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Zinc isotope investigation of surface and pore waters in a mountain watershed impacted by acid rock drainage

The pollution of natural waters with metals derived from the oxidation of sulfide minerals like pyrite is a global environmental problem. However, the metal loading pathways and transport mechanisms associated with acid rock drainage reactions are often difficult to characterize using bulk chemical data alone. In this study, we evaluated the use of zinc (Zn) isotopes to complement traditional geochemical tools in the investigation of contaminated waters at the former Waldorf mining site in the Rocky Mountains, Colorado, U.S.A. Geochemical signatures and statistical analysis helped in identifying two primary metal loading pathways at the Waldorf site. The first was characterized by a circumneutral pH, high alkalinity, and high Zn/Cd ratios. The second was characterized by acidic pHs and low Zn/Cd ratios. Zinc isotope signatures in surface water samples collected across the site were remarkably similar (the δ 66 Zn, relative to JMC 3-0749-L, for most samples ranged from 0.20 to 0.30‰ ± 0.09‰ 2σ). This probably suggests that the ultimate source of Zn is consistent across the Waldorf site, regardless of the metal loading pathway. The δ 66 Zn of pore water samples collected within a nearby metal-impacted wetland area, however, were more variable, ranging from 0.20 to 0.80‰ ± 0.09‰ 2σ. Here the Zn isotopes seemed to reflect differences in groundwater flow pathways. However, a host of secondary processes might also have impacted Zn isotopes, including adsorption of Zn onto soil components, complexation of Zn with dissolved organic matter, uptake of Zn into plants, and the precipitation of Zn during the formation of reduced sulfur species. Zinc isotope analysis proved useful in this study; however, the utility of this isotopic tool would improve considerably with the addition of a comprehensive experimental foundation for interpreting the complex isotopic relationships found in soil pore waters.

Colorado↗

Hydrothermal vents and methane seeps: Rethinking the sphere of influence

Although initially viewed as oases within a barren deep ocean, hydrothermal vent and methane seep communities are now recognized to interact with surrounding ecosystems on the sea floor and in the water column, and to affect global geochemical cycles. The importance of understanding these interactions is growing as the potential rises for disturbance from oil and gas extraction, seabed mining and bottom trawling. Here we synthesize current knowledge of the nature, extent and time and space scales of vent and seep interactions with background systems. We document an expanded footprint beyond the site of local venting or seepage with respect to elemental cycling and energy flux, habitat use, trophic interactions, and connectivity. Heat and energy are released, global biogeochemical and elemental cycles are modified, and particulates are transported widely in plumes. Hard and biotic substrates produced at vents and seeps are used by “benthic background” fauna for attachment substrata, shelter, and access to food via grazing or through position in the current, while particulates and fluid fluxes modify planktonic microbial communities. Chemosynthetic production provides nutrition to a host of benthic and planktonic heterotrophic background species through multiple horizontal and vertical transfer pathways assisted by flow, gamete release, animal movements, and succession, but these pathways remain poorly known. Shared species, genera and families indicate that ecological and evolutionary connectivity exists among vents, seeps, organic falls and background communities in the deep sea; the genetic linkages with inactive vents and seeps and background assemblages however, are practically unstudied. The waning of venting or seepage activity generates major transitions in space and time that create links to surrounding ecosystems, often with identifiable ecotones or successional stages. The nature of all these interactions is dependent on water depth, as well as regional oceanography and biodiversity. Many ecosystem services are associated with the interactions and transitions between chemosynthetic and background ecosystems, for example carbon cycling and sequestration, fisheries production, and a host of non-market and cultural services. The quantification of the sphere of influence of vents and seeps could be beneficial to better management of deep-sea environments in the face of growing industrialization.

Frontiers in Marine Science↗

"Sour gas" hydrothermal jarosite: Ancient to modern acid-sulfate mineralization in the southern Rio Grande Rift

As many as 29 mining districts along the Rio Grande Rift in southern New Mexico contain Rio Grande Rift-type (RGR) deposits consisting of fluorite-barite??sulfide-jarosite, and additional RGR deposits occur to the south in the Basin and Range province near Chihuahua, Mexico. Jarosite occurs in many of these deposits as a late-stage hydrothermal mineral coprecipitated with fluorite, or in veinlets that crosscut barite. In these deposits, many of which are limestone-hosted, jarosite is followed by natrojarosite and is nested within silicified or argillized wallrock and a sequence of fluorite-barite??sulfide and late hematite-gypsum. These deposits range in age from ???10 to 0.4 Ma on the basis of 40Ar/39Ar dating of jarosite. There is a crude north-south distribution of ages, with older deposits concentrated toward the south. Recent deposits also occur in the south, but are confined to the central axis of the rift and are associated with modern geothermal systems. The duration of hydrothermal jarosite mineralization in one of the deposits was approximately 1.0 my. Most ??18OSO4-OH values indicate that jarosite precipitated between 80 and 240 ??C, which is consistent with the range of filling temperatures of fluid inclusions in late fluorite throughout the rift, and in jarosite (180 ??C) from Pen??a Blanca, Chihuahua, Mexico. These temperatures, along with mineral occurrence, require that the jarosite have had a hydrothermal origin in a shallow steam-heated environment wherein the low pH necessary for the precipitation of jarosite was achieved by the oxidation of H2S derived from deeper hydrothermal fluids. The jarosite also has high trace-element contents (notably As and F), and the jarosite parental fluids have calculated isotopic signatures similar to those of modern geothermal waters along the southern rift; isotopic values range from those typical of meteoric water to those of deep brine that has been shown to form from the dissolution of Permian evaporite by deeply circulating meteoric water. Jarosite ??34S values range from -24??? to 5???, overlapping the values for barite and gypsum at the high end of the range and for sulfides at the low end. Most ??34S values for barite are 10.6??? to 13.1???, and many ??34S values for gypsum range from 13.1??? to 13.9??? indicating that a component of aqueous sulfate was derived from Permian evaporites (??34 S=12??2???). The requisite H2SO4 for jarosite formation was derived from oxidation of H2S which was likely largely sour gas derived from the thermochemical reduction of Permian sulfate. The low ??34S values for the precursor H2S probably resulted from exchange deeper in the basin with the more abundant Permian SO42- at ???150 to 200 ??C. Jarosite formed at shallow levels after the pH buffering capacity of the host rock (typically limestone) was neutralized by precipitation of earlier minerals. Some limestone-hosted deposits contain caves that may have been caused by the low pH of the deep basin fluids due to the addition of deep-seated HF and other magmatic gases during periods of renewed rifting. Caves in other deposits may be due to sulfuric acid speleogenesis as a result of H2S incursion into oxygenated groundwaters. The isotopic data in these "sour gas" jarosite occurrences encode a record of episodic tectonic or hydrologic processes that have operated in the rift over the last 10 my. ?? 2004 Elsevier B.V. All rights reserved.

