Spatiotemporal patterns of PFAS in water and crop tissue at a beneficial wastewater reuse site in central Pennsylvania.

Per- and polyfluoroalkyl substances (PFAS) are a collective name for thousands of synthetic compounds produced to enhance consumer and industrial products since the 1940s. They do not easily degrade, and some are known to pose serious ecological and human health concerns at trace concentrations (ng L-1 levels). Per- and polyfluoroalkyl substances persist in treated wastewater and are inadvertently introduced into the environment when treated wastewater is reused as an irrigation source. The Pennsylvania State University (PSU) has been spray-irrigating its wastewater at a 2.45 km2 mixed-use agricultural and forested site known as the "Living Filter" since the 1960s. To understand the spatiotemporal patterns of 20 PFAS at the Living Filter, water samples were collected bimonthly from fall 2019 through winter 2021 from the PSU's wastewater effluent and from each of the site's 13 monitoring wells. Crop tissue was collected at the time of harvest to assess PFAS presence in corn silage and tall fescue grown at the study site. Total measured PFAS concentrations in the monitoring wells ranged from nondectable to 155 ng L-1 , with concentrations increasing with the direction of groundwater flow. Concentrations within each well exhibited little temporal variability across sampling events, with mixed relationships between PFAS and groundwater elevation observed between wells. Further, >84% of the PFAS present in livestock feed crops were short-chain compounds, with PFAS consumed annually by livestock fed crops harvested from the site estimated to be 2.46-7.67 mg animal-1 yr-1 . This research provides insight into the potential impacts of long-term beneficial reuse of treated wastewater on groundwater and crop tissue quality.

Impacts of the COVID-19 pandemic on pharmaceuticals in wastewater treated for beneficial reuse: Two case studies in central Pennsylvania.

During the COVID-19 pandemic, wastewater surveillance was leveraged as a powerful tool for monitoring community-scale health. Further, the well-known persistence of some pharmaceuticals through wastewater treatment plants spurred concerns that increased usage of pharmaceuticals during the pandemic would increase the concentrations in wastewater treatment plant effluent. We collected weekly influent and effluent samples from May 2020 through May 2021 from two wastewater treatment plants in central Pennsylvania, the Penn State Water Reclamation Facility and the University Area Joint Authority, that provide effluent for beneficial reuse, including for irrigation. Samples were analyzed for severe acute respiratory syndrome coronavirus 2 (influent only), two over-the-counter medicines (acetaminophen and naproxen), five antibiotics (ampicillin, doxycycline, ofloxacin, sulfamethoxazole, and trimethoprim), two therapeutic agents (remdesivir and dexamethasone), and hydroxychloroquine. Although there were no correlations between pharmaceutical and virus concentration, remdesivir detection occurred when the number of hospitalized patients with COVID-19 increased, and dexamethasone detection co-occurred with the presence of patients with COVID-19 on ventilators. Additionally, Penn State decision-making regarding instruction modes explained the temporal variation of influent pharmaceutical concentrations, with detection occurring primarily when students were on campus. Risk quotients calculated for pharmaceuticals with known effective and lethal concentrations at which 50% of a population is affected for fish, daphnia, and algae were generally low in the effluent; however, some acute risks from sulfamethoxazole were high when students returned to campus. Remdesivir and dexamethasone persisted through the wastewater treatment plants, thereby introducing novel pharmaceuticals directly to soils and surface water. These results highlight connections between human health and water quality and further demonstrate the broad utility of wastewater surveillance.

Sorption and desorption behavior of four antibiotics at concentrations simulating wastewater reuse in agricultural and forested soils.

Due to rises in antibiotic resistance, fate and transport of antibiotics in soil systems requires greater understanding to determine potential risks to human and animal health. Adsorption coefficients (Kd and Kf) are standard measures for determining sorption capacity and partitioning behavior of organic contaminants in solid matrices. Frequently, sorption studies use higher antibiotic concentrations (mg L-1) and larger spiked water volume to mass of soil (>5:1), which may not reflect sorption behaviors of antibiotics at low concentrations (ng L-1 - µg L-1) in natural soils. The aim of this study was to determine sorption and desorption behaviors of four antibiotics commonly found in soils due to wastewater reuse using parameters replicating typical soil conditions. Concentrations (µg L-1) of sulfamethoxazole (SMX), trimethoprim (TMP), lincomycin (LIN) and ofloxacin (OFL) were equilibrated with four soil types at a 2:1 ratio of spiked water volume to mass of soil, which better represents field conditions. Log Kf and log Kfoc value ranges in this study were 1.88-1.95 and 3.2-4.7 for TMP, 0.43-1.4 and 2.7-3.2 for SMX, and 0.65-1.4 and 2.0-4.1 for LIN, respectively. Ofloxacin adsorbed tightly to soil particles, and adsorption coefficients could not be calculated. Sorption values were higher than previous studies that used similar soil types but had higher ratios of spiking solution to mass of soil (>5:1). Overall, OFL and TMP are expected to strongly interact with soil particles and be less mobile, while SMX and LIN are expected to be more mobile due to weaker sorption interactions.

