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Redox chemistry and natural organic matter (NOM): Geochemists' dream, analytical chemists' nightmare

Natural organic matter (NOM) is an inherently complex mixture of polyfunctional organic molecules. Because of their universality and chemical reversibility, oxidation/reductions (redox) reactions of NOM have an especially interesting and important role in geochemistry. Variabilities in NOM composition and chemistry make studies of its redox chemistry particularly challenging, and details of NOM-mediated redox reactions are only partially understood. This is in large part due to the analytical difficulties associated with NOM characterization and the wide range of reagents and experimental systems used to study NOM redox reactions. This chapter provides a summary of the ongoing efforts to provide a coherent comprehension of aqueous redox chemistry involving NOM and of techniques for chemical characterization of NOM. It also describes some attempts to confirm the roles of different structural moieties in redox reactions. In addition, we discuss some of the operational parameters used to describe NOM redox capacities and redox states, and describe nomenclature of NOM redox chemistry. Several relatively facile experimental methods applicable to predictions of the NOM redox activity and redox states of NOM samples are discussed, with special attention to the proposed use of fluorescence spectroscopy to predict relevant redox characteristics of NOM samples.

ACS Symposium Series↗

Overview of the morphology and chemistry of diagenetic features in the clay-rich Glen Torridon Unit of Gale Crater, Mars

The clay-rich Glen Torridon region of Gale crater, Mars, was explored between sols 2300 and 3007. Here, we analyzed the diagenetic features observed by Curiosity , including veins, cements, nodules, and nodular bedrock, using the ChemCam, Mastcam, and Mars Hand Lens Imager instruments. We discovered many diagenetic features in Glen Torridon, including dark-toned iron- and manganese-rich veins, magnesium- and fluorine-rich linear features, Ca-sulfate cemented bedrock, manganese-rich nodules, and iron-rich strata. We have characterized the chemistry and morphology of these features, which are most widespread in the higher stratigraphic members in Glen Torridon, and exhibit a wide range of chemistries. These discoveries are strong evidence for multiple generations of fluids from multiple chemical endmembers that likely underwent redox reactions to form some of these features. In a few cases, we may be able to use mineralogy and chemistry to constrain formation conditions of the diagenetic features. For example, the dark-toned veins likely formed in warmer, highly alkaline, and highly reducing conditions, while manganese-rich nodules likely formed in oxidizing and circumneutral conditions. We also hypothesize that an initial enrichment of soluble elements, including fluorine, occurred during hydrothermal alteration early in Gale crater history to account for elemental enrichment in nodules and veins. The presence of redox-active elements, including Fe and Mn, and elements required for life, including P and S, in these fluids is strong evidence for habitability of Gale crater groundwater. Hydrothermal alteration also has interesting implications for prebiotic chemistry during the earliest stages of the crater’s evolution and early Mars.

JGR - Planets↗

Variability of the carbonate chemistry in a shallow, seagrass-dominated ecosystem: implications for ocean acidification experiments

Open ocean observations have shown that increasing levels of anthropogenically derived atmospheric CO 2 are causing acidification of the world's oceans. Yet little is known about coastal acidification and studies are just beginning to characterise the carbonate chemistry of shallow, nearshore zones where many ecologically and economically important organisms occur. We characterised the carbonate chemistry of seawater within an area dominated by seagrass beds (Saint Joseph Bay, Florida) to determine the extent of variation in pH and p CO 2 over monthly and daily timescales. Distinct diel and seasonal fluctuations were observed at daily and monthly timescales respectively, indicating the influence of photosynthetic and respiratory processes on the local carbonate chemistry. Over the course of a year, the range in monthly values of pH (7.36-8.28), aragonite saturation state (0.65-5.63), and calculated pCO2 (195-2537 μatm) were significant. When sampled on a daily basis the range in pH (7.70-8.06), aragonite saturation state (1.86-3.85), and calculated p CO 2 (379-1019 μatm) also exhibited significant range and indicated variation between timescales. The results of this study have significant implications for the design of ocean acidification experiments where nearshore species are utilised and indicate that coastal species are experiencing far greater fluctuations in carbonate chemistry than previously thought.

