Science of the Total Environment 715 (2020) 136810

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Science of the Total Environment

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

DGT: A promising technology for in-situ measurement of metal

speciation in the environment
Li Gao a,b, Bo Gaoa,b,⁎, Dongyu Xu b, Linghua Liu a,b
a
State Key Laboratory of Simulation and Regulation of Water Cycle in River Basin, China Institute of Water Resources and Hydropower Research, Beijing 100038, China
b
Department of Water Environment, China Institute of Water Resources and Hydropower Research, Beijing 100038, China

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

Article history: Toxicity, bioavailability, and mobility of a metal depend on its speciation rather than its total concentration. In
Received 17 November 2019 this discussion, we emphasize the need for field-based metal speciation analysis methods, given the flaws of tra-
Received in revised form 15 January 2020 ditional techniques. We express a science-based opinion that the diffusive gradients in thin-films (DGT) is a
Accepted 17 January 2020
promising and powerful technique for performing in-situ measurement of metal species or speciation in different
Available online 18 January 2020
environmental samples. Several limitations and challenges in further application of DGT are also highlighted in
Editor: Jay Gan this discussion.
© 2020 Elsevier B.V. All rights reserved.
Keywords:
Heavy metals
Environmental samples
In-situ measurement
Metal speciation
Diffusive gradient in thin-films (DGT)

1. Introduction 2. Traditional methods for measuring metal speciation

Heavy metal contamination is a severe global environmental prob-
lem because it is persistent, non-degradable, and irreversible. Heavy
metals not only degrade the quality of the atmosphere, water bodies,
soils, and sediments, but also threaten human health via the food
chain. As a matter of fact, the toxicity, bioavailability and mobility of a
metal depend on its speciation rather than its total concentration. Par-
ticular metal species have different toxicities and impacts on organisms.
For example, Cr(III) is poorly soluble and necessary for human health,
whereas Cr(VI) is highly mobile, carcinogenic, and mutagenic. The
quantification of specific metal species is therefore more important
than knowledge about their total concentration. Metal speciation anal-
ysis is not only crucial to environmental hazard risk-assessment, but
also to pollution remediation.
⁎ Corresponding author at: Department of Water Environment, China Institute of Water
Resources and Hydropower Research, Beijing 100038, China.
E-mail address: gaobo@iwhr.com (B. Gao).
Significant attention has been devoted to the measurement of metal
species in different environmental media (e.g. water, soil, and sedi-
ment). The most commonly used method involves analyzing samples
in the laboratory after field sampling. In water samples, metal species
are complexed and detected directly. For soils and sediments, metal
species are quantified in the laboratory using chemical extraction. Re-
garding the detection of metal species, a single species is detected
using spectrophotometry and atomic absorption. Multi-element species
are detected using electrochemical techniques (e.g., competitive-ligand
exchange-cathodic stripping voltammetry, absence of gradients and
nernstian equilibrium stripping) (Companys et al., 2017) and a combi-
nation of techniques (e.g., high-performance liquid chromatography
(HPLC) coupled with inductively coupled plasma mass spectrometry
(ICP-MS) (Timerbaev, 2013). However, these approaches are flawed
for the following reasons: (i) Ex-situ analyses. These procedures cannot
reflect the actual information on metal species; (ii) Metal species pres-
ervation. Even the most rigorous metal species prevention technique

https://doi.org/10.1016/j.scitotenv.2020.136810
0048-9697/© 2020 Elsevier B.V. All rights reserved.
2 L. Gao et al. / Science of the Total Environment 715 (2020) 136810

cannot completely prevent the on-going chemical and biological

changes that occur during sample collection, transportation, storage,
and processing, with the complete preservation of samples being nearly
impossible (Menegário et al., 2017); (iii) Insufficiently sensitive. These
methods are insufficiently sensitive in detecting metal speciation in nat-
ural environments, especially for samples having low metal concentra-
tions. (iv) Difficult comparison. The concentration of metal species in
solid media varies based on different extractants and experimental pro-
cedures employed, rendering the results from different laboratories
incomparable.

