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31 Mercury in Water TO RECEIVER

S. NISHI (1974, 1982) B. G. LIPTK (1995, 2003) AT

Flow Sheet Symbol

Pretreatment of Sample: Wet oxidation is used for the detection of the total mercury level, and solvent extrac-
tion is used for the detection of organic mercury.

Method of Detection: A. Colorimetric detection of total mercury level

B. Atomic absorption spectrophotometry of total mercury level
C. Gas chromatograph with electron capture detector for organic mercury
D. Thin-layer chromatographic detection of organic mercury
E. Ultraviolet detector preceded by wet chemistry package

Ranges: The detection ranges for A and D are approximately 0.02 to 0.5 ppm of mercury in
water, and for B and C, approximately 0.1 to 10 ppb of mercury in water. For E, the
measuring ranges are from 01 g/l to 0100 ppm.

Costs: A. Colorimetric spectrophotometers for laboratory applications range from $2000 to

B. About $100,000, depending on pretreatment of sample
C. About $35,000 for laboratory application
E. $50,000 or more

Partial List of Suppliers: (For a more complete list, for chromatograph suppliers, see Section 8.12; for colo-
rimeter suppliers, see Section 8.15; for atomic absorption analyzers, see Section 8.22;
for chromatographs, see Section 8.12; for ultraviolet analyzer, see Section 8.61; and
for wet chemistry analyzer, see Section 8.66.)
ABB (www.abb.com/analytical)
AMETEK, Process and Analytical Instruments Co. (E) (www.ametekpi.com)
Aurora Instruments (www.aurora-instr.com)
Bacharach Inc. (www.bacharach-inc.com)
Brooks Rand LLC (www.brooksrand.com)
Buck Scientific (www.bucksci.com)
Cetac (www.cetac.com)
Cole-Parmer (A) (www.coleparmer.com)
Davis Inotek Instr. (www.inotek.com)
EcoChem Analytics (www.ecochem.biz)
Fisher Scientific (www.fishersci.com)
LECO Corp. (www.leco.com)
Leeman Labs Inc. (www.leemanlabs.com)
Mercury Instr. GmbH (www.mercury-instruments.de)
Milestone (www.milestonesc.com)
Perkin-Elmer Corp. (B, E) (www.instruments.perkinelmer.com)
P.S. Analytical (www.psanalytical.com)
Rigaku MSC (www.rigakumsc.com)
Roentec GmbH (www.roentec.de)
Sick (www.sickmahaihak.com)
Shimadza Scientific Instruments
Tekran Inc. (www.tekran.com)
Thermo Automation Syst. (www.thermo.com)

2003 by Bla Liptk
1414 Analytical Instrumentation


While Section 8.30 described the analyzers used in the mon- C. REFLUX CONDENSER.
itoring of mercury concentration in ambient air samples, this E. RESERVOIR FOR DISTILLATE. C
section is devoted to the measurement of mercury in water.
There is unavoidably some overlap between the two sections.
The analyzers used for the measurement of mercury are
discussed in more detail in other sections of this chapter:
chromatographs are covered in Section 8.12, colorimeters in
Section 8.15, atomic absorption analyzers in Section 8.22, C
ultraviolet (UV) analyzers in Section 8.61, and wet chemistry
analyzers in Section 8.66. Because these analyzers are mostly
on-line, the emphasis in this section is placed on, but not
limited to, the laboratory procedures, while the discussion of
on-line units is not as detailed in this section.
The continuous on-line mercury monitors are used in
many industrial processes, including both effluent and quality I II
controls in chlorinealkali plants, quality controls of drinking
water and of sulfuric acid, control of industrial sewage and FIG. 8.31a
purification plants, monitoring the scrubber water in power Digestion flasks for detection of mercury (I) in water and (II) in
organic materials.
plants and of waste incinerators, just to mention a few.

