A powerful tool for the wide-screening of organic contaminants in citizen science initiatives : development and validation of a SBSE GC-QToF-HRMS method.
Date: 2025-02-18
Institutions: Joint Research Centre
Subjects: EU Member State, European citizens' initiative, citizen science, environmental monitoring, pesticide residue, pollution control, research method, research report, water analysis, water pollutant, water pollution

ISSN 1831-9424 

A Powerful Tool for the Wide-Screening of 
Organic Contaminants in Citizen Science 
Initiatives: Development and Validation of 
a SBSE GC-QToF-HRMS Method 

Cacciatori, C., Mariani, G., Tavazzi, S., 
Comero, S., Gawlik, B.M. 

2025 

 EUR 40235 

 
 
  
 
This document is a publication by the Joint Research Centre (JRC), the European Commission’s science and knowledge 
service. It aims to provide evidence-based scientific support to the European policymaking process. The contents of this 
publication do not necessarily reflect the position or opinion of the European Commission. Neither the European 
Commission nor any person acting on behalf of the Commission is responsible for the use that might be made of this 
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part of the European Union concerning the legal status of any country, territory, city or area or of its authorities, or 
concerning the delimitation of its frontiers or boundaries. 

 Contact information                                                                                                                                                       
Name: Caterina Cacciatori                                                                                                                                             
Email: caterina.cacciatori@ec.europa.eu 

EU Science Hub                                                                           
https://joint-research-centre.ec.europa.eu 

JRC141026 

EUR 40235 

PDF  

ISBN 978-92-68-24985-7   ISSN 1831-9424   doi:10.2760/9603874  

KJ-01-25-104-EN-N 

Luxembourg: Publications Office of the European Union, 2025  

© European Union, 2025  

The reuse policy of the European Commission documents is implemented by the Commission Decision 2011/833/EU of 12 December 2011 
on the reuse of Commission documents (OJ L 330, 14.12.2011, p. 39). Unless otherwise noted, the reuse of this document is authorised 
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How to cite this report: European Commission: Joint Research Centre, Cacciatori, C., Mariani, G., Tavazzi, S., Comero, S. and Gawlik, B.M., A 
Powerful Tool for the Wide-Screening of Organic Contaminants in Citizen Science Initiatives: Development and Validation of a SBSE GC-QToF-
HRMS Method, Publications Office of the European Union, Luxembourg, 2025, https://data.europa.eu/doi/10.2760/9603874, JRC141026

 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
Contents 

Abstract ...................................................................................................................................................................................................... 3 

1  Introduction ....................................................................................................................................................................................... 4 

2  Materials and Methods ............................................................................................................................................................... 8 

2.1  Materials and chemicals .................................................................................................................................................. 8 

2.2  Standard analytical procedure ..................................................................................................................................... 9 

2.2.1  Calibration Curve .................................................................................................................................................... 9 

2.2.2  Sample preparation and extraction ............................................................................................................. 9 

2.3  Instrumentation ................................................................................................................................................................. 10 

2.3.1  Gas Chromatography method ..................................................................................................................... 10 

2.3.2  QToF Mass Spectrometry acquisition method ................................................................................... 11 

3  Instrumental and injection reproducibility .................................................................................................................... 13 

3.1 Experimental design .......................................................................................................................................................... 13 

3.2 Results ...................................................................................................................................................................................... 14 

3.3 Discussion ............................................................................................................................................................................... 15 

4  Reproducibility and recovery of the stir bar................................................................................................................. 16 

4.1  Experimental design ........................................................................................................................................................ 16 

4.2  Results .................................................................................................................................................................................... 16 

4.3  Discussion ............................................................................................................................................................................. 18 

5  Testing of passive extraction ............................................................................................................................................... 19 

5.1  Materials and methods ................................................................................................................................................. 19 

5.2  Results .................................................................................................................................................................................... 20 

5.3  Discussion ............................................................................................................................................................................. 22 

6  Testing of isochronous stability .......................................................................................................................................... 23 

6.1  Statistical Analysis ........................................................................................................................................................... 23 

6.2  Study design ........................................................................................................................................................................ 24 

6.3  Results .................................................................................................................................................................................... 25 

6.4  Discussion ............................................................................................................................................................................. 30 

7 Conclusions ....................................................................................................................................................................................... 31 

References ............................................................................................................................................................................................. 32 

7  List of abbreviations and definitions ............................................................................................................................... 35 
1 

 
 
 
8  List of Figures ............................................................................................................................................................................... 36 

9  List of tables .................................................................................................................................................................................. 37 

10 Annexes ............................................................................................................................................................................................ 38 

Annex 1. List of screened compounds with respective methods parameters .......................................... 38 

Annex 2. List of screened compounds, their categories and additional information ........................... 45 

Annex 3. Calibration curve equations, Limit of Detection (LOD), Limit of Quantification (LOQ) and 
Method Detection Limit (MDL) for screened compounds ..................................................................................... 52 

Annex 4. Desorption, injection and Gas Chromatography analysis parameters ..................................... 60 

Annex 5. List of selected pesticides for recovery and reproducibility study ............................................. 61 

Annex 6. Recoveries of individual pesticides, reported alongside standard deviations and 
coefficient of variations .......................................................................................................................................................... 63 

Annex 7. Recoveries of individual pesticides with standard deviations for extraction test .............. 66 

Annex 8. Statistical results of isochronous stability testing for individual pesticides (b = slope, ub 
= standard error of the slope, U = Uncertainty, we = weeks) ............................................................................ 69 

2 

 
 
 
Abstract 

In the framework of “The Gems of Water” citizens’ engagement activities, a new methodological 
approach was studied. The report presents the development and optimisation of a method for wide-
screening of organic apolar pesticides in surface waters using Stir Bar Sorptive Extraction (SBSE) 
coupled with Gas Chromatography-Quadruple Time of Flight-High Resolution Mass Spectrometry 
(GC-QToF-HRMS). The report describes the optimisation of water extraction and instrumental 
parameters for around 200 pesticides. Calibration curves, limits of detection, and limits of 
quantification were determined. The method was optimized through reproducibility and recovery 
tests, as well as isochronous stability testing. Different passive and active extraction modalities 
were investigated. Based on the obtained results, most suitable parameters among those tested 
were selected to improve the methodology employed for measuring of pesticides in water samples. 
The report concludes that the method developed herewith has the potential to be applied in citizen 
science initiatives for water quality monitoring. 

3 

 
1 

Introduction 

Insight of increasing contamination of water bodies globally by organic contaminants, strengthening 
water quality monitoring capacity becomes urgent to understand, mitigate and protect such 
valuable resource. In view of this, in 2019, United Nations Environment Assembly (UNEA) Resolution 
3/10 mandated the establishment of the World Water Quality Alliance (WWQA)1 to “Address water 
pollution to protect and restore water-related ecosystems” (UNEA 2017).  

The World Water Quality Alliance (WWQA) brings together institutions at global, regional and local 
scale to assess the status of global water bodies, based on data from environmental monitoring, 
earth observation, laboratory analysis and, last but not least, citizen science. The Water Laboratory, 
as part of the WWQA and in support of the United Nations Global Environment Monitoring System 
(GEMS/Water), contributes to the assessment through the development of “The Gems of Water” 
citizens’ engagement activity.  

The activity, aligned with Zero Pollution Action Plan set out by the European Commission for the 
years 2019-2024, seeks to test a water quality monitoring system for pesticides based on the 
combination of advanced wide screening technology and citizens’ engagement. “The Gems of 
Water” functioning is based on the following steps:  

Figure 1. Workflow of “The Gems of Water” activity. 

Source: (Caterina Cacciatori et al. 2024) 

1 https://wwqa.info/ 

4 

 
 
 
 
1.  A method of sampling, extraction and analysis of surface water samples is designed and 

tested at the JRC Water Laboratory.  

2.  The sampling and extraction procedures as well as the background of the activity are 

written and explained in user-friendly protocols accompanied by simple videos for citizens 
involved. 

3.  Communication is established with local groups and contact points (NGOs, Universities, 

Community Groups) interested in understanding local water contamination by organic 
pesticides. The primary source of contact points is the World Water Quality Alliance network. 

4.  A monitoring plan is designed with the local groups, while logistics are discussed and 

explained.  

5.  The kit containing the necessary material for sampling and extraction is shipped to the local 

contact points.  

6.  Local groups organise and carry out sampling and extraction activities using the stir bars, 

after which they return the extracted samples to the JRC Water Laboratory.  

7.  At the JRC, samples are analysed by High Resolution Gas Chromatography with Quadruple 

Time of Flight Mass Spectrometry (HRGC-QToF-MS). 

8.  Feedback surveys are collected from participants to improve the design and structure of the 

activity.  

9.  Quantitative and qualitative results are shared with the participants in a raw format, on 

online platform and through scientific publications. 

This report summarises the first step outlined above, describing the development of a method of 
wide-screening of organic apolar pesticides in surface waters by stir bar sorptive extraction (SBSE), 
for their use in citizens’ engagement activities. Protocols mentioned in step 2 and the application of 
the methodology in real case studies can be found in Cacciatori et al. (2023, 2024). While cited 
literature so far focuses on the pilot case in the Caribbean region of Costa Rica, “The Gems of 
Water” is currently deployed in four other countries around the globe:Kenya, Romania, Bulgaria and 
Australia.  

The analytical method developed is based on the stir bar sorptive extraction (SBSE) technology. The 
technology was chosen as it is capable of monitoring a wide selection of organic contaminants 
including pesticides, pharmaceuticals and industrial chemicals (Ochiai et al. 2011; Sargazi, Bücking, 
and Kaykhaii 2020), while being easily applicable and logistically feasible for citizens’ engagement 
applications. Such a method allows a wide range of contaminants to be tested per sample, and to 
better address the diversity of pesticides used globally. Furthermore, the use of wide-screening 
detection technologies reflects the current tendency of water quality monitoring towards a more 
comprehensive and trace-level description of water bodies (Hollender et al. 2019; Brack et al. 
2018). Such an approach is fundamental to address the increasing urban, agricultural and industrial 
contamination of the water cycle by human activities. At the same time, new organic chemicals are 
added to the market every day. Wide-screening water quality results can provide additional eco-
toxicological analysis, with an insight into the cumulative effects of pesticides in the samples. While 
some of the screened compounds have already been banned or their use restricted, the limitations 
linked to single-substance screening methods implemented to comply with EU? water regulations 
hinder a more comprehensive understanding of their environmental behaviour (Dulio et al. 2018). In 
2022, an on-going consultation was initiated to discuss the pollutants list included in the European 

5 

 
Commission Water Framework Directive (EC WFD) and its daughter directives, particularly the 
Environmental Quality Standard (EQS) Directive (European Council and European Parliament 2013) 
for surface and ground waters. The debate triggered the question of whether extending the number 
of chemical compounds monitored actually helps achieve the goal of good ambient water quality2.  

The diffusion of wide screening and non-target screening methods for water quality testing has 
been accompanied by the development of miniaturised extraction methods to allow for faster, more 
sustainable and easier pre-concentration procedures of a variety of organic compounds. Among 
such methods, the stir bar sorptive extraction counts on some characteristics which makes it 
particularly interesting for application in “The Gems of Water”. The SBSE, developed in 1999, is one 
of the most implemented sorbent-based methods of micro-extraction (Sargazi, Bücking, and 
Kaykhaii 2020). SBSE is based on the implementation of a glass magnetic stir bar coated with a 
sorbent layer of either Polydimethylsiloxane (PDMS) or ethylene glycol (EG-Silicone), depending on 
whether hydrophobic or polar compounds are the objective of monitoring. PDMS is mostly the 
preferred absorption phase especially in the case of volatile/semi-volatile non-polar compounds, 
with a partition coefficient of logKow > 3 (David, Ochiai, and Sandra 2019). The extraction is 
performed through magnetic rotation until equilibrium is reached. The advantages of SBSE include 
reduced glassware use, limited solvent utilisation and sample manipulation, limiting opportunities of 
errors in the measurements especially at ultra-trace levels (David, Ochiai, and Sandra 2019). 

SBSE is often used coupled with gas chromatography with quadruple time of flight mass 
spectrometry (GC-QTOF-HRMS). Because of its thermal stability, PDMS-coated stir bars allow for 
direct automated injection through thermal desorption (TD) in a GC-QTOF-HRMS, reducing bleeding 
and, consequently, background chromatographic noise. GC-QTOF-HRMS allow for accurate mass 
definition with high resolution, higher selectivity and sensitivity and reliable quantification and 
identification of a wide number of compounds present in the water samples based on ion 
composition (Sargazi, Bücking, and Kaykhaii 2020). Thus, the coupling of SBSE with GC-QTOF-HRMS 
responds to the need to screen a wide number of chemicals, while the advantages of the stir bar 
sorptive extraction makes it an attractive method for application in citizen science. According to 
previous research, PDMS as an absorbent phase has delivered good results in terms of 
reproducibility and repeatability between predicted and theoretical recoveries and similar or higher 
recovery in respect to direct injection and other extraction methods (Sargazi, Bücking, and Kaykhaii 
2020; Campanale et al. 2021; Ochiai et al. 2011). The extraction recovery is influenced by various 
parameters and research effort has been channelled in the optimisation of the sample preparation 
and analysis. In this direction, Lerch et al. (2018) worked on a protocol with the PDMS coated stir 
bar (10 mm*1 mm) with more than 100 compounds, taken from the WFD watch lists (Posada-Ureta 
et al. 2016). Using 100 ml samples, they set the extraction time to 5 hours at 800 rpm, and 
proposed a second extraction, to account for the recovery disturbances generated through the 
presence of suspended particles in the sampled water.   

Ochai et al. (2011) used SBSE coupled with TD and GC-QTOF-HRMS to determine the occurrence of 
23 organochlorines pesticides (OCPs in river water, accompanying the analysis with a non-target 
screening of pesticides, polyaromatic hydrocarbons (PAHs) and polychlorinated biphenyls (PCBs). 
Implementing stir bars (10 mm*0.5 mm; 20 mm*0.5 mm) on 50 ml samples, the extraction was run 

2 https://ec.europa.eu/environment/water/water-dangersub/pri_substances.htm, accessed on 07.08.2024 

6 

 
 
 
for 3 hours at a rotation speed of 1,500 rpm and compared to traditional Liquid Phase Extraction 
(LPE) on 20 L samples, achieving agreeing results.  

Sargazi et al. studied the influence of varied parameters such as temperature, rotation speed, 
extraction time, sample volume, ionic strength and pH on extraction of ultra-trace amounts of 
pesticides lambda-cyhalotrhrin, alpha-cypermethrin, teflurthin, dimefluthrin in river and tap water 
samples, after which extraction parameters were set at 180 min at 700 rpm at 40°C with a sample 
volume of 20 ml (Sargazi, Bücking, and Kaykhaii 2020). 

Among the advantages of the stir bar sorptive extraction method, the easiness of application, the 
reduced use of solvents and the limited needed laboratory equipment are a few (Nasiri, 
Ahmadzadeh, and Amiri 2020). Although, SBSE extraction is limited to the dissolved fraction, 
extraction on a stir bar on site simplifies logistical procedures, guaranteeing smoother shipment of 
samples and improved stability. SBSE has the potential to streamline the already eased analytical 
and logistic burden of the JRC-developed MARIANI box (Mariani et al. 2020), which allows for on-
site solid phase extraction by, as mentioned, reducing the high sample volumes needed and the use 
of solvents. The controlled and restricted sample volume parameter (100 ml) obtained through 
grab-sampling has the advantage of providing quantitative data in the form of concentrations, thus 
avoiding the complexity of average flow calculations when using passive samplers such as Polar 
Organic Chemical Integrative Sampler (POCIS) or Chemcatcher (Posada-Ureta et al. 2016).  

Therefore, in the context of “The Gems of Water” citizens’ engagement project and according to 
previous research, an analytical screening method was developed for sampling and extraction by 
citizens groups and for analysis at the JRC Water Laboratory. As explained in the following chapters 
of this report, the method development included defining a pesticide screening list. The compounds 
were chosen due to the interest in addressing water quality contamination in rural areas of the first 
five pilot locations of “The Gems of Water” project and considering the applicability of the SBSE 
extraction and GC-QToF-HRMS to the physicochemical characteristics of the compounds. The list is 
constantly updated based on analysis of local uses, in consideration of the input provided by the 
local contact points. In fact, after a consultation with local groups, new compounds were added, 
based on local use of products as investigated at local level, for which stability and recovery test 
are not reported in this first work. limits of detection (LOD) and limits of quantification (LOQ) were 
defined along with the establishment of linearity and working range for 201 pesticides. The method 
development included the evaluation of the injection reproducibility to define instrumental 
parameters for the analysis by GC-QToF-HRMS. A subset of 88 pesticides were selected for further 
optimisation studies, allowing to find a compromise between representativeness of the different 
pesticides categories and analytical burden. The pesticides selected belonged to the classes of 
herbicide methyl esters (3), organochlorines (33), organonitrogen (20), organophosphorous (27) and 
synthetic pyrethroid (5). The optimisation exercises included recovery and reproducibility of the stir 
bars extraction method and an exercise of passive extraction allowed to determine the most 
effective extraction procedure. Stability testing was also carried out for 6 weeks to guarantee an 
acceptable level of uncertainty in the quantification of compounds, accounting for the logistics of 
shipping the stir bars around the world.  

7 

 
 
 
2  Materials and Methods  

2.1  Materials and chemicals  

All the native and labelled analytical standards were purchased from the main suppliers as 
Cambridge Isotope Laboratories Inc. (Massachusetts, USA), Wellington Laboratories (Ontario, 
Canada), Restek (Pennsylvania, USA), SigmaAldrich (Missouri, USA). All the solvents (toluene, 
acetone) for residual grade were obtained from SigmaAldrich (Missouri, USA). Stir bars were 
purchased by Gerstel (Germany).  

The total number (201) of native standards used in the method belongs to three main categories of 
pesticides, namely fungicides, herbicides, and insecticides (Figure 2).  

Figure 2. Share of pesticides categories in the screen method 

 Source: JRC Water Laboratory 

As for the internal standards, organochlorine pesticides have their own labelled standards, while 
trans-Nonachlor C13 (Cambridge Isotope Laboratories, Inc.) has been chosen to cover the other 
pesticides groups. Annex 1 and Annex 2 report all relevant information of the native compounds 
included in the screen, such the associated internal standard, Chemical Abstract Service (CAS) 
registry number, ion masses (m/z) and the retention times. Ion masses and retention time were 
obtained according to the method developed by MassHunter Agilent Pesticides Personal Compound 
Database and Library (PCDL)(Agilent Technologies 2016), the Octanol-Water coefficient of partition 
LogKow values were collected from Chemspider website3 and from the Pesticides Properties 
DataBase (PPDB) (Agriculture & Environment Research Unit (AERU) 2018). 

3 http://www.chemspider.com/ accessed 07.08.2024 

8 

 
 
 
2.2  Standard analytical procedure 

2.2.1  Linearity study  

A native compounds solution containing all pesticides (1 ng/µl) and a total (24 organochlorine 
pesticides) internal standards solution (1 ng/µl) were composed. Native compounds and internal 
standards solutions were used to spike water samples for the exercise of reproducibility (Section 3) 
and recovery (Section 4), testing passive extraction (Section 6), for the isochronous stability testing 
(Section 7), and for the determination of the calibration curve levels. Each of the calibration point 
were analysed in 3 replicates, except for L1, which, prepared in 6 replicates, were used to determine 
method detection limit (MDL), LOD and LOQ, according to the methodology of the United States 
Environmental Protection Agency (EPA)4. MDL is calculated by multiplying the standard deviation of 
the 6 (L1) replicates by one-sided t-test result (United States Environmental Protection Agency 
(EPA) 2016), while LOD and LOQ are 3 and 10 times respectively the calculated standard deviation. 

Table 1. Calibration curve levels  

Levels 

Concentration [ng/l] 

L1 

10 

L2 

25 

L3 

50 

L4 

100 

L5 

250 

A total of 5 ng/l of individual internal standards were added to each sample, prior to the extraction. 
Annex 3 summarises the equation and the R2 values of the calibration factor (CF), MDL, LOD and 
LOQ for each compound. The majority of compounds show linear behaviour with R2 > 0.9. Few 
compounds, including metalaxyl, linuron, acequinocyl, hexazinone, pyriproxifen, menvinphos, THPI 
(Tetrahydrophtalimide), fludioxonil, fluridone, biphenyl, pyrimethanil and tricyclazole, based on 
computation of the calibration curve, show low compatibility with the stir bar extraction method, 
therefore they have been excluded from this study.  

2.2.2  Sample preparation and extraction  

The wide-screening method of the 88 chemicals was established with the implementation of the 
stir bar sorptive extraction performed according to the slightly modified procedure developed by 
Lerch et al. (2018). The stir bars are glass magnetic bars coated with a layer of PDMS, which, as 
mentioned in the introduction, allow for the adsorption of volatile apolar compounds present in 
water. The stir bars used in the exercise are 10 mm long and have a PDMS layer of thickness of 1 
mm (Figure 3).  

4 https://www.epa.gov/cwa-methods/method-detection-limit-frequent-questions#intro, accessed on 08.08.2024 

9 

 
 
 
Figure 3. Stir bars in their vials 

Source: JRC Water Laboratory 

Since stir bars act as passive sampler, a preconditioning step is necessary to guarantee that they 
are clean from possible contamination from the surrounding environment. The stir bars are 
preconditioned at 310°C degrees for 5 hours under N2 flow in conditioning tubes and 50 stir bars 
can be conditioned simultaneously in a Thermal Conditioning Unit (Gerstel, Germany).  

Drinking water taken from a dispenser inside the JRC premises was used. Water was collected in 
pre-cleaned 1l glass bottles and used to fill pre-cleaned 100 ml sample glass bottles. The samples 
were then spiked with native and internal standard solutions diluted in 1 ml of acetone to obtain a 
better mixing of chemicals in the samples. Depending on the exercise, and as specified further for 
each case, the standard solution was either diluted and pipetted into the water samples before 
extraction or injected directly before analysis with the use of the Multipurpose Sampler (MPS).  

According to the standard analytical procedure, the extraction step involves magnetic stirring of the 
stir bar in the spiked water sample. The extraction lasts for five hours at room temperature, with a 
rotation speed of 800 rpm (Lerch et al. 2018). After the extraction, the stir bars are removed from 
the water samples using a magnetic stick and dried of visible drops by nitrogen flow for around 1 
min. The stir bars are positioned for direct injection in the desorption tubes or stored in vials at 4°C 
before the analysis is conducted. The second extraction proposed by Gerstel (Germany) using 
toluene and methanol to capture compounds bound to particulate matter present in the sampled 
water was excluded because it is not suitable to reducing risks of citizens involved in “The Gems of 
Water” activity and to simplify logistics of shipping and retrieving samples around the world. 
Therefore, extraction is limited to compounds in the dissolved phase.  

2.3  Instrumentation 

2.3.1  Gas Chromatography method 

The analysis were performed by using a Gas Chromatograph 8890 with Quadruple Time-Of-Flight 
7250 (Agilent Technology, USA) coupled with a Multi-Purpose Sampler connected to a Thermal 
Desorption Unit TDU2, and a Programmable Temperature Vaporizer (PTV) CIS-4 (Cooling Injection 
System) and a cryostatic cooling system CCD2 (Gerstel, Germany), as shown in figure 4. A Multi-

10 

 
Purpose Sampler (MPS) is in place to automatically move the desorption tubes with the stir bars 
from the trays to the TDU.  

All chemicals were separated and analysed on a HP-5MS UI capillary column (length = 30 m, 
internal diameter = 0.25 mm, film thickness = 0.25 um, Agilent Technology, USA).  

Figure 4. GC-QTOF-HRMS 

Source: JRC Water Laboratory 

Desorption, injection and gas chromatographic analysis parameters were kept same through all 
exercises and are reported in Annex 4. In the table in Annex 4, injection parameters for cooling 
injection system and thermal desorption unit which differ from desorption parameters are reported 
in parenthesis. Injection volume was 2 µl with an injection speed of 50 µl/s. Injection method 
parameters and liners specificities for the reproducibility of injection exercise are described 
separately in Section 3, as they differ from those of all the other exercises.  

Data acquisition, instrument control and raw data analysis were performed with MassHunter Agilent 
Qualitative and Quantitative Analysis software (Version 12.1), MassHunter Agilent Pesticides PCDL 
workflow for GC-QToF (PCDL Manager B.08.00), as well as with pandas library in Python 3.6.2. All 
exact masses used for identification and quantification are reported in Annex 1, as reported in 
section 2.1. 

2.3.2  QToF Mass Spectrometry acquisition method 

The mass spectrometer used for wide target screening analysis was a Quadrupole Time of Flight 
(QToF). The instrument operated always in high-resolution full scan, with operational parameters 
reported in table 2. 

