Journal of Chromatography A: Susana Grimalt, Pieter Dehouck

Journal of Chromatography A, 1433 (2016) 1–23
Contents lists available at ScienceDirect
Journal of Chromatography A
journal homepage: www.elsevier.com/locate/chroma
Review of analytical methods for the determination of pesticide

residues in grapes
Susana Grimalt, Pieter Dehouck ∗
European Commission, Directorate General Joint Research Centre, Institute for Reference Materials and Measurements, Retieseweg 111, 2440 Geel, Belgium
a r t i c l e i n f o a b s t r a c t
Article history: This review presents an overview of analytical methods for the analysis of pesticide residues in grapes
Received 13 July 2015 and by-products in the last decade. The most widely used detection technique for the determination of
Received in revised form pesticides in grapes is mass spectrometry combined with gas and/or liquid chromatography. In general,
23 December 2015
multi-residue methods with selective sample treatment methodologies have been developed for this
Accepted 28 December 2015
purpose. However, this review focuses not only on these common multi-residue methods but also on
Available online 2 January 2016
specific methodologies as single-residue methods for the analysis of pesticides in grapes and by-products.
Finally, the limitations of multi-residue methods, the future perspectives and the trends for pesticide
Keywords:
Grapes
residue analysis in grapes are reviewed.
Pesticides © 2016 The Authors. Published by Elsevier B.V. This is an open access article under the CC BY-NC-ND
Multi-residue method license (http://creativecommons.org/licenses/by-nc-nd/4.0/).
Single-residue method
LC–MS
GC–MS
Contents
1. Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1
2. Use and occurrence of pesticides in grape cultivation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2
3. Analytical methods . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 5
3.1. Sampling and sample preparation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 5
3.2. Sample extraction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 5
3.3. Clean-up of the extract . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 16
3.4. Common instrumental techniques for analysis . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 17
3.4.1. GC–MS based methods . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 17
3.4.2. LC–MS based methods. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .18
3.4.3. High resolution MS-based methods . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 18
3.5. Quantitative analysis and matrix effect . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 18
4. Limitations of multi-residue methods . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 19
5. Future perspectives . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 19
6. Conclusions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 20
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 20
1. Introduction nutritional properties of grapes and their ancient domestication

leading to a large variety of by-products [2]. Grapes are consumed
Nowadays, the cultivation of grapes is widely spread around the both as fresh and as processed products such as wine, jam, juice,
world with an estimated surface area of 7.6 million of hectares in jelly, grape seed extract, raisins, vinegar and grape seed oil. In 2014
2014 [1]. Grape production is an important activity due to the high the global grape production was estimated at 73.7 million tons.
From this, 41% was produced in Europe, 29% in Asia and 21% in
America. Approximately 45% of the grape production consists of
∗ Corresponding author. unpressed grapes, while the other 55% is mainly used for wine pro-
E-mail address: Pieter.Dehouck@ec.europa.eu (P. Dehouck). duction. Up to 78% (24.8 million tons in 2014) of the unpressed
http://dx.doi.org/10.1016/j.chroma.2015.12.076
0021-9673/© 2016 The Authors. Published by Elsevier B.V. This is an open access article under the CC BY-NC-ND license (http://creativecommons.org/licenses/by-nc-nd/4.0/).
2 S. Grimalt, P. Dehouck / J. Chromatogr. A 1433 (2016) 1–23
grapes is consumed as fresh grapes [1]. All this shows that the grape tories to have free choice of methods, which is beneficial for the
market plays a very important role in the world food consumption. continuous development of the analytical methods. Laboratories
In grape production, pesticides are used to control pests and performing analyses of pesticide residues also tend to work under
diseases in vineyards to increase crop yield. The most common a quality system like ISO/EC 17025 [14] to ensure a consistent and
fungal diseases in vineyards are powdery mildew (Uncinula neca- reliable approach with the use of quality control measures like
tor), downy mildew (Plasmopora viticola) and gray mold (Botrytis certified reference materials and participation in proficiency tests
cinerea) [3]. The most menacing insects in grape plants are the Euro- [15,16].
pean grapevine moth (Lobesia botrana), vine mealybug (Planococcus This paper presents an overview of the evolution in analytical
ficus), and the citrus mealybug (Planoccoccus citri) [4]. To prevent methods for pesticide residue analysis in grapes during the last
these, a large variety of pesticides, especially fungicides and insec- decade. By illustrating the large variety of pesticides occurring in
ticides, are applied frequently during the cultivation of grapes the vineyard, it aims to explain the large range of analytical meth-
(Table 1). In some cases, unsuitable agricultural practices are used ods developed for the analysis of pesticides in grapes until today.
during the application of these active materials in the vineyard. The review focuses on the limitations of these methods and on
As a result the level of pesticide residues in or on grapes at the potential future perspectives.
moment of harvest is higher than the permitted level by regula-
tion [5]. Apart from the environmental risk, a high level of pesticide
residues can affect the quality of the grapes and its processed prod- 2. Use and occurrence of pesticides in grape cultivation
ucts and it may ultimately reach the consumer and cause health
hazards. Therefore, in order to prevent health risks it is impor- According to the principles of integrated pest management the
tant to monitor the presence of pesticides and regulate their levels monitoring of pesticide residues is essential in order to predict the
in grapes. In the European Union, Regulation 396/2005/EC estab- proper concentrations and number of applications of pesticides
lishes the maximum residue levels (MRLs) of pesticides permitted needed and to determine the pre-harvest interval. The applica-
in products of animal or vegetable origin intended for human or tion of the principles of integrated pest management and good
animal consumption [6]. The MRLs for pesticide residues in grapes agricultural practices resulted in a reduction of pesticide usage
mostly range between 0.01 mg/kg and 5 mg/kg depending on the with the tendency to reduce the most environmental dangerous
pesticide, but in some cases higher limits are established, e.g., for pesticides [17]. Because of this the number of common pesticides
fosetyl-aluminium 100 mg/kg [6]. applied and found as residues at harvest is normally lower than
To measure these low concentrations highly selective, sensitive the number of pesticides registered by the relevant authorities in
and accurate analytical methods are needed. Due to the large num- each country (Table 1). For instance, there are around 450 pes-
ber of pesticides on the market, the use of multi-residue methods ticides in the EU database [6,18] for which the MRLs have been
capable of analysing large numbers of pesticides in one single run established in table and wine grapes, but according to the litera-
is the most common and most efficient approach. In the European ture less than half of them are actually applied for pest control in
Union (EU) a joint work of European Union Reference Laborato- vineyards (see Table 1 for common pesticides and MRL values in
ries (EURLs) and National Reference Laboratories (NRLs) of each Europe). Another example can be found in the common integrated
EU member state maintain and improve the quality, accuracy and pest management guidelines for grapes where the number and
comparability of the measurements and results between Official the quantity of broad-spectrum organophosphate and carbamate
Laboratories. The EURLs are responsible for guiding and provid- products dropped considerably [19].
ing analytical methods, organising proficiency tests, and promoting A number of studies dealing with the monitoring of pesti-
the development and validation of new analytical methods. The cides in grapes have been published. A study by Česnik et al.
EURL for pesticides in fruit and vegetables (EURL-FV) published [20] in which pesticide residues in wine grapes were monitored
on its website a multi-residue method called the Mini-Luke sam- in three different regions in Slovenia showed that the most fre-
ple extraction, which is based on the original Luke method [7]. quently found pesticides in grapes were folpet (97,9%), cyprodinil
This analytical method has recently been improved, validated and (51.1%), dithiocarbamates (44.7%), chlorothalonil (23.4%), chlorpy-
implemented in routine in the Dutch NRL by Lozano et al. [8]. Also riphos (19.1%) and pyrimethanil (14.9%). The concentration range
other organizations as the European Committee for Standardiza- of these pesticide residues found in grapes were below the MRLs
tion (CEN) assist laboratories by providing some standard methods described in the EU regulation [4], except in case of cyprodinil
for the determination of pesticide residues in foods of plant ori- and fludioxonil which exceeded the MRL in 38,3 % of the sam-
gin. In 2008, three analytical multi-residue methods based on gas ples. Two surveys [21,22] for table grapes carried out in three
chromatography coupled to mass spectrometry (GC–MS) [9,10] different regions in Turkey showed that chlorpyrifos-methyl and
and/or liquid chromatography coupled to tandem mass spectrome- chlorpyrifos-ethyl, besides deltamethrin and ␭-cyhalothrin, were
try (LC–MS/MS) [10,11] were published, where grapes were tested the most frequently found pesticides [21]. Moreover the pesticides
as one of the representative fruit matrices. The Association of Offi- azoxystrobin, boscalid, cyprodinil, dimethomorph, flufenoxuron,
cial Analytical Chemists (AOAC) International also published an hexythiazox, imazalil, methomyl, penconazole and thiophonate
official method for the analysis of pesticide residues in represen- methyl were detected in concentrations above the MRLs [22]. In
tative matrices as grapes, lettuces and oranges, with a common a survey of the Egyptian market [23] the most detected pesticides
sample treatment followed by GC–MS and LC–MS/MS analysis [12]. in grapes were carbendazim, acetamiprid, boscalid, ␭-cyhalothrin,
Besides the use of official methods, many laboratories develop profenofos and pyraclostrobin. Other frequently found pesticides
and validate their own method for pesticide residues analysis in grapes were cyprodinil, chlorpyrifos, delthamethrin and iprodi-
because depending on the analytical technique chosen, different one. An exhaustive analysis carried out during 1998 and 2003 by
approaches for sample treatment may be considered. Even when the National Food Institute in Denmark on imported grapes from 17
using the same technique, different equipment or equipment set- different countries (considering as main exporters Italy and South
tings can be selected, making it difficult to reach a universally Africa) [24] concluded that some samples from Italy exceeded the
accepted analytical method. The European Commission’s Direc- MRLs for the pesticides phosalone, fenitrothion and bromopropy-
torate for Health and Food Safety (DG SANTE) provides guidance late, while samples from South Africa had residues of prothiofos.
to laboratories for the validation of methods for pesticide residues Another study in fruits and vegetables reported the presence of the
analysis in food and feed. [13] This guidance allows the labora- pesticides captan and methomyl at concentrations higher than the
S. Grimalt, P. Dehouck / J. Chromatogr. A 1433 (2016) 1–23 3
Table 1
Most common pesticides used in vineyards.
Pesticide Family-activity Pest control MRL Table/Wine grapes (mg/kg)
Acetamiprid Neonicotinoid insecticide Leafhoppers and other small insect pests 0.5
Azinphos-methyl Organothiophosphate Insect and mite pests 0.05
acaricide/insecticide
Azoxystrobin Strobilurin fungicide Downy mildew 2
Phomopsis cane and leaf spot
Powdery mildew
Rotbrenner
Benalaxyl Anilide fungicide Downy mildew 0.3a
Benalaxyl-M (or Kiralaxyl) Anilide fungicide Downy mildew 0.3a
Bifenthrin Pyrethroid insecticide Insect and mite pests 0.2
Boscalid Anilide-pyridine fungicide Grey mould 5
Powdery mildew
Bromopropylate Diphenyl acaricide Mite pest 0.01
Captan Phatalamide fungicide 0.02
Carbaryl Carbamate acaricide/insecticide Grape leaffolder and leafroller 0.01
Grape berry moth
Carbendazim Benzimidazole fungicide Broad-spectrum of fungi diseases 0.3/0.5b
Chlorothalonil Aromatic fungicide Downy mildew 3
Chlorpyrifos Organothiophosphate European grapevine moth 0.5
acaricide/insecticide Vine and citrus mealybugs
Chlorpyrifos-methyl Organothiophosphate insecticide Grape moth 0.2
Vine and citrus mealybugs
Cyazofamid Imidazole-sulfonamide fungicide Downy mildew 0.5
Cyfluthrin Pyrethroid insecticide 0.3
-Cyhalothrin Pyrethroid insecticide Insect and mite pests 0.2
Cymoxanil Aliphatic nitrogen fungicide Downy mildew 0.2
Cypermethrin Pyrethroid insecticide Insect and mite pests 0.5
Cyprodinil Anilinopyrimidine fungicide Grey mould 5
Deltamethrin Pyrethroid insecticide Insect and mite pests 0.2
Dichlofluanid Phenyldulfamide fungicide/acaricide Downy mildew 0.01
Dimethoate Organothiophosphate Vine and citrus mealybugs 0.02c
Dimethomorph Morpholine fungicide Downy mildew 3d
Endosulfan Organochlorine insecticide Insect and mite pests 0.05
Famoxadone Dicarboximide-oxazole fungicide Downy mildew 2
Fenamidone Imidazole fungicide Downy mildew 0.5
Fenarimol Pyrimidine fungicide Broad-spectrum of fungi diseases 0.3
Fenhexamid Anilide fungicide Grey mould 5
Fenitrothion Organothiophosphate insecticide 0.01
Fenpropathrin Pyrethroid insecticide Insect and mite pests 0.2
Fenthion Organothiophosphate insecticide 0.01e
Fluazinam Pyridine fungicide Grey mould 0.05/3
Flusilazole Conazole fungicide Botrytis 0.01
Fludioxonil Pyrrole fungicide Grey mould 5/4
Flufenoxuron Benzoylphenylurea chitin synthesis Grape moth 1/2
inhibitors insecticide/acaricide
Fluquinconazole Conazole fungicide Foliar fungi and rust diseases 0.1/0.5
Folpet Phthalimide fungicide Downy mildew 0.02/10
Phomopsis cane and leaf spot
Powdery mildew
Rotbrenner
Hexythiazox Thiazolidine acaricide Mite growt regulator 1
Imazalil Conazole fungicide Prevent fruit fungi diseases in transport and 0.05
storage
Imidacloprid Neonicotinoid insecticide Grape moth 1
Vine and citrus mealybugs
Indoxacarb Carbamate insecticide Grape moth 2f
Iprodione Imidazol fungicide Grey mold 10
Iprovalicarb Carabamate fungicide Downey mildew 2
Kresoxim-methyl Strobilurin fungicide Powdery mildew 1
Lufenuron Benzoylphenylurea chitin synthesis Grape moth 1
inhibitors insecticide
Malathion Organothiophosphate 0.02g
Mandipropamid Amide fungicide Downy mildew 2
Maneb-group Dithiocarbamate fungicide 5
Mepanipyrim Anilinopyrimidine fungicide Grey mold 2
Metalaxyl Anilide fungicide Downy mildew 2/1h
Methidathion Organothiophosphate insecticide 0.02
Methomyl Oxime carbamate insecticide Insect and mite pests 0.02/0.5
Methoxyfenozide Moulting hormone agonist Lepidoptera pest 1
Metrafenone Aryl phenyl ketone fungicide Powdery mildew 5
Myclobutanil Conazole fungicide Powdery mildew 1
Omethoate Organothiophosphate Insect and mite pests 0.02
insecticide/acaricide
Parathion-methyl Organothiophosphate insecticide 0.01i
Table 1 (Continued)
Pesticide Family-activity Pest control MRL Table/Wine grapes (mg/kg)
Penconazole Conazole fungicide Powdery mildew 0.2

