Critical Reviews in Analytical Chemistry

ISSN: 1040-8347 (Print) 1547-6510 (Online) Journal homepage: http://www.tandfonline.com/loi/batc20

A review on recent applications of high

performance liquid chromatography in metal
determination and speciation analysis

Heena , Susheela Rani, Neha Sharma & Ashok Kumar Malik

To cite this article: Heena , Susheela Rani, Neha Sharma & Ashok Kumar Malik (2017):
A review on recent applications of high performance liquid chromatography in metal
determination and speciation analysis, Critical Reviews in Analytical Chemistry, DOI:
10.1080/10408347.2017.1343659

To link to this article: http://dx.doi.org/10.1080/10408347.2017.1343659

Accepted author version posted online: 23

Jun 2017.

Submit your article to this journal

View related articles

Full Terms & Conditions of access and use can be found at

http://www.tandfonline.com/action/journalInformation?journalCode=batc20

Download by: [The UC San Diego Library] Date: 24 June 2017, At: 02:10
ACCEPTED MANUSCRIPT

A review on recent applications of high performance liquid chromatography in metal

determination and speciation analysis

Heena, Susheela Rani, Neha Sharma and Ashok Kumar Malik*

Department of Chemistry, Punjabi University, Patiala-147002, India

*Corresponding author: e-mail: malik_chem2002@yahoo.co.uk

Abstract

High performance liquid chromatography has several advantages over the conventional methods

due to their operational simplicity. It is a vital tool to determine metal ions having same mass but

different electronic configuration, to separate complex mixtures and to resolve ions that may be

indistinguishable by mass spectrometry alone. Metal ions play vital role in many biological

processes and involved in setting up of many diseases. Therefore the development of simple

methods for the detection and quantification of metals in real samples might serve as diagnostic

tools for various diseases. This review article focuses on the recent main feature of this technique

i.e. speciation of metal ions and their applications to series of problem of metal ion chemistry in

different environmental matrixes. Speciation of metals is of increasing interest and has a great

importance because of bioavailability, environmental mobility, toxicity and potential risk of

metals. With the capability of partitioning the complex species of different metal ions, high

performance liquid chromatography (HPLC) is an efficient technique for this task. This review

summarizes recent advances in the development of HPLC to the fundamental understanding of

metal ion chemistry in the environment and discusses all the issues that still need a lot of

1
ACCEPTED MANUSCRIPT
ACCEPTED MANUSCRIPT

consideration. It has been classified in to different sections depending on the role of HPLC in

separation used and metal speciation furthermore, the underlying sample preconcentration

techniques and detection systems involved for the determination of metal ions and their

applications were discussed.

Keywords: Speciation; Organic ligands; Preconcentration methods; HPLC; Metal ions;

complexation

2
ACCEPTED MANUSCRIPT
ACCEPTED MANUSCRIPT

Abbreviations

AAS Atomic Absorption Spectrometry

ACN Acetonitrile

AES Atomic Emission Spectrometry

APDC Ammonium Pyrolidine Dithiocarbamate

AsC Arsenocholine

AsB Arsenobetaine

CE Capillary Electrophoresis

CPE Cloud Point Extraction

CTAB Cetyl Trimethyl Ammonium Bromide

DDTC Diethyl Dithiocarbamate

DLLME Dispersive Liquid-Liquid Microextraction

DMAA Dimethyl Arsinic Acid

DNTB 5,5’-Dithiobis-(2-Nitrobenzoic Acid)

DZ Dithizone

EDTA Ethylenediammine Tetraacetic Acid

3
ACCEPTED MANUSCRIPT
ACCEPTED MANUSCRIPT

FLD Fluorescence Detector

HPLC High Performance Liquid Chromatography

HPLC-IP High Performance Liquid Chromatography-Ion Pair

HPLC-AEC High Performance Liquid Chromatography-Anion Exchange

Chromatography

HPLC-CL High Performance Liquid Chromatography-Chemiluminiscence

HG-AFS Hydride Generation-Atomic Fluorescence Spectrometry

HF Hollow Fiber

8-HQ 8-Hydroxyquinoline

ICP-MS Inductive Coupled Plasma-Mass Spectrometry

LC-MS Liquid Chromatography-Mass Spectrometry

LLME Liquid-Liquid Microextraction

LOD Limit Of Detection

LOQ Limit Of Quantification

LPME Liquid Phase Microextraction

MDTC Morpholinedithiocarbamate

4
ACCEPTED MANUSCRIPT
ACCEPTED MANUSCRIPT

MMA Monomethyl arsenate

MeOH Methanol

PAR 4-(2-Pridylazo)resorcinol

PDA Photodiode Array

PDTC Pyrolidine dithiocarbamate

PMDTC Pentamethylene dithiocarbamate

PTFE Polytetrafluoro Ethylene

RSD Relative Standard Deviation

RP Reverse Phase

Secys Selenocysteine

Semet Selenomethionine

SDME Single Drop Microextraction

SPME Solid Phase Microextractioon

SPE Solid Phase Extraction

SLM Supported Liquid Membrane

TAN [4-(2-Thiazolylazo)-1-napthol)

5
ACCEPTED MANUSCRIPT
ACCEPTED MANUSCRIPT

THF Tetrahydrofuran

TFA Trifluoroacetic Acid

TDNT Titanium Dioxide Nanotubes

ODS Octadodecyl Silica

UV Ultraviolet

Introduction

Toxic metal ions represent a threat to human health and to the surrounding environment

and this toxic nature of metals sometimes imitates the action of essential elements in the body,

by interfering with the metabolic processes to cause illness (Frausto et al., 2001;). Majority of the

toxic pollutants are waste products of industrial and metallurgical operations and is a major

threat aggravated by the low mineral content of most of our food supply. Therefore, this increase

in metal concentration is an important environmental issue and needs careful monitoring of the

trace element concentration in body and tissues to maintain the homeostasis.

Nowadays various metals like Hg, As, Pb, Be, Cr, V, Ni, Cu, As and Se, etc are major

threat to environment. Among these lead and mercury are of the greatest concern in the urban

atmosphere whereas other toxic metals found predominantly as particulate matter in polluted

atmosphere are known to be hazardous to human health (Manahan, 2000;). However Cd, Cr, Ni,

Cu, Hg, Zn are known as immediate concern to environment according to WHO sayings

(Pytlakowska et al., 2013). So metal determination being a needful aspect in a complex matrix is

usually very complicated despite of modern analytical instrumentation availability and adequate

6
ACCEPTED MANUSCRIPT
ACCEPTED MANUSCRIPT

sensitivity. Such complicated cases of determination should be proceeded through

preconcentration steps which enables minimizing/eliminating matrix effects and contaminants

and lowers the detection limit of many metals by liquid chromatography and increases the

detectability for others.

Due to strong environmental impact of metal ion determination speciation has received

particular attention in last few years. Within the past decades, the term “speciation” has become

increasingly important in the field of toxicology, geochemistry, environmental chemistry and

analytical chemistry (Bernhard et al., 1986;). The chemical form of speciation is essential for

discussing chemical reactivity of trace metal constituents in the environment such as biological

and geochemical behavior of chemical species and aims for identifying the quantities of one or

more individual species in a sample whereas speciation of metal aims to know the quantification

and distribution of element among defined chemical species (Adamu et al., 2013;).

There is a need of complexing agent in order to make the metal ion UV sensitive so that

we can easily determine the proportion of metal ion present in a particular composition. Apart

from their importance in the materials and catalysis areas, metal ions and their complexes play an

important role in vital functions of living organisms. Literature reveals that traditional methods

of sample preparation are typically time consuming, employ multistep procedures having high

risk for loss of analytes and use of extensive amounts of organic solvents (Farajzaden et al.,

2010;). Therefore there is a demand of special attention on the techniques which are

characterized by a considerable reduction of organic solvents and overcome the drawbacks of

previous ones. A various unconventional LLE methodologies have been reported like single drop

7
ACCEPTED MANUSCRIPT
ACCEPTED MANUSCRIPT

microextraction (SDME) (Kokosa, 2015;), solid phase extraction (SPE) (Turker, 2012;), cloud

point extraction (CPE) (Lopez-Garcia wt al., 2015;), solid phase microextraction (SPME)

(Chahal et al., 2012;), liquid phase microextraction (LPME) (Martinis e al., 2010; Wei et al.,

2003;) and dispersive liquid-liquid microextraction (DLLME) based on solidification of a

floating organic drop (DLLME-SFO) (Miro et al., 2005; Anthemidis and Loannou, 2009).

HPLC is greatly acknowledged as the most versatile, useful and sensitive method for the

separation and determination of species present in chemical mixtures. This investigation effort

provides a review involving the determination, preconcentration and speciation of metal ions in a

various sample matrices (aqueous environmental samples, urine, blood etc) via reversed phase

ion interaction and chelation chromatographic separation. This review focuses on HPLC oriented

work coupled with different detectors that involves the complexation of metals with ligands

before injection into the HPLC system.

Role of HPLC in separation and determination of different metal ions

HPLC has become the most flexible tool for separating the different species and its

coupled behavior with different detectors enables the determination of specific metal ions. HPLC

is widely used technique for the separation, determination in the preparation of organometallic

compounds and metallic co-ordination compounds and has gained considerable popularity in this

field due to its rapid performance under ambient temperatures and also prevent the metal

complexes from contacting the atmosphere and light (Harrington, 2000; Kuba et al., 2005;).

However other techniques are also known for the same purpose, like CE is more effective,

efficient, simple and low sample injection but the biggest problem with CE is its reproducibility

8
ACCEPTED MANUSCRIPT
ACCEPTED MANUSCRIPT

and the higher detection limit compared to HPLC. Another limitation which led to less use of CE

is its production by only a few companies which results in its much higher price than HPLC. The

other most widely used instruments (e.g. Atomic absorption and inductively coupled plasma

atomic emission spectrometers etc) used for metal determination suffers from both spectral and

chemical interferences and even not suitable for studies on metal speciation.

The first reported use of HPLC for the separation of organometallic compounds was

made by Veening et al in 1969 (Veening et al., 1969). The reversed-phase (RP) high-

performance liquid chromatographic (HPLC) technique with pre-column derivatization proved to

be a reliable technique for the separation and determination of trace amount of metal ions. Many

reagents (such as 8-quinolinol derivatives, azo dyes, β-diketones, hydrazones, dithiocarbamate,

cyclohexanediamine, dithizone and porphyrin) have been examined as pre-column derivatization

reagent (Heena et al., 2015; Daud and Alakili, 2001; Kaur and Malik, 2007; Lu et al., 2015).

During the past few years, the rapid developments of detection techniques have made it suitable

for the separation and determination of metal complexes.

Regarding future research trends and development in this rapidly expanding field, it is

ensured that HPLC attains the status of a comprehensive analytical technique for the

determination of metal complexes. The process of metal complexation commonly known as

chelation is an important which influences the mobility and solubility of heavy metal ions. This

process involves the formation of two or more separate coordinate bonds between a polydentate

ligand and a central metal atom. Strong metal complexes with organic ligands had been

recognized before 1980 (Hirose, 1994) and to characterize this complexation the most important

9
ACCEPTED MANUSCRIPT
ACCEPTED MANUSCRIPT

parameter is the stability constant, which is thermodynamically unique for a complex between a

metal ion and an organic ligand. Various complexing agents results from chelation process, such

as diphenylthiocarbazone (dithizone), dithiocarbamate, cupferron, and 8-quinolinol (oxine), can

be used for the determination of a large variety of metal ions using chromatography in

combination with expensive techniques like integrated coupled plasma-mass spectrometry (ICP-

MS), ion chromatography-ICP-MS, flame atomic absorption spectrophotometry (AAS), capillary

electrophoresis and ICP-AES. Table 1 summarizes many of the HPLC applications in the

analysis of metal complexes and an attempt has nailed for the speciation of different

organocompounds such as organomercury, organotin, organoselenium, organochromium by

using chromatographic techniques.

