Abstract
Emerging contaminants (ECs) are substances that have no defined environmental quality standards or regulations, and have the potential to pose major adverse impacts on the environment and human health. The detection of contaminants in the natural environment is the key step for establishing precise environmental risk assessment approach for ECs. However, ECs come from different origins with various physicochemical properties, making their detection a complicated process. Moreover, their presence in the aquatic environment at trace concentration range (ng/L-µg/L), requires an accurate detection at low concentration levels. This study aims to develop an efficient analytical method for simultaneous determination of 5 different ECs in aqueous solution based on solid phase extraction technique (SPE) followed by liquid chromatography-mass spectrometry (LC–MS/MS). High recovery rates (72% to 114%) were achieved for all targeted compounds. Ciprofloxacin (CIP), diuron (DIU), terbutryn (TER) and diclofenac (DIC) had a limit of detection (LOD) of 5 µg/L and a limit of quantification (LOQ) of 10 ng/L, while LOD and LOQ for EE2 were 25 µg/L and 50 ng/L, respectively. These results confirm that the optimized method can be applied for extraction and analysis of ECs from different classes in the aquatic environment.
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1 Introduction
Emerging contaminants (ECs) are the pollutants for which no regulations are currently established (Tavengwa & Dalu, 2022). According to NORMAN association that is funded by the European Union (EU), the most frequently identified ECs include more than 4000 compounds which are categorized in 20 classes including pharmaceuticals, personal care products, steroid hormones, pesticides, plasticizers, surfactants etc. (NORMAN Database System, n.d.). Moreover, the EU is periodically issuing watch lists of priority substances that should be monitored for establishing environmental quality standards. Starting from the Directive 2013/39/EU that published the water quality limit for the first revised list of priority substances, there are three more EU watch lists that have been established for ECs including Decision (EU) 2015/495, Decision (EU) 2018/840 and Decision (EU) 2020/1161 (Alexa et al., 2022). Nonetheless, due to the continuous increase in daily use and/or consumption of the sources of ECs, the list of ECs is expected to constantly expand over time, while there are more than 500 thousand chemical substances currently identified in the Chemical Abstracts Service (CAS) (Jacobs et al., 2022).
These contaminants enter the environment from multiple sources, e.g., agricultural runoff, hospital wastewater, domestic and industrial effluent discharges, etc. ECs are most frequently detected in various aquatic environmental matrices such as seawater, freshwater and wastewater (AJIBOLA et al., 2021; Cipriani-avila et al., 2023; Klaic & Jirsa, 2022; Linke et al., 2021; Mostafa et al., 2023a, 2023b; Palma et al., 2021; ZIND et al., 2021). Moreover, ECs were also detected in drinking water and even the deep groundwater aquifers (Lapworth et al., 2018; López-Serna et al., 2013; Sui et al., 2015; Tijani et al., 2016; Wilkinson et al., 2017; G. Yang et al., 2014; Zainab et al., 2021). Although ECs are detected at trace concentration range of ng/L to µg/L (Chaturvedi et al., 2021; Gwenzi & Chaukura, 2018), they could pose detrimental effects on the living organisms due to their persistent nature in the environment, toxicity and bioaccumulation potential(T. H. Y. Lee et al., 2021; Parida et al., 2021; Saidulu et al., 2021; J. Yang et al., 2019). These adverse effects could span across various biological scopes, such as nephrotoxic, genotoxic, and hepatotoxic effects (T. H. Y. Lee et al., 2021). Therefore, the occurrence of these substances in the environment has become a matter of concern globally, and there are continues efforts to develop advanced analytical measurement techniques for taccurate monitoring and fate assessment of ECs in different environmental matrices (Angeles et al., 2021; Castillo-Zacarías et al., 2021; Hajeb et al., 2022; Martín-Pozo et al., 2019; Ofrydopoulou et al., 2021; Rao et al., 2023; Ryu et al., 2021).
