T 260 METHODS OF SAMPLING AND TESTING

Standard Method of Test for

Sampling and Testing for Chloride Ion in Concrete and Concrete Raw Materials

AASHTO DESIGNATION: T 260-94

1. SCOPE representative sample of sufficient size 3. REAGENTS

for testing.
1.1 This method covers procedures for 2.1.2.1 Sample containers capable of 3.1 Concentrated HNO3 (sp gr 1.42).
the determination of the total chloride ion maintaining the sample in an
uncontaminated state. 3.2 Sodium chloride, NaCl, reagent grade
content or the water-soluble chloride ion (primary standard).
content of aggregates, portland cement, 2.1.2.2 Spoons of adequate size to collect
mortar or concrete. the sample from the drilled holes. 3.3 Standard 0.01 normality NaCI
solution. Dry reagent grade NaCl in an
1.2 The age of concrete mortar, or 2.1.2.3 A "blow out" bulb or other oven at 105°C. Cool, in a dessicator,
hydrated portland cement at the time of suitable means of removing excess determine the mass of approximately
sampling will have an affect on the pulverized material from the hole prior to 0.5844 grams to the nearest 0.0001 gram,
tivater-soluble chloride ion content. re-drilling operations. dissolve in distilled H2O, and transfer to a
Therefore, unless early age studies are 2.1.2.4 A device capable of determining 1 liter volumetric flask. Make up to the
desired, it is recommended that the the location and depth of steel mark with distilled H2O and mix.
material be well cured and at least 28 reinforcement to ± 3 mm (± ⅛ in.). Calculate the exact normality as follows:
days of age before sampling.
2.2 Equipment for Chemical Testing: (Wactual )
1.3 This Standard provides for the N NaCl = (0.0100)
2.2.1 Chloride ion or silver/sulfide ion 0.5844
determination of chloride ion content by
three procedures: Procedure A, selective electrode and manufacturer Wactual = actual mass of NaCl
Determination of Total Chloride Ion recommended filling solutions. NnaCl = normality of NaCl solution
Content and WaterSoluble Chloride Ion 3.4 Standard 0.01 normality AgNO3.
Content by Potentiometric Titration or NOTE 1-Suggested electrodes are the Orion Determine the mass of 1.7 grams of
Ion-Selective Electrode-Laboratory Tes i 96-17 Combination Chloride Electrode or the reagent AgNO3, dissolve in distilled H2O,
Method, Procedure B, Total Chloride Ion Orion 94-6 Silver/Sulfide Electrode or filter into a 1 liter brown glass bottle, fill,
by Atomic Absorption-Laboratory Test equivalents. The Silver/Sulfide electrode
and mix thoroughly. Standardize against
Method, and Procedure C, Total Ion requires use of an appropriate reference
electrode (Orion 90-02 or equivalent). 25.00 mL of the NaCl solution by the
Using Specific Ion Probe-Field Test titration method given in Section 5.4.
Method. Calculate the exact normality as follows:
1.4 Sulfides are known to interfere with 2.2.2 A millivoltmeter compatible with
the determination of chloride content. the ion electrode.
Blast-furnace slag aggregates and NagNO3 = normality of AgNO3 solution
cements contain sulfide sulfur in VnaCl = volume (mL) of NaCl solution
NOTE 2-Suggested millivoltmeter is the
concentrations that can cause such Orion Model 701 A Digital ph/mV meter or NnaCl = normality of NaCl solution
interference. which can be eliminated by equivalent. VagNO3 = volume (mL) of AgNO3
treatment as noted in the test procedures.
solution
Other materials that produce a strong
odor of H2S when acid is added to them 2.2.3 Magnetic stirrer and teflon
should be similarly treated. stirring bars. 3.5 Distilled Water.
1.5 The values stated in SI units are to be 2.2.4 Burette with 0.1 mL graduations.
regarded as the standard. 2.2.5 Balance complying with M 231, NOTE 4-Deionized water may be used in
Class A. place of distilled water for samples where
2.2.6 Balance complying with M 231, extreme precision and accuracy are not
PROCEDURE A-Total Ion and Water- demanded.
Soluble Ion by Potentiometric Class G 2.
Titration or Ion Selective Electrode - 2.2.7 Hot plate, 250 to 400°C heating
Laboratory Test Method surface temperature. 3.6 Methyl orange indicator.
2.2.8 Glassware, 100 and 250 mL 3.7 Ethanol, denatured or methanol,
2. APPARATUS beakers, filter funnels, stirring rods, technical.
watch glasses, dropper, wash bottles. 3.8 Hydrogen Peroxide (30 percent).
2.2.9 Sieve, U.S. Standard 0.300mm
2.1 Sampling equipment for Procedures
(Nº 50).
A and B are listed in Sections 2.1.1 or 4. METHOD OF SAMPLING
2.1.2. 2.2.10 Whatman Nº 40 and Nº 41 filter
papers (or equivalent).
2.1.1 Core drill. 4.1 Concrete Sample:
2.1.2 Rotary impact type drill with a 4.1.1 Determine the depth within the
depth indicator and drill or pulverizing NOTE 3-If equivalent filter papers are used,
they should be checked to confirm they do not concrete for which the chloride content is
bits of sufficient diameter to provide a desired.
contain chloride which will contaminate
the sample.
574
T 260 METHODS OF SAMPLING AND TESTING