2. Metal Speciation

In the last decades speciation of metals has increased considerable interest due to their

toxicity and mobility dependence on the oxidation state of metal ion (Turker, 2012;). Speciation

of elements is important for two main reasons the one is biological which includes the

bioaccumulation, bioconcentration, bioavailability, toxicity and the other is geochemical which

includes transport, adsorption and the precipitation of element (Pan et al., 2010;). Any variation

in the chemical species defines the toxicity and essentiality of analytes and this information is

very much crucial for toxicological and environmental investigations. Thus, speciation analysis

is integral for the determination of metal ion in a specific matrix and it can only be achieved by

the combination of two different techniques where one is providing an efficient and reliable

separation procedure and the other is detection and quantification (Tchounwou et al., 2012;).

10
ACCEPTED MANUSCRIPT
ACCEPTED MANUSCRIPT

Appearance of different toxic heavy metal will depend on the chemical nature of given heavy

metal, environmental conditions, presence of chelating ligands, colloid dispersion, etc (Wuana

and Okieimen, 2011).

For understanding of properties of speciation, i.e., the determination of the individual

physico-chemical forms in which the element occurs, provides the necessary detailed

information (Gomez and Callao, 2006;). Toxicity dependence speciation is now well known and

metal behaviour may be completely changed by its oxidation state or its association with specific

ligands. Exemplified by the contrasting toxicities of methyl mercury, inorganic mercury species

or arsenic(III) and arsenic(V) species (Fang et al., 2016;). The metalloid tin also shows markedly

different health threats depending on its association with specific ligands. Metallic and inorganic

form of tin does not present any health threats whereas organotin compounds which are created

by human industrial processes are highly toxic in nature.

Speciation studies of some metal ions

Selenium

Selenium is considered one of the most relevant an essential element for health but at the same

time, it can be potentially toxic at higher doses. There is increasing interest in the availability of

techniques to determine organoselenium compounds at low concentrations as it has fruitful

importance in the field of medicine and nutrition. Selenium is known to develop its biological

activity via selenocysteine residue in the catalytically active centre of selenoproteins (Falandysz,

2008;) as well its speciation in mainly edible mushrooms has been collected in europe by Ferri et

al (Ferri et al., 2007;). Speciation of some other organic selenium compounds like

11
ACCEPTED MANUSCRIPT
ACCEPTED MANUSCRIPT

selenomethonine, selenocystine has also been reported in literature (Pedrero and Madrid, 2009;

Gosetti et al., 2007;)

Various methods have been developed for the speciation of selenium in environmental as well as

biological samples. Wrobel et al (Wrobel et al., 2004;) developed the mass spectrometry

detection method to study the speciation of selenium in selenium enriched onion leaves.

Yingying et al (Su et al., 2008;) developed a novel HPLC-UV/ Tio2-chemiluminescence system

for the determination of selenocysteine (Secys) and selenomethionine (Semet). This method was

applied for the simultaneous determination of Secys and Semet in real samples examined

preliminary in rabbit serum and garlic samples in the presence of Co2+, Secys and Semet can be

decomposed rapidly by UV radiation on the surface of nano-Tio2 immobilized on the inner

surface of PTFE tube.

Chromium

Chromium is the most controversial element among heavy metal ions that exist in two different

oxidation states i.e., trivalent chromium; Cr(III) and hexavalent chromium; Cr(VI) (Cervantes et

al., 2001;). Cr(III) ion is an essential nutrient that maintains a glucose tolerance factor in human

body (Vincent, 2014;) and involved in mechanism of action of pancreatic insulin (Pyrzynska,

2012;). Cr(VI) ion is toxic and does not occur naturally and is introduced to the environment by

various kinds of manufacturing units such as plastics, dyes, ink, metal casting and paint

industries (Rakhunde et al., 2012;). Discussions of the chromatographic techniques with

preconcentration for the chromium can be found in literature on CPE (Markiewicz at al., 2015;

Wang et al., 2007; Liang and Sang, 2008; Altunay et al., 2017; Samaddar and Sen, 2014). The

12
ACCEPTED MANUSCRIPT
ACCEPTED MANUSCRIPT

different oxidation states of a particular metal ion possess different physical and chemical

properties and have different toxicities. In order to study the toxicity, bioavailability,

bioaccumulation and transport of trace elements it is necessary to have more information about

the pH, temperature rather than the total concentration.

Chen et al (Chen et al., 2014;) used titanium dioxide nanotubes (TDNTs) as a solid phase

extraction adsorbent for chromium species by a packed micro-column coupled with inductively

coupled plasma mass spectrometry (ICP-MS), including total, suspended and soluble chromium

as well as Cr(III) and Cr(VI) in tea leaves and tea infusion. Chromium species has also been

determined by Wang et al (Wang et al., 2010;) in lake sediments after preconcentration by cloud

point extraction (CPE) and by Chehrehghani et al (Chehrehghani et al., 2014;) in water samples

after preconcentration by dispersive liquid-liquid microextraction (DLLME). Kaur et al (Kaur

and Malik, 2009;) has developed high-performance liquid chromatographic method with UV

detection, based on chelation with morpholine-4-carbodithioate (MDTC), for the speciation of

chromium. Another simple and rapid method for the simultaneous determination of Cr(VI) and

Cr(III) based on the formation of their different complexes with ammonium pyrrolidine

dithiocarbamate (APDC) has been developed by Hossain et al (Hossain et al., 2005;). The

relative standard deviations of peak areas in five measurements using a sample solution of 200

µgL1 are less than 2% for Cr(VI) and 4% for Cr(III), indicating good reproducibility for this

analytical method applied to the various synthetic waste water containing heavy metal ions.

2.1.2 Arsenic

13
ACCEPTED MANUSCRIPT
ACCEPTED MANUSCRIPT

Exposure to arsenic (As) is a global public health concern due to the wide distribution in

environment of arsenic and its close association with numerous adverse effects. Arsenic

speciation has become increasingly important and received considerable attention due to the

ubiquitous presence in environment and the high toxicity and carcinogenicity to organism of the

arsenic compounds (Frumkin and Thun, 2001;). The toxicity and carcinogenicity of arsenic

compounds depend not only on the total concentration but also on the different arsenic species

(Pizarro et al., 2003;). The forms of arsenic subjected to speciation analysis are anions e.g.

arsenite As(III), arsenate As(V), monomethyl arsonate(MMA), dimethyl arsinate(DMA) or

cations e.g., arsenobetaine (AsB), arsenocholine (AsC) or uncharges compounds at neutral pH

e.g. arsenous acid for arsenic speciation (Hymer and Caruso, 2004;).

Wang et al (Wang et al., 2010;) has been developed a novel method to detect two organic arsenic

animal feed additives including roxarsone and p-arsanilic acid, as well as other arsenic species

such as arsenite, dimethylarsinic acid, monomethylarsonic acid, arsenate, and 4-

hydroxyphenylarsonic acid, by using HPLC coupled to an inductively coupled plasma mass

spectrometer (HPLC-ICP- MS). Liquid chromatography coupled to tandem mass spectrometry

(LC-MS/MS) was used as an assistant tool to screen arsenobetaine (AsB) in the feed samples.

Narukawa et al (Narukawa et al., 2014;) investigated arsenic (As) species present in rice flour

samples using different extracting solvents, and the concentration of each species was

determined by HPLC-ICP-MS after heat assisted extraction. The extraction efficiencies for total

arsenic species and especially for arsenite [As(III)] and arsenate [As(V)] were investigated. Here,

the author also reported a heat block extraction method using a dry heating block system with

14
ACCEPTED MANUSCRIPT
ACCEPTED MANUSCRIPT

0.15 mol L1 HNO3 and water as the extracting solvents, and the method has been assessed by

application to actual rice flour samples.

Recently Carioni et al (Carioni et al., 2017;) has provided important information for

epidemiological studies by the speciation analysis of arsenic in urine samples containing low

level of As by LC-ICP-MS. Method was also established by Zmozinski et al (Zmozinski et al.,

2015;) for arsenic species determination in sea food. The extraction of arsenic (As) species

present in different samples was investigated using various extracting solvents and the

concentration of each species was determined by HPLC-ICP-MS after heat assisted extraction.

The extraction efficiencies for total arsenic species and especially for arsenite [As(III)] and

arsenate [As(V)] were investigated (Amaral et al., 2014; Marcinkowska et al., 2015; Cao et al.,

2014;).

3. Sample pretreatment for metal ion analysis

Sample pretreatment/preconcentration is showing much importance to ensure the generation of

an accurate and precise data. After the optimization of the separation and detection conditions,

the developed LC method can be directly applied to the real-sample analysis. Some of the

samples don’t need any pretreatment other than dilution or filtration. Some of them like soil

sample, alloys, creams, milk etc need specific sample preparation for elemental speciation and

determination.

3.1 Sample Pretreatment

The separation/preconcentration step is the most important step for the purification of

samples and determination of trace metal ions. Preconcentration of analytes may be defined as

15
ACCEPTED MANUSCRIPT
ACCEPTED MANUSCRIPT

collection of the analytes from the large volume of a solvent to a smaller volume of the solvent.

In preconcentration technique, elution or desorption procedure follows the separation step and

proves an effective way for enriching the target analytes. In order to achieve higher PF the eluent

volume should be as small as possible and the sample solution volume should be as high as

possible. Separation of the trace metals from the drinking water, river water, ground water, tap

water has been widely applied to the purification of these samples. Inspite of availability of

various modern analytical instrumentation techniques, the determination of trace amount of

metals in complex matrix is usually complicated. In such matrices, determination should be

proceeded by separation and preconcentration steps prior to HPLC analysis. Several of the off-

line techniques listed below can be employed not only to remove the interferences from the

complex matrix but also to concentrate the samples.

Dispersive liquid liquid microextraction was used to preconcentrate various types of

metal complexes and used for the subsequent analysis with HPLC [117-122]. Razmisleviciene et

al (Razmisleviciene et al., 2011;) and Asghari et al (Asghari et al., 2014;) has developed ionic

liquid-based DLLME combined with liquid chromatography for the determination of metal ions.

Cloud-point extraction (CPE) has also become an attractive area of research due to its easy, safe,

rapid, environmental friendly and inexpensive methodology for preconcentration and separation

of trace metals from aqueous solutions. Watanabe and coworkers in the early 1980’s (Watanabe

and Tanaka, 1978; Watanabe et al., 1987; Watanabe et al., 1992;) were the first to study this

effective pre-concentration technique of low cost, simplicity and lower toxicity to the

environment. Cloud point Extraction can be used for the preconcentration and extraction of

various inorganic species. After complexation, analyte ions are extracted in Triton-X-114,

16
ACCEPTED MANUSCRIPT
ACCEPTED MANUSCRIPT

followed by centrifugation. It is an alternative technique of liquid-liquid extraction and is applied

for the analysis of real samples (Mohsen Nia et al., 2009;). Different oxidation states of some

metals and metalloids namely Cr(VI, III) (Chen et al., 2009; Tang et al., 2004;) can be separated

by using this method. Another simple, inexpensive sample preparation technique SPME which

involves the use of a fiber coated with an extracting phase, that can be a liquid (polymer) or a

solid (sorbent), which extracts different kinds of analytes from different kinds of media of liquid

or gas phase. The most important stage is Sorption of analyte on a suitably coated silica fiber or

stationary phase. In case of SPME-HPLC, the analytes are thermally desorbed into the injector of

the chromatograph (Malik et al., 2006;). The methods using SPME techniques save preparation

time, solvent purchase, disposal cost and can improve the detection limits. Yates et al (Yates et

al., 2002;) has elaborated the conducting polymer film system, that can offer analytical

applications for the convenient preconcentration and subsequent analysis of neutral

environmental species. Another one of preconcentration technique is Solid phase extraction that

offers a number of important benefits. SPE is probably the most widely adopted technique for

preparing samples in the analysis of toxic metal ions. The large variety of commercially

available sorbents makes this technique suitable for the determination of analytes. As a result

current research focuses mainly in the development of novel sorbents allowing higher loading

capacities, higher efficiency for the retention of highly polar analytes from the aqueous matrices

