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D. B. Smith

Publications and source records attributed to D. B. Smith.

At least 19 recordsLinked to original sources

Low-density geochemical mapping and the robustness of geochemical patterns

Geochemical mapping of entire continents and, ultimately, the world is still a challenge for applied geochemists. At sample densities traditionally used for geochemical exploration (1 site per 1-25 km2), geochemical mapping of whole continents is logistically extremely demanding and tremendously expensive. The first low-density geochemical surveys (1 site per 200 km2) were carried out during the late 1960s in Africa. Later surveys conducted in various parts of the world had sample densities ranging from 1 site per 300 km2 to 1 site per 18 000 km2. Although these surveys were deemed successful by the investigators in defining variations in background element content on a regional scale, the scientific community was sceptical that low-density geochemical mapping was possible and would provide useful information. The main area of criticism centred around the concern that at such low sample densities the resulting maps would not be robust, i.e. if the same area were resampled and remapped, different geochemical patterns would emerge. Different examples from the USA, Europe, China and Africa demonstrate that low-density geochemical mapping will result in stable and robust geochemical patterns at the continental scale. Such maps are urgently needed for a wide variety of applications. ?? 2008 AAG/ Geological Society of London.

Geochemistry: Exploration, Environment, Analysis

The distribution of uranium over Europe: Geological and environmental significance

The variation of baseline levels of uranium in soil and stream sediments over Europe is described, based on new data prepared by the Forum of European Geological Surveys (FOREGS). The samples have been collected and analysed according to the protocols established for the International Union of Geological Sciences/International Association of Geochemistry and Cosmochemistry (IUGS/IAGC) Working Group on Global Geochemical Baselines. The baseline levels of U vary between 0??21 to 53 mg kg-1 in topsoils, 0??19 to 30 mg kg-1 in subsoils and < 1 to 59 mg kg-1 in stream sediments. There is generally good agreement between the levels of U in the three sample types, and the median concentration in all three media is approximately 2 mg kg-1. The most anomalous baseline levels occur over the Variscan orogen, especially areas into which late post-orogenic radiothermal high heat production (HHP) granites were emplaced. Spiderdiagrams based on trace element levels and rare earth element (REE) plots, confirm the association between the highest U anomalies and evolved radiothermal granites. High values are also associated with parts of the Alpine terrain especially in Slovenia, where there are historical U workings, and Southern Italy, where high values of U reflect contemporary volcanism. In contrast, much of the Caledonides of North West Europe and the Precambrian of the Baltic Shield and East European craton and its overlying sedimentary cover have very low values, generally < 4 mg kg-1. The results suggest that the main concern for the environment and human health from U, and the Th and K with which it is generally associated, is the naturally occurring total gamma radiation and radon potential associated with radiothermal granites. This is likely to be especially important where the granites are mineralised and have been worked historically, for example in the North West of the Iberian Peninsula where U and its decay products are likely to be more dispersed in the surface environment. The study also indicates the value of multi-element data in distinguishing between anthropogenic and naturally occurring anomalies.

Transactions of the Institution of Mining and Meta

Water-soluble material on aerosols collected within volcanic eruption clouds

In February and March of 1978, filter samplers mounted on an aircraft were used to collect the aerosol fraction of the eruption clouds from three active Guatemalan volcanoes (Fuego, Pacaya, and Santiaguito). The samples were collected on Teflon (Fluoropore) filters with a nominal pore diameter of 0.5μm. The mass of air sampled by the filters ranged from 0.15 to 6.6 kg. The particulate material collected consisted of fragments of angular silicate ash and droplets of what is interpreted as dilute H 2 SO 4 and HCl. After collection of the samples, each filter was rinsed with 60 ml of distilled-deionized water. Splits of each extract were centrifuged to remove particles greater than or equal to 0.1 μm in diameter, acidified, and analyzed for B, Ba, Be, Ca, Cd, Co, Cu, Fe, Li, Mg, Mn, Mo, Na, Pb, Si, Sr, V, and Zn by inductively coupled plasma—optical emission spectroscopy. Separate splits were analyzed for F and Cl by specific-ion-electrode methods and for U by a fission track technique. The elements dissolved in the aqueous extracts represent components of water-soluble material either formed directly in the eruption cloud or derived from interaction of ash particles and aerosol components of the plume. Calculations of enrichment factors, based upon concentration ratios, showed the elements most enriched in the extracts relative to bulk ash composition were Cd, Cu, V, F, Cl, Zn, and Pb. These elements represent a subset (with the addition of Cl and F) of elements previously reported enriched in atmospheric aerosols in remote regions as well as in volcanic areas. This suggests that some of the enriched elements were widely dispersed as volatile halides emitted from a volcanic source.

