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Ronald C. Antweiler

Publications and source records attributed to Ronald C. Antweiler.

At least 19 recordsLinked to original sources

Geochemical characterization of groundwater evolution south of Grand Canyon, Arizona (USA)

Better characterization of the geochemical evolution of groundwater south of Grand Canyon, Arizona (USA), is needed to understand natural conditions and assess potential effects from breccia-pipe uranium mining in the region. Geochemical signatures of groundwater at 28 sampling locations were evaluated; baseline concentrations for select trace elements (As, B, Ba, Cr, Li, Mo, Rb, Se, Sr, Th, Tl, U, V) were established, and anomalous chemistry characteristics were identified. Concentrations at some groundwater sites exceeded the USEPA drinking water standard for As of 10 μg/L (Red Canyon, Miners, JT, Havasu, and Warm Springs) and U of 30 μg/L (Salt Creek Spring). Four springs from the study area (Blue, Havasu, Fern, and Warm Springs) had unique chemistry, which may indicate a deep flow path or potential contribution of fluids from lower in the crust. Other springs in the study area were distinguished by major anion water type: sulfate, bicarbonate, and a mixture of the two. Water type distinctions were somewhat spatially segregated, with sulfate type present on the western side of the study area, bicarbonate type on the eastern side, and a mixture of the two interspersed between the endmember sites. Sulfate-type water from this study area had low strontium isotopic ratio (87Sr/86Sr) values. The location of spring discharge within single drainages of the Grand Canyon may influence chemistry, as groundwater discharging from bedrock was altered after flowing through alluvial material. Geochemical analysis of groundwater in Grand Canyon indicates the importance of continued monitoring and better understanding of short-term chemical fluctuations.

Arizona

Data quality from a community-based, water-quality monitoring project in the Yukon River basin

This paper examines the quality of data collected by the Indigenous Observation Network, a community-based water-quality project in the Yukon River Basin of Alaska and Canada. The Indigenous Observation Network relies on community technicians to collect surface-water samples from as many as fifty locations to achieve their goals of monitoring the quality of the Yukon River and major tributaries in the basin and maintaining a long-term record of baseline data against which future changes can be measured. This paper addresses concerns about the accuracy, precision, and reliability of data collected by non-professionals. The Indigenous Observation Network data are examined in the context of a standard data life cycle: plan, collect, assure, and describe; as compared to professional scientific activities. Field and laboratory protocols and procedures of the Indigenous Observation Network are compared to those utilized by professional scientists. The data of the Indigenous Observation Network are statistically compared to those collected by professional scientists through a retrospective analysis of a set of water-quality parameters reported by all three projects over a number of years. No statistical differences were found among the three projects for pH, Calcium, Magnesium, or Alkalinity, although statistically significant differences were found for Sodium, Chloride, Sulfate, and Potassium concentrations. The statistical differences found were small and likely not significant in terms of interpreting the data for a variety of uses. Our results suggest that Indigenous Observation Network data are of high quality, and with consistent protocols and participant training, community based monitoring projects can collect data that are accurate, precise, and reliable.

Alaska, British Columbia, Yukon Territory

Permafrost stores a globally significant amount of mercury

Changing climate in northern regions is causing permafrost to thaw with major implications for the global mercury (Hg) cycle. We estimated Hg in permafrost regions based on in situ measurements of sediment total mercury (STHg), soil organic carbon (SOC), and the Hg to carbon ratio (R HgC ) combined with maps of soil carbon. We measured a median STHg of 43 ± 30 ng Hg g soil −1 and a median R HgC of 1.6 ± 0.9 μg Hg g C −1 , consistent with published results of STHg for tundra soils and 11,000 measurements from 4,926 temperate, nonpermafrost sites in North America and Eurasia. We estimate that the Northern Hemisphere permafrost regions contain 1,656 ± 962 Gg Hg, of which 793 ± 461 Gg Hg is frozen in permafrost. Permafrost soils store nearly twice as much Hg as all other soils, the ocean, and the atmosphere combined, and this Hg is vulnerable to release as permafrost thaws over the next century. Existing estimates greatly underestimate Hg in permafrost soils, indicating a need to reevaluate the role of the Arctic regions in the global Hg cycle.

