An American National Standard

Designation: D 2331 – 80 (Reapproved 2003)

Standard Practices for

Preparation and Preliminary Testing of Water-Formed
Deposits1
This standard is issued under the fixed designation D 2331; 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 (e) indicates an editorial change since the last revision or reapproval.

1. Scope D 1128 Method for Identification of Types of Microorgan-

1.1 These practices provide directions for the preparation of isms and Microscopic Matter in Water and Waste Water3
the sample for analysis, the preliminary examination of the D 1129 Terminology Relating to Water
sample, and methods for dissolving the analytical sample or D 1193 Specification for Reagent Water
selectively separating constituents of concern. D 1245 Practice for Examination of Water-Formed Deposits
1.2 The general practices given here can be applied to by Chemical Microscopy
analysis of samples from a variety of surfaces that are subject D 2332 Practice for Analysis of Water-Formed Deposits by
to water-formed deposits. However, the investigator must Wavelength-Dispersive X-Ray Fluorescence
resort to individual experience and judgement in applying these E 11 Specification for Wire Cloth Sieves for Testing Pur-
procedures to specific problems. poses
1.3 The practices include the following: 3. Terminology
Sections
Preparation of the Analytical Sample 8 3.1 Definitions—For definitions of terms used in these
Preliminary Testing of the Analytical Sample 9 practices, refer to Terminology D 1129.
Dissolving the Analytical Sample 10

1.4 This standard does not purport to address all of the 4. Significance and Use
safety concerns, if any, associated with its use. It is the 4.1 Deposits in piping from aqueous process streams serve
responsibility of the user of this standard to establish appro- as an indicator of fouling, corrosion or scaling. Rapid tech-
priate safety and health practices and determine the applica- niques of analysis are useful in identifying the nature of the
bility of regulatory limitations prior to use. For a specific deposit so that the reason for deposition can be ascertained.
warning statement, see Note 2. 4.2 Possible treatment schemes can be devised to prevent
deposition from reoccurring.
2. Referenced Documents 4.3 Deposits formed from or by water in all its phases may
2.1 ASTM Standards: 2 be further classified as scale, sludge, corrosion products or
D 887 Practices for Sampling Water-Formed Deposits biological deposits. The overall composition of a deposit or
D 932 Test Method for Iron Bacteria in Water and Water- some part of a deposit may be determined by chemical or
Formed Deposits spectrographic analysis; the constituents actually present as
D 933 Practice for Reporting Results of Examination and chemical substances may be identified by microscope or
Analysis of Water-Formed Deposits X ray.
D 934 Practices for Identification of Crystalline Com-
pounds in Water-Formed Deposits by X-Ray Diffraction 5. Reagents and Materials
D 993 Test Method for Sulfate-Reducing Bacteria in Water 5.1 Purity of Reagents—Reagent grade chemicals shall be
and Water-Formed Deposits3 used in all tests. Unless otherwise indicated, it is intended that
all reagents shall conform to specifications of the Committee
on Analytical Reagents of the American Chemical Society,
1
These practices are under the jurisdiction of ASTM Committee D19 on Water where such specifications are available. 4 Other grades may be
and are the direct responsibility of Subcommittee D19.03 on Sampling of Water and used, provided it is first ascertained that the reagent is of
Water-Formed Deposits, Analysis of Water for Power Generation and Process Use,
On-Line Water Analysis, and Surveillance of Water.
Current edition approved July 3, 1980. Published September 1980. Originally
4
approved in 1965. Last previous edition approved in 1980 as D 2331 – 80. Reagent Chemicals, American Chemical Society Specifications, American
2
For referenced ASTM standards, visit the ASTM website, www.astm.org, or Chemical Society, Washington, DC. For suggestions on the testing of reagents not
contact ASTM Customer Service at [email protected]. For Annual Book of ASTM listed by the American Chemical Society, see Analar Standards for Laboratory
Standards volume information, refer to the standard’s Document Summary page on Chemicals, BDH Ltd., Poole, Dorset, U.K., and the United States Pharmacopeia
the ASTM website. and National Formulary, U.S. Pharmaceutical Convention, Inc. (USPC), Rockville,
3
Withdrawn. MD.

