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USGS2018

Laboratory evaluation of the Sea-Bird Scientific HydroCycle-PO4 phosphate sensor

Sea-Bird Scientific’s HydroCycle-PO 4 phosphate sensor is a single-analyte wet-chemistry sensor designed for in situ environmental monitoring. The unit was evaluated at the U.S. Geological Survey Hydrologic Instrumentation Facility to assess the accuracy of the sensor in solutions with known phosphorous concentration and to test the effects of chromophoric (colored) dissolved organic matter (CDOM) and natural water matrixes on sensor accuracy. Accuracy was tested with three standards: 0.110, 0.174, and 0.260 milligram per liter, as phosphorous (mg/L as P). The 0.110- and 0.260-mg/L standards were made from a dilution of a National Institute of Standards and Technology-traceable phosphate-phosphorous standard with Type I deionized water (DIW). Average measured phosphate concentrations of the tested standards (0.110, 0.174, and 0.260 mg/L as P) in DIW were 0.132, 0.181, and 0.310 mg/L as P, for differences of 20, 4, and 19 percent, respectively. Measured phosphate concentration of a tested standard was biased by the addition of tea water filtered through a 0.45-micrometer pore size filter (filtered tea water [FTW]) simulating the effect of CDOM. An aliquot of the filtered tea solution was sent to a certified environmental laboratory, which reported a less than reporting level (<0.004 mg/L as P) phosphate concentration. True color of the FTW was measured at 380 platinum-cobalt units by using Standard Methods 8025. For this FTW test, the measured phosphate concentration for the clear 0.260 mg/L as P standard averaged 0.366 mg/L as P. This concentration increased to an average of 0.653 mg/L as P with the addition of 10 percent FTW, and to an average of 0.859 mg/L as P with the addition of 20 percent FTW. These test results indicate a positive bias of up to 40 percent of the concentrations of the measured phosphate concentrations when CDOM is present and indicate a proportional increase in an apparent concentration of phosphorus instrument response as CDOM concentration increases.

Open-File Report↗

USGS1996

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↗

USGS2011

Simultaneous speciation of arsenic, selenium, and chromium: species, stability, sample preservation, and analysis of ash and soil leachates

An analytical method using high-performance liquid chromatography separation with inductively coupled plasma mass spectrometry (ICP-MS) detection previously developed for the determination of Cr(III) and Cr(VI) has been adapted to allow the determination of As(III), As(V), Se(IV), Se(VI), Cr(III), and Cr(VI) under the same chromatographic conditions. Using this method, all six inorganic species can be determined in less than 3 min. A dynamic reaction cell (DRC)-ICP-MS system was used to detect the species eluted from the chromatographic column in order to reduce interferences. A variety of reaction cell gases and conditions may be utilized with the DRC-ICP-MS, and final selection of conditions is determined by data quality objectives. Results indicated all starting standards, reagents, and sample vials should be thoroughly tested for contamination. Tests on species stability indicated that refrigeration at 10° C was preferential to freezing for most species, particularly when all species were present, and that sample solutions and extracts should be analyzed as soon as possible to eliminate species instability and interconversion effects. A variety of environmental and geological samples, including waters and deionized water [leachates] and simulated biological leachates from soils and wildfire ashes have been analyzed using this method. Analytical spikes performed on each sample were used to evaluate data quality. Speciation analyses were conducted on deionized water leachates and simulated lung fluid leachates of ash and soils impacted by wildfires. These results show that, for leachates containing high levels of total Cr, the majority of the chromium was present in the hexavalent Cr(VI) form. In general, total and hexavalent chromium levels for samples taken from burned residential areas were higher than those obtained from non-residential forested areas. Arsenic, when found, was generally in the more oxidized As(V) form. Selenium (IV) and (VI) were present, but typically at low levels.