Geophysical Research Letters

Geochemical characterization of groundwater discharging from springs north of the Grand Canyon, Arizona, 2009–2016

A geochemical study was conducted on 37 springs discharging from the Toroweap Formation, Coconino Sandstone, Hermit Formation, Supai Group, and Redwall Limestone north of the Grand Canyon near areas of breccia-pipe uranium mining. Baseline concentrations were established for the elements As, B, Li, Se, SiO 2 , Sr, Tl, U, and V. Three springs exceeded U.S. Environmental Protection Agency drinking water standards: Fence Spring for arsenic, Pigeon Spring for selenium and uranium, and Willow (Hack) Spring for selenium. The majority of the spring sites had uranium values of less than 10 micrograms per liter (μg/L), but six springs discharging from all of the geologic units studied that are located stratigraphically above the Redwall Limestone had uranium values greater than 10 μg/L (Cottonwood [Tuckup], Grama, Pigeon, Rock, and Willow [Hack and Snake Gulch] Springs). The geochemical characteristics of these six springs with elevated uranium include Ca-Mg-SO 4 water type, circumneutral pH, high specific conductance, correlation and multivariate associations between U, Mo, Sr, Se, Li, and Zn, low 87 Sr/ 86 Sr, low 234 U/ 238 U activity ratios (1.34–2.31), detectable tritium, and carbon isotopic interpretation indicating they may be a mixture of modern and pre-modern waters. Similar geochemical compositions of spring waters having elevated uranium concentrations are observed at sites located both near and away from sites of uranium-mining activities in the present study. Therefore, mining does not appear to explain the presence of elevated uranium concentrations in groundwater at the six springs noted above. The elevated uranium at the six previously mentioned springs may be influenced by iron mineralization associated with mineralized breccia pipe deposits. Six springs discharging from the Coconino Sandstone (Upper Jumpup, Little, Horse, and Slide Springs) and Redwall Limestone (Kanab and Side Canyon Springs) contained water with corrected radiocarbon ages as much as 9,300 years old. Of the springs discharging water with radiocarbon age, Kanab and Side Canyon Springs contain tritium of more than 1.3 picocuries per liter (pCi/L), indicating they may contain a component of modern water recharged after 1952. Springs containing high values of tritium (greater than 5.1 pCi/L), which may suggest a significant component of modern water, include Willow (Hack), Saddle Horse, Cottonwood (Tuckup), Hotel, Bitter, Unknown, Hole in the Wall, and Hanging Springs. Fence and Rider Springs, located on the eastern end of the study area near the Colorado River, have distinctly different geochemical compositions compared to the other springs of the study. Additionally, water from Fence Spring has the highest 87 Sr/ 86 Sr for samples analyzed from this study with a value greater than those known in sedimentary rocks from the region. Strontium isotope data likely indicate that water discharging at Fence Spring has interacted with Precambrian basement rocks. Rider Spring had the most depleted values of stable O and H isotopes indicating that recharge, if recent, occurred at higher elevations or was recharged during earlier, cooler-climate conditions.

Arizona

Continuous lake-sediment records of glaciation in the Sierra Nevada between 52,600 and 12,500 14C yr B.P.

The chemistry of the carbonate-free clay-size fraction of Owens Lake sediments supports the use of total organic carbon and magnetic susceptibility as indicators of stadial-interstadial oscillations. Owens Lake records of total organic carbon, magnetic susceptibility, and chemical composition of the carbonate-free, clay-size fraction indicate that Tioga glaciation began ~24,500 and ended by ~13,600 14C yr B.P. Many of the components of glacial rock flour (e.g., TiO2, MnO, BaO) found in Owens Lake sediments achieved maximum values during the Tioga glaciation when valley glaciers reached their greatest extent. Total organic carbon and SiO2 (amorphous) concentrations reached minimum values during Tioga glaciation, resulting from decreases in productivity that accompanied the introduction of rock flour into the surface waters of Owens Lake. At least 20 stadial-interstadial oscillations occurred in the Sierra Nevada between 52,600 and 14,000 14C yr B.P. Total organic carbon data from a Pyramid Lake sediment core also indicate oscillations in glacier activity between >39,500 and ~13,600 14C yr B.P. Alpine glacier oscillations occurred on a frequency of ???1900 yr in both basins, suggesting that millennial-scale oscillations occurred in California and Nevada during most of the past 52,600 yr.

