Chemical Contaminants
Pharmaceuticals and Personal Care Products
Pharmaceuticals and personal care products (PPCPs) are a class of emerging contaminants that include prescription (such as antibiotics) and non-prescription drugs (including ibuprofen), fragrances, detergents, steroids, reproductive hormone drugs and others used for personal health or cosmetic reasons.
These contaminants get washed into household drains including toilets via human waste and also from improper disposal of pharmaceuticals (flushing them down the toilet). Consumers can also wash off personal care products in the shower. These chemicals are carried in household sewage to water pollution control plants, where treatment technologies are not usually designed for their removal specifically. The result is discharge of the PPCP chemicals from these plants to surface waters (streams, rivers and lakes).
Because of the major benefits of PPCPs to people, their use and release to the environment will continue. Research, development and monitoring need to provide information in order to effectively manage these contaminants for the protection of the environment.
A number of studies have occurred recently or are underway in the Lake Simcoe watershed. They are aimed at developing a better understanding of PPCPs in the watershed.
What are pharmaceuticals and personal care products (PPCPs)?
Pharmaceuticals and personal care products (PPCPs) are a class of emerging contaminants that include prescription and non-prescription drugs, fragrances, surfactants (detergents), steroids, hormonal drugs used for contraception and hormone replacement therapy, and others. Use of PPCPs for personal health or cosmetic reasons can contribute chemicals to the natural environment via wastewater from water pollution control plants (WPCP), as well as from urban, industrial and agricultural wastewater (Chen et al., 2006; Helm et al, 2012; Lishman et al., 2006; Metcalfe et al., 2003; Metcalfe et al., 2010; Sultana et al., 2017; Yang and Metcalfe, 2006). Veterinary pharmaceuticals, including products to boost growth and health of livestock, can enter the environment through animal wastes leaking out of storage structures or land application (Meyer et al., 2000).
Initial concerns of possible adverse ecological effects of pharmaceuticals in municipal wastewater date back to the 1960s and 1970s (Snyder et al., 2003; Stumm-Zollinger and Fair, 1965; Tabak and Bunch, 1970). However, research was hindered due to the inability of laboratories to detect the very low concentrations of these substances in the environment. As sampling and analytical capabilities improved over time, and interest gathered momentum (including from the public), a wide variety of PPCPs were reported as contaminants in the environment including antibiotics, X-ray contrast media, analgesics, antiseptics, anti-inflammatories, anti-depressives, blood lipid regulators and many others.
Mobility and fate of PPCPs in the environment
The occurrence of PPCPs in aquatic systems is mainly due to therapeutic use and the resultant excretion or end-use disposal of pharmaceuticals (Herberer, 2002), the use and wash-off of personal care products by consumers (Daughton and Ternes, 1999) and subsequent effluent discharge from WPCPs. In a study of the nearshore area of Lake Ontario, Helm et al. (2012) found that the highest levels of PPCPs were generally in the vicinity of a large capacity WPCP outfall. Certain compounds, such as ibuprofen and caffeine, are more persistent in the water than others (see half-lives listed by the authors) and were more broadly distributed in the nearshore due to movement from alongshore currents, rather than being more concentrated near the outfall.
The authors also found that non-point sources (including stormwater runoff) had relatively minor contributions of PPCPs to receiving waters compared to effluent from WPCPs, though some substances including ibuprofen occurred at significant levels in tributaries. Stormwater runoff can contribute to high levels of ibuprofen in surface waters where combined sewer overflows are present and from leaking at cross-connections of domestic waste pipes to storm sewers (Buser et al., 1999).
