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Blood levels of polychlorinated dibenzodioxins, polychlorinated dibenzofurans and polychlorinated biphenyls in the general population of a Spanish Mediterranean city
~
Pergamon
Chemosphere, Vol. 36, No. 3, pp. 419-426, 1998
1997 ElsevierScienceLtd All rightsreserved.Printedin GreatBritain 0045-6535/98 $19.00+0.00
PII: S0045-6535(97) 10015-7 BLOOD LEVELS OF POLYCHLORINATED DIBENZODIOXINS, POLYCHLORINATED DIBENZOFURANS AND POLYCEILORINATED BIPHENYLS IN THE GENERAL POPULATION OF A SPANISH MEDITERRANEAN CITY.
CA. GONZALEZ CA (1) (a), M. KOGEVINAS (2), A. HUICI (3), E. GADEA (3), M. LADONA (2), A. BOSCH (4) and MJ. BLEDA (1). (1) Institut of Epidemiological and Clinical Research (IREC). Jordi Joan 5, 08301. Matar6 (Barcelona). Spain. Fax:34/3/7906802; E-mail: [email protected] (2)Municipal Institut of Medical Research (IMIM). Barcelona. (3) National Institut for Occupational Safety and Health (CNCT). Barcelona. (4) Laboratory of Consorci Sanitari de Matar6 (CSM). (Receivedin Germany2 April1997;accepted31 July 1997)
ABSTRACT Polychlorinated dibenzodioxins (PCDDs), Polychlorinated dibenzofurans (PCDFs) and Polychlorinated biphenyls (PCBs) are among the most toxic environmental pollutants. We determined blood levels of these compounds in a population sample of the city of Matar6, Spain. Blood samples were drawn from a randomly selected sample of 198 subjects, of both genders, aged 18 to 69 years. These samples were pooled into 10 groups for laboratory analysis. For males, total level of PCDDs was 505.7 ppt, of PCDFs was 26.7 ppt, and the international toxic equivalent (I-TEQ) was 12.5. For females the levels were 739 ppt, 28.8 ppt and 14.7 I-TEQ, respectively. The most important contributors to the total ITEQ were HexaCDD, PentaCDD and PentaCDF. The blood concentration of total PCBs was 2.02 mg/l in males, and 1.58 mg/1 in females. Levels ofPCDDs, PCDFs and PCBs increased by age in both sexes. The levels of PCDDs and PCDFs in residents of this Mediterranean city are among the lowest observed in industrialized countries. © 1997 Elsevier Science Ltd
INTRODUCTION Dioxins (1) and PCBs (2) are among the most important toxic chemicals for humans in the environment. Concern over contamination from dioxins from waste incinerators (3) and other sources (4) has risen in recent years in developed countries. The evaluation of environmental risk due to exposure to these chemicals requires sufficient information of the degree of exposure at population and/or individual levels. Human exposure to these compounds has mostly been estimated by measuring concentrations in air, water, soil, or other media. The external exposure, however, can only be considered as a rough estimate of the internal dose of exposure to chemical agents (5). Most measurements of these compounds in humans have been done in north America, northern Europe and . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
(a) To whomreprintrequest and correspondenceshouldbe adresssed. 419
420 selected other countries such as Vietnam (6). It is considered that human tissue levels among industrialized nations are similar, without significant differences between males and females (4).
There is limited
knowledge, however, of levels in wide areas of Europe, including the Mediterranean countries. These analyses were conducted in the context of a study to evaluate the emissions of a large, newly constructed, municipal solid waste incinerator near the city of Matarr. In this paper we present the baseline levels of PCDDs/Fs and PCBs in this population before the incinerator started functioning.
MATERIAL AND METHODS The study was carried out in Mataro, a Mediterranean city of approximately 100,000 inhabitants, 25 km north of Barcelona. A total of 201 adults (100 males and 101 females), aged between 18 and 69 years, were randomly selected from the municipal list of inhabitants in March-June 1995. Two groups were selected. The first was a group of 104 "potentially exposed" individuals living in districts near the incinerator (less than 1 kin). The second was a group of 97 "unexposed" individuals, frequency matched to the first by sex and age-group,
living in districs far (about 4 km)
from the plant. No
socioeconomic differences were found between them. Whole blood samples (about 50 ml) were collected by routine veinpuncture for 198 of the 201 participating subjects.
Blood sample for each individual was
collected in two chemically clean 25 ml glass bottles and kept frozen at -30 °C until the time of analysis in a laboratory in Germany. All techniques for extraction, clean up and analysis by gas chomatography-mass spectometry, have been previously described (7) and were perfomed by a laboratory that meets the WHO certification standards. For analysis of PCDDs, PCDFs and PCBs whole blood samples were pooled in 10 groups: 5 from the "potentially exposed " and 5 from the "unexposed" subjects.
