Methods for the Determination of Endocrine-Disrupting Phthalate Esters.

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Methods for the determination of endocrine disrupting phthalate esters. ae

a

a

Munawar Saeed Qureshi , Abdull Rahim bin Mohd Yusoff , Mohd Dzul Hakim Wirzal , c

b

c

d

Sirajuddin , Jiri Barek , Hassan Imran Afridi & Zafer Üstündag a

Institute of Environmental & Water Resource Management (IPASA), Universiti Teknologi Malaysia, Malaysia b

Charles University in Prague, Faculty of Science, University Research Centre UNCE, Department of Analytical Chemistry, UNESCO Laboratory of Environmental Electrochemistry, Albertov 6, CZ-128 Prague 2, Czech Republic c

National Center of Excellence in Analytical Chemistry, University of Sindh, Jamshoro, Pakistan d

Dumlupinar University, Faculty of Arts and Sciences, Department of Chemistry, Kutahya, Turkey e

Government College & Postgraduate Center, Education & Literacy Department, Govt of Sindh, Pakistan Accepted author version posted online: 01 Apr 2015.

To cite this article: Munawar Saeed Qureshi, Abdull Rahim bin Mohd Yusoff, Mohd Dzul Hakim Wirzal, Sirajuddin, Jiri Barek, Hassan Imran Afridi & Zafer Üstündag (2015): Methods for the determination of endocrine disrupting phthalate esters., Critical Reviews in Analytical Chemistry, DOI: 10.1080/10408347.2015.1004157 To link to this article: http://dx.doi.org/10.1080/10408347.2015.1004157

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ACCEPTED MANUSCRIPT Methods for the determination of endocrine disrupting phthalate esters. Munawar Saeed Qureshia,e, Abdull Rahim bin Mohd Yusoffa, Mohd Dzul Hakim Wirzala, Sirajuddinc, Jiri Barek*b, Hassan Imran Afridic, Zafer Üstündagd

a

Institute of Environmental & Water Resource Management (IPASA), Universiti Teknologi


Malaysia, Malaysia. b

Charles University in Prague, Faculty of Science, University Research Centre UNCE,

Department of Analytical Chemistry, UNESCO Laboratory of Environmental Electrochemistry, Albertov 6,CZ-128 Prague 2,Czech Republic. c

National Center of Excellence in Analytical Chemistry, University of Sindh, Jamshoro.

Pakistan. d

Dumlupinar University, Faculty of Arts and Sciences, Department of Chemistry, Kutahya,

Turkey. e

Government College & Postgraduate Center. Education & Literacy Department, Govt of Sindh,

Pakistan *

Corresponding author, E-mail: [email protected]

Key words Phthalates, Endocrine disruptors, Carcinogens

Abstract Phthalates are endocrine disruptors frequently occurring in general and industrial environment and in may industrial products. Moreover, they are also suspected of being

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ACCEPTED MANUSCRIPT carcinogenic, teratogenic, and mutagenic and they show diverse toxicity profiles depending on their structures. The European Union and United States Environmental Protection Agency (US EPA) have included many phthalates into the list of priority substances with potentially endocrine disrupting action. Namely they are: dimethyl phthalate (DMP), diethyl phthalate (DEP), dibutyl phthalate (DBP), butylbenzyl phthalate (BBP), diethylhexyl phthalate (DEHP),


di-iso-nonyl phthalates (DINP), di-iso-decyl phthalate (DIDP), di-n-decyl phthalate (DNDP), and dioctyl phthalate (DOP). There is an ever increasing demand for new analytical methods suitable for monitoring of different phthalates in various environmental, biological and other matrices. Separation and spectrometric methods are most frequently used. However, modern electroanalytical methods can also play useful role in this field because of their high sensitivity, reasonable selectivity, easy automation and miniaturization, and especially low investment and running costs which makes them suitable for large scale monitoring. Therefore, this review outlines possibilities and limitations of various analytical methods for determination of endocrine disruptor phthalate esters in various matrices including somewhat neglected electroanalytical methods.

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ACCEPTED MANUSCRIPT 1. Introduction

Phthalates (dialkyl or alkyl aryl esters of phthalic acid) are organic chemicals that are used in a large variety of industrial and consumer applications. They are the most commonly used plasticizers worldwide [1, 2]. Phthalates have been approved for the use and also detected


in a wide range of consumer products [3, 4], including personal care products [5], children's toys [3,6,7], food packaging [8], pharmaceuticals, nutritional supplements, cleaning materials, lubricants, insecticides, solvents, adhesives, paints, lacquers, etc. They were detected in indoor air [9-11], indoor dust [12-15], and air inside vehicles [16]. The general population may be exposed since phthalates are ubiquitous environmental contaminants [17-19]. The presence of phthalates in human breast milk was reported in various countries e.g. USA, Canada, Italy, or Denmark [20-23]. The aim of this review is to show advantages and disadvantages of various analytical methods for determination of those dangerous substances. At first attention is paid to prevalent separation and spectrometric methods followed by electroanalytical methods. Various electroanalytical methods are nowadays regularly used in environmental analysis [24] and their possibilities are continually improved [25]. Today they are simple, sensitive, selective and dynamic techniques applicable for determination of pollutants, pesticides, drugs and other analytes of environmental importance [26,27,28]. Voltammetric methods today have different modes: Differential pulse voltammetry (DPV), Square wave voltammetry (SWV), Cyclic voltammetry (CV), Anodic stripping voltammetry (ASV), Adsorptive stripping voltammetry (AdSV), Linear sweep voltammetry (LSV), etc. and can be applied successfully for the

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ACCEPTED MANUSCRIPT detrmination of different environmentally hazardous compounds. Nowadays, CV, DPV and SWV are the most preferable techniques for the determinations of organic compounds at trace levels [29-35]. Different electrodes, e.g. glassy carbon electrode (GCE), boron doped diamond electrode (BDDE), carbon paste electrodes (CPE), and hanging mercury drop electrode (HMDE) are most frequently used. Chemically modified electrodes (CME), are frequently applied in


AdSV [32,36,37].

