doc022.53.80225

DOC022.53.80225

Hydraulic Fracturing Water Analysis HandbookFor use with DR 900 Colorimeters

07/2013, Edition 5

2Introduction

This manual is made up of test procedures and additional explanatory notes for testing of oil and gas field waters. The first part of the manual contains the test procedure documents. Explanatory documents are found in the second part of the manual.

Explanatory documents include information about the purpose of a test, recommended instrumentation, interpreting test results, and information about test interferences and challenges.

1 Alkalinity

Alkalinity, DT, 8203

Alkalinity DOC316.53.01308Phenolphthalein and Total Alkalinity Method 1024410 to 4000 mg/L as CaCO3 Digital TitratorScope and Application: For oil and gas field shale waters.

Test preparation

Before starting the test:

Four drops of Bromcresol Green-Methyl Red Indicator Solution1 can be substituted for the Bromcresol Green-Methyl Red Indicator Powder Pillow.

Four drops of Phenolphthalein Indicator Solution1 can be substituted for the Phenolphthalein Indicator Powder Pillow.

1 Refer to Optional reagents and apparatus on page 8.

For added convenience when stirring, use the TitraStir stirring apparatus1.

meq/L Alkalinity = mg/L as CaCO3 50

Collect the following items:

Description Quantity

Bromcresol Green-Methyl Red Indicator Powder Pillow 1

Phenolphthalein Indicator Powder Pillow 1

pH Meter and probe (highly colored samples only) each

Sulfuric acid titration cartridge (refer to Table 1 on page 3) 1

Digital titrator 1

Delivery tube for digital titrator 1

Graduated cylinder 1

Erlenmeyer flask, 250-mL 1

Refer to Consumables and replacement items on page 7 for reorder information.

Alkalinity 2

Alkalinity

Test procedure

1. Select a sample volume and titration cartridge from Table 1 on page 3. Note: Typical oil and gas field water levels are 100600 mg/L CaCO3.

2. Insert a clean delivery tube into the 1.600 N Sulfuric Acid titration cartridge. Attach the cartridge to the titrator.Note: Other titrant strengths are available.

3. Turn the delivery knob to eject air and a few drops of titrant. Reset the counter to zero and wipe the tip.

4. Use a graduated cylinder or pipet to measure the sample volume from Table 1 on page 3.

5. Transfer the sample into a clean, 250-mL Erlenmeyer flask. If the sample volume is less than 100 mL, dilute to approximately 100 mL with deionized water.Note: A pH meter may be used in highly colored samples. If a pH meter is used, the Phenolphthalein Indicator Powder Pillow is not required in the next step.

6. Add the contents of one Phenolphthalein Indicator Powder Pillow. Swirl to mix. If the solution turns pink or the measured pH is greater than 8.3, proceed to step 7. If the solution is colorless or the measured pH is less than 8.3, the Phenolphthalein (P) alkalinity is zero. Proceed to step 9.

7. Place the delivery tube into the solution and swirl the flask. Turn the knob on the titrator to add titrant to the solution. Continue to swirl the flask and add titrant until the color changes from pink to colorless or until a pH of 8.3 is reached.Write down the number of digits displayed on the counter.

8. Use the multiplier in Table 1 on page 3 to calculate the concentration:digits x multiplier = mg/L as CaCO3 P alkalinityExample: 100 mL of sample was titrated with the 1.600 N cartridge and 250 digits were used to reach the end point. The concentration is 250 x 1.0 = 250 mg/L as CaCO3.

SeeTable 1

Alkalinity

3 Alkalinity

9. Add the contents of one Bromcresol Green-Methyl Red Indicator Powder Pillow. Swirl to mix. Note: The Bromcresol Green-Methyl Red Indicator Powder Pillow is not required if a pH meter is used.

10. Continue the titration with sulfuric acid to a light pink color or to a pH of 4.5. Write down the number of digits displayed on the counter.Note: A pH meter may be used to titrate to a specific pH as required by sample composition. Refer to Table 2. A pH of 4.5 is recommended.

11. Use the multiplier in Table 1 to calculate the concentration:digits x multiplier = mg/L as CaCO3 total alkalinityExample: 100 mL of sample was titrated with the 1.600 N cartridge and 250 digits were used to reach the end point. The concentration is 250 x 1.0 = 250 mg/L as CaCO3.

12. Calculate the bicarbonate, carbonate and hydroxide alkalinities with Table 4 on page 6.

Table 1 Range-specific informationRange (mg/L as CaCO3) Sample volume (mL) Titration cartridge (N H2SO4) Multiplier

1040 100 0.1600 0.1

40160 25 0.1600 0.4

100400 100 1.600 1.0

200800 50 1.600 2.0

5002000 20 1.600 5.0

10004000 10 1.600 10.0

Table 2 End point pHSample composition Total alkalinity Phenolphthalein alkalinity

Alkalinity about 30 mg/L pH 4.9 pH 8.3



Silicates or phosphates present pH 4.5 pH 8.3

Industrial wastes or complex system pH 4.5 pH 8.3

Routine or Automated Analyses pH 4.5 pH 8.3

Test procedure (continued)

SeeTable 4

Alkalinity 4

Alkalinity

InterferencesTable 3 lists substances that can interfere with this test.

Maintenance of pH probesTo measure the complex oil and gas shale waters, probe maintenance is essential. Follow the probe maintenance or cleaning procedures provided in the probe documentation.

Clean the probe when the following conditions occur:

Drifting/inaccurate readings

Slow stabilization times

Calibration errors

The type of contamination will determine the cleaning solution needed.

For general contaminants:

1. Rinse the probe with deionized water and blot dry with a lint-free cloth.

2. Soak the glass bulb for 1216 hours in Hach Probe Cleaning Solution.

3. Rinse or soak the probe for 1 minute in deionized water.

4. Soak the probe in pH 4 buffer for up to 20 minutes, then rinse with deionized water.

5. Blot dry with a lint-free cloth.

For mineral deposits:

1. Rinse the probe with deionized water and blot dry with a lint-free cloth.

2. Soak the glass bulb for 1015 minutes in 0.1 M HCI.




For fats, grease and oils:

1. Soak the glass bulb in a warm detergent solution for up to 2 hours.




Table 3 Interfering substancesInterfering substance Interference level

ChlorineChlorine at levels above 3.5 mg/L may cause a yellow-brown color when the Bromcresol Green-Methyl Red Powder Pillow is added. Add one drop of 0.1 N Sodium Thiosulfate to the sample to remove chlorine before the test is started.

Color or turbidity

Do not filter, dilute or alter the sample. Color or turbidity can mask the color change of the end point. Use a pH meter instead of the color indicators and titrate to a pH of 8.3 for phenolphthalein acidity. For total alkalinity, refer to Table 2 on page 3 for the correct end point pH.

Soaps, oily matter, suspended solids and precipitates

Oils or solids may cover the pH probe and cause a slow or sluggish response. Clean the probe immediately after use (refer to Maintenance of pH probes).

Alkalinity

5 Alkalinity

Sample collection, preservation and storageAlkalinity measurements are best done immediately on-site to prevent loss or gain of carbon dioxide or other gases when exposed to air or excessive agitation. When immediate analysis is not possible:

Collect samples in clean plastic or glass bottles. Fill completely and tighten the cap.

Prevent excessive agitation or prolonged exposure to air. Complete the test procedure as soon as possible after collection for best accuracy.

The sample can be stored for 24 hours if cooled to 4 C (39 F) or below. If biological activity is suspected, analyze the sample within 6 hours.

Alkalinity measurements with a pH meterSample color or turbidity might mask or hide the color change of the Phenolphthalein and Bromcresol Green-Methyl Red Indicators in steps 7 and 10. These samples can be titrated and measured with a pH probe. Use a pH probe to determine the 8.3 end point in step 7 and the 4.5 pH end point in step 10. When a pH probe is used, the Phenolphthalein Indicator and Bromcresol Green-Methyl Red Indicator Powder Pillows are not required.

Alkalinity relationship tableTotal alkalinity primarily includes hydroxide, carbonate and bicarbonate alkalinities. The concentration of these alkalinities in a sample may be determined when the phenolphthalein and total alkalinities are known (refer to Table 4 on page 6).

To use the table, follow these steps:

1. Does the phenolphthalein alkalinity equal zero? If yes, refer to Row 1.

2. Does the phenolphthalein alkalinity equal total alkalinity? If yes, refer to Row 2.

3. Divide the total alkalinity by 2 to give one-half the total alkalinity.

4. Compare the result of step c (one-half total alkalinity) with the total alkalinity, and then refer to row 3, 4 or 5.

5. Perform the required calculations in the appropriate row, if any calculations for that row are required.

6. Check your results. The sum of the three alkalinity types will equal the total alkalinity.

For example:A sample has 170 mg/L as CaCO3 phenolphthalein alkalinity and 250 mg/L as CaCO3 total alkalinity. What is the concentration of hydroxide, carbonate and bicarbonate alkalinities?

The phenolphthalein alkalinity does not equal 0 (it is 170 mg/L).

