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USGS2022

Sources and characteristics of dissolved organic carbon in the McKenzie River, Oregon, related to the formation of disinfection by-products in treated drinking water

Executive Summary This study characterized the concentration and quality of dissolved organic carbon (DOC) in the McKenzie River, a relatively undeveloped watershed in western Oregon, and its link to forming disinfection by-products (DBPs) in treated drinking water. The study aimed to identify the primary source(s) of DOC in source water for the Eugene Water & Electric Board’s (EWEB) conventional treatment plant on the McKenzie River near river mile 11, upstream of Hayden Bridge. The two classes of regulated compounds examined—trihalomethanes (THMs) and haloacetic acids (HAAs)—form when organic carbon in raw source water reacts with chlorine and (or) bromine during water treatment. The objectives of the study were to: characterize the amount and quality of DOC in the McKenzie River and select tributaries during storms; identify the most common types of carbon using UV-vis spectroscopy and other methods; evaluate optical properties for predicting DBP precursors in surface water; and identify land cover classes or vegetation types that may be important sources of organic carbon and DBP precursors in EWEB’s source water. Eleven storms were sampled synoptically in upstream-to-downstream fashion to provide a “snapshot” of water quality conditions at four sites on the McKenzie River from Frissell Bridge (6 miles downstream from Trail Bridge Reservoir) to the EWEB water treatment plant at Hayden Bridge and nine contributing tributaries. Storms included late summer and early autumn “first flush” events and late autumn, winter, and spring storms spanning a range in streamflows from 3,000 to 26,000 cubic feet per second as measured in the main stem McKenzie River at the EWEB water intake. Water samples were analyzed for DOC concentrations and optical properties (fluorescence and ultraviolet absorbance [UVA]) across a range of wavelengths to characterize the quantity and quality of dissolved organic matter (DOM) in the McKenzie River at the drinking water intake and upstream locations. Paired sets of source and finished water samples were collected at the EWEB treatment plant to identify DOC quality parameters in raw source water that might predict DBP concentrations in finished drinking water. DOC concentrations were relatively low in the McKenzie River (0.4–3 milligrams per liter [mg/L]; average 1.5 mg/L) but much higher in the tributaries. The highest DOC concentrations occurred during “first flush” storms in October 2012 and September 2013; the highest value (16 mg/L) was measured at the 52nd Street stormwater outfall. The average DOC concentration in the lower basin-tributaries was 3.8 mg/L; three middle basin tributaries—Quartz, Gate, and Haagen Creeks, which drain private forestland with less coniferous forest compared with other higher elevation tributaries— had slightly lower average DOC concentrations (2.8 mg/L). These middle-basin watersheds may be important sources of DOC and DBP precursors to the McKenzie River, even more so than the lower basin tributaries, depending on their flows (and loads). This is particularly true after the September 2020 Holiday Farm fire, which burned much of this area. DOC concentrations increased 68 percent in the McKenzie River between the uppermost reference site at Frissell Bridge and Vida; this includes drainage from Quartz Creek, Blue River Lake and Cougar Reservoir, which all contributed DOC to the main stem. In contrast, the lowermost tributaries draining most of the agricultural and urban land did not have a large effect on DOC in the McKenzie River despite their higher DOC concentrations because of their presumed relatively low streamflows and, consequently, DOC loads. Apart from the continuous flow monitors in the McKenzie River and some tributaries (Blue River and South Fork McKenzie River, and streamflow at Hayden Bridge and Vida, Camp Creek and some other locations), streamflow was not assessed during sample collection for this study. This lack of streamflow data precludes a detailed analysis of loads, which is discussed in the future studies section. All DBP concentrations in finished drinking water were less than EPA maximum contaminant levels (MCLs) of 0.080 mg/L for the four trihalomethanes (THM4) and 0.060 mg/L for five haloacetic acids (HAA5). During the 11 storm sampling events the maximum summed concentrations were about 0.040 mg/L for both THM4 and HAA5. Compliance monitoring samples, collected separately by EWEB, yielded some higher concentrations—0.046 mg/L THM4 and 0.047 HAA5—during the December 2012 storm. The corresponding benchmark quotient (BQ) values, which indicate how close a measured DBP concentration is to the MCL, were 0.58 and 0.78, respectively, for THM4 and HAA5. Compared with a similar 2007–08 McKenzie River study that did not target storm events, concentrations of THM4 and HAA5 in finished water were 68 percent and 33 percent higher, respectively, during the current study. Due to the high dilution rates in the McKenzie River main stem, many of the individual fluorescence excitation-emission measurements were low (<0.1 Raman units) and approached analytical detection limits. Parallel factor analysis (PARAFAC) resulted in a five-component model (C1–C5) that represents five unique organic fluorophores. Components C1, C2, and C3 represent DOM associated with soil-derived, humic-like, more degraded organic matter. In contrast, components C4 and C5 represent “fresher” DOM, derived from terrestrial and aquatic plants, including