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Contaminant exposure and potential effects on terrestrial vertebrates residing in the National Capital Region network and Mid-Atlantic network

Part of the mission of the National Park Service is to preserve the natural resources, processes, systems, and associated values of its units in an unimpaired condition. Environmental contamination and pollution processes are well recognized stressors addressed by its management policies and plans. A recent study indicates that contemporary terrestrial vertebrate ecotoxicological data are lacking for 59 of 126 Park Service units located in coastal watersheds exhibiting serious water quality problems or high vulnerability to pollution. Based upon these findings, a more in-depth evaluation of contaminant threats and ecotoxicological data gaps related to terrestrial vertebrates was undertaken at 23 Inventory and Monitoring National Park units in National Capital Region and Mid-Atlantic Networks. Ecotoxicological data were compiled for each park unit through literature searches and meetings with Park Service personnel. Information on contemporary and on persistent legacy pollutants in air, water, soil, and terrestrial vertebrates (amphibians, reptiles, birds and mammals) were evaluated. To identify contaminant threats in proximity to the 23 Park Service study units, data was gathered on National Priority List Superfund sites, Section 303(d) Impaired Waterbodies, the number and relative toxicity of current use pesticides and herbicides, Toxic Release Inventory sites and discharge of priority pollutants, and Fish Consumption Advisories. A metric was derived that described the quality and quantity of existing data for each park, and in combination with known contaminant threats, park units in need of additional study were identified. Results demonstrated that over half of the Park Service study units are near Toxic Release Inventory sites discharging dioxins, polychlorinated biphenyls, lead or mercury into air or water, and fish consumption advisories are in effect at or near 22 of the 23 study units. Pesticide and herbicide use at the park units is minimal, with the exception of those units with significant agricultural leases. Despite highly regulated use, many of the pesticides and herbicides applied are believed to be highly toxic to amphibians, and some of the compounds are also highly toxic to birds. Only 70 reports were found that describe terrestrial vertebrate ecotoxicology data on or near the study units. Of the greater than 75,000 compounds in commerce in the United States, existing terrestrial vertebrate exposure and effects data in the pr esent study were limited to 58 legacy organochlorine pesticides, polychlorinated biphenyls and individual congeners, insecticides and rodenticides, metals, and some contemporary compounds (e.g., polybrominated diphenyl ether flame retardants, and alkylphenol and ethoxylate surfactants). Based upon these and other findings, ecotoxicological monitoring and research investigations of terrestrial vertebrates are warranted at several National Parks. These include Shenandoah National Park, Richmond National Battlefield, Chesapeake & Ohio Canal National Historic Park, Valley Forge National Historic Park, Hopewell Furnace National Historic Site, Monocacy National Battlefield, and Harpers Ferry National Historic Park. The types of investigations vary according to the species present at these parks and potential contaminant threats, but should focus on contemporary use pesticides and herbicides, polychlorinated biphenyls, mercury, lead, and perhaps, emerging contaminants including antibiotics, flame retardants, pharmaceuticals, and surfactants. Other management recommendations include additional training for natural resource staff members in the area of ecotoxicology, inclusion of terrestrial vertebrate contaminant monitoring and the Contaminant Assessment Process (U.S. Geological Survey Biomonitoring of Environmental Status and Trends Project) into the National Park Service Vital Signs Program, development of protocols for hand ling and toxicological analysis of dead or seemingly affected wildlife, consideration of some alternative methods and compounds for pest management and weed control, and use of non-toxic fishing tackle by visitors.

Maryland, Pennsylvania, Virginia

100 years of Pb deposition and transport in soils in Champaign, Illinois, U.S.A

In Illinois, atmospheric deposition is one major source of heavy metal inputs to agricultural land. The atmospheric Pb deposition and transport record in agricultural soils in Champaign, Illinois, was established by studying surface and subsurface soil samples collected during the past 100 years from the Morrow Plots on the campus of the University of Illinois at Urbana-Champaign. The Pb content in the soil samples was measured and the Ph deposition fluxes were calculated. The Pb content in surface soils increased sharply in the first half of the 20th century, and stayed invariant since. The maximum Pb flux from the atmosphere was estimated to be 27 (??14) ??g cm-2 yr-1 around 1940. The major pollution source for this increase probably was residential coal burning. It was estimated that in 50 yr, more than 50% of the Pb input had been lost from the surface soils.

