A Hydrogeological Study of Coldwater Spring, Minneapolis, MN

Sophie Kasahara

Submitted under the supervision of E. Calvin Alexander, Jr. to the University Honors Program at the University of Minnesota-Twin Cities in partial fulfillment of the requirements for the degree of Bachelor of Science, summa cum laude, in Geo- engineering.

[6 May 2016]

Table of Contents Abstract ...... iii Introduction ...... 1 Historical Background ...... 1 Salinity Effects on Wildlife ...... 1 The Sample Sites ...... 2 Methods and Data ...... 3 Chemistry/Field Parameters ...... 3 Dye Trace ...... 4 Interpretation and Discussion ...... 4 Dye Trace ...... 4 Chloride...... 6 Temperature ...... 11 Three Inlet Pipes ...... 15 Nitrate-Nitrogen ...... 17 Major Ion Chemistry ...... 19 Summary and Conclusions ...... 20 Acknowledgements ...... 21 References ...... 22

Table of Figures

Figure 1: Aerial View of Coldwater Spring Area ...... 2 Figure 2: Dye Inputs and Sampling Locations ...... 5 Figure 3: Historical 1880 Chloride Data ...... 6 Figure 4: MnDOT Coldwater Spring Chloride Data ...... 7 Figure 5: Chloride Content Field Data for Coldwater Spring and Wetland A ...... 7 Figure 6: Coldwater Spring Chloride from MnDOT and Field Data ...... 8 Figure 7: Coldwater Spring Chloride MnDOT and Field Data Projection ...... 9 Figure 8: Yearly U.S. Highway Salt Sales ...... 9 Figure 9: Chloride Content from all Three Sampling Periods ...... 9 Figure 10: Chloride to Bromide Mass Ratios ...... 10 Figure 11: Temperature Field Data for Coldwater Spring ...... 12 Figure 12: Temperature Field Data with Air Temperature ...... 12 Figure 13: Temperature Field and Data Logger Data ...... 14 Figure 14: Coldwater Spring House Northwest Face Inside Wall ...... 15 Figure 15: Overhead Map with Sample Locations at Coldwater Spring ...... 15 Figure 16: Three Inlet Sources into Coldwater Spring House ...... 16 Figure 17: Chloride Concentrations from Ten Different Sample Locations ...... 17 Figure 18. Nitrate-Nitrogen Levels for Coldwater Spring and Wetland A ...... 18 Figure 19: 3D Piper Diagram for Coldwater Spring and Wetland A ...... 19

i Table of Appendixes

Appendix A: Field Data for Coldwater Spring, Wetland A, Wetland H, Big Culvert ...... 24 Appendix B: Field Data for Additional Sample Locations ...... 47 Appendix C: Past Coldwater Spring Data ...... 50

Appendix A: Field Data for Coldwater Spring, Wetland A, Wetland H, and Big Culvert Appendix B: Field Data for Additional Sample Locations Appendix C: Past Coldwater Spring Data

ii Abstract

This project has monitored the water chemistry of Coldwater Spring, Minneapolis, MN to document human impacts on the spring’s water quality. Temperature, dissolved oxygen, conductivity, pH and anions were monitored weekly and cations and alkalinity monitored monthly at Coldwater Spring and the adjacent Wetland A from 15 February 2013 through 18 January 2015. A dye trace was conducted at the Coldwater Spring site from 6 June 2015 through 6 February 2016. Dye was injected into two rain gardens in the Veteran’s hospital parking lot, located northwest of Coldwater Spring. Coldwater Spring’s water flows through fractures in Platteville Limestone of Ordovician age. The basic chemistry of Coldwater Spring should be the calcium magnesium bicarbonate water typical of carbonate springs. However, on an equivalent basis, Coldwater Spring’s water currently contains almost as much sodium as calcium + magnesium and more chloride than bicarbonate.

The chloride concentrations are about 100 times the levels from 1880. Maguire (1880) reported the chloride levels of Coldwater Spring were about 4.5 ppm. During the current study the chloride content in the spring increased from about 320 ppm from March 2013 to about 410 ppm in December 2014. In April, May and June of 2013 and 2014, the chloride rose about an additional 100 ppm in three month-long pulses. The chloride concentration of the water in Wetland A ranges from about 400 ppm to over 600 ppm with a pattern that is a mirror image of the Coldwater Spring pattern. This major anthropogenic chloride component has a chloride to bromide ratio of 2,500 ± 300, well within the range of chloride to bromide ratios of road salt, 1,000 to 10,000. Road salt is applied to two major multi-lane highways close to the spring and is used extensively in this heavily urbanized area throughout the winter.

The temperature of the spring is variable and higher than its pre-settlement temperature. Nicollet (1841) recorded the temperature of Coldwater Spring multiple times in summer of 1836 as 46 °F (7.8 °C) and multiple times in winter of 1837 as 45.5 °F (7.5 °C). More recently the temperature of Coldwater Spring fluctuates smoothly between 10.7 and 13.1 °C. The higher temperature of the springs’ discharge also indicates an anthropogenic source of heat within the spring-shed or spring recharge area. The spring water is coldest in May and June and warmest in October and November. The temperature of the water in Wetland A fluctuates from 6.4 to 13.8 °C – in a pattern that is opposite of that in Coldwater Spring. Coldwater Spring also contained a significant, increasing nitrate-nitrogen component, which ranged from 2.5 to 5.2 ppm – with dips at the same times as the chloride pulses. Wetland A’s nitrate-nitrogen level varied between 0.2 to almost 6 ppm with large pulses at the same time as Coldwater Spring’s dips. A 2014 study performed by the U.S. Geological Survey came to the conclusion that increasing chloride levels in lakes and streams are likely driven by increasing road salt application, rising baseline concentrations, as well as an increase in snowfall in the Midwestern area of the U.S. during the time of the study (Corsi 2014). The significant chloride, temperature and nitrate levels are likely to be driven by anthropogenic sources.

The dye trace conducted at Coldwater Spring was inconclusive. No positive results were detected at eight different sample locations in the Coldwater Spring area.

Three different water sources with different chemistries were observed to be flowing into the Coldwater springhouse through three inlets. This water combined in the springhouse and left the springhouse through the outfall pipe, which is where the Coldwater Spring field samples were obtained. The outfall pipe was determined to contain about 80% of the water from Inlet A, 10% of the water from Inlet B, and 10% from Inlet C.

iii Introduction

This project monitored the water quality in Coldwater Spring, Minneapolis, Minnesota, to evaluate the impact of anthropogenic pollutants on the spring and an adjacent wetland (“Wetland A”). Coldwater Spring in Minneapolis, Minnesota was the water supply for Fort Snelling from the 1840s to 1920. The spring site has been declared a sacred site by some federally recognized Native American tribes. The site is managed by the National Park Service. This report expands and adds a third year of data to Kasahara et al.’s (2015) report on the first two year’s results and to Kasahara’s (2014) report on the first year’s results of this project.

Historical Background

In the early 1820’s, troops lived at Camp Coldwater Spring during the construction of a military base called Fort Snelling. Camp Coldwater Spring was later the home to settlers in the 1830’s, including a mix of nationalities such as Dakota, Ojibwe, French and English (White, 2000). In 1837, Peter Garrioch, under the recommendation of Martin McLeod, formed one of the first public schools of Minnesota at the site of Camp Coldwater Spring. Coldwater Spring continued to serve as a water source for Fort Snelling until 1920 (White, 2000).

As further discussed in the Data and Interpretation section, two historical samples from Coldwater Spring provide background data for this project. The first sample, taken in 1880 by Army Captain Maguire, reported the chloride level in Coldwater Spring to be 0.26 grains per gallon, equivalent to 4.5 ppm in modern units. In 1836 and 1837, a French explorer named Joseph Nicollet measured the temperature of Coldwater Spring in both the summer and the winter months (Nicollet, 1845). Converting the temperatures from Fahrenheit to degrees centigrade, the measured temperature average of Coldwater Spring was about 7.8 °C in July and 7.5 °C in the winter.

Salinity Effects on Wildlife

In the Twin Cities Metropolitan area (TCMA), roughly 350,000 tons of de-icing road salt is applied to the TCMA roads every year (Sander et al., 2007). The majority of this salt dissolves in snowmelt that either flows overland to surface water bodies or infiltrates to recharge the water table. According to a recent study about 70% of the road salt applied in the Twin Cities area stays in the regions’ watershed (Rastogi, 2010). The road salt used is about 60% chloride and 40% a positive ion, usually sodium, and is generically referred to as NaCl (Keseley, 2007). This road salt runoff can lead to high levels of salinity in freshwater areas due to the dissolution of NaCl in the water. This is harmful to freshwater aquatic life, regional mammals and birds, and plants native to Minnesota.

Ten percent of freshwater species can die off after just 30 days at salinity concentrations of 220- 240 ppm, trout behavior is affected at levels as low as 250 ppm, and the overall diversity of aquatic species decreases as the salinity concentration rises (Keseley, 2007). According to the Minnesota Pollution Control Agency’s (MPCA) 2010 draft report, 11 metro-area streams have levels of chloride concentration above 230 ppm (Homstad, 2010). Road salt particles may attract moose and deer to roadsides, where cars or trucks may strike them, and birds, such as sparrows, can die after eating only two salt particles. Plants as far as 200 feet away from the roadside can

1 still be affected by the rise in salinity, and just a 30 ppm concentration can lead to damage to coniferous species such as the pine tree (Keseley, 2007). Because groundwater is the source for drinking wells, high levels of salinity can also affect humans on restricted-sodium diets (Rastogi, 2010).

The Sample Sites

Coldwater Spring is located at 44° 53’ 57.61” N; 93° 11’ 47.81” W. Coldwater Spring is an important Native American cultural site (NPS, 2012) and is an integral part of the history of Fort Snelling and Minneapolis. The spring site is now a part of the National Park Service’s Mississippi River National River and Recreation Area (NPS, 2012) and is open to the public.

The Minnesota Department of Health test results of the spring water in 2005 revealed the presence of bacteriological contamination of total coliform indicating organisms, but did not detect E. coli. The NPS has posted signage at the spring indicating the water is not suitable for drinking.

Figure 1: Aerial View of Coldwater Spring Area Coldwater Spring is in a highly urbanized area in the southeast corner of Minneapolis, Minnesota. A major trunk highway/light rail interchange is immediately west of the spring. The large white squares visible northwest of the spring are buildings of a VA Medical center. Runway 22-4 of the MSP International Airport extends into the southwest corner of Figure 1. St. Paul, Minnesota is across the Mississippi River to the east- northeast.

The groundwater in the Coldwater Spring region typically flows from west to east toward the Mississippi River, and recharges from precipitation and lakes such as Lake Nokomis and Mother

2 Lake. The bedrock geology of this area is of about 26 feet of Platteville Limestone and a variety of soils, which overlays about 3 feet of Glenwood Shale (Howe 2014). Both these layers overlie a highly permeable layer of St. Peter Sandstone. The Platteville Limestone is often described as being two different layers, Upper and Lower Platteville, because of the differing amounts of shale content. In the Lower Platteville Limestone, the shale comprises greater than 30% of the Platteville’s composition, while the Upper Platteville has much lower shale content. The Lower Platteville Limestone thus has a lower conductivity and acts as a confining layer for the Upper Platteville Limestone. Water in the Upper Platteville Limestone has access to easy horizontal flow paths (Howe 2014). Coldwater Spring’s water flows through fractures in the upper layers of the Platteville Limestone of Ordovician age. Studies of this formation have shown that these layers are ineffective at filtering out many of the contaminants from the recharge areas, in this case runoff from residential housing and major highways (NPS, 2012).

The Wetland A sample site is a reconstructed wetland. The Wetland A previously had a building from the former Bureau of Mines, Twin Cities Research Center (TCRC) situated adjacent to it. The TCRC was closed in 1996 and the building removed in 2012. The adjacent historic springhouse and reservoir were left intact as the restoration of the Coldwater Spring site was completed by the National Park (NPS, 2012). Wetland A is located at 44° 53’ 55.14” N; 93° 11’46.91” W.

The “Big Culvert” is a 6-foot diameter storm water outlet that drains the area southwest of the Coldwater Spring site. It flows perennially and was sampled twice late in this project. The Big Culvert is located at 44° 53’ 47.91” N; 93° 11’44.81” W. Methods and Data

Chemistry/Field Parameters

Weekly visits were conducted to Coldwater Spring and Wetland A to record the temperature, to measure the conductivity, dissolved oxygen and pH levels of the spring using a Thermo Orion multi-meter, and to collect weekly anion samples. The Coldwater Spring samples were collected at the outfall pipe on the southwest corner of the springhouse structure. The Wetland A samples were collected from a small spring on the SW corner of the wetland. The anion samples were analyzed using ion chromatography [EPA 300.0]. Samples were collected monthly for alkalinity analyses by digital titration [ASTM 1067 02] and cation analyses by ICP/OES [EPA 200.7]. Water samples were collected from the two sites from the beginning of February 2013 to the middle of January 2015. The timing of this data collection was intended to study any impact to the springs’ salinity levels during snow melt, when deicing salt would presumably be washing into and through groundwater supplies. A temperature data logger was installed in Coldwater Spring. The data logger was inserted into a round pipe (“Pipe Inlet C”, Fig. 14) along the north side of the springhouse about 3 meters from the outfall pipe.

A full listing of the anion, cation, alkalinity, and field parameters measured in this study are listed in Appendices A, B and C.

3 Dye Trace

Rhodamine and uranine/fluorescein dyes were poured into two separate rain gardens, upper and lower respectively, located in the Veteran’s Hospital parking lot on June 6th, 2015. The Veteran’s Hospital is located northwest of Coldwater Spring, on the opposite side of Highway 55.

Eight charcoal “bug” packets were placed at various Coldwater Spring sample sites to track the flow of the dye through the groundwater system. Figure 2 shows the dye injection points as well as the eight monitoring points. These bugs were monitored weekly and then monthly until the end of the sampling period on February 6th, 2016 (small culvert bug removed April 16th, 2016).

Interpretation and Discussion

Dye Trace

Past Dye Trace

Alexander et al. (2001) conducted a dye trace at Coldwater Spring. This study was the first dye trace conducted in the Twin Cities Platteville Limestone and provides initial background information as to how the groundwater flows close to Coldwater Spring.

Phloxine B, Eosin Y, and fluorescein dyes were injected into three input locations near Coldwater Spring. Charcoal “bug” detectors were placed at sample locations around Coldwater Spring to check for the positive detection of dye in the groundwater. An auto-sampler collected direct water samples at Coldwater Spring. The results of the dye trace are shown in Figure 2.

The Eosin Y dye was injected into a trench in the Platteville Limestone. This dye input yielded positive results, and traveled about 125 meters to Camp Coldwater Spring in less than 1.5 hours. The calculated minimum velocity for the flow through the fractured Platteville Limestone was therefore about 83 m/hr. The fluorescein dye was injected into a water-filled construction pit. The fluorescein showed a positive result, and passed through glaciofluvial sediments to reach the water table. This dye traveled roughly 305 meters in about 16 days. The Phloxine dye was injected into a small collapse feature adjacent to a road. The Phloxine was not recovered at any of the monitoring stations.