NOTE 5-A convenient method of determining 4.2.1 Cement samples shall be taken continuous stirring until a faint pink or
the location and depth of reinforcement bars is and prepared as prescribed in T 127, red color persists in the solution. Cover
a pachometer capable of determining the Sampling Hydraulic Cement. with a watch glass, retaining the stirring
location and depth of steel reinforcement to ±
4.2.2 Coarse and fine aggregate rod in the beaker. Heat the acid solution
3 nun (0.125 in.).
samples shall be taken as prescribed in T or slurry to boiling on a hot plate at
2, Sampling Stone, Slag, Gravel, Sand medium heat (250 to 400°C) and boil for
4.1.2 Core Method-Drill the core to and Stone Block for Use in Highway about 1 minute. Remove from the hot
chosen depth and retrieve. Materials. Samples shall be reduced in plate, filter through double filter paper
4.1.2.1 When samples are received in the accordance with T 248, Reducing Field (Whatman Nº 41 over Nº 40 filter paper
laboratory in other than pulverized Samples of Aggregate to Testing Size. or equivalent).
condition, the sample shall be crushed 4.2.3 Test samples shall contain the 5.2.2 Wash the filter paper 10 times
and ground to a powder. All sawing or following minimum sizes: cement-100 g, with hot distilled H2O, being careful not
crushing shall be done dry (i.e. without Sand-300 g, coarse aggregate-3000 g to lift the paper away from the funnel
water). All material shall pass a 0.300mm surface. Finally, lift the filter paper
4.2.4 Coarse aggregate samples shall carefully from the funnel and wash the
(Nº 50) sieve. All pulverizing tools and
be crushed to pass a 4.75-mm (Nº 4) outside surface of the paper with hot
sieves shall be washed with alcohol or
sieve and then reduced down to about distilled H2O; then wash the tip of the
distilled water and shall be dry before use
300 g. The final 300 g of coarse or fine funnel. The final volume of the filtered
with each separate sample (see note
aggregate shall be ground to a minus solution should be 125 to 150 mL. Cover
following Section 4.1.3.7).
0.300-mm (Nº 50) sieve. with a watch glass and allow to cool to
4.1.3 Pulverizing Method:
room temperature in an HCl fumefree
4.1.3.1 Set the rotary hammer depth atmosphere.
indicator so that it will drill to 13 nun 5. PROCEDURE
(0.5 in.) above the desired depth.
Two distinct procedures are presented NOTE 9-Due to the presence of relatively
4.1.3.2 Using a drill or pulverizing bit,
here for determination of total chloride insoluble materials in the sample, the solution
drill until the depth indicator seats itself generally will have a strong gray color,
on the concrete surface. ion or water-soluble chloride ion content. making the detection of indicator color
For total chloride ion content follow difficult at times. Running of several trial
4.1.3.3 Thoroughly clean the drilled hole
Sections 5.1 and 5.2, then continue with samples is suggested to give the analyst
and surrounding area utilizing the "blow
Section 5.4. For water-soluble chloride practice in detecting the indicator color.
out" bulb or other suitable means.
ion content follow Sections 5.1 and 5.3, NOTE 10-A sample prepared to 100 percent
4.1.3.4 Reset the depth indicator to per- then continue with Section 5.4. passing 0.300-mm (Nº 50) sieve should
mit 13 mm (0.5 in.) additional drilling. generally allow determination of any expected
5.1 Determine the mass to the nearest
4.1.3.5 Pulverize the concrete until the milligram of a 3 g powdered sample chloride level with adequate precision an
depth indicator again seats itself on the accuracy. Samples containing highly siliceous
representative of the material under tests. aggregates may require finer grinding to
concrete.
minimize bumping during step 5.2. This may
NOTE 8-Some users dry the sample to also be the case when the concrete contains
NOTE 6-Care must be exercised during this constant mass in a 105°C oven and determine modifiers such as latex or polymer.
pulverizing operation to prevent the drill bit the dry sample prior to analysis. This optional
from abrading concrete from the sides of the procedure provides a constant base for
hole above the sampling depth. To insure comparison of all results by eliminating
5.3 Procedure for Water-Soluble
against this, some users utilize a 6-mm moisture content as a variable. It is generally Chloride Ion Content:
(0.25in.) smaller diameter bit in this step than believed that drying is only necessary when 5.3.1 Transfer the sample quantitative-
that used in Section 4.1.3.2.1 very high accuracy is desired (see Reference t ly to a beaker, add 60-70 mL distilled
for data in this area). H2O. Cover the beaker with a watch glass
4.1.3.6 Collect at least 10 grams of the and bring to a boil on a hot platemagnetic
material remaining in the hole using a 5.2 Procedure for Total Chloride Ion stirrer using a small magnet. Boil for 5
spoon and place in the sample container. Content: minutes, then let stand for 24 hours in an
HCI fume-free atmosphere.
4.1.3.7 If the sample, as collected, does 5.2.1 Transfer the sample quantitative-
not completely pass a 0.300-mm (Nº 50) ly to a beaker, add 10 mL of distilled 5.3.2 Filter the clear supernatant liquid
sieve, additional pulverizing shall be per- H2O, swirling to bring the powder into in the beaker through double filter paper
formed in the laboratory until the entire suspension. Add 3 mL of concentrated (Whatman Nº 41 over Nº 40 or equiva-
sample is finer than 0.300-mm (Nº 50). HNO3 with continued swirling until the lent) into a 250-mL beaker: take care to
material is completely decomposed. quantitatively transfer any adhering drops
Break up any lumps with a stirring rod on the watch glass, and use a stirring rod
NOTE 7-During sample collection and to aid transfer. Add sufficient hot
pulverizing, personnel shall use caution to and dilute with hot H2O to 50 mL. Stir
thoroughly to ensure complete sample distilled H2O to cover any residue left in
prevent contact of the sample with hands, or
other sources of body perspiration or digestion. the original beaker, stir 1 minute on a
contamination. Further, all sampling tools magnetic stirrer, and. filter into the 250-
If the sample contains blast-furnace slag
(drill bits, spoons, bottles, sieves, etc.) shall be mL beaker with a swirling action. Wash
or other sulfide-bearing material. add 3
washed with alcohol or distilled water and the beaker and the stirring rod once into
shall be dry prior to use on each separate ml- of hydrogen peroxide (30 percent
the filter with hot distilled H2O. Wash the
sample. Alcohol is normally preferred for solution).
filter paper once with hot distilled H2O.
washing because of the rapid drying which Add five drops of methyl orange Lift the filter paper carefully from the
naturally occurs. indicator and stir. If yellow to yellow- funnel and wash the outside surface of
orange color appears, solution is not the paper with hot distilled H2O. Set
4.2 Raw Material Sample: sufficiently acidic. Add additional aside the paper and wash the interior of
concentrated HNO3 dropwise with the funnel and its tip with hot distilled
575
T 260 METHODS OF SAMPLING AND TESTING