Marine and Freshwater Research↗

A blood chemistry profile for lake trout

A blood chemistry profile for lake trout Salvelinus namaycush was developed by establishing baseline ranges for several clinical chemistry tests (glucose, total protein, amylase, alkaline phosphatase, alanine aminotransferase, aspartate aminotransferase, creatine kinase, calcium, and magnesium). Measurements were made accurately and rapidly with a Kodak Ektachem DT60 Analyzer and the Ektachem DTSC Module. Blood serum was collected from both laboratory-reared lake trout (1978 and 1986 year-classes) and feral spawning trout from Lake Michigan and then analyzed in the laboratory. No clinically significant differences were found between samples analyzed fresh and those frozen for 1 or 6 weeks. The ranges in chemistry variables for feral lake trout were generally wider than those for laboratory-reared lake trout, and significant differences existed between male and female feral lake trout for several tests. Blood chemistry profiles also varied seasonally on fish sampled repeatedly.

Journal of Aquatic Animal Health↗

Comparison of blood chemistry values for samples collected from juvenile chinook salmon by three methods

Thirteen blood chemistry indices were compared for samples collected by three commonly used methods: caudal transection, heart puncture, and caudal vessel puncture. Apparent biases in blood chemistry values for samples obtained by caudal transection were consistent with dilution with tissue fluids: alanine aminotransferase (ALT), aspartate aminotransferase (AST), lactate dehydrogenase (LDH), creatine kinase (CK), triglyceride, and K+ were increased and Na+ and Cl- were decreased relative to values for samples obtained by caudal vessel puncture. Some enzyme activities (ALT, AST, LDH) and K+ concentrations were also greater in samples taken by heart puncture than in samples taken by caudal vessel puncture. Of the methods tested, caudal vessel puncture had the least effect on blood chemistry values and should be preferred for blood chemistry studies on juvenile salmonids.

Journal of Aquatic Animal Health↗

Response of lake chemistry to atmospheric deposition and climate in selected Class I wilderness areas in the western United States, 1993-2009

The U.S. Geological Survey, in cooperation with the U.S. Department of Agriculture Forest Service, Air Resource Management, conducted a study to evaluate long-term trends in lake-water chemistry for 64 high-elevation lakes in selected Class I wilderness areas in Colorado, Idaho, Utah, and Wyoming during 1993 to 2009. Understanding how and why lake chemistry is changing in mountain areas is essential for effectively managing and protecting high-elevation aquatic ecosystems. Trends in emissions, atmospheric deposition, and climate variables (air temperature and precipitation amount) were evaluated over a similar period of record. A main objective of the study was to determine if changes in atmospheric deposition of contaminants in the Rocky Mountain region have resulted in measurable changes in the chemistry of high-elevation lakes. A second objective was to investigate linkages between lake chemistry and air temperature and precipitation to improve understanding of the sensitivity of mountain lakes to climate variability.

Colorado;Idaho;Utah;Wyoming↗

Characterization of the hydrology, water chemistry, and aquatic communities of selected springs in the St. Johns River Water Management District, Florida, 2004

The hydrology, water chemistry, and aquatic communities of Silver Springs, De Leon Spring, Gemini Springs, and Green Spring in the St. Johns River Water Management District, Florida, were studied in 2004 to provide a better understanding of each spring and to compile data of potential use in future water-management decisions. Ground water that discharges from these and other north-central Florida springs originates from the Upper Floridan aquifer of the Floridan aquifer system, a karstic limestone aquifer that extends throughout most of the State's peninsula. This report summarizes data about flow, water chemistry, and aquatic communities, including benthic invertebrates, fishes, algae, and aquatic macrophytes collected by the U.S. Geological Survey, the St. Johns River Water Management District, and the Florida Department of Environmental Protection during 2004, as well as some previously collected data. Differences in water chemistry among these springs reflect local differences in water chemistry in the Upper Floridan aquifer. The three major springs sampled at the Silver Springs group (the Main Spring, Blue Grotto, and the Abyss) have similar proportions of cations and anions but vary in nitrate and dissolved oxygen concentrations. Water from Gemini Springs and Green Spring has higher proportions of sodium and chloride than the Silver Springs group. Water from De Leon Spring also has higher proportions of sodium and chloride than the Silver Springs group but lower proportions of calcium and bicarbonate. Nitrate concentrations have increased over the period of record at all of the springs except Green Spring. Compounds commonly found in wastewater were found in all the springs sampled. The most commonly detected compound was the insect repellant N,N'-diethyl-methyl-toluamide (DEET), which was found in all the springs sampled except De Leon Spring. The pesticide atrazine and its degradate 2-chloro-4-isopropylamino-6-amino-s-triazine (CIAT) were detected in water from the Silver Springs group and in both boils at Gemini Springs. No pesticides were detected in water samples from De Leon Spring and Green Spring. Evidence of denitrification was indicated by the presence of excess nitrogen gas in water samples from most of the springs. Aquatic communities varied among the springs. Large floating mats of cyanobacteria (blue-green algae), identified as Lyngbya wollei, were observed in De Leon Spring during all sampling events in 2004. At Gemini Springs, the dominant periphyton was Rhizoclonium sp. Of the three springs sampled for benthic invertebrates, De Leon Spring had the highest overall species richness and most disturbance intolerant species (Florida Index = 4). Green Spring had the lowest species richness of the springs sampled. Based on qualitative comparisons, overall macroinvertebrate species richness seemed to be negatively related to magnesium, potassium, sodium, and specific conductance. Invertebrate abundance was greatest when dissolved oxygen and nitrate were high but phosphorus and potassium concentrations were low. Dipteran abundance seemed to be positively associated with specific conductance and total organic carbon but negatively associated with nitrate-N. Amphipods were the numerically dominant group collected in most (six of nine) collections. Shifts in amphipod abundance of the two species collected (Gammarus sp. and Hyalella azteca) varied by season among the three springs, but there were no trends evident in the variation. Fish populations were relatively species-rich at the Silver Springs group, De Leon Spring, and Gemini Springs, but not at Green Spring. Nonindigenous fish species were observed at all springs except Green Spring.

