Abstract
Background
Growing anthropogenic water demands, combined with climate change-driven decreases in precipitation, are decreasing streamflow in many regions throughout the world, creating river systems which frequently dry completely down to isolated, standing water pools (Dodds et al., 2013; Milly et al., 2005). Land-use change, both for agricultural and urban development, can significantly increase anthropogenic pollutant loading into rivers and streams. Isolated pools of standing water are often more susceptible to anthropogenic contaminant loading than perennial flowing water, with these conditions more often allowing for the growth of toxic algae and pathogenic bacteria (Davis et al., 2009; Pandey et al., 2014). Nitrogen and phosphorus loading into standing waters by urban effluent and agricultural sources can increase the severity of eutrophication and cyanobacterial blooms, which affect the water directly via turbid conditions, foul odor, increased fish kills, and anoxia (Wang et al., 2001). Nutrient loading may be a potential risk to human health by promoting conditions favorable for the growth of waterborne diseases, particularly those contracted from bacterial sources (Dixit et al., 2017; Matthews & Bernard, 2015).
Although much effort has been focused on understanding how land use change impacts groundwater and perennial systems, relatively little monitoring has been conducted to understand how land use change impacts water quality in isolated pools in intermittent and ephemeral streams and how impacts may vary temporally. A case in point is the Edwards Aquifer region in south-central Texas. Some research has been conducted on stormwater runoff in ephemeral stream segments within the region, revealing steadily increasing concentrations of nutrients, pesticides, and trace metals (Opsahl, 2012). However, studies of isolated pools are rare and most previous research has been conducted on the water quality of perennial surface and groundwater systems. A study by Musgrove et al. (2016) revealed an increase in the concentration of nitrates into segments of the Edwards Aquifer most likely attributed to contamination from urban wastewater. Smith and Hunt (2018) further supported these findings during their analysis of the Barton Springs Aquifer, where increased pollutant loading called for the installation of an automated control system, in the form of a concrete vault with valves which closed during storm events and opened after to reduce contaminated storm water loading, as a best management practice to protect the resource. These studies show increasing impacts from urban development on water resources in the region, and suggest a potential impact on ephemeral stream pools, which warrants further study.
The objective of this study was to investigate whether and how urban land development impacts temporal patterns of water quality in standing water bodies within the Edwards Aquifer region. Two study approaches were taken to help accomplish the objective. First, levels of nitrates, total dissolved phosphorus,
Methods
Study area
The Edwards Aquifer region has a moderately arid climate (Gustafson, 2015). Annual rainfall ranges from 76 to 89 cm in the Eastern portion and 51 to 64 cm in the Western portion, with the highest rates of rainfall occurring in the spring and fall. Periods of drought are common for the region, as temperatures may exceed 38°C, causing rapid evaporation of water from the region’s thin soils (Fowler, 2005). The main geological subtype within the region is karstic limestone, which is a highly permeable system of faults and fractures that allows efficient recharge of the aquifer (George et al., 2011). Soils and surface water in the region are neutral to alkaline pH due to the limestone geology, but water in the aquifer is fresh, with total dissolved solids less than 500 mg/L. The aquifer itself serves as invaluable habitat for various endemic species, helps reduce inputs of freshwater into downstream estuaries, and provides drinking water for millions of people, including San Antonio (Bowles & Arsuffi, 1993; Fowler, 2005; George et al., 2011). Surface water sources over the aquifer are commonly owned and protected by the state, with landowners and other users of water needing legal permission to extract water from rivers (Gustafson, 2015). Temporal patterns of flow in the region result from the karst topography and precipitation patterns, which are characterized by short periods of intense precipitation within longer periods of drought. During periods of drought, surface flow ceases in streams and rivers not fed by groundwater springs, leaving only isolated pools in otherwise dry channels. Streamflow returns during intense precipitation events, refilling pools, and may persist for several days to weeks following precipitation.
Field collection of water quality samples was conducted at three locations within the Edwards Aquifer region: Ingram, Albert and Bessie Kronkosky State Natural Area (ABK Ranch), and Fair Oaks Ranch (Figure 1). All sites were similar regarding vegetation composition, temporal weather patterns, and presence of an isolated standing water pool. Soils were similar at sites as well, with Fair Oaks Ranch and ABK primarily gravelly clay loams in the Brackett-Real association, and soils at Ingram primarily clays in the Harper-Eckrant complex. However, sites differed in terms of surrounding land use; ABK Ranch was in a protected natural area and had no urban cover in the contributing watershed, Ingram was in a rural area, but also had no urban cover in the contributing watershed, and Fair Oaks Ranch was in a suburban housing development with 12% developed cover and 3.3% impervious cover in the contributing watershed. In addition, the specific type of standing water body varied between sites. Fair Oaks Ranch and ABK Ranch were isolated pools in ephemeral streams, which filled during rainfall and streamflow and dried slowly in between rainfall and flow events. Ingram was a pond fed by a spring via feeder pipe. This site served as a control for temporal variability because the water level remained stable throughout the duration of research, and thus fluctuations in water quality at this site could not be attributed to precipitation-driven runoff from the surrounding watershed.

