pubs.acs.

org/EF Review

Methods for Total and Speciation Analysis of Mercury in the

Petroleum Industry
Maxime Enrico,∥ Aurore Mere,∥ Honggang Zhou, Matthieu Loriau, Emmanuel Tessier,
and Brice Bouyssiere*

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ABSTRACT: Mercury is one of most dangerous contaminants of natural gas and petroleum and petroleum fractions present in the
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crude oil industry due to its corrosive properties. The determination of Hg levels in petroleum products is a prerequisite for risk
evaluation and ensuring an efficient Hg removal. This Review focuses on total and speciation analyses of Hg in the petroleum
industry. We describe the constraints related to sampling and analysis for both natural gas and liquid petroleum products and the
different methodologies developed over the past decades. Despite the low detection limits reached with various methodologies, the
reliability of measurements might strongly depend on sampling and storage practices. The preservation of all Hg species from
sampling to analysis might require some further evaluation. We evaluated the speciation methodologies based on reported
performances. We however conclude that the lack of reference material for Hg speciation analysis in petroleum hampers a robust
evaluation of the methods. Future developments might allow a better characterization of the different Hg species, helpful to
understand the partitioning of Hg between the different petroleum phases.

1. INTRODUCTION supposes that Hg is present in its volatile form of Hg0.1,3 The

Mercury is a naturally occurring and problematic component partitioning of Hg between these phases is governed by
of petroleum products. This heavy metal is present in all Henry’s law. Although this approach sometimes gives
petroleum fractions at levels varying by several orders of satisfactory results, the gas-phase Hg concentration is some-
magnitude ranging from 0.01 ppb to 10 ppm.1 Its presence in times overestimated by more than an order of magnitude.4 It
hydrocarbon fluids might result from Hg present in organic has been noted that this was particularly the case when H2S
matter prior to burial, mantle degassing of gaseous Hg0 and was present. The presence of H2S and other sulfur compounds
scavenging by petroleum or mobilization of mineral Hg from is known to affect Hg speciation.5 The initial assumption of
surrounding rocks.9,77 Hg is a toxic and volatile heavy metal. In Hg0 being the only species is therefore erroneous when sulfur
its metallic form (Hg0), it is generally found as a gas, although is present at high concentrations, and the presence of soluble
it might also occur as liquid drops when the gas phase is Hg species concentrates Hg in the relatively heavy hydro-
saturated. Upon oxidation, Hg0 might be converted to salts carbon fractions. A better understanding of Hg chemistry in
(such as HgCl2) or complexes (thiolates, amines, etc.). The petroleum is therefore required to better anticipate Hg
most toxic forms of Hg are methylated Hg neurotoxins that are partitioning and implement appropriate structures and
soluble (monomethylmercury) or volatile (dimethylmercury, maintenance procedures.
DMHg). The assessment of Hg levels in hydrocarbon streams is
In addition to being problematic for both health and the complicated by several constraints. The exposure of fluids to
environment, Hg catalyzes the corrosion of aluminum pipeline inner surfaces allows for some reactions that might
components, with potentially dramatic consequences in affect Hg chemistry. These different issues presented in the
petroleum processing plants.2 Failures of a liquefied natural first section of this work need to be taken into account when
gas due to Hg-induced corrosion were responsible for sampling and analyzing Hg in hydrocarbons streams. Different
numerous deaths. The implementation of mercury removal
methods have been developed over the past few decades to
units (MRUs) efficiently prevents such failure, yet some
reliably determine the Hg concentration in both gas and liquid
maintenance is necessary. In particular, each MRU can remove
a given amount of Hg that depends on the amount of
hydrocarbons treated and their Hg concentration. Reliable Received: August 13, 2020
evaluation of Hg concentrations in hydrocarbon streams is Revised: October 7, 2020
therefore necessary to avoid saturation of the MRU, which Published: October 19, 2020
could lead to inefficient Hg removal.
Hg partitioning between the different phases of petroleum
can be estimated by thermodynamics. This, however, generally

© 2020 American Chemical Society https://dx.doi.org/10.1021/acs.energyfuels.0c02730

