Biological, chemical and physical effects of land use on Limestone
Run, Union County, Pennsylvania
Senior Thesis in Environmental Studies
Bucknell University
April 30, 2004
Student:
Courtney Dohoney
Environmental Studies Program
Class Year: 2004
Address: C-208
Phone: 577-4370
Email: [email protected]
Faculty Advisors:
Dr. Carl Kirby
Department of Geology
Dr. Matthew McTammany
Department of Biology and Environmental Studies Program
Abstract:
Limestone Run, upstream of its confluence with the Susquehanna River, flows through
areas of both agricultural and urban land use. Five locations along the main stream and three
tributaries were chosen to reflect the diversity of land usage adjacent to the stream. Samples and
field data were collected at two other local streams to serve as reference streams for comparison.
Each site was sampled twice in early fall to assess the impact of land use on water quality. An
aquatic macroinvertebrate study was performed once at main branch sites and one reference site.
Published maps including geology, land use, and topography of Limestone Run
watershed were collected in a geographic information system database. The resulting maps were
used to present water quality data to show spatial relationships. The Save Our Streams
Multimetric Index provided a biological assessment of the health at each site on the main stream
based on the benthic macroinvertebrate assemblage. Scores from 0-6 were considered an
“unacceptable ecological condition” and sites with a score of 7-12 were considered an
“acceptable ecological condition”. Only two sites scored high enough to be considered
acceptable, while the other four sites were deemed unacceptable. All sites contained at least
traces of Escherichia coli indicating the presence animal of waste. The concentration of E. coli,
expressed as colonies/100 mL, ranged from 90-1150. Sites that had high E. coli densities
colonies also had the greatest concentrations of algal biomass (range of chlorophyll: undetectable
to 1.259 µg/cm2), likely due to the increased nutrients available in the water from animal waste.
Dissolved oxygen concentrations (5.31 to 12.7 mg/L) were supersaturated, with respect to
atmospheric oxygen, at most sites as a result of high primary production by algae.
Compared to the reference streams, Limestone Run had much higher concentrations of
calcium, iron, magnesium, manganese, nitrate, and sodium. The pH and temperature varied little
ii
among sites (7.17-7.88 and 15.49-20.18°C). Alkalinity was higher in Limestone Run and its
tributaries (average 191 mg/L) than in the control streams (average 53 mg/L) likely due to the
limestone geology of the Limestone Run watershed. Water quality data and biological stream
health scores suggest that every site has at least one area of water quality concern. Thus, this
study illustrates the negative effects that land use, especially agriculture, can have on streams.
iii
Table of Contents
Abstract……………………………………………………………………………………………ii
Table of Contents…………………………………………………………………………………iv
List of Tables……………………………………………………………………………………..vi
List of Figures……………………………………………………………………………………vii
Introduction………………………………………………………………………………………..1
Objectives…………………………………………………………………………………1
Land Use…………………………………………………………………………………..1
Limestone Run…………………………………………………………………………….3
Methods……………………………………………………………………………………………8
Site Descriptions…………………………………………………………………………..8
Field Measurements……………………………………………………………………...11
Laboratory Analysis……………………………………………………………………...12
Results and Discussion…………………………………………………………………………..15
Field Measurements……………………………………………………………………...15
Anions……………………………………………………………………………………21
Cations…………………………………………………………………………………...23
Specific Conductance…………………………………………………………………….27
E. coli…………………………………………………………………………………….30
Turbidity…………………………………………………………………………………32
Organic and Inorganic Deposition……………………………………………………….35
Biological Assessment…………………………………………………………………...39
iv
Acknowledgments………………………………………………………………………………..43
References Cited…………………………………………………………………………………44
Appendix I-A – ActLabs Chemical Analysis 9/20/03…………………………………………...46
Appendix I-B – ActLabs Chemical Analysis 10/18/0303……………………………………….48
Appendix II – VA SOS Stream Quality Survey…………………………………………………50
Appendix III – Photographs…………………………………………………………………...…55
v
List of Tables
Table 1. September 20th and October 18th, 2003 field measurements…………………………..16
Table 2. September 20th and October 18th, 2003 anion concentrations……………………….....21
Table 3. September 20th and October 18th, 2003 cation concentrations………………………...24
Table 4. Mass and percents of inorganic and organic material…………………………….……38
Table 5. Virginia Save Our Streams Biological Multimetric Index Score……………………...40
vi
List of Figures
Figure 1. Topographic map of the Limestone Run watershed with watershed
boundary, and sampling sites…………………………………………………………...…5
Figure 2. Land use map of the Limestone Run watershed with sampling sites…………………..6
Figure 3. Geologic map of the Limestone Run watershed with watershed boundary, and
sampling sites……………………………………………………………………………...7
Figure 4. Alkalinity concentrations for Buffalo Creek, Limestone Run, and Turtle Creek
tributary on October 18, 2003……………………………………………………………19
Figure 5. Specific conductance of Buffalo Creek, Limestone Run, and Turtle Creek
tributary on October 18, 2003……………………………………………………………28
Figure 6. E. coli concentrations of Buffalo Creek, Limestone Run, and Turtle Creek
tributary on November 6, 2003…………………………………………………………..31
Figure 7. Turbidity measurements for Buffalo Creek, Limestone Run, and Turtle
Creek tributary on October18, 2003………………………………………………...…...33
Figure 8. Chlorophyll a concentrations of Buffalo Creek, Limestone Run, and Turtle
Creek tributary on December 12, 2003…………………………………………………..36
vii
INTRODUCTION
Objectives
The purpose of this project was to link water quality and stream health of Limestone Run,
located in Union county, Pennsylvania with land use surrounding the stream. To achieve this
objective, I quantified biological, chemical, and physical characteristics of the stream,
characterized the land use surrounding the stream, determined potential point and non-point
source pollution, and then explored relationships among the water characteristics, pollutants, and
land use.
Land use
Land use can have can have dramatic effects on water quality and health of streams and
rivers. Agriculture is a primary concern when examining land use surrounding a stream as it
poses a variety of risks to the stream, specifically soil erosion, fertilizer and pesticide run-off,
and livestock waste.
Agriculture contributes to soil erosion in a variety of ways. The main source of erosion
comes from farmland where crops are not planted. When farmland is tilled and left without
vegetative ground cover to hold the soil in place, sediment can easily wash into nearby streams
during rain (Ribaudo, 1998). Soil erosion also occurs when farm animals have access to the
stream or stream bank. When large farm animals such as cows, walk along the banks of streams,
they break down the banks and inhibit growth of riparian vegetation, which would ordinarily
hold sediment in place. Degraded stream banks and loss of riparian vegetation allow sediment to
wash into the stream, just as it does when farmland is not covered by crops (Harman et al.,
2000).
1
Excess sediment in streams can be problematic for a variety of reasons. The most visible
effect of sediment is higher turbidity. High turbidity reduces the amount of light available to
algae and aquatic macrophytes for photosynthesis. Algae and aquatic macrophytes are primary
producers and serve as food for macroinvertebrates in the stream, and without this food source,
feeding structure of streams can be disrupted (Hellawell, 1989). Increased sediment in streams
can also alter the substrate of the stream when it is deposited. Changing substrate in streams has
negative impacts on benthic invertebrates that inhabit the stream bottom. For maximum benthic
invertebrate diversity, stream substrate should contain a mix of gravel, pebbles, and cobbles
(Waters, 1995). When large amounts of sediment are introduced to streams, rock and pebble
substrate becomes covered and eventually buried by fine silt. As a result, pebbles and cobbles
that many aquatic invertebrates use as shelter are buried resulting in lower density and diversity
of invertebrates in agricultural (sedimented) streams. The decrease in diversity allows
burrowing, pollution tolerant organisms like oligochaete worms to populate the stream (Waters,
1995).
In addition to sediment, fertilizers, pesticides, and herbicides that were applied to fields
wash into the stream. The introduction of excess nutrients such as nitrogen and phosphorus,
which are commonly found in fertilizers, can cause productivity to increase dramatically in
aquatic ecosystems (Wetzel, 2001). Increased productivity from elevated nutrient concentrations
becomes problematic when algae die and begin to decompose. Decomposition of algae can
lower dissolved oxygen concentrations to levels that are inhospitable to macroinvertebrates and
fish (David and Gentry, 2000). Fertilizers, pesticides and herbicides that wash into streams can
also be problematic for humans if the stream is used as a source of drinking water. Nitrogen, a
common nutrient in fertilizer often finds its way into drinking water. Elevated nitrogen levels in
2
drinking water have recently been linked to Non-Hodgkin’s lymphoma and methemoglobinemia
in humans (David and Gentry, 2000). Studies conducted in Iowa and North Carolina found that
men exposed to common pesticides and herbicides such as, Atrazine and methyl bromide, had a
significantly greater chance of developing prostate cancer (Alavanja et. al, 2003).
In addition to increasing sediment load, livestock access to streams allows animal waste
to enter the stream. Animal waste in streams causes problems for two different reasons. First,
animal waste contributes nutrients directly to streams, which as explained earlier can lead to
eutrophication. Second, animal waste in streams can contain pathogenic bacteria that are
harmful to humans (Ribaudo, 1998). Pathogenic strains of E. coli can cause fevers, nausea, and
even death in humans (Vesilind and Morgan, 2004).
Urban land use affects nearby streams in many ways similar to agriculture. For example,
sediments, chemicals, nutrients, and bacteria can wash into urban streams just as they do in
agricultural settings. The rate of soil erosion in urban environments can be greater than
agricultural settings due largely to the vast amounts of exposed ground at construction sites
(Waters, 1995). Fertilizers and pesticides may not be used in the same quantities in urban as in
agricultural areas, but residential application of these compounds has the same effect once they
enter the stream. Unlike agricultural streams, urban streams tend to have higher concentrations of
metals as a result of increased industrial activity in urban areas. Despite the lack of livestock,
bacteria can be introduced to urban streams through sewage discharge and septic leaching. Both
agricultural and urban influences can severely affect water quality and health in nearby streams.
