Selective Extractions To Assess The Biogeochemically Relevant Fractionation of Inorganic Mercury in Sediments and Soils
Selective Extractions To Assess The Biogeochemically Relevant Fractionation of Inorganic Mercury in Sediments and Soils
Selective Extractions To Assess The Biogeochemically Relevant Fractionation of Inorganic Mercury in Sediments and Soils
Abstract
Here we present a new method for sequential selective extractions (SSEs) for Hg in geological solids, validated with ex-
tensive quality assurance procedures. Mercury was separated into fractions which “make sense” biogeochemically, rather
than being identified by specific compounds. Experiments elucidated the effects of extraction time, solids-to-liquid ra-
tio, and alternate solvents in natural samples, reference materials, and pure compounds. Compounds tested included HgS
(red and black), HgCl2 , Hg0 , Hg2 Cl2 , HgSe, HgO, Hg(II) adsorbed on goethite, Hg–humate, and gold amalgamated Hg.
Based on these findings, a five-step sequence of extractions was established to separate the compounds into biogeochemi-
cally distinct categories. The fractions and leaching media were as follows: F1 (deionized water), F2 (0.01 M HCl + 0.1 M
CH3 COOH), F3 (1 M KOH), F4 (12 M HNO3 ), and F5 (aqua regia). Method blanks and method detection limits (MDLs)
of 0.1–5 ng/g were obtained for the various analytical fractions, depending on the reagent concentrations used. Preci-
sion ranged from 2 to 8% for the major fractions in a sample, but increased to 2–40% for fractions making up <5%
of the total. Recovery of total Hg by the sum of species in reference materials showed that the accuracy of the method
ranges from 90 to 105%. Methylation potential, determined by anoxic incubation sample aliquots with biologically ac-
tive sediments, showed that inorganic Hg extracted in the F3 fraction is most strongly correlated with methylation po-
tential. In most natural and sediment incubation samples, the majority of Hg present was found either in the F3 or F5
fractions.
© 2002 Elsevier Science B.V. All rights reserved.
Keywords: Mercury; Speciation; Sediment; Sequential extraction
0003-2670/03/$ – see front matter © 2002 Elsevier Science B.V. All rights reserved.
doi:10.1016/S0003-2670(02)01550-7
234 N.S. Bloom et al. / Analytica Chimica Acta 479 (2003) 233–248
2.1.4. Fraction 3 (F3), 1 M KOH by adding 1.25 ml of 0.2 M BrCl before the rinse was
A 2.0 l Teflon bottle was half filled with reagent- added. The F3 fraction, owing to its high acid neutral-
grade deionized water, and 132 g of reagent-grade izing capacity, is oxidized by adding 10.0 ml of BrCl
KOH pellets (85% KOH, 15% water) were added solution.
with constant swirling. After dissolution, the bottle As a rinse step, the extraction vials containing the
was filled to the neck with reagent water and shaken sediment pellet were refilled with the same extrac-
to homogenize. tant, shaken vigorously to resuspend the sediment,
re-centrifuged, and filtered. The rinse was then added
2.1.5. Fraction 4 (F4), 12 M HNO3 to the extract from the same sample and the combined
To a 2.0 l Teflon bottle, 500 ml of reagent-grade sample diluted to 125 ± 1 ml with deionized water,
water was added, followed by the slow addition of as marked by the base of the bottle neck. After the
concentrated HNO3 up to the neck of the bottle. The rinse step, the next sequential extractant was added,
bottle was then capped and shaken to homogenize. the vials shaken to resuspend the sediment, and the
This reagent was stored in the dark to avoid the for- 18 h extraction and rinse procedure was repeated for
mation of brown NO2 . It is critical that the HNO3 and each extraction fraction except the last. After oxida-
Teflon bottle used are trace chlorine-free. tion with BrCl and dilution to volume, all selective
