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USGS1996

Test system for exposing fish to resuspended, contaminated sediment

We describe a new test system for exposing fish to resuspended sediments and associated contaminants. Test sediments were resuspended by revolving test chambers on rotating shafts driven by an electric motor. The timing, speed, and duration of test-chamber revolution were controlled by a rheostat and electronic timer. Each chamber held 45 litres of water and accommodated about 49 g of test fish. The system described had three water baths, each holding six test chambers. We illustrate the performance of this system with results from a 28-day test in which juvenile bluegills Lepomis macrochirus were exposed to resuspended, riverine sediments differing in texture and cadmium content. The test had one sediment-free control and five sediment treatments, with three replicates (chambers) per treatment and 25 fish per replicate. Two-thirds (30 litres) of the test water and sediment in each chamber was renewed weekly. The mean concentration of total suspended solids (TSS) did not vary among treatments; the grand-mean TSS in the five sediment treatments was 975 mg litre −1 , similar to the target TSS of 1000 mg litre −1 . At the end of the test, an average of 50% of the introduced cadmium was associated with the suspended sediment compartment, whereas the filtered (0.45 μm) water contained 0.4% and bluegills 1.8% of the cadmium.

Environmental Pollution↗

USGS1979

Regional and local networks of horizontal control, Cerro Prieto geothermal area

The Cerro Prieto geothermal area in the Mexicali Valley 30 km southeast of Mexicali, Baja California, is probably deforming due to (1) the extraction of large volumes of steam and hot water, and (2) active tectonism. Two networks of precise horizontal control were established in Mexicali Valley by the U.S. Geological Survey in 1977 - 1978 to measure both types of movement as they occur. These networks consisted of (1) a regional trilateration net brought into the mountain ranges west of the geothermal area from survey stations on an existing U.S. Geological Survey crustal-strain network north of the international border, and (2) a local net tied to stations in the regional net and encompassing the area of present and planned geothermal production. Survey lines in this net were selected to span areas of probable ground-surface movements in and around the geothermal area. Electronic distance measuring (EDM) instruments, operating with a modulated laser beam, were used to measure the distances between stations in both networks. The regional net was run using a highly precise long-range EDM instrument, helicopters for transportation of men and equipment to inaccessible stations on mountain peaks, and a fixed wing airplane flying along the line of sight. Precision of measurements with this complex long-range system approached 0-2 ppm of line length. The local net was measured with a medium-range EDM instrument requiring minimal ancillary equipment. Precision of measurements with this less complex system approached 3 ppm for the shorter line lengths. The detection and analysis of ground-surface movements resulting from tectonic strains or induced by geothermal fluid withdrawal is dependent on subsequent resurveys of these networks. ?? 1979.

Geothermics↗

USGS1980

Physio-chemical and morphological characteristics of avian encephalomyelitis virus

Avian encephalomyelitis virus (AEV) was purified from infected chick embryos by a gradient centrifugation in cesium chloride. The virus had a buoyant density of 1.31 to 1.32 g/ml and a sedimentation coefficient of 148 S. The purified AEV was resistant to treatments with chloroform, acid pH or trypsin. The presence of Mg++ stabilized the virus against heat inactivation (56°C, 1 h). Electron microscopic study showed the virus to be 24 to 32 nm in diameter. The surface structure of the purified virus was not easily discernable. Nevertheless, with uranyl acetate-stained particles, Markham's rotation technique revealed that AEV has five-fold symmetry with 32 or 42 capsomers. Exact classification of AEV awaits characterization of the viral nucleic acid.

