Test 12 Water Quality with Computers 12 - 1 Total Dissolved Solids INTRODUCTION Solids are found in streams in two forms,

suspended and dissolved. Suspended solids include silt, stirred-up bottom sediment, decaying plant matter, or sewage-treatment effluent. Suspended solids will not pass through a filter, whereas dissolved solids will. Dissolved solids in freshwater samples include soluble salts that yield ions such as sodium (Na + ), calcium (Ca 2+ ), magnesium (Mg 2+ ), bicarbonate (HCO3 ), sulfate (SO4 2 ), or chloride (Cl ). Total dissolved solids, or TDS, can be determined by evaporating a pre-filtered sample to dryness, and then finding the mass of the dry residue per liter of sample. A second method uses a Vernier Conductivity Probe to

determine the ability of the dissolved salts and their resulting ions in an unfiltered sample to conduct an electrical current. The conductivity is then converted to TDS. Either of these methods yields a TDS value in units of mg/L. The TDS concentration in a body of water is affected by many different factors. A high concentration of dissolved ions is not, by itself, an indication that a stream is polluted or unhealthy. It is normal for streams to dissolve and accumulate fairly high concentrations of ions from the minerals in the rocks and soils over which they flow. If these deposits contain salts (sodium chloride or potassium chloride) or limestone (calcium carbonate), then significant concentrations of Na + ,K + , Cl will result, as well as hard-water ions, such as Ca 2+ and HCO3 from limestone. TDS is sometimes used as a watchdog environmental test. Any change in the ionic composition between

testing sites in a stream can quickly be detected using a Conductivity Probe. TDS values will change when ions are introduced to water from salts, acids, bases, hardwater minerals, or soluble gases that ionize in solution. However, the tests described here will not tell you the specific ion responsible for the increase or decrease in TDS. They simply give a general indication of the level of dissolved solids in the stream or lake. Further tests described in this book can then help to determine the specific ion or ions that contributed to changes in the initial TDS reading. There are many possible manmade sources of ions that may contribute to elevated TDS readings. Fertilizers from fields and lawns can add a variety of ions to a stream. Increases in TDS can also result from runoff from roads that have been salted in the winter. Organic matter from wastewater treatment plants may contribute higher levels of nitrate or phosphate ions. Treated wastewater may also have higher TDS readings than surrounding streams if urban drinking water has been highly chlorinated. Irrigation water that is returned to a stream will often have higher concentrations of sodium or chloride ions. Acidic rainwater, with dissolved gases like CO2, NO2, or SO2, often yields elevated H + ion concentrations. Sources of Total Dissolved Solids Hard-Water Ions - Ca 2+ - Mg 2+ - HCO3 Fertilizer in agricultural runoff - NH4

+ - NO3 - PO4 3 - SO4 2 Urban runoff - Na + - Cl Salinity from tidal mixing, minerals, or returned irrigation water - Na + -K + - Cl Acidic rainfall -H + - NO3 - SO3 2

, SO4 2Test 12 12 - 2 Water Quality with Computers TDS If TDS levels are high, especially due to dissolved salts, many forms of aquatic life are affected. The salts act to dehydrate the skin of animals. High concentrations of dissolved solids can add a laxative effect to water or cause the water to have an unpleasant mineral taste. It is also possible for dissolved ions to affect the pH of a body of water, which in turn may influence the health of aquatic species. If high TDS readings are due to hard-water ions, then soaps may be less effective, or significant boiler plating may occur in heating pipes. Expected Levels TDS values in lakes and streams are typically found to be in the range of 50 to 250 mg/L. In areas of especially hard water or high salinity, TDS values may be as high as 500 mg/L. Drinking water will tend to be 25 to 500 mg/L TDS. United States Drinking Water Standards1 include a recommendation that TDS in drinking water should not exceed 500 mg/L TDS. Fresh distilled water, by comparison, will usually have a conductivity of 0.5 to 1.5 mg/L TDS. Table 1: TDS in Selected Rivers Site Season TDS (mg/L) Season TDS (mg/L) Rio Grande River, El Paso, TX Spring 510 Fall 610 Mississippi River, Memphis, TN Spring 133 Fall 220 Sacramento River, Keswick, CA Spring 71 Fall 60 Ohio River, Benwood, WV Spring 300 Fall 143 Hudson River, Poughkeepsie, NY Spring 90 Fall 119 Summary of Methods

