Dioxins and furans in the Jordanian environment part 2: Levels of PCDD and PCDF in human milk samples from Jordan

PII: s0045-6535(%)00347-5

Chemosphere, Vol. 33, NO. 12. pp. 2469-2474, 1996 Copyright Q 1996 Elsevier Science Ltd Printed in Great Britain All rights rewed 004S-6535/96 $lS.OOtO.OO

DIOXINSAND FURANSIN THE JORDANIANENVIRONMENT PART 2: LE!IELS OF PCDD AND FCDF IN HUMAN MILK SAMPLES FROM JORDAN

M. A. Alaw?), H. Wtimanr~~,

W. Lore&J,

M. Bahadir2)

1) Department of Analytical Chemistry, University of Jordan, ll942-Amman,

Jordan

2) Institute of Ecological Chemistry and Waste Analysis, Technical University of Braunschweig, Hagenring 30, 38106 Braunschweig, F. R. Germany

(Received in Germany 19 February 1996; accepted 11 September 1996)

Abstract Thirty individual human milk sades

were gathered from five main towns in Jordan. They were mixed to

six pooled samples and analyzed for PCDD and KDF.

All examined sades

1,2,3,4,6,7&HeptaCDD (3.2 - 96.0 ng/kg fat) and CktaCDD (29.0 - 147 r&g @GA)-values range between 0.26 and 6032 ng X&g concentration of 019 ng TEQ/kg milk fat. Copyright

were contaminated with fat). The cakzulated TEQ

fat, which are all above the calculated tolerable 0 1996 Elsevier

Science Ltd

1. Introduction Polychlorinated dibenzo-pdioxins (PCDD) and dibenzofurans (PC09 are widely spread in the environment. These ubiiitous

contaminants were found eg. in soil, sludge, filter dust, external and indoor air, bleached

paper, foodstuff, human adipose tissue and in human mother’s milk [l]. The tolerable daily intake (TDI) of PCDDpcDF according to the former German Federd Health Department (BGA) is 1 pg toxicii

equivalencies (TEQ) per kg body weight and day 111.Ca. 90% of the human burden

with PCDD/FCDF entered the body by nutriiion and the major part by consuming milk and milk products [l-4]. It has been shown, that breast-fed infants in developed countries ingest these compounds at levels

that are about 30 times higher than the calculated tolerable daily intake [5,6]. Fiirst et al. and others [2,7,8] 2469

2470 showedthat the concentration differences of PCDDpcDF in mothers’ milk are based on the fdlowing parameters: - number of breast-fed babies, - length of breast-feeding periods, - mother’s age and - nutrition habits.

They also found that there are no diierences

between the PCDD/PClX

concentrations

in mothers’ milk

from urban and country regions in Germany [2]. Humans in Jordan are exposed to dioxins and furans from different sources, such as - open combustion of municipal waste whii

contains a huge amount of plastic materials (PVC), heavy

metals and chlorine-containing industriil waste, - burning of old tyres or - the combustion of organic residues such as the resiiue of olive pressing.

The results, published in part

1 [9], showthat Jordan’s oldest municipal landfill site at Marka - Amman is

highly contaminated with PCDD and PCDF. This paper presents the results of analyses performed to determine PCDD and PCDF concentrations in six poded human mothers’ milk samples from five main towns in Jordan.

2. Experimental

2.1 Materials All standard solutions were from Promochem wesel,

Germany), solvents were from Baker (Deventer, Ne-

therlands) and adsorbents were purchased from ICN (Eschwege, Germany).

2.2 Sampling

Human milk samples were collected in five different towns in Jordan in 1994. From each area four to six individual human milk samples were pooled by mixing aliquots of 25 g of each sample. All samples were stored at -20°C until analysis. Table 1 delivers informations that are necessary to characterize the pooled samples. 2.3 Extraction,

fat determination and clean-up

Milk samples were extracted according to a method described by Acker et al. [lo]. Briefly, 80 - 120 g of milk were spiked with 25 pl of 15 13C-labelled2,3,7&substituted PCDDF congeners of 50 pg/ul concentration as internal standard. 80 ml saturated potassium oxalate and 300 ml ethanol were added and mixed. The

2471 Tab. 1: Characterizationof the pooled mothers’milk samples

sample

town

number of

range of

average

fat content of

pregnancies

feeding time*

mother’s age

pooled sample

Ways1

bears1

I”/01

Gl

lrbii

1

5 - 270

26

G2

Aqaba

2

15 - 300

24

4.04

G3

Madaba

3

5 - 150

29

3.60

G4

Zarka

4

68 - 230

28

3.63

G5

Amman

8

30 - 62

G6

Amman

5

1 - 14

I

5.60

--I 65

62

I

67

* Only for the last baby

mixture was extracted twice, each time with 150 ml diethyl ether and 210 ml petroleum ether. The pooled extracts were dried over anhydrous sodium sulfate, filtered into a preweighed flask and the sdvent was evaporated to drynessat 40°C and 100 hPa. The amount of fat determined was used for the calculation of the level of PCDD/PCDF on fat basis.