Map showing study sites, precipitation stations, and supplementary sites in relation to San Antonio. The Edwards Aquifer drainage, recharge, and artesian zones are shown in the gray outline.
Water quality sampling
Surface grab samples of water at Ingram, ABK Ranch, and Fair Oaks Ranch were collected weekly over the course of a 5-month period ranging from June to October of 2018. No water samples were collected in September at ABK Ranch, because the area was closed for access for the entire month due to substantial flooding and trail damage. Water for analysis of nitrate and total dissolved phosphorus was collected in 1-L acid-cleaned, polyethylene bottles and placed on ice until return to the laboratory located at the University of Texas at San Antonio (UTSA) campus. Upon return to the laboratory, samples were stored in a refrigerator at 4°C until processing, typically within 24 hours of collection. Laboratory blanks were analyzed in conjunction with field samples to identify any areas of potential contamination; nitrate, phosphorus,
Nitrate concentrations in water samples were analyzed using a brucine sulfate colorimetric reaction (EPA Method 352.1: Nitrogen, Nitrate (Colorimetric, Brucine) by Spectrophotometer). Samples and standards were mixed with a brucine sulfate solution and the final absorbance was read on a BioMate™ 3S spectrophotometer at 410 nm. Nitrate concentrations of samples were determined using an absorbance-concentration standard curve.
Amounts of total dissolved phosphorus in water samples were determined using an ammonium persulfate digestion procedure (EPA Method 365.3: Phosphorus, All Forms (Colorimetric, Ascorbic Acid, Two Reagent)). Following digestion, samples were mixed with an ascorbic acid solution and the final absorbance was read on a BioMate™ 3S spectrophotometer at 650 nm. Concentrations of total dissolved phosphorus of samples were determined using an absorbance-concentration standard curve.
Coliform count plates (3M™ Petrifilm™) were used to measure the presence of
To determine the impact of precipitation on water quality, mean daily precipitation was determined at each site for the week prior to, and including the day of, each sampling event. Rainfall data for all three sites was obtained from Weather Underground (wunderground.com) at the stations nearest to the sampling sites (Kerrville Municipal-Schreiner Station for Ingram, Pipe Creek HQ/ABK Unit Station for ABK Ranch, and Cibolo Trails Station for Fair Oaks Ranch (Figure 1).
Supplemental water quality data
Data on nitrate, phosphorus,
Analysis strategy
Weekly values of nitrate, total dissolved phosphorus, coliform counts, and
Median values of nitrate, total phosphorus,
Results
Highest average monthly rainfall totals occurred in September and October at Ingram, whereas July had the highest average monthly rainfall at ABK Ranch and Fair Oaks Ranch (Figure 2). Temporal patterns at both ABK Ranch and Fair Oaks Ranch were similar for the duration of research, most likely due to the closer proximity of these sensors as compared to the sensor for the Ingram site. The highest daily precipitation total was 15.75 cm, which was recorded at Fair Oaks Ranch during the month of July. Following this rainfall event, flow rate increased substantially, and the site experienced a significant flood (Love & Laub, 2021). The stream at ABK Ranch did not flow during the summer months, but underwent significant flooding during the month of September, causing a delay in sample collection. As Ingram was an isolated pond, it underwent no visible water level changes throughout the duration of research, even during and following significant precipitation events.

Average weekly rainfall per month for the study sites from June to October 2018. Stations at ABK Ranch and Fair Oaks Ranch collected identical measurements over the duration of research due to their close proximity. Error bars indicate standard error in monthly precipitation rates at each study site.
Nitrates
Fair Oaks Ranch was consistently higher in nitrate concentrations than the other two study sites, with the highest average concentration of nitrates, 0.166 mg/L, occurring at this site during the month of July (Figure 3). Concentrations at ABK Ranch and Ingram remained low (<0.05 mg/L) throughout the duration of research, with ABK Ranch recording only slightly higher concentrations during dry conditions (

Monthly averages of pollutant concentrations at Ingram, ABK Ranch, and Fair Oaks Ranch from June to October 2018. ABK Ranch did not have a value in the month of September due to site closure. Error bars indicate variation in pollutant concentration averages during each month; errors bars are not present for pollutants that only had one measurement collected within the month.