Veterinary Microbiology↗

USGS1993

Surface chemical effects on colloid stability and transport through natural porous media

Surface chemical effects on colloidal stability and transport through porous media were investigated using laboratory column techniques. Approximately 100 nm diameter, spherical, iron oxide particles were synthesized as the mobile colloidal phase. The column packing material was retrieved from a sand and gravel aquifer on Cape Cod, MA. Previous studies have indicated enhanced stability and transport of iron oxide particles due to specific adsorption of some inorganic anions on the iron oxide surface. This phenomenon was further evaluated with an anionic surfactant, sodium dodecyl sulfate. Surfactants constitute a significant mass of the contaminant loading at the Cape Cod site and their presence may contribute to colloidal transport as a significant transport mechanism at the site. Other studies at the site have previously demonstrated the occurrence of this transport mechanism for iron phosphate particles. Photon correlation spectroscopy, micro-electrophoretic mobility, and scanning electron microscopy were used to evaluate particle stability, mobility and size. Adsorption of negatively charged organic and inorganic species onto the surface of the iron oxide particles was shown to significantly enhance particle stability and transport through alterations of the electrokinetic properties of the particle surface. Particle breakthrough generally occurred simultaneously with tritiated water, a conservative tracer. The extent of particle breakthrough was primarily dependent upon colloidal stability and surface charge.

Massachusetts↗

USGS1993

Aquatic photolysis: photolytic redox reactions between goethite and adsorbed organic acids in aqueous solutions

Photolysis of mono and di-carboxylic acids that are adsorbed onto the surface of the iron oxyhydroxide (goethite) results in an oxidation of the organic material and a reduction from Fe(III) to Fe(II) in the iron complex. There is a subsequent release of Fe2+ ions into solution. At constant light flux and constant solution light absorption, the factors responsible for the degree of photolytic reaction include: the number of lattice sites that are bonded by the organic acid; the rate of acid readsorption to the surface during photolysis; the conformation and structure of the organic acid; the degree of oxidation of the organic acid; the presence or absence of an ??-hydroxy group on the acid, the number of carbons in the di-acid chain and the conformation of the di-acid. The ability to liberate Fe(III) at pH 6.5 from the geothite lattice is described by the lyotropic series: tartrate>citrate> oxalate > glycolate > maleate > succinate > formate > fumarate > malonate > glutarate > benzoate = butanoate = control. Although a larger amount of iron is liberated, the series is almost the same at pH 5.5 except that oxalate > citrate and succinate > maleate. A set of rate equations are given that describe the release of iron from the goethite lattice. It was observed that the pH of the solution increases during photolysis if the solutions are not buffered. There is evidence to suggest the primary mechanism for all these reactions is an electron transfer from the organic ligand to the Fe(III) in the complex. Of all the iron-oxyhydroxide materials, crystalline goethite is the least soluble in water; yet, this study indicates that in an aqueous suspension, iron can be liberated from the goethite lattice. Further, it has been shown that photolysis can occur in a multiphase system at the sediment- water interface which results in an oxidation of the organic species and release of Fe2+ to solution where it becomes available for further reaction. ?? 1993.

Journal of Photochemistry and Photobiology A: Chem↗

USGS1992

Correlation of Pliocene and Pleistocene tephra layers between the Turkana Basin of East Africa and the Gulf of Aden

Electron-microprobe analyses of glass shards from volcanic ash in Pliocene and Pleistocene deep-sea sediments in the Gulf of Aden and the Somali Basin demonstrate that most of the tephra layers correlate with tephra layers known on land in the Turkana Basin of northern Kenya and southern Ethiopia. Previous correlations are reviewed, and new correlations proposed. Together these data provide correlations between the deep-sea cores, and to the land-based sections at eight levels ranging in age from about 4 to 0.7 Ma. Specifically, we correlate the Moiti Tuff (???4.1 Ma) with a tephra layer at 188.6 m depth in DSDP hole 231 and with a tephra layer at 150 m depth in DSDP hole 241, the Wargolo Tuff with a tephra layer at 179.7 m in DSDP Hole 231 and with a tephra layer at 155.3 m depth in DSDP Hole 232, the Lomogol Tuff (defined here) with a tephra layer at 165 m in DSDP Hole 232A, the Lokochot Tuff with a tephra layer at 140.1 m depth in DSDP Hole 232, the Tulu Bor Tuff with a tephra layer at 160.8 m depth in DSDP Hole 231, the Kokiselei Tuff with a tephra layer at 120 m depth in DSDP Hole 231 and with a tephra layer at 90.3 m depth in DSDP Hole 232, the Silbo Tuff (0.74 Ma) with a tephra layer at 35.5 m depth in DSDP Hole 231 and possibly with a tephra layer at 10.9 m depth in DSDP Hole 241. We also present analyses of other tephra from the deep sea cores for which correlative units on land are not yet known. The correlated tephra layers provide eight chronostratigraphic horizons that make it possible to temporally correlate paleoecological and paleoclimatic data between the terrestrial and deep-sea sites. Such correlations may make it possible to interpret faunal evolution in the Lake Turkana basin and other sites in East Africa within a broader regional or global paleoclimatic context. ?? 1992.