The clean-up of the extracts was performed according to Hagenmaier et al. [ll] and as describedin [9] with the only exception that the first and third cdumn were identical.The cleaned eluate from the third column was concentrated to 40 ul.

2.4 Analysis

The PCDD and PCDF were analyzed by GC/MS (El) using the SIM-mode. The conditions are described in [9]. 2,3,7,&substituted 13C-labelledPCDD/F standard substanceswere used for evaluation. 2.5 Recoveries and blank A fresh cow milk sample was extracted and analyzed as describedabove. As expected, the concentrationsof all PCDD/F congeners in this blank sample were under the detection limit. 150 g of the same sample were spiked with a 2,3,7,8substituted PCDD/PClX standard mixture and analyzed. The recoveries of the five homdogue groups, tetra to octa, ranged between 94% and US% for PCDD and 93% to 110% for PCDF.

2412 3. Results and discussion The concentrations of the 2,3,7,8-sr&ituted

specific congeners of the PCDD/F and the EQ-values

of the

Jordanian mothers’ milk samples are listed in table 2.

Tab. 2: PCDD and PCDF concentrations in Jordanian pooled human milk samples [pg/g fat]

Gl

G2

G3

G4

G5

G6

3.7

7.8

< 2.6

t 6.3

t 32

21.3

< 4.5

55.0

61

t 6.3

< 32

1,2,3,4,7,8HxCDD

< 3.7

< 4.5

11.0

< 2.6

t 6.3

t 32

123,6,7,8-Hx~

56.5

19.0

11.0

9.6

t 6.3

< 32

1,2,3,7,8,9HxCDD

< 3.7

< 4.5

Il.0

< 2.6

< 6.3

t 32

lW%4,6;1&Hp~D OCCDD I

47.2

14.5

96.0

14.0

15.7

3.2

75.8

46.9

147

29.0

561

64.6


2,37&TeCDD 12,3,7,8-PeCDD

8.3

< 4.5

111

4.5

‘2,3,4,7,8-PeCDF

75.9

‘12>,4,7,8HxCDF

161

;1,2,3,6,7,8-lixCDF

104

2,3,7,8-TeCDF

,X2,3,7,8-PeCDF

1,2,3,7,8,9HxCDF


< 2.6

t 6.3

< 3.2

16.8

2.6

t 6.3

< 32

101

841

4.4

t 6.3

t 32

17.9

112

5.2

t 6.3

t 32

< 4.5

961

4.4

t 6.3

t 3.2

7.4

t 4.5

< 11

< 2.6

t 6.3

t 3.2

54.6

t 3.2

t 4.5

<11

< 2.6

t 6.3

,123,4,6,7,8+KDP

391

t 4.5


< 2.6

t 6.3

9.6

1,23,4;1,8,9HpCDF

106

t 4.5

<11

t 2.6

t 6.3

t 32

OcCDF

189

2,3,4,6,7,&HxCDF

EQ(BGA) I-TEQ

< 22

< 22

< 17

t 31

t 32

60.32

13.l4

40.82

3.40

0.372

0261

96.69

17.96

90.61

7.47

0.216

0193

G 1 - G 6: See Tab. 1 In this table, the samples G 2 - G 6 (Aqaba, Madaba, Zarka and Amman) show typical congener patterns of PCDD and PCDF. In all samples, except G 1 (Irbii, PCDF, with OCDD quantitatively 1,2,3,4,6,7,8ljKDF.

the PCDD-concentration was higher than that of the

dominating. In sample G 1 the highest concentration was found for

In general, in G 1 the concentrations of the PCDF were higher than those of the PCDD,

which is in contradiction to findings by P. Fiirst et al. [12], too. In G 2 - G 6, OCDD represents more than 50% of the total dioxin amounts. The levels of the other homologues decrease with a decrease of the

2473

degree of chlorination. 1,2,3,6,7,8HxCDD is domrnating its group of isomers and amounted to more than 70% of the sum of the three identified HxCDD, which was found elsewhere, too [6,12].

The results of the pooled mothers’ milk sample G 1 from Irbii, located in northern Jordan, are totally different from all other samples and from all typical patterns published in literature [S]. The sum of the PCDF amounts to about 83% of the total PCDD/PClX contamination. The citizens of this town still have no central heating; therefore they use open fires for heating. The public bakeries use either diesel or a mixture of diesel and dd motor oil for baking bread. Mostly, the PCJX quantitatively dominate in case of PCDD/KDFformation by open combustion. Considering sample G 1, this might probably explain the unusual findings, because open combustion is clearly the major source for direct KDDF-contamination

in Irbid.

