Hydraulic Fracturing Handbook

DOC022.53.
80225
Hydraulic Fracturing Water Analysis Handbook

For use with DR/820, DR/850 or DR/890 Colorimeters
08/2012, Edition 4
Table of Contents
Introduction ......................................................................................................................................... 2
Alkalinity .............................................................................................................................................. 3
Bacteria, Acid-producing ............................................................................................................... 11
Bacteria, Heterotrophic Aerobic................................................................................................... 15
Bacteria, Slime-forming.................................................................................................................. 19
Bacteria, Sulfate-reducing ............................................................................................................. 23
Bacteria, Iron-related ...................................................................................................................... 27
Barium ................................................................................................................................................ 31
Boron .................................................................................................................................................. 37
Chloride .............................................................................................................................................. 43
Chloride, HR ...................................................................................................................................... 49
Conductivity ...................................................................................................................................... 55
Hardness, Calcium .......................................................................................................................... 61
Hardness, Total ................................................................................................................................ 69
Iron, Total ........................................................................................................................................... 77
pH ........................................................................................................................................................ 83
Sulfate................................................................................................................................................. 87
Sulfide................................................................................................................................................. 93
TPH (Total Petroleum Hydrocarbons) ......................................................................................... 99
Procedures Explained
Barium .................................................................................................................................................. 1
Hardness, Total and Calcium .......................................................................................................... 3
Iron ........................................................................................................................................................ 4
Conductivity and Total Dissolved Solids ..................................................................................... 6
Turbidity and Total Suspended Solids ....................................................................................... 10
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.
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 10.
Collect the following items:

Description
Quantity
Bromcresol Green-Methyl Red Indicator Powder Pillow
Phenolphthalein Indicator Powder Pillow
pH Meter and probe (highly colored samples only)
each
Sulfuric acid titration cartridge (refer to Table 1 on page 5)
Digital titrator
Delivery tube for digital titrator
Graduated cylinder
Erlenmeyer flask, 250-mL
Refer to Consumables and replacement items on page 9 for reorder information.
Alkalinity
Page 3
Alkalinity
Test procedure
See
Table 1
1. Select a sample
volume and titration
cartridge from Table 1 on
page 5.
Note: Typical oil and gas
field water levels are 100
600 mg/L CaCO3.
5. Transfer the sample

into a clean, 250-mL
Erlenmeyer flask. If the
sample volume is less
than 100 mL, dilute to
approximately 100 mL with
deionized water.
Note: A pH meter may be
used in highly colored
samples. If a pH meter is
used, the Phenolphthalein
Indicator Powder Pillow is
not required in the next
step.
Alkalinity
Page 4
2. Insert a clean delivery

tube into the 1.600 N
Sulfuric Acid titration
cartridge. Attach the
cartridge to the titrator.
3. Turn the delivery knob

to eject air and a few drops
of titrant. Reset the
counter to zero and wipe
the tip.
4. Use a graduated
cylinder or pipet to
measure the sample
volume from Table 1 on
page 5.
7. Place the delivery tube

into the solution and swirl
the flask. Turn the knob on
the titrator to add titrant to
the solution. Continue to
swirl the flask and add
titrant until the color
changes from pink to
colorless or until a pH of
8.3 is reached.
8. Use the multiplier in

Table 1 on page 5 to
calculate the
concentration:
Note: Other titrant

strengths are available.
6. Add the contents of

one Phenolphthalein
Swirl to mix.
If the solution turns pink or
the measured pH is
greater than 8.3, proceed
to step 7. If the solution is
colorless or the measured
pH is less than 8.3, the
Phenolphthalein (P)
alkalinity is zero. Proceed
to step 9.
Write down the number of

digits displayed on the
counter.
digits x multiplier =
mg/L as CaCO3
P alkalinity
Example: 100 mL of
sample was titrated with
the 1.600 N cartridge and
250 digits were used to
reach the end point. The
concentration is 250 x 1.0
= 250 mg/L as CaCO3.
Alkalinity
Test procedure (continued)
See
Table 4

one Bromcresol GreenMethyl Red Indicator
Powder Pillow. Swirl to
mix.
Note: The Bromcresol
Green-Methyl Red
Indicator Powder Pillow is
not required if a pH meter
is used.
10. Continue the titration

with sulfuric acid to a light
pink color or to a pH of 4.5.

Table 1 to calculate the
concentration:

counter.
mg/L as CaCO3
total alkalinity
Note: A pH meter may be

used to titrate to a specific
pH as required by sample
composition. Refer to
Table 2. A pH of 4.5 is
recommended.
Example: 100 mL of
concentration is 250 x 1.0
= 250 mg/L as CaCO3.
12. Calculate the

bicarbonate, carbonate
and hydroxide alkalinities
with Table 4 on page 8.
Table 1 Range-specific information

Range (mg/L as CaCO3)
Sample volume (mL)
Titration cartridge (N H2SO4)
Multiplier
1040
100
0.1600
0.1
40160
25
0.1600
0.4
100400
100
1.600
1.0
200800
50
1.600
2.0
5002000
20
1.600
5.0
10004000
10
1.600
10.0
Table 2 End point pH

Sample composition
Total alkalinity
Phenolphthalein alkalinity
Alkalinity about 30 mg/L
pH 4.9
pH 8.3
pH 4.6
pH 8.3
pH 4.3
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
Alkalinity
Page 5
Alkalinity
Interferences
Table 3 lists substances that can interfere with this test.
Table 3 Interfering substances

Interfering substance
Interference level
Chlorine
Chlorine at levels above 3.5 mg/L may cause a yellow-brown color when the Bromcresol
Green-Methyl Red Powder Pillow is added. Add one drop of 0.1 N Sodium Thiosulfate to the
sample to remove chlorine before the test is started.
Color or turbidity
Do not filter, dilute or alter the sample. Color or turbidity can mask the color change of the
end point. Use a pH meter instead of the color indicators and titrate to a pH of 8.3 for
phenolphthalein acidity. For total alkalinity, refer to Table 2 on page 5 for the correct end point
pH.
Soaps, oily matter, suspended

solids and precipitates
Oils or solids may cover the pH probe and cause a slow or sluggish response. Clean the
probe immediately after use (refer to Maintenance of pH probes).
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 1216 hours in Hach Probe Cleaning Solution.
3. Rinse or soak the probe for 1 minute in deionized water.
4. Soak the probe in pH 4 buffer for up to 20 minutes, then rinse with deionized water.
5. Blot dry with a lint-free cloth.
For mineral deposits:
1. Rinse the probe with deionized water and blot dry with a lint-free cloth.
2. Soak the glass bulb for 1015 minutes in 0.1 M HCI.
For fats, grease and oils:
1. Soak the glass bulb in a warm detergent solution for up to 2 hours.
Alkalinity
Page 6
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 8).
To use the table, follow these steps:
1. Does the phenolphthalein alkalinity equal zero? If yes, refer to Row 1.
2. Does the phenolphthalein alkalinity equal total alkalinity? If yes, refer to Row 2.
3. Divide the total alkalinity by 2 to give one-half the total alkalinity.
4. Compare the result of step c (one-half total alkalinity) with the total alkalinity, and then refer to
row 3, 4 or 5.
5. Perform the required calculations in the appropriate row, if any calculations for that row are
required.
6. Check your results. The sum of the three alkalinity types will equal the total alkalinity.
For example:
A sample has 170 mg/L as CaCO3 phenolphthalein alkalinity and 250 mg/L as CaCO3 total
alkalinity. What is the concentration of hydroxide, carbonate and bicarbonate alkalinities?
The phenolphthalein alkalinity does not equal 0 (it is 170 mg/L).
The phenolphthalein alkalinity does not equal total alkalinity (170 mg/L vs. 250 mg/L).
One-half of the total alkalinity (250 mg/L) equals 125 mg/L. Because the phenolphthalein alkalinity
(170 mg/L) is greater than one-half the total alkalinity (125 mg/L), refer to row 5.
The hydroxide alkalinity is equal to:
2 x 170 = 340
340 250 = 90 mg/L hydroxide alkalinity
The carbonate alkalinity is equal to:
250 170 = 80
80 x 2 = 160 mg/L carbonate alkalinity
Alkalinity
Page 7
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

Row
Sample result
Hydroxide alkalinity
equals:
Carbonate alkalinity
equals:
Bicarbonate alkalinity
equals:
Total Alkalinity
Phenolphthalein Alkalinity = 0
Phenolphthalein Alkalinity equal

to Total Alkalinity
Total Alkalinity
Phenolphthalein Alkalinity less

than one-half of Total Alkalinity
Phenolphthalein Alkalinity
times 2
Total Alkalinity minus two

times Phenolphthalein
Alkalinity
Phenolphthalein Alkalinity equal

to one-half of Total Alkalinity
Total Alkalinity
greater than one-half of Total
Alkalinity
2 times Phenolphthalein
Alkalinity minus Total
Alkalinity
2 times the difference

between Total and
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 alkalinityAdd 50 mL of deionized water to a flask. Add one pH 8.3

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

Required for accuracy check:
Alkalinity Voluette Ampule Standard Solution, 0.500 N
Ampule breaker
TenSette Pipet, 0.11.0 mL and Pipet Tips
1. Open the standard solution ampule.

2. Use the TenSette Pipet to add 0.1 mL of the standard to the titrated sample. Swirl to mix.
3. Titrate the spiked sample to the end point. Write down the amount of titrant that was used to
reach the end point.
4. Repeat steps 2 and 3 with two more additions of 0.1 mL. Titrate to the end point after each
addition.
5. Each 0.1 mL of standard that was added will use approximately 25 digits of the 1.600 N
titration cartridge or 250 digits of the 0.1600 N titration cartridge to reach the end point. If more
or less titrant was used, there may be an interference (refer to Interferences on page 6) or the
concentration of the titrant has changed.
Alkalinity
Page 8
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
Alkalinity Reagent Set (approximately 100 tests)
Item no.
2271900
(1) Bromcresol Green-Methyl Red Powder Pillows
100/pkg
94399
(1) Phenolphthalein Indicator Powder Pillows
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
Quantity/Test
Unit
Item no.
each
1690001
each
50546
Cylinder, graduated, 10-mL
each
50838
each
50840
each
50841
each
50842
Unit
Item no.
16/pkg
1427810
Required apparatus
Description
Digital Titrator
Flask, Erlenmeyer, graduated, 250-mL
Graduated cylinderselect one or more based on range:
Recommended standards
Description
Alkalinity Standard Solution, Voluette Ampule 0.500 N Na2CO3, 10-mL
Alkalinity
Page 9
Alkalinity
Optional reagents and apparatus

Description
Unit
Item no.
Buffer Powder Pillows, pH 4.5
25/pkg
89568
Buffer Powder Pillows, pH 8.3
25/pkg
89868
each
2095352
Stir bar, octagonal 28.6 mm x 7.9 mm

TenSette Pipet, 0.1 to 1.0 mL
each
1970001
500 mL
27249
Pipet, volumetric, Class A, 10 mL
each
1451538
each
1451520
Water, deionized
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:

In the U.S.A. Call toll-free 800-227-4224
Outside the U.S.A. Contact the HACH office or distributor serving you.
On the Worldwide Web www.hach.com; E-mail techhelp@hach.com
Hach Company, 2011. All rights reserved. Printed in U.S.A.
HACH COMPANY
WORLD HEADQUARTERS
Telephone: (970) 669-3050
FAX: (970) 669-2932
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

from the outer tube.
5. Invert the tube for 30

seconds to dissolve the
dye under the cap.
2. Collect at least 20 mL
of sample in the outer
tube.
6. Write the date and

sample name on the outer
tube.
3. Fill the inner tube with

the sample to the fill line.
Tighten the cap on the
inner tube.
4. Put the inner tube in

the outer tube and tighten
the cap on the outer tube.
7. Incubate the tube at

room temperature and
away from direct sunlight.
Do not move the tube.
8. Examine the tube

each day for 8 days.
Record the date when a
reaction is first seen. Refer
to Test results.
Do not shake or swirl the

tube!
Page 11
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
800,000
High
70,000
High
9,000
High
1500
Moderate
500
Moderate
150
Moderate
<100
Low
<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.
Page 12
Figure 1 Disposal

Required reagents and apparatus
Description
BART Test for acid-producing bacteria
Quantity/Test
Unit
Item no.
9/pkg
2831409
Page 13

HACH COMPANY
WORLD HEADQUARTERS
Telephone: (970) 669-3050
FAX: (970) 669-2932
08/2012, Edition 1
Chloride, HR, 10255
Bacteria, Heterotrophic Aerobic
DOC316.53.01329
HAB-BART*
Semi-quantitative
Scope and Application: For the determination of total aerobic bacteria in brine solutions, produced waters and
*HAB-BART is a trademark of Droycon Bioconcepts Inc.
Test preparation
Procedure notes:
invert the cap.
Test procedure

5. Invert the tube for 30

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

tube.

inner tube.


8. Examine the tube

to Test results.

tube!

Page 15
Test results
Presence/Absence
When heterotrophic aerobic bacteria are present, the color of the solution changes from a blue to a
light or medium yellow color. The solution often becomes cloudy.
Negative (absent/non-aggressive)the color stays blue.
Positive (present/aggressive)the color becomes yellow. The solution can be cloudy.


