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USGS2004

Engelmann Spruce (Picea engelmannii) as a biological monitor of changes in soil metal loading related to past mining activity

Engelmann spruce (Picea engelmannii) is the dominant tree species in many abandoned mine areas of the Rocky Mountains. It is long-lived, and therefore, may act as a long term biological monitor of changes in soil chemistry caused by past mining activity. In this study, laser ablation inductively coupled mass spectrometry (LA-ICPMS) was used to analyze individual tree rings of Engelmann spruce for Fe, Zn, Cu, Cd, Mn, Pb and Sr concentrations. Cores were obtained from trees growing in tailings-impacted and control (non-tailings impacted) sites near the Waldorf mine (Waldorf, CO, USA). Zinc, Cu, Fe, Cd, Pb and Sr concentrations remained low and consistent over time in the control tree rings. However, in the tailings impacted cores, concentrations of Zn, Cu, Fe and Cd increase significantly in post-mining rings. In addition, Zn, Cu, Fe, and Cd concentrations in pre-mining rings of both the control and tailings impacted cores are similar, indicating that present day soil concentrations of these elements in the control area are a reasonable estimation of background for this area. Lead and Sr concentrations in control and tailings-impacted rings remained similar and relatively constant through time and are not useful in determining changes in soil chemistry due to past mining activity. ?? 2004 Elsevier Ltd. All rights reserved.

Applied Geochemistry↗
USGS2004

Comparison of in situ uranium KD values with a laboratory determined surface complexation model

Reactive solute transport simulations in groundwater require a large number of parameters to describe hydrologic and chemical reaction processes. Appropriate methods for determining chemical reaction parameters required for reactive solute transport simulations are still under investigation. This work compares U(VI) distribution coefficients (i.e. KD values) measured under field conditions with KD values calculated from a surface complexation model developed in the laboratory. Field studies were conducted in an alluvial aquifer at a former U mill tailings site near the town of Naturita, CO, USA, by suspending approximately 10 g samples of Naturita aquifer background sediments (NABS) in 17-5.1-cm diameter wells for periods of 3 to 15 months. Adsorbed U(VI) on these samples was determined by extraction with a pH 9.45 NaHCO3/Na2CO3 solution. In wells where the chemical conditions in groundwater were nearly constant, adsorbed U concentrations for samples taken after 3 months of exposure to groundwater were indistinguishable from samples taken after 15 months. Measured in situ K D values calculated from the measurements of adsorbed and dissolved U(VI) ranged from 0.50 to 10.6 mL/g and the KD values decreased with increasing groundwater alkalinity, consistent with increased formation of soluble U(VI)-carbonate complexes at higher alkalinities. The in situ K D values were compared with KD values predicted from a surface complexation model (SCM) developed under laboratory conditions in a separate study. A good agreement between the predicted and measured in situ KD values was observed. The demonstration that the laboratory derived SCM can predict U(VI) adsorption in the field provides a critical independent test of a submodel used in a reactive transport model. ?? 2004 Elsevier Ltd. All rights reserved.

Applied Geochemistry↗
USGS2004

The springs of Lake Pátzcuaro: chemistry, salt-balance, and implications for the water balance of the lake

Lake Pa??tzcuaro, the center of the ancient Tarascan civilization located in the Mexican altiplano west of the city of Morelia, has neither river input nor outflow. The relatively constant lake-salinity over the past centuries indicates the lake is in chemical steady state. Springs of the south shore constitute the primary visible input to the lake, so influx and discharge must be via sub-lacustrine ground water. The authors report on the chemistry and stable isotope composition of the springs, deeming them representative of ground-water input. The springs are dominated by Ca, Mg and Na, whereas the lake is dominated by Na. Combining these results with previously published precipitation/rainfall measurements on the lake, the authors calculate the chemical evolution from spring water to lake water, and also calculate a salt balance of the ground-water-lake system. Comparing Cl and ??18O compositions in the springs and lake water indicates that 75-80% of the spring water is lost evaporatively during evolution toward lake composition. During evaporation Ca and Mg are lost from the water by carbonate precipitation. Each liter of spring water discharging into the lake precipitates about 18.7 mg of CaCO3. Salt balance calculations indicate that ground water input to the lake is 85.9??106 m3/a and ground water discharge from the lake is 23.0??106 m3/a. Thus, the discharge is about 27% of the input, with the rest balanced by evaporation. A calculation of time to reach steady-state ab initio indicates that the Cl concentration of the present day lake would be reached in about 150 a. ?? 2004 Elsevier Ltd. All rights reserved.

