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200	Federal  Register /  Vol.  49,  No. 209 /  Friday.  October 26.  1984 /  Rules and  Regulations
 the line emission of high concentration
 elements. The first of these effects can be
 compensated by utilizing a computer
 correction of the raw data, requiring the
 monitoring and measurement of the
 interfering element The second effect may
 require selection of an alternate wavelength.
 The third and fourth effects can usually be
 compensated by a background correction
 adjacent to  the analyte line. In addition, users
 of simultaneous multi-element
 instrumentation must assume the
 responsibility of verifying the absence of
 spectral interference from an element that
 could occur in a sample but for which there is
 no channel in the instrument array. Listed in
 Table 2 are  some interference effects for the
 recommended wavelengths given in Table 1.
 The data  in Table 2 are intended for use only
 as a rudimentary guide for the indication of
 potential  spectral interferences. For this
 purpose, linear relations between
 concentration and intensity for the analytes
 and the interferents can be assumed. The
 Interference information, which was
 collected at the Ames Laboratory,1 is
 expressed as analyte concentration
 equivalents (i.e. false analyte concentrations]
 arising from 100 mg/L of the interferent
 element. The suggested use of this
 information is as follows: Assume that
 arsenic (at 193.696 nm) is to be determined in
 a sample containing approximately 10 mg/L
 of aluminum. According to Table Z. 100 mg/L
 of aluminum would yield a false signal for
 arsenic equivalent to approximately 1.3 mg/L.
 Therefore, 10 mg/L of aluminum would result
 in a false signal for arsenic equivalent to
 approximately 0.13 mg/L The reader is
 cautioned that other analytical systems may
 exhibit somewhat different levels of
 interference than those shown in Table 2, and
 that the interference effects must be
 evaluated for each individual system.
  Only those interferents listed were
 investigated and the blank spaces in Table 2
 indicate that measurable interferences were
 not observed for the interferent
 concentrations listed in Table 3. Generally.
 interferences were discernible if they
 produced peaks or background shifts
 corresponding to 2-5% of the peaks generated
 by the analyte concentrations also listed in
 Table 3.
  At present, information on the listed silver
 and potassium wavelengths are not available
 but it has been reported that second order
 energy from the magnesium 383.231 nm
 wavelength  interferes with the listed
 potassium line at 766.491 nm.
  5.1.2  Physical interferences are generally
 considered to be effects associated with the
 sample nebuhzation and transport processes.
 Such properties as change in viscosity dnd
 surface tension can cause significant
 inaccuracies especially in samoles which
 may contain high dissolved solids and/or
 acid concentrations. The use of a peristaltic
 pump may lessen these interferences. If these
 types of interferences are operative, they
 must be reduced by dilution of the sample
and/or utilization of standard addition
 techniques. Another problem which can
  1 Ames La bora lory. USDOE. Iowa Slate
University. Ames Iowa 50011
 occur from high dissolved solids is salt
 buildup at the tip of the nebulizer. This
 affects aersol flow rate causing instrumental
 drift. Wetting the argon prior to nebulization,
 the use of a tip washer, or sample dilution
 have been used to control this problem. Also,
 it has been reported that better control of the
 argon flow rate improves instrument
 performance. This is accomplished with the
 use of mass flow controllers.
  5.1.3   Chemical Interferences are
 characterized by molecular compound
 formation, ionization effects and solute
 vaporization effects. Normally these effects
 are not pronounced with the ICP technique,
 however, if observed they can be minimized
 by careful selection of operating conditions
 (that is, incident power, observation position.
 and so forth), by buffering of the sample, by
 matrix matching, and by standard addition
 procedures. These types of interferences can
 be highly dependent on matrix type and the
 specific analyte element.
  5.2  It is recommended that whenever a
 new or unusual sample matrix is
 encountered, a series of tests be performed
 prior to reporting concentration data for
 analyte elements. These tests, as outlined in
 5.2.1 through 5.2.4. will ensure the analyst
 that neither positive nor negative interference
 effects are operative on any of the analyte
 elements thereby distorting the accuracy of
 the reported values.
  5.2.1  Serial dilution—If the analyte
 concentration is sufficiently high (minimally a
 factor of 10 above the instrumental detection
 limit after dilution), an analysis of a dilution
 should agree within 5 percent of the original
 determination (or within some acceptable
 control limit (14.3) that has been established
 for that matrix.). If not, a chemical or physical
 interference effect should be suspected.
  5.2.2  Spike addition— The recovery of a
 spike addition added at a minimum level of
 10X  the instrumental detection limil
 (maximum 100X) to the original
 determination should be recovered to  within
 90 to 110 percent or within the established
 control limit for that matrix. If not, a matrix
 effect should be suspected. The use of a
 standard addition analysis procedure  can
 usually compensate for this effect.
  Caution: The standard addition technique
 does not detect coincident spectral overlap. If
 suspected, use of computerized
 compensation, an alternate wavelength, or
 comparison with an alternate method  is
 recommended (See 5.2.3).
  5.2.3  Comparison with alternate method
 of analysis—When investigating a new
 sample matrix, comparison tests may be
 performed with other analytical techniques
 such as atomic absorption spectrometry, or
 other approved methodology.
  5.2.4  Wavelength scanning of analyte line
 region—If the appropriate equipment is
 available, wavelength scanning can be
 performed to detect potential spectral
 interferences.

6. Apparatus
  6.1  Inductively Coupled Plasma-Atomic
Emission Spectrometer.
  6.1.1  Computer controlled atomic
emission spectrometer with background
correction.
   6.1.2  Radiofrequency generator.
   6.1.3  Argon gas supply, welding grade or
 better.
   6.2  Operating conditions—Because of the
 differences between various makes and
 models of satisfactory instruments, no
 detailed operating instructions can be
 provided. Instead, the analyst should follow
 the instructions provided by the manufacturer
 of the particular instrument. Sensitivity.
 instrumental detection limit, precision, linear
 dynamic range, and interference effects must
 be investigated and established for each
 individual analyte line on that particular
 instrument. It is the responsibility of the
 analyst to verify that the instrument
 configuration and operating conditions used
 satisfy the analytical requirements and to
 maintain quality control data confirming
 instrument performance and analytical
 results.

 7. Reagents and Standards
   7.1  Acids used in the preparation of
 standards and  for sample processing must be
 ultra-high purity grade or equivalent.
 Redistilled acids are acceptable.
   7.1.1  Acetic acid.  cone, (sp gr 1.06).
   7.1.2  Hydrochloric acid. cone, (sp gr 1.19).
   7.1.3  Hydrochloric acid. (1+1): Add 500
 mL cone. HO (sp gr 1.19) to 400 mL deionized,
 distilled water  and dilute to 1 liter.
   7.1.4  Nitric acid.  cone, (sp gr 1.41).
   7.1.5  Nitric acid.  (1+1): Add 500 mL cone.
 HNO, (sp gr 1.41) to 400 mL deionized,
 distilled water  and dilute to 1 liter.
   7.2  Deionized distilled water Prepare by
 passing distilled water through a mixed bed
 of cation and anion exchange resins. Use
 deionized, distilled water for the preparation
 of all reagents,  calibration standards and as
 dilution water.  The purity of this water must
 be equivalent to ASTMType II reagent water
 of Specification D1193 (14.6).
   7.3  Standard stock solutions may be
 purchased or prepared from ultra high purity
 grade chemicals or metals. All salts must be
 dried for 1 h at  105 *C unless otherwise
 specified.
   (CAUTION: Many metal salts are
 extremely toxic and may be fatal if
 swallowed. Wash hands thoroughly after
 handling.)
   Typical stock solution preparation
 procedures follow:
   7.3.1  Aluminum solution, stock. 1 mL = /ig
 Al: Dissolve 0.100 g of aluminum metal in an
 acid mixture of 4 mL of (1 +\) HCI and l mL
 of cone. HNO] in a beaker. Warm gently to
 effect solution.  When solution is complete.
 transfer quantitatively to a liter flask add an
 additional 10 mL of (1 +1) HCI and dilute to
 1,000 mL with deionized. distilled water.
  7.3.2  Antimony solution stock, 1 mL = 100
 Hg Sb: Dissolve 0.2669 g K(SbO)C.H4O, in
 deionized distilled water, add 10 mL (1 + IJ
 HCI and dilute to 1,000 mL with deionized.
 distilled water.
  7.3.3  Arsenic solution, stock. 1 mL = 100
(ig As: Dissolve 0.1320 g of AsjO] in 100 mL of
deionized. distilled water containing 0.4 g
NaOH. Acidify  the solution with 2 mL cone.
 HNO] and dilute to 1.000 mL with deionized.
distilled water.
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             Federal Register /  Vol.  49, No. 209 /  Friday,  October  26,  1984 /  Rules and  Regulations         201
  7.3.4  Barium solution, stock. 1 mL=100 fig
Ba: Dissolve 0.1516 g BaCI, (dried at 250 *C
for 2 hrs) in 10 mL deionized. distilled water
with 1 mL (1+1! HC1. Add 10.0 mL (1+1) HC1
and dilute to 1.000 with mL deionized.
distilled water.
  7.3.5  Beryllium solution, stock. 1 raL^lOO
fig Be: Do not dry. Dissolve 1.966 g
BeSO. -4H.O. in deionized. distilled water.
add 10.0 mL cone. HNO» and dilute to 1.000
mL with deionized. distilled water.
   7.3.6  Boron solution, stock. I mL—lOO fig
B: Do not dry. Dissolve 0.5716 g anhydrous
Hi BO] in deionized. distilled water and dilute
to 1.000 mL. Use a reagent meeting ACS
specifications, keep the bottle tightly
stoppered and store in a desiccator to
prevent the entrance of atmospheric
moisture.
   7.3.7  Cadmium solution, stock. 1 mL = 100
fig Cd: Dissolve 0.1142 g CdO in a minimum
amount of (1 +1) HNOj. Heat to increase rate
of dissolution. Add 10.0 mL cone. HNOj and
dilute to  1.000 mL with  deionized. distilled
water.
   7.3.8  Calcium solution, stock. 1 mL=100
fig Ca: Suspend 0.2498 g CaCOj dried at 180
'C for 1 h before weighing in deionized.
distilled water and dissolve cautiously with a
minimum amount of(1+1) HNOj. Add 10.0
mL cone. HNOj and dilute to 1.000 mL with
deionized. distilled water.
   7 3.9  Chromium solution, stock. 1 mL=100
fig Cr: Dissolve 0.1923 g of CrOj in deionized.
distilled water. When solution is complete,
acidify with 10 mL cone. HNO> and dilute to
1.000 mL with deionized. distilled water.
   7 3.10  Cobalt solution, stock. 1 ml=100
fig Co: Dissolve 0.1000 g of cobalt metal in a
minimum amount of (1 +1) HNOj. Add 10.0
mL (1 + 1) HC1 and dilute to 1.000 mL with
deionized. distilled water.
   7.3.11  Copper solution, stock. 1 mL=100
fig Cu: Dissolve 0.1252 g CuO in a minimum
amount of (1+1) HNOj. Add 10.0 mL cone.
HNOj and dilute to 1.000 mL with deionized.
distilled water.
   7.112  Iron solution, stock. 1 mL=100 fig
Fe: Dissolve 0.1430 g Fe>O> in a warm mixture
of 20 mL (1 +1) HCI and 2 mL of cone. HNO>.
Cool, add an additional 5 mL of cone. HNOj
and  dilute to 1.000 mL with deionized.
distilled water.
   7.3.13  Lead solution, stock. \ mL = 100fig
Pb: Dissolve 0.1599 g Pb(NOj)i in a minimum
amount of (1 +1) HNOj. Add 10.0 mL cone.
HNOi and dilute to 1.000 mL with deionized.
distilled water.
   7314  Magnesium solution, stock. 1
mL ---100 fiij Mg:  Dissolve 0.1658 " MgO in a
minimum jmount of (1  -Ml HNOi.  Add 10.0
ml. r.onc UNO, and dilute to 1,000 mL with
: Do not dry. Dissolve 0.4730 g NaiSiOj
«9HtO in deionized. distilled water. Add 10.0
mL cone HNO> and dilute to 1,000 mL with
deionized, distilled water.
  7.3.21  Silver solution, stock.  1 mL=100 fig
Ag: Dissolve 0.1575 g AgNOj in 100 mL of
deionized, distilled water and 10 mL cone.
HNOj. Dilute to 1.000 mL with deionized.
distilled water.
  7.3.22  Sodium solution, stock. 1 mL = 100
fig Na: Dissolve 0.2542 g NaCl in deionized.
distilled water. Add 10.0 mL cone. HNOj and
dilute to 1.000 mL with deionized. distilled
water.
  7.3.23  Thallium solution, stock. 1 mL = 100
fig Tl: Dissolve 0.1303 g TlNCs in deionized.
distilled water. Add 10.0 mL cone. HNOj and
dilute to 1.000 mL with deionized. distilled
water.
  7.3.24  Vanadium solution, stock. 1
mL=100 fig V: Dissolve 0.2297 NH.VO, in a
minimum amount of cone HNOi. Heat to
increase rate of dissolution. Add 10.0 mL
cone. HNOj and dilute to 1.000 mL with
deionized. distilled water.
  7.3.25  Zinc solution, stock. 1 mL = 100 fig
Zru Dissolve 0.1245 g ZnO in a minimum
amount of dilute HNOj. Add 10.0 mL cone.
HNOj and dilute to 1.000 mL deionized.
distilled water.
  7:4  Mixed calibration standard
solutions—Prepare mixed calibration
standard solutions by combining appropriate
volumes of the stock solutions in volumetric
flash*. (See 7.4.1 thro 7.4.5) Add 2 mL of
(1+1) HNOi and 10 mL of (1 + 1) HCl and
dilute to 100 mL with deionized, distilled
water. (See Notes 1 and 6.) Prior to preparing
the mixed standards, each stock solution
should be analyzed separately to determine
possible spectral interference or the presence
of impurities. Care should be taken when
preparing the mixed standards that the
elements are compatible and stable. Transfer
the mixed standard solutions to a FEP
fluorocarbon or unused polyethylene bottle
for storage. Fresh mixed standards should be
prepared as needed with the realization that
concentration can change on aging.
Calibration standards must be initially
verified using a quality control sample and
monitored weekly for stability (See 7 6.3).
Although not specifically required, some
typical calibration standard combinations
follow when using those specific wavelengths
listed m Table 1.
  7.4.1  Mixed standard solution I—
Manganese, beryllium, cadmium, lead, and
zinc.
  7.4.2  Mixed standard solution II—Barium.
copper, iron, vanadium, and cobalt.
  7.4.3  Mixed standard solution III—
Molybdenum, silica, arsenic, and selenium.
  7.4.4  Mixed standard solution IV—
Calcium, sodium, potassium, aluminum.
chromium and nickel.
  7.4.5  Mixed standard solution V—
Antimony, boron, magnesium, silver, and
thallium.
  Note 1.—If the addition of silver to the
recommended acid combination results in an
initial precipitation, add 15 mL of deionized
distilled water and warm the flask until the
solution clears. Cool and dilute to 100 mL
with deionized, distilled water. For this acid
combination the silver concentration should
be limited to 2 mg/U Silver under these
conditions is stable in a tap water matrix for
30 days. Higher concentrations of silver
require additional HCI.
  7.5 Two types of blanks are required for
the analysis. The calibration blank (3.13) is
used in establishing the analytical curve
while the reagent blank (3.12)  is used to
correct for possible contamination resulting
from varying amounts of the acids used in the
sample processing.
  7.5.1  The calibration blank is prepared by
diluting 2 mL of (1 +1) HNOj and 10 mL of
(1+1) HCI to 100 mL with deionized. distilled
water. (See Note 6.) Prepare a sufficient
quantity to be used to flush the system
between standards and samples.
  7.5.2  The reagent blank must contain all
the reagents and in the same volumes as used
in the processing of the samples. The reagent
blank must be carried through the complete
procedure and contain  the same acid
concentration in the final solution as the
sample solution used for analysts.
  7.8  In addition  to the calibration
standards, an instrument check standard
(3.7), an interference check sample (3.8) and a
quality control sample  (3.9) are also required
for the analyses.
  7,6.1  The instrument check standard is
prepared by the analyst by combining
compatible elements at a concentration
equivalent to the midpoint of their respective
calibration curves. (See 12.1.1.)
  7.6.2  The interference check sample is
prepared by the analyst in the following
manner. Select a representative sample
which contains minimal concentrations of the
analytes of interest but known concentration
of interfering elements  that will provide an
adequate test of the correction factors. Spike
the sample with the elements  of interest at
the approximate concentration of either 100
fig/L or 5 times the estimated detection limits
given in Table 1. (For effluent samples of
expected high concentrations, spike at an
appropriate level.) If the type of samples
analyzed are varied, a  synthetically prepared
sample may be used if  the above criteria and
intent are met. A limited supply of a synlhetic
interference check sample will be available
from the Quality Assurance Branch of EMSL-
Cincmnati. (See 12.1.2).
  7 6.3  The quality control sample should
be prepared in the  same acid matrix as the
calibration standards at a concentration near
1 mg/L and in accordance with the
instructions  provided by the supplier. The
Quality Assurance Branch of EMSL-
Cincinnati will either supply a quality control
sample or information where one of equal
quality can be procured. (See  12.1.3.)
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  202
Federal  Register /  Vol. 49.  No.  209  / Friday. October  26.  1984 / Rules  and Regulations
 8. Sample Handling and Preservation
   8.1  For the determination of trace
 elements, contamination and loss are of
 prime concern. Dust in the laboratory
 environment, impurities in reagents and
 impurities on laboratory apparatui which the
 sample contacts are all sources of potential
 contamination. Sample containers can
 introduce either  positive or negative errors in
 the measurement of trace elements by (a)
 contributing contaminants through leaching
 or surface desorption and (b) by depleting
 concentrations through adsorption. Thus the
 collection and treatment of the sample prior
 to analysis requires particular attention.
 Laboratory glassware including the sample
 bottle (whether polyethylene, polyproplyene
 or FEP-fluorocarbon) should be thoroughly
 washed with detergent and tap water rinsed
 with (1+1) nitnc acid, tap water. (1 + 1)
 hydrochloric acid, tap and finally deiomzed.
 distilled water in that order (See Notes 2 and
 3).
   Note 2.—Chromic acid may be useful to
 remove organic deposits from glassware:
 however, the analyst should be cautioned
 that the glassware must be thoroughly rinsed
 with water to remove the last traces  of
 chromium. This is especially important if
 chromium is to be included in the analytical
 scheme. A commercial product.
 NOCHROMIX available from Godax
 Laboratories, 8 Vanck St., New York, NY
 10013, may be used in place of chromic acid.
 Chromic acid should not be used with plastic
 bottles.
   Note 3.—If it can be documented through
 an active analytical quality control program
 using spiked samples and reagent blanks.
 that certain steps in the cleaning procedure
 are not required for routine samples,  those
 steps  may be eliminated from the procedure.
   8.2  Before collection of the sample a
 decision must be made as to the type of data
 desired, that is dissolved, suspended or total,
 so that the appropriate preservation and
 pretreatment steps may be accomplished.
 Filtration, acid preservation, etc., are to be
 performed at the  time the sample is collected
 or as soon as possible thereafter.
   8.2.1 For the determination of dissolved
 elements the sample must be filtered  through
 a 0.45-^m membrane filter as soon as
 practical after collection. (Class or plastic
 filtering apparatus are recommended to avoid
 possible contamination.) Use the first 50-100
 mL to  rinse the filter flask. Discard this
 portion and collect the required volume of
 filtrate. Acidify the filtrate with (1 +1) HNO3
 to a pH of 2 or less. Normally. 3 mL of (1 +1)
 acid per liter should be sufficient to preserve
 the sample.
  8.2.2 For the determination of suspended
 elements a measured volume of unpreserved
 sample must be filtered through  a OAS-pm
 membrane  filter as soon as practical after
 collection. The filter plus suspended material
 should be transferred to A suitable container
 for storage and/or shipment. No preservative
 is required.
  8.2.3  For the determination of total or
 total recoverable elements, the sample is
acidified with (1 +1) HNOj to pH 2 or  less as
soon as possible, preferably at the time of
collection. The sample is not filtered before
processing.
                               9. Sample Preparation
                                 9.1  For the determinations of dissolved
                               elements, the filtered, preserved sample may
                               often be analyzed as received. The acid
                               matrix and concentration of the samples and
                               calibration standards must be the same. (See
                               Note 8.) If a precipitate formed upon
                               acidification of the sample or during transit
                               or storage, it must be redissolved before the
                               analysis by adding additional acid and/or by
                               heat as described in 9.3.
                                 9.2  For the determination of suspended
                               elements, transfer the membrane filter
                               containing the insoluble material to a 150-mL
                               Griffin beaker and add 4 mL cone. HNCv
                               Cover the beaker with a watch glass and heat
                               gently. The warm acid will soon dissolve the
                               membrane. Increase the temperature of the
                               hot plate  and digest the material. When the
                               acid has nearly evaporated, cool the beaker
                               and watch glass and add another 3 mL of
                               cone. HNOj. Cover and continue heating until
                               the digestion is complete, generally indicated
                               by a light colored digestate. Evaporate to
                               near dryness (2 mL). cool, and 10 mL HC1
                               (1+1) and 15 mL deionized, distilled water
                               per 100 mL dilution and warm the beaker
                               gently for 15 min. to dissolve any precipitated
                               or residue material. Allow to cool, wash
                               down the watch glass and beaker walls with
                               deionized distilled water and filter the
                               sample to remove insoluble material that
                               could clog the nebulizer. (See Note 4.) Adjust
                               the volume based on the expected
                               concentrations of elements present. This
                               volume will vary depending on the elements
                               to be determined (See Note 8). The sample is
                               now ready for analysis. Concentrations so
                               determined shall be reported as "suspended."
                                 Note 4.—In place of filtring, the sample
                               after diluting and mixing may be centrifuged
                               or allowed to settle by gravity overnight to
                               remove insoluble material.
                                9.3   For the determination of total
                               elements,  choose a measured volume of the
                               well mixed acid preserved sample
                               appropriate for the expected level of
                               elements and transfer to a Griffin beaker.
                               (See Note 5.) Add 3 mL of cone. HNOi. Place
                               the beaker on a hot plate and evaporate to
                               near dryness cautiously, making certain that
                               the sample does not boil and that no area of
                               the bottom of the beaker is allowed to go dry.
                               Cool the beaker and add another 5 mL
                               portion of cone. HNOi. Cover the beaker with
                              a watch glass and return to the hot plate.
                              Increase the temperature of the hot plate so
                              that a gently reflux action occurs. Continue
                              heating, adding additional acid as necessary.
                              until the digestion is complete (generally
                              indicated when the digestate is light in color
                              or does not change in appearance with
                              continued  refluxmg.) Again, evaporate to
                              near dryness and cool the beaker. Add 10 mL
                              of 1 +1  HC1 and 15 mL of deionized, distilled
                              water per 100 mL of final solution and warm
                              the beaker gently for 15 mm. to dissolve any
                              precipitate or residue resulting from
                              evaporation. Allow to cool, wash down the
                              beaker walls and watch glass with deionized
                              distilled water and filter the sample to
                              remove insoluble material  that could clog the
                              nebulizer. (See Note 4.) Adjust the sample to
                              a predetermined volume based on the
                              expected concentrations of elements present.
  The sample is now ready for analysis (See
  Note 6). Concentrations so determined shall
  be reported as "total."
    Note 5.—If low determinations of boron are
  critical, quartz glassware should be used.
    Note 6.—If the sample analysis solution
  has a different acid concentration from that
  given in 9.4, but does not introduce a physical
  interference or affect the analytical result, the
  same calibration standards may be used.
    9.4  For the determination of total
  recoverable elements, choose a measured
  volume of a well mixed, acid preserved
  sample appropriate for the expected level of
  elements and transfer to a Griffin beaker.
  (See Note 5.) Add 2 mL of (1 + 1) HNO> and 10
  mL of (1 +1) HC1 to the sample  and heat on a
  steam bath or hot plate until the volume has
  been reduced to near 25 mL making certain
  the sample does not boil. After this treatment.
  cool the sample and filter to remove insoluble
  material that could clog the nebulizer. (See
  Note 4.) Adjust the volume to 100 mL and
  mix. The sample is now ready for analysis.
  Concentrations so determined shall be
  reported as "total."

  10. Procedure
    10.1  Set up instrument with  proper
  operating parameters established in Section
  8.2. The instrument must be allowed to
  become thermally stable before beginning.
  This usually requires at least 30 min. of
  operation prior to calibration.
    10.2  Initiate appropriate operating
  configuration of computer.
    10.3  Profile and calibrate instrument
  according- to instrument manufacturer's
  recommended procedure*, using the typical
  mixed calibration standard solutions
 described in Section 7.4. Flush the system
  with the calibration blank (7.5.1} between
 each standard. (See Note 7.) (The use of the
 average intensity of multiple exposures for
 both  standardization and sample analysis
 has been found to reduce random error.)
   Note 7.—For boron concentrations greater
 than 500 j*g/L extended flush times of 1 to 2
 minutes may be required.
   10.4  Before beginning the sample run.
 reanalyze the highest mixed calibration
 standard as if it were a sample.
 Concentration values obtained should not
 deviate from the actual values by more than
 +5 percent (or the established control limits
 whichever is lower). If they do, follow the
 recommendations of the instrument
 manufacturer to correct for this condition.
   10.5  Begin the sample run flushing the
 system with the calibration blank solution
 (7.5.1) between each sample. (See Note 7.)
 Analyze the instrument check standard  (761)
 and the calibration blank (7 5.1)  each 10
 samples.
   10.6  If it has been found that  methods of
 standard addition are required, the following
 procedure is recommended.
   10.6.1   The standard addition  technique
 (14.2)  involves preparing new standards in
 the sample matrix by adding known amounts
 of standard to one or more aliquots of the
processed sample solution. This technique
compensates for a sample constitutent that
enhances or depresses the analyte signal thus
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               Federal  Register /  Vol. 49.  No. 209 /  Friday. October  26.  1984 /  Rules and Regulations
 producing a different slope from that of the
 calibration standards. It will not correct for
 additive interference which causes a baseline
 shift. The simplest version of this technique is
 the single-addition method. The procedure is
 as follows. Two identical aliquots of the
 sample solution, each of volume V,. are
 taken. To the first (labeled A) is added a
 small volume V. of a standard analyte
 solution of concentration c,. To the second
 (labeled B) is added the same volume V, of
 the solvent. The analytical signals of A and  B
 are measured and corrected for nonanalyte
 signals. The unknown sample concentration
 c, is calculated:


                     S.V.C,
                   (SA-S.) V,
 where SA and S, are the analytical signals
 (corrected fur the blank) of solutions A and B.
 respectively. V, and c, should be chosen 50
 that S» is roughly twice SB on the average. It
 is best if V, is made much less than V,. and
 thus c, is much greater than c,. to avoid
 excess dilution of the sample matrix. If a
 separation or concentration step is used, the
 additions are best made first and carried
 through  the entire procedure. For the results
 from this technique to be valid, the following
 limitations must be taken into consideration:
   1. The analytical curve must be linear.
   2. The chemical form of the analyte added
 must respond the same as the analyte in the
 sample.
   3. The interference effect must be constant
 over the working range of concern.
   4. The signal must be corrected for any
 additive interference.