Quaternary Research

Evaluation of statistical treatments of left-censored environmental data using coincident uncensored data sets. II. Group comparisons

The main classes of statistical treatments that have been used to determine if two groups of censored environmental data arise from the same distribution are substitution methods, maximum likelihood (MLE) techniques, and nonparametric methods. These treatments along with using all instrument-generated data (IN), even those less than the detection limit, were evaluated by examining 550 data sets in which the true values of the censored data were known, and therefore “true” probabilities could be calculated and used as a yardstick for comparison. It was found that technique “quality” was strongly dependent on the degree of censoring present in the groups. For low degrees of censoring (<25% in each group), the Generalized Wilcoxon (GW) technique and substitution of √2/2 times the detection limit gave overall the best results. For moderate degrees of censoring, MLE worked best, but only if the distribution could be estimated to be normal or log-normal prior to its application; otherwise, GW was a suitable alternative. For higher degrees of censoring (each group >40% censoring), no technique provided reliable estimates of the true probability. Group size did not appear to influence the quality of the result, and no technique appeared to become better or worse than other techniques relative to group size. Finally, IN appeared to do very well relative to the other techniques regardless of censoring or group size.

Environmental Science & Technology

The occurrence and distribution of selected trace elements in the upper Rio Grande and tributaries in Colorado and Northern New Mexico

Two sampling trips were undertaken in 1994 to determine the distribution of trace elements in the Upper Rio Grande and several of its tributaries. Water discharges decreased in the main stem of the Rio Grande from June to September, whereas dissolved concentrations of trace elements generally increased. This is attributed to dilution of base flow from snowmelt runoff in the June samples. Of the three major mining districts (Creede, Summitville, and Red River) in the Upper Rio Grande drainage basin, only the Creede District appears to impact the Rio Grande in a significant manner, with both waters and sediments having elevated concentrations of some trace elements considerably downriver. For example, dissolved zinc concentrations upriver of Willow Creek, which primarily drains the Creede District, were about 2-3 μg/L; immediately downstream of the Willow Creek confluence, concentrations were above 20 μg/L; and elevated concentrations occurred in the Rio Grande for the next 100 km. The Red River District does not significantly impact the Upper Rio Grande for most trace elements. Because of current water management practices, it is difficult to assess the impact of the Summitville District on the Upper Rio Grande. There are, however, large increases in many dissolved trace element concentrations as the Rio Grande passes through the San Luis Valley, coincident with elevated concentrations of those same trace elements in tributaries. Among these elements are As, B, Cr, Li, Mn, Mo, Ni, Sr, U, and V. None of the trace elements exceeded U.S. EPA primary drinking water standards in either survey, with the exception of cadmium in Willow Creek. Secondary drinking water standards were frequently violated, especially in tributaries draining areas where mining has occurred. Dissolved zinc (in Willow Creek in both June and September) was the only element that exceeded the EPA Water Quality Criteria for aquatic life of 120 μg/L.

Archives of Environmental Contamination and Toxico

Evaluation of wastewater contaminant transport in surface waters using verified Lagrangian sampling

Contaminants released from wastewater treatment plants can persist in surface waters for substantial distances. Much research has gone into evaluating the fate and transport of these contaminants, but this work has often assumed constant flow from wastewater treatment plants. However, effluent discharge commonly varies widely over a 24-hour period, and this variation controls contaminant loading and can profoundly influence interpretations of environmental data. We show that methodologies relying on the normalization of downstream data to conservative elements can give spurious results, and should not be used unless it can be verified that the same parcel of water was sampled. Lagrangian sampling, which in theory samples the same water parcel as it moves downstream (the Lagrangian parcel), links hydrologic and chemical transformation processes so that the in-stream fate of wastewater contaminants can be quantitatively evaluated. However, precise Lagrangian sampling is difficult, and small deviations – such as missing the Lagrangian parcel by less than 1 h – can cause large differences in measured concentrations of all dissolved compounds at downstream sites, leading to erroneous conclusions regarding in-stream processes controlling the fate and transport of wastewater contaminants. Therefore, we have developed a method termed “verified Lagrangian” sampling, which can be used to determine if the Lagrangian parcel was actually sampled, and if it was not, a means for correcting the data to reflect the concentrations which would have been obtained had the Lagrangian parcel been sampled. To apply the method, it is necessary to have concentration data for a number of conservative constituents from the upstream, effluent, and downstream sites, along with upstream and effluent concentrations that are constant over the short-term (typically 2–4 h). These corrections can subsequently be applied to all data, including non-conservative constituents. Finally, we show how data from other studies can be corrected.

