J . Sci. Food Agric.

1985,36,794-798

A Simplified Method for the Extraction of the Metals Fe, Zn,

Cu, Ni, Cd, Pb, Cr, Co and Mn from Soils and Sewage Sludges
Stephen P. McGrath and Caroline H. Cunliffe

Soils and Plant Nutrition Department, Rothamsted Experimental Station, Harpenden, Herts A L5 2JQ
(Manuscript received 2 October 1984)

The method described for digestion of soil samples with aqua regia is simple,
flexible and safe to operate with large sample throughout. At least nine metals can
be determined in the resulting solutions with errors of 4%. The results compare
favourably with those from reflux aqua regia and averaged 88% of the certified
total values for reference soils and 88% of those for reference sewage sludges.
Keywords: Inductively-coupled plasma atomic emission spectrometry (ICP or
ICPAES); atomic absorption spectrophotometry (AAS); soil analysis; trace ele-
ments; heavy metals; trace metals; aqua regia.

1. Introduction
The use of atomic absorption and emission spectrophotometry permits rapid measurement of
many metals of agricultural, environmental and geochemical importance. This is especially true
of computer-controlled, multi-element inductively-coupled plasma atomic emission spectrometry
(ICP). Sample preparation and digestion processes for soils, sediments and sludges are in many
cases the most time-consuming parts of such analytical procedures. To increase sample
throughput rates, techniques are required which can be carried out on large numbers of samples
with minimum amounts of attention and manipulation.
Digestion with aqua regia (4 :1HCI : H N 0 3 by vol.) has been used in trace metal analysis, and
does not have unusual safety hazards associated with its use. The method described in this paper
is based on the use of aqua regia in tubes which are heated in block digesters. It has the following
advantages:
1. The method is simple and safe to operate and uses block digesters, which are often readily
available because of their use for Kjeldahl N determinations.
2. A large throughput of samples is possible.
3. Many elements can be determined in a single digest solution.
4. 'The digest solutions are compatible with ICP for multi-element detection, and also atomic
absorption spectrophotometry (AAS). The solutions produced are controlled with respect to
acidity and the amounts of dissolved solids, both factors of paramount importance for ICP and
AAS analyses.
5. Some automation of the digestion procedure is possible, using electronic timehemperature
controllers; indeed, the process is sufficiently safe to be carried out automatically overnight.
6. Specialised equipment needed when H F and HC104 are used is not required.
The method was tested on soils and sludges of certified composition obtained from the EEC
Bureau of Reference.
194
Extraction of metals from soils and sludges 795

2. Experimental
2.1. Materials
2.1.1. Standard materials
Three soils and three sludges were obtained from the Community Bureau of Reference (BCR),
(Table 1).
Table 1. Description of reference soils and sludges supplied by BCR
Sample Description
BCR 141 Calcareous loam
142 Light sandy soil
143 Sewage sludge amended soil with 50% organic matter
BCR 144 Sewage sludge of domestic origin
145 Sewage sludge of mixed origin
146 Sewage sludge of mainly industrial origin

2.1.2. Digestion apparatus

Straight-sided Pyrex glass tubes 150x24 mm diameter, or Pyrex Kjeldahl tubes 245 x28 mm
diameter with a constriction near the top were conditioned in 5% H N 0 3 prior to use. The
heating blocks were manufactured by Grant Instruments, Cambridge, Scienco Western,
Cambridge, or Technicon Instruments, Basingstoke, the latter two also manufacture time/
temperature controllers for use with heating blocks.

2.1.3. Reagents
The digestion acids were HCI (36% by wt.), H N 0 3 (70% by wt.) both AristaR grades. Deionised
water was used to prepare all solutions and reagents.

2.1.4. Analysis
All the determinations were made using a multi-channel inductively coupled plasma source
spectrometer (ARL 34000726) with appropriate corrections for spectral interferences.

2.2. Method
Ground soil (0.5 g) was weighed into a glass test tube, 8 ml conc. HCI and 2 ml conc. H N 0 3
added, and the mixture allowed to digest overnight at room temperature (or for 2-3 h at 60°C).
The tubes were placed in a digestion block at 105°C for 1h and the temperature then increased to
140°C until the samples were dry. After cooling, 12.5 ml of 20% (by vol.) HCI were added and
the mixture re-warmed at 80°C for 20 min. After cooling, the solution was mixed with a vortex
test tube mixer and filtered through a Whatman no. 40 filter paper into a 50ml volumetric flask,
rinsed and made up to volume with deionised water.

