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USGS2016

Potential sources of analytical bias and error in selected trace element data-quality analyses

Potential sources of analytical bias and error associated with laboratory analyses for selected trace elements where concentrations were greater in filtered samples than in paired unfiltered samples were evaluated by U.S. Geological Survey (USGS) Water Quality Specialists in collaboration with the USGS National Water Quality Laboratory (NWQL) and the Branch of Quality Systems (BQS). Causes for trace-element concentrations in filtered samples to exceed those in associated unfiltered samples have been attributed to variability in analytical measurements, analytical bias, sample contamination either in the field or laboratory, and (or) sample-matrix chemistry. These issues have not only been attributed to data generated by the USGS NWQL but have been observed in data generated by other laboratories. This study continues the evaluation of potential analytical bias and error resulting from matrix chemistry and instrument variability by evaluating the performance of seven selected trace elements in paired filtered and unfiltered surface-water and groundwater samples collected from 23 sampling sites of varying chemistries from six States, matrix spike recoveries, and standard reference materials. Filtered and unfiltered samples have been routinely analyzed on separate inductively coupled plasma-mass spectrometry instruments. Unfiltered samples are treated with hydrochloric acid (HCl) during an in-bottle digestion procedure; filtered samples are not routinely treated with HCl as part of the laboratory analytical procedure. To evaluate the influence of HCl on different sample matrices, an aliquot of the filtered samples was treated with HCl. The addition of HCl did little to differentiate the analytical results between filtered samples treated with HCl from those samples left untreated; however, there was a small, but noticeable, decrease in the number of instances where a particular trace-element concentration was greater in a filtered sample than in the associated unfiltered sample for all trace elements except selenium. Accounting for the small dilution effect (2 percent) from the addition of HCl, as required for the in-bottle digestion procedure for unfiltered samples, may be one step toward decreasing the number of instances where trace-element concentrations are greater in filtered samples than in paired unfiltered samples. The laboratory analyses of arsenic, cadmium, lead, and zinc did not appear to be influenced by instrument biases. These trace elements showed similar results on both instruments used to analyze filtered and unfiltered samples. The results for aluminum and molybdenum tended to be higher on the instrument designated to analyze unfiltered samples; the results for selenium tended to be lower. The matrices used to prepare calibration standards were different for the two instruments. The instrument designated for the analysis of unfiltered samples was calibrated using standards prepared in a nitric:hydrochloric acid (HNO 3 :HCl) matrix. The instrument designated for the analysis of filtered samples was calibrated using standards prepared in a matrix acidified only with HNO 3 . Matrix chemistry may have influenced the responses of aluminum, molybdenum, and selenium on the two instruments. The best analytical practice is to calibrate instruments using calibration standards prepared in matrices that reasonably match those of the samples being analyzed. Filtered and unfiltered samples were spiked over a range of trace-element concentrations from less than 1 to 58 times ambient concentrations. The greater the magnitude of the trace-element spike concentration relative to the ambient concentration, the greater the likelihood spike recoveries will be within data control guidelines (80–120 percent). Greater variability in spike recoveries occurred when trace elements were spiked at concentrations less than 10 times the ambient concentration. Spike recoveries that were considerably lower than 90 percent often were associated with spiked concentrations substantially lower than what was present in the ambient sample. Because the main purpose of spiking natural water samples with known quantities of a particular analyte is to assess possible matrix effects on analytical results, the results of this study stress the importance of spiking samples at concentrations that are reasonably close to what is expected but sufficiently high to exceed analytical variability. Generally, differences in spike recovery results between paired filtered and unfiltered samples were minimal when samples were analyzed on the same instrument. Analytical results for trace-element concentrations in ambient filtered and unfiltered samples greater than 10 and 40 μg/L, respectively, were within the data-quality objective for precision of ±25 percent. Ambient trace-element concentrations in filtered samples greater than the long-term method detection limits but less than 10 μg/L failed to meet the data-quality objective for precision for at least one trace element in about 54 percent of the samples. Similarly, trace-element concentrations in unfiltered samples greater than the long-term method detection limits but less than 40 μg/L failed to meet this data-quality objective for at least one trace-element analysis in about 58 percent of the samples. Although, aluminum and zinc were particularly problematic, limited re-analyses of filtered and unfiltered samples appeared to improve otherwise failed analytical precision. The evaluation of analytical bias using standard reference materials indicate a slight low bias for results for arsenic, cadmium, selenium, and zinc. Aluminum and molybdenum show signs of high bias. There was no observed bias, as determined using the standard reference materials, during the analysis of lead.