Science of the Total Environment

The presence and distribution of polycyclic aromatic hydrocarbons and inorganic elements in water and lakebed materials and the potential for bioconcentration in biota at established sampling sites on Lake Powell, Utah and Arizona

The National Park Service is responsible for monitoring the effects of visitor use on the quality of water, lakebed material (bottom sediments), and biota, in Lake Powell, Utah and Arizona. A sampling program was begun in 2010 to assess the presence, distribution, and concentrations of organic and inorganic compounds in the water column and bottom sediment. In response to an Environmental Impact Statement regarding personal watercraft and as a continuation from previous studies by the U.S. Geological Survey and the National Park Service, Glen Canyon National Recreation Area, water samples were collected and analyzed for polycyclic aromatic hydrocarbons (PAHs) using semipermeable membrane devices and inorganic elements using a fixed-bottle sampler deployed at established monitoring sites during 2010 and 2011. Lakebed material samples were also analyzed for polycyclic aromatic hydrocarbons and inorganic elements, some of which could be harmful to aquatic biota if present at concentrations above established aquatic life criteria. Of the 44 PAH compounds analyzed, 26 individual compounds were detected above the censoring limit in the water column by semipermeable membrane devices. The highest number of compounds detected were at Lone Rock Beach, Wahweap Marina, Rainbow Bridge National Monument, and Antelope Marina which are all located in the southern part of Lake Powell where visitation and boat use is high. Because PAHs can remain near their source, the potential for bioconcentration is highest near these sites. The PAH compound found in the highest concentration was phenol (5,902 nanograms per liter), which is included in the U.S. Environmental Protection Agency’s priority pollutants list. The dissolved inorganic chemistry of water samples measured at the sampling sites in Lake Powell defined three different patterns of elements: (1) concentrations were similar between sites in the upper part of the lake near Farley Canyon downstream to Halls Crossing Marina, a distance of about 36 lake miles, (2) concentrations varied depending on the element between Halls Crossing Marina downstream to the mouth of the Escalante River, a distance of about 33 lake miles, and (3) concentrations were similar between sites from below the mouth of the Escalante River to Glen Canyon Dam, a distance of about 68 lake miles. Analysis of lakebed bottom sediment material samples detected PAH compounds at all sampling sites except at Halls Crossing Marina, Stanton Creek, and Forgotten Canyon. Twenty-four of 44 PAHs analyzed in lakebed material were detected above the reporting limit. Perylene was the most prevalent compound detected above the reporting limit in lakebed material and was detected at three sampling sites. Concentrations of perylene ranged from an estimate of 24.0 to 47.9 micrograms per kilogram (μg/kg). Fluoranthene had the highest concentration of any PAH and was detected at the Wahweap Marina with a concentration of 565 μg/kg. The highest sum of concentrations for all compounds found in lakebed material samples at one site was at the Wahweap Marina, which had concentrations five times higher than the next highest site. The three major tributaries to Lake Powell—the Colorado, Escalante, and San Juan Rivers—all showed elevated concentrations of inorganic elements in their delta sediments for most elements relative to the majority of the sediment samples taken from the lake itself. However, there were four lake sites that had concentrations for most inorganic elements that equaled or exceeded those of the tributaries. Two of these sites were at the northeast part of the lake, nearest to the Colorado River as it enters Lake Powell (Farley Canyon and Blue Notch Canyon), one was at the Escalante River below 50-Mile Canyon, and other was at Antelope Marina.