Journal of Geophysical Research - Oceans

Analytical results for municipal biosolids samples from a monitoring program near Deer Trail, Colorado (U.S.A.), 2009

Since late 1993, Metro Wastewater Reclamation District of Denver, a large wastewater treatment plant in Denver, Colo., has applied Grade I, Class B biosolids to about 52,000 acres of nonirrigated farmland and rangeland near Deer Trail, Colo., U.S.A. In cooperation with the Metro District in 1993, the U.S. Geological Survey began monitoring groundwater at part of this site. In 1999, the Survey began a more comprehensive monitoring study of the entire site to address stakeholder concerns about the potential chemical effects of biosolids applications to water, soil, and vegetation. This more comprehensive monitoring program has recently been extended through the end of 2010. Monitoring components of the more comprehensive study include biosolids collected at the wastewater treatment plant, soil, crops, dust, alluvial and bedrock groundwater, and stream-bed sediment. Streams at the site are dry most of the year, so samples of stream-bed sediment deposited after rain were used to indicate surface-water effects. This report presents analytical results for the biosolids samples collected at the Metro District wastewater treatment plant in Denver and analyzed for 2009. In general, the objective of each component of the study was to determine whether concentrations of nine trace elements ('priority analytes') (1) were higher than regulatory limits, (2) were increasing with time, or (3) were significantly higher in biosolids-applied areas than in a similar farmed area where biosolids were not applied. Previous analytical results indicate that the elemental composition of biosolids from the Denver plant was consistent during 1999-2008, and this consistency continues with the samples for 2009. Total concentrations of regulated trace elements remain consistently lower than the regulatory limits for the entire monitoring period. Concentrations of none of the priority analytes appear to have increased during the 11 years of this study.

Open-File Report

Pilot studies for the North American Soil Geochemical Landscapes Project - Site selection, sampling protocols, analytical methods, and quality control protocols

In 2004, the US Geological Survey (USGS) and the Geological Survey of Canada sampled and chemically analyzed soils along two transects across Canada and the USA in preparation for a planned soil geochemical survey of North America. This effort was a pilot study to test and refine sampling protocols, analytical methods, quality control protocols, and field logistics for the continental survey. A total of 220 sample sites were selected at approximately 40-km intervals along the two transects. The ideal sampling protocol at each site called for a sample from a depth of 0-5 cm and a composite of each of the O, A, and C horizons. The <2-mm fraction of each sample was analyzed for Al, Ca, Fe, K, Mg, Na, S, Ti, Ag, As, Ba, Be, Bi, Cd, Ce, Co, Cr, Cs, Cu, Ga, In, La, Li, Mn, Mo, Nb, Ni, P, Pb, Rb, Sb, Sc, Sn, Sr, Te, Th, Tl, U, V, W, Y, and Zn by inductively coupled plasma-mass spectrometry and inductively coupled plasma-atomic emission spectrometry following a near-total digestion in a mixture of HCl, HNO 3 , HClO 4 , and HF. Separate methods were used for Hg, Se, total C, and carbonate-C on this same size fraction. Only Ag, In, and Te had a large percentage of concentrations below the detection limit. Quality control (QC) of the analyses was monitored at three levels: the laboratory performing the analysis, the USGS QC officer, and the principal investigator for the study. This level of review resulted in an average of one QC sample for every 20 field samples, which proved to be minimally adequate for such a large-scale survey. Additional QC samples should be added to monitor within-batch quality to the extent that no more than 10 samples are analyzed between a QC sample. Only Cr (77%), Y (82%), and Sb (80%) fell outside the acceptable limits of accuracy (% recovery between 85 and 115%) because of likely residence in mineral phases resistant to the acid digestion. A separate sample of 0-5-cm material was collected at each site for determination of organic compounds. A subset of 73 of these samples was analyzed for a suite of 19 organochlorine pesticides by gas chromatography. Only three of these samples had detectable pesticide concentrations. A separate sample of A-horizon soil was collected for microbial characterization by phospholipid fatty acid analysis (PLFA), soil enzyme assays, and determination of selected human and agricultural pathogens. Collection, preservation and analysis of samples for both organic compounds and microbial characterization add a great degree of complication to the sampling and preservation protocols and a significant increase to the cost for a continental-scale survey. Both these issues must be considered carefully prior to adopting these parameters as part of the soil geochemical survey of North America.