algae and cyanobacteria that are common in the McKenzie River and its tributaries and reservoirs. The fluorescence data and PARAFAC modeling suggest that most of the DOC in the McKenzie River originated from terrestrial sources (primarily components C1 and C2). The largest increases in DOC in the main stem occurred in the reach upstream of Vida, from inflows by Quartz Creek, Blue River, South Fork McKenzie River, and other tributaries. Concentrations of DBPs in EWEB’s finished drinking water were positively correlated with DOC concentrations in raw source water (THM4, p <0.05; HAA5, p <0.01) for paired samples collected 12−24 hours apart. DOC concentrations were significantly positively correlated ( p <0.001) with laboratory-based fluorescent dissolved organic matter (fDOM) measurements, suggesting fDOM as a useful parameter for monitoring and predicting DOC concentration in surface water and DBP concentrations in finished water. Of all the PARAFAC components in surface water, C5 had the highest correlations with DBPs in finished water (rho = 0.77–0.84, p <0.01), followed by components C1 and C2 (rho = 0.75 and 0.71, respectively, p <0.01). This C5 carbon is associated with recently produced DOM, possibly from decomposed terrestrial and aquatic vegetation. Model loadings of these three components were considerably higher in the sampled tributaries relative to the main stem McKenzie River, with most of the observed increases in the main stem apparent at Vida. This points to Quartz Creek or other tributaries in the reach between Frissell Bridge and the sampling site near Vida (South Fork McKenzie and Blue Rivers) as potentially key contributors of DOM source material that leads to the production of DBPs in treated drinking water. A limited load analysis showed that the reservoirs contributed 8–37 percent of the instantaneous DOC loads observed at Vida at the time of sampling, which suggests other sources such as Quartz Creek and other streams in the reach between Frissell Bridge and Vida are more important. Random forest analyses identified PARAFAC components C1 and C5 and fluorescence peaks A, C, M, T and N as the best predictors for HAA5 concentrations in finished drinking water, explaining 62.5 percent of the variation. The best predictors for THM4 were C1, C4 + C5, and peaks T, A, and N, which explained 33 percent of the variation. Several land cover and vegetation classes were correlated with DOC concentration and other optical measurements. The percentage of evergreen forest in each of the subwatersheds sampled was negatively correlated ( p <0.001) with DOC concentration and many optical indicators of DOM quantity: UVA 254 , fDOM, and all of the fluorescence peaks. In contrast, mixed (deciduous) forest was positively correlated ( p <0.001) with DOC, fDOM, UVA 254 , and several fluorescence peaks, demonstrating the importance of deciduous leaf fall in generating DOC and DBP precursors. The high level of human activities in the middle and lower portion of the basin—including timber harvesting and road construction on private forestland, agricultural, rural, industrial, and urban development—have resulted in the greatest loss in native coniferous and mixed deciduous forests in the basin. DOC loading from these tributaries and reservoir releases, which contain DOC from terrestrial and aquatic productivity, both enrich the McKenzie River. Concentrations of DOC increased an average of 71 percent (range 30–120 percent) in the McKenzie River between Frissell Bridge, the upstream reference site, and Vida. PARAFAC components C1, C2, and C5—which were correlated with DBPs in finished water—increased, on average, 109–136 percent (range 20–250 percent) in this same Frissell-to-Vida reach. These increases occur from input of tributaries in the middle basin such as Quartz Creek and others, as noted above. Future monitoring, field, and lab studies can improve our understanding of seasonal and spatial sources of organic carbon contributing DBP precursors to the McKenzie River and allow detection of long-term trends resulting from the recent Holiday Farm Fire, which burned 173,393 acres of forestland, including riparian areas along the main stem, and numerous structures, homes, and outbuildings in September 2020. Future studies could examine DOC fluxes and flushing of carbon from the watershed, investigate the role of precipitation amount and intensity in mobilizing carbon and sediment, and evaluate impacts to aquatic communities and human health as part of a post-fire assessment. Other areas ripe for study include evaluating the impacts of potential temperature increases on carbon sequestration and decomposition in the burned and unburned forests and identifying practices that foster sequestration of carbon in forest soils. The use of fluorescence sensors such as fDOM to monitor the concentration and composition of raw water supplies may be improved for detection of specific DBP precursors, to provide continuous and real-time information to treatment plant operators. Future studies that monitor DOM amount and quality, and DBP Formation Potential (FP), particularly during storm events, paired with streamflow measurements, as suggested above, could help identify areas that contribute high DOC loads and thus help managers identify the key areas to focus restoration activities. Other studies could examine treatment options for currently regulated DBPs and potentially unregulated compounds, including advanced biological treatments for their removal. This study was a collaboration between the U.S. Geological Survey (USGS) and EWEB in Eugene, Oregon, with additional funding provided from USGS Cooperative Matching Funds Program.