Arizona;Utah

In-stream attenuation of neuro-active pharmaceuticals and their metabolites

In-stream attenuation was determined for 14 neuro-active pharmaceuticals and associated metabolites. Lagrangian sampling, which follows a parcel of water as it moves downstream, was used to link hydrological and chemical transformation processes. Wastewater loading of neuro-active compounds varied considerably over a span of several hours, and thus a sampling regime was used to verify that the Lagrangian parcel was being sampled and a mechanism was developed to correct measured concentrations if it was not. In-stream attenuation over the 5.4-km evaluated reach could be modeled as pseudo-first-order decay for 11 of the 14 evaluated neuro-active pharmaceutical compounds, illustrating the capacity of streams to reduce conveyance of neuro-active compounds downstream. Fluoxetine and N -desmethyl citalopram were the most rapidly attenuated compounds ( t 1/2 = 3.6 &plusmn; 0.3 h, 4.0 &plusmn; 0.2 h, respectively). Lamotrigine, 10,11,-dihydro-10,11,-dihydroxy-carbamazepine, and carbamazepine were the most persistent ( t 1/2 = 12 &plusmn; 2.0 h, 12 &plusmn; 2.6 h, 21 &plusmn; 4.5 h, respectively). Parent compounds (e.g., buproprion, carbamazepine, lamotrigine) generally were more persistent relative to their metabolites. Several compounds (citalopram, venlafaxine, O -desmethyl-venlafaxine) were not attenuated. It was postulated that the primary mechanism of removal for these compounds was interaction with bed sediments and stream biofilms, based on measured concentrations in stream biofilms and a column experiment using stream sediments.

Environmental Science & Technology

Distribution and geochemistry of selected trace elements in the Sacramento River near Keswick Reservoir

The effect of heavy metals from the Iron Mountain Mines (IMM) Superfund site on the upper Sacramento River is examined using data from water and bed sediment samples collected during 1996-97. Relative to surrounding waters, aluminum, cadmium, cobalt, copper, iron, lead, manganese, thallium, zinc and the rare-earth elements (REE) were all present in high concentrations in effluent from Spring Creek Reservoir (SCR), which enters into the Sacramento River in the Spring Creek Arm of Keswick Reservoir. SCR was constructed in part to regulate the flow of acidic, metal-rich waters draining the IMM Superfund site. Although virtually all of these metals exist in SCR in the dissolved form, upon entering Keswick Reservoir they at least partially converted via precipitation and/or adsorption to the particulate phase. In spite of this, few of the metals settled out; instead the vast majority was transported colloidally down the Sacramento River at least to Bend Bridge, 67 km from Keswick Dam. The geochemical influence of IMM on the upper Sacramento River was variable, chiefly dependent on the flow of Spring Creek. Although the average flow of the Sacramento River at Keswick Dam is 250 m 3 /s (cubic meters per second), even flows as low as 0.3 m 3 /s from Spring Creek were sufficient to account for more than 15% of the metals loading at Bend Bridge, and these proportions increased with increasing Spring Creek flow. The dissolved proportion of the total bioavailable load was dependent on the element but steadily decreased for all metals, from near 100% in Spring Creek to values (for some elements) of less than 1% at Bend Bridge; failure to account for the suspended sediment load in assessments of the effect of metals transport in the Sacramento River can result in estimates which are low by as much as a factor of 100.

California

Sediment fluxes from California Coastal Rivers: the influences of climate, geology, and topography

The influences of geologic and climatic factors on erosion and sedimentation processes in rivers draining the western flank of the California Coast Range are assessed. Annual suspended, bedload, and total sediment fluxes were determined for 16 river basins that have hydrologic records covering all or most of the period from 1950 to 2006 and have been relatively unaffected by flow storage, regulation, and depletion, which alter the downstream movement of water and sediment. The occurrence of relatively large annual sediment fluxes are strongly influenced by the El Nino&ndash;Southern Oscillation (ENSO) and the Pacific Decadal Oscillation (PDO). The frequency of relatively large annual sediment fluxes decreases from north to south during La Nina phases and increases from north to south during El Nino phases. The influence of ENSO is modulated over a period of decades by the PDO, such that relatively large annual sediment fluxes are more frequent during a La Nina phase in conjunction with a cool PDO and during an El Nino phase in conjunction with a warm PDO. Values of mean annual sediment flux, , were regressed against basin and climatic characteristics. Basin area, bedrock erodibility, basin relief, and precipitation explain 87% of the variation in from the 16 river basins. Bedrock erodibility is the most significant characteristic influencing . Basin relief is a superior predictor of compared with basin slope. is nearly proportional to basin area and increases with increasing precipitation. For a given percentage change, basin relief has a 2.3-fold greater effect on than a similar change in precipitation. The estimated natural from all California coastal rivers for the period 1950&ndash;2006 would have been approximately 85 million tons without flow storage, regulation, and depletion; the actual has been approximately 50 million tons, because of the effects of flow storage, regulation, and depletion.

