Geology topics

Matthew P. Miller

Publications and source records attributed to Matthew P. Miller.

At least 37 records · Page 2Linked to original sources

USGS2020

Relating hydroclimatic change to streamflow, baseflow, and hydrologic partitioning in the Upper Rio Grande Basin, 1980 to 2015

Understanding how changing climatic conditions affect streamflow volume and timing is critical for effective water management. In the Rio Grande Basin of the southwest U.S., decreasing snowpack, increasing minimum temperatures, and decreasing streamflow have been observed in recent decades, but the effects of hydroclimatic changes on baseflow, or groundwater discharge to streams, have not been investigated. In this study, we determine how trends in precipitation, snowpack accumulation, and snowmelt rate relate to total streamflow, baseflow, and the hydrologic partitioning of baseflow and runoff at 12 sites in the Upper Rio Grande Basin (URGB) during 1980 to 2015. Total streamflow was partitioned into baseflow and runoff components at a daily time step using conductivity-mass-balance hydrograph separation. Trends in annual total streamflow, baseflow, runoff, baseflow index, precipitation, snowmelt rate, and peak snow water equivalent (SWE) were evaluated from 1980 to 2015 using the non-parametric Mann-Kendall trend test. Results indicate that baseflow forms a large component of total streamflow, contributing an average of 49% of total discharge upstream of Albuquerque, NM. During 1980 to 2015, decreasing trends in total streamflow occurred at 9 of 12 sites and were almost always associated with decreases in baseflow, suggesting that baseflow volumes can respond to changing climatic and anthropogenic conditions within decades. Decreasing snowmelt rates were more frequently associated with decreases in baseflow and total streamflow than were decreases in precipitation and peak SWE, highlighting the importance of snowmelt rate as a process controlling streamflow generation. If snow accumulation and snowmelt rates continue to decrease in the future, results indicate that total streamflow and baseflow volumes will decline, and that baseflow will become a larger fraction of total streamflow in the URGB.

Colorado, New Mexico↗

USGS2019

Response of nitrogen loading to the Chesapeake Bay to source reduction and land use change scenarios: A SPARROW‐informed analysis

In response to concerns regarding the health of streams and receiving waters, the United States Environmental Protection Agency established a total maximum daily load for nitrogen in the Chesapeake Bay watershed for which practices must be in place by 2025 resulting in an expected 25% reduction in load from 2009 levels. The response of total nitrogen (TN) loads delivered to the Bay to nine source reduction and land use change scenarios was estimated using a Spatially Referenced Regression on Watershed Attributes model. The largest predicted reduction in TN load delivered to the Bay was associated with a scenario in which the mass of TN as fertilizer applied to agricultural lands was decreased. A 25% decrease in the mass of TN applied as fertilizer resulted in a predicted reduction in TN loading to the Bay of 11.3%, which was 2.5–5 times greater than the reductions predicted by other scenarios. Eliminating fertilizer application to all agricultural land in the watershed resulted in a predicted reduction in TN load to the Bay of 45%. It was estimated that an approximate 25% reduction in TN loading to the Bay could be achieved by eliminating fertilizer applied to the 7% of subwatersheds contributing the greatest fertilizer‐sourced TN loads to the Bay. These results indicate that management strategies aimed at decreasing loading from a small number of subwatersheds may be effective for reducing TN loads to the Bay, and similar analyses are possible in other watersheds.

Delaware, Maryland, New York, Pennsylvania, Virgin↗

USGS2019

Salinity yield modeling of the Upper Colorado River Basin using 30-meter resolution soil maps and random forests

