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Article

Validation of a Method Scope Extension for Simple Biomonitoring of 353 Pollutants in Serum Samples

by
Cristian Rial-Berriel
1,*,†,
Álvaro Ramos-Luzardo
1,†,
Andrea Acosta-Dacal
1,
Ana Macías-Montes
1,
Pilar Fernández-Valerón
1,
Luis Alberto Henríquez-Hernández
1,2,
Manuel Zumbado
1,2,
Luis D. Boada
1,2 and
Octavio P. Luzardo
1,2
1
Toxicology Unit, Research Institute of Biomedical and Health Sciences (IUIBS), Universidad de Las Palmas de Gran Canaria, Paseo Blas Cabrera s/n, 35016 Las Palmas de Gran Canaria, Spain
2
Spanish Biomedical Research Center in Physiopathology of Obesity and Nutrition (CIBERObN), Instituto de Salud Carlos III, 28029 Madrid, Spain
*
Author to whom correspondence should be addressed.
†
These authors contributed equally to this work.
Toxics 2023, 11(6), 498; https://doi.org/10.3390/toxics11060498
Submission received: 19 April 2023 / Revised: 17 May 2023 / Accepted: 29 May 2023 / Published: 31 May 2023
(This article belongs to the Section Human Toxicology and Epidemiology)
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Versions Notes

Abstract

:
Animals and humans are exposed to various residues that can have a detrimental impact on health, including carcinogenic potential, endocrine disruption, or fatal toxicity. The toxic burden can be evaluated in several biological samples, with serum being one of the preferred and most convenient options. In this study, we have applied and validated a method for detecting several hundred toxins in serum samples. This technique involved a single-step QuEChERS (quick, easy, cheap, effective, rugged, and safe) extraction followed by analysis using gas and liquid chromatography coupled with mass spectrometry. With this methodology, we could detect and quantify up to 353 compounds, including persistent organic pollutants (POPs), pesticides, pharmaceuticals, and rodenticides, using just 250 µL of serum. Among them, 92% could be measured at concentrations below 1.25 ng/mL, making it ideal for biomonitoring. We applied this method to samples collected from camels (n = 40) and humans (n = 25). We detected naproxen, ketoprofen, paracetamol, levamisole, and some POPs in these samples. This study validated the ability to simultaneously detect a broad range of compounds in small volumes of serum.

1. Introduction

Environmental pollution is poised to be one of the most significant challenges of the upcoming years, and its sources vary depending on the compounds involved. There exist thousands of toxic chemicals, including pesticides widely used in agriculture and farming, medicines such as nonsteroidal anti-inflammatory drugs (NSAIDs), antibiotics, and persistent organic pollutants (POPs). Some examples of POPs include polychlorinated biphenyls (PCBs), polybrominated diphenyl ethers (PBDEs), polycyclic aromatic hydrocarbons (PAHs), organochlorine pesticides (OCPs), and new flame retardants (NFRs), among others [1,2]. The compounds referred to as PAHs are created as byproducts of industrial processes, while PCBs and PBDEs are intentionally manufactured for use in industrial applications, specifically as thermal and electrical insulation. On the other hand, OCPs, such as DDT, are utilized as powerful pesticides due to their toxicity. These substances share the common characteristics of being highly persistent in the environment and having the ability to accumulate in living organisms, which can result in developmental or neurological issues, disruption of the endocrine system, and the development of cancer [2,3,4]. Due to their persistence, these compounds are still commonly detected in both living organisms and the environment, despite many of them having been banned several decades ago [5].
On the other hand, the overuse of semipersistent pesticides, including carbamates, pyrethroids, neonicotinoids, and organophosphates, particularly in agriculture to meet the demands for high food and feed production, can result in exposure to these chemicals, primarily through food consumption. These pesticides are known to be endocrine disruptors, carcinogens and pose significant environmental hazards to beneficial insects [6,7,8,9,10]. Similarly, in both human and veterinary medicine, the excessive use of medications, such as antibiotics and NSAIDs, can result in the presence of their residues in food, either directly or indirectly through water contamination, such as sewage sludge or seawater. [11,12]. Apart from their potential toxicity to living organisms (for example, acetaminophen is hepatotoxic, salicylic acid can cause haematological disorders, and some antibacterial and antifungal compounds are nephrotoxic), the use of antibiotics can also contribute to the emergence and spread of bacterial resistance, which is considered one of the most significant threats to human health [13,14,15].
Due to the significant environmental impact of these chemicals, biomonitoring is a critical tool to assess the toxic burden on the body [16,17,18]. For biomonitoring studies, the preferred sample types include whole blood, umbilical cord blood, urine, or breast milk [1,19,20,21]. However, serum is the preferred choice because is easily obtained and can be used to study the entire population, regardless of age or gender, unlike breast milk [1,22]. Compared to whole blood, serum offers several advantages in biomonitoring studies. It is a simpler and more homogeneous matrix, containing no fibrin or erythrocytes, fewer proteins (which may interfere with ionization in the detection of these substances [23,24]), and higher levels of sodium and potassium [16,19].
Therefore, it is essential to have access to straightforward, accurate, and reliable multicompound analytical methods that comply with the standards established by international analytical agencies [25,26] and work with small sample volumes [12]. To achieve this, the extraction of analytes from the matrix and subsequent detection and quantification are required. The most-used extraction methods for serum analysis are solid-phase extraction (SPE), liquid–liquid extraction (LLE), and, more recently, solid-phase microextraction (SPME) [3,6,21,27]. In recent years, QuEChERS (quick, easy, cheap, effective, rugged, and safe) based extraction methods have been developed and validated, as they allow for customization and optimization for specific purposes [9,16,17,18,28]. This type of extraction can handle the processing of large numbers of samples using a simple methodology, unlike SPE or LLE, which commonly require a larger volume of solvents that may be more harmful to the environment [10,21] or involve additional steps such as pH adjustment [1,11,13,14], making them more time-consuming and expensive [6,16,27,29].
Different types of detectors and chromatography are employed depending on the intended use. Most of the recently optimized methods utilize liquid chromatography (LC) and gas chromatography (GC) coupled to a mass spectrometer (MS/MS), high-resolution mass spectrometry (HRMS/QTOF), or flame ionization detector (FID) [3,13,19,28,30]. These detection and quantification methods are recommended and the most frequently used to cover a broad range of analyte groups with varying physicochemical characteristics in targeted analyses [21,25,28].
The objective of this study was to expand and validate a versatile QuEChERS and LC- and GC-MS/MS method that had previously been optimized for whole blood. This method was used for analysing a variety of substances, including persistent organic pollutants (POPs), semipersistent pesticides like rodenticides, carbamates, pyrethroids, and neonicotinoids, as well as antibiotics, antifungal agents, and nonsteroidal anti-inflammatory drugs (NSAIDs) used for human and animal medicines. Finally, we applied this method to two sets of camel and human serum samples to verify its usefulness in real-world scenarios.

2. Materials and Methods

2.1. Chemicals and Solutions

The solvents involved were MS/MS grade acetonitrile (ACN), formic acid (FA), and methanol (MeOH), provided by Honeywell (Morristown, NJ, USA). Water (18.2 MΩ/cm) was purified daily in the laboratory using a Millipore MiliQ A10 Gradient system (Molsheim, France). Foetal bovine serum (FBS) provided by ThermoFisher (Waltham, MA, USA) was used as a blank matrix (tested before the start of validation experiments), till real serum could be quite heterogeneous, with detectable quantities of our analytes of interest.
Premixed QuEChERS salts for the AOAC (Association of Official Agricultural Chemists) method (1.5 g of sodium acetate and 6 g of magnesium sulphate) were purchased from Agilent Technologies (Palo Alto, CA, USA). Ammonium acetate (MS/MS grade, for LC mobile phases) was purchased from Fisher Scientific (Loughborough, UK).
MS/MS grade standards (93 to 99% purity) for all the analytes and deuterated compounds included were obtained from European Pharmacopoeia Reference Standards (Strasbourg, France), CPA Chem (Stara Zagora, Bulgaria), A2S—Analytical Standard Solutions (Saint Jean D’Illac, France), Dr. Ehrenstorfer (Augsburg, Germany), and Sigma-Aldrich (Augsburg, Germany), according to availability, purity, and presentation (solid/liquid, preferably solid for its greater stability).
Three independent working solutions (one for pesticides (diluted in ACN), another for pharmaceuticals (in ACN), and one for POPs (in acetone)) at 1 ug/mL each were prepared for the validation experiments. A procedural internal standard (P-IS) mix composed of 11 deuterated compounds (acenaphthene-d10, atrazine-d5, carbendazim-d3, chlorpyrifos-d10, chrysene-d12, cyromazine-d4, diazinon-d10, linuron-d3, PCB 200, pirimicarb-d6, and phenanthrene-d10) were prepared at 1 µg/mL and added to all samples before extraction to check for whole-method errors. These working solutions were kept at −20 °C for not more than 1 year and checked before each use.

2.2. Instrumental Analysis

As we published previously, two consecutive analyses in LC- and GC-MS/MS are needed to achieve the scope of the method. Since this method is an extension of an existing procedure [17,31], the chromatographic and mass-spectrometry parameters will be presented in a summarised form [17,31]. MassHunter Quantitative and Qualitative software were used for data acquisition and analysis.

2.2.1. UHPLC-MS/MS

Eight microlitres of the final extract were injected at a flow of 0.4 mL/min in an ultrahigh-performance liquid chromatograph (UHPLC), model 1290 Infinity II, coupled to a triple quadrupole mass spectrometer (MS/MS) model 6460 with positive/negative switching mode, obtained from Agilent Technologies (Palo Alto, CA, USA). Since we used no cleanup step, an online filter and a guard precolumn to retain particles were coupled to the analytical column (InfinityLab Poroshell 120). Mobile phases consisted of (A) 2 mM ammonium acetate, 0.1% FA in MiliQ water and (B) 2 mM acetate in MeOH. Mobile phase B gradient was started at 5% (up to 0.5 min), followed by 20% at 1 min, 40% at 2.5 min, 85% at 8 min and 100% from 10 min to 14 min. The total running time was 18 min. Nitrogen (99.9999%) was used as the collision gas. The temperatures, flows, and pressures of chromatographic and mass spectrometer were the same as the original method [17,31]. Optimized retention time (RT) and transitions are shown in Table 1.