Oregon↗

USGS1983

Preliminary plasma spectrometric analyses for selected elements in some geothermal waters from Cerro Prieto, Mexico

As part of a cooperative study with Dr. Alfred Truesdell, water samples collected from geothermal power production wells at Cerro Prieto, Mexico, were analyzed for selected elements by d.c. argon plasma emission spectroscopy. Spectral interferences due to the presence of high concentrations of Ca, Si, Na and K in these water affected the apparent concentration values obtained. These effects were evaluated and correction techniques were developed and applied to the analytical values. Precipitates present in the samples at the time of analysis adversely affected the accuracy, precision and interpretability of the data. (USGS)

Water-Resources Investigations Report↗

USGS1994

Characterization of the hydrogeology and water quality at the Management Systems Evaluation Area near Princeton, Minnesota, 1991-92

The Management Systems Evaluation Area (MSEA) program is part of a multi-scale, inter-agency initiative to evaluate the effects of agricultural management systems on water quality in the midwest corn belt. The Minnesota MSEA project is one of five projects selected to represent the principal hydrogeologic settings and geographic diversity of prevailing management systems in the midwest corn belt. The Minnesota MSEA research area is located in the Anoka Sand Plain about 5 kilometers southwest of Princeton, Minnesota. The water-quality monitoring network within the 65-hectare research area consists of 29 observation wells and 22 multiport wells. Thirteen observation wells also are located outside the research area. Glacial deposits beneath the research area generally consist of fine to medium sand in the unsaturated zone and coarse to very coarse sand and gravel in the saturated zone. The average depth to the water table is about 3.6 meters below land surface. Ground-water recharge during 1992 was lower (4.9-13.2 centimeters) than during 1991 (11.7-25.7 centimeters) because of reduced precipitation (58.5 centimeters during 1992 and 94.5 centimeters during 1991). Estimates of saturated horizontal hydraulic conductivity for the surficial aquifer were made using five methods. Results were within about two orders of magnitude and also agree favorably with estimates from a previous study of the Anoka Sand Plain. The smallest hydraulic conductivities were obtained using laboratory analyses (0.0052 centimeters per second) and the largest estimate was obtained from results of an aquifer test (0.2820 centimeters per second). The estimate of hydraulic conductivity based on the time of travel of chloride (0.0655 centimeters per second) is considered most accurate and representative of the surficial aquifer in the research area. Anthropogenic effects of previous land use were detected in water samples collected during April 1991, prior to implementation of the MSEA farming systems. Concentrations of nitrate-nitrogen (nitrate-N) in the surficial aquifer equaled or exceeded the U.S. Environmental Protection Agency's recommended maximum contaminant level of 10 milligrams per liter (mg/L) in 4 of the 7 wells in the research area. The maximum concentration of nitrate-N in ground water from these wells was 23 mg/L with a median of 10 mg/L. The median concentration of nitrate-N for these wells exceeded the median in wells located upgradient from the research area (2.1 mg/L). Similarly, the median concentration of chloride from wells in the research area (11 mg/L) exceeded the median in upgradient wells (3.8 mg/L). On-site sources of the elevated nitrate-N include decomposition of alfalfa, grown on-site during 1981-89, and application of nitrogen fertilizer to corn during 1990. A likely on-site source of the elevated chloride is application of potassium-chloride fertilizer to crops prior to 1991. Atrazine was detected by gas chromatography mass spectroscopy in 2 of the 7 wells in the research area at concentrations of 0.04 and 0.17 micrograms per liter (ug/L), well below the U.S. Environmental Protection Agency's recommended maximum contaminant level of 3 ug/L. The median concentration in these Wells was less than the qualitative detection limit of 0.01 ug/L. Atrazine metabolite de-ethylatrazine was the most frequently detected herbicide or herbicide metabolite. De-ethylatrazine was detected in 5 of the 7 wells in the research area at concentrations ranging from 0.12 to 0.32 ug/L with a median concentration of 0.14 ug/L. Atrazine metabolite de-isopropylatrazine was not detected above the qualitative detection limit of 0.06 ug/L. The most likely sources of atrazine are applications to the research area during 1990 or from precipitation.

Minnesota↗

USGS2009

A proposed origin for fossilized Pennsylvanian plant cuticles by pyrite oxidation (Sydney Coalfield, Nova Scotia, Canada)

Fossilized cuticles, though rare in the roof rocks of coal seam in the younger part of the Pennsylvanian Sydney Coalfield, Nova Scotia, represent nearly all of the major plant groups. Selected for investigation, by methods of Fourier transform infrared spectroscopy (FTIR) and elemental analysis, are fossilized cuticles (FCs) and cuticles extracted from compressions by Schulze's process (CCs) of Alethopteris ambigua. These investigations are supplemented by FTIR analysis of FCs and CCs of Cordaites principalis, and a cuticle-fossilized medullosalean(?) axis. The purpose of this study is threefold: (1) to try to determine biochemical discriminators between FCs and CCs of the same species using semi-quantitative FTIR techniques; (2) to assess the effects chemical treatments have, particularly Schulze's process, on functional groups; and most importantly (3) to study the primary origin of FCs. Results are equivocal in respect to (1); (2) after Schulze's treatment aliphatic moieties tend to be reduced relative to oxygenated groups, and some aliphatic chains may be shortened; and (3) a primary chemical model is proposed. The model is based on a variety of geological observations, including stratal distribution, clay and pyrite mineralogies associated with FCs and compressions, and regional geological structure. The model presupposes compression-cuticle fossilization under anoxic conditions for late authigenic deposition of sub-micron-sized pyrite on the compressions. Rock joints subsequently provided conduits for oxygen-enriched ground-water circulation to initiate in situ pyritic oxidation that produced sulfuric acid for macerating compressions, with resultant loss of vitrinite, but with preservation of cuticles as FCs. The timing of the process remains undetermined, though it is assumed to be late to post-diagenetic. Although FCs represent a pathway of organic matter transformation (pomd) distinct from other plant-fossilization processes, global applicability of the chemical models remains to be tested. CCs and FCs are inferred endpoints on a spectrum of pomd which complicates assessing origin of in-between transformations (partially macerated cuticles). FCs index highly acidic levels that existed locally in the roof rocks.

