Methods

Ammonium, Nitrate, Nitrit Samples for ammonium and nitrate or nitrite are collected together with a peristaltic pump and tubing and in-line filtered (through a 0.40 micron polycarbonate filter) into new, 20 ml HDPE plastic containers with conical caps. The samples are stored frozen until analysis, which should occur within 6 months. The samples are analyzed for ammonium (and nitrateornitrite) simultaneously by automated colorimetric spectrophotometry, using a segmented flow autoanalyzer. Ammonium is determined by utilizing the Berthelot Reaction, producing a blue colored indophenol compound, where the absorption is monitored at 660 nm. The detection limit for ammonium is approximately 3 ppb and the analytical range for the method extends to 4000 ppb. The detection limit for nitrateornitrite is approximately 2 ppb and the analytical range for the method extends to 4000 ppb. Method Log: Prior to January 2006 samples, ammonium was determined on a Technicon segmented flow autoanalyzer. From 2006 to present, ammonium is determined by an Astoria-Pacific Astoria II segmented flow autoanalyzer. Chloride, Sulfate Samples for chloride and sulfate are collected together with a peristaltic pump and tubing and in-line filtered (through a 0.40 micron polycarbonate filter) into new, 20 ml HDPE plastic containers with conical caps. The samples are stored refrigerated at 4 degrees Celsius until analysis, which should occur within 6 months. The samples are analyzed for chloride (and sulfate) simultaneously by Ion Chromatography, using a hydroxide eluent. The detection limit for chloride is approximately 0.01 ppm and the analytical range for the method extends to 100 ppm. The detection limit for sulfate is approximately 0.01 ppm and the analytical range for the method extends to 60 ppm. Method Log: Prior to January 1998 samples, chloride was determined on a Dionex DX10 Ion Chromatograph, using a chemical fiber suppressor. From 1998 to 2011, chloride was determined by a Dionex model DX500, using an electro-chemical suppressor. From January 2011 until present, chloride is determined by a Dionex model ICS 2100 using an electro-chemical suppressor. Calcium, magnesium, sodium, potassium, iron, and manganese Samples for calcium analysis (as well as dissolved nitrogen and phosphorus, magnesium, sodium, potassium, iron, and manganese) are collected together with a peristaltic pump and tubing and in-line filtered (through a 40 micron polycarbonate filter) into 120 ml LDPE bottles and acidified to a 1percent HCl matrix by adding 1 ml of ultra pure concentrated HCl to 100 mls of sample. For every sample acidification event, three acid blanks are created by adding the same acid used on the samples to 100 mls of ultra pure water supplied from the lab. Once acidified, the samples are stable at room temperature until analysis, which should occur within one year. Until acidification, the samples should be refrigerated at 4 degrees Celsius. Calcium, as well as magnesium, sodium, potassium, iron, and manganese are analyzed simultaneously on an optical inductively-coupled plasma emission spectrophotometer (ICP-OES). The acidified samples are directly aspirated into the instrument without a digestion. Calcium is analyzed at 317.933 nm and at 315.887 nm and viewed axially for low-level analysis and radially for high level analysis. The detection limit for calcium is 0.06 ppm with an analytical range of the method extends to 50 ppm. The detection limit for iron is 0.02 ppm with an analytical range of the method extends to 20 ppm. The detection limit for magnesium is 0.03 ppm with an analytical range of the method extends to 50 ppm. The detection limit for manganese is 0.01 ppm with an analytical range of the method extends to 2 ppm. The detection limit for potassium is 0.06 ppm with an analytical range of the method extends to 10 ppm. The detection limit for sodium is 0.06 ppm with an analytical range of the method extends to 50 ppm. Method Log: Prior to January 2002, calcium, magnesium, sodium, potassium, iron, and manganese were determined on a Perkin-Elmer model 503 Atomic Absorption Spectrophotometer. Lanthanum at a 0.8percent concentration was added as a matrix modifier to suppress chemical interferences. From January 2002 to present, samples are analyzed for calcium on a Perkin-Elmer model 4300 DV ICP. Inorganic and organic carbon Samples for inorganic and organic carbon are collected together with a peristaltic pump and tubing and in-line filtered, if necessary, (through a 0.40 micron polycarbonate filter) into glass, 24 ml vials (that are compatible with the carbon analyzer autosampler), and capped with septa, leaving no head space. The samples are stored refrigerated at 4 degrees Celsius until analysis, which should occur