Salinity loading in the Upper Colorado River Basin (UCRB) costs local economies upwards of $300 million US dollars annually. Salinity source models have generally included coarse spatial data to represent non‐agriculture sources. We developed new predictive soil property and cover maps at 30 m resolution to improve source representation in salinity modeling. Salinity loading erosion risk indices were also created based on soil properties, remotely sensed bare ground exposure, and topographic factors to examine potential surface soil erosion drivers. These new maps and data from previous SPARROW models were related to recently updated records of salinity at 309 stream gauges in the UCRB using random forest regressions. Resulting salinity yield predictions indicate more diffuse salinity sources, with slightly higher yields in more arid portions of the UCRB, and less overall load coming from irrigated agricultural sources. Model simulations still indicate irrigation to be the major human source of salinity (661,000 Mg, or 12%), but also suggest that 75,000 Mg (1.4%) of annual salinity in the UCRB is coming from areas with excessive exposed bare ground in high elevation mountain areas. Model inputs allow for field scale screening of locations that could be targeted for salinity control projects. Results confirm recent studies indicating limited surface erosional influence on salinity loading in UCRB surface waters, but impacts of monsoonal runoff events are still not fully understood, particularly in drylands. The study highlights the utility of new predictive soil maps and machine learning for environmental modeling.

Arizona, Colorado, New Mexico, Utah, Wyoming↗

USGS2019

Monitoring the Riverine Pulse: Applying high-frequency nitrate data to advance integrative understanding of biogeochemical and hydrological processes

Widespread deployment of sensors that measure river nitrate (NO3-) concentrations has led to many recent publications in water resources journals including review papers focused on data quality assurance, improved load calculations, and better nutrient management. The principal objective of this paper is to review and synthesize studies of high-frequency NO3- data that have aimed to improve understanding of the hydrologic and biogeochemical processes underlying episodic, diel, and long-term stream NO3- dynamics. Investigations have provided unprecedented detail on hysteresis and flushing patterns during high flow, seasonal variation during baseflow, and responses to multi-year climate variation. Analyses of high-frequency data have led to notable advances in understanding how climate variation affects spatial and temporal NO3- patterns, especially dry-wet cycles and antecedent moisture. Further advances have been limited by few investigations that include high-frequency measurements outside the channel and the short duration of many records. High-frequency data for multiple constituents have provided new insight to the relative roles of hydrology and biogeochemistry as highlighted by studies of the roles of autotrophic uptake, denitrification, riparian evapotranspiration, and temperature-driven changes in viscosity as drivers of diel patterns. Comparisons of short-duration high-frequency data with long-duration low frequency data have described similarities and differences in concentration – discharge patterns and highlighted the role of legacy stores. Investigators have applied innovative analysis approaches not previously possible with low-frequency or temporally-irregular data. Future availability of long-duration high-frequency data will provide new insight to processes, resulting in improved conceptual models and a deeper understanding of the role of climate variation.

WIREs Water↗

USGS2018

Stream‐centric methods for determining groundwater contributions in karst mountain watersheds

Climate change influences on mountain hydrology are uncertain, but likely to be mediated through changes in subsurface hydrologic residence times and flowpaths. The heterogeneity of karst aquifers add complexity in assessing the resiliency of these water sources to perturbation, suggesting a clear need to quantify contributions from and losses to these aquifers. Here we develop a stream centric method that combines mass and flow balances to quantify net and gross gains and losses at different spatial scales. We then extend these methods to differentiate between karst conduit and matrix contributions from the aquifer. In the Logan River watershed in Northern Utah we found significant amounts of the river water repeatedly gained and then lost through a 35 km study reach. Further, the direction and amount of water exchanged varied over space, time, and discharge. Streamflow was dominated by discharge of karst conduit groundwater after runoff with increasing, yet still small, fractions of matrix water later in the summer. These findings were combined with geologic information, prior subsurface dye tracing, and chemical sampling to provide additional lines of evidence that repeated groundwater exchanges are likely occurring and river flows are highly dependent on karst aquifer recharge and discharge. Given the large population dependent on karst aquifers throughout the world, there is a continued need to develop simple methods, like those presented here, for determining the resiliency of karst groundwater resources.