Days to reaction
Approximate HAB population (cfu/mL)
Aggressivity
7,000,000
Very high
500,000
High
50,000
Moderate
7,000
Low

If the test result is positive, examine the tubes for dominant bacteria. Refer to Figure 1.
Figure 1 Dominant bacteria
The color is
bleached from the
bottom to the top.
Aerobic bacteria
The color is
bleached from the
top to the bottom.
Facultative anaerobic bacteria
Summary of method
When heterotrophic aerobic bacteria (HAB) are in the sample, the bacteria consume oxygen
during incubation. When the oxygen is depleted, the bacteria react with the methylene blue dye in
the HAB-BART vial and reduce the dye to its colorless form. The faster the color change, the
higher the level of respiration and the larger or more aggressive the bacteria population.
Aerobic bacteria can cause several problems in water, including slime formations, turbidity, taste
and odor, corrosion, health risks and hygiene risks. When a problem is found, more tests are
recommended to give more information about the microbial problem. This method does not give
information about the particular groups of bacteria that can be present.
Disposal

Page 16

Figure 2 Disposal

Description
Quantity/Test
Unit
Item no.
BART Test for heterotrophic aerobic bacteria
9/pkg
2490409
BART Test for heterotrophic aerobic bacteria
27/pkg
2490427

Page 17

HACH COMPANY
WORLD HEADQUARTERS
Telephone: (970) 669-3050
FAX: (970) 669-2932
08/2012, Edition 1
Chloride, HR, 10255
Bacteria, Slime-forming
DOC316.53.01327
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.
tube.


inner tube.

tube!
7. Examine the tube

to Test results.
Page 19
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

glowing ring is seen
under UV light and/or
there is slime growth at
the bottom of the tube.
The solution stays

clear, with no visible
growth or glow under
UV light.
Negative (absent/non-aggressive)
Positive (present/aggressive)


Days to reaction
Approximate slime population (cfu/mL)
Aggressivity
1,800,000
Very high
350,000
High
66,500
High
12,500
Moderate
2500
Moderate
500
Moderate
100
Low
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

or slime ring around
balldense slime
bacteria
Page 20
Cloudy growth or
layered platesslimeforming bacteria
Glows pale blue

under UV light
fluorescing
pseudomonads
Blackened liquid
pseudomonads
and enterics
Thread-like
strands
tight slime
bacteria
Summary of method
When slime-forming bacteria are in the sample, one or more types of slime will grow in the SLYMBART 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

Description
Quantity/Test
Unit
Item no.
BART Test for slime-forming bacteria
9/pkg
2432509
BART Test for slime-forming bacteria
27/pkg
2432527
Page 21

HACH COMPANY
WORLD HEADQUARTERS
Telephone: (970) 669-3050
FAX: (970) 669-2932
08/2012, Edition 1
Chloride, HR, 10255
Bacteria, Sulfate-reducing
DOC316.53.01326
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.
tube.


inner tube.

tube!
7. Examine the tube

to Test results.
Page 23
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
and/or there is
a black slime
growth at the
bottom of the
tube.
The solution
has no black
slime.


Days to reaction
Aggressivity
6,800,000
Very high
700,000
High
100,000
High
18,000
Moderate
5000
Moderate
1200
Moderate
500
Moderate
200
Low

If the test result is positive, examine the tubes for dominant bacteria. Refer to Figure 2.
Black in the bottom onlydense

anaerobic bacteria dominated by
Desulfovibrio
Page 24
Black around the ball only

aerobic SRB with
aerobic slime forming heterotrophs
Black in the bottom and

around the ballaerobic
and anaerobic SRB
Cloudy solution
anaerobic bacteria
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. Sulfatereducing bacteria can cause problems such as strong odors, blackening of equipment, slime
formations and the start of corrosive processes.
Disposal
Figure 3 Disposal

Description
Quantity/Test
Unit
Item no.
BART Test for sulfate-reducing bacteria
9/pkg
2432509
BART Test for sulfate-reducing bacteria
27/pkg
2432527
Page 25

HACH COMPANY
WORLD HEADQUARTERS
Telephone: (970) 669-3050
FAX: (970) 669-2932
08/2012, Edition 1
Chloride, HR, 10255
Bacteria, Iron-related
DOC316.53.01325
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.
tube.


inner tube.

tube!
7. Examine the tube

to Test results.
Page 27
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
around the ball
and/or there is a
brown slime growth
at the bottom of the
tube.
The solution has

no foam or
brown slime.


Days to reaction
Aggressivity
540,000
Very high
140,000
High
35,000
High
9,000
Moderate
2300
Moderate
500
Moderate
150
Moderate
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.
Foam around
ballanaerobic
bacteria
Brown rings, gel and/or clouds

iron-related bacteria
Page 28
Green cloudy
pseudomonads
Red
cloudy
enteric
bacteria
Cloudy
heterotrophic
bacteria
Black solution
pseudomonads
and enterics
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

Description
Quantity/Test
Unit
Item no.
BART Test for iron-related bacteria
9/pkg
2432309
BART Test for iron-related bacteria
27/pkg
2432327
Page 29

HACH COMPANY
WORLD HEADQUARTERS
Telephone: (970) 669-3050
FAX: (970) 669-2932
08/2012, Edition 1
Barium
DOC316.53.01311
Turbidimetric Method1
Method 10251
(080, 0800 and 08000 mg/L)
Powder Pillows
Scope and Application: For oil and gas field waters.

1
Adapted from Snell and Snell, Colorimetric Methods of Analysis, Vol. II, 769 (1959).
Test procedure
1. Push PRGM.
The display shows
PRGM ?
Initial setup: go to
Instrument Setup on
page 33 to add the
program to the
instrument.
5. If the sample volume

is less than 10 mL, add
deionized water to the
10-mL line. Tighten the
cap on the sample cell
and invert to mix.
Note:A 10-mL graduated
mixing cylinder can be used
in steps 4 and 5.
2. Push 125 ENTER.

The display shows
mg/L, Ba LR, Ba MR or
Ba HR and the ZERO
icon.
3. Push CONC to select

the test range:
Ba LR: 080 mg/L
Ba MR: 0800 mg/L
Ba HR: 08000 mg/L
4. Add the specified

sample volume to a clean
sample cell:
Ba LR: 10 mL
Ba MR: 1.0 mL
Ba HR: 0.1 mL
Note:Use a TenSette or
glass pipet to measure
0.1 mL or 1.0 mL.
6. Put the sample cell in

the cell holder. Put the
instrument cap over the
sample cell.
7. Push ZERO.
The cursor moves to the
right, then the display
shows:
0 mg/L Ba and LR, MR
or HR
8. Remove the cap and

add the contents of one
BariVer Barium Reagent
Powder Pillow to the
sample cell. Tighten the
cap on the cell and invert
to mix.
Note:The sample will
become cloudy if barium is
in the sample.
Note:Accuracy is not
affected by undissolved
powder.
Barium
Page 31
Barium
9. Push
TIMER ENTER
A 5-minute reaction
period starts.
Do not move the sample
cell during the reaction
period.
10. Within five minutes

after the timer beeps, put
the prepared sample in
the instrument. Put the
sample cell.
11. Push READ.

The cursor moves to the right, then the result in mg/L
barium is shown.
Notice! Do not push the CONC key at the end of the
test to change the range. The result is applicable only
to the test range that was selected in step 3.
Clean the sample cells with soap and a brush.
Note:For best results use the Standard Adjust option. Refer
to Standard Adjust on page 33.
Sampling and Storage

Collect the sample in a clean plastic or glass bottle. Samples can be used for up to 28 days if they
are kept at or less than 4 C (39 F). Let the sample temperature increase to room temperature
before analysis.
Interferences
Known interferences are shown in Table 1. The interference levels are applicable to an undiluted
10-mL sample. The interference levels increase proportionally as the sample is diluted.
Table 1 Interferences
Substance
Interference Level
Calcium
10,000 mg/L as CaCO3
Sodium chloride
130,000 mg/L as NaCl
Magnesium
Silica
500 mg/L as CaCO3
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.
Turbidity
Filter samples that have a high level of turbidity
Accuracy Check
Standard Additions Method
Use the standard additions method to validate the test procedure, reagents and instrument and to
find if there is an interference in the sample.
1. Fill three sample cells with sample as specified in steps 4 and 5 of the test procedure.
2. Use a TenSette Pipet to add 0.1, 0.2 and 0.3 mL of a 1000 mg/L Barium Standard Solution to
the sample cells. Mix fully.
3. Complete the test procedure for each sample.
Barium
Page 32
Barium
4. Review the results. The barium concentration should increase by 10 mg/L for Ba LR,
100 mg/L for Ba MR or 1000 mg/L for Ba HR for each 0.1 mL of standard that is added.
5. If the concentration does not increase by the correct amount, refer to Standard Additions in
Section 1 of the procedures manual.
Standard Solution Method
Use a 50 mg/L Barium Standard Solution to validate the test procedure, reagents and the
instrument. Select the Ba LR test range in step 3 and use 10 mL of the standard solution instead of
the sample in step 4. To adjust the result, refer to Standard Adjust.
To prepare this standard solution, add 5.0 mL of a 1000 mg/L Barium Standard Solution to a 100mL volumetric flask. Dilute to the mark with deionized water and mix fully.
Standard Adjust
The standard adjust option is recommended when program 125 is used.
1. Measure the concentration of a 50 mg/L Barium Standard Solution. Select the Ba LR range
and use 10 mL of the standard solution. Keep the sample cell in the instrument.
2. Push the SETUP key and use the arrow keys to scroll to the STD option.
3. Push ENTER.
4. Push the numbers 50 to make the instrument read the value of the standard solution
concentration.
5. Push ENTER to complete the adjustment.
Note: The MR and HR calibration curves are adjusted proportionally when the Ba LR calibration curve is
adjusted. Refer to Section 1, Standard Curve Adjustment of the procedures manual.
Method Performance
Precision
In a single laboratory, with a 70 mg/L barium standard solution, two representative lots of powder
pillows and the instrument, a single operator got a standard deviation of 1.2 mg/L barium.
Estimated Detection Limit (EDL)
The EDL for program 125 Ba LR is 2 mg/L Ba. For more information on derivation and use of the
estimated detection limit, refer to Section 1 of the procedures manual.
Instrument Setup
This procedure adds program 125 to a DR/820, DR/850 or DR/890 instrument.
1. Push the ON key to turn on the instrument.
2. Push the SETUP key.
3. Push the down arrow key until the prompt line shows USER.
4. Push the ENTER key.
5. Push the numbers 8138, then push ENTER.
6. Refer to Table 2. Find the number from the Enter column that corresponds to Line Number 1
on the display. Push these numbers on the keypad, then push ENTER. Continue to add the
numbers that correspond to each line number on the display.
Note: Use the arrow keys to scroll and review or change numbers at any time.
Barium
Page 33
Barium
Table 2 Instrument setup
Line Number
Enter
Line Number
Enter
125
29
82
24
30
66
72
31
97
32
32
33
72
34
82
35
65
36
32
37
10
38
11
39
66
12
66
40
200
13
169
41
14
125
42
15
112
43
16
44
88
17
45
18
46
19
47
30
20
66
48
21
97
49
44
22
32
50
23
76
51
24
82
52
25
66
53
26
97
54
25
27
32
55
28
77
56
255
Summary of Method
Barium ions in the sample react with the BariVer 4 Barium Reagent to make a barium sulfate
precipitate, which is held in suspension by a protective colloid. The amount of precipitate is
proportional to the barium concentration. The BariVer 4 Method is especially useful for brines and
produced waters where both barium and sulfate are in the sample and precipitation cannot be
started by the addition of more sulfate.
Barium
Page 34
Barium
REQUIRED REAGENTS AND APPARATUS

Description
BariVer 4 Barium Reagent Powder Pillows
Sample Cell, 10-20-25 mL, with cap
Quantity Per Test
Units
Item No.
1 pillow
100/pkg
1206499
6/pkg
2401906
OPTIONAL REAGENTS
Description
Barium Standard Solution, 1000 mg/L
Water, deionized
Units
Item No.
100 mL
1461142
4L
27256
OPTIONAL APPARATUS
Description
Units
Item No.
2088638
100/pkg
189457
Flask, volumetric, 100 mL, Class A
1457442
Funnel, poly, 65 mm
108367
Pipet, TenSette, 0.1 to 1.0 mL
1970001
Pipet Tips, for 19700-01 Pipet
50/pkg
2185696
Cylinder, graduated mixing, 10 mL

Filter Paper, folded, 12.5 cm
1970010
50/pkg
2199796
Pipet, volumetric, 5.00 mL, Class A
1451537
1465100
Barium
Page 35

HACH COMPANY
WORLD HEADQUARTERS
Telephone: (970) 669-3050
FAX: (970) 669-2932
09/2011, Edition 1
Boron
DOC316.53.01309
Carmine Method
Method 10252
0 to 50 mg/L B
Powder Pillows
Scope and Application: For oil and gas field waters
Test procedure
1. Push: PRGM
The display shows:
PRGM ?
Instrument Setup on
page 39 to add the
program to the
instrument.
2. Push: 126 ENTER

The display shows
mg/L, B HR and the
ZERO icon.
To do an accuracy proof,
use a 30 mg/L boron
standard as an alternative
to the sample.
3. Put the COD/TNT vial

adapter in the cell holder.
Rotate the adapter until it
goes in. Then push the
adapter down until click is
heard.

one BoroVer 3 Reagent
Powder Pillow to the flask.
Swirl immediately to mix.
Let the powder dissolve
fully (no more than five
minutes).
After the powder has
dissolved fully, put a cap
on the flask.
The solution can be used
for 48 hours when it is
stored at 20 C or below.
6. Remove the caps

from two clean 16-mm
screw-capped vials.
Refer to How to use and
clean glass vials on
page 38.
7. Add 0.2 mL of sample

to one vial (the sample)
and 0.2 mL of deionized
water to the other vial (the
blank).
Note: A diffuser band covers

the light path holes on the
adapter. For best
performance, do not remove
the diffuser band.
Note: As an alternative, use

0.4 mL of sample or DI
water. Use 7.0 mL of
BoroVer 3 in step 8.
4. Use a 100-mL
graduated cylinder to
measure 75 mL of
concentrated sulfuric acid.
Add the acid to a 250 mL
plastic Erlenmeyer flask.
Notice! Prepare the
solution in a wellventilated area or use a
fume hood to prevent
injury.
8. Add 3.5 mL of the

BoroVer 3 solution
prepared in step 5 to the
sample vial. Tighten the
cap and immediately
invert to mix.
The solution in the vials
will become warm.
Note: As an alternative, use
7.0 mL of BoroVer 3 solution
with 0.4 mL of sample if a
3.5- mL pipet is not available.
Boron
Page 37
Boron
9. Add 3.5 mL of the

BoroVer 3 solution
prepared in step 5 to the
blank vial. Tighten the cap
and invert to mix.
10. Push: Timer Enter

