METHOD 9031

EXTRACTABLE SULFIDES

1.0 SCOPE AND APPLICATION

1.1 The extraction procedure described in this method is designed for

the extraction of sulfides from matrices that are not directly amenable to the
distillation procedure Method 9030. Specifically, this method is designed for
the extraction of soluble sulfides. This method is applicable to oil, solid,
multiphasic, and all other matrices not amenable to analysis by Method 9030.
This method is not applicable for reactive sulfide. Refer to Chapter Seven for
the determination of reactive sulfide.

1.2 Method 9031 is suitable for measuring sulfide in solid samples at

concentrations above 1 mg/kg.

2.0 SUMMARY OF METHOD

2.1 If the sample contains solids that will interfere with agitation
and homogenization of the sample mixture, or so much oil or grease as to
interfere with the formation of a homogeneous emulsion in the distillation
procedure, the sample may be filtered and the solids extracted with water at pH
> 9 and < 11. The extract is then combined with the filtrate and analyzed by the
distillation procedure. Separation of sulfide from the sample matrix is
accomplished by the addition of sulfuric acid to the sample. The sample is
heated to 70EC and the hydrogen sulfide (H2S) which is formed is distilled under
acidic conditions and carried by a nitrogen stream into zinc acetate gas
scrubbing bottles where it is precipitated as zinc sulfide.

2.2 The sulfide in the zinc sulfide precipitate is oxidized to sulfur

with a known amount of excess iodine. Then the excess iodine is determined by
titration with a standard solution of phenylarsine oxide (PAO) or sodium
thiosulfate until the blue iodine starch complex disappears. The use of standard
sulfide solutions is not possible because of their instability to oxidative
degradation. Therefore quantitation is based on the PAO or sodium thiosulfate.

3.0 INTERFERENCES

3.1 Samples with aqueous layers must be taken with a minimum of

aeration to avoid volatilization of sulfide or reaction with oxygen which
oxidizes sulfide to sulfur compounds that are not detected.

3.2 Sulfur compounds such as sulfite and hydrosulfite decompose in acid

and may form sulfur dioxide. This gas may be carried over to the zinc acetate
gas scrubbing bottles and subsequently react with the iodine solution yielding
false high values. The addition of formaldehyde into the zinc acetate gas
scrubbing bottles removes this interference. Any sulfur dioxide entering the
scrubber will form an addition compound with the formaldehyde which is unreactive
towards the iodine in the acidified mixture. This method shows no sensitivity
to sulfite or hydrosulfite at concentrations up to 10 mg/kg of the interferant.

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 3.3 The iodometric method suffers interference from reducing substances
that react with iodine including thiosulfate, sulfite, and various organic
compounds.

3.4 Interferences have been observed when analyzing samples with high
metal content such as electroplating waste and chromium containing tannery waste.

4.0 APPARATUS AND MATERIALS

4.1 Extractor - Any suitable device that sufficiently agitates a sealed

container of one liter volume or greater. For the purpose of this analysis,
agitation is sufficient when:

1. All sample surfaces are continuously brought into contact

with extraction fluid, and

2. The agitation prevents stratification of the sample and

fluid.

Examples of suitable extractors are shown in Figures 2 and 3. The tumble-

extractors turn the extraction bottles end-over-end at a rate of about 30 rpm.
The apparatus in Figure 2 may be easily fabricated from plywood. The jar
compartments must be padded with polyurethane foam to absorb shock. The drive
apparatus is a Norton jar mill.

4.2 Buchner funnel apparatus

4.2.1 Buchner funnel - 500-mL capacity, with 1-liter vacuum

filtration flask.

4.2.2 Glass wool - Suitable for filtering, 0.8 Fm diameter such

as Corning Pyrex 3950.

4.2.3 Vacuum source - Preferably a water driven aspirator. A

valve or stopcock to release vacuum is required.

