DOC022.53.80225 8ed

DOC022.53.
80225
Hydraulic Fracturing Water Analysis Handbook

For use with DR 900 Colorimeters
01/2016, Edition 8
Introduction
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.
2
Alkalinity, DT, 8203
Alkalinity DOC316.53.01308
Phenolphthalein and Total Alkalinity Method 10244

10 to 4000 mg/L as CaCO3 Digital Titrator
Scope 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.
For added convenience when stirring, use the TitraStir® stirring apparatus1.
meq/L Alkalinity = mg/L as CaCO3 ÷ 50
1 Refer to Optional reagents and apparatus on page 8.
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.
1 Alkalinity
Alkalinity
Test procedure
See
Table 1
1. Select a sample 2. Insert a clean delivery 3. Turn the delivery knob 4. Use a graduated
volume and titration tube into the 1.600 N to eject air and a few drops cylinder or pipet to
cartridge from Table 1 on Sulfuric Acid titration of titrant. Reset the measure the sample
page 3. cartridge. Attach the counter to zero and wipe volume from Table 1 on
Note: Typical oil and gas cartridge to the titrator. the tip. page 3.
field water levels are 100– Note: Other titrant
600 mg/L CaCO3. strengths are available.
5. Transfer the sample 6. Add the contents of 7. Place the delivery tube 8. Use the multiplier in
into a clean, 250-mL one Phenolphthalein into the solution and swirl Table 1 on page 3 to
Erlenmeyer flask. If the Indicator Powder Pillow. the flask. Turn the knob on calculate the
sample volume is less Swirl to mix. the titrator to add titrant to concentration:
than 100 mL, dilute to If the solution turns pink or the solution. Continue to digits x multiplier =
approximately 100 mL with the measured pH is swirl the flask and add mg/L as CaCO3
deionized water. greater than 8.3, proceed titrant until the color P alkalinity
Note: A pH meter may be to step 7. If the solution is changes from pink to
colorless or until a pH of Example: 100 mL of
used in highly colored colorless or the measured sample was titrated with
samples. If a pH meter is pH is less than 8.3, the 8.3 is reached.
the 1.600 N cartridge and
used, the Phenolphthalein Phenolphthalein (P) Write down the number of 250 digits were used to
Indicator Powder Pillow is alkalinity is zero. Proceed digits displayed on the reach the end point. The
not required in the next to step 9. counter. concentration is 250 x 1.0
step. = 250 mg/L as CaCO3.
Alkalinity 2
Alkalinity
Test procedure (continued)
See
Table 4
9. Add the contents of 10. Continue the titration 11. Use the multiplier in 12. Calculate the
one Bromcresol Green- with sulfuric acid to a light Table 1 to calculate the bicarbonate, carbonate
Methyl Red Indicator pink color or to a pH of 4.5. concentration: and hydroxide alkalinities
Powder Pillow. Swirl to Write down the number of digits x multiplier = with Table 4 on page 6.
mix. digits displayed on the mg/L as CaCO3
Note: The Bromcresol counter. total alkalinity
Green-Methyl Red Note: A pH meter may be Example: 100 mL of
Indicator Powder Pillow is used to titrate to a specific sample was titrated with
not required if a pH meter pH as required by sample the 1.600 N cartridge and
is used. composition. Refer to 250 digits were used to
Table 2. A pH of 4.5 is reach the end point. The
recommended. concentration is 250 x 1.0
= 250 mg/L as CaCO3.
Table 1 Range-specific information

Range (mg/L as CaCO3) Sample volume (mL) Titration cartridge (N H2SO4) Multiplier
10–40 100 0.1600 0.1

40–160 25 0.1600 0.4
100–400 100 1.600 1.0
200–800 50 1.600 2.0
500–2000 20 1.600 5.0
1000–4000 10 1.600 10.0
Table 2 End point pH

Sample 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
3 Alkalinity
Alkalinity
Interferences
Table 3 lists substances that can interfere with this test.
Table 3 Interfering substances
Interfering substance Interference level
Chlorine at levels above 3.5 mg/L may cause a yellow-brown color when the Bromcresol
Chlorine 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.
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
Color or turbidity
phenolphthalein acidity. For total alkalinity, refer to Table 2 on page 3 for the correct end point
pH.
Soaps, oily matter, suspended Oils or solids may cover the pH probe and cause a slow or sluggish response. Clean the
solids and precipitates probe immediately after use (refer to Maintenance of pH probes).
Maintenance of pH probes
To 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 12–16 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:
2. Soak the glass bulb for 10–15 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.
Alkalinity 4
Alkalinity
Sample collection, preservation and storage

Alkalinity 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 meter

Sample 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 table

Total 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
5 Alkalinity
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.
Table 4 Alkalinity relationships

Hydroxide alkalinity Carbonate alkalinity Bicarbonate alkalinity
Row Sample result
equals: equals: equals:
1 Phenolphthalein Alkalinity = 0 0 0 Total Alkalinity
2 Phenolphthalein Alkalinity equal Total Alkalinity 0 0
to Total Alkalinity
3 Phenolphthalein Alkalinity less 0 Phenolphthalein Alkalinity Total Alkalinity minus two
than one-half of Total Alkalinity times 2 times Phenolphthalein
Alkalinity
4 Phenolphthalein Alkalinity equal 0 Total Alkalinity 0
to one-half of Total Alkalinity
5 Phenolphthalein Alkalinity 2 times Phenolphthalein 2 times the difference 0
greater than one-half of Total Alkalinity minus Total between Total and
Alkalinity Alkalinity Phenolphthalein Alkalinity
Accuracy check
End point confirmation
Use a buffer pillow with the same pH as the end point with the indicator to make sure the end point
color is accurate.
• Phenolphthalein alkalinity—Add 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 alkalinity—Add 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, 0.1–1.0 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.
Alkalinity 6
Alkalinity
Summary of method
The 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 cylinder—select 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
7 Alkalinity
Alkalinity
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
FOR TECHNICAL ASSISTANCE, PRICE INFORMATION AND ORDERING: HACH COMPANY

In the U.S.A. – Call toll-free 800-227-4224 WORLD HEADQUARTERS
Outside the U.S.A. – Contact the HACH office or distributor serving you. Telephone: (970) 669-3050
On the Worldwide Web – www.hach.com; E-mail – techhelp@hach.com FAX: (970) 669-2932
© Hach Company, 2011. All rights reserved. Printed in U.S.A. 06/2011, Edition 1
Chloride, HR, 10255
Bacteria, Acid-producing DOC316.53.01328
Visual determination APB-BART™*

Semi-quantitative
Scope 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 2. Collect at least 20 mL 3. Fill the inner tube with 4. Put the inner tube in
from the outer tube. of sample in the outer the sample to the fill line. the outer tube and tighten
tube. Tighten the cap on the the cap on the outer tube.
inner tube. Do not shake or swirl the
tube!
5. Invert the tube for 30 6. Write the date and 7. Incubate the tube at 8. Examine the tube
seconds to dissolve the sample name on the outer room temperature and each day for 8 days.
dye under the cap. tube. away from direct sunlight. Record the date when a
Do not move the tube. reaction is first seen. Refer
to Test results.
1 Bacteria, Acid-producing
Bacteria, Acid-producing
Interferences
If 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 results
Presence/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 population
If 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.
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 <100 Low
8 <100 Low
Advanced test information

If the test result is positive, examine the tubes for dominant bacteria. The dominant bacteria for
this test is gRAM-negative fermenting bacteria.
Summary of method
When 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).
Disposal
Sterilize the reacted sample before disposal. Refer to Figure 1.
Bacteria, Acid-producing 2
Bacteria, Acid-producing
Figure 1 Disposal

Required reagents and apparatus
BART Test for acid-producing bacteria 1 9/pkg 2831409
3 Bacteria, Acid-producing
©Hach Company, 2012. All rights reserved. Printed in the U.S.A. 08/2012, Edition 1
Bacteria, Heterotrophic Aerobic DOC316.53.01329
Visual determination
Semi-quantitative HAB-BART™1
Scope and application: For the determination of total aerobic bacteria in brine solutions, produced waters and
1 HAB-BART is a trademark of Droycon Bioconcepts Inc.
Test preparation
Before starting
Do not touch the inner surface of the tube or lid. Keep contamination out of the tube and lid. Use the aseptic technique.
Set the caps on a clean surface with the flat surface down.
Review the Safety Data Sheets (MSDS/SDS) for the chemicals that are used. Use the recommended personal protective
equipment.
Dispose of reacted solutions according to local, state and federal regulations. Refer to the Safety Data Sheets for disposal
information for unused reagents. Refer to the environmental, health and safety staff for your facility and/or local regulatory
agencies for further disposal information.
Sterilize the reacted sample before disposal. Refer to Disposal on page 3.
Items to collect
BART Test for heterotrophic aerobic bacteria (HAB) 1
Refer to Consumables and replacement items on page 3 for order information.
Test procedure
1. Remove the inner tube 2. Pour at least 20 mL of 3. Fill the inner tube to the 4. Put the inner tube in the
from the outer tube. sample in the outer tube. fill line with the sample that empty outer tube. Tighten
is in the outer tube. Tighten the cap on the outer tube.
the cap on the inner tube. Do not shake or swirl the
Discard the unused sample tubes after the sample is
in the outer tube. added. Let the ball float to
the top with no help.
1
5. Invert the tube for 6. Write the date and 7. Keep the tube at room 8. Examine the tube each
30 seconds to dissolve the sample name on the outer temperature and away from day. Record the date when
dye under the cap. For tube. direct sunlight for 4 days. a reaction is first seen.
saline waters, invert the Do not move the tube. Refer to Test results
tube for 5 minutes. on page 2.
Test results
Presence/Absence
When heterotrophic aerobic bacteria are in the sample, the color of the solution changes
from a blue to a light or medium yellow color. The solution frequently becomes cloudy.
• Negative (absent/non-aggressive)—The color stays blue.
• Positive (present/aggressive)—The color becomes yellow. The solution frequently
becomes cloudy.

If 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.
Days to reaction Approximate HAB population (cfu/mL) Aggressivity
1 5,400,000 Very high
2 575,000 High
3 61,000 Moderate
4 6500 Moderate to low
5 700 Low
6 Less than 75 Very low

If the test result is positive, examine the tubes for dominant bacteria. Refer to Figure 1.
Figure 1 Dominant bacteria
Aerobic bacteria Facultative anaerobic bacteria

The color is bleached from the bottom to the top. The color is bleached from the top to the bottom.
2 Bacteria, Heterotrophic Aerobic, HAB-BART

Summary of method
When heterotrophic aerobic bacteria (HAB) are in the sample, the bacteria consume
oxygen during incubation. When the oxygen is gone, the bacteria react with the
methylene blue dye in the HAB-BART tube and change the dye to the 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 (e.g., slime formation, 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 in
the sample.
Disposal
Figure 2 Disposal

Required reagents
BART Test for heterotrophic aerobic bacteria (HAB) 1 9/pkg 2490409

BART Test for heterotrophic aerobic bacteria (HAB) 1 27/pkg 2490427
Bacteria, Heterotrophic Aerobic, HAB-BART 3

© Hach Company/Hach Lange GmbH, 2012–2016. All rights reserved. 01/2016, Edition 3
Chloride, HR, 10255
Bacteria, Slime-forming DOC316.53.01327
Visual determination SLYM-BART™*

Semi-quantitative
Scope and Application: For the determination of slime-forming bacteria in brine solutions, produced waters and
*SLYM-BART is a trademark of Droycon Bioconcepts Inc.
Test preparation
Procedure notes:
invert the cap.
Test procedure
tube!
5. Write the date and 6. Incubate the tube at 7. Examine the tube
sample name on the outer room temperature and each day for 8 days.
tube. away from direct sunlight. Record the date when a
to Test results.
1 Bacteria, Slime-forming
Bacteria, Slime-forming
Test results
Presence/Absence
When slime-forming bacteria are present, the solution becomes cloudy. Refer to Figure 1.
Figure 1 Negative versus positive test results
The solution is cloudy. A

The solution stays
glowing ring is seen
clear, with no visible
under UV light and/or
growth or glow under
there is slime growth at
UV light.
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

If 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.
Dense slime in bottom Glows pale blue Thread-like

Cloudy growth or Blackened liquid—
or slime ring around under UV light— strands—
layered plates—slime- pseudomonads
ball—dense slime fluorescing tight slime
forming bacteria and enterics
bacteria pseudomonads bacteria
Bacteria, Slime-forming 2
Bacteria, Slime-forming
Summary of method
When 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.
Disposal
Figure 3 Disposal

BART Test for slime-forming bacteria 1 9/pkg 2432509
BART Test for slime-forming bacteria 1 27/pkg 2432527
3 Bacteria, Slime-forming
Chloride, HR, 10255
Bacteria, Sulfate-reducing DOC316.53.01326
Visual determination SRB-BART™*

Semi-quantitative
Scope 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:
invert the cap.
SRB grow predominantly deep within biofilms and not directly in water. Make sure to get a representative sample.
Test procedure
tube!
to Test results.
1 Bacteria, Sulfate-reducing
Bacteria, Sulfate-reducing
Interferences
If 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.
Test results
Presence/Absence
When sulfate-reducing bacteria are present, a black slime forms in the tube. Refer to Figure 1.
A black slime
ring forms
around the ball
The solution
and/or there is
has no black
a black slime
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

If the test result is positive, examine the tubes for dominant bacteria. Refer to Figure 2.
Black in the bottom only—dense Black around the ball only— Black in the bottom and
Cloudy solution—
anaerobic bacteria dominated by aerobic SRB with around the ball—aerobic
anaerobic bacteria
Desulfovibrio aerobic slime forming heterotrophs and anaerobic SRB
Bacteria, Sulfate-reducing 2
Bacteria, Sulfate-reducing
Summary of method
When 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.
Disposal
Figure 3 Disposal

BART Test for sulfate-reducing bacteria 1 9/pkg 2432409
BART Test for sulfate-reducing bacteria 1 27/pkg 2432427
3 Bacteria, Sulfate-reducing
©Hach Company, 2012-2013. All rights reserved. Printed in the U.S.A. 07/2013, Edition 2
Chloride, HR, 10255
Bacteria, Iron-related DOC316.53.01325
Visual determination IRB-BART™*

Semi-quantitative
Scope and Application: For the determination of iron-related bacteria in brine solutions, produced waters and
*IRB-BART is a trademark of Droycon Bioconcepts Inc.
Test preparation
Procedure notes:
invert the cap.
IRB grow predominantly on surfaces and not directly in water. Make sure to get a representative sample.
Test procedure
tube!
to Test results.
1 Bacteria, Iron-related
Bacteria, Iron-related
Test results
Presence/Absence
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.
Foam or a brown
slime ring forms
The solution has around the ball
no foam or and/or there is a
brown slime. 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

If 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.
Red
Foam around Cloudy— Black solution—
Brown rings, gel and/or clouds— Green cloudy— cloudy—
ball—anaerobic heterotrophic pseudomonads
iron-related bacteria pseudomonads enteric
bacteria bacteria and enterics
bacteria
Bacteria, Iron-related 2
Bacteria, Iron-related
Summary of method
When 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.
Disposal
Figure 3 Disposal

BART Test for iron-related bacteria 1 9/pkg 2432309
BART Test for iron-related bacteria 1 27/pkg 2432327
3 Bacteria, Iron-related
Barium DOC316.53.01315
Turbidimetric Method1 Method 10251

2 to 100, 20 to 1000, 200 to 10,000 mg/L Ba (spectrophotometers) Powder Pillows
2 to 80, 20 to 800, 200 to 8000 mg/L Ba (colorimeters)
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 information
Table 1 shows all of the instruments that have the program for this test. The table also
shows sample cell and orientation requirements for reagent addition tests, such as
powder pillow or bulk reagent tests.
To use the table, select an instrument, then read across to find the applicable information
for this test.
Table 1 Instrument-specific information
Instrument Sample cell orientation Sample cell
DR 6000 The fill line is to the right. 2495402
DR 3800
DR 2800
DR 2700
DR 1900
DR 5000 The fill line is toward the user.
DR 3900
DR 900 The orientation mark is toward the user. 2401906
Before starting
For turbidimetric methods, install the instrument cap or cover on all instruments before ZERO or READ is pushed.
Use the Standard Adjust option with each new lot of reagent for the best results. Refer to the Standard solution method in
Accuracy check on page 4.
For the best results, measure the reagent blank value for each new lot of reagent. Replace the sample with deionized water
in the test procedure to determine the reagent blank value. Subtract the reagent blank value from the sample results
automatically with 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.
equipment.
1
Items to collect
BariVer™ 4 Barium Reagent Powder Pillows 1

Sample cells (For information about sample cells, adapters or light shields, refer to Instrument-
2
specific information on page 1.)
Sample collection and storage

• Collect samples in clean glass or plastic bottles that have been cleaned with 6 N (1:1)
hydrochloric acid and rinsed with deionized water.
• To preserve samples for later analysis, adjust the sample pH to less than 2 with
concentrated nitric acid (approximately 2 mL per liter). No acid addition is necessary if
the sample is tested immediately.
• Keep the preserved samples at room temperature for a maximum of 6 months.
• Before analysis, adjust the pH to 5 with 5 N sodium hydroxide solution.
• Correct the test result for the dilution caused by the volume additions.
Powder pillow procedure
Start
1. Start program 20 2. Prepare the blank: Add 3. If the sample volume is 4. Swirl to mix.
Barium. For information the sample volume that is less than 10 mL, add Refer to Set the dilution
about sample cells, specified for the test range deionized water to the factor on page 3. A
adapters or light shields, to a clean sample cell: 10-mL line. 10-mL graduated mixing
refer to Instrument-specific cylinder can be used in
information on page 1. • 2–100 mg/L: 10 mL steps 2 and 3.
• 20–1000 mg/L: 1.0 mL
Note: Although the program
name can be different • 200–10,000 mg/L:
between instruments, the 0.1 mL
program number does not
change. Use a pipet to add the
1.0 mL and 0.1 mL volumes.
Zero
5. Clean the blank sample 6. Insert the blank into the 7. Push ZERO. The display 8. Remove the sample cell
cell. cell holder. shows 0 mg/L Ba2+. from the cell holder.
2 Barium, Turbidimetric Method (multi-range: 100, 1000, 10,000 mg/L)