2.2.2. GC-MS/MS

The analysis of most nonpolar compounds involved the use of an Agilent Gas Chromatograph 7890B connected to a Triple Quad 7010 mass spectrometer equipped with Electron Impact ionization, manufactured by Agilent Technologies in Palo Alto, CA. To facilitate the analysis, two columns with a length of 15 m each, a diameter of 0.25 mm, and a film thickness of 0.25 µm, J&W HP-5MS from Agilent Technologies, were joined by an ultimate purged union, which enabled the application of back flush after each analysis. The oven temperature was increased according to a specific ramp protocol, starting at 80 °C for 1.8 min and then increasing at a rate of 40 °C per minute until reaching 170 °C. The temperature was then raised by 10 °C per minute until it reached 310 °C, where it was maintained for 3 min, resulting in a total run time of 21.05 min. The carrier gas used was helium (99.999%) which was kept at a constant flow rate of 1 mL/min, while nitrogen (99.9999%) was used as a collision gas (supplied by Linde, Dublin, Ireland). An aliquot of 1.5 µL was injected through an ultrainert glass–wool inlet liner, in spitless mode. Details of the inlet, backflush, and source parameters have been previously published [17,31]. Transitions and retention time are shown in Table 1.

2.3. Sample Preparation and Extraction Procedure

The extraction method is a modification of the original technique proposed by Anastassiades et al. in 2003 [32]. Since its invention, numerous modifications have been made to adapt it to new matrices [33]. The present study is a scope extension of a method previously presented by our group on whole-blood matrix [17,31]. In brief, a 2 mL tube was used to add P-IS mix to 250 µL of homogenized serum, which was then vortexed for 30 s. These samples were then fortified to be used for the calibration curve, quality control (QC) samples, and validation experiments. Afterward, the samples were left on an orbital shaker for 1 h to ensure proper mixing and equilibration between the matrix components and analytes. Next, 500 µL of acidified acetonitrile (ACN) containing 1% formic acid (FA) was added. This step results in the precipitation of proteins, which enables higher extraction efficiency for the compounds at acidic pH [11]. Subsequently, the samples were thoroughly mixed and subjected to ultrasonic treatment for 20 min to promote contact between the analytes and the solvent and to facilitate the separation of analytes from the matrix. The samples were then microcentrifuged for 10 min at −2 °C and 4200 RPM (RCF = 1992× g, radius 101 mm) to facilitate lipid coagulation and sedimentation. The resulting supernatant was filtered through a 0.2 um pore filter manufactured by Macherey-Nagel in Düren, Germany and collected in a vial with an insert suitable for injection into LC and GC systems. It is important to note that all samples and QC samples were subjected to the same extraction method.

2.4. Validation Experiments/Procedures

Validation assays were performed in accordance with two analytical guides: the Scientist Working Group for Forensic Toxicology (SWGTOX) [26] and the European guide for pesticide analysis in food and feed (SANTE) [25]. The validation parameters included identity (qualifier ratio, retention time, signal-to-noise ratio, and peak shape), selectivity (determination of interferences in blank matrix samples at each analyte retention time), linearity (determination of working range), accuracy (bias and precision), carryover, limit of quantification (LOQ), uncertainty (based on intralaboratory validation/data), and matrix effect (ME). For linearity, a 12-point matrix-matched calibration curve was prepared for each experiment, covering a range of 0.1 to 40 ng/mL. Precision and accuracy were assessed in quintuplicate using relative standard deviation (RSD) and bias, respectively. LOQ was determined as the lowest concentration meeting the criteria for identity, accuracy, and precision. Carryover was evaluated by injecting a blank sample after a sample fortified at 50 ng/mL. Uncertainty was calculated following the 1st approach of SANTE 2021, based on bias and precision, from intralaboratory QC data [25] with an expanded coverage factor k = 2. Finally, ME was assessed by comparing responses between an extract of blank matrix (fortified at least three levels in triplicate) and spiked acetonitrile.

2.5. Applicability of the Method

Two sets of serum samples were selected to assess the method’s applicability for detecting 353 analytes: one from human patients (n = 25) at the Complejo Hospitalario Materno-Insular in Las Palmas de Gran Canaria, Spain, and the other from camels (n = 40) in a tourist excursion herd in the dunes of Maspalomas in the south of Gran Canaria. Human serum samples were collected after obtaining informed consent from the patients and approved by Drug Research Ethics Committee (CEIm code: 2022-266-1). Serum samples were obtained by centrifuging whole blood without anticoagulants. Camel serum samples were obtained by venipuncture and were received in the laboratory ready for processing, having been refrigerated.

3. Results and Discussion

3.1. Optimization of Extraction, Separation and Detection

Numerous methods exist for detecting and measuring various substances but they typically target specific analytes within a particular group, such as POPs [16,34], pesticides [9,19], or pharmaceuticals [30]. These methods involve SPE, LLE, or derivatization processes, which can make analysis time-consuming and complex. To our knowledge, this study is the first that involves one-step extraction and quantitative detection of a large number of compounds with diverse physicochemical properties, based on QuEChERs extraction for serum samples.
In this study, we validated a pre-existing method that was initially designed for whole blood, for use in serum [17,31]. Even slight differences between these two matrices can significantly impact the extraction and quantification of certain compounds due to potential interferences with proteins, fats, and other molecules that may affect the detection process. Therefore, a thorough validation process was necessary for this modified method. The method allows for the quantitative detection of 353 compounds in serum, including 56 POPs, 10 anticoagulant rodenticides, 233 pesticides, and 54 pharmaceuticals, without any changes to the mobile phase, oven ramp, or other chromatographic parameters. Only the retention times, qualifier ratios, and qualifier/quantifier transitions were adjusted for technical reasons. Table 1 provides a complete list of compounds and summarizes the chromatographic and spectrometer parameters used in the study.
As mentioned in Section 2.3, we opted not to perform a cleanup step (such as PSA, C18, EMR-lipid) to prevent any loss of analytes [19,25]. Furthermore, this method saves both material and time while still ensuring the effectiveness and durability of the equipment. It allows for the analysis of 353 compounds while complying with the criteria parameters established in international analytical guides such as SANTE and SWGTOX [25,26]. The validation parameters studied include selectivity, linearity, accuracy, precision, LOQ, uncertainty, carryover, and matrix effect.

3.2. Validation Experiments

For this analytical validation work, of the 353 compounds covered in this work, 129 were analyzed by GC and 224 by LC, from a single QuEChERS extraction. Compared to the previously validated whole-blood method, which was able to detect 360 substances, six analytes were found to meet validation criteria in serum but not in whole blood (four pesticides: dichlorvos, metalaxyl, methiocarb-sulfone, pirimicarb-desmethyl, and two pharmaceuticals: moxidectin and sulfapiridine). Conversely, thirteen compounds met the same validation criteria in whole blood but not in serum (five pesticides: carbosulfan, methomyl oxime, nitenpyram, paraoxon methyl, and parathion ethyl, and eight pharmaceuticals: cloxacillin, dicloxacillin, marbofloxacin, nafcillin, penicillin g, piperacillin, sarafloxacin, and sulfapyridine). All 56 COPs and 10 anticoagulant rodenticides were validated with similar LOQs. To verify the selectivity of the method, a blank matrix was analyzed and no interferences were detected at concentrations near the LOQ (Figure 1).
Table 1 presents the regression coefficients (R2) achieved during the linearity assessment for each analyte within the working range (minimum of five levels, ranging from LOQ to 40 ng/mL). Due to the broad-spectrum and multiresidue nature of the method, which targets several hundred substances from diverse groups, not all compounds attained ideal regression coefficients of 0.999. The lowest coefficient value was obtained for endosulfan sulfate (0.9251). For formetanate, enrofloxacin, diphacinone, p,p′-DDT, benfuracarb, chlorophacinone, phenylbutazone, and danofloxacin, the R2 was below 0.95. However, for the remaining compounds (92% of the total list), the R2 was >0.97, comparable to the linearity outcomes of whole blood, where 95% of compounds showed R2 > 0.95.
To test the recovery and precision, at least five levels were examined in quintuplicate measurements for all 353 compounds included in the method, comparing the spiked and extracted FBS response with the spiked blank extracts. Both inter- and intraday precision were calculated as % RSD. According to the guidelines, satisfactory recovery ranges from 70–120% with RSD < 20% [25]. The recoveries ranged from 70.85 to 126.43, with RSD ranging from 0.28 to 24.98% (Appendix A). Despite not strictly meeting the criteria mentioned above, certain important compounds for poison diagnostic studies and biomonitoring were included, such as flusilazole (recovery 126%, intraday precision 13.07%) and sulfamonomethoxine (120%, 11.58%, respectively). When RSDs are low, accuracy (60–140%) exceptions are permitted [25]. Following SANTE’s recommendation, expanded uncertainties were calculated using the first approach in Appendix C of the SANTE guide [25]. All MUs were below 60.01% (individual MUs for each compound were shown in Appendix A.
To determine the LOQs for each chemical, recoveries and precision were calculated in quintuplicate at low concentrations of the curve. The lowest concentration that could be quantified with acceptable accuracy and precision was considered the LOQ for each compound. All compounds had LOQs below 5 ng/mL, and up to 92.35% of the substances included in the method could be quantified at concentrations below 1.25 ng/mL, as shown in Table 1. This is comparable to the previously published method for whole blood, where up to 95% of the compounds were detected below 1.5 ng/mL [17,31], as well as to other multiresidue studies for pesticides [19] and POPs [27] in serum.
The presence of a high concentration of analyte in a sample that remains on the column and interferes with the quantification of subsequent injections is known as carryover. To test for carryover, FBS fortified to 50 ng/mL was injected, followed by a blank. Carryover was considered present if quantification exceeded 10% of the LOQ. No carryover effect was observed for any of the 353 compounds.
Serum or blood are biological matrices that are known to be complex and contain various components such as lipids, proteins, pigments, and cellular debris, which can vary between seemingly similar matrices [35]. Serum is considered a more homogeneous sample with a lower matrix burden compared to other biological matrices such as blood, which contain various components such as lipids, proteins, pigments, and cellular debris that can differ even in similar matrices [9]. Matrix components can interfere with compound ionization and significantly affect quantification, necessitating evaluation of ME. This was done by testing three identified concentrations (2, 10, and 20 ng/mL, each triplicate) in spiked serum extracts, quantified using a calibration curve made with ACN. ME was observed in both liquid and gas chromatography techniques (Table 1), ranging from 14.81 to 543.45%. Among the 353 compounds, 206 (58.35%) had acceptable ME within 80–120% range according to the SANTE analytical guide [25]. On the other hand, it was observed that 90 out of 353 compounds (25.5%) showed signal enhancement, while 57 (16.15%) exhibited signal suppression due to matrix components (as shown in Figure 2). Furthermore, in the present study, a greater number of compounds underwent matrix effects in LC compared to GC (61% versus 53.6%, respectively), which is in line with previous findings [16,17,25]. In conclusion, a matrix-matched calibration was selected as the preferred method of calibration, which was recommended by the SANTE analytical guide [25,26]. This choice was supported by the ME results, which showed that over 41% of the compounds had medium or strong ME.
Given its ability to monitor hundreds of compounds, including POPs, nonbanned pesticides such as anticoagulant rodenticides and commonly used pharmaceuticals, the present method appears to be a valuable option for biomonitoring purposes. Furthermore, it can be applied to cases involving pesticide and pharmaceutical poisoning or overdose.

