Analysis method of mercury, arsenic, cadmium, lead and

chromium in fertilizer
Analysis method of mercury and arsenic
1. Summary
After digestion, thiourea was added to prereduce arsenic pentavalent to arsenic
trivalent. Mercury in acid medium, potassium borohydride reduction into atomic
state mercury, arsenic reduction to generate hydrogen arsenide, quartz loaded by
argon gas atomization device, in a special mercury, arsenic, inspired by the launch
of hollow cathode lamp light produce atomic fluorescence, using fluorescence
intensity under certain conditions and the measured liquid is directly proportional
to the concentration of mercury, arsenic, determination of mercury, arsenic.
2. Reagents
Hydrochloric acid, superior grade pure.
Nitric acid, excellent grade pure.
Aqua regia: Mix hydrochloric acid and nitric acid according to the volume ratio of
3:1, put for 20min before use.
Hydrochloric acid: ψ (HCI)=3%.
Hydrochloric acid solution: ψ (HCl)=50%.
Nitric acid solution: ψ (HNO3)=3%.
Potassium hydroxide solution: ρ(KOH)=5g/L.
Potassium borohydride solution: ρ(KBH)=20g/L. 10.0g potassium borohydride
was weighed, dissolved in 500mL potassium hydroxide solution, and mixed (this
solution can be stored in the refrigerator for 10 days, and should be used daily at
room temperature).
Thiourea solution: ρ(NH2CSNH2)=50g/L.
Potassium dichromate - nitric acid solution: ρ(K2Cr2O7)=0.5g/L. 0.5g potassium
dichromate was weighed and dissolved in 1000mL nitric acid solution.
Mercury standard reserve solution: ρ(Hg)=1000μg/mL. Arsenic standard reserve
solution: ρ(As)=1000μg/mL.
 Mercury standard solution: ρ(Hg)=10μg/mL. Draw 10.0mL of 1000μg/mL
standard reserve solution of mercury, adjust the volume to 1000mL with
potassium dichromate - nitric acid solution, and mix well.
Mercury standard solution: (Hg)=0.1μg/mL. Take 10.0mL of 10μg/mL mercury
standard solution, fix the volume to 1000mL with potassium dichromate - nitric
acid solution, and mix well.
Arsenic standard solution: ρ(As)=100ug/mL. Draw 10.0mL of 1000ug/mL arsenic
standard reserve solution, fix the volume to 100mL with hydrochloric acid
solution, and mix well.
Arsenic standard solution: ρ(As)=1μg/mL. Take 10.0mL of 100μg/mL arsenic
standard solution, set the volume to 1000 mL of water, and mix well.
3. Apparatus
General laboratory instruments.
Hollow cathode lamp for atomic fluorescence photometer with encoded Arsenic
and mercury hollow cathode lamp.
Electric heating plate: the temperature is adjustable from room temperature to
250℃.
4. Procedure
4.1 Preparation of test sample
After the solid sample has been reduced for several times, about 100g is taken out
and ground to pass through 0.50mm aperture sieve (if the sample is wet, it can
pass through 1.00mm sieve), mixed evenly, and placed in a clean and dry
container; After repeated shaking of the liquid sample, approximately 100mL was
quickly removed and placed in a clean, dry container.
4.2 Preparation of test sample solution
Weigh the sample 0.2g~2g(accurate to 0.0001g) into a 100mL beaker, add 20mL
aqua aqua, cover the surface dish, and digest it on an adjustable electric heating
plate at 150℃~200℃ (it is recommended to soak it overnight for water-soluble
fertilizer containing humic acid and fertilizer containing a large amount of organic
matter). When the beaker contents are nearly dry, add hydrochloric acid with an
 eyedropper for a few drops to drive away the remaining nitric acid. Repeat several
times until adding hydrochloric acid again without brown-yellow smoke. Rinse
the surface dish and the inner wall of the beaker with a small amount of water and
continue to boil for 5min. Remove and cool, filter, and collect the filtrate directly
in a 50mL volumetry bottle. After filtration, rinse with a small amount of water for
more than 3 times, combine with filtrate, add 10.0mL thiourea solution and 3mL
hydrochloric acid, set volume with water, mix well, and leave for at least 30min
before testing.
