This article was downloaded by: [Erciyes University]

On: 29 December 2014, At: 21:05

Publisher: Taylor & Francis
Informa Ltd Registered in England and Wales Registered Number: 1072954 Registered office: Mortimer House,
37-41 Mortimer Street, London W1T 3JH, UK

Critical Reviews in Analytical Chemistry

Publication details, including instructions for authors and subscription information:
http://www.tandfonline.com/loi/batc20

Determination of Thiocyanate within Physiological

Fluids and Environmental Samples: Current Practice
and Future Trends
a b
M. Valdés & M. Díaz-García
a
Department of Analytical Chemistry, University of Havana , Havana, Cuba
b
Department of Physical and Analytical Chemistry, University of Oviedo , Oviedo, Spain
Published online: 10 Aug 2010.

To cite this article: M. Valdés & M. Díaz-García (2004) Determination of Thiocyanate within Physiological Fluids and
Environmental Samples: Current Practice and Future Trends, Critical Reviews in Analytical Chemistry, 34:1, 9-23, DOI:
10.1080/10408340490273726

To link to this article: http://dx.doi.org/10.1080/10408340490273726

PLEASE SCROLL DOWN FOR ARTICLE

Taylor & Francis makes every effort to ensure the accuracy of all the information (the “Content”) contained
in the publications on our platform. However, Taylor & Francis, our agents, and our licensors make no
representations or warranties whatsoever as to the accuracy, completeness, or suitability for any purpose of the
Content. Any opinions and views expressed in this publication are the opinions and views of the authors, and
are not the views of or endorsed by Taylor & Francis. The accuracy of the Content should not be relied upon and
should be independently verified with primary sources of information. Taylor and Francis shall not be liable for
any losses, actions, claims, proceedings, demands, costs, expenses, damages, and other liabilities whatsoever
or howsoever caused arising directly or indirectly in connection with, in relation to or arising out of the use of
the Content.
This article may be used for research, teaching, and private study purposes. Any substantial or systematic
reproduction, redistribution, reselling, loan, sub-licensing, systematic supply, or distribution in any
form to anyone is expressly forbidden. Terms & Conditions of access and use can be found at http://
www.tandfonline.com/page/terms-and-conditions
 Critical Reviews in Analytical Chemistry, 34:9–23, 2004
Copyright c Taylor and Francis Inc.
ISSN: 1040-8347 print
DOI: 10.1080/10408340490273726

Determination of Thiocyanate within Physiological

Fluids and Environmental Samples: Current Practice
and Future Trends
M. Granda Valdés
Department of Analytical Chemistry, University of Havana, Havana, Cuba
M. E. Dı́az-Garcı́a
Department of Physical and Analytical Chemistry, University of Oviedo, Oviedo, Spain
Downloaded by [Erciyes University] at 21:05 29 December 2014

As the toxicological and physiological importance of thiocyanate has become more and more
evident during the past 20 years, there has been an increasing interest in this anion. Thiocyanate
is a detoxication product of cyanide and its content in human saliva is considered as a biomarker
for identification of nonsmokers and smokers. Chronically elevated levels of thiocyanate in body
fluids are known to be toxic and its relation to local goiter, vertigo, or unconciousness has been
pointed out. On the other hand, thiocyanate-containing waste discharged into rivers is harmful
to aquatic life due to its degradation to cyanide in the presence of oxidants. Therefore, precise
knowledge of the thiocyanate content in biological fluids and environmental samples is manda-
tory. An overview of the existing analytical methodologies for thiocyanate is presented and their
advantages and limitations are highlighted. This review is intended not only to provide a com-
parison of the different methods employed, but also to make it possible for the interested reader
to quickly find developments and relevant work that have transpired over the past 10 years.

Keywords anions, biological fluids, cyanide, environmental samples, thiocyanate analysis

The toxicological importance of thiocyanate has become ev- tion which is catalyzed by the mitochondrial enzyme rhodanese
ident during the past 20 years. Thiocyanate is hardly as toxic as (produced in the liver and kidneys) (3, 5).
cyanide and as such it has received attention from researchers The determination of SCN− is particularly important in
in diverse fields such as medicine, food chemistry, and envi- saliva, urine, and blood serum because it is considered to be
ronmental sciences. Thiocyanate ion is naturally present in hu- a biomarker in distinguishing smokers from nonsmokers. This
man body fluids and its concentration varies according to diet, is due to the fact that the low levels of thiocyanate present in
among other factors. It is derived endogenously as a detoxifica- body fluids (especially saliva) increase when there is an “expo-
tion product of cyanide in the liver (1); this being the major route sure” to cyanide. Therefore, the concentration of SCN− in the
of biological cyanide degradation (2, 3). Inorganic cyanide can body of a smoker increases because it is a metabolic product of
enter the body in several natural ways (4), yet the most impor- substances in tobacco smoke that contain cyanide (6–8).
tant source is tobacco smoke. Renal elimination of low levels While the saliva of nonsmokers contains concentrations be-
of CN− from the body occurs by its conversion to SCN− , reac- tween 0.5 and 2 mM (1, 9), in smokers concentrations as high
as 6 mM can be found. Lower values are detected in urine and
blood serum, but they are always higher in individuals who
smoke (especially cigarette smokers) compared to nonsmokers
The authors thank Dr. Recalde Ruiz who contributed to the work (8–10). Some authors have determined that the SCN− content
described herein. Dr. Mayra Granda Valdés is grateful to the University decreases from saliva to blood to urine and that this implies thio-
of Oviedo and the University of Havana for support provided through cyanate is accumulated in blood from the mouth, while it be-
the International Exchange Programme during fall 2002. comes diluted when excreted (11). Yet in other papers, mention
Address correspondence to Prof. Dr. M. E. Dı́az-Garcı́a, Depart-
ment of Physical and Analytical Chemistry, Faculty of Chemistry, has been made of higher contents in urine than in blood (7, 10).
Av. Julián Claverı́a, 8 33006-Oviedo, Spain. E-mail: medg@sauron. There are other several reasons why this anion is of medical
quimica.uniovi.es interest. Among them, we can include:
9
 10 M. GRANDA VALDÉS AND M. E. DÍAZ-GARCÍA

a. Chronically high levels of thiocyanate can inhibit the nor- manufacture of thiourea (20), while sodium thiocyanate solu-
mal uptake of iodine in the thyroid gland, thus reducing tion serves as a dispersive medium for copolymers obtained in
the formation of thyroxine and is therefore possibly re- the manufacture of acrylic fiber (21). Thiocyanate is also used
lated to goiter (12–14). as a petroleum tracer in oil fields to investigate the distribu-
b. Monitoring patients that have needed lengthy treatments tion of oil deposits and the stratigraphic structure as well as the
of sodium nitroprusside, after heart surgery or malignant effectiveness of water blocking (22).
hypertension, is important since this hypotensive agent The thiocyanate anion is a reductor and is very stable at any
metabolizes into SCN− (6). pH value (23). It forms colored complexes with several cations,
c. SCN− plays an important role in antimicrobial systems the best known being the red ferric ion complex which is used
by acting as a substrate for peroxidases (1). for the identification of Fe(III) (24–26) as well as for SCN− as
d. High concentrations may conduce to vertigo, nasal bleed- will be seen in the present article. This anion is also employed
ing, or unconsciousness (15). for the qualitative determination of iodate and the cuprous ion
e. Saliva thiocyanate may have an antibacterial role thereby (27, 28).
reducing the possibility of corrosion of amalgams or the Its analytical application not only is in qualitative analysis
danger of caries (13). since it is mostly used as reagent in several quantitative deter-
f. The negative effect of this anion on protein iodination has minations. For example, it forms numerous ion pair systems
been studied (14). (ternary complex or ion-associate complex) which are used for
Downloaded by [Erciyes University] at 21:05 29 December 2014

