Hydrological variability, organic matter supply and denitrification in the Garonne River ecosystem

1. Groundwater nitrate contamination has become a worldwide problem as increasing amounts of nitrogen fertilisers are used in agriculture. Alluvial groundwater is uniquely juxtaposed between soils and streams. Hydrological connections among these subsystems regulate nutrient cycling. 2. We measured denitrification using an in situ acetylene‐block assay in a nitrate‐contaminated portion of the Garonne River catchment along a gradient of surface water–ground water mixing during high (snowmelt) and low flow. 3. During high flow (mid‐April to early June) the water table rose an average of 35 cm and river water penetrated the subsurface to a great extent in monitoring wells. Denitrification rates averaged 5.40 μgN₂O L^?1 min^?1 during the high flow period, nearly double the average rate (2.91 μgN₂O L^?1 min^?1) measured during base flow. This was driven by a strong increase in denitrification in groundwater under native riparian vegetation. Nitrate concentrations were significantly lower during high flow compared with base flow. Riparian patches had higher dissolved organic carbon concentrations that were more aromatic compared with the gravel bar patch closest to the river. 4. Multiple linear regression showed that the rate of denitrification was best predicted by the concentration of low molecular weight organic acids. These molecules are probably derived from decomposition of soil organic matter and are an important energy source for anaerobic respiratory processes like denitrification. The second best predictor was per cent surface water, reflecting higher denitrification rates during spring when hydrological connection between surface water and ground water was greatest. 5. Our results indicate that, while denitrification rates in Garonne River alluvium were spatially and temporally variable, denitrification was a significant NO₃ sink during transport from the NO₃‐contaminated floodplain to the river. DOC availability and river–floodplain connectivity were important factors influencing observed spatial and temporal patterns.     

Nitrate retention in a sand plains stream and the importance of groundwater discharge

We measured net nitrate retention by mass balance in a 700-m upwelling reach of a third-order sand plains stream, Emmons Creek, from January 2007 to November 2008. Surface water and groundwater fluxes of nitrate were determined from continuous records of discharge and from nitrate concentrations based on weekly and biweekly sampling at three surface water stations and in 23 in-stream piezometers, respectively. Surface water nitrate concentration in Emmons Creek was relatively high (mean of 2.25 mg NO₃?CN l^?1) and exhibited strong seasonal variation. Net nitrate retention averaged 429 mg NO₃?CN m^?2 d^?1 and about 2% of nitrate inputs to the reach. Net nitrate retention was highest during the spring and autumn when groundwater discharge was elevated. Groundwater discharge explained 57?C65% of the variation in areal net nitrate retention. Specific discharge and groundwater nitrate concentration varied spatially. Weighting groundwater solute concentrations by specific discharge improved the water balance and resulted in higher estimates of nitrate retention. Our results suggest that groundwater inputs of nitrate can drive nitrate retention in streams with high groundwater discharge.     

Denitrification in a nitrogen-limited stream ecosystem

Denitrification was measured in hyporheic, parafluvial, and bank sediments of Sycamore Creek, Arizona, a nitrogen-limited Sonoran Desert stream. We used three variations of the acetylene block technique to estimate denitrification rates, and compared these estimates to rates of nitrate production through nitrification. Subsurface sediments of Sycamore Creek are typically well-oxygenated, relatively low in nitrate, and low in organic carbon, and therefore are seemingly unlikely sites of denitrification. However, we found that denitrification potential (C & N amended, anaerobic incubations) was substantial, and even by our conservative estimates (unamended, oxic incubations and field chamber nitrous oxide accumulation), denitrification consumed 5–40% of nitrate produced by nitrification. We expected that denitrification would increase along hyporheic and parafluvial flowpaths as dissolved oxygen declined and nitrate increased. To the contrary, we found that denitrification was generally highest at the upstream ends of subsurface flowpaths where surface water had just entered the subsurface zone. This suggests that denitrifiers may be dependent on the import of surface-derived organic matter, resulting in highest denitrification rate at locations of surface-subsurface hydrologic exchange. Laboratory experiments showed that denitrification in Sycamore Creek sediments was primarily nitrogen limited and secondarily carbon limited, and was temperature dependent. Overall, the quantity of nitrate removed from the Sycamore Creek ecosystem via denitrification is significant given the nitrogen-limited status of this stream.     