Quaternary International↗

USGS1994

Direct chemical analysis of uv laser ablation products of organic polymers by using selective ion monitoring mode in gas chromatography/mass-spectrometry

Trace quantities of laser ablated organic polymers were analyzed by using commercial capillary column gas chromatography/mass spectrometry; the instrument was modified so that the iaser ablation products could be introduced into the capillary column directly and the constituents of each peak in the chromatogram were identified by using a mass spectrometer. The present study takes advantage of the selective ion monitoring mode for significantly improving the sensitivity of the mass spectrometer as a detector, which is critical in anatyzing the trace quantities and confirming the presence or absence of the species of interest in laser ablated polymers. The initial composition of the laser ablated polymers was obtained by using an electron impact reflectron time-of-flight mass spectrometer and the possible structure of the fragments observed in the spectra was proposed based on the structure of the polymers.

Journal of the American Society for Mass Spectrome↗

USGS1990

High temperature annealing of fission tracks in fluorapatite, Santa Fe Springs oil field, Los Angeles Basin, California

Annealing of fission tracks is a kinetic process dependent primarily on temperature and to a laser extent on time. Several kinetic models of apatite annealing have been proposed. The predictive capabilities of these models for long-term geologic annealing have been limited to qualitative or semiquantitative at best, because of uncertainties associated with (1) the extrapolation of laboratory observations to geologic conditions, (2) the thermal histories of field samples, and (3) to some extent, the effect of apatite composition on reported annealing temperatures. Thermal history in the Santa Fe Springs oil field, Los Angeles Basin, California, is constrained by an exceptionally well known burial history and present-day temperature gradient. Sediment burial histories are continuous and tightly constrained from about 9 Ma to present, with an important tie at 3.4 Ma. No surface erosion and virtually no uplift were recorded during or since deposition of these sediments, so the burial history is simple and uniquely defined. Temperature gradient (???40??C km-1) is well established from oil-field operations. Fission-track data from the Santa Fe Springs area should thus provide one critical field test of kinetic annealing models for apatite. Fission-track analysis has been performed on apatites from sandstones of Pliocene to Miocene age from a deep drill hole at Santa Fe Springs. Apatite composition, determined by electron microprobe, is fluorapatite [average composition (F1.78Cl0.01OH0.21)] with very low chlorine content [less than Durango apatite; sample means range from 0.0 to 0.04 Cl atoms, calculated on the basis of 26(O, F, Cl, OH)], suggesting that the apatite is not unusually resistant to annealing. Fission tracks are preserved in these apatites at exceptionally high present-day temperatures. Track loss is not complete until temperatures reach the extreme of 167-178??C (at 3795-4090 m depth). The temperature-time annealing relationships indicated by the new data from Santa Fe Springs conflict with predictions based on previously published, commonly used, kinetic annealing models for apatite. Work is proceeding on samples from another area of the basin that may resolve this discrepancy.