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Figure 2: Dye Inputs and Sampling Locations Figure 2 is a map showing the relationships between the TH62/TH55 traffic interchange, the Minneapolis VA Medical Center and the Coldwater Spring Mississippi National River & Recreation Area. The two blue circles show Coldwater Spring (upper) and Wetland A Spring (lower). The orange (Eosin Y) and green (fluorescein) arrows show the results of 2001 dye traces (Alexander et al., 2001). The orange square shows the Phloxine dye injection point, which yielded no positive results (Alexander et. al., 2001). The two red triangles show the 2015 dye input points in the northern parking lot rain garden (upper) and southeastern parking lot rain garden (lower). The green triangles show the outfall pipes of drainage and storm water drains. The two black crosses are sampling locations under the foot bridges across the Coldwater and Wetland A spring runs. Charcoal detectors were placed and periodically changed at the eight locations shown by the blue circles, black crosses and green triangles.

Current Dye Trace

The 2015 dye trace at Coldwater Spring yielded no positive results during the sampling period. Generally, negative results in a dye trace are attributed to one or more of three main reasons. One reason for negative results is that there may not have been enough dye inputted into the rain garden system. If the dye did show up at Coldwater Spring undetected, this could be because the dye was diluted or absorbed before the dye reached the sample locations.

Another reason for negative results is that the dye may not have reached the sampling points by the time this study was concluded. Dye travels through the groundwater at different rates,

5 depending on the material that the dye is traveling through. Many dye traces are conducted during the spring, as the fresh snowmelt can flush dye through a groundwater system. This study was conducted in the summer, fall and winter, so the dye may still be traveling towards Coldwater Spring.

A third possible reason for why there are no positive dye results could be because the dye is going to a location that is not being sampled. Although eight possible areas where the dye might have shown up were identified at Coldwater Spring, the dye may have been rerouted to an area that was not being sampled. Given that one of the dyes in Alexander et al.’s (2001) traces was not detected and neither of the dyes in this trace were detected, one possibility is that the extensive storm and/or sanitary sewer systems captured the dye.

Chloride

Historical Chloride Data

During the 19th Century Coldwater Spring was the water source of the U.S. Army’s Fort Snelling in Minneapolis. Army Captain Maguire (1880) reported the chloride level in Coldwater Spring to be 0.26 grains per gallon, which is equivalent to 4.5 ppm in modern units. [Early analyses of chloride were done by titration with a clear end-point and are quite reliable.]

Figure 3: Historical 1880 Chloride Data Figure 3 shows the results of the chloride measurement of Coldwater Spring from 1880, measured by Army Captain Maguire.

Previous Chloride Study

Previous to this study, the water chemistry at Coldwater Spring was monitored from June of 1998 to March of 2001. This study was part of a comprehensive study conducted by MnDOT to ensure the expansion of Highway 55 did not seriously impact the flow and water chemistry of Coldwater Spring (Received through personal communication with Mike Panzer, 10 December 2016. Data listed in Appendix C).

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Figure 4: MnDOT Coldwater Spring Chloride Data This figure shows the chloride data collected from the MnDOT study of Coldwater Spring. This data did not show any clear seasonal trends, although the two highest peaks of 320 ppm occurred near the end of August in 1998 and 2000. The chloride levels ranged between about 240 and 320 ppm.

Field Data

Figure 5: Chloride Content Field Data for Coldwater Spring and Wetland A This figure shows that the chloride content of Coldwater Spring’s water increased from 320 ppm in March 2013 to 410 ppm in January 2015. Superimposed on the increase of about 45 ppm/year were two pulses between roughly April and July of 2013 and 2014. The first pulse reached 432 ppm on 10 June 2013. The second pulse rose to 455 ppm on 20 May 2014. These chloride levels are about 100 times the levels from 1880.

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Deicing salt is applied to two major multi-lane highways close to the springs throughout the late fall, winter and early spring. If the pulses are attributable to infiltration of road salt runoff, these data suggest it takes about five months for the winter road salt input to reach Coldwater Spring. The magnitude of each year’s pulse should depend on the severity of the winter – which fluctuates significantly from year to year depending on the severity of each winter. Ignoring the chloride pulses, chloride levels in Coldwater Spring are very high and increasing at about 45 ppm per year over the time period of this study.

Comparison of Historical and Field Chloride Data

Figure 6: Coldwater Spring Chloride from MnDOT and Field Data This figure shows a comparison between the MnDOT collected Coldwater Spring data and the field data that was collected during this study.

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Figure 7: Coldwater Spring Chloride MnDOT and Field Data Projection Figure 7 (left) shows the Figure 6 data projected backward in time to about 1957.

Figure 8: Yearly U.S. Highway Salt Sales Figure 8 (right) shows the yearly U.S. highway salt sales, with the rise in applied road salt occurring in roughly the late 1950’s and early 1960’s. This data was obtained from: https://illinois.edu/blog/view/789/62191 (Kelly, 2011).

Figure 9: Chloride Content from all Three Sampling Periods This figure shows a comparison between the MnDOT chloride data, the chloride data from this study, and the sample collected in 1880 by Army Captain Maguire. The chloride levels ranged from 4.5 ppm in 1880, between 240 and 320 ppm in the 1998-2001 data, and between 300 and 450 ppm in the 2012-2015 data.

In Figure 6, there is a clear increasing trend in the chloride levels in Coldwater Spring. The average chloride content in Coldwater Spring rose from about 280 ppm in 1998-2001, to 380 ppm in 2012-2015. This shows about a 6.7 ppm/year increase in chloride levels, which is a lower rate than the 45-ppm/year increase seen in the 2012-2015 data.

9 Figure 7 shows that the time trend defined by the MnDOT 1998-2001 data set and the data from this work extrapolate back to about 1960, Kelly’s (2011) compilation of U.S. Highway Road salt usage is shown in Figure 8. Road salt usage began in the 1940’s, rose through 3 million tons/year in the late 1950’s, reached 10 million tons/year in the early 1970’s, and has fluctuated between 10 to 20 million tons/year for the past roughly twenty years.

Figure 9 shows the data from 1880 to the present for Coldwater Spring. The data is sparse, but is consistent with the road salt usage history in Figure 8. The chloride content of Coldwater Spring probably remained low up until road salt usage began in the 1940’s and began to rise rapidly about 1960 and continues to rise in 2015.

Wetland A

Wetland A chloride levels (Figure 5) were higher than the chloride levels at Coldwater Spring, and displayed an inverse relationship to Coldwater Spring. Wetland A’s chloride levels were low when Coldwater Spring’s chloride pulses were high – and vice versa. The dips in Wetland A chloride concentrations were greater than the pulses in Coldwater Spring’s concentrations, but occurred at essentially the same time. Wetland A’s chloride levels ranged from 313 ppm to 632 ppm. This mirror image behavior of Coldwater Spring and Wetland A’s water quality is repeated in several of the other parameters discussed below. This behavior is cryptic and is surprising. We are not aware of any other system that displays this mirror image behavior. Chloride is the most common anion in both Coldwater Spring and Wetland A’s water.

Big Culvert

Only one sample was collected from the Big Culvert. Big Culvert’s value is shown in Figure 2 and subsequent graphs. This result is similar to the data seen at Wetland A.

Chloride to Bromide Mass Ratios

Figure 10: Chloride to Bromide Mass Ratios This figure shows Chloride to bromide mass ratios for Coldwater Spring, Wetland A, Big Culvert, and for two road salt samples taken from different sites on the University of Minnesota campus.

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Salts from different sources have different, characteristic chloride to bromide ratios (Davis et al., 1998). In addition to the sewage and rainfall Cl/Br ratios, Panno et al. (2006) found Cl/Br ratios for softened water ranging between 175 and 1,122 and for agrichemical-affected water with tile drains, from 108 to 1974. The road salt ratio minimum was 1,164 and ranged up to 4,225. Measurements of the chloride to bromide ratios in Coldwater Spring, Wetland A and Big Culvert help to identify the source of the salt. Figure 10 shows the chloride to bromide mass ratios from the sample sites. It also shows the chloride to bromide mass ratios of three road salt samples taken from different sites on the University of Minnesota campus in winter 2014.

Coldwater Spring, Wetland A and Big Culvert

The chloride to bromide ratios in all three sample sites scatter from about 2,000 to 4,500 - well within the range of reported values for road salt. The ratios from the three samples of road salt taken at three different sites around the University of Minnesota campus are in the same range. These data suggest that road salt is the primary contributor to the high chloride levels in Coldwater Spring, Wetland A and the Big Culvert.

Temperature

Historical Temperature Data For Coldwater Spring

In 1836 and 1837, a French explorer named Joseph Nicollet measured the temperature of Coldwater Spring in both the summer and the winter months (Nicollet, 1845). He described Coldwater Spring’s temperature as:

“Of the numerous springs that issue from the foot of the…bluffs [adjoining Fort Snelling] there is one particularly deserving of notice. It is very abundant and perfectly shaded. It goes by the name of Baker’s spring. Having taken its temperature three times a day during twenty days of the month of July, 1836, and then again during the following winter months, I never found it to vary more than 46°F in July, and 45.5°F in January.”

Converting the temperatures from Fahrenheit to degrees centigrade, the measured temperature average of Coldwater Spring was about 7.8 °C in July and 7.5 °C in the winter. This indicates that in the summer of 1836 and the winter of 1837, Coldwater Spring’s temperature was essentially constant. The temperature of shallow springs is typically the average annual air temperature of that region. The shallow ambient groundwater temperature in this part of Minnesota is about 8 °C.

11 Temperature Records

Figure 11: Temperature Field Data for Coldwater Spring This figure displays the weekly temperatures of Coldwater Spring and Wetland A. The temperature was measured using an ASTM calibrated glass thermometer.

Figure 12: Temperature Field Data with Air Temperature This figure contrasts the weekly temperature records for Coldwater Spring and Wetland A with the average air temperatures on the days that samples were collected. The air temperature data, measured at the Minneapolis/St. Paul Airport and which is two kilometers from Coldwater Spring, are from the National Weather Service website, as follows: http://www.crh.noaa.gov/mpx/Climate/MSPClimate.php

12 Temperature at Coldwater Spring

The field thermometer temperature of Coldwater Spring (Figure 11) fluctuated seasonally between 10.7 °C and 13.1 °C in a sinusoidal pattern. This is a 3- to 5- degree increase from the 1836 and 1837 temperature levels. Since the temperature fluctuates over a 2.4 degree range, it is clear that Coldwater Spring is no longer a constant temperature spring. The increases and fluctuations of temperatures may reflect increased urbanization where snow is cleared from roads and parking areas allowing greater frost depths and much higher temperatures under summer sun.

The lowest point in the temperature fluctuations occurs in early June, roughly coincident with the chloride peaks. The highest temperatures occur in early November. In comparison the air temperatures (Figure 12) peak in late July or early August and the minimum temperatures occur in late January to early February. The temperature fluctuations in Coldwater Spring lag air temperature fluctuations by about four to five months.

Temperature in Wetland A

Wetland A thermometer temperatures ranged between 6.4 and 13.8 °C, with the temperature peaking at the end of August. Wetland A is also not feed by a constant temperature spring. The Wetland A’s water source temperature fluctuation is out of phase with the air temperature by about two months. Wetland A temperatures range from well above to below the average groundwater temperatures of roughly 8 °C. Wetland A’s temperatures can be explained as being driven by the air temperatures in a very shallow flow system.

Data Logger

The data logger record (Figure 13) has relatively smooth, linear temperature profiles with minimal short-term variation. The absence of hours to days temperature excursions indicate that the flow path to this sampling point is long enough to even out variations due to storm events but not long enough to average out seasonal effects.

The data logger temperature record is surprisingly different from the thermometer readings record. The shape is closer to a linear zig zag than a sine wave. The maximum and minimum temperatures of the data logger record are 0.3 to 1 °C higher than those in hand measured temperature record using the thermometer.

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Figure 13: Temperature Field and Data Logger Data In Figure 13 the 15-minute interval data logger temperature record from Coldwater Spring is shown in blue. The gaps in the data logger plot are due to equipment problems. The weekly thermometer data from Coldwater Spring (from Figures 4 and 5) is shown in red.

Discrepancies in the two temperature records proved to be due to the location of the temperature samples taken. The data logger was located in one of the entrance pipes on the north side of the springhouse, and the thermometer samples were taken from the south side of the springhouse in the exit pipe, about ten feet from the data logger. The apparent discrepancies were evidence for multiple, different water inputs to the Coldwater Springhouse. Such different sources (fed by different flow paths) could be the start of an explanation for the observed chemical and temperature variations.

14 Three Inlet Pipes

Figure 14: Coldwater Spring House Northwest Face Inside Wall This figure shows a map of the northwest face inside wall of the springhouse, with the location shown in Figure 15. This inside wall contained three water inlets, from which water flowed into the springhouse.

Figure 15: Overhead Map with Sample Locations at Coldwater Spring This figure shows an overhead map of the Coldwater Spring area. The field samples taken from Coldwater Spring in this study were collected from the outflow pipe shown in this figure. All of the water that filled this reservoir flowed in the direction of the red flow arrows, toward Coldwater Spring Bridge.

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Figure 16: Three Inlet Sources into Coldwater Spring House This figure shows a nitrate, chloride, and temperature comparison between the three inlet sources and the outflow pipe. These four anion samples were obtained on 26 July 2015.

Varying Water Sources

Based on the discrepancies between the data logger and outfall temperatures, as well as the temperature differences shown in Figure 13, late in this study an investigation of the subwater level water inlets found that three different inlets contribute water to the Coldwater Spring House, Figure 14. These three inlets proved to have different water chemistries and temperatures. The nitrate vs. chloride and the temperature vs. nitrate plots in Figure 16 indicate that the outfall pipe is composed of about 80% water flowing from Inlet A, 10% water from Inlet B, and 10% water from Inlet C. This is based off the assumption that the water temperature did not change significantly in the period that the water was exposed to air temperature between the inlet pipes and the outflow pipe.

16 Chloride Input Sources

Figure 17: Chloride Concentrations from Ten Different Sample Locations This figure shows chloride concentrations obtained from ten different sample locations around Coldwater Spring, as percentages of the highest and lowest chloride concentrations. The first seven locations are labeled in Figures 14 and 15, and the Wetland A north sample was obtained roughly five yards north of the Wetland A gravel sample location. This data was obtained January 4th, 2016.

The differences in chemistry and temperature of the three inlet pipes in the Coldwater Springhouse were not found and documented until late in this study. On 4 January 2016 a synoptic sampling of ten water sources was conducted in Coldwater Spring and Wetland A. The results of this sampling are listed in Appendix B and illustrated in Figure 17. The lowest chloride content (390 ppm) was observed in Inlet Pipe C in the Coldwater Springhouse. The highest chloride content (580 ppm) was observed at Tufa Drops in the southwest corner of lower Coldwater Spring Pond.