extracts can be stored indefinitely in glass bottles with
2.1.6. Fraction 5 (F5), aqua regia Teflon-lined caps until analysis.
This reagent is produced in situ at the final extrac- For the aqua regia extraction (F5), the reagents were
tion step. The procedure generates copious-free Cl2 added to the sediment pellet directly in the origi-
gas, so it must be conducted in a fume hood. Ten nal 40 ml vial. The samples were allowed to digest
milliliters of concentrated HCl was added to the sedi- overnight at room temperature in loosely capped vials,
ment pellet remaining in the 40 ml vial. After swirling and then diluted to 40.0 ml with deionized water. Aqua
the sample to dislodge the sediment, 3.0 ml of concen- regia extracts all known Hg species in most environ-
trated HNO3 was added, and the vials were loosely mental matrices, so it can be used for the direct de-
capped. As nitrosyl chloride (NOCl) and free Cl2 are termination of total Hg on sediments and soils, using
generated, the solution turns a dark orange color. sample aliquots of up to 2.00 g, dry weight basis [19].
In the case of crystalline metal ores such as bauxite
2.2. Selective extraction procedure and hematite, a significant residue of Hg remains after
aqua regia digestion [20]. In such cases, a sixth step
Extractions were carried out using 0.40 ± 0.04 g incorporating the dissolution of the final pellet in a
of dry solid, or the equivalent mass of wet sedi- mixture of HF + HNO3 + HCl at elevated temperature
ments, in 40.0 ml trace metal clean borosilicate vials and pressure may be warranted.
with Teflon-lined caps. All materials should be finely
ground or sieved to <100 m prior to extraction. Each 2.3. Analytical procedure for total mercury
step of the extraction procedure except for the final
(F5) step included a rinse between each new extractant. Total Hg in each oxidized fraction extract was
An initial aliquot of extractant was added to the solids determined using SnCl2 reduction, purge and trap
for 18±4 h with end-over-end tumbling at 30 rpm. The gold amalgamation preconcentration, and cold vapor
vials were then centrifuged at 3000 rpm for 20 min, atomic fluorescence spectrometry (CVAFS) detection
and the supernatant liquid decanted for filtration. [17,19,21]. This method has recently been validated
For the first three fractions, centrifuged extracts and promulgated for aqueous samples as US EPA
were filtered through disposable 0.4 m nitrocellu- Method 1631 [22]. A sample aliquot was pipetted
lose filter units. The last two fractions (F4 and F5) into a pre-purged bubbler containing 100 ml of 1%
do not employ a filtration step because those solu- HCl in deionized water, and 0.3 ml of 25% SnCl2
tions dissolve cellulose nitrate membranes. The ex- solution. For the 12 M HNO3 and aqua regia digests,
tractant from fractions F1, F2, and F4 were placed into no more than 5.0 ml of solution should be analyzed,
clean 125 ml borosilicate glass bottles and oxidized due to potential signal inhibition from the high acid
236 N.S. Bloom et al. / Analytica Chimica Acta 479 (2003) 233–248
concentration of these extracts. The Hg(II) in the bub- 24 h to allow gas phase equilibration. For our analysis,
bler is converted to Hg0 , which was then purged with the headspace gas was injected into an argon stream
N2 (20 min at 300 ml/min) onto a gold-coated sand passing through a gold-sand trap, which was then ana-
trap. Mercury collected on the trap was then ther- lyzed using the dual amalgamation/CVAFS procedure.
mally desorbed (2.5 min at 450 ◦ C) under argon flow The presence of Hg0 in the headspace at equilibrium
onto a similar “analytical” trap, which is part of the concentrations (15.54 ng/ml at 22.0 ◦ C), confirms the
CVAFS detector. The Hg collected on the analytical presence of free liquid elemental Hg in a sample. In
trap was then thermally desorbed (1.5 min at 450 ◦ C) cases where free elemental Hg was confirmed, the to-
under argon flow into the atom cell of the CVAFS tal Hg measured in the F4 fraction was assumed to
detector. Signals were quantified by chart recorder largely represent the Hg0 content of the sample.
