Pharmaceuticals, hormones, plasticizers, and pesticides in drinking water

https://doi.org/10.1016/j.jhazmat.2021.127327Get rights and content

Highlights

  • A simpler tool for identification of multiclass EDCs in drinking water analysis.

  • The method was verified and 15 multiclass EDCs were detected in tap water.

  • EDC levels significantly varied, with a maximum level of 17.63 ng/L observed.

  • No risk of EDC exposure via drinking water intake (risk quotient < 1).

  • The method is applicable for tracing multiclass EDCs in tap water elsewhere.

Abstract

Humans are exposed to endocrine disrupting compounds (EDCs) in tap water via drinking water. Currently, most of the analytical methods used to assess a long list of EDCs in drinking water have been made available only for a single group of EDCs and their metabolites, in contrast with other environmental matrices (e.g., surface water, sediments, and biota) for which more robust methods have been developed that allow detection of multiple groups. This study reveals an analytical method of one-step solid phase extraction, incorporated together with liquid chromatography–tandem mass spectrometry for the quantification of multiclass EDCs (i.e., pharmaceuticals, hormones, plasticizers, and pesticides) in drinking water. Fifteen multiclass EDCs significantly varied in amount between field samples (p < 0.05), with a maximum concentration of 17.63 ng/L observed. Daily exposure via drinking water is unlikely to pose a health risk (risk quotient < 1). This method serves as an analytical protocol for tracing multiclass EDC contamination in tap water as part of a multibarrier approach to ensure safe drinking water for good health and well-being. It represents a simpler one-step alternative tool for drinking water analysis, thereby avoiding the time-consuming and expensive multi-extraction steps that are generally needed for analyzing multiclass EDCs.

Introduction

Endocrine disrupting compounds (EDCs) had been recognized as emerging environmental contaminants, although their possible ecological and human health effects are not yet fully understood. The variety of EDCs used in daily products—namely, pharmaceuticals, personal care products, flame retardants, surfactants, pesticides, and plasticizers—has contributed to human exposure to EDCs daily (e.g., ingestion, inhalation, and dermal absorption). EDCs are commonly known for disrupting the endocrine system even at low exposure levels, although the precise mechanism behind this phenomenon remains to be fully established (Diamanti-Kandarakis et al., 2009). Endocrine system effects caused by EDCs include alterations in the immune system, metabolic disorders, abnormalities in the reproductive system, behavioral changes, cardiovascular diseases, neurological effects, distorted development and growth, diabetes, obesity, and cancers. The effects on human health are linked to the exposure age, duration of exposure, dosage, and interaction with other pollutants (i.e., combined effects) (Kabir et al., 2015).

Because of the increasing usage and manufacturing of EDC-containing products and the existence of undesignated wastewater and sewage treatment plants specifically for attenuation of emerging pollutants, EDCs enter not only the various terrestrial and aquatic food chains and webs but also the drinking water supply system (Ismail et al., 2021, Liu et al., 2015, Núñez et al., 2015, Omar et al., 2019a, Wee and Aris, 2017). Effluent-impacted drinking water sources (with ubiquitous EDC contamination) are being used for the daily drinking water supply. This issue is exacerbated by several drivers such as socioeconomic functions and environmental changes since the distances between effluent discharge points and drinking water sources are slowly being reduced over time. Particularly, climate change has caused the entrance of a variety of EDCs with associated risks into the drinking water supply system (Boholm and Prutzer, 2017, Chiu et al., 2017, Coppens et al., 2015). Also, the adaptation and implementation of drinking waterworks may be different according to varied financial and technical resources, policy and regulatory frameworks, community and stakeholder support, and scientific knowledge and information (Boholm and Prutzer, 2017, Wee and Aris, 2019).

