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: D8084 − 17

Standard Test Method for

Photoelectrochemical Oxygen Demand of Freshwater
Sources for Drinking Water Treatment Plants and Treated
Drinking Water1
This standard is issued under the fixed designation D8084; 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 It is the user’s responsibility to ensure the validity of this test

1.1 This test method covers a protocol for the determination method for waters of untested matrices.
of the photoelectrochemical oxygen demand of freshwater 1.6 This test method is applicable to oxidizable matter, <50
sources for drinking water treatment plants and treated drink- µm that can be introduced into the sensor.
ing water in the range of 0.7 mg/L to 20 mg/L. Higher levels
NOTE 1—This test method can be performed (1) immediately in the
may be determined by sample dilution. field or laboratory on an unpreserved sample, and (2) in the laboratory on
1.2 Photoelectrochemical oxygen demand is determined a properly preserved sample following the stated hold times.
using the current generated from the photoelectrochemical 1.7 The values stated in SI units are to be regarded as
oxidation of the sample using titanium dioxide (TiO2) irradi- standard. No other units of measurement are included in this
ated with ultraviolet (UV) light from a light-emitting diode standard.
(LED).
1.8 This standard does not purport to address all of the
1.3 This test method does not require the use of the safety concerns, if any, associated with its use. It is the
hazardous reagents, such as mercuric sulfate, potassium di- responsibility of the user of this standard to establish appro-
chromate and silver sulfate, that are often associated with the priate safety and health practices and determine the applica-
determination of chemical oxygen demand (that is, Test Meth- bility of regulatory limitations prior to use. For specific hazard
ods D1252). It can also provide a result rapidly, as samples do statements, see Section 9.
not require reflux. 1.9 This international standard was developed in accor-
1.4 Determination of photoelectrochemical oxygen demand dance with internationally recognized principles on standard-
in freshwater sources for drinking water treatment plants and ization established in the Decision on Principles for the
treated drinking water matrices has important implications for Development of International Standards, Guides and Recom-
assessing treatment efficacy. Photoelectrochemical oxygen de- mendations issued by the World Trade Organization Technical
mand can be used as a bulk surrogate measure of natural Barriers to Trade (TBT) Committee.
organic matter, a key target for drinking water treatment. In
aerobic biological treatment processes, determination of pho- 2. Referenced Documents
toelectrochemical oxygen demand can provide an estimation of 2.1 ASTM Standards:2
the oxygen required by microorganisms to degrade organic D1129 Terminology Relating to Water
matter. This test method is complementary to existing natural D1193 Specification for Reagent Water
organic matter (NOM) monitoring techniques and will help D1252 Test Methods for Chemical Oxygen Demand (Di-
scientists and engineers further the understanding of NOM in chromate Oxygen Demand) of Water
water with a rapid oxygen demand test. D2777 Practice for Determination of Precision and Bias of
1.5 This test method was used successfully with reagent Applicable Test Methods of Committee D19 on Water
grade water spiked with pure compounds, freshwater sources D3370 Practices for Sampling Water from Closed Conduits
for drinking water treatment plants and treated drinking water. D5847 Practice for Writing Quality Control Specifications
for Standard Test Methods for Water Analysis

1
This test method is under the jurisdiction of ASTM Committee D19 on Water
2
and is the direct responsibility of Subcommittee D19.06 on Methods for Analysis for For referenced ASTM standards, visit the ASTM website, www.astm.org, or
Organic Substances in Water. contact ASTM Customer Service at [email protected]. For Annual Book of ASTM
Current edition approved July 15, 2017. Published August 2017. DOI: 10.1520/ Standards volume information, refer to the standard’s Document Summary page on
D8084-17. the ASTM website.