 :;. Calculation
   11.1   Reagent blanks (7.5.2) should be
 subtracted from all samples. This is
 particularly important for digested samples
 requiring large quantities of acids to complete
 the digestion.
   11.2   If dilutions were performed, the
 appropriate factor must be applied to sample
 values.
  11.3   Data should be rounded  to the
 thousandth place and all results should be
 reported in mg/L up to three significant
 figures.

 !2. Quality Control (Instrumental)
  12.1  Check the instrument standardization
by aridlyzmg appropriate quality control
check standards as follow:
   12.1.1  Analyze and appropriate
 instrument check standard (7.6.1) containing
 the elements of interest at a frequency of 10%.
 This check standard is used to determine
 instrument drift. If agreement is not within
 ±5% of the expected values or within the
 established control limits, whichever is
 lower, the analysis is out of control. The
 analysis should be terminated, the problem
 corrected, and the instrument recalibrated.
   Analyze the calibration blank (7.5.1) at a
 frequency of 10%. The result should be within
 the established control limits of 2 standard
 deviations of the mean value. If not. repeat
 the analysis two more times and average the
 three results. If the average is not within the
 control limit, terminate the analysis, correct
 the problem and recalibrate the instrument.
   12.1.2  To verify interelement and
 background correction factors analyze the
 interference check sample (7.6.2) at the
 beginning, end. and at periodic intervals
 throughout the sample run. Results should fall
 within the established control limits of 1.5
 times the standard deviation of the mean
 value. If not, terminate the analysis, correct
 the problem and recalibrate the instrument.
   12.1.3  A quality control sample (7.6.3)
 obtained from an outside source must first be
 used for the initial verification of the
 calibration standards. A fresh dilution of this
 sample shall be analyzed every week
 thereafter to monitor their stability. If the
 results are not within ±591 of the true value
 listed for the control sample, prepare  a new
 calibration standard and recalibrate the
 instrument. If this does not correct the
 problem, prepare a new stock standard and a
 new calibration standard and repeat the
 calibration.

 13. Precision and Accuracy
   13.1  In an EPA round robin phase  1 study.
 even laboratories applied the IGP technique
 to acid-distilled water matrices that had been
 dosed with various metal concentrates. Table
 4 lists the true value, the mean reported value
 and the mean * relative standard deviation.

 14. References
  14.1  Winge. R.K.. V.J. Peterson, and V.A.
 Fassel. "Inductively Coupled Plasma-Atomic
 Emission Spectroscopy: Prominent Lines.
 EPA-600/4-79-017.
  14.2  Winefordner. J.D.. 'Trace Analysis:
Spectroscopic Methods for Elements."
Chemical Analysis. Vol. 48. pp. 41-42.
  14.3  Handbook for Analytical Quality
Control in Water and Wastewater
Laboratories. EPA-600/4-79-019.
   14.4  Garbarino. J.R. and Taylor. H.E.. "An
 Inductively-Coupled Plasma Atomic Emission
 Spectrometric Method for Routine Water
 Quality Testing." Applied Spectroscopy 33.
 No. 3 (1979).
   14.5  "Methods for Chemical Analysis of
 Water and Wastes." EPA-600/4-79-020.
   14.8  Annual Book of ASTM Standards.
 Part 31.
   14.7  "Carcinogens—Working With
 Carcinogens." Department of Health.
 Education, and Welfare. Public Health
 Service. Center for Disease Control. National
 Institute for Occupational Safety and Health.
 Publication No. 77-206. Aug. 1977
   14.8  "OSHA Safety and Health
 Standards. General Industry." (29 CFR 1910).
 Occupational Safety and Health
 Administration. OSHA 2206. (Revised.
 January 1976).
   14.9  "Safety in Academic Chemistry
 Laboratories. American Chemical Society
 Publication. Committee on Chemical Safety.
 3rd Edition. 1979.

   TABLE 1 —RECOMMENDED WAVELENGTHS '
  and Estimated Instrumental  Detection Limits
_
Aluminum .. 	
Anamc 	 	 	 .
Antimony
Banum 	
Beryllium 	
Boron 	
Cadmium 	
Cataum
Cnromum 	
Coba*. 	
Copper 	
Iron 	
L4ad 	
Maona*um ,!...'.. " '.!'.' 	 '.'.".'. ..'.....
Manganese 	
Mofybdtnum 	 ....
Ndiai 	
Potaaawm
5elenmn
Sifcca (SO,)
SJver 	
Sodium...
Thanum 	
Vanadun . ..
Zinc . . 	
Wvjtn.
nm
309215
•33696
2C€ 933
455 4^3
313 042
249 773
226 502
3 1 ? 933
267 718
229616
32« 754
259340
220353
2T9 079
257610
202030
231 604
766 491

2!S 158
329068
568 995

292 J02
2-3956 {
Estimated
detection
MIM.
45



0 3
e
4

7
7
6
7
42
30
2
9
15

75
58
7

40
8
2
  'The wevewjngtns  luted am recommended Because of
me» sensnvily and overall acceptance Ounr wavetangtnj
may be substituted 4 they can provide the needed sensitivity
and are treated  «mi me same correcave leotmaues for
spectral interference. (See 511).
  'The estimated instrumental detection »rvs IS snown are
laken  from "Inductively Coupled  Rasr-^.*iorr»c Emission
Specvoacopy-Promnenl  Unes." EPA-600'i-79-017  They
are grven as a guide for an  instrumental  >
-------
 204	Federal  Register / Vol.  49. No. 209  /  Friday. October 26.  1984 /  Rules and Regulations
          TABLE 1.—ANALYTE CONCENTRATION EQUIVALENTS (MG/L) ARISING FROM INTERFERENTS AT THE 100 MG/L LEVEL—Continued


1 eat)
MaQneaum
IHaUaqMiaM 	 	 , ...... u 	 . . „... ,,...
Molybdenum
Nicttel
Setonum
«-brfln
Sodwn 	 - 	 	 _ 	 .
ThaNum
Vanednim
Zinc

Wave-
nm
220353
279079
2*7810

231.804
19ft (KM
206 198
S88.9BS
190.884
292.402
213.8S6


A1
017

0.005
O.OS

0.23


0.30




Ca

0.02











Cr

0.11
0.01



007


DOS



Cu










0 14

Wart*
F.

013
0.002
0.03

009



0005


rant—
"0


0.002










Mn

0.25











Mi













Ti

007





006



	

V








	



           TABLE 3. INTERFERENT AND ANALYTE ELEMENTAL CONCENTRATIONS USED FOR INTERFERENCE MEASUREMENTS IN TABLE 2

























AnalyWa
At
AS 	
8
Ba
Be
Ca
Cd 	
Co
Cr
Cu 	
Fe
Mg 	
Mn
Mo
Na
Mi 	
PtJ ...
Sb 	 „ 	
Se
$i
Tl
V
Zn . ...

(mg/u
10
to
10
1
1
1
10
1
1
1
1
t
t
10
10
10
10
10
10
1
10
1
10


























Intarierents
Al .
Ca
Cr 	
Cu 	
Fa
Mg
Mn
Ni 	
Ti
V















MfVMa)
vital j*/L
733
349
749
206>
f49
239
594
(96
40
512
245
236
201
32


Mean
p«an»MB
62
2.7
1 (
75
38
51
30
56
12
10
58
16
56
21 9


TnMvakM
MS/1
20
15
TO
22

11
20
60
25

30
24
)«


Samp**No. 2
Mean
repoftw*
vatua»ig/L

15














Mean
perc*rtRSO
















Tnwvvlua
M4/1









*





Sampla No. 3
Maan
rcpoflad
valua^g/L
















Wean
percent flSD





"





14
14


   h4ot M uloiiionia war* anatyud by aH labonrtonaa.

[Doc. 84-26189 Filed 10-23-84: 8:45 am)
BILLING COO€ 65«O-50-*I
                                                  D-341
-------
        SUP6RSCAN ELEMENTS, WAVELENGTHS, i, LTL
    Element

   Aluminum
   Ant tmony
   Arsenic
   Barium
   Bury I Hum
   Bismuth
   Baron
   Cadmium
   Calcium
   Cerium
   Chr om ium
   Cobalt
   Copper
   Dysprosium
   Erbium
   Europium
   Sado1inium
   Gallium
   Germanium
   Sold
   Hafnium
   Holmium
   Indium
   Iodine
   I r i d i urn
   Iron
   Lanthanum
   Lead
   Lithium
   Lutetium
   Magnesium
   Manganese
   Mercury
   Molybdenum
   Neodymium
   Nickel
   Niobium
   Osmium
   Palladium
   Phosphorus
   PI a t i num
   Potassium
   Praseodymium
   Rhenium
   Rhod ium
   Ruthenium
   Samar ium
   Scandium
   Selenium
   Si 1 icon
   Silver
   Sod ium
   Strontium
   Sulfur
   Tantalum
   Tellurium
   Teroium
   Thallium
   Thar ium
   Thulium
   Tin
   Ti tanium
   Tungsten
   Uranium
   Vanadium
   Ytterbium
   Yttrium
   Zinc
   Zirconium
Symbo1

fll-SS
Sb-SS
A»-SS
9a-SS
Se-SS
9i-SS
B-SS
Cd-SS
Ca-SS
Ce-SS
Cr-SS
Co-SS
Cu-SS
Dy-SS
Er-SS
Eu-SS
Gd-SS
G»-SS
G«-SS
Au-SS
Hf-SS
Ho-SS
In-SS
I-S3
Ir-SS
Fe-SS
La-SS
Pb-SS
Li-SS
Lu-SS
ng-SS
nn-SS
Hg-SS
Mo-SS
Nd-SS
Ni-SS
Nb-SS
Os-SS
Pd-SS
P-SS
Pt-SS
K-SS
Pr-SS
Re-SS
Rh-SS
Ru-SS
Sm-SS
Se-SS
Se-SS
Si-S3
Ag-SS
Na-SS
Sr-SS
s-ss
Ta-SS
Te-SS
Tb-SS
Tl-SS
Th-SS
Tm-SS
Sn-SS
Ti-SS
UI-SS
u-ss
V-SS
Yb-SS
Y-SS
Zr>-SS
Zr-SS
Wavelength*

  396. i3a
  306.833
  197. 197
  313.0*2
  S23.061
  2<»9.773
  393.366
  M3.76S
  203 . 332
  238.892
  333 . 1 70
  3<»9.910
  381.967
  263. 113
  2^2.763
  277.336
  32
  279.333
  237.610
  19<».232
  202.030
  309.<4l8
  231 .60
-------
EPA METHOD
 NO. 350.2
         D-343
-------
                             NITROGEN, AMMONIA

            Method 350.2 (Colorimetric; Titrimetric; Potentiometric -
                                Distillation Procedure)

                                                          STORET NO. Total 00610
                                                                      Dissolved 00608

1.    Scope and Application
     1.1   This distillation method covers the determination of ammonia-nitrogen exclusive of total
           Kjeldahl nitrogen, in drinking, surface and saline waters, domestic and industrial wastes.
           It is the method of choice where economics and sample load do not warrant the use of
           automated equipment.
     1.2   The method covers the range from about 0.05 to 1.0 mg NH3-N/1 for the colorimetric
           procedure, from 1.0 to 25 mg/1 for the titrimetric  procedure, and  from 0.05 to 1400
           mg/1 for the electrode method.
     1.3   This method  is described for  macro glassware; however,  micro distillation equipment
           may also be used.
2.    Summary of Method
     2.1   The sample is buffered at a pH of 9.5 with a borate buffer in order to decrease hydrolysis
           of cyanates and organic nitrogen compounds, and is then distilled into a solution of boric
           acid. The ammonia in the distillate can be determined colorimethcally by nesslerization,
           titrimetrically with standard sulfuric  acid with the use  of a mixed  indicator, or
           potentiometrically  by  the  ammonia electrode. The choice between  the first  two
           procedures depends on the concentration of the ammonia.
3.    Sample Handling and Preservation
     3.1   Samples may be preserved with 2 ml of cone. H2SO4 per liter and stored at 4*C.
4.    Interferences
     4.1   A number of aromatic and aliphatic amines, as well as other compounds, both organic
           and inorganic,  will cause turbidity upon the addition of  Nessler  reagent, so direct
           nesslerization (i.e., without distillation), has been discarded as an official method.
     4.2   Cyanate, which may be encountered in certain industrial effluents, will  hydroiyze to
           some extent even at the pH of 9.5 at which distillation is  carried out.  Volatile alkaline
           compounds, such as certain ketones, aldehydes, and alcohols, may cause an off-color
           upon nesslerization in the distillation method. Some of these,  such as formaldehyde, may
           be eliminated by boiling off at a low pH (approximately 2  to 3) prior, to distillation and
           nesslerization.
     4.3   Residual chlorine must also be removed by pretreatment of  the sample with sodium
           thiosulfate before distillation.
Approved fcr NPDES
Issued 1971
Editorial region 1974

                                         D-344
-------
5.    Apparatus
     5.1   An all-glass distilling apparatus with an 800-1000 ml flask.
     5.2   Spectrophotometer or filter photometer for use at 425 nm and providing a light path of 1
           cm or more.
     5.3   Nessler tubes: Matched Nessler tubes (APHA Standard) about 300 mm long, 17 mm
           inside diameter, and marked at 225 mm ±1.5 mm inside measurement from bottom.
     5.4   Erlenmeyer flasks: The distillate  is collected in 500 ml glass-stoppered flasks. These
           flasks should be marked at the 350 and the 500 ml volumes. With such marking, it is not
           necessary to transfer the distillate to volumetric flasks.
6.    Reagents
     6.1   Distilled water should  be free of ammonia.  Such water is best prepared by passage
           through an ion exchange column containing a strongly acidic cation exchange resin
           mixed with a strongly basic anion exchange resin. Regeneration of the column should be
           carried out according to the manufacturer's instructions.
           NOTE 1: All solutions must be made with ammonia-free water.
     6.2   Ammonium chloride, stock solution: 1.0 ml = 1.0 mg NH3-N. Dissolve 3.819 g NH4C1
           in distilled water and bring to volume in a 1 liter volumetric flask.
     6.3   Ammonium chloride, standard solution: 1.0  ml = 0.01 mg.  Dilute 10.0 ml of stock
           solution (6.2) to 1 liter in a volumetric flask.
     6.4   Boric acid solution (20 g/1): Dissolve 20 g H3BO3 in distilled water and dilute to 1 liter.
     6.5   Mixed indicator: Mix 2 volumes of 0.2%  methyl  red in 95% ethyl alcohol with 1 volume
           of 0.2% methylene blue in 95%  ethyl alcohol. This solution should be prepared fresh
           every 30 days.
           NOTE 2: Specially denatured ethyl alcohol conforming to Formula 3 A or 30 of the U.S.
           Bureau of Internal Revenue may be substituted for 95% ethanol.
     6.6   Nessler reagent: Dissolve 100 g of mercuric iodide and 70 g of potassium iodide in a small
           amount of water. Add this mixture slowly, with stirring, to a cooled solution of 160 g of
           NaOH in 500 ml of water. Dilute the mixture to 1 liter. If this reagent is stored in a Pyrex
           bottle out of direct sunlight, it will remain stable for a period of up to 1 year.
           NOTE 3:  This reagent should give the characteristic color with ammonia within  10
           minutes  after addition, and should  not  produce a precipitate with small amounts of
           ammonia (0.04 mg in a 50 ml volume).
     6.7   Borate buffer:  Add 88 ml of 0.1 N NaOH  solution to 500 ml of 0.025 M sodium
           tetraborate solution (5.0 g anhydrous Na2B4O7 or 9.5 g Na2BtO7»10H;,O per liter) and
           dilute to 1 liter.
     6.8   Sulfuric acid, standard  solution: (0.02 N, 1 ml  = 0.28 mg NH3-N). Prepare a stock
           solution of approximately 0.1 N acid by diluting 3 ml of cone.  H2SO4 (sp. gr. 1.84) to 1
           liter with CO2-free distilled water. Dilute 200 ml of this solution to 1 liter with CO2-free
           distilled water.
           NOTE 4:  An  alternate  and perhaps preferable  method  is to  standardize  the
           approximately 0.1 N H,SO4  solution against a 0.100 N Na2CO3 solution. By proper
           dilution the 0.02 N acid can then be prepared.
                                          D-345
-------
          6.8.1 Standardize the approximately 0.02 N acid against 0.0200 N Na:CO3 solution.
                This last solution is prepared by dissolving 1.060 g anhydrous Na:CO3, oven-dried
                at 140'C, and diluting to 1000 ml with CO:-free distilled water.
     6.9  Sodium hydroxide, I N: Dissolve 40 g NaOH in ammonia-free water and dilute to 1 liter.
     6.10 Dechlorinating reagents: A number of dechlorinating reagents may be used to remove
          residual chlorine prior to distillation. These include:
          a.    Sodium thiosulfate (1/70 N): Dissolve 3.5 g Na,S,O3»5H:O in distilled water and
                dilute to 1 liter. One ml of this solution will remove 1 mg/1 of residual chlorine in
                500 ml of sample.
          b.    Sodium arsenite (1/70 N): Dissolve 1.0 g NaAsO: in distilled water and dilute to 1
                liter.
7.    Procedure
     7.1  Preparation of equipment: Add 500 ml of distilled water to an 800 ml Kjeldahl flask. The
          addition of boiling  chips which have been previously treated with dilute NaOH will
          prevent bumping. Steam out the distillation apparatus until the distillate shows no trace
          of ammonia with Messier reagent.
     7.2  Sample  preparation:   Remove the residual  chlorine  in  the sample  by  adding
          dechlorinating agent equivalent to the chlorine residual. To 400 ml of sample add 1 N
          NaOH (6.9), until the pH is 9.5, checking the pH during addition with a pH meter or by
          use of a short range pH paper.
     7.3  Distillation: Transfer the sample, the pH of which has been adjusted to 9.5, to an 800 ml
          Kjeldahl flask and add 25 ml of the borate buffer (6.7). Distill 300 ml at the rate of 6-10
          ml/min. into 50 ml of 2% boric acid (6.4) contained in a 500 ml Erlenmeyer flask.
          NOTE 5: The condenser tip  or an extension of the condenser tip must extend below the
          level of the boric acid solution.
          Dilute the distillate to 500 ml with distilled water and nesslerize an aliquot to obtain an
          approximate value of the ammonia-nitrogen concentration. For concentrations above 1
          mg/1 the ammonia should be determined titrimetrically. For concentrations below this
          value it is determined colorimetncally. The electrode method may also be used.
     7.4  Determination of ammonia in distillate: Determine the ammonia content of the distillate
          titrimetrically, colorimetrically or potentiometrically as described below.
          7.4.1 Titrimetric determination: Add 3 drops of the  mixed indicator to the distillate and
                titrate the ammonia with the 0.02 N H:SO^ matching the end point against a blank
                containing the same volume of distilled water and H,BO3 solution.
                                          D-346
-------
          7.4.2 Colorimetric determination: Prepare a series of Nessler tube standards as follows:

                    ml of Standard
               1.0 mi  = 0.01  mg NH3-N                        mg NH3-N/50.0 ml

                       0.0                                            0.0
                       0.5                                          0.005
                        1.0                                           0.01
                       2.0                                           0.02
                       3.0                                           0.03
                       4.0                                           0.04
                       5.0                                           0.05
                       8.0                                           0.08
                       10.0                                           0.10

                Dilute each tube to 50 ml with distilled water, add 2.0 ml of Nessler reagent (6.6)
                and mix. After 20 minutes read the absorbance at 425 nm against the blank. From
                the values obtained  plot absorbance vs. mg NH3-N for the  standard curve.
                Determine the ammonia in the distillate by nesslerizing 50 ml or an aliquot diluted
                to 50 ml and reading the  absorbance at 425 nm as described above  for the
                standards. Ammonia-nitrogen content is read from the standard curve.
          7.4.3 Potentiometric determination: Consult the method entitled Nitrogen, Ammonia:
                Selective Ion Electrode Method (Method 350.3) in this manual.
     7.5  It is not imperative that all standards be distilled in the same manner as the samples. It is
          recommended that at least two standards (a high and low) be distilled and compared to
          similar values on the curve to insure that the distillation technique is reliable. If distilled
          standards do not agree with undistilled standards the operator should find the cause of
          the apparent error before proceeding.
8.    Calculations
     8.1  Titrimetric

                                  ,.  KI1J     v.    A x 0.28 x 1.000
                               mg/1  NHi -  N =  	s	'	
           where:
           A = ml0.02NH2SO4used.
           S = ml sample.
     8.2   Spectrophotometric
                                                           x
           where:
           A = mg NH3-N read from standard curve.
           B = ml total distillate collected, including boric acid and dilution.
           C = ml distillate taken for nesslerization.
           D = ml of original sample taken.
                                            D-347
-------
     8.3  Potentiometric
9.
                                  mg/l NH, - N = —  x A
                                                   D
     where:
     A = mgNHj-N/l from electrode method standard curve.
     D = ml of original sample taken.
Precision and Accuracy
9.1   Twenty-four analysts in sixteen laboratories analyzed natural water samples containing
     exact increments of an ammonium salt, with the following results:
      Increment as
   Nitrogen, Ammonia
       mg  N/Uter

          0.21
          0.26
           1.71
           1.92
                         Precision as
                     Standard Deviation
                         mgN/liter

                           0.122
                           0.070
                           0.244
                           0.279
          Accuracy as
 Bias,
 -5.54
-18.12
+0.46
 -2.01
   Bias,
mg N/liter

   -0.01
   -0.05
   4-0.01
   -0.04
(FWPCA Method Study 2, Nutrient Analyses)
                                      Bibliography

1.    Standard Methods for the Examination of Water  and Wastewater, 14th Edition, p  410,
     Method 418A and 41 SB (1975).
2.    Annual Book of ASTM Standards, Part 31, "Water", Standard D1426-74, Method A, p 237
     (1976).
                                          D-348
-------
EPA METHOD
 NO. 350.3
      D-349
-------
                             NITROGEN, AMMONIA

             Method  350.3  (Potentiometric, Ion  Selective  Electrode)

                                                         STORET  NO.  Total  00610
                                                                      Dissolved  00608

1.    Scope and Application
     1.1   This method is applicable to the measurement of ammonia-nitrogen in drinking, surface
          and saline waters, domestic and industrial wastes.
     1.2   This method covers the range from 0.03 to 1400 mg NH3-N/1. Color and turbidity have
          no effect on the measurements, thus, distillation may not be necessary.
2.    S ummary of Method
     2.1   The ammonia is determined potentiometrically using an ion selective ammonia electrode
          and a pH meter having an expanded millivolt scale or a specific ion meter.
     2.2   The ammonia electrode uses a hydrophobic gas-permeable membrane to separate the
          sample solution from an ammonium chloride internal solution. Ammonia in the sample
          diffuses through the membrane and alters the pH of the  internal solution, which is sensed
          by a pH electrode. The constant level of chloride in the internal solution is sensed by a
          chloride selective ion electrode which acts as the reference electrode.
3.    Sample Handling and Preservation
     3.1   Samples may be preserved with 2 ml of cone. HjSO4 per  liter and stored at 4°C.
4.    Interferences
     4.1   Volatile amines act as a positive interference.
     4.2  Mercury interferes by forming a strong complex with ammonia. Thus the samples cannot
          be preserved with mercuric chloride.
5.    Apparatus
     5.1   Electrometer (pH meter) with expanded m V scale or a specific ion meter.
     5.2  Ammonia selective electrode, such as Orion Model 95-10 or EIL Model 8002-2.
     5.3   Magnetic stirrer, thermally insulated, and Teflon-coated stirring bar.
6.    Reagents
     6.1    Distilled water: Special precautions must be taken to insure that the distilled water is free
           of ammonia. This is accomplished by passing distilled water through an ion exchange
           column containing a strongly acidic cation  exchange resin mixed  with a strongly basic
           anion exchange resin.
     6.2   Sodium hydroxide, ION: Dissolve 400 g of sodium hydroxide in 800 ml of distilled water.
           Cool and dilute to 1 liter with distilled water (6.1).
     6.3   Ammonium chloride, stock solution:  1.0 ml =  1.0 mg  NH3-N. Dissolve 3.819 g NH4C1
           in water and bring to volume in a 1 liter volumetric flask using distilled water (6.1).
Issued 1974

                                           D-350
-------
     6.4  Ammonium chloride, standard solution: 1.0 ml = 0.01 mg NH3-N. Dilute 10.0 ml of the
          stock solution (6.3) to 1 liter with distilled water (6.1) in a volumetric flask.
          NOTE 1: When analyzing saline waters, standards must be made up in synthetic ocean
          water (SOW); found in Nitrogen, Ammonia: Colorimetric, Automated Phenate Method
          (350.1).
7.    Procedure
     7.1  Preparation of standards:  Prepare  a series  of standard  solutions  covering the
          concentration range of the samples by diluting either the stock or standard solutions of
          ammonium chloride.
     7.2  Calibration of electrometer:  Place 100 ml of each standard solution in clean 150 ml
          beakers. Immerse electrode into standard of lowest concentration and add  1 ml of ION
          sodium hydroxide solution while mixing. Keep  electrode in the solution until a stable
          reading is obtained.
          NOTE 2: The pH of the solution after the addition of NaOH must be above 11.
          Caution: Sodium hydroxide  must  not be added  prior to electrode immersion, for
          ammonia may be lost from a basic solution.
     7.3  Repeat this procedure with the  remaining  standards, going from lowest to  highest
          concentration. Using semilogarithmic graph paper, plot the concentration of ammonia in
          mg NH3-N/1 on the log axis vs. the electrode potential developed in the standard on the
          linear axis,  starting with the lowest concentration at the bottom of the scale.
     7.4  Calibration of a specific ion  meter: Follow the directions of the manufacturer for the
          operation of the instrument.
     7.5  Sample measurement: Follow the procedure in (7.2) for 100 ml of sample in 150 ml
          beakers.  Record the stabilized potential of each  unknown sample and  convert the
          potential reading to the ammonia concentration using the standard curve.  If a specific
          ion meter is used, read the ammonia level directly in mg NH3-N/1.
8.    Precision and Accuracy
     8.1  In a single laboratory (EMSL), using surface water samples at concentrations of 1.00,
          0.77, 0.19,  and 0.13 mg NH3-N/1, standard deviations were   ±0.038, ±0.017, ±0.007,
          and ±0.003, respectively.
     8.2  In a single laboratory (EMSL), using surface water samples at concentrations of 0.19 and
          0.13 mg NH3-N/1, recoveries were 96% and 91 %, respectively.

