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USGS1974

WATEQ, a computer program for calculating chemical equilibria of natural waters

The computer program, WATEQ, calculates the equilibrium distribution of inorganic aqueous species of major and important minor elements in natural waters using the chemical analysis and in situ measurements of temperature, pH, and redox potential. From this model, the states of reaction of the water with solid and gaseous phases are calculated. Thermodynamic stabilities of aqueous species, minerals, and gases have been selected from a careful consideration of all available experimental data. The program is written in PL-1 for IBM 360 computers.

Journal of Research of the U.S. Geological Survey↗

USGS1996

Automated, colorimetric methods for determination of nitrate plus nitrite, nitrite, ammonium and orthophosphate ions in natural water samples

The apparatus and methods used for the automatic, colorimetric determinations of dissolved nutrients (nitrate plus nitrite, nitrite, ammonium and orthophosphate) in natural waters are described. These techniques allow for the determination of nitrate plus nitrite for the concentration range 0.02 to 8 mg/L (milligrams per liter) as N (nitrogen); for nitrite, the range is 0.002 to 1.0 mg/L as N; for ammonium, the range is 0.006 to 2.0 mg/L as N; and for orthophosphate, the range is 0.002 to 1.0 mg/L as P (phosphorus). Data are presented that demonstrate the accuracy, precision and quality control of the methods.

Open-File Report↗

USGS1973

An empirical NaKCa geothermometer for natural waters

An empirical method of estimating the last temperature of water-rock interaction has been devised. It is based upon molar Na, K and Ca concentrations in natural waters from temperature environments ranging from 4 to 340°C. The data for most geothermal waters cluster near a straight line when plotted as the function log ( Na K ) + β log [ √ (Ca) Na ] "> log (NaK) + β log [ √(Ca)Na] vs reciprocal of absolute temperature, where β is either 1 3 "> 13 or 4 3 "> 43 depending upon whether the water equilibrated above or below 100°C. For most waters tested, the method gives better results than the Na K "> NaK methods suggested by other workers. The ratio Na K "> NaK should not be used to estimate temperature if √ ( M Ca ) M Na "> √ (MCa)MNa is greater than 1. The Na K "> NaK values of such waters generally yield calculated temperatures much higher than the actual temperature at which water interacted with the rock. A comparison of the composition of boiling hot-spring water with that obtained from a nearby well (170°C) in Yellowstone Park shows that continued water-rock reactions may occur during ascent of water even though that ascent is so rapid that little or no heat is lost to the country rock, i.e. the water cools adiabatically. As a result of such continued reaction, waters which dissolve additional Ca as they ascend from the aquifer to the surface will yield estimated aquifer temperatures that are too low. On the other hand, waters initially having enough Ca to deposit calcium carbonate during ascent may yield estimated aquifer temperatures that are too high if aqueous Na and K are prevented from further reaction with country rock owing to armoring by calcite or silica minerals. The Na-K-Ca geothermometer is of particular interest to those prospecting for geothermal energy. The method also may be of use in interpreting compositions of fluid inclusions.

Wyoming↗

USGS1984

Gold in natural water: A method of determination by solvent extraction and electrothermal atomization

A method has been developed using electrothermal atomization to effectively determine the amount of gold in natural water within the nanogram range. The method has four basic steps: (1) evaporating a 1-L sample; (2) putting it in hydrobromic acid-bromine solution; (3) extracting the sample with methyl-isobutyl-ketone; and (4) determining the amount of gold using an atomic absorption spectrophotometer. The limit of detection is 0.001 μg gold per liter. Results from three studies indicate, respectively, that the method is precise, effective, and free of interference. Specifically, a precision study indicates that the method has a relative standard deviation of 16–18%; a recovery study indicates that the method recovers gold at an average of 93%; and an interference study indicates that the interference effects are eliminated with solvent extraction and background correction techniques. Application of the method to water samples collected from 41 sites throughout the Western United States and Alaska shows a gold concentration range of < 0.001 to 0.036 μ g gold per liter, with an average of 0.005 μg/L.