The detection of multiple ECs in the environmental samples are mostly performed by liquid chromatography-mass spectrometry (LC–MS/MS) and gas chromatography-mass spectrometry (GC–MS) (Gimeno et al., 2014; Harati et al., 2020; Krupčík et al., 2013; Pitne et al., 2017; Rasheed et al., 2016; Vittoria et al., 2019; W. Wang et al., 2023a, 2023b). However, GC–MS can only deal with volatile and semi-volatile compounds, and a prolonged derivatization process is usually mandatory in order to ensure the volatility of the sample analytes (Bekele et al., 2014; Kanani et al., 2008; Sodré et al., 2010). Therefore, LC–MS/MS is the most preferred analytical technique for the measurement of the vast majority of ECs in environmental matrices due to its versatility and sensitivity (Mackeown et al., 2022; Martín-Pozo et al., 2019). LC/MS/MS is usually combined with selective extraction, clean-up and pre-concentration techniques for the accurate measurement of ECs at trace concentrations, and for the elimination of possible interferences from environmental matrices (Etteieb et al., 2020). Solid phase extraction (SPE) is the most widely utilized technique for the pre-treatment of environmental samples because of its simplicity and enhanced selectivity (Aalizadeh et al., 2022; Ajibola et al., 2020; Bain et al., 2021; Barbieri et al., 2019; Do & Stuckey, 2019; Junaid et al., 2018; Kovacs et al., 2021; Riva et al., 2021; Schmidt et al., 2018; Vittoria et al., 2019).
Most of the developed pre-treatment and measurement methods for the quantification of ECs have exclusively focused on one group of compounds (e.g., pesticides, pharmaceuticals) (X. Chen et al., 2022; Kunene & Mahlambi, 2020; Mostafa et al., 2023a, 2023b; Peleshok et al., 2021), while there are numerous number of ECs that belong to various classes and chemical groups such as pharmaceuticals, endocrine disrupters, pesticides, steroid hormones, plasticizers and surfactants with distinct physicochemical properties. Therefore, there is an urgent need for the development of new methods for the simultaneous detection of ECs in the natural environmental samples that is considered as the current challenge of monitoring the ECs in the environment (L. Chen et al., 2023). Thus, the aim of this study was to optimize a fast, selective and sensitive method for the simultaneous extraction and measurement of multiclasses of ECs in water matrices by SPE–LC–MS/MS analysis technique.
ECs for this study were chosen based on their distinct physicochemical properties such as different solubilities in water and organic solvents, as well as various chemical structures including phenylacetic acid (Diclofenac), carbonyl diamide (Diuron), heterocyclic N,S triazines (Terbutryn), quinolinecarboxylic acid (Ciprofloxacin) and steroids (EE2). These ECs also have diverse sources and applications (anti-inflammatory drugs, pesticides, herbicides, antibiotics and oestrogens). Moreover, these contaminanats are included in the EU watch list of substances that should be monitored (European Commission, 2013) and are among the most frequently used and detected ECs in the aqueous environment worldwide (Böger et al., 2021; Deich et al., 2021; Duan et al., 2020; Fahimi et al., 2020; Lagunas-Basave et al., 2022; Palma et al., 2021; Parolini, 2020; Rehberger et al., 2020; Sol et al., 2022; R. Wang et al., 2023a, 2023b; Zhang et al., 2021; ZIND et al., 2021).
2 Materials and Methods
Target compounds were obtained in powder form: diclofenac sodium salt (15307–79-6), terbutryn (886–50-0), ciprofloxacin (85721–33-1), 17α-ethynylestradiol (EE2) (57–63-6) (Sigma-Aldrich, China) and diuron (330–54-1) (Sigma-Aldrich, Germany). All chemicals were of high purity grade ≥ 97%. Methanol (99.9%), methyl tert–butyl ether (MTBE) (99.8%), acetonitrile (ACN, > 95%), ethylacetate (99.8%), acetone (98%), isopropyl (98%), dichloromethane (99.8%) and hexane (99.8%) were of gradient grade for liquid chromatography and purchased from Sigma Aldrich. Deuterium-labeled hydrogen isotopes, Diclofenac-d4 (CDN, purity 99.0%), Ciproflaxin-d8 (CDN, purity > 98%), 17-alpha -ethinylestradiol-d4 (CDN, purity 99.0%), Diuron-d6 (LGC, purity > 98%), Terbutrin-d5 (LGC, purity 99.0%) are used for LC/MS internal standard solution preparation (stored at 4 ℃) in order to quantify sensitive measurements with LC/MS–MS. Oasis HLB SPE cartridges (60 mg, 3 mL), Thermo Scientific SolEx C18 cartridges and HyperSep Retain PEP cartridges were purchased from Agilent Technologies.