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hydrocarbon samples. We summarize these methods in The net enthalpy for this reaction is −155 kJ·mol−1, which is
sections 2 and 3 of this Review. more likely than reaction 1a. Pyrite (FeS2) formation could
In addition to Hg concentration, the efficiency of the MRUs explain the adsorption of Hg. The surface of pyrite contains
depends in part on the Hg species present. The different Hg pyritic groups (S-S) and Fe (hydr)oxides. Sorption of Hg(II)
species that can be found in liquid hydrocarbons (including on the pyrite surface occurred at both the oxide and pyritic
Hg0, ionic Hg, organic Hg and particulate Hg) have different sites,14,15 with Hg bound to an additional counterion (as S-
chemical properties.6−8 In natural gas, it is usual to consider Hg-Cl, S-Hg-OH, O-Hg-Cl, and O-Hg-OH). In
Hg0 to be the only significant species due to its high volatility natural gas streams, however, Hg is present in its elemental
compared to those of the other, more soluble species. The form (Hg0) and therefore requires an oxidation step for such
study of Hg speciation in liquid hydrocarbons is of interest surface complexation. In these studies, precipitation of HgS
because of the need for sufficient treatment procedures. was excluded, but these studies were not conducted on
Although Hg0 might be the dominant form of Hg in deep hydrocarbon samples.
reservoirs,9 the presence of oxidized Hg, particulate Hg and 2.1.2. Implication of Adsorption Problems for New Pipes.
alkylated Hg species was reported.10,11 For Hg concentration, The concentration of Hg in natural gas can vary over time,
various techniques are used to evaluate the relative abundance making it difficult to determine precisely. In particular, the
of these species. Section 4 is dedicated to the description of analysis of natural gas from a new well may not be informative
these techniques. of the concentration of Hg in the reservoir. Indeed, Hg
Among the numerous method developments for both Hg adsorption may occur on the inner surfaces of the reservoirs,
concentration and speciation determination in petroleum and the gas is therefore depleted of Hg. Hg analysis could
streams, only few gave rise to standard methods. The present therefore underestimate the Hg content of a gas stream by
standard methods are also relatively old and were only adapted several orders of magnitude.
through minor revisions and did not consider the major recent In addition, gases that first reach the Earth’s surface may be
developments in the field. depleted of Hg relative to that in the reservoir because sorption
can occur on the well walls. It is therefore important to
2. GENERAL CONSTRAINTS RELATED TO THE regularly monitor the Hg concentration in natural gas until a
SAMPLING AND QUANTITATIVE ANALYSIS OF stable value is reached.
MERCURY In addition, Ryzhov et al.16 observed an oscillation in Hg
2.1. Natural Gas. The objective of Hg analysis in concentration during sampling campaigns. A 25-hour cycle was
petroleum products is to assess any risk to downstream attributed to the lunar tidal cycle, while higher frequency
operations. Therefore, Hg analysis must be representative for oscillations were observed but not included. These oscillations
such an assessment. Several constraints need to be considered sometimes do not significantly affect the Hg concentration
for reliably estimate Hg levels. We first focus on general issues range. In some cases, however, the fluctuations could lead to an
that apply to any sampling methodology. error of more than 20% if a single sample is analyzed. Diurnal
2.1.1. Hg Adsorption. 2.1.1.1. Current Knowledge. The Hg and annual cycles can also be anticipated, as temperature
adsorption process is not yet completely resolved. However, affects adsorption/desorption of Hg in pipes and thus increase
significant losses of Hg are observed for H2S-containing the Hg concentration during the summer.17
streams, which probably indicates a reaction involving both 2.1.3. Implication of Adsorption Problems for the
H2S and Hg. Two studies reported the following reactions:12,13 Sampling System. Natural gas sampling requires a bypass of
the main gas stream. This sampling system is not constantly
H 2S + Fe2O3 → 2FeO + S0 + H 2O (1a) filled with natural gas, so the initial gas stream is not in
equilibrium with respect to Hg adsorption. An equilibration
Hg 0 + S 0 → HgS (1b) time is therefore necessary before sampling with the chosen
Cinnabar (HgS) is a solid mineral and can therefore methodology. This time depends on the total internal surface
accumulate in pipes. These two studies did not show this area of the bypass line. A reduced line is therefore preferable.
reaction but cited an earlier study2 to support this concept. Adsorption also depends on temperature. An experimental
Larsson et al.13 observed that a gas containing both H2S and study on the efficiency of Hg transport in stainless steel tubes
Hg had no loss of Hg when flowing through PTFE tubes, but showed that heating from 70 to 100 °C hinders Hg
significant losses were observed in stainless steel tubes. This adsorption.13 Therefore, a heated bypass line would signifi-
suggests that the Hg and H2S gases do not react directly, which cantly reduce sampling times.
would support the mechanism described by eqs 1a and 1b. 2.2. Liquid Petroleum Products. Sampling procedures
2.1.1.2. Thermodynamic Considerations. The standard must be appropriate to preserve the stability of Hg in liquid
free enthalpy of formation of the iron oxide Fe2O3 is −825.5 hydrocarbons. The different species of Hg found in liquid
kJ·mol−1, while that of FeO is −272.04 kJ·mol−1. Balancing eq hydrocarbons (including Hg0, ionic Hg, organic Hg, and
1a (taking into account H2O, S0 and H2S) gives a net enthalpy particulate Hg) have different chemical properties and
of +18 kJ·mol−1. A positive net standard reaction enthalpy behaviors.6−8 To determine the mercury species composition
indicates that the reaction should not take place at room of a hydrocarbon, it is very important that Hg is preserved in
temperature. Adsorption of Hg on stainless steel surfaces in the the sample during sampling, storage, and sample preparation
presence of H2S was observed at 25 °C, so the proposed prior to analysis. Several studies have shown that inappropriate
reaction seems unlikely. sampling and treatment could lead to an underestimation of
However, from our point of view, another reaction between the Hg concentration in the condensate.3,20 The different
iron oxide and H2S is more favorable: mechanisms to be avoided are discussed below.
2.2.1. Volatile Hg Loss. Two species of Hg are particularly
4H 2S + Fe2O3 → 2FeS2 + H 2 + 3H 2O (2) volatile: Hg0 and DMHg.10,18 DMHg is generally very low in
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concentration and often below the limit of detection.19 the use of a Swagelok cylinder lined internally with PTFE
Therefore, the main issue is the loss of Hg0. In the study of could preserve anoxic conditions for Hg(II) preservation.
Hg speciation in condensates in Egypt, Ezzeldin et al.3 found 2.2.3. Precipitation of Hg-Containing Minerals. Particulate
that following a pressure drop between the first and second Hg is potentially naturally present in condensates. However, no
separators, Hg0 was transferred to the gas phase. A similar studies have actually identified this. Only one study showed the
process may occur during sampling or sample storage, as existence of metacinnabar (β-HgS, black cinnabar) in crude oil
condensate samples are taken at atmospheric pressure. In the residues.24 However, it has been shown that Hg can precipitate
same study, the authors compared their speciation results to with S to form HgS minerals when the sample is exposed to
the total Hg measurements. For condensate samples ambient air.5 This is particularly true when H2S is present in
containing mainly Hg0 (untreated condensate), the summed the sample. While Hg does not react directly with H2S,19
concentration of the detected Hg species was only half of the contact with air can promote the oxidation of H2S, leading to
total Hg concentration measured independently. This the generation of elemental sulfur. HgS minerals can then
unsatisfactory mass balance was attributed to losses of Hg0. precipitate from Hg and elemental sulfur. This is an additional
Wilhelm et al.20 observed that the Hg concentration in crude reason why contact with ambient air should be avoided prior to
oil samples decreased with the number of bottle openings. Hg analysis.
During sample storage, dissolved Hg0 may also volatilize into Another potential precipitation process may occur. Snell et
the free space of a container. These results suggest that sample al.21 observed that when the two Hg species Hg0 and Hg(II)
containers should be filled without free space and that the are present in a condensate sample, they can react and form a
opening of containers should be avoided to prevent metallic bond, giving rise to insoluble Hg(I) species:
evaporation and/or transformation of Hg species over time.
Snell et al.21 also observed a significant loss of Hg0 in mixed Hg 0 + HgCl2 → Hg 2Cl 2 (3)
hydrocarbon solutions over time.
Different sampling procedures can be designed to avoid The factors that might affect this precipitation reaction are
volatile Hg losses. Pressurized cylinders can be used to poorly understood (pressure, temperature, chemical character-
preserve the initial sample pressure conditions.5 The use of a istics of the sample, etc.), so it may be advisable to remove Hg0
container with a septum cap could be practical, as a syringe from the condensate sample after sampling. Such a procedure
could be used to take an aliquot of the sampled gas without exists and is part of a speciation procedure.25
opening the container. The ASTM protocol for “Sampling, 2.2.4. Sample Homogeneity. Any analysis performed on a
Storage, and Handling of Hydrocarbons for Mercury sample aliquot assumes that the Hg is homogeneously
Analysis” 22 recommends the use of glass vials with PTFE- distributed in the sample. Heterogeneous samples can lead
lined septum caps. In this way, it is possible to limit the to a poor estimate of Hg concentration and inconsistent repeat
volatilization of Hg0 by filling the sample vial with no free analyses.26 Depending on the Hg species present, the different
space. mechanisms described above (adsorption on container walls,
2.2.2. Ionic Hg Adsorption on Container Walls. Hg is volatilization of Hg0, as well as sedimentation of particles)
known to bind to the walls of storage and/or sampling need to be taken into account.
containers/containers. Despite its relative inertness compared Wilhelm et al.20 tested different homogenization procedures
to other materials, glass tends to be negatively charged and can and found that ultrasonic treatment at 30 °C gave Hg
attract cationic forms of Hg that will absorb onto the glass recoveries >80%, while the heating and stirring procedure
surface. Acidification of the glass surface can repel Hg species exhibited only a 30% recovery. Ultrasonic treatment is
and stabilize them within the sample, thus preventing further therefore recommended prior to aliquoting for total mercury
Hg loss.3 and speciation analysis.
The adsorption of Hg depends on the nature of the material
but also on the chemical species of Hg contained in the matrix.
3. MERCURY ANALYSIS IN NATURAL GAS
Bloom et al.23 showed that Hg0 and DMHg diffuse through the
walls of plastic containers. 3.1. Sampling Method. 3.1.1. Bubbling System. This
The composition of the sample matrix may play a role in this sampling procedure involves bubbling natural gas into a
adsorption effect. Bloom10 tested the stability over time of Hg0, trapping solution. This solution is a mixture of potassium
inorganic Hg, and dimethyl- and methylmercury chloride permanganate and sulfuric acid.27 Usually, three bubblers are
species contained in doped paraffin oil and in composite oil in used in series to monitor the potential inefficiency of Hg
different containers (borosilicate glass containers with Teflon- trapping in the first bubbler. This mixture oxidizes the Hg0
lined caps, Teflon FEP bottles, polyethylene bottles, stainless contained in the gas into soluble ionic Hg(II). This soluble
steel bottles (No. 316) and glass bottles lined with aluminum). ionic Hg(II) is retained in the trapping solution and can then
A significant loss of inorganic Hg was observed in doped be analyzed. The sampling time must be long enough to reach
paraffin oil in a glass container, whereas no loss of inorganic a mercury concentrate that is sufficient for quantification. The
Hg was observed in composite oil contained in the same glass amount of Hg recovered in solution (sum of three trapping
container. This shows that the composition of the matrix, solutions) divided by the volume of gas bubbled into the
especially its polarity, can influence this adsorption phenom- solution gives the Hg concentration in natural gas. This
enon. method was recently adapted to allow for sampling at pressures
This adsorption induces an underestimation of the measured up to 100 bar with direct connection to distribution and
Hg concentration. Various studies have shown that this transportation networks.41 The results showed that more than
problem can be solved by using appropriate sample containers. 90% of Hg was trapped in the solution of the first bubbler with
The ASTM D7482-17 protocol suggests the use of glass vessels insignificant Hg breakthrough, showing the efficiency and
with a PTFE-lined cap.22 Recently, Gaulier et al.5 showed that reliability of this sampling system.
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Table 1. Commercial Instruments Dedicated to Hg Analysis in Gases

DL accuracy weight flow rate
brand name detector analysis (ng/m3) (%) (kg) (L/min)
Brooks Rand Model III AFS lab, gold traps (requires 0.1
amalgamation)

Nippon Instrument WA-5A AAS Au traps, Tedlar bags, gas 1 pg 13 0.1−1

Corp. cylinders
WA-5F AFS Au traps, Tedlar bags, gas <0.1 pg 13 0.1−1
cylinders
EMP (three different instruments) AAS in situ 100− 10 0.3−1
50000
AM-4 AAS air monitoring 0.01 2 0.1−0.5

LUMEX RA-915+ AAS direct gas analysis 2 7.5

RA-915M AAS direct gas analysis 2 7
Light 915 AAS direct gas analysis 100 3.3
RA-915M + RP-91NG AAS in situ (special NG) 10
AMNG AAS monitoring for NG 1−1000

Arizona Jerome 431-X gold film in situ 3000 5 3.2 0.75

Instruments Jerome J405 gold film in situ 500 5−10 2.4 0.75
Jerome 451 gold film in situ, monitoring 3000 8 24 0.75
Jerome J505 AFS in situ 50 10−15 3 1

PSA PSA 10.54X Sampling System + AFS in situ, monitoring (special

PSA 10.670 Process Analyzer NG)
10.525 Sir Galahad AFS lab, gold traps <0.1 pg

Ion Science MVI mercury vapor detector UV abs. in situ 100 10

Mercury VM-3000 AAS in situ, monitoring 100 7

Instruments 3000-IP in situ 100 5
UT-3000 AAS in situ, monitoring 0.1 9
UT-3000 + NG-sampling system 3000 AAS in situ, for NG 0.1 50
MMS AAS in situ, monitoring 100 35−175
MMS-NG AAS in situ, monitoring, for NG 1

TEKRAN 2600 NG AFS in situ, monitoring, for NG 1

2537A and 2537B AFS in situ, monitoring, ambient 0.1
air
2500 AFS lab

Hg recovery is, however, significantly reduced in the several processing steps can lead to higher background signals
presence of high H2S concentrations. Brombach and Pichler28 and possibly more potential for contamination.
observed that in the presence of H2S, the recovery of Hg in 3.1.3. Gold Amalgamation. The system is based on
potassium permanganate dropped by nearly 50% due to the trapping Hg from natural gas by directing the flow through a
formation of mercury sulfide (HgS). This issue was overcome tube of a solid sorbent containing gold.31 However, this
by bubbling the gas in a solution of sodium borohydride process has a major advantage over the use of iodine-
upstream of the Hg trapping solutions to trap H2S and avoid impregnated sorbents. Gold amalgamators can indeed be
any interference in Hg oxidation. analyzed without any digestion steps.3 After sampling, the
3.1.2. Hg-Selective Sorption. For this sampling method, a amalgamator is heated, and Hg is released in an atomic
absorbance spectroscopy (AAS) or atomic fluorescence
stream of natural gas is carried through a glass tube containing
spectroscopy (AFS) detector. The most widely used metal
iodine-impregnated silica gel. The Hg is trapped by
for trapping Hg is gold, but Hg can form amalgams with the
chemisorption inside this tube. The adsorbed Hg is then most noble metals. Different studies have investigated the use
extracted from this tube by dissolving it in an ammonium of metal alloys and their efficiency for Hg trapping.13,32 Silver,
iodide/iodine (NH4I/I2) solution.29 This solution is then gold and platinum−gold alloys allow for quantitative Hg
analyzed to determine the total Hg content of a natural gas, retention.
taking into account the volume of gas sampled. Quantitative By using the thermal release procedure, the analysis can be
recovery of Hg (91−109%) was achieved using this method- performed on the site if a detector is available (Table 1). This
ology in gas wells from China.30 However, the existence of a allows a direct evaluation of the sampling efficiency, and the
liquid extraction stage hinders in situ analysis. In addition, the sampling time and volume can be directly adjusted. A
simplest procedures are always preferred, as the addition of reduction in pressure is necessary, however, as the amalga-
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Figure 1. Schematic presenting the different methodologies for Hg quantification in natural gas, from sampling (top boxes) to sample processing
(middle boxes) and detection (right boxes).