Journal of Geochemical Exploration↗

USGS1996

Problems associated with using filtration to define dissolved trace element concentrations in natural water samples

Field and laboratory experiments indicate that a number of factors associated with filtration other than just pore size (e.g., diameter, manufacturer, volume of sample processed, amount of suspended sediment in the sample) can produce significant variations in the “dissolved” concentrations of such elements as Fe, Al, Cu, Zn, Pb, Co, and Ni. The bulk of these variations result from the inclusion/exclusion of colloidally associated trace elements in the filtrate, although dilution and sorption/desorption from filters also may be factors. Thus, dissolved trace element concentrations quantitated by analyzing filtrates generated by processing whole water through similar pore-sized filters may not be equal or comparable. As such, simple filtration of unspecified volumes of natural water through unspecified 0.45-μm membrane filters may no longer represent an acceptable operational definition for a number of dissolved chemical constituents.

Environmental Science & Technology↗

USGS1976

Measurement of "turbidity" and related characteristics of natural waters

The U.S. Geological Survey, Water Resources Division has adopted the following principles to be used in selecting methods for the measurement of light transmitting characteristics of natural waters: (1) standard instruments and methods are to be adopted to measure and report in optical units, avoiding ' turbidity ' as a quantitative measure; (2) reporting of ' turbidity ' in JTU 's, Hellige units, severity, or NTU 's will be phased out; (3) the basis for estimations of sediment concentrations based on light measurements must be documented adequately; and (4) use of transparency measurement by Secchi disk is not changed, although light transmittance may prove to be more precise means of obtaining the same information. A schedule has been established to implement new methods beginning October 1, 1976, and with the transition to be completed at all stations by October 1, 1977. Provisions are provided to meet requirements of cooperators who have legal requirements for ' turbidity ' data. (Woodard-USGS)

Open-File Report↗

USGS1975

Uranium determination in natural water by the fissiontrack technique

The fission track technique, utilizing the neutron-induced fission of uranium-235, provides a versatile analytical method for the routine analysis of uranium in liquid samples of natural water. A detector is immersed in the sample and both are irradiated. The fission track density observed in the detector is directly proportional to the uranium concentration. The specific advantages of this technique are: (1) only a small quantity of sample, typically 0.1–1 ml, is needed; (2) no sample concentration is necessary; (3) it is capable of providing analyses with a lower reporting limit of 1 μg per liter; and (4) the actual time spent on an analysis can be only a few minutes. This paper discusses and describes the method.

Journal of Geochemical Exploration↗

USGS1996

Inductively coupled plasma-mass spectrometric method for the determination of dissolved trace elements in natural water

An inductively coupled plasma-mass spectrometry method was developed for the determination of dissolved Al, As, B, Ba, Be, Cd, Co, Cr, Cu, Li, Mn, Mo, Ni, Pb, Sr, Tl, U, V, and Zn in natural waters. Detection limits are generally in the 50-100 picogram per milliliter (pg/mL) range, with the exception of As which is in the 1 microgram per liter (ug/L) range. Interferences associated with spectral overlap from concomitant isotopes or molecular ions and sample matrix composition have been identified. Procedures for interference correction and reduction related to isotope selection, instrumental operating conditions, and mathematical data processing techniques are described. Internal standards are used to minimize instrumental drift. The average analytical precision attainable for 5 times the detection limit is about 16 percent. The accuracy of the method was tested using a series of U.S. Geological Survey Standard Reference Water Standards (SWRS), National Research Council Canada Riverine Water Standard, and National Institute of Standards and Technology (NIST) Trace Elements in Water Standards. Average accuracies range from 90 to 110 percent of the published mean values.

Open-File Report↗

USGS1980

Additional and revised thermochemical data and computer code for WATEQ2: a computerized chemical model for trace and major element speciation and mineral equilibria of natural waters

A computerized chemical model, WATEQ2, has resulted from extensive additions to and revision of the WATEQ model of Truesdell and Jones (Truesdell, A. H., and Jones, B. F., 1974, WATEQ, a computer program for calculating chemical equilibria of natural waters: J. Res. U. S. Geol, Survey, v. 2, p. 233-274). The model building effort has necessitated searching the literature and selecting thermochemical data pertinent to the reactions added to the model. This supplementary report manes available the details of the reactions added to the model together with the selected thermochemical data and their sources. Also listed are details of program operation and a brief description of the output of the model. Appendices-contain a glossary of identifiers used in the PL/1 computer code, the complete PL/1 listing, and sample output from three water analyses used as test cases.