within 2-3 weeks. The detection limit for inorganic carbon is 0.15 ppm, and the analytical range for the method is 60 ppm. The detection limit for organic carbon is 0.30 ppm and the analytical range for the method is 30 ppm. Method Log: Prior to May 2006 samples, inorganic carbon was analyzed by phosphoric acid addition on an OI Model 700 Carbon Analyzer. From May 2006 to present, inorganic carbon is still analyzed by phosphoric acid addition, but on a Shimadzu TOC-V-csh Total Organic Carbon Analyzer. Method Log: Prior to May 2006 samples, organic carbon was analyzed by heated persulfate digestion on an OI Model 700 Carbon Analyzer. From May 2006 to present, Organic carbon is analyzed by combustion, on a Shimadzu TOC-V-csh Total Organic Carbon Analyzer. Dissolved reactive silicon Samples for silicon are collected with a peristaltic pump and tubing and in-line filtered (through a 40 micron polycarbonate filter) into 120 ml LDPE bottles and acidified to a 1percent HCl matrix by adding 1 ml of ultra pure concentrated HCl to 100 mls of sample. For every sample acidification event, three acid blanks are created by adding the same acid used on the samples to 100 mls of ultra pure water supplied from the lab. Once acidified, the samples are stable at room temperature until analysis, which should occur within one year. Until acidification, the samples should be refrigerated at 4 degrees Celsius. Dissolved reactive silica is determined by the Heteropoly Blue Method and the absorption is measured at 820 nm. The detection limit for silicon is 6 ppb and the analytical range is 15000 ppb. Method Log These determinations were performed manually using a Bausch and Lomb Spectrophotometer from the beginning of the project until April 1984. From 1984 through 2005, dissolved reactive silicon was determined on a Technicon Auto Analyzer II. From January 2006 to present, samples are run on an Astoria-Pacific Astoria II Autoanalyzer. total and dissolved nitrogen and phosphorus Samples for total and dissolved nitrogen and phosphorus analysis are collected together with a peristaltic pump and tubing and in-line filtered, when necessary, (through a 40 micron polycarbonate filter) into 120 ml LDPE bottles and acidified to a 1percent HCl matrix by adding 1 mL of ultra pure concentrated HCl to 100 mls of sample. For every sample acidification event, three acid blanks are created by adding the same acid used on the samples to 100 mls of ultra pure water supplied from the lab. Once acidified, the samples are stable at room temperature until analysis, which should occur within one year. Until acidification, the samples should be refrigerated at 4 degrees Celsius. The samples must first be prepared for analysis by adding an NaOH–Persulfate digestion reagent and heated for an hour at 120 degrees C and 18-20 psi in an autoclave. The samples are analyzed for total nitrogen and total phosphorus simultaneously by automated colorimetric spectrophotometry, using a segmented flow autoanalyzer. Total nitrogen is determined by utilizing the automated cadmium reduction method, as described in Standard Methods, where the absorption is monitored at 520 nm. The detection limit for total and dissolved nitrogen is approximately 21 ppb and the analytical range for the method extends to 2500 ppb. The detection limit for total phosphorus is approximately 3 ppb and the analytical range for the method extends to 800 ppb. Method Log: Prior to January 2006 samples, total nitrogen was determined on a Technicon segmented flow autoanalyzer. From 2006 to present, total nitrogen is determined by an Astoria-Pacific Astoria II segmented flow autoanalyzer. pH We sample at the deepest part of the lake using a peristaltic pump and tubing, monthly during open water and approximately every five weeks during ice cover. We collect two types of pH samples at each sampling depth: one in 20ml vials with cone cap inserts to exclude all air from the vial, and one in 125ml bottles to be air equilibrated before analysis. The depths for sample collection are based on thermal stratification: top and bottom of the epilimnion, mid thermocline, and top, middle,and bottom of the hypolimnion. During mixis we sample at the surface, mid water column, and bottom. We analyze for pH the same day that samples are collected, keeping them cold and dark until just before analysis. Samples are warmed to room temperature in a dark container, and the air equilibrated samples are bubbled with outside air for at least 15 minutes prior to measurement. We measure pH using a Radiometer combination pH electrode and Orion 4Star pH meter. Protocol Log: 1981-1988 -- used a PHM84 Research pH meter. 1986 -- began analyzing air equilibrated pH. 1988 - July 2010 -- used an Orion model 720 pH meter.</p>