Applied Geochemistry↗
USGS2005

Historical deposition and fluxes of mercury in Narraguinnep Reservoir, southwestern Colorado, USA

Narraguinnep Reservoir has been identified as containing fish with elevated Hg concentrations and has been posted with an advisory recommending against consumption of fish. There are presently no point sources of significant Hg contamination to this reservoir or its supply waters. To evaluate potential historical Hg sources and deposition of Hg to Narraguinnep Reservoir, the authors measured Hg concentrations in sediment cores collected from this reservoir. The cores were dated by the 137Cs method and these dates were further refined by relating water supply basin hydrological records with core sedimentology. Rates of historical Hg flux were calculated (ng/cm 2/a) based on the Hg concentrations in the cores, sediment bulk densities, and sedimentation rates. The flux of Hg found in Narraguinnep Reservoir increased by approximately a factor of 2 after about 1970. The 3 most likely sources of Hg to Narraguinnep Reservoir are surrounding bedrocks, upstream inactive Au-Ag mines, and several coal-fired electric power plants in the Four Corners region. Patterns of Hg flux do not support dominant Hg derivation from surrounding bedrocks or upstream mining sources. There are 14 coal-fired power plants within 320 km of Narraguinnep Reservoir that produce over 80 ?? 106 MWH of power and about 1640 kg-Hg/a are released through stack emissions, contributing significant Hg to the surrounding environment. Two of the largest power plants, located within 80 km of the reservoir, emit about 950 kg-Hg/a. Spatial and temporal patterns of Hg fluxes for sediment cores collected from Narraguinnep Reservoir suggest that the most likely source of Hg to this reservoir is from atmospheric emissions from the coal-fired electric power plants, the largest of which began operation in this region in the late-1960s and early 1970s.

Applied Geochemistry↗
USGS2005

Factors controlling tungsten concentrations in ground water, Carson Desert, Nevada

n investigation of a childhood leukemia cluster by US Centers for Disease Control and Prevention revealed that residents of the Carson Desert, Nevada, are exposed to high levels of W and this prompted an investigation of W in aquifers used as drinking water sources. Tungsten concentrations in 100 ground water samples from all aquifers used as drinking water sources in the area ranged from 0.27 to 742 μg/l. Ground water in which W concentrations exceed 50 μg/l principally occurs SE of Fallon in a geothermal area. The principal sources of W in ground water are natural and include erosion of W-bearing mineral deposits in the Carson River watershed upstream of Fallon, and, possibly, upwelling geothermal waters. Ground water in the Fallon area is strongly reducing and reductive dissolution of Fe and Mn oxyhydroxides may be releasing W; however, direct evidence that the metal oxides contain W is not available. Although W and Cl concentrations in the Carson River, a lake, and water from many wells, appear to be controlled by evaporative concentration, evaporation alone cannot explain the elevated W concentrations found in water from some of the wells. Concentrations of W exceeding 50 μg/l are exclusively associated with Na &#x2013; HCO 3 "> Na–HCO3 and Na–Cl water types and pH > 8.0; in these waters, geochemical modeling indicates that W exhibits <10% adsorption. Tungsten concentrations are strongly and positively correlated with As, B, F, and P, indicating either common sources or common processes controlling their concentrations. Geochemical modeling indicates W concentrations are consistent with pH-controlled adsorption of W. The geochemical model PHREEQC was used to calculate IAP values, which were compared with published Ksp values for primary W minerals. FeWO 4 , MnWO 4 , Na 2 WO 4 , and MgWO 4 were undersaturated and CaWO 4 and SrWO 4 were approaching saturation. These conclusions are tentative because of uncertainty in the thermodynamic data. The similar behavior of As and W observed in this study suggests ground water in areas where elevated As concentrations are present also may contain elevated W concentrations, particularly if there is a mineral or geothermal source of W and reducing conditions develop in the aquifer.