2.1 SPE Method Development
A SPE method was optimized for the simultaneous extraction of five different ECs including diclofenac (anti-inflammatory drug), ciprofloxacin (antibiotic), EE2 (oestrogen), terbutryn (herbicide) and diuron (pesticide). Their logKow values ranges from 2.68 to 4.51 and their water solubility varies between 2 and 2000 mg/L (Table 1).
The extractions were carried out in duplicates for each sample containing 1 µg/L of the targeted analytes mixture and 50 µL of 1000 ppb internal standard in 500 mL. Solvents to be used for extaction, conditioning and elution were selected by a literature review to determine the possible appropriate solvent candidates of each contaminant. The selected solvents for the optimization of SPE method are limited to the low boiling point-having solvents to avoid losses of volatile analytes and to minimize the time required for evaporation step (HU et al., 2008). Dichloromethane, hexane, methanol, ethyl acetate, acetone, acetonitrile, isopropyl and MTBE were used for conditioning and eluting the SPE cartridges with a volume of 5 mL for each solvent. After conditioning, in order to remove any impurity coming from cartridge manufacturing and to activate the cartridge’s surface by wetting the sorbent material, 500 mL sample of contaminants mixture (1 µg/L) was percolated through the cartridges under vacuum by maintaining a flowrate of 5 mL/min. Afterward, the cartridges were rinsed with 5 mL ultrapure water (UPW) or a mixture of solvent:UPW in order to remove any undesired contaminants attached to the surface of the sorbent.
Then, the cartridges were left to dry under vacuum for 30 min in order to completely eliminate water because it could negatively affect the analytes recovery rates of the analytes. The analytes were eluted from the cartridges by successively adding the organic solvents and the final extract was dried under a gentle stream of nitrogen overnight. After complete dryness, the extracts were reconstituted to 1 mL by a mixture of UPW and organic solvent for LC–MS analysis.
2.2 Instrumental Analysis
After SPE, 100 µL of reconstituted extracts are directly injected in the LC–MS/MS instrument under the following optimized conditions.
2.2.1 LC/MS Optimization
LC–MS/MS measurements were conducted with Thermo TSQ Fortis Model Tandem Mass Spectrometer (MS–MS) connected to Thermo Ultimate 3000 Model Ultra Pressure Liquid Chromatograph (UPLC). Atmospheric Pressure Ionization (APCI) is used as the ionization source. First of all, MS parameters were optimized to insure that the targeted contaminants are recognized by the detector, then, the conditions that provide sufficiently high signals are determined and the appropriate peak integration for quantitative analysis was made. Afterwards, LC parameters were optimized.
2.2.2 Optimization of MS Parameters
Each analytical standard was prepared at a concentration of 1 mg/L by diluting from their stock solutions, and injected directly into the ionization source in the MS. 1:1 mixture of Methanol containing 5 mM Ammonium fluoride: UPW containing 5 mM Ammonium fluoride was used as the mobile phase solvent for screening after trials with ammonium formate, ammonium fluoride and formic acid as basic buffers. The mass/ion (m/z) ratios of the main substance and the ionization products were determined for each analytical standard. In this part, the ionization occurs in a triple quadrupole structure at a certain pressure and temperature. Determination of the mass weights require the optimization of the various pressure values with the "Compound Optimization Workspace".