H2O. Finally, add 1-2 drops of methyl (i.e., the midpoints between successive volume added and the millivoltmeter
orange indicator to the 150-mL beaker; additions). reading.
then add concentrated HNO3 dropwise Continue to titrate in 0.50-mL increments
with continuous stirring until a recording the volume added and the
Raw Data Differences
permanent pink to red color is obtained. Titrant Milli volt Titrant Millivolt millivoitmeter reading for each
If the sample contains blast-furnace slag Volume Reading Midpoints Difference increment. Add and record the data for at
or other sulfide-bearing material, add 3 4.2 mL 130.0 4.25 mL 5.0 least five increments. Empty, clean, dry
mL of hydrogen peroxide (30-percent 4.3 mL 135.0 4.35 mL 7.0 and determine the mass of the beaker.
solution). Make up the volume to 125 to 4.4 mL 142.0 4.45 mL 10.0 Subtract beaker mass from beaker +
150 mL with distilled H2O. 4.5 mL 152.0 etc. solution mass determined above to define
5.4 Three alternate methods are available etc. solution mass.
to determine the Cl- content of the Example shown in Figure 1. Additional
solution. All methods utilize an ion The endpoint will be near the midpoint information on the Gran Method is given
selective electrode (Cl- or,Ag`) and all which produced the largest change in in Reference 2.
methods for the purpose of this analysis millivoltmeter reading. It may be
give results of essentially equal accuracy 5.4.2.1 Gran Method Calculations:
determined by plotting midpoints versus
and precision. differences and defining the AgN03 Calculate corrected values for each of the
5.4.1 Method 1: Potentiometric Tttra- volume which corresponds to the volumes recorded in Section 5.4.2 by the
tion-Fill the Cl- or the Ag' electrode with maximum difference on a smooth, equation:
the solution(s) recommended by the symmetrical curve drawn through the Vrecord
Vcorrect =
manufacturer, plug it into the millivolt- points. However, it can usually be W / 100
meter (preferably the type with a digital estimated accurately without plotting the W = original solution mass in grams
rather than a dial readout), and determine curve by choosing the midpoint which
the approximate equivalence point by corresponds to the maximum difference Vrecord = volumes recorded in mL
immersing the electrode in a beaker of and adjusting for asymmetry, if any. In If any of the V correct values are greater
distilled H2O. Note the approximate other words, if the differences on each than 10, see Section 5.4.2.2. If less than
millivoltmeter reading (which may be side of the largest difference are not 10, plot these corrected values versus the
unsteady in H2O. Take the cooled sample symmetrical, adjust the endpoint corresponding millivolt readings on
beaker from Section 5.3 and carefully mathematically in the direction of the Orion Gran Plot Paper (10-percent
add 4.00 mL of 0.0100 normality NaCl, largest differences. Detailed examples of volume corrected type with each major
swirling constantly. Remove the beaker this adjustment are contained in vertical scale division equal to five
of distilled H2O from the electrode, wipe Reference 1. millivolts) or equivalent. Draw the best
the electrode with absorbent paper, and 5.4.1.1 Calculations: straight line through the points and read
immerse the electrode in the sample the endpoint at the intersection of the line
Determine the endpoint of the titration as with the horizontal axis of the graph.
solution. Place the entire beakerelectrode
described in Section 5.4.1 by either Calculate the actual endpoint by the
assembly on a magnetic stirrer and begin
plotting a curve or estimating from the equation:
gentle stirring. Using a calibrated buret,
numerical data. Calculate the percent
add gradually and record the amount of
Clion from the equation: ⎛W ⎞
standard 0.01 normality AgNO3 solution Ea, ACTUALENDPOINT = Eg ⎜ ⎟
necessary to bring the millivoltmeter (3.5453 (V1N1 - V2 N 2 ) ⎝ 100 ⎠
Cl - percent =
reading to -40 mV of the equivalence W where:
point determined in distilled H2O. Then where: Eg = endpoint determined from graph in
add standard 0.01 normality AgNO3 mL
solution in 0.10 mL increments recording V1 = Endpoint in mL of AgN3
the millivoltmeter reading after each N1 = Normality of AgNO3 W = mass of solution in grams
addition. W = mass of original concrete sample in 3.5453 Ea N
Then percent CI =
As the equivalence point is approached, grams Wc
the equal additions of AgNO3 solution V2 = volume of NaCI solution added, in where:
will cause larger and larger changes in mL
the millivoltmeter reading. Past the Ea = actual endpoint, in mL
N2 = normality of NaCl solution N = normality of AgNO3 solution
equivalence point, the changes per unit
volume will again decrease. Continue the 5.4.2 Method II: Gran Plot Method- Wc = concrete sample mass in grams
titration until the millivoltmeter reading This method is compatible with either a
Cl- or Ag+ ion selective electrode. Attach 5.4.2.2 Supplementary Gran Method
is at least 40 mV past the approximate
the electrode of choice to a compatible Calculations:
equivalence point.
digital millivoltmeter after filling the When the V correct volumes determined
The endpoint of the titration usually is
required solutions as per the electrode in Section 5.4.2.1 are greater than 10,
near the approximate equivalence point
manufacturer's instructions. Clean the discard the values and follow the
in distilled water and may be determined
electrode with distilled H2O and pat dry following procedure.
by (1) plotting the volume of AgN03
with absorbent paper. Choose a constant which, when
solution added versus the millivoltmeter
readings. The endpoint will correspond to Determine the mass of the solution and subtracted from all V record volumes,
the point of inflection of the resultant beaker from Section 5.3 without the yields values less than 10 mL.
smooth curve, or (2) calculating the watch glass and record the mass. Using a
differences in millivoltmeter readings calibrated buret, titrate the sample to 225
NOTE 11-This constant, designated as X in
between successive AgNO, additions and ± 5 mV (Cl- electrode) or 310 - 5 mV the formulas below, is normally assigned an
calculating the total volume of AgNO3 (Ag+ electrode) with standard 0.01 even value such as 5, 10. 15, 20, etc.
which corresponds with each difference normality AgNO3 solution. Record the

