2.6.01 (h) Other standard solutions.

—Dilute aliquots of solutions (b),

AOAC Official Method 965.09
Nutrients (Minor) in Fertilizers
Atomic Absorption Spectrophotometric Method
First Action 1965
Final Action 1969
AOAC–AACC Method
A. Apparatus and Reagent
(a) Atomic absorption spectrophotometer.—Several commer-
cial models are available. Since each design is somewhat different,
with varying requirements of light source, burner flow rate, and de-
tector sensitivity, only general outline of operating parameters is
given in Table 965.09. Operator must become familiar with settings
and procedures adapted to his own apparatus and use table only as
guide to concentration ranges and flame conditions.
(b) Disodium EDTA solution.—2.5%. Dissolve 25 g Na2H2 EDTA
in 1 L H2O and adjust to pH 7.0 with 5N NaOH, using pH meter.
B. Standard Solutions
(Do not use <2 mL pipets of <25 mL volumetric flasks. Automatic
dilution apparatus may be used. Prepare standard solutions in
0–20 µg range fresh daily.)
(a) Calcium solutions.—(1) Stock solution.—25 µg Ca/mL. Dis-
solve 1.249 g CaCO3 in minimum amount 3M HCl. Dilute to 1 L. Di-
lute 50 mL to 1 L. (2) Working standard solutions—0, 5, 10, 15, and
20 µg Ca/mL containing 1% La. To 25 mL volumetric flasks add 0,
5, 10, 15, and 20 mL Ca stock solution. Add 5 mL La stock solu-
tion and dilute to 25 mL.
(b) Copper stock solution.—1000 µg Cu/mL. Dissolve 1.000 g
pure Cu metal in minimum amount HNO3 and add 5 mL HCl. Evap-
orate almost to dryness and dilute to 1 L with 0.1M HCl.
(c) Iron stock solution.—1000 µg Fe/mL. Dissolve 1.000 g pure
Fe wire in ca 30 mL 6M HCl with boiling. Dilute to 1 L.
(d) Lanthanum stock solution.—50 g La/L. Dissolve 58.65 g
La2O3 in 250 mL HCl, adding acid slowly. Dilute to 1 L.
(e) Magnesium stock solution.—1000 µg Mg/mL. Place 1.000 g
pure Mg metal in 50 mL H2O and slowly add 10 mL HCl. Dilute to
1 L.
(f) Manganese stock solution.—1000 µg Mn/mL. Dissolve
1.582 g MnO2 in ca 30 mL 6M HCl. Boil to remove Cl and dilute to
1 L.
(g) Zinc stock solution.—1000 µg Zn/mL. Dissolve 1.000 g pure
Zn metal in ca 10 mL 6M HCl. Dilute to 1 L.
(c), and (e)–(g) with 0.5M HCl to make ≥4 standard solutions of
each element within range of determination.
C. Preparation of Test Solutions
(Caution: See Appendix B, safety notes on wet oxidation, hydro-
fluoric acid, and perchloric acid.)
(a) Inorganic materials and mixed fertilizers.—Dissolve 1.00 g
well-ground test sample in 10 mL HCl in 150 mL beaker. Boil and
evaporate solution nearly to dryness on hot plate. Do not bake resi-
due. Redissolve residue in 20 mL 2M HCl, boiling gently if neces-
sary. Filter through fast paper into 100 mL volumetric flask, washing
paper and residue thoroughly with H2O. Measure absorption of solu-
tion directly, or dilute with 0.5M HCl to obtain solutions within
ranges of instrument. If Ca is to be determined, add enough La stock
solution to make final dilution 1% La (i.e., 5 mL La to 25 mL flask,
20 mL to 100 mL flask, etc.).
(b) Fertilizers containing organic matter (tankage, corncobs,
cottonseed hulls, etc.).—Place 1.00 g test sample in 150 mL beaker
(Pyrex, or equivalent). Char on hot plate and ignite 1 h at 500°C with
muffle door propped open to allow free access of air. Break up cake
with stirring rod and dissolve in 10 mL HCl as in (a).
(c) Fertilizers containing fritted trace elements.—Dissolve
≤1.00 g well-ground test sample in 5 mL HClO4 and 5 mL HF. Boil
and evaporate to dense HClO4 fumes. Dilute carefully with H2O, fil-
ter, and proceed as in (a). Alternatively, dissolve test sample in
10 mL HCl, 5 mL HF, and 10 mL methanol. Evaporate to dryness.
Add 5 mL HCl and evaporate. Repeat HCl addition and evaporation.
Dissolve residue as in (a). (Normally Pt ware should be used; Pyrex
or other glassware may be used if Na, K, Ca, and Fe are not to be de-
termined.)
(d) For manganese.—(1) Acid-soluble, for both Mn2+ and
Mn4+.—See (a)–(c) and 972.02(b) (see 2.6.22). (2) Acid-soluble, for
Mn2+ only.—See 972.02(a) (see 2.6.22), 940.02 (see 2.6.23), and
941.02« (see 2.6.24). (3) Water-soluble, for Mn2+ only.—See
972.03 (see 2.6.25).
(e) For iron and zinc.—(1) Aqueous extraction.—Place 1.00 g
test sample in 250 mL beaker, add 75 mL H2O, and boil 30 min. Fil-
ter into 100 mL volumetric flask, washing paper with H2O. Dilute to
volume and redilute if necessary. (2) Chelation extraction.—Place
1.00 g test sample in 250 mL beaker, and add 5 cm (2 in.) magnetic
stirrer bar and 100 mL 2.5% EDTA solution (w/v). Stir exactly