                                      Bibliography

1.    Booth, R. L., and Thomas, R. P., "Selective Electrode Determination of Ammonia in Water
     and Wastes", Envir. Sci.  Technology, 7, p 523-526 (1973).
2.    Banwart, W. L., Bremner, J. M., and Tabatabai, M. A., "Determination of Ammonium in Soil
     Extracts and Water  Samples by an Ammonia Electrode", Comm. Soil Sci. Plant.,3,p 449
     (1952).
3.    Midgley, D., and Torrance, K., "The Determination of Ammonia in Condensed Steam and
     Boiler Feed-Water with a Potentiometric Ammonia Probe", Analyst. 97 p 626-633 (1972).
                                         D-351
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D-352
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EPA METHOD
 NO. 405.1
    D-353
-------
                      BIOCHEMICAL  OXYGEN DEMAND

                            Method 405.1  (5 Days, 20°O

                                                                STORET  NO.  00310
                                                                Carbonaceous 80082
1.    Scope and Application
     1.1  The biochemical oxygen demand (BOD) test is used for determining the relative oxygen
          requirements of municipal and industrial wastewaters. Application of the  test to organic
          waste discharges  allows calculation of the effect of the discharges, on  the  oxygen
          resources of the receiving water. Data from BOD tests are used for the development of
          engineering criteria for the design of wastewater treatment plants.
     1.2  The BOD test is an empirical  bioassay-type procedure which measures the dissolved
          oxygen consumed by microbial life while assimilating and oxidizing the organic matter
          present. The standard test conditions include dark incubation at 20'C for a specified time
          period (often 5 days).  The actual environmental conditions of temperature,  biological
          population, water movement, sunlight, and oxygen concentration cannot be accurately
          reproduced in the laboratory. Results obtained must take into account the above factors
          when  relating BOD results to stream oxygen demands.
2.    Summary of Method
     2.1  The sample of waste, or an appropriate dilution, is incubated for 5 days  at 20°C in the
          dark.  The reduction in dissolved oxygen concentration  during  the incubation period
          yields a measure of the biochemical oxygen demand.
3.    Comments
     3.1  Determination of dissolved oxygen in the BOD test may be made by use of either the
          Modified Winkler with Full-Bottle Technique or the Probe Method in this  manual.
     3.2  Additional information relating to oxygen demanding characteristics of wastewaters can
          be gained by applying the Total Organic Carbon and Chemical  Oxygen  Demand tests
          (also found in this manual).
     3.3  The use of 60 ml incubation bottles in place of the usual 300 mi incubation  bottles, in
          conjunction with the probe, is often convenient.
4.    Precision and Accuracy
     4.1  Eighty-six analysts in  fifty-eight laboratories analyzed natural water samples  plus an
          exact  increment of biodegradable organic compounds. At a mean value of 2.1 and 175
          mg/1  BOD,  the standard deviation was tO.7 and  -26 mg/1. respectively (EPA Method
          Research Study 3).
     4.2  There is no acceptable procedure for determining the accuracy of the BOD test.
Appmvrd fm  NPDKS C.HOO: pending .ippioval loi SCMIOII  il)l(li). (A\ A
Issued 1971
Editorial revision 1974

                                         D-354
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 5.    References
5.1    The procedure to be used for this determination is found in:                             /
      Standard Methods for the Examination of Water and Wastewater,  15th
      Edition, p. 483, Method 507 (1980).
5.2    Young, J. C., "Chemical Methods for Nitrification Control," J. Water
      Poll. Control Fed., 45, p. 637 (1973).
                                   D-355
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D-356
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EPA METHOD
  NO. 300
      D-357
-------
                               United States
                               Environmental Protection
                               Agency
                               Environmental Monitoring and
                               Support Laboratory
                               Cincinnati OH 45268
                               Research and Development
                                EPA-600/ 4-84-017  Mar. 1984
vvEPA
Test  Method
The  Determination  of
Inorganic  Anions  in
Water by Ion  Chromatography
Method  300.0
                               James W. O'Oell. John 0. Pfaff. Morris E. Gales, and Gerald 0. McKee
                               1.  Scope and Application

                               1.1 This method covers the
                               determination of the following
                               inorganic anions.
Analvte
Chloride
Fluoride
Nitrate-N
Nitrtte-N
Ortho-Phosphate-P
Sulfate
Storet No.
Total Dissolved
00940 —
00951 00950
00620 —
00615 —
— 00671
00945 —
                               1.2  This is an ion chromatographic
                               (1C) method applicable to the
                               determination of the anions listed
                               above in drinking water, surface
                               water, and mixed domestic and
                               industrial wastewater.

                               1.3  The Method Detection Umit
                               (MOL defined m Section 13) for the
                               above analytes is listed in Table 1.
                               The MDL for a specific matrix may
                               differ from those listed, depending
                               upon the nature of the sample.

                               1.4  This method is restricted to use
                               by or under the supervision of
                               analysts experienced in the use of ion
                               Chromatography and in the
                               mtrepretation of the resulting ion
                               chromatogram. Each analyst must
                               demonstrate the ability to generate
                               acceptable results with this method.
                               using the procedure described in
                               Section 10.2.
                                1.5  When this method is used to
                                analyze unfamiliar samples for any of
                                the above anions. anion identification
                                should be supported by the addition
                                of  spike solutions covering the anions
                                of  interest. The spike procedure is
                                described in Section 11.6.
                         —      2.  Summary of Method

                                2.1 A small volume of sample.
                                typically 2 to 3 mL. is introduced into
                                an ion chromatograph. The anions of
                                interest are separated and measured.
                                using a system comprised of a guard
                               .column, separator column, suppressor
                                column, and conductivity detector.

                                3.  Definitions

                                3.1  Stock standard solution — a
                                concentrated solution containing a
                                certified standard that is a method
                                analyte. Stock standard solutions are
                                used to prepare secondary standard
                                solutions.

                                3.2  Calibration standards — a
                                solution of analytes prepared in the
                                laboratory from stock standard
                                solutions and diluted as needed to
                                prepare aqueous calibration solutions.

                                3.3  Quality control check sample —
                                a solution containing known
                                concentrations of analytes. prepared
                                by a laboratory other than the
                                laboratory performing the analysis.
                                The analyzing laboratory uses this
                                solution to demonstrate that it can
                                             D-358
                                                       an  J384
-------
obtain acceptable identifications and
measurements with a method.

3.4  Performance evaluation sample
— a solution of method analytes
distributed by the Quality Assurance
Branch (QAB). Environmental
Monitoring and Support Laboratory
(EMSL-Cincmnati).  USEPA, Cincinnati.
Ohio, to multiple laboratories for
analysis. A volume of the solution is
added to a known volume of reagent
water and analyzed with procedures
used for samples. Results of analyses
are used by the QAB to determine
statistically the accuracy and precision
that can be expected when a method
is performed by a competent analyst.
Analyte true values are unknown to
the analyst.

3.5  Laboratory control standards —
a solution of analytes prepared in the
laboratory by adding appropriate
volumes of the stock standard
solutions to reagent water.

3.6  Laboratory duplicates — two
aliquots of the same sample that are
treated exactly the  same throughout
laboratory analytical procedures.
Analyses of laboratory duplicates
indicate precision associated with
laboratory procedures but not the
sample collection, preservation, or
storage procedures.

3.7  Field duplicates — two samples
taken at the same time and place
under identical circumstances and
treated exactly the  same throughout
field and laboratory procedures.
Analyses of field duplicates indicate the
precision associated with sample
collection, preservation and storage,
as well as with laboratory procedures.

4.   Interferences

4.1  Interferences can be caused by
substances with retention times that
are similar to and overlap those of the
anion of interest. Large amounts of an
an ion can interfere with the peak
resolution of an adjacent anion.
Sample dilution and/or spiking can be
used to solve most interference
problems.

4.2  The water dip or negative peak
that elutes near and can interfere
with the fluoride peak can  be
eliminated by the addition of the
equivalent of 1  mL of concentrated
eluent (7.3 100X) to 100 mL of each
standard and sample.

4.3  Method interferences may be
caused by contaminants in the
reagent water, reagents, glassware,
and other sample processing
apparatus that lead to discrete
artifacts or elevated baseline in ion
chromatograms.

4.4  Samples that contain particles
larger than 0.45 microns and reagent
solutions that contain particles larger
than 0.20 microns require filtration to
prevent damage to  instrument
columns and flow systems.

5.   Safety

5.1  Normal, accepted laboratory
safety practices should be followed
during reagent preparation and
instrument operation. No known
carcinogenic materials are  used in
this method.


6.   Apparatus and Materials

6.1  Balance — Analytical, capable of
accurately weighing to the  nearest
0.0001 g.

6.2  Ion chromatograph — Analytical
system complete with ion
chromatograph and all required
accessories including syringes,
analytical columns, compressed air,
detector, and stripchart recorder. A
data system is recommended for peak
integration.

6.2.1  Anion guard column: 4 x 50
mm. Dionex P/N 030825. or
equivalent.

6.2.2  Anion separator column: 4 x
250 mm, Dionex P/N 030827, or
equivalent.

6.2.3  Anion suppressor column:
fiber, Dionex P/N 35350. or
equivalent

6.2.4  Detector — Conductivity cell:
approximately 6 i/L volume, Dionex, or
equivalent.

7.   Reagents and
Consumable Materials

7.1  Sample bottles: Glass or
polyethylene of sufficient volume to
allow replicate analyses of anions of
interest.

7.2  Reagent water: Distilled or
deionized water, free of the anions of
interest. Water should contain
particles no larger than 0.20 microns.

7.3  Eluent solution: Sodium
bicarbonate (CAS RN 144-55-8) 0.003
M, sodium carbonate (CAS RN 497-
19-8)0.0024M. Dissolve 1.0081 g
sodium bicarbonate (NaHCOs) and
1.0176 g of sodium carbonate
(NajCOj) in reagent water  and dilute
to 4 liters.
7.4  Regeneration solution (fiber
suppressor): Sulfunc acid (CAS RN
7664-93-9) 0.025N. Dilute 2.8 mL
cone, sulfuric acid (HgSO*) to 4 liters
with reagent water.

7.5  Stock standard solutions, 1000
mg/L(1 mg/mL): Stock standard
solutions may be purchased as
certified solutions or prepared from
ACS reagent grade materials (dried
at 105°C for 30 mm.) as listed below.

7.5.1  Chloride (CL1 1000 mg/L
Dissolve 1.6485 g sodium chloride
(NaCL  CAS RN 7647-14-5) in reagent
water and dilute to 1 liter.

7.5.2  Fluoride (f~] 1000 mg/L:
Dissolve 2.2100 g sodium fluoride
(NaF, CAS RN 7681 -49-4) in reagent
water and dilute to 1 liter.

7.5.3  Nitrate (NdJ-N) 1000 mg/L:
Dissolve 6.0679 g sodium nitrate
(NaNOs, CAS RN 7631-99-4) in
reagent water and dilute to 1  liter.

7.5.4  Nitrite (NO*-N) 1000 mg/L
Dissolve 4.9257 g sodium nitrite
(NaNOi CAS RN 7632-00-0) in
reagent water and dilute to 1  liter.

7.5.5  Phosphate (POl-P) 1000 mg/L
Dissolve 4.3937 g potassium
phosphate (KH2PO4. CAS RN 7778-77-
0) in reagent water and dilute to 1
liter.

7.5.5  Sulfate (SOT) 1000 mg/L
Dissolve 1.8141 g potassium sulfate
(KjSCu. CAS RN 7778-80-5) in
reagent water and dilute to 1  liter.

7.5.7  Stability of standards: Stock
standards (7.5) are  stable for at least
one month when stored at 4°C. Dilute
working standards should be prepared
weekly, except those that contain
nitrite and phosphate should be~
prepared fresh daily.

8.   Sample Collection,
Preservation and Storage

8.1  Samples should be collected in
scrupulously clean  glass or
polyethylene bottles.

8.2  Sample preservation and holding
times for the anions that can be
determined by this  method are as
follows:
                             noiumy
Analyte	Preservation    Time
Chloride       None required 28 days
Fluoride       None required 28 days
Nitrate-N      Cool to 4°C   48 hours
Nitrite-N      Cool to 4°C   48 hours
O-Phosphate-P Filter and cool 48 hours
               to4°C
Sulfate
Cool to 4°C    28 days
                                      Jtn. 1984
                D-359
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8.3  The method of preservation and
the holding time for samples analyzed
by this method are determined by the
anions of interest. In a given sample.
the anion that requires the most
preservation treatment and the
shortest holding time will determine
the preservation treatment and
holding time for the total sample.

9.   Calibration and
Standardization

9.1  Establish ion chromatographic
operating parameters equivalent to
those indicated  in Table  1.

9.2  For each analyte of interest.
prepare calibration standards at a
minimum of three concentration
levels and a blank by adding
accurately measured volumes of one
or more stock standards (7.5) to a
volumetric flask and diluting to
volume with reagent water. If the
working range exceeds the linear
range of the system, a sufficient
number of standards must be
analyzed to allow an accurate
calibration curve to be established.
One of the standards should be
representative of a concentration
near, but above, the method detection
limit if the system is operated on an
applicable attenuator range.  The other
standards should correspond to the
range of concentrations  expected in
the sample or should define  the
working range of the detector. Unless
the attenuator range settings are
proven to be linear, each setting must
be calibrated individually.

9.3  Using injections of 0.1  to 1.0 mL
(determined by  infection loop volume)
of each calibration standard, tabulate
peak height or area responses against
the concentration. The results are
used to prepare a calibration curve for
each analyte. During this procedure.
retention times must be recorded. The
retention time is inversely
proportional to the concentration.

9.4 The working calibration curve
must be verified on each working day,
or whenever the anion eluent is
changed, and after every 20 samples.
If the response or retention time for
any analyte vanes from  the expected
values by more than = 10%. the test
must be repeated, using fresh
calibration standards. If  the results
are still more than r 10%. an entire
new calibration curve must be
prepared for that analyte.

9.5  Nonlinear response can result
when  the separator column  capacity
is exceeded (overloading). Maximum
column loading (all anions) should not
exceed about 400 ppm.

10.  Quality Control

10.1  Each laboratory using this
method should have a formal quality
control program. The minimum
requirements of this program consist
of an initial demonstration of
laboratory capability (10.2) and the
analysis of spiked samples as a
continuing check on performance. The
laboratory should maintain
performance records to define the
quality of data that are generated.

10.1.1  In recognition of the rapid
advances occurring in
chromatography. the analyst is
permitted  certain options to improve
the separations or lower the cost of
measurements. Each time such
modifications to the method are made,
the analyst is required to repeat the
procedure in Section 10.2

10.1.2  The laboratory should spike
and analyze a minimum of 10% of all
samples to monitor continuing
laboratory performance. Field and
laboratory duplicates should also be
analyzed.

10.2   Before performing  any
analyses,  the analyst should
demonstrate the ability to generate
acceptable accuracy and precision
with this method, using a laboratory
control standard.

10.2.1   Select a representative
spike  concentration for each analyte
to be  measured. Using stock
standards, prepare a quality control
check sample concentrate in reagent
water 100 nmes more concentrated
than the selected concentrations.

 10.2.2  Using a pipet. add 1.00 mL
of the check sample concentrate
(10.2.1) to each of a minimum of four
 100-mL aliquots of reagent water.
Analyze the aliquots according to the
procedure in Section 11.

 10.2.3  Calculate the average
percent recovery (R), and  the standard
deviation^) of the percent recovery, for
the results.

 10.2.4  Using the appropriate data
from Table 2. determine the recovery
and single operator precision expected
for the method, and compare these
results to the values calculated in
 Section 10.2.3. If the data are not
comparable within control limits
(10.3.1). review potential problem
 areas and repeat the test.
10.3   The analyst must calculate
method performance criteria and
define the performance of the
laboratory for aach spike
concentration of analyte being
measured.

10-3.1   Calculate upper  and lower
control limits for method performance
as follows:

  Upper Control Limit (UCL) = R + 3 s
  Lower Control  Limit (LCD - R - 3 s
where R and s are calculated as in
Section 10.2.3. The UCL and LCL can
be used to construct control Chans
that are useful in observing trends in
performance.

10.4   The laboratory should develop
and maintain separate accuracy
statements of laboratory performance
for water and wastewater samples.
An accuracy statement for the method
is defined as R ± s. The accuracy
statement should be developed by the
analyses of four aliquots of water or
wastewater. as described in Section
10.2.2. followed by the calculation of
R and s.

10.5   Sefore processing any
samples, the analyst must
demonstrate through the analysis of
an aliquot of reagent water that all
glassware and reagent interferences
are under control. Each time there is
a change in reagents, a laboratory
reagent blank must be processed as a
safeguard against laboratory
contamination.

10.6   It is recommended that the
laboratory adopt additional quality
assurance practices for use with this
method. The specific practices that
are most productive depend upon  the
needs of the laboratory andnhe nature
of the samples. Field duplicates may
be analyzed to monitor the precision
of the sampling technique. When
doubt exists over the identification of
a peak in the chromatogram,
confirmatory techniques such as
sample dilution and spiking, must be
used. Whenever possible, the
laboratory should perform analysis of
quality control check samples and
participate in relevant performance
evaluation sample studies.


 11.   Procedure

 11.1  Table 1  summarizes the
 recommended operating  conditions for
 the ion chromatograph. Included m
 this table are estimated retention
 times that can be achieved by this
 method. Other columns.
 chromatographic conditions, or
                                                  D-360
                                                                 Jan.
-------
 detectors may be used if the
 requirements of Section 10.2 are met.

 11.2  Check system calibration daily
 and, if required, recalibrate as
 described in Section 9.

 11.3  Load and inject a fixed amount
 of well mixed sample. Flush injection
 loop thoroughly, using each new
 sample. Use the same size  loop for
 standards and samples. Record the
 resulting peak size in  area or peak
 height units. An automated constant
 volume injection system may also be
 used.

 11.4  The width of the retention time
 window used to make identifications
 should be based upon measurements
 of actual retention time variations of
 standards over the course of a day.
 Three times the standard deviation of
 a retention time can be used to
 calculate a suggested window size for
 a compound. However, the  experience
 of the analyst should weigh heavily in
 the interpretation of chromatograms.

 11.5  If the response for the peak
 exceeds the working range  of the
 system, dilute the sample with an
• appropriate amount of reagent water
 and reanalyze.

 11.6  If the resulting chromatogram
 fails to produce adequate resolution.
 or if identification of specific anions is
 questionable, spike the sample with
 an appropriate amount of standard
 and reanalyze.
  Note: Retention time is inversely
 proportional to concentration. Nitrate
 and sulfate exhibit the greatest
 amount of change, although all anions
 are affected to some degree. In some
 cases, this peak migration can
 produce poor resolution or
 misidentification.

 12.   Calculation

 12.1  Prepare separate calibration
 curves for each anion of interest by
 plotting peak size in area, or peak
 height units of standards against
 concentration values.  Compute
 sample concentration by comparing
 sample peak response with the
 standard curve.

 12.2  Report results  in mg/L
zero. The MDL concentrations listed m
Table 1 were obtained using reagent
water.

13.2  Single-operator accuracy and
precision for reagent, drinking and
surface water,  and mixed domestic
and industrial wastewater are listed in
Table 2.

14.  References

14.1  An nual  Book of ASTM
Standards. Part 31 Water, proposed
test method for "Anions in Water by
Ion Chromatography." p. 1485-1492
(1982).

14.2  Standard Methods for the
Examination of Water and
Wastewater, Method 400Z. "Anions
by Ion Chromatography" proposed for
the 16th Edition of Standard Methods.

14.3  Dionex, 1C 16 operation and
maintenance manual. PN 30579,
Oionex Corp., Sunnyvale, California
94086.

14.4  Method detection limit (MOD
as described in 'Trace Analyses for
Wastewater." J. Glaser. 0. Foerst.
G. McKee. S. Quave. W. Budde.
Environmental Science and
Technology. Vol. 15,  Number 12, p.
1426, December 1981.
13.  Precision and Accuracy
— Method Detection Limit
13.1  The method detection limit
(MOD is defined as the minimum
concentration of a substance that can
be measured and  reported with 99%
confidence that the value is above
                                      J»n. 1384
                                                        D-361
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Table I.    Chramatographic Conditions and Method Detection Limits in Reagent
           Water
                       Retention'          Relative             Method1
                          Time           Retention         Detection Limit
Analyte	(Mint	Time	mg/L
Fluoride
Chloride
Nitrite-N
0-Phosphate-P
Nitrate-N
Sulfate
1.2
3.4
4.5
3.0
11.3
21.4
1.0
2.8
3.8
7.5
9.4
17.8
0.005
0.015
0.004
0.061
0.013
0.206
                                  Sample Loop — 10O (iL
                                  Pump Volume — 2.30 mL/Min
Standard Conditions:
  Columns — 4s specified in 6.2
  Detector — As specified in 6.2
  Sluent — As specified in 7.3
1  Concentrations of mixed standard fmg/U
  Fluoride 3.0         0-Phosphate-P 9.0
  Chloride 4.0            Nitrate-N 30.0
  Nitrite-N 10.0            Sulfate 50.0
*• MDL calculated from data obtained using an attenuator setting of 1 itMHO full
scale. Other settings would produce an MDL proportional to their value.
Table 2. Single-Operator Accuracy and Precision
Number
Sample Spike of
Anelvte Type fmg/LJ Replicates
Chloride



Fluoride



Nitrate-N



Nitrite-N



0-Phosphate-P



Sulfate



RW
ow .
sw
ww
RW
OW
SW
ww
RW
DW
SW
WW
RW
DW
SW
WW
RW
DW
SW
ww
RW
DW
SW
ww
0.050
10.0
1.0
7.5
0.24
9.3
0.50
1.0
0.10
31.0
0.50
4.0
0.10
19.6
0.51
0.52
0.50
46.7
0.51
4.0
1.02
98.5
10.0
12.5
7
7
7
7
7
7
7
7
7
7
7
7
7
7
7
7
7
7
7
7
7
7
7
7
Mean
Recovery
%
97.7
98.2
10S.O
82.7
103.1 -
87.7
74.0
920
100.9
100,7
100.0
94.3
97.7
103.3
88.2
10O.O
100.4
102.5
94.1
97.3
102.1
104.3
111.6
134.9
Standard
Deviation
(mo/Li
0.0047
0.289
0.139
0.445
0.0009
0.075
0.0038
0.011
0.0041
0.356
0.0058
0.058
0.0014
0.1 SO
0.0053
0.018
0.019
0.386
0.020
0.04
0.066
1.475
0.709
0.466
RW = Reagent Water
DW * Drinking Water
                        SW = Surface Water
                        WW - Wastawater
                                                   D-362
                                                                 J»n. 198'-
                                                                                           TBCPO: 1984-759-102-862
-------
    FREE CHLORINE
(FIELD DETERMINATION)
         D-363
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    FREE CHLORINE

    Liquid samples were tested  in the  field  for  free  chlorine content orior
to the addition of any preservatives.  This  was  done  to determine whether A
VOfl vial preserved with sodium  thiosulfate was necessary.   Free chlorine
tests were conducted using a chlorine  test kit made by Coastal Chemical
Cornoany.  The kit is equiped with a cell  in  which  to  place the test sample,
a color chart to compare the sample with, and a  small bottle of orthotoli-
dine.   The color chart ranges from pale yellow  (0.2 ppm chlorine)  to bright
yellow  (1.0 ppm chlorine).  The chart  measures color  changes corresponding
to quantities of 0.2, 8.4, 0.6, 0.8, and  1.0 ppm chlorine.  Intermediate
chlorine levels can be estimated.