(Latorre et al., 2013;). It is also applicable in the synthesis of class-selective immune-sorbents

(ISPEs) and molecular imprinted polymers (MIPs) for the improved selectivity during the

retention process. SPE involves partitioning between the liquid and a solid phase whereby

intermolecular forces between the phases influences retention and elution. It was performed

17
ACCEPTED MANUSCRIPT
ACCEPTED MANUSCRIPT

using a vacuum manifold from Supelco (Bellefonte, PA, USA). Procedures are used not only to

extract traces of organic compound from environmental samples but also to remove the

interfering components of the complex matrices in order to obtain a cleaner extract containing

the analytes of interest (Latorre et al., 2013;).. SPE is a convenient approach for the sample

preparation in the chromatographic analysis of edible fats as it requires a small amount of the test

sample, low volumes of organic solvents and the treatment by this is accomplished in a greatly

shorter period of time than any other technique (Buszewskia and Szultkaa, 2012;). Xiong et al

(Xiong et al., 2008;) used an SPE-microcolumn packed with a new sorbent, a

cetyltrimethylammonium bromide (CTAB)-modified alkyl silica, for the preconcentration of

Se(VI) and its separation from total selenium. Hashempur et al (Hashempur etal., 2008;)

elaborated a highly sensitive and accurate method for preconcentration and determination of ultra

trace amounts of inorganic mercury and organomercury compounds in different water samples is

proposed. LPME emerged from liquid-liquid extraction (LLE), which is another most popular

sample-extraction procedure in organic and inorganic analysis. LPME techniques overcome the

main disadvantages of LLE, such as a relatively long time of analysis, high consumption of

solvents and its tedious application. For the evolution of analytical chemistry towards

automation, miniaturization and simplification, new extraction procedures based on the LPME

principles were introduced recently for inorganic analysis (Herrador et al., 2011; Stanisz et al.,

2014;)

Detection Systems

In the recent decades, the commercial use of metals and organometallic compounds has

increased. This leads to a direct interaction of metals with the environment and cause toxicity

18
ACCEPTED MANUSCRIPT
ACCEPTED MANUSCRIPT

problems. Identification and determination of different metal ions using HPLC technique

coupled with a specific detector makes determination and speciation more reliable, improves the

sensitivity. Different used hyphenated detectors are described below.

4.1 Inductively coupled plasma mass spectrometry

From the last two decades, inductively coupled plasma-mass spectrometer (ICP-MS) detector

developed by Houk and Gray research groups (Houk et al., 1980; Date and Gray, 1981;)

constitute an important feature of considering the toxicity of some metal compounds and

provides the best level of sensitivity. The ICP-MS detector, when coupled with high performance

liquid chromatography (HPLC), offers the versatility of determination for both organic and

inorganic metal compounds. ICP-MS offers several advantages for speciation analysis detection

over other traditional detectors including: multi-element and multi-isotope detection. It shows

high sensitivity along with a wide linear dynamic range of detection (Timerbaev, 2013;) and

there is much freedom in choosing the separation electrolyte that prevents the loss in speciation

information. We limited the complete description of the ICP as it has been described earlier in

the literature (Caruso et al., 2003; Montes- Bayon et al., 2003; Caruso and Bayon, 2003; Scancar

et al., 2015;).

Hsieh et al (Hsieh and Jiang, 2012;) applied the HPLC-ICP-MS procedure for speciation of

arsenic in sea weeds. The arsenic species studied were arsenite [As(III)], arsenate [As(V)],

monomethylarsonic acid (MMA), dimethylarsinic acid (DMA), arsenobetaine (AsB), and

arsenocholine (AsC). Chromatographic separation was achieved in less than 9 min in gradient

elution mode using (NH4)2CO3 and methanol at pH 8.5. A typical chromatogram of a solution

containing 5 μg/L of As(III), As(V), MMA, DMA, AsB, and AsC is shown in Figure 1. Further,

19
ACCEPTED MANUSCRIPT
ACCEPTED MANUSCRIPT

as shown in Figure 1b, the elution peak caused by ArCl+, which might interfere with the

determination of arsenic, was well separated from As(V) and MMA.

4.2 Inductively coupled plasma atomic emission spectrometry (ICP-AES)

Comparative to above mentioned detectors, ICP-AES has a limited use as a specific detector for

HPLC because of its inferior sensitivity. It offers one advantage as compare to ICP-MS and that

is the speciation analysis of lighter metals such as cadmium and magnesium. ICP-AES detection

is feasible for cadmium, copper and zinc. Lewen et al (Lewen and Nugent, 2010;) use ICP-AES

in the determination of lithium in cleaning validation swabs. This work examines the use of

inductively coupled plasma atomic emission spectroscopy (ICP-AES) to evaluate the

effectiveness of procedures to clean equipment after its use with lithium carbonate drug products.

4.3 Ultraviolet detection system

UV absorbance detection is one of the most popular universal detection method used in

micro separations due to its simplicity, ease-of-use and low cost. The majority of organic

complexes of metal ions can be analyzed by UV detectors and most of the HPLC analyses are

performed using UV detectors. So the hyphenation of UV system with HPLC is of very high

importance. Chromatographic UV detection can be done at wavelengths where absorbance of the

dissolved sample is much stronger than the absorbance of the solvent itself. UV detectors can

sometimes give great selectivity and sometimes sensitivity in the analysis of specific compounds,

and they are relatively insensitive to changes in ambient temperature and the flow-rate of the

mobile phase. While they can be used in gradient elution applications on occasion, base-line drift

can be troublesome. Arain et al (Arain et al., 2002;) determined metal ions in canal water and

20
ACCEPTED MANUSCRIPT
ACCEPTED MANUSCRIPT

coal samples with RSD values within 4.15%. HPLC separation was carried out from LiChrosorb

ODS, 5mm column and complexes eluted with methanol: water: 1 mM sodium acetate (70:28:2,

v/v) with a flow-rate of 1.2 ml/ml and UV detection was at 260 nm. Amoli et al (Petsch et al.,

2004;) analysed the metal ions in crude oil by reversed-phase high performance liquid

chromatography with UV detector.

5. Conclusions and perspectives

In conclusion recent applications of HPLC to metal analysis includes an enormous

variety of chelating agents for the complexation studies of metal complexes. The stable

complexes between transition metal ions and chelating ligands enable the co-ordinating

interactions which enable their use for the detection of metal ions. Brief account on elemental

speciation analysis and a complete description on the recent progress in the application of high

performance liquid chromatography for the study of metal ion chemistry in the environment is

presented. Therefore it can be concluded that by the use of remarkable advancement of the

preconcentration technique, many of the previously formidable tasks, such as visualizing the

distribution of metal ions in environment at parts per quadrillion level, chemistry of metal

complexes and probing the mixture of different oxidation states of a single metal ion etc can be

achieved. This innovation in HPLC technique will surely lead to development of various

processes during the oxidation/reduction processes. This review will assist researchers to

understand and improve various performances on recent applications of high performance liquid

chromatography to metal analysis for the dynamic chemical evolution of metal ion chemistry in

environment. We hope our effort in this review will generate such capabilities for the better

fundamental understanding of the metal ion behavior.

21
ACCEPTED MANUSCRIPT
ACCEPTED MANUSCRIPT

6. References

Adamu, H.; Luter, L.; Lawan, M.M.; Umar, B.A. Chemical Speciation: A Strategic

Pathway for Insightful Risk Assessment and Decision Making for Remediation of Toxic metal

Contamination. Environ. Pollut. 2013, 2, 92-99.

Afton, S.; Kubachka, K.; Catron, B.; Caruso, J.A. Simultaneous characterization of

selenium and arsenic analytes via ion-pairing reversed phase chromatography with inductively

coupled plasma and electrospray ionization ion trap mass spectrometry for detection

Applications to river water, plant extract and urine matrices. J. Chromatogr. A 2008, 1208, 156-

163.

Ali, I.; Hassan, Y.; Ali, A.E.I. Speciation of arsenic and chromium metal ions by reversed

phase high performance liquid chromatography. Chemosphere. 2002, 48, 275-278.

Altunay, N.; Gurkan, R.; Orhan, U. Indirect determination of the flavor enhancer maltol

in foods and beverages through flame atomic absorption spectrometry after ultrasound assisted-

cloud point extraction. Food Chem. 2017, 235, 308-317.

Amaral, C.D.B.; Nóbrega, J.A.; Rita, A.; Nogueira, A. Investigation of arsenic species

stability by HPLC-ICP-MS in plants stored under different conditions for 12 months.

Microchem. J. 2014, 117, 122-126.

Amoli, H.S.; Porgam, A.; Bashiri Sadr, Z.; Mohanazade, F. Analysis of metal ions in

crude oil by reversed-phase high performance liquid chromatography using short column. J.

Chromatogr. A. 2006, 1118, 82-84.

22
ACCEPTED MANUSCRIPT
ACCEPTED MANUSCRIPT

Anthemidis, N.A.; Loannou, G.K.L. Recent developments in homogeneous and

dispersive liquid--liquid extraction for inorganic elements determination: A review. Talanta.

2009, 80, 413-421.

Arain, M.A.; Khuhawar, M.Y.; Bhanger, M.I. Gas and liquid chromatography of metal

chelates of pentamethylene dithiocarbamate. J. Chromatogr. A. 2002, 973, 235--241.

Arain, M.A.; Wattoo, F.H.; Wattoo, M.H.S.; Ghanghro, A.B.; Tirmizi, S.A.; Iqbal, J.;

Arain, S.A. Simultaneous determination of metal ions as complexes of pentamethylene

dithiocarbamate in Indus river water. Arabian J. Chem. 2009, 2, 25-29.

Aranjo-Barbosa, U.; Pena-Vazquez, E.; Barciela-Alonso, M.C.; Ferreira, S.L.C.; Santos,

A.M.P.D.; Bermezjo-Barrera, P. Simultaneous determination and speciation analysis of arsenic

and chromium in iron supplements and speciation analysis used for iron deficiency anemia

treatment by HPLC-ICP-MS. Talanta. 2017, 170, 523-529

Asghari, A.; Ghazaghi, M.; Rajabi, M.; Behzad, M.; Ghaedi, M. Ionic liquid-based

dispersive liquid--liquid microextraction combined with high performance liquid

chromatography-UV detection for the simultaneous pre-concentration and determination of Ni,

Co, Cu and Zn in water samples. J. Serb. Chem. Soc. 2014, 79, 63-76.

Atanassova, A.; Lam, R.; Zamble, D.B. A high-performance liquid chromatography

method for determining transtion metal content in proteins. Anal. Biochem. 2004, 335, 103--111.

Baralkiewicz, D.; Kózka, M.; Piechalak, A.; Tomaszewska, B.; Sobczak, P.

Determination of cadmium and lead species and phytochelatins in pea (Pisum sativum) by

HPLC--ICP-MS and HPLC--ESI-MS. Talanta. 2009, 79, 493-498.

23
ACCEPTED MANUSCRIPT
ACCEPTED MANUSCRIPT

Bernhard, M.; Brinckman, F.E.; Sadler, P.J. The importance of chemical speciation in

environmental processes. Springer. Verlag, Berlin. 1986.

Bourhis, K.; Blanc, S.; Mathe, C.; Dupin, J.C.; Vieillescazes, C. Spectroscopic and

chromatographic analysis of yellow flavonoidic lakes: quercetin chromophore. Appl. Clay Sci.

2011, 53, 598-607.

Buszewskia, B. Szultkaa, M. Past, Present and Future of Solid Phase Extraction: A

Review. Crit. Rev. Anal. Chem. 2012, 42, 198-213.