Phosalone Organothiophosphate European grapevine moths 0.01
Procymidone Dichlorophenyl dicarboximide Grey mold 0.01
fungicide
Profenofos Organothiophosphate insecticide Insect pest 0.01
Propiconazole Conazole fungicide Powdery mildew 0.3
Proquinazid Unclassified fungicide Powdery mildew 0.5
Pyraclostrobin Strobilurin fungicide Broad-spectrum of fungi diseases 1/2
Pyrimethanil Anilinopyrimidine fungicide Grey mould 5
Quinalphos Organothiophosphate 0.05
Quinoxyfen Quinoline fungicide Powdery mildew 1
Spiroxamine Unclassified fungicide Powdery mildew 1
Tebuconazole Conazole fungicide Powdery mildew 0.5/1
Tebufenozide Moulting hormone agonist insecticide Grape moth 3
Tetraconazole Conazole fungicide Powdery mildew 0.5
Thiabendazole Benzimidazole-thiazole fungicide Prevent fruit fungi diseases in transport and 0.05
storage
Thiophanate methyl Carbamate fungicide 0.1/3
Triadimefon Conazole fungicide 2
Trifloxystrobin Strobilurin fungicide Black rot 5
Downy mildew
Powdery mildew
Valifenalate Acylamino acid fungicide Downy mildew 0.2
Vinclozolin Oxazole fungicide Grey mold 0.05
Zoxamide Benzamide fungicide Downy mildew 5
a
MRL defined as benalaxyl including other mixtures of constituent isomers including benalaxyl-M (sum of isomers).
b
MRL defined as carbendazim and benomyl (sum of benomyl and carbandazim expressed as carbendazim) (R).
c
MRL defined as dimethoate (sum of dimethoate and omethoate expressed as dimethoate).
d
MRL defined as dimethomorph (sum of isomers).
e
MRL defined as fenthion (fenthion and its oxygen analogue, their sulfoxides and sulfone expressed as parent) (F).
f
MRL defined as indoxacarb (sum of indoxacarb and its R enantiomer).
g
MRL defined as malathion (sum of malathion and malaoxon expressed as malathion).
h
MRL defined as metalaxyl and metalaxyl-M (metalaxyl including other mixtures of constituent isomers including metalaxyl –M (sum of isomers)).
i
MRL defined as parathion-methyl (sum of parathion-methyl and paraoxon-methyl expressed as parathion-methyl).
MRL in table grapes from Chile [25]. A recent study carried out in La be concluded that consumer intake of pesticides from grapes sig-
Rioja region in Spain monitored the pesticides in the soils of sev- nificantly decreased as a result of water washing [32]. In reference
enteen vineyards. The highest concentrations were found for the [33], a multi-residue method for the analysis of 175 pesticides was
fungicides metalaxyl and triadimenol, the herbicides fluometuron used to investigate the peel and pulp distribution ratio of 25 pes-
and terbuthylazine and the insecticide methoxyfenozide [26]. ticides detected in grape samples. Four groups of pesticides were
Four studies carried out in different areas of India examined the distinguished depending on their distribution between peel and
persistence of the pesticides azoxystrobin [27], fluopicolide [28], the whole grape. The first group with a peel/whole grape distribu-
tebuconazole [29] and kresoxim methyl [30] in grapes. In each tion of 100%, meaning that the pesticides were exclusively located
study one pesticide was applied to the grapes. All studies con- in the peel, consisted of pesticides with a strong lipid solubil-
cluded that the residue of the pesticide was below the quantifiable ity (fenvalerate, p,p’-DDE, chlorpyrifos, cypermethrin, cyhalothrin,
limit (azoxystrobin, fluopicolide, tebuconazole) or well below the pyridaben, chlorfenapyr or bifenthrin). A second group had a
EU MRL (kresoxim methyl) at the time of harvest when grapes peel/whole grape distribution of 80–99.9% (difenoconazole, pyra-
were treated with the recommended dose of pesticide and the clostrobin, famoxadone, prochloraz, hexaconazole, chlorothalonil,
pre-harvest interval was respected. flusilazole, azoxystrobin and iprodione). A third group of pesticides
Other interesting studies on grapes deal with the potential vari- with a 50–80% of peel/whole grape distribution showed a 20–50%
ability in the levels of pesticide residues in single grapes [31], migration into the pulp (dimethomorph, cyprodinil, tebuconazole,
depending on the growth conditions, the different localisations propiconazole, kresoxim-methyl and procymidone). In case of the
(grape peel or pulp) and the different modes of action [32]. A study fourth group (0–50% peel/whole grape distribution) more than half
carried out with the pesticides acetamiprid and cypermethrin in of the pesticide residue can migrate into the pulp (pyrimethanil and
grapes concluded that the distribution patterns of both pesticide metalaxyl). As the main part of the pesticide residues of the first
residues were influenced by complex factors such as differences and second group can be removed by peeling or washing, these
in crop species, plant cultivation methods, application rates, pre- pesticides can be recommended for grapes cultivation based on
harvest intervals and physicochemical properties of pesticides [31]. their distribution pattern, while the third and fourth group should
In another study [32], fourteen pesticides (13 fungicides and 1 not be recommended for grapes cultivation [33]. In a recent work
insecticide) were selected to investigate the mobility from peel to from Lagunas-Allué et al. [34], the mobility and distribution of
pulp in grapes, considering lipophilicity and concentration of the eight fungicides (vinclozolin, dichlofluamid, captan, penconazol,
active ingredients as the essential parameters for residue transfer quinoxyfen, fluquinconazol, boscalid, pyraclostrobin) in surface,
from peel to pulp. The results obtained were difficult to inter- skin and pulp of grapes was studied. One of the most interesting
pret: most systemic pesticides such as cymoxanil and oxadixyl outcomes was that the sorption of the fungicide did not depend
were found in the pulp, while only the contact pesticide folpet was on the initial spiked concentration but on the time that grapes had
detected in the peel and not in the whole grape. The removal of been in contact with the fungicide solution. Although all fungicides
pesticides from grapes by washing did not exceed 70%, but it could showed penetration into the pulp, residues were mainly found in
the skin. In this study, pyraclostrobin showed a higher penetration fruits and vegetables, with a common extraction step and clean-up
than the other fungicides. followed by chromatography and MS detection.
In many cases grapes are processed in order to make other During this review, the references were separated in two groups
products, and then it is possible that residues of pesticides pass using two criteria: first, the number of pesticides included in
from grapes to those products. For instance in wine processing, the method, and second the matrices analyzed by the method.
pesticide residues in grapes may transfer to the must and influ- The methods including a large number of pesticides from differ-
ence the selection and development of yeast strains [4]. In these ent families were considered as multi-residue methods. These are
contexts, a high number of analytical studies has focussed on commonly applied to different matrices including grapes. They
the dissipation rates and/or concentration factors of pesticides in are presented in Table 2 [5,33,48–72]. The methods focussing on
different parts of the derived products during the grapes process- the matrix grape and not including a large number of pesticides
ing, like drying, juice/wine-making, alcoholic beverage distillation, were considered as single-residue methods or specific methods
food supplements extracts or pharmaceutical/cosmetic applica- for grapes. These methods often include some of the by-products
tions. The dissipation rate describes the dissipation kinetics of the of grapes as additional matrices. They are presented in Table 3
pesticide in grapes which often follows a first-order model. It is [32,38,73–98]. In both Tables 2 and 3, the papers are classified
used to calculate the pre-harvest interval, which is the time period in a chronological order to outline the evolution of the analytical
(in days) required for dissipation of the initial residue deposits to methodologies.
below the MRL, and the half life, t1/2 , which is the time at which
the concentration of initial deposits reaches the 50% level. [35,36] 3.1. Sampling and sample preparation
In a review of P. Cabras and A. Angioni [37], 9 fungicides and 9
insecticides residues in grapes were monitored at 5 harvest inter- This section deals with the sub-sampling in the laboratory
vals, resulting in different decay rates till dissipation 21 or 28 days and not with field sampling or acceptance sampling. Correct
after application for most of them. In this study, it was shown that sample preparation techniques and sub-sampling are needed in
penconazole, fluazinam, kresoxim-methyl and organophosphorous order to obtain a homogeneous and representative sample. In
insecticides disappear quickly from the grapes after treatment, general, the starting material consists of 0.5 kg–2 kg of grapes
whereas the fungicides fludioxonil and pyrimethanil showed a [32,48–64,73–98], which represents the sample arriving in the lab-
slower decay rate (half life, t1/2, of 24 and 57 days, respectively) oratory for analysis. These are removed from the stems and the
and were detectable at harvest time. For pyrimethanil this might be whole berries with the peel are blended. In some cases, the grapes
explained by its migration into the pulp, as shown in reference [33]. are first frozen and the sample is homogenised by cryogenic milling
During the drying process for raisins production the residues level [48]. Once the sample is homogenised a sub-sample, ranging from
could theoretically increase by a factor of 4. However, for seven 0.5 g to 100 g (but typically 10 g) is taken for further extraction and
monitored pesticide residues (benalaxyl, dimethoate, iprodione, analysis.
metalaxyl, phosalone, procymidone and vinclozolin) the values
of concentration decreased for all except iprodione and phosa- 3.2. Sample extraction
lone which showed a higher concentration (factor of 1.6 and 2.8,
respectively). The same study showed that in the case of wine pro- The complexity of the sample treatment is linked to the
duction, pesticide residues (13 fungicides and 9 insecticides) were potential matrix interferences and the used separation tech-
distributed over a biphasic system made up of a liquid phase (the nique, most commonly GC [48,52,53,55,57–62,64,66,68,70,71] or
must) and a solid phase (cake and lees) after pressing of the grapes. LC [5,48–57,63,65,67,69,72]. Also the physicochemical properties
In general pesticide residues in the must were remarkably lower of the analyte, mainly the polarity of the pesticide, have to be
than those on the grapes showing the great affinity of most pes- considered. An evolution in extraction methods together with the
ticides for the solid phase. After fermentation, pesticide residue parallel improvement of the analytical techniques has allowed
levels in wine were always lower than those on the grapes and a reduction in the complexity of the sample treatment and has
in the must; the only exception were those pesticides which pref- increased the accuracy and precision of the analysis. One of the
erentially partition in the liquid phase (azoxystrobin, dimethoate first multi-residue methods for organochlorine pesticides analysis
and pyrimethanil). These pesticides were present in the wine at in food was developed in 1963 using acetonitrile and petroleum
the same concentration as in grapes. In case of alcoholic beverages ether [99]. To be able to analyse more polar pesticides than the
derived from wine by-products, only fenthion, quinalphos and vin- organochlorine group, Luke et al. [100] validated a method based
clozolin pass into the distillate from the lees when present in very on acetone followed by dichloromethane and petroleum ether par-
high concentrations [37]. Other studies of pesticide residues dissi- titioning and clean-up with Florisil. An acetone based extraction
pation in wine have been carried out [38–47], and dissipation rates method was also developed in 1983 by the Dutch Food and Con-
were estimated for different compounds. However, this review arti- sumer Products Safety Authority-Food Inspection Service [101]
cle has not as a purpose to go into detail in this wine production which was routinely applied for pesticide monitoring during more
process. than 25 years. The Swedish National Food Administration devel-
oped an analytical method using ethyl acetate combined with a
clean-up by gel permeation chromatography in 1989 [53]. Ethyl
3. Analytical methods acetate is less polar (polarity index 4.4) than acetone (polarity index
5.1) and so polar pesticides partition less in ethyl acetate. To push
According to the guidelines given by the European Commis- the polar pesticides into the organic solvent large amounts of the
sion’s Directorate for Health and Food Safety (DG SANTE), grapes anhydrous sodium sulphate (Na2 SO4 ) are added to the water phase.
have been classified in the commodity group of ‘high acid content’ In 2003, Anastassiades at al. [102] introduced a new strategy based
and ‘high water content’ together with small fruit and berries [13]. on acetonitrile extraction followed by a clean-up using disper-
However, grapes are often considered as a medium acid matrix sive solid phase extraction (dSPE) with a primary and a secondary
with a high sugar content when multi-residue methods for pesti- amine (PSA) and octadecylsilyl (C18 ). They termed this sample
cide analysis in fruit and vegetables are developed [5,48]. Therefore treatment procedure as QuEChERS (Quick, Easy, Cheap, Effective,
these multi-residue methods used for the analysis of pesticides in Rugged, Safe). This method became popular because of its mini-
grapes often follow the general strategies for pesticide analysis in mal use of traditional analytical steps, solvent and glassware. This
Table 2
Overview of published multi-residue methods for the analysis of pesticides in grapes. Recovery is expressed in percentage between the theoretical value and the experimental.
Repeatability is expressed as relative standard deviation percentage.
Number of Sample Determination Trueness (mg/kg) Recovery (%) Repeatability (%) Sensitivity LOD Reference
analytes treatment technique (mg/kg) 10−3
38 - SLE: 8 g sample + 50 LC-ESI-MS/MS 0.01–0.8 73–92 4.5–17.7 1a [49]