Open-File Report↗

Effects of low-level radioactive-waste disposal on water chemistry in the unsaturated zone at a site near Sheffield, Illinois, 1982-84

A 1982-84 field study defined the chemistry of water collected from the unsaturated zone at a low-level radioactive-waste disposal site near Sheffield, Bureau County, Illinois. Chemical data were evaluated to determine the principal naturally occurring geochemical reactions in the unsaturated zone and to evaluate waste-induced effects on pore-water chemistry. Samples of precipitation, unsaturated-zone pore water, and saturated-zone water were analyzed for specific conductance, pH, alkalinity, major cations and anions, dissolved organic carbon, gross alpha and beta radiation, and tritium. Little change in concentration of most major constituents in the unsaturated-zone water was observed with respect to depth or distance from disposal trenches. Tritium and dissolved organic carbon concentrations were, however, dependent on proximity to trenches. The primary reactions, both on- site and off-site, were carbonate and clay dissolution, cation exchange, and the oxidation of pyrite. The major difference between on-site and off-site inorganic water chemistry resulted from the removal of the Roxana Silt and the Radnor Till Member of the Glasford Formation from on-site. Off-site, the Roxana Silt contributed substantial quantities of sodium to solution from montmorillonite dissolution and associated cation-exchange reactions. The Radnor Till Member provided exchange surfaces for magnesium. Precipitation at the site had an ionic composition of calcium zinc sulfate and an average pH of 4.6. Within 0.3 meter of the land surface, infiltrating rain water or snowmelt changed to an ionic canposition of calcium sulfate off-site and calcium bicarbonate on-site and had an average pH of 7.9; below that depth, pH averaged 7.5 and the ionic composition generally was calcium magnesium bicarbonate. Alkalinity and specific conductance differed primarily according to composition of geologic materials. Tritium concentrations ranged from 0.2 (detection limit) to 1,380 nanocuries per liter. The methods of constructing, installing, and sampling with lysimeters were evaluated to ensure data reliability. These evaluations indicate that, with respect to most constituents, the samples retrieved from the lysimeters accurately represented pore-water chemistry.

Open-File Report↗

Snowpack chemistry at selected sites in northwestern Colorado during spring 1995

Samples of the alpine and subalpine snowpack were collected in and near the headwater basins of the Yampa River in northwestern Colorado during maximum annual accumulation of snowpack in spring 1995. Sampling protocol at seven selected sites at more than 2,500 meters above sea level divided the snowpack into two distinct strata to enable separate chemical analyses of upper and lower layers of the annual snow cover. These two layers correspond to the early snow season beginning in September until December 12, 1994, and the remainder of the season from January 1 until the sampling date in spring 1995. At one site these two strata were resampled at closely spaced intervals defining substrata to observe variance within the two strata dividing the snow season. Analytical results of snowpack chemistry are presented in support of investigations of seasonal effects on ion concentrations in the snowpack. Chemical concentrations of major anions and cations, dissolved organic carbon, and alkalinity; measured pH; calculated charge balance between anions and cations; the stable-sulfur isotope ratio (34S/32S); and summary statistics of chemical concentrations are tabulated. Sampling sites are plotted on a map of the area. Spatial distributions of the concentrations of the hydrogen, nitrate, and sulfate ions and stable- sulfur isotope ratios also are mapped. Several unusual, late-season, snowfall events occurred during April and May of 1995 after the snowpack was sampled at most of the seven sites in the study area. Consequently, a considerable fraction of the total annual snowpack was not sampled. At one site, the full snowpack was sampled again in June, after the late-spring storms, for comparison to the chemistry of the snowpack sampled earlier in April. Precipitation chemistry from a National Atmospheric Deposition Program (NADP) collector located near the site is presented for comparison of the chemistry of the late-season snow to that of the typical annual snowpack season.

