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Body Loadings and Health Risk Assessment of Polychlorinated


Dibenzo-p-dioxins and Dibenzofurans at an Intensive Electronic
Waste Recycling Site in China

Janet K.Y. ,Guan Hua Xing,Ying Xu,Ying Liang,Ling Xuan Chen,Sheng Chun Wu,Chris K. C.
Wong,Clement K. M. Leung,# andMing H. Wong*
Croucher Institute for Environmental Sciences, and Department of Biology, Hong Kong Baptist University,
G/F, Block 5, Low-Rise Buildings, 32 Renfrew Road, Kowloon Tong, Hong Kong SAR, People's Republic
of China, State Key Laboratory of Freshwater Ecology and Biotechnology, Institute of Hydrobiology,
Chinese Academy of Sciences, 430072, Wuhan, Hubei Province, People's Republic of China, Luqiao
Hospital of Traditional Chinese Medicine, 318050, Taizhou Region, Zhejiang Province, People's Republic
of China, Centre for Disease Control and Prevention of Luqiao District, 318050, Taizhou Region, Zhejiang
Province, People's Republic of China, and IVF Centre Limited, Hong Kong Sanatorium and Hospital, 2
Village Road, Happy Valley, Hong Kong SAR, People's Republic of China
Environ. Sci. Technol., 2007, 41 (22), pp 76687674
DOI: 10.1021/es071492j
Publication Date (Web): October 6, 2007
Copyright 2007 American Chemical Society

Abstract
This study is one of the very few investigating the dioxin body burden of a group of child-bearing-
aged women at an electronic waste (e-waste) recycling site (Taizhou, Zhejiang Province) (24 2.83
years of age, 40% were primiparae) and a reference site (Lin'an city, Zhejiang Province, about 245
km away from Taizhou) (24 2.35 years of age, 100% were primiparae) in China. Five sets of
samples (each set consisted of human milk, placenta, and hair) were collected from each site. Body
burdens of people from the e-waste processing site (human milk, 21.02 13.81 pg WHO-TEQ1998/g
fat (World Health Organization toxic equivalency 1998); placenta, 31.15 15.67 pg WHO-TEQ1998/g
fat; hair, 33.82 17.74 pg WHO-TEQ1998/g dry wt) showed significantly higher levels of
polychlorinated dibenzo-p-dioxins and polychlorinated dibenzofurans (PCDD/Fs) than those from the
reference site (human milk, 9.35 7.39 pg WHO-TEQ1998/g fat; placenta, 11.91 7.05 pg WHO-
TEQ1998/g fat; hair, 5.59 4.36 pg WHO-TEQ1998/g dry wt) and were comparatively higher than other
studies. The difference between the two sites was due to e-waste recycling operations, for example,
open burning, which led to high background levels. Moreover, mothers from the e-waste recycling
site consumed more foods of animal origin. The estimated daily intake of PCDD/Fs within 6 months
by breast-fed infants from the e-waste processing site was 2 times higher than that from the
reference site. Both values exceeded the WHO tolerable daily intake for adults by at least 25 and 11
times, respectively. Our results implicated that e-waste recycling operations cause prominent
PCDD/F levels in the environment and in humans. The elevated body burden may have health
implications for the next generation.

Introduction

Electronic waste, e-waste or waste electrical and electronic equipment (WEEE) defined by the
European Community Directive 2002/96/EC, is a waste type consisting of any broken or unwanted
electrical or electronic appliance. Obsolete e-waste has become a serious problem. The average
lifespan of computers in developed countries has dropped from 6 years in 1997 to 2 years in 2005
(1). According to the State Environmental Protection Administration of China, 70% of worldwide e-
waste has been sent to China (2). In the western United States, up to 80% of the e-waste collected
for recycling is exported to Asia, of which 90% is sent to China due to lower environmental standards
and cheaper labor (3). Moreover, in China alone, 4 million PCs are discarded annually (4).

There are several e-waste processing sites in China, of which Taizhou region in Zhejiang Province
and Guiyu town in Guangdong Province are the most intensive (2). The recycling is done by
rudimentary methods, which include burning wire piles to recover metals, melting circuit boards over
coal grills to release valuable chips, cooking computer casings to remove combustible plastics and
isolate metals, and extracting metals in acid baths (5, 6). Our previous studies conducted in Guiyu
showed that persistent organic pollutants (POPs) and heavy metals caused serious contamination in
air, soil, sediment, and freshwater (511). Dioxins (PCDD/Fs), i.e., polychlorinated dibenzo-p-dioxins
(PCDDs) and polychlorinated dibenzofurans (PCDFs), are of particular concern as burning of solid
waste releases large amounts of these toxic compounds (12). Open burning and acid leaching were
found to release the largest amount of dioxins of all e-waste operation processes (8), and open
dumping sites are potential sources of dioxins due to uncontrolled burning (13). Therefore,
uncontrolled burning and disposal of waste could impose serious threats to the health of workers
and local residents. The World Health Organization (WHO) has coordinated exposure studies on
dioxins in human milk since 1987 (1416). Human milk samples were collected from several regions
in China to determine levels of dioxins (1721). However, information concerning human body
burdens of dioxins at e-waste recycling sites is limited. Thus, the major objective of this study is to
carry out a health risk assessment to investigate the body burdens of dioxins of local residents at
Taizhou region.

Experimental Section

Sampling Site Description. The e-waste recycling site is Taizhou region (TZ) which is located in
Zhejiang Province, eastern China (Figure 1). Taizhou is situated at the central coastal section of
Zhejiang (28 N latitude and 122 E longitude) and has a coastline of 745 km, accounting for 28% of
that of Zhejiang Province (22). E-waste recycling activities are mainly executed in a city called
Luqiao situated in the southern part of Taizhou, with a total area of 274 km2 and a population of
400000.

Figure 1 Sampling locations at Zhejiang Province, China.

The e-waste recycling activities in Taizhou started in the late 1970s and dealt mostly with
domestically generated e-waste (23). In the early 1990s, Taizhou began to process imported e-
waste. Currently, the imported e-waste contributes 90% of the total and originates mainly from
Japan, the United States, Western European countries, and Russia. In recent years, Taizhou has
become one of the main receivers of e-waste in China. It mainly receives scrap metals, obsolete
electric capacitors, household appliances, electric generators, and cable wires. The annual volume
of dismantled e-waste has exceeded 2.2 million metric tons, and the sales volume has reached 4
billion Chinese Yuans (approximate U.S. $5.16 hundred million). Forty thousand people are working
in the e-waste recycling sector. Most of the recycling operations involve open air burning, acid
leaching, and physical dismantling by hammer, chisel, screw driver, and bare hand.
The reference site is Lin'an city (HZ) (30 N latitude and 118 E longitude), Hangzhou prefecture,
Zhejiang Province (24). It is about 245 km away from Taizhou. Lin'an is situated inland, at the
northern part of Hangzhou, and it is a city with a land area of 3127 km2 and a population of 520000.

Study Population. Human milk, placenta, and hair samples were collected at the two study sites
from 10 women who gave birth between August and December 2005. These 10 women were
selected randomly under the conditions that they had been living in the study site for at least 2 years
and they were willing to donate sufficient amounts of hair and milk for the chemical analysis. A set of
specimens was collected from each individual. The donors were accessed through Luqiao Hospital
of Traditional Chinese Medicine, Lin'an Hospital of Traditional Chinese Medicine, and the local
Centers for Disease Control and Prevention. Before the collection of specimens, the donors
completed an informed consent. A survey on their personal characteristics was conducted (see
Table S1, Supporting Information).

Data Collection. Socio-demographic data and food consumption habits of the study population were
obtained from face-to-face interviews and semiquantitative food intake questionnaires, respectively.
During the interview, the donors answered questions modified from the second round of WHO's
PCDDs, PCDFs, and PCBs exposure study (14). The intakes of different types of food were
assessed (see Table S2, Supporting Information). Weekly intake (g/week) for each food item was
computed for each individual. Dietary change over the course of pregnancy was ignored. The
response rate was 100%.

Sample Collection. Human milk (100 mL) was collected from each donor when the infant was 45
days old. The sample was manually expressed and collected in hexane-rinsed reagent bottles with
Teflon-lined caps. Placenta was collected on the day of delivery and individually placed into cleaned
glass containers. Hair (3 g) was collected on the first day after the delivery and was sampled from
near the scalp and from the nape of the neck using stainless steel scissors. It was then put into a
sealable polyethylene bag. All the specimens were frozen immediately after collection and stored at
20 C until chemical analysis.

Laboratory Analysis. The chemical analyses were conducted by The State Key Laboratory for
Freshwater Ecology and Biotechnology, Institute of Hydrobiology, Chinese Academy of Sciences,
China. Human milk and placenta samples were freeze-dried and then homogenized. Hair was
washed with commercial detergent (1%) for 5 min, followed by distilled water, to remove on-surface
impurities, e.g., hair care products, which may interfere with the chemical analysis (25). It was then
oven-dried at 70 C. Each sample was spiked with surrogate EDF-8999 and then Soxhlet-extracted
based on U.S. EPA Method 3540C (26). The lipid contents of human milk and placenta samples
were gravimetrically determined from an aliquot of the extract. A cleanup process was then carried
out by using three columns filled with silica gel (27), activated basic alumina (28), and florisil (29),
respectively. Internal standard (EDF-5999, 13C12 1,2,3,4-TCDD, and 13C12 1,2,3,7,8,9-HxCDD) (10 L)
was added to the concentrated sample for high-resolution gas chromatography/high-resolution mass
spectrometry (HRGC/HRMS) analysis (30). The analyses were performed on an Agilent 5890II gas
chromatograph (Agilent Technologies, U.S.A.) coupled to a Finnigan MAT 95s mass spectrometer
(Thermo Electron, U.S.A.) equipped with a CTC A200S autosampler (CTC, Switzerland) at a
resolution of 10000. An RTX-DIOXIN2 capillary column (60 m 0.25 mm i.d. 0.25 m f.t., Restek
Co.) was used for the compound separation. The PCDD/Fs were identified by mass spectrometry in
the EI and multiple ion detection modes.

Expression of PCDD/F Concentration. Levels of PCDD/Fs were indicated as mass concentrations


and toxic equivalency (TEQ) of WHO 1998 (31). The body burdens were expressed as picograms of
dioxin TEQs per gram of fat in human milk and placenta. They were also expressed as picograms of
dioxin TEQs per gram of dry weight when comparison was made among three types of samples.
The undetected values were treated as zero.

Data Analysis. The Statistical Package for Social Sciences (SPSS of Windows, version 11.0; SPSS
Inc., Chicago, IL) was used for the quantitative data analysis. The differences among groups were
assessed by the Student's t test or analysis of variance (ANOVA). Pearson correlation coefficients
were used for determining the relationship among different parameters. The significant level was p <
0.05 and two-tailed. Data are presented as means SD.

Results and Discussion

Factors Affecting Dioxin Levels: Demographic Characteristics and Food Intake. Various
factors were reported to be associated with the POP concentrations in human milk such as parity,
age of mother, food intake preferences, and period of breast-feeding (32). In this study, the total
TEQs increased with the length of residence in TZ (r = 0.993 and p = 0.01 for human milk, r = 0.950
and p = 0.013 for placenta) and the number of spontaneous abortions of the donor (r = 0.929
and p = 0.023 for hair). Increased spontaneous abortion was observed in dioxin-contaminated sites
at Seveso and Chapaevsk, Russia (33). However, Takekuma et al. (34) did not find any significant
correlation between residence years and TEQ values of human milk. Dioxin levels in human
specimens were found to be positively correlated with the mother's age (17, 34, 35). Nevertheless, in
the present study, the levels did not significantly vary with age (p < 0.05). This result was consistent
with other studies related to POPs (19, 36). Narrow age range, recent exposure of the contaminants
(37), and limited sample size are possible reasons for the result. Parity did not show any correlation
with body burden in this study (p < 0.05). Others studies also revealed such result (36, 38). In
contrast, Beck et al. (35) and Iida et al. (39) reported dioxin levels in human milk from primiparae
were higher than multiparae. TEQ values in human milk from the dumping site of India showed a
negative correlation with the number of deliveries (38).

