INORGANIC NONMETALS (4000)

4-186

Method
4500-sO,2- B. Iodometric solution/100 mL sample. Cool
mL EDTA
diately by adding l below. Do not filter. hot
1. General Discussion
samples to 50°C or mL H,SO, and 0.1 gl NH,SO,H crystals to
1
b. Titration: Add flask or other suitable titration vese
a. Principle: An acidiied sample' containing sulfte (S0,) a 250-mL erlenmeyer
mL EDTA-stabilized
sample i
is titrated with a standardized potassium iodide-iodate titrant. Accurately measure 50 to 100 liquid surface. Add 1 mi.
Free iodine, liberated by the iodide-iodate reagent, reacts with tip below
flask, keeping pipetTitrate
so,-. The titration endpoint is signalled by the blue color immediately with standard KLKIO
indicator solution. until a faint permanent
blue col
resuling from the frst excess of iodine reacting with a starch while swirling flask,
titrant, using distilled water instead
indicator.
develops. Analyze a reagent blank
b. Interferences: The presence of other oxidizable materials, of sample.
such as sulfide, thiosulfate, and Fe* ions, can cause apparently
high results for sulfte. Some metal ions, such as Cu*, may cata
lyze the oxidation of So, to So when the sample is exposed 4. Calculation
to air, thus leading to low results. NO, will react with SO, in the
acicic reacion medium and lead to low sulfite results unless sulfa (A - B) X M >X6X 40 000
mic acid is added to destroy nitrite. Addiion of EDTA as a com mg S0,L= mL sample
plexing agent at the time of sample collection inhibits Cu'* catal
ysis and promotes oxidation of ferrous to ferric iron before analysis.
Sulfide and thiosulfate ions normally would be expected only in where:
samples containing certain industrial discharges, but must be ac
counted for if present. Sulfide may be removed by adding about A = mL titrant for sample,
05 g zinc acetate and analyzing the supernatant of the settled B= mL titrant for blank, and
sample. However, thiosulfate may have to be determined by an M= molarity of KI-KIO, titrant.
independent method (e.g. the formaldehydefodometric method'),
and then the sulfite determined by difference. 5. Precision and Bias
c. Minimum detectable concentration: 2 mg So, L.
d Quality control (0C): The QC practices considered to be an Three laboratories analyzed five replicate portions of a stan
integral part of each method are summarized in Table 4020:I. dard sulfte solution and of secondary treated wastewater effuent
to which sulfite was added. The data are summarized below.
2. Reagents Individual analyst's precision ranged from 0.7 to 3.6% standard
a. Sulfuric acid: H,SO4, 1 + 1. deviation (N = 45).
b. Standard potassium iodide-iodate titrant, 0.0125M: Dis
solve 0.4458 g primary-grade anhydrous KIO, (dried for 4 h at Relative
120°C), 4.35 gKI, and 310 mg sodium bicarbonate (NaHCO,) in Standard Standard
distilled water and dilute to 1000 mL; 1.00 mL= 500 g SO,2. X Deviation, ¡ Deviation
c. Sulfamic acid, NH,SO,H, crystalline. Sample mg/L mg/
d. EDTA reagent: Dissolve 2.5 g disodium EDTA in 100 mL
distilled water. Standard,
e. Starch indicator: To 5 g starch (potato, arrowroot, or 6.3 mg SO,-L 4.5 0. 25 5.5
soluble) in a mortar, add a little cold distilled water and grind to Secondary
effiuent with 2.1 13.4
a paste. Add mixture to 1L boiling distilled water, stir, and let
0.28
2.0 mg S0,L
settle overmight. Use clear supernatant. Preserve by adding either Secondary effluent with
1.3 g salicylic acid, 4 g ZnClz, or a combination of 4 g sodium 4.0 mg SO,?-L 3.6 0.17 4.8
propionate and 2 g sodium azide to 1L starch solution.
6. Reference
3. Procedure

a. Sample collection: Collect a fresh sample, taking care to 1. KURTENACKER, A. 1924. The aldehyde-bisulfite reaction in mass na
minimize contact with air. Fix cooled samples (<S0°C) imme ysis. Z Anal. Chem. 64:56.
 e. Alkaline Add 150 mL 22%
solution to 85 H solution.
f. Reagents tric titration method: See Section
4500-SF.
3. Procedure
Add 15 mL stannous chloride/hydrochloric acid solution to
digestion vessel and 100 mL alkaline zinc solution to each trap.
Adjust nitrogen flow rate to approximately 40 to 60 m/min and
fiush system for l0 min. Add approximately 6 g fresh wet
sediment to digestion vessel using a 5-mL syringe with its distal
ends removed. Close outlets with clamps and gently stir the
suspension. Allow H,S generation to take place at room temper
ature (25+3°C) for 3 h while stirring and with the nitrogen
flowing. Combine the solutions from the two traps and titrate as
described in 4500-S?-E.
4. Precision and Bias
For marine sediment samples (n=6), an average of 97% of the
added ferrous monosulfide was recovered by the diffusion
method. Reproducibility of this measurement performed on four
samples with concentrations of around 40 to 150 umols/g ry
weight (1.3 to 4.8 mg S/g) was better than 5%.
4500-S0? SULFITE*
4500-SO,
1. Occurrence
Sulfite ions (SO,2) may occur in boilers and boiler feedwa
ters treated with sulfite for dissolved oxygen control, in natural
waters or wastewaters as a result of industrial pollution, and in
treatment plant effluents dechlorinated with sulfur dioxide (SO,).
Excess sulfite ion in boiler waters is deleterious because it lowers
the pH and pronotes corosion. Control of sulfite ion in waste
"Approved by Standard Methods Committee, 2000. Editorial revisions, 2011.
The quality control practices considered to be an integral part
of each method are summarized in Table 4020:1.
6. Bibliography
CHANTON, J.P. &C.S. MARTENS. 1985. The effects of heat and stannous
chioride on the active distillation of acid volatile sulfide from
Pyrite-rich marine sediment samples. Biogeochemistry l:375.
MORSE, J.W. &J.C. CORNWEL, 1987. Analysis and distribution of iron
sulide minerals in recent anoxic marine sediments. Mar. Chem.
22:55.
HsIEH, Y.P. & C.H. YANG, 1989. Diffusion methods for the determina
tion of reduced inorganic sulfur species in sediments. Limnol.
Oceanogr. 34:1126.
ALLEN, H.E., G.-M. FU &B.-L. DENG. 1993. Analysis of acid-volatile
Sulhde (AVS) and simultaneously extracted netals (SEM) for the
estimation of potential toxicity in aquatic sediments. Environ. Toxi
col. Chem. 12:1441.
LASORSA, B. & A. CASAS. 1996. A comparison of sample handling and
analytical methods for determination of acid volatile sulfides in
sediment. Mar. Chem. 52:211.
LEONARD, EN., A.M. CoTTER &G.T. ANKLEY. 1996. Modified diffusion
method for analysis of acid volatile sulfides and simultaneously
extracted metals in freshwater sediment. Environ. ToxicoL. Chem.
15:1479.
A. Introduction
water treatment and discharge may be important environmen
tally, principally because of its toxicity to fish and other aquatic
life and its rapid oxygen demand.
2. Selection of Method
The iodometric titration method is suitable for relatively clean
waters with concentrations above 2 mg S0,L. The phenan
throline colorimetric determination, following evolution of sul
fite fromn the sample matrix as SO2, is preferred for low levels of
sulfite.