Water Resources Research↗

USGS2018

A database of natural monthly streamflow estimates from 1950 to 2015 for the conterminous United States

Quantifying and understanding the natural streamflow regime, defined as expected streamflow that would occur in the absence of anthropogenic modification to the hydrologic system, is critically important for the development of management strategies aimed at protecting aquatic ecosystems. Water balance models have been applied frequently to estimate natural flows, but are limited in the number of predictor variables that can be included. Here, a statistical machine learning technique — random forest modeling — was applied to estimate natural flows at a monthly time‐step from 1950 to 2015 for >2.5 million stream reaches in the conterminous United States (U.S.) using 200 potential predictor variables. We describe the development and documentation of this dataset and assess model performance. Model fit statistics (mean Nash–Sutcliffe efficiency = 0.85; observed/expected ratio = 0.94) indicate good correspondence between predicted and observed flows at nearly 2,000 streamgages. As an example application of the dataset, the observed streamflow record at a site prior to and after the construction of an upstream reservoir was compared with estimated natural flows to demonstrate the magnitude of seasonal depletions in streamflow due to the reservoir. This dataset can be applied to quantify natural and anthropogenic processes contributing to streamflow depletion or augmentation, and assess associated ecological effects.

Journal of the American Water Resources Associatio↗

USGS2018

Managing salinity in Upper Colorado River Basin streams: Selecting catchments for sediment control efforts using watershed characteristics and random forests models

Elevated concentrations of dissolved-solids (salinity) including calcium, sodium, sulfate, and chloride, among others, in the Colorado River cause substantial problems for its water users. Previous efforts to reduce dissolved solids in upper Colorado River basin (UCRB) streams often focused on reducing suspended-sediment transport to streams, but few studies have investigated the relationship between suspended sediment and salinity, or evaluated which watershed characteristics might be associated with this relationship. Are there catchment properties that may help in identifying areas where control of suspended sediment will also reduce salinity transport to streams? A random forests classification analysis was performed on topographic, climate, land cover, geology, rock chemistry, soil, and hydrologic information in 163 UCRB catchments. Two random forests models were developed in this study: one for exploring stream and catchment characteristics associated with stream sites where dissolved solids increase with increasing suspended-sediment concentration, and the other for predicting where these sites are located in unmonitored reaches. Results of variable importance from the exploratory random forests models indicate that no simple source, geochemical process, or transport mechanism can easily explain the relationship between dissolved solids and suspended sediment concentrations at UCRB monitoring sites. Among the most important watershed characteristics in both models were measures of soil hydraulic conductivity, soil erodibility, minimum catchment elevation, catchment area, and the silt component of soil in the catchment. Predictions at key locations in the basin were combined with observations from selected monitoring sites, and presented in map-form to give a complete understanding of where catchment sediment control practices would also benefit control of dissolved solids in streams.

Upper Colorado River Basin↗

USGS2017

Estimating discharge and nonpoint source nitrate loading to streams from three end‐member pathways using high‐frequency water quality data

The myriad hydrologic and biogeochemical processes taking place in watersheds occurring across space and time are integrated and reflected in the quantity and quality of water in streams and rivers. Collection of high‐frequency water quality data with sensors in surface waters provides new opportunities to disentangle these processes and quantify sources and transport of water and solutes in the coupled groundwater‐surface water system. A new approach for separating the streamflow hydrograph into three components was developed and coupled with high‐frequency nitrate data to estimate time‐variable nitrate loads from chemically dilute quick flow, chemically concentrated quick flow, and slowflow groundwater end‐member pathways for periods of up to 2 years in a groundwater‐dominated and a quick‐flow‐dominated stream in central Wisconsin, using only streamflow and in‐stream water quality data. The dilute and concentrated quick flow end‐members were distinguished using high‐frequency specific conductance data. Results indicate that dilute quick flow contributed less than 5% of the nitrate load at both sites, whereas 89 ± 8% of the nitrate load at the groundwater‐dominated stream was from slowflow groundwater, and 84 ± 25% of the nitrate load at the quick‐flow‐dominated stream was from concentrated quick flow. Concentrated quick flow nitrate concentrations varied seasonally at both sites, with peak concentrations in the winter that were 2–3 times greater than minimum concentrations during the growing season. Application of this approach provides an opportunity to assess stream vulnerability to nonpoint source nitrate loading and expected stream responses to current or changing conditions and practices in watersheds.