9. Prepare the sample: 10. Swirl to mix. 11. Start the instrument 12. Clean the prepared
Add the contents of one The sample will become timer. A 5-minute reaction sample cell.
BariVer™ 4 Barium Reagent cloudy if barium is in the time starts.
Powder Pillow to the sample sample. Accuracy is not Do not move the sample cell
cell. affected by undissolved during the reaction period.
The solution will get cloudy powder.
if barium is in the sample.
Read
13. Within 5 minutes after 14. Push READ. Results 15. Clean the sample cell
the timer expires, insert the show in mg/L Ba2+. immediately after each test
prepared sample into the with soap, water and a
cell holder. brush.
Interferences
Calcium 10,000 mg/L as CaCO3
Magnesium 100,000 mg/L as CaCO3
Silica 500 mg/L
Sodium Chloride 130,000 mg/L as NaCl
Strontium 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 best
results occur when the barium concentration is less than 20 mg/L and when the strontium
concentration (as mg/L) is equal to or less than the barium concentration.
Highly buffered samples or Can prevent the pH adjustment by the reagent(s) and cause incorrect results.
extreme sample pH
Set the dilution factor

Instruments that have a dilution factor option can include the dilution factor in the result
and show the concentration of the original, undiluted sample. For example, if the sample
is diluted by a factor of 10, the instrument multiplies the result by 10 and shows the
calculated result in the instrument display.
Barium, Turbidimetric Method (multi-range: 100, 1000, 10,000 mg/L) 3

1. Select Options>More>Dilution factor from the instrument menu.
Note: DR 1900: Select Options>Advanced Options>Dilution Factors>On.
Note: Colorimeters include a dilution factor when the chemical form is set. Go to
Options>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 check
Use the standard additions method (for applicable instruments) to validate the test
procedure, 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®, 0.1–1.0 mL
• Pipet tips
1. 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 0.1 mL, 0.2 mL and
0.3 mL 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 the
instrument.
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 that
the sample volumes and sample spikes are measured accurately. The sample volumes and
sample spikes that are used should agree with the selections in the standard additions menu. If
the results are not within acceptable limits, the sample may contain an interference.
Standard solution method

Use the standard solution method to validate the test procedure, the reagents and the
instrument.
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 water
1. 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 the
volumetric 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.
4 Barium, Turbidimetric Method (multi-range: 100, 1000, 10,000 mg/L)

3. Compare the expected result to the actual result.
Note: The factory calibration can be adjusted slightly with the standard adjust option so that the
instrument shows the expected value of the standard solution. The adjusted calibration is then
used for all test results. This adjustment can increase the test accuracy when there are slight
variations in the reagents or instruments.
Method performance
The method performance data that follows was derived from laboratory tests that were
measured on a spectrophotometer during ideal test conditions. Users can get different
results under different test conditions.
Program Standard Precision (95% confidence interval) Sensitivity
Concentration change per 0.010 Abs change
20 30 mg/L Ba 25–35 mg/L Ba 1 mg/L Ba
Summary of method
The BariVer™ 4 Barium Reagent Powder combines with barium to form a barium sulfate
precipitate, which is held in suspension by a protective colloid. The amount of precipitate
is proportional to the barium concentration. The measurement wavelength is 450 nm for
spectrophotometers or 520 for colorimeters.
Required reagents
Description Quantity/test Unit Item no.
BariVer™ 4 Barium Reagent Powder Pillow 1 100/pkg 1206499
Barium Standard Solution, 1000-mg/L Ba 100 mL 1461142

Water, deionized 4L 27256
Brush, test tube each 69000

Filter paper, 2–3-micron, pleated, 12.5-cm 100/pkg 189457
Flask, volumetric, Class A, 100-mL glass 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, 0–14 pH range 100/pkg 2601300
®
Pipet, TenSette , 0.1–1.0 mL each 1970001
®
Pipet tips for TenSette Pipet, 0.1–1.0 mL 50/pkg 2185696
®
Pipet, volumetric 5.00-mL each 1451537
Pipet filler, safety bulb each 1465100
Sodium Hydroxide Standard Solution, 5.0 N 100 mL MDB 245032
Barium, Turbidimetric Method (multi-range: 100, 1000, 10,000 mg/L) 5

Boron DOC316.53.01313
Carmine Method Method 10252

2 to 50 mg/L B Powder Pillows
Scope and application: For oil and gas field waters
Test preparation
shows adapter and light shield requirements for the instruments that use them.
for this test.
Table 1 Instrument-specific information for test tubes
Instrument Adapters Light shield
DR 6000, DR 5000 — —
DR 3900 — LZV849
DR 3800, DR 2800, DR 2700 — LZV646
DR 1900 9609900 (D1) —
DR 900 4846400 Cover supplied with the instrument
1 The D adapter is not available with all instrument versions.
Before starting
Install 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 with
running water.
equipment.
Items to collect
BoroVer 3 Reagent Powder Pillow 1

Sufuric Acid, Concentrated 75 mL
Water, deionized 2 mL
Tubes, 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
1
Items to collect (continued)
Light shield or adapter (For information about sample cells, adapters or light shields, refer to
1
Instrument-specific information on page 1.)
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
OR
Pipet, 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 collection
Collect samples in clean polyethylene or polypropylene bottles.
Prepare the glass tubes for first use
New glass tubes can contain residual amounts of reactive boron from the glass
manufacturing 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.
Start
1. Start program 41 Boron 2. Use a 100-mL graduated 3. In a well-ventilated area 4. Swirl the flask
HR. For information about cylinder to measure 75 mL or fume hood, add the immediately to mix. Swirl for
sample cells, adapters or of concentrated sulfuric contents of one BoroVer 3 up to 5 minutes to dissolve
light shields, refer to acid. Pour the acid into a Reagent Powder Pillow to the powder completely.
Instrument-specific plastic 250-mL Erlenmeyer the flask.
information on page 1. flask.
name can be different
between instruments, the
change.
2 Boron, Carmine Method (50 mg/L)

5. Prepare the blank: 6. Prepare the sample: 7. Add 3.5 mL of the 8. Put the cap on the
Remove the cap from a Remove the cap from a BoroVer 3 Solution from prepared sample and invert
clean 16-mm tube. Add clean 16-mm tube. Add step 4 to the prepared to mix.
0.2 mL of deionized water. 0.2 mL of sample. sample tube. The solution in the tube will
Refer to Prepare the glass Note: If a 3.5-mL pipet is Note: If a 3.5-mL pipet is get warm.
tubes for first use on page 2 not available, 0.4 mL of not available, 7.0 mL of
and Clean the glass tubes sample can be used. BoroVer 3 Solution can be
after use on page 4. used with 0.4 mL of sample.
Note: If a 3.5-mL pipet is
not available, 0.4 mL of DI
water can be used.
9. Add 3.5 mL of the 10. Put the cap on the 11. Start the instrument 12. When the timer expires,
BoroVer 3 Solution from blank. Iinvert to mix. timer. A 30-minute reaction clean the blank sample cell.
step 4 to the blank sample The solution in the tube will time starts.
tube. get warm.
Note: If a 3.5-mL pipet is
not available, 7.0 mL of
BoroVer 3 Solution can be
used with 0.4 mL of
deionized water.
Zero
13. Insert the blank into the 14. Push ZERO. The 15. Clean the prepared 16. Insert the prepared
cell holder. display shows 0.0 mg/L B sample cell. sample into the cell holder.
HR.
Boron, Carmine Method (50 mg/L) 3

Read
17. Push READ. Results

show in mg/L B.
Reagent preparation
More than 75 mL of the BoroVer 3/Sulfuric Acid Solution can be prepared for use in
multiple analyses.
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 a maximum of 48 hours when kept 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. Determine the amount of sulfuric acid and powder pillows that are necessary for the
number of samples to be analyzed. Use 75 mL of sulfuric acid for each analysis. Use
one BoroVer 3 Reagent Powder Pillow for each 75 mL of sulfuric acid.
2. Under a fume hood, measure the concentrated sulfuric acid with a graduated
cylinder.
3. Pour the acid into a Erlenmeyer flask.
4. Stir the acid and add the contents of one BoroVer 3 Reagent Powder Pillow to the
flask. Swirl to mix. Wait for the powder to completely dissolve. Continue to add one
powder pillow at a time. Stir to dissolve after each powder pillow is added.
5. Pour this solution into plastic containers and use within 48 hours.
Clean the glass tubes after use
NOTICE
The BoroVer 3/Sulfuric Acid solution is highly acidic. Neutralize the solution to pH 6–9 before
disposal. Refer to a current SDS (Safety Data Sheet) for safe handling and disposal instructions of
reacted 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 check
instrument.
4 Boron, Carmine Method (50 mg/L)

Items to collect:
• 1000 mg/L Boron Standard Solution
• 3-mL volumetric pipet, Class A and pipet filler
• Deionized water
1. 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 the
volumetric flask.
solution.
Method performance
41 25 mg/L B 24.2–25.8 mg/L B 2.2 mg/L B
Summary of method
Boron is determined by its reaction with carminic acid in the presence of sulfuric acid to
produce a reddish to bluish color. The amount of color is directly proportional to the boron
concentration. The measurement wavelength is 605 nm for spectrophotometers or
610 nm for colorimeters.
Required reagents

®
BoroVer 3 Boron Reagent Powder Pillow 1 pillow/1 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 vials 2 6/pkg 2241106
Cylinder, graduated, polypropylene, 100-mL 1 each 108142
Flask, Polymethylpentene, screw cap, 250-mL, 125-mL 1 each 2089846
Pipet, adjustable volume, 0.2–1.0 mL 1 each BBP078
Pipet tips, for 0.2–1.0 mL pipet 2 100/pkg BBP079
Boron, Carmine Method (50 mg/L) 5

Required apparatus (continued)

OR
®
Pipet, TenSette , 0.1–1.0 mL 1 each 1970001
®
Pipet Tips, for TenSette Pipet, 0.1–1.0 mL 2 50/pkg 2185696
®
Pipet, TenSette 1.0–10.0 mL 1 each 1970010
®
Pipet Tips, for TenSette Pipet, 1.0–10.0 mL 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 apparatus
Gloves, chemical resistant, size 10 pair 2410105

Goggles, safety, standard each 2927902
®
®
Test tube rack, stainless steel each 1864100
Pipets, adjustable volume, includes one 0.2–1.0 mL and one 1.0–5.0 mL pipet plus
each LZP320
tips

Chloride, DT, 8207
Chloride DOC316.53.01306
Silver Nitrate Method Method 10246

100 to 200,000 mg/L as Cl– Digital Titrator
Scope and Application: For the measurement of high concentrations (1 M) of chloride in brine solutions,
produced waters and hydraulic fracturing 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.
Chloride 2 Indicator Powder Pillow 1
Silver Nitrate titration cartridge, 1.128 N 1
Digital titrator 1
Graduated cylinder or TenSette Pipet, (0.1–1.0 mL) with pipet tips 1
Water, deionized 4 liters
Refer to Consumables and replacement items for reorder information.
Determine sample sizes

To estimate the chloride concentration of gas and oil shale water samples, prescreen the samples.
1. Add approximately 75–100 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.
Table 1 Guidelines to estimate sample sizes
Number of digits Sample size (mL)
250 0.1
125 0.2
1 Chloride
Chloride
Table 1 Guidelines to estimate sample sizes (continued)

Number of digits Sample size (mL)
50 0.5
25 1.0
10 2.0
5 5.0
2 20
1 50
Chloride test procedure
See
Table 1
1. Select a sample 2. Insert a clean delivery 3. Hold the Digital 4. Use a TenSette
volume from Table 2 on tube into the 1.128 N Titrator with the cartridge graduated cylinder or pipet
page 3. Refer to Silver Nitrate titration tip pointing up. Turn the to measure the sample
Determine sample sizes cartridge. Attach the delivery knob to eject a volume from Table 2 on
on page 1. cartridge to the titrator. few drops of titrant. Reset page 3 into a 250 mL
Note: Put the Silver Nitrate the counter to zero and Erlenmeyer flask.
Titration Cartridge in a wipe the tip.
dark area when not in use.
5. Dilute the measured 6. Add the contents of 7. Place the delivery tube 8. Use the multiplier in
sample to approximately one Chloride 2 Indicator into the solution and Table 2 on page 3 to
100 mL with deionized Powder Pillow. Swirl to rapidly swirl the flask. Turn calculate the
water. The amount of mix. the knob on the titrator to concentration:
dilution water added is not Results will still be add titrant to the solution. digits x multiplier =
critical. accurate if a small amount Continue to swirl the flask mg/L Cl–
of powder does not and add titrant until the
color changes from yellow Example: 1.0 mL of
dissolve. sample was titrated with
to red-brown. Refer to
Technique tips on page 3. the 1.128 N cartridge and
200 digits were used to
Write down the number of reach the end point. The
digits displayed on the concentration is 200 x 50 =
counter. 10,000 mg/L Cl–.
Chloride 2
Chloride
Chloride test procedure (continued)
Table 2 Range-specific information
Range (mg/L as Cl–) Sample volume (mL) Titration cartridge (N AgNO3) Multiplier
100–400 50 1.128 1.0

250–1000 20 1.128 2.5
1000–4000 5 1.128 10.0
2500–10,000 2 1.128 25.0
5000–20,000 1 1.128 50
10,000–40,000 0.5 1.128 100
25,000–100,000 0.2 1.128 250
50,000–200,000 0.1 1.128 500

Collect 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.
• 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 50–75% 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.
Interferences
Table 3 lists substances that can interfere with this test.
Interfering substance Interference level1
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.
3 Chloride
Chloride
Table 3 Interfering substances (continued)

Interfering substance Interference level1
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
pH
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.
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.
Sulfide 2. Mix for one minute.
3. Filter through folded filter paper.
4. Use the filtered sample in the chloride test procedure.
Concentrations above 10 mg/L interfere with this method. To eliminate sulfite interference,
Sulfite
add three drops of Hydrogen Peroxide, 30%, to the sample before the test is started.
1 Interference level limits increase with smaller sample sizes.
Accuracy check
Use 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, 0.1–1.0 mL
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 3) or a problem with
reagents or apparatus.

Use 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.
Chloride 4
Chloride
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 method
The 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.

Required reagents
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
Delivery tubes w/ 180° hook 1 each 1720500
TenSette Pipet, 0.1–1.0 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
5 Chloride
Chloride

Filter paper, 12.5 cm 100/pkg 69257
Funnel, analytical, poly, 65 mm each 108367
Hydrogen Peroxide, 30%, ACS 473 mL 14411
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
pH Test Strip, 0–14 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, 1.0–10.0 mL each 19700-10
Delivery tubes w/ 90° hook each 4157800
Pipet tips, for 1.0–10.0 mL TenSette Pipet 50/pkg 2199796
Pipet tips, for 1.0–10.0 mL TenSette Pipet 250/pkg 2199725
Chloride 6
Chloride
7 Chloride
Chloride

© Hach Company, 2011, 2014. All rights reserved. Printed in U.S.A. 07/2014, Edition 2
Chloride, HR DOC316.53.01322
Direct ISE method Method 10255

3.55 g/L to 35 g/L Cl– Powder Pillow ISA
Scope and application: For the measurement of high concentrations (1 M) of chloride in brine solutions,
produced waters and hydraulic fracturing waters.
Test preparation
This procedure is applicable to the meters and probes that are shown in Table 1.
Procedures for other meters and probes can be different.
Meter Probe
HQ40d or HQ30d IntelliCAL ISECL181 combination chloride ISE
HQ440d or HQ430d
Before starting
Refer to the meter documentation for meter settings and operation. Refer to probe documentation for probe preparation,
maintenance and storage information.
Condition the probe before use. To condition the probe, put the probe in a 3.55 g/L Chloride Standard solution for a minimum
of 30 minutes.
Stir the standards and samples at a slow and constant rate to prevent the formation of a vortex.
Air bubbles under the sensor tip can cause slow response or measurement errors. To remove the bubbles, carefully shake
the probe.
Calibrate the probe regularly for the best measurement accuracy. Refer to Calibration on page 3.
During calibration, measure the standard solutions from lowest to highest concentration for best results.
Between measurements, rinse the probe with deionized water. Blot dry with a lint-free cloth.
Make sure that the calibration solutions and the samples are at the same temperature (± 2 °C (± 3.6 °F)) for best results.
equipment.
This procedure is specified for the HQd meters. The sensION+ meters can be used, but the menus and navigation will be
different.
Items to collect
Chloride Ionic Strength Adjustor (ISA) Buffer Powder Pillows varies

Sodium chloride 11.55 g
Beaker, polypropylene, 50-mL, low form 4
Volumetric flask, 200-mL 3
Water, deionized varies
1
Stir bar, magnetic, 2.2 x 0.5 cm (7/8 x 3/16 in.) 4

Stirrer, magnetic 1
Wash bottle with deionized water 1
Lint-free cloth 1
Sample collection
• Collect samples in clean glass or plastic bottles.
• If immediate analysis is not possible, keep the samples at room temperature for a
maximum of 28 days.
Configure the meter

Adjust the meter* for high-range measurements. Save the configuration as a new method.
1. Connect the probe to the meter.

2. Push .
3. Select ISECl181 Settings>Modify Current Settings.
4. Change the measurement and calibration options for high-range measurements:
Option Description
Measurement options • Units—g/L
• Measurement limits—Set the lower limit to 3 g/L
Calibration options • Std set—Custom

• Calibration units—g/L
• Std set values—3.55, 12.5 and 35 g/L
5. Enter a method name for the new configuration, for example "HR Cl".
6. Push EXIT until the display shows the measurement mode.
Test procedure
1. Add 25 mL of sample to a 2. Add the contents of one 3. Add a stir bar and put the 4. Rinse the probe with
beaker. Chloride Ionic Strength beaker on a magnetic deionized water. Dry the
Adjustment (ISA) Powder stirrer. Stir at a moderate probe with a lint-free cloth.
Pillow for each 25 mL of rate.
sample.
* Navigation and menus are different for SensION+ meters. Refer to the meter documentation.
2 Chloride, ISE Method (35 g/L Cl–)

5. Put the probe in the 6. Push Read. A progress 7. Rinse the probe with
solution. Do not let the bar is shown. When the deionized water. Dry the
probe touch the stir bar, measurement is stable, the probe with a lint-free cloth.
bottom or sides of the lock icon is shown.
container. Remove air
bubbles from under the
probe tip.
Sample dilution
If the chloride concentration is more 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. Dilute to the mark with deionized water. Mix well.
3. Pour the diluted sample into a beaker.
4. Use the test procedure to measure the concentration of the sample.
5. Multiply the result by 10 to get the concentration of the sample before dilution.
Calibration
Prepare the standard solutions
Prepare the standard solutions for calibration as follows.
Items to collect:
• Sodium chloride (NaCl)
• 200-mL volumetric flasks (3), Class A
• Laboratory balance
• Deionized water
1. Prepare a 35-g/L Chloride Standard Solution as follows:

a. Weigh 11.5 g of sodium chloride.
b. Quantitatively move the NaCl into a 200-mL volumetric flask.
c. Dilute to the mark with deionized water. Mix well.
2. Prepare a 12.5-g/L Chloride Standard Solution as follows:
a. Move 71.43 mL (or g) of the 35-g/L Chloride Standard Solution into a 200-mL
volumetric flask.
b. Dilute to the mark with deionized water. Mix well.
3. Prepare a 3.55-g/L Chloride Standard Solution as follows:
a. Move 56.8 mL (or g) of the 12.5-g/L Chloride Standard Solution into a 200-mL
volumetric flask.
b. Dilute to the mark with deionized water. Mix well.
Chloride, ISE Method (35 g/L Cl–) 3

Calibration procedure
1. Add 25 mL of the lowest 2. Add the contents of one 3. Add a stir bar and put the 4. Rinse the probe with
concentration standard Chloride Ionic Strength beaker on a magnetic deionized water. Dry the
solution to a beaker. Adjustment (ISA) Powder stirrer. Stir at a moderate probe with a lint-free cloth.
Pillow for each 25 mL of rate.
sample.
5. Put the probe in the 6. Push Calibrate. The 7. Push Read. A progress 8. Rinse the probe with
solution. Do not let the standard solution value is bar is shown. When the deionized water. Dry the
probe touch the stir bar, shown. measurement is stable, the probe with a lint-free cloth.
bottom or sides of the lock icon is shown.
container. Remove air
bubbles from under the
probe tip.
9. Measure the remaining 10. Push Done. A 11. Push Store to accept
standard solutions. calibration summary is the calibration.
shown when the minimum
number of calibration
standards are measured.
4 Chloride, ISE Method (35 g/L Cl–)

Interferences
The sensing element reacts to chloride as well as other ions. Typically, probe response to
another ion increases the potential, and causes a positive error. If Chloride ISA is added
to the standards and samples, the effect of interfering ions is decreased. Refer to Table 2.
Oxidizing agents such as Copper (Cu2+), Iron (Fe2+) and Do not interfere.
Permanganate (MnO4–)
Mercury Interferes at all levels.
Ions that form insoluble salts of silver Can form a layer of salt on the sensing surface and cause probe
errors.
Strong reducing solutions Can form a surface layer of silver.