Open-File Report↗

Geologic, water-chemistry, and hydrologic data from multiple-well monitoring sites and selected water-supply wells in the Santa Clara Valley, California, 1999-2003

To better identify the three-dimensional geohydrologic framework of the Santa Clara Valley, lithologic, geologic, geophysical, geomechanical, hydraulic, and water-chemistry data were collected from eight ground-water multiple-well monitoring sites constructed in Santa Clara County, California, as part of a series of cooperative studies between the U.S. Geological Survey and the Santa Clara Valley Water District. The data are being used to update and improve the three-dimensional geohydrologic framework of the basin and to address issues related to water supply, water chemistry, sequence stratigraphy, geology, and geological hazards. This report represents a compilation of data collected from 1999 to 2003, including location and design of the monitoring sites, cone penetrometer borings, geologic logs, lithologic logs, geophysical logs, core analysis, water-chemistry analysis, ground-water-level measurements, and hydraulic and geomechanical properties from wells and core samples. Exploratory cone penetrometer borings taken in the upper 17 to 130 feet at six of the monitoring sites identified the base of Holocene as no deeper than 75 feet in the central confined area and no deeper than 35 feet in the southern unconfined areas of the valley. Generalized lithologic characterization from the monitoring sites indicates about four to six different aquifer units separated by relatively fine-grained units occur within the alluvial deposits shallower than 860 feet deep. Analysis of geophysical logs indicates that coarse-grained units varied in thickness between 10 and 25 feet in the southeastern unconfined area of the valley and between 50 and 200 feet in the south-central and southwestern areas of the valley. Deviations from temperature-gradient logs indicate that the majority of horizontal ground-water flow occurs above a depth of 775 feet in the south central and above 510 feet in the southeastern areas of the valley. Bulk physical properties from more than 1,150 feet of core samples indicate an average primary-wave velocity of about 5,515 feet per second, a bimodal distribution of density between 2.19 and 2.32 grams per cubic centimeter with an average of 2.16 grams per cubic centimeter, and a magnetic susceptibility that generally ranged between 9 and 40 with an average of 22. Water-chemistry data indicate that the ground water in the alluvial aquifers generally is low in total dissolved solids and chloride and of good quality. Isotopic data indicate that water from artificial recharge is present throughout the shallower parts of the aquifer system but may not be present toward the center of the valley. The percentage of water from artificial recharge present in ground water ranges from 0 to 61 percent for water-supply wells. The age of most shallow ground water is less than 2,000 years before present, and the age of deeper ground water is as much as 39,900 years before present, as determined from carbon age dates. Initial water-level data from the multiple-well monitoring sites indicate seasonal water-level fluctuations as great as 60 feet and water-level differences between aquifers as great as 10 feet. The water-level hydrographs indicate different water-level changes and relations between aquifers in different parts of the basin. However, most of these hydrographs indicate the potential for downward water-level gradients, with lower hydraulic heads in the deeper monitoring wells. Hydraulic properties of selected new monitoring wells indicate that horizontal hydraulic conductivities range from 0.1 to 583 feet per day. Hydraulic testing of selected core samples yielded vertical hydraulic conductivity values ranging from 8 x 10-4 to 0.3 feet per day, and effective porosity values ranging from 0.21 to 0.4. Geomechanical properties estimated from one-dimensional consolidation tests of selected core samples resulted in geometric mean inelastic and elastic specific storage values of 1.5 x 10-

Scientific Investigations Report↗

Questa baseline and pre-mining ground-water quality investigation. 20. Water chemistry of the Red River and selected seeps, tributaries, and precipitation, Taos County, New Mexico, 2000-2004

