Summary Report of Spring Water Quality Sampling Karst Pilot Project Viroqua Wisconsin

Margaret Thielke Lynn Chakoian Doug Avoles, Vernon County Land Information Dept. Sarah Grainger, Valley Stewardship Network October 2011

Introduction
Water quality of springs within the Karst Pilot Project area in the vicinity of Viroqua Wisconsin was determined as part of the pilot project funded by the Nuzum Foundation Kickapoo Valley Resforestation Fund. This support was made available through the University of Wisconsin (Groundwater Vulnerability in the Kickapoo Watershed WI.) Several dynamics are revealed in the water quality of springheads. One is a rough measure of the response time of surface aquifers after rainstorms, and the other is evidence of the movement of pollutants in the system. The Valley Stewardship Network (VSN) water quality specialist worked with Kevin Rodolfo and Lynn Chakoian to identify springs in the study area that were suitable for water quality monitoring. In July of 2009 temperature dataloggers were deployed. Margaret Thielke assisted in creating a QUAPP (appendix A) for the chemical sampling program, and later in coordination with VSN staff and Lynn Chakoian compiled these results.

Overview of Water Quality Concerns

Water quality is measurement of a surface water's ability to support aquatic life and be used as recreational resource. In the case of groundwater, it is the ability to be used for human consumption. There are lists of various chemicals and bacteria which provide the measure of pollution (parameters.) Safe levels of contaminates in surface water are called standards, and are developed based on the use of water. The cleanest surface water use is for fishing and recreation. Wisconsin's State Standards list the limits of concentrations of pollutants which the water tested is considered healthy. The levels of parameters are measured in milligrams per liter. For groundwater the standards are based on the potability of groundwater . The parameters in this study are the two basic indicators of human health. These are nitrite plus nitrate (NO 2 +NO3) and the number of E. coli (cfus/100 millimeters) or colony forming units in 100 milliliters of a water sample.

Nitrite plus nitrate (NO2 +NO3) can substitute for oxygen in the bloodstream, especially in infants, causing "blue baby syndrome. The dangerous level is 10 mg/L of nitrate. E. coli is a bacteria that is found in the guts of warm-blooded animal. It indicates the groundwater is contaminated from human or animal feces. E. coli is measured also because it represents the presence many other bacteria. These bacteria range from harmless to life-threatening. The sources of contamination are leaking septic tanks, runoff from feeding lots, erosion from farm fields, overuse of pesticides and herbicides, leaking landfills and industrial discharge. There are many other contaminants in groundwater that make it unfit to drink. Atrazine has been found in wells in the study area and DATCP issued an atrazine application ban on acreage north of Viroqua along US Hwy 14. There are many pollutants from metals waste, pesticides, herbicides, other man-made chemicals that were not part of this pilot study.

Methods and Materials

The Karst Pilot Project included water quality sampling that occurred from July 2009 to the fall of 2010. The sampling completed provided measurements from both in-field and laboratory analysis. The field sampling measured instantaneous air temperature, instantaneous and continuous water temperature, dissolved oxygen concentration and saturation, pH and specific conductivity. Air temperature was measured using a mercury thermometer. A thermometer was placed in a shaded area at the sample site and read when the thermometer had stabilized, roughly 5 minutes. Depending on the equipment available at the time of sampling, one of two instruments was used to measure dissolved oxygen and temperature. When available a YSI 85 handheld dissolved oxygen/conductivity instrument was used which also allowed for conductivity testing. If that instrument was not available a YSI 550 A handheld dissolved oxygen instrument was used. Prior to field measurement the instrument was calibrated according to manufacturer instructions. Calibration occurred at the beginning of sampling for that day and repeated as necessary. The measurement was taken in-spring after the probe stabilized, approximately two to three minutes after submersion. Measurement of pH was made using an Oakton Acorn pH 5. Instrument calibration was completed as per manufacturer instructions. Calibration was performed before sampling for the day and repeated as necessary. Readings were taken with the probe in-spring after the instrument had stabilized, approximately two to three minutes after submersion of probe. Transparency was measured using either a 30 inch or 120 cm Plexiglas transparency tube. Depending on the depth of the spring, the sample was collected either by submerging the tube to mid-depth in the flowing spring water or collected in a container and transferred to the tube. Caution was taken not to stir up the bottom sediment before and during sampling. Transparency measurement was recorded when the Secchi disk at the bottom of the tube was just distinguishable. The measurement was taken before the sample had settled and out of direct sunlight. Transparency depth corresponds to a measure of turbidity as nephelometric turbidity units (NTU).

