Current through Register Vol. 54, No. 44, November 2, 2024
(a) In addition to the requirements of §
252.401 (relating to basic
requirements), laboratories performing testing or analysis of environmental
samples in the area of chemistry shall comply with this section.
(b) When the method selected by an
environmental laboratory in accordance with §
252.307 (relating to methodology)
contains more stringent requirements than the requirements of this section, the
environmental laboratory shall follow the more stringent requirements contained
in the method.
(c) Initial
calibration requirements are as follows:
(1)
An environmental laboratory shall follow the initial calibration requirements
of the method.
(2) The results of
testing or analysis of environmental samples shall be determined from an
initial calibration and may not be determined from any continuing calibration
verification, unless otherwise required by regulation, method or
program.
(3) The details of the
initial calibration procedures including calculations, integrations, acceptance
criteria and associated statistics shall be included or referenced in the
laboratory's standard operating procedure.
(4) Raw data records shall be retained to
permit reconstruction of the initial calibration, including identification or
reference to the reagents, standards and supplies used, dates of analysis,
instrument identification, results of the initial calibration, calibration
criteria and analyst identification.
(5) Initial calibrations shall be verified
with a standard obtained from a second manufacturer or with a standard from the
same manufacturer if the verification standard is documented by the
manufacturer as prepared independently of the standard used during initial
calibration.
(6) The lowest
standard used for initial calibration may not be below the detection limit. The
lowest standard must be at or below the lower limit of the range of
quantitation.
(d) Except
for methods that explicitly allow initial calibration using a single
concentration of standard, initial calibration shall be done using multiple
concentrations of standards according to the requirements of this subsection.
(1) Unless otherwise specified in the method,
the initial calibration must meet one of the following criteria:
(i) A relative standard deviation of less
than 20% for the calculated response factors.
(ii) A coefficient of determination
(r2) of 0.99 for a linear calibration
curve.
(iii) A coefficient of
determination (r2) of 0.999 for a nonlinear
calibration curve determined with the use of at least 6 calibration standards
or as otherwise specified by the Department.
(2) If the initial calibration fails to meet
established acceptance criteria, corrective action shall be performed and all
associated environmental samples shall be reanalyzed after an acceptable
initial calibration is obtained. If reanalysis of the environmental samples is
not possible, a new environmental sample shall be collected.
(3) If the results of testing or analysis of
environmental samples that are below the initial calibration range are
reported, the results shall be reported with appropriate data
qualifiers.
(4) If the results of
testing or analysis of environmental samples are above the initial calibration
range, the environmental sample shall be diluted and reanalyzed or the results
reported with appropriate data qualifiers. Sample results within the
established calibration range will not require data qualifiers.
(5) The lowest calibration standard may not
be below the detection limit and may not be above the MCL.
(6) If the method does not specify the number
of calibration standards, the minimum number of calibration standards for a
response factor or linear calibration, not including blanks or a zero standard,
shall be determined as follows:
(i) For an
initial calibration covering a range up to 20 times the lowest quantitation
level, a minimum of three calibration standards shall be used.
(ii) For an initial calibration covering a
range from greater than 20 times and up to 50 times the lowest quantitation
level, a minimum of four calibration standards shall be used.
(iii) For an initial calibration covering a
range greater than 50 times and up to 100 times the lowest quantitation level,
a minimum of five calibration standards shall be used.
(e) For a method that explicitly
allows calibration using a single concentration of a standard, not including a
blank or zero concentration standard, the initial calibration shall meet the
requirements of this subsection.
(1) Prior to
the testing or analysis of environmental samples, the linear range of the
instrument shall be established by analyzing a series of standards, one of
which shall be at the lowest quantitation level.
(2) An initial calibration using a single
calibration standard and a zero point shall be performed at the beginning of
each analysis day.