Analytical and Bioanalytical Chemistry↗

USGS2023

Stream sediment geochemistry in mineral exploration: A review of fine-fraction, clay-fraction, bulk leach gold, heavy mineral concentrate and indicator mineral chemistry

Stream sediment surveys support early-stage reconnaissance mineral exploration and regional assessment programmes, enhanced by recent improvements in analytical method detection limits, continuously improving mineral chemistry, and new approaches to the interpretation of geochemical data. Sediment surveys may be used to predict catchment basin lithology, mineralization type based on pathfinder geochemistry, and geological features based on indicator mineral chemistry. Sediment surveys that target a finer-fraction sediment sample led to the discovery of the La Colosa gold deposit, Colombia. The Batu Hijau porphyry Cu–Au deposit in Indonesia was discovered based on an anomalous clay-sized fraction sample 12 km downstream. In an arid region with poorly developed drainages and minor topographic relief, the Ag-base-metal Navidad District in Argentina was discovered with clay-fraction sediment geochemistry. Heavy mineral concentrate (HMC) sediment surveys that include mineral chemistry determinations have led to global diamond discoveries. HMC surveys contributed to discovery of the Ring of Fire Ni–Cu–PGE and chromite district, Ontario, Canada. Discoveries and geochemical mapping can assist advancement of the application of stream sediment geochemistry in those global areas for which lithologies and deposits are exposed. Stream sediment surveys continue to be one of the most cost-effective geochemical methods for covering large areas for mineral exploration.

Geochemistry: Exploration, Environment, Analysis↗

USGS2022

Hydrogen isotope behavior during rhyolite glass hydration under hydrothermal conditions

The diffusion of molecular water (H 2 O m ) from the environment into volcanic glass can hydrate the glass up to several wt% at low temperature over long timescales. During this process, the water imprints its hydrogen isotope composition (δD H2O ) to the glass (δD gl ) offset by a glass-H 2 O fractionation factor (ΔD gl-H2O = δD gl – δD H2O ) which is approximately −33‰ at Earth surface temperatures. Glasses hydrate much more rapidly at higher, sub-magmatic temperatures as they interact with H 2 O during eruption, transport, and emplacement. To aid in the interpretation of δD gl in natural samples, we present hydrogen isotope results from vapor hydration experiments conducted at 175–375 °C for durations of hours to months using natural volcanic glasses. The results can be divided into two thermal regimes: above 250 °C and below 250 °C. Lower temperature experiments yield raw ΔD gl-H2O values in the range of −33 ± 11‰. Experiments at 225 °C using both positive and negative initial ΔD gl-H2O values converge on this range of values, suggesting this range represents the approximate equilibrium fractionation for H isotopes between glass and H 2 O vapor (10 3 lnα gl-H2O ) below 250 °C. Variation in ΔD gl-H2O (−33 ± 11‰) between different experiments and glasses may arise from incomplete hydration, analytical uncertainty, differences in glass chemistry, and/or subordinate kinetic isotope effects. Experiments above 250 °C yield unexpectedly low δD gl values with ΔD gl-H2O values of ≤–85‰. While alteration alone is incapable of explaining the data, these run products have more extensive surface alteration and are not interpreted to reflect equilibrium fractionation between glass and H 2 O vapor. Fourier transform infrared spectroscopy (FTIR) shows that glass can hydrate with as much as 5.9 wt% H 2 O m and 1.0 wt% hydroxl (OH − ) in the highest P-T experiment at 375 °C and 21.1 MPa. Therefore, we employ a 1D isotope diffusion–reaction model of glass hydration to evaluate the roles of equilibrium fractionation, isotope diffusion, water speciation reactions internal to the glass, and changing boundary conditions (e.g. alteration and dissolution). At lower temperatures, the best fitting model results to experimental data for low silica rhyolite (LSR) glasses require only an equilibrium fractionation factor and yield 10 3 lnα gl-H2O values of −33‰ ± 5‰ and −25‰ ± 5‰ at 175 °C and 225 °C, respectively. At higher temperatures, ΔD gl-H2O is dominated by boundary layer effects during glass hydration and glass surface alteration. The modeled bulk δD gl value is highly responsive to changes in the δD gl boundary condition regardless of the magnitude of other kinetic effects. Observed glass dissolution and surficial secondary mineral formation are likely to impose a disequilibrium boundary layer that drives extreme δD gl fractionation with progressive glass hydration. These results indicate that the observed ΔD gl-H2O of ∼−33 ± 11‰ can be cautiously applied as an equilibrium 10 3 lnα gl-H2O value to natural silicic glasses hydrated below 250 °C to identify hydration sources. This approximate ΔD gl-H2O may be applicable to even higher temperature glasses hydrated on short timescales (of seconds to minutes) in phreatomagmatic or submarine eruptions before H 2 O in the glass is primarily affected by boundary layer effects associated with alteration on the glass surface.