Chemical Geology↗

Science support for evaluating natural recovery of polychlorinated biphenyl concentrations in fish from Crab Orchard Lake, Crab Orchard National Wildlife Refuge, Illinois

Introduction Crab Orchard Lake in southern Illinois is one of the largest and most popular recreational lakes in the state. Construction of the nearly 7,000-acre reservoir in the late 1930s created employment opportunities through the Works Progress Administration, and the lake itself was intended to supply water, control flooding, and provide recreational opportunities for local communities (Stall, 1954). In 1942, the Department of War appropriated or purchased more than 20,000 acres of land around Crab Orchard Lake and constructed the Illinois Ordnance Plant, which manufactured bombs and anti-tank mines during World War II. After the war, an Act of Congress transferred the property to the U.S. Department of the Interior. Crab Orchard National Wildlife Refuge was established on August 5, 1947, for the joint purposes of wildlife conservation, agriculture, recreation, and industry. Production of explosives continued, but new industries also moved onsite. More than 200 tenants have held leases with Crab Orchard National Wildlife Refuge and have operated a variety of manufacturing plants (electrical components, plated metal parts, ink, machined parts, painted products, and boats) on-site. Soils, water, and sediments in several areas of the refuge were contaminated with hazardous substances from handling and disposal methods that are no longer acceptable environmental practice (for example, direct discharge to surface water, use of unlined landfills). Polychlorinated biphenyl (PCB) contamination at the refuge was identified in the 1970s, and a PCB-based fish-consumption advisory has been in effect since 1988 for Crab Orchard Lake. The present advisory covers common carp ( Cyprinus carpio ) and channel catfish ( Ictalurus punctatus ); see Illinois Department of Public Health (2017). Some of the most contaminated areas of the refuge were actively remediated, and natural ecosystem recovery processes are expected to further reduce residual PCB concentrations in the lake. The U.S. Fish and Wildlife Service sought technical support to understand environmental drivers of current (2017) PCB residues in fish tissue and patterns in PCB residues through time to inform the fish-consumption advisory for Crab Orchard Lake. This project is planned in two phases (Tasks 1 and 2); the first phase is included in this report. Task 1, reported here, includes a review of existing literature and a brief overview focused on environmental and biochemical/physiological processes that drive PCB residues in fish tissue. This review specifically targets processes that are relevant for freshwater lacustrine environments such as those at Crab Orchard Lake. In addition to discussions of environmental fate, metabolism, and accumulation of PCBs, this review includes a brief scientifically based explanation of approaches used to establish fish-consumption advisories. A planned second task (Task 2) will include a compilation and summary of existing data on PCB residues in fish tissue samples from Crab Orchard Lake. This summary will also place Crab Orchard Lake data in a broader geographic context through a comparison with fish data from other Midwestern lakes. When Task 1 and Task 2 are complete, resource managers will have (a) a synthesis of existing literature that characterizes the processes influencing the fate of residual PCBs remaining in systems such as Crab Orchard Lake, (b) a summary of natural PCB attenuation processes for use in risk communication with the public, and (c) a summary of existing data on PCBs in fish tissues from Crab Orchard Lake, including exploratory plots of tissue residues through time. Overall, this project will provide data to help resource managers better understand the ecological and public health consequences of residual PCBs in Crab Orchard Lake.

Illinois↗

Methods of analysis by the U.S. Geological Survey National Water Quality Laboratory-Arsenic speciation in natural-water samples using laboratory and field methods

Analytical methods for the determination of arsenite [As(III)], arsenate [As(V)], dimethylarsinate (DMA), monomethylarsonate (MMA), and roxarsone in filtered natural-water samples are described. Various analytical methods can be used for the determination, depending on the arsenic species being determined. Arsenic concentration is determined by using inductively coupled plasma-mass spectrometry (ICP-MS) as an arsenic-specific detector for all methods. Laboratory-speciation methods are described that use an ion chromatographic column to separate the arsenic species; the column length, column packing, and mobile phase are dependent on the species of interest. Regardless of the separation technique, the arsenic species are introduced into plasma by eithe rpneumatic nebulization or arsine generation. Analysis times range from 2 to 8 minutes and method detection limits range from 0.1 to 0.6 microgram-arsenic per liter (ug-As/L), 10 to 60 picograms absolute (for a 100-microliter injection), depending on the arsenic species determined and the analytical method used. A field-generation specciation method also is described that uses a strong anion exchange cartridge to separate As(III) from As(V) in the field. As(III) in the eluate and the As(V) in the cartridge extract are determined by direct nebulization ICP-MS. Methylated arsenic species that also are retained on the cartridge will positively bias As(V) results without further laboratory separations. The method detection limit for field speciation is 0.3 ug-As/L. The distribution of arsenic species must be preserved in the field to eliminate changes caused by photochemical oxidation or metal oxyhydroxide precipitation. Preservation techniques, such as refrigeration, the addition of acides, or the additoin of ethylene-diaminetetraacetic acid (EDTA) and the effects of ambient light were tested. Of the preservatives evaluated, EDTA was found to work best with the laboratory- and field-speciation methods for all sample matrices tested. Storing the samples in opaque polytethylene bottles eliminated the effects of photochemical oxidation. The percentage change in As(III):As(V) ratios for an EDTA-preserved acid mine drainage (AMD) sample and ground-water sample during a 3-month period was -5 percent and +3 percent, respectively. The bias and variability of the methods were evaluated by comparing results for total arsenic and As(III), As(V), DMA, and MMA concentrations in ground water, AMD, and surface water. Seventy-one ground-water, 10 AMD, and 24 surface-water samples were analyzed. Concentrations in ground-water samples reached 720 ug-As/L for As(III) and 1080 ug-As/L for As(V); AMD samples reached 12800 ug-As/L for As(III) and 7050 ug-As/L for As(V); and surface-water samples reached 5 ug-As/L for As(III) and As(V). Inorganic arsenic species distribution in the samples ranged from 0 to 90 percent As(III). DMA and MMA were present only in surface-water samples from agricultural areas where the herbicide monosodium methylarsonate was applied; concentrations never exceeded 6 ug-As/L. Statistical analyses indicated that the difference between As(III) and As(V) concentrations for samples preserved with EDTA in opaque bottles and field-speciation results were analytically insignificant at the 95-percent confidence interval. There was no significant difference among the methods tested for total arsenic concentration. Percentage recovery for field samples spiked at 50 ug-As/L and analyzed by the laboratory-speciation method (n=2) ranged from 82 to 100 percent for As(III), 97 to 102 percent for As(V), 90 to 104 percent for DMA, and 81 to 96 percent for MMA; recoveries for samples spiked at 100 ug-As/L and analyzed by the field-speciation method ranged from 102 to 107 percent for As(III) and 105 to 106 percent for As(V). Laboratory-speciation results for Environment Canada reference material SLRS-2 closely matched reported concentrations. Laboratory-speciation metho