International Journal of Radiation Applications an↗

USGS2014

Iron oxide minerals in dust of the Red Dawn event in eastern Australia, September 2009

Iron oxide minerals typically compose only a few weight percent of bulk atmospheric dust but are important for potential roles in forcing climate, affecting cloud properties, influencing rates of snow and ice melt, and fertilizing marine phytoplankton. Dust samples collected from locations across eastern Australia (Lake Cowal, Orange, Hornsby, and Sydney) following the spectacular “Red Dawn” dust storm on 23 September 2009 enabled study of the dust iron oxide assemblage using a combination of magnetic measurements, Mössbauer spectroscopy, reflectance spectroscopy, and scanning electron microscopy. Red Dawn was the worst dust storm to have hit the city of Sydney in more than 60 years, and it also deposited dust into the Tasman Sea and onto snow cover in New Zealand. Magnetization measurements from 20 to 400 K reveal that hematite, goethite, and trace amounts of magnetite are present in all samples. Magnetite concentrations (as much as 0.29 wt%) were much higher in eastern, urban sites than in western, agricultural sites in central New South Wales (0.01 wt%), strongly suggesting addition of magnetite from local urban sources. Variable temperature Mössbauer spectroscopy (300 and 4.2 K) indicates that goethite and hematite compose approximately 25–45% of the Fe-bearing phases in samples from the inland sites of Orange and Lake Cowal. Hematite was observed at both temperatures but goethite only at 4.2 K, thereby revealing the presence of nanogoethite (less than about 20 nm). Similarly, hematite particulate matter is very small (some of it d < 100 nm) on the basis of magnetic results and Mössbauer spectra. The degree to which ferric oxide in these samples might absorb solar radiation is estimated by comparing reflectance values with a magnetic parameter (hard isothermal remanent magnetization, HIRM) for ferric oxide abundance. Average visible reflectance and HIRM are correlated as a group ( r 2 = 0.24), indicating that Red Dawn ferric oxides have capacity to absorb solar radiation. Much of this ferric oxide occurs as nanohematite and nanogoethite particles on surfaces of other particulate matter, thereby providing high surface area to enhance absorption of solar radiation. Leaching of the sample from Orange in simulated human-lung fluid revealed low bioaccessibility for most metals.

Aeolian Research↗

USGS2016

Iron oxide minerals in dust-source sediments from the Bodélé Depression, Chad: Implications for radiative properties and Fe bioavailability of dust plumes from the Sahara

Atmospheric mineral dust can influence climate and biogeochemical cycles. An important component of mineral dust is ferric oxide minerals (hematite and goethite) which have been shown to influence strongly the optical properties of dust plumes and thus affect the radiative forcing of global dust. Here we report on the iron mineralogy of dust-source samples from the Bodélé Depression (Chad, north-central Africa), which is estimated to be Earth’s most prolific dust producer and may be a key contributor to the global radiative budget of the atmosphere as well as to long-range nutrient transport to the Amazon Basin. By using a combination of magnetic property measurements, Mössbauer spectroscopy, reflectance spectroscopy, chemical analysis, and scanning electron microscopy, we document the abundance and relative amounts of goethite, hematite, and magnetite in dust-source samples from the Bodélé Depression. The partition between hematite and goethite is important to know to improve models for the radiative effects of ferric oxide minerals in mineral dust aerosols. The combination of methods shows (1) the dominance of goethite over hematite in the source sediments, (2) the abundance and occurrences of their nanosize components, and (3) the ubiquity of magnetite, albeit in small amounts. Dominant goethite and subordinate hematite together compose about 2% of yellow-reddish dust-source sediments from the Bodélé Depression and contribute strongly to diminution of reflectance in bulk samples. These observations imply that dust plumes from the Bodélé Depression that are derived from goethite-dominated sediments strongly absorb solar radiation. The presence of ubiquitous magnetite (0.002–0.57 wt%) is also noteworthy for its potentially higher solubility relative to ferric oxide and for its small sizes, including PM < 0.1 μm. For all examined samples, the average iron apportionment is estimated at about 33% in ferric oxide minerals, 1.4% in magnetite, and 65% in ferric silicates. Structural iron in clay minerals may account for much of the iron in the ferric silicates. We estimate that the mean ferric oxides flux exported from the Bodélé Depression is 0.9 Tg/yr with greater than 50% exported as ferric oxide nanoparticles (<0.1 μm). The high surface-to-volume ratios of ferric oxide nanoparticles once entrained into dust plumes may facilitate increased atmospheric chemical and physical processing and affect iron solubility and bioavailability to marine and terrestrial ecosystems.