Nevada↗
USGS2005

Selenium mobilization during a flood experiment in a contaminated wetland: Stewart Lake Waterfowl Management Area, Utah

Constructed and natural wetlands can accumulate elevated levels of Se; however, few data are available on cost-effective methods for remobilization and removal of Se from these areas. A field experiment was conducted to assess the effectiveness of flooding on the removal of Se from dry surface sediments. The 83-m2 flood-experiment plot contained 10 monitoring wells, a water-quality minimonitor (continuous measurement of pH, specific conductance, water temperature, and dissolved O2), a down-hole Br electrode, and 2 pressure transducers. Flooding was initiated on August 27, 2002, and a Br tracer was added to water delivered through a pipeline to the flood plot during the first 1.2 h. Standing water depth in the flood plot was maintained at 0.3 m through September 1, 2002. The Br tracer data indicate a dual porosity system that includes fracture (mud cracks) and matrix flow components. Mean vertical water velocities for the matrix flow component were estimated to range from 0.002 to 0.012 m/h. Dissolved (less than 0.45 ??m) Se increased from pre-flood concentrations of less than 10 ??g/L to greater than 800 ??g/L during flooding in samples from deep (2.0 m below land surface) ground water. Selenium concentrations exceeded 5500 ??g/L in samples from shallow (0.8 m below land surface) ground water. Ratios of Se to Br in water samples indicate that Se moved conservatively during the experiment and was derived from leaching of near-surface sediments. Cumulative Se flux to the deep ground water during the experiment ranged from 9.0 to 170 mg/m2. Pre- and post-flood surface soil sampling indicated a mean Se flux of 720 mg/m2 through the top 15 cm of soil. Ground-water samples collected 8 months after termination of the flood experiment contained Se concentrations of less than 20 ??g/L. The minimonitor data indicate a rapid return to chemically reducing conditions in the deep ground water, limiting the mobility of the Se dissolved in the water pulse introduced during the flood experiment. Ratios of Se to Br in deep ground-water samples collected 8 months after the experiment confirmed the removal of Se from the aqueous phase. Based on the median Se flux rate estimated during the experiment of 0.65 mg/h/m2 (n = 52), 7 flooding cycles would be required to meet the 4 ??g/g remediation goal in surface soils from the SLWMA wetland.

Applied Geochemistry↗
USGS2005

Baseline models of trace elements in major aquifers of the United States

Trace-element concentrations in baseline samples from a survey of aquifers used as potable-water supplies in the United States are summarized using methods appropriate for data with multiple detection limits. The resulting statistical distribution models are used to develop summary statistics and estimate probabilities of exceeding water-quality standards. The models are based on data from the major aquifer studies of the USGS National Water Quality Assessment (NAWQA) Program. These data were produced with a nationally-consistent sampling and analytical framework specifically designed to determine the quality of the most important potable groundwater resources during the years 1991-2001. The analytical data for all elements surveyed contain values that were below several detection limits. Such datasets are referred to as multiply-censored data. To address this issue, a robust semi-parametric statistical method called regression on order statistics (ROS) is employed. Utilizing the 90th-95th percentile as an arbitrary range for the upper limits of expected baseline concentrations, the models show that baseline concentrations of dissolved Ba and Zn are below 500 ??g/L. For the same percentile range, dissolved As, Cu and Mo concentrations are below 10 ??g/L, and dissolved Ag, Be, Cd, Co, Cr, Ni, Pb, Sb and Se are below 1-5 ??g/L. These models are also used to determine the probabilities that potable ground waters exceed drinking water standards. For dissolved Ba, Cr, Cu, Pb, Ni, Mo and Se, the likelihood of exceeding the US Environmental Protection Agency standards at the well-head is less than 1-1.5%. A notable exception is As, which has approximately a 7% chance of exceeding the maximum contaminant level (10 ??g/L) at the well head.

Applied Geochemistry↗
USGS2005

Combined use of 15N and 18O of nitrate and 11B to evaluate nitrate contamination in groundwater

