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Trakia Journal of Sciences, Vol.1, No 3, pp 19-22, 2003

Copyrigh ! 2003 Trakia "ni#ersiy$#aila%le on line a&

HTTP://WWW.UNI-SZ.BG

ISSN 1312-1723

 Review Article

CURRENT STATE OF ANALYTICAL METHODS FOR THE DETECTION

OF RESIDUES IN BEE PRODUCTS

St. B!"#$%

S'iss (ee )esearch Cenre, *e+eral airy )esearch Saion, (ern, S'ierlan+.

ABSTRACT

The o%eci#e of his paper is o re#ie' shorly he curren sae of he analyical /eho+s, use+ for heea/inaion of %ee pro+ucs. The principle of +ifferen /eho+s is gi#en an+ he a+#anages an+ he

shorco/ings of each /eho+ are +iscusse+. *irsly, here is a focus on he /eho+s, use+ for+eer/inaion of he /ain cona/inans in %ee pro+ucs, especially of ani%ioics in honey. *or

+eer/inaion of ani%ioics he screening /eho+s Char/ Tes an+ S$ are use+. Secon+ly, all posii#e sa/ples are +eer/ine+ 4uaniai#ely %y 56C, C-7S. 7eho+s for +eer/inaion of

 persisen acarici+es an+ pesici+es, as 'ell as for he +eer/inaion of so/e #olaile cona/inans inhoney an+ oher %ee pro+ucs, are +escri%e+ an+ +iscusse+.

&'( )*"+: (ee pro+ucs, )esi+ues, Cona/inaion, $nalyical /eho+s, Curren saus.

The o%eci#e of his paper is o re#ie' shorly

he curren sae of he analyical /eho+s,

use+ for he ea/inaion of %ee pro+ucs,

focusing on he /ain cona/inans in %ee

 pro+ucs. The +ifferen /eho+s for he

+eer/inaion of ani%ioics in honey are

re#ie'e+.

1. ANTIBIOTICS IN HONEY

6resenly ani%ioics ha#e %een he /ain

cona/inans in honey. The follo'ing

ani%ioics ha#e %een +eece+ in honey 8see

)eference lis.

• Sulfona/i+es& sulfahiaole,

sulfa/ehaine, sulfa/ehaaole,

sulfanila/i+e

• $/inoglycosi+es& srepo/ycine

• Teacyclines& :yeracycline,

chloreracycline

• $/phenicols& Chlora/phenicol

The follo'ing ani%ioics ha#e %een

repore+ o %e use+ in apiculure, %u here are

no pu%lishe+ 'orks on heir +eecion&

(ea-laca/s 8penicillins an+ /acroli+es&

ylosine, eryhro/ycin

.; Correspon+ence o& Sefan (og+ano#,

ie%efel+, Sch'aren%urgsrasse 1<<, C5-3003(ern, S'ierlan+, Tel& =>18031 323 ?2 0?,

*a& =>18031 323 2@ 02,

-/ail& sefan.%og+ano#Afa/.a+/in.ch hp&BB'''.apis.a+/in.ch

n rouine analysis of honey ani%ioics are

generally ese+ %y&

1. Screening, +eer/inaion of posii#e

sa/ples& Char/ Tes, S$

2. uaniai#e +eer/inaion of posii#e

sa/ples %y 56C, C-7S

S,*''$$! 't"+

 ELISA

lisa a ra+io-i//uno assay, in 'hich

ani%ioics are 4uaniai#ely assaye+ %y

specific ani%o+ies. has %een ese+

successfully in honey 81. The +eecion li/i

is 10 o <0 pp%. Dih his /eho+ he

concenraion range of in+i#i+ual ani%ioics

can %e 4uaniai#ely +eer/ine+. (ecause of

cross reaci#iy 'ih oher ani%ioics fro/ he

sa/e group he /eho+ can %e use+ only forse/i-4uaniai#e +eer/inaion. No' his

screening /eho+ has %een largely replace+

 %y he Char/ es.

Charm II Test 

The Char/ es 'as pro+uce+ %y Char/

Sciences nc. "S$. is a screening es, use+

for +ifferen foo+ as /ea an+ /ilk, 'hich has

 %een a+ape+ for honey esing. There are

 pu%lishe+ repors on he use of he /eho+ 82,

3. is %ase+ on he specific %in+ing ofani%ioics o recepors. The 4uaniaion is

+eer/ine+ %y /easuring of ra+ioaci#iy& 5 3

or C1> . The Char/ es can +eec he 'hole

group of ani%ioics. There are ess for esing

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in honey of& sulfona/i+es, eracyclines, %ea-

laca/s, /acroli+es, a/phenicols an+

a/inoglycosi+es of he srepo/ycin ype.

