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Techniques for detecting effects of urban and rural land-use practices on stream-water chemistry in selected watersheds in Texas, Minnesota,and Illinois

Although considerable effort has been expended during the past two decades to control nonpoint-source contamination of streams and lakes in urban and rural watersheds, little has been published on the effectiveness of various management practices at the watershed scale. This report presents a discussion of several parametric and nonparametric statistical techniques for detecting changes in water-chemistry data. The need for reducing the influence of natural variability was recognized and accomplished through the use of regression equations. Traditional analyses have focused on fixed-frequency instantaneous concentration data; this report describes the use of storm load data as an alternative. Selected statistical techniques were applied to three urban watersheds in Texas and Minnesota and three rural watersheds in Illinois. For the urban watersheds, single- and paired-site data-collection strategies were considered. The paired-site strategy was much more effective than the singlesite strategy for detecting changes. Analysis of storm load regression residuals demonstrated the potential utility of regressions for variability reduction. For the rural watersheds, none of the selected techniques were effective at identifying changes, primarily due to a small degree of management-practice implementation, potential errors introduced through the estimation of storm load, and small sample sizes. A Monte Carlo sensitivity analysis was used to determine the percent change in water chemistry that could be detected for each watershed. In most instances, the use of regressions improved the ability to detect changes.

Illinois, Minnesota, Texas↗

Ground-water, surface-water, and water-chemistry data, Black Mesa area, northeastern Arizona, 1996

The Black Mesa monitoring program is designed to document long-term effects of ground-water pumping from the N aquifer by industrial and municipal users. The N aquifer is the major source of water in the 5,400-square-mile Black Mesa area, and the ground water occurs under confined and unconfined conditions. Monitoring activities include continuous and periodic measurements of (1) ground-water pumpage from the confined and unconfined parts of the aquifer, (2) ground-water levels in the confined and unconfined areas of the aquifer, (3) surface-water discharge, and (4) chemistry of the ground water and surface water. In 1996, ground-water withdrawals for industrial and municipal use totaled about 7,040 acre-feet, which is less than a 1-percent decrease from 1995. Pumpage from the confined part of the aquifer decreased by about 3 percent to 5,390 acre-feet, and pumpage from the unconfined part of the aquifer increased by about 9 percent to 1,650 acre-feet. Water-level declines in the confined area during 1996 were recorded in 11 of 13 wells, and the median change was a decline of about 2.7 feet as opposed to a decline of 1.8 feet for 1995. Water-level declines in the unconfined area were recorded in 11 of 18 wells, and the median change was a decline of 0.5 foot in 1996 as opposed to a decline of 0.1 foot in 1995. The average low-flow discharge at the Moenkopi streamflow-gaging station was 2.3 cubic feet per second in 1996. Streamflow-discharge measurements also were made at Laguna Creek, Dinnebito Wash, and Polacca Wash during 1996. Average low-flow discharge was 2.3 cubic feet per second at Laguna Creek, 0.4 cubic foot per second at Dinnebito Wash, and 0.2 cubic foot per second at Polacca Wash. Discharge was measured at three springs. Discharge from Moenkopi School Spring decreased by about 2 gallons per minute from the measurement in 1995. Discharge from an unnamed spring near Dennehotso decreased by 1.3 gallons per minute from the measurement made in 1995; however, discharge increased slightly at Burro Spring. Regionally, long-term water-chemistry data for wells and springs have remained stable.

Open-File Report↗

Vertical gradients in water chemistry and age in the southern High Plains Aquifer, Texas, 2002

The southern High Plains aquifer is the primary source of water used for domestic, industrial, and irrigation purposes in parts of New Mexico and Texas. Despite the aquifer's importance to the overall economy of the southern High Plains, fundamental ground-water characteristics, such as vertical gradients in water chemistry and age, remain poorly defined. As part of the U.S. Geological Survey's National Water-Quality Assessment Program, water samples from nested, short-screen monitoring wells installed in the southern High Plains aquifer at two locations (Castro and Hale Counties, Texas) were analyzed for field parameters, major ions, nutrients, trace elements, dissolved organic carbon, pesticides, stable and radioactive isotopes, and dissolved gases to evaluate vertical gradients in water chemistry and age in the aquifer. Tritium measurements indicate that recent (post-1953) recharge was present near the water table and that deeper water was recharged before 1953. Concentrations of dissolved oxygen were largest (2.6 to 5.6 milligrams per liter) at the water table and decreased with depth below the water table. The smallest concentrations were less than 0.5 milligram per liter. The largest major-ion concentrations generally were detected at the water table because of the effects of overlying agricultural activities, as indicated by postbomb tritium concentrations and elevated nitrate and pesticide concentrations at the water table. Below the zone of agricultural influence, major-ion concentrations exhibited small increases with depth and distance along flow paths because of rock/water interactions and mixing with water from the underlying aquifer in rocks of Cretaceous age. The concentration increases primarily were accounted for by dissolved sodium, bicarbonate, chloride, and sulfate. Nitrite plus nitrate concentrations at the water table were 2.0 to 6.1 milligrams per liter as nitrogen, and concentrations substantially decreased with depth in the aquifer to a maximum concentration of 0.55 milligram per liter as nitrogen. Dissolved-gas and nitrogen-isotope data from the deep wells in Castro County indicate that denitrification occurred in the aquifer, removing 74 to more than 97 percent of the nitrate originally present in recharge. There was no evidence of denitrification in the deep part of the aquifer in Hale County. After correcting for denitrification effects, the background concentration of nitrate in water recharged before 1953 ranged from 0.4 to 3.2 milligrams per liter as nitrogen, with an average of 1.6 milligrams per liter as nitrogen. The d15N composition of background nitrate at the time of recharge was estimated to range from 9.6 to 12.3 per mil. Mass-balance models indicate that the decreases in dissolved oxygen and nitrate concentrations and small increases in major-ion concentrations along flow paths can be accounted for by small amounts of silicate-mineral and calcite dissolution; SiO2, goethite, and clay-mineral precipitation; organic-carbon and pyrite oxidation; denitrification; and cation exchange. Mass-balance models for some wells also required mixing with water from the underlying aquifer in rocks of Cretaceous age to achieve mole and isotope balances. Carbon mass transfers identified in the models were used to adjust radiocarbon ages of water samples recharged before 1953. Adjusted radiocarbon ages ranged from less than 1,000 to 9,000 carbon-14 years before present. Radiocarbon ages were more sensitive to uncertainties in the carbon-14 content of recharge than uncertainties in carbon mass transfers, leading to 1-sigma uncertainties of about ?2,000 years in the adjusted ages. Despite these relatively large uncertainties in adjusted radiocarbon ages, it appears that deep water in the aquifer was considerably older (at least 1,000 years) than water near the water table. There was essentially no change in ground-water age with depth in deeper parts of the aquifer, indicating that water in that