Copyright © ASTM International, 100 Barr Harbor Drive, PO Box C700, West Conshohocken, PA 19428-2959. United States

1
 D8084 − 17
3. Terminology TABLE 1 Photoelectrochemical Oxygen Demand Recovery of
Various Pure Compounds in Reagent Grade WaterA
3.1 Definitions—For definitions of terms used in this Range of Theoretical
standard, refer to Terminology D1129. Pure Compound Oxygen Demand Slope (mx+b)
3.1.1 chemical oxygen demand, n—the amount of oxygen Added—mg/L

required under specified test conditions for the oxidation of Caffeine 1.2–24.2 0.69x – 0.36
Phenylalanine 0.9–17.8 1.14x – 1.18
water borne organic and inorganic matter. Sodium Acetate 0.7–13.3 0.79x – 1.34
Sodium Formate 0.3–6.7 0.96x – 0.58
3.2 Definitions of Terms Specific to This Standard: Sodium Oxalate 0.2–3.3 1.47x – 0.13
3.2.1 theoretical oxygen demand, n—the calculated amount Tryptophan 0.9–18.8 1.01x – 0.62
of oxygen required to oxidize a compound to its final oxidation Tyrosine 0.9–17.0 1.01x – 0.87
A
products based on stoichiometry. Adapted from Stoddart, A., K., and Gagnon, G. A., “Application of Photoelectro-
chemical Chemical Oxygen Demand to Drinking Water,” Journal of American
Water Works Association, Vol 106, No. 9, 2014, pp. 383–390.
4. Summary of Test Method
4.1 Photoelectrochemical oxygen demand is determined by
photoelectrochemical oxidation. A sample is mixed with an
electrolyte containing lithium nitrate (LiNO3) and introduced 5. Significance and Use
into a sensor containing TiO2 nanoparticles immobilized on a
thin film. The TiO2 is irradiated with a UV LED, oxidizing the 5.1 This test method describes a rapid method to determine
sample and generating an electrical signal proportional to the the maximum quantity of oxygen that may be consumed by
chemical oxygen demand of the sample. A schematic of this impurities in water. As outlined in Test Methods D1252,
working principle is provided in Fig. 1. chemical oxygen demand is typically used to monitor and
control oxygen-consuming pollutants, both organic and
4.2 Photoelectrochemical oxygen demand recovery of inorganic, in domestic and industrial wastewaters. This photo-
known amounts of theoretical oxygen demand (as pure com- electrochemical oxygen demand test method is specific for
pound) in reagent grade water are shown in Table 1. measuring organics and inorganics in freshwater sources for
4.2.1 A slope of unity for a given compound in Table 1 drinking water treatment plants and treated drinking water
demonstrates that photoelectrochemical oxygen demand was a matrices. This photoelectrochemical oxygen demand test
complete predictor of theoretical oxygen demand over the method is not intended for domestic and industrial wastewaters
theoretical oxygen demand range tested. Each range comprised to replace Test Methods D1252.
five concentrations.
5.2 This test method does not require the use of the
4.3 Photoelectrochemical oxygen demand recovery of hazardous reagents, such as mercuric sulfate, potassium di-
known amounts of theoretical oxygen demand (as sorbitol) in chromate and silver sulfate, that are associated with chemical
reagent grade water, surface water, filtered drinking water and oxygen demand. It can also provide a result more rapidly than
finished drinking water are shown in Fig. 2. chemical oxygen demand as samples do not require reflux.

Adapted from Zhao, H., Jiang, D., Zhang, S., Catterall, K., and John, R.,
“Development of a Direct Photoelectrochemical Method for Determination of
Chemical Oxygen Demand,” Analytical Chemistry, Vol 76, No. 1, 2004, pp.
155–160.

