ASTM D5788-95(2017)
(Guide)Standard Guide for Spiking Organics into Aqueous Samples
Standard Guide for Spiking Organics into Aqueous Samples
SIGNIFICANCE AND USE
5.1 Matrix spiking of samples is commonly used to determine the bias under specific analytical conditions, or the applicability of a test method to a particular sample matrix, by determining the extent to which the added spike is recovered from the sample matrix under these conditions. Reactions or interactions of the analyte or component of interest with the sample matrix may cause a significant positive or negative effect on recovery and may render the chosen analytical, or monitoring, process ineffectual for that sample matrix.
5.2 Matrix spiking of samples can also be used to monitor the performance of a laboratory, individual instrument, or analyst as part of a regular quality assurance program. Changes in spike recoveries from the same or similar matrices over time may indicate variations in the quality of analyses and analytical results.
5.3 Spiking of samples may be performed in the field or in the laboratory, depending on what part of the analytical process is to be tested. Field spiking tests the recovery of the overall process, including preservation and shipping of the sample and may be considered a measure of the stability of the analytes in the matrix. Laboratory spiking tests the laboratory process only. Spiking of sample extracts, concentrates, or dilutions will be reflective of only that portion of the process subsequent to the addition of the spike.
5.4 Special precautions shall be observed when nonlaboratory personnel perform spiking in the field. It is recommended that all spike preparation work be performed in a laboratory by experienced analysts so that the field operation consists solely of adding a prepared spiking solution to the sample matrix. Training of field personnel and validation of their spiking techniques are necessary to ensure that spikes are added accurately and reproducibly. Consistent and acceptable recoveries from duplicate field spikes can be used to document the reproducibility of sampling and the spiking technique....
SCOPE
1.1 This guide covers the general technique of “spiking” aqueous samples with organic analytes or components. It is intended to be applicable to a broad range of organic materials in aqueous media. Although the specific details and handling procedures required for all types of compounds are not described, this general approach is given to serve as a guideline to the analyst in accurately preparing spiked samples for subsequent analysis or comparison. Guidance is also provided to aid the analyst in calculating recoveries and interpreting results. It is the responsibility of the analyst to determine whether the methods and materials cited here are compatible with the analytes of interest.
1.2 The procedures in this guide are focused on “matrix spike” preparation, analysis, results, and interpretation. The applicability of these procedures to the preparation of calibration standards, calibration check standards, laboratory control standards, reference materials, and other quality control materials by spiking is incidental. A sample (the matrix) is fortified (spiked) with the analyte of interest for a variety of analytical and quality control purposes. While the spiking of multiple sample test portions is discussed, the method of standard additions is not covered.
1.3 This guide is intended for use in conjunction with the individual analytical test method that provides procedures for analysis of the analyte or component of interest. The test method is used to determine an analyte or component's background level and, again after spiking, its now elevated level. Each test method typically provides procedures not only for samples, but also for calibration standards or analytical control solutions, or both. These procedures include preparation, handling, storage, preservation, and analysis techniques. These procedures are applicable by extension, using the analyst's judgement on a case-by-case basis, to spiking solutions, ...
General Information
Relations
Buy Standard
Standards Content (Sample)
This international standard was developed in accordance with internationally recognized principles on standardization established in the Decision on Principles for the
Development of International Standards, Guides and Recommendations issued by the World Trade Organization Technical Barriers to Trade (TBT) Committee.
Designation: D5788 − 95 (Reapproved 2017)
Standard Guide for
Spiking Organics into Aqueous Samples
This standard is issued under the fixed designation D5788; the number immediately following the designation indicates the year of
original adoption or, in the case of revision, the year of last revision.Anumber in parentheses indicates the year of last reapproval.A
superscript epsilon (´) indicates an editorial change since the last revision or reapproval.
1. Scope 1.4 Theseproceduresapplyonlytoanalytesthataresoluble
in water at the concentration of the spike plus any background
1.1 This guide covers the general technique of “spiking”
material, or to analytes soluble in a solvent that is itself
aqueous samples with organic analytes or components. It is
water-soluble. The system used in the later case must result in
intended to be applicable to a broad range of organic materials
a homogeneous solution of analyte and sample. Meaningful
in aqueous media. Although the specific details and handling
recovery data cannot be obtained if an aqueous solution or
procedures required for all types of compounds are not
homogeneous suspension of the analyte of interest in the
described,thisgeneralapproachisgiventoserveasaguideline
sample cannot be attained.
to the analyst in accurately preparing spiked samples for
subsequent analysis or comparison. Guidance is also provided 1.5 Matrix spiking may be performed in the field or in the
to aid the analyst in calculating recoveries and interpreting laboratory,dependingonwhichpartoftheanalyticalprocessis
results. It is the responsibility of the analyst to determine to be tested. Field spiking tests the recovery of the overall
whether the methods and materials cited here are compatible process, including preservation and shipping of the sample.
with the analytes of interest. Laboratoryspikingteststhelaboratoryprocessonly.Spikingof
sample extracts, concentrates, or dilutions will test only that
1.2 The procedures in this guide are focused on “matrix
portion of the process subsequent to the addition of the spike.
spike” preparation, analysis, results, and interpretation. The
applicability of these procedures to the preparation of calibra- 1.6 The values stated in SI units are to be regarded as
tion standards, calibration check standards, laboratory control standard. No other units of measurement are included in this
standards, reference materials, and other quality control mate- standard.
rials by spiking is incidental.Asample (the matrix) is fortified
1.7 This standard does not purport to address all of the
(spiked) with the analyte of interest for a variety of analytical
safety concerns, if any, associated with its use. It is the
and quality control purposes. While the spiking of multiple
responsibility of the user of this standard to establish appro-
sample test portions is discussed, the method of standard
priate safety, health, and environmental practices and deter-
additions is not covered.
mine the applicability of regulatory limitations prior to use.