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

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 D 2331 – 80 (2003)
sufficiently high purity to permit its use without lessening the loss in weight of the thimble and contents, dried at 105°C, as
accuracy of the determination. chloroform-extracted matter. If important to the solution of the
5.2 Purity of Water—Unless otherwise indicated, references problem, evaporate the solvent, and examine the residue.
to water shall be understood to mean Type II reagent water 7.5.2 The extraction may be repeated with other volatile
conforming to Specification D 1193. organic solvents if exploratory tests warrant such procedure.
7.6 Pulverizing—Whether the sample is dry as received,
6. Sampling
air-dried or air-dried extracted, it must be pulverized to
6.1 Collect and preserve the sample in accordance with adequate homogeneity. Grind the entire sample, or enough of it
Practices D 887. to be representative of the whole, to pass a No. 100 (150-µm)
7. Preparation of Analytical Sample sieve, as specified in Specification E 11. Continue the grinding
until all the material passes through the sieve, except for
7.1 Preliminary Examination—Examine the sample as col- fragments such as splinters of fiber, wood, and metal.
lected, using a microscope if available, for structure, color, 7.6.1 Identify fragments separated from the sample during
odor, oily matter, appearance of mother liquor if any, and other grinding by standard methods if this information is valuable.
characteristics of note (for example, attraction to magnet). 7.6.2 Mix the sieved material thoroughly by tumbling in a
Record results for future reference. closed dry container that is no more than two thirds full.
7.1.1 Filtration and other steps in the preparation of the 7.6.3 Transfer 5 to 10 g of the thoroughly mixed material to
analytical sample may frequently be bypassed; for example, a a weighing bottle. This is the analytical sample. Unless the
moist sample that contains no separated water shall be started determinations are to be made on an air-dried basis, dry at
in accordance with 7.3.1, and a dry sample shall be started in 105°C and store in a desiccator.
accordance with 7.4, 7.5, or 7.6. Partitioning, 7.4, is not always
practical or even desirable. Solvent extraction, 7.5, is unnec- 8. Preliminary Testing of Analytical Sample
essary if the sample contains no oily or greasy matter. 8.1 This section outlines methods for the preliminary ex-
7.2 Filtration of Sample (see Note 1)—If the sample in- amination of samples of water-formed deposits. Use one or
cludes an appreciable quantity of separated water, remove the more of these methods to disclose the component elements of
solid material by filtration. Save the filtrate, undiluted, pending the sample and whether the concentrations are major, minor, or
decision as to whether or not its chemical examination is trace, an essential guide to planning the analysis. This prelimi-
required. Transfer all of the solid portion to the filter, using the nary testing frequently also provides important guidance to-
filtrate to rinse the sample container if necessary. Air-drying or ward defining technological problems associated with the
partial air-drying of the filter is frequently helpful toward occurrence of the deposits. The methods include spectrogra-
effecting a clean separation of the deposit. phy, atomic absorption spectrophotometry, X-ray diffraction,
NOTE 1—If the sample obviously contains oily matter, its extraction X-ray fluorescence, microscopy, and ordinary qualitative
with a suitable solvent (see 7.5) is essential before filtration or air-drying analysis.
is attempted. Likewise, if the sample is suspected to contain easily 8.2 Spectrography—Make the spectrographic analysis by a
oxidizable materials, such as sulfide, analysis for these materials should be suitable method, for example, as outlined in 8.2.2 to 8.2.7.
completed before air-drying. 8.2.1 Although superior results are obtainable with a spec-
7.3 Air-Drying—Remove the drained solid sample from the trograph and associated equipment, data of lesser degree of
filter, being careful to avoid gross contamination with filter accuracy can frequently be obtained with less formal equip-
paper. ment such as a visual-arc spectroscope.
7.3.1 Air-dry the entire quantity of solid, spread in a thin 8.2.2 For best results use a spectrograph having a suitable
layer on a nonreactive, impervious surface. A record of the loss reciprocal linear dispersion, associated adjuncts and optics, a
of weight during air-drying is often used. microphotometer for measuring the transmittances of spectra-
7.4 Partitioning the Sample—Many samples are obviously line images, and associated equipment for determining inten-
heterogeneous. If useful to explain the occurrence of the sity ratios.
water-formed deposit, separate clearly defined layers or com- 8.2.3 Mix 50 mg of the pulverized sample, obtained in
ponents, and approximate the relative percentages. accordance with 7.6.2, with 900 mg of graphite powder and
7.4.1 Retain the individual air-dried fractions for separate 250 mg of lithium carbonate. Pack the mixture into graphite-
analysis, preferably storing over an effective desiccant such as cup electrodes.
anhydrite. 8.2.4 Record the spectra obtained upon excitation with a d-c
7.5 Solvent Extraction—This step is essential only if the arc.
air-dried sample smears or agglomerates when tested for 8.2.5 Measure the transmittances of the analytical and
pulverization (smears caused by graphite are possible but rare lithium lines (internal standards other than lithium are pre-
with water-formed deposits). ferred by some operators). Determine intensity ratios from
7.5.1 Weigh no more than 10 g of air-dried sample and place these data.
this, wrapped in fine-textured filter paper, in a prepared 8.2.6 Use the intensity ratios to estimate concentrations
(extracted and dried) Soxhlet thimble. Paper clips are useful for from standard analytical curves.
preventing unfolding of the paper. Weigh the thimble and its 8.2.7 The metallic constituents can frequently be deter-
contents and extract in a Soxhlet apparatus until the solvent mined within 20 % of their content in the deposit, which is
(chloroform) in the extraction chamber is colorless. Record the sufficiently close for classification as major, minor, or trace.