3.3. Application to Real Samples

The method developed was utilized to analyze two sets of actual serum samples: one from humans (n = 25) and the other from camels (n = 40) to validate its suitability for the intended purpose. Appendix B provides a summary of the identified/quantified compounds. No nonbanned pesticides were found in either series. This result was expected, given the existing legislation that establishes maximum residue levels (MRLs) for food and feed, which implies that exposure to anticoagulant rodenticides and pesticides was not anticipated. Likewise, although rodenticides are prevalent in food chains, anticoagulant rodenticides were absent in both humans and camels. However, while camels were free of the analysed toxics, measurable concentrations of pharmaceuticals and some POPs were found in human serum samples. The camels were young, had not received any pharmacological treatments, were herbivorous, and were fed commercial feed, which was subject to stringent controls.
In contrast, human serums showed detection of six POPs above LOQs, including PCB congeners 138, 153, 180, p,p′-DDE, hexachlorobenzene (HCB), hexachlorocyclohexane beta (β-HCH), and naphthalene (Appendix B). These findings were consistent with earlier research in the Canary Islands where the most commonly identified compounds were p,p′-DDE, HCB, β-HCH, naphthalene, and PCB congeners 138, 153, and 180 [2,34].
In the end, four pharmaceuticals (acetaminophen, ketoprofen, naproxen, and levamisole) were detected in nine (36%), three (12%), three (12%), and two (8%) human samples, respectively. Among them, naproxen, ketoprofen, and acetaminophen are commonly used NSAIDs for humans, with maximum concentrations of 4058.04, 539.64, and 30.93 ng/mL, respectively, which suggests recent pharmaceutical use. Interestingly, levamisole was unexpectedly present in two human samples. Levamisole is an antiparasitic used in veterinary medicine that is frequently used as a cocaine adulterant, implying that exposure to this pharmaceutical could be related to cocaine inhalation, posing a potential health risk, not only due to cocaine but also because levamisole can cause agranulocytosis in humans [36].

4. Conclusions

The described approach is an expansion of an analytical technique used to identify 353 compounds (encompassing 56 POPs, 233 pesticides, 10 rodenticides, and 54 pharmaceuticals) in 250 µL of serum. The technique utilizes QuEChERS extraction, quantification with LC and GC-MS/MS, and conforms to international analytical standards. The proposed method enables the determination of 95% of compounds at levels below 1.25 ng/mL, with reliable reproducibility and recoveries, making it suitable for the analysis of trace residues. Its applicability to authentic samples confirms its usefulness for biomonitoring studies and diagnostic applications in cases of poisoning.

Author Contributions

Conceptualization, Á.R.-L., C.R.-B. and O.P.L.; methodology, A.A.-D., C.R.-B. and A.M.-M.; software, L.A.H.-H., Á.R.-L. and C.R.-B.; validation, A.A.-D., A.M.-M. and C.R.-B.; formal analysis, C.R.-B. and M.Z.; investigation, A.A.-D., C.R.-B., M.Z. and P.F.-V.; resources, O.P.L. and M.Z.; data curation, L.A.H.-H.; writing—original draft preparation, C.R.-B.; writing—review and editing, O.P.L. and L.A.H.-H.; visualization, O.P.L.; supervision, O.P.L. and M.Z.; project administration, O.P.L.; funding acquisition, O.P.L. and L.D.B. All authors have read and agreed to the published version of the manuscript.

Funding

This research was partially supported by the Catalina Ruiz research staff training aid program of the Regional Ministry of Economy, Knowledge, and Employment of the Canary Islands Government and the European Social Fund granted to the University of Las Palmas de Gran Canaria via a postdoctoral grant to the authors Cristian Rial-Berriel (APCR2022010002) and Andrea Acosta-Dacal (APCR2022010003), and by a predoctoral grant to Álvaro Ramos-Luzardo from the University of Las Palmas de Gran Canaria (ULPGC-2021-2022).

Institutional Review Board Statement

The study was conducted in accordance with the Declaration of Helsinki and approved by the Drug Research Ethics Committee (CEIm code: 2022-266-1).

Informed Consent Statement

Not applicable.

Data Availability Statement

The data presented in this study are available on request from the corresponding author.

Conflicts of Interest

The authors declare no conflict of interest.

Appendix A. Summary of Method Validation Results (Measured Uncertainty (MU), Recoveries and Inter- and Intraday Precisions (n = 5))

