Method 425

Determination of Total Chromium

and Hexavalent Chromium
Emissions from Stationary Sources

Adopted: January 22, 1987

Amended: September 12, 1990
Amended: July 28, 1997
 Method 425

Determination of Total Chromium and Hexavalent Chromium

Emissions from Stationary Sources

TABLE OF CONTENTS Page

1 APPLICABILITY AND PRINCIPLES . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1

2 DEFINITIONS . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2

3 PRE-TEST PROTOCOL . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3

4 BIASES AND INTERFERENCES . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 9

5 SENSITIVITY . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 10

6 RANGE . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 10

7 EQUIPMENT . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 11

8 PREPARATION OF EQUIPMENT . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 13

9 REAGENTS . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 14

10 PREPARATION OF REAGENTS . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 17

11 CALIBRATION PROCEDURE . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 18

12 SAMPLING PROCEDURE . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 20

13 RECOVERY PROCEDURE . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 21

14 Cr6 IC-C ANALYTICAL PROCEDURES . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 22

15 Cr6 M-C ANALYTICAL PROCEDURES . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 23

16 Cr GF-AA ANALYTICAL PROCEDURES . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 23

17 QUALITY ASSURANCE / QUALITY CONTROL (QA/QC) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 24

18 RECORDING DATA . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 27

19 CALCULATING RESULTS . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 27

20 REPORTING RESULTS . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 30

21 ALTERNATIVE TEST METHODS . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 31

July 28, 1997 M425 Page i

22 REFERENCES . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 32

23 FIGURES . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 32

Figure 1. Sample Collection and Recovery for Hexavalent and Total Chromium

Figure 2. Hexavalent Chromium Analysis

Figure 3. Total Chromium Analysis

July 28, 1997 M425 Page ii

 Method 425

Determination of Total Chromium and Hexavalent Chromium

Emissions from Stationary Sources
1 APPLICABILITY AND PRINCIPLES

1.1 Applicability

This method applies to the determination of hexavalent chromium (Cr6) and total chromium (Cr)
emissions from stationary sources. Applicability has been demonstrated for the metal finishing and
glass industries. Its applicability has not been demonstrated for sources with high particulate mass
emission rates.

The ion chromatographic-colorimetric (IC-C) analytical procedure described is applicable to filter

extracts and emission samples collected in impinger solutions of 0.1M sodium hydroxide solution. It
is also applicable to samples in water or in the ammonium hydroxide/ammonium sulfate eluent
solution described herein. Preconcentration of larger volumes of the sample on an anion guard
column prior to injection to increase the sensitivity of the procedure cannot be recommended at this
time due to the levels of chromate and interfering compounds found in the commonly available
grades of sodium hydroxide and because of the tendency of sodium hydroxide to act as an internal
eluent on the preconcentration column.

Any modification of this method shall be subject to approval by the Executive Officer. The term
"Executive Officer", as used in this document, shall mean the Executive Officer of the Air Resources
Board, or his or her authorized representative.

1.2 Sampling Principle

Particulate emissions are collected from the source in an alkaline medium by use of CARB Method 5,
with modifications noted in this method.

1.3 Recovery Principle

The components of the collected sample are each divided into two equal portions with one portion of
each component used for total chromium analysis and the other portion used for hexavalent
chromium analysis.

1.4 Cr6 Ion Chromatographic-Colorimetric (IC-C) Analytical Principle

This procedure, as described, uses direct sample injection and post column derivatization with a 1,5
diphenylcarbazide colorimetric reagent and photometric detection at 540 nm. Hexavalent chromium
is separated from other metallic anions as chromate by a high capacity anion separator column and a
colored product having a wide absorption band centered at approximately 540 nm is formed by
reaction with the colorimetric reagent. The colored reaction product is detected photometrically and
quantitation as Cr6 is accomplished by linear regression of either peak area or peak height on the
concentration of a series of Cr6 calibration standards.

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1.5 Cr6 Manual-Colorimetric (M-C) Analytical Principle

For the hexavalent chromium analysis the collected sample component portions are extracted in an
alkaline solution and analyzed by the diphenylcarbazide colorimetric method which requires 35mL of
sample liquid per analysis.

1.6 Cr Graphite Furnace-Atomic Absorption (GF-AA) Analytical Principle

For the total chromium analysis the collected samples shall be prepared in order to convert organic
forms of chromium to inorganic forms, to minimize organic interferences, and to convert the sample
to a suitable solution for analysis. Samples are then subjected to an acid digestion procedure.
Following the appropriate dissolution and dilution of the sample, a representative aliquot is placed
manually or by means of an automatic sampler into a graphite tube furnace. The sample aliquot is
then slowly evaporated to dryness, charred (ashed), and atomized. The absorption of hollow cathode
radiation during atomization will be proportional to the chromium concentration.

2 DEFINITIONS

2.1 End User

For the purposes of this method, the regulating agency or its authorized representative shall be
considered the end user if a determination of Cr and Cr6 emissions from a stationary source is
required as part of a regulatory process. Otherwise the end user shall be the party who defrays the
cost of performing this method. The pre-test protocol must identify the end user.

2.2 Tester

Usually the tester is a contract engineering firm that performs the sampling procedures and delegates
responsibility for specific analytical procedures to an analytical group (usually part of a
subcontracting laboratory firm). The tester shall ultimately be responsible for performance of this
method whether directly or indirectly through co-ordination of the efforts of the sampling and
analytical groups.

2.3 Source Target Concentration

This is the target concentration for hexavalent chromium (Cr6) specified by the end user of the test
results. The target concentration shall be expressed in units of Cr6 mass per volume of emissions;
typical units are nanograms per dry standard cubic meter or micrograms per dry standard cubic meter
(ng/m3 or µg/m 3).

2.4 Limit of Detection

The limit of detection (LOD) is a limit of the performance of the analytical procedures below which
quantitative results must not be reported. The LOD is based on the absolute value of the x-intercept
of the calibration plot for absorbance versus concentration adjusted by three times the standard
deviation of the absorbance for a mid-point concentration.

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2.5 Reporting Limit

The reporting limit (RL) is a limit of the performance of the entire test method below which
quantitative mass analyses must not be reported for a given sample run. The RL is based on the
minimum analyte mass that must be collected in the sampling train to allow detection by the
laboratory according to the requirements of this method. Such mass is the product of the LOD and
the liquid volume used to collect the analyte in the sampling train.

2.6 Source Reporting Limit

The source reporting limit (SRL) is a limit of the performance of the entire test method below which
quantitative emission results must not be reported.

3 PRE-TEST PROTOCOL

3.1 Responsibilities of the End User and Tester

3.1.1 The End User

Before testing may begin, the end user of the test results must specify the source target
concentration to be determined by this method using the guidelines of § 3.2.1.

The end user shall approve the pre-test protocol after reviewing the document and determining
that the minimum requirements for the pre-test protocol (§ 3.2) have been met.

3.1.2 The Tester

The tester shall have primary responsibility for the performance of the test method, and shall co-
ordinate the efforts of the sampling and analytical groups.

The tester shall plan the test based on the information provided by the end user and the tester's
calculations of target source testing parameters.

The tester shall be responsible for selection of an analyst qualified for use of the method. The
tester shall make that decision based on information supplied by the analyst.

The tester shall obtain all relevant data that are required for pre-test calculations of sampling
parameters. The tester shall develop and write a pre-test protocol before performing this method
to help ensure satisfactory results.

The tester shall be responsible for ensuring that all sampling and analytical reporting
requirements are met.

3.2 Pre-Test Protocol

The pre-test protocol should include the test performance criteria of the end user and all assumptions,
required data and calculated targets for the following testing parameters:

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 (1) source target concentration of Cr6 (§ 3.2.1),
(2) preliminary analytical data (§ 3.3) for Cr6, and
(3) planned sampling parameters (§ 3.5).