Within both the exposed and unexposed
groups (See foot note of Table 1), there were 3 subgroups of males subdivided by age (18-29 years, 30-49 years and 50-69 years) and 2 subgroups of females (18-39 years and 40-69 years). Concentration in both the 5 sex and age subgroups of"exposed" and the 5 subgroups of"unexposed" are presented together because all subjects represent the same background level of exposure. This means that each value in the tables represents the arithmetic mean of two measurements from the pooled blood samples of 34, 38, 27, 47 and 52 subjects respectively. Results were obtained of the concentration of the main PCDD and PCDF congeners, for the total PCDDs and PCDFs, and toxic equivalents according to the International Dioxin Toxic Equivalent (I-TEQ) factor methods (8) . For PCBs, results on the concentrations of tri, tetra, penta, hexa and hepta PCBs were obtained. Values of TEQ do not include I-TEQs for PCBs. Given that the analysis was based on the value of pooled blood samples, SDs are not known, and statistical differences between groups of sex and age can not be tested.
RESULTS The concentration (Table 1) of total PCDDs increased with age in both sexes and was slightly higher in females than in males. The total level of PCDDs was 505.7 ppt for males and 739.0 ppt for females. Almost
421 77 % of the total PCDD was contribuited by OctaCDD. The total level of PCDFs was 26.7 ppt in males and 28.8 ppt in females. Small differences were found by sex and age-group. HexaCDF was the main contributor to total PCDF. TetraCDD and TetraCDF are the least abundant isomers. Toxic equivalents (I-TEQs) were 14.7 in females and 12.5 in males. It increased with age in both sexes. PCDDs which represent 95 % of the total PCDDs and PCDFs contributed 68.5 % of the total I-TEQ (Table 2) while PCDFs which represent only 5 % of the total dioxins and furans, contributed 31.5 %. The most important toxic isomers were HexaCDD, PentaCDF and PentaCDD. The blood concentration of total PCB (Table 3) was slightly higher in males (2.02 mg/1) than in females (1.58 mg/1). In both sexes the concentration of PCB increased with age.
DISCUSSION There exists very limited data on levels of PCDDs, PCDFs and PCBs in the human population of countries in the south of Europe.
Matar6 is a mixed residential-industrial city on the Mediterranean sea. Textile
manufacture is the main industrial activity, and, besides the new incinerator, there are no other known industrial sources of exposure to dioxins. Another advantage of our study is that blood levels were measured in population sample of the city.
a
randomly selected general
One limitation is that using pooled blood data, statistical differences
between sex and age can not be tested. However
it is considered that such studies can rapidly and
economically provide useful public health information on average population dioxin levels. (9). Total levels of PCDDs found in Mataro (507.8 ppt) were similar to those found in a sample of male blood donors, aged 19 to 55 years, with no known occupational exposure to dioxin in Madrid (515.3 ppt) (10). However, the concentration of PCDFs in Mataro ( 26.7 ppt) was lower than in Madrid (66.7 ppt). The relative contribution of different congeners to total PCDD and PCDF in Mataro and the increasing concentration with age, are similar to other studies in other countries (6,11) and Madrid (10). The total I-TEQ (12) level found in males in Mataro (12.5 ppt), is among the lowest in the world, even when compared to levels in population from geographical areas without environmental contamination,like Baikalsk in
Siberia, and Hanoi in Vietnam (6,9 ppt). It is between 3 and 4 times lower than the
concentration levels observed in population from exposed areas in the south of Vietnam, that were sprayed with Agent Orange by the U.S.A. military forces. Among industrialized countries, dioxin blood concentrations are considered to be geographically fairly uniform (4) and toxics equivalents in the general population are between 20 and 40 ppt, lipids (13). One possible explication is that these low levels found in Spain are due to the absence of industrial sources of exposure, combined with a Mediterranean diet low in animal fat. Dietary intake of foods of animal origin is the most important source (> 90 % ) of the accumulation of dioxins in the human body and is was estimated that dairy products accounted for about half of the 2,3,7,8 TCDD intake (14). Mediterranean diet typically included small amounts of dairy products. The proportion of lipids provided by butter and other dairy products was 4 times higher in some north European countries
422 than in Spain (15). Another explanation for the lower levels observed in Matar6 compared to north European countries is that samples were collected at different times. During the last few years a tendency of decreasing PCDDs and PCDFs levels has been observed in some industrialized countries. The level of I-TEQ in samples from the population of Germany was in 1992 lower than in 1989 (16).
