Declining nitrogen (primarily nitrate) concentrations in the Upper Floridan aquifer within the Santa Fe River Basin, Florida (2014‐2024)

Groundwater from the surficial aquifer system and Upper Floridan aquifer in the Dougherty Plain and Marianna Lowlands in southwestern Georgia, northwestern Florida, and southeastern Alabama is affected by elevated nitrate concentrations as a result of the vulnerability of the aquifer, irrigation water-supply development, and intensive agricultural land use. The region relies primarily on groundwater from the Upper Floridan aquifer for drinking-water and irrigation supply. Elevated nitrate concentrations in drinking water are a concern because infants under 6 months of age who drink water containing nitrate concentrations above the U.S. Environmental Protection Agency maximum contaminant level of 10 milligrams per liter as nitrogen can become seriously ill with blue baby syndrome. In response to concerns about water quality in domestic wells and in springs in the lower Apalachicola–Chattahoochee–Flint River Basin, the Florida Department of Environmental Protection funded a study in cooperation with the U.S. Geological Survey to examine water quality in groundwater and springs that provide base flow to the Chipola River. A three-dimensional, steady-state, regional-scale groundwater-flow model and two local-scale models were used in conjunction with particle tracking to identify travel times and areas contributing recharge to six groundwater sites—three long-term monitor wells (CP-18A, CP-21A, and RF-41) and three springs (Jackson Blue Spring, Baltzell Springs Group, and Sandbag Spring) in the lower Apalachicola–Chattahoochee–Flint River Basin. Estimated nitrate input to groundwater at land surface, based on previous studies of nitrogen fertilizer sales and atmospheric nitrate deposition data, were used in the advective transport models for the period 2002 to 2050. Nitrate concentrations in groundwater samples collected from the six sites during 1993 to 2007 and groundwater age tracer data were used to calibrate the transport aspect of the simulations. Measured nitrate concentrations (as nitrogen) in wells and springs sampled during the study ranged from 0.37 to 12.73 milligrams per liter. Average apparent ages of groundwater calculated from measurements of chlorofluorocarbon, sulfur hexafluoride, and tritium from wells CP-18A, CP-21A,and RF-41 were about 23, 29, and 32 years, respectively. Average apparent ages of groundwater from Baltzell Springs Group, Sandbag Spring, and Jackson Blue Spring were about 16, 18, and 19 years, respectively. Simulated travel times of particles from the six selected sites ranged from less than 1 day to 511 years; both the minimum and maximum particle travel times were estimated for water from Jackson Blue Spring. Median simulated travel times of particles were about 30, 38, and 62 years for Jackson Blue Spring, Sandbag Spring, and Baltzell Springs Group, respectively. Study results indicated that travel times for approximately 50 percent of the particles from all spring sites were less than 50 years. The median simulated travel times of particles arriving at receptor wells CP-18A, CP-21A, and RF-41 were about 50, 35, and 36 years, respectively. All particle travel times were within the same order of magnitude as the tracer-derived average apparent ages for water, although slightly older than the measured ages. Travel time estimates were substantially greater than the measured age for groundwater reaching well CP-18A, as confirmed by the average apparent age of water determined from tracers. Local-scale particle-tracking models were used to predict nitrate concentrations in the three monitor wells and three springs from 2002 to 2050 for three nitrogen management scenarios: (1) fixed input of nitrate at the 2001 level, (2) reduction of nitrate inputs of 4 percent per year (from the previous year) from 2002 to 2050, and (3) elimination of nitrate input after 2001. Simulated nitrate concentrations in well CP-21A peaked at 7.82 milligrams per liter in 2030, and concentrations in background well RF-41 peaked at 1.10 milligrams per liter in 2020. The simulated particle travel times were longer than indicated by age dating analysis for groundwater in well CP-18A; to account for the poor calibration fit at this well, nitrate concentrations were shifted 21 years. With the shift, simulated nitrate concentrations in groundwater at CP-18A peaked at 13.76 milligrams per liter in 2026. For groundwater in Baltzell Springs Group, Jackson Blue Spring, and Sandbag Spring, simulated nitrate concentrations peaked at 3.77 milligrams per liter in 2006, 3.51 milligrams per liter in 2011, and 0.81 milligram per liter in 2018, respectively, under the three management scenarios. In management scenario 3 (elimination of nitrate input after 2001), simulated nitrate concentrations in Baltzell Springs Group decreased to less than background concentrations (0.10 milligram per liter) by 2033, and in Sandbag Spring concentrations decreased to less than background by 2041. Simulations using nitrate management scenarios 1 (fixed input of nitrate at 2001 levels) and 2 (reduction of 4.0 percent per year) indicate that nitrate concentrations in groundwater may remain above background concentrations through 2050 at all sites.

