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Volatilization of benzene and eight alkyl-substituted benzene compounds from water

Predicting the fate of organic compounds in streams and rivers often requires knowledge of the volatilization characteristics of the compounds. The reference-substance concept, involving laboratory-determined ratios of the liquid-film coefficients for volatilization of the organic compounds to the liquid-film coefficient for oxygen absorption, is used to predict liquid-film coefficients for streams and rivers. In the absence of experimental data, two procedures have been used for estimating these liquid-film coefficient ratios. These procedures, based on the molecular-diffusion coefficient and on the molecular weight, have been widely used but never extensively evaluated. Liquid-film coefficients for the volatilization of benzene and eight alkyl-substituted benzene compounds (toluene through n-octylbenzene) from water were measured in a constant-temperature, stirred water bath. Liquid-film coefficients for oxygen absorption were measured simultaneously. A range of water mixing conditions was used with a water temperature of 298.2 K. The ratios of the liquid-film coefficients for volatilization to the liquid-film coefficient for oxygen absorption for all of the organic compounds were independent of mixing conditions in the water. Experimental ratios ranged from 0.606 for benzene to 0.357 for n-octylbenzene. The molecular-diffusion-coefficient procedure accurately predicted the ratios for ethylbenzene through n-pentylbenzene with a power dependence of 0.566 on the molecular-diffusion coefficient, in agreement with published values. Predicted ratios for benzene and toluene were slightly larger than the experimental ratios. These differences were attributed to possible interactions between the molecules of these compounds and the water molecules and to benzene-benzene interactions that form dimers. Because these interactions also are likely to occur in natural waters, it was concluded that the experimental ratios are more correct than the predicted ratios for application purposes in the reference-substance concept. Predicted ratios for n-hexylbenzene, n-heptylbenzene, and n-octylbenzene were larger than the experimental ratios. These differences were attributed to a sorption-desorption process between these compounds and the surfaces of the constant-temperature water bath. Other experimental problems associated with preparing water solutions of these slightly soluble compounds also may have contributed to the differences. Because these processes are not part of the true volatilization process, it was concluded that the predicted ratios for these three compounds are probably more correct than the experimental ratios for application purposes in the reference-substance concept. Any model of the fate of these compounds in streams and rivers would have to include terms accounting for sorption processes, however. The molecular-weight procedure accurately predicted the ratios for ethylbenzene through n-pentylbenzene, but only if the power dependence on the molecular weight was decreased from the commonly used -0.500 to -0.427. Deviations for the low- and high-molecular-weight compounds were similar to those observed for the molecular-diffusion-coefficient procedure.

Water Supply Paper

Tests of subsurface storage of freshwater at Hialeah, Dade County, Florida, and numerical simulation of the salinity of recovered water

Injection and observation wells were drilled in late 1974 for the purpose of conducting tests of storage and recovery of potable water in the brackish Upper Floridan aquifer. Three tests, involving storage and recovery cycles of varying volumes and storage period lengths, were performed between July 1975 and January 1980. Recovery was by natural artesian flow, and recovery efficiencies were 32.9, 47.8, and 38.5 percent. Wellbore plugging occurred during the injection stages, but injectivity was restored by periodic 2- to 3-hour backflushes at the natural artesian flow rate. An interval of shelly limestone between 1,015 and 1,050 feet below land surface contained the flow zone. Data from an analysis of 18 spinner flowmeter logs indicated that the principal part of the flow zone extended from 1,024 to 1,036 feet below land surface and that minor amounts of flow occurred to a depth of about 1,047 feet. A neutron porosity log indicated the bulk porosity of both the flow zone and confining layers to be 35 percent. Chloride and dissolved-solids concentrations of water in the flow zone were 1,200 and 2,700 milligrams per liter, respectively. A three-dimensional, finite-difference flow and solute-transport code was used to simulate pressure data measured during an aquifer test and observed salinity increases in recovered water during storage and recovery cycles. The aquifer test conducted in February 1975 was simulated by using a hydraulic conductivity estimate of 800 feet per day and a rock compressibility estimate of 0.0000400 (pound per square inch)-1. The equivalent transmissivity and storage coefficients were 9,600 cubic feet per day per square foot times foot of aquifer thickness and 7.8×10-5, respectively. Simulation of observed salinity increases during the three recoveries required dispersivities of 65 feet, a molecular diffusivity of 0.0002 foot squared per day, and a regional pore velocity of 260 feet per year. Central differencing in space and time was used for the solute-transport computations as well as an experimental method of computing vertical dispersion that used a scaling factor of 0.013. Additional simulations of the aquifer-test data and recovery salinities were obtained based on assumptions that (1) the flow zone was 21 feet thick, (2) flow-zone effective porosity was 20 percent, and (3) flow-zone hydraulic conductivity was bipolar anisotropic by a ratio of 10:1. The four sets of simulation values were used in model runs in which 10 years of annual injection, storage, and recovery cycles were simulated. Computed recovery efficiencies increased from 40 percent in the first year to 68 percent in later cycles. The high regional pore velocity required for model calibration substantially limited the recovery efficiency achieved in later cycles.

Florida

Groundwater-flow model and effects of projected groundwater use in the Ozark Plateaus Aquifer System in the vicinity of Greene County, Missouri — 1907-2030