Geochimica et Cosmochimica Acta↗

USGS2011

Gas and isotope chemistry of thermal features in Yellowstone National Park, Wyoming

This report presents 130 gas analyses and 31 related water analyses on samples collected from thermal features at Yellowstone between 2003 and 2009. An overview of previous studies of gas emissions at Yellowstone is also given. The analytical results from the present study include bulk chemistry of gases and waters and isotope values for water and steam (delta18O, dealtaD), carbon dioxide (delta13C only), methane (delta13C only), helium, neon, and argon. We include appendixes containing photos of sample sites, geographic information system (GIS) files including shape and kml formats, and analytical results in spreadsheets. In addition, we provide a lengthy discussion of previous work on gas chemistry at Yellowstone and a general discussion of the implications of our results. We demonstrate that gases collected from different thermal areas often have distinct chemical signatures, and that differences across the thermal areas are not a simple function of surface temperatures or the type of feature. Instead, gas chemistry and isotopic composition are linked to subsurface lithologies and varying contributions from magmatic, crustal, and meteoric sources.

Wyoming↗

USGS2005

Surface complexation studied via combined grazing-incidence EXAFS and surface diffraction: Arsenate on hematite (0001) and (10-12)

X-ray diffraction [crystal-truncation-rod (CTR)] studies of the surface structure of moisture-equilibrated hematite reveal sites for complexation not present on the bulk oxygen-terminated surface, and impose constraints on the types of inner-sphere sorption topologies. We have used this improved model of the hematite surface to analyze grazing-incidence EXAFS results for arsenate sorption on the c (0001) and r (10–12) surfaces measured in two electric vector polarizations. This work shows that the reconfiguration of the surface under moist conditions is responsible for an increased adsorption density of arsenate complexes on the (0001) surface relative to predicted ideal termination, and an abundance of “edge-sharing” bidentate complexes on both studied surfaces. We consider possible limitations on combining the methods due to differing surface sensitivities, and discuss further analysis possibilities using both methods.

Analytical and Bioanalytical Chemistry↗

USGS2015

Developing analytical approaches to explore the connection between endocrine-active pharmaceuticals in water to effects in fish

The emphasis of this research project was to develop and optimize a solid-phase extraction method and highperformance liquid chromatography-electrospray ionizationmass spectrometry method, such that a linkage between the detection of endocrine-active pharmaceuticals (EAPs) in the aquatic environment and subsequent effects on fish populations could eventually be studied. Four EAPs were studied: tamoxifen (TAM), exemestane (EXE), letrozole (LET), anastrozole (ANA); and three TAM metabolites: 4- hydroxytamoxifen, e/z endoxifen, and n-desmethyl tamoxifen. In aqueous matrices, the use of isotopically labeled standards for the EAPs allowed for the generation of good recoveries, greater than 80 %, and low relative standard deviations (% RSDs) (3 to 27 %). TAM metabolites had lower recoveries in the spiked water matrices: 35 to 93 % in waste/source water compared to 58 to 110 % in DI water. The precision in DI water was acceptable ranging from 8 to 38 % RSD. However, the precision in real environmental wastewaters could be poor, ranging from 15 to 120 % RSD, dependent upon unique matrix effects. In plasma, the overall recoveries of the EAPs were acceptable: 88 to 110 %, with %RSDs of 6 to 18 % (Table 3). The spiked recoveries of the TAM metabolites from plasma were good, ranging from 77 to 120 %, with %RSDs ranging from 27 to 32 %. Two of the TAM metabolites, 4- hydroxytamoxifen and n-desmethyl tamoxifen, were confirmed in most of the environmental aqueous samples. The discovery of TAM metabolites demonstrates that the source of the TAM metabolites, TAM, is constant, introducing a pseudo-persistence of this chemical into the environment.