Repeat sampling and age tracers were used to examine trends in nitrate, arsenic, and uranium concentrations in groundwater beneath irrigated cropland. Much higher nitrate concentrations in shallow modern groundwater were observed at both the Columbia Plateau and High Plains sites (median values of 10.2 and 15.4 mg/L as N, respectively) than in groundwater that recharged prior to the onset of intensive irrigation (median values of <1 and <4 mg/L as N, respectively). Repeat sampling of these well networks indicates that high nitrate concentrations in modern, shallow groundwater have been sustained for decades, posing a future risk to older, deeper groundwater used for drinking water. In fact, nitrate concentrations in older modern water (30-60 years since recharge) at the High Plains site have increased in the past decade. Groundwater irrigated areas in the Columbia Plateau tend to have higher nitrate concentrations in groundwater than surface water irrigated areas,suggesting repeated dissolution of land applied fertilizer during recirculation may be an important factorcausing high nitrate concentrationsin groundwater. Mobilization of uranium and arsenic by land surface activities is suggested by the higher concentrations of these constituents in modern, shallow groundwater than in older, deeper groundwater at the Columbia Plateau site. Bicarbonate concentrations in modern groundwater are positively correlated with uranium (r = 0.72, p < 0.01), suggesting bicarbonate may mobilize uranium in this system. A positive correlation between arsenic and phosphorus concentrations in modern groundwater (r = 0.55, p < 0.01) suggests that phosphate from fertilizer outcompetes arsenate for sorption sites, mobilizing sorbed arsenic derived from past pesticide use or other sources.

Septic-tank wastewater disposed in 30-foot-deep seepage pits (dry wells) at 46,000 residences is estimated to equal about 18 percent of natural recharge to the sole-source aquifer beneath the upper Mojave River Basin, which is rapidly becoming urbanized, in the high desert northeast of Los Angeles. Nitrogen in the downward-infiltrating wastewaters represents a significant potential source of nitrate contamination to underlying ground water, but increases in nitrate concentration in ground water have not yet been observed. The low nitrate concentration in the ground water may be the result of lateral dispersion in the unsaturated zone, dilution below the water table, or denitrification of wastewater nitrate in the unsaturated zone. Measured vertical rates of movement of wastewater wetting fronts through the unsaturated zone at three newly occupied residences ranged from 0.07 to 1 foot per day. Those measurements, along with moisture-content profiles at older residences, indicate that some wastewater has reached the water table beneath communities that are older than 5 to 10 years. As wastewater percolates from seepage pits into the unsaturated zone, reduced nitrogen is converted rapidly to nitrate at shallow depths. Analyses of water extracts of soil cores and of soil moisture from suction lysimeters deep beneath seepage pits at several residences indicate that nitrate concentrations commonly decrease with depth. The largest nitrate decreases seem to coincide with increased content of fine-grained sediments or proximity to the water table. Nitrate-reducing bacteria were found in soil cores collected from two residences. Between lysimeters at 160 and 199 feet at one residence, the decrease in nitrate concentration coincided with a large increase in sulfate, decrease in alkalinity, and increase in 815N in nitrate. Those data are consistent with denitrification by oxidation of iron sulfide to produce ferric oxides; but if such a reaction occurs, it must be in domains that are small in comparison with the sampled volumes because the waters also contain substantial quantities of dissolved oxygen. The predominantly low nitrate concentrations in the area's ground water are consistent with the operation of a nitrogen-removal mechanism, possibly denitrification, as wastewater moves through an unsaturated zone that averages 150 feet in thickness. However, the reducing capacity of the sediments to maintain denitrification is not known. INTRODUCTION Septic-tank wastewater disposed in 30-foot-deep seepage pits (dry wells) at 46,000 residences in the communities of Victorville, Apple Valley, and Hesperia, is estimated to equal about 18 percent of natural recharge to the sole-source aquifer in the upper Mojave River Basin, which is rapidly becoming urbanized, in the high desert 80 mi northeast of Los Angeles (fig. 1). Introduction 1