Bulletin of Geosciences↗

USGS2020

Mineralogy and lithology of the Upper Cretaceous Niobrara Formation determined by hyperspectral core imaging

Sections of the Upper Cretaceous (Coniacian to Campanian) Niobrara Formation in two cores from Kansas and Colorado, the Amoco Rebecca Bounds and USGS Portland 1, respectively, were examined by hyperspectral core imaging and analysis. A spectral imaging system combining high-resolution photography (50 μm), 3D laser profiling (20 μm), and near-visible + short-wave infrared reflectance spectroscopy (wavelengths from 450 to 2500 nm, 500 μm pixel size) was applied to these cores to provide spectral and textural data facilitating creation of continuous mineral and lithology class maps. In addition, compositing of pixel-based results to group pixels to create mineralogical and lithological logs (0.5 ft resolution) was performed to facilitate comparisons to other geochemical datasets. The results show general correspondence in trends identified by previous geochemistry studies, with some exceptions due to instrumental limitations related to low reflectance of some rock intervals and the limited range of infrared wavelengths examined. This study provides a cursory overview of an extensive dataset meant to demonstrate the utility of hyperspectral core scanning to studies of mudrocks in petroleum systems as well as the kinds of information this technique can provide for detailed examination of stratigraphic features in sedimentary systems more generally.

Mountain Geologist↗

USGS2022

Geochemical studies of the Green River Formation in the Piceance Basin, Colorado: I. Major, minor, and trace elements

The Eocene Green River Formation contains the largest oil shale deposits in the world and is a welldocumented example of a lacustrine depositional system. In addition, mineral resources associated with oil shale in the Piceance Basin nahcolite [NaHCO3] and dawsonite [NaAl(CO3)(OH)2)] are of current and potential economic value, respectively. Detailed geochemical analysis across the basin can aid in the understanding of the depositional environment, sedimentary processes, and water-chemistry evolution in this system. Quantitative geochemical data for Green River oil shale from the Piceance Basin of Colorado were collected by inductively coupled plasma optical emission spectroscopy and mass spectrometry as part of this study. The basin margin is represented by samples from exposures at Douglas Pass (Garfield County) and the basin center area is characterized by core samples from two drilled wells: the Shell 23X-2 and John Savage 24-1 (Rio Blanco County). Major elements and groups of elements are used as proxies for clastic influx (Si, Al, K, Ti), carbonate deposition (Ca, Mg), salinity (Na), paleo-productivity (P), and redox state (Fe, S), respectively. Minor and trace elements reinforce observations based on major elements, including Rb, Zr, Nb for clastic influx and Mn, Sr for carbonate. Trace elements are used to characterize redox conditions (As, Mo, U, V, Co, Ni, Cu, Zn) and salinity (Rb/K, B/Ga). Chemical distinctions between the basin margin and the basin center, in terms of these components and total organic carbon concentrations, support the model of a permanently stratified lake through most of the depositional interval. A primary purpose of the study was to conduct more extensive sampling to confirm conclusions of a previous reconnaissance study. Geochemical data from this study indicates elevated Na around the basin margin occurring earlier than in the deeper basin. Early in the history of Lake Uinta, the salinity may have been elevated first in the shallower marginal waters, due to increased evaporation, which then led to elevated salinity in the basin center through transport of saline density currents. Other indicators of salinity (Rb/K, B/Ga) do not track Na content in intervals where clay minerals are absent due to diagenetic alteration under hypersaline conditions but may be used to indicate the salinities at which authigenic Na-bearing minerals begin to form. Most Na-rich samples show high proportions of clastic constituents (Si, Al, K, Ti) compared to conventional carbonate constituents (Ca, Mg). Redox-sensitive period IV transition metal elements (V, Co, Ni, Cu, Zn) show only local occurrence of significant enrichment relative to average shale abundances. Analysis of Fe/Al ratios for this dataset suggests that the depletion of these elements may be related to source rocks depleted in mafic constituents, with apparent redox-related enrichments subdued by this effect. The basin margin samples reflect generally oxic bottom waters, with some intervals deposited under more reducing, possibly dysoxic to anoxic conditions. The basin center results indicate more reducing conditions, with Mo and U enrichment factors suggesting operation of a particulate shuttle mechanism that scavenged Mo on Fe/Mn-oxyhydroxides that redissolved at depth, with Mo precipitating along with sulfides and/or organic matter at or near the sediment/water interface.