Water, Air, & Soil Pollution

Effects of the flood of 1993 on the chemical characteristics of bed sediments in the Upper Mississippi River

Concentrations of pollutants stored in the surficial bed sediments in the navigation pools of the Upper Mississippi River showed a general decrease after the record flood of 1993. Percent clay and total organic carbon in the surficial sediments decreased as a result of an increase in the proportion of coarser sediment. Decreases in pollutant concentration may have been a result of the dilution by coarser and relatively less polluted sediment that was mobilized and transported into the Upper Mississippi River from its tributaries or from mainstem locations upstream but outside of the sampling area.

Water, Air, & Soil Pollution

Changing regional emissions of airborne pollutants reflected in the chemistry of snowpacks and wetfall in the Rocky Mountain region, USA, 1993–2012

Wintertime precipitation sample data from 55 Snowpack sites and 17 National Atmospheric Deposition Program (NADP)/National Trends Network Wetfall sites in the Rocky Mountain region were examined to identify long-term trends in chemical concentration, deposition, and precipitation using Regional and Seasonal Kendall tests. The Natural Resources Conservation Service snow-telemetry (SNOTEL) network provided snow-water-equivalent data from 33 sites located near Snowpack- and NADP Wetfall-sampling sites for further comparisons. Concentration and deposition of ammonium, calcium, nitrate, and sulfate were tested for trends for the period 1993–2012. Precipitation trends were compared between the three monitoring networks for the winter seasons and downward trends were observed for both Snowpack and SNOTEL networks, but not for the NADP Wetfall network. The dry-deposition fraction of total atmospheric deposition, relative to wet deposition, was shown to be considerable in the region. Potential sources of regional airborne pollutant emissions were identified from the U.S. Environmental Protection Agency 2011 National Emissions Inventory, and from long-term emissions data for the period 1996–2013. Changes in the emissions of ammonia, nitrogen oxides, and sulfur dioxide were reflected in significant trends in snowpack and wetfall chemistry. In general, ammonia emissions in the western USA showed a gradual increase over the past decade, while ammonium concentrations and deposition in snowpacks and wetfall showed upward trends. Emissions of nitrogen oxides and sulfur dioxide declined while regional trends in snowpack and wetfall concentrations and deposition of nitrate and sulfate were downward.

Colorado, Idaho, Montana, New Mexico, Utah, Wyomin

Historical trace metal accumulation in the sediments of an urbanized region of the Lake Champlain watershed, Burlington, Vermont

This study documents the history of pollution inputs in the Burlington region of Lake Champlain, Vermont using measurements of anthropogenic metals (Cu, Zn, Cr, Pb, Cd, and Ag) in four age-dated sediment cores. Sediments record a history of contamination in a region and can be used to assess the changing threat to biota over time and to evaluate the effectiveness of discharge regulations on anthropogenic inputs. Grain size, magnetic susceptibility, radiometric dating and pollen stratigraphy were combined with trace metal data to provide an assessment of the history of contamination over the last 350 yr in the Burlington region of Lake Champlain. Magnetic susceptibility was initially used to identify land-use history for each site because it is a proxy indicator of soil erosion. Historical trends in metal inputs in the Burlington region from the seventeenth through the twentieth centuries are reflected in downcore variations in metal concentrations and accumulation rates. Metal concentrations increase above background values in the early to mid nineteenth century. The metal input rate to the sediments increases around 1920 and maximum concentrations and accumulation rates are observed in the late 1960s. Decreases in concentration and accumulation rate between 1970 and the present are observed, for most metals. The observed trends are primarily a function of variations in anthropogenic inputs and not variations in sediment grain size. Grain size data were used to remove texture variations from the metal profiles and results show trends in the anthropogenic metal signals remain. Radiometric dating and pollen stratigraphy provide well-constrained dates for the sediments thereby allowing the metal profiles to be interpreted in terms of land-use history.This study documents the history of pollution inputs in the Burlington region of Lake Champlain, Vermont using measurements of anthropogenic metals (Cu, Zn, Cr, Pb, Cd, and Ag) in four age-dated sediment cores. Sediments record a history of contamination in a region and can be used to assess the changing threat to biota over time and to evaluate the effectiveness of discharge regulations on anthropogenic inputs. Grain size, magnetic susceptibility, radiometric dating and pollen stratigraphy were combined with trace metal data to provide an assessment of the history of contamination over the last 350 yr in the Burlington region of Lake Champlain. Magnetic susceptibility was initially used to identify land-use history for each site because it is a proxy indicator of soil erosion. Historical trends in metal inputs in the Burlington region from the seventeenth through the twentieth centuries are reflected in downcore variations in metal concentrations and accumulation rates. Metal concentrations increase above background values in the early to mid nineteenth century. The metal input rate to the sediments increases around 1920 and maximum concentrations and accumulation rates are observed in the late 1960s. Decreases in concentration and accumulation rate between 1970 and the present are observed for most metals. The observed trends are primarily a function of variations in anthropogenic inputs and not variations in sediment grain size. Grain size data were used to remove texture variations from the metal profiles and results show trends in the anthropogenic metal signals remain. Radiometric dating and pollen stratigraphy provide well-constrained dates for the sediments thereby allowing the metal profiles to be interpreted in terms of land-use history.