Continuous temperature measurements were taken with Onset Corporation Tidbit v2 data loggers. These temperature sensors were placed immediately downstream of the spring outlet and submerged in the spring flow. Sensors were secured to anchors (metal plates and large rocks) attached with metal wire. Approximately every 3 months the data was downloaded from the sensor. Unfortunately, during monitoring three sensors were lost due to flood waters, which resulted in data being lost for a three month period. The following chart indicates measurement range and accuracy for each parameter measured. Parameter Measurement Range Accuracy Instrument Conductivity, 0 to 499.9 S/cm 0.5% full scale YSI 85 specific 0 to 4999 S/cm 0 to 49.99 mS/cm 0 to 200.0 mS/cm Dissolved Oxygen, 0 to 20 mg/L +/- 0.3 or +/- 2% of YSI 550A, YSI 85 concentration reading, whichever is greater Dissolved Oxygen, 0 to 200% +/- 2% of air YSI 550A, YSI 85 percent saturation saturation or +/- 2% of reading, whichever is greater pH 0 to 14 +/- 0.2 Oakton Acorn pH 5 Temperature -5 to +45C +/- 0.3C YSI 550A, YSI 85 Temperature -20 to +30C +/- 0.2C Onset Corp. Tidbit v2 Transparency 0 to 120 cm N/A Transparency Tube Samples were collected for laboratory analysis of ammonium, total phosphorus, nitrate plus nitrite and Escherichia coli (E.coli). Samples were analyzed by University of Stevens Points Water and Environmental Analysis Laboratory. Ammonium, total phosphorus and nitrate plus nitrite samples were collected from the springs in clean collection bottles that were rinsed at least three times in the spring bottles and the sample was poured into the pre-acidified (using sulfuric acid) sample bottles provided by the laboratory. E.coli samples were collected by submersing pre-sterilized bottles in the spring waters. After samples were collected they were immediately put on ice and delivery to the laboratories within 24hrs of collection. Laboratory samples were analyzed using the following methods. Parameter Method Ammonium (N) EPA Method 350.1, Lachat Method #10-107-06-1B Nitrate + Nitrite Standard Methods* - 4500 NO3 F, Automated Cadmium (N) Reduction Total Phosphorus Standard Methods* - 4500 P F, Block Digester, Automated E-COLI cfu/100 Colilert, Enzyme Substrate mls * Standard Methods for Examination of Water and Wastewater

The Springhead Sites Studied

Data was gathered on a wide range of sites initially. Some spring configurations were determined to be more reliable in terms of yielding consistent samples, others were judged representative of a certain flow rate of the springhead. In the final analysis we chose three sites that represented high, medium and low flowing springs, and a mix of land uses. All the sites are described below. Site #1 Roger Widner property N 43 37.462 W 090 47.321 tidbit #2016448 Spring is located at the west end of Rogers spring pond, and flows out of the hillside at the Eastern border of Viroqua town line. The spring is a tributary to the West Fork Kickapoo. Site #2 Amy Murphy property N 43 36.611 W 090 47.336 tidbit #2016450 Spring is located southwest of Leum Rd., near the eastern border of the Viroqua town line. The spring is a tributary to the West Fork Kickapoo. Site #3 - Crume Spring N 43 36.397 W 090 50.457 tidbit #2016451 Spring is located on the Randy Crume property, just west of Seas Branch Rd., town of Viroqua. This spring (one of a two @ this location) has a high capacity discharge of approximately 1500 2000 gal./min., which flows into Seas Branch creek, a tributary to the West Fork Kickapoo. Site #4 Doris Johnson property N 43 34.232 W 090 50.858 tidbit #2016452 Spring is approximately mile east of the bridge crossing, South Asbury Rd., town of Viroqua. Although this is a tributary to Maple Dale creek, it exemplifies the classic disappearing stream, appearing and disappearing several times before reaching Maple Dale. Site #5 Springville Spring N 43 35.019 W 090 56.293 tidbit #2016463 This is the familiar high capacity spring beneath the large concrete silo, west of Viroquas municipal treatment plant, just off CTH B, at Springville, town of Viroqua. This creek is part of the Bad Axe River watershed. Site #6 Cook Quarry Spring N 43 32.561 W 090 51.224 tidbit #2016439 This spring is directly below the Kraemer and Sons LLC rock quarry, just south of State Hwy. 56, town of Viroqua. This is the beginning of Cook creek, a tributary to Bishop Branch creek, and eventually the West Fork Kickapoo.

Land use characteristics of the intensively studied springs

Spring sites 2, 3 and 6 were studied for longer duration and are described here in more detail. We assessed the value of each sampling site during the study, and determined that Site 2 (Amy Murphy's Farm), Site 3 (Crume Spring) and Site 6 (Cook Quarry) were the most reliable and reflected a range of sizes (base flow levels.) We sampled these in detail throughout the study

period, and provide these results in the comparative analysis that follows. The data from the other sites can be found in appendix B. Relative flow rates for intensively studied springs: Amy Murphy Site 2 0.03 (feet3/sec) Crume Site 3 3.5 (feet3/sec) Cook Quarry Site 6 0.1 (feet3/sec)

We approximated the ground watershed influence by making the assumption that surface watershed would be related. The comparisons that follow show some expected correlations, and some discontinuities that need further explanation. For instance sites 3 and 6 have similar surface watershed area, but are an order of magnitude different in flow. These differences will be examined in the geologic setting summary paper being prepared by Kelvin Rodolfo.

