706

PICKARD G MARTIN-MERCURY

IN SOIL

DETERMINATION OF MERCURY IN SOIL

By J. A. PICKARD and J. T. MARTIN
An analytical procedure for the determination of mercury in soil is described. After the digestion of organic matter, the mercury is removed from the soil by distillation in hydrochloric acid gas, extracted from the distillate with dithizone and measured spectrophotometrically.

Introduction An earlier report1 described a method for the determination of mercury in plant material. I n work on the uptake of mercury by plants2? a method was required for the determination of mercury in soil. Stock and his c o - w o r k e r ~ ~ - ~ powdered minerals a t 800' for several hours, heated and the 'volatilised mercury was collected and electrolytically deposited on copper, from which it was distilled to condense as droplets whose sizes were measured. Substances such as coal which gave interfering distillates were wet-digested to bring the mercury into solution. Arable and forest soils showed 0.01-0.3p.p.m. and compost from gardens contained 0.8 p.p.m. of Hg. Stock' also used the electrolytic deposition procedure to examine soils and other materials ; soils showed 0.03-0.3 p.p.m., coal 0,02 p.p.m., street dust 0.9 p.p.m. and soot up to 28 p.p.m. Hg. Polley & Millers destroyed the organic matter in minerals with hydrogen peroxide and determined mercury by the dithizone reaction. Popea & Jem5neanug digested soils with potassium nitrate-sulphuric acid, removed interfering metals with potassium thiocyanate and ethylenediaminetetra-acetate (EDTA), and determined mercury with dithizone. We have found that interference by metals such as copper in soil is severe, but may be overcome by separation of the mercury from the soil by distillation in a current of hydrochloric acid gas. The mercury is then extracted from the distillate with dithizone and measured spectrophotometrically. Experimental Preparation of sample and destrwtion of organic matter A soil sample of up to 40 g. is used, depending upon the amount of mercury present. The
sample is air-dried, sieved from stones if present, and ground to pass a 2-mm. sieve. Organic matter is destroyed by digestion with sulphuric acid-nitric acid, with the addition of selenium.

Distillation and extraction of mercury

After digestion, the mercury is distilled from the mixture with hydrochloric acid gas of purity 99.8% supplied from a cylinder of liquefied hydrogen chloride. The purification of reagents (see below) and the incorporation of EDTA treatment in the extraction process reduce blank values to a low level. The mono-colour method discussed earlier1 is used for the determination of the mercury.

Preparation of reagents
Reagents should be of analytical grade wherever possible.
Ammonium hydroxide solution (5yo).-Dilute aq. ammonia sp. gr. 0.880 (I vol.) with water (19 vol.). Buffer solution.-Prepare a N-sodium acetate solution. Test with dithizone for freedom from interference and purify if necessary as described below for hydroxylamine hydrochloride solution. To 50 ml. add 13 ml. of N-hydrochloric acid and dilute t o 250 ml. Carbon tetrachloride.-Fractionate through a Widmer column. Dilhizone stock solution.-Dissolve 50--60 mg. of dithizone in 20 ml. of carbon tetrachloride and filter. Extract with 100 ml. of 5% ammonium solution and wash the alkaline layer twice with 5-ml. portions of carbon tetrachloride. Make the alkaline layer just acid with hydrochloric acid, add 5 ml. of hydroxylamine hydrochloride solution (see below) and re-extract with 1 0 0 ml. of carbon tetrachloride. Wash the carbon tetrachloride solution twice with 15-ml. portions of water and store in the refrigerator. Dithizone dilute solution.-Dilute the stock solution ten times with carbon tetrachloride. EDTA soluti0n.-4~~ disodium ethylenediaminetetra-acetate dihydrate. Hydroxylamine hydrochloride solution (20 % w/v) ,-Extract by shaking with small quantities of diluted dithizone solution until the extract is colourless after removal of excess dithizone with 5% ammonium hydroxide solution. Extract any remaining dithizone with carbon tetrachloride until two successive washings are

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colourless. Filter the hydroxylamine hydrochloride solution through a wetted Whatman No. 54 paper t o remove any entrained carbon tetrachloride. Selenium powder.-Selected for low mercury content. Sodium metubisulphite solution (20 yo w/v) .-Treat as for hydroxylamine hydrochloride solution. The extraction is slow and a mechanical shaker is helpful. Sodium hypochlorite solution.-Titrate the approx. 15 % commercial product, and dilute t o 5% available chlorine. Store in refrigerator. (A suitable ' low in mercury ' product is available on the market.lO) Sodium thiosulphute solution.-1.5 % (w/v), freshly prepared.