HQd meters and probes
HQ40d multi-parameter portable meter (2 probe inputs) each HQ40d53000000

HQ30d multi-parameter portable meter (1 probe input) each HQ30d53000000
HQ440d multi-parameter benchtop meter (2 probe inputs) each HQ440d
HQ430d multi-parameter benchtop meter (1 probe input) each HQ430d
IntelliCAL ISECL181 digital combination chloride ISE, 1 meter cable each ISECL18101
IntelliCAL ISECL181 digital combination chloride ISE, 3 meter cable each ISECL18103
Recommended reagents and standards
Chloride Ionic Strength Adjustor (ISA) Buffer Powder Pillows 100/pkg 2318069
Sodium Chloride, ACS 454 g 18201H
Accessories
Beaker, polypropylene, 50-mL, low form each 108041

Bottle, wash, 500-mL each 62011
Graduated cylinder, polypropylene, 25-mL each 108140
Flask, volumetric, Class A, 200-mL each 1457445
Probe clips, color-coded, for IntelliCAL probes 50/pkg 5818400
sensION+ 9652 Chloride combination ISE probe, 1 m cable each LZW9652C.97.002
Probe holder, 3 probes, for sensION+ benchtop meters each LZW9321.99
Probe stand, universal each 8508850
Stir bar, magnetic, 2.2 x 0.5 cm (7/8 x 3/16 in.) each 4531500
Stirrer, electromagnetic, 120 VAC, with electrode stand each 4530001
Chloride, ISE Method (35 g/L Cl–) 5

© Hach Company/Hach Lange GmbH, 2012, 2014. All rights reserved. 07/2014, Edition 2
Conductivity DOC316.53.01324
USEPA direct measurement method1, 2 Method 10256

0.01 µS/cm to 200.0 mS/cm Conductivity meter
Scope and application: For brine solutions, produced waters and hydraulic fracturing waters.
1 USEPA accepted for reporting for Standard Method 2510-B
2 Procedure is equivalent to Standard Method 2510-B for wastewater.
Test preparation
Meter Standard probe Rugged probe
HQ40d, HQ30d or HQ14d CDC40101, CDC40103 CDC40105, CDC40110, CDC40115, CDC40130
Before starting
If solutions are not at the reference temperature, the meter automatically adjusts the conductivity value to the value at the
reference temperature.
Measurement errors can occur if the correct temperature correction value is not selected. Refer to Table 3 on page 3 for
typical correction values.
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 fully rinse with deionized water.
Remove mineral build-up on the probe with a dilute (1:1) hydrochloric acid solution. Refer to the meter documentation.
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. Refer to the meter documentation for calibration instructions.
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.
Refer to the meter documentation to show other units such as TDS, salinity or resistivity.
equipment.
Items to collect
Beaker, 100-mL, polypropylene 1

Conductivity standard solution, refer to Recommended standards on page 4. 1
1
• To preserve samples for later analysis, keep the samples at or below 6 °C (43 °F) for
a minimum of 24 hours.
• Let the sample temperature increase to room temperature before analysis.
Test procedure
1. Rinse the probe with 2. Laboratory test: Put the 3. Push Read. A progress 4. Rinse the probe with
deionized water. Dry the probe in a beaker that bar is shown. When the deionized water. Dry the
probe with a lint-free cloth. contains the solution. measurement is stable, the probe with a lint-free cloth.
Remove air bubbles from lock icon is shown.
under the probe tip. Stir the
sample at a slow to
moderate rate.
Field test: Put the probe in
the sample. Move the probe
up and down to remove
bubbles from the electrode.
Make sure that the
temperature sensor is put
fully into the sample.
Conversions
Table 2 shows the conversions to change the readings on the display to other
conductivity units.
Table 2 Unit conversion
From To Use this equation
mS/cm μS/cm mS/cm × 1000
μS/cm mS/cm μS/cm × 0.001
μS/cm μmhos/cm μS/cm × 1
mS/cm mmhos/cm mS/cm × 1
μS/cm mg/L TDS μS/cm × 0.641
g/L TDS mg/L TDS g/L TDS × 1000
mS/cm g/L TDS mS/cm × 0.64
mg/L TDS g/L TDS mg/L TDS × 0.001
mg/L TDS gpg TDS mg/L TDS × 0.05842
g/L TDS gpg TDS g/L TDS × 58.42
2 Conductivity, Direct Measurement Method (200.00 mS/cm)

Table 2 Unit conversion (continued)
From To Use this equation
μS/cm ohms cm 1,000,000 ÷ μS/cm
mS/cm ohms cm 1,000 ÷ mS/cm
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.
Table 3 shows typical temperature correction values for selected solutions from the linear
temperature correction option.
Table 3 Temperature correction
Solution 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
Interferences
To remove the conductivity that results from hydroxide ions, neutralize the pH of the
sample:
1. Add 4 drops of phenolphthalein indicator solution to 50 mL of sample. The solution
becomes pink.
2. Add 1 drop of gallic acid solution at a time until the pink color is gone.
3. Measure the conductivity.
Accuracy check
instrument.
Items to collect:
• Sodium chloride standard solution with a conductivity value that is close to the value
of typical samples.
1. Use the test procedure to measure the concentration of the standard solution.
Method performance
The accuracy of the measurements depends on many factors that are related with the
overall system, which includes the meter, the probe and calibration solutions. Refer to the
meter or probe documentation for more information.
Summary of method
Electrolytic 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 good estimate of the
concentration.
Conductivity, Direct Measurement Method (200.00 mS/cm) 3

Conductivity meters measure the resistance that occurs in an area of the solution that is
defined by the physical design of the probe. A voltage is applied between the electrodes,
and the voltage drop caused by the resistance of the solution is used to calculate the
conductivity per centimeter. The basic unit of measure for conductivity is the Siemen (or
mho), which is the reciprocal of the ohm. Other common units for aqueous solutions are
milliSiemens/cm (10–3 S or mS/cm) and microSiemens/cm (10–6 S or μS/cm).

HQ14d portable conductivity meter each HQ14d53
IntelliCAL™ standard conductivity probe, 1 m cable each CDC40101
IntelliCAL™ standard conductivity probe, 3 m cable each CDC40103
IntelliCAL™ rugged conductivity probe, 5 m cable each CDC40105
NaCl conductivity standards:

Sodium chloride standard solution, 180 ± 10 mS per cm, 90 ± 1 mg per L TDS 100 mL 2307542
Sodium chloride standard solution, 18,000 ± 50 mS per cm, 9000 ± 25 mg per L TDS 100 mL 2307442
KCI conductivity standards:
0.1 M KCI, 12.88 mS per cm at 25 °C (77 °F) 500 mL C20C250
0.01 M KCI, 1413 µS per cm at 25 °C (77 °F) 500 mL C20C270
0.001 M KCI, 148 µS per cm at 25 °C (77 °F) 500 mL C20C280
Certified conductivity standards:
KCI, 1 Demal, 111.3 mS per cm ± 0.5% at 25 °C (77 °F) 500 mL S51M001
KCI, 0.1 Demal, 12.85 mS per cm ± 0.35% at 25 °C (77 °F) 500 mL S51M002
KCI, 0.01 Demal, 1408 mS per cm ± 0.5% at 25 °C (77 °F) 500 mL S51M003
NaCl, 0.05%, 1015 µS per cm ± 0.5% at 25 °C (77 °F) 500 mL S51M004
Optional reagents and accessories
Beaker, polypropylene, 100-mL each 108042

Gallic acid solution 50 mL SCDB 1442326
Hydrochloric Acid Solution, 6 N, 1:1 500 mL 88449
Phenolphthalein indicator solution 15 mL SCDB 16236
4 Conductivity, Direct Measurement Method (200.00 mS/cm)

Optional reagents and accessories (continued)
Wash bottle, 125-mL each 62014

Conductivity, Direct Measurement Method (200.00 mS/cm) 5

Barium, 8014
Hardness, Calcium DOC316.53.01318
Titration Method using EDTA Method 10253

(100 to 200,000 mg/L as CaCO3) Digital Titrator
Scope and Application: For brine solutions, produced waters and hydraulic fracturing waters.
Test preparation
Magnesium is not included in the results but must be present for a sharp endpoint. If magnesium is not present, add one to
two drops of Magnesium Standard Solution, 10-g/L as CaCO3 to the sample before the test is started.
mg/L Ca = Ca hardness in mg/L as CaCO3 x 0.40
A 0.1-g scoop of CalVer® 2 Calcium Indicator Powder can be used in place of the CalVer 2 Calcium Indicator Powder Pillow.
If samples cannot be analyzed immediately, refer to Sample collection, preservation and storage. Adjust the pH of preserved
samples before analysis.
For added convenience, use the TitraStir® stir plate1.

1 Refer to Optional reagents and apparatus.
CalVer 2 Calcium Indicator Powder Pillow 1 pillow
Potassium Hydroxide Standard Solution, 8 N 1 bottle
0.800 M EDTA titration cartridge 1 cartridge
Digital titrator 1
Water, deionized 4L
1 Hardness, Calcium
Hardness, Calcium
Test procedure
See
Table 1
or
Table 2
1. Select a sample 2. Put a clean delivery 3. Hold the digital titrator 4. Use a graduated
volume and titration tube into the 0.800 M with the cartridge tip up. cylinder or pipet to
cartridge from Table 1. EDTA titration cartridge. Turn the delivery knob to measure the sample
Refer to Identify the Put the cartridge in the eject air and a few drops of volume identified in step 1.
sample volume if the titrator. titrant. Wipe the tip. Put the sample in a clean,
concentration ranges are Reset the counter to zero. 250-mL Erlenmeyer flask.
unknown. If the sample volume is
less than 100 mL, dilute to
about 100 mL with
deionized water.
5. If the sample volume 6. Add the contents of 7. Put the delivery tube 8. Use the multiplier in
is 100 mL, add 2 mL of one CalVer 2 Calcium in the solution and swirl Table 1 to calculate the
8 N Potassium Hydroxide Indicator Powder Pillow. the flask. Turn the knob on concentration:
Standard Solution. Swirl to mix. the titrator to add titrant to digits x multiplier =
If the sample volume is the solution. mg/L Ca as CaCO3
50 mL or less, add 1 mL of Continue to swirl the flask
8 N Potassium Hydroxide and add titrant until the
Standard Solution. color changes from red to
Swirl to mix. pure blue.
Record the number of
digits that are shown on
the counter.
Example:
50 mL of sample was titrated with the 0.800 M EDTA titration cartridge and 250 digits were used to
get to the endpoint. The calcium concentration is 250 x 2 = 500 mg/L as CaCO3.
Hardness, Calcium 2
Hardness, Calcium
Table 1 Range-specific information—mg/L

Range (mg/L as CaCO3) Sample volume (mL) Multiplier
100–400 100 1
200–800 50 2
500–2000 20 5
1000–4000 10 10
2000–8000 5 20
5000–20,000 2 50
10,000–40,000 1 100
20,000–80,000 0.5 200
50,000–200,000 0.2 500
Identify the sample volume

Screen the samples to estimate the calcium hardness concentration when the concentration
ranges are unknown.
1. Add 75–100 mL of deionized or hardness-free water to a clean titration flask.
3. Add 1.0 mL of 8 N potassium hydroxide. Swirl to mix.
4. Add one CalVer 2 Calcium Indicator Powder Pillow and swirl to mix. The sample will change to
red.
5. Titrate the solution quickly with the 0.800 M EDTA titrant to the blue endpoint. Record the
number of digits that were added.
6. Find the estimated sample volume from Table 2. Use this sample volume for the test
procedure.
7. Rinse the titration flask fully with deionized water.
Table 2 Guidelines to estimate the sample volume

Number of digits Sample volume (mL)
200 0.2
100 0.5
50 1
25 2
10 5
5 10
1 20

Collect the sample in a clean plastic or glass bottle.
To clean the bottle:
1. Clean the bottles with detergent, then rinse with tap water.
2. Rinse the bottles in 1:1 nitric acid solution, then rinse with deionized water.
3 Hardness, Calcium
Hardness, Calcium
Samples can be used for up to 6 months if preserved and kept at room temperature. Preserve
samples only when immediate analysis is not possible.
To preserve the sample:
1. Add 1.5 mL of nitric acid per 1 liter (1 quart) of sample to the sample. Mix fully.
2. Measure the sample pH.
3. If the sample pH is greater than 2, add more nitric acid in 0.5-mL increments. Mix fully and
check the pH of the sample after each addition until the sample pH is 2 or less.
Before analysis:
1. Add Potassium Hydroxide Standard Solution to the preserved sample in increments. Mix fully
and check the pH of the sample after each addition until the sample pH is 7.
2. Make a volume correction for the nitric acid and hydroxide added.
Total volume = sample + acid + hydroxide

Volume correction = (total volume) divided by (sample volume)
Corrected test result = (test result) x (volume correction)
Interferences
WARNING
Chemical hazard. Potassium cyanide is toxic. Always add potassium cyanide after the
potassium hydroxide. Obey local hazardous waste regulations for disposal of all cyanide-
containing waste.
An interfering substance can prevent the color change at the titration endpoint. A dilution can often
reduce the interference to a level at which the substance does not interfere. If an interference is
suspected, decrease the sample volume, dilute to about 100 mL and do the test again. Table 3
shows substances that can interfere with this test.

Substance Interference levels and treatments
Acidity This test can tolerate 10,000 mg/L acidity.
Alkalinity This test can tolerate 10,000 mg/L alkalinity.
Causes a slow endpoint but up to 200 mg/L aluminum can be tolerated if sufficient time is
Aluminum
given for the color change.
Barium is a by-product from the drilling process and can be present in very high
concentrations in process and flow back waters. The barium will be titrated directly with the
calcium titration.
Barium If strontium and calcium are not present in the sample, the barium will precipitate at pH 13
similar to magnesium. However, most produced and flow back water samples have
strontium, calcium and barium present at high concentrations. If the barium concentration is
known, it can be subtracted from the calcium hardness by converting the mg/L Ba
concentration to mg/L as CaCO3 by multiplying the Ba concentration by 0.729.
Chloride Saturated solutions do not give a distinct endpoint. The test can be run directly in sea water.
Interferes at all levels. 0.5 grams of potassium cyanide can be added after the potassium
Cobalt
hydroxide solution to remove interference from up to 20 mg/L cobalt.
Interferes at 0.1 mg/L copper. 0.5 grams of potassium cyanide can be added after the
Copper
potassium hydroxide solution to remove interference from up to 100 mg/L copper.
Hardness, Calcium 4
Hardness, Calcium

Interferes at levels greater than 8 mg/L by causing an orange-red to green endpoint.
Accurate results can still be obtained up to 20 mg/L iron with this endpoint. The iron
interference can be removed by the addition of a CDTA powder pillow when the
concentrations are greater than 100 mg/L.
Iron
However, since the hardness concentrations in these fracing fluids are very high, the use of a
smaller sample volume will decrease the iron interference. If when using a smaller sample
volume the iron concentration is still present at a concentration greater than 100 mg/L, add
the CDTA powder pillow to decrease this interference.
Interference from magnesium is prevented up to 200 mg/L by the formation of magnesium
Magnesium
hydroxide at the high test pH but higher levels prevent a distinct endpoint.
Manganese Interferes at levels greater than 5 mg/L.
Interferes at 0.5 mg/L nickel. 0.5 grams of potassium cyanide can be added after the
Nickel
potassium hydroxide solution to remove interference from up to 200 mg/L nickel.
Causes a slow endpoint but does not interfere if the calcium phosphate that forms is given
Orthophosphate
time to dissolve again during the titration.
Polyphosphates Interfere directly and must be absent.
Strontium is a by-product from the drilling process and can be present in very high
concentrations in process and flow back waters.
Strontium The strontium will be titrated directly with the Ca hardness titration. If the strontium
concentration of the sample is known, it can be subtracted from the result by converting the
mg/L Sr concentration to mg/L as CaCO3 by multiplying the Sr concentration by 1.142.
Samples at 20 °C (68 °F) or colder should be titrated slowly near the endpoint to provide
Temperature
sufficient time for the color change.
Interferes at 5 mg/L zinc. 0.5 grams of potassium cyanide can be added after the potassium
Zinc
hydroxide solution to remove interference from up to 100 mg/L zinc.
Highly buffered samples or May be greater than the buffering capacity of the reagents. Adjust the pH before starting the
extreme sample pH test (refer to Sample collection, preservation and storage).
Accuracy check
Use the standard additions method to identify if the sample has an interference and to make sure
that the test procedure was completed correctly.
Prerequisites:
• Calcium Hardness Voluette Ampule Standard Solution, 10,000-mg/L as CaCO3
• Ampule breaker
• Pipet tips
3. Titrate the spiked sample to the endpoint. Record the amount of titrant that was used to get to
the endpoint.
4. Repeat steps 2 and 3.
Each 0.1 mL of standard that was added should use 10 digits of the 0.800 M titration cartridge to
get to the endpoint.
5 Hardness, Calcium
Hardness, Calcium
If more or less titrant was used, the problem can be due to user technique, an interference (refer to
Interferences) or a problem with reagents or apparatus.
Summary of method
The sample is made alkaline (pH 12 to 13) with potassium hydroxide to precipitate magnesium as
magnesium hydroxide. CalVer 2 Calcium Indicator is added and combines with any calcium to give
a red color. As the EDTA is added, it reacts with all the free calcium, barium (as long as both
strontium and calcium are present) and strontium present. At the endpoint of the titration, when no
free calcium ions are present, the EDTA removes the calcium complexed with the indicator. The
indicator then changes from red to blue.