As part of a multi-year project to infer the pre-mining ground-water quality at Molycorp's Questa mine site, surface-water samples of the Red River, some of its tributaries, seeps, and snow samples were collected for analysis of inorganic solutes and of water and sulfate stable isotopes in selected samples. The primary aim of this study was to document diel, storm event, and seasonal variations in water chemistry for the Red River and similar variations in water chemistry for Straight Creek, a natural analog site similar in topography, hydrology, and geology to the mine site for inferring pre-mining water-quality conditions. Red River water samples collected between 2000 and 2004 show that the largest variations in water chemistry occur during late summer rainstorms, often monsoonal in nature. Within hours, discharge of the Red River increased from 8 to 102 cubic feet per second and pH decreased from 7.80 to 4.83. The highest concentrations of metals (iron, aluminum, zinc, manganese) and sulfate also occur during such events. Low-pH and high-solute concentrations during rainstorm runoff are derived primarily from alteration 'scar' areas of naturally high mineralization combined with steep topography that exposes continually altered rock because erosion is too rapid for vegetative growth. The year 2002 was one of the driest on record, and Red River discharge reflected the low seasonal snow pack. No snowmelt peak appeared in the hydrograph record, and a late summer storm produced the highest flow for the year. Snowmelt was closer to normal during 2003 and demonstrated the dilution effect of snowmelt on water chemistry. Two diel sampling events were conducted for the Red River, one during low flow and the other during high flow, at two locations, at the Red River gaging station and just upstream from Molycorp's mill site. No discernible diel trends were observed except for dissolved zinc and manganese at the upstream site during low flow. Straight Creek drainage water was sampled periodically from 2001 to 2004 at the down stream end of surface drainage near the point at which it disappeared into the debris fan. This water has a minimal range in pH (2.7 to 3.2) but a substantial concentration range in many solutes; for example, sulfate concentrations varied from 525 to 2,660 mg/L. Many elements covary with sulfate suggesting that dilution is the primary control of the range in solute concentrations. A transect of water samples higher in the scar area were collected in October of 2003. They had a lower range in pH (2.44 to 3.05) and higher solute concentrations than those collected periodically from lower in the catchment. Water isotopes for the upper transect samples indicated slight evaporation, and in part, may account for the higher solute concentrations. Drainage waters also were collected from Hottentot, Junebug, Hansen, Little Hansen, and Goat Hill Gulch drainages. Most constituents from other scar drainage waters showed ranges of concentration similar to those of the Straight Creek waters. An exception was water collected from Goat Hill Gulch, which has some of the highest concentrations of any surface-water sample collected but also contained waste-rock leachates.

New Mexico↗

Geohydrology and water chemistry of the Alexander Valley, Sonoma County, California

This study of the geohydrology and water chemistry of the Alexander Valley, California, was done to provide an improved scientific basis for addressing emerging water-management issues, including potential increases in water demand and changes in flows in the Russian River. The study tasks included (1) evaluation of existing geohydrological, geophysical, and geochemical data; (2) collection and analysis of new geohydrologic data, including subsurface lithologic data, ground-water levels, and streamflow records; and (3) collection and analysis of new water-chemistry data. The estimated total water use for the Alexander Valley for 1999 was approximately 15,800 acre-feet. About 13,500 acre-feet of this amount was for agricultural use, primarily vineyards, and about 2,300 acre-feet was for municipal/industrial use. Ground water is the main source of water supply for this area. The main sources of ground water in the Alexander Valley are the Quaternary alluvial deposits, the Glen Ellen Formation, and the Sonoma Volcanics. The alluvial units, where sufficiently thick and saturated, comprise the best aquifer in the study area. Average recharge to the Alexander Valley is estimated from a simple, basinwide water budget. On the basis of an estimated annual average of 298,000 acre-feet of precipitation, 160,000 acre-feet of runoff, and 113,000 to 133,000 acre-feet of evapotranspiration, about 5,000 to 25,000 acre-feet per year is available for ground-water recharge. Because this estimate is based on differences between large numbers, there is significant uncertainty in this recharge estimate. Long-term changes in ground-water levels are evident in parts of the study area, but because of the sparse network and lack of data on well construction and lithology, it is uncertain if any significant changes have occurred in the northern part of the study area since 1980. In the southern half of the study area, ground-water levels generally were lower at the end of the 2002 irrigation season than at the end of the 1980 season, which suggests that a greater amount of ground water is being pumped in the southern half of the study area in recent years compared with that pumped in the early 1980s. Water-chemistry data for samples collected from 11 wells during 2002-04 indicate that water quality in the study area generally is acceptable for potable use. Two wells, however, each contained one constituent (241 ?g/L of manganese and 1,350 ?g/L of boron) in excess of the recommended standards for drinking water (50 ?g/L and 1,000 ?g/L, respectively). The chemical composition of water from most of the wells sampled for major ions plot as a mixed cation-bicarbonate, magnesium-bicarbonate, or calcium-bicarbonate type water. The ionic composition of the historical and recent samples from wells in the Alexander Valley is similar to that of the historical surface-water samples collected from the Russian River near Healdsburg. This suggests a similar source of water, particularly for wells that are less than 200 feet total depth and perforated in Quaternary alluvial deposits. Water from deeper, non-alluvial wells may contain slightly higher concentrations of sodium as a result of cation exchange. Water samples collected from several wells over an approximately 30-year period suggest a progressive change in water chemistry over time. Samples from the southern part of the valley show a trend towards higher ionic concentrations and increasing concentrations of particular constituents such as sulfate.

