Standard Guide for On-Line Monitoring Systems for Water Analysis

ABSTRACT
This guide covers the selection, establishment, application, and validation and verification of monitoring systems for determining water characteristics by continual sampling, automatic analysis, and recording or otherwise signaling of output data. This guide provides a unified approach to the use of on-line monitoring systems for water quality analysis. Safety precautions, system design and installation, calibration techniques, operating procedures, and validation and verification procedures shall be in accordance with the specified requirements.
SIGNIFICANCE AND USE
5.1 Many of the manual and automated laboratory methods for measurement of physical, chemical, and biological parameters in water and waste water are adaptable to on-line sampling and analysis. The resulting real-time data output can have a variety of uses, including confirming regulatory compliance, controlling process operations, or detecting leaks or spills.  
5.2 This guide is intended to be a common reference that can be applied to all water quality monitoring systems. However, calibration, validation, and verification sections may be inappropriate for certain tests since the act of removing a sample from a flowing stream may change the sample.  
5.3 Technical details of the specific methodology are contained in the pertinent ASTM standard test methods, which will reference this standard for guidance in selection of systems and their proper implementation.  
5.4 This guide complements descriptive information on this subject found in the ASTM STP 442.
SCOPE
1.1 This guide covers the selection, establishment, application, and validation and verification of monitoring systems for determining water characteristics by continual sampling, automatic analysis, and recording or otherwise signaling of output data. The system chosen will depend on the purpose for which it is intended: whether it is for regulatory compliance, process monitoring, or to alert the user of adverse trends. If it is to be used for regulatory compliance, the method published or referenced in the regulations should be used in conjunction with this guide and other ASTM methods.  
1.2 The values stated in SI units are to be regarded as standard. No other units of measurement are included in this standard.  
1.3 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, health, and environmental practices and determine the applicability of regulatory limitations prior to use. Specific hazard statements are given in Section 7.  
1.4 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.

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Publication Date
31-Dec-2020
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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: D3864 − 12 (Reapproved 2021)
Standard Guide for
On-Line Monitoring Systems for Water Analysis
This standard is issued under the fixed designation D3864; 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 D4210Practice for Intralaboratory Quality Control Proce-
dures and a Discussion on Reporting Low-Level Data
1.1 This guide covers the selection, establishment,
(Withdrawn 2002)
application, and validation and verification of monitoring
D5540Practice for Flow Control and Temperature Control
systems for determining water characteristics by continual
for On-Line Water Sampling and Analysis
sampling, automatic analysis, and recording or otherwise
E178Practice for Dealing With Outlying Observations
signalingofoutputdata.Thesystemchosenwilldependonthe
2.2 ASTM Special Technical Publication:
purpose for which it is intended: whether it is for regulatory
STP 442Manual on Water
compliance, process monitoring, or to alert the user of adverse
trends.Ifitistobeusedforregulatorycompliance,themethod
3. Terminology
published or referenced in the regulations should be used in
3.1 Definitions:
conjunction with this guide and other ASTM methods.
3.1.1 For definitions of terms used in this standard, refer to
1.2 The values stated in SI units are to be regarded as
Terminology D1129.
standard. No other units of measurement are included in this
standard. 3.2 Definitions of Terms Specific to This Standard:
3.2.1 Calibrations:
1.3 This standard does not purport to address all of the
3.2.1.1 laboratory calibration curve for flow-through
safety concerns, if any, associated with its use. It is the
systems, n—calibration curve calculated from withdrawn
responsibility of the user of this standard to establish appro-
samples or additional standards that may be spiked or diluted
priate safety, health, and environmental practices and deter-
and analyzed using the appropriate laboratory analyzer.
mine the applicability of regulatory limitations prior to use.
Specific hazard statements are given in Section 7. 3.2.1.2 laboratory calibration curve for flow-through
systems, n—type of sample used to generate a laboratory
1.4 This international standard was developed in accor-
dance with internationally recognized principles on standard- calibration curve for flow-through systems.
ization established in the Decision on Principles for the
3.2.1.3 line sample calibration, n—coincidentalcomparison
Development of International Standards, Guides and Recom-
ofalinesampleandadjustmentofacontinuousanalyzertothe
mendations issued by the World Trade Organization Technical
comparedlaboratoryanalyzerorasecondcontinuousanalyzer.
Barriers to Trade (TBT) Committee.
3.2.1.4 multiple standard calibration, n—where the calibra-
tion curve is calculated from a series of calibration standards
2. Referenced Documents
covering the range of the measurements of the sample being
2.1 ASTM Standards:
analyzed.
D1129Terminology Relating to Water
3.2.1.5 probe calibration, n—where the probe is removed
D1193Specification for Reagent Water
from the sample stream and exposed to a calibration solution
D3370Practices for Sampling Water from Flowing Process
and the analyzer is adjusted to indicate the appropriate value.