Limestone Run
The headwaters of Limestone Run, also known as Bull Run, are located in an agricultural
area west of the town of Lewisburg, Pennsylvania (Figure 1). The stream flows through
3
downtown Lewisburg and the Bucknell University campus before emptying into the
Susquehanna River. Six tributaries feed Limestone Run; all are unnamed on the topographic
map except for Miller Run. Limestone Run and its tributaries flow primarily through
agricultural land with some urban development mainly concentrated in the town of Lewisburg
(Figure 2). The tributaries flow through geologic formations similar to Limestone Run and thus
should not differ significantly in mineral composition from Limestone Run (Figure 3).
4
Figure 1. U.S. Geologic Survey Lewisburg, PA 7.5-minute quadrangle topographic map of the
Limestone Run watershed with watershed boundary and sampling sites labeled.
5
Figure 2. Land use map (Myers, Bishop, 1999) of the Limestone Run watershed with sampling
sites marked.
6
Figure 3. Geologic map (Environmental Resources Research Institute, 1994) of the Limestone
Run watershed with watershed boundary and sampling sites labeled.
Water is not the only part of streams potentially affected by land use. Streams can be
channelized and straightened to fit in urban landscapes. Limestone Run has not escaped these
alterations. The downstream portion of Limestone Run that flows through Lewisburg has been
straightened, and stream banks have been covered with rocks. Much of the Limestone Run
watershed has been deforested, in both agricultural and urban settings. Very little of Limestone
7
Run flows through forested area (Figure 2), and the stream appears impacted visually with
frequently turbid water and substrate covered with fine sediment and organic matter.
METHODS
Water samples were collected and biological assessments were carried out at eight
locations to measure health and water quality of Limestone Run and its tributaries. Five
sampling sites were located on the main stem of Limestone Run, and three sites were on
tributaries. Two reference sites, one located on Buffalo Creek and the second located on a
tributary of Turtle Creek, were sampled to provide a comparison to Limestone Run. The
tributary is located in an area that has been less impacted by both agricultural and urban land
uses than Limestone Run. Buffalo Creek is a larger stream than Limestone Run, but faces many
of the same anthropogenic impacts. Water samples were collected two times, the first on
September 20, 2003 and the second on October 18, 2003.
Site descriptions
The choice of sampling sites on the main stem of Limestone Run reflected agricultural
and urban land uses surrounding the stream from the headwaters to the Susquehanna River. The
main stem sites are numbered from 1 to 5 with numbers increasing downstream. Tributary sites
were assigned letters from A to C, with the most upstream tributary site labeled A and the most
downstream tributary site labeled C. Site 1 on the main stem of Limestone Run was located near
the headwaters on Hoffa Mill Road. This site is surrounded by active farms with corn crops and
is immediately downstream of a field where livestock have direct access to the headwaters,
although Site 1 itself was shaded by a small wooded area. Site 2 was approximately 3 km
8
downstream of Site 1 and is located on PA Route 45. Site 2 was also primarily surrounded by
agriculture, mainly wheat and corn crops. Site 3 is located immediately upstream of Fairground
Road and the town of Lewisburg. Sampling the stream directly prior to its entering the town of
Lewisburg allowed the agricultural influence on Limestone Run to be assessed before urban
influences affect the stream. Sites 4 and 5 on the main branch of Limestone Run were located in
Lewisburg to explore the influences of the town on Limestone Run. Site 4 was adjacent to the
parking lot of Peking Garden Restaurant, which is located just upstream of U.S. Route 15. Site 5
was located on the Bucknell University campus approximately 500 meters upstream of
Limestone Run’s confluence with the Susquehanna River.
In addition to these five sites on the main stem, I sampled three sites on tributaries of
Limestone Run. Site A was located on the most upstream tributary of Limestone Run near the
intersection of Smoketown Road and Fairground Road. This site was immediately surrounded
by woods, but its headwaters originate in agricultural fields and pastures where livestock have
access to the water. Site B was located on a middle tributary of Limestone Run near Township
Road 456. Similar to the other sites, B was almost entirely surrounded by agriculture. Site C was
located on Miller Run behind the parking lot of Hunt Hall on the Bucknell University campus.
The headwaters of Miller Run are on the Bucknell University golf course, and Miller Run flows
primarily through urban areas.
Two reference sites were sampled to provide typical characteristics of less impacted by
land use, but still in the same geographic area. The reference site that closely compares to the
size of Limestone Run is a tributary of Turtle Creek. The tributary of Turtle Creek flows through
wooded areas, and thus provides a reference for what water quality of an unimpacted stream
found in central Pennsylvania should be. This Turtle Creek tributary sampling site was located
9
on Furnace Road, east of Stein Lane. Buffalo Creek is much larger in size than Limestone Run,
but it provided another comparison for stream characteristics in the same geographic area. The
sampling site on Buffalo Creek was located near PA Route 192, just east of the village of
Cowan.
Sampling sites were located in four geologic formations. Sites 2, 3, 4, 5, A, B, and C are
all located in the Devonian and Silurian age Keyser and Tonoloway formations (Dskt). These
formations are primarily composed of limestone. Site 1 is positioned in the Silurian age Wills
Creek formation (Swc) which is largely made up of calcareous shale. The Buffalo Creek
sampling site is found in the Devonian age Onondaga and Old Port formations (Doo), which, like
the Wills Creek formation, consists mainly of calcareous shale. Water reaching the Turtle Creek
tributary sampling site flows through Silurian age Clinton Group formations (Sc) composed
mainly of shale and the Bloomsburg and Mifflintown formations (Sbm) which are also largely
comprised of shale (Pennsylvania Geological Society, 2001).
Land use at the sampling sites progresses from agricultural to urban as Limestone Run
flows downstream. Sites 1, 2, and B were surrounded entirely by agriculture. Sampling site A
was located in a forested area, but the headwaters of the stream begin in an agricultural setting
not far from the sampling site. Site 3 was located on the fringe of the town of Lewisburg and
could be classified as either urban or agricultural. Site 4 was the only site located in an entirely
urban area. Sites 5 and C were located in an urban setting (the town of Lewisburg) but were
situated in areas where there was a foliage canopy.
10
Field measurements
Dissolved oxygen (DO), pH, specific conductance (SC), and temperature were measured
at all ten sites on both sampling dates using a YSI multimeter. Based on temperature and DO
concentration, the multimeter calculated the dissolved oxygen percent saturation (DO%). The
multimeter was calibrated with pH 4 and 7 buffers at the first site visited each day. I checked pH
on the multimeter with the pH 7 buffer numerous times throughout the day to ensure that the
meter remained properly calibrated. Turbidity was measured at all sites using a Hach™ 2100P
turbidimeter. The turbidimeter was calibrated at the beginning of the sampling session and was
checked periodically using a blank sample to ensure that the meter remained properly calibrated.
Alkalinity concentrations were also determined in the field. I collected 25 mL of stream
water from each site and determined alkalinity using a Hach™ colorimetric titration kit with a
digital titrator. Titrations were done according to Standard Methods (Eaton et al., 1995), except
that a phenolphthalein indicator, which was not used. Phenolphthalein is used as an indicator
when pH levels are greater than 8.3 and bromcresol green-methyl red indicator is used when the
pH is between 4.3 and 8.3 (Ashland Specialty Chemical Co., 2004). Based on pre-existing
knowledge of the area, it was estimated that the pH would be less than 8.3, and thus the
phenolphthalein titration was not performed. This method resulted in alkalinity being reported in
mg CaCO3/L, this was converted mathematically to mg/L as HCO3-.
I conducted an aquatic macroinvertebrate assessment on main stem sites of Limestone
Run and the Turtle Creek tributary reference site because Limestone Run tributary sites were too
narrow and shallow to sample effectively and consistently. The protocol for this survey was
based on the Izaak Walton League of America’s Save Our Streams (SOS) multimetric index,
which was developed for the state of Virginia (Appendix II for the SOS protocol including the
11
index and tally sheet) (VASOS, 2003). To conduct this analysis, I selected a riffle area at each
sampling site and placed a square kick-net (1m2, 353-μm mesh) perpendicular to the water flow.
The bottom of the net was anchored with rocks to prevent macroinvertebrates from escaping.
Once the net was in place, I disrupted the substrate upstream of the net by digging into the
sediment with my feet and hand-rubbing rocks and stones to free any attached organisms.
Disturbance of the substrate lasted for 30 seconds, at which time the net was removed from the
stream. The net was then placed on a flat surface, and I removed macroinvertebrates from the
net and placed them into containers. If the number of organisms in the first net was less than
200, I collected another 30-second sample and repeated the sorting. Once the total number of
organisms reached 200 or four nets were collected, the organisms were identified using drawings
found on the SOS tally sheet and enumerated. Individual metrics were calculated to give the
percent of beetles, common netspinners, lunged snails, mayflies, stoneflies, caddisflies, noninsects, and pollution tolerant. Percentages for each metric were assigned a value of 0, 1, or 2
based on ranges of each metric from polluted and non-polluted streams, with low scores
indicating poor water conditions in the stream. The multimetric index score at each site was
calculated by adding the scores of each individual metric. Scores between 0 and 6 indicate that
the site represented an unacceptable ecological condition in the stream, and scores between 7 and
12 indicate that the site was in an acceptable ecological condition.
Laboratory Analysis
Water samples for anion analysis were collected as grab samples and filtered (0.45 µm)
into a new 30-mL high density polyethylene (HDPE) bottle. Samples were iced in the field and
then refrigerated until analysis in the Bucknell University Environmental lab. Anion
12
concentrations were determined using a high pressure liquid chromatograph (HPLC) with an
estimated detection limit of approximately 0.1 milligram per liter (mg/L).