g. It is used as a drug treatment in certain thyroid conditions extraction or precipitation purposes (11, 13, 29–32) in the quan-
and arterial hypertension (7, 10, 15). titative analysis of different inorganic as well as organic com-
h. Recently, its capacity to detoxify ingested carcinogens ponents by several instrumental methods. In the chloride ion
has also been investigated (1). spectrophotometric determination, mercury thiocyanate is em-
ployed as the color reagent (33, 34).
On the other hand, the normal concentrations of thiocyanate The anion is also the basis of the indirect determination
in the body originate fundamentally from food. The ingestion of various species. Sulfide, for example, is determined indi-
of vegetables of the genus Brassica (5), such as turnips, kale, rectly through the SCN− formed when S2− reacts with CN−
and cabbage (7) that contain glucosinolates, or milk and cheese and I2 .; thiocyanate is then measured spectrophotometrically
that actually contain inorganic thiocyanate (4) are the most im- with Fe(III) (23). The same basic procedure is employed in
portant sources of this anion in the body. the determination of rhodanese enzyme activity, where thiosul-
SCN− is formed as a degradation product of indol-3- fate in the presence of cyanide produces the thiocyanate anion
ylmethyl-glucosinolates and other glucosinolates which give which is then monitored using capillary zone electrophoresis;
a carbonium ion and the thiocyanate ion in nonenzymatic and the rate of the enzymatic reaction depends on rhodanese con-
enzyme catalyzed reactions. This anion is thus considered to be centration (2).
important when the quality of certain vegetables is to be studied Many analytical methods have been used for thiocyanate
(12). Plasma thiocyanate is also important when studying pop- determination, beginning with the traditional gravimetric and
ulations that consume cyanogenic plant foods (6). Metabolism volumetric methods used for larger quantities of the anion to
of vitamin B12 and foods that contain cyanogenic glucosides, the costly and sophisticated gas chromatography/mass spec-
such as nuts and almonds, increase saliva thiocyanate (1). Yet, trometry (GC/MS) employed for the analysis of traces (35).
only extreme eating habits can considerably elevate the levels The major difficulty in its quantitation in most methods is the
of thiocyanate (7). potential interference of cyanide which usually accompanies
Another important sample where the determination of the thiocyanate in real samples (36).
thiocyanate anion is of interest is in water, especially wastewa- In the past 10 years or so three types of instrumental tech-
ters. This not only is so because of the content of SCN− itself, niques stand out: spectroscopy (especially molecular methods),
but because when wastewaters that contain the anion are chlo- electrochemical sensors (ion selective electrodes [ISEs]), and
rinated highly toxic cyanogen chloride is formed (16). At low chromatography (in several varieties). The scope of this review
pH values, thiocyanate contained in wastewaters (17) which is to provide a tighter focus on these techniques for thiocyanate
are discharged into natural waters converts into cyanide in the determination with a particular emphasis on their applicability.
presence of oxidants and thereby causes profound damage to
aquatic life (18). Its monitoring in plant outlets of certain in- SPECTROSCOPY
dustries (metallurgic and coal gasification) cannot be underes- Molecular (spectrophotometry and spectrofluorimetry) as
timated (19). well as atomic (atomic absorption) spectroscopic methods have
Areas of use of the anion include the application of thio- been used for the determination of thiocyanate, the first being
cyanate salts (ammonium and alkali) in several fields such as the most applied.
agricultural chemicals (as weed killers), dyeing and printing The spectrophotometric method most widely employed for
of textiles, in paints (inhibiting rust), and in photography (18). thiocyanate determination is the one based on the red com-
Ammonium thiocyanate is an important starting material in the plex (λ = 480 nm) formed with ferric ion, Fe(SCN)2+ , in acid
 DETERMINATION OF THIOCYANATE CONTENT 11

TABLE 1
Application of the Fe(III)-SCN− Spectrophotometric Method

Analyte Sample Comments Ref.

SCN− Saliva Comparison between smokers and nonsmokers (1)
SCN− and CN− Extract of bitter almonds (only After retention on a melanine-formaldehyde resin, SCN− is eluted (38)
CN− ) and then determined
SCN− Industrial wastewaters and Optimization of a sequential injection system (SIA) (19)
process solutions
SCN− Biological reactor in a steel plant Flow injection system (FIA) and continuous flow system (CFA) (39)
are optimized and a miniature spectrophotometer is constructed
SCN− Saliva, urine, and serum The spectrophotometric method is used as reference (11)
SCN− Saliva and serum The spectrophotometric method is used as reference (14)
Cl− (indirect) Cigarettes The spectrophotometric method is used to monitor the SCN− , (34)
after reaction of Cl− with mercury thiocyanate
S2− (indirect) Natural waters The spectrophotometric method is used to monitor the SCN− (23)
formed in the reaction of sulfide
Downloaded by [Erciyes University] at 21:05 29 December 2014

medium (37). The method is simple, straightforward, nontoxic, nation of SCN− using the Fe(III) spectrophotometric method:
and cyanide does not interfere, yet it has some disadvantages. flow injection system (FIA), continuous flow system (CFA),
Several species can be formed between Fe(III) and SCN− , and (CFA) with coupled fiber optics (CFA-FO). The first two
therefore ferric ion must be in excess; there is a wide range were applied to the analysis of the anion at the entrance and
of interference and color stability depends on the acid used and exit of a biological reactor installed in a coke plant of a steel
its concentration (19). industry for the treatment of wastewaters. The results obtained
Although this method dates back a long time (20) and despite were in good agreement with the official manual method while
its disadvantages, it is still valid and has extensive use not only the rate of sampling and the analytical characteristics were su-
for the quantitation of the anion in diverse samples, but also perior. For the CFA-FO system, a flow cell was designed and
for its detection in the indirect determination of other species constructed in the lab; the complete system is shown in Figure 1.
where thiocyanate is formed. It also has been employed by This configuration was employed in the continuous monitoring
many authors as a reference method against which the results of of the biological degradation process of SCN− in a minireactor.
their proposed methods were compared. It is the recommended The same authors (39) went even further in the application
method for the analysis of drinking water and wastewaters (16). of the systems studied, designing and constructing a miniature
Some examples of these applications are shown in Table 1. flow spectrophotometer for the in situ control of the anion us-
Of those used for determining SCN− as such, the most inter- ing the ferric ion method and the CFA. The small dimensions
esting ones are those in which some sort of flow system is of the detector and flow cell make the system ideal for field
employed instead of the traditional batch analysis. measurements. A linear calibration curve was obtained when
In the recent sequential injection system (SIA) automated employed, and present work is being done in the application to
determination (19), the physical (flow rates, loop volumes, real samples.
coil lengths) and chemical (reagent concentrations) parameters Many other spectrophotometric reagents have been em-
are optimized. The system is totally computerized and sample ployed for the determination of thiocyanate. Some of those
throughput is 24 h−1 . The advantages of the SIA technique developed within the past decade or so are listed in Table 2.
overcome one of the disadvantages of the spectrophotometric One of the best known, and oldest, reactions for the deter-
determination, the color instability, and therefore a great mination of cyanide is that which occurs, after halogenation
number of samples can be analyzed on-line without any lack with bromine, with a mixture of pyridine and benzidine to form
of reproducibility. a strongly colored dye (44). This method, first described by
Analytical characteristics are determined and interferences Aldridge and based on the modified König (45) reaction, has
are studied; the species commonly interfering in the Fe(III) suffered modifications due to replacement by less toxic reagents
method do so here, but most are not present in the type of (46), and for a faster reaction and a more highly colored prod-
samples investigated or are below the interfering level. Several uct (40). Yet, whatever the combination of reagents, thiocyanate
samples are analyzed and results are in good agreement with interferes positively since it also reacts after halogenation. Be-
those obtained with the same spectrophotometric method but cause of this, the method is used by many authors for the spec-
in a batch approach and using a diode array spectrophotometer. trophotometric simultaneous determination of both anions.
Dı́az-Garcı́a et al. (39) optimized three different flow sys- Masking or separation of one of these anions is necessary
tems (physical as well as chemical parameters) for the determi- if simultaneous determination is to be made when using some
 12 M. GRANDA VALDÉS AND M. E. DÍAZ-GARCÍA
Downloaded by [Erciyes University] at 21:05 29 December 2014

FIG. 1. Schematic diagram of a flow system for continuous monitoring thiocyanate degradation in a simulated bioreactor using
an optical fiber setup.

modification of Aldridge’s method. Sweileh (41), for example, saliva, requiring only centrifugation and dilution of the sample,
masked cyanide with a nickel salt, while Tanaka et al. (47) previous to determination. Detection is made using a three-
made use of the different diffusion rates of each ion through channel system where each reagent, besides the carrier, is
a microporous membrane and combined this with their differ- mixed with the sample producing an intensely colored product
ent reactivities toward chloramine T to differentiate them. The (λ = 570 nm). Reaction kinetics and conditions avoid cyanide
method recommended (16) is cyanide masking with formalde- interference. The method has an ostensible disadvantage: a large
hyde, a technique employed by Meeussen (40). This author background signal.
found that for effective masking of 250 ng/mL of CN− , the sam- A complex continuous flow configuration was used by
ple must be heated at 50◦ for at least 15 min or left overnight Meeussen et al. (40) where all the necessary steps (sample de-
at room temperature. When masking by formaldehyde was composition under ultraviolet [UV] light, distillation, chlorina-
adapted to a stopped flow setup, less effectivity was found (48). tion, cyanide masking, and color reaction) occur on-line. This
Since Ruzicka and Hansen (49) introduced flow injection complexity is due to the fact that both cyanide and thiocyanate
methods in analytical chemistry, the advantages of flow tech- as well as iron-cyanide complexes are determined. In spite of
niques, combined fundamentally with spectrophotometry, over the system employed, sampling rate is reported as 22 h−1 .
traditional manual methods, have encouraged their use by many Themelis and Tzanavaras (13) also used an FIA for the
researchers for the quantitation of a wide variety of analytes, on-line extractive-photometric determination of thiocyanate
thiocyanate included. plus cyanide. Simultaneous extraction with chloroform oc-
A flow injection configuration was proposed by Bendtsen curs after the anions react with DPQH (Table 2) forming
and Hansen (7) for the sole determination of thiocyanate in ternary complexes (λ = 540 nm); therefore, for the individual
 DETERMINATION OF THIOCYANATE CONTENT 13

TABLE 2
Spectrophotometric Reagents Used for SCN− Determination

Reagent Sample Characteristics Ref.

