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YORK STATE
Department of Earth and Atmospheric Sciences 230 Riley-Robb Hall, Cornell University Tel: (607) 254-7163 Ithaca, NY 14853-5701 Fax: (607) 255-4080 Email: [email protected] Target Screening for Micropollutants in the Hudson River Estuary
during the 2015 Recreational Season
Amy Pochodylo and Damian E. Helbling School of Civil and Environmental Engineering Cornell University [email protected], [email protected] Abstract
Monitoring studies aimed at assessing water quality and environmental risk from micropollutants are challenging to
implement due to the large number of potential analytes and the spatial and temporal variability at which
micropollutants occur in surface water systems. We addressed these challenges by collecting samples during the 2015
recreational season from eight sites along the Hudson River Estuary from the confluence with the Mohawk River to the
Tappan Zee Bridge. We used solid-phase extraction and high performance liquid chromatography mass spectrometry
(HPLC-MS) to quantify the occurrence of 117 micropollutants in each sample. We selected a diverse set of
micropollutants including pharmaceuticals, pesticides, and industrial chemicals. We confirmed the occurrence of 83 of
the micropollutants in at least one of the collected samples. Eight micropollutants were quantified in every sample
collected: atenolol (β-blocker), atenolol acid (metabolite of atenolol), venlafaxine (anti-depressant), caffeine
(stimulant), paraxanthine (metabolite of caffeine), sucralose (artificial sweetener), methyl benzotriazole (an industrial
chemical), and DEET (an insect repellant). These data represent the first comprehensive survey of micropollutants in
the Hudson River Estuary and will be invaluable for developing future research projects aimed at assessing spatial and
temporal variability of micropollutant occurrence and the consequent environmental risk.


First comprehensive monitoring for micropollutants in the Hudson River Estuary.
The number and types of pesticides measured were spatially and temporally stable.
The number and types of pharmaceuticals measured were determined by proximity to wastewater treatment Keywords: micropollutants, emerging contaminants, pharmaceuticals, pesticides, mass spectrometry Target Screening for Micropollutants in the Hudson River Estuary during the 2015 Recreational Season

to two dozen compounds to study and risk assessments An estimated 84,000 synthetic organic chemicals are are conducted based on the resulting dataset. This used daily in domestic, commercial, or industrial strategy has been shown to significantly underestimate applications (Schnoor, 2014). The life cycle of these the potential risk associated with micropollutants in chemicals often results in their accumulation in the surface water resources (Moschet et al., 2014). environment, with many of the more polar and semi- The waters of the Hudson River Estuary (delineated in polar chemicals (including most pesticides and Figure 1) are used for recreational purposes (i.e.,
pharmaceuticals) known to occur globally in surface swimming, boating, fishing) and as a source of drinking water resources (Kolpin et al., 2002; Richardson and water for over 100,000 people. The Hudson River is also Ternes, 2014; Richardson, 2012; Schwarzenbach et al., a receiver of a number of industrial and sewage treatment plant (STP) discharges, storm sewer outfalls, Concern over the occurrence of these so-called and combined sewer overflows (New York State micropollutants in water resources is predicated on the Department of Environmental Conservation, 2015). notion that exposure to them poses a significant risk to Further, the land use in the Hudson River watershed is aquatic ecosystem or human health. Although mixed, with significant areas of urban, agricultural, and toxicological data are limited relative to the large industrial uses (New York State Department of number of micropollutants known to occur in the Environmental Conservation, 2015). As such, the Hudson environment, the emerging view is that complex River is expected to be impacted by a wide variety of mixtures of environmentally relevant concentrations of wastewater-derived, micropollutants can lead to developmental or genotoxic micropollutants. However, there exists a limited amount effects (Altenburger et al., 2012; Pomati et al., 2006). of data on the occurrence of micropollutants in the Additionally, for the small subset of chemicals that have Hudson River Estuary. Therefore, it is difficult to assess been rigorously studied with respect to toxicity, there water quality in the Hudson River Estuary with respect to have been reports of significant developmental, these emerging contaminants. reproductive, endocrine disrupting, and other chronic health effects (Brody and Rudel, 2003; Colburn et al., 1993; Daughton and Ternes, 1999; McKinlay et al., 2008; Murray et al., 2010; Toppari et al., 1996). The main sources of micropollutants are domestic and industrial wastewater treatment plant discharges, storm sewer outfalls, combined sewer overflows, and diffuse runoff from agricultural or urban landscapes (Brown and van Beinum, 2009; Wittmer et al., 2010). As such, the occurrence and concentration of micropollutants in any watershed is dependent on a variety of local features including land use, weather, hydrology, type of sewer system, and number and type of wastewater treatment plant discharges. Therefore, it is expected that the occurrence and concentration of micropollutants in any surface water system will vary significantly both temporally and spatially within the watershed. The large number of micropollutants and the inherent spatial and temporal variability of their occurrence levels makes it challenging to develop appropriate monitoring programs to assess the potential for exposure and risk to aquatic ecosystems and downstream human populations. Figure 1: Hudson River Estuary Program boundaries.
micropollutants generally starts with the selection of one Image from: http://www.dec.ny.gov/lands/4920.html This report was prepared for the New York State Water Resources Institute (WRI) and the Hudson River Estuary program of the New York State Department of Environmental Conservation, with support from the NYS Environmental Protection Fund Target Screening for Micropollutants in the Hudson River Estuary during the 2015 Recreational Season