Recent and historical periods of rapid growth have increased the stress on the groundwater resources in the Ozark aquifer in the Greene County, Missouri area. Historical pumpage from the Ozark aquifer has caused a cone of depression beneath Springfield, Missouri. In an effort to ease its dependence on groundwater for supply, the city of Springfield built a pipeline in 1996 to bring water from Stockton Lake to the city. Rapid population growth in the area coupled with the expanding cone of depression raised concern about the sustainability of groundwater as a resource for future use. A groundwater-flow model was developed by the U.S. Geological Survey in cooperation with Greene County, Missouri, the U. S. Army Corps of Engineers, and the Missouri Department of Natural Resources to assess the effect that increased groundwater demand is having on the long-term availability of groundwater in and around Greene County, Missouri. Three hydrogeologic units were represented in the groundwater-flow model: the Springfield Plateau aquifer, the Ozark confining unit, and the Ozark aquifer. The Springfield Plateau aquifer is less than 350 feet thick in the model area and generally is a low yield aquifer suitable only for domestic use. The Ozark aquifer is composed of a more than 900-foot thick sequence of dolomite and sandstone in the model area and is the primary aquifer throughout most of southern Missouri. Wells open to the entire thickness of the Ozark aquifer typically yield 1,000 gallons per minute or more. Between the two aquifers is the Ozark confining unit composed of as much as 98 feet of shale and limestone. Karst features such as sinkholes, springs, caves, and losing streams are present in both aquifers, but the majority of these features occur in the Springfield Plateau aquifer. The solution-enlarged fracture and bedding plane conduits in the karst system, particularly in the Springfield Plateau aquifer, are capable of moving large quantities of groundwater through the aquifer in relatively short periods of time. Pumpage rates in the model area increased from 1,093,268 cubic feet per day in 1962 to 2,693,423 cubic feet per day in 1987 to 4,330,177 cubic feet per day in 2006. Annual precipitation ranged from 25.21 inches in 1953 to 62.45 inches in 1927 from 1915 to 2006 in the model area. Recharge to the model was calculated as 2.53 percent of the annual precipitation and was varied annually. Recharge was distributed over the model area based on land slope and was adjusted in the city limits of Springfield to account for the impervious surface. A groundwater model with annual stress periods from 1907 to 2030 was developed using a transient calibration period from 1987 to 2006 and a prediction period from 2007 to 2030 to simulate flow in the Springfield Plateau aquifer and the Ozark aquifer. For the model area of approximately 2,870 square miles, the model hydrogeologic units and hydraulic properties were discretized into 253 rows, 316 columns, and 3 layers with the layer boundaries crossing hydrogeologic unit boundaries in some areas. The horizontal cell spacing was 1,000 feet by 1,000 feet. The model was calibrated by minimizing the difference between simulated head and observed water levels and simulated and observed flows in rivers and springs. Population and the associated groundwater use were estimated for 12 communities and the unincorporated area of Greene County based on past growth. Each was analyzed individually, and a low and high annual rate of growth relative to the 2006 population was computed for each community or group. Low growth rates ranged from 0.215 percent per year in Springfield to 6.997 percent per year in Rogersville. Total growth from 2006 to 2030 at the low growth rate ranged from 5.2 percent in Springfield to 167.9 percent in Rogersville. High growth rates ranged from 0.236 percent per year in Springfield to 7.345 percent per year in Rogersville. Total growth from 2006 to 2030 at the high growth rate ranged from 5.7 percent in Springfield to 176.3 percent in Rogersville. Response of the flow system to selected hypothetical pumping stresses and recharge conditions was simulated using the calibrated model. Seven hypothetical scenarios were simulated from 2007 to 2030 to test the effects of various stresses on the head in the Ozark aquifer. Hypothetical scenario 1 continued the 2006 pumping rates without change to the end of 2030. Scenario 2 assumed a low population growth rate with a 4-year drought at the beginning of the prediction period. Scenario 3 assumed a low population growth rate with a 4-year drought at the end of the prediction period. Scenario 4 assumed a high population growth rate with a 4-year drought at the beginning of the prediction period. Scenario 5 assumed a high population growth rate with a 4-year drought at the end of the prediction period. Scenario 6 and 7 had one new industrial well installed within the city limits of Springfield and one new industrial well installed about 3.5 miles east of Rogersville. Scenario 6 assumed a low population growth rate and scenario 7 assumed a high population growth rate. Results were compared by examining differences in head at the end of the simulation period. All scenarios examined resulted in potentiometric-surface declines from 2006 levels. Results from scenario 1 indicated that even with no increase in pumping, the potentiometric surface in the Springfield area continued to decline. The maximum decline of approximately 62 feet from the 2006 potentiometric surface occurred in Springfield. The maximum decline from the 2006 potentiometric surface in scenarios 2 and 3 was approximately 203 feet and in scenarios 4 and 5 was approximately 207 feet. The drought occurring at the end of the simulation period tended to broaden the drawdown area relative to the drought at the beginning. Drought timing did not substantially affect the potentiometric surface in the Ozark aquifer except for where the Ozark aquifer was exposed. Although not a substantial difference, the high population growth rate scenarios tended to have larger declines than the low population growth rate scenarios. As in the previous scenarios, little difference was noted between the low and high growth rate in scenario 6 and 7. Scenarios 6 and 7 showed declines of more than 640 feet from the 2006 potentiometric surface at the new well located in Springfield. The drawdown at the new wells decreased relatively quickly with increased distance from the well. Simulated head in the nearby cities of Nixa, Ozark, and Republic was nearly the same for scenarios 2 through 7 and was lower than the head predicted for scenario 1. Results from scenarios 2 through 7 indicate that the potentiometric surface in 2030 near these cities could decline 100 feet or more from the 2006 levels. Because model layers 2 and 3, representing the Ozark confining unit and most of the thickness of the Ozark aquifer, were simulated as confined, drawdown in the wells in the area of the Ozark aquifer that is unconfined or becomes unconfined during the simulation period will likely be under predicted.

Missouri

Evaluation of effects of changes in canal management and precipitation patterns on salinity in Biscayne Bay, Florida, using an integrated surface-water/groundwater model

Biscayne National Park, located in Biscayne Bay in southeast Florida, is one of the largest marine parks in the country and sustains a large natural marine fishery where numerous threatened and endangered species reproduce. In recent years, the bay has experienced hypersaline conditions (salinity greater than 35 practical salinity units) of increasing magnitude and duration. Hypersalinity events were particularly pronounced during April to August 2004 in nearshore areas along the southern and middle parts of the bay. Prolonged hypersaline conditions can cause degradation of water quality and permanent damage to, or loss of, brackish nursery habitats for multiple species of fish and crustaceans as well as damage to certain types of seagrasses that are not tolerant of extreme changes in salinity. To evaluate the factors that contribute to hypersalinity events and to test the effects of possible changes in precipitation patterns and canal flows into Biscayne Bay on salinity in the bay, the U.S. Geological Survey constructed a coupled surface-water/groundwater numerical flow model. The model is designed to account for freshwater flows into Biscayne Bay through the canal system, leakage of salty bay water into the underlying Biscayne aquifer, discharge of fresh and salty groundwater from the Biscayne aquifer into the bay, direct effects of precipitation on bay salinity, indirect effects of precipitation on recharge to the Biscayne aquifer, direct effects of evapotranspiration (ET) on bay salinity, indirect effects of ET on recharge to the Biscayne aquifer, and maintenance of mass balance of both water and solute. The model was constructed using the Flow and Transport in a Linked Overland/Aquifer Density Dependent System (FTLOADDS) simulator, version 3.3, which couples the two-dimensional, surface-water flow and solute-transport simulator SWIFT2D with the density-dependent, groundwater flow an solute-transport simulator SEAWAT. The model was calibrated by a trial-and-error method to fit observed groundwater heads, estimated base flow, and measured bay salinity and temperatures from 1996 to 2004, as well as the location of the freshwater-saltwater interface in the aquifer, by adjusting ET rate limiters, canal vertical hydraulic conductance, leakage rate coefficients (transition-layer thickness and hydraulic conductivity), Manning's n value, and delineation of rainfall zones. Although flow budget calculations indicate that precipitation, ET, and groundwater flux into the bay represent a small portion of the overall budget, these factors may be important in controlling salinity in some parts of the bay, for example the southern parts of the bay where the canal system is not extensively developed or controlled. The balance of precipitation and ET during the wet season generally results in a reduction of bay salinity, whereas the balance of precipitation and ET during the dry season generally results in an increase in bay salinity. During years when wet season precipitation is lower than average, for example less than 70 percent total precipitation for an average year, ET could outweigh precipitation over the bay for essentially the entire year. Hypersaline conditions are prone to occur near the end of the dry season because precipitation rates are generally lower, canal discharge rates (which are strongly correlated to precipitation rates) are also generally lower, and ET rates are higher than during the rest of the year. The hypersalinity event of 2004 followed several years of relatively low precipitation and correspondingly reduced canal structure releases and was unusually extensive, continuing into July. Thus, hypersalinity is ultimately the result of a cumulative deficit of precipitation. The model was used to test the effects of possible changes in canal flux and precipitation. Simulation results showed that by increasing, reducing, or modifying canal discharge rates, the effects on salinity in the bay were more pronounced in the northern part of the bay where there are more canals and canal-control structures. By doubling and halving precipitation, the effects on bay salinity were more pronounced in the southern part of the bay than in the northern part of the bay where there are fewer canals and canal-control structures. The model is designed to quantify factors that contribute to hypersaline conditions in Biscayne Bay and may be less appropriate for addressing other issues or examining conditions substantially different from those described in this report. Model results must be interpreted in light of model limitations, which include representation of the system and conceptual model, uncertainty in physical properties used to describe the system or processes, the scale and discretization of the system, and representation of the boundary conditions.

