbon concentration resulting from biodegradation along the transect correlated with a continuous shift in fluorescent DOM HC from shorter to longer wavelengths. Moreover, ultrahigh resolution mass spectrometry showed a shift from low molecular weight (MW) aliphatic, reduced compounds to high MW, unsaturated (alicyclic/aromatic), high oxygen compounds that are consistent with carboxyl-rich alicyclic molecules. The degree of condensed aromaticity increased downgradient, indicating that compounds with larger, conjugated aromatic core structures were less susceptible to biodegradation. Nuclear magnetic resonance spectroscopy showed a decrease in alkyl (particularly methyl) and an increase in aromatic/olefinic structural motifs. Collectively, data obtained from the combination of these complementary analytical techniques indicated that changes in the DOM HC composition of a groundwater plume are gradual, as relatively low molecular weight (MW), reduced, aliphatic compounds from the oil source were selectively degraded and high MW, alicyclic/aromatic, oxidized compounds persisted.

Minnesota↗

USGS2021

Uranium(VI) attenuation in a carbonate-bearing oxic alluvial aquifer

Uranium minerals are commonly found in soils and sediment across the United States at an average concentration of 2–4 mg/kg. Uranium occurs in the environment primarily in two forms, the oxidized, mostly soluble uranium(VI) form, or the reduced, sparingly soluble reduced uranium(IV) form. Here we describe subsurface geochemical conditions that result in low uranium concentrations in an alluvial aquifer with naturally occurring uranium in soils and sediments in the presence of complexing ligands under oxidizing conditions. Groundwater was saturated with respect to calcite and contained calcium (78–90 mg/L) with elevated levels of carbonate alkalinity (291–416 mg/L as HCO 3 − ). X-ray adsorption near edge structure (XANES) spectroscopy identified that sediment-associated uranium was oxidized as a uranium(VI) form (85%). Calcite was the predominant mineral by mass in the ultrafine fraction in uranium-bearing sediments (>16 mg/kg). Groundwater geochemical modeling indicated calcite and/or a calcium-uranyl-carbonate mineral such as liebigite in equilibrium with groundwater. The δ 13 C (0.57‰ ± 0.15‰) was indicative of abiotic carbonate deposition. Thus, solid-phase uranium(VI) associated with carbonate is likely maintaining uranium(VI) groundwater levels below the maximum contaminant level (MCL; 30 µg/L), presenting a deposition mechanism for uranium attenuation rather than solely a means of mobilization.

Nebraska↗

USGS2023

Photochemical mobilization of dissolved hydrocarbon oxidation products from petroleum contaminated soil into a shallow aquifer activate human nuclear receptors

Elevated non-volatile dissolved organic carbon (NVDOC) concentrations in groundwater monitoring wells under oil-contaminated hydrophobic soils originating from a pipeline rupture at the National Crude Oil Spill & Natural Attenuation Research Site near Bemidji, MN are documented.. We hypothesized the elevated NVDOC is comprised of water-soluble photooxidation products transported from the surface to the aquifer. We use field and laboratory samples in combination with complementary analytical methods to test this hypothesis and determine the biological response to these products. Observations from optical spectroscopy and ultrahigh-resolution mass spectrometry reveal a significant correlation between the chemical composition of NVDOC leached from photochemically weathered soils and groundwater monitoring wells with high NVDOC concentrations measured in the aquifer beneath the contaminated soil. Conversely, the chemical composition from the uncontaminated soil photoleachate, matches the NVDOC observed in the uncontaminated wells. Contaminated groundwater and photodissolution leachates from contaminated soil activated biological targets indicative of xenobiotic metabolism and exhibited potential for adverse effects. Newly formed hydrocarbon oxidation products (HOPs) from fresh oil could be distinguished from those downgradient. This study illustrates another pathway for dissolved HOPs to infiltrate groundwater and potentially affect human health and the environment.

