determination of glyphosate residues in human urine samples from 18 european countries

7/25/2019 Determination of Glyphosate residues in human urine samples from 18 European countries

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Document Title Determination of Glyphosate residues in humanurine samples from 18 European countries

Test Compound Glyphosate and AMPA

Study Initiation Date March 2013

Study Completion Date June 6 2013

Test Facility Medical !a"oratory #remen$afer%ende 12283&' #remen Germany

Sponsor #()D *oE

Date of the Document June 12 2013


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MLHB Report Glyphosate MLHB-2013-06-06

+,(D- !./A,.)

The preparation of standards and analyses of samples were carried out at the

Test Facility:

Medical !a"oratory #remen$afer%ende 12

283&' #remen Germany

Under the responsibility of the Study Director, Dr. Hans-Wolfan Hoppe,

accordin to the rele!ant "peratin #rocedures.

$ontact Dr. Hoppe:

%%&' (%) &*+ *%* -*+

Hans-Wolfan.Hoppemlhb.de

The analytical phase of the study was started on /arch *0, *%+1 and was

completed 2une 3, *%+1.

The hardcopy raw data will be scanned and stored as electronic media and 4eptat 5remen 6ab for a period of at least + year. 7 copy of the electronic media andthe oriinal hardcopy raw data will be sent to sponsor for archi!al purposes ondemand.

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,A#!E .* /.),E),+

+,(D-6"$7T8"9

;#"T 7##"


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+. "52;$T8 Fo;aainst the bac4round of increasin =lyphosate use in some ;uropeancountries.

*. /anaement of 5ioloical Samples

We recei!ed shipments from +0 ;uropean countries durin the period of /arch** (5elium) to /ay *+ (Spain, #oland). ;ach shipment included 0-+* samples.The Spanish samples made a detour !ia 5udapest. 7ll urines were ice cold andin a ood condition at receipt and were stored at ?+0@$ until date of samplewor4-up. 7t reception, /6H5 sent a confirmation of receipt to the Sponsor andhas chec4ed for any mismatch between the shipment and the list pro!ided by theSponsor. "n completion of the assays, the samples were 4ept deep froAen. Thestudy samples will be stored for a period of + year.

1. 7nalytical procedures

The human urine samples were analyAed by means of a !alidated =$-/S/Smethod. 8n addition we determined creatinine to correct for diurese, if needed.5rief descriptions and the rele!ant specifications are listed below.

7nalytical /ethod for =lyphosate and 7/#7

Sample preparation:+) ;!aporation and dissolution of the residue in methanol,

*) deri!atiAation usin trifluoroethanol and trifluoroactic acid anhydride

8nternal Standards:+1$*

+9-=lyphosateB +1$+9-7/#7

/easurement: =$-/S/S, 9$8 mode$apillary $olumn: H#-8nnowaC

#recision: 0 eacheco!ery: ' each6inearity: %,* - *% E>6 each6imit of uantitation (6"): %,+ E>6 each

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=lyphosate and 7/#7 concentrations. $reatinine concentrations were only usedto chec4 whether the spot urine samples are !alid. 7ll creatinine le!els are insidethe reference rane (see table *). The analytical results of =lyphosate and 7/#7are not creatinine corrected. 7 mean blan4 !alue of %.%1 E>6 was subtractedfrom the measured concentrations of the urine samples and controls (Table * and

1).uality control samples showed ood precision and accuracy throuhout themeasurement of the study samples as an indication of the ood methodperformance (see table 1). 7 brief statistical e!aluation includin freIuency ofdetection, mean and maCimum !alues sorted by ;U countries is i!en in table &.

Table * =lyphosate and 7/#7 concentrations in human urine samples

Participant Glyphosate AMPA Creatinine

g/L g/L g/L

Belgium no 2


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)* (o "


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Malta (o %


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ungary (o 10


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Georgia # 0,## 0,1%& 1,$1

Georgia "


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Mean ,21 ,2! 1,0 0,1

C6 475 ",2 2, %,#" $,%$

Accuracy 475 10",2" 10,%! 10"," 101,0"

Table &: StatisticsTo calculate the mean !alues, results below the 6" (%,+ E>6) are replacedwithJ 6" (%,% E>6).

=lypho =lypho =lypho =lypho 7/#7 7/#7 7/#7 7/#7

;U country SubKects FreIuency ofDete4tion

FreIuency ofDete4tion

/ean /aCimum6 n E>6 E>6

5elium 5 ++ 3 &, %,+0 %, &,& %,*' +,*3

6at!ia 6< ++ 3 &, %,&+ +,0* &,& %,+' %,+

=reat 5ritain =5 +% %,%% %,& +,3& %,%% %,*1 %,3

France F +% 1 1%,%% %,+* %,*1 1 1%,%% %,+& %,&+

$Aechepublic $L +% 3 3%,%% %,*& %,'* %,%% %,+ %,1%

5ularia 5= +% + +%,%% %,%' %,+0 * *%,%% %,+% %,*%

/alta / +% ' '%,%% %,0* +,3 0 0%,%% %,&% %,0'

/acedonia /M +% + +%,%% %,%' %,*& % %,%% %,%0 %,%0

7ustria 7 +% * *%,%% %,+% %,*% * *%,%% %,%' %,+3

$roatia H +% & &%,%% %,+& %,&* + +%,%% %,11 *,31

Hunary H +% 1 1%,%% %,+% %,+0 * *%,%% %,+% %,*

SwitAerland $H +* * +3,3 %,%' %,+3 % %,%% %,%0 %,%0

9etherlands 96 0 3*, %,1& +,%* 3*,% %,* %,3&

=ermany D +% %,%% %,* %,&' 3 3%,%% %,*1 %,%

$yprus $N +% %,%% %,+& %,* & &%,%% %,*3 %,3

=eoria =; +% * *%,%% %,++ %,1 1 1%,%% %,++ %,+'

Spain ; +% & &%,%% %,+* %,** 1 1%,%% %,+ %,0*

#oland #6 +% %,%% %,1+ %,3 3 3%,%% %,*% %,&+

Total +0* 0% &1,' %,*+ +,3 3 1,+ %,+0 *,31

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3. $onclusions

8n this study, +0* urine samples recei!ed from +0 ;uropean countries wereanalyAed for =lyphosate and 7/#7 residues usin a new =$-/S/S method(see table *). With a 6" of %,+ E>l, on a!erae && and 13 of the urine

samples analyAed were found to contain Iuantifiable le!els of =lyphosate and7/#7, respecti!ely. Howe!er the freIuency of detection calculated for eachindi!idual ;U-state raned from +% to '% (see Table &). The hihest=lyphosate concentration was +,0 E>6 (6at!ia 3), the hihest 7/#7concentration was *,3 E>6 ($roatia 1). 7ll in all +* (3,3) participants of thestudy sinificantly eCceeded the tentati!e reference !alue of %,0 E>6 for=lyphosate (see section &).8n eneral, =lyphosate and 7/#7 urinary le!el do not correlate !ery well. Thisis due to the findin that the ratio 7/#7>=lyphosate (7=) in human urine is!ery !ariable probably reflectin the !ariable 7=s in diet. 7 hih 7=suests an additional eCposure aainst 7minopolyphosphonate based

tensides li4e 7T/T or ;DT/#, which easily derade to 7/#7.The results i!e a first idea to which eCtent adults in +0 ;uropean countriesare eCposed to =lyphosate. The reional and indi!idual !ariations are lare.Diet seems to be the main sources of eCposure. Howe!er, more scientificwor4 is needed to distinuish between different eCposure situations.

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determination of glyphosate residues in human urine samples from 18 european countries

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