A 30-minute reaction
period starts.
11. Clean the outer

surface of the vial with a
damp cloth. Dry the vial
with a dry cloth to remove
fingerprints and other
marks.
12. After the timer beeps,

put the blank into the
adapter. Push straight
down on the top of the vial
until it is fully installed.
The vial must not move,
because this can cause
reading errors.
13. Put the instrument

cap over the vial.
14. Push: ZERO

shows:
0.00 mg/L B HR
15. Put the prepared

sample in the adapter.
Put the instrument cap
over the vial. Push
straight down on the top
of the vial until it is fully
installed. The vial must
not move, because this
can cause reading errors.
16. Push: READ

right, then the result in
mg/L B HR is shown.
Note: For best results, use
the Standard Adjust option.
Refer to the procedures
manual for more information
about Standard Adjust.
Sample Collection, Preservation and Storage

Collect the samples in clean polyethylene bottles.
Reagent preparation
Mix one BoroVer 3 Reagent Powder Pillow per 75 mL of concentrated sulfuric acid. Add the
powder pillow while stirring. The preparation of this solution generates gaseous HCl when the
indicator pillow is added to the sulfuric acid. Prepare the solution in a well-ventilated area or use a
fume hood to prevent injury. This solution is stable for up to 48 hours if stored in plastic containers.
Do not store in borosilicate glassware (Pyrex or Kimax) for more than one hour. The solution
may pull boron from these containers.
How to use and clean glass vials

The glass vials and caps can be used again. Discard the reacted BoroVer 3 Reagents correctly.
Refer to the current material safety data sheets (MSDS) for safety protocols and disposal
information. Flush the vials many times with deionized water and let them dry before use.
Note: Let the empty vials drain fully before flushing with water.
New vials can contain residual amounts of reactive boron from the glass manufacturing process.
For best results, fill the vials with 34 mL of the prepared BoroVer 3 Reagent for 30 minutes.
Discard the reacted solution. Flush and dry the vials for use in other analysis.
Boron
Page 38
Boron
The BoroVer 3/Sulfuric Acid solution is very acidic. Make sure that the solution is neutral (pH 69)
before disposal. Refer to the current material safety data sheets (MSDS) for safety protocols and
disposal information.
Accuracy Check
Use a 30 mg/L Boron Standard Solution to validate the test procedure, reagents and the
instrument.
1. To prepare the standard solution, add 3.0 mL of a 1000 mg/L Boron Standard Solution to a
100-mL volumetric flask. Add deionized water to the mark, stopper and mix fully.
2. Use the 30 mg/L Boron Standard Solution as an alternative to the sample in step 7 of the
procedure.
Standard Adjust
Use the reading with the 30 mg/L Boron Standard Solution to adjust the calibration curve.
2. Push ENTER.
3. Push the numbers 30 to measure the value of the standard solution concentration.
4. Push ENTER to complete the adjustment. Refer to Section 1 Standard Adjust of the
procedures manual for more information.
Method Performance
Precision
In a single laboratory, with a standard solution of 25 mg/L boron and two representative lots of
reagent with the instrument, a single operator obtained a standard deviation of 0.8 mg/L boron.
Estimated Detection Limit
The estimated detection limit for program 126 is 2.2 mg/L B. For more information on derivation
and use of the estimated detection limit, refer to Section 1 of the procedures manual.
Summary of Method
Boron reacts with a mixture of carminic acid and sulfuric acid and then shows a reddish to bluish
color. The amount of color is directly proportional to the boron concentration.
Instrument Setup
This procedure adds the program 126 to a DR/850 or DR/890 instrument.
1. Push ON to turn on the instrument.
2. Push SETUP.
3. Push the down arrow until the prompt line shows USER and push ENTER.
Boron
Page 39
Boron
Boron
Page 40
Line Number
Enter
Line Number
Enter
1
2
126
29
42
30
72
31
32
33
34
35
64
36
117
37
10
40
38
11
140
39
12
65
40
13
211
41
14
79
42
15
222
43
16
44
55
17
45
128
18
46
19
47
20
20
66
48
21
32
49
22
72
50
23
82
51
24
52
25
53
26
54
143
27
55
28
56
255
Boron
REQUIRED REAGENTS AND APPARATUS (Using Powder Pillows)

Description
Quantity Per Test
Unit
Item No.
1pp/10 tests
100/pkg
1417099
Sulfuric Acid, ACS, concentrate
75mL/20 tests
500 mL
97949
Water, deionized
BoroVer 3 Boron Reagent Powder Pillow
4.0 mL/20 tests
100 mL
27242
Vials, glass, 16 mm x 100 mm
6/pk
2275806
Caps, white,Teflon lining, for 16 mm vials
6/pk
2350206
Flask, polymethylpentene, screw cap, 250 mL
2089846
Cylinder, graduated, polypropylene, 100 mL
108142
Pipet, 0.21.0 mL
BBP078
Pipet Tip for BBP078
100/pk
BBP079
Pipet, 1.05.0 mL
BBP065
Pipet Tip for BBP065
75/pk
BBP068
Pipet, TenSette 0.11.0 mL
1970001
Pipet Tips, 0.11.0 mL for 1970001 Pipet
50/pk
2185696
OR
Pipet, TenSette 1.010.0 mL
1970010
Pipet Tips, 1.010.0 mL for 1970010 Pipet
50/pk
2199796
OPTIONAL REAGENTS
Description
Unit
Item No.
Boron Standard Solution, 1000 mg/L as B
100 mL
191442
Sodium Hydroxide, 6 N
1000 mL
2332453
Unit
Item No.
Pipet Tips, 0.11.0 mL for 1970001 TenSette Pipet
1000/pk
2185628
Pipet Tips, 1.010.0 mL for 1970010 TenSette Pipet
250/pk
2199725
Rack, Test Tube, for holding ten 16-mm vials
1864100
Pipets, includes one BBP078 and BBP065 pipet plus tips
LZP320
Goggles, safety, standard
2927902
pair
2410105
6/pk
2930004
188/pk
293280
OPTIONAL APPARATUS
Description
Gloves, chemical-resistant, size 10

Bottle, storage, write on, HDPE, 1000 mL
Wipes, disposable 28 x 37 cm
Boron
Page 41

HACH COMPANY
WORLD HEADQUARTERS
Telephone: (970) 669-3050
FAX: (970) 669-2932
09/2011, Edition 1
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 gas and oil field shale waters.
Test preparation
mg/L sodium chloride = mg/L chloride x 1.65
meq/L chloride = mg/L chloride / 35.45
For added convenience when stirring, use the TitraStir stirring apparatus.

Description
Quantity
Chloride 2 Indicator Powder Pillow
Silver Nitrate titration cartridge, 1.128 N
Digital titrator
Graduated cylinder or TenSette Pipet, (0.11.0 mL) with pipet tips
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 75100 mL of deionized or chloride free water to a clean titration flask.
2. Use a TenSette Pipet to add 0.1 mL of the sample to the titration flask. Swirl to mix.
3. Add the contents of one Chloride 2 Indicator Powder Pillow to the flask. Swirl to dissolve. The
solution will be yellow.
4. Titrate the solution quickly with the 1.128 N Silver Nitrate titrant to the red-brown end point.
Record the number of digits added. Table 1 on page 43 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
50
0.5
Chloride
Page 43
Chloride
Table 1 Guidelines to estimate sample sizes (continued)
Number of digits
Sample size (mL)
25
1.0
10
2.0
5.0
20
50
Chloride test procedure
See
Table 1
1. Select a sample
page 45. Refer to
Determine sample sizes
on page 43.
2. Insert a clean delivery

tube into the 1.128 N
Silver Nitrate titration
cartridge. Attach the
cartridge to the titrator.
Note: Put the Silver Nitrate
Titration Cartridge in a
dark area when not in use.
3. Hold the Digital

Titrator with the cartridge
tip pointing up. Turn the
delivery knob to eject a
few drops of titrant. Reset
the counter to zero and
wipe the tip.
4. Use a TenSette
graduated cylinder or pipet
to measure the sample
page 45 into a 250 mL
Erlenmeyer flask.
5. Dilute the measured

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

one Chloride 2 Indicator
Powder Pillow. Swirl to
mix.
7. Place the delivery tube

into the solution and
rapidly swirl the flask. Turn
the knob on the titrator to
add titrant to the solution.
Continue to swirl the flask
and add titrant until the
color changes from yellow
to red-brown. Refer to
Technique tips on page 45.

Table 2 on page 45 to
calculate the
concentration:
Results will still be

accurate if a small amount
of powder does not
dissolve.

counter.
Chloride
Page 44
mg/L Cl
Example: 1.0 mL of
concentration is 200 x 50 =
10,000 mg/L Cl.
Chloride
Table 2 Range-specific information

Range (mg/L as Cl)
Sample volume (mL)
Titration cartridge (N AgNO3)
Multiplier
100400
50
1.128
1.0
2501000
20
1.128
2.5
10004000
1.128
10.0
250010,000
1.128
25.0
500020,000
1.128
50
10,00040,000
0.5
1.128
100
25,000100,000
0.2
1.128
250
50,000200,000
0.1
1.128
500

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 5075% of
the expected end point. The solution will have a milky white precipitate.
3. Add the Chloride 2 Indicator and swirl to dissolve. The solution will turn yellow. Continue to
titrate with the Silver Nitrate titrant to the red-brown end point.
4. If the sample turns red-brown after the addition of the Chloride 2, the end point has been
exceeded and the procedure must be repeated with less titrant.
Interferences
Table 3 lists substances that can interfere with this test.
Interference level1
Bromide
Interferes directly and is included in the test result.
Cyanide
Iron
Concentrations above 10 mg/L mask the end point.
Iodide
Orthophosphate
Concentrations above 25 mg/L will precipitate the silver.
pH
Neutralize strongly alkaline or acidic samples to a pH of 2 to 7 with 5.25 N sulfuric acid or

5.0 N sodium hydroxide. If a pH meter is used in the pH adjustment, use a separate sample
to find the correct amount of acid or base to use. Then add the same amount of acid or base
to the sample to be tested. pH electrodes will contaminate the sample.
Chloride
Page 45
Chloride
Table 3 Interfering substances (continued)
Interference level1
Sulfide
Complete the following steps to remove sulfide interference:

1. Add the contents of one Sulfide Inhibitor Reagent Powder Pillow to approximately
125 mL of sample.
2. Mix for one minute.
3. Filter through folded filter paper.
4. Use the filtered sample in the chloride test procedure.
Sulfite
Concentrations above 10 mg/L interfere with this method. To eliminate sulfite interference,
add three drops of Hydrogen Peroxide, 30%, to the sample before the test is started.
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, 0.11.0 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 45) or a problem with
reagents or apparatus.
Standard solution method
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.
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.
Chloride
Page 46
Chloride
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 45).
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
Description
Quantity/Test
Unit
Chloride Reagent Set (approximately 100 tests):

(2) Chloride 2 Indicator Powder Pillows
Item no.
2288000
1 pillow
50/pkg
105766
varies
each
1439701
Quantity/Test
Unit
Item no.
Digital Titrator
each
1690001
each
50546
each
50838
each
50840
each
50841
(1) Silver Nitrate Titration Cartridge, 1.128 N
Required apparatus
Description
each
50842
Delivery tubes w/ 180 hook
each
1720500
each
1970001
Pipet tips
50/pkg
2185696
Unit
Item no.
16/pkg
1425010
2196800
Description
Chloride Standard Solution, Voluette Ampule, 12,500-mg/L Cl, 10-mL
Voluette breaker
Chloride
Page 47
Chloride

Description
Filter paper, 12.5 cm
Funnel, analytical, poly, 65 mm
Hydrogen Peroxide, 30%, ACS
Unit
Item no.
100/pkg
69257
each
108367
473 mL
14411
100 mL MDB
245032
each
2095352
Sulfide Inhibitor Reagent Powder Pillow
100/pkg
241899
Sulfuric Acid Standard Solution, 5.25 N
Sodium Hydroxide Standard Solution, 5.0 N

100 mL MDB
244932
TitraStir Stir Plate, 115 VAC
each
1940000
TitraStir Stir Plate, 230 VAC
each
1940010
4L
27256
Water, deionized
pH Test Strip, 014 pH
100/pkg
2601300
Pipet tips
1000/pkg
2185628
Chloride standard solution, 1000 mg/L
500 mL
18349
Sampling bottle
250 mL
2087076
Dropper, glass
5/pkg
1419705
each
19700-10
Delivery tubes w/ 90 hook
each
4157800
Pipet tips, for 1.010.0 mL TenSette Pipet
50/pkg
2199796
Pipet tips, for 1.010.0 mL TenSette Pipet
250/pkg
2199725

HACH COMPANY
WORLD HEADQUARTERS
Telephone: (970) 669-3050
FAX: (970) 669-2932
05/2011, Edition 1
Chloride, HR, 10255
Chloride, HR
DOC316.53.01322
Direct Measurement ISE Method

3.55 g/L to 35 g/L Cl
Method 10255
Powder Pillow ISA
Scope and Application: For the determination of high concentrations (1 M) of chloride in brine solutions,
produced waters and hydraulic fracturing waters.
Test preparation
Procedure notes:
The instructions in this procedure are specific to the HQd meters. The SensION+ meters can also be used but the navigation
and menus will be different.
Refer to the meter user manual for meter operation. Refer to the probe user manual for probe maintenance.
Set the date and time in the meter before the probe is attached. The probe must have the correct service-life time stamp.
If complete traceability is necessary, enter a sample ID and operator ID. Refer to the HQd meter manual
for more information.
Calibrate the probe regularly for the best measurement accuracy. Refer to Calibrate the probe.
Stir the standards at a slow and steady rate to prevent the formation of a vortex.
Air bubbles under the probe tip can cause slow response or measurement errors. Gently shake the probe to remove
bubbles.
Keep the temperature of the calibration standards within 2 C for best results.
Between measurements, rinse the probe with deionized water. Blot dry with a lint-free cloth.
Items to collect:
Description
Quantity
Beaker, 100-mL, polypropylene
Bottle, wash, 500-mL
Chloride ion-selective electrode
Chloride Ionic Strength Adjustor (ISA) Buffer Powder Pillows
Deionized water
varies
Meter, ion-selective electrode

Sodium chloride
1
11.55 g
Stir bars
Stirrer, electromagnetic
Volumetric flask, 200-mL
See Consumables and replacement items for reorder information.
Prepare the probe

1. Remove the sensor protection cap from the probe.
Chloride, HR
Page 49
Chloride, HR
2. Rinse the probe with deionized water. Blot dry with a lint-free cloth.
3. Put the probe in a 3.55 g/L chloride standard solution for a minimum of 30 minutes. Refer to
Prepare the calibration standards.
Set up the meter

Change the default settings in the meter for high-range measurements. Save the new settings as a
new method.
1. Connect the probe to the meter.
2. Push
3. Go to ISECl181 Settings>Modify Current Settings>Measurement Options.

