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Serum levels of PCDDs, PCDFs and PCBs in non-occupationally exposed population groups living near two incineration plants in Tuscany, Italy
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Chemosphere 72 (2008) 25–33 www.elsevier.com/locate/chemosphere
Serum levels of PCDDs, PCDFs and PCBs in non-occupationally exposed population groups living near two incineration plants in Tuscany, Italy Elena De Felip a,*, Annalisa Abballe a, Francesco Casalino c, Alessandro di Domenico a, Pierangela Domenici b, Nicola Iacovella a, Anna Maria Ingelido a, Elisabetta Pretolani b, Maurizio Spagnesi b a
Istituto Superiore di Sanita`, Viale Regina Elena 299, 00161 Roma, Italy U.F. Igiene e Sanita` Pubblica, Az. USL 9 Grosseto, 58022 Follonica, Italy c Servizio Trasfusionale Ospedale Sant’Andrea, Az. USL 9 Grosseto, 58025 Massa Marittima, Italy b
Received 11 June 2007; received in revised form 19 February 2008; accepted 19 February 2008 Available online 14 April 2008
Abstract A pilot study was carried out in Tuscany, Italy, to provide preliminary information on the concentrations of polychlorinated dibenzodioxins (PCDDs), polychlorinated dibenzofurans (PCDFs), dioxin-like polychlorobiphenyls (DL-PCBs), and selected non-dioxin-like PCBs (NDL-PCBs) in groups of subjects living in the vicinity of two incineration plants. Seventy-four volunteers were enrolled from areas identified as under a potential impact from incinerator emissions and from not exposed areas. No significant differences were observed between subjects living in the two types of areas. Total concentrations of PCDDs, PCDFs, and DL-PCBs resulted to be in the range 23–30 pg WHO–TEQ g1, lipid base, for subjects in the 27–54 year age groups, while concentrations increased to 40–44 pgTEQ g1 for the two 55–67 year age groups. The levels of PCDDs and PCDFs were in good agreement with those observed for unexposed population groups in Italy, while the contribution to total TEQ from DL-PCBs was appreciably higher than those currently observed in the general population in Italy and other countries. As to NDL-PCBs, serum levels of the six ‘‘indicator” congeners were in the range 240–300 ng g1, lipid base, for subjects in the 27– 54 year age groups. A raise in NDL-PCB body burden (430–470 ng g1, lipid base) was observed for the two 55+ year age groups, in agreement with the expected age-dependent increase. The findings from this study do not show an incremental exposure to PCDDs and PCDFs in the samples from subjects living around the two incineration plants, whereas PCB congener profiles in all samples suggest a possible impact on the area of interest of industrial activities from near industrial settlements. Ó 2008 Elsevier Ltd. All rights reserved. Keywords: Dioxins; PCDDs; PCDFs; PCBs; Human exposure; Incineration emissions
1. Introduction Two incineration plants, distant about 10 km from each other and located in the province of Grosseto, Tuscany, have been cause of concern for the residential communities living in the surrounding areas. The first plant (Valpiana, *
Corresponding author. Tel.: +39 06 49902904; fax: +39 06 49387068. E-mail address: [email protected] (E. De Felip).
0045-6535/$ - see front matter Ó 2008 Elsevier Ltd. All rights reserved. doi:10.1016/j.chemosphere.2008.02.046
generally processing about 18 000 tons/year), burned municipal solid waste and, although discontinuously, sanitary waste between 1976 and 2000 (within this period, activities were discontinued from December 1989 to December 1991 to install a post-combustion chamber). The second plant (Casone), located within a wide industrial area, burned municipal solid waste (mainly Refuse Derived Fuel) and waste wood between 1997 and 2003. It has burned clean wood since 2003. Its capacity is of 120 000 tons/year.
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Local people’s concerns about a possible exposure to pollutants released from incineration activities were mainly related to polychlorodibenzodioxins (PCDDs) and polychlorodibenzofurans (PCDFs), since both plants were old generation incinerators and had been in function before the present regulation entered into force. In Italy, Regions have been allowed to work out their own implementation plans giving the existing incineration plants a few years to comply with the emission limit of 0.1 ng TEQ Nm3 fixed by the European Directive EC/2000/76, or to close. People concerns prompted the local authorities to carry out an investigation to assess a possible incremental exposure of the communities resident in the areas near the two plants, with respect to communities living in nearby areas at presumable background level of exposure. Exposure assessment was carried out through biomonitoring, by measuring the serum levels of the 17 toxic congeners of PCDDs and PCDFs, and of the 12 dioxin-like polychlorobiphenyls (DL-PCBs). The non-dioxin-like (NDL) PCB congeners in serum was also characterized, by analysing the six congeners referred to as ‘‘indicators” (PCBs 28, 52, 101, 138, 153 and 180) traditionally used to estimate the total PCB content of a matrix. Biomonitoring is at present considered the most powerful tool to determine human exposure to persistent pollutants (Needham et al., 2007), and the best dose-metric for the purpose of an adequate risk assessment. This particularly applies to those persistent organic pollutants that are families of various congeners with different toxicological activities and/or potencies, as in the case of PCDDs, PCDFs and PCBs (Needham et al., 2005). Congener-specific metabolic rates lead in fact to different bioaccumulation rates, and determine congener-specific profiles in human tissues which may differ from what observed in the environmental and dietary matrices humans are exposed to (De Felip et al., 2004a). The present study among a number of studies launched in response to public concerns and carried out in different countries to determine if exposure to incinerator emissions may be responsible for an increase in PCDD, PCDF and DL-PCB body burden in people living in the vicinity of the plants. While the majority of the studies has not provided evidence of an increase in contaminant body burden in people exposed to incinerator emissions (Deml et al., 1996; Evans et al., 2000; Chen et al., 2004; Agramunt et al., 2005; Reis et al., 2007a; Yang et al., 2007), the few studies that have found such an increase attributed the differences in exposure to regular consumption of locally produced foods (Fierens et al., 2007; Pascal et al., 2007). Indeed, food intake is known to account for over 90% of general population exposure, while the contribution of occupational and environmental sources in building up PCDD and PCDF body burden is less clear (Pless-Mulloli et al., 2005). Moreover, the relationship between levels of these contaminants in incinerator emissions and increase in body burden of the exposed population has never been adequately characterized. It has been estimated by some
authors (Fierens et al., 2003) that ‘‘a 10% rise in body burden is likely to occur only when dioxin emissions exceed 5 ng TEQ Nm3”, in the case of exposed population regularly consuming local food, but a number of variables may intervene (e.g. length of exposure, local conditions) and likely affect this estimate in an unpredictable way. In Italy, the application of Directives EC/94/67 and EC/ 2000/76 has progressively reduced the impact from incineration. The amounts of PCDDs, PCDFs and DL-PCBs emitted into the environment before compliance with the stringent emission standards set by the aforesaid Directives cannot be readily estimated but, as in other European countries (Pirard et al., 2005), it may be assumed that potentially large amounts of PCDDs and PCDFs have been released into the environment. Especially in the case of a lack of an adequate quantitative information on the amounts of PCDDs, PCDFs, and PCBs biomonitoring represents the most powerful and decisive tool to answer people concerns. Moreover, because of their high persistency in biological tissues (half lives in humans P3 years), PCDD, PCDF, and PCB levels in human tissues may be considered to reflect medium to long term exposure (Pless-Mulloli et al., 2005). The present study, prompted and supported by local authorities (Provincia di Grosseto), was carried out on pooled serum samples, with the main aim to rapidly and economically respond to public concerns on a specific exposure situation, and to obtain preliminary data to orient an eventual further investigation.