Water-Resources Investigations Report↗

Diel changes in water chemistry in an arsenic-rich stream and treatment-pond system

Arsenic concentrations are elevated in surface waters of the Warm Springs Ponds Operable Unit (WSPOU), located at the head of the upper Clark Fork River Superfund site, Montana, USA. Arsenic is derived from historical deposition of smelter emissions (Mill and Willow Creeks) and historical mining and milling wastes (Silver Bow Creek). Although long-term monitoring has characterized the general seasonal and flow-related trends in As concentrations in these streams and the pond system used to treat Silver Bow Creek water, little is known about solubility controls and sorption processes that influence diel cycles in As concentrations. Diel (24-h) sampling was conducted in July 2004 and August 2005 at the outlet of the treatment ponds, at two locations along a nearby reconstructed stream channel that diverts tributary water around the ponds, and at Silver Bow Creek 2 km below the ponds. Dissolved As concentration increased up to 51% during the day at most of the stream sites, whereas little or no diel change was displayed at the treatment-pond outlet. The strong cycle in streams is explained by pH- and temperature-dependent sorption of As onto hydrous metal oxides or biofilms on the streambed. Concentrations of dissolved Ca 2+ and HCO 3 − at the stream sites showed a diel temporal pattern opposite to that of As, and geochemical modeling supports the hypothesis that the concentrations of Ca 2+ and HCO 3 − were controlled by precipitation of calcite during the warm afternoon hours when pH rose above 9.0. Nightly increases in dissolved Mn and Fe(II) concentrations were out of phase with concentrations of other divalent cations and are more likely explained by redox phenomena.

Montana↗

Mercury contamination from historic mining in water and sediment, Guadalupe River and San Francisco Bay, California

The New Almaden mercury mines in California (USA), which collectively represent the largest historic producers of mercury in North America, are a persistent source of mercury contamination to the San Francisco Bay estuary. An estimate based on total mercury concentration (HgTOT) and provisional stream flow data measured at a gauging station in the Guadalupe River during base flow conditions yields a base flow flux of 30 g of mercury for the month of October 2000. In contrast to this base flow estimate, one 2-day rain event in October 2000 resulted in a flux of 22 g of mercury past this site. An estimate of mercury transport from the entire Guadalupe River watershed based on a sediment transport model and our measured suspended particulate HgTOT (0.5-4 ??g g-1) results in a total of 4-30 kg year-1 transported to the southern reach of the estuary. Sediments in the southern reach have lower HgTOT (most ??? 0.4 ??g g-1 dry wt) and monomethyl-mercury (MMHg, c. 1 ng g-1 dry wt) concentrations than those in the Guadalupe River (HgTOT, 0.41-33 ??g g-1 dry wt; MMHg, 1-10 ng g-1 dry wt). Because the most elevated methylmercury concentrations (8-12 ng g-1 dry wt) were found in sediments deposited immediately upstream of hydraulic structures (e.g. diversion dams and weirs) within the river, it is proposed that such physical structures may represent important zones of MMHg production and fluxes to San Francisco Bay.

Geochemistry: Exploration, Environment, Analysis↗

Peralkaline- and calc-alkaline-hosted volcanogenic massive sulfide deposits of the Bonnifield District, East-Central Alaska

Volcanogenic massive sulfide (VMS) Zn-Pb-Cu-Ag-Au deposits of the Bonnifield mining district formed during Late Devonian-Early Mississippian magmatism along the western edge of Laurentia. The largest deposits, Dry Creek and WTF, have a combined resource of 5.7 million tonnes at 10% Zn, 4% Pb, 0.3% Cu, 300 grams per tonne (g/t) Ag, and 1.6 g/t Au. These polymetallic deposits are hosted in high field strength element (HFSE)- and rare-earth element (REE)-rich peralkaline (pantelleritic) metarhyolite, and interlayered pyritic argillite and mudstone of the Mystic Creek Member of the Totatlanika Schist Formation. Mystic Creek metarhyolite and alkali basalt (Chute Creek Member) constitute a bimodal pair that formed in an extensional environment. A synvolcanic peralkaline quartz porphyry containing veins of fluorite, sphalerite, pyrite, and quartz intrudes the central footwall at Dry Creek. The Anderson Mountain deposit, located ~32 km to the southwest, occurs within calc-alkaline felsic to intermediate-composition metavolcanic rocks and associated graphitic argillite of the Wood River assemblage. Felsic metavolcanic rocks there have only slightly elevated HFSEs and REEs. The association of abundant graphitic and siliceous argillite with the felsic volcanic rocks together with low Cu contents in the Bonnifield deposits suggests classification as a siliciclastic-felsic type of VMS deposit. Bonnifield massive sulfides and host rocks were metamorphosed and deformed under greenschist-facies conditions in the Mesozoic. Primary depositional textures, generally uncommon, consist of framboids, framboidal aggregates, and spongy masses of pyrite. Sphalerite, the predominant base metal sulfide, encloses early pyrite framboids. Galena and chalcopyrite accompanied early pyrite formation but primarily formed late in the paragenetic sequence. Silver-rich tetrahedrite is a minor late phase at the Dry Creek deposit. Gold and Ag are present in low to moderate amounts in pyrite from all of the deposits; electrum inclusions occur in Dry Creek sphalerite. Contents and ratios of trace elements in graphitic argillite that serve as proxies for the redox state of the bottom waters in the basin indicate that Dry Creek mineralization took place in suboxic to periodically anoxic bottom waters. Trace element data show higher contents of Tl-Mn-As in pyrite from the Anderson Mountain deposit compared to the Dry Creek or WTF deposits and thus suggest that Anderson Mountain may have formed at lower temperatures or under slightly more oxidizing conditions. No exact modern analogue for the tectonic setting of the Bonnifield VMS deposits is known, although the back-arc regions of the Okinawa Trough and Woodlark Basin satisfy the requirement for a submarine, extensional setting adjacent to a continental margin. Limited occurrences of peralkaline volcanic rocks occur in these two potential analogues, but the peralkalinity of those rocks is much less than that of the Mystic Creek Member metarhyolites in the Bonnifield district. The highly elevated trace element (e.g., Zr, Nb) contents of Mystic Creek metarhyolites suggest that a better analogue may be a submarine rifted continental margin. The calc-alkaline composition of the host rocks to the Anderson Mountain deposit suggests that mineralization there formed in a continental margin arc, outboard of the extended continental margin setting of the peralkaline-hosted Dry Creek and WTF deposits.