Ammonium fluoride was chosen by considering the intensities of the electrical signals given by the ionization products. With MS/MS scanning, "spray voltage", "volatile temperature", "tube lens offset" parameters were also automatically optimized by considering the intensities of the received signals. “Nitrogen gas pressure”; “carrier gas pressure”, “ion stripping gas pressure”, and “additional gas pressure” were optimized by trial and error. The most effective parameter for the ionization process was the "collision energy" parameter.
2.2.3 Optimization of LC Parameters
Samples in the autosampler are passed through proper analytical columns to separate target compounds from the sample. Separation mechanism depends on the adsorption capability of the target compound on column package material and its solubility in the mobile phase that carries the sample from autosampler to LC–MS. Therefore, the type of column, including the characteristics of package material, types and gradient of mobile phase are optimized for the effective separation of the target compound from the sample. Moreover, temperature of the column and auto sampler, sample injection volume and mobile phase velocity should be considered for the high recovery of target compound from the LC column.
3 Results and Discussion
3.1 Optimization of SPE
3.1.1 Trial 1
OASIS HLB (Hydrophilic-lipophilic balanced N-vinylpyrrolidone-co-divinylbenzene) SPE cartridges were used for the first trial. As shown in Table 2, CIP and TER had the highest recovery percentages in the first method (88% and 114%, respectively), while the recovery rates of diuron, diclofenac and EE2 were at unacceptable levels (0%-44%). At first method, an elution mixture of UPW, methanol, and acetonitrile (70:20:10) were used as elution solvents. In the second method, replacing the methanol and acetonitrile with acetone led to a decrease in recoveries for all ECs except for EE2. Conditioning with MTBE and acetonitrile and eluting with isopropyl: UPW (15:85) resulted in low recoveries except for TER (Table 2). Changing the reconstitution solution with acetonitrile instead of UPW: isopropyl mixture did not increase the recoveries. The effect of the solution pH was also studied by changing it to 2 and 9. The recovery rates of targeted compounds except TER increased with decreasing pH value from 9 to 2 with using the same conditioning and elution solvents in method 6; however, they were still not in the acceptable range. The acidic pH could enhance the recovery rate of the targeted pollutants especially by avoiding the precipitation of DIC and improve the retention of EE2 compound on the SPE cartridge (Česen & Heath, 2017a; Kosjek et al., 2009; Valdés et al., 2015). Therefore, methanol and acetonitrile were further examined with other types of SPE cartridges and different elution solvents at acidic pH in the second trail.
3.1.2 Trial 2
In addition to OASIS HLB cartridge, the Thermo Scientific SolEx C18 (Silica) cartridge, which is a nonpolar cartridge and mainly chosen for its sufficient selectivity for the steroidal and nonpolar to moderately polar compounds (Kopperi et al., 2013; Riva et al., 2021; Valdés et al., 2015; Wu et al., 2014; Zuo et al., 2013) and HyperSep Retain PEP (HyperSep Urea-Modified Polystyrene DVB) cartridge, which is also a frequently used cartridge for the extraction of ECs were examined. In this trial, all three cartridges had relatively similar recovery rates. However, C18 and HLB are known to retain a wider range of structures compared to PEP which could prohibit the adsorption of highly polar compounds on its surface due to its low polarity (Vaudreuil et al., 2022). C18 and HLB cartridges have the tendency of increasing the retention of high polar substances by the special polar trapping groups that are generated in their sorbent material by the polymerization of hydrophilic N-vinylpyrrolidone and lipophilic divinylbenzene monomers (Liu et al., 2015). Thermo Scientific SolEx C18 and HLB cartridges were chosen for further examination in following trails. Adjusting the pH of solvent to 2 improved the recoveries for TER and DIU for all cartridges (Table 3), as these compounds are weakly acidic (pKa 4.4 and 3.7 respectively), their dissociation and solubility in water is expected to increase under acidic conditions, thus enhancing their adsorption to the sorbent material (Barriuso et al., 1992; Cosgrove et al., 2019). Elution with acetonitrile and methanol increased the recovery of CIP while the recoveries of TER and DIU were still high. The high recovery rate of CIP with acetonitrile and methanol compared to other solvents was also observed in other studies (H. B. Lee et al., 2007; Martínez Bueno et al., 2009; A. F. Martins et al., 2008; Pápai et al., 2010). This could be due to the higher capability of these solvents to disrupt the interactions between the functional groups of targeted analytes and the sorbent surface, which depend upon the retention mechanism of the analyte such as its polarity.