mL ethyl acetate + 70 (QqQ)
g Na2 SO4 + 2 g
NaHCO3
- Low volume
evaporation:
2 × (10 mL methanol
to 2 mL final volume)
57 - SLE: 75 g LC-ESI-MS/MS 0.01–0.5 44–118 3–30 1a [50]

sample + 200 mL (QqQ)
ethyl acetate + 40 g
Na2 SO4 + (NaOH for
acid matrices)
- Dryness evaporation
of aliquot and
dissolved in
methanol
74 - SLE: 20 g LC-ESI-MS/MS 0.01–1 63–158 3–31 1a [51]

water + pH
adjustment 6 − 7 +
40 mL ethyl acetate
aliquot of 5 mL and
dissolved in 1 mL
methanol
446 - SLE: 20 g GC–MS (Q) 0.01–3.00 55–134 2.1–39.1 0.5–25 (LOD) [52]
sample + 40 mL LC-ESI-MS/MS
acetonitrile + 5 g (QqQ)
NaCl
- SPE: Envi-18 elution
acetoni-
trile + evaporation 1
mL–SPE: Envi-Carb
connected to
aminopropyl
Sep-Pak, elution
25 mL
acetonitrile:toluene
(3:1 v/v) evaporation
to 0.5 mL, for GC
2 × 5 mL hexane and
evaporation to 1 mL,
for LC–MS/MS
evaporation to
dryness and
dissolution in 1 mL
acetonitrile:water
(3:2 v/v)
309 - SLE: 75 g sample + GC–MS/MS 0.01–0.05 57–122 2–30 1a [53]