2. Materials and methods 2.1. Selection of study areas The analysis of atmospheric dispersion, obtained through the application of a model (CALPUFF Modelyng System, Scire et al., 1999) that simulated the atmospheric dispersion from each plant using meteorological and topographic information, allowed the identification of the areas at potential exposure and the areas at presumable no impact from the facilities. Potentially exposed areas (classified as ‘‘near”) resulted to be within a distance of about 3 km from each facility, whereas areas at a distance greater than 5 km could be considered as not exposed (or ‘‘distant”). This kind of distinction is in agreement with what indicated in other studies (Andre et al., 2004; Reis et al., 2007b) that identified the distance of 5 km as the distance beyond which no impact from an incineration plant could be observed. In addition to ‘‘near” and ‘‘distant” areas, an area at an intermediate distance (3–5 km) from the Casone plant, located in the peripheral part of the town of Follonica, was also deemed to be of interest due to its population density, comparatively higher than that of the other areas. The areas included in the study were therefore as follows (Fig. 1):
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– Valpiana (area V), near the incineration plant of Valpiana; – Massa Marittima (area M), distant from the incineration plant of Valpiana; – Scarlino (area S), near the incineration plant of Casone; – Follonica (area FL), distant from the incineration plant of Casone; – Follonica (area F), at an intermediate distance (3–5 km) from the incineration plant of Casone.
2.2. Enrolling of subjects Seventy-four subjects resident in the aforesaid areas were enrolled by local sanitary authorities belonging to the Azienda Unita` Sanitaria Locale (AUSL) 9 of Grosseto, settled in Follonica (Ufficio Igiene e Sanita` Pubblica), and in Massa Marittima (Servizio Trasfusionale dell’Ospedale S. Andrea), a municipality a few kilometres north–east of Valpiana. Sampling began in May 2005 and ended in December 2006. Enrollment criteria were a residence in the areas of at least 20 years and, for women, not to have breast-fed in the last 20 years. The reference age-range was of indicatively 30–50 years. Fifty-four of the enrolled subjects were of age between 27 and 54 years. Twenty subjects of higher age (55–67 years) were also enrolled, ten living in the area of Scarlino, near the incineration plant of
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Casone, ten living in the area of Follonica distant from the aforesaid incineration plant. 2.3. Blood withdrawal and pooling of specimens Prior to blood withdrawal, each participant signed an informed consent form and compiled a questionnaire aimed to ascertain that no occupational exposure to the contaminants of interest had occurred, and to gather information on sociodemographic factors, smoking habits, medical history, use of drugs, and reproductive/nursing history in women. The questionnaire contained detailed questions on dietary habits. Consumption of local foods was also investigated. About 30 ml blood were withdrawn from each participant and centrifuged to obtain serum. Individual specimens were pooled to yield the eight serum samples shown in Table 1. To obtain pools, equal amounts of serum from 8 to 10 individuals were combined together. As dioxin body burden is known to be age-dependent (Wittsiepe et al., 2000), pools were formed so that a similar age distribution (27–54 years) was guaranteed in all of them. Overlapping of age distribution was also ensured for the two pools of greater mean age. Table 1 shows the characteristics of pools obtained for analysis. One pool was formed for each of the studied areas
Fig. 1. Map of the investigated area, in the province of Grosseto (Tuscany, Italy), indicating the position of the two incineration plants (Casone and Valpiana), the surrounding areas (Follonica, Scarlino, Valpiana and Massa Marittima), the industrial pole of Piombino, and the power plant of Torre del Sale.
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Table 1 Characteristics of pooled serum samples from the donors enrolled in the five studied areas Serum pools Pool
F
FL
FLA
S
SA
V
M1
M2
Geographic area
Follonica 3–5 km from incinerator 9
Follonica >5 km from incinerator 9
Follonica >5 km from incinerator 10
Scarlino
Scarlino
Valpiana
8
10
8
Massa Marittima 10
Massa Marittima 10
38 27–54 2 F, 7 M
42 30–52 9M
60 55–64 1 F, 9 M
44 36–51 3 F, 5 M
60 55–67 3 F, 7 M
44 38–53 4 F, 4 M
44 30–53 3 F, 7 M
41 29–54 3 F, 7 M
Number of donors in the pool Age, mean (years) Age, range (years) Gender
(pools identified as F, FL, S, V), except in the case of Massa Marittima (two pools, M1 and M2), because of the larger number of available blood donors. The two pools from subjects at greater mean age were identified as FLA and SA. 2.4. Analysis The procedure used for the analytical determination was adapted from previously published methods (Pa¨pke et al., 1989; De Felip et al., 2004b). Serum pools were spiked with 13 C-labelled PCDD, PCDF and PCB internal standards and liquid/liquid extracted with n-hexane. The amount of the extracted lipids was gravimetrically determined. Clean-up was performed by a multi-step procedure (Ingelido et al., 2007). The analytes quantified were the 17 2,3,7,8-chlorosubstituted PCDD and PCDF congeners, the 12 DL-PCBs (‘‘non-ortho” congeners: PCBs 77, 81, 126, and 169; and ‘‘mono-ortho” congeners: PCBs 105, 114, 118, 123, 156, 157, 167, and 189). The NDL-PCBs analysed were the six ‘‘indicator” congeners (PCBs 28, 52, 101, 138, 153, 180), plus PCBs 128, 141, 170, 183, 187, 194, 206, and 209. The PCDD, PCDF, and DL-PCB levels determined in the serum samples were converted into toxic equivalents (TEQ) by the use of the WHO–TEF system (Van den Berg et al., 1998). To estimate cumulative results, half of the limit of determination (LD) was entered in calculations for each non-detected congener (medium bound approach). Analytical reliability was warranted by the analysis of frequent blind replicates and blanks. Accuracy was assessed by in-house reference matrices fortified with 13C-labelled PCDD, PCDF and PCB congeners at concentrations close to background levels. 3. Results and discussion The characteristics of the studied population are shown in Table 1. Subjects in all groups were well matched regarding body mass index. The analysis of administered questionnaires, specifically aimed to estimate the total consumption of fats of animal origin, revealed a substantial overlapping of alimentary habits. Cheese and fish resulted to be the only categories for which a
