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P. J. Mulholland

Publications and source records attributed to P. J. Mulholland.

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Hydrology and biogeochemistry linkages

This chapter provides an overview of the linkages between hydrology and biogeochemistry in terrestrial and aquatic systems. Selected topics include hydrological pathways on drainage basin slopes, mountain environments, within-river (or in-stream) processes, wetlands, groundwater (and groundwater–surface water interactions), and lakes. Beginning from catchment headwaters, This chapter introduces mechanisms delivering water from hillslopes to stream channels, highlighting the relative importance of biogeochemical processes along hydrological pathways. It considers processes affecting components of the water budget, including snow formation and ablation processes, and interactions with the soil below snow cover and during snowmelt. It presents the concept of nutrient spiraling and the importance of temperature and stream flow variability on biogeochemistry, as well as groundwater–surface water interactions through hyporheic and riparian zones. This chapter contrasts important processes in hydrologically isolated wetlands with those temporally connected to streams and rivers. It addresses stream and groundwater inputs, stratification, and within-lake processes, interactions with sediments, and a discussion about limiting nutrients. This chapter presents information about typical reactions controlled by hydrological pathways, lithology (mineralogy) and biota, the importance of residence time in biogeochemical evolution, and linkages between groundwater Acidic atmospheric deposition

Book chapter

Nitrous oxide emission from denitrification in stream and river networks

Nitrous oxide (N 2 O) is a potent greenhouse gas that contributes to climate change and stratospheric ozone destruction. Anthropogenic nitrogen (N) loading to river networks is a potentially important source of N 2 O via microbial denitrification that converts N to N 2 O and dinitrogen (N 2 ). The fraction of denitrified N that escapes as N 2 O rather than N 2 (i.e., the N 2 O yield) is an important determinant of how much N 2 O is produced by river networks, but little is known about the N 2 O yield in flowing waters. Here, we present the results of whole-stream 15 N-tracer additions conducted in 72 headwater streams draining multiple land-use types across the United States. We found that stream denitrification produces N 2 O at rates that increase with stream water nitrate (NO 3 − ) concentrations, but that <1% of denitrified N is converted to N 2 O. Unlike some previous studies, we found no relationship between the N 2 O yield and stream water NO 3 − . We suggest that increased stream NO 3 − loading stimulates denitrification and concomitant N 2 O production, but does not increase the N 2 O yield. In our study, most streams were sources of N 2 O to the atmosphere and the highest emission rates were observed in streams draining urban basins. Using a global river network model, we estimate that microbial N transformations (e.g., denitrification and nitrification) convert at least 0.68 Tg·y −1 of anthropogenic N inputs to N 2 O in river networks, equivalent to 10% of the global anthropogenic N 2 O emission rate. This estimate of stream and river N 2 O emissions is three times greater than estimated by the Intergovernmental Panel on Climate Change. Humans have more than doubled the availability of fixed nitrogen (N) in the biosphere, particularly through the production of N fertilizers and the cultivation of N-fixing crops ( 1 ). Increasing N availability is producing unintended environmental consequences including enhanced emissions of nitrous oxide (N 2 O), a potent greenhouse gas ( 2 ) and an important cause of stratospheric ozone destruction ( 3 ). The Intergovernmental Panel on Climate Change (IPCC) estimates that the microbial conversion of agriculturally derived N to N 2 O in soils and aquatic ecosystems is the largest source of anthropogenic N 2 O to the atmosphere ( 2 ). The production of N 2 O in agricultural soils has been the focus of intense investigation (i.e., >1,000 published studies) and is a relatively well constrained component of the N 2 O budget ( 4 ). However, emissions of anthropogenic N 2 O from streams, rivers, and estuaries have received much less attention and remain a major source of uncertainty in the global anthropogenic N 2 O budget. Microbial denitrification is a large source of N 2 O emissions in terrestrial and aquatic ecosystems. Most microbial denitrification is a form of anaerobic respiration in which nitrate (NO 3 − , the dominant form of inorganic N) is converted to dinitrogen (N 2 ) and N 2 O gases ( 5 ). The proportion of denitrified NO 3 − that is converted to N 2 O rather than N 2 (hereafter referred to as the N 2 O yield and expressed as the mole ratio) partially controls how much N 2 O is produced via denitrification ( 6 ), but few studies provide information on the N 2 O yield in streams and rivers because of the difficulty of measuring N 2 and N 2 O production in these systems. Here we report rates of N 2 and N 2 O production via denitrification measured using whole-stream 15 NO 3 − -tracer experiments in 72 headwater streams draining different land-use types across the United States. This project, known as the second Lotic Intersite Nitrogen eXperiment (LINX II), provides unique whole-system measurements of the N 2 O yield in streams. Although N 2 O emission rates have been reported for streams and rivers ( 7 , 8 ), the N 2 O yield has been studied mostly in lentic freshwater and marine ecosystems, where it generally ranges between 0.1 and 1.0%, although yields as high as 6% have been observed ( 9 ). These N 2 O yields are low compared with observations in soils (0–100%) ( 10 ), which may be a result of the relatively lower oxygen (O 2 ) availability in the sediments of lakes and estuaries. However, dissolved O 2 in headwater streams is commonly near atmospheric equilibrium and benthic algal biofilms can produce O 2 at the sediment–water interface, resulting in strong redox gradients more akin to those in partially wetted soils. Thus, streams may have variable and often high N 2 O yields, similar to those in soils ( 11 ). The N 2 O yield in headwater streams is of particular interest because much of the NO 3 − input to rivers is derived from groundwater upwelling into headwater streams. Furthermore, headwater streams compose the majority of stream length within a drainage network and have high ratios of bioreactive benthic surface area to water volume ( 12 ).