Minnesota↗

USGS2025

Mercury speciation and stable isotopes in emperor penguins: First evidence for biochemical demethylation of methylmercury to mercury-dithiolate and mercury-tetraselenolate complexes

Apex marine predators, such as toothed whales and large petrels and albatrosses, ingest mercury (Hg) primarily in the form of methylmercury (MeHg) via prey consumption, which they detoxify as tiemannite (HgSe). One of the most intriguing current questions in Hg research is how more abundant lower trophic level predators detoxify MeHg, particularly in marine environments where tissue Hg burdens can be elevated. To address this need, we used high energy-resolution X-ray absorption near edge structure spectroscopy paired with nitrogen (N) and Hg stable isotopes to identify the chemical forms of Hg, Hg source, and species-specific δ 202 Hg isotopic values in emperor penguin, a mesopredator feeding primarily on Antarctic silverfish. The penguin liver contains variable proportions of MeHg and two inorganic Hg species (IHg), Hg-dithiolate (Hg(SR) 2 ) and Hg-tetraselenolate (Hg(Sec) 4 ) complexes, each characterized by a specific isotopic value (δ 202 MeHg = 0.3 ± 0.2‰, δ 202 Hg(SR) 2 = −1.6 ± 0.2‰, δ 202 Hg(Sec) 4 = −2.0 ± 0.1‰). Using δ 15 N as tracer of food source, we show that Hg(SR) 2 is not dietary but a biochemical demethylation product of MeHg metabolism. Penguin females transfer Hg to the egg as MeHg in the egg albumen, 89% MeHg and 11% IHg in the membrane, and 32% MeHg and 68% Hg(Sec) 4 in the yolk, on average (n = 15). Despite IHg species in eggs, MeHg is the main species quantitatively transferred by the mother to the chick because of the disproportionate mass of the MeHg-rich albumen compared to the yolk (n = 18). Further research is needed to elucidate the MeHg to Hg(SR) 2 demethylation pathway firmly documented here for the first time in multicellular organisms, and to understand why the thiolate ligands are not exchanged for Se ligands to form Hg(Sec) 4 , as the liver does not suffer from Se deficiency.

Adelie Land↗

USGS2026

Evolution of arsenic speciation during thermal treatment simulating wildfire heating in arsenic-rich sediments

Understanding arsenic transformations during wildfires can help better constrain the environmental impacts of increased wildfire intensity, frequency, and burned area. Previous studies have monitored the evolution of metal(loid) speciation at specific time/temperature endpoints, hampering the comprehension of the dynamic transformations of metal(loid)s during wildfires. Here, a novel approach, namely in situ time-resolved X-ray absorption near edge structure (TR-XANES) spectroscopy, was used for the first time to monitor the heat-induced redox transformations of arsenic (As) in two As-rich sediments with different characteristics. No arsenic transformations were observed in either sediment at room temperature or when the sediments were heated to a maximum temperature of 400 ºC. When heated to a maximum temperature of 600 or 700 ºC, As underwent complex, dynamic, and partially reversible redox transformations, the extent of which varied with sediment properties, initial As speciation, and heating temperature and duration. In the case of sediments initially containing As(V) and a low sulfide/sulfate ratio, the As(V) was reduced to As(III) over a short period of time, followed by immediate reoxidation of As(III) to As(V). The extent of the transient As reduction increased with increasing maximum temperature. The final As speciation at the end of the heating experiment was not substantially different from that at the beginning of the experiment. In contrast, in sediments that were best described by a more complex combination of reference compounds (As(V) coprecipitated with or adsorbed on iron oxide, arseniosiderite, arsenopyrite) with a high sulfide/sulfate ratio, As(V) phases were reduced to As(III) and As(III) was further reduced to As(-I) (at 700 ºC, only), followed by delayed reoxidation of As(-I) to As(III) (at 700 ºC, only) and reoxidation of As(III) to As(V). Approximately 9% and 26% of all As remained as As(III) ( i.e., was not reoxidized to As(V)) at the end of the experiment when heated to a maximum temperature of 600 and 700 ºC, respectively, which is higher than the relative abundance of As(III) in the native sediment. These fire-induced As transformations can potentially enhance As mobilization to surface water and groundwater, posing risks to environmental and human health.