Chloramine T and Water Modification of Aldridge method (40)
1,3-dimethyl-barbituric Simultaneous determination where cyanide is masked
acid + isonicotinic acid with formaldehyde
Continuous flow system
Sodium isonicotinate and sodium — Flow injection method (41)
barbiturate Two-step procedure for simultaneous determination
where CN− is masked with Ni(II)
2-(5-Br-2-pyridylazo)-5-diethyl Saliva Turned around procedure formally used for bromate (7)
aminophenol and dichromate determination
Cyanide does not interfere
Flow injection system
— Saliva Sample is hydrolyzed in concentrated acid medium (10)
and volatile octadecyl silica (OCS) is generated
Downloaded by [Erciyes University] at 21:05 29 December 2014

Cryogenic preconcentration system

The vapor is determined directly in the ultraviolet
(UV) using a continuous flow cell
I2 –azide Saliva Iodine concentration changes are monitored using (42)
starch solution
Stopped-flow kinetic method where reaction is
induced by thiocyanate
Cu(II) and 2,2 -dipyridyl- Saliva and pralidoxime Ternary complexes are extracted into chloroform (13)
2-quinolyl hydrazone (DPQH) solutions using a flow injection system
CN− is masked on-line with formaldehyde;
simultaneous determination is possible
NaOCl and 1,3-dimethyl- Plasma and urine Modification of Aldridge method (43)
barbituric acid + isonicotinic SCN− is isolated from alkaline solution of sample
acid on an ion exchange resin and eluted with NaClO4
Sodium nitroprusside (SNP) interferes
NaOCl and 1,3-dimethyl- Plasma Sample treatment with 5% trichloroacetic acid (6)
barbituric acid + isonicotinic SNP shows no inhibitory effect
acid

determination of SCN− , cyanide is masked with formaldehyde. termination of thiocyanate, since the polymethine dye formed
In this case masking was successful because a binary inlet static was found to be fluorescent. The best reagent mixture was the
mixer, that allowed efficient mixing, was used. Cyanide was de- combination of isonicotinic acid and barbituric acid and a four-
termined by difference after total analyte concentration was de- channel flow injection procedure was proposed. Cyanide can
termined in another run in which no masking agent was present. also be determined by the same method, and therefore it in-
A 60 h−1 sample throughput was reported. terferes in thiocyanate analysis. All analytical parameters were
A spectrophotometer equipped with a stopped-flow module optimized, but various practical problems were encountered for
(42) was used for the kinetic determination of thiocfanate and real sample application: several on-line operations require dif-
thiosulfate monitoring the decrease of the absorbance of the ferent pH values, while heating (at 60◦ C) and then cooling in
iodine-starch complex near zero time reaction. This initial rate an ice bath are necessary operations.
of decrease is found to be related to the anion concentration. Some reported spectrofluorimetric methods for thiocyanate
The proposed method is reported to be faster, more economic, are not based on the fluorescent product formed when SCN−
accurate, precise, and sensitive than the corresponding batch reacts with adequate reagents, but on its inhibitory effects on a
method where measurement is made after reaction is completed. reaction where fluorescence is quenched, thereby increasing the
Other molecular spectroscopic methods used for thiocyanate signal as thiocyanate concentration increases. In this line Zhang
determination are based on fluorescence measurements. Tanaka et al. (15) reported the thiocyanate determination in saliva and
et al. (50) studied several combinations of reagents, all based urine without pretreatment of the samples, based on the inhi-
on the modified König reaction, for the spectrofluorimetric de- bition produced by the anion on the bromate oxidation of the
 14 M. GRANDA VALDÉS AND M. E. DÍAZ-GARCÍA

fluorescent dye Rhodamine 6G (the molecular structure of the low cost, simplicity, and wide linear range. In the past decades
dye is destroyed). A kinetic approach was used and excellent polymeric membrane-based ISEs have reached outstanding de-
results were obtained for traces of the anion; the method proved velopment. The key component in the sensor is the ionophore
to be simple, accurate, highly sensitive, and selective. (or ion carrier) contained in the membrane, which is capable of
Gong (14) also used a similar technique to determine SCN− interacting selectively with the analyte in the sample solution.
in saliva and serum. In this case, the reaction in which iodine Much has been done in the search (or design, including
and the strongly fluorescent 2 ,7 -dichlorofluorescein molecule biomimetic strategies) (54, 55) of selective ionophores for the
form a weakly fluorescent compound was hampered, due to the determination of cations and anions using ISEs and, although
iodine consumption: some of these electrodes are now commercially available, there
is a limited number of ion carriers that are really useful for an-
SCN− + 4I2 + 4H2 O → ICN + SO2− +
4 + 8H + 7I
−
ions. It seems that the synthesis of selective anion-carriers is
Therefore, fluorescence intensity increased with increasing more complex, due to some inherent characteristics of anions
thiocyanate concentration. For the reaction to proceed, heat- (ionic radii, hydration in protic solvents, shapes, and so forth)
ing in a boiling water bath for 3 min was necessary. Cyanide (56, 57). Therefore, the demand for selectivity in the field of
interference must be separated by distillation. Good agreement anion ISEs is very high; thiocyanate is not an exception.
between the proposed method and reference method was ob- Besides the polymer matrix (usually PVC) and the plasticizer
tained when samples were analyzed. (membrane solvent), the ionophore-impregnated membrane
Downloaded by [Erciyes University] at 21:05 29 December 2014

Fluorimetry has also been applied in optical sensing, al- also contains ionic additives in order to increase selectivity (58–
though the use of this type of sensor for thiocyanate determi- 61). We recommend readers interested in the subject view pa-
nation is not as widespread as electrochemical sensing (ISEs) pers by Bakker, Buhlmann, and Pretsch (59, 62) on the general
as will be seen below. characteristics of carrier-based ISEs where considerations are
A fluorimetric optical sensing approach comprising a fluo- made about the requirements of the different membrane compo-
rophore host based on a crown ether (PIP) has been developed nents, all of which influence the selectivity of these electrodes.
for monitoring thiocyanate in aqueous environments (51). The Most of the work done in the past 10 years or so, dealing
PIP acted as a logical AND chemosensor for the recognition of with SCN− sensors, is dedicated to the study of ionophores
SCN− , being its fluorescence quenched only in the presence of (usually organometallic compounds) that strongly interact with
both an alkali earth metal AND the thiocyanate anion. In a pre- the anion and interact only weakly with all others. If this inter-
vious work (52), we have reviewed this type of chemosensing action is purely electrostatic, selectivity is governed only by the
action. lipophilicity of the anions (the well-known Hofmeister pattern)
Another fluorescent chemical sensor for SCN− was de- (63–65). Although SCN− occupies one of the first places among
scribed by Kopelman et al. (53). An optode based on a the inorganic anions in this series, “real” selectivity (sometimes
ruthenium(II)-porphyrin ionophore combined with a universal referred to as anti-Hofmeister behavior) can be found only when
pH chromoionophore responds to log [aH+ aSCN− ]. As will be the anion and the ionophore interact by some sort of chemical
seen later, this organometallic compound is mainly employed binding (generally, metal-ligand interaction where the ligand is
in thiocyanate determination when using ISEs. the anion and the metal is part of the host molecule).
Atomic absorption spectroscopy is also used for the indi- It has been demonstrated by several authors (57, 58, 60,
rect determination of thiocyanate employing several metal com- 66–69) that the stronger or weaker metal-ligand interaction,
plexes (binary or ternary) extracted into different solvents. The and therefore selectivity and sensitivity, depends fundamen-
anion is then determined through the absorbance signal of the tally on the structure of the ionophore (also considering the
corresponding metal ion. The indirect atomic absorption tech- nature of the substituents and their position in the molecule,
nique for thiocyanate determination does not seem to have much and the nature of the central metal) as well as on the possibil-
acceptance by authors as in the past decade there has been a ity of thiocyanate to act as an axial ligand to the metal center
dearth of papers using this approach. Good results were ob- of the carrier molecule,thus forming a mixed ligand complex.
tained by Chattaraj and Das (11) when analyzing thiocyanate The stability constant (or the association constant at the fifth
in several biological fluids using the [Cu2-benzoylpyridine or sixth coordination site) of the so-formed compound should
thiosemicarbazone–SCN]+ complex extracted into isoamyl al- determine the order of selectivity (70, 71). Overall, qualitative
cohol. The organic phase, after two extractions, was directly and quantitative composition of the ISE determines its analyt-
aspirated into the air-acetylene flame and copper was deter- ical performance toward the ion of interest; the role played by
mined. The method is straightforward and analytical figures of coordination chemistry has been proven without doubt (64, 72).
merit are satisfactory. Since 1990, and even before, many papers can be found in
the field of carrier-based membrane anion selective electrodes
ION SELECTIVE ELECTRODES that include thiocyanate as part of the anions studied in order to
ISEs have become one of the most important types of chemi- establish a selectivity series (56, 58, 68, 73–76). We will make
cal sensors due to several advantages: relatively rapid response, reference to only those that center their research on thiocyanate
 DETERMINATION OF THIOCYANATE CONTENT 15

TABLE 3
Characteristics of Carrier-Based Membrane Ion Selective Electrodes (ISEs) for Thiocyanate

(−) Slope Resp.