Colorado↗

USGS2022

Geochemical studies of the Green River Formation in the Piceance Basin, Colorado: II. Chemofacies from hierarchical cluster analysis

Hierarchical cluster analysis (HCA) was applied to a geochemical dataset representing the Eocene Green River Formation in the Piceance Basin of Colorado to identify chemofacies in core and outcrop samples from the basin margin and the basin center. The input dataset consisted of inductively coupled plasma optical emission spectroscopy and mass spectrometry and total organic carbon (TOC) content analyses of 186 basin margin outcrop samples and 190 basin center core samples discussed in Part 1 of this study (this volume). TOC values and twenty-five major and trace elements were used as variables to define statistical clusters of samples for the overall dataset, for the two basin center cores, and for each separate core or outcrop dataset by HCA applying Euclidean distance and Ward’s method algorithms. For each dataset, five cluster-defined chemofacies were identified. The chemofacies for each dataset show chemical affinities with five informally defined rock types– mudstone, marlstone, carbonate-rich mudstone, siliciclastic-rich mudstone/siltstone/sandstone, and Na-rich (saline) mudstone, with each showing variations in TOC content and abundance of redox sensitive minor and trace elements. A close relationship between enrichment of redox sensitive elements, particularly As and Mo, and TOC is identified in the basin center. Whereas enrichment factors (relative to average shale) are relatively low for many Period IV (PIV) transition metals, as discussed in Part 1 of this study, their consistent coherence in enrichment or depletion in HCA-defined chemofacies demonstrates the expected relationship between redox state and organic richness. Enrichment in PIV transition metals also shows a correlation to enrichment in elements with affinity for siliciclastic sediment. Enrichment/depletion among several groups of redox indicators is not everywhere consistent, with some chemofacies showing, for example, enrichment of PIV transition metals and depletion of sulfur and arsenic. Early timing of saline conditions in the basin margin is clearly displayed in the chemofacies log display, consistent with observations based on geochemical interpretations of concentrations and elemental ratios discussed in Part 1. Overall, the chemofacies are consistent with major mineralogical units and lake history stages defined in previous work, but provide more detail on the fluctuations in lake chemistry that occurred during deposition of Green River oil shale in the Piceance Basin.

Colorado↗

USGS2023

Weak degassing from remote Alaska volcanoes characterized with a new airborne Imaging DOAS instrument and a suite of in situ sensors

Gas emissions from volcanoes occur when volatile species exsolve from magmatic and hydrothermal systems and make their way to the surface. Measurements of emitted gases therefore provide insights into volcanic processes. On 16 July 2021, we made airborne measurements of weak gas plumes emitted from four remote Alaska volcanoes: Iliamna Volcano, Mount Douglas, Mount Martin, and Mount Mageik. Integrated into a small fixed-wing aircraft, a new Imaging Differential Optical Absorption Spectroscopy (DOAS) instrument was used to map the spatial extent of SO 2 plumes as they drifted downwind. Contrary to conventional Mobile DOAS instruments, which provide only a single viewing direction, the Imaging DOAS simultaneously measures SO 2 column density along 48 individual viewing directions oriented in a swath above or below the aircraft. Each of the individual measurements have a comparable precision and sensitivity to those obtained by conventional instruments. Together, they provide high resolution 2D imagery of the volcanic plumes and allow calculation of limited emission rate time series information. Although zenith-facing DOAS measurements achieve greater accuracy and are performed here, the application of the Imaging DOAS in a nadir-facing setup is also discussed and compared to satellite observations made in similar geometries. Also onboard the aircraft, a suite of electrochemical and optical sensors measured the relative abundances of the six major volcanic volatile species H 2 O, CO 2 , SO 2 , H 2 S, HCl, and HF as the aircraft passed through the plumes. Mean SO 2 emission rates of 90 ± 10, 20 ± 3, and 13 ± 3 t/d were measured at Iliamna Volcano, Mount Douglas, and Mount Martin, respectively. SO 2 emissions were below the DOAS detection limit at Mount Mageik but CO 2 and H 2 S could be measured with the in situ sensors. The information gleaned from these measurements was used to assess and compare activity at these volcanoes, all of which were found to be in a state of background degassing but whose emissions pointed to different source conditions ranging from mixed magmatic-hydrothermal to purely hydrothermal in character. Additional measurements at Mount Spurr, Redoubt Volcano, and Augustine Volcano failed to detect the very weak gas concentrations downwind of these persistently degassing vents.

Alaska↗

USGS2023

A novel non-destructive workflow for examining germanium and co-substituents in ZnS

