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Comparative study of hotplate wet digestion methods for the determination

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 Chemosphere 72 (2008) 1420–1424

Contents lists available at ScienceDirect

Chemosphere
journal homepage: www.elsevier.com/locate/chemosphere

Comparative study of hotplate wet digestion methods for the determination

of mercury in biosolids
Cristina Lomonte a,b,*, David Gregory c, Alan J.M. Baker b, Spas D. Kolev a
a
School of Chemistry, The University of Melbourne, Parkville, Victoria 3010, Australia
b
School of Botany, The University of Melbourne, Parkville, Victoria 3010, Australia
c
Research and Technology Division, Melbourne Water Corporation, East Melbourne, Victoria 3001, Australia

a r t i c l e i n f o a b s t r a c t

Article history: The re-use of biosolids is becoming increasingly popular for land applications. However, biosolids may
Received 3 March 2008 contain elevated levels of metals and metalloids (including mercury) relative to background environmen-
Received in revised form 13 May 2008 tal concentrations. Consequently, reliable mercury analysis is important to allow classification of bioso-
Accepted 15 May 2008
lids and to determine appropriate options for beneficial uses.
Available online 3 July 2008
This paper reports on a comparative study of 12 hotplate wet digestion methods for their suitability for
the determination of mercury in biosolids. The methods were applied to mercury biosolids samples from
Keywords:
four localities of two different sewage treatment plants in the State of Victoria, Australia. Samples were
Biosolids
Sewage sludge
also spiked with methylmercury chloride and mercury sulphide to evaluate the Hg recovery in each hot-
Mercury plate digestion method. Aqua regia (HCl:HNO3 = 3:1), reverse aqua regia (HCl:HNO3 = 1:3), nitric, hydro-
Hotplate wet acid digestion chloric, sulphuric acid and their combinations with or without hydrogen peroxide were studied as wet
Cold vapour atomic absorption digestion solutions. The method providing the best mercury recoveries was optimized. Under optimal
spectrometry conditions the corresponding analytical procedure consisted of 1 h pre-digestion of 0.4 g biosolids sample
with 10 ml reverse aqua regia with temperature increasing to 110 °C and 3 h digestion at this tempera-
ture. In the last 10 min of the digestion step, 2 ml hydrogen peroxide were added to ensure complete
decomposition of all mercury containing compounds. After filtering and dilution with deionised water
(1:10), the concentration of mercury was determined by cold vapour atomic absorption spectrometry.
It is expected, that the wet acid digestion method developed in this study will be also applicable to
biosolids from other sewage treatment plants and to other types of solid mercury samples with elevated
levels of organic matter.
Ó 2008 Elsevier Ltd. All rights reserved.

1. Introduction environmental and public health concern. This is due to its extre-
mely high toxicity in both its organic and inorganic compounds
Biosolids (sewage sludge) are the stabilized organic materials and its ability to bioaccumulate (Kelly et al., 2006; Human Expo-
produced in the final stages of the domestic and industrial waste- sure, USEPA). Therefore, strict regulations on the use of biosolids
water treatment process (Bright and Healey, 2003). To avoid envi- in agriculture or for their safe disposal are in place in most coun-
ronmental and economic costs of disposal and taking up space in tries (Lavado et al., 2005) making the development of reliable ana-
landfills, the reuse of biosolids has been advocated. Currently, the lytical methods for the analysis of mercury in biosolids of critical
main use of biosolids is as fertilizers or composts in land applica- importance (Nevado et al., 2005).
tions to improve and maintain soil productivity and stimulate Currently, the majority of analytical methods for the determina-
plant growth and to establish sustainable vegetation at mine sites tion of mercury in solid samples (e.g. soil and sediments) are based
(Kelling et al., 1977; Sopper et al., 1981; Fresquez et al., 1990). on wet digestion (Page et al., 1982; US EPA Methods 245.5, 1991;
Heavy metals and metalloids are of particular concern in the Adeloju et al., 1994; US EPA Methods 3051, 1994; US EPA Methods
land applications outlined above as they are frequently present 7471a, 1994; US EPA Methods 3050B, 1996; Lamble and Hill, 1998;
at elevated concentrations in biosolids. Among the heavy metals US EPA Methods 7474, 1998; Loredo et al., 1999; Anderson, 2000;
frequently present in biosolids, mercury is arguably of the highest Navarro et al., 2006; Han et al., 2006; Butler et al., 2007). This pro-
cess results in the partial decomposition of the sample matrix
* Corresponding author. Address: School of Chemistry, The University of
involving the oxidation of all organic and inorganic mercury-con-
Melbourne, Victoria 3010, Australia. Tel.: +61 3 83447093. taining compounds. This process allows the detection of all mercury
E-mail address: [email protected] (C. Lomonte). species initially present in the sample as the Hg(II) ion (Page et al.,