Cabanero, A. Madrid, Y. Cámara, C. Study of mercury--selenium interaction in chicken

liver by size exclusion chromatography inductively coupled plasma mass spectrometry. J. Anal.

At. Spectrom. 2005, 20, 847-855.

Cabanero, A.I.; Carvalho, C.; Madrid, Y.; Batoréu C.; Cámara, C. Quantification and

speciation of mercury and selenium in fish samples of high consumption in Spain and Portugal.

Biol. Trace Elem. Res. 2005, 103, 17-25.

Campenhout, K.V.; Infante, H.G.; Goemans, G.; Belpaire, C.; Adams, F.; Blust, R.;

Bervoets, L. A field survey of metal binding to metallothionein and other cytosolic ligands in

liver of eels using an online isotope dilution method in combination with size exclusion high

pressure liquid chromatography couples to inductively coupled plasma time of flight mass

spectrometry (ICP-TOFMS). Sci. Total Environ. 2008, 394, 379-389.

Cao, Y.; Duan, J.; Guo, J.; Li, W.; Tao, W. Pharmacokinetic properties of arsenic species

after oral administration of Sargassum pallidum extract in rats using an HPLC-HG-AFS method.

J. Pharmaceut. Biomed. Anal. 2014, 96, 213-219.

24
ACCEPTED MANUSCRIPT
ACCEPTED MANUSCRIPT

Carioni, V.M.O.; Mcelory, J.A.; Guthrie, J.M.; Ngwenyama, R.A.; Brockman, J.D. Fast

and reliable method for As speciation in urine samples containing low levels of As by LC-ICP-

MS: Focus on epidemiological studies. Talanta. 2017, 165, 76-83

Caruso, J.A.; Bayon, M.M. Elemental speciation studies-new directions for trace metal

analysis. Ecotoxicol. Environ. Saf. 2003, 5, 148-163.

Caruso, J.A.; Klaue, B.; Michalke, B.; Rocke, D.M. Group assessment: elemental

speciation. Ecotoxicol. Environ. Saf. 2003, 56, 32-44.

Catalani, S.; Fostinelli, J.; Gilberti, M.E.; Apostoli, P. Application of a metal free high

performance liquid chromatography with inductively coupled plasma mass spectrometry (HPLC-

ICP-MS) for the determination of chromium species in drinking and tap water. Int. J. mass

Spectromet. 2015, 387, 31-37.

Cervantes, C.; Campos-Garcĺa, J.; Devars, S.; Gutiérrez-Corona, F.; Loza-Tavera, H.;

TorresGuzmán, J.C.; Moreno-Sánchez, R. Interactions of chromium with microorganisms and

plants. FEMS Microbiol. Rev. 2001, 25, 335-347.

Chahal, V.K.; Singh, R.; Malik, A.K.; Matysik, F.M.; Puri, J.K. Preconcentration method

on modified silica fiber for chromium speciation. J. Chromatogr. Sci. 2012, 50, 26-32.

Chehrehghani, A.; Samadi, N.; Vardast, M.R. Optimization of dispersive liquid-liquid

microextraction followed by HPLC-DAD determination of Cr (III) and Co (II) based on the

complexation reaction with morpholin-4-carodithioate. J. Chem. Biol. Phys. Sci. 2014, 4, 116-

130.

25
ACCEPTED MANUSCRIPT
ACCEPTED MANUSCRIPT

Chen, B.; Zeng, Y.; Hu, B. Study on speciation of aluminum in human serum using

zwitterionic bile acid derivative dynamically coated C18 column HPLC separation with UV and

on-line ICP-MS detection. Talanta. 2010, 81, 180-186.

Chen, H.; Chen, J.; Jin, X.; Wei, D. Determination of trace mercury species by high

performance liquid chromatography--inductively coupled plasma mass spectrometry after cloud

point extraction. J. Hazard. Mater. 2009, 172, 1282-1287.

Chen, J.; Chen, H.; Jin, X.; Chen, H. Determination of ultra-trace amount methyl-, phenyl

and inorganic mercury in environmental and biological samples by liquid chromatography with

inductively coupled plasma mass spectrometry after cloud point extraction preconcentration.

Talanta. 2009, 77, 1381-1387.

Chen, S.; Zhu, L.; Lu, D.; Cheng, X.; Zhou, X. Separation and chromium speciation by

single-wall carbon nanotubes microcolumn and inductively coupled plasma mass spectrometry.

Microchim. Acta. 2010, 169, 123-128.

Chen, S.; Zhu, S.; He, Y.; Lu, D. Speciation of chromium and its distribution in tea leaves

and tea infusion using titanium dioxide nanotubes packed microcolumn coupled with inductively

coupled plasma mass spectrometry. Food Chem. 2014, 150, 254-259.

Date, R.A.; Gray, A.L. Determination of rare earth elements in plasma source mass

spectrometry using an ICP and a high resolution quadrupole mass spectrometer. Analyst. 1981,

106, 1255-1267.

Daud, M.J.; Alakili, I.M. High performance liquid chromatographic separations of metal

pyrrolidine dithiocarbamate complexes. Malaysian J. Anal. Sci. 2001, 7, 113-120.

26
ACCEPTED MANUSCRIPT
ACCEPTED MANUSCRIPT

Davis, R.A.H.; Goncalves, R.A.; Lourenc, R.; Reinaldo, Z.; Campos, C.D. A novel report

of metallothioneins in fish bile: SDS-PAGE analysis, spectrophotometry quantification and metal

speciation characterization by liquid chromatography coupled to ICP-MS. Aquat. Toxicol. 2012,

116, 54-60.

Falandysz, J. Selenium in edible mushrooms. J. Environ Sci Health C Environ Carcinog

Ecotoxicol Rev. 2008, 26, 256-99

Fang, Y.; Pan, Y.; Li, P.; Xue, M.; Pei, F.; Yang, W.; Ma, N.; Hu, Q. Simultaneous

determination of arsenic and mercury species in rice by ion-pairing reversed phase

chromatography with inductively coupled plasma mass spectrometry. Food Chem. 2016, 213,

609-615.

Farajzadeh, M.A.; Bahram, M.; Vardast, M.R. Central composite design applied to

optimization of dispersive liquid-liquid microextraction of Cu(II) and Zn(II) in water followed

by high performance liquid chromatography determination. Clean-Soil, Air, Water. 2010, 38,

466-477.

Ferri, T.; Favero, G.; Frasconi, M. Selenium speciation in foods: Preliminary results on

potatoes. Microchem. J. 2007, 85, 222-227.

Frankawski, M.; Frankowska, A.Z. Speciation analysis of aluminium and aluminium

fluoride compexes by HPLC-UV. Talanta. 2010, 82, 379-389.

Frausto da Silva, J.J.R.; Williams, R.J.P. The Biological Chemistry of the Elements.

second ed. Oxford University Press. Oxford. UK. 2001.

Frumkin, H.; Thun, M.J. Arsenic. C.A. Cancer J. Clin. 2001, 51, 254-262.

27
ACCEPTED MANUSCRIPT
ACCEPTED MANUSCRIPT

Gao, Z. Ma, X. Speciation analysis of mercury in water samples using dispersive liquid-

liquid microextraction combined with high-performance liquid chromatography. Anal. Chim.

Acta. 2011, 702, 50-55.

Gomez, V.; Callao, M.P. Chromium determination and speciation since 2000. Trends

Anal. Chem. 2006, 25, 10-20.

Gosetti, F.; Frascarolo, P.; Polati, S.; Medana, C.; Gianotti, V.; Palma, P.; Aigotti, R.;

Baiocchi, C.; Gennaro, M.C. Speciation of selenium in diet supplements by HPLC-MS/MS

methods. Food Chem. 2007, 105, 1738-1747.

Gregoria, I.D.; Quiroza, W.; Pinocheta, H.; Pannier, F.; Potin-Gautierb, M. Speciation

analysis of antimony in marine biota by HPLC-(UV)-HG-AFS: Extraction procedures and

stability of antimony species. Talanta. 2007, 73, 458-465.

Harrington, C.F. The speciation of mercury and organomercury compounds by using

high-performance liquid chromatography. Trends. Anal. Chem. 2000, 19, 167-179.

Hashempur, T.; Rofouei, M.K.; Khorrami, A.R. Speciation analysis of mercury

contaminants in water samples by RP-HPLC after solid phase extraction on modified C18

extraction disks with 1,3-bis(2-cyanobenzene)triazene. Microchem. J. 2008, 89, 131-136.

Heena, Kumar, R.; Rani, S.; Malik, A.K. Development of a rapid and sensitive method

for the determination of aluminum by reverse phase high performance liquid chromatography

using a fluorescence detector. J. Chromatogr. Sci. 2015, 53 (5), 800-806.

Herrador, E.A.; Lucena, R.; Cárdenas, S.; Valcárcel, M. Sample Treatments Based on

Ionic Liquids. Appl. Perspect. Ionic Liq. 2011, 181-205.

28
ACCEPTED MANUSCRIPT
ACCEPTED MANUSCRIPT

Hirose, K. Conditional stability constants of metal complexes of organic ligands in sea

water: past and present, and a simple coordination chemistry model. Anal. Chim. Acta. 1994,

284, 621-634.

Hossain, M.A. Yoshimasa, M.K. Tajmeri, M. Islam, S.A. Mori, S. Rapid speciation

analysis of Cr(VI) and Cr(III) by reversed-phase high-performance liquid chromatography with

UV detection. J. Chromatogr. Sci. 2005, 43, 98-103.

Houk, R.S.; Fassel, V.A.; Flesch, G.D.; Ivec, H.L. Gray, A.L. Taylor, C.E. Inductively

coupled argon plasma as an ion source for mass spectrometric determination of trace elements.

Anal. Chem. 1980, 52, 2283-2289.

Hsieh, Y.J.; Jiang, S.J. Application of HPLC-ICP-MS and HPLC-ESI-MS Procedures for

Arsenic Speciation in Seaweeds. J. Agric. Food Chem. 2012, 60, 2083-2089.

Hymer, C.B.; Caruso, J.A. Arsenic and its speciation analysis using high-performance

liquid chromatography and inductively coupled plasma mass spectrometry. J. Chromatogr. A.

2004, 1045, 1-13.

Ipolyi, I.; Corns, W.; Fodor, P.; Stockwell, P. Speciation of inorganic selenium and

selenoamino acids by an HPLC-UV-HG-AFS system. J. Autom. Methods Manag. Chem. 2001,

23, 167-172.

Jia, X.; Han, Y.; Liu, X.; Duan, T.; Chen, H. Speciation of mercury in water samples by

dispersive liquid--liquid microextraction combined with high performance liquid

chromatography-inductively coupled plasma mass spectrometry. Spectrochim. Acta. B. 2011, 66,

8892-8899.

29
ACCEPTED MANUSCRIPT
ACCEPTED MANUSCRIPT

Kalman, D.A.; Dills, R.L.; Steinmaus, C.; Yunus, M.; Khan, A.F.; Prodhan, M.M.; Yuan,

Y.; Smith, A.H. Occurrence of trivalent monomethyl arsenic and other urinary arsenic species in

a highly exposed juvenile population in Bangladesh. J. Expo. Sci. Environ. Epidemiol. 2013, 23,

1-8.

Kannamkumarath, S.S.; Wroabel, K.; Caruso, J.A.; Wrobel, K. Speciation of Arsenic in

Different Types of Nuts by Ion Chromatography-Inductively Coupled Plasma Mass

Spectrometry. J. Agric. Food Chem. 2004, 52, 1458-1463.

Kaur, V.; Aulakh, J.S.; Malik, A.K. A new approach for simultaneous determination of

Co(II), Ni(II), Cu(II) and Pd(II) using 2- thiophenaldehyde-3-thiosemicarbazone as reagent by

solid phase microextraction-high performance liquid chromatography. Anal. Chim. Acta. 2007,

603, 44-50.