Enhanced hyporheic exchange flow around woody debris does not increase nitrate reduction in a sandy streambed

Anthropogenic nitrogen pollution is a critical problem in freshwaters. Although riverbeds are known to attenuate nitrate, it is not known if large woody debris (LWD) can increase this ecosystem service through enhanced hyporheic exchange and streambed residence time. Over a year, we monitored the surface water and pore water chemistry at 200 points along a ~ 50 m reach of a lowland sandy stream with three natural LWD structures. We directly injected ¹⁵N-nitrate at 108 locations within the top 1.5 m of the streambed to quantify in situ denitrification, anammox and dissimilatory nitrate reduction to ammonia, which, on average, contributed 85, 10 and 5% of total nitrate reduction, respectively. Total nitrate reducing activity ranged from 0 to 16 µM h^?1 and was highest in the top 30 cm of the stream bed. Depth, ambient nitrate and water residence time explained 44% of the observed variation in nitrate reduction; fastest rates were associated with slow flow and shallow depths. In autumn, when the river was in spate, nitrate reduction (in situ and laboratory measures) was enhanced around the LWD compared with non-woody areas, but this was not seen in the spring and summer. Overall, there was no significant effect of LWD on nitrate reduction rates in surrounding streambed sediments, but higher pore water nitrate concentrations and shorter residence times, close to LWD, indicated enhanced delivery of surface water into the streambed under high flow. When hyporheic exchange is too strong, overall nitrate reduction is inhibited due to short flow-paths and associated high oxygen concentrations.     

Nitrogen transformations at the sediment–water interface across redox gradients in the Laurentian Great Lakes

The capacity of a lake to remove reactive nitrogen (N) through denitrification has important implications both for the lake and for downstream ecosystems. In large oligotropic lakes such as Lake Superior, where nitrate (NO₃ ^?) concentrations have increased steadily over the past century, deep oxygen penetration into sediments may limit the denitrification rates. We tested the hypothesis that the position of the redox gradient in lake sediments affects denitrification by measuring net N-fluxes across the sediment–water interface for intact sediment cores collected across a range of sediment oxycline values from nearshore and offshore sites in Lake Superior, as well as sites in Lake Huron and Lake Erie. Across this redox gradient, as the thickness of the oxygenated sediment layer increased from Lake Erie to Lake Superior, fluxes of NH₄ ⁺ and N₂ out of the sediment decreased, and sediments shifted from a net sink to a net source of NO₃ ^?. Denitrification of NO₃ ^? from overlying water decreased with thickness of the oxygenated sediment layer. Our results indicate that, unlike sediments from Lake Erie and Lake Huron, Lake Superior sediments do not remove significant amounts of water column NO₃ ^? through denitrification, likely as a result of the thick oxygenated sediment layer.     

Microelectrode Measurements of Nitrate Gradients in the Littoral and Profundal Sediments of a Meso-Eutrophic Lake (Lake Vechten, The Netherlands)

NO₃⁻ concentration profiles were measured in the sediments of a meso-eutrophic lake with a newly developed microelectrode. The depth of penetration of NO₃⁻ varied from only 1.3 mm in organic-rich profundal silty sediments to 5 mm in organic-poor littoral sandy sediments. The thickness of the zone of denitrification in the organic-rich sediments was <500 μm. Oxygen profiles measured simultaneously revealed that the zone of denitrification was directly adjacent to the aerobic zone. The results demonstrate high denitrification rates (0.26 to 1.31 mmol m⁻² day⁻¹) at in situ nitrate concentrations in the overlying water (0.030 mmol liter⁻¹) and limitation of denitrification by nitrate availability.     

Importance of transient storage zones for ammonium and phosphate retention in a sandy-bottom Mediterranean stream

1. The ability of hyporheic sediments to exchange water and retain ammonium and phosphate in the Riera Major stream ,North-East Spain, under different discharge conditions was measured by conducting short-term nutrient and chloride additions. 2. The mean exchange coefficients from free-flowing water to the storage zone (k₁) and vice versa (k₂) were 0.82 × 10–4 s^??1 and 7 × 10^??3 s^??1, respectively. The ratio of storage zone cross-sectional area to stream cross-sectional area (A_S/A) averaged 2.8 × 10–2 and was negatively correlated with discharge (r = –0.85, d.f. = 13, P < 0.001). 3. The percentage of hyporheic zone water which came from surface water varied as a function of discharge and hyporheic depth, ranging between 33% and 95% at 25 cm depth, and between 78% and 100% at 10 cm depth. 4. The nutrient retention efficiency in the hyporheic zone at 10 cm depth measured as uptake length (S_wh) was less than 3.3 cm for ammonium and 37 cm for phosphate. Higher nutrient retentions were measured in the sediments at 10 cm depth than at 25 cm, indicating that near-surface sediments were involved more actively in phosphate retention than the deeper hyporheic sediments. The lack of ammonium at any depth of the hyporheic zone showed that ammonium was very rapidly taken up in the surfacial sediments.     

