NJWSC Archived Project
Concentrations of arsenic in four segments (reaches) of the Wallkill River and one segment of the Papakating Creek (a major tributary to the Wallkill River) have been found to exceed the New Jersey surface-water-quality standard of 0.0170 micrograms per liter. As a result, the U.S. Geological Survey (USGS) New Jersey Water Science Center, in cooperation with the New Jersey Department of Environmental Protection (NJDEP), initiated a study to determine the sources of arsenic to the Wallkill River to support the NJDEP in its effort to develop a total maximum daily load (TMDL) for arsenic in the watershed. Possible sources of arsenic in the watershed include geologic materials, pesticides, herbicides, septic-system effluent, industrial discharges, and residual material from historic ore smelting and coal burning. Once arsenic reaches the river, its concentrations are affected by geochemical and physical processes that include adsorption to and desorption from clays, iron-manganese oxides, and organic matter; transport on suspended sediments; and exchange between ground water and surface water.
Wallkill Arsenic Sources
START DATE: 01-AUG-2004
END DATE: 30-SEP-2007
PROJECT NUMBER: 2454BPT
Project Objectives
The overall objective of the project is to identify sources of arsenic to the Wallkill River Watershed. Individual objectives include:
- Determining whether arsenic (and other trace element) concentrations in surface water vary diurnally, in order to select an optimum time for sampling;
- Verifying reaches of the Wallkill River where arsenic concentrations are elevated relative to New Jersey surface-water-quality standards and determining concentrations of associated trace elements;
- Determining potential anthropogenic sources by evaluation of historic and existing land uses;
- # Determining the constituents that have increased (likely from increased development) in stream water over time by analysis of historic water-quality data; Determining the combinations of other elements associated with arsenic that can be used as chemical fingerprints of the three major groups of arsenic sources (geologic, disturbed geologic, and anthropogenic); fingerprinting would start with sediments, and the concept would be extended, if possible, to surface and ground water;
- Determining whether water that has flooded the abandoned Franklin and Sterling Hill mines contains high levels of arsenic leached from the surrounding bedrock, as well as other elements useful in establishing a chemical fingerprint for water in contact with the highly mineralized marble bedrock formation;
- Identifying whether domestic wells in different lithologies are tapping water with elevated concentrations of arsenic and whether ground water is a major source of arsenic in base flow.
Statement of Problem
Arsenic concentrations in water from the Wallkill River and Papakating Creek have been found to exceed the SWQS. Background data needs to be collected to support establishment of TMDLs by NJDEP at five sites on the Wallkill and one on the Papakating. Ground water in wells in the watershed also may tap water with arsenic levels that could exceed the proposed NJDWS. Potential sources of arsenic to water from the Papakating Creek and the Wallkill River include runoff containing residues of land applications of arsenical compounds, arsenic released from direct discharges to the streams, discharge of ground water containing trace elements contributed by geologic materials, and desorption of arsenic from stream sediments derived from soils and geologic materials.
Strategy and Approach
- To characterize potential arsenic sources, GIS coverages of the region’s geology, both bedrock and surficial (including metadata) will be created from the USGS GIS library, or, if needed, acquired. Land-use data, including GIS coverage of agricultural areas and mine locations (including metadata) will be compiled, and historic aerial photography of the watershed will be evaluated.
- To determine diurnal variations in metal concentrations in stream water during active photosynthesis, two ISCO samplers will be deployed during August to obtain trace-element data for stream water from the Wallkill River.
- On the basis of results of bi-hourly samples, optimum sampling time for obtaining the highest concentrations of arsenic in stream water will be determined and samples will be collected at that time for analysis of arsenic and other trace elements, major ions, nutrients, and chemical characteristics such as pH and Eh. Surface-water samples under base-flow conditions will be collected at 6 locations along the Wallkill River and two locations on Papakating Creek.