0045-6535/$ - see front matter Ó 2008 Elsevier Ltd. All rights reserved.
doi:10.1016/j.chemosphere.2008.05.033
 C. Lomonte et al. / Chemosphere 72 (2008) 1420–1424 1421

1982; Anderson, 2000). Therefore, digestion mixtures usually con- Solutions of hydrochloric and sulphuric acids and hydrogen per-
tain strong oxidizing agents (e.g. H2O2) and mineral acids (e.g. oxide were prepared by dilutions of the corresponding concen-
HNO3, HCl and H2SO4), some of which can also act as oxidizing trated reagents. Aqua regia and reverse aqua regia were made by
agents. Depending on the heat source, wet digestion methods are mixing concentrated nitric and hydrochloric acids in ratios 1:3
either microwave or hotplate based. On the one hand, microwave and 3:1, respectively.
digestion is faster and uses lower quantities of reagents and sam- Fresh solution of 0.4% (w/v) NaBH4, used for the determination
ples, but on the other, high pressures are required, which increases of Hg by CV-AAS, was prepared daily by dissolving the appropriate
the cost of equipment and complicates the experimental procedure amount of sodium borohydride in 0.5% (w/v) NaOH.
with respect to sample and reagent addition. Hotplate digestion Mercury stock solutions (1000 mg l 1 Hg) were prepared by dis-
procedures are conducted at atmospheric pressure and do not suf- solving HgCl2 in 0.1 M HCl solution or by dissolving CH3HgCl in
fer from the problems associated with pressure build-up. This ap- 50% (v/v) methanol. These stock solutions were kept in sealed con-
proach also allows the mineralization of several samples at the tainers at 4 °C. Standard solutions (100 ml) of HgCl2 and CH3HgCl
same time. Biosolids are rich in organic matter and care must be ta- (5–60 lg l 1 Hg) were made up daily by appropriate dilutions of
ken to control the temperature of the digestion mixture to prevent the corresponding stock solutions with 10 ml of digestion reagent
the loss of Hg by volatilization and frothing (Page et al., 1982). The and deionised water.
hotplate approach allows a better temperature and froth control A solid mercury standard for spiking the biosolids samples was
and is thus more suitable for the digestion of biosolids samples. prepared by mixing 15 mg mercury(II) sulphide with 51.72 g cal-
The majority of the wet digestion methods currently used for cium carbonate.
mercury analysis in solid samples focus on soils and sediments
(Page et al., 1982; US EPA Methods 245.5, 1991; Adeloju et al., 2.3. Biosolids characterization
1994; US EPA Methods 3051, 1994; US EPA Methods 7471a,
1994; US EPA Methods 3050B, 1996; Lamble and Hill, 1998; US The pH, conductivity and sulphate content of biosolids were
EPA Methods 7474, 1998; Loredo et al., 1999; Anderson, 2000; Nav- determined after extraction in deionised water in 1:5 mass ratio
arro et al., 2006; Han et al., 2006; Butler et al., 2007). However, the of biosolids to water (Environmental Protection Authority, Victoria,
organic content of biosolids is substantially higher than that of soil Australia, 2000). Conductivity and pH in the extracts were mea-
and sediments and this can cause frothing during conventional wet sured with a combined pH-conductivity meter (SmartChem-Lab,
digestion procedures conducted at elevated temperatures. This fact TPS, Australia). The sulphate composition of the extracts was
emphasizes the need for a systematic evaluation of the suitability of determined by a Dionex DX-120 ion chromatograph (IC) using
existing hotplate based wet digestion methods for mercury analysis Peak Net Chromatography Work Station software (Dionex).
in biosolids. This paper reports on such a study in which biosolids Total sulphur was determined after digestion of the biosolids
samples from four localities of two different sewage treatment samples (AIM500 digestion block, A.I.Scientific, Australia). The fil-
plants in the State of Victoria, Australia, spiked with methylmer- tered (41 filter paper) digests were measured by inductively cou-
cury chloride (CH3HgCl) or mercury sulphide (HgS) were analyzed. pled plasma optical emission spectrometry (Vista-AX-CCD
Methylmercury chloride and mercury(II) sulphide were selected as Simultaneous, Varian Australia).
a model organic and inorganic mercury compound, respectively, The concentration of Hg(II) in the digested biosolids samples
because of their resistance to wet digestion. In addition, these was determined after filtering (41 filter paper) by CV-AAS using a
two Hg compounds represent the most common forms of organic Shimadzu AA-3600 double beam atomic absorption spectrometer
and inorganic mercury compounds found in soil and biosolids. equipped with a HVG-1 hydride generator (Shimadzu, Japan). All
Mercury(II) in the digests was determined by cold vapour- measurements were conducted in triplicate. The calibration curve
atomic absorption spectrometry (CV-AAS). The wet digestion method was used in this study. It was compared with the standard
method offering the best mercury recovery was further optimized addition method in the CV-AAS determination of mercury in di-
to improve its sampling rate. gests obtained under optimal conditions to check for matrix
effects.