Apparatus Digestion apparatus.-A 500-ml. two-necked, round-bottomed digestion flask carrying an aircondenser (30 x 3.5 cm.) in the central neck (B.34 joint) and a 50-ml. cylindrical separating funnel in the side neck (B.19 joint). The air condenser supports a double-surface water condenser (20 cm.). A 500-ml. 250-W heating mantle, controlled by an auto-transformer, is used for heating purposes. Distillation apparatus (Fig. I).-The gas-scrubber A contains sulphuric acid, sp. gr. 1-84. The distillation flask B (used for the digestion) carries an air-leak C and air-condenser D (IS x 3.5 cm.). The double-surface condenser E (Quickfit & Quartz Catalogue No. C 11/23) leads to a 500-ml. receiver F. The U-tubes G, containing sufficient distilled water to close the bends, are connected to a water pump. Procedure To a representative sample (up to 40 g.) of soil in the 500-ml. reaction flask, add 0.1 g. of selenium powder. Add a mixture of 50 ml. of sulphuric acid (sp. gr. 1.84) and 5 ml. of nitric acid (sp. gr. 1.42); mix well and digest slowly a t low heat for about 2 h. Carefully add more nitric acid, sp. gr. 1.50,I ml. a t a time, if there is any indication of charring. Maintain simmering gently for 30 min. Allow the digest to cool thoroughly and wash down the condenser slowly with 40 ml. of water, swirling the flask. Transfer the reaction flask to the distillation apparatus and add 50 ml. of sulphuric acid (sp. gr. 1.84). Assemble the apparatus and ensure that all the joints are gas-tight. With the air-leak partially open, draw a slow steady stream of air through the apparatus by means of the water pump, and apply gentle heat to the reaction flask. When the reaction mixture is boiling steadily and two-thirds of the water has distilled over, with the air-leak still partially open allow a steady stream of hydrochloric acid gas (about 25-30 ml./min.) to pass through the reaction flask. Maintain sufficient suction to ensure a steady flow through the absorption tubes, and adjust the air-leak as necessary. Continue the distillation with hydrochloric acid gas for 1k-2 h. Allow the apparatus to cool and remove the distillate. Wash the condenser and U-tubes with water and add the washings to the distillate. The volume of distillate and washings should be about 125 ml. Filter if necessary through a Whatman No. 541 filter paper into a 600-ml. graduated beaker and just neutralise to litmus with ammonia solution (sp. gr. 0.880). Make just acid to litmus

FIG. I-Distillation

apparatus

For A-G see text

J. Sci. Fd Agric., 1963, Vol. 14, October

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PICKARD & MARTIN-MERCURY

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by the addition, drop by drop, of concentrated hydrochloric acid. Add 10 ml. of sodium metabisulphite solution, mix well, add 25 ml. of buffer solution and 5 ml. of EDTA solution and dilute t o 250-300 ml. The pH of the solution should be 5 ; test with indicator paper and adjust if necessary. Transfer t o a 400-ml. separating funnel and extract with 10-,5- and 5-ml. portions of dilute dithizone solution. If mercury is suspected in the third extract (indicated by a change of colour of the dithizone solution), a fourth extraction with 5 ml. of dithizone solution should be made. Transfer the dithizone extracts to a 100-ml. separating funnel containing 25 ml. of o-IN-hydrochloric acid. Add 5 ml. of hydroxylamine hydrochloride solution, shake well and after separation transfer the carbon tetrachloride layer to a second Ioo-ml. separating funnel containing 50 ml. of o.IN-hydrochloric acid. Wash the aqueous layer with 5 ml. of carbon tetrachloride and add the washings t o the second separating funnel. Add 2 ml. of sodium thiosulphate solution and shake for I min. Run off the carbon tetrachloride layer and discard. Wash the acid layer with two 3-ml. portions of carbon tetrachloride and discard the washings. Add 3 ml. of sodium hypochlorite solution, shake vigorously for I min., blow off any chlorine and shake again. Extract twice with 3-ml. portions of carbon tetrachloride and reject the extracts. Add 20 ml. of buffer solution, 2 ml. of EDTA solution and mix. Add 7 ml. of carbon tetrachloride and I ml. of dilute dithizone solution and extract with vigorous shaking. I f necessary add dithizone solution a few drops a t a time until an excess of dithizone is present. Repeat the extraction using 4 ml. of carbon tetrachloride and a few drops of dithizone solution. Combine the dithizone extracts in a Ioo-ml. separating funnel and extract the excess of dithizone by shaking twice with 15-ml. portions of 5% ammonium hydroxide solution. Run the carbon tetrachloride solution containing the mercury-dithizone complex through 1-2 g. of granulated anhydrous sodium sulphate into a zo-ml. graduated amber glass flask and adjust the volume to 20 ml. with carbon tetrachloride. Measure the optical density (2-cm. cell) a t 490 mP-