The phenolphthalein alkalinity does not equal total alkalinity (170 mg/L vs. 250 mg/L).

One-half of the total alkalinity (250 mg/L) equals 125 mg/L. Because the phenolphthalein alkalinity (170 mg/L) is greater than one-half the total alkalinity (125 mg/L), refer to row 5.

The hydroxide alkalinity is equal to: 2 x 170 = 340

340 250 = 90 mg/L hydroxide alkalinity

The carbonate alkalinity is equal to: 250 170 = 80

80 x 2 = 160 mg/L carbonate alkalinity

Alkalinity 6

Alkalinity

The bicarbonate alkalinity equals 0 mg/L.Check: (Refer to step 6.)

90 mg/L hydroxide alkalinity + 160 mg/L carbonate alkalinity + 0 mg/L bicarbonate alkalinity = 250 mg/L

The above answer is correct; the sum of the three alkalinity types equals the total alkalinity.

Accuracy checkEnd point confirmationUse a buffer pillow with the same pH as the end point with the indicator to make sure the end point color is accurate.

Phenolphthalein alkalinityAdd 50 mL of deionized water to a flask. Add one pH 8.3 buffer powder pillow and one Phenolphthalein Indicator Powder Pillow and swirl to mix. Use this solution for comparison during the titration with the sample.

Total alkalinityAdd 50 mL of deionized water to a flask. Add one pH 4.5 buffer powder pillow and one Bromcresol Green-Methyl Red Indicator Powder Pillow and swirl to mix. Use this solution for comparison during the titration with the sample.

Standard additions method (sample spike)Required for accuracy check:

Alkalinity Voluette Ampule Standard Solution, 0.500 N

Ampule breaker

TenSette Pipet, 0.11.0 mL and Pipet Tips

1. Open the standard solution ampule.

2. Use the TenSette Pipet to add 0.1 mL of the standard to the titrated sample. Swirl to mix.

3. Titrate the spiked sample to the end point. Write down the amount of titrant that was used to reach the end point.

4. Repeat steps 2 and 3 with two more additions of 0.1 mL. Titrate to the end point after each addition.

5. Each 0.1 mL of standard that was added will use approximately 25 digits of the 1.600 N titration cartridge or 250 digits of the 0.1600 N titration cartridge to reach the end point. If more or less titrant was used, there may be an interference (refer to Interferences on page 4) or the concentration of the titrant has changed.

Table 4 Alkalinity relationships

Row Sample result Hydroxide alkalinity equals:Carbonate alkalinity

equals:Bicarbonate alkalinity

equals:

1 Phenolphthalein Alkalinity = 0 0 0 Total Alkalinity

2 Phenolphthalein Alkalinity equal to Total Alkalinity

Total Alkalinity 0 0

3 Phenolphthalein Alkalinity less than one-half of Total Alkalinity

0 Phenolphthalein Alkalinity times 2

Total Alkalinity minus two times Phenolphthalein

Alkalinity

4 Phenolphthalein Alkalinity equal to one-half of Total Alkalinity

0 Total Alkalinity 0

5 Phenolphthalein Alkalinity greater than one-half of Total Alkalinity

2 times Phenolphthalein Alkalinity minus Total

Alkalinity

2 times the difference between Total and

Phenolphthalein Alkalinity

0

Alkalinity

7 Alkalinity

Summary of methodThe sample is titrated with sulfuric acid to a colorimetric end point corresponding to a specific pH. Phenolphthalein alkalinity is determined by titration to a pH of 8.3, as evidenced by the color change of phenolphthalein indicator and indicates the total hydroxide and one half the carbonate present. The M (methyl orange) or T (total) alkalinity is determined by titration to a pH between 4.3 and 4.9 and includes all carbonate, bicarbonate and hydroxide. Alternatively, to determine the total alkalinity end points, use a pH meter and titrate to the specific pH required for the sample composition.

Consumables and replacement items Required reagents

Description Quantity/Test Unit Item no.

Alkalinity Reagent Set (approximately 100 tests) 2271900

(1) Bromcresol Green-Methyl Red Powder Pillows 1 100/pkg 94399

(1) Phenolphthalein Indicator Powder Pillows 1 100/pkg 94299

(1) Sulfuric Acid Titration Cartridge, 0.1600 N varies each 1438801

(1) Sulfuric Acid Titration Cartridge, 1.600 N varies each 1438901

Required apparatus


Digital Titrator each 1690001

Flask, Erlenmeyer, graduated, 250-mL 1 each 50546

Graduated cylinderselect one or more based on range:

Cylinder, graduated, 10-mL 1 each 50838




Recommended standards

Description Unit Item no.

Alkalinity Standard Solution, Voluette Ampule 0.500 N Na2CO3, 10-mL 16/pkg 1427810

HACH COMPANYWORLD HEADQUARTERSTelephone: (970) 669-3050FAX: (970) 669-2932

FOR TECHNICAL ASSISTANCE, PRICE INFORMATION AND ORDERING:Call 800-227-4224

Contact the HACH office or distributor serving you.www.hach.com [email protected]

In the U.S.A. Outside the U.S.A. On the Worldwide Web ; E-mail

toll-free

Alkalinity

Hach Company, 2011. All rights reserved. Printed in the U.S.A. 06/2011, Edition 1

Optional reagents and apparatus


Buffer Powder Pillows, pH 4.5 25/pkg 89568

Buffer Powder Pillows, pH 8.3 25/pkg 89868

Stir bar, octagonal 28.6 mm x 7.9 mm each 2095352

TenSette Pipet, 0.1 to 1.0 mL each 1970001

Water, deionized 500 mL 27249

Pipet, volumetric, Class A, 10 mL each 1451538

Pipet, volumetric, Class A, 20 mL each 1451520

Pipet Filler, safety bulb each 1465100

Bottles, sampling, poly, 500 mL each 2087079

Bromphenol Green-Methyl Red indicator solution 100 mL MDB 2329232

Phenolphthalein Indicator solution, 5 g/L 100 mL MDB 16232

pH meter each

TitraStir stir plate, 115 Vac each 1940000

TitraStir stir plate, 230 Vac each 1940010

1 Bacteria, Acid-producing

Chloride, HR, 10255

Bacteria, Acid-producing DOC316.53.01328Visual determination APB-BART*Semi-quantitativeScope and Application: For the determination of acid-producing bacteria in brine solutions, produced waters and hydraulic fracturing waters.

*APB-BART is a trademark of Droycon Bioconcepts Inc.

Test preparation

Procedure notes:

Do not touch or contaminate the inside of the tube or lid. Use aseptic technique.

To prevent contamination when the cap is removed from the inner tube, set the cap down directly on a clean surface. Do not invert the cap.

Do not shake or swirl the tube after the sample is added. Let the ball float to the top at its own speed.

Test procedure

1. Remove the inner tube from the outer tube.

2. Collect at least 20 mL of sample in the outer tube.

3. Fill the inner tube with the sample to the fill line. Tighten the cap on the inner tube.

4. Put the inner tube in the outer tube and tighten the cap on the outer tube. Do not shake or swirl the tube!

5. Invert the tube for 30 seconds to dissolve the dye under the cap.

6. Write the date and sample name on the outer tube.

7. Incubate the tube at room temperature and away from direct sunlight. Do not move the tube.

8. Examine the tube each day for 8 days. Record the date when a reaction is first seen. Refer to Test results.

Bacteria, Acid-producing 2

Bacteria, Acid-producing

InterferencesIf the original sample is acidic (pH < 6.0), neutralize the pH (pH 6.9 to 7.2) with sterile KOH. This adjustment stresses the bacteria, so subtract 2 days from the Days to reaction in Table 1.

Water samples that contain more than 6% salt can give false negatives. Dilute all samples that have more than 6% salt with sterile distilled water until the salt concentration is less than 6%.

Test resultsPresence/Absence

When acid-producing bacteria are present, the color of the solution changes from a purple to a yellow-orange color. The solution often becomes cloudy.

Negative (absent/non-aggressive)the color stays purple.

Positive (present/aggressive)the color becomes yellow-orange. The solution can be cloudy.

Make an estimate of the bacteria populationIf the test result is positive, make an estimate of the bacteria population and the aggressivity. Refer to Table 1. A faster reaction occurs when the bacteria population is high.

If the APB population is highly or moderately aggressive (< 7 days), a total coliform test is recommended on a fresh sample to see if there is a hygiene risk.

Advanced test informationIf the test result is positive, examine the tubes for dominant bacteria. The dominant bacteria for this test is gRAM-negative fermenting bacteria.

Summary of methodWhen acid-producing bacteria are in the sample, the sample becomes acidic (pH 3.5 to 5.5) during incubation. A pH indicator, bromocresol purple, in the APB-BART vial changes from a purple to a orange or yellow color as the pH decreases. This change occurs at a pH of 5.2 to 5.8.

The acid-producing bacteria produce acids in very reductive (oxygen-free) environments. If oxygen is present, then the APB do not generate acidity in the water, but can generate acidity at the interface between the biofilm and the supporting material (e.g., concrete, steel).