Method 1: TDS Using a Conductivity Probe A Vernier Conductivity Probe is used on site, or placed into samples collected at sites, to measure TDS concentration of the solution. It offers the advantage that it can be performed without filtration, providing instantaneous feedback about total dissolved solids concentration in a stream. Method 2: TDS By Evaporation Using this method, samples are first filtered to remove suspended solids. A precise amount of sample is added to a carefully cleaned, dried, and weighed beaker. The water is then evaporated in a drying oven. The difference in mass between the two weighings is the mass of the total dissolved solids. Calculations are then performed to convert the change in mass to mg/L of TDS. This procedure does not require a sensor, but does require an analytical balance (0.001 or 0.0001-g resolution).

1 Established by 1986 Amendments to the Safe Drinking Water ActTotal Dissolved Solids Water Quality with Computers 12 - 3 TDS Method 1: TDS USING A CONDUCTIVITY PROBE Materials Checklist ___ laptop computer (Power Mac or Windows) ___ wash bottle with distilled water ___ Vernier computer interface, battery-powered ___ tissues or paper towels ___ Logger Pro ___ small paper or plastic cup (optional) ___ Vernier Conductivity Probe ___ 50 mg/L TDS standard solution (optional) ___ 500 mg/L TDS standard solution Collection and Storage of Samples 1. This test can be conducted on site or in the lab. A 100-mL water sample is required.

2. It is important to obtain the water sample from below the surface of the water as far away from shore as is safe. If suitable areas of the stream appear to be unreachable, samplers consisting of a rod and container can be constructed for collection. Refer to page Intro-4 of the Introduction of this book for more details. 3. If the testing cannot be conducted within a few hours, place the samples in an ice chest or a refrigerator. Testing Procedure 1. Position the computer safely away from the water. Keep water away from the computer at all times. 2. Prepare the computer for data collection by opening Test 12 Total Dissolved Solids from the Water Quality with Computers experiment files of Logger Pro. On the Graph window, the vertical axis has concentration scaled from 0 to 1000 mg/L TDS. The horizontal axis has time scaled from 0 to 10 seconds. There is also a Meter window which displays live TDS concentration readings. 3. Prepare the Conductivity Probe for data collection. a. Plug the Conductivity Probe into Port 1 or Channel 1 of the Vernier computer interface. b. Set the switch on the probe box to the 0-2000 S range (2000 S = 1000 mg/L TDS). 4. You are now ready to prepare the computer and the Conductivity Probe for calibration. If your instructor directs you to use the calibration stored in the experiment file, then proceed to Step 5. If your instructor directs you to perform a new calibration for the Conductivity Probe, follow this procedure:Test 12

12 - 4 Water Quality with Computers TDS First Calibration Point a. Choose Calibrate from the Experiment menu and then click . b. Perform the first calibration point with the probe in the air (e.g., out of any solution). c. Type 0 in the edit box. d. When the displayed voltage reading for Input 1 stabilizes, click Keep . Second Calibration Point e. Place the Conductivity Probe into the 500 mg/L TDS standard solution. The hole near the tip of the probe should be covered completely. f. Type 500 (the concentration in mg/L TDS) in the edit box. g. When the displayed voltage reading for Input 1 stabilizes, click Keep , then click OK . 5. You are now ready to collect TDS concentration data. a. Rinse the probe tip with distilled water. b. Place the tip of the probe into the stream, or into a cup with sample water from the stream. The hole near the tip of the probe should be completely covered. c. If the TDS value appears stable, simply record it on the Data & Calculations sheet and proceed to Step 7. 6. If the TDS value displayed in the Meter window is fluctuating, determine the mean (or average) value. To do this: a. Click Collect to begin a 10-second sampling run. Important: Leave the probe tip submerged for the 10 seconds that data is being collected. b. Click on the Statistics button, , to

display the statistics box on the graph. c. Record the mean TDS value on the Data & Calculations sheet. 7. Return to Step 5 to obtain a second reading.Total Dissolved Solids Water Quality with Computers 12 - 5 TDS DATA & CALCULATIONS Method 1: TDS Using a Conductivity Probe Stream or lake: ___________________________ Time of day: __________________________ Site name: ______________________________ Student name: ________________________ Site number: ____________________________ Student name: ________________________ Date: __________________________________ Student name: ________________________ Column A Reading TDS (mg/L) 1 2 Average Column Procedure: A. Record the TDS value (in mg/L) from the computer. Field Observations (e.g., weather, geography, vegetation along stream) _________________________ _____________________________________________________________________________ _____________________________________________________________________________ _____________________________________________________________________________ Test Completed: ________________ Date: ______Test 12