1.8 This international standard was developed in accor-
1.3 This guide is intended for use in conjunction with the
dance with internationally recognized principles on standard-
individual analytical test method that provides procedures for
ization established in the Decision on Principles for the
analysis of the analyte or component of interest. The test
Development of International Standards, Guides and Recom-
method is used to determine an analyte or component’s
mendations issued by the World Trade Organization Technical
background level and, again after spiking, its now elevated
Barriers to Trade (TBT) Committee.
level. Each test method typically provides procedures not only
for samples, but also for calibration standards or analytical
2. Referenced Documents
control solutions, or both. These procedures include
preparation, handling, storage, preservation, and analysis tech-
2.1 ASTM Standards:
niques.Theseproceduresareapplicablebyextension,usingthe
D1129Terminology Relating to Water
analyst’s judgement on a case-by-case basis, to spiking
D1193Specification for Reagent Water
solutions, and are not reiterated in this guide. See also Practice
D3694Practices for Preparation of Sample Containers and
E200 for preparation and storage information.
for Preservation of Organic Constituents
D3856Guide for Management Systems in Laboratories
Engaged in Analysis of Water
This guide is under the jurisdiction ofASTM Committee D19 on Water and is
the direct responsibility of Subcommittee D19.06 on Methods for Analysis for
Organic Substances in Water. For referenced ASTM standards, visit the ASTM website, www.astm.org, or
Current edition approved Dec. 15, 2017. Published January 2018. Originally contact ASTM Customer Service at service@astm.org. For Annual Book of ASTM
approved in 1995. Last previous edition approved in 2011 as D5788–95 (2011). Standards volume information, refer to the standard’s Document Summary page on
DOI: 10.1520/D5788-95R17. the ASTM website.
Copyright © ASTM International, 100 Barr Harbor Drive, PO Box C700, West Conshohocken, PA 19428-2959. United States
D5788 − 95 (2017)
D4375Practice for Basic Statistics in Committee D19 on 5.3 Spiking of samples may be performed in the field or in
Water thelaboratory,dependingonwhatpartoftheanalyticalprocess
E200Practice for Preparation, Standardization, and Storage is to be tested. Field spiking tests the recovery of the overall
of Standard and Reagent Solutions for ChemicalAnalysis process,includingpreservationandshippingofthesampleand
may be considered a measure of the stability of the analytes in
3. Terminology
the matrix. Laboratory spiking tests the laboratory process
only.Spikingofsampleextracts,concentrates,ordilutionswill
3.1 Definitions:
be reflective of only that portion of the process subsequent to
3.1.1 For definitions of terms used in this standard, refer to
the addition of the spike.
Terminology D1129.
5.4 Special precautions shall be observed when nonlabora-
3.2 Definitions of Terms Specific to This Standard:
tory personnel perform spiking in the field. It is recommended
3.2.1 matrix spike, n—the quantity (mass) of a component
thatallspikepreparationworkbeperformedinalaboratoryby
(analyte) of interest which is added to a sample (matrix) in
experienced analysts so that the field operation consists solely
order to test bias as measured by recovery (of that component
of adding a prepared spiking solution to the sample matrix.
under specific analytical conditions) and reported as percent
Training of field personnel and validation of their spiking
recovery (P).
techniques are necessary to ensure that spikes are added
3.2.2 spike, v—the addition of a known amount of an
accurately and reproducibly. Consistent and acceptable recov-
analyte of known identity to a measured volume of a sample
eries from duplicate field spikes can be used to document the
(from a specific matrix) to determine the efficiency with which
reproducibility of sampling and the spiking technique. When
the added analyte can be “recovered” from (measured in) that
environmentally labile compounds are used as spikes, the
matrix by the analytical system after exposure to a specific
spiking solution shall be protected up to the time of use by
portionofananalyticalprocess.Matrixspikingisaprocessfor
appropriate means such as chilling, protection from sunlight
accomplishing this. The precision and bias estimates from
and oxygen, or chemical preservation.
several trials under specific analytical conditions represent the
NOTE1—Anyfieldspikedsample,ifknowntothelaboratory,shouldbe
measurement efficiency with which the analyte may be deter-
labeledasafieldspikeinthefinalresultsreport.Also,wheneverpossible,
mined under these conditions.
field spiking of volatile compounds should be avoided.