2. Toxicity of phthalates The widespread use of phthalates resulting in potential human exposure has captured enormous attention to their monitoring by National Health and Nutrition Examination Survey (NHANES). A report was published by Center for Disease Control (CDC, USA) about monoester phthalates determination in urine [38] that reflects the human exposure to phthalates. Other papers also reported exposure to phthalates [39-44]. This exposure can create a number of adverse effects on both humans and animals. The most alarming is the damaging of the developing male reproductive systems. The detrimental effects on male reproductive system include decreased sperm count, infertility, hypospadias, cryptorchidism, the hypothesized testicular dysgenesis syndrome and other disorders [45-47]. The effect of phthalate monoester was also observed on thyroid hormones in pregnant women [48]. The toxic effect of phthalates in pregnant women resulted in venereal enlargement of the male offspring. Various forms of genital alterations in newborn males were observed. This is known as “testicular infertility symptom”. According to CDC, one-quarter of women is exposed to undesirable effects of phthalates [4952]. The BBP, DBP, DEHP, DINP, DIDP, and DNDP were banned by European Parliament in

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ACCEPTED MANUSCRIPT children’s toys and childcare articles [53]. Toddlers and children can be exposed to phthalates through several dietary sources [54-58]. Neonates and children can be exposed to phthalates through mouthing of plastic toys and use of plastic eating containers. Phthalates, mainly DEHP and DINP, were found in toys and plastic food containers [59-61] and they can be extracted from these products into a solution that mimics saliva [62, 63]. Another study by the Consumer


Product Safety Commission, USA, concluded that levels of DINP leached from different toys did not pose a significant risk to children [64]. Phthalate concentrations in particulate dust collected in homes suggested that inhalation of phthalates may be an important route of exposure for some children [65-69]. The potential sources of DMP are mainly waste waters from production and application of phthalate esters [70-72]. The long term exposure to DMP can cause functional disturbances in the nervous system and liver of animals. The exposure to DBP, DEP and their mixture in zebra fish embryos during their premature developmental stages leads to the stimulation of antioxidant enzyme activities and transcription level of immune related gene [7375]. DMP has been listed as a priority pollutant by the USEPA [76]. The significant correlation between urine concentrations of DBP metabolites and neuropsychological dysfunction have been found in children aged 8–11 years [77]. Other researchers analyzed DBP microarray data in the testes [78-81] with respect to either individual gene expression changes or changes in the expression of specific genes that are important in testicular development and testosterone synthesis. BBP have weak estrogenic activity and compete with estradiol for binding to estrogen receptor (ER) [82]. BBP promotes activation of breast cancer and may reduce clinical effectiveness of chemotherapy. Morover, it promotes resistance to tamoxifen by inhibiting tamoxifen-induced apoptosis in breast cancer cells [83]. The effect of BBP on sexual maturation

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ACCEPTED MANUSCRIPT in female animals is unclear, with several studies providing divergent findings. DEHP acts as an estrogenic, anti androgenic endocrine disruptor in mammals, and this compound can cause reproductive and developmental toxicity in animal models [84-86]. DEHP is recognized as an endocrine disruptor that alters reproductive hormone regulation in rats by producing Leydig cell hyperplasia and by affecting systemic physiology [87-88]. It has been reported that DEHP is not


acutely toxic but exposure over a prolong time may cause harm. The main routes of human exposure to phthalates are inhalation, ingestion followed by an inhalation of indoor air and intravenous exposure with less prevalence of dermal and oral exposure [89].

3. Analytical methods used for determination of phthalates 3.1. Chromatographic methods Most commonly used methods for the determination of phthalates are based on gas chromatography (GC), e.g. GC with flame ionization detector (GC-FID), solid phase microextraction coupled with GC (SPME-GC-FID), single drop microextraction coupled to GC (SDME-GC-FID), headspace solid phase microextraction with GC (HS-SPME-GC), dummy molecularly imprinted solid-phase extraction with GC (DMI-SPE-GC), gas chromatographymass spectroscopy (GC-MS), solid phase microextraction coupled with GC-MS (SPME-GCMS), molecularly imprinted solid-phase micro-extraction coupled with GC-MS (MI-SPME-GCMS), liquid-phase microextraction-GC-MS (LPME-GC-MS), stir bar sorptive extraction with liquid desorption followed by large volume injection (SBSE-LD/LVI-GC–MS), dispersive liquid–liquid microextraction coupled with GC-MS (DLLME-GC-MS), pressurized liquid extraction and GC-MS (PLE-GC-MS). High-performance liquid chromatography (HPLC) is

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ACCEPTED MANUSCRIPT another important group of methods for phthalates monitoring, e.g. reversed phase HPLC (RPHPLC), magnetic solid phase extraction-HPLC (MSPE-HPLC), solid phase microextractionHPLC (SPME-HPLC), solid phase extraction-HPLC (SPE-HPLC), liquid chromatography coupled with MS (LC-MS), LC-tandem MS(LC-MS/MS), LC-time of flight mass spectroscopy (LC-TOF/MS), ultra fast liquid chromatography- MS (UPLC-MS), ultra HPLC coupled with


electronic spray mass spectrum (UPLCMS/MS) and cyclodextrin modified micellar electrokinetic chromatography (MEKC). Figure of merits of various chromatographic techniques are summarized in Table 1.

It can be seen that above mentioned separation methods are extremely sensitive and highly selective. This is especially valid for various types of extremely sensitive and selective MS detection. Nevertheless, a preliminary separation and preconcentration is frequently used to increase both sensitivity and selectivity. HPLC seems to prevail recently in this field over GC which is a trend observable in many other fields as well. Critical evaluation of techniques summarized in Table 1shows that separation methods are rather expensive, labor intensive and time consuming which limits their application for large scale phthalates monitoring and for screening purposes. Therefore, in some respects and in selected particular applications, spectrometric and electroanalytical methods mentioned further can successfully compete with separation methods especially in the field of site and large scale monitoring because of easy portability of necessary equipment and lower cost of analysis.