Table 2. High-resolution operational parameters 

Ion source 

EI 

Source temperature 

280 °C 

Electron energy 

EI Emission 

70 eV 

5 μA 

11 

 
Solvent delay 

4 min 

Mass range 

5 – 650 (m/z) 

Acquisition rate 

5 spectra/s 

Acquisition time 

200 ms/spectrum 

The reference calibration mass, their accuracy and the power resolution are reported in table 3  

Table 3. QToF reference calibration mass, accuracy and power resolution 

Target Mass 
(m/z) 

Actual Mass 
(m/z) 

Accuracy 
(ppm) 

Abundance 

Resolution 

Time of Flight 
(ns) 

68.9947 

68.9947 

130.992 

130.9915 

218.985 

218.9851 

263.987 

263.9866 

413.977 

413.9771 

0.14 

0.32 

-0.1 

0.11 

0.35 

1 493 298.10 

19422 

997 239.80 

25399 

388 426.30 

32864 

266 761.30 

34180 

51 417.20 

35550 

463.974 

463.9736 

-0.35 

18 485.40 

34206 

501.971 

501.9708 

613.964 

613.9643 

0.45 

0.18 

37 796.40 

35891 

7 490.10 

35493 

25271 

34353 

44054 

48248 

60108 

63561 

66063 

72931 

12 

 
 
 
3 

Instrumental and injection reproducibility  

To verify the consistency and repeatability of results of the analysis method using Stir Bar Sorptive 
Extraction (SBSE) coupled with Multipurpose sampler for Gas Chromatography –Mass Spectrometry 
(acronym?), several reproducibility tests were carried out. The instrumental and injection 
reproducibility test assessed internal standard injection performance by changing injector 
parameters. The instrumental and injection reproducibility test are important as they serve as a 
reference for reproducibility tests and recovery of pesticides, as well to evaluate their isochronous 
stability with the SBSE. This test was used to optimize operational parameters for injection. The test 
consists of injecting internal standard solution into the thermal desorption tubes. The tubes are then 
automatically positioned, one at time, by the Multipurpose Sampler into the stir bar-containing 
Thermal Desorption Unit (Figure 5), where analytes are heated up to 300°C. For the subsequent stir 
bar analysis, compounds are released from the stir bar to the chromatographic column, after being 
cooled down to 40°C in the Cooling Injection System. 

Figure 5. Thermal Desorption Unit and Cooled Injection System 

Source: Gerstel (Germany) 

3.1 Experimental design 

The reproducibility was tested over 10 injections for each method. The volume of injected internal 
standard solution was 2 µl for all three methods. The responses were analysed for Polychlorinated 
Byphenils (PCBs). PCB congeners have been chosen as they have a wide range of volatility and thus 
can be representative for the different compounds screened in the other tests. 

Instrumental and injection reproducibility was studied for three different injection methods, 
summarised in Table 4. The differences of the three methods applied refer to (1) the removal or 
retaining of the desorption tubes after desorption and to (2) the type of liners used. The desorption 
tube can be retained until the end of the GC analysis (Methods 2, 3) or removed right after the 
release of contaminants from the Cooled Injection System into the column, before the start of the 
GC analysis (Method 1). Two liners were tested: an empty baffled liner and a liner filled with 
silanised glass wool. The choice of the liner might play a role on the peak shape and reproducibility 
of the analysis. All injections were splitless. The solvent vent is open for 5 minutes at 40 mL/min, 
while the split vent is closed before and throughout the desorption time, as indicated by the split 
less time, set at 50 sec for all three methods.  

13 

 
Table 4. Injections methods for instrumental reproducibility testing  

Method 1 

Method 2 

Method 3 

Injection mode 
Split less mode,  
with removal of tube 
Split less mode 
with retaining of the tube 
Split less mode  
With retaining of the tube 

Liner 
Baffled 

Baffled 

Silanized glass wool ID = 1mm 

The GC-QToF-MS method for desorption and syringe injection was run according to parameters 
reported in Annex 4 (Section 2.3 Instrumentation). 

Quantitative analysis method had been prepared on the MassHunter Agilent Quantitative Analysis 
Software (Version 11.0). Data reported include mean, standard deviation and coefficient of variation 
(CV) of responses. 

3.2 Results 

Table 5 reports mean response, standard deviation, and coefficient of variation for the three 
injection methods, averaged over 10 injections. Generally, it can be noted that Method 3 resulted to 
have higher-counts, while having lower coefficient of variation for all PCB congeners. 

Table 5. Averaged instrument response, standard deviation (SD), and coefficient of variation (CV) over 10 
injections for the three different injection methods for 6 PCB congener 

Standards 

 PCBs 
PCB-28_13C 
PCB-52_13C 
PCB-101_13C 
PCB-138_13C 
PCB-153_13C 
PCB-180_13C 

Method 
Method 
Method 
3 
2 
1 
Mean response (n=10) 
31924 
23284 
25490 
22822 
24919 
22078 

37215 
27139 
29602 
26030 
28375 
24239 

44795 
32110 
33918 
29166 
31752 
27695 

Method 
1 

5647 
3901 
4795 
4048 
4369 
4127 

Method 
2 
SD 
5379 
4184 
4756 
3700 
4250 
3642 

Method 
3 

Method 
1 

6649 
4674 
4744 
4378 
4664 
3949 

15 
14 
16 
16 
15 
17 

Method 
2 
CV [%] 
17 
18 
19 
16 
17 
16 

Method 
3 

15 
15 
14 
15 
15 
14 

Figure 6 reports the instrument response for the three different injection methods averaged for the 
6 PCB congeners over 10 injections. As an overview, the PCBs showed a response, in form of peak 
area average over the 10 replicates and over the 6 compounds, of 286766 ± 4481.2 for Method 1, 
25086 ± 4318.5 for Method 2, and 33239 ± 4842.9 for Method 3. The maximum response 44795 
was obtained for PCB-28_13C using Method 3, while the minimum was 22078 for PCB-180_13C, 
using Method 2. The average coefficient of variation was 16% for Method 1, 17% for Method 2 and 
15% for Method 3. The highest coefficient of variation was 19% reported for PCB-101_13C using 
Method 2, while the lowest was 14% for PCB-101_13C and PCB-180_13C using Method 3, and for 
PCB-52_13C using Method 1. 

14 

 
 
Figure 6. Responses for the 6 PCBs compounds averaged over the 10 injections 

60000

50000

e
s
n
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R

40000

30000

20000

10000

0

PCB-28_13C

PCB-52_13C

PCB-101_13C PCB-138_13C PCB-153_13C PCB-180_13C

PCBs Compounds

Method 1

Method 2

Method 3

Source: JRC Water Laboratory 

3.3 Discussion 

Despite injection results and chromatogram observations suggest that Method 3 as the most  
suitable for further studies on recovery, extraction and stability exercises, it was observed that 
using a liner filled with glass wool led to an increase in the initial toluene noise during acquisition 
time (5-6 minutes). This increase in noise was less significant for injection Method 1 and Method 2. 
No substantial differences were noted in the responses between Method 1 and 2. Method 1, for 
which the desorption tubes are removed during the analysis process, has the additional risk, in case 
of instrumental fault during the tube removal procedure, of letting the injector open allowing air to 
circulate in the column. For this last reason, we decided to adopt Method 2 for all tests reported.  

15 

 
 
4  Reproducibility and recovery of the stir bar 

The reproducibility and recovery of the Stir Bar Sorptive Extraction were tested to proceed in the 
development of a stir bar method for extraction of pesticides in water. 

4.1  Experimental design 

The recovery of SBSE extraction was tested comparing the response ratio factor (RRF) between the 
area of natives and internal standards for the recovery and reproducibility samples and for the 
reference standards. The reference standards were spiked with native and internal standards 
together before extraction. After extraction, the reference standards were desorbed directly into the 
column. The recovery and reproducibility samples were spiked only with native standards before 
extraction, while the internal standards were injected directly before thermal desorption. For 
recovery and reproducibility samples, the internal standard injections is used as a reference to 
calculate stir bar response factor.  

The recovery of SBSE extraction was calculated based on equation below.  

REC [%] = 

𝑅𝑅𝐹 𝑟𝑒𝑐𝑜𝑣𝑒𝑟𝑦 𝑎𝑛𝑑 𝑟𝑒𝑝𝑟𝑜𝑑𝑢𝑐𝑖𝑏𝑖𝑙𝑖𝑡𝑦 𝑠𝑎𝑚𝑝𝑙𝑒 
𝑅𝑅𝐹 𝑟𝑒𝑓𝑒𝑟𝑒𝑛𝑐𝑒 𝑠𝑡𝑎𝑛𝑑𝑎𝑟𝑑𝑠

* 100 

A solution of 2 ml of acetone, containing 5 ng/µl of pesticides mix natives solution and 5 ng/µl of 
internal standard trans-Nonachlor C13 was added to 100 ml water samples for making the 
reference standards. For recovery and reproducibility samples, a solution of 2 ml of acetone 
containing 5 ng/µl of pesticides mix natives solution only was added to 100 ml water samples, 
while 2 µl of internal standard solution (5 ng) was injected during desorption. The reproducibility 
was tested in triplicates. Desorption and injection method parameters are reported in Annex 4.  

The analysis of recovery and reproducibility study was performed on a subset of 88 selected 
pesticides, belonging to the categories of herbicide methyl esters (3), organochlorines (33), 
organonitrogen (20), organophosphorous (27) and synthetic pyrethroid (5). The complete list of 
selected pesticides is reported in Annex 5. 

4.2  Results 

Measurements of average recoveries are calculated from average of triplicates. Reproducibility is 
calculated as coefficient of variation of individual pesticides, as reported in Annex 6. In Table 6, 
simple statistics is reported for recovery and reproducibility calculation.  

The overall recovery rates of the assessed pesticides, showed an average of 88.2 %. The median 
recovery rate was 96.2 %, with 1st and 3rd quartile at 69 % and 111.1 % respectively (Table 6). 
Grouping pesticides by categories, it was observed that organonitrogen pesticides had the lowest 
average recovery (67.7 %) and the lowest 1st quartile value (33 %). Average recoveries for 
organochlorines, organophosphorous and synthetic pyrethroid pesticides were above 80%. 1st 
quartile was 100.3 % for organochlorines compounds, 64.7 % for organophosphorous compounds 
and 110.6 % for synthetic pyrethroids. Average recoveries for herbicide methyl esters were 73.6 %, 
with the first quartile 48.9 %. Recoveries of individual pesticides with standard deviations and 
coefficient of variations are reported in Annex 6. Recovery results for all 88 pesticides are shown in 
Figure 7, ordered by category.  

16 

 
Table 6. Average, median, quartiles of recovery and reproducibility reported for pesticides categories. 

Recovery [%] 

Reproducibility [%] 

Overall (n=88) 

Herbicide  
methyl  
esters (n=3) 

Organochlorines  
(n=33) 

Organonitrogen  
(n=20) 

Organophosphorous  
(n=27) 

Synthetic  
pyrethroid (n=5) 

Average 
Median  
1st Quartile  
3rd Quartile  
Average 
Median  
1st Quartile  
3rd Quartile  
Average 
Median  
1st Quartile  
3rd Quartile 
Average 
Median  
1st Quartile  
3rd Quartile  
Average 
Median  
1st Quartile  
3rd Quartile  
Average 
Median  
1st Quartile  
3rd Quartile  

88.2 
96.2 
69 
111.1 
73.6 
70.6 
48.9 
96.8 
105.1 
105.5 
100.3 
113.2 
67.7 
64.9 
33 
96.3 
80.2 
79.6 
64.7 
96.2 
111.2 
121.4 
110.6 
128.2 

57.1 
55 
37.4 
73.8 
70.5 
72.9 
50.8 
91.4 
41.8 
39.4 
25.6 
50.1 
70.5 
69.4 
55.1 
76.8 
59 
53.1 
47.3 
71.1 
69.9 
59 
55.3 
59.8 

Figure 7. Average recovery for all 88 pesticides, ordered by categories 

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Pesticides

Herbicide methyl esters

Organochlorines

Organonitrogen

Organophosphorous

Synthetic pyrenthroid

Source: JRC Water Laboratory 

17 

 
 
 
  
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
The average reproducibility observed for the 88 selected pesticides (Table 6) was 57.1 %, with 75 
% of compounds above the 1st Quartile of 37.4 %. Looking at the reproducibility by pesticides 
groups, the 1st Quartile is always around 50%, while the overall 1st Quartile average is lower. This 
discrepancy is likely due to the organochlorines results. Among the pesticides categories, 
organochlorines exhibit the lowest reproducibility with a 1st Quartile value of 25.6 %. This is 
attributed to the fact that they are the only pesticides group for which individual internal standards 
wereused.  

4.3  Discussion 

The recovery and reproducibility exercise, obtained using the standard extraction method (Section 
2.2.2), helped to understand the absorption of different pesticides onto the stir bar. The results 
show that recoveries among groups vary; nonetheless, average recovery for 88 pesticides range 
between 69 % and 111.1 % for 1st and 3rd quartiles, respectively, with 75 % of compounds having a 
satisfactory recovery above 70%. Within groups recovery varies, with organochlorines reaching 
highest recoveries. Reproducibility for majority of compounds lies above 50 %, except for 
organochlorines. This is partly expected because of the high number of compounds included in this 
category, which cover a wide spectrum of physico-chemical characteristics, such as volatility, weight 
and hydrophobicity. Best performance of organochlorines pesticides in terms of recovery is not 
surprising as individual internal standards were used for this pesticide group. However, using 
individual internal standards is not feasible in case of wide-screening for citizen science projects. 
Therefore, trans-Nonachlor C13 was confirmed as internal standard of choice. Trans-Nonachlor C13 
is located at the median among all compounds, considering gas-chromatographic retention time.  

18 

 
5  Testing of passive extraction 

In sight of simplifying future application of the SBSE for citizens’ engagement initiatives, it was 
decided to assess whether the stir bar sorptive extraction could achieve acceptable recoveries even 
when carried out passively, meaning without use of magnetic stirring, as per the standard extraction 
procedure described in Section 2.2. A passive extraction protocol would further simplify the 
procedure for participants, ease logistics and reduce the material sent by the JRC to the citizens 
groups engaged in the activity.  

5.1  Materials and methods 

The passive extraction exercise testing scheme is reported in Table 7 and exemplified by the 
sketches (Figure 8).  

Table 7. Scheme of extraction exercise  

Tests 
Standard reference 
extraction 
Passive extraction 

Manual agitation 

Protocol 
5h 800 rotation per minutes 

24h, 48h, 72h, 96h, 144h, 
168h (1 to 6 days) 
5h, handshake every 30 min 
for 1 min 

Replicates 

Total sample number 

3x 

3x 

3x 

3 

18 

3 

The standard extraction protocol is used for three replicates and serves as reference recovery 
respectively to the two other extraction procedures. Passive extraction was run leaving the stir bar 
in the water samples for 24h, 48h, 72h, 96h, 144h, and 168h, after which the stir bars were stored 
in vials at 4°C, before analysis. Manual agitation, on the other hand, was done for a total duration 
of 5 hours, during which the water samples with the stir bars were manually shaken for 1 minute 
every 30 minutes. For all extraction exercises, the 100 ml Milli-Q water samples were spiked with a 
solution of 2 ml of acetone, containing 5 ng/µl of pesticides mix natives solution, while 2 µl of 
internal standard solution (5 ng) were injected directly into the desorption tubes before analysis 
with the Gas Chromatographer. Calculations of recovery are carried out according to the method 
described in Section 4 and were done on the same subset of 88 pesticides. 

The analysis with GC-QToF-HRMS was carried out for all exercises together for the three respective 
replicates. The instrumental method can be consulted in Section 2.3. 

Figure 8. Sketch of extraction exercise i). passive extraction, ii). manual agitation 

i). 

19 

 
 
ii).  

5.2  Results 

Source: JRC Water Laboratory 

The results of all three passive extraction exercises have been averaged over the three replicates 
and normalised over the reference standard, representing the standard extraction procedure. This 
analysis allowed for comparison of percentage recovery and for validation of the three different 
extraction protocols. Results are shown in Table 8 and Figure 9. Recovery values of individual 
pesticides with standard deviations for the different extraction tests and for the standard reference 
extraction are reported in Annex 7. 

Table 8. Average, median, 1st and 3rd quartiles recoveries of different extraction tests for 5 different 
pesticides groups  

Recovery [%] 

24h 

48h 

72h 

96h 

144h 

168h 

Manual  
agitation 

Overall (n=88) 

Herbicide  
methyl  
esters (n=3) 

Organochlorines  
(n=33) 

Organonitrogen  
(n=20) 

Organophosphorous  
(n=27) 

Average 

Median  

1st Quartile  

3rd Quartile  

Average 

Median  

1st Quartile  

3rd Quartile  

Average 

Median  

1st Quartile  

3rd Quartile  

Average 

Median  

1st Quartile  

3rd Quartile  

Average 

Median  

1st Quartile  

3rd Quartile  

Average 

23.4 

9.1 

7.1 

11.2 

48.8 

29.1 

28.8 

59 

10.6 

8.9 

7.7 

10.1 

47.1 

10.0 

8.9 

14.3 

21.3 

7.3 

6.1 

10 

8.9 

35.1 

25.0 

19 

34.1 

61.9 

50.9 

32.8 

85.4 

29.5 

27.1 

23.2 

31.5 

45.0 

26.3 

21.1 

33.6 

31.7 

20.5 

16.8 

34.5 

34.4 

50.7 

43.1 

29.4 

54.1 

93.5 

86.1 

47.8 

47.1 

36.9 

22.5 

49.1 

86.0 

79.3 

43.6 

135.5 

125.0 

50.0 

47.4 

40.5 

52.9 

74.8 

51.1 

41.6 

63.0 

31.3 

31.1 

25 

40.2 

38.7 

43.1 

41.5 

33.8 

45.4 

69.9 

42.8 

31.7 

56.7 

33.5 

29.2 

20.4 

37.9 

31.7 

11.9 

5.7 

4.2 

12.1 

30.5 

21.2 

17.9 

38.4 

5.5 

4.3 

3.8 

5.6 

19.7 

9.5 

4.8 

17.3 

9 

6.7 

4.6 

9.1 

26.6 

33.4 

24.3 

19.2 

32.7 

71.3 

51 

30.1 

102.4 

29.9 

24.8 

23.1 

28.7 

46.9 

25.8 

21.7 

34.9 

22.7 

19.3 

16.0 

25.9 

36.9 

29 

17.3 

14.7 

23.9 

73.3 

54.4 

47.1 

90.1 

19.3 

16.5 

15.9 

18.2 

50.1 

23.6 

20.1 

33.7 

22.3 

16.2 

12.6 

19.1 

17.5 

20 

 
  
  
 
Recovery [%] 

24h 

48h 

72h 

96h 

144h 

168h 

Synthetic  
pyrethroid (n=5) 

Median  

1st Quartile  

3rd Quartile  

9.4 

8.5 

10 

16.0 

13.6 

22.5 

32.5 

22.7 

57.5 

27.4 

24.4 

47.3 

25.3 

23.0 

56.7 

19.4 

16.7 

44.2 

Manual  
agitation 

15.2 

13.2 

20.3 

Figure 9. Pesticides passive extraction exercise results 

]

%

[

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120

100

80

60

40

20

0

Herbicide methyl
esters

Organochlorines

Organonitrogen

Organophosphorous Synthetic pyrenthroid

Pesticides categories

Average of 24h
Average of 144h

Average of 48h
Average of 168h

Average of 72h
Average of Manual agitation

Average of 96h
Average of Reference

Source: JRC Water Laboratory 

Passive extraction for 144h recorded the highest recovery for overall 88 pesticides and for all 
groups, except for organophosphorous, for which maximum recovery was recorded after 168h. 
Herbicide methyl esters and organonitrogen recoveries (144h, 168h) are at the same level or higher 
than those of the reference standard extraction. Organochlorines, organophosphorous and synthetic 
pyrethroids recoveries, even at the maximums (144h, 168h), range between 30 and 50%, values 
that are significantly lower than the reference standard extraction (80 - 110 %). Manual agitation 
recoveries go from 5.5 % (Organochlorines) to 30.5 % (Herbicide methyl esters), while overall aver-
age recovery is 11.9%. For both passive extraction and manual agitation exercises, the 1st Quartile 
of the average recovery was always below 50 %. 

21 

 
  
  
 
 
 
5.3  Discussion 

The passive extraction exercise was useful in defining the development of the protocol to be 
implemented in the citizen science project “The Gems of Water”, in which citizens are asked to 
collect and extract water samples using the stir bars. Based on the results obtained from the 
passive extraction and manual agitation exercises, for which only herbicide methyl esters and 
organonitrogen pesticides showed satisfactory recoveries, and for which 1st Quartile was always 
below 50%, it was decided that reference standard extraction using magnetic stirring is the most 
suitable method of extraction. Therefore, the kit provided to citizens as part of “The Gems of Water” 
project should include magnetic stirrers. 

22 

 
6  Testing of isochronous stability 

Isochronous stability testing was carried out to investigate how shipping and storing water samples 
can alter those and impact the detected concentrations of analytes. In the “The Gems of Water” 
project, statistical analysis is used to assess the stability of organic compounds in water samples 
with the SBSE. Thus, the isochronous stability study aims to understand the stability of compounds 
at different temperatures and to establish a protocol for transport and storage of the stir bars, 
after extraction. This test is essential in the deployment of the stir bars for water quality monitoring 
exercises worldwide, therefore different logistic conditions and timings need to be considered. The 
isochronous stability test was performed on 88 pesticides and 7 PCBs, as quality control and 
stability control. 

6.1  Statistical Analysis 

In an isochronous stability study, where isochronous refers to the method’s scheme, samples are 
exposed at a testing temperature for specified intervals of time, after which they are stored back at 
4°C, the reference temperature, before being analysed under repeatability conditions (i.e. a single 
analytical run). 

The calculated stability and related uncertainty are based on regression analysis of concentration 
measurements over time intervals and on significance testing of the regression line (Linsinger et al. 
2001). 

The study design was based on previous isochronous exercised by Gawlik et al. (2012) and on 
stability of reference material by Linsinger at al. (Linsinger et al. 2001). 

The stability of the measured compounds concentration is evaluated through a linear equation, with 
the assumption of a linear degradation over time. Thus, the slope (Equation 1) and the standard 
uncertainty of the slope (seb) (Equation 2) must be considered according to the following equations: 

(1) Slope = b = 

∑(𝑥𝑖−𝑥)(𝑦𝑖−𝑦)
∑(𝑥𝑖−𝑥)2

(2) Standard Uncertainty of the slope = seb = 

𝑆𝑦∗𝑥
√∑(𝑥𝑖−𝑥)2 

In the reported equations, xi and yi are the individual time points and their relative measurement 
results, 𝑥 and 𝑦 are the average of all the xi and yi over the total number of measurements. It 
follows that the number of measurements and the time-lap between measurements affect the 
uncertainty of the slope (seb) (Equation 2), which will result smaller, the more analytical 
measurements are performed, and the more time points are distanced from the average time.  

Isochronous stability data must firstly be analysed for the absence of any evident significant trend 
of degradation. The significance of degradation trend can be determined using t-test or F-test.  

Using a t-test, the standard error of the slope can be calculated (Equation 3), with x corresponding 
to the time values of the measurement points,  𝑥 to the average of all x values and Sy,x to the 
standard error of the estimate.  

(3) Standard Error of the Slope = ub = 

𝑆𝑦,𝑥
√(𝑥𝑖−𝑥)

23 

 
 
 
ub results to be dependent on the standard error of the estimate (Sy,x) and the number of relative 
position of the measurement times x.  

Sy,x can finally be considered as the standard deviation around the regression line (Equation 4):  

(4) 𝑆𝑦,𝑥 = √∑(𝑦−𝑦^)2

𝑛−2

where y are the measured concentrations, ŷ the concentration from the regression line and n is the 
total number of measurements. The slope is tested for significance by comparing b/ub to the value 
of t-statistic with a given confidence level and n-2 degree of freedom. Likewise, the standard error 
of the slope (Equation 4) can be used to identify, for a defined time (i.e. 6 weeks), the uncertainty 
(Equation 5), which is itself used compared to an acceptable range of uncertainty (i.e. 20%) to 
compute the shelf-life time or expiry date for a sample. 

The shelf-life, defined generally as “the length of time a product may be stored without becoming 
unsuitable for use” (Tanner 2016), can indeed be interpreted as an expression of the acceptable 
uncertainty attributable to degradation or volatility of certain compounds. Obviously, if the slope 
value (b/ub) is significantly different from 0, indicating degradation, the shelf-life is not computed. 
Statistical analysis was performed using Excel software. 

(5) If slope ≠ 0, Uncertainty [%] = 𝑢𝑏 ∗ 6 𝑤𝑒𝑒𝑘𝑠 ∗ 100 

6.2  Study design 

The isochronous stability study included the exposure of stir bars according to the scheme below 
(Figure 10).  

