Spectrochimica Acta Part B 160 (2019) 105690

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Spectrochimica Acta Part B

journal homepage: www.elsevier.com/locate/sab

Invited Review

Recent advances in sample preparation methods for elemental and isotopic T

analysis of geological samples
⁎
Wen Zhang, Zhaochu Hu
State Key Laboratory of Geological Processes and Mineral Resources, Faculty of Earth Sciences, China University of Geosciences, Wuhan 430074, China

A R T I C LE I N FO A B S T R A C T

Keywords: Knowledge of the elemental compositions and isotopic ratios of geological samples is a prerequisite for geo-
Sample digestion chemical research. For whole-rock elemental composition and isotopic analyses, sample digestion is a crucial
Geological sample step and often the limiting factor for achieving reproducible and accurate analytical results. This review focuses
ICP-MS on the recent advances in sample digestion methods, especially on open-vessel acid digestion, high-pressure acid
LA-ICP-MS
digestion, microwave digestion, alkali fusion, high-pressure asher, and sample preparation methods for laser
Ammonium bifluoride
ablation-inductively coupled plasma-mass spectrometry (LA-ICP-MS) analysis. This review addresses concerns
Ammonium fluoride
and discusses the attributes and limitations of these sample digestion methods along with examples of their
applications in geochemical analysis. Particular attention is placed on sample digestion with ammonium fluoride
(NH4F) and ammonium bifluoride (ammonium hydrogen fluoride, NH4HF2), which are recent new research
hotspots. Whole-rock analysis by LA-ICP-MS is becoming a promising technique because of rapid developments
in sample preparation. It is evident that only the appropriate sample digestion methods can provide us with high-
quality analytical results and guarantee the success of further investigations.

1. Introduction multielement analytical results. This is particularly true for geological

Knowledge of the elemental compositions and isotope ratios in
geological samples is of high significance to research in earth science
and other disciplines. Even with modern instruments, geological sample
digestion is the basis for accurate analysis of elemental and isotopic
compositions [1–3]. Mass spectrometry has been a dominant technique
to determine a comprehensive range of trace elements and isotopic
ratio analysis of geochemical interest [4]. The major purpose of sample
digestion is to convert a sample into a form that is suitable for accurate
and stable chemical analysis in an analytical instrument (e.g., mass
spectrometer). In many cases, solid samples are converted to the solu-
tion form because of adequate homogeneity of a solution. Modern in-
strumental analysis poses many requirements with regard to the prop-
erties of the final sample solution. Taking inductively coupled plasma-
mass spectrometry (ICP-MS) as an example, which is by far the major
technique of choice for elemental analysis at the trace level, the total
dissolved solids (TDS) in the final solution is required to be low to avoid
serious matrix effects, clogging of cones, and signal instability. Poten-
tial sources of contamination should be carefully controlled, including
reagent purity, cleanliness of test vessels and environment, and cross-
contamination during operational processing. Moreover, complete
sample digestion is an important prerequisite for achieving accurate
samples, which usually contain refractory minerals. The loss of ele-
ments in the form of precipitation or volatilization should also be
avoided. To summarize, sample digestion is a fundamental and critical
stage in the process of sample analysis, which directly affects the ac-
curacy and precision of the analysis. In addition, sample digestion is
often tedious and time-consuming, especially for geological samples. It
is thus the limiting factor for sample throughput [1,3,5–7].
Natural geological samples are polyphase systems consisting of
heterogeneous admixtures of minerals of contrasting chemical compo-
sitions and physical properties. Specifically, some resistant accessory
minerals (e.g., zircon and garnet) generally control the whole-rock
budget for some of the key trace elements (e.g., Nb, Ta, Zr, Hf, rare
earth elements (REEs), U, and Th), which are important geological
process indicators. In addition, because of the differences in the oc-
curring state of minerals and physicochemical properties such as
melting point, boiling point, volatility, chemical valence, and ionic
radius, elements have different behaviors during the sample digestion
procedure. As a result, there is still no single, universal sample pre-
paration method that can provide quantitative recovery of all elements
in all types of geological sample [3]. The development of multiple in-
dependent sample digestion methods is an inevitable requirement in the
field of sample digestion, and it is also essential to evaluate and

⁎
Corresponding author.
E-mail address: zchu@vip.sina.com (Z. Hu).