Aeolian Research↗

USGS2007

Progressive oxidation of pyrite in five bituminous coal samples: An As XANES and 57 Fe Mössbauer spectroscopic study

Naturally occurring pyrite commonly contains minor substituted metals and metalloids (As, Se, Hg, Cu, Ni, etc.) that can be released to the environment as a result of its weathering. Arsenic, often the most abundant minor constituent in pyrite, is a sensitive monitor of progressive pyrite oxidation in coal. To test the effect of pyrite composition and environmental parameters on the rate and extent of pyrite oxidation in coal, splits of five bituminous coal samples having differing amounts of pyrite and extents of As substitution in the pyrite, were exposed to a range of simulated weathering conditions over a period of 17 months. Samples investigated include a Springfield coal from Indiana (whole coal pyritic S = 2.13 wt.%; As in pyrite = detection limit (d.l.) to 0.06 wt.%), two Pittsburgh coal samples from West Virginia (pyritic S = 1.32–1.58 wt.%; As in pyrite = d.l. to 0.34 wt.%), and two samples from the Warrior Basin, Alabama (pyritic S = 0.26–0.27 wt.%; As in pyrite = d.l. to 2.72 wt.%). Samples were collected from active mine faces, and expected differences in the concentration of As in pyrite were confirmed by electron microprobe analysis. Experimental weathering conditions in test chambers were maintained as follows: (1) dry Ar atmosphere; (2) dry O 2 atmosphere; (3) room atmosphere (relative humidity &sim;20–60%); and (4) room atmosphere with samples wetted periodically with double-distilled water. Sample splits were removed after one month, nine months, and 17 months to monitor the extent of As and Fe oxidation using As X-ray absorption near-edge structure (XANES) spectroscopy and 57 Fe Mössbauer spectroscopy, respectively. Arsenic XANES spectroscopy shows progressive oxidation of pyritic As to arsenate, with wetted samples showing the most rapid oxidation. 57 Fe Mössbauer spectroscopy also shows a much greater proportion of Fe 3+ forms (jarosite, Fe 3+ sulfate, FeOOH) for samples stored under wet conditions, but much less difference among samples stored under dry conditions in different atmospheres. The air-wet experiments show evidence of pyrite re-precipitation from soluble ferric sulfates, with As retention in the jarosite phase. Extents of As and Fe oxidation were similar for samples having differing As substitution in pyrite, suggesting that environmental conditions outweigh the composition and amount of pyrite as factors influencing the oxidation rate of Fe sulfides in coal.

Applied Geochemistry↗

USGS2009

A regional-scale study of chromium and nickel in soils of northern California, USA

A soil geochemical survey was conducted in a 27,000-km 2 study area of northern California that includes the Sierra Nevada Mountains, the Sacramento Valley, and the northern Coast Range. The results show that soil geochemistry in the Sacramento Valley is controlled primarily by the transport and weathering of parent material from the Coast Range to the west and the Sierra Nevada to the east. Chemically and mineralogically distinctive ultramafic (UM) rocks (e.g. serpentinite) outcrop extensively in the Coast Range and Sierra Nevada. These rocks and the soils derived from them have elevated concentrations of Cr and Ni. Surface soil samples derived from UM rocks of the Sierra Nevada and Coast Range contain 1700-10,000 mg/kg Cr and 1300-3900 mg/kg Ni. Valley soils west of the Sacramento River contain 80-1420 mg/kg Cr and 65-224 mg/kg Ni, reflecting significant contributions from UM sources in the Coast Range. Valley soils on the east side contain 30-370 mg/kg Cr and 16-110 mg/kg Ni. Lower Cr and Ni concentrations on the east side of the valley are the result of greater dilution by granitic sources of the Sierra Nevada. Chromium occurs naturally in the Cr(III) and Cr(VI) oxidation states. Trivalent Cr is a non-toxic micronutrient, but Cr(VI) is a highly soluble toxin and carcinogen. X-ray diffraction and scanning electron microscopy of soils with an UM parent show Cr primarily occurs within chromite and other mixed-composition spinels (Al, Mg, Fe, Cr). Chromite contains Cr(III) and is highly refractory with respect to weathering. Comparison of a 4-acid digestion (HNO 3 , HCl, HF, HClO 4 ), which only partially dissolves chromite, and total digestion by lithium metaborate (LiBO 3 ) fusion, indicates a lower proportion of chromite-bound Cr in valley soils relative to UM source soils. Groundwater on the west side of the Sacramento Valley has particularly high concentrations of dissolved Cr ranging up to 50 ??g L -1 and averaging 16.4 ??g L -1 . This suggests redistribution of Cr during weathering and oxidation of Cr(III)-bearing minerals. It is concluded that regional-scale transport and weathering of ultramafic-derived constituents have resulted in enrichment of Cr and Ni in the Sacramento Valley and a partial change in the residence of Cr.