Figure 10. Isochronous stability design over 6 weeks 

Isochronous stability scheme

3x Sample 6

3x Sample 5

3x Sample 4

3x Sample 3

3x Sample 2

3x Sample 1

3x Reference sample

0

1

2

3

4

5

6

Weeks

25°C

4 °C

Source: modified from Gawlik et al. (2012) 

24 

 
 
The testing temperature is 25°C. Such temperature was chosen to accommodate different 
environmental and room temperature condition considering a potential global rollout of the stir bar 
monitoring method (Figure 11). Reference temperature was 4°C. The total duration of the study was 
6 weeks and stir bars incubation conditions were changed based on the scheme above (Figure 10). 
Measurements were carried out at the end of the sixth week. Stir bars were analysed with GC-qTOF 
MS according to the procedure described in Section 2.2. 

Figure 11. Samples for stability testing are kept in the oven at 25°C 

Source: JRC Water Laboratory 

The water samples analysed in the isochronous stability study were taken from a drinking water 
dispenser located at the JRC Ispra site. The volume for each sample was 100 ml and each 
observation was in triplicates (Figure 10). Each water sample was spiked with 10 µl of native 
solutions (1 ng/µl), diluted in 1 ml of acetone, the details of which are described in section 2.1 
Materials and Methods. 2 µl of Internal standard solution (5 ng/µl) was injected directly in the 
desorption tube before analysis, with the Multipurpose Sampler Injection system.  

All samples spiked with natives solutions were extracted according to the standard extraction 
method, previously described in Section 2.2.2. After extraction, the stir bars were taken out from the 
water samples with help of a magnetic stick and stored in their respective vials at defined 
temperature according to the above described isochronous stability design scheme (Figure 10). 

6.3  Results 

To better understand the results of the many compounds included in this study, based on the 
calculated statistical uncertainty over a period of 6 weeks, compounds can be classified in regards 
to their stability as very good (<25%), good (25-50%), bad (50-75%) and very bad (>75%). For the 
example compounds discussed below, Table 9 shows the results of the statistical analysis. If slope 
is not equal to 0, uncertainty was computed over a period of 6 week, while the shelf-life was 
determined for a fixed uncertainty of 20%.  

PCBs were introduced in the study for their known stability over time, thus they are used as quality 
control for potential analytical variability or even failure. Results of PCBs stability and data are 
reported in Table 9 for individual PCBs and in form of simple statistics, while graphical 
representations (Figure 12, 13) of results are shown only for few example compounds.  

25 

 
Table 9. Uncertainty and shelf-life for 7 individual PCBs with overall statistics (U = Uncertainty; we = weeks)  

Uncertainty  
[-]  
(6 we)  

Uncertainty  
[%]  
(6 we)  

Shelf-life [we]  
(U=20%)  

PCB-28 

PCB-52 

PCB-101 

PCB-118 

PCB-138 

PCB-153 

PCB-180 

Average 

Median 

1st Quartile 

3rd Quartile 

0.81 

0.07 

0.09 

0.10 

0.09 

0.08 

0.09 

0.19 

0.09 

0.08 

0.10 

Overall 

81 

7 

9 

10 

9 

8 

9 

19 

9 

8 

10 

1 

16 

13 

12 

14 

15 

13 

12 

13 

12 

14 

The isochronous stability study confirmed stability of 7 PCBs present in the native solution for the 
whole duration of the exercise at 25 °C. The average calculated uncertainty was 19%, with a 
minimum value of 7% calculated for PCB-52, and a maximum value of 81% for PCB-28. 
Considering an acceptable uncertainty of 20%, this means corresponds to an average shelf-life C of 
12 weeks at 25°. All compounds, except for PCB-28, fall into the “very good” category, according to 
a qualitative classification based on the calculated statistical uncertainty.  

Because of the extensive amount of compounds included in the stability study, graphs of stability 
reports are presented only for PCB-52 and PCB-118 (Figure 12, 13). It might be interesting to note 
that the trend within and between samples is similar for the 2 compounds, signifying reproducibility 
of the method. Looking at the results of the statistical analysis, for a shelf-life of 6 weeks, the 
uncertainty of quantification is 9% for PCB-118 and 7% for PCB-52. If uncertainty is set at 20%, 
the shelf-life extends to 12 weeks for PCB-118 and 16 weeks for PCB-52. 

26 

 
  
 
Figure 12. Stability slope for 3 replicates for PCB-52 

Stability of PCB-52

Slope ≠0 
Set Shelf-life [we] 
Uncertainty [%} 
Set Uncertainty [%] 
Shelf life [we] 

NO 
6 
7.40 
20 
16 

0

1

2

3
Weeks

4

5

6

Replicate 1

Replicate 2

Replicate 3

Source: JRC Water Laboratory 

Figure 13. Stability slope for 3 replicates for PCB-52 

Stability PCB-118

Slope ≠ 0 
Set Shelf-life [we] 
Uncertainty [%} 
Set Uncertainty [%] 
Shelf life [we] 

NO 
6 
9.91 
20 
12 

160

140

120

100

80

60

40

20

0

160

140

120

100

80

60

40

20

0

]

%

[

y
r
e
v
o
c
e
R

]

%

[

y
r
e
v
o
c
e
R

0

1

2

3

4

5

6

Replicate 1

Weeks
Replicate 2

Replicate 3

Source: JRC Water Laboratory 

Isochronous stability was tested for 88 pesticides included in the native solutions. For five of the 
tested pesticides (diazinon, isazophos, disulfoton, fenchlorphos and terbufos) the regression slope 
was significantly different from 0, thus indicating degradation. For those compounds the shelf-life 
and the uncertainty were not computed and are therefore excluded from statistical analysis and 
discussion. Results are presented per group in Table 10: herbicide methyl esters, organochlorines, 
organonitrogen, organophosphorous and synthetic pyrethroids. Individual results are reported in 
Annex 8.  

27 

 
 
 
 
 
 
 
Table 10. Average, median, 1st and 3rd quartiles uncertainty over 6 weeks and shelf-life for a set uncertainty 
of 20% for 5 different pesticides groups (U = Uncertainty; we = weeks) 

When Slope = 0 

Overall (n=83) 

Herbicide  
methyl  
esters (n=3) 

Organochlorines  
(n=33) 

Organonitrogen  
(n=20)  

Organophosphorous  
(n=22) 

Synthetic  
pyrethroid (n=5) 

Average 

Median  

1st Quartile  

3rd Quartile  

Average 

Median  

1st Quartile  

3rd Quartile  

Average 

Median  

1st Quartile  

3rd Quartile  

Average 

Median  

1st Quartile  

3rd Quartile  

Average 

Median  

1st Quartile  

3rd Quartile  

Average 

Median  

1st Quartile  

3rd Quartile  

Uncertainty 
[-]  
(6 we) 
0.4 

Uncertainty  
[%] 
(6 we) 
36 

Shelf-life 
[we]  
(U=20%) 
8 

0.2 

0.1 

0.3 

0.5 

0.4 

0.3 

0.7 

0.1 

0.1 

0.1 

0.1 

0.5 

0.3 

0.1 

0.3 

0.5 

0.3 

0.2 

0.4 

0.7 

0.3 

0.3 

0.3 

22 

10 

30 

51 

40 

26 

71 

13 

10 

8 

14 

49 

27 

12 

34 

51 

29 

24 

44 

67 

28 

28 

32 

5 

4 

12 

5 

3 

2 

7 

12 

12 

8 

14 

6 

4 

4 

10 

4 

4 

3 

5 

4 

4 

4 

4 

Overall, at an acceptable uncertainty of 20%, the average shelf-life is 8 weeks, with 1st and 3rd 
quartile range going from 4 up to 12 weeks. Looking at the single pesticides groups, syntethic 
pyrethroid and organophosphorous compounds resulted in an average shelf-life of 4 weeks. They 
did not show significant difference between 1st and 3rd quartile and the average calculated shelf-
life, indicating that individual pesticides within these groups have similar chemical behaviour.  

Organochlorines resulted in the most stable group, with an average shelf-life of 12 weeks and the 
3rd quartile of 14 weeks. The group of herbicide methyl esters, represented only by 3 individual 
pesticides, showed biggest variability between the 1st (2) and 3rd (7) quartile. 2-phenylphenol is the 
most stable of the group, with 10 weeks of shelf-life, followed by chlozolinate with 3 weeks of 
shelf-life. Chlorpropham is the least stable, with only 1 week of shelf-life. 

Figure 14 to 16 show examples of slopes plotted for stability test calculations for 3 compounds, 
endosulfan I, carbophenthion and pyrachlofos, covering three different stability situations. The 
shelf-life of the three compounds ranged from 1 week (pyrachlofos), to 4 (carbophenthion) to 12 
weeks (endosulfan I). 

28 

 
  
 
]

%

[

y
r
e
v
o
c
e
R

Figure 14. Stability slope for 3 replicates for endosulfan I 

Stability of endosulfan I 

Slope ≠ 0 

Set Shelf-life [we] 
Uncertainty [%} 
Set Uncertainty [%] 
Shelf life [we] 

NO 

6 
7.97 
20 
15 

160

140

120

100

80

60

40

20

0

0

1

2

Replicate 1

3
Weeks
Replicate 2

4

5

6

Replicate 3

Source: JRC Water Laboratory 

Figure 15. Stability slope for 3 replicates for carbophention 

Stability of carbophenthion

]

%

[

y
r
e
v
o
c
e
R

Slope ≠ 0 
Set Shelf-life [we] 
Uncertainty [%} 
Set Uncertainty [%] 
Shelf life [we] 

NO 
6 
29 
20 
4 

500

400

300

200

100

0

0

1

2

Replicate 1

3
Weeks
Replicate 2

4

5

6

Replicate 3

Source: JRC Water Laboratory 

29 

 
 
 
 
 
 
 
 
 
 
 
 
 
 
]

%

[

y
r
e
v
o
c
e
R

1200

1000

800

600

400

200

0

0

Figure 16. Stability slope for 3 replicates for pyrachlofos 

Stability of pyrachlofos

Slope ≠ 0 
Set Shelf-life [we] 
Uncertainty [%} 
Set Uncertainty [%] 
Shelf life [we] 

NO 
6 
99 
20 
1 

1

2

Replicate 1

3
Weeks
Replicate 2

4

5

6

Replicate 3

Source: JRC Water Laboratory 

6.4  Discussion 

Results of PCBs confirmed their stability over a period of 6 weeks, therefore, ensuring the quality of 
the analytical experiment as no external event compromised the test. The only exception was the 
variability recorded for PCB-28, probably due to its volatility. In the wide diversity of compounds 
tested for stability, only 5 showed instability under chosen conditions. Overall, the majority of 
pesticides belonging to the groups (72.7%) are on average stable for 4 weeks at 25°C, as indicated 
by the shelf-life 1st Quartile averaged for the 88 pesticides.  

30 

 
 
7 Conclusions  

The study described in this report allowed the Authors to define a suitable method parameters and 
protocols for the combined use of Stir Bar Sorptive Extraction, to be performed by citizen scientists, 
and Gas Chromatography Quadruple Time of Flight High Resolution Mass Spectrometry, to be con-
ducted at the JRC Water Laboratory, in citizens’ engagement activities for monitoring pesticides in 
water. The results of the reproducibility and recovery tests show that the method is robust and reli-
able. The method of extraction is relatively simple and easy to apply. It is, therefore, a good candi-
date for citizen science initiatives, even if it is limited to the extraction of the dissolved fraction of 
pesticides occurring in water. In this study, different active and passive extraction modalities were 
tested to identify possible protocol simplifications. Extraction using magnetic stirring for 5h showed 
the best performance in terms of recovery, compared to passive extraction and manual agitation. 
Therefore, this was adopted for “The Gems of Water” citizens’ engagement initiative. Furthermore, 
given its small size, the stir bar facilitates shipment of samples between countries, and outside of 
Europe, while guaranteeing compounds stability. Stability during transport and storage was tested 
in this study following an isochronous design. In the vast diversity of compounds tested for stability, 
only 5 out of 88 compounds showed instability under chosen conditions. Overall, the majority of 
pesticide groups are, on average stable for at least 4 weeks at 25°C, theoretically guaranteeing sta-
bility during shipment when the temperature cannot be controlled. Four weeks time can be consid-
ered sufficient to deliver the stir bars within and outside Europe. The method developed in this 
study is planned to be used to sample surface water in different worldwide countries, including 
Costa Rica, Kenya, Romania, Bulgaria and Australia. The development of new screening methods 
and technologies for water quality monitoring is essential for addressing the increasing contamina-
tion by pesticides of water bodies globally. 

31 

 
 
8 References 

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90010_Pesticide_PCDL_QuickStart.pdf. 

Agriculture & Environment Research Unit (AERU). 2018. “IUPAC Pesticide Properties DataBase 
(PPDB).” University of Hertfordshire. http://sitem.herts.ac.uk/aeru /ppdb/en/. 

Brack, Werner, Beate I. Escher, Erik Müller, Mechthild Schmitt-Jansen, Tobias Schulze, Jaroslav 
Slobodnik, and Henner Hollert. 2018. “Towards a Holistic and Solution-Oriented Monitoring of 
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Cacciatori, C., G. Mariani, A. Carollo, S. Tavazzi, Elelman Elelman, N. Glowacka, T. Sullivan, T. Casado 
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Cacciatori, Caterina, Giulio Mariani, Sara Comero, Daniela Marin, Maria Cabrera, Jennifer Bon-
Tavarnese, Joel Gaggstatter, et al. 2024. “‘The Gems of Water’: A Co-Created Scientist-Citizen 
Approach for Water Quality Monitoring.” Frontiers in Water 6. 
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Campanale, Claudia, Carmine Massarelli, Daniela Losacco, Donatella Bisaccia, Mariangela Triozzi, 
and Vito Felice Uricchio. 2021. “The Monitoring of Pesticides in Water Matrices and the Analytical 
Criticalities: A Review.” TrAC Trends in Analytical Chemistry 144 (November): 116423. 
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David, Frank, Nobuo Ochiai, and Pat Sandra. 2019. “Two Decades of Stir Bar Sorptive Extraction: A 
Retrospective and Future Outlook.” TrAC Trends in Analytical Chemistry 112: 102–11. 
https://doi.org/10.1016/j.trac.2018.12.006. 

Dulio, Valeria, Bert van Bavel, Eva Brorström-Lundén, Joop Harmsen, Juliane Hollender, Martin 
Schlabach, Jaroslav Slobodnik, Kevin Thomas, and Jan Koschorreck. 2018. “Emerging Pollutants in 
the EU: 10 Years of NORMAN in Support of Environmental Policies and Regulations.” Environmental 
Sciences Europe 30 (1): 5. https://doi.org/10.1186/s12302-018-0135-3. 

European Council, and European Parliament. 2013. “Directive 2013/39/EU of the European 
Parliament and of the Council of 12 August 2013 Amending Directives 2000/60/EC and 
2008/105/EC as Regards Priority Substances in the Field of Water Policy Text with EEA Relevance.” 

Gawlik, Bernd Manfred, Robert Loos, Giovanni Bidoglio, Gisela Fauler, Xinghua Guo, Ernst Lankmayr, 
and Thomas Linsinger. 2012. “Testing Sample Stability in Short-Term Isochronous Stability Studies 
for EU-Wide Monitoring Surveys of Polar Organic Contaminants in Water.” TrAC Trends in Analytical 
Chemistry 36 (June): 36–46. https://doi.org/10.1016/j.trac.2012.04.001. 

Hollender, Juliane, Bert van Bavel, Valeria Dulio, Eivind Farmen, Klaus Furtmann, Jan Koschorreck, 
Uwe Kunkel, et al. 2019. “High Resolution Mass Spectrometry-Based Non-Target Screening Can 
Support Regulatory Environmental Monitoring and Chemicals Management.” Environmental Sciences 
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Lerch, Oliver, Jasmin Zbron, Ken Brady, and Juan-Luis Aybar. 2018. “Highly Sensitive Determination 
of Contaminants in Surface Water in the Context of the EU Water Framework Directive Using Stir 
Bar Sorptive Extraction (SBSE) and GC-MS/MS.” GERSTEL Application Note, no. 196. 

Linsinger, Thomas P. J., J. Pauwels, Andr&#x000E9;e Lamberty, H.G. Schimmel, Adriaan M. H. van der 
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Mariani, Giulio, Simona Tavazzi, Helle Skejo, Sara Comero, Peter Oswald, Marina Litvinona, Bernd 
Manfred Gawlik, and Georg Hanke. 2020. “EMBLAS Plus - Joint Black Sea Survey 2019: ‘JRC 
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33 

 
 
9  List of abbreviations and definitions 

Abbreviations 

Definitions 

CF 
CIS 
CV 
EG 
EI 
EPA 
EQS 

GC-QToF-HRMS 

GEMS/Water 
JRC  
LOD 
LOQ 
LPE 
MDL 
MPS 
OCP 
PAH 
PCB 
PCDL 
PDMS 
POCIS 
PPDB 
PTV 
RPM 
RRF 
SBSE 
SD 
TD 
TDU 
UNEA 
WFD 
WWQA  

Calibration Factor 
Cooling Injection System  
Coefficient of Variation 
Ethylene glycol 
Electron Ionization 
United States Environmental Protection Agency 
Environmental Quality Standard  
Gas Chromatography Quadruple Time of Flights High Resolution 

Mass Spectrometry  

United Nations Global Environment Monitoring System  
Joint Research Centre 
Limit of Detection 
Limit of Quantification 
Liquid Phase Extraction 
Method Detection Limit 
Multipurpose Sampler  
Organochlorines Pesticides 
Polyaromatic Hydrocarbons 
Polychlorinated Biphenyls 
Personal Compound Database and Library  
Polydimethylsiloxane 
Polar Organic Chemical Integrative Sampler 
Pesticides Properties DataBase  
Programmable Temperature Vaporizer  
Rotation per Minute 
Response Ratio Factor 
Stir Bar Sorptive Extraction 
Standard Deviation 
Thermal Desorption 
Thermal Desorption Unit 
United Nations Environment Assembly 
Water Framework Directive 
World Water Quality Alliance 

34 

 
 
 
10  List of Figures 

Figure 1. Workflow of “The Gems of Water” activity. ...................................................................................................... 4 

Figure 2. Share of pesticides categories in the screen method ................................................................................ 8 

Figure 3. Stir bars in their vials ................................................................................................................................................. 10 

Figure 4. GC-QTOF-HRMS ............................................................................................................................................................. 11 

Figure 5. Thermal Desorption Unit and Cooled Injection System .......................................................................... 13 

Figure 6. Response over the 10 injections averaged for all PCBs compounds ............................................. 14 

Figure 7. Average recovery for all 88 pesticides, ordered by categories ......................................................... 17 

Figure 8. Sketch of extraction exercise i). passive extraction, ii). manual agitation ................................... 19 

Figure 9. Pesticides passive extraction exercise results ............................................................................................. 21 

Figure 10. Isochronous stability design over 6 weeks ................................................................................................ 24 

Figure 11. Samples for stability testing are kept in the oven at 25°C .............................................................. 25 

Figure 12. Stability slope for 3 replicates for PCB-52 ................................................................................................ 27 

Figure 13. Stability slope for 3 replicates for PCB-52 ................................................................................................ 27 

Figure 14. Stability slope for 3 replicates for endosulfan I...................................................................................... 29 

Figure 15. Stability slope for 3 replicates for carbophention.................................................................................. 29 

Figure 16. Stability slope for 3 replicates for pyrachlofos ....................................................................................... 30 

35 

 
 
11  List of Tables 

Table 1. Calibration curve levels.................................................................................................................................................. 9 

Table 2. High-resolution operational parameters........................................................................................................... 11 

Table 3. QToF reference calibration mass, accuracy and power resolution .................................................... 12 

Table 4. Injections methods for instrumental reproducibility testing ................................................................. 14 

Table 5. Averaged instrument response over 10 injections for the three different injection methods 
for 6 PCB congeners .......................................................................................................................................................................... 14 

Table 6. Average, median, quartiles of recovery and reproducibility reported for pesticides 
categories. ............................................................................................................................................................................................... 17 

Table 7. Scheme of extraction exercise................................................................................................................................ 19 

Table 8. Average, median, 1st and 3rd quartiles recoveries of different extraction tests for 5 
different pesticides groups ............................................................................................................................................................ 20 

Table 9. Uncertainty and shelf-life for 7 individual PCBs with overall statistics (U = Uncertainty; we 
= weeks) ................................................................................................................................................................................................... 26 

Table 10. Average, median, 1st and 3rd quartiles uncertainty over 6 weeks and shelf-life for a set 
uncertainty of 20% for 5 different pesticides groups (U = Uncertainty; we = weeks) ............................... 28 

36 

 
12  Annexes  

Annex 1. List of screened compounds with respective methods parameters 

Compound Method 

Name 

2,3,5,6-Tetrachloroaniline 

2,4'-DDD 

2,4'-DDE 

2,4'-DDT 

2,4'-Methoxychlor 
2,6-Dichlorobenzonitrile (Dichlo-
benil) 
2-Phenylphenol 

3,4-Dichloroaniline 

4,4'-DDD 

4,4'-DDE 

4,4'-DDT 

4,4'-Dichlorobenzophenone 

4,4'-Methoxychlor olefin 

Acequinocyl 

Acetochlor 

Alachlor 

Aldrin 

Allidochlor 

alpha-BHC 

Anthraquinone 

Atrazine 

Azinphos methyl 

Benfluralin 

Mass ions (m/z) 
Qualifier 
1 
232.8958 

Qualifier 
2 
228.9018 

Quanti-
fier 
230.8988 

RT 

12.818 

23.719 

235.0086 

237.0052 

165.0701 

22.249 

317.9352 

315.9381 

246.0002 

25.039 

235.0080 

237.0050 

165.0700 

26.73 

121.0654 

227.1078 

152.0623 

7.71 

170.9660 

172.9616 

174.9580 

10.679 

170.0736 

169.0654 

141.0701 

9.098 

160.9798 

162.9767 

164.9737 

24.939 

235.0090 

237.0052 

165.0700 

23.418 

246.0001 

247.9973 

317.9352 

26.262 

235.0084 

165.0701 

237.0052 

20.009 

138.9949 

140.9918 

249.9951 

26.013 

308.0375 

310.0345 

238.0993 

33.938 

342.2197 

343.2232 

188.0470 

18.055 

146.0967 

223.0762 

147.1037 

18.422 

188.1073 

237.0919 

189.1108 

19.549 

262.8568 

264.8539 

292.9272 

6.768 

138.0917 

158.0372 

160.0341 

14.321 

180.9376 

182.9346 

218.9113 

19.565 

208.0524 

209.0555 

180.0574 

15.321 

200.0700 

202.0670 

215.0934 

29.364 

132.0446 

160.0508 

77.0386 

14.027 

292.0549 

318.1069 

276.0597 

37 

ISTD Method 

Qualifier 
3 

Name 

trans-Nonachlor_C13 

2,4'-DDD_C13 

2,4'-DDE_C13 

2,4'-DDT_C13 

Mass ions (m/z) 
Qualifier 
1 
420.8154 

Qualifier 
2 
416.8213 

Quanti-
fier 
418.8182 

247.0485 

249.0455 

177.1106 

329.9755 

331.9726 

258.0405 

247.0484 

249.0455 

177.1106 

trans-Nonachlor_C13 

418.8182 

420.8154 

416.8213 

trans-Nonachlor_C13 

418.8182 

420.8154 

416.8213 

trans-Nonachlor_C13 

418.8182 

420.8154 

416.8213 

trans-Nonachlor_C13 

418.8182 

420.8154 

416.8213 

2,4'-DDD_C13 

4,4-DDE_C13 

4,4'-DDT_C13 

247.0485 

249.0455 

177.1106 

329.9756 

327.9785 

258.0405 

247.0484 

249.0455 

177.1105 

trans-Nonachlor_C13 

418.8182 

420.8154 

416.8213 

trans-Nonachlor_C13 

418.8182 

420.8154 

416.8213 

trans-Nonachlor_C13 

418.8182 

420.8154 

416.8213 

trans-Nonachlor_C13 

418.8182 

420.8154 

416.8213 

trans-Nonachlor_C13 

418.8182 

420.8154 

416.8213 

Aldrin_13C 

269.8804 

271.8775 

304.9676 

trans-Nonachlor_C13 

418.8182 

420.8154 

416.8213 

alpha-BHC_13C 

224.9314 

226.9284 

186.9576 

trans-Nonachlor_C13 

418.8182 

420.8154 

416.8213 

trans-Nonachlor_C13 

418.8182 

420.8154 

416.8213 

trans-Nonachlor_C13 

418.8182 

420.8154 

416.8213 

trans-Nonachlor_C13 

418.8182 

420.8154 

416.8213 

 
 
  
  
  
  
  
  
  
  
  
  
  
  
  
  
  
  
  
  
  
  
  
  