Riverkeeper is a member-supported organization dedicated to monitoring and protecting the waters of the Hudson River Estuary. Riverkeeper uses a patrol boat equipped with a mobile laboratory to collect water samples from 74 sites along the Hudson River Estuary. Samples have been collected monthly throughout the recreational season (May through October) since 2008 and are analyzed for fecal-indicating bacteria of the genus Enterococcus along with a suite of other standard water quality indicators including pH, salinity, dissolved oxygen, and turbidity. Records of these data collection efforts are maintained on the Riverkeeper website (Riverkeeper, 2015a). We partnered with Riverkeeper to collect samples from eight of their 74 sampling locations along the Hudson River Estuary. The sites were sampled in June, July, September and October of 2015. The sites included Hudson above Troy Lock, Dunn Memorial Bridge, Kingston Sewage Treatment Plant Outfall, Port Ewen Drinking Water Intake, Poughkeepsie Drinking Water Intake, Newburgh Launch Ramp, West Point Sewage Treatment Plant Outfall, and Orangetown Sewage Treatment Plant Outfall. A map of the sampling sites are provided in Figure 2. Samples were collected in one liter
pharmaceutical (blue) and pesticide (brown) detections amber glass, trace clean bottles and shipped to our during each sampling month. laboratory at Cornell for analysis. Brief details on sampling and analytical methods are provided below. recreational season and along the length of the Hudson River. This suggests that the main sources of pesticides Results & Discussion
into the Hudson River are diffuse, likely from agricultural We collected samples during four months of the runoff, spray drift, or groundwater infiltration. recreational season at eight discrete locations along the Understanding the influence of application seasons Hudson River Estuary, for a total of 32 samples. Of those would require higher sampling frequency with greater 32 samples, two were lost during sample processing in temporal resolution, though literature data suggests that our laboratory and six were lost during shipping (broken the types and concentrations of pesticides will spike during transit). Therefore, 24 samples were processed during the spring application season (Gilliom, 2007). and analyzed and the results of those analyses are There were a total of 64 pharmaceuticals on our target list. Of those, 50 were detected in at least one sample. Of the 117 target micropollutants, 83 were detected in Contrary to pesticides, the number of pharmaceuticals at least one of the 24 samples (for a list of target measured was quite sensitive to location. The three micropollutants and details on their frequency of sewage treatment plant outfall sites contained the detection, see Appendix A). Data on the spatial and
largest numbers of pharmaceuticals. Sites distant from temporal variability of pharmaceutical and pesticide outfalls had much lower and less variable numbers of detection are provided in Figure 2. There were a total of
pharmaceuticals detected. This observation highlights 36 pesticides on our target list. Of those, 20 were the importance of sewage outfalls as a source of detected in at least one sample and 9 of those were pharmaceutical micropollutants in the Hudson River measured in at least half of the samples. In general, every sample measured contained approximately 8 – 10 The high number of micropollutants detected at sewage pesticides, a number that was stable throughout the outfalls could be a cause for concern in communities This report was prepared for the New York State Water Resources Institute (WRI) and the Hudson River Estuary program of the New York State Department of Environmental Conservation, with support from the NYS Environmental Protection Fund Target Screening for Micropollutants in the Hudson River Estuary during the 2015 Recreational Season