Modelling the effect of physical and chemical characteristics of shallow aquifers on water and nitrate transport in small agricultural catchments

The nitrate concentrations in shallow groundwater of the Yogyakarta City and its surroundings has increased to about twenty times in the period 1985-2018. The objective of this study was to analyse the distribution of nitrate concentrations in water well around the Code River, Yogyakarta. Flownets mapping was performed to find out the distribution and direction of potential groundwater pollution. Nitrate concentration was analysed by taking 18 groundwater samples scattered in the upstream, midstream and downstream areas of the Code River. The results of this study indicate that nitrate concentrations in the water well of upstream and downstream areas could still be used as a source of drinking water and recreation-irrigation-livestock. Meanwhile, the nitrate concentration in water well of the midstream area of the Code River, Yogyakarta City, mostly (80% of the sample) did not meet all classes of water quality standards. Human activities in the densely populated settlements were the main factors that influence nitrate pollution. Furthermore, groundwater flow in the study area leads from north to south and towards the Code River. This condition indicates that the nitrate concentrations in the groundwater can be a source of a pollutant for the Code River.

This study evaluates processes that affect nitrate concentrations in groundwater beneath riparian zones in an agricultural watershed. Nitrate pathways in the upper 2 m of groundwater were investigated beneath wooded and grass‐shrub riparian zones next to cultivated fields. Because trees can be important components of the overall nitrate pathway in wooded riparian zones, water sources used by riparian trees and possible effects of trees on nitrate concentrations in groundwater were also investigated. Average nitrate concentrations in shallow groundwater beneath the cultivated fields were 5.5 mg/L upgradient of the wooded riparian zone and 3.5 mg/L upgradient of the grass‐shrub zone. Shallow groundwater beneath the fields passed through the riparian zones and discharged into streams that had average nitrate concentrations of 8.5 mg/L (as N). Lateral variations of δD values in groundwater showed that mixing among different water sources occurred beneath the riparian zones. In the wooded riparian zone, nitrate concentrations in shallow groundwater were diluted by upwelling, nitrate‐poor, deep groundwater. Upwelling deep groundwater contained ammonium with a δ15N of 5‰ that upon nitrification and mixing with nitrate in shallow groundwater caused nitrate δ15N values in shallow groundwater to decrease by as much as 19.5‰. Stream water penetrated laterally beneath the wooded riparian zone as far as 19 m from the stream's edge and beneath the grass‐shrub zone as far as 27 m from the stream's edge. Nitrate concentrations in shallow groundwater immediately upgradient of where it mixed with stream water averaged 0.4 mg/L in the wooded riparian zone and 0.8 mg/L near the grass‐shrub riparian zone. Nitrate concentrations increased toward the streams because of mixing with nitrate‐rich stream water. Because nitrate concentrations were larger in stream water than shallow groundwater, concentrated nitrate in the streams cannot have come from shallow groundwater at these sites. Water sources of riparian trees were identified by comparing δD values of sap water, soil water, groundwater, and stream water. Soil water was the main water source for trees in the outer 4 to 6 m of one part of the wooded riparian zone and outer 10 m of another part. Groundwater was a significant water source for trees closer to the streams where the water table was less than about 2.1 to 2.7 m below the surface. No evidence was found in the nitrate concentration profiles that trees close to the streams that took up groundwater through their roots also took up nitrate from groundwater. The lack of such evidence is attributed to the nitrate concentration profiles being insufficiently sensitive indicators of nitrate removal by trees.