Florida

Sampling design for groundwater solute transport: Tests of methods and analysis of Cape Cod tracer test data

Tests of a one-dimensional sampling design methodology on measurements of bromide concentration collected during the natural gradient tracer test conducted by the U.S. Geological Survey on Cape Cod, Massachusetts, demonstrate its efficacy for field studies of solute transport in groundwater and the utility of one-dimensional analysis. The methodology was applied to design of sparse two-dimensional networks of fully screened wells typical of those often used in engineering practice. In one-dimensional analysis, designs consist of the downstream distances to rows of wells oriented perpendicular to the groundwater flow direction and the timing of sampling to be carried out on each row. The power of a sampling design is measured by its effectiveness in simultaneously meeting objectives of model discrimination, parameter estimation, and cost minimization. One-dimensional models of solute transport, differing in processes affecting the solute and assumptions about the structure of the flow field, were considered for description of tracer cloud migration. When fitting each model using nonlinear regression, additive and multiplicative error forms were allowed for the residuals which consist of both random and model errors. The one-dimensional single-layer model of a nonreactive solute with multiplicative error was judged to be the best of those tested. Results show the efficacy of the methodology in designing sparse but powerful sampling networks. Designs that sample five rows of wells at five or fewer times in any given row performed as well for model discrimination as the full set of samples taken up to eight times in a given row from as many as 89 rows. Also, designs for parameter estimation judged to be good by the methodology were as effective in reducing the variance of parameter estimates as arbitrary designs with many more samples. Results further showed that estimates of velocity and longitudinal dispersivity in one-dimensional models based on data from only five rows of fully screened wells each sampled five or fewer times were practically equivalent to values determined from moments analysis of the complete three-dimensional set of 29,285 samples taken during 16 sampling times.

Water Resources Research

Summary appraisals of the nation's ground-water resources – California region

Most people in the California Region live in a semiarid or arid climate, with precipitation less than the potential evapotranspiration- environments of perennial water deficiency. The deficiency becomes most onerous during the characteristically rainless summers and during recurrent droughts that may continue for 10--20 years. However, water from winter rain and snow can be stored for use during the dry summer months, and water stored during a wet climatic period can be used in a succeeding dry period; moreover, perennial deficiency can be overcome by bringing water from areas of perennial surplus. Ground-water reservoirs have especial significance in arid and semiarid regions as repositories where water is stored or can be stored with minimum loss by evaporation. Nearly all the ground-water reservoirs of the California Region are in alluvial sediments of valleys and plains that flank the mountain ranges. The largest, underlying the vast Central Valley, occupies 10 percent of the area of the region, has an estimated usable capacity exceeding 100 million acre-feet (125 cubic kilometres), and has an annual pumpage from wells of about 13 million acre-feet (16 cubic kilometres). Another 10 percent of the region is occupied by 55 developed ground-water reservoirs that are widely distributed; aggregate annual pumpage from them is about 3 1/2 million acre-feet (4 cubic kilometres). In the southeastern desert about 60 ground-water reservoirs occupy still another 10 percent of the region; these have been explored only enough to show that most have some usable water, but current use is negligible. In northeastern California and adjacent Oregon and Nevada, ground-water reservoirs are identified only in valleys and lowlands where wells are feasible, but basaltic rocks of the Cascade Range and Modoc Plateau are excellent aquifers distributed over an area constituting about 15 percent of the region. In sum, slightly less than half the California Region is underlain by ground-water reservoirs, either in valley fill or in volcanic rocks, which can yield significant quantities of water to wells. The rest of the California Region includes the mountains, canyons, slopes, and foothills of the Sierra Nevada, Coast Ranges, and Basin Ranges, whose consolidated rocks and products of their weathering may be permeable locally but are not generally so. Here, the prevailing method of ground-water development is still mostly trial and error, and while in many places a well can yield enough water for a family, some families might have to do without amenities such as flush toilets and automatic washers. For more than half a century the California Region has led all others in North America in pumping of ground water as well as in the area, variety, yield, and export of crops irrigated by water from wells. It has led in the development and use of deep-well turbine pumps for large yield and in the drilling of water wells to great depths. At the same time, such developments have resulted in the elimination of artesian pressures that produced thousands of flowing wells in the 19th century and led to the wide distribution of "falling water tables." Also, California was first to induce encroachment of seawater into wells (in 1906); first to recognize subsidence of land caused by pumping from wells (in 1933), generating news about land sinking in San Jose, Long Beach, and along the Delta-Mendota and Friant-Kern Canals; and first to experience pollution of ground-water reservoirs by brines, chemicals, industrial wastes, and petroleum byproducts including gasoline. The region has led in research in several fields leading to solution of many of these problems. Ground-water problems developed rapidly after World War II with booming population, agriculture, industry, and water demand during several years of regionwide drought. Water levels in wells trended downward almost everywhere as a natural effect of the drought and at accelerated rates in areas of pumping for new enterprises or to supplement subnormal surface-water supplies. The declines in many pumping areas exceeded 100 feet (30 metres), and in some confined aquifers the potentiometric surface was drawn down more than 330 feet (100 metres). The depletion of ground-water storage has had "permanent" side effects, including subsidence of the land exceeding 10 feet (3 metres) in extensive areas, and seawater intrusion that ended the useful lives of many wells along the coast and as much as 6 miles (10 kilometres) inland. Some problems have been solved, but these solutions have at times created other problems. Many ground-water reservoirs have gone through one or more stages - exploration for productive aquifers, exploitation and development for use of the water, restriction to the perennial supply or "safe" yield, importation of surface water, artificial recharge of ground water, conjunctive use of surface and ground water, protection of water quality, and integrated management of use and disposal of water. This evolutionary sequence is unique for each reservoir, and so generalizations become difficult in a regional appraisal; also, the changes with time are significant and varied, and knowledge of prior events is a prerequisite in an appraisal of the resource in a specific year. As of 1970, water levels in many wells had risen significantly from the minimum levels of record reached during the 1960's or earlier; only in areas of new development and in desert areas of long-continued "mining" of nonreplenished water was ground-water storage still being depleted. Land subsidence has continued at diminishing rates and practically has come to a halt in some areas; invading seawater has been stopped or nudged back in most places where problems were significant. The current, favorable situation has been helped by climatic variations, from drought in 1945-52 and exceedingly dry years in 1959 and 1961 to above-normal precipitation in 1969 and 1970; but most of the serious problems have been solved by human efforts, including especially the implementation of the California Water Plan, transporting water from areas of perennial surplus to areas where it is used in lieu of ground water or for ground-water replenishment. All major urban areas now import water to supplement or replace the water pumped from wells. Extensive agricultural areas that formerly were irrigated solely by ground water now obtain some of their water from surface reservoirs and canals, especially in the Central Valley. With surface water available as an alternative supply, well owners can view their ground water with complacency. But complacency can lead to neglect and carelessness and consequent deterioration of the ground-water resource by pollution. Claiming heritage from the English Common Law, the existing California law grants to the landowner (riparian) and private enterprise (appropriator) rights to the water stored in ground-water reservoirs or discharged from them, including the base flow of streams. Ground-water development has been by private and local enterprise, and the California legislature has protected and encouraged local responsibility, control, and management of ground water. As to surface water, a constitutional amendment in 1928 limited riparian rights to the quantities of water that were "reasonably required for the beneficial use to be served." The surpluses have become public waters which are collected, stored, transported, and delivered under various contracts by Federal, State, and other agencies. The agencies have not stored water underground because of uncertainty as to their rights, but some local agencies have been encouraged with favorable pricing schedules to undertake the artificial recharge and management of ground-water reservoirs. Thus, conjunctive use of surface and ground water has become a matter of interagency negotiation. Of all the constraints on effective use of ground-water reservoirs, the most formidable may be the attitudes of people. Assurance of water supply is vital in areas of water deficiency, and Government has assumed increasing responsibility for the welfare of people in these areas. Unfortunately, when Government provides this assurance, most beneficiaries demand continued subsidy to the exclusion of perhaps cheaper private development. Indeed, as the water resources are presently segregated-with private rights predominant in ground water and public interest dominant in surface water-ground-water development has suffered for lack of public concern. The region has the scientific and technologic capability for effective use of groundwater reservoirs, as shown by the achievements and programs of several districts, but many districts are not organized or staffed for such comprehensive management and will need assistance and scientific expertise available from State and Federal agencies. Those agencies, in turn, may not have the scientific data that are essential to prevent haphazard activities and to enable programs to be organized for the most effective and attractive utilization of the water resources. In these days of increasing concern over pollution, existing data are generally inadequate to assess the natural deterioration of ground waters as a basis for defining pollution.