  
Compound Method 

Name 

beta-BHC 

Bifenthrin 

Bioallethrin 

Biphenyl 

Bromfenvinfos-methyl 

Bromfenviphos 

Bromophos ethyl 

Bromophos methyl 

Bromopropylate 

Bupirimate 

Captafol 

Captan 

Carbophenthion 

Carfentrazone ethyl 

Chlorbenside 

Chlorfenapyr 

Chlorfenson (Ovex) 

Chlorfenvinphos 

Chlorobenzilate 

Chloroneb 

Chlorothalonil 

Chlorpropham 

Chlorpyrifos 

Chlorpyrifos methyl 

Chlorthiophos 

Chlozolinate 

cis-Chlordane 

Mass ions (m/z) 
Qualifier 
1 
218.9112 

Qualifier 
2 
182.9345 

Quanti-
fier 
180.9375 

ISTD Method 

Qualifier 
3 

Name 

gamma-BHC_13C 

RT 

15.36 

Mass ions (m/z) 
Qualifier 
1 
226.9286 

Qualifier 
2 
186.9577 

Quanti-
fier 
224.9315 

28.325 

181.1047 

182.1048 

166.0778 

21.6 

123.1172 

136.0884 

124.1206 

8.268 

154.0814 

153.0700 

155.0811 

21.486 

294.9704 

296.9674 

340.9177 

23.03 

266.9387 

268.9358 

323.0015 

22.239 

358.9105 

356.9127 

302.8476 

20.594 

330.8799 

328.8815 

315.8554 

28.103 

340.9005 

342.8979 

338.9019 

24.005 

273.1023 

274.1050 

316.1572 

26.977 

79.0543 

77.0387 

312.9315 

21.429 

149.0473 

79.0543 

116.9062 

25.89 

341.9746 

343.9715 

156.9880 

26.096 

312.0593 

310.0193 

330.0256 

21.816 

125.0164 

127.0124 

267.9880 

24.459 

363.9412 

361.9434 

247.0482 

22.865 

174.9618 

176.9588 

110.9998 

21.548 

323.0017 

324.9990 

266.9389 

24.618 

251.0035 

253.0001 

138.9949 

10.576 

190.9664 

192.9634 

205.9899 

16.709 

265.8789 

267.8759 

263.8817 

13.336 

213.0554 

215.0526 

154.0420 

19.993 

96.9508 

124.9821 

168.9248 

18.111 

285.9261 

287.9231 

124.9822 

25.301 

268.9270 

270.9240 

359.9590 

21.405 

258.9801 

260.9773 

185.9874 

22.555 

372.8262 

376.8203 

236.8412 

38 

trans-Nonachlor_C13 

418.8182 

420.8154 

416.8213 

trans-Nonachlor_C13 

418.8182 

420.8154 

416.8213 

trans-Nonachlor_C13 

418.8182 

420.8154 

416.8213 

trans-Nonachlor_C13 

418.8182 

420.8154 

416.8213 

trans-Nonachlor_C13 

418.8182 

420.8154 

416.8213 

trans-Nonachlor_C13 

418.8182 

420.8154 

416.8213 

trans-Nonachlor_C13 

418.8182 

420.8154 

416.8213 

trans-Nonachlor_C13 

418.8182 

420.8154 

416.8213 

trans-Nonachlor_C13 

418.8182 

420.8154 

416.8213 

trans-Nonachlor_C13 

418.8182 

420.8154 

416.8213 

trans-Nonachlor_C13 

418.8182 

420.8154 

416.8213 

trans-Nonachlor_C13 

418.8182 

420.8154 

416.8213 

trans-Nonachlor_C13 

418.8182 

420.8154 

416.8213 

trans-Nonachlor_C13 

418.8182 

420.8154 

416.8213 

trans-Nonachlor_C13 

418.8182 

420.8154 

416.8213 

trans-Nonachlor_C13 

418.8182 

420.8154 

416.8213 

trans-Nonachlor_C13 

418.8182 

420.8154 

416.8213 

trans-Nonachlor_C13 

418.8182 

420.8154 

416.8213 

trans-Nonachlor_C13 

418.8182 

420.8154 

416.8213 

trans-Nonachlor_C13 

418.8182 

420.8154 

416.8213 

trans-Nonachlor_C13 

418.8182 

420.8154 

416.8213 

trans-Nonachlor_C13 

418.8182 

420.8154 

416.8213 

trans-Nonachlor_C13 

418.8182 

420.8154 

416.8213 

trans-Nonachlor_C13 

418.8182 

420.8154 

416.8213 

trans-Nonachlor_C13 

418.8182 

420.8154 

416.8213 

trans-Nonachlor_C13 

418.8182 

420.8154 

416.8213 

 
 
  
  
  
  
  
  
  
  
  
  
  
  
  
  
  
  
  
  
  
  
  
  
  
  
  
  
  
Compound Method 

Name 

cis-Nonachlor 

cis-Permethrin 

Clomazone (Command) 

Coumaphos 

Cycloate 

Cyfluthrin 

Cypermenthrin 

Cyprodinil 
DCPA methyl ester (Chlorthal-dime-
thyl) 
delta-BHC 

Deltamethrin 

Diallate (cis and trans) 

Diazinon 

Dichlofluanid 

Dichloran 

Dieldrin 

Dimethachlor 

Diphenamid 

Diphenylamine 

Disulfoton 

Edifenphos 

Endosulfan ether 

Endosulfan I 

Endosulfan II 

Mass ions (m/z) 
Qualifier 
1 
410.7813 

Qualifier 
2 
406.7872 

Quanti-
fier 
408.7843 

ISTD Method 

Qualifier 
3 

Name 

cis-Nonachlor_C13 

Mass ions (m/z) 
Qualifier 
1 
239.8610 

Qualifier 
2 
418.8183 

Quanti-
fier 
241.8580 

183.0824 

181.0651 

163.0078 

trans-Nonachlor_C13 

418.8182 

420.8154 

416.8213 

204.1023 

205.1056 

125.0154 

trans-Nonachlor_C13 

418.8182 

420.8154 

416.8213 

RT 

25.021 

31.594
2 
15.392 

31.979 

362.0145 

364.0120 

333.9831 

13 

154.1230 

186.0951 

155.1263 

33.108 

163.0079 

165.0050 

33.778 

181.0651 

182.0685 

20.903 

224.1217 

225.1264 

206.0604 
163.0079  209.0836 
226.1291 

20.147 

300.8815 

302.8779 

331.8993 

16.517 

180.9375 

182.9345 

218.9112 

36.509 

252.9050 

254.9029 

296.8949 

14.203 

234.0719 

236.0689 

192.0247 

16.145 

179.1181 

137.0710 

304.1010 

19.446 

167.0641 

223.9503 

225.9473 

14.776 

205.9645 

207.9616 

175.9665 

23.391 

262.8567 

264.8537 

276.8724 

17.789 

197.0605 

199.0577 

134.0968 

20.656 

167.0862 

165.0701 

239.1309 

12.728 

168.0816 

141.0698 

169.0909 

88.0343 

274.0285 

185.9936 

16.503
6 
26.026 

trans-Nonachlor_C13 

418.8182 

420.8154 

416.8213 

trans-Nonachlor_C13 

418.8182 

420.8154 

416.8213 

trans-Nonachlor_C13 

418.8182 

420.8154 

416.8213 

trans-Nonachlor_C13 

418.8182 

420.8154 

416.8213 

trans-Nonachlor_C13 

418.8182 

420.8154 

416.8213 

trans-Nonachlor_C13 

418.8182 

420.8154 

416.8213 

gamma-BHC_13C 

224.9315 

226.9286 

186.9577 

trans-Nonachlor_C13 

418.8182 

420.8154 

416.8213 

trans-Nonachlor_C13 

418.8182 

420.8154 

416.8213 

Diazinon_d10 

183.1429 

314.1641 

184.1483 

trans-Nonachlor_C13 

418.8182 

420.8154 

416.8213 

trans-Nonachlor_C13 

418.8182 

420.8154 

416.8213 

Dieldrin_C13 

269.8806 

271.8776 

284.8996 

trans-Nonachlor_C13 

418.8182 

420.8154 

416.8213 

trans-Nonachlor_C13 

418.8182 

420.8154 

416.8213 

trans-Nonachlor_C13 

418.8182 

420.8154 

416.8213 

trans-Nonachlor_C13 

418.8182 

420.8154 

416.8213 

310.0258 

172.9829 

201.0142 

trans-Nonachlor_C13 

418.8182 

420.8154 

416.8213 

17.168 

306.8830 

304.8861 

308.8802 

22.428 

338.8730 

340.8700 

236.8409 

24.523 

338.8732 

336.8762 

340.8703 

trans-Nonachlor_C13 

418.8182 

420.8154 

416.8213 

Endosulfan I_C13 

347.9035 

349.9005 

241.8580 

Endosulfan II_C13 

241.8581 

239.8609 

273.9117 

39 

 
 
  
  
  
  
  
  
  
  
  
  
  
  
  
  
  
  
  
  
  
  
  
  
  
Compound Method 

Name 

Endosulfan sulfate 

Endrin 

Endrin aldehyde 

Endrin ketone 

EPN 

Ethalfluralin 

Ethion 

Ethylan (Perthane) 

Etonfenprox 

Etridiazole 

Fenamiphos 

Fenarimol 

Fenchlorphos (Ronnel) 

Fenitrothion 

Fenpropathrin 

Fenson 

Fenthion 

Fenvalerate 

Fipronil 

Fluazifop-p-butyl 

Fluchloralin 

Flucythrinate 

Fludioxinil 

Fluquinconazole 

Fluridone (Sonar) 

Flusilazole 

Mass ions (m/z) 
Qualifier 
1 
386.8403 

Qualifier 
2 
273.8071 

Quanti-
fier 
271.8101 

RT 

26.08 

24.168 

262.8568 

264.8538 

242.9532 

25.226
5 
27.707 

344.8990 

346.8961 

249.8489 

316.9040 

318.9011 

344.8991 

28.137 

156.9875 

169.0414 

141.0101 

13.59 

276.0596 

316.0911 

292.0547 

25.195 

230.9749 

232.9703 

383.9889 

24.381 

223.1518 

224.1520 

167.0858 

33.912 

163.1161 

164.1155 

376.2043 

9.564 

210.9496 

182.9183 

212.9466 

22.978 

303.1067 

288.0831 

260.0516 

30.32 

18.66 

138.9948 

140.9918 

330.0327 

284.9329 

286.9290 

269.9080 

19.187 

277.0172 

260.0144 

124.9821 

28.558 

181.0651 

182.0686 

265.0740 

20.337 

267.9960 

141.0006 

269.9933 

19.905 

278.0222 

280.0174 

245.0404 

35.099 

225.0789 

226.0821 

419.1295 

21.652 

366.9441 

368.9410 

212.9484 

24.461 

282.0747 

283.0776 

254.0426 

16.56 

306.0705 

326.0160 

310.0209 

33.811 

199.0934 

200.0970 

157.0463 

23.392 

248.0402 

249.0429 

182.0478 

31.94 

340.0409 

342.0379 

298.0185 

34.539 

328.0971 

329.1014 

285.0763 

23.863 

233.0610 

234.0623 

315.1001 

40 

ISTD Method 

Qualifier 
3 

Name 

Endosulfan sul-
fate_C13 
Endrin_C13 

Mass ions (m/z) 
Qualifier 
1 

Qualifier 
2 

Quanti-
fier 

276.8271 

278.8242 

235.9194 

269.8805 

271.8776 

291.9642 

trans-Nonachlor_C13 

418.8182 

420.8154 

416.8213 

trans-Nonachlor_C13 

418.8182 

420.8154 

416.8213 

trans-Nonachlor_C13 

418.8182 

420.8154 

416.8213 

trans-Nonachlor_C13 

418.8182 

420.8154 

416.8213 

trans-Nonachlor_C13 

418.8182 

420.8154 

416.8213 

trans-Nonachlor_C13 

418.8182 

420.8154 

416.8213 

trans-Nonachlor_C13 

418.8182 

420.8154 

416.8213 

trans-Nonachlor_C13 

418.8182 

420.8154 

416.8213 

trans-Nonachlor_C13 

418.8182 

420.8154 

416.8213 

trans-Nonachlor_C13 

418.8182 

420.8154 

416.8213 

trans-Nonachlor_C13 

418.8182 

420.8154 

416.8213 

Fenitrothion_d6 

283.0545 

266.0513 

253.0794 

trans-Nonachlor_C13 

418.8182 

420.8154 

416.8213 

trans-Nonachlor_C13 

418.8182 

420.8154 

416.8213 

Fenthion_d6 

284.0572 

281.0515 

251.0778 

trans-Nonachlor_C13 

418.8182 

420.8154 

416.8213 

trans-Nonachlor_C13 

418.8182 

420.8154 

416.8213 

trans-Nonachlor_C13 

418.8182 

420.8154 

416.8213 

trans-Nonachlor_C13 

418.8182 

420.8154 

416.8213 

trans-Nonachlor_C13 

418.8182 

420.8154 

416.8213 

trans-Nonachlor_C13 

418.8182 

420.8154 

416.8213 

trans-Nonachlor_C13 

418.8182 

420.8154 

416.8213 

trans-Nonachlor_C13 

418.8182 

420.8154 

416.8213 

trans-Nonachlor_C13 

418.8182 

420.8154 

416.8213 

 
 
  
  
  
  
  
  
  
  
  
  
  
  
  
  
  
  
  
  
  
  
  
  
  
  
  
  
Compound Method 

Name 

Flutolanil 

Flutriafol 

Folpet 

Fonofos 

gamma-BHC 

Heptachlor 

Heptachlor epoxide (isomer B) 

Hexachlorobenzene 

Hexazinone 

Iodofenphos 

Iprodione 

Isazophos 

Isodrin 

Isopropalin 

lambda-Cyhalothrin 

Lenacil 

Leptophos 

Linuron 

Malathion 

Metalaxyl 

Metazachlor 

Methacrifos 

Methoxychlor 

Methyl parathion 

Mass ions (m/z) 
Qualifier 
1 
174.0246 

Qualifier 
2 
281.0665 

Quanti-
fier 
173.0236 

ISTD Method 

Qualifier 
3 

Name 

trans-Nonachlor_C13 

RT 

23.138 

Mass ions (m/z) 
Qualifier 
1 
420.8154 

Qualifier 
2 
416.8213 

Quanti-
fier 
418.8182 

22.75 

219.0619 

164.0621 

123.0244 

21.669 

259.9338 

261.9309 

296.8999 

trans-Nonachlor_C13 

418.8182 

420.8154 

416.8213 

trans-Nonachlor_C13 

418.8182 

420.8154 

416.8213 

15.957
7 
15.582 

108.9876 

137.0187 

246.0300 

trans-Nonachlor_C13 

418.8182 

420.8154 

416.8213 

180.9375 

218.9112 

182.9345 

gamma-BHC_13C 

224.9315 

226.9286 

186.9577 

18.299 

271.8099 

273.8069 

236.8409 

21.11 

352.8443 

354.8413 

262.8567 

14.592 

283.8100 

285.8070 

281.8130 

26.665 

171.0895 

252.1584 

172.0899 

23.059 

376.8688 

378.8644 

249.9625 

27.801 

314.0101 

316.0073 

186.9589 

16.889 

256.9788 

258.9758 

285.0103 

20.664 

192.9375 

262.8568 

194.9346 

20.947 

280.1303 

238.0828 

309.1692 

197.0342 

199.0313 

208.0759 

30.271
6 
26.149 

Heptachlor_13C 
Heptachlor epox-
ide_C13 
Hexachlorben-
zene_13C 
trans-Nonachlor_C13 

276.8270 

278.8240 

346.8831 

362.8782 

364.8753 

360.8810 

289.8303 

291.8273 

254.8613 

418.8182 

420.8154 

416.8213 

trans-Nonachlor_C13 

418.8182 

420.8154 

416.8213 

Iprodione_d5 

319.0412 

321.0380 

318.0342 

trans-Nonachlor_C13 

418.8182 

420.8154 

416.8213 

Isodrin_13C 

199.9610 

201.9581 

269.8803 

trans-Nonachlor_C13 

418.8182 

420.8154 

416.8213 

trans-Nonachlor_C13 

418.8182 

420.8154 

416.8213 

153.0670 

136.0395 

177.0660 

trans-Nonachlor_C13 

418.8182 

420.8154 

416.8213 

29.46 

376.8996 

374.9017 

378.8968 

19.267 

248.0119 

250.0091 

159.9718 

19.654 

173.0817 

124.9827 

127.0396 

18.636 

206.1177 

249.1362 

160.1122 

21.1 

209.0606 

211.0577 

133.0886 

10.458 

207.9962 

209.0029 

240.0224 

28.38 

227.1102 

228.1105 

274.0760 

18.103 

263.0017 

264.0048 

109.0051 

trans-Nonachlor_C13 

418.8182 

420.8154 

416.8213 

Linuron_d6 

254.0490 

256.0463 

253.0175 

Malathion_d10 

183.1439 

132.0704 

157.9622 

trans-Nonachlor_C13 

418.8182 

420.8154 

416.8213 

trans-Nonachlor_C13 

418.8182 

420.8154 

416.8213 

trans-Nonachlor_C13 

418.8182 

420.8154 

416.8213 

trans-Nonachlor_C13 

418.8182 

420.8154 

416.8213 

trans-Nonachlor_C13 

418.8182 

420.8154 

416.8213 

41 

 
 
  
  
  
  
  
  
  
  
  
  
  
  
  
  
  
  
  
  
  
  
  
  
  
  
Mass ions (m/z) 
Qualifier 
1 
240.0971 

Qualifier 
2 
162.1283 

Quanti-
fier 
238.0998 

ISTD Method 

Qualifier 
3 

Name 

trans-Nonachlor_C13 

RT 

19.778 

Mass ions (m/z) 
Qualifier 
1 
420.8154 

Qualifier 
2 
416.8213 

Quanti-
fier 
418.8182 

9.0697 

127.0161 

192.0186 

224.0447 

20.56 

164.0708 

275.1885 

210.1489 

trans-Nonachlor_C13 

418.8182 

420.8154 

416.8213 

trans-Nonachlor_C13 

418.8182 

420.8154 

416.8213 

271.8102 

273.8072 

236.8410 

N-(2,4-Dimethylphenyl)formamide 

9.946 

149.0837 

150.0870 

179.0248 

181.0219 

150.0108  206.0735 
120.0810 

Compound Method 

Name 

Metolachlor 

Mevinphos 

MGK-264 

Mirex 

Myclobutanil 

Nitralin 

Nitrofen 

Norfluorazon 

Oxadiazon 

Oxyfluorfen 

Paclobutrazol 

Parathion (ethyl parathion) 

Pebulate 

Penconazole 

Pendimethalin 

Pentachloroaniline 

Pentachloroanisole 

Pentachlorobenzene 

29.632
6 
23.731 

20.019
2 
9.622 

27.513 

316.0607 

300.0657 

345.0998 

24.168 

282.9805 

284.9777 

202.0183 

26.194 

303.0387 

305.0360 

302.0310 

23.666 

174.9591 

176.9561 

258.0328 

23.89 

361.0334 

300.0042 

317.0070 

22.278 

236.0590 

238.0561 

167.0261 

291.0332 

155.0038 

96.9510 

21.217 

248.0957 

250.0924 

158.9766 

21.194 

252.0987 

281.1379 

208.0722 

17.328 

264.8602 

266.8572 

262.8631 

14.781 

279.8596 

281.8567 

236.8410 

10.859 

249.8492 

251.8460 

214.8800 

Pentachlorobenzonitrile 
Pentachloronitrobenzene (quinto-
zene) 
Pentachlorothioanisole 

Phenothrin (cis & trans) 

Phorate 

15.824 

274.8446 

276.8417 

272.8476 

15.758 

236.8412 

238.8383 

294.8344 

19.221 

295.8367 

297.8336 

245.8442 

29.231 

183.0808 

184.0859 

123.1172 

14.219 

75.0265 

230.9736 

260.0128 

42 

Mirex_C13 

276.8269 

278.8240 

341.8440 

trans-Nonachlor_C13 

418.8182 

420.8154 

416.8213 

trans-Nonachlor_C13 

418.8182 

420.8154 

416.8213 

trans-Nonachlor_C13 

418.8182 

420.8154 

416.8213 

trans-Nonachlor_C13 

418.8182 

420.8154 

416.8213 

trans-Nonachlor_C13 

418.8182 

420.8154 

416.8213 

trans-Nonachlor_C13 

418.8182 

420.8154 

416.8213 

trans-Nonachlor_C13 

418.8182 

420.8154 

416.8213 

trans-Nonachlor_C13 

418.8182 

420.8154 

416.8213 

Parathion_d10 

301.0957 

115.0426 

302.0987 

trans-Nonachlor_C13 

418.8182 

420.8154 

416.8213 

Pendimethalin_d5 

255.1168 

210.0841 

256.1202 

trans-Nonachlor_C13 

418.8182 

420.8154 

416.8213 

trans-Nonachlor_C13 
Pentachlorben-
zene_13C 
trans-Nonachlor_C13 

418.8182 

420.8154 

416.8213 

255.8691 

257.8662 

220.9002 

418.8182 

420.8154 

416.8213 

trans-Nonachlor_C13 

418.8182 

420.8154 

416.8213 

trans-Nonachlor_C13 

418.8182 

420.8154 

416.8213 

trans-Nonachlor_C13 

418.8182 

420.8154 

416.8213 

Phorate_d10 

241.0360 

243.0321 

270.0749 

128.1072 

132.0844 

161.0871 

trans-Nonachlor_C13 

418.8182 

420.8154 

416.8213 

 
 
  
  
  
  
  
  
  
  
  
  
  
  
  
  
  
  
  
  
  
  
  
  
  
Compound Method 

Name 

Phosalone 

Phosmet 

Piperonyl butoxide 

Pirimiphos ethyl 

Pirimiphos methyl 

Pretilachlor 

Prochloraz 

Procymidone 

Prodiamine 

Profenofos 

Profluralin 

Propachlor 

Propanil 

Propargite 

Propisochlor 

Propyzamide 

Prothiofos 

Pyraclofos 

Pyrazophos 

Pyridaben 

Pyridafenthion 

Pyrimethanil 

Pyriproxyfen 

Quinalphos 

Resmethrin 

Sulfotepp 

Mass ions (m/z) 
Qualifier 
1 
132.0444 

Qualifier 
2 
160.0506 

Quanti-
fier 
182.0005 

ISTD Method 

Qualifier 
3 

Name 

trans-Nonachlor_C13 

RT 

29.386 

Mass ions (m/z) 
Qualifier 
1 
420.8154 

Qualifier 
2 
416.8213 

Quanti-
fier 
418.8182 

27.979 

160.0395 

96.9508 

316.9945 

27.205 

176.0848 

177.0897 

193.0862 

20.901 

333.1278 

168.0592 

318.1043 

19.308 

290.0729 

276.0571 

124.9329 

23.447 

176.1074 

177.1107 

238.0998 

32.088 

308.0016 

309.9987 

180.1136 

21.838 

283.0167 

255.0215 

285.0139 

19.355 

321.0813 

279.0342 

333.1178 

23.306 

338.9653 

336.9673 

373.9341 

318.0706 

330.1070 

347.1097 

16.066
8 
12.572 

trans-Nonachlor_C13 

418.8182 

420.8154 

416.8213 

trans-Nonachlor_C13 

418.8182 

420.8154 

416.8213 

trans-Nonachlor_C13 

418.8182 

420.8154 

416.8213 

trans-Nonachlor_C13 

418.8182 

420.8154 

416.8213 

trans-Nonachlor_C13 

418.8182 

420.8154 

416.8213 

trans-Nonachlor_C13 

418.8182 

420.8154 

416.8213 

trans-Nonachlor_C13 

418.8182 

420.8154 

416.8213 

trans-Nonachlor_C13 

418.8182 

420.8154 

416.8213 

trans-Nonachlor_C13 

418.8182 

420.8154 

416.8213 

trans-Nonachlor_C13 

418.8182 

420.8154 

416.8213 

176.1074 

177.1107 

196.0528 

trans-Nonachlor_C13 

418.8182 

420.8154 

416.8213 

17.731 

160.9797 

162.9766 

217.0059 

27.033 

135.0807 

173.0965 

201.0584 

18.595 

223.0762 

224.0832 

240.0790 

15.991
7 
23.191 

172.9560 

174.9530 

254.0140 

308.9949 

310.9918 

266.9476 

30.905 

360.0469 

362.0441 

194.0245 

30.657 

221.0799 

373.0865 

265.0884 

31.787 

147.1181 

309.0830 

364.1382 

27.951 

340.0648 

188.0581 

124.9822 

16.156 

198.1075 

199.1105 

184.0866 

29.608 

136.0787 

137.0791 

226.0991 

21.63 

146.0476 

118.0526 

156.0684 

27.308 

171.0807 

143.0857 

338.1884 

14.103 

322.0237 

324.0207 

237.9292 

43 

trans-Nonachlor_C13 

418.8182 

420.8154 

416.8213 

trans-Nonachlor_C13 

418.8182 

420.8154 

416.8213 

trans-Nonachlor_C13 

418.8182 

420.8154 

416.8213 

Propyzamide_d3 

175.9746 

177.9716 

258.0396 

trans-Nonachlor_C13 

418.8182 

420.8154 

416.8213 

trans-Nonachlor_C13 

418.8182 

420.8154 

416.8213 

trans-Nonachlor_C13 

418.8182 

420.8154 

416.8213 

trans-Nonachlor_C13 

418.8182 

420.8154 

416.8213 

trans-Nonachlor_C13 

418.8182 

420.8154 

416.8213 

trans-Nonachlor_C13 

418.8182 

420.8154 

416.8213 

trans-Nonachlor_C13 

418.8182 

420.8154 

416.8213 

trans-Nonachlor_C13 

418.8182 

420.8154 

416.8213 

trans-Nonachlor_C13 

418.8182 

420.8154 

416.8213 

trans-Nonachlor_C13 

418.8182 

420.8154 

416.8213 

 
 