Assuming that all ten samples are linear mixtures of two end members represented by the highest and lowest two samples, the relative proportions of the two end members are shown in Figure 17. This assumption is probably not valid, however. The Tufa Drips sample is probably itself a mixture of two or more water sources – as are all of the others. An interesting observation is that the highest chloride concentrations occur (at least in the 4 January 2016 sampling) near the middle of the sampling array. The chloride contamination is not uniform over the recharge areas of the different water outlets. Nitrate-Nitrogen

The 1974 Safe Drinking Water Act set a national maximum contaminant level (MCL) for nitrate of 10 ppm as an enforceable standard (Water, 2013). Although the nitrate levels in each sample

17 site are below this drinking standard, maximum contaminant levels are purposely set as close as possible to the health goals. Nitrate-nitrogen is an indicator parameter of contamination, and is often accompanied with other pollutants such as pathogenic viruses, bacteria and synthetic organic compounds. Therefore, the elevated levels found in Coldwater Spring and Wetland A are significant and, in this urban setting, suggest contamination from human sources such as lawn fertilizer runoff or leaking sanitary sewage lines.

Figure 18. Nitrate-Nitrogen Levels for Coldwater Spring and Wetland A This figure shows the field data for the Nitrate-Nitrogen levels in Coldwater Spring.

Nitrate-Nitrogen Levels in Coldwater Spring

The nitrate-nitrogen levels in Coldwater Spring (Figure 18) varied between 2.6 ppm to 5.2 ppm during this study. The concentration of nitrate-nitrogen rose by about 2 ppm over two years, and also displayed a sinusoidal pattern. The annual nitrate minima occur almost simultaneously with the highest chlorides.

One potential source of nitrate-nitrogen is leaking sanitary sewer lines, but one would expect a more constant nitrate source year-round. An additional possible source of the nitrate-nitrogen is from lawn fertilizer application. Seasonal application of lawn fertilizers occurs roughly opposite the use of road salt – mainly in the spring and summer months.

Nitrate-Nitrogen Levels in Wetland A

Wetland A had a wider nitrate-nitrogen level range than Coldwater Spring, varying between about 0.3 ppm and 6.0 ppm. Wetland A’s nitrate-nitrogen levels vary much more than do Coldwater Spring’s but are rising when Coldwater’s levels are dropping and vice versa. The

18 nitrate levels at Wetland A may reflect the more locally dominated recharge and lack of fertilizer application on the Coldwater Spring property.

Major Ion Chemistry

Figure 19: 3D Piper Diagram for Coldwater Spring and Wetland A This figure shows a 3D Piper diagram of major cation and anion composition.

Piper Diagrams are a 2D graphical technique for displaying and interpreting the major ion chemistries of water samples (Piper, 1944). The lower left triangle is a ternary diagram of the major dissolved cations. The lower right triangle is a ternary diagram of the major anions. The two triangles are projected into the middle square. Figure 19 is a 3D Piper Diagram where the total concentrations of the dissolved ions are shown by the vertical bars. Figure 19 illustrates that the waters from Coldwater Spring and the waters from Wetland A have roughly similar major ion chemistries, but differ enough to be able to be able to be distinguished. Wetland A’s waters contain higher levels anthropogenic ions of sodium, chloride, and nitrate, than Coldwater Spring’s waters.

Most springs from carbonate rocks in Minnesota fall closer to the bicarbonate corner of the anion triangle than do the waters Coldwater Spring and Wetland A. Solution of the Platteville Limestone produces calcium, magnesium and bicarbonate ions. Coldwater Spring’s anions are about 50% chloride and Wetland A’s anions are about 60% chloride in terms of milliequivalents per liter. Both numbers are a measure of the large chloride and nitrate contamination of the spring and wetland water sources.

The large concentrations of chloride in the waters from both sources are not balanced by the sodium concentrations. Cation exchange has occurred along the groundwater pathways in the

19 time between the applications of the road salt, and when the dissolved road salt reaches the springs.

Both Coldwater Spring and Wetland A’s waters have relatively constant elevated sulfate ion concentrations of about 80 to 90 ppm. These values are probably produced naturally from the oxidation of sulfides present in the Platteville Limestone.

Summary and Conclusions

1. The temperature and water chemistry of the groundwater flowing from Coldwater Spring and Wetland A appear to have been significantly impacted by human activities.

2. The chloride concentrations in Coldwater Spring’s waters have increased 100-fold between 1880 and the present. In recent years, the chloride concentration of Coldwater Spring appears to be increasing at a faster rate than between 1880 and 1998 and between 1998 and 2012. The chloride contents in Wetland A’s waters are even higher than those in Coldwater Spring. The chloride/ bromide ratios in both springs suggest that road salt is likely the primary source of the chloride. The chloride contents of Coldwater Spring and Wetland A fluctuate in mirror image fashion: one is high when the other is low and vice versa.

3. Coldwater Spring is no longer a constant temperature spring. Coldwater Spring’s temperature fluctuates smoothly by 2.4 °C. The temperatures are 3 to 5 °C warmer than the temperatures of the spring in 1837. The temperature fluctuations are not in phase with seasonal air temperatures. Coldwater Spring’s waters are coolest in June and warmest in November. Dense urbanization of the region around Coldwater Spring has driven larger seasonal variation in soil temperature and higher temperatures overall.

4. Wetland A is fed by a shallow and more local ground water recharge area than Coldwater Spring. Wetland A has larger temperature fluctuations than Coldwater Spring and is only slightly out of phase with the seasonal air temperature.

5. Coldwater Spring’s nitrate-nitrogen levels rose from about 3 ppm in February 2013 to over 5 ppm in January 2015. One potential source of nitrate-nitrogen is leaking sanitary sewage lines, but one would expect that input would be a more constant nitrate source year-round. A second source is larger pulses of nitrate from seasonal lawn fertilizer applications, which occur during the spring and summer – in different seasons than the road salt applications.

6. Wetland A’s nitrate levels peak in the spring at 6 ppm but are generally lower than Coldwater Spring, around 1 ppm through most of the summer and winter. This may reflect the more locally dominated recharge and lack of fertilizer application on the Coldwater Spring property and adjacent roadways.

7. Annual fluctuation cycles in nitrate and chloride contents are superimposed on longer term increasing trends of both parameters. The nitrates decrease at the same time that the chlorides are increasing – in a mirror image.

8. The dye trace conducted at Coldwater Spring was inconclusive. No positive results were detected at eight different sample locations in the Coldwater Spring area.

20 9. Three different water chemistries were determined to be flowing into the Coldwater springhouse through three inlets. The water exiting the outflow pipe was determined to be composed of about 80% of the water from Inlet A, 10% of the water from Inlet B, and 10% of the water from Inlet C.

Acknowledgements

A special thanks goes to the National Park Service for partial funding of this project and for NPS staff assistance and encouragement. Another special thanks to the University of Minnesota’s Undergraduate Research Opportunities Program for partially funding this project and for the opportunity to present the preliminary results at the National Conference on Undergraduate Research in April 2014. SMK would like to thank her previous coauthors, Professor E. Calvin Alexander, Jr. and Scott Alexander, for their contribution to this paper and for their support and mentorship throughout this project. SMK would like to thank her advisor Randal Barnes for editing and providing feedback on this paper. SMK would also like to thank her father Hisanao for taking her sampling every week throughout the school year and the cold Minnesota winter, and to her mother Susan for driving her to and from the University of Minnesota campus during the summer. We thank Betty Wheeler for her editing earlier versions of this paper.

21 References Alexander EC Jr, Alexander SC, Barr K.2001 Dye Tracing to Camp Coldwater Spring, Minneapolis, MN. Minn. Groundwater Assoc. Newsletter 20(4): 4-6. Corsi S, De Cicco L, Lutz M, Hirsch R. 2014. River chloride trends in snow-affected urban watersheds: increasing concentrations outpace urban growth rate and are common among all seasons. Science of The Total Environment 508: 488-497. Available from: http://www.sciencedirect.com/science/article/pii/S0048969714017148 Davis SN, Whittemore DO, Fabryka-Martin J. 1998. Uses of Chloride/Bromide Ratios in Studies of Potable Water. Ground Water 36(2): 338-350. Homstad, Maia. 2010. Hold the salt. In: Minnesota Conservation Volunteer. January-February, 2010. St. Paul (MN): Minnesota Department of Natural Resources: 62-63. Available from: http://www.dnr.state.mn.us/mcvmagazine/archive.html Howe C, Lauzon B. 2014. Safeguarding Coldwater Spring. Minnesota Department of Transportation Right- of-Way. Kelly VR, Findlay SEG, Schlesinger WH, Menking K, Chatrchyan AM. 2010. Road Salt: Moving Toward the Solution. The Cary Institute of Ecosystem Studies. Available from: http://www.caryinstitute.org/sites/default/files/public/reprints/report_road_salt_2010.pdf Kasahara, SM. 2014. Chloride monitoring at Coldwater Spring. In: Snow DM, Guerrant B, co-chairs. 28th National Conference on Undergraduate Research, April 3-5, 2014. Lexington (KY): The University of Kentucky. Available from: http://www.ncurproceedings.org/ojs/index.php/NCUR2014 Kasahara, SM., Alexander Jr. EC, Alexander SC. 2015. Human Impacts on Water Quality in Coldwater Spring, Minneapolis, Minnesota. In: Veni G, La Moreaux J, Barr K, co-chairs. 14th Annual Sinkhole Conference, October 5-9, 2015. Rochester (MN): Rochester Convention Center. Available from: http://scholarcommons.usf.edu/sinkhole_2015/ProceedingswithProgram/Upper_Mississippi_Valley_ Karst_Aquifers/2/ Kelly, Walt. 2011. Road Salt (Part 1). [Internet]. Illinois State Water Survey. Available from: https://illinois.edu/blog/view/789/62191 Keseley, Shaina. 2007. From icy roads to salty waters: road salt effects on our environment. [Internet]. [Place of publication unknown]: The Illinois Association of Public Procurement Officials, Inc. Available from: http://juarezprojectcitizen.wikispaces.com/file/view/IAPPO07_RoadSalt.pdf Local climate records. [Internet]. 1995. [Place of publication unknown]: National Weather Service Weather Forecast Office. National Oceanic and Atmospheric Administration. Available from: http://www.crh.noaa.gov/mpx/Climate/MSPClimate.php Maguire E. 1880. Press copies of office letters sent by Captain Edward Maguire, Chief Engineer, June 26, 1880. In: The Water. Department of Dakota., p. 2 MAR 4725. 2013. Minnesota Administrative Rules, Chapter 4725. Wells and borings. [Internet]. St. Paul (MN): State of Minnesota. Office of the Revisor of Statutes. Available from: https://www.revisor.mn.gov/rules/?id=4725

Mohseni O, Stefan HG. 2006. Study of environmental effects of de-icing salt on water quality in Minnesota. [Internet]. Minneapolis (MN): University of Minnesota Center for Transportation Studies. Available from: http://www.cts.umn.edu/Research/ProjectDetail.html?id=2006071 Nicollet JN. 1845. Report intended to illustrate a map of the hydrographical basin of the Upper Mississippi River. [Internet]. 1845. Document of the US House of Representatives. 28th Congress, 2nd Session, no. 52. Washington (DC): Blair and Rives. http://www.worldcat.org/title/report-intended-to-illustrate-a- map-of-the-hydrographical-basin-of-the-upper-mississippi- river/oclc/166586906?referer=di&ht=edition

22 NPS. 2012. Coldwater Spring Restoration Project. Mississippi National River and Recreation Area. [Internet]. [Place of publication unknown]: National Park Service. US Department of the Interior. Available from: http://www.nps.gov/miss/parkmgmt/bomcurr.htm Panno S, Hackley K, Hwang H, Greenberg S, Krapac I, Landsberger S, O’Kelly D. 2006. Characterization and Identification of Na-Cl Sources in Groundwater. Groundwater 44 (2): 176-187. PCCC. 2012. Preserve Camp Coldwater coalition. [Internet]. [Place of publication unknown]: Preserve Camp Coldwater Coalition. Available from: http://www.preservecampcoldwater.org/index.html Piper AM. 1944. A graphical procedure in the geochemical interpretation of water analyses. American Geophysical Union Transactions 25: 914-923. Rastogi N. [Internet] 2010. Does road salt harm the environment? [Place of publication unknown]: Slate.com. Available from: http://www.slate.com/articles/health_and_science/the_green_lantern/2010/02/salting_the_earth.html Sander A, Novotny E, Mohseni O, Stefan H. 2007. Inventory of road salt use in the Minneapolis/St. Paul Metropolitan Area. Minneapolis (MN): St. Anthony Falls Laboratory. Available from:http://purl.umn.edu/115332 Shen Z, Konishi H, Brown PE, Xu H. 2013. STEM investigation of exsolution lamellae and “c” reflections in Ca-rich dolomite from the Platteville Formation, western Wisconsin. American Mineralogist: 98(4): 760-766. Available from: http://www.minsocam.org/MSA/AmMin/TOC/2013/Apr13.html

Stefan HG, Novotny E, Sander A, Mohseni O. 2008. Study of environmental effects of de-icing salt on water quality in the Twin Cities Metropolitan Area, Minnesota. Report no. MN/RC 2008-42. St. Paul (MN): Minnesota Department of Transportation. Available from: http://www.lrrb.org/media/reports/200842.pdf

UMCTS. 2006. Minneapolis (MN): University of Minnesota Center for Transportation Studies. Available from: http://www.cts.umn.edu/Research/ProjectDetail.html?id=2006071 Water. 2013. Basic information about regulated drinking water contaminants. [Internet]. [Place of publication not available]: US Environmental Protection Agency. Available from: http://water.epa.gov/drink/contaminants/basicinformation/

White, BM. 2000. Highway 55 and the Camp Coldwater Settlement: An Independent Investigation. Turnstone Historical Research. St. Paul (MN). Available from: http://www.tc.umn.edu/~white067/

23 Appendix A: Field Data for Coldwater Spring, Wetland A, Wetland H, and Big Culvert

This Appendix contains field data from 2012 to 2016 for the four main sample sites at Coldwater Spring. The Wetland H location was a wetland located to the North of Coldwater Spring, near the Northeast corner of the parking lot.