California

Groundwater quality in relation to drinking water health standards and geochemical characteristics for 54 domestic wells in Clinton County, Pennsylvania, 2017

Despite the reliance on groundwater by approximately 2.4 million rural Pennsylvania residents, publicly available data to characterize the quality of private well water are limited. As part of a regional effort to characterize groundwater in rural areas of Pennsylvania, samples from 54 domestic wells in Clinton County were collected and analyzed in 2017. The samples were evaluated for a wide range of constituents and compared to drinking-water health standards and geochemical characteristics. The sampled wells were completed to depths ranging from 46 to 500 feet in bedrock that was of predominantly sandstone, shale, or carbonate lithology. Results of this study show that the sampled groundwater quality in Clinton County generally met most drinking-water standards that apply to public water supplies. However, a percentage of samples exceeded drinking-water maximum contaminant levels (MCLs) for total coliform bacteria (57.4 percent), Escherichia coli ( E. coli ) (25.9 percent), nitrate (1.9 percent), and arsenic (1.9 percent); and secondary maximum contaminant levels (SMCLs) for pH (31.5 percent), manganese (29.6 percent), iron (13 percent), total dissolved solids (7.4 percent), aluminum (1.9 percent), and chloride (1.9 percent). Sodium concentrations exceeded the U.S. Environmental Protection Agency drinking-water advisory recommendation in 16.7 percent of the samples. Radon-222 activities exceeded the proposed drinking-water standard of 300 picocuries per liter (pCi/L) in 59.3 percent of the samples. The only volatile organic compounds (VOCs) detected were acetone and methyl ethyl ketone in two separate samples; neither constituent exceeded drinking-water standards. Higher median nitrate concentrations were found in the carbonate (3.26 milligrams per liter [mg/L]) versus shale (less than 0.04 mg/L) and sandstone (0.27 mg/L) aquifer subsets. Most of the elevated nitrate concentrations were associated with E. coli detections in the carbonate aquifers, where transmissive bedrock can facilitate groundwater contamination by human activities at the land surface. The median pH of groundwater from the sandstone aquifers (6.53) was less than those for the shale aquifers (7.31) and carbonate aquifers (7.43). Generally, the lower pH samples had greater potential for elevated concentrations of dissolved metals, including beryllium, copper, lead, nickel, and zinc, whereas the higher pH samples had greater potential for elevated concentrations of total dissolved solids, sodium, fluoride, boron, and uranium. Near-neutral samples (pH 6.5 to 7.5) had greater hardness and alkalinity concentrations than other samples with pH outside this range. Many samples from the shale or sandstone aquifers, particularly those with pH less than 6.5, were identified as having serious potential corrosivity based on the combination of the calcite saturation index and the chloride to sulfate mass ratio; however, none of the samples from the carbonate aquifers was identified as seriously corrosive. Groundwater from 3.7 percent of the wells had concentrations of methane greater than the Pennsylvania action level of 7 mg/L, and 48 of the 54 wells (88.9 percent) had detectable concentrations of methane greater than the 0.0002 mg/L detection limit. Greater methane concentrations were found more frequently in groundwater sampled from the shale aquifers than the carbonate or sandstone aquifers in the study area. Most of the samples containing elevated methane (greater than 0.2 mg/L) were located outside the area of the Appalachian Plateaus. The elevated concentrations of methane generally were associated with suboxic groundwater (dissolved oxygen less than 0.5 mg/L) that had near-neutral to alkaline pH and were correlated with concentrations of iron, manganese, ammonia, sodium, lithium, barium, fluoride, and boron. The stable carbon and hydrogen isotopic compositions of methane in two of four samples analyzed for isotopes were consistent with compositions reported for mud-gas logging samples from gas-bearing geologic units (thermogenic gas) in the Appalachian Plateaus region, whereas two others were consistent with methane of microbial origin or a mixture of microbial and thermogenic gas. Forty-two percent of samples had chloride concentrations greater than 20 mg/L with variable bromide concentrations. Corresponding chloride/bromide ratios are consistent with low-bromide sources such as road-deicing salt and septic effluent or animal waste, or, in a few cases, high-bromide brine. Brines characterized by relatively high bromide are naturally present in deeper parts of the regional groundwater system and, in some cases, may be mobilized by gas drilling. The chloride, bromide, and other constituents in road-deicing salt or brine solutions tend to be diluted by mixing with fresh groundwater in shallow aquifers used for water supply. One of the four groundwater samples with methane concentrations greater than 4 mg/L had chloride and bromide concentrations and a chloride/bromide ratio that indicates mixing with a salinity source such as road-deicing salt, whereas the chloride and bromide concentrations and ratios for the other three high-methane samples indicate mixing with a small amount of brine (0.03 percent or less). In two other eastern Pennsylvania county studies where gas drilling is absent, groundwater with comparable chloride/bromide ratios, bromide, and chloride concentrations plus other element associations have been reported. Additional sampling and analysis, such as isotopic analysis of the dissolved gas, fracture analysis, and more detailed evaluation of surrounding land uses, may be warranted to better understand the origin of the methane and brine constituents in groundwater at specific locations.