or peak integrator. The instrument was calibrated by
reducing and purging known masses of pure Hg(II) 2.5. Analytical procedure for methyl mercury
aqueous standard solution (0.05–10 ng Hg), made
up by dilution of certified NIST-3133 solution. The Sediments and soils (0.5 g aliquots) were first ex-
instrumental detection limit is approximately 0.1 pg tracted from a KBr/H2 SO4 /CuSO4 mixture into 10 ml
Hg, although method detection limits (MDLs) are of CH2 Cl2 by vigorous shaking for 1 h. After cen-
ultimately determined by the reagent blanks. trifugation to separate the aqueous and organic lay-
ers a 2.0 ml subaliquot of the CH2 Cl2 layer was then
2.4. Analytical procedure for elemental mercury back-extracted by solvent volatilization into 60 ml of
pure water. This procedure avoids positive analytical
Elemental Hg (Hg0 ) was directly determined on the artifacts associated with the distillation extraction pro-
unpreserved deionized water extract (F1) prior to de- cedure [23,24]. Aliquots of the final extract were ana-
canting or filtering (to avoid volatilization losses) us- lyzed by aqueous phase ethylation, purge and trap onto
ing the same instrumentation as described for total Carbotrap, isothermal GC separation, and CVAFS de-
Hg. The only difference was that the extract aliquot tection [25,26]. The system was calibrated by ethyla-
was added to a bubbler containing pre-purged 1% HCl tion of known masses (5–200 pg) of CH3 Hg contained
in deionized water, with no addition of SnCl2 . The in a 10 g/l standard, which was calibrated for total
reduction reaction is so sensitive that a bubbler that Hg against NIST-3133 as described above. The ab-
has never been in contact with SnCl2 must be used solute detection limit of the system is approximately
to purge out the Hg0 , which is intrinsically volatile. 0.1 pg Hg as CH3 Hg, which results in a method detec-
The analytical system was calibrated using the same tion limit of approximately 0.005 ng/g Hg under the
Hg(II) standards, reduced with SnCl2 , in separate bub- conditions described.
blers, as described for total Hg. Because Hg0 reaches
saturation in water at approximately 50 g/l, values 2.6. Toxic characteristic leaching procedure (TCLP)
measured at or near this concentration in the F1 frac-
tion suggest that the sample contains free liquid metal- The TCLP procedure employs a solution of 0.5 M
lic mercury. In these cases, the total Hg measured sodium acetate and 0.5 M glacial acetic acid (pH of
in the F4 fraction gives a good estimate of the total 4.9 ± 0.1) to simulate leachability of solids within the
elemental Hg in the sample. If a significant amount moderately acidic environment of a municipal landfill
(greater than 1 ml) of the F1 extract is used for Hg0 [6,15]. Because only finely powdered samples were
analysis, a volume correction factor must be intro- analyzed for this study, sample heterogeneity was
duced in the calculation of the total Hg in the F1 not a significant problem, thus allowing a miniatur-
fraction. ized version of the TCLP procedure to be employed.
Confirmation of the presence of free liquid Hg0 can Instead of extracting 100 g of solids with 2.0 l of so-
be alternatively determined by the syringe removal of lution, 2.0 g of solids were extracted with 40.0 ml of
an aliquot (0.10–5.00 ml) of the headspace gas over a solution, maintaining the same 20:1 solution to solids
5–20 g aliquot of sediment in a closed glass jar. The ratio as the standard procedure. Samples were ex-
sample must remain at a known temperature for at least tracted for 18 ± 4 h in 40 ml borosilicate glass vials,
N.S. Bloom et al. / Analytica Chimica Acta 479 (2003) 233–248 237
Table 1
Example of method blank and estimated method detection limit (eMDL) study, method detection limit (MDL) study with standard
NIST-1646, and recoveries for a number of certified reference materials
Sample name Mercury concentrations (ng/g)
Register) by quantifying eight replicate extractions illustrate the typical detection limits obtained when
of a very low-level marine sediment (Table 1). The the method is applied to low-level samples.
MDLs were calculated as t × S.D. of the eight repli-
cates, where t = 2.96 for n − 1 degrees of freedom. 3.5. Pure compound speciation fingerprints
Because the speciation was not evenly distributed in
this natural sample, some of the fractions had con- Once the leaching parameters were established, a
centrations that were too high or too low to meet the series of 10 pure Hg compounds dispersed in pow-
(1–3)× of the MDL concentration criteria mandated dered kaolin were selectively extracted using this
by strict adherence to 40 CFR 136. We have found method to establish “extraction fingerprints” for each
on subsequent MDL studies that the values measured compound, and to help identify leachability classes
for all fractions vary by a factor of 3 from those re- (Fig. 4). All the compounds except the Hg–humics and
ported here, so that this data set serves adequately to Hg–Au amalgam were introduced as the powdered
N.S. Bloom et al. / Analytica Chimica Acta 479 (2003) 233–248 241
mercury or gold mining site, in which case most of the headspace or F1 extract, we have detected sub-
the Hg was found in the F5 fraction. This discrepancy stantial quantities (5–30%) of the total as volatile Hg.