A suite of complementary techniques was used to examine germanium (Ge), a byproduct critical element, and co-substituent trace elements in ZnS and mine wastes from four mineral districts where germanium is, or has been, produced within the United States. This contribution establishes a comprehensive workflow for characterizing Ge and other trace elements, which captures the full heterogeneity of samples through extensive pre-characterization. This process proceeded from optical microscopy, to scanning electron microscopy and cathodoluminescence (CL) imaging, to electron microprobe analysis, prior to synchrotron-based investigations. Utilizing non-destructive techniques enabled reanalysis, which proved essential for verifying observations and validating unexpected results. In cases where the Fe content was <0.3 wt% in ZnS, cathodoluminescence imaging proved to be an efficient means to qualitatively identify trace element zonation that could then be further explored by other micro-focused techniques. Micro-focused X-ray diffraction was used to map the distribution of the non-cubic ZnS polymorph, whereas micro-focused X-ray fluorescence (μ-XRF) phase mapping distinguished between Ge 4+ hosted in primary ZnS and a weathering product, hemimorphite [Zn 4 Si 2 O 7 (OH) 2 ·H 2 O]. Microprobe data and μ-XRF maps identified spatial relationships among trace elements in ZnS and implied substitutional mechanisms, which were further explored using Ge and copper (Cu) X-ray absorption near-edge spectroscopy (XANES). Both oxidation states of Ge (4+ and 2+) were identified in ZnS along with, almost exclusively, monovalent Cu. However, the relative abundance of Ge oxidation states varied among mineral districts and, sometimes, within samples. Further, bulk XANES measurements typically agreed with micro-focused XANES (μ-XANES) spectra, but unique micro-environments were detected, highlighting the importance of complementary bulk and micro-focused measurements. Some Ge μ-XANES utilized a high energy resolution fluorescence detector, which improved spectral resolution and spectral signal-to-noise ratio. This detector opens new opportunities for exploring byproduct critical elements in complex matrices. Overall, the non-destructive workflow employed here can be extended to other byproduct critical elements to more fully understand fundamental ore enrichment processes, which have practical implications for critical element exploration, resource quantification, and extraction.

Frontiers in Earth Science↗

USGS2019

Soil aggregates as a source of dissolved organic carbon to streams: An experimental study on the effect of solution chemistry on water extractable carbon

Over the past two decades, headwater streams of the northern hemisphere have shown increased amounts of dissolved organic carbon (DOC), coinciding with decreased acid deposition. The exact nature of the mechanistic link between precipitation composition and stream water DOC is still widely debated in the literature. We hypothesize that soil aggregates are the main source of stream water DOC and that DOC release is greater in organic rich, riparian soils vs. hillslope soils. To test these hypotheses, we collected soils from two main landscape positions (hillslope and riparian zones) from the acid-impacted Sleepers River Research Watershed in northeastern Vermont. We performed aqueous soil extracts with solutions of different ionic strength (IS) and composition to simulate changes in soil solution. We monitored dynamic changes in soil particle size, aggregate architecture and composition, leachate DOC concentrations, dissolved organic matter (DOM) characteristics by fluorescence spectroscopy and trends in bioavailability. In low IS solutions, extractable DOC concentrations were significantly higher, particle size (by laser diffraction) was significantly smaller and organic material was separated from mineral particles in scanning electron microscope observations. Furthermore, higher DOC concentrations were found in Na + compared to Ca 2+ solutions of the same IS. These effects are attributed to aggregate dispersion due to expanding diffuse double layers in decreased IS solutions and to decreased bridging by divalent cations. Landscape position impacted quality but not quantity of released DOC. Overall, these results indicate that soil aggregates might be one important link between Critical Zone inputs (i.e., precipitation) and exports in streams.

Vermont↗

USGS2021

Using fission-track radiography coupled with scanning electron microscopy for efficient identification of solid-phase uranium mineralogy at a former uranium pilot mill (Grand Junction, Colorado)

At a former uranium pilot mill in Grand Junction, Colorado, mine tailings and some subpile sediments were excavated to various depths to meet surface radiological standards, but residual solid-phase uranium below these excavation depths still occurs at concentrations above background. The combination of fission-track radiography and scanning electron microscope energy-dispersive X-ray spectroscopy (SEM-EDS) provides a uniquely efficient and quantitative way of determining mineralogic associations of uranium that can influence uranium mobility. After the creation of sample thin sections, a mica sheet is placed on those thin sections and irradiated in a nuclear research reactor. Decay of the irradiated uranium creates fission tracks that can be viewed with a microscope. The fission-track radiography images indicate thin section sample areas with elevated uranium that are focus areas for SEM-EDS work. EDS spectra provide quantitative elemental data that indicate the mineralogy of individual grains or grain coatings associated with the fission-track identification of elevated uranium. For the site in this study, the results indicated that uranium occurred (1) with coatings of aluminum–silicon (Al/Si) gel and gypsum, (2) dispersed in the unsaturated zone associated with evaporite-type salts, and (3) sorbed onto organic carbon. The Al/Si gel likely formed when low-pH waters were precipitated during calcite buffering, which in turn retained or precipitated trace amounts of Fe, As, U, V, Ca, and S. Understanding these mechanisms can help guide future laboratory and field-scale efforts in determining long-term uranium release rates to groundwater.