The results of the present study showed that there was a statistically significant increase in TZ milk
dioxin levels with the intakes of crab (r = 0.888 and p = 0.044) and egg (r = 0.921, p = 0.026).
Moreover, the TEQ values for TZ placenta also significantly correlated with the intake of crab (r =
0.924, p = 0.025), whereas TZ milk fat proportion showed a significant correlation with the intake of
shellfish (r = 0.886, p = 0.045). There were statistical correlations between HZ body loadings and the
intake of foods of animal origin: bivalve (r = 0.954, p = 0.012 for human milk, r = 0.920, p = 0.027 for
placenta), pork (r = 0.904, p = 0.035 for human milk, r = 0.953, p = 0.012 for placenta), beef/lamb
(r = 0.917, p = 0.028 for human milk), chicken (r = 0.913, p = 0.028 for human milk), and animal
stomach (r = 0.981 and p = 0.019 for hair). However, there was no significant correlation between
total TEQs and the personal characteristics. These indicated that consumption of foods of animal
origin was the main dietary exposure to dioxins. According to the results of dioxin surveys conducted
in Taiwan and Japan, fish and shellfish contained the highest TEQ levels among foods of animal
origin (40, 41). Previous investigations showed that this group was the principal dietary source of
PCDD/F intake accounting for 5080%, while the secondary source was meat and eggs (4042).

Comparison: Dioxin Body Burden of Mothers in the E-Waste Recycling Site and the
Reference Site. The PCDD/F concentrations in human milk, placenta, and hair collected from the
two sites are shown in Table 1. The total TEQ value of TZ human milk (21.02 13.81, 11.5944.60
pg WHO-TEQ/g fat) was about 2 times higher than that of HZ human milk (9.35 7.39, 2.0421.35
pg WHO-TEQ/g fat), although the difference was not significant (p > 0.05). However, TZ placenta
(31.15 15.67, 18.1543.20 pg WHO-TEQ/g fat) and TZ hair (33.82 17.74, 14.5762.43 pg WHO-
TEQ/g dry wt) showed statistically higher concentrations than the samples from HZ (placenta, 11.91
7.05, 4.8913.39 pg WHO-TEQ/g fat; hair, 5.59 4.36, 2.4113.38 pg WHO-TEQ/g dry wt) (p <
0.05). Background pollution level, dietary habit, and personal characteristics of the sample donors
are the most important factors affecting the body burden. Although previous studies showed that
less than 2% of human dioxin intake is from direct inhalation (43), TZ people are exposed more to
the toxic chemicals via inhalation, in addition to dermal contact and consumption of local foods due
to relatively high background contamination level. Human exposure to dioxins begins with
atmospheric emissions (35), of which incineration releases the largest quantity of dioxins (12). Open
burning of e-waste releases extremely high levels of dioxins (2031100 pg WHO-TEQ/g dry wt in
soil) (8). Moreover, significant amounts of dioxin-related POPs, e.g., PAHs (2065 g/kg dry wt in soil,
124 44.1 g/m3 in total suspended particles of air samples) and PBDEs (3300097400 ng/g dry wt
in combusted residue of plastic chips and cables) were found at the areas near e-waste recycling
workshops (57). Hence, the background contamination in TZ should be more serious than that in
HZ. This can be further confirmed by the dioxin hair analysis since dioxin levels in hair reflect those
in the atmosphere (4447). Our results showed that the level of dioxins in TZ hair (33.82 17.74 pg
WHO-TEQ/g dry wt) was significantly higher than that in HZ samples (5.59 4.43 pg WHO-TEQ/g
dry wt) (p < 0.05). Moreover, Nakao et al. (45) pointed out that hair collected from municipal solid
waste (MSW) incineration workers contained total TEQ levels (4.37 pg WHO-TEQ/g) that were 2.5
times higher than those from the general population (1.74 pg WHO-TEQ/g). This implied that the
higher background dioxin level at TZ compared with HZ was due to the e-waste recycling operation,
particularly burning of wastes. Thus, the body loadings were significantly greater for TZ mothers than
for HZ mothers.

Table 1. Concentration (pg/g and pg WHO-TEQ/g) of PCDD/Fs in Human Specimens from the E-
Waste Recycling Site (TZ) and the Reference Site (HZ)a,b,c

e-wasterecyclingsite(TZ) referencesite(HZ)

congener WHO- humanmilk placenta hair humanmilk placenta hair


TEF pg/gfat pg/gfat pg/gdrywt pg/gfat pg/gfat pg/gdrywt

PCDDcongeners
2,3,7,8-TCDD 1 3.59 4.88 2.31 3.11 4.74 4.48

1,2,3,7,8-PeCDD 1 4.65 10.56 7.45 1.47 2.46 0.326

1,2,3,4,7,8- 0.1 2.11 2.43 2.42 1.21 1.66 0.106


HxCDD

1,2,3,6,7,8- 0.1 4.76 1.10 4.08 2.80 0.717 0.106


HxCDD

1,2,3,7,8,9- 0.1 2.30 0.606 2.10 0.948 0.539 0.065


HxCDD

1,2,3,4,6,7,8- 0.01 10.2 7.06 12.4 5.08 5.85 1.31


HpCDD

OCDD 0.0001 80.9 49.8 22.6 41.0 52.7 6.80

PCDD-TEQ 9.27 15.93 10.74 5.13 7.55 4.84

PCDFcongeners
2,3,7,8-TCDF 0.1 9.54 5.95 46.6 1.35 1.60 1.16

1,2,3,7,8-PeCDF 0.05 6.86 8.70 23.7 0.404 0.725 0.142

2,3,4,7,8-PeCDF 0.5 15.4 31.4 24.6 6.06 6.51 0.705

1,2,3,4,7,8- 0.1 10.4 14.53 14.8 3.81 3.74 1.01


HxCDF

1,2,3,6,7,8- 0.1 9.23 6.76 15.2 3.08 2.77 0.744


HxCDF

2,3,4,6,7,8- 0.1 6.12 2.73 14.0 2.66 1.55 0.740


HxCDF

1,2,3,7,8,9- 0.1 0.323 0.372 2.71 0.134 0.436 0.0652


HxCDF

1,2,3,4,6,7,8- 0.01 13.0 4.49 24.9 6.29 4.84 2.05


HpCDF

1,2,3,4,7,8,9- 0.01 1.23 1.01 2.01 0.134 0.967 0.0652


HpCDF
OCDF 0.0001 1.45 2.03 6.62 0.417 7.18 1.87

PCDF-TEQ 11.7 19.22 23.1 4.22 4.36 0.752

PCDD/F-TEQ 21.0 35.1c 33.8c 9.35 11.9 5.59

a
Abbreviations: HpCDD, hetachlorodibenzodioxin; HpCDF, heptachlorodibenzofuaran; HxCDF,
hexachlorodibenzofuaran; HxCDD, hexahetachlorodibenzodioxin; OCDD, octachlorodibenzodioxin;
OCDF, octachlorodibenzofuaran; TCDD, tetrahetachlorodibenzodioxin; TCDF,
tetrachlorodibenzofuaran.bDetection limit (pg/g): milk, TCDD/F = 0.100.13, PeCDD/F = 0.100.17,
HxCDD/F and HpCDD/F = 0.070.13, OCDD/F = 0.130.23; placenta, TCDD/F = 0.060.08,
PeCDD/F = 0.060.10, HxCDD/F and HpCDD/F = 0.040.08, OCDD/F = 0.080.14; hair, TCDD/F =
0.150.20, PeCDD/F = 0.150.25, HxCDD/F and HpCDD/F = 0.100.20, OCDD/F =
0.200.35.cSignificant difference between TZ and HZ samples (p < 0.05).

Such difference could also be explained by personal characteristics and dietary intake. Of all the
personal characteristics, parity and the number of breast-fed children showed significant differences
between the two sites (p < 0.05) (see Table S1, Supporting Information). Forty percent of TZ
mothers were primiparae, while all HZ mothers were primiparae. These women were selected
according to the criteria mentioned in the Study Population section. Previous studies showed that
increased parity or increased period of breast-feeding was directly related to a lighter body burden of
PCDD/Fs (35, 38, 39). However, this phenomenon was not observed in this study. Thus, these two
parameters did not appear to affect the body burden. On the other hand, according to the results of
the food consumption survey, TZ mothers generally consumed more foods of animal origin, whereby
the consumption of pork and animal stomach was significantly higher (p < 0.05) (see Table S2,
Supporting Information). Foods of animal origin are considered to be the major dietary sources of
dioxins since POPs are fat-seeking and accumulate in the fat of animals (48). As mentioned before,
statistical analysis showed that higher intakes of this food class lead to greater body loadings in TZ
mothers (p < 0.05).
Congener Concentrations and Homologue Profiles. The most toxic congener, 2,3,7,8-TCDD,
was present in all samples from both sites. On average, 2,3,7,8-TCDD, 2,3,4,7,8-PeCDF, and
1,2,3,7,8-PeCDD contributed 780%, 645%, and 630%, respectively, to the total TEQs. These
three congeners constituted up to 6592%. The homologue profiles indicate the environmental fate
and sources of dioxins (49). The samples of each TZ or HZ donor showed similar profiles to those of
the representative profiles (obtained by using the average concentrations). All samples from both
sites, except TZ hair, showed similar homologue profiles where PCDDs (TCDD, 1864%; OCDD,
2040%) contributed largely to the total concentration (see Figures S1aS1d and S1f, Supporting
Information). In contrast, TZ hair showed a distinct homologue profile which was dominated by tetra
through hexachlorinated furans (73%) (see Figure S1e, Supporting Informa tion). The reasons for
the contradiction among TZ samples are unknown. The detailed fates of dioxins after entering
human bodies via different exposures are not clearly recognized. It is suggested that the profile for
hair might indicate more recent exposure of dioxins since hair directly contacts with the exposure
media (atmosphere), whereas those for milk and placenta might reflect the historical exposures.
However, this speculation may only be applied in highly contaminated areas since such difference
was not observed in HZ samples. The profile for TZ hair closely resembled that for hair of workers at
an emission source, such as an MSW incinerator (45). Both profiles were markedly different from
those for the reference group or for the general population. Nakao et al. (44) also concluded that
although the hair samples had been washed for chemical analysis, dioxins produced in the
combustion process in the MSW incinerator was one of the exposures leading to dioxins in workers'
hair as similar isomer patterns were also found in precipitation ash. Therefore, high levels of dioxins
in TZ hair were caused by atmospheric exposure in addition to body accumulation. This gave further
support that the e-waste recycling activity accounted for the fresh input of dioxins, leading to greater
body burdens in TZ mothers.

Use of Human Specimens as Biological Indicators for Dioxin Contamination. Different types of
human specimens showed advantages and disadvantages for assessing exposure. Dioxins in hair
indicated body accumulation and atmospheric deposition onto the hair surface (25). Hair can be
applied to all population groups. Its sampling is very convenient and noninvasive (50). Relatively
high lipid content (3.54%) shows stability for the chemical analysis (51, 52). However, it is difficult
to distinguish between exogenous and endogenous contamination (53). Concentrations may be
varied if hair from different positions of the head is collected (25). Moreover, different concentrations
are found along the length of hair (54). Placenta provides a good indication for prenatal exposure
(21). The variations among different donors can be reduced due to the same sampling time, usually
on the day of labor. Moreover, placenta is ideal for biomonitoring as it is large enough to allow assay
of several pollutants during the same sampling. Nevertheless, it is restricted to females and not
easily available. Tissues need to be obtained by more invasive procedures (53). Human milk reflects
maternal body burden and the postnatal transfer of dioxin from mothers to infants (15). Moreover,
collection of human milk is convenient and noninvasive and is easily replicated. The high content of
fat (25%) makes the extraction method easier and improves the precision of the measurements.
However, human milk is restricted to lactating women. Furthermore, all the milk samples should be
collected at the same breast-feeding time as dioxin levels vary along the breast-feeding period (35).

