Fixed bed column experiments using cotton gin waste and walnut shells-derived biochar as low-cost solutions to removing pharmaceuticals from aqueous solutions.

Acetaminophen (ACT), sulfapyridine (SPY), ibuprofen (IBP) and docusate (DCT) are pharmaceuticals with widespread usage that experience incomplete removal in wastewater treatment systems. While further removal of these pharmaceuticals from wastewater effluent is desired prior to beneficial reuse, additional treatment technologies are often expensive and energy intensive. This study evaluated the ability of biochar produced from cotton gin waste (CG700) and walnut shells (WS800) to remove four pharmaceuticals (ACT, SPY, IBP, and DCT) from aqueous solution. Physico-chemical properties of the biochars were characterized by Brunauer-Emmett-Teller (BET) analysis, scanning electron microscopy (SEM), Fourier Transform Infrared Spectroscopy (FT-IR), and zeta potential. The increased pyrolysis temperature during the production of WS800 led to an increase in the specific surface area and increased dehydration of the biochar represented by the loss of the OH-group. Fixed-bed column experiments were performed to determine the difference in removal efficiency between the biochars and elucidate the effects of biochar properties on the adsorption capacity for the pharmaceuticals of interest. Results showed that CG700 had a greater affinity for removing DCT (99%) and IBP (50%), while WS800 removed 72% of SPY and 68% of ACT after 24 h. Adsorption was influenced by the solution pH, surface area, net charge, and functional groups of the biochars. The mechanisms for removal included pore filling and diffusion, hydrophobic interactions, hydrogen bonding, and π-π electron donor acceptor interactions. To conduct predictive modeling of the column breakthrough curves, the Thomas, Adams-Bohart, and Yoon-Nelson models were applied to the experimental data. Results demonstrated that these models generally provided a poor fit for the description of asymmetrical breakthrough curves. Overall, the results demonstrate that biochars from cotton gin waste and walnut shells could be used as cost-effective, environmentally friendly alternatives to activated carbon for the removal of pharmaceuticals from aqueous solutions.

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.

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.

The emergence, trajectory, and impacts of emerging contaminants publications in the Journal of Environmental Quality.

As analytical capabilities in the early 2000s began to enable the detection of chemicals in environmental media at increasingly small concentrations, chemicals with the potential to cause adverse human and ecosystem health effects began to be found nearly ubiquitously worldwide. The types of chemicals that were targeted for analysis included natural and synthetic hormones, human and veterinary pharmaceuticals, chemicals in personal care products, novel pesticides, nanoparticles, microplastics, and other chemicals of natural and synthetic origin. The impacts of these chemicals on environmental and human health in many cases remain unknown. Collectively, these chemicals became known as "emerging contaminants" or "contaminants of emerging concern." Much progress has been made toward understanding the sources of these contaminants in the environment, the processes that control their fate and transport once they are released into the environment, and the ability of technology and/or best management practices to mitigate their occurrence. As the Journal of Environmental Quality (JEQ) celebrates its 50th anniversary, we sought to understand how publications in the journal have made impactful contributions in the research area of emerging contaminants. Here, we present the trajectory of publications in JEQ that have shaped knowledge in this field, highlight the importance of these contributions, and conclude with opportunities for JEQ to continue attracting high-quality emerging contaminants research.

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.

Relationship between total dissolved solids and electrical conductivity in Marcellus hydraulic fracturing fluids.

The production of hydraulic fracturing fluids (HFFs) in natural gas extraction and their subsequent management results in waste streams highly variable in total dissolved solids (TDS). Because TDS measurement is time-consuming, it is often estimated from electrical conductivity (EC) assuming dissolved solids are predominantly ionic species of low enough concentration to yield a linear TDS-EC relationship: TDS (mg/L) = ke × EC (µS/cm) where ke is a constant of proportionality. HHFs can have TDS levels from 20,000 to over 300,000 mg/L wherein ion-pair formation and non-ionized solutes invalidate a simple TDS-EC relationship. Therefore, the composition and TDS-EC relationship of several fluids from Marcellus gas wells in Pennsylvania were assessed. Below EC of 75,000 µS/cm, TDS (mg/L) can be estimated with little error assuming ke = 0.7. For more concentrated HFFs, a curvilinear relationship (R2 = 0.99) is needed: TDS = 27,078e1.05 × 10-5*EC. For hypersaline HFFs, the use of an EC/TDS meter underestimates TDS by as much as 50%. A single linear relationship is unreliable as a predictor of brine strength and, in turn, potential water quality and soil impacts from accidental releases or the suitability of HFFs for industrial wastewater treatment.