4.3 Gas Evolution apparatus as shown in Figure 1

4.3.1 Three neck flask - 500-mL, 24/40 standard tapered joints.

4.3.2 Dropping funnel - 100-mL, 24/40 outlet joint.

4.3.3 Purge gas inlet tube - 24/40 joint with course frit.

4.3.4 Purge gas outlet - 24/40 joint reduced to 1/4 inch tube.

4.3.5 Gas scrubbing bottles - 125-mL, with 1/4 in. o.d. inlet and
outlet tubes. Impinger tube must not be fritted.

4.3.6 Tubing - 1/4 in. o.d. Teflon or polypropylene. Do not use

rubber.

4.4 Hot plate stirrer.

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 4.5 pH meter.

4.6 Nitrogen regulator.

4.7 Flowmeter.

4.8 Separatory funnels - 500-mL.

4.9 Tumbler - See Figures 2 and 3.

4.10 Top-loading balance - capable of weighing 0.1 g.

5.0 REAGENTS

5.1 Reagent grade chemicals shall be used in all tests. Unless

otherwise indicated, it is intended that all reagents shall conform to the
specifications of the Committee on Analytical Reagents of the American Chemical
Society, where such specifications are available. Other grades may be used,
provided it is first ascertained that the reagent is of sufficiently high purity
to permit its use without lessening the accuracy of the determination.

5.2 Reagent water. All references to water in this method refer to

reagent water, as defined in Chapter One.

5.3 Zinc acetate (for sample preservation) (2N), Zn(CH3C00)2 C 2H 2 O.

Dissolve 220 g of zinc acetate dihydrate in 500 mL of water.

5.4 Sodium hydroxide (50% w/v in water), NaOH. Commercially available.

5.5 Tin (II) chloride, SnCl2 C 2H2O, granular.

5.6 n-Hexane, C6H .

14
5.7 Nitrogen, N2.

5.8 Sulfuric acid (concentrated), H2SO4.

5.9 Zinc acetate for the scrubber (approximately 0.5M). Dissolve 110
g zinc acetate dihydrate in 200 mL of water. Add 1 mL concentrated hydrochloric
acid, HCl, to prevent precipitation of zinc hydroxide. Dilute to 1 liter.

5.10 Formaldehyde (37% solution), CH2O. Commercially available.

5.11 Starch solution. Use either an aqueous solution or soluble starch

powder mixtures. Prepare an aqueous solution as follows. Dissolve 2 g soluble
starch and 2 g salicylic acid, C7H6O3, as a preservative, in 100 mL hot water.

5.12 Iodine solution (approximately 0.025N). Dissolve 25 g of potassium

iodide, KI, in 700 mL of water in a 1-liter volumetric flask. Add 3.2 g of
iodine, I2. Allow to dissolve. Dilute to 1 liter and standardize as follows.
Dissolve approximately 2 g KI in 150 mL of water. Pipet exactly 20 mL of the
iodine solution to be titrated and dilute to 300 mL with water. Titrate with
0.025N standard phenylarsine oxide, or 0.025N sodium thiosulfate, Na2S2O3, until
the amber color fades. Add starch indicator solution until the solution turns

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deep blue. Continue titration drop by drop until the blue color disappears.
Run in replicate. Calculate the normality as follows:

Normality (I2) = mL of titrant x normality of titrant

Volume of sample (mL)

5.13 Sodium sulfide nonanhydrate Na2S C 9H 2 O, for the preparation of

standard solutions to be used for calibration curves. Standards must be prepared
at pH > 9 and < 11.

5.14 Titrant.

5.14.1 Standard phenylarsine oxide (PAO) solution (0.025N),

C6H5AsO. This solution is commercially available.

CAUTION: PAO is toxic.

5.14.2 Standard sodium thiosulfate solution (0.025N), Na2S2O3 C

5H2O. Dissolve 6.205 + 0.005 g Na2S2O3 C 5H2O in 500 mL of water. Add 9
mL 1N NaOH and dilute to 1 liter.