Analytical and Bioanalytical Chemistry↗

USGS2019

Isolation of methylmercury using distillation and anion-exchange chromatography for isotopic analyses in natural matrices

The development of mercury (Hg) stable isotope measurements has enhanced the study of Hg sources and transformations in the environment. As a result of the mixing of inorganic Hg (iHg) and methylmercury (MeHg) species within organisms of the aquatic food web, understanding species-specific Hg stable isotopic compositions is of significant importance. The lack of MeHg isotope measurements is due to the analytical difficulty in the separation of the MeHg from the total Hg pool, with only a few methods having been tested over the past decade with varying degrees of success, and only a handful of environmentally relevant measurements. Here, we present a novel anion-exchange resin separation method using AG 1-X4 that further isolates MeHg from the sample matrix, following a distillation pretreatment, in order to obtain ambient MeHg stable isotopic compositions. This method avoids the use of organic reagents, does not require complex instrumentation, and is applicable across matrices. Separation tests across sediment, water, and biotic matrices showed acceptable recoveries (98 ± 5%, n = 54) and reproducible δ 202 Hg isotope results (2 SDs ≤ 0.15‰) down to 5 ng of MeHg. The measured MeHg pools in natural matrices, such as plankton and sediments, showed large deviations from the non-speciated total Hg measurement, indicating that there is an important isotopic shift during methylation that is not recorded by typical measurements, but is vital in order to assess sources of Hg during bioaccumulation.

Analytical and Bioanalytical Chemistry↗

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↗

USGS1978

A computer-assisted graphical method for identification and correlation of igneous rock chemistries

We have devised a computer-assisted graphical method for correlating chemical analyses in suites of related igneous rocks. The method provides a direct and empirical means of sample identification using all of the reported chemistry. In a study of basalt of the Columbia River plateau, the method has been used for (1) checking field identifications of rocks, (2) spotting analytical errors in analyses of samples of known chemical type, (3) identifying repetitions of chemistry in thick stratigraphic sections, and (4) matching analyses of dikes to those of flows that the dikes may have fed. Program OXVAR creates a set of oxide-oxide variation diagrams on a CALCOMP plotter; any oxide may be used as the base (for example, MgO, SiO 2 ). For each oxide-oxide variation diagram, program CTSET creates the smallest convex polygon that encloses all the data points as well as a larger polygon that takes into account the error in determination of each data point. A set of nested polygons, one for each oxide, then represents a chemical type. Program CTYPE identifies unknown analyses by comparing them with all defined chemical types. If all the elements or oxides of an analysis plot within the defined polygons for a given chemical type, then an identification is printed. If at least one element of an analysis falls outside the set of polygons defined for each chemical type, then “unidentified” is printed, and qualitative information on the amount of deviation from the defined chemical types is given.

Geology↗

USGS2010

Effects of selected low-impact-development (LID) techniques on water quality and quantity in the Ipswich River Basin, Massachusetts: Field and modeling studies