When comparing the three types of specimens from TZ, hair contained the highest dioxin
concentration (33.82 17.74 pg WHO-TEQ/g dry wt; p = 0.001), followed by human milk (2.96
1.30 pg WHO-TEQ/g dry wt), and then placenta (2.06 1.30 pg WHO-TEQ/g dry wt). Samples from
HZ also showed a similar trend whereby PCDD/F concentrations in hair (5.59 4.43 pg WHO-TEQ/g
dry wt) were significantly higher than those in placenta (0.63 0.28 pg WHO-TEQ/g dry wt; p =
0.032); however, there was no significant difference with those in human milk (2.20 1.45 pg WHO-
TEQ/g dry wt; p > 0.05). The TEQ values of the three types of TZ specimens showed significant
positive correlations with each other (r = 0.995 and p < 0.001 for human milk and placenta; r = 0.900
and p = 0.037 for human milk and hair; r = 0.892 and p = 0.042 for placenta and hair). For HZ
samples, only dioxin concentration in human milk showed a significant positive correlation with
concentration in placenta (r = 0.930, p = 0.022). These results appeared to indicate that at highly
contaminated sites, hair may be used as a reliable bioindicator for dioxin body burden. However,
further investigations are needed for proving this hypothesis and for finding out the causes leading to
different homologue profiles for different types of samples.

Comparison with Worldwide and Domestic PCDD/F Levels. Human Milk. All TZ samples and
80% of the HZ samples exceeded the EU's maximum permitted level in milk (3 pg WHO-TEQ/g lipid)
(55). The concentrations of the former were high, whereas those of the latter were moderate when
compared with the 26 countries involved in the WHO Third Exposure Study on Human Milk Dioxins
(15) (see Figure S2, Supporting Information). For example, the concentrations in TZ human milk
would be ranked number 2 after Egypt, whereas HZ showed concentrations similar to Ireland and
Norway. Moreover, TZ human milk showed the highest concentrations among the samples collected
from other parts of China during 20002005 (see Table S3, Supporting Information). HZ samples
contained comparable concentra tions with those from Dalian and Shenyang (19), Taiwan (17, 21),
Shijiazhuang, and Tangshan (56). This further confirmed that the relatively heavy body burden of TZ
mothers was due to e-waste recycling activities which are absent from the areas of other studies.
Schecter and co-workers (57, 58) investigated the dioxin contamination levels in an area which had
been heavily sprayed with sodium pentachlorophenol (NaPCP) to control schistosomiasis. NaPCP
is a pesticide which is contaminated with higher chlorinated PCDDs. Human milk samples collected
from the sprayed areas contained concentrations that were 4-fold lower than those from TZ.
However, those collected from the residents living near Ya-Er Lake, which had been heavily polluted
by effluent from a chloroalkali manufacturing plant nearby, contained extremely high TEQ values
(59).

Placenta. Concentrations in TZ samples were 23-fold higher than specimens from the general
population of central Taiwan (21, 60), the United States (61), and Germany (62) and were
comparable with those from Japan (63) (see Table S3, Supporting Information). However, those
collected from six mothers with Yu-Cheng disease caused by the consump tion of PCB-
contaminated rice oil in Taiwan showed markedly higher dioxin levels (64) than all other studies.

Hair. There are only a few studies on dioxins in human hair (see Table S3, Supporting Information).
The highest TEQ value was found by the present study, followed by Luksemburg et al. (65) who
collected samples from barber shops at an e-waste recycling site (Guiyu, Guangdong Province) in
China. The total TEQs in hair and ash samples reported by this study were relatively high (21.0 and
5858.33 pg WHO-TEQ/g, respectively), suggesting that e-waste processing activities release a
significant amount of dioxins. Hair collected from residents living close to Ya-Er Lake contained
concentrations that were 25 times lower than TZ hair (66). However, human milk collected from Ya-
Er Lake revealed higher levels than those from TZ (59). Such contradiction may imply that there was
fresh input of dioxins to the atmospheric environment in TZ as hair is a good indicator for
atmospheric dioxins (44, 46, 47, 63).

Health Risk Assessment for Infants. In order to evaluate the risk faced by infants via breast-
feeding, the estimated daily intake (EDI) of PCDD/Fs should be determined (see the Supporting
Information for the calculation). TZ infants consumed 102.98 67.65 pg TEQ/kg body wt/day which
is 2 times higher than that of HZ infants (45.83 36.22 pg TEQ/kg body wt/day). Both values would
exceed the WHO tolerable daily intake (TDI) (14 pg TEQ/kg body wt/day) (67) by at least 25 and 11
times, respectively. Assuming that 90% of the ingested dioxins are absorbed (68), the infant's
exposure would still be serious. The WHO TDI includes the exposure to dioxin-like PCBs; thus, the
EDI for TZ infants might underestimate the risk. Although the TDI has been estimated for humans
over their entire lifetime, the acute exposure via high intake exceeding the toxicological limit during
breast-feeding is of concern due to the long half-life of the compounds and immature body defense
of infants. Studies found that postnatal exposure to dioxins affects thyroid hormone system and
immunological functions of infants and children (69, 70). Moreover, it should be noted that infants
and children absorb dioxins at a faster rate than adults due to their high growth rate (71). In addition,
TZ infants are at greater risk due to higher background levels, implying that they would absorb more
dioxins via dermal contact, inhalation, and prenatal exposure. However, breast-feeding should be
encouraged, given that the infant receives nutritional advantages and protection against infectious
diseases (17, 18).

This is the first study investigating the PCDD/F levels in human milk, placenta, and hair collected
from mothers at an intense e-waste recycling site and a reference site in China. Although a limited
number of samples were analyzed, the results indicated that e-waste recycling operations caused
elevated PCDD/F levels in humans and in the environment. The body burdens of dioxins in people
from the e-waste processing site were ranked among the highest when compared on an
international basis. The elevated body burden may impose health implications for the next genera
tion. This study would be more comprehensive if the sample size is increased. However, the costs of
chemical analysis of dioxins should be considered. On the other hand, work should be done on
reducing the negative impacts of the e-waste recycling activities to the environment and humans.
For example, education supported by the central and local governments should be carried out to
teach local residents realize e-waste recycling is a problem and should be addressed. Moreover,
further investigations on epidemiological studies of health impacts caused by e-waste recycling
operations, dioxin levels in local foods, and kinetics about the POP partitions among different human
tissues should be conducted.

Acknowledgment

We thank the mothers who contributed to the study and donated milk, placenta, and hair samples.
This research is supported by The Research Grants Council of the University Grants Committee of
Hong Kong (Central Allocation Group Research Project HKBU 1/03C), Match Fund from Hong Kong
Baptist University, and a private donation.

Supporting Information Available


Experimental Section, data collection, Discussion section, health risk assessment for infants, Tables
S1S3, and Figures S1aS1f and S2. This material is available free of charge via the Internet
at http://pubs.acs.org.
PDF
o es071492j-file002.pdf (172.83 kB)

This article references 71 other publications.

1. (1)

Silicon Valley Toxics Coalition. Just say no to e-waste: background document on hazards and
waste from computers. http://www.svtc.org/cleancc/pubs/sayno.htm (accessed October 4,
2006).

2. (2)

Xinhua Online. Seventy percent of worldwide electronic-waste goes to China. Dated January 1,
2007.http://news3.xinhuanet.com/tech/2007-01/09/content_5581834.htm (in Chinese)
(accessed March 1, 2007).

3. (3)

The Basel Action Network and Silicon Valley Toxics Coalition. Exporting harm: the high-tech
trashing of Asia. http://www. ban.org/E-waste technotrashfinalcomp.pdf (accessed February
16, 2007).

4. (4)

UNEP. Meeting the challenge of e-waste. http://www.basel.int/pub/leaflet170806-


2.pdf#search='unep%202005%20ewaste' (ac cessed November 1, 2006).

5. (5)

Leung, A.; Cai, Z. W.; Wong, M. H. Environmental contamination from electronic waste
recycling at Guiyu, Southeast China. J. Mater. Cycles Waste Manage. 2006, 8, 2133.

[Crossref], [CAS]

6. (6)

Yu, X. Z.; Gao, Y.; Wu, S. C.; Zhang, H. B.; Cheung, K. C.; Wong, M. H. Distribution of
polycyclic aromatic hydrocarbons in soils at Guiyu area of China affected by recycling
electronic waste using primitive technologies. Chemosphere 2006, 65, 15001509.

[Crossref], [PubMed], [CAS]

7. (7)
Deng, W. J.; Louie, P. K. K.; Liu, W. K.; Bi, X. H.; Fu, J. M.; Wong, M. H. Atmospheric levels
and cytotoxicity of PAHs and heavy metals in TSP and PM2.5 at an electronic waste recycling
site in Southeast China. Atmos. Environ. 2006, 40, 69456955.

[Crossref], [CAS]

8. (8)

Leung, A. O. W.; Luksemburg, W. J.; Wong, A. S.; Wong, M. H. Spatial distribution of


polybrominated diphenyl ethers and polychlorinated dibenzo-p-dioxins and dibenzofurans in
soil and combusted residue at Guiyu, an electronic waste recycling site in Southeast
China. Environ. Sci. Technol. 2007, 41, 27302737.

[ACS Full Text ], [CAS]

9. (9)

Wang, D. L.; Cai, Z. W.; Jiang, G. B.; Leung, A.; Wong, M. H.; Wong, W. K. Determination of
polybrominated diphenyl ethers in soil and sediment from an electronic waste recycling
facility.Chemosphere 2005, 60, 810816.

[Crossref], [PubMed], [CAS]

10. Wong, C. S. C.; Duzgoren-Aydin, N. S.; Aydin, A.; Wong, M. H. Evidence of excessive
releases of metals from primitive e-waste processing in Guiyu, China. Environ.
Pollut. 2007, 148, 6272.

[Crossref], [PubMed], [CAS]

11. (11)

Wong, S. C.; Wu, S. C.; Duzgoren-Aydin, N. S.; Aydin, A.; Wong, M. H. Trace metal
contamination of sediments in an e-waste processing village in China. Environ.
Pollut. 2007, 145, 434442.

[Crossref], [PubMed], [CAS]

12. (12)

WHO. Fact sheet: dioxin and their effects on human


health.http://www.who.int/mediacentre/factsheets/fs225/en/ (ac cessed June 24, 2004).

13. (13)

Minh, N. H.; Minh, T. B.; Watanabe, M.; Kunisue, T.; Monirith, I.; Tanabe, S.; Sakai, S.;
Subramanian, A.; Sasikumar, K.; Viet, P. H.; Tuyen, B. C.; Tana, T. S.; Prudente, M. S. Open
dumping site in Asian developing countries: a potential source of polychlorinated dibenzo-p-
dioxins and polychlorinated dibenzofurans. Environ. Sci. Technol. 2003, 37, 14931502.

[ACS Full Text ], [CAS]

14. (14)
Liem, A. K. D.; Ahlborg, U. G.; Back, H.; Haschke, F.; Nygren, M.; Younes, M.; Ynanheikke,
E. Levels of PCBs, PCDDs and PCDFs in Human Milk: Second Round of WHO-Coordinated
Exposure Study; Environmental Health in Europe No. 3. EUR/ICP EHPM02 03 05; WHO
European Centre for Environment and Health: Copenhagen, Denmark, 1996.

15. (15)

Malisch, R.; van Leeuwen, F. X. R. Results of the WHO-coordinated exposure study on the
levels of PCBs, PCDDs, and PCDFs in human milk. Organohalogen Compds. 2003, 56,
311316.