12 - 6 Water Quality with Computers TDS Method 2: TDS BY EVAPORATION Materials Checklist ___ sampling bottles ___ drying oven ___ one 600-mL beaker for filtration container ___ 100-mL graduated cylinder ___ large funnel (>10 cm diameter) ___ two 250-mL beakers ___ filter paper to fit large funnel ___ milligram balance (0.001 g) ___ tongs or gloves to hold beaker Collection and Storage of Samples 1. This test can be conducted on site or in the lab. Collect a 500-mL water sample per site so that you can run two 200-mL trials. Note: If your stream or lake could have low levels of TDS, then collect a larger sample volume (see Step 6 of the Testing Procedure). 2. It is important to obtain the water sample from below the surface of the water as far away from shore as is safe. If suitable areas of the stream appear to be unreachable, samplers consisting of a rod and container can be constructed for collection. Refer to page Intro-4 of the Introduction of this book for more details. 3. If samples cannot be tested immediately upon returning to the lab, they should be refrigerated until the time of analysis to avoid microbiological decomposition of solids. Samples should not be tested after seven days. Testing Procedure Day 1 1. Filter any solid particles or suspended solids from your sample. a. Set up a funnel and funnel support on a ring stand. Place a 600-mL beaker or other large container below the funnel. b. Place a folded piece of filter paper in the funnel and moisten it with distilled water so that it adheres to the funnel sides.

c. Slowly add your 500-mL sample to the funnel, being sure not to let the level of liquid in the funnel go above the top of the filter paper. Continue adding your sample to the funnel until you have more than 400 mL of filtrate in the beaker below the funnel. 2. Prepare two 250-mL beakers for drying and sample evaporation. a. Carefully clean two 250-mL beakers and place them in a 100105C drying oven for one hour to dry. b. Remove the beakers from the oven. Allow them to cool. c. Using a pencil, number your beakers 1 and 2. Do not use label tape. d. From this point on, always handle the beakers with tongs or gloves to prevent the oils on your hands from affecting their mass. Weigh each beaker on a milligram balance to the nearest 0.001 g. Record the data on the Data & Calculations sheet. e. If you complete Step 2 before collecting samples, leave the beakers in a clean, dry, dust-free space until you return to the lab.Total Dissolved Solids Water Quality with Computers 12 - 7 TDS 3. Transfer the samples to the beakers. a. Using a 100-mL graduated cylinder, carefully measure 200.0 mL of filtered sample water into each beaker. b. Place the remaining sample water into a refrigerator for possible future use. 4. Using tongs or gloves, place the beakers into the oven and allow the water to evaporate overnight at 104C. Day 2 5. Measure the mass of the beakers and solids. a. Using tongs or gloves, remove the beakers from the oven and place them in

a dessicator, if available, to cool. A dessicator will keep the samples from absorbing any water from the air that would increase their mass. If no dessicator is available, the beakers can be cooled on a table top. Proceed to the next step as soon as possible to minimize any absorption of water. b. Use an analytical balance to measure the mass of each beaker with the solids now left behind. Record the values on the Data & Calculations sheet (round to the nearest 0.001 g). c. Obtain the mass of the solids by subtracting the mass of the empty beaker from the mass of the beaker with the solids. If the mass of the solids is at least 0.025 g, proceed to Step 7. If the mass of the solids is less than 0.025 g, proceed to Step 6. 6. If the mass of the solids is less than 0.025 g, add another 200.0 mL of sample to each beaker and repeat Steps 4 and 5. Make a note on the Data & Calculations sheet that your total volume is now 400.0 mL instead of 200.0 mL. 7. Record the mass of each beaker plus the solids on the Data & Calculations sheet. 8. Soak the beakers in hot soapy water. Cool sample in a dessicator, if available.Test 12 12 - 8 Water Quality with Computers TDS