576
T 260 METHODS OF SAMPLING AND TESTING

Calculate a revised solution mass Wr as

Wr = W + X
where:
W = original solution in grams
X = the constant.
Then calculate corrected volumes for
each recorded volume as:
Vrecord − X
Vcorrect =
Wr / 100
Plot these values and determine the graph
endpoint Eg as described in Section
5.4.2.1. The actual endpoint E, is then:
⎛W ⎞
Ea = E g ⎜ r ⎟ + X
⎝ 100 ⎠
Where:
Ea = actual endpoint in ml,
Eg = endpoint from graph in mL
Wr = revised solution mass in grams
X = the constant chosen above.
Calculate the chloride content using the
formula given in Section 5.4.2.1.
5.4.3 Method III: Automatic Tarator-
This method is compatible with either a
Cl- or Ag` ion-selective electrode. The
millivolt endpoint determination and
testing procedure shall be in accordance
with the instrument manufacturer's
recommendation.
5.4.3.1 Automatic Titrator Calculations:
Having determined the endpoint with the
automatic titrator, calculations will be
identical with Section 5.4.1.1.
5.5 The percent chloride may be
converted to kg of Cl/m3 (lb/yd3) of
concrete as follows:
Multilaboratory Precision
⎛ UW ⎞
kg Cl/m3 = percent Cl ⎜ ⎟
⎝ 100 ⎠
Percent Chloride Multilaboratory Precision Acceptable Range of Two
Concentration Standard Deviation' Results' ⎛ ⎛ UW ⎞ ⎞
⎜ lbs Cl - /yd 3 = percent Cl ⎜ ⎟ ⎟⎟
⎜
0.0176 0.0030 0.0085 ⎝ ⎝ 100 ⎠ ⎠
0.0268 0.0031 0.0088 where:
0.0313 0.0032 0.0091
UW = Unit mass of concrete per cubic
0.0592 0.0037 0.0105 meter (cubic yard)
0.1339 0.0048 0.0136
0.2618 0.0069 0.0195
NOTE 12-A unit mass of 2323 kg/m3 (3915
NOTE-The figures given in Column 2 are the standard deviations that have been found to be
lb/yd3) is often assumed for normal structural
appropriate for the chloride ion concentrations described in column I. The figures given in Column mass concrete when the actual unit mass is
3 are the limits that should not be exceeded by the difference between the results of two properly unknown.
conducted tests.
a
These numbers represent, respectively, the (IS) and (D2S) limits as described in ASTM C 670,
6. PRECISION
Recommended Practice for Preparing Precision Statements for Test Methods for Construction
Materials.
6.1 The precision statements presented
below are based on guidelines presented
in ASTM C 670, "Preparing Precision
Statements for Test Methods for
Construction Materials." They are, of
necessity slightly different since the
within-laboratory standard deviation was
essentially constant over the chloride