contribution of local origin could be of some relevance, while the other food categories resulted to be unrelated to local production. Regarding both fish and dairy products consumption, no statistically significative differences were found between the eight pools (Kruskal–Wallis test, p > 0.01) and between subjects living near the incineration plants and controls (Mann–Whitney U test, p > 0.01). Table 2 shows the results of congener-specific analytical determinations carried out on PCDDs, PCDFs, and nonortho- and mono-ortho-PCBs in the pooled serum samples. Cumulative values, obtained from converting analytical congener-specific data expressed in pg g1, lipid base, to pg WHO–TEQ g1, lipid base, are also summarized in the table. PCDD and PCDF serum levels in the enrolled subjects were in the range 7.7–9.3 pg WHO–TE g1, lipid base, for the 27–54 year age groups. In the two pools FLA and SA (mean age about 60 years), the same value of 11 pg WHO–TEQ g1, lipid base, was found. Cumulative concentrations of PCDDs, PCDFs, and DL-PCBs in pg WHO–TEQ g1, lipid base, ranged from 23 to 30 in the 27–54 year age groups. In the two 55+ year age groups, values of 40 (FLA) and 44 (SA) were observed. Levels of NDL-PCBs, as the sum of the fourteen congeners of major abundance in human blood, were in the range of 300–380 ng g1, lipid base, in the 27–54 year age groups, and of 590–640 in the two 55+ year age groups (Table 3). The sum of the six ‘‘indicator” congeners was 240–290 and 430–470 ng g1, lipid base, respectively. For both the age ranges studied, no significant differences in serum TEQ and in NDL-PCB levels were observed between groups from the areas under suspected impact from waste incineration with respect to those assumed to be at background exposure. The higher TEQ values observed in the two 55+ year age groups is compatible with the age dependent increase of PCDD, PCDF, and PCB body burden normally observed (Consonni et al., 2006). Also for NDL-PCBs, the higher levels observed in the older subject groups are compatible with an age-dependent increase observed in other studies (Jursa et al., 2006; Harden et al., 2007; Hue et al., 2007). For comparative purposes, results of previous biomonitoring studies carried out by our group on the same fami-
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Table 2 PCDD, PCDF, and DL-PCB concentrations (pg g1 lipid base) in human pooled serum samples from the five studied areas in the province of Grosseto, Tuscanya Analytes
F
FL
FLAb
S
SAb
V
M1
M2
PCDDs and PCDFs 2,3,7,8-T4CDD 1,2,3,7,8-P5CDD 1,2,3,4,7,8-H6CDD 1,2,3,6,7,8-H6CDD 1,2,3,7,8,9-H6CDD 1,2,3,4,6,7,8-H7CDD O8CDD 2,3,7,8-T4CDF 1,2,3,7,8-P5CDF 2,3,4,7,8-P5CDF 1,2,3,4,7,8-H6CDF 1,2,3,6,7,8-H6CDF 1,2,3,7,8,9-H6CDF 2,3,4,6,7,8-H6CDF 1,2,3,4,6,7,8-H7CDF 1,2,3,4,7,8,9-H7CDF O8CDF
<1c 2.5 1.6 6.9 1.7 12 110 <1 <1 5.4 3.7 2.5 <1 <1 4.1 <1 <3
<1 2.3 2.2 8.2 1.5 10 78 <1 <1 6.2 2.8 2.7 <1 <1 3.8 <1 <2
1.0 3.4 3.7 11 2.0 16 120 <1 <1 8.2 4.8 3.8 <1 <1 4.5 <1 <3
<1 2.6 1.7 9.7 1.7 13 110 <1 <1 6.2 4.1 3.2 <1 <2 4.9 <2 <4
<1 3.1 2.8 11 1.6 15 110 <1 <1 8.9 4.4 4.2 <1 <1 3.0 <1 <2
1.1 2.5 1.8 7.1 1.4 8.8 85 <1 <1 7.3 3.0 3.2 <1 <1 5.7 <1 <3
<1 3.0 2.1 9.0 1.7 12 140 <1 <1 6.7 3.2 3.2 <1 <1 3.7 <1 <2
<1 2.6 1.7 8.9 1.8 13 110 <1 <1 6.4 3.2 2.7 <1 <1 3.5 <1 <2
Dioxin-like PCBs, non-ortho PCB-77 PCB-81 PCB-126 PCB-169
<40 1.7 55 51
<50 1.7 59 63
<40 2.3 120 85
<60 <2 49 66
<40 2.7 120 98
<40 1.9 76 64
<40 1.7 77 63
<40 1.5 72 48
Dioxin-like PCBs, mono-ortho PCB-105 3100 PCB-114 1100 PCB-118 17 000 PCB-123 280 PCB-156 12 000 PCB-157 2500 PCB-167 3800 PCB-189 1500
2900 960 17 000 220 11 000 2200 3700 1700
5800 1600 30 000 520 19 000 3700 6500 2800
2500 810 14 000 240 12 000 2400 3200 1800
6600 2100 37 000 490 23 000 4900 7400 3100
6400 1500 30 000 500 14 000 2800 4500 1700
4200 1300 22 000 350 14 000 2800 4400 1800
4200 1000 22 000 360 10 000 2000 3900 1400
WHO–TEQd P (PCDDs+PCDFs) P P(non-ortho PCBs) (mono-ortho PCBs) Total TEQ
8.0 6.5 9.6 24
11 12 16 40
8.6 5.6 9.5 24
11 13 20 44
9.3 8.2 13 30
9.1 8.3 12 29
8.5 7.7 9.5 26
7.7 6.0 9.8 23
Values rounded off to two figures. a Follonica, 3–5 km from Casone incinerator (F), Follonica more than 5 km from Casone incinerator (FL), Scarlino (S), Valpiana (V), Massa Marittima (M). b Mean age of donors, 60 years. c The sign < indicates limit of determination (LD). d 1998 WHO–TEQ (Van den Berg et al., 1998). Medium bound approach.
lies of analytes are shown in Table 4. All studies refer to Italian women of reproductive age (overall age range: 18– 40 years) from Rome and Venice (De Felip et al., 2004b; Abballe et al., 2005, 2008). A good agreement is observed between the cumulative TEQ concentrations in serum of PCDDs, PCDFs, and DL-PCBs assessed in this study and those measured in serum and milk from the examined Italian women. As to the separate contributions of PCDDs and PCDFs and DL-PCBs to the overall TEQ values, it is noteworthy to highlight that, while dioxin levels are in the same order of magnitude as that observed in Italian women, DL-PCB concentrations are at the upper end of the range of observed values, and contribution to total TEQ from DL-PCBs (both non-ortho and mono-ortho
congeners) is consistently higher than that currently observed in our studies and in most investigations carried out on the general population in other countries (Van Leeuween and Malisch, 2002; De Felip et al., 2004b; Consonni et al., 2006; Wittsiepe et al., 2007). In fact, from available literature data (EU Dioxin Exposure and Health Data, 1999; Buckland et al., 2001; Koppen et al., 2002; Malisch and Van Leeuwen, 2003; Harden et al., 2004; Costopoulou et al., 2006), it may be observed that the ratio: 1
½DL-PCBsðTEQÞ ½PCDDs þ PCDFsðTEQÞ
is generally included in the range 0.6–1.2, whereas in the present study the ratio is in the range 1.7–3 with the upper end value associated to older population groups.