In a study with considerable spatial coverage in the U.S., Kolpin et al. (2002) tested for a number of PPCPs in water samples from 139 susceptible streams (draining highly urbanized areas and agricultural areas, particularly with livestock production) across 30 states in 1999 and 2000. A large portion of the sampled streams detected concentrations of PPCPs. Because of the presence of many PPCPs in aquatic systems, as reported by Kolpin at al. (2002), it is apparent that at least a portion of many existing compounds can endure wastewater treatment and biodegradation, and can persist in the environment. Additionally PPCPs can degrade into their metabolites, which also need to be considered when determining the overall effects on the health of the environment (Kolpin et al., 2002). Since this study advances in wastewater treatment technologies have improved the ability of WPCPs to retain some PPCPs (e.g. the use of tertiary treatment or reverse osmosis membranes in WPCPs) and innovative technologies continue to be investigated.
Environmental impacts
Potential issues of PPCPs in the environment include abnormal physiological and reproductive processes for fish, birds and mammals, bacterial resistance to antibiotics and increased toxicity from mixing of these compounds in the environment (see citations in Kolpin et al., 2002). Certain synthetic and natural compounds, known as endocrine-disrupting compounds (EDCs), can mimic natural hormones that are part of an organisms endocrine system and can cause adverse effects to the organism (Snyder et al., 2003).
Exposure to PPCPs may also cause endocrine disruption in aquatic species [National Institute of Environmental Health Sciences (NIEHS), 2017]. Effects of endocrine disruptors, including skewed gender ratios and feminization of males, have been well documented for fish and amphibians. For example, intersex and reproductive impairment occurred to wild fish in relation to municipal wastewater effluent discharge into the Grand River of Ontario (Tetreault et al., 2011), but with subsequent decreases in intersex incidence after treatment process upgrades at one of the WPCPs (Hicks et al., 2017).
Of the hundreds of PPCPs in use, acute ecotoxicity guidelines or thresholds are only available for a small portion, and for chronic toxicity the data is even sparser. This is a key consideration as many pharmaceuticals may be released to aquatic environments at a low level but as a continuous input (Monteiro and Boxall, 2010), thus subjecting organisms to a constant low-level exposure (Daughton and Ternes, 1999). This is in contrast to other pollutants such as seasonally applied herbicides that may enter aquatic ecosystems as pulses. In some instances chronic effects to aquatic biota could be of greater concern than acute effects. Specifically exposing bacteria to low levels of antibiotics in the environment could increase the ability of pathogenic bacteria to develop resistance (see citations in Kolpin et al., 2002).
Although the scientific community has established that pharmaceuticals are ubiquitous in aquatic systems, the fate of these compounds in the environment is still poorly understood, such as the derivation of half-lives and partitioning in environmental matrices (i.e., soil and sediment) and biological uptake (Kummerer, 2009; Burns et al., 2017).
Efforts are underway to identify which, out of the numerous pharmaceuticals (and personal care products) currently found in the environment, have the most potential to harm non-target organisms and what their ecological fate and effects may be (Roos et al., 2012; Guo et al., 2016). Burns et al. (2017) summarizes some studies of this nature as well as applying an innovative approach where a large range of compounds (95 compounds) were assessed using a modelling tool while accounting for environmental variables such as hydrology and season.
PPCPs in the Lake Simcoe watershed
As with microplastics, the Ministry of Environment, Conservation and Parks (MECP) sampled microplastics in Lake Simcoe in 2018. In conjunction with that program, PPCP samples were collected using methods similar to the Great Lakes work performed by Helm et al. (2012; passive samplers). Once analyzed this information can be used to develop a baseline of PPCP concentrations in Lake Simcoe waters and sediments.
A number of studies have occurred or are underway in the Lake Simcoe watershed, aimed at developing a better understanding of PPCPs in the watershed. A number of such studies focus on the evaluation of various wastewater treatment technologies, both current and innovative, that can intentionally reduce PPCPs in the waste stream, or indirectly through successive and advanced treatments mainly intended for phosphorus reduction.
