Geology topics

Michael J. Pribil

Publications and source records attributed to Michael J. Pribil.

At least 19 recordsLinked to original sources

USGS2026

Insights into Mountain Pass carbonatite formation from in-situ sulfur isotopes and geochemistry of sulfate and sulfide minerals

The Mountain Pass carbonatite stock hosts a world-class rare earth element deposit and may be classified as a carbonate-sulfate igneous rock, as it contains on average > 50 volume percent carbonate minerals and 20 to 30 volume percent sulfate minerals. The sulfates range in composition from barite to celestine and locally occur with sparse sulfide minerals. We investigate the origin of sulfur enrichment and the occurrence of sulfur-bearing minerals in the Mountain Pass carbonatite with in-situ sulfur isotope and mineral chemistry. Barite cores with δ 34 S of 1 to 3‰ do not coexist with sulfides, whereas celestine rims with δ 34 S of > 3‰ are associated with sulfides with δ 34 S < -10‰. We propose a model in which sulfur-bearing sediments were subducted during episodes of plate convergence in the Mojave Province that preceded Mountain Pass magmatism. Metasomatism of the overlying mantle by melts derived from the subducted sediments generated an unusually carbon- and sulfur-rich source to yield carbonatite magmas. Sulfur from primary carbonatite magmas and ~ 1 to 7% sulfur from subducted sediment melts yielded a slightly enriched δ 34 S composition (relative to depleted mantle δ 34 S of -1‰) for early crystallizing barite. Celestine rims on magmatic barite cores formed at low, hydrothermal temperatures (< 350 °C) based on S isotope thermometry for equilibrium celestine-galena and celestine-pyrite pairs. The sparse sulfides in the carbonatite stock are not in equilibrium with the primary barite cores and therefore do not permit S isotope thermometry estimates of magmatic temperatures. The S/Se ratios of sulfide minerals (> 3,400) typically exceed primitive mantle values (S/Se of 3,340), also consistent with their derivation from hydrothermal fluids. Trace occurrences of sulfide and sulfate minerals in alkaline silicate stocks related to the carbonatite stock have similar δ 34 S compositions and yield similarly low formation temperatures, suggesting regionally extensive and chemically similar sulfur-bearing hydrothermal fluids that imparted lithologically diverse rocks with a consistent sulfur isotope fingerprint.

California, Nevada↗

USGS2022

Increased mercury and reduced insect diversity in linked stream-riparian food webs downstream of a historical mercury mine

Historical mining left a legacy of abandoned mines and waste rock in remote headwaters of major river systems in the western United States. Understanding the influence of these legacy mines on culturally and ecological important downstream ecosystems is not always straight-forward because of elevated natural levels of mineralization in mining-impacted watersheds. To test the ecological effects of historic mining in the headwaters of the upper Salmon River watershed (USA), we measured multiple community and chemical endpoints in downstream linked aquatic-terrestrial food webs. Mining inputs impacted downstream food webs through increased mercury accumulation and decreased insect biodiversity. Total mercury (THg) in seston, aquatic insect larvae, adult aquatic insects, riparian spiders, and fish at sites up to 7.6 km downstream of mining was in much higher concentrations (1.3 to 11.3-fold) and isotopically distinct compared with sites immediately upstream of mining inputs. Methylmercury (MeHg) concentrations in bull trout and riparian spiders were sufficiently high (732 – 918 and 347 – 1,140 ng MeHg g -1 dw) to affect humans, birds, and piscivorous fish. Furthermore, the alpha-diversity of benthic insects was locally depressed by 12-20% within 4.3 to 5.7 km downstream of from the mine. However, because total insect biomass was not affected by mine inputs, the mass of mercury in benthic insects at a site (i.e., ng Hg m -2 ) was extremely elevated downstream (10 – 1,778-fold) compared with directly upstream of mining inputs. Downstream adult aquatic insect-mediated fluxes of total mercury were also high (~16 ng THg m -2 d -1 ). Abandoned mines can have ecologically important effects on downstream communities, including reduced biodiversity and increased mercury flux to higher order consumers, including fish, birds, and humans.