California↗

Water chemistry, seepage investigation, streamflow, reservoir storage, and annual availability of water for the San Juan-Chama Project, northern New Mexico, 1942-2010

The Albuquerque Bernalillo County Water Utility Authority supplements the municipal water supply for the Albuquerque metropolitan area, in central New Mexico, with surface water diverted from the Rio Grande. The U.S. Geological Survey, in cooperation with the Albuquerque Bernalillo County Water Utility Authority, undertook this study in which water-chemistry data and historical streamflow were compiled and new water-chemistry data were collected to characterize the water chemistry and streamflow of the San Juan-Chama Project (SJCP). Characterization of streamflow included analysis of the variability of annual streamflow and comparison of the theoretical amount of water that could have been diverted into the SJCP to the actual amount of water that was diverted for the SJCP. Additionally, a seepage investigation was conducted along the channel between Azotea Tunnel Outlet and the streamflow-gaging station at Willow Creek above Heron Reservoir to estimate the magnitude of the gain or loss in streamflow resulting from groundwater interaction over the approximately 10-mile reach. Generally, surface-water chemistry varied with streamflow throughout the year. Streamflow ranged from high flow to low flow on the basis of the quantity of water diverted from the Rio Blanco, Little Navajo River, and Navajo River for the SJCP. Vertical profiles of the water temperature over the depth of the water column at Heron Reservoir indicated that the reservoir is seasonally stratified. The results from the seepage investigations indicated a small amount of loss of streamflow along the channel. Annual variability in streamflow for the SJCP was an indication of the variation in the climate parameters that interact to contribute to streamflow in the Rio Blanco, Little Navajo River, Navajo River, and Willow Creek watersheds. For most years, streamflow at Azotea Tunnel Outlet started in March and continued for approximately 3 months until the middle of July. The majority of annual streamflow at Azotea Tunnel Outlet occurred from May through June, with a median duration of slightly longer than a month. Years with higher maximum daily streamflow generally are associated with higher annual streamflow than years with lower maximum daily streamflow. The amount of water that can be diverted for the SJCP is controlled by the availability of streamflow and is limited by several factors including legal limits for diversion, limits from the SJCP infrastructure including the size of the diversion dams and tunnels, the capacity of Heron Reservoir, and operational constraints that limit when water can be diverted. The average annual streamflow at Azotea Tunnel Outlet was 94,710 acre-feet, and the annual streamflow at Azotea Tunnel Outlet was approximately 75 percent of the annual streamflow available for the SJCP. The average annual percentage of available streamflow not diverted for the SJCP was 14 percent because of structural limitations of the capacity of infrastructure, 1 percent because of limitations of the reservoir storage capacity, and 29 percent because of the limitations from operations. For most years, the annual available streamflow not diverted for unknown reasons exceeded the sum of the water not diverted because of structural, capacity, and operational limitations.

Colorado, New Mexico↗

Groundwater hydrology and chemistry of Jamestown Island, Virginia—Potential effects of tides, storm surges, and sea-level rise on archaeological, cultural, and ecological resources