4. Set the measurement options for high-range measurements:
Unitsg/L
Measurement limitsset the lower limit to 3 g/L.
5. Go to Calibration Options.
6. Set the calibration options for high-range measurements:
Std setcustom
Calibration unitsg/L
Std set values3.55, 12.5 and 35 g/L
7. Enter a name for the new settings, for example HR Cl.

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

Prepare the calibration standards
Prepare a 3.55 g/L, a 12.5 g/L and a 35 g/L chloride standard solution for calibration.
Items to collect:
Sodium chloride, NaCl
Volumetric flasks (3x), 200 mL, Class A
Laboratory balance
Deionized water
1. Prepare a 35 g/L chloride standard solution:

a. Weigh 11.55 g of sodium chloride.
b. Quantitatively transfer the NaCl into a volumetric flask.
c. Dilute to the mark with deionized water. Mix fully.
2. Prepare a 12.5 g/L chloride standard solution:
a. Transfer 71.43 mL (or g) of the 35 g/L standard solution into a volumetric flask.
b. Dilute to the mark with deionized water. Mix fully.
3. Prepare a 3.55 g/L chloride standard solution:
a. Transfer 56.8 mL (or g) of the 12.5 g/L standard solution into a volumetric flask.
Chloride, HR
Page 50
Chloride, HR
b. Dilute to the mark with deionized water. Mix fully.
HR chloride calibration procedure
1. Add 25 mL of the
3.55 g/L, 12.5 g/L and
35 g/L chloride standard
solution to three beakers.
2. Add a stir bar and stir

at a moderate rate.

one Chloride Ionic
Strength Adjustment (ISA)
Powder Pillow to each
standard solution.
4. Rinse the probe with

deionized water. Blot dry
with a lint-free cloth.
4-7
5. Put the probe into the
3.55 g/L chloride standard
solution. Tap the probe to
remove any air bubbles.
6. Push Calibrate. The

display shows the
standard solution value.
9. Push Done to view the

calibration summary.
10. Push Store to accept

the calibration.
7. Push Read. The

display shows
Stabilizing. When the
reading is stable, the
display shows the next
standard solution value.
8. Repeat steps 4 to 7 for

the 12.5 g/L and the 35 g/L
chloride standard
solutions.
Rinse the probe with

deionized water and blot
dry.
Chloride, HR
Page 51
Chloride, HR
Measure samples
Dilute samples that are greater than 35 g/L
If the chloride concentration is greater than 35 g/L (1 M), dilute the sample to a lower
concentration. Complete the steps that follow to make a 1:10 (10-fold) dilution.
1. Measure 2.5 mL of the sample in a 25-mL graduated cylinder.
2. Add deionized water to the 25-mL line.
3. Pour the diluted sample into a beaker.
4. Measure the concentration with the HR chloride measurement procedure.
5. Multiply the result by 10 to get the concentration of the sample before dilution.
HR chloride measurement procedure
1. Add 25 mL of sample
to a 50-mL beaker.
2. Add a stir bar and stir

at a moderate rate.

one Chloride Ionic
Strength Adjustment (ISA)
Powder Pillow per 25 mL
of sample.
4. Rinse the probe with

deionized water. Blot dry
with a lint-free cloth.
1-6
5. Put the probe into the
sample. Tap the probe to
remove any air bubbles.
Chloride, HR
Page 52
6. Push Read. The

display shows Stabilizing
and then the chloride
concentration of the
sample.
7. Repeat steps 1
8. When done, rinse the
through 6 for each sample. probe.
Chloride, HR

Collect samples in clean plastic or glass containers. Samples can be stored for a minimum of 28 days at room
temperature.
Interferences
The sensing element can respond to other ions in addition to chloride and cause a positive error. If
Chloride ISA is added to the standards and samples, the effect of interfering ions is minimized.
Samples can contain oxidizing agents such as Copper (Cu2+), Iron (ferrous) (Fe2+) and
Permanganate (MnO4-). Refer to Table 1.

Substance
Interference
Mercury
Must be absent from samples.
Ions that form insoluble

salts of silver
Can deposit a layer of salt on the sensing surface and cause probe errors.
Strong reducing solutions
Can form a surface layer of silver.

Description
Quantity/Test
Unit
Item no.
Chloride Ionic Strength Adjustor (ISA) Buffer Powder Pillows
100/pkg
2318069
Beaker, 50-mL, polypropylene
108041
IntelliCAL Chloride Ion Selective Electrode (ISE), 1 m cable
ISECL18101
Description
Unit
Item no.
Sodium chloride, ACS grade
454 g
18201H
Unit
Item no.
Bottle, wash, 500 mL
62011
Cylinder, graduated, 25-mL, poly
108140
4L
27256
ISECL18103
LZW9652C.97.002
1457445

Description
Deionized water
IntelliCAL Chloride Ion Selective Electrode (ISE), 3 m cable
sensION+ 9652C Chloride Combination Ion Selective Electrode (ISE), 1 m
Volumetric flask, 200 mL, Class A, glass
1
cable1
Use with sensION+ meters or other meters that have a BNC connection.
Chloride, HR
Page 53

HACH COMPANY
WORLD HEADQUARTERS
Telephone: (970) 669-3050
FAX: (970) 669-2932
05/2012, Edition 1
Conductivity
DOC316.53.01324
USEPA1 Direct Measurement Method2
Method 10256
(0.01 S/cm to 200.00 mS/cm)
Conductivity Meter

1
USEPA accepted for reporting for Standard method 2510-B
Procedure is equivalent to Standard Method 2510-B for wastewater.
Test preparation
How to use instrument-specific information

Table 1 shows the meter and probe options for this test. To use this table, select a meter, then read
across to find the probe options.
Table 1 Instrument-specific information
Meter
Standard probe
Rugged probe1
HQ40d, HQ30d or HQ14d
CDC40101, CDC40103
CDC40105, CDC40110, CDC40115, CDC40130
Designed for field use.

Collect samples in clean plastic or glass bottles. Fill completely and cap tightly.
Measure samples as soon as possible after collection. If immediate measurement is not possible, samples can be kept at
0 to 6 C (32 to 43 F) for a minimum of 24 hours.
If solutions are not at the reference temperature, the meter automatically adjusts the conductivity value to the value at the
reference temperature.
Water samples that contain oils, grease or fats will add a layer of residue on the electrode and can decrease the accuracy of
the readings. If this occurs, clean the probe with a strong detergent solution, then thoroughly rinse with deionized water.
Mineral build-up on the probe can be removed with a dilute (1:1) hydrochloric acid solution. Refer to the meter user manual.
For the best results, calibrate before use or measure the conductivity of a standard solution to make sure that the measured
conductivity agrees with the known value of the standard. Calibration instructions are given in the meter user manual.
For the most accurate results with high conductivity samples, calibrate the cell constant or check the accuracy of the meter
with a 111.3 mS/cm (1 Demal) certified conductivity standard.
Measurement errors can occur if the correct temperature correction value is not selected. Refer to Table 3 for typical
correction values.
To display other units such as TDS, salinity or resistivity, refer to the meter user manual.
Items to collect:
Description
Quantity
Beaker, poly, 100-mL
HQd meter and conductivity IntelliCAL probe
Conductivity
Page 55
Conductivity
Items to collect: (continued)
Description
Quantity
One of the following conductivity standard solutions

NaCl conductivity standards:
NaCl standard solution, 180 10 S/cm
NaCl standard solution, 18 10 mS/cm
KCl conductivity standards:

0.1 Molar KCl, 12.88 mS/cm at 25 C
500 mL
0.01 Molar KCl, 1413 S/cm at 25 C
500 mL
0.001 Molar KCl, 148 S/cm at 25 C
500 mL
Certified conductivity standards:

KCl, 1 Demal, 111.3 mS/cm 0.5% at 25 C
500 mL
KCl, 0.1 Demal, 12.85 mS/cm 0.35% at 25 C
500 mL
KCl, 0.01 Demal, 1408 S/cm 0.5% at 25 C
500 mL
NaCl, 0.05%, 1015 S/cm 0.5% at 25 C
500 mL
Conductivity
1. Prepare the electrode

and the meter. Refer to the
documentation for the
electrode or the meter.
The meter selects the
range automatically.
2. Laboratory tests: Put

the probe in a beaker that
contains the sample. Move
the probe up and down
and tap it on the beaker to
remove bubbles.
Field tests: Put the probe
in the sample. Move the
probe up and down to
remove bubbles from the
electrode.
The vent holes must be
completely submerged.
Conductivity
Page 56
3. Turn the meter on.

Make sure that the meter
is set to measure
conductivity.
When the conductivity
value is stable, store or
record the value.
4. Rinse the probe

thoroughly with deionized
water after each
measurement.
Conductivity
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
S/cm
mS/cm 1000
S/cm
mS/cm
S/cm 0.001
S/cm
mhos/cm
S/cm 1
mS/cm
mmhos/cm
mS/cm 1
S/cm
mg/L TDS
S/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
S/cm
ohms cm
1,000,000 S/cm
mS/cm
ohms cm
1,000 mS/cm
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 from hydroxide ions, neutralize the pH of the sample:
a. Add 4 drops of phenolphthalein indicator solution to 50 mL of sample. The solution
becomes pink.
b. Add gallic acid solution by drops until the pink color completely goes away.
c. Measure the conductivity.
For more information on conductivity measurements in oil and gas field waters, refer to the
Conductivity and Total Dissolved Solids Procedures Explained section of the Hydraulic
Fracturing Water Analysis Handbook.
Conductivity
Page 57
Conductivity
Accuracy check
Measure the conductivity of a sodium chloride (NaCl) standard solution that has a similar value to
the conductivity of typical samples. The measured conductivity should be close to the known value
of the standard solution. If the value is outside of the accuracy limits on the standard solution label,
complete a calibration with this standard solution. Refer to the meter user manual.
Method performance
The accuracy of a conductivity measurement depends on many factors that are associated with
the overall conductivity system, which includes the meter, electrode and calibration solutions.
Refer to the documentation for the electrode or the meter for more information.
Summary of 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 useful estimate of concentration.
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 (103 S or mS/cm) and
microSiemens/cm (106 S or S/cm).

Required apparatus
Description
Unit
Item no.
HQ40d meter
HQ40d53000000
HQ30d meter
HQ30d53000000
HQ14d meter
HQ14d53000000
IntelliCAL conductivity probe, standard, with 1 m cable
CDC40101
IntelliCAL conductivity probe, standard, with 3 m cable
CDC40103
IntelliCAL conductivity probe, rugged, with 5 m cable
CDC40105
CDC40110
CDC40115
CDC40130
Unit
Item no.
Sodium chloride standard solution, 180 10 mS/cm, 90 1 mg/L TDS
100 mL
2307542
100 mL
1440042
100 mL
210542
Select one meter and one probe:
Description
NaCl conductivity standards:
Conductivity
Page 58
Conductivity
Description
Unit
Item no.
100 mL
2307442
0.1 M KCl, 12.88 mS/cm at 25 C
500 mL
C20C250
0.01 M KCl, 1413 S/cm at 25 C
500 mL
C20C270
0.001 M KCl, 148 S/cm at 25 C
500 mL
C20C280
KCl, 1 Demal, 111.3 mS/cm 0.5% at 25 C
500 mL
S51M001
KCl, 0.1 Demal, 12.85 mS/cm 0.35% at 25 C
500 mL
S51M002
KCl, 0.01 Demal, 1408 S/cm 0.5% at 25 C
500 mL
S51M003
NaCl, 0.05%, 1015 S/cm 0.5% at 25 C
500 mL
S51M004
Unit
Item no.
108042
50 mL SCDB
1442326
500 mL
88449
15 mL SCDB
16236
62014
4L
27256
Sodium chloride standard solution, 18,000 50 mS/cm, 9000 25 mg/L TDS

KCl conductivity standards:
Certified conductivity standards:

Description
Beaker, poly, 100-mL
Gallic acid solution
Hydrochloric acid solution, 1:1
Phenolphthalein indicator solution
Wash bottle, 125-mL
Water, deionized
Conductivity
Page 59

HACH COMPANY
WORLD HEADQUARTERS
Telephone: (970) 669-3050
FAX: (970) 669-2932
08/2012, Edition 1
Barium, 8014
Hardness, Calcium
DOC316.53.01318
Titration Method using EDTA
Method 10253
(100 to 200,000 mg/L as CaCO3)
Digital Titrator
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.