Idaho↗

USGS2022

Nanoscale isotopic evidence resolves origins of giant Carlin-type ore deposits

The western North American Great Basin's Carlin-type deposits represent the largest accumulation of gold in the Northern Hemisphere. The controversy over their origins echoes the debate between Neptunists and Plutonists at the birth of modern geology: were the causative processes meteoric or magmatic? Sulfur isotopes have long been considered key to decoding metal cycling in the Earth's crust, but previous studies of Carlin-type pyrite lacked the spatial resolution to quantify differences among the numerous generations of sulfide mineralization. We developed a new dual-method, nanoscale approach to examine the fine-grained ore pyrite. The δ 34 S of the ore pyrite varies systematically with Au concentration at the nanoscale, indicating that both magmatic and meteoric fluids contributed during mineralization, but the magmas brought the gold. Repeated oscillations in fluid ratios upgraded the metal content, resulting in high gold endowment. Our results demonstrate that high-spatial-resolution studies are key to elucidate the spatiotemporal evolution of complex hydrothermal systems.

Nevada↗

USGS2022

Occurrence and sources of lead in private wells, Sturbridge, Massachusetts

Lead (Pb) occurrence and sources and aqueous geochemistry were assessed in private wellhead and tap water at a targeted area of concern for possible exceedances and at a control area in the same geologic formation, and in wells at a nearby landfill in south-central Massachusetts (MA). Total Pb concentrations were below the U.S. Environmental Protection Agency (USEPA) Action Level of 15 μg/L in all samples, and about 6% of unfiltered samples contained Pb concentrations that exceeded 1.0 μg/L. Pb concentrations were higher under conditions that are acidic and oxic (pH ≤ 6.5 and dissolved oxygen [DO] ≥ 2 mg/L), in which minerals that could sequester lead or manganese typically are undersaturated, and adsorption by hydrous ferric oxide is limited. Under more neutral to alkaline conditions, the precipitation of Pb in solid solution series minerals such as (Ca,Pb)CO 3 and (Ba,Pb)SO 4 −2 , and adsorption by amorphous ferric hydroxides, could limit Pb solubility in the bedrock aquifer or in the plumbing. The low Pb concentrations and the absence of distinctive Pb and strontium (Sr) isotope ratio patterns in samples indicate that a nearby landfill is not likely a significant Pb source. Dissolved concentrations of Pb, copper (Cu), and zinc (Zn) in tap samples were significantly greater than those in wellhead samples, indicating that some Pb is derived from plumbing. Wellhead or tap samples with the highest Pb concentrations also had the greatest corrosivity potential based on the calcite saturation index and the PPGC (Potential to Promote Galvanic Corrosion) and supports the premise that Pb concentrations in tap samples were derived partly from corrosion of plumbing. Concentrations of other constituents, including arsenic (As), uranium (U), Sr, boron (B), and lithium (Li) were not statistically different between the tap and wellhead samples but, apart from Sr, all were statistically higher in the control area than in the target area. This variation in constituent concentrations suggests geochemical variation within the host Paxton Formation, possibly related to faulting and contact with the Ayer granite east of the control area.

Massachusetts↗

USGS2020

Assessing mercury distribution using isotopic fractionation of mercury processes and sources adjacent and downstream of a legacy mine district in Tuscany, Italy

Mercury (Hg) concentrations and isotopic compositions in a range of sample types collected from the legacy Abbadia San Salvatore Mine (ASSM) area were used to evaluate the distribution of Hg in the region. The district generated more than 100,000 metric tons of Hg releasing extensive amounts of gaseous Hg emissions and producing large amounts of mine waste calcine from which Hg can be mobilized into the local and regional environments. Direct and indirect impact from cinnabar ore mining and processing resulted in elevated Hg concentrations in the calcine, soils, lake and stream sediments, and fish samples collected at and downstream of ASSM. The contribution of Hg from the different sources and processes resulted in a wide range of 202Hg and 199Hg isotopic compositions (-2.25 to 0.96‰, -0.12 to 0.72‰ respectively). Fish samples resulted in negative values for 202Hg (-0.53 to -1.21‰) and positive Hg (0.12 to 0.73‰). Primary cinnabar ore and present-day geothermal water and precipitate showed distinctly negative 202Hg (-0.96 to -2.25‰), whereas waste calcine were enriched in 202Hg (202Hg from about -1 to +1‰); soils and sediments show intermediate compositions, reflecting different extents of contributions from the various Hg sources and processes. These sources and processes of Hg include weathering cinnabar, gaseous Hg emissions from ore processing, and geothermal activity to a lesser extent. Hg speciation in concert with Hg isotope ratios can better ascertain source attribution and assist in identifying Hg pathways into the environment to distinguish the more bioavailable forms of Hg entering the ecosystem.