mators operate at ambient pressure. This method can be used inertness of the coating is compromised by repeated sampling
to determine the total Hg content ranging from 0.01 to 100 μg· of natural gas samples.35
m3 in natural gas samples.31 Adapted sampling flow rates are Alternatively, natural gas can also be sampled using inert
also required to avoid Hg breakthrough. Frech et al.33,34 plastic bags (Tedlar bags).37−39 Despite its ease of use, this
suggested that the maximum natural gas flow rate should be 2 sampling technique does not allow for natural gas to be
L·min−1, and the maximum sample volume should be 10 L sampled under pressure, and the conservation of compounds in
when using a Pt−Au amalgamator. Despite these results, the gas samples over time is not assured within these bags.40,41
Larsson et al.13 obtained Hg recoveries greater than 90% with Although the onsite sampling portion can be simplified by the
amalgamators similar to Frech et al.,34 with higher flow rates use of cylinders, the processing of samples in the laboratory
(up to 10 L min−1) and higher sampling volumes (up to 100 may require more time. All disadvantages associated with the
L). This difference can be explained by the different use of amalgamators (discussed in the gold amalgamation
compositions of natural gas that could influence the transport section) remain, as an amalgamation is required prior to
efficiency of Hg on these traps, although this has not been analysis. Despite this constraint, the use of such samplers
proven.13 Despite this, a recent study has shown that the allows for a reduction in sampling time in the field, which can
efficiency of Hg trapping on gold traps is much lower or almost be advantageous.
nil when the natural gas sample contains H2S.28 3.2. Hg Analysis. In natural gas, mercury exists almost
Heating the amalgamator during sampling generally exclusively as Hg0.1,3 Therefore, the analyses performed
increases Hg recovery. The aim is to avoid condensation of provide only the total amount of Hg in natural gas, i.e., Hg0.
liquids that could poison the amalgamator and thus reduce the The trapping solutions (KMNO4/H2SO4 solution) obtained
trapping efficiency. The temperature to which the amalgamator
after bubbling the gas sample as well as the ammonium iodide/
can be heated depends on the alloy used. Frech et al.34 showed
iodine (NH4I/I2) solutions obtained after extraction of the Hg
that Pt−Au amalgamators could be heated up to 200 °C
contained in the iodine-impregnated silica gel can be analyzed
without any loss in trapping efficiency, whereas gold
by cold vapor generation (CV)-AFS, CV-AAS, and inductively
amalgamators were ineffective at over 170 °C.
3.1.4. Gas Samplers: Cylinders and Tedlar Bags. The use coupled plasma mass spectrometry (ICP-MS).27,29 For the first
of pressurized cylinders is generally very convenient for two analytical techniques, the detector is based on AAS or
sampling natural gas. Because pressurized cylinders can handle AFS, respectively (Figure 1). During analysis, a reducing agent
high pressures, sampling is fast. Hg measurements can be made (SnCl2, NaBH4) must be added to the solution to convert
once back in the laboratory by releasing some or all of the Hg2+ to Hg042 during CV.
sampled gases through a gold amalgamator, which is then For gold traps (direct sampling and/or after release of
analyzed by AAS or AFS.31 Although sampling is made easier natural gas sampled in Tedlar cylinders/bags), the usual
with such a system, its reliability is of great concern. Hg is method for Hg quantification is based on thermal desorption.
known to adsorb to most surface materials, including the inner The sampled gold trap is heated to ∼500 °C under an inert gas
walls of most cylinders.2,12,35 Measuring the concentration of stream carrying Hg to another gold trap. This other trap is
Hg would therefore underestimate the true concentration of heated again to ∼500 °C, and the released gases are directed to
natural gas. Solutions have been developed to overcome this the detector. The detector can be either an AAS43 or an AFS.44
problem. The application of a silicon coating on the walls The AFS typically has a detection limit (DL) 10 times lower
inside the cylinders to make it inert to Hg adsorption. A silicon than that of the AAS with the ability to detect up to a few
coating (SilcoNert 2000, Siltek, or Sulfinert) was specifically picograms of Hg (Table 1). For a robust measurement, the Hg
designed for this purpose. Its effectiveness has been tested by trapped in the amalgamator must be above the quantitation
the manufacturer and has shown stable Hg concentrations for a limit of the device because gold amalgamators may contain
period of at least 2 months.36 Other tests showed that the small amounts of Hg even after a cleaning procedure.
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Table 2. Summary of Sample Preparation Methods Used for Total Hg Concentration Analysis
reference sample type sample processing analysis MDL sample size
By Liquid−Liquid Extraction
Schickling and gas condensates aqua regia extraction CV-AAS 0.01 ng/g NR
Broekaert53
Liang et al.45 gasoline, kerosene diesel, BrCl extraction CV-AFS 0.01 ng/g 5 mL
heating oil
Zhenquan gas condensates and brines aqua regia extraction CV-AAS 100 ng/mL NR
et al.30
Bloom10 crude oil, condensates, light BrCl extraction CV-AFS 0.17 ng/g 0.5−1.5 g
distillates, fuel oil, asphalt
Liang et al.51 crude oil and related products BrCl extraction CV-AFS 0.05−0.12 ng/g 1g
Brandão et al.54 gasoline BrCl extraction CV-AAS 0.14 μg/L (BrCl 5 mL
extraction)
Conaway et al.55 gasoline and diesel BrCl extraction CV-AFS NR NR
Uddin et al.56 crude oil and petroleum dilution in toluene, extraction with BrCl/HCl CV-AFS 0.38 ng/g 5g
products
Vicentino et al.46 oil products (diesel, biodiesel, emulsion (Triton X-100 + HNO3) CV-AAS 0.6 ng/mL 20 mL
mineral oil)

By Sample Digestion
Knauer and crude, fuel, and light oil HNO3/H2SO4 digestion, distillation CV-AAS 10 ng/g 5g
Milliman50
Kelly et al.52 crude oil and diesel fuel digestion by closed system combustion with ID-CV-ICP-MS 0.01 ng/g 0.25−0.5 g
SRMs HNO3 + isotope dilution
Liang et al.51 coke (solid) HNO3/H2SO4 digestion at 95 °C CV-AFS 0.15 ng/g 1g
Munoz et al.49 crude oil and diesel fuel microwave digestion stripping voltammetry 194 ng/g 0.1 g
stripping 104 ng/g 0.1 g
chronopotentiometry
Wilhelm et al.26 oil autoclave HNO3 digestion (300 °C, 130 bar) CV-AFS
Yun et al.57 crude oil and gasoline microwave digestion with HNO3/H2O2 CV-AFS <0.26 ng/g 0.1−0.2 g
Pontes et al.47 crude oil, oil sludge HNO3 digestion in closed pressurized system CV-AAS 1.3 ng/g 0.25 g
aqua regia digestion in coldfinger system 8.6 ng/g 0.5 g
alumina digestion in thermal decomposition 3.3 ng/g 0.0253 g
technique
Ezzeldin et al.3 gas condensates autoclave HNO3 digestion (90 °C) CV-AFS 0.01−0.08 ng/g ∼1 mL
Gajdosechova Petroleum hydrocarbon microwave digestion (90 °C) with HNO3 CV-AFS 0.3 g
et al.11 ICP-MS 0.3 g
Pereira et al.48 oily sludge microwave digestion with HNO3, HCl, and H2O2 CV-AFS 0.07 ng/g 0.1 g
HPLC-ICP-MS 0.01 ng/g

By Thermal Decomposition
Knauer and crude, fuel and light oil combustion CV-AAS 5 ng/g 20 g
Milliman50
Osborne58 C5 to C14 electrothermal vaporization (graphite furnace, ETV-ICP-MS 3 ng/g
GF)
Tao et al.59 crude oil, naphtha, and thermal decomposition AAS <1.5 ng/g
condendates
Shafawi et al.60 gas condensates combustion and amalgamation AFS 0.7−2.5 ng/mL 0.25 mL
Ceccarelli et naphthas thermal decomposition AFS 32 ng/g
al.,61 ETV (GF) AAS
Liang et al.62 crude oil combustion and amalgamation AFS 0.2 ng/g 0.04 g
Liang et al.51 crude oil and related products combustion and amalgamation AFS 0.05−0.12 ng/g 0.04 g
Bouyssiere gas condensates combustion and amalgamation AAS 0.3 ng/mL 0.1 mL
et al.63
Wilhelm et al.26 oil combustion and amalgamation AFS 0.5 ng/g
Torres et al.64 gasoline dilution by ethanol, CV generation, and transfer in AAS 0.14 ng/mL 1.5 g
an oven graphite furnace
dilution by ethanol, CV generation, 0.08 ng/mL 1.5 g
amalgamation, and transfer in an oven graphite
furnace
Pontes et al.47 crude oil, oil sludge pyrolysis AAS 3.3 ng/g <0.0253 g
Gaulier et al.5 crude oil, condensates adsorption of 20 μL in a pellet, combustion AAS 0.02 mL
Lambertsson crude oil thermal decomposition AAS 0.03 ng/g
et al.9