DisposalSterilize the reacted sample before disposal. Refer to Figure 1.

Table 1 Approximate bacteria population

Days to reaction Approximate APB population (cfu/mL) Aggressivity

1 800,000 High

2 70,000 High

3 9,000 High

4 1500 Moderate

5 500 Moderate

6 150 Moderate

7

Bacteria, Acid-producing

3 Bacteria, Acid-producing

Figure 1 Disposal

Consumables and replacement itemsRequired reagents and apparatus


BART Test for acid-producing bacteria 1 9/pkg 2831409





toll-free


1 Bacteria, Heterotrophic Aerobic

Chloride, HR, 10255

Bacteria, Heterotrophic Aerobic DOC316.53.01329Visual determination HAB-BART*Semi-quantitativeScope and Application: For the determination of total aerobic bacteria in brine solutions, produced waters and hydraulic fracturing waters.

*HAB-BART is a trademark of Droycon Bioconcepts Inc.

Test preparation

Procedure notes:




Test procedure





5. Invert the tube for 30 seconds (5 minutes in saline waters) to dissolve the dye under the cap.




Bacteria, Heterotrophic Aerobic 2

Bacteria, Heterotrophic Aerobic


When heterotrophic aerobic bacteria are present, the color of the solution changes from a blue to a light or medium yellow color. The solution often becomes cloudy.

Negative (absent/non-aggressive)the color stays blue.

Positive (present/aggressive)the color becomes yellow. The solution can be cloudy.


Advanced test informationIf the test result is positive, examine the tubes for dominant bacteria. Refer to Figure 1.

Summary of methodWhen heterotrophic aerobic bacteria (HAB) are in the sample, the bacteria consume oxygen during incubation. When the oxygen is depleted, the bacteria react with the methylene blue dye in the HAB-BART vial and reduce the dye to its colorless form. The faster the color change, the higher the level of respiration and the larger or more aggressive the bacteria population.

Aerobic bacteria can cause several problems in water, including slime formations, turbidity, taste and odor, corrosion, health risks and hygiene risks. When a problem is found, more tests are recommended to give more information about the microbial problem. This method does not give information about the particular groups of bacteria that can be present.



Days to reaction Approximate HAB population (cfu/mL) Aggressivity

1 7,000,000 Very high

2 500,000 High

3 50,000 Moderate

4 7,000 Low

Figure 1 Dominant bacteria

The color is bleached from the bottom to the top.

The color is bleached from the top to the bottom.

Aerobic bacteria Facultative anaerobic bacteria

Bacteria, Heterotrophic Aerobic

3 Bacteria, Heterotrophic Aerobic

Figure 2 Disposal



BART Test for heterotrophic aerobic bacteria 1 9/pkg 2490409

BART Test for heterotrophic aerobic bacteria 1 27/pkg 2490427





toll-free


1 Bacteria, Slime-forming

Chloride, HR, 10255

Bacteria, Slime-forming DOC316.53.01327Visual determination SLYM-BART*Semi-quantitativeScope and Application: For the determination of slime-forming bacteria in brine solutions, produced waters and hydraulic fracturing waters.*SLYM-BART is a trademark of Droycon Bioconcepts Inc.

Test preparation

Procedure notes:




Test procedure








Bacteria, Slime-forming 2

Bacteria, Slime-forming


When slime-forming bacteria are present, the solution becomes cloudy. Refer to Figure 1.


Advanced test informationIf the test result is positive, examine the tubes for dominant bacteria. Refer to Figure 2. If the dominant bacteria is pseudomonads or enterics with a high or very high aggressivity, a fecal coliform test is recommended on a fresh sample to determine if there is a hygiene risk.

Figure 1 Negative versus positive test results

The solution stays clear, with no visible growth or glow under

UV light.

The solution is cloudy. A glowing ring is seen

under UV light and/or there is slime growth at the bottom of the tube.

Negative (absent/non-aggressive) Positive (present/aggressive)


Days to reaction Approximate slime population (cfu/mL) Aggressivity

1 1,800,000 Very high

2 350,000 High

3 66,500 High

4 12,500 Moderate

5 2500 Moderate

6 500 Moderate

7 100 Low

8 10 Low


Dense slime in bottom or slime ring around balldense slime

bacteria

Cloudy growth or layered platesslime-

forming bacteria

Glows pale blue under UV light

fluorescing pseudomonads

Blackened liquidpseudomonads

and enterics

Thread-like strandstight slime bacteria

Bacteria, Slime-forming

3 Bacteria, Slime-forming

Summary of methodWhen slime-forming bacteria are in the sample, one or more types of slime will grow in the SLYM-BART vial during incubation. The slime is typically seen as a cloudy or gel-like growth, which can be in one location or occur throughout the sample. These growths are usually white, grey, yellow or beige in color and can darken over time. Slime-forming bacteria typically produce the thickest slime under aerobic (oxidative) conditions, which can be seen around the floating ball.

Iron-related bacteria also produce slime, but it is typically thinner and involves the accumulation of various forms of iron. Slime-forming bacteria can make large amounts of slime without iron.


Figure 3 Disposal



BART Test for slime-forming bacteria 1 9/pkg 2432509

BART Test for slime-forming bacteria 1 27/pkg 2432527





toll-free


1 Bacteria, Sulfate-reducing

Chloride, HR, 10255

Bacteria, Sulfate-reducing DOC316.53.01326Visual determination SRB-BART*Semi-quantitativeScope and Application: For the determination of sulfate-reducing bacteria in brine solutions, produced waters and hydraulic fracturing waters.*SRB-BART is a trademark of Droycon Bioconcepts Inc.

Test preparation

Procedure notes:




SRB grow predominantly deep within biofilms and not directly in water. Make sure to get a representative sample.

Test procedure








Bacteria, Sulfate-reducing 2

Bacteria, Sulfate-reducing

InterferencesIf the sample contains more than 20 ppm hydrogen sulfide (H2S), the test can give a false positive. To remove hydrogen gas from the sample, add 30 mL of sample to the outer tube, cap and shake for 10 seconds. Let stand for 20 seconds.


When sulfate-reducing bacteria are present, a black slime forms in the tube. Refer to Figure 1.


Advanced test informationIf the test result is positive, examine the tubes for dominant bacteria. Refer to Figure 2.


The solution has no black

slime.

A black slime ring forms

around the ball and/or there is a black slime growth at the bottom of the

tube.




1 6,800,000 Very high

2 700,000 High

3 100,000 High

4 18,000 Moderate

5 5000 Moderate

6 1200 Moderate

7 500 Moderate

8 200 Low


Black in the bottom onlydense anaerobic bacteria dominated by

Desulfovibrio

Black around the ball onlyaerobic SRB with

aerobic slime forming heterotrophs

Black in the bottom and around the ballaerobic

and anaerobic SRB

Cloudy solutionanaerobic bacteria

Bacteria, Sulfate-reducing

3 Bacteria, Sulfate-reducing

Summary of methodWhen sulfate-reducing bacteria are in the sample, sulfate is reduced to hydrogen sulfide (H2S) in the SRB-BART vial during incubation. The H2S reacts with the ferrous iron in the test vial to form black iron sulfides. This sulfide commonly forms either in the base as a black precipitate and/or around the ball as an irregular black ring.

SRB tend to grow in anaerobic conditions deep within biofilms (slimes) as a part of a microbial community. SRB may not be present in the free-flowing water over the site of the fouling. Sulfate-reducing bacteria can cause problems such as strong odors, blackening of equipment, slime formations and the start of corrosive processes.


Figure 3 Disposal



BART Test for sulfate-reducing bacteria 1 9/pkg 2432409

BART Test for sulfate-reducing bacteria 1 27/pkg 2432427





toll-free

Hach Company, 2012-2013. All rights reserved. Printed in the U.S.A. 07/2013, Edition 2

1 Bacteria, Iron-related

Chloride, HR, 10255

Bacteria, Iron-related DOC316.53.01325Visual determination IRB-BART*Semi-quantitativeScope and Application: For the determination of iron-related bacteria in brine solutions, produced waters and hydraulic fracturing waters.*IRB-BART is a trademark of Droycon Bioconcepts Inc.

Test preparation

Procedure notes:




IRB grow predominantly on surfaces and not directly in water. Make sure to get a representative sample.

Test procedure








Bacteria, Iron-related 2

Bacteria, Iron-related


When iron-related bacteria are present, a foam or a brown slime ring forms around the ball and/or a brown slime forms at the bottom of the tube. Refer to Figure 1.


Advanced test informationIf the test result is positive, examine the tubes for dominant bacteria. Refer to Figure 2. If the dominant bacteria is enteric or pseudomonads and has a high or very high aggressivity, a fecal coliform test is recommended on a fresh sample to determine if there is a hygiene risk.


The solution has no foam or

brown slime.

Foam or a brown slime ring forms around the ball

and/or there is a brown slime growth at the bottom of the

tube.