California↗

USGS2014

Investigating organic matter in Fanno Creek, Oregon, Part 3 of 3: identifying and quantifying sources of organic matter to an urban stream

The sources, transport, and characteristics of organic matter (OM) in Fanno Creek, an urban stream in northwest Oregon, were assessed and quantified using: (1) optical instruments to calculate transported loads of dissolved, particulate, and total organic carbon, (2) fluorescence spectroscopy and stable isotope ratios (δ 13 C, δ 15 N) to elucidate sources and chemical properties of OM throughout the basin, and (3) synoptic sampling to investigate seasonal and hydrologic variations in the characteristics and quantity of OM. Results from this study indicate that of the roughly 324 (±2.9%) metric tons (tonnes, t) of organic carbon exported from the basin during March 2012 to March 2013, most of the OM in Fanno Creek was dissolved (72%) and was present year-round at concentrations exceeding 3–4 milligrams of carbon per liter, whereas particulate carbon typically was mobilized and transported only by higher-flow conditions. The isotopic and fluorescence characteristics of Fanno Creek OM indicate that the carbon originates primarily from terrestrial inputs, most likely riparian vegetative biomass that enters the stream via litterfall and overland transport and then travels through the system episodically as a result of hydrologic processes. The amount of OM exported from the Fanno Creek drainage over the course of a year in this study is consistent with previous estimates of annual riparian litterfall in or near the creek. Although the creek channel is actively eroding, most bank material has too little OM for that to be a dominant source of OM to the stream. Fluorescence data revealed that the OM contains primarily humic and fulvic-like components that become less aromatic as the OM moves downstream. The most significant seasonal variation was associated with OM transported in the first storms of the autumn season (fall flush). That material was characteristically different, with a larger fraction of microbially derived OM that probably resulted from an accumulation of easy-to-mobilize and decomposing material in the streambed during previous months of summertime low-flow conditions. The first fall flush produced the highest concentrations of OM of the entire year, and the resulting load of mobilized and decomposing OM resulted in a significant oxygen demand immediately downstream in the Tualatin River.

Oregon↗

USGS2013

Applying UV cameras for SO 2 detection to distant or optically thick volcanic plumes

Ultraviolet (UV) camera systems represent an exciting new technology for measuring two dimensional sulfur dioxide (SO 2 ) distributions in volcanic plumes. The high frame rate of the cameras allows the retrieval of SO 2 emission rates at time scales of 1 Hz or higher, thus allowing the investigation of high-frequency signals and making integrated and comparative studies with other high-data-rate volcano monitoring techniques possible. One drawback of the technique, however, is the limited spectral information recorded by the imaging systems. Here, a framework for simulating the sensitivity of UV cameras to various SO 2 distributions is introduced. Both the wavelength-dependent transmittance of the optical imaging system and the radiative transfer in the atmosphere are modeled. The framework is then applied to study the behavior of different optical setups and used to simulate the response of these instruments to volcanic plumes containing varying SO 2 and aerosol abundances located at various distances from the sensor. Results show that UV radiative transfer in and around distant and/or optically thick plumes typically leads to a lower sensitivity to SO 2 than expected when assuming a standard Beer–Lambert absorption model. Furthermore, camera response is often non-linear in SO 2 and dependent on distance to the plume and plume aerosol optical thickness and single scatter albedo. The model results are compared with camera measurements made at Kilauea Volcano (Hawaii) and a method for integrating moderate resolution differential optical absorption spectroscopy data with UV imagery to retrieve improved SO 2 column densities is discussed.

Journal of Volcanology and Geothermal Research↗

USGS2015

Quantitative imaging of volcanic plumes — Results, needs, and future trends

Recent technology allows two-dimensional “imaging” of trace gas distributions in plumes. In contrast to older, one-dimensional remote sensing techniques, that are only capable of measuring total column densities, the new imaging methods give insight into details of transport and mixing processes as well as chemical transformation within plumes. We give an overview of gas imaging techniques already being applied at volcanoes (SO 2 cameras, imaging DOAS, FT-IR imaging), present techniques where first field experiments were conducted (LED-LIDAR, tomographic mapping), and describe some techniques where only theoretical studies with application to volcanology exist (e.g. Fabry–Pérot Imaging, Gas Correlation Spectroscopy, bi-static LIDAR). Finally, we discuss current needs and future trends in imaging technology.