Kaur, V.; Malik, A.K. A new method for simultaneous determination of Co(II), Ni(II)

and Pd(II) as morpholine-4-carbodithioate complex by SPME-HPLC-UV system. Talanta. 2007,

73, 425-430.

Kaur, V.; Malik, A.K. Speciation of Chromium Metal Ions by RP-HPLC. J. Chromatogr.

Sci. 2009, 47, 238-242.

Khuhawar, M.Y.; Arain, G.M. Liquid chromatographic determination of cis-platin as

platinum(II) in pharmaceutical preparation, serum and urine samples of cancer patients. Talanta.

2005, 66, 34-39.

Kodamatani, H.; Matsuyama, A.; Saito, K.; Kono, K.; Kanzaki, R.; Tomiyasu, T.

Sensitive determination method for mercury ion, methyl-, ethyl-and phenyl-mercury in water and

30
ACCEPTED MANUSCRIPT
ACCEPTED MANUSCRIPT

biological samples using high performance liquid chromatography with chemiluminescence

detection. Anal. Sci. 2012, 28, 959-965.

Kokosa, J.M. Recent trends in using single-drop microextraction and related techniques

in green analytical methods. Trends. Aanl. Chem. 2015, 70, 194-204.

Kuba, P.; Guchardi, R.; Hauser, P.C. Trace-metal analysis with separation methods.

Trends Anal. Chem. 2005, 24, 192-198.

Lal, S.K.; Tan, G.H.; Tiah, N.H.; Das, V.G.K. Speciation of phenyltin(IV) compounds

using high performance liquid chromatography: the direct analysis of mixed standard solutions

of tetraphenyltin, triphenyltin chloride, triphenyltin hydroxide and tiphenyltin acetate. Appl.

Organometal. Chem. 2002, 16, 250-257.

Lambropoulou, D.A.; Albanis, T.A. Liquid-phase micro-extraction techniques in

pesticide residue analysis. J. Biochem. Biophys. Methods. 2007, 70, 195-228.

Latorre, C.H.; García, J.B.; Martín, S.G.; Crecente, R.M.P. Solid phase extraction for the

speciation and preconcentration of inorganic selenium in water samples: A review. Anal. Chim.

Acta. 2013, 804, 37-49

Lewen, N.; Nugent, D. The use of inductively coupled plasma-atomic emission

spectroscopy (ICP-AES) in the determination of lithium in cleaning validation swabs. J.

Pharmaceut. Biomed. Anal. 2010, 52, 652-655.

Lian, H.; Kang, Y.; Bi, S.; Arkin, Y.; Shao, D.; Li, D.; Chen, Y.; Dai, L.; Gan, N.; Tian,

L. Direct determination of trace aluminum with quercetin by reversed-phase high performance

liquid chromatography. Talanta. 2004, 62, 43-50.

31
ACCEPTED MANUSCRIPT
ACCEPTED MANUSCRIPT

Liang, P.; Sang, H. Speciation of chromium in water samples with cloud point extraction

separation and preconcentration and determination by graphite furnace atomic absorption

spectrometry. J. Hazard. Mater. 2008, 154, 1115-1119.

Lin, L.Y.; Chang, L.F.; Jiang, S.J. Speciation Analysis of Mercury in Cereals by Liquid

Chromatography Chemical Vapor Generation Inductively Coupled Plasma-Mass Spectrometry.

J. Agric. Food Chem. 2008, 56, 6868-6872.

Lopez-García, I.; Vicente-Martinez, Y.; Hernandez-Cordoba, M.; Non-chromatographic

speciation of chromium at sub-ppb levels using cloud point extraction in the presence of

unmodified silver nanoparticles. Talanta. 2015, 132, 23-28.

Lu, M.Y.; Wang, N.; Wu, W.H.; Lai, C.W.; Kuo, P.H.; Chiang, P.H.; Lin, K.H.; Wu,

T.H. Simultaneous Determination of Plasma Deferasirox and Deferasirox-Iron Complex Using

an HPLC-UV System and Pharmacokinetics of Deferasirox in Patients With β-Thalassemia

Major: Once-daily Versus Twice-daily Administration. Clinical Therapeut. 2015, 37, 1751-1760.

Malik, A.K.; Kaur, V.; Verma, N. A review on solid phase microextraction-High

performance liquid chromatography as a novel tool for the analysis of toxic metal ions. Talanta.

2006, 68, 842-849.

Manahan, S.E. Environmental Chemistry. Lewis Publishers. 2000.

Marcinkowska, M.; Komorowicz, I.; Barałkiewicz, D. Study on multielemental

speciation analysis of Cr(VI), As(III) and As(V) in water by advanced hyphenated technique

HPLC/ICP-DRC-MS. Talanta. 2015, 144, 233-240.

32
ACCEPTED MANUSCRIPT
ACCEPTED MANUSCRIPT

Marcinkowska, M.; Lorenc, W.; Barałkiewicz, D. Study of the impact of bottles material

and color on the presence of AsIII, AsV, SbIII, SbV and CrVI in matrix-rich mineral water-

Multielemental speciation analysis by HPLC/ICP-DRC-MS. Microchem. J. 2017, 132, 1-7

Markiewicz, B.; Komorowicz, I.; Sajnog, A.; Belter, M.; Baralkiewicz, D. Chromium and

its speciation in water samples by HPLC/ICP-MS-Technique establishing metrological

traceability: A review since 2000. Talanta. 2015, 132, 814-828.

Martinis, E.M.; Berton, P.; Monasterio, R.P.; Wuilloud, R.G. Emerging ionic liquid-

based techniques for total-metal and metal-speciation analysis. Trends. Anal. Chem. 2010, 29,

1184-1201.

Matsumiya, H.; Nobuhiko, I.K.; Miyano, S. Sulfonylcalix[4] arene tetrasulfonate as a

column chelating agent for the selective determination of aluminium(III), iron(III) and

titanium(IV) by ion pair reversed-phase high-performance liquid chromatography with

spectrophotometric detection. Talanta. 2004, 62, 337-342.

Mester, Z.; Lord, H.; Pawliszyn, J. Speciation of trimethyl lead and triethyl lead by in-

tube solid phase microextraction high-performance liquid chromatography electrospray

ionization mass spectrometry. J. Anal. At. Spectrum. 2000, 15, 595-600.

Miro, M.; Estela, J.M.; Cerda, V. Recent Advances in On-line Solvent Extraction

Exploiting Flow Injection/Sequential Injection Analysis. Curr. Anal. Chem. 2005, 1, 329-343.

Mitchell, R.J.; Christian, R.; Hughes, H.; Miah, A.; Walker, D.K. The application of fully

automated on-line solid phase extraction in bioanalysis. J. Pharm. Biomed. Anal. 2010, 52, 86-

92.

33
ACCEPTED MANUSCRIPT
ACCEPTED MANUSCRIPT

Mohsen-Nia, M.; Jazi, B.; Amiri, H. Binodal curve measurements for (water + propionic

acid + dichloromethane) ternary system by cloud point method. J. Chem. Thermo. 2009, 41, 859-

863.

Montes-Bayon, M.; DeNicola, K.; Caruso, J.A. Liquid chromatography--inductively

coupled plasma mass spectrometry. J. Chromatogr. A 2003, 1000, 457-476.

Moreda-Pineiro, J.; Alonso-Rodrıguez, E.; Moreda-Pineiro, A.; Moscoso-Perez, C.;

Lopez-ah, P.; Muniategui-Lorenzo, S.; Prada-Rodrıguez, D. Use of pressurized hot water

extraction and high performance liquid chromatography--inductively coupled plasma-mass

spectrometry for water soluble halides speciation in atmospheric particulate matter. Talanta.

2012, 101, 283-291.

Narukawa, T.; Suzuki, T.; Inagaki, K.; Hioki, A. Extraction techniques for arsenic species

in rice flour and their speciation by HPLC--ICP-MS. Talanta. 2014, 130, 213-220.

Niedzielski, P. The new concept of hyphenated analytical system: Simultaneous

determination of inorganic arsenic(III), arsenic(V), selenium(IV) and selenium(VI) by high

performance liquid chromatography--hydride generation-(fast equential) atomic absorption

spectrometry during single analysis. Anal. Chim. Acta. 2005, 551, 199-206.

Palacios, O.; Encinar, J.R.; Schaumloffel, D.; Lobinski, R. Fractionation of selenium-

containing proteins in serum by multiaffinity liquid chromatography before size-exclusion

chromatography-ICPMS. Anal. Bioanal. Chem. 2006, 384, 1276-1283.

Pan, M.; Wang, J.; Fang, G.; Tang, W.; Wang, S. Synthesis and characterization of a

molecularly imprinted polymer and its application as SPE enrichment sorbent for determination

of trace methimazole in pig samples using HPLC-UV. J. Chromatogr. B. 2010, 878, 1531-1536.

34
ACCEPTED MANUSCRIPT
ACCEPTED MANUSCRIPT

Paul, B.; Twohill, E.; Basher, W. Determination of trace cadmium in environmental

water samples using ion interaction reverse phase liquid chromatography with fluorescence

detection. J. Chromatogr. A. 2000, 877, 123-132.

Pedrero, Z.; Madrid, Y. Novel approaches for selenium speciation in foodstuffs and

biological specimens: A review. Anal. Chim. Acta. 2009, 634, 135-152.

Pena-Pereira, F.; Lavilla, I.; Bendicho, C. Liquid-phase microextraction techniques

within the framework of green chemistry. Green Anal. Chem. 2010, 29, 617-628.

Pena-Pereira, F.; Lavilla, I.; Bendicho, C. Miniaturized preconcentration methods based

on liquid--liquid extraction and their application in inorganic ultra trace analysis and speciation.

Spectrochimica. Acta. B. 2009, 64, 1-15.

Pena-Pereira, F.; Lavilla, I.; Bendicho, C.; Canals, L.V.A. Speciation of mercury by ionic

liquid-based single-drop microextraction combined with high- performance liquid

chromatography-photodiode array detection. Talanta. 2009, 78, 537-541.

Peng, H.; Zhang, N.; He, M.; Chen, B.; Hu, B. Simultaneous speciation analysis of

inorganic arsenic, chromium and selenium in environmental waters by 3-(2-aminoethylamino)

propyltrimethoxysilane modified multi-wall carbon nanotubes packed microcolumn solid phase

extraction and ICP-MS. Talanta. 2015, 131, 266-272.

Petsch, M.; Seipelt, J.; Mayer- Helm, B.X. A novel pre-column derivatization reaction for

the determination of dithiocarbamates in plasma by high performance liquid chromatography.

Anal. Chim. Acta. 2004, 516, 119-124.

Pilar, M.; Reino, R.; Fernández, R.R.; Vázquez, E.P.; González, R.D.; Barrera, P.B.;

Pineiro, A.M. Mercury speciation in seawater by liquid chromatography-inductively coupled

35
ACCEPTED MANUSCRIPT
ACCEPTED MANUSCRIPT

plasma-mass spectrometry following solid phase extraction pre-concentration by using an ionic

imprinted polymer based on methyl-mercury--phenobarbital interaction. J. Chromatogr. A. 2015,

1391, 9-17.

Pizarro, I.; Gomez, M.; Camara, C.; Palacios, M.A. Arsenic speciation in environmental

and biological samples: Extraction and stability studies. Anal. Chim. Acta 2003, 495, 85-98.

Pyrzynska, K. Redox speciation of chromium using sorption based systems. Trends anal.

chem. 2012, 32, 100-111.

Pytlakowska, K.; Kozik, V.; Dabioch, M. Complex forming organic ligands in cloud

point extraction of metal ions: Review. Talanta. 2013, 110, 202-228.

Rakhunde, R.; Deshpande, L.; Hjuneja, H.D. Chemical speciation of chromium in water.

Crit. Rev. Env. Sci. Technol. 2012, 42, 776-810.