1 540,000 Very high

2 140,000 High

3 35,000 High

4 9,000 Moderate

5 2300 Moderate

6 500 Moderate

7 150 Moderate

8 25 Low


Foam around ballanaerobic

bacteria

Brown rings, gel and/or cloudsiron-related bacteria

Green cloudypseudomonads

Red cloudyenteric

bacteria

Cloudyheterotrophic

bacteria

Black solutionpseudomonads

and enterics

Bacteria, Iron-related

3 Bacteria, Iron-related

Summary of methodWhen iron-related bacteria are in the sample, a series of reactions occur in the redox and nutrient gradients that develop in the IRB-BART vial during incubation. The IRB use the nutrients and ferric iron in the vial to grow and can be seen as foam, clouding, slime and/or color changes.

The bacteria that can be seen in this test include iron oxidizing and reducing bacteria, the sheathed iron bacteria, Gallionella, pseudomonads and enteric bacteria. Positive results can be a possible cause of biofouling problems such as plugging, corrosion, cloudiness and color.


Figure 3 Disposal



BART Test for iron-related bacteria 1 9/pkg 2432309

BART Test for iron-related bacteria 1 27/pkg 2432327





toll-free


Barium DOC316.53.01315Turbidimetric Method1 Method 102512 to 100, 20 to 1000, 200 to 10,000 mg/L Ba (spectrophotometers)2 to 80, 20 to 800, 200 to 8000 mg/L Ba (colorimeters)

Powder Pillows

Scope and application: For oil and gas field waters.1 Adapted from Snell and Snell, Colorimetric Methods of Analysis, Vol. II, 769 (1959).

Test preparation

Instrument specific informationThe table in this section shows all of the instruments that have the program for this test. Table 1 shows sample cell and orientation requirements for reagent addition tests, suchas powder pillow or bulk reagent tests.To use the table, select an instrument, then read across to find the correspondinginformation for this test.Table 1 Instrument-specific information for reagent addition

Instrument Sample cell orientation Sample cellDR 6000 DR 3800 DR 2800 DR 2700

The fill line is to the right. 2495402

DR 5000 DR 3900

The fill line is toward the user.

DR 900 The orientation mark is toward the user. 2401906

Before startingInstall the instrument cap on the DR 900 cell holder before ZERO or READ is pushed.Use the Standard Adjust option with each new lot of reagent for the best results.For best results, measure the reagent blank value for each new lot of reagent. Replace the sample with deionized water inthe test procedure to get the reagent blank value. Subtract the reagent blank value from the sample results automaticallywith the reagent blank adjust option.Filter samples that are turbid with filter paper and a funnel.Do not use the Pour-Thru Cell or sipper module (for applicable instruments) with this test.Review the Safety Data Sheets (MSDS/SDS) for the chemicals that are used and use any recommended personal protectiveequipment.Dispose of reacted solutions according to local, state and federal regulations. Use the Safety Data Sheets for disposalinformation for unused reagents. Consult the environmental, health and safety staff for your facility and/or local regulatoryagencies for further disposal information.

1

Items to collectDescription Quantity

BariVer 4 Barium Reagent Powder Pillows 1 Sample cells (For information about sample cells, adapters or light shields, refer to Instrumentspecific information on page 1.) 2


Sample collection and storage Collect samples in clean glass or plastic bottles. To preserve samples for later analysis, adjust the sample pH to less than 2 with

concentrated nitric acid (about 2 mL per liter). No acid addition is necessary if thesample is tested immediately.

Keep preserved samples at room temperature for a maximum of 6 months. Before analysis, adjust the pH to 5 with 5.0 N sodium hydroxide standard solution. Correct the test result for the dilution from the volume additions.

Powder pillow procedure

Start

1. Start program20 Barium. For informationabout sample cells,adapters or light shields,refer to Instrument specificinformation on page 1.Note: Although the programname may vary betweeninstruments, the programnumber does not change.

2. Prepare the blank: Addthe sample volume that isspecified for the test rangeto a clean sample cell: 280 mg/L: 10 mL 20800 mg/L: 1.0 mL 2008000 mg/L: 0.1 mLUse a pipet to add the1.0 mL and 0.1 mL volumes.

3. If the sample volume isless than 10 mL, adddeionized water to the 10-mL line.

4. Swirl to mix.Refer to Set the dilutionfactor on page 3. A 10-mL graduated mixingcylinder can be used insteps 2 and 3.

5. Clean the blank. 6. Insert the blank into thecell holder.

Zero

7. Push ZERO. The displayshows 0 mg/L Ba2+.

8. Remove the sample fromthe cell holder.

2 Barium, Turbidimetric Method (multi-range: 100, 1000, 10,000 mg/L)

9. Prepare the sample:Add the contents of oneBariVer 4 Barium ReagentPowder Pillow to the samplecell.The solution will get cloudyif barium is in the sample.

10. Swirl to mix.The sample will becomecloudy if barium is in thesample. Accuracy is notaffected by undissolvedpowder.

11. Start the instrumenttimer. A 5-minute reactiontime starts.Do not move the sample cellduring the reaction period.

12. Clean the preparedsample.

13. Within 5 minutes afterthe timer expires, insert theprepared sample into thecell holder.

Read

14. Push READ. Resultsshow in mg/L Ba2+.

15. Clean the sample cellimmediately after each testwith soap, water and abrush.

InterferencesInterfering substance Interference levelCalcium 10,000 mg/L as CaCO3Magnesium 100,000 mg/L as CaCO3Silica 500 mg/LSodium Chloride 130,000 mg/L as NaClStrontium The interference level is dependent on the sample matrix and the barium concentration.

When the barium concentration is zero, there is no interference from strontium. The bestresults occur when the barium concentration is less than 20 mg/L and when the strontiumconcentration (as mg/L) is equal to or less than the barium concentration.

Highly buffered samples orextreme sample pH

Can prevent the pH adjustment by the reagent(s) and cause incorrect results.

Set the dilution factorInstruments that have a dilution factor option can include the dilution factor in the resultand show the concentration of the original, undiluted sample. For example, if the sampleis diluted by a factor of 10, the instrument multiplies the result by 10 and shows thecalculated result in the instrument display.1. Select Options>More>Dilution factor from the instrument menu.

Barium, Turbidimetric Method (multi-range: 100, 1000, 10,000 mg/L) 3

Note: Colorimeters include a dilution factor when the chemical form is set. Go toOptions>Advanced Options>Chemical Form and select LR, MR or HR.

2. Enter the dilution factor: 1 mL sample diluted to 10 mL: dilution factor is 10. 0.1 mL sample diluted to 10 mL: dilution factor is 100.

3. Push OK to confirm. Push OK again.4. Push RETURN to go back to the measurement screen.

Accuracy checkStandard additions method (sample spike)

Use the standard additions method (for applicable instruments) to validate the testprocedure, reagents and instrument and to find if there is an interference in the sample.Items to collect: Barium Standard Solution, 1000-mg/L Ba Pipet, TenSette, 0.11.0 mL Pipet tips1. Use the test procedure to measure the concentration of the sample, then keep the

(unspiked) sample in the instrument.2. Go to the Standard Additions option in the instrument menu.3. Select the values for standard concentration, sample volume and spike volumes.4. Open the standard solution.5. Prepare three spiked samples: use the TenSette pipet to add of the standard solution,

respectively, to three 10-mL portions of fresh sample. Mix well.6. Use the test procedure to measure the concentration of each of the spiked samples.

Start with the smallest sample spike. Measure each of the spiked samples in theinstrument.

7. Select Graph to compare the expected results to the actual results.Note: If the actual results are significantly different from the expected results, make sure thatthe sample volumes and sample spikes are measured accurately. The sample volumes andsample spikes that are used should agree with the selections in the standard additions menu. Ifthe results are not within acceptable limits, the sample may contain an interference.

Standard solution methodUse the standard solution method to validate the test procedure, reagents andinstrument.Items to collect: Barium Standard Solution, 1000-mg/L Ba 100-mL volumetric flask, Class A 5-mL volumetric pipet, Class A and pipet filler Deionized water1. Prepare a 50.0-mg/L barium standard solution as follows:

a. Use a pipet to add 5.00 mL of 1000-mg/L barium standard solution into thevolumetric flask.

b. Dilute to the mark with deionized water. Mix well. Prepare this solution daily.2. Use the test procedure to measure the concentration of the prepared standard

solution.3. Compare the expected result to the actual result.

Note: The factory calibration can be adjusted slightly with the standard adjust option so that theinstrument shows the expected value of the standard solution. The adjusted calibration is thenused for all test results. This adjustment can increase the test accuracy when there are slightvariations in the reagents or instruments.

4 Barium, Turbidimetric Method (multi-range: 100, 1000, 10,000 mg/L)

Method performanceThe method performance data that follows was derived from laboratory tests that weremeasured on a spectrophotometer during ideal test conditions. Users may get differentresults under different test conditions.