Isotopic composition of NO3 (??15NNO3 and ??18ONO3) and B (??11B) were used to evaluate NO3 contamination and identify geochemical processes occurring in a hydrologically complex Basin and Range valley in northern Nevada with multiple potential sources of NO3. Combined use of these isotopes may be a useful tool in identifying NO3 sources because NO3 and B co-migrate in many environmental settings, their isotopes are fractionated by different environmental processes, and because wastewater and fertilizers may have distinct isotopic signatures for N and B. The principal cause of elevated NO3 concentrations in residential parts of the study area is wastewater and not natural NO3 or fertilizers. This is indicated by some samples with elevated NO3 concentrations plotting along ??15NNO3 and NO3 mixing lines between natural NO3 from the study area and theoretical septic-system effluent. This conclusion is supported by the presence of caffeine in one sample and the absence of samples with elevated NO3 concentrations that fall along mixing lines between natural NO3 and theoretical percolate below fertilized lawns. Nitrogen isotopes alone could not be used to determine NO3 sources in several wells because denitrification blurred the original isotopic signatures. The range of ??11B values in native ground water in the study area (-8.2??? to +21.2???) is large. The samples with the low ??11B values have a geochemical signature characteristic of hydrothermal systems. Physical and chemical data suggest B is not being strongly fractionated by adsorption onto clays. ??11B values from local STP effluent (-2.7???) and wash water from a domestic washing machine (-5.7???) were used to plot mixing lines between wastewater and native ground water. In general, wells with elevated NO3 concentrations fell along mixing lines between wastewater and background water on plots of ??11B against 1/B and Cl/B. Combined use of ??15N and ??11B in the study area was generally successful in identifying contaminant sources and processes that are occurring, however, it is likely to be more successful in simpler settings with a well-characterized ??11B value for background wells.

Applied Geochemistry↗
USGS2005

Inorganic, isotopic, and organic composition of high-chloride water from wells in a coastal southern California aquifer

Chloride concentrations were as high as 230 mg/L in water from the surface discharge of long-screened production wells in Pleasant Valley, Calif., about 100 km NW of Los Angeles. Wells with the higher Cl − concentrations were near faults that bound the valley. Depending on well construction, high-Cl − water from different sources may enter a well at different depths. For example, Cl − concentration in the upper part of some wells completed in overlying aquifers influenced by irrigation return were as high as 220 mg/L, and Cl − concentrations in water sampled within wells at depths greater than 450 m were as high as 500 mg/L. These high-Cl − waters mix within the well during pumping and produce the water sampled at the surface discharge. Changes in the major ion, minor ion, trace element, and δ 34 S and δ 13 C isotopic composition of water in wells with depth were consistent with changes resulting from SO 4 reduction, precipitation of calcite, and cation exchange. The chemical and isotopic composition of high-Cl − water from deep wells trends towards the composition of oil-field production water from the study area. Chloride concentrations in oil-field production water present at depths 150 m beneath freshwater aquifers were 2200 mg/L, and Cl − concentrations in underlying marine rock were as high as 4400 mg/L. High-Cl − concentrations in water from deeper parts of wells were associated with dissolved organic C composed primarily of hydrophobic neutral compounds believed to be similar to those associated with petroleum in underlying deposits. These compounds would not be apparent using traditional sampling techniques and would not be detected using analytical methods intended to measure contamination.

Applied Geochemistry↗
USGS2005

Ferric iron in sediments as a novel CO2 mineral trap: CO 2-SO2 reaction with hematite

Thermodynamic simulations of reactions among SO2-bearing CO 2-dominated gas, water and mineral phases predict that Fe III in sediments should be converted almost entirely to dissolved FeII and siderite (FeCO3), and that SO2 should simultaneously be oxidized to dissolved sulfate. The reactions are however, subject to kinetic constraints which may result in deviation from equilibrium and the precipitation of other metastable mineral phases. To test the prediction, a laboratory experiment was carried out in a well stirred hydrothermal reactor at 150??C and 300 bar with hematite, 1.0 m NaCl, 0.5 m NaOH, SO2 in quantity sufficient to reduce much of the iron, and excess CO2. The experiment produced stable siderite and metastable pyrite and elemental S. Changes in total dissolved Fe are consistent with nucleation of pyrite at ???17 h, and nucleation of siderite at ???600 h. Dissolution features present on elemental S at the conclusion of the experiment suggest nucleation early in the experiment. The experiment did not reach equilibrium after ???1400 h, as indicated by coexistence of hematite with metastable pyrite and elemental sulfur. However, the results confirm that FeIII can be used to trap CO2 in siderite if partly oxidized S, as SO2, is present to reduce the Fe with CO2 in the gas phase. ?? 2005 Elsevier Ltd. All rights reserved.

