Emerging Endocrine Disrupting Chemicals and Pharmaceuticals in

Downloaded by UNIV OF IDAHO on December 11, 2016 | http://pubs.acs.org Publication Date (Web): December 7, 2016 | doi: 10.1021/bk-2016-1244.ch010

Chapter 10

Emerging Endocrine Disrupting Chemicals and Pharmaceuticals in Vietnam: A Review of Environmental Occurrence and Fate in Aquatic and Indoor Environments Tran Manh Tri,1 Duong Hong Anh,2 Pham Manh Hoai,2 Nguyen Hung Minh,3 Vu Duc Nam,4 Pham Hung Viet,2 and Tu Binh Minh*,1 1Faculty

of Chemistry, VNU University of Science, 19 Le Thanh Tong Street, Hoankiem, Hanoi, Vietnam 2Center for Environmental Technology and Sustainable Development, VNU University of Science, 334 Nguyen Trai Street, Thanhxuan, Hanoi, Vietnam 3Center for Environmental Monitoring, Vietnam Environment Administration, Ministry of Natural Resources and Environement, 556 Nguyen Van Cu Street, Hanoi, Vietnam 4Center for Training, Consultancy and Technology Transfer, Vietnam Academy of Science and Technology, 18 Hoang Quoc Viet Road, Hanoi, Vietnam *E-mail: [email protected]

This chapter provides an overview of the most up-to-date information on the occurrences of several emerging environmental contaminants, which are known to possess active endocrine disrupting properties, and pharmaceuticals in indoor and aquatic environment from Vietnam. The groups of endocrine disrupting chemicals under investigation consist of siloxanes, phthalates, parabens, bisphenol A diglycidyl ether (BADGE), bisphenol A, bisphenol F, tetrabromobisphenol A (TBBPA), alkylphenolic compounds, some synthetic phenolic antioxidants and their metabolites. In addition, occurrences and distributions of several groups of pharmaceuticals such © 2016 American Chemical Society Loganathan et al.; Persistent Organic Chemicals in the Environment: Status and Trends in the Pacific Basin Countries II ... ACS Symposium Series; American Chemical Society: Washington, DC, 2016.


as antibiotics, anti-inflammatory, analgesic and lipid regulator drugs in aquatic environments were also reviewed. Systematic surveys of the occurrences of siloxanes, phthalates, parabens, bisphenol A diglycidyl ether (BADGE), bisphenol A and some synthetic phenolic antioxidants in indoor dust were conducted in several micro-environments such as homes, public places, laboratories, and offices in the Hanoi, Hungyen, Thaibinh, and Hatinh provinces in northern Vietnam. Indoor dust collected from Hanoi metropolitan area contained higher concentrations of most of EDCs as compared to other provinces, suggesting the role of extensive human and industrial activities increase the occurrence of these chemicals. In general, the frequency of detection and residue levels of most EDCs were higher in house dust than other micro-environments such as public places (supermarkets/grocery shops, electronic stores, pharmacies), laboratories, and offices, which could be related to their sources and usage. In particular, higher levels of siloxanes, phthalates, and parabens in dust samples from homes can be explained by their extensive use in personal care products and various household items. In general, indoor dust from Vietnam was in the lower range of EDCs contamination as compared to other countries in the world. In aquatic environments, widespread occurrences of some alkylphenolic compounds and bisphenol A were observed in surface water and sediment from landfill dumping sites for municipal wastes and coastal areas of some important agricultural and industrial areas in northern Vietnam. Higher levels of 4-nonyl phenols and bis-phenol A were encountered in Ba Lat estuary within the area receiving domestic and industrial wastewater discharges along the Red River Delta. A comprehensive survey to examine fluoroquinolone antibiotics in surface water and sediment from lakes and rivers in Hanoi metropolitan area revealed relatively higher concentrations of ciprofloxacin as compared to those reported from other locations in the world, indicating extensive use of this human antibiotic in Vietnam. Daily intakes of EDCs through dust ingestion in Vietnam were estimated to be the highest for phthalates, followed by bisphenol A, synthetic phenolic antioxidants, BADGEs, and TBBPA. In general, intakes of EDCs in Vietnam were lower than those estimated for industrialized countries. Further comprehensive studies should focus on examined occurrences and distributions of EDCs in environmental and human samples from suspected hotspots of pollutions.

224 Loganathan et al.; Persistent Organic Chemicals in the Environment: Status and Trends in the Pacific Basin Countries II ... ACS Symposium Series; American Chemical Society: Washington, DC, 2016.