Program Standard Precision (95% Confidence Interval) SensitivityConcentration change per 0.010 Abs change

20 30 mg/L Ba 2535 mg/L Ba 1 mg/L Ba

Summary of methodThe BariVer 4 Barium Reagent Powder combines with barium to form a barium sulfateprecipitate, which is held in suspension by a protective colloid. The amount of precipitateis proportional to the barium concentration. The measurement wavelength is 450 nm forspectrophotometers or 520 for colorimeters.

Consumables and replacement itemsRequired reagents

Description Quantity/test Unit Item no.

BariVer 4 Barium Reagent Powder Pillows 1 100/pkg 1206499



Barium Standard Solution, 1000-mg/L Ba 100 mL 1461142 Water, deionized 4 L 27256



Brush, test tube each 69000Filter paper, 12.5-cm 100/pkg 189457Flask, volumetric, Class A, 100-mL each 1457442 Funnel, poly, 65-mm each 108367 Liqui-Nox Phosphate-free detergent 946 mL 2088153 Nitric Acid Solution, 1:1 500 mL 254049 Paper, pH, 014 pH range 100/pkg 2601300 Pipet, TenSette, 0.11.0 mL each 1970001 Pipet tips for TenSette Pipet 1970001 50/pkg 2185696 Pipet tips for TenSette Pipet 1970001 1000/pkg 2185628 Pipet, volumetric 5.00-mL each 1451537 Pipet filler, safety bulb each 1465100

Sodium Hydroxide Standard Solution, 5.0 N 100 mLMDB 245032

Barium, Turbidimetric Method (multi-range: 100, 1000, 10,000 mg/L) 5





toll-free


Boron DOC316.53.01313Carmine Method Method 102522 to 50 mg/L B Powder PillowsScope and application: For oil and gas field waters

Test preparation

Instrument specific informationThe table in this section shows all of the instruments that have the program for this test. Table 1 shows adapter and light shield requirements for the instruments that use them.To use the table, select an instrument, then read across to find the correspondinginformation for this test.

Table 1 Instrument-specific information for test tubesInstrument Adapters Light shieldDR 6000 DR 5000 DR 900 4846400 Cover supplied with the instrumentDR 3900 LZV849 DR 3800 LZV646 DR 2800

Before startingInstall the instrument cap on the DR 900 cell holder before ZERO or READ is pushed.DR 3900, DR 3800, DR 2800 and DR 2700: Install the light shield in Cell Compartment #2 before this test is started.The reagent that is used in this test is corrosive. Use protection for eyes and skin and be prepared to flush any spills withrunning water.Review the Safety Data Sheets (MSDS/SDS) for the chemicals that are used and use any recommended personal protectiveequipment.Dispose of reacted solutions according to local, state and federal regulations. Use the Safety Data Sheets for disposalinformation for unused reagents. Consult the environmental, health and safety staff for your facility and/or local regulatoryagencies for further disposal information.

Items to collectDescription Quantity

BoroVer 3 Reagent Powder Pillow 1 Sufuric Acid, Concentrated 75 mLWater, deionized 2 mLTubes, glass, 16 mm x 100 mm 2 Caps, white Teflon 2 Flask, poly, screw-on cap, 250-mL 1 Cylinder, graduated, poly, 100-mL 1 Light shield or adapter (For information about sample cells, adapters or light shields, refer to Instrument specific information on page 1.) 1

1

Items to collect (continued)Description Quantity

Select:Pipet, 0.2 - 1.0 mL , BBP078 1 Pipet Tip, for BBP078 2 Pipet, 1.0 - 1.0 mL, BBP065 1 Pipet Tip for BBP065 2 ORPipet, TenSette, 0.1- to 1.0-mL 1 Pipet tips for 0.1- to 1.0-mL TenSette 2 Pipet, TenSette, 1.0- to 10.0-mL 1 Pipet tips for 1.0- to 10.0-mL TenSette 2


Sample collectionCollect samples in clean polyethylene or polypropylene bottles.

Prepare the glass tubes for first useNew glass tubes can contain residual amounts of reactive boron from the glassmanufacturing process. For best results, precondition the tubes before the first use.Previously used tubes do not need to be preconditioned.1. Prepare the BoroVer 3/Sulfuric Acid Solution.2. Add 3 to 4 mL of the prepared BoroVer 3/Sulfuric Acid Solution into the tubes.3. After 30 minutes, discard the solution.4. Rinse and dry the tubes before use.

Powder pillow procedure

Start

1. Start Boron HR. Refer to Instrument setupon page 5 forprogramming instructions.For information aboutsample cells, adapters orlight shields, refer to Instrument specificinformation on page 1.Note: Although the programname may vary betweeninstruments, the programnumber does not change.

2. Use a 100-mL graduatedcylinder to measure 75 mLof concentrated sulfuricacid. Pour the acid into aplastic 250-mL Erlenmeyerflask.

3. In a well-ventilated areaor fume hood, add thecontents of one BoroVer3 Reagent Powder Pillow tothe flask.

4. Swirl the flaskimmediately to mix. Swirl forup to 5 minutes to dissolvethe powder completely.

2 Boron, Carmine method (50 mg/L)

5. Prepare the blank:Remove the cap from aclean 16-mm tube. Add0.2 mL of deionized water.Refer to Prepare the glasstubes for first use on page 2and Clean the glass tubesafter use on page 4.Note: If a 3.5-mL pipet isnot available, 0.4 mL of DIwater can be used.

6. Prepare the sample:Remove the cap from aclean 16-mm tube. Add0.2 mL of sample.Note: If a 3.5-mL pipet isnot available, 0.4 mL ofsample can be used.

7. Add 3.5 mL of theBoroVer 3 Solution fromstep 4 to the preparedsample tube.Note: If a 3.5-mL pipet isnot available, 7.0 mL ofBoroVer 3 Solution can beused with 0.4 mL of sample.

8. Put the cap on theprepared sample and invertto mix.The solution in the tube willget warm.

9. Add 3.5 mL of theBoroVer 3 Solution fromstep 4 to the blank sampletube.Note: If a 3.5-mL pipet isnot available, 7.0 mL ofBoroVer 3 Solution can beused with 0.4 mL ofdeionized water.

10. Put the cap on theblank. Iinvert to mix.The solution in the tube willget warm.

11. Start the instrumenttimer. A 30-minute reactiontime starts.

12. When the timer expires,clean the blank.

13. Insert the blank into thecell holder.

Zero

14. Push ZERO. Thedisplay shows 0.0 mg/L BHR.

15. Clean the preparedsample.

16. Insert the preparedsample into the cell holder.

Boron, Carmine method (50 mg/L) 3

Read

17. Push READ. Resultsshow in mg/L B.

Reagent preparationTo prepare additional BoroVer 3/Sulfuric Acid Solution, mix one BoroVer 3 ReagentPowder Pillow per 75 mL of concentrated sulfuric acid.Preparation notes Gaseous hydrochloric acid (HCl) forms when the powder pillow is added to sulfuric

acid. Always mix under a fume hood. The solution is stable for up to 48 hours when it is stored in plastic containers. To prevent boron contamination from the glassware, do not keep the solution in

borosilicate glassware (Pyrex or Kimax) for more than 1 hour. The BoroVer 3/Sulfuric Acid Solution is highly acidic. Refer to the current MSDS/SDS

for safe handling and disposal instructions.1. Under a fume hood, measure the concentrated sulfuric acid with a graduated

cylinder.2. Pour the acid into a Erlenmeyer flask.3. Stir the acid and add the contents of one BoroVer 3 Reagent Powder Pillow to the

flask. Swirl to mix. Allow up to 5 minutes for the powder to completely dissolve. Addone powder pillow at a time and stir to dissolve after each powder pillow is added.

4. Pour this solution into plastic containers.Clean the glass tubes after use

N O T I C E The BoroVer 3/Sulfuric Acid solution is highly acidic. Neutralize the solution to pH 69 beforedisposal. Refer to a current SDS (Safety Data Sheet) for safe handling and disposal instructions ofreacted boron.

Glass tubes and caps can be reused.1. Thoroughly drain the boron solution.2. Rinse the vials several times with deionized water.3. Let the vials dry completely before the next use.

Accuracy checkStandard solution method

Use the standard solution method to validate the test procedure, reagents andinstrument.Items to collect: 1000 mg/L Boron Standard Solution 100-mL volumetric flask, Class A 3-mL volumetric pipet, Class A and pipet filler


Deionized water1. Prepare a 30.0 mg/L boron standard solution as follows:

a. Use a pipet to add 3.0 mL of 1000 mg/L boron standard solution into thevolumetric flask.

b. Dilute to the mark with deionized water. Mix well. Prepare this solution daily.2. Use the test procedure to measure the concentration of the prepared standard

solution.3. Compare the expected result to the actual result.

Note: The factory calibration can be adjusted slightly with the standard adjust option so that theinstrument shows the expected value of the standard solution. The adjusted calibration is thenused for all test results. This adjustment can increase the test accuracy when there are slightvariations in the reagents or instruments.

Method performanceThe method performance data that follows was derived from laboratory tests that weremeasured on a spectrophotometer during ideal test conditions. Users may get differentresults under different test conditions.