Samples from Madrid ( 10 ) and from
Matar6 have beeen taken several years after. The highest site of concentration of dioxins in mammals are the liver and adipose tissues (1). The background exposure to dioxins by sexes are considered very similar (4). We found, however, that the levels of PCDDs and PCDFs in females are slightly higher than in males. Despite the fact that nursing infants lower the body level of dioxins in women (1) it could be possible that the greater quantity of adipose tissues in women with a high prevalence of obesity, could explain the higher levels of dioxins found. The blood concentration levels of PCBs found in the general population of Mataro are similar to the concentration observed in population from non-exposed geographical areas (2). In another study in the south of Spain (17) in polulation living in an area of high exposure to organochlorine compounds from agriculture, where the concentration of PCBs in blood taken from mothers during delivery was measured, the concentration of PCB138 was 1.44 mg/1 and for PCBI80 was 2.12 mg/1. These levels are higher than those found in Mataro. A(~KNOWLEDGEMENTS: To O. Piipke for the laboratory analysis of blood samples, Cristina Mas for her important work in the study office, and Gisela Carretero and Roser Fernandez for their field work.
423 Table 1. Blood levels (ppt/g fat weight) of PCDDs and PCDFs by sex and age-group. Male(n=99) a
Female (n---99)b
Total
(n=l~ Conseners
18-29c
30-49d
50-69e
Total
18-39f
40--698 Total
2,3,7,8 TetraCDD
1.5
1.5
1.9
1.6
0.8
2.3
1.5
1.
1,2,3,7,8 PentaCDD
3.2
4.7
5.8
4.5
4.7
6.1
5.4
4.
1,2,3,4,7,8; 1,2,3,6,7,8; 1,2,3,7,8,9 HexaCDD
27.2
38.8
43.3
36.4
35.9
51.5
43.7
39.
1,2,3,4,6,7,8 HeptaCDD
46.4
62.2
70.1
59.6
72.6
99.1
85.8
70.
OetaCDD
335.6
429.0
452.3
405.7
516.6
688.4
602.5
484.
TotalCDD
413.9
536.2
573.4
507.8
630.5
847.4
739.0
600.
1.1
1.3
1.2
1.2
1.4
1.3
1.
2,3,7,8-TetraCDF 1,2,3,7,8 2,3,4,7,8 PentaCDF
5.2
5.5
6.8
5.9
5.0
.8.3
6.6
6.
1,2,3,4,7,8 1,2,3,6,7,8 1,2,3,7,8,9 2,3,4,6,7,8 HexaCDF
9.6
9.3
11.2
10.0
10.0
13.0
11.5
10.
1,2,3,4,6,7,8 1,2,3,4,7,8,9 HeptaCDF
7.9
6.8
6.8
7.2
6.2
7.8
7.0
7.
OctaCDF
2.5
2.5
2.5
2.5
2.5
2.2
2.4
2.
Total CDF
25.2
25.2
28.6
26.8
24.9
32.6
28.8
27.
Total CDD+CDF
439.1
561.4
602.0
534.6
655.4
880.0
767.8
627.
10.0
12.5
15.0
12.5
11.7
17.6
14.7
13.
I-TEQ
a 6 individual analyses; b 4 individual analyses c 2 individual analyses, 1 pool, n= 20; 1 pool, n=14 d 2 individual analyses, 1 pool, n= 16; 1 pool, n= 22 e 2 individual analyses, 1 pool, n =12; 1 pool, n= 15
f I pool, n--26; 1 pool, n= 21. g 1 pool, n=28; 1 pool, n= 24.