Applied Geochemistry↗
USGS2005

Statistical characterization of a large geochemical database and effect of sample size

The authors investigated statistical distributions for concentrations of chemical elements from the National Geochemical Survey (NGS) database of the U.S. Geological Survey. At the time of this study, the NGS data set encompasses 48,544 stream sediment and soil samples from the conterminous United States analyzed by ICP-AES following a 4-acid near-total digestion. This report includes 27 elements: Al, Ca, Fe, K, Mg, Na, P, Ti, Ba, Ce, Co, Cr, Cu, Ga, La, Li, Mn, Nb, Nd, Ni, Pb, Sc, Sr, Th, V, Y and Zn. The goal and challenge for the statistical overview was to delineate chemical distributions in a complex, heterogeneous data set spanning a large geographic range (the conterminous United States), and many different geological provinces and rock types. After declustering to create a uniform spatial sample distribution with 16,511 samples, histograms and quantile-quantile (Q-Q) plots were employed to delineate subpopulations that have coherent chemical and mineral affinities. Probability groupings are discerned by changes in slope (kinks) on the plots. Major rock-forming elements, e.g., Al, Ca, K and Na, tend to display linear segments on normal Q-Q plots. These segments can commonly be linked to petrologic or mineralogical associations. For example, linear segments on K and Na plots reflect dilution of clay minerals by quartz sand (low in K and Na). Minor and trace element relationships are best displayed on lognormal Q-Q plots. These sensitively reflect discrete relationships in subpopulations within the wide range of the data. For example, small but distinctly log-linear subpopulations for Pb, Cu, Zn and Ag are interpreted to represent ore-grade enrichment of naturally occurring minerals such as sulfides. None of the 27 chemical elements could pass the test for either normal or lognormal distribution on the declustered data set. Part of the reasons relate to the presence of mixtures of subpopulations and outliers. Random samples of the data set with successively smaller numbers of data points showed that few elements passed standard statistical tests for normality or log-normality until sample size decreased to a few hundred data points. Large sample size enhances the power of statistical tests, and leads to rejection of most statistical hypotheses for real data sets. For large sample sizes (e.g., n > 1000), graphical methods such as histogram, stem-and-leaf, and probability plots are recommended for rough judgement of probability distribution if needed. ?? 2005 Elsevier Ltd. All rights reserved.

Applied Geochemistry↗
USGS2005

Net alkalinity and net acidity 1: Theoretical considerations

Net acidity and net alkalinity are widely used, poorly defined, and commonly misunderstood parameters for the characterization of mine drainage. The authors explain theoretical expressions of 3 types of alkalinity (caustic, phenolphthalein, and total) and acidity (mineral, CO2, and total). Except for rarely-invoked negative alkalinity, theoretically defined total alkalinity is closely analogous to measured alkalinity and presents few practical interpretation problems. Theoretically defined "CO 2-acidity" is closely related to most standard titration methods with an endpoint pH of 8.3 used for determining acidity in mine drainage, but it is unfortunately named because CO2 is intentionally driven off during titration of mine-drainage samples. Using the proton condition/mass- action approach and employing graphs to illustrate speciation with changes in pH, the authors explore the concept of principal components and how to assign acidity contributions to aqueous species commonly present in mine drainage. Acidity is defined in mine drainage based on aqueous speciation at the sample pH and on the capacity of these species to undergo hydrolysis to pH 8.3. Application of this definition shows that the computed acidity in mg L -1 as CaCO3 (based on pH and analytical concentrations of dissolved FeII, FeIII, Mn, and Al in mg L -1):aciditycalculated=50{1000(10-pH)+[2(FeII)+3(FeIII)]/56+2(Mn)/ 55+3(Al)/27}underestimates contributions from HSO4- and H+, but overestimates the acidity due to Fe3+ and Al3+. However, these errors tend to approximately cancel each other. It is demonstrated that "net alkalinity" is a valid mathematical construction based on theoretical definitions of alkalinity and acidity. Further, it is shown that, for most mine-drainage solutions, a useful net alkalinity value can be derived from: (1) alkalinity and acidity values based on aqueous speciation, (2) measured alkalinity minus calculated acidity, or (3) taking the negative of the value obtained in a standard method "hot peroxide" acidity titration, provided that labs report negative values. The authors recommend the third approach; i.e., net alkalinity = -Hot Acidity. ?? 2005 Elsevier Ltd. All rights reserved.