  
  
  
  
  
  
  
  
  
  
  
  
  
  
  
  
  
  
  
  
  
  
  
  
  
  
Compound Method 

Name 

Sulprofos 

tau-Fluvalinate 

Tebuconazole 

Tebufenpyrad 

Tefluthrin 

Terbacil 

Terbufos 

Terbuthylazine 
Tetrachloronitrobenzene (Tec-
nazene) 

Tetrachlorvinphos 

Tetradifon 

Tetramethrin 

Mass ions (m/z) 
Qualifier 
1 
324.0260 

Qualifier 
2 
279.9822 

Quanti-
fier 
322.0294 

ISTD Method 

Qualifier 
3 

Name 

trans-Nonachlor_C13 

RT 

25.574 

Mass ions (m/z) 
Qualifier 
1 
420.8154 

Qualifier 
2 
416.8213 

Quanti-
fier 
418.8182 

35.514 

250.0613 

252.0581 

181.0651 

26.747 

250.0746 

252.0719 

125.0154 

28.621 

171.0324 

318.1378 

276.0906 

16.881 

177.0351 

178.0358 

197.0342 

16.642 

161.0114 

163.0086 

116.9978 

15.871 

230.9745 

232.9701 

288.0447 

15.879 

214.0859 

216.0829 

229.1092 

12.435 

202.8800 

260.8731 

200.8828 

22.532
4 
29.023 

328.9317 

330.9288 

332.9257 

228.8859 

226.8889 

158.9668 

28.037 

164.0709 

331.1782 

164.0710 

trans-Nonachlor_C13 

418.8182 

420.8154 

416.8213 

trans-Nonachlor_C13 

418.8182 

420.8154 

416.8213 

trans-Nonachlor_C13 

418.8182 

420.8154 

416.8213 

trans-Nonachlor_C13 

418.8182 

420.8154 

416.8213 

trans-Nonachlor_C13 

418.8182 

420.8154 

416.8213 

trans-Nonachlor_C13 

418.8182 

420.8154 

416.8213 

trans-Nonachlor_C13 

418.8182 

420.8154 

416.8213 

trans-Nonachlor_C13 

418.8182 

420.8154 

416.8213 

trans-Nonachlor_C13 

418.8182 

420.8154 

416.8213 

trans-Nonachlor_C13 

418.8182 

420.8154 

416.8213 

trans-Nonachlor_C13 

418.8182 

420.8154 

416.8213 

THPI (Tetrahydrophtalimide) 

8.152 

151.0630 

152.0663 

123.0679 

trans-Nonachlor_C13 

418.8182 

420.8154 

416.8213 

Tloclofos-methyl 

Tolyfluanid 

trans-Chlordane 

Transfluthrin 

trans-Nonachlor 

trans-Permethrin 

Triadimefon 

Triadimenol 

Triallate 

Triazophos 

Tricyclazole (Beam) 

Triflumizole 

Trifluralin 

18.274 

264.9891 

266.9833 

249.9625 

21.381 

237.9661 

239.9631 

181.0799 

21.99 

372.8261 

374.8232 

271.8101 

18.382 

163.0161 

165.0049 

335.0463 

22.743 

408.7845 

410.7815 

406.7875 

31.855 

183.0821 

184.0845 

255.0574 

20.105 

208.0275 

210.0246 

236.0223 

21.635 

168.1134 

128.0025 

130.0289 

16.837 

268.0330 

270.0301 

142.9221 

25.644 

162.0662 

172.0871 

313.0651 

23.158 

189.0358 

162.0247 

161.0171 

22.026 

278.0561 

287.0438 

205.9982 

13.945 

264.0232 

306.0703 

290.0754 

44 

trans-Nonachlor_C13 

418.8182 

420.8154 

416.8213 

trans-Nonachlor_C13 

418.8182 

420.8154 

416.8213 

trans-Chlordane_C13 

382.8600 

384.8571 

276.8271 

trans-Nonachlor_C13 

418.8182 

420.8154 

416.8213 

trans-Nonachlor_C13 

418.8182 

420.8154 

416.8213 

trans-Nonachlor_C13 

418.8182 

420.8154 

416.8213 

trans-Nonachlor_C13 

418.8182 

420.8154 

416.8213 

trans-Nonachlor_C13 

418.8182 

420.8154 

416.8213 

trans-Nonachlor_C13 

418.8182 

420.8154 

416.8213 

trans-Nonachlor_C13 

418.8182 

420.8154 

416.8213 

trans-Nonachlor_C13 

418.8182 

420.8154 

416.8213 

trans-Nonachlor_C13 

418.8182 

420.8154 

416.8213 

Trifluralin_d14 

315.1262 

349.1970 

267.0416 

 
 
  
  
  
  
  
  
  
  
  
  
  
  
  
  
  
  
  
  
  
  
  
  
  
  
  
  
Compound Method 

Name 

Vinclozolin 

RT 

18.199 

Mass ions (m/z) 
Qualifier 
1 
214.0006 

Qualifier 
2 
284.9961 

Quanti-
fier 
212.0032 

ISTD Method 

Qualifier 
3 

Name 

trans-Nonachlor_C13 

Mass ions (m/z) 
Qualifier 
1 
420.8154 

Qualifier 
2 
416.8213 

Quanti-
fier 
418.8182 

Annex 2. List of screened compounds, their categories and additional information 

Compound name 
2,3,5,6-Tetrachloroaniline 
2,4'-DDD 
2,4'-DDE 
2,4'-DDT 
2,4'-Methoxychlor 
2,6-Dichlorobenzonitrile (Dichlobenil) 
2-Phenylphenol 
3,4-Dichloroaniline 
4,4'-DDD 
4,4'-DDE 
4,4'-DDT 
4,4'-Dichlorobenzophenone 
4,4'-Methoxychlor olefin 
Acequinocyl 
Acetochlor 
Alachlor 
Aldrin 
Allidochlor 
alpha-BHC 
Anthraquinone 
Atrazine 
Azinphos methyl 

Category 
Pesticide 
Pesticide 
Pesticide 
Pesticide 
Pesticide 
Pesticide 
Pesticide 
Pesticide 
Pesticide 
Pesticide 
Pesticide 
Pesticide 
Pesticide 
Pesticide 
Pesticide 
Pesticide 
Pesticide 
Pesticide 
Pesticide 
Pesticide 
Pesticide 
Pesticide 

Sub category 
Metabolite 
Insecticide 
Breakdown product 
Insecticide 
Insecticide 
Herbicide 
Microbiocide 
Breakdown product 
Insecticide 
Breakdown product 
Insecticide 
Breakdown product 
Breakdown product 
Insecticide 
Herbicide 
Herbicide 
Insecticide 
Herbicide 
Insecticide 
Bird Repellent 
Herbicide 
Insecticide 

CAS number 
3481-20-7  
53-19-0  
3424-82-6  
789-02-6  
30667-99-3  
1194-65-6  
90-43-7  
95-76-1 
72-54-8 
72-55-9 
50-29-3 
90-98-2  
2132-70-9  
57960-19-7  
34256-82-1  
15972-60-8  
309-00-2  
93-71-0  
319-84-6  
84-65-1  
1912-24-9  
86-50-0 

45 

LogKow 
4.1 

2.7 
3.1 
2.7 
6.0 
6.5 
6.9 
4.4 

3.8 

6.5 
1.8 
3.8 
3.4 
5.8 
3.0 

 
 
  
  
  
  
  
  
  
  
Compound name 
Benfluralin 
beta-BHC 
Bifenthrin 
Bioallethrin 
Biphenyl 
Bromfenvinphos-methyl 
Bromfenviphos 
Bromophos ethyl 
Bromophos methyl 
Bromopropylate 
Bupirimate 
Captafol 
Captan 
Carbophenthion 
Carfentrazone ethyl 
Chlorbenside 
Chlorfenapyr 
Chlorfenson (Ovex) 
Chlorfenvinphos 
Chlorobenzilate 
Chloroneb 
Chlorothalonil 
Chlorpropham 
Chlorpyrifos 
Chlorpyrifos methyl 
Chlorthiophos 
Chlozolinate 
cis-Chlordane 
cis-Nonachlor 

Category 
Pesticide 
Pesticide 
Pesticide 
Pesticide 
Pesticide 
Pesticide 
Pesticide 
Pesticide 
Pesticide 
Pesticide 
Pesticide 
Pesticide 
Pesticide 
Pesticide 
Pesticide 
Pesticide 
Pesticide 
Pesticide 
Pesticide 
Pesticide 
Pesticide 
Pesticide 
Pesticide 
Pesticide 
Pesticide 
Pesticide 
Pesticide 
Pesticide 
Pesticide 

CAS number 
1861-40-1  
319-85-7 
82657-04-3  
584-79-2  
92-52-4  
13104-21-7  
33399-00-7  
4824-78-6  
2104-96-3  
18181-80-1  
41483-43-6  
2425-06-1  
133-06-2  
786-19-6  
128639-02-1  
103-17-3  
122453-73-0  
80-33-1 
470-90-6  
510-15-6 
2675-77-6 
1897-45-6 
101-21-3  
2921-88-2  
5598-13-0 
21923-23-9  
84332-86-5 
5103-71-9  
5103-73-1 

46 

Sub category 
Herbicide 
Insecticide 
Insecticide 
Insecticide 
Fungicide 
Insecticide 
Insecticide 
Insecticide 
Insecticide 
Insecticide 
Fungicide 
Fungicide 
Fungicide 
Insecticide 
Herbicide 
Insecticide 
Insecticide 
Insect Growth Regulator 
Insecticide 
Insecticide 
Fungicide 
Fungicide 
Herbicide 
Insecticide 
Insecticide 
Insecticide 
Fungicide 
Insecticide 
Insecticide 

LogKow 
5.2 
3.8 
6.6 
4.7 
4.0 

4.7 
6.2 
5.2 
5.4 
3.7 
3.8 
2.5 
4.8 
3.4 
5.6 
5.2 
4.2 
3.8 
4.6 
3.6 
3.1 
3.8 
4.7 
4.0 
4.3 
3.3 
2.8 
6.4 

 
  
Compound name 
cis-Permethrin 
Clomazone (Command) 
Coumaphos 
Cycloate 
Cyfluthrin 
Cypermenthrin 
Cyprodinil 
DCPA methyl ester (Chlorthal-dimethyl) 
delta-BHC 
Deltamethrin 
Diallate (cis and trans) 
Diazinon 
Dichlofluanid 
Dichloran 
Dieldrin 
Dimethachlor 
Diphenamid 
Diphenylamine 
Disulfoton 
Edifenphos 
Endosulfan ether 
Endosulfan I 
Endosulfan II 
Endosulfan sulfate 
Endrin 
Endrin aldehyde 
Endrin ketone 
EPN 
Ethalfluralin 

Category 
Pesticide 
Pesticide 
Pesticide 
Pesticide 
Pesticide 
Pesticide 
Pesticide 
Pesticide 
Pesticide 
Pesticide 
Pesticide 
Pesticide 
Pesticide 
Pesticide 
Pesticide 
Pesticide 
Pesticide 
Pesticide 
Pesticide 
Pesticide 
Pesticide 
Pesticide 
Pesticide 
Pesticide 
Pesticide 
Pesticide 
Pesticide 
Pesticide 
Pesticide 

CAS number 
61949-76-6  
81777-89-1  
56-72-4  
1134-23-2  
68359-37-5  
52315-07-8 
121552-61-2  
1861-32-1  
319-86-8  
52918-63-5  
2303-16-4 
333-41-5 
1085-98-9 
99-30-9  
60-57-1 
50563-36-5  
957-51-7  
122-39-4  
298-04-4  
17109-49-8  
3369-52-6  
959-98-8  
33213-65-9  
1031-07-8  
72-20-8  
7421-93-4  
53494-70-5  
2104-64-5 
55283-68-6 

47 

Sub category 
Insecticide 
Herbicide 
Insecticide 
Herbicide 
Insecticide 
Insecticide 
Fungicide 
Herbicide 
Insecticide 
Insecticide 
Herbicide 
Insecticide 
Fungicide 
Fungicide 
Insecticide 
Herbicide 
Herbicide 
Plant Growth Regulator 
Insecticide 
Insecticide 
Metabolite 
Insecticide 
Insecticide 
Breakdown product 
Insecticide 
Breakdown product 
Breakdown product 
Insecticide 
Herbicide 

LogKow 
6.5 

4.1 
4.1 
6.0 
5.6 
4.0 
4.3 
3.8 
4.6 

3.7 
5.0 
2.8 
3.7 
2.2 
2.2 
3.8 
4.0 
3.8 

4.8 
3.8 

3.2 

4.1 
5.0 

 
  
  
  
  
  
  
Compound name 
Ethion 
Ethylan (Perthane) 
Etonfenprox 
Etridiazole 
Fenamiphos 
Fenarimol 
Fenchlorphos (Ronnel) 
Fenitrothion 
Fenpropathrin 
Fenson 
Fenthion 
Fenvalerate 
Fipronil 
Fluazifop-p-butyl 
Fluchloralin 
Flucythrinate 
Fludioxonil 
Fluquinconazole 
Fluridone (Sonar) 
Flusilazole 
Flutolanil 
Flutriafol 
Folpet 
Fonofos 
gamma-BHC 
Heptachlor 
Heptachlor epoxide (isomer B) 
Hexachlorobenzene 
Hexazinone 

Category 
Pesticide 
Pesticide 
Pesticide 
Pesticide 
Pesticide 
Pesticide 
Pesticide 
Pesticide 
Pesticide 
Pesticide 
Pesticide 
Pesticide 
Pesticide 
Pesticide 
Pesticide 
Pesticide 
Pesticide 
Pesticide 
Pesticide 
Pesticide 
Pesticide 
Pesticide 
Pesticide 
Pesticide 
Pesticide 
Pesticide 
Pesticide 
Pesticide 
Pesticide 

CAS number 
563-12-2  
72-56-0  
80844-07-1  
2593-15-9  
22224-92-6  
60168-88-9  
299-84-3  
122-14-5 
39515-41-8  
80-38-6  
55-38-9  
51630-58-1  
120068-37-3 
79241-46-6  
33245-39-5 
70124-77-5  
131341-86-1  
136426-54-5  
59756-60-4  
85509-19-9  
66332-96-5  
76674-21-0  
133-07-3  
944-22-9  
58-89-9 
76-44-8  
1024-57-3  
118-74-1  
51235-04-2  

48 

Sub category 
Insecticide 
Insecticide 
Insecticide 
Fungicide 
Insecticide 
Fungicide 
Insecticide 
Insecticide 
Insecticide 
Insecticide 
Insecticide 
Insecticide 
Insecticide 
Herbicide 
Herbicide 
Insecticide 
Fungicide 
Fungicide 
Herbicide 
Fungicide 
Fungicide 
Fungicide 
Fungicide 
Insecticide 
Insecticide 
Insecticide 
Breakdown product 
Fungicide 
Herbicide 

LogKow 
5.1 

6.9 
3.4 
3.3 
3.7 
4.9 
3.3 
6.0 
3.6 

5.0 
3.8 
4.5 
5.1 

4.1 

3.9 
3.7 
2.3 
3.0 
3.9 
3.8 
5.4 
5.0 
3.9 
1.2 

 
  
  
  
  
  
Compound name 
Iodofenphos 
Iprodione 
Isazophos 
Isodrin 
Isopropalin 
lambda-Cyhalothrin 
Lenacil 
Leptophos 
Linuron 
Malathion 
Metalaxyl 
Metazachlor 
Methacrifos 
Methoxychlor 
Methyl parathion 
Metolachlor 
Mevinphos 
MGK-264 
Mirex 
Myclobutanil 
N-(2,4-Dimethylphenyl)formamide 
Nitralin 
Nitrofen 
Norfluorazon 
Oxadiazon 
Oxyfluorfen 
Paclobutrazol 
Parathion (ethyl parathion) 
Pebulate 

Category 
Pesticide 
Pesticide 
Pesticide 
Pesticide 
Pesticide 
Pesticide 
Pesticide 
Pesticide 
Pesticide 
Pesticide 
Pesticide 
Pesticide 
Pesticide 
Pesticide 
Pesticide 
Pesticide 
Pesticide 
Pesticide 
Pesticide 
Pesticide 
Pesticide 
Pesticide 
Pesticide 
Pesticide 
Pesticide 
Pesticide 
Pesticide 
Pesticide 
Pesticide 

CAS number 
18181-70-9 
36734-19-7 
42509-80-8  
465-73-6  
33820-53-0  
91465-08-6 
2164-08-1 
21609-90-5  
330-55-2  
121-75-5  
57837-19-1  
67129-08-2  
62610-77-9 
72-43-5 
298-00-0  
51218-45-2  
7786-34-7  
113-48-4  
2385-85-5  
88671-89-0 
60397-77-5  
4726-14-1  
1836-75-5  
27314-13-2  
19666-30-9  
42874-03-3  
76738-62-0 
56-38-2 
1114-71-2  

49 

Sub category 
Insecticide 
Fungicide 
Insecticide 
Insecticide 
Herbicide 
Insecticide 
Herbicide 
Insecticide 
Herbicide 
Insecticide 
Fungicide 
Herbicide 
Insecticide 
Insecticide 
Insecticide 
Herbicide 
Insecticide 
Synergist 
Insecticide 
Fungicide 
Breakdown product 
Herbicide 
Herbicide 
Herbicide 
Herbicide 
Herbicide 
Plant Growth Regulator 
Insecticide 
Herbicide 

LogKow 
5.5 
3.0 
3.1 
6.8 
5.3 
5.5 
1.7 
6.3 
3.0 
2.8 
1.8 

1.5 
5.8 
2.9 
2.9 
0.1 
3.7 
5.3 
2.9 

3.4 

5.3 
4.9 
3.1 
3.8 
4.0 

 
  
  
  
  
Compound name 
Penconazole 
Pendimethalin 
Pentachloroaniline 
Pentachloroanisole 
Pentachlorobenzene 
Pentachlorobenzonitrile 
Pentachloronitrobenzene (quintozene) 
Pentachlorothioanisole 
Phenothrin (cis & trans) 
Phorate 
Phosalone 
Phosmet 
Piperonyl butoxide 
Pirimiphos ethyl 
Pirimiphos methyl 
Pretilachlor 
Prochloraz 
Procymidone 
Prodiamine 
Profenofos 
Profluralin 
Propachlor 
Propanil 
Propargite 
Propisochlor 
Propyzamide 
Prothiofos 
Pyraclofos 
Pyrazophos 

Category 
Pesticide 
Pesticide 
Pesticide 
Pesticide 
Pesticide 
Pesticide 
Pesticide 
Pesticide 
Pesticide 
Pesticide 
Pesticide 
Pesticide 
Pesticide 
Pesticide 
Pesticide 
Pesticide 
Pesticide 
Pesticide 
Pesticide 
Pesticide 
Pesticide 
Pesticide 
Pesticide 
Pesticide 
Pesticide 
Pesticide 
Pesticide 
Pesticide 
Pesticide 

CAS number 
66246-88-6  
40487-42-1  
527-20-8  
1825-21-4  
608-93-5 
20925-85-3  
82-68-8 
1825-19-0  
51186-88-0 
298-02-2  
2310-17-0 
732-11-6  
51-03-6  
23505-41-1  
29232-93-7 
51218-49-6 
67747-09-5  
32809-16-8  
29091-21-2  
41198-08-7  
26399-36-0 
1918-16-7  
709-98-8  
2312-35-8  
86763-47-5  
23950-58-5  
34643-46-4  
77458-01-6 
13457-18-6  

50 

Sub category 
Fungicide 
Herbicide 
Breakdown product 
Metabolite 
Impurity 
Fragrance 
Fungicide 
Metabolite 
Insecticide 
Insecticide 
Insecticide 
Insecticide 
Synergist 
Insecticide 
Insecticide 
Herbicide 
Fungicide 
Fungicide 
Herbicide 
Insecticide 
Herbicide 
Herbicide 
Herbicide 
Insecticide 
Herbicide 
Herbicide 
Insecticide 
Insecticide 
Fungicide 

LogKow 
3.7 
5.4 
4.8 
5.5 
4.6 

4.5 
5.8 

3.9 
4.0 

4.8 
4.9 
4.2 
4.1 
3.5 
3.3 
4.1 
1.7 
5.6 
1.6 

5.7 
3.3 
3.3 
5.7 
3.8 
3.8 

 
  
  
  
  
Compound name 
Pyridaben 
Pyridafenthion 
Pyrimethanil 
Pyriproxyfen 
Quinalphos 
Resmethrin 
Sulfotepp 
Sulprofos 
tau-Fluvalinate 
Tebuconazole 
Tebufenpyrad 
Tefluthrin 
Terbacil 
Terbufos 
Terbuthylazine 
Tetrachloronitrobenzene (Tecnazene) 
Tetrachlorvinphos 
Tetradifon 
Tetramethrin 
THPI (Tetrahydrophtalimide) 
Tloclofos-methyl 
Tolyfluanid 
trans-Chlordane 
Transfluthrin 
trans-Nonachlor 
trans-Permethrin 
Triadimefon 
Triadimenol 
Triallate 

Category 
Pesticide 
Pesticide 
Pesticide 
Pesticide 
Pesticide 
Pesticide 
Pesticide 
Pesticide 
Pesticide 
Pesticide 
Pesticide 
Pesticide 
Pesticide 
Pesticide 
Pesticide 
Pesticide 
Pesticide 
Pesticide 
Pesticide 
Pesticide 
Pesticide 
Pesticide 
Pesticide 
Pesticide 
Pesticide 
Pesticide 
Pesticide 
Pesticide 
Pesticide 

CAS number 
96489-71-3 
119-12-0  
53112-28-0  
95737-68-1 
13593-03-8  
10453-86-8 
3689-24-5  
35400-43-2  
69409-94-5  
107534-96-3  
119168-77-3  
79538-32-2  
5902-51-2  
13071-79-9  
13071-79-9  
117-18-0  
22248-79-9 
116-29-0  
7696-12-0  
1469-48-3  
57018-04-9  
731-27-1  
5103-74-2  
118712-89-3 
39765-80-5  
61949-77-7  
43121-43-3  
55219-65-3  
2303-17-5  

51 

Sub category 
Insecticide 
Insecticide 
Fungicide 
Insect Growth Regulator 
Insecticide 
Insecticide 
Insecticide 
Insecticide 
Insecticide 
Fungicide 
Insecticide 
Fungicide 
Insecticide 
Insecticide 
Fungicide 
Fungicide 
Insecticide 
Insecticide 
Insecticide 
Flame retardant 
Fungicide 
Fungicide 
Insecticide 
Insecticide 
Insecticide 
Insecticide 
Fungicide 
Fungicide 
Herbicide 

LogKow 
6.4 

2.8 
5.4 
4.4 
5.4 
4.0 
5.5 
7.0 
3.7 
4.9 
6.4 
1.8 
4.5 
3.4 
4.4 

4.6 
4.6 

3.8 

6.2 
5.5 
6.4 
6.1 
3.2 
3.2 
4.1 

 
  
  
  
  
Compound name 
Triazophos 
Tricyclazole (Beam) 
Triflumizole 
Trifluralin 
Vinclozolin 

CAS number 
24017-47-8  
41814-78-2  
68694-11-1 
1582-09-8 
50471-44-8 

Category 
Pesticide 
Pesticide 
Pesticide 
Pesticide 
Pesticide 

Sub category 
Insecticide 
Fungicide 
Fungicide 
Herbicide 
Fungicide 

LogKow 
3.6 
1.4 
4.8 
5.3 
3.0 

Annex 3. Calibration curve equations, Limit of Detection (LOD), Limit of Quantification (LOQ) and Method Detection Limit 