Coldwater Coldwater Coldwater Coldwater Coldwater Coldwater Coldwater Coldwater Coldwater Sample Name Spring Spring Spring Spring Spring Spring Spring Spring Spring UTM E (NAD83) 484,477 484,477 484,477 484,477 484,477 484,477 484,477 484,477 484,477 UTM N (NAD83) 4,971,784 4,971,784 4,971,784 4,971,784 4,971,784 4,971,784 4,971,784 4,971,784 4,971,784 Sample Date 23-Feb-2012 15-Feb-2013 2-Mar-2013 10-Mar-2013 16-Mar-2013 23-Mar-2013 2-Apr-2013 8-Apr-2013 15-Apr-2013

Field Parameters Temp (ºC) --- 12.7 12.3 12.1 12.1 11.9 11.8 11.7 11.6 pH --- 7.12 ------7.13 7.13 7.13 7.11 --- Cond (mS/cm) 1.665 1.455 1.802 1.820 1.832 1.718 DO (ppm) ------1.44 1.48 --- 1.32 ---

Cations (in ppm) Ca 201 177.0 139.0 Mg 56.7 50.5 49.62 Na 158.1 111 110.4 K 3.1 2.70 ------2.810 ------Al 0.013 0.001 ------nd ------Fe 0.015 0.21 ------0.128 ------Mn 0.7450 0.0005 ------0.0022 ------Sr 0.256 0.297 ------0.207 ------Ba 0.2937 0.195 ------0.308 ------Si 11.6 10.7 ------10.9 ------

Anions (in ppm)

Alk. (as CaCO 3) 357.5* 338 ------351 ------Cl 436.7 331 321.0 320.3 320.7 320.4 322.2 324.2 328.4 Br 0.152 0.148 0.155 0.146 0.159 0.166 0.153 0.142 0.161

NO 3 -N 3.118 3.022 3.100 3.101 3.041 3.018 3.016 3.182 2.855

NO 2 -N <0.006 0.022 <0.002 <0.002 <0.002 <0.002 <0.002 <0.002 <0.002

SO4 94.75 87.5 88.847 88.664 88.724 88.535 88.01 89.162 88.432

PO4 -P 0.017 <0.005 <0.005 <0.005 <0.005 <0.005 <0.005 <0.005 <0.005 Total P 0.022 0.035 0.015 F 0.071 0.064 0.096 0.083 0.091 0.085 0.062 0.083 0.092

CH 3 CO 2- <0.010 <0.010 <0.010 <0.010 <0.010 <0.010 <0.010 <0.010 <0.010

HCO 2- <0.010 <0.010 <0.010 <0.010 <0.010 <0.010 <0.010 <0.010 <0.010

Calculated Data Charge Balance Cations (meq/kg) 21.66 17.89 ------15.90 ------Anions (meq/kg) * 18.14 18.16 % difference * -0.67 ------6.62 ------

Cl/Br (wt ratio) 2,873 2,236 2,071 2,194 2,017 1,930 2,106 2,283 2,039

Sodium Mass Ratio 22.99 45.98

Cl = 313 ppm * alkalinity by titration calculated to balance cations

24 Appendix A- Continued

Coldwater Coldwater Coldwater Coldwater Coldwater Coldwater Coldwater Coldwater Coldwater Coldwater Coldwater Spring Spring Spring Spring Spring Spring Spring Spring Spring Spring Spring 484,477 484,477 484,477 484,477 484,477 484,477 484,477 484,477 484,477 484,477 484,477 4,971,784 4,971,784 4,971,784 4,971,784 4,971,784 4,971,784 4,971,784 4,971,784 4,971,784 4,971,784 4,971,784 21-Apr-2013 27-Apr-2013 4-May-2013 12-May-2013 20-May-2013 28-May-2013 1-Jun-2013 10-Jun-2013 20-Jun-2013 25-Jun-2013 2-Jul-2013

11.6 11.5 11.4 11.4 11.3 11.3 11.3 11.3 11.3 11.3 11.25 --- 7.11 7.11 7.10 7.64* 7.14 7.25 7.00 7.19 7.99 8.24 1.767 1.866 1.912 1.637 1.983 1.994 2.023 1.971 1.926 1.921 --- 1.53 1.86 1.98 --- 1.54 1.4 1.43 1.99 2.38 1.55

142.1 188.97 50.82 53.252 121.8 156.09 --- 2.825 ------3.2995 ------0.0038 ------nd ------0.128 ------0.00172 ------0.0011 ------0.0191 ------0.212 ------0.22646 ------0.277 ------0.4224 ------10.89 ------11.304 ---

--- 340 ------343 ------353 --- 337.2 350.4 378.0 400.5 388.3 413.3 414.3 432.1 424.0 417.4 387.8 0.154 0.155 0.135 0.133 0.120 0.164 0.141 0.17 0.156 0.175 0.141 2.791 2.787 2.665 2.706 2.558 2.527 2.557 2.711 2.692 2.531 2.662 <0.002 <0.002 <0.004 <0.004 <0.004 <0.004 <0.006 <0.004 <0.004 <0.004 <0.006 86.991 86.186 85.8 85.8 86.2 85.0 80.8 83.6 84.9 83.2 82.7 <0.005 <0.005 <0.010 <0.010 <0.010 <0.010 <0.015 <0.010 <0.010 <0.010 <0.015 0.005 0.033 0.076 0.073 0.066 0.068 0.098 0.083 0.105 0.07 0.092 0.083 0.094 <0.010 <0.010 <0.020 <0.020 <0.020 <0.020 0.454 <0.020 <0.020 <0.020 0.176 <0.010 <0.010 <0.020 <0.020 <0.020 <0.020 0.123 <0.020 <0.020 <0.020 0.073

--- 16.65 0.00 20.70 18.68 20.47 20.75 --- -5.74 -100.00 -0.12

2,190 2,261 2,800 3,011 3,236 2,520 2,947 2,542 2,718 2,385 2,758

* measured * there was a * used a with a Mettler man in the different Toledo meter Spring thermometer

25 Appendix A- Continued

Coldwater Coldwater Coldwater Coldwater Coldwater Coldwater Coldwater Coldwater Coldwater Coldwater Spring Spring Spring Spring Spring Spring Spring Spring Spring Spring 484,477 484,477 484,477 484,477 484,477 484,477 484,477 484,477 484,477 484,477 4,971,784 4,971,784 4,971,784 4,971,784 4,971,784 4,971,784 4,971,784 4,971,784 4,971,784 4,971,784 8-Jul-2013 15-Jul-2013 24-Jul-2013 29-Jul-2013 3-Aug-2013 12-Aug-2013 19-Aug-2013 25-Aug-2013 30-Aug-2013 8-Sep-2013

11.25 11.35 11.35 11.45 11.55 11.65 11.85 11.85 12.15 12.25 9.34 7.17 7.09 7.08 7.08 7.08 7.07 7.09 7.08 7.09 1.897 1.860 1.816 1.778 1.711 1.758 1.751 1.724 1.735 1.744 2.1 2.51 1.84 1.86 1.83 2.32 1.86 2.12 2.19 2.28

176.2 172.8367 49.518 48.251 137.36 126.557 ------2.9078 ------2.9629 ------0.004 ------0.0044 ------nd ------0.0044 ------0.001 ------0.0039 ------0.2019 ------0.206 ------0.2137 ------0.2044 ------11.2115 ------11.0733 ------

------346 ------335 ------382.9 372.8 358.1 378.2 359.3 345.8 341.3 340.6 339.6 339.4 0.138 0.135 0.135 0.147 0.137 0.130 0.133 0.134 0.134 0.132 2.744 2.771 2.756 4.012 2.879 2.844 3.167 3.12 3.297 3.364 <0.006 <0.006 <0.006 0.025 <0.006 0.014 <0.006 <0.006 0.009 0.007 81.9 82.0 81.2 87.9 83.0 82.2 82.1 81.8 82.546 82.296 <0.015 <0.015 <0.015 <0.015 0.023 <0.015 <0.015 <0.015 0.021 <0.015 0.030 0.025 0.062 0.076 0.076 0.093 0.098 0.099 0.102 0.108 0.110 0.109 0.196 0.234 <0.029 <0.030 <0.030 <0.030 <0.030 <0.030 <0.030 <0.030 0.059 0.038 0.038 <0.030 <0.030 <0.030 <0.030 <0.030 <0.030 <0.030

18.92 18.18 18.91 18.26 0.04 -0.22

2,782 2,767 2,658 2,573 2,622 2,660 2,566 2,542 2,534 2,571

* started using a new pH meter

* used a * used a * used a * used a * used a * used a * used a * used a * used a different different different different different different different different different thermometer thermometer thermometer thermometer thermometer thermometer thermometer thermometer thermometer

26 Appendix A- Continued

Coldwater Coldwater Coldwater Coldwater Coldwater Coldwater Coldwater Coldwater Coldwater Coldwater Spring Spring Spring Spring Spring Spring Spring Spring Spring Spring 484,477 484,477 484,477 484,477 484,477 484,477 484,477 484,477 484,477 484,477 4,971,784 4,971,784 4,971,784 4,971,784 4,971,784 4,971,784 4,971,784 4,971,784 4,971,784 4,971,784 14-Sep-2013 21-Sep-2013 28-Sep-2013 5-Oct-2013 13-Oct-2013 19-Oct-2013 26-Oct-2013 2-Nov-2013 9-Nov-2013 16-Nov-2013

12.25 12.35 12.45 12.45 ------12.25 12.55 12.45 12.65 7.10 7.09 7.08 7.11 7.08 7.07 7.05 7.07 7.05 7.06 1.723 1.742 1.752 1.763 1.774 1.791 1.784 1.801 1.827 1.834 2.69 2.35 2.18 1.46 --- 1.88 2.36 2.78 2.55 2.78

176.365 182.255 186.98 48.448 50.574 52.0365 117.095 119.225 115.55 2.9711 ------3.0831 ------3.1892 --- 0.0047 ------0.0055 ------nd --- 0.0036 ------0.0002 ------0.001 --- nd ------nd ------0.0016 --- 0.2025 ------0.2074 ------0.217 --- 0.1908 ------0.2004 ------0.2053 --- 10.6895 ------11.303 ------11.417 ---

338 ------322 ------324 --- 340.8 344.2 346.4 348.3 351.7 349.1 351.8 353.2 356.2 358.3 0.136 0.139 0.141 0.143 0.144 0.133 0.136 0.140 0.141 0.142 3.513 3.653 3.744 3.822 3.901 3.852 3.91 3.96 4.004 4.028 <0.006 <0.006 <0.006 <0.006 <0.006 <0.006 <0.006 <0.006 <0.006 <0.006 82.284 83.0 83.3 83.3 83.3 82.3 82.4 82.6 82.9 83.2 <0.015 0.03 0.022 <0.015 <0.015 0.041 0.027 0.022 0.023 <0.015 0.033 0.038 0.037 0.090 0.091 0.092 0.093 0.092 0.087 0.089 0.089 0.089 0.089 <0.030 <0.030 <0.030 <0.030 <0.030 <0.030 <0.030 <0.030 <0.030 <0.030 <0.030 <0.030 <0.030 <0.030 <0.030 <0.030 <0.030 <0.030 <0.030 <0.030

17.96 18.53 18.73 18.34 18.37 18.54 -1.03 0.42 0.51

2,506 2,476 2,456 2,436 2,442 2,625 2,587 2,523 2,526 2,523

* used a * used a * used a * no * no different different different * used a * used a * used a * used a thermometer thermometer thermometer thermometer thermometer different different different different and no RDO and new RDO * new RDO and new RDO and new RDO and new RDO thermometer thermometer thermometer thermometer cap cap cap cap cap cap

27 Appendix A- Continued

Coldwater Coldwater Coldwater Coldwater Coldwater Coldwater Coldwater Coldwater Coldwater Coldwater Spring Spring Spring Spring Spring Spring Spring Spring Spring Spring 484,477 484,477 484,477 484,477 484,477 484,477 484,477 484,477 484,477 484,477 4,971,784 4,971,784 4,971,784 4,971,784 4,971,784 4,971,784 4,971,784 4,971,784 4,971,784 4,971,784 24-Nov-2013 1-Dec-2013 8-Dec-2013 15-Dec-2013 21-Dec-2013 28-Dec-2013 4-Jan-2014 11-Jan-2014 18-Jan-2014 25-Jan-2014

12.45 12.55 12.45 12.45 12.35 12.45 12.45 12.4 12.3 12.2 7.05 7.07 6.95 6.89 6.94 6.96 6.96 6.93 6.89 6.89 1.835 1.855 1.853 1.852 1.849 1.854 1.851 2.256 2.145 2.104 3.32 2.45 2.9 2.6 2.24 ------2.49 2.52 2.77

190.6867 194.45 52.6057 53.071 115.78 117.66 ------3.1744 ------3.0406 ------0.0131 ------nd ------0.0294 ------nd ------0.0043 ------nd ------0.2216 ------0.2211 ------0.209 ------0.2113 ------11.4763 ------11.369 ------

------339 ------344 ------362.1 366.0 368.0 370.0 372.7 374.1 377.0 378.2 381.0 380.0 0.139 0.142 0.142 0.145 0.146 0.148 0.148 0.153 0.154 0.154 4.009 4.041 4.069 4.049 4.07 4.04 4.08 4.023 4.07 4.001 <0.006 <0.006 <0.006 <0.006 <0.006 <0.006 <0.006 0.013 <0.006 <0.006 82.2 82.5 82.7 83.2 83.7 83.7 84.3 83.5 83.7 84.1 0.029 0.027 0.022 0.057 0.027 0.022 0.017 0.034 <0.015 <0.015 0.034 0.029 0.087 0.087 0.086 0.084 0.086 0.086 0.085 0.136 0.107 0.131 <0.030 <0.030 <0.030 <0.030 <0.030 <0.030 <0.030 <0.015 <0.015 <0.015 <0.030 <0.030 <0.030 <0.030 <0.030 <0.030 <0.030 <0.015 <0.015 <0.015

18.97 19.27 19.17 19.56 -0.54 -0.74

2,605 2,578 2,592 2,552 2,553 2,528 2,547 2,472 2,474 2,467

* everything was calibrated

* used a * used a * used a * used a * used a different different different different different * used a * used a * used old * used old * used old thermometer thermometer thermometer thermometer thermometer different different thermometer thermometer thermometer and new RDO and new RDO and new RDO and new RDO and new RDO thermometer, thermometer, and a fixed and a fixed and a fixed cap cap cap cap cap no DO no DO RDO cap RDO cap RDO cap

28 Appendix A- Continued

Coldwater Coldwater Coldwater Coldwater Coldwater Coldwater Coldwater Coldwater Coldwater Coldwater Spring Spring Spring Spring Spring Spring Spring Spring Spring Spring 484,477 484,477 484,477 484,477 484,477 484,477 484,477 484,477 484,477 484,477 4,971,784 4,971,784 4,971,784 4,971,784 4,971,784 4,971,784 4,971,784 4,971,784 4,971,784 4,971,784 9-Feb-2014 16-Feb-2014 23-Feb-2014 1-Mar-2014 8-Mar-2014 15-Mar-2014 25-Mar-2014 29-Mar-2014 6-Apr-2014 12-Apr-2014

12.1 12 11.9 11.8 11.7 11.6 11.5 --- 11.2 11.2 7.00 7.00 --- 6.87 6.85 6.83 6.80 --- 6.85 6.90 2.118 2.117 --- 2.170 2.100 2.076 2.166 --- 2.084 2.279 3.28 2.85 --- 2.86 2.72 3.97 2.46 --- 2.74 2.92