- To determine trace-element content of bottom sediment samples and upland sources of sediments to the river and creek, samples of stream-bottom sediments will be collected at the same locations as surface-water samples during the first (low-flow) sampling event. Additional stream-bottom sediment samples from the Wallkill River at Lake Mohawk and from Franklin Pond; from tributaries to the Wallkill River at two locations above Ogdensburg, at the Wildcat Brook, above and below Hamburg, at Beaver Run, and above Wantage; from two additional locations on the Papakating Creek and a tributary, above and below Sussex, and farther up the Papakating, near Wykertown, will be collected upstream of road crossings.
- To amplify existing data for the quality of the area’s ground water, particularly that from domestic wells, previously unsampled domestic wells within 0.5 mile of the Papakating Creek and the Wallkill River channels will be sampled—3-4 domestic wells completed in the Quaternary deposits (stratified drift), 3-4 in the area’s clastic rock formations (primarily the Martinsburg Shale), 3-4 completed in the carbonate formations (Allentown Dolomite, Leithsville Formation, Jacksonburg Limestone), 5-6 in the Franklin Marble (if possible), 4-5 in the gneisses with preference given to those closest to the Franklin and Sterling Hill mines.
- To determine relations between arsenic and other chemical constituents in stream water and hydrologic conditions, existing water-quality data will be analyzed for correlations between constituents, for trends with stream flow, for seasonal trends, and, where possible, analyzed for trends in constituent concentrations over time. To develop chemical fingerprints for possible arsenic sources, statistical and graphical techniques used in previous investigations (Barringer et al., 1998; Barringer et al., 2001) will be tailored to the proposed study
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STUDY OBJECTIVES
The study objectives are to
- identify possible anthropogenic sources of arsenic
- identify geologic sources of arsenic to the streamwater and riverbed sediments
- determine the ground-water contribution of arsenic to the system
- determine the physical, geochemical, and (or) biogeochemical processes that cause variations in arsenic concentrations in the river.
LAND USE
The Wallkill River watershed encompasses about 208 square miles in Sussex County in northwestern New Jersey (figure 1). The watershed is approximately 60 percent forested, 20 percent agricultural, 10 percent urban, and 10 percent wetlands, water, and barren land (figure 2).
GEOLOGY OF THE WALLKILL RIVER BASIN
The river begins at a small dam on Lake Mohawk (figure 3). From Lake Mohawk, it flows north through Franklin Pond (figures 1 and 2), through wetlands, and across the New Jersey-New York border, and ultimately discharges to the Hudson River. Along its course, the river encounters several different geologic substrates (figure 4). It flows through valley-fill glacial deposits that overlie faulted carbonate rocks that consist of dolomite at the headwaters; marble (with some granite and gneiss) in the middle segment; and dolomite again at the extreme northern (downstream) end. The valley fill consists of sediments eroded from the geologic materials. Each of these lithologic units may contribute arsenic to the ground water, which then discharges to the river.
POSSIBLE SOURCES OF ARSENIC TO THE WALLKILL RIVER
Selected locations along the river are shown in figures 5 to 7, which illustrate some of the possible anthropogenic sources and environments that may affect arsenic concentrations in the river. At its origin at Lake Mohawk, the Wallkill River is surrounded by unsewered residential land and a golf course. The outfall of Lake Mohawk is shown in figure 5.
The river flows north from Lake Mohawk to Franklin Pond (figs. 1, 2, and 6). The Franklin area is famous for the now-closed Franklin mines, where substantial quantities of rare zinc-bearing ore minerals were extracted from the early 1800s until 1986. Iron ores were roasted near Franklin Pond (fig. 6) in the 18th and 19th centuries. A short distance (about 1,000 feet) downstream from the pond and bordering the Wallkill River is the Buckwheat Dump, which contains tailings from the zinc-ore mining. Because zinc-bearing ores contain arsenic, sediments derived from weathering of the rock formation, as well as the tailings, are possible sources of arsenic to the river.