DATA & CALCULATIONS Method 2: TDS by Evaporation Stream or lake: __________________________ Time of day: _________________________ Site name: _____________________________ Student name: _______________________ Site number: ____________________________ Student name: _______________________ Date: _________________________________ Student name: _______________________ Column A B C D E F Beaker Number Mass of empty beaker (g) Mass of beaker plus solids (g) Mass of solids (g) Mass of solids (mg) Total volume (L) TDS (mg/L) Example 95.245 g 95.277 g 0.032 g 32 mg 0.200 L 160 mg/L 1 2

Average TDS (mg/L) Column Procedure: A. Mass of empty beaker B. Mass of beaker with dried solids C. Mass of solids (g) = B A D. Mass of solids (mg) = C5 1000 E. Total volume (L) = mL water / 1000 F. TDS = D / E Field Observations (e.g., weather, geography, vegetation along stream) ________________________ _____________________________________________________________________________ _____________________________________________________________________________ _____________________________________________________________________________ Test Completed: ________________ Date: ______Total Dissolved Solids Water Quality with Computers 12 - 9 TDS ADDITIONAL INFORMATION Tips for Instructors Method 1: TDS Using a Conductivity Probe 1. There is a nearly linear relationship between conductivity and total dissolved solid concentration (of dissolved ionic substances). A curve similar to the one shown here can be obtained using standard TDS solutions. In the figure shown here, the ratio of TDS concentration in mg/L to conductivity in S/cm is 0.5 to 1, and represents the approximate relationship between TDS concentration as sodium chloride and conductivity.

2. Step 4 of the student procedure provides several alternatives for loading or performing a TDS calibration: The easiest option is to use the TDS calibration that is stored with the Logger Pro experiment file, Test 12 Total Dissolved Solids. The stored calibration corresponds to your range setting on the switch box (0 2000 S/cm, corresponding to 0 1000 mg/L TDS). This calibration measures mg/L TDS as NaCl; therefore, it is based on a sodium chloride standard, and does not take into account the variation in ion composition of different streams. If your purpose in measuring TDS is to monitor a stream for changes in total ion concentration, this calibration will work very well. If you want to determine a precise TDS concentration value at one location, either of the next two options will provide better results. The stored TDS calibrations the Logger Pro experiment file, Test 12 Total Dissolved Solids, make use of the equation, TDS = 0.50 5 Conductivity (in S/cm)a relationship based on sodium chloride calibrations. Most freshwater streams, however, have higher concentrations of hard-water ions (Ca 2+ and HCO3 ) than salt ions (Na + and Cl ). Large variations in ionic composition of streams result in the 0.50 constant actually ranging from 0.50 to 0.90. An average value of 0.70 is often used in freshwater studies TDS = 0.70 5 Conductivity (in S/cm) If you are making measurements in a freshwater (non-brackish) samples, improved TDS

data can usually be obtained if you use a calibration that reflects the 0.70 value. Simply open Test 12 Total Dissolved Solids, then choose Calibrate from the Experiment menu. Click on the Details tab. In the Details dialog box, you will see the values for the intercept and slope values displayed for the TDS calibration. Click on the Unlock button. You can now manually enter the intercept and slope values for a calibration based on the constant, 0.70. The values to be manually entered are 2 Intercept = 0 Slope = 593 This calibration will give TDS readings (in mg/L TDS) over a range of 0-1400 mg/L when using the 0-2000 S/cm switch setting of the Conductivity Probe. 3 To save the calibration values, choose Save As from the File menu and resave the file as Test 12 Total Dissolved Solids. When the file is reopened, the new calibration values stored with the file will be used during data collection.