16. (16)

Yrjnheikki E. J., Ed. Levels of PCBs, PCDDs, and PCDFs in Breast Milk. Results of WHO-
Coordinated Interlaboratory Quality Control Studies and Analytical Field Studies;
Environmental Health Series Report No. 34; WHO Regional Office for Europe: Copenhagen,
Denmark, 1989.

17. (17)

Chao, H. R.; Wang, S. L.; Lee, C. C.; Yu, H. Y.; Lu, Y. K.; Ppke, O. Level of polychlorinated
dibenzo-p-dioxins, dibenzofurans and biphenyls (PCDD/Fs, PCB) in human milk and the input
to infant body burden.Food Chem. Toxicol. 2004, 42, 12991308.

[Crossref], [PubMed], [CAS]

18. (18)

Hedley, A. J.; Wong, T. W.; Hui, L. L.; Malisch, R.; Nelson, E. A. S. Breast milk dioxins in Hong
Kong and Pearl River Delta. Environ. Health Perspect. 2006, 114, 202208.

[Crossref], [PubMed], [CAS]

19. (19)

Kunisue, T.; Someya, M.; Kayama, F.; Jin, Y.; Tanabe, S. Persistent organochlorines in human
breast milk collected from primiparae in Dalian and Shenyang China. Environ.
Pollut. 2004, 131, 381392.

[Crossref], [PubMed], [CAS]

20. Soechitram, S. D.; Chan, S. M.; Nelson, E. A. S.; Brouwer, A.; Sauer, P. J. J. Comparison of
dioxin and PCV concentrations in human breast milk samples from Hong Kong and the
Netherlands. Food Addit. Contam. 2003, 20, 6569.

[Crossref], [PubMed], [CAS]

21. (21)
Wang, S. L.; Lin, C. Y.; Guo, L. Y. L.; Lin, L. Y.; Chou, W. L.; Chang, L. W. Infant exposure to
polychlorinated dibenzo-p-dioxins, dibenzofurans and biphenyls (PCDD/Fs, PCBs)correlation
between prenatal and postnatal exposure. Chemosphere 2004, 54, 14591473.

[Crossref], [PubMed], [CAS]

22. (22)

Taizhou Municipality, China. http://www.zjtz.gov.cn/ksp/ english/ (accessed March 3, 2007).

23. (23)

Taizhou Economic Committee, China. http://www.tzsjw.gov.cn/index.php (in Chinese)


(accessed August 5, 2007).

24. (24)

Lin'an Government, China. http://www.linan.gov.cn/ (in Chinese) (accessed March 3, 2007).

25. (25)

Covaci, A.; Tutudaki, M.; Tsatsakis, A. M.; Schepens, P. Hair analysis: another approach for
the assessment of human exposure to selected persistent organochlorine
pollutants. Chemosphere 2002, 46, 413418.

[Crossref], [PubMed], [CAS]

26. (26)

Method 3540C. Soxhlet extraction. In Test Methods for Evaluating Solid Waste,
Physical/Chemical Methods; SW-846; U.S. EPA: Washington, DC, 1996.

27. (27)

Method 3630C: Silica gel cleanup. In Test Methods for Evaluating Solid Waste,
Physical/Chemical Methods; SW-846; U.S. EPA: Washington, DC, 1996.

28. (28)

Method 3610B. Alumina cleanup. In Test Methods for Evaluating Solid Waste,
Physical/Chemical Methods; SW-846; U.S. EPA: Washington, DC, 1996.

29. (29)

Method 3620B: Florisil cleanup. In Test Methods for Evaluating Solid Waste,
Physical/Chemical Methods; SW-846; U.S. EPA: Washington, DC, 1996.

30. Method 1613B. Tetra- through octachlorinated dioxins and furans by isotope dilution
HRGC/HRMS. InTest Methods for Evaluating Solid Waste, Physical/Chemical Methods; SW-
846; U.S. EPA: Washington, DC, 1997.

31. (31)
Van den Berg, M.; Birnbaum, L.; Bosveld, A. T. C.; Brunstrm, B.; Cook, P.; Feeley, M.; Giesy,
J. P.; Hanberg, A.; Hasegawa, R.; Kennedy, S. W.; Kubiak, T.; Larsen, J. C.; van Leeuwen, F.
X. R.; Liem, A. K. D.; Nolt, C.; Peterson, R. E.; Peollinger, L.; Stephen, S.; Schrenk, D.; Tillitt,
D.; Tysklind, M.; Younes, M.; Wrn, F.; Zacharewski, T. Toxic equivalency factors (TEFs) for
PCBs, PCDDs, PCDFs for humans and wildlife. Environ. Health Perspect. 1998, 106,
775792.

[Crossref], [PubMed], [CAS]

32. (32)

Harris, C. A.; Woolridge, M. W.; Hay, A. W. M. Factors affecting the transfer of organochlorine
pesticide residues to breast milk. Chemosphere 2001, 43, 243256.

[Crossref], [PubMed], [CAS]

33. (33)

Revich, B.; Aksel, E.; Ushakova, T.; Ivanova, I.; Zhuchenko, N.; Klyuev, N.; Brodsky, B.;
Sotskov, Y. Dioxin exposure and public health in Chapaevsk, Russia. Chemosphere 2001, 43,
951966.

[Crossref], [PubMed], [CAS]

34. (34)

Takekuma, M.; Saito, K.; Ogawa, M.; Matumoto, R.; Kobayashi, S. Levels of PCDDs, PCDFs
and Co-PCBs in human milk in Saitama, Japan, and epidemiological
research. Chemosphere 2004, 54, 127135.

[Crossref], [PubMed], [CAS]

35. (35)

Beck, H.; Dross, A.; Mathar, W. PCDD and PCDF exposure and levels in humans in
Germany. Environ. Health Perspect. 1994, 102, 173185.

[PubMed], [CAS]

36. (36)

Falcn, M.; Oliva, J.; Osuna, E.; Barba, A.; Luna, A. HCH and DDT residues in human
placentas in Murcia (Spain). Toxicology 2004, 195, 203208.

[Crossref], [PubMed], [CAS]

37. (37)

Tanabe, S.; Kunisue, T. Persistent organic pollutants in human breast milk from Asian
countries. Environ. Pollut. 2007, 146, 400413.

[Crossref], [PubMed], [CAS]


38. (38)

Kunisue, T.; Watanabe, M.; Iwata, H.; Subramanian, A.; Monirith, I.; Minh, T. B.;
Baburajendran, R.; Tana, T. S.; Viet, P. H.; Prudente, M.; Tanabe, S. Dioxins and related
compounds in human breast milk collected around open dumping sites in Asian developing
countries: bovine milk as a potential source. Arch. Environ. Contam. Toxicol. 2004, 47,
414426.

[Crossref], [PubMed], [CAS]

39. (39)

Iida, T.; Hirakawa, H.; Matsueda, T.; Takenaka, S.; Nagayama, J. Polychlorinated dibenzo-p-
dioxins and related compounds in breast milk of Japanese primiparas and
multiparas. Chemosphere 1998, 38, 34973502.

[Crossref]

40. Hsu, M. S.; Cheng, P. S.; Ma, E.; Chou, U.; Chen, L. P.; Jone, C. H.; Chou, S. S.; Cheng, C.
C.; Yu, C. Y.; Liao, C. H.; Ling, Y. C. A preliminary total diet study of PCDD/Fs-intake from food
in Taiwan.Organohalogen Compds. 2002, 55, 231234.

[CAS]

41. (41)

Sasamoto, T.; Ushio, F.; Kikutani, N.; Saitoh, Y.; Yamaki, Y.; Hashimoto, T.; Horii, S.;
Nakagawa, J.; Ibe, A. Estimation of 19992004 dietary daily intake of PCDDs, PCDFs and
dioxin-like PCBs by a total diet study in Metropolitan Tokyo, Japan. Chemosphere 2006, 64,
634641.

[Crossref], [PubMed], [CAS]

42. (42)

Tsutsumi, T.; Yanagi, T.; Nakamura, M.; Kono, Y.; Uchibe, H.; Iida, T.; Hori, T.; Nakagawa, R.;
Tobiishi, K.; Matsuda, R.; Sadaki, K.; Toyoda, M. Update of daily intake of PCDDs, PCDFs,
and dioxin-like PCBs from food in Japan. Chemosphere 2001, 45, 11291137.

[Crossref], [PubMed], [CAS]

43. (43)

Hong Kong Environmental Protection Department. A review of dioxin emissions in Hong Kong:
Final report. http://www. epd.gov.hk/epd/english/environmentinhk/waste/studyrpts/files/review
report.pdf (accessed June 21, 2004).

44. (44)

Nakao, T.; Aozasa, O.; Ohta, S.; Miyata, H. Assessment of human exposure to PCDDs,
PCDFs and Co-PCBs. Using hair as a human pollution indicator sample I: development of
analytical method for human hair and evaluation for exposure
assessment. Chemosphere 2002, 48, 885896.

[Crossref], [PubMed], [CAS]

45. (45)

Nakao, T.; Aozasa, O.; Ohta, S.; Miyata, H. Survey of human exposure to PCDDs, PCDFs,
and coplanar PCBs using hairs an indicator. Arch. Environ. Contam. Toxicol. 2005, 17,
124130.

[Crossref]

46. (46)

Schramm, K. W.; Keuttnear, T.; Weber, S.; Ltzke, K. Dioxin hair analysis as monitoring
pool.Chemosphere 1992, 24, 351358.

[Crossref], [CAS]

47. (47)

Tirler, W.; Voto, G.; Donega, M. PCDD/F, PCB and hexachlorobenzene level in
hair. Organohalogen Compds. 2001, 52, 290292.

[CAS]

48. (48)

Hooper, K.; Petreas, M. X.; Chuvakova, T.; Kazbekova, G.; Druz, N.; Seminova, G.;
Sharmanov, T.; Hayward, D.; She, J. W.; Visita, P.; Winkler, J.; McKinney, M.; Wade, T. J.;
Grassman, J.; Stephens, R. D. Analysis of breast milk to assess exposure to chlorinated
contaminants in Kazakhstan: high levels of 2,3,7,8-tetrachlorodibenzo-p-dioxin (TCDD) in
agricultural villages of Southern Kazakhstan. Environ. Health Perspect. 1998, 106, 797806.

[Crossref], [PubMed], [CAS]

49. (49)

Duarte-Davison, R.; Sewart, A.; Alcock, R. E.; Cousins, I. T.; Jones, K. C. Exploring the
balance between sources, deposition and the environmental burden of PCDD/Fs in the U.K.
terrestrial environment: an aid to identifying uncertainties and research needs. Environ. Sci.
Technol. 1997, 31, 111.

[ACS Full Text ]

50. Tsatsakis, A.; Tutudaki, M. Progress in pesticide and POPs hair analysis for the assessment of
exposure.Forensic Sci. Int. 2004, 145, 195199.

[Crossref], [PubMed], [CAS]

51. (51)
Neuber, K.; Merkel, G.; Randow, F. F. E. Indoor air pollution by lindane and DDT indicated by
head hair samples of children. Toxicol. Lett. 1999, 107, 189192.

[Crossref], [PubMed], [CAS]

52. (52)

Covaci, A.; Schepens, P. Chromatographic aspects of the analysis of selected persistent


organochlorine pollutants in human hair. Chromatographia 2001, 53, 366371.

[Crossref], [CAS]

53. (53)

Altshul, L.; Covaci, A.; Hauser, R. The relationship between levels of PCBs and pesticides in
human hair and blood: preliminary results. Environ. Health Perspect. 2004, 112, 11931199.

[Crossref], [PubMed], [CAS]

54. (54)

Paustenbach, D.; Galbraith, D. Biomonitoring and biomarkers: exposure assessment will never
be the same. Environ. Health Perspect. 2006, 114, 11431149.

