Microchemical Journal 121 (2015) 99106

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Microchemical Journal

journal homepage: www.elsevier.com/locate/microc

Review article

The role of derivatization techniques in the analysis of glyphosate and

aminomethyl-phosphonic acid by chromatography
T. Arkan, I. Molnr-Perl
Institute of Chemistry, Department of Analytical Chemistry, L. Etvs University, H-1117 Budapest, Pzmny Pter stny 1/A, Hungary

a r t i c l e i n f o a b s t r a c t

Article history: Derivatization, prior to the chromatographic analysis of the particularly polar herbicide N-(phosphonomethyl)
Received 14 February 2015 glycine (glyphosate, GLYP) and its main metabolite aminomethylphosphonic acid (AMPA)] proved to be a key
Accepted 24 February 2015 step: also in cases applying liquid chromatographic techniques.
Available online 6 March 2015
In this paper the analytical proposals for GLYP and AMPA are reviewed: performing analyses by chromatography.
First sorting was based on the chromatographic separation method. Within the same chromatographic tech-
Keywords:
Glyphosate
niques, like gas chromatography (GC) and liquid chromatography (LC), distinction was made between GLYP
Sample-enrichment and AMPA separations in their initial forms (without derivatization) and as various derivatives. The examined
Derivatization matrix, enrichment, derivatization, acquisition protocols, limit of detection (LOD), limit of quantitation (LOQ)
Chromatography data were listed; additional herbicide(s), analyzed in a single run, were also shown. Special attention was paid
Analytical performance characteristics to the selectivity and sensitivity properties of methods. Analytical performance characteristics were documented
and commented in details.
2015 Elsevier B.V. All rights reserved.

Contents

1. Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 99
1.1. Sample and method selection . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 100
2. GC of GLYP and AMPA . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 100
2.1. Quantitation of GLYP without derivatization . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 100
2.1.1. Simultaneous acylation and esterication . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 100
2.1.2. Trialkylsilylation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 101
3. LC of GLYP and AMPA . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 101
3.1. Quantitation in their initial forms, without derivatization . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 101
3.2. Identication and quantication as various derivatives . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 101
4. Analysis of GLYP and AMPA via miscellaneous techniques . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 104
5. Conclusions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 104
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 104

1. Introduction
The relevancy and continued interest towards chromatographic
analyses of GLYP and its main metabolite, AMPA can be explained by
the foreseeable exponential production and use of GLYP taking into con-
sideration its application forecasts up to 2020: global glyphosate de-
mand was over 700 kt in 2013, which is expected to exceed 1000 kt
by 2020 [1].
Corresponding author.
E-mail address: perlne@chem.elte.hu (I. Molnr-Perl).
The role of derivatization for GLYP and AMPA analyses can be best
characterized by the fact that independent on the chromatographic
techniques used, (published in the last two decades, summed up on Sci-
ence Direct basis, according to our selection), in 99% of contributions,
expressed in the total of representative papers, was performed with
derivatized species.
Thus, the utility of an overview from the points of view comparing
methodologies, sensitivity, selectivity, reliability and reproducibility of
proposals applying underivatized and derivatized GLYP and AMPA, con-
trasting suitability for their simultaneous identication and quantica-
tion in different matrices, (environmental waters, soils/sewages, fruits/