https://doi.org/10.1016/j.sab.2019.105690
Received 25 March 2019; Received in revised form 10 July 2019; Accepted 27 August 2019
Available online 29 August 2019
0584-8547/ © 2019 Published by Elsevier B.V.
W. Zhang and Z. Hu
compare data with each other. Commonly used sample digestion
methods can be divided into two classes, acid digestion and fusion.
These two classes also can be subdivided into a number of different
categories, depending on the combinations of reagents, digestion
parameters, and digestion devices. In addition, techniques such as
Carius tube and high-pressure asher (HPA) system (HPAeS) are pro-
posed separately, although they also use acid reagents for digestion. For
the basic knowledge of these methods, other publications [1,3,8,9] are
recommended.
Compared to the rapid development of instrument hardware and
mass spectrometric analytical technology, the progress in geological
sample digestion method is overall very slow [10]. Fortunately, many
conventional sample digestion methods have had new technological
innovations during the past few years. In addition to ensuring complete
recovery of elements and good analytical reproducibility, new sample
digestion methods focus on multielement capability at ultra-low con-
tent. Many aspects have also been actively investigated, including high
sample throughput, reduced labor and reagent consumption, simple
digestion processes, and operator safety. A significant advancement is
the use of two digestion reagents: ammonium fluoride (NH4F) and
ammonium bifluoride (ammonium hydrogen fluoride, NH4HF2). These
reagents can replace hydrofluoric acid in acid digestion [11,12]. On the
other hand, there has been increasing interest in the quantitative ana-
lysis of major and trace elements by laser ablation-ICP-MS (LA-ICP-MS)
bulk analysis, which provides several advantages over solution ICP-MS,
including minimal sample preparation, low blanks, high sample
throughput, and green chemistry concept [13–16].
This review focuses on the recent advances in sample digestion for
geological samples. The authors do not attempt to discuss all dissolution
methods; rather, common (or typical) methods that are routinely used
in the laboratory are presented. Detailed introductions about the NH4F
and NH4HF2 digestion methods and the sample preparation of LA-ICP-
MS analysis are summarized. Additionally, research progress on con-
ventional acid digestion, fusion method, and HPA-S is also presented.
2. Acid digestion
2.1. Open-vessel acid digestion
Open-vessel acid digestion has long been a popular and simple
method for the digestion of inorganic and organic materials in chemical
laboratories. Open-vessel acid digestions refer to acid attack in open
containers or screw-top vials (lowly pressurized) placed on a hot plate
[3]. Strong mineral acids (HNO3, HCl, and HClO4) and the weak mi-
neral acid HF are generally used for digestion of geological samples.
Open-vessel acid digestion is successful when applied to most fine-
grained mafic rocks or geological samples without refractory minerals.
Ma et al. [17] investigated the reproducibility of elemental analysis of
basaltic samples by open-vessel acid digestion with a HNO3 + HF
mixture at 120 °C for > 12 h. For more than forty elements, the ana-
lytical results obtained from open-vessel acid digestion were consistent
with those obtained from high-pressure acid digestion, indicating the
reliability of open-vessel digestion. The complete dissolution of FeeMn
nodules with open-vessel acid digestion was reported by Berezhnaya
and Dubinin [18] for the determination of platinum group elements
(PGEs, Ru, Pd, Ir, and Pt) and Au. Good agreement was achieved be-
tween open-vessel acid digestion and microwave digestion operated
under elevated temperature and pressure. In addition, open-vessel acid
digestion is widely used in isotopic analysis of geological samples such
as Li [19], Mg [20], Ca [21], Cu-Fe-Zn [22], Ba [23], Ag [24], and
others, which are considered to be absent or present only in trace
quantities in refractory minerals.
However, the maximum digestion temperature for open-vessel acid
digestion is limited by the boiling point of the corresponding acid or
acid mixture (e.g., boiling points of 38.3% HF = 112 °C, 68%
HNO3 = 122 °C, and 20.24% HCl = 110 °C) under ambient pressure,
2
Spectrochimica Acta Part B 160 (2019) 105690
which is a major limitation [3]. It is thus difficult to apply open-vessel
acid digestion to felsic rocks because of the incomplete dissolution of
refractory minerals such as zircon [4,25–27], which requires more
vigorous digestion conditions. Generally, high-pressure acid digestion
(bomb digestion) or alkali fusion is recommended for the digestion of
granites.
2.2. High-pressure acid digestion
Modern high-pressure acid digestions (bomb digestion) consist of a
polytetrafluoroethylene (PTFE) beaker with a lid, which fits tightly into
an outer, stainless-steel pressure jacket [3]. These bombs withstand
very high pressures (7–12 MPa) when the sample and acids are sub-
jected to high temperatures (110–250 °C) [28,29]. This method enables
effective digestion of refractory phases, which are not decomposed or
only partially decomposed in the open vessel and microwave digestion.
Other advantages of the high-pressure digestion include shortening the
digestion time, reducing acid reagent consumption, avoiding the losses
of volatile elements, and a lower procedure blank [3]. Therefore, high-
pressure acid digestion is particularly suitable for trace and ultra-trace
analysis. Note that high-pressure acid digestion does not include the
closed-vessel microwave digestion method, which is discussed sepa-
rately in Section 2.3.
Effective digestion of refractory accessory minerals is an important
advantage of the high-pressure acid digestion, which has been shown
constantly and consistently in recent reports. The results of the GeoPT
proficiency testing programme provide an opportunity to recognize that
inappropriate acid digestion schemes lead to unsuccessful multielement
analysis in some special samples. Potts et al. [4] compared the analysis
results of a basalt sample and those of a sediment sample in GeoPT. The
former is considered a “well-behaved” rock, but the latter contains
zircon or other refractory minerals. The ICP-MS and acid digestion test
results of most elements in the basalt sample obtained from different
laboratories were consistent with the results of other independent
analyses. However, the variably low results for Y, heavy rare earth
elements (HREEs), and Zr were observed for the sediment sample. A
comparison of the reported procedures revealed that the poor re-
coveries were caused by the incomplete digestion of zircon when open-
vessel digestions and microwave digestions were used. In contrast,
when the samples were digested even under relatively mild acid con-
ditions but under high pressure, such as 2 ml HF per 100 mg of sample,
digestion temperature of 180 °C, and digestion time of 48 h, complete
recovery can be obtained. Potts et al. [4] thus recommended this con-
dition as a reliable dissolution method for silicate rock that could be
expected to contain zircon or other refractory minerals. In addition, a
comparison between high-pressure acid digestion and open-vessel acid
digestion was studied for analyzing trace elements in the iron-formation
reference materials [26]. Lower recoveries of HREEs were observed in
the open-vessel acid digestion due to incomplete digestion of the re-
fractory phases. In contrast, quantitative recoveries of HREEs were
achieved with high-pressure acid digestion.
The dissolution process of geological materials in complex matrix is
still not fully understood. Use of HF alone has been considered a more
efficient way to digest geological materials than with HF-HNO3 mixture
[30]. Recently, Okina et al. [31,32] conducted a series of studies on the
conventional high-pressure acid digestion to understand the effect of
acid mixture during digestion and evaporation. The results indicated
that the digestion of refractory accessory minerals is controlled by the
concentration of HF in the acid mixture. Quantitative recoveries of Zr
and Hf can be achieved only when the HF concentration in an acid
mixture is > 35%, with the digestion performed at > 180 °C for > 16 h.
The absolute amount of HF requirement for rock digestion is 5–10 times
higher than the theoretical one based on stoichiometry. In contrast, the
source of HF is not important [31]. Further investigations were focused
on the effects of the residual fluoride ion in the final solution during
evaporation [32]. The authors found that the critical concentration of
W. Zhang and Z. Hu
fluoride ion is in the range of 20–80 μg ml−1, depending on the ele-
mental compositions of the rock sample. When the residual fluoride ion
was below the critical concentration, the recoveries of Ta and Nb were
reported to be low. Moreover, the concentration of residual fluoride ion
in the final solution prepared for the analysis mainly depends on the
type of acid mixtures used during evaporation. Evaporation with HClO4
alone or an HClO4 + H3BO3 mixture would significantly reduce the
residual fluoride ion compared to evaporation with HNO3 only, re-
sulting in hydrolysis of high-field strength elements (HFSE) and low
recoveries of Ta and Nb. However, to eliminate fluoride influence,
evaporation with HClO4 alone or an HClO4 + HNO3 mixture was pro-
posed, but it should be finished shortly after the appearance of HClO4
vapor.
The formation of insoluble fluorides that coprecipitate trace ele-
ments is a problem [10,30]. To suppress the formation of insoluble
fluorides, many methods have been studied, including evaporation with
HClO4 [30,33–35] or boric acid [36–38], adjustment of the
[(Mg + Ca)/Al] ratio of the sample [10,34,39,40], reduction of pres-
sure in the digestion process [11,12], decrease in the sample amount
[30], and control of sample dryness during evaporation [5,41]. How-
ever, a thorough understanding of the fluoride formation mechanism
and complete inhibition of fluoride formation remains unclear. Chen
et al. [42] thought that insoluble fluorides could exist in various forms
of fluoro complexes including (Ca, Mg)F2, AlF3, Al(OH)3, or Al(OH, F)3.
The authors suggested that a re-dissolution process, after evaporation
with HNO3 at 190 °C for 2 h under high pressure, could dissolve these
fluorides. In addition, the reagents of NH4HF2 and NH4F have been
recently reported to prevent the formation of fluorides in open-vessel
acid digestion and microwave digestion [11,12,43].
The new sample preparation methods for some trace elements that
are not commonly measured were developed by high-pressure acid
digestion [44,45]. He et al. [44] reported on the analysis of Br and I in
soils and sediments by ICP-MS. Samples were digested with an
HNO3 + HF mixture under high pressure. A serious loss of Br and I was
found at a high digestion temperature of 190 °C due to volatile forms of
Br and I (e.g., as HBr, HI, and I2). Therefore, an optimized digestion
procedure of heating at 140 °C for 15 min was recommended. A dilution
with 5% ammonia solution was used to stabilize Br and I and eliminate
their memory effects on the sample introduction system of ICP-MS.
2.3. Microwave digestion
Microwave digestion is based on the ability of a certain substance
(solvent and/or reagent) to absorb microwave radiation and transform
its energy into heat energy [3,46–51]. Compared with conventional
heating, microwave heating is many times more efficient. The inter-
action of microwave radiation with sample and reagents causes both
ionic migration and dipole rotation, resulting in rapid bulk heating of
the reaction mixture with consequent decomposition of the sample.
Microwave digestion procedures are classified according to their op-
erational modes: open-vessel microwave-assisted digestion and closed
(pressurized)-vessel procedures [3]. The latter have the advantages of
reducing the digestion time, contamination, loss of volatile species, and
reagent and sample consumption. Online microwave-assisted digestion
of solid samples is also known [52]. Microwave digestions have been
developed to include a variety of sample matrices such as basalts, soils,
sediments, coals, airborne particulates, sludge, and organic
Table 1
General physical properties of NH4F and NH4HF2.
Formula Phys. form Molar mass (g mol−1)
Ammonium fluoride NH4F white crystal, hydroscopicity 37.037
Ammonium bifluoride NH4HF2 white crystal, hydroscopicity 57.044
Data taken from “CRC Handbook of Chemistry and Physics. 97st ed”.
3
Spectrochimica Acta Part B 160 (2019) 105690
environmental and biological samples [3,5,8].
However, several authors have reported that microwave digestion
does not always allow for the accurate analyses of elements such as Cr,
Zr, Hf, and HREEs because of the relatively short digestion time com-
monly used in a microwave system, especially when refractory minerals
(e.g., zircon, chromite, rutile, corundum, and cassiterite) are present.
Therefore, its applicability seems restricted to dissolve basalts [5] or to
obtain part of trace elements from rocks [53], ores [54], and soils [55].
Fedyunina et al. [56] made efforts for the complete digestion of re-
fractory minerals by microwave digestion. They found that the con-
ventional microwave digestion with an HF + HNO3 mixture at 210 °C
for 1 h could quantitatively digest basic rocks but not felsic rocks. The
addition of HCl and H3BO3 in the digestion process significantly en-
hanced the digestion efficiency and quantitatively transformed ande-
sites and some types of granites. However, some syenite, granodiorite,
and granite, which are rich in albite (NaAlSi3O8), are still non-
quantitatively digested. The main reason was attributed to the in-
complete digestion of the complex aluminum-silicates in the microwave
field. Magaldi et al. [43] evaluated the NH4HF2 microwave digestion
method for multielement analysis in geological reference materials
from felsic to ultramafic composition. Low recoveries of Zr and Hf in
granodiorite GSP-2 and granite G-2 were reported, indicating the in-
complete digestion of zircon. Therefore, microwave digestion cannot be
treated as the universal technique for all types of rocks [56].
2.4. NH4F and NH4HF2 digestion
In recent years, the traditional reagents NH4F and NH4HF2 have
been utilized for new applications in geological sample digestion for
trace element determination by ICP-MS. [11,12,40,43,57,58]. These
two reagents are very similar in their working principle and digestion
process; therefore, they can be considered as one type of digestion
method. However, some physicochemical differences between them,
such as digestion temperature and digestion time, should be noted.
Additionally, to the best of our knowledge, there is currently no com-
prehensive review on these two digestion reagents. Therefore, the
content presented in this section is expanded slightly beyond the field of
geological analysis sample preparation. In this section, we extensively
discuss the applications of NH4F and NH4HF2 in radioanalytical
chemistry, environmental science, agriculture science, and metallurgy
for multielement analysis or elemental extraction and cover some pre-
viously published papers.
NH4F and NH4HF2 are white, water-soluble crystalline salts, and
soluble in water. The physical properties of NH4F and NH4HF2 are
summarized in Table 1. Much of the commercial interest in NH4F and
NH4HF2 stems from their chemical reactivity as less hazardous sub-
stitutes for hydrofluoric acid [59,60]. > 2072 papers on NH4F have
been published (Fig. 1, data from Web of Science). These publications
show that NH4F is mainly used as an electrolyte solution or fluorine
precursor to synthesize high-purity materials or nanomaterials in the
field of material science, such as TiO2 [61,62], CeO2 [63], LaF3 [64],
CaF2 [65], etc. In addition, certain physical properties of nanomaterials
can be improved through their modification with NH4F. For example,
fluorine was doped to enhance the photocatalytic activity of TiO2 with
NH4F treatment [66,67]. NH4F is also a traditional surface treatment
agent for surface morphology modification, substrate activation, and
silica-based substance etching. NH4F has attracted much recent
Density (g cm−3) Melting point (°C) Boiling point (°C) CAS Reg. No.
1.015 238 – 12,125-01-8
1.5 125 240 (decomposes) 1341-49-7
W. Zhang and Z. Hu
Fig. 1. Statistics of research based on NH4F and NH4HF2 collected from “Web of Science” and breakdown according to their application areas.
research attention in the search for high-performance materials for
electrochemical energy storage [68–71] and is also widely applied in
semiconductor technology to etch or clean the surface of silica-based
substances [72–76]. Similarly, NH4HF2 is also applied to areas of new
material synthesis [77–80], formation of electroless coatings [81–83],
modification of surface morphology [84,85], and etching of glasses and
other silicon materials [86–88]. However, its focus in research is not as
prevalent as NH4F (Fig. 1, only 178 publications).
We found that only a small fraction of NH4F (4%) and NH4HF2 (8%)
reported applications are related to analytical chemistry (Fig. 1). NH4F
tends to release ammonia gas on heating and is converted to the more
stable form NH4HF2 (Eq. (1)) [60]. NH4HF2 can release ammonia gas
and hydrogen fluoride gas on heating (Eq. (2)).
2NH 4 F → NH 4 HF2 + NH3
NH 4 HF2 → NH3 + 2HF
Therefore, NH4F and NH4HF2 can replace HF and take part in re-
actions with many substances (such as oxides, hydroxides, and salts) at
room temperature or on heating to form ammonium fluorometallates or
oxofluorometallates. They are considered promising reagents for
fluorination of minerals, metal oxides, ores, and geological samples.
Analysts in different fields have established sample pretreatment
methods based on NH4F and NH4HF2 for subsequent chemical analysis.
Alternatively, these reagents can effectively extract elements from
concentrates, ores, or rocks in the metallurgical industry.
2.4.1. Geochemistry analysis
NH4F and NH4HF2 reagents can be used as promising sample di-
gestion reagents in lieu of HF acid to break the SieO bond in minerals.
The fluorination reactions of silicon-containing minerals of different
compositions and structures with NH4HF2 have been summarized by
Laptash and Maslennikova [89]. In the mid-1980s to early 1990s, Ko-
likova et al. [90,91] already reported the interactions between NH4F/
NH4HF2 and silicate minerals by stirring solid NH4F/NH4HF2 with
powdered minerals at ambient temperatures, resulting in partial de-
composition of the silicates. However, these reagents have long been
ignored in the field of trace element analysis of geological samples. In
the last decade, Mariet et al. [92] suggested the use of
HNO3 + H2O2 + NH4F mixture instead of HNO3 + HF + HClO4 in
conventional open acid digestion for lichen, basalt, and soil. In their
study, 50 mg (100 mg for lichen) of reference materials was weighed
into Teflon flasks, and the flasks were placed on a sand bath at 240 °C
for 10 h with an HNO3-NH4F mixture containing 1 ml NH4F (47%).
Thirteen elements in the basalt reference material were determined
with an estimated bias of < 10%. Subsequently, Hu et al. [57] reported
Spectrochimica Acta Part B 160 (2019) 105690
the application of NH4F to high-pressure bomb digestion of geological
samples for multi-element analysis by ICP-MS. Thirty-three trace ele-
ments present in a wide variety of geological samples were completely
recovered by digestion lasting for 24 h with a NH4F + HNO3 mixture at
190 °C. These two pioneering studies showed the capacity of the NH4F
reagent to release trace elements from geological samples, ranging from
mafic rocks to felsic rocks. However, the processes are time consuming.
In the study reported by Hu et al. [57], a sample amount of > 150 mg
under the high-pressure bomb digestion condition yielded white pre-
cipitates in the final solution, resulting in significant losses of some
trace elements such as Sc, Y, Sr, REEs, and Th.
Further investigations on the use of NH4F or NH4HF2 reagents for
geological sample digestion were carried out by Hu's group. Use of
NH4F or NH4HF2 along with open-vessel digestion (Savillex screw-top
(1)
Teflon vial) was developed to digest various rock reference materials
(2) for multielement analysis [11,12]. The high boiling points of NH4F and
NH4HF2 allow the use of an elevated digestion temperature, which
enables rapid decomposition of refractory phases in open vessels.
Thirty-seven elements at trace levels were completely recovered. From
the results reported in these two representative papers, the advantages
of NH4F and NH4HF2 digestion technologies are summarized as follows:
(1) Efficient and complete digestion of geological samples in the open-
vessel technique
The open-vessel acid digestion has long been a popular and simple
method for the digestion of inorganic and organic materials in chemical
laboratories. It is a low-pressure (technically speaking, lowly pressur-
ized) digestion conducted using open vials or screw-top Teflon vials.
Therefore, the maximum digestion temperatures are limited by the
boiling point of the corresponding acid or acid mixture under ambient
pressure. The limited digestion temperature not only prolongs digestion
time but also is often insufficient for the dissolution of refractory mi-
nerals such as zircon. The high boiling points of NH4F and NH4HF2
(260 °C and 239.5 °C) allow elevated digestion temperatures in open
vessels. Consequently, the rock samples can be completely digested by
NH4F at 250 °C in 1.5–2 h or by NH4HF2 at 230 °C in 2–3 h. The ap-
plicable sample types include felsic igneous rocks, which contain re-
fractory minerals such as zircon. It is worth noting that mixing of NH4F
or NH4HF2 reagents with water, in particular with HNO3 and HCl,
moderates their digestion ability. We speculate that the added HNO3 or
HCl reacts with NH4F or NH4HF2 and releases HF rapidly. The released
HF is rapidly lost through evaporation at elevated temperature, re-
sulting in a decrease in F− ion concentration in the residual reagent,
leading to a reduced digestion capability in open vessels.
(2) NH4F/NH4HF2 open-vessel acid digestion methods are not hampered
by the formation of insoluble fluorides due to the low-pressure digestion
environment
4
W. Zhang and Z. Hu Spectrochimica Acta Part B 160 (2019) 105690

