Food Anal.
Methods
DOI 10.1007/s12161-014-9994-4
A Survey on Long-Term Stability of Stock Standard Solutions
in Pesticide Residue Analysis
Patrizia Stefanelli & Danilo Attard Barbini &
Graziella Amendola & Tiziana Generali &
Silvana Girolimetti & Patrizia Pelosi & Angela Santilio
Received: 23 April 2014 / Accepted: 8 September 2014
# Springer Science+Business Media New York 2014
Abstract The aim of this study was to highlight the need to
extend the lifetime of stock standard solutions employed for the
analysis of pesticide residues with respect to the quality control
standards in use. The importance of this survey concerns the
possibility to extend the solution lifetime up to year when the
standard solutions are stored in refrigerator at 4 °C. In order to
allocate a solution lifetime up to year, the guideline document
SANCO/12571/2013 was followed. During the time 2010–
2013, the stability data were collected for 82 different active
substances from the Italian National Reference Laboratory
(NRL) for pesticide residues, accredited to the ISO/IEC
17025. A statistical analysis was performed on the overall data.
Some aspects have been monitored such as the solvent and
detection method used, the relative standard deviations (RSDs)
of the mean responses of the old and fresh stock solutions
investigated, the percentage difference of the mean responses
of the old and fresh stock solutions, and finally the uncertainty
measurement of the standard preparation.
Keywords Pesticide residues . Quality assurance . Stability .
Stock solution
Introduction
Pesticide residue analysis plays a crucial role in the evaluation
of the human and environmental exposure to pesticides, for
Electronic supplementary material The online version of this article
(doi:10.1007/s12161-014-9994-4) contains supplementary material,
which is available to authorized users.
P. Stefanelli (*) : D. A. Barbini : G. Amendola : T. Generali :
S. Girolimetti : P. Pelosi : A. Santilio
Department of Environmental and Primary Prevention, Pesticide
Section, National Institute of Health (Istituto Superiore di Sanità),
Viale Regina Elena, 299-00161 Rome, Italy
e-mail: patrizia.stefanelli@iss.it
controlling the farmers compliance to good agricultural prac-
tices, to facilitate regulatory decisions and to strengthen the
consumers trust towards food safety (European Communities
2004; European Union 2009).
Member states carry out official controls on pesticide res-
idues in order to enforce compliance with maximum residue
levels (European Commission 2011; European Council 2005;
European Council 2008; Italian Ministerial 1992).
In the European Union (EU), accreditation in the area of
food and feed testing (according to ISO/IEC 17025) is a
prerequisite for the laboratories involved in the official control
in order to verify the compliance with food regulation
(European Parliament and Council 2004). The standard ISO/
IEC 17025 and the European technical guidance SANCO/
12571/2013 on Method Validation and Quality Procedures
for Pesticide Residues in Food and Feed requires to test the
stability of standard solutions (European Standard 2005;
Directorate General for Health and Consumer Affairs (DG
SANCO) 2013).
During the accreditation audit of the analytical laboratories,
the inspectors frequently demand experimental evidence of
the stability of the standard solutions; as consequence, the
laboratories have to check their collection of the standard
solutions. To achieve the data on stability solutions, the labo-
ratories have to replace continuously the stock standard solu-
tions with great waste of time and resources, even if sufficient
experience exists on a certain stable pesticides following
specified storage conditions.
In addition, the costs related to the continuous monitoring
of standard solutions have to be taken into consideration.
Furthermore, the stability information could be obtained not
only from experimental data but also from literature, even if
limited literature data was available, at least in part, on the
pesticides due to the fact that data collected in each laboratory
are part of their quality system and so rarely published
(Berendsen et al. 2011; Tsong 2003; Karinen et al. 2011;