3.1.3 Trial 3
This trial was conducted to test the OASIS HLB and C18 cartridges to increase the recoveries of DIC and EE2 as shown in Table 4. C18 cartridge provided the highest recovery rates for all targeted compounds especially for EE2 which ranged from 56% to 74.6% with C18 while EE2 either was not recovered at all or had unacceptable recovery rates for most of the tested methods with HLB cartridge. Compared to Oasis HLB which is preferred for the extraction of high polarity compounds (Dias & Poole, 2002), silica C18 is a nonpolar cartridge and have sufficient selectivity for the steroidal and nonpolar to moderately polar compounds (Nodeh et al., 2016). Thus, it would be more suitable for the retention of oestrogens and aliphatic compounds such as EE2 by the strong interactions of electron lone pair (Ciofi et al., 2013).
The addition of ethyl acetate solvent for elution with C18 cartridge enhanced the recovery of DIC and EE2 from 16 to 32% and 66% to 77.2%, respectively (methods 2 and 4). Removing of methanol and acetone from the elution solvents and methanol and acetonitrile from the conditioning combination did not affect the recovery rate of any compound (methods 5, 6, 7 and 8). The presence of other solvents in the elution and conditioning steps such as MTBE could have a dominant influence on the recovery rates of analytes over other types of solvents due to polarity differences. Therefore, methanol and acetone had minor role in SPE and it were excluded from the next trials. However, the exclusion of ethyl acetate from conditioning and elution (5, 6, 7, 8) decreased the recoveries of EE2 significantly. As oestrogens are medium polarity-compounds, and the elution step depends mainly on the resemblance of solvents’ and analytes’ polarity levesl, ethyl acetate might be matching or approaching the polarity of EE2 compound. As a result of this, elution with ethyl acetate can provide high recovery rate for EE2 that is also observed in other studies such as Česen & Heath, 2017b; Isobe et al., 2003; Liu et al., 2015; Zuo et al., 2007, 2013.
The combination of MTBE, acetonitrile and ethyl acetate solvents had further enhanced the recovery rates of all targeted compounds without the need of acidifying the solvents. Therefore, these solvents with C18 cartridge were further examined in the next trial with different analytes concentration and re-solution mixtures.
3.1.4 Trial 4
In this trial, modifications were made to increase the recovery of DIC which was still at unacceptable levels. Combination of MTBE and ethyl acetate increased the recovery for DIC and EE2 as seen in Table 5 (Method 3). The elution with the reverse order of conditioning solvent combination gave the best results for the recoveries of all ECs. The selected solvents from Trial 4 had been further examined with lower concentration (50 µg/L) of ECs and two different re-solution mixtures. As shown in Tables 5 and 6, all the extracted compounds had acceptable recovery rates at 50 µg/L and 500 µg/L. The reconstitution with the mixture of methanol: UPW (30:70 v/v %) had given higher recovery for EE2 (65% to 90%) and the relatively similar recovery rates for other analytes.
Based on the findings of four experimental trials conducted for the SPE of selected compounds, the method that was determined as the best possible method for the simultaneous recovery of all the targeted analytes from the aqueous phase by SPE is presented in Table 7.
3.2 Optimization of LC Parameters
The auto sampler temperature in the developed method has been optimized to 10 ℃. In order to reduce the measurement limit for EE2, the injection volume was kept as high as 100 µL. For this reason, both different material structures and volumes have been tried in order to achieve the highest recovery efficiency from the column.