Applied Geochemistry↗

USGS2013

Tracing groundwater with low-level detections of halogenated VOCs in a fractured carbonate-rock aquifer, Leetown Science Center, West Virginia, USA

Measurements of low-level concentrations of halogenated volatile organic compounds (VOCs) and estimates of groundwater age interpreted from 3 H/ 3 He and SF 6 data have led to an improved understanding of groundwater flow, water sources, and transit times in a karstic, fractured, carbonate-rock aquifer at the Leetown Science Center (LSC), West Virginia. The sum of the concentrations of a set of 16 predominant halogenated VOCs (TDVOC) determined by gas chromatography with electron-capture detector (GC–ECD) exceeded that possible for air–water equilibrium in 34 of the 47 samples (median TDVOC of 24,800 pg kg −1 ), indicating that nearly all the water sampled in the vicinity of the LSC has been affected by addition of halogenated VOCs from non-atmospheric source(s). Leakage from a landfill that was closed and sealed nearly 20 a prior to sampling was recognized and traced to areas east of the LSC using low-level detection of tetrachloroethene (PCE), methyl chloride (MeCl), methyl chloroform (MC), dichlorodifluoromethane (CFC-12), and cis-1,2-dichloroethene (cis-1,2-DCE). Chloroform (CHLF) was the predominant VOC in water from domestic wells surrounding the LSC, and was elevated in groundwater in and near the Fish Health Laboratory at the LSC, where a leak of chlorinated water occurred prior to 2006. The low-level concentrations of halogenated VOCs did not exceed human or aquatic-life health criteria, and were useful in providing an awareness of the intrinsic susceptibility of the fractured karstic groundwater system at the LSC to non-atmospheric anthropogenic inputs. The 3 H/ 3 He groundwater ages of spring discharge from the carbonate rocks showed transient behavior, with ages averaging about 2 a in 2004 following a wet climatic period (2003–2004), and ages in the range of 4–7 a in periods of more average precipitation (2008–2009). The SF 6 and CFC-12 data indicate older water (model ages of 10s of years or more) in the low-permeability shale of the Martinsburg Formation located to the west of the LSC. A two-a record of specific conductance, water temperature, and discharge recorded at 30-min intervals demonstrated an approximately 3-month lag in discharge at Gray Spring. The low groundwater ages of waters from the carbonate rocks support rapid advective transport of contaminants from the LSC vicinity, yet the nearly ubiquitous occurrence of low-level concentrations of halogenated VOCs at the LSC suggests the presence of long-term persistent sources, such as seepage from the closed and sealed landfill, infiltration of VOCs that may persist locally in the epikarst, exchange with low-permeability zones in fractured rock, and upward leakage of older water that may contain elevated concentrations of halogenated VOCs from earlier land use activities.