Applied Geochemistry

Continental-scale patterns in soil geochemistry and mineralogy: results from two transects across the United States and Canada

In 2004, the US Geological Survey (USGS) and the Geological Survey of Canada (GSC) initiated a pilot study that involved collection of more than 1500 soil samples from 221 sites along two continental transects across Canada and the United States. The pilot study was designed to test and refine protocols for a soil geochemical survey of North America. The two transects crossed a wide array of soil parent materials, soil ages, climatic conditions, landforms, land covers and land uses. Sample sites were selected randomly at approximately 40-km intervals from a population defined as all soils of the continent. At each site, soils representing 0 to 5 cm depth, and the O, A, and C horizons, if present, were collected and analyzed for their near-total content of over 40 major and trace elements. Soils from 0–5 cm depth were also collected for analysis of organic compounds. Results from the transects confirm that soil samples collected at a 40-km spacing reveal coherent, continental- to subcontinental-scale geochemical and mineralogical patterns that can be correlated to aspects of underlying soil parent material, soil age and climate influence. The geochemical data also demonstrate that at the continental-scale the dominance of any of these major factors that control soil geochemistry can change across the landscape. Along both transects, soil mineralogy and geochemistry change abruptly with changes in soil parent materials. However, the chemical influence of a soil’s parent material can be obscured by changing climatic conditions. For the transects, increasing precipitation from west to east and increasing temperature from north to south affect both soil mineralogy and geochemistry because of climate effects on soil weathering and leaching, and plant productivity. Regional anomalous metal concentrations can be linked to natural variations in soil parent materials, such as high Ni and Cr in soils developed on ultramafic rocks in California or high P in soils formed on weathered Ordovician limestones in central Kentucky. On local scales, anomalous metal concentrations recognized in soil profiles, such as high P in soils from animal confinement sites, are consistent with local anthropogenic disturbances. At a larger scale, the distribution of Hg across the west to east transect demonstrates that it can be difficult to distinguish between natural or anthropogenic contributions and that many factors can contribute to an element’s spatial distribution. Only three samples in a subset of seventy-three 0–5 cm depth soil samples from the north to south transect had organochlorine pesticides values above the method detection limit, apparently related to historic usage of the pesticides DDT and dieldrin.

Applied Geochemistry

Mineralogy of soils from two continental-scale transects across the United States and Canada and its relation to soil geochemistry and climate

Quantitative mineralogy correlates with major-, minor- and trace-element chemistry for 387 samples of A-horizon and deeper soils collected from east-west and north-south transects across the USA and Canada, where the deeper soils were collected beneath the A-horizon samples. Concentrations of the major elements correlate with specific mineral phases. Minor- and trace-element concentrations correlate with the same phases as the major elements with which they share similar geochemical behavior. Concentrations of quartz and feldspar correlate with precipitation trends east of the Rocky Mountains, and are independent of the underlying rock type and age, indicating that the weathering of soils in this region may have reached a steady-state mineralogy. Other trends in mineralogy relate to physiographic province. The combination of quantitative mineralogy and chemical analysis yields a much richer portrait of soils than can be gained from chemistry alone, because the origins of chemical trends and the chemical availability of specific elements are related to mineralogy.