2
 D 2331 – 80 (2003)
8.3 Atomic Absorption—Make the atomic absorption analy- 8.4 X-Ray Diffraction—Perform the X-ray diffraction analy-
sis in accordance with appropriate method. sis in accordance with Practices D 934.
8.3.1 The required apparatus shall include an atomizer and 8.4.1 The required apparatus shall include a radiation
burner, suitable pressure-regulating devices, a multielement source, of which more than one may be needed, a camera or
hollow-cathode lamp (alternatively, a hollow-cathode lamp for other device for sensing or recording radiation intensity, and
each metal to be tested), an optical system capable of isolating adjuncts for interpreting the recorded data.
the desired wavelengths of radiation as lines, and adjuncts for 8.4.2 Regrind a portion of the pulverized sample, obtained
obtaining amplified measurements and readout. in accordance with 7.6.2, to pass a No. 270 (53-µm) sieve (or
8.3.2 Prepare standards as in the selected or multiple stan- as directed by a specific manufacturer). Mount the powdered
dards if a multielement is used. Follow the manufacturer’s material in the shape or form required for the sensing device
recommendations for instrument start-up and optimization of that is used.
test conditions. Calibrate the instrument for each element to be 8.4.3 Record the diffraction pattern on photographic film, or
determined by aspirating prepared standard solutions and its equivalent while the mounted sample is exposed to the
noting the corresponding instrument read out. Aspirate a blank X-ray beam for the required interval.
solution between each standard to assure instrument stability.
Each element absorbs energy from the line source at a 8.4.4 The radiation pattern shall be translated into lines and
characteristic wavelength which results in a decrease in energy intensities, using the adjuncts available for this purpose, and
noted at the detector. Record the instrument readings, and plot these shall be compared with standard diffraction patterns for
against the occurrence of the absorbing atom in milligrams per known compounds.
litre of the aspirated solution. 8.4.5 Identification of a substance is made when sufficient
8.3.3 Prepare the solubilized sample (9.2, 9.3, or 9.4, characteristic lines of a standard pattern occur in the pattern
depending on the solubility of the water-formed deposit). derived from the sample, in essentially the same relative
Using volumetric flasks, make 100 mL each of the two intensity. However, owing to the poor crystallization charac-
dilutions, 1 + 9 and 1 + 99, by adding enough water to 10 and teristic of many water-formed deposits, the sensitivity of this
1 mL of the solubilized sample, respectively. evaluation is often much poorer than the 1 percent usually
cited.
8.3.4 Aspirate the solubilized sample and the two dilutions
prepared from it, aspirating water before going from one 8.5 X-Ray Fluorescence—Perform the X-ray fluorescence
dilution to another. Record the instrument readings for the analysis in accordance with Practice D 2332.
wavelengths of interest. 8.5.1 The required apparatus shall include sample prepara-
8.3.5 Determine the concentration of each metal tested in tion equipment, excitation source, devices for housing the
each dilution of the solubilized sample by referring the sample, a spectrometer assembly, and adjuncts for obtaining
absorbance obtained to a prepared calibration curve that relates and interpreting data.
the concentration of prepared standard solutions and their 8.5.2 Regrind the pulverized sample obtained in accordance
corresponding absorbances. Alternatively, when direct readout with 7.6.2 to pass a No. 270 (53-µm) sieve. For order of
in terms of concentration is possible, note the concentration of magnitude determinations the ground sample shall be briquet-
metal for each sample aspirated. Correct the sample readings ted to form a wafer (alternatively, the powdered sample may be
for baseline drift or contaminants, or both, in the reagents used tamped into a specimen holder that is supplied with the
to solubilize the sample by subtracting the blank reading from apparatus).
the sample reading. 8.5.3 For more accurate evaluations, fuse the sample with a
8.3.6 Calculate the concentration of each element deter- flux to improve homogeneity. Even higher degrees of precision
mined in the original sample as follows: are often obtainable through chemical pretreatment to segre-
C3F gate or isolate the constituents of major concern.
6
Concentration, mg/L 5 D 3 10 8.5.4 Radiate the mount with an X-ray beam of short
wavelength (high energy). Use sensitive detectors to measure
where: intensities at selected wavelengths of the dispersed character-
C = concentration of element in the solubilized sample,
istic X rays of each constituent emitted or fluoresced upon
mg/L,
absorption of the primary or incident X rays.
F = dilution of the solubilized test sample, if required, and
D = weight of the original deposit sample diluted to a 1-L 8.5.5 Use the K spectral lines to identify elements of atomic
volume, mg. number 11 to 50. Use either the K or L lines for elements with
8.3.7 Atomic absorption may be increased or decreased by an atomic number of 54 or higher, depending on the available
chemical interferences. For example, calcium absorbance is instrumentation.
lowered in the presence of phosphate, silica can interfere with 8.5.6 Relate detector output (radiation pattern) to constitu-
iron, and aluminum interferes with the determination of mag- ent concentration by reference to calibration curves or charts,
nesium. If these constituents are suspected to be present and as appropriate.
more quantitative results are desired, refer to the methods 8.6 Microscopy—Perform the microscopical examinations
provided by the manufacturers of the equipment for suppress- in accordance with Practice D 1245, Method D 1128, Test
ing these interferences. Method D 932, and Test Method D 993.