3. In-situ measurement of metal speciation using DGT

Owing to the above-mentioned limitations of the existing tech-

niques, there is a need for field-based metal speciation sampling and
analysis methods. Diffusive gradients in thin-films (DGT) is are a robust
in situ passive sampling technique for measuring labile components in
waters, soils, and sediments (Davison and Zhang, 1994; Kreuzeder
et al., 2015). Different species can be selectively accumulated using dif-
ferent binding gels. For example, Chelex-100 DGT can be used to detect
metal cations and ferrihydrite DGT can be used to detect oxyanions
(Garmo et al., 2003; Luo et al., 2010). DGT enables the measurement
of a time-weighted, rather than instant concentration of a wide range
of elements. Compared with traditional speciation techniques, DGT
can be performed in situ and detect dynamic, pre-concentrate analytes
at high resolution. DGT can be applied to soils and sediments where it
provides both equilibrium speciation and dissociation kinetics of com-
plexes. In addition, DGT has the advantage of being relevant to the bio-
available species (Zhang and Davison, 2015).
During its evolution, DGT technique has been used to measure metal
species in recent years, as a result of additional research. Some studies
have focused on alternative binding layers and the uptake of specific
species, with emphasis on the most toxic elemental species. Different
kinds of binding gels have been designed to accumulate metal species,
based on two approaches (Fig. 1): (i) selective binding of a species of
an element, followed by measurement using ICP-MS after elution Fig. 1. Two research ideas for metal speciation analysis using DGT.
(e.g., N-methyl-D-glucamine-DGT can be used to selectively bind Cr
(VI) (Pan et al., 2015) and (ii) simultaneous uptake of all chemical spe- both Sb(III) and Sb(V), Cr(III) and Cr(VI) (Fontanella and Beone, 2016;
cies of an element, after which these all species are eluted and separated Gao et al., 2019)? Although relevant studies have been published, the
using HPLC before being measured via ICP-MS. For example, dimethyl uptake and elution mechanisms require further clarification. (4) The re-
arsenate, monomethyl arsenate, and inorganic As(III) and As(V) can sults of the DGT performed on different batches are not consistent. As
be simultaneously accumulated by ferrihydrite-DGT (Österlund et al., DGT techniques have evolved over more than twenty years, the tradi-
2012) and ZrO-DGT has been used to measure both Cr(III) and Cr(VI) tional DGT types such as Chelex-100 DGT and Fe-oxide DGT have
(Gao et al., 2019). shown stable performance. In contrast, some of the newer binding
gels used have not produced stable performance. Further improvements
4. Existing limitations of metal speciation analysis using DGT are needed to produce more consistent performance of binding gels.
(5) The commercialization of DGT has only included a few types (such
Although DGT is already used in in-situ metal speciation analysis, as Chelex, Fe-oxide, Zr-oxide DGT). Most researches on in situ metal
some problems also exist, that limit its popularization and application. speciation analysis using DGT has been performed with individually
(1) The differences in concentrations of the various species. The huge produced DGT devices (Bennett et al., 2011; Hong et al., 2011;
difference of species concentration poses a challenge to the metal speci- Devillers et al., 2016; Li et al., 2006; Pelcová et al., 2015). This is not con-
ation detection. For the same dilution rate, low-concentration species ducive to its widespread adoption and application.
was under the detection limit. (2) A lack of quality assurance. The lack
of standard operating procedure and standard materials for DGT mea- 5. Challenges and prospects of metal speciation analysis using DGT
surement pose a challenge for quality control. Although there are oper-
ating instructions provided by Zhang (2003), they are not standardized. Although DGT has successfully been applied for the in situ speciation
Different studies may be produce different results for the same samples. detection of several elements (e.g., As, Sb, and Cr), various challenges
In the absence of standard materials, it's difficult to distinguish the accu- and research directions need to be addressed in future research. First,
racy of the results obtained. (3) The mechanisms of uptake and elution binding gels materials. New binding gels need to be developed to accu-
are not clear. For example, why does ferrihydrite-DGT uptakes all four mulate other target species stably and selectively. Second, kinetic pro-
kinds of As species, why does Fe-oxide DGT uptakes Sb(III) and Sb cess of metal species. The dynamic model (DGT induced fluxes in
(V) simultaneously, why does Zr-oxide DGT uptakes Cr(III) and Cr(VI) sediments and soils, DIFS) does not take metal speciation into consider-
simultaneously (Fontanella and Beone, 2016; Devillers et al., 2016)? ation, Hence, a dynamic model for metal species needs to be established,
The accumulation mechanism of the binding gel with regard to metal and the labile pool size and dissociation rate of different metal species
species is still unclear. Similar to uptake, the elution mechanism is also from the solid phase to the solution phase in soils and sediments should
unclear. For example, why can EDTA be used as the eluent to extract be determined. Third, predicting toxicity and bioavailability. Based on
 L. Gao et al. / Science of the Total Environment 715 (2020) 136810
toxicity tests, the corresponding relationship between DGT and metal
biotoxicity to bioindicator animals/plants in different environmental
conditions needs to be established. Subsequently, environmental
standards regarding labile metal concentrations can be advanced.
Fourth, method standardization. A standard procedure for sample
collection, pretreatment, and analysis should be established, to aid the
expansion of the use of the DGT technique and enable the results from
different laboratories to be compared. Taking all these issues into
consideration, DGT has promising application prospects in metal
speciation analysis.
6. Conclusion
Metal speciation is related to its mobility and toxicity. Therefore,
metal speciation analysis is crucial to environmental hazard risk-
assessment and pollution remediation. Metal species can change during
the traditional ex-situ sampling, transportation, and analysis. As an in-
situ technique, DGT has been successfully used for metal speciation
analysis. Despite its success in-situ metal speciation analysis, it has
several limitations and faces several challenges. We believe that DGT
can be a promising technique for measuring the chemical speciation of
heavy metals in different environmental samples, which could
ultimately aid the control, reduction, or elimination of heavy metals
contamination.
Declaration of competing interest
The authors declare that they have no known competing financial
interests or personal relationships that could have appeared to influ-
ence the work reported in this paper.
Acknowledgments
This work was supported by National Natural Science Foundation of
China (41977292, 41773143, 51879280), the Special Fund Projects of
State Key Laboratory of Simulation and Regulation of Water Cycle in
River Basin, China Institute of Water Resources and Hydropower Re-
search (SKL2018TS03), and the Research & Development Support Pro-
gram of China Institute of Water Resources and Hydropower Research
(WE0145B662017, WE0145B072019, WE0145B062017).
3
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