There is consensus that use of HF to digest silicate samples in a high- NH4F digesiton method NH4HF2 digesiton method
pressure acid digestion environment could cause formation of insoluble
fluorides, which subsequently incorporate large proportions of trace 50 mg samples + 300 mg NH4F 50 mg samples + 200 mg NH4HF2
elements [10,30,34,35]. Previous studies reported that factors influ-
encing the formation of insoluble fluorides are the relative proportions A screw-top PFA vial A screw-top PFA vial
of Al:Mg:Ca in the sample, digestion pressure, and test portion mass of
Heat for 2 hour at 250oC Heat for 3 hour at 230oC
the sample powder [10,30,34]. However, the procedures for NH4F or
in an electric oven in an electric oven
NH4HF2 open-vessel digestion methods are performed in a low-pressure
environment. Zhang et al. [11] reported that no insoluble fluorides
1.5 ml HNO3 2 ml HNO3
were observed when using NH4HF2 in the open-vessel technique for
granodiorite GSP-2, even when the test portion size of GSP-2 was in-
Evaporating at 160oC to dryness Vial is capped and heated
creased to 200 mg. Hu et al. [12] performed digestion of six geological for 1 hr at 160oC
reference materials, with amounts ranging from 50 mg to 200 mg, using 1.5 ml HNO3 Evaporating at 160oC to dryness
NH4F by open-vessel acid digestion, and they also did not observe the
formation of insoluble fluorides with the naked eye. In addition, ex- Evaporating at 160oC to dryness
1 ml HNO3+1 ml water
cellent agreement between the measured and the reference values were
+1 ml In solution
achieved in both studies. The absence of insoluble fluorides was at- 1 ml HNO3+1 ml water
tributed to the low-pressure digestion environment. This advantage +1 ml In solution
Vial is capped and heated
guarantees the accurate analysis of some important and fluoride pre- for 6 hr at 120oC
cipitate-sensitive elements (e.g., Rb, Sr, REEs, and Th) in geological Vial is capped and heated
samples. for 6 hr at 120 oC Transfer to bottle and
(3) Commercial NH4F and NH4HF2 reagents can be effectively purified diluted to 100g by 2% HNO3
Transfer to bottle and
by the sub-boiling distillation purification system, similar to HF, HNO3, and
diluted to 100g by 2% HNO3
HCl
Modern ICP-MS instrumentation enables the measurement of ex- Fig. 2. Flowchart showing details of NH4F/NH4HF2 open vessel acid digestion
tremely low concentrations of elements in geological samples. The in- methods presented in Hu et al. [12] and Zhang et al. [11].
fluence of reagent blank, which, in many cases, determines the lower
limit of quantitation in the analytical results, becomes increasingly
higher digestion temperature in open vessels. Therefore, digestion with
important with decreasing elemental concentrations. For unpurified
NH4F can be reduced to 2 h at 250 °C compared to that by the NH4HF2
NH4F and NH4HF2, significant contamination levels for some transition
method, which requires 3 h at 230 °C. However, according to our un-
metal elements such as V, Cr, Co, Ni, Cu, and Zn, have been reported.
derstanding, the NH4HF2 reagent is receiving more attention and wider
After purification treatment with sub-boiling distillation, the purified
application, possibly because high-purity NH4HF2 is more readily
NH4F and NH4HF2 provide satisfactory reagent background similar to
available than NH4F. Gaschnig et al. [93,94] employed the NH4HF2
that obtained with the conventional HF-HNO3 acid digestion method
open-vessel method to digest their subset of glacial diamictite samples
[12,13,58]. Ultrapure NH4F and NH4HF2 reagents are beneficial for
for trace element analysis. O'Neil et al. [95] found that the simple
ultra-trace multi-element determination. In addition to the use of sub-
HNO3 + HF digestion in closed Savillex Teflon beakers cannot effec-
boiling distillation to obtain ultrapure NH4F and NH4HF2, commercial
tively dissolve amphibolite samples, resulting in Zr and Hf contents.
high-purity reagents are currently available, for example, from Sigma-
Then, a second dissolution with NH4HF2 in screw-top Teflon vials was
Aldrich as trace-metal grade NH4F (99.99%) and NH4HF2 (99.999%).
performed following the procedure described by Zhang et al. [11]. The
The latter has been used for trace element analysis by O'Hara et al. [58].
measured Zr and Hf concentrations in the NH4HF2 open-vessel acid
(4) NH4F or NH4HF2 digestion methods are comparatively safer to
digestion method were reported to be comparable to previously de-
handle and economical
termined results.
Compared to the corrosive and toxic HF, which is in the solution
Furthermore, bauxite was digested with NH4F or NH4HF2 in open
form, NH4F and NH4HF2 are solids and thus are comparatively safe for
vessel for trace element analysis [40]. Bauxite is composed principally
the operator during handling. The NH4F or NH4HF2 digestion method
of aluminum hydroxides and different minerals including refractory
does not require the use of large amounts of acid reagents as in con-
ores (zircon, tourmaline, and rutile). The conventional bomb digestion
ventional open digestion methods and avoids the expensive high-pres-
method with HF/HNO3 results in a significant loss of REEs due to the
sure digestion bomb. The relatively economical price of NH4F and
formation of insoluble AlF3 precipitates. The NH4F or NH4HF2 open-
NH4HF2 compared to HF renders another advantage in reducing costs.
vessel digestion method was reported to be able to completely digest
(5) There is largely reduced risk in introducing high total dissolved solids
resistant minerals in bauxite samples in a short period of time (5 h).
(TDS) and complex polyatomic ion interference
White precipitates and semi-transparent gels were obtained in both
Excessive NH4F and NH4HF2 reagents can be effectively removed
digestion methods, but these precipitates and gels can be dissolved by
during the evaporation process, and thus, they do not remain in the
HClO4. O‘Hara et al. [58] systematically evaluated the efficiency of
final solution. For digestion of silicate minerals, NH4F and NH4HF2
using NH4HF2 to digest a range of inorganic sample types. Their study
reagents release hydrofluoric acid and break the strong SieO bonds,
focused on the effects of NH4HF2-to-sample ratios and the NH4HF2 di-
ultimately forming (NH4)2SiF6. Subsequent thermal treatment in the
gestion time. The results showed that the required NH4HF2-to-sample
presence of HNO3 will result in the formation of SiF4, thus removing
ratio depends on the specific material being decomposed. For glass and
this major elemental component from the silicate matrix, which further
quartz, the required ratios are consistent with predictions from stoi-
reduces TDS in the final solution. The constituents of NH4F and NH4HF2
chiometry, whereas with soil and low-grade U ore standards, mass ra-
reagents (H, N, and F) are consistent with those of the HF and HNO3
tios in excess of stoichiometric estimations are more effective.
mixture. Additional polyatomic ion interferences are not present,
The advantages of the NH4F and NH4HF2 reagents described above
making digestion methods with NH4F and NH4HF2 suitable and com-
attract analysts to use them in other sample preparation techniques
patible for ICP-MS analysis.
(Table 2). Husáková et al. [96] reported an NH4F microwave digestion
The processes of NH4F/NH4HF2 open-vessel acid digestion methods
method to determine silicon and boron in fertilizers, sludge, plants, and
described by Hu et al. [12] and Zhang et al. [11] are listed in Fig. 2.
fly ash. Fifty milligrams of the sample was digested with 5 mL of
NH4F has a higher boiling point than NH4HF2, which allows the use of a

