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Geology topics

Richard L. Smith

Publications and source records attributed to Richard L. Smith.

At least 19 recordsLinked to original sources

Influence of four veterinary antibiotics on constructed treatment wetland nitrogen transformation

The use of wetlands as a treatment approach for nitrogen in runoff is a common practice in agroecosystems. However, nitrate is not the sole constituent present in agricultural runoff and other biologically active contaminants have the potential to affect nitrate removal efficiency. In this study, the impacts of the combined effects of four common veterinary antibiotics (chlortetracycline, sulfamethazine, lincomycin, monensin) on nitrate-N treatment efficiency in saturated sediments and wetlands were evaluated in a coupled microcosm/mesocosm scale experiment. Veterinary antibiotics were hypothesized to significantly impact nitrogen speciation (e.g., nitrate and ammonium) and nitrogen uptake and transformation processes (e.g., plant uptake and denitrification) within the wetland ecosystems. To test this hypothesis, the coupled study had three objectives: 1. assess veterinary antibiotic impact on nitrogen cycle processes in wetland sediments using microcosm incubations, 2. measure nitrate-N reduction in water of floating treatment wetland systems over time following the introduction of veterinary antibiotic residues, and 3. identify the fate of veterinary antibiotics in floating treatment wetlands using mesocosms. Microcosms containing added mixtures of the veterinary antibiotics had little to no effect at lower concentrations but stimulated denitrification potential rates at higher concentrations. Based on observed changes in the nitrogen loss in the microcosm experiments, floating treatment wetland mesocosms were enriched with 1000 μg L −1 of the antibiotic mixture. Rates of nitrate-N loss observed in mesocosms with the veterinary antibiotic enrichment were consistent with the microcosm experiments in that denitrification was not inhibited, even at the high dosage. In the mesocosm experiments, average nitrate-N removal rates were not found to be impacted by the veterinary antibiotics. Further, veterinary antibiotics were primarily found in the roots of the floating treatment wetland biomass, accumulating approximately 190 mg m −2 of the antibiotic mixture. These findings provide new insight into the impact that veterinary antibiotic mixtures may have on nutrient management strategies for large-scale agricultural operations and the potential for veterinary antibiotic removal in these wetlands.

Toxics

Spatial, seasonal, and diel controls of nitrogen-carbon-oxygen cycling during lake-water infiltration to an aquifer

Many freshwater lakes are groundwater flow-through systems. Although lakes commonly are considered to be sinks for nitrogen inputs, relatively little is known about carbon and nitrogen export from lakes to groundwater. The current study focused on lake-bottom biogeochemical processes accompanying the transport of nitrogen, dissolved oxygen (O 2 ), and dissolved organic carbon (DOC) during lake-water recharge from a groundwater flow-through lake. Lake-water and porewater (15–100 cm below lakebed) samples were collected along transects within the lake downwelling zone. Infiltrating porewater O 2 and DOC concentrations decreased with depth while nitrate (NO 3 − ) concentrations increased, indicating nitrification of organic matter within the profiles. The depth of NO 3 − production and transport was seasonally dependent. In winter, NO 3 − and O 2 were exported beyond 100-cm depth; whereas in summer, shallow nitrification zones were underlain by deeper NO 3 − reduction zones, and diel patterns of O 2 and NO 3 − penetration depths were observed. Microbial community compositions and stable isotope profiles (δ 15 N[NO 3 − ], δ 18 O[NO 3 − ], δ 18 O[O 2 ]) were consistent with apparent C–N–O reaction stoichiometries indicating O 2 reduction and nitrification in shallower porewater, followed by varying NO 3 − reduction at depth. Maximum porewater NO 3 − concentrations (∼10–20 μM) were limited by infiltrating O 2 concentrations and C/N ratios of reacting organic matter. Lake-water level variations caused changes in shoreline position and porewater velocities, while variations in lake-water temperature, DOC, and O 2 contributed to changes in reaction rates and depth of O 2 and NO 3 − penetration into the lakebed. The quality of groundwater recharged by lake water reflected temporally and spatially varying physical and biogeochemical processes in the sediment porewater.