3.2.3 spiking solution—the solution in which one or more
5.5 It is often tacitly assumed that the analyte component is
spikes are dissolved (along with any necessary preservatives).
recovered from the sample to approximately the same extent
This solution acts as a carrier to provide ease of measurement
that a spike of the same analyte is recovered from a spiked
and more rapid and thorough mixing of the spike into the
sample. One reason that this assumption may be incorrect is
sample, as compared to adding the spike as a pure compound.
thatthespikemaynotbeboundupinthesample(forexample,
with suspended matter) in the same way that the naturally
4. Summary of Guide
occurring analyte is bound in the sample. The spike may
4.1 This guide describes a technique for the addition of a
therefore be recovered from the sample differently than the
known amount of an organic analyte to an aqueous sample.
background level of the analyte. For this reason, as well as the
Instructions are given to help prevent loss of volatile analytes
fact that bias corrections can add variability, it is not good
in the sample headspace and to provide a homogeneous
practicetocorrectanalyticaldatausingspikerecoveries.Spike
solutionforsubsequentanalysis.Appropriateconcentrationsof
recovery information should, however, be reported along with
thespikerelativetotheoriginalconcentrationinthesampleare
the related sample analysis results.
discussed. Applications of the technique and aids in the
5.6 This guide is also applicable to the preparation and use
interpretation of results obtained are described.
ofspikesforquantificationbythemethodofstandardadditions
and to the addition of surrogates and internal standards.
5. Significance and Use
5.1 Matrix spiking of samples is commonly used to deter-
6. Apparatus
mine the bias under specific analytical conditions, or the
applicability of a test method to a particular sample matrix, by 6.1 StirringApparatus—Borosilicateglassbeads,4to6mm
determining the extent to which the added spike is recovered in diameter, or small TFE-coated magnetic stirring bars. A
from the sample matrix under these conditions. Reactions or small non-heating variable-speed magnetic stirrer is recom-
interactions of the analyte or component of interest with the mended for use with the stirring bar.
sample matrix may cause a significant positive or negative
6.2 Microsyringes—Standard gas chromatographic mi-
effect on recovery and may render the chosen analytical, or
crosyringes of borosilicate glass with stainless steel needles,
monitoring, process ineffectual for that sample matrix.
suitableforinjectionofspikingsolutionsthroughaTFE-coated
5.2 Matrix spiking of samples can also be used to monitor silicone septum. The TFE-tipped plungers may be contami-
the performance of a laboratory, individual instrument, or nated by certain analytes. If this is determined to be likely, a
analystaspartofaregularqualityassuranceprogram.Changes syringe may be dedicated to a single process, or a plain-tipped
inspikerecoveriesfromthesameorsimilarmatricesovertime stainless steel plunger may be used to avoid cross-
mayindicatevariationsinthequalityofanalysesandanalytical contamination. Sizes from 10 to 500 µL are appropriate,
results. depending on the concentration and sample volumes used.
D5788 − 95 (2017)
6.3 Micropipettors—Stainless steel micropipettors with dis- 7.3 Methanol—Spectrograde, HPLC grade, or ultrapure
posable glass tips are preferable to syringes for introduction of grade methanol is preferable for use as a solvent for water-
spiking solutions into open sample containers, since they insoluble analytes in most trace-level analyses. Other water-
deliver more reproducibly and are less prone to cross- soluble solvents may be useful for certain analytes. Solvents
contamination. Sizes from 5 to 200 µL are appropriate. shall be checked before use for interfering substances by
analysis.
6.4 Syringes—Borosilicate glass syringes with demountable
stainless steel needles may be used to measure volumes of 7.4 Spiking Solutions—Spiking solutions of each analyte of
samples(spikedorunspiked)tobeinjectedintopurge-and-trap interest are prepared individually or in combination, either
sample introduction systems. gravimetrically or volumetrically, correcting for density (for
liquid or solution standards). The preservation and storage
6.5 Volumetric Transfer Pipets—Class A, used to deliver
criteria found in the applicable analytical test method for its
knownvolumesofsampleandtoaddlargervolumesofspiking
calibration or check standards apply likewise to spiking solu-
solutions.
tions.Thestabilityofastoredspikingsolutionshallbeverified
6.6 Volumetric Flasks—Class A volumetric flasks may be
routinely by the appropriate dilution of a portion of spiking
used to measure known volumes of sample.
solution to the laboratory’s analyte concentration of interest.
Stability is demonstrated whenever the analyzed concentration
6.7 Balance—An analytical (0.1-mg), semimicro (0.01-
mg), or micro (0.001-mg) balance. of a diluted spiking solution falls within the control limits for
a routine laboratory control sample of the same concentration.
7. Reagents
Where solubilities permit, stock spiking solutions are custom-
arilyprepared25to1000timesasconcentratedastheworking
7.1 Purity of Reagents—At a minimum, reagent grade
spiking solution, and are diluted volumetrically to produce the
chemicalsshallbeusedinallspikepreparations.Spectrograde,
working spiking solution at the time of use. In some cases,
high-pressure liquid chromatography (HPLC) grade, pesticide
concentrated solutions may be stable at 4°C for substantially
grade, or ultrapure grade solvents shall be used to prepare
longer periods than dilute solutions. Alternatively, prepare
spikingsolutions.Reagentsofthehighestavailablepurityshall
spike or spiking solution fresh for each batch of samples.
be used for spike analytes and demonstrated to be free of
interfering substances for the subsequent test methods to be
8. Sampling
performed. If possible, a primary standard grade shall be used.