Alaska↗

Concentration, distribution, and translocation of mercury and methylmercury in mine-waste, sediment, soil, water, and fish collected near the Abbadia San Salvatore mercury mine, Monte Amiata district, Italy

The distribution and translocation of mercury (Hg) was studied in the Paglia River ecosystem, located downstream from the inactive Abbadia San Salvatore mine (ASSM). The ASSM is part of the Monte Amiata Hg district, Southern Tuscany, Italy, which was one of the world’s largest Hg districts. Concentrations of Hg and methyl-Hg were determined in mine-waste calcine (retorted ore), sediment, water, soil, and freshwater fish collected from the ASSM and the downstream Paglia River. Concentrations of Hg in calcine samples ranged from 25 to 1500 μg/g, all of which exceeded the industrial soil contamination level for Hg of 5 μg/g used in Italy. Stream and lake sediment samples collected downstream from the ASSM ranged in Hg concentration from 0.26 to 15 μg/g, of which more than 50% exceeded the probable effect concentration for Hg of 1.06 μg/g, the concentration above which harmful effects are likely to be observed in sediment-dwelling organisms. Stream and lake sediment methyl-Hg concentrations showed a significant correlation with TOC indicating considerable methylation and potential bioavailability of Hg. Stream water contained Hg as high as 1400 ng/L, but only one water sample exceeded the 1000 ng/L drinking water Hg standard used in Italy. Concentrations of Hg were elevated in freshwater fish muscle samples and ranged from 0.16 to 1.2 μg/g (wet weight), averaged 0.84 μg/g, and 96% of these exceeded the 0.3 μg/g (methyl-Hg, wet weight) USEPA fish muscle standard recommended to protect human health. Analysis of fish muscle for methyl-Hg confirmed that > 90% of the Hg in these fish is methyl-Hg. Such highly elevated Hg concentrations in fish indicated active methylation, significant bioavailability, and uptake of Hg by fish in the Paglia River ecosystem. Methyl-Hg is highly toxic and the high Hg concentrations in these fish represent a potential pathway of Hg to the human food chain.

Monte Amiata↗

Geochemical investigations by the U.S. Geological Survey on uranium mining, milling, and environmental restoration

Recent research by the U.S. Geological Survey has characterized contaminant sources and identified important geochemical processes that influence transport of radionuclides from uranium mining and milling wastes. 1) Selective extraction studies indicated that alkaline earth sulfates and hydrous ferric oxides are important hosts of 226 Ra in uranium mill tailings. The action of sulfate-reducing and ironreducing bacteria on these phases was shown to enhance release of radium, and this adverse result may temper decisions to dispose of uranium mill tailings in anaerobic environments. 2) Field studies have shown that although surface-applied sewage sludge/wood chip amendments aid in revegetating pyritic spoil, the nitrogen in sludge leachate can enhance pyrite oxidation, acidification of groundwater, and the consequent mobilization of metals and radionuclides. 3) In a U.S. Environmental Protection Agencyfunded study, three permeable reactive barriers consisting of phosphate-rich material, zero-valent iron, or amorphous ferric oxyhydroxide have been installed at an abandoned uranium upgrader facility near Fry Canyon, UT. Preliminary results indicate that each of the permeable reactive barriers is removing the majority of the uranium from the groundwater. 4) Studies on the geochemistry of rare earth elements as analogues for actinides such as uranium and thorium in acid mine drainage environments indicate high mobility under acid-weathering conditions but measurable attenuation associated with iron and aluminum colloid formation. Mass balances from field and laboratory studies are being used to quantify the amount of attenuation. 5) A field study in Colorado demonstrated the use of 234 U/ 238 U isotopic ratio measurements to evaluate contamination of shallow groundwater with uranium mill effluent.

Utah↗

Ecosystem services: developing sustainable management paradigms based on wetland functions and processes