Journal of Geophysical Research: Biogeosciences

Nitrogen biogeochemistry in a boreal headwater stream network in interior Alaska

High latitude, boreal watersheds are nitrogen (N)-limited ecosystems that export large amounts of organic carbon (C). Key controls on C cycling in these environments are the biogeochemical processes affecting the N cycle. A study was conducted in Nome Creek, an upland headwater tributary of the Yukon River, and two first-order tributaries to Nome Creek, to examine the relation between seasonal and transport-associated changes in C and N pools and N-cycling processes across varying hydrologic gradients using laboratory bioassays of water and sediment samples and in-stream tracer tests. DON exceeded dissolved inorganic nitrogen (DIN) in Nome Creek except late in the summer season, with little variation in organic C:N ratios with time or transport distance. DIN was dominant in the 1st order tributaries. Rates of organic N mineralization and denitrification in laboratory incubations were related to sediment organic C content, while nitrification rates differed greatly between two 1st order tributaries with similar drainages. Additions of DIN or urea did not stimulate microbial activity. In-stream tracer tests with nitrate and urea indicated that uptake rates were slow relative to transport rates; simulated rates of uptake in stream storage zones were higher than rates assessed in the laboratory bioassays. In general, N-cycle processes were more active and had a greater overall impact in the 1st order tributaries and were minimized in Nome Creek, the larger, higher velocity, transport-dominated stream. Understanding key controls on N-cycling processes in these watersheds has important implications for DIN speciation and down-stream impacts of potential increased N loads in response to climate warming.

Alaska

Seasonal and spatial variation in the location and reactivity of a nitrate-contaminated groundwater discharge zone in a lakebed

Groundwater discharge delivering anthropogenic N from surrounding watersheds can impact lake nutrient budgets. However, upgradient groundwater processes and changing dynamics in N biogeochemistry at the groundwater-lake interface are complex and difficult to resolve. In this study, hydrograph variations in a groundwater flow-through lake altered discharge patterns of a wastewater-derived, groundwater contaminant plume, thereby affecting biogeochemical processes controlling N transport. Groundwater geochemistry 15 cm under the lakebed along transects perpendicular to shore varied from oxic to anoxic with increasing nitrate concentrations (10-75 M) and corresponding gradients in nitrite and nitrous oxide. Porewater depth profiles of nitrate concentrations and stable isotope compositions largely reflected upgradient groundwater N sources and N-cycle processes, with minor additional nitrate reduction in the shallowest lakebed sediments. Potential denitrification rates determined in laboratory microcosms were 10-100 fold higher in near-surface sediments (0-5 cm) than in deeper sediments (5-30 cm) and were correlated with sediment carbon content and abundance of denitrification genes (nirS, nosZI, and nosZII). Potential anammox-driven N2 production was highest in deeper anoxic sediments. Injection of bromide and nitrite in the lake sediments indicated a vertical porewater velocity of 4-5 cm hr-1, with highest nitrite consumption rates above 10 cm. However, short residence times in the shallow sediments allowed only a small fraction of the contaminant nitrate to be removed before discharging into the lake. Results demonstrate the importance of resolving local versus upgradient biogeochemical processes affecting contaminant distribution in discharge areas, and transient migration of local gradients and processes in response to changing lake levels and groundwater flow paths.

Journal of Geophysical Research: Biogeosciences

Constraining the oxygen isotopic composition of nitrate produced by nitrification