8.1 Although sampling methodology is beyond the scope of
Unless otherwise indicated, it is intended that all reagents
this guide, a properly split or duplicate sample is of utmost
conform to the specifications of the Committee on Analytical
3 importance to the successful measurement of spike recovery.
Reagents of the American Chemical Society. Other grades
This is especially critical in samples containing suspended
maybeused,provided(1)thatreagentpurityisunspecifiedand
sediment or volatile analytes.
(2) that it is first ascertained that the reagent is of sufficiently
8.2 Sample containers shall be selected and prepared, and
high purity to permit its use without adversel
...
NOTICE: This standard has either been superseded and replaced by a new version or withdrawn.
Contact ASTM International (www.astm.org) for the latest information
Designation: D5788 − 95 (Reapproved 2017)
Standard Guide for
Spiking Organics into Aqueous Samples
This standard is issued under the fixed designation D5788; the number immediately following the designation indicates the year of
original adoption or, in the case of revision, the year of last revision. A number in parentheses indicates the year of last reapproval. A
superscript epsilon (´) indicates an editorial change since the last revision or reapproval.
1. Scope 1.4 These procedures apply only to analytes that are soluble
in water at the concentration of the spike plus any background
1.1 This guide covers the general technique of “spiking”
material, or to analytes soluble in a solvent that is itself
aqueous samples with organic analytes or components. It is
water-soluble. The system used in the later case must result in
intended to be applicable to a broad range of organic materials
a homogeneous solution of analyte and sample. Meaningful
in aqueous media. Although the specific details and handling
recovery data cannot be obtained if an aqueous solution or
procedures required for all types of compounds are not
homogeneous suspension of the analyte of interest in the
described, this general approach is given to serve as a guideline
sample cannot be attained.
to the analyst in accurately preparing spiked samples for
subsequent analysis or comparison. Guidance is also provided 1.5 Matrix spiking may be performed in the field or in the
to aid the analyst in calculating recoveries and interpreting laboratory, depending on which part of the analytical process is
results. It is the responsibility of the analyst to determine to be tested. Field spiking tests the recovery of the overall
whether the methods and materials cited here are compatible process, including preservation and shipping of the sample.
with the analytes of interest. Laboratory spiking tests the laboratory process only. Spiking of
sample extracts, concentrates, or dilutions will test only that
1.2 The procedures in this guide are focused on “matrix
portion of the process subsequent to the addition of the spike.
spike” preparation, analysis, results, and interpretation. The
applicability of these procedures to the preparation of calibra- 1.6 The values stated in SI units are to be regarded as
tion standards, calibration check standards, laboratory control standard. No other units of measurement are included in this
standards, reference materials, and other quality control mate- standard.
rials by spiking is incidental. A sample (the matrix) is fortified
1.7 This standard does not purport to address all of the
(spiked) with the analyte of interest for a variety of analytical
safety concerns, if any, associated with its use. It is the
and quality control purposes. While the spiking of multiple
responsibility of the user of this standard to establish appro-
sample test portions is discussed, the method of standard
priate safety, health, and environmental practices and deter-
additions is not covered.
mine the applicability of regulatory limitations prior to use.
1.8 This international standard was developed in accor-
1.3 This guide is intended for use in conjunction with the
dance with internationally recognized principles on standard-
individual analytical test method that provides procedures for
ization established in the Decision on Principles for the
analysis of the analyte or component of interest. The test
Development of International Standards, Guides and Recom-
method is used to determine an analyte or component’s
mendations issued by the World Trade Organization Technical
background level and, again after spiking, its now elevated
Barriers to Trade (TBT) Committee.
level. Each test method typically provides procedures not only
for samples, but also for calibration standards or analytical
2. Referenced Documents
control solutions, or both. These procedures include
preparation, handling, storage, preservation, and analysis tech-
2.1 ASTM Standards:
niques. These procedures are applicable by extension, using the
D1129 Terminology Relating to Water
analyst’s judgement on a case-by-case basis, to spiking
D1193 Specification for Reagent Water
solutions, and are not reiterated in this guide. See also Practice
D3694 Practices for Preparation of Sample Containers and
E200 for preparation and storage information.
for Preservation of Organic Constituents
D3856 Guide for Management Systems in Laboratories
Engaged in Analysis of Water
This guide is under the jurisdiction of ASTM Committee D19 on Water and is
the direct responsibility of Subcommittee D19.06 on Methods for Analysis for
Organic Substances in Water. For referenced ASTM standards, visit the ASTM website, www.astm.org, or
Current edition approved Dec. 15, 2017. Published January 2018. Originally contact ASTM Customer Service at service@astm.org. For Annual Book of ASTM
approved in 1995. Last previous edition approved in 2011 as D5788 – 95 (2011). Standards volume information, refer to the standard’s Document Summary page on
DOI: 10.1520/D5788-95R17. the ASTM website.