between standards and real samples is probably an ar- Thus, the thermal volatilization method may substan-
tifact of using pure kaolin as an “inert” carrier for the tially overestimate the amount of Hg0 present in natu-
standards. ral samples. We infer from measurements of 1 M KOH
extractable Hg and/or TOC that this volatile Hg is a
3.6. Elemental and volatile mercury result of the breakdown of organo-complexed Hg(II),
although at some chlor-alkali sites, it may have re-
The accurate determination of Hg0 in solids is sulted from HgCl2 volatilization. Because of the ubiq-
problematic, and generally must be diagnosed using uity and magnitude of the error associated with this
a weight of evidence approach. The F1 (deionized method, it is not recommended for the routine quan-
water) extraction can be used to determine levels of tification of Hg0 in environmental samples.
Hg0 in the samples which are less than approximately Previous research shows that all free Hg0 present
5 g/g under the conditions of this extraction, assum- in a sample will dissolve in the cold 12 M HNO3
ing that Hg0 is not adsorbed on particles or oxidized (F4) step [4]. Although this measurement is poten-
to Hg(II). All samples exhibiting saturated Hg0 in tially confounded by other compound classes such as
the F1 fraction have contained macroscopic or micro- Hg(I), and Hg bound up in amorphous organo-sulfur,
scopic liquid Hg0 . Even if values of less than 50 g/l Hg–Ag amalgams, or crystalline Fe/Mn oxide phases,
Hg in F1 are interpreted ambiguously, mercury at it may be interpreted as an estimate of total Hg0 in
water saturation levels can be used to confirm the cases where Hg0 was confirmed by saturation of the F1
presence of significant Hg0 levels in soil samples. fraction or visual identification. Interestingly, in cases
Historically, Hg0 has been defined as that which where small balls of liquid Hg0 were added to natural
is volatilized upon heating the sample for 5 days at soils and sediments, we observed a rapid loss of Hg0 in
150 ◦ C [2]. To investigate the validity of this approach, the headspace. In these same samples, the bulk of the
we looked at the volatility of Hg0 and HgS (investi- Hg remained in the F4 fraction, even after periods of
gated by Revis) and several other mercury compounds up to 6 months. This suggests that in the natural envi-
(Fig. 5). As in Revis’ experiment, we found that vir- ronment microscopic balls of Hg0 are quickly coated
tually all of the Hg0 and none of the HgS (cinnabar with a gas-impervious layer, preserving the mass of
or metacinnabar) was volatilized. Unfortunately, we the droplets from further oxidation and/or diffusion.
also found high rates of volatilization for HgCl2 and
Hg bound to humic matter. In every case where we 3.7. Comparison with other extraction procedures
have applied thermal volatilization to environmental
samples that contained no detectable Hg0 in either Because selective extractions are used to make as-
sertions about bioavailability, we compared the cur-
rent procedure to two other extractions commonly
used to assess “bioaccessable” Hg. Bioaccessability
refers to the amount of the compound that can poten-
tially dissolve from the sample and become an aque-
ous exposure route to an organism. This differs from
bioavailability, the fraction of the compound of inter-
est that actually enters the organism, which can only
be determined using in vivo tests [1]. Although ex-
periments have yet to be performed with Hg, previous
work with Pb and As have shown a very good corre-
lation between bioaccessability measured in vitro and
bioavailability measured in vivo. In this study, the sol-
Fig. 5. Percent of mercury volatilized in compounds heated at uble Hg determined as the sum of the F1 and F2 extrac-
150 ◦ C for 5 days. tion fractions compares quite favorably with both the
N.S. Bloom et al. / Analytica Chimica Acta 479 (2003) 233–248 243
Table 2
Comparison of TCLP and in vitro methods to extract “bioavailable inorganic Hg” with the sum of F1 (deionized water) and F2 (acetic
acid/HCl) extracted mercury
Sample description Lab code Total Hg (g/g) TCLP Hg (g/l) Percent of total Hg leached
F1 + F2 TCLP In vitro
Hg extracted by the TCLP extraction and the in vitro NIST-2710 was extracted by F2 , compared to <1%
simulated human stomach extraction test (Table 2). typically found in our F2 fraction. The increased Hg
Small differences observed between the methods were found in F2 resulted in less Hg observed in the F4 and
likely a result of between-method variations in ex- F5 fractions, suggesting that a significant amount of
traction time, solids-to-liquid ratio, and temperature. Hg in this CRM may be bound up in crystalline Fe/Mn
Overall, the sum of F1 + F2 showed the greatest ex- oxides. Further investigation of the behavior of this
traction, probably due to the low solids-to-liquid ratio extractant with environmental samples is warranted.