Comparison of POCIS and grab sampling techniques for monitoring PPCPs in vernal pools in central Pennsylvania.

Active ingredients in pharmaceuticals and personal care products (PPCPs) can persist through wastewater treatment plants and be released into the environment where they can inadvertently pose risks to non-target organisms. Emerging contaminants (ECs), including PPCPs, are commonly detected in wastewater effluent. With the increasing beneficial re-use of treated wastewater globally, there is a need to understand how spray-irrigation activities affect the occurrence and persistence of ECs in the environment to which they are introduced. Here, we explore the impacts of wastewater spray-irrigation on nearby ephemeral wetlands (e.g., vernal pools) through the use of grab and Polar Organic Chemical Integrative Sampling (POCIS) techniques. This study sought to determine whether integrative sampling techniques are better suited than traditional grab sampling techniques in assessing the presence and concentrations of ECs in vernal pools by evaluating 34 ECs in six vernal pools in central Pennsylvania. Three pools were impacted by wastewater spray-irrigation activities and three were in a nearby forested area. Results of this study found that POCIS detected a wide range of 25 ECs (log Kow between -2.6 and 9.37) more or, in some cases, equally frequently, relative to grab samples. Additionally, grab samples were found to best capture short-lived elevated inputs of ECs (from irrigation events) while POCIS were found to best capture ECs that were present in vernal pools over a longer period of time (weeks to months). For ECs detected more frequently in grab samples, concentrations were higher compared to time weighted average aqueous concentrations estimated from POCIS. This study advances understanding of the potential impact of wastewater beneficial reuse on vernal pools and informs how best to monitor the presence of ECs in vernal pools using integrative and grab sampling techniques.

Modeling carbamazepine transport in wastewater-irrigated soil under different land uses.

The pharmaceutical compound carbamazepine (CBZ) is a contaminant of emerging concern. Wastewater irrigation can be a long-term, frequent source of CBZ; therefore, understanding the fate and transport of CBZ as a result of wastewater reuse practices has important environmental implications. The objective of this study was to estimate long-term soil transport of CBZ originating from treated wastewater irrigation on plots under different land uses. Field data from a previous study comparing CBZ concentrations in soil under different land uses were used in numerical modeling with HYDRUS-2D for the estimation of CBZ soil transport during 20 yr of irrigation with treated wastewater. This study showed high CBZ retention in soil under all investigated land uses. Adequate modeling results were obtained by using soil organic carbon-water partitioning coefficient (Koc ) for the CBZ linear sorption coefficient (Kd ) estimation, yet an underestimation of CBZ concentration in soil was still noted. Thus, results suggest that, although highly important, organic carbon content is probably not the only soil property governing CBZ sorption at this site, indicating the potential research perspective. Modeling results showed wastewater irrigation containing CBZ for 20 yr increased the CBZ concentration in the soil profile and its vertical movement, with the slowest vertical transport rate occurring on the forested plots. Overall results suggest that a beneficial management practice could be to increase soil organic carbon (e.g., compost addition) when using treated wastewater for irrigation in order to retain CBZ in the surface soil and thus limit its leaching through the soil profile.

Influence of hydrologic and anthropogenic drivers on emerging organic contaminants in drinking water sources in the Susquehanna River Basin.