I also collected samples from each of the main branch sites and both reference sites for
determination of an additional 67 elements. I collected a 60-mL grab water sample and filtered
(0.45 µm) the stream water into a HDPE bottle. Each sample was then fixed with nitric acid to
lower the pH of the sample to approximately 2. Fixed samples were then shipped to Activation
Laboratories in Ancaster, Ontario for testing.
Two Escherichia coli tests were performed for each sample site, the first to determine
whether there was E. coli present and the second to measure the concentration of the bacteria.
First, I collected water from each site and tested for the presence of E. coli using a drinking water
bacteriological kit (Carolina Biological Supply Company, 1987). To determine the
concentration of fecal coliforms, I filtered 10 mL of water from each site onto a 0.45-µm filter.
This filter was then placed on an eosin methylene blue (EMB) agar plate. The agar plate was
then incubated at 37° C for 24 hours. After the incubation period, I counted dark red colonies
growing on the filter. This colony count was then multiplied by ten to convert to E. coli colonies
per 100 mL of water.
Chlorophyll a (chl-a) concentrations were measured to determine algal biomass at each
sample site using a method adapted from Steinman and Lamberti (1996). To measure chl-a,
three unglazed, 2.8 cm x 2.75 cm ceramic tiles, were placed at each site for a period of 10 days.
After 10 days, I collected the tiles and removed algae by scraping each tile with a hard bristle
brush and rinsing with distilled water. These samples were filtered onto glass fiber filters (1-μm
pore size), and placed in 10 mL of 90% basic acetone to extract chlorophyll for 3 hours. After
extraction, 6 mL of the chl-a extract was transferred into a 1 cm cuvette. Absorbance was
13
measured using a spectrophotometer at 750 nm and 664 nm. To account for the presence of
pheophytin, a result of chlorophyll breakdown, samples were acidified with 0.1 mL of 0.1 N
HCl, and absorbance of the acidified samples was measured at 750 nm and 665 nm. Absorbance
was measured at 750 nm to correct for absorbance of light by dissolved and suspended particles.
Chl-a biomass was determined from these absorbance values using the following equation:
Chlorophyll a (µg/cm2) = 26.7*(664b-665a)*Vext
___________________________________________
SA*L
where:
26.7 is the absorbance correction for chlorophyll a
664b = absorbance of sample at 664 nm – absorbance of sample at 750 nm, before
acidification
665a = absorbance of sample at 665 nm – absorbance of sample at 750 nm, after
acidification
Vext = volume of 90% basic acetone used in extraction (mL)
SA = tile surface area (cm2)
L = path length of cuvette (cm)
In addition to algal growth, sediments can be deposited on the stream bottom. To assess
deposition of inorganic material, I placed 3 tiles at each sampling site for 10 days. After 10 days,
tiles were collected, scraped to remove material, and rinsed with distilled water into a container.
Samples from each tile were then filtered onto previously weighed glass fiber filters (1.0 μm
pore size) and dried at 50° C. I weighed each filter to determine total dry weight. Filters were
then placed in an oven at 550° C for 1 hour to volatilize all organic components and leave only
the inorganic material of each sample. After ashing, I re-weighed each filter to determine mass
of inorganic material remained and calculated the mass of organic material present before ashing.
From these weights, I calculated the percent of organic and inorganic material on the tile
surfaces.
To assess the types of minerals present in the fine stream sediment, I performed an x-ray
diffraction analysis from one site. A rock was selected from the stream bed and scrubbed in the
14
lab with a hard bristle brush and distilled water. The sample was dried at 40° C and acetone
slurry mounted on a low background silicon plate. On January 31, 2004, a 4 to 80° 2θ x-ray
analysis was conducted using a Philips X’Pert diffractometer set at 40 mA and 45 kV. Peaks
produced from the x-ray diffraction were then matched to a library of existing minerals to
provide an idea of the mineral constituents of sediment in Limestone Run.
RESULTS AND DISCUSSION
Field Parameters
Dissolved oxygen (DO) measurements ranged from 5.3 to 10.9 mg/L on September 20,
2003 and from 9.3 to 12.7 mg/L on October 18, 2003 (Table 1). DO concentrations at the
reference sites were similar to concentrations found at Limestone Run sampling sites. DO
concentrations at the Turtle Creek tributary site on the two sampling dates were 8.8 and 11.1
mg/L respectively. DO concentration at Buffalo Creek on 10/18/03 was 12.4 mg/L. Site 1 had
the lowest concentrations on both of these dates likely due to its proximity to the headwaters of
the stream. The headwaters of Limestone Run come from an underground source (Picture A in
Appendix III); underground water sources tend to have lower DO concentrations than surface
water because they cannot diffuse oxygen from the air and there is often more decaying organic
material present in the water which depletes existing oxygen (Wetzel, 2001). This site also
allowed cows’ access to the stream; their excrement could introduce decaying organic material to
the stream at an aboveground site. The remaining sampling sites were located far enough
downstream that oxygen was able to diffuse into the water and increase the DO concentrations.
Site 2 contained the greatest concentration of DO on both sampling dates. The greatest DO
concentration at Site 2 is likely due to a much greater density of aquatic macrophytes (Picture B
15
in Appendix III). With a greater number of macrophytes in the water, more photosynthesis can
take place to produce oxygen in the water, which increases DO.
Table 1. Field measurements recorded on September 20, 2003 and October 18, 2003.
Field Parameters 9/20/2003
DO% DO
Site 1 59
5.3
Site 2 116 10.9
Site 3 101
9.8
Site 4 104 10.1
Site 5 98
9.6
Site A 84
8.4
Site B 91
8.8
Site C 99
9.3
Turtle Ck. Trib. 95
8.8
pH
7.6
7.6
7.6
7.6
7.3
7.2
7.7
7.9
7.8
T
20.2
17.9
16.8
16.8
16.1
15.5
17.3
18.4
18.9
S.C. Turbidity TDS Alk. HCO3
0.446
4.2
0.290
203
0.598
11.9
0.388
252
0.566
9.1
0.368
135
0.573
8.2
0.372
134
0.559
8.6
0.364
132
0.490
10.2
0.318
113
0.581
8.8
0.378
262
0.429
6.3
0.279
97
0.123
6.3
0.080
36
-
pH
7.6
7.7
7.5
7.5
7.2
7.6
7.7
7.5
7.9
7.9
T
12.3
10.1
10.3
9.9
9.5
10.7
11.8
9.8
10.6
9.0
S.C. Turbidity TDS Alk. HCO3
0.444
6.3
0.289
197
0.583
25.3
0.380
246
0.584
11.6
0.379
228
0.586
12.6
0.381
231
0.581
6.6
226
0.494
6.2
0.321
187
0.581
6.1
0.378
250
0.403
6.0
0.262
167
0.127
2.7
0.083
37
0.220
2.9
0.143
85
-
Field Parameters 10/18/2003
Site 1
Site 2
Site 3
Site 4
Site 5
Site A
Site B
Site C
Turtle Ck. Trib.
Buffalo Creek
DO%
87
111
107
106
111
95
102
111
100
108
DO
9.3
12.5
12.0
12.0
12.7
10.6
11.0
12.5
11.1
12.4
DO% represents the percent of dissolved oxygen saturation with respect to atmospheric O2.
DO is the dissolved oxygen in milligrams per liter (mg/L).
T is the temperature in degrees celsius (° C).
S.C. is the specific conductance measured in milliSiemens per centimeter (mS/cm).
Turbidity is measured in nephelometric turbidity units (ntu).
TDS is total dissolved solids calculated in grams per liter (g/L).
Alk. HCO3- is alkalinity measured as milligrams per liter (mg/L) of bicarbonate (HCO3-), +/- 5%.
Temperature varied little among Limestone Run and reference sites on the same day
ranging from 15.5 to 20.2°C on 9/20/03 and 9.5 to 12.3°C on 10/18/03 (Table 1). However,
noticeable differences occurred between sampling dates. Temperatures were between 4 and 8°C
16
cooler on 10/18/03 than on 9/20/03. The differences in water temperature can be attributed to
the colder air temperatures that result from sampling later in the fall. In late summer, when the
first sampling occurred, stream temperatures were at their peak as a result of being heated all
summer by the air. By mid October, air temperatures had started to decrease and as a result so
had stream temperatures
Measuring the DO and temperature at sampling sites allows for the DO% to be
calculated. DO% represents the percent of saturation of dissolved oxygen at a specific
temperature. When the DO% is greater than 100%, the water is said to be “supersaturated” with
oxygen. The DO% on the first sampling date ranged from 59 to 116%, with Sites 2, 3, and 4
having supersaturated DO concentrations (Table 1). On the second sampling date, sites ranged
in DO% from 87 to 111%, with 8 of the 10 sites beyond supersaturated levels. Reference sites
were comparable to Limestone Run sites with regard to DO%, with values near the middle of the
Limestone Run ranges. The lowest DO% on both sampling days was at Site 1, and the highest
DO% on both dates was measured at Site 2. As explained earlier with regard to DO
concentrations, the two extremes of DO% are related to the source of the water at Site 1 and the
presence of aquatic macrophytes photosynthesizing and producing oxygen at Site 2.
The pH of Limestone Run and reference sites were very consistent between sampling
dates and varied little among sites. pH values ranged from 7.2 to 7.9 on both sampling dates
(Table 1). The Buffalo Creek and Turtle Creek tributary sites were at the higher end of the pH
range, measuring 7.9 and 7.8 respectively. The pH measured at every site was within a healthy
range for plant and animal life. The pH of rainwater in Pennsylvania averages around 4.15
(Drohan et al., 1996), thus to maintain a pH between 7.2 and 7.9 in Limestone Run, alkalinity in
this area must be high to maintain a nearly neutral stream pH.