Avramides 2005). This work provides statistical assessment
on the standard stability obtained from a planned survey of the
Italian National Reference Laboratory (NRL) for pesticide
residues.
The aim of this study was to provide data on pesticide
standard solution stability collected over the period 2010–
2013. In order to reduce the frequency of the quality control
and the relative costs of analysis, a statistical evaluation of the
overall stability data were performed.
In this study, the standard solution stability has been
checked by comparison of the detector response of a solution
freshly prepared with the detector response of an existing
standard solution. To evaluate the solution stability, the mean
measurements (at least in triplicate) for the solutions (old and
new) were considered and the average of the replicates should
not differ by more than ±10 %. The mean of the detector
response of the new solution was set up at 100 %.
Several polar and non-polar active substance stock solu-
tions prepared and diluted in acetonitrile or toluene have been
investigated by using liquid and gas chromatography-mass
spectrometry.
A large amount of stability data was presented in this study
even if we cannot considered complete due to the continuous
introduction of new active substances in the market.
Materials and Methods
Reagents
Pure analytical standards of investigated pesticides were pro-
vided by Chemservice (West Chester, PA, USA). Purities for
all compounds ranged between 95 and 99.8 %. High-
performance liquid chromatography (HPLC)-grade acetoni-
trile and toluene pure for analysis (Sigma-Aldrich, MO, USA)
were used. Milli-Q water was prepared using Milli-Q system
(Millipore, MA, USA).
Apparatus
A Varian System ProStar HPLC (Walnut Creek, CA),
equipped with a Varian 1200L Quadrupole MS/MS detector,
was employed. The liquid chromatography was equipped with
a Varian 410 autosampler (Walnut Creek, CA). A Valco valve
of injection with a loop of 100 μl was used. The injection
mode was partial loopfill. The detection was achieved by mass
spectrometry equipped with electrospray ionization interface
(ESI). Typical source parameters were as follows: ionization
voltage was 1,400 V; capillary voltage was −40 V; and the
nebulizer gas was synthetic air at 30 psi. The solvent evapo-
ration in the source was assisted by a drying gas (heater
synthetic at 200 °C at 30 psi). Data analyses were performed
by software Varian MS Workstation version 6.8. An Agilent
Food Anal. Methods
Technologies 7890A gas chromatograph (Wilmington, DE,
USA), equipped with a 7000 GC/MS Triple Quad detector
was employed. The gas chromatograph was equipped with a
Agilent Technologies 7693 autosampler (Wilmington, DE,
USA). A Programmed Temperature Vaporising (PTV) injector
was used. Sample injection was carried out using the PTV
solvent vent mode. The mass spectrometer was used in elec-
tron ionization (EI) operating in MS/MS acquisition mode.
The transfer line temperature was kept at 280 °C. Data acquisi-
tion was accomplished by Agilent Mass Hunter Workstation GC/
MS Acquisition Software, version B.05.00. Data processing was
accomplished by Agilent Mass Hunter Workstation Qualitative
and Quantitative Analysis Software, version B.03.00 and
B.04.00, respectively. A gas chromatograph (Agilent
Technologies 6890 Plus, Wilmington, DE, USA) equipped with
a 5973 Network Mass Selective Detector was employed. The gas
chromatograph was equipped with an Agilent Technologies
7683 autosampler (Wilmington, DE, USA). A split/splitless
injector was used. A quadrupole mass filter was used with a
transfer line temperature set at 280 °C. The mass spectrometer
was used in electronic ionization (EI) operating in single-ion
monitoring (SIM) or full-scan acquisition mode with ionization
energy of 70 eV. Both data acquisition and processing were
accomplished by Chemstation software. Table 1 shows the oven
temperature program of the gas chromatographs. Figure 1 shows
the instrumental signals of a standard solution.
Methodology
To prepare the primary stock solutions, accurately weigh at
least 20 mg (±0.01 mg) of pure standard and transfer it to a
50-mL volumetric flask, up to a volume of appropriate solvent
to obtain a stock solution between 0.5 and 1 mg/mL.
Working solutions were prepared by dilution of the stock
solution to a final concentration of 10 μg/mL, usually, 0.5 mL
(V1) was diluted to the final volume of 50 mL (V2), after 1 mL
of this solution were diluted (V3) in 10-mL (V4) volumetric
flask to a final concentration of 1 μg/mL. All solutions were
stored at 4–6 °C following the provider’s indication of storage.
Stock solutions for a selection of pesticides were prepared in
acetonitrile and toluene, respectively.
Table 1 Gas chroma-
tography instrumental Oven temperature program
conditions
Temp (°C) Rate Hold (min)
(°C/min)
50 – 0.1
70 120 1.8
150 25 –
200 3 –
280 8 10
Food Anal. Methods
Fig. 1 GC/MS/MS instrumental
signals of a standard solution
The freshly prepared standard solutions were analyzed with
the stored standard solutions in the same instrumental se-
quence. First, the freshly prepared solutions were injected,
followed by the stored standard solutions. The average peak
areas of the three replicate injections of each original stored
standard solution were compared to the average peak areas
generated by the three replicate injections of each freshly
prepared standard solutions. The results were expressed as
the difference percentage (Δ%) by using Eq. 1.
The mean of the detector response of the new solution is
taken at 100 %. In particular, the mean measurements (n=3)
for the solutions (old and new) should not normally differ by
more than ±10 %. Table 1S reports the compounds investi-
gated, in some cases, repeatedly over time.
All elaborations were accomplished by software SPSS
Statistics (version 20).