3. Results
For these materials recommended values are given for both total metal concentrations, obtained
by a large number of laboratories using various methods for both sample preparation and
determination of analytes, and for the amounts extracted by aqua regia under reflux. The results
for the block digests of these materials are tabulated in Tables 2 and 3 together with the ‘EEC’
aqua regia and total values,’ and percent solubilities of the block digests compared with these
totals. The solubilities using the block method were around 90% for most elements in these BCR
samples, with the exception of chromium in the soils BCR 141 and 142 which had the smallest
concentrations of chromium. Of the three soil samples, cadmium was detectable in the BCR 143
soil only, and was 96% soluble. In other soils, however, such as the Canadian subsoil CANMET
1% S. P. McGrath and C. H. Cunlie

Table 2. Metal concentrationss hgg-’) of Community Bureau of Reference soils BCR 141-3
determined using aqua regia digestions
Reference soils

Metal BCR 141 BCR 142 BCR 143

Zinc Block mean & CV (%)” 62.5 (1.3) 76.5 (1.6) 1109 (0.8)
Reflux mean & CV ( % ) b 70.0 (16) 79.6 (15) 1301 (4.6)
Rec. total valueC 81.3k3.7 92.4f4.4 I272f30
Solubility ( %) d 77 83 87
Copper Block mean & CV (%) 33.2 (3.7) 26.5 (0.8) 243 (0.8)
Reflux mean & CV (%) 31.2 (7.4) 25.3 (7.9) 236 (5.5)
Rec. total value 32.6f1.4 27.5f0.6 237 f8.2
Solubility (%), 102 96 103
Nickel Block mean & CV (%) 24.3 (3.5) 23.7 (3.2) 87.6 (1.3)
Reflux mean & CV (%) 28.0 (18) 28.9 (28) 92.7 (5.1)
Rec. total value 30.9 29.2k2.5 99.5 k5 .5
Solubility (%) 79 81 88
Cadmium Block mean & CV (%) <DL‘ <DL 30.0 (1.1)
Reflux mean & CV (%) 0.30 (43) 0.22 (45) 31.5 (6.0)
Rec. total value 0.36k0.1 0.25f0.09 31.3f1.2
Solubility (%) - - 96
Chromium Block mean & CV (%) 49.1 (5.0) 39.7 (2.5) 190 (1.1)
Reflux mean & CV (%) 53 (17) 44.4 (12) 208 (9.6)
Rec. total value 75.0 74.9 228
Solubility (%) 65 53 83
Lead Block mean & CV (%) CDL~ <DL 1247 (0.7)
Reflux mean & CV (%) 26.3 (22) 30.9 (22) 1317 (4.2)
Rec. total value 29.4k2.6 37.8+ 1.9 1333k39
Solubility (%) - - 94
Cobalt Block mean & CV (%) 8.28 (2.9) 7.42 (1.6) 11.6 (5.5)
Reflux mean & CV (%) - - -
Rec. total value 9.2 7.9 11.8
Solubility (%) 90 94 98
Manganese Block mean & CV (%) 509 (0.7) 536 (1.6) 958 (0.7)
Reflux mean & CV (%) 512 (12) 527 (6.6) 935 (11)
Rec. total value 547 569 999
Solubility (%) 93 94 96
Iron (%) Block mean & CV (a) 2.17 (0.9) 1.72 (1.5) 2.41 (0.8)
Reflux mean & CV (%) 2.37 1.75 2.58
Rec. total value 2.62 1.96 2.62
Solubility (%) 83 88 92
“Values are means of four replicate digestions by aqua regia block digestion.
hConcentrations published by the EEC for the aqua regia reflux method.
‘Recommended values with 95% confidence limits; those without confidence limits are indicative
but not certified.
dResult of proposed aqua regia method as % of recommended total value.
e<4pgCdg-’ soil (detection limit).
f<SOpgPbg-’ soil (detection limit).

SO-2, the solubilities were lower, in this case Zn49%, Cd59%, Cr47%, Mn37%, and Fe68%,
emphasising the fact that silicate-bound elements will not be fully dissolved by aqua regia.
In general, the results using the proposed block digest method are very close to those obtained
using the EEC reflux method fm the BCR reference soils and sludges, as shown in Table 4.
The CVs for the metals were generally 4%(tables 2 and 3) except when the concentration of
Co was near the detection limits in the sludge BCR145. The mean CV for the nine elements in
the six reference materials was 1.9%, much better than for the recommended values for reflux.
Extraction of metals from soils and sludges 797

Table 3. Metal concentrations bgg-’) of Community Bureau of Reference sludges BCR 144-6
determined using aqua regia digestions
Reference sludges
-