Journal of Volcanology and Geothermal Research↗

USGS2017

Olivine-melt relationships and syneruptive redox variations in the 1959 eruption of Kīlauea Volcano as revealed by XANES

The 1959 summit eruption of Kīlauea Volcano exhibited high lava fountains of gas-rich, primitive magma, containing olivine + chromian spinel in highly vesicular brown glass. Microprobe analysis of these samples shows that euhedral rims on olivine phenocrysts, in direct contact with glass, vary significantly in forsterite (Fo) content, at constant major-element melt composition, as do unzoned groundmass olivine crystals. Ferric/total iron (Fe + 3 /Fe T )ratios for matrix and interstitial glasses, plus olivine-hosted glass inclusions in eight 1959 scoria samples have been determined by micro X-ray absorption near-edge structure spectroscopy (μ-XANES). These data show that much of the variation in Fo content reflects variation in oxidation state of iron in the melt, which varies with sulfur concentration in the glass and (locally) with proximity to scoria edges in contact with air. Data for 24 olivine-melt pairs in the better-equilibrated samples from later in the eruption show K D averaging 0.280 ± 0.03 for the exchange of Fe and Mg between olivine and melt, somewhat displaced from the value of 0.30 ± 0.03 given by Roeder and Emslie (1970). This may reflect the low SiO 2 content of the 1959 magmas, which is lower than that in most Kīlauea tholeiites. More broadly, we show the potential of μ-XANES and electron microprobe to revisit and refine the value of K D in natural systems. The observed variations of Fe + 3 /Fe T ratios in the glasses reflect two distinct processes. The main process, sulfur degassing, produces steady decrease of the Fe + 3 /Fe T ratio. Melt inclusions in olivine are high in sulfur (1060–1500 ppm S), with Fe + 3 /Fe T = 0.160–0.175. Matrix glasses are degassed (mostly S < 200 ppm) with generally lower Fe + 3 /Fe T (0.114–0.135). Interstitial glasses within clumps of olivine crystals locally show intermediate levels of sulfur and Fe + 3 /Fe T ratio. The correlation suggests that (1) the 1959 magma was significantly reduced by sulfur degassing during the eruption and (2) the melts originally had Fe + 3 /Fe T ≥ 0.175, consistent with oxygen fugacity ( f O 2 ) at least 0.4 log units above the fayalite-magnetite-quartz (FMQ) buffer at 1 atm and magmatic temperature of 1200 °C. The second process is interaction between the melts and atmospheric oxygen, which results in higher Fe + 3 /Fe T ratios. Detailed μ-XANES traverses show gradients in Fe + 3 /Fe T of 0.145 to 0.628 over distances of 100–150 μm in thin, visibly reddened matrix glass bordering some scoriae, presumably caused by contact with air. This process was extremely rapid, giving insight into how fast the Fe + 3 /Fe T ratio can change in response to changes in external conditions.

Hawaii↗

USGS2025

The ghost plume phenomenon and its impact on zenith-facing remote sensing measurements of volcanic SO2 emission rates