Tuscany↗

USGS2020

Lead speciation, bioaccessibility and source attribution in Missouri's Big River watershed

The Southeast Missouri Lead District is among the most productive lead deposits exploited in modern times. Intensive mining conducted prior to regulations resulted in a legacy of lead contaminated soil, large piles of mine tailings and elevated childhood blood lead levels. This study seeks to identify the source of the lead contamination in the Big River and inform risk to the public. Isotopic analysis indicated the mine tailing piles at the head of the Big River are the primary source of the lead contamination. The isotopic signature of the lead in these mine tailings matched the lead over 100 km downstream. All of the other potential lead sources investigated had different isotopic signatures. Lead concentrations in soils and sediments decrease with distance downstream of the mine tailings piles. Additionally, the speciation of the lead changes from predominantly mineralized forms, such as galena, to adsorbed lead. This is reflected in the in-vitro bioaccessibility assay (IVBA) analysis which shows higher bioaccessibility further downstream, demonstrating the importance of speciation in risk evaluation.

Missouri↗

USGS2019

Magmatic-hydrothermal gold mineralization at the Lone Tree Mine, Battle Mountain district, Nevada

The Lone Tree deposit is located in the northern Battle Mountain mining district, Nevada. Prior to mine closure in 2006, Santa Fe Pacific Gold and Newmont produced 4.2 Moz of gold at an average grade of 2.06 g/t at Lone Tree, primarily from the N-S– to NNW-SSE–striking Wayne zone. The ore is located between the Roberts Mountain and Golconda thrusts in siliciclastic rocks of the Ordovician Valmy Formation and in the Pennsylvanian-Permian Battle Mountain and Edna Mountain Formations, and above the Golconda thrust in siliciclastic and carbonate rocks of the Mississippian to Permian Havallah sequence. Ore is also hosted by rhyolitic dikes that were emplaced at 40.95 ± 0.06 Ma based on zircon U-Pb chemical abrasion-thermal ionization mass spectrometry. The gold is associated with sericitic and argillic alteration of the siliciclastic rocks and dikes and with decarbonatization and Fe carbonate alteration of the carbonate-bearing units, as well as in Fe-As sulfide and finegrained quartz alteration of all rock types. Oxidation affects 30 to 45% of the deposit, penetrating into the stratigraphy along numerous steeply dipping north-south, east-west, and north-northeast–south-southwest structures. Gold is positively correlated with Ag, As, Hg, and Sb. The highest Au grades occur in quartz-sulfide ore hosted in siliciclastic and carbonate sedimentary rocks and rhyolitic intrusions. In this ore style, fine-grained quartz and sericite are intergrown with disseminated sulfide minerals (quartz-sericite-pyrite alteration), constituting cores of weakly mineralized pyrite or marcasite, which are surrounded by fuzzy arsenopyrite rims that contain up to ~2,000 ppm Au. Low gold grades occur in late-stage banded pyrite breccias consisting of a finely zoned Au-poor pyrite matrix surrounding jigsaw-fit clasts of quartz-, illite-, barite-, and adularia-altered siliciclastic rock. The timing of main-stage mineralization is bracketed between the emplacement of the dikes and an adularia 40 Ar/ 39 Ar age of 40.14 ± 0.74 Ma. Sericite intergrown with arsenopyrite-rimmed pyrite in phenocrysts of the rhyolite dikes gave δ 18 O values of 1.6 to 9.5‰ and δ D values of –105 to –145‰. For temperatures of 300 ± 100°C, the calculated fluid isotopic compositions are consistent with felsic magmatic water and minor modifications by mixing with meteoric water and exchange with wall rocks. In the silica-sulfide ore, in situ isotopic laser ablation-multicollector-inductively coupled plasma-mass spectrometry (LA-MC-ICP-MS) analyses of pyrite cores yielded δ 34 S values ranging from 3.4 to 7.7‰, with average values of 5.6‰ in the felsic dikes, 4.5‰ in the siliciclastic rocks, and 5.3‰ in the carbonate rocks. These values match conventional pyrite δ 34 S data reported for Eocene porphyry systems elsewhere in the district. Nanoscale secondary ion mass spectrometry analyses show that gold and associated trace elements occur in submicron-scale zones within arsenopyrite rims on pyrite. The average δ 34 S values of the arsenopyrite rims are 5.3 to 6.5‰ heavier than the pyrite cores, indicating cooling and an increasing H 2 S/SO 2 ratio. The highest grades resulted from episodic pulses of a gold-rich fluid that was partly derived from, or exchanged with, the sedimentary host rocks. In situ LA-MC-ICP-MS δ 34 S values for the late-stage banded pyrite breccia become progressively lighter from veinlet margin to center, reaching a low of –32‰. These veinlets indicate a shift from main-stage quartz-sericite-pyrite and intermediate argillic alteration to more neutral pH and oxidizing conditions during late-stage mineralization, indicating either increasing interaction between the fluid and sedimentary sulfur sources in the host-rock package or bacterial sulfate reduction and supergene sulfide precipitation.