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Table 3 Selected PCB congener concentrations (ng g1, lipid base) and distribution in human serum pools from five areas of Tuscany regiona Analytes PCB-28 PCB-52 PCB-101 PCB-128 PCB-138 PCB-141 PCB-153 PCB-170 PCB-180 PCB-183 PCB-187 PCB-194 PCB-206 PCB-209 P (PCBs)d,e P6 e 14(PCBs)
FL
FLAb
S
SAb
V
M1
M2
<5 <0.6 <1 <0.4 62 <0.4 86 20 86 12 25 7.3 1.7 4.2
<5 <0.6 <1 <0.4 60 <0.5 89 25 93 12 26 9.3 1.8 4.1
<4 <0.5 <1 0.75 100 <0.4 150 43 180 22 55 22 5.0 10
<7 <0.7 <2 <0.6 54 <0.6 81 25 96 9.5 23 9.2 1.8 4.7
<5 <0.5 1.1 0.77 110 0.45 160 40 200 22 67 21 5.9 8.4
<5 <0.6 <1 0.41 82 <0.4 110 28 100 13 29 11 2.1 4.3
<4 <0.5 <1 0.53 76 <0.4 110 27 100 13 30 10 2.2 7.3
<5 <0.6 <1 0.42 70 <0.4 90 19 80 13 25 5.8 2.1 4.7
240 300
250 320
430 590
240 300
470 640
300 380
290 380
240 310
F c
Values rounded off to two figures. a Follonica, 3–5 km from Casone incinerator (F), Follonica more than 5 km from Casone incinerator (FL), Scarlino (S), Valpiana (V), Massa Marittima (M). b Mean age of donors, 60 years. c The sign < indicates limit of determination (LD). d Sum of PCBs 28, 52, 101, 138, 153, and 180. e Medium bound approach.
Table 4 PCDD, PCDF, NDL-PCB congener concentrations (pg WHO–TEQ g1, lipid base) and distribution in human serum and milk from different Italian areas
Matrix Year of sampling Age range (years) P d,e P(PCDDs + PCDFs) (non-ortho PCBs)d,e P (mono-ortho PCBs)d,e P (dioxin-like PCBs)d,e Total TEQd,e P e,f,g 6(PCBs)
This study
This study
Romea
Romeb
Romec
Venicec
Serum 2006 30–54 7.7–9.3 5.6–8.3 9.5–13 15–21 23–30 240–290
Serum 2006 55+ 11 12–13 16–20 28–33 40–44 430–470
Serum 2001 18–40 8.9 3.9 4.8 8.8 18 250–340
Serum 2004 20–40 – – – – – 210
Milk 2001 28–40 9.4 4.2 6.8 11 20 200
Milk 2000 21–38 12–15 6.5–8.8 6.9–11 13–20 25–34 200–320
Values rounded off to two figures. a De Felip et al. (2004a,b). b Porpora et al. (2006). c Abballe et al. (2008). d 1998 WHO–TEQ (Van den Berg et al., 1998). e Medium bound approach. f Sum of PCBs 28, 52, 101, 138, 153 and 180. g ng g1, lipid base.
As to NDL-PCBs (only the sums of the six ‘‘indicator” congeners are reported in Table 4 to allow an easier comparison between studies), it may be observed that the serum levels assessed in this study are in the upper part of the range of values measured in our previous studies. NDL-PCB levels appear to be significantly correlated with DL-PCB levels (Fig. 2), expressed either in analytical units or in toxicity equivalent units, this indicating that sources of contamination for both groups of PCBs were possibly the same. NDL-congener profiles of all pools, restricted to the three most abundant PCB congeners 138, 153, and 180, are shown in Fig. 3. The relative con-
tribution of the more chlorinated PCB 180, with the longest half-life among the most abundant NDL-PCBs (Ryan et al., 1993), results to be consistently higher than that observed in our previous studies (De Felip et al., 2004a,b; Porpora et al., 2006; Ingelido et al., 2007) and in the majority of studies carried out on samples of the general population in other countries (Gabrio et al., 2000; Pauwels et al., 2001; Demers et al., 2002; Marchand et al., 2004). In summary, our findings are in agreement with results obtained in other similar studies (Deml et al., 1996; Evans et al., 2000; Chen et al., 2004; Agramunt et al., 2005; Reis
Σ12(DL-PCBs, ng g-1 lipid base)
90
y = (0.1754 ± 0.0053) x 70
50
30 200
250
300
350
6(NDL-PCB,
400
450
500
Σ12(DL-PCBs, pg WHO-TEQ g-1 lipid base)
E. De Felip et al. / Chemosphere 72 (2008) 25–33
31
y = (0.0681 ± 0.0011) x 30
20
10 200
ng g-1 lipid base)
250
300
6(NDL-PCB,
350
400
450
500
ng g-1 lipid base)
Fig. 2. Correlation between DL-PCBs (Van den Berg et al., 1998) and NDL-PCBs, as sum of the six ‘‘indicators”: PCBs 28, 52, 101, 138, 153, and 180. DL-PCBs are reported in analytical units (left box) and in toxicity equivalent units (right box); in both cases, correlation is high (R = 0.96, pR 0.001, F 1,7 = 81, pF = 0.0001, and R = 0.99, pR 0.001, F1,7 = 320, pF 0.0001, respectively) between DL-PCBs and NDL-PCBs, this likely indicating a common source of exposure. The correlation is still significant when the results relative to the two most contaminated pools (55+ age groups) are omitted (pF = 0.03 and pF = 0.005, respectively).
Fig. 3. Selected NDL-PCB congener profiles in pooled human serum samples from the five studied areas in Tuscany, and from a group of nulliparous women (40 subjects, mean age, 26.9 years) from Rome (Porpora et al., 2006). Relative ratios between the three most abundant congeners PCBs 138, 153, and 180 observed in pooled serum samples from Tuscany are quite different from that observed in the group of women from Rome and in the majority of studies carried out on general population in other countries. Relative contribution of PCB 180 results to be consistently higher than that observed in our studies carried out on the Italian general population.
et al., 2007a; Yang et al., 2007) that did not provide evidence of a significant increase in PCDD and PCDF body burden in subjects living in the vicinity of incineration plants, in the absence of a regular consumption of local animal product. The observed increase of the TEQ contribution from DL-PCB congeners to total TEQ, together with the significant correlation between DL- and NDL-PCBs, and the relative enrichment in blood levels of some highly persistent PCB congeners (DL-PCBs and PCB 180) suggest that a (past) exposure of the whole area to PCBs may have occurred. This hypothesis is worthwhile of a further exploration, also aimed to assess the possible environmental impact of the moderately distant electric power plant of Torre del Sale and/or of the industrial pole of Piombino on the areas we examined in the present study.