Pennsylvania

LANDFIRE 2010 - updated data to support wildfire and ecological management

Wildfire is a global phenomenon that affects human populations and ecosystems. Wildfire effects occur at local to global scales impacting many people in different ways (Figure 1). Ecological concerns due to land use, fragmentation, and climate change impact natural resource use, allocation, and conservation. Access to consistent and current environmental data is a constant challenge, yet necessary for understanding the complexities of wildfire and ecological management. Data products and tools from the LANDFIRE Program help decision-makers to clarify problems and identify possible solutions when managing fires and natural resources. LANDFIRE supports the reduction of risk from wildfire to human lives and property, monitoring of fire danger, prediction of fire behavior on active incidents, and assessment of fire severity and impacts on natural systems [1] [2] [3]. LANDFIRE products are unique in that they are nationally consistent and provide the only complete geospatial dataset describing vegetation and wildland fuel information for the entire U.S. As such, LANDFIRE data are useful for many ecological applications [3]. For example, LANDFIRE data were recently integrated into a decision-support system for resource management and conservation decision-making along the Appalachian Trail. LANDFIRE is a joint effort between the U.S. Department of the Interior Office of Wildland Fire, U.S. Department of Agriculture Forest Service Fire & Aviation Management, and The Nature Conservancy. To date, seven versions of LANDFIRE data have been released, with each successive version improving the quality of the data, adding additional features, and/or updating the time period represented by the data. The latest version, LANDFIRE 2010 (LF 2010), released mid-2013, represents circa 2010 landscape conditions and succeeds LANDFIRE 2008 (LF 2008), which represented circa 2008 landscape conditions. LF 2010 used many of the same processes developed for the LF 2008 effort [3]. Ongoing refinement of the LANDFIRE vegetation and fuel data is necessary to improve the quality and usability of the data and to capture landscape disturbance. LANDFIRE relies on Landsat multi-spectral imagery to produce and update vegetation and fuel data. The deep Landsat archive provides data needed for vegetation classification, change analysis, and historical disturbance characterization, for which LANDFIRE has used more than 24,000 image scenes since the program’s inception. In addition, LF 2010 used airborne and spaceborne lidar, and spaceborne synthetic aperture radar (SAR) to map vegetation structure in areas where ground-based field information was lacking, including Alaska and U.S.-affiliated islands in the Caribbean and the Pacific. The mapping of insular areas is new for the 2010 data release; previous versions of LANDFIRE were limited to the conterminous U.S., Alaska, and Hawaii.

Earthzine

Vadose zone attenuation of organic compounds at a crude oil spill site - Interactions between biogeochemical reactions and multicomponent gas transport

Contaminant attenuation processes in the vadose zone of a crude oil spill site near Bemidji, MN have been simulated with a reactive transport model that includes multicomponent gas transport, solute transport, and the most relevant biogeochemical reactions. Dissolution and volatilization of oil components, their aerobic and anaerobic degradation coupled with sequential electron acceptor consumption, ingress of atmospheric O 2 , and the release of CH 4 and CO 2 from the smear zone generated by the floating oil were considered. The focus of the simulations was to assess the dynamics between biodegradation and gas transport processes in the vadose zone, to evaluate the rates and contributions of different electron accepting processes towards vadose zone natural attenuation, and to provide an estimate of the historical mass loss. Concentration distributions of reactive (O 2 , CH 4 , and CO 2 ) and non-reactive (Ar and N 2 ) gases served as key constraints for the model calibration. Simulation results confirm that as of 2007, the main degradation pathway can be attributed to methanogenic degradation of organic compounds in the smear zone and the vadose zone resulting in a contaminant plume dominated by high CH 4 concentrations. In accordance with field observations, zones of volatilization and CH 4 generation are correlated to slightly elevated total gas pressures and low partial pressures of N 2 and Ar, while zones of aerobic CH 4 oxidation are characterized by slightly reduced gas pressures and elevated concentrations of N 2 and Ar. Diffusion is the most significant transport mechanism for gases in the vadose zone; however, the simulations also indicate that, despite very small pressure gradients, advection contributes up to 15% towards the net flux of CH 4 , and to a more limited extent to O 2 ingress. Model calibration strongly suggests that transfer of biogenically generated gases from the smear zone provides a major control on vadose zone gas distributions and vadose zone carbon balance. Overall, the model was successful in capturing the complex interactions between biogeochemical reactions and multicomponent gas transport processes. However, despite employing a process-based modeling approach, honoring observed parameter ranges, and generally obtaining good agreement between field observations and model simulations, accurate quantification of natural attenuation rates remains difficult. The modeling results are affected by uncertainties regarding gas phase saturations, tortuosities, and the magnitude of CH 4 and CO 2 flux from the smear zone. These findings highlight the need to better delineate gas fluxes at the model boundaries, which will help constrain contaminant degradation rates, and ultimately source zone longevity.

Minnesota

Estimating Concentrations of Road-Salt Constituents in Highway-Runoff from Measurements of Specific Conductance

Discrete or composite samples of highway runoff may not adequately represent in-storm water-quality fluctuations because continuous records of water stage, specific conductance, pH, and temperature of the runoff indicate that these properties fluctuate substantially during a storm. Continuous records of water-quality properties can be used to maximize the information obtained about the stormwater runoff system being studied and can provide the context needed to interpret analyses of water samples. Concentrations of the road-salt constituents calcium, sodium, and chloride in highway runoff were estimated from theoretical and empirical relations between specific conductance and the concentrations of these ions. These relations were examined using the analysis of 233 highwayrunoff samples collected from August 1988 through March 1995 at four highway-drainage monitoring stations along State Route 25 in southeastern Massachusetts. Theoretically, the specific conductance of a water sample is the sum of the individual conductances attributed to each ionic species in solution-the product of the concentrations of each ion in milliequivalents per liter (meq/L) multiplied by the equivalent ionic conductance at infinite dilution-thereby establishing the principle of superposition. Superposition provides an estimate of actual specific conductance that is within measurement error throughout the conductance range of many natural waters, with errors of less than ?5 percent below 1,000 microsiemens per centimeter (?S/cm) and ?10 percent between 1,000 and 4,000 ?S/cm if all major ionic constituents are accounted for. A semi-empirical method (adjusted superposition) was used to adjust for concentration effects-superposition-method prediction errors at high and low concentrations-and to relate measured specific conductance to that calculated using superposition. The adjusted superposition method, which was developed to interpret the State Route 25 highway-runoff records, accounts for contributions of constituents other than calcium, sodium, and chloride in dilute waters. The adjusted superposition method also accounts for the attenuation of each constituent's contribution to conductance as ionic strength increases. Use of the adjusted superposition method generally reduced predictive error to within measurement error throughout the range of specific conductance (from 37 to 51,500 ?S/cm) in the highway runoff samples. The effects of pH, temperature, and organic constituents on the relation between concentrations of dissolved constituents and measured specific conductance were examined but these properties did not substantially affect interpretation of the Route 25 data set. Predictive abilities of the adjusted superposition method were similar to results obtained by standard regression techniques, but the adjusted superposition method has several advantages. Adjusted superposition can be applied using available published data about the constituents in precipitation, highway runoff, and the deicing chemicals applied to a highway. This semi-empirical method can be used as a predictive and diagnostic tool before a substantial number of samples are collected, but the power of the regression method is based upon a large number of water-quality analyses that may be affected by a bias in the data.