Measurements of the stable isotope ratios of nitrogen ( 15 N/ 14 N) and oxygen ( 18 O/ 16 O) in nitrate (NO 3 – ) enable identification of sources, dispersal, and fate of natural and contaminant NO 3 – in aquatic environments. The 18 O/ 16 O of NO 3 – produced by nitrification is often assumed to reflect the proportional contribution of oxygen atom sources, water, and molecular oxygen, in a 2:1 ratio. Culture and seawater incubations, however, indicate oxygen isotopic equilibration between nitrite (NO 2 – ) and water, and kinetic isotope effects for oxygen atom incorporation, which modulate the NO 3 – 18 O/ 16 O produced during nitrification. To investigate the influence of kinetic and equilibrium effects on the isotopic composition of NO 3 – produced from the nitrification of ammonia (NH 3 ), we incubated streamwater supplemented with ammonium (NH 4 + ) and increments of 18 O-enriched water. Resulting NO 3 – 18 O/ 16 O ratios showed (1) a disproportionate sensitivity to the 18 O/ 16 O ratio of water, mediated by isotopic equilibration between water and NO 2 – , as well as (2) kinetic isotope discrimination during O atom incorporation from molecular oxygen and water. Empirically, the NO 3 – 18 O/ 16 O ratios thus produced fortuitously converge near the 18 O/ 16 O ratio of water. More elevated NO 3 – 18 O/ 16 O values commonly reported in soils and oxic groundwater may thus derive from processes additional to nitrification, including NO 3 – reduction.

Environmental Science & Technology

Methane and nitrous oxide temporal and spatial variability in two midwestern USA streams containing high nitrate concentrations

Concentrations and emissions of greenhouse gases CO 2 , CH 4 , and N 2 O commonly are examined individually in aquatic environments in which each is expected to be relatively important; however, their co-occurrence and dynamic interactions in fluvial settings could provide important information about their controlling biogeochemical processes and potential contributions to global climate change. Spatial and temporal variability of CH 4 , N 2 O, and CO 2 concentrations were measured from June 1999 to September 2003 in two nitrate-rich (40–1200 μM) streams draining agricultural land in the midwestern USA that differed ~13-fold in flow. Seasonal (biweekly), diel (hourly), and transport-oriented (reach-scale) sampling approaches were compared. Dissolved gas concentrations exceeded atmospheric equilibrium values up to 700- and 16-fold, for CH 4 and N 2 O, respectively. Mean concentrations were higher in the larger stream than in the smaller stream. In both streams, CH 4 emissions were generally higher in summer-fall and negatively correlated with flow and NO 3 − concentration while N 2 O emissions were generally higher in winter/spring and positively correlated with flow and NO 3 − . In the small stream, diel variations in the concentrations, emissions, and isotopic compositions of CH 4 , N 2 O, and NO 2 − resulted from diel variations in sources, sinks, and air-water gas exchange velocities. Seasonal mean total (CH 4 + N 2 O) area-normalized emission rates, expressed as CO 2 warming potential equivalents, were similar for the two streams, but the total reach-scale emission rate for the larger stream, including CO 2 , was about 2.9 times that of the smaller stream (131.6 vs 46.0 kg CO 2 equivalents km −1 day −1 , respectively). The CH 4 contribution to this flux was 9–28%, despite the relatively high NO 3 − and O 2 concentrations in the streams, indicating contributions from upwelling groundwater or reactions in streambed sediment.

Illinois, Indiana

Reactive transport modeling to understand attenuation of arsenic concentrations in anoxic groundwater during Fe(II) oxidation by nitrate

A previously published field-experimental investigation showed that injection of nitrate in anoxic groundwater that contained aqueous and sediment-bound Fe(II) diminished concentrations of As(V) and As(III) to below drinking-water limits. In the current study, reactive transport modeling confirmed that the observed attenuation was consistent with oxidation of Fe(II) by nitrate, leading to precipitation of hydrous ferric oxide, which, in turn, sorbed both As(V) and As(III). After calibration with site-specific observations, reactive transport modeling could aid in designing effective treatment to remove arsenic using injection of nitrate to oxidize Fe(II).