Acknowledgements This study has been supported by Provincia di Grosseto and Fondazione Monte dei Paschi di Siena. The analysis of the atmospheric dispersion of the pollutants has been carried out by Dr. Andrea Corti and Dr. Paolo Giambini, Universita` degli Studi di Siena. The authors wish to thank Mariangela Gucci and Nicla Vigetti (U.F. Igiene e Sanita` Pubblica Az. USL 9 Grosseto, Follonica), Sandra Venturi and Moreno Viligiardi (Ospedale S. Andrea, Massa Marittima) for their technical contribution. References Abballe, A., Ballard, T.J., De Felip, E., Dellatte, E., Ferri, F., Fulgenzi, A.R., Iacovella, N., Ingelido, A.M., Malisch, R., Miniero, R.,
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Chemosphere 72 (2008) 25–33 www.elsevier.com/locate/chemosphere
Serum levels of PCDDs, PCDFs and PCBs in non-occupationally exposed population groups living near two incineration plants in Tuscany, Italy Elena De Felip a,*, Annalisa Abballe a, Francesco Casalino c, Alessandro di Domenico a, Pierangela Domenici b, Nicola Iacovella a, Anna Maria Ingelido a, Elisabetta Pretolani b, Maurizio Spagnesi b a
Istituto Superiore di Sanita`, Viale Regina Elena 299, 00161 Roma, Italy U.F. Igiene e Sanita` Pubblica, Az. USL 9 Grosseto, 58022 Follonica, Italy c Servizio Trasfusionale Ospedale Sant’Andrea, Az. USL 9 Grosseto, 58025 Massa Marittima, Italy b
Received 11 June 2007; received in revised form 19 February 2008; accepted 19 February 2008 Available online 14 April 2008
Abstract A pilot study was carried out in Tuscany, Italy, to provide preliminary information on the concentrations of polychlorinated dibenzodioxins (PCDDs), polychlorinated dibenzofurans (PCDFs), dioxin-like polychlorobiphenyls (DL-PCBs), and selected non-dioxin-like PCBs (NDL-PCBs) in groups of subjects living in the vicinity of two incineration plants. Seventy-four volunteers were enrolled from areas identified as under a potential impact from incinerator emissions and from not exposed areas. No significant differences were observed between subjects living in the two types of areas. Total concentrations of PCDDs, PCDFs, and DL-PCBs resulted to be in the range 23–30 pg WHO–TEQ g1, lipid base, for subjects in the 27–54 year age groups, while concentrations increased to 40–44 pgTEQ g1 for the two 55–67 year age groups. The levels of PCDDs and PCDFs were in good agreement with those observed for unexposed population groups in Italy, while the contribution to total TEQ from DL-PCBs was appreciably higher than those currently observed in the general population in Italy and other countries. As to NDL-PCBs, serum levels of the six ‘‘indicator” congeners were in the range 240–300 ng g1, lipid base, for subjects in the 27– 54 year age groups. A raise in NDL-PCB body burden (430–470 ng g1, lipid base) was observed for the two 55+ year age groups, in agreement with the expected age-dependent increase. The findings from this study do not show an incremental exposure to PCDDs and PCDFs in the samples from subjects living around the two incineration plants, whereas PCB congener profiles in all samples suggest a possible impact on the area of interest of industrial activities from near industrial settlements. Ó 2008 Elsevier Ltd. All rights reserved. Keywords: Dioxins; PCDDs; PCDFs; PCBs; Human exposure; Incineration emissions
1. Introduction Two incineration plants, distant about 10 km from each other and located in the province of Grosseto, Tuscany, have been cause of concern for the residential communities living in the surrounding areas. The first plant (Valpiana, *
Corresponding author. Tel.: +39 06 49902904; fax: +39 06 49387068. E-mail address: [email protected] (E. De Felip).
0045-6535/$ - see front matter Ó 2008 Elsevier Ltd. All rights reserved. doi:10.1016/j.chemosphere.2008.02.046
generally processing about 18 000 tons/year), burned municipal solid waste and, although discontinuously, sanitary waste between 1976 and 2000 (within this period, activities were discontinued from December 1989 to December 1991 to install a post-combustion chamber). The second plant (Casone), located within a wide industrial area, burned municipal solid waste (mainly Refuse Derived Fuel) and waste wood between 1997 and 2003. It has burned clean wood since 2003. Its capacity is of 120 000 tons/year.
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Local people’s concerns about a possible exposure to pollutants released from incineration activities were mainly related to polychlorodibenzodioxins (PCDDs) and polychlorodibenzofurans (PCDFs), since both plants were old generation incinerators and had been in function before the present regulation entered into force. In Italy, Regions have been allowed to work out their own implementation plans giving the existing incineration plants a few years to comply with the emission limit of 0.1 ng TEQ Nm3 fixed by the European Directive EC/2000/76, or to close. People concerns prompted the local authorities to carry out an investigation to assess a possible incremental exposure of the communities resident in the areas near the two plants, with respect to communities living in nearby areas at presumable background level of exposure. Exposure assessment was carried out through biomonitoring, by measuring the serum levels of the 17 toxic congeners of PCDDs and PCDFs, and of the 12 dioxin-like polychlorobiphenyls (DL-PCBs). The non-dioxin-like (NDL) PCB congeners in serum was also characterized, by analysing the six congeners referred to as ‘‘indicators” (PCBs 28, 52, 101, 138, 153 and 180) traditionally used to estimate the total PCB content of a matrix. Biomonitoring is at present considered the most powerful tool to determine human exposure to persistent pollutants (Needham et al., 2007), and the best dose-metric for the purpose of an adequate risk assessment. This particularly applies to those persistent organic pollutants that are families of various congeners with different toxicological activities and/or potencies, as in the case of PCDDs, PCDFs and PCBs (Needham et al., 2005). Congener-specific metabolic rates lead in fact to different bioaccumulation rates, and determine congener-specific profiles in human tissues which may differ from what observed in the environmental and dietary matrices humans are exposed to (De Felip et al., 2004a). The present study among a number of studies launched in response to public concerns and carried out in different countries to determine if exposure to incinerator emissions may be responsible for an increase in PCDD, PCDF and DL-PCB body burden in people living in the vicinity of the plants. While the majority of the studies has not provided evidence of an increase in contaminant body burden in people exposed to incinerator emissions (Deml et al., 1996; Evans et al., 2000; Chen et al., 2004; Agramunt et al., 2005; Reis et al., 2007a; Yang et al., 2007), the few studies that have found such an increase attributed the differences in exposure to regular consumption of locally produced foods (Fierens et al., 2007; Pascal et al., 2007). Indeed, food intake is known to account for over 90% of general population exposure, while the contribution of occupational and environmental sources in building up PCDD and PCDF body burden is less clear (Pless-Mulloli et al., 2005). Moreover, the relationship between levels of these contaminants in incinerator emissions and increase in body burden of the exposed population has never been adequately characterized. It has been estimated by some
authors (Fierens et al., 2003) that ‘‘a 10% rise in body burden is likely to occur only when dioxin emissions exceed 5 ng TEQ Nm3”, in the case of exposed population regularly consuming local food, but a number of variables may intervene (e.g. length of exposure, local conditions) and likely affect this estimate in an unpredictable way. In Italy, the application of Directives EC/94/67 and EC/ 2000/76 has progressively reduced the impact from incineration. The amounts of PCDDs, PCDFs and DL-PCBs emitted into the environment before compliance with the stringent emission standards set by the aforesaid Directives cannot be readily estimated but, as in other European countries (Pirard et al., 2005), it may be assumed that potentially large amounts of PCDDs and PCDFs have been released into the environment. Especially in the case of a lack of an adequate quantitative information on the amounts of PCDDs, PCDFs, and PCBs biomonitoring represents the most powerful and decisive tool to answer people concerns. Moreover, because of their high persistency in biological tissues (half lives in humans P3 years), PCDD, PCDF, and PCB levels in human tissues may be considered to reflect medium to long term exposure (Pless-Mulloli et al., 2005). The present study, prompted and supported by local authorities (Provincia di Grosseto), was carried out on pooled serum samples, with the main aim to rapidly and economically respond to public concerns on a specific exposure situation, and to obtain preliminary data to orient an eventual further investigation.