No.CompoundMU0.3 ng/mL1.25 ng/mL5 ng/mL20 ng/mL40 ng/mL
Precision (RSD %) Precision (RSD %) Precision (RSD %) Precision (RSD %) Precision (RSD %)
Rec. (%)IntradayInterdayRec. (%)IntradayInterdayRec. (%)IntradayInterdayRec. (%)IntradayInterdayRec. (%)IntradayInterday
12-Phenylphenol22.71 111.2011.9211.2993.2617.7820.06100.2417.6518.5498.447.688.21
24,4′-Dichlorobenzophenone (metabolite of dicofol)24.8693.7217.1819.30113.4815.0914.0089.5613.2315.5599.4014.6915.56103.478.378.51
3Abamectine31.79 97.9413.7114.7498.5111.0411.80101.4310.9811.40
4Acenaphthene25.0194.4115.2617.0297.824.084.4094.6911.0612.2996.6118.2319.86101.848.608.89
5Acenaphtylene33.02 114.9721.8219.98100.1114.3915.1398.1518.6520.0198.3511.2212.00
6Acephate16.55 97.419.8510.6598.763.854.10101.745.625.82
7Acetaminophen (Paracetemol)16.63 118.4015.1313.4587.5811.0413.2799.237.337.77102.055.615.78
8Acetamiprid7.32107.5810.199.9798.112.903.1194.216.357.09102.364.514.6499.412.482.63
9Acrinathrin25.44 87.1812.9015.5796.8113.0114.15100.458.458.8698.888.679.23
10Albendazole10.4293.437.738.70104.123.763.81102.984.434.52103.285.395.5096.072.302.52
11Aldicarb9.0699.938.508.9598.971.741.8598.056.316.77102.214.945.0998.222.843.05
12Aldicarb-sulfone8.85 105.033.633.6490.043.363.9298.996.727.14102.242.662.74
13Aldicarb-sulfoxide6.33 116.106.355.7590.445.736.6699.843.553.75101.222.022.10
14Aldrin31.42106.1818.1618.01106.6916.8616.6488.9815.5318.3795.668.759.63102.9010.7911.04
15Anthracene18.57 100.9810.6811.1496.3311.8112.9192.189.8411.24103.895.926.00
16Atrazine10.3196.113.583.92105.402.882.88101.076.817.10102.474.204.3297.192.933.17
17Azinphos-methyl8.39101.158.538.88103.856.776.8699.0710.1010.73102.814.284.3897.242.152.32
18Azoxystrobin10.5098.046.276.73104.372.983.0197.566.326.8299.065.255.58100.423.613.79
19BDE-2836.70104.3114.9815.12101.587.567.8390.0516.1818.9193.6713.5215.19105.1712.4512.46
20BDE-4732.4699.4711.2311.88111.522.642.4996.1615.9817.4997.6514.9516.12100.1811.1911.75
21BDE-8558.3594.4519.1221.30104.2117.6717.8592.6010.4511.8894.0810.6211.89100.7020.1621.08
22BDE-9942.81104.6620.5720.68103.8313.8814.0890.6712.9114.9990.8310.2311.86105.4114.6614.63
23BDE-10052.3096.8512.3813.46107.8819.1418.6796.3017.8219.4897.1410.9811.9099.8518.0018.97
24BDE-15336.24102.1218.2918.85104.0916.3716.5695.4918.0919.9499.6514.5915.41101.8012.5312.96
25BDE-15443.7097.7113.2714.29105.0320.1920.2493.8610.0811.3195.119.4010.41101.4015.1315.70
26BDE-18359.57108.6011.5411.18101.1023.5124.4889.534.875.73100.6115.1015.80101.5620.6521.40
27Benalaxyl11.73101.5214.4815.01101.594.494.6595.514.745.22100.234.634.8699.994.044.25
28Bendiocarb8.45105.797.777.7395.964.865.3397.215.105.52102.515.035.1698.612.732.91
29Bendiocarb metabolite (2, 2-dimethylbenzo-1, 3-dioxol-4-ol)54.51 96.6112.0513.1392.355.165.89102.3718.9319.47
30Benfuracarb52.63 97.7712.4813.43112.3114.7813.85105.3120.9020.8995.6117.4419.20
31Benzo[a]anthracene23.00100.9513.3413.91104.587.807.8586.8612.3114.92104.4613.9414.0497.667.668.26
32Benzo[a]pyrene18.9797.8614.3715.46105.419.739.7190.2817.8820.8596.058.269.06101.856.476.68
33Benzo[b]fluoranthene37.06107.8912.4612.16100.8114.2714.9091.949.5710.9591.7611.4613.15105.8812.4612.39
34Benzo[ghi]perylene39.8996.4610.5811.55103.878.899.0198.5813.3114.2197.6810.1910.98100.5013.7714.42
35Benzo[k]fluoranthene31.4099.9021.3622.51107.597.487.3285.4121.8123.8893.198.189.24104.3810.6210.71
36Bifenthrin25.99107.068.548.40109.666.376.1190.4011.8813.84103.209.749.9498.168.779.41
37Bitertanol8.81101.7222.4523.23106.2312.3912.2890.033.624.2399.495.665.99101.652.842.94
38Boscalid (formerly nicobifen)47.03100.6319.3620.25104.118.228.3189.0712.4814.7495.1216.2017.93103.6116.3016.56
39Brodifacoum28.3084.1911.7614.71103.8013.5913.7894.4411.4512.76103.3610.9511.1598.979.6710.28
40Bromadiolone25.0290.1118.9122.0995.4211.3812.5694.544.725.25102.5212.5412.8799.438.589.09
41Bromopropylate39.80103.9810.9611.09110.519.168.7386.7015.4318.73104.7615.0615.1399.6613.6814.45
42Bromuconazole (two isomers)30.91106.5515.2315.17108.8110.7010.2087.9714.4517.3296.3814.5115.79103.1410.5810.82
43Bupirimate10.8585.4618.3622.62104.464.394.42105.8510.8810.82102.496.136.3096.402.742.99
44Buprofezin18.1095.663.403.74107.597.257.1096.265.465.9799.525.866.20100.456.246.54
45Cadusafos (ebufos)20.5787.818.3610.02117.526.956.23108.464.484.35104.396.466.5193.165.095.75
46Carbaryl11.5597.617.538.1297.442.602.8199.407.227.65101.885.765.9597.763.623.90
47Carbendazim (azole)10.14101.4821.8422.65102.712.202.2697.105.656.12103.152.872.9397.853.133.37
48Carbofuran9.9493.674.444.98102.643.523.61100.795.856.11102.983.433.5196.872.612.84
49Carbofuran-3-hydroxy10.85 104.106.646.7290.767.168.31100.991.161.21100.993.693.85
50Cefuroxima axetil (two isomers)10.45107.6310.029.8097.713.854.1492.715.916.71102.925.685.8199.413.573.78
51Chloramphenicol15.42 88.1614.2316.9998.5214.6815.68101.475.255.45
52Chlorantraniliprole9.55108.9615.7815.2599.656.496.8695.006.387.06101.513.723.8599.523.263.45
53Chlorfenapyr11.15 96.0511.0112.06104.1912.0112.1495.6614.4715.92101.293.763.91
54Chlorfenvinphos15.1393.0816.1818.30107.342.552.50103.434.194.26103.446.186.2995.444.054.47
55Chlorobenzilate21.0597.8714.1215.19108.687.887.6398.2916.8818.0795.4012.2913.56101.327.247.52
56Chlorophacinone55.65 94.2520.3324.10105.3913.8313.81100.3619.2020.14
57Chlorpropham39.9492.7311.9613.57110.619.519.0596.0913.8015.1298.4514.9716.00100.4613.7814.44
58Chlorpyrifos39.8392.5715.3817.49105.528.878.8592.2616.5618.8996.3210.1611.10103.0913.7714.06
59Chlorpyrifos methyl9.9392.6415.6117.73107.158.338.1894.0615.6217.4896.3716.9718.54103.832.222.25
60Chlorthal dimethyl41.2088.5010.5612.56106.0510.6510.5893.1912.0113.57103.4212.8313.0697.5413.9015.00
61Chrysene12.16 108.262.412.3494.174.885.4699.745.926.25100.654.184.37
62Clindamycin12.5472.0414.1320.64112.6314.5013.56108.567.377.14102.465.055.1995.272.773.06
63Clofentezine7.68 99.1424.9824.5294.919.2610.27101.495.135.3299.882.642.78
64Clothianidin10.99 98.2811.1011.8997.349.8010.60100.775.375.6199.703.773.98
65Cortiscosterone 21 acetate22.42 94.8318.7320.79105.1722.7722.79109.5113.7313.2095.937.047.72
66Coumachlor21.24 107.3111.4911.27107.087.046.92103.116.146.2795.476.467.12
67Coumaphos12.93 95.9419.8621.7993.3915.0616.97101.106.937.2199.474.424.68
68Coumatetralyl10.65 100.622.322.43102.0411.5311.89102.086.666.8797.233.083.34
69Cyazofamid13.8193.4712.3513.9199.455.135.43103.026.376.51101.385.495.7097.054.234.59
70Cyflufenamid37.37 96.6010.5811.5392.9511.2212.71103.7912.8513.03
71Cyfluthrin (sum of four isomers)24.66 98.7412.5513.37101.216.887.16100.318.508.92
72Cyhalothrin (lambda isomer)10.29 107.255.735.6295.426.797.49101.834.314.4699.673.533.73
73Cymoxanil36.58 105.214.954.9594.598.189.1198.8816.0017.03101.3412.6513.14
74Cypermethrin (sum of four isomers)10.29105.207.637.6496.505.245.7195.788.259.07100.636.827.1399.763.543.73
75Cyproconazole (two isomers)15.50 104.498.198.2599.159.5910.18104.9111.7611.8097.825.065.45
76Cyprodinil7.00 92.4612.1813.86100.997.517.8399.582.392.53
77Cyromazine42.82 103.529.9010.0697.4124.4724.44116.0520.0018.14
78Danofloxacin23.8675.9814.9920.77117.2912.7111.4093.7215.0816.94105.4016.0316.0197.737.978.58
79Dazomet13.5495.5619.3821.35103.506.076.1795.2612.1913.4799.2913.1713.96100.394.664.89
80Deltamethrin33.4693.8620.0422.47105.0415.8515.8892.3716.0918.3492.7813.8515.71109.549.919.52
81Demeton-S-methyl47.32 116.1612.8211.6289.9516.4319.2398.0324.6624.4893.5322.9223.79
82Demeton-S-methyl-sulfone (Dioxydemeton)39.00 111.7311.5710.9090.6610.8712.62100.5113.7314.38100.5513.4614.09
83Dexamethasone11.0692.138.539.75105.547.707.68101.606.306.53101.945.305.4797.203.233.50
84Diazinon3.06 92.466.307.1893.383.994.50101.495.215.41100.061.051.11
85Dibenzo[a,h]anthracene16.68 112.6414.3813.4390.0310.0011.6997.977.568.12101.525.695.90