424 Table 2. Contribution (%) of each isomer to the total I-TEQ by sex.
Congeners
I-TEF
I-TEQ Male
Female
Total
2,3,7,8 Te~aCDD
1
12.8
10.4
11.8
1,2,3,7,8Pent~DD
0,5
18.0
18.4
18.2
1,2,3,4,7,8 1,2,3,6,7,8 1,2,3,7,8,9HexaCDD
0,1
29.0
29.9
29.4
1,2,3,4,6,7,8 HeptaCDD
0,01
5.O
6.0
5.4
OctaCDD
0,001
3.3
4.3
3.8
68.l
69.0
68.5
TotalCDD 2,3,7,8-Te~DF
0,1
0.6
0.7
0.6
1,2,3,7,8 2,3,4,7,8Pent~DF
0,05 0,5
22.5
21.7
22.2
1,2,3,4,7,8 1,2,3,6,7,8 1,2,3,7,8,9 2,3,4,6,7,8Hex~DF
0,1
8.0
7.9
8.0
1,2,3,4,6,7,8 1,2,3,4,7,8,9 HeptaCDF
0,01
0.8
0.7
0.7
OctaCDF
0,001
0.0
0.0
0.0
31.9
31.0
31.5
100.0
100.0
100.0
TotalCDF TotalCDD+CDF
425 Table 3. Blood levels (mg/l) of PCBs sex and age-group.
Male
Female
Total
Congeners 18-29 30-49 50-69 Total 18-39 40-69 Total
2.4.4'-Tri-PCB28
nd
nd
nd
nd
nd
2.2'.5.5'-Tetra PCB52
nd
nd
nd
nd
nd
2.2'.4.5.5'-Penta-PCB101
0.09
0.06
0.04
2.2'.3.4.4'.5'-Hexa-PCB138
0.39
0 . 5 3 0.67
2.2'.4.4'.5.5'-Hexa-PCB153
0.52
0.79
0.89
2.2'.3.4.4'.5.5'-HeptaPCB180
0.43
0.70
0 . 8 1 0.65
0.39
PCBTotal
1.48
2.13
2.46
1 . 2 9 1 . 8 7 1 . 5 8 1.85
0.06
0.01
0.04
0 . 5 3 0.34
0 . 5 1 0.42
0.49
0 . 7 3 0.49
0.69
0.59
0.67
0.60
0.49
0.59
2.02
0 . 0 1 0.02
REFERENCES:
(1) Lilienfeld DE, Gallo MA. 2,4-D, 2,4,5-T, and 2,3,7,8-TCDD: An overview. Epidemiol Rev 11, 28-58 (1989). (2) Polyehlorinated biphenyls and Terphenyls (second edition) (Enviromental health criteria 140), International programme on chemical safety (IPCS). WHO, p. 199-203 (1993). (3) Cleverly DH, Morrison RM, Riddle BL, Kellan RG. Regulatory analysis of pollutant emissions, including polychlorinated dibenzo-p-dioxins (CODs) and dibenzofurans (CDFs), from the stacks of municipal waste conbustors. Chemosphere 18, 1143-1153 (1989). (4) US Environmental Protection Agency, Office of Research and Development. Health Assessment Document for 2,3,7,8-Tetraehlorodibenzeno-p-Dioxin (TCDD) and Related Compounds. Volume III of III. Washington, DC: US Government Printing Oftiee, Report n* EPA/600/BP92/001c. (1994). (5) Greim H, Csanady G, Filser JG, Kreuzer P, Sehwarz L, Wolff T. Biomarkers as tools in human health risk assessment. Clin Chem 41, (12 Pt 2), 1804-1808 (1995). (6) Sehecter A, Fiirst P. Fttrst C, Papke O, Ball M, Ryan JJ, Hoang Dirda Cau, Le Cao Dai, Hoang Trong Quynh, H.Q. Cuong, Nguyen Thi Ngoe Phuong, Pham Hoang Phiet, Albert Beim, Constable J, Startin J, Samedy M, Yit Kim Seng. Chlorinated dioxins and dibenzofurans in human tissue fi'om general populations: A selective review. Environ Health Perspect Supplements 102, 159-170 (1994).
426 (7) P~ipkeO, Ball M, Lis ZA, Scheunert K. Determination ofPCDD/PCDF m whole blood from persons involved in fire incidents. Cbemosphere 20, 959-966 (1990). (8) Eadon G, Kaminsky L, Silkworth J, et al. Calculation of 2.3.7.8-TCDD equivalent concentrations of complex environmental contaminant mixtures. Environ Health Perspect 70, 221-227 (1986). (9) Schecter A, Dai LC, Thuy LTB, Quynh HT, Minh DQ, Cau HD, et al. Agent orange and the Vietnamese: The persistence of elevated Dioxin levels in human tissues. Am J Public Health 85, 516522 (1995). (10)Jim6nez B, Hern~dez LM, Gonz~lez MJ. Levels of PCDDs ans PCDFs in serum samples of non exposed individuals living in Madrid (Spain). Organohalogen compounds 26, 249-253 (1995). (ll)PleB T, Scheneider F, Steiner M, Karmaus W. Impact of body-mass-index and age on the bloodconcentration of PCDD/PCDF of adults and children. Chemosphere 26, 1109-1118 (1993). (12)Bimbaum LS, Devito MJ. Use of toxic equivalency factors for risk assessment for dioxins and related compounds. Toxicology 105, 391-401 (1995). (13) Schecter AJ. Dioxins and related chemicals in humans and the environment. In: Gallo M. Scheuplein ILl, Vander Heijden KA, eds. Biological basis for risk assessment of Dioxins and related compounds. Cold Spring Harbor, NY: Cold Spring Harbor p. 169-213. Banbury Report 35 (1991). (14) Huisman M, Eerenstein SE, Koopman-Esseboom C, Brouwer M, Fidler V, Muskier FA, Sauer PJ, Boersma ER. Perinatal exposure to polychlorinated biphenyls and dioxins through dietary intake. Chemosphere 31(10), 4273-87 (1995). (15) Riboli E, P6quignot G, Repetto F, Axerio M, Raymond L, Boffetta P, Zubiri A, Del Moral A, Est6ve J, Tuyns AJ. A comparative study of smoking, drinkings and dietary habits in population samples in France, Italy, Spain and Switzerland. Rev Epid6m. et Sant6 Publ 36, 151-165 (1988). (16) Papke O., Ball M., Lis A. PCDD/PCDF in Humans. A 1993 Update of background data. Chemosphere 29, 2355-2360 (1994). (17) Marttnez E, Romanos A, Praena M, Repetto M, Martinez D. Organochlorine compound: blood levels in mother, newborn babies and breast and bottle fed babies. A study in the province of Huelva. Anales Espafioles de Pediatria 39, 46-52 (1993).