Water-Resources Investigations Report

Proceedings of a workshop on the development and evaluation of habitat suitability criteria: A compilation of papers and discussions presented at Colorado State University, Fort Collins, Colorado, December 8-12, 1986

The development of reliable habitat suitability criteria is critical to the successful implementation of the Instream Flow Incremental Methodology (IFIM), or any other habitat based evaluation technology. It is also a fascinating topic of research, for several reasons. First, the “science” of habitat quantification is relatively young. Descriptions of habitat use and partitioning can be traced back to Darwin, if not further. Attempts to actually quantify habitat use can be found predominantly during the last two decades, with most of the activity occurring in about the last five years. Second, this work is challenging because we are usually working with fish or some other organism that lives out of sight in an environment that is foreign to humans. Most of the data collection techniques that have been developed for standard fisheries work are unsuited, without modification, for criteria development. These factors make anyone involved in this type of research a pioneer, of sorts. Pioneers often make new and wonderful discoveries, but they also sometimes get lost. In our opinion, however, there is an even more rewarding aspect to criteria development research. It seems that the field of biology has tended to become increasingly clinical over the years. Criteria development demands the unobtrusive observation of organisms in their natural environment, a fact that allows the biological to be a naturalist and still get paid for it. The relative youth and importance of habitat quantification have resulted in rapid advancements in the state of the art. The expansion of methods is vividly demonstrated simply by comparing the two Instream Flow Information Papers written on the subject in 1978 and in 1986. One of the missions of the Aquatic Systems Branch (formerly the Instream Flow Group) is to serve as a clearinghouse for new techniques and methods. In keeping with this role, a workshop was conducted during December 1986 to discuss current and newly evolving methods for developing and evaluating habitat suitability criteria. Participation in this workshop was largely by invitation only. The objective was to obtain insights into problems and possible solutions to criteria development, from the perspective of professionals closely involved with the subject. These proceedings of that workshop are intended to supplement the information contained in Instream Flow Information Paper 21, "Development and Evaluation of Habitat Suitability Criteria for Use in the Instream Flow Incremental Methodology." The workshop was closely arranged in five sessions, roughly following the outline of Information Paper 21. The first session dealt with various aspects of study design and how they can influence the outcome of a study. Session two investigated techniques for developing criteria from professional judgment, and some of the problems encountered when personal or agency prejudice enters the picture. Session three concentrated on field data collection procedures, whereas session four examined methods of converting field data into curves. Field verification studies were discussed in session five. Each presentation in the workshop was followed by a question and answer period of 15 to 30 minutes. These discussions were recorded, transcribed, and appended to the end of each paper in these proceedings. We have attempted to capture the essence of these discussions as accurately as possible, but hope that the reader can appreciate the difficulty in translating a free-ranging discussion (from a barely audible tape) to something that makes sense in print. These question and answer sessions constitute the peer review for each of the papers. This provides the reader with the unique opportunity to review the interactions between authors and reviewers.

Book

Deep geothermal brine near Salton Sea, California

A well drilled for geothermal power near Salton Sea in Imperial Valley, Calif., is 5,232 feet deep; it is the deepest well in the world (1962) in a high-temperature hot spring area. In the lower half of the hole temperatures are too high to measure with available equipment, but are at loast 270°C, and may be as much as 370°C. For comparison, maximum temperature heretofore reported at depth (1962) for hot spring areas is 295°C. The well taps a very saline brine of Na-Ca-K-Cl type (about 185,000 ppm Cl) with exceptionally high potassium, and with the highest content of minor alkali elements known for natural waters; Fe, Mn, Zn, Pb, Cu, Ag, and some other metals are also exceptionally high. This brine may be connate, but present evidence favors a source in the magma chamber at depth that supplied late Quaternary rhyolite domes of the area. If the latter is correct, the brine is an undiluted magmatic water that is residual from the separation of a more volatile phase high in CO 2 , H 2 S, and with some alkali halides. Elsewhere, the hypothesized volatile phase may account for near-surface hot spring activity of most thermal areas of volcanic association. The residual brine of high salinity may ordinarily remain relatively deep in the volcanic systems because of high specific gravity and low content of volatiles, seldom appearing at the surface except in a greatly diluted form. The hot springs of Arima, Japan, may be a rare example of this type of magmatic water discharging at the surface in moderate concentration (Cl as much as 42,000 ppm). Independent evidence from fluid inclusions in minerals of high-temperature base-metal deposits also favors the existence of magmatic water high in Na, Ca, and Cl, and low in CO 2 and other volatile components. During a three-month production test several tons of material precipitated in the horizontal discharge pipe from the well. Amorphous silica with iron and manganese, and bornite are the dominant recognized components. This material contains the astonishingly high contents of about 20 percent copper, 2 percent silver, and notable sulfur, arsenic, bismuth, lead, antimony, and some other minor elements. Total quantities of all elements in the original whole brine are not yet known, but calculated amounts corresponding to 1 to 3 ppm of copper and 0.1 to 0.3 ppm of silver were precipitated from the brine to form the pipe deposits. The brine, therefore, may be man’s first sample of an « active » ore solution. Equally fascinating to many geologists is the possibility that in the lower part of the hole temperatures are so high and pressures are sufficient for young sedimentary rocks to be undergoing transformation into rocks with mineral assemblages of the greenschist facies of metamorphism. Drill cores from 4,400 to 5,000 feet in depth contain chlorite, albite, K-feldspar, epidote, mica, and quartz, with some indication of increase in metamorphic grade downward. Regional geological and geophysical studies favor a depth of about 20,000 feet to pre-Tertiary basement rocks in the general area. A shallow basement or local upfaulting of old metamorphic rocks are not likely possibilities for the thermal area.

California

User's guide to revised method-of-characteristics solute-transport model (MOC--version 31)

The U.S. Geological Survey computer model to simulate two-dimensional solute transport and dispersion in ground water (Konikow and Bredehoeft, 1978; Goode and Konikow, 1989) has been modified to improve management of input and output data and to provide progressive run-time information. All opening and closing of files are now done automatically by the program. Names of input data files are entered either interactively or using a batch-mode script file. Names of output files, created automatically by the program, are based on the name of the input file. In the interactive mode, messages are written to the screen during execution to allow the user to monitor the status and progress of the simulation and to anticipate total running time. Information reported and updated during a simulation include the current pumping period and time step, number of particle moves, and percentage completion of the current time step. The batch mode enables a user to run a series of simulations consecutively, without additional control. A report of the model's activity in the batch mode is written to a separate output file, allowing later review. The user has several options for creating separate output files for different types of data. The formats are compatible with many commercially available applications, which facilitates graphical postprocessing of model results. Geohydrology and Evaluation of Stream-Aquifer Relations in the Apalachicola-Chattahoochee-Flint River Basin, Southeastern Alabama, Northwestern Florida, and Southwestern Georgia By Lynn J. Torak, Gary S. Davis, George A. Strain, and Jennifer G. Herndon Abstract The lower Apalachieola-Chattahoochec-Flint River Basin is underlain by Coastal Plain sediments of pre-Cretaceous to Quaternary age consisting of alternating units of sand, clay, sandstone, dolomite, and limestone that gradually thicken and dip gently to the southeast. The stream-aquifer system consism of carbonate (limestone and dolomite) and elastic sediments, which define the Upper Floridan aquifer and Intermediate system, in hydraulic connection with the principal rivers of the basin and other surface-water features, natural and man made. Separate digital models of the Upper Flori-dan aquifer and Intermediate system were constructed by using the U.S. Geological Survey's MODular Finite-Element model of two dimensional ground-water flow, based on concep- tualizations of the stream-aquifer system, and calibrated to drought conditions of October 1986. Sensitivity analyses performed on the models indicated that aquifer hydraulic conductivity, lateral and vertical boundary flows, and pumpage have a strong influence on groundwater levels. Simulated pumpage increases in the Upper Floridan aquifer, primarily in the Dougherty Plain physiographic district of Georgia,. caused significant reductions in aquifer discharge to streams that eventually flow to Lake Seminole and the Apalachicola River and Bay. Simulated pumpage increases greater than 3 times the October 1986 rates caused drying ofsome stream reaches and parts of the Upper Floridan aquifer in Georgia. Water budgets prepared from simulation results indicate that ground- water discharge to streams and recharge by horizontal and vertical flow are the principal mechanisms for moving water through the flow system. The potential for changes in ground-water quality is high in areas where chemical constituents can be mobilized by these mechanisms. Less than 2 percent of ground-water discharge to streams comes from the Intermediate system; thus, it plays a minor role in the hydrodynamics of the stream- aquifer system.