The screening %y he Char/ es 'ill eclu+e

he negai#e sa/ples. The posii#e sa/ples

ha#e o %e confir/e+ %y oher /eho+s

856C, C-7S, see %elo'. The rae of he

correcly classifie+ posii#e sa/ples +epen+s

on he eperience of he la%oraory. Thus 0 o30 E of he posii#ely ese+ sa/ples 'ill %e

confir/e+ %y oher /eho+s. $lso, he ess

for so/e ani%ioics 8e.g. srepo/ycine are

safer for ohers 8e.g. sulfona/i+es. has %een

foun+ ou, ha 6ara $/ino (enoic $ci+

86$($, a naural honey consiuen, can

+isur% he es for sulfona/i+es an+ yiel+

Ffalse posii#eG resuls. $lso, here are /ari

effecs, especially in honey+e' an+ chesnu

honey, 'hich lea+ o an increase+ rae of

Ffalse posii#eG sa/ples. see/s ha he

+eecion le#el for each ani%ioic group

+epen+s on he honey ype. $s a 'hole, he

Char/ es for honey is a #alua%le ool for

rouine esing for honey pro+ucers an+

 packers. s /ain a+#anages are&

• ess a 'hole group of ani%ioics

• is consi+era%ly cheaper han he oher

4uaniai#e /eho+s

0#$tt#t$

The resuls of he Char/ es are 4ualiai#e o

se/i-4uaniai#e. The posii#ely ese+

sa/ples are furher analyse+ %y 56C an+

C-7S /eho+s for 4uaniaion of he

resi+ues.

 HPLC 

:nly he recen lieraure 'ill %e consi+ere+,

as ol+er /eho+s ha#e +eecion li/is in he

 pp/ +eer/inaion range. )eferences fro/

earlier lieraure can %e foun+ in Hauf/ann e

al. 8>. The 56C is goo+ for rouine 'ork,

'here kno'n ani%ioics are analyse+. The+ra'%acks of 56C are&

• ach ani%ioic class has o %e ese+

separaely

• There is no 100 E cerainy regar+ing he

safe i+enificaion of he ani%ioics

)ecenly auo/aic 56C syse/s 'hich

inclu+e sa/ple eracion an+ 56C

+eer/inaion ha#e %een +e#elope+

8hp&BB'''.applica-analyik.+e. This is a

 pro/ising +e#elop/en, ai/ing a a less

la%our inensi#e an+ cheaper ani%ioic+eer/inaion.

Sulfona/i+es are %oun+ o honey sugars.

Tha is 'hy an aci+ hy+rolysis sep is

inclu+e+ in he /eho+. The sulfona/i+es are

+eri#aise+ for fluori/eric +eecion an+ afer

separaion %y re#erse+-phase 56C are

+eece+ %y io+e $rray eecor or %y a

fluorescence +eecor 8<, @. The li/i of

+eecion is a%ou < pp%, he li/i of

4uaniaion lies a 10-1< pp%, he reco#eries

of 11 +ifferen su%sances #ary fro/ I0 o 100

E.

Srepo/ycin  is  analyse+ %y re#erse+- phase 56C, follo'e+ %y pos-colu/n

+eri#aisaion o ena%le fluorescence +eecion

82, I, ?. The li/i of +eecion is a%ou <

 pp%, he li/i of 4uaniaion is 10 pp%.

Teracycline  an+  oyeracycline  'ere

+eer/ine+ %y re#erse+-phase 56C 'ih "V

+eecion in a su+y of he +egra+aion in

honey, %u he li/i of +eecion 'as 4uie

high, a%ou 1 pp/ 89. :yeracyline

8erra/ycine +egra+es 'ihin <- 9 'eeks 89,

10 ino +ifferen /ea%olies 89. n a recen

ring rial, con+uce+ %y *$6$S 811 +ifferen

56C /eho+s 'ih fluorescence +eecion

ha#e use+, he +eecion li/i %eing a%ou <0

 pp% 8>,12. The resi+ue le#el of 0.@ pp/

chloreracycline ese+ in his colla%orai#e

su+y 'as far a%o#e he le#els, epece+ in he

 prais.

 LC/MS-MS 

This is he /os /o+ern an+ pro/ising

/eho+. The analysis is %ase+ on clean up %y

S6, separaion %y re#erse+-phase 56C an+su%se4uen +eecion %y 7S-7S. The 7S-7S

insures an al/os F100 E-safeG specific

+eecion 'ih a #ery lo' %ackgroun+ noise.