Required reagents
Reagent set (100 tests): 2447500
(1) CalVer 2 Calcium Indicator Powder Pillows 1 pillow 100/pkg 85299
(1) Potassium Hydroxide Standard Solution, 8 N 1–2 mL 100 mL MDB 28232H
(1) EDTA titration cartridge, 0.800 M varies 1 1439901
Required apparatus
Description Quantity/Test Item no.
Digital titrator 1 1690001
Flask, Erlenmeyer, graduated, 250-mL 1 50546
Cylinder, graduated, 10-mL 1 50838
TenSette Pipet, 0.1–1.0 mL 1 1970001
Tensette Pipet tips 50/pkg 2185696
Delivery tube, 180° hook 5/pkg 1720500
Calcium Hardness Standard Solution, Voluette ampule, 10,000-mg/L as CaCO3, 10-mL 16/pkg 218710
Hardness Quality Control Standard, high range 500 mL 2833349
Hardness, Calcium 6
Hardness, Calcium

CalVer® 2 Calcium Indicator Powder 113 g 28114H

Magnesium Standard Solution, 10-g/L as CaCO3 29 mL 102233
CDTA Magnesium Salt Powder Pillow 100/pkg 1408099
Hardness 2 Indicator Solution 100 mL 42532
HexaVer Hardness Titrant, 0.020 N 1L 74053
ManVer 2 Hardness Indicator Powder 113 g 28014
Nitric Acid Solution, ACS 500 mL 15249
Sodium Hydroxide Standard Solution, 5 N 50 mL 245026
Potassium Cyanide 125 g 76714
Stir bar, octagonal 28.6 mm x 7.9 mm 1 2095352
TitraStir stir plate, 115 VAC 1 1940000
Potassium Hydroxide, 8 N 500 mL 28249
Pipet, volumetric, Class A, 10 mL 1 1451538
Pipet, volumetric, Class A, 20 mL 1 1451520
Pipet filler, safety bulb 1 1465100
Bottles, sampling, poly, 500 mL 1 2087079
Bromphenol green-methyl red indicator solution 100 mL MDB 2329232
Phenolphthalein Indicator Solution, 5 g/L 100 mL MDB 16232
pH meter 1 —
Pipet tips 50/pkg 2185696
Spoon, measuring, 1 g 1 51000
Spoon, measuring, 0.5 g 1 90700
Voluette Ampule breaker, 10 mL 1 2196800
Sampling bottle with cap, low density polyethylene, 250 mL 12/pkg 2087076
7 Hardness, Calcium
Hardness, Calcium

Hardness, Total, DT, 8213
Hardness, Total DOC316.53.01317
Titration Method using EDTA Method 10247

(100 to 200,000 mg/L as CaCO3) Digital Titrator
Scope and Application: For brine solutions, produced waters and hydraulic fracturing waters.
Test preparation
Four drops of Hardness 2 Indicator Solution or a 0.1-g scoop of ManVer 2 Hardness Indicator Powder can be added instead
of the ManVer 2 Hardness Indicator Powder Pillow.
Total Hardness as Ca = mg/L Total Hardness as CaCO3 x 0.40
mg/L Total Hardness as CaCO3 = mg/L Ca as CaCO3 + mg/L Mg as CaCO3.
If samples cannot be analyzed immediately, refer to Sample collection, preservation and storage. Adjust the pH of preserved
samples before analysis.
For added convenience, use the TitraStir® stir plate1.

1 Refer to Optional reagents and apparatus.
ManVer 2 Hardness Indicator Powder Pillow 1
Hardness 1 Buffer Solution 2 mL
0.800 M EDTA titration cartridge 1 cartridge
Digital titrator 1
Water, deionized 4L
1 Hardness, Total
Hardness, Total
Test procedure
See
Table 1
or
Table 2
1. Select a sample 2. Put a clean delivery 3. Hold the digital titrator 4. Use a graduated
volume from Table 1. tube into the 0.800 M with the cartridge tip up. cylinder or pipet to
Refer to Identify the EDTA titration cartridge. Turn the delivery knob to measure the sample
sample volume if the Put the cartridge in the eject air and a few drops of volume identified in step 1.
concentration ranges are titrator. titrant. Wipe the tip. Put the sample in a clean,
unknown. Reset the counter to zero. 250-mL Erlenmeyer flask.
If the sample volume is
less than 100 mL, dilute to
about 100 mL with
deionized water.
5. Add 2 mL of Hardness 6. Add the contents of 7. Put the delivery tube 8. Use the multiplier in
1 Buffer Solution. Swirl to one ManVer 2 Hardness in the solution and swirl Table 1 to calculate the
mix. Indicator Powder Pillow. the flask. Turn the knob on concentration:
Swirl to mix. the titrator to add titrant to digits x multiplier =
the solution. mg/L total hardness as
Continue to swirl the flask CaCO3
and add titrant until the
color changes from red to
pure blue.
Record the number of
digits that are shown on
the counter.
Example:
50 mL of sample was titrated with the 0.800 M EDTA titration cartridge and 250 digits were used to
get to the endpoint. The total hardness concentration is 250 x 2 = 500 mg/L as CaCO3.
Hardness, Total 2
Hardness, Total
Table 1 Range-specific information—mg/L

Range (mg/L as CaCO3) Sample volume (mL) Multiplier
100–400 100 1
200–800 50 2
500–2000 20 5
1000–4000 10 10
2000–8000 5 20
5000–20,000 2 50
10,000–40,000 1 100
20,000–80,000 0.5 200
50,000–200,000 0.2 500
Identify the sample volume

Screen the samples to estimate the hardness concentration when the concentration ranges are
unknown.
1. Add 75–100 mL of deionized or hardness-free water to a clean titration flask.
3. Add 2 mL of Hardness 1 Buffer Solution. Swirl to mix.
4. Add one ManVer 2 Hardness Indicator Powder Pillow and swirl to mix. The sample will change
to red.
5. Titrate the solution quickly with the 0.800 M EDTA titrant to the blue endpoint. Record the
number of digits that were added.
6. Find the estimated sample volume from Table 2. Use this sample volume for the test
procedure.
7. Rinse the titration flask fully with deionized water.
Table 2 Guidelines to estimate the sample volume

Number of digits Sample volume (mL)
200 0.2
100 0.5
50 1
25 2
10 5
5 10
1 20

Collect the sample in a clean plastic or glass bottle.
To clean the bottle:
1. Clean the bottles with detergent, then rinse with tap water.
2. Rinse the bottles in 1:1 nitric acid solution, then rinse with deionized water.
3 Hardness, Total
Hardness, Total
Samples can be used for up to 7 days if preserved and kept at or less than 4 °C (39 °F). Preserve
samples only when immediate analysis is not possible.
To preserve the sample:
1. Add 1.5 mL of nitric acid per 1 liter (1 quart) of sample to the sample. Mix fully.
2. Measure the sample pH.
3. If the sample pH is greater than 2, add more nitric acid in 0.5-mL increments. Mix fully and
check the pH of the sample after each addition until the sample pH is 2 or less.
Before analysis:
1. Let the sample temperature increase to room temperature.
2. Add 5.0 N sodium hydroxide to the preserved sample to change the pH to 7. Mix fully.
3. If a significant amount of nitric acid was added to the sample, make a volume correction for the
add nitric acid and hydroxide.
Total volume = sample + acid + hydroxide

Volume correction = (total volume) divided by (sample volume)
Corrected test result = (test result) x (volume correction)
Interference
WARNING
Chemical hazard. Potassium cyanide is toxic. Always add potassium cyanide after the
potassium hydroxide. Obey local hazardous waste regulations for disposal of all cyanide-
containing waste.
An interfering substance can prevent the color change at the titration endpoint. A dilution can often
reduce the interference to a level at which the substance does not interfere. If an interference is
suspected, decrease the sample volume, dilute to about 100 mL and do the test again. Table 3
shows substances that can interfere with this test.

Acidity This test can tolerate 10,000 mg/L acidity.
Alkalinity This test can tolerate 10,000 mg/L alkalinity and can be done directly in sea water.
Aluminum interferes at levels greater than 0.20 mg/L aluminum. 0.5 grams of potassium
cyanide can be added after the buffer solution to remove interference of up to 1 mg/L
Aluminum aluminum.
As an alternative, the interference can be removed by the addition of a CDTA powder pillow.
Refer to Table 4 and Table 5.
Barium is a by-product from the drilling process and can be present in very high
Barium
The barium will be titrated directly with the total hardness titration. If the barium concentration
of the sample is known, it can be subtracted from the result. Refer to Table 5.
Interferes at all levels. 0.5 grams of potassium cyanide can be added after the potassium
hydroxide solution to remove interference from up to 20 mg/L cobalt.
Cobalt
Hardness, Total 4
Hardness, Total

Interferes at 0.1 mg/L copper. 0.5 grams of potassium cyanide can be added after the
potassium hydroxide solution to remove interference from up to 100 mg/L copper.
Copper
Interferes at levels greater than 8 mg/L by causing an orange-red to green endpoint.
Accurate results can still be obtained at levels up to 20 mg/L iron with this endpoint. The iron
concentrations are greater than 100 mg/L. Refer to Table 4 and Table 5.
Iron
However, since the hardness concentrations in these fracing fluids are very high, the use of a
smaller sample volume will decrease the iron interference. If when using a smaller sample
volume the iron concentration is still present at a concentration greater than100 mg/L, add
the CDTA powder pillow to decrease this interference.
Interferes at levels greater than 5 mg/L. The interference can be removed by the addition of
Manganese
a CDTA powder pillow. Refer to Table 4 and Table 5.
Interferes at 0.5 mg/L nickel. 0.5 grams of potassium cyanide can be added after the
potassium hydroxide solution to remove interference from up to 200 mg/L nickel.
Nickel
Causes a slow endpoint but does not interfere if the calcium phosphate that forms is given
Orthophosphate
time to redissolve during the titration.
Polyphosphates Interferes directly and must be absent.
Although less common than calcium and magnesium, other polyvalent metal ions cause the
Polyvalent metal ions
same hardness effects and will be included in the results.
Sodium chloride Saturated solutions do not give a distinct endpoint.
Strontium is a by-product from the drilling process and can be present in very high
Strontium
The strontium will be titrated directly with the total hardness titration. If the strontium
concentration of the sample is known, it can be subtracted from the result. Refer to Table 5.
Interferes at 5 mg/L zinc. 0.5 grams of potassium cyanide can be added after the potassium
hydroxide solution to remove interference from up to 100 mg/L zinc.
Zinc
Highly buffered samples or May exceed the buffering capacity of the reagents. Adjust the pH before starting the test
extreme sample pH (refer to Sample collection, preservation and storage).
The addition of one CDTA Magnesium Salt Powder Pillow will remove metals interferences at or
below the levels shown in Table 4. If more than one metal is present at or greater than the
concentrations in Table 4, the addition of another CDTA Magnesium Salt Powder Pillow may be
necessary.
Table 4 Interference level with CDTA pillow
Substance Interference level (mg/L)
Aluminum 50
Cobalt 200
Copper 100
Iron 100
Manganese 200
Nickel 400
Zinc 300
5 Hardness, Total
Hardness, Total
The results given with CDTA Magnesium Salt include the hardness contributed by the metals. If
the concentration of each metal is known, a correction can be made to get the hardness
contributed by calcium and magnesium only. The hardness contributed per mg/L metal ion is
shown in Table 5.
Metal hardness = (mg/L of metal in the sample) x (hardness equivalence factor)
Calcium and magnesium hardness = (total hardness) minus (metal hardness)
Table 5 Hardness equivalence factors
Substance Hardness equivalence factors (mg/L as CaCO3)
Aluminum 3.710
Barium 0.729
Cobalt 1.698
Copper 1.575
Iron 1.792
Manganese 1.822
Nickel 1.705
Strontium 1.142
Zinc 1.531
Accuracy check
Use the standard additions method to identify if the sample has an interference and to make sure
that the analytical technique is correct.
Prerequisites:
• Hardness Voluette Ampule Standard Solution, 10,000-mg/L as CaCO3
• Ampule breaker
• Pipet tips
3. Titrate the spiked sample to the endpoint. Record the amount of titrant that was used to get to
the endpoint.
4. Repeat steps 2 and 3.
Each 0.1 mL of standard that was added should use 10 digits of the 0.800 M titration cartridge to
get to the endpoint.
If more or less titrant was used, the problem can be due to user technique, an interference (refer to
Interference) or a problem with reagents or apparatus.
Hardness, Total 6
Hardness, Total

Complete the following test to make sure that the reagents and user technique are accurate.
Prerequisites:
• Calcium Chloride Standard Solution, 1000-mg/L as CaCO3
1. Add 20.0 mL of the standard solution to an Erlenmeyer flask.
2. Dilute to 100 mL with deionized water and mix fully.
3. Add the Hardness 1 Buffer Solution and ManVer 2 indicator. Swirl to mix.
4. Titrate the standard to the endpoint with the titration cartridge and calculate the result. The
result should be close to 1000 mg/L as CaCO3.
Summary of method
In the total hardness test procedure, the water sample is first buffered (using an organic amine and
one of its salts) to a pH of 10.1. An organic dye, calmagite, is added as the indicator for the test.
The organic dye reacts with calcium and magnesium ions to give a red-colored complex.
EDTA (ethylenediaminetetraacetic acid) is added as a titrant. The EDTA reacts with all free
calcium, magnesium, barium and strontium in the sample. At the endpoint of the titration, when
free magnesium ions are no longer available, EDTA removes magnesium ions from the indicator.
The indicator then changes from red to blue.

Required reagents
Reagent set (100 tests): 2448100
(1) ManVer 2 Hardness Indicator Powder Pillows 1 100/pkg 85199
(1) Buffer Solution, Hardness 1 2 mL 100 mL MDB 42432
Required apparatus
Digital titrator 1 1 1690001
Flask, Erlenmeyer, graduated, 250-mL 1 1 50546
Cylinder, graduated, 10-mL 1 1 50838
TenSette Pipet, 0.1–1.0 mL 1 1 1970001
Tensette Pipet tips 1 50/pkg 2185696
Delivery tube, 180° hook 1 5/pkg 1720500
Calcium Chloride Standard Solution, 1000-mg/L as CaCO3 1L 12153
Hardness Standard Solution, Voluette ampule, 10,000-mg/L as CaCO3, 10-mL 16/pkg 218710
7 Hardness, Total
Hardness, Total

CDTA Magnesium Salt Powder Pillow 100/pkg 1408099
ManVer 2 Hardness Indicator Powder 113 g 28014
Hardness 2 Indicator Solution 100 mL 42532
HexaVer Hardness Titrant, 0.020 N 1L 74053
Sodium Hydroxide Standard Solution, 5 N 50 mL 245026
Nitric Acid Solution, ACS 500 mL 15249
Potassium Cyanide 125 g 76714
Stir bar, octagonal 28.6 mm x 7.9 mm 1 2095352
Pipet, volumetric, 10 mL Class A 1 1451538
Pipet, volumetric, 20 mL Class A 1 1451520
Pipet filler safety bulb 1 1465100
Spoon, measuring, 1 g 1 51000
Pipet tips, for TenSette Pipet 1970010 50/pkg 2199796
Voluette breaker 1 2196800
Sampling bottle with cap, low density polyethylene, 250 mL 12/pkg 2087076

Iron, Total DOC316.53.01314
FerroVer® Method1 Method 10249

0.1 to 3.0, 1.0 to 30.0 and 10.0 to 300.0 mg/L Fe Powder Pillows
Scope and application: For brine solutions, produced waters and hydraulic fracturing waters; digestion is
required for total iron determinations.2
1 USEPA approved for reporting wastewater analysis, Federal Register, June 27, 1980; 45 (126:43459).
2 Adapted from Standard Methods for the Examination of Water and Wastewater.
Test preparation
for this test.
DR 3800
DR 2800
DR 2700
DR 1900
DR 3900
Before starting
To make sure that all forms of the metal are measured, digest the sample with heat and acid. Use the mild or vigorous
digestion. Refer to the Water Analysis Guide for more information.
equipment.
1
Items to collect
®
FerroVer Iron Reagent Powder Pillow, 10-mL 1
EDTA solution, 1M 2 drops
1

• Collect samples in clean glass or plastic bottles that have been cleaned with 6 N (1:1)
hydrochloric acid and rinsed with deionized water.
• 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 the
sample is tested immediately.
• To measure only dissolved iron, filter the sample immediately after collection and
before acidification.
• Keep the preserved samples at room temperature for a maximum of 6 months.
• Before analysis, adjust the pH to 3–5 with 5.0 N sodium hydroxide standard solution.
• Correct the test result for the dilution caused by the volume additions.
Test procedure
Start
1. Start program 265 Iron, 2. Fill a clean sample cell 3. If the sample volume is 4. Swirl to mix.
FerroVer. For information with sample: less than 10 mL, add
about sample cells, deionized water to the
adapters or light shields, • Use 10 mL of sample 10-mL line.
refer to Instrument-specific for the 0.02 to 3.0 mg/L
information on page 1. range.
• Use 1.0 mL of sample
name can be different for the 0.2 to 30.0 mg/L
between instruments, the range with a dilution
program number does not factor of 10.
change. • Use 0.1 mL of sample
for the 2.0 to 300.0
range with a dilution
factor of 100.
Note: Refer to Set the
dilution factor on page 4.
2 Iron, Total, FerroVer Method (multi-range: 3.0, 30.0, 300.0 mg/L)

5. Add 2 drops of 1 M 6. Swirl to mix. 7. Clean the sample cell. 8. Insert the sample cell
EDTA Solution to the into the cell holder.
sample.
Zero
9. Push ZERO. The display 10. Remove the sample cell 11. Add the contents of one 12. Swirl to mix.
shows 0.0 mg/L Fe. from the cell holder. FerroVer Iron Reagent Accuracy is not affected by
Powder Pillow to the sample undissolved powder.
cell.
Read
13. Start the instrument 14. When the timer expires, 15. Insert the sample cell 16. Push READ. Results
timer. A 3-minute reaction clean the sample cell. into the cell holder. show in mg/L Fe.
time starts.
If iron is present in the
sample, an orange color will
show.
Interferences
Interfering Interference level
substance
Barium, Ba2+ The dilution of samples lowers most barium concentrations below interference levels. No effects are
seen on analyzed samples that contain less than 50 mg/L of Ba. No effects are seen when a 1.0 or
0.1 mL sample volume is used in the test procedure. A turbidity may show at higher levels. Use
5 drops of EDTA Solution in the test procedure and allow the sample to react for 5 minutes.
Calcium, Ca2+ No effect at less than 10,000 mg/L as CaCO3.
Chloride, Cl– No effect at less than 185,000 mg/L.
Iron, Total, FerroVer Method (multi-range: 3.0, 30.0, 300.0 mg/L) 3

substance
Copper, Cu2+ No effect. Masking agent is contained in FerroVer Reagent.
High iron levels Inhibit color development. Dilute sample and re-test to verify results.
Magnesium No effect at 100,000 mg/L as CaCO3.
Molybdate No effect at 50 mg/L as Mo.
molybdenum
High sulfide levels, Pretreat the sample in a fume hood or in an area with sufficient airflow before analysis:
S2–
1. Add 5 mL of 6.0 N (1:1) hydrochloric acid solution to 100 mL of sample in a 250-mL Erlenmeyer
flask.
2. Boil for 20 minutes.
3. Let the solution cool to room temperature.
4. Adjust the pH to 3–5 with 5 N sodium hydroxide solution.
5. Add deionized water until the volume is 100 mL.
6. Use the treated sample in the test procedure.
Strontium, Sr2+ Strontium by itself does not interfere. Strontium in combination with Barium will cause a precipitate to
form. The dilution of samples lowers most strontium concentrations below interference levels. No
effects are seen on analyzed samples that contain less than 50 mg/L of combined Ba and Sr. No
effects are seen when a 1.0 or 0.1 mL sample volume is used in the test procedure. A turbidity may
show at higher levels. Use 5 drops of EDTA Solution in the test procedure and allow the sample to
react for 5 minutes.
Highly buffered Can prevent the correct pH adjustment of the sample by the reagents. Sample pre-treatment may be
samples or extreme necessary. Adjust the sample pH to 3–5 before the test is started. Correct the test result for the
sample pH dilution from the volume addition.