Nevada↗

USGS2018

Magmatic origin for sediment-hosted Au deposits, Guizhou Province, China: In situ chemistry and sulfur isotope composition of pyrites, Shuiyindong and Jinfeng deposits

The southwest Guizhou Province, China, contains numerous sediment-hosted Au deposits with Au reserves greater than 700 tonnes. To date, the source of ore fluids that formed the Guizhou sediment-hosted Au deposits is controversial, hampering the formulation of genetic models. In this study, we selected the Shuiyindong and Jinfeng Au deposits, the largest strata-bound and fault-controlled deposits in Guizhou, respectively, for detailed research on pyrite chemistry and S isotope composition using laser ablation-inductively coupled plasma-mass spectrometry (LA-ICP-MS) and laser ablation-multicollector-inductively coupled plasma-mass spectrometry (LA-MC-ICP-MS), respectively. Petrography and pyrite chemistry studies distinguished five generations of pyrite. Among these, pre-ore pyrite 2 and ore pyrite are the most abundant types in the deposits. Pre-ore pyrite 2 is anhedral to euhedral and with ~2,639 ppm As and wider ranges of Cu, Sb, and Pb (<~22–4,837 ppm, <~6 to 532 ppm, and <~4 to 1,344 ppm, respectively). Gold in pre-ore pyrite 2 is below the detection limit of LA-ICP-MS (~2 ppm). Pre-ore pyrite 2 is interpreted to have a sedimentary (syngenetic or diagenetic) origin. Ore pyrite commonly rims the four identified pre-ore pyrites or occurs as individual, anhedral to euhedral crystals. Ore pyrite is enriched in Au (~641 ppm), As (~9,147 ppm), Cu (~1,043 ppm), Sb (~188 ppm), Hg (~43 ppm), and Tl (~22 ppm) in both deposits. Ore pyrite formed mainly by sulfidation of Fe in Fe-bearing host rocks, mainly Fe dolomite, and As, Cu, Sb, Hg, and Tl, also in ore fluids, were incorporated into ore pyrite. In situ δ 34 S isotope ratios for pre-ore pyrite 2 and ore pyrite were measured by LA-MC-ICP-MS. Pre-ore pyrite 2 from Shuiyindong and Jinfeng deposits resulted in δ 34 S values ranging from −0.8 to +3.4‰ and from 5.1 to 10.5‰, respectively. Analyses of ore pyrite from the Shuiyindong have δ 34 S values that vary from −3.3 to +2.5‰, with a median of 0.7‰; analyses of ore pyrite from the Jinfeng range from 8.9 to 11.2‰, with a median at 10.3‰. Available bulk and in situ δ 34 S data in the literature for pre-ore pyrites 1 and 2 and ore-related sulfide minerals including ore pyrite, arsenopyrite, and late ore-stage stibnite, realgar, orpiment, and cinnabar from several Guizhou sediment-hosted Au deposits were compiled for comparison. Pre-ore-stage pyrites from Guizhou sediment-hosted Au deposits have a broad range of δ 34 S values, from −33.8 to + 17.9‰ (including in situ and available bulk δ 34 S data). Ore-related sulfide minerals in all Guizhou sediment-hosted Au deposits, except Jinfeng, have very similar δ 34 S values, and most data plot between ~−5 and +5‰. In the Jinfeng deposit, the ore-related sulfide minerals exhibit δ 34 S values ranging from 1.9 to 18.1‰, with most data plotting between 6 and 12‰. The broad range of S isotope compositions for the sedimentary pyrites (pre-ore pyrites 1 and 2) indicate that S in these pre-ore pyrites was most likely generated by bacterial reduction from marine sulfate. The narrow range of δ 34 S values (~−5–+5‰) for ore-related sulfide minerals in all Guizhou sediment-hosted Au deposits, excepting the Jinfeng deposit, suggests that the deposits may have formed in response to a single widespread metallogenic event. As the S isotope fractionation between hydrothermal fluids and sulfide minerals in a sulfide-dominated system is small (<2‰) at ~250°C, the initial ore fluids that formed the Guizhou sediment-hosted Au deposits would have had δ 34 S values similar to the ore-related sulfide minerals, between ~−5 and +5‰. At Jinfeng, initial ore fluids may have mixed with local fluids with heavier δ 34 S, possibly basin brine ( δ 34 S basin brine >18‰), resulting in elevated δ 34 S values of ore-related sulfide minerals and especially late ore-stage sulfide minerals. Although few igneous rocks are exposed in the mining area around these deposits, there is evidence of magmatic activity ~20 km away. Furthermore, gravity and magnetic geophysical investigations indicate the presence of a pluton ~5 km below the surface of the Shuiyindong district. Based on in situ S isotope results and recent data indicating proximal intrusions, we interpret a deep magmatic S source for the ore fluids that formed the Guizhou sediment-hosted Au deposits. However, as the age for Au mineralization of Guizhou sediment-hosted Au deposits is still debated, the mineralization-magma connection remains hypothetical. Identifying an ore fluid source and time frame for Guizhou Au mineralization continues to be a critically important research goal for this district.