FRiold −FRinew
Δ%  100 ð1Þ
FRinew
where factor response (FR) is
Areai
FRi ¼ ð2Þ
Conci
In order to allocate a lifetime to standard solutions, a
statistical procedure was performed to evaluate all data. In
particular, descriptive statistics (frequency distributions, cen-
tral tendency, and box plot of the quartiles) were used to
present quantitative descriptions in a manageable form. The
descriptive statistics permit to simplify large amounts of data
in a sensible way to reduce lots of data into a simpler summa-
ry. In fact, the control charts as the only statistic tool, could not
be sufficient for an accurate analysis.
Estimation of Uncertainty Measurement
Moreover, an estimation of uncertainty of measurement of the
preparation of calibration standard, using a bottom-up ap-
proach, was performed and how this contributes has impacted
on the overall uncertainty of the method. In particular, in the
estimation of the overall uncertainty measurement of a
pesticide residue method, the contributions have taken into
account introduced by the various acceptance criteria of the
method. The bottom-up approach, adopted by the
International Organization for Standardization (ISO) and by
the EURACHEM/CITAC guide, estimates the overall uncer-
tainty by identifying, by estimating, and by combining all
sources of uncertainty associated to the analytical result
(CITAC/EURACHEM 2012; International Organization for
Standardization ISO TC 21748 2010).
In order to estimate the overall uncertainty measurement,
six main contributions were considered: the uncertainty joined
to the precision of method, the linearity, the drift between
bracketing injections of the same calibration standard, the
stability of standard solutions, the preparation of stock solu-
tions, and the sample weight. As concern the first four contri-
butions, we have taken in account the acceptance criteria
established in the document SANCO/12571/2013 for the an-
alytical methods employed in the analysis of pesticide residue.
The standard uncertainty contribution of the weight and
volumetric equipment was assumed to be rectangular distributed
(type B evaluation), and these values are given by the Eq. 3:
toleranceðaÞ
ua ð%Þ ¼ pffiffiffi ð3Þ
a 3
and also from the purity of standard to be a rectangular
distribution.
The standard uncertainty contribution of the linearity and the
instrumental drift were assumed to be triangular distributed
(type B evaluation), and these values are given by the Eq. 4:
toleranceðaÞ
ua ð%Þ ¼ pffiffiffi ð4Þ
a 6
Results and Discussion
According to the European Standard ISO/IEC 17025, an
internal quality control procedure is required for the monitor-
ing of the test validity. Registration of the resulting data and

Fig. 2 Control chart of the stability data of stock standard solution
trends should be detectable together with a practical review of
the results (Bertoni Olivares and Antunes Lopes 2012; Egea
Gonzales et al. 2004). The process of internal quality control is
based on a description of the parameters of an ongoing ana-
lytical system in normal operation. These internal quality
strategies are mandatory for accredited testing laboratories in
order to assure that the analytical process remains stable, with
statistical control data. The implementation of the internal
quality assurance allows to demonstrate the performance of
the tests, as well as to avoid mistakes (Stefanelli et al. 2013;
Konieczka 2007). The same reference materials should be
checked by using procedures valid for their technical and
Fig. 3 Box plot diagrams of three
different groups clustering the
stability data: group 1 <6 months;
group 2 ≥6 months, <12 months;
group 3 ≥12 months
Food Anal. Methods
economic feasibility. Moreover, to assess the long-term stabil-
ity of the stock standard solutions, the accredited laboratory
routinely employs control charts as monitoring tools for each
internal quality control.
In this study, the descriptive statistics have been added in
order to outline the spread of the data collection and to assess
the whole population. These specific statistical controls could
be considered as additional monitoring tools of the current
protocol of the analysis.
Moreover, the stability of stock solutions has been checked
by preparing a new solution and comparing the detector
responses from freshly prepared solutions of old and new
Food Anal. Methods