    To test for free chlorine,   liquid  is  placed  in the test  cell up to a
measured limit.   Four drops of  orthotolidine are added and the cell con-
tents are mixed.  Any color change is  compared to  the color chart.
                                    D-364
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EPA METHOD
NO. 410.4M
       D-365
-------
                        CHEMICAL OXYGEN  DEMAND

                Method 410.4  (Colorimetric,  Automated; Manual)

                                                                STORET NO. 00340

1.    Scope and Application
     1.1   This method covers the determination of COD in surface waters, domestic and industrial
           wastes.
     1.2   The applicable range of the automated method is 3-900 mg/1 and the range of the
           manual method is 20 to 900 mg/1.
2.    Summary of Method
     2.1   Sample, blanks and standards in sealed tubes are heated in an oven or block digester in
           the presence of dichromate at 15CTC. After two hours, the tubes are removed from the
           oven or digester, cooled and measured spectrophotometrically at 600 nm.
3.    Sample Handling and Preservation
     3.1   Collect the samples in glass bottles if possible. Use of plastic containers is permissible if it
           is known that no organic contaminants are present in the containers.
     3.2   Samples should be preserved with sulfuric acid to a pH < 2 and maintained at 4*C until
           analysis.
4.    Interferences
     4.1   Chlorides are  quantitatively  oxidized by dichromate and  represent  a positive
           interference. Mercuric sulfate is added to the digestion tubes to complex the chlorides.
5.    Apparatus
     5.1   Drying oven or block digestor, 150"C
     5.2   Corning culture tubes, 16 x 100 mm or 25 x 150 mm with Teflon lined screw cap
     5.3   Spectrophotometer or Technicon AutoAnalyzer
     5.4   Muffle furnace, SOOTC.
6.    Reagents
     6.1   Digestion solution: Add 10.2 g K2Cr2O7, 167 ml cone. H2SO4 and 33.3 g HgSO4 to 500 ml
           of distilled water, cool and dilute to 1 liter.
     6.2   Catalyst  solution: Add 22 g Ag2SO4 to a 4.09kg bottle of cone. H7SO4. Stir until
           dissolved.
     6.3   Sampler wash solution: Add 500 ml of cone H7SOt to 500 ml of distilled water.
     6.4   Stock potassium acid phthalate: Dissolve 0.850 g in 800 ml of distilled water and dilute to
           1 liter. 1ml =  ImgCOD
           6.4.1  Prepare  a series  of standard  solutions that  cover the  expected sample
                concentrations by diluting appropriate volumes of the stock standard.
7.    Procedure
     7.1   Wash all culture tubes and screw caps with 20% H2SO4 before their first use to prevent
           contamination. Trace contamination may be removed from the tubes by  igniting them in
           a muffle oven at 500*C for 1 hour.

Issued  1978

                                        D-366
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      7.2   Automated
           7.2.1 Add 2.5 ml of sample to the 16 x 100 mm tubes.
           7.2.2 Add 1.5 ml of digestion solution (6.1) and mix.
           7.2.3 Add 3.5 ml of catalyst solution (6.2) carefully down the side of the culture tube.
           7.2.4 Cap tightly and shake to mix layers.
           7.2.5 Process standards and blanks exactly as the samples.
           7.2.6 Place in oven or block digestor at 150°C for two hours.
           7.2.7 Cool,  and place standards in sampler  in order of decreasing concentration.
                Complete filling sampler tray with unknown samples.
           7.2.8 Measure color intensity on Auto Analyzer at 600 nm.
      7.3   Manual
           7.3.1 The following procedure  may be used if a  larger sample  is  desired or  a
                spectrophotometer is used in place of an Auto Analyzer.
           7.3.2 Add 10 ml of sample to 25 x 150 mm culture tube.
           7.3.3 Add 6 ml of digestion solution (6.1) and mix.
           7.3.4 Add 14 ml of catalyst solution (6.2) down the side of culture tube.
           7.3.5 Cap tightly and shake to mix layers.
           7.3.6 Place in oven or block digestor at 150°C for 2 hours.
           7.3.7 Cool, allow any precipitate to settle and measure intensity in spectrophotometer at
                 600 nm.  Use only optically matched culture tubes or  a single cell for spectro-
                 photometric measurement.
8.     Calculation
      8.1   Prepare a standard curve by plotting peak height or percent transmittance against known
           concentrations of standards.
      8.2   Compute concentration of samples by comparing sample response to standard curve.
9.     Precision and Accuracy
      9.1   Precision and accuracy data are not available at this time.

                                      Bibliography

1.     Jirka, A. M., and M. J. Carter, "Micro-Semi-Automated Analysis of Surface and Wastewaters
      for Chemical Oxygen Demand." Anal. Chem. ^7:1397. (1975).
                                        D-367
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D-368
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EPA METHOD
 NO. 335.2
      D-369
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                                 CYANIDE,  TOTAL

                  Method  335.2 (Titrimetric;  Spectrophotometric)

                                                                 STORET NO. 00720

 1.    Scope and Application
     1.1   This method is applicable to the determination of cyanide in drinking, surface and saline
           waters, domestic and industrial wastes.
     1.2   The titration  procedure  using silver nitrate with  p-dimethylamino-benzal-rhodanine
           indicator is used  for measuring concentrations of cyanide exceeding I  mg/1  (0.25
           mg/250 ml of absorbing liquid).
     1.3   The colorimetric procedure is used for concentrations below 1  mg/1 of cyanide and is
           sensitive to about 0.02 mg/1.
2.    Summary of Method
     2.1   The cyanide as hydrocyanic acid (HCN) is released from cyanide complexes by means of
           a reflux-distillation operation and absorbed in a scrubber containing sodium hydroxide
           solution. The cyanide ion in the absorbing solution is then determined by volumetric
           titration or colorimetrically.
     2.2   In the colorimetric measurement the cyanide is converted to cyanogen chloride, CNC1.
           by reaction with chloramme-T at a pH less than 8 without hydrolyzing to the cyanate.
           After the reaction is complete, color is formed on the addition of pyridine-pyrazolone or
           pyndine-barbituric acid reagent. The absorbance is read at 620 nm when using pyndine-
           pyrazolone or 378 nm for pyridine-barbitune  acid. To obtain colors  of comparable
           intensity,  it is essential to have the same  salt content in both  the sample and the
           standards.
     2.3   The titrimetrie measurement uses a standard solution of silver nitrate to titrate cyanide in
           the presence of a silver sensitive indicator.
3.    Definitions
     3.1   Cyanide is defined as cyanide ion and complex cyanides converted to hydrocyanic acid
           (HCN) by reaction in a reflux system of a mineral acid in the presence of magnesium ion.
4.    Sample Handling and Preservation
     4.1   The sample should be collected in  plastic or glass  bottles of 1  liter or larger size. All
           bottles must be thoroughly cleansed and thoroughly rinsed  to remove soluble material
           from containers.
     4.2   Oxidizing agents such as chlorine decompose most of the cyanides. Test a drop of the
           sample with potassium  iodide-starch test paper (Kl-starch paper); a blue color indicates
           the need for treatment. Add ascorbic acid, a few crystals at a  time, until a drop of sample
           produces no color on the indicator paper. Then add an additional 0.06 g ol .i
           ,K id lor each liter  of sample volume.

Approved  for  NPDES
Issued  1974
Editorial revision 1974 and 1978
Technical  Revision 1980
                                         D-370
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      4.3   Samples must be preserved with 2 ml of 10 N sodium hydroxide per liter of sample
           (pH > 12) at the time of collection.
      4.4   Samples should be analyzed as rapidly as possible after collection. If storage is required,
           the samples should be stored in a refrigerator or in an ice chest filled with water and ice to
           maintain temperature at 4°C.
 5.    Interferences
      5.1   Interferences are eliminated or reduced by using the distillation procedure described
           in Procedure 8.1, 8.2 and 8.3.
      5.2   Su If ides adversely affect the colorimetric  and titration procedures. Samples  thai
           contain hydrogen sulfide, metal sulfides or other compounds that may pioduce
           hydrogen sulfide during the distillation should be distilled by the optional procedure
           described in Procedure 8.2. The apparatus for  this procedure is shown in Figure 3.
      5.3   Fatty acids will distill and form soaps under the alkaline titration conditions, making the
           end point almost impossible to detect.
           5.3.1  Acidify the sample with acetic acid (1+9) to pH 6.0 to 7.0.
                 Caution: This operation must be performed in the hood and the sample left there
                 until it can be made alkaline again after the extraction has been performed.
           5.3.2  Extract with iso-octane, hexane, or chloroform (preference in order named) with a
                solvent volume equal to 20% of the sample volume.  One extraction is usually
                adequate to reduce the  fatty  acids below the interference level. Avoid multiple
                extractions or a long contact time at low pH in order to keep the loss of HCN at a
                minimum.  When the extraction is completed, immediately raise the pH  of the
                sample to above 12 with NaOH solution.
      5.4   High results may be obtained for samples that contain nitrate and/or nitrite. During
           the distillation nitrate and nitrite will form nitrous acid which will react with some
           organic compounds to form oximes. These compounds formed will decompose under
           test conditions to generate HCN. The interference of nitrate and nitrite is eliminated
           by pretreatment with sulfamic acid.
6.    Apparatus
      6.1   Reflux distillation apparatus such as shown in Figure 1 or Figure 2. The boiling P.ask
           should be of 1 liter size with inlet tube and provision for condenser. The gas absorber may
           be a Fisher-Milligan scrubber.
      6.2   Microburet, 5.0 ml (for titration).
      6.3   Spectrophotometer suitable for measurements at 578 nm or 620 nm with a 1.0 cm cell or
           larger.
      (i. 1   Reflux distillation apparatus for sulfide removal a.s shown in Figuif .1 The boiling
           I task same as (i.l. The suit idesnuhbei may be a Wheaton Rubber *709ti82 with 29  11'
           joints, sue 100 ml. The air inlet tube should not IK- fritted. The cyanide absoipumi
           vessel  should be the same as the sulfide scrubber. The air inlet tube should \H- li itted.
      f>  ">   Flow meter, such as Lab Crest with stainless steel flout (Fisher  1l-164-.">(».
7.     Reagents
      7.1   Sodium hydroxide solution, 1.25N: Dissolve 50 g of NaOH in distilled water, and dilute
           to 1  liter with distilled water.
                                        D-371
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7.2  Lead acetate: Dissolve 30 g of Pb(C2H3O2)«3H2O in 950 ml of distilled water. Adjust
     the pH to 4.5 with acetic acid. Dilute to 1 liter.
7.5  Sulfuric acid; 18N: Slowly add 500 ml of concentrated HaSO4 to 500 rnl of distilled
     water.
7.6  Sodium dihydrogenphosphate, 1  M: Dissolve 138  g  of NaH2PO4«H2O in 1 liter of
     distilled water. Refrigerate this solution.
7.7  Stock cyanide solution: Dissolve 2.51 g of KCN and 2 g KOH in 900 ml of distilled
     water. Standardize with 0.0192 N AgNO3- Dilute to appropriate concentration so thai
     1  ml = 1  mg CN.
7.8  Standard cyanide solution, intermediate: Dilute 100.0 ml of stock (I ml = I rngC.N) to
     1000 ml with distilled water (1 ml = 100.0 ug).
7.9  Working standard cyanide  solution: Prepare fresh daily by diluting 100.0  ml  ot
     intermediate cyanide solution to 1000 ml with distilled water and store in a glass
     stoppered bottle. 1 ml = 10.0 ugCN.
7.10 Standard  silver  nitrate solution, 0.0192 N: Prepare by  crushing approximately  5 g
     AgNO3 crystals and drying to constant weight at 40"C. Weigh out 3.2647 g  of dried
     AgNO], dissolve in distilled water, and dilute to 1000 ml (1 ml = 1 mg CN).
7.11 Rhodanine indicator: Dissolve 20 mg of p-dimethyl-amino-benzalrhodanine in 100 ml of
     acetone.
7.12 Chloramine T solution: Dissolve 1.0 g of white, water soluble Chloramine T in 100 ml of
     distilled water and refrigerate until ready to use. Prepare fresh daily.
7.13 Color Reagent — One of the following may be used:
     7.13.1      Pyridine-Barbituric Acid Reagent: Place 15 g of barbituric acid in a 250 mi
                volumetric flask and add just enough distilled water to wash the sides of the
                flask and wet the barbituric acid. Add 75  ml of pyridine and mix. Add 15 ml
                of cone.  HC1, mix, and cool to room temperature. Dilute to 250 ml with
                distilled water and mix. This reagent is stable for approximately six months
                if stored in a cool, dark place.
     7.13.2      Pyridine-pyrazolone solution:
          7.13.2.1   3-Methyl-I-phenyl-2-pyrazolin-5-one reagent, saturated solution: Add
                     0.25  g of 3-methyI-l-phenyl-2-pyrazolin-5-one to  50 ml of distilled
                     water, heat to 60°C with stirring. Cool to room temperature.
          7.13.2.2   3,3'Dimethyl-l, l'-diphenyl-[4,4'-bi-2  pyrazoline]-5,5'dion« (bispyra-
                     zolone): Dissolve 0.01 g of bispyrazolone in 10 ml of pyridine.
          7.13.2.3   Pour solution (7.13.2.1) through non-acid-washed filter paper. Collect
                     the filtrate. Through  the same  filter paper  pour solution (7 13.2.2)
                     collecting the filtrate in the same container as filtrate from (7 13.2.1).
                     Mix until the filtrates are homogeneous. The mixed reagent develops a
                     pink color but this does not affect the color production with cyanide if
                     used within 24 hours of preparation.
7.14 Magnesium chloride solution: Weight 510 g of MgCl2«6H;O into a 1000 ml flask, dissolve
     and dilute to 1 liter with distilled water.
7.1") Sulfamu arid.
                                    D-372
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8.    Procedure
     8.1   For samples without sulfide.
          8.1.1    Place 500 ml of sample, or an aliquot diluted to 500 ml in the 1 liter boiling
                  flask. Pipet 50 ml of sodium hydroxide (7.1) into the absorbing tube. If the
                  apparatus in Figure 1 is used, add distilled water until the spiral is covered.
                  Connect the boiling flask, condenser, absorber and trap in the train. (Figure 1
                  or 2)
          8.1.2    Start a slow stream of air entering the boiling flask by adjusting the vacuum
                  source. Adjust the vacuum so that approximately two bubbles of air per second
                  enters the boiling flask through the air inlet tube. Proceed to 8.4.
     8.2   For samples that contain sulfide.
          8.2.1    Place 500 ml of sample, or an aliquot diluted to 500 ml in the 1 liter boiling
                  flask. Pipet 50 ml of sodium hydroxide (7.1) to the absorbing tube. Add 25 ml of
                  lead acetate (7.2) to the sulfide scrubber. Connect the boiling flask, condenser.
                  scrubber and absorber in the train. (Figure3) The flow meter is connected to the
                  outlet tube of the cyanide absorber.
          8.2.2    Start a stream of air entering the boiling flask by adjusting the vacuum source.
                  Adjust the vacuum so that approximately  1.5 liters per minute enters the
                  boiling flask through the air inlet tube. The bubble  rate may not remain
                  constant while heat is being applied to the flask. It may be necessary to readj ust
                  the air rate occasionally. Proceed to 8.4.
     8.3   If samples contain NOS and or NO2 add 2 g of sulfamic acid solution (7.15) after the air
          rate is set through the air inlet tube. Mix for 3 minutes prior to addition of HjSO^
     8.4   Slowly add 50 ml 18N sulfuric aeid (7.5) through the air inlet tube. Rinse the tube with
          distilled water and allow the airflow to mix the  flask contents for 3 min. Pour 20 ml  of
          magnesium chloride (7.14) into the air inlet and wash down with a stream of water.
     8.5   Heat the solution to boiling. Reflux for one houF. Turn oil heat and continue the
          airflow for at least 15 minutes. After cooling the boiling flask, disconnect absorber and
          close off the vacuum source.
     8.6   Drain the solution from the absorber into a 250 mt volumetric flask. Wash the absorber
          with distilled water and add the washings to the flask. Dilute to the mark with distilled
          water.
     8.7   Withdraw 50 ml or less of the solution from the flask and transfer to a 100 ml volumetric
          flask. If less than 50 ml is taken, dilute to 50 ml with 0.25N sodium hydroxide solution
          (7.4). Add 15.0 ml of sodium phosphate solution (7.6) and mix.
          8.7.1    Pyridine-barbituric acid method: Add 2 ml of chloramine T (7.12) and mix.
                  See Note 1. After 1 to 2 minutes, add 5 ml of pyridine-barbituric acid solution
                  (7.13.1) and mix. Dilute to  mark with distilled water and mix again. Allow 8
                  minutes for color development then read absorbance at 578 nm in a 1 cm cell
                  within 15 minutes.
          8.7.2    Pyridine-pyrazolene method: Add 0.5 ml of chloramine T (7.12) and mix. See
                  Note  1 and 2. After 1 to 2 minutes add 5 ml of pyridine-pyrazolone solution
                                              D-373
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             (7.13.1) and mix. Dilute to mark with distilled water and mix again. After 40
             minutes read absorbance at 620 nm in a I cm cell.
             NOTE 1: Some distillates  may  contain  compounds that  have a chlorine
                       demand. One minute after the  addition of chloramine T, test for
                      residual chlorine with Kl-starch  paper. If the test is negative, add an
                      additional 0.5 ml of chlorine T. After one minute, recheck the sample.
             NOTE 2: More than 05.  ml of chloramine T will prevent the color from
                      developing with pyridine-pyrazolone.
8.8  Standard curve for samples without sulfide.
     8.8.1    Prepare a series of standards by pipeting suitable volumes of standard solution
             (7.9) into 250 ml volumetric flasks.  To each standard add 50 ml of 1.25 X
             sodium hydroxide and dilute to 250 ml with distilled water. Prepare as follows:
              ML of Working Standard Solution             Cone,  fjg CN
                      (1  ml = 10//gCN)                       per 250 ml
                              0                                BLANK
                              1.0                                  10
                              2.0                                  20
                              5.0                                  50
                             10.0                                 100
                             15.0                                 150
                             20.0                                 200
     8.8.2    It is not imperative that all standards be distilled in the same manner as the
             samples. It is recommended that at least two standards (a high and low) be
             distilled and compared to similar values on the curve to insure that the distil-
             lation technique is reliable.  If distilled standards do not agree within ±10%
             of the undistilled standards the analyst should find the cause of the apparent
             error before proceeding.
     8.8.3    Prepare a standard curve by  plotting absorbance  of standard  vs.  cyanide
             concentrations.
     8.8.4    To check the efficiency of the sample distillation, add an increment of cyanide
             from either the intermediate standard (7.8) or the working standard (7.9) to
             500 ml of sample to insure a level of 20 pg/1.  Proceed  with the analysis as in
             Procedure (8.1.1).
8.9  Standard curve for samples with sulfide.
     8.9.1    It is imperative that all standards be distilled in the same manner as the samples.
             Standards distilled by this  method will give a  linear curve, but as the concen-
             tration increases, the recovery decreases. It is recommended that  at least 3
             standards be distilled.
     8.9.2    Prepare a standard curve by plotting absorbance of standard vs. cyanide con-
             centrations.
                                    D-374
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    8.10 Titrimetric method.
         8.10.1  If the sample contains more than 1 mg/1 of CM, transfer the distillate or a
               suitable aliquot diluted to 250 ml, to a 500 ml Erlenmeyer flask. Add 10-12 drops
               of the benzalrhodanine indicator.
        8.10.2  Titrate with standard silver nitrate to the first change in color from yellow to
               brownish-pink. Titrate a distilled water blank using the same amount of sodium
               hydroxide and indicator as in the sample.
        8.10.3  The analyst should familiarize himself with the end point of the titration and the
               amount of indicator to be used before actually titrating the samples.
9.    Calculation
     9.1   If the  colorimetric procedure is used, calculate the cyanide, in ug/1, in the original
           sample as follows:

                                  CN,ug/l =  A x 1.000 x 50
                                                  B        C

             where:

             A = ug CN read from standard  curve
             B =  ml of original  sample  for distillation
             C =  ml taken for colorimetric analysis
                                         D-375
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      9.2   Using the titrimetric procedure, calculate concentration of CN as follows:
     -M    ,,     (A - B)1.000      	250	
     CN, mg/l =  -^-.—:—L-i—— x  —:—7.—r	:	?
                 ml ong. sample     ml ot aliquot titrated

           where:

           A = volume of AgNO3 for titration of sample.
           B = volume of AgNO3 for deration of blank.

10.  Precision and Accuracy
     10.1  In a single laboratory (EMSL),  using mixed industrial and domestic waste samples at
           concentrations of 0.06, 0.13, 0.28 and 0.62 mg/l CN,  the standard deviations were
           ±0.005, ;0.007,  -0.031  and ±0.094, respectively.
     10.2  In a single laboratory (EMSL),  using mixed industrial and domestic waste samples at
           concentrations of 0.28 and 0.62 mg/l CN, recoveries were 85% and 102%, respectively.

                                      Bibliography

1.    Bark, L. S., and Higson, H. G. "Investigation of Reagents for the Colorimetric Determination
     of Small Amounts of Cyanide", Talanta. 2:471^*79(1964).
2.    Elly, C. T. "Recovery of Cyanides by Modified Seifass Distillation". Journal Water Pollution
     Control Federation 40:848-856 (1968).
3.    Annual Book of ASTM Standards, Part 31, "Water", Standard D2036-75, Method A, p 503
     (1976).
4.    Standard Methods for the Examination of Water and Wastewater, 14th Edition, p 367 and 370,
     Method 413B and D( 1975).
5..  Egekeze.  J. Q.. and Oehne, F. W., "Direct Potentiometric  Determination of Cyanide in
     Biological Materials." J. Analytical Toxicology, Vol. 3, p. 119, May/June 1979.
6.    Casey, J. P., Bright, J. W., and Helms, B. D., "Nitrosation Interference in Distillation Tests
     for Cvanide." Gulf Coast Waste Disposal Authority, Houston. Texas.
                                        D-376
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ALLIHN CONDENSER

AIR INLET TUBE
— CONNECTING TUBING
ONE LITER	
BOILING FLASK
                                    SUCTION
                 FIGURE 1
   CYANIDE DISTILLATION APPARATUS
                   D-377
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   COOLING WATER
   INLET TUBE^
        HEATER*
SCREW CLAMP

     &

    TO  LOW VACUUM
       SOURCE


- ABSORBER
                           DISTILLING FLASK
                  O
             FIGURE 2
CYANIDE DISTILLATION  APPARATUS
                  D-378
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EPA METHOD
 NO. 340.1
    D-379
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                               FLUORIDE, TOTAL

        Method 340.1  (Colorimetric, SPADNS with Bellack Distillation)

                                                       STORET  NO. Total 00951
                                                                    Dissolved 00950

1.    Scope and Application
     1.1  This method is applicable to the measurement of fluoride in drinking, surface, and saline
          waters, domestic and industrial wastes.
     1.2  The method covers the range from 0.1 to about 2.5 mg/1 F. This range may be extended
          to  1000  mg/l  using the  Fluoride Ion Selective Electrode Method  (340.2) after
          distillation.
2.    Summary of Method
     2.1  Following distillation to remove interferences, the sample is treated with the SPADNS
          reagent The loss of color resulting from the reaction of fluoride with the zirconyl-
          SPADNS dye is a function of the fluoride concentration.
3.    Comments
     3.1  The SPADNS reagent is more tolerant of interfering  materials than other accepted
          fluoride  reagents.  Reference  to  Table 414:1,  p 388,  Standard  Methods  for  the
          Examination of Waters and Wastewaters, 14th Edition, will help the analyst decide if
          distillation is required. The addition of the highly colored SPADNS reagent must be
          done with utmost accuracy because the fluoride concentration is measured as a difference
          of absorbance in the blank and the sample. A small error in reagent additon is the most
          prominent source of error in this test.
     3.2  Care must be taken to avoid overheating the flask above  the level of the solution. This is
          done by maintaining an even flame entirely under the boiling flask.
4.    Apparatus
     4.1  Distillation apparatus:  A  1-liter  round-bottom, long-necked  pyrex boiling flask,
          connecting tube, efficient condenser, thermometer adapter and thermometer reading to
          200*C. All connections should be ground glass. Any apparatus equivalent to that shown
          in Figure 1 is acceptable.
     4.2  Colorimeter One of the following
          4.2.1 Spectrophotometer for use at 570 nm providing a light path of at least 1 cm.
          4.2.2 Filter photometer equipped with a  greenish yellow filter  having maximum
               transmittance at 550 to 580 nm and a light path of at least 1 cm.
5.    Reagents
     5.1  Sulfuric acid, H2SO4, cone.
Approved for NPDES and SDWA
Issued 1971
Editorial revision 1974 and 1978

                                       D-380
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      5,2   Silver sulfate, Ag2SO4 crystals.
      5.3   Stock fluoride  solution: Dissolve 0.221 g anhydrous sodium fluoride, NaF, in distilled
           water in a 1-liter volumetric flask and dilute to the mark with distilled water; 1.00 ml =
           O.lmgF.
      5.4   Standard fluoride solution: Place  100 ml stock fluoride solution (5.3)  in  a  1 liter
           volumetric flask and dilute to the mark with distilled water; 1.00 ml = 0.010 mg F.
      5.5   SPADNS solution:  Dissolve  0.958 g SPADNS, sodium  2-(parasulfophenylazo)-l,8-
           dihydroxy-3,6-naphthalene disulfonate, in distilled water in a 500 ml volumetric flask
           and dilute to the mark. Stable indefinitely if protected from direct sunlight.
      5.6   Zirconyl-acid reagent: Dissolve 0.133 g zirconyl chloride octahydrate, ZrOCI2»8H2O in
           approximately  25 ml distilled water in a 500 ml volumetric flask. Add 350 ml cone HCI
           and dilute to the mark with distilled water.
      5.7   Acid-zirconyl-SPADNS reagent: Mix equal  volumes of SPADNS solution (5.5) and
           zirconyl-acid reagent (5.6). The combined reagent is stable for at least 2 years.
      5.8   Reference solution: Add 10 ml SPADNS solution (5.5) to 100 ml distilled water. Dilute 7
           ml cone HCI to 10 ml and add to the dilute SPADNS solution. This solution is used for
           zeroing the spectrophotometer or photometer. It is stable and may be used indefinitely.
      5.9   Sodium arsenite solution: Dissolve 5.0 g NaAsO2 in distilled water in a 1-liter volumetric
           flask and dilute to the mark with distilled water (CAUTION: Toxic-avoid ingestion).
6.     Procedure
      6.1   Preliminary distillation
           6.1.1 Place 400 ml distilled water in the distilling flask.
           6.1.2 Carefully add 200 ml cone. H2SO4 and swirl until contents are homogeneous.
           6.1.3 Add 25 to 35 glass beads, connect the apparatus (Figure 1) making sure all joints
                are tight.
           6.1.4 Heat slowly at first, then as rapidly as the efficiency  of the condenser will  permit
                (distillate must be cool) until the temperature of the flask contents reaches exactly
                180'C.  Discard the distillate.  This process removes fluoride contamination and
                adjusts the acid-water ratio for subsequent distillations.
           6.1.5 Cool to 120*C or below.
           6.1.6 Add 300  ml sample, mix thoroughly, distill as in 6.1.4 until temperature reaches
                180*C. Do not heat above 180*C to prevent sulfate carryover.
           6.1.7 Add Ag,SO4 (5.2) at a rate of 5 mg/mg Cl when high chloride samples are distilled.
           6.1.8 Use the sulfuric acid solution  in the flask repeatedly  until the contaminants from
                the samples accumulate to such an extent that recovery is affected or interferences
                appear in the distillate. Check periodically by distilling standard fluoride samples.
           6.1.9 High fluoride samples may require that the still be flushed by using distilled water
                and combining distillates.
     6.2   Colorimetric Determination:
           6.2.1 Prepare fluoride standards in the range 0 to 1.40 mg/1 by diluting appropriate
                quantities of standard fluoride solution (5.4) to 50 ml with distilled water.
                                        D-381
-------
              CONNECTING TUBE
        THERMOMETER
THERMOMETER ADAPTER ^
             1-liter
    ROUND BOTTOM
        FLASK
CONDENSER
              BURNER

                                       300-ml
O                                       VOLUMETRIC
                                       FLASK

      FIGURE 1  DIRECT DISTILLATION APPARATUS
               FOR  FLUORIDE. .
                       D-382
-------
          6.2.2 Pipet 5.00 ml each of SPADNS solution (5.5) and zirconyl-acid reagent (5.6) or
                10.00 ml of the mixed acid-zirconyl-SPADNS reagent (5.7) to each standard and
                mix well.
          6.2.3 Set  photometer to zero with reference solution (5.8) and immediately obtain
                absorbance readings of standards.
          6.2.4 Plot absorbance versus concentration. Prepare a new standard curve whenever
                fresh reagent is made.
          6.2.5 If residual chlorine is present pretreat the sample with 1 drop (0.05 ml) NaAsO2
                solution  (5.9)  per 0.1  mg residual  chlorine  and  mix.  Sodium  arsenite
                concentrations of 1300 mg/1 produce an error of 0. 1 mg/1 at 1 .0 mg/1 F.
          6.2.6 Use a 50 ml sample or a portion diluted to 50 ml. Adjust the temperature of the
                sample to that used for the standard curve.
          6.2.7 Perform step 6.2.2 and 6.2.3.
7.    Calculations
     7. 1  Read the concentration in the 50 ml sample using the standard curve (6.2.4)
     7.2  Calculate as follows:

                    mgF x 1.000
          mg/1 F =   ml sample

     7.3  When a sample (ml sample) is dilutee! to a volume (B) and then a portion (C) is analyzed,
          use:
8.    Precision and Accuracy
     8. 1  On a sample containing 0.83 mg/1 F with no interferences, 53 analysts using the Bellack
          distillation and the SPADNS reagent obtained a mean of 0.81 mg/1 F with a standard
          deviation of ±0.089 mg/1.
     8.2  On  a  sample containing  0.57  mg/1  F (with 200 mg/1  SO4 and  10 mg/1 Al  as
          interferences) 53 analysts using the Bellack distillation obtained a mean of 0.60 mg/IF
          with a standard deviation of ±0. 103 mg/1.
     8.3  On a sample containing 0.68 mg/1 F (with 200 mg/1 SO4, 2 mg/1 Al and 2.5 mg/1
          [Na(PO3)6] as interferences), 53 analysts using the Bellack distillation obtained a mean of
          0.72 mg/1 F with a standard deviation of ±0.092 mg/1. (Analytical Reference Service,
          Sample 1 1 1-B water, Fluoride, August, 1961.)