Yunnan-Guizhou-Guangxi region↗

USGS2018

Sulfur cycle in the Valles Caldera volcanic complex, New Mexico – Letter 1: Sulfate sources in aqueous system, and implications for S isotope record in Gale Crater on Mars

Initial in situ sulfur (S) isotope measurements of the Martian bedrock in Gale Crater have revealed an unexpectedly wide range of δ 34 S values (−47 to +28%). Generally, it is unclear what processes could have contributed to these large isotope fractionations. Therefore, we studied S sources and aqueous SO 2− 4 cycling in the Valles Caldera volcanic complex, New Mexico to better understand S isotope fractionations related to S degassing, hydrothermal activity, and low-temperature processes in aqueous environment. Overall, our study demonstrates that volcanic systems show large spatial heterogeneity in δ 34 S. Magmatic S sources are obvious in steam-dominated H 2 S degassing and precipitation of secondary minerals from hydrothermal fluids with low δ 34 S values of +0.9 ±3%. Locally, however, hydrothermal processes have resulted in more negative δ 34 S values in sulfide minerals (−18 to −4%) and more positive δ 34 S values in sulfate minerals (−1 to +3%). Major aqueous SO 2− 4 sources are oxidation of H 2 S from modern hydrothermal gas emission, and oxidation and dissolution of sulfide and sulfate minerals present in the hydrothermally altered bedrock and crater-lake sediments. The δ 34 S of aqueous SO 2− 4 in surface water and groundwater varies widely (−8 to +5%) and is similar to major S endmembers that undergo oxidation and/or dissolution by active hydrological system. Minor SO 2− 4 contributions with more positive δ 34 S values (+9 to +14%) come from deeply circulating geothermal fluids and negligible amounts from atmospheric deposition (+5 to +7% in snow). Elevated SO 2− 4 contents are mainly associated with modern and past H 2 S emissions and oxidations near the surface. On regional scale, however, most of the intracaldera bedrock is S-depleted, thus the SO 2− 4 contents are usually low in the surface aquatic system and younger sedimentary lake deposits formed at times of negligible near surface hydrothermal activity. In general, magmatic-hydrothermal processes apparently cause the largest δ 34 S variation in S-bearing minerals on volcanic terrains. Therefore, we infer that the measured wide range of δ 34 S values in the Gale sediments by the Curiosity rover on Mars can be explained by S isotope composition of magmatic-hydrothermal sulfide and sulfate minerals that were present in the initial igneous/volcanic rocks prior to crater formation. Later aqueous processes involved oxidation and dissolution of S minerals initially present in these rocks and led to subsequent formation of diagenetic fluids and alteration products enriched in SO 2− 4 with relatively large δ 34 S variation. Additionally, physical erosion, transport and deposition of detrital hydrothermal S minerals from igneous/volcanic rocks might be in part responsible for the measured wide range of δ 34 S in Gale Crater. These unique S isotope results, measured in situ on another planet for the first time, imply the importance of magmatic-hydrothermal fluids in S transport on early Mars and their subsequent alteration in low-temperature aqueous environments.