The protocol must demonstrate that the testing parameters calculated by the tester will meet the
needs of the end user. In addition, the pre-test protocol should include information on equipment,
logistics, personnel and other resources necessary for an efficient and coordinated test.

At a minimum, the pre-test protocol shall identify the end user of the results, the tester, the analytical
group, and the sampling group, and the protocol shall be approved by the end user of the results and
the tester.

The tester should not proceed with the performance of the remainder of this method unless the pre-
test protocol is approved by the tester and the end user.

3.3 Source Target Concentration (STC)

The tester shall not proceed with the test unless a target concentration has been chosen. The end user
shall select a basis for determining each target concentration from: a) regulatory limits, b)
environmental risk assessments, and (c) the interests of the end user, the tester, and the stationary
source.

(1) Regulatory Limits

The regulatory limit shall be the basis for determining a target concentration for stationary
source emissions in those cases where the purpose of the emissions test is to demonstrate
compliance with the established regulatory limit.

(2) Environmental Risk Assessments

In some cases testing is conducted for an environmental risk assessment. A pre-test estimate of
the permissible risk shall then be used to determine the target concentration for stationary source
emissions.

(3) Interests of the End User, the Tester, and the Stationary Source

In cases where the emissions test is not being performed to demonstrate compliance with a
regulation, nor is it required for a risk assessment, the end user may use emissions results from
previous tests of the facility or from similar sources. This target concentration is necessary for
the calculation of the target sampling parameters required by § 3.5.

3.4 Preliminary Calculations

3.4.1 Determining the Limit of Detection (LOD)

The "Analytical Calibration Procedure" of this test procedure which is appropriate for the target
substance shall be used for the analytical calibration and the determination of the limit of
detection (LOD) described below. Such analytical calibration shall be performed prior to

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 sampling by the same analytical personnel who perform the analytical calibration subsequent to
sampling; this does not exclude the use of documentation for analytical calibration performed for
prior tests.

(1) Plotting Absorbance versus Concentration

Plot absorbance as the dependent variable (y-axis) and concentration as the independent
variable (x-axis).

(2) Determining the Standard Deviation at the Midpoint

Prepare a standard solution of the target substance with a concentration near the midpoint of
the calibration curve.

Analyze four or more aliquots of this solution and plot the results.

Calculate the standard deviation, smid, of the absorbance.

(3) Calculating the X-Intercept and Slope

Using the least squares method, determine the x-intercept, a, and slope, n, of the line through
the data.

Equation 425-1 shall be used to calculate the LOD.

3smid
LOD ' *a* % 425-1
n

Where:

LOD = limit of detection, ng/mL

*a* = absolute value of x-intercept, ng/mL

3smid = three times the standard deviation of the midpoint absorbance,

absorbance units

n = slope of the calibration line, (absorbance units)/(ng/mL)

3.4.2 Determining the Reporting Limit (RL)

To obtain the lowest RL, assume that:

(1) all of the Cr6 in the gas sampled is recovered from the liquid of the probe rinse and the first
impinger and

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 (2) the volume of the liquid of the probe rinse and the first impinger is 220 mL.
Equation 425-2 shall be used to calculate the RL.

RL ' LOD × 220 425-2

Where:

RL = analytical mass reporting limit, ng

LOD = limit of detection, ng/mL

220 = liquid volume of probe rinse and first impinger, mL

3.5 Sampling Runs, Time, and Volume

3.5.1 Sampling Runs

A test shall include at least three sampling runs in series and a blank sampling train.

3.5.2 Minimum Sample Volume (MSV)

This is the minimum sample volume that must be collected in the sampling train to provide
sufficient Cr6 for analytical quantitation. The MSV must be based on the reporting limit and the
source target concentration. The MSV will be adjusted, based on further practical limitations, to
yield the planned sample volume (PSV) in subsequent sections.

Equation 425-3 shall be used to calculate the MSV.

1
MSV ' RL × 425-3
STC

Where:

MSV = minimum sample volume, dscm

RL = analytical mass reporting limit, ng

STC = source target concentration, ng/dry standard cubic meters (dscm)

3.5.3 Minimum Sampling Time (MST)

This is the minimum time required to collect the minimum sample volume at the expected
volumetric sampling rate. The tester should use an average volumetric sampling rate (VSR)

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 appropriate for the source to be tested. If the VSR cannot be achieved in the field, the sampling
time shall be revised using the following equation to achieve the target MSV. The sampling time
must be such that the emissions test is conducted during representative operating conditions of
the source.

Equation 425-4 shall be used to calculate the MST.

MSV
MST ' 425-4
VSR

Where:

MST = minimum sampling time, hours

MSV = minimum sample volume, dscm

VSR = volumetric sampling rate, dscm/hour

3.5.4 Planned Sample Volume (PSV)

The planned sample volume (PSV) is the volume of emissions that must be sampled to collect
for analysis a mass of Cr6 between the RL and the limit of linearity. The PSV is the primary
sampling target whenever practically feasible. Calculate the PSV using the largest value for F
that will give a practical sample volume.

Equations 425-5 and 425-6 shall be used to calculate the PSV.

PSV ' MSV × F 425-5

PSV ' PST × VSR 425-6

Where:

PSV = minimum sampling time, hours

MSV = minimum sample volume, dscm

F = safety factor for detection (F $ 1)

PST = planned sampling time, hours

VSR = volumetric sampling rate, dscm/hour

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 Typically, when the value of F is one or greater, it is safe to assume that Cr6 will be detected at
or above the source target concentration (STC). Greater values of F provide greater assurance.
Typically, when the value of F is less than one, it is unsafe to assume that Cr6 will be detected at
the source target concentration (STC).

3.5.5 Planned Sampling Time (PST)

The planned sampling time (PST) is calculated using Equation 425-7.

PST ' MST × F 425-7

Where:

PST = planned sampling time, hours

MST = minimum sampling time, hours

F = safety factor for detection (F $ 1)

3.5.6 Pre-Test Calculation of Source Reporting Limit (SRL)

Before the test proceeds, the end user and the tester shall agree on a preliminary estimate of the
reporting limit for emissions of Cr6 from the source. Notice that the SRL is higher than the STC
if F is less than one in which case it is unsafe to assume that Cr6 will be detected at the STC.

Equation 425-4 shall be used to calculate the SRL.

RL
SRL ' 425-8
PSV

Where:

SRL = source concentration reporting limit, ng/dscm

RL = analytical mass reporting limit, ng

PSV = planned sampling volume, dscm

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4 BIASES AND INTERFERENCES

4.1 Sample Instability

Chromium is subject to changes in valence state during the time between sampling and recovery.
Take all reasonable precautions, some of which are required in various sections of this method, to
minimize all influences which may change the valence states of chromium in each sample. Factors
which influence such changes are hold time, pH, and other chemical species.

Recovery of trains shall take place within 24 hours of sampling. Storage between recovery and
analysis shall be at or below 4C and shall be limited to two weeks.

4.2 Cr6 IC-C Interferences

A high ionic concentration in the sample may overload the chromatographic column, altering the
retention time and/or the shape of the chromate peak. Anionic species such as molybdate or vanadate
which will react with the 1,5 diphenylcarbazide post-column reagent to form a colored product
absorbing at 520-540 nm may obscure or interfere with the quantitation of the chromate peak by
coeluting with or overlapping with it, if the concentration of the interfering compounds is sufficiently
high. Some known interferences are:

4.2.1 Molybdenum

Molybdenum as a solution of molybdic acid (H2MoO4.H2O) in water produced a peak which

eluted at 3.55 minutes when Cr6 was eluting at 4.25 minutes. The Mo6+ peak was resolved
from a peak representing 50 ng Cr6/mL up to a concentration of approximately 500 µg
Mo6+/mL.