5
 W. Zhang and Z. Hu

Table 2
Selection of typical sample treatment procedures for NH4F and NH4HF2 digestion methods
Materials Determined elements or isotope ratios Sample treatment Reference

Reagent Digestion temperature Digestion time Digestion vessel

Geological materials
Lichen, basalt, soil Sc, Cr, Co, Ni, Zn, As,Rb, Sr, Mp, Sb, Cs, HNO3 + NH4F + H2O2 240 °C in a sand bath 10 h Closed flask Mariet et al. [92]
Ba, La, Ce, Nd, Sm, Eu, Gd, Tb, Yb, Hf, Ta,
Pb, Th, U
Basalt, andesite, granodiorite, granite Li, Sc, V, Co, Ga, Rb, Sr, Y, Zr, Nb, Cs, Ba, NH4F + HNO3 190 °C in an electric oven 24 h PTFE-lined stainless- Hu et al. [57]
REEs, Ta, W, Tl, Pb, Th, U steel bomb
Basalt, andesite, granodiorite, granite, rhyolite, Li, Be, Sc, V, Cr, Co, Ni, Cu, Zn, Ga, Rb, Sr, NH4HF2 230 °C in an electric oven 3h 7-mL screw-top PFA Zhang et al. [11]
sedimentary Y, Zr, Nb, Cs, Ba, REEs, Ta, Tl, Pb, Th, U vial
Basalt, andesite, granodiorite, granite, rhyolite, Li, Be, Sc, V, Cr, Co, Ni, Cu, Zn, Ga, Rb, Sr, NH4F 250 °C in an electric oven 2h 7-mL screw-top PFA Hu et al. [12]
sedimentary, soil Y, Zr, Nb, Cs, Ba, REEs, Ta, W, Tl, Pb, Th, vial
U
Solid Si and B NH4F 180 °C in a microwave system 15 min 100-mL pressure- Husáková et al.
resistant PTFE vessel [96]
Coal Be, V, Cr, Mn, Co, Ni, Cu, Zn, As, Rb, Sr, HNO3 + NH4HF2 + H2O2 From 150 °C to 200 °C in a 5–10 min PTFE vessel Krishna et al.
Mo, Cd, Sb, Cs, Ba, W, Tl, Pb, Th, U and microwave digestion system at [97]

6
REEs by ICP-MS 600 W
Na, K, Ca, Mg, Fe, Al, Sc, Ti by ICP-OES
Bauxite Li, Be, V, Cr, Co, Ni, Cu, Zn, Ga, Rb, Sr, Y, NH4HF2 or NH4F + HClO4 240 °C in an electric oven 5h 7-mL screw-top PFA Zhang et al. [40]
Zr, Nb, Mo, Cs, Ba, REEs, Ta, Tl, Pb, Th, U vial
Soil, U ore Sr, Ba, Y, La, Ce, Nd, Ti, V, Mn, Fe, Cu, Zn, NH4HF2 230 °C in an electric oven 1–6 h PFA jar O'Hara et al. [58]
Mo, Zr, Ag, Hf, Pb, Th, U
Basalt, andesite, granodiorite, granite, Li, Be, Sc, V, Cr, Co, Ni, Cu, Zn, Ga, Rb, Sr, NH4HF2 + H2O + HNO3 for low-silica Approximately 200 °C in a 30 min Vessel Magaldi et al.
microgabbro, rhyolite, nepheline syenite, Y, Zr, Nb, Mo,Cd, Sn, Sb, Cs, Ba, REEs, W, rocks microwave digestion system at [43]
diabase, dolerite, shale Pb, Bi, Th, U NH4HF2 + H2O for felsic rocks 1500 W