Pergamon
Chemosphere, Vol. 36, No. 3, pp. 419-426, 1998
1997 ElsevierScienceLtd All rightsreserved.Printedin GreatBritain 0045-6535/98 $19.00+0.00
PII: S0045-6535(97) 10015-7 BLOOD LEVELS OF POLYCHLORINATED DIBENZODIOXINS, POLYCHLORINATED DIBENZOFURANS AND POLYCEILORINATED BIPHENYLS IN THE GENERAL POPULATION OF A SPANISH MEDITERRANEAN CITY.
CA. GONZALEZ CA (1) (a), M. KOGEVINAS (2), A. HUICI (3), E. GADEA (3), M. LADONA (2), A. BOSCH (4) and MJ. BLEDA (1). (1) Institut of Epidemiological and Clinical Research (IREC). Jordi Joan 5, 08301. Matar6 (Barcelona). Spain. Fax:34/3/7906802; E-mail: [email protected] (2)Municipal Institut of Medical Research (IMIM). Barcelona. (3) National Institut for Occupational Safety and Health (CNCT). Barcelona. (4) Laboratory of Consorci Sanitari de Matar6 (CSM). (Receivedin Germany2 April1997;accepted31 July 1997)
ABSTRACT Polychlorinated dibenzodioxins (PCDDs), Polychlorinated dibenzofurans (PCDFs) and Polychlorinated biphenyls (PCBs) are among the most toxic environmental pollutants. We determined blood levels of these compounds in a population sample of the city of Matar6, Spain. Blood samples were drawn from a randomly selected sample of 198 subjects, of both genders, aged 18 to 69 years. These samples were pooled into 10 groups for laboratory analysis. For males, total level of PCDDs was 505.7 ppt, of PCDFs was 26.7 ppt, and the international toxic equivalent (I-TEQ) was 12.5. For females the levels were 739 ppt, 28.8 ppt and 14.7 I-TEQ, respectively. The most important contributors to the total ITEQ were HexaCDD, PentaCDD and PentaCDF. The blood concentration of total PCBs was 2.02 mg/l in males, and 1.58 mg/1 in females. Levels ofPCDDs, PCDFs and PCBs increased by age in both sexes. The levels of PCDDs and PCDFs in residents of this Mediterranean city are among the lowest observed in industrialized countries. © 1997 Elsevier Science Ltd
INTRODUCTION Dioxins (1) and PCBs (2) are among the most important toxic chemicals for humans in the environment. Concern over contamination from dioxins from waste incinerators (3) and other sources (4) has risen in recent years in developed countries. The evaluation of environmental risk due to exposure to these chemicals requires sufficient information of the degree of exposure at population and/or individual levels. Human exposure to these compounds has mostly been estimated by measuring concentrations in air, water, soil, or other media. The external exposure, however, can only be considered as a rough estimate of the internal dose of exposure to chemical agents (5). Most measurements of these compounds in humans have been done in north America, northern Europe and . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
(a) To whomreprintrequest and correspondenceshouldbe adresssed. 419
420 selected other countries such as Vietnam (6). It is considered that human tissue levels among industrialized nations are similar, without significant differences between males and females (4).
There is limited
knowledge, however, of levels in wide areas of Europe, including the Mediterranean countries. These analyses were conducted in the context of a study to evaluate the emissions of a large, newly constructed, municipal solid waste incinerator near the city of Matarr. In this paper we present the baseline levels of PCDDs/Fs and PCBs in this population before the incinerator started functioning.
MATERIAL AND METHODS The study was carried out in Mataro, a Mediterranean city of approximately 100,000 inhabitants, 25 km north of Barcelona. A total of 201 adults (100 males and 101 females), aged between 18 and 69 years, were randomly selected from the municipal list of inhabitants in March-June 1995. Two groups were selected. The first was a group of 104 "potentially exposed" individuals living in districts near the incinerator (less than 1 kin). The second was a group of 97 "unexposed" individuals, frequency matched to the first by sex and age-group,
living in districs far (about 4 km)
from the plant. No
socioeconomic differences were found between them. Whole blood samples (about 50 ml) were collected by routine veinpuncture for 198 of the 201 participating subjects.
Blood sample for each individual was
collected in two chemically clean 25 ml glass bottles and kept frozen at -30 °C until the time of analysis in a laboratory in Germany. All techniques for extraction, clean up and analysis by gas chomatography-mass spectometry, have been previously described (7) and were perfomed by a laboratory that meets the WHO certification standards. For analysis of PCDDs, PCDFs and PCBs whole blood samples were pooled in 10 groups: 5 from the "potentially exposed " and 5 from the "unexposed" subjects.