Scientific Investigations Report↗
USGS1995

Hydrologic data for the Fristoe Unit of the Mark Twain National Forest, southern Missouri, 1988-93

Background hydrologic data were collected from 1988 to 1993 in the Fristoe Unit of the Mark Twain National Forest. Water-quality data collected from area streams, springs, and wells were analyzed using trilinear diagrams, stiff diagrams, boxplots, and summary statistics. The water is a calcium- magnesium-bicarbonate type. Streams generally have slightly larger potassium, barium, and total organic carbon concentrations than spring or well water. Well water has larger bicarbonate and zinc concen- trations and larger variability in sodium, chloride, and nitrate concentrations than stream and spring water samples. The bulk mineralogy for streambed material is primarily coarse grain quartz. Quantitative elemental (chemistry) analysis on the less than 63 micrometer fraction of bulk material was performed. The heavy mineral concentrate in the streambed material was analyzed using semi- quantitative optical mineralogy and 37-element semi- quantitative emission spectrography. Water levels were measured in 57 area wells in the spring and fall from 1990 to 1993 to determine ground-water level fluctuations. Ground-water fluctuations ranged from less than 1.0 to 205.1 feet in these wells. Continuous water-level recorders were installed on three area wells. Depth to water ranged from 289.68 to 333.39 feet in the lower Eleven Point well, which is completed in the Ozark aquifer. Depth to water ranged from 78.73 to 90.20 feet in Ozark Lead Well 1 which is completed in the Ozark aquifer and St. Francois confining unit. Depth to water ranged from 127.53 to 135.67 feet in Ozark Lead Well 2, which is completed in the St. Francois confining unit and the St. Francois aquifer.

Open-File Report↗
USGS2022

Effects of return flows on stream water quality and availability in the Upper Colorado, Delaware, and Illinois River Basins

Understanding effects of human water use and subsequent return flows on the availability and suitability of water for downstream uses is critical to efficient and effective watershed management. We compared spatially detailed estimates of stream chemistry within three watersheds in diverse settings to available standards to isolate effects of wastewater and irrigation return flows on the suitability of downstream waters for maintaining healthy aquatic ecosystems and for selected human uses. Mean-annual flow-weighted total and source-specific concentrations of nitrogen and phosphorus in individual stream reaches within the Upper Colorado, Delaware, and Illinois River Basins and of total dissolved solids within stream reaches of the Upper Colorado River Basin were estimated from previously calibrated regional watershed models. Estimated concentrations of both nitrogen and phosphorus in most stream reaches in all three watersheds (at least 78%, by length) exceed recommended standards for the protection of aquatic ecosystems, although concentrations in relatively few streams exceed such standards due to contributions from wastewater return flows, alone. Consequently, efforts to reduce wastewater nutrient effluent may provide important local downstream benefits but would likely have minimal impact on regional ecological conditions. Similarly, estimated mean-annual flow-weighted total dissolved solids concentrations in the Upper Colorado River Basin exceed standards for agricultural water use and (or) the secondary maximum contaminant level (SMCL) for drinking water in 52% of streams (by length), but rarely due to effects of irrigation return flows, alone. Dissolved solids in most tributaries of the Upper Colorado River are attributable primarily to natural sources.

Upper Colorado, Delaware, and Illinois River Basin↗
USGS2000

Spatial distribution, temporal variability, and chemistry of the salt wedge in the lower Charles River, Massachusetts, June 1998 to July 1999