6.0 SAMPLE COLLECTION, PRESERVATION, AND HANDLING

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

6.2 All samples must be preserved with zinc acetate and sodium
hydroxide. Use four drops of 2N zinc acetate solution per 100 mL of aqueous or
multiphasic sample. Adjust the pH to greater than 9.0 with 50% NaOH. Fill the
sample bottle completely and stopper with a minimum of aeration. For solid
samples, fill the surface of solid with 2N zinc acetate until moistened. Samples
must be cooled to 4EC during storage.

7.0 PROCEDURE

7.1 Assemble the Buchner funnel apparatus. Unroll the glass wool and
fold the fiber over itself several times to make a pad about 1 cm thick when
lightly compressed. Cut the pad to fit the Buchner funnel. Dry and weigh the
pad, then place it in the funnel. Turn on the aspirator and wet the pad with a
known amount of water.

7.2 Transfer a sample that contains between 1 and 50 mg of sulfide to

the Buchner funnel. Rinse the sample container with known amounts of water and
add the rinses to the Buchner funnel. When no free water remains in the funnel,
slowly open the stopcock to allow air to enter the vacuum flask. A small amount
of sediment may have passed through the glass fiber pad. This will not interfere
with the analysis.

7.3 Transfer the solid and the glass fiber pad to a dried tared
weighing dish. Since most greases and oils will not pass through the fiber pad,
solids, oils, and greases will be extracted together. If the filtrate includes
an oil phase, transfer the filtrate to a separatory funnel. Collect and measure
the volume of the aqueous phase. Transfer the oil phase to the weighing dish
with the solid and glass fiber pad.

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 7.4 Weigh the dish containing solid, oil (if any), and glass fiber pad.
Subtract the weight of the dry glass fiber pad. Calculate the volume of water
present in the original sample by subtracting the total volume of rinses from the
measured volume of the filtrate.

7.5 Place the following in a 1-liter wide-mouth bottle:

500 mL water
5 mL 50% w/v NaOH
1 g SnCl2 C 2H2O
50 mL n-hexane (if an oil or grease is present).

Cap the bottle with a Teflon or polyethylene lined cap and shake vigorously to
saturate the solution with stannous chloride. Direct a stream of nitrogen gas
at about 10 mL/min into the bottle for about 1 minute to purge the headspace of
oxygen. If the weight of the solids (Step 7.4) is greater than 25 g, weigh out
a representative aliquot of 25 g and add it to the bottle while still purging
with nitrogen. Otherwise, add all of the solids. Cap the bottle; avoid the
influx of air.

7.6 The pH of the extract must be maintained at > 9 or < 11 throughout

the extraction step and subsequent filtration. Since some samples may release
acid, the pH must be monitored as follows. Shake the extraction bottle and wait
1 minute. Open the bottle under a stream of nitrogen and check the pH. If the
pH is below 9, add 50% NaOH in 5 mL increments until it is at least 9. Recap the
bottle, and repeat the procedure until the pH does not drop. The bottle must be
thoroughly purged of oxygen before each recapping. Oxygen will oxidize sulfide
to elemental sulfur or other sulfur containing compounds that will not be
detected.

7.7 Place the bottle in the tumbler, making sure there is enough foam
insulation to cushion the bottle. Turn the tumbler on and allow the extraction
to run for about 18 hours.

7.8 Prepare a Buchner funnel apparatus as in Step 7.1 with a glass

fiber pad filter.

7.9 Decant the extract to the Buchner funnel.

7.10 If the extract contains an oil phase, separate the aqueous phase
using a separatory funnel. Neither the separation nor the filtration are
critical, but are necessary to be able to measure the volume of the aqueous
extract analyzed. Small amounts of suspended solids and oil emulsions will not
interfere with the extraction.

7.11 At this point, an aliquot of the filtrate of the original sample

may be combined with an aliquot of the extract in a proportion representative of
the sample. Calculate the proportions as follows:

Aliquot of the Filtrate(mL) = Solid Extracted(g)a x Total Sample Filtrate(mL)c

Aliquot of the Extract(mL) Total Solid(g)b Total Extraction Fluid(mL)d

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a
From Step 7.5. Weight of solid sample used for extraction.

b
From Step 7.4. Weight of solids and oil phase with the dry weight of filter and
tared dish subtracted.

c
Includes volume of all rinses added to the filtrate (Steps 7.1 and 7.2).

d
500 mL water plus total volume of NaOH solution. Does not include hexane, which
is subsequently removed (Step 7.10).