2. Materials and methods 2.1. Selection of study areas The analysis of atmospheric dispersion, obtained through the application of a model (CALPUFF Modelyng System, Scire et al., 1999) that simulated the atmospheric dispersion from each plant using meteorological and topographic information, allowed the identification of the areas at potential exposure and the areas at presumable no impact from the facilities. Potentially exposed areas (classified as ‘‘near”) resulted to be within a distance of about 3 km from each facility, whereas areas at a distance greater than 5 km could be considered as not exposed (or ‘‘distant”). This kind of distinction is in agreement with what indicated in other studies (Andre et al., 2004; Reis et al., 2007b) that identified the distance of 5 km as the distance beyond which no impact from an incineration plant could be observed. In addition to ‘‘near” and ‘‘distant” areas, an area at an intermediate distance (3–5 km) from the Casone plant, located in the peripheral part of the town of Follonica, was also deemed to be of interest due to its population density, comparatively higher than that of the other areas. The areas included in the study were therefore as follows (Fig. 1):
E. De Felip et al. / Chemosphere 72 (2008) 25–33
– Valpiana (area V), near the incineration plant of Valpiana; – Massa Marittima (area M), distant from the incineration plant of Valpiana; – Scarlino (area S), near the incineration plant of Casone; – Follonica (area FL), distant from the incineration plant of Casone; – Follonica (area F), at an intermediate distance (3–5 km) from the incineration plant of Casone.
2.2. Enrolling of subjects Seventy-four subjects resident in the aforesaid areas were enrolled by local sanitary authorities belonging to the Azienda Unita` Sanitaria Locale (AUSL) 9 of Grosseto, settled in Follonica (Ufficio Igiene e Sanita` Pubblica), and in Massa Marittima (Servizio Trasfusionale dell’Ospedale S. Andrea), a municipality a few kilometres north–east of Valpiana. Sampling began in May 2005 and ended in December 2006. Enrollment criteria were a residence in the areas of at least 20 years and, for women, not to have breast-fed in the last 20 years. The reference age-range was of indicatively 30–50 years. Fifty-four of the enrolled subjects were of age between 27 and 54 years. Twenty subjects of higher age (55–67 years) were also enrolled, ten living in the area of Scarlino, near the incineration plant of
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Casone, ten living in the area of Follonica distant from the aforesaid incineration plant. 2.3. Blood withdrawal and pooling of specimens Prior to blood withdrawal, each participant signed an informed consent form and compiled a questionnaire aimed to ascertain that no occupational exposure to the contaminants of interest had occurred, and to gather information on sociodemographic factors, smoking habits, medical history, use of drugs, and reproductive/nursing history in women. The questionnaire contained detailed questions on dietary habits. Consumption of local foods was also investigated. About 30 ml blood were withdrawn from each participant and centrifuged to obtain serum. Individual specimens were pooled to yield the eight serum samples shown in Table 1. To obtain pools, equal amounts of serum from 8 to 10 individuals were combined together. As dioxin body burden is known to be age-dependent (Wittsiepe et al., 2000), pools were formed so that a similar age distribution (27–54 years) was guaranteed in all of them. Overlapping of age distribution was also ensured for the two pools of greater mean age. Table 1 shows the characteristics of pools obtained for analysis. One pool was formed for each of the studied areas
Fig. 1. Map of the investigated area, in the province of Grosseto (Tuscany, Italy), indicating the position of the two incineration plants (Casone and Valpiana), the surrounding areas (Follonica, Scarlino, Valpiana and Massa Marittima), the industrial pole of Piombino, and the power plant of Torre del Sale.
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Table 1 Characteristics of pooled serum samples from the donors enrolled in the five studied areas Serum pools Pool
F
FL
FLA
S
SA
V
M1
M2
Geographic area
Follonica 3–5 km from incinerator 9
Follonica >5 km from incinerator 9
Follonica >5 km from incinerator 10
Scarlino
Scarlino
Valpiana
8
10
8
Massa Marittima 10
Massa Marittima 10
38 27–54 2 F, 7 M
42 30–52 9M
60 55–64 1 F, 9 M
44 36–51 3 F, 5 M
60 55–67 3 F, 7 M
44 38–53 4 F, 4 M
44 30–53 3 F, 7 M
41 29–54 3 F, 7 M
Number of donors in the pool Age, mean (years) Age, range (years) Gender
(pools identified as F, FL, S, V), except in the case of Massa Marittima (two pools, M1 and M2), because of the larger number of available blood donors. The two pools from subjects at greater mean age were identified as FLA and SA. 2.4. Analysis The procedure used for the analytical determination was adapted from previously published methods (Pa¨pke et al., 1989; De Felip et al., 2004b). Serum pools were spiked with 13 C-labelled PCDD, PCDF and PCB internal standards and liquid/liquid extracted with n-hexane. The amount of the extracted lipids was gravimetrically determined. Clean-up was performed by a multi-step procedure (Ingelido et al., 2007). The analytes quantified were the 17 2,3,7,8-chlorosubstituted PCDD and PCDF congeners, the 12 DL-PCBs (‘‘non-ortho” congeners: PCBs 77, 81, 126, and 169; and ‘‘mono-ortho” congeners: PCBs 105, 114, 118, 123, 156, 157, 167, and 189). The NDL-PCBs analysed were the six ‘‘indicator” congeners (PCBs 28, 52, 101, 138, 153, 180), plus PCBs 128, 141, 170, 183, 187, 194, 206, and 209. The PCDD, PCDF, and DL-PCB levels determined in the serum samples were converted into toxic equivalents (TEQ) by the use of the WHO–TEF system (Van den Berg et al., 1998). To estimate cumulative results, half of the limit of determination (LD) was entered in calculations for each non-detected congener (medium bound approach). Analytical reliability was warranted by the analysis of frequent blind replicates and blanks. Accuracy was assessed by in-house reference matrices fortified with 13C-labelled PCDD, PCDF and PCB congeners at concentrations close to background levels. 3. Results and discussion The characteristics of the studied population are shown in Table 1. Subjects in all groups were well matched regarding body mass index. The analysis of administered questionnaires, specifically aimed to estimate the total consumption of fats of animal origin, revealed a substantial overlapping of alimentary habits. Cheese and fish resulted to be the only categories for which a