Copyright © ASTM International, 100 Barr Harbor Drive, PO Box C700, West Conshohocken, PA 19428-2959. United States
D5788 − 95 (2017)
D4375 Practice for Basic Statistics in Committee D19 on 5.3 Spiking of samples may be performed in the field or in
Water the laboratory, depending on what part of the analytical process
E200 Practice for Preparation, Standardization, and Storage is to be tested. Field spiking tests the recovery of the overall
of Standard and Reagent Solutions for Chemical Analysis process, including preservation and shipping of the sample and
may be considered a measure of the stability of the analytes in
3. Terminology
the matrix. Laboratory spiking tests the laboratory process
only. Spiking of sample extracts, concentrates, or dilutions will
3.1 Definitions:
be reflective of only that portion of the process subsequent to
3.1.1 For definitions of terms used in this standard, refer to
the addition of the spike.
Terminology D1129.
5.4 Special precautions shall be observed when nonlabora-
3.2 Definitions of Terms Specific to This Standard:
tory personnel perform spiking in the field. It is recommended
3.2.1 matrix spike, n—the quantity (mass) of a component
that all spike preparation work be performed in a laboratory by
(analyte) of interest which is added to a sample (matrix) in
experienced analysts so that the field operation consists solely
order to test bias as measured by recovery (of that component
of adding a prepared spiking solution to the sample matrix.
under specific analytical conditions) and reported as percent
Training of field personnel and validation of their spiking
recovery (P).
techniques are necessary to ensure that spikes are added
3.2.2 spike, v—the addition of a known amount of an
accurately and reproducibly. Consistent and acceptable recov-
analyte of known identity to a measured volume of a sample
eries from duplicate field spikes can be used to document the
(from a specific matrix) to determine the efficiency with which
reproducibility of sampling and the spiking technique. When
the added analyte can be “recovered” from (measured in) that
environmentally labile compounds are used as spikes, the
matrix by the analytical system after exposure to a specific
spiking solution shall be protected up to the time of use by
portion of an analytical process. Matrix spiking is a process for
appropriate means such as chilling, protection from sunlight
accomplishing this. The precision and bias estimates from
and oxygen, or chemical preservation.
several trials under specific analytical conditions represent the
measurement efficiency with which the analyte may be deter- NOTE 1—Any field spiked sample, if known to the laboratory, should be
labeled as a field spike in the final results report. Also, whenever possible,
mined under these conditions.
field spiking of volatile compounds should be avoided.
3.2.3 spiking solution—the solution in which one or more
5.5 It is often tacitly assumed that the analyte component is
spikes are dissolved (along with any necessary preservatives).
recovered from the sample to approximately the same extent
This solution acts as a carrier to provide ease of measurement
that a spike of the same analyte is recovered from a spiked
and more rapid and thorough mixing of the spike into the
sample. One reason that this assumption may be incorrect is
sample, as compared to adding the spike as a pure compound.
that the spike may not be bound up in the sample (for example,
with suspended matter) in the same way that the naturally
4. Summary of Guide
occurring analyte is bound in the sample. The spike may
4.1 This guide describes a technique for the addition of a
therefore be recovered from the sample differently than the
known amount of an organic analyte to an aqueous sample.
background level of the analyte. For this reason, as well as the
Instructions are given to help prevent loss of volatile analytes
fact that bias corrections can add variability, it is not good
in the sample headspace and to provide a homogeneous
practice to correct analytical data using spike recoveries. Spike
solution for subsequent analysis. Appropriate concentrations of
recovery information should, however, be reported along with
the spike relative to the original concentration in the sample are
the related sample analysis results.
discussed. Applications of the technique and aids in the
5.6 This guide is also applicable to the preparation and use
interpretation of results obtained are described.
of spikes for quantification by the method of standard additions
5. Significance and Use and to the addition of surrogates and internal standards.
5.1 Matrix spiking of samples is commonly used to deter-
6. Apparatus
mine the bias under specific analytical conditions, or the
applicability of a test method to a particular sample matrix, by 6.1 Stirring Apparatus—Borosilicate glass beads, 4 to 6 mm
determining the extent to which the added spike is recovered in diameter, or small TFE-coated magnetic stirring bars. A
from the sample matrix under these conditions. Reactions or small non-heating variable-speed magnetic stirrer is recom-
interactions of the analyte or component of interest with the mended for use with the stirring bar.
sample matrix may cause a significant positive or negative
6.2 Microsyringes—Standard gas chromatographic mi-
effect on recovery and may render the chosen analytical, or
crosyringes of borosilicate glass with stainless steel needles,
monitoring, process ineffectual for that sample matrix.
suitable for injection of spiking solutions through a TFE-coated
5.2 Matrix spiking of samples can also be used to monitor silicone septum. The TFE-tipped plungers may be contami-
the performance of a laboratory, individual instrument, or nated by certain analytes. If this is determined to be likely, a
analyst as part of a regular quality assurance program. Changes syringe may be dedicated to a single process, or a plain-tipped
in spike recoveries from the same or similar matrices over time stainless steel plunger may be used to avoid cross-
may indicate variations in the quality of analyses and analytical contamination. Sizes from 10 to 500 µL are appropriate,
results. depending on the concentration and sample volumes used.