577
T 260 METHODS OF SAMPLING AND TESTING

levels examined while the between- 7.2.5 Pipettes of suitable sizes, which (primary standard).
laboratory precision varied with chloride meet or exceed the tolerances specified in 8.7 Sodium nitrate, reagent grade.
level. Both statements, however, are NBS circular 602 for Class A
based on the difference two-sigma limit, Volumetricware. 8.8 Water, distilled.
(D2S). The (D2S) index is the difference 7.2.6 Analytical balance sensitive to
between two individual test results that 0.0001 g complying with M 231 Class A. 9. METHOD OF SAMPLING
would be equaled or exceeded in the long
run in only 1 case in 20 in the normal and 7.2.7 Fisher filtrator (vacuum) with
correct operation of the chemical either a glass or plastic bell jar, tall See Section 4 for method of sampling.
analysis. enough to place a 100-niL volumetric
flask underneath.
6.2 Single-Operator-The singleoperator 10. STANDARDIZATION
standard deviation has been found to be 7.2.8 Hot plates (electric).
0.0024 percent chloride2. Therefore, 7.2.9 Vacuum source.
results of two properly conducted tests by 10.1 Dry a sufficient quantity of
7.2.10 Vinyl tubing.
the same operator on the same material standard materials (AgNO3, NaCl,
should not differ by more than 0.0068 CaCO3, and NaNO3) at 105°C to constant
percent chloride1. 8. REAGENTS mass. Cool and retain in a dessicator.
6.3 Multilaboratory Precision-Criteria 10.1.1 Determine the mass of a
for judging the acceptability of chloride 8.1 Calcium carbonate, reagent grade. sufficient sample of each of the above
ion concentration test results obtained by standards to effect the following
8.2 Hydrogen peroxide (30 percent). solutions:
different laboratories by this test method
are given in the table entitled 8.3 Methyl orange. Ag+ - 100 mg/L
"Multilaboratory Precision." 8.4 Nitric acid, concentrated (sp gr 1.42). Cl- - 100 mg/L
8.5 Silver nitrate, reagent grade (primary Na+ - 00 mg/L
standard).
PROCEDURE B-Total Ion by Atomic Ca++ - 500 mg/L
Absorption – Laboratory Test Method 8.6 Sodium chloride, reagent grade

7. APPARATUS

7.1 See Section 2.1 for sampling

equipment.
7.2 Equipment for Chemical Testing.
7.2.1 Atomic Absorption Spectropho-
tometer.

NOTE 13-The text of this method is most

applicable to the use of a Perkin Elmer Model
503 A.A., with a 50-mm (2-in.) path length
burner and digital readout. Laboratories using
instruments other than Perkin Elmer should
utilize the method to the fullest extent
possible.

7.2.2 Millipore filter assembly Nº

XX1104710 (47 mm in diameter), or
equivalent. Millipore filter membrane Nº
HAWPO4700 (0.45 p.m membrane), or
equivalent.

NOTE 14-If equivalent filter membranes are

used, they should be checked to confirm they
do not contain chloride which will contaminate
the sample.

7.2.3 100-mL volumetric flasks with

glass stoppers (clear glass).
7.2.4 100-mL volumetric flasks (low
actinic with glass stoppers).

1
The numbers represent, respectively, the (IS) and
(DS2) limits as described in ASTM Recommended
Practice C 670, for Preparing Precision Statements
for Test Methods for Construction Materials.

578
T 260 METHODS OF SAMPLING AND TESTING

10.2 Add 10 mL of 1 + 9 HNO3 to mL volumetric flask. Wash the procedures for silver, including
each of eight 100-mL low actinic precipitate with three or four small measurements of suitable standards
volumetric flasks. Aliquot sufficient portions of distilled water. Dilute to during the determinations.
chloride solution so that each flask will volume (see Figure 2B). 11.7.4 Enter the curve (see Figure 1)
contain a chloride ion concentration of 11.7 Aliquot 10 mL of the filtered with Ag' remaining, and determine the
0.0, 0.1, 0.25, 0.50, 0.75, 1.0, 2.0, and 3.0 sample solution into a 100-mL volume- chloride concentration (mg/L).
mg/L, respectively. The 0.0 concentration tric flask (low actinic). Save balance of
will be the 10 mg/L silver standard. the sample; other dilutions may be
10.3 Proceed with the eight volumetric needed if concentration is relatively high. 12. CALCULATION
flasks following Sections 11.7.1 through 11.7.1 Add 1.5-mL hydrogen peroxide
11.7.3. and agitate for one minute. Calculate the percentage of chloride in
10.4 Set the operating parameters for 11.7.2 Add 10 mL of the 100 mg/L the concrete or concrete raw material, as
A.A. in accordance with the manufactu- silver nitrate solution. Agitate the flask indicated below:
rer’s procedures when using a silver lamp once again and let stand for one hour. ⎛ 1 ⎞⎛ mg / L Cl − ⎞
percent Cl- = ⎜ ⎟⎜ ⎟
10.5 Aspirate the 10 mg/L Ag+ 11.7.3 Vacuum filter, using above ⎝ V ⎠⎝ W ⎠
standard with a zero chloride ion Millipore or equivalent equipment, into a
concentration, and set 10 mg/L in the where:
100-mL volumetric flask (low actinic)
readout window. containing 5 mL of the sodium solution V = volume of aliquot used in Section
10.6 Aspirate the remaining seven and 1 mL of the calcium solution. Wash 11.7, in milliliters,
volumetrics containing 0.1 through 3.0 the precipitate with three or four small W = mass of original concrete sample,
mg/L chloride ion concentrations, and portions of distilled water. Dilute to in grams.
note the readings. Repeat this procedure volume (see Figure 3). This filtrate This equation assumes that the aliquot is
at least three times on three different days contains the unreacted silver ions from diluted to 100 mL.
to obtain an average reading. Develop the the silver chloride precipitation which are
standardization data by aspirating found by standard atomic absorption
randomly.
10.7 Prepare a curve on linear graph
paper, plotting remaining Ag+ ions
determined by A.A. against the seven
chloride standards (see Figure 2A).