This paper is the result of a study which was carried out in order to verify if the traditional methods to evaluate the intrinsic vulnerability or vulnerability related parameters, are able to clarify the problem of nitrate pollution in groundwater. In particular, the aim was to evaluate limitations and problems connected to aquifer vulnerability methods applied to nitrate contamination prevision in groundwater. The investigation was carried out by comparing NO3− concentrations, measured in March and November 2004 in the shallow aquifer, and the vulnerability classes, obtained by using GOD and TOT methods. Moreover, it deals with a comparison between NO3− concentrations and single parameters (depth to water table, land use and nitrogen input). The study area is the plain sector of Piemonte (Northern Italy), where an unconfined aquifer nitrate contamination exists. In this area the anthropogenic presence is remarkable and the input of N-fertilizers and zootechnical effluents to the soil cause a growing amount of nitrates in groundwater. This approach, used in a large area (about 10,000 km2) and in several monitoring wells (about 500), allowed to compare the efficiency of different vulnerability methods and to verify the importance of every parameter on the nitrate concentrations in the aquifer. Furthermore it allowed to obtain interesting correlations in different hydrogeological situations. Correlations between depth to water table, land use and nitrogen input to the soil with nitrate concentrations in groundwater show unclear situations: in fact these comparisons describe the phenomenon trend and highlight the maximum nitrate concentrations for each circumstance but often show wide ranges of possible nitrate concentrations. The same situation could be observed by comparing vulnerability indexes and nitrate concentrations in groundwater. These results suggest that neither single parameters nor vulnerability methods (GOD and TOT) are able to describe individually the complex phenomena affecting nitrate concentrations in soil, subsoil and groundwater. In particular, the traditional methods for vulnerability analysis do not analyze physical processes in aquifers, such as denitrification and nitrate dilution. According to a recent study in the shallow unconfined aquifer of the Piemonte plain, dilution can be considered as the main cause for nitrate attenuation in groundwater.

Historical data on nutrient (nitrogen and phosphorus species) concentrations in ground-and surface-water samples were compiled from 20 study units of the National Water-Quality Assessment (NAWQA) Program and 5 supplemental study areas. The resultant national retrospective data sets contained analyses of about 12,000 Found-water and more than 22,000 surface-water samples. These data were interpreted on regional and national scales by relating the distributions of nutrient concentrations to ancillary data, such as land use, soil characteristics, and hydrogeology, provided by local study-unit personnel. The information provided in this report on environmental factors that affect nutrient concentrations in ground and surface water can be used to identify areas of the Nation where the vulnerability to nutrient contamination is greatest. Nitrate was the nutrient of greatest concern in the historical ground-water data. It is the only nutrient that is regulated by a national drinking-water standard. Nitrate concentrations were significantly different in ground water affected by various land uses. Concentrations in about 16 percent of the samples collected in agricultural areas exceeded the drinking-water standard. However, the standard was exceeded in only about 1 percent of samples collected from public-supply wells. A variety of ancillary factors had significant relations to nitrate concentrations in ground water beneath agricultural areas. Concentrations generally were highest within 100 feet of the land surface. They were also higher in areas where soil and geologic characteristics promoted rapid movement of water to the aquifer. Elevated concentrations commonly occurred in areas underlain by permeable materials, such as carbonate bedrock or unconsolidated sand and gravel, and where soils are generally well drained. In areas where water movement is impeded, denitrification might lead to low concentrations of nitrate in the ground water. Low concentrations were also related to interspersion of pasture and woodland with cropland in agricultural areas. Elevated nitrate concentrations in areas of more homogeneous cropland probably were a result of intensive nitrogen fertilizer application on large tracts of land. Certain regions of the United States seemed more vulnerable to nitrate contamination of ground water in agricultural areas. Regions of greater vulnerability included parts of the Northeast, Midwest, and West Coast. The well-drained soils, typical in these regions, have little capacity to hold water and nutrients; therefore, these soils receive some of the largest applications of fertilizer and irrigation in the Nation. The agricultural land is intensively cultivated for row crops, with little interspersion of pasture and woodland. Nutrient concentrations in surface water also were generally related to land use. Nitrate concentrations were highest in samples from sites downstream from agricultural or urban areas. However, concentrations were not as high as in ground water and rarely exceeded the drinking-water standard. Elevated concentrations of nitrate in surface water of the Northeastern United States might be related to large amounts of atmospheric deposition (acid rain). High concentrations in parts of the Midwest might be related to tile drainage of agricultural fields. Ammonia and phosphorus concentrations were highest downstream from urban areas. These concentrations generally were high enough to warrant concerns about toxicity to fish and accelerated eutrophication. Recent improvements in wastewater treatment have decreased ammonia concentrations downstream from some urban areas, but the result has been an increase in nitrate concentrations. Information on environmental factors that affect water quality is useful to identify drainage basins throughout the Nation with the greatest vulnerability for nutrient contamination and to delineate areas where ground-water or surface-water contamination is most likely to oc