One such assessment (Sultana et al., 2017) monitored PPCPs in the influent and effluent of six WPCPs in the Lake Simcoe watershed in 2012 and 2013. These particular WPCPs had been recently upgraded to various types of tertiary treatment for the purpose of removing phosphorus from the waste stream. Specialized sampling equipment [Polar Organic Chemical Integrative Sampler (POCIS) and Semipermeable Membrane Devices (SPMDs)] were incorporated in this study to monitor hydrophilic and hydrophobic PPCPs. Some PPCPs may be more hydrophobic, binding to stream sediments, while others are hydrophilic, remaining in the water column. Types of PPCPs measured included two anti-inflammatory drugs (one being ibuprofen), an anti-epileptic drug, a cholesterol reducing drug, two natural hormones (an estrogen and an androgen), two antibiotics, two antibacterial compounds and two synthetic fragrances. Artificial sweeteners were included in the analyses as they are useful chemical tracers of contamination from wastewaters (Lange et al., 2012). The WPCPs did not effectively remove artificial sweeteners nor the more water-soluble pharmaceuticals (including the antibiotics and the anti-epileptic and cholesterol-reducing drugs) which would therefore enter surface waters through effluent. However, WPCPs with tertiary treatment were effective at removing the more hydrophobic compounds (ibuprofen, steroid hormones, antibacterials and the fragrances). The authors concluded that although the tertiary treatment technologies do not effectively remove all PPCPs, there are only low loads of PPCPs to the Lake Simcoe watershed that are, currently, not likely a threat to aquatic organisms or drinking water sources.
A pilot study at the Keswick WPCP is evaluating the use of ultraviolet (UV)-based advanced oxidation process as a possible solution to reduce micropollutants (such as pharmaceuticals) in wastewater [Meteer, unpublished; Ministry of Environment and Climate Change (MOECC), 2014]. This technology could potentially be used to treat wastewater in future and an additional project goal was to do a cost-benefit analysis of the process. By adding on pretreatment of the secondary effluent to reduce organic matter, the UV-oxidation process was more effective such that lower doses of chemical treatment were required. This combination of pretreatment and a lower dose treatment was demonstrated as the most cost-effective method for this WPCP. Variations in pretreatment options, UV transmittance and chemical doses might be more suitable at other plants depending on specific water characteristics.
Additional Ontario studies and resources
There are studies being carried-out across Ontario by various agencies to explore the capabilities of water treatment technologies for the reduction of PPCPs in wastewater. For example, it was observed that certain PPCPs were reduced in concentration during treatment of municipal wastewater in six lagoons (Pileggi et al, 2016), though further work is required to understand how the PPCP compounds are removed (such as through volatilization or adsorption to sludge) in order to improve lagoon design.
Actions to reduce PPCPs in the environment
When regulators want to assess the risks associated to the environment from a PPCP, not only the properties of the chemical itself need to be considered but also the complexity of environmental systems it is exposed to. The ability of a chemical, including a PPCP, to persist in the environment is a key consideration for regulation. The behaviour of a pharmaceutical in the lab can be very different than in environmental media, as noted by differences between half-lives measured in the lab and field for the few pharmaceuticals that have environmental persistence data available (Bu et al., 2016). The ability of a pharmaceutical to endure, or persist, in the environment is partly determined by chemical-specific characteristics but also partly by environmental conditions that affect degradation processes (for example, sunlight exposure can affect degradation by photolysis). This information, together with bioaccumulative capacity and toxicity, is important for creating environmental risk assessments required for regulation. It has been suggested that risk assessments should consider long-term and non-lethal consequences to ecosystems as well as persistence (Arnold et al., 2013).
Pharmaceuticals have been considered as “pseudo-persistent” as there is a relatively constant supply from waste treatment, such that their inputs are faster than their rates of removal from the environment. Differentiating between the longevity of chemicals and their continuous release creates challenges for regulating pharmaceuticals and controlling them. Once understood, it may be found that while some chemicals may be used a lot, they degrade more readily in the environment and so reducing that volume through regulation would be a key strategy (e.g., antibiotic over-prescription). For others that degrade more slowly, focusing on alternatives might be a component of future regulations (Bu et al., 2016).