Streams
Alternately, two probes are exposed to the same solution and
the on-line analyzer is adjusted to coincide with the pre-
This guide is under the jurisdiction ofASTM Committee D19 on Water and is
calibrated laboratory instrument.
the direct responsibility of Subcommittee D19.03 on Sampling Water and Water-
3.2.1.6 reference sample calibration, n—coincidental com-
Formed Deposits, Analysis of Water for Power Generation and Process Use,
On-Line Water Analysis, and Surveillance of Water.
parison of a reference sample and adjustment of a continuous
Current edition approved Jan. 1, 2021. Published January 2021. Originally
analyzer to the compared laboratory analyzer results.
approved in 1979. Last previous edition approved in 2012 as D3864–12. DOI:
10.1520/D3864-12R21.
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 The last approved version of this historical standard is referenced on
Standards volume information, refer to the standard’s Document Summary page on www.astm.org.
the ASTM website. Available from ASTM International Headquarters.
Copyright © ASTM International, 100 Barr Harbor Drive, PO Box C700, West Conshohocken, PA 19428-2959. United States
D3864 − 12 (2021)
3.2.2 cycle time, n—the interval between repetitive sample 3.2.15 response time, n—the time interval from a step
introductions in a monitoring system with discrete sampling. change in the input or output reading to 90% of the ultimate
reading.
3.2.3 drift, n—the change in system output, with constant
3.2.15.1 lag time, n—thetimeintervalfromastepchangein
input over a stated time period of unadjusted, continuous
operation; usually expressed as percentage of full scale over a input to the first corresponding change in output.
24-h period.
3.2.15.2 total time, n—the time interval from a step change
in the input to a constant analyzer signal output.
3.2.3.1 span drift, n—drift when the input is at a constant,
stated upscale value.
3.2.16 sampleport,n—thatpointinthesample-conditioning
system where samples for laboratory analysis are taken.
3.2.3.2 zero drift, n—drift when the input is at zero.
3.2.17 samples:
3.2.4 full scale, n—the maximum measuring limit of the
3.2.17.1 line sample, n—a process sample withdrawn from
system for a given range.
the sample port (3.2.16) during a period when the process
3.2.5 input, n—thevalueoftheparameterbeingmeasuredat
stream flowing through the continuous analyzer is of uniform
the inlet to the analyzer.
qualityandtheanalyzerresultdisplayedisessentiallyconstant.
3.2.6 interference, n—an undesired output caused by a
Laboratory tests or results from a second continuous analyzer
substance or substances other than the one being measured.
are obtained from each sample and compared with the con-
3.2.6.1 Discussion—The effect of interfering substance(s)
tinuous analyzer results obtained at the time of sampling.
on the measured parameter of interest should be expressed as
3.2.17.2 reference sample, n—can be a primary standard or
a percentage change (6) in the measured component as the
adilutionofaprimarystandardofknownreferencevalue.The
interference varies from 0 to 100% of the measuring scale. If
reference value must be established through multiple testing
theinterferenceisnonlinear,analgebraicexpressionshouldbe
using an appropriate ASTM or other standard laboratory test
developed (or curve plotted) to show the varying effect.
method.Bulkquantitiesofthereferencesamplemustbestored
3.2.7 laboratory analyzer, n—a device that measures the
and handled to avoid contamination or degradation. One or
chemical composition or a specific physical, chemical, or
more reference samples encompassing the range of the ana-
biological property of a sample.
lyzer may be required.
3.2.17.2 (1) Discussion—It is essential that the laboratory
3.2.8 limit of detection, n—a concentration of twice the
analyzer be checked carefully before these tests are performed
criterion of detection when it has been decided that the risk of
toensurecompliancewiththerequirementsofthestandardtest
making a Type II error is equal to a Type I error as described
procedure. To further ensure proper operation, it is recom-
in Practice D4210.
mended that a previously calibrated reference sample or an
3.2.9 linearity, n—the extent to which an actual analyzer
in-house control standard of known concentration be tested to
reading agrees with the reading predicted by a straight line
validate the operations of the laboratory analyzer.
drawnbetweenupperandlowercalibrationpoints—generally
3.2.18 validations, n—a one-time comprehensive examina-
zero and full-scale. (The maximum deviation from linearity is
tion of analytical results.
frequently expressed as a percentage of full-scale.)
3.2.18.1 line sample validations, n—a line sample is ana-
3.2.10 monitoring system, n—the integrated equipment
lyzed coincidentally a minimum of seven times by an appro-
package comprising sampling system, analyzer, and data out-
priate continuous analyzer and an appropriate laboratory ana-
put equipment, required to perform water quality analysis
lyzer or a second continuous analyzer. A comparison is made
automatically.
on the differences between the coincidental results using the
3.2.10.1 analyzer, n—adevicethatcontinuallymeasuresthe
Student’s t test at 95% confidence coefficient, two-tailed test,
specificphysical,chemical,orbiologicalpropertyofasample.
to evaluate whether the average difference is statistically
3.2.10.2 data acquisition equipment, n—analog or digital significantlydifferentfromzerodifferenceasdescribedin14.2.