4.3 Hybrid working curve drawing
Absorb 0mL, 0.20mL, 0.40mL, 0.60mL, 0.80mL, 1.00mL of mercury standard
solution, absorb 0mL, 0.50mL, 1.00mL, 150mL, 2.00mL, 2.50mL of arsenic
standard solution into six 50mL volumetric bottles. Add 10mL thiourea solution
and 3mL concentrated hydrochloric acid, set volume with water, mix well.
The mass concentration of this mixture standard series solution is: mercury
0ng/mL, 0.40ng/mL, 0.80ng/mL, 1.20ng/mL, 1.60ng/mL, 2.00ng/mL; Arsenic
0ng/mL, 10.00ng/mL, 20.00ng/mL, 30.00ng/mL, 40.00ng/mL, 50.00ng/mL.
According to the requirements of the manual of atomic fluorescence photometer,
the working conditions of the instrument are selected.
Instrument reference conditions: photomultiplier tube negative high voltage 270V;
Hollow cathode lamp: mercury hollow cathode lamp: current 30mA; Hollow
cathode lamp: Arsenic L24mA; Atomizer temperature 200 ℃ ; Height 9 mm;
Argon flow rate 400mL/min; Shielding gas 1000 ml/min; Measurement method:
fluorescence intensity or concentration direct reading; Reading mode: peak area;
Integration time: 12s.
The fluorescence intensity of each standard solution was measured using
hydrochloric acid solution and potassium borohydride solution as carriers, and the
standard solution containing 0ng/mL mercury and arsenic as reference.
The mass concentration of mercury and arsenic in each standard solution (ng/mL)
was taken as the abscess coordinate, and the corresponding fluorescence intensity
was taken as the ordinate coordinate to draw the working curve.
4.4 Determination
The fluorescence intensity of the sample solution was measured directly (or
appropriately diluted) under the same conditions as the standard series solution,
and the corresponding mass concentration of mercury and arsenic (ng/mL) was
detected on the working curve.
4.5 Blank test
Except without the sample, the other steps are the same as the sample solution
determination.
5. Calculation
The content of mercury and arsenic, w, is expressed as mg/kg. It is calculated
according to equation (1):
(ρ -ρ0)D×50
w = -------------------------- (1)
m×103
Where:
ρ -- The mass concentration of mercury or arsenic in the sample solution as
determined by the working curve, in nanograms per milliliter (ng/mL);
ρ0-- the mass concentration of mercury or arsenic in the blank solution as
determined by the working curve in nanograms per milliliter (ng/mL);
D-- dilution of sample solution during measurement;
50-- volume of sample solution, in milliliters (mL);
m -- mass of the test material in grams (g);
103 -- the coefficient for converting grams into milligrams.
6. Deviation
The mass fraction of mercury, mg/kg 0.2≤w<2.5 2.5≤w≤4.0 w>4.0
The mass fraction of arsenic, mg/kg 0.5≤w<5.0 5.0≤w≤8.0 w>8.0
The ratio between the difference of two
measurements and the mean of two ≤50 ≤30 ≤10
measurements, %
Analysis method of cadmium, lead and chromium
1. Summary
After the sample is digested by aqua regia, cadmium, lead and chromium in the
sample solution are atomized in the ICP light source and excited to the high
energy state. When the atoms in the high energy state transition to the ground state,
electromagnetic radiation with characteristic wavelength is generated, and the
radiation intensity is proportional to the concentration of cadmium, lead and
chromium atoms.
2. Reagents
Hydrochloric acid, superior grade pure.
Nitric acid, excellent grade pure.
Aqua regia: Mix hydrochloric acid and nitric acid according to the volume ratio of
3:1, put for 20min before use.
Hydrochloric acid solution: φ(HCl)=50%.
Cadmium standard reserve solution: ρ(Cd)=1mg/mL.
Cadmium standard solution: ρ(Cd)=100μg/mL. Absorb 10.00mL of cadmium
standard reserve solution into a 100mL volumetric flask, add 5mL of hydrochloric
acid solution, set the volume with water, and mix well.
Cadmium standard solution: ρ(Cd)=20μg/mL. Absorb 20.00mL of cadmium
standard solution into a 100mL volumetric flask, add 5 mL of hydrochloric acid
solution, set the volume with water, and mix well.
Lead standard reserve solution: ρ(Pb)=1mg/mL.
Lead standard solution: ρ(Pb)=50μg/mL. Draw 5.00mL of lead standard reserve
solution into a 100 mL volumetric flask, add 5mL of hydrochloric acid solution,
set the volume with water, and mix well.
Chromium standard stock solution: ρ(Cr)=1mg/mL.