Occurrence of emerging organic contaminants (EOCs) in surface water bodies can cause adverse effects on non-target organisms. When surface waters are used as drinking water sources, temporal variability in EOC concentrations can potentially impact drinking water quality and human health. To better understand spatiotemporal variability of EOCs in drinking water sources in Central Pennsylvania, EOCs were evaluated in six drinking water sources during a two-year study period (April 2016-June 2018) in the Susquehanna River Basin (SRB). The study was conducted in two phases: Phase I was a spatially distributed sampling approach within the SRB focusing on seven human pharmaceuticals and Phase II was a temporally intensive sampling regime at a single site focusing on a broader range of EOCs. Concentration-discharge relationships were utilized to classify EOC transport dynamics and understand the extent to which hydrologic and anthropogenic factors, such as surface runoff and wastewater effluent, may contribute to EOC occurrence. Overall, EOCs were present at higher concentrations in colder seasons than warmer seasons. Thiamethoxam, a neonicotinoid insecticide, and caffeine exhibited accretion dynamics during high-flow periods, suggesting higher transport during surface runoff events. Human pharmaceuticals known to persist in wastewater effluent were inversely correlated with discharge, indicating dilution characteristics consistent with diminished wastewater signals during high-flow periods. Acetaminophen exhibited near-chemostatic transport dynamics, indicating nonpoint source inputs during high-flow periods. Risk calculations revealed that although EOCs posed medium-to-high risk to aquatic organisms, human health risk through fish consumption was low.

Occurrence, Concentrations, and Risks of Pharmaceutical Compounds in Private Wells in Central Pennsylvania.

Over-the-counter and prescription medications are routinely present at detectable levels in surface and groundwater bodies. The presence of these emerging contaminants has raised both environmental and public health concerns, particularly when the water is used for drinking either directly or with additional treatment. However, the frequency of occurrence, range of concentrations, and potential human health risks are not well understood, especially for groundwater supplies. Private wells are often not tested for contaminants regulated by drinking water standards and are even less frequently tested for emerging contaminants. By partnering with the Pennsylvania Master Well Owner Network, water samples were collected from 26 households with private wells in the West Branch of the Susquehanna River basin in central Pennsylvania in winter 2017. All samples were analyzed for six pharmaceuticals (acetaminophen, ampicillin, naproxen, ofloxacin, sulfamethoxazole, and trimethoprim) and one over-the-counter stimulant (caffeine). At least one compound was detected at each site. Ofloxacin and naproxen were the most and least frequently detected compounds, respectively. Concentrations from the groundwater wells were higher than those of nearby surface water samples. However, risk calculations revealed that none of the concentrations measured in groundwater samples posed significant human health risk. A simple, physicochemical-based modeling approach was used to predict pharmaceutical transport from septic absorption field to groundwater and further elucidate variations in detection frequencies. Findings indicate that although septic tanks may act as contaminant sources for groundwater wells, the human health impacts from trace-level pharmaceuticals that may be present are likely minimal.

Fate of pharmaceuticals in a spray-irrigation system: From wastewater to groundwater.

Land application of wastewater effluent is beneficial for recharging groundwater aquifers and avoiding direct pollutant discharges to surface waters. However, the fate of non-regulated organic wastewater pollutants, such as pharmaceuticals and personal care products (PPCPs), in such wastewater reuse systems is understudied. Here, a 14-month study (October 2016 through December 2017) was conducted to evaluate the fate and potential risks of seven commonly used PPCPs in a local wastewater treatment plant (WWTP) and from 13 groundwater monitoring wells at a spray-irrigation site where effluent has been spray-irrigated since the early 1980s. Acetaminophen and trimethoprim were the most frequently detected (93%) PPCPs in WWTP influent, while in the effluent, caffeine and trimethoprim were detected most frequently (70%). Wastewater treatment generally reduced concentrations of acetaminophen and caffeine by >88%; however, some compounds had low removal or were present at higher concentrations in the effluent compared with influent (e.g. naproxen, sulfamethoxazole, trimethoprim and ofloxacin). Seasonal trends were observed, with higher PPCP concentrations in the WWTP influent and effluent in the winter. Risk calculations conducted on the wastewater effluent suggest that the risk posed by PPCPs that persisted in the effluent are medium to high to aquatic organisms. Detection frequencies of PPCPs were lower in groundwater samples compared to the effluent, with sulfamethoxazole (40%) and caffeine (32%) as the most frequently detected compounds. Similarly, average concentrations of PPCPs in groundwater were found to be nearly two orders of magnitude lower than concentrations in the effluent. Minimal seasonal influence was observed for groundwater samples. Human health risk assessments indicate that concentrations in groundwater, which is used as a drinking water source, appear to pose minimal risk.

Assessment of Soil to Mitigate Antibiotics in the Environment Due to Release of Wastewater Treatment Plant Effluent.