Rao, R.M.; Aggarwal, S.K. Determination of boron at sub-ppm levels in uranium oxide

and aluminum by hyphenated system of complex formation reaction and high-performance

liquid chromatography (HPLC). Talanta. 2008, 75, 585--588.

Razmisleviciene, I.; Olsauskaite, V.; Padarauskas, A. Ionic liquid-based dispersive

liquid-liquid microextraction combined with ultra performance liquid Chromatography for the

determination of metal ions. Chemija. 2011, 22, 197-203.

Rezaee, M.; Assadi, Y.; Hosseini, M.R.M.; Aghaee, E.; Ahmadi, F.; Berijani, S.

Determination of organic compounds in water using dispersive liquid--liquid microextraction. J.

Chromatogr. A. 2006, 1116, 1-9.

Saleh, A.; Yaminia, Y.; Faraji, M.; Shariati, S.; Rezaee, M. Hollow fiber liquid phase

microextraction followed by high performance liquid chromatography for determination of ultra-

36
ACCEPTED MANUSCRIPT
ACCEPTED MANUSCRIPT

trace levels of Se(IV) after derivatization in urine, plasma and natural water samples. J.

Chromatogr. B. 2009, 877, 1758-1764.

Samaddar, P.; Sen, K. Cloud point extraction: A sustainable method of elemental

preconcentration and speciation. J. Ind. Eng. Chem. 2014, 20, 1209-1219.

Sanchez, D.M.; Martin, R.; Morante, R.; Marin, J.; Munuera, M.L. Preconcentration

speciation method for mercury compounds in water samples using solid phase extraction

followed by reversed phase high performance liquid chromatography. Talanta. 2000, 52, 671-

679.

Sarafraz-Yazdi, A.; Amizi, A. Liquid-phase microextraction. Trends Anal. Chem. 2010,

29, 1-14.

Scancar, J.; Berlinger, B.; Thomassen, Y.; Milacic, R. Simultaneous speciation analysis

of chromate, molybdate, tungstate and vanadate in welding fume alkaline extracts by HPLC--

ICP-MS. Talanta. 2015, 142, 164-169.

Stalikas, C.D.; Flamengos, Y.C. Microextraction combined with derivatization. Trends

Anal. Chem. 2008, 27, 533-542.

Stanisz, E.; Werner, J.; Kowiak, A.Z.G. Liquid-phase microextraction techniques based

on ionic liquids for preconcentration and determination of metals. Trends Anal. Chem. 2014, 61,

54-66.

Su, Y.; Chan, H.; Gao, Y.; Li, X.; Hau, X.; Lu, Y. A novel high pressure liquid

chromatography with ultraviolet detection/ nano TiO2 chemiluminiscence system for the

determination of selenocysteine and selenomethionine. J. Chromatogr. B. 2008, 870, 216-221.

37
ACCEPTED MANUSCRIPT
ACCEPTED MANUSCRIPT

Tabrizi, A.B.; Development of a dispersive liquid--liquid microextraction method for iron

speciation and determination in different water samples. J. Hazard. Mater. 2010, 183, 688-693.

Takeuchi, T.; Inoue, S.; Yamamoto, M.; Tsuji, M.; Miwa, T. Fluorimetric determination

of magnesium and aluminum via complexation with oxine in high-performance liquid

chromatography. J. Chromatogr. A. 2001, 910, 373-376.

Tang, A.N.; Jiang, D.Q.; Jiang, Y.; Wang, S.W.; Yan, X.P. Cloud point extraction for

high-performance liquid chromatographic speciation of Cr(III) and Cr(VI) in aqueous solutions.

J. Chromatogr. A. 2004, 36, 183-188.

Taumer, U.; Yates, B.; Galal, A.; Gbatu, T.; Larue, R.; Schmiesing, C.; Temsamani, K.;

Ceylan, O.; Mark, H.B. Electrochemically Aided Control of Solid Phase Micro-Extraction

(EASPME) Using Conducting Polymer-Coated Solid Substrates Applicable to Neutral Analytes.

J. Microchim. Acta. 2003, 143, 205-215.

Tchounwou, P.B.; Yedjou, C.G.; Patlolla, A.K.; Sutton, D.J. Heavy Metals Toxicity and

the environment. Mol. Clin. Environ. Toxicol.2012, 101, 133-164.

Threeprom, J.; Purachaka, S.; Potipan, L. Simultaneous determination of Cr(III)--EDTA

and Cr(VI) by ion interaction chromatography using a C18 column. J.Chromatogr. A. 2005,

1073, 291-295.

Timerbaev, A.R. Elemental speciation analysis using Capillary electrophoresis: twenty

years of development and applications. Chem. Rev. 2013, 113, 778-812.

Todorovi, Z.; Poli, P.; Saboand, T.; Caki, M. Preconcentration method for trace metals in

natural waters using 4-morpholine dithiocarbamate. J. Serb. Chem. Soc. 2002, 67, 879-885.

38
ACCEPTED MANUSCRIPT
ACCEPTED MANUSCRIPT

Tsoi, Y.K.; Leung, K.S.Y. Toward the use of surface modified activated carbon in

speciation: Selective preconcentration of selenite and selenate in environmental waters. J.

Chromatogr. A. 2011, 1218, 2160-2164.

Turker, A.R. Separation, Preconcentration and speciation of metal ions using solid phase

extraction. Sep. Purification. Rev. 2012, 41, 169-206.

Veening, H.; Greenwood, J.M.; Shanks, W.H.; Willeford, B.R. J. Chem. Soc. Chem.

Commun. 1969, 22, 1305-1306.

Vela, N.P.; Heitkemper, D.T.; Stewart, K.R. Arsenic extraction and speciation in carrots

using accelerated solvent extraction, liquid chromatography and plasma mass spectrometry.

Analyst. 2001, 126, 1011-1017.

Vincent, J.B. Is chromium pharmacologically relevant?. J. Trace Elem. Med Biol. 2014,

28, 397-405.

Wang, L.; Jiang, G.; Cai, Y.; He, B.; Wang, Y.; Shen, D. Cloud point extraction coupled

with HPLC-UV for the determination of phthalate esters in environmental water samples. J.

Environ. Sci. 2007, 19, 874-878.

Wang, L.L.; Wang, J.Q.; Zheng, Z.X.; Xiao, P. Cloud point extraction combined with

high-performance liquid chromatography for speciation of chromium(III) and chromium(VI) in

environmental sediment samples. J. Hazard. Mater. 2010, 177, 114-118.

Wang, P.; Zhao, G.; Tian, J.; Su, X. High-performance liquid chromatography

inductively coupled plasma mass spectrometry based method for the determination of organic

arsenic feed additives and speciation of anionic arsenics in animal feed. J. Agric. Food Chem.

2010, 58, 5263-5270.

39
ACCEPTED MANUSCRIPT
ACCEPTED MANUSCRIPT

Watanabe, H.; Kamidate, T.; Kawamorita, S.; Haraguchi, K.; Miyajima, M. Distribution

of Nickel(II), Cadmium(II) and Copper(II) Chelates of 2-(2-Pyridylazo)-5-methylphenol in two

phases separated from micellar solution of nonionic surfactant. Anal. Sci. 1987, 3, 433-436.

Watanabe, H.; Saitoh, T.; Kamidate, T.; Haraguchi, K. Kinetics of complexation of nickel

(II) and copper (II) with some azophenol derivatives in aqueous nonionic surfactant solution.

Microchim. Acta. 1992, 106, 83-90.

Watanabe, H.; Tanaka, H. A non-ionic surfactant as a new solvent for liquid-liquid

extraction of zinc(II) with 1-(2-pyridylazo)-2-naphthol. Talanta. 1978, 25, 585-589.

Wei, G.T.; Yang, Z.; Chen, C.J. Room temperature ionic liquid as a novel medium for

liquid/liquid extraction of metal ions. Anal. Chim. Acta. 2003, 488, 183-192.

Wrobel, K.; Wrobel, K.; Kannamkumarath, S.S.; Caruso, J.A.; Irena, A.; Wysocka, B.;

Bulska, E.; Swiatek, J.; Wierzbicka, M. HPLC--ICP-MS speciation of selenium in enriched

onion leaves- a potential dietary source of Se-methylselenocysteine. Food Chem. 2004, 86, 617-

623.

Wuana, R.A.; Okieimen, F.E. Heavy Metals in Contaminated Soils: A Review of

Sources, Chemistry, Risks and Best Available Strategies for Remediation. ISRN Ecology. 2011,

1-20.

Xia, L.; Hu, B.; Wu, Y. Hollow fiber-based liquid-liquid-liquid microextraction

combined with high-performance liquid chromatography for the speciation of organomercury. J.

Chromatogr. A. 2007, 1173, 44-51.

Xiong, C.M.; He, M.; Hu, B. On-line separation and preconcentration of inorganic

arsenic and selenium species in natural water samples with CTAB-modified alkyl silica

40
ACCEPTED MANUSCRIPT
ACCEPTED MANUSCRIPT

microcolumn and determination by inductively coupled plasma-optical emission spectrometry.

Talanta. 2008, 76, 772-779.

Yates, B.J.; Temsamani, K.R.; Ceylan, O.; Oztemiz, S.; Gbatu, T.P.; LaRue, R.A.;

Tamer, U.; Mark, H.B. Electrochemical control of solid phase micro-extraction: conducting

polymer coated film material applicable for preconcentration/analysis of neutral species. Talanta.

2002, 58, 739-745.

Zhou, Q.; Xing, A.; Zhao, K. Simultaneous Determination of nickel, cobalt and mercury

ions in water samples by solid phase extraction using multiwalled carbon Nanotubes as

adsorbent after chelating with sodium diethyldithiocarbamate prior to high performance liquid

chromatography. J. Chromatogr. A. 2014, 1360, 76-81.

Zmozinski, A.V.; Lorente-Mirandes, T.; Lopez Sonchez, J.F.; De Silva, M.M.

Establishment of a method for determination of arsenic species in sea food by LC-ICP-MS. Food

Chem. 2015, 173, 1073-1082.

41
ACCEPTED MANUSCRIPT
 ACCEPTED MANUSCRIPT
Table 1: Recent applications of HPLC to some metal complexes
S. No. Chelating Reagent Metal ion Mobile phase Column Wavelength/ pH/ Flow rate LOD/ LOQ Matrix Reference

detector

1 8-HQ Cu(II) and Zn(II) Methanol: water Zorbax Eclipse XDB C18 380 nm/ HPLC- 6.0/ 1.0 mL/min 3/10 µg/L Water samples (Farjzadeh et al., 2010;)

(75:25) containing Column DLLME

0.03M 8-hydroxy (250  4.6) mm

quinoline

2 Sodium DDTC Methylmercury (MeHg+) and mercury 0.06 mol/L XBridge C18 Column HPLC-DLLME 1.0 mL/min 0.0014, 0.0076/ 0.004, Water samples (Jia et al., 2011;)

(150  4.6) mm; 5 µm

2+)
(Hg ammonium acetate 0.025 ng/mL

3 8-Hydroxy quinoline- 5 Al(III) Acetonitrile, Ascentis express C18 λ ex 410 λ em 8.5/0.50 ml/min 0.05/0.15 Environmental (Heena et al., 2015;)

sulfonic acid methanol and water Column 510 nm/HPLC- aqueous

FLD sample
(10 cm1 4.6 mm)

4 DDTC Cr(III) and Cr(VI) Methanol, RP-C18 column 254 nm/HPLC- 7.0/1.0 ml/min 3.4-5.2/10.2-15.6 µg/L Aqueous (Daud and Alakili, 2001;)

acetonitrile and (Maxsil ODS 5 m, 25 cm × 4.6 mm) UV samples

buffer of pH 3.6

5 MDTC Co(II),Ni(II), Pd(II) Acetonitrile and RP-C18 column 300nm/ HPLC- 6.0/1.0 ml/min 0.06-0.17/0.18-0.51 Alloys and (Kaur and Malik, 2007;)

water (250 × 4.6) mm, 5µm UV ng/ml aqueous

sample

6 DDTC Ni(II), Co(II), Hg(II) Methanol and water Agilent Eclipse XDB C18 320 nm / HPLC 1.00 ml/min 0.04-0.9/ 0.12-2.7 µg/L Water samples (Lu et al., 2015;)