4.2.2 Vanadium

Vanadium as a solution of ammonium vanadate (NH4VO3) in water produced a broad peak at

2.80 minutes when Cr6 was eluting at 4.25 minutes. This peak was resolved from a peak
representing 50 ng Cr6/mL up to a concentration of approximately 10 µg V 5+/mL.

4.3 Cr6 M-C Interferences

Molybdenum, mercury and vanadium react with diphenylcarbazide to form a color; however,
approximately 20 mg of these elements can be present in a sample without creating a problem. Iron
produces a yellow color, but this effect is not measured photometrically at 540 nm.

4.4 Cr GF-AA Interferences

The long residence time and high concentrations of the atomized sample in the optical path of the
graphite furnace can result in severe physical and chemical interferences. Furnace parameters shall
be optimized to minimize these effects. If the analyte is not completely volatilized and removed from
the furnace during atomization, memory effects will occur. If this situation is detected, the tube shall
be cleaned by operating the furnace at higher atomization temperatures.

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 Nitrogen shall not be used as the purge gas because of a possible CN band interference.

Low concentrations of calcium may cause interferences; at concentrations above 200 mg/L calcium's
effect is constant. Calcium nitrate is therefore added to ensure a known constant effect. This step
may be omitted if the sample is known to be free of calcium or no analytical interferences are
expected.

5 SENSITIVITY

The test method sensitivity is dependent on the parameters chosen during the required pre-test protocol in
the ?PRE-TEST PROTOCOL” section. In general, the higher the planned sampling volume, the better
(lower) the test method sensitivity.

5.1 Cr6 IC-C Sensitivity

Based on the procedures given in the "Pre-Test Protocol," an LOD as low as 0.5 ng/mL has been
observed; this is not a default value as achievement of such low levels depends upon the skill of the
analytical team.

5.2 Cr6 M-C Sensitivity

Based on the procedures given in the "Pre-Test Protocol," an LOD as low as 4.0 ng/mL has been
observed; this is not a default value as achievement of such low levels depends upon the skill of the
analytical team.

5.3 Cr GF-AA Sensitivity

EPA Method 306, Determination of Chromium Emissions from Decorative and Hard Chromium
Electroplating and Anodizing Operations, reports a value of 1.0 ng/mL, based on method 7191 of
SW-846. For some sample matrices, the Cr GF-AA sensitivity can be lower than the Cr6 IC-C
sensitivity.

6 RANGE

6.1 Cr6 IC-C Range

Using sample loops of 10 uL to 250 uL, the linear range of this procedure without dilution or
concentration of the sample is approximately 0.5 ng Cr6/mL to 40 µg Cr6/mL.

6.2 Cr6 M-C Range

A straight line response curve was obtained in the range 0.5 µg Cr6 /50 mL to 3.0 µg Cr6 /50 mL
(10 to 60 ng/mL). The range can be expanded to 0.5 to 50 µg/mL, provided that the residuals are
less than 10%. For a minimum analytical accuracy of 100 + 10 percent, the lower limit of the range
is 2 µg/100mL. The upper limit can be extended by appropriate dilution or by using a smaller cell
path length after recalibration for the smaller cell.

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6.3 Cr GF-AA Range

EPA Method 306, Determination of Chromium Emissions from Decorative and Hard Chromium
Electroplating and Anodizing Operations, reports an optimum range of 5 to 100 ng/mL, based on
method 7191 of SW-846. For some sample matrices, the Cr GF-AA range can be broader than the
Cr6 IC-C range.

7 EQUIPMENT

All surfaces which may come in contact with sample shall be glass, quartz, Teflon, or other similarly non-
metallic (stainless steel may be a source of chromium contamination) inert material.

Although Teflon is not the required material of construction for sampling train components, it can be
used to reduce problems with equipment contamination and cleaning.

Any other sampling apparatus which, after review by the Executive Officer, is deemed equivalent for the
purposes of this test method, may be used.

7.1 Sampling Equipment

Except where otherwise noted in this method, same as CARB Method 5, Section 2.1. Exceptions
include a glass nozzle, a glass lined stainless steel probe, 0.1 N NaOH in the first two impingers, a
Teflon-coated glass fiber filter, and a silica gel moisture trap after the filter. As shown in Figure 1,
sample flow shall be through the probe first, then the impingers, and then the filter.

7.2 Recovery Equipment

Except where otherwise noted in this method, same as CARB Method 5, Section 2.2.

7.3 Analytical Equipment

7.3.1 Cr6 IC-C Analytical Equipment

The following system has been found suitable for hexavalent chromium analysis as described in
this procedure. Specifications, analytical ranges, and detection limits were determined using this
system. An equivalent system may be used so long as it is demonstrated to be capable of
separating and detecting hexavalent chromium, and the sensitivity and precision of the system is
determined to be adequate.

7.3.1.1 DIONEX Ion Chromatography System 4000i (or equivalent), including:

Gradient Pump Module

Advanced Chromatography Module

Variable Wavelength Detection Module

Automated Sampler

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 Eluant Degas Module

Advanced Computer Interface

IBM-AT Compatible Computer, running the DIONEX Autoion 450 (or equivalent) Data
System Chromatography Software

Chromatographic Columns
Organic compound guard column: DIONEX MPIC-NG1 (or equivalent) neutral guard
column.

Anion guard column (can also used as a preconcentrater column): DIONEX HPIC-AG7 (or
equivalent) high-capacity anion guard column.

Separator column: DIONEX HPIC-AS7 or equivalent high-capacity anion separator

column.

7.3.1.2 Post-Column Reagent System, including:

Pressurized reagent reservoir.

120 cm Packed Bed Reaction Coil.

7.3.2 Cr6 M-C Analytical Equipment

7.3.2.1 100 mL beakers

7.3.2.2 Filtration Apparatus

Vacuum unit constructed of glass, to accommodate sintered glass funnels. Medium porosity
filter paper is optional. Wherever filtering is specified, centrifuging may also be performed
at the analyst's option.

7.3.2.3 Volumetric Flasks

100-mL and other appropriate volumes.

7.3.2.4 Hot Plate

7.3.2.5 Pipettes

Assorted sizes, as needed.

7.3.2.6 Spectrophotometer

To measure absorbance at 540nm.

July 28, 1997 M425 Page 12

7.3.3 Cr GF-AA Analytical Equipment

7.3.3.1 Philips Beakers

Borosilicate, 125mL, with digestion covers.

7.3.3.2 Chromium Hollow Cathode Lamp or Electrodeless Discharge Lamp.

7.3.3.3 Graphite Furnace

Any graphite furnace device with the appropriate temperature and timing controls.

7.3.3.4 Strip Chart Recorder

A recorder is recommended for furnace work so that there will be a permanent record and so
that any problems with the analysis such as drift, incomplete atomization, losses during
charring, changes in sensitivity, etc., can easily be recognized.

8 PREPARATION OF EQUIPMENT

The following sections specify a recommended cleaning procedure for sampling equipment and
extremely stringent cleaning performance criteria. An alternative cleaning procedure is allowed providing
that experimental documentation is provided which demonstrates that the alternative cleaning procedure
has been established and is at least as effective at achieving the cleaning performance criteria as the
recommended procedure.

The chosen cleaning procedure shall be applied to all equipment surfaces (not only the probe surfaces)
which can come in contact with the sample.

8.1 Recommended Cleaning Procedure

All surfaces which can come in contact with sample shall be glass, Teflon, or other similarly non-
metallic (even stainless steel may be a source of chromium contamination) inert material and shall be
prewashed with detergents, soaked in 1:1 HNO3 for several hours, rinsed with Type II water, and
finally rinsed with 0.1 N NaOH batch solution. For awkward objects, such as long glass probes,
soaking may be replaced by careful wiping.