downstream who rely on the river as their drinking water 2005; Kuroda et al., 2012), but no clear relationship source. The Kingston sewage treatment plant discharges between the number or type of micropollutants into Rondout Creek near its confluence with the Hudson detected and the Enterococcus counts was readily River; four miles downstream is the drinking water intake apparent in this study. Ongoing research aims to analyze for Port Ewen. While Kingston had the largest number of these data along with relevant metadata such as rainfall micropollutants detected in all months, the number of to determine whether any stronger relationships micropollutants detected at the Port Ewen intake was on become apparent. par with that seen at the rest of the non-outfall sites There were eight compounds detected in all 24 of the sampled. This suggests that the micropollutants measured samples, with six others being detected in at measured in the Kingston outfall are either being diluted least 20 of the samples. The compounds detected in all or are degraded once they enter the waters of the samples included atenolol (β-blocker), atenolol acid Hudson. For example, five β-blocker pharmaceutical (metabolite of atenolol), venlafaxine (anti-depressant), compounds (acebutolol, atenolol, metoprolol, nadolol, and propranolol) were detected in the June sample from sucralose (artificial sweetener), methyl benzotriazole Kingston outfall. Only atenolol and metoprolol were (industrial chemical), and DEET (insect repellant). The detected downstream in the Port Ewen sample from additional compounds detected in at least 20 samples June, and both were at much lower concentrations than included 2,4-D (herbicide), atrazine (herbicide), cotinine those in the Kingston outfall. While dilution likely plays a (metabolite of nicotine, a stimulant), lidocaine role, β-blockers are also known to adsorb to natural (anesthetic), metolachlor (herbicide), and metoprolol (β- minerals (Kibbey et al., 2007), undergo photolysis in water (Liu and Williams, 2007), and can be microbially Grab samples are excellent for confirming the presence transformed (Helbling et al., 2010). Thus, there are many of a particular micropollutant in a given sample (Ort et possible fates for micropollutants in water, increasing al., 2010). However, the absence of a micropollutant the complexity of understanding their occurrence, does not necessarily mean that the compound is not transport, and effects in the Hudson River Estuary. present in the Hudson River Estuary. A negative Because our samples were collected at the same time as detection could mean that the micropollutant was simply those used for the Enterococcus measurements not present at a detectable level in the sample collected conducted by Riverkeeper, it was possible to compare at a particular location and a particular time. Therefore, the micropollutant findings to the fecal coliform counts conclusions should be drawn only on what was detected, at each site. Of the 24 samples, six had Enterococcus not on was not detected. Similarly, reporting counts above 60 per 100 mL, the EPA Beach Action Value representative concentrations in a particular surface (Riverkeeper, 2015b). At sites that have counts above water sample is not always recommended when grab this level, public notification is recommended and samples are collected (Ort et al., 2010). Nevertheless, we temporary beach closures may be considered. Three of present a summary of the pharmaceutical and pesticide these samples were from the Kingston outfall site and all concentrations measured during the June sampling three likewise had high pharmaceutical compound event in Figure 3. What we can confirm from the
counts. However, the September sample at Kingston contained a similar number of pharmaceuticals as in the other months and passed the fecal indicator water quality test. The other three failed samples were all collected at the Hudson above Troy Lock site, which had pharmaceutical and pesticide counts similar to those of other non-outfall sites. Because this is a limited data set, it is difficult to draw conclusions about the relationship between Enterococcus counts and the micropollutant counts seen in our study. There have been some efforts Figure 3: Boxplots of pharmaceutical and pesticide
made to use micropollutants as indicators of water concentrations at each sample location in June 2015. quality in place of indicator bacteria (Glassmeyer et al., This report was prepared for the New York State Water Resources Institute (WRI) and the Hudson River Estuary program of the New York State Department of Environmental Conservation, with support from the NYS Environmental Protection Fund Target Screening for Micropollutants in the Hudson River Estuary during the 2015 Recreational Season