17
Alkalinity is a measurement of the ability of a stream to buffer against drastic changes in
pH from an influx of H+ ions to the stream. Buffering occurs when there are enough acid
neutralizing ions in the water to react with the excess H+. The most common buffering ion in
natural waters with pH below 8.3 is carbonate (HCO32-), and one of the most abundant minerals
that releases HCO3- is calcite (CaCO3). When calcite dissolves in water, CO32- and HCO3(bicarbonate) ions are freed and attach to the excess H+ or OH- ions. Binding these ions together
results in a compound of HCO3- and a neutral pH near 7.
CO32- + CaCO3 → 2HCO3- + Ca+
Alkalinity from this reaction can be measured by titrating water samples with sulfuric acid
(H2SO4) and determining the amount of HCO3- or CaCO3 necessary to neutralize the known
amount of acid (Abandoned Mine Reclamation Clearinghouse, 2004).
Alkalinity concentrations reflected a major difference between sites in the Limestone Run
watershed and the two reference streams (Table 1). Limestone Run sites ranged in concentration
from 97 to 262 mg/L of HCO3- on 9/20/03 and from 167 to 250 mg/L of HCO3- on 10/18/03.
Alkalinity at Buffalo Creek and Turtle Creek tributary sites was much lower than Limestone Run
sites. The Turtle Creek tributary had concentrations of 36 and 37 mg/L of HCO3- on the two
sampling dates, respectively, and Buffalo Creek had an alkalinity concentration of 85 mg/L of
HCO3- on 10/18/03. Figure 5 shows the difference in alkalinity values between the Limestone
Run sites and reference sites very clearly.
18
Figure 4. Alkalinity concentrations in mg/L of HCO3- on October 18, 2003 with sampling site
dots scaled to alkalinity concentrations overlaid on a geologic map (Environmental Resources
Research Institute, 1994).
The difference in alkalinity among sites is attributable to the geology of the sampling
sites. Sites 2, 3, 4, 5, A, B, and C were all found in the Keyser and Tonoloway formation. This
formation is composed primarily of limestone: a major component of limestone is calcite. As the
stream flows through the limestone stream bed bicarbonate ions from the calcite are released,
resulting in high alkalinity measurements for sampling sites in the limestone formation. Site 1 is
19
located in the Wills Creek formation, and is predominately composed of calcareous shale.
Calcareous shale, like limestone, contains calcite and thus can contribute a large amount of
alkalinity to a stream. However, the amount of carbonate and bicarbonate ions that can be
released from calcareous shale is much less than limestone, making the stream alkalinity in
calcareous shale formations less than that which is characteristic of limestone areas. Before
flowing through the Onondaga and Old Port formation where the sampling site is, Buffalo Creek
runs through the Keyser and Tonoloway formation. This formation contributes substantial
alkalinity to Limestone Run, as exhibited by Sites 2, 3, 4, 5, A, B, and C. Even though the
geology of the Buffalo Creek streambed becomes calcareous shale as it flows into the Onondaga
and Old Port formation, much of the alkalinity contributed by the limestone is still present at the
Buffalo Creek sampling site. The Turtle Creek tributary is located in Bloomsburg and
Mifflintown formations where the geology is very unlike other sample sites. Shale is the main
component of the Bloomsburg and Mifflintown formation and contains very little calcite.
Because there is little calcite, there are fewer- HCO3- ions found in the water. As a result of
fewer carbonate and bicarbonate ions in solution, alkalinity concentrations at the Turtle Creek
tributary site were considerably lower than all other sites. Compared to the Turtle Creek
tributary on 9/20/03, alkalinity at Site B was seven times greater. Despite a much lower
concentration of alkalinity, the Turtle Creek tributary maintained a pH similar to that of all the
other sites. Thus, alkalinity does not need to be as high as Limestone Run site to effectively
prevent stream acidification.
20
Anions
Anion concentrations from Limestone Run showed variations between dates as well as
sites (Table 2). Nitrate concentrations ranged from 1.2 to 6.2 mg/L on 9/20/03 and from 2.5 to
7.6 mg/L on 10/18/03. Buffalo Creek and Turtle Creek tributary sites had lower concentrations
of nitrate, ranging from 0.4 mg/L at the Turtle Creek tributary on both sampling dates, to 1.6
mg/L at Buffalo Creek on 10/18/03. On both 9/20/03 and 10/18/03 nitrate concentrations were 3
to 10 times greater at each Limestone Run site, than they were at the Turtle Creek tributary
reference site.
Table 2. Anion concentrations of samples collected on September 20, 2003 and October 18,
2003.
9/20/2003
10/18/2003
Site Nitrate Phosphate Chloride Sulfate Nitrate Phosphate Chloride Sulfate
1 1.2
0.3
8.2
21.8
5.0
0.1
7.5
25.5
2 6.2
0.0
19.5
33.5
7.6
0.0
20.0
37.3
3 4.4
0.0
20.0
36.9
5.4
0.0
20.3
40.7
4 3.9
0.0
21.4
38.3
5.0
0.0
21.5
42.1
5 3.6
0.0
21.5
40.2
4.9
0.0
21.5
41.8
A 3.5
0.0
17.3
34.4
3.9
0.0
17.5
36.2
B 4.6
0.0
11.3
36.4
4.9
0.0
10.5
39.4
C 2.6
0.0
17.5
31.2
2.5
0.0
18.0
29.3
TCT 0.4
0.0
7.7
10.4
0.4
0.0
7.8
10.7
BC n.d.
n.d.
n.d.
n.d.
1.6
0.0
7.1
13.9
All concentrations expressed in milligrams per liter (mg/L), n.d. means concentrations were not determined
Nitrogen is a common component in agricultural fertilizers. As a result of runoff, rain
washes nitrogen from the field into streams. Limestone Run flows primarily through agricultural
land, which explains elevated nitrate concentrations in Limestone Run. The Turtle Creek
tributary site was not exposed to as much agricultural land and resulting runoff as Limestone
Run which explained the lower nitrate concentrations found in this reference site. The Buffalo
Creek watershed contains a considerable amount of agricultural land however, unlike Limestone
21
Run, agriculture is not the only land use in the Buffalo Creek watershed. Buffalo Creek flows
through large areas of forested land, especially in riparian zones. So although agriculture does
contribute to nitrate concentrations in Buffalo Creek, forested riparian zones help to combat
these effects.
Phosphate was undetectable at all Limestone Run and reference sites, with the exception
of Site 1 (Table 2). Phosphate concentrations at Site 1 were barely detectable measuring 0.3 and
0.1 mg/L on the two sampling dates respectively. Phosphorus, along with nitrogen, is a common
component in fertilizer. Phosphorus washes into streams from nearby crop land and results in
unnaturally high phosphate concentrations in water as the phosphorus oxidizes. Site 1 was the
only site where phosphate was present in concentrations high enough to be detectable. The
presence of phosphate at only the most upstream site in a stream is not surprising. Phosphorus is
often the limiting nutrient in a stream, meaning that of all nutrients that are necessary for plant
and algal growth, phosphorus is the least available. Because plants and algae are often starved
for phosphorus, when it is available they absorb it very quickly, and leave very little in the water.
This is most likely the case at Site 1, where algae and plants in the water at this site absorb all the
phosphorus before it can be transported downstream.
Chloride concentrations in Limestone Run were nearly identical at each site between the
two sampling dates. The greatest difference in concentration between the two dates was at Site
B where chloride concentrations decreased from 11.3 to 10.5 mg/L, a decrease of only 0.8 mg/L.
Concentration of chloride at Limestone Run sites ranged from 8.2 to 21.5 mg/L on 9/20/03 and
from 7.5 to 21.5 mg/L on 10/18/03. Chloride concentrations were noticeably lower at Buffalo
Creek and the Turtle Creek reference sites. The Turtle Creek tributary had chloride
concentrations of 7.7 and 7.8 mg/L and Buffalo Creek had an even lower concentration of 7.1
22
mg/L on 10/18/03. Similar to Limestone Run sites, chloride concentrations were very stable at
the Turtle Creek tributary site, increasing by only 0.1 mg/L between the two sampling dates.
Chloride may have been introduced to the stream as the result of roadway salting that
occurred in the winter. The snow dissolved the salt (NaCl), and released sodium and chloride
ions into the environment. These ions then washed into Limestone Run when the snow melted
(Koryak et al., 2001). The impact of roadway salting during the winter would also explain why
chloride concentrations were much lower at Buffalo Creek, Sites 1, B, the Turtle Creek tributary,
than other Limestone Run sites. The four sites with low chloride concentrations were located
near roads that receive appreciably less vehicle traffic than roads near the remaining where the
Limestone Run sites. Because these roads received less traffic it is likely that they were not
salted this winter and therefore salt runoff did not affect these sites.
Sulfate concentrations were 2 to 4 times higher at Limestone Run sites than at the Turtle
Creek tributary reference site (Table 2). Limestone Run sulfate concentrations ranged from 21.8
to 40.2 mg/L on 9/20/03 and from 25.5 to 42.1 mg/L on 10/18/03 while the Turtle Creek
tributary had sulfate concentrations of just 10.4 and 10.7 mg/L. Buffalo Creek had sulfate
concentrations similar to Turtle Creek, measuring 13.9 mg/L on 10/18/03. There was little
variation of sulfate concentrations between sampling dates. The biggest change in sulfate
concentration between sampling dates occurred at Sites 2 and 3, where concentrations both
increased by 3.8 mg/L.
Cations
Cation concentrations (Table 3) revealed many elements that were present in measurable
quantities (Full cation analysis in Appendix I). Sodium concentrations of main stem Limestone
Run sites ranged from 2.66 to 16.30 mg/L on 9/20/03 and from 3.47 to 7.93 mg/L on 10/18/03.