196.5667 196.0717 198.9633 54.5197 54.0443 55.2163 118.3567 125.3433 128.26 3.2385 ------3.1449 ------3.17 --- nd ------nd ------0.0018 --- nd ------nd ------nd --- nd ------nd ------0.0001 --- 0.2303 ------0.2274 ------0.2318 --- 0.2149 ------0.2134 ------0.2135 --- 11.3377 ------11.3332 ------11.3187 ---

341 ------343 ------333 --- 383.1 381.5 382.4 382.2 380.2 378.6 384.5 384.9 390.3 399.3 0.154 0.148 0.144 0.139 0.134 0.153 0.149 0.150 0.147 0.142 3.971 4.008 4.007 3.988 3.942 3.812 3.706 3.674 3.633 3.653 <0.006 <0.006 <0.006 <0.006 <0.006 0.023 0.029 0.031 0.037 <0.006 84.9 84.8 85.5 85.6 85.3 84.3 84.1 84.0 84.4 84.5 <0.015 <0.015 <0.015 <0.015 <0.015 <0.015 <0.015 <0.015 <0.015 <0.015 0.037 0.030 0.031 0.145 0.113 0.115 0.115 0.114 0.056 0.067 0.070 0.068 0.076 <0.015 <0.015 <0.015 <0.015 <0.015 <0.015 <0.015 <0.015 <0.015 <0.015 <0.015 <0.015 <0.015 <0.015 <0.015 <0.015 <0.015 <0.015 <0.015 <0.015

19.53 19.77 20.14 19.68 19.64 19.69 -0.38 0.33 1.13

2,488 2,577 2,656 2,750 2,837 2,474 2,581 2,566 2,655 2,812

* used old * used old * used old * used old * used old * used old thermometer thermometer thermometer thermometer thermometer thermometer * used Therm and new and new and no Thermo and old and old and old #8487 and old Thermo Orion Thermo Orion Orion Thermo Orion Thermo Orion Thermo Orion Thermo Orion eqiupment eqiupment eqiupment eqiupment eqiupment eqiupment eqiupment

29 Appendix A- Continued

Coldwater Coldwater Coldwater Coldwater Coldwater Coldwater Coldwater Coldwater Coldwater Coldwater Spring Spring Spring Spring Spring Spring Spring Spring Spring Spring 484,477 484,477 484,477 484,477 484,477 484,477 484,477 484,477 484,477 484,477 4,971,784 4,971,784 4,971,784 4,971,784 4,971,784 4,971,784 4,971,784 4,971,784 4,971,784 4,971,784 19-Apr-2014 28-Apr-2014 4-May-2014 11-May-2014 20-May-2014 24-May-2014 31-May-2014 8-Jun-2014 17-Jun-2014 6-Jul-2014

11.1 11 10.9 10.9 10.8 10.8 10.8 10.8 10.7 10.9 6.82 --- 6.89 6.80 6.70 6.82 7.07 7.09 7.04 7.16 2.301 --- 2.164 2.128 2.207 2.151 2.208 2.144 2.034 2.188 2.53 --- 2.97 2.55 2.16 1.9 2.34 2.75 1.87 2.4

203.0033 204.23 180.0933 56.1483 56.0645 49.9293 142.68 156.845 150.4133 ------3.1735 ------3.3241 ------3.0613 ------0.0138 ------0.0153 ------0.0097 ------0.0098 ------0.0196 ------0.0024 ------0.0004 ------0.0023 ------0.0003 ------0.2369 ------0.2352 ------0.2066 ------0.2184 ------0.2254 ------0.2004 ------11.2933 ------11.3925 ------11.2293

------349 ------362 ------365 415.2 414.5 422.4 448.4 455.2 458.0 455.2 420.1 407.7 377.0 0.142 0.142 0.180 0.177 0.177 0.175 0.165 0.151 0.145 0.136 3.67 3.508 3.329 3.421 3.407 3.345 3.381 3.269 3.311 3.6 <0.006 <0.006 <0.006 <0.006 <0.006 <0.006 <0.006 <0.006 <0.006 <0.006 84.7 83.4 82.3 82.0 82.8 82.7 83.7 78.3 78.1 78.5 <0.015 <0.015 <0.015 0.023 0.022 0.018 0.017 0.041 0.025 <0.015 0.030 0.037 0.038 0.083 0.082 0.083 0.082 0.082 0.082 0.082 0.080 0.080 0.082 <0.015 <0.015 <0.015 <0.015 <0.015 <0.015 <0.015 <0.015 <0.015 <0.015 <0.015 <0.015 <0.015 <0.015 <0.015 <0.015 <0.015 <0.015 <0.015 <0.015

21.05 21.72 19.72 20.85 22.06 19.83 0.48 -0.79 -0.26

2,924 2,919 2,347 2,533 2,572 2,617 2,759 2,782 2,812 2,772

Therm #8487 Therm #8487 Therm #8487 Therm #8487 Therm #8487 Therm #8487

30 Appendix A- Continued

Coldwater Coldwater Coldwater Coldwater Coldwater Coldwater Coldwater Coldwater Coldwater Coldwater Spring Spring Spring Spring Spring Spring Spring Spring Spring Spring 484,477 484,477 484,477 484,477 484,477 484,477 484,477 484,477 484,477 484,477 4,971,784 4,971,784 4,971,784 4,971,784 4,971,784 4,971,784 4,971,784 4,971,784 4,971,784 4,971,784 12-Jul-2014 20-Jul-2014 26-Jul-2014 2-Aug-2014 10-Aug-2014 17-Aug-2014 24-Aug-2014 29-Aug-2014 7-Sep-2014 14-Sep-2014

11.1 12.1 11.9 12.2 12.1 12.4 12.3 12.5 12.6 12.7 6.94 6.99 7.03 7.05 7.00 7.10 7.14 7.13 6.99 7.01 2.505 1.947 1.924 1.888 1.848 1.854 2.291 2.024 1.794 1.819 1.98 2.18 2.67 2.69 --- 2.73 2.36 2.33 ------

175.68 184.655 47.765 50.1995 129.315 118.21 ------3.8774 ------3.8027 ------0.0049 ------nd ------0.0051 ------0.0676 ------nd ------nd ------0.2 ------0.2069 ------0.1916 ------0.1975 ------11.2655 ------11.4275 ------

--- 341 333 377.1 364.6 356.4 350.5 349.1 350.8 355.9 360.0 362.3 368.4 0.104 0.109 0.100 0.100 0.087 0.126 0.131 0.149 0.149 0.148 3.699 3.664 3.718 3.838 4.018 4.158 4.337 4.386 4.54 4.668 <0.010 <0.010 <0.010 <0.010 <0.010 <0.010 <0.010 <0.010 <0.007 <0.007 80.9 79.6 79.1 78.9 78.1 79.5 79.0 79.1 80.5 80.7 0.082 0.056 0.046 0.039 0.065 0.039 0.034 <0.025 <0.018 <0.018 0.040 0.039 0.086 0.085 0.085 0.088 0.084 0.087 0.083 0.084 0.088 0.087 <0.025 <0.025 <0.025 <0.025 <0.025 <0.025 <0.025 <0.025 <0.018 <0.018 <0.025 <0.025 <0.025 <0.025 <0.025 <0.025 <0.025 <0.025 <0.018 <0.018

18.43 18.59 18.62 18.77 -0.53 -0.49

3,626 3,345 3,564 3,505 4,013 2,784 2,716 2,416 2,431 2,489

Therm #8487 Therm #8434 Therm #8434 Therm #8434 Therm #8434 Therm #8434 Therm #8434 Therm #8434 Therm #8434 Therm #8434

31 Appendix A- Continued

Coldwater Coldwater Coldwater Coldwater Coldwater Coldwater Coldwater Coldwater Coldwater Coldwater Spring Spring Spring Spring Spring Spring Spring Spring Spring Spring 484,477 484,477 484,477 484,477 484,477 484,477 484,477 484,477 484,477 484,477 4,971,784 4,971,784 4,971,784 4,971,784 4,971,784 4,971,784 4,971,784 4,971,784 4,971,784 4,971,784 21-Sep-2014 27-Sep-2014 4-Oct-2014 12-Oct-2014 19-Oct-2014 26-Oct-2014 2-Nov-2014 9-Nov-2014 16-Nov-2014 22-Nov-2014

12.8 12.9 12.8 13.0 13.0 13.0 13.1 13.1 13.1 13.1 6.97 6.93 6.93 6.91 6.93 6.91 7.09 7.01 7.16 7.03 1.851 1.875 1.917 1.951 1.983 1.991 1.982 1.946 2.015 2.068 ------2.90 2.84 --- 3.14

190.543 199.2825 200.8533 53.266 55.4908 57.2343 117.08 128.1375 130.76 --- 3.055 ------3.3357 ------3.4306 --- 0.043 ------0.0023 ------0.0048 --- 0.004 ------0.0095 ------0.01 --- 0.001 ------0.0008 ------0.0012 --- 0.224 ------0.2256 ------0.2265 --- 0.211 ------0.214 ------0.2201 --- 11.347 ------11.2633 ------11.4097

331 343 337 375.3 380.9 390.3 396.1 400.0 402.2 403.2 399.9 401.6 402.9 0.151 0.151 0.153 0.157 0.155 0.158 0.158 0.157 0.155 0.170 4.762 4.814 4.989 5.034 5.089 5.113 5.116 5.151 5.159 5.205 <0.007 <0.007 <0.010 <0.010 <0.010 <0.010 <0.010 <0.010 <0.010 <0.010 80.9 81.1 82.3 82.4 82.8 83.0 83.1 81.5 82.1 82.7 <0.018 <0.018 <0.025 <0.025 <0.025 <0.025 <0.025 <0.025 <0.025 <0.025 0.033 0.037 0.032 0.086 0.086 0.080 0.082 0.082 0.082 0.083 0.085 0.090 0.091 <0.018 <0.018 <0.025 <0.025 <0.025 <0.025 <0.025 <0.025 <0.025 <0.025 <0.018 0.030 <0.025 <0.025 <0.025 <0.025 <0.025 <0.025 <0.025 <0.025

19.07 20.18 20.52 19.40 20.30 20.20 -0.85 -0.30 0.78

2,485 2,522 2,551 2,523 2,581 2,545 2,552 2,547 2,591 2,370

Therm #8434 Therm #8434 Therm #8434 Therm #8434 Therm #8434 Therm #8434 Therm #8434 Therm #8434 Therm #8434 Therm #8434

32 Appendix A- Continued

Coldwater Coldwater Coldwater Coldwater Coldwater Coldwater Coldwater Coldwater Coldwater Coldwater Spring Spring Spring Spring Spring Spring Spring Spring Spring Spring Overflow 484,477 484,477 484,477 484,477 484,477 484,477 484,477 484,477 484,477 484,477 4,971,784 4,971,784 4,971,784 4,971,784 4,971,784 4,971,784 4,971,784 4,971,784 4,971,784 4,971,784 30-Nov-2014 7-Dec-2014 14-Dec-2014 20-Dec-2014 30-Dec-2014 3-Jan-2015 10-Jan-2015 18-Jan-2015 26-Jul-2015 30-Oct-2015

13.1 13.0 13.0 13.0 12.9 12.9 12.8 12.7 12.1 13.2 7.03 7.01 7.02 7.06 7.13 7.04 --- 7.05 7.01 2.043 2.013 2.032 2.084 2.194 2.034 --- 2.145 2.168 3.88 2.87 2.95 3.27 4.69 ------

201.575 57.0075 129.835 ------3.4894 ------0.0035 ------0.0058 ------0.0012 ------0.2403 ------0.2205 ------11.3185 ------

345 344 406.2 407.2 409.6 366.1 366.5 366.0 437.7 415.2 0.165 0.173 0.182 0.147 0.148 0.153 0.160 0.220 5.233 5.223 5.22 4.074 4.046 4.014 3.279 3.325 <0.010 <0.010 <0.010 <0.010 <0.010 <0.010 <0.010 <0.010 <0.004 <0.008 83.8 84.2 84.9 73.4 73.6 73.8 78.4 83.282 <0.025 <0.025 <0.025 <0.025 0.138 <0.025 <0.025 <0.025 0.138 <0.040 0.032 0.091 0.092 0.090 0.093 0.075 0.072 0.072 0.087 0.093 <0.025 <0.025 <0.025 <0.025 <0.025 <0.025 <0.025 <0.025 <0.020 <0.040 <0.025 <0.025 <0.025 <0.025 <0.025 <0.025 <0.025 <0.025 <0.020 <0.040

20.50 --- 19.03 3.71 ---

2,462 2,354 2,251 2,491 2,476 2,392 2,736 1,887

Suspected of being wrong

Therm #8434 Therm #8434 Therm #8434 Therm #8434 Therm #8434 Therm #8434

33 Appendix A- Continued

Coldwater Coldwater Coldwater Coldwater Coldwater Coldwater Coldwater Coldwater Coldwater Coldwater Spring Wetland A Wetland A Wetland A Wetland A Wetland A Wetland A Wetland A Wetland A Wetland A Outfall 484,477 484,492 484,492 484,492 484,492 484,492 484,492 484,492 484,492 484,492 4,971,784 4,971,711 4,971,711 4,971,711 4,971,711 4,971,711 4,971,711 4,971,711 4,971,711 4,971,711 4-Jan-2016 15-Feb-2013 2-Mar-2013 10-Mar-2013 16-Mar-2013 23-Mar-2013 2-Apr-2013 8-Apr-2013 15-Apr-2013 21-Apr-2013

12.9 8.6 8.6 8.1 8.5 7.8 8 8.4 7.8 7.7 7.12 ------7.01 7.06 7.09 7.06 ------2.16 2.720 2.698 2.718 2.551 ------1.88 2.16 --- 1.88 ------

208 162 57.7 56.21 231 233.8 --- 2.93 ------2.871 ------0.5 ------nd ------0.55 ------0.125 ------0.069 ------0.00152 ------0.268 ------0.263 ------0.272 ------0.326 ------11.2 ------10.34 ------

366 ------334 ------415.4 573 616.3 562.0 586.0 584.8 607.2 585.9 568.3 544.1 0.173 0.183 0.201 0.193 0.208 0.206 0.208 0.199 0.196 0.177 3.087 0.688 0.562 0.794 0.823 0.632 0.322 0.517 0.415 0.460 <0.008 0.014 <0.002 <0.002 <0.002 <0.002 <0.002 <0.002 <0.002 <0.002 80.967 82.3 82.9 105.28 88.2 82.85 88.51 89.28 86.79 84.13 <0.040 <0.005 <0.005 <0.005 <0.005 <0.005 <0.005 <0.005 <0.005 <0.005 0.056 nd 0.120 --- 0.083 0.083 0.087 0.077 0.055 0.08 0.076 0.077 <0.040 <0.010 <0.010 <0.010 <0.010 <0.010 <0.010 <0.010 <0.010 <0.010 <0.040 <0.010 <0.010 <0.010 <0.010 <0.010 <0.010 <0.010 <0.010 <0.010