Probes are generally the most difficult sampling apparatus to clean. Therefore, before use in
sampling, to ensure that sampling equipment is clean and free of chromium contamination, apparatus
which may come in contact with sample shall be cleaned and a sample of the final rinse for each
probe shall be analyzed for Cr (total chromium). If Cr is detected in the final rinse, each probe shall
be re-cleaned until a sample of the final rinse contains no detectable Cr. "Cr GF-AA ANALYTICAL
PROCEDURES" shall be followed for this contamination check.

8.2 Alternative Cleaning Procedure

If the specified glass probes are in short supply, the recommended cleaning procedure could double
the number of days necessary to complete a series of tests.
Time can be saved by using the following options:

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8.2.1 Development, Testing, and Documentation

An alternative cleaning procedure may be used if it is developed, tested, and documented as

achieving the objective of no detectable chromium in the last probe cleaning rinse. Testing and
documentation shall include: a pre-test visit to the intended site, collection of samples from an
intended test point with the highest expected concentration of chromium, trials of other cleaning
procedures, and documentation of those alternative cleaning procedures which pass the
contamination check of the "Recommended Cleaning Procedure".

8.2.2 Advanced Preparation

The best protection against lost time is to procure enough pre-cleaned equipment before a field
trip so that no equipment needs to be re-cleaned and re-used during field sampling. Procure extra
pre-cleaned equipment to allow for breakage, etc.

9 REAGENTS

Unless otherwise indicated, all reagents shall conform to the specifications established by the Committee
on Analytical Reagents of the American Chemical Society. Where such specifications are not available,
use the best available grade.

9.1 Sampling Reagents

9.1.1 Method 5 Reagents

Except where otherwise noted in this method, same as CARB Method 5, Section 3.1, except
Teflon-coated glass fiber filters are used, and 0.1 N NaOH is used in the first two impingers.

9.1.2 Batch of 0.1N NaOH Solution, Analytical Reagent Grade

The most important purpose of this solution is to maintain hexavalent chromium in a high pH
solution so that it is not reduced to trivalent chromium. In particular, liquid samples must be
taken and transported at a pH of 8.0 or higher.

Any other solution which can meet this and the other performance specifications of this method
is also acceptable.

See "PREPARATION OF REAGENTS."

9.2 Recovery Reagents

Except where otherwise noted in this method, same as CARB Method 5, Section 3.2.

9.3 Cr6 IC-C Analytical Reagents

Unless otherwise indicated, all chemicals shall conform to the specifications established by the
Committee on Analytical Reagents of the American Chemical Society. All reagents shall be
analyzed before testing is begun using the IC-C system to be employed in the analysis of the
samples, and the Cr6 concentration shall be less than the detection limit.

July 28, 1997 M425 Page 14

9.3.1 Batch of 0.1N NaOH Solution

See "PREPARATION OF REAGENTS."

9.3.2 Water

All water used in this procedure shall, at minimum, conform to the specifications of American
Society for Testing and Materials (ASTM) Type II reagent water as specified in ASTM Test
Procedure D 1193. Use of ASTM Type I reagent water shall be an acceptable alternative.

9.3.3 Eluent

Dissolve 33 g of ammonium sulfate in water in a 1 L Class A volumetric flask. Add 6.5 mL of

29% ammonium hydroxide and make to volume. The concentration of the prepared eluent is 250
mM (NH4)2SO4 and 100 mM NH4OH.

9.3.4 Post-Column Reagent

Dissolve 0.5 g of 1,5 diphenylcarbazide in 100 mL of glass distilled HPLC grade methanol. Add
to approximately 500 mL of degassed or nitrogen purged or helium purged water containing 28
mL of 96-98% sulfuric acid, and make to 1 L with degassed or nitrogen purged or helium purged
water. High purity sulfuric acid such as EM Science Suprapur grade or JT Baker Ultrex grade is
recommended. The stability of the post-column reagent is enhanced by preparing it in a nitrogen
atmosphere, pressurizing the reagent reservoir with nitrogen, and shielding it from light.

9.3.5 Cr6 Stock Solution

Prepare a standard solution containing 1000 µg Cr6 /mL as a solution of potassium dichromate
in water. Use analytical reagent grade K2Cr2O7 which has been dried at 105o C for at least one
hour. Dissolve 2.8289 g of the dried K2Cr2O7 in water in a class A volumetric flask and make to
volume with water. Alternatively, obtain a chromate standard solution in water prepared
specifically for use in ion chromatography.

Storage shall be at or below 4oC and shall be limited to four weeks.

9.3.6 Regenerant Solution for the DIONEX MPIC-NG1 Guard Column (or equivalent)

In this application, the DIONEX MPIC-NG1 guard column (or equivalent) is used to trap
organic compounds which could adversely affect the anion chromatographic columns. The
trapped organic compounds shall be flushed from the column periodically using a 70-90%
solution of acetonitrile or methanol in water.

9.4 Cr6 M-C Analytical Reagents

9.4.1 Batch of 0.1N NaOH Solution

See "PREPARATION OF REAGENTS."

July 28, 1997 M425 Page 15

9.4.2 Type II Water

Type II water is deionized and distilled, meeting American Society for Testing and Materials
(ASTM) specification for type reagent - ASTM Test Method D 1193-77. The water shall be
monitored for impurities.
9.4.3 Potassium Dichromate Stock Solution

Dissolve 2.829 g of analytical reagent grade potassium dichromate (K2Cr2O7) in water, and
dilute to 1 liter (1 mL = 1000 µg Cr6).

9.4.4 Potassium Dichromate Standard Solution

Dilute 10.00 mL potassium dichromate stock solution to 100 mL (1 mL = 100 µg Cr6 with
water.

9.4.5 Sulfuric Acid, 6N, Analytical Reagent Grade

Dilute 166 mL sulfuric acid to 1000 mL in water.

9.4.6 Diphenylcarbazide Solution, Analytical Reagent Grade

Dissolve 0.5 g of 1,5-diphenylcarbazide in 100 mL acetone. Store in a brown bottle. Discard

when the solution becomes discolored.

9.4.7 0.1% Potassium Permanganate Solution

Analytical Reagent Grade

9.4.8 0.01% Potassium Permanganate Solution

Analytical Reagent Grade

9.5 Cr GF-AA Analytical Reagents

9.5.1 Batch of 0.1N NaOH Solution

See "PREPARATION OF REAGENTS."

9.5.2 ASTM Type II Water (ASTM D1193)

9.5.3 Concentrated Nitric Acid

Reagent preparation shall use Ultrex (or equivalent) grade HNO3.

Glassware cleaning shall use ACS reagent grade HNO3.

9.5.4 Hydrogen Peroxide (30%) (Optional), Analytical Reagent

July 28, 1997 M425 Page 16

9.5.5 Matrix Modifier

Follow manufacturer's recommendations, when interferences are suspected.

9.5.6 Total Chromium Standard Stock Solution (1000 mg/L)

Either procure a certified aqueous standard from a supplier (Spex Industries, Alpha Products,
Fisher Scientific, etc.) and verify by comparison with a second standard, or dissolve 2.829 g of
Potassium Dichromate (K2Cr207, analytical reagent grade) in Type II water and dilute to 1 liter
in a volumetric flask.

9.5.7 Total Chromium Working Standards

All total chromium preparations injected for analysis shall be prepared to contain 1.0% (v/v)
HN03. The zero standard shall be 1.0 % (v/v) HNO3.

10 PREPARATION OF REAGENTS

10.1 Preparation of Reagents for Sampling

10.1.1 Batch of 0.1N NaOH Solution, Analytical Reagent Grade

The same batch of 0.1N NaOH solution shall be used for impinger sampling, sample recovery,
preparation, extraction, and analysis.

This is necessary to avoid the use of different 0.1N NaOH solutions with different levels of
contamination, especially of Cr6, but also of analytical interferents.