About 4.5 miles downstream from Franklin Pond, the river leaves the bedrock part of the basin and widens as it flows over glacial outwash. Before it leaves the State, it flows through the Wallkill River National Wildlife Refuge (fig. 7), a 4,500-acre protected, restricted-access area made up of grasslands, upland forests and shrublands, and wetlands that includes a 9-mile stretch of the Wallkill River. The refuge was established in 1991 by the U.S. Fish and Wildlife Service.
SAMPLING
Water samples were collected at all five of the sites on the river's main stem and at the nine sites on its eight tributaries (figures 1-3) in the fall of 2004. The five main-stem sites were sampled again in early spring 2005, when discharge was relatively low. In both fall and spring sampling rounds, streamwater samples were collected and pH, dissolved-oxygen concentration, specific conductivity, and flow were measured. During the fall 2004 sampling, bed-sediment samples also were collected. Water samples were analyzed for major ions (calcium, magnesium, sodium, potassium, chloride, and sulfate), nutrients (nitrogen and phosphorus species), organic carbon, and trace elements (arsenic, barium, beryllium, cadmium, chromium, copper, iron, lead, manganese, molybdenum, nickel, uranium, vanadium, and zinc). Bed-sediment samples were analyzed for major ions and trace elements. At two of the sites (WAL-2 and WAL-4), water samples were collected multiple times over a 24-hour period to determine whether arsenic concentrations vary diurnally with temperature and pH.
Because arsenic exists in several forms in the environment, the arsenic speciation was determined in water samples collected at the sites along the main stem of the river. The goal was to determine whether arsenic is present in the oxidized form or the more toxic reduced form. Concentrations of trace elements other than arsenic are being used to develop a chemical "fingerprint" that may aid in identifying the different possible sources of arsenic.
In addition to the streamwater samples, water samples collected from two depths in a flooded mine shaft at the Sterling Hill Mine and Museum in Ogdensburg, N.J., were analyzed. The zinc ores in the Sterling Hill Mine area are similar to the ore extracted from the Franklin Mine, and contain many arsenic-bearing minerals. Zinc ores were mined from the early 1800s until the mine's closure in 1986. The water from the flooded mine shaft was sampled and subsequently analyzed to determine whether minerals in the mine could be leaching arsenic to the ground water and, ultimately, to the river.
Soil cores have been collected from the edge of Franklin Pond to determine the arsenic content of the soils. Temporary piezometers were installed at various locations in the riverbed to study the geochemistry of the water at the ground-water/surface-water interface. During the summer of 2005, samples of ground-water discharge were collected along the river's gaining reaches to determine whether ground water is a major contributor of arsenic to the river system.
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SELECTED REFERENCES
Drake, A.A., Volkert, R.A., Monteverde, D.H., Herman, G.C., Houghton, H.F., Parker, R.A., Dalton, R.F., 1996, Bedrock geologic map of northern New Jersey: U.S. Geological Survey Miscellaneous Investigations Series Map I-2540, 1 plate.
Drake, A.A., and Monteverde, D.H. 1992, Bedrock geologic map of the Branchville quadrangle, Sussex County, New Jersey: U.S. Geological Survey Geological Quadrangle Map GQ-1700, 2 plates.
Dunn, P.J., 1995, Franklin and Sterling Hill, New Jersey: The world's most magnificent mineral deposits: Franklin, N.J., The Franklin-Ogdensburg Mineralogical Society, 7 volumes.
---
Photographs courtesy of Michael J. Deluca and Richard L. Walker of the USGS.
Thanks are given to Susan Colarullo and Kara Watson, also of the USGS, for their assistance with land-use and geologic maps.
----
DISCLAIMER: This webpage contains information about completed or inactive projects from the NJ Water Science Center. It has been created for historical purposes and may be a utility to locate published information. This page should not be considered an authoritative source. You are encouraged to contact the NJ WSC for more current information.