Methods

Chloride, Sulfate Samples for chloride and sulfate are collected together with a peristaltic pump and tubing and in-line filtered (through a 0.40 micron polycarbonate filter) into new, 20 ml HDPE plastic containers with conical caps. The samples are stored refrigerated at 4 degrees Celsius until analysis, which should occur within 6 months. The samples are analyzed for chloride (and sulfate) simultaneously by Ion Chromatography, using a hydroxide eluent. The detection limit for chloride is approximately 0.01 ppm and the analytical range for the method extends to 100 ppm. The detection limit for sulfate is approximately 0.01 ppm and the analytical range for the method extends to 60 ppm. Method Log: Prior to January 1998 samples, chloride was determined on a Dionex DX10 Ion Chromatograph, using a chemical fiber suppressor. From 1998 to 2011, chloride was determined by a Dionex model DX500, using an electro-chemical suppressor. From January 2011 until present, chloride is determined by a Dionex model ICS 2100 using an electro-chemical suppressor.

Methods

Chloride, SulfateSamples for chloride and sulfate are collected together with a peristaltic pump and tubing and in-line filtered (through a 0.40 micron polycarbonate filter) into new, 20 ml HDPE plastic containers with conical caps. The samples are stored refrigerated at 4 degrees Celsius until analysis, which should occur within 6 months. The samples are analyzed for chloride (and sulfate) simultaneously by Ion Chromatography, using a hydroxide eluent.The detection limit for chloride is approximately 0.01 ppm and the analytical range for the method extends to 100 ppm.The detection limit for sulfate is approximately 0.01 ppm and the analytical range for the method extends to 60 ppm.Method Log: Prior to January 1998 samples, chloride was determined on a Dionex DX10 Ion Chromatograph, using a chemical fiber suppressor. From 1998 to 2011, chloride was determined by a Dionex model DX500, using an electro-chemical suppressor. From January 2011 until present, chloride is determined by a Dionex model ICS 2100 using an electro-chemical suppressor.