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Table 2. continued
reference sample type sample processing analysis MDL sample size
Other Methods
Olsen et al.65 condensates and naphthas dilution in xylene ICP-MS 0.13 ng/g 2g
Kumar and naphthas emulsion with Triton X-100 aqueous solution ICP-MS 0.12 ng/mL 2 mL
Gangadharan66
Bouyssiere gas condensate dilution in 2-propanol ICP-MS (HR) <9 ng/mL
et al.67
Brandão et al.54 gasoline microemulsion with 2-propanol + HNO3 CV-AAS 0.10 μg/L 20 mL
Bouyssiere gas condensate microflow injection ICP-MS 0.5 ng/mL 0.0025 mL
et al.63
Vorapalawut crude oil and asphaltene silica gel plate impregnation LA-ICP-MS 11 ng/g
et al.68
da Silva et al.69 bio ethanol addition of formic or acetic acid, dilution PVG-AAS 0.05−0.09 ng/g >50 mL
de Jesus et al.70 naphtha and condensates microemulsion (sample + propan-1-ol + water PVG-AAS 0.6 ng/mL 1 mL
25:24:1)
Lambertsson crude oil isotope spike, heating at 200 °C ID-HS-GC-ICP-MS 0.03 ng/g
et al.9

3.3. Direct In Situ Analysis. A few companies offer in the sample. Digestion by heating with the addition of HNO3
instruments for the determination of Hg gas in the field (Table is the most widespread (Table 2). Pontes et al.47 showed that
1). Among them, some are dedicated to natural gas. Ryzhov et thermal digestion coupled with this solution made it possible
al.16 used a system based on AAS with Zeeman correction for to obtain a very satisfactory recovery rate as well as a method
direct monitoring of Hg concentration in natural gas. The detection limit (MDL) of 1.3 ng·g−1 and 8.6 ng·g−1,
analysis is fast and can be used to monitor the evolution of Hg respectively, which were much lower than those obtained
concentration over time. This method is very convenient with digestion by a cold system and the addition of aqua regia.
because sampling and analysis are performed simultaneously. This technique is simple, fast and inexpensive.48 Munoz et al.49
Such a tool would be very effective for natural gas with high Hg showed that when using a closed-tank microwave oven, they
concentrations (a few μg·m−3), although it may also be useless did not observe any loss of Hg, including volatile Hg. Despite
if there are only a few ng·m−3 of Hg in the natural gas. Ryzhov this, several studies have shown that wet digestion by heating is
et al.16 reported DLs of approximately 10 ng·m−3. This highly vulnerable to contamination and Hg loss.11,50,51 Isotopic
instrument (LUMEX RA915M coupled to RP-91NG) can be dilution, as mentioned by Kelly et al.,52 corrects for Hg losses
easily transported and is a good alternative to other by assuming they are the same for the spike and the
quantification methods because no sampling steps are required. hydrocarbon liquid sample. This digestion therefore seems to
Other automated instruments based on amalgamation and be the most advantageous for Hg analysis, and Kelly et al. also
AAS or AFS also exist and are suitable for natural gas (Table noted that isotopic dilution allows for correction of potential
1). These automated instruments are, however, more losses (with the addition of a Hg spike) during digestion.52
expensive, require some maintenance and cannot be easily Digestion combined with isotope dilution therefore appears to
moved. Such an instrument could be recommended for sites be the most advantageous method for Hg analysis.
where variable Hg concentrations have been detected to 4.1.1.3. Thermal Decomposition. The most common
monitor any changes over time and to avoid any downstream method for sample preparation is the use of thermal
problems. decomposition of samples, followed by gold amalgamation.
Direct in situ analysis via direct AAS analysis can monitor In the first step, Hg is thermally released from the sample, and
the concentration of Hg in the gas over time, even during the the Hg compounds are decomposed so that only Hg0 remains.
equilibration time. This can provide additional information on Produced gases are transferred to a gold amalgamator by a
the adsorption process of Hg, especially in natural gases carrier gas that is then analyzed.26,60,63 Other systems use the
containing H2S.12,13 same principle without any amalgamation step. The sample is
thermally decomposed in a graphite furnace (GF), and the
4. MERCURY ANALYSIS IN HYDROCARBON LIQUIDS gases are analyzed directly in the graphite furnace coupled with
4.1. Total Hg Analysis. 4.1.1. Preparation. AAS.9,47,64 However, without the fusion stage, the DLs are
4.1.1.1. Liquid−Liquid Extraction. Mercury can be extracted usually relatively high. In fact, Pontes et al.47 wanted to
from liquid hydrocarbons by liquid−liquid extraction. The compare their method, which did not have an amalgamation
oxidant solution of BrCl seems to be the most used (Table 2). stage, with that of Liang et al.62 who did have an amalgamation
This technique is simple and rapid because the oxidation and stage. Pontes et al.,47 obtained a DL of 3.3 ng·g−1 with GF-
recovery of mercury in the BrCl solution is carried out at the AAS, which was higher than the MDL of 0.2 ng·g−1 reported
same time.45 BrCl solution converts the mercury present in the by Liang et al.,62 when using an amalgamation step (Table 2).
samples to its oxidized ionic form (Hg2+), so a reducer must be Comparisons between thermal decomposition and liquid−
used, prior to any analysis, to convert the recovered Hg2+ in liquid extraction or sample digestion procedures generally
Hg0. It has also been shown that the use of an HCl solution show a better recovery with thermal decomposition than
does not allow an optimal recovery of Hg from a NaBH4 without this step. Thermal decomposition is therefore
solution45 and more recently from a Triton X-100 + HNO3 preferred for Hg analysis.26,51
solution.46 4.1.1.4. Other Methods. Several methods of sample
4.1.1.2. Sample Digestion. Unlike the liquid−liquid preparation for the determination of total Hg may also be
extraction mentioned above, here, the organic matrix remains used (Table 2). Sample injection into a carrier solvent was
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Figure 2. Summary of the different methodologies for total Hg analysis in liquid petroleum, from sample treatment (left boxes) to processing
(middle boxes) and detection (right boxes).

shown to be a practical method that does not require sample SnCl2. In addition, Gajdosechova et al.11 reported an
treatment and fast analysis.63,65,67 This technique makes it underestimation of the Hg concentration when using SnCl2
possible to use very small quantities of samples, with a DL because of the consumption of SnCl2 for reducing sulfates to
comparable to those of thermal desorption-AAS or AFS.9,63 sulfides. In addition, Da Silva et al.69 noted that the reducing
Several authors investigated the possibility of analyzing agents are often unstable and costly. We concluded that sample
microemulsions by CV-AAS or photochemical vapor gen- preparations avoiding the use of reducing agents should be
eration (PVG)-AAS. This technique uses a very small sample favored for Hg analysis. Cold vapor generation can also be
and reagent volume,70 and the DLs are comparable to those achieved through the photochemical reduction of Hg. The DLs
obtained by extraction with a solution of BrCl: 0.10 ng·g−1 for reported for PVG-AAS are relatively high (1.1 ng·g−1).69,70
a microemulsion and 0.14 ng·g−1 for extraction.54 Gajdosechova et al.11 found that CV-AFS should be used
Lambertsson et al.9 recently developed a new method for with alkaline samples, i.e., the use of a 2% SnCl2 solution
determining Hg in liquid oil samples: ID-HS-GC-ICP-MS, prepared in NaOH (5 M), to avoid underestimating the
which is based on the concentration of Hg in the head space amount of Hg.
(HS) of a sample vial combined with isotope dilution (ID), Analysis of hydrocarbon samples by ICP-MS after dilution
GC separation, and ICP-MS detection. An isotopic compound or emulsification was also found to yield an acceptable MDL
(198HgCl2) is added to the sample to accurately trace the Hg (0.2 ng·mL−1).
concentration in the samples. The procedure includes one ICP-MS analysis has advantages over the AAS or AFS
heating step that allows for the complete conversion of all Hg analyses because the samples can be analyzed directly without
species to Hg0. Hg0 then balances between the gas and the pretreatment, and the analysis is faster than the other methods
dissolved phase. An aliquot of the headspace gas is injected mentioned above.63,65 However, the DL of ICP-MS (0.5 ng·
into a gas chromatography (GC)-ICP-MS system. Both 202Hg mL−1) is slightly higher than those of the other analytical
and 198Hg are monitored to allow for isotope addition procedures, which could interfere with the analysis of very low
correction. This method provides a DL similar to that of Hg concentrations.63
thermal desorption coupled to AAS (0.3 ng·g−1). Laser ablation coupled to ICP-MS enables a relatively fast
Dilution of the condensate may sometimes be necessary to and accurate analysis of petroleum samples. This procedure
reduce its viscosity or to provide a reasonably stable eliminates the typical drawbacks of ICP-MS analysis of organic
background for mercury signals. Benzene, toluene, and xylene solutions, such as matrix signal suppression, carbon deposition,
are universal solvents, but some condensates may be dissolved and the formation of interfering ions in plasma.68 However, the
in hexane, isooctane, or isopropanol, which may be useful in DL of this method is too high (11 ng·g−1) for application to
some cases.56,71 liquid hydrocarbons.
4.1.2. Analysis. The detection limit of a method depends on 4.2. Hg Speciation. Speciation analysis of Hg in liquid
the detector used, the dilution factors, the sample matrix after hydrocarbons can be performed by different methods. At
processing and the sample size (Table 2). Analyses by AAS, present, there is no method capable of simultaneously
AFS, and ICP-MS are the most widely used and produce very detecting all species contained in liquid hydrocarbon samples
low MDLs of approximately 0.1 ng·g−1 (Table 1). Several because of the different properties of Hg species.1
studies have shown that these three analytical systems provide Different methods have been tested for the determination of
similar MDL, accuracy and repeatability values.11,52,54,61,63 Hg speciation in liquid hydrocarbons. We can categorize Hg
For liquid−liquid extraction and digestion methods coupled separation methods into two classes: chromatographic
with CV-AAS and CV-AFS (Figure 2), a reducer must be techniques and sequential extractions. Since a review published
added to the solution prior to analysis to convert Hg2+ to in 2000,71 few studies have attempted new methodologies for
Hg0.42 A SnCl2 solution can be used,10,53 but Brandao et al.54 the speciation of Hg in liquid hydrocarbons. Table 3 shows the
demonstrated that NaBH4 provides better repeatability and commercial analytical devices dedicated to the analysis of Hg
sensitivity and a lower DL than those achieved when using speciation without the use of liquid samples.
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Table 3. Commercial Instruments Dedicated to Hg Analysis in Liquid and Solid Samples and to Hg Speciation in Liquid
Samples
determined weight
brand name Hg species detector analysis samples DL (kg)
Leco AMA-254 total Hg AAS direct analysis (thermal decomposi- solid/liquids 46
tion), lab