200 mL ethyl (QqQ)
acetate + 15 g LC-ESI–MS/MS
NaHCO3 + 40 g (QTrap)
Na2 SO4
100 mL and dissolve
in 5 mL ethyl
acetate: cyclohexane
(1:1 v/v)
- Dilute 5 times with
ethyl acetate:
cyclohexane (1:1
v/v) for GC
aliquot 0.5 mL and
dissolve to 1.5 mL
methanol for LC
Table 2 (Continued)
82 - SLE: 10 g sample + 10 mL LC–MS/MS 0.0025–0.05 36.5–120.5 0.3–19 0.1–3.3 [54]

ethyl acetate + 10 g (QTrap)
Na2 SO4
- dSPE: aliquot
5 mL + 25 mg PSA
- Clean aliquot of 4
mL + 200 ␮L 10%
diethylene glycol in
methanol
- Dryness evaporation and
dissolution in 2 mL
methanol:water 0.1%
acetic acid 1:1 v/v
341 - SLE: 25 g sample + 40 mL GC–MS (Q) 0.001–0.5 60–140 15–30 1 for most pesticides [55]
ethyl acetate + 25 g LC-ESI-MS/MS
Na2 SO4 (QqQ)
- For GC, DSPE: 0.8 mL
extract sample + 0.2 mL
toluene + 25 mg PSA + 25
mg GCB
- For LC, dryness
evaporation in 10%
diethylene glycol and
dissolution in methanol.
Dilution 1:1 mobile
phase
171 - SLE: 15–7.5 g LC–MS/MS (QqQ) 0.01–0.1 21–114 1–50 ≤10a [56]
sample + 30 mL acetone +
30 mL
dichloromethane + 30 mL
light petroleum
(+Na2 SO4 )
1.1 mL aliquot, disolution
1.0 mL methanol 0.02%
acetic acid
80 - QuEChERS: 10 g GC–MS/MS 0.005–0.2 60–127 0.2–16.7 10a [48]

acetonitrile + 4 g LC–MS/MS
MgSO4 + 1 g NaCl + 0.5 g (QTrap)
disodiumhydrogen
citrate
sesquihydrate + 1 g
trisodiumcitrate
dehydrate
- dSPE: aliquot
extract + 150 mg
MgSO4 + 25 mg PSA/mL
extract
- Re-acidify extract: 10 ␮L
formic acid 5% (v/v)/mL
extract
151 - QuEChERS: 10 g GC–MS (Q) 0.05–0.5 33–120 0.7–14.5 0.4–115 ␮g/kg [57]
sample + 10 mL LC–MS/MS (IT)
acetonitrile + 4 g
MgSO4 + 1 g NaCl + 1 g
citrate dehydrate + 0.5 g
di-sodium hydrogen
citrate sesquihydrate
- dSPE: 6 mL aliquot
extract + 150 mg
PSA + 950 mg MgSO4
- Acidification before LC
injection: 1.5 mL
extract + 15 ␮L 5% formic
acid
dissolution in 150 ␮L
acetone/ethyl acetate
(1:1 v/v)
Table 2 (Continued)
51 - SLE: 10 g sample + 10 GCxGC–MS (TOF) 0.01 70–109 3–10 0.2–3.0 [58]

mL ethyl acetate + 10
g Na2 SO4
- dSPE: 1 mL
extract + 25 mg PSA
38 - MSPD: 500 mg GC–MS (Q) 0.5 62–102 1–21 9–250 GC–MS; 0.005–3.6 GCxGC-␮ECD [59]
sample + 500 mg C8 GCxGC-␮ECD
+ 700 ␮L elution
ethyl acetate
of extract and
dissolution isooctane
160 - SLE.: 10 g GCxGC–MS (TOF) 0.01–0.05 67–135 1–12 – [60]

sample + 10 mL ethyl
acetate + 10 g Na2 SO4
- dSPE: 1 mL
aliquot + 25 mg PSA
346 - SLE: 15/20 g GC–MS (Q) 0.01–0.2 30–136 ≤10–20 1.7–266 [61]
sample + 15/40 mL
acetonitrile + 6 g
MgSO4 + 1.5 g NaCl-
Method A: dSPE:
extract + 0.3 g
PSA + 1.8 g MgSO4
- Method B: SPE:
Envi-18, Envi-carb,
sep-pak NH2;
elution 25 mL 3:1
acetonitrile:toluene
- Method C: SPE: 1 mL
extract + 20 mL
water; Oasis
HLB + NH2 cartriges;
elution 5 mL 80:20,
50:50 and
20:80ethyl
acetate:hexane
- Evaporation from
7.5 mL to 0.5 mL
excahnge with
hexane (2 × 5mL) till
1 mL
50 - SLE: 10 g sample + pH GC–MS/MS 0.01–0.05 71–117 3–18 5.0–19.2 [62]

ajustment 4 acetic (QTrap)
acid + 10 mL ethyl
acetate + 10 g
Na2 SO4 + 5 mL ice
cold water
- dSPE: 1 mL
extract + 25 mg PSA
150 - SLE: 10 g LC–MS/MS 0.01–0.1 40–109 1–25 10a [63]

sample + 10 mL (QTrap)
acetonitrile + 4 g
MgSO4 + 1 g NaCl + 1
g trisodium citrate
dehydrate + 5 g
disodium
hydrogencitrate
sesquihydrate
4 mL aliquot,
disolution in 4 mL
methanol: water
(1:1, v/v)
135 - SLE grape: 10 g GC–MS (TOF) 0.001–0.650 70–120 1–32 0.03–0.38 [64]
acetate + 10 g
Na2 SO4 ;
- dSPE: 1 + mL
extract + 25 mg PSA
Table 2 (Continued)
209 - SLE: 10 g sample + 10 LC–MS/MS 0.01–0.5 77–121 9–33 0.1–10 [65]

mL acetonitrile + 4 g (QTrap)
MgSO4 + 1 g NaCl
- dSPE: ca. 9 mL
extract + 400 mg
PSA + 1200 mg
MgSO4
82 - SLE: 15 g GC-NCI-MS/MS 0.01–0.02b 58.7–124.4b 3.9–15.9b 0.01–1.82 [66]

acetonitrile + 6 g
MgSO4 + 1.5 g
NaOAc + 0.1% acetic
acid
10 mL, dissolution
2 mL acetonitrile
- dSPE: 2 mL + 350 mg
C18 + 100 mg
PSA + 200 mg MgSO4
175 - SLE: 2.5 g peel/5 g GPC-GC–MS (Q) 0.01–0.2 46.5–145 2.0–34.6 0.4–10 [33]
pulp + 20 mL
acetonitrile + 1 g
NaCl + 4 g MgSO4
- dSPE: 5 mL
extract + 250 mg
MgSO4 + 60 mg PSA
4 mL extract
dissolved 1 mL
cyclohexane:acetone
(7:3, v/v)
48 - SLE: 0.5 g LC–MS/MS (QqQ) 0.01–0.25 64–121 4–20 0.8–10.3 [67]

sample + 900 ␮L
acetonitrile.
Vortex + Ultrasonic
bath
- On-line
chromatographic
cleanup
349 - SLE: 10 g GC–MS/MS 0.005–0.025 70–120 <20 5–10 [68]

sample + 10 mL ethyl (QqQ)
- dSPE: 1 mL extract +
25 mg PSA + 7 mg
GCB
and dissolution
800 ␮L ethyl acetate
71 - Pressurised liquid UHPLC–MS/MS 0.001–0.01 70.8–119.1 <20 0.12–2.16 [5]

solvent extraction: (QqQ)
10 g sample + 1.0 mL
tetrafluoroethane-
toluene = 100 mbar
pressure + 15 mL
1,1,1,2-TFE. Vortex
- Evaporation till
toluene remains
166 - SLE: 15 g UHPLC- 0.01 0.4 42.9–123.8 5.2–28.3 <5 [69]

sample + 15 mL ESI–MS/MS
acetonitrile 1% acetic (QOrbitrap)
acid + 1.5 g
NaOAc + 6 g MgSO4
- dSPE: extract + 900
mg MgSO4 + 150 mg
C18 + 300 mg PSA
- Evaporation to
0.1–0.2 mL,
methanol addition to
0.5 mL + 1 mL 0.1 M
NH4 OAc
Table 2 (Continued)
47 - SLE: 10 g GC–MS (Q) 0.01–0.02 67–120 1–19 <0.01–0.02 mg/kg LOQ [70]
- dSPE: 1 mL
extract + 25 mg PSA
341 - SLE: 10 g GC–MS/MS – – – – [71]

sample + 10 mL ethyl (QqQ)
- dSPE: 1 mL + 25 mg
PSA + 7 mg GCB
60 - SLE: 10 g sample + 25 UHPLC–MS (TOF) 0.05–0.2 73–111 1–4 0.8–11.8 [72]

mL acetoni-
trile:methanol
(90:10, v/v) + 5 g
NaCl
of extract and
dissolution 2 mL ace-
tonitrile:methanol
(95:5, v/v)
- SPE: 0.5g GCB/PSA,
elution 10 mL ace-
tonitrile:methanol
(95:5, v/v)
dissolution 1 mL
methanol
a
Sensitivity defined as LOQ as the lowest level assayed during validation when the LOD or other LOQ estimation is provided in the paper.
b
Validation of the method in cabbage and apple.
resulted in the publication of two reference methods: the first one ces showed that the acetate-buffered method was more efficient
published by the European Committee for Standardisation (CEN- and appropriate for grapes [103].
15662) [10] which used acetonitrile with a citrate buffer during The extraction solvents used for the solid-liquid extraction in
the extraction; the second one published by AOAC International as the case of specific methods for grapes and their by-products
“Method 2007.01”, using acetonitrile with an acetate buffer during (Table 3) show a higher versatility. Apart from the use of ace-
the extraction [12]. tonitrile [38,74,80,89,93,94] and ethyl acetate [75,76,81,85,86,98],
Many of the methods published for the analysis of pesticides other organic solvents have also been used: acetone [82,84,88];
in grapes are based on the QuEChERS methodology. Tables 2 and 3 methanol [32,79,90]; ethanol [95]; and, deionized water [83,87].
show the increasing popularity of QuEChERS during the last decade. One of the reasons for this higher variability in extraction solvents
Out of a total of 55 published multi-residue methods between 2000 may be that specific methods are developed and optimised for a
and 2014, 21 (or 38 %) are based on the QuEChERS methodology small group of pesticides (often from the same chemical family and
(taking both acetonitrile and ethyl acetate as possible extraction analysed by GC).
solvents in the QuEChERS methodology). This percentage increases A study of the extraction solvent selection for 6 organophos-
in the case of multi-residue methods (Table 2) to 63 % when only phorus pesticides with a low molecular mass, very polar and/or
the last 5 years (2009–2014) are taken into account (10 out of 16). thermolabile has been conducted in reference [104]. The solvents
In general, the common procedure to analyse a large investigated were water, methanol, acetone (with and with-
number of pesticide residues in grapes (Table 2) uses out partitioning in dichloromethane-petroleum ether) and ethyl
acetonitrile [33,48,52,57,61,63,65,66,69] or ethyl acetate acetate. Ethyl acetate was most favourable with respect to matrix
[49–51,53–55,58–60,62,64,70,71] as organic solvents (Fig. 1). effects, interferences in LC–MS/MS and extraction efficiency. After
In the outline of the extraction performance with ethyl acetate an analysing all methods included in Table 2 and 3, the preferred sol-
evolution is observed from a larger volume (40–200 mL) of ethyl vents for pesticide residue analysis in grapes are ethyl acetate and
acetate [49–51,53,55,76] to a reduction of the solvent volume acetonitrile, as shown in Fig. 1.
to around 10 mL [54,58–60,62,64,68,70,71,81,86] This decrease In a few of the published methods bases like sodium hydrox-
of volume allowed the elimination of the drying step for sample ide [38,66], ammonium formate [89] or ammonium acetate [90,95]
pre-concentration before sample injection into the LC or GC instru- are added to the extraction solvent in order to neutralise the acid
ment. One of the shortcomings of the ethyl acetate extraction is matrices.
the loss of basic pesticides in acidic crops like grapes. To overcome The most common mixing and homogenising tools used
this problem NaHCO3 was added successfully by Pihlström et al. in the extraction process are a probe blender or UltraTurrax
[53]. Three exceptions from this common procedure can be found [49,55,76,77,82,84,96]. As alternative techniques, the application of
in Table 2: an extraction based on acetone [56], a procedure the ultrasonic assisted extraction (UAE) [67,79,81,97], microwave
using tetrafluoroethane-toluene and pressurised liquid solvent assisted extraction (MAE) [88], or pressurised liquid extraction
extraction [5] and a mixture of acetonitrile and methanol (90:10, (PLE) [5,97] have been described. A comparison of 4 extraction
v/v) [72]. A recent comparison of two QuEChERS methods (one approaches have been carried out for 8 pesticides (dichlofluanid,
citrate-buffered and one acetate-buffered) in different fruit matri- vincozolin, penconazole, captan, quinoxyfen, fluquinconazol, pyr-
Table 3
Overview of published specific methods for the analysis of pesticides in grapes and derived products. Recovery is expressed in percentage between the theoretical value and the experimental. Repeatability is expressed as relative
standard deviation percentage.
Number of Matrix Sample Determination Trueness (mg/kg) Recovery (%) Repeatability (%) Sensitivity LOD Reference
12 multiclass Grape - SLE(1) : 5g/50 mL GC-ECD 0.01–0.5 78–107 17.5–0.6 0.77–5.16 [73]
fungicides Must sample + 30 mL GC-NPD
Wine acetone:dichloromethane GC-EI-MS (Q)
(1:1 v/v) + 2g NaCl (Probe
blender)
- Dryness evaporation + 5 mL
isooctane-toluene (1:1, v/v)
S. Grimalt, P. Dehouck / J. Chromatogr. A 1433 (2016) 1–23