Water Resources Research↗

USGS2017

The role of baseflow in dissolved solids delivery to streams in the Upper Colorado River Basin

Salinity has a major effect on water users in the Colorado River Basin, estimated to cause almost $300 million per year in economic damages. The Colorado River Basin Salinity Control Program implements and manages projects to reduce salinity loads, investing millions of dollars per year in irrigation upgrades, canal projects, and other mitigation strategies. To inform and improve mitigation efforts, there is a need to better understand sources of salinity to streams and how salinity has changed over time. This study explores salinity in the baseflow fraction of streamflow, assessing whether groundwater is a significant contributor of dissolved solids to streams in the Upper Colorado River Basin (UCRB). Chemical hydrograph separation was used to estimate baseflow discharge and baseflow dissolved solids loads at stream gages ( n = 69) across the UCRB. On average, it is estimated that 89% of dissolved solids loads originate from the baseflow fraction of streamflow, indicating that subsurface transport processes play a dominant role in delivering dissolved solids to streams in the UCRB. A statistical trend analysis using weighted regressions on time, discharge, and season was used to evaluate changes in baseflow dissolved solids loads in streams ( n = 27) from 1986 to 2011. Decreasing trends in baseflow dissolved solids loads were observed at 63% of streams. At the three most downstream sites, Green River at Green River, UT, Colorado River at Cisco, UT, and the San Juan River near Bluff, UT, baseflow dissolved solids loads decreased by a combined 823,000 metric tons (mT), which is approximately 69% of projected basin‐scale decreases in total dissolved solids loads as a result of salinity control efforts. Decreasing trends in baseflow dissolved solids loads suggest that salinity mitigation projects, landscape changes, and/or climate are reducing dissolved solids transported to streams through the subsurface. Notably, the pace and extent of decreases in baseflow dissolved solids loads declined during the most recent decade; average decreasing loads during the 2000s (28,200 mT) were only 54% of average decreasing loads in the 1990s (51,700 mT).

Upper Colorado River Basin↗

USGS2017

Predicting redox-sensitive contaminant concentrations in groundwater using random forest classification

Machine learning techniques were applied to a large (n > 10,000) compliance monitoring database to predict the occurrence of several redox-active constituents in groundwater across a large watershed. Specifically, random forest classification was used to determine the probabilities of detecting elevated concentrations of nitrate, iron, and arsenic in the Fox, Wolf, Peshtigo, and surrounding watersheds in northeastern Wisconsin. Random forest classification is well suited to describe the nonlinear relationships observed among several explanatory variables and the predicted probabilities of elevated concentrations of nitrate, iron, and arsenic. Maps of the probability of elevated nitrate, iron, and arsenic can be used to assess groundwater vulnerability and the vulnerability of streams to contaminants derived from groundwater. Processes responsible for elevated concentrations are elucidated using partial dependence plots. For example, an increase in the probability of elevated iron and arsenic occurred when well depths coincided with the glacial/bedrock interface, suggesting a bedrock source for these constituents. Furthermore, groundwater in contact with Ordovician bedrock has a higher likelihood of elevated iron concentrations, which supports the hypothesis that groundwater liberates iron from a sulfide-bearing secondary cement horizon of Ordovician age. Application of machine learning techniques to existing compliance monitoring data offers an opportunity to broadly assess aquifer and stream vulnerability at regional and national scales and to better understand geochemical processes responsible for observed conditions.

Water Resources Research↗

USGS2017

Variability of dissolved organic carbon in precipitation during storms at the Shale Hills Critical Zone Observatory