3.2. Spectrometric methods

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ACCEPTED MANUSCRIPT In comparison with above discussed separation method, spectrometric methods are usually less selective and in some cases less sensitive as well. Nevertheless, in many cases they can be method of choice and present less expensive and faster alternative to prevalent chromatographic methods. Moreover, they are frequently combined with a suitable preliminary separation and preconcentration techniques to increase their selectivity and sensitivity. In addition,


spectrometric methods are frequently used to monitor the fate of various phthalates in environment and/or in various products. Janis and Byler [124] developed method for isolation and determination of dialkyl phthalates (DAP) in pork meat using TLC and column chromatography followed by FTIR. However, this paper is focused more on phthalates identification using the ester carbonyl (C=O) stretching frequencies than on their quantification. Rie et al [125] examined migration of DHEP from PVC products used in medical devices. The PVC sheets and PVC tubing were subjected to UV and VIS irradiation to determine whether they are deteriorated by these treatments. The surface structure was examined by FTIR. Qian and Birgit [126] paid attention to plasticizers DOP and DCHP used in PVC tubes and monitored their extraction using FTIR, DSC and TGA technique. They compared these results with those obtained by GC and GC-MS. Monakhova et al [127] proposed direct UV spectrophotometric method for the determination of DEP in surrogate alcohols. Multivariate curve resolution and spectra computation methods were used to confirm the presence of DEP in the investigated beverages. UV spectrophotometry at 227 nm gave linear calibration curves from 2 to 150 mg/L of DEP and limit of detection 2.5 mg/L whereas in 1HNMR the linear calibration range for DEP from 100-7000 mg/L was obtained with limit of detection 90 mg/L. Myhre and Nielsen [128] developed UV spectrophotometric method

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ACCEPTED MANUSCRIPT for of some organic acids relevant to tropospheric aerosols including phthalic acid. Qureshi et al [129] used UV-VIS spectrophotometry for the determination of DEP, DBP, DDP and DAP at 224, 223, 225 and 226 nm. The results were better than at second absorption maximum around 275 nm. They obtained linear calibration dependencies from 1×10-4 to 2×10-5 mol.L-1 and from 1×10-5 to 2×10-6 mol.L-1 and limits of quantification 4, 5, 2, 1 µmol×L-1 for DEP, DBP, DDP, and


DAP, respectively. Zhang and Chen [130] demonstrated that SFG (sum frequency generation vibrational spectroscopy) is very sensitive to detect phthalate (e.g. DEP and DBP) leaching from PVC films (detection limit as low as 30 ng) It can be concluded that spectrometric methods are not too frequently used for determination of phthalates and that greater attention should be paid to their application in this field. Their sensitivity and selectivity is sufficient for many practical applications, they are usually faster than separation techniques with similar figures of merits and they are in most cases less expensive.

3. Electrochemical methods For the last four decades the modern electroanalytical techniques received great attention due to the introduction of new types of working electrodes providing broader potential window, lower noise, higher resistance to passivation, better mechanical and chemical stability and easier mechanical, chemical or electrochemical pretreatment. Those qualities enabled number of application of modern electroanalytical methods for the determination of above mentioned phthalates in various matrices. Most of them are based on reduction of phthalates which occurs at

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ACCEPTED MANUSCRIPT rather negative potentials and thus requires mercury electrodes or silver amalgam electrodes with sufficiently broad potential window. 3.1. Polarographic methods Mercury is undoubtedly the best available electrode material for cathodic processes in spite of somewhat unreasonable fears of mercury toxicity. Especially for phthalates which are


usually difficult to reduce mercury electrodes are unsurpassable as demonstrated in following paragraphs. The polarographic reduction of DEP at the dropping mercury electrode (DME) was investigated by Whitnack et al [131]. This reduction occurs in two steps. The first step corresponds to the four electron exchange resulting in phthaladehyde or phthalide (see Figure 2) while in the second step two electrons exchange results in so far unidentified product. Moreover, standards of phthaldehyde and phthalide were used for the confirmation of polarographic waves assignement. Phthaldehyde produced two waves at more positive potentials than diethyl phthalate at half wave potential -1.15V and -1.57V vs Hg pool. The 1st wave disappeared after some time of standing the solution whereas the 2nd wave appeared to overlap slightly with the 1st wave of DEP. Polarogram of phthalide shows one wave with a half wave potential nearly the same as that for the 2nd wave of DEP. Thus phthalide can be the intermediate product in this electrode reaction, the addition of phthalide to a solution of DEP should increase only the 2nd wave which was experimentally confirmed. So far, the end product of the electrode process was not indentified.

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ACCEPTED MANUSCRIPT Gonzalez et al [132] and Cortes et al [133] suggested a dc polarographic method for the investigation of DEP and DBP in micellar solutions using cationic surfactant Hyamine 1622 as emulsified agent. They calculated the value of αna using a) the slopes of the E vs log(i/iL-i) plots from current-samples dc polarograms b) the application of the E3/4 – E1/4 criterion, c) log i vs E plots obtained at the foot of the waves for the reduction process of DEP and DBP in micellar


solution in 0.1 molL-1 Britton Robinson buffer pH 4.0, 8.0, and 10.0, respectively. Their observations were consistent with a four electron exchange in the DBP and DEP reduction process with α = 0.5 at pH 10.0, possibly leading to the formation of phthalide (see Fig.3).