During the months of August and September, flows in the Ipswich River, Massachusetts, dramatically decrease largely due to groundwater withdrawals needed to meet increased residential and commercial water demands. In the summer, rates of groundwater recharge are lower than during the rest of the year, and water demands are higher. From 2005 to 2008, the U.S. Geological Survey, in a cooperative funding agreement with the Massachusetts Department of Conservation and Recreation, monitored small-scale installations of low-impact-development (LID) enhancements designed to diminish the effects of storm runoff on the quantity and quality of surface water and groundwater. Funding for the studies also was contributed by the U.S. Environmental Protection Agency’s Targeted Watersheds Grant Program through a financial assistance agreement with Massachusetts Department of Conservation and Recreation. The monitoring studies examined the effects of (1) replacing an impervious parking lot surface with a porous surface on groundwater quality, (2) installing rain gardens and porous pavement in a neighborhood of 3 acres on the quantity and quality of stormwater runoff, and (3) installing a 3,000-square foot (ft2) green roof on the quantity and quality of stormwater runoff. In addition, the effects of broad-scale implementation of LID techniques, reduced water withdrawals, and water-conservation measures on streamflow in large areas of the basin were simulated using the U.S. Geological Survey’s Ipswich River Basin model. From June 2005 to 2007, groundwater quality was monitored at the Silver Lake town beach parking lot in Wilmington, MA, prior to and following the replacement of the conventional, impervious-asphalt surface with a porous surface consisting primarily of porous asphalt and porous pavers. Changes in the concentrations of the water-quality constituents, phosphorus, nitrogen, cadmium, chromium, copper, lead, nickel, zinc, and total petroleum hydrocarbons, were monitored. Increased infiltration of precipitation did not result in discernible increases in concentrations of these potential groundwater contaminants. Concentrations of dissolved oxygen increased slightly in groundwater profiles following the removal of the impervious asphalt parking lot surface. In Wilmington, MA, in a 3-acre neighborhood, stormwater runoff volume and quality were monitored to determine the ability of selected LID enhancements (rain gardens and porous paving stones) to reduce flows and loads of the above constituents to Silver Lake. Flow-proportional water-quality samples were analyzed for nutrients, metals, total petroleum hydrocarbons, and total-coliform and Escherichia coli bacteria. In general, when all storms were considered, no substantial decreases were observed in runoff volume as a result of installing LID enhancements. However, the relation between rainfall and runoff did provide some insight into how the LID enhancements affected the effective impervious area for the neighborhood. A decrease in runoff was observed for storms of 0.2 inches (in.) or less of precipitation, which indicated a reduction in effective impervious area from approximately 10 percent to about 4.5 percent for the 3-acre area. Water-quality-monitoring results were inconclusive; there were no statistically significant differences in concentrations or loads when the pre- and post-installation-period samples were compared. Three factors were probably most important in minimizing differences: (1) the small decrease in effective impervious area, (2) the differences in the size of storms sampled for water-quality constituents before and after installation of the infiltration enhancing measures, and (3) small sample sizes. In a third field study, the characteristics of runoff from a vegetated “green” roof and a conventional, rubber-membrane roof were compared. The amount of precipitation and the length of the antecedent dry period were the two primary factors affecting the green roof’s water-storage capacity. The green roof retained more than 50 percent of the precipitation from storms with 0.04 to 1.0 in. of rain. Approximately 95 percent of the precipitation from one storm of nearly 2 in. was retained by the green roof. On the rubber-membrane roof, only a small, shallow puddle of insubstantial volume ever remained after a storm. Bulk precipitation from 10 storms was monitored for the same constituents (nutrients, metals, and total petroleum