Texas↗

Trends in streamflow, sedimentation, and sediment chemistry for the Wolf River, Menominee Indian Reservation, Wisconsin, 1850-1999

Historical trends in streamflow, sedimentation, and sediment chemistry of the Wolf River were examined for a 6-mile reach that flows through the southern part of the Menominee Indian Reservation and the northern part of Shawano County, Wis. Trends were examined in the context of effects from dams, climate, and land-cover change. Annual flood peaks and mean monthly flow for the Wolf River were examined for 1907-96 and compared to mean annual and mean monthly precipitation. Analysis of trends in sedimentation (from before about 1850 through 1999) involved collection of cores and elevation data along nine valley transects spanning the Wolf River channel, flood plain, and backwater and impounded areas; radioisotope analyses of impounded sediment cores; and analysis of General Land Office Survey Notes (1853-91). Trends in sediment chemistry were examined by analyzing samples from an impoundment core for minor and trace elements. Annual flood peaks for the Wolf River decreased during 1907-49 but increased during 1950-96, most likely reflecting general changes in upper-atmospheric circulation patterns from more zonal before 1950 to more meridional after 1950. The decrease in flood peaks during 1907-49 may also, in part, be due to forest regrowth. Mean monthly streamflow during 1912-96 increased for the months of February and March but decreased for June and July, suggesting that spring snowmelt occurs earlier in the season than it did in the past. Decreases in early summer flows may be a reflection earlier spring snowmelt and large rainstorms in early spring rather than early summer. These trends also may reflect upper-atmospheric circulation patterns. The Balsam Row Dam impoundment contains up to 10 feet of organic-rich silty clay and has lost much of its storage capacity. Fine sediment has accumulated for 1.8 miles upstream from the Balsam Row Dam. Historical average linear and mass sedimentation rates in the Balsam Row impoundment were 0.09 feet per year and 1.15 pounds per square foot per year for 1927-62 and 0.10 feet per year and 1.04 pounds per square foot per year for 1963-99. Sedimentation in the impoundment was episodic and was associated with large floods, especially the flood-related failure of the Keshena Falls Dam in 1972 and a large flood in 1973. Sand deposition is common in the Wolf River upstream from the impounded reach for 2.5 miles and is caused by the base-level increase associated with the Balsam Row Dam. Some sand deposition also may have been associated with logging and log drives in the late 1800s and the failure of the Keshena Falls Dam. In the upstream 1.5-mile part of the studied reach, the substrate is mainly rocky; however, about 2,000 feet downstream from Keshena Falls, the channel has narrowed and incised since the 1890s, likely related to human alterations associated with logging, log drives, and (or) changes in hydraulics and sediment characteristics associated with completion of the Keshena Falls Dam and head race in 1908. Minor- and trace-element concentrations in sediment from Balsam Row impoundment and other depositional areas along the Wolf River generally reflect background conditions as affected by watershed geology and historical inputs from regional and local atmospheric deposition.

Wisconsin↗

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↗

Atmospheric Deposition and Surface-Water Chemistry in Mount Rainier and North Cascades National Parks, U.S.A., Water Years 2000 and 2005-2006

High-elevation aquatic ecosystems in Mount Rainier and North Cascades National Parks are highly sensitive to atmospheric deposition of nitrogen and sulfur. Thin, rocky soils promote fast hydrologic flushing rates during snowmelt and rain events, limiting the ability of basins to neutralize acidity and assimilate nitrogen deposited from the atmosphere. Potential effects of nitrogen and sulfur deposition include episodic or chronic acidification of terrestrial and aquatic ecosystems. In addition, nitrogen deposition can cause eutrophication of water bodies and changes in species composition in lakes and streams. This report documents results of a study performed by the U.S. Geological Survey, in cooperation with the National Park Service, of the effects of atmospheric deposition of nitrogen and sulfur on surface-water chemistry in Mount Rainier and North Cascades National Parks. Inorganic nitrogen in wet deposition was highest in the vicinity of North Cascades National Park, perhaps due to emissions from human sources and activities in the Puget Sound area. Sulfur in wet deposition was highest near the Pacific coast, reflecting the influence of marine aerosols. Dry deposition generally accounted for less than 30 percent of wet plus dry inorganic nitrogen and sulfur deposition, but occult deposition (primarily fog) represents a potentially substantial unmeasured component of total deposition. Trend analyses indicate inorganic nitrogen in wet deposition was relatively stable during 1986-2005, but sulfur in wet deposition declined substantially during that time, particularly after 2001, when emissions controls were added to a large powerplant in western Washington. Surface-water sulfate concentrations at the study site nearest the powerplant showed a statistically significant decrease between 2000 and 2005-06, but there was no statistically significant change in alkalinity, indicating a delayed response in surface-water alkalinity. Seasonal patterns in surface-water chemistry and streamflow are strongly influenced by melting of seasonal snowpacks, which release large amounts of dilute, slightly acidic water to terrestrial and aquatic ecosystems during spring snowmelt. Concentrations of sulfate, alkalinity, and base cations in surface water declined rapidly during snowmelt, then gradually recovered during summer and fall. Preferential elution of acidic solutes from the snowpack at the beginning of snowmelt may cause episodic acidification in small alpine streams; evidence is provided by a stream sample collected at one of the sites during spring 2006 that was acidic (pH = 4.8, alkalinity = -18 microequivalents per liter) and had high concentrations of nitrate and sulfate and low concentrations of weathering products. Rain-on-snow events caused sharp declines in specific conductance, which was measured continuously using an in-stream sensor. A strong correlation was observed between measured specific conductance and measured alkalinity (r2 = 0.76), permitting estimation of alkalinity from specific-conductance data using a regression equation. Estimated alkalinity declined by an order of magnitude during the rain-on-snow events, in one case to 8 microequivalents per liter. Actual declines in alkalinity might be greater because the regression equation accounts only for dilution effects; at low concentrations, the relation between specific conductance and alkalinity is likely to be nonlinear and have a negative intercept (negative alkalinity). Thus, episodic acidification is possible during rain-on-snow events. The scale of episodic acidification is unknown, but if it occurs, it could have detrimental effects on aquatic life and amphibians. Historical lake-survey data indicate that most lakes are oligotrophic and have low nitrogen and phosphorus concentrations. Nitrogen limitation is more common in lakes in Mount Rainier National Park than in North Cascades National Park due to higher nitrate concentrations at North Cascades. T