As the site of the first permanent English settlement in North America in 1607, Jamestown Island, Colonial National Historical Park (COLO), Virginia, contains a rich archaeological record that extends from the Paleoindian period (15,000 to 8,000 years ago) through the 20th century. The island is located on the lower James River near the mouth of Chesapeake Bay. Jamestown Island vegetation is dominated by upland forests surrounded by tidal, freshwater-to-oligohaline marshes. Along the Virginia coast, relative sea-level rise was more than 2.5 times the global average during the 20th century. Consequently, the National Park Service (NPS) has identified COLO as one of the 25 national parks most threatened by climate change. Surface waters across the island are hydraulically connected to the laterally continuous Surficial aquifer. The land-surface altitude of the island is low, with two-thirds of the island less than 5 feet (ft) above the North American Vertical Datum of 1988 (NAVD 88). Consequently, sea-level rise, combined with tides and storm surges, threatens the island and its resources as surface-water and groundwater levels rise, saltwater enters the Surficial aquifer, and groundwater chemistry changes. The impact of sea-level rise on the island’s surface-water resources has been well studied, but groundwater effects have been largely ignored. Quantifying the effects of tides, storm surges, and sea-level rise on groundwater levels and chemistry is essential to developing an effective strategy for managing climate-induced changes. The first step in developing a response strategy includes a parkwide general risk assessment for archaeological sites on the island, so that sites can be prioritized for management actions. The U.S. Geological Survey and the NPS began a study in 2015 to develop a long-term groundwater-monitoring program to evaluate this risk and to develop an updated management strategy. The groundwater-monitoring program consists of 45 wells and piezometers in two individual clusters and three transects across the island in different hydrologic and chemical settings. Samples for water quality were collected from the wells and piezometers from October 2015 through September 2018 at variable time intervals. Results of the monitoring identified disparate hydrologic and chemical responses to saltwater intrusion across the island. Specific conductance (an indicator of salinity) of groundwater beneath several marshes responded differently to changes in James River salinity. Groundwater response to changes in James River specific conductance appeared to be controlled by land-surface altitude and slope, differences in lateral and vertical sediment characteristics, distance from surface waters, and the degree of surface water/groundwater connectivity between channels and the aquifer. Groundwater chemistry data from monitoring wells at Black Point, a low-altitude, upland setting, are in contrast with conditions observed in Island House observation wells, a high-altitude, upland setting. Specific conductance (less than 200 microsiemens per centimeter [μS/cm]) and pH (greater than 5.0) of groundwater beneath much of the uplands that characterize the Island House observation wells are typical of groundwater in noncarbonate sedimentary aquifers recharged by precipitation. At Black Point, specific conductance ranged from 2,490 to 15,200 μS/cm, and pH ranged from 3.1 to 6.6 standard units. At the Black Point observation wells, the most saline and dense water was at the water table rather than deeper in the aquifer, causing a density inversion that persisted throughout the study. The density inversion likely resulted from differences in permeability between the shallow clay and fine-grained sands and the deeper coarse-grained sand and gravel. Groundwater with the lowest pH was at the water table. As saline groundwater flows through organic sediment beneath the marshes, bacterial biodegradation of organic matter creates anoxic conditions. Continued biodegradation concomitantly reduces iron-oxide minerals in the sediment and sulfate in saline water. When oxygen is reintroduced into groundwater, iron and sulfur can reoxidize to form sulfuric acid, locally lowering the pH of the water. This report describes the groundwater monitoring network design, rationale for site selection, monitoring approach, and results of monitoring from October 2015 through September 2018. Maps of inundation at selected water-level altitudes are included to identify the risk to archaeological, cultural, and ecological resources. The monitoring results of the hydrology and chemistry data are interpreted, and the different hydrologic and chemical settings are described. The implications of the study results for management decisions are presented, and suggestions for improving the monitoring network are included.

Virginia↗

Nutrient and carbonate chemistry patterns associated with Karenia brevis blooms in three West Florida Shelf estuaries 2020-2023

Ocean acidification (OA) driven by eutrophication, riverine discharge, and other threats from local population growth that affect the inorganic carbonate system is already affecting the eastern Gulf of Mexico. Long-term declines in pH of ~ -0.001 pH units yr -1 have been observed in many southwest Florida estuaries over the past few decades. Coastal and estuarine waters of southwest Florida experience high biomass harmful algal blooms (HABs) of the dinoflagellate Karenia brevis nearly every year; and these blooms have the potential to impact and be impacted by seasonal to interannual patterns of carbonate chemistry. Sampling was conducted seasonally along three estuarine transects (Tampa Bay, Charlotte Harbor, Caloosahatchee River) between May 2020 and May 2023 to obtain baseline measurements of carbonate chemistry prior to, during, and following K. brevis blooms. Conductivity, temperature and depth data and discrete water samples for K. brevis cell abundance, nutrients, and carbonate chemistry (total alkalinity, dissolved inorganic carbonate (DIC), p CO 2, and pH T were evaluated to identify seasonal patterns and linkages among carbonate system variables, nutrients, and K. brevis blooms. Karenia brevis blooms were observed during six samplings, and highest p CO 2 and lowest pH T was observed either during or after blooms in all three estuaries. Highest average pH and lowest p CO 2 were observed in Tampa Bay. In all three estuaries, average DIC and pH T were higher and p CO 2 was lower during dry seasons than wet seasons. There was strong influence of net community calcification (NCC) and net community production (NCP) on the carbonate system; and NCC : NCP ratios in Tampa Bay, Charlotte Harbor, and the Caloosahatchee River were 0.83, 0.93, and 1.02, respectively. Linear relationships between salinity and dissolved ammonium, phosphate, and nitrate indicate strong influence of freshwater inflow from river input and discharge events on nutrient concentrations. This study is a first step towards connecting observations of high biomass blooms like those caused by K. brevis and alterations of carbonate chemistry in Southwest Florida. Our study demonstrates the need for integrated monitoring to improve understanding of interactions among the carbonate system, HABs, water quality, and acidification over local to regional spatial scales and event to decadal time scales.