Ionophores (mV/decade) Linear range (M) pH DL (M) time (sec) Life time Ref.
Mn(III)-porphyrins 59 ∼10−5 – 10−1.8 5.5 — — — (71)
Co(II)-Tetrakis (o-amino phenyl) 43 ∼10−5 –10−2.5 6 5 × 10−7 <25 At least 2 m (77)
porphyrin
Benzyltin-dichlorides 52.8 From 5.3 × 10−5 7 7.3 × 10−6 — — (69)
Au(III)-Triisobutylphosphine ∼55 10−4 –10−1 6.6 — ∼5.8–7 12 days (70)
sulfide
µ-Oxotetraphenyl porphyrinatoiron 53 10−6 –10−1 ∼3–5 3.9 × 10−7 — — (64)
Mn(III)-porphyrins ∼50 10−4 –10−1 6.5 3.2 × 10−5 — — (72)
Mn(II)-N,N -bis-(4- 57.3 7.0 × 10−6 –10−1 5.38 — <10 At least 2 m (66)
phenylazosalicylidene)
o-phenylene diamine
Ni(II)-phthalocyanine chloride 58.4 5 × 10−7 –10−1 3–10 5 × 10−7 2 At least 2 m (60)
Downloaded by [Erciyes University] at 21:05 29 December 2014

BenzoN4 nickel(II) macrocyclic 59.8 1.4 × 10−7 –10−1 3.5–10.5 1.4 × 10−7 5 At least 3 m (57)
complexes
1,8-dibenzyl-1,3,6,8,10,13- 58.4 3.3 × 10−6 –10−1 4.0–9.2 3 × 10−6 15 At least 2 m (67)
hexaazacyclotetradecane
Ni(II) perchlorate

selective electrodes. Table 3 lists a number of the more recent satisfactorily with the traditional colorimetric Fe(III)-SCN−
SCN− electrochemical sensors of the type mentioned. In those method.
cases where the information that appears in the table has been Transitional metal chelates of Schiff bases have also been
calculated from the data given by the authors, the numbers are used as neutral carriers for SCN− by Li and coworkers (66).
preceded by an approximation symbol (∼). The base, as well as different metal chelates, were synthesized
Most of these papers put their main attention on the study and four electrodes (varying in central metal, additive, and so
of the different parameters that can influence the ISE’s analyt- forth) were prepared and studied. In this paper, the mechanism
ical performance (in order to obtain the optimum conditions), of response was also investigated and conclusions similar to
as well as on the determination of the possible mechanism of Gao et al. (64) (coordination of the anion to the metal of the
response, according to the carrier used. Some also dedicate part host molecule) were obtained. The selectivity of the electrodes
of the research to the synthesis of the ionophore. However, few was tested and the Mn(II)-chelate electrode was applied to thio-
of the ISEs developed are applied to real thiocyanate-containing cyanate determination in wastewaters. The results were com-
samples, probably because selectivity is not always high or be- pared with a high-performance liquid chromatography (HPLC)
cause application of the electrode was not an objective of the method and good accordance was obtained. Unfortunately, the
work. Since real life is what determines the functionality or not authors did not report the detection limits (DL).
of a sensor, we will discuss fundamentally those that have been A similar work was done by Amini et al. (60) with thio-
applied to SCN− determination in some type of sample. cyanate selective electrodes based on nickel and iron(III) ph-
Gao et al. (64) selected µ-oxotetraphenyl porphyrinatoiron thalocyanines, but the carriers were not synthesized. Several
among several metalloporphyrins as thiocyanate carrier for the electrodes were prepared and their performance studied. After
preparation of an ISE because better potentiometric character- conditions were optimized, the nickel carrier electrode proved
istics were expected due to the stability of the binuclear com- to have somewhat better sensitivity and selectivity for SCN−
pound and because it has two coordination sites, as well as when compared to the iron compound. These authors also pre-
higher lipophilicity in comparison with mononuclear metallo- pared similar electrodes with both carriers but containing dif-
porphyrins. Effect of pH, as well as influence of solvent me- ferent additives (cationic and anionic), and demonstrated how
diators, on response characteristics were studied. The authors the nature of the additive can change the selectivity pattern. In
confirm the interaction mechanism by obtaining UV/Vis spec- this case, the anionic additive seemed to improve selectivity of
tra which indicate that two thiocyanates (through the N atoms) one of the carriers, but not of the other. Cationic additives only
were coordinated with the two central iron atoms. Smokers’ and worsened the responses.
nonsmokers’ urine samples, after 10-fold dilution, were ana- These results are opposite to that obtained by the previous
lyzed at pH 3 using the proposed ISE; results correlated very authors (66), which proved only that the ionophores involved
 16 M. GRANDA VALDÉS AND M. E. DÍAZ-GARCÍA

were in one case neutral (66), and in the other (60) charged. by the authors; all the system was automated. The reported
Two electrodes (one with each metal compound and no addi- figures of merit were quite good (e.g., the DL 0.78 µM, the
tives) were used to evaluate thiocyanate concentration in urine linear range 1 to 50 µM, and slope of calibration graph 121
(60). Again, results were compared with the spectrophotometric nA/µM). Thiocyanate determination in saliva samples of
method and agreed. smokers and nonsmokers (after 100-fold dilution and at pH 2)
In the most recent papers by Ardakani (67) and by Abbaspour using a standard addition procedure compared well with the
(57), two different nickel-based compounds were employed conventional spectrophotometric method.
as ionophores. In both cases, the authors synthesized the
ionophores, prepared several electrodes of different composi- ION CHROMATOGRAPHY
tion (changing the structure of the ionophore slightly, the plas- Since Small et al. (80) introduced ion chromatography (IC),
ticizer, or the percentage of the components), and studied the the two-column system using conductimetric detection has de-
electrodes’ response characteristics in order to optimize the veloped into a simple single-column system employing several
composition and select the best one. types of detectors: direct or indirect photometry, conductime-
Abbaspour (57) also investigated the coordination of the try, or amperometry. Also, stationary phases as well as eluents
central metal with the analyte anion and concluded that the can be greatly varied according to the nature of the species to be
unique saddle structure of the group of unsymmetrical benzo N4 determined and the accompanying components of the sample.
nickel(II) macrocyclic complexes favored axial coordination, The literature discussed previously in this review shows that
Downloaded by [Erciyes University] at 21:05 29 December 2014

and therefore selectivity of the electrode. Both Abbaspour (57) thiocyanate determination is of most interest when biological
and Ardakani (67) reported that their electrode was more selec- fluids, such as saliva, urine, and blood or serum, are concerned.
tive to SCN− than previous ones and, as can be seen in Table 3, According to Singh (81), IC is the method of choice for the
the macrocyclic compound showed the best performance. Thio- analysis of certain anions (SCN− included) and cations in these
cyanate concentration was determined by applying the proposed types of samples. Evidently this seems to be the case when
electrodes in both papers to clinical chemistry, urine, and saliva the simultaneous determination of several of these inorganic
samples of smokers’ and nonsmokers. The two authors com- species is desired due to the possibility not only of the sep-
pared their results with the standard colorimetric method; good aration of the analytes but also of their quantitation, whether
correlation was obtained in the comparison. In both cases the or not employing derivatization and/or postcolumn reactions
urine samples were pretreated in the same manner (1:10 dilu- (PCR) and different detectors. Because of UV absorption of
tion and pH adjusted to 5 with phosphoric acid and potassium thiocyanate around 210 nm, this type of detector is satisfactory
hydroxide), but the results obtained were not always similar, for its IC determination; usually lower detection limits are ob-
probably due to the difference in the population studied. tained when compared with conductimetric detection (82–84).
Although in their work Florido et al. (70) did not apply the On the other hand, new sorbents are constantly being synthe-
ISE developed, there are so few of these electrodes combined sized and studied for the ion chromatographic determination of
with flow injection methods that attention must be taken to anions (among them thiocyanate) (85).
this work. The ionophore, Au(III)-triisobutylphosphine sulfide, Although SCN− is quite hydrophobic and therefore strongly
was synthesized and electrodes with two different compositions retained on most columns, several IC methods have been suc-
were prepared. The electrodes were first characterized in the cessful in its elution in short periods of time and with rather
conventional configuration, but also in a flow-through tubular sharp peaks. Table 4 shows the general characteristics of some
system. Although optimized flow parameters were given the of these. Only in those papers related to biological samples has
actual configuration did not appear in the paper, but is referred thiocyanate been specifically determined. In the cases where
to a previous work (78). In order to stabilize the baseline, the the sample matrix was water (whether lake, ground, or spring),
carrier solution consisted of a pH 6.6 buffer containing a small it was part of the anions studied but its analysis was not under-
concentration of SCN− . Changes in analyte concentration were taken. The units for the DL reported by the authors have been
measured as changes in potential relative to the baseline. The respected.
analytical characteristics of the flow-through electrode seemed Chinaka et al. (3) and Michigami et al. (84) have determined
satisfactory and so was the sample throughput (80 h−1 ); yet, trace thiocyanate in human serum and blood using simple pre-
the lifetime of the sensor was shorter due to stripping of the treatments for the samples. In blood, extraction using water
ionophore by the carrier stream. and methanol was sufficient while the serum was deproteinized
Another flow injection determination of thiocyanate was using acetonitrile. In both cases conditions affecting retention
made by Cookeas and Efstathiou (79), but in this case the times and separation factors (choice of eluent, pH, µ), as well
electrode was a cobalt phthalocyanine modified carbon paste as wavelength of the detection, were studied. Samples of smok-
electrode (CoPC-CPE) and the detection was not potentiomet- ers and nonsmokers were analyzed and SCN− recoveries were
ric but amperometric. The preparation of the electrodes was over 95%. Chinaka simultaneously determined cyanide in the
quite simple and the flow system was a FIAstar analyzer cou- blood samples of fire victims using prior derivatization and flu-
pled to a wall-jet–type amperometric flow detector developed orescence detection.
 Downloaded by [Erciyes University] at 21:05 29 December 2014

TABLE 4
Determination of Thiocyanate by Ion Chromatography

Retention
Stationary phase Eluent Other anions Sample matrix time (min) DL Detector Ref.