A large source of error in SO 2 emission rates derived from mobile Differential Optical Absorption Spectroscopy (DOAS) of volcanic gas plumes is the uncertainty in atmospheric light paths between the sun and the instrument, particularly under non-ideal atmospheric conditions, such as the presence of low clouds. DOAS instruments measure the SO 2 column density along the effective light path, so changes to that pathway directly affect the measured SO 2 signal. Due to complex radiative transfer mechanisms when a cloud is between the DOAS viewing position and a volcanic plume, measured plumes can appear spatially offset from their true location, a phenomenon informally referred to as “ghost plumes.” In addition to the appearance of ghost plumes, DOAS measurements recorded in non-ideal conditions have poorly characterized errors and are often discarded, limiting the data available to characterize volcanic degassing. In this study we simulate the radiative transfer associated with zenith-facing mobile DOAS traverses using the McArtim radiative transfer model for scenarios when there is a cloud layer between the instrument and the volcanic plume. In total, 217 permutations of atmospheric optical conditions are considered with varying cloud opacities (AOD = 0, 1, 2, 4, 8, 20), plume opacities (AOD = 0, 1, 2, 4, 8), solar zenith angles (SZA = 1°, 30°, 60°), and cloud thicknesses (200, 400, 800 m). We first develop objective criteria for selecting SO 2 baseline absorption levels and plume spatial extents. The simulated plume traverses are then integrated to obtain the SO 2 cross-sectional burdens which, after multiplication with the wind speed, yield SO 2 emission rates. We find large modification in the shape of the modeled cross-sectional burdens even under translucent (low AOD) cloud conditions in our modeled scenarios. Despite modification of the plume shape, the presence of a low cloud layer is typically not a large source of error in the SO 2 cross-sectional burden or emission rate obtained from zenith-facing DOAS traverses. We find that all measured cross-sectional burdens simulated using an aerosol-free plume in the above conditions and SZA ≤ 30° are within ±25% of the true value.

Journal of Volcanology and Goethermal Research↗

USGS2025

The crystalline silica respiratory hazard from rhyolitic lava dome eruptions in New Zealand's Taupo Volcanic Zone: A case study from the 1315 CE Kaharoa eruption

The rhyolitic Kaharoa 1315 CE eruption was a complex, long-lived event from Tarawera volcano, New Zealand. Explosive phases were followed by around 5 years of lava dome extrusion and collapse which produced block-and-ash flows (BAF). Lava domes generate crystalline silica in the form of cristobalite, and rhyolitic magmas often contain quartz phenocrysts. Fine-grained ash containing crystalline silica can be formed through dome collapses or explosions, generating a respiratory health hazard for communities affected by ashfall. The aims of this study are to: i) determine whether the Kaharoa eruption dome-forming phase generated substantial quantities of crystalline silica and, therefore, to determine the potential for future dome-forming eruptions of Tarawera to do the same; ii) consider the potential hazard of the crystalline silica by studying the crystal habit and chemistry compared to other lava domes, globally; and iii) assess the particle size and crystalline silica content of the Kaharoa ash, to inform a respiratory hazard assessment. Five co-BAF ash samples and one co-ignimbrite (explosive) ash sample from the Kaharoa pyroclastic deposits were analysed for health-pertinent factors: particle size distribution and crystalline silica content. Eight dome-rock samples were collected from the dome complex and associated BAF deposits and groundmass texture (especially forms of crystalline silica) and quantity of crystalline silica were assessed. Cristobalite was present in the 4 ash samples analysed by X-ray diffraction (XRD; 1.3–3.7 wt%) as was quartz (5.7–12.5 wt%). For the 4 dome samples analysed by XRD, all samples contained quartz (4.1–10.4 wt%) and two contained significant quantities of cristobalite (24.7 and 27.3 wt%). Of the two dome samples with minimal cristobalite (visible as individual vapour-phase crystals by SEM but not quantifiable by XRD), one was from the non-devitrified dome carapace and the other was from the compacted interior but had not undergone devitrification. The two dome samples with substantial cristobalite were from dome interiors and were highly devitrified, with well-developed spherulitic textures. Using energy-dispersive X-ray spectroscopy, cristobalite in all samples contained minor aluminium, as has been seen for volcanic cristobalite from other lava domes, which may ameliorate its toxicity. By laser diffraction, the quantities of ash in the health pertinent size fractions varied, with a range of 1.3–8.1 vol% for particles of <4 μm diameter and 1.7–15.6 vol% for particles of <10 μm diameter, which is lower than measured in ash from large-scale dome collapse events at other volcanoes. The findings suggest a potential for substantial crystalline silica to be formed in future Kaharoa-style eruptions, but that cristobalite generation is site-specific, depending on location within the dome and whether the dome remains sufficiently hot for spherulite formation and glass devitrification. Respiratory hazard will therefore vary depending on the collapse of (or explosions through) individual lobes – although all lava is expected to contain quartz phenocrysts – as well as the size and energy of those collapses, which will influence particle size and quantity of ash generated and dispersed.

Taupo Volcanic Zone↗