Therefore, sampling and analytical personnel shall coordinate their plans so that all steps in
sampling and analysis use the same batch of solution which will be prepared fresh for each
source test. Typically, dissolve 4.0 g NaOH in water in a 1 liter volumetric flask and dilute to
the mark. Repeat, as necessary, so that a single batch of sufficient volume is prepared to serve
all of the needs of sampling and analysis. Store the solution in a tightly capped polyethylene
bottle.

The most important purpose of this solution is to maintain hexavalent chromium in a high pH
solution so that it is not reduced to trivalent chromium. In particular, liquid samples must be
taken and transported at a pH of 8.0 or higher.

Any other solution which can meet this and the other performance specifications of this method
is also acceptable.

10.1.2 Removal of Reducing Agents in the Reagents

The 0.1 N NaOH extraction solution and the 6N sulfuric acid solution may contain small
amounts of reducing agents that can react with the hexavalent chromium. Potassium
permanganate (KMnO4) is added to these reagents in order to neutralize these reducing agents.

Determine the amount of KMnO4 needed as follows:

July 28, 1997 M425 Page 17

 Pipette 3 mL of the extraction solution into cuvettes A and B. Use cuvette A as a sample cell
and cuvette B as a reference cell. Zero the instrument at 528 nm with both cuvettes.
Wait 10 minutes. Add an adequate amount (uL) of 0.01% potassium permanganate solution to
cuvette A so that after 10 minutes a slight change in absorbance is observed. This step may have
to be repeated a number of times in order to determine the required amount of potassium
permangante.

From the change in absorbance, calculate the amount of potassium permanganate per unit
volume needed to neutralize the reducing agents found in the reagents.

Determine the amount of higher concentration 0.1% potassium permanganate solution needed to
treat the volume of reagent. Pipette this amount of 0.1% KMnO4 into the reagents.

Repeat this procedure with the 6N sulfuric acid solution.

10.2 Preparation of Reagents for Recovery

The same batch of 0.1N NaOH solution shall be used for impinger sampling, sample recovery,
preparation, extraction, and analysis.

10.3 Preparation of Reagents for Analysis

The same batch of 0.1N NaOH solution shall be used for impinger sampling, sample recovery,
preparation, extraction, and analysis.

11 CALIBRATION PROCEDURE

11.1 Sampling Calibration Procedure

Perform all of the calibrations described in CARB Method 5, Section 5, with any modifications
appropriate for this method.

11.2 Recovery Calibration Procedure

Follow the appropriate analytical calibration procedure.

11.3 Cr6 IC-C Analytical Calibration Procedure

Inject a series of Cr6 calibration standards which brackets the sample concentrations. Also, use a
zero standard. Typically, 4 to 6 calibration standards will be sufficient to establish the calibration
curve. The recommended procedure is to inject one series of calibration standards before the
samples, to establish that the system is working properly and has reached equilibrium so that a linear
response is attained. A second set of calibration standards is injected at the end of the analytical run
to confirm constancy of response throughout the run. If the peak areas or peak heights of the two
sets of calibration standards differs by more than 5% the run shall usually be repeated. If any drift in
response which may have occurred is within acceptable limits, use the concentration and response
values of the two sets of calibration standards to establish a calibration curve which is used to

July 28, 1997 M425 Page 18

 quantitate the Cr6 concentration in the samples.

Inject a check standard prior to the tenth run of the instrument since its last calibration run.

11.4 Cr6 M-C Analytical Calibration Procedure

(1) Calibrate the wavelength scale of the spectrophotometer every 6 months. The calibration may be
accomplished by using an energy source with an intense line emission such as a mercury lamp, or
by using a series of glass filters spanning the measuring range of the spectrophotometer.
Calibration materials are available commercially and from the National Institute of Standards
and Technology. Specific details on the use of such materials shall be supplied by the vendor;
general information about calibration techniques can be obtained from general reference books
on analytical chemistry. The wavelength scale of the spectrophotometer shall read correctly
within +5 nm at all calibration points; otherwise, the spectrophotometer shall be repaired and
recalibrated. Once the wavelength scale of the spectrophotometer is in proper calibration, use
540 nm as the optimum wavelength for the measurement of the absorbance of the standards and
samples.

(2) Alternatively, a scanning procedure may be employed to determine the proper measuring
wavelength. If the instrument is a double-beam spectrophotometer, scan the spectrum between
530 and 550 nm using a 50 µg Cr6 standard solution in the sample cell and a reagent blank
solution in the reference cell. If a peak does not occur, the spectrophotometer is malfunctioning
and shall be repaired. When a peak is obtained within the 530 to 550 nm range, the wavelength
at which this peak occurs shall be the optimum wavelength for the measurement of absorbance
of both the standards and the samples. For a single-beam spectrophotometer, follow the
scanning procedure described above, except that the reagent blank and standard solutions shall
be scanned separately. The optimum wavelength shall be the wavelength at which the maximum
differences in absorbance between the standard and the reagent blank occurs.

(3) Either (1) run a series of 4 to 6 chromium calibration standards and construct a calibration curve
by plotting the concentrations of the standards against the absorbances or (2) if matrix effects
require the method of standard additions (see 17.2.1), plot added concentration versus
absorbance.

(4) Freshly make up each standard for Cr6 in a separate 50 mL volumetric flask starting with 35
mL of the same batch of NaOH solution reserved for its sample set. Then add an appropriate
amount of Cr6 to each calibration standard, starting with none for the zero standard. Then add
6N sulfuric acid and diphenylcarbazide solution in the same manner as in sample preparation.

(5) Inject a check standard prior to the tenth run of the instrument since its last calibration run.

11.5 Cr GF-AA Analytical Calibration Procedure

(1) Calibration standards for total chromium shall start with 1% v/v HNO3 with no chromium for
the reagent blank with appropriate increases in total chromium concentration in the other
calibration standards. The calibration standards shall be prepared following the steps outlined for
sample preparation in the analytical procedures.

(2) Check standards shall be prepared in the same manner as calibration standards. Check standards
shall be prepared separately and independently from the calibration standards and shall serve to
protect against errors in the preparation of the calibration standards.

July 28, 1997 M425 Page 19

 (3) Either (1) run a series of chromium standards and reagent blanks and construct a calibration
curve by plotting the concentrations of the standards against the absorbances or (2) if matrix
effects require the method of standard additions (see 17.2.1), plot added concentration versus
absorbance. For instruments that read directly in concentration, set the curve corrector to read
out the proper concentration.

(4) Re-run the lowest calibration standard after approximately every 10 sample injections.
Standards are run in part to monitor the life and performance of the graphite tube. Lack of
reproducibility or a significant change in the signal for the standards indicates that the tube shall
be replaced.

(5) Duplicates, spiked samples, and check standards shall be routinely analyzed. This requirement is
further specified in the quality assurance/quality control procedures.

(6) Calculate Cr concentrations (1) from a calibration curve, or (2) by the method of standard
additions, or (3) directly from the instrument's concentration readout. All dilution or
concentration factors shall be taken into account.

(7) Calibration curves shall be composed of a minimum of a reagent blank and three total chromium
standards. A calibration curve shall be made for every batch of samples, unless check standards
remain within 10% of the last calibration curve.

(8) Dilute samples with reagent blank solution if they are more concentrated than the highest
standard or if they fall on the plateau of a calibration curve.

12 SAMPLING PROCEDURE

At all times during sampling and transport of samples, the pH of the impinger solutions shall be
maintained above a pH of 8.0 as determined by the use of a clean rod and color indicating paper for pH.

12.1 Method 5 Sampling Procedure and Exceptions

Except where otherwise indicated in this method, all samples are collected from the source by use of
CARB Method 5. Exceptions include a glass nozzle, a glass lined stainless steel probe, 0.1 N NaOH
in the first two impingers, and a Teflon-coated glass fiber filter. As shown in Figure 1, sample flow
shall be through the probe first, then the impingers, and then the filter.