[Crossref], [PubMed], [CAS]

55. (55)

Department of the Environment and Water Resources, Australian Government. Dioxins in


Fauna in Australia; Technical Report No.
7.http://www.environment.gov.au/settlements/publications/chemicals/dioxins/report7/guidelines
.html (ac cessed February 23, 2007).

56. (56)

Sun, S. J.; Zhao, J. H.; Liu, H. J.; Liu, D. W.; Ma, Y. X.; Li, L.; Horiguchi, H.; Uno, H.; Iida, T.;
Koga, M.; Kiyonari, Y.; Nakamura, M.; Sasaki, S.; Fukatu, H.; Clark, G. C.; Kayama, F. Dioxin
concentration in human milk in Hebei Province in China and Tokyo Japan: potential dietary
risk factors and determination of possible sources. Chemosphere 2006, 62, 18791888.

[Crossref], [PubMed], [CAS]

57. (57)

Schecter, A. J.; Jiang, K.; Ppke, O.; Frst, P.; Frst, C. Comparison of dibenzodioxin levels in
blood and milk in agricultural workers and others following pentachlorophenol exposure in
China. Chemosphere1994, 29, 23712380.

[Crossref], [PubMed], [CAS]

58. (58)
Schecter, A. J.; Li, L. J.; Jiang, K.; Frst, P.; Frst, C.; Ppke, O. Pesticide application and
increased dioxin body burden in male and female agricultural workers in China. J. Occup.
Environ. Med. 1996, 38, 906911.

[Crossref], [PubMed], [CAS]

59. (59)

Wu, W. Z.; Schramm, K. W.; Kettrup, A. Bioaccumulation of polychlorinated dibenzo-p-dioxins


and dibenzofurans in the foodweb of Ya-Er Lake area China. Water Res. 2001, 35,
11411148.

[Crossref], [PubMed], [CAS]

60. Chao, H. R.; Wang, S. L.; Lin, L. Y.; Lee, W. J.; Ppke, O. Placental transfer of polychlorinated
dibenzo-p-dioxins, dibenzofurans, and biphenyls in Taiwanese mothers in relation to menstrual
cycle characteristics.Food Chem. Toxicol. 2007, 45, 259265.

[Crossref], [PubMed], [CAS]

61. (61)

Schecter, A.; Kassia, I.; Ppke, O. Partitioning of dioxins, dibenzofurans, and coplanar PCBs in
blood milk adipose tissue placenta and cord blood from five American
women. Chemposphere 1998, 98, 18171823.

[Crossref]

62. (62)

Abraham, K.; Ppke, O.; Gross, A.; Kordonouri, O.; Wiegand, S.; Wahn, U.; Helge, H. Time
course of PCDD/PCDF/PCB concentrations in breast-feeding mothers and their
infants. Chemosphere 1998, 37, 17311741.

[Crossref], [PubMed], [CAS]

63. (63)

Nakano, S.; Noguchi, T.; Takekoshi, H.; Suzuki, G.; Nakano, M. Maternalfetal distribution and
transfer of dioxins in pregnant women in Japan and attempts to reduce maternal transfer with
chlorella (Chlorella pyrenoidosa) supplements. Chemosphere 2005, 61, 12441255.

[Crossref], [PubMed], [CAS]

64. (64)

Schecter, A.; Startin, J.; Wright, C.; Ppke, O.; Ball, M.; Lis, A. Concentrations of
polychlorinated dibenzo-p-dioxins and dibenzofurans in human placental and fetal tissues from
the U.S. and in placentas from Yu-Cheng exposed mothers. Chemosphere 1996, 32, 551557.

[Crossref], [PubMed], [CAS]


65. (65)

Luksemburg, W. J.; Mitzel, R. S.; Peterson, R. G.; Hedin, J. M.; Maier, M. M.; Schuld, M.;
Zhou, H. D.; Wong, A. S. Polychlorinated dibenzodioxins and dibenzofurans (PCDD/PCDFs)
levels in environmental and human hair samples around an electronic waste processing site in
Guiyu, Guangdong Province China. Organohalogen Compds. 2002, 55, 347349.

[CAS]

66. (66)

Wu, W. Z.; Xu, Y.; Schramm, K. W.; Kettrup, A. Persistence of polychlorinated dibenzo-p-
dioxins and dibenzofurans (PCDD/F) in Ya-Er Lake area China. Environ. Int. 2001, 26,
323326.

[Crossref], [PubMed], [CAS]

67. (67)

Van Leeuwen, F. X. R.; Feeley, M.; Schrenk, D.; Larsen, J. C.; Farland, W.; Younes, M.
Dioxins: WHO's tolerable daily intake (TDI) revisited. Chemosphere 2000, 40, 10951101.

[Crossref], [PubMed], [CAS]

68. (68)

Hooper, K.; Chuvakova, T.; Kazbekova, G.; Hayward, D.; Tulenova, A.; Petreas, M. X.; Wade,
T. J.; Benedict, K.; Cheng, Y. Y.; Grassman, J. Analysis of breast milk to assess exposure to
chlorinated contaminants in Kazakhstan: sources of 2,3,7,8-tetrachlorodibenzo-p-dioxin
(TCDD) exposures in an agricultural region of Southern Kazakhstan. Environ. Health
Perspect. 1997, 107, 447457.

[Crossref]

69. (69)

Nagayama, J.; Kohno, H.; Kunisue, T.; Kataoka, K.; Shimomura, H.; Tanabe, S.; Konishi, S.
Concentrations of organochlorine pollutants in mothers who gave birth to neonates with
congenital hypothyroidism. Chemosphere 2007, 68, 972976.

[Crossref], [PubMed], [CAS]

70. Weisglas-Kuperus, N.; Patandin, S.; Berbers, G. A. M.; Sas, T. C. J.; Mulder, P. G. H.; Sauer,
P. J. J.; Hooijkaas, H. Immunologic effects of background exposure to polychlorinated
biphenyls and dioxins in Dutch preschool children. Environ. Health Perspect. 2000, 108,
12031207.

[Crossref], [PubMed], [CAS]

71. (71)
Gies, A.; Neumeier, G.; Rappolder, M.; Konietzka, R. Risk assessment of dioxins and dioxin-
like PCBs in foodComments by the German Federal Environmental
Agency. Chemosphere 2007, 67, S344S349.

[Crossref], [PubMed], [CAS]

http://pubs.acs.org/doi/full/10.1021/es071492j

Terjemahan

Body Loadings and Health Risk Assessment of Polychlorinated


Dibenzo-p-dioxins and Dibenzofurans at an Intensive Electronic
Waste Recycling Site in China

Janet K.Y. ,Guan Hua Xing,Ying Xu,Ying Liang,Ling Xuan Chen,Sheng Chun Wu,Chris K. C.
Wong,Clement K. M. Leung,# andMing H. Wong*
Croucher Institute for Environmental Sciences, and Department of Biology, Hong Kong Baptist University,
G/F, Block 5, Low-Rise Buildings, 32 Renfrew Road, Kowloon Tong, Hong Kong SAR, People's Republic
of China, State Key Laboratory of Freshwater Ecology and Biotechnology, Institute of Hydrobiology,
Chinese Academy of Sciences, 430072, Wuhan, Hubei Province, People's Republic of China, Luqiao
Hospital of Traditional Chinese Medicine, 318050, Taizhou Region, Zhejiang Province, People's Republic
of China, Centre for Disease Control and Prevention of Luqiao District, 318050, Taizhou Region, Zhejiang
Province, People's Republic of China, and IVF Centre Limited, Hong Kong Sanatorium and Hospital, 2
Village Road, Happy Valley, Hong Kong SAR, People's Republic of China
Environ. Sci. Technol., 2007, 41 (22), pp 76687674
DOI: 10.1021/es071492j
Publication Date (Web): October 6, 2007
Copyright 2007 American Chemical Society

Abstract
This study is one of the very few investigating the dioxin body burden of a group of child-bearing-
aged women at an electronic waste (e-waste) recycling site (Taizhou, Zhejiang Province) (24 2.83
years of age, 40% were primiparae) and a reference site (Lin'an city, Zhejiang Province, about 245
km away from Taizhou) (24 2.35 years of age, 100% were primiparae) in China. Five sets of
samples (each set consisted of human milk, placenta, and hair) were collected from each site. Body
burdens of people from the e-waste processing site (human milk, 21.02 13.81 pg WHO-TEQ1998/g
fat (World Health Organization toxic equivalency 1998); placenta, 31.15 15.67 pg WHO-TEQ1998/g
fat; hair, 33.82 17.74 pg WHO-TEQ1998/g dry wt) showed significantly higher levels of
polychlorinated dibenzo-p-dioxins and polychlorinated dibenzofurans (PCDD/Fs) than those from the
reference site (human milk, 9.35 7.39 pg WHO-TEQ1998/g fat; placenta, 11.91 7.05 pg WHO-
TEQ1998/g fat; hair, 5.59 4.36 pg WHO-TEQ1998/g dry wt) and were comparatively higher than other
studies. The difference between the two sites was due to e-waste recycling operations, for example,
open burning, which led to high background levels. Moreover, mothers from the e-waste recycling
site consumed more foods of animal origin. The estimated daily intake of PCDD/Fs within 6 months
by breast-fed infants from the e-waste processing site was 2 times higher than that from the
reference site. Both values exceeded the WHO tolerable daily intake for adults by at least 25 and 11
times, respectively. Our results implicated that e-waste recycling operations cause prominent
PCDD/F levels in the environment and in humans. The elevated body burden may have health
implications for the next generation.

Terjemahan
Body Loadings dan Penilaian Risiko Kesehatan Polychlorinated Dibenzo-p-dioxins dan
Dibenzofurans di Situs Daur Ulang Limbah Digital Intensif di China

Janet K.Y. , Guan Hua Xing, Ying Xu, Ying Liang, Ling Xuan Chen, Sheng Chun Wu, Chris
K. C. Wong, Clement K. M. Leung, # andMing H. Wong *
Croucher Institute for Environmental Sciences, dan Department of Biology, Universitas Baptis Hong
Kong, G / F, Blok 5, Bangunan dengan Kebangkitan Rendah, 32 Jalan Renfrew, Kowloon Tong,
Hong Kong SAR, Republik Rakyat Cina, Laboratorium Kunci Negara Ekologi Air Tawar dan
Bioteknologi, Institut Hidrobiologi, Akademi Ilmu Pengetahuan China, 430072, Wuhan, Provinsi
Hubei, Republik Rakyat Cina, Rumah Sakit Luqiao Pengobatan Tradisional China, 318050, Daerah
Taizhou, Provinsi Zhejiang, Republik Rakyat Cina, Pusat Pengendalian dan Pencegahan Penyakit
Distrik Luqiao, 318050, Daerah Taizhou, Provinsi Zhejiang, Republik Rakyat Cina, dan Pusat IVF
Limited, Sanatorium dan Rumah Sakit Hong Kong, 2 Jalan Desa, Happy Valley, Hong Kong SAR,
Republik Rakyat Cina
Mengepung. Sci. Technol., 2007, 41 (22), hlm 7668-7674
DOI: 10.1021 / es071492j