Column

42
ACCEPTED MANUSCRIPT
 ACCEPTED MANUSCRIPT
(4.6  250) mm, 5 µm

7 - TMSe, SeMet, Se(IV), Se(VI), SeCys2 Pyridineformeate Agilent C8 column 280 nm/ ICP- 4.5/0.5ml/min - Selenium (Wrobel et al., 2004;)

and methanol MS ion pairing methyl

(150  4.6 mm) 5 µm
selenocysteine,

fish oyster

8 - Selenocysteine selenomethionine Water:phosphate Poly styrene DVB exchange 253.7 nm/UV 7/ 0.6 ml/min 6.4,12/ Garlic (Su et al., 2008;)

buffer (50:50) Column

19.2,36
(250  4.1) mm 10 µm

µg/L

9 - Selenocysteine,selenomethionine Ammonium acetate C18 column with HPLC-UV-HG- Gradient 0.5- 0.31-0.43/ 0.93-1.29 Urine sample (Ipolyi et al., 2001;)

and acetonitrile didodecyldimethylammonium AFS 1.00 ml/min ng/mL

bromide

10 TiO2 adsorbent Cr(III) and Cr(VI) Nitric acid and PTFE microcolumn ICP-MS 5-8.0/0.09 0.0075/ 0.022 ng/mL Tea leaves and (Chen et al., 2014;)

distilled water ml/min infusion

(20 × 3.0) mm

11 TAN Cr(III) and Cr(VI) A mixture of C-18 Column HPLC-CPE 5.5/0.8 mL/min 7.5, 3.5 and 24.7, 11.5 Sediments (Wang et al., 2010;)
1
methanol--water (30  0.25) mm 0.5 µm μg L

(69:31, v/v) solution

and 4.5 mmolL−1 18

CTMAB buffered

with 0.03 mol L−1

NaAc--HAc solution

12 MDTC Cr(III) and Co(II) Acetonitrile and Zorbax Eclipse XDB C18 HPLC-DLLME 6.0/1.0 mL /min 3/ Aqueous (Chehrehghani et al., 2014;)

water (50:50) (25 cm x 4.6 mm) 9.9 environmental

1
μg L samples

43
ACCEPTED MANUSCRIPT
 ACCEPTED MANUSCRIPT
13 MDTC Cr(III), Cr(VI) Acetonitrile and Dionex Acclaim 120 C18 320/HPLC-UV 4.0/1.00 0.005,0.007/0.015,0.021 Drinking water (Kaur and Malik, 2009;)

water Column mL/min ng/mL

(4.6 × 250) mm

14 - As(III), As(V), DMA, MMA, AsB, AsC Ammonium Hamilton PRP-X100 anion HPLC-ICP-MS 8.5/0.9 mL/min 0.006-0.015/0.018- Seaweeds (Hsieh and Jiang, 2012;)

carbonate and exchange column 0.045

methanol (4.1 × 250)

µg/L
mm 10 µm

15 PMDTC Cu(II), Ni(II), Co(III), Fe(II), Mn(II) Methanol and Lichrosorb C18 260/UV 5/1.2 mL/min 2-6 mg/ mL Coal samples (Arain et al., 2002;)

acetate buffer

16 8-HQ V, Ni, Fe and Cu Methanol and water RP-C18 370/UV 3.6/0.5 mL/min 2.5,4.5,2/ 7.5,13.5,6 Crude oil (Amoli et al., 2006;)

(100 × 4.6) mm µg/L

17 PDTC Co(III),Co(II) Methanol: Hypersil C18 330 nm/UV 7.00/ 0.3 0.46 / Human Plasma (Petsch et al., 2004;)

Phosphate buffer ml/min

(150  2.1) mm 5µm 1.38 µg/L
(50:50)

18 Metalothionine cystosolic Zn(II), Pb(II), Ni(II), Cd(II), Cu(II) Tris buffer Gel filtration column ICP-TOFMS 7.4 0.6-10.8 µg/L Liver of eels (Campenhout et al., 2008;)

ligands (7.8 mm, 30 cm, 6 µm

19 Tiron Al(III) and AlF Ammonium chloride Ion Exchange column 310/ UV 3/1.0 mL/min 4.5-5.78 µg/L Soil samples (Frankaswki and Frankowska, 2010;)

and acidified water (50 mm) 9 µm

20 - AsB Ammonium PRP-X 100 anion exchange ICP-MS SPME 4/ 1.0 mL/min - - (Taumer et al., 2003;)

carbonate and water

21 EDTA Trimethyl lead Trifluoro acetic acid C18 column ES-MS 0.5 mL/min 11.3& 12.6 ng/mL - (Mester et al., 2000;)

and water 5 µm
Triethyl lead

44
ACCEPTED MANUSCRIPT
 ACCEPTED MANUSCRIPT
22 Sulfonylcalix[4] arene Al(III), Fe(III), Sn(IV) Methanol and Reverse phase C18 column 330/UV 4.7/2.5 mL/min 0.24-0.80 ng/mL River and tap (Matsumiya et al., 2004;)

ettrasulfonate acetate buffer (4.6  100) mm water samples

23 - Triphenyltin Acetonitrile and Water spherisorb SSW ODS- 254/UV 1.0 ml/min 0.1-0.02 mg/L Enviromental (Lal et al., 2002;)

water 2 column 10 µm water samples

Tetraphenyltin

24 8-Hydroxy quinoline Cadmium Acetonitrile and C18 column λex 360nm 4.8-5.4/ 1.5 2 µg/L River samples (Paul et al., 2000;)

tetra butyl (300  3.9 mm) mL/min

λem 500nm/FLD
ammonium

hydroxide

25 Penta methylene Fe(II), Cr(III), Mn(II), Cu(II), Ni(II), Methanol and buffer Li chrosorb ODS Column 260/UV 5/1.2 mL/min 14.2/22.6 µg/L River Indus (Arain, 2009;)

dithiocarbamate Co(II) acetate (150  4.6 mm) 5 µm sample

26 EDTA Cr(III),Cr(VI) Orthophosphate Nucleosil-100 C18 ion 200/UV 4.00/1.00 0.02,0.3/0.06, 0.6 µg/L Aqueous (Threeprom et al., 2005;)

buffer and water exchange column mL/min matrix

(250  4.6 mm) 5 µm

27 - As and Cr Acetonitrile and Econosil C18 column 194 &360 6.00/1.0mL/min 0.01,0.4/0.03, 1.2 µg/L Aqueous (Ali et al., 2002;)

water (250  4.6 mm) 10 µm nm/UV matrix

28 8-HQ Mg and Al Acetonitrile and ODS C18 column λex 360 nm 1.00 mL/min 18-16 ng/mL River, rain and (Takeuchi et al., 2001;)

buffer with oxime (150  4.6 mm) tap water

λem 516 nm

29 DNTB Zn(II), Cu(II), Pb(II) Tris HCl BUFFER Size exclusion column, 417 nm / ICP- 7.00/0.7 - Fish Bile (Davis et al., 2012;)

Superdex75 MS mL/min

30 - As(III), As(V), DMA, AsB Aqueous Anion exchange column, ICP/MS - 18.7/56.1 Carrots (Vela et al., 2001;)

Ammonium isocratic
µg/L
carbonate

45
ACCEPTED MANUSCRIPT
 ACCEPTED MANUSCRIPT
31 - As(III), MMA, DMA, AsB Aqueous ammonium Micro Mist glass concentric ICP-MS /1.15 mL/min 0.3-1/0.9-3 µg/L Urine (Kalman et al., 2013;)

carbonate, gradient nebulize

32 Curcumin Boron TBABr: Methanol Chrome C18 column ICP-MS /AES 0.8 mL/min 0.02-0.5/.061.5 µg/L Uranium oxide (Rao and Aggarwal, 2008;)

(15 cm x 4.6 mm) 5µm

33 Phyto chelatins Cd(II), Pb(II) Acetonitrile and Alltech Ultima, C18 HPLC/ ESI-MS 4.5/0.2 mL/min - Pea (Bardkiewicz et al., 2009;)

formic acid Column

150 × 2.1 mm) 5 µm

34 Carbon nanotubes Cr(III) and Cr(VI) Nitric acid and PTFE microcolumn ICP-MS 3.0/1.2 mL/min 0.024 /0.072 ng/mL Mineral water, (Chen et al., 2010;)

distilled water (20 × 3.0 mm lake water

35 - Sb(III), Sb(V), trimethyl antimony(V) EDTA and KHP Anion exchange column 217 nm HPLC- 1.00 mL/min 7/21 ng/L Marine biota (Gregoria et al., 2007;)

salts in diammonium (UV)-HG-AFS. sample

hydrogen phosphate

buffer solution

36 3-(2-amino ethylamino) Cr(VI), Se(VI), As(III), As(V), Cr(III) Nitric acid and PTFE micro-column ICP-MS 3/ 0.8 mL/min 15,16/45,48 ng/L Enviro mental (Peng et al., 2015;)

Propyl trimethoxy silane acetonitrile (20  2.0 mm samples

37 - As(III), As(V), DMA, MMA Hexanesulfonic acid C18 Alltima, HPLC-IP 4.5/0.9 mL/min 40,12/120, 36 µg/L Nut oils (Kannamkumrath et al., 2004;)

and citric acid (4.6 × 150) mm, 5 µm

38 - Methylmercury, ethylmercury, mercury 2-mercaptoethanol Perkin-Elmer C8 (3 × 30 CV-ICP-MS 4.7/1.2 mL/min 0.003-0.006/0.009- Cereals (Lin et al., 2008;)

and methanol mm). 0.018

ng/mL

39 - Cr(III) and Cr(VI) EDTA2(Na) 5 mM Reverse phase C8 column HPLC-ICP-MS 7.0/1.2 ml/min 0.1/ 5.1 µg/L Drinking and (Catalani et al., 2015;)

pH 7 Agilent part number tap water

(150 x 4.6 mm) 3.5 μm samples

46
ACCEPTED MANUSCRIPT
 ACCEPTED MANUSCRIPT
40 - Bromide, iodate, iodide Ammonium nitrate Ion pack anion-exchange HPLC-AEC 1.5ml/min 0.01-0.12/0.03-0.36 Atmospheric (Moreda-Pineiro et al., 2012;)

and methanol column ng/ml particulate

(250  4 mm) matter

41 - Selenium and arsenic 5 mmol l−1 TBAH in ZORBAX Eclipse XDB-C18 ICP-ESI-MS 6.0/1.00 ml/min 19 to 22 ng L−1 for As River, Plant (Afton et al., 2008;)
−1 −1
2.5 mmol Column and 312 to 442 ng L extract and

(NH4)3PO4 (pH 6.0) (250 mm x 4.6 cm) 5 µm for Se urine matrices

42 Quercetin Aluminium(III) Perchloric acid and Nova-Pak C 18 415/UV 3.5/1.0ml/min .014/.042 µg/L Aqueous (Lian et al., 2004;)

methanol (150 × 3.9) mm

43 CHAPS Al(III) Tris HNO3 and CHAPS coated C18 Column 220/UV 0.7 ml/min 0.74,0.83/ 2.22, 2.49 Human serum (Chen et al., 2010;)

CHAPS (250 × 4.6) mm ng/mL

44 Quercetin Al(III) Trifluoroacetic acid column Shield RP18 350/ HPLC- 7/0.7 ml/min - water (Bourhis et al., 2011;)

and water (4.6 × 250 mm) 5 μm PDA

45 - As(III), As(V), Se(IV), Se(VI) Phosphate buffer Anion exchange column 196 nm/ HPLC- 5.5/ 3.0 ml/min 7.8-18/23.4-54 ng/ml Ground water (Niedzielski et al., 2005;)

and Na2HO4 (250 × 4.6) mm 5 µm HG-AAS

46 PAR Mn(II), Fe(II), Co(II), Ni(II), Cu(II) and Tris buffer Ion Pac CG5A guard column. 530/PDA 0.5 ml/min - Proteins (Atanassova et al., 2004;)