However, in acidic medium two electrons electrode process is possible. Proposed four electron exchange using a drop time of 0.4 s and mercury flow rate of 3.10 mg s-1 gave the value of diffusion coefficient 2.6×10-6 and 2.9×10-6 cm2 s-1 for DEP and DBP, respectively. Williams and Kenyon [134] developed a polarographic method for the determination of DBP additive in nitroglycerine as propellant using so called cathode rays polarography (CRP). DBP showed two waves with half wave potential at –1.5V and –1.85V, respectively. Nitroglycerine somewhat influenced both the peak height of DBP (increased) and the peak potential (slight shift towards negative potential). Townend and Macintosh [135] described polarographic method for determination of DMP and DBP in different propellants samples. They used zinc amalgam which reduced the interference from nitroglycerine still keeping good recoveries of phthalates in different types of propellant samples. They added DMP into synthetic propellant (1.89, 1.98, 2.19, 2.39, and 2.44%, respectively), and found 1.90, 1.98, 2.18, 2.38, and

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ACCEPTED MANUSCRIPT 2.46%, respectively, proving very good recoveries. Similarly, they added DBP in synthetic propellant (6.49% and 6.95%) and found 6.49% and 6.97%, respectively, again with very good recovery. Whitnack and Gantz [136] suggested a DC polarographic method for the determination of some phthalates such as DMP, DEP, DBP, DPhP and DOP, particularly in plastic, but also in explosives or resins. They prepared all standard solutions in 75% ethanol or acetone medium and


used 0.1M tetramethylammonium chloride (TMACl) as a csupporting electrolyte to broaden potential window. They observed two reduction waves for tested phthalates with 1st half-wave potential at –1.83V vs SCE and 2nd half-wave potential at –2.17 V vs SCE. They have selected first wave for all phthalates due to less negative and thus more favorable potential. Maynard and Ronald [137] developed similar polarographic method for the determination of terephthalic acid and phthalic acid isomers such as isophthalic acid and ortho phthalic acid. They used 1M tetramethylammonium hydroxide (TMAOH) as a supporting electrolyte and prepared all standards solutions in 1.0 M LiOH. Under these conditions phthalic acid and isophthalic acid gave one reduction wave, while terephthalic acid isomers gave two reduction waves. However the reduction waves are overlapping so that it is difficult to separate reduction peak of phthalic and isophthalic acid. Terephthalic acid isomers were determined in mixture of phthalic acid isomers using 1M lithium hydroxide (LiOH) as supporting electrolyte. Demotrios et al [138] proposed DC polarographic method at DME for the determination of phthalic anhydride using mixture of water and acetone as a solvent. They investigated polarographic behavior of phthalic acid anhydride in acidic and neutral media (acetone, water and HCl) and obtained half-wave potentials between –0.9V and –1.2V vs. SCE. They observed the effect pH on the limiting current and half-wave potential and effect of pH on hydrolysis rate of phthalic acid anhydride in

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ACCEPTED MANUSCRIPT various media at 23ºC. Phthalic acid anhydride was determined with a relative standard deviation (RSD) of ± 5%. Philip and Clifford [139] suggested a polarographic method for organic compounds facilitated with halogen bond fission in the iodobenzoic acid, phthalic anhydrides and phthalates. They used ammonium chloride and ammonium hydroxide as supporting electrolyte. For orthopthalic anhydride they found two reduction waves with E1/2 –1.10 V and –


1.20 V vs SCE in KCl–HCl buffer at pH 1.7. They also tested the effect of iodine and determined 4-iodophthalic anhydride, 3,4 diiodophthalic anhydride, 3,6–diiodophthalic anhydride, 3,5– diiodophthalic acid, 3,4,6–triiodophthalic anhydride and 3,4,5,6tertraiodophthalaic anhydrid. They used different pH ranges from 1.7 to 11.5 with different sodium salt concentration from 0.13 to 0.20 mmol L-1. Several diiodophthalic anhydrides and iodobenzoic acids with 3,4,5 triiodo and 3,4,5,6 tetraiodophthalic anhydrides were investigated and four reductions waves at E1/2 –1.41, –0.76, –0.94 and –1.34V for 3,4,5,6 tetraiodophthalic anhydrides were found. The most negative wave coincides with the third wave of 3,4,5 triiodophthalic anhydrides at E1/2 – 1.33 V. The third wave of tetraiodophthalic anhydride coincides with the second wave of triisophthalic anhydride. Another polarographic method was described by Paul and Esther [140] for the determination of phthalic acid anhydride in nitrocellulose resins. At first they saponified the samples, then dissolved the precipitated potassium phthalate alcoholate in aqueous solution of sulphuric acid (pH 1.5 to 1.6) and finally measured the diffusion current at DME. Phthalic acid gave a well-defined polarographic wave in aqueous sulfuric acid with supporting electrolyte of tetramethyl ammonium bromide (TMABr). Richard et al [141] developed a polarographic and chronopotentiometric method for the o-phthalic acid in acidic medium. They measured limiting currents for a series of solutions at different pH of phosphate buffer and they found pH 4.0

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ACCEPTED MANUSCRIPT phosphate buffer optimal. The rate of the kinetically limited electrochemical reaction decreased with increased inert salt concentration. Furman and Bricker [142] described a polarographic method for o-phthalic acid and phthalates. They studied reduction of o-phthalic acid by using different salts in the pH range of 1–9. They studied distribution of total phthalate in the form of undissociated molecules, biphthalate ions and phthalate ions in pH region 0–8. They obtained


three reproducible polarographic waves of phthalates in non buffered solutions near pH 4. In the case of buffered medium obtained phthalate waves suitable for quantitative analysis. Saeed et al [143] employed DPP at DME for the determination of aliphatic phthalates from polymeric products such as baby toys, nipples, teethes, infusion blood bags and shopping bags. They optimized composition and supporting electrolyte concentration of 0.1M TMAB, methanol as solvent, initial potential -1.4, pulse amplitude 0.05V, voltage step 0.006V, and voltage step time 0.00595 s. They observed reduction peak potential of dibutyl phthalate (DBP) at –1.75V vs SCE at optimized conditions. They added different phthalates such as dipentyl phthalate, diethylhexyl phthalate, and dioctyl phthalate with peak potential ranging from –1.73 to –1.75 V for all phthalates. The found it is very difficult to separate individual peaks of phthalates. They found negligible interference effect of different organic compounds which are used in polymeric materials such as hydroquinone, picric acid, 4-nitrophenol, maleic acid, acrylamide, and vinyl chloride mixed in 1:1 ratio. Tanaka and Takeshita [144] developed a method for determination of total phthalate esters as phthalic acid in waste waters using differential pulse polarography (DPP). They converted phthalate esters into phthalic acid by extraction and by refluxing in the presence of some organic and inorganic compounds. They got recoveries 83 – 90% for DBP and DEHP.