2 These calibration values were obtained by multiplying the calibration for the 0-2000 S/cm conductivity calibration by the constant, 0.70: Intercept = 0 5 0.70 = 0, Slope = 847.2 5 0.70 = 593. 3 If you are using the low-range switch setting (0-200 S/cm) for samples with low TDS values, you can manually enter a calibration corresponding to the 0.70 constant: Intercept value = 0, Slope = 46.0 conductivity 1000 mg/L 2000 S TDS concentrationTest 12

12 - 10 Water Quality with Computers TDS A third option has students perform a two-point calibration. To obtain a standard that reflects the unique ionic composition of your particular stream, you can collect a 1-liter water sample, and determine the TDS concentration of 500 mL of the sample using Method 2 of Test 12: TDS by Evaporation. After finding its concentration, you can now use the remaining 500 mL of the water sample as a standard solution. To do this, choose Calibrate from the Experiment menu. For the first calibration point, simply hold the probe in the air (out of solution), and enter a value of 0 (mg/L TDS). For the second calibration point, place the Conductivity Probe into the water sample, and enter the value you obtained using Method 2 (e.g., 142 mg/L TDS). 3. Having accurate standard solutions is essential for performing good calibrations. The Sodium Chloride Calibration Solution that was included with your Conductivity Probe (500 mg/L TDS) can last you a long time if you take care not to contaminate it with a wet or unrinsed probe. You should perform and save a calibration with your probe while the solution is new and uncontaminated. To prepare your own standard solutions using solid NaCl, use a container with accurate volume markings (e.g., volumetric flask) and add the amount of solid shown in the first column of Table 2. This standard can be used to calibrate Conductivity Probe for Test 12, using the amount shown in mg/L as TDS (second column). Table 2 Add this amount of NaCl to make 1 liter of solution TDS and Conductivity values equivalent to the NaCl concentration in the first column Total dissolved solids (TDS) Conductivity 0.0474 g (47.4 mg/L) 50 mg/L as TDS 100 S/cm 0.491 g (491 mg/L) 500 mg/L as TDS 1000 S/cm

1.005 g (1005 mg/L) 1000 mg/L as TDS 2000 S/cm 5.566 g (5566 mg/L) 5000 mg/L as TDS 10,000 S/cm 4. Flinn Scientific (P.O. Box 21, Batavia, IL 60510, Tel: 800-452-1261, www.flinnsci.com) sells a set of four standard solutions in 500-mL bottles. The concentrations correspond to the four solutions shown in Table 2. Here is the ordering information: Conductivity Calibration Kit with four 500-mL bottles (50 mg/L, 500 mg/L, 1000 mg/L, and 5000 mg/L TDS, order code AP 9111) 5. Your Vernier Conductivity Probe is automatically temperature compensated between temperatures of 5 and 35C. Readings are automatically referenced to a conductivity value at 25C. The Conductivity Probe will, therefore, give the same conductivity reading in a solution that is at 15C as it would if the same solution were warmed to 25C. This means you can calibrate your probe in the lab, and then use these stored calibrations to take readings in colder (or warmer) water in a lake or stream. If the probe was not temperature compensated, you would notice a change in the conductivity reading as temperature changed, even though the actual ion concentration did not change. Method 2: TDS by Evaporation 6. A larger sample size should reduce the percent error in this test. The problem with a very large sample is that most analytical balances do not have the capacity to weigh beakers larger than about 250 mL. You could use a larger beaker if your balance has the capacity to do so. Alternatively, as stated in Step 5 of the procedure, you can add a second sample of water to the beaker. If the water has very low TDS, you could continue adding daily samples of water until the mass change is in the 0.025-g range. You would need to know this ahead of time,Total Dissolved Solids Water Quality with Computers 12 - 11 TDS however, to ensure that you initially collect a large enough water sample. If you use this approach, make sure you keep the sample in the refrigerator to cut down on any microbial action that may affect the results. Change your calculations on the Data & Calculations sheet