Correlation analysis results at Fair Oaks Ranch showing (a) relationship between weekly precipitation (cm) and
Total dissolved phosphorus
Concentrations of total dissolved phosphorus were below detection limits (<0.01 mg/L) for most of this study at all three sites (Figure 3). The highest individual weekly value was 0.036 mg/L, recorded at Ingram in July. Monthly averages at both ABK Ranch and Fair Oaks Ranch did not exceed 0.002 mg/L. There was no significant difference in means between dry (
Escherichia coli
Other coliform bacteria
Other coliform bacterial CFU counts were considerably higher than those of
Supplementary sites
Water quality parameters at sampled ephemeral sites were within the range of values found at sites across the Edwards Aquifer region for nitrate (0.07–7.8 mg/L),
Information for Supplementary Sites Analyzed, Including Median Concentrations of Water Quality Constituents.
Units are colony forming units (CFUs) per 100 mL.
Direction of Relationships Between Mean Weekly Antecedent Discharge and Water Quality Measures for Supplementary Sites.
Discussion
The main objective of this study was to compare water quality conditions of two ephemeral stream systems that differed in urban land cover within the Edwards Aquifer region. ABK Ranch, a site with no urban development, and Fair Oaks Ranch, a site surrounded by a housing development and golf course, were subject to significant changes in water level over the course of research. Both varied from flowing streams to isolated pools, whereas Ingram, a site with light vegetation maintenance efforts but no immediate urban development, remained a consistently level pool.
While there were no consistent differences in most of the parameters between dry and wet conditions, some parameters were significantly different in dry versus wet conditions for at least one site. Analyses identified a strong positive correlation between weekly antecedent precipitation and
At ABK Ranch, elevated levels of
A significant peak in nitrates was observed at Fair Oaks Ranch following a sampling on July 10th; the week leading up to this sampling had high precipitation (15.75 cm), with the highest amount of precipitation occurring up to 2 days prior to sampling. Several lines of evidence suggest that urban development around the site contributed to the nitrate peak. Runoff from fertilized golf courses, lawns, and public parks, all of which are near the Fair Oaks Ranch sampling site, have been attributed to increased nitrate loading into other standing water bodies (Enwright & Hudak, 2009; Hudak, 2000; Winter & Dillon, 2005). Previous work has also shown that suspended solids, fine particles, heavy metals, and various nutrients and chemicals are often highest in concentration within the first 30 minutes of the runoff event, or the “first flush” (Baek et al., 2015; Ma et al., 2011; Park et al., 2010), whereas
Interestingly, phosphorus levels did not rise in equal concentrations as nitrates at Fair Oaks Ranch, whereas phosphorus levels were predicted to increase due to the two pollutants being commonly found in conjunction during nutrient loading into water sources (Pandey et al., 2014). One possibility for the lack of phosphorus response is that the precipitation event diluted phosphorus concentrations, such that they stayed at low levels during the runoff event. In support of this possibility, most supplementary sites that had a significant total phosphorus response to antecedent discharge showed a negative relationship. Since phosphorus levels were already near or below detection limits, further decreases in concentrations would not have been observed. Low phosphorus concentrations were found to be common in the study region, with more than half of supplementary sites having total phosphorous concentrations frequently below detection limits, including sites on Cibolo Creek upstream of the Fair Oaks Ranch sampling site.
Unlike the sites at both ABK Ranch and Fair Oaks Ranch, the isolated pool at Ingram remained at a consistent level throughout the duration of research and was only influenced by light vegetation management in its surrounding area. Thus, Ingram was used as a control site to observe whether water quality parameters fluctuated in the absence of a strong stormwater runoff influence. Ingram did record the highest individual weekly value of phosphorus, 0.036 mg/L, in July. Analysis performed on this parameter did not indicate a correlation with monthly precipitation levels, suggesting that a factor other than rainfall may have been a contributor to the increase in phosphorus concentrations. While not formally measured, visually noticeable levels of algae and, on occasion, significant “fishy” odors were emanating from the Ingram water source, suggesting the pool may have been subject to the process of eutrophication at minor levels (Matthews & Bernard, 2015). Additionally, this process may have been exacerbated by minor degradation of the surrounding pool bank following the vegetation management processes that occurred at this site during research. Importantly, other parameters besides phosphorus remained consistently low throughout the study at Ingram, and nitrate and
On average, the residential community of Fair Oaks Ranch saw a higher average monthly nitrate and
Mammalian presence may also be a contributor to anthropogenic pollutant loading into standing water sources, with prior studies indicating that deer, feral hogs, and raccoons may play a direct role in the degradation of standing water sources through increased soil disturbance, water turbidity, and loading of fecal indicator bacteria (McDowell, 2007; Parker et al., 2013; Ram et al., 2007). These effects are often enhanced during periods of drought, where animals are more likely to congregate near the water sources and negatively influence already strained riparian resources through more direct defecation and concentrated use. However, the relatively low background levels of nitrate and
Conclusions
Based on results of this study, anthropogenic pollutant loading into the standing water bodies of the Edwards Aquifer region, particularly nitrates and
