Estrogen Transport in Surface Runoff from Agricultural Fields Treated with Two Application Methods of Dairy Manure.

This study compares two methods of dairy manure application-surface broadcast and shallow disk injection-on the fate and transport of natural estrogens in surface runoff from 12 field plots in central Pennsylvania. Ten natural surface runoff events were sampled over a 9-mo period after fall manure application. Results show that the range of estrogen concentrations observed in surface runoff from the broadcast plots was several orders of magnitude higher (>5000 ng L) than the concentrations in runoff from the shallow disk injection plots (<10 ng L). Additionally, the transport dynamics differed, with the majority of the estrogen loads from the surface broadcast plots occurring during the first rainfall event after application, whereas the majority of the loads from the shallow disk injection plots occurred more than 6 mo later during a hail storm event. Total estrogen loads were, on average, two orders of magnitude lower for shallow disk injection compared with surface broadcast. Independent of the method of manure application, 17α-estradiol and estrone were preserved in the field for as long as 9 mo after application. Overall, injection of manure shows promise in reducing the potential for off-site losses of hormones from manure-amended soils.

Assessing impacts of land-applied manure from concentrated animal feeding operations on fish populations and communities.

Concentrated animal feeding operation (CAFO) manure is a cost-effective fertilizer. In the Midwest, networks of subsurface tile-drains expedite transport of animal hormones and nutrients from land-applied CAFO manure to adjacent waterways. The objective of this study was to evaluate impacts of land-applied CAFO manure on fish populations and communities. Water chemistry including hormone, pesticide, and nutrient concentrations was characterized from study sites along with fish assemblage structure, growth, and endocrine disruption assessed in selected fish species. Although most CAFO water samples had hormone concentrations <1 ng/L, equivalent concentrations for 17ß-E2 and 17α-TB peaked at >30 ng/L each during the period of spawning, hatching, and development for resident fishes. CAFO sites had lower fish species richness, and fishes exhibited faster somatic growth and lower reproductive condition compared to individuals from the reference site. Fathead minnows (Pimephales promelas) exposed to CAFO ditchwater during early developmental stages exhibited significantly skewed sex ratios toward males. Maximum observed hormone concentrations were well above the lowest observable effect concentrations for these hormones; however, complexities at the field scale make it difficult to directly relate hormone concentration and impacts on fish. Complicating factors include the consistent presence of pesticides and nutrients, and the difference in temperature and stream architecture of the CAFO-impacted ditches compared to the reference site (e.g., channelization, bottom substrate, shallow pools, and riparian cover).

Hormone discharges from a midwest tile-drained agroecosystem receiving animal wastes.

Manure is increasingly being viewed as a threat to aquatic ecosystems due to the introduction of natural and synthetic hormones from land application to agricultural fields. In the Midwestern United States, where most agricultural fields are tile-drained, there is little known about hormone release from fields receiving animal wastes. To this end, seven sampling stations (four in subsurface tile drains and three in the receiving ditch network) were installed at a Midwest farm where various types of animal wastes (beef, dairy, and poultry lagoon effluent, dairy solids, and subsurface injection of swine manure) are applied to agricultural fields. Water flow was continuously monitored and samples were collected for hormone analysis during storm events and baseline flow for a 15 month study period. The compounds analyzed included the natural hormones 17α- and 17ß-estradiol, estrone, estriol, testosterone, and androstenedione and the synthetic androgens 17α- and 17ß-trenbolone and trendione. Hormones were detected in at least 64% of the samples collected at each station, with estrone being detected the most frequently and estriol the least. Testosterone and androstendione were detected more frequently than synthetic androgens, which were detected in fewer than 15% of samples. Hormone concentrations in subsurface tile drains increased during effluent irrigation and storm events. Hormones also appeared to persist over the winter, with increased concentrations coinciding with early thaws and snowmelt from fields amended with manure solids. The highest concentration of synthetic androgens (168 ng/L) observed coincided with a snowmelt. The highest concentrations of hormones in the ditch waters (87 ng/L for total estrogens and 52 ng/L for natural androgens) were observed in June, which coincides with the early life stage development period of many aquatic species in the Midwest.

A review of studies on androgen and estrogen exposure in fish early life stages: effects on gene and hormonal control of sexual differentiation.