http://dx.doi.org/10.1016/j.microc.2015.02.007
0026-265X/ 2015 Elsevier B.V. All rights reserved.
100 T. Arkan, I. Molnr-Perl / Microchemical Journal 121 (2015) 99106
vegetables, serum/plasma/urines, derivatization/standard impurity, or
adsorption/degradation/antibody studies) is not questionable.
Literature reviews, published in the last thirteen years [216], were
related primarily on method and matrix selection [214]. In this
contexts gas chromatography (GC: [2,3,5,7]), liquid chromatography
(LC: [49,11,14]) and capillary electrophoresis (CE: [7,10,12,13,16])
techniques were compiled. Focusing, all, on sample preparation strategy
[216] and herbicide residues analysis: in foods [35,8,11,13], in envi-
ronmental waters [2,3,68,11,13], in soil [9] and in sediment [13]. Re-
views, on bioanalytical approaches are worth mentioning [15,16] such
as discussing GLYP's phytotoxicity [15] and developing method for the
comparative analysis of metabolic proles from transgenic soybean,
distinguishing its glyphosate resistant alternative [16].
In this review those relevant papers were compiled without com-
pleteness in which for GLYP and AMPA analysis GC [1746], LC
[4770], CEC [71,72], ion chromatography (IC) [7375], spectrophotom-
etry [76,77] and neutron magnetic resonance (NMR) [7880] protocols
were used. Further classications were listed according to the matrix
they had to be extracted from and/or to the detailed process they
were subjected to, prior to their identication and quantitation analysis.
1.1. Sample and method selection
The aim of this compilation was to assess the involvement of GLYP
and AMPA, these, freely water soluble herbicides, emerging in various
matrices we are faced by. Distribution of polluted matrices reveals
that the most frequently analyzed sample types vary from 35.1% (envi-
ronmental waters) to 5.9% (adsorption/degradation/antibody studies),
expressed in the total of our selection (Fig. 1).
In favor of unambiguous transparency and easy traceability, all the
expressions used together with their abbreviated forms are compiled
in Table 1A, the structure and physical/chemical properties of the target
analytes (GLYP, AMPA) in Table 1B.
From methodological point of view, regarding selected papers
[1780] we examined in details the GC based, simultaneous acylation
and esterication (Table 2), the various alkylsilylation techniques
(Table 3) and the different liquid chromatographic (Table 4) proposals.
Evaluation is also based on our earlier experiences being deeply in-
volved in the analysis of organics even as environmental pollutants
[8185].
Fig 1. Distribution of the most frequently analyzed sample types to identify and quantify GLYP and AMPA residues in various matrices, by chromatography.
In general, it is worth mentioning that derivatization does have a
particular importance in the chromatographic protocols. This time con-
suming and tedious process, by research and application chemists,
equally, was and it is still regarded as the main disadvantage of sample
preparation, needed primarily, prior to GC analyses, only. However, this
so called disadvantage is dwarfed in comparison to several advantages
associated with the analysis of derivatized compounds (increased selec-
tivity, sensitivity and the possible identication and quantication of
species in question, in a single column, simultaneously). In the present
case meaning the polar herbicide analysis derivatization does have
a particular importance, it is a key issue, even prior to LC separations;
the preliminary derivatization step proved to be unavoidable necessary.
Out of the reviewed LC selections [4770], in three, author declared
their method as direct derivatization [62,67,68]: however, having a
look inside the method, it turns out that this statement in two pro-
posals [62,67] is questionable.
2. GC of GLYP and AMPA
2.1. Quantitation of GLYP without derivatization
Recently, two trials were found [39,44]: in one of them authors con-
rmed that The method developed for 32 pesticide residues in
vegetableswas only incapable of adequately determining four of the
pesticides from Regulation MS 518/2004: glyphosatewas not suit-
able for direct GC determination [39]. Similarly, a method for the
rapid simultaneous screening and identication of multiple pesticide
residues in vegetables was established using a novel database and gas
chromatography in combination with hybrid quadrupole time-of-
ight mass spectrometry (GC-QTOF MS). A total of 187 pesticides with
different chemical species were measured includingglyphosate
herbicide which could not be detected at all [44]. It means there is
no method in the literature suitable for GLYP and AMPA analysis, with-
out derivatization, by GC.
2.1.1. Simultaneous acylation and esterication
Papers were sorted in line of their appearences representing all
matrices of interest (Table 2). Enrichment protocols were cation
or anion exchange cleanings, including, ltering, centrifugation,
evaporation. Solid samples were mainly water extracted. Except a
 T. Arkan, I. Molnr-Perl / Microchemical Journal 121 (2015) 99106 101