23
The range of sodium concentrations may not actually be as large as what was reported. There is
a large discrepancy between two samples taken at Site 3 on 9/20/03. The sodium concentration
at Site 3 was reported as 16.300 mg/L, however a duplicate sample taken at that same site had a
reported concentration of only 6.150 mg/L, a difference of more than 10.150 mg/L. The sodium
concentration at Site 3 on 10/18/03 was determined to be 7.130 mg/L, a concentration much
closer to the duplicate value and consequently making the 16.300 mg/L concentration very
suspect. Both reference sites had sodium concentrations comparable to Limestone Run sites.
Sodium concentrations at the Turtle Creek tributary were measured at 4.030 and 5.570 mg/L and
Buffalo Creek had a sodium concentration of 3.750 mg/L on 10/18/03.
Table 3. Selected cation concentrations in μg/L, of samples collected on September 20, 2003
and October 18, 2003.
9/20/2003
Site
1
1 Rep.
2
3
3 Dup.
4
5
TCT
Na
2.66
2.59
5.50
16.30
6.15
6.93
7.20
4.03
Mg
18.30
17.90
23.20
21.30
21.90
21.20
19.20
3.23
K
4.19
4.00
2.34
1.87
2.00
2.23
2.30
1.65
Ca
Al Mn Fe
49.30 13 340 264
48.20 13 341 269
64.40 149 28.8 304
60.60 11 35.5 115
61.20 5 37.4 105
62.40 5 37.7 112
59.90 9 29.3 99.8
12.20 13 27.3 52.8
Cu
0.9
1.0
1.1
1.4
1.0
0.9
1.1
0.9
Zn
Cd
Pb
3.1 0.02 0.06
3.2 0.02 0.06
3.7 0.06 0.24
1.6 0.01 0.05
1.8 0.01 0.03
2.4 0.03 0.06
0.6 -0.01 0.02
2.5 -0.01 0.05
10/18/2003
Site
1
2
3
4
5
5 Dup.
TCT
BC
Na
3.47
6.98
7.13
7.73
7.93
7.47
5.57
3.75
Mg
19.20
26.50
24.30
24.80
25.10
24.10
3.96
6.73
K
2.5
1.67
1.43
1.56
1.65
1.68
1.61
1.24
Ca
48.40
67.10
66.20
69.80
69.90
66.60
13.30
24.10
Cu
0.7
0.5
0.4
0.6
1.6
2.4
0.4
0.5
Zn
2.1
0.5
1.1
1.1
5.6
7.5
0.8
0.9
Al
15
14
8
9
9
7
11
29
Mn
71.2
53.3
29.9
40.1
24.9
27.2
16.4
21.8
Fe
135
103
103
115
106
119
61
140
Cd
0.01
-0.01
-0.01
-0.01
0.02
0.06
-0.01
0.01
Pb
0.04
0.02
-0.01
-0.01
0.02
0.10
0.02
0.04
Negative values indicate that the concentration was below the detection limit.
Sodium, magnesium, potassium, and calcium expressed in mg/L
24
As with chloride, much of the sodium found in the stream most likely resulted from salt
runoff when adjacent roads were salted during the winter. Sodium concentrations peaked at the
same sites that chloride concentrations did. Site 5 had the greatest concentration of sodium as
well as chloride on both sampling dates. Site 1 had the lowest sodium concentrations and the
second lowest chloride concentrations on both sampling dates. Looking at the relationship
between concentrations of the two components of road salt, sodium and chloride, gives a strong
indication that these two elements were being introduced to the stream together, most likely as
the result of salt runoff.
Magnesium concentrations at the main stem sites on Limestone Run were an order of
magnitude larger than those found in the two reference sites (Table 3). Limestone Run sites
ranged in magnesium concentration from 17.900 to 26.500 mg/L where Buffalo Creek and Turtle
Creek tributary sites only had magnesium concentrations between 3.230 and 6.730 mg/L.
Aluminum concentrations were very small in both Limestone Run and reference streams
(Table 3). With the exception of Site 2 on 9/20/03 when aluminum concentration was measured
at 0.149 mg/L, aluminum concentration ranged from 0.005 to 0.029 mg/L.
Limestone Run and reference sites did not have noteworthy differences with regard to
potassium concentrations. Among all sites, potassium ranged in concentration from 1.650 to
4.820 mg/L on 9/20/03 and from 1.240 to 2.500 mg/L on 10/18/03.
Calcium concentrations varied drastically between Limestone Run and Buffalo Creek and
Turtle Creek tributary sites but had little variation (Table 3). Over both dates, Limestone Run
sites ranged in calcium concentration from 48.200 to 69.900 mg/L, but Turtle Creek tributary
and Buffalo Creek sites had substantially lower concentrations ranging from 12.200 to 24.100
mg/L.
25
The presence of high concentrations of calcium in the streams was most likely linked to
the elevated levels of alkalinity. As mentioned earlier, alkalinity often results from the
weathering of calcite. Calcite (CaCO3) is composed of carbonate and calcium. Comparing
calcium concentrations to alkalinity levels reveals a strong positive relationship between the two
measurements (i.e., sites with high calcium also had high alkalinity). For instance, on 9/20/03,
Site 2 had the greatest concentration of alkalinity of all main stem sites (252 mg/L of HCO3), and
it also recorded the highest concentration of calcium (64.400 mg/L). The same day that Site 2
recorded the greatest alkalinity and calcium concentrations, the Turtle Creek tributary site had
the lowest alkalinity (36 mg/L of HCO3-) and calcium (12.200 mg/L) concentrations.
Stoichiometry at the Turtle Creek tributary site reveals just how closely related the number of
millimoles of Ca and HCO3 are. The chemical reaction that occurs when calcite is exposed to
water and carbon dioxide is shown below:
CaCO3 + CO2 +H2O → Ca2+ + 2HCO3Concentrations of HCO3 at Turtle Creek resulted in 0.6 mmol HCO3/L. Ca was shown to have
0.3 mmol Ca/L. The balanced equation shows that if Ca2+ and 2HCO3- are related that there
should be twice as many moles of Ca2+ as HCO3, which is proven in the Turtle Creek tributary
example.
Iron concentrations at Limestone Run sites and reference sites were consistent between
the two sampling dates with the exception of Sites 1 and 2 (Table 3). Iron concentrations on
9/20/03 at Site 1 were recorded as 0.264 and 0.269 mg/L and 0.304 mg/L at Site 2. Iron
concentrations on 9/20/03 were twice as large as concentrations measured on 10/18/03 (0.135
and 0.103 mg/L respectively). Excluding Sites 1 and 2, iron concentrations were consistent
between dates and were very similar among sites. Limestone Run main stem sites ranged from
26
0.100 to 0.115 mg/L on 9/20/03 and from 0.106 to 0.119 mg/L on 10/18/03. Turtle Creek
tributary iron concentrations were roughly half as large as Limestone Run sites, measuring 0.053
and 0.061 mg/L on the two sampling dates respectively.
Copper, zinc, lead, and cadmium were found in low concentrations at a variety of sites
(Table 3). There was essentially no difference between Limestone Run sites and reference sites
with regard to concentrations of these metals. Of the metals found in small quantities,
concentrations of zinc were the highest, ranging from 0.0005 to 0.0037 mg/L. Copper
concentrations were slightly lower than zinc, they ranged from 0.0004 - 0.0024 mg/L. Lead was
present in very small concentrations, ranging from 0.00002 - 0.00024 mg/L. On 10/18/03 lead
was not even detectable at Sites 3 and 4. Cadmium was the least detectable metal, ranging from
a concentration of 0.00001 - 0.00006 mg/L among Limestone Run sites. Concentrations of
cadmium were so low on 10/18/03 that four sites had concentrations below the detection limit of
the instrument.
Specific Conductance
Individual cations such as sodium, magnesium, aluminum, potassium, calcium, and iron
in measurable concentrations not only affect streams but also, influence the specific conductance
of streams when combined with anions and alkalinity (Murphy, 2002). Specific conductance
among Limestone Run sites varied little between sampling dates. SC values ranged from 0.429
mS/cm at Site C to 0.598 mS/cm at Site 2 on 9/20/03 and from 0.403 mS/cm at Site C to 0.586
mS/cm at Site 4 on 10/18/03. Reference sites had much lower SC than Limestone Run sites.
The Turtle Creek tributary site had SC values of 0.123 mS/cm and 0.127 mS/cm on 9/20/03 and
10/18/03, respectively. Specific conductance in Buffalo Creek was 0.220 mS/cm on 10/18/03,
which was slightly higher than the Turtle Creek measurement (Figure 6).
27
Figure 5. Specific conductance, measured in mS/cm, on October 18, 2003 with sampling site
dots scaled to specific conductance measurements.
Specific conductance measures the ability of water to conduct an electric current. For
conductance to occur, positive and negative ions must be dissolved in the water. The presence or
28
absence of ions can therefore be greatly affected by the geology of an area. In areas that are
composed of rocks with calcite, such as limestone or calcareous shale, ions are easily dissolved
into solution. The ease in which ions are dissolved increases the number of ions and thereby
increases the SC of the water (Murphy, 2002). Limestone Run sites flowed through geologic
areas with large quantities of calcite, thereby leading to a high SC. Geologic formations that
contain rocks which do not dissolve easily such as quartz or shale, such as those found in the
geology of the reference sites, release fewer ions into the water and thus contribute many less
ions to increase SC values. The difference in geology provides an idea as to why the SC
measurements were very different Limestone Run and reference sites. Another factor that may
have reduced SC in reference sites is the presence of riparian buffer zones. Riparian cover
surrounding reference sites provided a filter for runoff from both agriculture and roads nearby
and reduced the number of ions that reached the stream.