Teleost fish are unique among vertebrates in that phenotypic sex or onset of sex inversion can be easily manipulated by hormonal treatments. In recent years, researchers have begun reporting concentrations of synthetic and natural hormones in the environment. Although concentrations are very low (in the parts per trillion to low parts per billion), they are still of concern because of the high potency of synthetic hormones and the enhanced susceptibility of teleost fishes, especially early life stages, to hormonal exposures. In this review, we will focus on sex differentiation in teleost fishes and how these processes in fish early life stages may be impacted by environmental hormones which are known to contaminate aquatic environments. We will start by reviewing information on sources and concentrations of hormones in the environment and continue by summarizing the state of knowledge of sex differentiation in teleost gonochoristic fishes, including information on genes involved (e.g. cyp19, dmrt1, sox9 and foxl2). We will end our review with a summary of studies that have examined the effects of androgens and estrogens on fish sex differentiation after exposure of fish embryos and larvae and with ideas for future 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.

Continuous Hydrologic and Water Quality Monitoring of Vernal Ponds.

Vernal ponds, also referred to as vernal pools, provide critical ecosystem services and habitat for a variety of threatened and endangered species. However, they are vulnerable parts of the landscapes that are often poorly understood and understudied. Land use and management practices, as well as climate change are thought to be a contribution to the global amphibian decline. However, more research is needed to understand the extent of these impacts. Here, we present methodology for characterizing a vernal pond's morphology and detail a monitoring station that can be used to collect water quantity and quality data over the duration of a vernal pond's hydroperiod. We provide methodology for how to conduct field surveys to characterize the morphology and develop stage-storage curves for a vernal pond. Additionally, we provide methodology for monitoring the water level, temperature, pH, oxidation-reduction potential, dissolved oxygen, and electrical conductivity of water in a vernal pond, as well as monitoring rainfall data. This information can be used to better quantify the ecosystem services that vernal ponds provide and the impacts of anthropogenic activities on their ability to provide these services.

Comparison of export dynamics of nutrients and animal-borne estrogens from a tile-drained Midwestern agroecosystem.

Concentrated animal feeding operations (CAFOs) are known to be a source of nutrients and hormones found in surface water bodies around the world. While the fate and transport of nutrients have been studied for decades, much less research has been conducted on the fate and transport of hormones. To facilitate a comparison of nutrient and hormone export dynamics from farm fields, nitrate + nitrite (N), dissolved reactive phosphorus (DRP), 17α- and 17ß-estradiol (E2), estrone (E1), and estriol (E3) were monitored in a tile drain and receiving ditch for one year on a working farm in north central Indiana. Repeated animal waste applications led to high frequency detection of hormones (>50% in tile drain; >90% in the ditch) and nutrients (>70% for DRP; 100% for N). Hydrologic variability was found to be a dominant factor controlling export of N, DRP, and E1 to the drain and ditch. Of the estrogens, the temporal trend in E1 export was most similar to that of DRP. Differences in temporal export between P and the other estrogens likely were due to differences in the biogeochemical processes that affect their fate and transport within the agroecosystem. During short periods when the flowrate exceeded the 80(th) percentile for the year, over 70% of the total mass export of DRP and E1 occurred for the year in both the tile drain and ditch, demonstrating the importance of high-flow events. Therefore, best management practices must be effective during large flow events to substantially reduce transport to downstream locations.

Implications of hydrologic connectivity between hillslopes and riparian zones on streamflow composition.

Hydrological responses in mountainous headwater catchments are often highly non-linear with a distinct threshold-related behavior, which is associated to steep hillslopes, shallow soils and strong climatic variability. A holistic understanding of the dominant physical processes that control streamflow generation and non-linearity is required in order to assess potential negative effects of agricultural land use and water management in those areas. Therefore, streamflow generation in a small pre-Alpine headwater catchment (Upper Rietholzbach (URHB), ~1km(2)) was analyzed over a 2-year period by means of rainfall-response analysis and water quality data under explicit consideration of the joint behaviors of climate forcing and shallow groundwater dynamics. The runoff coefficients indicate that only a small fraction of the total catchment area (1-26%) generates streamflow during rainfall events. Hereby, the valley bottom areas (riparian zones) were the most important event-water source whereas only the lower parts of the hillslopes became hydrologically connected to the river network with higher antecedent moisture conditions. However, a distinct threshold-like behavior could not be observed, suggesting a more continuous shift from a riparian-zone to a more hillslope-dominated streamflow hydrograph. Regular manure application on the hillslopes in combinations with lateral hillslope groundwater flux and long groundwater residence times in the riparian zones resulted in a higher mineralization (e.g., total phosphorous) and significant denitrification in the valley bottom area. Despite the important role of the riparian zones for event-flow generation in the URHB, their nutrient buffer capacity is expected to be small due to the low permeability of the local subsurface material. The findings of this integrated analysis are summarized in a conceptual framework describing the hydrological functioning of hillslopes and riparian zones in the URHB.