Scientific Investigations Report↗

Hydrogeology, Water Chemistry, and Factors Affecting the Transport of Contaminants in the Zone of Contribution of a Public-Supply Well in Modesto, Eastern San Joaquin Valley, California

Ground-water chemistry in the zone of contribution of a public-supply well in Modesto, California, was studied by the U.S. Geological Survey National Water Quality Assessment (NAWQA) Program's topical team for Transport of Anthropogenic and Natural Contaminants (TANC) to supply wells. Twenty-three monitoring wells were installed in Modesto to record baseline hydraulic information and to collect water-quality samples. The monitoring wells were divided into four categories that represent the chemistry of different depths and volumes of the aquifer: (1) water-table wells were screened between 8.5 and 11.7 m (meter) (28 and 38.5 ft [foot]) below land surface (bls) and were within 5 m (16 ft) of the water table; (2) shallow wells were screened between 29 and 35 m (95 and 115 ft) bls; (3) intermediate wells were screened between 50.6 and 65.5 m (166 and 215 ft) bls; and (4) deep wells are screened between 100 to 106 m (328 and 348 ft) bls. Inorganic, organic, isotope, and age-dating tracers were used to characterize the geochemical conditions in the aquifer and understand the mechanisms of mobilization and movement of selected constituents from source areas to a public-supply well. The ground-water system within the study area has been significantly altered by human activities. Water levels in monitoring wells indicated that horizontal movement of ground water was generally from the agricultural areas in the northeast towards a regional water-level depression within the city in the southwest. However, intensive pumping and irrigation recharge in the study area has caused large quantities of ground water to move vertically downward within the regional and local flow systems. Analysis of age tracers indicated that ground-water age varied from recent recharge at the water table to more than 1,000 years in the deep part of the aquifer. The mean age of shallow ground water was determined to be between 30 and 40 years. Intermediate ground water was determined to be a mixture of modern (Post-1950) and old (Pre-1950) ground water. As a result, concentrations of age tracers were detectable but diluted by older ground water. Deep ground water generally represented water that was recharged under natural conditions and therefore had much older ages. Ground water reaching the public-supply well was a mixture of older intermediate and deep ground water and young shallow ground water that has been anthropogenically-influenced to a greater extent than intermediate ground water. Uranium and nitrate pose the most significant threat to the quality of water discharged from the public-supply well. Although pesticides and VOCs were present in ground water from the public-supply well and monitoring wells, currently concentrations of these contaminants are generally less than one-hundredth the concentration of drinking water standards. In contrast, both uranium and nitrate were above half the concentration of drinking water standards for public-supply well samples, and were above drinking water standards for several water-table and shallow monitoring wells. Shallow ground water contributes roughly 20 percent of the total flow to the public-supply well and was the entry point of most contaminants reaching the public-supply well. Naturally-occurring uranium, which is commonly adsorbed to aquifer sediments, was mobilized by oxygen-rich, high-alkalinity water, causing concentrations in some monitoring wells to be above the drinking-water standard of 30 ug/L (microgram per liter). Adsorption experiments, sediment extractions, and uranium isotopes indicated uranium in water-table and shallow ground water was leached from aquifer sediments. Uranium is strongly correlated to bicarbonate concentrations (as measured by alkalinity) in ground water. Bicarbonate can effectively limit uranium adsorption to sediments. As a result, continued downward movement of high-alkalinity, oxygen-rich ground water will likely lead to larger portions of the aquifer having

Scientific Investigations Report↗

Groundwater Hydrology and Chemistry in and near an Emulsified Vegetable-Oil Injection Zone, Solid Waste Management Unit 17, Naval Weapons Station Charleston, North Charleston, South Carolina, 2004-2009

The U.S. Geological Survey and the Naval Facilities Engineering Command Southeast investigated the hydrology and groundwater chemistry in the vicinity of an emulsified vegetable-oil injection zone at Solid Waste Management Unit (SWMU) 17, Naval Weapons Station Charleston, North Charleston, South Carolina. In May 2004, Solutions-IES initiated a Phase-I pilot-scale treatability study at SWMU17 involving the injection of an edible oil emulsion into the aquifer near wells 17PS-01, 17PS-02, and 17PS-03 to treat chlorinated solvents. The Phase-I injection of emulsified vegetable oil resulted in dechlorination of trichloroethene (TCE) to cis-1,2-dichloroethene (cDCE), but the dechlorination activity appeared to stall at cDCE, with little further dechlorination of cDCE to vinyl chloride (VC) or to ethene. The purpose of the present investigation was to examine the groundwater hydrology and chemistry in and near the injection zone to gain a better understanding of the apparent remediation stall. It is unlikely that the remediation stall was due to the lack of an appropriate microbial community because groundwater samples showed the presence of Dehalococcoides species (sp.) and suitable enyzmes. The probable causes of the stall were heterogeneous distribution of the injectate and development of low-pH conditions in the injection area. Because groundwater pH values in the injection area were below the range considered optimum for dechlorination activity, a series of tests was done to examine the effect on dechlorination of increasing the pH within well 17PS-02. During and following the in-well pH-adjustment tests, VC concentrations gradually increased in some wells in the injection zone that were not part of the in-well pH-adjustment tests. These data possibly reflect a gradual microbial acclimation to the low-pH conditions produced by the injection. In contrast, a distinct increase in VC concentration was observed in well 17PS-02 following the in-well pH increase. Adjustment of the pH to near-neutral values in well 17PS-02 may have made that well relatively favorable to VC production compared with much of the rest of the injection zone, possibly accounting for acceleration of VC production at that well. Following a Phase-II injection in which Solutions-IES, Inc., injected pH-buffered emulsified vegetable oil with an improved efficiency injection approach, 1,1-dichloroethene, TCE, and cDCE rapidly decreased in concentration and are now (2009) undetectable in the injection zone, with the exception of a low concentration (43 micrograms per liter, August 2009) of cDCE in well 17PS-01. In August 2009, VC was still present in groundwater at the test wells in concentrations ranging from 150 to 640 micrograms per liter. The Phase-II injection, however, appears to have locally decreased aquifer permeability, possibly resulting in movement of contamination around, rather than through, the treatment area.