                                      Bibliography

1.    Standard Methods for the Examination of Water and Wastewater, p. 389-390 (Method No.
     414A, Preliminary Distillation Step) and p. 393-394 (Method 414C SPADNS) 14th Edition,
     (1975).
2.    Annual Book of ASTM Standards, Part 3 1 , "Water", Standard D 1 1 79-72, Method A, p. 3 1 0
     (1976).

                                         D-383
-------
t>

00
00
-------
         PH
(FIELD DETERMINATION)
        D-385
-------
    oH
    Liquid and sludge  samoles  were tested for- oH in the field  orior  to  tne
addition of any preservatives.   Values of oH were measured usinq  "AlKacia
Test Ribbon" manufactured  by Fiscner Scientific Cornoany.  Tnis  oH paoer
provides 5 distinct color  changes ranqing from violet  ( DH = cl)  to dark  olue
(pH = 10) .   fl color comparison chart is included with the paoer.   The cnart
indicates the colors for pH  values of S,  4,  6,  8, and  liZl. Intermediate  oH
values can be estimated.

    To determine the pH a  liquid  sample,  a section of the oH ribbon  is
removed from the dispenser and a  small amount of liquid  (a few  droos)  is
aoplied to the paper.  flny color  change will occur immediately  and  is corn-
pared to the color chart while the paper is still wet.  To determine the DH
of a sludge sample, a  small amount of sludge is aoplied to the  paper.   Time
is allowed for the fluid content  of the sludge to absorb into  the oH rib-
bon. Once this has occurred, any  color change is compared to the  chart.
                                    D-386
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EPA METHOD
 NO. 150.1
      D-387
-------
                                          pH

                            Method 150.1 (Electrometric)

                                                                       STORET NO.
                                                          Determined on  site   00400
                                                                   Laboratory   00403

1.    Scope and Application
     1.1  This method is applicable to drinking, surface, and saline waters, domestic and industrial
          wastes.
2.    Summary of Method
     2.1  The pH of a sample is determined electrometrically using either a glass electrode in
          combination with a reference potential or a combination electrode.
3.    Sample Handling and Preservation
     3.1  Samples should be analyzed as soon as possible preferably in the field  at the time of
          sampling.
     3.2  High-purity waters and waters not at equilibrium with the atmosphere are subject to
          changes when exposed to the atmosphere, therefore the sample containers should be
          filled completely and kept sealed prior to analysis.
4.    Interferences
     4.1  The glass electrode,  in general,  is not subject to solution interferences from color,
          turbidity, colloidal matter, oxidants, reductants or high salinity.
     4.2  Sodium error at pH levels greater than  10 can be reduced or eliminated by using a "low
          sodium error" electrode.
     4.3  Coatings of oily material or paniculate matter can impair electrode response. These
          coatings can  usually  be removed by gentle wiping or detergent washing, followed by
          distilled water rinsing. An additional treatment with hydrochloric acid (1+9) may be
          necessary to remove any remaining film.
     4.4  Temperature effects on the electrometric measurement of pH arise from two sources.
          The first is caused by the change in electrode output at various temperatures. This
          interference can be controlled with instruments having temperature compensation or by
          calibrating the electrode-instrument system at the temperature  of the samples. The
          second source is the change of pH inherent in the sample at various temperatures. This
          error is sample dependent and cannot be controlled, it should therefore be noted by
          reporting both the pH and temperature at the time of analysis.
5.    Apparatus
     5.1  pH Meter-laboratory or field model. A wide variety of instruments are commercially
          available with various specifications and optional equipment.


Approved for NPDES
Issued  1971
Editorial revision 1978

                                          D-388
-------
     5.2  Glass electrode.
     5.3  Reference electrode-a calomel, silver-silver chloride or other reference electrode of
          constant potential may be used.
          NOTE  1:  Combination electrodes  incorporating  both measuring and  reference
          functions are convenient to use and are available with solid, gel type filling materials that
          require minimal maintenance.
     5.4  Magnetic stirrer and Teflon-coated stirring bar.
     5.5  Thermometer or temperature sensor for automatic compensation.
6.    Reagents
     6.1  Primary standard buffer salts are available from the National Bureau of Standards and
          should be used in situations where extreme accuracy is necessary.
          6.1.1  Preparation of reference solutions from these salts require some special precautions
                and handling'" such as low conductivity dilution water, drying ovens, and carbon
                dioxide free purge gas. These solutions  should be replaced at least once each
                month.
     6.2  Secondary standard buffers may be prepared from NBS salts or purchased as a solution
          from commercial vendors. Use of these commercially available solutions, that have been
          validated by comparison to NBS standards, are recommended for routine use.
7.    Calibration
     7.1  Because of the wide variety of pH meters and accessories, detailed operating procedures
          cannot be incorporated into this  method. Each analyst must be acquainted with  the
          operation of each system and familiar with all instrument functions. Special attention to
          care of the electrodes is recommended.
     7.2  Each instrument/electrode system must be calibrated at a minimum of two points that
          bracket the expected pH of the samples and are approximately  three pH units or more
          apart.
          7.2.1  Various instrument designs may involve use of a "balance" or "standardize" dial
                and/or a slope adjustment as outlined in the manufacturer's instructions. Repeat
                adjustments  on successive portions of the  two buffer solutions as outlined in
                procedure 8.2 until readings are within 0.05 pH units of the buffer solution value.
8.    Procedure
     8.1  Standardize the meter and electrode system as outlined in Section 7.
     8.2  Place the sample or buffer solution in  a clean glass beaker using a sufficient volume to
          cover  the sensing  elements  of the electrodes and to give adequate clearance for  the
          magnetic stirring bar.
          8.2.1  If field measurements are being made the electrodes may be immersed directly in
                the sample stream to an adequate depth and moved in a manner to insure sufficient
                sample movement across the electrode sensing element as indicated by drift free
                (< 0.1 pH) readings.
     8.3  If the sample temperature differs by more than 2°C from the buffer solution the measured
          pH values must be  corrected. Instruments are equipped with automatic  or  manual
                  '"National Bureau of Standards Special Publication 260.

                                          D-389
-------
9.
10.
     compensators  that  electronically  adjust  for  temperature  differences.  Refer  to
     manufacturer's instructions.
8.4  After rinsing and gently wiping the electrodes,  if necessary, immerse them into the
     sample beaker or sample stream and stir at a constant rate to provide homogeneity and
     suspension of solids. Rate of stirring should minimize the air transfer rate at the air water
     interface  of  the sample.  Note and  record  sample pH and temperature.  Repeat
     measurement on successive volumes of sample until values differ by less than 0.1 pH
     units. Two or three volume changes are usually sufficient.
Calculation
9.1  pH meters read directly in pH units. Report pH to the nearest 0.1 unit and temperature
     to the nearest *C.
Precision and Accuracy
10.1  Forty-four analysts  in twenty  laboratories  analyzed six  synthetic  water samples
     containing exact increments of hydrogen-hydroxyl ions, with the following results:
        pH Units
           3.5
           3.5
           7.1
           7.2
           8.0
           8.0
                      Standard Deviation
                          pH Units

                            0.10
                            0.11
                            0.20
                            0.18
                            0.13
                            0.12
 Bias,
                                                                   Accuracy as
 -0.29
 -0.00
+ 1.01
 -0.03
 -0.12
+0.16
  Bias,
pH  Units

  -0.01

  +0.07
  -0.002
  -0.01
  +0.01
(FWPCA Method Study I, Mineral and Physical Analyses)
      10.2  In a single laboratory (EMSL), using surface water samples at an average pH of 7.7, the
           standard deviation was tO.l.

                                       Bibliography

1.     Standard Methods for the Examination of Water and Wastewater, 14th Edition, p 460, (1975).
2.     Annual Book of ASTM Standards, Part 31, "Water", Standard D1293-65, p 178 (1976).
                                          D-390
-------
EPA METHOD
 NO. 413.1
       D-391
-------
                OIL AND GREASE, TOTAL,  RECOVERABLE

           Method  413.1  (Gravimetric,  Separatory  Funnel Extraction)

                                                                STORET NO. 00556

1.    Scope and Application
     1.1  This method includes the measurement of fluorocarbon-113 extractable matter from
          surface  and saline waters,  industrial and domestic wastes. It is applicable  to  the
          determination of relatively non-volatile hydrocarbons, vegetable oils, animal fats, waxes,
          soaps, greases and related matter.
     1.2  The method is not applicable to measurement of light hydrocarbons  that volatilize at
          temperatures below 70*C. Petroleum fuels from  gasoline through #2 fuel oils  are
          completely or partially lost in the solvent removal operation.
     1.3  Some crude oils and heavy fuel oils contain  a significant percentage of residue-type
          materials that are  not soluble  in fluorocarbon-113. Accordingly, recoveries of these
          materials will be low.
     1.4  The method covers the range from 5 to 1000 mg/1 of extractable material.
2.    Summary of Method
     2.1  The sample is acidified to a low pH (< 2) and serially extracted with fluorocarbon-113 in
          a separatory funnel. The solvent is evaporated from the extract and the residue weighed.
3.    Definitions
     3.1  The definition of oil and grease is based on the procedure used. The  nature of the oil
          and/or grease, and the presence of extractable non-oily matter will influence the material
          measured and interpretation of results.
4.    Sampling and Storage
     4.1  A representative sample of 1 liter volume should be collected in a glass bottle. If analysis
          is to be delayed for more than a few hours, the sample is preserved by the addition of 5 ml
          HC1 (6.1) at the time of collection and refrigerated at 4*C.
     4.2  Because losses of grease will occur on sampling equipment, the collection of a composite
          sample is impractical. Individual portions collected at prescribed time intervals must be
          analyzed separately to obtain the average concentration over an extended period.
5.    Apparatus
     5.1  Separatory  funnel, 2000 ml, with Teflon stopcock.
     5.2  Vacuum pump, or other source of vacuum.
     5.3  Flask, boiling, 125 ml (Corning No. 4100 or equivalent).
     5.4  Distilling head, Claisen or equivalent.
     5.5  Filter paper, Whatman No. 40,11 cm.
6.    Reagents
     6.1  Hydrochloric acid, 1:1. Mix equal volumes of cone. HC1 and distilled water.

Approved for  NPDES
Issued  1974
Editorial revision  1978

                                        D-392
-------
      6.2   Flurocarbon-113,(l,l,2-trichloro-l,2,2-trifluoroethane), b. p. 48°C.
      6.3   Sodium sulfate, anhydrous crystal.
7.    Procedure
      7.1   Mark the sample bottle at the water meniscus for later determination of sample volume.
           If the sample was not acidified at time of collection, add 5 ml hydrochloric acid (6.1) to
           the sample bottle. After mixing the sample, check the pH by touching pH-sensitive paper
           to the cap to insure that the pH is 2 or lower. Add more acid if necessary.
      7.2   Pour the sample into a separatory funnel.
      7.3   Tare a boiling flask (pre-dried in an oven at 103°C and stored in a desiccator).
      7.4   Add 30 ml fluorocarbon-113 (6.2) to the sample bottle and rotate the bottle to rinse the
           sides. Transfer the solvent into the separatory funnel. Extract by shaking vigorously for 2
           minutes. Allow the layers to separate, and filter the solvent layer into the flask through a
           funnel containing solvent moistened filter paper.
           NOTE: An emulsion that fails to dissipate can be broken by pouring about 1 g sodium
           sulfate (6.3) into the filter paper cone and slowly draining the emulsion through the salt.
           Additional 1 g portions can be added to the cone as required.
      7.5   Repeat (7.4) twice more, with additional portions of fresh solvent, combining all solvent
           in the boiling flask.
      7.6   Rinse the tip of the separatory funnel, the filter paper, and then  the runnel with a total of
           10-20 ml solvent and collect the rinsings in the flask.
      7.7   Connect the boiling flask to the distilling head and evaporate the solvent by immersing
           the lower half of the flask in water at 70*C. Collect the solvent for reuse. A solvent blank
           should accompany each set of samples.
      7.8   When the temperature in the distilling head reaches 50°C or the flask appears dry remove
           the distilling head. Sweep out the flask for 15 seconds with air to remove solvent vapor by
           inserting a glass tube connected to a vacuum source. Immediately remove the flask from
           the heat source and wipe the outside to remove excess moisture and fingerprints.
      7.9   Cool the boiling flask in a desiccator for 30 minutes and weigh.
8.    Calculation
      8.1   mg/1 total oil and grease =
           where:

           R = residue, gross weight of extraction flask minus the tare weight, in milligrams.
           B  =  blank determination, residue  of equivalent volume of extraction  solvent,  in
                milligrams.
           V = volume of sample, determined  by refilling  sample bottle to calibration line and
                correcting for acid addition if necessary, in liters.
                                           D-393
-------
(              9.   Precision and Accuracy
                    9.1   The two oil and grease methods in this manual were tested by a single laboratory (EMSL)
                          on sewage. This method determined the oil and grease level in the sewage to be 12.6
                          mg/1. When 1 liter portions of the sewage were dosed with 14.0 mg of a mixture of #2
                          fuel oil and Wesson oil, the recovery was 93% with a standard deviation of ±0.9 mg/1.

                                                     Bibliography

               1.   Standard Methods for.the Examination of Water and Wastewater,  14th Edition, p 515,
                    Method 502A,( 1975).
               2.   Blum, K. A., and Taras, M. J., "Determination of Emulsifying Oil in Industrial Wastewater",
                    JWPCF Research Suppl. 40, R404 (1968).
                                                       D-394
-------
OIL AND GREASE ANALYSIS OF SLUDGE  SAMPLES
             -RETORT METHOD-
                  D-395
-------
          Oil and Grease Analysis of Sludge Samples
 A study was performed to determine a quick,  reliable method for
 the determination of oil and grease in sludge samples.   Oil and
 grease is defined to mean that material which can be extracted
 from the sample by freon extraction and which is determined by
 gravimetry after evaporating the freon from  sodium sulfate dried
-extract.  Three methods were compared: the straight freon
 extraction method (A); the sonication assisted freon extraction
 method (8) and the freon extraction following retort (C).  A
 brief description of each method will be given below.

      Method A:  A weighed aliquot (approximately 10 grams) of
      well mixed sludge is acidified to pH 2  by addition a few
      drops of dilute HC1.  The sample is extracted by shaking
      with three successive portions (30 mL each) of freon.  The
      extracts are dried by passing them through anhydrous sodium
      sulfate contained in a filter tube plugged with glass wool.
      The sodium sulfate is rinsed with an additional aliquot of
      clean freon which is then combined with the extracts.  The
      freon is then removed by evaporation over a steam-bath and
      the oil and grease residue is determined by gravimetric
      analysis.

      Method B:  Method 8 is identical to Method A except that the
      extraction is assisted by sonicating the freon and sludge to
      attempt to get a better recovery of oil and grease.

      Method C--  A weighed aiiquot (approximately 20 grama) of
      well mixed sludge is acidified to pH 2  by addition of a feu
      drops of dilute HC1.  The sample is then placed in a retort
      apparatus.  The sample is heated frow ambient to approxim-
      ately 500 degrees centigrade over 30 minutes.  The
      distillate is condensed and collected in a aide arm
      receiver.  The oil and grease is determined in the
      distillate by the procedure outlined in Method A.

 The results of this study suggest that the retort  step (Method C)
 yields a higher oil and grease result with considerably  lass
 variability than either Methods A or  8.  The sonication  step
 (Method B) actually yielded a lower oil and grease result than
 either Methods A or C.  This was contrary to our expectations,
 however, there was no  specific attempt to discover  the reason  for
 the  lower results.

 The  results of this study are presented graphically in  figures  1
 and  2.  Two actual  field samples were used.  One was considered
 to have a moderate oil  and  grease value and  the other a  high
 value.
                                  D-396
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                                                                                             46 1320
VO
--a
-------
CO
OS
 I
Q
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EPA METHOD
 NO. 160.1
      D-399
-------
                             RESIDUE, FILTERABLE

                    Method 160.1 (Gravimetric,  Dried at 180°Q

                                                                 STORET  NO.  70300

1.    Scope and Application
     1.1   This method is applicable to drinking, surface, and saline waters, domestic and industrial
           wastes.
     1.2   The practical range of the determination is 10 mg/1 to 20,000 mg/1.
2.    Summary of Method
     2.1   A well-mixed sample is  filtered through a standard glass fiber filter. The filtrate is
           evaporated and dried to constant weight at 180*C.
     2.2   If Residue, Non-Filterable is  being determined, the filtrate from that method  may be
           used for Residue, Filterable.
3.    Definitions
     3.1   Filterable residue is defined as those solids capable of passing through a glass fiber filter
           and dried to constant weight at 18CTC.
4.    Sample Handling and Preservation
     4.1   Preservation of the sample is not practical; analysis should begin as soon as possible.
           Refrigeration or icing to  4*C, to minimize microbiological decomposition of solids, is
           recommended.
5.    Interferences
     5. 1   Highly mineralized waters containing significant concentrations of calcium, magnesium,
           chloride and/or  sulfate  may be  hygroscopic and will require prolonged  drying,
           desiccation and rapid weighing.
     5.2   Samples containing high concentrations of bicarbonate will require careful and possibly
           prolonged drying at 180*C to insure that all the bicarbonate is converted to carbonate.
     5.3   Too much residue in the evaporating dish will crust over and entrap water that will not
           be driven off during drying. Total residue should be limited to about 200 mg.
6.    Apparatus
     6.1   Glass fiber filter discs, 4.7 cm  or 2.1 cm, without organic binder, Reeve Angel type 934-
           AH, Gelman type A/E, or equivalent.
     6.2   Filter holder,, membrane filter funnel or Gooch crucible adapter.
     6.3   Suction flask, 500 ml.
     6.4   Gooch crucibles, 25 ml (if 2.1 cm filter is used).
     6.5   Evaporating  dishes, porcelain,  100 ml  volume. (Vycor or platinum dishes  may be
           substituted).
     6.6   Steam bath.
     6.7   Drying oven, 180*C ±2*C.
     6.8   Desiccator.

Approved for  NPDES
Issued  1971

                                          D-400
-------
     6.9   Analytical balance, capable of weighing to 0.1 mg.
7.   Procedure
     7.1   Preparation of glass fiber filter disc: Place the disc on the membrane filter apparatus or
           insert into bottom of a suitable Gooch crucible. While vacuum is applied, wash the disc
           with three successive 20 ml volumes of distilled water. Remove all traces of water by
           continuing to apply vacuum after water has passed through. Discard washings.
     7.2   Preparation of evaporating dishes: If Volatile Residue is also to be measured heat the
           clean dish to 550 ±50°C for one hour in a muffle furnace. If only Filterable Residue is to
           be measured heat the clean dish to 180 ±2°C for one hour. Cool in desiccator and store
           until needed. Weigh immediately before use.
     7.3   Assemble the filtering apparatus and begin suction. Shake the sample vigorously and
           rapidly transfer 100 ml to the funnel by means of a 100 ml graduated cylinder. If total
           filterable residue is low, a larger volume may be filtered.
     7.4   Filter the sample through the glass fiber filter, rinse with three 10 ml portions of distilled
           water and continue to apply vacuum for about 3 minutes after filtration is complete to
           remove as much water as possible.
     7.5   Transfer 100 ml (or a larger volume) of the filtrate to a weighed evaporating dish and
           evaporate to dryness on a steam bath.
     7.6   Dry the evaporated sample for at least one hour at 180  ±2°C. Cool in a desiccator and
           weigh. Repeat the drying cycle until a constant weight is obtained or until weight loss is
           less than 0.5 mg.
8.   Calculation
     8.1   Calculate filterable residue as follows:
           FUterable residue, mg/1  =  ^	-tr-—'•—
           where:

           A = weight of dried residue + dish in mg
           B = weight of dish in mg
           C = volume of sample used in ml
9.    Precision and Accuracy
     9.1   Precision and accuracy are not available at this time.