Applied Geochemistry

Application of in vitro extraction studies to evaluate element bioaccessibility in soils from a transect across the United States and Canada

In vitro bioaccessibility tests (IVBA) are inexpensive, physiologically-based extraction tests designed to estimate the bioaccessibility of elements along ingestion exposure pathways. Published IVBA protocols call for the testing to be done on the <250-??m fraction of soil, as these particles are most likely to adhere to the hands of children and be ingested. Most IVBA in the literature to date have been applied to soil samples from highly contaminated sites or to spiked samples, and relatively little work has been done to evaluate bioaccessibility of elements in a wide variety of uncontaminated 'background' soils. In 2004, the US Geological Survey and the Geological Survey of Canada sampled soils along north-south and east-west transects across the two countries to test and refine sampling and analytical protocols recommended for the planned soil geochemical survey of North America. Samples were collected at 220 sites selected randomly at approximately 40-km intervals. The focus of the investigation presented in this paper was twofold: (1) to begin to examine variations in bioaccessibility of As, Cd, Cr, Ni and Pb in a number of 'background' (i.e., unpolluted) soils from around North America and (2) to determine if there are significant differences that would preclude using the standard size fraction of <2 mm for extraction with a simulated gastric fluid as an expeditious and inexpensive bioaccessibility screening tool for the large numbers of future samples to be collected by this continental-scale project. A subset of 20 soil samples collected along the north-south transect at a depth of 0-5 cm was used for this study. Two separate size fractions (<2 mm and <250 ??m) were extracted using a simulated human gastric fluid consisting of a solution of HCl and glycine adjusted to a pH of 1.5. In general, the leachate results for the <2-mm size fraction were not substantially different than those for the <250-??m size fraction for concentrations of As, Cd, Cr, Ni and Pb. Leachate concentrations for Cd, Ni and Pb appear to be controlled to some extent by the total concentration of the element in soil. Bioaccessibility of the elements in this study decreased in the order, Cd > Pb > Ni > As > Cr.

Applied Geochemistry

The potential of mid- and near-infrared diffuse reflectance spectroscopy for determining major- and trace-element concentrations in soils from a geochemical survey of North America

In 2004, soils were collected at 220 sites along two transects across the USA and Canada as a pilot study for a planned soil geochemical survey of North America (North American Soil Geochemical Landscapes Project). The objective of the current study was to examine the potential of diffuse reflectance (DR) Fourier Transform (FT) mid-infrared (mid-IR) and near-infrared (NIRS) spectroscopy to reduce the need for conventional analysis for the determination of major and trace elements in such continental-scale surveys. Soil samples (n = 720) were collected from two transects (east-west across the USA, and north-south from Manitoba, Canada to El Paso, Texas (USA), n = 453 and 267, respectively). The samples came from 19 USA states and the province of Manitoba in Canada. They represented 31 types of land use (e.g., national forest, rangeland, etc.), and 123 different land covers (e.g., soybeans, oak forest, etc.). The samples represented a combination of depth-based sampling (0-5 cm) and horizon-based sampling (O, A and C horizons) with 123 different depths identified. The set was very diverse with few samples similar in land use, land cover, etc. All samples were analyzed by conventional means for the near-total concentration of 49 analytes (C total , C carbonate and C organic , and 46 major and trace elements). Spectra were obtained using dried, ground samples using a Digilab FTS-7000 FT spectrometer in the mid- (4000-400 cm -1 ) and near-infrared (10,000-4000 cm -1 ) at 4 cm -1 resolution (64 co-added scans per spectrum) using a Pike AutoDIFF DR autosampler. Partial least squares calibrations were develop using: (1) all samples as a calibration set; (2) samples evenly divided into calibration and validation sets based on spectral diversity; and (3) samples divided to have matching analyte concentrations in calibration and validation sets. In general, results supported the conclusion that neither mid-IR nor NIRS would be particularly useful in reducing the need for conventional analysis of soils from this continental-scale geochemical survey. The extreme sample diversity, likely caused by the widely varied parent material, land use at the site of collection (e.g., grazing, recreation, agriculture, etc.), and climate resulted in poor calibrations even for C total , C organic and C carbonate . The results indicated potential for mid-IR and NIRS to differentiate soils containing high concentrations (>100 mg/kg) of some metals (e.g., Co, Cr, Ni) from low-level samples (<50 mg/kg). However, because of the small number of high-level samples, it is possible that differentiation was based on factors other than metal concentration. Results for Mg and Sr were good, but results for other metals examined were fair to poor, at best. In essence, it appears that the great variation in chemical and physical properties seen in soils from this continental-scale survey resulted in each sample being virtually unique. Thus, suitable spectroscopic calibrations were generally not possible.

