Analytical Methods for Pesticide Residues H. C. Liang1*, Navdeep Bilon2, Michael T. Hay3

ABSTRACT: A review of literature published in 2013 on

Abbreviations and Acronyms Used

analytical methods for pesticides, including mostly

AChE – Acetyl Cholinesterase Enzyme

insecticides but also some herbicides, is presented here and

CPE– Cloud point extraction

includes papers on analytical methods such as biochemical

CV – Cyclic voltammetry

assays and immunoassays, electrochemical methods,

DDE – Dichlorodiphenyldichloroethene

review articles on analytical methods, chromatographic or

DDT – Dichlorodiphenyltrichloroethane

mass

spectrophotometric

DLLME – Dispersive liquid–liquid microextraction

chemiluminescence

dSPE – Dispersive solid–phase extraction

spectrometric

techniques,

techniques,

fluorescence,

and

techniques. There is also a section on extraction techniques

ECD – Electron capture detection

because of their importance in pesticide residue analyses.

EIS – Electrochemical Impedance Spectroscopy ESI – Electrospray ionization

KEYWORDS: analytical methods, pesticides, pesticide

ELISA – Enzyme–linked immunosorbent assay

residues, organochlorine, organophosphate, GC, MS, LC,

FPD – Flame photometric detection

analytical chemistry, immunoassays, fluorescence

GC – Gas chromatography GC–EI–MS – Gas chromatography mass spectrometry in

doi: 10.2175/106143014X13975035526185

electron ionization mode GC–MS – Gas chromatography mass spectrometry

————————— GC–QqQ–MS/MS – Gas chromatographic triple 1*

Senior Engineer/Water Chemistry and Process Technical Lead,

quadrupole tandem mass spectrometry

Tetra Tech, Inc., 1576 Sherman Street, Denver, Colorado 80203; Tel.

720–931–9314;

Fax.

303–825–0642;

GCB – Graphite carbon black

e–mail:

[email protected]

HPLC – High performance liquid chromatography

2

HRMS – High resolution mass spectrometry

Process Development Chemist, Biosearch Technologies,

Novato, California 3

LOD – Limit of detection

Associate Professor, Penn State Beaver, Monaca, Pennsylvania

LOQ – Limit of quantitation LC – Liquid chromatography LLE – Liquid–liquid extraction

2132 Water Environment Research, Volume 86, Number 10—Copyright © 2014 Water Environment Federation

LP–GC/MS–MS – Fast low pressure gas chromatography

synthetic

triple quadrupole tandem mass spectrometry

peptides;

they

termed

nanopeptamers,

to

recognize the analyte–antibody immunocomplex during a

MIP – molecularly imprinted polymer

lateral

MS – Mass spectrometry

noncompetitive assay for small molecules. Zhang et al.

MS/MS – tandem mass spectrometry

(2013) reported on a simple, portable and inexpensive

MSPD – Matrix solid–phase dispersion

method for determining exposure to organophosphorus

MRL – Maximum residue limit

pesticides by detecting the presence of a characteristic

MWCNTs – Multi–walled carbon nanotubes

biomarker – organophosphorylated butyrlcholinesterase –

MSPE – Magnetic solid–phase extraction

in human plasma. Their method used electrochemical

NPD – Nitrogen phosphorous detector

immunosensors derived from Fe3O4 at TiO2 nanoparticles

OCP – Organochlorine pesticide

which were linked to antibodies that were selective for the

OPP – Organophosphorus pesticide

biomarker. They also used the inherent magnetic properties

PLE – Pressurized liquid extraction

of the nanoparticles to separate the immunosensor from the

PSA – Primary Secondary Amine Sorbent

plasma sample using an external magnetic field.

QuEChERS – Quick Easy Cheap Effective Rugged and Safe

flow test.

Their

system provided

a rapid

A variety of authors reported on the use of

RSD – Relative standard deviation

ELISA to detect various pesticides. Deng et al. (2013)

SDME – Single–drop microextraction

developed a detection method for parathion. The authors

SERS – Surface–enhanced Raman Spectroscopy

injected New Zealand rabbits with a derivative of

SPE – Solid phase extraction

thiophosphoryl chloride coupled to bovine serum albumin

SPME – Solid–phase microextraction

in order to obtain anti–parathion polyclonal antibodies. The

SWV – Square Wave Voltammetry

resulting antibodies were then used in an indirect

UHPLC–MS/MS – Ultra high performance liquid

competitive chemiluminescence ELISA to detect parathion

chromatography–tandem mass spectrometry

in spiked vegetables and water samples. Methyl parathion

WHO/FAO – World Health Organization/Food and

was detected by Yuan et al. (2013) using a biotin–

Agriculture Organization of the United Nations

streptavidin indirect competitive ELISA. Their method showed a six–fold increase in sensitivity over traditional

Analytical Methods

indirect competitive ELISA. Hua et al. (2013) reported a

Biochemical Assays and Immunoassays. An

method for the detection of eight different OPPs as well as

approach using an immunoassay to detect the small

two different neonicotinoid insecticides using ELISA.

molecular herbicides, molinate and clomazone was

There method used monoclonal antibodies with antigen

published by Vanrell et al. (2013). The authors used

binding sites for the two different classes of insecticides

2133 Water Environment Research, Volume 86, Number 10—Copyright © 2014 Water Environment Federation

and was applied to tap water, pond water, grape, cucumber,

chemiluminescence ELISA. They claimed that their

and soil samples.

method was faster and more sensitive than the traditional

Mortl et al. (2013) used ELISA to detect

ELISA method.

glyphosate in surface and ground water samples. The

Groups also reported advancements in the use of

sampling was conducted over a two year period, 2010–

carbon

2011, in three different locations in Hungary: Bekes

immunosensors. One group, Liu, Song, et al. (2013), used

county, the Danube River, and Lake Velencei. The reasons

single walled nanotubes on a glassy carbon electrode to

for the different glyphosate concentrations in the various

detect paraoxon. They were able to chemically attach a

water sources were discussed. An ELISA method was also

paraoxon hapten to the surface of the nanotube forest,

reported by Navarro et al. (2013) that detected chlorpyrifos

which then selectively bound paraoxon antibodies. Using

and fenthion pesticides in tangerine juices. Chlorpyrifos

the resulting electrode in a displacement assay the

ethyl residues found in water and sediment samples were

researchers were able to detect paraoxon at parts per billion

also showed by Otieno et al. (2013) to be successfully

levels. Another group, Pan et al. (2013), fabricated a

detected by ELISA. The authors stated that their results

piezoelectric immunosensor for detecting metolcarb – a

were comparable to those obtained by HPLC analysis –

carbamate pesticide. Their sensor consisted of a multi–wall

which is a less commonly available analytic method.

carbon nanotube/poly(amidoamine) dendrimer hybrid,

Desmet et al. (2013) showed that multiplex microarray

which they report absorption performance studies with

ELISA had increased sensitivity and reproducibility over

Langmuir and Freundlich isotherm models. The resulting

the classical ELISA method for detecting the presence of

sensor was able to detect metolcarb in spiked apple and

2,4–dichlorophoxyacetic acid in spiked water samples.

orange juice samples.