3
 D 2331 – 80 (2003)
8.6.1 Perform these microscopical tests on the sample as use of this solvent is advantageous in that it is not oxidizing,
received to ensure that the selection of sample portions for and possible interference from sulfate or nitrate is not intro-
examination is made competently. duced.
8.6.2 The microscopical examination shall include observa- 9.2.1 Reagents—The reagents for this solubilizing method
tions relating to sample description, as required in Practices are as follows:
D 887. Describe outstanding characteristics such as structure 9.2.1.1 Hydrochloric Acid (sp gr 1.19)—Concentrated hy-
and homogeneity as seen through the microscope. drochloric acid (HCl).
8.6.3 Follow the directions and technique given in Practice 9.2.1.2 Hydrochloric Acid (1 + 4)—Mix 1 volume of con-
D 1245 to test selected components of the deposit on micro- centrated HCl (sp gr 1.19) with 4 volumes of water.
scope slides. 9.2.1.3 Hydrochloric Acid (1 + 9)—Mix 1 volume of con-
8.6.3.1 Add the reagents recommended for qualitative test- centrated HCl (sp gr 1.19) with 9 volumes of water.
ing. Observe and interpret the test results obtained. 9.2.2 Weigh approximately 0.5 g of the analytical sample
8.6.3.2 Use polarized light and refractive index standards to obtained in accordance with 7.6.3, into a 250-mL beaker. Add
identify selected crystals from optical characteristics. Amor- 50 mL of HCl (1 + 4) and evaporate to dryness on a hot plate
phous materials may also have optical characteristics that contained in a hood. Add 10 mL of concentrated HCl (sp gr
provide a basis for identification under a microscope. 1.19) and again evaporate to dryness. Add 10 mL of HCl
8.6.4 Identify microorganisms as one of the types tabulated (1 + 9), bring to a boil, and separate the solution by filtration
in Method D 1128, using stains where applicable to differen- through a medium-texture, ashless filter paper. Wash the
tiate the organisms from the background. Specific identifica- residue and dilute with water the combined filtrate and wash-
tion of each species of bacteria, molds, and other organisms ings to a measured volume. Aliquots of this solution shall be
can be made by experienced personnel, but this identification is used for the analysis of the constituents to be determined.
not usually required. 9.2.3 The residue may be retained for further examination.
8.6.5 Test for iron bacteria in corrosion deposits formed at 9.3 Solution in Mixed Hydrochloric Acid-Nitric Acid—This
temperatures below 55°C, consulting Test Method D 932 for solvent is more effective in eliminating traces of organic
the identification of the bacteria. Where required, apply the material and in dissolving more refractory components which
chemical microscopy in this method to verify identification. resist hydrochloric acid alone. The nitric acid, however, may
8.6.6 Test for sulfate-reducing bacteria in corrosion deposits interfere with some analytical procedures unless it is thor-