Concentrations of arsenic in four segments (reaches) of the Wallkill River and one segment of the Papakating Creek (a major tributary to the Wallkill River) have been found to exceed the New Jersey surface-water-quality standard of 0.0170 micrograms per liter. As a result, the U.S. Geological Survey (USGS) New Jersey Water Science Center, in cooperation with the New Jersey Department of Environmental Protection (NJDEP), initiated a study to determine the sources of arsenic to the Wallkill River to support the NJDEP in its effort to develop a total maximum daily load (TMDL) for arsenic in the watershed. Possible sources of arsenic in the watershed include geologic materials, pesticides, herbicides, septic-system effluent, industrial discharges, and residual material from historic ore smelting and coal burning. Once arsenic reaches the river, its concentrations are affected by geochemical and physical processes that include adsorption to and desorption from clays, iron-manganese oxides, and organic matter; transport on suspended sediments; and exchange between ground water and surface water.
Wallkill Arsenic Sources
START DATE: 01-AUG-2004
END DATE: 30-SEP-2007
PROJECT NUMBER: 2454BPT
Project Objectives
The overall objective of the project is to identify sources of arsenic to the Wallkill River Watershed. Individual objectives include:
- Determining whether arsenic (and other trace element) concentrations in surface water vary diurnally, in order to select an optimum time for sampling;
- Verifying reaches of the Wallkill River where arsenic concentrations are elevated relative to New Jersey surface-water-quality standards and determining concentrations of associated trace elements;
- Determining potential anthropogenic sources by evaluation of historic and existing land uses;
- # Determining the constituents that have increased (likely from increased development) in stream water over time by analysis of historic water-quality data; Determining the combinations of other elements associated with arsenic that can be used as chemical fingerprints of the three major groups of arsenic sources (geologic, disturbed geologic, and anthropogenic); fingerprinting would start with sediments, and the concept would be extended, if possible, to surface and ground water;
- Determining whether water that has flooded the abandoned Franklin and Sterling Hill mines contains high levels of arsenic leached from the surrounding bedrock, as well as other elements useful in establishing a chemical fingerprint for water in contact with the highly mineralized marble bedrock formation;
- Identifying whether domestic wells in different lithologies are tapping water with elevated concentrations of arsenic and whether ground water is a major source of arsenic in base flow.
Statement of Problem
Arsenic concentrations in water from the Wallkill River and Papakating Creek have been found to exceed the SWQS. Background data needs to be collected to support establishment of TMDLs by NJDEP at five sites on the Wallkill and one on the Papakating. Ground water in wells in the watershed also may tap water with arsenic levels that could exceed the proposed NJDWS. Potential sources of arsenic to water from the Papakating Creek and the Wallkill River include runoff containing residues of land applications of arsenical compounds, arsenic released from direct discharges to the streams, discharge of ground water containing trace elements contributed by geologic materials, and desorption of arsenic from stream sediments derived from soils and geologic materials.
Strategy and Approach
- To characterize potential arsenic sources, GIS coverages of the region’s geology, both bedrock and surficial (including metadata) will be created from the USGS GIS library, or, if needed, acquired. Land-use data, including GIS coverage of agricultural areas and mine locations (including metadata) will be compiled, and historic aerial photography of the watershed will be evaluated.
- To determine diurnal variations in metal concentrations in stream water during active photosynthesis, two ISCO samplers will be deployed during August to obtain trace-element data for stream water from the Wallkill River.
- On the basis of results of bi-hourly samples, optimum sampling time for obtaining the highest concentrations of arsenic in stream water will be determined and samples will be collected at that time for analysis of arsenic and other trace elements, major ions, nutrients, and chemical characteristics such as pH and Eh. Surface-water samples under base-flow conditions will be collected at 6 locations along the Wallkill River and two locations on Papakating Creek.