Program Standard Precision (95% Confidence Interval) SensitivityConcentration change per 0.010 Abs change

As entered 25 mg/L B 24.225.8 mg/L B 2.2 mg/L B

Instrument setupSome spectrophotometers do not have the Boron HR method in the stored programs.List. Use the instructions in this section to add the test.1. Set the instrument power to on. The instrument will complete a self-check.2. From the Main Menu, go to User Programs>Program Options>New>Program

Number.3. Enter a program number. Push OK.4. Enter Boron_HR for the program name. Push Next.5. Set the program type to Single Wavelength. Push Next.6. Set the units to mg/L. Push Next.7. Enter 605 for the wavelength. Push Next.8. Enter 1 for the concentration resolution. Push Next.9. Enter B for the chemical form. Push Next.10. Select Enter Formula for Calibration. Push Next.11. Enter: C = a + bA.12. Enter: C = a + bA = cA2. Push OK.13. Enter the values for the equations.

Option DescriptionDR 2700 a = 0.0, b= 25.51, c = 4.12DR 2800 a = 0.0, b= 25.51, c = 4.12DR 3800 a = 0.0, b= 25.51, c = 4.12DR 3900 a = 0.0, b= 25.51, c = 4.12DR 6000 a = 0.0, b= 25.51, c = 4.12DR 5000 a = 0.0, b = 25.02, c = 4.22

14. Push OK, then Done.15. In the User Program for Number Assigned screen, enter Upper Limit. Select EDIT.16. Enter ON>2. Push OK twice.


17. In the User Program for Number Assigned screen, enter Timer1. Select EDIT.18. Enter 1>30.00. Push OK twice.19. In the User Program for Number Assigned screen, enter Store.20. Record the User Program Number Assigned.

Summary of methodBoron is determined by its reaction with carminic acid in the presence of sulfuric acid toproduce a reddish to bluish color. The amount of color is directly proportional to the boronconcentration. The measurement wavelength is 605 nm for spectrophotometers or610 nm for colorimeters.



BoronVer 3 Boron Reagent Powder Pillows 1pillow/10 tests 100/pkg 1417099 Sulfuric Acid, concentrated, ACS varies 500 mL 97949 Water, deionized varies 100 mL 27242

Required apparatus


Tubes, glass, 16 mm x 100 mm 1 6/pkg 2275806 Caps, white, Teflon lining, for 16-mm tubes 2 6/pkg 2241106 Cylinder, graduated, polypropylene, 100 mL 1 each 108142 Flask, Polymethylpentene, screw cap, 250 mL, 125 mL 1 each 2089846 Pipet, 0.2 1.0 mL 1 each BBP078 Pipet Tip for BBP078 2 100/pkg BBP079 Pipet, 1.05.0 mL 1 each BBP065 Pipet Tip for BBP065 1 75/pkg BBP068 ORPipet, TenSette, 0.1- to 1.0-mL 1 each 1970001 Pipet Tips, for TenSette Pipet 1970001 2 50/pkg 2185696 Pipet, TenSette 1.010.0 mL 1 each 1970010 Pipet Tips, for TenSette Pipet 1970010 varies 50/pkg 2199796 Tubes, glass, 16 mm x 100 mm 1 6/pkg 2275806

Optional reagents


Boron Standard Solution, 1000 mg/L as B 100 mL 191442

Optional apparatusDescription Unit Item no.

Gloves, chemical resistant, size 10 pair 2410105 Goggles, safety, standard each 2927902 Pipet tips for TenSette Pipet 1970001 1000/pkg 2185628


Consumables and replacement items (continued)Description Unit Item no.

Pipet tips for TenSette Pipet 1970010 250/pkg 2199725 Test tube rack each 1864100 Pipets, includes one BBP078 and BBP065 pipet plus tips each LZP320






toll-free


1 Chloride

Chloride, DT, 8207

Determine sample sizesTo estimate the chloride concentration of gas and oil shale water samples, prescreen the samples.

1. Add approximately 75100 mL of deionized or chloride free water to a clean titration flask.

2. Use a TenSette Pipet to add 0.1 mL of the sample to the titration flask. Swirl to mix.

3. Add the contents of one Chloride 2 Indicator Powder Pillow to the flask. Swirl to dissolve. The solution will be yellow.

4. Titrate the solution quickly with the 1.128 N Silver Nitrate titrant to the red-brown end point. Record the number of digits added. Table 1 on page 1 shows the guidelines to estimate sample sizes.

5. Rinse the titration flask thoroughly with deionized water and then perform the steps in the Chloride test procedure.

Chloride DOC316.53.01306Silver Nitrate Method Method 10246100 to 200,000 mg/L as Cl Digital TitratorScope and Application: For gas and oil field shale waters.

Test preparation


mg/L sodium chloride = mg/L chloride x 1.65

meq/L chloride = mg/L chloride / 35.45

For added convenience when stirring, use the TitraStir stirring apparatus.

Collect the following items:


Chloride 2 Indicator Powder Pillow 1

Silver Nitrate titration cartridge, 1.128 N 1

Digital titrator 1

Delivery tube for digital titrator 1

Graduated cylinder or TenSette Pipet, (0.11.0 mL) with pipet tips 1

Water, deionized 4 liters

Erlenmeyer flask, 250-mL 1

Refer to Consumables and replacement items for reorder information.

Table 1 Guidelines to estimate sample sizes

Number of digits Sample size (mL)

250 0.1

125 0.2

50 0.5

Chloride 2

Chloride

5. Rinse the titration flask thoroughly with deionized water and then perform the steps in the Chloride test procedure.

Table 1 Guidelines to estimate sample sizes

Number of digits Sample size (mL)

250 0.1

125 0.2

50 0.5

25 1.0

10 2.0

5 5.0

2 20

1 50

Chloride test procedure

1. Select a sample volume from Table 2 on page 3. Refer to Determine sample sizes on page 1.

2. Insert a clean delivery tube into the 1.128 N Silver Nitrate titration cartridge. Attach the cartridge to the titrator. Note: Put the Silver Nitrate Titration Cartridge in a dark area when not in use.

3. Hold the Digital Titrator with the cartridge tip pointing up. Turn the delivery knob to eject a few drops of titrant. Reset the counter to zero and wipe the tip.

4. Use a TenSette graduated cylinder or pipet to measure the sample volume from Table 2 on page 3 into a 250 mL Erlenmeyer flask.

SeeTable 1

Chloride

3 Chloride

Sample collection, preservation and storageCollect samples in clean plastic or glass bottles. The sample can be stored for up to 7 days before the analysis.

Technique tips Demineralized water or other sources of chloride-free water may be used in place of the

deionized water.

The TitraStir stirring apparatus can provide a more convenient or reproducible stirring technique.

5. Dilute the measured sample to approximately 100 mL with deionized water. The amount of dilution water added is not critical.

6. Add the contents of one Chloride 2 Indicator Powder Pillow. Swirl to mix. Results will still be accurate if a small amount of powder does not dissolve.

7. Place the delivery tube into the solution and rapidly swirl the flask. Turn the knob on the titrator to add titrant to the solution. Continue to swirl the flask and add titrant until the color changes from yellow to red-brown. Refer to Technique tips on page 3.Write down the number of digits displayed on the counter.

8. Use the multiplier in Table 2 on page 3 to calculate the concentration:digits x multiplier = mg/L Cl

Example: 1.0 mL of sample was titrated with the 1.128 N cartridge and 200 digits were used to reach the end point. The concentration is 200 x 50 = 10,000 mg/L Cl.

Table 2 Range-specific information

Range (mg/L as Cl) Sample volume (mL) Titration cartridge (N AgNO3) Multiplier

100400 50 1.128 1.0

2501000 20 1.128 2.5

10004000 5 1.128 10.0

250010,000 2 1.128 25.0

500020,000 1 1.128 50

10,00040,000 0.5 1.128 100

25,000100,000 0.2 1.128 250

50,000200,000 0.1 1.128 500

Chloride test procedure (continued)

Chloride 4

Chloride

If the precipitate formed is red or orange, but the solution color is yellow, the test will give low results. Greater agitation or swirling is required during the titration. The test should be repeated. To eliminate the red or orange precipitate formation:

1. Do not add the Chloride 2 indicator in step 6 and go directly to step 7.

2. Titrate the sample solution directly with the Silver Nitrate solution to approximately 5075% of the expected end point. The solution will have a milky white precipitate.

3. Add the Chloride 2 Indicator and swirl to dissolve. The solution will turn yellow. Continue to titrate with the Silver Nitrate titrant to the red-brown end point.

4. If the sample turns red-brown after the addition of the Chloride 2, the end point has been exceeded and the procedure must be repeated with less titrant.

InterferencesTable 3 lists substances that can interfere with this test.

Accuracy checkUse the standard additions method to determine whether the sample has an interference and confirm the analytical technique.