New Mexico↗

USGS2017

Mobilization of mercury and arsenic from a carbonate-hosted ore deposit, central Idaho, U.S.A.

The Cinnabar and Fern mine sites in central Idaho are primary source areas for elevated mercury and arsenic entering the South Fork of the Salmon River, which provides critical spawning habitat for bull trout and Chinook salmon. Mercury mineralization is hosted by carbonate rocks, which generate waters dominated by Ca2+ and HCO3 - at pH 7 to 9. A synoptic sampling was conducted on headwater tributaries to determine geologic background concentrations and quantify trace metal concentrations in stream water associated with historical mining. Geologic background concentrations in unfiltered Cinnabar Creek water were 8 - 14 ng Hg L-1 and 4.8 - 9.5 µg As L-1. Immediately downstream from the mine site, concentrations increased to 257 ng Hg L-1 and 20.6 µg As L-1. Groundwater inflow diluted these concentrations by approximately half before the confluence of Cinnabar Creek with Sugar Creek. As expected, mercury and arsenic concentrations increased downstream in Sugar Creek below the confluence with Cinnabar Creek. However, the final downstream reach on Sugar Creek showed an increase in unfiltered mercury, methylmercury, and iron concentrations relative to the upstream reach. This increase is associated with historical mining activity in a mineralized area of carbonate rock that intersects the reach.

Idaho↗

USGS2017

Iron isotope systematics of shale-derived soils as potentially influenced by small mineral particle loss

Loss of small mineral particles from soil has been suggested as a process that can produce net isotopic fractionation in the remaining soil. We extracted water dispersible colloids (WDCs) from bulk soil collected at the Susquehanna/Shale Hills Critical Zone Observatory (SSHO) and measured their Fe isotopic composition for comparison to published data from the site. The goal was to explain soil δ56Fe values that become lighter as Fe is lost from soil. The range of δ56Fe values for WDCs was 0.22 to 0.59 ‰, barely intersecting the value of ~0.8 ± 0.3‰ predicted by mass balance for particulate Fe loss by a previous study. The WDCs extracted likely represent a mixture of unfractionated Fe inherited from shale minerals and secondary Fe fractionated by weathering zone processes. Thus, although the WDC compositions do not confirm small mineral particle losses as causing overall Fe isotope fractionation in SSHO soils, they are compatible with that interpretation.

Conference Paper↗

USGS2016

Linking silicate weathering to riverine geochemistry—A case study from a mountainous tropical setting in west-central Panama

Chemical analyses from 71 watersheds across an ∼450 km transect in west-central Panama provide insight into controls on weathering and rates of chemical denudation and CO 2 consumption across an igneous arc terrain in the tropics. Stream and river compositions across this region of Panama are generally dilute, having a total dissolved solute value = 118 ± 91 mg/L, with bicarbonate and silica being the predominant dissolved species. Solute, stable isotope, and radiogenic isotope compositions are consistent with dissolution of igneous rocks present in Panama by meteoric precipitation, with geochemical signatures of rivers largely acquired in their upstream regions. Comparison of a headwater basin with its entire watershed observed considerably more runoff production from the high-elevation upstream portion of the catchment than in its much more spatially extensive downstream region. Rock alteration profiles document that weathering proceeds primarily by dissolution of feldspar and pyroxene, with base cations effectively leached in the following sequence: Na > Ca > Mg > K. Control on water chemistry by bedrock lithology is indicated through a linking of elevated ([Na + K]/[Ca + Mg]) ratios in waters to a high proportion of catchment area silicic bedrock and low ratios to mafic bedrock. Sr-isotope ratios are dominated by basement-derived Sr, with only very minor, if any, contribution from other sources. Cation weathering of Ca sil + Mg sil + Na + K spans about an order in magnitude, from 3 to 32 tons/km 2 /yr. Strong positive correlations of chemical denudation and CO 2 consumption are observed with precipitation, mean watershed elevation, extent of land surface forest cover, and physical erosion rate.