Book chapter

Anoxic nitrate reduction coupled with iron oxidation and attenuation of dissolved arsenic and phosphate in a sand and gravel aquifer

Nitrate has become an increasingly abundant potential electron acceptor for Fe(II) oxidation in groundwater, but this redox couple has not been well characterized within aquifer settings. To investigate this reaction and some of its implications for redox-sensitive groundwater contaminants, we conducted an in situ field study in a wastewater-contaminated aquifer on Cape Cod. Long-term (15 year) geochemical monitoring within the contaminant plume indicated interacting zones with variable nitrate-, Fe(II)-, phosphate-, As(V)-, and As(III)-containing groundwater. Nitrate and phosphate were derived predominantly from wastewater disposal, whereas Fe(II), As(III), and As(V) were mobilized from the aquifer sediments. Multiple natural gradient, anoxic tracer tests were conducted in which nitrate and bromide were injected into nitrate-free, Fe(II)-containing groundwater. Prior to injection, aqueous Fe(II) concentrations were approximately 175 μM, but sorbed Fe(II) accounted for greater than 90% of the total reactive Fe(II) in the aquifer. Nitrate reduction was stimulated within 1 m of transport for 100 μM and 1000 μM nitrate additions, initially producing stoichiometric quantities of nitrous oxide (>300 μM N). In subsequent injections at the same site, nitrate was reduced even more rapidly and produced less nitrous oxide, especially over longer transport distances. Fe(II) and nitrate concentrations decreased together and were accompanied by Fe(III) oxyhydroxide precipitation and decreases in dissolved phosphate, As(III), and As(V) concentrations. Nitrate N and O isotope fractionation effects during nitrate reduction were approximately equal (ε 15 N/ε 18 O = 1.11) and were similar to those reported for laboratory studies of biological nitrate reduction, including denitrification, but unlike some reported effects on nitrate by denitrification in aquifers. All constituents affected by the in situ tracer experiments returned to pre-injection levels after several weeks. Additionally, Fe(II)-oxidizing, nitrate-reducing microbial enrichment cultures were obtained from aquifer sediments. Growth experiments with the cultures sequentially produced nitrite and nitrous oxide from nitrate while simultaneously oxidizing Fe(II). Field and culture results suggest that nitrogen oxide reduction and Fe(II) oxidation in the aquifer are a complex interaction of coupled biotic and abiotic reactions. Overall, the results of this study demonstrate that anoxic nitrate-dependent iron oxidation can occur in groundwater; that it could control iron speciation; and that the process can impact the mobility of other chemical species (e.g., phosphate and arsenic) not directly involved in the oxidation–reduction reaction.

Massachusetts

Hydrologic controls on nitrogen cycling processes and functional gene abundance in sediments of a groundwater flow-through lake

The fate and transport of inorganic nitrogen (N) is a critically important issue for human and aquatic ecosystem health because discharging N-contaminated groundwater can foul drinking water and cause algal blooms. Factors controlling N-processing were examined in sediments at three sites with contrasting hydrologic regimes at a lake on Cape Cod, MA. These factors included water chemistry, seepage rates and direction of groundwater flow, and the abundance and potential rates of activity of N-cycling microbial communities. Genes coding for denitrification, anaerobic ammonium oxidation (anammox), and nitrification were identified at all sites regardless of flow direction or groundwater dissolved oxygen concentrations. Flow direction was, however, a controlling factor in the potential for N-attenuation via denitrification in the sediments. Potential rates of denitrification varied from 6 to 4500 pmol N/g/h from the inflow to the outflow side of the lake, owing to fundamental differences in the supply of labile organic matter. The results of laboratory incubations suggested that when anoxia and limiting labile organic matter prevailed, the potential existed for concomitant anammox and denitrification. Where oxic lake water was downwelling, potential rates of nitrification at shallow depths were substantial (1640 pmol N/g/h). Rates of anammox, denitrification, and nitrification may be linked to rates of organic N-mineralization, serving to increase N-mobility and transport downgradient.