Zn(II) (250  4 mm)

47 - Arsenic As(III), As(V) and chromium 1 mM TBAH+0.7 Phenomenex Kinetex C18 ICP-MS 7.2/ 0.7mL/min 0.009 Iron (Araujo-Barbosa et al., 2017;)

Cr(III), Cr(VI) mM EDTA (100 mm × 4.6 mm id, 2.6 and 0.027 µg/g 0.029 supplements

µm) and 0.089 µg/g

48 2-acetylpyridine-4-phenyl- Pt(II), cis platin Acetonitrile, Phenomenex C-18 380/UV 1.0 mL/min 50-90 ng/mL Serum and (Khuhawar and Arain, 2005;)

3-thiosemicarbazone methanol and (150 × 4.6) mm urine samples

tetrabutylammonium

bromide

47
ACCEPTED MANUSCRIPT
 ACCEPTED MANUSCRIPT
49 Emetine-dithiocarbamate Mercury, methy, ethyl, Acetonitrile and L-column ODS2 HPLC-CL 6/0.3 mL/min 30 ng /L, 21 ng /L Water, (Kodamatani et al., 2012;)

citrate buffer Column biological

phenyl mercury
(250 × 4.6) mm 5 μm

50 Sodiumdibenzyl Cd(II), Cu(II), Zn(II),Pb(II), Fe(II) Methanol and Alltech C18 column 254/HPLC- 5.2 0.1-1.8 / 0.3-5.4 ng/mL Water samples (Todorovi et al., 2002;)

dithiocarbamate. acetonitrile (150 × 4.6 mm) AAS

51 - TMSe, SeMet, Se(IV), Se(VI) Triethylamine and Hamilton PRP-X100 ICP-MS 5.0 - Yeast (Cabanero et al., 2005;)

acetic acid (250 × 4.1 mm) 10 µm

SeCys2

52 - Soluble proteins Tris HCl and KCl BioSep SEC 2000 HPLC-UV/ICP- 6.8 Chicken liver (Cabanero et al., 2005;)

MS

53 2-thiophenaldehyde-3- Co(II), Pd(II), Ni(II), Cu(II) Acetonitrile and Dionex Acclaim 120 C18 390/HPLC-UV 8.0/0.80 ml/min 0.001-0.009/ 0.003- Alloys and (Kaur et al., 2007;)

thiosemicarbazone water Column 0.027 drinking water

(250 × 4.6) mm 5 µm

54 APDC Cr(VI), Co(II), Cu(II) and Ni(II) Acetonitrile and UPLC BEH C8 waters 256 nm/ HPLC- 3.0/0.5 mL/min 0.5-1.5/1.6-4.9 µg/L Tap water (Razmisleviciene et al., 2011;)

water (70:30) 100  2.1) mm 1.7 µm DLLME

55 Salophen Ni(II), Co(II), Cu(II) and Zn (II) Methanol: Perfect sil target C18 Column 436 nm/ HPLC- 6.5/ 1.0 mL/min 0.8-2.8/ 2.6-9.2 µg/L Tap water and (Asghari et al., 2014;)

acetonitrile: water (250  4.6) mm DLLME mineral water

56 Sodium DDTC Methylmercury (MeHg+) and mercury 90% (v/v) methanol- Supelco (USA) Discovery HPLC-CPE 0.8 mL/min 4 and 10 / 13.2 and 33 Enviromental (Chen et al., 2009;)
2+)
(Hg 10% (v/v) water C18 column ng/L and biological

containing DDTC (4.6 x 15 mm) 5 µm samples

1.0  104 mol/L

57 DDTC Hg Triton --X-114 and Waters C18 ODS Column HPLC-CPE 5.5/0.8 mL/min 8.0-13 / 24.7, 39.5 ng/L Environmental (Chen et al., 2009;)

methanol (150 cm x 4.6 mm) 5 µm ICPMS aqua &

biological

48
ACCEPTED MANUSCRIPT
 ACCEPTED MANUSCRIPT
samples

human hair &

ocean fish

58 DDTC Cr(III) and Cr(VI) Methanol: water: Waters ODS Column 254 nm/ HPLC- 3.6/1.0 mL/min 3.4-5.2 / 11.2-17.1 µg/L Snow, river, (Tang et al., 2004;)

acetonitrile (150 cm x 4.6 mm) 5 µm CPE sea and waste

(65:21:14) water samples

59 - Tetraphenyltin, triphenultin hydroxide, Acetonitrile and Waters spherisorb ODS HPLC-UV/254 1.0 mL/min 0.01 µg/mL Aqueous (Mitchell et al., 2010;)

trihenyltin acetate water (150 cm x 4.6 mm) 5 µm nm environmental

samples

60 EDTA As(III), As(V), Cr(VI), Sb(III) and Sb(V) 3 mM EDTANa2, 36 Anion-exchange HPLC HPLC-ICP- 9.0/ 1.2 mL/min 0.7-3.7 µg/L Drinking and (Marcinkowska et al., 2017;)

mM NH4NO3 column PRPX100 DRC-MS tap Water

(4.6 mm × 150 mm) samples

61 - Inorganic mercury and organic mercury Methanol: Spherisorb ODS column HPLC-SPE 7.5/ 1.5 mL/min 1.9-2.2 6.2-7.2 ng/L Water samples (Tsoi and Leung, 2011;)

acetonitrile: 0.1 M Perkin Elmer

sodium acetate 22 cm x 4.6 mm, 5 µm

acetic acid

(40:38:22)

62 Mercapto ethanol Inorganic mercury, methyl mercury and (0.4% (v/v) 2- Kinetex C18 Column HPLC-SPE 2.5/0.7 mL/min 3.3, 2.0, and 3.6/ 11, Sea water (Pilar et al., 2015;)

ethyl mercury mercapto ethanol, (100 × 2.10) mm 5.0 µm 6.7, and 12 ng/L

10% (v/v) methanol)

63 DDTC Nickel, cobalt and mercury Methanol and water C18 Column 320 nm/ HPLC- 1.0 mL/min 0.1-2.7/ 0.33-8.9 µg/L Environmental (Zhou et al., 2014;)

(80:20) (4.6  250) mm, 5 µm SPE samples

64 - Methylmercury, ethyl mercury and phenyl Methanol and 30% RP C18 Column 254 nm/ HPLC- 6.0/ 1.0 mL/min 0.3--3.8 / 0.9-12.5 ng Seafood and (Xia et al., 2007;)

water containing (Lichrospher-ODS) environmental

49
ACCEPTED MANUSCRIPT
 ACCEPTED MANUSCRIPT
mercury 0.001%2- (200  4.6) mm HF-LLME mL−1 samples

mercaptoethanol, 20

mmolL1 buffer

solution

65 o-phenyl-enediam-mine Se(VI) 50 mM ammonium ODS-3 Column 332 nm / 4.6 0.1 and 0.02 / 0.3 and Urine, natural (Saleh et al., 2009;)

acetate and (100  4.0) mm, 3 µm HPLC-LPME 0.06 µg L−1 water and

methanol with plasma

gradient program samples

66 - MeHg+, EtHg+ and PhHg+ THF/MeOH/0.1M Phenomnex C-18 HPLC-IL- 4.0/ 0.8 mL/min 1.0 and 22.8 / 3.3 and Tap, river and (Pena-Pereira et al., 2009;)
−1
sodium acetate with 150  4.6mm 3 µm SDME 75.24 µg L waste water

50 µm EDTA

(36/32/32)

67 Dithizone (DZ) Mercury species Hg2+ methyl mercury Methanol/ Octa dodecyl silica Column 475 nm/ HPLC- 4.0/ 1.0 mL/min 0.32, 0.96 and 1.91 µg Environmental (Gao and Ma., 2011;)
−1
(MeHg+) and phenylmercury (PhHg+) tetrahydrofuran/ (0.1 150 × 4.6mm DLLME L aqueous

M acetic/sodium samples like

acetate pH 4.0; 100 tap water, lake

µM EDTA) water and river

(32/35/33,v/v) water

68 - Inorganic mercury Hg2+ methyl mercury methanol,35% Nova-Pak Reverse phase C18 475 nm /HPLC- 4.00 mL/min 0.58, 0.66 and 0.54/ Sea Water (Sanchez et al., 2000;)
+ +
(MeHg ) and phenylmercury (PhHg ) tetrahydrofuran, Column DLLME 1.9,2.2, 1.8 ng/L

35% (0.1 M sodium 300 × 3.9 mm

acetate--acetic acid,

pH 4 EDTA), 30%.

69 - Selenium Phosphate buffer Multi affinity removal Extraction 6.0/1.0 mL/min - Human serum (Palacios et al., 2006;)

column process/Multi

50
ACCEPTED MANUSCRIPT
 ACCEPTED MANUSCRIPT
4.6  50 mm affinity

chromatography

70 APDC Cr(III) and Cr(VI) Acetonitrile: water Non end capped octa-decyl 540 nm Liquid 4.6/0.6 mL/min 2.2 µg/L for Cr(VI)and Industrial (Frumkin and Thun, 2001;)

(2:1) silica gel liquid 4.5 µg/L for Cr(III). waste water

(15 × 4.6 cm) 5 µm extraction/

HPLC-UV

71 - As(III), As(V), DMAA, 4- Methanol: TBAH or (Zorbax-SB C18, Agilent ICP-MS 6.25/0.7-1.0 <1.7 µg of As/Kg Animal feed (Narukawa et al., 2014;)

Hydroxyphenylarsonic acid TFA (8:92) Technologies150  4.6 mm mL/min

3.5 μm

72 - As(III), As(V), DMAA, Tetramethyl CAPCELL PAK C MG C18 HPLC-ICP-MS 3/0.75 mL/min 0.01, 0.01, 0.03 ng/g Rice flour (Carioni et al., 2017;)

ammonium column samples

hydroxide: methanol (250  4.6) mm

73 - As(III), As(V). DMA, MMA, AsB, AsC, Ammonium Ion Pac AG7 Dionex Guard LC-ICP-MS 8.2/0.1 mL/min 0.003-0.051 ng/g Urine (Zmozinski et al., 2015;)

TMAO Phosphate 2.5 mM Column

74 - As(III), As(V). DMA, MA, AsB, AsC, Pyridine 20 mM Hamilton PRP-X 100 LC-ICP-MS 2.6/ 1.5 mL/min 0.006, 0.021 mg/Kg Sea food (Amaral et al., 2014;)

TMAO 250  4.1 mm 10 µm

75 1,3-bis(2-cyanoben-zene) Hg2+, MeHg, PhHg Methanol: Spherisorb ODS column RP-SPE-HPLC 4/1.0 mL/min 0.8, 1.0 and 1.3 ng/L Water samples (Houk et al., 1980;)

triazene acetonitrile: 0.1 M Perkin Elmer USA

sodium acetate 4.6 mm × 22 cm 5 μm

buffer (40:38:22)

51
ACCEPTED MANUSCRIPT
ACCEPTED MANUSCRIPT

Figure 1: Typical element-selective chromatogram for (a) 5 ng/mL (as element) each of AsC,

AsB, As(III), DMA, MMA and As(V) and 100 ng/ml of Cl and (b) 100 mg/l of Cl. With

gradient program running from 0-0.1 min 100% A ramp to 100% B; 0.1-8 min 100% B 1

mL/min (A: 0.5 mM ammonium carbonate, 1% MeOH; B: 50 mM ammonium carbonate, 1%

MeOH) at a flow rate of 1mL/min (Arien et al., 2002;).

52
ACCEPTED MANUSCRIPT