Alternatively, the samples may be distilled and analyzed separately,

concentrations for each phase reported separately, and the amounts of each phase
present in the sample reported separately.

7.12 Distillation of Sulfide

7.12.1 In a preliminary experiment, determine the approximate

amount of sulfuric acid required to adjust a measured amount of the sample
to pH less than or equal to 1. The sample size should be chosen so that
it contains between 1.0 and 50 mg of sulfide. Place a known amount of
sample or sample slurry in a beaker. Add water until the total volume is
200 mL. Stir the mixture and determine the pH. Slowly add sulfuric acid
until the pH is less than or equal to 1.

CAUTION: Toxic hydrogen sulfide may be generated from the acidified sample.
This operation must be performed in the hood and the sample left
in the hood until the sample has been made alkaline or the sulfide
has been destroyed.

From the amount of sulfuric acid required to acidify the sample and the
mass or volume of the sample acidified, calculate the amount of acid
required to acidify the sample to be placed in the distillation flask.

7.12.2 Prepare the gas evolution apparatus as shown in Figure 1

in a fume hood.

7.12.2.1 Prepare a hot water bath at 70EC by filling a

crystallizing dish or other suitable container with water and place
it on a hotplate stirrer. Place a thermometer in the bath and
monitor the temperature to maintain the bath at 70EC.

7.12.2.2 Assemble the three neck 500-mL flask, fritted

gas inlet tube, and exhaust tube. Use Teflon sleeves to seal the
ground glass joints. Place a Teflon coated stirring bar into the
flask.

7.12.2.3 Place into each gas scrubbing bottle 10 + 0.5

mL of the 0.5M zinc acetate solution, 5.0 + 0.1 mL of 37%
formaldehyde and 100 + 5.0 mL water.

7.12.2.4 Connect the gas evolution flask and gas

scrubbing bottles as shown in Figure 1. Secure all fittings and
joints.

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 7.12.3 Carefully place an accurately weighed sample which contains
1.0 to 50 mg of sulfide into the flask. If necessary, dilute to
approximately 200 mL with water.

7.12.4 Place the dropping funnel onto the flask making sure its
stopcock is closed. Add the volume of sulfuric acid calculated in Step
7.1.1 plus an additional 50 mL into the dropping funnel. The bottom
stopcock must be closed.

7.12.5 Attach the nitrogen inlet to the top of the dropping funnel
gas shut-off valve. Turn on the nitrogen purge gas and adjust the flow
through the sample flask to 25 mL/min. The nitrogen in the gas scrubbing
bottles should bubble at a rate of about five bubbles per second.
Nitrogen pressure should be limited to approximately 10 psi to prevent
excess stress on the glass system and fittings. Verify that there are no
leaks in the system. Open the nitrogen shut-off valve leading to the
dropping funnel. Observe that the gas flow into the sample vessel will
stop for a short period while the pressure throughout the system
equalizes. If the gas flow through the sample flask does not return
within a minute, check for leaks around the dropping funnel. Once flow
has stabilized, turn on the magnetic stirrer. Purge the system for 15
minutes with nitrogen to remove oxygen.

7.12.6 Heat sample to 70EC. Open dropping funnel to a position

that will allow a flow of sulfuric acid of approximately 5 mL/min. Monitor
the system until most of the sulfuric acid contained within the dropping
funnel has entered the sample flask. Close the dropping funnel while a
small amount of acid remains. Immediately close the gas shut-off valve to
the dropping funnel.

7.12.7 Purge, stir, and maintain a temperature of 70EC for a total

of 90 minutes from start to finish. Shut off nitrogen supply. Turn off
heat.