North Carolina↗

Hydrogeology, water chemistry, and transport processes in the zone of contribution of a public-supply well in Albuquerque, New Mexico, 2007-9

The National Water-Quality Assessment Program (NAWQA) of the U.S. Geological Survey began a series of groundwater studies in 2001 in representative aquifers across the Nation in order to increase understanding of the factors that affect transport of anthropogenic and natural contaminants (TANC) to public-supply wells. One of 10 regional-scale TANC studies was conducted in the Middle Rio Grande Basin (MRGB) in New Mexico, where a more detailed local-scale study subsequently investigated the hydrogeology, water chemistry, and factors affecting the transport of contaminants in the zone of contribution of one 363-meter (m) deep public-supply well in Albuquerque. During 2007 through 2009, samples were collected for the local-scale study from 22 monitoring wells and 3 public-supply (supply) wells for analysis of major and trace elements, arsenic speciation, nutrients, dissolved organic carbon, volatile organic compounds (VOCs), dissolved gases, stable isotopes, and tracers of young and old water. To study groundwater chemistry and ages at various depths within the aquifer, the monitoring wells were divided into three categories: (1) each shallow well was screened across the water table or had a screen midpoint within 18.3 m of the water level in the well; (2) each intermediate well had a screen midpoint between about 27.1 and 79.6 m below the water level in the well; and (3) each deep well had a screen midpoint about 185 m or more below the water level in the well. The 24-square-kilometer study area surrounding the "studied supply well" (SSW), one of the three supply wells, consists of primarily urban land within the MRGB, a deep alluvial basin with an aquifer composed of unconsolidated to moderately consolidated deposits of sand, gravel, silt, and clay. Conditions generally are unconfined, but are semiconfined at depth. Groundwater withdrawals for public supply have substantially changed the primary direction of flow from northeast to southwest under predevelopment conditions, to west to east under modern conditions. Analysis of age tracers indicates that groundwater from most sampled wells is dominated by old (pre-1950) water, ranging in mean age from about 4,000 years to more than 22,000 years, but includes a fraction of young (post-1950) recharge. Patterns in chemical and isotopic data are consistent with the conclusions that shallow groundwater in the area typically includes a fraction that evaporated prior to recharge and (or) flushed accumulated solutes out of the unsaturated zone during recharge, and that shallow groundwater has mixed to deeper parts of the aquifer, which receives recharge mainly by seepage from the Rio Grande. Among shallow and intermediate wells that produced water with a fraction of young recharge, that fraction ranged between 1.5 and 46 percent. Samples from the two deep wells had groundwater ages exceeding 18,000 years, with no fraction of young recharge. Two supply wells (including the SSW) had a fraction of young recharge, which ranged between about 3 and 11 percent, despite mean groundwater ages exceeding 10,000 years. The fraction of young recharge to the SSW varied seasonally, probably because seasonal pumping patterns affected local hydraulic gradients and (or) because of flow through the well bore when the SSW is not pumping. Well-bore flow data collected during winter (low-pumping season) indicated that about 61 percent of the water pumped from the SSW entered the well from the intermediate part of the aquifer, and that the remaining 39 percent entered from the deep part of the aquifer. Volatile organic compounds (VOCs) were detected in samples from most shallow and intermediate monitoring wells and from two of three supply wells, including the SSW. Detected VOCs were primarily chlorinated solvents or their degradation products. Many of the wells in which most of these VOCs were detected are located near known sites of solvent contamination that were targeted for sampling because trichloroethylene (TCE) and cis-1,2-dichloroethylene had been detected in the SSW, and several of these wells may have become contaminated at least partly because of enhanced vertical migration associated with the pumping of and (or) direct migration down deep well bores. Except for TCE in the sample from a shallow monitoring well, all detections of VOCs were at concentrations below Maximum Contaminant Levels (MCLs) set by the U.S. Environmental Protection Agency. Concentrations of all VOCs detected in the supply wells were less than one-tenth of the corresponding MCLs. However, the presence of VOCs in all but deep groundwater, including the detection of chloroform (a chlorination byproduct) in several shallow wells, indicates that groundwater in the study area commonly is affected by human activities, even to substantial depths. The only natural contaminant detected at concentrations near or above its MCL was arsenic, which has been detected at elevated concentrations across broad areas of the MRGB. Concentrations of arsenic, present primarily as arsenate, exceeded the MCL of 10 micrograms per liter (μg/L) in water from the two deep wells (one of which had the highest concentration, 35 μg/L), from one intermediate well, and from two supply wells, including the SSW. Water-quality and solid-phase data from this study are consistent with elevated arsenic concentrations in groundwater being related to pH-dependent desorption of arsenic from ferric oxyhydroxides in sediments in deep parts of the aquifer. Concentrations of nitrate ranged between 1.3 and 5.4 milligrams per liter (mg/L) in water from shallow wells screened across the water table, but were less than 0.9 mg/L in water from all but one deeper well. Nitrogen isotopes and chloride/bromide ratios for shallow wells were consistent with natural soil nitrogen. Nitrate concentrations and nitrogen isotopes indicated that denitrification is occurring at intermediate aquifer depths, and that the progress of the denitrification reaction typically is greatest for wells that include a fraction of groundwater associated with particular recharge sources or with known sites of contamination contributing organic compounds that can provide a carbon source for microbial respiration. Overall, hydrologic and chemical data from the study area indicate that young recharge is reaching the aquifer across broad areas and is migrating from shallow to intermediate depths of the aquifer as a result of mixing that is associated with human development of groundwater. Consequently, groundwater that human activities in the urban study area have affected is present at depths that are within the screened intervals of public-supply wells, resulting in detections of VOCs and implying greater vulnerability to anthropogenic contamination than might be assumed based on the dominantly old age of the regional groundwater. However, the fractions of old groundwater that public-supply wells produce substantially dilute the anthropogenic contaminants, while contributing natural contaminants (primarily arsenic) to the wells. Based on data from the SSW, vulnerability of public-supply wells to natural and anthropogenic contaminants in the area changes through time, including with seasonal changes in pumping stresses that alter the fractions of young and old water being contributed to wells.

