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USGS2005

"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↗

USGS2006

Hydrogeologic framework refinement, ground-water flow and storage, water-chemistry analyses, and water-budget components of the Yuma area, southwestern Arizona and southeastern California

The ground-water and surface-water system in the Yuma area in southwestern Arizona and southeastern California is managed intensely to meet water-delivery requirements of customers in the United States, to manage high ground-water levels in the valleys, and to maintain treaty-mandated water-quality and quantity requirements of Mexico. The following components in this report, which were identified to be useful in the development of a ground-water management model, are: (1) refinement of the hydrogeologic framework; (2) updated water-level maps, general ground-water flow patterns, and an estimate of the amount of ground water stored in the mound under Yuma Mesa; (3) review and documentation of the ground-water budget calculated by the Bureau of Reclamation, U.S. Department of the Interior (Reclamation); and (4) water-chemistry characterization to identify the spatial distribution of water quality, information on sources and ages of ground water, and information about the productive-interval depths of the aquifer. A refined three-dimensional digital hydrogeologic framework model includes the following hydrogeologic units from bottom to top: (1) the effective hydrologic basement of the basin aquifer, which includes the Pliocene Bouse Formation, Tertiary volcanic and sedimentary rocks, and pre-Tertiary metamorphic and plutonic rocks; (2) undifferentiated lower units to represent the Pliocene transition zone and wedge zone; (3) coarse-gravel unit; (4) lower, middle, and upper basin fill to represent the upper, fine-grained zone between the top of the coarse-gravel unit and the land surface; and (5) clay A and clay B. Data for the refined model includes digital elevation models, borehole lithology data, geophysical data, and structural data to represent the geometry of the hydrogeologic units. The top surface of the coarse-gravel unit, defined by using borehole and geophysical data, varies similarly to terraces resulting from the down cutting of the Colorado River. Clay A is nearly the same as the previous conceptual hydrogeologic model definition (Olmsted and others, 1973), except for a minor westward extension from the city of Yuma. Clay B is extended to the southerly international boundary and increased in areal extent by about two-thirds of the original extent (Olmsted and others, 1973). The other hydrogeologic units generally are the same as in the previous conceptual hydrogeologic model. Before development, the Colorado and Gila Rivers were the sources of nearly all the ground water in the Yuma area through direct infiltration of water from river channels and annual overbank flooding. After construction of upstream reservoirs and clearing and irrigation of the floodplains, the rivers now act as drains for the ground water. Ground-water levels in most of the Yuma area are higher now than they were in predevelopment time. A general gradient of ground-water flow toward the natural discharge area south of the Yuma area still exists, but many other changes in flow are evident. Ground water in Yuma Valley once flowed away from the Colorado River, but now has a component of flow towards the river and Mexicali Valley. A ground-water mound has formed under Yuma Mesa from long-term surface-water irrigation; about 600,000 to 800,000 acre-ft of water are stored in the mound. Ground-water withdrawals adjacent to the southerly international boundary have resulted in water-level declines in that area. The reviewed and documented water budget includes the following components: (1) recharge in irrigated areas, (2) evapotranspiration by irrigated crops and phreatophytes, (3) ground-water return flow to the Colorado River, and (4) ground-water withdrawals (including those in Mexicali Valley). Recharge components were calculated by subtracting the amount of water used by crops from the amount of water delivered. Evapotranspiration rates were calculated on the basis of established methods, thus were appropriate for input to the ground-water flow model developed by the Bureau of Reclamation (William Greer, hydrologist, Bureau of Reclamation, written commun., 2005). Evapotranspiration by crops and phreatophytes were calculated by using crop coefficient methods and meteorological data. Other methods of calculating evapotranspiration rates by using combinations of satellite imagery and ground-based data could be used for higher spatial and temporal resolution. Ground-water return flow during years of low flow on the Colorado River (1972–82, 1987–92, and 1994–96) averaged 79,000 acre-ft per year. Ground-water withdrawal data for 1970–99 were similar to other estimates made by the U.S. Geological Survey for the Yuma area. New water-chemistry data were collected in 12 wells and 8 canals/drains to characterize spatial patterns in chemical constituents, determine isotopic ages of water, infer possible sources of ground water, and locate the vertical intervals of the aquifer that contribute most water to wells. Depth-dependent samples were collected at one of the wells (YM-10). A large quantity of water-quality data were compiled from Bureau of Reclamation and U.S. Geological Survey records and merged into the U.S. Geological Survey National Water Information System database. New samples were analyzed for major ions, nutrients, stable isotopes of oxygen and hydrogen, tritium ( 3 H), and carbon-14 ( 14 C) (along with C 13 /C 12 ratios). Light values of oxygen-18 ( 18 O) and deuterium ( 2 H, D) in well 242-2 indicate recharge from the Colorado River. Heavy water samples from wells 242-22, CADC, and Mesa del Sol indicate local recharge sources. Tritium data indicate there is young water in wells in the valleys and near the edge of Yuma Mesa, while older water is found far from the Colorado River. 14 C data indicate that water from wells near the southerly international boundary is at least several thousand years old.