The following columns are used in the trials;
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Thermo Accucore C18 brand 2.6 µm pore diameter 100*2.1 mm size
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Thermo Acclaim Polar Advantage 2.2 µm pore diameter 100*2.1 mm size
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Terra C18 3.5 µm pore diameter 100*2.1 mm size
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X-Bridge C18 3.5 µm pore diameter 50*4.6 mm size
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Waters Symetry C18 3.5 µm pore diameter 50*4.6 mm size
The columns showed the necessary selectivity for the separation of substances, and attention was paid to the tolerance of high sample volume, especially due to their different pore diameters. Thermo Accucore C18 brand column with a medium pore size of 100*2.1 mm and a pore diameter of 2.6 µm was selected.
Mobile phase solutions were selected in accordance with the polarities of the substances measured. Methonal and UPW were preferred as mobile phase solvents due to their common usage in different methods. As multiple measurements are made in a single injection, an optimization has been made to obtain a polarity gradient that will allow the separation of the substances, taking into account the degree of polarity of the substances to be separated. Since the mobile phase solvent also carries the substances to the MS where ionization takes place, a buffer solution is added to the mobile phase. The concentration for ammonium fluoride, which provides the most effective ionization during the optimization of MS parameters, was determined as 5 mM by trial and error, taking into account the pH levels in which the substance ionized. The mobile phase gradient, in which the measured substances are separated efficiently from each other, is shown in Table 8.
Accordingly, the mobile phase gradient starting with methanol containing 10% of 5 Mm ammonium fluoride is kept constant for 0.2 min, then increased to 70% within 2 min, increased to 90% between 2 and 5 min, and it remained stable at 90% for 2 min, and it then returned to its initial conditions for 2 min. The other mobile phase was ultrapure water containing 1 mM ammonium fluoride. Therefore, the developed method takes 7 min. Then, chromatographic conditions such as injection volume, mobile phase velocity and column temperature were tested and optimized so that all the substances to be measured were efficiently separated and formed non-intermingled peaks (Table 8). The optimized injection volume was 100 µL and the mobile phase velocity was 0.300 mL/min. While the column temperature was determined as 40 ℃.
3.3 Optimized MS Parameters
The optimized parameter values are summarized in Table 9. In MS/MS scanning systems, attention has been paid to using at least two ionization products in order to make precise measurements. The higher signal ion is used to quantify, and the other is used to verify the substance (Bester & Schlu, 2005). The ionization products detected in LC–MS/MS belonging to the selected contaminants are shown in Table 10. After the ionization products are detected, the parameters of the peak width, scan width, scan time, micro scan number, which determine the quality of the peak, have been tested and optimized and are summarized in Table 9.
3.4 Method Validation
In order to ensure the suitability of the optimized method for applications in routine analysis, the analytical quality parameters were evaluated including selectivity, stability, robustness, linearity, sensitivity, accuracy and precision.
3.4.1 Selectivity
Selectivity is an essential qualitative assessment for the analytical method which test the capability of the extraction method and it represents to which extent the interferences were avoided and the targeted analytes were distinguished among other organic compounds in the matrix. For this reason, the extraction of blank samples was performed using UPW, synthetic surface water and surface water matrices. The results were compared to the UPW matrice that was spiked with the targeted analytes. The recovery rates of the blank samples (0%—0.05%) and samples spiked with targeted analytes were (90%—114%) in an acceptable range. Moreover, there was no interference peaks in the chromatogram of blanks which indicates a good selectivity for the separation and extraction of the targeted analytes by the developed method.
3.4.2 Stability and Robustness
Stability and robustness parameters measure the capacity of the optimized method to remain unaffected by little but dynamic alterations in different factors or experimental conditions such as sample storage time and water matrix. The stability was evaluated by applying the optimized SPE method on 4 different sets including the targeted analytes at 50 µg/L. The first set was extracted immediately, while the other three sets were stored in dark at 4 °C and extracted after 24 h, 48 h and 72 h. The robustness of the method, which test the effect of the optimized method in different matrix, was examined by extracting 3 different sets including UPW and two synthetic surface water matrices with different TOC concentration (4.5 mg/L and 13.6 mg/L). The recovery percentages of all the analytes in the stability and robustness experiments did not exhibit any significant variation and were in the acceptable range (85%—115%) which confirm the robustness and stability of the optimized method.