- To determine trace-element content of bottom sediment samples and upland sources of sediments to the river and creek, samples of stream-bottom sediments will be collected at the same locations as surface-water samples during the first (low-flow) sampling event. Additional stream-bottom sediment samples from the Wallkill River at Lake Mohawk and from Franklin Pond; from tributaries to the Wallkill River at two locations above Ogdensburg, at the Wildcat Brook, above and below Hamburg, at Beaver Run, and above Wantage; from two additional locations on the Papakating Creek and a tributary, above and below Sussex, and farther up the Papakating, near Wykertown, will be collected upstream of road crossings.
- To amplify existing data for the quality of the area’s ground water, particularly that from domestic wells, previously unsampled domestic wells within 0.5 mile of the Papakating Creek and the Wallkill River channels will be sampled—3-4 domestic wells completed in the Quaternary deposits (stratified drift), 3-4 in the area’s clastic rock formations (primarily the Martinsburg Shale), 3-4 completed in the carbonate formations (Allentown Dolomite, Leithsville Formation, Jacksonburg Limestone), 5-6 in the Franklin Marble (if possible), 4-5 in the gneisses with preference given to those closest to the Franklin and Sterling Hill mines.
- To determine relations between arsenic and other chemical constituents in stream water and hydrologic conditions, existing water-quality data will be analyzed for correlations between constituents, for trends with stream flow, for seasonal trends, and, where possible, analyzed for trends in constituent concentrations over time. To develop chemical fingerprints for possible arsenic sources, statistical and graphical techniques used in previous investigations (Barringer et al., 1998; Barringer et al., 2001) will be tailored to the proposed study
---
STUDY OBJECTIVES
The study objectives are to
- identify possible anthropogenic sources of arsenic
- identify geologic sources of arsenic to the streamwater and riverbed sediments
- determine the ground-water contribution of arsenic to the system
- determine the physical, geochemical, and (or) biogeochemical processes that cause variations in arsenic concentrations in the river.
LAND USE
The Wallkill River watershed encompasses about 208 square miles in Sussex County in northwestern New Jersey (figure 1). The watershed is approximately 60 percent forested, 20 percent agricultural, 10 percent urban, and 10 percent wetlands, water, and barren land (figure 2).
GEOLOGY OF THE WALLKILL RIVER BASIN
The river begins at a small dam on Lake Mohawk (figure 3). From Lake Mohawk, it flows north through Franklin Pond (figures 1 and 2), through wetlands, and across the New Jersey-New York border, and ultimately discharges to the Hudson River. Along its course, the river encounters several different geologic substrates (figure 4). It flows through valley-fill glacial deposits that overlie faulted carbonate rocks that consist of dolomite at the headwaters; marble (with some granite and gneiss) in the middle segment; and dolomite again at the extreme northern (downstream) end. The valley fill consists of sediments eroded from the geologic materials. Each of these lithologic units may contribute arsenic to the ground water, which then discharges to the river.
POSSIBLE SOURCES OF ARSENIC TO THE WALLKILL RIVER
Selected locations along the river are shown in figures 5 to 7, which illustrate some of the possible anthropogenic sources and environments that may affect arsenic concentrations in the river. At its origin at Lake Mohawk, the Wallkill River is surrounded by unsewered residential land and a golf course. The outfall of Lake Mohawk is shown in figure 5.
The river flows north from Lake Mohawk to Franklin Pond (figs. 1, 2, and 6). The Franklin area is famous for the now-closed Franklin mines, where substantial quantities of rare zinc-bearing ore minerals were extracted from the early 1800s until 1986. Iron ores were roasted near Franklin Pond (fig. 6) in the 18th and 19th centuries. A short distance (about 1,000 feet) downstream from the pond and bordering the Wallkill River is the Buckwheat Dump, which contains tailings from the zinc-ore mining. Because zinc-bearing ores contain arsenic, sediments derived from weathering of the rock formation, as well as the tailings, are possible sources of arsenic to the river.