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ACCEPTED MANUSCRIPT Critical evaluation of above summarized results leads us to the conviction that even classical polarographic methods, which are usually considered obsolete, old-fashioned and not too useful in modern analytical laboratories, can be successfully applied for the determination of various phthalates in different matrices. And extension of this conclusion to the application of modern potential programs (DPV, SWW, AdSV) in combination with HMDE or its miniaturized


variations is obvious. 3.2. Voltammetric methods These methods include predominantly cathodic voltammetry at hanging mercury drop electrode (HMDE), at meniscus modified silver solid amalgam electrode (mAgSAE) or at various solid electrodes with sufficiently broad potential window in negative region. Saeed el al [145] determined total water soluble phthalates from plastic water bottles on glassy carbon electrode (GCE) by square wave voltammetry (SWV). They optimized some parameters such as supporting electrolyte (0.05M tetrabutylammonium bromide (TBABr)), stirring rate 1400 rpm, deposition time 20s, scan rate 0.9 Vs-1, frequency 100 Hz and pH 4.0. They obtained two cathodic peaks of di-n-butyl phthalate at potentials -1.68 V and -1.88 V vs. SCE. Barek et al [146] developed a DPV method for four aliphatic phthalates (DBP, DEP, DDP, and DAP) at a hanging mercury drop minielectrode (HMDmE) and at m-AgSAE. They have optimized most important parameters such as supporting electrolyte (0.1M TMABr), methanol as solvent, pulse amplitude -50 mV, scan rate -20mVs-1 and pulse width 100 ms. Well-developed reduction peak of every individual phthalate on both electrodes was obtained. Limit of quantification (LOQ) of DEP, DBP, DDP, and DAP was found to be 0.3, 0.3, 0.5 and 0.3 µmolL-1, respectively, at HMDmE, and 3, 2, 4, and 4 µmolL-1 , respectively, at m-AgSAE.

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The parameters of existing polarographic and voltammetric methods are summarized in Table 2.

Voltammetric methods are usually faster, more sensitive and they provide lower limits of detection compared to polarographic ones. Moreover, in the case of mercury electrodes, they


significantly decrease the consumption of mercury resulting in “greener” analytical methods. However, in the case of more complex matrices with greater danger of electrode passivation, polarographic methods at dropping mercury electrode, the surface of which is periodically renewed during measurement, are to be preferred because they are less prone to problems connected with electrode passivation which is more probable in the case of HMDE than DME.

4. Conclusions It is obvious that modern separation methods summarized in the first part of this review are most frequently used because of their high sensitivity and selectivity. However, it is worth mentioning that simpler, faster, and less expensive spectrophotometric methods can be methods of choice in many cases. The same holds for polarographic and/or voltammetric methods. It is interesting to note that most polarographic studies were carried out as early as 1950s-1960s. As polarographic technique was one of the most popular electroanalytical techniques at that time, all the studies were carried out using classical polarographic techniques which is capable of to determine the phthalates to mmol/l levels. However determination of individual phthalates in mixtures was not achieved due to very small half-wave potential differences between individual phthalates. The interest in electrochemical determination of phthalates was renewed in 1990’s with the onset of

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ACCEPTED MANUSCRIPT new electrode materials and arrangements and of pulse techniques. Nevertheless, up to now only few studies were published using voltammetric techniques at other than the classical HMDE, the only exception being silver solid amalgam electrode which can serve as a suitable substitute for HMDE because of comparable electrochemical properties. It is probably possible to determine phthalates by using modified glassy carbon electrodes with various agents such as diazonium


salts, gold nanoparticles and graphene oxide due to their large potential window and surface area plus their catalytic electrochemical properties [147-157]. Moreover, boron doped diamond electrodes with broad potential window in cathodic region [158-160] are suitable candidates for voltammetric determination of phthalates. The research in this direction is going on in our laboratories.

Acknowledgements This research was financially supported by Grant Agency of the Czech Republic (Project P206/12/G151).

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ACCEPTED MANUSCRIPT Table 1 Parameters of chromatographic methods for determination of phthalates in various


matrices

Method

Analyte

GC-FID

DMP DEP DBP DEHP

Linear range Mol.L-1 5.1×10-8 - 9.3×10-8 4.5×10-8 - 8.1×10-8 3.6×10-8 - 6.5×10-8 2.6×10-8 - 4.6×10-8

LOD Mol.L-1 1.4×10-10 1.2×10-10 1.5×10-10 6.9×10-11

Matrices

Ref

Waste water

[90]

from river GC-FID

DMP

5.1×10-6 – 2.6×10-3

1.0×10-6

Fatty food

SPME–GC– FID

DMP DEP DnPP DBP DnBP DEHP

1.0×10-8 - 2.6×10-7 9.0×10-9 - 2.2×10-7 8.0×10-9 – 2.0×10-7 7.2×10-9 - 1.8×10-7 7.2×10-9- 1.8×10-7 5.1×10-9 - 1.3×10-7

2.1×10-8 9.0×10-9 6.0×10-9 2.2×10-9 1.1×10-9 5.1×10-10

Water

DMP DEP DnOP BBP

1.7×10-11 – 2.1×10-7 1.4×10-11 - 1.8×10-7 1.4×10-11 - 2.0×10-7 8.3×10-11 - 2.6×10-7

5.1×10-12 4.2×10-12 4.4×10-12 2.5×10-11

Waste

SDME-GGFID

samples

water

[91]

[92]

[93]

samples SPME-GC

HS-SPMEGC

DMI-SPEGC

DMP DEP DPP

5.1×10-8 – 5.1×10-7 4.5×10-8 – 4.5×10-7 4.0×10-8 – 4.0×10-7

1.9×10-8 1.6×10-8 2.0×10-8

Mineral

DBP DAP DEHP DnOP DNP DDP DEP DBP BBP DIOP

5.7×10-10 - 5.7×10-6 5.2×10-9 - 5.2×10-6 1.2×10-9 - 1.2×10-6 1.2×10-9 - 1.2×10-6 1.9×10-9- 1.9×10-6 1.8×10-8- 1.8×10-6 2.2×10-8- 3.4×10-6 1.8×10-8 - 2.7×10-6 1.6×10-8- 2.4×10-6 1.3×10-8- 1.9×10-6