hydrocarbons) as the roof runoff, and the results were compared with those for roof-runoff samples. The use of fertilizers to help establish the vegetation during the study probably distorted any effect the plants and growing medium may have had on the retention of target analytes. As a result of the fertilizer and growing medium chemistry, median concentrations of total nitrogen, total phosphorus, cadmium, copper, and nickel in runoff from the green roof were greater than in the runoff from the conventional roof or in bulk precipitation. Concentrations of lead and zinc were greater in runoff from the conventional roof, probably a result of passage through the old, metal drainpipes. Simulations of the effects of LID on streamflow in the Ipswich River Basin were conducted with a previously calibrated Hydrological Simulation Program-FORTRAN (HSPF) precipitation-runoff model. Simulations were conducted at multiple spatial scales to evaluate the effects of (1) updated water withdrawals for the towns of Reading and Wilmington; (2) potential land-use changes at buildout (potential future development); (3) effective impervious area reductions upstream from the South Middleton streamgage to represent the effects of widespread implementation of LID retrofit techniques; (4) basin-scale water withdrawal reductions scaled up (expanded to the town level) from water-conservation pilot programs conducted by the Massachusetts Department of Conservation and Recreation; and (5) land-use change and LID techniques at a local scale, which is smaller than the HSPF subbasin. Effects on streamflow generally were evaluated by comparing results of two or more related simulations for selected reaches in the basin; thus, relative rather than absolute changes in simulated flow were the focus of the assessment. Simulations indicated that reduced withdrawals for the towns of Reading and Wilmington led to substantially higher medium and low flows in most of the reaches upstream from the South Middleton streamgage. Simulations of water-conservation measures resulted in negligible effects on streamflow. Overall, simulations indicated that spatial scale is an important factor in determining the effects of land-use change and LID practices on streamflow. Potential land-use changes at buildout had modest (percent differences of less than 20 percent) effects on streamflow in most subbasins because relatively little land in the basin was available for development (about 17 percent); moreover, most of the available open land is zoned for low-density residential development, and this land-use category was simulated to contain relatively little effective impervious area and to be similar hydrologically to the forested land in place prior to development. Results of the simulations conducted to evaluate widespread effective impervious area reductions upstream from the South Middleton streamgage indicated that the percentage of urban land use and associated effective impervious area was too small for a 50-percent reduction of effective impervious area to appreciably affect streamflow (percent differences of less than 20 percent) in most subbasins. In contrast, the results of the hypothetical local-scale simulations indicated that for smaller streams, where the percentage of urban land use and associated effective impervious area in the drainage area may be substantially higher, land-use change, development patterns, and LID practices potentially have much greater effects on streamflow. Modeling results also indicated that LID was potentially most beneficial for minimizing streamflow alteration when applied to dense urban development, largely because larger tracts of effective impervious area were available for reduction than were available for other land-use categories. For example, commercial-industrial-transportation land use is composed of 37 percent pervious area and 63 percent effective impervious area in the HSPF model, whereas low-density residential area is composed of 97.5 percent pervious area and only 2.5 percent effective impervious area. Field and modeling studies concurred in the assessment that LID enhancements would likely have the greatest effect on decreasing stormwater runoff when broadly applied to highly impervious urban areas. A measurable effect for small rainfall events (less than 0.25 inch) was determined in the small, highly pervious area that was monitored in this study, but the volume difference was not great.