Within both the exposed and unexposed
groups (See foot note of Table 1), there were 3 subgroups of males subdivided by age (18-29 years, 30-49 years and 50-69 years) and 2 subgroups of females (18-39 years and 40-69 years). Concentration in both the 5 sex and age subgroups of"exposed" and the 5 subgroups of"unexposed" are presented together because all subjects represent the same background level of exposure. This means that each value in the tables represents the arithmetic mean of two measurements from the pooled blood samples of 34, 38, 27, 47 and 52 subjects respectively. Results were obtained of the concentration of the main PCDD and PCDF congeners, for the total PCDDs and PCDFs, and toxic equivalents according to the International Dioxin Toxic Equivalent (I-TEQ) factor methods (8) . For PCBs, results on the concentrations of tri, tetra, penta, hexa and hepta PCBs were obtained. Values of TEQ do not include I-TEQs for PCBs. Given that the analysis was based on the value of pooled blood samples, SDs are not known, and statistical differences between groups of sex and age can not be tested.
RESULTS The concentration (Table 1) of total PCDDs increased with age in both sexes and was slightly higher in females than in males. The total level of PCDDs was 505.7 ppt for males and 739.0 ppt for females. Almost
421 77 % of the total PCDD was contribuited by OctaCDD. The total level of PCDFs was 26.7 ppt in males and 28.8 ppt in females. Small differences were found by sex and age-group. HexaCDF was the main contributor to total PCDF. TetraCDD and TetraCDF are the least abundant isomers. Toxic equivalents (I-TEQs) were 14.7 in females and 12.5 in males. It increased with age in both sexes. PCDDs which represent 95 % of the total PCDDs and PCDFs contributed 68.5 % of the total I-TEQ (Table 2) while PCDFs which represent only 5 % of the total dioxins and furans, contributed 31.5 %. The most important toxic isomers were HexaCDD, PentaCDF and PentaCDD. The blood concentration of total PCB (Table 3) was slightly higher in males (2.02 mg/1) than in females (1.58 mg/1). In both sexes the concentration of PCB increased with age.
DISCUSSION There exists very limited data on levels of PCDDs, PCDFs and PCBs in the human population of countries in the south of Europe.
Matar6 is a mixed residential-industrial city on the Mediterranean sea. Textile
manufacture is the main industrial activity, and, besides the new incinerator, there are no other known industrial sources of exposure to dioxins. Another advantage of our study is that blood levels were measured in population sample of the city.
a
randomly selected general
One limitation is that using pooled blood data, statistical differences
between sex and age can not be tested. However
it is considered that such studies can rapidly and
economically provide useful public health information on average population dioxin levels. (9). Total levels of PCDDs found in Mataro (507.8 ppt) were similar to those found in a sample of male blood donors, aged 19 to 55 years, with no known occupational exposure to dioxin in Madrid (515.3 ppt) (10). However, the concentration of PCDFs in Mataro ( 26.7 ppt) was lower than in Madrid (66.7 ppt). The relative contribution of different congeners to total PCDD and PCDF in Mataro and the increasing concentration with age, are similar to other studies in other countries (6,11) and Madrid (10). The total I-TEQ (12) level found in males in Mataro (12.5 ppt), is among the lowest in the world, even when compared to levels in population from geographical areas without environmental contamination,like Baikalsk in
Siberia, and Hanoi in Vietnam (6,9 ppt). It is between 3 and 4 times lower than the
concentration levels observed in population from exposed areas in the south of Vietnam, that were sprayed with Agent Orange by the U.S.A. military forces. Among industrialized countries, dioxin blood concentrations are considered to be geographically fairly uniform (4) and toxics equivalents in the general population are between 20 and 40 ppt, lipids (13). One possible explication is that these low levels found in Spain are due to the absence of industrial sources of exposure, combined with a Mediterranean diet low in animal fat. Dietary intake of foods of animal origin is the most important source (> 90 % ) of the accumulation of dioxins in the human body and is was estimated that dairy products accounted for about half of the 2,3,7,8 TCDD intake (14). Mediterranean diet typically included small amounts of dairy products. The proportion of lipids provided by butter and other dairy products was 4 times higher in some north European countries
422 than in Spain (15). Another explanation for the lower levels observed in Matar6 compared to north European countries is that samples were collected at different times. During the last few years a tendency of decreasing PCDDs and PCDFs levels has been observed in some industrialized countries. The level of I-TEQ in samples from the population of Germany was in 1992 lower than in 1989 (16).
Samples from Madrid ( 10 ) and from
Matar6 have beeen taken several years after. The highest site of concentration of dioxins in mammals are the liver and adipose tissues (1). The background exposure to dioxins by sexes are considered very similar (4). We found, however, that the levels of PCDDs and PCDFs in females are slightly higher than in males. Despite the fact that nursing infants lower the body level of dioxins in women (1) it could be possible that the greater quantity of adipose tissues in women with a high prevalence of obesity, could explain the higher levels of dioxins found. The blood concentration levels of PCBs found in the general population of Mataro are similar to the concentration observed in population from non-exposed geographical areas (2). In another study in the south of Spain (17) in polulation living in an area of high exposure to organochlorine compounds from agriculture, where the concentration of PCBs in blood taken from mothers during delivery was measured, the concentration of PCB138 was 1.44 mg/1 and for PCBI80 was 2.12 mg/1. These levels are higher than those found in Mataro. A(~KNOWLEDGEMENTS: To O. Piipke for the laboratory analysis of blood samples, Cristina Mas for her important work in the study office, and Gisela Carretero and Roser Fernandez for their field work.