                                       Bibliography

1.    Standard Methods for the Examination of Water and Wastewater, 14th Edition, p 92, Method
     208B,(1975).
                                           D-401
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t
£>
O
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EPA METHOD
 NO. 160.2
      D-403
-------
                          RESIDUE,  NON-FILTERABLE

                 Method  160.2 (Gravimetric, Dried  at 103-105°O

                                                                 STORET  NO.  00530

1.    Scope and Application
     1.1  This method is applicable to drinking, surface, and saline waters, domestic and industrial
          wastes.
     1.2  The practical range of the determination is 4 mg/1 to 20,000 mg/1.
2.    Summary of Method
     2.1  A well-mixed sample is filtered through a glass fiber filter, and the residue retained on the
          filter is dried to constant weight at 103-105*C.
     2.2  The filtrate from this method may be used for Residue, Filterable.
3.    Definitions
     3.1  Residue, non-filterable, is defined as those solids which are retained by a glass fiber filter
          and dried to constant weight at 103-105*C.
4.    Sample Handling and Preservation
     4.1  Non-representative particulates such as leaves, sticks,  fish, and lumps of fecal matter
          should be excluded from the sample if it is determined that their inclusion is not desired
          in the final result.
     4.2  Preservation of the sample is not practical; analysis should begin as soon as possible.
          Refrigeration or icing to 4*C, to minimize microbiological  decomposition of solids, is
          recommended.
5.    Interferences
     5.1  Filtration apparatus, filter material, pre-washing, post-washing, and drying temperature
          are specified because these variables have been shown to affect the results.
     5.2  Samples high in Filterable Residue (dissolved solids), such as saline waters, brines and
          some wastes, may be subject to a positive interference. Care must be taken in selecting the
          filtering apparatus so that washing of the filter and any dissolved solids in the filter (7.5)
          minimizes this potential interference.
6.    Apparatus
     6.1  Glass fiber filter discs, without organic binder,  such as Millipore AP-40, Reeves Angel
          934-AH, Gelman type A/E, or equivalent.
          NOTE: Because of the physical nature of glass fiber filters, the absolute pore size cannot
          be controlled or measured. Terms such as "pore size", collection efficiencies and effective
          retention are used to define this property in glass fiber filters. Values for these parameters
          vary for the  filters listed above.
     6.2  Filter  support: filtering apparatus with reservoir and a coarse (40-60 microns) fritted
          disc as a filter support.
Approved for NPDES
Issued 1971

                                          D-404
-------
          NOTE: Many funnel designs are  available in glass  or porcelain. Some of the most
          common are Hirsch or Buchner funnels, membrane filter holders and Gooch crucibles.
          All are available with coarse fritted disc.
     6.3  Suction flask.
     6.4  Drying oven, 103-105°C.
     6.5  Desiccator.
     6.6  Analytical balance, capable of weighing to 0.1 mg.
7.    Procedure
     7.1  Preparation of glass fiber filter disc: Place the glass fiber filter on the membrane filter
          apparatus or insert into bottom of a suitable Gooch crucible with wrinkled surface up.
          While vacuum is applied, wash the disc with three successive 20 ml volumes of distilled
          water. Remove all traces of water by continuing to apply vacuum after water has passed
          through. Remove filter from membrane filter apparatus or both crucible and filter if
          Gooch  crucible is used, and dry in an oven at 103-105°C for one  hour. Remove to
          desiccator and store until needed.  Repeat the drying cycle until a constant weight is
          obtained (weight loss is less than 0.5 mg). Weigh immediately before use. After weighing,
          handle the filter or crucible/filter with forceps or tongs only.
     7.2  Selection of Sample Volume
          For a 4.7 cm diameter filter, filter 100  ml of sample. If weight of captured residue is less
          than  1.0 mg, the sample volume must be increased to provide at least 1.0 mg of residue. If
          other filter diameters are used, start with a sample volume equal to 7 ml/cm2 of filter area
          and collect at least a weight of residue proportional to the 1.0 mg stated above.
          NOTE: If during filtration of this  initial volume the  filtration rate drops rapidly, or if
          filtration time exceeds 5 to 10 minutes,  the following scheme is recommended:  Use an
          unweighed glass fiber filter of choice affixed in the filter assembly. Add a known volume
          of sample to the  filter funnel and record the  time elapsed after selected volumes have
          passed through the filter. Twenty-five  ml increments for timing are suggested. Continue
          to record the time and volume increments until fitration  rate  drops rapidly.  Add
          additional sample if the filter funnel volume is inadequate to reach a  reduced rate. Plot
          the observed time versus volume filtered. Select the proper filtration volume as that just
           short of the time a significant change in filtration rate occurred.
     7.3   Assemble the filtering apparatus and begin suction. Wet the filter with a small volume of
           distilled water to seat it against the fritted support.
     7.4   Shake  the  sample vigorously and quantitatively transfer the predetermined  sample
           volume selected in 7.2 to the filter using a graduated cylinder. Remove all traces of water
           by continuing to apply vacuum after sample has passed through.
     7.5   With suction on, wash the graduated cylinder, filter, non-filterable residue and filter
           funnel  wall with three  portions  of distilled water allowing complete drainage between
           washing. Remove all traces of water by continuing  to apply vacuum after water has
           passed through.
           NOTE: Total volume of wash water used should equal approximately 2 ml per cm:. For a
           4.7 cm filter the total volume is 30 ml.
                                           D-405
-------
     7.6   Carefully remove the filter from the filter support. Alternatively, remove crucible and
           filter from crucible adapter. Dry at least one hour at 103-105*C. Cool in a desiccator and
           weigh. Repeat the drying cycle until a constant weight is obtained (weight loss is less than
           0.5 mg).
8.    Calculations
     8.1   Calculate non-filterable residue as follows:
           Non-filterable residue, mg/1 = ^	Bj* 1.000
           where:

           A = weight of filter (or filter and crucible) -t- residue in mg
           B = weight of filter (or filter and crucible) in mg
           C = ml of sample filtered
9.    Precision and Accuracy
     9.1   Precision data are not available at this time.
     9.2   Accuracy data on actual samples cannot be obtained.

                                       Bibliography

1.    NCASI Technical Bulletin No. 291, March 1977. National Council of the Paper Industry for
     Air and Stream Improvement, Inc., 260 Madison Ave., NY.
                                           D-406
-------
EPA METHOD
 NO. 160.3
        D-407
-------
                                 RESIDUE,  TOTAL

                 Method  160.3 (Gravimetric, Dried at  103-105T)

                                                                 STORET NO. 00500

1.    Scope and Application
     1.1  This method is applicable to drinking, surface, and saline waters, domestic and industrial
          wastes.
     1.2  The practical range of the determination is from 10 mg/1 to 20,000 mg/1.
2.    Summary of Method
     2.1  A well mixed  aliquot of  the  sample is quantitatively  transferred to a  pre-weighed
          evaporating dish and evaporated to dryness at 103-105°C.
3.    Definitions
     3.1  Total Residue  is defined  as  the  sum of the homogenous suspended and dissolved
          materials in a sample.
4.    Sample Handling and Preservation
     4.1  Preservation of the sample is not  practical;  analysis should begin as soon as possible.
          Refrigeration or icing to 4°C, to minimize microbiological  decomposition of solids, is
          recommended.
5.    Interferences
     5.1  Non-representative particulates such as leaves, sticks, fish  and lumps of fecal matter
          should be excluded from the sample if it is determined that their inclusion is not desired
          in the final result.
     5.2  Floating oil and grease, if present,  should be included in  the sample and dispersed by a
          blender device before aliquoting.
6.    Apparatus
     6.1  Evaporating dishes, porcelain, 90 mm, 100 ml capacity. (Vycor or platinum dishes may
          be substituted and smaller size dishes may be used if required.)
7.    Procedure
     7.1  Heat the clean evaporating dish to 103-105'C for one hour,  if Volatile Residue is  to be
          measured, heat at 550  ±50"C for one hour in a muffle furnace. Cool, desiccate, weigh and
          store in desiccator until ready for use.
     7.2  Transfer a measured aliquot of sample to the pre-weighed dish and evaporate to dryness
          on a steam bath or in a drying oven.
          7.2.1  Choose an aliquot of sample sufficient to contain a residue of at  least 25 mg. To
                obtain a weighable residue, successive aliquots of sample may be added to the same
                dish.
          7.2.2  If evaporation is performed in a drying oven, the temperature should be lowered to
                approximately 98*C to prevent boiling and splattering of the sample.
Approved for NPDES
Issued 1971

                                         D-408
-------
     7.3   Dry the evaporated sample for at least 1 hour at  103-105'C. Cool in a desiccator and
           weigh. Repeat the cycle of drying at 103-105°C, cooling, desiccating and weighing until a
           constant weight is obtained or until loss of weight is less than 4% of the previous weight,
           or 0.5 mg, whichever is less.
8.    Calculation
     8.1   Calculate total residue as follows:
           Total residue, mg/1 = 
-------
D-410
-------
EPA METHOD
 NO. 120.1
     D-411
-------
                                  CONDUCTANCE

              Method 120.1  (Specific Conductance,  umhos at 25°O

                                                                STORET NO.  00095

1.    Scope and Application
     1.1  This method is applicable to drinking, surface, and saline waters, domestic and industrial
          wastes.
2.    Summary of Method
     2.1  The specific conductance of a sample is measured by use of a self-contained conductivity
          meter, Wheatstone bridge-type, or equivalent.
     2.2  Samples are preferably analyzed at 25*C. If not, temperature corrections are made and
          results reported at 25*C.
3.    Comments
     3.1  Instrument must be standardized with KC1 solution before daily use.
     3.2  Conductivity cell must be kept clean.
     3.3  Field measurements with comparable instruments are reliable.
4.    Precision and Accuracy
     4.1  Forty-one analysts in  17 laboratories  analyzed six synthetic water samples containing
          increments of inorganic salts, with the following results:

      Increment  as            Precision as                          Accuracy as
   Specific Conductance      Standard Deviation              Bias,                  Bias,
   	      ——————               %                 mnhos/cm

           100                     7.55                   -2.02                  -2.0
           106                     8.14                   -0.76                  -0.8
           808                    66.1                   -3.63                  -29.3
           848                    79.6                   -4.54                  -38.5
          1640                    106                     -5.36                  -87.9
          1710                    119                     -5.08                  -86.9

(FWPCA Method Study 1, Mineral and Physical Analyses.)

     4.2  In a single laboratory (EMSL) using surface water samples with an average conductivity
          of 536 umhos/cm at 25*C, the standard deviation was ±6.
5.    References
     5.1  The procedure to be used for this determination is found in:
          Annual Book of ASTM Standards, Part 31, "Water", Standard D1125-64, p 120 (1976).
          Standard Methods for the Examination of Water and Wastewater,  14th Edition, p 71,
           Method 205, (1975).
Approved for NPDES
Issued 1971
-------
EPA METHOD
 NO. 376.2
     D-413
-------
                                                     SULFIDE

                                  Method 376.2 (Colorimetric, Methylene  Blue)

                                                                        STORET NO. Total  00745
                                                                                     Dissolved  00746

               1.   Scope and Application
                    1.1   This method is applicable to the measurement of total and dissolved sulfides in drinking,
                          surface and saline waters, domestic and industrial wastes.
                    1.2   Acid insoluble sulfides are not measured by this method. Copper  sulfide is the only
                          common sulfide in this class.
                    1.3   The method is suitable for the measurement of sulfide in concentrations up to 20 mg/1.
               2.   Summary of Method
                    2.1   Sulfide reacts with  dimethyl-p-phenylenediamine (p-aminodimethyl aniline) in the
                          presence of ferric chloride to produce methylene blue, a dye which is measured at a
                          wavelength maximum of 625 nm.
               3.   Comments
                    3.1   Samples must be taken with a minimum  of aeration. Sulfide may be volatilized by
                          aeration and any oxygen inadvertently added to the sample may convert the sulfide to an
                          immeasurable form. Dissolved oxygen should not be present in any water used to dilute
                          standards.
                    3.2   The analysis must be started immediately.
                    3.3   Color and turbidity may interfere with observations of color or with photometric
                          readings.
               4.   Apparatus
                    4.1   Matched test tubes, approximately 125 mm long and 15 mm O. D.
                    4.2   Droppers, delivering 20 drops/ml. To obtain uniform drops, hold dropper in  vertical
                          position and allow drops to form slowly.
                    4.3   Photometer, use either 4.3.1 or 4.3.2.
                          4.3.1 Spectrophotometer, for use at 625 nm with cells of 1 cm and 10 cm light path.
                          4.3.2 Filter photometer, with filter providing transmittance near 625 nm.
               5.   Reagents
                    5.1   Amino-sulfuric acid  stock solution: Dissolve 27 g N,N-dimethyl-p-phenylenediamine
                          oxalate (p-aminodimethylaniline) in a cold mixture of 50 ml cone. H2SO4 and 20 ml
                          distilled water in a 100 ml volumetric flask. Cool and dilute to the mark. If dark discard
                          and purchase fresh reagent. Store in dark glass bottle.
                    5.2   Amino-sulfuric acid reagent: Dissolve 25 ml amino-sulfuric acid stock solution (5.1) with
                          975 ml of 1 +1 H,SO4 (5.4). Store in a dark glass bottle. This solution should be clear.
                    5.3   Ferric chloride solution: Dissolve 100 g FeCl3«6H2O in 40 ml distilled water.
               Approved for NPDES
/               Issued 1978


                                                        D-414
-------
     5.4   Sulfuric acid solution, H2SO4,1 +1
     5.5   Diammonium hydrogen phosphate solution: Dissolve 400 g (NH4)2HPO4 in  800 ml
           distilled water.
     5.6   Methylene blue solution I: Dissolve 1.0 g of methylene blue in distilled water in a 1  liter
           volumetric flask  and dilute to the mark.  Use U.S.P. grade or one certified by the
           Biological Stain Commission. The dye content reported on the label should be 84% or
           more. Standardize  (5.8) against sulfide solutions  of known  strength  and  adjust
           concentration so that 0.05 ml (1 drop) equals 1.0 mg/1 sulfide.
     5.7   Methylene blue solution II: Dilute 10.00 ml of adjusted methylene blue solution I (5.6) to
           100 ml with distilled water in a volumetric flask.
     5.8   Standardization of methylene blue I solution:
           5.8.1 Place several  grams of clean, washed crystals of sodium sulfide Na2S«9H2O  in a
                small beaker.
           5.8.2 Add somewhat less than enough water to cover the crystals.
           5.8.3 Stir occasionally for a few minutes. Pour the solution into another  vessel. This
                reacts slowly  with oxygen but the change is insignificnat over a few hours. Make
                the solution daily.
           5.8.4 To 1 liter of distilled water add 1 drop of solution and mix.
           5.8.5 Immediately determine the sulfide concentration by the methylene blue procedure
                (6) and by the titrimetric iodide procedure (Method 376.1, this manual).
           5.8.6 Repeat using more than one drop of sulfide solution or less water until at least five
                tests have been made in the range of 1 to 8 mg/1 sulfide.
           5.8.7 Calculate the average  percent  error of the methylene blue procedure  (6) as
                compared to the titrimetric iodide procedure (Method 376.1).
           5.8.8 Adjust by dilution or by adding more dye to methylene blue solution I (5.6).
6.    Procedure
     6.1   Color development
           6.1.1  Transfer 7.5 ml of sample to each of two matched test tubes using a special wide
                tipped pipet or filling to a mark on the test tubes.
           6.1.2  To tube A add 0.5 ml amine-sulfuric acid reagent (5.2) and 0.15 ml (3 drops) FeCl3
                solution (5.3).
           6.1.3 Mix immediately by inverting the tube only once.
           6.1.4 To tube B add 0.5 ml 1 +1 H2SO4 (5.4) and 0.15 ml (3 drops) JFeCl3 solution (5.3)
                and mix.
           6.1.5 Color will develop in tube A in the presence  of sulfide. Color development is
                usually complete in about 1 minute, but a longer time is often required for the
                fading of the initial pink color.
           6.1.6 Wait 3 to 5 minutes.
           6.1.7 Add 1.6 ml (NH4)2HPO4 solution (5.5) to each tube.
           6.1.8  Wait 3 to 5 minutes and make color comparisons. If zinc acetate was used wait at
                least 10 minutes before making comparison.
                                          D-415
-------
                    6.2  Color comparison
 _                            6.2.1 Visual
' .                                   6.2.1.1     Add methylene blue solution  I (5.6) and/or II (5.7) (depending on
                                              sulfide concentration and accuracy desired) dropwise to tube B (6.1.4)
                                              until the color matches that developed in the first tube.
                                    6.2.1.2     If the concentration exceeds 20 mg/1, repeat 6.2.1.1 using a portion of
                                              the sample diluted to one tenth.
                               6.2.2 Photometric
                                    6.2.2.1     Use a 1 cm cell for 0.1 to 2.0 mg/1. Use a 10 cm cell for up to 20 mg/1.
                                    6.2.2.2     Zero instrument with portion of sample from tube B (6.1.4).
                                    6.2.2.3     Prepare  calibration  curve from  data  obtained  in methylene  blue
                                              standardization (5.8), plotting  concentraton obtained from  titrimetric
                                              iodide procedure (Method 376.1) versus absorbance. A straight  line
                                              relationship can be assumed from 0 to 1.0 mg/1.
                                    6.2.2.4     Read the sulfide concentration  from the calibration curve.
                    7.    Calculations
                         7.1   Visual comparison: With methylene blue solution I (5.6), adjusted so  that 0.05 ml (1
                               drop) = 1.0 mg/1 sulfide and a 7.5 ml sample

                               mg/1 sulfide  = number drops methylene  blue solution I (5.6) + 0.1 x [number of drops
                                              methylene blue solution II (5.7)].
                         7.2   Photometric: see 6.2.2.4
                    8.    Precision and Accuracy:
                         8.1   The precision has not been determined. The accuracy is about ±10%.

                                                           Bibliography

                    1.    Standard Methods for he Examination of Water and Wastewater, 14th edition, p. 503, Method
                         428C(1975).
                                                             D-416
-------
EPA METHOD
 NO. 415.1
       D-417
-------
                          ORGANIC CARBON, TOTAL

                     Method 415.1  (Combustion or  Oxidation)

                                                         STORET NO. Total  00680
                                                                     Dissolved  00681

1.    Scope and Application
     1.1   This method includes the measurement of organic carbon in drinking, surface and saline
          waters,  domestic and industrial wastes. Exclusions are noted under Definitions and
          Interferences.
     1.2   The method is most applicable to measurement of organic carbon above 1 mg/1.
2.    Summary of Method
     2.1   Organic carbon in a sample is converted to carbon dioxide (CO2) by catalytic combustion
          or wet chemical oxidation. The CO2 formed can  be measured directly by an infrared
          detector or converted to methane (CH4) and measured by a flame ionization detector.
          The amount of CO2 or CH« is directly proportional to the concentration of carbonaceous
          material in the sample.
3.    Definitions
     3.1   The carbonaceous analyzer measures all of the carbon in a sample.  Because of various
          properties of carbon-containing compounds in liquid samples, preliminary treatment of
          the sample prior to analysis dictates the definition of the carbon as it is measured. Forms
          of carbon that are measured by the method are:
          A)   soluble, nonvolatile organic carbon; for instance, natural sugars.
          B)   soluble, volatile organic carbon; for instance, mercaptans.
          C)   insoluble, partially volatile carbon; for instance, oils.
          D)   insoluble, particulate carbonaceous materials, for instance; cellulose fibers.
          E)   soluble or insoluble carbonaceous materials adsorbed or entrapped on insoluble
               inorganic suspended matter, for instance, oily matter adsorbed on silt particles.
     3.2   The final  usefulness  of the carbon measurement is in assessing the potential oxygen-
          demanding load  of  organic material on a receiving  stream. This statement  applies
          whether the carbon measurement is made on a sewage plant effluent,  industrial waste, or
          on water taken directly from the stream. In this light, carbonate and bicarbonate carbon
          are not a part of the oxygen demand in the stream and therefore should be discounted in
          the final calculation or removed prior to analysis. The manner of preliminary treatment
          of the sample and instrument settings defines the types of carbon which are measurer1
          Instrument manufacturer's instructions should be followed.
Approved for  NPDES
Issued 1971
Editorial revision 1974
                                         D-418
-------
4.    Sample Handling and Preservation
     4.1   Sampling and storage of samples in glass bottles is preferable. Sampling and storage in
           plastic bottles such as conventional polyethylene and cubitainers is permissible if it is
           established that the containers do not contribute contaminating organics to the samples.
           NOTE 1: A brief study performed in the EPA Laboratory indicated that distilled water
           stored in new, one quart cubitainers did not show any increase in organic carbon after
           two weeks exposure.
     4.2   Because  of the possibility of oxidation or bacterial decomposition of some components of
           aqueous  samples, the lapse of time between collection of samples and start of analysis
           should be kept to a minimum. Also, samples should be kept cool (4°C) and protected
           from sunlight and atmospheric oxygen.
     4.3   In instances where analysis cannot be performed within two hours (2 hours) from time of
           sampling, the sample is acidified (pH < 2) with HC1 or H2SO4.
5.    Interferences
     5.1   Carbonate and bicarbonate carbon represent an interference under the terms of this test
           and must be removed or accounted for in the final calculation.
     5.2   This procedure is applicable only to homogeneous samples which can be injected into the
           apparatus reproducibly by means of a microliter type syringe or pipette. The openings of
           the syringe or pipette limit the maximum size of particles which may be included in the
           sample.
6.    Apparatus
     6.1   Apparatus for blending or homogenizing samples: Generally, a Waring-type blender is
           satisfactory.
     6.2   Apparatus for total and dissolved organic carbon:
           6.2.1 A  number of  companies manufacture systems for measuring carbonaceous
                material in liquid samples. Considerations should  be made as to the  types of
                samples to be analyzed, the expected concentration range, and forms of carbon to
                be  measured.
           6.2.2 No specific analyzer is recommended as superior.
7.    Reagents
     7.1   Distilled water used in preparation of standards and for dilution of samples should be
           ultra pure to reduce the carbon concentration of the blank. Carbon dioxide-free,  double
           distilled  water is recommended. Ion exchanged waters are not recommended because of
           the possibilities of contamination with organic materials from the resins.
     7.2   Potassium hydrogen phthalate, stock solution, 1000 mg carbon/liter: Dissolve 0.2128 g
           of potassium hydrogen phthalate (Primary Standard Grade) in distilled water and dilute
           to 100.0 ml.
           NOTE 2: Sodium oxalate and acetic acid are not recommended as stock solutions.
     7.3   Potassium hydrogen phthalate, standard solutions: Prepare standard solutions  from the
           stock solution by dilution with distilled water.
     7.4   Carbonate-bicarbonate, stock solution, 1000 mg carbon/liter: Weigh 0.3500 g of sodium
           bicarbonate and 0.4418 g of sodium carbonate and transfer both to the  same 100 ml
           volumetric flask. Dissolve with distilled water.
                                           D-419
-------
     7.5   Carbonate-bicarbonate, standard solution: Prepare a series of standards similar to step
           7.3.
           NOTE 3: This standard is not required by some instruments.
     7.6   Blank solution: Use the same distilled  water (or similar quality water) used  for the
           preparation of the standard solutions.
8.    Procedure
     8.1   Follow  instrument manufacturer's  instructions for  calibration,  procedure, and
           calculations.
     8.2   For calibration of the  instrument, it  is recommended that  a series of standards
           encompassing the expected concentration range of the samples be used.
9.    Precision and Accuracy
     9.1   Twenty-eight analysts in twenty-one laboratories analyzed distilled  water solutions
           containing exact increments of oxidizable organic compounds, with the following results:
      Increment as
          TOC
        mg/liter

           4.9
           107
   Precision as
Standard  Deviation
  TOC. mg/liter

       3.93
       8.32
(FWPCA Method Study 3, Demand Analyses)
  Bias,
   %
           Accuracy as
 Bias,
mg/liter
+ 15.27
+  1.01
 +0.75
 + 1.08
                                       Bibliography

1.    Annual Book of ASTM Standards, Part 31, "Water", Standard D 2574-79, p 469 (1976).
2.    Standard Methods  for the Examination of Water and Wastewater,  14th  Edition, p 532,
     Method 505, (1975).
                                           D-420
-------
EPA METHOD
 NO. 9060
 D-421
-------
                                 METHOD 9060

                            TOTAL ORGANIC CARBON
1.0  SCOPE AND APPLICATION
     1.1  Method 9060 1s used to determine the concentration of organic carbon
in ground  water,  surface  and  saline  waters,   and  domestic and industrial
wastes.  Some restrictions are noted 1n Sections  2.0 and 3.0.

     1.2  Method 9060 1s  most  applicable  to measurement  of organic carbon
above 1 mg/L.


2.0  SUMMARY OF METHOD

     2.1  Organic carbon 1s  measured  using  a  carbonaceous  analyzer.  This
instrument converts the organic carbon in  a sample to carbon dioxide (C02)  by
either catalytic combustion or wet chemical oxidation.  The C02 formed is then
either measured directly by an infrared detector  or converted to methane (CH^.)
and measured by a flame ionization detector.    The  amount of C02 or CH^ in a
sample is directly proportional to  the concentration of carbonaceous material
in the sample.

     2.2  Carbonaceous analyzers are capable of  measuring all forms of carbon
in a sample.    However,  because  of  various properties of carbon-containing
compounds 1n liquid samples,  the  manner  of  preliminary sample treatment as
well as the  instrument  settings  will  determine  which  forms of carbon are
actually measured.  The forms of  carbon   that  can be measured by Method 9060
are:

       1.  Soluble, nonvolatile organic carbon:  e.g., natural  sugars.

       2.  Soluble, volatile organic  carbon:    e.g., mercaptans, alkanes, low
          molecular weight alcohols.

       3.  Insoluble,  partially volatile   carbon:    e.g.,  low  molecular weight
          oils.

       4.  Insoluble,   particulate  carbonaceous  materials:    e.g.,  cellulose
          fibers.

       5.  Soluble  or  insoluble   carbonaceous  materials   adsorbed or  entrapped
          on Insoluble inorganic suspended matter:   e.g.,  oily matter adsorbed
          on silt  particles.

      2.3  Carbonate  and bicarbonate  are  inorganic   forms  of carbon  and  must be
 separated from the total  organic carbon   value.    Depending  on  the  instrument
 manufacturer's instructions,  this separation  can   be accomplished  by either  a
 simple mathematical  subtraction,  or  by   removing  the  carbonate and  bicarbonate
 by converting  them to C02  with degassing  prior to  analysis.


                                  9060    D-422
                                                          Revision       Q
                                                          Date  September  1986
-------
3.0  INTERFERENCES

     3.1  Carbonate and bicarbonate carbon represent an interference under the
terras of this test and must be  removed or accounted for in the final  calcula-
tion.

     3.2  This procedure 1s-applicable  only  to homogeneous samples which can
be injected into  the  apparatus  reproducibly  by  means of a microliter-type
syringe or pipet.  The openings of the syringe or pipet limit the maximum size
of particle which may be included in the sample.

     3.3  Removal of carbonate  and  bicarbonate  by acidification and purging
with nitrogen, or other inert gas, can  result in the loss of volatile organic
substances.
4.0  APPARATUS AND MATERIALS

     4.1  Apparatus  for  blending  or  homogenizing  samples:    Generally,  a
War1 ng-type blender is satisfactory.

     4.2  Apparatus for total and dissolved organic carbon;

          4.2.1  Several  companies   manufacture   analyzers   for  measuring
     carbonaceous material in  liquid  samples.    The most appropriate system
     should be selected based on consideration  of  the types of samples to be
     analyzed, the expected concentration range, and the forms of carbon to be
     measured.

          4.2.2  No specific analyzer  is  recommended  as  superior.   If the
     technique of chemical oxidation is  used,  the laboratory must be certain
     that the instrument is  capable  of  achieving  good carbon recoveries in
     samples containing parti culates.


5.0  REAGENTS

     5.1  ASTM Type II water  (ASTM  D1193) :    Water  should be monitored for
impurities, and should be boiled and cooled to remove
     5.2  Potassium hydrogen  phthalate,  stock  solution.  1,000 mg/L carbon:
Dissolve 0.2128 g of potassium  hydrogen phthalate (primary standard grade) in
Type II water and dilute to 100.0 ml.
     NOTE;  Sodium  oxalate  and  acetic  acid  are  not  recommended as stock
          solutions.

     5.3  Potassium hydrogen phthalate, standard  solutions;  Prepare standard
solutions from the stock solution by dilution with Type II water.
                                  9060
                                                         Revision      0
                                                         Date  September 1986
-------
     5.4  Carbonate-bicarbonate,  stock  solution,   1,000  mg/L  carbon:   Weigh
0.3500 g of sodium bicarbonate and  0.4418  g of sodium carbonate and transfer
both to the same 100-mL volumetric flask.   Dissolve with Type II water.

     5.5  Carbonate-bicarbonate,   standard  solution;     Prepare  a  series of
standards similar to Step 5.3.
     NOTE;  This standard 1s not required  by some instruments.