Description
Quantity
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
Graduated cylinder
Water, deionized
4L
1
Hardness, Calcium
Page 61
Hardness, Calcium
Test procedure
See
Table 1
or
Table 2
1. Select a sample
volume and titration
cartridge from Table 1.
2. Put a clean delivery

tube into the 0.800 M
EDTA titration cartridge.
Refer to Identify the

sample volume if the
concentration ranges are
unknown.
Put the cartridge in the

titrator.

is 100 mL, add 2 mL of
8 N Potassium Hydroxide
Standard Solution.

one CalVer 2 Calcium
Swirl to mix.
If the sample volume is

50 mL or less, add 1 mL of
8 N Potassium Hydroxide
Standard Solution.
Swirl to mix.
3. Hold the digital titrator

with the cartridge tip up.
Turn the delivery knob to
eject air and a few drops of
titrant. Wipe the tip.
Reset the counter to zero.
4. Use a graduated
measure the sample
volume identified in step 1.
Put the sample in a clean,
250-mL Erlenmeyer flask.
less than 100 mL, dilute to
about 100 mL with
deionized water.
7. Put the delivery tube

in the solution and swirl
the solution.
color changes from red to
pure blue.

concentration:
mg/L Ca as CaCO3
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
Page 62
Hardness, Calcium
Table 1 Range-specific informationmg/L

Sample volume (mL)
Multiplier
100400
100
200800
50
5002000
20
10004000
10
10
20008000
20
500020,000
50
10,00040,000
100
20,00080,000
0.5
200
50,000200,000
0.2
500
Identify the sample volume

Screen the samples to estimate the calcium hardness concentration when the concentration
ranges are unknown.
1. Add 75100 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
25
10
10
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.
Hardness, Calcium
Page 63
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 cyanidecontaining 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.
Aluminum
Causes a slow endpoint but up to 200 mg/L aluminum can be tolerated if sufficient time is
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.
Cobalt
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.
Copper
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.
Hardness, Calcium
Page 64
Hardness, Calcium
Substance

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.
Magnesium
Interference from magnesium is prevented up to 200 mg/L by the formation of magnesium

hydroxide at the high test pH but higher levels prevent a distinct endpoint.
Manganese
Interferes at levels greater than 5 mg/L.
Nickel
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.
Orthophosphate
Causes a slow endpoint but does not interfere if the calcium phosphate that forms is given
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.
Temperature
Samples at 20 C (68 F) or colder should be titrated slowly near the endpoint to provide
sufficient time for the color change.
Zinc
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.
Highly buffered samples or

extreme sample pH
May be greater than the buffering capacity of the reagents. Adjust the pH before starting the
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.
Hardness, Calcium
Page 65
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
Description
Quantity/Test
Unit
Reagent set (100 tests):
Item no.
2447500
(1) CalVer 2 Calcium Indicator Powder Pillows
1 pillow
100/pkg
85299
(1) Potassium Hydroxide Standard Solution, 8 N
12 mL
100 mL MDB
28232H
varies
1439901
(1) EDTA titration cartridge, 0.800 M
Required apparatus
Description
Quantity/Test
Item no.
Digital titrator
1690001
50546
50838
50840
50841
50842
1970001
Tensette Pipet tips
50/pkg
2185696
Delivery tube, 180 hook
5/pkg
1720500
Unit
Item no.
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
Description
Hardness, Calcium
Page 66
Hardness, Calcium

Description
Unit
Item no.
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
29 mL
102233
Hardness 2 Indicator Solution
100 mL
42532
1L
74053
113 g
28014
Nitric Acid Solution, ACS
500 mL
15249
Nitric Acid Solution, 1:1
500 mL
254049
Sodium Hydroxide Standard Solution, 5 N
50 mL
245026
Potassium Cyanide
125 g
76714
2095352
TitraStir stir plate, 115 VAC
1940000
1940010
4L
27256
500 mL
28249
1451538
1451520
Pipet filler, safety bulb
1465100
Bottles, sampling, poly, 500 mL
2087079
Bromphenol green-methyl red indicator solution
100 mL MDB
2329232
Phenolphthalein Indicator Solution, 5 g/L
100 mL MDB
16232
pH meter
Pipet tips
50/pkg
2185696
1970010
Spoon, measuring, 1 g
51000
Spoon, measuring, 0.5 g
90700
51100
HexaVer Hardness Titrant, 0.020 N

ManVer 2 Hardness Indicator Powder
Water, deionized
Potassium Hydroxide, 8 N
Voluette Ampule breaker, 10 mL

Sampling bottle with cap, low density polyethylene, 250 mL
2196800
12/pkg
2087076
Hardness, Calcium
Page 67

HACH COMPANY
WORLD HEADQUARTERS
Telephone: (970) 669-3050
FAX: (970) 669-2932
09/2011, Edition 1
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
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.

Description
ManVer 2 Hardness Indicator Powder Pillow
Hardness 1 Buffer Solution
0.800 M EDTA titration cartridge
Quantity
1
2 mL
1 cartridge
Digital titrator
Graduated cylinder
Water, deionized
4L
1
Hardness, Total
Page 69
Hardness, Total
Test procedure
See
Table 1
or
Table 2
1. Select a sample
volume from Table 1.
Refer to Identify the
sample volume if the
concentration ranges are
unknown.
2. Put a clean delivery

tube into the 0.800 M
EDTA titration cartridge.
Put the cartridge in the
titrator.
3. Hold the digital titrator

with the cartridge tip up.
Turn the delivery knob to
eject air and a few drops of
titrant. Wipe the tip.
Reset the counter to zero.
4. Use a graduated
measure the sample
volume identified in step 1.
Put the sample in a clean,
250-mL Erlenmeyer flask.
less than 100 mL, dilute to
about 100 mL with
deionized water.
5. Add 2 mL of Hardness
1 Buffer Solution. Swirl to
mix.

one ManVer 2 Hardness
Swirl to mix.
7. Put the delivery tube

in the solution and swirl
the solution.
color changes from red to
pure blue.

concentration:
mg/L total hardness as
CaCO3
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
Page 70
Hardness, Total
Table 1 Range-specific informationmg/L

Sample volume (mL)
Multiplier
100400
100
200800
50
5002000
20
10004000
10
10
20008000
20
500020,000
50
10,00040,000
100
20,00080,000
0.5
200
50,000200,000
0.2
500
Identify the sample volume

Screen the samples to estimate the hardness concentration when the concentration ranges are
unknown.
1. Add 75100 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
25
10
10
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.
Hardness, Total
Page 71
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 cyanidecontaining 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
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
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.
As an alternative, the interference can be removed by the addition of a CDTA powder pillow.
Refer to Table 4 and Table 5.
Barium
Cobalt
Hardness, Total
Page 72
Barium is a by-product from the drilling process and can be present in very high
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.
Hardness, Total
Substance

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
a CDTA powder pillow. Refer to Table 4 and Table 5.
Manganese
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
Orthophosphate
Causes a slow endpoint but does not interfere if the calcium phosphate that forms is given
time to redissolve during the titration.
Polyphosphates
Interferes directly and must be absent.
Polyvalent metal ions
Although less common than calcium and magnesium, other polyvalent metal ions cause the
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

extreme sample pH
May exceed the buffering capacity of the reagents. Adjust the pH before starting the test
(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
Hardness, Total
Page 73
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
Page 74
Hardness, Total
Standard solution method
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
Description
Quantity/Test
Unit
Reagent set (100 tests):
Item no.
2448100
(1) ManVer 2 Hardness Indicator Powder Pillows
100/pkg
85199
2 mL
100 mL MDB
42432
Description
Quantity/Test
Unit
Item no.
Digital titrator
1690001
50546
50838
50840
50841
50842
1970001
Tensette Pipet tips
50/pkg
2185696
Delivery tube, 180 hook
5/pkg
1720500
Description
Unit
Item no.
Calcium Chloride Standard Solution, 1000-mg/L as CaCO3
1L
12153
16/pkg
218710
(1) Buffer Solution, Hardness 1
Required apparatus
Hardness Standard Solution, Voluette ampule, 10,000-mg/L as CaCO3, 10-mL
Hardness, Total
Page 75
Hardness, Total
Description
CDTA Magnesium Salt Powder Pillow
Unit
Item no.
100/pkg
1408099
ManVer 2 Hardness Indicator Powder
113 g
28014
29 mL
102233
Hardness 2 Indicator Solution
100 mL
42532
1L
74053
Sodium Hydroxide Standard Solution, 5 N
50 mL
245026
Nitric Acid Solution, ACS
500 mL
15249
Nitric Acid Solution, 1:1
500 mL
254049
125 g
76714
2095352
1940000
HexaVer Hardness Titrant, 0.020 N
Potassium Cyanide
1940010
4L
27256
Pipet, volumetric, 10 mL Class A
1451538
Pipet, volumetric, 20 mL Class A
1451520
Water, deionized
Pipet filler safety bulb
1465100
1970010
Spoon, measuring, 1 g
51000
90700

Pipet tips, for TenSette Pipet 1970010
Voluette breaker
Sampling bottle with cap, low density polyethylene, 250 mL

51100
50/pkg
2199796
2196800
12/pkg
2087076
HACH COMPANY
WORLD HEADQUARTERS
Telephone: (970) 669-3050
FAX: (970) 669-2932
09/2011, Edition 1
Iron, Total
DOC316.53.01310
FerroVer Method
Method 10249
03.0, 030.0 and 0300.0 mg/L Fe
Powder Pillows
Scope and Application: For oil and gas field waters; digestion is required for determining total iron
USEPA approved for reporting wastewater analysis (digestion is required)
Test procedure
1. Push: PRGM
The display shows:
PRGM ?
Instrument setup on
page 80 to add the
program to the
instrument.
2. Push: 127 ENTER

The display shows
mg/L, Fe LR, Fe MR or
Fe HR and the ZERO
icon.
3. Push: CONC to select

the test range.
Fe LR 03.0 mg/L Fe
Fe MR 030.0 mg/L Fe
Fe HR 0300.0 mg/L Fe
Identify test ranges: First
analyze samples with
unknown iron
concentrations with the
Fe HR test. If no iron is
found in step 13, analyze
the samples with the MR
and LR test ranges.

sample cell.
Fe LR: 10 mL
Fe MR: 1.0 mL
Fe HR: 0.1 mL
Use a TenSette or glass
pipet to measure the 1.0
or 0.1 mL sample sizes.
6. Tighten the cap on

the sample cell and invert
to mix.
7. Remove the cap from

the sample cell and add
2 drops of 1 M EDTA
Solution to the sample.
sample cell and invert to
mix.
8. Put the sample cell

into the cell holder. Put
the instrument cap over
the sample cell.
Note: Adjust the pH of

stored samples before
analysis.

is less than 10 mL, fill the
sample to the 10 mL line
with deionized or ironfree water.
Iron, Total
Page 77
Iron, Total
9. Push: ZERO
shows:
0.0 mg/L Fe LR, Fe MR
or Fe HR

FerroVer Iron Reagent
Powder Pillow to the
sample cell. Tighten the
and invert to mix.
The accuracy is not
powder.
11. Push:
TIMER ENTER
A three-minute reaction
period starts.
An orange color will form
if iron is present.
If the sample contains
visible rust or if five drops
of EDTA were used in
step 7, the sample should
be allowed to react for at
least five minutes.
12. Put the prepared

sample into the cell
holder. Put the
sample cell.
13. Push: READ

The cursor will move to the right, then the result for the
selected test range in mg/L iron (Fe) is shown.
Note:For best results use the Standard Adjust option. Refer to
the procedures manual for more information about Standard
Adjust.

Collect samples in acid-cleaned glass or plastic containers. No acid addition is necessary if the
sample is analyzed immediately. To preserve samples, adjust the pH to 2 or less with nitric acid
(about 2 mL per liter). Keep preserved samples in a storage up to six months at room temperature.
Adjust the pH to between 3 and 5 with 5.0 N Sodium Hydroxide Standard Solution before analysis.
Correct the test result for volume additions; refer to Section 1 Correcting for Volume Additions of
the procedures manual for more information. Filter the sample before the acid addition to find
dissolved iron only.
Accuracy Check
Iron, Total
Page 78
Iron, Total
2. Open a 25 mg/L Iron Voluette Ampule Standard Solution.
3. Use the TenSette Pipet to add 0.1, 0.2, and 0.3 mL of the 25 mg/L standard, respectively, to
the samples and mix fully.
5. Examine the results. The iron concentration should increase by 0.25 mg/L for Fe LR,
2.5 mg/L for Fe MR and 25.0 mg/L for Fe HR for each 0.1 mL of standard that is added.
6. If these increases do not occur, refer to Section 1 Standard Additions of the procedures
manual for troubleshooting information.
Prepare a 1.0-mg/L iron standard solution.
Dilute 1.00 mL of Iron Standard Solution, 100 mg/L Fe, to 100 mL with deionized water.
Use 10 mL of the standard in step 4 to complete the Fe LR procedure for powder pillows. Results
should be between 0.90 mg/L and 1.10 mg/L Fe.
Method Performance
Precision
In a single laboratory, with a standard solution of 2.0 mg/L Fe and two of powder pillows with the
instrument, a single operator got a standard deviation of 0.02 mg/L Fe.
The EDL for program 127 is 0.1 mg/L Fe. For more information on derivation and use of the
estimated detection limit, refer to Section 1 of the procedures manual.
Interferences
Interfering Substances and Suggested Treatments
Interfering Substance
Interference Level and Treatment
Barium, Ba2+
The dilution of samples to measure iron lowers most barium concentrations below
interference levels. No effects are seen on analyzed solutions which contain less
than 50 mg/L of Ba. No effects are seen when 1.0 or 0.1 mL of sample is used in step
4. A turbidity may show at higher levels. Add 5 drops of EDTA Solution to the solution
in step 5 and do the analysis again. Allow the sample to react for 5 minutes.
Calcium, Ca2+
No effect at less than 10,000 mg/L as CaCO3
Cl-
No effect at less than 185,000 mg/L.
Cu2+
No effect. Masking agent is contained in FerroVer Iron Reagent.
Chloride,
Copper,
High Iron Levels
Prevents color development. Dilute the sample and test again to verify results.
Magnesium
No effect at 100,000 mg/L as CaCO3.
Molybdate, Molybdenum
High Sulfide Levels,
S2-
No effect at 25 mg/L as Mo.