California

Selected trace elements in the Sacramento River, California: Occurrence and distribution

The impact of trace elements from the Iron Mountain Superfund site on the Sacramento River and selected tributaries is examined. The concentration and distribution of many trace elements—including aluminum, arsenic, boron, barium, beryllium, bismuth, cadmium, cerium, cobalt, chromium, cesium, copper, dysprosium, erbium, europium, iron, gadolinium, holmium, potassium, lanthanum, lithium, lutetium, manganese, molybdenum, neodymium, nickel, lead, praseodymium, rubidium, rhenium, antimony, selenium, samarium, strontium, terbium, thallium, thulium, uranium, vanadium, tungsten, yttrium, ytterbium, zinc, and zirconium—were measured using a combination of inductively coupled plasma-mass spectrometry and inductively coupled plasma-atomic emission spectrometry. Samples were collected using ultraclean techniques at selected sites in tributaries and the Sacramento River from below Shasta Dam to Freeport, California, at six separate time periods from mid-1996 to mid-1997. Trace-element concentrations in dissolved (ultrafiltered [0.005-μm pore size]) and colloidal material, isolated at each site from large volume samples, are reported. For example, dissolved Zn ranged from 900 μg/L at Spring Creek (Iron Mountain acid mine drainage into Keswick Reservoir) to 0.65 μg/L at the Freeport site on the Sacramento River. Zn associated with colloidal material ranged from 4.3 μg/L (colloid-equivalent concentration) in Spring Creek to 21.8 μg/L at the Colusa site on the Sacramento River. Virtually all of the trace elements exist in Spring Creek in the dissolved form. On entering Keswick Reservoir, the metals are at least partially converted by precipitation or adsorption to the particulate phase. Despite this observation, few of the elements are removed by settling; instead the majority is transported, associated with colloids, downriver, at least to the Bend Bridge site, which is 67 km from Keswick Dam. Most trace elements are strongly associated with the colloid phase going downriver under both low- and high-flow conditions.

Archives of Environmental Contamination and Toxico

Lagrangian mass-flow investigations of inorganic contaminants in wastewater-impacted streams

Understanding the potential effects of increased reliance on wastewater treatment plant (WWTP) effluents to meet municipal, agricultural, and environmental flow requires an understanding of the complex chemical loading characteristics of the WWTPs and the assimilative capacity of receiving waters. Stream ecosystem effects are linked to proportions of WWTP effluent under low-flow conditions as well as the nature of the effluent chemical mixtures. This study quantifies the loading of 58 inorganic constituents (nutrients to rare earth elements) from WWTP discharges relative to upstream landscape-based sources. Stream assimilation capacity was evaluated by Lagrangian sampling, using flow velocities determined from tracer experiments to track the same parcel of water as it moved downstream. Boulder Creek, Colorado and Fourmile Creek, Iowa, representing two different geologic and hydrologic landscapes, were sampled under low-flow conditions in the summer and spring. One-half of the constituents had greater loads from the WWTP effluents than the upstream drainages, and once introduced into the streams, dilution was the predominant assimilation mechanism. Only ammonium and bismuth had significant decreases in mass load downstream from the WWTPs during all samplings. The link between hydrology and water chemistry inherent in Lagrangian sampling allows quantitative assessment of chemical fate across different landscapes.