11. PROCEDURE

11.1 The sample as received shall be

made to pass a 0.300-mm (Nº 50) sieve.
after removing any free iron that may
have been introduced in sample
preparation. If received sample is
excessively large, quartering may be
necessary before grinding.
11.2 Dry sample at 105°C to constant
mass and cool in dessicator.
11.3 Determine the mass to the nearest
mg of a one (1) g powdered sample
representative of the material under test.
Transfer to a 150-mL beaker, and add 10
mL of dilute nitric acid (1+9) to dissolve
as much of the sample as possible. Break
up any lumps with a stirring rod.
11.4 If carbonates are present, let
sample stand until all effervescence is
completed.
11.5 If the solution is not acid at this
point, add only enough nitric acid to
produce a red color with methyl orange.
11.6 Heat the slurry on a hot plate to
just under boiling, and digest for five
minutes or until all reaction ceases.
Remove from hot plate and cool.
Vacuum filter (Fisher filtrator or equiva-
lent through a 0.45-µm membrane (Milli-
pore filter assembly Nº XX1104710,
Millipore filter membrane Nº
HAWPO4700, or equivalents) into a 100-

579
T 260 METHODS OF SAMPLING AND TESTING

13. PRECISION 15. INTERFERENCES recommended for a maximum coarse

aggregate size of 19 mm (0.75 in.). The
bit grinds the concrete to a fineness of 99
Data are being compiled that will be 15.1 This test procedure is unsuitable percent passing the 850-µm (Nº 20)
suitable for use in developing precision for determining the chloride contents of sieve. The finely ground powder is drawn
statements for this method. concretes containing mineral aggregates into the collection unit through a coaxial
having significant quantities of pyrite. hole in the bit.
PROCEDURE C-Total Ion Using 15.2 The operational response of the 16.3 Sample Collection Unit-A
Specific Ion Probe - Field Test Method specific ion electrode is interfered with cylindrical Polymethol Methacrylate
by the presence of OH, S, Br, I, and CN vacuum sample collection chamber is
in the measured solution and is based on connected to the carbide bit through a
14. SUMMARY OF TEST METHOD the electrode manufacturer's allowable vacuum hose. Vacuum is provided by a
chloride interference ratio. 2.25HP wet/dry shop vacuum unit.
14.1 A 3.0-g concrete drilled powder Figures 6 through 10 present the details
sample is digested in 20 mL of digestion 16. APPARATUS of the sample collection unit that is to be
solution and stabilized by the addition of attached to the wet/dry shop vacuum unit.
80 mL of stabilizing solution. Millivolt 16.4 Filter-An inexpensive coffee
readings taken for the final solution using 16.1 Impact Hammer-A heavyduty
filter works best to collect the powdered
a chloride specific ion probe are rotary impact hammer with a drilling stop
concrete samples in the Polymethol
converted mathematically into equivalent gage is used. See Figures 3 through 5.
Methacrylate chamber.
total percent chloride content or chloride 16.2 Bit-A vacuum bit with a diameter
16.5 Plastic Containers-30-ml, plastic
content in kg/m3(lb/yd3) of concrete. equivalent to 1.5 times the maximum
containers are needed to store the concre-
aggregate size in the concrete is used. A
te samples collected in the coffee filter.
28-mm (1.125-in.) bit size is
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T 260 METHODS OF SAMPLING AND TESTING