Guo, Tian, et al. (2013) also found improved results with a

nanotubes

in

Electrochemical

preparing

Methods.

electrochemical

A

variety

of

multiplex assay rather than the traditional ELISA. The

electrochemical methods for pesticide analysis were

authors

competitive

reported this past year. Chen and Chen (2013) developed a

immunoassay using suspension array technology to

CV technique for quantifying pesticides, while Svorc et al.

simultaneously detect three different pesticides: triazophos,

(2013) used SWV with a boron–doped diamond electrode

carbofuran, and chlorpyrifos in spiked vegetables. Their

to detect nanomolar levels of atrazine. Tran et al. (2013)

method exhibited multi–target detection with wider

also developed a method for detecting aztrazine using an

detection ranges and better precision than the traditional

immunoaffinity approach combined with EIS. Fan, Zhao,

methods. Liu, Ge, et al. (2013) also demonstrated an

et al. (2013) used an aptasensor based on EIS to detect

improved method to detect phosmet, azinphos–methyl, and

acetamiprid in wastewater and tomatoes. The researchers

azinphos–ethyl in vegetable samples using an enhanced

used a gold electrode surface that had been electroplated

used

multiplex

bead–based

2134 Water Environment Research, Volume 86, Number 10—Copyright © 2014 Water Environment Federation

with gold nanoparticles to immobilize the aptamer. When

coated with a MIP–ionic liquid–graphene composite film to

an acetamiprid–aptamer complex formed, a corresponding

detect methyl parathion. And finally, Wang, Dai, et al.

increase in the electron transfer resistance was correlated to

(2013) used a MIP film on TiO2 nanotubes that had been

nanomolar concentration levels of the insecticide. Li, Li, et

modified with gold nanoparticles to detect chlorpyrifos.

al. (2013) developed a photoelectrochemical method that

Bucur et al. (2013) reported on the optimal

detected 4–nitro–phenolate – the hydrolysis product of

conditions for using acetylthiocholine iodide, rather than

methyl parathion. The authors used a modified glassy

the more expensive chloride salt, as a pseudosubstrate for

carbon electrode with TiO2 nanoparticles coated with

an amperometric biosensor. This class of biosensor detects

perylene–3,4,9,10–tetracarboxylic acid. Their system was

insecticides that inhibit AChE – an enzyme that hydrolyzes

used to detect methyl parathion in green vegetables. Liu,

acetylthiocholine to thiocholine. When the insecticide

Jing, et al. (2013) also developed a system for detecting

inhibits the enzyme, the thiocholine levels decrease and is

methyl parathion. Their system used a glassy carbon

no longer present to be oxidized. Unfortunately, iodide can

electrode coated with a graphene–Fe3O4 nanocomposite

be oxidized giving false signals; therefore conditions were

film immobilized AChE. The resulting electrochemical

optimized to avoid a false analytical signal or reduced

biosensor

sensitivity.

detected

methyl

parathion

with

good

reproducibility and acceptable stability. In addition, Xue,

Spectroscopy. Some groups reported the use of

Kang, et al. (2013) reported on a graphene–Nafion

SERS for detection of pesticides. Liu, Ye, et al. (2013) used

modified glassy carbon electrode that detected methyl

SERS to detect the organophosphorus pesticide dimethoate.

parathion in vegetables. Wagheu et al. (2013) reported on a

Their method of using confocal Raman micro–spectrometry

series of glassy carbon electrodes that had been chemically

with a Klarite substrate was compared with the traditional

modified with smectite–type clay to detect the herbicide

Raman technique and shown to give significantly enhanced

mesotrione. The sodium cation in the clay was exchanged

detection capabilities. A second group, Tang et al. (2013),

with two different cationic surfactants to enhance the

also used SERS for in situ detection of thiram using gold

mesotrione absorption capacity. It was found that the

nanoparticles grafted onto dendritic α–Fe2O3 substrate.

didodecyldimethyl ammonium cation was the most

With an optical microscope, the authors were able to

effective at detecting the herbicide.

visualize the pesticide residue on both tea leaves and fruit.

Multiple

groups

used

MIPs

to

prepare

Review Articles. In 2013, review articles were

electrochemical sensors. Duan et al. (2013) created a sensor

published covering a various pesticide analysis techniques.

from a glassy carbon electrode coated with a MIP thin film

Liang et al. (2013) highlighted the 2012 advancements in

capable of detecting acephate in aqueous solution, while

pesticide residue analysis. Their survey covered six major

Zhao, Zhao, et al. (2013) used a glassy carbon electrode

areas – chromatographic and spectrometric techniques,

2135 Water Environment Research, Volume 86, Number 10—Copyright © 2014 Water Environment Federation

spectrophotometric

techniques,

fluorescence

and

highest in all the three cases, comprising 55–71% of total

chemiluminescence techniques, biochemical assays and

DDT, followed by p,p–DDE, 26–39%, and the least, p,p–

immunoassays, electrochemical methods, and review

DDD of 2–5%. The mean estimated daily intake of DDT by

articles on analytical methods. Wang and Yu (2013)

infants from mother's milk in the three locations was found

focused their review on the advancement in gold

to be 62.17 µg kg–1 body weight, which is about three times

nanoparticle sensors. The authors highlighted the synthesis,

higher than the acceptable daily intake set by WHO/FAO

fabrication and functionalization of the gold nanoparticles

for total DDT.

as well as on their use in detecting aqueous pollutants.

Gomez–Ramos et al. (2013) reported on using

Spectrometric

LC–HRMS techniques to analyze pesticides in fruit–based

Techniques. Hernandez, Cervera, et al. (2013) reported on

and vegetable–based matrices is a far cheaper and more

the application of GC–QqQ–MS/MS for pesticide residue

effective technology than the more commonly used QqQ–

analysis of different food and environmental sample

MS method. LC–HRMS is a better alternate technology to

matrices. The article highlighted the advantages for using

utilize when analyzing large numbers of pesticides.

this technique over traditional GC methods by reliably

However, optimization of its operational parameters using

quantifying and identifying low pesticide concentrations for

non–target analysis in full–scan mode and of its software

compounds from different chemical classifications. Forster

still need to be undertaken in order to reduce the number of

et al. (2013) described a sensitive HPLC method, with MS

drawback when using HRMS.