Proceedings of the National Academy of Sciences of

Inter-regional comparison of land-use effects on stream metabolism

1. Rates of whole-system metabolism (production and respiration) are fundamental indicators of ecosystem structure and function. Although first-order, proximal controls are well understood, assessments of the interactions between proximal controls and distal controls, such as land use and geographic region, are lacking. Thus, the influence of land use on stream metabolism across geographic regions is unknown. Further, there is limited understanding of how land use may alter variability in ecosystem metabolism across regions.2. Stream metabolism was measured in nine streams in each of eight regions (n = 72) across the United States and Puerto Rico. In each region, three streams were selected from a range of three land uses: agriculturally influenced, urban-influenced, and reference streams. Stream metabolism was estimated from diel changes in dissolved oxygen concentrations in each stream reach with correction for reaeration and groundwater input.3. Gross primary production (GPP) was highest in regions with little riparian vegetation (sagebrush steppe in Wyoming, desert shrub in Arizona/New Mexico) and lowest in forested regions (North Carolina, Oregon). In contrast, ecosystem respiration (ER) varied both within and among regions. Reference streams had significantly lower rates of GPP than urban or agriculturally influenced streams.4. GPP was positively correlated with photosynthetically active radiation and autotrophic biomass. Multiple regression models compared using Akaike's information criterion (AIC) indicated GPP increased with water column ammonium and the fraction of the catchment in urban and reference land-use categories. Multiple regression models also identified velocity, temperature, nitrate, ammonium, dissolved organic carbon, GPP, coarse benthic organic matter, fine benthic organic matter and the fraction of all land-use categories in the catchment as regulators of ER.5. Structural equation modelling indicated significant distal as well as proximal control pathways including a direct effect of land-use on GPP as well as SRP, DIN, and PAR effects on GPP; GPP effects on autotrophic biomass, organic matter, and ER; and organic matter effects on ER.6. Overall, consideration of the data separated by land-use categories showed reduced inter-regional variability in rates of metabolism, indicating that the influence of agricultural and urban land use can obscure regional differences in stream metabolism. ?? 2010 Blackwell Publishing Ltd.