86Dichlorodiphenyldichloroethane (p,p′ DDD)37.6295.5316.4718.15107.327.257.1189.4815.3418.0590.2418.8121.94106.7612.5012.32
87Dichlorodiphenyldichloroethylene (p,p′ DDE)34.11106.0713.7613.6699.578.408.8894.2014.1215.7898.308.739.35101.2311.7912.26
88Dichlorodiphenyltrichloroethane (p,p′ DDT)14.94 108.604.093.9790.6614.4116.73103.9714.1614.3499.705.135.42
89Diclofenac11.14 105.644.064.0593.245.486.1899.124.975.28101.603.703.84
90Dicloran10.23 100.3922.8823.99105.927.347.2998.483.343.57
91Diclorvos38.24 111.2323.6022.3393.4717.1019.2694.6211.4312.72102.1313.2313.64
92Dieldrin11.4398.6414.6415.62102.413.653.7596.376.186.75100.666.977.2999.813.934.14
93Diethathyl ethyl14.8688.247.959.48108.702.582.50105.933.973.95102.904.634.7395.313.874.27
94Diethofencarb20.11102.7217.0817.51101.573.864.0099.438.589.09102.329.129.3897.626.647.16
95Difenacoum12.2580.9611.5515.01102.725.455.59100.398.058.44102.924.945.0597.203.694.00
96Difenoconazole19.48 102.7414.9315.30101.4714.0014.52103.119.159.3496.676.196.74
97Difethialone45.00 101.597.317.5894.7014.7716.42103.0515.6015.93
98Difloxacin19.08 90.3718.3621.39102.4415.1123.80105.0911.2811.3096.335.946.49
99Diflubenzuron25.9996.8818.6520.26107.5414.7114.3997.2417.6222.9096.4110.4211.37103.538.778.92
100Diflufenican10.7596.033.563.91104.441.691.7097.505.986.4599.885.876.18100.003.703.90
101Dimethenamid-P (and its R-isomer)9.82 102.255.365.5195.046.056.70101.974.955.1199.493.363.55
102Dimethoate12.6794.4316.6618.57100.316.336.64101.639.079.40101.577.888.1697.784.044.35
103Dimethomorph (two isomers)37.3789.4812.2314.39111.117.126.7493.8417.3719.4995.2810.4711.57103.9512.8312.99
104Dimethylphenylsulfamide (DMSA, metabolite of dichlofluanid)24.15111.5219.4018.3199.566.106.4589.5313.9516.4094.1412.4413.91104.157.988.06
105Diniconazole-M25.63 98.3321.6823.21105.7511.6811.62102.3611.8812.2196.918.429.15
106Dinocap54.01 106.9818.7518.4590.909.6211.14104.0318.7718.99
107Diphacinone30.2670.8517.5219.03105.7617.4417.3695.7415.7017.2697.1216.7818.18101.0910.4510.88
108Diphenylamine30.91 101.837.157.3996.1310.3411.32101.689.009.3299.3710.6011.23
109N,N-dimethylformamidine (DMF, metabolite of amitraz)26.22 94.686.707.45103.3311.7311.9497.948.829.48
110Dodine11.59 110.754.013.8193.527.938.93100.226.757.09100.393.994.18
111Endosulfan alfa17.85 98.843.864.11100.614.544.75101.957.047.2797.485.826.28
112Endosulfan beta8.72 91.546.437.39100.395.325.57103.116.746.8897.252.302.49
113Endosulfan sulfate44.34102.0312.5912.99106.4716.2416.0691.4614.5116.7098.1911.2112.02102.1315.3715.84
114Endrin28.51105.6211.4711.43104.8714.8914.9490.3512.3514.3997.3310.7211.59103.119.739.94
115Enrofloxacin49.49115.1110.889.9592.2310.1511.5890.6016.6619.36101.2123.8024.76103.6624.2424.62
116EPN30.69 118.434.974.4293.3621.8624.6596.8115.3116.65106.319.949.84
117Epoxiconazole44.58 98.8118.2219.4196.3224.4124.67103.5122.5122.89
118Eprinomectin47.23109.5810.8810.4599.076.166.5486.3712.6215.38103.2717.3317.6798.9216.1617.19
119Eritromicin10.61112.0610.029.4295.455.646.2392.987.308.26101.465.405.6099.723.643.85
120Esfenvalerate47.92 99.0914.5515.4594.548.799.7891.9514.8517.00
121Ethion (diethion)17.38107.846.556.40100.923.323.4794.934.635.13102.776.046.1998.595.866.26
122Ethirimol28.11 97.9914.2115.2694.7016.8818.7798.4112.0812.92101.629.7010.05
123Ethofumesate16.2191.2511.6413.43110.474.314.11106.916.926.81102.245.815.9895.564.565.02
124Ethoprophos10.21 101.692.292.3792.727.468.47102.494.214.3299.823.513.70
125Etofenprox53.62100.2015.9316.73109.555.225.0292.0714.2616.3098.9718.4019.57109.1818.1317.48
126Etoxazole12.5282.1711.5014.74106.774.944.87103.526.526.63102.935.055.1795.933.203.52
127Famoxadone29.1885.4214.4517.81115.746.235.6794.8112.3013.6598.5914.0114.96100.2710.0610.56
128Fenamidone34.5496.209.4310.31106.753.343.2997.385.535.9897.706.436.93104.3411.7711.87
129Fenamiphos16.04 103.9716.6816.8998.6013.2614.16103.766.176.2696.774.975.40
130Fenamiphos sulfone21.5479.8011.1114.66104.8511.9111.95104.6113.5113.59102.757.747.9395.116.437.12
131Fenamiphos sulfoxide13.37103.0414.9715.2997.127.017.6098.0312.1313.02100.276.166.4699.914.604.85
132Fenarimol15.17107.008.528.38102.183.353.4593.406.066.83100.786.326.60100.055.235.50
133Fenazaquin13.05 105.7316.6316.5696.326.587.1999.415.946.2999.694.484.73
134Fenbendazole42.7896.2319.9521.82109.395.345.1489.9010.8212.6695.3517.1218.9093.8913.6415.30
135Fenbuconazole19.6098.0610.3511.12102.233.413.5196.796.166.7098.966.156.54100.656.767.07
136Fenbutatin oxide10.7897.948.118.7299.881.641.73103.727.347.44103.527.087.2095.972.412.64
137Fenhexamid40.0790.088.8210.30114.4414.0512.9294.2711.5012.8493.5013.1214.77103.8513.8114.00
138Fenitrothion40.9195.7612.4013.6495.287.348.1191.705.976.8599.2910.0710.68101.6614.1614.66
139Fenoxycarb12.29 86.8413.7216.6391.5817.1719.73100.489.069.4999.834.234.46
140Fenpropathrin35.65 86.5620.7824.2781.2514.3818.6398.1318.2619.58103.8512.2212.39
141Fenpropidin12.1595.066.497.19106.468.007.91105.998.988.92102.437.547.7595.332.612.88
142Fenpropimorph35.90 103.2813.3313.5890.3413.7516.02103.556.987.0997.5012.0813.04
143Fenpyroximate12.1495.445.245.78101.852.692.78102.167.027.24101.626.066.2897.483.754.05
144Fenthion9.3890.367.358.5698.882.963.1597.476.226.72102.026.887.1097.912.863.08
145Fenthion oxon10.5584.9013.6916.97103.862.512.55104.886.936.95103.806.096.1895.421.751.93
146Fenthion oxon sulfone20.4396.7111.1012.08102.965.145.2588.9015.2418.0599.536.947.34101.397.027.29
147Fenthion oxon sulfoxide9.9085.6611.3013.88105.854.414.39101.775.585.78102.665.415.5496.462.332.55
148Fenthion sulfone10.05 107.976.706.5392.794.164.71100.245.776.06100.923.423.57
149Fenthion sulfoxide7.50 99.964.855.1092.766.527.39101.155.185.3999.992.582.72
150Fenvalerate18.02 106.5110.3410.2294.204.124.60100.527.738.10100.126.216.53
151Fipronil10.85 102.942.322.3796.574.164.54101.766.997.2398.213.493.74
152Fipronil sulfide27.97 100.0611.1411.7296.6112.6713.8198.4212.2913.14100.619.6510.10
153Flocoumafen32.20103.3118.6819.03106.3011.2811.1784.2219.6924.6192.2917.7620.25106.0110.6010.52
154Fluazinam46.45 114.7314.0612.9095.4720.1022.1692.1116.3118.64103.7716.0916.32
155Flubendiamide24.2286.8815.7319.06102.457.197.38105.559.729.70103.5213.1913.4194.987.388.18
156Flucythrinate (two isomers)10.65 100.279.519.9896.644.825.25100.575.455.70100.223.673.85
157Fludioxonil8.71 104.1520.6320.8595.6613.3514.69103.648.368.4997.762.542.74
158Flufenoxuron33.7998.8617.2318.38109.096.896.6388.1811.9314.2596.1414.1215.49100.1711.6312.25
159Flumequine38.2891.3516.9319.51109.0317.0916.5095.0011.8113.0896.709.8310.70107.3912.6112.36
160Flunixin27.62 97.466.487.00107.679.389.17103.829.759.8995.158.679.59
161Fluopyram21.85105.274.004.0096.444.454.86102.225.465.63103.096.897.0497.637.257.82
162Fluoranthene13.72 104.438.698.76100.363.653.83104.454.684.7296.534.004.36
163Fluorene20.70101.4323.1824.05113.3118.0516.7789.6714.1116.5798.3014.6515.69101.257.127.41
164Fluquinconazole29.9595.4220.5522.67100.088.518.9590.3513.5715.8198.3914.1715.16101.8210.3310.68
165Flusilazole32.98 126.4313.0710.8897.8910.7211.5297.2423.6124.55100.3811.3811.93
166Flutolanil60.0092.6612.4014.08101.1814.9415.5495.1319.1821.2293.6215.3017.20101.9120.9321.62
167Flutriafol16.7986.6817.6021.3796.1516.2117.75106.5916.3216.11103.955.996.0795.044.545.03
168Fluvalinate tau11.3292.5212.0213.68106.675.425.3596.335.225.70100.645.535.7899.843.894.11
169Fonofos24.2090.078.019.36108.254.634.5094.2312.7214.2198.247.488.01101.488.348.65
170Formetanate41.20 99.703.013.1893.958.379.3896.0113.0714.33101.9014.2714.74
171Fosthiazate28.6589.3216.6219.59101.726.977.2290.2510.0911.7793.7816.0317.99106.619.048.93
172Heptachlor56.79 98.5614.4315.41104.0421.8722.1399.7719.5320.61
173Hexachlorobencene10.3595.586.306.94101.591.161.2099.576.006.34102.205.315.4797.653.143.38
174Hexachlorocyclohexane (alpha)29.68100.2318.0118.91101.887.487.7386.9713.3316.1397.0615.7317.06104.2510.0110.10