West Virginia↗

USGS2015

Persistent U(IV) and U(VI) following in-situ recovery (ISR) mining of a sandstone uranium deposit, Wyoming, USA

Drill-core samples from a sandstone-hosted uranium (U) deposit in Wyoming were characterized to determine the abundance and distribution of uranium following in-situ recovery (ISR) mining with oxygen- and carbon dioxide-enriched water. Concentrations of uranium, collected from ten depth intervals, ranged from 5 to 1920 ppm. A composite sample contained 750 ppm uranium with an average oxidation state of 54% U(VI) and 46% U(IV). Scanning electron microscopy (SEM) indicated rare high uranium (&sim;1000 ppm U) in spatial association with P/Ca and Si/O attributed to relict uranium minerals, possibly coffinite, uraninite, and autunite, trapped within low permeability layers bypassed during ISR mining. Fission track analysis revealed lower but still elevated concentrations of U in the clay/silica matrix and organic matter (several 10 s ppm) and yet higher concentrations associated with Fe-rich/S-poor sites, likely iron oxides, on altered chlorite or euhedral pyrite surfaces (but not on framboidal pyrite). Organic C (<1.62%), total S (<0.31%), and P (<0.03%) were in low abundance relative to the overall bulk composition. Microbial community analysis showed a diverse group of bacteria present with a wide range of putative metabolisms, and provides evidence for a variety of redox microenvironments co-existing in core samples. Although the uranium minerals persisting in low permeability areas in association with organic carbon were less affected by oxidizing solutions during mining, the likely sequestration of uranium within labile iron oxides following mining and sensitivity to changes in redox conditions requires careful attention during groundwater restoration.

Wyoming↗

USGS2017

Assessing changes in the physico-chemical properties and fluoride adsorption capacity of activated alumina under varied conditions

Adsorption using activated alumina is a simple method for removing fluoride from drinking water, but to be cost effective the adsorption capacity must be high and effective long-term. The intent of this study was to assess changes in its adsorption capacity under varied conditions. This was determined by evaluating the physico-chemical properties, surface charge, and fluoride (F − ) adsorption capacity and rate of activated alumina under conditions such as hydration period, particle size, and slow vs. fast titrations. X-ray diffraction and scanning electron microscopy analyses show that the mineralogy of activated alumina transformed to boehmite, then bayerite with hydration period and a corresponding reduction in adsorption capacity was expected; while surface area analyses show no notable changes with hydration period or particle size. The pH dependent surface charge was three times higher using slow potentiometric titrations as compared to fast titrations (due largely to diffusion into pore space), with the surface acidity generally unaffected by hydration period. Results from batch adsorption experiments similarly show no change in fluoride adsorption capacity with hydration period. There was also no notable difference in fluoride adsorption capacity between the particle size ranges of 0.5–1.0 mm and 0.125–0.250 mm, or with hydration period. However, adsorption rate increased dramatically with the finer particle sizes: at an initial F − concentration of 0.53 mmol L −1 (10 mg L −1 ), 90% was adsorbed in the 0.125–0.250 mm range after 1 h, while the 0.5–1.0 mm range required 24 h to achieve 90% adsorption. Also, the pseudo-second-order adsorption rate constants for the finer vs. larger particle sizes were 3.7 and 0.5 g per mmol F − per min respectively (24 h); and the initial intraparticle diffusion rate of the former was 2.6 times faster than the latter. The results show that adsorption capacity of activated alumina remains consistent and high under the conditions evaluated in this study, but in order to increase adsorption rate, a relatively fine particle size is recommended.

Applied Geochemistry↗

USGS2019

Organic geochemistry and toxicology of a stream impacted by unconventional oil and gas wastewater disposal operations

Water and sediment extracts samples were analyzed for extractable hydrocarbons by gas chromatography/mass spectrometry (GC/MS) using an Agilent (Agilent Technologies, Palo Alto, CA, USA) 7890 series GC and 5975 electron ionization (EI) mass selective detector (MSD) operated in scan mode. Agilent ChemStation software was used for data acquisition and analysis (version E.02.00.493 on GC/MS computer and version F.01.03.2357 on laptop for data workup). A 30 m x 250 m x 0.25 m HP-5MS column (95% dimethyl 5% diphenyl polydimethylsiloxane) was used for GC/MS under the following conditions: 1.0 L splitless injection, constant flow of 0.7 mL/min, solvent delay of 7.5 min, injector temperature of 280C, interface at 300C, temperature program of 50-150C at 7C/min, 150-230C at 6C/min, and 230-300C at 3C/min with mass scanned from 35-500 Da.