15 multiclass Skin/Whole - SLE: 100–25 g LC-DAD – 30.7–79.4 19.2–39.4 1.7 average [32]
pesticides grape sample + 100–25 mL
methanol
dilution in 25 mL
water:methanol (88:12 v/v)
- SPE: 500 mg C8 , elution
mixtures
dichloromethane:methanol
dissolved in 500 ␮L
water:methanol (45:55, v/v)
12 botanical Grape - SLE: 5 g sample + 10 mL LC-DAD 0.01–5 73–115 0.1–12.2 0.1–0.01 [74]
insecticides acetonitrile + 4 g NaCl + 1 g LC-APCI-MS
MgSO4
6 multiclass Grape - SLE/LLE: 5 g/5 mL + 10 mL LC-DAD 0.25–2.00 96–105 6–12 0.1–0.3 [75]
fungicides Wine ethyl acetate:hexane (1:1 GC–MS(Q)
v/v)
- Dryness evaporation of 1 mL
and disolved with 1 mL of
methanol:water (80:20 v/v)
for LC and 0.5 mL of Ethyl
acetate:hexane (1:1 v/v)
10 multiclass Grape - SLE: 50 g sample + 100 mL LC–MS/MS (QqQ) 0.01–0.1 78–104 6–15 5–10 [76]
pesticides ethyl acetate + 75 g Na2 SO4
- Dryness evaporation of 2 mL
aliquot and dissolved with
0.45 mL methanol
11
12
Table 3 (Continued)
3 multiclass Grape - SLE: 10 g/10 mL sample + 10 GC-NPD 0.05–2.0 81–102 3–12 5–50 GC-ECD; 10–100 GC-NPD [77]
fungicides Wine mLcyclohex- GC-ECD
ane:dichloromethane (9:1, GC–MS/MS (IT)
v/v).
- Dryness evaporation aliquot
5 mL, dissolution to 1 mL
cyclohexane
8 organophos- Grape juice - Dilution juice: 10 mL GC-NPD 0.15–1.35 75–103 1.9–6.3 1.85–7.32 [78]
phorus sample + 10 mL MilliQ water,
pesticides pH ajustment 6.0 with NaOH
1.0 M
- SPE: 40 mg MWCNTs;

elution 20 mL
dichloromethane
- Dryness evaporation,
disolution 1 mL
cyclohexane + Na2 SO4 ;
filtration PTFE
18 multiclass Grape - SLE: 10 g sample + 10 mL GC–MS (Q) 72–122 3–20 6.7–40.0 [79]
pesticides Must methanol (UAE)
Wine - SBSE: 20 mm x 0.5 mm PDMS
Vinegard 1000 rpm 25 ◦ C 150 min
27 multiclass Grape - QuEChERS: 10 g sample + 10 LP-GC–MS (Q) 0.04–5 57–120; 63–120; 52–121 5–20; 3–17; 3–18 1.0–12.5; 1.2–14.0; 1.3–19 ng/g [80]
pesticides Must mL acetonitrile + 4 g
Wine MgSO4 + 1 g NaCl manual
shaking and centrifugation
- dSPE: 1 mL aliquot
extract + 150 mg MgSO4 + 50
mg PSA + 50 mg C18
11 fungicides White/Red Grape - SLE.: 15 g/15 mL sample + 15 GC–MS (IT) 0.05–0.5 76–147 2–16 <1–24 [81]
White/Red Wine mL ethyl acetate: hexane
(1:1 v/v) Ultrasound bath
10 min. + 1 g NaCl + 5 g
Na2 SO4
- Dryness evaporation 12 mL
aliquot dissolution 3 mL
acetonitrile
- SPE: envi Carb –II/PSA,
elution 20 mL
acetonitrile:toluene (3:1 v/v)
dissolution 0.5 mL
acetone + protectants
19 fungicides Grape - SLE: 15 g grape + 200 mL GC-NPD 0.05–1.2 79–92 GC; 51–91 LC [82]
Seed oil acetone GC-ECD
Meal grape - LLE partition: 650 mL LC–MS/MS (QqQ)
saturated Na2 SO4 , extraction
1 × 100 mL + 2 × 50 mL
dichloromethane
- Na2 SO4 drying column,
inverted 10 mL hexane
(other extraction for seed and
meal)
8 multiclass Grape - SLE: 1 g sample + 5 mL LC-DAD 0.005–0.5 64–100 1.7–9.1 0.65–5.44 [83]
pesticides acetonitrile + 2 g MgSO4 + 0.5
g NCl + 0.5 g sodium
citrate + 0.25 g sodium

hydrogenitrate
sesquihydrate
- DLLME: 88 mg
[C6 MIM][PF6 ] + 714 ␮L
methanol, centrifugation;
20 ␮L dissolved 125 ␮L
6 pyrethroid Grape - SLE.: 10 g sample + 30 mL GCxGC-FID 0.02–0.5 94–113 2.6–18.4 3–6 [84]
pesticides acetone GCxGC-␮ECD
- LLE partition: 30 mL
dichloromethane + 30 mL
light petroleum + 10 g
Na2 SO4 . Ultraturrax
Dryness evaporation
dissolution 1.0 mL ethyl
acetate
8 fungicides Red Grape - MSPD: 0.5 g sample + 1.5 g GC–MS (Q) 0.01–0.06 76–120 3.5–9.0 1.0–2.6 [85]
C18 , elution 10 mL
dichloromethane:ethyl
acetate (1:1, v/v)
- Evaporation extract to 5 mL
21 pyrethroid Grape - SLE.: 10 g sample + 10 mL (PTV-LVI)- 0.01–0.05 77–115 1.5–19.6 0.5–3.2 [86]
pesticides ethyl acetate + 10 g Na2 SO4 GC–MS/MS
- dSPE: aliquot 1 mL + 25 mg (IT)
PSA
25 multiclass Grape - SLE: 500 g grape + 200 mL GC–MS (Q) 0.4–3.6 61–108 4.0–12.4 2–12 [87]
pesticides deionized water
- Hollow fibre sorptive
extraction: SiO2 , desorb
0.2 mL ethyl acetate
13
14
Table 3 (Continued)
8 fungicides Grape - SLE: 2 g GC–MS (Q) 0.01–0.05 82–107 2–8 0.7–1.7 [88]
sample + hexane:acetone
(1:1, v/v). MAE: 105 ◦ C, 10
min
7 multiclass Grape - QuEChERS + dilution LC–MS (Q) 0.1–0.5 90–104 0.3–4.1 – [89]
pesticides acetonitrile: 10 mM
ammonium formate (1:4,
v/v)
- HTpSPE in aluminium foil
silica gel 60 NH2 F245s

12 plant growth Grape - SLE: 5 g sample + 5 mL LC–MS/MS (QqQ) 0.01–0.1 78–130 4–57 1.0–10.0 [90]
regulators methanol 1% HCl + 0.5 g
ammonium acetate
- SPE: Oasis HLB 200 mg,
elution 5 mL methanol
- Dryness evaporation,
dissolution 2 mL
methanol:water (1:1, v/v)
5 multiclass Grape juice - Microextraction: dynamic GC-FID 0.5–2 mg/L 72–106 1–7 2–11.2 [91]
pesticides single drop in a narrow-bore
tube, 23 mL sample + 30 ␮L
n-hexanol:n-hexane (50:50,
v/v)
9 organophos- Grape - MSPDE: 0.5 g sample + 1.0 g LC–MS/MS (QqQ) 0.0005–0.2 71.2–102.8 1.8–11.8 0.06–0.15 [92]
phorus MWCNT blended, elution
pesticides 20 mL acetone:ethyl acetate
(1:1, v/v) 1 mL/min
dissolved 2 mL
acetonitrile:water (1:1,
v/v) + formic acid pH 5.0
18 multiclass Red/Green Grape - SLE: 10 g sample + 10 mL LC–MS/MS (QqQ) 0.0001–0.025 97–101 0.01–5.21 0.027–0.087 [93]
pesticides acetonitrile + 6 g MgSO4 + 1.5
g NaOAc
- dSPE: extract + 400 mg
PSA + 1200 mg MgSO4
- Dryness evaporation extract
dissolution 1 mL acetonitrile
30 multiclass Grape - SLE: 10 g sample + 10 mL GC–MS-SIM (Q) 0.02–0.2 75–109 3–13 2–15 [94]
pesticides acetonitrile + 1 g NaCl + 4 g
MgSO4
- Reverse-DSPE: 1 mL
extract + 10 mg
MWCNTs + 150 mg MgSO4
13 multiclass Grape - SLE: 10 g sample + 10 mL LC–MS/MS (QqQ) 0.01 70–95 0.1–60 0.2–1.2 [38]
pesticides Must acetonitrile + 4 g MgSO4 + 1 g
Wine NaCl + 0.5 g disodium
hydrogencitrate
sesquihydrate + 1 g
trisodium citrate dehydrate
- dSPE: 5 mL extract + 125 mg
PSA + 750 mg MgSO4 -
Dryness evaporation 1 mL
extract, dissolution 1 mL