FIG. 1 Working Principle of Photoelectrochemcial Oxygen De-

mand Determination

2
 D8084 − 17

FIG. 2 Demonstration of Photoelectrochemical Oxygen Demand Recovery from Reagent Grade Water, Surface Water, Filtered Drinking
Water and Finished Drinking Water

6. Interferences internal ports, valves and tubing may limit the maximum size
6.1 Chloride is a known interfering agent. Results shown in of particles that can be introduced into the sensor.
Fig. 3 indicate that sorbitol recovery (target concentrations of
7. Apparatus
2, 3, 5, 10, 15 and 20 mg/L) was biased high at increasing
chloride concentrations. 7.1 Photoelectrochemcial Oxygen Demand Analyzer,4—An
analyzer consisting of a reagent and sample introduction
6.2 Similar to Test Methods D1252, some compounds are
mechanism, an electrode block, UV LED, a sensor and a
resistant to oxidation, while others are more easily oxidized.
detector.
Photoelectrochemical oxidation demand has shown that all
7.1.1 Electrode Block—A block housing the reference and
organic materials do not oxidize uniformly.3
auxiliary electrodes.
6.3 Analysis of samples at pH ≥ 9 may bias results low. 7.1.2 UV LED—A light source for illuminating the working
Results shown in Table 2 indicate that sorbitol recovery (target electrode.
concentration of 5 mg/L) was biased low at pH 9. 7.1.3 Sensor—A microcell containing a TiO2 nanoparticle
6.4 This test method is applicable to oxidizable matter that working electrode.
can be introduced into the sensor. For large particles, the
4
The sole source of supply of the photoelectrochemical oxygen demand analyzer
known to the committee at this time is Mantech, Inc., Guelph, Ontario, Canada. If
3
Stoddart, A., K., and Gagnon, G. A., “Application of Photoelectrochemical you are aware of alternative suppliers, please provide this information to ASTM
Chemical Oxygen Demand to Drinking Water,” Journal of American Water Works International Headquarters. Your comments will receive careful consideration at a
Association, Vol 106, No. 9, 2014, pp. 383–390. meeting of the responsible technical committee,1 which you may attend.

3
 D8084 − 17

FIG. 3 Demonstration of Chloride Interference

TABLE 2 Photoelectrochemical Oxygen Demand Recovery of 8.2 Purity of Water—Unless otherwise indicated, references
Sorbitol at Varying pH to water shall be understood to mean reagent grade water
pH Photoelectrochemical Oxygen Demand Recovery—mg/L conforming to Specification D1193, Type I.
5.85A 4.5 ± 0.1
5.81A 4.8 ± 0.1 8.3 Reagents:
5.01B 4.6 ± 0.1 8.3.1 Calibrant, 20 mg/L.
7.02B 4.4 ± 0.1
7.44B 4.8 ± 0.2
8.3.1.1 Discussion—Reagent is prepared from sorbitol
8.02B 4.5 ± 0.2 (<2% by weight) and water. Weigh 20 mg of sorbitol. Dissolve
8.61B 4.5 ± 0.1 the sorbitol in 1 L of water. 1 mg/L of calibrant is equivalent to
9.00B 3.7 ± 0.1
1 mg/L of theoretical oxygen demand.
A
B
Unadjusted pH. 8.3.2 Electrolyte, (<25 mg/L range), (proprietary).6
pH adjusted with sulfuric acid or sodium hydroxide, or both.
8.3.2.1 Discussion—reagent is prepared from lithium nitrate
(<20% by weight), water and sorbitol. Electrolyte is used to
dilute the sample for photocatalytic oxidation and to prepare
7.1.4 Detector—a potentiostat capable of detecting the pho- electrolyte blank solution (8.3.3). The sorbitol in the electrolyte
tocurrent generated. provides a baseline photocurrent.
8.3.3 Electrolyte Blank Solution, mix three parts water and
8. Reagents and Materials one part electrolyte (8.3.2).
8.1 Purity of Reagents—Reagent grade chemicals shall be 8.3.3.1 Discussion—Electrolyte blank solution is used to
used in all tests. Unless otherwise indicated, it is intended that determine the photocurrent generated from the oxidation of
all reagents shall conform to the specifications of the Commit- water. The photocurrent generated from the oxidation of water
tee on Analytical Reagents of the American Chemical Society.5 is subtracted from the total photocurrent generated during the
Other grades may be used, provided it is first ascertained that oxidation of the sample to determine the photocurrent gener-
the reagent is of sufficiently high purity to permit its use ated due to the oxidation of the organic compounds in the
without lessening the accuracy of the determination. sample.