standards. The approach described in this work is what it is

suggested by the document SANCO 12571/2013. In particu-
lar, measurements to determine the mean detector response
have been analyzed (at least in triplicate) for the solutions (old
and new) in the same analytical sequence and the difference of
detector response should not normally differ by more than
±10 %. The mean of the detector response of the new solution
is taken to be 100 %.
The value of ±10 % has been set as our acceptance criteria,
and the solutions are considered stable if the difference per-
centage is still within the required range. Discrepancies be-
tween the concentrations of new and old solution can be due to
a number of factors such as analyte precipitation, solvent
evaporation, differences in the purities between the old and
new standards, and error in weighing other than the analyte
degradation. Where sufficient evidence exists that a certain
pesticide is stable using specified storage conditions (time,
solvent, or storage temperature) is important that a laboratory
reproduces these storage conditions. Currently available data
show that most of pesticide stock solutions, when stored in Fig. 4 Frequency of stability data collected for group 1
tightly closed glass containers in low temperature, are stable in
toluene, acetone, ethyl acetate, or acetonitrile (Data Pool of the of the central tendency with respect to the interquartile range is
European Union Reference Laboratory of pesticide). Also, the shown. In our cases, the median was positioned toward the
variability of replicate injections (expressed as repeatability— lower end of the data (negative side) with a good central
relative standard deviation (RSD)) should be taken into ac- tendency. A typical data values and the degree to which those
count and typically not exceed 10 % for both the old and new values are atypical can be identified. In our cases, all groups
standard solutions, as suggested by the SANCO document. presented outliers.
The control chart (Fig. 2) reports all results collected in Figures 4, 5, and 6 show the plots of the data sets as normal
temporal distribution. In some cases, the acceptance criteria frequency distribution curves superimposed to histograms.
were exceeded. This graphical representation had not shown The storage was at 4–6 °C up to 6 months (group 1) and
significant trend; therefore, a clustering study has been per- 12 months (group 2). The distributions are homogeneous with
formed to give a better understanding. The descriptive statis-
tical tools such as central tendency and box plot of the quar-
tiles and frequency distributions have been performed.
According to the time interval between the preparation
dates of the old and new stock solutions, the collected data
were clustered in three different groups, listed as follows:

1. Group 1, <6 months

2. Group 2, ≥6 months, <12 months
3. Group 3, ≥12 months

In Fig. 3, the data were shown as box plots where the

measure of dispersion was known as the interquartile range;
in particular, the yellow-shaded box represents the interquar-
tile range bounded by the data values that correspond to the
25th and 75th quartiles. The black line running though the box
was the median. The whiskers were the largest and smallest
data values that were not outliers, where an outlier can be
considered an atypical data value. Data values that are be-
tween 1.5 and 3 interquartile ranges below or above the 25th
or 75th quartiles are considered outliers and represented in the
diagram with an open circle. Using the box plot, the position Fig. 5 Frequency of stability data collected for group 2
 Food Anal. Methods

Fig. 6 Frequency of stability data

collected for group 3

very limited cases exceeding the acceptance criteria. These instead of a systematic bias (Thompson and Wood 1995).
cases could be imputed to run effect exemplifying by a ran- Unacceptable case improvement was observed (group 3)
dom deviation of the analytical system during a particular run when the storage time exceeded 12 months, particularly in

Fig. 7 Uncertainty contribution 4

in standard preparation

0
Total m (std) Purity stand V1 V4 V2 V3
Food Anal. Methods

Table 2 Results of individual,

combined, and expanded uncer- Components Criterion Distribution k ν Rel. type uncertainty
tainties in the analysis of pesticide
residues Precision method 20 % Uniform √2 inf. 14 %
Standard preparation – Rectangular √3 inf. 3.2 %
Stability standard solution 10 % Uniform 1 inf. 10 %
Instrumental drift 30 % Triangular √6 inf. 12 %
Sample weight – Rectangular √3 inf. 1.2 %
Linearity 20 % Triangular √6 inf. 8%
Combined uncertainty (uc) 23 %
Freedom degree (ν) inf.
Coverage factor (k) 2
Relative expanded uncertainty (U%) 46 %