formed below 40°C, following the procedures in Test Method oughly removed during the dehydration step.
D 993. Use preferred or less precise methods for detecting the 9.3.1 Reagents—The reagents for this solubilizing method
presence of such bacteria in the deposits. Estimate their relative are as follows:
number by the process of incubation and determination of the 9.3.1.1 Hydrochloric Acid (1 + 1)—Mix 1 volume of con-
amount of hydrogen sulfide formed in the culture. centrated hydrochloric acid (HCl, sp gr 1.19) with 1 volume of
8.7 Qualitative Testing—Use qualitative testing, either on a water.
macro or a micro scale, when optical instrumentation is not 9.3.1.2 Nitric Acid (sp gr 1.42)—Concentrated nitric acid
readily available. (HNO3).
8.7.1 Use qualitative testing as an adjunct to testing by 9.3.2 Add 5 mL of HNO3(sp gr 1.42) to approximately 0.5
optical methods. For example, effervescence of the air-dried g of the analytical sample that has been weighed into a 250-mL
sample with acids suggests the presence of carbonate, and the beaker, and evaporate to near dryness on a hot plate contained
deposit probably contains iron if it is attracted by a magnet. in a hood.
8.7.2 Include under qualitative testing the metals more 9.3.3 Add 50 mL of HCl (1 + 1) and 5 mL of HNO3(sp gr
commonly found in water-formed deposits; also, carbonate, 1.42). Evaporate to dryness on a hot plate in a hood.
sulfate, and phosphate. 9.3.4 Cool and add 10 mL of HCl (1 + 1) acid and 1 mL of
HNO3(sp gr 1.42) and repeat the evaporation.
9. Dissolving the Analytical Sample 9.3.5 Allow the beaker to cool and then add 50 mL of HCl
9.1 Selective Isolation or Segregation of Constituents—The (1 + 1). Boil until the volume is decreased to approximately 25
preliminary examination (8.1 to 8.6) will disclose which mL and filter through a medium-texture, ashless filter paper.
constituents comprise the deposit and provide an estimate of 9.3.6 Wash the residue and dilute with water the combined
the content of each. A considerable number of quantitative filtrate and washings to a measured volume. Aliquots of this
determinations can be made directly on the analytical sample, solution shall be used for the analysis of the constituents to be
obtained in accordance with 7.6.3, utilizing special methods of determined.
extraction. These solubilizing procedures are usually specific 9.4 Solution in Mixed Sulfuric Acid— The reagents listed in
to a particular determination and are included with that 9.4.1 are considered good universal solvents for water-formed
determination. deposits containing silica, but sulfate and silica must be
9.2 Solution in Hydrochloric Acid— This treatment will determined on a different portion of the sample.
dissolve water-formed deposits that do not contain a substantial 9.4.1 Reagents—The reagents for this solubilizing method
percentage of stubborn components, including calcium sulfate, are as follows:
various silicates, and some of the more refractory spinels. The 9.4.1.1 Hydrofluoric Acid (48 to 51 %) (HF).