More specific to Lake Simcoe, the Lake Simcoe Protection Plan (LSPP) specifies that emerging issues (including pharmaceuticals and personal care products) are addressed in policies regarding WPCPs in the Lake Simcoe watershed such that restrictions are placed on the establishment or replacement of a WPCP (MOE, 2009). Due to urban growth in the Lake Simcoe watershed, innovative wastewater treatment technologies, such as those described above, should continue to be assessed. Because of the major benefits of the various chemicals that comprise PPCPs, their use and release to the environment will continue. Research, development and monitoring need to provide information in order to effectively manage these contaminants for the protection of the environment.
References
Arnold KE, Boxall ABA, Brown AR, Cuthbert RJ, Gaw S, Hutchinson TH, Jobling S, Madden JC, Metcalfe CD, Naidoo V, et al. 2013. Assessing the exposure risk and impacts of pharmaceuticals in the environment on individuals and ecosystems. Biol. Lett. 9: 1-4.
Bu Q, Shi X, Yu G, Huang J and Wang B. 2016. Assessing the persistence of pharmaceuticals in the aquatic environment: Challenges and needs. Emerging Contaminants 2: 145-147.
Buser H-R, Poiger T and Müller MD. 1999. Occurrences and environmental behavior of the chiral pharmaceutical drug ibuprofen in surface waters and in domestic wastewater. Environ. Sci. Technol. 33: 2529–2535.
Chen M, Ohman K, Metcalfe C, Ikonomou MG, Amatya PL and Wilson JJ. 2006. Pharmaceuticals and endocrine disruptors in wastewater treatment effluents and in the water supply system of Calgary, Alberta. Canada. Water Qual. Res. J. Can. 41:351-364.
Daughton CG and Ternes TA. 1999. Pharmaceuticals and personal care products in the environment: Agents of subtle change? Environ. Health Perspect. 107: 907-938.
Guo J, Sinclair CJ, Selby K and Boxall ABA. 2016. Toxicological and ecotoxicological risk-based prioritization of pharmaceuticals in the natural environment. Environ. Toxicol. Chem. 35: 1550–1559.
Helm PA, Howell ET, Li H, Metcalfe TL, Chomicki KM and Metcalfe CD. 2012. Influence of nearshore dynamics on the distribution of organic wastewater-associated chemicals in Lake Ontario determined using passive samplers. J. Great Lakes Res. 38: 105-115.
Herberer T. 2002. Occurrence, fate, and removal of pharmaceutical residues in the aquatic environment: A review of recent research data. Toxicol. Lett. 131: 5-17.
Hicks KA, Fuzzen MLM, McCann EK, Arlos MJ, Bragg LM, Kleywegt S, Tetreault GR, McMaster ME, Servos MR. 2017. Reduction of intersex in a wild fish population in response to major municipal wastewater treatment plant upgrades. Environ. Sci. Technol. 51: 1811-1819.
Kolpin D, Furlong E, Meyer M, Thurman EM and Zaugg S. 2002. Pharmaceuticals, hormones, and other organic wastewater contaminants in U.S. streams, 1999-2000: A national reconnaissance. Environ. Sci. Technol. 36: 1201-1211.
Kümmerer K. 2009. The presence of pharmaceuticals in the environment due to human use – Present knowledge and future challenges. J. Environ. Manage. 90: 2354-66.
Lange FT, Scheurer M and Brauch HJ. 2012. Artificial sweeteners—A recently recognized class of emerging environmental contaminants: A review. Anal. Bioanal. Chem. 403: 2503-2518.
Lishman L, Smyth SA, Sarafin K, Kleywegt S, Toito J, Peart T, Lee B, Servos M, Beland M and Seto P. 2006. Occurrence and reductions of pharmaceuticals and personal care products and estrogens by municipal wastewater treatment plants in Ontario, Canada. Sci. Total Environ. 367: 544-558.
Metcalfe CD, Chu S, Judt C, Li H, Oakes KD, Servos MR and Andrews DM. 2010. Antidepressants and their metabolites in municipal wastewater, and downstream exposure in an urban watershed. Environ. Toxicol. Chem. 29: 79-89.