Applied Geochemistry

A regional soil and sediment geochemical study in northern California

Regional-scale variations in soil geochemistry were investigated in a 20,000-km 2 study area in northern California that includes the western slope of the Sierra Nevada, the southern Sacramento Valley and the northern Coast Ranges. Over 1300 archival soil samples collected from the late 1970s to 1980 in El Dorado, Placer, Sutter, Sacramento, Yolo and Solano counties were analyzed for 42 elements by inductively coupled plasma-atomic emission spectrometry and inductively coupled plasma-mass spectrometry following a near-total dissolution. These data were supplemented by analysis of more than 500 stream-sediment samples from higher elevations in the Sierra Nevada from the same study site. The relatively high-density data (1 sample per 15 km 2 for much of the study area) allows the delineation of regional geochemical patterns and the identification of processes that produced these patterns. The geochemical results segregate broadly into distinct element groupings whose distribution reflects the interplay of geologic, hydrologic, geomorphic and anthropogenic factors. One such group includes elements associated with mafic and ultramafic rocks including Cr, Ni, V, Co, Cu and Mg. Using Cr as an example, elevated concentrations occur in soils overlying ultramafic rocks in the foothills of the Sierra Nevada (median Cr = 160 mg/kg) as well as in the northern Coast Ranges. Low concentrations of these elements occur in soils located further upslope in the Sierra Nevada overlying Tertiary volcanic, metasedimentary and plutonic rocks (granodiorite and diorite). Eastern Sacramento Valley soil samples, defined as those located east of the Sacramento River, are lower in Cr (median Cr = 84 mg/kg), and are systematically lower in this suite compared to soils from the west side of the Sacramento Valley (median Cr = 130 mg/kg). A second group of elements showing a coherent pattern, including Ca, K, Sr and REE, is derived from relatively silicic rocks types. This group occurs at elevated concentrations in soils overlying volcanic and plutonic rocks at higher elevations in the Sierras (e.g. median La = 28 mg/kg) and the east side of the Sacramento Valley (median 20 mg/kg) compared to soils overlying ultramafic rocks in the Sierra Nevada foothills (median 15 mg/kg) and the western Sacramento Valley (median 14 mg/kg). The segregation of soil geochemistry into distinctive groupings across the Sacramento River arises from the former presence of a natural levee (now replaced by an artificial one) along the banks of the river. This levee has been a barrier to sediment transport. Sediment transport to the Valley by glacial outwash from higher elevations in the Sierra Nevada and, more recently, debris from placer Au mining has dominated sediment transport to the eastern Valley. High content of mafic elements (and low content of silicic elements) in surface soil in the west side of the valley is due to a combination of lack of silicic source rocks, transport of ultramafic rock material from the Coast Ranges, and input of sediment from the late Mesozoic Great Valley Group, which is itself enriched in mafic elements. A third group of elements (Zn, Cd, As and Cu) reflect the impact of mining activity. Soil with elevated content of these elements occurs along the Sacramento River in both levee and adjacent flood basin settings. It is interpreted that transport of sediment down the Sacramento River from massive sulfide mines in the Klamath Mountains to the north has caused this pattern. The Pb, and to some extent Zn, distribution patterns are strongly impacted by anthropogenic inputs. Elevated Pb content is localized in major cites and along major highways due to inputs from leaded gasoline. Zinc has a similar distribution pattern but the source is tire wear.

Applied Geochemistry

Analytical Results for Municipal Biosolids Samples from a Monitoring Program Near Deer Trail, Colorado (U.S.A.), 2008