Site 2: Amy Murphy

Land use within surface watershed site #2

Land use description Coniferous Forest Cropland Deciduous Forest Fallow Ag Land Farmstead Mixed Deciduous/Coniferous Forest Old Fields and Abandoned Lands Permanent Pasture and Hay Rural Residential Shrubland Transportation Lands Acres 1.33325745868 22.48958957660 162.54767357800 25.32229688170 1.58420677256 0.23816149375 1.59902588497 65.28226245480 2.63009035790 1.21920148854 4.68943853478 288.93520448228 Percent of total 0.4614465298 7.7837502428 56.2584963756 8.7641632512 0.5483012399 0.0824287868 0.5534302028 22.5944908645 0.9102863524 0.4219712347 1.6230362146 100.0018012952

This is a largely forested watershed, relatively small (under 300 acres) and few farmsteads (only 2 structures identified.)

Site 3: Cook Quarry

Land use within surface watershed site #3

Land use description Active Quarry Coniferous Forest Cropland Deciduous Forest Farmstead Institutional Mixed Deciduous/Coniferous Forest Old Fields and Abandoned Lands Open Water Permanent Pasture and Hay Residential Cluster Rural Residential Shrubland Transportation Lands Acres 9.41174398970 0.49066133325 870.34011556900 228.39525815100 47.51889900900 22.34932889830 148.82829549700 68.28624340880 0.58364244920 360.81912353700 0.36316311446 72.31273205980 117.54907282300 59.42784084600 2006.67612068550 Percent of total area 0.4690159959 0.0244511553 43.3717105481 11.3816344322 2.3680121099 1.1137354312 7.4165692678 3.4029124139 0.0290846888 17.9807207623 0.018097529 3.6035646614 5.8578299109 2.9614711141 99.9988100207

This watershed is largely agricultural use and probably larger farms since the farmsteads take up 2.4% of the watershed area. Forested areas comprise less than 20% of the surface watershed. This sub-basin has 62 structures, which would indicate that this many septic systems are likely.

Site 6: Crume Spring

Land use within surface watershed site #6 Land Use Description Active Quarry Commercial and Industrial Coniferous Forest Cropland Deciduous Forest Farmstead Institutional Old Fields and Abandoned Lands Open Water Permanent Pasture and Hay Rural Residential Shrubland Transportation Lands Urban Development Total: Acres 21.09847985410 28.52222729120 43.95511840660 879.75661566100 263.44297483800 26.09589144170 74.70677033370 83.30658550210 1.36960977418 162.44878408500 89.78235831720 111.81135387400 69.94675331650 245.24279731500 2101.48632001028 Percent of area 1.004211321 1.3575548449 2.0921046362 41.8732325398 12.5389326434 1.2420700353 3.5557720292 3.9650921229 0.0651884709 7.7319744924 4.2733154839 5.3218159864 3.3292124377 11.6726700293 100.0231470733

Crume Spring is a high flow site, yet with a surface watershed area similar to the Cook Quarry area. The watershed has 48 rural structures, and is affected by the southeastern quadrant of the City of Viroqua. The watershed is less than 15% forested.

Individual Parameters
The concentration of contaminants is dependent on the geology, which can chemically interact with the pollutants. Movement of water and pollutants are regulated by rainfall and geology of the aquifer. In our area karst formation transports contaminants quickly with rainfall and this dynamic resulted in all the sampling occurring as base flow, not storm as projected in the QAPP (appendix A). The temperature data for even large flow springs, indicated that the response to a storm was a matter of hours, and the constraints on delivery of samples to the Stevens Point limited our ability to sample in this timeframe. Data from results of analysis of temperature, total phosphorus, nitrite + nitrate, dissolved oxygen and E. coli will be examined.

Comparative Analysis by Parameter Temperature

The temperature dataloggers were installed in July and August of 2009. Over the course of the study several units were lost through vandalism and storms. Some early data was not retrievable because of a fault in the download in the field. Even with these failures, useful data was collected. We predicted that the most sensitive indicator of groundwater change under the influence of rain would be the spring's water temperature. The rain introduces water at a much higher temperature than the groundwater temperature and would be expected to be evident in the datalogger numbers. Sites 3 and 6 are springs with larger flow volumes, and turned out to be relatively unresponsive to the influence of rainfall. Site 2, however, which is a smaller flow volume and watershed catchment area, exhibits more dramatic peaks and lows. The best example is the peak temperature on 8/15/09 which correlates with a rainfall event. The rapid response, and return to normal temperatures shows how capturing water quality data on an event basis would require automated sampling equipment, which was beyond the scope of this project.