Table 1A Table 1B
Abbreviations used in this review. Structure and chemical/physical characteristics of GLYP (1) and AMPA (2): on Science Di-
rect basis.
Acetic acid anhydride AA
Acetonitrile ACN Structure CAS Molecular Acidity
Aminomethylphosphonic acid AMPA number mass pKa
Ampropylfos AMPP
1071-83-6 169.07 1.22 0.10
Bialaphos BIAL
10.30 0.30
N,O-bis(trimethysilyl)triuoroacetamide BSTFA
(1)
Diazomethane C2N2
Cation/Anion exchange cat/an exch
Capillary electrophoresis CE
Centrifugation cfg 1066-51-9 111.04 1.48 0.10
Chemical ionization CI 9.93 0.29
Colorimetric reagent CR (2)
Deproteinization depr
Dimethylformamide DMF
2,5-dimethoxybenzenesulfonyl chloride DMOSC
Electrochemiluminescence ECL
Extraction extr
Fluorescence detection FD characteristics were simply neglected [17,26,27,29,31,40,43,45], while
Flame ionization detector FID in two cases either LOQ [19,20], or LOD [32,36] data were given,
Fluorenylmethoxycarbonyl FMOC
exclusively.
Flame photometric detector FPD
Gas chromatography GC
Glufosinate GLUF
Glyphosate; N-(phosphonomethyl)glycine) GLYP 2.1.2. Trialkylsilylation
Heptauorobutanol HFB This popular technique was optimized partly for basic research studies
Heptauorobutyric acid HFBA [18,41,47], partly to determine herbicide poisoning via serum and urine
High performance liquid chromatography HPLC
analysis [28,35,42,46]. MTBSTFA was declared as the right reagent selec-
Inductively coupled plasma ICP
Isopropyl chloroformate ISPCF
tion, providing the expected molecular ions of three TBDMS groups
Ion trap IT (GLYP, [M] m/z, 511; AMPA m/z, [M] 451), and their characteristic frag-
Liquid chromatography LC ment ions formed by the loss of common characteristic masses as a meth-
Liquid-liquid extraction L/L yl (m/z 15) or a TBDMS (m/z 57) group, for both herbicides in question.
2-mercaptoethanol MCE
BSTFA derivatization was suggested to the impurity proling of
3-mercaptopropionic acid MPA
3-methylphosphinico propionic acid MPPA AMPA and GLYP, only [41,47]. Forced techniques (90 C, 150 min)
Mass spectrometry MS with 10% TMCS catalyst, proved to be less comfortable [41] than the
N-Methyl-N-tert-butyldimethylsilyltriuoroacetamide MTBSTFA use of a benecial reagent medium (BSTFA:PYR, in ratio 0.6:1, v/v)
Nuclear magnetic resonance NMR resulting in a fast, practically utilizable method [47].
Nitrogen-phosphorous detector NPD
Nanoparticles NPs
As to the analytical performance characteristics, in spite of selective
1,2-naphtoquinone-4-sulfonate NQS acquisition processes (GCMS and GCMSSIM), because of methods'
O-phthalaldehyde OPA low sensitivity they have not been full documented [18,28,35,41,42,
Pentauoropropionic acid PFPAA 46,47]; few have been presented with numerical data. Reliable values,
Pulsed ame photometric detector PFPD
suitable for serum and urine analyses [28,35,46] were found, only. In