acetonitrile:water (10:90,
v/v)
7 strobilurin Grape - 5g sample + 2 mL LC-DAD 10–175 89–101 2–9 0.3–2.0 [95]

fungicides ethanol–Supernatant diluted
to 14 mL acetate buffer (0.04
M) + NaCl 5%
- SBSE: 200 rpm, 45 ◦ C, 20
min; desorption 100 ␮L
50:50, v/v acetonitrile:water
10 triazole Grape - SPME: PDMS/DVB, 15 min GC–MS (TOF) 0.01–0.5 84–114 1.7–14.6 0.25–5 [96]
fungicides extraction in direct
immersion mode 50 ◦ C,
stirring 500 rpm. Rinsed
deionized water. Desortion
5 min 260 ◦ C
11 fungicides Grape bagase - UAE: GC–MS (Q) 0.1–1 81–120 5.1–12 0.16–1.96 [97]
15 min + 25–45 ◦ C + 0–20% GC–MS/MS
NaCl + 0.5 g sample + 5 mL (QqQ)
ethyl
acetate/hexane:CH3 OCH3
(1:1 v/v)/methanol/hexane
- PLE: 0.5 g sample + 1 g
cleaned sand + 20 mL
hexane:CH3 OCH3 (1:1,
v/v) + 80–120 ◦ C + 5–15min
130 pesticides Grape seed - SLE: 2 g sample + 10 mL ethyl GC–MS/MS 0.01–0.1 60–120 1–21 0.5–5 [98]
extracts acetate + 5 g MgSO4 (QqQ)
- dSPE: 1.4 mL extract + 50 mg
PSA + 50 mg GBC + 50 mg Z
Sep+ + 50 mg C18
- Dilution extract with ethyl
acetate (1:1, v/v)
15
Fig. 1. Scheme summarising the information of the analytical methods included in Tables 2 and 3: (a) sample treatment; and, (b) instrumental techniques for analysis.
aclostrobin and boscalid) in grapes by Lagunas-Allué et al. [105]. Solid phase extraction (SPE) is widely accepted as an alterna-
MAE, solid–liquid extraction (SLE), QuEChERS and matrix solid- tive clean-up method for LLE (Figure 1). Advantages are smaller
phase dispersion (MSPD) were compared in this study. Recoveries volume of solvents and cleaner extracts. The typical SPE columns
were in the range 78–100% (MAE), 66–102% (MSPD), 58–88% (SLE) used for the clean-up of multiple types of pesticides in fresh
and 68–96% (QuEChERS). The lowest LOQs were achieved with MAE fruits and vegetables (including grapes) were evaluated by Schenck
and the highest with QuEChERS and SLE. et al. [106]. This study included reverse phase columns such as
octadecylsilyl (C18 ), aminopropyl (-NH2 ) and primary-secondary
amine (PSA), anion exchange columns such as trimetyl ammonium
strong anion exchange (SAX) and adsorbents such as graphi-
3.3. Clean-up of the extract
tized carbon black (GCB). This work concluded that the bonded
normal phase SPE columns (-NH2 and PSA) were the most effec-
The preliminary extraction with organic solvents is mostly
tive in removing the matrix co-extractants, especially fatty acids
followed by a clean-up step. Different approaches are described
(hexadecanoic and octadecanoic acids), while the GCB sorbent
below.
removed pigments but did not remove noticeable chromatographic
Partitioning with liquid–liquid extraction (LLE) is the most
interferants. The C18 and SAX phases also removed relatively lit-
traditional strategy for clean-up. It is derived from the Luke
tle of the co-eluting matrix co-extractants of the tested fruits
method [100] and nowadays is not commonly used in multi-
and vegetables. Melo et al. [107] also compared in-house made
residue methods (Table 2). Just like in the Luke method LLE often
polysiloxanes (aminopropyl-terminated poly(dimethylsiloxane)
follows an acetone extraction and uses a solvent mixture con-
and poly(methyloctadecylsiloxane)) SPE columns with the com-
taining dichloromethane. Dichloromethane has been used alone
mercial NH2 and C18 . For the 6 pesticides checked in grapes in
or combined with e.g., light petroleum [56] or petroleum ether
this paper, cartridges with amino-based material generated better
[39]. LLE has been more often applied in specific methods for
results than the octadecyl sorbents, with the best performance for
grapes and by-products (Table 3) than in multi-residue meth-
the 40% aminopropyl-loading SPE columns. SPE was only imple-
ods (Table 2). This may be related to the fact that in specific
mented in two of the multi-residue methods included in Table 2
methods the solvents can be more easily adapted to the spe-
[52,72] and four of the specific methods for grapes and by-products
cific pesticides to be analysed. Some methods are based on a
in Table 3 [32,78,81,90]. Different phases were applied in these
mixture of acetone:dichloromethane [73,82,84]. Additionally other
studies. It is remarkable the large range of recoveries obtained
solvent mixtures have been used such as ethyl acetate combined
for the different pesticides when using SPE (Table 2 and Table 3)
with hexane [75,81], dichloromethane [85] or acetone [92]; ace-
showing that care should be taken when selecting the SPE sorbent.
tone combined with hexane [88]; and cyclohexane combined with
Nowadays, dSPE is mostly selected for the clean-up (Fig. 1).
dichloromethane [77]. In some cases [81,82,84] salts like anhydrous
More than half of the multi-residue methods in Table 2 selected
sodium sulphate or sodium chloride are added in order to increase
dSPE as a clean-up option. The dSPE methodology is based on SPE
the separation between the liquid phases or increase the recovery
principles, but the solid phase (commonly PSA, C18 and/or GCB) is
of the pesticides.
added directly to the extract without conditioning, and the clean- hollow fibre as extraction sorbent has been applied by Li et al. [87]
up is easily performed by shaking and centrifugation. This clean-up obtaining suitable recoveries of 25 diverse pesticides.
became very common with the implementation of the QuEChERS
method in pesticide residue analysis. Its use is normally combined 3.4. Common instrumental techniques for analysis
with the solvents acetonitrile [33,38,48,57,61,65,69,80,89,93,94]
and ethyl acetate [54,58,60,63,64,68,70,71,86,98]. The preferred Data in Tables 2 and 3 shows that two analytical strategies
adsorbent for this application is PSA that removes sugars and fatty based on GC and LC are used for pesticide residue analysis in
acids, and which is included in all the dSPE strategies shown in grape samples (Fig. 1). The first analytical approach for pesticides
Tables 2 and 3. The use of magnesium sulphate is also standard- residue analysis used GC, 3 detectors designed for GC appear in
ized in dSPE, especially for GC applications to eliminate water the oldest methods in Table 3: electron capture detector (ECD),
from the organic solvent. Additionally, GCB is included in dSPE nitrogen and phosphorus detector (NPD), and flame photometric
to remove pigments and sterols in samples, while C18 is used detector (FPD). These detectors presented high sensitivity and
to remove non-polar interferences such as lipids. Different com- selectivity for particular pesticides of interest: the ECD seemed
binations of solid phases used for the dSPE in grape analysis especially useful for halogenated compounds such as organochlo-
have been described: (a) 25 mg/mL PSA is the most simple dSPE rine pesticides [59,47,61,65,70,72]; the NPD [61,65,66,70] was a
introduced by the group of K. Banerjee [54,58,60,62,64,70,86]; very sensitive detector for organophosphorous and nitrogenated
(b) 12–40 mg/mL of PSA and 50–160 mg/mL magnesium sul- pesticides; and the FPD [72,79] was a specific analyser for sulphur
phate [38,48,57,61,65,66,93]; (c) 20–50 mg/mL PSA, 60–150 mg/mL and phosphorous pesticides. This explains why these detectors
magnesium sulphate and 10–175 mg/mL C18 [69,80,98]; and, (d) are more often used in the specific methods (Table 3) and less
25 mg/mL PSA and 7–25 mg/mL GCB [68,71]. Mol et al. [55] inves- in the multi-residue methods (Table 2) as the latter want to
tigated the adsorption of pesticides with planar functionality on analyse all classes of pesticides at once. The original detectors
GCB during dSPE. Different ratios of toluene/GCB for the dSPE were used for LC based methods were the UV or diode array detec-
evaluated for the recovery of 35 pesticides with a planar function- tor (DAD) [32,47,62,63,71]. However, nowadays the use of MS
ality (out of a total number of 341 pesticides in the multi-residue [5,33,38,48,49–57,59–77,79–82,85–90,92–94,96–98] is preferred
method), concluding that 20% of toluene was the most satisfactory by most laboratories due to its higher selectivity and sensitivity
approach. for all the pesticides (Fig. 1). The current trend is the use of tandem
A simultaneous extraction and clean-up, MSPD, has also been MS (MS/MS) and high resolution MS (HRMS). The most com-
applied as an elegant alternative. It uses solid phases like C8 [59] or mon MS analyzers used in grape analysis are: single quadrupole
C18 [85]. The difference between MSPD and SPE is that MSPD can (Q) [33,52,55,57,59,61,70,73–75,79,80,85,87–89,94,97], triple
handle solid or viscous liquid samples directly, while SPE needs a quadrupole (QqQ) [5,38,48,53,55,56,66,67,68,71,76,82,90,92,93,97
previous solid-liquid extraction. In MSPD, the sample is homoge- ,98], ion trap (IT) [57,77,81], hybrid quadrupole ion trap (QTrap)
neously mixed with the solid phase and then placed in a column to [48,53,62,63,65], time of flight (TOF) [54,60,64,72,96] and Orbitrap
proceed to the elution like in SPE. Reversed-phase materials such [69].
as C8 and C18 with a lipophilic character enable a good disrup-
tion of the matrix and a good adsorption of the compounds on the 3.4.1. GC–MS based methods
adsorbent. Ramos et al. [59] developed and validated an analytical The most conventional GC–MS detector for pesticide analysis
method for 38 multiclass pesticides in different matrices including in grapes is the single quadrupole. After injection of the sample,
grapes, with the remarkable miniaturised C8 -MSPD-based method separation is typically done on a fused-silica capillary column (5%
involving a small amount of sample and solvent (i.e., 100 mg and phenyl, 95% dimethylpolysiloxane; 30 m × 0.25 mm × 0.25 ␮m),
700 ␮L of ethyl acetate). In the work of Lagunas-Allué et al. [85] a followed by electron ionization (EI, 70 eV) using split/splitless
C18 -MSPD-based sample treatment for the analysis of 8 fungicides injection [52,57,59,61,70,73,75,77,85,87,88,94]. Compared to the
in grapes is described. classical EI, chemical ionization (CI) is less commonly used for the
In order to reduce the use of organic solvents, other approaches analysis of pesticide residues in grapes [42,66]. EI and positive CI
have also been applied such as the stir bar sorptive extraction (SBSE) can be applied for nearly every analyte (even neutral analytes). In
for the determination of 18 multiclass pesticides [79] and 7 strobil- negative CI the analytes need the presence of an acidic group or
urin fungicides [95]; and, such as the solid phase microextraction an electronegative group (like halogen atoms) in order to stabilise
(SPME) to determine 10 triazole fungicides in grapes [96]. These in the negative charge. Therefore the negative CI mode provides
techniques are based on adsorption of organic analytes from liquid better selectivity for most typical pesticides as they possess these
samples on to a stationary phase of polydimethylsiloxane (PDMS), electronegative groups. The group of Dong et al. [66] developed and
which is a fused-silica fiber in the case of SPME and a magnetic validated an analytical method based on GC with negative CI for the
stirring bar for SBSE. After the analytes are transferred to the poly- analysis of 82 pesticides in cabbage and apple, which they applied
mer coating, they are thermally desorbed in the GC injector. The on a grapes sample. Two pesticide residues were detected in the
advantages of these two approaches are good analytical perfor- grapes sample at levels lower than the current European MRL [6]:
mance, simplicity, low cost and elimination of organic solvents. pyrifenox-E at 0.27 ␮g/kg and pyridaben at 0.32 ␮g/kg.
The disadvantages of those recent techniques are the relatively long When MS analyzer is used, the acquisition modes mainly
equilibrium time and the possible carry-over. In the same line but selected are single ion monitoring (SIM) and full scan m/z 50–600.
with lower extraction time, a novel extraction technique called dis- In order to achieve a valuable identification and quantification of
persive liquid–liquid microextraction (DLLME) has been applied for the analyte at least 2–3 ions are selected in SIM mode.
8 multiclass pesticides in table grapes [83]. This approach is based As an alternative to the single quadrupole, the ion trap (IT) has
on a ternary component solvent extraction system: extraction sol- also been applied, in which a scan acquisition mode allows the ion
vent, disperser solvent and aqueous samples containing the analyte selection to be monitored post-acquisition.
of interest. The hollow fibre sorptive extraction (HFSE) is also con- Nowadays, combinations of most MS analyzers are possible,
sidered as a simple treatment technique based on the partitioning allowing tandem-MS (QqQ) to be performed. The use of QqQ has
of the analytes between sorbent and sample solution. HFSE SiO2 been introduced in routine-analysis of pesticide residues in grapes
[48,53,66,68,97,98]. This resulted in an improvement of the sensi-
tivity and selectivity of the analytical methods. Tandem MS gives
the possibility of measuring in selected reaction monitoring (SRM), grapes are the QTOF [58,60,64,72,96] and QOrbitrap [69]. One of
which is a very selective acquisition mode. The potential matrix the main attributes of the HRMS analyzers is their accurate mass
interferences are minimized or eliminated achieving lower limits of measurements, increasing the reliability of the analyte detection
detection by reducing the chemical noise of the chromatogram. The by providing extra selectivity by elemental composition of parent
QqQ proposed methods in grapes select in general at least 2 SRM and fragment ion spectra.
transitions per analyte. However, due to the small m/z ratio of the Only few papers have described the use of HRMS for quanti-
pesticide and the use of EI as ionization source, the number and/or tative purposes in grape pesticide residue analysis. A quantitative
abundance of ions may be poor or make it difficult to obtain two method for 10 triazole pesticides in grapes by GC-TOF was validated
suitable transitions, for example: mepanipyrim with the transitions by Souza-Silva et al. [96]. One m/z ion was selected for quantifi-
223 > 222, 222 > 220 and 222 > 118 [48]; binapacryl or pyrimethanil cation and specific software for the deconvolution was applied in
which SRM were 83 > 55 and 83 > 83, or 199 > 198 and 198 > 118, order to obtain pure mass spectra used for identification in case of