5
Reagent Chemicals, American Chemical Society Specifications, American
6
Chemical Society, Washington, DC. For suggestions on the testing of reagents not The sole source of supply of the calibrant and proprietary electrolyte known to
listed by the American Chemical Society, see Analar Standards for Laboratory the committee at this time is Mantech, Inc., Guelph, Ontario, Canada. If you are
Chemicals, BDH Ltd., Poole, Dorset, U.K., and the United States Pharmacopeia aware of alternative suppliers, please provide this information to ASTM Interna-
and National Formulary, U.S. Pharmacopeial Convention, Inc. (USPC), Rockville, tional Headquarters. Your comments will receive careful consideration at a meeting
MD. of the responsible technical committee,1 which you may attend.

4
 D8084 − 17
NOTE 2—Follow manufacturers’ instructions regarding product storage photoelectrochemical oxygen demand analyzer (7.1). Ensure
and shelf life. pump volume settings are within the limits recommended by
8.4 Materials: the manufacturer.
8.4.1 Sample Vials, disposable 50-mL centrifuge tubes. 11.4 Introduce the electrolyte blank solution (8.3.3) to the
8.4.2 Racks, suitable for sample vials. blank solution port of the photoelectrochemical oxygen de-
8.4.3 Macropipette, 1–10 mL mand analyzer (7.1) and prime the flow line three times.
8.4.4 Graduated Cylinders, various sizes.
12. Calibration and Standardization
9. Hazards
12.1 Calibration:
9.1 Warning—The UV light is automatically turned off 12.1.1 Using a macropipette (8.4.3), prepare an adequate
when the photoelectrochemical oxygen demand analyzer is volume of calibrant for calibration by mixing three parts
opened. However, as a safety measure, do not look directly into calibrant (8.3.1) with one part electrolyte (8.3.2) in a sample
the UV light source at any time. vial (8.4.1).
9.2 Warning—The electrolyte solution contains lithium 12.1.1.1 The rate of use of the calibrant (8.3.1) will depend
nitrate, which is a skin irritant. on the pump volume settings of the photoelectrochemical
oxygen demand analyzer (7.1). Ensure pump volume settings
10. Sampling, Test Specimens, and Test Units are within the limits recommended by the manufacturer.
12.1.2 Swirl gently to homogenize.
10.1 Collect the sample in accordance with Practices 12.1.3 Introduce the sample vial (8.4.1) to the sample port
D3370. of the photoelectrochemical oxygen demand analyzer (7.1) and
10.2 Preserve samples by cooling to 4°C. Samples that have prime the flow line three times.
been preserved to pH < 2.5 with sulfuric or nitric acid and 12.1.4 Prompt the photoelectrochemical oxygen demand
stored for up to seven days can be adjusted to pH 7 with analyzer (7.1) to run a calibration.
sodium hydroxide and analyzed without significant change in 12.1.5 Record the calibration criteria reported by the pho-
photoelectrochemical oxygen demand as shown in Table 3. toelectrochemical oxygen demand analyzer (7.1).