Arizona, California↗

USGS1989

Characterization of coal-derived hydrocarbons and source-rock potential of coal beds, San Juan Basin, New Mexico and Colorado, U.S.A.

Coal beds are considered to be a major source of nonassociated gas in the Rocky Mountain basins of the United States. In the San Juan basin of northwestern New Mexico and southwestern Colorado, significant quantities of natural gas are being produced from coal beds of the Upper Cretaceous Fruitland Formation and from adjacent sandstone reservoirs. Analysis of gas samples from the various gas-producing intervals provided a means of determining their origin and of evaluating coal beds as source rocks. The rank of coal beds in the Fruitland Formation in the central part of the San Juan basin, where major gas production occurs, increases to the northeast and ranges from high-volatile B bituminous coal to medium-volatile bituminous coal ( R m values range from 0.70 to 1.45%). On the basis of chemical, isotopic and coal-rank data, the gases are interpreted to be thermogenic. Gases from the coal beds show little isotopic variation ( δ 13 C 1 values range −43.6 to −40.5 ppt), are chemically dry (C 1 /C 1–5 values are > 0.99), and contain significant amounts of CO 2 (as much as 6%). These gases are interpreted to have resulted from devolatilization of the humic-type bituminous coal that is composed mainly of vitrinite. The primary products of this process are CH 4 , CO 2 and H 2 O. The coal-generated, methane-rich gas is usually contained in the coal beds of the Fruitland Formation, and has not been expelled and has not migrated into the adjacent sandstone reservoirs. In addition, the coal-bed reservoirs produce a distinctive bicarbonate-type connate water and have higher reservoir pressures than adjacent sandstones. The combination of these factors indicates that coal beds are a closed reservoir system created by the gases, waters, and associated pressures in the micropore coal structure. In contrast, gases produced from overlying sandstones in the Fruitland Formation and underlying Pictured Cliffs Sandstone have a wider range of isotopic values ( δ 13 C 1 values range from −43.5 to −38.5 ppt), are chemically wetter (C 1 /C 1–5 values range from 0.85 to 0.95), and contain less CO 2 (< 2%). These gases are interpreted to have been derived from type III kerogen dispersed in marine shales of the underlying Lewis Shale and nonmarine shales of the Fruitland Formation. In the underlying Upper Cretaceous Dakota Sandstone and Tocito Sandstone Lentil of the Mancos Shale, another gas type is produced. This gas is associated with oil at intermediate stages of thermal maturity and is isotopically lighter and chemically wetter at the intermediate stage of thermal maturity as compared with gases derived from dispersed type III kerogen and coal; this gas type is interpreted to have been generated from type II kerogen. Organic matter contained in coal beds and carbonaceous shales of the Fruitland Formation has hydrogen indexes from Rock-Eval pyrolysis between 100 and 350, and atomic H:C ratios between 0.8 and 1.2. Oxygen indexes and atomic O:C values are less than 24 and 0.3, respectively. Extractable hydrocarbon yields are as high as 7,000 ppm. These values indicate that the coal beds and carbonaceous shales have good potential for the generation of liquid hydrocarbons. Voids in the coal filled with a fluorescent material that is probably bitumen is evidence that liquid hydrocarbon generation has taken place. Preliminary oil-source rock correlations based on gas chromatography and stable carbon isotope ratios of C 15+ hydrocarbons indicate that the coals and (or) carbonaceous shales in the Fruitland Formation may be the source of minor amounts of condensate produced from the coal beds at relatively low levelsof thermal maturity ( R m =0.7).