Methods

Site SelectionBecause lakes are a dominant feature of the region and stream characteristics could potentially differ based on their hydrologic connections to lakes, we classified streams into three categories as a function of their hydrologic connections to lakes. The first category was streams that had no lakes within the drainage network upstream of the sampling location. The second category was streams that originated from headwater lakes (i.e., no stream inlet but a stream outlet) and the headwater lake was the only lake in the drainage network above the sampling location. The final category had at least a single drainage lake (i.e., a lake with both stream inlet(s) and outlet) in the drainage network above the sampling location. We then used these categories to select sampling sites using a stratified random design for a variety of chemical and physical characteristics.All streams identified on 1:24,000 7.5 inch USGS topographical maps that crossed access points were selected as potential sampling locations and assigned to one of the three stream types. A stream could be classified by more than a single category depending on the sampling location within the drainage network. However, a single drainage network was never sampled more than once to ensure sample independence. Of the 500 possible sampling locations, 52 sites were selected and sampled.SamplingAll streams were sampled 7-10 channel widths upstream of an access point to minimize any influences caused by culverts and other features. Water samples were collected from the center of the channel using a peristaltic pump. Stream discharge was measured after Gore (2007) using cross sectional area and water velocity.Chemical AnalysesAll samples for both studies were collected and processed following the North Temperate Long Term Ecological Research (NTL-LTER) protocols (http://lter.limnology.wisc.edu). Filtering was done in the field using an in-line 0.45 μm membrane filter. All samples were stored on ice and returned to the laboratory where they were preserved according to NTL-LTER protocols. Acid neutralizing capacity (ANC) was determined by Gran titration (APHA 2005). DOC was measured on a Shimadzu TOC-V carbon analyzer. Total nitrogen and phosphorus (unfiltered, TN and TP; filtered, TDN and TDP), nitrate+nitrite (NO3-N), and ammonium (NH4-N) were quantified with an Astoria-Pacific segmented flow auto-analyzer. Soluble reactive phosphorus (SRP) in streams was measured colormetrically on a Beckman DU-800 spectrophotometer (APHA 2005). Anions (Cl- and SO4 2-) were measured using a Dionix DX-500 ion chromatograph and cations (Ca, Mg, Na, K, Fe, K, and Mn) on a Perkin Elmer ICP mass spectrometerDissolved inorganic carbon (DIC) and pH were quantified differently in the lakes and stream data sets. For the lakes data, DIC was determined with a Shimadzu TOC-V carbon analyzer, whereas DIC for the streams dataset was determined by headspace equilibration of acidified water samples in the field and direct measurement of carbon dioxide (CO2) gas on a Shimadzu gas chromatograph (Cole et al. 1994). pH measurements for the lakes dataset were quantified on non-air equilibrated samples in the lab with a Accumet 950 pH meter while direct measurements were taken in the field for the streams dataset using a hand-held Orion model 266 pH meter that was allowed to equilibrated about 20 min in the center for the stream channel.Several variables presented in this study were determined from calculations based on measured values. In streams, dissolved organic nitrogen and phosphorus (DON and DOP, respectively) were determined by the difference between inorganic nutrients and total dissolved nutrients (e.g., DOP = TDP-SRP). We were unable to determine DON in lakes due to the lack of inorganic nitrogen data. It was assumed that DOP approximately equals TDP in lakes because dissolved inorganic phosphorus concentrations in the region are typically below detection limits in the epilimnion during the summer months and consequently not quantified (NTL-LTER unpublished data).

Methods

Chloride, SulfateSamples for chloride and sulfate are collected together with a peristaltic pump and tubing and in-line filtered (through a 0.40 micron polycarbonate filter) into new, 20 ml HDPE plastic containers with conical caps. The samples are stored refrigerated at 4 degrees Celsius until analysis, which should occur within 6 months. The samples are analyzed for chloride (and sulfate) simultaneously by Ion Chromatography, using a hydroxide eluent.The detection limit for chloride is approximately 0.01 ppm and the analytical range for the method extends to 100 ppm.The detection limit for sulfate is approximately 0.01 ppm and the analytical range for the method extends to 60 ppm.Method Log: Prior to January 1998 samples, chloride was determined on a Dionex DX10 Ion Chromatograph, using a chemical fiber suppressor. From 1998 to 2011, chloride was determined by a Dionex model DX500, using an electro-chemical suppressor. From January 2011 until present, chloride is determined by a Dionex model ICS 2100 using an electro-chemical suppressor.Calcium, silicon, magnesium, sodium, potassium, iron, and manganeseSamples for calcium analysis (as well as dissolved nitrogen and phosphorus, silicon, magnesium, sodium, potassium, iron, and manganese) are collected together with a peristaltic pump and tubing and in-line filtered (through a 40 micron polycarbonate filter) into 120 ml LDPE bottles and acidified to a 1percent HCl matrix by adding 1 ml of ultra pure concentrated HCl to 100 mls of sample. For every sample acidification event, three acid blanks are created by adding the same acid used on the samples to 100 mls of ultra pure water supplied from the lab. Once acidified, the samples are stable at room temperature until analysis, which should occur within one year. Until acidification, the samples should be refrigerated at 4 degrees Celsius.Calcium, as well as magnesium, sodium, potassium, iron, and manganese are analyzed simultaneously on an optical inductively-coupled plasma emission spectrophotometer (ICP-OES). The acidified samples are directly aspirated into the instrument without a digestion. Calcium is analyzed at 317.933 nm and at 315.887 nm and viewed axially for low-level analysis and radially for high level analysis.The detection limit for calcium is 0.06 ppm with an analytical range of the method extends to 50 ppm.The detection limit for iron is 0.02 ppm with an analytical range of the method extends to 20 ppm.The detection limit for magnesium is 0.03 ppm with an analytical range of the method extends to 50 ppm.The detection limit for manganese is 0.01 ppm with an analytical range of the method extends to 2 ppm.The detection limit for potassium is 0.06 ppm with an analytical range of the method extends to 10 ppm.The detection limit for sodium is 0.06 ppm with an analytical range of the method extends to 50 ppm.Method Log: Prior to January 2002, Calcium, magnesium, sodium, potassium, iron, and manganese were determined on a Perkin-Elmer model 503 Atomic Absorption Spectrophotometer. Lanthanum at a 0.8percent concentration was added as a matrix modifier to suppress chemical interferences. From January 2002 to present, samples are analyzed for calcium on a Perkin-Elmer model 4300 DV ICP.Dissolved reactive silica is determined by the Heteropoly Blue Method and the absorption is measured at 820 nm.The detection limit for silicon is 6 ppb and the analytical range is 15000 ppb.Method Log These determinations were performed manually using a Bausch and Lomb Spectrophotometer from the beginning of the project until April 1984. From 1984 through 2005, dissolved reactive silicon was determined on a Technicon Auto Analyzer II. From January 2006 to present, samples are run on an Astoria-Pacific Astoria II Autoanalyzer.