Total Phosphorus
Phosphorus carried by groundwater is a source of pollution thought to be rare. Since phosphorus adsorbs to the soil, finding it mobile in groundwater is remarkable. Phosphorus found in groundwater indicates fecal pollution and over-application of agricultural fertilizers. We did find measurable levels of phosphorus in the spring water sampled. The initial phosphorus concentration for Site 2 is extremely high on 8/15/09. Sites 3 and 6 seem to be at a constant concentration.

These sites have little or no variation of response to rainfall or season. The phosphorus concentrations for each site are generally under the surface water standard of 0.075 mg/L.

Nitrate + Nitrite
Nitrate +Nitrite measures the complete amount nitrogen in water. The nitrogen level in groundwater is of the utmost importance because it is the cause of "blue baby syndrome". Every site has some level of nitrite + nitrate. The concentrations of nitrate + nitrite are below the groundwater quality drinking standard of 10 mg/l. All sites have concentrations that are approximately half of the water quality standard and are at a level which requires close

monitoring of nitrate + nitrate to identify the sources of it and any rise in the contaminant that brings it close to the level of 10 mg/l.

The remarkable aspect of this data is that each spring seems to possess a consistent nitrogen concentration. These data are also correlated with watershed size and land use.

Dissolved Oxygen
Dissolved oxygen (DO) is the most important parameter for supporting all the various animals and plants in a river. The usual concentration in a healthy stream is 6.0 to 8.0 mg/L. Below that number a stream can only provide support to life that uses low levels of oxygen. At 8.0 mg/L a stream can support a great diversity of life, including trout. At very high levels of DO it is considered saturated and is too high a level for fish to use. As a spring emerges, its cold temperature and high turbulence increases DO. If there are contaminants that prevent DO being absorbed at the emergence point this can indicate high levels of pollution. The data on dissolved oxygen are the most responsive of all the parameters to rainfall. Site 2 shows similar response in DO as it had with temperature. The other sites also have responses to rainfall but less dramatic shifts.

The concentrations of DO range from quite high to a low of 5.5 mg/L. Although these are at the very edges of healthy levels of DO, the smaller watershed and lower flow-rate spring was most volatile. Explaining the dynamics involved is not straightforward since the temperature data do not track with the shifts in DO.

E. coli
We did not expect to find any measurable levels of E. coli in at any spring head sites. In general the sampling results found no bacteria. There were two remarkable sampling dates for two of the sampled sites. On 8/17 and 8/24 of 2009 several of the sites had E. coli present and in the case of Crume Spring, the levels were quite high. When this extreme result was reported, the team decided to return the next week to verify the results. E. coli levels (cfu's/100 mls) Date 08/17/09 08/24/09 Crume Spring (#3) >2420 308 Amy Murphy (#2) 25 4

Conclusions
There is ample evidence from this study that human activity is affecting the groundwater resource. When waste and fertilizers are applied to the surface it is the goal that these materials do not escape the zone that provides nutrients to crops. It is also assumed that the onsite waste treatment through septic system will prevent nitrogen, phosphorus and bacteria from leaving the site. All of these assumptions are challenged by this study. If we assume that the surface watershed approximates the groundwater catchment area, then the density of housing would not seem to support septic systems being the main contributor to the escape of nutrients and bacteria. The presence of E. coli in August of 2009 also suggests that some surface application, or dumping was affecting the water resource. The relatively constant levels of P and Nitrate in the spring water might suggest that the overapplication of nutrients has loaded the system to a point of saturation. While this pollution does not affect drinking water (although some people do drink from local springs) the geologic setting analysis will provide the potential vulnerability of the deeper aquifers to this relatively surficial source of pollution. Future Studies Due to the nature of rainfall events and quick response time of the groundwater system, an automated sampler that is sensitive to rainfalls from 0.5 in. to 1.0 in. or greater needs to be installed at the appropriate sample sites. This will also improve our understanding of the sensitivity of the springs as we observe changes in water chemistry. Some sites were eliminated because of equipment failures. Although these are not uncommon when sampling flowing waters, all the alternatives of automated sampling should be explored. Bundled sensors that measure and record data in a downloadable memory device is a desirable alternative. We extend our thanks to the Nuzum Foundation Kickapoo Valley Resforestation Fund for their funding of this project, and Dr. Fred Madison, who sponsored this research proposal.

Appendix A
QUAPP http://www.scribd.com/doc/69850068

Appendix B
Water quality results for all sites http://www.scribd.com/doc/69850161