Chagras and Pacora watersheds↗

USGS2016

Isotopically constrained lead sources in fugitive dust from unsurfaced roads in the southeast Missouri mining district

The isotopic composition of lead (Pb) in fugitive dust suspended by a vehicle from 13 unsurfaced roads in Missouri was measured to identify the source of Pb within an established long-term mining area. A three end-member model using 207 Pb/ 206 Pb and concentration as tracers resulted in fugitive dust samples plotting in the mixing field of well characterized heterogeneous end members. End members selected for this investigation include the 207 Pb/ 206 Pb for 1) a Pb-mixture representing mine tailings, 2) aerosol Pb-impacted soils within close proximity to the Buick secondary recycling smelter, and 3) an average of soils, rock cores and drill cuttings representing the background conditions. Aqua regia total concentrations and 207 Pb/ 206 Pb of mining area dust suggest that 35.4–84.3% of the source Pb in dust is associated with the mine tailings mixture, 9.1–52.7% is associated with the smelter mixture, and 0–21.6% is associated with background materials. Isotope ratios varied minimally within the operational phases of sequential extraction suggesting that mixing of all three Pb mixtures occurs throughout. Labile forms of Pb were attributed to all three end members. The extractable carbonate phase had as much as 96.6% of the total concentration associated with mine tailings, 51.8% associated with smelter deposition, and 34.2% with background. The next most labile geochemical phase (Fe + Mn Oxides) showed similar results with as much as 85.3% associated with mine tailings, 56.8% associated with smelter deposition, and 4.2% associated with the background soil.

Missouri↗

USGS2015

Tracing historical trends of Hg in the Mississippi River using Hg concentrations and Hg isotopic compositions in a lake sediment core, Lake Whittington, Mississippi, USA

Concentrations and isotopic compositions of mercury (Hg) in a sediment core collected from Lake Whittington, an oxbow lake on the Lower Mississippi River, were used to evaluate historical sources of Hg in the Mississippi River basin. Sediment Hg concentrations in the Lake Whittington core have a large 10-15 y peak centered on the 1960s, with a maximum enrichment factor relative to Hg in the core of 4.8 in 1966. The Hg concentration profile indicates a different Hg source history than seen in most historical reconstructions of Hg loading. The timing of the peak is consistent with large releases of Hg from Oak Ridge National Laboratory (ORNL), primarily in the late 1950s and 1960s. Mercury was used in a lithiumisotope separation process by ORNL and an estimated 128Mg (megagrams) of Hgwas discharged to a local stream that flows into the Tennessee River and, eventually, the Mississippi River. Mass balance analyses of Hg concentrations and isotopic compositions in the Lake Whittington core fit a binary mixing model with a Hg-rich upstream source contributing about 70% of the Hg to Lake Whittington at the height of the Hg peak in 1966. This upstream Hg source is isotopically similar to Hg isotope compositions of stream sediment collected downstream near ORNL. It is estimated that about one-half of the Hg released from the ORNL potentially reached the LowerMississippi River basin in the 1960s, suggesting considerable downstream transport of Hg. It is also possible that upstream urban and industrial sources contributed some proportion of Hg to Lake Whittington in the 1960s and 1970s.

Chemical Geology↗

USGS2015

Sulfate and sulfide sulfur isotopes (δ34S and δ33S) measured by solution and laser ablation MC-ICP-MS: An enhanced approach using external correction

Isotope ratio measurements using a multi-collector inductively coupled plasma mass spectrometer (MC-ICP-MS) commonly use standard-sample bracketing with a single isotope standard for mass bias correction for elements with narrow-range isotope systems measured by MC-ICP-MS, e.g. Cu, Fe, Zn, and Hg. However, sulfur (S) isotopic composition (δ 34 S) in nature can range from at least − 40 to + 40‰, potentially exceeding the ability of standard-sample bracketing using a single sulfur isotope standard to accurately correct for mass bias. Isotopic fractionation via solution and laser ablation introduction was determined during sulfate sulfur (S sulfate ) isotope measurements. An external isotope calibration curve was constructed using in-house and National Institute of Standards and Technology (NIST) S sulfate isotope reference materials (RM) in an attempt to correct for the difference. The ability of external isotope correction for S sulfate isotope measurements was evaluated by analyzing NIST and United States Geological Survey (USGS) S sulfate isotope reference materials as unknowns. Differences in δ 34 S sulfate between standard-sample bracketing and standard-sample bracketing with external isotope correction for sulfate samples ranged from 0.72‰ to 2.35‰ over a δ 34 S range of 1.40‰ to 21.17‰. No isotopic differences were observed when analyzing S sulfide reference materials over a δ 34 S sulfide range of − 32.1‰ to 17.3‰ and a δ 33 S range of − 16.5‰ to 8.9‰ via laser ablation (LA)-MC-ICP-MS. Here, we identify a possible plasma induced fractionation for S sulfate and describe a new method using external isotope calibration corrections using solution and LA-MC-ICP-MS.