Colorado↗

USGS2019

Comparison of methods for modeling fractional cover using simulated satellite hyperspectral imager spectra

Remotely sensed data can be used to model the fractional cover of green vegetation (GV), non-photosynthetic vegetation (NPV), and soil in natural and agricultural ecosystems. NPV and soil cover are difficult to estimate accurately since absorption by lignin, cellulose, and other organic molecules cannot be resolved by broadband multispectral data. A new generation of satellite hyperspectral imagers will provide contiguous narrowband coverage, enabling new, more accurate, and potentially global fractional cover products. We used six field spectroscopy datasets collected in prior experiments from sites with partial crop, grass, shrub, and low-stature resprouting tree cover to simulate satellite hyperspectral data, including sensor noise and atmospheric correction artifacts. The combined dataset was used to compare hyperspectral index-based and spectroscopic methods for estimating GV, NPV, and soil fractional cover. GV fractional cover was estimated most accurately. NPV and soil fractions were more difficult to estimate, with spectroscopic methods like partial least squares (PLS) regression, spectral feature analysis (SFA), and multiple endmember spectral mixture analysis (MESMA) typically outperforming hyperspectral indices. Using an independent validation dataset, the lowest root mean squared error (RMSE) values were 0.115 for GV using either normalized difference vegetation index (NDVI) or SFA, 0.164 for NPV using PLS, and 0.126 for soil using PLS. PLS also had the lowest RMSE averaged across all three cover types. This work highlights the need for more extensive and diverse fine spatial scale measurements of fractional cover, to improve methodologies for estimating cover in preparation for future hyperspectral global monitoring missions.

Remote Sensing↗

USGS2021

Presence of microplastics in the food web of the largest high-elevation lake in North America

Microplastics have been documented in aquatic and terrestrial ecosystems throughout the world. However, few studies have investigated microplastics in freshwater fish diets. In this study, water samples and three trophic levels of a freshwater food web were investigated for microplastic presence: amphipods ( Gammarus lacustris ), Yellowstone cutthroat trout ( Oncorhynchus clarkii bouvieri ), and lake trout ( Salvelinus namaycush ). Microplastics and other anthropogenic materials were documented in water samples, amphipods, and fish, then confirmed using FTIR (Fourier-transform infrared) and Raman spectroscopy. Our findings confirmed the presence of microplastics and other anthropogenic materials in three trophic levels of a freshwater food web in a high-elevation lake in a national park, which corroborates recent studies implicating the global distribution of microplastics. This study further illustrates the need for global action regarding the appropriate manufacturing, use, and disposal of plastics to minimize the effects of plastics on the environment.

Wyoming↗

USGS2026

Geochemical geodatabase of sedimentary strata (coal, coal-adjacent rocks, tuffaceous oil shale, phosphate-rich rocks) and produced water in the Uinta region, Utah and Colorado

The Geochemical Geodatabase of Sedimentary Strata (Coal, Coal-adjacent Rocks, Tuffaceous Oil Shale, Phosphate-rich Rocks) and Produced Water in the Uinta Region, Utah and Colorado, consists of compiled datasets acquired as part of the Carbon Ore, Rare Earth, and Critical Mineral (CORE-CM) Uinta Region assessment funded by the U.S. Department of Energy (DEFE0032046, 2021–2024; Birgenheier et al., 2024). The CORE-CM assessment focused on providing comprehensive geological and geochemical characterization of current and prospective sedimentary-hosted resources including coal, oil shale, phosphatic limestone, and produced water from oil and gas targets present in eastern Utah and northwestern Colorado (Figure 1). This Data Series includes a geodatabase that consists of analytical geochemical data collected September 2021 through December 2024 via portable X-ray fluorescence (pXRF), and laboratory measured analyses produced by inductively coupled plasma mass spectrometry (ICP-MS) and inductively coupled plasma optical emission spectroscopy (ICP-OES). The coal-related geochemical data are derived primarily from the Cretaceous Blackhawk Formation and Ferron Sandstone of Utah, and the Mesaverde Group of Colorado. Additional non-coal resources assessed include oil shale-bearing strata of the Eocene upper Green River Formation (Utah and Colorado), phosphate-rich limestone of the Permian Park City Formation (Utah) and produced water from oil and gas-bearing strata of the Eocene Green River and Wasatch Formations (Uinta Basin) and the Pennsylvanian Paradox Formation (Paradox Basin) (Table 1). The CORE-CM assessment included a wide range of lithologies present in the coal, oil shale, and phosphate geologic resource systems whether or not the specific lithology has current economic value. Geochemical analyses of produced water from oil and gas wells focused on current and emerging hydrocarbon targets in the central Uinta Basin and northern Paradox Basin. A total of 13,092 geochemical analyses from these geologic systems is provided in the included geodatabase. A series of coal quality data (e.g., composition and maceral analyses) is also included in the database and was digitized from archived coal samples from the Utah Geological Survey (Appendix A).

Colorado, Utah↗

USGS2009

The weathering of a sulfide orebody: Speciation and fate of some potential contaminants