16.6 Weighing Papers-76 X 76 mm (3 16.9.2 Resolution at minimal range shall 17.3.2 Chloride content: ≥ 0.4 mg/L.
X 3 in.) pieces of treated paper are be 100 µV 17.3.3 Normality: 17.4.
needed for determining the mass of the 16.9.3 Accuracy shall be +(0.25 percent
powdered concrete samples. 17.4 Isopropyl Alcohol-Reagent grade
of the reading + 1 digit). having the following properties: 17.4.1
16.7 Balances-An electronic balance 16.9.4 Operating temperature range shall Density at 25°C: 0.781 to 0.783.
sensitive to 0.1 g is needed to determine be 0 to 50°C (32 to 122°F).
the mass of the specimens. An electronic 17.4.2 Boiling point: 82.3 ± 0.1°C.
balance sensitive to 0.00019 is needed to 16.9.5 Input impedance shall be greater 17.5 Distilled Water-Distilled water
determine the mate of sodium chloride than 2 MΩ conforming to ASTM D 1193, Type IV.
for the calibration and stabilizing 17.6 Concrete Sample-The concrete
solutions. NOTE 2-The Orion Model 250A is a suitable sample to be analyzed shall be in
16.8 Specific Chloride Ion Electrode- meter. powdered form, 99 percent passing the
The specific ion electrode used to 850-µm (Nº 20) sieve, as taken from the
measure the concentration of chlorides 16.10 Spatula-The spatula used to rotary impact hammer extraction
present in solution must conform to the measure the powdered concrete samples procedure.
following specifications: shall be designed to extract material from 17.7 Nalgene® Containers-Two sizes
16.8.1 Concentration measuring range 1 the storage contained in small quantities. of wide-mouth Nalgene® containers are
m to 5 X 10-5 m, or 35500 to 1.8 mg/L. 16.11 Digestion Solution-20 mL is needed.
16.8.2 The electrode resistance shall be needed for each measurement. 17.7.1 For calibration solutions: five, 40
less than 1.0 megohm. 16.12 Stabilizing Solution-80 mL of mL.
16.8.3 Reproducibility shall be ± 2 stabilizing solution is needed for each 17.7.2 For digestion solution: one, 125
percent. test. mL.
16.8.4 Operating temperature range shall 16.13 Calibration Solution-Five cali-
be 10 to 100°C. bration solutions with 0.01, 0.03, 0.3, 0.6, 18. REAGENTS
and 1.25-percent chloride concentration
based on a 3.0-g powdered concrete
NOTE 1-A suitable specific ion electrode has 18.1 Digestion Solution-The digestion
been found to be the Orion Combination specimen are needed to calibrate the
instrument. solution -is produced by combining
Chloride Electrode Model 96-17B with
chamber filling solution number 900017 (for acetic acid, isopropyl alcohol, and
use with chloride solution concentrations up to distilled water. Measure 940 g of distilled
355 mg/L). 17. MATERIALS water in a 1-liter container. Add 60 g of
glacial acetic acid and 50 g of isopropyl
17.1 Sodium Chloride-Reagent. alcohol to the distilled water. Thoroughly
16.9 Multimeter-The multimeter used stir the solution. Dispense the solution
in the procedure must conform to the 17.2 Ethyl Alcohol-Reagent grade. into the 125-mL Nalgene® bottles in
following specifications: 17.3 Acetic Acid-Glacial acetic acid 20mL volumes.
16.9.1 Maximum common mode voltage having the following properties:
shall be 1500 VDC or peak AC. 17.3.1 Specific gravity: 1.05.

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T 260 METHODS OF SAMPLING AND TESTING

18.2 Calibration Solutions-The cali- by temperature variations, ensure that the equation for the combination used to
bration solutions are made by dissolving calibration, digestion, and stabilizing determine the chloride contents of
sodium chloride in distilled water. The solutions are maintained at 22.2±1.1°C powdered concrete samples. The
concentration levels are 1.25, 0.6, 0.3, (72±2°F). minimum of five calibration solution
0.03, and 0.01 percent by mass Cl based concentrations is needed to adequately
on a 3.0-g concrete sample. To achieve calibrate the equipment combination.
the respective concentration levels, mix 19. SAMPLE PREPARATION Any alterations to equipment combi-
the following quantities of sodium nations shall require the formulation of a
chloride with 1 liter of distilled water: 19.1 Obtain a sample from the new calibration equation.
0.6169 g, 0.2961 g, 0.1481 g, 0.0148 g, concrete structure using the rotary impact 20.2 The calibration equation is
and 0.0049 g. (This will result in hammer with depth gage and the carbide determined as follows:
solutions having chloride concentrations vacuum bit.
of 374, 180, 90, 9, and 3 mg/L, 20.2.1 Calculate the logo of the mg/L
19.2 Using the sample collection unit, chloride concentrations of the calibration
respectively, which in turn correspond to
collect at least 10.0 g of powdered solutions,e.g.,log10 (374 mg/L Cl)=2.573.
the previously listed percentages by mass
concrete in the filter. A 28.6-mm (1 ⅛- 20.2.2 Perform a linear regression of the
of concrete.) Dispense 20 mL into the 40-
in.) diameter hole, 12.7 mm (½-in.) deep millivolt responses (X) versus the logo of
mL Nalgene® bottles and label each
will yield approximately 25 g of the chloride concentrations of the
appropriately.
powdered concrete sample. respective calibration solutions (Y),
18.3 Stabilizing Solution-The stabili-
19.3 Place the filter containing the producing an equation in the following
zing solution is a dilution, standard
sample in the 30-mL sample container. format:
chloride addition solution. It is prepared
as follows: Dissolve 0.1545 g of sodium logo (mg/L Cl) = constant (1)
chloride in distilled water in a one liter 20. CALIBRATION OF THE + coefficient X mV
flask and as necessary add more distilled SPECIFIC ION ELECTRODE NOTE 3-The constant and coefficient will
water to make up 1 liter volume solution. vary with varying equipment combinations.
Take 40 mL of this solution and dilute it However, the constant is numerically
to give a volume of 1 liter by adding 20.1 The measurement of the
characterized by X.XXX and the coefficient is
distilled water. calibration solutions determines the characterized by –0.0XXX, where X
response characteristics of the specific represents digits. The slope should be between
18.4 Temperature-The temperature of ion electrode in combination with the 54 and 60 mV/decade at 25°C. If not, then
the solution during testing significantly multimeter. Mathematical regression of consult the troubleshooting section of the
affects the determined chloride the responses produces a representative manual for the electrode or the manufacturer.
concentration. To minimize errors caused
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T 260 METHODS OF SAMPLING AND TESTING