12.2 Sampling Runs

The performance of this test method shall include three or more sampling runs.

The performance criteria documented in the pre-test protocol shall be used by the test crew to
maximize, in the test crew’s judgement, the degree to which each sampling run occurs during an
interval or intervals of time during which the source facility operations are representative of the
conditions intended by the pre-test protocol.
A narrative field log shall be kept by the sampling crew to document observations which
subsequently can be used by others to evaluate the degree to which the source facility operations are
representative of the conditions intended by the pre-test protocol.

July 28, 1997 M425 Page 20

12.3 Field Blank Run

The performance of this test method shall include one or more field blank runs. Every step of the test
method shall be followed for each field blank run with the exception that sample gas shall not be
withdrawn from the source facility by the field blank train.

13 RECOVERY PROCEDURE

At all times during sampling and transport of samples, the pH of the probe rinse and impinger solutions
shall be maintained above a pH of 8.0 as determined by the use of a clean rod and color indicating paper
for pH.

13.1 Silica Gel Recovery

For stack gas moisture determination, weigh the spent silica gel or silica gel plus impinger to the
nearest 0.5 g using a balance. This step may be conducted in the field.

13.2 Probe Recovery

Rinse the probe with at least 100 mL of 0.1 N NaOH ; measure and record the probe rinse volume
and store the probe rinse in Container 1. Transport the probe rinse to a clean room or to a site with
laboratory conditions. Split the probe rinse into two approximately equal volumes; measure and
record the volume of each split. Label one split for Cr6 analysis and label the other split for total Cr
analysis.

13.3 Impinger and Filter Recovery

This method does not require impinger rinses.

The sampling and analytical personnel shall discuss the expected sample concentrations and the
analytical limits of detection for hexavalent and total chromium. The impinger catch and filter shall
be handled one of two ways depending on these expectations as directed below in the "Higher
Concentrations” and "Lower Concentrations” sections below.

13.3.1 Higher Concentrations

If it is not considered important to minimize the dilution of any sample component, then the
contents of both impingers (~200 mL total) shall be combined and stored in container 2.
(Measure the volume.) As soon as possible, the filter is transported in a filter container to a site
with laboratory conditions where it shall be extracted in all of the impinger solution from
Container 2. The extraction shall include shaking for a minimum of 30 minutes. The alkaline
impinger medium will retard reduction of hexavalent chromium.
Split the extract solution with half saved for hexavalent chromium analysis and half saved for
total chromium analysis. Each sample split is ~100 mL. (Measure the volumes.)

13.3.2 Lower Concentrations

If it is considered important to minimize the dilution of any sample component, then the

July 28, 1997 M425 Page 21

 contents of each impinger (~100 mL each) may be stored in Containers 2 and 3. (Measure the
volumes.) The filter shall be extracted in only one of the impinger contents, whichever is
suspected to have the higher concentration. The extraction shall include shaking for a minimum
of 30 minutes. The contents of the first impinger are stored in Container 2 and those of the
second impinger in Container 3. Whichever impinger contents are not used for extraction shall
be handled as a third sample recovery requiring separate analyses.

Split the extract solution with half saved for hexavalent chromium analysis and half saved for
total chromium analysis. Each sample split is ~50 mL. (Measure the volumes.)

14 Cr6 IC-C ANALYTICAL PROCEDURES

The ion chromatograph shall be set up and operated according to the instructions of the manufacturer of
the instrument. A generalized diagram of the system configuration is shown in Figure 1.

14.1 IC-C Preparation

If any of the samples are suspected to contain particulate material, they shall be filtered through a
0.45 µm or smaller pore size membrane filter prior to analysis.

14.2 IC-C Analysis

14.2.1 Eluent Flow Rate

Adjust the eluent flow rate to 1.5 mL/minute.

14.2.2 Post Column Reagent Flow Rate

Adjust the post column colorimetric reagent flow rate to 0.5 mL/minute. The flow rate from the
outlet line of the detector with the post column reagent delivery system on shall be confirmed to
be 2.0 mL/minute.

14.3 IC-C Detection

Absorbance of the colored product formed by the reaction of the 1,5 diphenylcarbazide colorimetric
reagent with Cr6 has been shown to be maximized at 540 nm for the system described and with the
reagents used. The optimum wavelength for detection of the colored Cr6 derivative may vary
depending on the source and batch of reagents used, and may be determined experimentally for each
system by running a series of Cr6 standards at a range of wavelengths of detection. Alternatively, or
in addition, the peak of the absorption band of the colored product can be determined by preparing a
Cr6 standard in eluent, adding 1 part of the colorimetric reagent to 3 parts of the Cr6 spiked eluent,
and recording a plot of the absorption band using a scanning spectrophotometer. The absorption
band of the colored product is relatively broad, and for most applications an adequate response can
be attained at wavelengths of 530-540 nm without the necessity of determining the exact wavelength
of maximum absorbance.

July 28, 1997 M425 Page 22

15 Cr6 M-C ANALYTICAL PROCEDURES

15.1 M-C Preparation

15.1.1 Cr6 Reagent Blank Preparation

For each preparation, transfer 35 mL of solution to a 100 mL beaker, adjust the pH to 1.0 + 0.2
with 6N sulfuric acid, add 1.0 mL of diphenylcarbazide solution, dilute to volume with water in a
50 mL volumetric flask, and let color develop for 10 minutes.

15.1.2 Hexavalent Chromium Sample Preparation

For each preparation, transfer 35 mL of solution to a 100 mL beaker, adjust the pH to 1.0 + 0.2
with 6N sulfuric acid, add 1.0 mL of diphenylcarbazide solution, dilute to volume with water in a
50 mL volumetric flask, and let color develop for 10 minutes. (This leaves at least 15 mL of
sample split for further analyses. The total volume of sample split shall be known at this point.)

15.2 M-C Analysis

(1) Filtration shall be an option for the analyst at this point, depending on the turbidity of the
prepared sample. Medium retention filter paper shall be used. The filter paper shall be pre-
wetted with a few mL of reagent blank and sample preparation. This will prime the filter so that
it won't absorb color complex.

(2) Transfer a portion of the filtered preparation into a 5 cm absorption cell.

(3) Measure the absorbance at the optimum wavelength of 540 nm.

(4) Subtract the sample blank absorbance reading to obtain a net reading.

(5) If the absorbance reading of a sample preparation exceeds the calibration range, dilute with
reagent blank or re-measure using less of the sample preparation. (There shall be about 15 mL
remaining at this point.)

16 Cr GF-AA ANALYTICAL PROCEDURES

16.1 Cr GF-AA Preparation

16.1.1 Cr Reagent Blank Preparation

For total chromium, the reagent blank is an aliquot of 1% HNO3.

16.1.2 Cr Sample Preparation

In a beaker, add 10 ml of concentrated nitric acid to the sample aliquot taken for analysis. Cover
the beaker with a digestion coverglass . Place the beaker on a hot plate and reflux the sample
down to near dryness. Add another 5 mL nitric acid to complete digestion. Reflux the sample
volume down to near dryness.

July 28, 1997 M425 Page 23

 Wash down the beaker walls and digestion cover with distilled water and filter the sample to
remove silicates and other insoluble material that could clog the nebulizer. Filtration shall be
done only if there is concern that insoluble materials may clog the nebulizer. Adjust the volume
to 50 mL or a predetermined value based on the expected Cr concentrations. The final
concentration of HNO3 in the solution shall be 1 % (v/v). The sample is now ready for analysis.
The applicability of a sample preparation technique shall be demonstrated by analyzing spiked
samples and/or relevant standard reference materials.

16.2 Cr GF-AA Analysis

16.2.1 Total Chromium Analysis

(1) The 357.9-nm wavelength line shall be used.

(2) Follow the manufacturer's operating instructions for all other spectrophotometer parameters.

