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.     

Protocol Development for Assessing Arsenic Background Concentrations in Florida Urban Soils

Knowledge of arsenic background concentrations in urban soils is important for making remediation decisions. The soil cleanup target level (SCTL) for arsenic in Florida lies within the range of arsenic background concentrations. The residential SCTL is also near the practical quantification limits using analytical procedures. Currently no standard protocols are available for determining arsenic background concentrations in urban soils, apart from site-specific cases. Therefore, a pilot study was conducted to develop and employ appropriate protocols to determine arsenic distribution in urban soils. This involved: site selection (e.g. size and sampling frame), sample collection (e.g. sampling technique), and statistical considerations (e.g. design). Factors such as ease of sample collection and maintaining anonymity of private properties were also considered as they influence the successful implementation of the study. Forty surface soil samples each were collected from five categories in three land use classes (residential-yard and right-of-way, commercial and public land-parks and public building), digested using EPA method 3051a and analysed using graphite furnace atomic absorption spectrometry. Experiences from the pilot study (e.g. complications during sample selection, digestion, data censoring etc.) were used in the development of the final protocol to be used in determining the distribution of arsenic in urban areas.     

Protocol Development for Assessing Arsenic Background Concentrations in Florida Urban Soils

Knowledge of arsenic background concentrations in urban soils is important for making remediation decisions. The soil cleanup target level (SCTL) for arsenic in Florida lies within the range of arsenic background concentrations. The residential SCTL is also near the practical quantification limits using analytical procedures. Currently no standard protocols are available for determining arsenic background concentrations in urban soils, apart from site-specific cases. Therefore, a pilot study was conducted to develop and employ appropriate protocols to determine arsenic distribution in urban soils. This involved: site selection (e.g. size and sampling frame), sample collection (e.g. sampling technique), and statistical considerations (e.g. design). Factors such as ease of sample collection and maintaining anonymity of private properties were also considered as they influence the successful implementation of the study. Forty surface soil samples each were collected from five categories in three land use classes (residential-yard and right-of-way, commercial and public land-parks and public building), digested using EPA method 3051a and analysed using graphite furnace atomic absorption spectrometry. Experiences from the pilot study (e.g. complications during sample selection, digestion, data censoring etc.) were used in the development of the final protocol to be used in determining the distribution of arsenic in urban areas.     

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.     

Inter-Urban Comparison of Ambient Volatile Organic Compound Concentrations in U.S. Cities

Airborne particulate matter from three ferrous foundries was sampled in granulometric fractions and analyzed by scanning electron microscopy with energy dispersive X-ray analysis (SEM-EDXA), X-ray photoelectron spectroscopy (XPS) and secondary ion mass spectrometry (SIMS) to determine morphology and qualitative bulk and surface chemical compositions. Cluster and principal components analyses (PCA) were used as an aid for interpretation of results. A clear pattern of composition as a function of size emerges; in particular, trace metals accumulate in fine particles and volatile species on the surface of these. Chemical composition changes are also related to daily schedules where applicable: trace metals appear during pouring operations, silicon is generated during mold making and unmolding. Cluster and PCA greatly ease examination of data and offer pictorial representations of results; in particular, the chemical composition versus particle size relationship is very neatly illustrated by PCA graphs.     

Arsenic Background Definition: Introduction and Objectives

Produced water samples from the Bacia de Campos oil field offshore Pargo and Pampo platforms were analyzed for Ba, 226 Ra, 228 Ra, V, Ni and Pb. The activity concentrations measured were in the range of 1.6-6.0 Bq/L for 226 Ra and 0.7-8.2 Bq/L for 228 Ra for both platforms. For Ba, V, Ni and Pb the concentrations measured were in the range of 5.6-25.7 mg/L, 0.15-0.46 µg/L, 4.85-12.14 µg/L and 4.04-12.37 µg/L. A strong correlation between barium and radium isotopes concentration was observed ( 226 Ra: R 2 = 0.897; 228 Ra: R 2 = 0.737). In order to evaluate the environmental impact from discharges of produced water into the sea, the seawater and sediment samples were collected at distances from 250 to 1000 m around the platforms. The seawater samples were analyzed for dissolved and particulate material and the sediment samples for total and leachable fraction. The results show that even for the shortest sampling distance (250 m) from the discharge point, Ba, 226 Ra, 228 Ra, V, Ni and Pb concentrations in seawater and sediment were similar to the local background, indicating that dispersion by local currents minimizes any environmental impact involving these parameters.     

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.     

Spatial and temporal pattern of eastern U.S. haziness: A summary

One of the key features of the optical environment over the eastern U.S. is the frequent occurrence of regional haziness, particularly during the summer season. Four historical data bases were examined for estimation of the regional trend in haziness over the past 80 years: the surface visibility observations currently operated by the National Weather Service; historical visibility at Blue Hill MA; the NOAA-WMO turbidity network measuring the extinction of solar radiation with a sun photometer since the 1960's; and a set of direct solar radiation monitoring stations operated since 1910.In the 1970's the lowest visibility occurred in the region of the Ohio River. The strongest increase of haziness was noted in the states adjacent to the Smoky Mountains: the average visibility there has decreased from 24 to 10 km since 1948. That region also exhibits the highest turbidity (vertical optical depth of the aerosol). The spatial trends of coal consumption indicate a consistency with the spatial trends in haziness.     