In the late nineteenth century and twentieth century, there was considerable interest and activity to develop the United States for agricultural, mining, and many other purposes to improve the quality of human life standards and prosperity. Most of the work to support this development was focused along disciplinary lines with little attention focused on ecosystem service trade-offs or synergisms, especially those that transcended boundaries of scientific disciplines and specific interest groups. Concurrently, human population size has increased substantially and its use of ecosystem services has increased more than five-fold over just the past century. Consequently, the contemporary landscape has been highly modified for human use, leaving behind a fragmented landscape where basic ecosystem functions and processes have been broadly altered. Over this period, climate change also interacted with other anthropogenic effects, resulting in modern environmental problems having a complexity that is without historical precedent. The challenge before the scientific community is to develop new science paradigms that integrate relevant scientific disciplines to properly frame and evaluate modern environmental problems in a systems-type approach to better inform the decision-making process. Wetland science is a relatively new discipline that grew out of the conservation movement of the early twentieth century. In the United States, most of the conservation attention in the earlier days was on wildlife, but a growing human awareness of the importance of the environment led to the passage of the National Environmental Policy Act in 1969. Concurrently, there was a broadening interest in conservation science, and the scientific study of wetlands gradually gained acceptance as a scientific discipline. Pioneering wetland scientists became formally organized when they formed The Society of Wetland Scientists in 1980 and established a publication outlet to share wetland research findings. In comparison to older and more traditional scientific disciplines, the wetland sciences may be better equipped to tackle today’s complex problems. Since its emergence as a scientific discipline, the study of wetlands has frequently required interdisciplinary and integrated approaches. This interdisciplinary/integrated approach is largely the result of the fact that wetlands cannot be studied in isolation of upland areas that contribute surface and subsurface water, solutes, sediments, and nutrients into wetland basins. However, challenges still remain in thoroughly integrating the wetland sciences with scientific disciplines involved in upland studies, especially those involved with agriculture, development, and other land-conversion activities that influence wetland hydrology, chemistry, and sedimentation. One way to facilitate this integration is to develop an understanding of how human activities affect wetland ecosystem services, especially the trade-offs and synergisms that occur when land-use changes are made. Used in this context, an understanding of the real costs of managing for a particular ecosystem service or groups of services can be determined and quantified in terms of reduced delivery of other services and in overall sustainability of the wetland and the landscapes that support them. In this chapter, we discuss some of the more salient aspects of a few common wetland types to give the reader some background on the diversity of functions that wetlands perform and the specific ecosystem services they provide to society. Wetlands are among the most complex ecosystems on the planet, and it is often difficult to communicate to a diverse public all of the positive services wetlands provide to mankind. Our goal is to help the reader develop an understanding that management options can be approached as societal choices where decisions can be made within a spatial and temporal context to identify trade-offs, synergies, and effects on long-term sustainability of wetland ecosystems. This will be especially relevant as we move into alternate climate futures where our portfolio of management options for mitigating damage to ecosystem function or detrimental cascading effects must be diverse and effective.

Book chapter↗

Geological and geochemical studies in the Wadi Bidah District, Kingdom of Saudi Arabia

Geological and geochemical followup studies of airborne electromagnetic anomalies in the Wadi Bidah district, southwestern Saudi Arabia, did not reveal metals of economic grade. Investigation of an anomaly enclosing the Rabathan ancient mine disclosed tightly folded and sheared Proterozoic tuffaceous rocks interlayered mostly with chert, dolomite, carbonaceous rocks, and volcanic wacke including cherty iron-manganese formations slightly anomalous in copper and zinc. Three drill holes placed to test anomalies within these formations yielded negative results. Studies of a long, narrow anomaly north of the Rabathan area indicated a similar geological environment. This northern area also contains limited zones that are highly anomalous in copper and zinc and extensive zones that are slightly anomalous in those metals. Drilling was not undertaken in this area. The Bilajimah airborne electromagnetic anomaly west of Wadi Bidah coincides with a broad synclinorium of layered felsic turfs and gossans. Geochemical studies indicated slightly anomalous copper, zinc, and silver values in gossans within the anomaly area. Two drill holes intersected carbonaceous rock that contained approximately 15 percent pyrrhotite and traces of sphalerite and chalcopyrite. Two geophysically anomalous areas west of Wadi Bidah surround ancient mines at Mahawiyah and Khayal al Masna'ah. Results of geochemical sampling at these workings were positive. An airborne electromagnetic anomaly located in the Assifar area in the southwestern corner of the Wadi Bidah district is underlain principally by metasedimentary rocks that include large linear zones of cherty iron-manganese formation and a few gossans .containing secondary base metal minerals. Detailed mapping and sampling of the Mulhal ancient mine, located west of Wadi Bidah, revealed two types of polymetallic gossans : (1) stratiform deposits interlayered with ignimbrites and mafic volcanic rocks and (2) barite-bearing gossanous material in shear zones that grade into hydrothermally altered shear zones and extend beyond the mine area. The gossans and gossanous shear zones contain anomalous amounts of gold, silver, lead, copper, zinc, barium, and selenium. Two gossans west of Wadi Bidah were mapped and sampled in detail; both gossans are interlayered, with siliceous volcanic rocks. Although the gossan at Jabal Mohr covers a large area, it contains low amounts of precious and base metals. The gossan at Mulhal No. 2 contains moderate to high amounts of gold, silver, copper, lead, and zinc.

Open-File Report↗

Legacy sediment as a potential source of orthophosphate: Preliminary conceptual and geochemical models for the Susquehanna River, Chesapeake Bay watershed, USA

Nutrient pollution from agriculture and urban areas plus acid mine drainage (AMD) from legacy coal mines are primary causes of water-quality impairment in the Susquehanna River, which is the predominant source of freshwater and nutrients entering the Chesapeake Bay. Recent increases in the delivery of dissolved orthophosphate (PO 4 ) from the river to the bay may be linked to long-term increases in pH, decreased acidity of precipitation, and decreased acidity, iron, and aluminum loading from widespread AMD. Since the 1950s, baseline pH increased from ~6.5 to ~8 in the West Branch and “North Branch” of the Susquehanna River, which drain bituminous and anthracite coalfields of Pennsylvania. A current baseline pH of ~8 and daily maxima exceeding 9 have been documented along the lower Susquehanna River. In response to improved river quality, bioavailable PO 4 now may be released into solution from legacy sediment that has filled major impoundments in lower reaches of the river. At typical pH (5–8) of natural water, aqueous PO 4 species tend to be adsorbed by hydrous iron, aluminum, and manganese oxides that coat soil and sediment particles; however, PO 4 may be substantially desorbed at pH >8. We created a geochemical model that simulates equilibrium aqueous/solid distributions of PO 4 as pH and other solution characteristics change. Considering current conditions in the lower Susquehanna River, the model demonstrates potential for extensive release of adsorbed PO 4 at pH >8. Empirical data from laboratory experiments corroborate model results. The transfer of PO 4 into the water column may increase algae growth, which removes CO 2 and drives pH to higher values, facilitating additional PO 4 release and exacerbating the potential for harmful algal blooms. Thus, legacy sediment is a currently unquantified source of PO 4 that warrants consideration by resource managers and programs collaborating to reduce phosphorus loads to the bay and similar settings worldwide.