Tanggal Publikasi (Web): 6 Oktober 2007


Hak Cipta 2007 American Chemical Society

Abstrak

Penelitian ini adalah salah satu dari sedikit investigasi beban tubuh dioksin sekelompok wanita balita
yang melahirkan anak di situs daur ulang limbah elektronik (e-waste) (Provinsi Taizhou, Zhejiang)
(usia 24 2.83 tahun, 40% adalah primiparae) dan situs referensi (kota Lin'an, Provinsi Zhejiang,
sekitar 245 km dari Taizhou) (24 2.35 tahun, 100% adalah primiparae) di China. Lima set sampel
(masing-masing set terdiri dari susu, plasenta, dan rambut) dikumpulkan dari masing-masing lokasi.
Beban tubuh orang-orang dari tempat pengolahan limbah elektronik (susu manusia, 21,02 13,81
pg lemak WHO-TEQ1998 / g lemak (Keragaman toksik Organisasi Kesehatan Dunia 1998);
plasenta, 31,15 15,67 pg lemak WHO-TEQ1998 / g; rambut, 33,82 17,74 pg WHO-TEQ1998 / g
dry wt) menunjukkan tingkat yang lebih tinggi secara signifikan pada dienzin poliporfinated dibenzo-
p-dioksin dan polychlorinated dibenzofurans (PCDD / Fs) dibandingkan dengan yang berasal dari
situs referensi (susu manusia, 9,35 7,39 pg lemak WHO-TEQ1998 / g lemak , plasenta, 11,91
7,05 pg lemak WHO-TEQ1998 / g; rambut, 5,59 4,36 pg WHO-TEQ1998 / g kering wt) dan relatif
lebih tinggi daripada penelitian lainnya. Perbedaan antara kedua lokasi itu karena operasi daur
ulang limbah elektronik, misalnya pembakaran terbuka, yang menyebabkan tingkat latar belakang
tinggi. Apalagi, para ibu dari situs daur ulang e-waste mengkonsumsi lebih banyak makanan hewani.
Diperkirakan asupan PCDD / F setiap hari dalam waktu 6 bulan oleh bayi yang diberi ASI dari
tempat pengolahan limbah elektronik 2 kali lebih tinggi dari pada situs referensi. Kedua nilai tersebut
melebihi asupan harian WHO yang dapat ditoleransi untuk orang dewasa setidaknya 25 dan 11 kali.
Hasil kami berimplikasi bahwa operasi daur ulang limbah e-mail menyebabkan tingkat PCDD / F
yang menonjol di lingkungan dan manusia. Beban tubuh yang meningkat mungkin memiliki implikasi
kesehatan bagi generasi berikutnya.
pengantar
Limbah elektronik, "e-waste" atau "waste electrical and electronic equipment" (WEEE) yang
didefinisikan oleh European Community Directive 2002/96 / EC, adalah jenis limbah yang terdiri dari
alat listrik atau elektronik yang rusak atau tidak diinginkan. Usahakan e-waste sudah menjadi
masalah serius. Rata-rata umur komputer di negara maju telah turun dari 6 tahun di tahun 1997
menjadi 2 tahun di tahun 2005 (1). Menurut Administrasi Perlindungan Lingkungan Negara China,
70% limbah e-mail di seluruh dunia telah dikirim ke China (2). Di Amerika Serikat bagian barat,
sampai 80% limbah elektronik yang dikumpulkan untuk didaur ulang diekspor ke Asia, dimana 90%
dikirim ke China karena standar lingkungan yang lebih rendah dan tenaga kerja yang lebih murah
(3). Apalagi di China sendiri, 4 juta PC dibuang setiap tahun (4).
Ada beberapa situs pengolahan limbah elektronik di China, dimana wilayah Taizhou di Provinsi
Zhejiang dan kota Guiyu di Provinsi Guangdong adalah yang paling intensif (2). "Daur ulang"
dilakukan dengan metode rudimenter, yang meliputi tumpukan kawat yang terbakar untuk
memulihkan logam, papan sirkuit lelehan di atas panggangan batubara untuk melepaskan chip
berharga, casing komputer untuk menghilangkan plastik yang mudah terbakar dan mengisolasi
logam, dan mengeluarkan logam di bak asam (5, 6). Penelitian kami sebelumnya yang dilakukan di
Guiyu menunjukkan bahwa polutan organik yang persisten (POPs) dan logam berat menyebabkan
kontaminasi serius di udara, tanah, sedimen, dan air tawar (5-11). Dioxin (PCDD / Fs), yaitu
polychlorinated dibenzo-p-dioxins (PCDDs) dan polychlorinated dibenzofurans (PCDFs), menjadi
perhatian khusus karena pembakaran limbah padat melepaskan sejumlah besar senyawa beracun
ini (12). Pembakaran terbuka dan pelindian asam ditemukan untuk melepaskan jumlah dioksin
terbesar dari semua proses operasi limbah elektronik (8), dan tempat pembuangan terbuka
merupakan sumber potensial dioksin karena pembakaran yang tidak terkendali (13). Oleh karena
itu, pembakaran dan pembuangan limbah yang tidak terkendali dapat menimbulkan ancaman serius
bagi kesehatan pekerja dan penduduk setempat. Organisasi Kesehatan Dunia (WHO) telah
mengkoordinasikan studi paparan tentang dioksin dalam susu manusia sejak 1987 (14-16). Sampel
susu manusia dikumpulkan dari beberapa daerah di China untuk menentukan tingkat dioksin (17-
21). Namun, informasi tentang beban tubuh manusia dioksin di tempat daur ulang limbah elektronik
terbatas. Dengan demikian, tujuan utama dari penelitian ini adalah untuk melakukan penilaian risiko
kesehatan untuk menyelidiki beban tubuh dioksin penduduk lokal di wilayah Taizhou.
Bagian eksperimental
Sampling Site Description. Situs daur ulang e-waste adalah daerah Taizhou (TZ) yang terletak di
Provinsi Zhejiang, Cina timur (Gambar 1). Taizhou terletak di bagian pesisir tengah Zhejiang (garis
lintang 28 LU dan garis bujur 122 BT) dan memiliki garis pantai 745 km, merupakan bagian dari
28% dari Provinsi Zhejiang (22). Kegiatan daur ulang limbah E terutama dilakukan di sebuah kota
bernama Luqiao yang terletak di bagian selatan Taizhou, dengan total luas 274 km2 dan populasi
400.000.
angka
Gambar 1 Lokasi pengambilan contoh di Provinsi Zhejiang, Cina.

Kegiatan daur ulang e-waste di Taizhou dimulai pada akhir 1970-an dan sebagian besar ditangani
dengan limbah elektronik buatan dalam negeri (23). Pada awal 1990-an, Taizhou mulai memproses
e-waste impor. Saat ini, limbah elektronik impor menyumbang 90% dari total dan berasal dari
Jepang, Amerika Serikat, negara-negara Eropa Barat, dan Rusia. Dalam beberapa tahun terakhir,
Taizhou telah menjadi salah satu penerima utama e-waste di China. Ini terutama menerima logam
bekas, kapasitor listrik usang, peralatan rumah tangga, generator listrik, dan kabel kabel. Volume
limbah pembongkaran e-tahunan telah melampaui 2,2 juta metrik ton, dan volume penjualan telah
mencapai 4 miliar Yuan Cina (sekitar US $ 5,16 juta). Empat puluh ribu orang bekerja di sektor daur
ulang limbah elektronik. Sebagian besar operasi daur ulang melibatkan pembakaran udara terbuka,
pelindian asam, dan pembongkaran fisik oleh palu, pahat, pengemudi sekrup, dan tangan kosong.
Situs referensi tersebut adalah kota Lin'an (HZ) (garis lintang 30 LU dan bujur 118 BT), prefektur
Hangzhou, Provinsi Zhejiang (24). Jaraknya sekitar 245 km dari Taizhou. Lin'an terletak di
pedalaman, di bagian utara Hangzhou, dan merupakan kota dengan luas tanah 3127 km2 dan
berpenduduk 520.000.
Studi Populasi. Susu manusia, plasenta, dan sampel rambut dikumpulkan di dua lokasi penelitian
dari 10 wanita yang melahirkan antara bulan Agustus dan Desember 2005. Ke-10 wanita ini dipilih
secara acak dengan kondisi dimana mereka tinggal di tempat studi paling sedikit 2 tahun dan
mereka bersedia menyumbangkan sejumlah besar rambut dan susu untuk analisis kimia. Satu set
spesimen dikumpulkan dari masing-masing individu. Para donor diakses melalui Rumah Sakit
Luqiao Pengobatan Tradisional China, Rumah Sakit Pengobatan Tradisional China Lin'an, dan
Pusat Pengendalian dan Pencegahan Penyakit setempat. Sebelum mengumpulkan spesimen, para
donor menyelesaikan sebuah informed consent. Survei tentang karakteristik pribadi mereka
dilakukan (lihat Tabel S1, Informasi Pendukung).
Pengumpulan data. Data sosial-demografi dan kebiasaan konsumsi makanan pada populasi
penelitian diperoleh dari wawancara tatap muka dan kuesioner asupan makanan semiquantitatif.
Selama wawancara, para donor menjawab pertanyaan yang dimodifikasi dari putaran kedua studi
paparan PCDD, PCDF, dan PCB oleh WHO (14). Asupan berbagai jenis makanan dinilai (lihat Tabel
S2, Informasi Pendukung). Asupan mingguan (g / minggu) untuk setiap makanan dihitung untuk
masing-masing individu. Perubahan diet selama kehamilan diabaikan. Tingkat responnya 100%.
Koleksi Sampel. Susu manusia (~ 100 mL) dikumpulkan dari masing-masing donor saat bayi
berumur 4-5 hari. Sampel secara manual diekspresikan dan dikumpulkan dalam botol reagen bekas
heksana dengan tutup berlapis Teflon. Plasenta dikumpulkan pada hari persalinan dan ditempatkan
secara terpisah ke dalam wadah gelas yang sudah dibersihkan. Rambut (~ 3 g) dikumpulkan pada
hari pertama setelah persalinan dan diambil sampelnya dari dekat kulit kepala dan dari tengkuk
leher dengan menggunakan gunting stainless steel. Kemudian dimasukkan ke dalam tas polietilen
yang dapat ditutup. Semua spesimen dibekukan segera setelah dikumpulkan dan disimpan pada
suhu -20 C sampai analisis kimia.
Analisis Laboratorium. Analisis kimia dilakukan oleh Laboratorium Kunci Negara untuk Ekologi dan
Bioteknologi Air Tawar, Institut Hidrobiologi, Akademi Ilmu Pengetahuan China, China. Sampel susu
dan plasenta manusia dikeringkan dan kemudian dihomogenisasi. Rambut dicuci dengan deterjen
komersial (1%) selama 5 menit, diikuti oleh air suling, untuk menghilangkan kotoran di permukaan,
misalnya, produk perawatan rambut, yang dapat mengganggu analisis kimia (25). Kemudian
dikeringkan dengan oven pada suhu 70 C. Setiap sampel dibubuhi dengan pengganti EDF-8999
dan kemudian diekstraksi Soxhlet berdasarkan Metode EPA A.S. 3540C (26). Kandungan lipid susu
manusia dan sampel plasenta ditentukan secara gravimetri dari aliquot ekstrak. Proses pembersihan
kemudian dilakukan dengan menggunakan tiga kolom yang diisi dengan silika gel (27), alumina
dasar teraktif (28), dan florisil (29). Standar internal (EDF-5999, 13C12 1,2,3,4-TCDD, dan 13C12
1,2,3,7,8,9-HxCDD) (10 L) ditambahkan ke sampel terkonsentrasi untuk kromatografi gas dengan
resolusi tinggi. / analisis spektrometri massa resolusi tinggi (HRGC / HRMS) (30). Analisis dilakukan
pada kromatografi gas Agilent 5890II (Agilent Technologies, AS) yang digabungkan dengan
spektrometer massa Finnigan MAT 95 (Thermo Electron, AS) yang dilengkapi dengan autosampler
CTC A200S (CTC, Swiss) pada resolusi 10.000. Sebuah RTX -DIOXIN2 kolom kapiler (60 m 0,25
mm id 0,25 m ft, Restek Co.) digunakan untuk pemisahan majemuk. PCDD / Fs diidentifikasi
dengan spektrometri massa di EI dan beberapa mode deteksi ion.