Introduction In recent years, the increasing use of wide range of chemicals in consumer products significantly contributed to the contamination of aquatic and indoor environments (1–7). Environmental contamination, human exposure and toxic effects of persistent organic pollutants such as polychlorinated biphenyls (PCBs), polycyclic aromatic hydrocarbons (PAHs), polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/Fs), polybrominated diphenyl ethers (PBDEs), and organochlorine pesticides (OCPs) have been extensively investigated during the past four decades (8–11). The widespread occurrences of novel organic chemicals such as phthalates, bisphenol A, tetrabromobisphenol A (TBBPA), bisphenol A diglycidyl ether (BADGE), siloxanes, parabens, alkylphenols and pharmaceuticals such as antibiotics have been reported in industrialized countries (2, 4–6, 12). Unlike the legacy of classic POPs, these chemicals are still being used in various consumer products and therefore are continuously released into the environment (13–17). These groups of chemicals exert endocrine disrupting effects, and studies revealed that certain chemicals such as phthalates exhibited on association between exposure and various toxic responses such as reproductive toxicity, allergies and hepatotoxicity (18–30). Many studies have investigated the occurrence of these endocrine disrupting chemicals (EDCs) in environments such as water, air, indoor dust, sediment, and tissue samples in industrialized countries (3, 4, 7, 31–36). In recent years, a number of extensive investigations have also been conducted in order to understand the occurrence and behavior of EDCs in indoor and aquatic environments in Vietnam through the context of other countries in the region and in the world (5, 7, 37, 38). This paper provides an overview of the studies conducted in Vietnam on the contamination levels, distributions and human exposure to the following EDCs: siloxanes, phthalates, parabens, bisphenol A diglycidyl ether (BADGE), bisphenol A, bisphenol F, tetrabromobisphenol A (TBBPA), alkylphenolic compounds, some synthetic phenolic antioxidants and their metabolites in indoor dust and some groups of pharmaceuticals such as antibiotics (quinolones, sulfonamide and macrolides), anti-inflamatory, analgesic and lipid regulator drugs in aquatic environment. In addition, data for other countries obtained from studies using similar analytical methods were also summarized in order to provide a comprehensive picture of contamination and occurrence in Vietnam.

Occurrence of Endrocrine Disrupting Chemicals in Indoor Environments in Vietnam Very few comprehensive studies on the occurrence of endocrine emerging chemicals (ECDs) in environments such as air, water, soil, sediment in Vietnam are available. The first investigations on the contamination of ECDs in indoor dust from Vietnam were reported by Tran et al. in 2015 (5, 6). The ECDs under investigation comprised siloxanes, phthalates, parabens, BDGEs, bisphenol A and some synthetic phenolic antioxidants. 225 Loganathan et al.; Persistent Organic Chemicals in the Environment: Status and Trends in the Pacific Basin Countries II ... ACS Symposium Series; American Chemical Society: Washington, DC, 2016.


During April and May 2014, 46 indoor dust samples were collected from north of Vietnam: Hanoi (n=18), Hatinh (n=12), Hungyen (n=8), and Thaibinh (n=8). The sampling locations were grouped into four categories: homes (living rooms and kitchens, n=16), supermarkets/grocery shops, electronic stores and pharmacies; n=18), laboratories (Hanoi only, n=7), and offices (n=5); all of the sites were built after the year 2000.

Figure 1. Total concentration of siloxanes, phthalates, parabens, and BADGEs in indoor dust collected from Vietnam.

Figure 2. Composition of siloxanes, phthalates, parabens, and BADGEs in indoor dust collected from Vietnam. Values in parentheses (next to microenvironment) refer to the number of samples. 226 Loganathan et al.; Persistent Organic Chemicals in the Environment: Status and Trends in the Pacific Basin Countries II ... ACS Symposium Series; American Chemical Society: Washington, DC, 2016.