The City ofTallahassee began applying effluent from a secondary sewage-treatment plant to a spray field site southeast of the city in 1980. Fertilizers containing inorganic nitrogen were also applied in conjunction with the operation of a commercial farm at this site. Analyses of ground water from both the surficial aquifer and the Upper Floridan aquifer have shown nitrate enrichment in some wells that exceeds the prescribed drinking water maximum contaminant level of 10 milligrams per liter (nitrate as nitrogen). Nitrate concentrations above the maximum contaminant level were not detected in samples from monitoring wells located outside the sprayfield boundary. The distribution of nitrate concentrations in ground water has probably been affected by the ground-water flow systems of the surficial aquifer and the Upper Floridan aquifer at the site. The flow system is controlled by the combined recharge from precipitation and effluent application in the surficial aquifer and by the high volume of ground water flowing roughly north to south in the Upper Floridan aquifer. Samples of water from the unsaturated zone, collected in lysimeters, showed that conversion of organic nitrogen and ammonia to nitrate was complete before the nitrogen-enriched water reached the water table. Water samples from wells completed in the surficial aquifer or at depths less than 100 feet in the Upper Floridan aquifer and located inside sprayed areas had mean nitrate concentrations of 7.9 and 4.4 milligrams per liter, respectively. This was higher than concentrations in samples from wells of similar depth located outside sprayed areas at the southeast sprayfield (0.5 and 0.6 milligrams per liter, respectively). Wells located inside the sprayed areas were the only wells in which the maximum contaminant level for nitrate in drinking water was exceeded. Water samples from wells greater than 100 feet deep in the Upper Floridan aquifer had a lower mean nitrate concentration (1.0 milligrams per liter) than did the shallower wells. Samples from this depth, located in the southern, downgradient part of the sprayfield, had a higher mean nitrate concentration than samples from wells in the northern, upgradient part of the sprayfield (3.8 compared to 0.78 milligrams per liter). Analyses of the nitrogen isotope ratios, 815Af, in nitrate in ground water were used to determine if the major source of nitrogen was treated sewage, inorganic fertilizers, or both. The 8 15Af values in nitrate in nitrate-enriched ground water at the southeast site were compared to 8 15Af values in ground water at another sprayfield southwest of the city where effluent was the sole source of nitrogen. Statistical analyses of the isotope ratios at the two sites showed a significant difference in the 815Af values, indicating that the contribution of nitrogen from fertilizers was significant at the southeast sprayfield.

Nitrate leaching in intensive grassland- and silage maize-based dairy farming systems on sandy soil is a main environmental concern. Here, statistical relationships are presented between management practices and environmental conditions and nitrate concentration in shallow groundwater (0.8 m depth) at farm, field, and point scales in The Netherlands, based on data collected in a participatory approach over a 7-yr period at one experimental and eight pilot commercial dairy farms on sandy soil. Farm milk production ranged from 10 to 24 Mg ha(-1). Soil and hydrological characteristics were derived from surveys and weather conditions from meteorological stations. Statistical analyses were performed with multiple regression models. Mean nitrate concentration at farm scale decreased from 79 mg L(-1) in 1999 to 63 in 2006, with average nitrate concentration in groundwater decreasing under grassland but increasing under maize land over the monitoring period. The effects of management practices on nitrate concentration varied with spatial scale. At farm scale, nitrogen surplus, grazing intensity, and the relative areas of grassland and maize land significantly contributed to explaining the variance in nitrate concentration in groundwater. Mean nitrate concentration was negatively correlated to the concentration of dissolved organic carbon in the shallow groundwater. At field scale, management practices and soil, hydrological, and climatic conditions significantly contributed to explaining the variance in nitrate concentration in groundwater under grassland and maize land. We conclude that, on these intensive dairy farms, additional measures are needed to comply with the European Union water quality standard in groundwater of 50 mg nitrate L(-1). The most promising measures are omitting fertilization of catch crops and reducing fertilization levels of first-year maize in the rotation.