Water-Resources Investigations Report↗

USGS2010

Calibrating biomonitors to ecological disturbance: a new technique for explaining metal effects in natural waters

Bioaccumulated toxic metals in tolerant biomonitors are indicators of metal bioavailability and can be calibrated against metal‐specific responses in sensitive species, thus creating a tool for defining dose–response for metals in a field setting. Dose–response curves that define metal toxicity in natural waters are rare. Demonstrating cause and effect under field conditions and integrated chemical measures of metal bioavailability from food and water is problematic. The total bioaccumulated metal concentration in any organism that is a net accumulator of the metal is informative about metal bioavailability summed across exposure routes. However, there is typically no one universal metal concentration that is indicative of toxicity, especially across species, largely because of interspecies differences in detoxification. Stressed organisms are also only present across a narrow range in the dose–response curve, limiting the use of singles species as both biomonitors and bioindicator of stress. Herein we show, in 3 field settings, that bioaccumulated Cu concentrations in a metal‐tolerant, riverine biomonitor (species of the caddisfly genus Hydropsyche spp.) can be calibrated against metal‐specific ecological responses across very wide ranges of contamination. Using the calibrated dose–response, we show that reduced abundance of species and individuals from particularly sensitive mayfly families (heptageniid mayflies) is more than 2‐fold more sensitive to bioavailable Cu than other traditional measures of stress like EPT or total number of benthic macroinvertebrate species. We propose that this field dose‐response curve be tested more widely for general application, and that calibrations against other stress responses be developed for biomonitors from lakes, estuaries, and coastal marine ecosystems.

Integrated Environmental Assessment and Management↗

USGS2000

Selective trace enrichment of chlorotriazine pesticides from natural waters and sediment samples using terbuthylazine molecularly imprinted polymers

Two molecularly imprinted polymers were synthesized using either dichloromethane or toluene as the porogen and terbuthylazine as the template and were used as solid-phase extraction cartridges for the enrichment of six chlorotriazines (deisopropylatrazine, deethylatrazine, simazine, atrazine, propazine, and terbuthylazine) in natural water and sediment samples. The extracted samples were analyzed by liquid chromatography/diode array detection (LC/DAD). Several washing solvents, as well as different volumes, were tested for their ability to remove the matrix components nonspecifically adsorbed on the sorbents. This cleanup step was shown to be of prime importance to the successful extraction of the pesticides from the aqueous samples. The optimal analytical conditions were obtained when the MIP imprinted using dichloromethane was the sorbent, 2 mL of dichloromethane was used in the washing step, and the preconcentrated analytes were eluted with 8 mL of methanol. The recoveries were higher than 80% for all the chlorotriazines except for propazine (53%) when 50- or 100-mL groundwater samples, spiked at 1 ??g/L level, were analyzed. The limits of detection varied from 0.05 to 0.2 ??g/L when preconcentrating a 100-mL groundwater sample. Natural sediment samples from the Ebre Delta area (Tarragona, Spain) containing atrazine and deethylatrazine were Soxhlet extracted and analyzed by the methodology developed in this work. No significant interferences from the sample matrix were noticed, thus indicating good selectivity of the MIP sorbents used.

Analytical Chemistry↗

USGS2023

Salinity and total dissolved solids measurements for natural waters: An overview and a new salinity method based on specific conductance and water type

The total concentration of dissolved constituents in water is routinely quantified by measurements of salinity or total dissolved solids (TDS). However, salinity and TDS are operationally defined by their analytical methods and are not equivalent for most waters. Furthermore, multiple methods are available to determine salinity and TDS, and these methods have inherent differences. TDS is defined as the mass of anhydrous residue remaining in a sample vessel after evaporation and subsequent oven drying at a defined temperature. Salinity is a measure of the mass of dissolved salts in a given mass of solution. In addition, there are approaches that quantify the total solute (TS) concentration, including gases. The purpose of this study is to develop a proxy method using specific conductance and major-ion water type to reliably predict salinity, TDS, and/or TS. Thus, we compared several methods to calculate salinity, TDS, and TS for 6391 surface water samples and conclude the following: TDS measurements are best suited for studies of anhydrous residue (e.g., evaporites); salinity determined by summing the speciated ion concentrations, termed S ∑spec , is the most comprehensive method to represent the concentration of dissolved constituents in natural waters; and TS determinations are useful if dissolved CO 2 and other gases are of interest. Thus, we utilized S ∑spec to compare differences between the various salinity, TDS, and TS methods, and to develop a new proxy method to predict salinity based on specific conductance (SC) and major ion water type, termed S SC_WT . For the surface waters used in this study, the median difference between TDS and S ∑Spec was between −19% and −24%, depending on the method. The median difference between S SC_WT and S ∑Spec was −2.4% for the samples in this study. The S SC_WT approach is cost effective, rapid, and capable of providing reliable real-time salinity determinations at surface water sites where SC data are available and water type is known.