positive side. These patterns also reflect the measure of dis-
persion observed in Fig. 3.
According to the evaluation used, a positive percentage
difference could indicate evaporation of solvent from the old
stock solution. In group 3, these cases are frequent and corre-
spond to trans-Chlordane; Chlorobenzilate; trans-HEPO, +
10 %, and Chlorpyrifos, +12 %, whereas only one case has
been verified in group 2 (alpha-HCH +19.1 %). Evaporation
of solvent during the storage occurred in particular for stock
solutions prepared in toluene in order to perform the analysis
in gas chromatography. A negative percentage difference
could indicate degradation of pesticide in the older stock
standard solution. The data set of group 3 reports again the
most frequent cases.
In Table 1S, specific and important additional information
have been reported such as the solvent and detection method
used, the RSDs of the mean responses of the old and fresh
stock solutions, and finally the percentage difference of the
mean responses of the old and fresh stock solutions. In case of
more than one time interval, the longest period has been
reported or if the acceptance criteria were exceeded, the cor-
responding period has been reported. The RSDs of our tripli-
cates did not exceed the value of 5 %, with the exception of six
cases with higher values in the range 6.24–12.1 %. About
30 % of our repeatability data did not exceed the value of 1 %
with a good precision. Although the data of this study are
referred to a limited selection of active substances, the assess-
ments could be applicable to most pesticides. The survey
supports the suggestion to prolong the expiry date of stock
standard solutions up to 1 year.
In conclusion, the laws of propagation for combining the
uncertainties were used to calculate the uncertainty on the
standard preparation. The combined uncertainty associated
to the calibration standards was a value of 3.2 %. All the
uncertainty components for determining the standard uncer-
tainty from standard preparation are shown in Fig. 7.
Concerning standard preparation, the contribution of the
uncertainty on the weighing procedure (labeled as m (std) in
Fig. 7) was the main and the purity standard is similar. The
uncertainty on the volume of the flask (50 ml) has virtually not
influenced on the overall uncertainty (labeled as Total in
Fig. 7). The m (std) component was calculated as a type B
evaluation with the Eq. 3, and it involves the weighing;
consequently, this contribution has a potential uncertainty
source identifiable with the balance. In addition, the purity
of standard was assumed a rectangular distribution and was
usually quoted in the supplier’s certificate as >95 %. The
tolerance on purity was given by the manufacturer and was

Fig. 8 Contribution of individual

uncertainties to the total
uncertainty

not higher than ±2.0 % (Stefanelli et al. 2012; Ratola et al.
2006).
Afterwards, the magnitude of uncertainty of a pesticide
residue method associated to the most relevant contributions,
in some specific cases using the fixed values of acceptance
criteria reported in the European guidance document, was
estimated. The results are shown in Table 2. The final result
is normally expressed as expanded uncertainty U, which is the
value of u(x) usually multiplied by a factor of coverage (k) of 2
(with 95 % confidence level).
This approach which centers on the maximum target
values for some contributions permits to estimate the
threshold of uncertainty measurement for a laboratory
that analyze pesticide residue using multiresidue meth-
od. In particular, for four main contributions, the own
specifications were considered as reported in Table 2—
the precision of method, the linearity, the drift between
bracketing injections of the same calibration standard,
and the stability of standard solutions— and finally
combining them to the contributions that arise from
the preparation of stock solutions and the sample
weight.
For linearity, the maximum specification is a value of
residuals of 20 % whereas the significant instrumental drift
of the bracketing calibration is a value of 30 %. For these
contributions, it is appropriate to assume a triangular distribu-
tion; consequently, the contributions to the uncertainty were
estimated by using the Eq. 4.
The method precision is studied via recovery experiments
in accordance with the SANCO guideline with a RSD not
exceeding the value of 20 %.
The uncertainty due to the repeatability represents the
most significant source of the total uncertainty; the
value was calculated as a type A evaluation assuming
a uniform distribution (Christensen et al. 2003). The share of
the uncertainty held by the standard preparation is not crucial
for the total uncertainty as shown in Fig. 8.
Finally, the relative combined uncertainty of 23 % gives an
estimate of the expanded uncertainty of 46 %. Moreover, the
calculated expanded uncertainty of 46 % is less than the
default value of 50 % (corresponding to a 95 % confidence
level), adopted from European guidance document SANCO
based on the fit-for-purpose (FFP) RSD (Medina-Pastor et al.
2011).
Conflict of Interest Patrizia Stefanelli declares that she has no conflict
of interest; Danilo Attard Barbini declares that he has no conflict of
interest; Graziella Amendola declares that she has no conflict of interest;
Tiziana Generali declares that she has no conflict of interest; Silvana
Girolimetti declares that she has no conflict of interest; Patrizia Pelosi
declares that she has no conflict of interest; and Angela Santilio declares
that she has no conflict of interest. This article does not contain any
studies with human or animal subjects.
Food Anal. Methods
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