Massachusetts

Role of anaerobic ammonium oxidation (anammox) in nitrogen removal from a freshwater aquifer

Anaerobic ammonium oxidation (anammox) couples the oxidation of ammonium with the reduction of nitrite, producing N 2 . The presence and activity of anammox bacteria in groundwater were investigated at multiple locations in an aquifer variably affected by a large, wastewater-derived contaminant plume. Anammox bacteria were detected at all locations tested using 16S rRNA gene sequencing and quantification of hydrazine oxidoreductase ( hzo ) gene transcripts. Anammox and denitrification activities were quantified by in situ 15 NO 2 – tracer tests along anoxic flow paths in areas of varying ammonium, nitrate, and organic carbon abundances. Rates of denitrification and anammox were determined by quantifying changes in 28 N 2 , 29 N 2 , 30 N 2 , 15 NO 3 – , 15 NO 2 – , and 15 NH 4 + with groundwater travel time. Anammox was present and active in all areas tested, including where ammonium and dissolved organic carbon concentrations were low, but decreased in proportion to denitrification when acetate was added to increase available electron supply. Anammox contributed 39–90% of potential N 2 production in this aquifer, with rates on the order of 10 nmol N 2 –N L –1 day –1 . Although rates of both anammox and denitrification during the tracer tests were low, they were sufficient to reduce inorganic nitrogen concentrations substantially during the overall groundwater residence times in the aquifer. These results demonstrate that anammox activity in groundwater can rival that of denitrification and may need to be considered when assessing nitrogen mass transport and permanent loss of fixed nitrogen in aquifers.

Environmental Science & Technology

Nitrogen cycling processes and microbial community composition in bed sediments in the Yukon River at Pilot Station

Information on the contribution of nitrogen (N)-cycling processes in bed sediments to river nutrient fluxes in large northern latitude river systems is limited. This study examined the relationship between N-cycling processes in bed sediments and N speciation and loading in the Yukon River near its mouth at the Bering Sea. We conducted laboratory bioassays to measure N-cycling processes in sediment samples collected over distinct water cycle seasons. In conjunction, the microbial community composition in the bed sediments using genes involved in N-cycling ( narG , napA , nosZ , and amoA ) and 16S rRNA gene pyrosequences was examined. Temporal variation was observed in net N mineralization, nitrate uptake, and denitrification rate potentials and correlated strongly with sediment carbon (C) and extractable N content and microbial community composition rather than with river water nutrient concentrations. The C content of the bed sediment was notably impacted by the spring flood, ranging from 1.1% in the midst of an ice-jam to 0.1% immediately after ice-out, suggesting a buildup of organic material (OM) prior to scouring of the bed sediments during ice break up. The dominant members of the microbial community that explained differences in N-processing rates belonged to the genera Crenothrix , Flavobacterium , and the family of Comamonadaceae. Our results suggest that biogeochemical processing rates in the bed sediments appear to be more coupled to hydrology, nutrient availability in the sediments, and microbial community composition rather than river nutrient concentrations at Pilot Station.

Alaska

Long-term groundwater contamination after source removal—The role of sorbed carbon and nitrogen on the rate of reoxygenation of a treated-wastewater plume on Cape Cod, MA, USA

The consequences of groundwater contamination can remain long after a contaminant source has been removed. Documentation of natural aquifer recoveries and empirical tools to predict recovery time frames and associated geochemical changes are generally lacking. This study characterized the long-term natural attenuation of a groundwater contaminant plume in a sand and gravel aquifer on Cape Cod, Massachusetts, after the removal of the treated-wastewater source. Although concentrations of dissolved organic carbon (DOC) and other soluble constituents have decreased substantially in the 15 years since the source was removed, the core of the plume remains anoxic and has sharp redox gradients and elevated concentrations of nitrate and ammonium. Aquifer sediment was collected from near the former disposal site at several points in time and space along a 0.5-km-long transect extending downgradient from the disposal site and analyses of the sediment was correlated with changes in plume composition. Total sediment carbon content was generally low (< 8 to 55.8 &mu;mol (g dry wt)&minus; 1) but was positively correlated with oxygen consumption rates in laboratory incubations, which ranged from 11.6 to 44.7 nmol (g dry wt)&minus; 1 day&minus; 1. Total water extractable organic carbon was < 10&ndash;50% of the total carbon content but was the most biodegradable portion of the carbon pool. Carbon/nitrogen (C/N) ratios in the extracts increased more than 10-fold with time, suggesting that organic carbon degradation and oxygen consumption could become N-limited as the sorbed C and dissolved inorganic nitrogen (DIN) pools produced by the degradation separate with time by differential transport. A 1-D model using total degradable organic carbon values was constructed to simulate oxygen consumption and transport and calibrated by using observed temporal changes in oxygen concentrations at selected wells. The simulated travel velocity of the oxygen gradient was 5&ndash;13% of the groundwater velocity. This suggests that the total sorbed carbon pool is large relative to the rate of oxygen entrainment and will be impacting groundwater geochemistry for many decades. This has implications for long-term oxidation of reduced constituents, such as ammonium, that are being transported downgradient away from the infiltration beds toward surface and coastal discharge zones.