Applied Geochemistry↗

USGS1978

Stability of fluoride complex with silica and its distribution in natural water systems

Fluoride reacts with silicic acid to form SiF 2− 6 . A fluoride electrode was used to obtain an equilibrium constant of 10 30.18 for the reaction: Si(OH) 0 6 + 6 F − +4 H + = SiF 2− 6 + 4 H 2 O "> Si(OH)06+ 6F−+4H+=SiF2−6+ 4H2O at 25°C Although there may be some experimental evidence for existence of traces of species containing less than six F − ions per silicon ( n = 6), the species SiF 2− 6 predominates for n values from about 0.1 to 6. Silicic-acid complexing with fluoride is important only in solutions which have rather low pH and low concentrations of other cations which compete with silicon for fluoride. Computations for cold volcanic condensates from Hawaii indicate that for some samples much of the silicon is complexed by fluoride as SiF 2− 6 . However, in most cooled acidic natural water samples Al and Fe are more important than Si in complexing fluoride.

Chemical Geology↗

USGS2009

Compensating for diminishing natural water: Predicting the impacts of water development on summer habitat of desert bighorn sheep

Artificial water sources have been used for decades to enhance and restore wildlife habitat but the benefits of their use have been subject to debate. During the past century, the number of natural springs in Joshua Tree National Park, California, USA, has declined. In response to concerns about the viability of the bighorn sheep (Ovis canadensis nelsoni) population, a number of water developments were constructed throughout the park. We modeled potential historical and present-day summer habitat of female bighorn sheep to evaluate the effectiveness of the artificial and remaining natural water sources in maintaining habitat and to determine how loss of artificial sources might affect future habitat availability. Prior to 1950, 583.5 km2 of summer habitat was potentially available. Presently, only 170.6 km2 of habitat is available around natural water sources and 153.5 km2 is available around guzzlers. When all perennial water sources are included in the habitat model (minus overlap), 302.3 km2 of summer habitat is potentially available. This represents only 51.7% of summer habitat available prior to 1950. Without artificial water developments, 47.7% of present-day summer habitat would be lost, which raises important management questions regarding the debate about what is natural or artificial within otherwise protected areas.

Journal of Arid Environments↗

USGS2002

Methylmercury in flood-control impoundments and natural waters of northwestern Minnesota, 1997-99

We studied methylmercury (MeHg) and total mercury (HgT) in impounded and natural surface waters in northwestern Minnesota, in settings ranging from agricultural to undeveloped. In a recently constructed (1995) permanent-pool impoundment, MeHg levels typically increased from inflow to outflow during 1997; this trend broke down from late 1998 to early 1999. MeHg levels in the outflow reached seasonal maxima in mid-summer (maximum of 1.0 ng L −1 in July 1997) and late-winter (maximum of 6.6 ng L −1 in February 1999), and are comparable to high levels observed in new hydroelectric reservoirs in Canada. Spring and autumn MeHg levels were typically about 0.1–0.2 ng L −1 . Overall, MeHg levels in both the inflow (a ditch that drains peatlands) and outflow were significantly higher than in three nearby reference natural lakes. Eleven older permanent-pool impoundments and six natural lakes in northwestern Minnesota were sampled five times. The impoundments typically had higher MeHg levels (0.071–8.36 ng L −1 ) than natural lakes. Five of six lakes MeHg levels typical of uncontaminated lakes (0.014–1.04 ng L −1 ) with highest levels in late winter, whereas a hypereutrophic lake had high levels (0.37–3.67 ng L −1 ) with highest levels in mid-summer. Seven temporary-pool impoundments were sampled during summer high-flow events. Temporary-pool impoundments that retained water for about 10–15 days after innundation yielded pronounced increases in MeHg from inflow to outflow, in one case reaching 4.6 ng L −1 , which was about 2 ng L −1 greater than the mean inflow concentration during the runoff event.