New York, Vermont

Variables that affect agricultural chemicals in groundwater in Nebraska

Agricultural chemicals from nonpoint sources in groundwater are present in the major provinces of the High Plains aquifer in Nebraska. Nitrate and triazine-herbicide concentrations in groundwater were assessed to establish preliminary relations between these constituents and selected hydrogeologic, climatic, and land-use variables. Also, macropore flow paths were measured in an attempt to delineate their contribution to non-point source pollution from the study areas. Water from 82 wells in six study areas was analyzed for nitrate; water from 57 of the 82 wells was analyzed for triazine herbicides. Twenty-one independent variables were identified that could potentially affect chemical concentrations in groundwater. Data for 9 of 21 independent variables suspected of affecting concentrations of nitrate and triazine herbicides in groundwater were collected from the well sites. The nine variables and their measured ranges were hydraulic gradient, 0.0006–0.0053; hydraulic conductivity, 1.5–45.4 m (5–149 ft) per day; specific discharge, 0.004–0.091 m (0.0128–0.2998 ft) per day; depth to water, 0.91–76 m (3–250 ft); well depth, 12–168 m (40–550 ft); annual precipitation, 30–100 cm (12.0–39.3 in.); soil permeability, 1.9–23 cm (0.76–9.0 in.); irrigation-well density, 0–8 irrigation wells per 2.59 km 2 (1 square mile); and annual nitrogen fertilizer use, 0–118 kg (0–260 lb) of nitrogen per acre. Macropore flow is listed in percent, average per study area based on determinations from dye studies. In this instance, macropore flow is used to also entail preferential flow paths. Nitrate concentrations ranged from 0.1 to 45 mgL −1 . Triazine-herbicide concentrations were detected in samples from five of the six study areas in concentrations ranging from 0.1 to 2.3 μL −1 . Analysis indicated that there were significant differences in nitrate concentrations (averages-at 95 % confidence level using Kendall Test) among the six study areas; no significant differences in triazineherbicide concentrations were found. Concentrations of nitrate and triazine herbicide were determined (using contingency-table analysis), to be significantly larger in more intensively irrigated areas compared to less intensively irrigated areas. Preliminary correlations with the independent variables and nitrate concentrations indicated significant relations at the 95%confidence level with variables hydraulic conductivity, well depth, and irrigation well density. Correlations with triazine-herbicide concentrations indicated significant relations with hydraulic conductivity, specific discharge, well depth, annual precipitation, and irrigation well density, as well as nitrate concentrations. Simple multiple-regression technique indicated that well depth and density and fertilizer use explained about 51 % of the variation in nitrate concentrations. Specific discharge and well depth explained about 60 % of the variation in triazine-herbicide concentrations. Macropore flow paths and specific discharge explained 84 % of the total variation in triazineherbicide concentrations. The use of trade names in this report is for identification purposes only and does not constitute endorsement by the U.S. Geological Survey.