Environmental Science & Technology

The cleaning of burned and contaminated archaeological maize prior to 87Sr/86Sr analysis

Accurate trace-metal and strontium-isotope analyses of archaeological corn cobs require that metal contaminants be removed prior to chemical analysis. Archaeological cobs are often coated with construction debris, dust, or soil which contains mineral particles. In addition, most archaeological cobs are partially or completely burned and the burned parts incorporate mineral debris in their hardened residual structures. Unburned cobs are weak ion exchangers and most metals within a cob are not firmly bound to cob organic matter; therefore, immersing cobs in acids and rinsing them in deionized water to remove mineral contaminants may result in the undesirable loss of metals, including strontium, from the cob. In this paper we show that some cob metal-pair ratios are not substantially changed when the cob is “cleaned” with deionized water, if the water-cob contact time does not exceed five minutes. Additionally, we introduce a method for eliminating mineral contaminants in both burned and unburned cobs, thus rendering them acceptable for strontium-isotope analysis. However, the decontamination procedure results in the rapid non-stoichiometric leaching of trace metals from the unburned cobs and it is possible that most metals will be extracted from the cobs during the lengthy decontamination process. Trace metals, in particular Al and Ca, should be analyzed in order to determine the presence and level of mineral contamination after cleaning.

Journal of Archaeological Science

Multi-scale measurements and modeling of denitrification in streams with varying flow and nitrate concentration in the upper Mississippi River basin, USA

Denitrification is an important net sink for NO 3 − in streams, but direct measurements are limited and in situ controlling factors are not well known. We measured denitrification at multiple scales over a range of flow conditions and NO 3 − concentrations in streams draining agricultural land in the upper Mississippi River basin. Comparisons of reach-scale measurements (in-stream mass transport and tracer tests) with local-scale in situ measurements (pore-water profiles, benthic chambers) and laboratory data (sediment core microcosms) gave evidence for heterogeneity in factors affecting benthic denitrification both temporally (e.g., seasonal variation in NO 3 − concentrations and loads, flood-related disruption and re-growth of benthic communities and organic deposits) and spatially (e.g., local stream morphology and sediment characteristics). When expressed as vertical denitrification flux per unit area of streambed ( U denit , in μmol N m −2 h −1 ), results of different methods for a given set of conditions commonly were in agreement within a factor of 2–3. At approximately constant temperature (~20 ± 4°C) and with minimal benthic disturbance, our aggregated data indicated an overall positive relation between U denit (~0–4,000 μmol N m −2 h −1 ) and stream NO 3 − concentration (~20–1,100 μmol L −1 ) representing seasonal variation from spring high flow (high NO 3 − ) to late summer low flow (low NO 3 − ). The temporal dependence of U denit on NO 3 − was less than first-order and could be described about equally well with power-law or saturation equations (e.g., for the unweighted dataset, U denit ≈26 * [NO 3 − ] 0.44 or U denit ≈640 * [NO 3 − ]/[180 + NO 3 − ]; for a partially weighted dataset, U denit ≈14 * [NO 3 − ] 0.54 or U denit ≈700 * [NO 3 − ]/[320 + NO 3 − ]). Similar parameters were derived from a recent spatial comparison of stream denitrification extending to lower NO 3 − concentrations (LINX2), and from the combined dataset from both studies over 3 orders of magnitude in NO 3 − concentration. Hypothetical models based on our results illustrate: (1) U denit was inversely related to denitrification rate constant ( k 1 denit , in day −1 ) and vertical transfer velocity ( v f,denit , in m day −1 ) at seasonal and possibly event time scales; (2) although k 1 denit was relatively large at low flow (low NO 3 − ), its impact on annual loads was relatively small because higher concentrations and loads at high flow were not fully compensated by increases in U denit ; and (3) although NO 3 − assimilation and denitrification were linked through production of organic reactants, rates of NO 3 − loss by these processes may have been partially decoupled by changes in flow and sediment transport. Whereas k 1 denit and v f,denit are linked implicitly with stream depth, NO 3 − concentration, and(or) NO 3 − load, estimates of U denit may be related more directly to field factors (including NO 3 − concentration) affecting denitrification rates in benthic sediments. Regional regressions and simulations of benthic denitrification in stream networks might be improved by including a non-linear relation between U denit and stream NO 3 − concentration and accounting for temporal variation.