7.13 Titration of Distillate

7.13.1 Pipet a known amount of standardized 0.025N iodine solution

(see Step 5.12) in a 500-mL flask, adding an amount in excess of that
needed to oxidize the sulfide. Add enough water to bring the volume to
100 mL. The volume of standardized iodine solution should be about 65 mL
for samples with 50 mg of sulfide.

7.13.2 Add 2 mL of 6N HCl to the iodine.

7.13.3 Pipet both of the gas scrubbing bottle solutions into the
flask, keeping the end of the pipet below the surface of the iodine
solution. If at any point in transferring the zinc acetate solution or
rinsing the bottles, the amber color of the iodine disappears or fades to
yellow, more 0.025N iodine must be added. This additional amount must be
added to the amount from Step 7.13.1 for calculations. Record the total
volume of standardized 0.025N iodine solution used.

7.13.4 Prepare a rinse solution of a known amount of standardized

0.025N iodine solution, 1 mL of 6N HCl, and water to rinse the remaining

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 white precipitate (zinc sulfide) from the gas scrubbing bottles into the
flask. There should be no visible traces of precipitate after rinsing.

7.13.5 Rinse any remaining traces of iodine from the gas scrubbing
bottles with water, and transfer the rinses to the flask.

7.13.6 Titrate the solution in the flask with standard 0.025N

phenylarsine oxide or 0.025N sodium thiosulfate solution until the amber
color fades to yellow. Add enough starch indicator for the solution to
turn dark blue and titrate until the blue disappears. Record the volume
of titrant used.

7.13.7 Calculate the concentration of sulfide in the sample as

follows:

[(mL of I2 x N of I2) - (mL of titrant x N of titrant)](16.03)

= sulfide(mg/kg)
sample weight (kg)

8.0 QUALITY CONTROL

8.1 All quality control data must be maintained and available for
reference or inspection for a period of three years. This method is restricted
to use by or under supervision of experienced analysts. Refer to the appropriate
section of Chapter One for additional quality control requirements.

8.2 A reagent blank should be run every twenty analyses or per

analytical batch, whichever is more frequent.

8.3 Check standards are prepared from water and a known amount of
sodium sulfide. A check standard should be run with each analytical batch of
samples or once every twenty samples. Acceptable recovery will depend on the
level and matrix.

8.4 A matrix spiked sample should be run for each analytical batch or
twenty samples, whichever is more frequent, to determine matrix effects. If
recovery is low, acid-insoluble sulfides are indicated. A matrix spiked sample
is a sample brought through the whole sample preparation and analytical process.

8.5 Verify the calibration with an independently prepared QC reference

sample every twenty samples or once per analytical batch, whichever is more
frequent.

9.0 METHOD PERFORMANCE

9.1 Accuracy - Accuracy for this method was determined by three

independent laboratories by measuring percent recoveries of spikes for waste
samples. The results are summarized below.

Accuracy for the entire method for four synthetic waste samples 70-104%
recovery

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 9.2 Precision

Precision of entire method for four synthetic waste samples

Percent coefficient of variation 1.0-34

10.0 REFERENCES

1. Test Methods for Evaluating Solid Waste, Physical/Chemical Methods, 3rd ed.;
U.S. Environmental Protection Agency. Office of Solid Waste and Emergency
Response. U.S. Government Printing Office: Washington, DC,1987; SW-846; 955-001-
00000-1.

2. Methods for Chemical Analysis of Water and Wastes; U.S. Environmental

Protection Agency. Office of Research and Development. Environmental Monitoring
and Support Laboratory. ORD Publications Office. Center for Environmental
Research Information: Cincinnati, OH, 1979; EPA-600/4-79-020, Method 376.1.

3. CRC Handbook of Chemistry and Physics, 66th ed.; Weast, R., Ed.; CRC: Boca
Raton, FL, 1985.

4. Standard Methods for the Examination of Water and Wastewater, 16th ed.;
Greenberg, A.E.; Trussell, R.R.; Clesceri, L.S., Eds.; American Water Works
Association, Water Pollution Control Federation, American Public Health
Association: Washington, DC, 1985; Methods 427, 427A, 427B, and 427D.