4
 D 2331 – 80 (2003)
NOTE 2—Warning: HF causes rapid and severe burns. Use face shield, 9.5.1.2 Sodium Hydroxide (NaOH), pellets (do not store in
rubber gloves, and aprons. glass bottle).
9.4.1.2 Nitric Acid (sp gr 1.42)—Concentrated nitric acid 9.5.2 Add nine sodium hydroxide pellets (approximately 1.5
(NHO3). g) to a 75-mL nickel crucible. Slowly heat the crucible over a
9.4.1.3 Sulfuric Acid (1 + 1)—Mix carefully 1 volume of Meker burner until the pellets are molten. Allow the crucible
concentrated sulfuric acid (H2SO4, sp gr 1.84) with 1 volume and its contents to cool to room temperature.
of water. 9.5.3 Weigh 0.5 g of the analytical sample, as described in
9.4.2 Add 3 mL of H2SO4(1 + 1) and 10 mL of HF to 7.6.3, and transfer to the crucible containing the NaOH.
approximately 0.5 g of the analytical sample, as described in 9.5.4 Reheat the crucible to remelt the hydroxide and swirl
7.6.3, in a 30-mL platinum crucible; perform these operations to mix in the weighed material. Use a nickel wire or rod to
in a hood. complete the mixing.
9.4.3 Evaporate until most of the hydrofluoric acid has been
volatilized, then add 1 mL of HNO3(sp gr 1.42) and continue 9.5.5 Continue heating for 3 min after mixing, then allow
heating until strong fumes of sulfur trioxide are evolved. Cool the melt to cool.
the crucible and contents. 9.5.6 Add 50 mL of water to the crucible and stir the
9.4.4 Slowly and cautiously add 15 mL of water and digest contents of the crucible occasionally until the melt is disinte-
for 1⁄2 h. grated completely (about 1 h).
9.4.5 Transfer the contents of the crucible quantitatively to 9.5.7 Transfer the contents to a 1-L-volumetric flask (pre-
a 250-mL volumetric flask and adjust to volume when cool. viously rinsed with HCl (1 + 1) containing about 400 mL of
Unless the quantity of insoluble matter (for example, barium, if water and 20 mL of HCl (1 + 1) (a plastic funnel with a stem
present, will form barium sulfate) in the flask is appreciable, it at least 152 mm (6 in.) long should be used so that the strong
may be ignored. alkaline extract will not contact the glass). Use a policeman to
9.4.6 If alkali metals are to be determined on this solubilized wash the crucible and to ensure complete transfer.
portion, a suitable aliquot for these determinations should be 9.5.8 Dilute to volume with water, and transfer the solution
withdrawn from the volumetric flask and stored in a plastic to a plastic bottle for storage.
bottle.
9.5 Alkali Fusion—This method of dissolving the sample is 10. Report
especially useful for the rapid determinations of silica and
10.1 Methods for reporting analytical results should follow
aluminum.
those described in Practice D 933, when applicable.
9.5.1 Reagents—The reagents for this solubilizing method
are as follows:
9.5.1.1 Hydrochloric Acid (1 + 1)—Mix 1 volume of con- 11. Keywords
centrated hydrochloric acid (HCl, sp gr 1.19) with 1 volume of 11.1 crystallographic examination; deposits; sample prepa-
water. ration; scale; spectrographic analysis

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