(3) A standard
corresponding to the lowest quantitation level must be analyzed with each
analytical batch and must meet the acceptance criteria established by the
method. When there are no established criteria in the method, an environmental
laboratory shall determine internal criteria and document the procedure used to
establish the acceptance limits.
(4) If the results of testing or analysis of
environmental samples that are below the lowest quantitation level verification
standard, specified in paragraph (3), are to be reported, the results shall be
reported with appropriate data qualifiers.
(5) If the results of testing or analysis of
environmental samples produce a result above the associated single point
standard, the environmental laboratory shall do one of the following:
(i) Analyze a standard at or above the sample
concentration that meets established acceptance criteria to validate
linearity.
(ii) Dilute the sample
so that the result falls below the single point calibration
concentration.
(iii) Report the
data with an appropriate data qualifier.
(f) Calibration verification requirements are
as follows:
(1) A calibration verification
standard shall be analyzed at the beginning and end of each analysis day. For
methods that use an internal standard, a calibration verification standard is
not required at the end of the analysis day unless specified in the method, or
State or Federal law or regulation.
(2) A calibration verification standard shall
be analyzed after every ten samples, unless a different frequency is specified
in the method.
(3) At a minimum,
the laboratory shall verify the calibration curve of each analytical batch with
calibration verification standards at a low and a high level.
(i) The concentration of the low calibration
verification standard shall be within the lower 20% of the calibration curve
and not more than five times the lowest quantitation level.
(ii) The concentration of the high
calibration verification standard shall be within the upper 20% of the
calibration curve.
(4)
Details of the calibration verification procedure including calculations,
integrations, acceptance criteria and associated statistics shall be included
or referenced in the laboratory's standard operating procedure.
(5) Raw data records shall be retained to
permit reconstruction of the calibration verification.
(6) Acceptance criteria for calibration
verification standards in the method shall be followed. When there are no
established criteria in the method, an environmental laboratory shall use the
acceptance criteria described in an equivalent method for the same type of
analysis. When an equivalent method is not available, the laboratory shall
establish control charts in accordance with Standard Methods for the
Examination of Water and Wastewater (available from the American
Public Health Association, 800 I Street, NW, Washington, D.C. 20001) to
determine internal criteria and document the procedure used to establish the
acceptance limits.
(7) If a
calibration verification standard fails the established acceptance criteria, an
environmental laboratory shall initiate corrective actions. If the corrective
actions fail to produce an immediate consecutive calibration verification
standard within the acceptance criteria, a new calibration verification
standard shall be prepared. If the freshly prepared calibration verification
standard fails to produce a result within the established acceptance criteria,
the environmental laboratory shall recalibrate the test or analysis according
to the method or as set forth in subsection (c) and as set forth in either
subsection (d) or (e).
(8) To the
extent possible, and as provided by paragraph (1), environmental samples not
bracketed by acceptable calibration verification standards shall be reanalyzed.
If the calibration verification standard is found to be out of control, and the
results of the testing or analysis of environmental samples are to be reported,
all environmental samples associated with the failed calibration verification
standard shall be documented and the results flagged in an unambiguous manner
on the sample analysis report with the appropriate data qualifiers.
(g) Method blank requirements are
as follows:
(1) A method blank must be
processed along with and under the same conditions as the associated
environmental samples including all steps of the analytical
procedure.
(2) A method blank must
be analyzed at a minimum of one per preparation batch. When no separate
preparation method is used (example: volatiles in water), the batch shall be
defined as no more than 20 environmental samples that are analyzed together
using the same method, personnel and lots of reagents.
(3) A method blank must consist of a matrix
that is similar to the associated environmental samples and is free of the
analytes of interest. When a matrix that is similar to the associated
environmental samples that is free of the analytes of interest is not
available, reagent water or an artificial or simulated matrix may be
used.
(4) A method blank is
considered contaminated if one of the following applies:
(i) The concentration of a target analyte in
the method blank is at or above the reporting limit established by the method,
by the laboratory or by regulation.