New Mexico↗

Biological assessment and streambed-sediment chemistry of streams in the Indianapolis metropolitan area, Indiana, 2003–2008

During 2003–2008, the U.S. Geological Survey sampled 13 sites in the Indianapolis metropolitan area in Indiana for benthic invertebrates, fish communities, and streambed-sediment chemistry. Data from seven White River sites and six tributary sites complement surface-water chemistry data collected by the Indianapolis Department of Public Works. The information is being used to assess changes in water quality in conjunction with the City's programs to reduce combined sewer overflows and other point and nonpoint sources of pollution in the Indianapolis area. During the study, 233 benthic-invertebrate taxa were identified from which the Ephemeroptera, Plecoptera, and Trichoptera (EPT) Index, the Hilsenhoff Biotic Index (HBI), and the Invertebrate Community Index (ICI) were calculated. EPT index scores ranged from 2 to 16 on the White River and from 2 to 17 on the tributaries. EPT index scores indicate that these pollution-intolerant taxa are more prevalent upstream from and away from the combined-sewer areas of Indianapolis. HBI scores from sites on the White River ranged from 4.67 (good) to 9.55 (very poor), whereas on the tributaries, scores ranged from 4.21 (very good) to 8.14 (poor). Lower HBI scores suggest that less organic pollution was present and, like the EPT scores, indicate better conditions where combined-sewer overflows (CSOs) are not present. Similarly, ICI scores indicated better conditions upstream from the CSO outfalls on the White River. White River scores ranged from 12 to 46, where higher ICI scores indicate better conditions in the benthic-invertebrate community. ICI scores at the tributary sites ranged from 12 to 52, with the highest scores on streams without CSOs.

Indiana↗

Hydrogeologic characterization, groundwater chemistry, and vulnerability assessment, Ute Mountain Ute Reservation, Colorado and Utah

The U.S. Geological Survey, in cooperation with the Ute Mountain Ute Tribe (UMUT), initiated a study in 2016 to increase understanding of the hydrogeology and chemistry of groundwater within select areas of the Ute Mountain Ute Reservation (UMUR) in Colorado and Utah, identify vulnerabilities to the system and other natural resources, and outline information needs to aid in the understanding and protection of groundwater resources. The results presented for this study can be used to support the UMUT’s goal of protecting their vital groundwater resources on the UMUR. Hydrogeologic conditions were characterized for the surficial aquifer contained in Quaternary-age unconsolidated surficial deposits and the Dakota aquifer contained in the Cretaceous-age Dakota Sandstone. In the surficial aquifer, median depth to water ranges from about 5.4 to 17.2 feet below land surface in the Farm and Ranch Enterprise area and 11 to 34 feet below land surface in the Towaoc area, and the water table slopes generally southwest or south. A map of depth to the top of the Dakota Sandstone was constructed from existing well data. Depths range from zero in outcrop areas to more than 3,000 feet below land surface on mesas in the southeastern part of the UMUR. Groundwater-chemistry data were collected by the UMUT from 13 springs and 31 wells from 1996 through 2017. Specific conductance was much lower for samples from springs than from wells; median values were 512 and 6,024 microsiemens per centimeter at 25 degrees Celsius, respectively. Spring samples were well oxygenated. A few well samples were anoxic (dissolved oxygen concentrations less than 0.5 milligrams per liter [mg/L]), indicating reducing conditions in the aquifer. About 75 percent of spring samples had fresh water (total dissolved solids concentrations less than 1,000 mg/L), and about 85 percent of well samples had brackish or highly saline water (total dissolved solids concentrations greater than 1,000 mg/L). Water type for springs on the Ute Mountains was calcium bicarbonate. Lower-altitude springs had a calcium-sulfate water type. Most well samples had sodium as the dominant cation, and sulfate, bicarbonate, and chloride as the dominant anions. Fluoride concentrations in about 45 percent of well samples were greater than an agricultural-use standard of 2 mg/L. Nitrate plus nitrite concentrations in most spring and well samples were less than about 1.6 mg/L per liter. Concentrations in samples from wells in the irrigated agricultural area were elevated; the maximum concentration was 78.5 mg/L. About one-half of the trace-element samples had concentrations that were less than laboratory reporting limits. Only aluminum, arsenic, and selenium in spring samples, and boron and selenium in well samples, were detected at concentrations greater than surface-water standards or water-quality standards for agricultural use of groundwater. Only three organic compounds, the pesticides alachlor and atrazine and the volatile organic compound di(2-ethylhexyl) phthalate, were detected in well samples. The Escherichia coli bacteria was detected in 47 and 23 percent of samples from wells and springs, respectively. The E. coli detections included samples from three culturally significant springs, which did not meet the UMUT cultural-use standard of total absence of E. coli. Tritium and carbon-14 were the primary environmental tracers used for interpreting groundwater ages for Lopez 2 Spring and five wells (AP–1, 5000 Block, Cottonwood Spring, Goodknight, and SE Toe). Water from the AP–1 well contained a mixture of pre- and post-1950s recharge. Tritium and carbon-14 recharge ages for Lopez 2 Spring (post-1950s in age), Goodknight and SE Toe wells (pre-1950s in age), and Cottonwood Spring well (primarily pre-1950s in age) are supported by helium-4 data. The helium-4 data for the 5000 Block well are inconsistent with the tritium and carbon-14 age of pre-1950s recharge because of interference caused by high methane concentrations in the water. Springs and surficial deposits are more vulnerable to contamination from anthropogenic chemicals than deeper bedrock wells. Bedrock aquifers are vulnerable in areas where the geologic formations containing the aquifers are exposed at the land surface. Groundwater in deep bedrock aquifers is likely thousands of years old and is not currently affected by present-day land uses. Both shallow and deep groundwater are vulnerable to naturally occurring salts and minerals, such as of total dissolved solids, major ions, nitrate, and trace elements. Effects of a changing climate on water resources and other ecological characteristics of the UMUR could include changes in evapotranspiration, a decrease in snowpack, decreased aquifer recharge and flow of springs, a decrease in soil moisture, and increased occurrence of wildfires and forest mortality. Of particular interest for the UMUT are possible effects of a changing climate on medicinal and culturally important plants and springs Several information needs were identified during this study that would aid in the understanding and protection of groundwater resources on the UMUR. These include well-completion information for bedrock wells, the collection of environmental tracer data at additional wells, the addition of methane and hydrocarbon analysis to well sampling plans, and the resampling of springs and wells that were last sampled in 2002 or earlier.