Imaging Hydrological Processes in Headwater Riparian Seeps with Time-Lapse Electrical Resistivity.

Delineating hydrologic and pedogenic factors influencing groundwater flow in riparian zones is central in understanding pathways of water and nutrient transport. In this study, we combined two-dimensional time-lapse electrical resistivity imaging (ERI) (depth of investigation approximately 2 m) with hydrometric monitoring to examine hydrological processes in the riparian area of FD-36, a small (0.4 km2 ) agricultural headwater basin in the Valley and Ridge region of east-central Pennsylvania. We selected two contrasting study sites, including a seep with groundwater discharge and an adjacent area lacking such seepage. Both sites were underlain by a fragipan at 0.6 m. We then monitored changes in electrical resistivity, shallow groundwater, and nitrate-N concentrations as a series of storms transitioned the landscape from dry to wet conditions. Time-lapse ERI revealed different resistivity patterns between seep and non-seep areas during the study period. Notably, the seep displayed strong resistivity reductions (∼60%) along a vertically aligned region of the soil profile, which coincided with strong upward hydraulic gradients recorded in a grid of nested piezometers (0.2- and 0.6-m depth). These patterns suggested a hydraulic connection between the seep and the nitrate-rich shallow groundwater system below the fragipan, which enabled groundwater and associated nitrate-N to discharge through the fragipan to the surface. In contrast, time-lapse ERI indicated no such connections in the non-seep area, with infiltrated rainwater presumably perched above the fragipan. Results highlight the value of pairing time-lapse ERI with hydrometric and water quality monitoring to illuminate possible groundwater and nutrient flow pathways to seeps in headwater riparian areas.

Linking nitrogen management, seep chemistry, and stream water quality in two agricultural headwater watersheds.

Riparian seepage zones in headwater agricultural watersheds represent important sources of nitrate-nitrogen (NO-N) to surface waters, often connecting N-rich groundwater systems to streams. In this study, we examined how NO-N concentrations in seep and stream water were affected by NO-N processing along seep surface flow paths and by upslope applications of N from fertilizers and manures. The research was conducted in two headwater agricultural watersheds, FD36 (40 ha) and RS (45 ha), which are fed, in part, by a shallow fractured aquifer system possessing high (3-16 mg L) NO-N concentrations. Data from in-seep monitoring showed that NO-N concentrations generally decreased downseep (top to bottom), indicating that most seeps retained or removed a fraction of delivered NO-N (16% in FD36 and 1% in RS). Annual mean N applications in upslope fields (as determined by yearly farmer surveys) were highly correlated with seep NO-N concentrations in both watersheds (slope: 0.06; = 0.79; < 0.001). Strong positive relationships also existed between seep and stream NO-N concentrations in FD36 (slope: 1.01; = 0.79; < 0.001) and in RS (slope: 0.64; = 0.80; < 0.001), further indicating that N applications control NO-N concentrations at the watershed scale. Our findings clearly point to NO-N leaching from upslope agricultural fields as the primary driver of NO-N losses from seeps to streams in these watersheds and therefore suggest that appropriate management strategies (cover crops, limiting fall/winter nutrient applications, decision support tools) be targeted in these zones.

Phosphorus partitioning in co-dewatering biosolids and water treatment residuals.