Milestone DMA-80 total Hg AAS direct analysis (thermal decomposi- solid/liquids 0.001 ng 56
DMA-1 total Hg AAS tion + amalgamation), lab solid/liquids 0.001 ng
FMA total Hg AFS and lab, liquids 0.01 ng/g
AAS

Nippon Instru- MA-3000 total Hg AAS direct analysis (thermal decomposi- lab 55
ment Corp. tion), lab
PE-1000 total Hg AFS direct analysis (petro-pyrolysis), lab specific liquid 40
hydrocarbons

Perkin Elmer SMS 100 total Hg AAS direct analysis (thermal decomposi- solid/liquids 0.005 ng 20
tion + amalgamation), lab

Brooks Rand Model III + MERX Total Hg total Hg AFS direct analysis (thermal decomposi- solid/liquids <0.03 ng/L
Purge and Trap Module tion + amalgamation), lab

PSA 10.025 Millenium Merlin total Hg AFS or AAS direct analysis (thermal decomposi- solid/liquids
tion + amalgamation), lab
LUMEX RA-915M + PYRO-915 total Hg AAS direct analysis (pyrolyze), lab liquid 0.01 ng/g

Buck Scientific 410 cold vapor mercury analyzer total Hg AAS lab solid/liquids 0.0005 ng/g 20

HIRANUMA HG-400 total Hg AAS lab solid/liquids 0.01−10 ng/g 4

Mercury Instru- LabAnalyzer LA 254 total Hg AAS lab only liquids 5 pg 10

ments AULA-254 Gold total Hg AAS direct analysis, lab only liquids 5 ng/L 18.6

Teledyne Hydra IIAA total Hg AAS direct analysis, lab liquids 0.001 g
Hydra IIC total Hg AAS direct analysis (thermal decomposi- solid and semi- 0.05 ng/L
tion + amalgamation), lab solid
M-8000 total Hg AFS lab liquids 0.5 ng/L
M-7600 total Hg AAS lab sub-pg

TEKRAN 2600 total Hg AFS lab

PSA 10.725 GC speciation GC-AFS lab liquids

10.820 speciation HPLC-AFS direct analysis (online UV diges- liquids
tion), lab

Brooks Rand MERX-M speciation GC-AFS direct analysis (Online ethylation), liquids 0.002 ng/L
lab

TEKRAN 2700 speciation GC-AFS lab liquids 0.002 ng/L

4.2.1. Sample Preparation: Operationally Defined Proce- chloride solution in water with a volume ratio of 1:5 for this
dures. The UOP938 protocol proposes a methodology for the liquid−liquid extraction.
speciation of Hg in liquid hydrocarbons (UOP Method 938- The MDL for each species depends, in part, on the
10, n.d, n.d.). This technique uses three extraction steps, the sensitivity of the detector. The volatile Hg and particulate Hg
first of which consists of sample filtration to determine the concentrations also depend on the size of the sample due to
particulate Hg fraction (Figure 3). The UOP938 method the preconcentration step (if the filters are analyzed after
thermal decomposition and amalgamation).
recommends performing pressure filtration with 0.22 μm
This method has both advantages and disadvantages: it
polyvinylidene fluoride filters. The second step consists of
allows for onsite sample processing for the first steps of the
purging and trapping the volatile Hg species (Hg0 and procedure, which is an important advantage because it prevents
eventually DMHg) contained in the sample. After this second Hg losses and species interconversion during storage.10 The
step, only soluble Hg (oxidized species) remains in the sample. purging step allows for the collection of volatile Hg0. In the
The third step consists of a liquid−liquid extraction step to second step volatile Hg0 can be removed from the sample to
separate the ionic and organic Hg species before their analysis. avoid its reaction with Hg(II) and, above all, the precipitation
The UOP938 method recommends using a 0.01% sodium of insoluble Hg(I) resulting from this reaction.21 However, it
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Analysis of the samples before and after derivatization

theoretically allows for complete speciation of Hg in a
condensate sample.
Despite the robustness and sensitivity of this technique,
some Hg compounds present in the samples may interfere with
the analysis. Gajdosechova et al.11 showed that the GC input
temperature can affect the Hg0 signal during analysis if
particulate HgS is present in the sample. They hypothesized
that particulate Hg could release Hg0 when it underwent
thermal decomposition when samples were introduced into the
GC instrument. Gajdosechova et al.11 therefore recommends
that these HgS particles be removed from the sample prior to
speciation analysis of the sample.
Although no speciation method can allow for the direct and
Figure 3. Diagram of mercury speciation analysis in liquid
hydrocarbon by UOP Method 938-10 (adapted with permission
complete speciation of Hg, GC coupled to ICP-MS is capable
from ref 5). of quantifying all Hg species (except for particulate Hg).
Presently, there is no other method capable of such
achievement. GC has been coupled to different detectors,
but to date, the most robust and the most sensitive is ICP-
has been found that when one species dominates a MS.67,74 The use of MIP-AES was found to be impractical
hydrocarbon sample, it can affect the results for other species.1 because of background interferences due to organic com-
In addition, this method does not allow for the identification of pounds; its use is, however, possible if the eluted Hg is first
organic species of Hg (MMHg, EtHg, etc.), and MMHg is preconcentrated in a gold amalgamator.75
generally the dominant species.1 Recently, Gaulier et al.5 4.2.3. HPLC Separation. HPLC is less commonly used than
optimized the three steps of the UOP938 method to make it GC for the separation of Hg species. Bouyssiere et al.71
more robust and accurate. They showed that the technique considered HPLC to be less effective than GC for the
could be more robust by measuring the Hg recovered from the separation of Hg species. This method does not require a
filter instead of quantifying the difference between the derivatization step, which allows for a shorter analysis time
unfiltered and filtered solutions, as suggested in the UOP938 than that of GC.59 Schickling and Broekaert53 coupled HPLC
method. Similarly, recovering the Hg0 purged using a gold separation with CV-AAS detection. Detection limits of
amalgamator with subsequent analysis provides a better approximately 10 ng·mL−1 were achieved for Hg species,
estimate of its concentration. Sodium chloride used for which were well above those found using the GC-ICP-MS
successive liquid−liquid extraction can damage some analyzers, methods (<1 ng·mL−1). In addition, transient signals and
and an alternative L-cysteine solution was reported to give baseline instability were observed.
similar extraction yields (95%) with fewer analytical issues than More recent studies have used HPLC for the separation of
those occurring with the use of sodium chloride.5 Hg species.57,76 Both of these studies must have used a
Recently, Gajdosechova et al.72 developed a method based digestion or extraction step before HPLC-ICP-MS detection.
on headspace gas sampling. Hg compounds present in the Yun et al.57 tested different extraction/digestion procedures
organic matrix were first extracted by chelation with dithizone and found the best recovery rates by microwave-assisted
(diphenylthiocarbazone), and then sodium tetrapropyl borate extraction with the addition of tetramethylammonium
was added to volatilize the mercury species. These species were hydroxide (TMAH). Despite this, the recovery rates were
then collected and preconcentrated on ITEX tubes (online only 87% and 71% for MeHg and EtHg, respectively. The
preconcentration using in-tube extraction). This sample addition of an extraction or digestion step before determining
preparation resulted in a very low DL for MeHg (0.06 ng· the speciation of Hg is impractical since the initial advantage of
g−1). Nevertheless, these preparation techniques are specific HPLC-based systems is to avoid treatment steps and promote
and generally allow for only certain Hg species to be extracted, the precision of the method.53 HPLC-ICP-MS analysis might
contrary to the UOP938 protocol. be combined with an isotope addition procedure to take into
4.2.2. Gas Chromatography. GC is a widely used technique account Hg species conversions and losses.76
for the analysis of Hg speciation in petroleum.3,11,59,67,72−75 4.2.4. Gel Permeation Chromatography. Size-exclusion
Coupled with suitable detection instruments such as AFS, ICP- chromatography (SEC) and gel permeation chromatography
MS, or MIP-AES, this technique is capable of separating all (GPC) are not yet widely used for the separation of Hg
volatile Hg species. species. Until now, only one study has investigated the
Only Hg0 and dialkyl-Hg species are volatile,10,18 while potential of this chromatographic technique for Hg speciation
monoalkyl-Hg and ionic Hg remain in solution. 3 A in liquid hydrocarbons.5 This method allows for the separation
derivatization step is necessary to convert Hg(II) to dibutyl- of species by hydrodynamic volume.
Hg and methyl-Hg to methylbutyl-Hg. A Grignard reagent, This method may have significant advantages over other Hg
generally butylmagnesium chloride (BuMgCl), must be used speciation procedures,71 such as the GC-ICP-MS technique, as
to carry out this derivatization step.11,74 it requires no chemicals and does not affect the association of
Hg with functional groups until they reach the plasma.
2BuMgCl + Hg 2 + → Bu 2Hg + (4) Separation by GPC is carried out according to the hydro-
dynamic volume, and the large molecules elute earlier than
small molecules, which can take a longer path in the porous
BuMgCl + CH3Hg + → BuCH3Hg+ (5) GPC column.
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This technique allows for the co-monitoring of various during short well tests. As explained above, due to possible
elements, particularly sulfur, which can provide crucial chemical reactions and adsorption−desorption equilibrium,
information on Hg-binding molecules. Indeed, some sulfur mercury can be retained on all kind of surface, including on the
compounds interact with mercury in liquid hydrocarbon surface of the well tubing and of the testing equipment. For
samples.9,24 The use of this technique, coupled with an ICP- this reason, mercury will take some time before its arrival at the
MS detector, makes it possible to simultaneously monitor separator gas outlet. The lower the mercury content of the gas,
various elements, including Hg and sulfur, and potentially to the higher the amount of the gas to be produced before being
identify the important blinding ligands for oxidized Hg. able to measure the actual mercury content.
However, this method was not evaluated quantitatively. Sampling or measuring mercury downhole during a well test
Although very good trends were observed for Hg0 species, no can be a solution to significantly increase the sensitivity and
linear relationship was found between the Hg concentration reduce the duration of the test. However, unlike surface
and the detection signal for other Hg species, presumably sampling, corrective action becomes nearly impossible in this
because of interactions of oxidized Hg with the column. case. Thus, traceability of the operation and consistency check
Further method developments might make GPC-ICP-MS a will be the key challenge in this case.
quantitative and powerful speciation technique for Hg analysis
in the future. 6. CONCLUSION
We compiled different sampling constraints and analytical
5. CHALLENGES AND PERSPECTIVES methods for the determination of Hg concentration and
Total Hg analysis itself in both natural gas and liquid speciation in petroleum hydrocarbons. Generally, almost all
petroleum products can be efficiently evaluated using the methods developed for the quantification of Hg have
above-described methods. However, the reliability of Hg sufficiently low detection limits. Hg speciation methods give
measurements is debatable, with the under-evaluated inter- variable information depending on the technique used. The
species conversion and losses by volatilization during sampling presence of different Hg species in petroleum might require
and sample storage prior to analysis. More investigations on further investigations using novel methodologies. Generally,
the evolution of Hg species concentrations after sampling are abundant oxidized Hg is only quantified as the sum of Hg
required to assess the reliability of laboratory measurements. species in the +2 oxidation state. Recent developments, such as
The development of robust storage procedure stabilizing Hg SEC separation or X-ray absorption fine structure spectrosco-
species is one of the potential next important steps. py, might better identify the different salts and/or complexes
Alternatively, onsite procedures might be better representative within a single oxidation state. Such information might be
of Hg concentration and speciation in streams. In particular, critical for a better understanding of Hg partitioning in the
the volatile Hg species were shown to be critical. different hydrocarbon phases.
Many studies reported a dominance of HgII species in Overall, Hg concentration and speciation measurements are
petroleum products, yet identifying Hg as HgII is not precise no longer a challenge, although some future developments
enough to anticipate its properties and behavior during might provide more detailed information on Hg behavior from
petroleum processing and in MRUs. A better characterization extraction to processing. The main concern in Hg analysis
of HgII (Hg salts, Hg thiolates, etc.) might lead to a better remains in sampling and storage procedures. Because sampling
understanding of Hg partitioning between the different induces a modification of the conditions (pressure, temper-
petroleum phases and help the development of more efficient ature), the partitioning coefficient between different Hg species
treatment units. We admit that combining such precise might be affected and might ultimately cause volatilization,
characterization to the onsite analysis we previously recom- oxidation, methylation or precipitation of Hg; thus, rapid
mended might be challenging, which further reinforces the onsite analysis is recommended.
need for more investigations relative to Hg species conversion
following sampling.
Our effort in reviewing all developed methodologies
■ AUTHOR INFORMATION
Corresponding Author
revealed a clear gap. The assessment of techniques, in Brice Bouyssiere − E2S UPPA, CNRS, IPREM, Institut des
particular for Hg speciation, is often based on Hg species Sciences Analytiques et de Physico-chimie pour l’Environnement
spiking and detection. Although this can be considered as a et les Materiaux, UMR5254, Hélioparc, Universite de Pau et des
good proof of concept, the development of an oil reference Pays de l’Adour, 64053 Pau, France; Joint Laboratory C2MC:
material with known Hg speciation seems to be necessary to Complex Matrices Molecular Characterization, Total Research
evaluate speciation methods. Presently, we could only compare & Technology, F-76700 Harfleur, France; orcid.org/0000-
the methods based on the number of Hg species detected and 0001-5878-6067; Phone: +33 (0) 559 407 752;
DLs, which is clearly insufficient for choosing the appropriate Email: [email protected]
technique. In addition, the different laboratories involved in
developing Hg (and especially speciation) research in the field Authors
also have the responsibility to provide additional evidence for Maxime Enrico − E2S UPPA, CNRS, IPREM, Institut des
the reliability of their measurements. For this purpose, we Sciences Analytiques et de Physico-chimie pour l’Environnement
suggest the implementation of laboratory inter-comparison et les Materiaux, UMR5254, Hélioparc, Universite de Pau et des
campaigns, consisting in the parallel analysis of several samples. Pays de l’Adour, 64053 Pau, France; Joint Laboratory C2MC:
Such campaigns conducted with seawater samples during the Complex Matrices Molecular Characterization, Total Research
past decade notoriously harmonized the results from different & Technology, F-76700 Harfleur, France
laboratories.77,78 Aurore Mere − E2S UPPA, CNRS, IPREM, Institut des Sciences
Another difficulty for upstream sector is to obtain reliable Analytiques et de Physico-chimie pour l’Environnement et les
estimation of the mercury content of the gas from new fields Materiaux, UMR5254, Hélioparc, Universite de Pau et des Pays
13317 https://dx.doi.org/10.1021/acs.energyfuels.0c02730
Energy Fuels 2020, 34, 13307−13320
Energy & Fuels pubs.acs.org/EF Review