175Hexachlorocyclohexane (beta)37.8087.877.488.96105.3211.0411.0396.6214.4615.76103.1320.1320.55108.9511.9711.57
176Hexachlorocyclohexane (delta)8.4092.1612.4314.19101.839.139.4489.9214.2116.64102.6114.7515.13100.232.893.04
177Hexaclorocyclohexane (gamma, lindane)29.92100.368.088.47103.6110.5210.6996.4621.7823.7699.0820.0221.28102.0310.3110.64
178Hexaconazole (two isomers)31.46 100.1010.0310.5588.5011.4513.6297.9318.9420.36103.5410.7510.93
179Hexaflumuron35.8897.069.5710.38113.2023.4021.7692.1510.1411.5896.8310.3011.20103.1712.3612.61
180Hexythiazox15.43 97.8010.1810.95105.358.078.06104.965.885.8994.593.674.09
181Imazalil (enilconazole)18.4597.7514.0115.09101.045.976.22100.017.818.22101.556.696.9497.446.026.50
182Imidacloprid7.84101.3522.1422.9998.353.043.2592.255.846.66101.606.376.60100.022.702.84
183Indeno [1,2,3-cd] pyrene12.29 97.2311.5512.5092.7210.4211.8398.824.885.20101.764.094.24
184Indoxacarb32.3899.7515.9216.80106.456.906.8295.3014.8116.36102.0415.4215.9199.4911.1111.76
185Iprodione26.46 97.522.642.8595.469.3010.25103.3111.1211.3398.008.919.57
186Iprovalicarb48.25 103.449.9910.1786.3415.0818.38101.3323.3724.2897.7716.3517.60
187Isocarbophos16.5881.009.9812.97111.090.640.61107.487.557.39104.415.945.9893.673.564.00
188Isofenphos methyl26.7390.4017.6020.50113.4213.9712.9692.5116.1418.3795.8511.9513.12102.599.159.39
189Isoprothiolane10.92102.5514.0914.46100.612.072.1799.197.147.58100.345.365.6399.873.763.96
190Ivermectin B1a16.5789.0514.1316.70112.8315.1314.1294.1210.8412.1296.437.658.35102.215.565.73
191Josamycin43.99 101.8920.7021.3999.7611.2911.91101.3011.8912.3599.6915.1215.97
192Ketoprofen15.53114.798.647.9397.824.084.3994.194.565.10101.276.166.40100.545.355.60
193Kresoxim methyl9.41 102.7318.0918.5397.668.809.4997.146.246.76101.483.103.21
194Leptophos18.10 99.4313.5914.39101.0416.0216.69104.545.935.9796.085.506.03
195Levamisole56.89105.3019.1519.1493.778.409.4385.5610.5312.9595.5015.7817.39104.7919.7819.87
196Lincomycin12.57 93.0712.6914.3699.8611.3711.9898.922.422.58100.264.334.55
197Linuron23.14 106.6013.6513.4899.476.166.5297.0913.7414.90101.717.958.23
198Lufenuron38.43 96.2215.9117.4094.3621.1123.5593.6021.3223.11105.1413.0913.10
199Malaoxon9.79 101.177.708.0197.989.5310.24103.114.584.6897.642.923.14
200Malathion11.2282.6213.1116.71100.256.927.26105.8613.5413.47102.327.467.6895.752.462.71
201Mandipropamid12.8993.285.576.29105.420.280.28103.465.545.63102.644.444.5596.423.623.95
202Mebendazole14.17101.0417.6418.38103.153.493.5696.366.427.01100.184.995.2599.954.885.14
203Mefenamic acid13.2690.249.1510.67108.423.343.24101.016.316.57103.486.316.4295.813.463.80
204Mefenoxam (metalaxyl-M)10.25103.3612.8813.12102.133.343.4496.295.546.06101.365.625.8399.723.523.72
205Meloxicam27.03 111.4123.5822.2887.667.849.41101.7610.5810.9599.949.319.80
206Mepanipyrim13.4897.4511.5912.52104.034.064.1096.005.275.78100.554.754.9799.834.644.89
207Mepiquat20.05 104.818.318.3491.468.619.9098.444.484.79100.486.917.24
208Metaflumizone34.41 116.299.648.7288.2213.3315.9095.7310.3611.39103.8011.7811.95
209Metalaxyl9.37 102.277.697.9292.086.457.37100.447.758.12100.703.203.35
210Metaldehyde24.07105.409.779.76102.177.067.2797.794.174.4999.764.734.99100.258.308.71
211Metconazole20.49104.0215.4315.62108.159.709.4491.8410.5012.0398.1911.3512.16101.687.027.27
212Methamidophos (two isomers)2.94 110.8718.6717.7290.486.127.12100.472.552.68100.920.800.83
213Methidathion11.9897.058.539.25103.754.624.6999.936.667.0198.824.464.75100.304.134.33
214Methiocarb15.30 93.857.218.0998.117.618.16101.605.205.38
215Methiocarb-sufone8.5995.914.454.88101.312.622.7394.977.057.81100.515.195.4399.782.953.11
216Methiocarb-sulfoxide13.2388.785.906.99104.866.826.84104.546.176.21101.825.305.4896.863.944.28
217Methomyl7.40 108.315.155.0193.677.238.1298.375.926.33101.472.362.45
218Methoxyfenozide9.06 101.823.153.2591.647.208.27102.143.703.81100.273.123.28
219Metoxychlor10.18 99.593.794.0097.396.356.86102.083.773.8998.233.263.49
220Metrafenone54.30 109.0319.3418.6786.4218.3422.34101.5319.5420.25105.4618.8218.79
221Metronidazole11.2297.1911.1512.07103.484.544.6297.545.866.3399.296.046.40100.333.864.05
222Mevinphos (phosdrin)14.0588.3512.6115.02114.311.581.46104.467.377.42103.895.305.3795.133.473.83
223Mirex11.87 111.149.418.9190.786.537.5797.507.317.89102.243.833.94
224Monocrotophos6.77 111.727.236.8192.909.2310.4699.613.944.16100.462.322.43
225Moxidectin41.0298.7613.8214.73103.0214.7215.0488.7912.8915.2897.7417.1618.4899.4214.0814.91
226Myclobutanil6.85 110.183.933.7692.899.4510.71100.335.385.65100.682.322.43
227N-(2,4-dimethylphenyl)-N’-methylformamidine (DMPF, metabolite of amitraz)42.13 106.1414.9814.8589.189.0810.7299.3614.8715.75101.6114.5915.11
228N,N-Dimethyl-N’-p-tolylsulphamide (DMST, metabolite of tolyfluanid)10.5697.3510.0210.83104.277.427.4998.606.496.9398.666.226.64100.293.643.82
229Naphtalene18.07 104.6924.2824.4284.2212.0215.0291.0421.6024.98105.575.045.02
230Naproxen18.08 104.7611.9912.0597.402.152.32100.446.236.53
231Novobiocin23.78 86.1521.5724.36101.536.136.35101.378.198.51
232Nuarimol21.3795.4214.0715.53114.1020.3718.7996.4118.1119.7797.4610.7411.60101.047.367.67
233Ofurace44.9299.427.147.56104.817.727.7590.1111.5013.43100.4618.0718.94102.9615.5715.92
234Omethoate8.16 104.847.417.4491.496.437.4098.854.194.46102.142.422.49
235Oxadixyl9.41 97.675.385.8095.258.269.12101.815.135.3099.403.213.39
236Oxamyl4.96109.005.355.1799.815.005.2894.775.406.00102.244.174.3099.231.621.72
237Oxfendazole14.43112.009.859.2698.202.863.0693.134.895.53100.757.357.68100.634.975.19
238Oxolinic acid8.60 103.854.004.0591.685.276.06101.154.744.93100.962.903.02
239Oxydemeton methyl22.47 102.565.856.0092.134.645.3099.176.156.52101.587.738.01
240Oxyfluorfen26.60107.1518.8418.51101.7818.1118.7393.7122.5424.3294.6810.1311.27104.328.858.93
241Paclobutrazol29.9490.3118.7321.83109.8519.3518.5590.9614.9117.2597.8911.8012.68102.2510.3110.62
242Parathion methyl19.4898.4118.2319.50104.653.643.6691.0613.2615.3397.1516.5617.94104.955.925.94
243PCB 2830.5990.8012.6714.68106.283.433.4095.7518.6620.5197.3613.8815.01101.5810.5610.95
244PCB 5249.5396.7616.6818.14110.075.965.7091.2715.7018.11100.9319.1219.94105.8617.0616.97
245PCB 7732.20103.3816.6016.90102.2710.8111.1298.2019.6321.0497.8811.5712.44102.2211.1111.44
246PCB 8152.37108.0216.7316.30103.9018.6018.8589.5616.7319.6687.5912.3314.81102.2621.6722.31
247PCB 10142.2787.0419.3923.45109.178.107.8192.0020.8223.8395.807.978.75103.4314.6214.87
248PCB 10527.3799.267.437.87100.3313.5814.2492.7213.1214.8993.1217.2819.53105.208.958.96
249PCB 11424.13103.7120.8721.1994.4612.1813.5791.1016.3618.9196.9917.6919.20102.778.208.40
250PCB 11828.1597.1913.1214.2199.865.105.3792.7620.7823.5896.308.309.07102.299.689.96
251PCB 12331.62101.0813.8514.43100.495.756.0295.0819.7021.8194.7514.6116.24102.6110.8811.16
252PCB 12619.2896.1718.8420.62107.2120.0619.7094.3617.4219.4396.6612.7513.88102.606.486.65
253PCB 13826.5596.298.959.78100.7115.3616.0593.6017.0119.1297.6612.3713.33100.799.169.57
254PCB 15333.5692.096.607.55101.9115.1315.6395.5516.1317.7698.4415.6116.69101.6011.6012.02
255PCB 15655.5289.305.796.82104.1117.8218.0292.5317.9220.38101.9221.3722.0799.3518.9420.07
256PCB 15726.8595.1317.2519.09104.7613.2713.3389.8515.1117.71102.6016.7217.1699.449.219.75
257PCB 16751.81113.9821.8820.2199.5717.1418.1287.5713.3015.9994.3518.4020.5393.2116.5718.72
258PCB 16952.09101.6018.2118.86103.248.558.7285.449.2511.4090.1520.5824.0397.1617.5619.02
259PCB 18013.23104.9614.3714.41106.939.309.1588.6714.2216.8893.6914.5616.36100.904.534.73
260PCB 18925.16103.0310.1510.37100.2819.1920.1489.1612.3014.5293.679.9011.13104.128.368.45
261Penconazole34.1695.7012.8014.08115.854.504.0995.5313.4014.7693.0811.7113.2499.4411.7212.41
262Pencycuron20.4898.169.039.69105.554.454.4396.264.835.28100.537.157.49100.127.067.42
