Groundwater munition residues and nitrate near Grand Island,Nebraska, U.S.A.

Munition residues from waste disposal on ordnance property have resulted in a defined plume of RDX contaminated groundwater stretching 6.5 km and underlying an area of 6.5 km². A smaller plume of TNT was detected near the plant's boundary. The relative positions of the plumes combined with an historical review of total plant output of RDX and TNT indicates that RDX is much more persistent than TNT. The estimated RDX transport velocity of 0.5 m day⁻¹ closely approximates the calculated Darcian velocity. The RDX plume sinks with recharge at a rate of about 0.5 m yr⁻¹.Nitrate is associated primarily with adjacent upgradient landuse and is not related to plant manufacture of ammonium nitrate. The average δ¹⁵N of the Nitrate was about + 10% and strongly suggests that animal wastes are the predominant source.     

Quantifying Metal Contributions from Multiple Sources to the Clark Fork River,Montana, U.S.A.

Identifying and quantifying the contributions of multiple sources of trace elements to stream sediments in a basin containing several possible inputs presents a unique problem related to the investigation of rivers impacted by industrial activity. A multi-source dilution–mixing model was developed and applied to determine the relative contributions to As, Cu and Pb burdens in the Clark Fork River, Montana, a recipient of historical mine wastes as a result of over a century of mining and milling operations. The results identified the Flint Creek drainage as a major source of anthropogenic As (47%) and Pb (35%) to sediments of the Clark Fork River and the Milltown Reservoir, in addition to the major sources associated with mining operations in Butte, MT. The Little Blackfoot River also contributes anthropogenic As (3%) and Pb (4%) to the Clark Fork River, while minor inputs of Cu (1%) and Pb (2%) emanate from the Blackfoot River. The model allows source quantification, and an understanding of the fate and transport of mine wastes in a basin, allowing identification and eventual prioritization of sites destined for remediation.     

Quantifying Metal Contributions from Multiple Sources to the Clark Fork River,Montana, U.S.A.

Identifying and quantifying the contributions of multiple sources of trace elements to stream sediments in a basin containing several possible inputs presents a unique problem related to the investigation of rivers impacted by industrial activity. A multi-source dilution-mixing model was developed and applied to determine the relative contributions to As, Cu and Pb burdens in the Clark Fork River, Montana, a recipient of historical mine wastes as a result of over a century of mining and milling operations. The results identified the Flint Creek drainage as a major source of anthropogenic As (47%) and Pb (35%) to sediments of the Clark Fork River and the Milltown Reservoir, in addition to the major sources associated with mining operations in Butte, MT. The Little Blackfoot River also contributes anthropogenic As (3%) and Pb (4%) to the Clark Fork River, while minor inputs of Cu (1%) and Pb (2%) emanate from the Blackfoot River. The model allows source quantification, and an understanding of the fate and transport of mine wastes in a basin, allowing identification and eventual prioritization of sites destined for remediation.     

Contributions of Pesticide use to Urban Background Concentrations of Arsenic in Denver,Colorado, U.S.A.

Soil investigations near a former smelter have revealed that historic use of arsenical pesticides has contributed significantly to anthropogenic background concentrations of arsenic on certain residential properties in Denver, Colorado, U.S.A. Remedial investigation data, based on samples collected in relatively undisturbed locations, had previously indicated that the "upper limit" of background arsenic concentrations was 28 mg/kg in the site vicinity. This value compares reasonably well with more regional data, which indicate increasing arsenic concentrations moving from rural to urban land use. Soil sampling during cleanup, however, revealed the presence of arsenic concentrations of a few hundred to more than 1000 mg/kg on a large number of residential lawns due to historic applications of a crabgrass killer, which was missed by the earlier investigation samples because of the sampling bias toward undisturbed land. Data from over 20,000 soil samples now show that several different populations comprise urban background levels of arsenic and that these populations may be stratified by land use and have spatial patterns that should be considered during any background study. A variety of forensic techniques, including spatial analysis, arsenic speciation, and calculation of metals ratios were necessary to separate the smelter impacts from pesticide impacts.     

Discriminating between Copper and Silver Mill Tailings in Silver Bow Creek Overbank Deposits,Butte, Montana,U.S.A.