such as that shown in Figure 8.31a prevents the small losses

due to vaporization of mercury during the digestion.
TOTAL MERCURY DETECTION Since upon completion of the digestion an excess of the
oxidizing agent is present in the digested solution, it becomes
Sample Treatment necessary to reduce the remaining oxidizing agent. Hydrox-
ylamine is best suited for the reduction of NO2 or KMnO4.
Mercury is present in the environment in organic and inor-
Hydroxylamine alone, however, cannot reduce nitrous acid
ganic compounds, either dissolved in water or adsorbed on
completely with nitric acid as a digesting liquor, and simul-
particulate matter or sediments. The total mercury level is the
taneous addition of urea is advisable. The samples thus
sum of organic mercury and inorganic mercury in a sample.
digested are then analyzed for mercury by one of the detec-
To analyze a variety of mercury compounds by the com- tors described below.
monly available methods, it is necessary to digest the sample
in order to effect decomposition of the accompanying sub-
stances, and thereby to convert the mercury present in the Colorimetric Detection
sample into inorganic mercury (Hg ). This digestion is car- Dithizone is widely used in the colorimetric analysis of mer-
ried out by mixing the sample with a mineral acid and a cury, where the absorption of visible light is detected as a
strong oxidizing agent and heating it. measure of mercury concentration. When an aqueous solution
The combinations in common use are H2SO4 KMnO4, of mercury with a wide pH range (0 to 13) is shaken with a
HNO3 KMnO4, H2SO4 H2O2, H2SO4 HNO3, and HCl solution of dithizone in chloroform, carbon tetrachloride, or
KClO3. The combination of H2SO4 KMnO4 or HNO3 benezene, a mercury complex is formed that dissolves in the
KMnO4 is best suited for analysis of water. The concentration organic layer. Dithizone is designated H2Dz, the mercuric
range most often used is 1 to 5 N for the acid and 1 to 5% 2+
(Hg ) dithizonate is represented as Hg (HDz)2, and the mer-
for KMnO4. 1+
curous (Hg ) dithizonate as Hg (HDz).
Heating is either by a water bath or by direct flame. The A solution of Hg (HDz)2 in carbon tetrachloride shows
digestion must be carried out in the presence of excess a maximum absorption at the wavelength of 485 to 490 nm.
KMnO4 and, therefore, a fresh addition must be made when- Mercury forms Hg (HDz) in the absence of water or a sec-
ever the color of the permanganate fades (the digestion being ondary dithizonate, HgDz, in aqueous alkaline solutions,
complete when the color of KMnO4 no longer fades). which are deficient in dithizone. This compound gives a
In case of biological materials where the samples are rich violet color.
in organic matter, the samples can best be digested by heating Dithizone reacts with silver (Ag), copper (Cu), gold (Au),
with H2SO4 HNO3 until white fumes (sulfuric acid) evolve. palladium (Pd), and platinum (Pt) in addition to Hg under
The digestion is complete when the solution becomes clear. acidic conditions, but it is generally sufficient to consider
When carbonization of organic matters occurs, the digestion interference of Cu alone in environmental analysis. Metals
is continued with fresh addition of nitric acid. An apparatus such as lead (Pb), cadmium (Cd), zinc (Zn), nickel (Ni),

2003 by Bla Liptk

8.31 Mercury in Water 1415

cobalt (Co), and iron (Fe) are not extracted from an acidic the concentration of dithizone do not affect the results. Hg
solution. Moreover, tin (Sn) and bismuth (Bi) are not extracted (HDz)2 gradually fades in the light. This tendency becomes
from a strongly acidic solution unless they are present in large pronounced when impure dithizone is used, whereas a solu-
quantities. tion of high-grade dithizone remains stable for several hours
in a lighted room.
Interference by Copper Interference of Cu may be elimi-
nated by one of the following methods: Atomic Absorption Spectrophotometry