2. Material and methods

2.4. Biosolids digestion

2.1. Samples
Wet biosolids samples (0.4 g) were digested in solutions con-
taining one or two components (in brackets): (a) 10 ml conc.
Biosolids samples were collected from four localities of two sew-
HNO3, (b) 10 ml aqua regia, (c) (6.6 ml conc H2SO4 + 3.3 ml conc.
age treatment plants in Victoria: Melbourne Water’s Western Treat-
HNO3) and (2 ml conc. HCl), (d) (10 ml conc. HNO3) and (2 ml
ment Plant (WTP) at Werribee and the Grampians Wimmera Mallee
H2O2), (e) (10 ml aqua regia) and (2 ml H2O2), (f) 10 ml reverse aqua
(GWM) treatment plants at Nhill and Dimboola. The WTP biosolids
regia, and (g) (10 ml reverse aqua regia) and (2 ml H2O2). The first
were between 2 and 30 years old with organic matter in the range
five digestion mixtures ((a)–(e)) were proposed by other research-
between 36% and 44% (w/w). The GWM biosolids were 2 years old,
ers (Page et al., 1982; US EPA Methods 245.5, 1991; Adeloju et al.,
with 29–36% (w/w) of organic matter at Nhill, and 22–33% (w/w)
1994; US EPA Methods 3051, 1994; US EPA Methods 7471a, 1994;
at Dimboola. Four samples were collected from the upper biosolids
US EPA Methods 3050B, 1996; Lamble and Hill, 1998; US EPA
layer (<20 cm), two at the WTP and one at each of the GWM treat-
Methods 7474, 1998; Loredo et al., 1999; Anderson, 2000; Han
ment plants. Fresh samples from each locality were collected ran-
et al., 2006; Butler et al., 2007). Hydrogen peroxide was chosen
domly, then ground manually by a ceramic pestle, sieved through
as the preferred oxidant to avoid eventual precipitation problems
a 2 mm mesh sieve, homogenized by a soil mixer, stored in polypro-
if permanganate had been used. Permanganate could precipitate
pylene containers at 4 °C and finally analysed in triplicate.
as manganese dioxide and does not totally oxidise some Hg deri-
vates, such as CH3HgCl and PhHgOAc (Kubasik et al., 1972; El-Awa-
2.2. Reagents dy et al., 1976; Hanna and Tyson, 1993). Each biosolids sample was
mixed with one of the components of a digestion solution and left
All reagents were of analytical reagent grade and were used as re- for 16 ± 1 h (overnight) at room temperature (pre-digestion step).
ceived. Deionised water was used for the preparation of all solutions. Then the suspension was heated at 110 °C for 5 h (digestion step).
1422 C. Lomonte et al. / Chemosphere 72 (2008) 1420–1424