The Charles River is of great recreational and ecological value to the Boston metropolitan region and the Commonwealth of Massachusetts. It is also the focus of the U.S. Environmental Protection Agency (USEPA) Region I, Clean Charles 2005 Task Force. The main goal of the Task Force is to make the Charles River 'fishable and swimmable' by the year 2005. Achieving 'fishable and swimmable' conditions will require continued progress in addressing a range of environmental conditions now degrading water quality, including the infiltration of saltwater from Boston Harbor into the freshwater Charles River.To better understand the pattern of saltwater intrusion, the U.S. Geological Survey (USGS), in cooperation with the U.S. Environmental Protection Agency (USEPA), Massachusetts Department of Environmental Management (MADEM), and New England Interstate Water Pollution Control Commission (NEIWPCC), collected data on the spatial distribution, temporal variability, and chemistry of the saltwater that entered the lower Charles River from June 1998 to July 1999. The purpose of this investigation is to extend and complement a regional-scale study of Charles River water quality conducted in 1996 (T. Faber, U.S. Environmental Protection Agency, written commun., 1997), and the ongoing water monitoring activities of the Massachusetts Water Resources Authority (MWRA) and the Charles River Watershed Association (CRWA). The data collected by this investigation supports the Clean Charles 2005 Task Force by providing detailed information concerning a major factor limiting 'fishable and swimmable' conditions in the lower Charles River. Finally, the study will be used to assist current planning efforts of the Metropolitan District Commission (MDC) to restore the historic parklands of the lower Charles River.The 'Basin' is the local term for the reach of the Charles River that begins at the Watertown Dam in Watertown, Mass., and extends about 8 mi through suburban and urban areas to Boston Harbor. Discharge to the harbor is controlled by the 'new' Charles River Dam in Boston (fig. 1). The Basin was created by construction of the 'old' Charles River Dam in 1908 to solve Boston's sanitary problems. Prior to the building of the old Charles River Dam, the lower Charles River was a tidal estuary in which the water levels rose and fell twice daily with the tidal cycle. Low tide would expose untreated sewage that was discharged directly into the river. Exposed sewage created noxious odors and served as a breeding ground for mosquitoes that caused sporadic epidemics of malaria and yellow fever (Jobin, 1998). Damming of the river interrupted the normal tidal cycle and flooded the estuary by creating a freshwater pool (the Basin) that had a constant water elevation of about 0.8 meters (m) above mean sea level. Flooding of the estuary initially improved sanitary conditions and the Basin became a source of enjoyment for the local population and the focus of a large waterfront park in Boston and Cambridge (Jobin, 1998).Although the infiltration of saltwater from the harbor into the Basin was anticipated when the old Charles River Dam was built, neither the magnitude nor the consequences of the infiltration was considered. By 1975, the Metropolitan District Commission (MDC) determined that harbor water covered about 80 percent of the river bottom within the Basin and composed about 50 percent of its depth. The MDC also concluded that fish kills and odors in the spring of 1975 were likely the result of the sulfide-rich saltwater mixing with the overlying freshwater (Metropolitan District Commission, 1975).Saltwater from Boston Harbor that enters the Basin is known as the 'salt wedge' because of the shape it assumes as it moves upstream. Freshwater discharge from upstream pushes against the intruding harbor water until the density differences cause stratification to occur; the freshwater then overrides the denser harbor water (Fischer and others, 1979). The depth from

Water-Resources Investigations Report↗
USGS2012

Atmospheric inputs to watersheds of the Luquillo Mountains in eastern Puerto Rico: Chapter D in Water quality and landscape processes of four watersheds in eastern Puerto Rico

Twenty years of precipitation-chemistry data from the National Atmospheric Deposition Program site at El Verde, Puerto Rico, demonstrate that three major sources control the composition of solutes in rain in eastern Puerto Rico. In order of importance, these sources are marine salts, temperate contamination from the Northern Hemisphere, and Sahara Desert dust. Marine salts are a source of roughly 82 percent of the ionic charge in precipitation; marine salt inputs are greatest in January. Evaluation of 15 years of U.S. Geological Survey data for four watersheds in eastern Puerto Rico suggests that large storms, including hurricanes, are associated with exceptionally high chloride concentrations in stream waters. Some of these storms were missed in sampling by the National Atmospheric Deposition Program, and therefore its data on the marine contribution likely underestimate chloride. The marine contribution is a weak source of acidity. Temperate contamination contributes about 10 percent of the ionic charge in precipitation; contaminants are primarily nitrate, ammonia, and sulfate derived from various manmade and natural sources. Peak deposition of temperate contaminants is during January, April, and May, months in which strong weather fronts arrive from the north. Temperate contamination, a strong source of acidity, is the only component that is increasing through time. Sahara Desert dust provides 5 percent of the ionic charge in precipitation; it is strongly seasonal, peaking in June and July during times of maximum dust transport from the Sahara and sub-Saharan regions. This dust contributes, on average, enough alkalinity to neutralize the acidity in June and July rains.