TSK-gel IC anion-SW (35◦ C) 4 mM KH2 PO4 /2 mM K2 HPO4 (pH Cl− Serum 10 5 ng mL−1 Ultraviolet (UV) (195 nm) (84)
6.5)
− −
IC-PAK anion exchange 0.01 mM sodium naphthalene NO−
2 , Br , I , — 17 0.02 µg/mL−1 Indirect UV (280 nm) (86)
−
trisulfonate/10% CH3 CN NO3 , SO2−4
Octadecyl silica (ODS) 1 mM citrate (pH 7.0) — Saliva, urine 16 0.02 µg/mL−1 UV (210 nm) (83)
column coated with
cetyldimethylamine (35◦ C)
2− −
Shim-Pack CLC-C8 15:85 CH3 OH/60 mM phosphate pH NO− 2 , S2 O3 , IO3 , Lakewater 7 104 ng/mL−1 Amperometry with glassy (87)
2−
5.5 buffer containing 0.1 mM S carbon indicator
EDTA and 3 mM tetrabutyl electrode
ammonium hydroxide
−
Bovine serum albumin 0.15 mM tartaric acid (pH 3.6) Br− , I− , NO− 3 , IO3 Saliva ∼9.5 82 µM UV (210 nm) (88)
immobilized on ODS
2−
TSK-gel IC anion-PW 0.006 M carbonate/15% CH3 CN S2− , S2 O2−
3 , SO3 Hot springwater 21.5 0.05 ng in 50 µL Postcolumn reactions (89)
(PCR) (350 nm)
TSK-gel IC anion-SW 10 µM phosphate buffer CN− Blood ∼8 86 pmol/mL−1 UV (210 nm) (3)
(pH 6.1)/50% CH3 OH
ODS 20:80 CH3 CN/H2 O (pH 5) with 6 S2 O2−
3 , Springwater 7.4 40 nM UV (230 nm) (90)
mM tetrapropyl ammonium salt polythionates
−
Dionex ion pac AS 16 Electrolytically generated KOH (in S2 O2−
3 , ClO4 , Groundwater 28 — Suppressed conductivity (91)
3−
gradient mode) AsO4
−
Phenomenex hypersil (ODS) 10 mM tetrabutyl ammonium NO− 2 , NO3 Urine 4.4 0.02 mg/L−1 UV (230 nm) (4)
column (45◦ C) phosphate in 20% CH3 OH
Coated Zwitterionic-charged Water I− Saliva ∼5 1.2 µM UV (230 nm) (92)
develosil ODS-5
− −
Coated Zwitterionic-charged 20 mM NaH2 PO4 /Na2 HPO4 NO−
2 , I , NO3 Saliva ∼13 — UV (230 nm) (93)
develosil ODS-5 (pH 6.8)

17
 18 M. GRANDA VALDÉS AND M. E. DÍAZ-GARCÍA

Michigami (83) also analyzed thiocyanate in human saliva

and urine, but in this case the stationary phase was an octadecyl
silica (ODS) column dynamically coated with cetyldimethy-
lamine. Here again various experimental conditions were opti-
mized: choice of reagent, eluent concentration, and pH, as well
as λ. Saliva and urine samples were simply diluted before in-
jection; the recovery experiments in both samples were over
95%. The results of SCN− analysis in smokers and nonsmok-
ers by the proposed IC method compared well with those of the
Fe(III)-SCN− spectrophotometric method.
Another short C18 column was used (4) at an elevated temper-
ature (45◦ C) and with a mobile phase of tetrabutyl ammonium
phosphate in order to obtain fast ion interaction and low reten-
tion times for thiocyanate (<5 min). Chromatographic condi-
tions (selection of ion pair reagent, of organic modifier, con-
centration and pH of the eluent, as well as temperature and
flow rate) were optimized. In this method, however, the urine
Downloaded by [Erciyes University] at 21:05 29 December 2014

samples were first pushed through an SPE C18 cartridge for the
FIG. 2. Analyte stationary phase interactions concurring in
removal of organic interferents. A standard addition technique
electrostatic ion chromatography.
was employed to quantify SCN− in the samples of smokers and
nonsmokers.
and amount of the adsorbed Zwitterionic compound, as well
Again a bovine serum albumin (BSA) modified ODS col-
as surface charge density.
umn was used by Zein et al. (88) for the separation of inorganic
The authors reached interesting conclusions on the retention
UV-absorbing anions. Proteins have amphoteric behavior and
mechanism and found that the elution order of the anions
therefore can be used as potential stationary phases for both an-
responded to Hofmeister’s series, being SCN− next to last
ion and cation exchange, all depending on the pH of the mobile
(ClO−4 ) among the anions studied. Therefore, they suggested
phase. Under acidic conditions (sulfuric, aspartic, and tartaric
that the hydration energies of the ions were responsible
acids were studied), several anions were eluted from the col-
for their separation. The analytical performance of the ion
umn. Tartaric acid provided the best separation in a reasonable
chromatographic system was evaluated only by measuring the
period of time. The authors applied the BSA column, after opti-
elution times of the many species investigated, but no figures
mizing experimental conditions, to the determination of nitrate,
of merit were determined.
iodide, and thiocyanate in saliva. Yet, no comparison with other
methods of analysis or recovery studies were done.
Hu et al. (92, 93) developed electrostatic ion chromatography OTHER METHODS
(EIC) for the separation and detection of thiocyanate and other Table 5 lists several other methods used for thiocyanate de-
anions in human saliva. For this, they used Zwitterionic surfac- termination which were not included above since the number
tants above the critical micellar concentration and passed the of papers dedicated to the quantification of this anion by the
corresponding solution through an ODS column for 30 min at particular method is rather limited. Of these, capillary elec-
a flow rate of 2.8 µL/min. The positive and negatively charged trophoresis (CE) seems to be the most important. According
stationary phase separated the anions using the simultaneous to some authors (96) CE will continue to be displaced by IC
electrostatic attraction and repulsion reactions (Figure 2). The for the determination of ions found in water and other liquid
mobile phase in the earlier paper (92) was simply water, and matrices, while others (97) have stated that IC may have met
in the later (93) a phosphate buffer. Resolution of nitrate and its match in CE. This deserves some comment on those papers
nitrite peaks was also achieved although the retention times in- where CE is used to determine SCN− in real samples.
creased. In another paper (94) these authors studied EIC, but The petroleum tracers, nitrate and thiocyanate, are deter-
from a more theoretical point of view (partitioning behaviors of mined by capillary ion electrophoresis in subterranean waters
cations, anions, and their corresponding ion pair-like forms). in spite of the high content of salts present. The authors (21)
Umemura et al. (95) also studied EIC by evaluating the examined the effect of NaCl in large concentrations in order to
analytical performance of dynamically coated ODS columns simulate the possible difficulties they could find when salty sam-
with three kinds of sulfobetaine-type surfactants, using water ples were to be analyzed. Their results showed that variations in
as eluent and a UV absorption detector for thiocyanate. These the salt content produced changes in the peak heights or widths,
authors studied the stability of the stationary phases prepared but not on peak area. By using 100 mM sodium chloride with 2.0
(more than 3 mon) and the different variables that affected the mM cetyltrimethylammonium chloride (electroosmotic flow
separation of a great number of anions and cations. Among modifier) as carrier electrolyte solution, both tracers could be
them were nature (ionic functional groups), hydrophobicity, determined in samples containing up to 200 mM of the salt.
 Downloaded by [Erciyes University] at 21:05 29 December 2014

TABLE 5
Other Methods for Thiocyanate Determination

Method Characteristics Other anions Sample DL Linear range Ref.

Gas chromatography (GC) Use of an extractive alkylation CN− Blood 0.003 µmol mL−1 0.02–1.0µmol mL−1 (35)
and GC/mass spectrometry technique
(MS)
High-performance liquid Derivatization to a fluorogenic — Saliva and plasma 165 fmol mL−1 0.5–10 nmol mL−1 (99)
chromatography (HPLC) compound
HPLC Ultraviolet (UV) detection after CN− and Gold cyanidation — — (100)
postcolumn derivatization metallocyanides leachates
Thin-layer chromatography Use of an Fe(III) chromogenic Several Spiked river water, — — (18)
reagent for detection seawater, and wastewaters
Ion-exchange Using amperometric or Halides, — 1 µM — (101)
2−
chromatography potentiometric detection NO− 2 , S2 O3
Potentiometric titration Using AgNO3 with a Ag indicator Halides — — — (102)
electrode and multivariate
calibration
Capillary electrophoresis Use of different electrolytes in I− , NO− 2, — 4 × 10−9 M 5 × 10−8 to (103)
−
nonaqueous media and N− ,
3 Cl 1 × 10−6 M
amperometric detection
Micellar electrokinetic Alkyltrimethyl ammonium I− , NO−2, Blood, plasma, and milk 0.15 mM Up to ∼ 38 mM (11)
capillary chromatography bromides were used as NO−3
surfactants in the separation
buffer: UV detection
Capillary ion electrophoresis Carrier electrolyte solution was I− , NO−2, Subterranean water 6286 ng/mL−1 — (22)
−
NaCl with cetyltrimethyl- NO−3 , Br
ammonium chloride: UV
detection
Capillary electrophoresis Suppressed electroosmotic flow is Halides, oxyhalides, — 0.9 mg/L−1 10 to 200 mg/L−1 (104)
used, as well as UV detection and metal oxoacids
Capillary electrophoresis Potentiometric detection with Several — — — (105)
coated-wire ion selective
electrodes (ISEs)
2−
Capillary electrophoresis Electrokinetic sample injection and SO2−
3 , SO4 , Open-pit mining 0.012 mg/L−1 — (98)
2−
conductivity detection S , S2 O2−
3 lake water
Capillary zone Enzymatic reaction monitored — — 2.5 µM 50 µM to 5 mM (2)
electrophoresis (CZE) through SCN− formation, which
is followed by CZE using UV
detection
CZE Application of the previous paper Br− , NO−
3 Serum, urine, 0.7–1.5 µM 25 to 500 µM (5)
to SCN− analysis and saliva (depending on sample)