Table 965.09 Operating parameters

Element Wavelength, Å Flame Range, µg/mL Remarks

Ca 4227 Rich Air–C2H2 2–20 1% La, 1% HCl
4227 Rich N2O–C2H2 2–20 Requires special burner
Cu 3247 Air–C2H2 2–20
Fe 2483 Rich Air–C2H2 2–20
Mg 2852 Rich Air–C2H2 0.2–2 May need La
Mn 2795 Air–C2H2 2–20
Zn 2138 Air–C2H2 0.5–5

© 2000 AOAC INTERNATIONAL

5 min, and filter through Whatman No. 41 paper, or equivalent. If fil- Read concentration of test solutions from plot of absorption against
trate is cloudy, refilter immediately through fine paper (Whatman µg/mL.
No. 5, or equivalent). Redilute, if necessary, with 0.5M HCl.
E. Calculations
D. Determination
(P interferes in Ca and may interfere in Mg determination with Percent element = (µg/mL) × (F/test portion weight) × 10–4
air–C2H2 burners. Eliminate interference by adding La stock solution
to standard and test solutions so that final dilutions contain 1% La. P F = mL original dilution × mL final dilution/mL aliquot, if original
does not interfere with Ca determination when N2O–C2H2 flame is 100 mL volume is diluted.
used.)
Set up instrument as in Table 965.09, or previously established References: JAOAC 48, 406, 1100(1965); 50, 401(1967);
optimum settings for apparatus to be used. Less sensitive secondary 51, 847(1968); 58, 928(1975).
lines [Gatehouse & Willis, Spectrochim. Acta 17, 710(1961)] may CAS-7440-70-2 (calcium)
be used to reduce necessary dilution, if desired. Read ≥4 standard so- CAS-7440-50-8 (copper)
lutions within analysis range before and after each group of 6–12 test CAS-7439-89-6 (iron)
solutions. Flush burner with H2O between test solution, and CAS-7439-95-4 (magnesium)
re-establish 0 absorption point each time. Prepare calibration curve CAS-7439-96-5 (manganese)
from average of each standard before and after test solutions group. CAS-7440-66-6 (zinc)

© 2000 AOAC INTERNATIONAL