Applied Geochemistry↗
USGS2005

Net alkalinity and net acidity 2: Practical considerations

The pH, alkalinity, and acidity of mine drainage and associated waters can be misinterpreted because of the chemical instability of samples and possible misunderstandings of standard analytical method results. Synthetic and field samples of mine drainage having various initial pH values and concentrations of dissolved metals and alkalinity were titrated by several methods, and the results were compared to alkalinity and acidity calculated based on dissolved solutes. The pH, alkalinity, and acidity were compared between fresh, unoxidized and aged, oxidized samples. Data for Pennsylvania coal mine drainage indicates that the pH of fresh samples was predominantly acidic (pH 2.5-4) or near neutral (pH 6-7); ??? 25% of the samples had pH values between 5 and 6. Following oxidation, no samples had pH values between 5 and 6. The Standard Method Alkalinity titration is constrained to yield values >0. Most calculated and measured alkalinities for samples with positive alkalinities were in close agreement. However, for low-pH samples, the calculated alkalinity can be negative due to negative contributions by dissolved metals that may oxidize and hydrolyze. The Standard Method hot peroxide treatment titration for acidity determination (Hot Acidity) accurately indicates the potential for pH to decrease to acidic values after complete degassing of CO2 and oxidation of Fe and Mn, and it indicates either the excess alkalinity or that required for neutralization of the sample. The Hot Acidity directly measures net acidity (= -net alkalinity). Samples that had near-neutral pH after oxidation had negative Hot Acidity; samples that had pH < 6.3 after oxidation had positive Hot Acidity. Samples with similar pH values before oxidation had dissimilar Hot Acidities due to variations in their alkalinities and dissolved Fe, Mn, and Al concentrations. Hot Acidity was approximately equal to net acidity calculated based on initial pH and dissolved concentrations of Fe, Mn, and Al minus the initial alkalinity. Acidity calculated from the pH and dissolved metals concentrations, assuming equivalents of 2 per mole of Fe and Mn and 3 per mole of Al, was equivalent to that calculated based on complete aqueous speciation of FeII/FeIII. Despite changes in the pH, alkalinity, and metals concentrations, the Hot Acidities were comparable for fresh and most aged samples. A meaningful "net" acidity can be determined from a measured Hot Acidity or by calculation from the pH, alkalinity, and dissolved metals concentrations. The use of net alkalinity = (Alkalinitymeasured - Hot Aciditymeasured) to design mine drainage treatment can lead to systems with insufficient Alkalinity to neutralize metal and H+ acidity and is not recommended. The use of net alkalinity = -Hot Acidity titration is recommended for the planning of mine drainage treatment. The use of net alkalinity = (Alkalinitymeasured - Aciditycalculated) is recommended with some cautions. ?? 2005 Elsevier Ltd. All rights reserved.

Applied Geochemistry↗
USGS2005

Historical backcasting of metal concentrations in the Chattahoochee River, Georgia: Population growth and environmental policy

The impact of increasing urbanization on the quality of a river system has been investigated by examining the current concentration of trace metals in the Chattahoochee River south of Atlanta, GA, and comparing these to previously published historical sediment data from reservoirs along the river. The lack of historical data for dissolved metal concentrations prior to ???1980 requires an approach using these historic metal data from sediment cores. Core data are combined with current suspended load and dissolved metal data to "backcast" dissolved metal concentrations in the metro-Atlanta portion of the Chattahoochee River. The data suggest that the per capita input of dissolved trace metals have actually decreased since the 1920s, but anthropogenic inputs of metal are still a substantial water quality issue. ?? 2005 Elsevier Ltd. All rights reserved.

Applied Geochemistry↗
USGS2005

Management scenarios for the Jordan River salinity crisis

Recent geochemical and hydrological findings show that the water quality of the base flow of the Lower Jordan River, between the Sea of Galilee and the Dead Sea, is dependent upon the ratio between surface water flow and groundwater discharge. Using water quality data, mass-balance calculations, and actual flow-rate measurements, possible management scenarios for the Lower Jordan River and their potential affects on its salinity are investigated. The predicted scenarios reveal that implementation of some elements of the Israel-Jordan peace treaty will have negative effects on the Jordan River water salinity. It is predicted that removal of sewage effluents dumped into the river (???13 MCM/a) will significantly reduce the river water's flow and increase the relative proportion of the saline groundwater flux into the river. Under this scenario, the Cl content of the river at its southern point (Abdalla Bridge) will rise to almost 7000 mg/L during the summer. In contrast, removal of all the saline water (16.5 MCM/a) that is artificially discharged into the Lower Jordan River will significantly reduce its Cl concentration, to levels of 650-2600 and 3000-3500 mg/L in the northern and southern areas of the Lower Jordan River, respectively. However, because the removal of either the sewage effluents or the saline water will decrease the river's discharge to a level that could potentially cause river desiccation during the summer months, other water sources must be allocated to preserve in-stream flow needs and hence the river's ecosystem. ?? 2005 Elsevier Ltd. All rights reserved.