The effects of land use on nitrate concentrations in ground water were examined by dividing the study area into five subareas on the basis of percentage of land use-agriculture/forest [approximately (~) 50 percent agriculture and ~40 percent forest, hereafter referred to as “ag/forest”], agriculture [greater than (>) 75 percent of total land use], forest (>75 percent of total land use), urban (>65 percent of total land use), and mixed (fig. 1). Mixed areas were defined as small isolated areas with two or more land uses and were not included in analyses. Nitrogen inputs, which were calculated from fertilizer and manure applications, nitrogen fixation, and atmospheric deposition, were highest in the agriculture areas followed by ag/forest, urban, and forest areas. If all other factors remained the same, then nitrate concentrations in ground water should correspond to rates of input. However, the highest median concentration of nitrate-N (5.45 mg/L), was found in the ag/forest areas. This is an order of magnitude higher than the median concentrations in agriculture and forest areas (0.32 and 0.23 mg/L, respectively) and two orders of magnitude higher than that in Fact Sheet FS-070-94

Nitrate concentration in ground water is a major problem in specific agricultural areas. Using regression and neural networks, this study models nitrate concentration in ground water as a function of iron concentration in ground water, season and distance of the well from a poultry house. Results from both techniques are comparable and show that the distance of the well from a poultry house has a significant effect on nitrate concentration in groundwater.

The Delmarva Peninsula is an extensively farmed region in which nitrate from commercial fertilizers and poultry has entered the ground water and streams. The peninsula contains forested wetlands in a variety of settings, and their size and location are a result of the surrounding hydrologic and soil conditions. Three regions, here referred to as hydrogeomorphic regions, were selected for study. Each region has characteristic geologic and geomorphic features, soils, drainage patterns, and distribution of farmland, forests, and forested wetlands. In all three regions, forested wetlands generally occupy poorly drained areas whereas farmlands generally occupy well-drained areas. The three hydrogeomorphic regions studied are the well-drained uplands, the poorly drained uplands, and the surficial-confined region. The well-drained uplands have the largest amount of farmland and the smallest amount of forested wetlands of the three regions; here the forested wetlands are generally restricted to narrow riparian zones. The poorly drained uplands contain forested wetlands in headwater depressions and riparian zones that are interspersed among well-drained farmlands. The surficial-confined region has the smallest amount of farmland and largest amount of forested wetlands of the three regions studied. Wetlands in this region occupy the same topographic settings as in the poorly drained uplands. Much of the farmland in the surficial-confined region was previously wetland. Nitrate concentrations in ground water and surface water on the peninsula range widely, and their distribution reflects (1) the interspersion of forests among farmland, (2) hydrogeologic conditions, (3) types of soils, and (4) the ground-water hydrology of forested wetlands. The well-drained uplands had higher median nitrate concentrations in ground water than the poorly drained uplands or the surficial-confined region. The highest nitrate concentrations were in oxic parts of the aquifer, which are beneath well-drained soils that are farmed, and the lowest were in anoxic parts of the aquifer, which are beneath poorly drained soils overlain by forested wetlands. The effect of forested wetlands on water quality depends on the hydrogeologic conditions, extent of farming, and type of soils. The three regions contain differing combinations of these factors and thus are useful for isolating the effects of forested wetlands on water quality.

In order to evaluate the factors influencing nitrate concentration in groundwater under agricultural fields or rural settlements, properties of groundwater collected from 465 irrigation wells in Aichi prefecture, Japan was analyzed. Nitrate concentration levels depended on the land use, well depth, and oxidation-reduction potential (Eh) of groundwater.Nitrate concentration in shallow groundwater with greater than 250mV of Eh were related to the land use of the surrounding area. Groundwater under upland field showed higher nitrate concentration than those collected from the sites of other land use types. Groundwater under rural settlements also showed a noticeably high nitrate concentration. Groundwater under paddy fields and forests were low in nitrate concentration. Nitrous oxide concentration was also high in oxic groundwater and significantly correlated with nitrate concentration, r=0.781.The nitrate concentration levels of groundwater in which Eh value was≤250mV, did not noticeably increase regardless of land use type. Judging from the Eh level and the existence of denitrifying bacteria in most shallow groundwater, denitrification is considered to be an important factor for maintaining low nitrate concentration in anoxic groundwater.

Comparative study of nitrate leaching models on a regional scale