Mercury, atomic absorption spectrometric, flameless

Parameters and Codes:

1. Application
1.1 This method may be used to analyze water 2.2 This method is based on a procedure
and water-suspended sediment containing at described by Hatch and Ott (1968) and is similar
least 0.5 µg/L of mercury. Samples containing in substance to the flameless atomic absorption
mercury concentrations greater than 10 µg/L method in "Methods for Chemical Analysis of
need to be diluted. Industrial and sewage effluent Water and Wastes," published by the Water
may be analyzed, as well as samples of fresh and Quality Office of the Environmental Protection
saline water. Agency (1979).
1.2 Suspended recoverable mercury is
calculated by subtracting dissolved mercury 3. Interferences
from total recoverable mercury. 3.1 Some samples may contain volatile organic
1.3 This method may be used to analyze compounds that absorb radiation at 253.7 nm
bottom material containing at least 0.01 µg/g of and that may be swept from the solution along
mercury. Usually, a 5-g sample of prepared with the mercury vapor. These constitute a
material (method P-0520) is taken for analysis. positive interference, and the possibility of their
For samples containing more than 1.0 µg/g, use presence must not be overlooked.
less sediment. 3.2 Selenium concentrations, either as
1.4 Total recoverable mercury in water- selenate or selenite, up to 10,000 µg/L do not
suspended sediment may be determined after interfere; higher concentrations were not tested.
each sample has been thoroughly mixed by
vigorous shaking and a suitable sample portion 4. Apparatus
has been rapidly withdrawn from the mixture. 4.1 Absorption cell (fig. 1). Mount and align
an absorption cell (10- to 20-cm path length) in
2. Summary of method the light path of the spectrometer. Position a
2.1 The cold-vapor, flameless, atomic 60-watt lamp over the cell (10 to 15 cm) to
absorption procedure is based on the absorption prevent condensation of water vapor. Attach a
of radiation at 253.7 nm by mercury vapor. sufficient length of tubing to the outlet of the
Organic mercury compounds, if present, are cell and vent to a hood. Connect the inlet of the
decomposed by hot (95°C) digestion with cell to the aerator with a minimum length of
potassium permanganate and potassium plastic tubing. Attach a water aspirator to the
persulfate in acid solution. The mercuric ions outlet of the stopcock (NOTE 1). Alternately, a
are then reduced to the elemental state with forced-air pump may be used.
stannous chloride, and the mercury vapor is NOTE 1. The stopcock must remain closed
subsequently removed from solution by aeration during analysis and be opened only briefly
and passed through a cell positioned in the light between samples to remove residual mercury
path of an atomic absorption spectrometer. vapor from the absorption cell.
4.2 Aerator (fig. 1).

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Figure 1. - Absorption cell and aerator

4.3 Atomic absorption spectrometer and NOTE 2. A larger volume of this reagent can be
recorder or a commerical mercury analyzer. prepared if it is kept refrigerated.
4.4 Refer to the manufacturer's manual to 5.2 Mercury standard solution I, 1.00 mL =
optimize instrument for the following: 100 µg Hg: Dissolve 0.1712 g Hg(NO3)2•H2O in
Grating……... Ultraviolet demineralized water. Add 1.5 mL concentrated
Wavelength … 253.7 nm HNO3 and dilute to 1,000 mL with
Source………….Mercury-vapor discharge, demineralized water.
hollow-cathode, or 5.3 Mercury standard solution II, 1.00 mL =
electrode-less-discharge 1.00 µg Hg: Dilute 5.00 mL mercury standard
lamp solution I and 1.5 mL concentrated HNO3 to 500
4.5 BOD bottle, 300-mL capacity. mL with demineralized water. This and the
4.6 Water bath or controlled-temperature following mercury standard solutions must be
oven, 95°C. prepared fresh daily.
5.4 Mercury standard solution III, 1.00 mL =
5. Reagents 0.050 µg Hg: Dilute 10.0 mL mercury standard
5.1 Hydroxylamine hydrochloride-sodium solution II and 1.5 mL concentrated HNO3 to
chloride solution: Dissolve 10 g NH2OH•HCl 200 mL with demineralized water. Use this
and 12 g NaCl in demineralized water and dilute solution to prepare working standards at the time
to 100 mL (NOTE 2). Prepare fresh daily. of analysis.
Alternatively, 12 g hydroxylamine sulfate may 5.5 Nitric acid, concentrated (sp gr 1.41), with
be used instead of the hydroxylamine low mercury content: duPont, reagent-grade acid
hydrochloride. has been found satisfactory.