respectively [53]; acenaphthene with SRM 154 > 153 and 152 > 150 co-elutions. Dasgupta et al. [64] validated a method for 135 pes-
[56]. In other cases the m/z of the fragment is too low to be selective, ticides based on GC-TOF by selecting a single diagnostic m/z ion
as it is the case of the m/z 35 for the chlorine atom. The selection for each analyte. Two-dimensional gas chromatography (GC × GC)
of m/z is very specific for chlorine but not good enough to discrim- coupled to TOF has also been applied for quantitative purposes by
inate between different chlorinated pesticides that can have very the group of Banerjee [58,60], leading to a method for the analysis
close retention times. Some of the examples are dicloran (206 > 35), of 160 pesticides within 38 min [60]. Sivaperumal et al. [72] devel-
quintozene (264.8 > 35), vinconzolin (241 > 35), tetrachlorvinphos oped and validated a method based on UHPLC-TOF for 60 pesticides
(405.6 > 35), or beta-endosulfan (405.6 > 35) [66]. In this low selec- in different commodities including grapes. In this work the accu-
tive SRM acquisition, the reliability of the identification and the rate mass measurements were discussed for qualitative purposes,
quantification of the analyte may be compromised. and the mass measurements were reported with an accuracy level
<2.3 ppm. Although the use of TOF analyzers is an attractive tool
3.4.2. LC–MS based methods for accurate mass measurements, it is not so much exploited for
Liquid chromatographic separation of pesticides has been per- quantitative purposes [108]. The papers presented [58,60,64,72,96]
formed by reversed phase (RP), due to the polarity of these have selected a single diagnostic ion for quantification. However,
analytes. The common stationary phases are based on C18 the extraction of the ion from the total ion chromatogram is not
[48,51–57,63,65,67,69,72,74,75,90,93,95]. In general the mobile specified by using a mass accuracy threshold or range.
phase for the analysis of pesticides with RP-LC consists of mix- The QOrbitrap [69] has also been applied in the determination of
tures of water-methanol [32,48–51,53–57,63,65,67,72,90], and 166 pesticides in different fruit samples. In this approach an acqui-
water-acetonitrile [52,69,74,75,83,93,95]. In order to improve sition is done either in full MS-SIM or in full MS/data dependant
the ionization capacity, the use of different additives to the MS2 , both in positive mode. In case of target compounds detected
mobile phases have been described, such as ammonium acetate inside the ion abundance threshold and mass error (10 ppm error
[49,50,69,82] or ammonium formate [46,48,53–56,63,65,67,76] mass window), the product-ion spectra were obtained by selec-
(concentration level of 5–10 mM), and formic acid [51,57,72,90,93] tion within a window 4.0 m/z in the quadrupole to be sent to the
(normally at a concentration level of 0.1%). The injection volumes HCD collision cell of the QOrbitrap mass spectrometer. The accurate
are usually between 5 and 25 ␮L for a flow rate of 200–300 ␮L/min. mass measurement was established at <5 ppm for identity con-
One technological revolution in LC has been the implementa- firmation of the analyte; as example carbendazim was identified
tion of ultra-high pressure liquid chromatography (UHPLC). In within 0.9 and 1.1 ppm for the precursor ion and the product ion.
UHPLC the particle size of the solid phase is reduced from 5 to Although the new generation of HRMS analyzers can be applied
3 ␮m [46,48–57,63,65,67,74,76,82,83,90,95] to sub-2 ␮m [5,69,72] for quantitative analysis, the typical purpose of these analyzers
resulting in enhanced resolution in a shorter runtime. For instance, is much more to focus on the development of screening meth-
the group of Sivaperumal et al. [72] achieved the separation of 60 ods for post-acquisition non-target analysis in food [108–110].
pesticides in less than 5 min with average peak widths of 10 s. The most common instruments for quantitative target analysis in
Ionization in LC–MS is usually performed by atmospheric pres- multi-residue methods remain the QqQ and QTrap, due to the high
sure ionization (API) sources. API has the capacity of obtaining sensitivity and selectivity in target multi-residue methods.
abundant intact protonated molecules. The most used API source
is electrospray (ESI) in positive mode. Only one paper [74] selected 3.5. Quantitative analysis and matrix effect
atmospheric pressure chemical ionization (APCI) for the analysis
of 12 botanical insecticides in grapes. APCI could be a very suitable The use of chromatographic techniques coupled to MS can often
alternative to obtain abundant ionization of analytes without acidic produce very reliable methods for the determination of pesticides
or basic centre, as was the case for these 12 botanical insecticides. at trace level in grapes. However, matrix interferences can com-
Due to the characteristic soft ionization source API, LC is cou- pete with the analyte of interest and compromise the selectivity
pled directly to tandem MS analyzers, such as the QqQ or Qtrap and specificity of the method. The effect of these matrix interfer-
(Fig. 1). This explains why the QqQ [46,49–51,56,76,82] and QTrap ences can be compensated for after studying them and applying
[48,52–55,57,63,65,90,93] are the most common MS analyzers in different approaches. The best choice is the use of stable isotopically
LC-based methods for pesticide residues analysis. Both MS/MS labeled standards for each analyte. However, this option can be very
analyzers are used for quantification and confirmation purposes. expensive, and therefore other alternatives have been proposed in
Typically 2 or 3 SRM transitions are selected for target analysis of the papers reviewed.
pesticide residues: one for quantification and an additional one for The most universally adopted strategy is the use of matrix-
confirmation purposes. The use of the QTrap presents the advantage matched calibration by preparing the standard solution in a blank
of very sensitive scan acquisition in the second analyzer. grape extract. In all multi-residue methods included in Table 2,
matrix-matched calibration has been used to correct the effects of
3.4.3. High resolution MS-based methods the matrix interferences. For instance, Taylor et al. [49], Hiemstra
Finally, the use of high resolution MS (HRMS) instruments has et al. [56] or Mol et al. [55] decided to check the matrix effect in each
been introduced for quantitative pesticide residues analysis in run by comparing the matrix-matched calibration with the stan-
grapes. The HRMS analyzers used for pesticide residue analysis in dard calibration. Like this they could evaluate the matrix effect over
a large number of analyses and study its influence on the accuracy The dithiocarbamate fungicide residues represent one of the
of quantification. most complex groups to be determined due to their low stability
In methods using matrix-matched calibration sometimes in vegetable matrices and low solubility in water or polar organic
an internal standard such as triphenylphosphate [48,57] or solvents. Therefore, it is difficult to include these pesticides in the
heptachlor-epoxide [61] was introduced to correct the errors scope of a multi-residue method. Three methods for the analysis
derived during the sample treatment and/or instrumental analysis. of dithiocarbamate fungicides in grapes have been described [116].
In a few methods, isotopically labelled pesticide standards were They all use an extraction with alkaline buffer followed by HILIC
added during the analysis [33,65,67,69]. For example, in the multi- chromatography and LC–MS/MS detection.
residue method of Zhang et al. [65] six deuterium labeled internal
standards were introduced (dimethoate-d6, dichlorvos-d6, diuron-
d6, linuron-d6, dichlorvos-d6 and malathion-d6). However, those
standards were used to check the quality of the analysis and to 5. Future perspectives
estimate the matrix effect, but not for quantitative purposes. Only
in two analytical methods [67,69] isotopic dilution mass spectrom- One tendency seen in the sample treatment for GC applications
etry was used for quantitative purposes. is the use of alternative solid phases, such as the multi-walled
Most of the single-residue methods for grapes carbon nanotubes (MWCNTs) [78,94]. This material has been effec-
included in Table 3 also used matrix-matched calibration tively used in SPE for grape juice [78], or in dSPE replacing PSA in the
[38,76–78,80,83–86,88–94,96,98]. Only few of them used a QuEChERS workflow [94]. Another interesting novelty for GC–MS
combined strategy with matrix-matched calibration and an applications is the introduction of the atmospheric pressure chemi-
internal standard, such as triphenylphosphate [78,80], tris-(1,3- cal ionization (APCI) source, which gives a more soft ionization and
dichloro-2-propyl) phosphate [89], diniconazole [91], tetradifon more selective fragmentation. The integration of the APCI at GC-
[85,88], tebuconazole-d6 [96], and parathion ethyl-d10 [98]. QqQ analyzers has demonstrated a strong potential to improve the
abundance of the product ions leading to increased sensitivity and
selectivity. For instance, Portoles at al. [117] have presented a work
to evaluate the performance of GC-APCI-QTOF for screening of 132
4. Limitations of multi-residue methods pesticide residues in several vegetable matrices including grapes.
In order to test the screening capacity of the method, blank sam-
The most common and efficient way to carry out pesticide ples were spiked with the 132 pesticides at 0.01 mg/kg. Detection
residue analysis for hundreds of different compounds is the use was based on the extracted ion chromatogram of one diagnostic
of multi-residue methods able to measure in the MRL range from ion (exact mass ± 75 ppm and time window ± 0.2 min). With this
0.01 to 10 mg/kg. Unfortunately, these multi-residue methods can- approach 89% of the pesticides in 20 samples were found.
not measure all pesticides with the required accuracy in one single In LC–MS analysis a further minimisation of the sample treat-
run. The high diversity in chemical composition of these hundreds ment is obtained with single solvent extraction and/or dilution and
of pesticides compromises the use of a single strategy for their direct injection in the LC system [118]. An even further simplifi-
simultaneous analysis. This explains why in some cases it is still cation without the use of an LC system can be achieved by the
necessary to develop single-residue methods for the analysis of use of flow injection FI-MS [119]. One of the main drawbacks in
one pesticide or a few pesticides from the same chemical family. the application of this strategy is the matrix effect, which endan-
Examples are pesticides with a high polarity or with an ionic charac- gers the traceability of the quantification. In the last two years,
ter. Another problem may be the low stability of specific pesticides the use of high-throughput planar solid phase extraction (HTpSPE)
during sample extraction. was established as a new clean-up concept, resulting in matrix-
In the case of compounds with a high polarity or ionic com- free extracts with almost no interferences. HTpSPE combined a
pounds, new approaches based on LC have been proposed. They fully automated sample application and plate development with
can be divided in three strategies: (i) the polarity of the analytes is the thin layer chromatography–MS interface as the essential tools
reduced by derivatization of the analytes or by addition of an ion- of the method. Oellig et al. [120] applied HTpSPE clean-up com-
pairing substance to the mobile phase before analysis by RP-LC. bined with FI-TOF-MS in a grape sample for screening analysis,
This decreased polarity leads to an increased retention and more omitting the LC separation step. In the recovery experiments for
adequate peak shape [111]. (ii) Use of hydrophilic interaction liq- 7 pesticides (azoxystrobin, chlorpyrifos, fenarimol, penconazole,
uid chromatography (HILIC) with carbon or ion exchange phases pirimicarb, mepanipyrim and acetamiprid) the use of HTpSPE for
instead of reversed phases. Also this leads to an increased reten- clean-up demonstrated a very efficient option in order to eliminate
tion of the analytes [112,113]. (iii) Elimination of the separation the matrix effect, obtaining near-100% recovery values.
technique and use of direct flow injection (FI) to MS/MS [114]. Recently, ambient desorption/ionization (ADI) appears to be a
For instance, a specific single method for the analysis of ethep- powerful method that reduces the need for sample preparation and
hon using UHPLC-QqQ has been described by Hanot et al. [115]. separation techniques like GC and LC. The ADI has been applied for
Ethephon is a stable molecule in aqueous solutions below pH 4 and pesticide residue analysis in grapes for qualitative and quantitative
is decomposed in ethylene and dihydrogen phosphate under alkali aims. Direct analysis in real time (DART) [121] and micro-fabricated
and high temperature conditions. Due to its high polarity it can- glow discharge plasma (MFGDP) [122] have proven to be useful in
not be included in a multi-residue method. Its chromatographic screening purposes, while a low-temperature plasma (LTP) probe
separation was obtained by using a HILIC column with addition of [123] has shown to be effective in quantitative analysis as well. In
ammonium hydroxide to the aqueous mobile phase. Anastassiades the work of Edison et al. [121] 132 pesticides were simply swabbed
et al. [113] studied ion chromatography using anion exchange for from the grapes surface, and then detected by DART-Orbitrap. Out
the analysis of highly polar pesticides in food (including grapes). of the 132 analytes, 86% of them were qualitatively detected at 10
This method was applied for ethephon, 2-hydroxyethephon (HEPA, ng/g concentration level. The great potential of ADI sources is the
ethephon metabolite), glyphosate, aminomethylphosphonic acid capability of providing a mapping of the pesticide distribution in the
(AMPA, glyphosate metabolite), N-acetyl AMPA, glufosinate, N- fruit [109]. However, the use of ADI for quantitative purpose could
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Journal of Chromatography A, 1433 (2016) 1–23