D5788 − 95 (2017)
6.3 Micropipettors—Stainless steel micropipettors with dis- 7.3 Methanol—Spectrograde, HPLC grade, or ultrapure
posable glass tips are preferable to syringes for introduction of grade methanol is preferable for use as a solvent for water-
spiking solutions into open sample containers, since they insoluble analytes in most trace-level analyses. Other water-
deliver more reproducibly and are less prone to cross- soluble solvents may be useful for certain analytes. Solvents
contamination. Sizes from 5 to 200 µL are appropriate. shall be checked before use for interfering substances by
analysis.
6.4 Syringes—Borosilicate glass syringes with demountable
stainless steel needles may be used to measure volumes of 7.4 Spiking Solutions—Spiking solutions of each analyte of
samples (spiked or unspiked) to be injected into purge-and-trap interest are prepared individually or in combination, either
sample introduction systems. gravimetrically or volumetrically, correcting for density (for
liquid or solution standards). The preservation and storage
6.5 Volumetric Transfer Pipets—Class A, used to deliver
criteria found in the applicable analytical test method for its
known volumes of sample and to add larger volumes of spiking
calibration or check standards apply likewise to spiking solu-
solutions.
tions. The stability of a stored spiking solution shall be verified
6.6 Volumetric Flasks—Class A volumetric flasks may be
routinely by the appropriate dilution of a portion of spiking
used to measure known volumes of sample.
solution to the laboratory’s analyte concentration of interest.
6.7 Balance—An analytical (0.1-mg), semimicro (0.01- Stability is demonstrated whenever the analyzed concentration
of a diluted spiking solution falls within the control limits for
mg), or micro (0.001-mg) balance.
a routine laboratory control sample of the same concentration.
7. Reagents Where solubilities permit, stock spiking solutions are custom-
arily prepared 25 to 1000 times as concentrated as the working
7.1 Purity of Reagents—At a minimum, reagent grade
spiking solution, and are diluted volumetrically to produce the
chemicals shall be used in all spike preparations. Spectrograde,
working spiking solution at the time of use. In some cases,
high-pressure liquid chromatography (HPLC) grade, pesticide
concentrated solutions may be stable at 4°C for substantially
grade, or ultrapure grade solvents shall be used to prepare
longer periods than dilute solutions. Alternatively, prepare
spiking solutions. Reagents of the highest available purity shall
spike or spiking solution fresh for each batch of samples.
be used for spike analytes and demonstrated to be free of
interfering substances for the subsequent test methods to be
8. Sampling
performed. If possible, a primary standard grade shall be used.
8.1 Although sampling methodology is beyond the scope of
Unless otherwise indicated, it is intended that all reagents
this guide, a properly split or duplicate sample is of utmost
conform to the specifications of the Committee on Analytical
importance to the successful measurement of spike recovery.
Reagents of the American Chemical Society. Other grades
This is especially critical in samples containing suspended
may be used, provided (1) that reagent purity is unspecified and
sediment or volatile analytes.
(2) that it is first
...
This document is not an ASTM standard and is intended only to provide the user of an ASTM standard an indication of what changes have been made to the previous version. Because
it may not be technically possible to adequately depict all changes accurately, ASTM recommends that users consult prior editions as appropriate. In all cases only the current version
of the standard as published by ASTM is to be considered the official document.
Designation: D5788 − 95 (Reapproved 2011) D5788 − 95 (Reapproved 2017)
Standard Guide for
Spiking Organics into Aqueous Samples
This standard is issued under the fixed designation D5788; the number immediately following the designation indicates the year of
original adoption or, in the case of revision, the year of last revision. A number in parentheses indicates the year of last reapproval. A
superscript epsilon (´) indicates an editorial change since the last revision or reapproval.
1. Scope
1.1 This guide covers the general technique of “spiking” aqueous samples with organic analytes or components. It is intended
to be applicable to a broad range of organic materials in aqueous media. Although the specific details and handling procedures
required for all types of compounds are not described, this general approach is given to serve as a guideline to the analyst in
accurately preparing spiked samples for subsequent analysis or comparison. Guidance is also provided to aid the analyst in
calculating recoveries and interpreting results. It is the responsibility of the analyst to determine whether the methods and materials
cited here are compatible with the analytes of interest.
1.2 The procedures in this guide are focused on “matrix spike” preparation, analysis, results, and interpretation. The
applicability of these procedures to the preparation of calibration standards, calibration check standards, laboratory control
standards, reference materials, and other quality control materials by spiking is incidental. A sample (the matrix) is fortified
(spiked) with the analyte of interest for a variety of analytical and quality control purposes. While the spiking of multiple sample
test portions is discussed, the method of standard additions is not covered.
1.3 This guide is intended for use in conjunction with the individual analytical test method that provides procedures for analysis
of the analyte or component of interest. The test method is used to determine an analyte or component’s background level and,
again after spiking, its now elevated level. Each test method typically provides procedures not only for samples, but also for
calibration standards or analytical control solutions, or both. These procedures include preparation, handling, storage, preservation,
and analysis techniques. These procedures are applicable by extension, using the analyst’s judgement on a case-by-case basis, to
spiking solutions, and are not reiterated in this guide. See also Practice E200 for preparation and storage information.