3.2×10-10 1.7×10-10 3.8×10-11 9.7×10-11 2.2×10-10 6.7×10-11 5.0×10-9 4.0×10-9 2.7×10-9 2.7×10-9

Beverages

46

water

[94]

[95]

Plastic bottled

[96]

ACCEPTED MANUSCRIPT

ACCEPTED MANUSCRIPT DnOP

1.3×10-8 - 1.9×10-6

3.5×10-9

beverage products


GC-MS

GC-MS

GC-MS

SPME-GCMS

SPME-GCMS

DBP DEHP DMEP NPIPP DNPP DIPP BBP

0- 2.9×10- 6 0- 5.1×10- 6 0- 7.1×10- 6 0- 3.3×10- 7 0- 3.3×10- 7 0- 3.3×10- 7 0- 3.2×10- 7

1.9×10- 7 1.2×10-7 4.3×10-7 1.6×10-8 2.0×10-8 2.0×10-8 3.8×10-8

Perfumes

DEHP

2.6×10- 7 - 2.6×10-6

3.5×10- 8

Toys

DiBP DnBP BBP DEHP DOP DMP DEP DiBP DBP DHP BBP DEHA DEHP DOP

2.2×10-7 – 3.6×10-5 2.2×10-7 - 3.6×10-5 1.9×10-7- 3.2×10-5 1.5×10-7-2.6×10-5 1.5×10-7 – 2.6×10-5 5.2×10-10 – 1.0×10-7 4.5×10-10 -9.0×10-8 3.6×10-10 -7.2×10-8 3.6×10-10 –7.2×10-8 3.0×10-10 – 6.0×10-8 3.2×10-10 – 6.4×10-8 2.7×10-10 - 54×10-8 2.6×10-10 – 5.1×10-8 2.6×10-10 – 5.1×10-8

1.8×10-8 5.8×10-8 2.2×10-8 1.3×10-7 2.8×10-8 6.2×10-11 2.2×10-10 2.3×10-10 2.2×10-10 1.1×10-10 2.7×10-10 4.6×10-11 1.3×10-10 7.7×10-12

Infant

DIBP DBP BMPP DPP DHXP BBP DCHP DEHP DIP DNOP DINP

3.6×10-7-3.6×10-4 3.6×10-7-3.6×10-4 3.0×10-7-3.0×10-4 3.3×10-7-3.3×10-4 3.0×10-7-3.0×10-4 3.2×10-7-3.2×10-4 3.0×10-7-3.0×10-4 3.0×10-7-2.6×10-4 3.1×10-7-3.1×10-4 2.6×10-7-2.6×10-4 2.4×10-7-2.4×10-4

5.0×10-8 5.7×10-8 2.7×10-8 2.0×10-8 1.2×10-8 4.8×10-8 1.5×10-8 1.3×10-8 5.7×10-8 5.1×10-8 5.5×10-8

Lake

47

[97]

[98]

food pack

[99]

Bottled

[100]

water

water

[101]

ACCEPTED MANUSCRIPT

ACCEPTED MANUSCRIPT

DMP DEP DBP DAP DNOP LPME-GCDMP MS DEP DAP DnBP BBP DCHP DEHP SBSEDMP LD/LVI-GC– DEP MS DBP BBP DEHA DEHP

5.2×10-11- 5.2×10-8 4.5×10-11- 4.5×10-8 3.6×10-11 – 3.610-8 3.6×10-11 – 3.6×10-8 5.1×10-11 – 2.6×10-8 2.6×10-10 -5.2×10-7 2.3×10-10 – 4.5×10-7 2.0×10-10 – 2.0×10-7 1.8×10-10 – 1.8×10-7 1.6×10-10 – 3.2×10-7 3.0×10-10 – 1.5×10-7 1.3×10-10 – 2.6×10-7 6.2×10-9 – 7.7×10-7 5.4×10-9 – 6.8×10-7 8.3×10-9 – 5.4×10-7 3.8×10-9 – 3.7×10-6 3.2×10-9 – 4.0×10-7 3.1×10-9 – 5.5×10-6

7.4×10-11 1.2×10-11 7.8×10-12 1.9×10-11 5.3×10-11 1.5×10-10 9.0×10-11 8.1×10-11 1.1×10-10 9.6×10-11 1.5×10-10 5.1×10-11 1.5×10-9 1.3×10-9 2.2×10-9 4.8×10-10 4.0×10-10 7.7×10-10

Bottled

DLLME-GC- DMP MS DEP DBP BBP DEHP DOP PLE-GC-MS DMP DEP DiBP DBP BBP DEHA DEHP DnOP

2.6×10-10 – 7.7×10-7 2.2×10-10 – 6.7×10-7 1.8×10-10 – 5.4×10-7 1.6×10-10 – 4.8×10-7 1.3×10-10 – 3.8×10-7 1.3×10-10 – 3.8×10-7 2.1×10-11 – 2.1×10-7 1.8×10-11 – 1.8×10-7 1.4×10-11 – 1.4×10-7 1.4×10-11 – 1.4×10-7 1.3×10-11 – 1.3×10-7 1.08×10-11 – 1.08×107 1.0×10-11 – 1.0×10-7 1.0×10-11 – 1.0×10-7

1.1×10-10 4.0×10-11 5.0×10-11 3.1×10-11 1.30×10-11 1.3×10-11 2.1×10-10 1.0×10-9 1.4×10-9 1.4×10-9 6.4×10-11 1.08×10-9 5.1×10-9 1.0×10-10

Bottled


MI-SPMEGC–MS.