Mining of the Butte deposit evolved over 100 years from placer mining starting in 1864 through silver mining to copper mining in the 1900s. Tailings resulting from milling during the period 1876–1924 were typically sluiced into the adjacent Silver Bow Creek (SBC) where they were washed downstream. The most significant flood event in 1908, among others, resulted in emplacement of approximately 2.9 m tons of sediment intermixed with tailings as overbank deposits along SBC between Butte and the Warm Springs Ponds. Apportioning the associated costs was contingent in part on discriminating between ownership of liability for the silver and copper tailings, which together formed the most significant portion of the overbank deposits. Samples were collected of tailings end-members and SBC deposits and their characteristic mineralogy (e.g. galena for silver tailings, and enargite for copper tailings) used to ascertain mixing of the tailings along SBC. This analysis identified Pb as a signature element for silver tailings and Cu for copper tailings. Two-hundred and twenty-four Cu and Pb chemical analyses representing 43 transects through the overbank deposits along SBC allowed calculation of the proportional contribution of the end members for each integrated transect. Accumulating the volumes from each transect resulted in an apportionment of 53% copper and 47% silver tailings in the overbank deposits.     

Discriminating between Copper and Silver Mill Tailings in Silver Bow Creek Overbank Deposits,Butte, Montana,U.S.A.

Mining of the Butte deposit evolved over 100 years from placer mining starting in 1864 through silver mining to copper mining in the 1900s. Tailings resulting from milling during the period 1876-1924 were typically sluiced into the adjacent Silver Bow Creek (SBC) where they were washed downstream. The most significant flood event in 1908, among others, resulted in emplacement of approximately 2.9 m tons of sediment intermixed with tailings as overbank deposits along SBC between Butte and the Warm Springs Ponds. Apportioning the associated costs was contingent in part on discriminating between ownership of liability for the silver and copper tailings, which together formed the most significant portion of the overbank deposits. Samples were collected of tailings end-members and SBC deposits and their characteristic mineralogy (e.g. galena for silver tailings, and enargite for copper tailings) used to ascertain mixing of the tailings along SBC. This analysis identified Pb as a signature element for silver tailings and Cu for copper tailings. Two-hundred and twenty-four Cu and Pb chemical analyses representing 43 transects through the overbank deposits along SBC allowed calculation of the proportional contribution of the end members for each integrated transect. Accumulating the volumes from each transect resulted in an apportionment of 53% copper and 47% silver tailings in the overbank deposits.     

Arsenic Background Concentrations in Florida,U.S.A. Surface Soils: Determination and Interpretation

Background concentrations of soil arsenic have been used as an alternative soil cleanup criterion in many states in the U.S. This research addresses issues related to the interpretation of background concentrations of arsenic in near pristine soils in Florida. Total arsenic was measured in 448 taxonomic and geographic representative surface soil samples using USEPA Method 3052 (HCl-HNO₃-HF, microwave digestion) and graphite furnace atomic absorption spectrophotometry analysis procedure. Values were log-normally distributed, with geometric mean and baseline concentration (defined as 95% of the expected range of background concentrations) providing the most satisfactory statistical results. An upper baseline concentration of 6.21 mg As/kg was estimated for undisturbed soils (n = 267) compared to 7.63 mg As/kg for disturbed soils (n = 181). Temporal trend of total soil arsenic concentrations from 1967 to 1989 paralleled decreased usage of arsenic in U.S. agriculture. Soil arsenic background concentrations were generally higher in south Florida than in north and central Florida, and associated with wet soils. Individual high arsenic sites were scattered throughout the state, but the most highly concentrated of these occurred in the Leon-Lee belt along the Ocala uplift district extending to the southwestern flatwoods district. Extrapolation of the data using a single arsenic value regardless of the taxonomic and geographical differences in soil arsenic distribution would underestimate potential arsenic contamination in upland soils.     

Arsenic Background Concentrations in Florida,U.S.A. Surface Soils: Determination and Interpretation

Background concentrations of soil arsenic have been used as an alternative soil cleanup criterion in many states in the U.S. This research addresses issues related to the interpretation of background concentrations of arsenic in near pristine soils in Florida. Total arsenic was measured in 448 taxonomic and geographic representative surface soil samples using USEPA Method 3052 (HCl-HNO 3 -HF, microwave digestion) and graphite furnace atomic absorption spectrophotometry analysis procedure. Values were log-normally distributed, with geometric mean and baseline concentration (defined as 95% of the expected range of background concentrations) providing the most satisfactory statistical results. An upper baseline concentration of 6.21 mg As/kg was estimated for undisturbed soils (n=267) compared to 7.63 mg As/kg for disturbed soils (n=181). Temporal trend of total soil arsenic concentrations from 1967 to 1989 paralleled decreased usage of arsenic in U.S. agriculture. Soil arsenic background concentrations were generally higher in south Florida than in north and central Florida, and associated with wet soils. Individual high arsenic sites were scattered throughout the state, but the most highly concentrated of these occurred in the Leon-Lee belt along the Ocala uplift district extending to the southwestern flatwoods district. Extrapolation of the data using a single arsenic value regardless of the taxonomic and geographical differences in soil arsenic distribution would underestimate potential arsenic contamination in upland soils.     