1.4 These procedures apply only to analytes that are soluble in water at the concentration of the spike plus any background
material, or to analytes soluble in a solvent that is itself water-soluble. The system used in the later case must result in a
homogeneous solution of analyte and sample. Meaningful recovery data cannot be obtained if an aqueous solution or homogeneous
suspension of the analyte of interest in the sample cannot be attained.
1.5 Matrix spiking may be performed in the field or in the laboratory, depending on which part of the analytical process is to
be tested. Field spiking tests the recovery of the overall process, including preservation and shipping of the sample. Laboratory
spiking tests the laboratory process only. Spiking of sample extracts, concentrates, or dilutions will test only that portion of the
process subsequent to the addition of the spike.
1.6 The values stated in SI units are to be regarded as standard. No other units of measurement are included in this standard.
1.7 This standard does not purport to address all of the safety concerns, if any, associated with its use. It is the responsibility
of the user of this standard to establish appropriate safety safety, health, and healthenvironmental practices and determine the
applicability of regulatory limitations prior to use.
1.8 This international standard was developed in accordance with internationally recognized principles on standardization
established in the Decision on Principles for the Development of International Standards, Guides and Recommendations issued
by the World Trade Organization Technical Barriers to Trade (TBT) Committee.
2. Referenced Documents
2.1 ASTM Standards:
D1129 Terminology Relating to Water
This guide is under the jurisdiction of ASTM Committee D19 on Water and is the direct responsibility of Subcommittee D19.06 on Methods for Analysis for Organic
Substances in Water.
Current edition approved May 1, 2011Dec. 15, 2017. Published June 2011January 2018. Originally approved in 1995. Last previous edition approved in 20052011 as
D5788 – 95 (2011). (2005). DOI: 10.1520/D5788-95R11.10.1520/D5788-95R17.
For referenced ASTM standards, visit the ASTM website, www.astm.org, or contact ASTM Customer Service at service@astm.org. For Annual Book of ASTM Standards
volume information, refer to the standard’s Document Summary page on the ASTM website.
Copyright © ASTM International, 100 Barr Harbor Drive, PO Box C700, West Conshohocken, PA 19428-2959. United States
D5788 − 95 (2017)
D1193 Specification for Reagent Water
D3694 Practices for Preparation of Sample Containers and for Preservation of Organic Constituents
D3856 Guide for Management Systems in Laboratories Engaged in Analysis of Water
D4375 Practice for Basic Statistics in Committee D19 on Water
E200 Practice for Preparation, Standardization, and Storage of Standard and Reagent Solutions for Chemical Analysis
3. Terminology
3.1 Definitions—Definitions: For definitions of terms used in this guide, refer to Terminology D1129.
3.1.1 For definitions of terms used in this standard, refer to Terminology D1129.
3.2 Definitions of Terms Specific to This Standard:
3.2.1 matrix spike, n—the quantity (mass) of a component (analyte) of interest which is added to a sample (matrix) in order to
test bias as measured by recovery (of that component under specific analytical conditions) and reported as percent recovery (P).
3.2.2 spike, v—the addition of a known amount of an analyte of known identity to a measured volume of a sample (from a
specific matrix) to determine the efficiency with which the added analyte can be “recovered” from (measured in) that matrix by
the analytical system after exposure to a specific portion of an analytical process. Matrix spiking is a process for accomplishing
this. The precision and bias estimates from several trials under specific analytical conditions represent the measurement efficiency
with which the analyte may be determined under these conditions.
3.2.3 spiking solution—the solution in which one or more spikes are dissolved (along with any necessary preservatives). This
solution acts as a carrier to provide ease of measurement and more rapid and thorough mixing of the spike into the sample, as
compared to adding the spike as a pure compound.
4. Summary of Guide
4.1 This guide describes a technique for the addition of a known amount of an organic analyte to an aqueous sample.
Instructions are given to help prevent loss of volatile analytes in the sample headspace and to provide a homogeneous solution for
subsequent analysis. Appropriate concentrations of the spike relative to the original concentration in the sample are discussed.
Applications of the technique and aids in the interpretation of results obtained are described.
5. Significance and Use
5.1 Matrix spiking of samples is commonly used to determine the bias under specific analytical conditions, or the applicability
of a test method to a particular sample matrix, by determining the extent to which the added spike is recovered from the sample
matrix under these conditions. Reactions or interactions of the analyte or component of interest with the sample matrix may cause
a significant positive or negative effect on recovery and may render the chosen analytical, or monitoring, process ineffectual for
that sample matrix.
5.2 Matrix spiking of samples can also be used to monitor the performance of a laboratory, individual instrument, or analyst
as part of a regular quality assurance program. Changes in spike recoveries from the same or similar matrices over time may
indicate variations in the quality of analyses and analytical results.