de l’Adour, 64053 Pau, France; Joint Laboratory C2MC: and ottaining a Ph.D. dealing with speciation of mercury and arsenic
Complex Matrices Molecular Characterization, Total Research in gas condensates at the University of Pau, he did a postdoctoral stay
& Technology, F-76700 Harfleur, France; TOTAL E&P, at the GKSS Geesthacht, Germany. His principal research interest is
CSTJF, 64018 Pau, France metals speciation in complex matrices.
Honggang Zhou − TOTAL E&P, CSTJF, 64018 Pau, France
Matthieu Loriau − TOTAL E&P, CSTJF, 64018 Pau, France
Emmanuel Tessier − E2S UPPA, CNRS, IPREM, Institut des
Sciences Analytiques et de Physico-chimie pour l’Environnement
■ REFERENCES
(1) Wilhelm, S. M.; Bloom, N. Mercury in Petroleum. Fuel Process.
et les Materiaux, UMR5254, Hélioparc, Universite de Pau et des Technol. 2000, 63, 1−27.
Pays de l’Adour, 64053 Pau, France; Joint Laboratory C2MC: (2) Leeper, J. Mercury-LNG’s Problem. Hydrocarbon Process. 1980,
Complex Matrices Molecular Characterization, Total Research 59, 237−240.
& Technology, F-76700 Harfleur, France (3) Ezzeldin, M. F.; Gajdosechova, Z.; Masod, M. B.; Zaki, T.;
Feldmann, J.; Krupp, E. M. Mercury Speciation and Distribution in an
Complete contact information is available at: Egyptian Natural Gas Processing Plant. Energy Fuels 2016, 30,
https://pubs.acs.org/10.1021/acs.energyfuels.0c02730 10236−10243.
(4) Rumayor, M.; Gallego, J. R.; Rodríguez-Valdés, E.; Díaz-
Author Contributions Somoano, M. An Assessment of the Environmental Fate of Mercury
∥ Species in Highly Polluted Brownfields by Means of Thermal
M.E. and A.M. contributed equally to this work.
Desorption. J. Hazard. Mater. 2017, 325, 1−7.
Notes (5) Gaulier, F.; Gibert, A.; Walls, D.; Langford, M.; Baker, S.;
The authors declare no competing financial interest. Baudot, A.; Porcheron, F.; Lienemann, C. P. Mercury Speciation in
Biographies Liquid Petroleum Products: Comparison between on-Site Approach
and Lab Measurement Using Size Exclusion Chromatography with
Maxime Enrico ([email protected]) is a young researcher
High Resolution Inductively Coupled Plasma Mass Spectrometric
focusing on mercury biogeochemistry. He obtained a Ph.D. studying
Detection (SEC-ICP-HR MS). Fuel Process. Technol. 2015, 131, 254−
environmental mercury cycling at the University of Toulouse before 261.
working on petroleum problematics at the University of Pau. He is (6) INRS. Fiche D’information à L’intention Des Médecins: Fiche No.
now a postdoctoral researcher at Harvard University, focusing his 1: Cannabis; Institut National de Recherche et de Sécurité: France,
research on temporal trends in environmental mercury levels and the 2014.
use of mercury stable isotope ratios as source and process tracers in (7) Lide, D. R. Handbook of Chemistry and Physics, 79th ed.; CRC
the environment. Press: Boca Raton, FL, 1999.
Aurore Mere ([email protected]) graduated in analytical (8) Strem. Chemicals for Research Metals, Inorganics and Organo-
metallic, 2001.
chemistry from the University of Pau and is presently a Ph.D.
(9) Lambertsson, L.; Lord, C. J.; Frech, W.; Björn, E. Rapid
student in partnership with Total. She is working on mercury and Dissolution of Cinnabar in Crude Oils at Reservoir Temperatures
arsenic in the petrochemical and petroleum industry. Facilitated by Reduced Sulfur Ligands. ACS Earth Space Chem. 2018,
Honggang Zhou ([email protected]) graduated from the 2, 1022−1028.
University Paris XI with a master’s degree in physics. He completed a (10) Bloom, N. S. Analysis and Stability of Mercury Speciation in
Ph.D. in physical chemistry at the University of Pau in 1988, to Petroleum Hydrocarbons. Fresenius' J. Anal. Chem. 2000, 366, 438−
become a Research Engineer at the IFP (French Petroleum Institute). 443.
He joined Total in 1992, where he specializes in fluids phase behavior (11) Gajdosechova, Z.; Boskamp, M. S.; Lopez-Linares, F.;
modeling, trace components sampling/analysis, and organic and Feldmann, J.; Krupp, E. M. Hg Speciation in Petroleum Hydro-
carbons with Emphasis on the Reactivity of Hg Particles. Energy Fuels
inorganic compounds precipitation risk evaluation and modeling.
2016, 30, 130−137.
Matthieu Loriau ([email protected]) graduated from the (12) Harfoushian, J. H. Quantification of Low Levels of Mercury in
engineering school ENSICAEN and completed a Ph.D. in analytical Gas Reservoirs Using Advanced Sampling and Analysis Techniques.
sciences at PSL University (ex. UPMC, Paris VI University) for the Proceedings of SPE Annual Technical Conference and Exhibition; Society
Arkema Group on Polymers in 2009. He joined Total in 2009 as a of Petroleum Engineers, 1995.
Research Engineer, where he has worked for 9 years on additives for (13) Larsson, T.; Frech, W.; Björn, E.; Dybdahl, B. Studies of
enhanced oil recovery applications and is currently head of an Transport and Collection Characteristics of Gaseous Mercury in
analytical service for fluid thermodynamics and organic geochemistry. Natural Gases Using Amalgamation and Isotope Dilution Analysis.
Analyst 2007, 132, 579−586.
Emmanuel Tessier ([email protected]) obtained a Ph.D. (14) Behra, P.; Bonnissel-Gissinger, P.; Alnot, M.; Revel, R.;
in water chemistry and microbiology. He has been a research engineer Ehrhardt, J. J. XPS and XAS Study of the Sorption of Hg(II) onto
at UPPA since 2013, in charge of the “Speciation and Mercury” Pyrite. Langmuir 2001, 17, 3970−3979.
instrumental platform and facility within the Environmental (15) Ehrhardt, J. J.; Behra, P.; Bonnissel-Gissinger, P.; Alnot, M. XPS
Chemistry and Microbiology cluster of the IPREM. His research Study of the Sorption of Hg(II) onto Pyrite Fes2. Surf. Interface Anal.
activity focuses on trace metals and organometals biogeochemistry, 2000, 30, 269−272.
reactivity, and transfer in aquatic systems, with analytical and (16) Ryzhov, V. V.; Mashyanov, N. R.; Ozerova, N. A.; Pogarev, S.
experimental skills in innovative methodologies based on isotopic E. Regular Variations of the Mercury Concentration in Natural Gas.
tools implementation. Sci. Total Environ. 2003, 304, 145−152.
(17) Klusman, R. W.; Jaacks, J. A. Environmental Influences Upon
Brice Bouyssiere ([email protected]) is Professor of Mercury, Radon and Helium Concentrations in Soil Gases at a Site
Analytical Chemistry at the University of Pau and one of the near Denver, Colorado. J. Geochem. Explor. 1987, 27, 259−280.
researchers responsible for the International Lab on Complex (18) Cameron, C. J.; Didilion, B.; Benayoun, D.; Dorbon, M.
Matrices Molecular Characterization (iC2MC Lab). After a Mercury: A Trace Contaminant in Natural Gas and Natural Gas
completing a chemical and process engineering school (ENSGTI) Liquids. Proceedings Eurogas 96, June 1996.