Since late 1993, Metro Wastewater Reclamation District of Denver (Metro District), a large wastewater treatment plant in Denver, Colo., has applied Grade I, Class B biosolids to about 52,000 acres of nonirrigated farmland and rangeland near Deer Trail, Colo. (U.S.A.). In cooperation with the Metro District in 1993, the U.S. Geological Survey (USGS) began monitoring groundwater at part of this site. In 1999, the USGS began a more comprehensive monitoring study of the entire site to address stakeholder concerns about the potential chemical effects of biosolids applications to water, soil, and vegetation. This more comprehensive monitoring program has recently been extended through 2010. Monitoring components of the more comprehensive study include biosolids collected at the wastewater treatment plant, soil, crops, dust, alluvial and bedrock groundwater, and stream-bed sediment. Streams at the site are dry most of the year, so samples of stream-bed sediment deposited after rain were used to indicate surface-water effects. This report will present only analytical results for the biosolids samples collected at the Metro District wastewater treatment plant in Denver and analyzed during 2008. Crock and others have presented earlier a compilation of analytical results for the biosolids samples collected and analyzed for 1999 thru 2006, and in a separate report, data for the 2007 biosolids are reported. More information about the other monitoring components is presented elsewhere in the literature. Priority parameters for biosolids identified by the stakeholders and also regulated by Colorado when used as an agricultural soil amendment include the total concentrations of nine trace elements (arsenic, cadmium, copper, lead, mercury, molybdenum, nickel, selenium, and zinc), plutonium isotopes, and gross alpha and beta activity. Nitrogen and chromium also were priority parameters for groundwater and sediment components.

Open-File Report

Analytical Results for Agricultural Soils Samples from a Monitoring Program Near Deer Trail, Colorado (USA)

Since late 1993, Metro Wastewater Reclamation District of Denver (Metro District, MWRD), a large wastewater treatment plant in Denver, Colorado, has applied Grade I, Class B biosolids to about 52,000 acres of nonirrigated farmland and rangeland near Deer Trail, Colorado, USA. In cooperation with the Metro District in 1993, the U.S. Geological Survey (USGS) began monitoring groundwater at part of this site. In 1999, the USGS began a more comprehensive monitoring study of the entire site to address stakeholder concerns about the potential chemical effects of biosolids applications to water, soil, and vegetation. This more comprehensive monitoring program has recently been extended through 2010. Monitoring components of the more comprehensive study include biosolids collected at the wastewater treatment plant, soil, crops, dust, alluvial and bedrock groundwater, and stream bed sediment. Soils for this study were defined as the plow zone of the dry land agricultural fields - the top twelve inches of the soil column. This report presents analytical results for the soil samples collected at the Metro District farm land near Deer Trail, Colorado, during three separate sampling events during 1999, 2000, and 2002. Soil samples taken in 1999 were to be a representation of the original baseline of the agricultural soils prior to any biosolids application. The soil samples taken in 2000 represent the soils after one application of biosolids to the middle field at each site and those taken in 2002 represent the soils after two applications. There have been no biosolids applied to any of the four control fields. The next soil sampling is scheduled for the spring of 2010. Priority parameters for biosolids identified by the stakeholders and also regulated by Colorado when used as an agricultural soil amendment include the total concentrations of nine trace elements (arsenic, cadmium, copper, lead, mercury, molybdenum, nickel, selenium, and zinc), plutonium isotopes, and gross alpha and beta activity (Colorado Department of Public Health and Environment, Hazardous Materials and Waste Management Division, 1997; Colorado Department of Public Health and Environment,1998; U.S. Environmental Protection Agency, 1993). Since these were the identified priority parameters for the biosolids, the soils have the same set of priority parameters. Although the composite soils' priority analytes have been reported earlier to Metro District, the remaining elemental datasets for both the composite soils samples and selected fields' individual subsamples' data are presented here for the first time. More information about the other monitoring components is presented elsewhere in the literature (http://co.water.usgs.gov/projects/CO406/CO406.html). In general, the objective of each component of the study was to determine whether concentrations of priority parameters (1) were higher than regulatory limits, (2) were increasing with time, and(or) (3) were significantly higher in biosolids-applied areas than in a similar farmed area where biosolids were not applied. The method chosen for sampling the soils proved to be an efficient and reliable representation of the average composition of each field. This was shown by analyzing individual subsamples, averaging the resulting values, and then comparing the values to the composited samples' values. The soil chemistry shows distinct differences between the two sites, most likely due to the different underlying parent material. Biosolids data were used to compile an inorganic-chemical biosolids signature that can be contrasted with the geochemical signature of the agricultural soils for this site. The biosolids signature and an understanding of the geology and hydrology of the site can be used to separate biosolids effects from natural geochemical effects. Elements of particular interest for a biosolids signature after application in the soils include bismuth, copper, silver, mercury, and phosphorus. This signat