1.
2.
3.
Strontium, Sr2+
Prepare in fume hood or well-ventilated area. Add

5 mL HCl to 100 mL sample in a 250-mL Erlenmeyer flask. Boil for 20 minutes.
Cool. Adjust the pH to 35 with NaOH. Adjust the volume to 100 mL with
deionized water.
Analyze.
Strontium by itself does not interfere. Strontium in combination with Barium will cause
a precipitate to form. The dilution of samples to measure iron lowers most strontium
concentrations below interference levels. No effects are seen on analyzed solutions
which contain less than 50 mg/L of combined Ba and Sr. No effects are seen when
1.0 or 0.1 mL of sample is used in step 4. A turbidity may start at higher levels. Add 5
drops of EDTA Solution to the solution in Step 5 and do the analysis again. Allow the
sample to react for 5 minutes
Iron, Total
Page 79
Iron, Total
Interfering Substance
Interference Level and Treatment
Sample pH (extreme)
Adjust pH to 3-5. Refer to Interferences in Section 1 of the procedures manual.
Highly Buffered Samples
Adjust pH to 3-5. Refer to Interferences in Section 1 of the procedures manual.
Summary of Method
FerroVer Iron Reagent reacts with all soluble iron and most insoluble forms of iron in the sample to
produce soluble ferrous iron. Ferrous iron reacts with 1,10-phenanthroline indicator in the reagent
to form an orange color in proportion to the iron concentration.
Instrument setup
This procedure adds the program 127 to a DR/820, DR/850 or DR/890 instrument.
Iron, Total
Page 80
Iron, Total

Line Number
Enter
Line Number
Enter
127
29
82
24
30
70
73
31
101
32
32
33
72
34
82
35
65
36
32
37
10
38
11
39
66
12
64
40
200
13
24
41
14
81
42
15
235
43
16
44
33
17
45
128
18
46
19
47
15
20
70
48
21
101
49
180
22
32
50
23
76
51
24
82
52
25
70
53
26
101
54
132
27
32
55
28
77
56
255
Iron, Total
Page 81
Iron, Total
REQUIRED REAGENTS & APPARATUS (Using Powder Pillows)

Description
Quantity Per Test
Unit
Item No.
1 pillow
100/pkg
2105769
6/pkg
2401906
2 drops
50 mL
2241926
FerroVer Iron Reagent Powder Pillows

Sample cell, 10-20-25 mL, with screw cap
EDTA Solution 1M
OPTIONAL REAGENTS
Description
Unit
Item No.
Hydrochloric Acid Standard Solution, 6 N
500 mL
88449
Iron Standard Solution, 100 mg/L
100 mL
1417542
Iron Ampule Standard, 25 mg/L
16/pkg
1425310
100 mL MDB
245032
4L
27256
Sodium Hydroxide Standard Solution, 5.0 N

Water, deionized
OPTIONAL APPARATUS
Description
Unit
Item No.
Ampule Breaker, Voluette Ampules
2196800
Cylinder, graduated, poly, 25 mL
108140
Cylinder, graduated, poly, 100 mL
108142
Flask, Erlenmeyer, 250 mL
50546
Flask, volumetric, Class A, 100 mL
1457442
1465100
Pipet, serological, 2 mL
53236
1970001
Pipet Tips, for 1970001 TenSette Pipet
50/pkg
2185696
1000/pkg
2185628
Pipet, volumetric, Class A, 1.00 mL
1451535
Pipet, TenSette 1.0 - 10.0 ml
1970010
50/pk
2199796
250/pk
2199725

HACH COMPANY
WORLD HEADQUARTERS
Telephone: (970) 669-3050
FAX: (970) 669-2932
09/2011, Edition 1
pH
pH
DOC316.53.01323
USEPA electrode method
Method 10255
pH meter
Scope and Application: For oil and gas field waters.1

1
Based on Standard Method 4500-H+B, ASTM Method D1293-84(90)/(A or B) and USEPA Method 150.
Test preparation

Table 1 shows the meter and probe options for this test. To use this table, select a meter, then read
across to find the probe options.
Meter
Standard probe
Rugged probe1
HQ40d, HQ30d or HQ11d
PHC10101, PHC10103 (gel)

PHC30101, PHC30103 (liquid)
PHC10105, PHC10110, PHC10115, PHC10130
Designed for field use.

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, the shroud may need to be removed before measurement and calibration.
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 Sample collection, preservation, general storage and
cleaning.
Items to collect:
Description
Quantity
pH meter and probe combination
pH buffers (4.0, 7.0, 10.0)
Beakers/sample containers
pH
Page 83
pH
Sample pH measurement (calibration required)
1. Prepare the electrode

and the meter. Refer to the
2. Connect the electrode

to the meter.
3. Turn the meter on.

Make sure that the meter
is set to measure pH.
4. Change any of the

setup options for
measurement or
calibration. Refer to the
5. In three separate
beakers or containers,
prepare fresh buffers of
4.0, 7.0 and 10.0 pH.
6. Calibrate the meter

and electrode. Refer to the
7. Rinse the electrode

with deionized water and
blot dry.
8. Put the electrode in

the sample and select
Read.
Make sure that the

calibration slope is good
(58 (3) mV per pH unit
at 25 C).
9. When the pH value is

stable, store or record the
pH value and the
temperature value.
pH
Page 84
For a faster response, stir

the sample at a slow to
moderate rate.
pH
Sample collection, preservation, general storage and cleaning
Collect samples in clean plastic or glass bottles. Fill completely and cap tightly.
Measure samples immediately, preferably in the field.
For general electrode storage, use the Hach storage solution or a 3 M potassium chloride
(KCl) solution.
A contaminated glass bulb or fouled electrode can cause a slow response time.
Do not clean the bulb too often because the bulb life can decrease.
To clean an electrode with general contamination:

a. Soak the electrode tip in 0.1 N hydrochloric acid (HCl) for 2 minutes.
b. Soak the electrode tip in 0.1 N sodium hydroxide (NaOH) for 2 minutes.
c. Soak the electrode tip in 0.1 N hydrochloric acid for 2 minutes.
d. Rinse with deionized water.
e. Soak in deionized water for a minimum of 15 minutes.
To clean an electrode that has contamination from oils and fats, put the electrode tip in a
detergent solution. Clean with a soft brush or ultrasonic bath. Do not scratch the glass bulb.
Interferences
The sodium error is low but increases at pH values that are higher than pH 11. The acid error is
negligible. For more information, refer to the documentation for the electrode or the meter.
Accuracy check
Electrode operation
The electrode operation is satisfactory when the calibration slope is within the specified range
(typically 58 (3) mV at 25 C).
Calibration accuracy
Measure the pH of a fresh buffer solution. A calibration is satisfactory when the measured pH
agrees with the known pH value of the buffer.
Method performance
The accuracy of a pH measurement depends on many factors that are associated with the overall
pH system, which includes the meter, electrode and calibration buffers. Refer to the
documentation for the electrode or the meter 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 log10 aH+, 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.
pH
Page 85
pH

Required apparatus and reagents
Description
Unit
Item no.
HQ40d meter
HQ40d53000000
HQ30d meter
HQ30d53000000
Select one meter and one probe:
HQ11d meter
HQ11d53000000
IntelliCAL pH gel probe, standard, with 1 m cable
PHC10101
IntelliCAL pH gel probe, standard, with 3 m cable
PHC10103
IntelliCAL pH liquid probe, standard, with 1 m cable
PHC30101
IntelliCAL pH liquid probe, standard, with 3 m cable
PHC30103
IntelliCAL pH gel probe, rugged, with 5 m cable
PHC10105
PHC10110
PHC10115
PHC10130
pH filling solution (for PHC301), 3M KCl, saturated with AgCl
30 mL
2841700
pH electrode storage solution
500 mL
2756549
Refill solution and storage:
Description
pH color-coded buffer solution kit (NIST), 500 mL, includes:
Unit
Item no.
2947600
pH 4.01 0.02 pH buffer (NIST)
500 mL
2283449
500 mL
2283549
500 mL
2283649
50/pkg
2226966
Powder
pillows1
pH 4.01 0.02 pH buffer powder pillow (NIST)

50/pkg
2227066
50/pkg
2227166
500 mL
S11M001
Radiometer Analytical (IUPAC Series certified pH standards):

pH 1.679 0.010 at 25 C
pH 4.005 0.010 at 25 C
500 mL
S11M002
pH 7.000 0.010 at 25 C
500 mL
S11M004
pH 10.012 0.010 at 25 C
500 mL
S11M007
pH buffer 1.09, technical
500 mL
S11M009
500 mL
S11M010
500 mL
S11M011
Unit
Item no.
Sample bottle, general purpose with screw-cap, polypropylene, 500-mL
2758101
Sample bottle, cleaned and certified, HDPE, suitable for EPA reporting, 500-mL
2758201

Description

HACH COMPANY
WORLD HEADQUARTERS
Telephone: (970) 669-3050
FAX: (970) 669-2932
08/2012, Edition 1
Sulfate
DOC316.53.01312
SulfaVer 4 Method1
Method 10248
(070, 0700 and 07000 mg/L)
Powder Pillows

1
Adapted from Standard Methods for the Examination of Water and Wastewater.
USEPA accepted for reporting wastewater analysis
Test procedure
1. Push PRGM.
The display shows
PRGM ?
Instrument Setup on
page 89 to add the
program to the
instrument.
2. Push 128 ENTER.

The display shows
mg/L, SO4 L, SO4 M or
SO4 H and the ZERO
icon.

10-mL line. Tighten the
and invert to mix.
6. Put the sample cell in

the cell holder. Put the
sample cell.
Note:A 10-mL graduated

mixing cylinder can be used
in steps 4 and 5.

the test range:
SO4 L: 070 mg/L
SO4 M: 0700 mg/L
SO4 H: 07000 mg/L

sample cell:
SO4 L: 10 mL
SO4 M: 1.0 mL
SO4 H: 0.1 mL
Note:Use a TenSette or
glass pipet to measure
0.1 mL or 1.0 mL.
7. Push ZERO.
shows:
0 mg/L SO4 and L, M or
H

SulfaVer 4 Sulfate
Reagent Powder Pillow
to the sample cell.
Tighten the cap and
invert to mix.
Note:The sample will
become cloudy if sulfate is
in the sample.
Note:Accuracy is not
powder.
Sulfate
Page 87
Sulfate
9. Push
TIMER ENTER
A 5-minute reaction
period starts.
Do not move the sample
cell during the reaction
period.
10. Within five minutes

after the timer beeps, put
the prepared sample in
the instrument. Put the
sample cell.
11. Push READ.

sulfate is shown.
Clean the sample cells with soap and a brush.
Note:For best results use the Standard Adjust option. Refer
to Standard Adjust on page 89.

Collect the sample in a clean plastic or glass bottle. Samples can be used for up to 28 days if they
are kept at or less than 4 C (39 F). Let the sample temperature increase to room temperature
before analysis.
Interferences
Known interferences are shown in Table 1. The interference levels are applicable to an undiluted
10-mL sample. The interference levels increase proportionally as the sample is diluted.
Substance
Interference Level
Barium
Interferes at all levels. The greater the barium concentration compared to the sulfate concentration,
the greater the error. Samples with high barium concentrations will generally give a result that is
20% lower than the actual sulfate concentration.
Calcium
Chloride
40,000 mg/L as Cl-
Magnesium
Silica
500 mg/L as CaCO3
Turbidity
Filter samples that have a high level of turbidity
Accuracy Check
Use the standard additions method to validate the test procedure, reagents and instrument and to
find if there is an interference in the sample.
2. Use a TenSette Pipet to add 0.1, 0.2 and 0.3 mL of a 1000 mg/L Sulfate Standard Solution to
the sample cells. Mix fully.
Sulfate
Page 88
Sulfate
4. Review the results. The sulfate concentration should increase by 10 mg/L for SO4 L,
100 mg/L for SO4 M or 1000 mg/L for SO4 H for each 0.1 mL of standard that is added.
5. If the concentration does not increase by the correct amount, refer to Standard Additions in
Section 1 of the procedures manual.
Use a 50 mg/L Sulfate Standard Solution to validate the test procedure, reagents and the
instrument. Select the SO4 L test range in step 3 and use 10 mL of the standard solution instead of
the sample in step 4. To adjust the result, refer to Standard Adjust.
To prepare this standard solution, add 5.0 mL of a 1000 mg/L Sulfate Standard Solution to a 100mL volumetric flask. Dilute to the mark with deionized water and mix fully.
Standard Adjust
The standard adjust option is recommended when program 128 is used.
6. Measure the concentration of a 50 mg/L Sulfate Standard Solution. Select the SO4 L range
and use 10 mL of the standard solution. Keep the sample cell in the instrument.
8. Push ENTER.
9. Push the numbers 50 to make the instrument read the value of the standard solution
concentration.
10. Push ENTER to complete the adjustment.
Note: The MR and HR calibration curves are adjusted proportionally when the SO4 L calibration curve is
adjusted. Refer to Section 1, Standard Curve Adjustment of the procedures manual.
Method Performance
Precision
In a single laboratory, with a 50 mg/L sulfate standard solution, two representative lots of powder
pillows and the instrument, a single operator got a standard deviation of 0.5 mg/L sulfate.
The EDL for program 128 SO4 L is 4.9 mg/L SO4. For more information on derivation and use of
the estimated detection limit, refer to Section 1 of the procedures manual.
Summary of Method
Sulfate ions in the sample react with barium in the SulfaVer 4 Sulfate Reagent to make an
insoluble barium sulfate precipitate. The amount of precipitate is proportional to the sulfate
concentration. The SulfaVer 4 also contains a stabilizing agent to hold the precipitate in
suspension.
Instrument Setup
This procedure adds program 128 to a DR/820, DR/850 or DR/890 instrument.
Sulfate
Page 89
Sulfate
Sulfate
Page 90
Line Number
Enter
Line Number
Enter
128
29
77
24
30
83
72
31
79
32
52
33
32
34
72
35
65
65
36
32
198
37
10
169
38
11
251
39
66
12
66
40
200
13
25
41
14
10
42
15
61
43
16
44
80
17
45
18
46
19
47
30
20
83
48
21
48
49
44
22
52
50
23
32
51
24
76
52
25
83
53
26
79
54
37
27
52
55
28
32
56
255
Sulfate
REQUIRED REAGENTS AND APPARATUS

Description
SulfaVer 4 Sulfate Reagent Powder Pillows
Sample Cell, 10-20-25 mL, with cap
Quantity Per Test
Units
Item No.
1 pillow
100/pkg
2106769
6/pkg
2401906
Units
Item No.
OPTIONAL REAGENTS
Description
Sulfate Standard Solution, 50 mg/L
500 mL
257849
Sulfate Standard Solution, 1000 mg/L
500 mL
2175749
4L
27256
Water, deionized
OPTIONAL APPARATUS
Description
Units
Item No.
2088638
100/pkg
189457
Flask, volumetric, 100 mL, Class A
1457442
Funnel, poly, 65 mm
108367
Filter Paper, folded, 12.5 cm
1970001
50/pkg
2185696
1970010
50/pkg
2199796

Pipet, volumetric, 5.00 mL, Class A
1451537
1465100
Sulfate
Page 91

HACH COMPANY
WORLD HEADQUARTERS
Telephone: (970) 669-3050
FAX: (970) 669-2932
06/2012, Edition 2
Sulfide
DOC316.53.01320
Methylene Blue Method1
Method 10254
(00.70, 07.00 and 070.00 mg/L)

1
Adapted from Standard Methods for the Examination of Water and Wastewater.
USEPA accepted for wastewater analysis. Procedure is equivalent to USEPA method 376.2 or Standard Method
4500-S2- D for wastewater.
Test procedure
1. Push PRGM.
The display shows
PRGM ?
Instrument setup on page
95 to add the program to
the instrument.
2. Push 129 ENTER.