Massachusetts

Linkages between denitrification and dissolved organicmatter quality, Boulder Creek watershed, Colorado

Dissolved organic matter (DOM) fuels the majority of in-stream microbial processes, including the removal of nitrate via denitrification. However, little is known about how the chemical composition of DOM influences denitrification rates. Water and sediment samples were collected across an ecosystem gradient, spanning the alpine to plains, in central Colorado to determine whether the chemical composition of DOM was related to denitrification rates. Laboratory bioassays measured denitrification potentials using the acetylene block technique and carbon mineralization via aerobic bioassays, while organic matter characteristics were evaluated using spectroscopic and fractionation methods. Denitrification potentials under ambient and elevated nitrate concentrations were strongly correlated with aerobic respiration rates and the percent mineralized carbon, suggesting that information about the aerobic metabolism of a system can provide valuable insight regarding the ability of the system to additionally reduce nitrate. Multiple linear regressions (MLR) revealed that under elevated nitrate concentrations denitrification potentials were positively related to the presence of protein-like fluorophores and negatively related to more aromatic and oxidized fractions of the DOM pool. Using MLR, the chemical composition of DOM, carbon, and nitrate concentrations explained 70% and 78% of the observed variability in denitrification potential under elevated and ambient nitrate conditions, respectively. Thus, it seems likely that DOM optical properties could help to improve predictions of nitrate removal in the environment. Finally, fluorescence measurements revealed that bacteria used both protein and humic-like organic molecules during denitrification providing further evidence that larger, more aromatic molecules are not necessarily recalcitrant in the environment.

Colorado

Groundwater-quality data for a treated-wastewater plume near the Massachusetts Military Reservation, Ashumet Valley, Cape Cod, Massachusetts, 2006-08

A plume of contaminated groundwater extends from former disposal beds at the Massachusetts Military Reservation's wastewater-treatment plant toward Ashumet Pond, coastal ponds, and Vineyard Sound, Cape Cod, Massachusetts. Treated sewage-derived wastewater was discharged to the rapid-infiltration beds for nearly 60 years before the disposal site was moved to a different location in December 1995. Water-quality samples were collected from monitoring wells, multilevel samplers, and profile borings to characterize the nature and extent of the contaminated groundwater and to observe the water-quality changes after the wastewater disposal ceased. Data are presented here for water samples collected in 2007 from 394 wells (at 121 well-cluster locations) and 780 multilevel-sampler ports (at 42 locations) and in 2006-08 at 306 depth intervals in profile borings (at 20 locations) in and near the treated-wastewater plume. Analyses of these water samples for field parameters (specific conductance, pH, dissolved oxygen and phosphate concentrations, and alkalinity); absorbance of ultraviolet/visible light; and concentrations of nitrous oxide, dissolved organic carbon, methylene blue active substances, selected anions and nutrients, including nitrate and ammonium, and selected inorganic solutes, including cations, anions, and minor elements, are presented in tabular format. The natural restoration of the sand and gravel aquifer after removal of the treated-wastewater source, along with interpretations of the water quality in the treated-wastewater plume, have been documented in several published reports that are listed in the references.