Siloxanes In one of the first studies on indoor environmental contamination from Vietnam, five cyclic siloxane including hexamethycyclotrisiloxane (D3), octamethylcyclotetrasiloxane (D4), decamethylcyclopentasiloxane (D5), dodecamethylcyclohexasiloxane (D6), octadecamethylcycloheptasiloxane (D7) and seven linear siloxanes including decamethyltetrasiloxane (L4), dodecamethylpentasiloxane (L5), tetradecamethylhexasiloxane (L6), and other linear polydimethylsiloxanes (L7, L8, L9, and L10) were found in indoor dust collected from four provinces (cities) in Vietnam (5). The total concentration of siloxanes in 46 dust samples ranged from 17.5 to 1970 ng/g (median: 411 ng/g) (Figure 1). Generally, the siloxane concentrations in indoor dust collected from Vietnam were mostly lower than developed countries (Table 1). The total concentration of cyclic siloxanes in 46 dust samples ranged from < 3.0 ng/g to 1060 ng/g (median: 225 ng/g). In particular, the siloxane concentration found in dust samples collected from homes were the highest with values ranging from 49.8 to 1060 ng/g (median: 385 ng/g). Following were dust samples collected from laboratories, ranging from 35.4 to 785 (median: 173 ng/g), public places (110 ng/g), and offices (105 ng/g). The highest concentration of cyclic siloxanes was found in dust collected from homes which can be explained as these chemicals are used widely in personal care products, up to a few percent in weight (13, 15). Personal care products and household items are known as the main source of siloxane emissions into the environment from homes. Generally, the total concentration of cyclic siloxanes collected from Hanoi was found at the highest levels in comparison with other provinces (median: 210 ng/g in Hanoi, followed by Hungyen (190 ng/g), Hatinh (122 ng/g), and Thaibinh (74 ng/g)). Among five cyclic siloxanes, D5 was found at the highest concentration in indoor dust. A median concentration of D5 was 67.9 ng/g, followed by D6 (45.7 ng/g) and D4 (15.2 ng/g) (Figure 2). This result suggests that D4, D5, and D6 are the most commonly used chemicals in personal care products (13, 15). Total concentrations of 7 linear siloxanes (L4-L10) in 46 dust samples ranged from below the detection limit (5 ng/g) to 1830 ng/g (median: 262 ng/g. These total concentrations were higher than the total concentrations of 5 cyclic siloxanes (153 ng/g) (5). Moreover, the total concentration of linear siloxanes in indoor durst collected in Hanoi had the highest levels in comparison with other provinces (median: 388 ng/g, ranged from 10.5 to 1830 ng/g). However, the total concentration of acyclic siloxanes in dust samples did not differ much, the median values were respectively 184, 182, and 175 ng/g for Hatinh, Hungyen, and Thaibinh (Figure 2). These results suggests that the relationship to the number of people living in different cities, Hanoi (2.6 million), Thaibinh (1.8 million), Hatinh (1.3 million), and Hungyen (1.1 million) (39), correspond to the consumption of personal care products and household items (considered as the main source of siloxane emissions into the environment). The emissions into indoor dust directly related to the composition of siloxanes present in personal care products and household items, as well as product consumption habits are different between people living in cities. 227 Loganathan et al.; Persistent Organic Chemicals in the Environment: Status and Trends in the Pacific Basin Countries II ... ACS Symposium Series; American Chemical Society: Washington, DC, 2016.

Among the linear siloxanes, L8 was found at the most abundant. Mean concentrations of L8, L9, L10, and L11 in indoor dust samples were 74.7, 43.3, 45.8, and 30.7 ng/g, respectively. Shorter chain siloxanes, such as L4, L5, and L6, were found at the lower levels (Figure 2).