(ii) The contamination in the method blank
otherwise affects the environmental sample results as described in the method
or in individual project data quality objectives.
(5) If a contaminant is detected in the
method blank, the source of contamination shall be investigated and measures
shall be taken to minimize or eliminate the problem.
(6) Raw data records shall be retained to
permit reconstruction of the method blank.
(7) To the extent possible, any environmental
samples associated with a contaminated method blank shall be reprocessed for
analysis. If a contaminated method blank is found to be out of control, and the
results of the testing or analysis of environmental samples are to be reported,
all environmental samples associated with the contaminated method blank shall
be documented and the results flagged in an unambiguous manner on the sample
analysis report with the appropriate data qualifiers.
(h) Laboratory control sample requirements
are as follows:
(1) A laboratory control
sample must be processed along with and under the same conditions as the
associated environmental samples, including all steps of the preparation and
analytical procedure.
(2) A
laboratory control sample must consist of a matrix that is similar to the
associated environmental samples and is free of the analytes of interest. When
a matrix that is similar to the associated environmental samples that is free
of the analytes of interest is not available, reagent water or an artificial or
simulated matrix may be used.
(3)
An environmental laboratory shall analyze a laboratory control sample at a
minimum of one per preparation batch. When no separate preparation method is
used, for example volatiles in water, the batch shall be defined as no more
than 20 environmental samples that are analyzed together with the same method,
personnel and lots of reagents.
(4)
All analyte concentrations in the laboratory control sample must be within the
calibration range of the method and at or below the maximum contaminant
level.
(5) The components to be
spiked into the laboratory control sample must be as specified by the method or
other regulatory requirement. In the absence of specified components, the
environmental laboratory shall use the following:
(i) For those components that interfere with
an accurate assessment, such as spiking simultaneously with technical
chlordane, toxaphene and PCBs, the laboratory control sample must represent the
chemistries and elution patterns of the components to be reported.
(ii) For methods with more than ten analytes,
a representative number may be chosen. The analytes selected shall be
representative of all chemistries and analytes reported and shall be chosen
using the following criteria:
(A) Targeted
components shall be included in the laboratory control sample over a 2-year
period.
(B) For methods that
include one to ten components, the laboratory control sample must contain all
components.
(C) For methods that
include 11-20 components, the laboratory control sample must contain at least
10 components or 80%, whichever is greater.
(D) For methods with more than 20 components,
the laboratory control samples must contain at least 16 components.
(6) Each individual
laboratory control sample shall be compared to the acceptance criteria in the
method. When there are no established criteria in the method, an environmental
laboratory shall use the acceptance criteria described in an equivalent method
for the same type of analysis. When an equivalent method is not available, the
laboratory shall establish control charts in accordance with Standard
Methods for the Examination of Water and Wastewater (available from
the American Public Health Association, 800 I Street, NW, Washington, D.C.
20001) to determine internal criteria and document the procedure used to
establish the limits.
(7) Raw data
records shall be retained to permit reconstruction of the laboratory control
sample.
(8) Environmental samples
associated with an out of control laboratory control sample shall be
reprocessed and reanalyzed from the beginning of the method or the results
reported with the appropriate data qualifiers.
(i) Sample duplicate requirements are as
follows:
(1) A sample duplicate or matrix
spike duplicate must be processed along with and under the same conditions as
the associated environmental samples, including all steps of the preparation
and analytical procedure.
(2) A
sample duplicate or matrix spike duplicate shall be analyzed at a minimum of
one per preparation batch. When no separate preparation method is used, for
example volatiles in water, the batch shall be defined as no more than 20
environmental samples that are analyzed together using the same method,
personnel and lots of reagents.
(3)
An environmental laboratory shall document the calculations used for
determining the relative percent difference or other statistical method for
evaluation of the duplicate pairs.