(MDL) for screened compounds 

Name 

Calibration Factor (CF) Formula 

Calibration Factor (CF) R2 

2,3,5,6-Tetrachloroaniline 
2,4'-DDD 
2,4'-DDE 
2,4'-DDT 
2,4'-Methoxychlor 
2,6-Dichlorobenzonitrile (Dichlobenil) 
2-Phenylphenol 
3,4-Dichloroaniline 
4,4'-DDD 
4,4'-DDE 
4,4'-DDT 
4,4'-Dichlorobenzophenone 
4,4'-Methoxychlor olefin 
Acequinocyl 
Acetochlor 
Alachlor 
Aldrin 
Allidochlor 
alpha-BHC 

y = 4.239495 * x  - 5.976065 
y = 4.732321 * x  - 2.647550 
y = 0.867584 * x  - 0.045999 
y = 1.474109 * x  + 0.308131 
y = 5.464714 * x  - 7.356543 
y = 1.071453 * x  - 1.996134 
y = 0.281291 * x  - 0.461680 
y = 0.046584 * x  - 0.093382 
y = 5.550588 * x  - 4.492542 
y = 3.128940 * x  - 0.856222 
y = 4.177966 * x  - 4.997613 
y = 7.384994 * x  - 4.272068 
y = 2.536573 * x  - 1.691020 
y = 2.302391E-004 * x  + 0.001269 
y = 0.288172 * x  - 0.424478 
y = 0.544564 * x  - 0.802139 
y = 0.837584 * x  - 0.684870 
y = 0.002941 * x  - 0.004420 
y = 2.725209 * x  - 3.888694 

52 

0.94548793 
0.9942508 
0.99481706 
0.98031849 
0.96339149 
0.91919106 
0.89307663 
0.92125846 
0.98830621 
0.99431172 
0.9786199 
0.98942236 
0.99275054 
0.26600994 
0.94346278 
0.94127985 
0.98635794 
0.90404569 
0.94198733 

LOD 
3.4 
1.0 
1.2 
1.6 
0.9 
7.6 
5.0 
4.8 
0.9 
1.4 
0.8 
2.1 
0.4 
82.1 
1.1 
0.9 
1.1 
8.9 
2.1 

LOQ 
11.2 
3.4 
4.1 
5.4 
3.1 
25.5 
16.5 
16.0 
3.1 
4.5 
2.6 
7.1 
1.4 
273.5 
3.7 
3.0 
3.7 
29.7 
6.9 

MDL 
3.8 
1.1 
1.4 
1.8 
1.1 
8.6 
5.6 
5.4 
1.0 
1.5 
0.9 
2.4 
0.5 
92.0 
1.3 
1.0 
1.2 
10.0 
2.3 

 
Name 

Anthraquinone 
Atrazine 
Azinphos methyl 
Benfluralin 
beta-BHC 
Bifenthrin 
Bioallethrin 
Biphenyl 
Bromfenvinfos-methyl 
Bromfenviphos 
Bromophos ethyl 
Bromophos methyl 
Bromopropylate 
Bupirimate 
Captafol 
Captan 
Carbophenthion 
Carfentrazone ethyl 
Chlorbenside 
Chlorfenapyr 
Chlorfenson (Ovex) 
Chlorfenvinphos 
Chlorobenzilate 
Chloroneb 
Chlorothalonil 
Chlorpropham 
Chlorpyrifos 
Chlorpyrifos methyl 
Chlorthiophos 

Calibration Factor (CF) Formula 

Calibration Factor (CF) R2 

y = 1.584857 * x  - 3.251386 
y = 0.033861 * x  - 0.060929 
y = 0.003685 * x  - 0.007016 
y = 4.096772 * x  - 5.485096 
y = 0.948391 * x  - 1.926679 
y = 0.122386 * x  + 0.218184 
y = 0.783501 * x  - 0.653185 
y = -0.179732 * x  + 5.004076 
y = 0.314291 * x  - 0.342857 
y = 0.518489 * x  - 0.378720 
y = 0.644658 * x  - 0.147223 
y = 2.894407 * x  - 2.367949 
y = 2.659141 * x  - 3.760332 
y = 1.347626 * x  - 1.578226 
y = 0.082966 * x  + 0.011583 
y = 0.070688 * x  - 0.014965 
y = 0.414406 * x  - 0.673402 
y = 0.513649 * x  - 0.600902 
y = 11.909409 * x  - 15.074245 
y = 0.055144 * x  + 0.007404 
y = 4.581406 * x  - 7.176760 
y = 0.284499 * x  - 0.383082 
y = 5.893873 * x  - 5.109597 
y = 1.651701 * x  - 2.198229 
y = 0.069522 * x  - 0.166126 
y = 0.221437 * x  - 0.424572 
y = 0.756029 * x  + 1.544329 
y = 3.694513 * x  - 4.728747 
y = 1.551918 * x  - 2.150855 

53 

0.89024251 
0.93161831 
0.65541971 
0.95962869 
0.85504368 
0.06427372 
0.92632103 
0.01489968 
0.96866011 
0.97831199 
0.99574415 
0.98283708 
0.95896915 
0.97144499 
0.93021679 
0.92133592 
0.9317453 
0.97210725 
0.967931 
0.99299876 
0.93970016 
0.97429643 
0.98606466 
0.94002418 
0.84411188 
0.85981375 
0.89621895 
0.96753933 
0.96994775 

LOD 
2.1 
5.8 
6.8 
2.4 
0.6 
0.0 
8.1 
208.8 
6.7 
0.6 
1.5 
1.2 
0.4 
0.3 
9.1 

1.2 
1.2 
1.0 
1.2 
1.0 
8.0 
0.7 
3.2 
0.3 
3.8 
9.6 
1.4 
1.5 

LOQ 
7.0 
19.2 
22.6 
8.1 
2.1 
0.0 
27.0 
696.0 
22.3 
2.1 
5.0 
4.2 
1.5 
0.9 
30.2 

3.9 
3.9 
3.4 
3.9 
3.2 
26.6 
2.3 
10.7 
0.9 
12.8 
31.9 
4.6 
5.0 

MDL 
2.4 
6.5 
7.6 
2.7 
0.7 
0.0 
9.1 
316.0 
7.5 
0.7 
1.7 
1.4 
0.5 
0.3 
10.2 

1.3 
1.3 
1.1 
1.3 
1.1 
8.9 
0.8 
3.6 
0.3 
4.3 
10.7 
1.6 
1.7 

 
  
  
  
Name 

Calibration Factor (CF) Formula 

Calibration Factor (CF) R2 

Chlozolinate 
cis-Chlordane 
cis-Nonachlor 
cis-Permethrin 
Clomazone (Command) 
Coumaphos 
Cycloate 
Cyfluthrin 
Cypermenthrin 
Cyprodinil 
DCPA methyl ester (Chlorthal-dimethyl) 
delta-BHC 
Deltamethrin 
Diallate (cis and trans) 
Diazinon 
Dichlofluanid 
Dichloran 
Dieldrin 
Dimethachlor 
Diphenamid 
Diphenylamine 
Disulfoton 
Edifenphos 
Endosulfan ether 
Endosulfan I 
Endosulfan II 
Endosulfan sulfate 
Endrin 
Endrin aldehyde 

y = 0.307327 * x  - 0.529194 
y = 0.963645 * x  - 1.472979 
y = 1.035742 * x  - 0.190591 
y = 4.650444 * x  - 3.097825 
y = 0.464705 * x  - 0.778088 
y = 0.338322 * x  - 0.680844 
y = 3.995421 * x  - 5.272061 
y = 0.108484 * x  - 0.040985 
y = 0.281089 * x  - 0.348541 
y = 6.350481 * x  - 11.431974 
y = 2.785977 * x  - 1.595781 
y = 1.220158 * x  - 2.215694 
y = 0.173688 * x  - 0.036964 
y = 1.775637 * x  - 2.392062 
y = 2.823700 * x  - 3.526885 
y = 0.254401 * x  - 0.299814 
y = 0.052363 * x  - 0.103972 
y = 0.378289 * x  - 0.221041 
y = 0.049025 * x  - 0.064663 
y = 0.197652 * x  - 0.330211 
y = 2.701367 * x  - 0.795015 
y = 3.541384 * x  - 6.044762 
y = 1.564931 * x  - 1.110492 
y = 0.286427 * x  - 0.289953 
y = 0.101029 * x  - 0.090334 
y = 0.076736 * x  - 0.052943 
y = 0.430837 * x  - 0.272801 
y = 0.230329 * x  - 0.375698 
y = 0.090656 * x  - 0.173906 

54 

0.90117224 
0.94003921 
0.99097678 
0.97978482 
0.92633871 
0.88655559 
0.95261165 
0.95568548 
0.96200929 
0.9716391 
0.99149162 
0.88886963 
0.95997903 
0.95537022 
0.95943695 
0.94908555 
0.88052335 
0.98979001 
0.93552208 
0.92898911 
0.90853715 
0.9269528 
0.99121101 
0.96963973 
0.9757626 
0.98687287 
0.98950985 
0.94291869 
0.91902161 

LOD 
0.4 
0.9 
1.2 
2.7 
1.3 
4.0 
2.2 
6.6 
3.7 
9.7 
0.7 
1.0 
6.3 
2.1 
1.7 
8.5 
4.5 
1.2 
2.1 
1.4 
12.6 
2.1 
0.4 
1.9 
1.0 
1.0 
1.0 
0.6 
3.1 

LOQ 
1.3 
3.0 
4.1 
9.1 
4.4 
13.5 
7.2 
22.2 
12.5 
32.3 
2.2 
3.2 
20.9 
6.9 
5.7 
28.5 
15.1 
4.1 
6.9 
4.5 
42.0 
7.0 
1.4 
6.2 
3.2 
3.3 
3.2 
2.1 
10.3 

MDL 
0.4 
1.0 
1.4 
3.1 
1.5 
4.5 
2.4 
7.5 
4.2 
10.9 
0.8 
1.1 
7.0 
2.3 
1.9 
9.6 
5.1 
1.4 
2.3 
1.5 
14.1 
2.3 
0.5 
2.1 
1.1 
1.1 
1.1 
0.7 
3.5 

 
Name 

Endrin ketone 
EPN 
Ethalfluralin 
Ethion 
Ethylan (Perthane) 
Etonfenprox 
Etridiazole 
Fenamiphos 
Fenarimol 
Fenchlorphos (Ronnel) 
Fenitrothion 
Fenpropathrin 
Fenson 
Fenthion 
Fenvalerate 
Fipronil 
Fluazifop-p-butyl 
Fluchloralin 
Flucythrinate 
Fludioxinil 
Fluquinconazole 
Fluridone (Sonar) 
Flusilazole 
Flutolanil 
Flutriafol 
Folpet 
Fonofos 
gamma-BHC 
Heptachlor 

Calibration Factor (CF) Formula 

Calibration Factor (CF) R2 

0.97502858 
y = 0.757014 * x  - 0.905774 
0.95038608 
y = 5.227213 * x  - 7.849512 
0.90567578 
y = 0.332472 * x  - 0.562431 
0.9644349 
y = 3.377192 * x  - 4.344625 
y = 11.492954 * x  - 21.385866 
0.98608451 
y = 1.914165E-005 * x  + 3.170002E-004  0.19945032 
0.93543776 
y = 0.669999 * x  - 1.013865 
0.88684678 
y = 0.050649 * x  - 0.100230 
0.93343936 
y = 0.455546 * x  - 0.695737 
0.9833293 
y = 4.262232 * x  - 3.772426 
0.94887148 
y = 0.422975 * x  - 0.534922 
0.99106296 
y = 1.525524 * x  - 1.349749 
0.96209559 
y = 0.522149 * x  - 0.693305 
0.95632232 
y = 4.047921 * x  - 5.876414 
0.96248601 
y = 0.302724 * x  + 1.431623E-004 
0.96782887 
y = 0.032159 * x  - 0.025425 
0.99427645 
y = 5.030750 * x  - 0.167670 
0.94803813 
y = 1.458401 * x  - 2.188679 
0.96281277 
y = 0.271313 * x  - 0.045689 
0.07879167 
y = 8.216432E-005 * x  + 0.002107 
y = 0.999988 * x  - 1.696522 
0.91540803 
y = 2.246617E-005 * x  + 8.637781E-004  0.02629023 
0.98104123 
y = 3.501597 * x  - 2.591486 
0.94362754 
y = 0.825338 * x  - 1.883037 
0.92533753 
y = 0.029562 * x  - 0.037219 
0.92776053 
y = 0.061113 * x  - 0.098961 
0.96837291 
y = 6.232573 * x  - 7.126255 
0.93572835 
y = 2.220763 * x  - 3.395432 
0.99339819 
y = 0.925610 * x  - 0.398521 

55 

LOD 
0.9 
0.9 
2.2 
0.5 
7.9 
120.4 
4.1 
6.2 
1.5 
1.9 
3.2 
3.8 
1.5 
1.2 
4.5 
3.7 
0.9 
1.7 
2.4 
165.2 
1.1 
382.6 
1.0 
0.2 
1.5 
2.2 
2.6 
1.3 
2.1 

LOQ 
3.0 
3.1 
7.2 
1.6 
26.2 
401.4 
13.7 
20.8 
5.0 
6.3 
10.5 
12.6 
4.9 
3.9 
15.0 
12.2 
2.9 
5.7 
8.0 
550.6 
3.6 
1275.0 
3.4 
0.5 
5.0 
7.4 
8.8 
4.3 
7.0 

MDL 
1.0 
1.0 
2.4 
0.6 
9.8 
135.1 
4.6 
7.0 
1.7 
2.1 
3.5 
4.2 
1.6 
1.3 
5.1 
4.1 
1.0 
1.9 
2.7 
185.3 
1.2 
429.2 
1.1 
0.2 
1.7 
2.5 
3.0 
1.4 
2.3 

 
Name 

Calibration Factor (CF) Formula 

Calibration Factor (CF) R2 

Heptachlor epoxide (isomer B) 
Hexachlorobenzene 
Hexazinone 
Iodofenphos 
Iprodione 
Isazophos 
Isodrin 
Isopropalin 
lambda-Cyhalothrin 
Lenacil 
Leptophos 
Linuron 
Malathion 
Metalaxyl 
Metazachlor 
Methacrifos 
Methoxychlor 
Methyl parathion 
Metolachlor 
Mevinphos 
MGK-264 
Mirex 
Myclobutanil 
N-(2,4-Dimethylphenyl)formamide 
Nitralin 
Nitrofen 
Norfluorazon 
Oxadiazon 
Oxyfluorfen 

0.97838613 
y = 1.035993 * x  - 1.104015 
0.97442443 
y = 4.150760 * x  - 4.078558 
0.23232693 
y = 1.648439E-004 * x  + 0.001936 
0.98504497 
y = 2.424934 * x  - 2.196095 
0.92670193 
y = 0.010750 * x  - 0.023370 
0.95448227 
y = 0.162382 * x  - 0.208243 
0.9942387 
y = 0.705056 * x  - 0.146915 
0.98366509 
y = 2.701481 * x  - 2.033445 
0.99077247 
y = 0.853961 * x  - 0.193207 
0.20829068 
y = 0.011504 * x  + 0.058034 
y = 1.971202 * x  - 2.876997 
0.95992369 
y = 6.826848E-005 * x  + 3.630304E-004  0.44329727 
0.93982785 
y = 0.179985 * x  - 0.134557 
0.48240363 
y = 0.009357 * x  + 0.008383 
0.91238836 
y = 0.016096 * x  + 0.001784 
0.93371271 
y = 0.421742 * x  - 0.647615 
0.9899692 
y = 7.113473 * x  - 13.906961 
0.90318376 
y = 0.288665 * x  - 0.477138 
0.92172757 
y = 1.250272 * x  - 2.055269 
0.18335781 
y = 1.759628E-004 * x  + 0.002249 
0.96097314 
y = 0.470914 * x  - 0.585039 
0.96994789 
y = 0.767969 * x  + 0.108821 
0.92927169 
y = 0.138713 * x  - 0.189683 
0.03142737 
y = 8.614312E-005 * x  + 0.004203 
0.8749975 
y = 0.220500 * x  - 0.415570 
0.93022122 
y = 2.480096 * x  - 4.167330 
0.98226902 
y = 0.023026 * x  - 0.012858 
0.98831536 
y = 2.578611 * x  - 1.930266 
0.95921167 
y = 0.306586 * x  - 0.351054 

56 

LOD 
0.8 
4.0 
103.0 
0.4 
3.3 
1.7 
1.5 
1.5 
2.3 
91.0 
0.9 
58.2 
2.0 
50.9 
4.8 
3.8 
3.8 
2.2 
0.6 
97.9 
1.0 
4.4 
6.3 
253.8 
1.4 
0.9 
1.7 
0.7 
1.2 

LOQ 
2.8 
13.3 
343.5 
1.4 
10.9 
5.6 
4.8 
4.9 
7.8 
303.4 
3.2 
194.1 
6.7 
169.8 
15.8 
12.6 
12.6 
7.4 
2.1 
326.4 
3.4 
14.8 
21.1 
846.0 
4.6 
3.0 
5.7 
2.3 
3.9 

MDL 
0.9 
4.5 
115.6 
0.5 
3.7 
1.9 
1.6 
1.7 
2.6 
102.1 
1.1 
65.3 
2.3 
57.1 
5.3 
4.2 
4.2 
2.5 
0.7 
109.8 
1.1 
5.0 
7.1 
284.7 
1.5 
1.0 
1.9 
0.8 
1.3 

 
Name 

Calibration Factor (CF) Formula 

Calibration Factor (CF) R2 

Paclobutrazol 
Parathion (ethyl parathion) 
Pebulate 
Penconazole 
Pendimethalin 
Pentachloroaniline 
Pentachloroanisole 
Pentachlorobenzene 
Pentachlorobenzonitrile 
Pentachloronitrobenzene (quintozene) 
Pentachlorothioanisole 
Phenothrin (cis & trans) 
Phorate 
Phosalone 
Phosmet 
Piperonyl butoxide 
Pirimiphos ethyl 
Pirimiphos methyl 
Pretilachlor 
Prochloraz 
Procymidone 
Prodiamine 
Profenofos 
Profluralin 
Propachlor 
Propanil 
Propargite 
Propisochlor 
Propyzamide 

y = 0.078652 * x  - 0.039970 
y = 0.396743 * x  - 0.397993 
y = 3.258270 * x  - 4.461298 
y = 1.655472 * x  - 1.278416 
y = 3.372139 * x  - 3.904965 
y = 5.324163 * x  - 7.642791 
y = 1.414910 * x  - 1.258158 
y = 4.984849 * x  - 4.466375 
y = 4.269344 * x  - 4.893177 
y = 1.623126 * x  - 2.077009 
y = 1.846531 * x  - 1.789310 
y = 1.129421 * x  - 1.066032 
y = 2.812439 * x  - 4.085848 
y = 1.203470 * x  - 1.995333 
y = 0.167005 * x  - 0.305477 
y = 6.471774 * x  - 9.260453 
y = 1.024206 * x  - 1.033594 
y = 2.335140 * x  - 2.761536 
y = 1.552819 * x  - 1.685555 
y = 0.116711 * x  - 0.198690 
y = 0.320005 * x  - 0.468880 
y = 0.626180 * x  - 0.632670 
y = 0.463750 * x  - 0.537935 
y = 1.159515 * x  - 1.839172 
y = 0.071023 * x  - 0.108594 
y = 0.015327 * x  - 0.028577 
y = 0.861351 * x  - 0.951821 
y = 0.296086 * x  - 0.396063 
y = 0.257087 * x  - 0.423289 

57 

0.96471022 
0.9710563 
0.94661946 
0.97295819 
0.97528721 
0.95209032 
0.98092073 
0.96836739 
0.97179381 
0.95890656 
0.97983335 
0.9851097 
0.94563416 
0.9233911 
0.90699296 
0.96150698 
0.97590234 
0.96506849 
0.97242179 
0.92082917 
0.93994165 
0.97572395 
0.96837069 
0.9348179 
0.91785787 
0.68117066 
0.94731033 
0.94008033 
0.91206501 

LOD 
2.2 
1.6 
3.0 
1.1 
1.0 
1.5 
3.0 
5.8 
2.4 
2.3 
1.5 
1.9 
3.3 
1.7 
3.1 
2.4 
0.6 
1.1 
0.9 
4.1 
0.5 
3.0 
0.5 
1.8 
2.4 
22.0 
4.2 
3.1 
3.0 

LOQ 
7.2 
5.4 
9.9 
3.7 
3.4 
5.0 
10.1 
19.4 
8.1 
7.8 
5.1 
6.2 
10.9 
5.8 
10.4 
8.0 
1.9 
3.5 
3.1 
13.6 
1.6 
10.2 
1.7 
6.0 
7.9 
73.3 
13.8 
10.4 
9.9 

MDL 
2.4 
1.8 
3.3 
1.2 
1.2 
1.7 
3.4 
6.5 
2.7 
2.6 
1.7 
2.1 
3.7 
2.0 
3.5 
2.7 
0.7 
1.2 
1.1 
4.6 
0.5 
3.4 
0.6 
2.0 
2.6 
24.7 
4.7 
3.5 
3.3 

 
Name 

Calibration Factor (CF) Formula 

Calibration Factor (CF) R2 

Prothiofos 
Pyraclofos 
Pyrazophos 
Pyridaben 
Pyridafenthion 
Pyrimethanil 
Pyriproxyfen 
Quinalphos 
Resmethrin 
Sulfotepp 
Sulprofos 
tau-Fluvalinate 
Tebuconazole 
Tebufenpyrad 
Tefluthrin 
Terbacil 
Terbufos 
Terbuthylazine 
Tetrachloronitrobenzene (Tecnazene) 
Tetrachlorvinphos 
Tetradifon 
Tetramethrin 
THPI (Tetrahydrophtalimide) 
Tloclofos-methyl 
Tolyfluanid 
trans-Chlordane 
Transfluthrin 
trans-Nonachlor 
trans-Permethrin 

0.97912949 
0.91794563 
0.89670704 
0.94298859 
0.90428733 
0.001806 

y = 1.149621 * x  - 1.334257 
y = 0.253258 * x  - 0.520035 
y = 2.078479 * x  - 4.101327 
y = 8.117327 * x  - 10.717026 
y = 0.113941 * x  - 0.198113 
y = -9.621463E-006 * x  + 0.001774 
y = 1.011390E-004 * x  + 9.166054E-004  0.22653854 
0.98150502 
y = 1.272241 * x  - 1.143658 
0.95347659 
y = 0.595237 * x  - 0.730215 
0.94788555 
y = 1.240542 * x  - 1.732949 
0.94182003 
y = 1.890092 * x  - 3.050975 
0.92054949 
y = 0.088063 * x  + 0.037750 
0.94203812 
y = 0.210901 * x  - 0.275823 
0.99077156 
y = 2.054895 * x  - 1.264141 
0.97618489 
y = 5.450234 * x  - 9.662084 
0.02958732 
y = 5.269167E-005 * x  + 0.004567 
0.97730241 
y = 1.951799 * x  - 2.386070 
0.97462645 
y = 0.239050 * x  - 0.223790 
0.93673323 
y = 1.741452 * x  - 2.364849 
0.93668294 
y = 0.414147 * x  - 0.582338 
0.95522805 
y = 1.397488 * x  - 2.009837 
0.89009189 
y = 1.858769 * x  - 2.546158 
0.14348785 
y = 2.681893E-004 * x  + 0.003021 
0.97949798 
y = 6.034623 * x  - 8.476711 
0.96879978 
y = 0.347674 * x  - 0.507033 
0.97820486 
y = 2.037837 * x  - 2.095344 
0.96575054 
y = 4.560175 * x  - 5.797731 
0.99065493 
y = 1.538877 * x  - 1.000714 
0.98225551 
y = 3.762137 * x  - 2.517179 

58 

LOD 
1.0 
3.7 
0.8 
1.3 
2.3 
938.5 
86.4 
1.2 
3.2 
2.8 
0.7 
6.4 
2.5 
3.5 
11.0 
272.5 
5.0 
2.5 
3.2 
1.3 
0.5 
11.5 
107.3 
9.8 
6.3 
0.6 
1.3 
0.8 
3.2 

LOQ 
3.3 
12.4 
2.8 
4.2 
7.7 
3128.0 
288.1 
3.9 
10.8 
9.4 
2.5 
21.4 
8.3 
11.7 
36.7 
908.4 
16.7 
8.5 
10.6 
4.3 
1.7 
38.3 
357.7 
32.7 
21.0 
2.2 
4.4 
2.8 
10.7 

MDL 
1.1 
4.2 
0.9 
1.4 
2.6 
1052.7 
96.9 
1.3 
3.6 
3.2 
0.8 
7.2 
2.8 
3.9 
12.4 
340.4 
5.6 
2.8 
3.6 
1.5 
0.6 
12.9 
120.4 
11.0 
7.1 
0.7 
1.5 
0.9 
3.6 

 
Name 

Triadimefon 
Triadimenol 
Triallate 
Triazophos 
Tricyclazole (Beam) 
Triflumizole 
Trifluralin 
Vinclozolin 