P-toluenesulfonyl chloride PTSCL
Pyridine PYR three papers [18,41,47] neither LOD nor LOQ data were given.
Vortexing at given temperature rtp
Selected ion monitoring SIM
Solid phase extraction SPE 3. LC of GLYP and AMPA
Tert.butyl dimethychlorosilane TBDMCS
Triuoroacetic acid TFA 3.1. Quantitation in their initial forms, without derivatization
Triuoroacetic acid anhydride TFAA
Triuoroethanol TFE
Trimethylchlorosilane TMCS Out of the reviewed LC selections [4770], in three [62,67,68]
Trimethyl orthoacetate TMOA authors declared their method as direct derivatization: however, in
Ultraviolet detection UV order to get further inside into the details of these three methods, it
turns out that in two of them derivatization is hidden [62,68]: designat-
ed with question marks in Table 4. In one, separation was carried out as
single case where diethylether was applied ensuring the intrinsic HFBA ion pairs [62], while in the other process target analytes were
miscibility with the acylation (ISPCF) and esterication (C 2N 2 ) enriched by diethyl ether extraction containing diazomethane to ester-
reagents [20]. ify GLYP and AMPA in the sample preparation process [68]. Consequent-
As combined acylation-esterication reactants out of twenty select- ly, these proposals are not straight-line direct derivatizations. It means
ed cases in fourteen [17,19,2225,29,3133,36,40,43,45] are consisting the case of polar herbicide analysis is a unique issue in sense of obliga-
of PFPAA or TFAA with TFE or HFB, in volume ratios of 2/1, applying tory derivation.
90100 C temperature and 60 min derivatization time.
The alternative combination based on AA acylation and TMOA es-
terication was carried out in TMOA excess [21,26,27,30,34], at en- 3.2. Identication and quantication as various derivatives
hanced temperature (135 C) and reaction time (180 min).
ISPCF acylation completed with C2N2 esterication, in diethyl ether, Prior to LC separations, the amino group labeling proved to be pre-
was performed at room temperature [20]. ferred, without exception (Table 4). According to this selection, out of
Regarding the acquisition techniques GCMSSIM and GCMSMS twenty protocols, independent on the matrix tested, in twelve [48,
proved to be the methods of choice [2225]: providing in all these prac- 5052,54,55,5759,61,64,66], the common enrichment technologies
tical cases acceptable LOD and LOQ values Unfortunately, regarding the (SPE, anion or cation exchange in aqueous solutions) are followed by
other proposals out of twenty in eight cases analytical performance using FMOC; uorescent derivatives of high responses are formed, in
 102
Table 2
Simultaneous acylation and esterication of GLYP and AMPA by gas chromatograpy (GC), acylated with triuoroacetic acid anhydride (TFAA) and triuoroacetic acid (TFA) or with Triuoroethanol (TFE) or with Heptauorobutanol (HFB).