Required items for accuracy check:

Chloride Voluette Ampule Standard Solution, 12,500-mg/L Cl

Ampule breaker

TenSette Pipet, 0.11.0 mL

Standard additions method (sample spike)


2. Use the TenSette Pipet to add 0.1 mL of the standard to the titrated sample. Swirl to mix.

Table 3 Interfering substances

Interfering substance Interference level1

1 Interference level limits increase with smaller sample sizes.

Bromide Interferes directly and is included in the test result.

Cyanide Interferes directly and is included in the test result.

Iron Concentrations above 10 mg/L mask the end point.

Iodide Interferes directly and is included in the test result.

Orthophosphate Concentrations above 25 mg/L will precipitate the silver.

pH

Neutralize strongly alkaline or acidic samples to a pH of 2 to 7 with 5.25 N sulfuric acid or 5.0 N sodium hydroxide. If a pH meter is used in the pH adjustment, use a separate sample to find the correct amount of acid or base to use. Then add the same amount of acid or base to the sample to be tested. pH electrodes will contaminate the sample.

Sulfide

Complete the following steps to remove sulfide interference:1. Add the contents of one Sulfide Inhibitor Reagent Powder Pillow to approximately

125 mL of sample. 2. Mix for one minute. 3. Filter through folded filter paper.4. Use the filtered sample in the chloride test procedure.

Sulfite Concentrations above 10 mg/L interfere with this method. To eliminate sulfite interference, add three drops of Hydrogen Peroxide, 30%, to the sample before the test is started.

Chloride

5 Chloride


4. Use the TenSette Pipet to add 0.2 mL of standard to the titrated sample. Swirl to mix.


6. Use the TenSette Pipet to add 0.3 mL of standard to the titrated sample. Swirl to mix.


Each 0.1 mL of standard that was added will use approximately 25 digits of the 1.128 N titration cartridge to reach the end point. If more or less titrant was used, the problem can be due to user technique, an interference (refer to Interferences on page 4) or a problem with reagents or apparatus.

Standard solution methodUse the Chloride Voluette Ampule Standard Solution (12,500 mg/L Chloride) to verify reagent quality, analyst technique and to become familiar with end point color change.


2. Use the TenSette Pipet to add 1.0 mL of the ampule standard solution to a 250 mL titration flask.

3. Dilute to approximately 100 mL with deionized water.

4. Add a Chloride 2 Powder Pillow. Swirl to mix.

5. Titrate the prepared solution from yellow to red-brown. The end point should be 250 digits 25 digits.

6. Calculate the actual standard concentration for a 1 mL sample size (refer to Table 2 on page 3).

Digits required x digit multipliers = mg/L Cl- (Example: 250 digits x 50 multiplier = 12,500 mg/L Cl-)

Summary of methodThe sample is titrated with Silver Nitrate Standard Solution in the presence of potassium chromate (from the Chloride 2 Indicator Powder). The silver nitrate reacts with the chloride present to produce insoluble white silver chloride. After all the chloride has been precipitated, the silver ions react with the excess chromate present to form a red-brown silver chromate precipitate, and marks the end point of the titration.

Chloride 6

Chloride



Chloride Reagent Set (approximately 100 tests): 2288000

(2) Chloride 2 Indicator Powder Pillows 1 pillow 50/pkg 105766

(1) Silver Nitrate Titration Cartridge, 1.128 N varies each 1439701

Required apparatus


Digital Titrator 1 each 1690001

Flask, Erlenmeyer, graduated, 250-mL 1 each 50546

Graduated cylinderselect one or more based on range:





Delivery tubes w/ 180 hook 1 each 1720500

TenSette Pipet, 0.11.0 mL 1 each 1970001

Pipet tips 1 50/pkg 2185696



Chloride Standard Solution, Voluette Ampule, 12,500-mg/L Cl, 10-mL 16/pkg 1425010

Voluette breaker 2196800

Chloride

7 Chloride



Filter paper, 12.5 cm 100/pkg 69257

Funnel, analytical, poly, 65 mm each 108367

Hydrogen Peroxide, 30%, ACS 473 mL 14411

Sodium Hydroxide Standard Solution, 5.0 N 100 mL MDB 245032

Stir bar, octagonal 28.6 mm x 7.9 mm each 2095352

Sulfide Inhibitor Reagent Powder Pillow 100/pkg 241899

Sulfuric Acid Standard Solution, 5.25 N 100 mL MDB 244932

TitraStir Stir Plate, 115 VAC each 1940000

TitraStir Stir Plate, 230 VAC each 1940010

Water, deionized 4 L 27256

pH Test Strip, 014 pH 100/pkg 2601300

Pipet tips 1000/pkg 2185628

Chloride standard solution, 1000 mg/L 500 mL 18349

Sampling bottle 250 mL 2087076

Dropper, glass 5/pkg 1419705

TenSette Pipet, 1.010.0 mL each 19700-10

Delivery tubes w/ 90 hook each 4157800

Pipet tips, for 1.010.0 mL TenSette Pipet 50/pkg 2199796

Pipet tips, for 1.010.0 mL TenSette Pipet 250/pkg 2199725

1 Chloride, HR

Chloride, HR, 10255

Prepare the probe1. Remove the sensor protection cap from the probe.

Chloride, HR DOC316.53.01322Direct Measurement ISE Method Method 102553.55 g/L to 35 g/L Cl Powder Pillow ISAScope and Application: For the determination of high concentrations (1 M) of chloride in brine solutions, produced waters and hydraulic fracturing waters.

Test preparation

Procedure notes:

The instructions in this procedure are specific to the HQd meters. The SensION+ meters can also be used but the navigation and menus will be different.

Refer to the meter user manual for meter operation. Refer to the probe user manual for probe maintenance.

Set the date and time in the meter before the probe is attached. The probe must have the correct service-life time stamp.

If complete traceability is necessary, enter a sample ID and operator ID. Refer to the HQd meter manualfor more information.

Calibrate the probe regularly for the best measurement accuracy. Refer to Calibrate the probe.

Stir the standards at a slow and steady rate to prevent the formation of a vortex.

Air bubbles under the probe tip can cause slow response or measurement errors. Gently shake the probe to remove bubbles.

Keep the temperature of the calibration standards within 2 C for best results.

Between measurements, rinse the probe with deionized water. Blot dry with a lint-free cloth.

Items to collect:


Beaker, 100-mL, polypropylene 4

Bottle, wash, 500-mL 1

Chloride ion-selective electrode 1

Chloride Ionic Strength Adjustor (ISA) Buffer Powder Pillows 4

Deionized water varies

Meter, ion-selective electrode 1

Sodium chloride 11.55 g

Stir bars 4

Stirrer, electromagnetic 1

Volumetric flask, 200-mL 3

See Consumables and replacement items for reorder information.

Chloride, HR 2

Chloride, HR

2. Rinse the probe with deionized water. Blot dry with a lint-free cloth.

3. Put the probe in a 3.55 g/L chloride standard solution for a minimum of 30 minutes. Refer to Prepare the calibration standards.

Set up the meterChange the default settings in the meter for high-range measurements. Save the new settings as a new method.

1. Connect the probe to the meter.

2. Push .

3. Go to ISECl181 Settings>Modify Current Settings>Measurement Options.

4. Set the measurement options for high-range measurements:

Unitsg/L

Measurement limitsset the lower limit to 3 g/L.

5. Go to Calibration Options.

6. Set the calibration options for high-range measurements:

Std setcustom

Calibration unitsg/L

Std set values3.55, 12.5 and 35 g/L

7. Enter a name for the new settings, for example HR Cl.

8. Push EXIT until the display shows the measurement mode.

Calibrate the probePrepare the calibration standards

Prepare a 3.55 g/L, a 12.5 g/L and a 35 g/L chloride standard solution for calibration.

Items to collect:

Sodium chloride, NaCl

Volumetric flasks (3x), 200 mL, Class A

Laboratory balance

Deionized water

1. Prepare a 35 g/L chloride standard solution:

a. Weigh 11.55 g of sodium chloride.

b. Quantitatively transfer the NaCl into a volumetric flask.

c. Dilute to the mark with deionized water. Mix fully.

2. Prepare a 12.5 g/L chloride standard solution:

a. Transfer 71.43 mL (or g) of the 35 g/L standard solution into a volumetric flask.

b. Dilute to the mark with deionized water. Mix fully.

3. Prepare a 3.55 g/L chloride standard solution:

a. Transfer 56.8 mL (or g) of the 12.5 g/L standard solution into a volumetric flask.

Chloride, HR

3 Chloride, HR

b. Dilute to the mark with deionized water. Mix fully.

HR chloride calibration procedure

1. Add 25 mL of the 3.55 g/L, 12.5 g/L and 35 g/L chloride standard solution to three beakers.

2. Add a stir bar and stir at a moderate rate.

3. Add the contents of one Chloride Ionic Strength Adjustment (ISA) Powder Pillow to each standard solution.


5. Put the probe into the 3.55 g/L chloride standard solution. Tap the probe to remove any air bubbles.

6. Push Calibrate. The display shows the standard solution value.

7. Push Read. The display shows Stabilizing. When the reading is stable, the display shows the next standard solution value.