The elevated EDC levels in drinking water sources (e.g., surface water) and the subsequent inadequate removal of EDCs especially by drinking water treatment plants has led to enhanced EDC loading in drinking water supplies (e.g., tap water) and contributed to greater human exposure to environmental chemicals via the daily intake of drinking water. In some cases, higher contamination levels of these EDCs were discovered to exist in the treated water than that in the corresponding raw water (Benotti et al., 2009, Padhye et al., 2014). To date, EDC contamination in the drinking water supply persists as a formidable issue despite that most countries are committed to adhering to the United Nations Sustainable Development Goals (Goal 6: Clean Water and Sanitation and Target 6.1: Drinking Water) regarding a safe drinking water supply for promoting the good health and well-being of the population. Besides health issues, economic loss due to diseases attributable to exposure to EDCs in drinking water could be a matter of concern (Trasande et al., 2015).

Given findings of trace concentrations of EDCs in the water cycle and the complex matrix interferences, the identification of the wide-ranging spread of EDCs in the environment is a perennial challenge. Effective analytical strategies employing solid phase extraction–liquid chromatography–tandem mass spectrometry (SPE-LC-MS/MS) have been used for the identification of environmental EDCs. The majority of investigations of multiclass EDCs have employed one-step SPE in environmental matrices such as surface water, sediment, and biota in riverine, estuarine, and marine ecosystems (Berlioz-Barbier et al., 2014, Ismail et al., 2019, Ismail et al., 2020, Ismail et al., 2021, Liu et al., 2015, Núñez et al., 2015, Omar et al., 2017, Omar et al., 2019a, Omar et al., 2019b, Paíga et al., 2015, Wee et al., 2019). Table 1 shows a comparison between the analysis of EDCs in aquatic environments and drinking water. Unlike in the aforementioned environmental matrices, the trace concentrations and the broad range of EDC characteristics limit EDC monitoring in drinking water and the efficacy of risk assessment; as such, the corresponding risks may be underestimated. Moreover, some EDCs remain to be uncovered. To date, most of the development of EDC extraction methods in drinking water analysis has been limited to only a single group of EDCs and their metabolites, with a subsequent long list of targeted compounds (Gaffney et al., 2015, Gros et al., 2012, Leung et al., 2013). Li et al. (2010) analyzed a total of only three compounds in two classes of EDCs. Moreover, methods in drinking water analysis established by the United States Environmental Protection Agency (US EPA) have been limited to a single EDC group, for example, pesticides (Method 523: 13 triazine pesticides and their degradates, Method 526: 11 semivolatile organic compounds including diazinon, Method 532: 8 phenylurea compounds, Method 536: 7 triazine pesticides and their degradates), hormones (Method 539: 7 compounds including testosterone, estrone, 17β-estradiol, and 17α-ethynylestradiol), pharmaceuticals and personal care products (Method 542: 12 compounds including sulfamethoxazole, diclofenac, and triclosan), cyanotoxins (Method 545: cylindrospermopsin and anatoxin-a), and other pollutant groups such as phenol groups, halogenated compounds, inorganic pollutants, disinfectants, disinfection by-products, radioactive particles, and microorganisms (Supplementary Table S1). As a result, sustainability of the analytical protocol is of great concern when detection and quantification of multiclass EDCs require multiple time-consuming and costly extraction steps.

The World Health Organization (WHO) has noted that the WHO Guidelines for Drinking Water Quality were insufficient based on the current EDCs in drinking water. The present study presented a protocol for the analysis of a group of multiclass EDCs composed of pharmaceuticals (i.e., dexamethasone, primidone, propranolol, ciprofloxacin, caffeine, sulfamethoxazole, diclofenac, chloramphenicol, and triclosan), hormones (i.e., testosterone, progesterone, estrone, 17β-estradiol, and 17α-ethynylestradiol), plasticizers (i.e., bisphenol A, 4-octylphenol, and 4-nonylphenol), and pesticides (i.e., diazinon), in a single extraction step, particularly to ensure safe drinking water. EDCs were targeted (i) based on their potential endocrine dysfunction effects, (ii) to ensure representative coverage of different EDC groups, (iii) appertaining to the wide usage of such chemicals in domestic and industrial applications, and (iv) considering monitored occurrences in drinking water sources of Malaysia and other countries (Aris et al., 2014, Gonzalez-Rey et al., 2014, Li et al., 2012, Li and Lin, 2015, Praveena et al., 2016, Sun et al., 2020, Wee et al., 2016, Wee et al., 2019, Xu et al., 2013). Several of the EDCs were listed in the US EPA Contaminant Candidate List (a list of priority drinking water contaminants for regulatory consideration). In particular, hormones such as estrone, 17β-estradiol, and 17α-ethynylestradiol were monitored under the Unregulated Contaminant Monitoring Rule (UCMR), whereas monitoring for 4-nonylphenol remained in method development.