Accuracy check
Items to collect:
• Iron Voluette® Ampule Standard, 25 mg/L
• Ampule breaker
• Pipet, TenSette®, 0.1–1.0 mL and tips
4 Iron, Total, FerroVer Method (multi-range: 3.0, 30.0, 300.0 mg/L)

Mix well.
instrument.

instrument.
Items to collect:
• Iron Standard Solution, 100 mg/L
• 2-mL volumetric pipet, Class A and pipet filler safety bulb
• Deionized water
1. Prepare a 2.00 mg/L iron standard solution as follows:

a. Use a pipet to add 2.00 mL of 100 mg/L iron standard solution into the volumetric
flask.
solution.
Method performance
265 2.00 mg/L Fe 1.99–2.01 mg/L Fe 0.021 mg/L Fe
Summary of method
FerroVer Iron Reagent converts all soluble iron and most insoluble forms of iron in the
sample to soluble ferrous iron. The ferrous iron reacts with the 1-10 phenanthroline
indicator in the reagent to form an orange color in proportion to the iron concentration.
The measurement wavelength is 510 nm for spectrophotometers or 520 nm for
colorimeters.
Iron, Total, FerroVer Method (multi-range: 3.0, 30.0, 300.0 mg/L) 5

Required reagents

®
FerroVer Iron Reagent Powder Pillow1, 10-mL 1 100/pkg 2105769
EDTA Solution, 1 M 2 drops 50 mL SCDB 2241926
1 FerroVer is a registered trademark of Hach Company
Iron Standard Solution, 100-mg/L Fe 100 mL 1417542

®
Iron Standard Solution, 10-mL Voluette Ampule, 25-mg/L Fe 16/pkg 1425310
®
®
®
Pipet, volumetric, Class A, 2-mL each 1451536
Hydrochloric Acid, concentrated 500 mL 13449

Nitric Acid, concentrated 500 mL 15249
Filter, glass fiber membrane, 1.5-micron, 47-mm 100/pkg 253000
Filter membrane filter holder, 47-mm each 234000
RoVer Rust Remover 454 g 30001
Spoon, measuring, 0.1-g each 51100

pH DOC316.53.01323
USEPA electrode method Method 10257

pH meter
Scope and application: For water, wastewater, brine solutions, produced waters and hydraulic fracturing
waters1.
1 Adapted from Standard Method 4500-H+B, ASTM Method D1293-84(90)/(A or B) and USEPA Method 150.
Test preparation
Meter Standard probe Rugged probe
HQ40d, HQ30d or HQ11d Gel: PHC101 PHC10105, PHC10110, PHC10115, PHC10130
Liquid: PHC301
Before starting
Condition the electrode for the best response time. To condition the electrode, soak the electrode for several minutes in a
solution that has almost the same pH and ionic strength as the sample.
For rugged electrodes, it may be necessary to remove the shroud before measurement and calibration.
Air bubbles under the sensor tip can cause slow response or measurement errors. To remove the bubbles, carefully shake
the probe.
To save data automatically, set the measurement mode to Press to Read or Interval. When the measurement mode is
Continuous, select Store to save data manually.
Rinse the electrode between measurements to prevent contamination.
Keep the electrode in a pH storage solution when not in use. Refer to the probe documentation.
equipment.
Items to collect
Beaker or sample containers 3

pH buffers (4.0, 7.0, 10.0) 3
1
Sample collection
• Samples must be analyzed immediately after collection and cannot be preserved for
later analysis.
Test procedure
1. Rinse the probe with 2. Laboratory test: Put the 3. Push Read. A progress 4. Rinse the probe with
deionized water. Dry the probe in a beaker that bar is shown. When the deionized water. Dry the
probe with a lint-free cloth. contains the solution. measurement is stable, the probe with a lint-free cloth.
Remove air bubbles from lock icon is shown.
under the probe tip. Stir the
sample at a slow to
moderate rate.
Field test: Put the probe in
the sample. Move the probe
up and down to remove
bubbles from the electrode.
Make sure that the
temperature sensor is put
fully into the sample.
Calibration procedure
1. Prepare two or three 2. Add a stir bar and put the 3. Rinse the probe with 4. Put the probe in the
fresh buffer solutions in beaker on a magnetic deionized water. Dry the solution. Do not let the
separate beakers. If two stirrer. Stir at a moderate probe with a lint-free cloth. probe touch the stir bar,
buffers are used, use a 7.0 rate. bottom or sides of the
and a 4.0 or a 7.0 and a container. Remove air
10.0 pH buffer solution. bubbles from under the
probe tip.
2 pH, USEPA electrode method for oil and gas field waters
5. Push Calibrate. The 6. Push Read. A progress 7. Measure the remaining 8. Push Done. A calibration
standard solution value is bar is shown. When the buffer solutions. summary is shown when the
shown. measurement is stable, the minimum number of
lock icon is shown. calibration standards are
measured.
9. Push Store to accept the

calibration.
Interferences
The sodium error is low but increases at pH values that are higher than pH 11. The acid
error is negligible. Refer to the electrode or the meter documentation.
Accuracy check
Slope test
The electrode operation is satisfactory when the calibration slope is within the specified
range (typically –58 mV (±3) at 25 °C).
Calibration accuracy
Measure the pH of a fresh buffer solution. A calibration is satisfactory when the measured
pH value agrees with the known pH value of the buffer solution.
Clean the probe
Clean the probe when:
• Drifting/inaccurate readings occur as a result of contamination on the glass sensor or
the probe being left dry for extended periods of time.
• Slow stabilization time occurs as a result of contamination on the glass sensor.
• A calibration error occurs as a result of contamination on the glass sensor.
For general contaminants:
2. Soak the glass bulb for 12 to 16 hours in Hach Electrode Cleaning Solution.
For fats, grease and oils:
pH, USEPA electrode method for oil and gas field waters 3
1. Soak the glass bulb in a warm detergent solution for up to 2 hours.
Method performance
The accuracy of the measurements depends on many factors that are related with the
overall system, which includes the meter, the probe and calibration solutions. Refer to the
meter or probe documentation for more information.
Summary of method
A combination pH electrode develops an electrical potential at the glass/liquid interface.
At a constant temperature, this potential varies linearly with the pH of the solution.
The pH is a measure of the hydrogen ion activity in a solution and is defined as –log10aH
+, where aH+ is the activity of the hydrogen ion. The sample pH can change when carbon
dioxide is absorbed from the atmosphere. In water that has a high conductivity, the buffer
capacity is typically high and the pH does not change significantly.

HQ11d portable pH meter each HQ11d53000000
IntelliCAL™ pH gel probe, standard with 1 m cable each PHC10101
IntelliCAL™ pH gel probe, standard with 3 m cable each PHC10103
IntelliCAL™ pH liquid probe, standard with 1 m cable each PHC30101
IntelliCAL™ pH liquid probe, standard with 3 m cable each PHC30103
IntelliCAL™ pH gel probe, rugged with 5 m cable each PHC10105
Refill solution and storage
pH filling solution1, 3 M KCl, saturated with AgCl 28 mL 2841700

pH electrode storage solution 500 mL 2756549
1 Use with the pH liquid probes.
pH color-coded buffer solution kit (NIST), 500 mL, includes: 1 2947600

pH 4.01 ± 0.02 pH buffer (NIST) 500 mL 2283449
4 pH, USEPA electrode method for oil and gas field waters
Recommended standards (continued)
Powder pillows:
pH 4.01 ± 0.02 pH buffer powder pillow (NIST) 50/pkg 2226966
Radiometer Analytical (IUPAC Series certified pH standards):
pH 1.679 ± 0.010 at 25 °C (77 °F) 500 mL S11M001
pH 4.005 ± 0.010 at 25 °C (77 °F) 500 mL S11M002
pH 7.000 ± 0.010 at 25 °C (77 °F) 500 mL S11M004
pH 10.012 ± 0.010 at 25 °C (77 °F) 500 mL S11M007
pH buffer 1.09, technical 500 mL S11M009
Accessories
Beaker, polypropylene, 50-mL, low form each 108041

Beaker, polypropylene, 100-mL each 108042
Bottle, wash, 500-mL each 62011
Stir bar, magnetic, 2.2 x 0.5 cm (7/8 x 3/16 in.) each 4531500
Sample bottle with screw-top cap, polypropylene, 500-mL each 2758101
pH, USEPA electrode method for oil and gas field waters 5
Sulfate DOC316.53.01316
SulfaVer 4 Method1 Method 10248

2 to 70, 20 to 700, 200 to 7000 mg/L SO42– Powder Pillows
Test preparation
for this test.
DR 3800
DR 2800
DR 2700
DR 1900
DR 3900
Before starting
For turbidimetric methods, install the instrument cap or cover on all instruments before ZERO or READ is pushed.
Use the Standard Adjust option with each new lot of reagent for the best results. Refer to the Standard solution method in
Accuracy check on page 4.
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.
The reagents that are used in this test contain barium chloride. Collect the reacted samples for proper disposal.
equipment.
1
Items to collect
®
SulfaVer 4 Reagent Powder Pillows, 10-mL 1
1

• To preserve samples for later analysis, keep the samples at or below 6 °C (43 °F) for
up to 28 days.
• Let the sample temperature increase to room temperature before analysis.
Start
1. Start program 680 2. Add the sample volume 3. If the sample volume is 4. Swirl to mix.
Sulfate. For information that is specified for the test less than 10-mL add
about sample cells, range to a sample cell: deionized water to the
adapters or light shields, 10-mL line.
refer to Instrument-specific • 2–70 mg/L: 10 mL For the dilution factor, refer
information on page 1. • 20–700 mg/L: 1.0 mL to Set the dilution factor
Note: Although the program • 200–7,000 mg/L: on page 3.
name can be different 0.1 mL
Use a TenSette Pipet or
change. glass pipet to measure
0.1 mL or 1.0 mL.
Zero
5. Clean the blank sample 6. Insert the blank into the 7. Push ZERO. The display 8. Add the contents of one
cell. cell holder. shows 0 mg/L SO42–. SulfaVer 4 Reagent Powder
Pillow to the sample cell.
The sample will get cloudy if
sulfate is present in the
sample.
2 Sulfate, SulfaVer 4 (multi-range: 70, 700, 7000 mg/L)

9. Swirl the sample cell to 10. Start the instrument 11. Clean the prepared 12. Within 5 minutes after
mix. Undissolved powder timer. A 5-minute reaction sample cell. the timer expires, insert the
will not affect accuracy. time starts. prepared sample into the
Do not move the sample cell cell holder.
during the reaction period.
Read
13. Push READ. Results 14. Clean the sample cell

show in mg/L SO42–. immediately after each test
with soap, water and a
brush.
Interferences
Barium Interferes at all levels. The higher the relative barium concentration when compared to the sulfate
concentration, the higher the error. Samples with high barium concentrations will generally give a
result that is 20% lower than the actual sulfate concentration.
Calcium More than 20,000 mg/L as CaCO3
Chloride More than 40,000 mg/L as Cl–
Magnesium More than 10,000 mg/L as CaCO3
Silica More than 500 mg/L SiO2


Sulfate, SulfaVer 4 (multi-range: 70, 700, 7000 mg/L) 3

Accuracy check
Items to collect:
• Sulfate Ampule Standard Solution, 2500 mg/L sulfate
• Ampule breaker
• Pipet, TenSette®, 0.1–1.0 mL and tips
• Mixing cylinders (3), 25 mL
Mix well.
instrument.

instrument.
Items to collect:
• Sulfate standard solution, 1000 mg/L
• 5-mL volumetric pipet, Class A and pipet filler safety bulb
• Deionized water
1. Prepare a 50 mg/L sulfate standard solution as follows:

a. Use a pipet to add 5.0 mL of 1000 mg/L sulfate standard solution into the
volumetric flask.
solution.
4 Sulfate, SulfaVer 4 (multi-range: 70, 700, 7000 mg/L)

Method performance
680 40 mg/L SO42– 30–50 mg/L SO42– 0.4 mg/L SO42–
Summary of method
Sulfate ions in the sample react with barium in the SulfaVer 4 and form a precipitate of
barium sulfate. The amount of turbidity formed is proportional to the sulfate concentration.
The measurement wavelength is 450 nm for spectrophotometers or 520 nm for
colorimeters.
Pollution prevention and waste management
Reacted samples contain barium and must be disposed of as a hazardous waste.
Dispose of reacted solutions according to local, state and federal regulations.
Required reagents

®
SulfaVer 4 Reagent Powder Pillow1, 10-mL 1 100/pkg 2106769
1 SulfaVer is a registered trademark of Hach Company.
Sulfate Standard Solution, 1000-mg/L as SO4 500 mL 2175749

Sulfate Standard Solution, 2500-mg/L, 10-mL ampules as SO4 16/pkg 1425210
Mixing cylinder, graduated, 25-mL each 189640

®
Ampule Breaker, 10-mL Voluette Ampules each 2196800
Pipet, volumetric 5.00-mL each 1451537
Pipet filler 1 1465000
®
®
®
®
Sulfate, SulfaVer 4 (multi-range: 70, 700, 7000 mg/L) 5

Sulfide, HR DOC316.53.01319
Methylene Blue Method1 Method 10254

0.01 to 0.70, 0.1 to 7.0, 1 to 70 mg/L S2– Reagent Solution
Test preparation
for this test.
DR 3800
DR 2800
DR 2700
DR 1900
DR 3900
Before starting
Samples must be analyzed immediately after collection and cannot be preserved for later analysis.
Some sulfide loss can occur if dilution is necessary.
equipment.
Items to collect
Sulfide 1 Reagent 1–2 mL

Sulfide 2 Reagent 1–2 mL
Pipet or mechanical pipettor (appropriate sample and reagent size) 1
1
2
Stoppers 2
Water, deionized 10 mL
Sample collection
• Samples must be analyzed immediately after collection and cannot be preserved for
later analysis.
• Collect samples in clean glass or plastic bottles with tight-fitting caps. Completely fill
the bottle and immediately tighten the cap.
• Prevent agitation of the sample or exposure to air.
Methylene Blue method
Start
1. Start program 691 2. Prepare the blank: Fill a 3. Prepare the sample: 4. Spectrophotometers:
Sulfide HR. For information sample cell with deionized Add the sample volume that Add deionized water to the
about sample cells, water. Use 10 mL for is specified for the test 10-mL line. Colorimeters:
adapters or light shields, spectrophotometers and range to a clean sample Add deionized water to the
refer to Instrument-specific 25 mL for colorimeters. cell. Refer to Table 2 25-mL line.
information on page 1. on page 3. To prevent sulfide loss, do
Note: Although the program Use a pipet to measure not mix the sample more
name can be different small volumes. than necessary.
change.
2 Sulfide, Methylene Blue Method (multi-range: 0.70, 7.0, 70 mg/L)

5. Add Sulfide 1 Reagent to 6. Swirl to mix. 7. Add Sulfide 2 Reagent to 8. Put the stopper on both
each sample cell. Use each sample cell. Use sample cells with a stopper.
0.5 mL of reagent for 0.5 mL of reagent for Invert to mix. The solution
spectrophotometers. Use spectrophotometers. Use shows pink and then blue if
1.0 mL of reagent for 1.0 mL of reagent for sulfide is in the sample.
colorimeters. colorimeters.
Zero
9. Start the instrument 10. When the timer expires, 11. Insert the blank into the 12. Push ZERO. The
timer. A 5-minute reaction clean the blank sample cell. cell holder. display shows 0 mg/L S2–.
time starts.
Read
13. Clean the prepared 14. Insert the prepared 15. Push READ. Results
sample cell. sample into the cell holder. show in mg/L S2–.
Select a sample volume

Table 2 Sample volumes and ranges
Range Spectrophotometer volume Colorimeter volume
0.01–0.70 mg/L (LR) 10 mL 25 mL
0.1–7.0 mg/L (MR) 1.0 mL 2.5 mL
1–70 mg/L (HR) 0.1 mL 0.25 mL

Sulfide, Methylene Blue Method (multi-range: 0.70, 7.0, 70 mg/L) 3


Soluble sulfides
To measure soluble sulfides, use a centrifuge to separate the solids. To make an
estimate of the amount of insoluble sulfides in the sample, subtract the soluble sulfide
concentration from the total (with solids) sulfide concentration.
1. Fill a centrifuge tube completely with sample and immediately cap the tube.
2. Put the tube in a centrifuge and run the centrifuge to separate the solids.
3. Use the supernatant as the sample in the test procedure.
Interferences
substance
Barium Concentrations more than 20 mg/L barium react with the sulfuric acid in Sulfide 1 Reagent and form a
BaSO4 (barite) precipitate. To correct for this interference:
1. Dilute the sample in the test procedure as follows:
• Spectrophotometers: use a 0.1-mL or 1.0-mL sample volume and add deionized water to the 10-
mL mark.
• Colorimeters: use a 0.25-mL or 2.5-mL sample volume and add deionized water to the 25-mL
mark.
2. Add both Sulfide 1 and Sulfide 2 reagents per the procedure steps.
3. After the 5-minute reaction period, pour the sample into a 50-mL beaker.
4. Pull the sample into a Luer-Lock syringe (10 cc for spectrophotometers or 60 cc for colorimeters).
5. Put a 0.45-μm filter disc on the Luer-Lock tip and filter the sample into a clean sample cell for
measurement. Use deionized water to prepare the blank.
6. Set the instrument zero and read the result, per the procedure steps.
7. Multiply by the appropriate dilution factor for the dilution used (10 or 100).
Strong reducing Prevent the full color development or reduce the blue color
substances such
as sulfite,
thiosulfate and
hydrosulfite
Sulfide, high High concentrations of sulfide can inhibit the full color development. Use a diluted sample in the test
levels procedure. Some sulfide loss can occur when the sample is diluted.
Turbidity Pre-treat the sample to remove sulfide, then use the pre-treated sample as the blank in the test procedure.
Prepare a sulfide-free blank as follows:
1. Measure 25 mL of sample into a 50-mL Erlenmeyer flask.