Ekspresi Konsentrasi PCDD / F. Tingkat PCDD / Fs ditunjukkan sebagai konsentrasi massa dan
ekuivalensi toksik (TEQ) WHO 1998 (31). Beban tubuh dinyatakan sebagai picogram dioxin TEQs
per gram lemak pada susu manusia dan plasenta. Mereka juga dinyatakan sebagai picogram dioxin
TEQs per gram berat kering bila perbandingan dilakukan di antara tiga jenis sampel. Nilai yang tidak
terdeteksi diperlakukan sebagai nol.
Analisis data. Paket Statistik untuk Ilmu Pengetahuan Sosial (SPSS of Windows, versi 11.0; SPSS
Inc., Chicago, IL) digunakan untuk analisis data kuantitatif. Perbedaan antar kelompok dinilai
dengan uji t Student atau analisis varians (ANOVA). Koefisien korelasi pearson digunakan untuk
menentukan hubungan antar parameter yang berbeda. Tingkat signifikan adalah p <0,05 dan ekor
dua. Data disajikan sebagai sarana SD.
Hasil dan Diskusi
Faktor-faktor yang Mempengaruhi Tingkat Dioxin: Karakteristik Demografi dan Intake Makanan.
Berbagai faktor dilaporkan terkait dengan konsentrasi POP pada susu manusia seperti paritas, usia
ibu, preferensi makanan, dan masa menyusui (32). Dalam penelitian ini, total TEQ meningkat
dengan lama tinggal di TZ (r = 0,993 dan p = 0,01 untuk susu manusia, r = 0,950 dan p = 0,013
untuk plasenta) dan jumlah aborsi spontan donor (r = 0,929 dan p = 0,023 untuk rambut).
Peningkatan aborsi spontan diamati di situs yang terkontaminasi dioksin di Seveso dan Chapaevsk,
Rusia (33). Namun, Takekuma dkk. (34) tidak menemukan hubungan yang signifikan antara tahun
tinggal dan nilai TEQ pada susu manusia. Tingkat dioxin pada spesimen manusia ditemukan
berkorelasi positif dengan usia ibu (17, 34, 35). Namun demikian, dalam penelitian ini, tingkat tidak
berbeda secara signifikan dengan usia (p <0,05). Hasil ini konsisten dengan penelitian lain yang
berkaitan dengan POPs (19, 36). Rentang usia yang sempit, paparan kontaminan baru-baru ini (37),
dan ukuran sampel terbatas adalah alasan yang mungkin untuk hasilnya. Paritas tidak menunjukkan
korelasi dengan beban tubuh dalam penelitian ini (p <0,05). Penelitian lain juga mengungkapkan
hasil tersebut (36, 38). Sebaliknya, Beck et al. (35) dan Iida et al. (39) melaporkan tingkat dioksin
pada susu manusia dari primiparae lebih tinggi daripada multiparae. Nilai TEQ pada susu manusia
dari lokasi pembuangan di India menunjukkan korelasi negatif dengan jumlah persalinan (38).
Hasil penelitian ini menunjukkan bahwa ada peningkatan secara signifikan pada tingkat susu dioksin
TZ dengan konsumsi kepiting (r = 0,888 dan p = 0,044) dan telur (r = 0,921, p = 0,026). Selain itu,
nilai TEQ untuk plasenta TZ juga berkorelasi signifikan dengan asupan kepiting (r = 0,924, p =
0,025), sedangkan proporsi lemak susu TZ menunjukkan korelasi yang signifikan dengan asupan
kerang (r = 0,886, p = 0,045). Ada korelasi statistik antara pembebanan tubuh HZ dan asupan
makanan yang berasal dari hewan: bivalve (r = 0,954, p = 0,012 untuk susu manusia, r = 0,920, p =
0,027 untuk plasenta), daging babi (r = 0,904, p = 0,035 untuk susu manusia, r = 0,953, p = 0,012
untuk plasenta), daging sapi / domba (r = 0,917, p = 0,028 untuk susu manusia), ayam (r = 0,913, p
= 0,028 untuk susu manusia), dan perut hewan = 0,981 dan p = 0,019 untuk rambut). Namun, tidak
ada korelasi yang signifikan antara total TEQ dan karakteristik pribadi. Ini menunjukkan bahwa
konsumsi makanan yang berasal dari hewan adalah yang utama d
Tabel 1. Konsentrasi (pg / g dan pg WHO-TEQ / g) PCDD / Fs pada Spesimen Manusia dari Situs
Daur Ulang E-Waste (TZ) dan Situs Referensi (HZ) a, b, c
situs referensi situs daur ulang limbah e-waste (TZ) (HZ)
kemas susu WHO-TEF pg / g lemak plasenta pg / g lemak rambut pg / g kering dengan susu
manusia pg / g lemak plasenta pg / g lemak rambut pg / g kering wt
PCDD congeners
2,3,7,8-TCDD 1 3,59 4,88 2,31 3,11 4,74 4,48
1,2,3,7,8-PeCDD 1 4,65 10,56 7,45 1,47 2,46 0,326
1,2,3,4,7,8-HxCDD 0,1 2,11 2,43 2,42 1,21 1,66 0,106
1,2,3,6,7,8-HxCDD 0,1 4,76 1,10 4,08 2,80 0,717 0,106
1,2,3,7,8,9-HxCDD 0,1 2,30 0,606 2,10 0,948 0,539 0,065
1,2,3,4,6,7,8-HpCDD 0,01 10.2 7.06 12.4 5.08 5.85 1.31

OCDD 0.0001 80,9 49,8 22,6 41,0 52,7 6,80


PCDD-TEQ 9.27 15.93 10.74 5.13 7.55 4.84
PCDF congeners
2,3,7,8-TCDF 0,1 9,54 5,95 46,6 1,35 1,60 1,16

1,2,3,7,8-PeCDF 0,05 6,86 8,70 23,7 0,404 0,725 0,142


2,3,4,7,8-PeCDF 0,5 15,4 31,4 24,6 6,06 6,51 0,705
1,2,3,4,7,8-HxCDF 0,1 10,4 14,53 14,8 3,81 3,74 1,01
1,2,3,6,7,8-HxCDF 0,1 9,23 6.76 15,2 3,08 2,77 0,744
2,3,4,6,7,8-HxCDF 0,1 6,12 2,73 14,0 2,66 1,55 0,740
1,2,3,7,8,9-HxCDF 0,1 0,323 0,372 2,71 0,123 0,436 0,0652
1,2,3,4,6,7,8-HpCDF 0,01 13,0 4,49 24,9 6,29 4,84 2,05
1,2,3,4,7,8,9-HpCDF 0,01 1,23 1,01 2,01 0,133 0,967 0,0652