Professional Paper↗
USGS2024

Multiple stressors mediate the effects of warming on leaf decomposition in a large regulated river

Predicting how increasing temperatures interact with other global change drivers to influence the structure and dynamics of Earth's ecosystems is a primary challenge in ecology. Our study made use of multiple simultaneous “natural experiments” to examine how rapid warming, declining nutrients, invasive consumers, and riparian invasive species management interact to influence leaf decomposition in a large and regulated river. Specifically, we compared the breakdown of cottonwood ( Populus fremontii ), willow ( Salix exigua ), and saltcedar ( Tamarix sp.) leaf litter in 2022 to a previous experiment from 1998 that occurred under much cooler water temperatures, and had higher water phosphorus concentrations, low numbers of invasive New Zealand mudsnails ( Potamopyrgus antipodarum ), and unaltered litter chemistry from the herbivory of saltcedar leaf beetles ( Diorhabda carinulata ). We found that the effects of up to 10°C warmer temperatures on leaf decomposition were mediated by the establishment and management of invasive species and declining water nutrient concentrations arising from upstream reservoir lowering. Such interactions led to accelerated breakdown of saltcedar, but relatively minor effects of warming on the rate of cottonwood and willow decomposition. Additionally, our results demonstrate the potential for favorable invasive species management outcomes in the terrestrial environment to produce unintended responses in adjacent freshwater ecosystems. As temperatures continue to rise, it is critical that future studies consider how warming interacts with multiple stressors and environmental factors to influence processes such as decomposition in freshwater ecosystems.

Arizona↗
USGS2021

Integrating high-resolution coastal acidification monitoring data across seven United States estuaries

Beginning in 2015, the United States Environmental Protection Agency’s (EPA’s) National Estuary Program (NEP) started a collaboration with partners in seven estuaries along the East Coast (Barnegat Bay; Casco Bay), West Coast (Santa Monica Bay; San Francisco Bay; Tillamook Bay), and the Gulf of Mexico (GOM) Coast (Tampa Bay; Mission-Aransas Estuary) of the United States to expand the use of autonomous monitoring of partial pressure of carbon dioxide ( p CO 2 ) and pH. Analysis of high-frequency (hourly to sub-hourly) coastal acidification data including p CO 2 , pH, temperature, salinity, and dissolved oxygen (DO) indicate that the sensors effectively captured key parameter measurements under challenging environmental conditions, allowing for an initial characterization of daily to seasonal trends in carbonate chemistry across a range of estuarine settings. Multi-year monitoring showed that across all water bodies temperature and p CO 2 covaried, suggesting that p CO 2 variability was governed, in part, by seasonal temperature changes with average p CO 2 being lower in cooler, winter months and higher in warmer, summer months. Furthermore, the timing of seasonal shifts towards increasing (or decreasing) p CO 2 varied by location and appears to be related to regional climate conditions. Specifically, p CO 2 increases began earlier in the year in warmer water, lower latitude water bodies in the GOM (Tampa Bay; Mission-Aransas Estuary) as compared with cooler water, higher latitude water bodies in the northeast (Barnegat Bay; Casco Bay), and upwelling-influenced West Coast water bodies (Tillamook Bay; Santa Monica Bay; San Francisco Bay). Results suggest that both thermal and non-thermal influences are important drivers of p CO 2 in Tampa Bay and Mission-Aransas Estuary. Conversely, non-thermal processes, most notably the biogeochemical structure of coastal upwelling, appear to be largely responsible for the observed p CO 2 values in West Coast water bodies. The co-occurrence of high salinity, high p CO 2 , low DO, and low temperature water in Santa Monica Bay and San Francisco Bay characterize the coastal upwelling paradigm that is also evident in Tillamook Bay when upwelling dominates freshwater runoff and local processes. These data demonstrate that high-quality carbonate chemistry observations can be recorded from estuarine environments using autonomous sensors originally designed for open-ocean settings.