Methods

Schell, Jeffery M., Carlos J. Santos-Flores, Paula E. Allen, Brian M. Hunker, Scott Kloehn, Aaron Michelson, Richard A. Lillie, and Stanley I. Dodson. 2001. Physical-chemical influences on vernal zooplankton community structure in small lakes and wetlands of Wisconsin, U.S.A. Hydrobiologia 445:37-50

Methods

A combination map, consisting of the information in both the population density map and the modified-distance map, was also created (Figure 2c). This map is simply based on a grid cell by grid cell multiplication of the reclassified values from the population density and the modified distance map. In this paper, I will refer to this map as the combination map.Data points for measuring soil P and associated factors were stratified by zone and randomly located within each zone according to the combination map&mdash;with approximately 70 data points per zone. Location and address of each point were determined using the Madison and Dane County parcel GIS layers. Permission was requested from landowners to take a soil sample, and the precise location of the sample on the property was determined using standard randomizing techniques. If permission was denied (2 cases out of 330) or if there was no one present at the location, a coin toss was used to determine movement one parcel to the right or to the left along the same road. Landowners were also asked about their fertilizer use practices, manure use, dog ownership, and the date the house was built, if known.Approximately 400 soil samples were taken in the top soil horizon to a depth of 13.5 cm with a standard soil corer (diameter = approximately 1.6 cm). This depth was always within the surface horizon and any grass thatch was removed from lawn samples. Other data collected include percent slope, convex or concave nature of the slope, land use, land-cover type, and percent vegetative cover. The visually perceived zone was also recorded. The visually perceived zone was determined by visual inspection using a predetermined set of definitions of each zone. For example, urban sites were those with the highest housing density or some industrial use; suburban sites were those of moderate housing density and residential character; suburban fringe were newer residential developments of low housing density and larger houses; agricultural fringe were older residential developments of low density; and agricultural were those areas that were actively farmed. A handheld global positioning device was used to determine the precise (&plusmn; 1 m) location of the soil sample.Soil samples were stored for no more than 3 weeks at room temperature before analysis. They were then dried for 15&ndash;24 hours at 50&ndash;55degreeC and sieved (1.8-mm mesh). Soil samples were then analyzed for Bray-1 P at the University of Wisconsin Soil and Plant Analysis Lab. Bray-1, a measure of extractable P, is a commonly used measure of phosphorus available to plants in agricultural systems. While relationships between extractable soil P and dissolved P in runoff have been noted in some systems (Sharpley and others 1993, Sharpley 1995), these extractions were generally developed to estimate plant available P, not to reflect P storage in the soil or P runoff. Therefore, we tested a subset (60) of our samples for total P, a better measure of P storage in soils. A regression of our samples indicates a reasonably close relationship between Bray-1 P and total P in our study area soils (Figure 3), indicating that our Bray-1 P results are probably a satisfactory estimate of both extractable P and the sorbed P that tends to accumulate in agricultural soils.