(3) Furnace parameters suggested by the manufacturer shall be employed as guidelines. Since
temperature-sensing mechanisms and temperature controllers can vary between instruments
or with time, the validity of the furnace parameters shall be periodically confirmed by
systematically altering the furnace parameters while analyzing a standard. In this manner,
losses of analyte due to higher than necessary temperature settings or losses in sensitivity
due to less than optimum settings can be minimized. Similar verification of furnace
parameters may be required for complex sample matrices.

(4) Inject a measured uL aliquot of preparation into the furnace and atomize. If the
concentration found exceeds the calibration range, the sample shall be diluted in the same
acid matrix and reanalyzed. The use of multiple injections can improve accuracy and help
detect furnace pipetting errors.

(5) Subtract a reagent blank reading from a sample reading to obtain a net reading.

17 QUALITY ASSURANCE / QUALITY CONTROL (QA/QC)

17.1 Sampling QA/QC

17.1.1 Pre-Test Protocol

At a minimum, the QA/QC of the pre-test protocol shall include:

(1) target concentration (TC) chosen by consent of interested parties

(2) limit of detection (LOD) based on four or more lab blanks

(3) planned sampling flow rate

(4) planned sampling time

July 28, 1997 M425 Page 24

17.1.2 Test Protocol

At a minimum, the QA/QC of the test protocol shall include:

(1) three or more sampling runs

(2) one or more field blanks

17.2 Cr6 IC-C Analytical QA/QC

17.2.1 Check for Matrix Effects on the Cr6 Results

As the analysis for Cr6 by colorimetry is sensitive to the chemical composition of the sample
(matrix effects), the analyst shall check at least one sample from each source using the following
method: Obtain two equal volume aliquots of the same sample solution. The aliquots shall each
contain between 6 and 10 µg of Cr6 (less if not possible). Spike one of the aliquots with an
aliquot of standard solution that contains between 6 and 10 µg of Cr6. Now analyze both the
spiked and unspiked sample aliquots as described in "Cr6 IC-C ANALYTICAL
PROCEDURES" above. Next, calculate the Cr6 mass, in µg, in the aliquot of the unspiked
sample solution, Cs, by using Equation 425-9:

As
Cs ' Ca × 425-9
At & As

Where:

Cs = Cr6 in the unspiked sample solution, µg.

Ca = Cr6 in the standard solution, µg.

As = absorbance of the unspiked sample solution.

At = Absorbance of the spiked sample solution.

Volume corrections will not be required since the solutions as analyzed have been made to the
same final volume. If the results of this method used on the single source sample do not agree to
within 10 percent of the value obtained by the routine spectrophotometric analysis, then
reanalyze all samples from the source using the method of standard additions procedure.

17.2.2 Blanks

Four or more lab blanks shall be analyzed before any performance of this test procedure.

For each set of three field sampling runs, one or more associated field blank runs shall be
analyzed.

July 28, 1997 M425 Page 25

17.2.3 Duplicates

For each set of three field sampling runs, one or more samples shall be injected in duplicate.

If the difference between the determined Cr6 concentrations of the sample duplicates exceeds 5%
of their mean value, the results for the associated sampling runs shall be considered invalid.

17.3 Cr6 M-C Analytical QA/QC

17.3.1 Check for Matrix Effects on the Cr6 Results

As the analysis for Cr6 by colorimetry is sensitive to the chemical composition of the sample
(matrix effects), the analyst shall check at least one sample from each source using the following
method: Obtain two equal volume aliquots of the same sample solution. The aliquots shall each
contain between 6 and 10 µg of Cr6 (less if not possible). Spike one of the aliquots with an
aliquot of standard solution that contains between 6 and 10 µg of Cr6. Now treat both the
spiked and unspiked sample aliquots as described in Section 15.1.2 above. Next, calculate the
Cr6 mass, in µg, in the aliquot of the unspiked sample solution, Cs, by using Equation 425-10:

As
Cs ' Ca × 425-10
At & As

Where:

Cs = Cr6 in the unspiked sample solution, µg.

Ca = Cr6 in the standard solution, µg.

As = absorbance of the unspiked sample solution.

At = Absorbance of the spiked sample solution.

Volume corrections will not be required since the solutions as analyzed have been made to the
same final volume. If the results of this method used on the single source sample do not agree to
within 10 percent of the value obtained by the routine spectrophotometric analysis, then
reanalyze all samples from the source using the method of standard additions procedure.

17.4 Cr GF-AA Analytical QA/QC

(1) Employ a minimum of one matrix-matched sample blank per sample batch to determine if
contamination or memory effects are occurring.

(2) Test the system with check standards after approximately every 15 samples.

(3) Run one duplicate sample for every 10 samples, providing there is enough sample for duplicate
analysis. A duplicate sample is a sample brought through the whole sample preparation.
(See "Cr GF-AA ANALYTICAL PROCEDURES")

July 28, 1997 M425 Page 26

 (4) Spiked samples or standard reference materials shall be used daily to ensure that correct
procedures are being followed and that all equipment is operating properly. This will serve as a
check on calibration standards, too.

(5) Whenever sample matrix problems are suspected, the method of standard additions shall be used
for the analysis of all extracts, or whenever a new sample matrix is being analyzed.

(6) All quality control data shall be maintained for easy reference or inspection.

18 RECORDING DATA

18.1 Data Records

At a minimum, the tester shall maintain records of field, laboratory, and office data sufficient to
support recalculation of reported results by an auditor.

18.2 Narrative Account

At a minimum, the tester shall maintain a narrative account characterizing source and testing
operations during the source testing and analysis. In the narrative, include the means by which the
values of the source and testing parameters, chosen for the pre-test protocol, were maintained; also
include a narrative of unplanned or unexpected events which caused a departure from the chosen
values.

19 CALCULATING RESULTS

Carry out the calculations, retaining at least one extra decimal figure beyond that of the acquired data.
Round off figures after final calculations.

19.1 Total Cr6 in the Sample Train (mCr6)

Calculate and report mCr6, the total µg Cr(VI) in the sample train. This can be obtained from the
calibration curve or from the method of standard additions. Note that mCr6 is the sum of the masses
of hexavalent chromium analyses performed on all sample portions. Also take into account any
dilutions when calculating mCr6.

Calculations shall include only sample portions which have values above the LOD.

Do not subtract the LOD from the sample train values.

19.1.1 Cr6 IC-C Analytical Calculations

Report these calculations based on net values, as determined by the instrument.

If instrument blank values are not automatically taken and subtracted by the instrument, report
these calculations based on net values, and report all instrument blank values, too.

These are zero standards.

July 28, 1997 M425 Page 27

 See below for determination of net values.

19.1.2 Cr6 M-C Analytical Calculations

Report these calculations based on net values using Equation 425-11. Report all instrument
blank values, too.

Net Value = Sample Train Component Value - Zero Blank Value 425-11

19.2 Total Cr in the Sample Train (mCr)

Calculate and report mCr, the total µg of chromium in the sample train. This can be obtained from
the calibration curve or from the method of standard additions. Note that mCr is the sum of the
masses of total chromium analyses performed on all sample portions. Also take into account the
necessary dilutions when calculating out mCr.

Calculations shall include only sample portions which have values above the LOD.

Do not subtract the LOD from the sample train values.

Report these calculations based on net values, and report all instrument blank values, too.

See above for determination of net values.

19.3 Method 5 Testing Parameters

Except where otherwise noted in this method, follow the procedures of ARB Method 5 to determine:

(1) Standard Volume of Gas Sample / (Vsample)

Typical units for Vsample are dry standard cubic meters, dscm.

(2) Isokinetic Variation

(3) Standard Volumetric Flow Rate of Stack Gas / (Qstack)

Typical units for Qstack are dry standard cubic meters per hour, dscm/hour.