Colorado↗

Vertical gradients in water chemistry in the central High Plains aquifer, southwestern Kansas and Oklahoma panhandle, 1999

The central High Plains aquifer is the primary source of water for domestic, industrial, and irrigation uses in parts of Colorado, Kansas, New Mexico, Oklahoma, and Texas. Water-level declines of more than 100 feet in some areas of the aquifer have increased the demand for water deeper in the aquifer. The maximum saturated thickness of the aquifer ranged from 500 to 600 feet in 1999. As the demand for deeper water increases, it becomes increasingly important for resource managers to understand how the quality of water in the aquifer changes with depth. In 1998?99, 18 monitoring wells at nine sites in southwestern Kansas and the Oklahoma Panhandle were completed at various depths in the central High Plains aquifer, and one monitoring well was completed in sediments of Permian age underlying the aquifer. Water samples were collected once from each well in 1999 to measure vertical gradients in water chemistry in the aquifer. Tritium concentrations measured in ground water indicate that water samples collected in the upper 30 feet of the aquifer were generally recharged within the last 50 years, whereas all of the water samples collected at depths more than 30 feet below the water table were recharged more than 50 years ago. Dissolved oxygen was present throughout the aquifer, with concentrations ranging from 1.7 to 8.4 mg/L. Water in the central High Plains aquifer was predominantly a calcium-bicarbonate type that exhibited little variability in concentrations of dissolved solids with depth (290 to 642 mg/L). Exceptions occurred in some areas where there had been upward movement of mineralized water from underlying sediments of Permian age and areas where there had been downward movement of mineralized Arkansas River water to the aquifer. Calcium-sulfate and sodium-chloride waters dominated and concentrations of dissolved solids were elevated (862 to 4,030 mg/L) near the base of the aquifer in the areas of upward leakage. Dissolution of gypsum or anhydrite and halite in sediments of Permian age by ground water was the likely source of calcium, sulfate, sodium, and chloride in those waters. Calcium-sodium-sulfate waters dominated, and concentrations of dissolved solids were as large as 4,916 mg/L near the water table in the area of downward leakage. Dissolution of minerals in sedimentary deposits of marine origin in upstream areas of the Arkansas River drainage were the likely sources of calcium, sodium, and sulfate in those waters. Nitrate was detected throughout the aquifer and the background concentration was estimated to be 2.45 mg/L as N. The largest nitrate concentrations (8.28, 22, and 54.4 mg/L as N) occurred in recently recharged water collected adjacent to irrigated fields. Three pesticides (atrazine, metolachlor, simazine) and five pesticide degradation products (alachlor ethanesulfonic acid, alachlor oxanilic acid, deethylatrazine, metolachlor ethanesulfonic acid, metolachlor oxanilic acid) were detected in recently recharged water from six water-table wells. Five of the six wells were adjacent to irrigated fields. These data indicate that concentrations of nitrate and pesticides increased over time in some areas of the aquifer as a result of agricultural activities. Results from this study indicate that vertical gradients in water chemistry existed in the central High Plains aquifer. The chemical gradients resulted from chemical inputs to the aquifer from underlying sediments of Permian age, from the Arkansas River, and from agricultural activities. In areas where those chemical inputs occurred, water quality in the aquifer was impaired and may not have been suitable for some intended uses.

Water-Resources Investigations Report↗

Ground-water, surface-water, and water-chemistry data, Black Mesa Area, northeastern Arizona — 2000–2001, and performance and sensitivity of the 1988 USGS numerical model of the N aquifer