8. Repeat steps 4 to 7 for the 12.5 g/L and the 35 g/L chloride standard solutions.

9. Push Done to view the calibration summary.

10. Push Store to accept the calibration.Rinse the probe with deionized water and blot dry.

4-7

Chloride, HR 4

Chloride, HR

Measure samplesDilute samples that are greater than 35 g/L

If the chloride concentration is greater than 35 g/L (1 M), dilute the sample to a lower concentration. Complete the steps that follow to make a 1:10 (10-fold) dilution.

1. Measure 2.5 mL of the sample in a 25-mL graduated cylinder.

2. Add deionized water to the 25-mL line.

3. Pour the diluted sample into a beaker.

4. Measure the concentration with the HR chloride measurement procedure.

5. Multiply the result by 10 to get the concentration of the sample before dilution.

HR chloride measurement procedure

1. Add 25 mL of sample to a 50-mL beaker.

2. Add a stir bar and stir at a moderate rate.

3. Add the contents of one Chloride Ionic Strength Adjustment (ISA) Powder Pillow per 25 mL of sample.


5. Put the probe into the sample. Tap the probe to remove any air bubbles.

6. Push Read. The display shows Stabilizing and then the chloride concentration of the sample.

7. Repeat steps 1 through 6 for each sample.

8. When done, rinse the probe.

1-6

Chloride, HR

5 Chloride, HR

Sample collection, preservation and storageCollect samples in clean plastic or glass containers. Samples can be stored for a minimum of 28 days at room temperature.

InterferencesThe sensing element can respond to other ions in addition to chloride and cause a positive error. If Chloride ISA is added to the standards and samples, the effect of interfering ions is minimized. Samples can contain oxidizing agents such as Copper (Cu2+), Iron (ferrous) (Fe2+) and Permanganate (MnO4-). Refer to Table 1.

Consumables and replacement items

Table 1 Interfering substancesSubstance Interference

Mercury Must be absent from samples.Ions that form insoluble salts of silver Can deposit a layer of salt on the sensing surface and cause probe errors.

Strong reducing solutions Can form a surface layer of silver.

Required reagents and apparatus


Chloride Ionic Strength Adjustor (ISA) Buffer Powder Pillows 1 100/pkg 2318069

Beaker, 50-mL, polypropylene 1 1 108041

IntelliCAL Chloride Ion Selective Electrode (ISE), 1 m cable 1 1 ISECL18101



Sodium chloride, ACS grade 454 g 18201H



Bottle, wash, 500 mL 1 62011

Cylinder, graduated, 25-mL, poly 1 108140

Deionized water 4 L 27256

IntelliCAL Chloride Ion Selective Electrode (ISE), 3 m cable 1 ISECL18103

sensION+ 9652C Chloride Combination Ion Selective Electrode (ISE), 1 m cable1

1 Use with sensION+ meters or other meters that have a BNC connection.

1 LZW9652C.97.002

Volumetric flask, 200 mL, Class A, glass 1 1457445

1 Conductivity

How to use instrument-specific informationTable 1 shows the meter and probe options for this test. To use this table, select a meter, then read across to find the probe options.

Conductivity DOC316.53.01324USEPA1 Direct Measurement Method2

1 USEPA accepted for reporting for Standard method 2510-B2 Procedure is equivalent to Standard Method 2510-B for wastewater.

Method 10256(0.01 S/cm to 200.00 mS/cm) Conductivity MeterScope and Application: For oil and gas field waters.

Test preparation

Table 1 Instrument-specific information

Meter Standard probe Rugged probe1

1 Designed for field use.

HQ40d, HQ30d or HQ14d CDC40101, CDC40103 CDC40105, CDC40110, CDC40115, CDC40130


Collect samples in clean plastic or glass bottles. Fill completely and cap tightly.

Measure samples as soon as possible after collection. If immediate measurement is not possible, samples can be kept at 0 to 6 C (32 to 43 F) for a minimum of 24 hours.

If solutions are not at the reference temperature, the meter automatically adjusts the conductivity value to the value at the reference temperature.

Water samples that contain oils, grease or fats will add a layer of residue on the electrode and can decrease the accuracy of the readings. If this occurs, clean the probe with a strong detergent solution, then thoroughly rinse with deionized water.

Mineral build-up on the probe can be removed with a dilute (1:1) hydrochloric acid solution. Refer to the meter user manual.

For the best results, calibrate before use or measure the conductivity of a standard solution to make sure that the measured conductivity agrees with the known value of the standard. Calibration instructions are given in the meter user manual.

For the most accurate results with high conductivity samples, calibrate the cell constant or check the accuracy of the meter with a 111.3 mS/cm (1 Demal) certified conductivity standard.

Measurement errors can occur if the correct temperature correction value is not selected. Refer to Table 3 for typical correction values.

To display other units such as TDS, salinity or resistivity, refer to the meter user manual.

Items to collect:


Beaker, poly, 100-mL 1

HQd meter and conductivity IntelliCAL probe 1

Conductivity 2

Conductivity

One of the following conductivity standard solutions

NaCl conductivity standards:

NaCl standard solution, 180 10 S/cm 1



NaCl standard solution, 18 10 mS/cm 1

KCl conductivity standards:

0.1 Molar KCl, 12.88 mS/cm at 25 C 500 mL

0.01 Molar KCl, 1413 S/cm at 25 C 500 mL

0.001 Molar KCl, 148 S/cm at 25 C 500 mL

Certified conductivity standards:

KCl, 1 Demal, 111.3 mS/cm 0.5% at 25 C 500 mL

KCl, 0.1 Demal, 12.85 mS/cm 0.35% at 25 C 500 mL

KCl, 0.01 Demal, 1408 S/cm 0.5% at 25 C 500 mL

NaCl, 0.05%, 1015 S/cm 0.5% at 25 C 500 mL

See Consumables and replacement items for reorder information.

Conductivity

1. Prepare the electrode and the meter. Refer to the documentation for the electrode or the meter. The meter selects the range automatically.

2. Laboratory tests: Put the probe in a beaker that contains the sample. Move the probe up and down and tap it on the beaker to remove bubbles.Field tests: Put the probe in the sample. Move the probe up and down to remove bubbles from the electrode. The vent holes must be completely submerged.

3. Turn the meter on. Make sure that the meter is set to measure conductivity. When the conductivity value is stable, store or record the value.

4. Rinse the probe thoroughly with deionized water after each measurement.

Items to collect: (continued)


Conductivity

3 Conductivity

ConversionsTable 2 shows the conversions to change the readings on the display to other conductivity units.

Table 3 shows typical temperature correction values for selected solutions from the linear temperature correction option.

Interferences To remove the conductivity from hydroxide ions, neutralize the pH of the sample:

a. Add 4 drops of phenolphthalein indicator solution to 50 mL of sample. The solution becomes pink.

b. Add gallic acid solution by drops until the pink color completely goes away.

c. Measure the conductivity.

For more information on conductivity measurements in oil and gas field waters, refer to the Conductivity and Total Dissolved Solids Procedures Explained section of the Hydraulic Fracturing Water Analysis Handbook.

Table 2 Unit conversionFrom To Use this equation

mS/cm S/cm mS/cm 1000S/cm mS/cm S/cm 0.001S/cm mhos/cm S/cm 1mS/cm mmhos/cm mS/cm 1S/cm mg/L TDS S/cm 0.641

1 TDS is an empirically-derived value from the conductivity measurement. A value of 0.64 is selected here for simplicity and suitability to oil and gas field waters.

g/L TDS mg/L TDS g/L TDS 1000mS/cm g/L TDS mS/cm 0.64

mg/L TDS g/L TDS mg/L TDS 0.001mg/L TDS gpg TDS mg/L TDS 0.05842g/L TDS gpg TDS g/L TDS 58.42S/cm ohms cm 1,000,000 S/cmmS/cm ohms cm 1,000 mS/cm

Table 3 Temperature correctionSolution Percent per C

Ultrapure water 4.55

Salt (NaCl) 2.125

NaOH 1.72

Dilute ammonia 1.8810

10% HCl 1.325

5% sulfuric acid 0.9698

Conductivity 4

Conductivity

Accuracy checkMeasure the conductivity of a sodium chloride (NaCl) standard solution that has a similar value to the conductivity of typical samples. The measured conductivity should be close to the known value of the standard solution. If the value is outside of the accuracy limits on the standard solution label, complete a calibration with this standard solution. Refer to the meter user manual.

Method performanceThe accuracy of a conductivity measurement depends on many factors that are associated with the overall conductivity system, which includes the meter, electrode and calibration solutions. Refer to the documentation for the electrode or the meter for more information.

Summary of methodElectrolytic conductivity is the movement of ions in a solution, which makes an electrical current and is the reciprocal of the solution resistivity. The ions come from inorganic dissolved solids (e.g., chloride, nitrate, sulfate and phosphate anions and sodium, calcium, magnesium, iron and aluminum cations). Organic material such as oils, phenols, alcohols and sugars do not have enough conductivity for a useful estimate of concentration.

Conductivity meters measure the resistance that occurs in

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