2. Add 30-g/L Bromine Water by drops with constant swirling until a yellow color remains.
3. Add 30-g/L Phenol Solution by drops with constant swirling until the yellow color is removed.
4. Use this solution to replace the deionized water blank in the test procedure.
4 Sulfide, Methylene Blue Method (multi-range: 0.70, 7.0, 70 mg/L)

Accuracy check
Sulfide standard solutions are not stable and must be prepared by the user. Refer to
Standard Methods, 4500S2– for preparation and standardization instructions.
Method performance
691 0.52 mg/L S2– 0.50–0.54 µg/L S2– 0.005 mg/L S2–
Summary of method
Hydrogen sulfide and acid-soluble metal sulfides react with N,N-dimethyl-p-
phenylenediamine sulfate to form methylene blue. The intensity of the blue color is
proportional to the sulfide concentration. High sulfide levels in oil field waters may be
determined after proper dilution. The measurement wavelength is 665 nm for
spectrophotometers or 610 nm for colorimeters.
Pollution prevention and waste management
Reacted samples contain hexavalent chromium and must be disposed of as a hazardous
waste. Dispose of reacted solutions according to local, state and federal regulations.
Required reagents
Water, deionized varies 4L 27256

Sulfide Reagent Set — — 2244500
Includes:
Sulfide 1 Reagent 1–2 mL 100 mL MDB 181632
Sulfide 2 Reagent 1–2 mL 100 mL MDB 181732
Required apparatus

®
®
®
Pipet, TenSette 1.0–10.0 mL 1 each 1970010
®
Pipet Tips, for TenSette Pipet, 1.0–10.0 mL varies 50/pkg 2199796
Sulfide, Methylene Blue Method (multi-range: 0.70, 7.0, 70 mg/L) 5

Beaker, 50-mL each 50041H

Bromine Water, 30-g/L 29 mL 221120
Flask, Erlenmeyer, 50-mL each 50541
Phenol Solution, 30-g/L 29 mL 211220
Pipet, serological, 10-mL each 53238
Syringe, 10-cc, Luer-Lock tip each 2202400
Syringe, 60 cc, Luer-Lock tip 1 2258700
Syringe filter, 0.45-µm, 33-mm PVDF 50/pkg 2513603

TPH (Total Petroleum Hydrocarbons)DOC316.53.01142
Immunoassay1 Method 10050
Scope and application: For soil, water, produced waters and hydraulic fracturing waters.
1 This test is semi-quantitative. Results are shown as more or less than the threshold value used.
Test preparation
Instrument specific information

Table 1 shows all of the instruments that can be used for this test. The table also shows
adapter requirements for the instruments that use them.
To use the table, select an instrument, then read across to find the corresponding
information for this test.
Instrument Adapter
DR 6000 —
DR 5000 A23618
DR 3900 LZV846 (A)
DR 1900 9609800 or 9609900 (A)
DR 3800, DR 2800, DR 2700 LZV583
Before starting
This method analyzes for TPH in soil or water samples. For soil analysis, do the Soil Extraction procedure before the
Immunoassay procedure. For water analysis, start with the Immunoassay procedure. The test requires about 20 to
30 minutes for complete analysis. A maximum of 10 tests can be prepared at the same time.
Before the procedure starts, read the full procedure. Identify and prepare all the necessary reagents, cuvettes and other
apparatus, then start the procedure.
Timing is very important in this procedure. Follow the instructions carefully.
It is very important to use a consistent technique to mix the solution in the cuvettes. Refer to Use of the 1-cm
MicroCuvette rack on page 7. If the cuvettes are individually mixed, the results can be less consistent.
Be careful with the cuvettes. A scratch on the inner or outer cuvette surfaces can cause incorrect results. Carefully clean the
outer surfaces with a clean, absorbent cloth or tissue before use.
Antibody cuvettes and enzyme conjugate are made in matched lots. Do not mix reagent lots.
Keep the color developing solution out of direct sunlight to prevent deterioration.
The cuvette rack can be inverted with the cuvettes in the rack. This lets the user prepare many samples at the same time.
The cuvettes stay in the rack until the results are read in the instrument.
The recommended temperature for reagent storage is 4 °C (39.2 °F). Let the reagent temperature increase to room
temperature before analysis.
The Soil Extractant contains methyl alcohol, which is poisonous and flammable. Review the Safety Data Sheets
(MSDS/SDS) for the chemicals that are used. Use the recommended personal protective equipment.
Each reagent set has 20 antibody cuvettes. Use one antibody cuvette for each calibrator and each sample. Cuvettes are not
reusable.
Use protective nitrile gloves for this procedure.
1
equipment.
Items to collect
TPH Reagent Set 1

Caps, flip spout 1
Cylinder, graduated 10-mL 1
Marker, laboratory 1
Pipet, TenSette, 0.1–1.0 mL 1
Pipet tips, for TenSette Pipet, 0.1–1.0-mL 1
Rack, for 1-cm Micro Cuvettes 1
Scoop, 5 g 1
Soil extraction kit varies
Water, deionized varies
Wipes, disposable 1
Wiretrol pipet 1

• Analyze the samples as soon as possible for best results.
• If sample storage is necessary, collect the samples in glass or Teflon® containers.
Clean the containers with soap and water, then rinse the containers with methanol.
Use Teflon-lined caps for the containers. If Teflon-lined caps are not available, use
aluminum foil as a substitute cap liner. Rinse the aluminum foil with methanol before
use.
• For water samples, completely fill the container (no head space) and immediately
tighten the cap.
• Keep soil samples in storage at 6 °C (43 °F) for a maximum of 14 days.
• Keep water samples in storage for a maximum of 24 hours. Put the sample in an ice
bath or a refrigerator to limit the loss of volatile compounds.
2 TPH in Soil, Immunoassay Method

Use of the Wiretrol Pipet
The Wiretrol Pipet accurately measures small quantities of liquids. The Wiretrol Pipet has
®
two parts: a Teflon -tipped plunger and a calibrated capillary tube. The plunger can be
used many times. Discard the capillary tubes after one use.
1. Make sure that the 2. Push the plunger tip to 3. Insert the capillary tube 4. To release the liquid,
plunger tip is wet with the the other end of the capillary below the surface of the insert the tip of the capillary
liquid. Carefully insert the tube. Stop when the plunger liquid. Slowly and smoothly, tube below the surface of
plunger tip into the end of tip barely extends beyond pull the plunger up until the the receiving solution, and
the capillary tube with the the end of the capillary tube. bottom of the plunger tip push the plunger downward
colored band. reaches the applicable in one smooth motion.
volume line. Touch the end Change capillary tubes for
of the tube to the side of the each calibrator and sample.
vessel to release drops that
remain on the capillary tube
tip.
Soil extraction procedure
1. Weigh 10 g of soil in the 2. Carefully pour the soil 3. Use the 5-gram scoop to 4. Use the graduated
plastic weighing boat. into an extraction vial. add one scoop of sodium cylinder to add 10 mL of Soil
sulfate to the extraction vial. Extractant into the extraction
vial.
TPH in Soil, Immunoassay Method 3

5. Put the cap on the 6. Let the particles settle for 7. Use the disposable pipet 8. Put the filtration plunger
extraction vial tightly. Shake a minimum of 1 minute. to remove 1.0 to 1.5 mL into the filtration barrel. Set
vigorously for 1 minute. Carefully open the from the top of the liquid the filtration assembly on a
extraction vial. layer. Add the removed table or flat surface. Push
liquid to the filtration barrel. firmly on the plunger until
Do not use more than the sample extract is forced
1.5 mL. The pipet can upward into the center of the
measure in 0.25-mL plunger.
increments. Use the resulting filtrate for
the immunoassay
procedure.
Immunoassay procedure
Start
1. Push SINGLE 2. Put marks on the 3. Insert the cuvettes into 4. Soil samples: Use a
WAVELENGTH>OPTIONS, cuvettes to identify the the rack. Make sure that the pipet to add 0.5 mL of
then the λ key. Enter 450 samples and calibrators. cuvettes are secure. Do not Diluent Solution into each
nm and push OK. use force to put them into calibrator and sample
Refer to the instrument position because the cuvette. The same pipette
documentation for cuvettes can spill or can be tip can be used for this step.
orientation. difficult to remove. Water samples: Use a pipet
to add 0.5 mL of each water
sample into a sample
cuvette. Use a new pipet for
each sample.

5. Use the Wiretrol pipet to 6. Soil samples: Use a 7. Immediately use a pipet 8. Start the instrument
add 50 µL of each Wiretrol pipet to add 50 µL to add 0.5 mL of TPH timer. The reaction time
calibrator to the applicable of the filtered extract from Enzyme Conjugate into starts.
calibrator cuvette. Mix the the soil extraction each calibrator and sample
cuvettes after each addition. procedure. Refer to Soil cuvette. The same pipette
Use a separate capillary extraction procedure tip can be used for this step.
tube for each solution. on page 3. Use a separate
Have the necessary capillary tube for each
apparatus ready for this solution. Mix the contents of
step and the next four the cuvettes after each
steps. Do not wait—do addition.
these steps quickly. Water samples: Use a
Wiretrol pipet to add 50 µL
of methanol into each
sample cuvette. Mix the
contents of the cuvettes
after each addition.
9. Immediately mix the 10. After 5 minutes, mix 11. At the end of the 12. Fully rinse each cuvette
cuvettes for 30 seconds. the contents of the rack a 10-minute reaction period, with deionized water four
Refer to Use of the 1-cm second time for 30 seconds. discard the contents of all times. Discard the contents
MicroCuvette rack the cuvettes into a waste into the waste container for
on page 7 for the correct container for disposal. disposal. Turn the cuvettes
mixing procedure. and rack upside down on a
paper towel to dry. Carefully
tap the cuvettes on the
towel to remove the liquid.

13. Start color 14. Start the instrument 15. Immediately mix the 16. After 5 minutes, mix
development: Timing is timer. The reaction time cuvettes for 30 seconds. the contents of the rack a
very important. Make sure starts. second time for 30 seconds.
that the cuvettes are still in
position in the rack. Use the
pipet to add 0.5 mL of Color
Developing Solution into
each Antibody Cuvette. Use
a new pipette tip for each
cuvette.
17. When the timer expires, 18. Slide the rack back and 19. Put a mark on a zeroing 20. Clean all of the
use a pipette to add 0.5 mL forth for 20 seconds. The cuvette to identify it as the cuvettes.
of Stop Solution into each blue solution color changes blank. Fill the cuvette with
cuvette with the same to yellow. deionized water.
pipette tip. Consistent
technique is very important.
Add the solution in the same
sequence that was used for
the Color Developing
Solution addition.
Zero Read
21. Insert the blank into the 22. Push ZERO. The 23. Insert the first calibrator 24. Push READ. Results
cell holder. display shows 0.000 Abs. into the cell holder. show in Abs. Record the
result.

25. Read the absorbance
values of the remaining
calibrators and samples.
Record the results. Refer to
Interpret and report the
results on page 8.
Interferences
Chlorine (water samples only) Interferes above 2 ppm. To remove chlorine from the sample,
add 1 drop of 0.1 N sodium thiosulfate per 100 mL of sample.
Use of the 1-cm MicroCuvette rack

Use the MicroCuvette rack to get accurate and precise results for the immunoassay
procedure during the analysis of several samples at a time. Refer to Figure 1.
Insert the cuvettes in the rack—Use the MicroCuvette rack to securely hold cuvettes
that are set in the rack. Before the procedure starts, identify each cuvette with a sample
or a calibrator number. Correctly insert the cuvettes in the rack. Do not force the cuvettes
into the rack because the sample can spill or the cuvettes can be difficult to remove. The
cuvettes must stay in position if the rack is inverted and carefully tapped.
Mix the sample—Put the rack on a hard, flat surface that is at least twice the length of
the rack. Refer to Figure 1. Hold one end of the rack, then vigorously slide the rack back
and forth along its axis for 30 seconds. The rack moves through a distance equal to its
own length in each direction.
Figure 1 MicroCuvette rack

Interpret and report the results
There is an inverse relationship between the concentration of TPH and the absorbance
reading. In other words, the higher the reading, the lower the concentration of TPH. Refer
to Table 2.
Table 2 Relative TPH concentration
If the sample absorbance reading is... then the sample concentration is...
Smaller than the calibrator reading Larger than the calibrator reading
Larger than the calibrator reading Smaller than the calibrator reading
For example, if the readings are:

• TPH Calibrator 1 (20 ppm as diesel fuel): 0.480 Abs
• TPH Calibrator 2 (50 ppm as diesel fuel): 0.360 Abs
• Sample 1: 0.200 Abs
The interpretation for a soil sample:
• Sample 1: The sample reading is smaller than the readings for both calibrators. The
sample concentration of TPH is larger than 50 ppm diesel fuel.
• Sample 2: The sample reading is between the readings for the calibrators. The
sample concentration of TPH is between 20 ppm and 50 ppm diesel fuel.
• Sample 3: The sample reading is larger than the readings for both calibrators. The
sample concentration of TPH is smaller than 20 ppm diesel fuel.
The interpretation for a water sample:
• Sample 1: The sample reading is smaller than the readings for both calibrators. The
sample concentration of in the sample is larger than 5 ppm diesel fuel.
• Sample 2: The sample reading is between the readings for the calibrators. The
sample concentration of TPH is between 2 and 5 ppm diesel fuel.
• Sample 3: The sample reading is larger than the readings for both calibrators. The
sample concentration of TPH is smaller than 2 ppm diesel fuel.
Reagent storage and handling

1. Always wear gloves and eyewear for protection.
2. For long-term storage, make sure that the reagents are not in direct sunlight. Keep
the reagent set at 4 °C (39.2 °F) when not in use. Warm the reagents to room
temperature before use.
3. When not in use, seal the foil pouch that contains the antibody cuvettes.
4. If the Stop Solution is in contact with the eyes, rinse fully for 15 minutes with cold
water and get immediate medical help.
Sensitivity
The antibodies used in the TPH Test Kit react with a variety of compounds found in
petroleum fuels. Each TPH calibrator is formulated to show a known concentration of
diesel fuel. Refer to Table 3 and Table 4 to use calibrators for other TPH compounds.
For example, to use the TPH calibrators for gasoline, find "Gasoline" in the correct table
column. Then, read across the row to find the ppm of that hydrocarbon for each
calibrator. For gasoline, TPH calibrator 1 = 15 ppm, TPH calibrator 2 = 35 ppm, etc.