Calibration Factor (CF) Formula 

Calibration Factor (CF) R2 

y = 0.072373 * x  + 0.149986 
y = 0.018326 * x  - 0.002837 
y = 1.503715 * x  - 2.147517 
y = 0.311332 * x  - 0.560291 
y = -2.094598E-006 * x  + 0.001690 
y = 0.414261 * x  - 0.389877 
y = 3.542580 * x  - 4.952055 
y = 0.582300 * x  - 0.818731 

0.93416563 
0.9222266 
0.94424134 
0.90901876 
0.00005667 
0.9742156 
0.95228596 
0.9515633 

LOD 
8.7 
10.8 
1.5 
2.9 
4890.0 
1.3 
2.4 
0.8 

LOQ 
28.9 
36.1 
4.9 
9.6 
16300.0 
4.4 
7.9 
2.8 

MDL 
9.7 
12.2 
1.7 
3.2 
5485.0 
1.5 
2.6 
0.9 

59 

 
 
Annex 4. Desorption, injection and Gas Chromatography analysis parameters 

Run time 

Oven 
Initial temperature  
Hold time 
Post run 

Program 
Ramp 1 
Rate 
Value 
Hold time 
Ramp 2 
Rate 
Value  
Hold time  

Mode 
Pressure 
Total flow 
Septum purge  
Septum purge flow mode 
Pre-Run flow test 
Gas saver 
Purge flow to split vent 
Vent flow 
Vent pressure 

Flow 
Setpoint 
Constant 

Gas Chromatography 
40.5 min 

60 °C 
1 min 
45 °C 

40 °C/min 
120 °C 
0 min 

5 °C/min 
310 °C 
0 min 

Front PTV Inlet He 

Solvent Vent 
6.6321 psi 
40.88 mL/min 
Off 
Switched 
Off 
On 15 after 10 min mL/min 
40 mL/min at 5 min 
40 mL/min per 5 min 
5 psi until 0 min 

Column 

On 
1 mL/min 

CIS 

Liner type 
Liner max temperature 

glass liner CIS4, baffled, non deactivated (013882-010-00 ) 
400 °C 

Temperature program 
Initial temperature  
Equilibration time 

-30 °C 
0.5 min 

60 

 
 
  
  
  
  
  
  
  
  
  
  
  
  
  
 
 
  
  
  
Temperature program 
Initial time 
Ramp 1 
Rate 
End temperature 
Hold time 
Ramp 2 
Rate 
End temperature 
Hold time 

Temperature program 
Initial temperature 
Delay time 
Initial time 
Ramp 1  
Rate  
End temperature 
Hold time 
Ramp 2 
Rate 1 

0.3 min 

12 °C/s 
(260) 310 °C 
(0.2) 10 min 

(12) 0 °C/s 
(310) °C 
(5) 0 min 

TDU  

50 °C 
0.5 min 
(0.5) 1.1 min 

200 °C/s 
310 °C 
10  min  

0 °C/s 

Settings 
Transfer temperature 
Transfer temperature mode  
Desorption mode 
Sample mode 
Standby temperature 
* in parenthesis () method parameters for injection of internal standards are reported 

300 °C 
Fixed 
Splitless 
Retain tube - no standby cooling 
50 °C 

Annex 5. List of selected pesticides for recovery and reproducibility study 

Compound 
Chlorpyrifos methyl 
Diazinon 
EPN 
Fenitrothion 
Isazophos 
Phosalone 
Pirimiphos ethyl 
Pirimiphos methyl 
Pyraclofos 
Pyrazophos 
Quinalphos 
2,4'-DDD 

LOD 
1.4 
1.7 
0.9 
3.2 
1.7 
1.7 
0.6 
1.1 
3.7 
0.8 
1.2 
1.0 

Category 
Organophosphorous 
Organophosphorous 
Organophosphorous 
Organophosphorous 
Organophosphorous 
Organophosphorous 
Organophosphorous 
Organophosphorous 
Organophosphorous 
Organophosphorous 
Organophosphorous 
Organochlorines 

61 

 
  
  
  
 
 
  
  
  
  
  
  
Compound 
2,4'-DDE 
2,4'-DDT 
2,4'-Methoxychlor 
4,4'-DDD 
4,4'-DDE 
4,4'-DDT 
4,4'-Dichlorobenzophenone 
4,4'-Methoxychlor olefin 
Aldrin 
alpha-BHC 
beta-BHC 
Chlorbenside 
Chlorfenson (Ovex) 
cis-Chlordane 
cis-Nonachlor 
delta-BHC 
Dieldrin 
Endosulfan ether 
Endosulfan I 
Endosulfan II 
Endosulfan sulfate 
Endrin aldehyde 
Fenson 
gamma-BHC 
Heptachlor 
Heptachlor epoxide (isomer B) 
Isodrin 
Pentachloroanisole 
Pentachlorothioanisole 
Tetradifon 
trans-Chlordane 
trans-Nonachlor 
3,4-Dichloroaniline 
Benfluralin 
Dichloran 
Ethalfluralin 
Tetrachloronitrobenzene (Tecnazene) 
Trifluralin 
Diphenamid 
Pebulate 
Bupirimate 
Chlorfenapyr 
Etridiazole 
Flusilazole 
Flutriafol 

LOD 
1.2 
1.6 
0.9 
0.9 
1.4 
0.8 
2.1 
0.4 
1.1 
2.1 
0.6 
1.0 
1.0 
0.9 
1.2 
1.0 
1.2 
1.9 
1.0 
1.0 
1.0 
3.1 
1.5 
1.3 
2.1 
0.8 
1.5 
3.0 
1.5 
0.5 
0.6 
0.8 
4.8 
2.4 
4.5 
2.2 
3.2 
2.4 
1.4 
3.0 
0.3 
1.2 
4.1 
1.0 
1.5 

Category 
Organochlorines 
Organochlorines 
Organochlorines 
Organochlorines 
Organochlorines 
Organochlorines 
Organochlorines 
Organochlorines 
Organochlorines 
Organochlorines 
Organochlorines 
Organochlorines 
Organochlorines 
Organochlorines 
Organochlorines 
Organochlorines 
Organochlorines 
Organochlorines 
Organochlorines 
Organochlorines 
Organochlorines 
Organochlorines 
Organochlorines 
Organochlorines 
Organochlorines 
Organochlorines 
Organochlorines 
Organochlorines 
Organochlorines 
Organochlorines 
Organochlorines 
Organochlorines 
Organonitrogen 
Organonitrogen 
Organonitrogen 
Organonitrogen 
Organonitrogen 
Organonitrogen 
Organonitrogen 
Organonitrogen 
Organonitrogen 
Organonitrogen 
Organonitrogen 
Organonitrogen 
Organonitrogen 

62 

 
Compound 
Folpet 
MGK-264 
Penconazole 
Propargite 
Terbuthylazine 
Triflumizole 
Vinclozolin 
Acrinathrin 
Bifenthrin 
lambda-Cyhalothrin 
Phenothrin (cis & trans) 
Transfluthrin 
2-Phenylphenol 
Chlorpropham 
Chlozolinate 
Carbophenthion 
Chlorthiophos 
Coumaphos 
Disulfoton 
Edifenphos 
Ethion 
Fenchlorphos (Ronnel) 
Fonofos 
Leptophos 
Methacrifos 
Phorate 
Piperonyl butoxide 
Profenofos 
Sulfotepp 
Terbufos 
Triazophos 

LOD 
2.2 
1.0 
1.1 
4.2 
2.5 
1.3 
0.8 

0.0 
2.3 
1.9 
1.3 
5.0 
3.8 
0.4 
1.2 
1.5 
4.0 
2.1 
0.4 
0.5 
1.9 
2.6 
0.9 
3.8 
3.3 
2.4 
0.5 
2.8 
5.0 
2.9 

Category 
Organonitrogen 
Organonitrogen 
Organonitrogen 
Organonitrogen 
Organonitrogen 
Organonitrogen 
Organonitrogen 
Synthetic pyrenthroid 
Synthetic pyrenthroid 
Synthetic pyrenthroid 
Synthetic pyrenthroid 
Synthetic pyrenthroid 
Herbicide methyl esters 
Herbicide methyl esters 
Herbicide methyl esters 
Organophosphorous 
Organophosphorous 
Organophosphorous 
Organophosphorous 
Organophosphorous 
Organophosphorous 
Organophosphorous 
Organophosphorous 
Organophosphorous 
Organophosphorous 
Organophosphorous 
Organophosphorous 
Organophosphorous 
Organophosphorous 
Organophosphorous 
Organophosphorous 

Annex 6. Recoveries of individual pesticides, reported alongside standard 

deviations (SD) and coefficient of variations 

Compound 

Category 

Chlorpyrifos methyl 
Diazinon 
EPN 
Fenitrothion 
Isazophos 
Phosalone 
Pirimiphos ethyl 
Pirimiphos methyl 
Pyraclofos 

Organophosphorous 
Organophosphorous 
Organophosphorous 
Organophosphorous 
Organophosphorous 
Organophosphorous 
Organophosphorous 
Organophosphorous 
Organophosphorous 

63 

Average 
[%] 
68.1 
77.7 
108.4 
39.7 
129.3 
124.2 
82.8 
51.3 
121.2 

SD 

15.7 
16.4 
61.4 
32.5 
31.1 
109.6 
45.8 
67.9 
156.3 

CV 
[%] 
23.0 
21.1 
56.6 
81.8 
24.0 
88.2 
55.3 
132.2 
129.0 

 
  
Compound 

Category 

Pyrazophos 
Quinalphos 
2,4'-DDD 
2,4'-DDE 
2,4'-DDT 
2,4'-Methoxychlor 
4,4'-DDD 
4,4'-DDE 
4,4'-DDT 
4,4'-Dichlorobenzophenone 
4,4'-Methoxychlor olefin 
Aldrin 
alpha-BHC 
beta-BHC 
Chlorbenside 
Chlorfenson (Ovex) 
cis-Chlordane 
cis-Nonachlor 
delta-BHC 
Dieldrin 
Endosulfan ether 
Endosulfan I 
Endosulfan II 
Endosulfan sulfate 
Endrin aldehyde 
Fenson 
gamma-BHC 
Heptachlor 
Heptachlor epoxide (isomer B) 
Isodrin 
Pentachloroanisole 
Pentachlorothioanisole 
Tetradifon 
trans-Chlordane 
trans-Nonachlor 
3,4-Dichloroaniline 
Benfluralin 
Dichloran 
Ethalfluralin 
Tetrachloronitrobenzene  
(Tecnazene) 
Trifluralin 
Diphenamid 
Pebulate 

Organophosphorous 
Organophosphorous 
Organochlorines 
Organochlorines 
Organochlorines 
Organochlorines 
Organochlorines 
Organochlorines 
Organochlorines 
Organochlorines 
Organochlorines 
Organochlorines 
Organochlorines 
Organochlorines 
Organochlorines 
Organochlorines 
Organochlorines 
Organochlorines 
Organochlorines 
Organochlorines 
Organochlorines 
Organochlorines 
Organochlorines 
Organochlorines 
Organochlorines 
Organochlorines 
Organochlorines 
Organochlorines 
Organochlorines 
Organochlorines 
Organochlorines 
Organochlorines 
Organochlorines 
Organochlorines 
Organochlorines 
Organonitrogen 
Organonitrogen 
Organonitrogen 
Organonitrogen 

Organonitrogen 
Organonitrogen 
Organonitrogen 
Organonitrogen 

64 

Average 
[%] 
76.6 
121.6 
101.4 
105.5 
108.1 
111.7 
103.5 
106.4 
110.6 
113.2 
102.7 
102.5 
110.0 
120.5 
102.0 
97.9 
103.7 
105.1 
116.5 
124.9 
114.4 
100.3 
110.9 
95.8 
120.1 
94.8 
106.0 
99.7 
131.6 
65.4 
125.6 
69.7 
86.4 
130.4 
72.0 
32.9 
33.0 
61.5 
30.7 

29.3 

32.7 
126.0 
43.9 

SD 

49.2 
69.0 
18.9 
28.5 
69.9 
44.9 
15.3 
29.1 
70.1 
31.9 
41.9 
28.7 
83.3 
108.5 
18.8 
41.5 
24.8 
27.5 
46.4 
58.1 
45.1 
23.5 
22.7 
32.9 
110.8 
42.3 
46.6 
50.0 
36.9 
49.6 
32.2 
51.4 
2.9 
29.3 
62.4 
53.1 
24.4 
24.7 
22.6 

25.5 

24.0 
94.6 
28.7 

CV 
[%] 
64.3 
56.7 
18.7 
27.0 
64.7 
40.2 
14.7 
27.4 
63.4 
28.2 
40.8 
28.0 
75.7 
90.0 
18.4 
42.4 
23.9 
26.2 
39.8 
46.5 
39.4 
23.4 
20.5 
34.4 
92.2 
44.7 
43.9 
50.1 
28.0 
75.7 
25.6 
73.8 
3.3 
22.4 
86.7 
161.1 
74.1 
40.1 
73.4 

87.1 

73.3 
75.0 
65.5 

 
Compound 

Category 

Bupirimate 
Chlorfenapyr 
Etridiazole 
Flusilazole 
Flutriafol 
Folpet 
MGK-264 
Penconazole 
Propargite 
Terbuthylazine 
Triflumizole 
Vinclozolin 
Acrinathrin 
Bifenthrin 
lambda-Cyhalothrin 
Phenothrin (cis & trans) 
Transfluthrin 
2-Phenylphenol 
Chlorpropham 
Chlozolinate 
Carbophenthion 
Chlorthiophos 
Coumaphos 
Disulfoton 
Edifenphos 
Ethion 
Fenchlorphos (Ronnel) 
Fonofos 
Leptophos 
Methacrifos 
Phorate 
Piperonyl butoxide 
Profenofos 
Sulfotepp 
Terbufos 
Triazophos 

Average 
Median   
1st Quartile  
3rd Quartile  

Organonitrogen 
Organonitrogen 
Organonitrogen 
Organonitrogen 
Organonitrogen 
Organonitrogen 
Organonitrogen 
Organonitrogen 
Organonitrogen 
Organonitrogen 
Organonitrogen 
Organonitrogen 
Synthetic pyrenthroid 
Synthetic pyrenthroid 
Synthetic pyrenthroid 
Synthetic pyrenthroid 
Synthetic pyrenthroid 
Herbicide methyl esters 
Herbicide methyl esters 
Herbicide methyl esters 
Organophosphorous 
Organophosphorous 
Organophosphorous 
Organophosphorous 
Organophosphorous 
Organophosphorous 
Organophosphorous 
Organophosphorous 
Organophosphorous 
Organophosphorous 
Organophosphorous 
Organophosphorous 
Organophosphorous 
Organophosphorous 
Organophosphorous 
Organophosphorous 

65 

Average 
[%] 
112.2 
79.5 
61.0 
110.4 
38.2 
74.3 
91.9 
114.3 
105.8 
14.3 
68.3 
93.1 
121.4 
110.6 
128.1 
147.2 
48.4 
70.6 
27.1 
123.0 
89.1 
82.4 
96.6 
61.4 
81.0 
75.0 
69.4 
38.4 
79.6 
31.6 
69.2 
95.8 
136.6 
32.6 
40.2 
85.3 

88.2 
96.2 
69.0 
111.1 

SD 

63.7 
43.5 
46.1 
61.0 
34.2 
23.2 
51.5 
65.1 
85.0 
4.9 
34.0 
111.7 
71.6 
61.2 
76.7 
69.2 
62.0 
20.3 
29.8 
89.7 
47.5 
43.6 
45.6 
52.9 
41.0 
35.4 
62.6 
27.0 
47.6 
25.6 
28.0 
45.4 
77.4 
23.9 
19.6 
32.8 

47.0 
43.6 
27.9 
61.5 

CV 
[%] 
56.8 
54.7 
75.7 
55.3 
89.6 
31.3 
56.1 
57.0 
80.3 
34.3 
49.8 
120.0 
59.0 
55.3 
59.8 
47.0 
128.3 
28.8 
109.9 
72.9 
53.3 
52.9 
47.2 
86.1 
50.7 
47.1 
90.2 
70.4 
59.7 
81.1 
40.4 
47.4 
56.7 
73.3 
48.9 
38.4 

57.1 
55.0 
37.4 
73.8 

 
  
  
  
  
  
 
Annex 7. Recoveries of individual pesticides with standard deviations (SD) for extraction test 

Compound 

Category 

24h 

SD 

48h 

SD 

72h 

SD 

96h 

SD 

144h 

SD 

168h 

SD 

Manual  
agitation 

SD 

Reference 

SD 

2,4'-DDD 

2,4'-DDE 

2,4'-DDT 

Organochlorines 

Organochlorines 

Organochlorines 

2,4'-Methoxychlor 

Organochlorines 

8.0 

9.5 

7.7 

6.1 

6.7 

6.0 

15.8 

18.3 

7.2 

6.7 

23.6 

28.3 

9.2 

4.5 

27.1 

31.3 

47.3 

99.9 

42.7 

41.5 

31.1 

34.5 

52.8 

132.2 

38.4 

17.2 

20.5 

17.3 

33.7 

24.2 

16.1 

29.8 

68.3 

47.8 

142.1 

33.8 

71.6 

29.9 

13.4 

83.6 

19.6 

20.1 

42.5 

36.2 

30.9 

102.2 

2-Phenylphenol 

Herbicide methyl esters 

88.8 

482.3 

125.8 

234.3 

153.8 

809.2 

184.8 

170.8 

938.1 

55.6 

13.5 

1041.
6 

53.3 

119.
9 

0.4 

21.9 

1048.
1 

3,4-Dichloroaniline 

Organonitrogen 

4,4'-DDD 

4,4'-DDE 

4,4'-DDT 

Organochlorines 

Organochlorines 

Organochlorines 

4,4'-Dichlorobenzophenone 

Organochlorines 

4,4'-Methoxychlor olefin 

Organochlorines 

Acrinathrin 

Aldrin 

alpha-BHC 

Benfluralin 

beta-BHC 

Bifenthrin 

Bupirimate 

Synthetic pyrethroid 

Organochlorines 

Organochlorines 

Organonitrogen 

Organochlorines 

Synthetic pyrethroid 

Organonitrogen 

Carbophenthion 

Organophosphorous 

Chlorbenside 

Chlorfenapyr 

Organochlorines 

Organonitrogen 

Chlorfenson (Ovex) 

Organochlorines 

Chlorpropham 

Herbicide methyl esters 

1.2 

6.7 

9.3 

8.1 

7.5 

7.0 

4.5 

8.0 

9.4 

9.2 

6.4 

5.9 

8.5 

10.7 

197.6 

1.1 

43.9 

0.9 

47.8 

2.8 

475.4 

0.8 

53.1 

3.6 

14.5 

8.0 

19.7 

17.6 

22.2 

24.1 

40.5 

88.3 

36.6 

44.7 

13.2 

37.4 

17.1 

16.3 

24.9 

18.2 

30.0 

31.0 

50.8 

117.1 

35.8 

29.1 

16.3 

41.6 

24.0 

26.6 

27.8 

86.2 

43.2 

157.5 

35.6 

162.3 

5.7 

14.6 

9.1 

24.6 

20.8 

23.9 

18.1 

44.1 

53.2 

48.5 

50.5 

20.2 

16.5 

70.0 

24.5 

31.1 

25.1 

41.7 

47.9 

20.4 

44.2 

41.9 

0.1 

6.0 

9.7 

0.2 

13.1 

0.2 

11.3 

0.1 

17.6 

0.2 

19.4 

0.1 

72.7 

14.8 

17.0 

24.8 

39.3 

21.5 

33.4 

28.8 

109.0 

14.8 

30.6 

13.8 

11.2 

25.7 

5.9 

51.6 

6.7 

301.8 

16.0 

437.1 

23.5 

54.4 

1090.
9 

49.9 

65.5 

71.6 

32.0 

112.4 

83.7 

40.0 

1691.
8 

71.3 

39.7 

94.3 

3625.
9 

67.1 

32.6 

50.9 

1832.
4 

7.4 

3.1 

115.7 

170.0 

202.5 

175.9 

119.5 

25.4 

40.4 

24.6 

106.
4 

47.3 

5.7 

22.5 

17.1 

58.8 

17.7 

15.9 

56.7 

6.7 

44.2 

290.4 

22.8 

497.5 

23.5 

195.6 

26.1 

191.3 

48.2 

416.4 

51.1 

17.7 

1496.
1 

105.8 

15.6 

186.6 

17.7 

131.6 

18.2 

85.5 

30.1 

167.0 

23.1 

145.4 

13.0 

30.5 

27.5 

7.3 

3.7 

7.3 

5.1 

7.5 

11.8 

8.9 

21.9 

8.8 

12.3 

19.4 

39.3 

20.4 

36.3 

21.9 

17.9 

43.6 

58.5 

39.9 

119.0 

16.2 

32.8 

22.1 

35.1 

23.2 

20.2 

44.3 

43.1 

41.7 

26.6 

29.1 

457.3 

54.4 

299.2 

51.0 

307.4 

50.9 

477.0 

86.1 

701.1 

79.3 

597.0 

14.6 

Chlorpyrifos methyl 

Organophosphorous 

Chlorthiophos 

Organophosphorous 

5.6 

7.2 

16.9 

10.2 

45.3 

14.5 

153.7 

12.8 

97.5 

19.2 

229.1 

15.6 

115.8 

3.1 

205.6 

16.2 

109.3 

17.7 

214.5 

20.1 

184.0 

33.5 

253.9 

27.1 

588.3 

13.2 

66 

3.6 

4.2 

3.6 

4.4 

1.0 

3.3 

3.4 

3.7 

3.8 

4.8 

15.2 

9.1 

7.3 

2.9 

9.8 

5.5 

55.6 

14.6 

21.2 

3.6 

4.2 

3.6 

4.4 

3.3 

3.4 

3.7 

3.8 

4.8 

101.4 

18.9 

105.5 

28.5 

108.1 

69.9 

111.7 

44.9 

70.6 

20.3 

32.9 

53.1 

103.5 

15.3 

106.4 

29.1 

110.6 

70.1 

113.2 

31.9 

102.7 

41.9 

121.4 

71.6 

102.5 

28.7 

7.4 

110.0 

83.3 

25.4 

33.0 

24.4 

108.
5 

61.2 

120.5 

110.6 

112.2 

63.7 

89.1 

47.5 

2.9 

5.5 

4.3 

3.8 

12.3 

102.0 

18.8 

2.9 

6.0 

4.2 

6.8 

5.7 

79.5 

43.5 

97.9 

41.5 

27.1 

29.8 

68.1 

15.7 

82.4 

43.6 

 
  
  
Compound 

Category 

24h 

SD 

48h 

SD 

72h 

SD 

96h 

SD 

144h 

SD 

168h 

SD 

Manual  
agitation 

SD 

Reference 

SD 

Herbicide methyl esters 

28.4 

0.2 

39.8 

0.4 

9.2 

0.1 

14.8 

0.2 

9.6 

0.1 

7.9 

0.0 

21.2 

Chlozolinate 

cis-Chlordane 

cis-Nonachlor 

Coumaphos 

delta-BHC 

Diazinon 

Dichloran 

Dieldrin 

Diphenamid 

Disulfoton 

Edifenphos 

Organochlorines 

Organochlorines 

Organophosphorous 

Organochlorines 

Organophosphorous 

Organonitrogen 

Organochlorines 

Organonitrogen 

Organophosphorous 

Organophosphorous 

Endosulfan ether 

Organochlorines 

Endosulfan I 

Endosulfan II 

Organochlorines 

Organochlorines 

Endosulfan sulfate 

Organochlorines 

Endrin aldehyde 

Organochlorines 

EPN 

Organophosphorous 

Ethalfluralin 

Organonitrogen 

Ethion 

Etridiazole 

Organophosphorous 

Organonitrogen 

Fenchlorphos (Ronnel) 