Minnesota↗

USGS1996

Re-evaluation of colorimetric Cl- data from natural waters with DOC

Colorimetric Cl- data from natural solutions that contain dissolved organic carbon (DOC) may be biased high. We evaluated aquatic Cl- concentrations in ecosystem compartments at the Bear Brook Watershed, Maine, and from lakes in Maine, using ion chromatography and colorimetry. DOC imparts a positive interference on colorimetric Cl- results proportional to DOC concentrations at approximately 0.8 ??eq Cl-/L per mg DOC/L. The interference is not a function of Cl- concentration. The resulting bias in concentrations of Cl- may be 50% or more of typical environmental values for Cl- in areas remote from atmospheric deposition of marine aerosols. Such biased data in the literature appear to have led to spurious conclusions about recycling of Cl- by forests, the usefulness of Cl- as a conservative tracer in watershed studies, and calculations of elemental budgets, ion balance, charge density of DOC, and dry deposition factors.

Water, Air, & Soil Pollution↗

USGS2002

Optical characteristics of natural waters protect amphibians from UV-B in the U.S. Pacific Northwest

Increased exposure to ultraviolet-B (UV-B) radiation has been proposed as a major environmental stressor leading to global amphibian declines. Prior experimental evidence from the U.S. Pacific Northwest (PNW) indicating the acute embryonic sensitivity of at least four amphibian species to UV-B has been central to the literature about amphibian decline. However, these results have not been expanded to address population-scale effects and natural landscape variation in UV-B transparency of water at amphibian breeding sites: both necessary links to assess the importance of UV-B for amphibian declines. We quantified the UV-B transparency of 136 potential amphibian breeding sites to establish the pattern of UV-B exposure across two montane regions in the PNW. Our data suggest that 85% of sites are naturally protected by dissolved organic matter in pond water, and that only a fraction of breeding sites are expected to experience UV-B intensities exceeding levels associated with elevated egg mortality. Thus, the spectral characteristics of natural waters likely mediate the physiological effects of UV-B on amphibian eggs in all but the clearest waters. These data imply that UV-B is unlikely to cause broad amphibian declines across the landscape of the American Northwest.

California, Oregon, Washington↗

USGS2003

Sulfur geochemistry of hydrothermal waters in Yellowstone National Park, Wyoming, USA. III. An anion-exchange resin technique for sampling and preservation of sulfoxyanions in natural waters

A sampling protocol for the retention, extraction, and analysis of sulfoxyanions in hydrothermal waters has been developed in the laboratory and tested at Yellowstone National Park and Green Lake, NY. Initial laboratory testing of the anion-exchange resin Bio-Rad??? AG1-X8 indicated that the resin was well suited for the sampling, preservation, and extraction of sulfate and thiosulfate. Synthetic solutions containing sulfate and thiosulfate were passed through AG1-X8 resin columns and eluted with 1 and 3 M KCl, respectively. Recovery ranged from 89 to 100%. Comparison of results for water samples collected from five pools in Yellowstone National Park between on-site IC analysis (U.S. Geological Survey mobile lab) and IC analysis of resin-stored sample at SUNY-Stony Brook indicates 96 to 100% agreement for three pools (Cinder, Cistern, and an unnamed pool near Cistern) and 76 and 63% agreement for two pools (Sulfur Dust and Frying Pan). Attempts to extract polythionates from the AG1-X8 resin were made using HCl solutions, but were unsuccessful. Bio-Rad??? AG2-X8, an anion-exchange resin with weaker binding sites than the AG1-X8 resin, is better suited for polythionate extraction. Sulfate and thiosulfate extraction with this resin has been accomplished with KCl solutions of 0.1 and 0.5 M, respectively. Trithionate and tetrathionate can be extracted with 4 M KCl. Higher polythionates can be extracted with 9 M hydrochloric acid. Polythionate concentrations can then be determined directly using ion chromatographic methods, and laboratory results indicate recovery of up to 90% for synthetic polythionate solutions using AG2-X8 resin columns. ?? The Royal Society of Chemistry and the Division of Geochemistry of the American Chemical Society 2003.

Geochemical Transactions↗