--- 25.26 ------22.96 ------25.24 25.67 --- 0.04 ------5.57 ------

2,401 3,131 3,066 2,912 2,817 2,839 2,919 2,944 2,899 3,074

34 Appendix A- Continued

Coldwater Coldwater Coldwater Coldwater Coldwater Coldwater Coldwater Coldwater Coldwater Coldwater Coldwater Wetland A Wetland A Wetland A Wetland A Wetland A Wetland A Wetland A Wetland A Wetland A Wetland A Wetland A 484,492 484,492 484,492 484,492 484,492 484,492 484,492 484,492 484,492 484,492 484,492 4,971,711 4,971,711 4,971,711 4,971,711 4,971,711 4,971,711 4,971,711 4,971,711 4,971,711 4,971,711 4,971,711 27-Apr-2013 4-May-2013 12-May-2013 20-May-2013 28-May-2013 1-Jun-2013 10-Jun-2013 20-Jun-2013 25-Jun-2013 2-Jul-2013 8-Jul-2013

8.5 8.6 9.3 10.8 9.5 10.8 10.5 11.3 11.9 11.55 11.85 7.06 7.06 7.06 7.51* 7.03 6.93 7.16 7.76 7.94 8.03 9.29 2.418 2.368 2.297 1.662 2.069 2.053 2.026 1.528 2.042 2.058 2.047 1.87 2.30. 2.28 --- 2.4 2.16 1.74 2.14 1.57 1.77 1.64

157 170.18 54.68 47.143 245 195.87 2.82 ------2.7714 ------nd ------0.00183 ------0.13 ------0.00024 ------0.00251 ------0.00245 ------0.26 ------0.2209 ------0.246 ------0.22921 ------10.15 ------10.477 ------

362 ------351 ------365 ------569.9 509.3 509.7 414.9 424.3 419.0 417.7 416.7 417.5 416.4 422.4 0.201 0.16 0.15 0.132 0.141 0.146 0.215 0.211 0.200 0.144 0.149379 2.334 3.46 2.768 1.66 6.044 5.044 4.198 2.988 3.076 4.244 3.760836 <0.002 <0.004 <0.004 <0.004 <0.004 <0.006 <0.004 <0.004 <0.004 <0.006 <0.006 82.5 83.32 80.39 77.15 91.49 85.72 83.51 79.75 80.45 83.24 81.36 <0.005 <0.010 <0.010 <0.010 <0.010 <0.015 <0.010 <0.010 <0.010 <0.015 <0.015 nd nd 0.00459 0.066 0.060 0.10 0.12 0.09 0.11 0.104 0.099 0.114 0.100 0.10 <0.010 <0.020 <0.020 <0.020 <0.020 <0.029 <0.020 <0.020 <0.020 0.152 0.13 <0.010 <0.020 <0.020 <0.020 <0.020 0 <0.020 <0.020 <0.020 <0.029 <0.029

23.07 ------0.00 20.97 25.20 21.32 20.97 -4.40 ------100.00 0.00

2,835 3,183 3,398 3,143 3,009 2,861 1,943 1,975 2,087 2,901 2,828

* measured * used a * used a with a Mettler different different Toledo meter thermometer thermometer

35 Appendix A- Continued

Coldwater Coldwater Coldwater Coldwater Coldwater Coldwater Coldwater Coldwater Coldwater Coldwater Coldwater Wetland A Wetland A Wetland A Wetland A Wetland A Wetland A Wetland A Wetland A Wetland A Wetland A Wetland A 484,492 484,492 484,492 484,492 484,492 484,492 484,492 484,492 484,492 484,492 484,492 4,971,711 4,971,711 4,971,711 4,971,711 4,971,711 4,971,711 4,971,711 4,971,711 4,971,711 4,971,711 4,971,711 15-Jul-2013 24-Jul-2013 29-Jul-2013 3-Aug-2013 12-Aug-2013 19-Aug-2013 25-Aug-2013 30-Aug-2013 8-Sep-2013 14-Sep-2013 21-Sep-2013

12.05 11.95 11.65 12.15 12.05 12.35 13.15 13.45 13.25 12.65 12.35 7.12 7.02 7.03 7.01 6.96 6.99 6.97 6.97 6.96 6.98 6.97 2.091 2.098 2.176 2.188 2.287 2.262 2.39 1.91 2.46 2.512 2.557 1.49 2.52 2.46 2.58 1.69 2.28 2.92 1.94 1.61 2.75 2.23

181.33 199.9033 225.4 49.882 53.814 57.503 200.36 213.18 221.64 --- 2.7932 ------2.8913 ------3.8186 ------nd ------0.0041 ------0.0369 ------nd ------0.0017 ------0.0736 ------0.0019 ------0.0058 ------0.0355 ------0.2267 ------0.2566 ------0.2766 ------0.2392 ------0.2575 ------0.2992 ------10.717 ------10.6347 ------10.4655 ---

--- 378 ------373 ------380 --- 428.1 456.5 492.2 502.0 527.0 528.4 549.7 556.9 581.6 594.5 610.8 0.152308 0.155237 0.169 0.166 0.171 0.181 0.182 0.134 0.132 0.136 0.208 3.166249 2.718112 2.55 2.087 1.981 1.222 1.071 1.197 1.091 1.035 1.239 <0.006 <0.006 <0.006 0.039 <0.006 <0.006 0.01 <0.006 0.01 0.008 <0.006 79.84 77.81 80.022 79.596 79.269 79.517 80.482 81.365 82.648 83.05 84.778 <0.015 <0.015 <0.015 <0.015 <0.015 <0.015 <0.015 <0.015 <0.015 <0.015 <0.015 0.0146 nd 0.0324 0.11 0.13 0.11 0.11 0.10 0.12 0.11 0.11 0.12 0.09 0.10 0.07 <0.029 <0.030 <0.030 <0.030 <0.030 <0.030 <0.030 <0.030 <0.030 <0.030 <0.029 0.08 <0.030 <0.030 0.06 <0.030 <0.030 <0.030 <0.030 <0.030 <0.030

21.95 23.76 25.73 22.25 24.11 26.17 -0.69 -0.73 -0.86

2,811 2,941 2,913 3,024 3,082 2,919 3,020 4,156 4,406 4,371 2,937

* started using a new pH meter

* used a * used a * used a * used a * used a * used a * used a * used a * used a * used a different different different different different different different different different different thermometer thermometer thermometer thermometer thermometer thermometer thermometer thermometer thermometer thermometer

36 Appendix A- Continued

Coldwater Coldwater Coldwater Coldwater Coldwater Coldwater Coldwater Coldwater Coldwater Coldwater Coldwater Wetland A Wetland A Wetland A Wetland A Wetland A Wetland A Wetland A Wetland A Wetland A Wetland A Wetland A 484,492 484,492 484,492 484,492 484,492 484,492 484,492 484,492 484,492 484,492 484,492 4,971,711 4,971,711 4,971,711 4,971,711 4,971,711 4,971,711 4,971,711 4,971,711 4,971,711 4,971,711 4,971,711 28-Sep-2013 5-Oct-2013 13-Oct-2013 19-Oct-2013 26-Oct-2013 2-Nov-2013 9-Nov-2013 16-Nov-2013 24-Nov-2013 1-Dec-2013 8-Dec-2013

13.05 12.55 ------10.15 10.45 10.25 9.65 8.25 8.55 6.65 6.95 6.98 6.97 6.98 6.92 6.97 6.96 6.98 7.01 7.08 6.90 2.558 2.562 2.64 2.63 2.66 2.711 2.749 2.672 2.602 2.653 2.709 1.7 1.14 --- 2.07 4.22 2.17 2.46 2 2.12 2.69 2.41

226.36 230.04 224.9067 59.6745 60.61 58.893 236.78 233.52 233.3533 ------3.9324 ------3.8925 ------3.6933 ------0.0121 ------0.0261 ------0.0667 ------0.033 ------0.0672 ------0.121 ------0.0175 ------0.0194 ------0.0427 ------0.2878 ------0.2961 ------0.2878 ------0.2901 ------0.2951 ------0.2854 ------11.6115 ------11.675 ------11.4547

------377 ------372 ------380 623.2 604.6 624.4 613.9 629.4 631.9 635.0 626.1 620.9 618.9 631.0 0.213 0.203 0.213 0.201 0.208 0.206 0.208 0.203 0.198 0.198 0.199 1.301 1.414 1.437 1.398 1.465 1.42 1.309 1.235 1.173 1.337 1.062 <0.006 <0.006 <0.006 <0.006 <0.006 <0.006 <0.006 <0.006 <0.006 <0.006 <0.006 85.39 92.812 87.517 89.125 87.709 88.072 89.08 88.697 87.578 88.115 88.074 <0.015 <0.015 <0.015 <0.015 <0.015 <0.015 <0.015 <0.015 <0.015 <0.015 <0.015 0.0195 0.0328 0.0415 0.10 0.10 0.10 0.10 0.10 0.10 0.10 0.10 0.09 0.09 0.09 <0.030 <0.030 <0.030 <0.015 <0.015 <0.015 <0.015 <0.015 <0.015 <0.015 <0.015 <0.030 <0.030 <0.030 <0.015 <0.015 <0.015 <0.015 <0.015 <0.015 <0.015 <0.015

26.62 26.73 26.32 27.08 27.30 27.31 -0.86 -1.05 -1.83

2,926 2,978 2,931 3,054 3,026 3,067 3,053 3,084 3,136 3,126 3,171

* used a * used a * used a * used a * used a * used a * no * no different different different different different different * used a * used a thermometer thermometer thermometer thermometer thermometer thermometer thermometer thermometer different different and no RDO and new RDO * new RDO and new RDO and new RDO and new RDO and new RDO and new RDO and new RDO thermometer thermometer cap cap cap cap cap cap cap cap cap

37 Appendix A- Continued

Coldwater Coldwater Coldwater Coldwater Coldwater Coldwater Coldwater Coldwater Coldwater Coldwater Coldwater Wetland A Wetland A Wetland A Wetland A Wetland A Wetland A Wetland A Wetland A Wetland A Wetland A Wetland A 484,492 484,492 484,492 484,492 484,492 484,492 484,492 484,492 484,492 484,492 484,492 4,971,711 4,971,711 4,971,711 4,971,711 4,971,711 4,971,711 4,971,711 4,971,711 4,971,711 4,971,711 4,971,711 15-Dec-2013 21-Dec-2013 28-Dec-2013 4-Jan-2014 11-Jan-2014 18-Jan-2014 25-Jan-2014 9-Feb-2014 16-Feb-2014 23-Feb-2014 1-Mar-2014

6.45 8.65 7.95 --- 7.4 6.8 6.9 7.3 6.9 6.5 --- 6.92 6.92 6.92 6.97 6.93 6.86 6.88 6.92 7.00 ------2.731 2.69 2.563 2.646 3.1 3.01 3.36 2.905 2.67 ------2.72 2.14 ------2.39 2.8 4.29 4.17 4.18 ------

218.9867 209.2667 56.3423 55.5107 227.8233 242.82 ------3.4842 ------3.4689 ------0.0562 ------0.0321 ------0.064 ------0.0403 ------0.0153 ------0.0091 ------0.2695 ------0.2677 ------0.2702 ------0.263 ------11.08 ------10.7623 ------

------377 ------374 ------627.8 622.9 597.5 601.1 606.0 597.0 595.6 586.7 567.4 537.7 545.0 0.199 0.193 0.186 0.188 0.194 0.189 0.188 0.184 0.164 0.144 0.147 0.899 0.84 0.758 0.727 0.841 0.693 0.692 0.706 0.603 0.441 0.53 <0.006 <0.006 <0.006 <0.006 <0.006 <0.006 <0.006 <0.006 <0.006 <0.006 <0.006 88.92 89.267 87.373 88.179 87.373 87.386 87.371 87.07 86.471 86.913 85.91 0.021 <0.015 <0.015 <0.015 <0.015 <0.015 <0.015 <0.015 <0.015 <0.015 <0.015 0.019 0.0238 0.09 0.09 0.09 0.09 0.16 0.16 0.15 0.16 0.12 0.12 0.13 <0.015 <0.015 <0.015 <0.015 <0.015 <0.015 <0.015 <0.015 <0.015 <0.015 <0.015 <0.015 <0.015 <0.015 <0.015 <0.015 <0.015 <0.015 <0.015 <0.015 <0.015 <0.015

25.57 25.67 26.39 25.90 -1.56 -0.44

3,155 3,227 3,212 3,198 3,123 3,159 3,168 3,189 3,460 3,734 3,707

* everything was calibrated

* used a * used a * used old * used old different different * used a * used a * used old * used old * used old thermometer * used old thermometer * used old thermometer thermometer different different thermometer thermometer thermometer and new thermometer and no thermometer and new RDO and new RDO thermometer, thermometer, and a fixed and a fixed and a fixed Thermo Orion and a fixed Thermo Orion and a fixed cap cap no DO no DO RDO cap RDO cap RDO cap equipment RDO cap equipment RDO cap

38 Appendix A- Continued

Coldwater Coldwater Coldwater Coldwater Coldwater Coldwater Coldwater Coldwater Coldwater Coldwater Coldwater Wetland A Wetland A Wetland A Wetland A Wetland A Wetland A Wetland A Wetland A Wetland A Wetland A Wetland A 484,492 484,492 484,492 484,492 484,492 484,492 484,492 484,492 484,492 484,492 484,492 4,971,711 4,971,711 4,971,711 4,971,711 4,971,711 4,971,711 4,971,711 4,971,711 4,971,711 4,971,711 4,971,711 8-Mar-2014 15-Mar-2014 25-Mar-2014 29-Mar-2014 6-Apr-2014 12-Apr-2014 19-Apr-2014 28-Apr-2014 4-May-2014 11-May-2014 20-May-2014

6.9 7.2 6.4 --- 7.2 8.2 7.5 7.8 8.3 9 9.3 6.80 6.85 6.70 --- 6.90 6.88 6.91 --- 6.99 6.83 6.81 2.63 2.785 3.06 --- 2.563 2.388 2.346 --- 2.128 2.29 2.07 3.3 3.03 2.8 --- 3.78 4.53 4.3 --- 4.86 4.41 10.08

204.945 187.58 164.7333 53.7007 50.722 44.099 240.7367 218.34 185.7633 3.3758 ------3.2441 ------2.8815 ------0.0085 ------0.2286 ------0.063 ------0.003 ------0.279 ------0.0715 ------0.0001 ------0.0409 ------0.018 ------0.2561 ------0.2378 ------0.2017 ------0.251 ------0.2304 ------0.1966 ------10.595 ------10.1997 ------9.6638 ------