3.4.3 Linearity
The linearity of the method tests the ability of the optimized method to provide directly proportional results to the real concentration of the analytes in samples. The linearity was examined by extraction of six spiked samples in the range of 10 µg/L – 750 µg/L (10 µg/L, 50 µg/L, 100 µg/L, 200 µg/L, 500 µg/L and750 µg/L). The correlation coefficients ( r2 values) for the targeted analytes ranged between 0.988–0.999, which is an evidence for a good linearity of the optimized analytical method within the studied range of concentrations (Figure S1 in Supplementary Information (SI)).
3.4.4 Accuracy and Precision
The accuracy of the method was tested at four different concentrations representing low, medium and high levels (10 µg/L, 50 µg/L, 100 µg/L and 500 µg/L) within the dynamic linear range. The recovery rates of the various concentrations of targeted analytes were in the range of 71%—117%, The precision was demonstrated by the replicate injection of the samples with a relative standard deviation of (RSD) less than 20%, which shows that the developed method has good repeatability and precision.
3.4.5 Sensitivity
Sensitivity parameter includes the determination of the limit of detection (LOD) taking three times value of the signal-to-noise ratio (S/N) for LOD and limit of quantification (LOQ) taking ten times S/N value after the application of SPE that provides the concentration factor for the calculations. SPE was applied for 500 mL of samples and the final volume is 1 mL after complete evaporation; therefore, the concentration factor is 500. The LODs values were 5 µg/L for ciprofloxacin, diuron, terbutryn and diclofenac, and 25 µg/L for EE2, while LOQs values for the targeted analytes were 0.01 µg/L for ciprofloxacin, diuron, terbutryn and diclofenac and 0.05 µg/L for EE2.
4 Conclusion
An analytical method was optimized for the simultaneous extraction and measurement of 5 different ECs in aqueous solutions based on a SPE-LC/MS/MS technique. The method optimization was achieved by examining the efficiency of different SPE cartridges and extraction solvents in multiple experimental trials. C18 cartridges along with acetonitrile, ethyl acetate and MTBE as extraction solvents have provided the highest recovery rate for all of the targeted compounds (90%—114%). The validity of the optimized method was inspected by the analytical quality parameter tests and the results confirmed the suitability, efficiency and sensitivity of this method for accurate and simultaneous detection of various ECs.
Data Availability
Data is available upon request to corresponding author.
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Acknowledgements
Authors would like to thank to Fahrettin Duyum and SUMER Laboratory at Gebze Technical University for their support measuring with LC-MS/MS.
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Open access funding provided by the Scientific and Technological Research Council of Türkiye (TÜBİTAK). This work was supported by generous grants from the Scientific and Technological Research Council of Turkey under the TUBITAK 2247-A Fellowship for Outstanding Researchers (no. 120C147). However, all scientific contributions made in this project are owned and approved solely by the author.
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Lama Ramadan: Conception and design, material preparation, data collection, and analysis, original draft manuscript preparation.
Irem Ozturk-Ufuk: Conception and design, material preparation, investigation, manuscript review and editing.
Ebubekir Yuksel: Conception and design, instrumentation, manuscript review and editing.
Emel Topuz: Conception and design, data analysis, supervision, grant owner, manuscript review and editing.
Ebubekir Yüksel. Emel Topuz provided supervision, contributed to writing, conceptualized the research, and conducted the investigation. Lama Ramadan initiated the original draft preparation and was involved in reviewing and editing. İrem Öztürk, H. Cengiz Yatmaz, Ebubekir Yüksel and Emel Topuz contributed to reviewing and editing. Lama Ramadan authored the first manuscript draft, and subsequent versions were collectively reviewed and commented on by all authors.
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Ramadan, L., Ozturk-Ufuk, I., Yuksel, E. et al. Development of LC–MS/MS Method for the Simultaneous Detection of Emerging Contaminants in Aquatic Matrices. Water Air Soil Pollut 235, 537 (2024). https://doi.org/10.1007/s11270-024-07342-8
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DOI: https://doi.org/10.1007/s11270-024-07342-8