Phthalates Similar to the first study, the occurrence of phthalates, including dimethyl phthalate (DMP), diethyl phthalate (DEP), diisobutyl phthalate (DIBP), di-n-butyl phthalate (DBP), di-n-hexyl phthalate (DNHP), benzyl butyl phthalate (BzBP), dicyclohexyl phthalate (DCHP), di(2-ethylhexyl) phthalate (DEHP), and di-n-octyl phthalate (DOP), were found in indoor dust samples collected from Vietnam (37). The mean and range of concentrations of phthalates found in dust samples collected from Vietnam are shown in Figure 1. DEP, DIBP, DBP, BzBP, and DEHP were found in all samples, whereas DOP, DMP, DCHP, and DNHP were detected in 96.9%, 69.6%, 60.0%, and 45.6% of the total collected samples, respectively. The total concentration of nine phthalates in dust ranged from 3,440 to 106,000 ng/g (median: 22,600 ng/g; mean: 30,200 ng/g). Dust samples collected from supermarkets contained the highest concentrations, ranging from 8,030 to 106,000 ng/g (median: 32,700 ng/g). The lowest phthalate concentration was found in dust samples from offices (range: 4,500 to 17,000 ng/g; median: 8,280 ng/g). The overall median concentrations of phthalates in indoor dust from Vietnam were 13 and 18 times lower than those from China (295,000 ng/g) and the USA (396,000 ng/g), respectively (31). The lower concentrations of phthalates in indoor dust from Vietnam than from China resemble the urinary phthalate metabolite concentrations observed for the Vietnamese population (median: 133 ng/mL), which were approximately two- to three fold lower than the values reported for the Chinese population (median: 234 to 331 ng/mL) (40, 41). These results imply that phthalate concentrations in dust can be a good predictor of urinary concentrations. The profile of the phthalates in indoor dust samples collected from Vietnam is shown in Figure 2. DEHP was the most abundant compound in indoor dust from Vietnam. The concentration of DEHP in dust samples ranged from 2,080 to 102,000 ng/g (median: 19,800 ng/g), followed by DBP (range: 73.7 to 1,240 ng/g; median: 737 ng/g) and DIBP (range: 18 to 4,580 ng/g; median: 562 ng/ g). Similarly, DEHP was found at the highest concentration in indoor dust from Canada (median: 462,000 ng/g) (2), France (median: 289,000 ng/g) (42), China (median: 228,000 ng/g), and the USA (median: 304 µg/g) (31). Among the four cities surveyed, the highest concentration of the sum of the nine phthalates was found in dust samples from Hanoi (median: 32,000 ng/g), followed by Hungyen (23,000 ng/g), Hatinh (16,000 ng/g), and Thaibinh (13,000 ng/g). Hanoi is the most populous urban center in Vietnam (2.6 million), followed by Thaibinh (1.8 million), Hatinh (1.3 million), and Hungyen (1.1 million) (39). These results suggest that dust from urban areas contained elevated concentrations of phthalates. 228 Loganathan et al.; Persistent Organic Chemicals in the Environment: Status and Trends in the Pacific Basin Countries II ... ACS Symposium Series; American Chemical Society: Washington, DC, 2016.


Parabens In similar rsearch, six parabens, including methyl paraben (MeP), ethyl paraben (EtP), propyl paraben (PrP), butyl paraben (BuP), benzyl paraben (BzP), and heptyl paraben (HepP), were found in indoor dust collected from four cities in Northern Vietnam (37). The total concentration of parabens in dust samples ranged from 40.0 to 842 ng/g (median: 132) (Figure 1). Among various microenvironments studied, dust samples collected from homes and laboratories contained similar median concentrations of parabens, at 205 and 211 ng/g, respectively; these concentrations were two times higher than in dust samples collected from retail stores (96.7 ng/g) and offices (120 ng/g). Paraben concentrations in indoor dust from Vietnam were 12, 4, 17, and 14 times lower than in dust samples collected from the USA (median: 1,560 ng/g), China (573 ng/g), South Korea (2,180 ng/g), and Japan (1,850 ng/g), respectively (43). Individual paraben concentrations in indoor dust from Vietnam were 30 times lower than in dust samples from Spain (median concentrations of MeP and PrP were at 2,440 and 910 ng/g, respectively) (44). Major sources of parabens in the indoor environment are cosmetics and personal care products (45). Among parabens, MeP was the most abundant compound, with a median concentration of 58.2 ng/g, followed by PrP (15.0 ng/g), BuP (14.9 ng/g), and EtP (12.7 ng/g). These results suggest that MeP and PrP co-exist in many consumer products (46, 47). The total concentrations of parabens in dust samples collected from the four cities in Vietnam were not significantly different (p>0.05), although the highest levels were found in samples from Hanoi (median: 196 ng/g), followed by Hatinh (124 ng/g), Thaibinh (122 ng/g), and Hungyen (100 ng/g). BADGEs In this report, bisphenol A diglycidyl ether (BADGE) and their derivatives, including bisphenol A (2,3-dihydroxypropyl) glycidyl ether (BADGE.H2O), bisphenol A (2,3-dihydroxypropyl) ether (BADGE.2H2O), and bisphenol A (3-chloro-2-hydroxypropyl) (2,3-dihydroxypropyl) ether (BADGE.HCl.H2O), were found in indoor dust collected from Vietnam (37). In general, the total concentrations of BADGEs in indoor dust samples collected from Vietnam ranged from 23 to 1,750 ng/g (median: 184 ng/g) (Figure 1). The concentrations of BADGEs in dust samples collected in four areas from Vietnam were 7, 8, 13, and 11 times lower than those from the USA (1,350 ng/g), China (1,410 ng/g), South Korea (2,380 ng/g), and Japan (2,020 ng/g), respectively (43). BADGE.H2O and BADGE.2H2O were the predominant compounds found in dust, followed by BADGE.HCl.H2O (detection rate: 97.8%), and BADGE (detection rate: 76.1%). The distribution profile of BADGEs in indoor dust from Vietnam was similar to that reported for the USA, China, South Korea, and Japan (43). Among the BADGEs, BADGE.2H2O was found at the highest concentrations, ranging from 7.58 to 1,630 ng/g (median: 129 ng/g), followed by BADGE.H2O (1.79 to 255 ng/g; median: 28.0 ng/g) (37). The concentrations of BADGE and BADGE.HCl.H2O were similar (11 ng/g) and they were 12 times lower than the concentration of BADGE.2H2O. Concentrations of BADGEs in dust samples were 229 Loganathan et al.; Persistent Organic Chemicals in the Environment: Status and Trends in the Pacific Basin Countries II ... ACS Symposium Series; American Chemical Society: Washington, DC, 2016.