Method Comparisons for Particulate Nitrate,Elemental Carbon,and PM2.5 Mass in Seven U.S. Cities

ABSTRACT

Methods that measure PM₂₅ mass, total particulate NO₃ ^-, and elemental carbon (EC) were evaluated in seven U.S. cities from 1997 to 1999. Sampling was performed in Bakersfield, CA; Boston, MA; Chicago, IL; Dallas, TX; Philadelphia, PA; Phoenix, AZ; and Riverside, CA. Evaluating and validating methods that measure the components of fine mass are important to the effort of establishing a speciation-monitoring network. The Harvard Impactor (HI), which measures fine particle mass, showed excellent agreement (r² = 0.99) with the PM₂₅ Federal Reference Method (FRM) for 81 24-hr samples in Riverside and Bakersfield. The HI also showed good precision (4.8%) for 243 24-hr collocated samples over eight studies.

The Aethalometer was employed in six of the sampling locations to measure black carbon (BC). These values were compared to EC as measured from a quartz filter using thermal analysis. For the six cities combined, the two methods were highly correlated (r² = 0.94; 187 24-hr samples); however, the BC values were approximately 24% less than the EC measurements consistently across all six cites. This compares well to results observed for EC/BC measurements observed in other semi-urban areas. Par-ticulate NO₃ ^- was measured using the Harvard-EPA Annular Denuder System (HEADS). This was compared to the NO₃ ^- measured from the HI Teflon (DuPont) filter to assess NO₃ ^- artifacts. Significant NO₃ ^- losses (approximately 50% of total NO₃ ^-) were found in Riverside, Philadelphia, and Boston, while minimal artifacts were observed in the other sites. Two types of HEADS configurations were employed in five cities. One system used a Na₂CO₃-coated glass fiber filter, and the other type used a nylon filter to collect volatilized NO₃ ^- from the Teflon filter. The HEADS with the Na₂CO₃-coated filter consistently underestimated the total particulate NO₃ ^- by approximately 20% compared to the nylon HEADS.     

Method comparisons for particulate nitrate, elemental carbon, and PM2.5 mass in seven U.S. cities

Methods that measure PM2.5 mass, total particulate NO3-, and elemental carbon (EC) were evaluated in seven U.S. cities from 1997 to 1999. Sampling was performed in Bakersfield, CA; Boston, MA; Chicago, IL; Dallas, TX; Philadelphia, PA; Phoenix, AZ; and Riverside, CA. Evaluating and validating methods that measure the components of fine mass are important to the effort of establishing a speciation-monitoring network. The Harvard Impactor (HI), which measures fine particle mass, showed excellent agreement (r2 = 0.99) with the PM2.5 Federal Reference Method (FRM) for 81 24-hr samples in Riverside and Bakersfield. The HI also showed good precision (4.8%) for 243 24-hr collocated samples over eight studies. The Aethalometer was employed in six of the sampling locations to measure black carbon (BC). These values were compared to EC as measured from a quartz filter using thermal analysis. For the six cities combined, the two methods were highly correlated (r2 = 0.94; 187 24-hr samples); however, the BC values were approximately 24% less than the EC measurements consistently across all six cites. This compares well to results observed for EC/BC measurements observed in other semi-urban areas. Particulate NO3- was measured using the Harvard-EPA Annular Denuder System (HEADS). This was compared to the NO3- measured from the HI Teflon (DuPont) filter to assess NO3- artifacts. Significant NO3- losses (approximately 50% of total NO3-) were found in Riverside, Philadelphia, and Boston, while minimal artifacts were observed in the other sites. Two types of HEADS configurations were employed in five cities. One system used a Na2CO3-coated glass fiber filter, and the other type used a nylon filter to collect volatilized NO3- from the Teflon filter. The HEADS with the Na2CO3-coated filter consistently underestimated the total particulate NO3- by approximately 20% compared to the nylon HEADS.