Chemical Geology↗

USGS2015

Isotopic geochemistry of Panama rivers

River water samples collected from 78 watersheds rivers along a 500-km transect across a Late Cretaceous-Tertiary andesitic volcanic arc terrane in west-central Panama provide a synoptic overview of riverine geochemistry, chemical denudation, and CO 2 consumption in the tropics. D/H and 18 O/ 16 O relationships indicate that bedrock dissolution of andesitic arc crust in Panama is driven by water-rock interaction with meteoric precipitation as it passes through the critical zone, with no evidence of a geothermal or hydrothermal input. Sr-isotope relationships suggest a geochemical evolution for Panama riverine waters that involves mixing of bedrock pore water with water having 87 Sr/ 86 Sr ratios between 0.7037-0.7043 and relatively high Sr-contents with waters of low Sr content that enriched in radiogenic Sr that are diluted by infiltrating rainfall to variable extents.

Procedia Earth and Planetary Science↗

USGS2015

Measurement of in situ sulfur isotopes by laser ablation multi-collector ICPMS: opening Pandora’s Box

Laser ablation multi-collector ICPMS is a modern tool for in situ measurement of S isotopes. Advantages of the technique are speed of analysis and relatively minor matrix effects combined with spatial resolution sufficient for many applications. The main disadvantage is a more destructive sampling mechanism relative to the ion microprobe technique. Recent advances in instrumentation allow precise measurement with spatial resolutions down to 25 microns. We describe specific examples from economic geology where increased spatial resolution has greatly expanded insights into the sources and evolution of fluids that cause mineralization and illuminated genetic relations between individual deposits in single mineral districts.

Procedia Earth and Planetary Science↗

USGS2015

Steep spatial gradients of volcanic and marine sulfur in Hawaiian rainfall and ecosystems

Sulfur, a nutrient required by terrestrial ecosystems, is likely to be regulated by atmospheric processes in well-drained, upland settings because of its low concentration in most bedrock and generally poor retention by inorganic reactions within soils. Environmental controls on sulfur sources in unpolluted ecosystems have seldom been investigated in detail, even though the possibility of sulfur limiting primary production is much greater where atmospheric deposition of anthropogenic sulfur is low. Here we measure sulfur isotopic compositions of soils, vegetation and bulk atmospheric deposition from the Hawaiian Islands for the purpose of tracing sources of ecosystem sulfur. Hawaiian lava has a mantle-derived sulfur isotopic composition (δ 34 S VCDT) of − 0.8&permil;. Bulk deposition on the island of Maui had a δ 34 S VCDT that varied temporally, spanned a range from + 8.2 to + 19.7&permil;, and reflected isotopic mixing from three sources: sea-salt (+ 21.1&permil;), marine biogenic emissions (+ 15.6&permil;), and volcanic emissions from active vents on Kilauea Volcano (+ 0.8&permil;). A straightforward, weathering-driven transition in ecosystem sulfur sources could be interpreted in the shift from relatively low (0.0 to + 2.7&permil;) to relatively high (+ 17.8 to + 19.3&permil;) soil δ 34 S values along a 0.3 to 4100 ka soil age-gradient, and similar patterns in associated vegetation. However, sub-kilometer scale spatial variation in soil sulfur isotopic composition was found along soil transects assumed by age and mass balance to be dominated by atmospheric sulfur inputs. Soil sulfur isotopic compositions ranged from + 8.1 to + 20.3&permil; and generally decreased with increasing elevation (0–2000 m), distance from the coast (0–12 km), and annual rainfall (180–5000 mm). Such trends reflect the spatial variation in marine versus volcanic inputs from atmospheric deposition. Broadly, these results illustrate how the sources and magnitude of atmospheric deposition can exert controls over ecosystem sulfur biogeochemistry across relatively small spatial scales.

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