Metal BCR 144 BCR 145 BCR 146

~

Zinc Block mean & CV (%y 2779 (1.4) 2354 (1.9) 3493 (1.0)
Reflux mean & CV ( % ) b 3090 (8.6) 2772 (7.5) 4002 (7.4)
Rec. total value‘ 3143f 103 2843f64 4059f90
Solubility ( %) d 88 83 86
Copper Block mean & CV (%) 697 (1.8) 410 (1.0) 934 (0.6)
Reflux mean & CV (%) 694 (6.3) 416 (5.6) 921 (5.1)
Rec. total value 713f26 429f10 934f24
Solubility (%) 98 96 100
Nickel Block mean & CV (%) 852 (1.1) 30.3 (5.4) 239 (0.9)
Reflux mean & CV (%) 947 (6.9) 38.5 (9.4) 269 (6.3)
Rec. total value 942f22 41.4f2.4 280f18
Solubility (%) 90 73 85
Cadmium Block mean & CV (7%) <DL‘ 14.9 (3.3) 70.1 (1.1)
Reflux mean & CV (%) 3.6 (8.3) 16.8 (9.5) 76.5 (6.4)
Rec. total value 4.8f0.97 18.0f1.2 71.1f2.6
Solubility (%) - 83 90
Chromium Block mean & CV (%) 445 (1.5) 73.7 (2.0) 680 (1.3)
Reflux mean & CV (%) 494 (12) 85.2 (19) 769 (10)
Rec. total value 485 105 784
Solubility (%) 92 70 87
Lead Block mean & CV (%) 440 (0.9) 299 (2.1) 1154 (1.1)
Reflux mean & CV (%) 479 (11) 332 (6.6) 1255 (3.3)
Rec. total value 495+19 394f15 1270f 28
Solubility (%) 89 76 91
Cobalt Block mean & CV (%) 8.40 (3.3) 6.45 (7.9) 9.90 (3.7)
Reflux mean & CV (%) 8.6 (5.8) 6.8 (15) 9.9 (8.1)
Rec. total value 9.06f0.6 8.38f0.7 11.8f0.7
Solubility (%) 93 80 84
Manganese Block mean & CV (%) 439 (0.8) 226 (1.3) 565 (0.9)
Reflux mean & CV (%) 436 (6.9) 220 (6.7) 555 (5.8)
Rec. total value 449f13 241f12 588f24
Solubility (%) 98 94 96
Iron (%) Block mean & CV (%) 4.44 (2.3) 0.73 (2.2) 1.69 (0.8)
Reflux mean & CV (%) 4.31 0.81 -
Rec. total value 4.43 0.91 1.85
Solubility (%) 100 80 91
“Values are means of four replicate digestions by aqua regia block digestion.
bConcentrations published by the EEC for the aqua regia reflux method.
‘Recommended values with 95% confidence limits; those without confidence limits are indicative
but not certified.
dResults of proposed aqua regia method as % of recommended total value.
‘<4 pg Cdg-’ soil (detection limit).

4. Discussion and conclusions

The proposed method using aqua regia and block digesters is faster and more economical than
the reflux methods currently used and gives results for different soils and sludges which are in
good agreement with the results by reflux digestions. Less attention is required during the
digestion than when carrying out reflux and most other types of sample digestion. In addition,
the method is well suited to routine operation and does not involve the expense of platinum
crucibles, PTFE digestion vessels or digestion bombs and the special apparatus and facilities
needed to operate some of the other sample digestion methods, e.g. when using HC104 and HF.
53
798 S. P. McCrath and C. H. Cunliffe

Table 4. Solubilities of the aqua regia block method as a

percentage of the EEC aqua regia reflux method
Metal Soils Sludges
Zinc Mean 90 87
Range 85-96 85-90
Copper Mean 105 100
Range 105-106 99-101
Nickel Mean 88 86
Range 82-94 7990
Cadmium Mean 95 91
Range - 8%92
Chromium Mean 91 88
Range 89-93 87-90
Lead Mean 95 91
Range - 9&92
Cobalt Mean 98
Range - 95-100
Manganese Mean 101 102
Range 99-102 101-103
Iron Mean 94 97
Range
I
92-98 90-103
"Reflux values not given.

Using the proposed method, percentage recoveries of most metals are good when compared with
results obtained by reflux (Tables 2-4).
The proposed method has proved to be flexible in operation. It can be very simply modified to
suit different types of soil. For example, excessive frothing when digesting highly calcareous soils
can be overcome by adding extra HN03 before the aqua regia and heating stages. Also for soils
containing much organic matter the temperature was raised slowly at first, easily done when a
timekemperature controller was used. Peaty soils however cannot be handled in this way and
have to be ashed at 450°C before digestion. Tests with peat showed that, for all the elements
determined, only with Cu was there significant loss on ashing, which is well-known.2 In addition,
the amounts of sample digested and final solution volume can be varied: tests using 0.25, 0.5, 1.0
and 2.0g of soil with proportionate changes in the amounts of acids added to smaller or larger
tubes gave similar results in all cases.
In soils which are uncontaminated it is likely that much of the metals present will be in the soil
matrix which is only completely dissolved when sodium carbonate fusion or HF dissolution are
used. Other acid dissolution methods, including aqua regia, are likely therefore to give smaller
recoveries for uncontaminated soils.
Although block digestion with aqua regia does not give absolute total contents the method has
given results sufficiently close to the accepted values for different types of soils and sludges
supplied as reference materials to be of value in the routine monitoring of the metal contents of
agricultural soils and sludges.
Acknowledgements
The authors thank V. Cosimini and A. J. Pope for operating the ICP instrument.
References
1 . Colinet, E.; Gonska, H.; Griepink, B.; Muntau, H. The certification of the contents of cadmium, copper, mercury, lead
and zinc in a calcareous loam soil. Comm. Eur. Communities, Report EUR 8833, 1984.
2. Gorsuch, T. T. The Destruction of Organic Matter. Pergamon Press, Oxford, 1970.