Contents lists available at ScienceDirect

Review of analytical methods for the determination of pesticide

1. Introduction nutritional properties of grapes and their ancient domestication

Pesticide Family-activity Pest control MRL Table/Wine grapes (mg/kg)

Pesticide Family-activity Pest control MRL Table/Wine grapes (mg/kg)

Penconazole Conazole fungicide Powdery mildew 0.2

38 - SLE: 8 g sample + 50 LC-ESI-MS/MS 0.01–0.8 73–92 4.5–17.7 1a [49]

57 - SLE: 75 g LC-ESI-MS/MS 0.01–0.5 44–118 3–30 1a [50]

74 - SLE: 20 g LC-ESI-MS/MS 0.01–1 63–158 3–31 1a [51]

309 - SLE: 75 g sample + GC–MS/MS 0.01–0.05 57–122 2–30 1a [53]

82 - SLE: 10 g sample + 10 mL LC–MS/MS 0.0025–0.05 36.5–120.5 0.3–19 0.1–3.3 [54]

80 - QuEChERS: 10 g GC–MS/MS 0.005–0.2 60–127 0.2–16.7 10a [48]

51 - SLE: 10 g sample + 10 GCxGC–MS (TOF) 0.01 70–109 3–10 0.2–3.0 [58]

160 - SLE.: 10 g GCxGC–MS (TOF) 0.01–0.05 67–135 1–12 – [60]

50 - SLE: 10 g sample + pH GC–MS/MS 0.01–0.05 71–117 3–18 5.0–19.2 [62]

150 - SLE: 10 g LC–MS/MS 0.01–0.1 40–109 1–25 10a [63]

209 - SLE: 10 g sample + 10 LC–MS/MS 0.01–0.5 77–121 9–33 0.1–10 [65]

82 - SLE: 15 g GC-NCI-MS/MS 0.01–0.02b 58.7–124.4b 3.9–15.9b 0.01–1.82 [66]

48 - SLE: 0.5 g LC–MS/MS (QqQ) 0.01–0.25 64–121 4–20 0.8–10.3 [67]

349 - SLE: 10 g GC–MS/MS 0.005–0.025 70–120 <20 5–10 [68]

71 - Pressurised liquid UHPLC–MS/MS 0.001–0.01 70.8–119.1 <20 0.12–2.16 [5]

166 - SLE: 15 g UHPLC- 0.01 0.4 42.9–123.8 5.2–28.3 <5 [69]

341 - SLE: 10 g GC–MS/MS – – – – [71]

60 - SLE: 10 g sample + 25 UHPLC–MS (TOF) 0.05–0.2 73–111 1–4 0.8–11.8 [72]

S. Grimalt, P. Dehouck / J. Chromatogr. A 1433 (2016) 1–23

S. Grimalt, P. Dehouck / J. Chromatogr. A 1433 (2016) 1–23

S. Grimalt, P. Dehouck / J. Chromatogr. A 1433 (2016) 1–23

S. Grimalt, P. Dehouck / J. Chromatogr. A 1433 (2016) 1–23

S. Grimalt, P. Dehouck / J. Chromatogr. A 1433 (2016) 1–23

7 strobilurin Grape - 5g sample + 2 mL LC-DAD 10–175 89–101 2–9 0.3–2.0 [95]

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