Open-File Report

Analytical Results for Municipal Biosolids Samples from a Monitoring Program Near Deer Trail, Colorado (USA), 1999 through 2006

Since late 1993, Metro Wastewater Reclamation District of Denver (Metro District), a large wastewater treatment plant in Denver, Colorado, has applied Grade I, Class B biosolids to about 52,000 acres of non-irrigated farmland and rangeland near Deer Trail, Colorado. In cooperation with the Metro District in 1993, the U.S. Geological Survey (USGS) began monitoring ground water at part of this site (Yager and Arnold, 2003). In 1999, the USGS began a more comprehensive monitoring study of the entire site to address stakeholder concerns about the potential chemical effects of biosolids applications. This more comprehensive monitoring program has recently been extended through 2010. Monitoring components of the more comprehensive study include biosolids collected at the wastewater treatment plant, soil, crops, dust, alluvial and bedrock ground water, and stream bed sediment. Streams at the site are dry most of the year, so samples of stream bed sediment deposited after rain were used to indicate surface-water effects. This report will present only analytical results for the biosolids samples collected at the Metro District wastewater treatment plant in Denver and analyzed during 1999 through 2006. More information about the other monitoring components is presented elsewhere in the literature (e.g., Yager and others, 2004a, 2004b, 2004c, 2004d). Priority parameters for biosolids identified by the stakeholders and also regulated by Colorado when used as an agricultural soil amendment include the total concentrations of nine trace elements (arsenic, cadmium, copper, lead, mercury, molybdenum, nickel, selenium, and zinc), plutonium isotopes, and gross alpha and beta activity. Nitrogen and chromium also were priority parameters for ground water and sediment components. In general, the objective of each component of the study was to determine whether concentrations of priority parameters (1) were higher than regulatory limits, (2) were increasing with time, or (3) were significantly higher in biosolids-applied areas than in a similar farmed area where biosolids were not applied. Analytical results indicate that the elemental composition of the biosolids from the Denver plant was consistent during 1999-2006, and total concentrations of regulated trace elements were consistently lower than the regulatory limits. Plutonium isotopes were not detected in any of the biosolids samples for the entire sampling period. Analytical results for gross and were highly imprecise and erratic. As a result of the cancelation of regulation requiring their monitoring in biosolids, the determination of both was discontinued mid-study. Data from this study were used to compile an inorganic-chemical biosolids signature that can be contrasted with the geochemical signature for this site. The biosolids signature and an understanding of the geology and hydrology of the site can be used to separate biosolids effects from natural geochemical effects. Elements of particular interest for a biosolids signature include bismuth, copper, silver, mercury, and phosphorus.

Open-File Report

Analytical Results for Municipal Biosolids Samples from a Monitoring Program near Deer Trail, Colorado (U.S.A.), 2007