Stabilization and dewatering methods for wastewater solids determine the concentration and nature of phosphorus (P) in biosolids and in-plant sidestreams recycled to the liquid treatment facility. Because water treatment residuals (WTR) exhibit strong immobilization of soluble P, this study evaluated the impact of co-dewatering WTR and biosolids on the P partitioning during dewatering and the environmental lability of biosolids-P measured by water-extractable P (WEP). Overall, P progressively partitioned into the water-insoluble particulate-bound form in dewatered cake with increasing blending ratio (BR) - defined as the dry mass ratio of WTR to biosolids. The reject water total P (TP) content from dewatering biosolids alone (250 mg L⁻¹) was reduced to 60 mg L⁻¹ for a BR = 1.5. Polymer addition resulted in statistically (α = 0.05) lower reject liquid TP, suggesting the cationic polyelectrolyte contributed to P binding. The WEP of the dewatered cake (∼20% solids) dropped from 2.36 g kg⁻¹ (biosolids only) to ∼0.14 g kg⁻¹ for BR = 1.5, meaning the P in land-applied co-processed cake is less susceptible to solubilization by surface runoff compared to unamended biosolids. Co-dewatering can reduce P in return flows and fix P in the dewatered solids in a form less prone to off-site migration following land application.

Influence of water treatment residuals on dewaterability of wastewater biosolids.

Co-dewatering of water treatment residuals (WTR) and wastewater biosolids can potentially benefit municipalities by reducing processing equipment and costs. This study investigated dewaterability (using capillary suction time, CST) of combined alum residuals (Al-WTR) and anaerobically digested biosolids at various blending ratios (BR), defined as the mass ratio of WTR to biosolids on a dry solids basis. Without polymer addition, the CST was 160 s for a BR of 0.75 compared with 355 s for the biosolids alone. The optimum polymer dose (OPD), defined as the polymer dose yielding CST of 20 s, was reduced from 20.6 g kg(-1) dry solids for the biosolids alone to 16.3 and 12.6 g kg(-1) when BR was 0.75 and 1.5, respectively. Precipitated Al hydrous oxides in the WTR likely caused flocculation of the biosolids particles through heterocoagulation or charge neutralization. The solids contents of the blended materials and biosolids at their respective OPDs were not statistically different (α = 0.05) following dewatering by a belt-filter press. We conclude addition of Al-WTR improved biosolids dewaterability and reduced polymer dosage. In practice, the extent of these benefits may be limited by the quantity of WTR produced relative to the amount of wastewater solids generated by a municipality.

Physicochemical properties related to long-term phosphorus retention by drinking-water treatment residuals.

Drinking-water treatment residuals (WTRs) are nonhazardous materials that can be obtained free-of-charge from drinking-water treatment plants to reduce soluble phosphorus (P) concentrations in poorly P sorbing soils. Phosphorus sorption capacities of WTRs can vary 1-2 orders of magnitude, on the basis of short-term equilibration times (up to 7 d), but studies dealing with long-term (weeks to months) P retention by WTRs are lacking. Properties that most affect long-term P sorption capacities are pertinent to the efficacy of WTRs as amendments to stabilize P in soils. This research addressed the long-term (up to 80 d) P sorption/desorption characteristics and kinetics for seven WTRs, including the influence of specific surface area (SSA), porosity, and total C content on the overall magnitude of P sorption by seven WTRs. The data confirm a strong but variable affinity for P by WTRs. Aluminum-based WTRs tended to have higher P sorption capacity than Fe-based WTRs. Phosphorus sorption with time was biphasic in nature for most samples and best fit to a second-order rate model. The P sorption rate dependency was strongly correlated with a hysteretic P desorption, consistent with kinetic limitations on P desorption from micropores. Oxalate-extractable Al + Fe concentrations of the WTRs did not effectively explain long-term (80 d) P sorption capacities of the WTRs. Micropore (CO2-based) SSAs were greater than BET-N2 SSAs for most WTRs, except those with the lowest (<80 g kg(-1)) total C content. There was a significant negative linear correlation between the total C content and the CO2/N2 SSA ratio. The data suggest that C in WTRs increases microporosity, but reduces P sorption per unit pore volume or surface area. Hence, variability in C content confounds direct relations among SSA, porosity, and P sorption. Total C, N2-based SSA, and CO2-based SSAs explained 82% of the variability in the long-term P sorption capacities of the WTRs. Prediction of long-term P sorption capacities for different WTRs may be achieved by taking into account the three proposed variables.