Matrix/amount, mL/g Enriched by Derivatization conditions Acquisition LOD LOQ Compounds Ref.

Reagent (v/v ratios) C min g/L, g/1000 g

Derivatizaion study, PFPAA/TFE = 2/1 100 60 GCMS GLYP, AMPA, N-methyl-GLYP, [17]

T. Arkan, I. Molnr-Perl / Microchemical Journal 121 (2015) 99106

0.001 GLYP standard N-methyl-AMPA, impurity analysis
Soil, crop, animal tissues, 2550; cat exch TFAA/HFB = 2/1 9297 60 GCMS 0.2 (water) GLYP, AMPA [19]
drinking water 50 50100 (soil)
Soil, carrot 0.5, River water (Rw) , extraction: diethyl ether 1. acylation: ISPCF rtp GCFPD 0.82, Rw 820 (soil/carrot) GLYP, AMPA,GLUF [20]
2. esterication: C2N2
Crops, 20 depr, cfg, an exch AA/TMOA = 1/4 80 90 GCFPD 20 50 GLYP, GLUF, MPPA [21]
Soil, 10; groundwater, 5001000 an exch TFAA/TFE = 2/1 100 60 GCMSSIM 0.05 (water) 0.1 (water) 0.006 (soil) GLYP, AMPA [22]
0.003 (soil)
Derivatizaion study TFAA/TFE = 2/1 95 30 GCMSSIM 0.09 65 1.15180 GLYP, AMPA, GLUF, AMPP, BIAL, MPPA [23]
Lake water, 50 Filtering [24]
Waters*, 500 An exch TFAA/HFB = 2/1 9297 60 GCMSMS 0.025 0.050 GLYP, AMPA [25]
River, surface, drinking waters, 1 L Filtering TFAA/TFA/TMOA = 1/1/8 100 90 GCCIMS GLYP, GLUF, [26,27]
(& GCFID) aminoalkanephosphosphonic acids
Soybean seed, canola, Water extraction, cfg, TFAA/HFB = 2/1 90 60 GCMS GLYP, AMPA [29,31,33]
1 resistance study cat. exch 0.25 0.83
Rice, soybean sprout, 5 depr, cfg, an. exch. AA/TMOA = 1/2 7090 30120 GCPFPD 1030 40100 GLYP, AMPA, GLUF, MPPA [30]
Leaching, 500 Water extraction, cfg, TFAA/HFB = 2/1 90 60 GCMS 0.010.05 GLYP, AMPA [32]
cat exch
Surface water, 50 Evaporation AA/TMOA = 1/2 110135 180 GCNPD 5 17 GLYP [34]
Soil, 5 Extraction, 2 M NH4OH TFAA/TFE = 2/1 100 60 GCNPDMS 10 GLYP [36]
GLYP, bio/enzyme degradation study TFAA/TFE = 2/1 100 60 GCMS GLYP, AMPA [40]
Sand/clay soil, 1 adsoption study Water extraction, cfg TFAA/TFE = 2/1 100 60 GCMSSIM GLYP, AMPA [43]
Plant seed, 1 resistance study Water extraction, cfg, TFAA/HFB = 2/1 90 60 GCMS GLYP [45]
cat exch

Indications, as in Tables 1A, 1B, as well as: = no data available; cat/an exch = cation/anion exchange; depr = deproteinization; cfg = centrifugation; GLYP = glyphosate; AMPA = aminoaminomethylphosphonic acid; GLUF = glufosinate; PFPAA =
pentauorpopropionic acid anhydride; TFE = triuoroethanol; TFAA = triuoroacetic acid anhydride; HFB = heptauorobutanol; ISPCF = isopropyl chloroformate; C2N2 = diazomethane; AA = acetic acid anhydride; TMOA = trimethyl
orthoacetate; CI = chemical ionization; FID = ame ionization dtection; FPD = ame photometric detection; PFPD = pulsed FPD; NPD = nitrogen-phosphorous detection; waters* = model waters of various hardnesses; leaching = leaching waters
from sand/loamy sites, tile drainage, ground waters; MPPA = 3-methylphosphinico propionic acid; BIAL = bialaphos; AMPP = ampropylfos.
 T. Arkan, I. Molnr-Perl / Microchemical Journal 121 (2015) 99106 103

Table 3
Analysis of glyphopsate and AMPA by gas chromatograpy (GC), derivatized with N-Methyl-N-tert-butyldimethylsilyltriuoroacetamide (MTBSTFA [18,28,35,42,46]) and with bis-
trimethylsilyl triuoroacetamide (BSTFA [41,47]).

Matrix/amount, L/mg Enriched by Derivatization conditions Acquisition LOD LOQ Compounds Ref.