concentration data is that the majority of the The sample pH was adjusted using an ammonium pharmaceuticals and pesticides are present in the range acetate buffer. A cocktail of 21 isotope labeled internal of 10 – 100 nanograms per liter. Studies of other surface standards were spiked in each sample to control for water bodies around the world report pharmaceutical losses during the solid phase extraction procedure and concentrations as high as the 1000 nanograms per liter matrix effects during analysis. All samples and a range (Bartelt-Hunt et al., 2009; Kim et al., 2007; Loos et complete, eight point calibration curve were then passed al., 2009). In our sampling of the Hudson River Estuary, over a manually constructed multi-layer SPE cartridge the only sites with comparably high concentrations were containing Oasis HLB, Strata X-AW, Strata X-CW, Isolute those at sewage treatment plant outfalls. A more ENV+, and envi-CARB. Elution from the cartridges was with ethyl acetate/methanol (50%/50%) with 0.5% concentrations could be obtained by collecting ammonia, ethyl acetate/methanol (50%/50%) with 1.7% composite samples that are proportional to the flow of formic acid and 100% methanol. Combined neutral the river (Ort et al., 2010). extracts were evaporated under nitrogen to 0.1 mL and In light of these findings, it is imperative to note that the reconstituted with 0.9 mL of nanopure water. results on the number and types of pharmaceuticals and Analytics and data processing. The analytical method pesticides identified in the Hudson River Estuary along was previously developed and validated for a broad with the relatively low concentrations are in line with range of micropollutants (Helbling et al., 2010). Briefly, data collected in other surface water systems around the chromatographic separation was carried out with an world (Bartelt-Hunt et al., 2009; Hernando et al., 2006; XBridge C18 column (Waters) using nanopure and Kim et al., 2007; Loos et al., 2009). Nothing in this dataset methanol acidified with 0.1% formic acid as mobile suggests that the Hudson River Estuary is more or less phase. High-resolution mass spectra and MS/MS impacted by micropollutants than other major acquisitions were collected from a QExactive (Thermo) waterways in the United States, Canada, or Europe. mass spectrometer. Separate positive and negative Nevertheless, the occurrence of micropollutants in the ionization full scans with a resolution (R) of 70,000 were Hudson River Estuary (and around the world) is a major run simultaneously with All Ion Fragmentation scans (R = environmental problem and studies have shown that 35,000). Blanks and QC samples were included in the their occurrence can cause a variety of negative effects measurement sequence for quality assurance. A target to aquatic ecosystems and exposed human populations. screening approach was used to quantify the It is imperative to continue studying micropollutants in concentrations of 117 micropollutants in each of the the Hudson River to get a better understanding of samples (see Appendix A for a list of micropollutants
sources and to ultimately implement best management included in the target screening). Quantification was practices to limit their occurrence. based on the calibration curves developed during sample preparation. The compounds in this list come from a variety of use classes (pesticides, pharmaceuticals, industrial chemicals) and are generally included due to Grab samples were collected by Riverkeeper in 1 L their known persistence or putative toxicity. Detection amber, trace clean glass bottles and maintained under limits are generally in the low ng/L range for the cold temperatures on the sampling vessel. The samples micropollutants on this list. were then shipped in a cooler to our laboratory at Cornell at the end of each sampling campaign. Samples were Outreach Comments
stored at -20°C and in the dark until sample preparation We plan to prepare a one page Fact Sheet describing our methods and results that will be available on our Sample preparation. We used a mixed bed solid phase laboratory website and at the Riverkeeper website. extraction method (SPE) to concentrate the 1 L samples as previously described (Moschet et al., 2013). Briefly, Student Training
samples were thawed and vacuum filtered through a All sample processing and analysis was conducted by glass microfiber filter to remove any particulate matter. Amy Pochodylo, a Ph.D. student. This report was prepared for the New York State Water Resources Institute (WRI) and the Hudson River Estuary program of the New York State Department of Environmental Conservation, with support from the NYS Environmental Protection Fund Target Screening for Micropollutants in the Hudson River Estuary during the 2015 Recreational Season

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Appendix A – List of target analytes and their frequency of detection.