Organic compounds are removed from the atmosphere and deposited to the earth's surface via precipitation. In this study, we quantified variations of dissolved organic carbon (DOC) in precipitation during storm events at the Shale Hills Critical Zone Observatory, a forested watershed in central Pennsylvania (USA). Precipitation samples were collected consecutively throughout the storm during 13 events, which spanned a range of seasons and synoptic meteorological conditions, including a hurricane. Further, we explored factors that affect the temporal variability by considering relationships of DOC in precipitation with atmospheric and storm characteristics. Concentrations and chemical composition of DOC changed considerably during storms, with the magnitude of change within individual events being comparable or higher than the range of variation in average event composition among events. While some previous studies observed that concentrations of other elements in precipitation typically decrease over the course of individual storm events, results of this study show that DOC concentrations in precipitation are highly variable. During most storm events concentrations decreased over time, possibly as a result of washing out of the below-cloud atmosphere. However, increasing concentrations that were observed in the later stages of some storm events highlight that DOC removal with precipitation is not merely a dilution response. Increases in DOC during events could result from advection of air masses, local emissions during breaks in precipitation, or chemical transformations in the atmosphere that enhance solubility of organic carbon compounds. This work advances understanding of processes occurring during storms that are relevant to studies of atmospheric chemistry, carbon cycling, and ecosystem responses.

Pennsylvania↗

USGS2017

Enhanced and updated spatially referenced statistical assessment of dissolved-solids load sources and transport in streams of the Upper Colorado River Basin

Approximately 6.4 million tons of dissolved solids are discharged from the Upper Colorado River Basin (UCRB) to the Lower Colorado River Basin each year. This results in substantial economic damages, and tens of millions of dollars are spent annually on salinity control projects designed to reduce salinity loads in surface waters of the UCRB. Dissolved solids in surface water and groundwater have been studied extensively over the past century, and these studies have contributed to a conceptual understanding of sources and transport of dissolved solids. This conceptual understanding was incorporated into a Spatially Referenced Regressions on Watershed Attributes (SPARROW) model to examine sources and transport of dissolved solids in the UCRB. The results of this model were published in 2009. The present report documents the methods and data used to develop an updated dissolved-solids SPARROW model for the UCRB, and incorporates data defining current basin attributes not available in the previous model, including delineation of irrigated lands by irrigation type (sprinkler or flood irrigation), and calibration data from additional monitoring sites. Dissolved-solids loads estimated for 312 monitoring sites were used to calibrate the SPARROW model, which predicted loads for each of 10,789 stream reaches in the UCRB. The calibrated model provided a good fit to the calibration data as evidenced by R 2 and yield R 2 values of 0.96 and 0.73, respectively, and a root-mean-square error of 0.47. The model included seven geologic sources that have estimated dissolved-solids yields ranging from approximately 1 to 45 tons per square mile (tons/mi 2 ). Yields generated from irrigated agricultural lands are substantially greater than those from geologic sources, with sprinkler irrigated lands generating an average of approximately 150 tons/mi 2 and flood irrigated lands generating between 770 and 2,300 tons/mi 2 depending on underlying lithology. The coefficients estimated for six landscape transport characteristics that influence the delivery of dissolved solids from sources to streams, are consistent with the process understanding of dissolved-solids loading to streams in the UCRB. Dissolved-solids loads and the proportion of those loads among sources in the entire UCRB as well as in major tributaries in the basin are reported, as are loads generated from irrigated lands, rangelands, Bureau of Land Management (BLM) lands, and grazing allotments on BLM lands. Model-predicted loads also are compared with load estimates from 1957 and 1991 at selected locations in three divisions of the UCRB. At the basin scale, the model estimates that 32 percent of the dissolved-solids loads are from irrigated agricultural land sources that compose less than 2 percent of the land area in the UCRB. This estimate is less than previously reported estimates of 40 to 45 percent of basin-scale dissolved-solids loads from irrigated agricultural land sources. This discrepancy could be a result of the implementation of salinity control projects in the basin. Notably, results indicate that the conversion of flood irrigated agricultural lands to sprinkler irrigated agricultural lands is a likely process contributing to the temporal decrease in dissolved-solids loads from irrigated lands.