Table 3 TPH compounds in soil
Compound TPH calibrator TPH calibrator TPH calibrator 3 (ppm) TPH calibrator 4 (ppm)
1 (ppm) 2 (ppm)
Diesel fuel 20 50 100 200
Gasoline 15 35 70 140
Kerosene 35 75 140 250
Benzene 20 45 85 160
Toluene 15 30 50 90
Ethylbenzene 5 15 35 75
m-Xylene 9 20 35 70
o-Xylene 10 20 40 80
p-Xylene 3 5 9 16
BTEX 5 15 25 45
Table 4 TPH compounds in water

Compound TPH calibrator TPH calibrator TPH calibrator TPH calibrator
1 (ppm) 2 (ppm) 3 (ppm) 4 (ppm)
Diesel fuel 2 5 10 20
Gasoline 1.5 3.5 4 14
Kerosene 3.5 7.5 14 24
Benzene 2 4.5 8.5 16
Toluene 1.5 3 5 9
Ethylbenzene 0.5 1.5 3.5 7.5
m-Xylene 0.9 2 3.5 7
o-Xylene 1 2 4 8
p-Xylene 0.3 0.5 0.9 16
BTEX 0.5 1.5 2.5 4.5
Dilute a water sample

For higher levels of TPH in water than those shown in Table 4 on page 9, dilute the
sample with deionized water. To dilute a sample, refer to Table 5, then add that sample
volume to a graduated cylinder and dilute to 50 mL with deionized water. Do the test.
Refer to Table 4 on page 9 again to multiply the calibrator levels by the dilution multiplier.
For example, if a 0.5 mL water sample is diluted to 50 mL, the calibrator levels in Table 4
on page 9 for diesel fuel are approximately 200, 500, 1000 and 2000 ppm.
Table 5 Dilution multipliers
mL sample Dilution multiplier
0.5 100
1.0 50
2.0 25
5.0 10
10.0 5
25.0 2

Summary of method
This method is the semi-quantitative screening for TPH based on thresholds as diesel
fuel in the concentrations that follow:
• Soil—20, 50, 100, 200 ppm as diesel fuel
• Water—2, 5, 10, 20 ppm as diesel fuel
Immunoassay tests use antigen/antibody reactions to detect specific organic compounds
in water and soil. The walls of plastic cuvettes are layered with antibodies that are specific
for TPH. The antibodies selectively remove TPH from complex sample matrices. A
prepared sample and a reagent with enzyme-conjugate molecules (analyte molecules
attached to molecules of an enzyme) are added to the Antibody Cuvettes. During
incubation, enzyme-conjugate molecules and TPH compete for binding sites on the
antibodies. Samples with higher levels of analyte have more antibody sites occupied by
the analyte and fewer antibody sites occupied by the enzyme-conjugate molecules.
After incubation, the sample and unbound enzyme conjugate are rinsed from the cuvette
and a color-development reagent is added. The enzyme in the conjugate catalyzes the
development of color. Thus, there is an inverse relationship between color intensity and
the amount of TPH in the sample. The resulting color is then compared with a calibrator
to determine if the analyte concentration in the sample is larger or smaller than the
threshold levels. The TPH concentration is inversely proportional to the color
development—the lighter the color, the higher the TPH concentration. The test results are
measured at 450 nm.
Required reagents
Soil Extraction Kit 1 each 2775100

TPH Reagent Set 1 20 cuvettes 2774300
Water, deionized varies 500 mL 27248
Required apparatus
Balance, portable, 300 g capacity 1 each 2796900

Caps, flip spout (for 500-mL deionized water bottle) 1 2/pkg 2581802
Marker, laboratory 1 each 2092000
Gloves, nitrile, medium 1 100/pkg 2550502
®
®
®
Pipet, Wiretrol , 10–50 µL 1 each 2852200
®
Pipet, Wiretrol , 50–1000 µL 1 each 2568905
Rack, for 1-cm Micro Cuvettes 1 each 4879900
Safety goggles, vented 1 each 2550700
Soil scoop, 5-g, 4.25-cc 1 20/pkg 2657205
Timer, talking 1 each 2764400
Wipes, disposable 1 280/pkg 2097000
Soil extraction refill kit, for 2775100, includes: 1 each 2775200
Dropper, LDPE, 0.5 and 1.0-mL 1 20/pkg 2124720

Required apparatus (continued)
Filter and barrel assembly 1 20/pkg 2567620

Sodium sulfate, anhydrous 1 250 g 709929
Soil extraction solution 1 200 mL 2567729
Soil sample container 1 20/pkg 2592920
Weighing boat, 8.9-cm square 1 20/pkg 2179020
Spatula, disposable 1 2/pkg 2569320
Graduated cylinder, 10-mL each 108138

Sodium Thiosulfate Standard Solution, 0.1 N 100 mL MDB 32332

© Hach Company/Hach Lange GmbH, 2007, 2010, 2012, 2014. All rights reserved. 07/2014, Edition 10
Procedures Explained
1
2
Procedures Explained: Barium
Barium
Introduction
Barium is a naturally occurring byproduct of the drilling process. Barium, along with
strontium, calcium and bicarbonate, can cause scale deposits in flow line pipes in the
presence of fracturing water with high sulfate concentrations. Barium and strontium react
with sulfate to form a white precipitate, which creates scaling inside the pipes.
Recommended Instrumentation
• BariVer 4 Reagent Powder Pillows (for 10 mL samples) part number 1206499
• Hach DR spectrophotometer/colorimeter suitable for use with Method 8014 or Method
10251 which is written specifically for oil and gas produced and flowback waters.
Matrix Challenges
Strontium will interfere with barium at concentration of 20 mg/L for both analytes. If the
sample concentration of barium and strontium are diluted to a concentration at or below
20 mg/L, the interference from strontium becomes negligible. When strontium is present in
the sample without barium, Sr is undetectable with the BariVer 4 reagent. A 100 mg Sr/L
spike in a sample without Ba produced a concentration of 2 mg Ba/L, which is the
method's lowest detectable concentration.
Figure 1 and Table 1 show the effect that strontium has on the barium concentration when
both Ba and Sr are present at the same concentrations.
Figure 1 Ba spike versus a combination of Ba and Sr at the same concentration levels
3
Procedures Explained: Barium
Table 1 Corresponding data for Figure 1

Ba Spike Concentration Sr Spike recovery at the same
Ba Spike recovery % Difference
(mg Ba/L) conc as the Ba spike (mg Ba/L)1
20 24 30 20
40 42 58 28
50 50 80 38
60 58 92 37
80 72 127 43
100 89 154 42
1 Both Ba and Sr are spiked at the same concentration. For example, the first combined standard set was spiked with 20 mg/L Ba and Sr, the
second set was spiked with both 40 mg/L of Ba and Sr, and so on. As the concentration of both analytes in the combination spike increases,
the % difference between the Ba spike and the combination spike of Ba and Sr increases based on the nature of the Sr interference with the
BariVer 4 chemistry.
If the barium and the strontium concentrations are close to the same concentration, the
analyst can dilute them within the appropriate concentration range for the Ba method (2 to
100 mg/L). Dilute the Ba and Sr concentrations so they are both at or below 20 mg/L to
avoid the Sr interference.
4
Procedures Explained: Hardness, Total and Calcium
Hardness, Total and Calcium
Introduction
Total hardness in water is caused by dissolved minerals, primarily divalent cations. In
natural water systems, calcium and magnesium are the main contributing ions for total
hardness. However, both produced and flowback waters have high levels of barium,
strontium and iron, along with elevated concentrations of calcium and magnesium. All of
these ions will titrate out directly with the EDTA titrant. Elevated levels of calcium can
inhibit the borate and zirconate crosslinking.
Calcium hardness is performed at a different pH than the total hardness titration. The pH
is elevated to at least 13 to precipitate magnesium so just the calcium ion is titrated.
• Digital Titrator Kit (Item number 1690001)
• Total Hardness Reagents, 100 4000 mg/L (Item number 2448100)
• Calcium Hardness Reagents, 100 4000 mg/L (Item number 2447500)
• CDTA Magnesium Salt Powder Pillows (iron interference removal) (Item no. 1408099)
Matrix Challenges
Total Hardness
Produced and flowback water can have elevated levels of barium, strontium and iron.
The presence of iron interference causes a redorange to green endpoint. The iron
concentrations are above 100 mg/L. However, since the hardness concentrations in these
matrices are very high, the use of a smaller sample volume will reduce the iron
interference. After using the smaller sample volume, if iron concentration is still believed to
be present at a concentration above 100 mg/L, the addition of the CDTA powder pillow will
reduce this interference. CDTA does not affect barium or strontium interference and these
ions will be titrated directly along with calcium and magnesium. Therefore, the total
hardness value will include the divalent cations of barium, strontium, calcium and
magnesium. If the barium and strontium concentrations of the sample are known, these
interfering cations can be subtracted from the total hardness value by performing a
molecular weight conversion of both barium and strontium to CaCO3. The hardness
equivalence factor for barium and strontium is 0.729 and 1.142, respectively. Multiply the
barium and strontium concentrations by these equivalence factors to convert their
concentrations to CaCO3 and subtract these values from the total hardness concentration
to achieve a more accurate hardness value for just magnesium and calcium hardness.
See the Hardness Equivalence Factor Table in the total hardness procedure for other
metal hardness equivalence factors. To report the true total hardness of the sample, do
not subtract out the barium and strontium concentrations.
Calcium Hardness
For the calcium hardness titration, laboratory studies have shown that a sample containing
barium and strontium will not precipitate at pH 13, and both will be titrated along with the
calcium in the sample. If strontium and calcium are not present in the sample, the barium
will precipitate at pH 13. However, most produced and flowback water samples have
strontium, calcium and barium present at high concentrations. If the concentrations of
barium and strontium are known, these ions can be subtracted from the calcium hardness
titration in the same manner as the total hardness titration. Convert the barium and
strontium to CaCO3 using the equivalence factors listed above. After subtracting out the
barium and strontium, the resulting value will be the calcium hardness as CaCO3. To
5
Procedures Explained: Hardness, Total and Calcium
convert calcium as CaCO3 to the elemental form of just calcium, multiply the Ca hardness
value by 0.4.
6
Procedures Explained: Iron
Iron
Introduction
Iron is a byproduct of the drilling process, with ferrous (Fe+2) being detrimental to the
fracing fluid. The fracing fluids have chemicals added to prevent the precipitation of metal
oxides, iron being one of the most important metals. When preparing the fracing fluid, the
ferrous iron concentration should be less than 10 mg/L to prevent fluid degradation. The
FerroVer chemistry will detect both ferrous and ferric (Fe+3) iron. Iron in ground water is
normally present in the ferrous form, which oxidizes quickly to ferric iron with exposure to
air.
• FerroVer Iron Reagent Powder Pillows (for 10 mL samples) (item number 2105769)
• EDTA Solution (1M) 50 mL (item number 2241926)
• Hach DR spectrophotometer/colorimeter suitable for measuring the FerroVer 8008
method or Method 10249 which is written specifically for oil and gas produced and
flowback waters.
Determination of iron
Test results are dependent upon sample pretreatment steps and the iron reagent reaction
conditions. The FerroVer Iron Reagent contains strong reducing agents plus 110
phenanthroline indicator. The reducing agents reduce ferric iron present in the sample to
ferrous iron. The phenanthroline indicator then reacts with the ferrous iron to form an
orange color in proportional to the iron concentration. The strong reducing agents in
FerroVer will convert most insoluble iron forms to soluble ferrous iron and be included in
the test results. A total iron test to determine soluble and insoluble iron will require a mild
acid digestion followed by analysis with FerroVer Iron Reagent. Samples that have been
filtered before analysis to remove particulates or samples that are analyzed with iron
reagents containing ascorbic acid as the reducing agent will usually give much lower test
results. It therefore becomes important to document the sample pretreatment steps when
comparing test results with previous analysis or with other outside laboratories using other
colorimetric or instrumental methods of analysis.
Matrix Challenges
In fracing fluids, barium and strontium can be present at high concentrations, and
concentrations above 50 mg/L will interfere with the iron analysis by forming a precipitate.
Strontium by itself will not interfere with the iron analysis, however; when strontium and
barium are in the solution together (this combination is common in fracing fluids) the
strontium acts as a catalyst increasing the barium interference. This precipitate / turbidity
interference can be eliminated with the addition of a 1 M EDTA solution. The EDTA does
not chelate the iron, but will remove barium and strontium from the sample. The amount of
EDTA needed to overcome this interference depends on the concentration of the barium
and strontium in the sample. Laboratory studies have shown that 1 to 2 drops of a 1 M
EDTA solution added to a 10 mL sample volume is sufficient to remove the barium
interference of approximately 50 to 200 mg/L Ba/Sr. Concentrations of 200 to 1000 mg/L
Ba/Sr, use up to 5 drops of 1 M EDTA to eliminate the interference. If there is precipitate in
the sample after the addition of the FerroVer reagent powder pillow, the analyst can add
more EDTA or dilute the sample to reduce the barium/strontium interference. Avoid
adding to much EDTA, up to 10 drops, to the 10 mL sample. Over dosing the sample with
EDTA will impede the color development of the FerroVer reagent. It was observed in the
laboratory that 10 drops of EDTA in a 10 mL sample caused the colorimetric reaction to
take up to 30 minutes to develop. The addition of EDTA will tie up the barium, strontium
and the iron, since they are all cations, but the phenanthroline indicator in the FerroVer
7
Procedures Explained: Iron
reagent has a stronger affinity to the iron than the EDTA does and will eventually complete
the colorimetric reaction. It is recommended to use 5 drops of EDTA or less with the 10 mL
sample volume. At extremely high concentrations of both Ba and Sr in the sample (above
500 mg/L for both), laboratory studies have shown that even with the addition of EDTA at
the upper end of the FerroVer concentration range (2.5 to 3.0 mg/L iron) the color
formation is slower and may take up to 10 minutes for complete color development. For
the most accurate results, it is recommended to dilute the sample to an iron concentration
around 1 mg/L and the barium/strontium combination to around 50 to 200 mg/L; where the
2 to 5 drops of EDTA will work the most effectively to remove the barium/strontium
interference.
8
Procedures Explained: Conductivity and Total Dissolved Solids
Conductivity and Total Dissolved Solids
Introduction
Conductivity is an important parameter for these highly saline industrial water samples.
Through the use of a conversion factor, the conductivity value can be used to determine
an estimated TDS value for the sample. Users can then use this TDS value, and past
sample results, to estimate the appropriate dilution factor needed to analyze other
parameters to track treatment process efficiencies and to identify water quality changes.
Produced and flowback water have conductivity values that are in the mS/cm range, ~10
200+ mS/cm (~10 150 g/L as TDS). As Figure 1 shows, to accurately measure
conductivity values at this elevated level it is necessary to use a 4pole conductivity cell
with an enhancement from either graphite, stainless steel, or platinum*.
Figure 1 Conductivity guidelines
Matrix Challenges
Due to the high ranges of conductivity in these sample matrices, it is recommended to use
a metal enhanced 4pole cell. Users that don't have this type of cell can dilute the sample
to get it into the appropriate range for the cell's specifications. However, laboratory studies
have shown it's possible to produce a 30% increase in conductivity values with the diluted
samples compared to the undiluted samples. Hach recommends not diluting the samples
for conductivity measurements to avoid this error.
Figure 2 shows some of the effects of an increase in conductivity on diluted samples.
* The enhanced 4-poled cells have a layer of metal (graphite, stainless steel, or platinum) on the poles to minimize the effects
of polarization and increase the concentration range. (For more information on conductivity theory, download the Conductivity
Theory and Practice from the Hach website.)
9
Figure 2 Effects of increased conductivity on diluted samples
Sample1 Undiluted Diluted %Diff

A 235 344 31.7
B 208 258.8 19.6
C 197.1 245.8 19.8
D 174.5 205.2 15.0
1 Samples were diluted 1:1 and the conductivity measured. The value was then multiplied by 2 to get the final diluted result.
Higher sample conductivities will produce larger positive errors when the sample is
diluted.
The conductivity cells were calibrated using a single point calibration using three different
standards, 1408 µS/cm, 12.85 mS/cm, and 111.3 mS/cm standard; none of the three
calibrations improved the difference between the undiluted and diluted samples. However,
it is always recommended to calibrate using a calibration standard that approximates the
range of conductivity values expected in the sample to be tested. Figure 3 provides
guidance on choosing the appropriate standard concentration.
10
Figure 3 Guidelines for choosing a conductivity cell and standard
Conductivity standards provided by Hach

• 111.3 mS/cm KCl Standard (1 D) part number S51M001
• 12.85 mS/cm KCl Standard (0.1D) part number S51M002
• 1408 µS/cm KCl Standard (0.01 D) part number S51M003
TDS factors
The different Hach Company meter platforms offer direct measurements for TDS; it is up
to the operator to select the type of conversion factor that best matches the true TDS
value. The TDS is typically used to estimate the amount of total dissolved solids in the
sample. The standard method to determine TDS is to filter and evaporate the sample to
dryness at 180°C, then weigh the residue. Hach Method 8163 is available for determining
the total dissolved solids using the standard method. If required, Method 8163 can be
used to determine the conversion factor for a specific solution or sample matrix.
To determine the conversion factor for a specific solution of a known TDS value, measure
the solution's conductivity and divide the mg/L TDS value by the conductivity value
reported. For example, a solution of a known TDS value of 64 g/L and the measured
conductivity value of 100 mS/cm has a conversion factor of 64/100 or 0.64. It is important
to know the conversion factor being used, especially when comparing your TDS results
with another lab's results, another test site or when comparing results with previously
published or referenced data.
The different TDS concentration conversion options for the HQd meters are as sodium
chloride (NaCl), a generic default factor of 0.5, or a userentered custom value. The
operator can choose any factor within the custom field; a common factor for high salinity
samples is 0.64. For the MP6 meter, the TDS factor options are as NaCl, as potassium
chloride (KCl), 442 and userentered. The MP6's meter default is the KCl which is used for
conductivity, the NaCl is used for resistivity (mineral/salt), the 442 factor is an algorithm
that is used for estimating TDS in natural waters, and the userentered factor option.
11
Maintenance
Due to the nature of the produced and flowback water, the operator needs to be sure to
rinse the conductivity cell off with clean water. Do not allow the cell to soak, or store the
cell in these samples. Once the cell has been rinsed off, blot and store dry.
Ordering information
To order one of the 4pole conductivity cells, refer to Table 1. For more meter and probe
options, visit www.hach.com.
Table 1 CDC401 Graphite Conductivity Cell ordering information

Description Item number
Conductivity Cell (lab), with 1 M cable CDC40101
Conductivity Cell (lab), with 3 M cable (lab) CDC40103
Conductivity Cell (rugged), with 5 M cable CDC40105
12
Procedures Explained: Turbidity and Total Suspended Solids
Turbidity and Total Suspended Solids
Introduction
Turbidity is a measurement of water clarity where solids in the water obstruct the
transmittance of light through the sample. Turbidity is an important water quality parameter
that can indicate the presence of dispersed suspended solids, algae and other
microorganisms, organic material and other minute particles.
Total suspended solids (TSS) is a laboratory gravimetric procedure where the solids from
the water sample are filtered through a 47mm glass fiber filter, dried and weighed to
determine the total nonfilterable residue (TNR) of the sample reported as mg/L.
Both turbidity and total suspended solids can be measured together with a TSS probe.
The probe, which utilizes a modified absorbance measurement, provides a qualitative
analysis for TSS. For the turbidity function, the probe uses a 2channel 90° scattered light
measurement. The units of measure for turbidity are NTU, FNU, and EBC; the units of
measure for the suspended solids are ppm, mg/L, g/L and %.
Turbidity and TSS can be used for process control in the treatment of the produced and
flowback water. At different stages in the treatment process the sample can be analyzed to
determine and trend the treatment's ability to remove the solids from the water. Figure 1
shows how TSS and turbidity measurements trend with the same samples. The data
generated by both methodologies provide the operator with process management
information.
Figure 1 TSS versus Turbidity
• Turbidity measurement: Portable Turbidimeter 2100Q (item number 2100QIS01).
• Laboratory Turbidimeter 2100N (part number 4700000), or 2100AN (item number
4700100)
• Total Suspended Solids: TSS portable probe (item number LXV322.99.00002)
• Laboratory method, Gravimetric method (Hach method 8158) for nonfilterable total
suspended solids.
Measuring turbidity and total suspended solids