The display shows
mg/L, S LR, S MR or
S HR and the ZERO
icon.

the test range.
S LR: 00.70 mg/L
S MR: 07.00 mg/L
5. Sample
preparation: Add the
sample volume that is
specified for the test
range to a clean sample
cell.

25-mL line.
7. Use the dropper to

add 1.0 mL of Sulfide 1
Reagent to each sample
cell.
S HR: 070.00 mg/L
4. Blank preparation:
Add 25 mL of deionized
water to a sample cell.
A 25-mL graduated
mixing cylinder can be
used in steps 4 and 5.
8. Swirl to mix.
S LR: 25 mL
S MR: 2.5 mL
S HR: 0.25 mL
Use a pipet to measure
0.25 mL or 2.5 mL.
Sulfide
Page 93
Sulfide
9. Use the dropper to

add 1.0 mL of Sulfide 2
Reagent to each sample
cell.
10. Immediately tighten

the cap on each sample
cell and mix.
13. Push ZERO.

shows
0.00 mg/L S and LR, MR
or HR
14. At the end of the

reaction period, put the
prepared sample in the
instrument. Put the
sample cell.
The solution becomes

pink and then blue if
sulfide is in the sample.
11. Push
TIMER, then ENTER.
A 5-minute reaction
period starts.
12. Put the blank in the

instrument. Put the
sample cell.
15. Push READ.

sulfide is shown.
Note: For best results use the Standard Adjust option. Refer
to the instrument manual.
Sampling and storage

Collect the samples in clean plastic or glass bottles. Fill the bottles completely, then put the caps
on tightly. Keep any agitation or air exposure to a minimum. Analyze the samples immediately.
Soluble sulfides
Complete the steps that follow to measure the concentration of soluble sulfides in the sample.
1. Use a centrifuge to make a separation of the soluble and insoluble sample components. Make
sure that the centrifuge tubes are filled completely and have a cap.
2. Use the liquid portion as the sample in the test procedure to measure the concentration of
soluble sulfides.
To make an estimate of the insoluble sulfides, subtract the soluble sulfide concentration from the
total sulfide concentration.
Pollution prevention and waste management

The Sulfide 2 Reagent contains potassium dichromate. Dispose of chemicals and wastes in
accordance with local, regional and national regulations.
Sulfide
Page 94
Sulfide
Interferences
The known interferences are shown in Table 1. The interference levels are applicable to an
undiluted 10-mL sample. The interference levels increase proportionally as the sample is diluted.
Substance
Interference
Barium
Concentrations greater than 20 mg/L react with the sulfuric acid in Sulfide 1 Reagent
and form a BaSO4 (barite) precipitate. To correct for this interference:
1. Use a 0.25-mL or 2.5-mL sample volume in the test procedure and add deionized
water to the 25-mL line.
2. Let the sample fully react with both reagents.
3. After the 5 minute reaction period, pour the sample into a 50-mL beaker.
4. Pull the sample into a 60 cc Luer-Lock syringe.
5. Put a 0.45-m 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.
Strong reducing substances (sulfite,

thiosulfate and hydrosulfite)
Can decrease the blue color or prevent the full color development.
Sulfide, high levels
Can prevent the full color development. Make a dilution if the sample has a high sulfide concentration. Some sulfide loss can occur when the sample is diluted.
Turbidity
Can be corrected with a prepared sulfide-free blank:

1. Measure 25 mL of sample into a 50-mL Erlenmeyer flask.
2. Swirl the flask and add bromine water by drops only until the solution has a
permanent yellow color.
3. Continue to swirl the flask and add phenol solution by drops only until the yellow
color is gone. Replace the deionized water in step 4 of the procedure with this
solution.
This procedure removes the sulfide from the sample but does not remove the turbidity
or background color. The interference from turbidity or color will be corrected when
the instrument is set to zero with this solution.
Accuracy check
Sulfide standard solutions are not stable and must be prepared by the user. Refer to Standard
Methods, 4500S for preparation and standardization instructions.
Method performance
Precision
In a single laboratory, with standard solutions of 0.73 mg/L sulfide and two representative lots of
reagent, a single operator got a standard deviation of 0.02 mg/L sulfide with the instrument.
Estimated detection limit (EDL)
The EDL for program 129 is 0.01 mg/L S2-.
Summary of method
Hydrogen sulfide and acid-soluble metal sulfides react with N, N-dimethyl-p-phenylenediamine to
form methylene blue. The intensity of the blue color is proportional to the sulfide concentration.
Instrument setup
This procedure adds program 129 to a DR/850 or DR/890 instrument.
1. Push SETUP.
2. Push the DOWN ARROW until the display shows USER.
3. Push ENTER.
4. Push the numbers 8138, then push ENTER. The display shows LINE 1?
Sulfide
Page 95
Sulfide
5. Refer to Table 2. Find the 1 in the Line Number column, then read across to find the numbers
in the Enter column. Push these numbers on the keypad, then push ENTER.
6. Continue to add the numbers that correspond to each line number on the display.
Sulfide
Page 96
Line number
Enter
Line number
Enter
129
29
42
30
83
74
31
32
32
72
33
82
34
35
65
36
32
37
10
38
11
39
66
12
63
40
200
13
129
41
14
202
42
15
184
43
16
44
80
17
45
18
46
244
19
47
20
20
83
48
21
32
49
44
22
76
50
23
82
51
24
52
25
83
53
26
32
54
167
27
77
55
28
82
56
255
Sulfide

Required reagents
Description
Sulfide reagent set, includes:
Sulfide 1 Reagent
Sulfide 2 Reagent
Quantity/Test
Unit
Item no.
2244500
1 mL
100 mL MDB
181632
1 mL
100 mL MDB
181732
10 mL
4L
27256
Quantity/Test
Unit
Item no.
Pipet, variable volume, 0.21.0 mL
BBP078
Pipet tips, 0.21.0 mL for BBP078 pipet
100/pkg
BBP079
Pipet, variable volume, 1.05.0 mL
BBP065
Pipet tips, 1.05.0 mL for BBP065 pipet
75/pkg
BBP068
Pipets, variable volume, one BBP078 and one BBP065 with tips
LZP320
Sample cell, 10-20-25 mL, with cap
6/pkg
2401906
Unit
Item no.
50041H
29 mL
221120
2088640
Flask, Erlenmeyer, 50 mL
50541
29 mL
211220
1451540
Water, deionized
Required apparatus
Description

Description
Beaker, 50 mL, low form
Bromine water, 30 g/L
Phenol solution, 30 g/L

Pipet, volumetric, Class A, 25.00 mL
Pipet filler, safety bulb
1465100
Syringe, 60 cc, Luer-Lock tip
2258700
50/pkg
2513603
Syringe filter, 0.45 m, 33 mm PVDF
Sulfide
Page 97

HACH COMPANY
WORLD HEADQUARTERS
Telephone: (970) 669-3050
FAX: (970) 669-2932
06/2012, Edition 2
TPH, 10050
TPH (Total Petroleum Hydrocarbons)

DOC316.53.01142
Immunoassay1
Method 10050
Scope and Application: For soil and water

1
This test is semi-quantitative. Results are expressed as greater or less than the threshold value used.
Test preparation

The Instrument-specific information table displays requirements that may vary between
instruments. To use this table, select an instrument then read across to find the corresponding
information required to perform this test.

Instrument
Cell orientation
Adapter
DR 6000
Arrow points right
LZV902.99.00020
DR 5000
Arrow points toward user
A23618
DR 3900
Arrow points toward user
LZV846 (A)
DR 3800, DR 2800, DR 2700
Arrow points right
LZV583 (A)

The TPH test can be used for both soil and water testing. When testing soil, start with the Soil Extraction Procedure. When
testing water samples only, start with the Immunoassay Procedure for Soil Extracts and Water Samples. The test requires
about 20 to 30 minutes for complete analysis. As many as 10 cuvettes can be run simultaneously.
Read the entire procedure before starting. Identify and make ready all the necessary reagents, cuvettes and other
apparatus before beginning the analysis.
Timing is critical; follow instructions carefully.
A consistent technique when mixing the cuvettes is critical to this test. The best results come from using the cuvette
rack and mixing as described in Using the 1-cm MicroCuvette Rack. Cuvettes can be mixed individually, but test results may
not be as consistent.
Handle the cuvettes carefully. Scratches on the inside or outside may cause erroneous results. Carefully clean the outside of
the cuvettes with a clean absorbent cloth or tissue before placing them into the instrument.
Antibody cuvettes and enzyme conjugate are made in matched lots. Do not mix reagent lots.
To avoid damaging the Color Developing Solution, do not expose it to direct sunlight.
The cuvette rack is designed to be inverted with the cuvettes in place. This is especially helpful when running many samples
at once; the cuvettes can remain in the rack and be processed together until they are read in the spectrophotometer.
Twenty Antibody Cuvettes are provided with each reagent set. One Antibody Cuvette will be used for each calibrator and
each sample. Cuvettes are not reusable.
Store the reagents at 4 C when they are not in use. Allow the reagents to reach room temperature before using them in an
analysis. Actual testing may be done at temperatures ranging from 1 38 C.
The Soil Extractant contains methyl alcohol which is poisonous and flammable. Before using this and other reagents, read
the Material Safety Data Sheet (MSDS) for proper use of protective equipment and other safety information.
Protective nitrile gloves are recommended for this procedure.

Page 99

Description
Quantity
TPH Reagent Set
Caps, flip spout
Marker, laboratory
Rack, for 1-cm Micro Cuvettes
Wipes, disposable
Pipet, TenSette, 0.11.0 mL
Pipet Tips, for TenSette Pipet 19700-01
Soil extraction procedure
1. Weigh out 10 g of soil

in the plastic weighing
boat.
2. Carefully pour the soil

into an extraction vial.

Page 100
3. Use the 5-gram scoop

to add one scoop of
sodium sulfate to the
extraction vial.
4. Use the graduated

cylinder to transfer 10 mL
of Soil Extractant into the
extraction vial.

Soil extraction procedure (continued)
5. Cap the extraction vial

tightly and shake
vigorously for one minute.
6. Allow to settle for at

least one minute. Carefully
open the extraction vial.
7. Using the disposable

bulb pipet, withdraw 1.0
1.5 mL from the liquid
layer at the top of the
extraction vial.
Transfer it into the filtration
barrel (the bottom part of
the filtering assembly).
Do not use more than
1.5 mL. The bulb is
marked in 0.25-mL
increments.
8. Insert the filtration

plunger into the filtration
barrel. Place the filtration
assembly on a table and
press firmly on the plunger
until the sample extract is
forced upward into the
center of the plunger.
Use the resultant filtrate as
the sample in the
Immunoassay procedure
for soil extracts and water
samples.
Immunoassay procedure for soil extracts and water samples
Single Wavelength
OK
1. Press
Single Wavelength.
Press OPTIONS and the
button.
Enter 450 nm and press
OK.
2. Label an Antibody
Cuvette for each calibrator
and each sample to be
tested.
3. Insert the cuvettes into

the rack snugly.
4. Pipet 0.5 mL of Diluent

Solution into each
Calibrator cuvette.
The same pipette tip can
be used repeatedly for this
step.
Insert an adapter if
required (Instrumentspecific information).

Page 101

Immunoassay procedure for soil extracts and water samples (continued)
5. If testing soil: Pipet

0.5 mL of Diluent Solution
into each sample cuvette.
If testing water: Pipet
0.5 mL of each water
sample into each sample
cuvette. Use a new pipette
tip for each sample.
9. Start the instrument

timer for 10 minutes.
A 10-minute reaction time
will begin. Immediately mix
the contents of the
cuvettes for 30 seconds
using the technique
described in Using the 1cm MicroCuvette Rack.
6. Have the necessary

apparatus at hand for the
next four steps as they
must be done without
delay.
Use a Wiretrol pipet to
transfer 50 L of each
calibrator to be used into
the calibrator cuvettes.
7. If testing soil: Use a

Wiretrol pipet to transfer
50 L of the filtered extract
from step 8 of the Soil
extraction procedure into
the appropriately labeled
cuvette. Use a separate
capillary tube for each
solution.
8. Immediately pipet
0.5 mL of TPH Enzyme
Conjugate into each
calibrator and sample
cuvette.
The same pipette tip can
be used repeatedly for this
step.
Mix the contents of the

cuvettes after each
addition. Use a separate
capillary tube for each
solution.

cuvettes after the addition
of each sample.
10. After 5 minutes, mix

the contents of the rack a
second time for a period of
30 seconds using the
same technique.

10-minute period, discard
the contents of all the
cuvettes into an
appropriate waste
container.
12. Wash each cuvette

forcefully and thoroughly
four times with deionized
water. Empty the rinse
water into the waste
container.
The simple TPH and

calibrator TPH will remain
attached to the cuvette
walls.
Make sure that most of the

water is drained from the
cuvettes. Turn the
cuvettes upside down and
tap them lightly on a paper
towel.

Page 102
If testing water: Use a

Wiretrol pipet to transfer
50 L of methanol into
each sample cuvette.

Immunoassay procedure for soil extracts and water samples (continued)
Color Development
Important Note: Timing is critical. Follow instructions carefully.
13. With the cuvettes still

held snugly in the rack,
pipet 0.5 mL of Color
Developing Solution into
each Cuvette.
Use a new pipette tip for
each cuvette.
14. Start the instrument

timer for 10 minutes.
A 10-minute reaction time
will begin. Immediately mix
the contents of the
using the technique
described in Using the 1cm MicroCuvette Rack.
15. After 5 minutes, mix

the contents of the rack a
second time for a period of
30 seconds using the
same mixing technique
that was used in step 14.
Solutions will turn blue in
some or all of the cuvettes.

10-minute reaction period,
pipette 0.5 mL of Stop
Solution into each cuvette
in the same order that was
used in step 13. The same
pipette tip can be used
repeatedly for this step.
using the same mixing
technique as in step 14.
Blue solutions will turn
yellow.
Zero
17. Label and fill a Zeroing

Cuvette with deionized
water. Wipe the outside of
all the cuvettes with a
tissue to remove water,
smudges and fingerprints.
18. Insert the filled

Zeroing Cuvette into the
cell holder.
Refer to Instrumentspecific information for cell
orientation.
19. ZERO the instrument.