423 Table 1. Blood levels (ppt/g fat weight) of PCDDs and PCDFs by sex and age-group. Male(n=99) a
Female (n---99)b
Total
(n=l~ Conseners
18-29c
30-49d
50-69e
Total
18-39f
40--698 Total
2,3,7,8 TetraCDD
1.5
1.5
1.9
1.6
0.8
2.3
1.5
1.
1,2,3,7,8 PentaCDD
3.2
4.7
5.8
4.5
4.7
6.1
5.4
4.
1,2,3,4,7,8; 1,2,3,6,7,8; 1,2,3,7,8,9 HexaCDD
27.2
38.8
43.3
36.4
35.9
51.5
43.7
39.
1,2,3,4,6,7,8 HeptaCDD
46.4
62.2
70.1
59.6
72.6
99.1
85.8
70.
OetaCDD
335.6
429.0
452.3
405.7
516.6
688.4
602.5
484.
TotalCDD
413.9
536.2
573.4
507.8
630.5
847.4
739.0
600.
1.1
1.3
1.2
1.2
1.4
1.3
1.
2,3,7,8-TetraCDF 1,2,3,7,8 2,3,4,7,8 PentaCDF
5.2
5.5
6.8
5.9
5.0
.8.3
6.6
6.
1,2,3,4,7,8 1,2,3,6,7,8 1,2,3,7,8,9 2,3,4,6,7,8 HexaCDF
9.6
9.3
11.2
10.0
10.0
13.0
11.5
10.
1,2,3,4,6,7,8 1,2,3,4,7,8,9 HeptaCDF
7.9
6.8
6.8
7.2
6.2
7.8
7.0
7.
OctaCDF
2.5
2.5
2.5
2.5
2.5
2.2
2.4
2.
Total CDF
25.2
25.2
28.6
26.8
24.9
32.6
28.8
27.
Total CDD+CDF
439.1
561.4
602.0
534.6
655.4
880.0
767.8
627.
10.0
12.5
15.0
12.5
11.7
17.6
14.7
13.
I-TEQ
a 6 individual analyses; b 4 individual analyses c 2 individual analyses, 1 pool, n= 20; 1 pool, n=14 d 2 individual analyses, 1 pool, n= 16; 1 pool, n= 22 e 2 individual analyses, 1 pool, n =12; 1 pool, n= 15
f I pool, n--26; 1 pool, n= 21. g 1 pool, n=28; 1 pool, n= 24.