Sites in agricultural areas as well as those near roadways tend to have higher SC
measurements. Increased SC at agricultural sites is caused by the presence of current conducting
nitrate and phosphate ions from fertilizers. Sodium and chloride ions that can result from road
salt dissolving during the winter season contribute a large number of ions to increase SC. Even
metals extremely low in concentration such as lead and copper, contribute to the overall SC of a
stream. Adding up the cumulative concentrations of all the above mentioned ions, it becomes
logical why the Limestone Run sites with their greater concentrations of anions, cations, and
alkalinity, have a much greater SC than the reference sites, which contain noticeably lower
concentrations of the same ions
29
E. coli
E. coli concentrations at Limestone Run sites ranged from 90 to 1150 colonies/100 mL
(Figure 7). Buffalo Creek and Turtle Creek tributary sites recorded E. coli concentrations of 280
and 140 colonies/100 mL respectively. The presence of E. coli is correlated with the presence of
animal or human feces. In Limestone Run, Buffalo Creek, and the Turtle Creek tributary, it is
likely that the majority, if not all of the E. coli, is attributable to livestock and waterfowl waste.
At sites 1, 2, A, and B, Limestone Run flows through agricultural land where livestock
have direct access to the water and, as a result, so does their waste. The presence of E. coli, a
potentially pathogenic bacterium, is likely attributable to livestock that have the freedom to move
about near the stream. High E. coli concentrations at Sites 3 and C are most likely caused by
waterfowl.
30
Figure 6. E. coli concentrations, in colonies/100 mL, on November 6, 2003 with sampling site
dots scaled to E. coli concentrations.
31
Site 3 is located at a local park just outside Lewisburg. Canada geese and wood ducks
congregate at this park and are fed by townspeople. Because there is a steady supply of food, the
ducks and geese remain at this site year round (Picture C in Appendix III). The park is very
hospitable to the waterfowl, thus the offspring who matured at this park remain at the site. The
headwaters of Miller Run, the stream on which Site C is located, is also habitat for waterfowl.
Miller Run’s headwaters begin from a small pond on the Bucknell University golf course. Golf
course ponds provide an ideal habitat for waterfowl because there is ample food, few competitors
and few humans to disrupt or chase them from their territory.
The sheer number of waterfowl that have access to Sites 3 and C make the concentration
of E. coli much higher than livestock affected sites, where there are many fewer animals.
Livestock also tend to inhabit a larger area of land and thus their feces are not as concentrated in
runoff from the land. From personal observation, waterfowl tend to remain close to the banks of
a stream or directly in the stream, which may result in higher concentration of feces and
therefore E. coli in the stream.
Turbidity
Turbidity values ranged from 4.2 to 11.9 ntu on 9/20/03 (Table 1) and from 2.7 to 25.3 on
10/18/03 (Figure 4). The highest turbidities on both dates were from Site 2. Comparing
Limestone Run sites in general, turbidity was fairly consistent among the sites and between the
days. Turbidity measurements, with the exception of Site 2, were greater on 9/20/03 than those
measured on 10/18/03. The elevated turbidity values on 9/20/03 can be attributed to rain the
night before the sampling date. Rain water likely washed exposed sediment into Limestone Run
and its tributaries, thereby increasing turbidity at each of the sites.
32
Figure 7. Turbidity measurements, in ntu, on October 18, 2003 with sampling site dots scaled to
turbidity measurements
33
The variation in turbidity between Limestone Run sites is likely the result of animal
influences and riparian vegetation. Site 2, which had the highest turbidity on both sampling
dates, had arguably the least amount of riparian cover to hold nearby soil in place. Site 2 was
also the site located nearest a major road (PA Route 45), sediment on the road could be blown
into Limestone Run by passing vehicles thereby contributing to its elevated turbidity. Although
turbidity at Site was higher on both days than other sites, the abnormally high turbidity at Site 2
on 10/18/03 cannot be explained. There was no rain in the area prior to sampling nor was a
disturbance of the water noticed that would have disrupted the substrate enough to result in
increased turbidity. It is not likely that increased traffic could contribute enough sediment to
increase turbidity at this site to 25.3 ntu. Increased turbidity at Site 2 also elevated turbidity at
main stem sites further downstream. Sediment in suspension moves downstream with the water
flow and thereby increases turbidity at successive downstream sites. Turbidity levels at Sites 3
and 4 were half of Site 2 turbidity measurements, but were still roughly twice as high as the other
Limestone Run sites where the sediment settled out.
Site 3 did not have the highest turbidity, but it was near the top on both dates. Site 3 has
the most animals with access to the water as a result of large quantity of waterfowl that inhabit
the park in where Site 3 is located. With so many geese and ducks entering and exiting the
water, they can disrupt the stream bottom and release sediment into the water thereby increasing
turbidity of the site.
Although Site 1 was downstream of an open pasture where cows had access to the
stream, it was far enough downstream and protected by riparian cover so that most of the
sediment had time to settle onto the substrate and little additional sediment could wash in. The
substrate of Site 1 might also partially explain why turbidity was lower at this site. Site 1
34
substrate contained pebbles and rocks, thus sediment could be deposited underneath the rocks
and would not be disturbed unless a severe disruption occurred.
Turbidity measurements at the two reference sites were lower than the Limestone Run
sites on both days. On 10/18/03 turbidity levels in Limestone Run sites were more than twice as
high as those found in Buffalo Creek and Turtle Creek tributary sites (see Figure 4). Lower
turbidity levels at the reference sites are the result of the limited impact of agriculture and urban
land use as well as protection by riparian forested land near these sites. Forested areas use their
deep root structure to hold sediment in place in both the riparian area as well as on the stream
bank (Waters, 1995).
Organic and Inorganic Deposition
Algal biomass in Limestone Run, Buffalo Creek and the Turtle Creek tributary was
measured by the biomass of chl-a from algae growing on tiles. Chl-a concentrations of
Limestone Run sampling sites ranged from undetectable to 1.7 μg/cm2 (Figure 8.). Only four of
the eight Limestone Run watershed sites produced chl-a biomass in a considerable quantity. The
greatest chl-a biomass was produced at Site 3 (1.7 μg/cm2). Sites 2, 5, and B had 1.0, 1.2, and,
0.8 μg/cm2 of chl-a, respectively. Buffalo Creek and the Turtle Creek tributary sites produced
barely measurable quantities of chl-a, 0.2 and 0.1 μg/cm2 respectively.
35
Figure 8. Chlorophyll-a (chl-a) concentrations, in μg/cm2, on December 12, 2003 with
sampling site dots scaled to chl-a concentrations.
36
The high chl-a productivity can be linked to elevated concentrations of organic material
from animal feces as well as nitrates in the water. Animal waste provides nutrients to the water
when nutrients that were not used by the animal’s body are released with waste. The presence of
nutrients in excess as a result of animal nutrient loading provides periphyton with the nutrients it
needs to be extremely productive. Site 3 had the greatest concentration of E. coli as well as the
largest amount of chl-a biomass which can be interpreted to mean that feces contribute a large
quantity of organic material to help the periphyton grow.
Site 2 had the highest turbidity measurements of any site, on both days, yet Site 2 also
had a considerable chl-a biomass of 1.0 μg/cm2. Previously I stated that high turbidity in streams
could prevent algal by blocking sunlight to the algae, Site 2 does not follow this trend. A
possible reason for this is that the depth of Limestone Run is not very great; as a result sunlight
did not need to penetrate very deep to reach the periphyton that grew on the tiles. Another factor
that may have contributed to the high amount of chl-a biomass at Site 2 was the high
concentration of nitrate. Nitrate is an important nutrient for algal growth, and Site 2 had the
greatest concentration of nitrate of all the Limestone Run sites. A high nitrate concentration
allowed the periphyton to be very productive.
Periphyton productivity as determined by chl-a biomass appears to have a positive
relationship with nitrates and nutrient loading from animal waste, however these factors are not
the only factors. Light availability is alos important. Site C is located in a shaded area which
may have prevented periphyton from photosynthesizing despite the high nutrient loading
indicated by the high E. coli count at the site.
The percentage of organic and inorganic material deposited on the tiles differed greatly
among sites (Table 4). Site 3 had the highest amount of matter on the tile (16.5 mg/cm2) and Site
37
1 had the lowest amount of matter at 0.1 mg/cm2. Other than these sites mass of organic and
inorganic deposition ranged from 0.4 to 10.4 mg/cm2. Reference sites had amounts of
accumulated material at the lower end of this range (Buffalo Creek, 1.3 mg/cm2; Turtle Creek
tributary, 0.6 mg/cm2). Of the accumulated material on tiles, inorganic sediment generally
accounted for a much larger percentage of the overall mass than organic. At Site 4, material on
tiles was 100% inorganic sediment. Site 1 had the highest percentage of organic material, but
only 27% of the material collected on the tile was found to be organic. Organic material ranged
from 6-14% of accumulated material among the remainder of the sites.
Table 4. Mass and percents of inorganic and organic material collected on tiles after 10 days.
Site Total growth on tiles Inorganic
1
0.1
0.1
2
9.2
9.2
3
16.5
16.5
4
0.4
0.4
5
10.4
10.4
A
0.8
0.8
B
7.2
7.2
C
0.7
0.7
TCT
0.6
0.6
BC
1.3
1.3
Organic
0.0
0.9
1.0
0.0
1.2
0.1
1.1
0.1
0.1
0.2
% Inorganic % Organic
73
27
92
8
94
6
100
BDL
90
10
91
9
86
14
88
12
92
8
89
11
BDL indicates below the detection limit
Total growth on tiles, Inorganic, and Organic values are reported as milligrams of chl. a per centimeter squared of tile (mg/cm2)
I initially hypothesized that the site with the highest percent of organic matter would be
the site combining the highest E. coli concentrations and chl-a biomass densities. However, Site
1 had the greatest percentage of organic material, despite the fact that it had no detectable chl-a
biomass and had an E. coli concentration in the middle of my observed values. Furthermore,
Site 3 had the largest amount of chl-a biomass, and the second highest E. coli concentration, but
it had the smallest percentage of organic material. While my data did not support my initial idea,
percentages of organic and inorganic material do not show the complete story. Site 1 had the
highest percent of organic material, but the total mass of material deposited on the tile was only
38
0.1 mg/cm2 , making determinations of organic or inorganic composition doubtful when using a
scale that can only measure to 0.1 mg. In contrast, Site 3, where I expected to have the highest
percentage of organic material had the third highest biomass of organic material. Site 3 did
accumulated a high mass of organic biomass but it in comparison to the very high deposition of
inorganic material, organic biomass seemed small. Thus, to get an accurate indication of the
deposition of organic and inorganic material, looking only at the mass or percentages of organic
and inorganic matter is not enough; both must be examined in conjunction with each other.