International Journal of Coal Geology↗

USGS1997

Ground Water Atlas of the United States: Segment 11, Delaware, Maryland, New Jersey, North Carolina, Pennsylvania, Virginia, West Virginia

Segment 11 consists of the States of Delaware, Maryland, New Jersey, North Carolina, West Virginia, and the Commonwealths of Pennsylvania and Virginia. All but West Virginia border on the Atlantic Ocean or tidewater. Pennsylvania also borders on Lake Erie. Small parts of northwestern and north-central Pennsylvania drain to Lake Erie and Lake Ontario; the rest of the segment drains either to the Atlantic Ocean or the Gulf of Mexico. Major rivers include the Hudson, the Delaware, the Susquehanna, the Potomac, the Rappahannock, the James, the Chowan, the Neuse, the Tar, the Cape Fear, and the Yadkin-Peedee, all of which drain into the Atlantic Ocean, and the Ohio and its tributaries, which drain to the Gulf of Mexico. Although rivers are important sources of water supply for many cities, such as Trenton, N.J.; Philadelphia and Pittsburgh, Pa.; Baltimore, Md.; Washington, D.C.; Richmond, Va.; and Raleigh, N.C., one-fourth of the population, particularly the people who live on the Coastal Plain, depends on ground water for supply. Such cities as Camden, N.J.; Dover, Del.; Salisbury and Annapolis, Md.; Parkersburg and Weirton, W.Va.; Norfolk, Va.; and New Bern and Kinston, N.C., use ground water as a source of public supply. All the water in Segment 11 originates as precipitation. Average annual precipitation ranges from less than 36 inches in parts of Pennsylvania, Maryland, Virginia, and West Virginia to more than 80 inches in parts of southwestern North Carolina (fig. 1). In general, precipitation is greatest in mountainous areas (because water tends to condense from moisture-laden air masses as the air passes over the higher altitudes) and near the coast, where water vapor that has been evaporated from the ocean is picked up by onshore winds and falls as precipitation when it reaches the shoreline. Some of the precipitation returns to the atmosphere by evapotranspiration (evaporation plus transpiration by plants), but much of it either flows overland into streams as direct runoff or enters streams as base flow (discharge from one or more aquifers). The distribution of average annual runoff (fig. 2) is similar to the distribution of precipitation; that is, runoff is generally greatest where precipitation is greatest. Runoff rates range from more than 50 inches per year in parts of western North Carolina to less than 12 inches in parts of North Carolina, Virginia, and West Virginia. Parts of the seven following physiographic provinces are in Segment 11: the Coastal Plain, the Piedmont, the Blue Ridge, the New England, the Valley and Ridge, the Appalachian Plateaus, and the Central Lowland. The provinces generally trend northeastward (fig. 3). The northeastern terminus of the Blue Ridge Province is in south-central Pennsylvania, and the southwestern part of the New England Province, the Reading Prong, ends in east-central Pennsylvania. The topography, lithology, and water-bearing characteristics of the rocks that underlie the Blue Ridge Province and the Reading Prong are similar. Accordingly, for purposes of this study, the hydrology of the Reading Prong is discussed with that of the Blue Ridge Province. The Coastal Plain Province is a lowland that borders the Atlantic Ocean. The Coastal Plain is as much as 140 miles wide in North Carolina but narrows northeastward to New Jersey where it terminates in Segment 11 at the south shore of Raritan Bay. Although it is generally a flat, seaward-sloping lowland, this province has areas of moderately steep local relief, and its surface locally reaches altitudes of 350 feet in the southwestern part of the North Carolina Coastal Plain. The Coastal Plain mostly is underlain by semiconsolidated to unconsolidated sediments that consist of silt, clay, and sand, with some gravel and lignite. Some consolidated beds of limestone and sandstone are present. The Coastal Plain sediments range in age from Jurassic to Holocene and dip gently toward the ocean. The boundary between the Coastal Plain and the Piedmont Provinces is called the