Chromatographic

or

Mass

and UV detection, for the analysis of up to 32 pesticides in

Banerjee et al. (2013) reported on a single

a mixture. Analytes like carbamates, organophosphates,

quadrupole GC–MS method optimized for multiresidue

pyrazoles, triazines, or ureas were separated on C18

determination of 47 pesticides in grapes with limit of

reversed–phase monolithic silica capillary columns using a

quantifications of each compound in compliance with the

gradient elution profile and directly transferred to a MS. A

EU–MRL requirements. Residues were estimated in

porcine kidney sample was spiked with a set of seven

selected

pesticides, and after a typical SPE procedure, all analyses

temperature vaporizer–large volume injection (8 µL). All

were conducted using LC–MS.

the GC and MS parameters were thoroughly optimized to

ion

monitoring

mode

with

programmable

OCP residues in human and cow's milk in

achieve satisfactory linearity (R–2 > 0.99) within 0.01–0.25

Ethiopia were analyzed using GC–ECD and were reported

mg kg–1 with minimum matrix interferences. Recoveries at

by Gebremichael et al. (2013). Mean levels of total DDT

0.01 and 0.02 mg kg–1 were within 67–120% with

in the human and cow milk samples in the three areas were

associated precision RSD below 19%. An improved LC

12.68 and 0389 µg g–1, respectively. In the human milk

MS/MS analytical methodology for residue determination

samples from the three locations, the p,p–DDT was the

of glyphosate and its metabolite in soils found in South

2136 Water Environment Research, Volume 86, Number 10—Copyright © 2014 Water Environment Federation

America used for soy, corn, or other crops, as reported by

spectrometer separated the matrix ions of red pepper easily

Botero–Coy et al. (2013). The methodology developed was

from the pesticides due to differences in their mass defect.

applied to the analysis of 26 soils from different areas of

Nakamura et al. (2013) reported on a method for

Colombia and Argentina, and the method robustness was

determining 305 pesticides by GC/MS using synchronous

demonstrated by analysis of quality control samples along

SIM/Scan acquisition in which 111 pesticides that could

four months. The analytical methodology was satisfactorily

not be detected adequately in the scan mode among the 305

validated in four soils from Colombia and Argentina

pesticides were selected for SIM acquisition.

fortified at 0.5 and 5 mg kg-1. Analysis by QTOF MS was

recoveries were obtained for about 80% of pesticides with

useful to confirm the presence of interferent compounds

values of between 70 and 120%. The feasibility of using

that shared the same nominal mass of analytes as well as

chemometric methods for rapid analysis of peptide

some of their main product ions.

mixtures was validated by Mei et al. (2013) using a

Good

Sensitive HPLC analytical methods were used to

simulated GC–MS data matrix of a three–component

assign the optical rotation and to prepare milligram-level

mixture. The practicability of the method was proved by

quantities

further

resolving the GC–MS data of the 40–pesticide mixture. The

characterization with respect to herbicidal activity of chiral

results showed that both the mass spectra and the

pesticides (Buerge et al., 2013). In miniaturized biotests

chromatographic information of the components were

with garden cress, (–)–beflubutamid showed at least 1000

extracted from the overlapping signals, and the pesticide

times higher herbicidal activity (EC50, 0.50 µM) than (+)–

mixture was analyzed with a 10 min elution with the help

beflubutamid, as determined by analysis of chlorophyll a in

of the proposed method.

of

the

pure

enantiomers

for

5–day–old leaves. In further biotests, the (+)–enantiomer of

Matrix effects on 110 pesticides in 28

the phenoxybutanoic acid metabolite showed effects on

tea matrixes of different varieties and origins by

root growth, possibly via an auxin type mode of action, but

LC/MS/MS were studied by Li, Pang, et al (2013). The

at 100x higher concentrations than the structurally related

multivariate tool called hierarchical cluster analysis was

herbicide (+)–mecoprop. Five pesticides from red pepper,

used to analyze the influence of physicochemical

hexaconazole, isazophos, isoxathion, kresoxim–methyl, and

characteristics of pesticides and tea varieties on the matrix

triazophos,

resolution

effects. Any type of tea can be chosen from each cluster as

chromatography and MS Thurman et al. (2013). In the

a corresponding representative matrix within that cluster to

research, high–resolution chromatography was found to be

make matrix–matched solutions, which could simplify

a valuable tool to separate the isobaric pesticides from one

analysis while guaranteeing its accuracy. Matrix effects on

another, whereas the high resolution of the mass

most pesticides were similar despite the physicochemical

were

analyzed

by

high

diversities of the pesticides.

A novel chiral liquid

2137 Water Environment Research, Volume 86, Number 10—Copyright © 2014 Water Environment Federation

chromatography coupled with tandem mass spectrometry

(2013) reported on common methods for overcoming

(LC–MS/MS)

matrix effects in LC/ESI/MS (matrix–matched calibration,

method

for

measuring

individual

enantiomers of nine pesticides including herbicides,

standard

insecticides, and fungicides in soil and water was evaluated

extrapolative dilution, and post–column flow splitting). The

by Li, Dong, et al. (2013). The separation and

methods were compared according to their ability to give

determination

both true and accurate results for pesticide determination in

were

performed

using reversed–phase

addition,

post–column

such

as

onion

infusion,

chromatography on an amylose chiral stationary phase, a

complicated

Chiralpak AD–RH column. The mean recoveries for all

Extrapolative dilution and standard addition were found to

enantiomers from the soil and water samples ranged from

give results statistically insignificantly different from the

77.8–106.2% with the RSD less than 14.2%. Good linearity

correct values. In addition extrapolative dilution – a hybrid

was obtained for all studied analytes in the soil and water

approach for both reducing and correcting for matrix

matrix calibration curves over the range of 2.0–125 µg L-1.

effects – was found to result in the highest accuracy of the

LOD for all enantiomers in the soil and water were less

measurements.

than 1.8 µg L-1, whereas the LOQ was less than 5.0 µg L-1.

matrices

standard

and

garlic.

An LC/MS/MS method was developed for the

A simple method for determining 73 pesticide

determination of 56 residual pesticides from commercial

residues in vegetables and fruit by GC–MS/MS was

crops by Lee et al. (2013). The study showed that the LOD

demonstrated by Lu et al. (2013). The LODs of the method

and mean recoveries of the pesticides were 11.54 µg kg-1,

were from 0.012–18.8 µg kg–1 and LOQs were in the range

and 65–82%, respectively. This method was evaluated as a

of 0.042–61.8 µg kg–1, which were much lower than the

way to monitor 345 agricultural products collected from

MRLs established by European legislation. The average

nine provinces in Korea. Fifteen pesticides were detected

recoveries of the method ranged from 86.7–124%, 85.6–

from 39 samples and two or more residual pesticides were

117%, and 89.2–111% at three spiked levels of 0.10, 0.20,

found in seven samples. Kittlaus et al. (2013) described a

0.50 mg kg–1 in leek samples, with RSDs of 1.84–11.3%,

fully automated 2D–LC–MS/MS system using analytical

2.40–9.50%,

reversed

and

0.79–8.30%,

respectively.