This temperature was chosen as the average digestion temperature 3. Results and discussion
of frequently used soil digestion methods. In the case of 2-compo-
nent digestion methods, the second component was added during 3.1. Biosolids characterisation
the digestion step. In the hydrogen peroxide based methods, this
was done either before the addition of the acid solution or 4.5 h The pH, conductivity, moisture, sulphur and sulphate content of
after the start of the digestion step. When the digestion mixture the biosolids samples collected at WTP, GMW-Nhill and GMW-
contained all three mineral acids used, hydrochloric acid was Dimboola are summarized in Table 2. The acidic character of the
added either at the beginning of the digestion step or 3 h after it biosolids studied was in agreement with their high sulphur/sul-
had started. The digestion step with this composition of the diges- phate content suggesting the production of sulphuric acid as a re-
tion solution was conducted at 60 °C (Page et al., 1982). A summary sult of the oxidation of sulphur containing compounds. The high
of the wet digestion procedures investigated in this work is pre- sulphur content also suggested that a substantial fraction of the
sented in Table 1. mercury present could be expected to be in the form of the highly
insoluble mercury(II) sulphide. This finding justified the use of HgS
2.5. Recovery studies and statistical data analysis as the model inorganic mercury compound in the recovery studies.

In the recovery studies 4 biosolids samples from each of the 4 3.2. Recovery comparison between the digestion methods studied
sampling sites at MWT and GMW were spiked with CH3HgCl or
HgS (5 lg Hg) and the corresponding acid digests were analysed Recovery experiments involving spiking of biosolids samples
for mercury by CV-AAS in triplicate. Each recovery value was ob- with CH3HgCl and HgS were conducted to compare the suitability
tained as the average for the four samples and mercury measure- of the digestion methods listed in Table 1 for Hg analysis in bioso-
ments in the digests were conducted in triplicate. lids. In some of the digestion methods (Methods 4–6, Table 1),
In addition, to assess statistically if the recovery values obtained hydrogen peroxide was added to the biosolids samples before the
by two digestion methods were significantly different at 95% con- addition of the acid solution (i.e., as the first component of the
fidence level, the Student’s t-test was used. digestion mixture), as oppose to the reverse order (Methods 7–9,
Table 1). In the latter case, the digestion solution was cooled in cold
2.6. Optimization of the pre-digestion and digestion steps water for 1 min before the addition of hydrogen peroxide. The
addition of 2 ml conc. HCl to the biosolids samples together with
Both steps of the wet digestion method offering best mercury both sulphuric and nitric acids (Method 12), as recommended by
recoveries (Method 9, Table 1) were optimized. The pre-digestion Page et al., 1982 to enhance the rate of decomposition of HgS, re-
step with a duration of 1 h and a final temperature of 110 °C was sulted in froth production and loss of sample. This procedure was
subdivided into four sub-steps, each with its own temperature pro- subsequently modified by adding the 2 ml hydrochloric acid 3 h
file. Each temperature profile was either characterized by a con- after the start of the digestion step when the biosolids samples
stant temperature or by a linear temperature ramp with a rate had been mineralized to a considerable extent.
between 1 and 3 °C/min. Both the duration and the temperature The recovery experiments (Fig. 1) allowed to reduce the initial
profile of each sub-step were varied to obtain the optimal set of set of 12 digestion methods (Table 1) to 4 (Methods 2, 3, 8 and
pre-digestion conditions with respect to mercury recovery. 9), which were further optimized to select the digestion method
The digestion temperature was varied between 95 and 130 °C. best suited to biosolids samples. These results confirmed previous
The volume of hydrogen peroxide added after 2 h and 50 min findings that aqua regia was a suitable digestion reagent for insol-
from the start of the optimized digestion step was varied between uble mercury compounds like HgS (Biester and Nehrke, 1997; Hall
1 and 3 ml and its contact time with the biosolids sample was var- et al., 2005) and at the same time demonstrated that reverse aqua
ied between 10 and 30 min. regia was equally suitable for the digestion of mercury containing
biosolids.