With low levels of human antibiotics in the environment due to release of wastewater treatment plant (WWTP) effluent, concern is rising about impacts on human health and antibiotic resistance development. Furthermore, WWTP effluent may be released into waterways used as drinking water sources. The aim of this study was to analyze three antibiotics important to human health (sulfamethoxazole, ofloxacin, and trimethoprim) in soil and groundwater at a long-term wastewater reuse system that spray irrigates effluent. Soil samples were collected (i) at a site that had not received irrigation for 7 mo (approximate background concentrations), and then at the same site after (ii) one irrigation event and (iii) 10 wk of irrigation. Water samples were collected three times per year to capture seasonal variability. Sulfamethoxazole was typically at the highest concentrations in effluent (22 ± 3.7 µg L) with ofloxacin and trimethoprim at 2.2 ± 0.6 and 1.0 ± 0.02 µg L, respectively. In the soil, ofloxacin had the highest background concentrations (650 ± 204 ng kg), whereas concentrations of sulfamethoxazole were highest after continuous effluent irrigation (730 ± 360 ng kg). Trimethoprim was only quantified in soil after 10 wk of effluent irrigation (190 ± 71 ng kg). Groundwater concentrations were typically <25 ng L with high concentrations of 660 ± 20 and 67 ± 7.0 ng L for sulfamethoxazole and ofloxacin, respectively. Given that antibiotics interacted with the soil profile and groundwater concentrations were frequently about 1000-fold lower than effluent, soil may be an adequate tertiary treatment for WWTP effluent leading to improved water quality and protection of human health.

Antibiotics in Agroecosystems: Introduction to the Special Section.

The presence of antibiotic drug residues, antibiotic resistant bacteria, and antibiotic resistance genes in agroecosystems has become a significant area of research in recent years and is a growing public health concern. While antibiotics are used in both human medicine and agricultural practices, the majority of their use occurs in animal production where historically they have been used for growth promotion, in addition to the prevention and treatment of disease. The widespread use of antibiotics and the application of animal wastes to agricultural lands play major roles in the introduction of antibiotic-related contamination into the environment. Overt toxicity in organisms directly exposed to antibiotics in agroecosystems is typically not a major concern because environmental concentrations are generally lower than therapeutic doses. However, the impacts of introducing antibiotic contaminants into the environment are unknown, and concerns have been raised about the health of humans, animals, and ecosystems. Despite increased research focused on the occurrence and fate of antibiotics and antibiotic resistance over the past decade, standard methods and practices for analyzing environmental samples are limited and future research needs are becoming evident. To highlight and address these issues in detail, this special collection of papers was developed with a framework of five core review papers that address the (i) overall state of science of antibiotics and antibiotic resistance in agroecosystems using a causal model, (ii) chemical analysis of antibiotics found in the environment, (iii) need for background and baseline data for studies of antibiotic resistance in agroecosystems with a decision-making tool to assist in designing research studies, as well as (iv) culture- and (v) molecular-based methods for analyzing antibiotic resistance in the environment. With a focus on the core review papers, this introduction summarizes the current state of science for analyzing antibiotics and antibiotic resistance in agroecosystems, discusses current knowledge gaps, and develops future research priorities. This introduction also contains a glossary of terms used in the core reivew papers of this special section. The purpose of the glossary is to provide a common terminology that clearly characterizes the concepts shared throughout the narratives of each review paper.

Uptake of Three Antibiotics and an Antiepileptic Drug by Wheat Crops Spray Irrigated with Wastewater Treatment Plant Effluent.

With rising demands on water supplies necessitating water reuse, wastewater treatment plant (WWTP) effluent is often used to irrigate agricultural lands. Emerging contaminants, like pharmaceuticals and personal care products (PPCPs), are frequently found in effluent due to limited removal during WWTP processes. Concern has arisen about the environmental fate of PPCPs, especially regarding plant uptake. The aim of this study was to analyze uptake of sulfamethoxazole, trimethoprim, ofloxacin, and carbamazepine in wheat ( L.) plants that were spray-irrigated with WWTP effluent. Wheat was collected before and during harvest, and plants were divided into grain and straw. Subsamples were rinsed with methanol to remove compounds adhering to surfaces. All plant tissues underwent liquid-solid extraction, solid-phase extraction cleanup, and liquid chromatography-tandem mass spectrometry analysis. Residues of each compound were present on most plant surfaces. Ofloxacin was found throughout the plant, with higher concentrations in the straw (10.2 ± 7.05 ng g) and lower concentrations in the grain (2.28 ± 0.89 ng g). Trimethoprim was found only on grain or straw surfaces, whereas carbamazepine and sulfamethoxazole were concentrated within the grain (1.88 ± 2.11 and 0.64 ± 0.37 ng g, respectively). These findings demonstrate that PPCPs can be taken up into wheat plants and adhere to plant surfaces when WWTP effluent is spray-irrigated. The presence of PPCPs within and on the surfaces of plants used as food sources raises the question of potential health risks for humans and animals.