Applied Geochemistry↗
USGS2005

Trace elements in streambed sediments of small subtropical streams on O'ahu, Hawai'i: Results from the USGS NAWQA program

Data are presented for trace element concentrations determined in the <63 ??m fraction of streambed sediment samples collected at 24 sites on the island of O'ahu, Hawai'i. Sampling sites were classified as urban, agricultural, mixed (urban/agricultural), or forested based on their dominant land use, although the mixed land use at selected sampling sites consisted of either urban and agricultural or forested and agricultural land uses. Forest dominated sites were used as reference sites for calculating enrichment factors. Trace element concentrations were compared to concentrations from studies conducted in the conterminous United States using identical methods and to aquatic-life guidelines provided by the Canadian Council of Ministers of the Environment. A variety of elements including Pb, Cr, Cu and Zn exceeded the aquatic-life guidelines in selected samples. All of the Cr and Zn values and 16 of 24 Cu values exceeded their respective guidelines. The potential toxicity of elements exceeding guidelines, however, should be considered in the context of strong enrichments of selected trace elements attributable to source rocks in Hawai'i, as well as in the context of the abundance of fine-grained sediment in the streambed of O'ahu streams. Statistical methods including cluster analysis, Kruskal-Wallis non-parametric test, correlation analysis, and principal component analysis (PCA) were used to evaluate differences and elucidate relationships between trace elements and sites. Overall, trace element distributions and abundances can be correlated to three principal sources of elements. These include basaltic rocks of the volcanic edifice (Fe, Al, Ni, Co, Cr, V and Cu), carbonate/seawater derived elements (Mg, Ca, Na and Sr), and elements enriched owing to anthropogenic activity (P, Sn, Cd, Sn, Ba and Pb). Anthropogenic enrichment gradients were observed for Ba, Cd, Pb, Sn and Zn in the four streams in which sediments were collected upstream and downstream. The findings of this study are generally similar to but differ slightly from previous work on sediments and suspended particulate matter in streams, from two urban watersheds of O'ahu, Hawai'i. Inter-element associations in the latter were often stronger and indicated a mixture of anthropogenic, agricultural and basaltic sources of trace elements. Some elements fell into different statistical categories in the two studies, owing in part to differences in study design and the hydrogeological constraints on the respective study areas.

Applied Geochemistry↗
USGS2006

The influence of hydrous Mn–Zn oxides on diel cycling of Zn in an alkaline stream draining abandoned mine lands

Many mining-impacted streams in western Montana with pH near or above neutrality display large (up to 500%) diel cycles in dissolved Zn concentrations. The streams in question typically contain boulders coated with a thin biofilm, as well as black mineral crusts composed of hydrous Mn–Zn oxides. Laboratory mesocosm experiments simulating diel behavior in High Ore Creek (one of the Montana streams with particularly high Zn concentrations) show that the Zn cycles are not caused by 24-h changes in streamflow or hyporheic exchange, but rather to reversible in-stream processes that are driven by the solar cycle and its attendant influence on pH and water temperature ( T ). Laboratory experiments using natural Mn–Zn precipitates from the creek show that the mobilities of Zn and Mn increase nearly an order of magnitude for each unit decrease in pH, and decrease 2.4-fold for an increase in T from 5 to 20 °C. The response of dissolved metal concentration to small changes in either pH or T was rapid and reversible, and dissolved Zn concentrations were roughly an order of magnitude higher than Mn. These observations are best explained by sorption of Zn 2+ and Mn 2+ onto the secondary Mn–Zn oxide surfaces. From the T -dependence of residual metal concentrations in solution, approximate adsorption enthalpies of +50 kJ/mol (Zn) and +46 kJ/mol (Mn) were obtained, which are within the range of enthalpy values reported in the literature for sorption of divalent metal cations onto hydrous metal oxides. Using the derived pH- and T -dependencies from the experiments, good agreement is shown between predicted and observed diel Zn cycles for several historical data sets collected from High Ore Creek.

Applied Geochemistry↗