Organophosphorous 

Fenitrothion 

Fenson 

Flusilazole 

Flutriafol 

Folpet 

Fonofos 

Organophosphorous 

Organochlorines 

Organonitrogen 

Organonitrogen 

Organonitrogen 

Organophosphorous 

9.3 

7.9 

5.9 

22.2 

7.5 

12.8 

17.2 

11.9 

28.2 

25.5 

31.6 

31.2 

55.1 

101.4 

42.6 

32.8 

0.7 

16.4 

5.0 

23.1 

3.5 

26.6 

29.4 

52.9 

68.7 

39.9 

32.3 

50.2 

13.9 

114.6 

15.2 

141.2 

16.1 

168.1 

32.0 

337.2 

30.4 

403.2 

4.3 

3.8 

4.1 

13.6 

34.8 

43.0 

23.2 

61.4 

25.3 

55.1 

22.0 

116.3 

161.5 

97.6 

71.8 

12.3 

11.9 

12.3 

21.5 

89.8 

17.5 

34.2 

30.5 

134.1 

26.8 

103.0 

5.1 

137.0 

181.8 

62.8 

65.5 

10.2 

5.5 

0.4 

10.9 

183.5 

11.3 

171.1 

1.0 

9.9 

16.6 

384.7 

12.3 

128.2 

13.0 

244.2 

27.2 

8.0 

0.9 

7.1 

1507.
8 

14.8 

16.7 

339.
3 

39.2 

1.7 

3.0 

7.6 

1705.
9 

22.9 

495.9 

6.4 

9.7 

11.3 

520.2 

31.1 

820.7 

72.7 

7.3 

592.4 

16.4 

673.9 

19.3 

292.2 

21.1 

419.1 

41.3 

765.4 

40.8 

53.3 

65.2 

32.3 

31.5 

18.4 

2.3 

9.4 

4641.
3 
2342.
6 

73.4 

13.0 

9.6 

8.0 

8.9 

7.8 

3.2 

9.7 

5.1 

25.8 

12.2 

41.9 

19.8 

34.7 

11.6 

58.0 

86.1 

59.8 

17.0 

6.8 

20.6 

11.9 

19.1 

27.7 

24.5 

30.5 

21.6 

29.8 

13.9 

38.5 

15.5 

18.2 

14.7 

42.6 

16.7 

17.2 

12.5 

8.9 

16.0 

2.3 

23.5 

8.7 

24.6 

9.6 

42.4 

67.9 

42.7 

42.1 

11.2 

10.5 

21.8 

30.4 

26.0 

25.7 

29.2 

33.2 

47.4 

33.5 

50.6 

36.8 

4.0 

9.0 

5.5 

95.2 

25.4 

6.3 

78.1 

4.9 

138.1 

3.4 

81.6 

4.3 

136.8 

3.4 

231.2 

20.4 

77.1 

30.5 

117.3 

29.2 

141.3 

48.8 

319.7 

37.3 

206.7 

584.0 

13.4 

321.9 

17.7 

362.0 

14.9 

465.8 

24.0 

1157.
8 

17.9 

884.4 

13.9 

196.7 

30.8 

135.7 

39.5 

545.8 

39.8 

520.9 

70.1 

954.0 

51.3 

448.0 

6.7 

4.7 

8.1 

4.3 

4.0 

4.1 

4.3 

4.1 

5.1 

4.5 

4.3 

1.0 

3.1 

123.0 

89.7 

103.7 

24.8 

105.1 

27.5 

96.6 

45.6 

116.5 

46.4 

77.7 

16.4 

61.5 

24.7 

124.9 

58.1 

126.0 

94.6 

61.4 

52.9 

81.0 

41.0 

114.4 

45.1 

100.3 

23.5 

18.4 

110.9 

22.7 

5.0 

4.1 

2.8 

95.8 

120.1 

32.9 

110.
8 

108.4 

61.4 

94.2 

30.7 

22.6 

4.4 

9.1 

9.8 

5.2 

9.1 

75.0 

35.4 

61.0 

46.1 

69.4 

62.6 

39.7 

32.5 

94.8 

42.3 

117.8 

110.4 

61.0 

2.9 

94.2 

5.6 

5.8 

6.0 

4.2 

6.8 

5.7 

6.7 

4.7 

5.0 

7.6 

5.2 

2.7 

7.6 

4.7 

9.1 

8.4 

1128.5 

12.5 

2349.2 

25.7 

10.2 

1.5 

7.2 

12.0 

22.4 

16.5 

2.9 

2.0 

47.0 

20.8 

10.4 

933.1 

23.8 

805.1 

27.1 

444.5 

4379.3 

366.4 

2761.5 

69.6 

12.2 

1.5 

36.0 

3.5 

11.6 

7.0 

632.6 

17.6 

700.3 

26.1 

15.8 

1095.
4 

73.4 

1.2 

2307.
9 

67 

9988.
4 

58.3 

18483
.2 

8.7 

46.8 

2.9 

24.2 

26.5 

17.0 

1007.
2 

51.3 

55.1 

41.0 

58.3 

10373
.6 

137.6 

71511
.3 

7.4 

68.1 

10.4 

53.1 

2922.
1 

45.7 

55.8 

47.7 

4822.
7 

82.3 

179.5 

110.0 

173.0 

98.7 

344.7 

117.8 

17.3 

38.2 

34.2 

8.5 

20.5 

0.3 

2486.
4 

16.5 

30.0 

0.8 

3436.
0 

8.6 

29.2 

1.3 

1977.
3 

17.3 

14.8 

74.3 

23.2 

4.6 

9.0 

38.4 

27.0 

 
Compound 

Category 

24h 

SD 

48h 

SD 

72h 

SD 

96h 

SD 

144h 

SD 

168h 

SD 

Manual  
agitation 

SD 

Reference 

SD 

gamma-BHC 

Heptachlor 

Organochlorines 

Organochlorines 

Heptachlor epoxide (isomer B) 

Organochlorines 

Isazophos 

Isodrin 

Organophosphorous 

Organochlorines 

lambda-Cyhalothrin 

Synthetic pyrethroid 

Leptophos 

Methacrifos 

MGK-264 

Pebulate 

Organophosphorous 

Organophosphorous 

Organonitrogen 

Organonitrogen 

Penconazole 

Organonitrogen 

Pentachloroanisole 

Organochlorines 

Pentachlorothioanisole 

Organochlorines 

Phenothrin (cis & trans) 

Synthetic pyrethroid 

Phorate 

Phosalone 

Organophosphorous 

Organophosphorous 

Piperonyl butoxide 

Organophosphorous 

Pirimiphos ethyl 

Organophosphorous 

Pirimiphos methyl 

Organophosphorous 

Profenofos 

Propargite 

Pyraclofos 

Pyrazophos 

Quinalphos 

Sulfotepp 

Terbufos 

Organophosphorous 

Organonitrogen 

Organophosphorous 

Organophosphorous 

Organophosphorous 

Organophosphorous 

Organophosphorous 

Terbuthylazine 

Organonitrogen 

11.8 

8.4 

9.6 

10.8 

8.4 

10.0 

8.5 

5.1 

3.2 

5.6 

8.1 

1.4 

25.1 

9.3 

50.3 

43.6 

35.4 

19.0 

70.6 

97.8 

58.4 

49.8 

13.9 

16.5 

23.4 

16.2 

17.8 

22.1 

19.1 

85.4 

15.0 

38.6 

16.2 

19.7 

4.3 

7.6 

28.7 

24.1 

27.7 

21.0 

51.2 

81.9 

45.4 

47.4 

24.8 

17.3 

24.9 

12.6 

31.6 

19.0 

29.8 

13.0 

16.8 

12.9 

26.0 

22.1 

25.8 

24.0 

33.2 

59.6 

16.9 

25.2 

8.1 

4.3 

4.0 

9.2 

4.1 

16.0 

3.0 

32.5 

2.1 

27.4 

2.4 

23.0 

0.9 

16.7 

1.2 

20.3 

2.2 

37.6 

4.2 

17.9 

3.6 

31.8 

2.1 

42.5 

2.7 

100.3 

1.9 

63.3 

17.8 

105.8 

38.7 

424.7 

50.3 

647.8 

45.4 

731.2 

59.8 

877.2 

53.9 

532.3 

4.9 

9.9 

16.9 

17.3 

18.4 

15.1 

3.1 

5.1 

4.7 

7.6 

9.2 

106.0 

46.6 

99.7 

50.0 

131.6 

36.9 

129.3 

31.1 

65.4 

49.6 

128.1 

76.7 

79.6 

47.6 

31.6 

25.6 

91.9 

51.5 

15.7 

108.4 

32.9 

130.5 

36.8 

91.5 

33.5 

9.6 

229.9 

24.3 

851.0 

33.2 

962.4 

34.0 

72.5 

1366.
6 

62.5 

56.9 

10.6 

610.9 

26.7 

841.8 

29.6 

659.1 

31.2 

341.3 

64.8 

5.5 

18.2 

4.2 

34.8 

16.9 

32.1 

27.7 

51.8 

59.2 

285.1 

14.8 

35.1 

2348.
4 
1009.
2 

48.5 

52.3 

65.5 

41.5 

1590.
6 
3277.
3 

19.4 

4.4 

9.0 

4.3 

4.1 

662.2 

43.9 

28.7 

10.1 

114.3 

65.1 

8.7 

3.0 

125.6 

32.2 

69.7 

51.4 

11.8 

18.8 

16.0 

32.2 

17.1 

34.2 

50.9 

52.0 

101.5 

43.5 

51.0 

2.4 

13.6 

5.2 

22.7 

2.2 

31.4 

1683.9 

28.1 

473.9 

9.7 

400.7 

24.4 

254.
2 

4.3 

25.3 

3.1 

6.1 

1.1 

11.6 

34.0 

147.2 

69.2 

21574
.3 

23.2 

760.8 

17.8 

662.0 

15.3 

8.4 

69.2 

28.0 

133.8 

16.5 

492.7 

17.3 

592.9 

17.6 

630.8 

29.5 

889.5 

25.7 

2168.5 

17.3 

876.7 

18.8 

1278.
8 

20.1 

213.8 

18.4 

532.9 

22.3 

284.2 

22.2 

3.9 

1.0 

17.4 

9.5 

7.8 

1.4 

41.0 

15.3 

35.2 

22.7 

1.0 

23.0 

1502.
7 

94.5 

8.7 

0.8 

37.2 

2681.
2 

35.0 

39.9 

281.7 

31.8 

893.8 

10.1 

42.9 

14.4 

45.6 

15.1 

28.0 

1.7 

27.7 

1.4 

8.7 

6.1 

1006.
8 
4962.
3 

124.2 

109.
6 

8.9 

13.2 

95.8 

45.4 

10.4 

150.8 

23.4 

216.2 

24.5 

466.3 

18.7 

78.8 

45.6 

318.1 

21.4 

336.7 

16.9 

5.8 

81.7 

15.3 

196.5 

11.3 

108.9 

17.5 

207.3 

25.9 

269.7 

22.8 

301.7 

3.0 

324.4 

55763.
2 

172.1 

19138.
7 

39.0 

2007.
1 

34.6 

722.1 

40.4 

2688.
1 

40.9 

2663.
6 

114.5 

20.1 

202.6 

21.4 

332.2 

21.8 

240.5 

35.6 

255.1 

31.0 

617.3 

4.1 

5.6 

5.8 

7.6 

2.7 

4.6 

4.9 

9.9 

82.8 

45.8 

51.3 

67.9 

136.6 

77.4 

105.8 

85.0 

121.2 

156.
3 

76.6 

49.2 

121.6 

69.0 

32.6 

23.9 

15.3 

40.2 

19.6 

34.0 

8.4 

4.6 

4.4 

12.8 

409.4 

16.9 

369.8 

11.9 

370.2 

14.5 

498.0 

11.0 

169.6 

3.8 

14.3 

11.6 

101.5 

2.6 

17.1 

4.0 

46.6 

2.8 

26.2 

44.2 

72.3 

32.8 

54.0 

39.2 

74.8 

38.3 

77.9 

55.5 

131.7 

171.9 

151.1 

65.3 

17.3 

8.9 

14.3 

4.9 

68 

11.4 

10.1 

8.5 

6.7 

9.8 

7.9 

7.7 

6.7 

8.5 

6.3 

3.9 

28.8 

 
  
  
Compound 

Category 

24h 

SD 

48h 

SD 

72h 

SD 

96h 

SD 

144h 

SD 

168h 

SD 

Tetrachloronitrobenzene (Tec-
nazene) 

Tetradifon 

Organonitrogen 

Organochlorines 

trans-Chlordane 

Organochlorines 

Transfluthrin 

Synthetic pyrethroid 

trans-Nonachlor 

Organochlorines 

9.7 

7.3 

10.0 

11.8 

10.1 

5.3 

6.0 

6.2 

155.0 

23.1 

193.6 

34.3 

18.2 

16.1 

60.3 

25.2 

1132.
8 

27.0 

33.0 

24.8 

1112.
5 

31.0 

56.1 

45.5 

2028.
3 

24.8 

45.8 

40.6 

1415.
1 

40.3 

17.6 

4.7 

29.7 

14.2 

30.6 

35.2 

53.7 

116.8 

41.5 

33.2 

Manual  
agitation 

SD 

Reference 

SD 

4.1 

5.1 

4.5 

6.1 

4.6 

4.4 

29.3 

25.5 

86.4 

2.9 

130.4 

29.3 

25.9 

12.9 

57.4 

21.9 

61.7 

23.0 

71.0 

28.8 

72.1 

39.0 

13.2 

33.9 

48.4 

62.0 

17.8 

5.5 

28.4 

9.4 

31.5 

37.9 

63.1 

95.0 

39.3 

26.5 

4.3 

72.7 

72.0 

62.4 

Triazophos 

Triflumizole 

Trifluralin 

Vinclozolin 

Organophosphorous 

Organonitrogen 

Organonitrogen 

Organonitrogen 

37.8 

677.5 

37.4 

154.7 

46.7 

89.6 

34.4 

180.9 

46.1 

223.8 

34.3 

422.4 

33.9 

15.2 

85.3 

32.8 

9.2 

5.7 

6.8 

67.1 

23.0 

335.7 

22.5 

420.7 

15.1 

416.3 

22.2 

17.9 

1686.
0 

24.3 

22.6 

71.8 

2390.
1 

40.9 

1.0 

9.0 

0.7 

17.8 

1.2 

11.5 

0.7 

8.7 

41.8 

270.3 

34.9 

270.9 

18.4 

20.3 

68.3 

34.0 

4666.
7 

0.7 

29.9 

3017.
4 

2.8 

11.6 

32.7 

24.0 

9.8 

1.2 

15.1 

13.2 

93.1 

111.
7 

Annex 8. Statistical results of isochronous stability testing for individual pesticides (b = slope, ub = standard error of the 

slope, U = Uncertainty, we = weeks) 

Compound 

Category 

b 

ub 

b/ub 

Slope ≠ 0 

Uncertainty  
 [6 we] 

Uncertainty 
[%}(6 we) 

Shelf-life  
[we] (U=20%) 

2-Phenylphenol 
Chlorpropham 
Chlozolinate 
2,4'-DDD 
2,4'-DDE 
2,4'-DDT 
2,4'-Methoxychlor 
4,4'-DDD 
4,4'-DDE 
4,4'-DDT 
4,4'-Dichlorobenzophenone 

Herbicide methyl esters 
2.45 
Herbicide methyl esters  28.96 
0.04 
Herbicide methyl esters 
1.53 
Organochlorines 
1.51 
Organochlorines 
3.67 
Organochlorines 
2.60 
Organochlorines 
1.73 
Organochlorines 
2.08 
Organochlorines 
3.32 
Organochlorines 
1.95 
Organochlorines 

NO 
NO 
NO 
NO 
NO 
NO 
NO 
NO 
NO 
NO 
NO 

1.06 
0.69 
0.01 
1.24 
0.88 
1.29 
1.31 
1.34 
1.18 
1.00 
1.16 

2.30 
42.26 
8.13 
1.24 
1.71 
2.83 
1.98 
1.29 
1.77 
3.34 
1.68 

69 

0.12 
1.02 
0.40 
0.07 
0.10 
0.15 
0.11 
0.08 
0.10 
0.17 
0.09 

12 
102 
40 
7 
10 
15 
11 
8 
10 
17 
9 

10 
1 
3 
16 
12 
8 
11 
16 
12 
7 
13 

 
 
Compound 

Category 

b 

ub 

b/ub 

Slope ≠ 0 

Uncertainty  
 [6 we] 

Uncertainty 
[%}(6 we) 

Shelf-life  
[we] (U=20%) 

4,4'-Methoxychlor olefin 
Aldrin 
alpha-BHC 
beta-BHC 
Chlorbenside 
Chlorfenson (Ovex) 
cis-Chlordane 
cis-Nonachlor 
delta-BHC 
Dieldrin 
Endosulfan ether 
Endosulfan I 
Endosulfan II 
Endosulfan sulfate 
Endrin aldehyde 
Fenson 
gamma-BHC 
Heptachlor 
Heptachlor epoxide (isomer B) 
Isodrin 
Pentachloroanisole 
Pentachlorothioanisole 
Tetradifon 
trans-Chlordane 
trans-Nonachlor 
3,4-Dichloroaniline 
Benfluralin 
Dichloran 

Organochlorines 
Organochlorines 
Organochlorines 
Organochlorines 
Organochlorines 
Organochlorines 
Organochlorines 
Organochlorines 
Organochlorines 
Organochlorines 
Organochlorines 
Organochlorines 
Organochlorines 
Organochlorines 
Organochlorines 
Organochlorines 
Organochlorines 
Organochlorines 
Organochlorines 
Organochlorines 
Organochlorines 
Organochlorines 
Organochlorines 
Organochlorines 
Organochlorines 
Organonitrogen 
Organonitrogen 
Organonitrogen 

1.68 
0.76 
2.19 
4.46 
-2.61 
1.21 
1.08 
1.48 
2.37 
3.67 
0.43 
1.56 
0.48 
0.95 
6.64 
4.99 
1.05 
1.83 
0.75 
1.34 
-0.37 
0.77 
1.34 
1.21 
1.17 

1.11 
1.51 
0.53 
1.43 
1.48 
1.48 
1.44 
3.09 
-1.08 
2.43 
1.15 
1.05 
0.62 
1.73 
0.85 
1.73 
0.97 
2.43 
1.18 
3.13 
0.34 
1.25 
1.13 
1.38 
0.39 
1.21 
0.77 
1.22 
1.30 
5.12 
0.25 
20.08 
0.48 
2.19 
0.97 
1.88 
0.42 
1.76 
0.86 
1.56 
-0.09 
4.25 
0.56 
1.38 
0.88 
1.52 
0.79 
1.54 
0.71 
1.65 
948.25  906.34  1.05 
1.27 
1.58 
1.50 
4.98 

2.00 
7.46 

70 

NO 
NO 
NO 
NO 
NO 
NO 
NO 
NO 
NO 
NO 
NO 
NO 
NO 
NO 
NO 
NO 
NO 
NO 
NO 
NO 
NO 
NO 
NO 
NO 
NO 
NO 
NO 
NO 

0.09 
0.08 
0.09 
0.17 
0.17 
0.06 
0.10 
0.10 
0.14 
0.17 
0.07 
0.08 
0.07 
0.07 
0.22 
0.72 
0.13 
0.10 
0.10 
0.09 
0.20 
0.08 
0.08 
0.09 
0.09 
2.76 
0.09 
0.25 

9 
8 
9 
17 
17 
6 
10 
10 
14 
17 
7 
8 
7 
7 
22 
72 
13 
10 
10 
9 
20 
8 
8 
9 
9 
276 
9 
25 

14 
14 
14 
7 
7 
19 
12 
12 
8 
7 
17 
15 
17 
17 
5 
2 
9 
12 
12 
13 
6 
16 
14 
13 
13 
0 
14 
5 

 
Compound 

Category 

b 

ub 

b/ub 

Slope ≠ 0 

Uncertainty  
 [6 we] 

Uncertainty 
[%}(6 we) 

Shelf-life  
[we] (U=20%) 

Ethalfluralin 
Organonitrogen 
Tetrachloronitrobenzene (Tecnazene)  Organonitrogen 
Organonitrogen 
Trifluralin 
Organonitrogen 
Diphenamid 
Organonitrogen 
Pebulate 
Organonitrogen 
Bupirimate 
Organonitrogen 
Chlorfenapyr 
Organonitrogen 
Etridiazole 
Organonitrogen 
Flusilazole 
Organonitrogen 
Flutriafol 
Organonitrogen 
Folpet 
Organonitrogen 
MGK-264 
Organonitrogen 
Penconazole 
Organonitrogen 
Propargite 
Organonitrogen 
Terbuthylazine 
Organonitrogen 
Triflumizole 
Organonitrogen 
Vinclozolin 
Organophosphorous 
Chlorpyrifos methyl 
Organophosphorous 
Diazinon 
Organophosphorous 
EPN 
Organophosphorous 
Fenitrothion 
Organophosphorous 
Isazophos 
Organophosphorous 
Phosalone 
Organophosphorous 
Pirimiphos ethyl 
Organophosphorous 
Pirimiphos methyl 
Organophosphorous 
Pyraclofos 
Organophosphorous 
Pyrazophos 
Organophosphorous 
Quinalphos 

1.68 
2.42 
1.44 
2.14 
-0.48 
-0.22 
1.72 
2.16 
1.26 
6.12 
-0.52 
-0.09 
1.78 
1.34 
0.75 
5.75 
1.11 
0.19 
5.62 
2.40 
0.43 
4.49 
-0.68 
-0.15 
6.75 
2.36 
0.35 
-13.43  32.25 
-0.42 
4.49 
1.33 
0.30 
5.81 
3.27 
0.56 
5.08 
2.75 
0.54 
7.73 
2.07 
0.27 
3.69 
2.22 
1.66 
0.23 
5.41 
1.23 
76.69  153.71  0.50 
2.00 
2.80 
5.59 
2.39 
2.96 
7.08 
0.83 
6.09 
5.07 
201.18  328.16  0.61 
2.12 
3.88 
8.24 
0.29 
12.49 
3.56 
3.76 
0.71 
5.28 
66.06  128.97  0.51 
0.33 
25.28 
8.35 
0.69 
27.28 
18.71 
-0.28 
5.49 
-1.53 

71 

NO 
NO 
NO 
NO 
NO 
NO 
NO 
NO 
NO 
NO 
NO 
NO 
NO 
NO 
NO 
NO 
NO 
NO 
YES 
NO 
NO 
YES 
NO 
NO 
NO 
NO 
NO 
NO 

0.09 
0.11 
0.09 
0.35 
0.10 
0.30 
0.28 
0.23 
0.34 
0.95 
0.26 
0.29 
0.27 
0.44 
0.12 
0.27 
2.25 
0.16 
slope≠0 
0.30 
2.21 
slope≠0 
0.56 
0.28 
2.15 
0.99 
0.82 
0.30 

9 
11 
9 
35 
10 
30 
28 
23 
34 
95 
26 
29 
27 
44 
12 
27 
225 
16 
slope≠0 
30 
221 
slope≠0 
56 
28 
215 
99 
82 
30 

13 
11 
13 
3 
12 
4 
4 
5 
4 
1 
5 
4 
4 
3 
10 
4 
1 
7 
slope≠0 
4 
1 
slope≠0 
2 
4 
1 
1 
1 
4 

 
Compound 

Category 

b 

ub 

b/ub 

Slope ≠ 0 

Uncertainty  
 [6 we] 

Uncertainty 
[%}(6 we) 

Shelf-life  
[we] (U=20%) 

Carbophenthion 
Chlorthiophos 
Coumaphos 
Disulfoton 
Edifenphos 
Ethion 
Fenchlorphos (Ronnel) 
Fonofos 
Leptophos 
Methacrifos 
Phorate 
Piperonyl butoxide 
Profenofos 
Sulfotepp 
Terbufos 
Triazophos 
Acrinathrin 
Bifenthrin 
lambda-Cyhalothrin 
Phenothrin (cis & trans) 
Transfluthrin 

Organophosphorous 
Organophosphorous 
Organophosphorous 
Organophosphorous 
Organophosphorous 
Organophosphorous 
Organophosphorous 
Organophosphorous 
Organophosphorous 
Organophosphorous 
Organophosphorous 
Organophosphorous 
Organophosphorous 
Organophosphorous 
Organophosphorous 
Organophosphorous 
Synthetic pyrethroid 
Synthetic pyrethroid 
Synthetic pyrethroid 
Synthetic pyrethroid 
Synthetic pyrethroid 

0.53 
5.49 
2.89 
0.60 
5.28 
3.19 
0.41 
5.10 
2.09 
2.61 
5.53 
14.42 
0.09 
6.30 
0.55 
0.83 
4.80 
3.98 
2.60 
5.94 
15.47 
0.21 
2.25 
0.47 
0.42 
6.02 
2.54 
0.61 
4.46 
2.71 
0.20 
5.08 
1.03 
0.78 
5.52 
4.33 
-0.89 
3.13 
-2.79 
-0.08 
2.18 
-0.17 
-3.80 
2.55 
-9.69 
0.58 
3.36 
1.95 
-1.83 
2.84 
-5.18 
-1.54 
3.38 
-5.22 
-1.89 
2.78 
-5.26 
-4.88 
-1.79 
2.73 
65.15  128.41  0.51 

NO 
NO 
NO 
YES 
NO 
NO 
YES 
NO 
NO 
NO 
NO 
NO 
NO 
NO 
YES 
NO 
NO 
NO 
NO 
NO 
NO 

0.29 
0.28 
0.27 
slope≠0 
0.34 
0.27 
slope≠0 
0.13 
0.30 
0.23 
0.47 
0.27 
0.23 
0.13 
slope≠0 
0.23 
0.28 
0.32 
0.28 
0.26 
2.19 

29 
28 
27 
slope≠0 
34 
27 
slope≠0 
13 
30 
23 
47 
27 
23 
13 
slope≠0 
23 
28 
32 
28 
26 
219 

4 
4 
4 
slope≠0 
4 
4 
slope≠0 
9 
4 
5 
3 
4 
5 
9 
slope≠0 
5 
4 
4 
4 
5 
1 

72 

 
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