California, Florida, Maine, New Jersey, Oregon, Te↗
USGS2016

Physical, chemical, and biological characteristics of selected headwater streams along the Allegheny Front, Blair County, Pennsylvania, July 2011–September 2013

The Altoona Water Authority (AWA) obtains all of its water supply from headwater streams that drain western Blair County, an area underlain in part by black shale of the Marcellus Formation. Development of the shale-gas reservoirs will require new access roads, stream crossing, drill-pad construction, and pipeline installation, activities that have the potential to alter existing stream channel morphology, increase runoff and sediment supply, alter streamwater chemistry, and affect aquatic habitat. The U.S. Geological Survey, in cooperation with Altoona Water Authority and Blair County Conservation District, investigated the water quality of 12 headwater streams and biotic health of 10 headwater streams. Channel morphology was characterized at 10 of 12 stream sites using 500-foot (minimum) longitudinal profiles, four cross-sections each, and pebble counts. Channel slopes ranged from 0.008 in Poplar Run near Newry to 0.045 in Mill Run. In general, streams draining watersheds of 5 square miles or less and at higher elevation had the steepest slopes. On the basis of the median particle size, determined during pebble counts, the streambed substrate can be characterized as cobble (Mill Run, Bells Gap Run, Tipton Run, and Sink Run), a mix of gravel and cobble (South Poplar Run, Dry Gap Run, Glenwhite Run, Sugar Run, Blair Gap Run), and gravel (Poplar Run, Newry). Daily mean values of gage height were determined, and continuous (30-minute interval) data consisting of specific conductance and water temperature were collected, at four sites; each site showed typical seasonal fluctuations and the effects of precipitation. Streamflow affected discrete water-quality. Dissolved oxygen always increased with increased streamflow. Most cations (including barium and strontium), along with pH, specific conductance, and total dissolved solids, decreased with greater streamflow, reflecting the dilution effect of moderately acidic surface runoff and precipitation on groundwater discharge (base flow) into the stream channels. Concentrations of trace elements varied by constituent and streamflow. On the basis of the results of water-quality analyses for the selected constituents, the water quality in 9 of the 12 streams can be considered fair or attaining with no measured constituent exceeding a U.S. Environmental Protection Agency maximum or secondary contaminant level. Abandoned mine drainage (AMD) affects Glenwhite Run, Blair Gap Run, and Sugar Run. For Sugar Run, the AMD is reflected in the elevated iron concentration (greater than 300 micrograms per liter). Manganese concentrations greater than 50 micrograms per liter were measured in Glenwhite Run, Sugar Run, and Blair Gap Run. A mixing curve based upon chloride/bromide ratios for two end points—precipitation and deicing salts—indicate that deicing salt is migrating to the streams. A similar curve representative of late-emerging flowback water from Marcellus gas wells indicated that the surface-water samples had not been influenced by such brines. On the basis of the concentration of major ions, the streams in the study area generally had mixed cation and anion compositions. Calcium is the dominant cation in one stream. Carbonate and bicarbonate are the dominant anions for two streams, and sulfate is dominant in three streams. The remaining six streams do not have a dominant ion. Biotic health was characterized at 10 of 12 stream sites; the two sites excluded were established late in the study period (May 2013) for refinement of water quality in the headwaters of Poplar Run and the location of Marcellus Formation gas wells. On the basis of the Maryland Index of Biotic Integrity (MdIBI) for fish assemblages, 8 of 10 streams can be considered in fair health. Tipton Run had the highest MdIBI score (3.75) and the greatest number of native species. South Poplar Run had the lowest MdIBI score (1.75); pollution tolerant blacknose dace was dominant. On the basis of the Pennsylvania Department of Environmental Protection macroinvertebrate index of biotic integrity, 9 of 10 streams were characterized as attaining, with scores as high as 88.9 at Tipton Run. Only Sugar Run was characterized as impaired, with a score of 40.4.

Pennsylvania↗
USGS1999

Soil calcium status and the response of stream chemistry to changing acidic deposition rates

Despite a decreasing trend in acidic deposition rates over the past two to three decades, acidified surface waters in the northeastern United States have shown minimal changes. Depletion of soil Ca pools has been suggested as a cause, although changes in soil Ca pools have not been directly related to long-term records of stream chemistry. To investigate this problem, a comprehensive watershed study was conducted in the Neversink River Basin, in the Catskill Mountains of New York, during 1991–1996. Spatial variations of atmospheric deposition, soil chemistry, and stream chemistry were evaluated over an elevation range of 817–1234 m to determine whether these factors exhibited elevational patterns. An increase in atmospheric deposition of SO 4 with increasing elevation corresponded with upslope decreases of exchangeable soil base concentrations and acid-neutralizing capacity of stream water. Exchangeable base concentrations in homogeneous soil incubated within the soil profile for one year also decreased with increasing elevation. An elevational gradient in precipitation was not observed, and effects of a temperature gradient on soil properties were not detected. Laboratory leaching experiments with soils from this watershed showed that (1) concentrations of Ca in leachate increased as the concentrations of acid anions in added solution increased, and (2) the slope of this relationship was positively correlated with base saturation. Field and laboratory soil analyses are consistent with the interpretation that decreasing trends in acid-neutralizing capacity in stream water in the Neversink Basin, dating back to 1984, are the result of decreases in soil base saturation caused by acidic deposition.