Risk-based Decision Process for Arsenic in Soils: Implications of Conservative Protocols

Making defensible risk-based decisions is a complex process that incorporates risk assessment into a risk management framework. Many site investigations require additional study, negotiations and/or actions for arsenic detected in soil samples, in many cases where no process related sources are identified and no other chemicals of concern are identified. Regulatory agencies develop guidance to standardize approaches to risk-based site investigations that focus on achieving “safe” concentrations. For arsenic, the action level is frequently in the “gray region”, a U.S. Environmental Protection Agency (USEPA) term associated with a region of high uncertainty for risk management decisions in the “decision performance curve” associated with the data quality objective (DQO) process. Recognizing the conservative nature of the risk-based screening value for arsenic, approaches to enforce this level (or proof of comparability to natural background) may have numerous consequences including ineffective use of resources, stigmas on properties or actions at industrial or hazardous sites that are inconsistent with their regional setting. Florida has developed regulations and guidance on investigation of brownfield sites and has supported a study by the University of Florida (UF) to evaluate natural background concentrations in Florida soils. This paper discusses the sources of uncertainty near the soil cleanup target levels (SCTLs) in the Florida decision-making framework.     

Risk-based Decision Process for Arsenic in Soils: Implications of Conservative Protocols

Making defensible risk-based decisions is a complex process that incorporates risk assessment into a risk management framework. Many site investigations require additional study, negotiations and/or actions for arsenic detected in soil samples, in many cases where no process related sources are identified and no other chemicals of concern are identified. Regulatory agencies develop guidance to standardize approaches to risk-based site investigations that focus on achieving "safe" concentrations. For arsenic, the action level is frequently in the "gray region", a U.S. Environmental Protection Agency (USEPA) term associated with a region of high uncertainty for risk management decisions in the "decision performance curve" associated with the data quality objective (DQO) process. Recognizing the conservative nature of the risk-based screening value for arsenic, approaches to enforce this level (or proof of comparability to natural background) may have numerous consequences including ineffective use of resources, stigmas on properties or actions at industrial or hazardous sites that are inconsistent with their regional setting. Florida has developed regulations and guidance on investigation of brownfield sites and has supported a study by the University of Florida (UF) to evaluate natural background concentrations in Florida soils. This paper discusses the sources of uncertainty near the soil cleanup target levels (SCTLs) in the Florida decision-making framework.     

Analysis of Mosses and Soils for Quantifying Heavy Metal Concentrations in Sicily: A Multivariate and Spatial Analytical Approach

- DOI: http://dx.doi.org/10.1065/espr2006.01.006 Background The use of vegetal organisms as indicators of contamination of the environment is partially replacing traditional monitoring techniques. Amongst the vegetal organisms available, mosses appear to be good bioindicators and are used for monitoring anthropogenic and natural fall-out on soils. This study has two objectives: the evaluation of the concentrations of heavy metals in soils and mosses of the Sicily Region, in Italy and the identification of the origin of fall-out of heavy metals. Methods Mosses and the surface soil were sampled at 28 sites, only the youngest segments of Hylocomium splendens and Hypnum cupressiforme, corresponding to the plant tissues produced during the last 3 years, were taken. The elements Cd, Cu, Ni, Pb and Zn were analysed by ICP-MS and Hg by AAS. Statistical analysis was by PCA and spatial representation by GIS. Results and Discussion In the mosses sampled in Sicily, the highest concentrations of Cd were found around the cities of Palermo and Messina. The highest concentrations of Hg were recorded in the northern part of the island between Trapani and Messina, similar to the distribution of Cu. Different areas with the highest concentrations of Ni were found near the south coast, in the vicinity of Palermo and around the Volcano Etna. The highest concentrations of Pb were found in the south-west coast near Agrigento, where important chemical plants and petroleum refineries are located. Except for a few locations, Zn fall-out was found to be evenly distributed throughout Sicily. Conclusion The sites where the concentrations of heavy metals cause greatest concern have been revealed by the PCA analysis and portrayed using GIS. Also of some concern is the diffuse and anthropogenic origin of Hg and Cd. The combined approach of using soil and mosses, together with pedological interpretation and application of multivariate statistical techniques has provided valuable insight into the environmental aspects of heavy metal deposition in a region of southern Europe. Recommendations and Outlook Further insight into the deposition of heavy metals will require more detailed sampling of soils and mosses in both new and previous study areas. This needs to be complemented by detailed pedological investigations in the study areas. Future research programmes will address these issues.     

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.     