OCDF 0,0001 1.45 2.03 6.62 0.417 7.18 1.87


PCDF-TEQ 11.7 19.22 23.1 4.22 4.36 0.752
PCDD / F-TEQ 21.0 35.1c 33.8c 9.35 11.9 5.59
Singkatan: HpCDD, hetachlorodibenzodioxin; HpCDF, heptachlorodibenzofuaran; HxCDF,
hexachlorodibenzofuaran; HxCDD, hexahetachlorodibenzodioxin; OCDD, octachlorodibenzodioxin;
OCDF, octachlorodibenzofuaran; TCDD, tetrahetachlorodibenzodioxin; TCDF,
tetrachlorodibenzofuaran.b Deteksi batas (pg / g): susu, TCDD / F = 0,10-0,13, PeCDD / F = 0,10-
0,17, HxCDD / F dan HpCDD / F = 0,07-0,13, OCDD / F = 0,13-0,23 ; plasenta, TCDD / F = 0,06-
0,08, PeCDD / F = 0,06-0,10, HxCDD / F dan HpCDD / F = 0,04-0,08, OCDD / F = 0,08-0,14;
rambut, TCDD / F = 0,15-0,20, PeCDD / F = 0,15-0,25, HxCDD / F dan HpCDD / F = 0,10-0,20,
OCDD / F = 0,20-0,35.c Perbedaan yang signifikan antara sampel TZ dan HZ (p <0,05 ).
Perbedaan tersebut juga bisa dijelaskan oleh karakteristik pribadi dan asupan makanan. Dari semua
karakteristik pribadi, paritas dan jumlah anak yang diberi ASI menunjukkan perbedaan yang
signifikan antara kedua lokasi (p <0,05) (lihat Tabel S1, Informasi Pendukung). Empat puluh persen
ibu TZ adalah primiparae, sementara semua ibu HZ adalah primiparae. Wanita-wanita ini dipilih
sesuai dengan kriteria yang disebutkan di bagian Populasi Studi. Penelitian sebelumnya
menunjukkan bahwa peningkatan paritas atau peningkatan masa menyusui berhubungan langsung
dengan beban tubuh yang lebih ringan dari PCDD / Fs (35, 38, 39). Namun, fenomena ini tidak
diamati dalam penelitian ini. Dengan demikian, kedua parameter ini nampaknya tidak
mempengaruhi beban tubuh. Di sisi lain, menurut hasil survei konsumsi makanan, ibu TZ umumnya
mengkonsumsi lebih banyak makanan hewani, dimana konsumsi daging babi dan perut hewan
secara signifikan lebih tinggi (p <0,05) (lihat Tabel S2, Informasi Pendukung). Makanan yang berasal
dari hewan dianggap sebagai sumber diet utama dioksin sejak POPs mencari lemak dan menumpuk
pada lemak hewan (48). Seperti yang telah disebutkan sebelumnya, analisis statistik menunjukkan
bahwa konsumsi yang lebih tinggi dari kelas makanan ini menyebabkan beban tubuh lebih besar
pada ibu TZ (p <0,05).
Konsentrasi Congener dan Profil Homolog. Congener paling beracun, 2,3,7,8-TCDD, hadir di semua
sampel dari kedua lokasi. Rata-rata 2,3,7,8-TCDD, 2,3,4,7,8-PeCDF, dan 1,2,3,7,8-PeCDD
memberikan kontribusi 7-80%, 6-45%, dan 6 -30%, masing-masing, terhadap total TEQs. Ketiga
penyangga ini terbentuk hingga 65-92%. Profil homolog menunjukkan nasib lingkungan dan sumber
dioksin (49). Sampel masing-masing donor TZ atau HZ menunjukkan profil yang serupa dengan
profil perwakilan (diperoleh dengan menggunakan konsentrasi rata-rata). Semua sampel dari kedua
lokasi, kecuali rambut TZ, menunjukkan profil homolog yang serupa dimana PCDD (TCDD, 18-64%;
OCDD, 20-40%) berkontribusi besar terhadap konsentrasi total (lihat Angka S1a-S1d dan S1f,
Informasi Pendukung). Sebaliknya, rambut TZ menunjukkan profil homolog yang berbeda yang
didominasi oleh tetra melalui fisi heksaklorinasi (73%) (lihat Gambar S1e, Informasi Pendukung).
Alasan kontradiksi di antara sampel TZ tidak diketahui. Nasib terperinci dioksin setelah memasuki
tubuh manusia melalui eksposur yang berbeda tidak dikenali dengan jelas. Disarankan agar profil
untuk rambut mungkin menunjukkan paparan dioksin yang lebih baru karena rambut langsung
kontak dengan media paparan (atmosfir), sedangkan untuk susu dan plasenta mungkin
mencerminkan eksposur sejarah. Namun, spekulasi ini hanya bisa diterapkan di daerah yang sangat
terkontaminasi karena perbedaan tersebut tidak diamati pada sampel HZ. Profil untuk rambut TZ
sangat mirip dengan rambut pekerja pada sumber emisi, seperti insinerator MSW (45). Kedua profil
itu sangat berbeda dari itu
Penggunaan Spesimen Manusia sebagai Indikator Biologis untuk Kontaminasi Dioksin. Berbagai
jenis spesimen manusia menunjukkan kelebihan dan kekurangan untuk menilai eksposur. Dioxin di
rambut menunjukkan akumulasi tubuh dan endapan atmosfir ke permukaan rambut (25). Rambut
bisa diaplikasikan ke semua kelompok populasi. Pengambilan sampelnya sangat mudah dan tidak
invasif (50). Kandungan lipida yang relatif tinggi (3,5-4%) menunjukkan stabilitas untuk analisis kimia
(51, 52). Namun, sulit untuk membedakan antara kontaminasi eksogen dan endogen (53).
Konsentrasi dapat bervariasi jika rambut dari berbagai posisi kepala dikumpulkan (25). Selain itu,
konsentrasi yang berbeda ditemukan sepanjang rambut (54). Placenta memberikan indikasi yang
baik untuk paparan prenatal (21). Variasi di antara berbagai donor dapat dikurangi karena waktu
sampling yang sama, biasanya pada hari persalinan. Selain itu, plasenta ideal untuk biomonitoring
karena cukup besar untuk memungkinkan pengujian beberapa polutan selama pengambilan sampel
yang sama. Meski demikian, ini terbatas pada betina dan tidak mudah didapat. Jaringan harus
diperoleh dengan prosedur yang lebih invasif (53). Susu manusia mencerminkan beban tubuh ibu
dan transfer dioksin setelah melahirkan dari ibu ke bayi (15). Apalagi koleksi susu manusia itu
nyaman dan noninvasive dan mudah direplikasi. Kandungan lemak yang tinggi (2-5%) membuat
metode ekstraksi lebih mudah dan meningkatkan ketepatan pengukuran. Namun, susu manusia
terbatas pada wanita menyusui. Selanjutnya, semua sampel susu harus dikumpulkan pada waktu
menyusui yang sama seperti tingkat dioxin bervariasi sepanjang masa menyusui (35).
Saat membandingkan tiga jenis spesimen dari TZ, rambut mengandung konsentrasi dioksin tertinggi
(33,82 17,74 pg WHO-TEQ / g kering wt; p = 0,001), diikuti oleh susu manusia (2,96 1,30 pg
WHO-TEQ / g kering wt ), dan kemudian plasenta (2,06 1,30 pg WHO-TEQ / g kering wt). Sampel
dari HZ juga menunjukkan kecenderungan yang sama dimana konsentrasi PCDD / F pada rambut
(5,59 4,43 pg WHO-TEQ / g kering wt) secara signifikan lebih tinggi daripada plasenta (0,63 0,28
pg WHO-TEQ / g dry wt; p = 0,032); Namun, tidak ada perbedaan yang signifikan dengan jumlah
susu manusia (2,20 1,45 pg WHO-TEQ / g kering wt; p> 0,05). Nilai TEQ dari ketiga jenis
spesimen TZ menunjukkan korelasi positif yang signifikan satu sama lain (r = 0,995 dan p <0,001
untuk susu manusia dan plasenta; r = 0,900 dan p = 0,037 untuk susu dan rambut manusia; r =
0,892 dan p = 0,042 untuk plasenta dan rambut). Untuk sampel HZ, hanya konsentrasi dioksin pada
susu manusia yang menunjukkan korelasi positif yang signifikan dengan konsentrasi plasenta (r =
0,930, p = 0,022). Hasil ini tampaknya menunjukkan bahwa di tempat yang sangat terkontaminasi,
rambut dapat digunakan sebagai bioindikator yang andal untuk beban tubuh dioksin. Namun,
penyelidikan lebih lanjut diperlukan untuk membuktikan hipotesis ini dan untuk mengetahui
penyebab yang menyebabkan profil homolog berbeda untuk berbagai jenis sampel.
Perbandingan dengan Tingkat PCDD / F di Seluruh Dunia dan Domestik. Susu Manusia Semua
sampel TZ dan 80% sampel HZ melebihi tingkat maksimum yang diizinkan Uni Eropa dalam susu (3
pg lipida WHO-TEQ / g) (55). Konsentrasi yang pertama tinggi, sedangkan yang kedua bersifat
moderat bila dibandingkan dengan 26 negara yang terlibat dalam Studi Paparan Ketiga WHO
tentang Dioksin Milk Manusia (15) (lihat Gambar S2, Informasi Pendukung). Misalnya, konsentrasi
dalam susu manusia TZ akan berada di peringkat 2 setelah Mesir, sedangkan HZ menunjukkan
konsentrasi yang serupa dengan Irlandia dan Norwegia. Selain itu, susu manusia TZ menunjukkan
konsentrasi tertinggi di antara sampel yang dikumpulkan dari bagian lain China selama 2000-2005
(lihat Tabel S3, Informasi Pendukung). Sampel HZ mengandung konsentrat yang sebanding dengan
yang dari Dalian dan Shenyang (19), Taiwan (17, 21), Shijiazhuang, dan Tangshan (56). Hal ini
semakin menegaskan bahwa beban tubuh ibu TZ yang relatif berat disebabkan oleh kegiatan daur
ulang limbah elektronik yang tidak ada dalam studi lain. Schecter dan rekan kerja (57, 58)
menyelidiki tingkat kontaminasi dioksin di daerah yang telah disemprot dengan natrium
pentachlorophenol (Na-PCP) untuk mengendalikan schistosomiasis. Na-PCP adalah pestisida yang
terkontaminasi dengan PCDD terklorinasi tinggi. Sampel susu manusia yang dikumpulkan dari
daerah semprotan mengandung konsentrasi yang 4 kali lipat lebih rendah daripada yang berasal
dari TZ. Namun, mereka yang dikumpulkan dari penduduk yang tinggal di dekat Danau Ya-Er, yang
telah sangat tercemar oleh limbah dari pabrik kloroalkali di dekatnya, mengandung nilai TEQ yang
sangat tinggi (59).
Plasenta Konsentrasi pada sampel TZ 2-3 kali lipat lebih tinggi daripada spesimen dari populasi
umum di Taiwan tengah (21, 60), Amerika Serikat (61), dan Jerman (62) dan sebanding dengan
yang dari Jepang (63) (lihat Tabel S3, Informasi Pendukung). Namun, mereka dikumpulkan dari
enam ibu dengan penyakit Yu-Cheng yang disebabkan oleh konsumsi minyak terkontaminasi PCB
di acara Taiwan
Plasenta Konsentrasi pada sampel TZ 2-3 kali lipat lebih tinggi daripada spesimen dari populasi
umum di Taiwan tengah (21, 60), Amerika Serikat (61), dan Jerman (62) dan sebanding dengan
yang dari Jepang (63) (lihat Tabel S3, Informasi Pendukung). Namun, mereka yang dikumpulkan
dari enam ibu dengan penyakit Yu-Cheng yang disebabkan oleh konsumsi minyak terkontaminasi
PCB di Taiwan menunjukkan tingkat dioksin yang jauh lebih tinggi (64) dibandingkan semua
penelitian lainnya.
Rambut. Hanya ada beberapa penelitian tentang dioksin pada rambut manusia (lihat Tabel S3,
Informasi Pendukung). Nilai TEQ tertinggi ditemukan oleh penelitian ini, diikuti oleh Luxemb et al.
(65) yang mengumpulkan sampel dari toko tukang cukur di sebuah lokasi daur ulang limbah e
(Guiyu, Provinsi Guangdong) di China. Total TEQs pada sampel rambut dan abu yang dilaporkan
oleh penelitian ini relatif tinggi (21,0 dan 5858,33 pg WHO-TEQ / g, masing-masing), menunjukkan
bahwa kegiatan pengolahan limbah elektronik melepaskan sejumlah besar dioksin. Rambut yang
dikumpulkan dari penghuni yang tinggal di dekat Danau Ya-Er mengandung konsentrasi 25 kali lebih
rendah dari rambut TZ (66). Namun, susu manusia yang dikumpulkan dari Danau Ya-Er
menunjukkan tingkat yang lebih tinggi daripada yang berasal dari TZ (59). Kontradiksi semacam itu
mungkin menyiratkan bahwa ada masukan segar dari dioksin ke lingkungan atmosfer di TZ karena
rambut merupakan indikator bagus untuk dioksin di atmosfer (44, 46, 47, 63).
Penilaian Resiko Kesehatan untuk Bayi. Untuk mengevaluasi risiko yang dihadapi bayi melalui
menyusui, perkiraan asupan harian (EDI) PCDD / Fs harus ditentukan (lihat Informasi Pendukung
untuk perhitungannya). Bayi TZ mengkonsumsi 102,98 67,65 pg TEQ / kg BB / hari yang 2 kali
lebih tinggi dari pada bayi HZ (45,83 36,22 pg TEQ / kg berat badan / hari). Kedua nilai tersebut
akan melebihi jumlah asupan harian WHO tolerable (TDI) (1-4 pg TEQ / kg berat badan / hari) (67)
paling sedikit 25 dan 11 kali. Dengan asumsi bahwa 90% dioksin yang tertelan diserap (68),
paparan bayi masih akan serius. WHO TDI mencakup paparan PCB seperti dioxin; Dengan
demikian, EDI untuk bayi TZ mungkin meremehkan risikonya. Meskipun TDI telah diperkirakan
untuk manusia selama seumur hidup mereka, paparan akut melalui asupan tinggi melebihi batas
toksikologi selama menyusui menjadi perhatian karena paruh waktu yang panjang dari senyawa dan
pertahanan tubuh yang belum matang pada bayi. Studi menemukan bahwa paparan postnatal pada
dioxin mempengaruhi sistem hormon tiroid dan fungsi imunologis pada bayi dan anak-anak (69, 70).
Selain itu, perlu dicatat bahwa bayi dan anak-anak menyerap dioksin pada tingkat yang lebih cepat
daripada orang dewasa karena tingkat pertumbuhannya yang tinggi (71). Selain itu, bayi TZ berisiko
lebih besar karena tingkat latar belakang yang lebih tinggi, menyiratkan bahwa mereka akan
menyerap lebih banyak dioksin melalui kontak kulit, inhalasi, dan paparan prenatal. Namun,
pemberian ASI harus didorong, mengingat bayi mendapat keuntungan dan perlindungan nutrisi dari
penyakit menular (17, 18).
Ini adalah studi pertama yang menyelidiki tingkat PCDD / F pada susu manusia, plasenta, dan
rambut yang dikumpulkan dari ibu di tempat daur ulang limbah intensif dan situs referensi di China.
Meskipun sejumlah sampel dianalisis, hasilnya menunjukkan bahwa operasi daur ulang e-waste
menyebabkan peningkatan kadar PCDD / F pada manusia dan lingkungan. Beban tubuh dioksin
pada orang-orang dari tempat pengolahan limbah elektronik menempati peringkat di antara yang
tertinggi bila dibandingkan secara internasional. Beban tubuh yang meningkat dapat menyebabkan
implikasi kesehatan untuk genera berikutnya. Penelitian ini akan lebih komprehensif jika ukuran
sampel meningkat. Namun, biaya analisis kimia dioksin harus dipertimbangkan. Di sisi lain,
pekerjaan harus dilakukan untuk mengurangi dampak negatif kegiatan daur ulang limbah elektronik
terhadap lingkungan dan manusia. Misalnya, pendidikan yang didukung oleh pemerintah pusat dan
daerah harus dilakukan untuk mengajari warga setempat mewujudkan daur ulang limbah elektronik
menjadi masalah dan harus diatasi. Selain itu, penyelidikan lebih lanjut mengenai studi epidemiologi
mengenai dampak kesehatan yang disebabkan oleh operasi daur ulang limbah elektronik, tingkat
dioksin pada makanan lokal, dan kinetika tentang partisi POP di antara jaringan manusia yang
berbeda harus dilakukan.
Pengakuan
Kami berterima kasih kepada para ibu yang berkontribusi dalam penelitian ini dan menyumbangkan
susu, plasenta, dan sampel rambut. Penelitian ini didukung oleh The Research Grants Council dari
University Grants Committee dari Hong Kong (Central Allocation Group Research Project HKBU
1/3C), Match Fund dari Hong Kong Baptist University, dan sebuah sumbangan pribadi.

Informasi Pendukung Tersedia


Bagian Eksperimental, pengumpulan data, bagian Diskusi, penilaian risiko kesehatan bayi, Tabel
S1-S3, dan Angka S1a-S1f dan S2. Materi ini tersedia gratis melalui internet di http://pubs.acs.org.

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