The

phase

separation of

pesticides

to

determine from

different

components from dry or semidry biological tissues could be

concentrations

various

food

extracted using the solvent and picked up by the needle for

commodities.

electrospray ionization mass spectrometry. As described

pesticides in cucumber, lemon, wheat flour, rocket, and

by Mandal et al. (2013), this technique was applied to real–

black tea. For the large majority of the analytes, the

time pesticide analysis of living plants. The results were

recovery was between 70–120% and the RSD was under

validated with that of a well–known system, liquid

20%. The LODs for nearly all the compounds were at least

extraction surface analysis mass spectrometry. Kruve et al.

at 0.01 mg kg-1.

The method was validated for over 300

For over 50% of the analytes, good

2138 Water Environment Research, Volume 86, Number 10—Copyright © 2014 Water Environment Federation

sensitivity was observed even at a concentration of 0.001

physicochemical properties in fresh vegetables including

mg kg-1.

OPPs, OCPs, pyrethroids, and carbamates. Pesticide A multiresidue method based on isotope dilution

residues above the MRL were detected in 15.89% of the

and final analysis by LC–ESI–MS/MS was developed for

total samples (168 from 1057 samples), but 83.90% of the

the determination of 26 pesticides and transformation

total samples (887 from 1057 samples) had no detected

products in sediment (Kock–Schulmeyer et al., 2013).

residues. The detected and most frequently found pesticide

Application of the method to the analysis of five real

residues were permethrin (45 times) and endosulfan (34

samples from four different Spanish rivers revealed the

times) followed by deltamethrin (27 times). A mix of 41

presence of chlorpyrifos, diuron and diazinon being the

pesticides, including OPPs, synthetic pyrethroids, and

most ubiquitous.

fungicides, was investigated in order to benchmark two–

The use of UV–MALDI MS, employing the

dimensional GC systems in terms of linearity, LOD, and

Orbitrap analyzer for solid–state assay of halogenated

peak shape measures. Engel et al. (2013) described the

phenyl–pesticides in mixtures, was evaluated by Ivanova et

performance and complementarities of FPD in phosphorus

al. (2013). The full method and technique for validation

and sulfur modes, micro ECD, NPD, flame ionization

was performed using the dried droplet sample preparation

detector, and time–of–flight MS for the comprehensive

technique on embedded analytes in a novel organic matrix

two–dimensional GC analysis of pesticides. These three

crystals of N–(1H–benzoimidazol–2–yl)–guanidine (M4)

detectors had improved detection limits of 3–7 times and

and (E)–phenyl–2–pyridyl ketone oxime (M5), resulting in

4–20 times lower LODs in GC x GC mode compared with

successful ionization of the analytes. Huang et al. (2013)

FID and time–of–flight MS, respectively. In contrast, FPD

reported on

using

in sulfur mode had poor peak shape (tailing factor 3.36–

atmospheric pressure solids analysis probe coupled to

5.12) and much lower sensitivity (10–20 fold lower

MS/MS for the detection of 13 commonly used multi–class

compared to FPD in phosphorus mode).

a rapid direct–analysis

method

pesticides in vegetables. The matrix effects of celery, leek

Fluorescence Techniques. Diaw et al. (2013)

and rape were analyzed, and had apparent influences.

described a new direct Laser Photo–Induced Fluorescence

Under the optimal conditions, the linear range was 5. 0–500

method developed for the determination of two phenylurea

µg L-1 with a correlation coefficient above 0.995. The

pesticides, namely fenuron and diflubenzuron. The method

LODs of analytes were 0. 04–0.89 µg kg-1, with a precision

uses a tunable Laser to obtain the photoproduct(s) and to

of 5. 1–13. 0% (n = 7).

simultaneously analyze their fluorescence. The calibration

Pesticide residues were measured in a study using

curves were linear over one order of magnitude and the

GC–MSD by El–Saeid, et al. (2013). This method was used

LODs were in the ng mL–1 range. Satisfactory recoveries

to measure 86 pesticide residues with a broad range of

were obtained in the analysis of both pesticides in river and

2139 Water Environment Research, Volume 86, Number 10—Copyright © 2014 Water Environment Federation

sea water spiked samples. Based on the inner filter effect

solvents, including water, methanol, methanol–water binary

of Au nanoparticles on the fluorescence of CdTe quantum

mixtures and cyclohexane, on the propanil photo–induced

dots, a fluorescence method for the rapid assay of

fluorescence properties was studied, and several parameters

carbamate pesticides has been developed.

The results,

(irradiation time, excitation and emission wavelengths,

reported by Guo, Luo, et al. (2013), show that the

medium) were optimized. The optimal photo–induced

calibration curve for methomyl was established in the range

fluorescence analytical performances were obtained in an

of 0.017–0.5 µg mL–1 with a LOD

of 0.011 µg mL–1

80/20% v:v methanol/water mixture, with a wide linear

(S/N=3) which is superior to the HPLC coupled with UV

dynamic range of nearly three orders of magnitude, low

detection method.

Inoue et al. (2013) reported on the

LOD and LOQ values of 1.3 and 4.7 ng mL–1, respectively,

stereoselective determination of dichlorprop enantiomers in

and a RSD of 1.3%. The optimized PIF method was applied

tea samples such as green, black, jasmine, and oolong was

to the estimation of propanil residues in various spiked

developed by ultra performance LC with fluorescence

natural water samples, collected in the Senegal River

spectrometry after covalent chiral derivatization. In the

valley, with satisfactory recovery values (97–117%). Meng

covalent chiral derivatization using (S)–(+)–4–(N,N–

et al. (2013) developed a method for the determination of

dimethylaminosulfonyl)–7–(3–aminopyrrolidin–1–yl)–

OPPs in real samples based on inhibition mechanism of

2,1,3–benzoxadiazole, the peak resolution between the S

AChE. The biosensor is composed of the enzymes AChE

and R–dichlorprop enantiomers was 2.6. LODs and LOQs

and choline oxidase, quantum dots, and acetylcholine. After

values were 10 and 50 ng mL-1 standard solution. The

the experimental conditions are optimized, the LOD for

linearity of the calibration curves yielded the coefficients

dichlorvos was found to be 4.49 nM. Two linear ranges

(r2 > 0.99, ranging from 0.05–5 g mL-1) of determination of

allowed a wide determination of DDVP concentration from

each of the dichlorprop enantiomers. SPE extraction was

4.49–6780 nM.

used for the sample preparation of dichlorprop in various

The LC method for simultaneous determination

tea samples. Recoveries were in the range of 82.4–97.6%

of seven carbamate pesticides was described. The method

with associated precision values (within–day: 82.4–95.8%,

employed a Zorbax Eclipsed XGB C–8, column and 30:70

n=6, and between–day: 83.7–97.6% for 3 days) for

acetonitrile–water mixture (v/v) as mobile phase with UV

repeatability and reproducibility.

detection at 235 nm. Prasad et al. (2013) reported that good spectral

separation of all these carbamates was achieved at 1 mL

properties of propanil, a contact anilide herbicide were

min-1 flow rate of the mobile phase at 25 ⁰C. Their recovery

investigated (Mbaye et al., 2013). In this study, non–

from food grains fenugreek leaves and apples was found to

fluorescent propanil was transformed by UV irradiation

be greater than 80%.