The N aquifer is the major source of water in the 5,400-square-mile area of Black Mesa in northeastern Arizona. Availability of water is an important issue in this area because of continued industrial and municipal use, a growing population, and precipitation of about 6 to 14 inches per year. The monitoring program in Black Mesa has been operating since 1971 and is designed to determine the long-term effects of ground-water withdrawals from the N aquifer for industrial and municipal uses. The monitoring program includes measurements of (1) ground-water pumping, (2) ground-water levels, (3) spring discharge, (4) surface-water discharge, and (5) ground-water chemistry. In 2000, total ground-water withdrawals were 7,740 acre-feet, industrial use was 4,490 acre-feet, and municipal use was 3,250 acre-feet. From 1999 to 2000, total withdrawals increased by 9 percent, industrial use increased by 7 percent, and municipal use increased by 12 percent. From 1999 to 2001, water levels declined in 10 of 15 wells in the unconfined part of the aquifer, and the median change was -0.4 foot. Water levels declined in 8 of 16 wells in the confined part of the aquifer, and the median change was -0.2 foot. From the prestress period (prior to 1965) to 2001, the median water-level change for 33 wells was -17.2 feet. Median water-level changes were -1.2 feet for 15 wells in the unconfined part of the aquifer and -31.0 feet for 18 wells in the confined part. Discharges were measured once in 1999 and once in 2001 at four springs. Discharges decreased by 5 percent and 33 percent at two springs and increased by 3 percent and 81 percent at two springs. For about the past 10 years, discharges did not significantly change in Burro Spring, the unnamed spring near Dennehotso, and Moenkopi School Spring. The record of discharge from a consistent measuring point for Pasture Canyon Spring is too short for statistical analysis of trends. Continuous records of surface-water discharge have been collected from July 1976 to 2000 at Moenkopi Wash, July 1996 to 2000 at Laguna Creek, June 1993 to 2000 at Dinnebito Wash, and April 1994 to 2000 at Polacca Wash. Median flows for November, December, January, and February of each water year were used as an index of ground-water discharge to those streams. There is no significant trend in the median winter flows for Moenkopi Wash from 1977 to 2000. The records for the other three streams are too short for a statistical analysis of trends. The median winter flows for Dinnebito Wash and Polacca Wash, however, appear to have decreased during the last 6 years. There is no apparent trend in the median winter flows for Laguna Creek since 1997. In 2001, water samples were collected from 12 wells and 4 springs and analyzed for selected chemical constituents. Dissolved-solids concentrations ranged from 102 to 628 milligrams per liter. Water samples from 9 of the wells and from the 4 springs had less than 350 milligrams per liter of dissolved solids. Water-chemistry data with sufficient years of record for a statistical analysis of trends over time are available from 7 wells and 4 springs. From about the mid-1980s or early 1990s to 2001 there are no significant trends in the concentrations of dissolved solids, chloride, and sulfate in water samples from 6 of the 7 wells. The concentration of one tested constituent (dissolved solids) in samples from Rocky Ridge PM3 significantly increased from 1990 to 2001. From the late 1980s to 2001, there are no significant trends in the concentrations of dissolved solids, chloride, and sulfate in water samples from Burro Spring, the unnamed spring near Dennehotso, and Pasture Canyon Spring. From 1987 to 2001, concentrations of chloride and sulfate significantly increased in water samples from Moenkopi School Spring and concentrations of dissolved solids did not significantly change. The performance and sensitivity of the 1988 USGS numerical model of the N aquifer were analyzed. The overall performance of the model in steady-state conditions is reasonable for residuals of heads (difference between observed and simulated steady-state heads); 80 percent of the absolute values of residuals are less than 38 feet. Simulated flows are about 40 percent different than estimated flows at two of three discharge areas; however, this comparison is only a rough approximation of performance because the accuracy of the estimated steady-state flows is uncertain. The overall performance of the model for transient conditions is fair for residuals of changes in head (difference between observed and simulated changes in head from steady state to 1999); 80 percent of the absolute values of residuals are less than 31 feet. The model is biased in two areas. In the Tuba City area, simulated changes in head are more negative than observed changes in head; all six residuals are positive, and three residuals are between 75 and 155 feet. In the confined area of the aquifer, observed changes in head are more negative than simulated changes in head; 12 of the 17 residuals are negative, and 8 residuals are between -57 and -20 feet. Analysis of model sensitivity indicates that recharge, transmissivity, and storage coefficient are the most important parameters for estimating heads, changes in heads, and flows. A strong correlation between recharge and transmissivity and a lack of independent and reliable estimates of recharge, transmissivity, and discharge create a uniqueness problem in model calibration. Several models could be constructed and calibrated with different values of recharge or transmissivity and still have similar fits to the observed data. Information from recent data and studies and more advanced modeling techniques could be used to develop a more representative and less uncertain model. Future data collection and studies should focus on obtaining a better definition of recharge, discharge, transmissivity, and storage coefficient.

Arizona↗

Relation of water chemistry of the Edwards aquifer to hydrogeology and land use, San Antonio Region, Texas

Water-chemistry data from the Edwards aquifer for 1976-85, consisting of nearly 1,500 chemical analyses from 280 wells and 3 springs, were used to statistically evaluate relations among ground-water chemistry, hydrogeology, and land use. Five land uses associated with sampled wells were classified on the basis of published information and field surveys. Four major subareas of the aquifer were defined to reflect the relative susceptibility of ground water to contamination originating from human activities using hydrogeologic and tritium data. Water from an agricultural area over the unconfined zone of the aquifer had the largest median concentration of nitrite plus nitrate. Large nitrite plus nitrate concentrations were spatially associated with large tritium concentrations and nitrogen isotopic ratios characteristic of streamflow recharge. Detections of fecal-coliform bacteria were associated mainly with water from wells completed in the unconfined zone. Most of the occurrences of tetrachloroethylene, l,2-(trans)-dichloroethylene, trichlorofluoromethane, 1,1,1-trichloroethane, and 2,4-D in ground water were associated with wells completed in the unconfined zone of the aquifer. Fatty acids detected in water from some wells may commonly be present naturally in ground water. The percentage of samples in which arsenic, barium, lead, and zinc were detected was similar among subareas; the samples were from the freshwater parts of the aquifer. Large lead and zinc concentrations were associated with volumes of pumpage less than 1,000 gallons. In general, the quality of ground water in the freshwater parts of the aquifer (north of the "bad-water" line) is suitable for all uses including human consumption. Two areas that are exceptions are: (1) Northeast of Garner Field in Uvalde, Texas, where PCE (tetrachloroethylene) has been detected in groundwater samples, and (2) north-central Bexar County near the former West Avenue landfill where PCE and benzene have been detected in ground-water samples. Concentrations of these organic compounds in water from many wells in the two areas exceed the maximum contaminant level for human consumption set by the U.S. Environmental Protection Agency.

Water-Resources Investigations Report↗

Geology, Streamflow, and Water Chemistry of the Talufofo Stream Basin, Saipan, Northern Mariana Islands

A study of the geology, streamflow, and water chemistry of Talufofo Stream Basin, Saipan, Commonwealth of the Northern Mariana Islands, was undertaken to determine the flow characteristics of Talufofo Stream and the relation to the geology of the drainage basin. The Commonwealth government is exploring the feasibility of using water from Talufofo Stream to supplement Saipan's stressed municipal water supply. Streamflow records from gaging stations on the principal forks of Talufofo Stream indicate that peak streamflows and long-term average flow are higher at the South Fork gaging station than at the Middle Fork gaging station because the drainage area of the South Fork gaging station is larger, but persistent base flow from ground-water discharge during dry weather is greater in the Middle Fork gaging station. The sum of the average flows at the Middle Fork and South Fork gaging stations, plus an estimate of the average flow at a point in the lower reaches of the North Fork, is about 2.96 cubic feet per second or 1.91 million gallons per day. Although this average represents the theoretical maximum long-term draft rate possible from the Talufofo Stream Basin if an adequate reservoir can be built, the actual amount of surface water available will be less because of evaporation, leaks, induced infiltration, and reservoir-design constraints. Base-flow characteristics, such as stream seepage and spring discharge, are related to geology of the basin. Base flow in the Talufofo Stream Basin originates as discharge from springs near the base of limestones located in the headwaters of Talufofo Stream, flows over low-permeability volcanic rocks in the middle reaches, and seeps back into the high-permeability limestones in the lower reaches. Water sampled from Talufofo Stream during base flow had high dissolved-calcium concentrations (between 35 and 98 milligrams per liter), characteristic of water from a limestone aquifer. Concentrations of potassium, sodium, and chloride ions in water samples from Talufofo Stream are characteristic of water draining a heavily vegetated basin near the ocean. The streamflow and water-chemistry data indicate that discharge from springs is in hydraulic connection with the limestone aquifer near the headwaters of the basin. The base flow therefore is subject to stresses placed on the nearby limestone ground-water system. Pumping from wells in the limestones at the headwaters of Talufofo Stream Basin may decrease spring flow in Talufofo Stream.