Colorado River Basin↗

USGS2016

Variation of organic matter quantity and quality in streams at Critical Zone Observatory watersheds

The quantity and chemical composition of dissolved organic matter (DOM) in surface waters influence ecosystem processes and anthropogenic use of freshwater. However, despite the importance of understanding spatial and temporal patterns in DOM, measures of DOM quality are not routinely included as part of large-scale ecosystem monitoring programs and variations in analytical procedures can introduce artifacts. In this study, we used consistent sampling and analytical methods to meet the objective of defining variability in DOM quantity and quality and other measures of water quality in streamflow issuing from small forested watersheds located within five Critical Zone Observatory sites representing contrasting environmental conditions. Results show distinct separations among sites as a function of water quality constituents. Relationships among rates of atmospheric deposition, water quality conditions, and stream DOM quantity and quality are consistent with the notion that areas with relatively high rates of atmospheric nitrogen and sulfur deposition and high concentrations of divalent cations result in selective transport of DOM derived from microbial sources, including in-stream microbial phototrophs. We suggest that the critical zone as a whole strongly influences the origin, composition, and fate of DOM in streams. This study highlights the value of consistent DOM characterization methods included as part of long-term monitoring programs for improving our understanding of interactions among ecosystem processes as controls on DOM biogeochemistry.

Water Resources Research↗

USGS2016

Climate regulates alpine lake ice cover phenology and aquatic ecosystem structure

High-elevation aquatic ecosystems are highly vulnerable to climate change, yet relatively few records are available to characterize shifts in ecosystem structure or their underlying mechanisms. Using a long-term dataset on seven alpine lakes (3126 to 3620 m) in Colorado, USA, we show that ice-off dates have shifted seven days earlier over the past 33 years and that spring weather conditions – especially snowfall – drive yearly variation in ice-off timing. In the most well-studied lake, earlier ice-off associated with increases in water residence times, thermal stratification, ion concentrations, dissolved nitrogen, pH, and chlorophyll-a. Mechanistically, low spring snowfall and warm temperatures reduce summer stream flow (increasing lake residence times) but enhance melting of glacial and permafrost ice (increasing lake solute inputs). The observed links among hydrological, chemical, and biological responses to climate factors highlight the potential for major shifts in the functioning of alpine lakes due to forecasted climate change.

Colorado↗

USGS2016

The importance of base flow in sustaining surface water flow in the Upper Colorado River Basin

The Colorado River has been identified as the most overallocated river in the world. Considering predicted future imbalances between water supply and demand and the growing recognition that base flow (a proxy for groundwater discharge to streams) is critical for sustaining flow in streams and rivers, there is a need to develop methods to better quantify present-day base flow across large regions. We adapted and applied the spatially referenced regression on watershed attributes (SPARROW) water quality model to assess the spatial distribution of base flow, the fraction of streamflow supported by base flow, and estimates of and potential processes contributing to the amount of base flow that is lost during in-stream transport in the Upper Colorado River Basin (UCRB). On average, 56% of the streamflow in the UCRB originated as base flow, and precipitation was identified as the dominant driver of spatial variability in base flow at the scale of the UCRB, with the majority of base flow discharge to streams occurring in upper elevation watersheds. The model estimates an average of 1.8 × 10 10 m 3 /yr of base flow in the UCRB; greater than 80% of which is lost during in-stream transport to the Lower Colorado River Basin via processes including evapotranspiration and water diversion for irrigation. Our results indicate that surface waters in the Colorado River Basin are dependent on base flow, and that management approaches that consider groundwater and surface water as a joint resource will be needed to effectively manage current and future water resources in the Basin.

Arizona, Colorado, New Mexico, Utah, Wyoming↗

USGS2016

Quantifying watershed-scale groundwater loading and in-stream fate of nitrate using high-frequency water quality data

We describe a new approach that couples hydrograph separation with high-frequency nitrate data to quantify time-variable groundwater and runoff loading of nitrate to streams, and the net in-stream fate of nitrate at the watershed-scale. The approach was applied at three sites spanning gradients in watershed size and land use in the Chesapeake Bay watershed. Results indicate that 58-73% of the annual nitrate load to the streams was groundwater-discharged nitrate. Average annual first order nitrate loss rate constants (k) were similar to those reported in both modelling and in-stream process-based studies, and were greater at the small streams (0.06 and 0.22 d -1 ) than at the large river (0.05 d -1 ), but 11% of the annual loads were retained/lost in the small streams, compared with 23% in the large river. Larger streambed area to water volume ratios in small streams result in greater loss rates, but shorter residence times in small streams result in a smaller fraction of nitrate loads being removed than in larger streams. A seasonal evaluation of k values suggests that nitrate was retained/lost at varying rates during the growing season. Consistent with previous studies, streamflow and nitrate concentration were inversely related to k. This new approach for interpreting high-frequency nitrate data and the associated findings furthers our ability to understand, predict, and mitigate nitrate impacts on streams and receiving waters by providing insights into temporal nitrate dynamics that would be difficult to obtain using traditional field-based studies.