19
 20 M. GRANDA VALDÉS AND M. E. DÍAZ-GARCÍA

Migration time for thiocyanate was around 12 min, good lin- their limited selectivity and lifetime are important drawbacks.
earity was found and recoveries in the samples were over 91%. It is likely that the most adaptable techniques for process analy-
Another paper centered on the analysis of environmental sis are the spectrophotometric ones (absorbance, fluorescence).
samples by CE was that of Hissner et al. (98). A method was The potentials of techniques such as CE, GC/MS, and micel-
developed for the determination of various sulfur-containing lar electrokinetic chromatography (MEC) may not yet be fully
anions and applied to the analysis of water from an open-pit realized for thiocyanate determination. There remain many op-
mining lake that had been contaminated with humic substances. portunities to develop and adapt methods that will be faster,
Separation conditions were determined (electrophoretic buffer), automated, and rugged especially when considering the need
and comparison was made of hydrodynamic versus electroki- to analyze thiocyanate in complex matrices (e.g., food science,
netic injection of sample. A standard addition procedure was wastewaters, body and plant fluids).
employed to correct for strong matrix influence. Thiocyanate
analysis using CE has also been applied in biological samples. REFERENCES
Glatz et al. (2) developed an indirect method of determining rho- 1. M. Lahti, J. Vilpo, and J. Hovinen, Spectrophotometric deter-
danese activity by monitoring through CE the SCN− produced mination of thiocyanate in human saliva. Journal of Chemical
in the following reaction, which is catalyzed by the enzyme: Education 76 (1999):1281–1282.
2. Z. Glatz, P. Bouchal, O. Janiczek, M. Mandl, and P. C̆esková,
− − Determination of rhodenase enzyme activity by capillary zone
3 + CN → SCN + SO3
S2 O2− 2−
electrophoresis. Journal of Chromatography A 838 (1999):139–
Downloaded by [Erciyes University] at 21:05 29 December 2014

148.
In the paper (2), the authors stated that the method developed
3. S. Chinaka, N. Takayama, Y. Michigami, and K. Ueda, Simul-
also has great potential for thiocyanate determination as such. taneous determination of cyanide and thiocyanate in blood by
Therefore, in a later paper (5) it was applied to the analysis of the ion chromatography with fluorescence and ultraviolet detection.
anion in human serum (after deproteinization with acetonitrile), Journal of Chromatography B 713 (1998):353–359.
saliva, and urine samples. Bromide was added as an internal 4. D. Connolly, L. Barron, and B. Paull, Determination of urinary
standard (it migrates closely before the SCN− peak). In this way, thiocyanate and nitrate using fast ion-interaction chromatogra-
correction for changes in sample composition was made. No phy. Journal of Chromatography B 767 (2002):175–180.
flow modifier was needed. Background electrolyte was 0.1 M 5. Z. Glatz, S. Nováková, and H. Štěrbová, Analysis of thiocyanate
β-alanine with HCl and the electroosmotic flow resulted to be in biological fluids by capillary zone electrophoresis. Journal of
minimal. Chromatography A 916 (2001):273–277.
6. C. Vesey, H. McAllister, and R. M. Langford, A safer method
Bjergegaard et al. (12) also analyzed biological samples,
for the measurement of plasma thiocyanate. Journal of Analytical
blood plasma, and milk. The micellar electrokinetic capillary
Toxicology 23 (1999):134–135.
chromatographic method using positively charged surfactants 7. A. B. Bendtsen and E. H. Hansen, Spectrophotometric flow injec-
(particularly dodecyltrimethylammonium bromide), was effec- tion determination of trace amounts of thiocyanate based on its
tive in the separation of several anions. According to the authors, reaction with 2-(5-Bromo-2-pyridylazo)-5-diethylaminophenol
in the case of thiocyanate, a low number of theoretical plates in- and dichromate: assay of the thiocyanate level in saliva from
dicates that improvements had to be made since this ion showed smokers and non-smokers. Analyst 116 (1991):647–651.
a tendency for asymmetric peaks. Interfering compounds in the 8. K. Tsuge, M. Kataoka, and Y. Seto, Cyanide and thiocyanate
samples were eliminated by a previous ion exchange technique levels in blood and saliva of healthy adult volunteers. Journal of
and evaporating the eluate to dryness in order to reduce volume. Health Science 46 (2000):343–350.
9. J. Gal, Y. Fovet, and M. Adib-Yadzi, About a synthetic saliva for
in vitro studies. Talanta 53 (2001):1103–1115.
10. S. Cabredo Pinillos, I. Sanz Vicente, J. Galbán Bernal, and J.
FINAL REMARKS Sanz Asensio, Determination of thiocyanate by carbonyl sul-
A number of methods are available for thiocyanate deter- phide (OCS) generation and gasphase molecular absorption spec-
mination. This review illustrates the most commonly applied trometry. Analytica Chimica Acta 318 (1996):377–383.
analytical and chromatographic methods for quantitating thio- 11. S. Chattaraj and A. K. Das, Indirect determination of thiocyanate
cyanate ion in both clinical and environmental samples, and in biological fluids using atomic absorption spectrometry. Spec-
highlights their strengths and weaknesses. The UV/Vis spec- trochimica Acta 47B (1992):675–680.
trophotometric based on the FeSCN2+ complex and that based 12. C. Bjergegaard, P. Møller, and H. Sørensen, Determination of
on the König reaction are the most common methods used. Ion thiocyanate, iodide, nitrate and nitrite in biological samples
by micellar electrokinetic capillary chromatography. Journal of
chromatography is a powerful separation technique which of-
Chromatography A 717 (1995):409–414.
fers low limits of detection (if adequate detectors are used), and
13. D. G. Themelis and D. Tzanavaras, Solvent extraction flow-
more specific and complementary information about accompa- injection manifold for the simultaneous spectrophotometric de-
nying anions (such as cyanide). This technique is useful for clin- termination of free cyanide and thiocyanate ions based upon on-
ical and environmental analysis. For process and on-line analy- line masking of cyanides by formaldehyde. Analytica Chimica
sis electrochemical sensors are probably well suited, although Acta 452 (2002):295–302.
 DETERMINATION OF THIOCYANATE CONTENT 21

14. B. Gong and G. Gong, Fluorimetric method for the determi- and palladium using the synergetic effect of 2-benzoylpyridine-2
nation of thiocyanate with 2 ,7 -dichlorofluorescein and iodine. pyridylhydrazone and thiocyanate ions. Talanta 47 (1998):161–
Analytica Chimica Acta 394 (1999):171–175. 167.
15. G. Zhang, B. Li, J. Fan, and S. Feng, Determination of trace thio- 32. S. Khalil and M. A. El-Ries, AAS and AES determination of
cyanate in body fluids by a kinetic fluorimetric method. Talanta furaltadone, methadone and trazodone in pharmaceutical formu-
44 (1997):1141–1147. lations. Journal of Pharmaceutical and Biomedical Analysis 27
16. A. Eaton, L. Clesceri, and A. Greenberg (Eds.), Standard Meth- (2002):117–122.
ods for the Examination of Waters and Wastewaters, American 33. J. Cirello-Egamino and I. D. Brindle, Determination of chlo-
Public Health Association, Washington DC. 19th ed. (1995). ride ions by reaction with mercury thiocyanate in the absence of
17. N. Csikai and A. J. Barnard Jr., Determination of total cyanide iron(III) using a UV-photometric, flow injection method. Analyst
in thiocyanate-containing wastewaters. Analytical Chemistry 55 120 (1995):183–186.
(1983):1677–1682. 34. L. Jing-fu and J. Bui-bin, Evaluation of a reagent-injection flow
18. A. Mohammad and J. P. S. Chahar, Thin-layer chromatographic injection technique for sample background absorption elim-
separation, colorimetric determination and recovery of thio- ination: determination of chloride in cigarettes. Talanta 54
cyanate from photogenic waste, river and sea waters. Journal (2001):329–332.
of Chromatography A 774 (1997):373–377. 35. S. Kage, T. Nagata, and K. Kudo, Determination of cyanide
19. J. van Staden and A. Botha, Spectrophotometric determination of and thiocyanate in blood by gas chromatography and gas
thiocyanate by sequential injection analysis. Analytica Chimica chromatography-mass spectrometry. Journal of Chromatogra-
Acta 403 (2000):279–286. phy B 675 (1996):27–32.
Downloaded by [Erciyes University] at 21:05 29 December 2014