The optimized method was validated based on several criteria, such as linearity, extraction recovery, precision, sensitivity, and matrix effects. The method was further verified using localized tap water, which is the main daily drinking water supply of consumers. Subsequently, this method serves as an analytical protocol for the identification of multiclass EDCs in tap water elsewhere with a similar range of physicochemical properties. This enhancement in EDC monitoring would therefore allow assessments not only in the environmental compartments (e.g., surface water, sediments, and biota) but also in drinking water, focusing on the human health risks via daily water intake aside from the associated ecological risks. Furthermore, a simpler one-step extraction of multiclass EDCs is expected to be more cost-effective and time-efficient. Thus, it is important to develop and apply valid and reliable analytical methods to address existing knowledge gaps and potential drinking water quality issues, providing an overview of the source and transport of multiclass EDCs in drinking water supply systems (i.e., from source to tap) as well as the subsequent health risk implications. Therefore, the present study is expected to be advantageous in the areas of water resources monitoring and management, especially in terms of promoting drinking water security and human health.

Section snippets

Chemicals and materials

Individual stock standards, i.e., dexamethasone, primidone, propranolol, ciprofloxacin, caffeine, sulfamethoxazole, diclofenac, chloramphenicol, triclosan, testosterone, progesterone, estrone, 17β-estradiol, 17α-ethynylestradiol, bisphenol A, 4-octylphenol, 4-nonylphenol, and diazinon, as depicted in Fig. 1, were collected from Dr. Ehrenstorfer GmbH (Augsburg, Germany). Meanwhile, primidone (D5, 98%), sulfamethoxazole (D4, 98%), diclofenac (D4, 98%), diazinon (D10, 98%), 17β-estradiol (D4,

Method performance

The presence of EDCs in the environment was commonly found in mixed form, where the toxicity of the EDC mixture was higher relative to that of a single EDC because of their combined consequences, such as additive, synergistic, potentiation, and antagonistic effects (Li and Lin, 2015, Li et al., 2012, Saili et al., 2013, Yuan et al., 2018). Further, the global contamination of the drinking water supply encompasses the broad scopes of different classes of EDCs (Wee and Aris, 2017). In the context

Conclusion

A simpler one-step alternative tool for drinking water analysis was successfully developed and validated, thereby avoiding the time-consuming and expensive multi-extraction steps that are generally needed for analyzing multiclass EDCs. Satisfactory method accuracy and sensitivity were observed at recovery ranging from 56% to 146% with a majority of 85–119%, associated with the MDL estimated from 0.01 to 2.56 ng/L. High method precision (RSD less than 15%) was observed for all the targeted

CRediT authorship contribution statement

Sze Yee Wee: Conceptualization, Methodology, Investigation, Formal analysis, Visualization, Writing – original draft, Writing – review & editing; Nur Afifah Hanun Ismail: Methodology; Didi Erwandi Mohamad Haron: Methodology, Validation; Fatimah Md. Yusoff: Writing – review & editing; Sarva Mangala Praveena: Writing – review & editing; Ahmad Zaharin Aris: Supervision, Funding acquisition, Writing – review & editing.

Declaration of Competing Interest

The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper.

Acknowledgments

This work was supported by the Ministry of Higher Education Malaysia under Trans-Disciplinary Research Grant Scheme [TRGS/1/2016/UPM/02/6/1] and the Ministry of Science and Technology in South Korea through the International Environmental Research Institute of Gwangju Institute of Science and Technology [IERI/2019].

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