Freshwater Biology

Nitrate removal in stream ecosystems measured by 15 N addition experiments: Total uptake

We measured uptake length of 15 NO- 3 in 72 streams in eight regions across the United States and Puerto Rico to develop quantitative predictive models on controls of NO- 3 uptake length. As part of the Lotic Intersite Nitrogen eXperiment II project, we chose nine streams in each region corresponding to natural (reference), suburban-urban, and agricultural land uses. Study streams spanned a range of human land use to maximize variation in NO- 3 concentration, geomorphology, and metabolism. We tested a causal model predicting controls on NO- 3 uptake length using structural equation modeling. The model included concomitant measurements of ecosystem metabolism, hydraulic parameters, and nitrogen concentration. We compared this structural equation model to multiple regression models which included additional biotic, catchment, and riparian variables. The structural equation model explained 79% of the variation in log uptake length (S Wtot ). Uptake length increased with specific discharge (Q/w) and increasing NO- 3 concentrations, showing a loss in removal efficiency in streams with high NO- 3 concentration. Uptake lengths shortened with increasing gross primary production, suggesting autotrophic assimilation dominated NO- 3 removal. The fraction of catchment area as agriculture and suburban-urban land use weakly predicted NO- 3 uptake in bivariate regression, and did improve prediction in a set of multiple regression models. Adding land use to the structural equation model showed that land use indirectly affected NO- 3 uptake lengths via directly increasing both gross primary production and NO- 3 concentration. Gross primary production shortened S Wtot , while increasing NO- 3 lengthened S Wtot resulting in no net effect of land use on NO- 3 removal. ?? 2009.

Limnology and Oceanography

Nitrate removal in stream ecosystems measured by 15 N addition experiments: Denitrification

We measured denitrification rates using a field 15 N-NO- 3 tracer-addition approach in a large, cross-site study of nitrate uptake in reference, agricultural, and suburban-urban streams. We measured denitrification rates in 49 of 72 streams studied. Uptake length due to denitrification (S Wden ) ranged from 89 m to 184 km (median of 9050 m) and there were no significant differences among regions or land-use categories, likely because of the wide range of conditions within each region and land use. N 2 production rates far exceeded N 2 O production rates in all streams. The fraction of total NO- 3 removal from water due to denitrification ranged from 0.5% to 100% among streams (median of 16%), and was related to NHz 4 concentration and ecosystem respiration rate (ER). Multivariate approaches showed that the most important factors controlling S Wden were specific discharge (discharge / width) and NO- 3 concentration (positive effects), and ER and transient storage zones (negative effects). The relationship between areal denitrification rate (U den ) and NO- 3 concentration indicated a partial saturation effect. A power function with an exponent of 0.5 described this relationship better than a Michaelis-Menten equation. Although Uden increased with increasing NO- 3 concentration, the efficiency of NO- 3 removal from water via denitrification declined, resulting in a smaller proportion of streamwater NO- 3 load removed over a given length of stream. Regional differences in stream denitrification rates were small relative to the proximate factors of NO- 3 concentration and ecosystem respiration rate, and land use was an important but indirect control on denitrification in streams, primarily via its effect on NO- 3 concentration. ?? 2009.

Limnology and Oceanography

Stream denitrification across biomes and its response to anthropogenic nitrate loading

Anthropogenic addition of bioavailable nitrogen to the biosphere is increasing and terrestrial ecosystems are becoming increasingly nitrogen-saturated, causing more bioavailable nitrogen to enter groundwater and surface waters. Large-scale nitrogen budgets show that an average of about 20-25 per cent of the nitrogen added to the biosphere is exported from rivers to the ocean or inland basins, indicating that substantial sinks for nitrogen must exist in the landscape. Streams and rivers may themselves be important sinks for bioavailable nitrogen owing to their hydrological connections with terrestrial systems, high rates of biological activity, and streambed sediment environments that favour microbial denitrification. Here we present data from nitrogen stable isotope tracer experiments across 72 streams and 8 regions representing several biomes. We show that total biotic uptake and denitrification of nitrate increase with stream nitrate concentration, but that the efficiency of biotic uptake and denitrification declines as concentration increases, reducing the proportion of in-stream nitrate that is removed from transport. Our data suggest that the total uptake of nitrate is related to ecosystem photosynthesis and that denitrification is related to ecosystem respiration. In addition, we use a stream network model to demonstrate that excess nitrate in streams elicits a disproportionate increase in the fraction of nitrate that is exported to receiving waters and reduces the relative role of small versus large streams as nitrate sinks. ??2008 Nature Publishing Group.