Frequency of
Compound
Detection
2,6-Dichlorobenzamide Herbicide degradation product (dichlobenil) 2,6-Dimethoxyphenol Natural component of wood smoke Pharmaceutical degradation product (primidone) Pharmaceutical (antiretroviral) Pharmaceutical (beta-blocker) Pharmaceutical (analgesic) Pharmaceutical (hormone) Pharmaceutical (asthma) Pharmaceutical (gout) Pharmaceutical (anti-depressant) Pharmaceutical (stimulant) Pharmaceutical (beta-blocker) Pharmaceutical metabolite (atenolol and metoprolol) Atrazin-2-hydroxy Herbicide degradation product (atrazine) Herbicide degradation product (atrazine) Benzotriazole methyl-1H Industrial chemical (corrosion inhibitor) Pharmaceutical (anti-depressant) Pharmaceutical (anti-convulsant) Pharmaceutical (muscle relaxant) Pharmaceutical (NSAID) Pharmaceutical (Ca channel blocker) Pharmaceutical (anti-depressant) Pharmaceutical (opiate) Degradation product of nicotine This report was prepared for the New York State Water Resources Institute (WRI) and the Hudson River Estuary program of the New York State Department of Environmental Conservation, with support from the NYS Environmental Protection Fund Target Screening for Micropollutants in the Hudson River Estuary during the 2015 Recreational Season

Pharmaceutical (corticosteroid) Dextromethorphan Pharmaceutical (antitussive) Pharmaceutical (NSAID) Pharmaceutical (antihistamine) Pharmaceutical (antiretroviral) Pharmaceutical (antibiotic) Pharmaceutical (hormone) Pharmaceutical (hormone) Ethyl butylacetylaminopropionate Pharmaceutical (antihistamine) Pharmaceutical (anti-depressant) Pharmaceutical (cholesterol reducer) Pharmaceutical (analgesic) Pharmaceutical (skin irritation) Pharmaceutical (NSAID) Pharmaceutical (contrast agent) Pharmaceutical (NSAID) Pharmaceutical (local anesthetic) Insectide degradation product (malathion) Pharmaceutical (anxiolytic) Pharmaceutical (muscle relaxant) Pharmaceutical (opioid) Pharmaceutical (muscle relaxant) Pharmaceutical (beta-blocker) Pharmaceutical (opiate) Pharmaceutical (beta-blocker) Pharmaceutical (NSAID) Pharmaceutical (anti-convulsant) This report was prepared for the New York State Water Resources Institute (WRI) and the Hudson River Estuary program of the New York State Department of Environmental Conservation, with support from the NYS Environmental Protection Fund Target Screening for Micropollutants in the Hudson River Estuary during the 2015 Recreational Season

Stimulant degradation product (caffeine) Pharmaceutical (antiviral) Pharmaceutical (muscle pain) Perfluorobutanoic acid (PFBA) Industrial chemical (fluorocarbon polymer) Perfluoroctanoic acid (PFOA) Industrial chemical (fluorocarbon polymer) Pharmaceutical (anti-convulsant) Pharmaceutical (anti-convulsant) Pharmaceutical (hormone) Herbicide degradation product (propachlor) Herbicide degradation product (propachlor) Pharmaceutical (beta-blocker) Pharmaceutical (decongestant) Pharmaceutical (antihyperglycemic) Artificial sweetener Sulfadimethoxine Pharmaceutical (antibiotic) Sulfamethoxazole Pharmaceutical (antibiotic) Pharmaceutical (antibiotic) Pharmaceutical (hormone) Pharmaceutical (methylxanthine) Pharmaceutical (diuretic) Tributyl phosphate (TBP) Industrial compound (organophosphorus) Pharmaceutical (antibiotic) Pharmaceutical (antibiotic) Trinexapac-ethyl Pharmaceutical (blood pressure) Pharmaceutical (anti-depressant) Pharmaceutical (Ca channel blocker) Pharmaceutical (anti-coagulant) This report was prepared for the New York State Water Resources Institute (WRI) and the Hudson River Estuary program of the New York State Department of Environmental Conservation, with support from the NYS Environmental Protection Fund

Source: https://wri.cals.cornell.edu/sites/wri.cals.cornell.edu/files/shared/documents/2015_Helbling_Final.pdf