Since late 1993, the Metro Wastewater Reclamation District of Denver (Metro District), a large wastewater treatment plant in Denver, Colorado, has applied Grade I, Class B biosolids to about 52,000 acres of nonirrigated farmland and rangeland near Deer Trail, Colorado (U.S.A.). In cooperation with the Metro District in 1993, the U.S. Geological Survey (USGS) began monitoring ground water at part of this site. In 1999, the USGS began a more comprehensive monitoring study of the entire site to address stakeholder concerns about the potential chemical effects of biosolids applications to water, soil, and vegetation. This more comprehensive monitoring program recently has been extended through 2010. Monitoring components of the more comprehensive study include biosolids collected at the wastewater treatment plant, soil, crops, dust, alluvial and bedrock ground water, and streambed sediment. Streams at the site are dry most of the year, so samples of streambed sediment deposited after rain were used to indicate surface-water effects. This report will present only analytical results for the biosolids samples collected at the Metro District wastewater treatment plant in Denver and analyzed during 2007. We have presented earlier a compilation of analytical results for the biosolids samples collected and analyzed for 1999 through 2006. More information about the other monitoring components is presented elsewhere in the literature. Priority parameters for biosolids identified by the stakeholders and also regulated by Colorado when used as an agricultural soil amendment include the total concentrations of nine trace elements (arsenic, cadmium, copper, lead, mercury, molybdenum, nickel, selenium, and zinc), plutonium isotopes, and gross alpha and beta activity. Nitrogen and chromium also were priority parameters for ground water and sediment components. In general, the objective of each component of the study was to determine whether concentrations of priority parameters (1) were higher than regulatory limits, (2) were increasing with time, or (3) were significantly higher in biosolids-applied areas than in a similar farmed area where biosolids were not applied. Previous analytical results indicate that the elemental composition of the biosolids from the Denver plant was consistent during 1999-2006 and this consistency continues with the samples for 2007; total concentrations of regulated trace elements remained consistently lower than the regulatory limits for the entire monitoring period. Our previously reported data (1999-2006) and data presented in this report were used to compile an inorganic-chemical biosolids signature that can be contrasted with the geochemical signature for this site. The biosolids signature and an understanding of the geology and hydrology of the site can be used to separate biosolids effects from natural geochemical effects. Elements of particular interest for a biosolids signature include bismuth, copper, silver, mercury, phosphorus, and silver. An alternative method of digestion of biosolids was also recently investigated, and the results are presented in this report. A microwave digestion using only nitric acid at controlled elevated temperature and pressure was tested to replace the much more time-consuming and labor-intensive, traditional four-acid, hotplate method for the preparation of solutions to be analyzed by inductively coupled plasma-mass spectrometry (ICP-MS). Elements of concern determined by ICP-MS following digestion include cadmium, copper, lead, molybdenum, nickel, and zinc. The microwave 'digestion' proved to be a strong acid leach, and it was less efficient at digesting the biosolids samples with consistently lower recoveries (compared to the four-acid digestion value) for most elements, but especially for the elements of concern - copper, nickel, and zinc. Other elements traditionally associated with the silicate or oxide minerals demonstrated low recoveries, especially titaniu

Open-File Report

Scale-dependent temporal variations in stream water geochemistry

A year-long study of four western Montana streams (two impacted by mining and two “pristine”) evaluated surface water geochemical dynamics on various time scales (monthly, daily, and bi-hourly). Monthly changes were dominated by snowmelt and precipitation dynamics. On the daily scale, post-rain surges in some solute and particulate concentra tions were similar to those of early spring runoff flushing characteristics on the monthly scale. On the bi-hourly scale, we observed diel (diurnal−nocturnal) cycling for pH, dissolved oxygen, water temperature, dissolved inorganic carbon, total suspended sediment, and some total recoverable metals at some or all sites. A comparison of the cumulative geochemical variability within each of the temporal groups reveals that for many water quality parameters there were large overlaps of concentration ranges among groups. We found that short-term (daily and bi-hourly) variations of some geochemical parameters covered large proportions of the variations found on a much longer term (monthly) time scale. These results show the importance of nesting short-term studies within long-term geochemical study designs to separate signals of environmental change from natural variability.

Montana

Biosolids, soils, ground-water, and streambed-sediment data for a biosolids-application area near Deer Trail, Colorado, 1999

In January 1999, the U.S. Geological Survey began an expanded monitoring program near Deer Trail, Colorado, in cooperation with the Metro Wastewater Reclamation District and the North Kiowa Bijou Groundwater Management District. Monitoring components were biosolids, soils, crops, ground water, and streambed sediments. The monitoring program addresses concerns from the public about chemical effects from applications of biosolids to farmland in the Deer Trail, Colorado, area. Constituents of primary concern to the public are arsenic, cadmium, chromium, copper, lead, mercury, molybdenum, nickel, selenium, zinc, plutonium, and gross alpha and beta activity and are included for all monitoring components. This report presents chemical data from the first year of the monitoring program, January?December 1999, for biosolids, soils, alluvial and bedrock ground water, and streambed sediments. The groundwater section of this report also includes climate data, lithologic descriptions, well-completion diagrams, water levels, summary statistics for the water-quality data, and results of statistical testing of selected data for trends and for exceedance of Colorado regulatory standards. Data in this report provide a geochemical baseline for each monitoring component prior to the planned water transfer in 2000 from the Lowry Landfill Superfund site to Metro Wastewater Reclamation District treatment facilities.

Open-File Report