About 4.5 miles downstream from Franklin Pond, the river leaves the bedrock part of the basin and widens as it flows over glacial outwash. Before it leaves the State, it flows through the Wallkill River National Wildlife Refuge (fig. 7), a 4,500-acre protected, restricted-access area made up of grasslands, upland forests and shrublands, and wetlands that includes a 9-mile stretch of the Wallkill River. The refuge was established in 1991 by the U.S. Fish and Wildlife Service.
SAMPLING
Water samples were collected at all five of the sites on the river's main stem and at the nine sites on its eight tributaries (figures 1-3) in the fall of 2004. The five main-stem sites were sampled again in early spring 2005, when discharge was relatively low. In both fall and spring sampling rounds, streamwater samples were collected and pH, dissolved-oxygen concentration, specific conductivity, and flow were measured. During the fall 2004 sampling, bed-sediment samples also were collected. Water samples were analyzed for major ions (calcium, magnesium, sodium, potassium, chloride, and sulfate), nutrients (nitrogen and phosphorus species), organic carbon, and trace elements (arsenic, barium, beryllium, cadmium, chromium, copper, iron, lead, manganese, molybdenum, nickel, uranium, vanadium, and zinc). Bed-sediment samples were analyzed for major ions and trace elements. At two of the sites (WAL-2 and WAL-4), water samples were collected multiple times over a 24-hour period to determine whether arsenic concentrations vary diurnally with temperature and pH.
Because arsenic exists in several forms in the environment, the arsenic speciation was determined in water samples collected at the sites along the main stem of the river. The goal was to determine whether arsenic is present in the oxidized form or the more toxic reduced form. Concentrations of trace elements other than arsenic are being used to develop a chemical "fingerprint" that may aid in identifying the different possible sources of arsenic.
In addition to the streamwater samples, water samples collected from two depths in a flooded mine shaft at the Sterling Hill Mine and Museum in Ogdensburg, N.J., were analyzed. The zinc ores in the Sterling Hill Mine area are similar to the ore extracted from the Franklin Mine, and contain many arsenic-bearing minerals. Zinc ores were mined from the early 1800s until the mine's closure in 1986. The water from the flooded mine shaft was sampled and subsequently analyzed to determine whether minerals in the mine could be leaching arsenic to the ground water and, ultimately, to the river.
Soil cores have been collected from the edge of Franklin Pond to determine the arsenic content of the soils. Temporary piezometers were installed at various locations in the riverbed to study the geochemistry of the water at the ground-water/surface-water interface. During the summer of 2005, samples of ground-water discharge were collected along the river's gaining reaches to determine whether ground water is a major contributor of arsenic to the river system.
---
SELECTED REFERENCES
Drake, A.A., Volkert, R.A., Monteverde, D.H., Herman, G.C., Houghton, H.F., Parker, R.A., Dalton, R.F., 1996, Bedrock geologic map of northern New Jersey: U.S. Geological Survey Miscellaneous Investigations Series Map I-2540, 1 plate.
Drake, A.A., and Monteverde, D.H. 1992, Bedrock geologic map of the Branchville quadrangle, Sussex County, New Jersey: U.S. Geological Survey Geological Quadrangle Map GQ-1700, 2 plates.
Dunn, P.J., 1995, Franklin and Sterling Hill, New Jersey: The world's most magnificent mineral deposits: Franklin, N.J., The Franklin-Ogdensburg Mineralogical Society, 7 volumes.
---
Photographs courtesy of Michael J. Deluca and Richard L. Walker of the USGS.
Thanks are given to Susan Colarullo and Kara Watson, also of the USGS, for their assistance with land-use and geologic maps.
----
DISCLAIMER: This webpage contains information about completed or inactive projects from the NJ Water Science Center. It has been created for historical purposes and may be a utility to locate published information. This page should not be considered an authoritative source. You are encouraged to contact the NJ WSC for more current information.