Chromium standard solution: ρ(Cr)=100μg/mL. Absorb 10.00mL of chromium
standard reserve solution into a 100mL volumetric flask, add 5mL of hydrochloric
acid solution, set the volume with water, and mix well.
Chromium standard solution: ρ(Cr)=20μg/mL. Absorb 20.00ml of cadmium
 standard solution into a 100mL volumetric flask, add 5mL of hydrochloric acid
solution, set the volume with water, and mix well.
High purity argon gas.
3. Apparatus
Electric heating plate: the temperature is adjustable from room temperature to
250℃.
Plasma emission spectrometer..
4. Procedure
4.1 Preparation of test sample
After the solid sample has been reduced for several times, about 100g is taken out,
and it is quickly ground to pass through 0.50mm aperture sieve (if the sample is
wet, it can pass through 1.00mm sieve), mixed evenly, and placed in a dry clean
and dry container; After repeated shaking of the liquid sample, approximately
100mL was quickly removed and placed in a clean, dry container.
4.2 Preparation of test sample solution
Weigh the sample 1g~5g(accurate to 0.001g), put it in a 100mL beaker, add 20mL
aqua regia, and cover the surface dish. When the contents of the beaker are nearly
dry, the beaker is gently boiled at 150℃~200℃ for 30min, and the surface dish
and inner wall of the beaker are washed with a small amount of water. After
cooling, add 2mL hydrochloric acid solution, heat to dissolve, remove to cool,
filter, filtrate directly collected in a 50mL volumetric bottle, after filtration, rinse
with a small amount of water for more than 3 times, combine in filtrate, constant
volume, mix well.
4.3 Hybrid working curve drawing
Absorb 0mL, 1.00 mL, 2.00 mL, 4.00mL, 8.00mL and 10.00mL of cadmium
standard solution, lead standard solution and chromium standard solution into six
100mL volumetric bottles, add 5mL hydrochloric acid solution, set the volume
with water, and mix well. The concentrations of cadmium in this standard series
solution were 0μg/mL, 0.20μg/mL, 0.40μg/mL, 0.80μg/mL, 1.60μg/m, 2.00μg/mL,
and the concentrations of lead were 0μg/mL, 0.50μg/mL, 1.00μg/mL, respectively.
 2.00 mu g/mL, 4.00 mu g/mL, 5.00 mu g/mL, the quality of chromium
concentration respectively 0 mu g/mL, 0.20 mu g/mL, 0.40 mu g/mL, 0.80 mu
g/mL, 1.60 mL, mu g 2.00 mu g/mL.
Before measurement, argon flow, observation height, RF generator power,
integration time and other measurement conditions were optimized according to
the properties of elements to be measured and instrument performance. Then, the
radiation intensity of each standard solution was measured by plasma emission
spectrometer at the characteristic wavelength of each element
(Cadmium :214.439nm, Lead :220.353nm, chromium: 267.716nm). The mass
concentration of each standard solution (μg/mL) was taken as the abscissa and the
corresponding radiation intensity was taken as the ordinate to draw the working
curve.
4.4 Determination
The radiation intensity of the element to be measured can be measured directly (or
appropriately diluted) under the same conditions as the standard series solution,
and the corresponding mass concentration (μg/mL) can be detected on the
working curve.
4.5 Blank test
Except without the sample, the other steps are the same as the sample solution
determination.
5. Calculation
The content of element under test, w, is expressed as mg/kg. It is calculated
according to equation (1):
(ρ -ρ0)D×50
w = -------------------------- (2)
m
Where:
ρ -- The mass concentration of element under test in the sample solution as
determined by the working curve, in nanograms per milliliter (mg/mL);
ρ0-- the mass concentration of element under test in the blank solution as
determined by the working curve in nanograms per milliliter (mg/mL);
 D-- dilution of sample solution during measurement;
50-- volume of sample solution, in milliliters (mL);
m -- mass of the test material in grams (g).
6. Deviation
The mass fraction of cadmium,
0.5≤w<5.0 5.0≤w≤8.0 w>8.0
mg/kg
The mass fraction of lead, mg/kg 10.0≤w<20.0 20.0≤w≤40.0 w>40.0
The mass fraction of chromium,
5.0≤w<10.0 10.0≤w≤40.0 w>40.0
mg/kg
The ratio between the difference of
two measurements and the mean of ≤50 ≤30 ≤10
two measurements, %