13318 https://dx.doi.org/10.1021/acs.energyfuels.0c02730
Energy Fuels 2020, 34, 13307−13320
Energy & Fuels pubs.acs.org/EF Review

(19) Wilhelm, S. M.; Liang, L.; Kirchgessner, D. Identification and (39) Pandey, S. K.; Kim, K. H. Experimental Bias Involved in the
Properties of Mercury Species in Crude Oil. Energy Fuels 2006, 20, Collection of Gaseous Elemental Mercury by the Gold Amalgam
180−186. Method. Environ. Eng. Sci. 2008, 25, 255−264.
(20) Wilhelm, S. M.; Kirchgessner, D. A.; Liang, L.; Kariher, P. H. (40) Beauchamp, J.; Herbig, J.; Gutmann, R.; Hansel, A. On the Use
Sampling and Analysis of Mercury in Crude Oil. J. ASTM Int. 2005, 2, of Tedlar® Bags for Breath-Gas Sampling and Analysis. J. Breath Res.
12985. 2008, 2, 046001.
(21) Snell, J.; Qian, J.; Johansson, M.; Smit, K. Stability and (41) Cachia, M.; Bouyssière, B.; Carrier, H.; Garraud, H.; Caumette,
Reactions of Mercury Species in Organic Solution. Analyst 1998, 123, G.; Le Hécho, I. Development of a High-Pressure Bubbling Sampler
905−909. for Trace Element Quantification in Natural Gas. Energy Fuels 2017,
(22) ASTM D7482-17. Standard Practice for Sampling, Storage, and 31, 4294−4300.
Handling of Hydrocarbons for Mercury Analysis; ASTM International: (42) Sánchez-Rodas, D.; Corns, W. T.; Chen, B.; Stockwell, P. B.
West Conshohocken, PA, 2017. Atomic Fluorescence Spectrometry: A Suitable Detection Technique
(23) Bloom, N. S.; Horvat, M.; Watras, C. J. Results of the in Speciation Studies for Arsenic, Selenium, Antimony and Mercury. J.
International Aqueous Mercury Speciation Intercomparison Exercise. Anal. At. Spectrom. 2010, 25, 933−946.
In Mercury as a Global Pollutant: Proceedings of the Third International (43) ASTM D5954-98. Standard Test Method for Mercury Sampling
Conference Held in Whistler, British Columbia; Porcella, D. B., and Measurement in Natural Gas by Atomic Absorption Spectroscopy;
Huckabee, J. W., Wheatley, B., Eds.; Springer Netherlands: Dordrecht, ASTM International: West Conshohocken, PA, 2014.
1995; pp 1257−1268. (44) ASTM D6350-14. Standard Test Method for Mercury Sampling
(24) Avellan, A.; Stegemeier, J. P.; Gai, K.; Dale, J.; Hsu-Kim, H.; and Analysis in Natural Gas by Atomic Fluorescence Spectroscopy;
Levard, C.; O’Rear, D.; Hoelen, T. P.; Lowry, G. V. Speciation of ASTM International: West Conshohocken, PA, 2014.
Mercury in Selected Areas of the Petroleum Value Chain. Environ. Sci. (45) Liang, L.; Horvat, M.; Cernichiari, E.; Gelein, B.; Balogh, S.
Technol. 2018, 52, 1655−1664. Simple Solvent Extraction Technique for Elimination of Matrix
(25) UOP Method 938-10. Total Mercury and Mercury Species in Interferences in the Determination of Methylmercury in Environ-
Liquids Hydrocarbon, Mercury (Element), Solubility; ASTM Interna- mental and Biological Samples by Ethylation-Gas Chromatography-
tional: West Conshohocken, PA, 2018. Cold Vapor Atomic Fluorescence Spectrometry. Talanta 1996, 43,
(26) Wilhelm, S. M.; Liang, L.; Cussen, D.; Kirchgessner, D. A. 1883−1888.
Mercury in Crude Oil Processed in the United States (2004). Environ. (46) Vicentino, P. O.; Brum, D. M.; Cassella, R. J. Development of a
Sci. Technol. 2007, 41, 4509−4514. Method for Total Hg Determination in Oil Samples by Cold Vapor
(27) Norme NF EN 13211. Qualité De L’air - É missions De Sources Atomic Absorption Spectrometry after its Extraction Induced by
Fixes - Methode Manuelle De Determination De La Concentration En Emulsion Breaking. Talanta 2015, 132, 733−738.
(47) Pontes, F. V. M.; Carneiro, M. C.; Vaitsman, D. S.; Monteiro,
Mercure Total (Air Quality - Fixed Source Emissions - Manual Method
M. I. C.; Neto, A. A.; Tristão, M. L. B.; Guerrante, M. F. Comparative
for Total Mercury Determination); Association Francaise De Normal-
Study of Sample Decomposition Methods for the Determination of
isation (AFNOR): Paris, France, 2001.
Total Hg in Crude Oil and Related Products. Fuel Process. Technol.
(28) Brombach, C. C.; Pichler, T. Determination of Ultra-Low
2013, 106, 122−126.
Volatile Mercury Concentrations in Sulfur-Rich Gases and Liquids.
(48) Pereira, L.; Maranhão, T. A.; Frescura, V. L. A.; Borges, D. L. G.
Talanta 2019, 199, 277−284. Multivariate Assessment of Extraction Conditions for the Fractiona-
(29) ISO 6978-1:2003, Natural GasDetermination of Mercury. Part
tion Analysis of Mercury in Oily Sludge Samples Using Cold Vapor
1: Sampling of Mercury by Chemisorption on Iodine, 2019. https:// Atomic Fluorescence Spectrometry. J. Anal. At. Spectrom. 2019, 34,
www.iso.org/standard/38600.html. 1932−1941.
(30) Zhenquan, T.; Quiju, W.; Bin, H. Determination of Mercury (49) Munoz, R. A. A.; Correia, P. R. M.; Nascimento, A. N.; Silva, C.
Content in Natural Gas by Chemisorption on Iodine-Impregnated S.; Oliveira, P. V.; Angnes, L. Electroanalysis of Crude Oil and
Silica Gel. Chem. Eng. Oil Gas 2009, 2009-03. (http://en.cnki.com. Petroleum-Based Fuel for Trace Metals: Evaluation of Different
cn/Article_en/CJFDTotal-STQG200903022.htm) Microwave-Assisted Sample Decompositions and Stripping Techni-
(31) ISO 6978-2:2003, Natural Gas−Determination of Mercury. Part ques. Energy Fuels 2007, 21, 295−302.
2: Sampling of Mercury by Amalgmation on Gold/Platinum Alloy, 2019. (50) Knauer, H. E.; Milliman, G. E. Analysis of Petroleum for Trace
https://www.iso.org/standard/38601.html Metals. Determination of Mercury in Petroleum and Petroleum
(32) Dumarey, R.; Dams, R.; Hoste, J. Comparison of the Collection Products. Anal. Chem. 1975, 47, 1263−1268.
and Desorption Efficiency of Activated Charcoal, Silver, and Gold for (51) Liang, L.; Horvat, M.; Fajon, V.; Prosenc, N.; Li, H.; Pang, P.
the Determination of Vapor-Phase Atmospheric Mercury. Anal. Chem. Comparison of Improved Combustion/Trap Technique to Wet
1985, 57, 2638−2643. Extraction Methods for Determination of Mercury in Crude Oil and
(33) Frech, W.; Baxter, D. C.; Bakke, B.; Snell, J.; Thomassen, Y. Related Products by Atomic Fluorescence. Energy Fuels 2003, 17,
Highlight. Determination and Speciation of Mercury in Natural Gases 1175−1179.
and Gas Condensates. Anal. Commun. 1996, 33, 7H−9H. (52) Kelly, W. R.; Long, S. E.; Mann, J. L. Determination of Mercury
(34) Frech, W.; Baxter, D. C.; Dyvik, G.; Dybdahl, B. On the in SRM Crude Oils and Refined Products by Isotope Dilution Cold
Determination of Total Mercury in Natural Gases Using the Vapor ICP-MS Using Closed-System Combustion. Anal. Bioanal.
Amalgamation Technique and Cold Vapour Atomic Absorption Chem. 2003, 376, 753−758.
Spectrometry. J. Anal. At. Spectrom. 1995, 10, 769−775. (53) Schickling, C.; Broekaert, J. A. C. Determination of Mercury
(35) Enrico, M.; Mere, A.; Zhou, H.; Carrier, H.; Tessier, E.; Species in Gas Condensates by on-Line Coupled High-Performance
Bouyssiere, B. Experimental Tests of Natural Gas Samplers Prior to Liquid Chromatography and Cold-Vapor Atomic Absorption
Mercury Concentration Analysis. Energy Fuels 2020, 34, 5205−5212. Spectrometry. Appl. Organomet. Chem. 1995, 9, 29−36.
(36) SilcoTek. Prevent Mercury Loss During Transport and Storage (54) Brandão, G. P.; de Campos, R. C.; Luna, A. S. Determination of
with Silconert; SilcoTek Corp.: Bellefonte, PA, 2019. Mercury in Gasoline by Cold Vapor Atomic Absorption Spectrometry
(37) Hirner, A. V.; Feldmann, J.; Krupp, E.; Grümping, R.; Goguel, with Direct Reduction in Microemulsion Media. Spectrochim. Acta,
R.; Cullen, W. R. Metal(Loid)Organic Compounds in Geothermal Part B 2005, 60, 625−631.
Gases and Waters. Org. Geochem. 1998, 29, 1765−1778. (55) Conaway, C. H.; Mason, R. P.; Steding, D. J.; Russell Flegal, A.
(38) Maillefer, S.; Lehr, C. R.; Cullen, W. R. The Analysis of Volatile Estimate of mercury emission from gasoline and diesel fuel
Trace Compounds in Landfill Gases, Compost Heaps and Forest Air. consumption, San Francisco Bay area, California. Atmos. Environ.
Appl. Organomet. Chem. 2003, 17, 154−160. 2005, 39, 101−105.