Methods

Johnson, M.D. (1984) Documentation and quality assurance of the computer files of historical water chemistry data from the Wisconsin Northern Highland Lake District (the Birge and Juday data).Wisconsin DNR Technical Report.Methods not included in Johnson (1984):Nitrite Nitrogen- Sulphanilic acid procedure. Standard methods for the examination of water and sewage, Pub. Health Assn., New York, 5th edition, 1923, 13. Other Documentation: Domogalla, B.P., Juday, C., and Peterson, W.H. 1925. The forms of nitrogen found in certain lake waters. Jour. Biol. Chem. 63: 269-285.Ferric Ion- First calculated by subtracting ferrous ion from total iron measurements. Standard methods of water analysis. 1936. Amer. Pub. Health Assoc. P. 309. New York. Procedure was modified to determine ferric ion by acidifying samples by adding 1 milliliter of 3 N HCL to 50mL of lake water. With the iron samples in readiness, add 5 ml of the thiocyanate solution to the sample and to the standards, mix and compare immediately. (Standard Methods, Amer. Public Health Assoc. 8th ed., p. 75, 1936). Other documentation: Domogalla, B.P., Juday, C., and Peterson, W.H. 1925. The forms of nitrogen found in certain lake waters. Jour. Biol. Chem. 63: 269-285.Ferrous Ion- First calculated by ferricyanide method. Procedure was modified to determine ferrous ion by subtracting ferric ion from total iron. Documentation: Domogalla, B.P., Juday, C., and Peterson, W.H. 1925. The forms of nitrogen found in certain lake waters. Jour. Biol. Chem. 63: 269-285.Manganese- Determined by the persulfate method using the procedure described in Standard Methods of Water Analysis, Amer. Public Health Assoc., p. 84, 1936.Chlorophyll-a- A photometric method was used, in which the color of the light was confined to the wave-length 6200-6800 A which are absorbed by chlorophyll. Water samples of 5 to 15 liters (18 liters in the case of very low plankton content) were taken from different depths by using a hand operated vacuum pump), the water was the centrifuged at 25,000 rpm (for about 30 minutes). Residue was then washed with 98percent acetone, and CaCO3 was added to neutralize organic acids. This residue-acetone mixture was ground to extract the chlorophyll. The acetone extract was then filtered through filter paper into a flask, the residue being thoroughly washed with pure acetone. The light absorption of the extract was then measured. Procedure was carried out in a single day, under minimal light. Documentation: Kemmerer, G.I., and Hallett, L.T. 1938. Amount and distribution of the chlorophyll in some lakes of northeastern Wisconsin. Trans. Wisconsin Acad. Sci. 31: 411-438.Phosphate- Ceruleomolybdic method employed. Documentation: Juday, C., Birge, E.A., Kemmerer, G.I., Robinson, R.J. 1927. Phosphorus content of lake waters of northeastern Wisconsin. Trans. Wisconsin. Acad. Sci. 23: 233-248. Other Documentation: Robinson, R.J., Kemmerer, G.I. 1930. Determination of organic phosphorus in lake waters. Trans. Wisconsin. Acad. Sci. 25: 117-121.Redox Potential- Determined in situ on a given sampling date by use of a bright platinum electrode. Eh readings were made in millivolts. Documentation: Allgeier, R.J., Hafford, B.C., and Juday, C. 1941. Oxidation-reduction potentials and pH of lake waters and lake sediments. Trans. Wisconsin Acad. Sci. 33: 115-133.Note: The methodology used to determine copper, alumnium, boron, and hydrogen sulfide could not be determined.

Methods

please see methods description in abstract

Methods

Methods are published in Glass, G.E. and Sorenson, J.A. (1994) USEPA ERLD-UMD acid deposition gradient-susceptibility database. U.S. EPA Environmental Research Laboratory - Duluth and University of Minnesota at Duluth, MN.