Photoelectrochemical oxygen demand cannot be reliably re- 12.1.6 Ensure that the calibration criteria reported by the
covered from samples preserved to pH < 2.5 with phosphoric photoelectrochemical oxygen demand analyzer (7.1) are within
acid. the limits recommended by the manufacturer.
10.2.1 The actual hold time possible without significant 12.2 Instrument Linearity Quality Check:
change in photoelectrochemical oxygen demand may be less 12.2.1 Instrument linearity should be checked after each
than seven days, especially when easily oxidizable substances new calibration.
are present. It is the responsibility of the user of the test method 12.2.2 Using a macropipette (8.4.3), prepare at least five
to ensure the maximum hold time for their samples. standards to span the expected concentration range of the
samples to be analyzed by diluting calibrant (8.3.1) in regent
11. Preparation of Apparatus
grade water.
11.1 Follow the manufacturer’s instructions for setting up 12.2.3 Using a macropipette (8.4.3), add electrolyte (8.3.2)
the photoelectrochemical oxygen demand analyzer and adjust- to each standard such that standards are three parts standard
ing reagent and sample flows. and one part electrolyte (8.3.2).
11.2 Turn the power on to the photoelectrochemical oxygen 12.2.4 Swirl gently to homogenize.
demand analyzer (7.1) and allow the instrument to equilibrate 12.2.5 Introduce the first standard to the sample port of the
in accordance with the manufacturer’s recommendations photoelectrochemical oxygen demand analyzer (7.1) and prime
the flow line threetimes.
11.3 Using a graduated cylinder (8.4.4), prepare an adequate 12.2.6 Prompt the photoelectrochemical oxygen demand
volume of electrolyte blank solution (8.3.3) by mixing three analyzer (7.1) to run a sample.
parts water and one part electrolyte (8.3.2). 12.2.7 Record the value reported by the photoelectrochemi-
11.3.1 The rate of use of the electrolyte blank solution cal oxygen demand analyzer (7.1).
(8.3.3) will depend on the pump volume settings of the 12.2.8 Repeat Steps 12.2.4 – 12.2.7 for each standard.
12.2.9 The resulting standard curve should have a coeffi-
cient of determination (r2) ≥ 0.99.
TABLE 3 Photoelectrochemical Oxygen Demand Recovery of 12.2.10 If linearity cannot be verified, recalibrate the pho-
Sorbitol at Varying Hold Times and with Varying Preservation toelectrochemical oxygen demand analyzer (7.1). (Refer to
Strategy 12.1.)
Preservative
Hold Time
None Sulfuric Acid Nitric Acid
13. Procedure
Immediate 4.8 ± 0.1 4.6 ± 0.2 4.8 ± 0.1 13.1 Using a macropipette (8.4.3), add an adequate volume
24 hours 4.5 ± 0.1 4.3 ± 0.2 4.6 ± 0.2 of sample to a sample vial (8.4.1).
48 hours 4.8 ± 0.1 4.6 ± 0.2 4.3 ± 0.1
7 days 4.6 ± 0.2 4.5 ± 0.2 4.6 ± 0.2 13.1.1 The rate of use of sample will depend on the pump
volume settings of the photoelectrochemical oxygen demand