263Pendimethalin17.7090.9114.4716.76105.217.437.4399.023.673.90102.025.045.2097.755.826.27
264Penicilina V26.71 96.645.846.3697.018.579.30101.269.229.58
265Permethrin36.34 105.6914.9414.8895.2721.9024.2090.2919.0622.2297.9112.2913.21
266Phenanthrene17.4598.0212.3113.2299.5512.4413.1693.4813.1014.7593.7412.8214.39103.695.555.63
267Phenylbutazone49.13 91.7415.7318.0593.5719.0121.39105.6516.9416.87
268Phosalone11.29100.317.808.18102.565.325.4794.924.354.8299.267.117.54100.093.894.09
269Phosmet13.71 104.017.487.5798.616.236.65103.074.474.5697.454.324.67
270Phosmet-oxon7.06 97.854.695.0597.358.449.13102.675.145.2798.021.992.13
271Pirimicarb10.3592.137.989.12108.261.331.29103.454.955.04103.133.944.0295.992.202.42
272Pirimicarb-desmethyl8.59102.897.117.27101.863.083.1896.806.767.35101.823.153.2698.622.782.97
273Pirimiphos ethyl49.0692.8219.2021.77118.122.682.3987.2911.0613.3496.7214.1115.36110.8615.9515.15
274Pirimiphos methyl46.5397.8611.3712.23106.891.771.7491.7911.3212.99101.9417.1417.69107.7915.6815.32
275Prochloraz11.7593.0913.0414.74109.389.579.21104.396.987.03103.145.345.4595.402.452.71
276Procymidone47.71 106.777.907.7988.9418.0421.3594.0911.3012.6596.1915.8817.38
277Profenofos19.09100.5011.0411.56101.678.809.11100.126.046.35101.117.818.1398.726.476.90
278Propamocarb5.99 103.074.644.7487.683.954.75100.883.743.90101.511.801.86
279Propargite20.4398.909.9210.56102.075.445.6197.645.696.1498.896.677.10100.757.047.36
280Propiconazole12.75 96.848.809.57100.378.048.43100.505.916.1998.024.134.43
281Propoxur7.88106.7712.2212.05100.745.195.4295.666.747.42102.834.634.7499.262.652.81
282Propyzamide (pronamide)7.0892.6519.3321.9695.896.006.5995.616.947.65100.375.715.9899.852.432.57
283Proquinazid20.1593.8312.2413.73108.786.045.85101.247.908.22102.346.016.1896.686.447.01
284Prothioconazol20.9899.1011.0311.71111.7711.2110.56101.2415.3015.91101.447.097.36100.397.237.58
285Prothiophos54.5299.7620.1721.29115.4519.5217.7990.4316.7919.5492.1510.7812.31106.1618.8518.69
286Pymetrozine12.11 104.529.459.5299.966.476.8198.857.407.88100.894.144.32
287Pyraclostrobin14.4692.856.847.76103.952.372.4097.435.666.11100.226.576.90100.044.985.24
288Pyrazophos13.8397.277.187.77104.118.909.00100.366.586.90100.045.665.9699.704.755.02
289Pyrene35.4884.484.355.42118.2715.2013.5390.7810.3512.0095.738.219.03102.8112.2412.53
290Pyridaben21.9299.3012.1612.89102.103.573.6897.395.956.4399.287.397.83100.307.567.93
291Pyridaphenthion13.23100.159.509.99101.735.425.6196.493.964.32100.264.925.1799.954.554.80
292Pyrimethanil21.2095.6616.0817.69105.1712.0012.0191.2011.1312.8494.1212.4613.94103.966.916.99
293Pyriproxifen17.6496.874.835.25105.332.022.0298.715.796.1897.285.566.0191.300.941.09
294Quinalfos11.6394.4810.5611.7696.906.477.03106.436.566.49101.726.646.8796.673.223.51
295Quinoxyfen17.5890.9011.9313.81100.168.478.90102.027.557.79102.265.095.2496.995.606.07
296Rifampicin38.32 95.118.519.4299.828.148.5899.3113.1413.93
297Rotenone38.71 116.0914.1212.80101.1419.8320.64103.0611.2611.5095.9012.7413.98
298Roxithromycin16.85 105.3912.5512.5490.667.648.8796.263.894.25103.645.335.41
299Simazine5.25106.2213.4813.3595.004.144.5993.846.297.06101.604.454.6199.671.791.89
300Spinosad (two isomers)22.35 105.887.757.70106.7613.2513.05100.516.116.4597.077.367.88
301Spiramycin (two isomers)6.56 95.126.276.9498.304.514.83101.252.102.19
302Spirodiclofen15.03 105.9510.5610.4996.954.554.94100.275.185.44
303Spiromesifen12.81 101.564.835.0099.436.186.5497.605.756.20100.244.414.63
304Spiroxamine11.5384.847.859.74105.101.891.90104.577.117.15102.724.874.9996.162.903.17
305Strychnine11.90 98.616.607.0492.658.239.35101.865.045.21100.734.084.27
306Sulfacetamide18.66 95.3812.8114.13101.547.677.95100.856.436.71
307Sulfachloropiridacine4.66 96.980.490.5392.425.446.1999.533.023.20100.561.561.64
308Sulfadiacine22.38 108.5215.9015.4291.455.346.1597.905.896.33102.457.617.82
309Sulfadimetoxine10.71110.2512.5511.9996.344.795.2496.185.926.47100.386.046.34100.473.683.86
310Sulfadoxine7.31107.497.967.7994.895.766.3994.436.427.16102.255.285.4499.732.512.64
311Sulfameracine6.60 103.872.732.7794.754.374.85100.537.968.33100.382.262.37
312Sulfametacine8.13 105.161.021.0292.798.309.42100.185.585.86100.612.782.90
313Sulfametizole4.48 105.554.454.4494.957.798.64102.755.575.7199.451.491.58
314Sulfametoxazole9.86 105.883.943.9293.128.769.90103.214.474.5698.893.293.50
315Sulfametoxipiridacine10.11 103.073.903.9989.726.587.72101.015.535.76100.773.463.61
316Sulfamonomethoxine30.69 120.1011.5810.1593.439.8511.10100.655.385.63100.7710.6011.07
317Sulfapyridine13.16 107.397.547.3995.057.027.7798.887.307.77101.094.494.68
318Sulfaquinoxaline19.01 108.108.288.0692.036.076.9598.127.237.76102.116.456.65
319Sulfatiazole13.98 107.2518.2317.8991.678.9210.24100.1810.8711.42100.134.825.06
320Sulfisoxazole6.76 95.645.526.0890.145.376.27101.963.793.9199.822.322.45
321Tebuconazole4.02 96.709.6510.5096.718.879.65100.975.135.3599.071.221.30
322Tebufenocide9.6698.709.299.90103.484.985.07100.379.8110.2998.746.146.55100.663.313.46
323Tebufenpyrad54.2598.4019.3120.65103.4214.2614.5187.2216.1819.5396.4316.3017.8093.9717.6119.73
324Teflubenzuron14.59 103.6116.1916.4591.9611.6113.2999.9210.4010.96100.045.035.29
325Tefluthrin18.9894.5018.4220.52109.305.134.9495.8313.3114.6297.1510.2611.12103.006.296.43
326Telodrin (isobenzan)31.1193.2519.3521.84116.6115.6414.1289.6317.2120.2194.4610.0011.14104.8610.4310.47
327Terbufos17.8989.8718.1021.20101.8416.5817.1498.7716.0217.0799.4614.7215.58105.005.245.25
328Terbuthylazine14.4393.294.254.80109.084.954.7896.044.635.0798.955.776.14100.314.975.22
329Tetrachlorvinphos15.0286.6816.4419.97104.085.785.84103.299.759.93100.974.694.8996.474.484.89
330Tetraconazole38.6789.0116.1519.10114.3310.309.4894.9719.8221.9799.6211.3612.01106.3312.9812.85
331Tetradifon21.5892.2517.2619.70108.829.058.7597.2610.0410.8798.9110.3511.0299.237.387.83
332Tetramethrin38.36 110.198.778.3887.0611.1813.5199.8813.1513.8596.1912.6813.88
333Thiabendazole6.96109.348.898.5699.894.644.8992.537.578.61102.953.303.3799.442.362.50
334Thiacloprid7.62100.279.339.7999.722.712.8696.755.676.17102.324.324.4498.862.492.65
335Thiamethoxam8.90 94.309.0110.05101.192.452.5599.733.063.23
336Thiophanate methyl9.8294.937.658.49102.701.972.02100.035.005.27101.785.035.2097.823.003.22
337Tolclofos methyl18.85 96.492.192.3993.057.468.44104.275.915.97
338Tolfenamic acid15.7096.6020.7222.58113.095.705.3193.6911.9313.4095.7717.2018.90101.955.295.46
339Triadimefon15.86 103.6922.5324.9296.3721.6323.6297.257.367.97100.425.475.73
340Triadimenol11.2190.2116.6819.46108.0110.3010.04104.182.942.97102.846.907.0795.942.602.86
341Triazophos (hostathion)11.28 107.1015.0814.8396.406.066.62100.084.214.4399.923.884.09
342Trichlorfon11.0997.098.268.96103.213.753.8297.445.315.7499.085.575.92100.423.824.00
343Trifloxystrobin7.09 94.3614.7816.4996.835.766.2698.874.985.31100.652.412.52
344Triflumizole14.9598.3811.6112.4399.913.854.0597.816.897.4199.875.896.21100.105.155.42
345Triflumuron10.5297.574.935.32100.944.594.7997.957.988.5899.435.305.62100.203.623.81
346Trifluralin18.05 94.4016.8718.8295.906.437.05103.367.858.0097.055.786.27
347Trimethoprim47.12 112.0712.0411.3196.2411.7812.88101.7420.9321.65108.4215.7915.33
348Triticonazole10.27 105.144.254.2695.266.477.1596.567.307.96102.902.963.03
349Tylmicosin10.97 113.7916.1914.9888.656.898.18101.936.096.2999.543.753.97
350Tylosin10.56 107.7211.2310.9896.695.966.4999.515.986.32100.643.623.79
351Vinclozolin18.2387.2612.2114.73113.3611.7310.8998.1218.8820.2596.4412.8814.06102.626.096.25
352Warfarin10.7787.7817.5721.0791.3723.0724.5895.236.457.13102.694.324.4398.143.453.70
353Zoxamide17.1980.2712.7816.76100.657.007.33106.219.249.16103.647.517.6294.404.354.85
Blank cells were set for compounds that have a higher LOQ than the lowest concentrations tested.