Turbidity
The 2100Q is a portable turbidimeter, with a measuring range of 0 to 1000 NTUs. When a
sample is over the 1000 NTU range, a 1:1 dilution will lower the NTU concentration within
appropriate range.
13
Procedures Explained: Turbidity and Total Suspended Solids
For laboratory turbidity measurements choose either the 2100N or AN; the N's measuring
range is 0 to 4000 NTUs, and the AN's measuring range is 0 to 10,000 NTUs.
The TSS portable probe's turbidity measuring range is 0 to 4000 NTUs.
Suspended solids
The laboratory total suspended solids method is the gravimetric procedure where the
sample is filtered, dried and weighed to determine the true quantitative TSS.
The TSS probe has an operating concentration range of 0.001 to 400 g/L.
Matrix Challenges
The laboratory turbidimeters, A and AN, can measure above 1000 NTUs because of the
ratio measurement feature that corrects for color interference. The laboratory
turbidimeters are not portable for field analysis, but they can be used in an onsite mobile
lab. However, for ease of use and smaller footprint, the 2100Q is adequate for most
produced and flowback water samples. If the sample is over range, a simple 1:1 dilution
should lower the turbidity concentration within the 0 to 1000 NTU range. High levels of
color may cause high results.
The challenge for the gravimetric TSS procedure is that this application is a laboratory
test. It is possible to perform the analysis in a mobile lab, but there is an abundance of lab
equipment needed for this procedure, i.e. oven, analytical balance, vacuum pump,
desiccators, etc. The method requires moderate laboratory skill, and test results are not
available for 3 to 4 hours. Samples having a high TSS load or high oil residual levels may
require sample size adjustments.
The TSS portable probe is ideal for measuring suspended solids in the field. Its 10 m cable
allows the probe to be lowered into the storage container to spot check the suspended
solids or turbidity of the produced or flowback water. The probe is best used after
calibration or correlation to the gravimetric TSS procedure. The TSS probe also provides
immediate results for process control and reduces the need for the time consuming
suspended solids lab analysis. Samples having high levels of oil or hydrocarbon residuals
may coat the probe and require routine cleaning. Samples having variable color or
particulate size can cause variable test results.
14
Sample pretreatment by digestion
Several procedures use sample digestion before the total metal content is found.
Digestion uses acid and heat to break organo-metallic bonds and free ions for analysis.
USEPA-approved digestions
For USEPA reporting, USEPA-approved digestions are necessary. There are two
methods for metals analysis: mild and vigorous.
USEPA mild digestion
1. Add concentrated nitric acid to the entire sample at the time of collection. Add 5 mL of
acid per liter (or quart) of sample.
2. Move 100 mL of well-mixed sample to a beaker or flask.
3. Add 5 mL of distilled 1:1 hydrochloric acid (HCl).
4. Increase the temperature of the liquid with a steam bath or hot plate until the volume
has been reduced to 15–20 mL. Do not boil.
5. Use a filter to remove any insoluble material from the sample.
6. Adjust the pH of the digested sample to pH 4. Add 5.0 N Sodium Hydroxide Standard
Solution a drop at a time. Mix thoroughly and examine the pH after each addition.
7. Pour the reduced sample into a 100-mL volumetric flask.
8. Use a small amount of demineralized water to rinse the beaker. Pour the rinse water
into the volumetric flask.
9. Repeat the rinse process a few more times to remove all of the reduced sample from
the beaker.
10. Add demineralized water to fill the volumetric flask to the 100-mL mark.
11. Use the diluted sample in the test procedure. Record the results.
12. Prepare a blank: Repeat steps 1-11 with demineralized water instead of the sample.
13. Subtract the results of the blank analysis from the results of the sample analysis.
USEPA vigorous digestion

For some samples mild digestion will not be sufficient. Use a vigorous digestion to make
sure that all of the organo-metallic bonds are broken.
1. Use redistilled 1:1 Nitric Acid Solution to acidify the entire sample to a pH of less than
pH 2. Do not filter the sample before digestion.
2. Move an appropriate sample volume into a beaker and add 3 mL of concentrated
redistilled nitric acid. Refer to Table 1.
3. Put the beaker on a hot plate and evaporate to near dryness. Make sure that the
sample does not boil.
4. Cool the beaker and add another 3 mL of the concentrated re-distilled nitric acid.
5. Put the cover on the beaker with a watch glass and return it to the hot plate. Increase
the temperature of the hot plate so that a gentle reflux occurs. Add additional acid, if
necessary, until the digestion is complete (generally shown when the digestate is light
in color or does not change color or appearance with continued refluxing).
6. Again, evaporate to near dryness (do not bake) and cool the beaker. If any residue or
precipitate results from the evaporation, add redistilled 1:1 hydrochloric acid (5 mL
per 100 mL of final volume). Refer to Table 1.
7. Warm the beaker. Adjust the sample to pH 4 by drop-wise addition of 5.0 N Sodium
Hydroxide Standard Solution. Mix thoroughly and examine the pH after each addition.
8. Pour the reduced sample into a 100-mL volumetric flask.
9. Use a small amount of demineralized water to rinse the beaker. Pour the rinse water
into the volumetric flask.
1
10. Repeat the rinse process a few more times to remove all of the reduced sample from
the beaker.
11. Add demineralized water to fill the volumetric flask to the 100-mL mark.
12. Use the diluted sample in the test procedure. Record the results.
13. Multiply the result by the correction factor in Table 1.
14. Prepare a blank: Repeat steps 1-13 with demineralized water instead of the sample.
15. Subtract the results of the blank analysis from the results of the sample analysis.
Table 1 Vigorous digestion volumes
Expected metal Suggested sample Suggested volume of Suggested final Correction factor
concentration volume for digestion 1:1 HCl volume after digestion
1 mg/L 50 mL 10 mL 200 mL 4
10 mg/L 5 mL 10 mL 200 mL 40
100 mg/L 1 mL 25 mL 500 mL 500
General Digesdahl digestion

Many samples may be digested with the Digesdahl Digestion Apparatus (2313020). It is
designed to digest samples such as oils, wastewater, sludges, feeds, grains, plating
baths, food and soils. In this procedure, the sample is oxidized by a mixture of sulfuric
acid and hydrogen peroxide. Less than 10 minutes is necessary for the digestion of a dry
sample. About 1 minute/mL is necessary for the digestion of liquid samples. The digestion
is done in a special flat-bottomed, 100-mL volumetric flask. Aliquots (sample portions) are
used for analysis with the colorimetric methods.
Procedures for digestion with the Digesdahl Digestion Apparatus are based on the type
and form of the sample. Refer to the Digesdahl Digestion Apparatus Instruction manual
supplied with the Digesdahl Digestion Apparatus.
Digesdahl digestion is a process that yields a digest that can be used to find metals, total
phosphorus and total Kjeldahl nitrogen (TKN). It is faster than traditional methods, but has
comparable accuracy and precision. The digest can be used with colorimetric,
turbidimetric or titrimetric tests.
The procedures for the Digesdahl Digestion Apparatus vary with the sample type. Sample
types include food products, feeds, grains, wastewater sludges, plating baths, plant
tissues, fertilizers, beverages and oils. Most procedures use a two-phase digestion
process that uses concentrated sulfuric acid and 50% hydrogen peroxide. Sulfuric acid
dehydrates and chars the sample. Hydrogen peroxide is added through the capillary flow
funnel to complete the decomposition. The analyst varies the volume of hydrogen
peroxide used to control the digestion time (exposure to the hydrogen peroxide).
Some samples are more difficult to digest completely (e.g., resistant or refractory
materials, such as nicotinic acid). Several minutes of continued peroxide digestion are
necessary after clearing to get 100% nitrogen recovery. To make sure that there is
complete sample digestion, think about variables such as sample size, solution
temperature and sample contamination. Refer to the Digesdahl Manual (2313018) for
complete information.
Frequently asked questions for digestion procedures
This section provides answers to common questions about digestion.
What should be done if the reading on the instrument is over-range?
The concentration range tables found in digestion procedures are only guidelines. Use a
smaller analysis volume and repeat the procedure. Record the new analysis volume and
use it in the calculation.
Should a reagent blank be prepared each time reagents with the same lot number
are used?
2
To decide, first find the reading of the reagent blank. Set the instrument to zero with
deionized or distilled water. If the reagent blank has an insignificant concentration reading
and the reagents have the same lot number, a reagent blank does not have to be
prepared every time. If the reagent blank shows a reading, analyze it daily or subtract the
reading from the sample reading. If a reagent blank is not analyzed daily, set the
instrument to zero with deionized water.
Does the exact sample amount and analysis volume given in each procedure need
to be used?
The sample amount and the analysis volume for each procedure are only suggested
guidelines. Digest any aqueous solution or suspension sample amount up to 40 mL. Less
than 0.5 g of anhydrous material is necessary for solid or organic liquid samples—as a
routine practice, 0.25 g of sample is used.
How can the initial amount of sample (necessary for digestion) and the analysis
volume to be used be refined?
The amount of sample to be digested is a critical aspect of the digestion. The aliquot size
of the digest to be used in the analysis is also very important. Tables are provided in each
method to find the amount of initial sample to be digested. In order to optimize the
specific test to be done, the equations that follow have been developed. Before these
equations are used, refer to the manual specifications for the sample type.
To use the equations, find the approximate concentration (in ppm, mg/L or mg/kg). Next,
find the range of the colorimetric test to be used (e.g., 0–50 mg/L) and the midpoint of the
test range. This midpoint range is optimum but can be lowered to accommodate very low
sample concentrations. To find the midpoint of the test range, subtract the lower limit of
the range from the higher limit and then divide by 2.
After these determinations are finished, use the equation that follows:
A = (B × C × D) ÷ (E x F)
Where:
A = approximate concentration of sample
B = midpoint of colorimetric test range
C = final volume of digest
D = final volume of analysis
E = sample amount to digest
F = analysis volume of digest
Use algebra to obtain the equations that follow:
Equation 1 is E = (B × C × D) ÷ (A × F)
Equation 2 is F = (B × C × D) ÷ (A × E)
Both equations contain two unknown values, E and F. Some trial and error may be
necessary to get the optimum values.
Use equation 1: If the analysis is for copper, use the CuVer™ method with an initial
sample that contains approximately 150 ppm Cu. The amount of sample necessary for
digestion and the aliquot volume to be used can be found as follows:
Find the test range. In this example, the test range is thought to be 0–5.0 ppm and the
midpoint is 2.5. When the Digesdahl system is used, the final volume of digest is 100 mL
and the procedure calls for a final analysis volume of 25 mL.
Therefore:
A = 150
B = 2.5
C = 100
D = 25
E = unknown
3
F = unknown
Substitute values into equation (1) gives:
E = (2.5 × 100 × 25) ÷ (150 × F) or E = 41.7 ÷ F
Since CuVer Copper Reagent is pH sensitive, a small analysis volume (0.5 mL) is
necessary so that pH adjustment would not be necessary.
With this in mind, a 0.5-mL analysis volume would give:
E = 41.7 ÷ 0.5 = 83.4 mL digestion sample amount
Because the maximum digestion sample amount is 40 mL for Digesdahl digestions, a 0.5-
mL analysis volume is not acceptable for the range. This is where trial and error is
necessary. Next, try a 5.0-mL analysis volume and the equation gives:
E = 41.7 ÷ 5.0 = 8.0 mL digestion sample amount
(Round to the nearest whole number for ease of measure.)
From the calculation, an 8.0 mL sample is digested and a 5.0-mL analysis volume is
taken. A pH adjustment is necessary before analysis.
Use equation 2: Equation 2 may be used when a minimum sample size is necessary or
when a sample has already been digested for one parameter (such as copper) and
measurement for another parameter (such as zinc) is necessary. Continue the example
for copper, above, a zinc test may also be done. The undigested sample contains
approximately 3 ppm zinc and the Zincon method is used. The analysis volume can be
found as follows.
In this example, the Zincon method test range is thought to be 0–2.5 ppm so that the
midpoint of the range is 1.25. Therefore values are:
A=3
B =1.25
C = 100
D = 50
E = 8 (as found above)
substitute: F = (1.25 × 100 × 50) ÷ (3 × 8) = 260 mL
This is an extreme example, but it shows the need to compare the values of D and F to
make sure that the analysis volume (F) is no more than the final analysis volume (D). If F
exceeds D, the analysis cannot be done. A test with a more applicable range is
necessary or a larger sample may be digested for this test. Care must also be taken to
make sure that the volume of digest taken for analysis (F) is higher than 0.1 mL because
accurately pipetting less than 0.1 mL is difficult.
As a comparison, think of the zinc concentration as 75 ppm (A = 75 instead of 3) and
substitute again to get:
F = (1.25 × 100 × 50) ÷ (75 × 8) = 10.5 mL
In this case, the aliquot volume is less than the final analysis volume so analysis may be
done as specified in the procedure.
Why is the factor in the calculation step 75, 2500 or 5000 (depends on the method
used) and where does the factor come from?
In all cases, the factor is a correction for sample dilution. For example, in some tests the
factor is 2500. The Digesdahl digestion total volume is 100 mL, the analysis total volume
is 25 mL and 100 x 25 = 2500. The mL units are not included with the factor because they
cancel out in the formula.
When a slurry is analyzed, how is the total concentration on a dry basis reported?
The sample must be analyzed for moisture content. For necessary apparatus, refer to
Table 2 and Table 3.
4
To find the dry basis weight:

1. Weigh an aluminum dish and record the weight as “A”.
2. Weigh out approximately 2 g of solid sample into the dish. Record the exact weight
added as “B.”
3. Put the dish in the oven (103–105 °C, 217–221 °F) for 2 hours.
4. Put in a desiccator and cool to room temperature.
5. Weigh the aluminum dish with the oven-dried sample. Record as “C.”
Note: The oven-dried material generally is not meant for additional testing and should be
discarded.
6. Use this formula to calculate the sample on a “dry basis.” Test result (dry basis) =
(C – A) ÷ (B – A).
Note: Multiply the test result on an “as is” basis, by the factor above, to report as “dry basis".
Table 2 Necessary apparatus for dry basis weight

Balance, analytical, 120-g 454 g 2936801
Desiccant, Drierite (without indicator) each 2285901
Desiccator, vacuum (uses ceramic plate) 100/pkg 2088800
Dish, moisture determination, aluminum, 63 x 17.5 mm each 2164000
Tongs, crucible each 56900
Oven, laboratory, 120 VAC each 1428900
or
Oven, laboratory, 240 VAC each 1428902
Table 3 Optional apparatus

Desiccator, without stopcock each 1428500
Adjust the pH
For a metals procedure
Note: If aliquots smaller than 0.5 mL are analyzed, pH adjustment is not necessary.
1. Find the necessary volume of sample for analysis from the Sample and Analysis
Volume Tables after each digestion procedure. Use a pipet to add this volume into a
graduated mixing cylinder.
Note: To use a pipet to add a volume into a volumetric flask or a regular graduated cylinder is
necessary for some methods.
2. Dilute to about 20 mL with deionized water.
3. Add one drop of 2,4 Dinitrophenol Indicator Solution.
4. Add one drop of 8 N Potassium Hydroxide (KOH) Standard Solution (28232H). Swirl
after each addition until the first flash of yellow shows (pH 3). If the sample is
analyzed for potassium, use 5 N sodium hydroxide (245026) instead. Do not use a
pH meter if the sample is analyzed for potassium or silver.
5. Add one drop of 1 N KOH (2314426). Put the stopper in the cylinder and invert
several times to mix. If the sample is analyzed for potassium, use 1 N sodium
hydroxide instead.
Note: Use pH paper to make sure that the pH is 3. If it is higher than 4, do not adjust again with
acid. Start over with a fresh aliquot.
6. Continue to add 1 N KOH in this manner until the first permanent yellow color shows
(pH 3.5–4.0).
5
7. Look at the cylinder from the top against a white background. Compare the cylinder to
a second cylinder filled to the same volume with deionized water.
Note: High iron content will cause precipitation (brown cloud) which will co-precipitate other
metals. Do this procedure again with a smaller aliquot volume.
8. Add deionized water to the volume specified in the colorimetric procedure for the
parameter under analysis.
9. Continue with the colorimetric procedure.
For the Total Kjeldahl Nitrogen colorimetric method

Consult the spectrophotometer or colorimeter procedure to complete the TKN analysis.
The procedure that follows is only a guide to use if a procedure is not available.
1. Use a pipet to add an appropriate analysis volume to a graduated mixing cylinder.

2. Add one drop of TKN Indicator (2251900).
3. Add one drop of 8 N KOH Standard Solution (28232H), swirl after each addition until
the first flash of pale blue shows (pH 3).
4. Add one drop of 1 N KOH (2314426). Put the stopper in the cylinder and invert
several times to mix.
Note: Look at the cylinder from the top against a white background. Compare the cylinder to a
second cylinder filled to the same volume with deionized water.
5. Continue to add 1 N KOH in this manner until the first permanent blue color shows.
6. Add deionized water to the volume shown in the colorimetric procedure for the
parameter under analysis.
7. Continue with the colorimetric procedure.
6
HACH COMPANY World Headquarters HACH LANGE GMBH HACH LANGE Sàrl
P.O. Box 389, Loveland, CO 80539-0389 U.S.A. Willstätterstraße 11 6, route de Compois
Tel. (970) 669-3050 D-40549 Düsseldorf, Germany 1222 Vésenaz
(800) 227-4224 (U.S.A. only) Tel. +49 (0) 2 11 52 88-320 SWITZERLAND
Fax (970) 669-2932 Fax +49 (0) 2 11 52 88-210 Tel. +41 22 594 6400
orders@hach.com info@hach-lange.de Fax +41 22 594 6499
www.hach.com www.hach-lange.de
© Hach Company/Hach Lange GmbH, 2011-2014, 2016. All rights reserved.

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Hydraulic Fracturing Water Analysis Handbook

Phenolphthalein and Total Alkalinity Method 10244

Before starting the test:

meq/L Alkalinity = mg/L as CaCO3 ÷ 50

1 Refer to Optional reagents and apparatus on page 8.

Collect the following items:

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

Delivery tube for digital titrator 1

Erlenmeyer flask, 250-mL 1

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

Test procedure (continued)

Table 1 Range-specific information

10–40 100 0.1600 0.1

Table 2 End point pH

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

5. Blot dry with a lint-free cloth.

For mineral deposits:

2. Soak the glass bulb for 10–15 minutes in 0.1 M HCI.

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

5. Blot dry with a lint-free cloth.

For fats, grease and oils:

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

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

4. Blot dry with a lint-free cloth.

Sample collection, preservation and storage

Alkalinity measurements with a pH meter

Alkalinity relationship table

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

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

The bicarbonate alkalinity equals 0 mg/L.

Table 4 Alkalinity relationships

1. Open the standard solution ampule.

Consumables and replacement items

Optional reagents and apparatus

FOR TECHNICAL ASSISTANCE, PRICE INFORMATION AND ORDERING: HACH COMPANY

Bacteria, Acid-producing DOC316.53.01328

Visual determination APB-BART™*

Advanced test information

Consumables and replacement items

BART Test for heterotrophic aerobic bacteria (HAB) 1

Refer to Consumables and replacement items on page 3 for order information.

Make an estimate of the bacteria population

Advanced test information

Figure 1 Dominant bacteria

Aerobic bacteria Facultative anaerobic bacteria

2 Bacteria, Heterotrophic Aerobic, HAB-BART

Consumables and replacement items

Description Quantity/Test Unit Item no.

BART Test for heterotrophic aerobic bacteria (HAB) 1 9/pkg 2490409

Bacteria, Heterotrophic Aerobic, HAB-BART 3

Bacteria, Slime-forming DOC316.53.01327

Visual determination SLYM-BART™*

Figure 1 Negative versus positive test results

The solution is cloudy. A

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