5
 D8084 − 17
analyzer (7.1). Ensure pump volume settings are within the The MDL was determined at a target calibrant (sorbitol)
limits recommended by the manufacturer. concentration of 2 mg/L. Each sample was measured in
13.1.2 Ensure that the sample is within the temperature triplicate. A sample blank of reagent grade water was measured
range recommended by the manufacturer. in triplicate after each set of three samples. The MDL was
13.1.3 Ensure that the sample is within the pH range calculated as follows with n = 10:
recommended by the manufacturer. As noted in 6.3, the test MDL 5 s*t ~ n 2 1 , 1 2 α 2 0.99! (2)
method does not introduce sample bias between a pH of 5.0 to
8.6. where:
13.2 Add electrolyte (8.3.2) to the sample vial (8.4.1) such n = number of replicate spike determinations,
that the sample is three parts sample and one part electrolyte s = standard deviation of measured concentrations of n spike
(8.3.2). determinations,
t = Student’s t value at n – 1 degrees of freedom and 1 – α
13.3 Swirl gently to homogenize. (99 percent) confidence level, and
13.4 Introduce the sample vial (8.4.1) to the sample port of α = level of significance.
the photoelectrochemical oxygen demand analyzer (7.1) and 15.3 Precision—The overall precision of the test method
prime the flow line 3 times. within the range from 1 to 20 mg/L varies with the quantity
13.5 Prompt the photoelectrochemical oxygen demand ana- being tested according to Fig. 4.
lyzer (7.1) to run a sample. 15.4 Bias—Recoveries of known amounts of calibrant (sor-
13.6 Record the photoelectrochemical oxygen demand re- bitol) in a series of prepared standards are shown in Fig. 5 and
ported by the photoelectrochemical oxygen demand analyzer tabulated in Table 5.
(7.1). 15.5 The data used in the calculation of precision and bias
are for calibrant (sorbitol) in reagent grade water at six
14. Calculation or Interpretation of Results
concentrations: 1, 3, 5, 10, 15 and 20 mg/L. Each mean value
14.1 The photocurrent generated is converted to photoelec- and standard deviation is comprised of 28 samples with the
trochemical oxygen demand internally by the photoelectro- exception of the 3 mg/L point which is comprised of 27
chemical oxygen demand analyzer (7.1) as follows: samples.
Photoelectrochemical oxygen demand, mg/L 5 k* ~ Q net 2 Q blank! 15.6 These precision and bias values were determined for
(1) calibrant (sorbitol) in reagent grade water and may not be
applicable to other compounds or more complex water matri-
where:
ces. It is the user’s responsibility to ensure the validity of this
k = constant, test method to waters of untested matrices.
Qnet = charge generated from reference oxidation, µC, and
Qblank = charge generated from the oxidation of the electro- 15.7 Since very carefully standardized samples of calibrant
lyte blank solution (8.3.3), µC. (sorbitol) in reagent grade water were used rather than natural
samples collected by usual sampling procedures, the precision
15. Precision and Bias and bias estimates do not include the change in precision and
15.1 This test method was evaluated and validated by a bias that may be attributed to sample collection activities.
single laboratory to meet the requirements of a not fully
validated standard, subject to full validation within five years 16. Quality Control (QC)
of its initial publication, as described in Practice D2777. These 16.1 In order to be certain that analytical values obtained
test data were obtained using calibrant (sorbitol) in reagent using this test method are valid and accurate within the
grade water. For other compounds and matrices, these data may confidence limits of the test, the following QC procedures must
not apply. be followed when running the test:
15.2 The method detection limit (MDL) is shown in Table 4. 16.2 Calibration and Calibration Verification:
16.2.1 Instrument Calibration:
TABLE 4 MDL Calculation 16.2.1.1 Calibrate the photoelectrochemical oxygen demand
Mean Concentration—mg/L
analyzer according to the manufacturer’s instructions. Ensure
2.01111112435657
the manufaturer’s calibration criteria are met prior to analysis
1.57777830759684 of samples.
2.32222223281860
2.07777789433797
16.3 Initial Demonstration of Laboratory Capability:
1.78888910475669 16.3.1 If a laboratory has not performed the test before or if
2.13333266705993 there has been a major change in the measurement system, for
2.32222239145762
2.33333310139717 example, new analyst, new instrument, etc., a precision and
2.33333340485891 bias study should be performed to demonstrate laboratory
2.15555564707845 capability.
MDL: 0.7 16.3.2 Analyze seven replicates of a reference standard
prepared from calibrant (sorbitol) in the range of 1–20 mg/L.