Ecological Applications↗
USGS1989

Water quality data for precipitation and storm runoff in Pennypack Creek Basin, Philadelphia, Pennsylvania

This report presents data on the chemistry of precipitation and storm runoff that were collected during 29 storms from July 1979 through November 1980, in an urban environment in the Pennypack Creek basin, Philadelphia, Pennsylvania. Daily mean and instantaneous stream discharge data were collected at two U.S. Geological Survey gaging stations. Water-quality data collected from these sites and from one storm-sewer sampling site included nutrients, chemical and biochemical oxygen demands, solids, metals, major anions, other constituents, and pH. Instantaneous loads of selected constituents were computed. Chemical oxygen demand, biochemical oxygen demand, sulfate, alkalinity, chloride, and dissolved solids generally were low in precipitation and runoff. During the November 5, 1980 storm at Pine Road, dissolved nitrate concentrations equaled or exceeded 10 milligrams per liter in 17 percent of the samples analyzed and dissolved ammonia nitrogen concentrations exceeded 2.5 milligrams per liter. Generally, a comparison of median concentration of copper, lead, or zinc in precipitation and runoff at the Tustin Street storm-sewer site showed that median concentrations in precipitation were greater than those in runoff.

Pennsylvania↗
USGS2012

Water quality and landscape processes of four watersheds in eastern Puerto Rico

Humid tropical regions occupy about a quarter of Earth's land surface, yet they contribute a substantially higher fraction of the water, solutes, and sediment discharged to the world's oceans. Nearly half of Earth's population lives in the tropics, and development stresses can potentially harm soil resources, water quality, and water supply and in addition increase landslide and flood hazards. Owing to Puerto Rico's steep topography, low water storage capacity, and dependence on trade-wind precipitation, the island's people, ecosystems, and water supply are vulnerable to extreme weather such as hurricanes, floods, and droughts. Eastern Puerto Rico offers a natural laboratory for separating geologic and land-cover influences from regional- and global-scale influences because of its various bedrock types and the changing land cover surrounding intact, mature forest of the Luquillo Experimental Forest. Accordingly, a multiyear assessment of hydrological and biogeochemical processes was designed to develop an understanding of the effects of these differences on local climate, streamflow, water quality, and ecosystems, and to form the basis for a long-term and event-based program of climate and hydrologic monitoring. Because infrequent, large storms play a major role in this landscape, we focused on high-runoff events, sampling 263 storms, including all major hurricanes from 1991 through 2005. The largest storms have profound geomorphic consequences, such as landslides, debris flows, deep gullying on deforested lands, excavation and suspension of sediment in stream channels, and delivery of a substantial fraction of annual stream sediment load. Large storms sometimes entrain ocean foam and spray causing high concentrations of seasalt-derived constituents in stream waters during the storm. Past deforestation and agricultural activities in the Cayaguás and Canóvanas watersheds accelerated erosion and soil loss, and this material continues to be remobilized during large storms. Nearly 5,000 routine and event samples were analyzed for parameters that allow determination of denudation rates based on suspended and dissolved loads; 860 of these samples were analyzed for a comprehensive suite of chemical constituents. The rivers studied are generally similar in water-quality characteristics, and windward or leeward aspect appears to exert a stronger influence on water quality than geology or land cover. Of samples analyzed for comprehensive chemistry and for sediment, 543 were collected at runoff rates greater than 1 millimeter per hour, 256 at rates exceeding 10 millimeters per hour, and 3 at rates exceeding 90 millimeters per hour. Streams have rarely been sampled during events with such high runoff rates. Rates of physical and chemical weathering are especially high, and physical denudation rates, forested watersheds included, are considerably greater than is expected for a steady-state system. The elevated physical erosion drives an increased particulate organic carbon flux, one that is large, important to the carbon cycle, and sustainable, because soil-carbon regeneration is rapid. The 15-year Water, Energy, and Biogeochemical Budget dataset, which includes discharge, field parameters, suspended sediment, major cations and anions, and nutrients, is available from the U.S. Geological Survey's National Water Information System (http://waterdata.usgs.gov/nwis). The dataset provides a baseline for characterizing future environmental change and will improve our understanding of the interdependencies of land, water, and biological resources and their responses to changes in climate and land use. Because eastern Puerto Rico resembles many tropical regions in terms of geology and patterns of development, implications from this study are transferable to other tropical regions facing deforestation, rapid land-use change, and climate change.