contribution of local origin could be of some relevance, while the other food categories resulted to be unrelated to local production. Regarding both fish and dairy products consumption, no statistically significative differences were found between the eight pools (Kruskal–Wallis test, p > 0.01) and between subjects living near the incineration plants and controls (Mann–Whitney U test, p > 0.01). Table 2 shows the results of congener-specific analytical determinations carried out on PCDDs, PCDFs, and nonortho- and mono-ortho-PCBs in the pooled serum samples. Cumulative values, obtained from converting analytical congener-specific data expressed in pg g1, lipid base, to pg WHO–TEQ g1, lipid base, are also summarized in the table. PCDD and PCDF serum levels in the enrolled subjects were in the range 7.7–9.3 pg WHO–TE g1, lipid base, for the 27–54 year age groups. In the two pools FLA and SA (mean age about 60 years), the same value of 11 pg WHO–TEQ g1, lipid base, was found. Cumulative concentrations of PCDDs, PCDFs, and DL-PCBs in pg WHO–TEQ g1, lipid base, ranged from 23 to 30 in the 27–54 year age groups. In the two 55+ year age groups, values of 40 (FLA) and 44 (SA) were observed. Levels of NDL-PCBs, as the sum of the fourteen congeners of major abundance in human blood, were in the range of 300–380 ng g1, lipid base, in the 27–54 year age groups, and of 590–640 in the two 55+ year age groups (Table 3). The sum of the six ‘‘indicator” congeners was 240–290 and 430–470 ng g1, lipid base, respectively. For both the age ranges studied, no significant differences in serum TEQ and in NDL-PCB levels were observed between groups from the areas under suspected impact from waste incineration with respect to those assumed to be at background exposure. The higher TEQ values observed in the two 55+ year age groups is compatible with the age dependent increase of PCDD, PCDF, and PCB body burden normally observed (Consonni et al., 2006). Also for NDL-PCBs, the higher levels observed in the older subject groups are compatible with an age-dependent increase observed in other studies (Jursa et al., 2006; Harden et al., 2007; Hue et al., 2007). For comparative purposes, results of previous biomonitoring studies carried out by our group on the same fami-
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Table 2 PCDD, PCDF, and DL-PCB concentrations (pg g1 lipid base) in human pooled serum samples from the five studied areas in the province of Grosseto, Tuscanya Analytes
F
FL
FLAb
S
SAb
V
M1
M2
PCDDs and PCDFs 2,3,7,8-T4CDD 1,2,3,7,8-P5CDD 1,2,3,4,7,8-H6CDD 1,2,3,6,7,8-H6CDD 1,2,3,7,8,9-H6CDD 1,2,3,4,6,7,8-H7CDD O8CDD 2,3,7,8-T4CDF 1,2,3,7,8-P5CDF 2,3,4,7,8-P5CDF 1,2,3,4,7,8-H6CDF 1,2,3,6,7,8-H6CDF 1,2,3,7,8,9-H6CDF 2,3,4,6,7,8-H6CDF 1,2,3,4,6,7,8-H7CDF 1,2,3,4,7,8,9-H7CDF O8CDF
<1c 2.5 1.6 6.9 1.7 12 110 <1 <1 5.4 3.7 2.5 <1 <1 4.1 <1 <3
<1 2.3 2.2 8.2 1.5 10 78 <1 <1 6.2 2.8 2.7 <1 <1 3.8 <1 <2
1.0 3.4 3.7 11 2.0 16 120 <1 <1 8.2 4.8 3.8 <1 <1 4.5 <1 <3
<1 2.6 1.7 9.7 1.7 13 110 <1 <1 6.2 4.1 3.2 <1 <2 4.9 <2 <4
<1 3.1 2.8 11 1.6 15 110 <1 <1 8.9 4.4 4.2 <1 <1 3.0 <1 <2
1.1 2.5 1.8 7.1 1.4 8.8 85 <1 <1 7.3 3.0 3.2 <1 <1 5.7 <1 <3
<1 3.0 2.1 9.0 1.7 12 140 <1 <1 6.7 3.2 3.2 <1 <1 3.7 <1 <2
<1 2.6 1.7 8.9 1.8 13 110 <1 <1 6.4 3.2 2.7 <1 <1 3.5 <1 <2
Dioxin-like PCBs, non-ortho PCB-77 PCB-81 PCB-126 PCB-169
<40 1.7 55 51
<50 1.7 59 63
<40 2.3 120 85
<60 <2 49 66
<40 2.7 120 98
<40 1.9 76 64
<40 1.7 77 63
<40 1.5 72 48
Dioxin-like PCBs, mono-ortho PCB-105 3100 PCB-114 1100 PCB-118 17 000 PCB-123 280 PCB-156 12 000 PCB-157 2500 PCB-167 3800 PCB-189 1500
2900 960 17 000 220 11 000 2200 3700 1700
5800 1600 30 000 520 19 000 3700 6500 2800
2500 810 14 000 240 12 000 2400 3200 1800
6600 2100 37 000 490 23 000 4900 7400 3100
6400 1500 30 000 500 14 000 2800 4500 1700
4200 1300 22 000 350 14 000 2800 4400 1800
4200 1000 22 000 360 10 000 2000 3900 1400
WHO–TEQd P (PCDDs+PCDFs) P P(non-ortho PCBs) (mono-ortho PCBs) Total TEQ
8.0 6.5 9.6 24
11 12 16 40
8.6 5.6 9.5 24
11 13 20 44
9.3 8.2 13 30
9.1 8.3 12 29
8.5 7.7 9.5 26
7.7 6.0 9.8 23
Values rounded off to two figures. a Follonica, 3–5 km from Casone incinerator (F), Follonica more than 5 km from Casone incinerator (FL), Scarlino (S), Valpiana (V), Massa Marittima (M). b Mean age of donors, 60 years. c The sign < indicates limit of determination (LD). d 1998 WHO–TEQ (Van den Berg et al., 1998). Medium bound approach.
lies of analytes are shown in Table 4. All studies refer to Italian women of reproductive age (overall age range: 18– 40 years) from Rome and Venice (De Felip et al., 2004b; Abballe et al., 2005, 2008). A good agreement is observed between the cumulative TEQ concentrations in serum of PCDDs, PCDFs, and DL-PCBs assessed in this study and those measured in serum and milk from the examined Italian women. As to the separate contributions of PCDDs and PCDFs and DL-PCBs to the overall TEQ values, it is noteworthy to highlight that, while dioxin levels are in the same order of magnitude as that observed in Italian women, DL-PCB concentrations are at the upper end of the range of observed values, and contribution to total TEQ from DL-PCBs (both non-ortho and mono-ortho
congeners) is consistently higher than that currently observed in our studies and in most investigations carried out on the general population in other countries (Van Leeuween and Malisch, 2002; De Felip et al., 2004b; Consonni et al., 2006; Wittsiepe et al., 2007). In fact, from available literature data (EU Dioxin Exposure and Health Data, 1999; Buckland et al., 2001; Koppen et al., 2002; Malisch and Van Leeuwen, 2003; Harden et al., 2004; Costopoulou et al., 2006), it may be observed that the ratio: 1
½DL-PCBsðTEQÞ ½PCDDs þ PCDFsðTEQÞ
is generally included in the range 0.6–1.2, whereas in the present study the ratio is in the range 1.7–3 with the upper end value associated to older population groups.