6
 D8084 − 17

FIG. 4 Precision of Determination as Overall Standard Deviation

FIG. 5 Photoelectrochemical Oxygen Demand Bias of Determina-

tions

TABLE 5 Recovery and Precision Data

Average Recovered
Theoretical Oxygen Demand Overall Standard Deviation
Photoelectrochemical Oxygen Bias—mg/L Bias—%
Added—mg/L (sT)—mg/L
Demand—mg/L
20.0 19.9 0.80 0.00 –0.49
15.0 14.7 1.36 –0.02 –1.79
10.0 9.9 1.34 –0.01 –0.83
5.0 4.6 1.76 –0.08 –7.7
3.0 2.8 1.92 –0.07 –7.4
1.0 1.1 1.53 0.08 7.6

16.3.3 Calculate the mean and standard deviation of these 16.3.4 This demonstration (16.3.1 – 16.3.3) should be
seven values and compare to the acceptable ranges of precision repeated until the single operator precision and the mean
provided in Section 15. recovery are within the limits provided in Section 15. If a

7
 D8084 − 17
concentration other than the recommended concentration is sample from each set of samples being analyzed by spiking an
used, refer to Practice D5847 for information on applying the aliquot of the sample with a known concentration of analyte
F test and t test in evaluating the acceptability of the mean and and taking it through the complete analytic method.
standard deviation. 16.6.1 The spike concentration plus the background concen-
16.4 Laboratory Control Sample (LSC): tration of the analyte must not exceed the upper limit of the test
16.4.1 To ensure that the test method is in control, analyze method. The spike must produce a concentration in the spiked
an LCS containing calibrant (sorbitol) at a theoretical oxygen sample 2 to 5 times the background concentration, or 10 to 50
demand of 20 mg/L at the beginning and end of a sequence of times the detection limit of the test method, whichever is
samples. If a large number of samples is analyzed in a single greater.
sequence, analyze an LCS after every 10 samples. The LCS 16.6.2 Calculate the percent recovery of the spike (P) using
must be taken through all of the steps of this analytical method the following formula:
including sample preservation and pretreatment. The value P 5 100@ A ~ V s 1 V ! 2 BV s # ⁄CV (3)
obtained for the LCS should be within 10 % of the true
where:
theoretical oxygen demand.
16.4.2 If the result is not within these limits, analysis of A = analyte concentration (mg/L) in spiked sample,
B = analyte concentration (mg/L) in unspiked sample
samples should be halted until the problem is corrected and
C = concentration (mg/L) of analyte in spiking solution,
either all samples in the batch must be reanalyzed, or the Vs = volume (mL) of sample used, and
results must be qualified with an indication that they do not fall V = volume (mL) added with spike.
within the performance criteria of the test method.
16.6.3 The percent recovery of the spike should fall within
16.5 Method Blank (Blank): limits to be specified in advance by the user, or within 80–120
16.5.1 Analyze a test blank of reagent grade water with each % if no values are specified. If the percent recovery is not
sequence of samples. The background photoelectrochemical within these limits, a matrix interference maybe present in the
oxygen demand in the blank should be ≤0.2 mg/L. If the sample selected for spiking. Under these circumstances, one of
background photoelectrochemical oxygen demand is found to the following remedies should be employed: (1) the matrix
be above this level, analysis of samples should be halted until interference must be removed, or (2) the results must be
the contamination is eliminated and the blank shows no qualified with an indication that the spiked sample did not fall
contamination above this level, or the results must be qualified within the performance criteria of the test method.
with an indication that they do not fall within the performance
criteria of the test method. 17. Keywords
16.6 Matrix Spike (MS)—To check for interferences in the 17.1 chemical oxygen demand; COD; demand; oxygen
specific matrix being tested, perform a MS on at least one demand; photoelectrochemical oxygen demand

APPENDIX

(Nonmandatory Information)

X1. ADDITIONAL CALIBRATION CRITERIA

X1.1 Instrument Calibration TABLE X1.1 Calibration Criteria and General Instrument Settings
Used to Generate Study Data
X1.1.1 Ensure the instrument manufacturer’s calibration Parameter Acceptable Value or Range
criteria are met prior to analysis of samples. The calibration Ratio of the expected theoretical oxygen 0.02–0.06 theoretical oxygen
criteria and general instrument settings used to generate the demand to charge generated during demand/µC
reference oxidation
study data for this test method are summarized in Table X1.1. Raw charge generated during reference ~100 µC
oxidation
Current measured at the end of reference >90 % of a 20 µA baseline
oxidation
Output from the UV LED during reference >50 mA
oxidation
UV wavelength 365 nm

8
 D8084 − 17
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