accordingly. 7. If you do not have a milligram balance, satisfactory results can usually be obtained by using a centigram balance and a larger sample size. Use the largest beaker that can be weighed on your balance and increase the sample size accordingly. You could add another sample of water on Day 2, as described in Step 5 of the Testing Procedure. 8. If you are concerned about the water boiling and splattering out of the beaker in the oven, you can dry the sample for a few hours at around 80C so that it wont boil. Then, when the water level has gone down sufficiently, turn the oven up to 104C and finish the drying process. 9. If you have trouble cleaning the dried residue out of the beaker, try swirling a little 1 M hydrochloric acid, HCl, in the bottom. Make sure you dispose of the acid properly. 10. Some substances, such as calcium, magnesium, chloride, and sulfate, may attract water. These types of substances are hygroscopic. If you have a sample containing high levels of hygroscopic substances, you should dry the samples for a longer period of time and weigh them as soon as possible after removing them from the oven. Dessicate the samples while they cool, if at all possible. 11. Do not turn up the heat in the oven to evaporate the water at a faster rate. A higher oven temperature will volatilize some of the organics and cause some heat-induced chemical decomposition. This will give a false reading for total solids. 12. If you will be testing water with unusually high levels of dissolved ions (brackish water or very hard water), students may encounter readings above the upper limit of the 1000-mg/L TDS range used in this test. Have them use the highest switch setting on the Conductivity Probe (020,000 S/cm), and load the calibration for 0 10,000 mg/L TDS. If readings exceed 10,000 mg/L, follow the directions in the next section. Sampling in Ocean Salt Water or Tidal Estuaries Salt-water samples may exceed the high range of the Conductivity Probe, 0 to 20,000 S/cm (0 to 10,000 mg/L TDS). Seawater from the mid-Atlantic ocean has a conductivity value of

53,000 S/cm (or a TDS concentration of about 26,500 mg/L). Samples in this range will need to be diluted in order for them to be measured using the high range. For example, you can take a sample of ocean water, and dilute it to _ of its original concentration by adding 100 mL of the salt-water sample to 300 mL of distilled water. This diluted sample can then be measured using the Conductivity Probe at the high-range setting. If the TDS value for the diluted sample is measured to be 6,600 mg/L, then this answer is multiplied by a factor of 4 to obtain the TDS value of the original sample: 456,600 = 26,400 mg/L TDS. How the Conductivity Probe Works The Vernier Conductivity Probe measures the ability of a solution to conduct an electric current between two electrodes. In solution, the current flows by ion transport; therefore, an increasing concentration of ions in the solution will result in higher conductivity values.Test 12 12 - 12 Water Quality with Computers TDS The Conductivity Probe is actually measuring conductance, defined as the reciprocal of resistance. When resistance is measured in ohms, conductance is measured using the SI unit, siemens (formerly known as a mho). Aqueous samples are commonly measured in microsiemens, or S. Even though the Conductivity Probe is measuring conductance, we are often interested in finding the conductivity of a solution. Conductivity, C, is found using the following formula C = G kc where G is the conductance, and kc is the cell constant. The cell constant is determined for a probe using the following formula kc = d/A where d is the distance between the two electrodes, and A is the area of the electrode surface. For example, the cell in the figure shown here has a cell constant of kc = d/A = 1.0 cm/ 1.0 cm2

= 1.0 cm-1 The conductivity value is found by multiplying conductance and the cell constant. Since the Vernier Conductivity Probe also has a cell constant of 1.0 cm-1 , its conductivity and conductance have the same numerical value. For a solution with a conductance value of 1000 S, the conductivity, C, would be C = G kc = (1000 S)5(1.0 cm-1 ) = 1000 S/cm A potential difference is applied to the two probe electrodes in the Conductivity Probe. The resulting current is proportional to the conductivity or TDS value of the solution. This current is converted into a voltage to be read by Logger Pro. Alternating current is supplied to prevent the complete ion migration to the two electrodes. As shown in the figure below, with each cycle of the alternating current, the polarity of the electrodes is reversed, which in turn reverses the direction of ion flow. This very important feature of the Conductivity Probe prevents most electrolysis and polarization from occurring at the electrodes. Thus, the solutions that are being measured for conductivity are not fouled. It also greatly reduces redox products from forming on the relatively inert graphite electrodes. The Vernier Conductivity Probe has three sensitivity range settings. 0 to 200 S/cm (0 to 100 mg/L TDS)

 0 to 2000 S/cm (0 to 1000 mg/L TDS) 0 to 20,000 S/cm (0 to 10,000 mg/L TDS) These ranges are selected using a toggle switch on the end of the amplifier box attached to the probe. It is very important to consider this setting when loading or performing a calibration; no single calibration can be used for all three settings. 1 cm 1 cm d = 1 cm graphite electrodes Epoxy body