1. When a small flow of a dithizone in carbon tetrachlo- In atomic absorption spectrophotometry, a solution contain-
ride solution is added to a weakly acidic solution con- ing mercury is introduced directly into a flame. This tech-
taining Hg and Cu, extraction of Hg is completed nique does not give high sensitivity in the analysis of mer-
before that of Cu begins. Separation of Hg and Cu is cury, and it is difficult to detect mercury at a concentration
thus possible. below 0.2 ppm. Mercury can be analyzed with high sensitiv-
2. Extraction of Hg and Cu can be carried out simulta- ity if the aqueous solution is first reduced to mercury vapor
neously with excess dithizone and then treated with a and then sent to the absorption cell by aeration, where it is
masking agent such as KBr, KI, and Na2S2O3 to analyzed by atomic absorption spectrophotometry without
2+ the use of flame. Stannous salts are best suited for reducing
decompose only Hg (HDz)2 and to transfer Hg into 2+
the aqueous layer. Thereafter, Hg is again extracted mercury in an aqueous solution. Mercuric (Hg ) ions are
with dithizone. reduced by stannous salts to metallic mercury (Hg ) accord-
3. Ethylenediaminetetraacetic acid (EDTA) in the form ing to Equation 8.31(1):
of the disodium salt can be added as a masking agent
2+ 2+ 0 4+
of Cu, and Hg alone is extracted with dithizone. The Hg + Sn Hg + Sn 8.31(1)
extraction is carried out at a pH of 2.5 or higher,
preferably 5.5, at which level CuEDTA is stable. The metallic mercury thus formed is vaporized by aeration
and is sent to the absorption cell (with quartz windows), where
A relatively large quantity of Cl also interferes with the its absorbance is measured at a wavelength of 253.7 nm.
extraction of Hg under strongly acidic conditions. For Figure 8.31b illustrates both the closed and open systems
instance, the extraction of Hg can be done without difficulty, of measurement. Beers law holds for the mercury levels of

when up to 1 M of Cl is in 50 ml of 1 N sulfuric acid.
Extraction becomes incomplete as Cl exceeds 2.5 M. Under
neutral to alkaline conditions, some interference is also
observed when NH1+ 4
is present in large quantities. S M C D R

Analysis Procedure The procedure generally followed in ABSORBANCE

the colorimetric determination of mercury by dithizone is as
follows: The sample solution is extracted repeatedly with
excess dithizone, and Hg is captured in the solvent layer as
Hg (HDz)2. Contaminants are also removed in this step. The
Hg (HDz)2 is then decomposed by a suitable masking or
oxidizing agent, and the Hg is liberated and transferred into CLOSED SYSTEM

the aqueous layer. Here it is reacted with a given excess if

dithizone, under specified conditions, and its concentration S M C D R
are measured colorimetrically.

The extraction immediately preceding the colorimetric

determination is carried out under acidic conditions. The SnSO4 F P
color developed is a mixture of orange (due to Hg (HDz)2)
and green (due to the excess of dithizone). The absorbance
of such mixed colors can be measured directly, or measure- TIME

ments may be made at 485 to 490 nm, which is the maximum SAMPLE

absorption wavelength of Hg (HDz)2. Higher sensitivity and OPEN SYSTEM

accuracy can be obtained at 605 to 620 nm, which is the S. LIGHT SOURCE. D. DETECTOR.
maximum absorption wavelength of dithizone. M. MONOCHROMETER. F. FILTER (COTTON OR DRYING AGENT.)
With the single-color method, mercury is extracted with
a solution of dithizone. The excess dithizone is removed by FIG. 8.31b
shaking it with dilute aqueous ammonia. The absorbance is Flameless atomic absorption spectrophotometer with reduction
measured at 485 to 490 nm. With this method, changes in aeration hardware.