Biological Assessment
While individual chemical and physical properties of Limestone Run have been proven to be
affected by land use, I also wanted to examine what impact these properties had on biological
communities in the stream. For that reason, I conducted a macroinvertebrate survey using the
Virginia Save Our Streams multimetric index of water quality. This index produced a range of
scores from 2 to 8 (Table 5). Site 5 was deemed the most ecologically acceptable with a score of
8, while Site 1 was judged to be the least ecologically healthy earning a score of 2. The Turtle
Creek tributary site was awarded a score of 6, one point away from being considered
ecologically acceptable. Of the six sites sampled for this index, only two sites scored high
enough to be considered ecologically healthy, Sites 3 and 5. According to this metric, the more
downstream a site was located in Limestone Run, the healthier the macroinvertebrate
assemblage. Upstream sites, which are surrounded by agriculture, were determined to be in
worse ecological health. For example, Site 1 had extremely high numbers of bloodworms
(larvae of the family Chironomidae) and lunged snails, both extremely tolerant of organic
pollution and low dissolved oxygen concentrations.
39
I expected the macroinvertebrate survey to provide accurate determinations of stream
health for each site, but several items made this index unreliable for Limestone Run. For
example, the only site that contained stoneflies was the Turtle Creek tributary. Stoneflies are
extremely sensitive to organic pollution and low dissolved oxygen, and the presence of stoneflies
generally suggests that a stream is “healthy.” However, according to the Virginia SOS score,
this site was deemed ecologically unacceptable with an index score of 6.
Table 5. Virginia Save Our Streams Biological Multimetric Index Score
Site
1
2
3
4
5
TCT
Score
2
3
7
6
8
6
Scores ranging from 0-6 are considered unacceptable ecological conditions.
Scores from 7-12 are considered acceptable ecological conditions.
The macroinvertebrate sampling was only conducted once. Having only a single score to
represent the health of a stream site, based on a single day and a single spot in the sampling site
could prove problematic. Depending on the weather, macroinvertebrates may move to different
areas of the stream. Because only a small area of the sampling site was tested, the presence or
absence of these migrating invertebrates could sway the index score both ways. In addition,
spots where I chose to place the net in the water were rifles so as to provide consistency in the
substrate. However, as much as I tried to find rifles some sites, like Site 3, did not have rifles
and I was forced to move upstream of the waterfowl flocks. Because the macroinvertebrate
index score was calculated in an area upstream of the waterfowl influence and original sample
site, the location of where the biological and chemical data were collected are not consistent. An
inconsistency such as that could result in the biological assessment indicating that the water is
40
ecologically healthy, whereas the chemistry data may suggest otherwise. These issues mentioned
could be especially controversial when a site is on the borderline between ecologically
acceptable or unacceptable, which is the case for four of the six sites that were sampled for this
study, including the Turtle Creek tributary site.
In addition to these sources of variability in multimetric index scores, the technique used
to calculate index scores was developed for use in Virginia streams. Pennsylvania streams might
have different types or abundances of aquatic macroinvertebrates than Virginia streams, and this
would profoundly affect our classification of sites using the multimetric index score. The
multimetric index is the sum of several individual metrics with values indicative of “good” or
“bad” ecological conditions based on study streams in Virginia. The ranges of these individual
metrics reflecting subjective judgments of stream health might be different in Pennsylvania
Insects found in Virginia that must be present in large quantities for a stream to be deemed
ecologically healthy may not exist in Pennsylvania, putting any site in Pennsylvania at a
disadvantage for being considered ecologically acceptable. By the same token, insects that are
common in healthy Pennsylvania streams may not be as prevalent in Virginia and thus, using the
metric may suggest that the Pennsylvania stream has an unhealthy quantity of naturally occurring
macroinvertebrates.
CONCLUSIONS
Limestone Run has undoubtedly been affected by upstream agricultural land use.
Biologically, chemically, and physically Limestone Run differs in a negative manner from the
Turtle Creek tributary reference site which has been much less impacted by agricultural and
urban land use than Limestone Run. There is not a single sampling site located in the Limestone
Run watershed that does not have at least one major area of concern when looking at the
41
ecological indicators such as biological index scores, E. coli concentrations, or chl-a biomass.
To restore Limestone Run to ecological health, action should be taken quickly. Such simple
measures as restricting livestock and waterfowl access to Limestone Run and its tributaries could
increase health. Planting riparian buffers along open stretches of the stream would help prevent
soil erosion. Such small, inexpensive, actions could improve the health of Limestone Run
dramatically and reverse some of the harsh impacts agriculture has had on this stream.
42
Acknowledgments
I would first like to thank Dr. Carl Kirby and Dr. Matt McTammany for their expertise,
guidance, and time throughout this entire process. I would like to thank Dr. Elaine Keithan for
her help in the Environmental Lab with both the anion analysis and E. coli testing. I would also
like to thank the Katherine Mabis McKenna Foundation for financial support allowing me to
send stream samples away to be analyzed for a myriad of elements.
43
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44
Murphy, S. (2002). “General information on specific conductance.” City of Boulder/USGS
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Waters, T.F. (1995). Sediments in Streams: Sources, Biological Effects and Control. American
Fisheries Society Monograph 7. Bethesda, Maryland.
Wetzel, R.G. (2001). Limnology: Lake and River Ecosystems (Third edition). Academic Press.
San Diego, California.
45
Appendix I-A:
ActLabs Chemical Analysis
9/20/03
46
Site 1
Site 1 Replicate
Site 2
Site 3
Site 3 Duplicate
Site 4
Site 5
Turtle Ck Trib
Li
2
2
2
2
2
2
2
-1
Be
-0.1
-0.1
-0.1
-0.1
-0.1
-0.1
-0.1
-0.1
Na
2,660
2,590
5,500
16,300
6,150
6,930
7,200
4,030
Mg
18,300