Infant Mortality and Air Pollution: A Comprehensive Analysis of U.S. Data for 1990

ABSTRACT

This paper uses U.S. linked birth and death records to explore associations between infant mortality and environmental factors, based on spatial relationships. The analysis considers a range of infant mortality end points, regression models, and environmental and socioeconomic variables. The basic analysis involves logistic regression modeling of individuals; the cohort comprises all infants born in the United States in 1990 for whom the required data are available from the matched birth and death records. These individual data include sex, race, month of birth, and birth weight of the infant, and personal data on the mother, including age, adequacy of prenatal care, and smoking and education in most instances. Ecological variables from Census and other sources are matched on the county of usual residence and include ambient air quality, elevation above sea level, climate, number of physicians per capita, median income, racial and ethnic distribution, unemployment, and population density. The air quality variables considered were 1990 annual averages of PM₁₀, CO, SO₂, SO₄ ^2-, and “non-sulfate PM₁₀” (NSPM₁₀—obtained by subtracting the estimated SO₄ ^2-mass from PM₁₀). Because all variables were not available for all counties (especially maternal smoking), it was necessary to consider various subsets of the total cohort.

We examined all infant deaths and deaths by age (neonatal and postneonatal), by birth weight (normal and low [<2500 g]), and by specific causes within these categories. Special attention was given to sudden infant death syndrome (SIDS). For comparable modeling assumptions, the results for PM₁₀ agreed with previously published estimates; however, the associations with PM₁₀ were not specific to probable exposures or causes of death and were not robust to changes in the model and/or the locations considered. Significant negative mortality associations were found for SO₄ ^2-. There was no indication of a role for outdoor PM_2.5, but possible contributions from indoor air pollution sources cannot be ruled out, given higher SIDS rates in winter, in the north and west, and outside of large cities.     

Determination of Fine Particulate Semi-Volatile Organic Material at Three Eastern U.S. Sampling Sites

ABSTRACT

Correct assessment of fine particulate carbonaceous material as a function of particle size is, in part, dependent on the determination of semi-volatile compounds, which can be lost from particles during sampling. This study gives results obtained for the collection of fine particulate carbonaceous material at three eastern U.S. sampling sites [Philadelphia, PA; Shenandoah National Park, VA; and Research Triangle Park (RTP), NC] using diffusion denuder technology. The diffusion denuder samplers allow for the determination of fine particulate organic material with no artifacts, due to the loss of semi-volatile organic particulate compounds, or collection of gas-phase organic compounds by the quartz filter during sampling. The results show that an average of 41, 43, and 59% of fine particulate organic material was lost as volatilized semi-volatile organic material during collection of particles on a filter at Philadelphia, RTP, and Shenandoah, respectively. The particle size distribution of carbonaceous material retained by a filter and lost from a filter during sampling was obtained for the samples collected at Philadelphia and Shenandoah. The carbonaceous material retained by the particles during sampling was found predominantly in particles smaller than 0.4 μm in aerodynamic diameter. In contrast, the semi-volatile organic material lost from the particles during sampling had a mass median diameter of ~0.5 μm.     

Determination of fine particulate semi-volatile organic material at three eastern U.S. sampling sites

Correct assessment of fine particulate carbonaceous material as a function of particle size is, in part, dependent on the determination of semi-volatile compounds, which can be lost from particles during sampling. This study gives results obtained for the collection of fine particulate carbonaceous material at three eastern U.S. sampling sites [Philadelphia, PA; Shenandoah National Park, VA; and Research Triangle Park (RTP), NC] using diffusion denuder technology. The diffusion denuder samplers allow for the determination of fine particulate organic material with no artifacts, due to the loss of semi-volatile organic particulate compounds, or collection of gas-phase organic compounds by the quartz filter during sampling. The results show that an average of 41, 43, and 59% of fine particulate organic material was lost as volatilized semi-volatile organic material during collection of particles on a filter at Philadelphia, RTP, and Shenandoah, respectively. The particle size distribution of carbonaceous material retained by a filter and lost from a filter during sampling was obtained for the samples collected at Philadelphia and Shenandoah. The carbonaceous material retained by the particles during sampling was found predominantly in particles smaller than 0.4 microm in aerodynamic diameter. In contrast, the semi-volatile organic material lost from the particles during sampling had a mass median diameter of approximately 0.5 microm.     

Pesticides in ground water in the united states: Monitoring,modeling, and risks from the U.S. perspective

Abstract

Scientific and regulatory interest in ground water contamination by pesticides increased significantly in 1979. This was prompted by findings of the nematicide 1,2‐dibromo‐3‐chloropropane (DBCP) and the nematicide/insecticide aldicarb (Temik®) in ground water in several states. Since that time, at least 130 pesticides and pesticide metabolites have been detected in ground water in over 150 studies, but detection frequencies are 4–10% nationally. Detection frequencies of pesticides over Health Advisory Levels are generally lower. Screening‐level models and detailed computer simulation models are useful for risk assessments and regulatory decisions. Attenuation Factor, CMLS, PRZM2, GLEAMS, and LEACHM are all useful models.     

A status report on the U.S. national dioxin study

In 1983, the US Environmental Protection Agency (EPA) embarked on an extensive investigation of the presence and extent of contamination of the national environment by CDDs/CDFs. This status report is a prelude to a final report to be delivered to the US Congress in December, 1985.