and pH, while TCLP averaged the lowest extraction,
probably due to the methods higher pH and extraction 3.8. Relationships of speciation to methylation
ratio. The simulated stomach test operated at a more potential
aggressive pH and temperature, though this was offset
by the short extraction time of 1 h, compared to 18 h Besides employing selective extractions to assess
for F1 + F2 and TCLP. the bioaccessability of solid phase Hg to mam-
Recent reports have indicated that sodium py- malian ingestion, the method can be used to infer
rophosphate (0.5 M Na4 P2 O7 at pH 10.5) may be a
more accurate and robust measure of organo-complexed Table 3
metals than the 1 M KOH extraction at pH 14 [27]. Results of an extraction sequence using glycine/HCl instead of
To assess the differences between the two extractants acetic acid/HCL for fraction 2 and pyrophosphate in place of 1N
for Hg analysis, a comparison was performed using KOH for fraction 3 on various standards
the entire extraction scheme, but substituting the pH Sample Percent of total mercury
1.5 glycine solution for F2 and the 0.5 M Na4 P2 O7 F1 F2 F3 F4 F5
solution for F3 (Table 3). Although these two sets
of extractants gave significant differences for their NIST-2710a 0.5 0.4 2.3 47.8 49.0
NIST-2710b 0.7 0.0 4.5 37.5 57.2
particular fractions, overall the conclusions about
the biogeochemical availability of most environmen- NIST-2711a 0.0 14.1 6.9 72.4 6.6
NIST-2711b 1.0 0.0 3.4 61.2 34.3
tal samples would be similar with either extraction
scheme, when data are compared as percentages of (Hg0 )a 2.7 1.3 0.0 95.7 0.2
the total Hg in the extracted sample. (Hg0 )b 0.1 0.2 0.3 96.7 2.8
In another study, the classic extractant for total Fe+ HgCl2 a 98.3 1.6 0.0 0.1 0.0
Mn oxides (25% CH3 COOH plus 1N HN2 OH (F2 ) HgCl2 b 96.5 3.2 0.2 0.1 0.0
[12]) was substituted for the F2 extractant of the cur- Hg2 Cl2 a 7.2 12.2 43.7 36.1 0.8
rent method on a series of deep soil cores. Almost none Hg2 Cl2 b 0.8 1.5 53.3 43.8 0.5
of the Hg was extracted in the Tessier F2 fraction. In- HgSa 0.0 0.1 0.0 0.5 99.4
stead it was found in the F3 and F4 fractions, as would HgSb 0.0 0.0 0.0 0.1 99.9
be expected from organic-rich samples. Conversely, a The substituted procedure.
in that extraction 40% of the Hg in control sample b The procedure presented in this paper.
244 N.S. Bloom et al. / Analytica Chimica Acta 479 (2003) 233–248
bioavailability of Hg to sediment bound methylating Hg methylated following anoxic incubation (Fig. 6).
organisms. We tested this by mixing various Hg com- All of the incubations were spiked such that the total
pounds and natural high mercury sediments with a Hg in the samples was increased from approximately
biologically active sediment, and then measured the 0.06 to 5 g/g (wet weight basis), and were incubated
anaerobically, with periodic shaking.