Massachusetts↗

USGS2022

Detecting algal toxins and organic contaminants of concern in the environment

The U.S. Geological Survey (USGS) Kansas Water Science Center Organic Geochemistry Research Laboratory (OGRL) was established in 1987. The OGRL is a multidisciplinary program that contributes knowledge about the distribution, fate, transport, and effects of new and understudied organic compounds that may affect human health and (or) ecosystems. The OGRL consists of two units: Algal and Other Environmental Toxins Unit and Environmental Organic Chemistry Unit. The OGRL does independent and collaborative research, develops robust analytical methods, and provides fee-for-service analytical laboratory analyses.

Fact Sheet↗

USGS2025

Assessment of treated wastewater infiltration in Bright Angel Wash and the potential for contaminants of emerging concern influencing spring water quality along the South Rim of the Grand Canyon in Grand Canyon National Park, Arizona

In April 2021, a synoptic study conducted by the U.S. Geological Survey (USGS) and National Park Service (NPS) identified wastewater-related contaminants of emerging concern (CECs) in springs along the South Rim of the Grand Canyon. These springs are located north of Bright Angel Wash, an ephemeral channel that receives treated effluent from the South Rim Wastewater Treatment Plant (SRWTP). Although water flows southwest and away from the canyon, there is evidence that treated wastewater is finding a flow path along fractures associated with the Bright Angel Fault back to water sources along the South Rim. The CECs identified during the April 2021 sampling included several per- and polyfluoroalkyl substances (PFAS) and pharmaceutical compounds. The PFAS compounds detected only consisted of perfluoroalkyl acids, and these were only detected at Bright Angel Wash (treated wastewater), Monument Spring, and upper Horn Bedrock Spring. The other five sampled springs (the Salt Creek, Horn East Alluvium, Garden, Pumphouse, and Pipe Springs) had no detections of PFAS compounds. The five perfluoroalkyl acids detected at Monument Spring (in descending order of concentration) were perfluorobutanesulfonic acid (PFBS), perfluoropentanoic acid, perfluorooctanoic acid, perfluorohexanoic acid, and perfluorooctanesulfonic acid. Only the short-chained PFBS and perfluorobutanoic acid compounds were detected at the upper Horn Bedrock Spring. All the same perfluoroalkyl acids were found at Bright Angel Wash, except for PFBS. Monument Spring was the only spring to have detections of pharmaceuticals. The two pharmaceuticals detected at the highest concentrations at Monument Spring were diphenhydramine (antihistamine) and carbamazepine (anticonvulsant or anti-epileptic drug). The other detected pharmaceuticals included (in descending order of concentration) fluconazole (antifungal), sulfamethoxazole (antibiotic), metformin (diabetes drug), tramadol (opioid analgesic), and venlafaxine (antidepressant and nerve pain medication). The same pharmaceuticals were detected in the wastewater at Bright Angel Wash but in greater concentrations. No CEC concentrations measured at Monument Spring exceeded any drinking water standards or human health benchmarks; however, most of the compounds detected have no regulatory standards. Studies of the ecological effects of these compounds show that some of the compounds detected can have endocrine and physiological effects, but generally, effects were observed at concentrations multiple orders of magnitude greater than what was measured during the April 2021 study. Data from 1980 through 2022 retrieved from the Water Quality Portal were combined with data from the one-time synoptic sampling in April 2021 to assess the usefulness of other analytes for identifying a wastewater connection to South Rim springs. Most of the historical water chemistry data showed a statistical difference between samples collected within and east of the Garden Creek watershed and samples collected from locations in watersheds to the west of Garden Creek, including the Horn Creek, Salt Creek, Monument Creek, and Hermit Creek watersheds, which roughly align with the Bright Angel Fault. Most of the historical analytes were inconclusive as potential wastewater tracers, but nitrate, chloride, and gadolinium data possibly support the historical contribution of wastewater to Monument Spring.

Arizona↗

USGS2019

The tangled tale of Kīlauea’s 2018 eruption as told by geochemical monitoring

Changes in magma chemistry that affect eruptive behavior occur during many volcanic eruptions, but typical analytical techniques are too slow to contribute to hazard monitoring. We used rapid energy-dispersive X-ray fluorescence analysis to measure diagnostic elements in lava samples within a few hours of collection during the 2018 Kīlauea eruption. The geochemical data provided important information for field crews and civil authorities in advance of changing hazards during the eruption. The appearance of hotter magma was recognized several days before the onset of voluminous eruptions of fast-moving flows that destroyed hundreds of homes. We identified, in near-real time, interactions between older, colder, stored magma – including the unexpected eruption of andesite – and hotter magma delivered during dike emplacement.

Hawaii↗

USGS2017

Updated operational protocols for the U.S. Geological Survey Precipitation Chemistry Quality Assurance Project in support of the National Atmospheric Deposition Program

The U.S. Geological Survey Branch of Quality Systems operates the Precipitation Chemistry Quality Assurance Project (PCQA) for the National Atmospheric Deposition Program/National Trends Network (NADP/NTN) and National Atmospheric Deposition Program/Mercury Deposition Network (NADP/MDN). Since 1978, various programs have been implemented by the PCQA to estimate data variability and bias contributed by changing protocols, equipment, and sample submission schemes within NADP networks. These programs independently measure the field and laboratory components which contribute to the overall variability of NADP wet-deposition chemistry and precipitation depth measurements. The PCQA evaluates the quality of analyte-specific chemical analyses from the two, currently (2016) contracted NADP laboratories, Central Analytical Laboratory and Mercury Analytical Laboratory, by comparing laboratory performance among participating national and international laboratories. Sample contamination and stability are evaluated for NTN and MDN by using externally field-processed blank samples provided by the Branch of Quality Systems. A colocated sampler program evaluates the overall variability of NTN measurements and bias between dissimilar precipitation gages and sample collectors. This report documents historical PCQA operations and general procedures for each of the external quality-assurance programs from 2007 to 2016.