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T 260 METHODS OF SAMPLING AND TESTING

20.2.3 The percent chloride is Concentration (Cl)% Allowable (mV) effervescence due to the reaction, and
determined from the logarithmic inverse 1.25 (374 mg/L) 1.5 then closed immediately.
of the regression equation (equation 1) 0.60 (180 mg/L) 1.5
21.4 Carefully remove the bottle cap
minus the chloride added by the 0.30 (90 mg/L) 1.5
0.03 (9 mg/L) 1.5
and add 80 mL of the stabilizing solution
stabilizing solution, converted to percent (a 3.75-mg/L chloride solution).
chloride by mass of concrete, as follows: 0.01 (3 mg/L) 4.5
21.5 Replace the cap and shake
%Cl = [l0(0.xxx-o.0xxxmv) - 3 mg/L] vigorously for 1 minute.
(0.0333) (2) 20.5 The calibration equation shall be
based on the data from 10 calibration 21.6 Remove the bottle cap and place
20.3 Although unnecessary for the electrode to a depth of midheight in
calibration, measurements of the runs, each consisting of measurements of
the five calibration solutions. the extraction solution.
calibration solutions are, at the beginning
and end of testing, recommended as a 21.7 Wait 3 minutes and record the
check on the operational integrity of the stable millivolt reading. The millivolt
21. PROCEDURE reading is stable when it oscillates by less
instrument combination. A deviation in
the calibration solution millivolt response than ± 0.5 mV.
indicates a problem involving one or 21.1 Place 20 mL of the digestion 21.8 After each millivolt
more of the following: solution in a clean, dry 125-mL plastic measurement, the electrode shall be
bottle. rinsed clean with distilled water.
20.3.1 Contamination of calibration
solutions. 21.2 Remove the powdered concrete
sample from the filter and return it to the
20.3.2 Contamination of the internal 22. CALCULATIONS
30-mL storage container. Shake and stir
filling solution of the specific ion
the powdered concrete sample to provide
electrode.
a uniform sample, and determine a mass Calculate the percent chloride content in
20.3.3 Defective specific ion electrode. of 3.0 ± 0.1 g on a weighing paper. the sample as follows:
20.3.4 Defective multimeter. 21.3 Place the concrete sample in the %C1 = (A + B y) (3)
20.4 The percent chlorides is based on bottle containing the 20-mL digestion in which:
a 3.0-g powdered concrete sample, and solution, place the cap on the bottle, and
y = [10(e+DmV) - 3](0.003) (4)
the mg/L chloride is the resulting shake vigorously to suspend the powder
concentration of a 100-mL solution. The in the solution. Let the powder digest for and
allowable deviations of the specific ion 3 minutes. The bottle may be opened A = a unique value for a combination
electrode are presented below: after shaking to relieve pressure from of a probe and a meter
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T 260 METHODS OF SAMPLING AND TESTING

determined from the relationship multiplying by the conversion factor concrete structures as a function of depth.
between a standard titration 39.15.) Using the values obtained, the chloride
method and this rapid method; a diffusion constant can be calculated and
typical value is 0.8984 the time to corrosion of embedded steel
24. PRECISION AND BIAS reinforcement can be estimated.
B = a unique value for a combination
of a probe and a meter
determined from the relationship 24.1 Precision-The single-operator NOTE 4-A statistical number of samples
between a standard titration within-laboratory standard deviation was should be taken on a structure to provide a
method and this rapid method; a found to be 1.91 mV (1 s). Therefore, the valid determination of the chloride content of
typical value is 1.165 results of two properly conducted tests by the concrete in the structure. A minimum of 12
the same operator on the same material samples for a concrete structure is
C and D = The constants determined recommended.
in the calibration step (see should not differ by more than 5.40 mV
Section 9); typical values are (d2 s).
2.855 and 0.01835,. respectively. 24.2 Bias-The test method was found 26. KEYWORDS
mV = potentiometer reading, mV to have no bias in comparing
experimental results with reference
values determined in accordance
23. REPORT procedure A of this method. 26.1 Chloride content, chloride profile,
concrete bridges, onsite testing,
reinforcement corrosion, specific ion
Report the percent chloride content to the 25. SIGNIFICANCE OF RESULTS probe.
third decimal (thousandth of a percent).
(Or, in kg/m3 (lb/yd3) to the first decimal
(tenths of a kg/m3 (lb/yd3)) by This test method permits determination
of the chloride contamination level of

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T 260 METHODS OF SAMPLING AND TESTING

586