Massachusetts

Potential For Denitrification near Reclaimed Water Application Sites in Orange County, Florida, 2009

The potential for denitrification was tested in water samples from four Upper Floridan aquifer wells near a reclaimed water application site, in west Orange County Florida, and two adjacent springs. Results of the study indicate that denitrifying bacteria are present in the groundwater and spring water samples, and that these bacteria can readily denitrify the waters when suitable geochemical conditions exist. The acetylene block technique was used to assess nitrous oxide in the samples that was produced by denitrification. The laboratory incubation experiment consisted of four different treatments to each of the six samples: (1) ambient water (no added nitrate or glucose), (2) ambient water amended with 1.4 milligrams per liter (mg/L) nitrate as nitrogen (N), (3) ambient water amended with 5.0 mg/L nitrate as N, and (4) ambient water amended with 5.0 mg/L nitrate as N and 10 mg/L glucose as C 6 H 12 O 6 . A companion set of incubations using treatment 2 tracked changes in nitrate and nitrite concentration with time. The rate of denitrification in treatment 2 ranged from 0.059 to 0.124 milligram per liter per day nitrogen [(mg/L)/d N] and in treatment 3 ranged from 0.071 to 0.226 (mg/L)/d N. At all of the sampling sites, treatment 4 yielded denitrification rates at least an order of magnitude greater than those measured for the other treatments; rates ranged from 2.3 to 4.4 (mg/L)/d N. The electron donor supply, dissolved organic carbon, in the groundwater and springwater is sufficient to remove at least 1.1-1.4 mg/L nitrate as N in 20 to 30 days, as indicated by nitrous oxide production rates under ambient conditions (treatment 1). The even higher nitrate removal observed with addition of supplemental carbon in treatment 4 suggests that carbon is a limiting nutrient in this reaction. Denitrifying activity might explain the low ambient nitrate concentrations in the Upper Floridan aquifer in this area.

Florida

Geochemistry of inorganic nitrogen in waters released from coal-bed natural gas production wells in the Powder River Basin, Wyoming

Water originating from coal-bed natural gas (CBNG) production wells typically contains ammonium and is often disposed via discharge to ephemeral channels. A study conducted in the Powder River Basin, Wyoming, documented downstream changes in CBNG water composition, emphasizing nitrogen-cycling processes and the fate of ammonium. Dissolved ammonium concentrations from 19 CBNG discharge points ranged from 95 to 527 μM. Within specific channels, ammonium concentrations decreased with transport distance, with subsequent increases in nitrite and nitrate concentrations. Removal efficiency, or uptake, of total dissolved inorganic nitrogen (DIN) varied between channel types. DIN uptake was greater in the gentle-sloped, vegetated channel as compared to the incised, steep, and sparsely vegetated channel and was highly correlated with diel patterns of incident light and dissolved oxygen concentration. In a larger main channel with multiple discharge inputs ( n = 13), DIN concentrations were >300 μM, with pH > 8.5, after 5 km of transport. Ammonium represented 25−30% of the large-channel DIN, and ammonium concentrations remained relatively constant with time, with only a weak diel pattern evident. In July 2003, the average daily large-channel DIN load was 23 kg N day −1 entering the Powder River, an amount which substantially increased the total Powder River DIN load after the channel confluence. These results suggest that CBNG discharge may be an important source of DIN to western watersheds, at least at certain times of the year, and that net oxidation and/or removal is dependent upon the extent of contact with sediment and biomass, type of drainage channel, and time of day.

Wyoming

Multi-scale measurements and modeling of denitrification in streams with varying flow and nitrate concentration in the upper Mississippi River basin, USA