The

photo–induced

fluorescence

into strongly fluorescent photo–product(s). The effect of

2140 Water Environment Research, Volume 86, Number 10—Copyright © 2014 Water Environment Federation

mercaptopropionic

Shing (2013) reported on the effects of poly(2–

whole cell fluorescence biosensor for the detection of the dichlorophenoxyacetic

acid

(2,4–D),

(3–MPA),

using

microwave

irradiation. The LODs were as low as 3.0 ng L–1.

hydroxyethyl methacrylate) (pHEMA) immobilization on a

pesticides

acid

Hernandez, Kergaravat, et al. (2013) reported on

and

a new method for the electrochemical detection of the

chlorpyrifos. The detection limits of the biosensor without

horseradish peroxidase enzymatic reaction by means of

pHEMA for 2,4–D and chlorpyrifos were both 0.025 μg L-

square wave voltammetry for the determination of phenolic

1

. The presence of pHEMA improved the LODs to 0.235

compounds in environmental samples. The calibration and

and 0.117 μg L-1, respectively. pHEMA is known to

validation sets were built and assessed. In the calibration

enhance the reproducibility of the biosensor with average

model, the LODs for phenolic compounds oscillated from

RSD of +/– 1.76% for all the pollutants tested, 48% better

0.6–1.4 x 10–6 mol L–1. Recoveries for prediction samples

than the biosensor without pHEMA (RSD = +/– 3.73%).

were higher than 85%.

A combination of a modified

IR

QuEChERS method and CPE before spectrophotometric

fluorescence

analysis was developed for the determination of carbaryl

spectroscopy (Wilson, et al., 2013). It was found to contain

residues in vegetable samples that include cucumber,

glycerin as well as another compound. IR and MS data

cabbage, Chinese cabbage, kale, and yard long bean as

were readily obtained for this second component, but it was

described by Karnsa–ard et al. (2013). The proposed

not easily identified as common instrument libraries had no

method gave a limit of detection (LOD) of 0.1 mg kg–1,

matching spectra. Xing et al. (2013) conducted a study on a

which

method for the determination of paraquat by cucurbit[7]uril

preconcentration, and below the MRL set in vegetable

(CB[7]) fluorescence quenching. The assay was based on

samples. Acceptable recoveries (> 79%) and precision with

the reaction of the CB[7] with acridine orange. Under the

the relative standard deviation less than 11% were

optimum conditions, a linear range of 3.0800 nmol L–1 and

obtained, in good agreement with the results obtained from

a LOD of 1.61 nmol L–1 for paraquat were obtained.

HPLC.

Spiromesifen spectroscopy,

GC–MS,

was and

analyzed X–ray

using

is

10–fold

lower

than

analysis

without

A spectrophotometric microfluidic bioreactor

Spectrometric Techniques. Based on the highly sensitive fluorescence change of water–soluble CdSe/ZnS

system

is

described

core–shell quantum dots by paraquat, a methodology was

organophosphorus pesticides (Rattankit et al., 2013). The

developed by Duran et al. (2013) to selectively determine

glass chip was designed and fabricated for in situ

paraquat in water samples. The methodology enabled the

monolithic

use of simple pretreatment procedure based on the simple

immobilization via a covalent bonding method. A linear

water solubilization of CdSe/ZnS quantum dots with

relationship between the absorbance and percentage

hydrophilic heterobifunctional thiol ligands, such as 3–

inhibitions was obtained over the concentration range of

preparation

for

and

the

determination

subsequently

of

AChE

2141 Water Environment Research, Volume 86, Number 10—Copyright © 2014 Water Environment Federation

0.25–2.50 mg L–1 paraoxon with a correlation coefficient

Chamkasem et al. (2013) developed a modified

(r(2)) of 0.9974. The LOD was 0.17 mg L–1 for paraoxon.

QuEChERS sample preparation method to improve the

The RSD of 1.0 mg L–1 paraoxon was 3.73% (n=5).

extraction recovery of 136 pesticides from avocado. The

Combining the optical properties with the inherent zeta

average recoveries for 79 pesticides quantified by LC–

potential induced instability in the properties of p–amino

MS/MS at 10, 50, and 200 ng g-1 were 86.1% or better,

benzenesulfonic acid functionalized gold nanoparticles, and

while GC–MS/MS analyses yielded 70.2% or better

a colorimetric detection method for carbaryl was developed

average recoveries from 57 compounds at the same spike

by by Sun et al. (2013). The results showed that both the

levels. The simultaneous analyses of 11 pesticide residues

color and zeta–potential of the sensor changed when

in tea was reported by Guan, Tang, et al. (2013) using a

carbaryl was added, and the LOD was determined to be

modified QuEChERS extraction method followed by LC–

0.25 µM (0.05025 mg L-1).

ESI–MS/MS. The study found that pesticides in real tea

Extraction Techniques. Although extraction

samples needed more time to be soaked and extracted than

techniques are technically not analytical methods, because

those in spiked tea samples for complete extraction. At

they are integral to the proper analyses of pesticide

fortification levels of 2–100 ng g–1, recoveries were within

residues, extraction methods are included in this review on

88–103%, and the LODs ranged from 0.02–0.38 ng g–1.

the analytical methods for pesticide residues. One common

Kaewsuya

extraction

\The

QuEChERS method using pipette tips fitted with filtration

quantification of 128 pesticides in banana using a modified

screens and containing PSA, magnesium sulfate, and

QuEChERS procedure followed by UHPLC–MS/MS was

graphitized carbon black to analyze for pesticides.

validated

Union

Recoveries between 70–117% were achieved for over 200

SANCO/12495/2011 guidelines and the Brazilian Manual

pesticides using the automated QuEChERS method and

of Analytical Quality Assurance for 10.0, 25.0, 50.0, and

GC–MS for various sample matrices. Korba et al. (2013)

100 µg kg–1 concentrations (Carneiro et al., 2013). The

developed

LODs were 5.00– 7.5 µg kg–1, the LOQs were 10.0–25 µg

determination of the pesticides chlorpyrifos, penconazole,

kg–1, and recoveries were between 67.5–120%. Fernandes

procymidone, bromopropylate, and lambda–cyhalothrin in

et al. (2013) reported on using modified QuEChERS with

wine

disposable pipette extraction and dispersive solid–phase

polypyrrole SPME fiber. The LODs were estimated to be

extraction for pesticides determination in soils.