20. W. Williams, Handbook of Anion Determination (London: 1979) 36. J. C. Wilmot, L. Solujič, and E. B. Milosavijevic, Formation
Butterworths. of thiocyanate during removal of sulfide as lead sulfide prior to
21. M. Blanco, J. Coello, H. Iturriaga, S. Maspoch, and J. Pagès, cyanide determination. Analyst 121 (1996):799–801.
Use of near-infrared spectrometry in control analyses of acrylic 37. R. G. Bowler, Determination of thiocyanate in blood serum. Bio-
fibre manufacturing processes. Analytica Chimica Acta 383 chemical Journal 38 (1944):385–388.
(1999):291–298. 38. G. Gümüş, B. Demirata, and R. Apak, Simultaneous spectropho-
22. L. Song, Determination of the petroleum tracers nitrate and thio- tometric determination of cyanide and thiocyanate after separa-
cyanate in subterranean waters by capillary ion electrophoresis. tion on a melamine-formaldehyde resin. Talanta 53 (2000):305–
Journal of Chromatography A 715 (1995):376–384. 315.
23. T. Koh, Y. Miura, N. Yamamuro, and T. Takaki, Spectrophoto- 39. D. Recalde, E. Andrés-Garcı́a, and M. E. Dı́az-Garcı́a, De-
metric determination of trace amounts of sulphide and hydrogen velopment of flow analytical systems for monitoring thio-
sulphide by formation of thiocyanate. Analyst 115 (1990):1133– cyanate biodegradation in waste waters. Analytical Letters 33
1137. (2000):1603–1614.
24. R. Cerdeira de Campos and A. Nova Araújo, Determination of 40. J. C. L. Meeussen, W. J. M. Temminghoff, M. G. Keizer,
Fe(III) and total Fe in wines by sequential injection analysis and and I. Novozamsky, Spectrophotometric determination of total
flame atomic absorption spectrometry. Analytica Chimica Acta cyanide, ion-cyanide complexes, free cyanide and thiocyanate
438 (2001):227–233. in water by a continuous-flow system. Analyst 114 (1989):959–
25. J. A. Sweileh, On-line flow injection solid sample introduction 963.
digestion and analysis: spectrophotometric and atomic absorp- 41. J. A. Sweileh, Determination of cyanide and thiocyanate by a
tion determination of iron, copper and zinc in multi-vitamin spectrophotometric flow-injection method. Analytica Chimica
tablets. Microchemical Journal 65 (2000):87–95. Acta 220 (1989):65–74.
26. J. de Gracia, M. L. M. F. S. Saravia, A. N. Araújo, J. L. F. C. Lima, 42. J. Kurzawa, K. Janowicz, and A. Suszka, Sopped-flow kinetic
M. del Valle, and M. Poch, Evaluation of natural computation determination of thiocyanates and thiosulphates with the ap-
techniques in the modelling and optimisation of a sequential plication of iodine-azide reaction. Analytica Chimica Acta 431
injection flow system for colorimetric iron (III) determination. (2001):149–155.
Analytica Chimica Acta 348 (1997):143–150. 43. P. Lundquist, B. Kagedal, L. Nilsson, L. Song, Q. Ou, W. Yu, L.
27. S. Arribas, Análisis Cualitativo de Iones Inorgánicos (Gráficas Fang, and Y. Jin, An improved method for the determination of
Summa, Madrid, Spain, 1974). thiocyanate in plasma and urine. European Journal of Clinical
28. F. Burriel, Quimica Analitica Cualitativa (Ed. Paraninfo, Madrid, Chemistry and Clinical Biochemistry 33 (1995):343–349.
Spain, 1979) 44. W. Aldridge, New method for the estimation of microquantities
29. M. M. Ayad, A. A. Shalaby, H. E. Abdellatef, and M. M. Hosny, of cyanide and thiocyanate. Analyst 69 (1944):262–265.
Spectrophotometric and AAS determination of ramipril and 45. W. König and J. Prakt, Über eine Klasse neuer Farbstoffe.
enalapril through ternary complex formation. Journal of Phar- Journal für Praktische Chemie 69 (1904):105–137.
maceutical and Biomedical Analysis 28 (2002):311–321. 46. S. Nagashima, Spectrophotometric determination of cyanide
30. N. El-Kousy and L. I. Bebawy, Determination of some antihis- with sodium isonicotinate and sodium barbiturate. Analytica
taminic drugs by atomic absorption spectrometry and colorimet- Chimica Acta 99 (1978):197–201.
ric methods. Journal of Pharmaceutical and Biomedical Analysis 47. A. Tanaka, K. Mashiba, and T. Deguchi, Simultaneous deter-
20 (1999):671–679. mination of cyanide and thiocyanate by the pyridine/barbituric
31. G. Zachariadis, D. G. Themelis, D. J. Kosseoglou, and J. A. acid method after diffusion through a microporous membrane.
Stratis, Flame AAS and UV-VIS determination of cobalt, nickel Analytica Chimica Acta 214 (1988):259–269.
 22 M. GRANDA VALDÉS AND M. E. DÍAZ-GARCÍA

48. B. Sun and B. N. Noller, Simultaneous determination of trace 65. C. Palet, M. Muñoz, S. Daunert, L. G. Bachas, and M. Valiente,
amounts of free cyanide and thiocyanate by a stopped-flow spec- Vitamin B12 derivatives as anion carriers in transport through sup-
trophotometric method. Water Research 32 (1998):3698–3704. ported liquid membranes and correlation with their behavior in
49. J. Ruzicka and E. Hansen, Flow injection analyses. Part I. A new ion-selective electrodes. Analytical Chemistry 65 (1993):1533–
concept of fast continuous flow analysis. Analytica Chimica Acta 1536.
78 (1975):145–157. 66. Z. Q. Li, A. Y. Wu, R. Yuan, M. Ying, G. L. Shen, and R.
50. A. Tanaka, K. Deguchi, and T. Deguchi, Spectrofluorimetric de- Q. Yu, Thiocyanate-selective PVC membrane electrodes based
termination of cyanide and thiocyanate based on a modified on MN(II) complex of N,N -bis(4-phenylazosalicylidene) o-
König reaction in a flow-injection system. Analytica Chimica phenylene diamine as a neutral carrier. Electrochimica Acta 44
Acta 261 (1992):281–286. (1999):2543–2548.
51. S. Iwata, H. Suda, and K. Tanaka, The logical cation and 67. M. M. Ardakani, A. A. Ensafi, M. S. Niasari, and S. M. Cha-
anion recognition of pyrido[1’,2’:1,2] imidazo[4,5-b]pyrazine chooki, Selective thiocyanate poly(vinyl chloride) membrane
fluorophore-host. Journal of Inorganic Biochemistry 67 based on a 1,8-dibenzyl-1,3,6,8,10,13-hexaazacyclotetradecane-
(1997):447. Ni(II) perchlorate. Analytica Chimica Acta 462 (2002):25–30.
52. M. Granda, R. Badı́a, G. Pina Luis, and M. E. Dı́az-Garcı́a, Pho- 68. E. Malinowska and M. E. Meyerhoff, Role of axial ligation on
toinduced electron transfer systems and their analytical applica- potentiometric response of Co(III) tetraphenylporphyrin-doped
tions in chemical sensing. Quimica Analitica 19 (2000):38–63. polymeric membranes to nitrite ions. Analytica Chimica Acta
53. R. Kopelman, M. R. Shortree, and S. L. R. Barker, Anion- 300 (1995):33–43.
selective liquid-polymer optodes with fluorescent pH chro- 69. S. Glazier and M. A. Arnold, Selectivity of membrane electrodes
Downloaded by [Erciyes University] at 21:05 29 December 2014