Chesapeake Bay watershed↗

Fluorine, fluorite, and fluorspar in central Colorado

Fluorine (F) is a widespread element that was deposited in a variety of rocks, minerals, and geologic environments in central Colorado. It occurs as a trace element, as a major component of the mineral fluorite (CaFs), and as a major economic source of fluorine in fluorspar deposits, which are massive concentrations of fluorite. This study has compiled available geochemical analyses of rocks, both unmineralized and mineralized, to determine the distribution of fluorine in specific age-lithologic categories, ranging from 1.8-giga-annum (Ga) metamorphic rocks to modern soils, throughout central Colorado. It also draws upon field studies of fluorine-rich mineral deposits, including fluorspar deposits, to decipher the nearly two-billion-year-long geologic history of fluorine in the study area, with implications for mineral-resource evaluations and exploration. The resulting compilation provides an important inventory of the naturally occurring levels and sources of fluorine that ultimately weather, erode, and become part of surface waters that are used for domestic water supplies in densely populated areas along the Colorado Front Range. Most commonly, fluorine is a trace element in virtually all rocks in the region. In the 3,798 unmineralized rocks that were analyzed for fluorine in the study area, the average fluorine content was 1,550 parts per million (ppm). The median was 640 ppm, nearly identical to the average crustal abundance of 650 ppm, and some high-fluorine rocks in the Pikes Peak area skewed the average to a value much greater than the median. Most unmineralized age-lithologic rock suites, including Proterozoic metamorphic rocks, 1.7- and 1.4-Ga granitic batholiths, Cambrian igneous rocks, Phanerozoic sedimentary rocks, and Laramide and Tertiary igneous rocks, had median fluorine values of 400 to 740 ppm fluorine. In all suites, however, a small number of analyzed samples contained more than 1 percent (10,000 ppm) fluorine. The 1.1-Ga plutonic rocks related to the Pikes Peak batholith had a mean fluorine content of 1,700 ppm, and primary magmatic fluorite and fluorite-bearing pegmatites are common throughout that igneous mass. Fluorine was deposited in many types of economic mineral deposits in central Colorado, and it currently is a significant trace element in some thermal springs. In the fluorspar deposits, fluorine contents were as high as 37 percent. Some fluorine-rich porphyry systems, such as Jamestown, had fluorine values that ranged from 200 ppm to nearly 37 percent fluorine, and veins in other deposits contained hydrothermal fluorite, although it was not ubiquitous. For the 495 samples from non-fluorspar mining districts (and excluding Jamestown), however, the median fluorine content was 990 ppm. This is above the crustal average but still relatively modest compared to the fluorspar deposits, and it indicates that the majority of the mineralizing systems in central Colorado did not deposit large amounts of fluorine. Nevertheless, the fluorine- and fluorite-rich mineral deposits could be used as guides for the evaluation and discovery of related but concealed porphyry and epithermal base- and precious-metal deposits. The Cenozoic geologic history of central Colorado included multiple periods during which fluorine-bearing rocks and mineral deposits were exposed, weathered, and eroded. This protracted history has released fluorine into soils and regoliths, and modern rainfall and snowmelt interact with these substrates to add fluorine to the hydrosphere. This study did not evaluate the fluorine contents of water or make any predictions about what areas might be major sources for dissolved fluorine. However, the abundant data that are available on fluorine in surface water and ground water can be coupled with the results of this study to provide additional insight into natural sources of fluorine in domestic drinking water.

Scientific Investigations Report↗

Summary of reconnaissance for radioactive deposits in Alaska, 1945-1954, and an appraisal of Alaskan uranium possibilities

In the period 1945-1954 over 100 investigations for radioactive source materials were made in Alaska. The nature of these investigations ranged from field examinations of individual prospects or the laboratory analysis of significantly radioactive samples submitted by prospectors to reconnaissance studies of large districts. In this period no deposits of uranium or thorium that would warrant commercial exploitation were discovered. The investigations, however, disclosed that radioactive materials occur in widely scattered areas of Alaska and in widely diverse environments. Many igneous rocks throughout Alaska are weakly radioactive because of uranium- and thorium-bearing accessory minerals, such as allanite, apatite, monazite, sphene, xenotime, and zircon; more rarely the radioactivity of these rocks is due to thorianite or thorite and their uranoan varieties. The felsic rocks, for example, granites and syenites, are generally more radioactive than the mafic igneous rocks. Pegmatites, locally, have also proved to be radioactive, but they have little commercial significance. No primary uranium oxide minerals have been found yet in Alaskan vein deposits, except, perhaps, for a mineral tentatively identified as pitchblende in the Hyder district of southeastern Alaska. However, certain occurrences of secondary uranium minerals, chiefly those of the uranite group, on the Seward Peninsula, in the Russian Mountains, and in the vicinity of Kodiak suggest that pitchblende-type ores may occur at depth beneath zones of alteration. Thorite-bearing veins have been discovered on Prince of Wales Island in southeastern Alaska. Although no deposits or carnotite-type minerals have been found in Alaska, several samples containing such minerals have been submitted by Alaskan prospectors. Efforts to locate the deposits from which these minerals were obtained have been unsuccessful, but review of available geologic data suggests that several Alaskan areas are potentially favorable for carnotite-type deposits. The chief of these areas is the Alaska Peninsula-Cook Inlet area which encompasses most of the reported occurrences of the prospectors' carnotite-type samples. Alaska is also potentially favorable for the occurrence of large bodies of the very low-grade uraniferous sedimentary rocks, such as phosphorites and black shales. This type of deposit, however, has not received much study because of the emphasis on the search for bonanza-type high-grade ores. Uraniferous phosphorites similar to those of Idaho, Montana, and Wyoming occur in northern Alaska on the north flank of the Brooks Range; black shales comparable to the uraniferous shales of the Chattanooga formation of southeastern United States have been noted along the Yukon River near the international boundary. Placer deposits in Alaska have some small potential for the production of the radioactive elements as byproducts of gold- and tin-placer mining. the placer area believed to have the relatively greatest potential in Alaska lies in the Kahiltna River valley where concentrates are known to contain such commercial minerals as ilmenite, cassiterite, platinum, and gold in addition to uranothorianite and monazite. The possibilities of the natural fluids--water and petroleum--have not yet been tested in Alaska to any great extent. Studies of fluids are in progress to determine whether they may be used to discover and define areas potentially favorable for the occurrence of uraniferous lodes.