Mean

between 0.073–1.659 ng mL–1 for the pesticides studied

recoveries of pesticides at levels between 10–300 µg kg–1

with recoveries from 92–107% were obtained for these

of soil ranged from 70–120% for 26 pesticides, and the

pesticides in wine.

technique

according

used

to

is

the

QuEChERS.

European

et

a

al.

(2013)

headspace

samples

using

developed

SPME

sodium

an

procedure

automated

for

the

dodecylsulfate–doped

LOD was < 7.6 µg kg–1.

2142 Water Environment Research, Volume 86, Number 10—Copyright © 2014 Water Environment Federation

pesticides were less than or equal to 20 ng g–1.

A new sample preparation procedure combining QuEChERS

and

DLLME

the

multiresidue pesticide analysis method based on sample

determination at trace levels of the pesticides 2,4–D,

preparation by modified QuEChERS and detection by GC–

acetamiprid, bentazone, cymoxanil, deltamethrin, dicamba,

MS was used to analyze 35 multiclass pesticides in melons

diuron,

metalaxyl–M,

(Sousa et al., 2013). Except for etridiazole, the recoveries

methomyl, pyraclostrobin, and tembotrione in tomato by

were 85–117% at concentrations between 0.05–0.20 mg

HPLC with diode array detection (Melo et al., 2013). The

kg–1. Magnetic GCB and PSA were used as adsorbent for a

recoveries of pesticides in tomato samples at spiking levels

modified QuEChERS method followed by GC–MS for

between 0.01 and 1.00 mg kg–1 ranged from 86– 116 %,

pesticide residue analysis in vegetables (Zheng et al.,

and the LOQs ranged from 0.0058–0.15 mg kg–1. Miao et

2013). The LODs were between 0.39–8.6 ng g–1, and the

al. (2013) reported on using a modified QuEChERS

recoveries were from 69.9–125.0%.

process coupled to GC–ECD for rapid extraction and

Lehotay (2013) reported on analyzing for pesticide residues

simultaneous determination of 36 pesticides in lotus seeds.

and other trace organics in catfish muscle using

The LODs of the developed GC–ECD method for the

QuEChERS followed by LP–GC/MS–MS. The LODs were

investigated pesticides ranged from 0.01–3.0 μg L–1, and

0.5–5 ng g–1 for select pesticides. Fan, Chang, et al. (2013)

the LOQs ranged from 0.05–10.0 μg L–1. Recoveries for

reported on the extraction efficiencies for pesticides in tea

spiked lotus seed samples were from 60.84–119.91%.

using three extraction techniques: 1) Extraction with 1%

Uncertainties of extraction and clean–up steps for pesticide

acetic acid in acetonitrile followed by cleaning with a SPE

foramsulfuron,

was

optimized

mesotrione,

for

A

14

Sapozhnikova and

C–labelled

cartridge; 2) using the QuEChERS approach where the

chlorpyrifos to analytical portions of tomato, orange, apple,

targets were cleaned up with graphitized carbon and PSA

green bean, cucumber, jackfruit, papaya, and star fruit

sorbent; 3) or using hydration of solid samples with tea

(Omeroglu et al., 2013). The relative standard uncertainty

hydrated before being extracted through salting out with

of the clean–up step with dSPE used in the QuEChERS

acetonitrile using the same cleanup procedures as the first

method was estimated to be approximately 1.5% for

method. The recoveries of 91.4% of the 201 pesticides and

tomato, apple, and green beans, and the highest variation of

other pollutants tested were within the range of 70–110%.

analyses were investigated by spiking

4.8% was observed in cucumbers.

Aguilera–Luiz

et

al.

(2013)

developed

a

Shoeibi et al. (2013) developed a QuEChERS

technique to monitor over 250 pesticides and veterinary

sample preparation technique followed by GC–MS

drugs in animal feed. Extraction with water and acetonitrile

selective ion monitoring mode for the analysis of 20

(1% formic acid) followed by a clean–up step with Florisil

pesticides in tea. The recovery of pesticides at 40, 60, and

cartridges was used, and the method was validated with

240 ng g–1 ranged from 79.5–111.4%, and the LOQs for all

recoveries ranging from 60–120% at 10, 50 and 100 µg kg–

2143 Water Environment Research, Volume 86, Number 10—Copyright © 2014 Water Environment Federation

1

, and the LOQs ranged from 4–200 µg kg–1 for most

varying the amount of Silica L 40/100 sorbent, flow–rate,

analytes. A method using acetonitrile ultrasound–assisted

and extract volume on the recoveries of the pesticides were

extraction, centrifugation, and evaporation without further

studied, and the recoveries for 1.0 g of dry soil samples

cleanup to analyze for pesticide residues in soil by ultrafast

containing 2.5 µg of each pesticide were 67–87% for the

liquid chromatography coupled to electrospray ionization

triazine pesticides and cloqiuntocet–mexyl and 40–57% for

mass spectrometry was developed (Ahumada et al., 2013).

the pyrethroids cypermethrin and permethrin.

Recoveries of 70–110% with relative standard deviation

Four extraction procedures were evaluated to

lower than 20% were obtained, and pesticide residues were

quantify 28 organochlorine pesticides in tap, surface, and

detected in soils in the range of 1–62 ng g–1. Akdogan et

sea waters by Concha–Grana et al. (2013), where the

al. (2013) developed a method using SPE for the trace

pesticide analyses were performed by large volume on–

determination of herbicides in aqueous samples using

column injector–GC–ECD, splitless–GC–ECD, and GC–

Amberlite XAD–4 resin as the adsorbent and methanol as

MS. The LODs were lower than 10 ng L–1, and most of the

the eluent. The LODs and linear ranges for the herbicides

recoveries were between 75–120%.

were 0.084–0.121 µg L–1 and 0.5–20 mg L–1, respectively,

method based on magnetic cobalt ferrite filled carbon

and the recoveries of simazine, atrazine, and their

nanotubes coupled with GC–ECD was developed by Du et

metabolities were in the range of 99.6–104.8%.

al. (2013) to analyze for OCPs in tea and honey samples.