356 ------335 ------347 ------564.9 564.7 563.1 511.5 498.3 490.8 484.8 382.2 385.2 409.9 313.2 0.177 0.171 0.193 0.144 0.161 0.148 0.142 0.12 0.116 0.14 0.097 0.692 0.438 0.723 0.908 2.51 1.647 1.791 1.508 2.569 3.191 1.144 <0.006 <0.006 <0.006 0.167 <0.006 <0.006 <0.006 <0.006 <0.006 <0.006 <0.006 86.483 87.789 86.064 87.827 88.249 87.532 88.146 72.215 89.649 96.004 70.464 <0.015 <0.015 <0.015 <0.015 0.046 <0.015 <0.015 <0.015 <0.015 <0.015 <0.015 0.0499 0.0413 0.0302 0.12 0.10 0.10 0.09 0.10 0.10 0.09 0.10 0.10 0.10 0.10 <0.015 <0.015 <0.015 <0.015 <0.015 <0.015 <0.015 <0.015 <0.015 <0.015 <0.015 <0.015 <0.015 <0.015 <0.015 <0.015 <0.015 <0.015 <0.015 <0.015 <0.015 <0.015

25.21 23.12 20.01 24.91 22.77 19.86 0.61 0.76 0.39

3,191 3,302 2,917 3,552 3,095 3,316 3,414 3,185 3,321 2,928 3,228

* used old * used old * used old thermometer thermometer thermometer and old and old and old Thermo Orion Thermo Orion Thermo Orion equipment equipment equipment

39 Appendix A- Continued

Coldwater Coldwater Coldwater Coldwater Coldwater Coldwater Coldwater Coldwater Coldwater Coldwater Coldwater Wetland A Wetland A Wetland A Wetland A Wetland A Wetland A Wetland A Wetland A Wetland A Wetland A Wetland A 484,492 484,492 484,492 484,492 484,492 484,492 484,492 484,492 484,492 484,492 484,492 4,971,711 4,971,711 4,971,711 4,971,711 4,971,711 4,971,711 4,971,711 4,971,711 4,971,711 4,971,711 4,971,711 24-May-2014 31-May-2014 8-Jun-2014 17-Jun-2014 6-Jul-2014 12-Jul-2014 20-Jul-2014 26-Jul-2014 2-Aug-2014 10-Aug-2014 17-Aug-2014

18.8 17.8 9.9 11.5 11.7 13.5 13.2 13.5 13.8 12.8 13.0 6.98 7.15 7.16 7.37 7.19 6.93 6.96 6.94 6.96 6.88 7.03 2.095 2.112 2.225 2.329 2.445 2.2 2.291 2.311 2.331 2.333 2.477 5.64 5.85 4.39 11.91 4.98 4.13 2.75 2.32 3.23 --- 1.58

177.915 153.2133 187.65 48.253 47.8507 49.852 184.975 183.2533 206.22 --- 2.887 ------3.8867 ------5.2829 ------0.0296 ------0.003 ------0.0086 ------0.0478 ------0.0189 ------0.0009 ------0.0464 ------0.0178 ------0.0033 ------0.2201 ------0.2037 ------0.2379 ------0.2194 ------0.179 ------0.298 ------9.9851 ------7.3476 ------11.062 ------

--- 368 ------309 ------388 ------399.3 424.2 395.5 387.6 407.7 422.1 469.1 483.1 490.8 489.5 511.0 0.133 0.153 0.127 0.107 0.112 0.099 0.132 0.149 0.12 0.146 0.179 1.862 2.307 2.489 0.256 1.209 2.284 2.548 2.664 2.718 2.784 2.186 <0.006 <0.006 <0.006 <0.006 <0.006 <0.010 <0.010 <0.010 <0.010 <0.010 <0.010 90.455 91.566 84.523 69.522 79.625 79.616 81.052 80.385 79.763 78.593 79.207 <0.015 <0.015 <0.015 <0.015 <0.015 0.055 0.045 <0.025 0.214 0.034 0.034 0.0556 0.0127 0.5319 0.10 0.10 0.10 0.09 0.09 0.10 0.09 0.09 0.10 0.09 0.09 <0.015 <0.015 <0.015 <0.015 <0.015 <0.015 <0.015 <0.015 <0.015 <0.015 <0.025 <0.015 <0.015 <0.015 <0.015 <0.015 <0.015 <0.015 <0.015 <0.015 <0.015 <0.025

20.98 19.66 22.58 21.40 19.42 23.46 -0.99 0.61 -1.91

3,002 2,772 3,114 3,622 3,640 4,263 3,554 3,242 4,090 3,352 2,854

40 Appendix A- Continued

Coldwater Coldwater Coldwater Coldwater Coldwater Coldwater Coldwater Coldwater Coldwater Coldwater Coldwater Wetland A Wetland A Wetland A Wetland A Wetland A Wetland A Wetland A Wetland A Wetland A Wetland A Wetland A 484,492 484,492 484,492 484,492 484,492 484,492 484,492 484,492 484,492 484,492 484,492 4,971,711 4,971,711 4,971,711 4,971,711 4,971,711 4,971,711 4,971,711 4,971,711 4,971,711 4,971,711 4,971,711 24-Aug-2014 29-Aug-2014 7-Sep-2014 14-Sep-2014 21-Sep-2014 27-Sep-2014 4-Oct-2014 12-Oct-2014 19-Oct-2014 26-Oct-2014 2-Nov-2014

13.2 13.1 13.5 12.3 12.9 13.3 12.0 11.8 11.9 11.7 10.4 7.06 7.04 6.87 6.89 6.93 6.88 6.83 6.83 6.83 6.81 6.90 2.507 2.382 2.310 2.323 2.352 2.347 2.427 2.450 2.452 2.506 2.539 2.22 1.47 ------1.47

197.445 197.85 204.46 51.847 53.649 55.6868 207.26 208.43 236.185 --- 4.6836 ------3.618 ------3.7323 ------0.0073 ------0.011 ------0.0041 ------0.052 ------0.093 ------0.0231 ------0.0126 ------0.075 ------0.0151 ------0.2446 ------0.256 ------0.2593 ------0.2502 ------0.255 ------0.2618 ------11.856 ------11.868 ------11.7875 ---

--- 400 ------392 ------400 --- 513.2 513.7 508.2 500.1 501.4 509.8 534.9 528.7 533.1 540.4 552.1 0.203 0.189 0.205 0.205 0.204 0.208 0.205 0.202 0.202 0.207 0.208 2.063 2.215 2.055 2.229 2.173 2.002 1.868 2.003 2.016 1.944 1.818 <0.010 <0.010 0.019 <0.007 <0.007 <0.007 <0.010 <0.010 <0.010 <0.010 <0.010 79.036 79.185 80.813 81.362 81.844 81.128 85.393 83.578 83.939 84.413 84.933 <0.025 <0.025 <0.018 <0.018 <0.018 <0.018 <0.025 <0.025 <0.025 <0.025 <0.025 0.0223 0.019 0.0251 0.09 0.09 0.10 0.10 0.10 0.10 0.09 0.09 0.09 0.09 0.09 <0.025 <0.025 <0.018 <0.018 <0.018 <0.018 <0.025 <0.025 <0.025 <0.025 <0.025 <0.025 <0.025 <0.018 <0.018 <0.018 <0.018 <0.025 <0.025 <0.025 <0.025 <0.025

23.26 23.46 25.16 24.30 24.05 25.14 -2.18 -1.26 0.05

2,528 2,718 2,479 2,440 2,458 2,451 2,609 2,617 2,639 2,610 2,654

41 Appendix A- Continued

Coldwater Coldwater Coldwater Coldwater Coldwater Coldwater Coldwater Coldwater Coldwater Coldwater Coldwater Wetland A Wetland A Wetland A Wetland A Wetland A Wetland A Wetland A Wetland A Wetland A Wetland A Wetland A 484,492 484,492 484,492 484,492 484,492 484,492 484,492 484,492 484,492 484,492 484,492 4,971,711 4,971,711 4,971,711 4,971,711 4,971,711 4,971,711 4,971,711 4,971,711 4,971,711 4,971,711 4,971,711 9-Nov-2014 16-Nov-2014 22-Nov-2014 30-Nov-2014 7-Dec-2014 14-Dec-2014 20-Dec-2014 30-Dec-2014 3-Jan-2015 10-Jan-2015 18-Jan-2015

11.0 10.6 10.3 9.5 9.7 10.2 9.9 9.5 9.3 9.1 9.0 6.94 6.95 6.95 6.98 6.98 6.93 6.96 7.02 6.98 --- 7.01 2.542 2.606 2.606 2.686 2.622 2.578 2.684 2.767 2.691 --- 2.798 2.72 --- 1.54 2.08 2.24 2.69 2.85 3.29 ------

205.8633 212.64 56.709 58.2175 243.15 233.48 ------3.6636 ------3.7491 ------0.0041 ------0.0746 ------0.0224 ------0.0165 ------0.0074 ------0.0055 ------0.2596 ------0.2774 ------0.2682 ------0.271 ------11.5823 ------11.187

398 397 395 558.0 558.4 563.0 560.6 564.0 572.7 524.5 526.7 524.8 0.21 0.235 0.229 0.228 0.228 0.247 0.204 0.21 0.202 1.742 1.752 1.716 1.921 1.902 1.9 1.189 1.164 1.223 <0.010 <0.010 <0.010 <0.010 <0.010 <0.010 <0.010 <0.010 <0.010 <0.010 <0.010 83.751 84.635 85.666 86.433 87.433 88.462 77.02 77.39 77.999 <0.025 <0.025 <0.025 <0.025 <0.025 <0.025 <0.025 <0.025 <0.025 <0.025 <0.025 0.0089 0.10 0.10 0.10 0.10 0.10 0.10 0.08 0.08 0.08 <0.025 <0.025 <0.025 <0.025 <0.025 <0.025

25.62 25.66 25.75 24.41 -0.25 2.49

2,657 2,376 2,459 2,459 2,474 2,319 2,571 2,508 2,598

Suspected of being wrong

42 Appendix A- Continued

Wetland A Coldwater Coldwater Coldwater Coldwater Coldwater Coldwater Coldwater Coldwater Coldwater Gravel Wetland H Wetland H Wetland H Wetland H Wetland H Wetland H Wetland H Wetland H Wetland H 484,492 484,394 484,394 484,394 484,394 484,394 484,394 484,394 484,394 484,394 4,971,711 4,972,096 4,972,096 4,972,096 4,972,096 4,972,096 4,972,096 4,972,096 4,972,096 4,972,096 4-Jan-2016 27-Apr-2013 4-May-2013 12-May-2013 20-May-2013 28-May-2013 1-Jun-2013 10-Jun-2013 20-Jun-2013 25-Jun-2013

8.6 14.5 6.7 21.7 21.9 15.5 21 27.9 24.1 32.9 7.96 7.84 8.14 8.20 7.09 7.70 7.81 8.52 7.77 1.561 2.824 2.840 0.773 1.316 1.231 2.112 2.438 1.188 12.95 15.36 16.68 --- 5.23 4.8 7.74 4.63 4.02

121 106.06 42.11 33.661 92 93.638 --- 7.799 ------6.403 --- 0.0245 ------nd --- 0.15 ------0.07146 --- 0.05399 ------0.99360 --- 0.236 ------0.18146 --- 0.117 ------0.1704 --- 6.425 ------3.9263

254 ------234.5 ------242 489.6 318.5 703.8 817.8 169.5 258.8 258.3 217.9 646.6 248.2 0.175 0.140 0.194 0.251 <0.02 0.078 0.105 0.186 0.303 <0.020 0.873 0.163 0.02 0.02 0.075 0.06 0.047 0.033 <0.002 0.04 <0.008 0.053 <0.004 <0.004 <0.004 <0.004 <0.006 <0.004 <0.004 <0.004 90.447 78.045 60.39 67.148 17.6 38.11 24.15 16.66 10.15 16.71 <0.040 <0.005 <0.010 <0.010 <0.010 <0.010 <0.015 <0.010 <0.010 <0.010 nd nd 0.0865 0.126 0.127 0.10 0.12 0.11 0.106 0.132 0.189 0.200 0.136 <0.040 <0.010 <0.020 <0.020 <0.020 <0.020 <0.029 <0.020 <0.020 <0.020 <0.040 <0.010 <0.020 <0.020 <0.020 <0.020 <0.029 <0.020 <0.020 <0.020

--- 13.71 ------0.00 ------12.31 15.71 12.79 12.19 --- -6.79 ------100.00 ------0.46

2,798 2,275 3,628 3,258 #DIV/0! 3,318 2,450 1,172 2,134 #DIV/0!

* there was a dead frog in the water near * measured the sample with a spot as well Mettler as many Toledo meter tadpoles

43 Appendix A- Continued

Coldwater Coldwater Coldwater Coldwater Coldwater Coldwater Coldwater Coldwater Coldwater Coldwater Coldwater Wetland H Wetland H Wetland H Wetland H Wetland H Wetland H Wetland H Wetland H Wetland H Wetland H Wetland H 484,394 484,394 484,394 484,394 484,394 484,394 484,394 484,394 484,394 484,394 484,394 4,972,096 4,972,096 4,972,096 4,972,096 4,972,096 4,972,096 4,972,096 4,972,096 4,972,096 4,972,096 4,972,096 2-Jul-2013 8-Jul-2013 15-Jul-2013 24-Jul-2013 29-Jul-2013 3-Aug-2013 12-Aug-2013 19-Aug-2013 25-Aug-2013 30-Aug-2013 8-Sep-2013

22.65 36.25 27.35 18.15 21.65 18.45 29.35 19.95 22.55 24.25 20.95 8.86 9.85 8.31 7.63 8.65 8.44 7.86 8.81 8.82 7.87 7.80 1.78 2.053 0.85 1.588 1.644 0.89 1.044 0.719 0.76 0.86 1.112 3.01 8.35 6.68 2.24 14.98 13.76 7.67 11.56 11.26 6.34 6.88

83.806 47.5893 55.816 24.1117 168.52 57.544 ------9.4881 ------5.5522 ------0.0119 ------0.0081 ------0.4443 ------0.2622 ------0.6504 ------0.0746 ------0.1895 ------0.0958 ------0.1242 ------0.0284 ------5.556 ------5.5238 ------

------177 ------114 ------384.0 583.3 185.4 543.0 482.6 182.8 205.4 156.9 177.5 190.5 235.3 0.226 0.419 0.126 0.369 0.417 0.158 0.154 0.19 0.219 0.198 0.211 0.059 0.029 0.059 0.172 0.018 0.017 0.017 0.006 0.004 <0.003 <0.003 <0.006 <0.006 <0.006 <0.006 <0.006 <0.006 <0.006 <0.006 <0.006 <0.006 <0.006 20.37 6.50 9.11 26.68 8.649 30.621 33.923 20.36 14.691 16.804 30.108 <0.015 <0.015 <0.015 <0.015 <0.015 <0.015 <0.015 <0.015 <0.015 <0.015 <0.015 0.1414 0.0352 0.149 0.249 0.146 0.429 0.19 0.14 0.17 0.13 0.13 0.14 0.14 <0.029 <0.029 <0.029 <0.029 <0.030 <0.030 <0.030 <0.030 <0.030 <0.030 <0.030 <0.029 <0.029 <0.029 <0.029 <0.030 <0.030 <0.030 <0.030 <0.030 <0.030 <0.030