The /eho+ 'as +e#elope+ %y Hauf/ann e

al. 813 for sulfona/i+es, eracyclines

8eracyclines, oyeracycline an+

chloroyeracyclines an+ flu/e4uine. The

li/i of +eecion is 0.< o 10 pp%, +epen+ing

on he su%sance. The /eho+ is %eing

 presenly een+e+ o inclu+e also

chlora/phenicol an+ srepo/ycine. The

o%eci#e is he +e#elop/en of a CB7S-7S

/eho+, capa%le of +eecing all ani%ioic

resi+ues in honey.

2. ACARICIDES AND PESTICIDES

2.1. A,#*,"'+ #$" '+t,"'+ $ $'(

$ lis of he recen /eho+s use+ is gi#en

 %elo'. (oh C an+ 56C /eho+s ha#e

 %een use+. C /eho+s 'ih 7S +eecion

see/ o %e /os pro/ising.

Gas Chromatographyn /os cases he echni4ues use eracion of

honey %y S6 or organic sol#ens, follo'e+

 %y separaion on capillary chro/aography

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'ih C, N6 or 7S +eecion. *or

/eho+s for he +eecion of he /os

co//only use+ acarici+es an+ pesici+es see

he reference lis %elo'. The li/i of

+eer/inaion lies %e'een 1 an+ 10 pp%. The

li/i of +eecion of hy/ol lies a a%ou 0.02

 pp/, he li/i of +eer/inaion %eing aroun+

0.1 /gBkg 81>.

 HPLC 

)e#erse+-phase 56C 'ih 6hoo io+e

$rray eecion is successfully use+. The

+eer/inaion li/i for synheic acarici+es is

higher han he one achie#e+ %y C /eho+s

an+ lies ypically %e'een 10 an+ <0 pp%. The

li/i of +eecion of organic aci+s lies a a%ou

1 pp/.

 E!yme aalysis

$ co/%ine+ +eer/inaion of oalic an+

for/ic aci+ can %e carrie+ ou 'ih he

(oerhinger Hi, er/any 81<. :alic aci+

can also %e +eer/ine+ 'ih a Sig/a Hi 81@.

The li/i of +eecion of hese /eho+s lies

 %e'een 3 an+ < pp/.

2.2. A,#*,"'+ #$" *+ $ 4''+)#5

The /eho+, /osly use+ for he

+eer/inaion of he /os co//on acaric+es

 %ro/opropylae, cou/phos, flu#alinae an+flu/ehirne is& eracion %y heane,

separaion fro/ high-/olecular co/poun+ %y

freeing cenrifugaion, purificaion on

*lorisil colu/ns an+ su%se4uen

+eer/inaion %y capillary C an+ C

+eecion 81I, 1?. The +eecion li/i is 0.1-

0.2< pp/. The o%eci#e is o enlarge he

+eer/inaion scope %y inclu+ing oher

#arroaci+es as a/ira, cy/iaole ec, as

 propose+ %y Hora e al. 819. :nly C-7S

+eecion 'ill allo' he +eecion of all

acarici+es, use+ for #arroa conrol.

3. 6OLATILE CONTAMINANTS

Volaile cona/inans can %e ese+ 'ih

hea+-space or S67 echni4ues 820, 21, 22&

• )epulsi#e su%sances use+ in honey

har#es 8phenol, niro%enene

• $ni-'a /oh su%sances& para-

+ichlor%enene, naphhalene

• Co/ponens of essenial oils& hy/ol

. 0UALITY ASSURANCE

The inro+ucion of ualiy $ssurance in

analyical la%oraories accor+ing o he N

><001 an+ S: 9000 nor/s allo' precise an+

repro+uci%le /easure/ens of race a/ouns

of resi+ues in %ee pro+ucs. Colla%orai#e

rials shoul+ %e regularly carrie+ ou o ensure

goo+ perfor/ance of he esing la%oraories.

Three colla%orai#e rials ha#e %een carrie+

ou recenly 'ih %ee pro+ucs & suflona/i+es

in honey, eracycline in honey an+ acarici+es

in %ees'a 8see reference lis.

REFERENCES

1. 5eering, D., "sle%er, ., ierich, ).,

7Krl%auer, ., //unoche/ical

screening for ani/icro%ial +rug resi+ues

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2I<9-2I@2, 199?.

2. Hocher, "., Nach'eis #on Srepo/ycin-

)LcksKn+en in 5onig /iels Char/ -

Tes un+ $%sicherung +er (efun+e +urch

56C /i NachsKulen+eri#aisierung un+

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