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3500-As ARSENIC*
3500-As A. Introduction
1. Occurrence and Significance the protection of aquatic life, the average concentration of As3
in water should not exceed 72 g/L and the maximum should not
Arsenic (As) is the third element in Group VA of the periodic exceed 140 g/L. The United Nations Food and Agriculture
table; it has an atomic number of 33, an atomic weight of 74.92, Organizations recommended maximum level for irrigation wa-
and valences of 3 and 5. The average abundance of As in the ters is 100 g/L. The U.S. EPA primary drinking water standard
earths crust is 1.8 ppm; in soils it is 5.5 to 13 ppm; in streams MCL is 0.05 mg/L.
it is less than 2 g/L, and in groundwater it is generally less than
100 g/L. It occurs naturally in sulfide minerals such as pyrite. 2. Selection of Method
Arsenic is used in alloys with lead, in storage batteries, and in
ammunition. Arsenic compounds are widely used in pesticides Methods are available to identify and determine total arsenic,
and in wood preservatives. arsenite, and arsenate. Unpolluted fresh water normally does not
Arsenic is nonessential for plants but is an essential trace contain organic arsenic compounds, but may contain inorganic
element in several animal species. The predominant form be- arsenic compounds in the form of arsenate and arsenite. The elec-
tween pH 3 and pH 7 is H2AsO4, between pH 7 and pH 11 it trothermal atomic absorption spectrometric method (3113B) is the
is HAsO42, and under reducing conditions it is HAsO2(aq) (or method of choice in the absence of overwhelming interferences.
H3AsO3). Aqueous arsenic in the form of arsenite, arsenate, and The hydride generation-atomic absorption method (3114B) is pre-
organic arsenicals may result from mineral dissolution, industrial ferred when interferences are present that cannot be overcome by
discharges, or the application of pesticides. The chemical form standard electrothermal techniques (e.g., matrix modifiers, back-
of arsenic depends on its source (inorganic arsenic from miner- ground correction). The silver diethyldithiocarbamate method (B),
als, industrial discharges, and pesticides; organic arsenic from in which arsine is generated by reaction with sodium borohydride in
industrial discharges, pesticides, and biological action on inor- acidic solution, is applicable to the determination of total inorganic
ganic arsenic). arsenic when interferences are absent and when the sample contains
Severe poisoning can arise from the ingestion of as little as no methylarsenic compounds. This method also provides the ad-
100 mg arsenic trioxide; chronic effects may result from the vantage of being able to identify and quantify arsenate and arsenite
accumulation of arsenic compounds in the body at low intake separately by generating arsine at different pHs. The inductively
levels. Carcinogenic properties also have been imputed to ar- coupled plasma (ICP) emission spectroscopy method (3120) is
senic compounds. The toxicity of arsenic depends on its chem- useful at higher concentrations (greater than 50 g/L) while the
ical form. Arsenite is many times more toxic than arsenate. For ICP-mass spectrometric method (3125) is applicable at lower con-
centrations if chloride does not interfere. When measuring arsenic
species, document that speciation does not change over time. No
* Approved by Standard Methods Committee, 1997. universal preservative for speciation measurements has been iden-
Joint Task Group: 20th EditionSee 3500-Al. tified.
1. General Discussion The sample is then acidified with hydrochloric acid and another
portion of sodium borohydride solution is added. The arsine
a. Principle: Arsenite, containing trivalent arsenic, is reduced formed from arsenate is collected in fresh absorber solution.