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 5.6 Potassium permanganate solution, 50 g/L: 6.3.3 Add 5 mL concentrated H2SO4 and 2.5
Dissolve 5 g KMnO4 in demineralized water and mL concentrated HNO3, mixing after each
dilute to 100 mL. Prepare fresh weekly. Store in addition.
brown glass bottle. 6.3.4 Add 15 mL KMnO4 solution and shake.
5.7 Potassium persulfate solution, 50 g/L: Add additional small amounts of KMnO4
Dissolve 5 g K2S2O8 in demineralized water and solution, if necessary, until the purple color
dilute to 100 mL. persists for at least 15 min.
5.8 Stannous chloride solution, 74 g/L: Add 22 g 6.3.5 Add 8 mL K2S2O8 solution, mix, and heat
SnCl2•2H2O to 250 mL 0.25M H2SO4. This for 2 h in a boiling-water bath or for 3 h in an
solution is unstable. Prepare fresh daily. oven at 95°C. Proceed to paragraph 6.5.
5.9 Sulfuric acid, concentrated (sp gr 1.84). 6.4 Follow instructions in paragraphs 6.4.1
5.10 Sulfuric acid, 0.25M: Cautiously add 14 mL through 6.4.5 for recoverable mercury from
concentrated H2SO4 (sp gr 1.84) to demineralized bottom material.
water and dilute to 1 L. 6.4.1 Place a weighed portion of sample
containing less than 1.0 µg Hg (5 g max) into a
6. Procedure 300-mL capacity BOD bottle and add approx 100
6.1 Immediately before each use, clean all mL demineralized water.
glassware used in this determination by rinsing, 6.4.2 Prepare a blank of demineralized water
first with warm, dilute HNO3 (1+4), and then and sufficient standards, and adjust the volume of
with demineralized water. each to approx 100 mL with demineralized water.
6.2 Follow instructions in paragraphs 6.2.1 6.4.3 Add 5 mL concentrated H2SO4 and 2.5
through 6.2.5 for dissolved mercury. mL concentrated HNO3, mixing after each
6.2.1 Pipet a volume of sample containing less addition.
than 1.0 µg Hg (100 mL max) into a 300-mL 6.4.4 Add 15 mL KMnO4 solution and shake.
capacity BOD bottle and adjust the volume to Add additional small amounts of KMnO4
approx 100 mL. solution, if necessary, until the purple color
6.2.2 Prepare a blank of demineralized water persists for at least 15 min.
and sufficient standards, and adjust the volume of 6.4.5 Add 8 mL K2S2O8 solution, mix, and heat
each to approx 100 mL with demineralized water. for 2 h in a boiling-water bath or for 3 h in an
6.2.3 Add 5 mL concentrated H2SO4 and 2.5 oven at 95°C. Proceed to paragraph 6.5.
mL concentrated HNO3, mixing after each 6.5 Remove from water bath, cool, and add
addition. NH2OH•HCl-NaCl solution in 2-mL increments
6.2.4 Add 5 mL KMnO4 solution and shake. to reduce the excess permanganate, as evidenced
Add additional small amounts of KMnO4 by the disappearance of the permanganate color.
solution, if necessary, until the purple color 6.6 Add 5 mL SnCl2 solution to one sample and
persists for at least 15 min. immediately attach the bottle to the aerator
6.2.5 Add 2 mL K2S2O8 solution, mix, and heat (NOTE 3). Record the maximum absorbance.
for 2 h in a boiling-water bath or for 3 h in an After maximum absorbance has been recorded,
oven at 95°C. Proceed to paragraph 6.5. remove the BOD bottle and open the stopcock to
6.3 Follow instructions in paragraph 6.3.1 the vacuum. Momentarily pinch off the vent tube
through 6.3.5 for total recoverable mercury. in order to remove residual mercury vapor from
6.3.1 Pipet a volume of well-mixed sample the absorption cell. Treat each succeeding
containing less than 1.0 µg Hg (100 mL max) sample, blank, and standard in a like manner.
into a 300-mL capacity BOD bottle and adjust the NOTE 3. Use the atomic absorption
volume to approx 100 mL. compressed-air supply or a peristaltic pump to
6.3.2 Prepare a blank of demineralized water aerate the sample. Adjust the rate of air flow to
and sufficient standards, and adjust the volume of approx 2 L/min.
each to approx 100 mL with demineralized water.