Appendix B. Detected Concentrations (Minimum (Min), Maximum (MAX) and Median (Me) Malues, with Frequencies of Detection) of Analytes in Human Series (n = 25)

POPs min–MAX (ng/mL) Me (ng/mL) n (%) Positives
DDE-p,p′0.36–51.43.7523 (92%)
Naphthalene1.17–3.351.6220 (80%)
HCB0.3–4.740.9912 (48%)
HCH-B0.29–4.091.3412 (48%)
PCB-1530.31–1.140.4810 (40%)
PCB-1800.32–0.920.4710 (40%)
PCB-1380.3–0.820.448 (32%)
Pharmaceuticalsmin–MAX (ng/mL)Me (ng/mL)n (%) Positives
Acetaminophen4–539.6416.659 (36%)
Naproxen30.46–4058.04650.333 (12%)
Ketoprofen7.41–30.9316.873 (12%)
Levamisole11.98–16.3714.182 (8%)
POP (persistent organic pollutant); DDE-p,p′ (dichlorodiphenyldichloroethylene); HCB (hexachlorobenzene); HCH-B (beta-hexachlorocyclohexane); and PCB (polychlorinated biphenyl).

References

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Toxics 11 00498 g001 550
Figure 1. GC- and LC-MS/MS chromatograms of blank and fortified (at 40 ng/mL) serum. (A) GC blank; (B) GC fortified; (C) LC blank; and (D) LC fortified. The color lines correspond to the chromatogram of each compound.
Figure 1. GC- and LC-MS/MS chromatograms of blank and fortified (at 40 ng/mL) serum. (A) GC blank; (B) GC fortified; (C) LC blank; and (D) LC fortified. The color lines correspond to the chromatogram of each compound.
Toxics 11 00498 g001
Toxics 11 00498 g002 550
Figure 2. Relative Matrix Effect (%) of 353 compounds (the red dotted line indicates the acceptable range, from −20% to +20%).
Figure 2. Relative Matrix Effect (%) of 353 compounds (the red dotted line indicates the acceptable range, from −20% to +20%).
Toxics 11 00498 g002
Table
Table 1. Summary of compounds (including compound class) and chromatographic and mass spectrometric conditions of analytes in serum, linearity, matrix effect (ME), and limit of quantification (LOQ).
Table 1. Summary of compounds (including compound class) and chromatographic and mass spectrometric conditions of analytes in serum, linearity, matrix effect (ME), and limit of quantification (LOQ).
No.CompoundClassTechnique Retention Time (min)PolarityQuantificationConfirmationFragmentor Voltage (V)Linearity (R2)ME (%)LOQ (ng/mL)
MRM (m/z)Collision Energy (eV)MRM (m/z)Collision Energy (eV)
12-PhenylphenolPGC6.28positive169.0 ➔ 115.030169.0 ➔ 141.015700.9802127.840.6
24,4′-Dichlorobenzophenone (metabolite of dicofol)PGC10positive250.0 ➔ 139.015250.0 ➔ 215.05700.976290.40.3
3AbamectinePLC10.98positive890.5 ➔ 567.110895.5 ➔ 751.4451600.981189.992.5
4AcenaphthenePOPGC5.93positive153.0 ➔ 152.025153.0 ➔ 151.035700.9846127.450.3
5AcenaphtylenePOPGC6.14positive152.0 ➔ 151.025152.0 ➔ 126.030700.9673143.840.6
6AcephatePLC1.65positive184.0 ➔ 143.015143.0 ➔ 95.015700.9941109.142.5
7Acetaminophen (Paracetemol)MLC2.76positive152.1 ➔ 65.040152.1 ➔ 93.0201500.9881160.91.25
8AcetamipridPLC4.44positive223.1 ➔ 126.027223.1 ➔ 90.0451400.998195.840.3
9AcrinathrinPLC10.71positive559.0 ➔ 208.010559.0 ➔ 181.030700.990489.030.6
10AlbendazoleMLC7.26positive266.1 ➔ 234.116266.1 ➔ 191.0321550.996690.750.15
11AldicarbPLC5.17positive208.0 ➔ 116.010116.0 ➔ 89.141000.997984.140.15
12Aldicarb-sulfonePLC2.8positive240.1 ➔ 76.016223.1 ➔ 86.113750.996690.210.6
13Aldicarb-sulfoxidePLC2.75positive207.1 ➔ 131.910207.1 ➔ 89.110860.997292.141.25
14AldrinPOPGC9.89positive255.0 ➔ 220.025263.0 ➔ 228.010700.9840116.270.3
15AnthracenePOPGC8.4positive178.0 ➔ 176.035178.0 ➔ 152.030700.9868133.330.6
16AtrazinePLC6.77positive216.0 ➔ 173.915216.0 ➔ 103.8301300.997485.710.15
17Azinphos-methylPLC7.28positive318.0 ➔ 132.18340.0 ➔ 160.010600.9969100.460.15
18AzoxystrobinPLC7.59positive404.1 ➔ 372.18404.1 ➔ 344.1241100.998589.930.15
19BDE-28POPGC12.23positive406.0 ➔ 246.020406.0 ➔ 167.025700.9768124.380.15
20BDE-47POPGC14.32positive326.0 ➔ 138.045484.0 ➔324.025700.9824128.480.3
21BDE-85POPGC17.1positive564.0 ➔ 404.025566.0 ➔ 406.025700.9618128.80.3
22BDE-99POPGC16.28positive566.0 ➔ 406.025564.0 ➔ 404.030700.9758141.830.3
23BDE-100POPGC15.86positive566.0 ➔ 406.025564.0 ➔ 404.025700.9698147.250.3
24BDE-153POPGC18.06positive644.0 ➔ 484.025486.0 ➔ 377.030700.9792141.230.15
25BDE-154POPGC17.5positive644.0 ➔ 484.025486.0 ➔ 377.030700.9776149.110.3
26BDE-183POPGC20.14positive561.6 ➔ 454.740563.6 ➔ 454.740700.9649233.140.15
27BenalaxylPLC8.98positive326.2 ➔ 148.020326.2 ➔ 208.012900.998582.410.15
28BendiocarbPLC5.92positive224.1 ➔ 166.98224.2 ➔ 108.9151200.9977101.280.3
29Bendiocarb metabolite (2, 2-dimethylbenzo-1, 3-dioxol-4-ol)PGC4.83positive166.0 ➔ 151.010166.0 ➔ 126.020700.9559347.742.5
30BenfuracarbPLC9.73positive411.2 ➔ 190.013411.2 ➔ 252.0151100.930422.531.25
31Benzo[a]anthracenePOPGC13.88positive228.0 ➔ 226.040228.0 ➔ 202.035700.9857126.760.15
32Benzo[a]pyrenePOPGC16.91positive252.0 ➔ 250.045252.0 ➔ 248.060700.9863138.960.15
33Benzo[b]fluoranthenePOPGC16.27positive252.0 ➔ 248.060252.0 ➔ 226.035700.9796141.040.3
34Benzo[ghi]perylenePOPGC19.65positive276.0 ➔ 274.050276.0 ➔ 272.060700.9828129.940.15
35Benzo[k]fluoranthenePOPGC16.3positive252.0 ➔ 250.045252.0 ➔ 224.040700.9801125.790.3
36BifenthrinPGC13.89positive440.0 ➔ 181.05440.0 ➔ 165.060940.989399.720.15
37BitertanolPLC9.22positive338.2 ➔ 70.04338.2 ➔ 269.251000.9961102.640.3
38Boscalid (formerly nicobifen)PGC16.55positive3434.0 ➔ 272.030343.0 ➔ 140.0451000.9721100.390.15
39BrodifacoumARLC10.64negative521.3 ➔ 79.050523.3 ➔ 135.0452200.987936.30.3
40BromadioloneARLC9.7negative525.3 ➔ 250.040527.3 ➔ 250.0402000.9892880.3
41BromopropylatePGC13.87positive341.0 ➔ 183.015341.0 ➔ 157.045700.9760100.520.15
42Bromuconazole (two isomers)PGC13.81positive295.0 ➔ 173.010295.0 ➔ 175.010700.976497.20.3
43BupirimatePLC8.4positive273.0 ➔ 108.015273.0 ➔ 193.05700.995396.560.3
44BuprofezinPLC9.88positive306.1 ➔ 201.012306.1 ➔ 116.0121400.997579.090.15
45Cadusafos (ebufos)PLC9.4positive271.1 ➔ 159.016271.1 ➔ 131.0221000.990388.950.3
46CarbarylPLC6.24positive202.1 ➔ 145.14202.1 ➔ 127.128950.9968101.80.15
47Carbendazim (azole)PLC3.4positive192.1 ➔ 160.14202.1 ➔ 127.128900.997770.730.3
48CarbofuranPLC5.95positive222.1 ➔ 123.120222.1 ➔ 165.130800.997393.770.15
49Carbofuran-3-hydroxyPLC4.27positive238.1 ➔ 163.110238.1 ➔ 181.1101100.997679.760.6
50Cefuroxima axetil (two isomers)MLC5.4positive533.0 ➔ 447.015533.0 ➔ 386.0201600.9970197.750.3
51ChloramphenicolMLC4.62negative321.0 ➔ 152.14323.0 ➔ 152.141130.9766115.612.5
52ChlorantraniliprolePLC7.33positive483.9 ➔ 452.916483.9 ➔ 285.981050.9979101.230.3
53ChlorfenapyrPGC12.01positive247.0 ➔ 200.030247.0 ➔ 227.015700.986493.610.6
54ChlorfenvinphosPLC9.08positive361.1 ➔ 98.934358.9 ➔ 155.181050.994796.770.3
55ChlorobenzilatePGC12.14positive251.0 ➔ 111.040251.0 ➔ 139.015700.986693.380.15
56ChlorophacinoneARLC8.75negative373.2 ➔ 201.020375.2 ➔ 203.0201600.934572.975
57ChlorprophamPGC7.12positive213.0 ➔ 127.015153.0 ➔ 90.025700.9818109.490.15
58ChlorpyrifosPGC9.93positive314.0 ➔ 258.015314.0 ➔ 286.05700.979898.630.15
59Chlorpyrifos methylPGC9.12positive286.0 ➔ 93.025286.0 ➔ 271.015700.983987.880.15
60Chlorthal dimethylPOPGC10.03positive300.9 ➔ 166.955300.9 ➔ 222.925700.9757103.060.15
61ChryseneMGC13.95positive228.0 ➔ 226.040228.0 ➔ 227.025700.9800123.040.3
62ClindamycinPLC5.65positive425.2 ➔ 126.120425.2 ➔ 377.2201500.996998.591.25
63ClofentezinePLC9.2positive303.1 ➔ 138.012303.1 ➔ 102.0401200.994092.230.3
64ClothianidinMLC3.9positive250.0 ➔ 169.08250.0 ➔ 131.981000.9959109.871.25
65Cortiscosterone 21 acetatePLC7.89positive389.1 ➔ 329.013389.1 ➔ 371.013800.996889.531.25
66CoumachlorPLC8.6positive343.1 ➔ 162.815342.1 ➔ 285.0151200.984994.860.6
67CoumaphosARLC8.99positive363.0 ➔ 227.030363.0 ➔ 306.9151200.9912107.110.6
68CoumatetralylPLC8.26negative291.1 ➔ 141.030291.1 ➔ 247.0201400.992293.550.6
69CyazofamidPLC8.48positive325.0 ➔ 108.020325.0 ➔ 261.115900.994690.540.6
70CyflufenamidPLC9.19positive413.1 ➔ 223.133413.1 ➔ 295.123700.995289.990.3
71Cyfluthrin (sum of four isomers)PGC16.21positive226.0 ➔ 206.025198.9 ➔ 170.125700.973576.972.5
72Cyhalothrin (lambda isomer)PLC10.48positive181.1 ➔ 152.110181.1 -> 127.146700.988397.582.5
73