5. Andreae, M.O.; Bernard, W.R. Anal. Chem. 1983, 55, 608-612.

6. Barclay, H. Adv. Instrum. 1980, 35(2), 59-61.

7. Bateson, S.W.; Moody, G.J.; Thomas, J.P.R. Analyst 1986, 111, 3-9.

8. Berthage, P.O. Anal. Chim. Acta 1954, 10, 310-311.

9. Craig, P.J.; Moreton, P.A. Environ. Technol. Lett. 1982, 3, 511-520.

10. Franklin, G.O.; Fitchett, A.W. Pulp & Paper Canada 1982, 83(10), 40-44.

11. Fuller, W. Cyanide in the Environment; Van Zyl, D., Ed.; Proceedings of
Symposium; December 1984.

12. Gottfried, G.J. "Precision, Accuracy, and MDL Statements for EPA Methods
9010, 9030, 9060, 7520, 7521, 7550, 7551, 7910, and 7911"; final report to the
U.S. Environmental Protection Agency (EMSL-CI); Biopheric.

13. Kilroy, W.P. Talanta 1983, 30(6), 419-422.

14. Kurtenacher, V.A.; Wallak, R. Z. Anorg. U. Chem. 1927, 161, 202-209.

15. Landers, D.H.; David, M.B.; Mitchell, M.J. Int. J. Anal. Chem. 1983, 14,
245-256.

16. Opekar, F.; Brukenstein, S. Anal. Chem. 1984, 56, 1206-1209.

17. Ricklin, R.D.; Johnson, E.L. Anal. Chem. 1983, 55, 4.

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18. Rohrbough, W.G.; et al. Reagent Chemicals, American Chemical Society
Specifications, 7th ed.; American Chemical Society: Washington, DC, 1986.

19. Snedecor, G.W.; Ghran, W.G. Statistical Methods; Iowa State University
Press: Ames, IA, 1980.

20. Umaña, M.; Beach, J.; Sheldon, L. "Revisions to Method 9010"; final report
to the Environmental Protection Agency on Contract No. 68-01-7266; Research
Triangle Institute: Research Triangle Park, NC, 1986; Work Assignment No. 1.

21. Umaña, M.; Sheldon, L. "Interim Report: Literature Review"; interim report
to the U.S. Environmental Protection Agency in Contract No. 68-01-7266; Research
Triangle Institute: Research Triangle Park, NC, 1986; Work Assignment No. 3.

22. Wang, W.; Barcelona, M.J. Environ. Inter. 1983, 9, 129-133.

23. Wronksi, M. Talanta 1981, 28, 173-176.

24. Application Note 156; Princeton Applied Research Corp.: Princeton, NJ.

25. Guidelines for Assessing and Reporting Data Quality for Environmental
Measurements; U.S. Environmental Protection Agency Office of Research and
Development: Washington, DC, 1983.

26. Fed. Regist. 1980, 45(98), 33122.

27. The Analytical Chemistry of Sulfur and Its Compounds, Part I; Karchmer,
J.H., Ed.; Wiley-Interscience: New York, 1970.

28. Methods for the Examination of Water and Associated Materials; Department
of the Environment: England, 1983.

29. "Development and Evaluation of a Test Procedure for Reactivity Criteria for
Hazardous Waste"; final report to the U.S. Environmental Protection Agency on
Contract 68-03-2961; EAL: Richmond, CA.

30. 1985 Annual Book of ASTM Standards, Vol. 11.01; "Standard Specification for
Reagent Water"; ATSM: Philadelphia, PA, 1985; D1193-77.

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 FIGURE 1.
GAS EVOLUTION APPARATUS

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 FIGURE 2.
TUMBLER-EXTRACTOR

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 FIGURE 3.
EXTRACTOR

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 METHOD 9031
SULFIDES

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 METHOD 9031
(Continued)

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 METHOD 9031
(Continued)

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