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E. De Felip et al. / Chemosphere 72 (2008) 25–33
Table 3 Selected PCB congener concentrations (ng g1, lipid base) and distribution in human serum pools from five areas of Tuscany regiona Analytes PCB-28 PCB-52 PCB-101 PCB-128 PCB-138 PCB-141 PCB-153 PCB-170 PCB-180 PCB-183 PCB-187 PCB-194 PCB-206 PCB-209 P (PCBs)d,e P6 e 14(PCBs)
FL
FLAb
S
SAb
V
M1
M2
<5 <0.6 <1 <0.4 62 <0.4 86 20 86 12 25 7.3 1.7 4.2
<5 <0.6 <1 <0.4 60 <0.5 89 25 93 12 26 9.3 1.8 4.1
<4 <0.5 <1 0.75 100 <0.4 150 43 180 22 55 22 5.0 10
<7 <0.7 <2 <0.6 54 <0.6 81 25 96 9.5 23 9.2 1.8 4.7
<5 <0.5 1.1 0.77 110 0.45 160 40 200 22 67 21 5.9 8.4
<5 <0.6 <1 0.41 82 <0.4 110 28 100 13 29 11 2.1 4.3
<4 <0.5 <1 0.53 76 <0.4 110 27 100 13 30 10 2.2 7.3
<5 <0.6 <1 0.42 70 <0.4 90 19 80 13 25 5.8 2.1 4.7
240 300
250 320
430 590
240 300
470 640
300 380
290 380
240 310
F c
Values rounded off to two figures. a Follonica, 3–5 km from Casone incinerator (F), Follonica more than 5 km from Casone incinerator (FL), Scarlino (S), Valpiana (V), Massa Marittima (M). b Mean age of donors, 60 years. c The sign < indicates limit of determination (LD). d Sum of PCBs 28, 52, 101, 138, 153, and 180. e Medium bound approach.
Table 4 PCDD, PCDF, NDL-PCB congener concentrations (pg WHO–TEQ g1, lipid base) and distribution in human serum and milk from different Italian areas
Matrix Year of sampling Age range (years) P d,e P(PCDDs + PCDFs) (non-ortho PCBs)d,e P (mono-ortho PCBs)d,e P (dioxin-like PCBs)d,e Total TEQd,e P e,f,g 6(PCBs)
This study
This study
Romea
Romeb
Romec
Venicec
Serum 2006 30–54 7.7–9.3 5.6–8.3 9.5–13 15–21 23–30 240–290
Serum 2006 55+ 11 12–13 16–20 28–33 40–44 430–470
Serum 2001 18–40 8.9 3.9 4.8 8.8 18 250–340
Serum 2004 20–40 – – – – – 210
Milk 2001 28–40 9.4 4.2 6.8 11 20 200
Milk 2000 21–38 12–15 6.5–8.8 6.9–11 13–20 25–34 200–320
Values rounded off to two figures. a De Felip et al. (2004a,b). b Porpora et al. (2006). c Abballe et al. (2008). d 1998 WHO–TEQ (Van den Berg et al., 1998). e Medium bound approach. f Sum of PCBs 28, 52, 101, 138, 153 and 180. g ng g1, lipid base.
As to NDL-PCBs (only the sums of the six ‘‘indicator” congeners are reported in Table 4 to allow an easier comparison between studies), it may be observed that the serum levels assessed in this study are in the upper part of the range of values measured in our previous studies. NDL-PCB levels appear to be significantly correlated with DL-PCB levels (Fig. 2), expressed either in analytical units or in toxicity equivalent units, this indicating that sources of contamination for both groups of PCBs were possibly the same. NDL-congener profiles of all pools, restricted to the three most abundant PCB congeners 138, 153, and 180, are shown in Fig. 3. The relative con-
tribution of the more chlorinated PCB 180, with the longest half-life among the most abundant NDL-PCBs (Ryan et al., 1993), results to be consistently higher than that observed in our previous studies (De Felip et al., 2004a,b; Porpora et al., 2006; Ingelido et al., 2007) and in the majority of studies carried out on samples of the general population in other countries (Gabrio et al., 2000; Pauwels et al., 2001; Demers et al., 2002; Marchand et al., 2004). In summary, our findings are in agreement with results obtained in other similar studies (Deml et al., 1996; Evans et al., 2000; Chen et al., 2004; Agramunt et al., 2005; Reis
Σ12(DL-PCBs, ng g-1 lipid base)
90
y = (0.1754 ± 0.0053) x 70
50
30 200
250
300
350
6(NDL-PCB,
400
450
500
Σ12(DL-PCBs, pg WHO-TEQ g-1 lipid base)
E. De Felip et al. / Chemosphere 72 (2008) 25–33
31
y = (0.0681 ± 0.0011) x 30
20
10 200
ng g-1 lipid base)
250
300
6(NDL-PCB,
350
400
450
500
ng g-1 lipid base)
Fig. 2. Correlation between DL-PCBs (Van den Berg et al., 1998) and NDL-PCBs, as sum of the six ‘‘indicators”: PCBs 28, 52, 101, 138, 153, and 180. DL-PCBs are reported in analytical units (left box) and in toxicity equivalent units (right box); in both cases, correlation is high (R = 0.96, pR 0.001, F 1,7 = 81, pF = 0.0001, and R = 0.99, pR 0.001, F1,7 = 320, pF 0.0001, respectively) between DL-PCBs and NDL-PCBs, this likely indicating a common source of exposure. The correlation is still significant when the results relative to the two most contaminated pools (55+ age groups) are omitted (pF = 0.03 and pF = 0.005, respectively).
Fig. 3. Selected NDL-PCB congener profiles in pooled human serum samples from the five studied areas in Tuscany, and from a group of nulliparous women (40 subjects, mean age, 26.9 years) from Rome (Porpora et al., 2006). Relative ratios between the three most abundant congeners PCBs 138, 153, and 180 observed in pooled serum samples from Tuscany are quite different from that observed in the group of women from Rome and in the majority of studies carried out on general population in other countries. Relative contribution of PCB 180 results to be consistently higher than that observed in our studies carried out on the Italian general population.
et al., 2007a; Yang et al., 2007) that did not provide evidence of a significant increase in PCDD and PCDF body burden in subjects living in the vicinity of incineration plants, in the absence of a regular consumption of local animal product. The observed increase of the TEQ contribution from DL-PCB congeners to total TEQ, together with the significant correlation between DL- and NDL-PCBs, and the relative enrichment in blood levels of some highly persistent PCB congeners (DL-PCBs and PCB 180) suggest that a (past) exposure of the whole area to PCBs may have occurred. This hypothesis is worthwhile of a further exploration, also aimed to assess the possible environmental impact of the moderately distant electric power plant of Torre del Sale and/or of the industrial pole of Piombino on the areas we examined in the present study.
Acknowledgements This study has been supported by Provincia di Grosseto and Fondazione Monte dei Paschi di Siena. The analysis of the atmospheric dispersion of the pollutants has been carried out by Dr. Andrea Corti and Dr. Paolo Giambini, Universita` degli Studi di Siena. The authors wish to thank Mariangela Gucci and Nicla Vigetti (U.F. Igiene e Sanita` Pubblica Az. USL 9 Grosseto, Follonica), Sandra Venturi and Moreno Viligiardi (Ospedale S. Andrea, Massa Marittima) for their technical contribution. References Abballe, A., Ballard, T.J., De Felip, E., Dellatte, E., Ferri, F., Fulgenzi, A.R., Iacovella, N., Ingelido, A.M., Malisch, R., Miniero, R.,
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