2003 by Bla Liptk

1416 Analytical Instrumentation

0.1 to 10 g involved in this method. An atomic absorption REAGENT SAMPLE RECORDER

spectrophotometer is best suited for this measurement, but
simpler apparatus are also commercially available.
If large quantities of metal ions are present, it can be
reduced by the addition of stannous salts. If these ions are VACUUM
not reduced, they may interfere with the reduction of mer- REAGENT SAMPLE
cury. Interfering elements, however, are rarely present in VALVE VALVE

ordinary environmental samples in sufficient quantities to

cause interference. If the aeration causes the vaporization of REAGENT
organic substances, which absorb UV rays, it will interfere
with the analysis of mercury. Hence, it is necessary to decom- GAS
pose organic substances thoroughly.
Analysis Procedure A suitable amount of water sample is PUMP DETECTOR
introduced into a 500-ml flask and 20 ml of sulfuric acid (1 + DRAIN

1), plus 15 to 20 ml of KMnO4 (6%) is added. After mixing, FIG. 8.31d

a reflux condenser is attached to the flask and the mixture is Continuous mercury monitor.
boiled. The KMnO4 solution is replenished when it has been
consumed. The flask is cooled when the color of KMnO4 no On-Line Measurement
longer disappears, and the excess KMnO4 is reduced with a
hydroxylamine sulfate solution. Figure 8.31d illustrates the components of an automatic mer-
A portion (containing 10 g or less of mercury) is trans- cury monitor with an UV detector. In the first step, the mer-
ferred into a flask such as the one shown in Figure 8.31b. cury is reduced to the elemental state by the addition of tin(II)
Two milliliters of sulfuric acid (1 + 1) and 2 ml of stannous chloride or NaBH4. Subsequently, mercury is stripped from
sulfate (10% in 2 N H2SO4) are added, and aeration is started the aqueous phase by an airstream and is carried into an
at a rate of 2 l/min. optical detector cell, which can be made of silica (Suprasil).
The vapor thus formed is driven into the vapor phase Here the mercury concentration is detected by UV absorption
and circulated in a closed circuit. The UV absorption at measurement at a wavelength of 253.7 nm.
253.7 nm is detected in the optical cell of an atomic absorp- This method of analysis is referred to as cold vapor
tion spectrophotometer. A typical record of the UV absor- atomic absorption spectroscopy (CVAAS). It is both sensitive
bance is shown in Figure 8.31c. A calibration curve is pre- (lowest range is 0 to 1 g/l) and selective for mercury. Mea-
pared with standard solutions containing known amounts of suring ranges are available from 0.01 ppb to 100 ppm. The
mercury to assist in the quantitative analysis. The relative reagent requirement is 3 l per week for each reagent. Trans-
standard deviation for this method is reportedly between 2 mitter outputs can be 4 to 20 mA analog or bidirectional RS
and 10%. 232. Some of these analyzers are fully automated.
Automatic operation can include unattended operation
guaranteed by self-diagnostics for alarming when malfunc-
10 ppb
tions are detected, for example, the loss of reagent, sample,
or stripping airflows; leakage of fluids; photometer lamp burn-
8 ppb out; or need for recalibration. The continuous-measurement
mode can also be switched to a periodic one. Automatic
calibration can also be performed. This is done by automat-

6 ppb
ically switching from the sample stream to a calibration solu-
tion. Similarly, the zero can also be automatically reset, and
4 ppb rinsing steps can be automatically initiated for the purpose
3 ppb of providing automatic self-cleaning. This analyzer is illus-
2 ppb
trated in Figure 8.31e.