Water-Resources Investigations Report

Coupling validation effort with in situ bioacoustic data improves estimating relative activity and occupancy for multiple species with cross-species misclassifications

The increasing complexity and pace of ecological change requires natural resource managers to consider entire species assemblages. Acoustic recording units (ARUs) require minimal cost and effort to deploy and inform relative activity, or encounter rates, for multiple species simultaneously. ARU-based surveys require post-processing of the recordings via software algorithms that assign a species label to each recording. The automated classification process can result in cross-species misidentifications that should be accounted for when employing statistical modelling for conservation decision-making. Using simulation and ARU-based detection counts from 17 bat species in British Columbia, Canada, we investigate three strategies for adjusting statistical inference for species misclassification: (a) ‘coupling’ ambiguous and unambiguous detections by validating a subset of survey events post-hoc, (b) using a calibration dataset on the software algorithm's (in)accuracy for species identification or (c) specifying informative Bayesian priors on classification probabilities. We explore the impact of different Bayesian prior specifications for the classification probabilities on posterior estimation. We then consider how the quantity of data validated post-hoc impacts model convergence and resulting inferences for bat species relative activity as related to nightly conditions and yearly site occupancy after accounting for site-level environmental variables. Coupled methods resulted in less bias and uncertainty when estimating relative activity and species classification probabilities relative to calibration approaches. We found that species that were difficult-to-detect and those that were often inaccurately identified by the software required more validation effort than more easily detected and/or identified species. Our results suggest that, when possible, acoustic surveys should rely on coupled validated detection information to account for false-positive detections, rather than uncoupled calibration datasets. However, if the assemblage of interest contains a large number of rarely detected or less prevalent species, an intractable amount of effort may be required, suggesting there are benefits to curating a calibration dataset that is representative of the observation process. Our findings provide insights into the practical challenges associated with statistical analyses of ARU data and possible analytical solutions to support reliable and cost-effective decision-making for wildlife conservation/management in the face of known sources of observation errors.

British Columbia

Integrated rangeland fire management strategy actionable science plan completion assessment: Invasives topic, 2015–20

Loss and degradation of sagebrush rangelands due to an accelerated invasive annual grass-wildfire cycle and other stressors are significant management, conservation, and economic issues in the western United States. These sagebrush rangelands comprise a unique biome spanning 11 states, support over 350 wildlife species, and provide important ecosystem services that include stabilizing the economies of western communities. Impacts to sagebrush ecosystem processes over large areas due to the annual grass-wildfire cycle necessitated the development of a coordinated, science-based strategy for improving efforts to achieve long-term protection, conservation, and restoration of sagebrush rangelands, which was framed in 2015 under the Integrated Rangeland Fire Management Strategy (IRFMS). Central to this effort was the development of an Actionable Science Plan (Plan) that identified 37 priority science needs (Needs) for informing the actions proposed under the 5 topics (Fire, Invasives, Restoration, Sagebrush and Sage-Grouse, Climate and Weather) that were part of the collective focus of the IRFMS. Notable keys to this effort were identification of the Needs co-produced by managers and researchers, and a focus on resulting science being “actionable.” Substantial investments aimed at fulfilling the Needs identified in the Plan have been made since its release in 2016. While the state of the science has advanced considerably, the extent to which knowledge gaps remain relative to identified Needs is relatively unknown. Moreover, new Needs have likely emerged since the original strategy as results from actionable science reveal new questions and possible (yet untested) solutions. A quantifiable assessment of the progress made on the original science Needs can identify unresolved gaps and new information that can help inform prioritization of future research efforts. This report details a systematic literature review that evaluated how well peer-reviewed journal articles and formal technical reports published between January 1, 2015, and December 31, 2020, addressed six needs (hereinafter “Needs”) identified under the Invasives topic in the Plan. The topic outlined research Needs related to the control of invasive plant species in sagebrush rangelands, with a special emphasis on invasive annual grasses. We established the level of progress towards addressing each Need following a standardized set of criteria, and developed summaries detailing how research objectives nested within Needs identified in the Plan (“Next Steps”) were either addressed well, partially addressed, or remain outstanding (that is, addressed poorly) in the literature through 2020. Our searches resulted in the inclusion of 198 science products that at least partially addressed a Need identified in the Invasives topic. The Needs that were well and partially addressed included: studies of natural and anthropogenic factors influencing the distribution and spread; methods of preventing, eradicating and controlling invasive plant species; development of mapping techniques that provide regularly updated annual grass and fine fuel projections; and assessment of the efficacy of potential cheatgrass biocontrol agents. Needs that were addressed poorly included (1) investigations of livestock grazing as a tool for managing invasive plants and (2) investigations of cheatgrass die-offs and identification and subsequent study of potential biocontrol agents associated with those die-offs. The information provided in this assessment will assist updating the Plan along with other science strategies.

western United States

Self-ordering and complexity in epizonal mineral deposits

Epizonal base and precious metal deposits makeup a range of familiar deposit styles including porphyry copper-gold, epithermal veins and stockworks, carbonate-replacement deposits, and polymetallic volcanic rock-hosted (VHMS) deposits. They occur along convergent plate margins and are invariably associated directly with active faults and volcanism. They are complex in form, variable in their characteristics at all scales, and highly localized in the earth’s crust. More than a century of detailed research has provided an extensive base of observational data characterizing these deposits, from their regional setting to the fluid and isotope chemistry of mineral deposition. This has led to a broad understanding of the large-scale hydrothermal systems within which they form. Low salinity vapor, released by magma crystallization and dispersed into vigorously convecting groundwater systems, is recognized as a principal source of metals and the gases that control redox conditions within systems. The temperature and pressure of the ambient fluid anywhere within these systems is close to its vapor-liquid phase boundary, and mineral deposition is a consequence of short timescale perturbations generated by localized release of crustal stress. However, a review of occurrence data raises questions about ore formation that are not addressed by traditional genetic models. For example, what are the origins of banding in epithermal veins, and what controls the frequency of oscillatory lamination? What controls where the phenomenon of mineralization occurs, and why are some porphyry deposits, for example, so much larger than others? The distinctive, self-organized characteristics of epizonal deposits are shown to be the result of repetitive coupling of fracture dilation consequent on brittle failure, phase separation (“boiling”), and heat transfer between fluid and host rock. Process coupling substantially increases solute concentrations and triggers fast, far-from-equilibrium depositional processes. Since these coupled processes lead to localized transient changes in fluid characteristics, paragenetic, isotope, and fluid inclusion data relate to conditions at the site of deposition and only indirectly to the characteristics of the larger-scale hydrothermal system and its longer-term behavior. The metal concentrations (i.e. grade) of deposits and their internal variation is directly related to the geometry of the fracture array at the deposit scale, whereas finer-scale oscillatory fabrics in ores may be a result of molecular scale processes. Giant deposits are relatively rare and develop where efficient metal deposition is spatially focused by repetitive brittle failure in active fault arrays. Some brief case histories are provided for epithermal, replacement, and porphyry mineralization. These highlight how rock competency contrasts and feedback between processes, rather than any single component of a hydrothermal system, govern the size of individual deposits. In turn, the recognition of the probabilistic nature of mineralization provides a firmer foundation through which exploration investment and risk management decisions can be made.