The display will show:
0.000 Abs
20. Insert the first

calibrator into the cell
holder.
READ the results. The
display will give an

absorbance reading.
Record the results for
each calibrator and
sample.
See Interpreting and
reporting results to find the
relative concentration.

Page 103
Using the Wiretrol* Pipet

The Wiretrol Pipet can accurately measure small quantities of liquids. It consists of two parts: a
Teflon-tipped plunger and a calibrated capillary tube. The plunger can be reused. The capillary
tubes must be discarded after one use.
1. Wet the orange

Teflon tip of the Wiretrol
plunger in the sample and
carefully insert it into the
end of the capillary tube
with the colored band.
2. Push the tip to the

other end of the capillary
tube until it barely extends
beyond the end of the
capillary tube.
3. Submerge the
capillary tube below the
surface of the liquid to be
pipetted. Slowly and
smoothly draw the Wiretrol
plunger up until the bottom
of the plunger tips reaches
the appropriate volume
line.
Touch the end of the tube
to the side of the vessel to
release remaining drops
on the capillary tube tip.
* Wiretrol is a registered trademark of Drummond Scientific.

Page 104
4. To discharge the pipet,

place the tip of the
capillary tube below the
surface of the solution
and push the Wiretrol
plunger down in one
smooth motion. Change
capillary tubes for each
calibrator and sample.
Using the 1-cm MicroCuvette Rack

The MicroCuvette rack (Figure 1) has been designed to aid in achieving precise and accurate
results when using the immunoassay technique to analyze several samples at the same time.
Figure 1 The 1-cm MicroCuvette Rack
Loading the RackThe cuvette rack is designed so that it may be inverted with the cuvettes in
place. Identify each cuvette with a sample or calibrator number and insert all the cuvettes in the
rack before beginning the procedure. Fit the cuvettes snugly into the rack, but do not force them or
they may be difficult to remove and their contents may spill. The cuvettes should remain in place
when the rack is inverted and tapped lightly.
MixingSet the rack on a hard, flat surface that is at least twice the length of the rack. Hold the
rack by one end and vigorously slide it back and forth along its long axis for 30 seconds. The rack
should move through a distance equal to its own length in each direction.

Page 105
Interpreting and reporting results

There is an inverse relationship between the concentration of TPH and the absorbance reading. In
other words, the higher the absorbance reading, the lower the concentration of TPH:
If sample reading < calibrator reading, TPH concentration in sample > calibrator reading
If sample reading > calibrator reading, TPH concentration in sample < calibrator reading
Example:
Readings
TPH Calibrator #1: 0.480 Abs
TPH Calibrator #2: 0.360 Abs
Sample #1: 0.200 Abs
Interpretation for a Soil Sample
Sample #1The sample reading (0.200 Abs) is less than the readings for both calibrators.
The concentration of TPH in the sample is greater than 50 ppm diesel fuel.
Sample #2The sample reading (0.400 Abs) is between the readings for the TPH calibrators.
The concentration of TPH in the sample is between 20 ppm and 50 ppm diesel fuel.
Sample #3The sample reading (0.550 Abs) is greater than the readings for both calibrators.
The concentration of TPH in the sample is less than 20 ppm diesel fuel.
Interpretation for a Water Sample
Sample #1The sample reading (0.200 Abs) is less than the readings for both calibrators.
The concentration of TPH in the sample is greater than 5 ppm diesel fuel.
Sample #2The sample reading (0.400 Abs) is between the readings for the TPH calibrators.
The concentration of TPH in the sample is between 2 ppm and 5 ppm diesel fuel.
Sample #3The sample reading (0.550 Abs) is greater than the readings for both calibrators.
The concentration of TPH in the sample is less than 2 ppm diesel fuel.
Storing and handling reagents

1. Wear protective gloves and eyewear.
2. When storing reagent sets for extended periods of time, keep them out of direct sunlight. Store
reagents at a temperature of 4 C when not in use.
3. Keep the foil pouch containing the Antibody Cuvettes sealed when not in use.
4. If Stop Solution comes in contact with eyes, wash thoroughly for 15 minutes with cold water
and seek immediate medical help.

Page 106
Sensitivity
The antibodies used in the TPH Test Kit react with a variety of compounds found in petroleum
fuels; however, each TPH calibrator has been formulated to represent a specific concentration of
diesel fuel. To use the calibrators for other TPH compounds, see Table 2 for soil or Table 3 for
water to select the proper TPH calibrator for the compound, sample and range you want to test.
Example:
To use the TPH calibrators for gasoline, find Gasoline in the first column of Table 2 or Table 3.
Read across the column to find the ppm represented by each calibrator. For gasoline,
calibrator #1 = 15 ppm, calibrator #2 = 35 ppm, etc.
Table 2 TPH compounds in soil

Compound
TPH calibrator #1
(ppm)
TPH calibrator #2
(ppm)
TPH calibrator #3
(ppm)
TPH calibrator #4
(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
15
35
75
m-Xylene
20
35
70
o-Xylene
10
20
40
80
p-Xylene
16
BTEX
15
25
45
Table 3 TPH compounds in water

Compound
TPH calibrator #1
(ppm)
TPH calibrator #2
(ppm)
TPH calibrator #3
(ppm)
TPH calibrator #4
(ppm)
Diesel fuel
10
20
Gasoline
1.5
3.5
14
Kerosene
3.5
7.5
14
25
Benzene
4.5
8.5
16
Toluene
1.5
Ethylbenzene
0.5
1.5
3.5
7.5
m-Xylene
0.9
3.5
o-Xylene
p-Xylene
0.3
0.5
0.9
16
BTEX
0.5
1.5
2.5
4.5

Page 107
Diluting water samples

To test for TPH in water at concentrations that are higher than those shown in Table 3, dilute the
sample with deionized water. Add a volume of sample from Table 4 to a graduated cylinder and
dilute to 50 mL with deionized water. Run the test. Multiply the calibrator levels shown in Table 3
by the dilution multiplier in Table 4.
Example:
If a 0.5 mL water sample is diluted to 50 mL and tested, the calibrator levels shown in Table 3 for
diesel fuel would represent 200, 500, 1000 and 2000 ppm respectively.
Table 4 Dilution multipliers

mL Sample
Dilution multiplier
0.5
100
1.0
50
2.0
25
5.0
10
10.0
25.0
Interferences
Interference level
Chlorine in water samples
Interferes above 2 ppm. Remove with 1 drop per 100 mL sodium thiosulfate (0.1 N).
Sample collection and storage
Analyze the samples as soon as possible after collection.
To store the samples, collect them in glass or Teflon containers that have been washed with
soap and water and rinsed with methanol. The container should be capped with a Teflon-lined
cap. If a Teflon cap is not available, aluminum foil rinsed in methanol may be used as a
substitute cap liner.
When collecting water samples, fill the container completely (no head space) and cover the
container with a tightly-sealed lid immediately after collection.
SoilStore the samples at 4 C (40 F) for no longer than 14 days.
WaterChill the sample in an ice bath or refrigerator to limit the loss of volatile compounds.
Store samples no longer than 24 hours.

Page 108
Summary of method
This method provides semi-quantitative screening for TPH based on thresholds as diesel fuel in
the following concentrations:
Soil20, 50, 100, 200 ppm as diesel fuel
Water2, 5, 10, 20 ppm as diesel fuel
Immunoassay tests use antigen/antibody reactions to test for specific organic compounds in water
and soil. Antibodies specific for TPH are attached to the walls of plastic cuvettes. They selectively
bind and remove TPH from complex sample matrices. A prepared sample and a reagent
containing 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 will have more
antibody sites occupied by TPH and fewer antibody sites occupied by the enzyme-conjugate
molecules.
After incubation, the sample and unbound enzyme conjugate are washed from the cuvette and a
color-development reagent is added. The enzyme in the conjugate catalyzes the development of
color. Therefore, 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 whether the TPH
concentration in the sample is greater or less than the threshold levels. The TPH concentration is
inversely proportional to the color development: the lighter the color, the higher the TPH
concentration. Test results are measured at 450 nm.

Required reagents
Description
Unit
Catalog Number
20 cuvettes
2774300
500 mL
27248
Description
Unit
Catalog Number
TPH Reagent Set1

Deionized water
1
Immunoassay components are manufactured by Beacon Analytical Systems, Inc.
Required apparatus
Caps, flip spout
2/pkg
2581802
Marker, laboratory
each
2092000
Pipet, TenSette, 0.11.0 mL
each
1970001
1000/pkg
2185628
Rack, for 1-cm Micro Cuvettes
each
4879900
Wipes, disposable
box
2097000
Pipet Tips, for TenSette Pipet 19700-01

Page 109
Soil extraction reagents and apparatus

Description
Unit
Balance, AccuLab Pocket Pro 250 B
each
2796900
medium1
each
2550502
Pipet tips for 1970001 Ten Sette Pipet
50/pkg
2185696
Soil Scoop, 5-g, 4.25-cc
20/pkg
2657205
each
2775200
Gloves, disposable, Nitrile,
Soil Extraction Refill Kit, includes:
Catalog Number
Dropper, LDPE, 0.5 and 1.0-mL
20/pkg
2124720
Filter and Barrel Assembly
20/pkg
2567620
Soil Extractant Solution
200 mL
2567729
Soil Sample Container
20/pkg
2592920
Weighing Boat, 8.9-cm square
20/pkg
2179020
Spatula, disposable
2/pkg
2569320
Sodium Sulfate, anhydrous
250 g
709929
Other sizes are available

Description
Unit
Catalog number
Analytical balance, 80 g capacity, 0.1 mg resolution
each
2936701
500/pkg
1473800
Safety goggles, vented
Weighing papers
each
2550700
Graduated cylinder, 10 mL
each
108138
Pipet, Wiretrol, 1050 L
20/pkg
2852200
Pipet, Wiretrol, 501000 L
250/pkg
2568905
100 mL MDB
32332
Sodium Thiosulfate standard solution, 0.1 N

HACH COMPANY
WORLD HEADQUARTERS
Telephone: (970) 669-3050
FAX: (970) 669-2932
09/2011 Edition 1
Procedures Explained
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
Procedures Explained: Barium

Table 1 Corresponding data for Figure 1
Ba Spike Concentration
(mg Ba/L)
Ba Spike recovery
Sr Spike recovery at the same

conc as the Ba spike (mg Ba/L)1
% Difference
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.
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
convert calcium as CaCO3 to the elemental form of just calcium, multiply the Ca hardness
value by 0.4.
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
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
Procedures Explained: Iron

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.
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.)
Procedures Explained: Conductivity and Total Dissolved Solids
Figure 2 Effects of increased conductivity on diluted samples
Sample1
Undiluted
Diluted
%Diff
235
344
31.7
208
258.8
19.6
197.1
245.8
19.8
174.5
205.2
15.0
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 S/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.
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 S/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 180C, 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.
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
CDC40110
CDC40115
CDC40130
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.
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.
10
Procedures Explained: Turbidity and Total Suspended Solids

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.
11
HACH COMPANY World Headquarters

P.O. Box 389, Loveland, CO 80539-0389 U.S.A.
Tel. (970) 669-3050
(800) 227-4224 (U.S.A. only)
Fax (970) 669-2932
orders@hach.com
www.hach.com
HACH LANGE GMBH

Willsttterstrae 11
D-40549 Dsseldorf, Germany
Tel. +49 (0) 2 11 52 88-320
Fax +49 (0) 2 11 52 88-210
info@hach-lange.de
www.hach-lange.de
Hach Company/Hach Lange GmbH, 2011-2012. All rights reserved. Printed in U.S.A.
HACH LANGE Srl

6, route de Compois
1222 Vsenaz
SWITZERLAND
Tel. +41 22 594 6400
Fax +41 22 594 6499

Hydraulic Fracturing Handbook

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DOC022.53.

Hydraulic Fracturing Water Analysis Handbook

Alkalinity, DT, 8203

Phenolphthalein and Total Alkalinity

10 to 4000 mg/L as CaCO3

Refer to Optional reagents and apparatus on page 10.

Collect the following items:

Bromcresol Green-Methyl Red Indicator Powder Pillow

Phenolphthalein Indicator Powder Pillow

pH Meter and probe (highly colored samples only)

Sulfuric acid titration cartridge (refer to Table 1 on page 5)

Delivery tube for digital titrator

Erlenmeyer flask, 250-mL

Refer to Consumables and replacement items on page 9 for reorder information.

5. Transfer the sample

2. Insert a clean delivery

3. Turn the delivery knob

7. Place the delivery tube

8. Use the multiplier in

Note: Other titrant

6. Add the contents of

Write down the number of

9. Add the contents of

10. Continue the titration

11. Use the multiplier in

Write down the number of

Note: A pH meter may be

12. Calculate the

Table 1 Range-specific information

Sample volume (mL)

Titration cartridge (N H2SO4)

Table 2 End point pH

Alkalinity about 30 mg/L

Alkalinity about 150 mg/L

Alkalinity about 500 mg/L

Silicates or phosphates present

Industrial wastes or complex system

Routine or Automated Analyses

Table 3 Interfering substances

Soaps, oily matter, suspended

Slow stabilization times

The type of contamination will determine the cleaning solution needed.

Sample collection, preservation and storage

Alkalinity measurements with a pH meter

Alkalinity relationship table

Table 4 Alkalinity relationships

Phenolphthalein Alkalinity equal

Phenolphthalein Alkalinity less

Total Alkalinity minus two

Phenolphthalein Alkalinity equal

2 times the difference

Phenolphthalein alkalinityAdd 50 mL of deionized water to a flask. Add one pH 8.3

Standard additions method (sample spike)

Alkalinity Voluette Ampule Standard Solution, 0.500 N

TenSette Pipet, 0.11.0 mL and Pipet Tips

1. Open the standard solution ampule.

Consumables and replacement items

Alkalinity Reagent Set (approximately 100 tests)

(1) Bromcresol Green-Methyl Red Powder Pillows

(1) Phenolphthalein Indicator Powder Pillows

(1) Sulfuric Acid Titration Cartridge, 0.1600 N

(1) Sulfuric Acid Titration Cartridge, 1.600 N

Cylinder, graduated, 10-mL

Cylinder, graduated, 25-mL