Fall Line (fig. 3) because falls and rapids commonly form where streams cross the contact between the consolidated rocks of the Piedmont (fig. 4) and the soft, semiconsolidated to unconsolidated sediments of the Coastal Plain. The increase in stream gradient at the Fall Line provided favorable locations for mills and other installations that harnessed water power during the early years of the Industrial Revolution, and on most major rivers, the Fall Line coincides with the head of navigation. The Piedmont Province is an area of varied topography that ranges from lowlands to peaks and ridges of moderate altitude and relief. The metamorphic and igneous rocks of this province range in age from Precambrian to Paleozoic and have been sheared, fractured, and folded. Included in this province, however, are sedimentary basins that formed along rifts in the Earth's crust and contain shale, sandstone, and conglomerate of early Mesozoic age, interbedded locally with basaltic lava flows and minor coal beds. The sedimentary rocks and basalt flows are intruded in places by diabase dikes and sills. The mountain belt of the Blue Ridge Province forms the northwestern margin of the Piedmont in most of Segment 11. This belt consists mostly of igneous and high-rank metamorphic rocks but also includes low-rank metamorphic rocks of late Precambrian age and small areas of sedimentary rocks of Early Cambrian age along its western margin. In this report, the Reading Prong of the New England Province, which is an upland that extends from east of the Susquehanna River in Pennsylvania northeastward into New Jersey (fig. 3), is treated as part of the Blue Ridge Province. Part of the Reading Prong in Pennsylvania and New Jersey and a small part of the Piedmont Province in northeastern New Jersey have been glaciated. Glacial deposits completely or partly fill some of the valleys, and the eroding action of the glacial ice removed some of the rock from the ridges. Thus, the glaciated parts of the province have a smoother topography and less relief than other parts. The Valley and Ridge Province is characterized by layered sedimentary rock that has been complexly folded and locally thrust faulted. As the result of repeated cycles of uplift and erosion, resistant layers of well-cemented sandstone and conglomerate form elongate mountain ridges and less resistant, easily eroded layers of limestone, dolomite, and shale form valleys. The rocks of the province range in age from Cambrian to Pennsylvanian. Parts of this province from central Pennsylvania into New Jersey have been glaciated, and glacial deposits fill or partially fill some of the valleys. The Appalachian Plateaus Province is underlain by rocks that are continuous with those of the Valley and Ridge Province, but in the Appalachian Plateaus the layered rocks are nearly flat-lying or gently tilted and warped, rather than being intensively folded and faulted. The boundary between the two provinces is a prominent southeast-facing scarp called the Allegheny Front in most of the northern part of Segment 11 (fig_ 5) and the Cumberland Escarpment in the southern part. The scarp faces the Valley and Ridge Province, and throughout most of the segment, the eastern edge of the Appalachian Plateaus Province is higher than the ridges in the Valley and Ridge. Like parts of the Reading Prong and the Valley and Ridge Province, the northern part of the Appalachian Plateaus Province in Pennsylvania has been glaciated. In the glaciated section, the surface is mantled by glacial drift, and the valleys are partly filled with glacial deposits. The northwestern corner of Segment 11 contains a small part of the Central Lowland Province. This flat lowland is underlain by gently dipping sedimentary rocks, some of which are the same geologic formations as those of the Appalachian Plateaus Province. The two provinces are separated by a northwest- facing scarp. Because of the small area of the Central Lowland Province within the segment and the similarity of aquifer properties with those of the glaciated part of the Appalachian Plateaus Province, the two provinces are discussed together in this report.

Delaware, Maryland, New Jersey, North Carolina, Pe↗