Alaska↗

Use of USGS earth-science products by county planning agencies in the San Francisco Bay region, California

An inventory of the use of USGS products in selected planning studies, plans, ordinances, and other planning activities was made for eight counties in the San Francisco Bay region--a region of almost five million people. This inventory was designed to determine and document the use of the 87 earth-science information products prepared as a part of the San Francisco Bay Region Environment and Resources Planning Study (SFBRS). The inventory showed that: (1) all eight counties had planning staffs who were very familiar with SFBRS products and had made frequent use of such products; (2) all eight counties had prepared planning documents which cite SFBRS products; (3) the types of planning applications most often indicated were: geologic hazards studies, seismic safety and public safety plan elements, general reference, and the preparation and review of environmental impact reports and statements; (4) over 90 percent of the 87 SFBRS products were used at least once, and nine of the products were used over 30 times each for various county planning activities; and (5) at least 85 other USGS products were also used for various county planning activities. After the inventory, selected county officials, employees, and consultants were interviewed and asked--among other things--to indicate any problems in the use of the SFBRS products, to suggest improvements, and to identify any needed or desired earth-science information. The responses showed that: (1) the scales commonly used for working maps were 1:62,500 or larger and for plan implementation were 1:24,000 or larger; (2) only one county had a geologist on its planning staff, although six others had the benefit of geotechnical services from private consulting firms, county engineering staffs, or the State Division of Mines and Geology; (3) seven of the eight counties expressed some problems in using the products, primarily because of their small scale or lack of detail; (4) all eight counties expected to continue to use the products and expressed a need or desire for additional earth-science, engineering, or other information; (5) all eight counties suggested specific improvements to future products, primarily larger scale or more detail and fewer technical or more interpretive products; and (6) all eight counties received educational, advisory, and review services from USGS personnel. Seventeen selected examples of the application of SFBRS products to various county planning activities are discussed and illustrated. These examples include four planning studies, seven plans, and two ordinances. From the inventory and responses to the interviews, it is concluded that the counties in the Bay region are very familiar with, have made frequent use of, and will continue to use SFBRS products for a wide range of county planning activities. Suggestions to ensure more effective use of earth-science information in the future include: (1) monitoring emerging critical issues and analyzing new state and federal laws and regulations so as to better anticipate and respond to county earth-science information needs; (2) creating a users advisory committee to help identify critical issues and user needs; (3) providing engineering interpretations and land- and water-use capability ratings to make earth-science information more readily usable; (4) giving priority to areas impacted by development so as to husband staff resources; (5) providing earth-science information at the larger scale and greater detail commonly used and needed by counties; (6) releasing earth-science information earlier and according to a formal distribution pattern; and (7) providing educational, advisory, and review services in connection with any earth-science information designed for planners and decisionmakers.

Open-File Report↗

Reconnaissance of potential alternate water supply sources for the City of Gary, West Virginia

Seven potential sources of water, consisting of free-flowing discharge from abandoned coal mines at six locations and one abandoned flooded underground coal mine air shaft, were sampled for chemical analysis to assess the quality of the groundwater emanating from the seven mine sources. The six free-flowing mine discharge sources were also assessed for discharge by current-meter measurements on two separate occasions. The U.S. Geological Survey assessed these seven sources to provide information to the City of Gary, West Virginia (W. Va.), and the City of Gary’s consulting engineer with groundwater-quality and flow data to allow them to assess the seven sites as potential alternate sources of water for the City of Gary to augment its existing supply. For the six sites where discharge could be measured, discharge ranged from a minimum of 0.082 cubic feet per second (ft 3 /s) to a maximum of 3.685 ft 3 /s. Of the six sites measured, only two, Harmon Branch at Thorpe, W. Va. (USGS site 372201081303501) and the abandoned public-supply water wells near Havaco, W. Va. (USGS site 372358081344601), had discharge in excess of 1.00 ft 3 /s. Discharge from the abandoned public supply wells was 3.685 ft 3 /s on September 20, 2023, and 2.888 ft 3 /s on October 16, 2023, and discharge from Harmon Branch at Thorpe, W. Va., was 1.049 ft 3 /s on September 22, 2023, and 1.038 ft 3 /s on October 17, 2023. Discharge in the abandoned underground mine air shaft (USGS site 372224081340901) could not be assessed, but the air shaft drains an abandoned mine that likely contains water stored in approximately 1.7 square miles (mi 2 ) of abandoned underground coal mines in the Pocahontas No. 3 coal seam, and possibly an additional 0.9 mi 2 of leakage from the overlying Pocahontas No. 4 coal seam. Discharge for the six sites measured for the study was measured during a period between September 20 and October 18, 2023, and corresponded to the 12th to the 15th percentile of flow-duration statistics for the Tug Fork downstream of Elkhorn Creek at Welch, W. Va. streamgage (USGS site 03212750). Water-quality data for the seven sites sampled overall were acceptable with respect to drinking water standards. Of the 203 constituents analyzed, only a few failed to meet applicable U.S. Environmental Protection Agency (EPA) drinking water standards. Iron exceeded the 300 micrograms per liter (μg/L) secondary maximum contaminant level (SMCL) at only 1 of the 7 sites (14.3 percent) sampled. Iron concentrations ranged from a minimum of less than (<) 5.00 μg/L to a maximum of 724 μg/L with a median concentration of 7.62 μg/L. Manganese exceeded the 50.0 μg/L SMCL at 2 of the 7 sites (28.6 percent) sampled. Manganese concentrations ranged from a minimum of 1.93 μg/L to a maximum of 271 μg/L with a median concentration of 4.03 μg/L. No sites sampled exceeded the arsenic maximum contaminant level (MCL) of 10 μg/L. Arsenic concentrations ranged from a minimum of <0.100 μg/L to a maximum of 2.35 μg/L with a median arsenic concentration of 0.200 μg/L. None of the seven sites sampled for selenium for this study exceeded the EPA MCL of 50.0 μg/L. Selenium concentrations ranged from a minimum of <0.050 μg/L to a maximum of 5.26 μg/L with a median concentration of 3.21 μg/L. All seven sites were sampled for volatile organic compounds (VOCs), semivolatile organic compounds (SVOCs), and polychlorinated biphenyls (PCBs), but most had concentrations below the detection limit. Of the 10 PCB compounds analyzed for the seven sites sampled, none contained detectable concentrations of PCBs or Aroclor compounds. Of the 44 SVOCs analyzed at each of the seven sites sampled, only 1 SVOC, acenaphthene, was detected, at a concentration of 0.02 μg/L. Of the 96 VOCs analyzed, from each of the seven sites sampled, only two were found at detectable concentrations. Trichloromethane was detected only at 1 of the 7 (14.3 percent) sites sampled at a concentration of 0.027 μg/L, and benzene was detected at the same site and 3 additional sites (4 of the 7 sites or 57.1 percent of the sites sampled) at concentrations of 0.028, 0.029, 0.021, and 0.035 μg/L, but none exceeded the EPA MCL for benzene of 5.00 μg/L. Total coliform bacteria are ubiquitous in the environment, and their presence only suggests the potential for contamination by near-surface processes. Escherichia coli ( E. coli ) bacteria are derived from either human or animal fecal material and can be an indicator of potential contamination by pathogenic bacteria or viruses. Total coliform bacteria were detected at all 7 sites sampled at concentrations ranging from 17.5 to greater than (>) 2,420 most probable number per 100 mL (MPN/100 mL) of sample, with a median total coliform concentration of 1,553 MPN/100 mL. Escherichia coli bacteria were detected at 4 of the 7 sites sampled at concentrations ranging from <1 to 11.9 MPN/100 mL, with a median E. coli concentration of 5.1 MPN/100 mL.