Denitrification is an important net sink for NO 3 − in streams, but direct measurements are limited and in situ controlling factors are not well known. We measured denitrification at multiple scales over a range of flow conditions and NO 3 − concentrations in streams draining agricultural land in the upper Mississippi River basin. Comparisons of reach-scale measurements (in-stream mass transport and tracer tests) with local-scale in situ measurements (pore-water profiles, benthic chambers) and laboratory data (sediment core microcosms) gave evidence for heterogeneity in factors affecting benthic denitrification both temporally (e.g., seasonal variation in NO 3 − concentrations and loads, flood-related disruption and re-growth of benthic communities and organic deposits) and spatially (e.g., local stream morphology and sediment characteristics). When expressed as vertical denitrification flux per unit area of streambed ( U denit , in μmol N m −2 h −1 ), results of different methods for a given set of conditions commonly were in agreement within a factor of 2–3. At approximately constant temperature (~20 ± 4°C) and with minimal benthic disturbance, our aggregated data indicated an overall positive relation between U denit (~0–4,000 μmol N m −2 h −1 ) and stream NO 3 − concentration (~20–1,100 μmol L −1 ) representing seasonal variation from spring high flow (high NO 3 − ) to late summer low flow (low NO 3 − ). The temporal dependence of U denit on NO 3 − was less than first-order and could be described about equally well with power-law or saturation equations (e.g., for the unweighted dataset, U denit ≈26 * [NO 3 − ] 0.44 or U denit ≈640 * [NO 3 − ]/[180 + NO 3 − ]; for a partially weighted dataset, U denit ≈14 * [NO 3 − ] 0.54 or U denit ≈700 * [NO 3 − ]/[320 + NO 3 − ]). Similar parameters were derived from a recent spatial comparison of stream denitrification extending to lower NO 3 − concentrations (LINX2), and from the combined dataset from both studies over 3 orders of magnitude in NO 3 − concentration. Hypothetical models based on our results illustrate: (1) U denit was inversely related to denitrification rate constant ( k 1 denit , in day −1 ) and vertical transfer velocity ( v f,denit , in m day −1 ) at seasonal and possibly event time scales; (2) although k 1 denit was relatively large at low flow (low NO 3 − ), its impact on annual loads was relatively small because higher concentrations and loads at high flow were not fully compensated by increases in U denit ; and (3) although NO 3 − assimilation and denitrification were linked through production of organic reactants, rates of NO 3 − loss by these processes may have been partially decoupled by changes in flow and sediment transport. Whereas k 1 denit and v f,denit are linked implicitly with stream depth, NO 3 − concentration, and(or) NO 3 − load, estimates of U denit may be related more directly to field factors (including NO 3 − concentration) affecting denitrification rates in benthic sediments. Regional regressions and simulations of benthic denitrification in stream networks might be improved by including a non-linear relation between U denit and stream NO 3 − concentration and accounting for temporal variation.

Biogeochemistry

Microbial and chemical factors influencing methane production in laboratory incubations of low-rank subsurface coals

Lignite and subbituminous coals were investigated for their ability to support microbial methane production in laboratory incubations. Results show that naturally-occurring microorganisms associated with the coals produced substantial quantities of methane, although the factors influencing this process were variable among different samples tested. Methanogenic microbes in two coals from the Powder River Basin, Wyoming, USA, produced 140.5-374.6 mL CH 4 /kg ((4.5-12.0 standard cubic feet (scf)/ton) in response to an amendment of H 2 /CO 2 . The addition of high concentrations (5-10 mM) of acetate did not support substantive methane production under the laboratory conditions. However, acetate accumulated in control incubations where methanogenesis was inhibited, indicating that acetate was produced and consumed during the course of methane production. Acetogenesis from H 2 /CO 2 was evident in these incubations and may serve as a competing metabolic mode influencing the cumulative amount of methane produced in coal. Two low-rank (lignite A) coals from Fort Yukon, Alaska, USA, demonstrated a comparable level of methane production (131.1-284.0 mL CH4/kg (4.2-9.1 scf/ton)) in the presence of an inorganic nutrient amendment, indicating that the source of energy and organic carbon was derived from the coal. The concentration of chloroform-extractable organic matter varied by almost three orders of magnitude among all the coals tested, and appeared to be related to methane production potential. These results indicate that substrate availability within the coal matrix and competition between different groups of microorganisms are two factors that may exert a profound influence on methanogenesis in subsurface coal beds.

International Journal of Coal Geology