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7. Calculations
7.1 Determine the micrograms of mercury in where
the sample from a plot of absorbances of ST = overall precision, micrograms per liter,
standards. Exact reproducibility is not obtained, and
and an analytical curve must be prepared with X = concentration of mercury, micrograms per
each set of samples. liter.
7.2 Determine the concentration of dissolved or The correlation coefficient is 0.9229.
total recoverable mercury in each sample as 9.2 Precision for dissolved mercury for six of
follows: the 23 samples expressed in terms of the percent
relative standard deviation is as follows:
1,000
Hg (µg/L) = µg Hg X ─────────── Number of Mean Relative standard deviation
mL sample aliquot laboratories (µg/L) (percent)
22 0.33 50
15 0.60 46
7.3 To determine the concentration of suspended 27 1.69 32
recoverable mercury, subtract dissolved-mercury 7 3.46 30
concentration from total-recoverable-mercury 7 6.54 18
concentration. 26 15.5 16
7.4 Determine the concentration of mercury in
air-dried bottom material as follows: 9.3 It is estimated that the percent relative
standard deviation for total recoverable and
suspended recoverable mercury and for
µg Hg in sample recoverable mercury in bottom material will be
Hg (µg/g) = ─────────── greater than that reported for dissolved mercury.
wt of sample (g) 9.4 Precision for total recoverable mercury
expressed in terms of percent relative standard
8. Report deviation for two water-suspended sediment
8.1 Report mercury, dissolved (71890), total- samples is as follows:
recoverable (71900), and suspended-recoverable
(71895), concentrations as follows: less than 10 Number of Mean Relative standard deviation
µg/L and greater than or equal to 0.5 µg/L, laboratories (µg/L) (percent)
nearest 0.1 µg/L; 10 µg/L and above, two
significant figures. 19 9.2 32
8.2 Report mercury, recoverable-from- 18 11.4 38
bottom-material (71921), concentrations as
follows: less than 1.00 µg/g, nearest 0.01 µg/g; References
1.0 µg/g and above, two significant figures.
Fishman, M.J., and Brown, Eugene, 1976, Selected methods
9. Precision of the U.S. Geological Survey for the analysis of
waste waters: U.S. Geological Survey Open-File
9.1 Precision for dissolved mercury for 23 Report 76-177, p. 51-60.
samples within the range of 0.3 to 15.5 µg/L may Hatch, W.R., and Ott, W.L., 1968, Determination of sub-
be expressed as follows: microgram quantities of mercury by atomic
absorption spectrophotometry: Analytical Chemistry,
ST = 0.152X + 0.164 v. 40, p. 2085-90.
U.S. Environmental Protection Agency, 1979, Methods for
chemical analysis of water and wastes: Cincinnati, p.
245.1-1.