Calibration with mercuric chloride Known amounts of mercury from o to 25 pg., as mercuric chloride in aqueous solution, were added to 50-ml. portions of o-IN-hydrochloric acid. Hydroxylamine hydrochloride solution (5 ml.), buffer solution (20 ml.) and EDTA solution (2 ml.) were added, the mercury was extracted with dithizone and the analysis continued as described. The optical densities recorded in a 2-cm. cell and corrected for the reagent blank (0.005) were as follows:
Mercury, pg. Optical density

5 0.170

0.338

I0

I5
0.512

20

0.681

0.860

25

Notes (I) The precautions necessary to avoid loss of mercury during the digestion and extraction processes have already been discussed.l The mixture of sulphuric and nitric acids must be evenly distributed throughout the sample before the digestion is commenced. During digestion, minimum heat from a controlled electric heating mantle is used, and charring must be avoided. A water-trap is not necessary. During distillation, the temperature of the mixture is maintained near that of boiling sulphuric acid ; a t lower temperatures the recovery is incomplete. ( 2 ) The cylinder containing liquefied hydrogen chloride and instructions for safe handling were obtained from Badische Anilin & Soda-Fabrik A.-G., Ludwigshafen am Rhein. The cylinder carried a reducing valve suitable for use with hydrochloric acid gas (obtained from The British Ermeto Corporation, Maidenhead). For safety, a three-way stop-tap was inserted between the reducing valve and gas-scrubber. Difficulty was met in finding suitable tubing t o convey the gas from the cylinder to the distillation apparatus. Polyvinyl chloride tubing was finally adopted ; fresh tubing gave high blank values, but the tubing became satisfactory after being in use. The gas flow-rate (about 25-30 ml./min.) was assessed visually from a knowledge of the performance of the sintered disc of the gas-scrubber when passing measured amounts of nitrogen through sulphuric acid.
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(3) The mercury-dithizone complex fades on exposure to sunlight ; this necessitates the use of a flask of low-actinic amber glass for the final solution. (4) Standard solutions of mercuric chloride in water ( j pg./ml.) lose strength when kept due to adsorption on the glass surface. Standard solutions should therefore be'freshly prepared.

Recoveries of mercury from soil samples Two soils that had not been treated with a mercurial compound showed on analysis 0.02 and 0.06 p.p.m. Hg. Mercury in the form of a freshly-prepared solution of mercuric chloride in water (5 pg. of Hg/ml.) was added, in known amounts up to 25 pg., to 40-g. samples of the soils before digestion. The added water on each occasion was adjusted to 5 ml. The recoveries by the method, allowing for the optical density value (0.01-0.015) given by the reagents and apparatus, are shown in Table I.

Table I
Recovevy of mercury f r o m soil
Original soil
0.02

Hg, p.p.m. Added Found 0.13 0.15, 0.14, 0.15 0.25 0.27, 0.27, 0.26 0.38 0.38, 0.38, 0.39 0.50 0'53, 0.52, 0'53

Original soil 0.06

Hg, p.p.m. Added Found 0.25 0.32 0.31 0.31 0.38 0.34 0'37 0.44 0.49, 0.51 0.56 0.62 0.59 0.63

The recoveries of added mercury were good, indicating that no losses occurred in the digestion, distillation and extraction processes. Whether the method yields all the naturallyoccurring mercury in soil is difficult to ascertain. The soil particles were small (98% passed a I-mm. and 70% passed a 0.05-mm. sieve) and the digestion procedure was severe, but some mercury may have been protected by occlusion within the particles. The method, however, was designed primarily for work on the levels and persistence of mercury after addition to soil, and for this purpose it should be satisfactory. Dept. of Agriculture & Horticulture Long Ashton Research Station University of Bristol
Received 15 February, 1963 : amended manuscript 13 May, 1963

References
1

Pickard, J. A,, & Martin, J. T., J . Sci. F d Agric., 1960, 11, 374 Pickard, J. Martin, J. T., Annu. Long Ashton Res. Sta., 1959, p. 93 Pickard, J. A,, & Martin, J . T., Annu. Rep, Long Ashton Res. Sta., 1960, p. 85 Stock, A., Lux, H., Cucuel, F., H.? . ' angew. Chem., 1933, 46, 62 Stock, A,, Cucuel, F., & Kohle, H., 2. angem. Chem., 1933. 46, 187

*
9

Stock, A . , & Cucuel, F., Naturwissenschaften, 1934. 22, 390 Stock, A , , Suensk, hem. T i d s k r , , 1938, 50, 242 Polley, Dorothy, & Miller, V. L., A n a l y t . Chem., 1955, 27, I162 popes, F,, & JemBneanu, M., Stud, Cercet&j Chi',, Bucuresti, 1960, 8, 607 Anon., Analyst, 1961, 86, 608

lo

J. Sci. Fd Agric., 1963, Vol. 14, October