5.3 Spiking of samples may be performed in the field or in the laboratory, depending on what part of the analytical process is
to be tested. Field spiking tests the recovery of the overall process, including preservation and shipping of the sample and may
be considered a measure of the stability of the analytes in the matrix. Laboratory spiking tests the laboratory process only. Spiking
of sample extracts, concentrates, or dilutions will be reflective of only that portion of the process subsequent to the addition of the
spike.
5.4 Special precautions shall be observed when nonlaboratory personnel perform spiking in the field. It is recommended that
all spike preparation work be performed in a laboratory by experienced analysts so that the field operation consists solely of adding
a prepared spiking solution to the sample matrix. Training of field personnel and validation of their spiking techniques are
necessary to ensure that spikes are added accurately and reproducibly. Consistent and acceptable recoveries from duplicate field
spikes can be used to document the reproducibility of sampling and the spiking technique. When environmentally labile
compounds are used as spikes, the spiking solution shall be protected up to the time of use by appropriate means such as chilling,
protection from sunlight and oxygen, or chemical preservation.
NOTE 1—Any field spiked sample, if known to the laboratory, should be labeled as a field spike in the final results report. Also, whenever possible,
field spiking of volatile compounds should be avoided.
5.5 It is often tacitly assumed that the analyte component is recovered from the sample to approximately the same extent that
a spike of the same analyte is recovered from a spiked sample. One reason that this assumption may be incorrect is that the spike
may not be bound up in the sample (for example, with suspended matter) in the same way that the naturally occurring analyte is
bound in the sample. The spike may therefore be recovered from the sample differently than the background level of the analyte.
For this reason, as well as the fact that bias corrections can add variability, it is not good practice to correct analytical data using
spike recoveries. Spike recovery information should, however, be reported along with the related sample analysis results.
D5788 − 95 (2017)
5.6 This guide is also applicable to the preparation and use of spikes for quantification by the method of standard additions and
to the addition of surrogates and internal standards.
6. Apparatus
6.1 Stirring Apparatus—Borosilicate glass beads, 4 to 6 mm in diameter, or small TFE-coated magnetic stirring bars. A small
non-heating variable-speed magnetic stirrer is recommended for use with the stirring bar.
6.2 Microsyringes—Standard gas chromatographic microsyringes of borosilicate glass with stainless steel needles, suitable for
injection of spiking solutions through a TFE-coated silicone septum. The TFE-tipped plungers may be contaminated by certain
analytes. If this is determined to be likely, a syringe may be dedicated to a single process, or a plain-tipped stainless steel plunger
may be used to avoid cross-contamination. Sizes from 10 to 500 μL are appropriate, depending on the concentration and sample
volumes used.
6.3 Micropipettors—Stainless steel micropipettors with disposable glass tips are preferable to syringes for introduction of
spiking solutions into open sample containers, since they deliver more reproducibly and are less prone to cross-contamination.
Sizes from 5 to 200 μL are appropriate.
6.4 Syringes—Borosilicate glass syringes with demountable stainless steel needles may be used to measure volumes of samples
(spiked or unspiked) to be injected into purge-and-trap sample introduction systems.
6.5 Volumetric Transfer Pipets—Class A, used to deliver known volumes of sample and to add larger volumes of spiking
solutions.
6.6 Volumetric Flasks—Class A volumetric flasks may be used to measure known volumes of sample.
6.7 Balance—An analytical (0.1-mg), semimicro (0.01- mg), or micro (0.001-mg) balance.
7. Reagents
7.1 Purity of Reagents—At a minimum, reagent grade chemicals shall be used in all spike preparations. Spectrograde,
high-pressure liquid chromatography (HPLC) grade, pesticide grade, or ultrapure grade solvents shall be used to prepare spiking
solutions. Reagents of the highest available purity shall be used for spike analytes and demonstrated to be free of interfering
substances for the subsequent test methods to be performed. If possible, a primary standard grade shall be used. Unless otherwise
indicated, it is intended that all reagents conform to the specifications of the Committee on Analytical Reagents of the American
Chemical Society. Other grades may be used, provided (1) that reagent purity is unspecified and (2) that it is first ascertained that
the reagent is of sufficiently high purity to permit its use without adversely affecting the bias and precision of subsequent
determinations. Purchased spiking solutions shall be demonstrated to be free of substances that would interfere with subsequent
analyses being performed, and the supplier’s stated concentration shall be verified by analysis prior to use. Compensatory errors
associated with self-referencing should be prevented by using spiking solutions of a standard originating from a source, when
available, different from that of the routine method calibration standards.
7.2 Purity of Water—Unless otherwise indicated, references to water shall be understood to mean reagent water as defined by
the individual test method to be used to analyze a sample after spiking. If more than one test method is to be utilized, the minimum
criteria of each test method must be met. If test method reagent water specifications are not available, references to water shall be
understood to mean reagent water conforming to Type I of Specification D1193 and demonstrated to be free of interfering
substances for the test(s) being performed.
7.3 Methanol—Spectrograde, HPLC grade, or ultrapure grade methanol is preferable for use as a solvent for water-insoluble
analytes in most trace-level analyses. Other water-soluble solvents may be useful for certain analytes. So
...
Questions, Comments and Discussion
Ask us and Technical Secretary will try to provide an answer. You can facilitate discussion about the standard in here.