Delaware, Pennsylvania, Maryland, New York, Virgin↗

USGS2016

Atmospheric inputs of organic matter to a forested watershed: Variations from storm to storm over the seasons

The objectives of this study were to determine the quantity and chemical composition of precipitation inputs of dissolved organic carbon (DOC) to a forested watershed; and to characterize the associated temporal variability. We sampled most precipitation that occurred from May 2012 through August 2013 at the Susquehanna Shale Hills Critical Zone Observatory (Pennsylvania, USA). Sub-event precipitation samples (159) were collected sequentially during 90 events; covering various types of synoptic meteorological conditions in all climatic seasons. Precipitation DOC concentrations and rates of wet atmospheric DOC deposition were highly variable from storm to storm, ranging from 0.3 to 5.6 mg C L −1 and from 0.5 to 32.8 mg C m −2 h −1 , respectively. Seasonally, storms in spring and summer had higher concentrations of DOC and more optically active organic matter than in winter. Higher DOC concentrations resulted from weather types that favor air advection, where cold frontal systems, on average, delivered more than warm/stationary fronts and northeasters. A mixed modeling statistical approach revealed that factors related to storm properties, emission sources, and to the chemical composition of the atmosphere could explain more than 60% of the storm to storm variability in DOC concentrations. This study provided observations on changes in dissolved organic matter that can be useful in modeling of atmospheric oxidative chemistry, exploring relationships between organics and other elements of precipitation chemistry, and in considering temporal changes in ecosystem nutrient balances and microbial activity.

Atmospheric Environment↗

USGS2016

Patterns of diel variation in nitrate concentrations in the Potomac River

The Potomac River is a large source of N to Chesapeake Bay, where reducing nutrient loads is a focus of efforts to improve trophic status. Better understanding of NO 3 – loss, reflected in part by diel variation in NO 3 – concentrations, may refine model predictions of N loads to the Bay. We analyzed 2 y of high-frequency NO 3 – sensor data in the Potomac to quantify seasonal variation in the magnitude and timing of diel NO 3 – loss. Diel patterns were evident, especially during low flow, despite broad seasonal and flow-driven variation in NO 3 – concentrations. Diel variation was ~0.01 mg N/L in winter and 0.02 to 0.03 mg N/L in summer with intermediate values in spring and autumn, equivalent to <1% of the daily mean NO 3 – concentration in winter and ~2 to 4% in summer. Maximum diel NO 3 – values generally occurred in mid- to late morning, with more repeatable patterns in summer and wider variation in autumn and winter. Diel NO 3 – loss reduced loads by 0.7% in winter and 3% in summer. These losses were less than estimates of total in-stream NO 3 – load loss across the basin that averaged 33% of the annual groundwater contribution to the river. Water temperature and discharge had stronger relationships to the daily magnitude of diel NO 3 – variation than did photosynthetically active radiation. Estimated diel areal NO 3 – loss rates were generally >1000 mg N m –2 d –1 , greater than most published values because measurements in this large river integrate over a greater depth/unit stream bottom area than do those from smaller rivers. These diel NO 3 – patterns are consistent with the influence of photoautotrophic uptake and related denitrification, but we cannot attribute these patterns to assimilation alone because the magnitude and timing of diel dynamics were affected to an unknown extent by processes, such as evapotranspiration, transient storage, and hydrodynamic dispersion. Improvements to diel loss estimates will require additional high-frequency measures, such as dissolved O 2 , dissolved organic N, and NH 4 + , and deployment of 2 measurement stations.

Potomac River↗