moionophores, tunable dynamic range and diffusion enhanced based on derivatives of dibenzyltin dichloride. Analytical Chem-
lifetimes. Sensors and Actuators B 35 (1996):217–221. istry 63 (1991):754–759.
54. M. M. G. Antonisse and D. N. Reinhoudt, Neutral anion 70. A. Florido, L. G. Bachas, M. Valiente, and I. Villaescusa, Anion-
receptors: design and application. Chemical Communications selective electrodes based on a gold(III)-triisobutylphosphine
(1998):443–448. sulphide complex. Analyst 119 (1994):2421–2425.
55. R. S. Hutchins, P. Bansal, P. Molina, M. Alajarı́n, A. Vidal, and L. 71. N. Chaniotakis, A. M. Chasser, and M. E. Meyerhoff, Influence
G. Bachas, Salicylate-selective electrode based on a biomimetic of porphyrin structure on anion selectivities of manganese(III)
guanidinium ionophore. Analytical Chemistry 69 (1997):1273– porphyrin based membrane electrodes. Analytical Chemistry 60
1278. (1988):185–188.
56. M. Rothmaier, U. Schaller, W. E. Morf, and E. Pretsch, Response 72. D. Gao, J. Gu, R. Q. Yu, and G. D. Zheng, Substituted met-
mechanism of anion-selective electrodes based on mercury or- alloporphyrin derivatives as anion carrier for PVC membrane
ganic compounds as ionophores. Analytica Chimica Acta 327 electrodes. Analytica Chimica Acta 302 (1995):263–268.
(1996):17–28. 73. R. Yuan, Y. Chai, D. Liu, D. Gao, J. Li, and R. Q. Yu, Shiff base
57. A. Abbaspour, M. A. Kamyabi, A. R. Esmaeilbeig, and R. complexes of cobalt(II) as neutral carriers for highly selective
Kia, Thiocyanate-selective electrode based on unsymmetri- iodide electrodes. Analytical Chemistry 65 (1993):2572–2575.
cal benzoN4 nickel(II) macrocyclic complexes. Talanta 57 74. J. Bricker, S. Daunert, L. G. Bachas, and M. Valiente, Selective
(2002):859–867. electrodes for silver and anions based on polymeric membranes
58. E. Bakker, E. Malinowska, R. D. Schiller, and M. E. Meyer- containing complexes of triisobutylphosphine sulfide with silver.
hoff, Anion-selective membrane electrodes based on metallo- Analytical Chemistry 63 (1991):1585–1589.
porphyrins: the influence of lipophilic anionic and cationic sites 75. V. J. Wotring, D. M. Johnson, and L. G. Bachas, Polymeric mem-
on potentiometric selectivity. Talanta 41 (1994):881–890. brane anion-selective electrodes based on diquaternary ammo-
59. E. Bakker, P. Bühlmann, and E. Pretsch, Carrier-based ion- nium salts. Analytical Chemistry 62 (1990):1506–1510.
selective electrodes and bulk optodes. I. General characteristics. 76. S. Daunert and L. G. Bachas, Anion-selective electrodes based
Chemical Reviews 97 (1997):3083–3132. on a hydrophobic vitamin B12 derivative. Analytical Chemistry
60. M. K. Amini, S. Shahrokhian, and S. Tangestaninejad, 61 (1989):499–503.
Thiocyanate-selective electrodes based on nickel and iron ph- 77. S. Daunert, S. Wallace, A. Florido, and L. G. Bachas, Anion-
thalocyanines. Analytica Chimica Acta 402 (1999):137–143. selective electrodes based on electropolymerized porphyrin
61. U. Schaller, E. Bakker, U. Spichlger, and E. Pretsch, Ionic ad- films. Analytical Chemistry 63 (1991):1676–1679.
ditives for ion-selective electrodes based on electrically charged 78. S. Daunert, J. Bricker, W. Dunaway, A. Florido, L. G. Bachas,
carriers. Analytical Chemistry 66 (1994):391–398. M. Muñoz, and M. Valiente, Complexes of triisobutyl phos-
62. P. Bühlmann, E. Pretsch, and E. Bakker, Carrier-based ion- phine sulfide with mercury as lonophores in the development of
selective electrodes and bulk optodes. 2. Ionophores for potentio- static and flow-through ion-selective electrodes. Electroanalysis
metric and optical sensors. Chemical Reviews 98 (1998):1593– 5 (1993):839–843.
1687. 79. E. G. Cookeas and C. E. Efstathiou, Flow injection amperomet-
63. F. Hofmeister, Lehre von der wirkung der salze, Archieves ric determination of thiocyanate and selenocyanate at a cobalt
of Experimental Pathology and Pharmakology 24 (1888):247– phthalocyanine modified carbon paste electrode. Analyst 119
260. (1994):1607–1612.
64. D. Gao, J. Z. Li, R. Q. Yu, and G. D. Zheng, Metalloporphyrin 80. H. Small, T. S. Stevens, and W. C. Bauman, Novel ion exchange
derivatives as neutral carriers for PVC membrane electrodes. chromatographic method using conductimetric detection. Ana-
Analytical Chemistry 66 (1994):2245–2249. lytical Chemistry 47 (1975):1801–1809.
 DETERMINATION OF THIOCYANATE CONTENT 23

81. R. P. Singh, S. A. Smesko, and N. M. Abbas, Ion chromatographic by electrostatic ion chromatography. Analytica Chimica Acta 285
characterization of toxic solutions: analysis and ion chemistry of (1994):335–341.
biological liquids. Journal of Chromatography A 774 (1997):21– 94. W. Hu, H. Tao, and H. Haraguchi, Electrostatic ion chromatog-
35. raphy, 2. Partitioning behaviours of analyte cations and anions.
82. S. Matsushita, Simultaneous determination of anions and metal Analytical Chemistry 66 (1994):2514–2520.
cations by single-column ion chromatography with ethylene- 95. T. Umemura, S. Kamiya, A. Itoh, K. Chiba, and H. Haraguchi,
diaminetetracetate as eluent and conductivity and ultraviolet Evaluation of sulfobetaine-type zwitterionic stationary phases
determination. Journal of Chromatography 312 (1984):327– for ion chromatographic separation using water as a mobile
336. phase. Analytica Chimica Acta 349 (1997):231–238.
83. Y. Michigami, K. Fujii, K. Ueda, and Y. Yamamoto, Determina- 96. E. Urbansky, Quantitation of perchlorate ion: practices and ad-
tion of thiocyanate in human saliva and urine by ion chromatog- vances applied to the analysis of common matrices. Critical Re-
raphy. Analyst 117 (1992):1855–1858. views of Analytical Chemistry 30 (2000):311–343.
84. Y. Michigami, T. Takahashi, F. He, Y. Yamamoto, and K. Ueda, 97. P. Dasgupta, Ion Chromatography, the state of the art. Analytical
Determination of thiocyanate in human serum by ion chromatog- Chemistry 64 (1992):775A–783A.
raphy. Analyst 113 (1988):389–392. 98. F. Hissner, J. Mattusch, and K. Heinig, Quantitative determina-
85. A. Pirogov, M. M. Platonov, and O. A. Shpigun, Polyelectrolyte tion of sulfur-containing anions in complex matrices with capil-
sorbents based on aliphatic ionenes for ion chromatography. lary electrophoresis and conductivity detection. Journal of Chro-
Journal of Chromatography A 850 (1999):53–63. matography A 848 (1999):503–513.
86. S. A. Maki and N. D. Danielson, Indirect photometric chromatog- 99. S. H. Chen, A. Y. Yang, H. L. Wu, H. S. Kou, and S. J. Lin,
Downloaded by [Erciyes University] at 21:05 29 December 2014

raphy of anions using sodium naphthalenetrisulfonate. Analytical Determination of thiocyanate anion by high-performance liquid
Chemistry 63 (1991):699–703. chromatography with fluorimetric detection. Journal of Analyt-
87. J. Xu, M. Xin, T. Takeuchi, and T. Miwa, Determination of oxi- ical Toxicology 20 (1996):38–42.
dizable inorganic anions by reversed-phase ion-pair chromatog- 100. P. A. Fagan, P. R. Haddad, I. Mitchell, and R. Dunne, Moni-
raphy with amperometric detection. Analytica Chimica Acta 276 toring the cyanidation of gold-copper ores with ion-interaction
(1993):261–264. chromatography. Determination of the CN− :Cu(I) molar ration.
88. R. Zein, E. Munaf, T. Takeuchi, and T. Miwa, Microcolumn ion Journal of Chromatography A 804 (1998):249–263.
chromatography of inorganic UV-absorbing anions using bovine 101. Z. Chen and D. B. Hibbert, Simultaneous amperometric and po-
serum albumin as stationary phases. Analytica Chimica Acta 335 tentiometric detection of inorganic anions in flow systems using
(1996):261–266. platinum and silver/silver chloride electrodes. Analytica Chimica
89. Y. Miura, K. Fukasawa, and T. Koh, Determination of sulfur Acta 350 (1997):1–6.
anions at the ppb level by ion chromatography utilizing their 102. Y. Ni and A. Wu, Simultaneous determination of halide and thio-
catalytic effects on the postcolumn reaction of iodine with azide. cyanate ions by potentiometric precipitation titration and multi-
Journal of Chromatography A 804 (1998):143–150. variate calibration. Analytica Chimica Acta 390 (1999):117–123.
90. Y. Miura and A. Kawaoi, Determination of thiosulfate, thio- 103. H. Salimi-Moosavi and R. M. Cassidy, Capillary electrophore-
cyanate and polythionates in a mixture by ion-pair chromatog- sis of inorganic anions in nonaqueous media with electro-
raphy with ultraviolet absorbance detection. Journal of Chro- chemical and indirect UV detection. Analytical Chemistry 67
matography A 884 (2000):81–87. (1995):1067–1073.
91. S. Polesello, S. Valsecchi, S. Cavalli, and C. Reschiotto, Ion- 104. T. Soga, Y. Inoue, and G. A. Ross, Analysis of halides, oxy-
chromatographic screening method for monitoring arsenate and halides and metal oxoacid by capillary electrophoresis with sup-
other anionic pollutants in ground waters of northern Italy. Jour- pressed electroosmotic flow. Journal of Chromatography A 718
nal of Chromatography A 920 (2001):231–238. (1995):421–428.
92. W. Hu, T. Takeuchi, and H. Haraguchi, Electrostatic ion chro- 105. T. Kappes, P. Schnierle, and P. C. Hauser, Potentiometric detec-
matography. Analytical Chemistry 65 (1993):2204–2208. tion of inorganic anions and cations in capillary electrophore-
93. W. Hu and H. Haraguchi, Simultaneous determination of organic sis with coated-wire ion-selective electrodes. Analytica Chimica
and inorganic ultraviolet-absorbing compounds in human saliva Acta 350 (1997):141–147.