------16.35 ------7.01 ------19.45 7.14 ------8.64 ------0.92 ------

1,703 1,393 1,472 1,472 1,157 1,157 1,334 826 810 962 1,115

*rain water filled up the *the regular normal spot *the regular *the regular *the regular *the regular spot dried up. so I sampled spot dried up. spot dried up. spot dried up. spot dried up. * started Sampled from from the Sampled from Sampled from Sampled from Sampled from using a new a different normal a different a different a different a different pH meter location location location location location location

* used a * used a * used a * used a * used a * used a * used a * used a * used a * used a different different different different different different different different different different thermometer thermometer thermometer thermometer thermometer thermometer thermometer thermometer thermometer thermometer

44 Appendix A- Continued

Coldwater Coldwater Coldwater Coldwater Coldwater Coldwater Coldwater Coldwater Coldwater Coldwater Wetland H Wetland H Wetland H Wetland H Wetland H Wetland H Wetland H Wetland H Wetland H Wetland H 484,394 484,394 484,394 484,394 484,394 484,394 484,394 484,394 484,394 484,394 4,972,096 4,972,096 4,972,096 4,972,096 4,972,096 4,972,096 4,972,096 4,972,096 4,972,096 4,972,096 14-Sep-2013 21-Sep-2013 28-Sep-2013 5-Oct-2013 13-Oct-2013 19-Oct-2013 26-Oct-2013 2-Nov-2013 9-Nov-2013 16-Nov-2013

14.45 13.75 17.05 14.15 ------5.55 4.95 4.25 4.75 7.58 7.61 7.86 7.74 7.67 7.60 7.95 7.78 7.92 7.76 1.322 1.189 1.275 1.1 1.272 1.13 1.178 1.266 1.262 1.447 10.42 8.43 7.45 6.69 --- 4.04 9.45 7.84 9.19 8.9

119.24 117.68 122.1475 41.095 39.499 39.3483 94.491 86.7725 77.9585 5.3647 ------7.2013 ------8.3489 --- 0.0199 ------0.0204 ------0.0381 --- 0.5942 ------0.8646 ------1.1189 --- 0.1679 ------0.593 ------0.8609 --- 0.1924 ------0.2023 ------0.2049 --- 0.07 ------0.1025 ------0.1156 --- 10.1007 ------8.5579 ------7.9001 ---

273 ------267 ------271 --- 259.5 236.4 265.1 219.2 244.5 212.4 218.8 226.4 227.2 258.9 0.197 0.19 0.265 0.208 0.224 0.203 0.224 0.228 0.228 0.261 <0.003 0.028 0.009 0.008 0.019 0.057 0.005 <0.003 <0.003 <0.003 <0.006 <0.006 <0.006 <0.006 <0.006 <0.006 <0.006 <0.006 <0.006 <0.006 48.74 51.174 44.787 36.28 40.608 38.591 38.041 39.713 39.574 42.414 <0.015 <0.015 <0.015 <0.015 <0.015 <0.015 <0.015 0.031 0.023 <0.015 0.0496 0.0588 0.1035 0.12 0.11 0.14 0.11 0.13 0.11 0.12 0.13 0.13 0.14 <0.030 <0.030 <0.030 <0.030 <0.030 <0.015 <0.015 <0.015 <0.015 <0.015 <0.030 <0.030 <0.030 <0.030 <0.030 <0.015 <0.015 <0.015 <0.015 <0.015

13.58 ------13.09 ------12.94 --- 13.80 13.09 12.66 -0.79 ------0.00 ------1.12 ---

1,317 1,244 1,001 1,054 1,091 1,046 977 993 996 992

*the regular *the regular *the regular *the regular *the regular *the regular *the regular *the regular *the regular *the regular spot dried up. spot dried up. spot dried up. spot dried up. spot dried up. spot dried up. spot dried up. spot dried up. spot dried up. spot dried up. Sampled from Sampled from Sampled from Sampled from Sampled from Sampled from Sampled from Sampled from Sampled from Sampled from a a different a different a different a different a different a different a different a different a different different location location location location location location location location location location

* used * used * no * no different different * used different * used a * used a * used a * used a thermometer thermometer thermometer thermometer thermometer different different different different and no RDO and new RDO * new RDO and new RDO and new RDO and new RDO thermometer thermometer thermometer thermometer cap cap cap cap cap cap

45 Appendix A- Continued

Big Culvert Big Culvert

27-Sep-2014 18-Jan-2015

170.403 146.795 40.038 34.8755 242.297 359.07 3.58 3.5814 0.237 0.008 0.636 0.0107 0.053 0.029 0.207 0.216 0.59 0.16 11.43 9.01

371 339 490.067 626.962 0.134 0.153 2.663 1.723 <0.007 0.008 90.413 66.928 <0.018 <0.025 0.056 0.0133 0.11 0.10 <0.018 <0.025 <0.018 <0.025

22.44 25.91 23.32 25.98 -1.91 -0.14

3,657 4,098

Suspected of being wrong

46 Appendix B: Field Data for Additional Sample Locations

This Appendix contains field data for the road salt samples, Big Culvert samples, the three inlet pipes at Coldwater Spring, the outflow pipe at Coldwater Spring, and several other sites located around Coldwater Spring and Wetland A.

University & Harvard & Beacon & Coldwater Sample Name Big Culvert Big Culvert Road Salt Road Salt 16th Pillsbury Union Spring A

UTM E (NAD83) 20x Mean* 40x Mean* 484,477

UTM N (NAD83) 56678 (D.F.) 28339 (D.F.) 4,971,784 Sample Date 27-Feb-2014 27-Feb-2014 27-Feb-2014 27-Sep-2014 18-Jan-2015 26-Jul-2015

Field Parameters Temp (ºC) 12 pH Cond (mS/cm) DO (ppm)

Cations (in ppm) Ca 101.33 119.59 118.9 170.403 146.795 3071.5 3294.1 Mg 66.6 49.39 77.83 40.038 34.8755 108.8 212.3 Na 6709.07 7659.5 6717.33 242.297 359.07 384716.1 374563.2 K 95.06 61.76 78.95 3.58 3.5814 716.4 1101.6 --- Al 0.660 0.210 nd 0.237 0.008 13.200 43.200 --- Fe 0.01 0.04 0.02 0.636 0.0107 8.8 22.9 --- Mn 0.160 0.180 0.070 0.053 0.029 1.100 1.400 --- Sr 0.800 1.620 1.600 0.207 0.216 5.400 9.700 --- Ba 0.80 0.66 0.59 0.59 0.16 0.80 1.50 --- Si 1.59 1.14 3.24 11.43 9.01 81.70 134.10 ---

Anions (in ppm)

Alk. (as CaCO3) 371 339 Cl 11948.966 13027.539 11864.49 490.067 626.962 577886 579289 442.7 Br 4.681 5.175 5.541 0.134 0.153 283 283 0.157

NO3-N 0.763 0.859 0.718 2.663 1.723 130 76 3.283

NO2-N 0.477 0.375 0.367 <0.007 0.008 113 113 <0.004

SO4 117.171 148.48 163.835 90.413 66.928 5220 5888 77.860

PO4-P 0.359 0.788 1.561 <0.018 <0.025 283 142 <0.020 Total P nd 0.72 1.41 0.056 0.0133 F 0.77 0.68 0.64 0.11 0.10 283 142 0.092

CH3CO2- 115.70 52.33 16.10 <0.018 <0.025 283 142 <0.020

HCO2- 6.57 7.96 7.08 <0.018 <0.025 283 142 <0.020

Calculated Data Charge Balance Cations (meq/kg) --- 22.44 25.91 ------Anions (meq/kg) 23.32 25.98 % difference --- -1.91 -0.14 ------

Cl/Br (wt ratio) 2,553 2,517 2,141 3,657 4,098 2,042 2,047 2,819

Suspected of being wrong

47 Appendix B- Continued

Coldwater Coldwater Coldwater Coldwater Coldwater Coldwater Coldwater Coldwater Coldwater Spring Spring Spring B Spring C Spring A Spring B Spring C Spring Bridge Spring A Overflow Overflow

484,477 484,477 484,477 484,477 484,477 484,477 484,477 484,477

4,971,784 4,971,784 4,971,784 4,971,784 4,971,784 4,971,784 4,971,784 4,971,784 26-Jul-2015 26-Jul-2015 26-Jul-2015 30-Oct-2015 30-Oct-2015 30-Oct-2015 30-Oct-2015 30-Oct-2015 4-Jan-2016

12.2 12.7 12.1 13.3 13.3 13.4 13.2 11.1 13.1 7.06 7.10 7.09 7.01 7.46 2.344 2.127 2.048 2.168 2.264

------

422.7 397.0 437.7 416.8 406.8 382.6 415.2 434.0 424.4 0.147 0.148 0.160 0.242 0.232 0.216 0.220 0.214 0.184 3.168 3.343 3.279 3.312 3.358 3.461 3.325 2.526 3.135 <0.004 <0.004 <0.004 <0.008 <0.008 <0.008 <0.008 <0.008 <0.008 79.201 81.871 78.394 82.802 83.962 86.097 83.282 82.666 81.305 <0.020 <0.020 <0.020 <0.040 <0.040 <0.040 <0.040 <0.040 <0.040

0.089 0.106 0.087 0.088 0.093 0.093 0.093 0.089 0.112 <0.020 <0.020 <0.020 <0.040 <0.040 <0.040 <0.040 <0.040 <0.040 <0.020 <0.020 <0.020 <0.040 <0.040 <0.040 <0.040 <0.040 <0.040

------

------

2,875 2,682 2,736 1,722 1,753 1,771 1,887 2,028 2,306

48 Appendix B- Continued

Coldwater Coldwater Coldwater Coldwater Coldwater Coldwater Spring SW Wetland A Wetland A Wetland A Spring Tufa Spring B Spring C Spring Outfall Spring Bridge Corner, Upper Bridge Gravel North Drips Pool

484,477 484,477 484,477 484,485 484,490 484,492 484,485

4,971,784 4,971,784 4,971,784 4,971,768 4,971,759 4,971,711 4,971,735 4-Jan-2016 4-Jan-2016 4-Jan-2016 4-Jan-2016 4-Jan-2016 4-Jan-2016 4-Jan-2016 4-Jan-2016 4-Jan-2016

13.0 12.8 12.9 4.5 6.2 --- 6.1 8.6 6.8

------

404.6 389.9 415.4 431.6 436.3 581.6 500.8 489.6 504.0 0.180 0.174 0.173 0.186 0.190 0.242 0.180 0.175 0.205 3.158 3.292 3.087 2.646 2.697 1.261 1.239 0.873 1.926 <0.008 <0.008 <0.008 <0.008 <0.008 <0.008 <0.008 <0.008 <0.008 81.271 83.678 80.967 80.666 80.867 74.340 79.460 90.447 76.575 <0.040 <0.040 <0.040 <0.040 <0.040 <0.040 <0.040 <0.040 <0.040

0.152 0.112 0.120 0.106 0.110 0.128 0.119 0.126 0.111 <0.040 <0.040 <0.040 <0.040 <0.040 <0.040 <0.040 <0.040 <0.040 <0.040 <0.040 <0.040 <0.040 <0.040 <0.040 <0.040 <0.040 <0.040

------

------

2,248 2,241 2,401 2,320 2,296 2,403 2,782 2,798 2,458

49 Appendix C: Past Coldwater Spring Field Data

This Appendix contains field data from 1998 to 2001 for the Coldwater Spring location. The data was collected by the Minnesota Department of Transportation. Coldwater Coldwater Coldwater Coldwater Coldwater Sample Name Spring Pool Spring Pool Spring Pool Spring Pool Spring Pool UTM E (NAD83) UTM N (NAD83) Sample Date 1-Jun-1998 1-Jul-1998 31-Jul-1998 1-Sep-1998 5-Oct-1998

Field Parameters pH 7.3 7.4 7.2 7.1 7.5 Cond (mS/cm) 1.6 1.7 1.7 1.8 1.7 Anions (in ppm) Cl 260 290 280 320 290

NO3-N 3.6 3.5 3.5 3.2 3.9

50 Appendix C- Continued

Coldwater Coldwater Coldwater Coldwater Coldwater Coldwater Coldwater Spring Pool Spring Pool Spring Pool Spring Pool Spring Pool Spring Pool Spring Pool

5-Nov-1998 4-Dec-1998 5-Jan-1999 1-Feb-1999 1-Mar-1999 2-Apr-1999 5-May-1999

7.1 7.1 7.2 7.8 7.3 7.2 1.7 1.7 1.7 1.6 1.7 1.7

310 280 250 270 300 290 4 4.3 4.7 4.8 4.6 4.2

51 Appendix C- Continued

Coldwater Coldwater Coldwater Coldwater Coldwater Coldwater Coldwater Spring Pool Spring Pool Spring Pool Spring Pool Spring Pool Spring Pool Spring Pool

7-Jun-1999 28-Jun-1999 12-Aug-1999 10-Sep-1999 1-Oct-1999 1-Nov-1999 2-Dec-1999

7.3 7.1 7.7 7.1 7.2 1.7 1.7 1.7 1.7 1.7

300 290 250 270 280 3.8 4.2 4.2 4.5 4.6

52 Appendix C- Continued

Coldwater Coldwater Coldwater Coldwater Coldwater Coldwater Coldwater Spring Pool Spring Pool Spring Pool Spring Pool Spring Pool Spring Pool Spring Pool

4-Jan-2000 4-Feb-2000 1-Mar-2000 3-Apr-2000 25-Apr-2000 25-Apr-2000 31-May-2000

7.4 7.1 7.3 7.1 8.3 8.1 1.7 1.7 0.0 1.7 1.6 1.4 1.1

270 260 270 310 290 4.5 4.5 3.8 3.9 4.1 4

53 Appendix C- Continued

Coldwater Coldwater Coldwater Coldwater Coldwater Coldwater Coldwater Spring Pool Spring Pool Spring Pool Spring Pool Spring Pool Spring Pool Spring Pool

26-Jun-2000 26-Jul-2000 29-Aug-2000 26-Sep-2000 23-Oct-2000 29-Nov-2000 27-Dec-2000

7.6 7.8 8.2 7.9 8.1 8.2 8.2 1.0 1.3 1.2 1.1 1.3 1.4 1.6

280 280 320 250 290 290 260 3.5 3.5 3.1 3.2 3.2 3 3

54 Appendix C- Continued

Coldwater Coldwater Coldwater Spring Pool Spring Pool Spring Pool

25-Jan-2001 28-Feb-2001 27-Mar-2001

7.7 8.4 7.7 1.1 1.6 1.4

280 300 310 2.6 3.4 2.8

55