Reagent (v/v ratios) C min g/L, g/1000 g

Derivatization study MTBSTFA/DMF = 1/1 80 30 GC-IT-MS 10500 GLYP, AMPA, GLUF, MPPA, [18]
BIAL and 19 amino acids
Serum, urine, 100 depr, cfg, SPE MTBSTFA/DMF = 1/1 80 30 GCMSSIM 0.011 g/100 L GLYP, AMPA,GLU,MPPA [28]
Serum, 200 depr, cfg, SPE MTBSTFA/ACN = 1/1 15 rtp GCMSSIM 250 3000 GLYP, AMPA,GLU [35]
AMPA, standard, 2.5 BSTFA (10% TMCS)/PYR = 10/1 90 150 GCMS AMPA impurity proling [41]
Serum, 200 depr, cfg, SPE MTBSTFA/ACN = 1/1 Vortexed 6, rtp GCMS 15 GLYP, AMPA, GLUF, MPPA [42]
Serum, urine, 200 depr, cfg, SPE MTBSTFA/ACN = 1/1 vortexed, 15 s, rtp GCMSSIM 5000 5000 GLYP, GLU, fenitrothion, [46]
malathion phenthoate
Derivatization study BSTFA (1% TMCS)/ACN or 60 30 GCMS AMPA impurity proling [47]
AMPA, standard, 2.5 PYR = 0.6/1(v/v)

Indications, as in Tables 1A, 1B and 2, as well as: DMF = dimethylformamide; GCITMS = GCiontrapMS; ACN = acetonitrile; MTBSTFA = containing 1% tert.butyl dimethychlorosilane
(TBDMCS); rtp = vortexing at giventemperature; BSTFA = N,O-bis(trimethysilyl)triuoroacetamide; TMCS = trimethylchlorosilane.

aqueous solutions, mostly at pH 9, under mild conditions (from room primarily for detection, only. (Authors' note: unfortunately there was
temperature up to 40 C, from 20 min up to 24 h). no suggestion for the simultaneous OPA-FMOC derivatizations [86],
Next to FMOC the use of the OPA-MCE reagent, providing also uo- proper for labeling both the primary and secondary amino groups. Prob-
rescent derivatives, revealed applicability in practical use [49,56,63], ably, this reagent pair might offer exponentially high responses).

Table 4
Analysis of GLYP and AMPA by liquid chromatography (LC), without derivatization [62,67,68], as uorenylmethoxycarbonyl (FMOC) derivatives, [48,5052,54,55,5759,61,64,66], or ob-
tained with the o-phthalaldehyde-2-mercaptoethanol (OPA-MCE) [49,56,63], with the p-toluenesulfonyl chloride (PTSCL) [53,65], with the 2,5-dimethoxybenzenesulfonyl chloride
(DMOSC) [69], with colorimetric (CR reagent, containing sulfanilamide 0.3% w/v and N-(1-naphtyl)ethylendiamine, 0.03%, w/v, in 4.5 M HCl) and with the 1,2-naphtoquinone-4-sulfonate
(NQS) [70] reagents.

Matrix/amount, mL/g Enriched by Derivatization conditions Acquisition LOD LOQ Compounds Ref.