Radioanalytical chemistry
Trinitite Al, Fe, Co, Ni, Cu, Rb, Sr, Zr, Nb, Cs, Ba, NH4HF2 230 °C on a hot block 3h 15 mL PFA vial Hubley et al.
La, Nd, Sm, Eu, Lu, Bi, Th, U, Pu [101]
Solid uranium oxides from swipe media U 1% NH4HF2 solution 80 °C in an oven 1h Sample vial Meyers et al.
[100]
Dolerite, mica schist, andesite, quartz latite, Al, Si, Ti, Fe, Co, Cu, Zn, Rb, Sr, Zr, Nb, Sn, NH4HF2 + HNO3 55 °C from the indirect sonication 5, 15, 30, 60, and 15 mL PFA vial Mason et al. [37]
basalt, obsidian, high alumina sand Cs, Ba, La, Ce, Nd, Sm, U horn 120 min
Dolerite, mica schist, andesite, quartz latite, Al, Si, Fe, Co, Ni, Cu, Rb, Sr, Zr, Nb, Mo, NH4HF2 230 °C on a hot block 10, 30, or Screw-top PFA tubes Hubley et al.
basalt, obsidian, high alumina sand Sn, Sb, Cs, Ba, La, Ce, Nd, Sm, U 180 min [38]
Surrogate post-detonation urban debris Al, Si, K, Ca, Fe, Mo, Cs, Ba, Sr, Nd, Ta, U, NH4HF2 230 °C on a hot plate 3h PFA vial Hubley et al.
235U/238U [104]
Soil and sediment Pu NH4HF2 250 °C on a hot plate 15 min 120 mL PFA vessel Wang et al.
[102]
Spectrochimica Acta Part B 160 (2019) 105690
W. Zhang and Z. Hu
100 g L−1 NH4F for 15 min at 180 °C. This method avoids the risk of
analyte loss owing to the volatile SiF4 and BF3 formed in the conven-
tional HF digestion process. The fluorination products of Si and B
formed with the use of NH4F, such as (NH4)2SiF6, NH4BF4, mixtures of
(NH4)2BOF3, (NH4)3B3O3F6, and other ammonium oxofluoroborates
and hydroxofluoroborates, are thermally stable. NH4HF2 was allowed
to react with pyrolyzed coal residue combined with microwave diges-
tion for developing a simple and reliable analytical method for coal
samples. The quantitative recoveries of thirty-four elements in coal
samples demonstrated that the NH4HF2 reagent can be used as a re-
placement to the highly toxic HF solution [97]. Magaldi et al. [43]
evaluated the NH4HF2 microwave digestion method for multielement
analysis of geological reference materials from felsic to ultramafic
composition. Samples (100 mg) were digested with a mixture of 2 ml
saturated solution of NH4HF2 and 2 ml of ultrapure water at ~200 °C
for 30 min. During the digestion procedure, no fluoride precipitations
were observed in nine felsic and intermediate rock matrices. Quanti-
tative recoveries of forty-one trace elements in twenty-one mafic and
igneous rocks were achieved, including shale. The recoveries of Cr in
two ultramafic rocks (DTS-1 and JP-1) were 90–110% but only 85% in
the ultramafic rock OKUM, which was attributed to the incomplete
digestion of the more resistant cores of the chromite grains. Low re-
coveries of Zr and Hf in granodiorites GSP-2 and granite G-2 were ob-
served, but the digestion was complete for the other four felsic rock
reference materials. The authors speculated that the difference in zircon
crystallinity, composition of the original zircon, or metamict degree
could lead to incomplete digestion. He et al. [98] developed a new
analytical method for the simultaneous determination of Cl, Br, and I in
geological materials based on NH4HF2 open-vessel digestion. The au-
thors found that Cl, Br, and I are not lost during NH4HF2 digestion at
temperatures of 200–240 °C for 0.5–12 h. They speculated that the al-
kaline atmospheric environment caused by NH3 during NH4HF2 di-
gestion can suppress the volatilization loss of Cl, Br, and I.
NH4HF2 open-vessel digestion has also been introduced as a pre-
treatment technique for LA-ICP-MS analysis of whole-rock sample
[16,99]. Zhang et al. [16] described an NH4HF2 digestion method as
sample preparation for rapid determination of major and trace elements
in silicate rocks using LA-ICP-MS. Powered rock after digestion with
NH4HF2 becomes ultrafine powder, which offers excellent cohesion and
homogeneity suitable for laser ablation without the addition of a
binder. Because of the complete destruction of silicate minerals by
NH4HF2, the digested products presented similar structure, mor-
phology, and particle size, achieving consistency in physical properties
in pressed powder pellets and matrix-matched ablation. Internal stan-
dard can be spiked into reference materials and samples. With this
method, ten major elements and thirty-five trace elements were si-
multaneously analyzed by LA-ICP-MS. The analytical results of six re-
ference materials were in general agreement with the recommended
values, with discrepancies of < 10% for most elements. The analytical
precision is within 5% for most major elements and within 10% for
most trace elements. Grate et al. [99] reported the use of NH4HF2 for
the digestion of uranium ore for subsequent LA-ICP-MS analysis. Spikes,
in the form of single element standards of In, Tb, and Bi, and isotopic
235
U were added into the uranium ore sample. LA-ICP-MS analysis of
the fluorinated products showed that the reproducibility of the isotope
ratio of 238U/235U can reach 0.1%, better than that of the elemental
ratios of 238U/115In, 238U/159Tb, and 238U/209Bi (8–12%). These results
provided a new concept of incorporating internal standards into a solid
for analysis by LA-ICP-MS to improve calibration and quantification in
solid-based analysis. In contrast to the preparation scheme presented by
Zhang et al. [16], who heated the fluorinated products to 400 °C to
remove the residual NH4HF2, Grate et al. [99] directly analyzed the
fluorinated products and emphasized that a common matrix can be
obtained from samples and reference materials, which is similar to
matrix-assisted laser desorption ionization (MALDI) and solution ana-
lysis; the initial sample is only a small fraction in the measured
7
Spectrochimica Acta Part B 160 (2019) 105690
material, so that the laser sampling is defined by a common matrix and
not by the sample itself.
2.4.2. Radioanalytical chemistry
In recent years, the NH4HF2 digestion method has attracted more
attention in nuclear forensics and emergency responses. Development
of in-field and rapid dissolution techniques is important for decreasing
response time following a nuclear event, for example, nuclear detona-
tion, nuclear accident, monitoring of nuclear material, or technology
for nuclear nonproliferation [100,101]. Conventional bulk analytical
methods (i.e., acid digestion methods and fusion methods) are difficult
to reach the requirements of in-field and rapid analyses. Acid digestion
methods are generally time-consuming and require the use of HF so-
lution for silicates and other refractory minerals that are expected to
occur in nuclear debris [101]. HF solution, which is corrosive and toxic,
is difficult for in-field use because of operator safety considerations and
their highly regulated transportation [100]. For conventional fusion
methods, high temperature (> 600 °C) and, thus, a furnace is needed. It
should be noted that in situ research usually does not allow the use of
these experimental conditions. For example, Wang et al. [102] reported
that analyzing Pu in the Fukushima Daiichi Nuclear Power Plant acci-
dent was strictly limited to a specific small area where the use of high-
temperature oven operation was restricted. In addition, high tempera-
tures for the melt could result in loss of Cs and other semi-volatile fis-
sion products [38,103].
NH4HF2 is considered as a replacement for HF to establish the low
temperature fusion method for in-field and rapid trace element and
isotope analysis. The dissolution method similar to that reported by
Zhang et al. [11] was adapted for the digestion of nuclear debris (tri-
nitite), geological reference materials, and urban canyon matrix for
trace element analyses [38,101]. The results showed that most of the
elements (with the exception of Zr) and the radiotracer can be com-
pletely recovered with a fusion time of 10 min at a digestion tempera-
ture of 230 °C. In the optimized procedure, the total dissolution time
was shortened to < 3 h. The new NH4HF2 dissolution method with in-
direct sonication at a low temperature of 55 °C was attempted by the
same group for the digestion of refractory nuclear debris [37]. Boric
acid was added to form monofluoroboric acid, which limits the for-
mation of insoluble fluorides. Quantitative recovery for most elements
in United States Geological Survey (USGS) and National Institute of
Standards and Technology (NIST) reference materials can be obtained
with 30 min of sonication, including DNC-1a (Dolerite), SDC-1 (Mica
Schist), QLO-1a (Quartz Latite), and BHVO-2 (Basalt) but not for Zr in
the DNC-1a and SDC-1. However, low recoveries of trace elements in
AGV-2 (andesite), NIST 278 (obsidian), and NIST 1413 (high-alumina
sand) were observed. The authors suspected that the low concentration
of HF (releasing from NH4HF2) and low digestion temperature in the
sonication technique caused difficulty to dissolve TiO2 and Al2O3
completely, resulting in low recoveries of many elements [37]. Hubley
et al. [104] reported the use of the NH4HF2 sonication method for the
digestion of the surrogate post-detonation urban debris, which is a vi-
trified material and contains high levels of Fe and Ca. Compared to the
conventional NH4HF2 digestion method and microwave digestion
method, the NH4HF2 sonication method resulted in Fe-bearing black
particles and lower determined concentrations for all elements.
In another study, a 1% NH4HF2 solution (w/v) was used to digest
uranium oxides (UO2 and U3O8) from simulated filter swipe media with
sample heating to 80 °C for 50–60 min [100]. These conditions yield
average uranium recoveries of 100% for U3O8 and 90% for UO2. A
digestion time of 1 h was considered suitable and timely for in-field
monitoring of nuclear material. For measurements of Pu concentration
and associated isotope ratios in soils and sediments, Wang et al. [102]
reported an NH4HF2 fusion method to extract Pu from the sample with
a hot plate with 15 min heating-up time and 15 min fusion at 250 °C.
The recovery of Pu was > 90% for a 0.5–1 g sample. The whole ana-
lytical procedure took merely 8 h, which is of benefit for rapid Pu
W. Zhang and Z. Hu
determination in environmental samples for nuclear emergency re-
sponse or environmental studies. Representative NH4HF2 digestion
methods used in radioanalytical chemistry are listed in Table 2.
2.4.3. Environmental science
In the field of industrial hygiene monitoring, occupational exposure
or skin contact to beryllium (Be) can cause Be sensitization and chronic
Be disease [105,106]. Therefore, fast and simple analytical methods
have been developed for Be analysis in the field. A new analytical
method that uses a dilute aqueous solution of NH4HF2 for extraction of
Be, followed by fluorescence measurement for the determination of
trace amounts of Be in airborne and surface samples, was developed
[100]. Dilute NH4HF2 (1–3%) solution has been demonstrated to be
effective in the digestion of Be metal and BeO [106,107], soil and se-
diment [108], BeO in polyvinyl alcohol wipes [105], or air filters [109].
2.4.4. Agriculture science
In agricultural soil research, the relationship between crop yields
and concentrations of phosphorus (P) in soils (P fertilizer) has been paid
attention for a long time. Phosphorus in soil can be extracted with a
mixture of NH4F (0.03 mol L−1) and H2SO4 (0.03 mol L−1) [110,111].
The modified extractant with 0.025 mol L−1 HOAc, 0.25 mol L−1
NH4OAc, and 0.015 mol L−1 NH4F was effective under a wide range of
soil conditions for simultaneous extraction of available phosphorus and
potassium [112]. To know the status of various P forms in calcareous
soils, a fractionation scheme of inorganic phosphorus was suggested.
NH4F was used to extract the P from Al oxyhydroxides (AleP)
[113–115].
In addition, Prietzel and Hirsh [116] reported the use of a 0.5 M
NH4F solution at a soil:solution ratio of 1:5 for the extraction of in-
organic sulfur in acid forest soils, followed by subsequent determination
of the SO42− concentration in the extract. The proposed method is more
efficient than conventional procedures in which inorganic S is extracted