Nebraska

Environmental fate of mercury discharged into the upper Wisconsin River

The authors studied the distribution of Hg in sediments, fish, and crayfish in a 60 km reach of the Upper Wisconsin River that formerly received Hg in discharges from pulp and paper mills. The most heavily contaminated strata of sediments were deposited during the 1950s and early 1960s and buried under subsequent deposits; however, surficial sediments remained substantially enriched at certain sites in 1981. Median concentrations of Hg in surficial sediments, adjusted for grain size, were at least 10-fold greater at the main study area than at an upstream reference site. Total concentrations exceeded 1.0 mu g g super(-1) wet weight in axial muscle tissue in only 2 of 173 fish analyzed from the study area; however, historical comparisons revealed that Hg contamination of fish (common carp Cyprinus carpio and walleye Stizostedion vitreum vitreum ) and crayfish (Orconectes ) in the river had not decreased since the early 1970s.

Water, Air, & Soil Pollution

Cooperative federal-state liming research on surface waters impacted by acidic deposition

In the eastern and north-central United States, lakes and streams with low acid neutralizing capacity are at risk from acidity. Resource management agencies are interested in developing mitigation strategies that protect or restore fisheries in these waters. Addition of limestone (calcium carbonate) to improve water quality and prevent episodic depressions of pH during precipitation events and spring runoff is one mitigation technique being used. The ecological changes that accompany such treatment of streams and lakes are being investigated in a cooperative program between the U.S. Fish and Wildlife Service and individual states. Streams in Massachusetts, West Virginia and Tennessee, and a lake in Minnesota are included in this 5-yr research program. Intensive monitoring during pre- and post-liming tracks a suite of physical, chemical and biological parameters that influence the re-establishment or maintenance of healthy fisheries. Supporting studies on liming being conducted at Adirondack lakes in New York focus on fisheries management. A model on the influence of liming on light attenuation and thermal stratification is also being developed. Management guidelines are to be generated from the program results.

Massachusetts, Minnesota, Tennessee, West Virginia

Episodic acidification of a coastal plain stream in Virginia

This study investigates the episodic acidification of Reedy Creek, a wetland-influenced coastal plain stream near Richmond, Virginia. Primary objectives of the study were to quantify the episodic variability of acid- base chemistry in Reedy Creek, to examine the seasonal variability in episodic response and to explain the hydrological and geochemical factors that contribute to episodic acidification. Chemical response was similar in each of the seven storms examined, however, the ranges in concentrations observed were commonly greater in summer/fall storms than in winter/spring storms. An increase in SO4/2- concentration with discharge was observed during all storms and peak concentration occurred at or near peak flow. Small increases in Mg2+, Ca2+, K+ concentrations and dissolved organic carbon (DOC) were observed during most storms. At the same time, ANC, Na+ and Cl- concentrations usually decreased with increasing discharge. In summer/fall storms, the absolute increase in SO4/2- concentration was one-third to 15 times the increase observed in winter/spring storms; the decrease in ANC during summer/fall storms was usually within the range of the decrease observed in winter/spring storms. In contrast, the decrease in Na+ and Cl- concentrations during winter/spring storms was much greater than that observed during summer/fall storms. Data show that while base flow anion deficit was higher in summer/fall than in winter/spring, anion deficit decreased during most summer/fall storms. In contrast, base flow anion deficit was lower in spring and winter, but increased during winter/spring storms. Increased SO4/2- concentration was the main cause of episodic acidification during storms at Reedy Creek, but increased anion deficit indicates organic acids may contribute to episodic acidification during winter/spring storms. Changes in SO4/2- concentration coincident with the hydrograph rise indicate quick routing of water through the watershed. Saturation overland flow appears to be the likely mechanism by which solutes are transported to the stream during storm flow.