Open-File Report↗

USGS1986

Quality-assurance results for field pH and specific-conductance measurements, and for laboratory analysis, National Atmospheric Deposition Program and National Trends Network; January 1980-September 1984

Five intersite comparison studies for the field determination of pH and specific conductance, using simulated-precipitation samples, were conducted by the U.S.G.S. for the National Atmospheric Deposition Program and National Trends Network. These comparisons were performed to estimate the precision of pH and specific conductance determinations made by sampling-site operators. Simulated-precipitation samples were prepared from nitric acid and deionized water. The estimated standard deviation for site-operator determination of pH was 0.25 for pH values ranging from 3.79 to 4.64; the estimated standard deviation for specific conductance was 4.6 microsiemens/cm at 25 C for specific-conductance values ranging from 10.4 to 59.0 microsiemens/cm at 25 C. Performance-audit samples with known analyte concentrations were prepared by the U.S.G.S.and distributed to the National Atmospheric Deposition Program 's Central Analytical Laboratory. The differences between the National Atmospheric Deposition Program and national Trends Network-reported analyte concentrations and known analyte concentrations were calculated, and the bias and precision were determined. For 1983, concentrations of calcium, magnesium, sodium, and chloride were biased at the 99% confidence limit; concentrations of potassium and sulfate were unbiased at the 99% confidence limit. Four analytical laboratories routinely analyzing precipitation were evaluated in their analysis of identical natural- and simulated precipitation samples. Analyte bias for each laboratory was examined using analysis of variance coupled with Duncan 's multiple-range test on data produced by these laboratories, from the analysis of identical simulated-precipitation samples. Analyte precision for each laboratory has been estimated by calculating a pooled variance for each analyte. Interlaboratory comparability results may be used to normalize natural-precipitation chemistry data obtained from two or more of these laboratories. (Author 's abstract)

Water-Resources Investigations Report↗

USGS1999

Loch Vale Watershed Project quality assurance report, 1995-1998

The Loch Vale Watershed (LVWS) project was initiated in 1980 by the National Park Service with funding from the Aquatic Effects Research Program of the National Acid Precipitation Assessment Program. Initial research objectives were to understand the processes that would either mitigate or accelerate the effects of pollution on soil and surface water chemistry, and to build a record in which long-term trends could be identified and examined. It is important for all data collected in Loch Vale to meet the high standards of quality set forth in previous LVWS QA/QC reports and LVWS Methods Manuals. Given the ever-widening usage of data collected in Loch Vale, it is equally important to provide users of that data with a report assuring that all data are sound. Parameters covered in this report are the quality of meteorological measurements, hydrological measurements, surface water chemistry, and similarities in catch efficiency of two raingage types in Loch Vale for the period of 1995-1998. Routine sampling of weather conditions, precipitation chemistry, and stream/lake water chemistry began in 1982. Since then, all samples and data have been analyzed according to widely accepted and published methods. Weather data have been collected, analyzed, and stored by LVWS project personnel. Methods for the handling of meteorological data are well documented (Denning 1988, Edwards 1991, Newkirk 1995,and Allstott 1995). Precipitation chemistry has always been collected according to National Atmospheric Deposition Program protocol (Bigelow 1988), and analyzed at the Central Analytical Laboratory of the Illinois State Water Survey in Champaign, IL. QA/QC procedures of the National Atmospheric Deposition Program are well documented (Aubertin 1990). Protocols for sampling surface waters are also well documented (Newkirk 1995). Analysis of surface water chemistry has been performed using standard EPA protocol at the US Forest Service's Rocky Mt. Station Biogeochemistry Laboratory since 1993.

Open-File Report↗