Biogeochemistry

Evaluation of statistical treatments of left-censored environmental data using coincident uncensored data sets: I. Summary statistics

The main classes of statistical treatment of below-detection limit (left-censored) environmental data for the determination of basic statistics that have been used in the literature are substitution methods, maximum likelihood, regression on order statistics (ROS), and nonparametric techniques. These treatments, along with using all instrument-generated data (even those below detection), were evaluated by examining data sets in which the true values of the censored data were known. It was found that for data sets with less than 70% censored data, the best technique overall for determination of summary statistics was the nonparametric Kaplan-Meier technique. ROS and the two substitution methods of assigning one-half the detection limit value to censored data or assigning a random number between zero and the detection limit to censored data were adequate alternatives. The use of these two substitution methods, however, requires a thorough understanding of how the laboratory censored the data. The technique of employing all instrument-generated data - including numbers below the detection limit - was found to be less adequate than the above techniques. At high degrees of censoring (greater than 70% censored data), no technique provided good estimates of summary statistics. Maximum likelihood techniques were found to be far inferior to all other treatments except substituting zero or the detection limit value to censored data.

Environmental Science & Technology

Environmental factors affecting mercury in Camp Far West Reservoir, California, 2001-03

This report documents water quality in Camp Far West Reservoir from October 2001 through August 2003. The reservoir, located at approximately 300 feet above sea level in the foothills of the northwestern Sierra Nevada, California, is a monomictic lake characterized by extreme drawdown in the late summer and fall. Thermal stratification in summer and fall is coupled with anoxic conditions in the hypolimnion. Water-quality sampling was done at approximately 3-month intervals on eight occasions at several stations in the reservoir, including a group of three stations along a flow path in the reservoir: an upstream station in the Bear River arm (principal tributary), a mid-reservoir station in the thalweg (prereservoir river channel), and a station in the deepest part of the reservoir, in the thalweg near Camp Far West Dam. Stations in other tributary arms of the reservoir included those in the Rock Creek arm of the reservoir, a relatively low-flow tributary, and the Dairy Farm arm, a small tributary that receives acidic, metal-rich drainage seasonally from the inactive Dairy Farm Mine, which produced copper, zinc, and gold from underground workings and a surface pit. Several water-quality constituents varied significantly by season at all sampling stations, including major cations and anions, total mercury (filtered and unfiltered samples), nitrogen (ammonia plus organic), and total phosphorus. A strong seasonal signal also was observed for the sulfurisotope composition of aqueous sulfate from filtered water. Although there were some spatial differences in water quality, the seasonal variations were more profound. Concentrations of total mercury (filtered and unfiltered water) were highest during fall and winter; these concentrations decreased at most stations during spring and summer. Anoxic conditions developed in deep parts of the reservoir during summer and fall in association with thermal stratification. The highest concentrations of methylmercury in unfiltered water were observed in samples collected during summer from deepwater stations in the anoxic hypolimnion. In the shallow (less than 14 meters depth) oxic epilimnion, concentrations of methylmercury in unfiltered water were highest during the spring and lowest during the fall. The ratio of methylmercury to total mercury (MeHg/HgT) increased systematically from winter to spring to summer, largely in response to the progressive seasonal decrease in total mercury concentrations, but also to some extent because of increases in MeHg concentrations during summer. Water-quality data for Camp Far West Reservoir are used in conjunction with data from linked studies of sediment and biota to develop and refine a conceptual model for mercury methylation and bioaccumulation in the reservoir and the lower Bear River watershed. It is hypothesized that MeHg is produced by sulfate-reducing bacteria in the anoxic parts of the water column and in shallow bed sediment. Conditions were optimal for this process during late summer and fall. Previous work has indicated that Camp Far West Reservoir is a phosphate-limited system - molar ratios of inorganic nitrogen to inorganic phosphorus in filtered water were consistently greater than 16 (the Redfield ratio), sometimes by orders of magnitude. Therefore, concentrations of orthophosphate were expectedly very low or below detection at all stations during all seasons. It is further hypothesized that iron-reducing bacteria facilitate release of phosphorus from iron-rich sediments during summer and early fall, stimulating phytoplankton growth in the fall and winter, and that the MeHg produced in the hypolimnion and metalimnion is released to the entire water column in the late fall during reservoir destratification (vertical mixing). Mercury bioaccumulation factors (BAF) were computed using data from linked studies of biota spanning a range of trophic position: zooplankton, midge larvae, mayfly nymphs, crayfish, threadfin shad, bluegill,

California