Professional Paper↗
USGS2024

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↗
USGS2011

Dissolved organic matter in the Florida everglades: Implications for ecosystem restoration

Dissolved organic matter (DOM) in the Florida Everglades controls a number of environmental processes important for ecosystem function including the absorption of light, mineral dissolution/precipitation, transport of hydrophobic compounds (e.g., pesticides), and the transport and reactivity of metals, such as mercury. Proposed attempts to return the Everglades to more natural flow conditions will result in changes to the present transport of DOM from the Everglades Agricultural Area and the northern conservation areas to Florida Bay. In part, the restoration plan calls for increasing water flow throughout the Everglades by removing some of the manmade barriers to flow in place today. The land- and water-use practices associated with the plan will likely result in changes in the quality, quantity, and reactivity of DOM throughout the greater Everglades ecosystem. The authors discuss the factors controlling DOM concentrations and chemistry, present distribution of DOM throughout the Everglades, the potential effects of DOM on key water-quality issues, and the potential utility of dissolved organic matter as an indicator of success of restoration efforts.

Florida↗
USGS2001

Topographic controls on the chemistry of subsurface stormflow

Models are needed that describe how topography and other watershed characteristics affect the chemical composition of runoff waters, yet little spatially distributed data exist to develop such models. A topographically driven flushing mechanism for nitrate (NO3-) and dissolved organic carbon has been described in recent literature; however, this mechanism has not yet been thoroughly tested. A 24 ha catchment in the Catskill Mountains of New York was clearcut in the winter of 1996-97, resulting in elevated NO3- concentrations in soil water, groundwater and streamflow. We sampled shallow subsurface stormflow (SSSF) and streamflow six times during the spring and summer of 1998, 1 year after the harvest. We used a spatially distributed network of piezometers to investigate the relationship between topography and SSSF chemistry. Several indices of topography were computed, including the commonly employed topographic index of Beven and Kirkby (1979; Hydrological Sciences Bulletin 24: 43-69). Topographic index was positively correlated with NO3- concentrations in SSSF. The strength of the NO3- -topography relationship was best explained by antecedent soil temperature and antecedent precipitation conditions. Results suggest a topographically driven flushing of high NO3- shallow soil at the site during storm events. Copyright ?? 2001 John Wiley & Sons, Ltd.

Hydrological Processes↗
USGS2019

The importance of groundwater flow to the formation of modern thrombolitic microbialites

Modern microbialites are often located within groundwater discharge zones, yet the role of groundwater in microbialite accretion has yet to be resolved. To understand relationships between groundwater, microbialites, and associated microbial communities, we quantified and characterized groundwater flow and chemistry in active thrombolitic microbialites in Lake Clifton, Western Australia, and compared these observations to inactive thrombolites and lakebed sediments. Groundwater flows upward through an interconnected network of pores within the microstructure of active thrombolites, discharging directly from thrombolite heads into the lake. This upwelling groundwater is fresher than lake water and is hypothesized to support microbial mat growth by reducing salinity and providing limiting nutrients in an osmotically stressful and oligotrophic habitat. This is in contrast to inactive thrombolites that show no evidence of microbial mat colonization and are infiltrated by hypersaline lake water. Groundwater discharge through active thrombolites contrasts with the surrounding lakebed, where hypersaline lake water flows downward through sandy sediments at very low rates. Based on an appreciation for the role of microorganisms in thrombolite accretion, our findings suggest conditions favorable to thrombolite formation still exist in certain locations of Lake Clifton despite increasing lake water salinity. This study is the first to characterize groundwater flow rates, paths, and chemistry within a microbialite‐forming environment and provides new insight into how groundwater can support microbial mats believed to contribute to microbialite formation in modern and ancient environments.

Geobiology↗