Various potentially toxic trace elements such as As, Cu, Pb and Zn have been remobilized by the weathering of a sulfide orebody that was only partially mined at Leona Heights, California. As a result, this body has both natural and anthropogeni- cally modified weathering profiles only 500 m apart. The orebody is located in a heavily urbanized area in suburban Oakland, and directly affects water quality in at least one stream by producing acidic conditions and relatively high concentrations of dissolved elements (e.g., ??500 ??g/L Cu, ??3700 ??g/L Zn). Micrometric-scale mineralogical investigations were performed on the authigenic metal-bearing phases (less than 10 ??m in size) using electron-probe micro-analysis (EPMA), micro-Raman, micro X-ray absorption spectroscopy (??XAS), scanning X-ray diffraction ((??SXRD) and scanning X-ray fluorescence (??-SXRF) mapping techniques. Those measurements were coupled with classical mineralogical laboratory techniques, X-ray diffraction (XRD) and scanning electron microscopy (SEM). Authigenic metal-bearing phases identified are mainly sulfates (jarosite, epsomite, schwertmannite), Fe (oxy-)hydroxides (goethite, hematite and poorly crystalline Fe products) and poorly crystalline Mn (hydr-)oxides. Sulfates and Fe (oxy-)hydroxides are the two main secondary products at both sites, whereas Mn (hydr-) oxides were only observed in the samples from the non-mining site. In these samples, the various trace elements show different affinities for Fe or Mn compounds. Lead is preferentially associated with Mn (hydr-)oxides and As with Fe (oxy-)hydroxides or sulfates. Copper association with Mn and Fe phases is questionable, and the results obtained rather indicate that Cu is present as individual Cu-rich grains (Cu hydroxides). Some ochreous precipitates were found at both sites and correspond to a mixture of schwertmannite, goethite and jarosite containing some potentially toxic trace elements such as Cu, Pb and Zn. According to the trace element distribution and relative abundance of the unweathered sulfides, this orebody still represents a significant reservoir of potential contaminants for the watershed, especially at the non-mining site, as a much greater proportion of sulfides is left to react and because of the lower porosity at this site.

Canadian Mineralogist↗

USGS2026

Remote compositional analyses of space-weathered lunar maria

Visible-to-shortwave infrared (VSWIR) reflectance spectroscopy has revolutionized our understanding of planetary surface compositions. However, space-weathering processes on airless bodies complicate quantitative compositional analyses. Here, we present a framework to isolate the signatures of space weathering in VSWIR spectra of lunar maria by leveraging radiative transfer modeling under the assumptions that (i) a space-weathered target can be expressed as a mixture of fresh and fully space-weathered components and (ii) remaining signatures can be modeled by including agglutinates as an end-member component. We first validate this approach against laboratory spectra of space-weathered Apollo mare soils of known mineral compositions using a probabilistic Markov Chain Monte Carlo implementation of the Hapke radiative transfer model. Second, we illustrate how this approach can be applied to orbital Moon Mineralogy Mapper data. The proposed space-weathering correction workflow for lunar maria could be expanded to other lunar lithologies and applied to existing and future data sets.

Planetary Science Journal↗

USGS2026

Morphometric properties of the CP-21 landing site on the Moon at Mons Gruithuisen Gamma

Characterizing terrain surface properties is an essential step in assessing the feasibility of landing successfully at a location on a planetary surface. Slopes and terrain ruggedness index (TRI) values derived from high-resolution (2 m pixel −1 ) digital terrain models provided important constraints in selecting the landing site for the upcoming Payloads and Research Investigations on the Surface of the Moon program as part of the Commercial Lunar Payload Services task order CP-21 mission. The selected landing site needed to balance safety requirements with the ability to achieve the science and exploration goals of the Lunar Vulkan Imaging and Spectroscopy Explorer payload. In this study, we compare several morphometric parameters in the context of the CP-21 landing site on Mons Gruithuisen Gamma, or the Gamma dome, and quantify the information they convey about lunar surface properties to assess their utility for future landing site evaluation. TRI was found to be a useful metric for assessing landing site safety. Metrics that better decouple slope and surface roughness, the vector ruggedness measure and the standard deviation of slope, provided additional information about surface characteristics and textures such as the degree to which roughness is isotropic.

Planetary Science Journal↗

USGS2026

Lunar-VISE landing site selection and characterization at Mons Gruithuisen Gamma

The Lunar Vulkan Imaging and Spectroscopy Explorer (Lunar-VISE) was selected for a Commercial Lunar Payload Services (CLPS) delivery to the Gruithuisen domes region of the Moon as part of NASA’s Payloads and Research Investigation on the Surface of the Moon (PRISM) program. The Gruithuisen domes are chemically and morphologically distinct from their surroundings with a thorium-rich, silicic composition. The Lunar-VISE instrument payload is designed to investigate the compositional and thermophysical properties of dome materials in order to understand how late-stage silicic volcanism occurred on the Moon. Selection of a landing site required balancing science and exploration goals with the safety requirements for landing and rover trafficability. Science required access to boulders, potential exposures of bedrock, and if possible, rover access to the dome edge to enable observations of the surrounding maria. Safety considerations included landing hazards, maintenance of line-of-sight communications between the lander and rover, and any early morning or late afternoon shadows that would limit the mission duration. After consideration of several candidate landing sites, a 100-meter diameter landing ellipse centered on 36.45715° N, 319.20398° E, was selected near the edge of a topographic step and blocky ejecta crater (recently named Mareta) near the summit of Mons Gruithuisen Gamma. This location enables access to a field of boulders excavated by a relatively fresh impact providing a diversity of boulders for investigations, as well as views to the surrounding mare and Mons Gruithuisen Delta dome off of the dome edge via only a short rover traverse outside the landing ellipse (traverse < 100 m) while meeting safety requirements in accord with the CLPS risk posture.

Planetary Science Journal↗