1 ppb

Sample Treatment
In organomercury compounds of the RHgX type, R is an
FIG. 8.31c organic group, such as alkyl and phenyl, and X is an electrone-
UV absorption record of vapor sample produced by aeration. gative group, such as halogen and hydroxyl. Those carrying

2003 by Bla Liptk

8.31 Mercury in Water 1417

FIG. 8.31e
Mercury process analyzer. (Courtesy of Mercury Instruments GmbH.)

methyl, ethyl, and propyl groups are known to be the causes where both R and R are organic groups and X is an elec-
of Minamata disease (a severe neurological disorder resulting tronegative group. Many of the organic compounds remain
from poisoning by organic mercury and leading to severe in the organic solvent phase, and the purpose of cleaning is
permanent neurological and mental disabilities or death). thereby accomplished.
When these compounds are present in water, it is first nec- The transfer of the organomercury compounds from the
essary to extract them with a suitable solvent. organic solvent phase to the aqueous phase is quantitative.
The solubility of a compound of the RHgX type in organic Therefore, when the backextraction is carried out by using a
solvents varies. If X is a halogen, the compound is soluble smaller volume of the aqueous solution against a known
in aromatic hydrocarbons such as benzene and toluene. If X volume of the organic solvent, concentration of the organo-

is an ion such as SO2 1
4 OH or CH 3CO 2 , the solubility in
mercury compounds may be determined simultaneously with
hydrocarbons is extremely low. Therefore, it is necessary first cleaning up.
to convert X to a halogen, and then the RHgX compound can The organomercury compounds extracted back into the
be extracted with an organic solvent such as benzene and aqueous layer are again liberated as RHgCl by addition
toluene. The aqueous solution is made acidic by addition of of hydrochloric acid to the aqueous solution according to
hydrochloric acid before extraction. The lower alkyl mercury Equation 8.31(3).
compounds are moderately soluble in water, and a relatively
large amount of solvent is necessary to effect quantitative RHgSR + HCI RHgCI + RSH 8.31(3)
The organomercury compounds extracted in the organic The RHgCl liberated is extracted with a small amount of
solvent are generally contaminated and must be cleaned. The benzene and analyzed by gas chromatographic techniques.
cleaning of an RHgX-type compound can be performed
effectively by backextraction with an aqueous solution of a Gas Chromatography
sulfur-containing compound such as cysteine. Organomer-
Lower alkylmercury and phenylmercury compounds vapor-
cury compounds react with a sulfhydryl compound according
ize upon heating and can be analyzed by gas chromatography.
to Equation 8.30(2) and move from the organic solvent phase
The use of an electron capture detector gives high sensitivity
to the aqueous phase.
and is best suited for analysis of traces of organic mercury.
For example, methylmercury can be detected to a level of
RHgX + RSH RHgSR + HX 8.31(2) 1 10 g.