with phosphate or bicarbonate solution because of its ability to extract
both SO42− that are absorbed on the mineral surfaces as well as pre-
cipitated as [Alx(OH)y(SO4)z] [116,117].
2.4.5. Metallurgy
In metallurgical industry, NH4HF2 has been used to extract elements
from concentrates, ores, or rocks. The fluoride processing of nonbauxite
aluminum ores with NH4HF2 was reported for the extraction of alu-
mina, aluminum fluoride, amorphous silica, and other useful compo-
nents [118]. The research groups of Medkov et al. [119] and Khanchuk
et al. [120] employed NH4HF2 for the extraction of noble metals and
lanthanides from carbon-bearing rocks. New separation processes for
niobium, tantalum, and scandium from tantalite or ferrocolumbite were
developed, with the use of NH4HF2 as an alternative to hydrofluoric
acid [121–123]. To extract zirconium from the refractory mineral of
zircon, microwave-assisted digestion with ammonium acid fluoride
(NH4F·1.5HF) was investigated, and complete digestion was achieved
by successive microwave digestion steps combined with an aqueous
wash procedure [124,125]. Other hydrometallurgical processes with
the use of NH4HF2 include extraction of REEs from monazite con-
centrate [126], high-purity ammonium hexafluorosilicate and amor-
phous silica from quartz sands [127], and titanium from titaniferous
concentrates [128]. In these applications, NH4HF2 is considered easier
and safer to handle than aqueous HF [122,123]. Another advantage of
NH4HF2 is its lower cost because NH4HF2 (including NH4F) is a by-
product of the production of superphosphates [129] and local plants
producingNF3, for example [123].
2.4.6. Reported problems
Although many of the publications described above have reported
successful digestion of samples and quantitative recovery of multiple
elements with NH4F or NH4HF2 reagents, some contrasting results have
been reported recently. Chiweshe et al. [130] attempted to digest
8
Spectrochimica Acta Part B 160 (2019) 105690
chromitite concentrates at 250 °C using NH4HF2 in a ratio of 1:20 for
1 h and then determined Ru, Os, and Pt by inductively coupled plasma
optical emission spectrometry (ICP-OES). Low recoveries of Ru, Os, and
Pt were observed and compared with the results obtained with the use
of ammonia and sodium phosphate fluxes at 800 °C. There are some
problems in Chiweshe's digestion procedure, for example, the use of
open platinum crucibles and too high a digestion temperature at 250 °C,
which exceeds the decomposition temperature of NH4HF2. According to
our experience, NH4HF2 decomposes and evaporates at 250 °C from an
open crucible, resulting in a decrease in digestion efficiency.
O'Hara et al. [58] used the NH4HF2 open-vessel digestion method to
digest 50 mg pure zircon powders (size of 90% of particles is ≤23 μm)
at 230 °C. Approximately 90% of the zircon can be decomposed when
the digestion time exceeds 12 h and the reagent amount (300 mg) is 6
times the sample amount (50 mg). The main reason for the slow and
incomplete digestion of pure zircon powders was reported to be the
highly coordinated crystal structure and the formation of a diffusional
fluoro-silicate-zirconate boundary that retards the rate of decomposi-
tion. However, the authors also pointed out that a small component of
zircon in natural samples (e.g., natural levels in soils, sediments, and
rocks) could be successively decomposed, given adequate stoichio-
metric excess of the NH4HF2 reagent. Zhang et al. [11] likewise de-
monstrated successful zircon decomposition in milled granodiorite
certified reference material (GSP-2).
Research from Magaldi et al. [43] showed low recoveries of Zr and
Hf in granodiorite GSP-2 and granite G-2 (mean recoveries of ca. 70%)
when digested with NH4HF2 in a microwave oven even when providing
enough amount of HF. The reason for the low recoveries is not clear,
and more investigations are needed in the future.
3. Alkali fusion
Alkali fusion is a rapid and effective technique for the decomposi-
tion of rocks that contain refractory minerals [3]. Fusion of rock sam-
ples with appropriate flux results in the formation of glasses that are
readily soluble in acids or water and can be subsequently introduced
into an ICP-MS through conventional means. Decomposition efficiency
by fusion is greater than that by acid digestion mainly because of the
high fusion temperature (480–1200 °C). Common fluxes are alkali salts
including LiBO2, Li2B4O7, K2B4O7, KOH, K2CO3, NaOH, Na2O2, and
Na2CO3 [3,131]. Alkali fusion requires a high flux-to-sample ratio for
complete decomposition of the sample. This resulted in high blank le-
vels, TDS content, and matrix effects. To reduce the TDS and matrix
effect, the final sample should be diluted by large amounts of acids,
which consequently increases the detection limit for trace element
analysis. Moreover, some elements cannot be analyzed in fusion sam-
ples due to volatilization (Pb, Sb, Sn, Zn, and Cs) or contamination (Li
and B from fluxes). Polyatomic interferences are generated from the
fluxes of LiBO2/Li2B4O7 [10]. Alkali fusion is thus traditionally used for
the analysis of major elements, and only part of trace elements in
geological samples is determined by X-ray fluorescence (XRF), ICP-MS,
and ICP-OES.
As alkali fusion always leads to substantial contamination of the
analyzed material by introduction of salts, many efforts have been
made to minimize the amount of the flux. Park et al. [27] reported a
revised alkali fusion method using a mixed flux of LiBO2 + Li2B4O7 for
the determination of trace elements in geological samples. The low
ratio of flux to sample (2:1) was applied to fuse rock powders at 1020 °C
for 10 min. The fused products (glass beads) were grounded and di-
gested with HF + HNO3 + HClO4 in PTFE vessels. The limit of quan-
tification (LOQ) for thirty trace elements was comparable with that of
conventional open-vessel acid digestion due to the limited amount of
high-purity flux.
Sintering or fusion with sodium peroxide (Na2O2) was considered as
a promising tool for sample preparation, as it offers several advantages
over fusion with lithium borate compounds [132]. Na2O2 is a strongly
W. Zhang and Z. Hu
oxidizing alkali flux. Most minerals (zircon, tourmaline, cassiterites, or
chromites) found in silicate rocks can be rapidly decomposed by sin-
tering with Na2O2 at a temperature of 480 ± 20 °C. Low-temperature
sintering with Na2O2 causes slight risk of analyte loss. The sintered cake
can be easily dissolved in water. Hydrolysis of Fe and Ti precipitate and
entrain lanthanides and other trace elements, especially the high-field
strength elements [132]. This process results in a separation between
some trace elements and matrix elements (such as Na and Si). The final
solution then has a low salt content. With this procedure, Cotta and
Enzweiler [10] accurately determined a large number of trace elements
in the precipitates, including REEs, Ni, Sc, Co, Sr, Y, Ba, Zr, Nb, Cd, Sn,
Sb, Hf, Pb, and Th. However, quantitative recoveries of Ta, Rb, and U
were limited due to the variable co-precipitation efficiency. Bokhari
and Mersel [132] proposed an optimized Na2O2 sintering method for
geological samples. A long digestion time of 120 min was required if
refractory minerals (such as zircon and chromite) were present;
otherwise, samples without refractory minerals could be digested in
30–45 min. Fifty elements could then be determined through the
combination of the supernatant and the precipitates including Si, Ti, Al,
Fe, Mg, Ca, K, and P.
Silicate remains in the alkali fusion method. When the melt is
poured into an acidic media, soluble silicic acid monomers (Si(OH)4)
are formed, and they continually condense to form silica gels [133].
Silica gel is a colloidal solution of silicic acid and always used as an
adsorbent [134,135]. The presence of silica gel could carry down some
elements, and this leads to loss of these elements. In addition, the
condensation products of silica gel will reduce flow in the following
separation-purification processing [133]. To overcome this problem,
Michaud and Larivière [133] performed flocculation with polyethylene
glycol polymer to remove silica before the pre-concentration processing
of both actinides and strontium in the environmental solid samples. The
high-molecular-weight polymer can interact with colloidal and sub-
colloidal silica in the acidic aqueous solution (through hydrogen
bonding) and form a precipitate, called a floc. Using the optimized
procedure, most of silica gel can be removed (97–99%), depending on
the analyst matrix and the vessel used for flocculation.
A flux-free fusion technique was an alternative method to eliminate
the problems caused by the fluxes. The rock samples are melted directly
at 1300 °C to 1800 °C, and glasses are formed by rapid quenching.
Shimizu et al. [136] used a SiC electric furnace to fuse powdered
sample at 1500 °C or 1600 °C with regulated oxygen fugacity. The
formed glasses were digested with a HF + HClO4 mixture, followed by
ICP-MS analysis. Twenty-four trace elements can be quantitatively re-
covered, including Zr and Hf in the zircon-bearing granitic samples.
However, the determination of highly volatile elements such as Pb and
Tl was not feasible. Bao et al. [137] reported a new flux-free fusion
method using a closed boron nitride vessel at 1400 °C or 1600 °C for
1 min for intrusive rocks or extrusive rocks, respectively. The high
temperature and minimum duration of heating are sufficient to melt the
rock samples and suppress evaporation of the volatile elements. The
fusion glass fragments then were digested by a three-step acid treat-
ment in closed screw-top Savillex vials on a hot plate, including
HF + HNO3 + HClO4, HF + HNO3 mixtures, and HNO3 alone. Al-
though undissolved small zircon grains were still found in the grano-
diorite after high-temperature fusion at 1600 °C, the high recovery for
Zr and Hf can be achieved due to the effective acid digestion processes
in 6 h at 150 °C. Low procedural blanks were obtained. Thirty-six trace
elements were completely recovered in different rock reference mate-
rials, including the highly volatile Rb, Cs, and Pb. Moreover, Bao et al.
[138] used this preparation method to accurately determine the Hf-Sr-
Nd isotopic compositions in a series of geological rock reference ma-
terials.
4. High-pressure asher
In the 1980s, Knapp designed a new sample digestion system to
9
Spectrochimica Acta Part B 160 (2019) 105690
solve the problems encountered in the traditional polytetra-
fluoroethylene (PTFE) bomb digestion method, such as low decom-
position temperature and leak-related element losses or contamination
[139,140]. He used a pure quartz vessel instead of a PTFE bomb and
placed the quartz vessel inside an autoclave that could be filled with
nitrogen [139,140]. The quartz vessel can be operated at a pressure up
to 100 bar and at the maximum temperature of 320 °C. This digestion
system was called high-pressure asher by Knapp. Its initial main pur-
pose is for the digestion of various organic materials. After years of
development, the HPA technology has also been combined with mi-
crowave technology for the digestion of the biological materials [141]
or used to directly digest various geological samples [142–152]. Cur-
rently, commercial high-pressure digestion systems, for example, the
HPA and Multiwave 7000 (HPA + Microwave) (Anton Paar GmbH,
Austria), are available. The new HPA systems (HPAeS) withstand a
high pressure of approximately 130 bar and a digestion temperature of
300–320 °C. HPA-S has been widely used in the determination of highly
siderophile elements (HSE: Re and platinum group elements (PGE))
[142–147], strongly chalcophile elements (S, Se, and Te) [146–150], Os
isotope ratios [151], and Se isotopes [150,152] in ultrabasic or basic
rocks. The advantages of HPA-S are the low-level blanks, low detection
limits, and hence better precision in low-concentration samples [145].
Generally, inverse aqua regia is used to digest the samples because most
siderophile and chalcophile elements are considered to be mainly