48

water

[102]

River water

[103]

Bottled mineral

[104]

water

water

[105]

Harbor air from

[106]

Tarragona

ACCEPTED MANUSCRIPT

ACCEPTED MANUSCRIPT SBSE–TD– GC–MS


HPLCUV/Visible detector

DMP DEP DBP BBP DEHP DOP DBP DEHP DINP DIDP DBP DEHP DINP DIDP

5.1×10-11 – 1.0×10-9 4.5×10-11 – 9.0×10-10 3.6×10-11 – 7.2×10-10 3.2×10-11 – 6.4×10-10 2.6×10-11 – 5.1×10-10 2.6×10-11 – 5.1×10-10 0- 3.6×10-9 0-2.6×10-9 0- 2.4×10-9 0- 2.3×10-9 0- 1.8×10-7 0- 1.3×10-7 0- 1.2×10-7 0- 1.1×10-7

1.0×10-11 9.0×10-11 1.8×10-12 5.8×10-12 2.6×10-13 5.6×10-12 7.9×10-11 7.2×10-11 1.3×10-10 1.1×10-10 4.0×10-11 3.6×10-11 6.2×10-11 5.8×10-11

Sea and estuarine

[107]

water

Landfill

[108]

water Leachate sediments

HPLC-UV detector

HPLC-UV detector

DMP DEP DPrP BBP DBP DAP DCHP DEHP

5.8×10-9 -1.2×10-7 4.8×10-9- 9.5×10-8 5.1×10-9- 1.0×10-7 3.9×10-9- 7.9×10-8 3.9×10-9- 7.8×10-8 3.4×10-9- 6.7×10-8 3.3×10-9- 6.1×10-8 2,7×10-9- 5.4×10-8

1.2×10-9 4.5×10-12 17×10-10 3.2×10-12 2.5×10-11 7.0×10-10 6.8×10-10 3.5×10-10

River water

[109]

DMP DEP DBP

5.2×10-10- 5.2×10-8 4.5×10-10- 4.5×10-8 3.6×10-10- 3.6×10-8

6.8×10-8 3.2×10-8 5.6×10-8

Food

[110]

contacted materials

HPLC-DAD detector

DEHP MEHP

1.30×10-7- 1.30×10-5 1.8×10-7 – 1.8×10-5

2.6×10-8 5.4×10-8

Human seminal

[111]

plasma RP-HPLCUV detector

BBP DEHP

3.2×10-9- 6.4×10-7 2.6×10-10- 2.6×10-8

1.6×10-7 2.6×10-7

Water

RP-HPLCUV detector

DME DEP DPP DIBP

2.6×10-5- 1.0×10-3 2.2×10-5- 9.0×10-4 2.5×10-5- 9.8×10-4 2.2×10-5- 7.2×10-4

2.1×10-6 1.8×10-6 2.0×10-6 1.8×10-6

Nail

49

Cosmetics

[112]

[113]

ACCEPTED MANUSCRIPT

ACCEPTED MANUSCRIPT


MSPEHPLCUV/visible detector

SPMEHPLC-DAD

SPE-HPLCUV detector

BBP DBP DEHP DAP DPP BBP DCP DEHP

1.6×10-5- 6.410-4 1.8×10-5- 7.2×10-4 1.3×10-5- 5.1×10-4 2.0×10-9- 8.1×10-7 2.5×10-9- 9.8×10-7 1.6×10-9- 6.4×10-7 1.5×10-9- 6.1×10-7 1.3×10-9- 5.1×10-7

DAP DPP BBP DCP DEHP DEP DPP BBP DBP AP DCHP DHP DEHP DOP

4.1×10-9- 8.1×10-7 4.9×10-9- 9.8×10-7 3.2×10-9- 6.4×10-7 3.0×10-9- 6.1×10-7 2.6×10-9- 5.1×10-7 9.0×10-9- 4.5×10-7 4.9×10-9- 2.5×10-7 3.2×10-9 - 1.6×10-7 3.6×10-9- 1.8×10-7 6.6×10-9- 3.3×10-7 6.1×10-9- 3.0×10-7 6.0×10-9 – 3.0×10-7 2.6×10-8- 1.3×10-6 2.6×10-8- 1.3×10-6

DEP DnPP DnBP DcHP DEHP

2.7×10-9 – 2.2×10-7 2.9×10-9 – 2.5×10-7 2.2×10-9 – 1.8×10-7 1.8×10-9 – 1.5×10-7 1.5×10-9 – 1.3×10-7

1.6×10-6 1.8×10-6 1.5×10-6 4.1×10-10 3.431×10-10 2.9×10-10 3.026×10-10 1.8×10-10 8.1×10-10 7.4×10-10 9.6×10-10 6.1×10-10 5.1×10-10

Water [114]

Soybean milk

9.0×10-10 1.50×10-9 1.9×10-9 1.8×10-9 3.3×10-9 3.0×10-9 4.8×10-9 1.0×10-8 9.8×10-9

Plastics

7.6×10-10 7.4×10-10 4.7×10-10 4.3×10-10 3.1×10-10

Environ-

and food

[115]

samples

[116]

mental water samples

LC-MS

DEHP

1.3×10-7- 2.6×10-6

5.1×10-8 7.7×10-11

Water

[117]

Soil LC-MS/MS

LC-MS/MS

DMP DEP BBP DBP

2,6×10-9 – 5.2×10-7 2.3×10-9 – 4.5×10-7 1.6×10-8- 3.2×10-7 1.4×10-7- 9.0×10-7

1,5×10-10 8.6×10-10 9.9×10-10 9.4×10-10

Contact

MEHP MEHHP

3.6×10-9 – 3.6×10-7 3.4×10-9 – 3.4×10-7

7.2×10-10 6.8×10-10

Human

50

[118]

lenses

[119]

ACCEPTED MANUSCRIPT

ACCEPTED MANUSCRIPT


LC-TOF/MS

Cyclodextrin modified MEKC

UFLC-MS

UPLC MS/MS

MEOHP 5cxMEPP 2cxMMHP DEP DPrP BBP DBP DPP DCHP DHP DEHA DEHP DINP DIDP DMP DEP DAP DPP DBP DNPP DCP BBP DEHP DMP DEP DPrP BBP DCHP DOP DBP BBP DOP DEHP DIDP DINP