Water-Resources Investigations Report↗

Results of ground-water, surface-water, and water-chemistry monitoring, Black Mesa area, northeastern Arizona, 1994

The Black Mesa monitoring program is designed to document long-term effects of ground-water pumping from the N aquifer by industrial and municipal users. The N aquifer is the major source of water in the 5,400-square-mile Black Mesa area, and the ground water occurs under confined and unconfined conditions. Monitoring activities include continuous and periodic measurements of (1) ground-water pumpage from the confined and unconfined areas of the aquifer, (2) ground-water levels in the confined and unconfined areas of the aquifer, (3) surface-water discharge, and (4) chemistry of the ground water and surface water. In 1994, ground-water withdrawals for industrial and municipal use totaled about 7,000 acre-feet, which is an 8-percent increase from the previous year. Pumpage from the confined part of the aquifer increased by about 9 percent to 5,400 acre-feet, and pumpage from the unconfined part of the aquifer increased by about 2 percent to 1,600 acre-feet. Water-level declines in the confined area during 1994 were recorded in 10 of 16 wells, and the median change was a decline of about 2.3 feet as opposed to a decline of 3.3 feet for the previous year. The median change in water levels in the unconfined area was a rise of 0.1 foot in 1994 as opposed to a decline of 0.5 foot in 1993. Measured low-flow discharge along Moenkopi Wash decreased from 3.0 cubic feet per second in 1993 to 2.9 cubic feet per second in 1994. Eleven low-flow measurements were made along Laguna Creek between Tsegi, Arizona, and Chinle Wash to determine the amount of discharge that would occur as seepage from the N aquifer under optimal base-flow conditions. Discharge was 5.6 cubic feet per second near Tsegi and 1.5 cubic feet per second above the confluence with Chinle Wash. Maximum discharge was 5.9 cubic feet per second about 4 miles upstream from Dennehotso. Discharge was measured at three springs. The changes in discharge at Burro and Whisky Springs were small and within the uncertainty of measurement. Discharge at Moenkopi School Spring decreased from 14.6 gallons per minute in 1993 to 12.9 gallons per minute in 1994. Regionally long-term water-chemistry data for wells and springs have shown no discernible change. A recent gradual increase in concentrations of dissolved solids, sulfate, and chloride in water from Forest Lake NTUA 1, however, indicates that, locally, water from the D aquifer may be mixing with water from the N aquifer.

Arizona↗

Effects of resource chemistry on the composition and function of stream hyporheic biofilms.

Fluvial ecosystems process large quantities of dissolved organic matter as it moves from the headwater streams to the sea. In particular, hyporheic sediments are centers of high biogeochemical reactivity due to their elevated residence time and high microbial biomass and activity. However, the interaction between organic matter and microbial dynamics in the hyporheic zone remains poorly understood. We evaluated how variance in resource chemistry affected the microbial community and its associated activity in experimentally grown hyporheic biofilms. To do this we fed beech leaf leachates that differed in chemical composition to a series of bioreactors filled with sediment from a sub-alpine stream. Differences in resource chemistry resulted in differences in diversity and phylogenetic origin of microbial proteins, enzyme activity, and microbial biomass stoichiometry. Specifically, increased lignin, phenolics, and manganese in a single leachate resulted in increased phenoloxidase and peroxidase activity, elevated microbial biomass carbon:nitrogen ratio, and a greater proportion of proteins of Betaproteobacteria origin. We used this model system to attempt to link microbial form (community composition and metaproteome) with function (enzyme activity) in order to better understand the mechanisms that link resource heterogeneity to ecosystem function in stream ecosystems.

Frontiers in Microbiology↗

Diverging mineral chemistry of iron and nickel throughout Earth’s changing redox conditions reveals foundation for their evolution as protein cofactors

Iron (Fe) and nickel (Ni) were both foundational to early metabolism, yet their biological trajectories diverged as Earth’s surface redox state changed. Here, we integrate mineral chemistry network analysis, protein metal-site coordination-sphere analysis, and curated redox comparisons to test how geochemistry and metalloprotein architecture co-evolved. Mineral network analyses show broader electronegativity variation and network diversity for Fe-bearing minerals through time relative to Ni-bearing minerals. In structural analyses of protein metal centers in a combined Fe/Ni protein structure set, it is shown that Fe- and Ni-associated environments differ in amino-acid composition, hydropathy structure, and cysteine representation. The greater chemical diversity and electronegativity variation in Fe minerals mirror the higher redox and structural versatility of Fe-binding proteins. The presence of Fe in a broader range of mineral and protein environments demonstrates the chemical adaptability of the metal, from the anoxic Archean to oxidative Earth surface conditions following the Great Oxidation Event. Iron, with its broad redox potential range in Fe-oxidoreductases, has a central role in both anaerobic and aerobic metabolisms. Nickel, by contrast, is less widespread in biology. Today, Ni is predominantly employed in deeply branching anaerobic pathways and by proteins with narrower redox potential ranges. Our results show that evolutionary processes, constrained by metal chemistry, habitually utilize Fe as a redox generalist while retaining Ni in specialized roles. The divergent paths of Ni and Fe, from rocks to proteins, demonstrate the intimate relationship between planetary geochemistry and metabolic origins on Earth and suggest that Fe/Ni geochemistry may inform habitability assessments in extraterrestrial environments when interpreted within specific planetary environmental contexts.

Life↗