3.3. Optimization studies

Table 1
Summary of the wet digestion methods investigated in this work for the determi-
The 4 digestion methods involving aqua regia, reverse aqua regia
nation of mercury in 0.4 g biosolids samples and hydrogen peroxide, selected for their good mercury recoveries,
were optimized with respect to: (i) the temperature profile of a
Method Pre-digestiona Digestion studiedb (component; time of contact)
pre-digestion step, substituting the overnight (i.e., 16 ± 1 h) pre-
(component)
digestion step (Table 1); (ii) the digestion temperature, (iii) the
1 10 ml HNO3 10 ml HNO3; 5 h
amount of hydrogen peroxide used and its contact time with the
2 10 ml aqua regia 10 ml aqua regia; 5 h
3 10 ml reverse 10 ml reverse aqua regia; 5 h biosolids samples.
aqua regia
4 2 ml H2O2 2 ml H2O2; 0.5 h + 10 ml HNO3; 4.5 h
5 2 ml H2O2 2 ml H2O2; 0.5 h + 10 ml aqua regia; 4.5 h Table 2
6 2 ml H2O2 2 ml H2O2; 0.5 h + 10 ml reverse aqua regia; 4.5 h Moisture, total sulphur (S) concentration (g kg 1) ± SD* and sulphate (SO24 ) concen-
7 10 ml HNO3 10 ml HNO3; 4.5 h + 2 ml H2O2; 0.5 h tration (g kg 1) ± SD* of biosolids samples from WTP, GWM – Nhill and GWM –
8 10 ml aqua regia 10 ml aqua regia; 4.5 h + 2 ml H2O2; 0.5 h Dimboola and pH and conductivity of their extracts
9 10 ml reverse 10 ml reverse aqua regia; 4.5 h + 2 ml H2O2; 0.5 h
Sample pH Conductivity Moisture S (SO24 )
aqua regia
(mS cm 1) content concentration concentration
10 6.7 ml H2SO4, 6.7 ml H2SO4, 3.3 ml HNO3;3 h + 2 ml HCl; 2 h
(w/w%) (g kg 1) ± SDa (g kg 1) ± SDa
3.3 ml HNO3
11 6.7 ml H2SO4, 6.7 ml H2SO4, 3.3 ml HNO3;3 h + 2 ml HCl; 2 h WTP – 1 5.21 1.49 8.79 7.10 ± 0.14 2.90 ± 0.02
3.3 ml HNO3 WTP – 2 5.23 4.27 8.86 8.24 ± 0.20 2.02 ± 0.13
12 6.7 ml H2SO4, 6.7 ml H2SO4, 3.3 ml HNO3 + 2 ml HCl; not suitable GWM – Nhill 6.37 4.32 18.61 9.25 ± 0.16 6.79 ± 0.63
3.3 ml HNO3 because of instantaneous frothing GWM – 6.14 1.70 51.63 5.66 ± 0.34 1.20 ± 0.07
a
Dimboola
At room temperature for 16 ± 1 h.
b a
At 110 °C for 5 h, except for Method 11 where the temperature was 60 °C. Standard deviation.
 C. Lomonte et al. / Chemosphere 72 (2008) 1420–1424 1423

a 110 110
100
105
90
100
80

Recovery (%)
Recovery (%)

70 95
60
90
50
40 85

30 80
20
75
10
0 90 95 100 105 110 115 120 125 130 135
1 2 3 4 5 6 7 8 9 10 11 Digestion T (°C)
Digestion Method
Fig. 2. Influence of the digestion temperature on the recovery of mercury in
biosolids samples (WTP (2), GWM – Nhill (1) and GWM – Dimboola (1)) spiked with
b 110 HgS. The error bars show the standard deviation of the recovery values at different
temperatures.
100