(4) Each duplicate relative percent
difference shall be compared to the acceptance criteria in the method. When
there are no established criteria in the method, an environmental laboratory
shall use the acceptance criteria described in an equivalent method for the
same type of analysis. When an equivalent method is not available, the
laboratory shall establish control charts in accordance with Standard
Methods for the Examination of Water and Wastewater (available from
the American Public Health Association, 800 I Street, NW, Washington, D.C.
20001) to determine internal criteria and document the procedure used to
establish the acceptance limits.
(5) For duplicate results outside established
criteria, corrective action shall be documented and the data reported with
appropriate data qualifiers.
(j) Surrogate spike requirements are as
follows:
(1) Surrogate compounds, when
commercially available, shall be added to all samples, standards and blanks for
all organic chromatography test methods.
(2) Surrogate compounds shall be chosen to
represent the various chemistries of the target analytes in the
method.
(3) The results of the
surrogate spike shall be compared to the acceptance criteria published in the
method. When there are no established acceptance criteria for surrogate
recovery in the method, the environmental laboratory shall use the acceptance
criteria described in an equivalent method for the same type of analysis. When
an equivalent method is not available, the laboratory shall establish control
charts in accordance with Standard Methods for the Examination of Water
and Wastewater (available from the American Public Health Association,
800 I Street, NW, Washington, D.C. 20001) to establish internal criteria and
document the method used to establish the acceptance limits.
(4) For surrogate spike results outside
established criteria, corrective action shall be documented and the data
reported with appropriate data qualifiers.
(k) Detection limit requirements are as
follows:
(1) A detection limit shall be
determined by the protocol in the method or regulation. If the protocol for
determining detection limits is not specified in the method or regulation, the
environmental laboratory shall select a procedure that reflects instrument
limitations and the intended application of the method.
(2) A detection limit study is not required
for any component for which spiking solutions or quality control samples are
not available, such as temperature. A detection limit study is not required for
testing or analysis where the results are logarithmic, such as pH, or when the
results are expressed as presence or absence.
(3) A detection limit shall be initially
determined for the compounds of interest in each method in a matrix in which
neither the target analyte nor interferences are at a concentration that would
impact the results. The detection limit shall be determined in the matrix of
interest.
(4) A detection limit
shall be determined each time there is a change in the method that affects how
the test is performed or that affects the sensitivity of the
analysis.
(5) The sample processing
steps of the method shall be included in the determination of the detection
limit.
(6) Supporting data shall be
retained to permit reconstruction of the detection limit study.
(7) An environmental laboratory shall have an
established procedure to relate detection limits with quantitation
limits.
(8) The method's lower
limit of quantitation shall be established and shall be above the detection
limit.
(l) When retention
times are used for the identification of an analyte, an environmental
laboratory shall develop and document acceptance criteria for retention time
windows. The laboratory shall document acceptance criteria for mass spectral
tuning.
(m) When manual
integrations are performed for chromatography methods, the laboratory shall
have written procedures for manual integrations and instrument manipulations.
(1) The manual integration procedures must
detail the steps taken to perform the integrations and define proper and
improper integrations.
(2) The
laboratory shall document manual integrations with the reason for the
integration and the initials of the individual performing the
integration.
(3) The laboratory
shall retain a copy of the data before and after manual integration.
(n) The laboratory shall employ
confirmation techniques to verify the compound identification when positive
results are detected on a sample from a location that has not been previously
tested by the laboratory or for a sample location that has not previously
yielded detectable results for a particular compound.
(1) The confirmations shall be performed when
analysis involves the use of an organic chromatography method not utilizing a
mass spectrometer.
(2) The
confirmations shall be documented.
(o) Records of all equipment, reference
materials, reagents, and supplies shall be maintained in accordance with §
252.306 (relating to equipment,
supplies and reference materials).
The provisions of this §252.402 amended under
27 Pa.C.S. §§
4103(a),
4104 and
4105; and section 1920-A
of The Administrative Code of 1929 (71 P.S. §
510-20).