Different

extraction

solvent

mixtures

A magnetic SPE

were

For eight OCPs tested, the enrichment factors were in the

compared by Canbay et al. (2013) for the analysis of

range of 52–68, and the LODs were from 1.3–3.6 ng L–1.

pesticides in 101 samples of human milk using GC/ECD

The recoveries of the OCPs were 83.2–128.7% for honey

and GC/NPD. LLE using chloroform/n–hexane (2:1, v/v)

and 72.6–111.0% for tea.

and dichloromethane/n–hexane (2:1, v/v) were used. The

A method was developed using MSPD extraction

LODs ranged between 0.04–0.027 ng g-1 lipid for the

and LC with UV diode array detector for determination of

studied pesticides, and the recoveries ranged from 89–

carbofuran, difenoconazole, beta–cyfluthrin, spirodiclofen

101%. Endosulfan was measured in three samples with a

and thiophanate–methyl in the stem of coconut palm

mean concentration of 0.190 ng g-1 lipid, while dichlorvos

(Ferreira et al., 2013). The best results were obtained using

was measured in five samples with a mean concentration of

2.0 g of stem, 1.6 g of Florisil as sorbent and a 4:1

0.188 ng g-1 lipid. An off–line flow–through extraction

cyclohexane:acetone mixture. The method was validated

method from soil samples for HPLC determination of

using stem samples spiked with pesticides from 0.05–2.0

methoxurone, atrazine, propazine, simazine, terbutrine,

µg g–1. Average recoveries ranged from 70–114.3%, and

cloquintocet–mexyl, cypermethrine, and permethrine was

the LODs and LOQs were from 0.02–0.03 and 0.05–0.1 µg

developed by Chalanyova et al. (2013). The effects of

g–1, respectively.

2144 Water Environment Research, Volume 86, Number 10—Copyright © 2014 Water Environment Federation

Gonzalez–Curbelo et al. (2013) reported on a

100.0 ng g–1 for the analytes under optimized conditions.

dSPE method using MWCNTs for the determination of 15

The LODs for the pyrethroids ranged from 0.01 to 0.02 ng

organophosphorus pesticides residues and some of their

g–1, and the recoveries for the six pyrethroid pesticides

metabolites by GC–NPD.

were from 90.0–103.7%.

Optimum conditions yielded

LODs between 1.16– 93.6 ng L-1 with recoveries of 67– 107%.

The determination of 37 LC–amenable pesticides

Guan, Li, et al. (2013) examined the ability of

in surface water samples using on–line SPE coupled to

amine–modified graphene to clean up fatty acids and other

UHPLC–MS/MS was evaluated (Hurtado–Sanchez et al.,

interfering substances from acetonitrile extracts of oil

2013). It was shown that under optimized conditions, 70

crops. Their research found that the CH3NH–graphene

extractions can be performed with the same cartridge. The

exhibited the best performance for removing interfering

LODs were lower than 6.0 ng L–1 and LOQs lower than

substances for pesticides analyses.

18.0 ng L–1 except for thifensulfuron methyl, whose LOD and LOQ were 10.0 and 33.0 ng L–1, respectively.

Hayward et al. (2013) developed and validated a method to analyze for 310 pesticides, isomers, and

An extraction method using magnetic titanium

pesticide metabolites in dried botanical dietary supplements

dioxide as sorbent to separate pyrethroid pesticides from

by adding an acetonitrile/water mixture to the botanical

environmental water samples has been established (Li and

along with anhydrous magnesium sulfate and sodium

Chen, 2013). The LODs and LOQs of the pesticides were

chloride for extraction followed by SPE cleanup using a

in the ranges of 2.8–6.1 ng L–1 and 9.3–20.3 ng L–1,

tandem cartridge consisting of graphitized carbon black and

respectively. And the recoveries were from 84.5–94.1 % at

PSA. Pesticides were measured by GC–MS/MS, and at

spiked levels of 25, 250, and 2,500 ng L–1. McManus et al.

fortifications of 10, 25, 100, and 500 μg kg–1, mean

(2013) described using SPME with a polyacrylate fiber

recoveries were 97%, 91%, 90%, and 90%, respectively.

prior to detection by GC–EI–MS to analyze for lindane, the

heptachlor, and two heptachlor transformation products in

determination of OCPs in fish and shellfish using

groundwater. Recoveries ranged from 96–101% at several

automated PLE and cleanup where the extract was passed

fortification levels, and the LOQ was 0.015 μg L–1. The

through gel permeation chromatography using 12 g of Bio–

disposable SPME polyacrylate fibers lasted up to 51

beads SX–3 for fat removal. The LODs ranged between

injections.

Helaleh

and

Al–Rashdan

(2013)

0.03–2.48 ng g–1 (w/w) for OCPs.

reported

on

Graphene–grafted

Pakade et al. (2013) developed a SDME method

ferroferric oxide microspheres were used to extract

for the determination of ten organochlorine pesticides in tea

pyrethroid pesticides from orange and lettuce samples prior

brews using GC–ECD. The LODs were from 0.01–0.025 g

to analyses by GC–MS (Hou et al., 2013). A linear

L–1, and the recovery ranged from 92–116%. Pelit et al.

response was obtained in the concentration range of 0.3–

(2013) described a GC method for the determination of

2145 Water Environment Research, Volume 86, Number 10—Copyright © 2014 Water Environment Federation

pesticides in wine samples using a florosil column after

were between 91.4–101.3%. Hybrid materials based on

LLE using a 1:1(v/v) cyclohexane/ethyl acetate mixture.

magnetic Fe3O4 nanoparticles and a synthetic macrocyclic

The recovery was 72–97%, and the LODs were 0.6–2.9 ng

receptor were prepared and used as a magnetic SPE

mL–1. A study presented an application of a multiresidue

adsorbent for the determination of trace pesticides in

method for the analysis of pesticide residues in fruits with

beverage samples by HPLC (Tian et al., 2013). The LODs

an

using

for seven pesticides were 5.0–11.3 ng mL–1, and the

diatomaceous earth as a dispersant and CH2Cl2 as the

recoveries for all target analytes were 70.6–106.8%. Tong

eluent (Radisic et al., 2013).

The pesticides were

et al. (2013) reported on a mixed mode SPE purification

determined using LC–ion trap–MS, and the recovery was

method for pesticide residue analysis using GC–MS/MS for

70–120 % for all tested matrices. Saadati et al. (2013)

the simultaneous determination of 100 pesticide residues in

investigated the analyses of 18 OCPs in water by SPE and

traditional Chinese medicine Flos chrysanthemi samples.

in sediment by Soxhlet extraction followed by GC–ECD.

The recoveries ranged from 65.3–124.7%, and the LOQs

The LOQs were 0.002 and 0.016 µg L–1 for water and

ranged from 0.03–11.88 µg kg–1.

sediment, respectively. A new selective material based on

(2013) developed a simple combining apparatus for

molecularly imprinted polymers was prepared and used as

performing magnetic stirring–assisted DLLME for the

SPE sorbent for sample enrichment of OPP residues prior

detection of trace carbamate and organophosphorus

to HPLC (Sanagi et al., 2013). The recovery was greater

pesticides in tea drinks using HPLC. Enrichment factors

than 91%, and the LODs were 0.83– 2.8 µg L–1.

between 130 and 185 were obtained, and the LOQs were in

Ultrasound–assisted

between 0.13–0.61 µg L–1 with recoveries between 79.4–

extraction

procedure

based

on

surfactant–enhanced

MSPD

emulsification

Wang, Cheng, et al.