424 Table 2. Contribution (%) of each isomer to the total I-TEQ by sex.
Congeners
I-TEF
I-TEQ Male
Female
Total
2,3,7,8 Te~aCDD
1
12.8
10.4
11.8
1,2,3,7,8Pent~DD
0,5
18.0
18.4
18.2
1,2,3,4,7,8 1,2,3,6,7,8 1,2,3,7,8,9HexaCDD
0,1
29.0
29.9
29.4
1,2,3,4,6,7,8 HeptaCDD
0,01
5.O
6.0
5.4
OctaCDD
0,001
3.3
4.3
3.8
68.l
69.0
68.5
TotalCDD 2,3,7,8-Te~DF
0,1
0.6
0.7
0.6
1,2,3,7,8 2,3,4,7,8Pent~DF
0,05 0,5
22.5
21.7
22.2
1,2,3,4,7,8 1,2,3,6,7,8 1,2,3,7,8,9 2,3,4,6,7,8Hex~DF
0,1
8.0
7.9
8.0
1,2,3,4,6,7,8 1,2,3,4,7,8,9 HeptaCDF
0,01
0.8
0.7
0.7
OctaCDF
0,001
0.0
0.0
0.0
31.9
31.0
31.5
100.0
100.0
100.0
TotalCDF TotalCDD+CDF
425 Table 3. Blood levels (mg/l) of PCBs sex and age-group.
Male
Female
Total
Congeners 18-29 30-49 50-69 Total 18-39 40-69 Total
2.4.4'-Tri-PCB28
nd
nd
nd
nd
nd
2.2'.5.5'-Tetra PCB52
nd
nd
nd
nd
nd
2.2'.4.5.5'-Penta-PCB101
0.09
0.06
0.04
2.2'.3.4.4'.5'-Hexa-PCB138
0.39
0 . 5 3 0.67
2.2'.4.4'.5.5'-Hexa-PCB153
0.52
0.79
0.89
2.2'.3.4.4'.5.5'-HeptaPCB180
0.43
0.70
0 . 8 1 0.65
0.39
PCBTotal
1.48
2.13
2.46
1 . 2 9 1 . 8 7 1 . 5 8 1.85
0.06
0.01
0.04
0 . 5 3 0.34
0 . 5 1 0.42
0.49
0 . 7 3 0.49
0.69
0.59
0.67
0.60
0.49
0.59
2.02
0 . 0 1 0.02
REFERENCES:
(1) Lilienfeld DE, Gallo MA. 2,4-D, 2,4,5-T, and 2,3,7,8-TCDD: An overview. Epidemiol Rev 11, 28-58 (1989). (2) Polyehlorinated biphenyls and Terphenyls (second edition) (Enviromental health criteria 140), International programme on chemical safety (IPCS). WHO, p. 199-203 (1993). (3) Cleverly DH, Morrison RM, Riddle BL, Kellan RG. Regulatory analysis of pollutant emissions, including polychlorinated dibenzo-p-dioxins (CODs) and dibenzofurans (CDFs), from the stacks of municipal waste conbustors. Chemosphere 18, 1143-1153 (1989). (4) US Environmental Protection Agency, Office of Research and Development. Health Assessment Document for 2,3,7,8-Tetraehlorodibenzeno-p-Dioxin (TCDD) and Related Compounds. Volume III of III. Washington, DC: US Government Printing Oftiee, Report n* EPA/600/BP92/001c. (1994). (5) Greim H, Csanady G, Filser JG, Kreuzer P, Sehwarz L, Wolff T. Biomarkers as tools in human health risk assessment. Clin Chem 41, (12 Pt 2), 1804-1808 (1995). (6) Sehecter A, Fiirst P. Fttrst C, Papke O, Ball M, Ryan JJ, Hoang Dirda Cau, Le Cao Dai, Hoang Trong Quynh, H.Q. Cuong, Nguyen Thi Ngoe Phuong, Pham Hoang Phiet, Albert Beim, Constable J, Startin J, Samedy M, Yit Kim Seng. Chlorinated dioxins and dibenzofurans in human tissue fi'om general populations: A selective review. Environ Health Perspect Supplements 102, 159-170 (1994).
426 (7) P~ipkeO, Ball M, Lis ZA, Scheunert K. Determination ofPCDD/PCDF m whole blood from persons involved in fire incidents. Cbemosphere 20, 959-966 (1990). (8) Eadon G, Kaminsky L, Silkworth J, et al. Calculation of 2.3.7.8-TCDD equivalent concentrations of complex environmental contaminant mixtures. Environ Health Perspect 70, 221-227 (1986). (9) Schecter A, Dai LC, Thuy LTB, Quynh HT, Minh DQ, Cau HD, et al. Agent orange and the Vietnamese: The persistence of elevated Dioxin levels in human tissues. Am J Public Health 85, 516522 (1995). (10)Jim6nez B, Hern~dez LM, Gonz~lez MJ. Levels of PCDDs ans PCDFs in serum samples of non exposed individuals living in Madrid (Spain). Organohalogen compounds 26, 249-253 (1995). (ll)PleB T, Scheneider F, Steiner M, Karmaus W. Impact of body-mass-index and age on the bloodconcentration of PCDD/PCDF of adults and children. Chemosphere 26, 1109-1118 (1993). (12)Bimbaum LS, Devito MJ. Use of toxic equivalency factors for risk assessment for dioxins and related compounds. Toxicology 105, 391-401 (1995). (13) Schecter AJ. Dioxins and related chemicals in humans and the environment. In: Gallo M. Scheuplein ILl, Vander Heijden KA, eds. Biological basis for risk assessment of Dioxins and related compounds. Cold Spring Harbor, NY: Cold Spring Harbor p. 169-213. Banbury Report 35 (1991). (14) Huisman M, Eerenstein SE, Koopman-Esseboom C, Brouwer M, Fidler V, Muskier FA, Sauer PJ, Boersma ER. Perinatal exposure to polychlorinated biphenyls and dioxins through dietary intake. Chemosphere 31(10), 4273-87 (1995). (15) Riboli E, P6quignot G, Repetto F, Axerio M, Raymond L, Boffetta P, Zubiri A, Del Moral A, Est6ve J, Tuyns AJ. A comparative study of smoking, drinkings and dietary habits in population samples in France, Italy, Spain and Switzerland. Rev Epid6m. et Sant6 Publ 36, 151-165 (1988). (16) Papke O., Ball M., Lis A. PCDD/PCDF in Humans. A 1993 Update of background data. Chemosphere 29, 2355-2360 (1994). (17) Marttnez E, Romanos A, Praena M, Repetto M, Martinez D. Organochlorine compound: blood levels in mother, newborn babies and breast and bottle fed babies. A study in the province of Huelva. Anales Espafioles de Pediatria 39, 46-52 (1993).