Water, Air, & Soil Pollution

Effects of cover materials on leaching of constituents from dolomitic lead mine tailings

Five raised-bed test plots were used to study the effects of cover materials on the leaching of constituents from dolomitic Pb mine tailings over a 2-yr period. The cover materials studied were a fertilizer and seed mixture, anaerobically digested sewage sludge, loam and sod, and fallen leaves from silver maples ( Acer Saccharinum ); one plot was not covered. Fresh leachates and receiving pool waters were analyzed for ten metals, Si, P, inorganic anions, filterable organic carbon (FOC), and alkalinity. The mixture of fertilizer and seed decreased leaching of Pb and Zn during the first year. The leaf cover increased leaching of Pb during both years; this effect decreased as the leaves weathered. Sludge caused some increase in Pb leaching during the first year, and increased Cd leaching during both years. Concentrations of most leachate constituents decreased, and pH increased in the receiving pools. Concentrations of Pb remained higher in the receiving pool for the leaf-covered plot than in the other pools. Increases in leaching of Pb and Cd with a sludge cover were moderate, and the ability of the material to support plant growth on the tailings suggested that it may be a good medium for inducing growth of vegetative cover on the dolomitic tailings. Other organic materials may cause pronounced increase in the concentration of toxic trace metals in leachate from the tailings.

Missouri

Chloride cycling in two forested lake watersheds in the west-central Adirondack Mountains, New York, U.S.A.

The chemistry of precipitation, throughfall, soil water, ground water, and surface water was evaluated in two forested lake-watersheds over a 4-yr period to assess factors controlling C1- cycling. Results indicate that C1- cycling in these watersheds is more complex than the generally held view of the rapid transport of atmospherically derived C1- through the ecosystem. The annual throughfall Cl- flux for individual species in the northern hardwood forest was 2 to 5 times that of precipitation (56 eq ha-1), whereas the Na+ throughfall flux, in general, was similar to the precipitation flux. Concentrations of soil-water Cl- sampled from ceramic tension lysimeters at 20 cm below land surface generally exceeded the Na+ concentrations and averaged 31 ??eq L-1, the highest of any waters sampled in the watersheds, except throughfall under red spruce which averaged 34 ??eq L-1. Chloride was concentrated prior to storms and mobilized rapidly during storms as suggested by increases in streamwater Cl- concentrations with increasing flow. Major sources of Cl- in both watersheds are the forest floor and hornblende weathering in the soils and till. In the Panther Lake watershed, which contains mainly thick deposits of till( > 3 m), hornblende weathering results in a net Cl- flux 3 times greater than that in the Woods Lake watershed, which contains mainly thin deposits of till. The estimated accumulation rate of Cl- in the biomass of the two watersheds was comparable to the precipitation Cl- flux.The chemistry of precipitation, throughfall, soil water, ground water, and surface water was evaluated in two forested lake-watersheds over a 4-yr period to assess factors controlling Cl- cycling. Results indicate that Cl- cycling in these watersheds is more complex than the generally held view of the rapid transport of atmospherically derived Cl- through the excosystem. The annual throughfall Cl- flux for individual species in the northern hardwood forest was 2 to 5 times that of precipitation (56 eq ha-1), whereas the Na+ throughfall flux, in general, was similar to the precipitation flux. Concentrations of soil-water Cl- sampled from ceramic tension lysimeters at 20 cm below land surface generally exceeded the Na+ concentrations and averaged 31 ??eq L-1, the highest of any waters sampled in the watersheds, except throughfall under red spruce which averaged 34 ??eq L-1. Chloride was concentrated prior to storms and mobilized rapidly during storms as suggested by increases in streamwater Cl- concentrations with increasing flow. Major sources of Cl- in both watersheds are the forest floor and hornblende weathering in the soils and till. In the Panther Lake watershed, which contains mainly thick deposits of till (> 3 m), hornblende weathering results in a net Cl- flux 3 times greater than that in the Woods Lake watershed, which contains mainly thin deposits of till. The estimated accumulation rate of Cl- in the biomass of the two watersheds was comparable to the precipitation Cl- flux.