hosted by base metal sulfides or oxides in mantle rocks [150]. More
rigorous digestion parameters are needed for highly siderophile ele-
ments, for example, digestion temperatures from 280 °C to 320 °C and
digestion pressures from 125 bar to 130 bar. However, a lower digestion
temperature of 220 °C is often used for SeSe and Te extraction together
with a lower digestion pressure of 100 bar. The digestion time for ele-
ment extraction in siderophile and chalcophile is variable and ranges
from 2 to 16 h depending on the sample types. Recently, studies have
indicated that some elements (e.g., Re, Pt, Pd, Ru, Se, and Te) could be
hosted inside the silicate minerals or glassy matrices of rock samples,
especially for basaltic rocks [150,153,154]. To improve the digestion of
the silicate minerals, an additional hot plate HF-desilicification step was
suggested [143,147,148,150,153,154].
In modern HPAeS, the quartz pressure vessel is replaced by a glassy
carbon tube so that HF can be used. Cotta and Enzweiler [10] reported
the complete digestion of rock samples containing refractory phases
using HPA-S with HF at 260 °C for 3 h, shortening considerably the
digestion time compared with that of conventional high-pressure acid
digestion. Wang et al. [155] used high-pressure acid digestion and HPA-
S digestion with HF-HNO3 to determine S, Cu, Se, Mo, Ag, Cd, In, Te,
Ba, Sm, W, Tl, and Bi in geological reference materials and carbonac-
eous chondrites. Both methods as described in Wang et al. [155]
yielded precise results, but HPA-S digestion provided higher digestion
efficiency. However, both studies reported encountering the formation
of insoluble fluoride precipitate during the HPA-S digestion process. A
combination of addition of Mg and evaporation with HClO4 was sug-
gested to eliminate the formation of fluoride precipitates [10]. More-
over, high blanks from glassy carbon vessels exist for some trace ele-
ments, for example, Mo [155]. Furthermore, glassy carbon vessels need
to be carefully handled, as they are fragile and expensive [155].
5. Preparation of geological samples for LA-ICP-MS
LA-ICP-MS is a powerful in situ micro-analytical technique for the
determination of major, minor, and trace elements as well as isotope
ratios in a wide variety of applications [2,156–158]. LA-ICP-MS pro-
vides several advantages, including the ability for multi-elemental
analysis, simple sample preparation, low blanks, and high-throughput
sample [2,159]. LA-ICP-MS not only permits the spatial characteriza-
tion of heterogeneities in solid materials with a high spatial resolution
[159–161] but also provides a means of whole-rock geochemical ana-
lysis (e.g., rocks, sediments, soils, and ores) [14,16,162–164]. LA-ICP-
W. Zhang and Z. Hu
MS is a micro-sampling technique. Production of a stable, homo-
geneous, and mechanically resistant target is a prerequisite for bulk
geological sample analysis by LA-ICP-MS. The pros and cons of LA-ICP-
MS are beyond the scope of this review but can be found elsewhere
[2,156–160].
5.1. Pressed powder pellets
The pressed powder pellet technique is a common method of sample
preparation for both XRF analysis and LA-ICP-MS. The pressed powder
pellet technique has several advantages including its simple and rapid
operation, flexible addition of internal standard elements or isotopic
spikes, and lack of volatile element loss. In recent years, an important
development of pressed powder pellet is the concept of ultrafine
powder. Summarizing the conclusion from previous studies, particle
size of the sample is the single most influential factor in controlling the
subsequent powder tableting, laser ablation behavior, sampling re-
presentativeness, and homogeneity of element or isotopic distribution.
Mukherjee et al. [14] concluded that small particle size, that is, < 10
μm, is a prerequisite for homogeneity and hence acceptable data
quality for micro-scale analysis. Moreover, granitic rocks or samples
containing refractory minerals such as zircon require extra grinding to
achieve grain sizes below 5 μm for better precision. Mechanical
grinding is still the most common approach to reduce particle size, al-
though there is a risk of contamination of the sample [162]. Dry milling
can reduce particle sizes to < 1 μm (20 min) but may result in loss of
volatile elements (e.g., Pb and Sn) due to overheating of the container
during grinding [165]. Wet milling has been used to avoid the heating
problem. Elaborated operating protocols of wet milling have been re-
ported, including ball-to-powder ratio, water-to-powder ratio, milling
time, and others. Research results indicated that for most rock samples,
30–45 min grinding with the planetary ball mill or the vibratory mill is
sufficient to reduce the particle size to below 10 μm [14,162–164]. The
mineral combination in the sample significantly affects the particle
grinding efficiency. It is more difficult to grind hard crystals (e.g., zir-
cons) in a soft matrix (e.g., feldspars or clay minerals) than grinding
mineral assemblages with a similar hardness [162]. After wet grinding
of granitoids, it was found that a small amount of large particles re-
mained [162,164].
The grounded powder is typically pressed to tablets with or without
binder. The addition of binder is considered to improve mechanical
resistance and cohesion of pellets. The cohesion of the test sample
played an important role in precision because the more compact the
pellet, the more reproducible was the laser–solid interaction [165].
Different substances have been investigated as binders including poly-
vinyl alcohol (PVA) [166,167], boric acid [168,169], Ag powder [170],
and vanillic acid [171]. However, sample dilution and contamination
are always concerning. Peters and Pettke [172] compared the effects of
six binders in the preparation of pressed powder tablets. Pellets bound
with graphite and PVA are very brittle. Poor repeatability was observed
when collagen hydrolysate was used. Microcrystalline cellulose (MCC)-
and vanillic acid-bound pellets had the smoothest ablation patterns, but
MCC was purer than vanillic acid and thus was chosen as the optimal
binder. The addition of 20% MCC did not significantly dilute the sample
and contaminate the element. Hennekam et al. [173] and Shaheen et al.
[174] applied high-purity epoxy resin to soak sediment powders or
basaltic rock powders for the preparation of rigid disks for LA-ICP-MS
analysis. To completely infiltrate the resin into the powders, a vacuum
impregnation device was applied to remove the interstitial air bubbles.
This method provided low-contamination disk with appropriate hard-
ness for LA-ICP-MS analysis. Rock samples and external standards can
be prepared simultaneously with the same process. However, the in-
troduction of resin leads to isobaric interferences with polyatomic ions
of carbon, for example, 40Ar12C on 52Cr, 12C12C on 24Mg, 12C18O1H on
31
P, and 23Na12C40Ar on 75As [174].
Because ultrafine powder offers good cohesive force, the nonbinder
10
Spectrochimica Acta Part B 160 (2019) 105690
pelleting method has become popular in recent years. The elimination
of binders simplifies sample preparation and avoids the potential risk of
elemental contamination. In some reports, ultrafine powder (< 10 μm)
pellets were reported to exhibit a very stable ablation signal that is
comparable to that of glasses [16,162]. However, Mukherjee et al. [14]
reported that the real-time signal fluctuation of a pressed pellet of ba-
salt powder standard (BHVO-2) was more severe than that of NIST SRM
612 glass. Wu et al. [164] also observed less stable transient signal in
pellets during laser ablation compared with fusion glasses. The less
stable signal of pellets can be attributed to the heterogeneous dis-
tribution of the polyphase minerals.
In summary, the pressed pellet prepared from ultrafine powder is
applicable for the analyses of 30–45 elements [162,164], independent
of whether a binder is used, in various geological samples (basic rocks,
intermediate-acidic rocks, granitoids, and sediments). The precision or
reproducibility (expressed in % relative standard deviation, RSD) of
repeated measurements is better than 5% for most major elements and
10% for most trace elements with concentrations higher than 1 μg g−1.
The analytical results of most elements were in general agreement with
the recommended values, with discrepancies typically < 10%. More-
over, some volatile elements (Hg) or trace elements not commonly
measured (flux elements like Li, B; chalcophile elements like As, Sb, Tl,
In, and Bi) also could be quantitatively analyzed [163,172].
However, the pressed powder pellet method has several short-
comings. First, the process of preparing a fine powder suffers the risk of
contamination, for example, from grinding reagents (water or ethyl
alcohol), abrasion of milling equipment (the milling ball and the milling
vial), pellet tableting procedure, or binder, if used [164]. Elements
reported to have susceptibility to contamination include B, Si, Cu, Zn,
Mo, W, and Pb [162,164,172]. Second, there is a nugget effect from
zircon and sulfides, even after the rock powder particle size is grounded
to < 10 μm or even to the nanometer level. Garbe-Schӧnberg and
Müller et al. [162] observed unstable Zr and Hf signals in the pellet of
granodiorite DR-N, which has a particle size of d50 < 1.5 μm. The
precisions of Zr and Hf (14% and 11%) were significantly degraded
than those of other elements (< 2–5% RSD), indicating the hetero-
geneous distribution of zircon in the pellets. Mukherjee et al. [14]
found that results of ultrafine powder pellets in granitic samples ex-
hibited the poorest precision for Zr, Hf, and some HFSEs, which are
generally associated with accessory zircon. Wu et al. [164] also re-
ported large RSDs for Zr, Hf, Th, and U in powder pellets from granitoid
rocks. The nugget effect of sulfides, which cause large discrepancies in
some of the chalcophile elements, was shown by Peters and Pettke
[172]. Therefore, further studies are needed to improve the pressed
powder pellet method.
Here, we once again propose the NH4HF2 digestion as a good sample
preparation method for the pressed powder pellet method. Zhang et al.
[16] found that the digestion products after NH4HF2 treatment were in
the form of ultrafine powder (d80 < 8.5 μm), allowing us to synthesize
pressed powder pellets without any binder (Fig. 3). In contrast to me-
chanical grinding, NH4HF2 digestion is a new strategy for pulverizing
and homogenizing geological samples by chemical means. Because of
the complete destruction of physical structures of silicate minerals by
NH4HF2 digestion, the nugget effect can be eliminated naturally. The
low process blank also can be achieved due to the purified NH4HF2
reagent.
5.2. Fusion glasses
Fusion glasses can be produced by alkali fusion or flux-free fusion.
The fusion product can be directly analyzed by XRF for major elements
and some trace elements and can also be measured using solution ICP-
MS after dissolution in dilute nitric or hydrochloric acids or with LA-
ICP-MS.
Alkali fusion is a conventional and efficient method to decompose
geologic samples that contain refractory minerals. Recently, Monsels
W. Zhang and Z. Hu
Fig. 3. SEM image of the NH4HF2 digestion products from BCR-2 (a); SEM image of surface and ablation crater on the pressed pellet of BCR-2 (b); laser ablation-
generated transient signals from the pressed powder pellet of BCR-2 (c). These figures are cited from Zhang et al. [16].
et al. [175] reported using lithium borate to fuse bauxites for the de-
termination of trace elements by LA-ICP-MS (sample:flux = 1:4). The
results showed that thirty trace elements were typically measured to
have within 20% of their reference values with an “external” precision
of < 20% (RSD), which confirmed the applicability of LA-ICP-MS after
lithium borate fusion for bauxite analysis.
However, the introduction of the flux agents dilutes the trace ele-