West Virginia↗

Mineralogy and environmental geochemistry of historical iron slag, Hopewell Furnace National Historic Site, Pennsylvania, USA

The Hopewell Furnace National Historic Site in southeastern Pennsylvania, which features an Fe smelter that was operational in the 18th and 19th centuries, is dominated by three slag piles. Pile 1 slag, from the Hopewell Furnace, and pile 2 slag, likely from the nearby Cornwall Furnace, were both produced in cold-blast charcoal-fired smelters. In contrast, pile 3 slag was produced in an anthracite furnace. Ore samples from the nearby Jones and Hopewell mines that fed the smelter are mainly magnetite-rich with some sulfides (pyrite, chalcopyrite, sphalerite) and accessory silicates (quartz, garnet, feldspar, and clay minerals). Slag piles 1 and 2 are similar mineralogically containing predominantly skeletal and dendritic aluminian diopside and augite, skeletal forsteritic olivine, glass, rounded blebs of metallic Fe, and exotic quartz. Olivine is a major phase in all samples from pile 2, whereas it occurs in only a few samples from pile 1. Samples of the <2 mm-size fraction of surface composite slag material or crushed slag from at depth in piles 1 and 2 are mineralogically similar to the large surface slag fragments from those piles with the addition of phases such as feldspars, Fe oxides, and clay minerals that are either secondary weathering products or entrained from the underlying bedrock. Pile 3 slag contains mostly skeletal forsteritic olivine and Ti-bearing aluminian diopside, dendritic or fine-grained subhedral melilite, glass, euhedral spinel, metallic Fe, alabandite–oldhamite solid solution, as well as a sparse Ti carbonitride phase. The bulk chemistry of the slag is dominated by Al 2 O 3 (8.5–16.2 wt.%), CaO (8.2–26.2 wt.%), MgO (4.2–24.7 wt.%), and SiO 2 (36.4–59.8 wt.%), constituting between 81% and 97% of the mass of the samples. Piles 1 and 2 are chemically similar; pile 1 slag overall contains the highest Fe 2 O 3 , K 2 O and MnO, and the lowest MgO concentrations. Pile 3 slag is high in Al 2 O 3 , CaO and S, and low in Fe 2 O 3 , K 2 O and SiO 2 compared to the other piles. In general, piles 1 and 2 are chemically similar to each other, whereas pile 3 is distinct – a conclusion that reflects their mineralogy. The similarities and differences among piles in terms of mineralogy and major element chemistry result from the different smelting conditions under which the slag formed and include the fuel source, the composition of the ore and flux, the type of blast (cold versus hot), which affects the furnace temperature, and other beneficiation methods. The three distinct slag piles at Hopewell are enriched in numerous trace elements, such as As (up to 12 mg/kg), Cd (up to 0.4 mg/kg), Co (up to 31.8 mg/kg), Cu (up to 647 mg/kg), Mn (up to 0.69 wt.%), Pb (up to 172 mg/kg) and Zn (up to 393 mg/kg), together with Fe (13.9 wt.%), when compared to the average for the continental crust, with the <2 mm-size fraction commonly containing the highest concentrations. Enrichments in various elements (e.g., Cd, Co, Cu, Pb, Zn) were also found in the ore samples. Despite these enrichments, comparison of bulk chemistry trace-element concentrations to the environmental guidelines suggests most elements are likely not problematic with the exception of As, Co, Fe and Mn. Leachate tests that simulate weathering indicate Fe (up to 973 μg/L) and Mn (up to 133 μg/L) are readily released in potentially harmful concentrations compared to secondary drinking water and some aquatic ecosystem toxicity criteria. Aluminum and Cu, although not high in the solid compared to environmental guidelines, also exceed relevant criteria in leachate extracts with maximum concentrations of 2700 μg/L and 17.7 μg/L, respectively. In contrast, As and Co, which are significant in the solids, are not leached in concentrations that exceed guidelines (i.e., 3 μg/L or less for both elements). The weathering rates of the Fe metal and Fe oxides, which host Cu and some Fe, are likely higher than the silicate glass, which hosts the majority of Al, Mn and some Fe, and the crystalline silicates and spinels affecting which elements and how much are released into the environment and surrounding aquatic ecosystem. The mineral assemblages and their chemical composition, the bulk sample chemistry, and leachability of trace elements are all important components in understanding the potential environmental impacts of the slag piles.

Pennsylvania↗