Reagent C min g/L, g/1000 g

Serum model study SPE, HFBA ion pair Direct injection?? LCMSMS 20 GLYP, GLU [62]
Rice, maize, soybean, 2 C2N2-extr optimized LCMS/MS 7120 20400 GLY [67]
Fruits, vegetables, 25 Water extr Direct injection LCMS/MS 12; 50 150;500 GLYP, AMPA [68]
Drinking, surface, On-line SPE FMOC 37 Overnight LCMSMS 0.03 0.05 GLYP, AMPA [48]
waste-water, 4
Streams, 125 SPE FMOC 40 24 h LCMSMS 0.1 GLYP, AMPA [50]
Water 10 On-line SPE FMOC 40 2h LCMS 0.084 GLYP, AMPA, GLU [51]
Drinking, surface, Amberlit-IRA-900, FMOC rtp 30 LCLCFD 0.10.02 GLYP, AMPA [52]
waste-water, 1.5 an exch
Water, 10; soil 5 SPE FMOC rtp overnight LCMSMS 0.005; 50 0.05;500 GLYP, AMPA, GLU [54]
Water, 50 Amberlit-IRA-900, FMOC rtp 25 LCFD 0.1 0.310 GLYP, AMPA [55]
an exch, isolute
Sewage sludge 5 An exch FMOC rtp 10 LCMSMS 1000 GLYP, AMPA diuron, [57]
atrazine, nonylphenol
Ground, surface, On-line SPE FMOC 40 24 h LCMSMS 0.02, 10 GLYP, AMPA, GLU [58]
rainfall waters,
200, soil, 5
Surface water, 15 Extr 2 by ether, FMOC rtp 60 LCFD GLYP, AMPA [59]
water phase (multivalent
derivatized cations complexation
study)
Ground, surface, SPE, as FMOC FMOC (10% ACN rtp 120 LCMSMS 200600 7002300 GLYP, AMPA, GLU [61]
river waters, 80 derivatives
Rat plasma, 0.2 Depr. ACN FMOC rtp 30 LCFD/MSSIM 500010,000, FD GLYP, AMPA [64]
4002000 MS
Soil, 3 1. Extr., cfg FMOC rtp 15 h LCMS/MS 4346.5 227889 GLYP, AMPA [66]
2. SPE, as FMOC
derivatives
Surface, ground On-line SPE, an/cat Post column, LCFD 0.02 GLYP, AMPA [49]
water, 100 exch OPA-MCE
Soil, 10 Cat exch, pH 7 Post column, . LCFD 0.2 GLU, phenmedipham, [56]
OPA-MCE ethofumesate,
metamitron
Water, (pH 9), 20 Micro scale Post column, rtp LC-FD 0.22 0.72 GLYP, AMPA [63]
membrane OPA-MCE
extraction
Fruit juice, 100 Liquid membrane PTSCL 50 10 LC-UV 10 25 GLYP, AMPA [53]
Urine, serum 2 Depr, L/L PTSCL 50 15 LCMSMS 20 50 GLYP, AMPA [65]
Derivatization study DMOSC 35 10 LCUV 640 5000 GLYP [69]
Derivatization study An exch Post 95 30s LC, 546 nm 800 N-NitosoGLYP [60]
column, CR impurity in
standard GLYP
Soil, 0.1 Extr, cfg NQS 60 5 LCUV 6498 GLYP, AMPA [70]