ment contents in samples, leading to increased limits of detection, and
causes inevitable contamination (e.g., Li and B) to the samples and the
ICP-MS instrument [156]. Park et al. [176] attempted to control the
amount of flux used in the production of fusion glasses for LA-ICP-MS
analysis. They compared normal (sample:flux = 1:5) and low-dilution
(sample:flux = 1:2) fusion methods for three USGS reference materials
(G-3 granite, AGV-2 and BHVO-2). The fused glasses from the low-di-
lution fusion method yielded reproducible and accurate results for 24
trace elements, including Zr and Hf. Zhang et al. [177] also used the
low-dilution fusion method to melt peridotites for trace element ana-
lysis using LA-ICP-MS. In fact, it is difficult to directly fuse peridotites
owing to their high liquidus temperatures (1725 ± 30 °C for garnet-
lherzolite and 1850 °C for dunite). Furthermore, peridotite melts cannot
be quenched to homogeneous glass owing to high MgO concentrations,
which lead to nucleation of olivine and other minerals. The authors
chose synthetic albite (NaAlSi3O8) as the flux agent (melting point at
1450 °C) to reduce the melting point of peridotite. The homogeneous
peridotite glasses were produced with albite heating at 1500–1550 °C
for 10–15 min with a sample-to-flux ratio of 1:2 (low-dilution fusion).
The albite flux did not introduce significant contamination except for
Ga, Rb, Ba and La.
The flux-free fusion method is another strategy for preparing fusion
glass. The principle is simple: the sample is directly fused at
1300–1800 °C and then rapidly quenched to form a homogeneous glass.
The development of this technology in recent years is focused mainly on
the choice of heat sources. Early studies used a self-made heater with
metal strips (W, Mo, and Ir) to rapidly melt the samples [178,179]. A
high-temperature furnace with a temperature control system is also
frequently used as the heat source [164,180]. Recently, Zhang et al.
[15] reported a new approach using a high-energy infrared laser to melt
the pressed pellet samples under optimized laser conditions (16 ms
pulse width and 5 pulse counts). In this study, fusion and instant
cooling take only tens of milliseconds for each sample, bypassing the
use of any chemical reagent or melting container (Fig. 4). Complete
fusion of rock samples was achieved, including intermediate-acidic in-
trusive rocks. In summary, current technologies can simultaneously
analyze more than forty major and trace elements in the flux-free fusion
glasses by LA-ICP-MS for different geological samples [13,15,180]. The
measured major elements matched the reference values to within
5–10%, and the measured trace element contents were generally
11
Spectrochimica Acta Part B 160 (2019) 105690
consistent with the reference values within 5–15%. The routine preci-
sion of fusion glasses was generally better than 5–10% (RSD).
How to suppress the loss of highly volatile elements (e.g., Zn and
Pb) and completely melt the refractory minerals in coarse-grained rocks
(e.g., granitoid) in the flux-free fusion methods are questions of interest.
The loss of highly volatile elements (Zn, Pb, Sn, and Ge) during fusion at
a high temperature was reported in cases where a metal strip heater or
high-energy infrared laser was used as the heat source. Zhu et al. [13]
suggested the use of a crucible of hexagonal boron nitride (h-BN) as a
capsule for the preparation of glass samples. Element volatilization
during high-temperature heating was effectively suppressed with the
use of the h-BN crucible. Bao et al. [137] also used the BN vessel and a
high-temperature furnace to prepare the fusion glasses for trace ele-
ments and Pb isotope ratio analysis. In addition, He et al. [180] em-
ployed a home-made Mo capsules with a graphite tube to load rock
powders. The results showed that volatile elements (e.g., Zn, Ga, Cs and
Pb) had a homogeneous distribution (< 10–20%) and could be quan-
titated, confirming the effectiveness of the sealing assembly to suppress
the loss of volatile elements. Wu et al. [164] selected a platinum cru-
cible with a lid to eliminate the depletion of volatile elements. How-
ever, significant losses of Pb and Sn were observed when the melting
time was > 2 h. In addition, it is difficult to completely melt the re-
fractory minerals with the flux-free fusion method, especially for
granites. He et al. [180] found the residual zircons in GPS-2 glasses
after fusion at 1600 °C for 35 min, resulting in heterogeneous distribu-
tions and the high RSD values (10–20%) for Zr and Hf. To solve this
problem, Wu et al. [164] designed a complex pretreatment scheme for
the melting of granite. They first melted the rock powders in a high-
temperature furnace at 1600 °C for 1 h. Next, the silicate melt was
quenched to glass and then ground in an automatic agate mortar for
15 min. The ground glass was melted again at 1600 °C for 1 h. The
grinding process significantly improved the homogeneity of the glass.
The RSD values of Zr and Hf in five granite reference materials were
better than 10%. However, one granite, JG-2, still had a relatively large
RSD values for Zr and Hf even after a total of 4 h of melting at 1600 °C
and two grinding steps. Complete fusion of zircon was reported by
Zhang et al. [15] with the use of a high-energy infrared laser to melt
rock powders. The interactions between laser and rock powders pro-
duce a sufficiently high temperature to melt the refractory minerals.
The recoveries of Zr and Hf in GPS-2 are high, indicating the complete
fusion of zircons. However, the relatively large RSD values of Zr and Hf
(~18%) confirmed slight heterogeneous distribution of these elements
in the glass. However, high losses (20–70%) of highly volatile elements
(Zn and Pb) are observed in the infrared laser fusion [15] (Fig. 4). The
infrared laser fusion technique has high development potential because
of its high efficiency and safe operation process, but the work to sup-
press the loss of volatile elements requires further research.
W. Zhang and Z. Hu
Fig. 4. Infrared laser fusion processes (a and b) and fused glasses of basalt reference materials (c and d).
In addition to the above-mentioned problems of volatile element
losses and refractory mineral residues, some other problems have been
observed in the current reported fusion glasses techniques. For ex-
ample, partial loss of transition metals (V, Cr, Co, Ni, and Cu) was re-
ported when a BN crucible was used as the container [13,137]. Re-
searchers thought that BN might reduce transition metal ions to their
metallic states owing to its strong reducing power at high temperature.
The metal segregation behavior could cause heterogeneity of some
transition metals in the fused glasses. Contamination during the fusion
process was also reported. The reactions between the melt and the fu-
sion container could lead to contamination of some metal elements (Cr,
Co, Cu, and Ni), especially for prolonged fusion process [164,180]. For
the alkali fusion methods, impure flux materials could be the main
contamination source for some elements such as Cr, V, Cd, and La, in
the lithium borate flux [175,177].
6. Conclusion
Sample decomposition is a fundamental and critical stage in the
process of geochemical sample analysis. Although the speed of ad-
vancements in conventional sample digestion methods lags behind the
development of modern instrumentation and analytical methods,
sample preparation methods are still the main tools for the elements
and isotopic ratio analysis in geological samples. The reagents NH4F
and NH4HF2 as a substitute of hydrofluoric acid in acid digestion are
important advancements in recent years. The NH4F/NH4HF2 open-
vessel acid digestion methods have been established and resolved the
fundamental problem of incomplete dissolution of refractory minerals
in conventional open-vessel acid digestion. Other advantages such as
easy purification, suppression of insoluble fluorides, simple and flexible
operation, low equipment and labor cost, and relatively safe property
make them suitable for geological sample preparation. LA-ICP-MS is a
fascinating technology for whole-rock elements and isotope ratio ana-
lysis in geological samples. Sample preparation methods for LA-ICP-MS
have received significant attention, such as ultrafine powder pellets and
fusion glasses. Nevertheless, the accurate bulk determination of trace
elements in some rock types (such as granite) was prevented due to the
heterogeneous element distribution in the analyzed samples. Therefore,
more works are needed to improve the sample preparation method to
meet the analytical requirements of natural geological samples.
We believe that the development and advancement of sample pre-
paration methods are mainly dependent on three important aspects.
The first is the innovation of modern instruments, which will change
the design thought and specific process of sample preparation methods.
For example, collision cell or high mass resolution technology in mass
spectrometers can effectively remove polyatomic isobaric interference.
12
Spectrochimica Acta Part B 160 (2019) 105690
This ability allows HCl, HClO4, H2SO4, or HPO3, which were previously
used with caution, to be considered again as sample digestion reagents
or solution media. If the problem of salt tolerance and matrix effect in
ICP-MS is solved in the future, the sample solution does not need to be
highly diluted (> 1000 times). The amount of sample thus can be sig-
nificantly reduced; of course, this must be accompanied by further re-
duction in the particle size of the sample powder to improve the re-
presentativeness. A smaller amount of sample and ultrafine powders
will reduce the consumption of digestion reagents and shorten the di-
gestion step and time, which is beneficial to the implementation of
automated digestion process. The second aspect is new element or
isotope analysis requirement. When new rock types or elements are
found to offer new information or important research meaning in earth
science, new sample preparation methods will also be rapidly devel-
oped to satisfy the needs of these specific sample or elemental analyses.
In this case, the research work often does not focus on efficiency but the
reliability of sample digestion to meet the requirements of high-preci-
sion and high-accuracy analysis. The third driving force for the devel-
opment of sample preparation methods is the actual production re-
quirements. A sample preparation method developed in a scientific
research laboratory is not entirely suitable for high-volume production
work, especially in the field of basic geological exploration and mineral
resource exploration due to the large number of samples to be tested.
The sample pretreatment method then is more concerned with the
optimization of the digestion process. The main evaluation indicators
are used to improve production efficiency, reduce labor intensity, re-
duce experimental cost, and eliminate environmental pollution as much
as possible. In summary, the development of sample preparation
methods should closely follow the progress of analytical instruments,
changes in scientific research content, and the actual production needs.
In addition, attention to new digestion reagents, new material-made
digestion vessels, and new experimental equipment can facilitate ad-
vances in sample preparation technology.
Acknowledgements
We are very grateful to Dr. George Chan and the two anonymous
reviewers for editorial work and constructive comments, which con-
siderably improved this manuscript. This research is supported by the
Chinese State Key Research and Development Program
(2016YFE0203000), the National Nature Science Foundation of China
(Grant No. 41603002, 41725013, and 41573015), the Science Fund for
Distinguished Young Scholars of Hubei Province (2016CFA047), and
the most special fund from the State Key Laboratories of Geological
Processes and Mineral Resources, China University of Geosciences
(MSFGPMR04 and MSFGPMR08).
W. Zhang and Z. Hu
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