significantly different among the four cities (p< 0.005). The highest concentration of the four BADGEs was found in indoor dust samples collected from Hungyen (median: 671 ng/g) followed by Thaibinh (297 ng/g), Hanoi (150 ng/g), and Hatinh (124 ng/g). The reason for this pattern is unclear, and further studies are needed to delineate the sources of BADGEs (37). Generally, the EDCs (including siloxanes, phthalates, parabens, and BADGEs) concentrations in indoor dust samples collected from Vietnam were mostly lower than from industrialized countries. Among microenviroments, dust samples collected from homes were mostly contaminated by the EDCs at the highest levels. The levels of EDCs in samples collected in Hanoi were shown to be at higher concentrations compared with other cities.

Bisphenol A (BPA), Bisphenol F (BPF), and Tetrabromobisphenol A (TBBPA) In this report, BPA, BPF, and TBBPA were found in 12 dust samples collected from Vietnam. The BPA concentrations ranged from 27 to 1,400 ng/g (mean and median: 330 and 230 ng/g) (6). The BPA concentration in indoor dust collected from Vietnam was much lower than other countries such as Japan (median: 1700 ng/g), Greece (1500 ng/g), the U.S. (1500 ng/g), and South Korea (720 ng/g) (Table 1). Similarly, the concentration of BPF in indoor dust collected from Vietnam was also lower than other countries. The BPF concentration in dust from Vietnam ranged from below the limit of quantification (1 ng/g) to 1500 ng/g (mean and median: 200 and 57 ng/g) (6). These results were five and four times lower than in dust collected from South Korea (median: 1000 ng/g) and Greece (780 ng/g), respectively. High concentrations of BPF found in dust from developed countries such as South Korea , Japan, and the U.S. indicated a high usage of this BP analogue in these countries. BPF has been reported as a major alternative to BPA in industrial applications in South Korea (48). The total concentrations of BPs (eight bisphenol analogues) in 12 indoor dust samples collected from Vietnam ranged from 66 to 1,600 ng/g (median: 400 ng/g) (Table 1) (6). Generally, the concentration of total BPs in indoor dust collected from Vietnam was also lower than other developed countries. Tetrabromobisphenol A (TBBPA) was found in 12 indoor dust samples collected from Vietnam. The TBBPA concentration in dust ranged from below the limit of quantification (1 ng/g) to 670 ng/g (mean and median: 99 and 1.6 ng/g) (6). High concentrations of TBBPA were found in house dust from Japan (range: 12–1,400 ng/g), South Korea (43–370 ng/g) and China (1–2,300 ng/g). Considering the high market demand for this flame retardant in eastern Asian countries, high concentrations of TBBPA found in dust from Japan, South Korea, and China can be related to the emission from commercial products. In 2001, the highest TBBPA consumption was registered in Asia (89,400 t/year) (49).

230 Loganathan et al.; Persistent Organic Chemicals in the Environment: Status and Trends in the Pacific Basin Countries II ... ACS Symposium Series; American Chemical Society: Washington, DC, 2016.

Table 1. Summary of EDCs levels in indoor dust collected from different countries Concentration of EDCs in indoor dust: median (range) (ng/g) Siloxanes

Phthalates

Parabens

BADGEs

BPs

TBBPA

SPAs

Vietnam

205 (n.d. 942) (5)

22,600 (3440 -106,000) (37)

132 (40 - 842) (37)

184 (23 - 1750) (37)

400 (66 1600) (6)

1.6 (

Emerging Endocrine Disrupting Chemicals and Pharmaceuticals in

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