90 that the highest initial heating temperature where frothing did

not occur was 32 °C. Best results in terms of mercury recovery
80 were obtained with the following sub-steps: (1) 25–32 °C in
70 7 min; (2) hold at 32 °C for 15 min, (3) ramp to 65 °C in 23 min
Recovery (%)

at a rate of 1 °C/min; and (4) ramp to 110 °C in 15 min at a rate

60 of 3 °C/min. The digestion step was conducted for a further 5-hour
50 period at 110 °C as described in Table 1. The recovery results for
Methods 2, 3, 8 and 9 were 87.05 ± 6.39%, 85.02 ± 7.71%,
40
94.76 ± 8.90% and 99.54 ± 4.57%, respectively. They indicate that
30 in the absence of hydrogen peroxide (Methods 2 and 3, Table 1)
lower recoveries were obtained due to incomplete digestion of
20
HgS. The Student’s t-test revealed that the recoveries for Methods
10 8 and 9 (Table 1) were statistically significantly different at 95%
confidence level. Thus, it was concluded that under the selected
0
duration of the pre-digestion and digestion steps, Method 9 pro-
1 2 3 4 5 6 7 8 9 10 11
Digestion Method vided the best mercury recovery.

Fig. 1. Mercury recovery obtained by each one of the digestion methods studied on 3.5. Digestion temperature
biosolids samples spiked with CH3HgCl (a) and HgS (b). Each recovery value is the
average for four samples collected from WTP (two samples), GWM – Nhill (one
sample) and GWM – Dimboola (one sample). Mercury measurements in the digests
The most frequently used temperature in the hot plate digestion
were conducted in triplicate and the error bars show the standard deviation of the of environmental and biological samples is 95 °C (US EPA Methods
corresponding recovery values. 245.5, 1991; US EPA Methods 7471a, 1994; US EPA Methods
3050B, 1996; Anderson, 2000). This temperature is just below
the boiling point of dimethylmercury (i.e. 96 °C, (Anderson,
3.4. Temperature profile during the pre-digestion step 2000)) thus minimizing the loss of this frequently encountered or-
ganic mercury compound during digestion. Biosolids often contain
Higher temperatures accelerate wet digestion. However, the the resistant to wet digestion HgS and surface active organic com-
high content of organic matter in biosolids prevents their wet pounds. It can be expected that digestion temperatures higher than
digestion from being conducted at high temperatures before the 95 °C may be required for the complete wet digestion of these
decomposition of their readily oxidisable organic constituents compounds. Otherwise, their incomplete digestion may result in
has taken place. Otherwise, the digestion process would result in not only low mercury recoveries but also in frothing in the gas-li-
frothing and loss of sample material. To avoid these undesirable quid separator during the cold vapour generation step of the CV-
processes, an overnight (16 ± 1 h) pre-digestion step at room tem- AAS measurements which will worsen their reproducibility. In
perature was required to precede the 5-hour digestion step at agreement with the above discussion, the recovery of mercury at
110 °C. However, this lengthy pre-digestion step reduced substan- 95 °C digestion temperature was found to be lower than 85%
tially the sampling rate of the digestion methods studied and thus (Fig. 2). With increasing the digestion temperature complete
an attempt was made to introduce a 1-hour pre-digestion step in- recovery was achieved at 110 °C. Loss of dimethylmercury, which
stead. Such a step was expected to involve an appropriate temper- could be expected at temperatures higher than 96 °C, was pre-
ature profile reaching 110 °C before the start of the 5-hour vented by the decomposition of this volatile mercury compound
digestion step. The temperature profile of the pre-digestion step during the pre-digestion step. With further increasing the diges-
was divided into 4 sub-steps with constant temperature or a linear tion temperature, the recovery started to decrease (Fig. 2). This
temperature ramp with a rate between 1 and 3 °C/min. The dura- was most probably due to mercury loss through evaporation of or-
tion and temperature profile of each one of these four sub-steps ganic mercury compounds. On the basis of the results obtained
in the pre-digestion of biosolids were varied. It was established (Fig. 2), 110 °C was selected as the optimal digestion temperature.
1424 C. Lomonte et al. / Chemosphere 72 (2008) 1420–1424

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Acknowledgements pennsylvania program for using municipal sludge for mined land reclamation.
In: Proceedings Symposium on Surface Mining, Hydrology and Sedimentology,
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