July 28, 1997 M425 Page 28

19.4 Cr6 Mass Emission Concentration / Cr6 MEC

Calculate and report the Cr6 mass emission concentration in the stack gas, dry basis, corrected to
standard conditions, using Equation 425-12:

Cr6 MEC ' mCr6 ÷ Vsample 425-11

Where:

Cr6 MEC = Cr6 concentration in the stack gas, ng/dscm

mCr6 = Cr6 mass in the sampling train, ng

Vsample = stack gas volume sampled, dscm

19.5 Cr6 Mass Emission Rate / Cr6 MER

Calculate and report the Cr6 mass emission rate in the stack gas, dry basis, corrected to standard
conditions, using Equation 425-13:

Cr6 MER ' Cr6 MEC × Qstack 425-12

Where:

Cr6 MER = Cr6 concentration in the stack gas, ng/dscm

mCr6 = Cr6 mass in the sampling train, ng

Vsample = stack gas volume sampled, dscm

19.6 Cr Mass Emission Concentration / Cr MEC

Calculate and report the Cr mass emission concentration in the stack gas, dry basis, corrected to
standard conditions, using Equation 425-14:

Cr MEC ' mCr ÷ Vsample 425-13

Where:

Cr MEC = Cr concentration in the stack gas, ng/dscm

July 28, 1997 M425 Page 29

 mCr = Cr mass in the sampling train, ng

Vsample = stack gas volume sampled, dscm

19.7 Cr Mass Emission Rate = Cr MER

Calculate and report the Cr mass emission rate in the stack gas, dry basis, corrected to standard
conditions, using Equation 425-15:

Cr MER ' Cr MEC × Qstack 425-14

Where:

Cr MER = Cr concentration in the stack gas, ng/dscm

mCr = Cr mass in the sampling train, ng

Vsample = stack gas volume sampled, dscm

20 REPORTING RESULTS

20.1 Calculated Results

At a minimum, the tester shall report all calculated results required above. Also, as required by the
end user of the test results, the tester shall include specified data records, as described above.

Clearly distinguish sample runs for which Cr6 or Cr were DETECTED above the LOD from sample
runs for which Cr6 or Cr were NOT DETECTED above the LOD.

20.2 Narrative Account

At a minimum, the tester shall report a narrative account characterizing source and testing operations
during the source testing and analysis. In the narrative, include the means by which the values of the
source and testing parameters, chosen for the pre-test protocol, were maintained; also include a
narrative of unplanned or unexpected events which caused a departure from the chosen values.

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20.3 Final Calculation of Source Reporting Limit (SRL)

Equation 425-14 shall be used to calculate the SRL. This equation is adapted from the pre-test
protocol; actual values shall be substituted for the pre-test values.

ARL
SRL ' 425-15
ASV

Where:

SRL = source concentration reporting limit, ng/dscm

ARL = actual reporting limit, ng

ASV = actual sample volume, dscm

21 ALTERNATIVE TEST METHODS

21.1 Direct Measurement of Gas Volumes through Pipes and Small Ducts

Air Resources Board Method 2A may be used, where applicable, as an alternative to pitot tube
methods specified in Method 5, as referenced herein.

21.2 Other Impinger Solutions (Instead of NaOH)

0.1 N KOH may be substituted for 0.1 N NaOH in the impinger solution. Other substitutions, e.g.
NaHCO3, may be made provided that at all times during sampling and transport of samples, the pH
of the impinger solutions shall be maintained above a pH of 8.0 as determined by the use of a clean
rod and color indicating paper for pH.

21.3 Total Chromium Determination by Flame Atomic Absorption Spectroscopy

For high total chromium concentrations which are within the detection range of flame atomic
absorption spectroscopy, this analytical method may be used instead of the furnace type method
specified in these pages. This option applies only to the analysis of total chromium. The remainder of
the test method shall be performed as specified.

21.4 Other Methods

Alternative test methods may be used provided that they are equivalent to Method 425 and approved
in writing by the Executive Officer of the California Air Resources Board. The ARB Executive
Officer may require the submittal of test data or other information to demonstrate equivalency.

July 28, 1997 M425 Page 31

22 REFERENCES

(1) EPA Method 5, Determination of Particulate Emissions from Stationary Sources, CFR 40, Part 60,
Appendix A.

(2) (Draft) Laboratory and Field Evaluations of Methodology for Determining Hexavalent Chromium
Emissions from Stationary Sources; Prepared by: Anna C. Carver, Entropy Environmentalists, Inc.,
Research Triangle Park, NC 27709; EPA Contract No. 68-02-4550; Prepared for: Dr. Joseph E.
Knoll, United States Environmental Protection Agency, Quality Assurance Division, Research
Triangle Park, North Carolina 27711, UNDATED.

23 FIGURES

The following figures summarize features of this method:

Figure 1.
Sample Collection and Recovery for Hexavalent and Total Chromium

Figure 2.
Hexavalent Chromium Analysis

Figure 3
Total Chromium Analysis

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 Figure 1

SAMPLE COLLECTION AND RECOVERY

FOR HEXAVALENT AND TOTAL CHROMIUM

0.1 N NaOH rinse at lab 0.1 N NaOH impingers

glass lined metal probe

#1 #2 * filter

sample

container 1 container 2 * to lab

>100mL ~200mL

Extract filter in 0.1 N ** * Note: **

NaOH impinger solution. The filter should be combined
with the impinger liquid at the
sample site if a clean room is
available. The volumes of
split split liquid in each of the
containers and in each of the
splits must be measured and
recorded.

probe impinger probe impinger

rinse liquid & rinse liquid &
filter filter

Hexavalent Total
Chromium Chromium
Analysis Analysis

*
Note:
Contingently, the protocol
for hexavalent chromium
can require extraction of the
filter in the first impinger and See Figures 2 & 3.
analysis of three samples:
(1) probe rinse,
(2) first impinger liquid & filter,
and (3) second impinger liquid.
M425 F1 05/95 Loop

July 28, 1997 M425 Page 33

 Figure 2

HEXAVALENT CHROMIUM ANALYSIS

Note:
Contingently, the protocol
for hexavalent chromium
can require extraction of the
filter in the first impinger and See Figure 1.
analysis of three samples:
(1) probe rinse,
(2) first impinger liquid & filter,
and (3) second impinger liquid.

Example shown is for

two separate analyses.

probe impinger
rinse liquid &
filter

Transfer ~ 35 mL to a 100 mL beaker.

Adjust pH to 1.0±0.2 with 6 N sulfuric acid and

add 1.0 mL diphenylcarbizide solution.

Transfer to a 50 mL volumetric flask and dilute to volume with water;

let color develop for 10 minutes.

Pre-wet medium retention filter paper with a few mL each of :

(1) reagent blank first and then
(2) sample.

Filter to remove suspended solids.

Measure absorbance of a sample aliquot and a reagent blank aliquot at

540 nanometers.

If reading is off of the calibration line,

dilute with reagent blank or
remeasure using less of remaining sample.
M425 F2 05/95 Loop

July 28, 1997 M425 Page 34

 Figure 3.
TOTAL CHROMIUM ANALYSIS
Note:
Contingently, the protocol
for hexavalent chromium
can require extraction of the
filter in the first impinger and See Figure 1.
analysis of three samples:
(1) probe rinse,
(2) first impinger liquid & filter,
and (3) second impinger liquid.

Example shown is for

two separate analyses.

probe impinger
rinse liquid &
filter

Add 10 mL nitric acid - - - reflux to near dryness.

Add 5 mL nitric acid - - - reflux to near dryness.

Transfer to a volumetric flask and

adjust to a pre-determined volume.

Inject a measured aliquot in

mL amounts into a furnace type
atomic absorption spectrophotometer.

Measure absorbance of a sample aliquot and a reagent blank aliquot at

357.9 nanometers.
M425 F3 05/95 Loop

July 28, 1997 M425 Page 35