114.4%.

microextraction coupled with HPLC–diode array detection

MSPE coupled with GC–MS was applied for the

was developed for the preconcentration and determination of five sulfonylurea herbicides in fruit samples using

analysis

Tween 20 as an emulsifier and chloroform as the extraction

functionalized Fe3O4@mSiO2 microspheres as the magnetic

solvent (Seebunrueng et al., 2013).

sorbents to extract and enrich OPPs from water samples

The LODs were

of

OPPs

in

water

samples

using

C18–

(Xie et al., 2013). The LODs were 1.8–5.0 μg L−1 and the

between 0.005–0.8 ng mL–1.

LOQs ranged from 6.1–16.7 μg L−1.

Su et al. (2013) developed a solventless

Xue, Xu, et al.

microwave–assisted extraction method coupled with low–

compared different sample pre–treatments for multi–

density

ultrasound–assisted

residue analysis of OCPs and pyrethoid pesticides in

emulsification microextraction for the determination of

chrysanthemum and determined that selected a combination

nine OPPs in soils by GC. LODs between 0.04–0.13 ng g–1

of gel permeation chromatography and SPE for the

for all target analytes were achieved, and the recoveries

determination 46 pesticide residues using GC–ECD. The

solvent–based

in–tube

2146 Water Environment Research, Volume 86, Number 10—Copyright © 2014 Water Environment Federation

recoveries ranged from 71.3– 102.6%, and the LOQs were

Ahumada, D. A.; Arias, L. A.; Bojaca, C. R. (2013) Multiresidue

between 0.0015–0.2 mg kg–1, while the LODs were

Determination and Uncertainty Analysis of Pesticides

between 0.0005– 0.1 mg kg–1. Zhao, Fan, et al. (2013)

in Soil by Ultrafast Liquid Chromatography Coupled to

developed

an

acetonitrile–based

sample

Mass Spectrometry. J. Brazilian Chem.Soc., 24 (7),

extraction

1188–1197.

technique to extract pesticide residues from fruits and Akdogan, A.; Divrikli, U.; Elci, L. (2013) Determination of

vegetables followed by clean–up using a multiwalled

Triazine Herbicides and Metabolites by Solid Phase

carbon nanotubes sorbent and anhydrous magnesium

Extraction with HPLC Analysis. Anal.Lett., 46 (15),

sulfate before analyses using LC–ESI–MS/MS. The

2464–2477.

method had recoveries from 71–117% for most pesticides,

Banerjee, K.; Mujawar, S.; Utture, S. C.; Dasgupta, S.; Adsule, P.

and the LOQs for 40 pesticides ranged from 2–50 g kg–1.

G. (2013) Optimization of Gas Chromatography–Single Quadrupole

Magnetic nanoparticles of nitrogen enriched carbon were

Mass

Spectrometry

Conditions

for

Multiresidue Analysis of Pesticides in Grapes in

developed for enrichment of DDT and its metabolite DDE

Compliance to EU–MRLS. Food Chem., 138 (1), 600–

that accumulated in zebra fish (Zhou et al., 2013). 607.

Recoveries of DDT and DDE from water ranged from 90–

Botero–Coy, A. M.; Ibanez, M.; Sancho, J. V.; Hernandez, F.

102% and 85–97%, respectively. The LODs were in the

(2013) Improvements in the Analytical Methodology

–1

low ng mL range using selected ion monitoring of GC–

for the Residue Determination of the Herbicide

MS.

Glyphosate in Soils by Liquid Chromatography Coupled to Mass Spectrometry. J. Chromatography A, 1292 132–141.

Acknowledgments

Bucur, M. P.; Bucur, B.; Radu, G. L. (2013) Critical Evaluation of

HCL thanks Dr. Eric Evans of HDR for his

Acetylthiocholine

Iodide

and

Acetylthiocholine

thorough and helpful review comments and Professor Chloride as Substrates for Amperometric Biosensors

Robert P. Metzger of San Diego State University and CeCe

Based on Acetylcholinesterase. Sensors, 13 (2), 1603–

Liang of the University of Colorado for their kind help.

1613. Buerge, I. J.; Bachli, A.; De Joffrey, J. P.; Muller, M. D.; Spycher,

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Selective

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2148 Water Environment Research, Volume 86, Number 10—Copyright © 2014 Water Environment Federation

Detection of Acetamiprid. Biosensors & Bioelectronics,

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2149 Water Environment Research, Volume 86, Number 10—Copyright © 2014 Water Environment Federation

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Quadrupole in Pesticide Residue Analysis in Food and

Ivanova, B.; Spiteller, M. (2013) A Novel UV–MALDI–MS

the Environment. Anal. Meth., 5 (21), 5875–5894.

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2150 Water Environment Research, Volume 86, Number 10—Copyright © 2014 Water Environment Federation

LC/ESI/MS on the Example of Pesticide Analyses.

Azinphos–Methyl and Azinphos–Ethyl Residues in

Anal. Meth., 5 (12), 3035–3044.

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J.

Mei, Z.; Cai, W. S.; Shao, X. G. (2013) Rapid Analysis of

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Sanagi, M. M.; Salleh, S.; Ibrahim, W. A. W.; Abu Naim, A.;

Su, Y. S.; Yan, C. T.; Ponnusamy, V. K.; Jen, J. F. (2013) Novel

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Tran, H. V.; Reisberg, S.; Piro, B.; Nguyen, T. D.; Pham, M. C.

Xing, X. Q.; Zhou, Y. Y.; Sun, J. Y.; Tang, D. B.; Li, T.; Wu, K.

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Zheng, H. B.; Zhao, Q.; Mo, J. Z.; Huang, Y. Q.; Luo, Y. B.; Yu, Q. W.; Feng, Y. Q. (2013) Quick, Easy, Cheap, Effective, Rugged and Safe Method with Magnetic Graphitized Carbon Black and Primary Secondary Amine as Adsorbent and Its Application in Pesticide Residue Analysis. J. Chromatography A, 1300 127– 133. Zhou, Y. E.; Xia, Q.; Ding, M. J.; Kageruka, H.; Jiang, H. Y.; Jiang, Y.; Jing, H. F.; Xiao, X.; Zhong, H. Y. (2013) Magnetic Nanoparticles of Nitrogen Enriched Carbon (Mnnec) for Analysis of Pesticides and Metabolites in Zebrafish by Gas Chromatography–Mass Spectrometry. J. Chromatography B–Anal. Technol. Biomed. Life Sci., 915 46–51.

2155 Water Environment Research, Volume 86, Number 10—Copyright © 2014 Water Environment Federation