2003 by Bla Liptk

1418 Analytical Instrumentation

Organomercury compounds are highly reactive with met- three times, the aqueous layer is discarded, and the combined
als; consequently, it is not desirable to use metal tubing as benzene layer is washed with distilled water.
column materials. A glass column is preferable. Also, a polar The benzene layer is separated and is extracted back with
substance as a liquid phase in the column yields better results. 10 ml of a 0.1% aqueous solution of 1-cysteine. The aqueous
The liquid phases most frequently used are polyethylene layer is also separated, and 1 ml of concentrated hydrochloric
glycol, polydiethylene glycol succinate, and polybutanediol acid and 2 ml of benzene are added. After mixing, the ben-
succinate. zene layer is separated and dried over a small amount of
The amount of the liquid phase to be coated on the anhydrous sodium sulfate. A 10-l sample is analyzed by gas
support is preferably 5 to 10% for analysis of alkylmercury chromatography.
and about 2% for analysis of phenylmercury. An increase in The column recommended contains 5% polydiethylene
the coating amount causes an increase in bleeding gas and a glycol succinate on Chromosorb W, 60 to 80 mesh, packed
decrease in the standing current of the detector, with resultant in glass tubing, 1 m long, and with a 3-mm inside diameter.
lower sensitivity when a high column temperature is used. Column temperature is set at 266F (130C), and the flow
The size of the liquid phase is reduced for high-sensitivity rate of carrier gas is maintained at 60 ml/min. Methylmercury
analysis. chloride is eluted in 3 to 5 min under these conditions, and
The use of the substractive technique is recommended concentrations of 1 g/l or less can be detected by this
for simplified identification of organomercury compounds by method.
gas chromatography. When an organic solvent, such as ben-
zene or toluene, which contains organomercury compounds,
is mixed with the aqueous solution of a bivalent sulfur com- Thin-Layer Chromatography
pound, such as Na2S2O3 or cysteine, the organomercury com-
pounds disappear from the organic solvent. If one compares Thin-layer chromatography offers a simple and inexpensive
the gas chromatograms before and after this treatment, one method for analysis of organomercury compounds. Silica gel
will be noticed that the peaks corresponding to the organo- and alumina are mainly used as the adsorbent layer. The Rf
mercury compounds disappeared or diminished markedly values of organomercury compounds for a variety of devel-
after treatment. opers are shown in Tables 8.31f and 8.31g. The mercury
The analysis procedure is as follows: Ten milliliters of compounds are visualized by spraying the plate with a solu-
concentrated hydrochloric acid is added to 500 ml of the sam- tion of dithizone. Ordinarily, mercury of the order of 0.5 g
ple water containing methylmercury compounds. The result- can be identified visually in this manner. When developed as
ant solution is mixed with 100 ml of benzene, and the mixture organomercury dithizonate, visualization becomes unneces-
is allowed to settle. The aqueous layer is separated and is sary and mercury on the order of 0.1 g can be identified
extracted again with 100 ml of fresh benzene. This is repeated visually.

TABLE 8.31f
Rf Value of Organomercury Compounds

Compound A B C D E
Methylmercuric chloride CH3HgCl 0.35 0.59 0.29 0.42
Methylmercuric iodide CH3HgI 0.04 0.03
Ethylmercuric chloride C2H5HgCl 0.41 0.74 0.50 0.72 0.46
Ethylmercuric phosphate (C2H5Hg)2HPO4 0 0 0.49 0.67
Methoxyethylmercuric chloride CH3OC2H4HgCl 0.23 0.49 0.46 0.74
Phenylmercuric chloride C6H5HgCl 0.51 0.73 0.56 0.76
Phenylmercuric iodide C6H5HgI 0.74 0.84 0.92 0.86
Phenylmercuric acetate C6H5HgCH3CO2 0.39 0.64 0.86 0.83 0.48
Adsorbent layer; silica gel
A. n-Phexane:acetone (85:15)
B. n-Hexane:acetone (70:30)
C. Butyl alcohol saturated with water
D. Isopropyl alcohol:water (90:10)
E. Chloroform

2003 by Bla Liptk

8.31 Mercury in Water 1419

TABLE 8.31g
Rf Value of Organomercury Dithiozonates

Compound 1 2 3 4 5 6
Methylmercury dithizonate CH3Hg(HDz) 0.64 0.48 0.57 0.77 0.89 0.86
Ethylmercury dithizonate C2H5Hg(HDz) 0.64 0.51 0.62 0.78 0.91 0.87
Methoxyethylmercury dithizonate CH3OC2H4Hg(HDz) 0.32 0.16 0.25 0.44 0.58 0.49
Ethoxyethylmercury dithizonate C2H5OC2H4Hg(HDz) 0.44 0.23 0.34 0.55 0.71 0.67
Phenylmercury dithizonate C6H5Hg(HDz) 0.48 0.34 0.46 0.62 0.72 0.69
Mercury dithizonate Hg(HDz)2 0.19 0.09 0.17 0.28 0.19 0.15
1. Hexane:acetone (9:1)
2. Hexane:acetone (19:1)
3. Hexane:acetone (93:7)
4. Petroleum ether:acetone (9:1)
5. Hexane:acetone (19:1)
6. Petroleum ether:acetone (19:1)
Adsorbent layer
14 silica gel
56 alumina
HDz = abbreviation for dithizonate ligand.

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2003 by Bla Liptk