West Virginia↗

USGS2020

Natural attenuation can lead to environmental resilience in mine environment

Four streams flowing in the Iglesiente and Arburese mine districts (SW Sardinia, Italy), exploited for zinc (Zn) and lead (Pb) extraction from sulphides and secondary non-sulphide mineralization (calamine ores), have been studied combining investigations from the macroscale (hydrologic tracer techniques) to the microscale (X-ray powder diffraction, scanning electron microscopy, X-ray absorption spectroscopy). In the investigated area, concerns arise from release of metals to water during weathering of ore minerals and mine-waste. Specifically, Zn is observed at extremely high concentrations (10s of mg/L or more) in waters in some of the investigated catchments. The results from synoptic sampling campaigns showed marked differences of Zn loads, from 6.3 kg/day (Rio San Giorgio) to 2000 kg/day (Rio Irvi). Moreover, natural attenuation of metals was found to occur i) through precipitation of Fe compounds (Fe oxy/hydroxides and “green rust”), ii) by means of the authigenic formation of metal sulphides promoted by microbial sulphate reduction, iii) by metal intake in roots and stems of plants ( Phragmites australis and Juncus acutus ) and by immobilization in the rhizosphere, and iv) by cyanobacterial biomineralization processes that lead to formation of Zn-rich phases (hydrozincite and amorphous Zn-silicate) The biologically mediated natural processes that lead to significant abatement and/or reduction of metal loads, are the response of environmental systems to perturbations caused from mine activities, and can be considered part of the resilience of the system itself. The aim of this study is to understand the effect of these processes on the evolution of the studied systems towards more stable and, likely, resilient conditions, e.g. by limiting metal mobility and favoring the improvement of the overall quality of water. The understanding of how ecosystems adapt and respond to contamination, and which chemical and physical factors control these natural biogeochemical barriers, can help to plan effective remediation actions.

Sardinia↗

USGS2025

Properties of solid bitumen formed during hydrous, anhydrous, and brine pyrolysis of oil shale: Implications for solid bitumen reflectance in source-rock reservoirs

Solid bitumen reflectance (BR o in %) is widely used as a thermal maturity proxy in source-rock reservoirs, yet solid bitumen texture and physical attributes may be affected by varying environmental constraints during its formation, e.g., water saturation, mineral catalysis, or salinity. Herein we investigated the development of solid bitumen properties during artificial maturation using three diverse (lacustrine to marine) oil shale samples containing abundant amorphous H-rich sedimentary organic matter (bituminite). The oil shales were treated via pyrolysis (320 °C, 72 h) using hydrous, anhydrous, and brine conditions, causing the development of a newly formed solid bitumen in the experiment residues from the thermal conversion of bituminite. The properties of the newly formed solid bitumen then were evaluated via geochemical screening tests, optical and electron microscopy, and infrared spectroscopy. Experimental residues also were treated via solvent extraction, allowing characterization of the effects of extraction on solid bitumen. Results showed that bituminite with higher resin and asphaltene components evolved to a solid bitumen with higher reflectance (as a percentage of the original value) when exposed to the same heat treatment, relative to bituminite with higher saturate and aromatic components. Aromatization of solid bitumen also was generally more pronounced in the presence of deionized water relative to anhydrous conditions, supporting prior observations. These results suggest the compositions of primary sedimentary organic matter, and the local concentration of water, affect the development of solid bitumen during thermal advance, potentially explaining the origin of multiple solid bitumen populations with varying reflectance in source-rock reservoir samples or in a single microscope field. Experiments using brine were inconclusive regarding enhanced/decreased aromatization, which could be attributed to the salinities of the brines used in the tests. Extraction of residues caused a consistent increase in BR o values, suggesting that migrating or expelled oils could cause an increase in BR o via natural solvation and absent an increase in temperature. This work provides insights into the development and evolution of BR o in source-rock reservoirs as a function of the composition of the original bituminite and changing environmental conditions, with potentially broad application for petroleum prospecting and resource estimation.

Colorado↗