Annual Review of Earth and Planetary Sciences

Low-flow characteristics of streams in Maryland and Delaware

Hydrologic information on the variability of streamflow during low-flow periods is needed for the effective management of surface-water resources in Maryland and Delaware. Low-flow characteristics derived from streamflow under natural conditions are presented for 94 continuousrecord gaging stations in Maryland, Delaware, and surrounding States, and for 131 low-flow partial-record gaging stations in Maryland and Delaware. Methods are developed to estimate low-flow characteristics at ungaged stream sites for average 7-, 14-, and 30-consecutive-day lowflow discharges for recurrence intervals of 2, 10, and 20 years. The methods are applicable to unregulated streams in Maryland and Delaware for watersheds having drainage areas ranging from 2.0 to 875 square miles. Maryland and Delaware are divided into four regions on the basis of physiography and the results of regression analyses. The regions are the Eastern Shore region in Maryland and Delaware, the eastern-Piedmont region in Maryland, the western region in Maryland, and the southern region in Maryland. Equations are developed from regression analyses to estimate lowflow characteristics at ungaged sites on ungaged streams for the Eastern Shore region, the easternPiedmont region, and the western region. A generalized least-squares multiple-regression technique is used to develop the estimation equations that relate average 7-, 14-, and 30- consecutive-day low-flow discharges for recurrence intervals of 2, 10, and 20 years to physical and climatological features of drainage basins in the study area. Adjustments are necessary to low-flow discharges estimated from the equation for the western region because of the effects of carbonate rocks on low flows. The adjustment method is based on analysis of the residuals of regional estimation equations and the percentage of the basin underlain by carbonate rocks. An equation is developed on the basis of a distance-weighted average of low-flow discharges at gaging stations to estimate low flow characteristics at ungaged sites on ungaged streams for the southern region. Estimates of the accuracy of low-flow characteristics determined from all regional equations are provided. Two methods are presented for estimating low-flow characteristics at ungaged sites on gaged streams. One method combines low-flow characteristics determined from gaging station data with results from the regional regression equation at the gaging station and at the ungaged site to estimate the low-flow characteristics either upstream or downstream from the gaging station. The other method estimates low-flow characteristics at ungaged sites between gaging stations using a graphical solution. Estimates of accuracy of the low-flow characteristics determined by these methods also are provided.

Delaware, Maryland

The source of groundwater and solutes to Many Devils Wash at a former uranium mill site in Shiprock, New Mexico

The Shiprock Disposal Site is the location of the former Navajo Mill (Mill), a uranium ore-processing facility, located on a terrace overlooking the San Juan River in the town of Shiprock, New Mexico. Following the closure of the Mill, all tailings and associated materials were encapsulated in a disposal cell built on top of the former Mill and tailings piles. The milling operations, conducted at the site from 1954 to 1968, created radioactive tailings and process-related wastes that are now found in the groundwater. Elevated concentrations of constituents of concern—ammonium, manganese, nitrate, selenium, strontium, sulfate, and uranium—have also been measured in groundwater seeps in the nearby Many Devils Wash arroyo, leading to the inference that these constituents originated from the Mill. These constituents have also been reported in groundwater that is associated with Mancos Shale, the bedrock that underlies the site. The objective of this report is to increase understanding of the source of water and solutes to the groundwater beneath Many Devils Wash and to establish the background concentrations for groundwater that is in contact with the Mancos Shale at the site. This report presents evidence on three working hypotheses: (1) the water and solutes in Many Devils Wash originated from the operations at the former Mill, (2) groundwater in deep aquifers is upwelling under artesian pressure to recharge the shallow groundwater beneath Many Devils Wash, and (3) the groundwater beneath Many Devils Wash originates as precipitation that infiltrates into the shallow aquifer system and discharges to Many Devils Wash in a series of springs on the east side of the wash. The solute concentrations in the shallow groundwater of Many Devils Wash would result from the interaction of the water and the Mancos Shale if the source of water was upwelling from deep aquifers or precipitation. In order to compare the groundwater from various wells to groundwater that has been affected by Mill activities, a classification system was developed to determine which wells were most likely to have been affected. Affects to groundwater by the Mill were determined by using the reported uranium alpha activity ratios measured in groundwater samples, along with the concentration of the uranium and the location of the wells relative to the Mill. Activity ratios of 1.2 or less were determined to be the most reliable indicator of Mill-affected groundwater. Wells with samples that had a reported activity ratio of 1.2 or less were classified as Mill affected. To compare groundwater with background water-quality, data from groundwater seeps and springs in the Upper Eagle Nest Arroyo and Salt Creek Wash, located north of the San Juan River, are also presented and analyzed. Based on groundwater elevations and tritium concentrations measured in wells located between the disposal cell and Many Devils Wash, Mill water is not likely to reach Many Devils Wash. The tritium concentrations also indicate that groundwater from the Mill has not substantially affected Many Devils Wash in the past. Upwelling from deep aquifers was also determined to be an unlikely source, primarily by comparing the composition of the stable isotopes of water in the shallow groundwater with those reported in groundwater samples from the deeper aquifers. The stable-isotope compositions of the shallow groundwater around the site are enriched relative to the San Juan River and local meteoric lines, which suggests that most of the shallow groundwater has been influenced by evaporation and therefore was recharged at the surface. Several observations indicate that focused recharge is the likely source of groundwater in the area of Many Devils Wash. The visible erosional features in Many Devils Wash provide evidence of piping and groundwater sapping, and the distribution and type of vegetation in Many Devils Wash suggest that the focused recharge of precipitation is occurring. The estimated recharge from precipitation was calculated to be 0.0008 inches per year (in/yr) by using the mass-balance approach from reported seep discharge and 0.0011 in/yr using the chloride mass-balance approach. A conceptual model of groundwater quality beneath Many Devils Wash is presented to explain the source of solutes in the groundwater beneath Many Devils Wash. The major-ion concentrations and geochemical evolution in the groundwater beneath Many Devils Wash and across the study area support the conceptual model that the underlying Mancos Shale is the source of solutes. Differences in the major-ion composition between groundwater samples collected around the site, result from the degree of weathering to the Mancos Shale. The cation distribution appears to be an indicator of effects from the Mill, with samples from the Mill-affected wells largely having a calcium/magnesium-sulfate composition that resembles the reported compositions of more weathered shale; however, that composition could change if the Mill-processed water flowed into areas where the Mancos Shale was less weathered. On the basis of the widespread presence of uranium in the Mancos Shale and the distribution of aqueous uranium in the analog sites and other sites in the region, it appears likely that uranium in the groundwater of Many Devils Wash is naturally sourced from the Mancos Shale.

New Mexico