Vadose Zone Transport of Natural and Synthetic Estrogen Hormones at Penn State's "Living Filter" Wastewater Irrigation Site.

The increase in endocrine-disrupting compounds in the environment has generated research focused on the behavior of these compounds in natural soil and water ecosystems. To understand how estrogens behave in the soil environment as a result of 25+ yr of wastewater irrigation, soils from Penn State's "Living Filter" wastewater irrigation site were extracted and analyzed for two natural estrogens (17ß-estradiol and estrone) and one synthetic estrogen (17α-ethynylestradiol). Soil estrogen concentrations were compared for two independent variables: type of land cover and sampling time. Soils were sampled from cropped and forested land areas, and soils were sampled 2 d and 3 wk after a single 12-h effluent irrigation event. A nonirrigated control site was sampled to provide natural background data. For 17ß-estradiol, the nonirrigated mean concentration was 0.68 ± 0.11 ng cm, and the irrigated values, including samples from both land areas and time frames, ranged from 0.99 ± 0.11 to 1.82 ± 0.69 ng cm. For estrone, the nonirrigated mean concentration was 2.36 ± 0.22 ng cm, and the irrigated values, including samples from both land areas collected and time frames, ranged from 2.18 ± 0.20 to 6.24 ± 3.14 ng cm. The 17α-ethynylestradiol nonirrigated mean concentration was 0.47 ± 0.40 ng cm. The irrigated values, including samples from both land areas and time frames, ranged from 0.25 ± 0.06 to 1.37 ± 0.39 ng cm. This study found that time of sampling, land cover, and irrigation can affect estrogen concentrations in soils, resulting in levels that exceed natural background and require improvements in management practices.

Occurrence of carbamazepine in soils under different land uses receiving wastewater.

Due to its resistance to many wastewater treatment processes, the antiepileptic drug carbamazepine (CBZ) is routinely found in wastewater effluent. Wastewater irrigation is an alternative to stream discharge of wastewater effluent, which utilizes the soil as a tertiary filter to remove excess nutrients and has the potential to remove pharmaceutical compounds. Previous data suggest that CBZ is strongly sorbed to soil; however, it is unknown what its fate is for long periods of irrigation and if land use affects its distribution. Therefore, the objectives of our research were to characterize CBZ concentrations in soils that have been receiving wastewater irrigation for >25 yr under three different land uses: cropped, grassed, and forested. Triplicate soil cores were collected at each of the land uses to a depth of 120 cm. Extractions for CBZ were performed using 5-g soil samples and 20 mL of acetonitrile. The extracted solutions were analyzed on a liquid chromatograph tandem mass spectrometer. The samples were also analyzed for supporting information such as organic carbon, pH, and electrical conductivity. Results suggest that there is accumulation of the CBZ in the surface soils, which have the highest organic carbon content. Average concentrations of CBZ in the surface soils were 4.92, 2.9, and 1.92 ng g, for the forested, grassed, and cropped land uses, respectively. The majority of the CBZ was found in the upper 30 cm of the profile. Our results suggest that the soils adsorb CBZ and slow its movement into groundwater, compared to the movement of nonadsorbed chemicals.

Adsorption of estrogens on laboratory materials and filters during sample preparation.

Despite improvements in analytical techniques for detecting hormones, such as estrogen in environmental samples, there is conflicting information regarding sample filtration before analyses. In addition, there is little information about estrogen adsorption onto other common laboratory materials, including glass, plastic, or stainless steel. Therefore, we have quantified the adsorption of three different types of estrogen (estrone [E1], 17alpha-ethynylestradiol [EE2], and 17beta-estradiol [E2]) onto 11 different types of filters and six other types of materials used for sample storage and laboratory experiments. We observed significant (p < 0.05) differences in the amount of estrogen adsorbed to the different filters. Glass fiber filters adsorbed the lowest amount, whereas nylon filters adsorbed nearly all of the estrogen that contacted them during filtration. Stainless steel and polycarbonate also adsorbed significant amounts of E1, E2, and EE2. The materials with which estrogen comes into contact should be chosen carefully to avoid potential losses due to sorption.