Nature

Effects of upland disturbance and instream restoration on hydrodynamics and ammonium uptake in headwater streams

Delivery of water, sediments, nutrients, and organic matter to stream ecosystems is strongly influenced by the catchment of the stream and can be altered greatly by upland soil and vegetation disturbance. At the Fort Benning Military Installation (near Columbus, Georgia), spatial variability in intensity of military training results in a wide range of intensities of upland disturbance in stream catchments. A set of 8 streams in catchments spanning this upland disturbance gradient was selected for investigation of the impact of disturbance intensity on hydrodynamics and nutrient uptake. The size of transient storage zones and rates of NH4+ uptake in all study streams were among the lowest reported in the literature. Upland disturbance did not appear to influence stream hydrodynamics strongly, but it caused significant decreases in instream nutrient uptake. In October 2003, coarse woody debris (CWD) was added to 1/2 of the study streams (spanning the disturbance gradient) in an attempt to increase hydrodynamic and structural complexity, with the goals of enhancing biotic habitat and increasing nutrient uptake rates. CWD additions had positive short-term (within 1 mo) effects on hydrodynamic complexity (water velocity decreased and transient storage zone cross-sectional area, relative size of the transient storage zone, fraction of the median travel time attributable to transient storage over a standardized length of 200 m, and the hydraulic retention factor increased) and nutrient uptake (NH4+ uptake rates increased). Our results suggest that water quality in streams with intense upland disturbances can be improved by enhancing instream biotic nutrient uptake capacity through measures such as restoring stream CWD. ?? 2007 by The North American Benthological Society.

Journal of the North American Benthological Societ

Catchment disturbance and stream metabolism: Patterns in ecosystem respiration and gross primary production along a gradient of upland soil and vegetation disturbance

Catchment characteristics determine the inputs of sediments and nutrients to streams. As a result, natural or anthropogenic disturbance of upland soil and vegetation can affect instream processes. The Fort Benning Military Installation (near Columbus, Georgia) exhibits a wide range of upland disturbance levels because of spatial variability in the intensity of military training. This gradient of disturbance was used to investigate the effect of upland soil and vegetation disturbance on rates of stream metabolism (ecosystem respiration rate [ER] and gross primary production rate [GPP]). Stream metabolism was measured using an open-system, single-station approach. All streams were net heterotrophic during all seasons. ER was highest in winter and spring and lowest in summer and autumn. ER was negatively correlated with catchment disturbance level in winter, spring, and summer, but not in autumn. ER was positively correlated with abundance of coarse woody debris, but not significantly related to % benthic organic matter. GPP was low in all streams and generally not significantly correlated with disturbance level. Our results suggest that the generally intact riparian zones of these streams were not sufficient to protect them from the effect of upland disturbance, and they emphasize the role of the entire catchment in determining stream structure and function. ?? 2005 by The North American Benthological Society.

Journal of the North American Benthological Societ

Relationships between hydraulic parameters in a small stream under varying flow and seasonal conditions

Twenty conservative tracer injections were carried out in the same reach of a small woodland stream in order to determine how variation in discharge and leaf accumulation affect stream hydraulic parameters. The injections were made at various discharge rates ranging from 2-6 to 40 1/s. Five of the injections were made during late autumn, when there were large accumulations of leaves in the stream. Estimates of hydraulic parameters were made by fitting a transient storage solute transport model to conservative tracer concentration profiles. Velocity increased almost linearly with increasing discharge, indicating a decline in the Darcy friction factor. Dispersion also increased with increasing discharge, especially for the lower flow injections. The relative size of the storage zone was small (???0??1). There was no definable relationship between discharge and the relative storage zone size, but the rates of exchange between the storage zone and the main channel increased markedly with increasing discharge. The presence of large accumulations of leaves had a clear effect on the hydraulic characteristics of the stream, producing much higher friction factors, larger storage zone sizes and lower velocity than would have been predicted by discharge alone. Copyright ?? 1999 John Wiley & Sons, Ltd.

Hydrological Processes