Fiirst et al. [2] found that there are no significant differences between the PCDD/PCDF concentrations in mothers’ milk samples from urban and country regions in Germany. Fiirst explained this finding by the fact that there is no region in Germany, where people only consume the locally produced food. That is to say, all food types in Germany are almost eqwlly distributed in all regions. There is a different situation in Jordan and this also contributes to the explanation of TEQ-values, differing from one region to another.

The high F’CDD/PCDF concentrations and lEQ-values

of sample G 1 (Irbii

can partly be explained by the

fact that all volunteering ladies, contributing to this pooled sample, nursed their first child. This fact coincides with the finding of Fiirst et al. [2, 121, that the FCDD/F concentration in mother’s milk is inversely proportional to the number of breast-fed children.

Based on the assumption that a breast-fed baby daily drinks 150 g of milk per kg body weight and based on the tolerable daily intake (TDl) vaue I of 1 pg TEQ/kg b. w. and day [l], the maximum PCDD/PCDF concentration in milk fat should not exceed 019 pg TEQ per gram milk fat.

(1 pg TEQ/d kg b.w. . 5 kg b.w.) : (5.25 g milk fat/d kg b.w. . 5 kg b.w.) = 019 pg TEQ/g milk fat

Further assumptions in this calculation are a share of milk fat of 3.5% and a 100% incorporation of the PCDD/F into the baby’s body. Rappe et al. found that for most of the PCDD/F congeners the absorption from the mothers’ milk of the ingested compounds are over 95%. Higher excretion was only noticed for HpCDD and DCDD [5].

I In table 2 it is shown that the calculated TEQ (BGA) vaues of all tested Jordanian mother’s milk samples exceed the value of 019 pg TEQ/g milk fat, which means that all samples are contaminated, especially sample G 1.

2414 4. Literature

[l] I. Lukassowitz (1990): Eintragsminimierung zur Reduzierung der Dioxinbelastung dringend erforderlich; Bundesgesundhbl. 8,350-354. [2) P. Fiirst, Chr. F&t,

K. Wilmers (1993): FCDD/F, Biienyle

UWSF - Z. Umweltchem. bkotox.

und Organochlorpestizide in Frauenmilch;

5,204206.

[3] H. Beck, K. Eckart, W. Mathar, R. Wtikowski

(1989): PCDD and PCDF body burden from food intake

in the Federal Republic of Germany; Chemosphere 18, 417-424. [4] P. First, Chr. Fiirst, W. Groebel (1990): Levels of PCDDs and PCDFs in food-stuffs from the Federal Republic of Germany; Chemosphere 20, 787-792. [S] D. Dahl, G. Lindst ram, K. Wberg, C. Rappe (1995): Absorption of polychlorinated biienyls,

dibenzo-p

dioxins and dibenzofurans by breast-fed infants; Chemosphere 30, 2297-2306. [6] P. Fiirst, Chr. F&t,

K. Wdmers (1994): Human milk as a bioindiiator

PCDFs, organochlorine pesticii

[I

for body burden of PCDDs,

and PCBs; Environ. Health Perspect. Suppl. 102, 187-193.

H. Beck, A. Dross, M. En&, Chr. Fiirst, P. Fiirst, A. Hille, W. Mathar, K. Wilmers (1991): Polychlorierte Diienzofurane und dioxine

in Frauenmilch: Ergebnisse von Riickstandsuntersuchungen aus Deutschland;

Bundesgesundhbl. 34, 564-568. [8] Chr. F&t,

P. F&t,

K. Wrlmers (1991): PCDD/PCDF in Frauenmilch 1984- 1991,wesentliche Ergebniie

der Auswertung von iiber 600 Proben; Organohalogen Compounds 6,145-165. [9] M. A. Alawi, H. Wchmann, W. Lorenz, M. Bahadir (1995): Dioxins and furans in the Jordanian environment, part 1: Preliminary study on a municipal landfill site with open combustion nearby Amman - Jordan; Chemosphere 32, 907-912. [lo] L. Acker, E. Schulte (1970): ijber das Vorkommen chlorierter Kohlenwasserstoffe im menschlichen Fettgewebe und in Humanmilch; Deutsche Lebensmittelrundschau 66, 385-390. [ll] H. Hagenmaier, H. Brunner, R. Haag, H.-J. Kunzendorf, M. Kraft, A. T~haczek, U. WebemS (1981): Stand der Dioxin-Analytik;

VDI-Beriiht Nr. 634, 61-89, VDI-Verlag, Dusseldorf.

[12] P. Fiirst, H.-A. Meekren, Chr. Kruger, W. Groebel (1987): Polychlorinated dibenzodioxins and diinzofurans in human milk samples from western Germany; Chemosphere 16, 1983-1988.