Florida↗

Predictive relations between acid-base chemistry and fish assemblages in streams of the Adirondack Mountains

Surface waters across much of New York State’s Adirondack Mountains were acidified in the late 20th century but began to recover following the 1990 Title IV Amendments to the Clean Air Act. Previous assessments of acidification recovery in the Adirondacks have generally been based on surface water chemistry data and inferred relationships to fish and other aquatic biota. Little data, however, has been available to characterize biological impacts and predict recovery of fish assemblages in streams of the region. Here, we use quantitative fish surveys combined with chemistry data from 48 headwater streams sampled during summer 2014–2016 to develop logistic (probability) models that characterize the status of contemporary fish assemblages and predict how different N and S deposition loads may affect future fish assemblages. Statistical models for inorganic aluminum (Al i ) and richness ≥1 species; and for acid neutralizing capacity (ANC) and total density >400 fish/0.1 ha, total biomass >1500 g/0.1 ha, brook trout Salvelinus fontinalis density >0 or >200 fish/0.1 ha, and brook trout biomass >1000 g/0.1 ha were suitable for evaluating community and population responses to changes in acid-base chemistry. Predictions of fish-assemblage responses using several of these models demonstrated that anticipated changes in national (U.S.) secondary standards for atmospheric emissions of NO x and SO x to achieve target N and S deposition loads are likely to alter the acid-base chemistry and the probabilities of observing various levels of brook trout population and fish-community metrics in streams across the region and elsewhere.

New York↗

Trends in the chemistry of precipitation and surface water in a national network of small watersheds

Trends in precipitation and surface water chemistry at a network of 15 small watersheds ( < 10 km2) in the USA were evaluated using a statistical test for monotonic trends (the seasonal Kendall test) and a graphical smoothing technique for the visual identification of trends. Composite precipitation samples were collected weekly and surface water samples were collected at least monthly. Concentrations were adjusted before trend analysis, by volume for precipitation samples and by flow for surface water samples. A relation between precipitation and surface water trends was not evident either for individual inorganic solutes or for solute combinations, such as ionic strength, at most sites. The only exception was chloride, for which there was a similar trend at 60% of the sites. The smoothing technique indicated that short-term patterns in precipitation chemistry were not reflected in surface waters. The magnitude of the short-term variations in surface water concentration was generally larger than the overall long-term trend, possibly because flow adjustment did not adequately correct for climatic variability. Detecting the relation between precipitation and surface water chemistry trends may be improved by using a more powerful sampling strategy and by developing better methods of concentration adjustment to remove the effects of natural variation in surface waters.

Hydrological Processes↗

Influence of climate on alpine stream chemistry and water sources

The resilience of alpine/subalpine watersheds may be viewed as the resistance of streamflow or stream chemistry to change under varying climatic conditions, which is governed by the relative size (volume) and transit time of surface and subsurface water sources. Here, we use end‐member mixing analysis in Andrews Creek, an alpine stream in Rocky Mountain National Park, Colorado, from water year 1994 to 2015, to explore how the partitioning of water sources and associated hydrologic resilience change in response to climate. Our results indicate that four water sources are significant contributors to Andrews Creek, including snow, rain, soil water, and talus groundwater. Seasonal patterns in source‐water contributions reflected the seasonal hydrologic cycle, which is driven by the accumulation and melting of seasonal snowpack. Flushing of soil water had a large effect on stream chemistry during spring snowmelt, despite making only a small contribution to streamflow volume. Snow had a large influence on stream chemistry as well, contributing large amounts of water with low concentrations of weathering products. Interannual patterns in end‐member contributions reflected responses to drought and wet periods. Moderate and significant correlations exist between annual end‐member contributions and regional‐scale climate indices (the Palmer Drought Severity Index, the Palmer Hydrologic Drought Index, and the Modified Palmer Drought Severity Index). From water year 1994 to 2015, the percent contribution from the talus‐groundwater end member to Andrews Creek increased an average of 0.5% per year (p < 0.0001), whereas the percent contributions from snow plus rain decreased by a similar amount (p = 0.001). Our results show how water and solute sources in alpine environments shift in response to climate variability and highlight the role of talus groundwater and soil water in providing hydrologic resilience to the system.

Colorado↗