13319 https://dx.doi.org/10.1021/acs.energyfuels.0c02730
Energy Fuels 2020, 34, 13307−13320
Energy & Fuels pubs.acs.org/EF Review

(56) Uddin, R.; Al-Fahad, M. A.; Al-Rashwan, A. K.; Al-Qarni, M. A. (73) Kawasaki, M.; Otsuka, M.; Yamada, J.; Kobayashi, A.
A Simple Extraction Procedure for Determination of Total Mercury in Identification of Mercury Species in Liquid Hydrocarbons. J. Jpn.
Crude Oil. Environ. Monit. Assess. 2013, 185, 3681−3685. Pet. Inst. 2016, 59, 235−240.
(57) Yun, Z.; He, B.; Wang, Z.; Wang, T.; Jiang, G. Evaluation of (74) Pontes, F. V. M.; Carneiro, M. C.; Vaitsman, D. S.; Monteiro,
Different Extraction Procedures for Determination of Organic M. I. C.; Neto, A. A.; Tristão, M. L. B. Investigation of the Grignard
Mercury Species in Petroleum by High Performance Liquid Reaction and Experimental Conditions for the Determination of
Chromatography Coupled with Cold Vapor Atomic Fluorescence Inorganic Mercury and Methylmercury in Crude Oils by GC−ICP-
Spectrometry. Talanta 2013, 106, 60−65. MS. Fuel 2014, 116, 421−426.
(58) Osborne, S. P. Quantitation of Mercury in Petroleum by ETV- (75) Snell, J. P.; Frech, W.; Thomassen, Y. Performance Improve-
ICP-MS. Appl. Spectrosc. 1990, 44, 1044−1046. ments in the Determination of Mercury Species in Natural Gas
(59) Tao, H.; Murakami, T.; Tominaga, M.; Miyazaki, A. Mercury Condensate Using an on-Line Amalgamation Trap or Solid-Phase
Speciation in Natural Gas Condensate by Gas Chromatography- Micro-Extraction with Capillary Gas Chromatography−Microwave-
Induced Plasma Atomic Emission Spectrometry. Analyst 1996, 121,
Inductively Coupled Plasma Mass Spectrometry. J. Anal. At. Spectrom.
1055−1060.
1998, 13, 1085−1093.
(76) Rahman, G. M. M.; et al. Speciation of Mercury in Crude Oil
(60) Shafawi, A.; Ebdon, L.; Foulkes, M.; Stockwell, P.; Corns, W.
Using Speciated Isotope Dilution Mass Spectrometry. Spectroscopy
Determination of Total Mercury in Hydrocarbons and Natural Gas 2010, 25.
Condensate by Atomic Fluorescence Spectrometry. Analyst 1999, (77) Filby, R. H. Origin and nature of trace element species in crude
124, 185−189. oils, bitumens and kerogens: implications for correlation and other
(61) Ceccarelli, C.; Picón, A. R.; Mariangel, P. P.; Greaves, E. D. geochemical studies. Geol. Soc. Spec. Publ. 1994, 78, 203−219.
Total Mercury Determination in naphthas by Either Atomic (78) Lamborg, C. H.; Hammerschmidt, C. R.; Gill, G. A.; Mason, R.
Fluorescence or Absorption Spectroscopy. Pet. Sci. Technol. 2000, P.; Gichuki, S. An intercomparison of procedures for the
18, 1055−1075. determination of total mercury in seawater and recomandations
(62) Liang, L.; Lazoff, S.; Horvat, M.; Swain, E.; Gilkeson, J. regarding mercury speciation during GEOTRACES cruises. Limnol.
Determination of Mercury in Crude Oil by In-Situ Thermal Oceanogr.: Methods 2012, 10 (2), 90−100.
Decomposition Using a Simple Lab Built System. Fresenius' J. Anal.
Chem. 2000, 367, 8−11.
(63) Bouyssiere, B.; Ordó ñ e z, Y. N.; Lienemann, C. P.;
Schaumlöffel, D.; Łobiński, R. Determination of Mercury in Organic
Solvents and Gas Condensates by μflow-Injection  Inductively
Coupled Plasma Mass Spectrometry Using a Modified Total
Consumption Micronebulizer Fitted with Single Pass Spray Chamber.
Spectrochim. Acta, Part B 2006, 61, 1063−1068.
(64) Torres, D. P.; Dittert, I. M.; Höhn, H.; Frescura, V. L. A.;
Curtius, A. J. Determination of Mercury in Gasoline Diluted in
Ethanol by GF AAS after Cold Vapor Generation, Pre-Concentration
in Gold Column and Trapping on Graphite Tube. Microchem. J. 2010,
96, 32−36.
(65) Olsen, S. D.; Westerlund, S.; Visser, R. G. Analysis of Metals in
Condensates and naphtha by Inductively Coupled Plasma Mass
Spectrometry. Analyst 1997, 122, 1229−1234.
(66) Kumar, S. J.; Gangadharan, S. Determination of Trace Elements
in naphtha by Inductively Coupled Plasma Mass Spectrometry Using
Water-in-Oil Emulsions. J. Anal. At. Spectrom. 1999, 14, 967−971.
(67) Bouyssiere, B.; Szpunar, J.; Lobinski, R. Gas Chromatography
with Inductively Coupled Plasma Mass Spectrometric Detection in
Speciation Analysis. Spectrochim. Acta, Part B 2002, 57, 805−828.
(68) Vorapalawut, N.; Pohl, P.; Bouyssiere, B.; Shiowatana, J.;
Lobinski, R. Multielement Analysis of Petroleum Samples by Laser
Ablation Double Focusing Sector Field Inductively Coupled Plasma
Mass Spectrometry (LA-ICP MS). J. Anal. At. Spectrom. 2011, 26,
618−622.
(69) da Silva, C. S.; Oreste, E. Q.; Nunes, A. M.; Vieira, M. A.;
Ribeiro, A. S. Determination of Mercury in Ethanol Biofuel by
Photochemical Vapor Generation. J. Anal. At. Spectrom. 2012, 27,
689−694.
(70) de Jesus, A.; Zmozinski, A. V.; Vieira, M. A.; Ribeiro, A. S.; da
Silva, M. M. Determination of Mercury in naphtha and Petroleum
Condensate by Photochemical Vapor Generation Atomic Absorption
Spectrometry. Microchem. J. 2013, 110, 227−232.
(71) Bouyssiere, B.; Baco, F.; Savary, L.; Lobinski, R. Analytical
Methods for Speciation of Mercury in Gas Condensates: Critical
Assessment and Recommendations. Oil Gas Sci. Technol. 2000, 55,
639−648.
(72) Gajdosechova, Z.; Pagliano, E.; Zborowski, A.; Mester, Z.
Headspace in-Tube Microextraction and GC-ICP-MS Determination
of Mercury Species in Petroleum Hydrocarbons. Energy Fuels 2018,
32, 10493−10501.

13320 https://dx.doi.org/10.1021/acs.energyfuels.0c02730
Energy Fuels 2020, 34, 13307−13320