devices for acquiring, processing, or recording, or a combina-
3.2.18.2 reference sample validations, n—a reference
tion thereof, the output signals from the analyzer.
sample is analyzed a minimum of seven times by an appropri-
ate continuous analyzer and by an appropriate laboratory
3.2.10.3 sampling system, n—equipment necessary to de-
liver a continual representative sample to the analyzer. analyzer.Acomparison is made between the average continu-
ous analyzer results and the average laboratory results using
3.2.11 output, n—a signal, usually electrical, that is related
the Student’s t test at 95% confidence coefficient, two-tailed
totheparametricmeasurementandistheintendedinputtodata
test as described in 14.1. Passing the Student’s t test signifies
acquisition equipment.
the continuous analyzer’s average analysis of the reference
3.2.12 range, n—the region defined by the minimum and
sample is not statistically significantly different from the
maximum measurable limits.
laboratory analyzer’s average analysis of the same reference
3.2.13 repeatability, n—a measure of the precision of one
sample(validationtestacceptable).Failingthe“t”testsignifies
analyzertorepeatitsresultsonindependentintroductionofthe
a statistically significant difference exists (validation test not
same sample at different time intervals.
acceptable).
3.2.14 reproducibility, n—a measure of the precision of 3.2.19 verification, n—a periodic or routine procedure to
different analyzers to repeat results on the same sample. ensure reliability of analytical results.
D3864 − 12 (2021)
3.2.19.1 line sample verification, n—a line sample is ana- teeonAnalyticalReagentsoftheAmericanChemicalSociety.
lyzed as described in 3.2.18.1, and the results of the difference Other grades may be used, provided it is first ascertained that
betweenthecontinuousanalyzerandthelaboratoryanalyzeror the reagent is of sufficiently high purity to permit its use
a second continuous analyzer is plotted on a control chart. If without lessening the accuracy of the determination.
the calculated difference between the continuous analyzer and
6.2 Purity of Water—Unless otherwise indicated, the refer-
the laboratory analyzer or a second continuous analyzer is
ence to water shall be understood to mean reagent water that
within 63 S ,thecontinuousanalyzerisconsideredverified.If
d
meetsthepurityspecificationofSpecificationD1193TypeIor
the calculated difference is outside 63 Sd the continuous
Type II water.
analyzer is considered out of control (not verified).
7. Hazards
3.2.19.2 reference sample verification, n—a reference
7.1 Each analyzer installation shall be given a thorough
sample is analyzed as described in 3.2.18.2 and the results of
safety engineering study.
the differences between the continuous analyzer and the
laboratory analyzer are plotted on a control chart. If the
7.2 Electrically, the monitoring system as well as the
calculated difference between the continuous analyzer and the
individual components, shall meet all code requirements for
laboratory analyzer is within 63 S the continuous analyzer is
d the particular area classification.
considered verified.
7.2.1 All analyzers using 120 V, alternating current, 60 Hz,
3.2.19.2 (1) Discussion—If the calculated difference is out-
3-wire systems shall observe polarity and shall not use me-
side 63 S , the continuous analyzer is considered out of
chanical adapters for 2-wire outlets.
d
control (not verified).
7.2.2 Check the neutral side of the power supply at the
analyzer to see that it is at ground potential.
3.3 Symbols:
7.2.3 Connect the analyzer’s ground connection to earth
S = standard deviation
ground and check for proper continuity.
d
7.2.4 The metallic framework of the analyzer shall be at
4. Summary of Guide ground potential.
7.2.5 Consider additional protection in the form of properly
4.1 This guide provides a unified approach to the use of
sized ground fault interrupters for each individual application.
on-line monitoring systems for water quality analysis. It
7.2.6 Analyzerscontainingelectricallyheatedsectionsshall
presentsdefinitionsofterms,safetyprecautions,systemdesign
have a temperature-limit device.
and installation considerations, calibration techniques, general
7.2.7 Theanalyzer,andanyrelatedelectricalequipment(the
operating procedures, and comments relating to validation and
system), shall have a properly sized power cutoff switch and a
verification procedures.
fuse or breaker on the “hot” side of the line(s) of each device.
7.3 Givefullconsiderationtosafedisposaloftheanalyzer’s
5. Significance and Use
spent samples and reagents.
5.1 Many of the manual and automated laboratory methods
7.4 Provide pressure relief valves, if applicable, to protect
for measurement of physical, chemical, and biological param-
both the analyzer and monitoring system.
eters in water and waste water are adaptable to on-line
sampling and analysis. The resulting real-time data output can 7.5 Takeprecautionswhenusingcylinderscontaininggases
have a variety of uses, including confirming regulatory or liquids under pressure. Helpful guidance may be obtained
from Refs (1-4).
compliance, controlling process operations, or detecting leaks
or spills. 7.5.1 Gas cylinders must be handled by trained personnel
only.
5.2 This guide is intended to be a common reference that
7.5.2 Fasten gas cylinders to a rigid structure.
can be applied to all water quality monitoring systems.
7.5.3 T
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