selectively by aqueous sodium borohydride solution to arsine, b. Interferences: Although certain metals chromium, co-
AsH3, in an aqueous medium of pH 6. Arsenate, methylarsonic balt, copper, mercury, molybdenum, nickel, platinum, silver, and
acid, and dimethylarsenic acid are not reduced under these seleniuminfluence the generation of arsine, their concentra-
conditions. The generated arsine is swept by a stream of oxygen- tions in water are seldom high enough to interfere, except in the
free nitrogen from the reduction vessel through a scrubber con- instance of acid rock drainage. H2S interferes, but the interfer-
taining glass wool or cotton impregnated with lead acetate so- ence is removed with lead acetate. Antimony is reduced to
lution into an absorber tube containing silver diethyldithiocar- stibine, which forms a colored complex with an absorption
bamate and morpholine dissolved in chloroform. The intensity of maximum at 510 nm and interferes with the arsenic determina-
the red color that develops is measured at 520 nm. To determine tion. Methylarsenic compounds are reduced at pH l to methyl-
total inorganic arsenic in the absence of methylarsenic com- arsines, which form colored complexes with the absorber solu-
pounds, a sample portion is reduced at a pH of about l. Alter- tion. If methylarsenic compounds are present, measurements of
natively, arsenate is measured in a sample from which arsenite total arsenic and arsenate are unreliable. The results for arsenite
has been removed by reduction to arsine gas at pH 6 as above. are not influenced by methylarsenic compounds.
3-62 METALS (3000)
2. Apparatus a. Arsenite:
1) Preparation of scrubber and absorberDip glass wool into
a. Arsine generator, scrubber, and absorption tube: See Fig- lead acetate solution; remove excess by squeezing glass wool.
ure 3500-As:1. Use a 200-mL three-necked flask with a sidearm Press glass wool between pieces of filter paper, then fluff it.
(19/22 or similar size female ground-glass joint) through which Alternatively, if cotton is used treat it similarly but dry in a desic-
the inert gas delivery tube reaching almost to the bottom of the cator and fluff thoroughly when dry. Place a plug of loose glass
flask is inserted; a 24/40 female ground-glass joint to carry the wool or cotton in scrubber tube. Add 4.00 mL silver diethyldithio-
scrubber; and a second side arm closed with a rubber septum, or carbamate solution to absorber tube (5.00 mL may be used to
preferably by a screw cap with a hole in its top for insertion of provide enough volume to rinse spectrophotometer cell).
a TFE-faced silicone septum. Place a small magnetic stirring bar 2) Loading of arsine generatorPipet not more than 70 mL
in the flask. Fit absorber tube (20 mL capacity) to the scrubber sample containing not more than 20.0 g As (arsenite) into the
and fill with silver diethyldithiocarbamate solution. Do not use generator flask. Add 10 mL acetate buffer. If necessary, adjust
rubber or cork stoppers because they may absorb arsine. Clean total volume of liquid to 80 mL. Flush flask with nitrogen at the
glass equipment with concentrated nitric acid. rate of 60 mL/min.
b. Fume hood: Use apparatus in a well-ventilated hood with 3) Arsine generation and measurementWhile nitrogen is
flask secured on top of a magnetic stirrer. passing through the system, use a 30-mL syringe to inject
c. Photometric equipment: through the septum 15 mL 1% sodium borohydride solution
1) Spectrophotometer, for use at 520 nm. within 2 min. Stir vigorously with magnetic stirrer. Pass nitrogen
2) Filter photometer, with green filter having a maximum through system for an additional 15 min to flush arsine into
transmittance in the 500- to 540-nm range. absorber solution. Pour absorber solution into a clean and dry
3) Cells, for spectrophotometer or filter photometer, 1-cm, spectrophotometric cell and measure absorbance at 520 nm
clean, dry, and each equipped with a tightly fitting cover (TFE against chloroform. Determine concentration from a calibration
stopper) to prevent chloroform evaporation. curve obtained with arsenite standards. If arsenate also is to be
determined for this sample by using the same sample portion,
3. Reagents save the liquid in the generator flask.
4) Preparation of standard curvesTreat standard arsenite
a. Reagent water: See Section 1080A. solution containing 0.0, 1.0, 2.0, 5.0, 10.0, and 20.0 g As
BERYLLIUM (3500-Be) 3-63