     5.6  Blank solution;  Use the same  Type  II water as was used to prepare
the standard solutions.
6.0  SAMPLE COLLECTION, PRESERVATION,  AND HANDLING

     6.1  All samples must be collected  using  a sampling plan that addresses
the considerations discussed in Chapter Nine of this manual.

     6.2  Sampling and storage  of  samples  in  glass  bottles is preferable.
Sampling and storage in plastic  bottles such as conventional polyethylene and
cubitainers is permissible if  it  is   established  that the containers do not
contribute contaminating organlcs to the samples.
     NOTE;  A brief study performed  in the EPA Laboratory indicated that Type
          II water stored 1n new,  1-qt  cubital ners did not show any increase
          in organic carbon after 2 weeks' exposure.

     6.3  Because of the possibility  of  oxidation or bacterial decomposition
o'f some components of aqueous samples,  the time between sample collection and
the start of analysis should be minimized.   Also, samples should be kept cool
(4*C) and protected from sunlight and atmospheric oxygen.
     6.4  In instances where analysis  cannot
time of sampling, the sample Is acidified (pH
                                               be  performed  within 2 hr from
                                                2} with HC1 or
7.0  PROCEDURE

     7.1  Homogenize  the sample in a blender.
     NOTE:   To  avoid  erroneously  high  results,  inorganic  carbon must be
          accounted for.  The preferred method  is to measure total  carbon and
          inorganic carbon and to  obtain  the  organic carbon by  subtraction.
          If this  1s  not possible, follow Steps 7.2 and 7.3 prior  to analysis;
          however, volatile organic carbon may be lost.

     7.2  Lower  the pH  of the sample to 2.

     7.3  Purge  the sample with nitrogen for  10 min.

     7.4  Follow  instrument  manufacturer's.   instructions   for   calibration,
procedure,  and calculations.

     7.5  For calibration of 'the  instrument,  a  series of standards should be
used that encompasses the expected concentration range of the samples.
                                   9060
                                          D-424
                                                          Revision       0
                                                          Date   Seotember  1986
-------
     7.6  Quadruplicate analysis is required.   Report both  the average and the
range.


8.0  QUALITY CONTROL

     8.1  All quality control data should be maintained and available for easy
reference or inspection.

     8.2  Employ a minimum  of  one  blank  per  sample  batch to determine 1f
contamination or any memory effects are occurring.

     8.3  Verify calibration  with  an  independently  prepared check standard
every 15 samples.

     8.4  Run one spike duplicate sample  for  every  10 samples.  A duplicate
sample is a sample brought through the whole sample preparation and analytical
process.


9.0  METHOD PERFORMANCE

     9.1  Precision and accuracy data are available in Method 415.1 of Methods
for Chemical Analysis of Water and Wastes.


10.0 REFERENCES

1.   Annual Book  of ASTM  Standards,  Part 31,  "Water,"  Standard D 2574-79,
p. 469 (1976).

2.   Standard Methods  for the Examination of Water and Wastewater,  14th ed.,
p. 532, Method 505 (1975).
                                  9060   D-425
                                                         Revision
                                                         Date  September 1986
-------

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-------
      EPA METHOD
      NO. 415.1M
TOTAL VOLATILE ORGANICS
             D-427
-------
                          ORGANIC CARBON, TOTAL

                     Method 415.1 (Combustion or Oxidation)

                                                         STORET NO. Total 00680
                                                                      Dissolved 00681

1.    Scope and Application
     1.1   This method includes the measurement of organic carbon in drinking, surface and saline
          waters, domestic and industrial wastes. Exclusions are noted under Definitions and
          Interferences.
     1.2   The method is most applicable to measurement of organic carbon above 1 mg/1.
2.    Summary of Method
     2.1   Organic carbon in a sample is converted to carbon dioxide (CO2) by catalytic combustion
          or wet chemical oxidation. The CO2 formed can be measured directly by an infrared
          detector or converted to methane  (CH4) and measured by a flame ionization detector.
          The amount of CO2 or CH4 is directly proportional to the concentration of carbonaceous
          material in the sample.
3.    Definitions
     3.1   The carbonaceous analyzer measures all of the carbon in a sample. Because of various
          properties of carbon-containing compounds in liquid samples, preliminary treatment of
          the sample prior to analysis dictates the definition of the carbon as it is measured. Forms
          of carbon that are measured by the  method are:-
          A)   soluble, nonvolatile organic carbon; for instance, natural sugars.
          B)   soluble, volatile organic carbon; for instance, mercaptans.
          C)   insoluble, partially volatile carbon; for instance, oils.
          D)   insoluble, paniculate carbonaceous materials, for instance; cellulose fibers.
          E)   soluble or insoluble carbonaceous materials adsorbed or entrapped on insoluble
               inorganic suspended matter,  for instance, oily matter adsorbed on silt particles.
     3.2   The final usefulness of the carbon measurement is in assessing the potential oxygen-
          demanding load  of  organic material on a receiving  stream. This statement applies
          whether the carbon measurement is made on a sewage plant effluent, industrial waste, or
          on water taken directly from the stream. In this light, carbonate and bicarbonate carbon
          are not a part of the oxygen demand in the stream and therefore should be discounted in
          the final calculation or removed prior to analysis. The manner of preliminary treatment
          of the sample and instrument settings defines the types of carbon which are measured
          Instrument manufacturer's instructions should be followed.
Approved for  NPDES
Issued 1971
Editorial revision 1974
                                          D-428
-------
4.    Sample Handling and Preservation
     4.1   Sampling and storage of samples in glass bottles is preferable. Sampling and storage in
           plastic bottles such as conventional polyethylene and cubitainers is permissible if it is
           established that the containers do not contribute contaminating organics to the samples.
           NOTE 1: A brief study performed in the EPA Laboratory indicated that distilled water
           stored in new, one quart cubitainers did not show any increase in organic carbon after
           two weeks exposure.
     4.2   Because of the possibility of oxidation or bacterial decomposition of some components of
           aqueous samples, the lapse of time between collection of samples and start of analysis
           should be kept to a minimum. Also, samples should be kept cool (4°C) and protected
           from sunlight and atmospheric oxygen.
     4.3   In instances where analysis cannot be performed within two hours (2 hours) from time of
           sampling, the sample is acidified (pH < 2) with HC1 or H2SO4.
5.    Interferences
     5.1   Carbonate and bicarbonate carbon represent an interference under the terms of this test
           and must be removed or accounted for in the final calculation.
     5.2   This procedure is applicable only to homogeneous samples which can be injected into the
           apparatus reproducibly by means of a microliter type syringe or pipette. The openings of
           the syringe or pipette limit the maximum size of particles which may be included in the
           sample.
6.    Apparatus
     6.1   Apparatus for blending or homogenizing samples: Generally, a Waring-type blender is
           satisfactory.
     6.2   Apparatus for total and dissolved organic carbon:
           6.2.1  A  number of companies manufacture systems for  measuring carbonaceous
                material in liquid samples. Considerations should  be  made as to the types  of
                samples to be analyzed, the expected concentration range, and forms of carbon to
                be measured.
           6.2.2 No specific analyzer  is recommended as superior.
7.    Reagents
     7.1   Distilled water used in preparation of standards and for dilution of samples should be
           ultra pure to reduce the carbon concentration of the blank. Carbon dioxide-free, double
           distilled  water is recommended. Ion exchanged waters are not recommended because of
           the possibilities of contamination with organic materials from the resins.
     7.2   Potassium hydrogen phthalate, stock solution, 1000 mg carbon/liter:  Dissolve 0.2128 g
           of potassium hydrogen phthalate (Primary Standard Grade) in distilled water and dilute
           to 100.0 ml.
           NOTE 2: Sodium oxalate and acetic acid are not recommended as stock solutions.
     7.3   Potassium hydrogen phthalate, standard solutions: Prepare standard solutions from the
           stock solution by dilution with distilled water.
     7.4   Carbonate-bicarbonate, stock solution, 1000 mg carbon/liter: Weigh 0.3500 g of sodium
           bicarbonate and 0.4418 g  of sodium carbonate and transfer both to  the  same 100 ml
           volumetric flask. Dissolve with distilled water.
                                          D-429
-------
f
     7.5   Carbonate-bicarbonate, standard solution: Prepare a series of standards similar to step
           7.3.
           NOTE 3: This standard is not required by some instruments.
     7.6   Blank solution: Use the same distilled  water (or similar quality water) used for the
           preparation of the standard solutions.
8.   Procedure
     8.1   Follow  instrument  manufacturer's  instructions for  calibration,  procedure, and
           calculations.
     8.2   For calibration of the  instrument, it  is recommended that  a series of standards
           encompassing the expected concentration range of the samples be used.
9.   Precision and Accuracy
     9.1   Twenty-eight analysts in twenty-one laboratories analyzed distilled water solutions
           containing exact increments of oxidizable organic compounds, with the following results:
                      Increment as
                          TOC
                        mg/liter

                           4.9
                           107
                              Precision  as
                           Standard Deviation
                             TOC. mg/liter

                                 3.93
                                 8.32
                (FWPCA Method Study 3, Demand Analyses)
  Bias,
   %
           Accuracy as
 Bias,
mg/liter.
+15.27
+  1.01
 +0.75
 + 1.08
                                                       Bibliography

                1.    Annual Book of ASTM Standards, Part 31, "Water", Standard D 2574-79, p 469 (1976).
                2.    Standard  Methods  for the Examination of Water and Wastewater,  14th Edition, p 532,
                     Method 505, (1975).
                                                          D-430
-------
 Tekmar Company^
 Telqnar Company"
            Comoairv"
                   LIQUID SAMPLE CONCENTRATOR

                        MODEL LSC-1

                      Instruction Manual


SECTION I
SECTION II





SECTION III




SECTION TV








TABLE OF CONTENTS

INTRODUCTION
INSTALLATION
1.
2.
3.
4.
5.
Utilities Required
Assembly
Interfacing with a G.C.
Interfacing with a Totals Detector
Conditioning Trap .Column
OPERATION
1.
2.
3.
4.
Description of Controls
Operation
Calibration
Trap Column

Page
1
2
2
2
2
3
3
5
5
6
7
8
ILLUSTRATIONS
1.
2.
3.
4.
5.
6.
LSC-1
Purge Mode Schematic
Desorb Mode Schematic
Direct Interface to G.C.
Tube-needle Interface to G.C.
Tube-needle Interface to Totals Detector
9
10
10
11
11
11
SECTION V
REPRINTS AND COMPONENT PARTS INFORMATION
                      D-431
P.O-Box 37202 • Cincinnati, Ohio 45222 • (513) 761-0633 • TELEX NO. 21-1221
-------
     Procedure  for  Purgeable  Organic  Carbon   
-------
                                              JcJqnar Company*
 SECTION I    INTRODUCTION

 The  LSC-1  is designed  to concentrate volatile organic
 contaminants found  in  fresh  and waste water.  By
 bubbling an  inert gas  through the aqueous  sample,
 the  volatile organic contaminants exhibiting low
 solubility in water will be  quantitatively
 partitioned  into the gas phase.  A trap column in
 the  LSC-1  concentrates the organics from the gas
 phase to complete the concentration step.  Following
 the  concentration step (Purge Mode, Figure 2) the
 sample  is  thermally desorbed from the trap column
 (Desorb  Mode, Figure 3) and  transferred via connect-
 ing  tubing to your measurement device.

 The  technique will quantitatively remove those
 organics exhibiting high volatility (less than
 150  C Boiling Point) and low solubility (less than
 5%)  in water.  At solubilities greater than 5% (apx.)
partitioning of the organic  compound is not quantita-
 tive.  In the latter case,  quantitative analysis is
possible by relating the amount of sample partitioned
 from the aqueous phase to the volume of purge gas
used.
                         D-433
-------
                                                      Company"
 SECTION II     INSTALLATION

 1.    Utilities Required:
      Power:    110V,  60 Hz,  2A
      Gases:    Purge  gas should be  zero grade Helium
               or Nitrogen.  Connect to Purge Gas on
               rear of LSC-1.  Set  delivery pressure
               to 20  psi.  A hydrocarbon trap should
               be used to scrub the purge gas before
               entering the  LSC-1.
               Desorb gas should be pre-purified grade
               Helium or Nitrogen.  Connect to Desorb
              Gas on rear of LSC-1.  Delivery pressure
              will be determined by type of  interfac-
               ing used.  (See Section U, 3  for
               further details on desorb gas.)
2.   Assembly
     Except for the sampler, the LSC-1 is completely
     assembled.  Remove the sampler from its packing
     and install as pictured in Figure 1.   The sampler
     is supported by the 1/4" compression fitting
     attached to the front panel bracket.  Connect the
     purge gas tube  (left side of bracket)  to the
     sampler arm running to the bottom of the frit.
     Connect the exit tube  (right side of bracket)
     to the right arm of the sampler.   Reasonable care
     should be exercised in attaching  the fittings  to
     avoid breakage of the saapler.
3.   Interfacing with a -Gas Chromatograph
     Interfacing to a G.C.  is best done by using  the
     G.C. carrier gas as the desorb gas for  the LSC-1
     (see Figure 4).   The output of the G.C.  flow
     controller is  connected directly  to  the desorb
                            D-434
-------
                                             Tckmar Company*
     gas input of the LSC-1.  The trap effluent port on
     the LSC-1 is connected directly .to the carrier input
     of the G.C. injection port using the 1/8" O.D.
     teflon tubing supplied.  Using this type of inter-
     facing, the G.C. carrier backflushes the LSC-1
     trap directly to the G.C. column in Desorb Mode.
     In Purge Mode, operation of the G.C. is unaffected.

     An alternate means of interfacing to a G.C. is the
     tube-needle coupling (see Figure 5).  In this case
     the trap effluent port of the LSC-1 is connected
     to the septa injector of the G.C. with teflon tubing
     and needle adaptor (supplied with LSC-1.)  Oesorb
     gas for the LSC-1 must be supplied at a pressure
     greater than the pressure of the carrier gas going
     to the G.C. (to prevent G.C. carrier from back-
     streaming to the LSC-1 during Desorb Mode.)  A flow
     rate of 20 cc/min. for the desorb gas is sufficient.
     An auxiliary flow controller is required between the
     desorb gas tank and the LSC-1 to regulate the desorb
     flow.
4.   Interfacing with a Totals Detector
     Interfacing to a totals detector (specific chlorine,
     TOC analyzer,  total hydrocarbon analyzer,  etc. )  is
     usually accomplished using the tube-needle coupling
     (Figure 6).  However, if the totals detector uses a
     carrier gas, that carrier could be used as the desorb
     gas for the LSC-1 (Figure 4).
5.   Conditioning Trap Column
     The trap column in, your LSC-1 was baked out prior to
     shipment but should be baked again prior to operation.
     Turn on the LSC-1, set the Purge/Desorb valve to
     Purge, set the Trap Bake/Operate switch to Trap Bake,
     and set the Trap Temperature Control to 250 C.
                          D-435
-------
                                        Te^rnar Company*
Leave the LSC-1 in this condition overnight for
a thorough cleaning of the trap.  This procedure
can be repeated whenever trap contamination is
suspected.
                      D-436
-------
                                                     Company"
SECTION III

1.
         OPERATION
Description of Controls
Trap Bake/Operate
          Operate:
          Trap Bake:
     Trap Temperature
          Control:
     Purge Timer:
                  Trap oven and fan are controlled by
                  position of purge/desorb valve.
                  Purge timer can be set for desired
                  purge time.
                  Used for conditioning trapping
                  column.   Fan is off and the oven is
                  on independent of purge/desorb valve
                  position.   (The purge/desorb valve
                  should be set in the purge position
                  during trap bake mode to avoid con-
                  tamination of the measurement device.

                  This is  a direct set proportional
                  temperature controller.   The red
                  light below the control  blinks when
                  the controller is proportioning  at
                  the set  temperature.   The control is
                  off in purge mode.   For  all other
                  instrument settings,  the controller
                  is on.   The range is  room temperature
                  to 350°C.
                  The timer controls  a  three-way valve
                  supplying  purge gas to the sampler.
                  The timer  can be set  from zero to
                  thirty minutes and is continuously
                  adjustable.   After  setting the time,
                  the timer  is  started  by  pressing  the
                  white button in the center of  the
                      D-437
-------
                                                     Company*
                 timer knob.  At the end of  the pre-set
                 time the purge valve closes and the timer
                 re-sets itself.  To terminate a run,
                 rotate the timer knob counter-clockwise
                 to zero.
     Purge/Desorb:
         Purge:  The flow of purge gas (controlled by
                 rotameter and purge timer) is directed
                 to the trap column and to vent.  The
                 desorb gas passes through the valve, by-
                 passing the trap column enroute to the
                 measurement device (Figure 2).
         Desorb: The sampler is connected to vent and the
                 desorb gas backflushes the heated trap
                 column enroute to the measurement device
                 (Figure 3).
     Purge Flow: Flowneter used to establish the flow of
                 purge gas'to the sampler.
     Trap
      Effluent:  For connection to measurement unit.
     In j ection
        Port:    Located on top of front  panel bracket
                 and uses standard G.C. septa.
2.    Operation
     Set main power switch to  On (no warm-up  required)  and
     set Trap Bake/Operate switch to Operate.  Establish
     a 40 cc/min.  flow rate of purge gas  with the  flov*neter
     (approximately 45  on the  flovroeter,  but  this must  be
     checked against a  bubble  type flowneter  or  similar
     calibrating device.)   Set the Trap Temperature Control
     to 130°C.  Fill the 5  ml  syringe with  sample by remov-
     ing the plunger and pouring  sample into  the barrel to
                             D-438
-------
                                             Tckpiar Company*
     overflowing.  Open the valve on the bottom of the
     syringe and reinsert the plunger into the syringe
     barrel  (avoid air bubbles between the liquid and
     plunger. )  Using the long needle, the sample is
     injected into the purge unit.  (If the sample is
     not injected immediately/ close the syringe valve
     to avoid loss of volatiles.)
     Set the purge timer to the required purge time
     (typically 11 minutes ) , and press the white button
     in the center of the timer knob.   Purge gas will
     now be bubbling through the sample and will stop
     automatically at the end of the pre-set purge time.
     During this interval, prepare your measurement
     device to receive the sample.  The concentrated
     sample is transferred to your measurement unit by
     turning the Desorb/Purge valve to Desorb.  This
     backflushes the trap column and turns on the
     Temperature Controller, causing a rapid temperature
     rise in the trap and thermal desorption.   After
     three or four minutes, return the system to purge
     mode and the LSC-1 is ready to accept a new sample.
     As mentioned above, the LSC-1 needs no warm-up.
     Indeed, if long delays occur between sample runs,
     it would be best to turn off the  LSC-1 to a>/cid
     needless running of the trap column cooling fan.

3.    Calibration
     Prepare a solution of your standards in methanol at
     a concentration of 1000 times the desired calibration
     level.   Inject 5 ul of the methanol solution directlv
                             D-439
-------
                                              Tckgiar Company*
     into the 5 ml sample syringe containing  organic free
     water using the 10 ul syringe supplied with the LSC-1.
     The 10 ul syringe needle is run through  the valve
     attached to the 5 ml sample syringe with the valve in
     the open position.  After injecting the  standard into
     the organic free water, withdraw the 10 ul syringe/
     close the valve, attach the long needle  to the valve
     and inject the 5 ml into the purge unit.
4.   Trap Column
     The trap installed in your LSC-1 contains 2/3 Tenax
     and 1/3 Silica Gel Oavisson Grade 15.   This is
     optimized for trapping organohalides but will also
     trap a broad range of organic compounds.  A blank.
     trap is supplied for making your own trap column if
     it is desired to optimize for a particular compound.
     The top of the column is identified by two grooves
     cut near the top end.   An all tenax trap is available
     and is  identified by one groove cut near the top end.
     The trap column is accessible through the rear panel.

          CAUTION:     Unplug power cord before
                                 i
                       removing  the back panel
                       or chassis.
     The fittings  at the top  of  the trap are finger tight
     and utilize  teflon ferrules.    Remove  the 1/16"  tube
     and fitting  from the top of the trap and loosen the
     fitting at the  base.   Lift  the trap vertically about
     one inch.  Swing the bottom of the  trap to  the rear
     of the  LSC-1  and the trap and  furnace  can be removed
     through the opening in the  rear of  the furnace housing.
                             D-440
-------
s
-------
Purge  gas  (He or N2)  is  bubbled through the
sample, partitioning volatile organics into the gas
phase for concentration by  the trap column.
                                                             Figure 2
           D«aortj G*» Ovrt
  Desortt Gas In
                                                Purge Mode
                                              (Trap Column 2S'C)
                                                                in
Desorfo Mode
The trap column is heated and backflushed with
carrier gas  (He orN2) to transfer the concentrated
sample to the measurement device.
Figure 3
       Oesorb Gas and Simple Out
                                               DesorfeMode
                                             (Trap Column 125'C)
                                                               In
Bake Mode
This is a service mode for cleaning the trap column
at elevated temperature while venting the effluent
to atmosphere.
                                    D-442
-------
                        LSC-1 Typical Detector Interfacings
    LSC1/GC
   Direct couple to GC using GC
   carrier as LSC-1 input.
    Figure 4
                                                      Carrier
                       From Flow Controller
Purge
                                                LSC-1
                                      <3C
      Effluent Out     Garner Input of Injection Port
   LSC-l/GC

   Tube-needle coupling to GC
   using alternate source of He or
   Ni as LSC-1 carrier input.
(    Figure 5
      Effluent Out
                                                                            Injection Port
   LSC-1/Specific Totals Detector

   Tube-needle coupling to totals
   detector using alternate source
   of He or Ns as LSC-1 carrier
   input.
   Figure  6
                            Total Organic Carbon Analyzer

                             Specific Chlorine Detector
                                                    Effluent Out
                            1 Sample Input
     Tekmar Company*
     P.O. Box 37202 • Cincinnati, Ohio 45222 • Telephone: 513/781-0633
                                                   D-443
-------
xf
xT
xf

o
-------
EPA METHOD
 NO. 1010
     D-445
-------
                                 METHOD 101C1

                       PENSKY-MARTENS CLOSED-CUP METHOD
1.0  Scope and Application

     1.1  Method 1010 uses the Pensky-Martens  closed-cup tester to determine
the flash point of fuel  oils,  lube oils,  suspensions  of solids, liquids that
tend to form a surface film under test conditions,  and  other liquids.


2.0  Summary of Method

     2.1  The sample is  heated at a slow,  constant  rate with continual
stirring.  A small  flame is directed into  the  cup at  regular intervals  with
simultaneous interruption of stirring.  The flash point is  the  lowest  temper-
ature at which application of  the test flame ignites  the vapor  above the
sample.


3.0  Interferences
     3.1  Ambient pressure,  sample homogeneity,  drafts,  and  operator  bias  can
affect flash point values.


4.0  Apparatus

     4.1  Pensky-Martens Closed Flash Tester,  as described  in  Annex Al  of  ASTM
Method D93-77.  (Automatic  flash point testers are  available and  may  be
advantageous since they save testing time,  permit the  use of smaller  samples,
and exhibit other advantages.   If automatic testers are  used,  the user  must  be
sure to follow all the manufacturer's instructions  for calibrating, adjusting,
and operating the instrument.   In any cases of dispute,  the  flash point as
determined manually shall  be considered the referee test.)

     4.2  Thermometers:  Two standard thermometers  shall  be  used  with the
ASTM Pensky-Martens tester.

          4.2.1  For tests  in  which the indicated reading  falls within  -7* to
     -f-110* C (20* to 230* F),  inclusive:  either (1) an  ASTM Pensky-Martens
     Low Range or Tag Closed Tester Thermometer having a range from  -7* to
     +110* C (20* to 230" F) and conforming to the  requirements  for  Thermometers
     SC (9F) and as prescribed in ASTM Specification El, or (2) an IP Thermo-
     meter 15C (15F) conforming to specifications given  in  Annex  A3  of  ASTM
     D93-77.
     iThis method is based on ASTM Method D93-77.   Refer to 093-77 or D93-80
for more information.
                                      D-446
-------
2 / CHARACTERISTICS - Ignitability


          4.2.2  For tests in which the indicated reading falls within 110*
     to 370* C (230* to 700* F):  either (1) an ASTM Pensky-Martens High
     Range Thermometer having a range from 90* to 370" C (200* to 700* F) and
     conforming to the requirements for Thermometers IOC (10F) as prescribed
     in Specification El, or (2) IP Thermometer 16C (16F) conforming to
     specifications given in Annex A3 of ASTM D93-77.


5.0  Reagents

     5.1  Calcium chloride.

     5.2  p-Xylene reference standard.


6.0  Sample Collection, Preservation, and Handling

     6.1  All samples must be collected using a sampling plan that addresses
the considerations discussed in Section One of this manual.

     6.2  Samples shall not be stored in plastic bottles since volatile
materials may diffuse through the walls of the bottle.


7.0  Procadure

     7.1  Preparation of samples:  Samples that do not contain volatile
contaminants shall be prepared in the following manner.  NOTE:  If the sample
is suspected of containing volatile contaminants, the  treatment described in
7.1.1 and 7.1.2 should be omitted.

          7.1.1  Samples of very viscous materials may be warmed until they
     are reasonably fluid before they are tested.  However,  no sample should
     be heated more than is absolutely necessary, and  no sample should ever
     be heated to a temperature that exceeds 17' C (30* F) below the sample's
     expected flash point.

          7.1.2  Samples containing dissolved or free  water  may be dehydrated
     with calcium chloride or by filtering through a qualitative filter paper
     or a loose plug or dry absorbent cotton.  Warming the sample is permitted,
     but it shall not be heatad for prolonged periods  or above a temperature
     of 17* C (30* F) below the sample's expected flash point.

     7.2  Routine procedure

         7.2.1  Thoroughly clean and dry all parts of  the cup and its
     accessories before starting the test.  Be sure to remove any solvent
     that was used to clean the apparatus.  Fill the cup with the sample to
                                       D-447
-------
 --                                                                       1010 / 3


            be tested to the level indicated by the filling mark.  Place the lid on
            the cup and set the latter in the stove.  Be sure to properly engage the
            locating or locking device.  Insert the thermometer.  Light the test
            flame and adjust it to a diameter of 5/32 in. (4 mm).  Supply the heat
            at such a rate that the temperature as indicated by the thermometer
            increases 5* to 6* C (9* to 11* F)/min.  Turn the stirrer 90 to 120 rpm,
            stirring in a downward direction.