Metcalfe CD, Koenig BG, Bennie DT, Servos M, Ternes TA and Hirsch R. 2003. Occurrence of neutral and acidic drugs in the effluents of Canadian sewage treatment plants. Environ. Toxicol. Chem. 22: 2872-2880.
Meteer, L. 2018. Removal of micropollutants from municipal wastewater: Lake Simcoe/Regional Municipality of York pilot project, solutions for the wastewater industry. Unpublished report.
Meyer MT, Burngarner JE, Varns JL, Daughtridge JV, Thurman EM and Hostetler KA. 2000. Use of radioimmunoassay as a screen for antibiotics in confined animal feeding operations and confirmation by liquid chromatography/mass spectrometry. Sci. Total Environ. 248: 181-187.
Ministry of the Environment (MOE). 2009. Lake Simcoe Protection Plan (LSPP), Chapter 4. Toronto, Ontario: Queen’s Printer for Ontario.
Ministry of the Environment and Climate Change (MOECC). 2014, July 30. Regional municipality of York: Micropollutant removal. Retrieved from: https://www.ontario.ca/page/regional-municipality-york-micropollutant-removal
Monteiro SC and Boxall AB. 2010. Occurrence and fate of human pharmaceuticals in the environment. In: DM Whitacre (Ed.), Reviews of Environmental Contamination and Toxicology, vol. 202. New York, NY: Springer.
National Institute of Environmental Health Sciences (NIEHS). 2017, August 28. Endocrine disrupters. Retrieved from: https://www.niehs.nih.gov/health/topics/agents/endocrine/index.cfm
Pileggi V, Kleywegt S, Murray C, Collins L, Metcalfe C and Fletcher T. 2016, November 15. Performance of selected Ontario municipal wastewater lagoons in the Great Lakes Basin. Presentation at National Water and Wastewater Conference, Toronto, Ontario.
Roos V, Gunnarsson L, Fick J, Larsson DGJ and Rudén C. 2012. Prioritising pharmaceuticals for environmental risk assessment: Towards adequate and feasible first-tier selection. Sci. Total. Environ. 421-422: 102-110.
Snyder SA, Westerhoff P, Yoon Y and Sedlak DL. 2003. Pharmaceuticals, personal care products, and endocrine disruptors in water: Implications for the water industry. Environ. Eng. Sci. 20: 449:469.
Stumm-Zollinger E and Fair GM. 1965. Biodegradation of steroid hormones. J. Water Pollut. Cont. Fed. 37: 1506–1510.
Sultana T, Murray C, Hoque ME and Metcalfe CD. 2017. Monitoring contaminants of emerging concern from tertiary wastewater treatment plants using passive sampling modelled with performance reference compounds. Environ. Monit. Assess. 189: 1-19.
Tabak HH and Bunch RL. 1970. Steroid hormones as water pollutants I. Metabolism of natural and synthetic ovulation-inhibiting hormones by microorganisms of activated sludge and primary settled sewage. Dev. Ind. Microbiol. 11: 367-376.
Tetreault GR, Bennett CJ, Shires K, Knight B, Servos MR and McMaster ME. 2011. Intersex and reproductive impairment of wild fish exposed to multiple municipal wastewater discharges. Aquat. Toxicol. 104: 278-290.
Yang JJ and Metcalfe CD. 2006. Fate of synthetic musks in a domestic wastewater treatment plant and in an agricultural field amended with biosolids. Sci. Total Environ. 363: 149-165.
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New Report
Chemical Contaminants in Lake Simcoe and its Tributaries
in 2015, a study was undertaken to investigate levels of chemical contaminants in the surface water and sediments of Lake Simcoe and its tributaries. The contaminants included in this study were chosen based on historical use within the watershed, previous research undertaken (such as the LSRCA 2004 study), and literature from similar areas in the Great Lakes Region.
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