3.2×10-9- 3.2×10-7 3.2×10-9 – 3.2×10-7 3.2×10-9 – 3.2×10-7

6.3×10-10 3.2×10-9 3.2×10-9

hair

2.5×10-9 – 4.5×10-7 2.5×10-9 – 4.9×10-7 1.6×10-9 – 3.2×10-7 1.8×10-9 – 3.9×10-7 1.6×10-9 – 3.3×10-7 1.5×10-9 – 3.0×10-7 1.5×10-9- 3.0×10-7 1.3×10-9 – 2.7×10-7 1.3×10-9 – 2.6×10-7 1.2×10-9 – 2.4×10-7 1.2×10-9 – 2.2×10-7 2.6×10-4 - 1.5×10-3 2.2×10-4 - 1.3×10-3 2.0×10-4 - 1.2×10-3 2.5×10-4 - 1.5×10-3 1.8×10-4 -11×10-3 1.6×10-4 - 9.8×10-4 1.5×10-4 – 9.1×10-4 1.6×10-4 - 9.6×10-4 1.3×10-4 - 7.7×10-4 1.0×10-9 – 2.6×10-7 9.0×10-10 - 2.2×10-7 9.8×10-10- 2.510-7 1.6×10-8- 3.2×10-7 6.1×10-10- 1.5×10-7 5.1×10-10 – 1.3×10-7 3.6×10-9- 3.6×10-7 6.4×10-19- 3.2×10-7 1.3×10-8- 2.6×10-7 1.3×10-8- 2.8×10-6 4.5×10-9- 2.3×10-7 4.8×10-9- 3.0×10-6

8.5×10-9 9.8×10-9 6.7×10-9 4.3×10-9 9.1×10-9 8.2×10-9 8.072×10-9 5.397×10-9 3.840×10-9 3.3×10-9 4.010-9 4.4×10-5 3.9×10-5 3.1×10-5 3.8×10-5 4.1×10-5 2.3×10-5 4.7×10-5 3,2×10-5 4.9×10-5 2.6×10-10 9.0×10-11 1.5×10-10 2.9×10-9 1.2×10-10 1.0×10-10 1.5×10-9 2.0×10-9 4.3×10-9 4.1×10-9 1.5×10-9 1.5×10-9

Edible

51

[120]

salts from food market

Perfumes

[121]

Saline

[122]

samples

Toys

[123]

industries

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ACCEPTED MANUSCRIPT Table 2. Parameters of polarographic and voltammetric methods for determination of phthalates in various matrices


Method Electrode

Analyte

Linear range (mol L-1) 4×10-7– 1×10-5 8×10-7 – 4×10-6 8×10-7 – 4×10-6 1×10-7 – 1×10-4

Detection limit (mol L-1) 1.1×10-7

DPP a

DME b

PA c esters

DPP

DME

DEP d DBP e

DPP

DME

DMP f

DPP

DME

DBP

3×10-7 – 1.6×10-4

5.9×10-8

DPV g

GCEh

DnBP i

2×10-6– 1.1×10-4

4.7×10-7

DCTP j

DME

Terephthalic acid

0.5×10-3 – 5×10-3

Not given

a

Differential pulse polarography;

b

6.7×10-8 7.4×10-7 1.1×10-7

Matrices

Waste water

Reference

[144]

Oil water [132] emulsions and Skimmed milk Cationic [133] surfactant Hyamine1622 Polymeric [143] products, Plastic water bottle and water coolers Mixture of phthalic acid isomers

Dropping mercury electrode;

c

[145]

[137]

Phthalic Acid;

d

phthalate; e Dibutyl phthalate; f Dimethyl phthalate; g Differential pulse voltammetry;

Diethyl h

Glassy

carbon electrode; i Di-n-butyl phthalate; j Direct current tast polarography

52

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Figure 1. Molecular structures of commonly used phthalates; a) Phthalate ester (general), b) DMP c) DEP, d) DBP, e) BBP, f) DEHP g)DINP, h) DIDP, i) DNDP.

53

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Figure 2. Equations showing reduction of diethylphthalate at a dropping mercury electrode.

54

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Figure 3. Reduction of diethyl phthalate and dibutyl phthalate at a droping mercury electrode using of emulsified surfactant Hyamine 1622 dissolved in 1:9 ratio of diethyl ether and ethyl acetate in supporting electrolyte 0.1molL-1 Britton-Robinson buffer pH at 10.

55

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Anionic surfactant micelle-mediated extraction coupled with dispersive magnetic microextraction for the determination of phthalate esters.

Phthalate esters: heartrate depressors in the goldfish.

Simultaneous determination of trace migration of phthalate esters in honey and royal jelly by GC-MS.

Identification and determination of phthalate esters in river water by high-performance liquid chromatography.

Determination of phthalate esters in Chinese spirits using isotope dilution gas chromatography with tandem mass spectrometry.

Graphene nanoplatelets as a highly efficient solid-phase extraction sorbent for determination of phthalate esters in aqueous solution.

Analysis of tissues of mallard ducks fed two phthalate esters.

Structure-dependent activity of phthalate esters and phthalate monoesters binding to human constitutive androstane receptor.

Comparison of chromatographic methods for the analysis of glycerol esters.

Uptake and Metabolism of Phthalate Esters by Edible Plants.

Determination of phthalate esters in liquor samples by vortex-assisted surfactant-enhanced-emulsification liquid-liquid microextraction followed by GC-MS.

MS.

Self-immolative phthalate esters sensitive to hydrogen peroxide and light.

Spectrophotometric methods for the determination of sulphathiourea.

Methods for determination of hirudin.

Surface molecularly imprinted polymers with synthetic dummy template for simultaneously selective recognition of nine phthalate esters.

The occurrence and ecological risk assessment of phthalate esters (PAEs) in urban aquatic environments of China.

Effects of phthalate esters on the respiration of rat liver mitochondria.

Phthalate esters in water and sediments of the Kaveri River, India: environmental levels and ecotoxicological evaluations.

FID for Determination of Trace Contamination of Phthalate Esters in Water Samples.

The influence of facility agriculture production on phthalate esters distribution in black soils of northeast China.

Effects of phthalate esters on the latent ATPase and swelling of mitochondria.

Development of Methods for Determination of Aflatoxins.

Molecular methods for serovar determination of Salmonella.