                 7.2.2  If the sample is expected to have a flash point of 110* C
            (230* F) or below, apply the test flame when the temperature of the
            sample is from 17* C (30* F) to 28* C (50* F) below the expected
            flash point and thereafter at a temperature reading that is a multiple
            of 1* C (2* F).  Apply the test flame by operating the mechanism on the
            cover which controls the shutter and test flame burner so-that the flame
            is lowered into the vapor space of the cup in 0.5 sec, left in its
            lowered position for 1 sec, and quickly raised to its high position.
            Do not stir the sample while applying the test flame.

                 7.2.3  If the sample is expected to have a flash point above 110* C
            (230* F), apply the test flame in the manner just described at each
            temperature that is a multiple of 2* C (5* F), beginning at a temperature
            of 17* C (30* F) to 28* C (50* F) below the expected flash point.
            NOTE:  When testing materials to determine if volatile contaminants are
 >--          present, it is not necessary to adhere to the temperature limits for
•C.          initial flame application as stated in 7.2.2 and 7.2.3.

                 7.2.4  Record as the flash point the temperature read on the
            thermometer at the time the test flame application causes a distinct
            flash in the interior of the Cup.  Do not confuse the true flash point
            with the bluish halo that sometimes surrounds the test flame at applica-
            tions preceding the one that causes the actual flash.  The actual flash
            will have occurred when a large flame propagates itself over the surface
            of the sample.

            7.3  Determination of flash point of suspensions of solids and highly
       viscous materials

                 7.3.1  Bring the material to be tested and the tester to a tempera-
            ture of 15* i 5* C (60* + 10* F) or 11* C (20* F) lower than the estimated
            flash point, whichever is lower.  Turn the stirrer 250+^10 rpm, stirring
            in a downward direction.  Raise the temperature throughout the duration
            of the test at a rate of not less than 1* nor more than 1.5" F (2 to 3* F)/
            min.  With the exception of these requirements for rates of stirring
            and heating, proceed as prescribed in Section 7.2.

            7.4  Calculation and report

                 7.4.1  Observe and record the ambient barometric pressure at the
            time of the test.  When the pressure differs from 760 mm Hg (101.3 kPa),
v           correct the flash point as follows:


                                              D-448
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4 / CHARACTERISTICS - Ignitability

          (A) Corrected flash point = C + 0.25 (101.3 - p)
          (B) Corrected flash point = F + 0.06 (760 - P)
          (C) Corrected flash point = C + 0.033 (760 - P)
     where:
          F = observed flash point, *F
          C = observed flash point, *C
          P = ambient barometric pressure, mm Hg
          p = ambient barometric pressure, kPa.
     NOTE:  The barometric pressure used in this calculation must be the
     ambient pressure for the laboratory at the time of test.  Many aneroid
     barometers, such as those used at weather stations and airports, are
     precorrected to give sea level readings.  These must not be used.
          7.4.2  Record the corrected flash point to the nearest
     0.5* C  (or r F).
          7.4.3  Report the recorded flash point as the Pensky-Martens Closed
     Cup Flash Point ASTM D93 - IP 34, of the sample tested.
     7.5  Refer to Method ASTM 093 77 for more details and background
on the Pensky-Marten method.

8.0  Quality Control
     8.1  All quality control data should be available for review.
     8.2  Duplicates and standard  reference materials should be routinely
analyzed.
     8.3  The flash point of the p-xylene reference standard must be deter-
mined in duplicate at least once'per sample batch.  The average of the two
analyses should be 27' + 0.8* C (81* +. 1.5* F).
                                  D-449
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a

.t-
Ul
o
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EPA METHOD
 NO. 1110
      D-451
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                                METHOD 1110

                          CORROSIVITY TOWARD STEEL
1.0  Introduction
     1.1  Method lllQl is used to measure the corrosivity toward steel of
both aqueous and nonaqueous liquid wastes.


2.0  Summary of Method

     2.1  This test exposes coupons of SAE Type 1020 steel  to the liquid
waste to be evaluated and, by measuring the degree to which the coupon has
been dissolved, determines the corrosivity of the waste.


3.0  Interferences

     3.1  In laboratory tests, such as this one, corrosion of duplicate
coupons is usually reproducible to within ^ 10%.  However,  large differences
in corrosion rates may occasionally occur under conditions  where the metal
surfaces become passivated.  Therefore, at least duplicate determinations of
corrosion rate should be made.
4.0  Apparatus and Materials

     4.1  A versatile and convenient apparatus should be used, consisting of
a kettle or flask of suitable size (usually 500 to 5000 milliliters),
a reflux condenser, a thermowell  and temperature regulating device, a heating
device (mantle, hot plate, or bath), and a specimen support system.  A
typical resin flask set up for this type test is shown in Figure 1.

     4.2  The supporting device and container should not be affected by or
cause contamination of the waste under test.

     4.3  The method of supporting the coupons will vary with the apparatus
used for conducting the test but should be designed to insulate the coupons
from each other physically and electrically and to insulate the coupons from
any metallic container or other device used in the test.  Some common support
materials include glass, fluorocarbon or coated metal.


     ^hTs~method is based on NACE Standard TM-01-69 (1972 Revision),
"Laboratory Corrosion Testing of Metals for the Process Industries," National
Association of Corrosion Engineers, 3400 West Loop South, Houston, TX
77027.
                                      D-452
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 2 /  CHARACTERISTICS -  Corrosivity
                                                              H
     Figure 1. Typical resin flask that can be used as a versatile and convenient apparatus to
conduct simple immersion tests.  Configuration of the flask top is such that more sophisticated
apparatus can be added as required by the specific test being conducted. A = thermowell, B =
resin flask,  C * specimens hung on supporting device, D * gas inlet, E a heating mantle, F a liquid
interface, G = opening in flask for additional apparatus that may be required, and H » reflux
condenser.
                                          D-453
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                                                                     1110 / 3


     4.4  The shape and form of the coupon support should ensure free contact
with the waste.

     4.5  A circular specimen of SAE 1020 steel  of about 3.75 cm (1.5 Inch)
diameter Is a convenient shape for a coupon.   With a thickness of approxi-
mately 0.32 cm (0.125 inch) and a 0.80-cra (0.4-1n.) diameter hold for
mounting, these specimens will readily pass through a 45/50 ground glass
joint of a distillation kettle.  The total surface area of a circular speci-
men 1s given by the following equation:

          A » 3.14/2(D2-d2) + (t)(3.14)(0) + (t)(3.14)(d)

where t * thickness, 0 * diameter of the specimen, and d * diameter of the
mounting hole.  If the hole 1s completely covered by the mounting support,
the last term (t)(3.14)(d) 1n the equation 1s omitted.

          4.5.1  All coupons should be measured carefully to permit accurate
     calculation of the exposed areas.  An area calculation accurate to +. 1%
     1s usually adequate.                                               ~

          4.5.2  More uniform results may be expected 1f a substantial layer
     of metal 1s removed from the coupons prior to testing the corrosivity of
     the waste.  This can be accomplished either by chemical treatment
     (pickling), electrolytic removal, or by grinding with a coarse abrasive.
     At least 0.254 mm (0.0001 inch) or 2 to 3 rag/cm* should be removed.
     Final surface treatment should Include finishing with #120 abrasive
     paper or cloth.  Final cleaning consists of scrubbing with bleachfree
     scouring powder, followed by rinsing in distilled water, then acetone or
     methanol, and finally air drying.  After final cleaning, the coupon
     should be stored 1n a desiccator until used.

          4.5.3  The minimum ratio of volume of waste to area of the metal
     coupon to be used in this test 1s 40 ml/cm2.


5.0  Reagents

     5.1  Sodium hydroxide  (20%).

     5.2  Zinc dust.

     5.3  Concentrated hydrochloric acid.

     5.4  Stannous chloride.

     5.5  Antimony chloride.
                                       D-454
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4 / CHARACTERISTICS - Corrosivity


6.0  Sample Collection. Presentation, and Handling

     6.1  All  samples should be collected using a sampling plan  that addresses
the considerations discussed in Section One of this manual.
7.0  Procedure

     7.1  Assemble the test apparatus as described in Section 4.0 above.

     7.2  Fill the container with the appropriate amount of waste.

     7.3  Begin agitation at a rate sufficient to ensure that the liquid  is
kept well mixed and homogeneous.

     7.4  Using the heating device bring the temperature of the waste to
55* C (130' F).

     7.5  An accurate rate of corrosion is not required but only a
determination as to whether the rate of corrosion is less than or greater
than 6.35 mm per year.  A 24-hour test period should be ample to determine
whether or not the rate of corrosion is greater than 6.35 mm per year.
                                                                   «
     7.6  In order to accurately determine the amount of material lost to
corrosion, the coupons have to be cleaned after immersion and prior to
weighing.  The cleaning procedure should remove all products of corrosion
while removing a minimum of sound metal.  Cleaning methods can be divided
into three general categories:  mechanical, chemical and electrolytic.

          7.6.1  Mechanical cleaning includes scrubbing, scraping, brushing
     and ultrasonic procedures.  Scrubbing with a bristle brush and mild
     abrasive is the most popular of these methods.  The others are used  in
     cases of heavy corrosion as a first step in removing heavily encrusted
     corrosion products- prior to scrubbing.  Care should be taken to avoid
     removing sound metal.

          7.6.2  Chemical cleaning implies the removal of material from the
     surface of the coupon by dissolution in an appropriate solvent.  Solvents
     such as acetone, dlchloromethane, and alcohol are used to remove oil,
     grease or resinous materials, and are used prior to immersion to remove
     the products of corrosion.  Solutions suitable for removing corrosion
     from the steel coupon are:

                Solution                       Soaking Time   Temperature

     20% NaOH +  200 g/1 zinc dust                 5 min        Boiling

                 or

     Cone. HC1 + 50 g/1 Snd2 + 20 g/1 SbCla   Until clean      Cold
                                       D-455
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                                                                     1110 / 5


          7.6.3  Electrolytic cleaning sheu1 •  be preceded by scrubbing to
     remove loosely adhering corrosion products.  One method of electrolytic
     cleaning that can be employed is:

          Solution                          "0 g/1  83804

          Anode                             *.rt>on  or lead

          Cathode                           l;eel  coupon

          Cathode current density           .3 amp/cm2 (129 amp/in.2)

          Inhibitor                         i  ;c organic inhibitor/liter

          Temperature                       "** C (165* F)

          Exposure Period                   j  minutes

     NOTE:  Precautions must be taken to ensure good electrical contact with
     the coupon, to avoid contamination of ths cleaning solution with easily
     reducible metal ions, and to ensure thac  inhibitor decomposition has not
     occurred.  Instead of using a proprietary inhibitor, 0.5 g/1  or either
     diorthotolyl thiourea or quinolin ethiodide can be used.

     7.7  Whatever treatment is employed to clean the coupons, its effect In
removing sound metal should be determined using a blank (i.e., a coupon that
has not been exposed to the waste).  The blank should be cleaned along witrt
the test coupon and its waste loss subtracted  from  that calculated for the
test coupons.

     7.8  After corroded specimens have been cleaned and dried, they are
reweighed.  The weight loss is employed as the principal  measure of corrosfon.
Use of weight loss as a measure of corrosion requires making the assumption
that all weight loss has been due to generalized corrosion and not localized
pitting.  In order to determine the corrosion  rate  for the purpose of this
regulation, the following formula is used:

          Corrosion Rate (mmpy) * weight loss  x 11.145
                                      area x time

          where weight loss is in milligrams,  area  in square centimeters,
          time in hours, and corrosion rate in millimeters per year
          (mmpy).


8.0  Quality Control

     8.1  All quality control data should b«  filed and available for
auditing.

     8.2  Duplicate samples should be analyzed on a routine basis.
                                     D-456
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HAZARDOUS WASTE CHARACTERISTICS
         -REACTIVITY-
         (FROM SW 846)
                D-457
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                   CHARACTERISTICS - Corrosivity; Reacfvity
     2.1.3  Reactivity

Introduction

     The regulation in 40 CFR 261.23 defines reactive wastes to include
wastes which have any of the following properties:   (1)  readily undergo
violent chemical change; (2) react violently or form potentially explosive
mixtures with water; (3) generate toxic fumes when  mixed with water or, in
the case of cyanide or sulfide-bearing wastes, when exposed to mild acidic
or basic conditions; (4) explode when subjected to  a strong initiating force;
(5) explode at normal temperatures and pressures; or (6) fit within the
Department of Transportation's forbidden explosives, Class A explosives, or
Class B explosives classifications.

     This definition is intended to identify wastes which, because of
their extreme instability and tendency to react violently or explode, pose
a problem at all stages of the waste management process.  The definition is
to a large extent a paraphrase of the narrative definition employed by the
National Fire Protection Association.  The Agency chose  to rely on a
descriptive, prose definition of reactivity because the  available tests
for measuring the variegated class of effects embraced by the reactivity
definition suffer from a number of deficiencies.


Regulatory Definition

     Characteristic of Reactivity Regulation

     A solid waste exhibits the characteristic of reactivity if a representa-
tive sample of the waste has any of the following properties:

      1.  It is normally unstable and readily undergoes  violent change
          without detonating.

      2.  It reacts violently with water.

      3.  It forms potentially explosive mixtures with water.

      4.  When mixed with water, it generates toxic gases, vapors or fumes
          in a quantity sufficient to present a danger to human health or
          the environment,

      5.  It is a cyanide-  or sulfide-bearing waste which, when exposed to pH
          conditions between 2 and 12.5, can generate toxic gases, vapors,
          or fumes in  a quantity sufficient to present a danger to human
          health or  the environment.   (Methods 9010 and 9030 can  be used to
          detect the presence of cyanide and sulfide in wastes.)

      6.  It is capable of  detonation or explosive  reaction if  it  is
          subjected  to a strong  initiating  source or if heated  under
          confinement.

                                      D-458
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2 / CHARACTERISTICS - Reactivity


      7.  It is readily capable of detonation or explosive decomposition or
          reaction at standard temperature and pressure.

      8.  It is a forbidden explosive as defined in 49 CFR 173.51, or a
          Class A explosive as defined in 49 CFR 173.53,  or a Class B
          explosive as defined in 49 CFR 173.88.

      9.  A solid waste that exhibits the characteristic  of reactivity, but
          is not listed as a hazardous waste in Subpart D, has the EPA
          Hazardous Waste Number of D003.
     Definition of Explosive Materials

     For purposes of this regulation, a waste is a reactive waste by reason
of explosivity if it meets one or more of the following descriptions:

      1.  Is explosive and ignites spontaneously or undergoes marked
          decomposition when subjected for 48 consecutive hours to a
          temperature of 75* C (167* F).

      2.  Firecrackers, flash crackers, salutes, or similar commercial
          devices which produce or are intended to produce an audible
          effect, the explosive content of which exceeds 12 grains each in
          weight; pest control bombs, the explosive content of which exceeds
          18 grains each in weight; and any such devices, without respect to
          explosive content, which on functioning are liable to project or
          disperse metal, glass or brittle plastic fragments.

      3.  Fireworks that combine an explosive and a detonator or blasting
          cap.

      4.  Fireworks containing an ammonium salt and a chlorate.

      5.  Fireworks containing yellow or white phosphorus.

      6.  Fireworks or firework compositions that ignite spontaneously or
          undergo marked decomposition when subjected for 48 consecutive
          hours to a temperature of 75* C (167* F).

      7.  Toy torpedoes, the maximum outside dimension of which exceeds
          7/8 inch, or toy torpedoes containing a mixture of potassium
          chlorate, black antimony and sulfur with an average weight of
          explosive composition in each torpedo exceeding four grains.

      8.  Toy torpedoes containing a cap composed of a mixture of red
          phosphorus and potassium chlorate exceeding an average of one-half
          (0.5) grain per cap.

      9.  Fireworks containing copper sulfate and a chlorate.

                                    D-459
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                                              Regulatory  Definition  / 3


10.   Explosives  containing  an  ammonium  salt  and  a  chlorate.

11.   Liquid nitroglycerin,  diethylene glycol  dinitrate  or other liquid
     explosives  not  authorized.

12.   Explosives  condemned by the  Bureau of Explosives  (except  properly
     packed samples  for  laboratory  examinations).

13.   Leaking or  damaged  packages  of explosives.

14.   Solid materials which  can be caused to  deflagrate  by contact with
     sparks or flame such as produced by safety  fuse or an electric
     squib, but  cannot be detonated (see Note 1) by  means of a No. 8
     test blasting  cap  (see Note  2).  Example:  Black  powder and low
     explosives.

15.   Solid materials which  contain  a  liquid  ingredient, and which, when
     unconfirmed  (see Note 3),  can be  detonated by  means of a No. 8 test
     blasting cap (see Note 2); or  which can be  exploded  in at least
     50 percent  of  the trials  in  the  Bureau  of Explosives' Impact
     Apparatus (see  Note 4) under a drop of  4 inches or more,  but
     cannot be exploded  in  more than  50 percent  of the  trials  under  a
     drop of less than 4 inches.   Example:   High explosives, commercial
     dynamite containing a  liquid explosive  ingredient.

16.   Solid materials which  contain  no liquid ingredient and which can
     be detonated,  when  unconfined  (see Note 3), by  means of No. 8 test
     blasting cap (see Note 2); or  which can be  exploded in at least
     50 percent  of  the trials  in  the Bureau  of Explosives' Impact
     Apparatus (see Note 4) under a drop of  4 inches or more,  but
     cannot be exploded  in  more than  50 percent  of the  trials  under  a
     drop of less than 4 inches.   Example:   high explosives, commercial
     dynamite containing no liquid  explosive ingredient,  trinitrotoluene,
     amatol, tetryl, picric acid, ureanitrate, pentolite, commercial
     boosters.

17.   Solid materials which  can be caused to  detonate when unconfined
     (see Note 3),  by contact  with sparks or flame such as produced by
     safety fuse or an  electric squib;  or which can be exploded in the
     Bureau of Explosives'  Impact Apparatus  (see Note 4), in more than
     50 percent of  the  trials  under a drop of less than 4 inches.
     Example:  initiating  and  priming explosives, lead azide,  fulminate
     of mercury, high explosives.

18.   Liquids which  may  be  detonated separately or when absorbed in
     sterile absorbent  cotton, by a No. 8 test blasting cap (see  Note
     2); but which  cannot  be exploded in the Bureau of Explosives'
     Impact Apparatus (see Note 4), by  a drop of less than 10 inches.
     The liquid must not be significantly more volatile than nitro-
     glycerine and must  not freeze at temperatures above minus  10" F.
     Example:  high explosives, desensitized nitroglycerine.

                                  D-460
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4 / CHARACTERISTICS - Reactivity


     19.  Liquids that can be exploded in the Bureau of Explosives'  Impact
          Apparatus (see Note 4) under a drop of less than 10 inches.
          Example:  nitroglycerine.

     20.  Blasting caps,  these are  small tubes, usually made of an  alloy of
          either copper or aluminum, or of molded plastic closed at  one end
          and loaded with a charge of initiating or priming explosives.
          Blasting caps (see Note 5) which have been provided with a means
          for firing by an electric  current,  and sealed, are known as
          electric blasting caps.

     21.  Detonating primers which contain a  detonator and an additional
          charge of explosives, all  assembled in a suitable envelope.

     22.  Detonating fuses, which are used in the military service to
          detonate the high explosive bursting charges of projectiles,
          mines, bombs, torpedoes, and grenades.  In addition to a powerful
          detonator, they may contain several ounces of a high explosive,
          such as tetryl or dry nitrocellulose, all  assembled in a heavy
          steel  envelope.  They may  also contain a small amount of radio-
          active component.  Those that will  not cause functioning of other
          fuses, explosives, or explosive devices in the same or adjacent
          containers are classes as  class C explosives and are not reactive
          waste.

     23.  A shaped charge, consisting of a plastic,  paper, or other  suitable
          container comprising a charge of not to exceed 8 ounces of a  high
          explosive containing no liquid explosive ingredient and with  a
          hollowed-out portion (cavity) lined with a rigid material.

     24.  Ammunition or explosive projectiles, either fixed, semi-fixed or
          separate components which  are made  for use in cannon, mortar,
          howitzer, recoil less rifle, rocket, or other launching device with
          a caliber of 20 mm or larger.

     25.  Grenades.  Grenades, hand  or rifle, are small metal  or other
          containers designed to be  thrown by hand or projected from a
          rifle.  They are filled with an explosive or a liquid, gas,  or
          solid material such as a tear gas or an incendiary or smoke
          producing material and a bursting charge.

     26.  Explosive bombs.  Explosive bombs are metal or other containers
          filled with explosives.  They are used in warfare and include
          airplane bombs and depth bombs.

     27.  Explosive mines.  Explosive mines are metal or composition
          containers filled with a high explosive.

     28.  Explosive torpedoes.  Explosive torpedoes, such as those used in
          warfare, are metal devices containing a means of propulsion  and a
          quantity of high explosives.

                                     D-461
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                                                    Regulatory  Definition  /  5


     29.   Rocket  ammunition.  Rocket ammunition  (including  guided  missiles)
          is  ammunition designed for launching from  a  tube,  launcher,  rails,
          trough, or other  launching device,  in  which  the propel 1 ant
          material  is  a solid propel!ant  explosive.   It  consists of an
          igniter,  rocket motor, and projectile  (warhead) either fused or
          unfused,  containing high explosives or chemicals.

     30.   Chemical  ammunition.  Chemical  ammunition  used in  warfare is all
          kinds  of explosive chemical  projectiles, shells,  bombs,  grenades,
          etc.,  loaded with tear, or other gas,  smoke  or incendiary agent,
          also such miscellaneous apparatus as cloud-gas cylinders, smoke
          generators,  etc.,.that may be utilized to  project  chemicals.

     31.   Boosters, bursters, and supplementary  charges. Boosters and
          supplementary charges consist of a  casing  containing  a  high
          explosive and are used to increase  the intensity  of explosion of
          the detonator of  a detonating fuse.  Bursters  consist of a  casing
          containing a high explosive  and are used to  rupture a projectile
          or  bomb to permit release of its contents.

     32.   Jet thrust units  or other rocket motors containing a  mixture of
          chemicals capable of  burning rapidly and producing considerable
          pressure.

     33.   Propellant mixtures  (i.e., any  chemical mixtures  which are
          designed to function  by rapid combustion with  little  or  no  smoke).

NOTE 1:  The  detonation test  is performed by  placing the sample in an open-end
fiber tube which is set on  the  end of  a lead  block approximately 1-1/2 in.
in diameter and 4 in.  high  which, in turn,  is placed on  a  solid base.   A
steel plate may be placed between the  fiber tube and the lead block.

NOTE 2:  A No. 8 test blasting  cap is  one containing two grams  of a mixture
of 80% mercury fulminate  and  20%  potassium chlorate, or  a  cap of equivalent
strength.

NOTE 3:  "Unconfined" as  used  in  this  section does  not exclude  the use of a
paper or soft fiber tube  wrapping to  facilitate  tests.

NOTE 4:  The Bureau of Explosives'  Impact Apparatus  is a testing device
designed so that a guided 8-1 b  weight  may be  dropped from predetermined
heights so as to impact  specific  quantities  of liquid or solid materials
under fixed conditions.   Detailed prints  of the  apparatus may be obtained
from the Bureau of Explosives,  Association of American Railroads, Operations
and Maintenance Dept., Bureau of  Explosives,  American Railroad Building,
Washington, D.C. 20036;  202-293-4048.   The procedures for operating this
apparatus are described in  the following paragraphs.

     Method for  Testing Liquids.   The anvil  is  inserted in the receptable in
     the anvil housing.A new cup  is  dropped into the  cup-positioning block.
     One drop of the sample liquid  (about 0.01  g) is dropped into the  cup

                                  B-462
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6 / CHARACTERISTICS - Reactivity; EP Toxicity


     from a pipette and the cup is revolved until an even film forms on base.
     The top striker and the main striker are inserted as far as possible
     into the upper housing.  The upper housing is then placed over the
     cup-positioning block so that the end of the main striker goes into the
     brass cup.  When the upper housing is removed from the cup-positioning
     block, the brass cup is picked up on the end of the main striker.  When
     the two housings are screwed together, the brass cup automatically rests
     firmly on the anvil.

     An 8-1b drop weight is dropped from predetermined heights until consistent
     failure results using the new sample portion and cup each time.  An
     explosion is evidenced by flame or flame and noise, but in either event
     the brass cup will be belled out or bulged.

     After making the drop, the drop weight is raised, the test assembly
     removed, and appropriate solvent is poured into the top end.  The two
     housings are then separated, the striker removed, and the brass cup
     removed from the striker end.

     All solvent is removed carefully and thoroughly before preparations are
     started for next drop and the apparatus cooled and cleaned.  The test is
     then repeated in the same manner, but with a filter paper disc in the
     base of the cup under the composition being tested.

     Method for Testing Solids.  The die is placed in the anvil assembly and
     a small amount (about 0.01 g)1 to make a thin film is placed into the
     die assembly.  The steel striker pellet (plug) is inserted carefully and
     then the striker (plunger).  The assembly is then placed in the apparatus
     and the drop weight allowed to rest on the striker top to effect even
     distribution of the explosive.

     The 8-1b drop weight is then dropped on the striker from predetermined
     heights until consistent failure results (i.e., explosion, etc.) using a
     new sample portion each time.

     The die assembly is removed carefully and the striker removed.  A few
     drops of appropriate solvent are poured into the die assembly before it
     is disassembled.

     All parts are cleaned and dried carefully before each test.

NOTE 5:  Blasting caps, blasting caps with safety fuse, or electric blasting
caps in quantities of 1,000 or less are classified as class 0 explosives and
not subject to regulation as a reactive waste.
              is suggested that a tiny spoon be devised to measure the proper
     amount of test sample, since this is much more convenient and safer than
     other methods of measuring the sample.
                                   D-463
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