17,900
23,200
21,300
21,900
21,200
19,200
3,230
Al
13
13
149
11
5
5
9
13
Si
2,890
2,910
3,360
3,430
3,250
3,410
3,200
3,140
K
4,190
4,000
2,340
1,870
2,000
2,230
2,300
1,650
Ca
49,300
48,200
64,400
60,600
61,200
62,400
59,900
12,200
Sc
1
1
1
1
1
1
-1
1
Site 1
Site 1 Replicate
Site 2
Site 3
Site 3 Duplicate
Site 4
Site 5
Turtle Ck Trib
Br
25
26
28
30
28
30
30
58
Rb
2.35
2.24
0.955
0.702
0.756
0.821
0.900
1.01
Sr
174
169
351
549
566
725
690
60.2
Y
0.110
0.117
0.241
0.193
0.080
0.078
0.086
0.037
Zr
0.09
0.09
0.08
0.06
0.06
0.03
0.05
0.04
Nb
-0.005
-0.005
-0.005
-0.005
-0.005
-0.005
-0.005
-0.005
Mo
0.4
0.4
0.3
0.4
0.5
0.6
0.7
-0.1
Ru
-0.01
-0.01
-0.01
-0.01
-0.01
-0.01
-0.01
-0.01
Pd
0.04
0.03
0.03
0.02
0.04
0.02
0.02
0.03
Site 1
Site 1 Replicate
Site 2
Site 3
Site 3 Duplicate
Site 4
Site 5
Turtle Ck Trib
Sm
0.010
0.010
0.037
0.014
0.006
0.006
0.006
0.006
Eu
0.007
0.006
0.012
0.004
0.004
0.004
0.004
0.003
Gd
Tb Dy
Ho
Er
0.011 0.002 0.010 0.002 0.005
0.010 0.002 0.006 0.002 0.006
0.038 0.005 0.026 0.004 0.014
0.022 0.003 0.013 0.003 0.007
0.007 -0.001 0.006 -0.001 0.004
0.006 -0.001 0.006 0.002 0.004
0.008 0.001 0.006 0.001 0.005
0.006 -0.001 0.004 -0.001 0.003
Tm
-0.001
-0.001
0.001
-0.001
-0.001
-0.001
-0.001
-0.001
Yb
0.004
0.004
0.010
0.005
0.002
0.003
0.004
0.003
Ti
1.6
1.6
2.0
1.0
0.9
0.8
1.0
0.8
Cr
-0.5
-0.5
-0.5
-0.5
-0.5
-0.5
-0.5
-0.5
Mn
340
341
28.8
35.5
37.4
37.7
29.3
27.3
Fe
264
269
304
115
105
112
100
53
Ag
Cd
In
-0.2 0.02 -0.001
-0.2 0.02 -0.001
-0.2 0.06 -0.001
-0.2 0.01 -0.001
-0.2 0.01 -0.001
-0.2 0.03 -0.001
-0.2 -0.01 -0.001
-0.2 -0.01 -0.001
Sn
-0.1
-0.1
-0.1
-0.1
-0.1
-0.1
-0.1
-0.1
Sb
0.05
0.05
0.04
0.04
0.04
0.04
0.06
0.04
W
-0.02
-0.02
-0.02
-0.02
-0.02
-0.02
-0.02
-0.02
Re
0.001
0.001
0.001
0.001
0.001
0.002
0.002
-0.001
Lu
-0.001
-0.001
0.001
-0.001
-0.001
-0.001
-0.001
-0.001
V
-0.1
-0.1
-0.1
-0.1
-0.1
-0.1
-0.1
-0.1
Hf
-0.001
-0.001
-0.001
0.002
-0.001
-0.001
-0.001
-0.001
Ta
-0.001
-0.001
-0.001
-0.001
-0.001
-0.001
-0.001
-0.001
Co
0.200
0.208
0.090
0.034
0.006
0.025
0.029
0.058
Ni
0.6
0.6
0.7
1.0
0.3
0.4
0.7
0.7
Cu
0.9
1.0
1.1
1.4
1.0
0.9
1.1
0.9
Zn
3.1
3.2
3.7
1.6
1.8
2.4
0.6
2.5
Ga
Ge As
0.01 0.01 0.63
0.01 0.01 0.65
0.04 -0.01 0.33
-0.01 0.01 0.33
-0.01 0.01 0.29
-0.01 0.01 0.38
-0.01 0.01 0.40
-0.01 -0.01 0.14
Se
-0.2
-0.2
0.3
-0.2
-0.2
-0.2
-0.2
-0.2
Te
I
Cs Ba
La
Ce Pr
Nd
-0.1 10 0.001 37.3 0.031 0.066 0.009 0.035
-0.1 9 0.002 36.7 0.031 0.067 0.009 0.035
-0.1 7 0.005 38.0 0.144 0.298 0.041 0.166
-0.1 8 0.001 40.8 0.070 0.057 0.016 0.063
-0.1 7 0.002 45.3 0.026 0.037 0.006 0.024
-0.1 9 0.002 43.6 0.023 0.036 0.006 0.023
-0.1 9 0.002 41.3 0.029 0.040 0.007 0.037
-0.1 6 0.002 12.9 0.012 0.023 0.004 0.013
Os
-0.002
-0.002
-0.002
-0.002
-0.002
-0.002
-0.002
-0.002
Pt
-0.3
-0.3
-0.3
-0.3
-0.3
-0.3
-0.3
-0.3
Au
-0.002
-0.002
-0.002
-0.002
-0.002
-0.002
-0.002
-0.002
Hg
-0.2
-0.2
-0.2
-0.2
-0.2
-0.2
-0.2
-0.2
Tl
0.001
0.001
-0.001
-0.001
-0.001
0.001
-0.001
-0.001
Pb
0.06
0.06
0.24
0.05
0.03
0.06
0.02
0.05
Bi
-0.3
-0.3
-0.3
-0.3
-0.3
-0.3
-0.3
-0.3
Th
0.003
0.004
0.003
0.003
0.002
0.001
0.002
-0.001
U
0.139
0.134
0.217
0.197
0.196
0.214
0.215
0.015
47
Appendix I-B:
ActLabs Chemical Analysis
10/18/03
48
Site 1
Site 2
Site 3
Site 4
Site 5
Site 5 Duplicate
Turtle Ck. Trib.
Buffalo Creek
Li
2
3
4
3
4
3
1
1
Be
-0.1
-0.1
-0.1
-0.1
-0.1
-0.1
-0.1
-0.1
Na
3,470
6,980
7,130
7,730
7,930
7,470
5,570
3,750
Mg
19,200
26,500
24,300
24,800
25,100
24,100
3,960
6,730
Al
15
14
8
9
9
7
11
29
Si
2,590
3,150
2,860
2,950
2,850
2,840
2,930
2,240
K
2,500
1,670
1,430
1,560
1,650
1,680
1,610
1,240
Ca
48,400
67,100
66,200
69,800
69,900
66,600
13,300
24,100
Sc
-1
1
-1
1
-1
-1
-1
-1
Ti
1.0
0.9
0.9
1.0
1.2
0.8
0.7
1.0
V
-0.1
-0.1
-0.1
-0.1
-0.1
-0.1
-0.1
-0.1
Cr
-0.5
-0.5
-0.5
-0.5
-0.5
-0.5
-0.5
-0.5
Mn
71.2
53.3
29.9
40.1
24.9
27.2
16.4
21.8
Fe
135
103
103
115
106
119
61
140
Co
0.051
0.023
0.005
0.041
0.076
0.088
0.045
0.072
Ni
0.6
0.4
0.3
0.5
0.7
1.5
0.5
0.9
Cu
0.7
0.5
0.4
0.6
1.6
2.4
0.4
0.5
Zn
2.1
0.5
1.1
1.1
5.6
7.5
0.8
0.9
Ga
0.01
0.01
-0.01
-0.01
-0.01
-0.01
-0.01
-0.01
Ge
-0.01
-0.01
-0.01
-0.01
-0.01
-0.01
-0.01
-0.01
As
0.32
0.29
0.13
0.14
0.16
0.16
0.13
0.12
Se
-0.2
-0.2
-0.2
-0.2
-0.2
-0.2
-0.2
-0.2
Site 1
Site 2
Site 3
Site 4
Site 5
Site 5 Duplicate
Turtle Ck. Trib.
Buffalo Creek
Br
22
27
24
25
24
24
66
17
Rb
1.23
0.612
0.634
0.641
0.674
0.691
0.809
0.698
Sr
105
409
658
758
752
735
62.5
171
Y
0.054
0.075
0.057
0.063
0.061
0.064
0.030
0.064
Zr
0.05
0.33
0.02
0.03
0.04
0.05
0.02
0.05
Nb
-0.005
-0.005
-0.005
-0.005
-0.005
-0.005
-0.005
-0.005
Mo
0.3
0.4
0.4
0.5
0.5
0.5
-0.1
0.1
Ru
-0.01
-0.01
-0.01
-0.01
-0.01
-0.01
-0.01
-0.01
Pd
0.06
0.04
0.04
0.03
0.04
0.04
0.03
0.03
Ag
-0.2
-0.2
-0.2
-0.2
-0.2
-0.2
-0.2
-0.2
Cd
0.01
-0.01
-0.01
-0.01
0.02
0.06
-0.01
0.01
In
-0.001
-0.001
-0.001
-0.001
-0.001
-0.001
-0.001
-0.001
Sn
-0.1
-0.1
-0.1
-0.1
-0.1
-0.1
-0.1
-0.1
Sb
0.04
0.03
0.02
0.03
0.05
0.06
0.03
0.02
Te
-0.1
-0.1
-0.1
-0.1
-0.1
-0.1
-0.1
-0.1
I
6
6
5
5
5
5
5
4
Cs
0.004
0.003
0.002
0.001
0.002
0.002
0.003
0.001
Ba
34.9
41.7
44.7
43.6
46.4
45.4
12.8
17.7
La
0.018
0.024
0.015
0.016
0.015
0.015
0.009
0.023
Ce
0.037
0.043
0.027
0.024
0.024
0.023
0.018
0.044
Pr
0.006
0.006
0.004
0.004
0.004
0.004
0.003
0.008
Nd
0.023
0.030
0.017
0.018
0.018
0.020
0.009
0.025
Site 1
Site 2
Site 3
Site 4
Site 5
Site 5 Duplicate
Turtle Ck. Trib.
Buffalo Creek
Sm
0.008
0.006
0.003
0.004
0.004
0.005
0.004
0.008
Eu
0.004
0.004
0.006
0.006
0.008
0.007
0.003
0.005
Gd
0.009
0.008
0.005
0.006
0.006
0.006
0.003
0.009
Tb
-0.001
0.001
-0.001
-0.001
-0.001
-0.001
-0.001
0.001
Dy
0.005
0.006
0.004
0.004
0.005
0.004
0.004
0.008
Ho
0.001
-0.001
-0.001
-0.001
-0.001
-0.001
-0.001
0.001
Er
0.004
0.003
0.002
0.002
0.002
0.003
0.002
0.004
Tm
-0.001
-0.001
-0.001
-0.001
-0.001
-0.001
-0.001
-0.001
Yb
0.002
0.003
0.001
0.002
0.002
0.003
0.002
0.004
Lu
-0.001
-0.001
-0.001
-0.001
-0.001
-0.001
-0.001
-0.001
Hf
-0.001
0.006
-0.001
-0.001
-0.001
-0.001
-0.001
-0.001
Ta
-0.001
-0.001
-0.001
-0.001
-0.001
-0.001
-0.001
-0.001
W
-0.02
-0.02
-0.02
-0.02
-0.02
-0.02
-0.02
-0.02
Re
-0.001
0.002
0.002
0.002
0.001
0.002
-0.001
-0.001
Os
-0.002
-0.002
-0.002
-0.002
-0.002
-0.002
-0.002
-0.002
Pt
-0.3
-0.3
-0.3
-0.3
-0.3
-0.3
-0.3
-0.3
Au
-0.002
-0.002
-0.002
-0.002
-0.002
-0.002
-0.002
-0.002
Hg
-0.2
-0.2
-0.2
-0.2
-0.2
-0.2
-0.2
-0.2
Tl
Pb Bi
Th
U
-0.001 0.04 -0.3 0.003 0.147
-0.001 0.02 -0.3 -0.001 0.200
-0.001 -0.01 -0.3 0.001 0.202
-0.001 -0.01 -0.3 0.001 0.221
-0.001 0.02 -0.3 0.001 0.222
-0.001 0.10 -0.3 0.001 0.225
-0.001 0.02 -0.3 0.001 0.017
-0.001 0.04 -0.3 0.003 0.074
49
Appendix II:
Virginia Save Our Streams
Stream Quality Survey
50
51
52
53
54
Appendix III
Photographs
55
A. Headwaters of Limestone Run
B. Aquatic macrophytes in the stream at Site 2
C. Waterfowl at Site
56
57