Water, Air, & Soil Pollution

Natural variance in pH as a complication in detecting acidification of lakes

Natural variance in the pH of three dilute lakes in the Flat Tops Wilderness Area, Colorado, complicates the detection of acidification. Variations in pH during July-September of 1983 were: 0.95 (Ned Wilson Lake), 1.36 (Upper Island Lake), and 1.53 (Oyster Lake). Mean diurnal variations in pH during 1983 were: 0.37 (Ned Wilson Lake), 0.54 (Upper Island Lake), and 0.39 (Oyster Lake). Replicate pH measurements indicate that pH can be measured with a mean variance due to measurement error of ?? 0.005. Regression analysis indicates that samples collected on the same day of different years may differ because of time of day and percentage of cloud cover. Differences in wind duration and intensity and primary productivity also may cause the pH to differ between years. Such differences can be either random or systematic. Comparisons of pH among 3 yr of data from Ned Wilson Lake indicate that natural variations in pH are much larger than variations in Colorado Lakes previously attributed to acidification by precipitation.

Water, Air, & Soil Pollution

Atmospheric deposition effects on the chemistry of a stream in Northeastern Georgia

The quantity and quality of precipitation and streamwater were measured from August 1985 through September 1986 in the Brier Creek watershed, a 440-ha drainage in the Southern Blue Ridge Province of northeastern Georgia, to determine stream sensitivity to acidic deposition. Precipitation samples collected at 2 sites had a volume-weighted average pH of 4.40 whereas stream samples collected near the mouth of Brier Creek had a discharge-weighted average pH of 6.70. Computed solute fluxes through the watershed and observed changes in streamwater chemistry during storm flow suggest that cation exchange, mineral weathering, SO 4 2− adsorption by the soil, and groundwater discharge to the stream are probable factors affecting neutralization of precipitation acidity. Net solute fluxes for the watershed indicate that, of the precipitation input, > 99% of the H + , 93% of the NH 4 + and NO 3 − , and 77% of the SO 4 2− were retained. Sources within the watershed yielded base cations, Cl − , and HCO 3 − and accounted for 84, 47, and 100% of the net transport, respectively. Although streamwater SO 4 2− and NO 3 − concentrations increased during stormflow, peak concentrations of these anions were much less than average concentrations in the precipitation. This suggests retention of these solutes occurs even when water residence time is short.

Georgia

Determining baseline element composition of lichens. I. Parmelia sulcata at Theodore Roosevelt National Park, North Dakota

Element-concentration baselines are given for Parmelia sulcata and associated soils. Parmelia chlorochroa was found sporadically and therefore only representative concentration ranges are reported for this species. Element data include (1) for lichens; Al, As, Ba, B, Ca, Cr, Cu, Fe, Hg, Mn, Ni, P, Sr, S, Ti, V, Y, and Zn; and (2) for soils: Al, Ba, Be, Ca, Cs, Cr, Cu, Fe, Hg, Mg, Mn, Ni, Nb, P, Pb, Sr, S, Ti, V, Y, and Zn. Very little (usually < 10 %) of the variability in the element data for lichen material occurs regionally (> 7.2 km); thus, P sukata is, in general, chemically similar throughout the park. This same uniformity was found for soil geochemistry. Numerous samples collected at close intervals would be required, therefore, to produce detailed element-concentration maps for P. sulcata and soils. No instances of elemental phytotoxic conditions were found; however, P. sulcata apparently possesses large concentrations of Ba, Cu, Fe, Pb, S, V, and possibly Zn.

North Dakota

Determining baseline element composition of lichens. II. Hypogymnia enteromorpha and Usnea spp. at Redwood National Park, California

Hypogymnia enteromorpha and Usnea spp. were collected in the Little Bald Hills ultramafic region of Redwood National Park, California, to establish element-concentration norms. Baselines are presented for Ba, Ca, Cu, Mn, Ni, P, Sr, V, and Zn for both lichen species; for Li, Mg, and K for H. enteromorpha ; and for Al, Ce, Cr, Co, Fe, Na, and Ti for Usnea . Element concentrations of future collections of this same material can be used to monitor possible air quality changes anticipated from mining activities planned nearby. The variability in the element concentrations was partitioned between geographical distance increments and sample preparation and analysis procedures. In general, most of this variability was found in samples less than a few hundreds of meters apart rather than those at about 1 km apart. Therefore, except for Ba and Co, no large geographical element-concentration trends were observed. Samples of both species contained elevated levels of Ni and Mg, which probably reflect the ultramafic terrain over which they occur.

California