Samples spiked with readily bioavailable com-
pounds such as HgCl2 show rapid distribution of Hg
to a similar species distribution as the initial sediment,
as well as a high degree of methylation. Although less
soluble compounds, such as HgS, are more inert, they
appeared to slowly convert to the speciation of the
ambient sediment, and were also methylated, albeit to
a lesser degree. All of the incubated Hg-contaminated
Table 4
Ancillary data for 11 natural sediment profiles
Sample Description Hg0 (g/m3 ) Total Hg Methyl Hg TCLP Hg
(g/g) (g/g) (g/l)
GM-1 Gold mine tailings (deep) 72.7 41.7 nd 407
GM-2 Gold mine tailings (surface) 5.6 635 nd 28.3
CM-1 HgS mine soil, retort area (surface) 3.3 511 0.01 0.73
CM-2 HgS mine soil, retort area (10 cm) 0.1 860 nd 0.14
CM-3 HgS mine soil, retort area (210 cm) 18000 7180 0.03 2900
CS-1 Hg0 spill impacted arid soil (90 days) 1240 37.2 nd 0.39
CS-2 Oak Ridge Hg(NO3 )2 floodplain soil (50 years) nd 546 0.03 nd
CS-3 Chlor-alkali plant cell area top soil 16800 73300 0.01 18900
CS-4 Red Devil Mine sediment 1 19.7 19900 9.85 nd
CS-5 Red Devil Mine sediment 2 8880 78400 7.11 nd
CS-6 Red Devil Mine sediment 3 2.3 3990 0.65 nd
246 N.S. Bloom et al. / Analytica Chimica Acta 479 (2003) 233–248
floodplain as aqueous Hg(II), and to upland soils as tion. Samples from the floodplain of East Fork Poplar
Hg0 adsorbed to foliage, and then deposited to the Creek are similar in age (30–50 years) and deposi-
soil as litterfall. Today, ∼90% of the Hg at both sites tion environment to those from the chlor-alkali plant
is bound to soil humic matter. Yet the fraction in the site, but >70% of the Hg, originally deposited from
methylated form is approximately 1000 times higher dissolved Hg(II) is now present as cinnabar (HgS),
in the upland forest than in the floodplain site. Differ- rather than organo-chelated Hg. The East Fork Poplar
ences like this beg for further research and explana- Creek soils contain methyl Hg fractions approximately
Fig. 9. Methyl mercury (as % of total mercury) correlated with each fraction in Thai marine sediments with unique mercury fingerprints
(n = 18).
N.S. Bloom et al. / Analytica Chimica Acta 479 (2003) 233–248 247
50 times lower than corresponding samples from the ral samples and laboratory sediment incubations, we
chlor-alkali floodplain site. These differences may be have identified that the F3 (organo-chelated) fraction
due to the difference in total Hg concentration between is most strongly correlated with sediment methyla-
the sites. One explanation is that inorganic Hg added tion potential. We have also shown that when added
to sediments or soils readily converts to cinnabar at to aquatic sediments, all Hg compounds will tend to
high concentrations but at lower levels complexation convert to an ambient Hg speciation profile dictated
by organic matter interferes with the formation of a by the specific biogeochemical properties of the re-
pure macroscopic crystalline phase. ceiving sediment. The question does not appear to be
if the more recalcitrant forms, such as HgS will be
3.10. Relationship of in situ inorganic Hg speciation methylated, rather, how long it will take to reach equi-
to methylation librium. Although more research is needed to quantify
the kinetic relationships in various climates and sed-
The relationship of in situ Hg speciation to methy- iment types, this finding has significant implications
lation is difficult to accurately represent because each for the management of Hg-contaminated sediments,
sediment type has a different methylation potential. soils, and tailings.
To examine this relationship, we looked at biogeo-
chemically similar surface marine sediments from the
Gulf of Thailand, which range in total Hg and specia- Acknowledgements
tion due to historic contamination by HgCl2 and Hg0
from natural gas extraction. Data relating the percent We would like to thank Alfred Rodarme for his
of methyl Hg found in these sediments to each of the skill in preparing the figures for this text, as well as
inorganic Hg extraction fractions obtained by selec- Sharon Goldblatt and Jennifer Parker for their helpful
tive extraction are presented in Fig. 9. The fraction of criticisms and editorial comments.
methylated mercury in these sediments shows a fairly
strong positive correlation with the F3 fraction, and
a negative correlation with the F4 and F5 fractions. References
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