Indications, as in Tables 1A, B, 2 and 3, as well as: L/L = liquid/liquid extraction; FD = uorescence detection.
104 T. Arkan, I. Molnr-Perl / Microchemical Journal 121 (2015) 99106
As to the analytical performance characteristics, it is worth
underlining the comparable efciency of mass spectrometric and uo-
rescence detections. Certainly, it is a matter of compromise taking into
consideration the type and amount of sample matrix, the derivatization
reagent and effect of interactive parameters involved in the process.
Having a look at LOD and LOQ values, manifesting the FMOC and
OPA-MCE derivatives, it turns out that
1) out of eighteen proposals, including non derivatized, FMOC and
OPA-MCE labeled matrices, in eight [4951,5659,62] LOQ values
were not given, et all.
2) The optimum LOQ values for drinking, surface and waste-water was
obtained with large volume injection (1.5 L), in a coupled column sys-
tem, applying uorescent detection (LC-LC-FD: LOQ 0.1-0.02 g/L)
[52].
3) The second best characteristics for waters proved to be tandem mass
spectrometric processes [48,54], both offering from 4 mL [48] and
10 mL [54] samples 0.05 g/L LOQ values.
4) In case of solid samples also LC-MS-MS acquisitions proved to be the
optimum selections (LOQ: 500 g/1000 g soil [68,54]).
5) All additional proposals like PTSCL, DMOSC, post column CR and NQS
labeling [60,65,69,70] are of marginal importance and serve as com-
pleting data, only.
4. Analysis of GLYP and AMPA via miscellaneous techniques
Capillary electrophoresis with electrochemiluminescence (CE-ECL)
[71] and mass selective [72] detections were published recently.
Microscale solid phase extraction on alumina-coated iron oxide
nanoparticles [71] was applied for GLYP and AMPA detection with a
total analysis time less than 1 h (including sample pretreatment, SPE,
and CE-ECL analysis). LODs for GLYP and AMPA, in water were
0.3 g/L and 30 g/L; in guava fruit extracts GLYP was detected only
(LOD: 10 g/1000 g). LOQ data are not available.
Analysis of phosphorous/amino acid type herbicides including GLYP
and AMPA using chemically modied amino groups coated capillary,
was modelized by spraying agricultural soils with herbicides [72]. With-
out LOD and LOQ values, authors investigated the remedies of GLYP and
AMPA formulation within 28 days after spraying [72].
Ion chromatography for polar organic micropollutants' analysis was
introduced with simple [73], followed with inductively coupled plasma
(ICP) mass selective detections [74,75]. In all cases [7375] water sam-
ples were tested. GLYP and AMPA contents of ground and surface wa-
ters were detected at a level of 1 g/L [73], 0.7 g/L [74] and 11.4 g/L
[75], respectively.
Direct spectrophotometric detections of GLYP [76,77] were based
on its reaction with ninhydrin [76] or carbon disulde to form
dithiocarbamic acid, which was subjected to complex formation
with Cu (II) in the presence of ammonia [77]. LOD and LOQ values
are given in both cases ([76]: LOD, 40 g/L and LOQ, 110 g/L; [77]:
LOD 1100 g/L and LOQ 3700 g/L). However, in lack of selectivity
both proposals are of marginal importance.
Quantitative determination of GLYP in biological uids [78] and in
human serum [79] was described applying 1H [78,79] and 31P NMR
[78] spectroscopy. Both proposals were performed to determine active
poisoning. Method sensitivities were in particular low ([78]: LOD
330,000 g/L; [79]: LOD, 5070 g/L and LOQ, 16,900 g/L). However, in
spite of low sensitivity, results conrmed methods' utility.
For sake of completeness it is worth mentioning the DNA-labeled
gold nanoparticles (NPs) suitable for the measurement of free GLYP con-
centration [80]. The reaction between the antigen double DNA gold
NPs and immobilized antibody on the substrate was carried out for 2 h.
The results of the antigen-antibody reaction were determined on the
basis of the uorescence intensity obtained from comparison with the
free antigens at concentrations of 0.01100 g/mL for the detection of
immobilized antigen-double DNA-gold NPs. The immunosensor
response also revealed the same detection range of GLYP using DNA
detection.
5. Conclusions
In compiling, the key issue to analyze of these highly polar herbi-
cide residues (GLYP, AMPA), in different matrices we are faced by
should be underlined: the key issue is derivatization. The competition
between the two main chromatographic techniques conrmed a new
phenomenon: the question to be answered is not the common one,
meaning, without or with derivatizations? No, the questions are unam-
biguous (next to sample preparations which is thoroughly associated
with the matrix to be tested and well documented), the questions are:
(1) LC or GC?
(2) Fluorescence or mass selective detections, or both? Certainly, as
primary importance
(3) derivatization reagent selection should be also suggested.
In response to these doubts, authors of this review, based on litera-
ture overview and on self experiences do try to give answer.
We are convinced that on basis of principles available, for GLYP and
AMPA analysis LC separation might be the method of choice: applying
simultaneous, uorenylmethoxycarbonyl chloride/o-phthalaldehyde-
3-mercaptopropionic acid (FMOC-OPA-MPA derivatization, with com-
plementary uorescence and mass selective detections. We also assume
that the trialkylsilylation techiques for GLYP and AMPA analysis are not
fully exhausted. We plan to contribute to clear up these possibilities, in
particular comparing trialkylsilyl deriavatizations as a function of the re-
agent applied. The relevancy of the topic is not questionable because of
the continuous demand of GLYP and its excepted enormously increased
production by 2020.
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