A mixing model analysis of stream solute dynamics and the contribution of a hyporheic zone to ecosystem function*

1. We monitored streamwater and streambed sediment porewaters from White Clay Creek (WCC), SE Pennsylvania, for dissolved organic carbon (DOC), dissolved oxygen (DO) and conductivity to investigate organic matter processing within the hyporheic zone. Dissolved organic carbon and DO concentrations were higher in the streamwater than in the porewaters and, in many cases, concentrations continued to diminish with increasing depth into the streambed. 2. Hydrological exchange data demonstrated that the permeability of the stream bed declines with depth and constrains downwelling, effectively isolating porewaters >30 cm from streamwater. 3. End‐member mixing analysis (EMMA) based on conductivity documented a DOC source and DO sink in the hyporheic zone. We calculated hyporheic streambed DOC fluxes and respiration from the EMMA results and estimates of water flux. Based upon our calculations of biodegradable DOC entering the hyporheic zone, we estimate that DOC supports 39% of the hyporheic zone respiration, with the remaining 61% presumably being supported by entrained particulate organic carbon. Hyporheic respiration averaged 0.38 g C m^?2 d^?1, accounted for 41% of whole ecosystem respiration, and increased baseflow ecosystem efficiency from 46 to 59%. 4. Advective transport of labile organic molecules into the streambed concentrates microbial activity in near‐surface regions of the hyporheic zone. Steep gradients in biogeochemical activity could explain how a shallow and hydrologically constrained hyporheic zone can dramatically influence organic matter processing at the ecosystem scale.     

FACTORS REGULATING THE SPATIAL DISTRIBUTION OF THE FILAMENTOUS ALGA PITHOPHORA OEDOGONIA (CHLOROPHYCEAE) IN AN INDIANA LAKE1

Pithophora oedogonia (Mont.) Wittr. biomass in Surrey Lake, Indiana was greater in the littoral than in the pelagial region. Although mean soluble reactive phosphorus concentrations did not differ between the two areas, nitrate concentrations were almost six times higher in the cove than in the open water. Using laboratory cultures of Pithophora, the half saturation constant (K_s at 20° C relating filament growth to external concentrations of nitrate-nitrogen was determined to be 1.23 mg L^?1 (=88 μM)and for phosphate-phosphorus, 0.1 mg L^?1 (=3.22 μM). These values were used to calculate a NO₃-N/PO₄-P atomic ratio of 27.6. Comparison of this value with NO₃-N/PO₄-P ratios in Surrey Lake showed that nitrogen limiting conditions were prevalent in the open water section of the lake. Alkaline phosphatase and dark ammonia uptake analyses on field collected filaments from the shallow and deep water sections confirmed the hypothesis that nitrate is the major factor limiting growth of Pithophora in Surrey Lake.     

Methanogenesis in Arizona,USA dryland streams

Methanogenesis was studied in five streams of central and southern Arizona by examining the distribution of methane in interstitial water and evasion of methane in three subsystems (hyporheic, parafluvial and bank sediments). In Sycamore Creek, the primary study site (studied during summer and early autumn), methane content of interstitial water exhibited a distinct spatial pattern. In hyporheic (sediments beneath the wetted channel) and parfluvial zones (active channel sediments lateral to the wetted channel), which were well oxygenated due to high hydrologic exchange with the surface stream and had little particulate organic matter (POM), interstitial methane concentration averaged only 0.03 mgCH₄-C/L. Bank sediments (interface between the active channel and riparian zone), in contrast, which were typically vegetated, had high POM, low hydrologic exchange and concomitantly low dissolved oxygen levels, had interstitial concentration averaging 1.5 mgCH4-C/L. Methane emission from Sycamore Creek, similar to methane concentration, averaged only 3.7 mgCH₄-C·m⁻²·d⁻¹ from hyporheic and parafluvial zones as opposed to 170 mgCH₄-C·m⁻²·d⁻¹ from anoxic bank sediments. Methane in four additional streams sampled (one sampling date during late winter) was low and exhibited little spatial variation most likely due to cooler stream temperatures. Interstitial methane in parafluvial and bank sediments of all four streams ranged from only 0.005 to 0.1 mgCH₄-C/L. Similarly methane evasion was also low from these streams varying from 0 to 5.7 mgCH₄-C·m⁻²·d⁻¹. The effects of organic matter and temperature on methanogenesis were further examined by experimentally manipulating POM and temperature in stoppered flasks filled with hyporheic sediments and stream water. Methane production significantly increased with all independent variables. Methane production is greatest in bank sediments that are relatively isolated hydrologically and lowest in hyporheic and parafluvial sediments that are interactive with the surface stream.     

Influence of hydrological connectivity of riverine wetlands on nitrogen removal via denitrification

Wetland ecosystems in agricultural areas often become progressively more isolated from main water bodies. Stagnation favors the accumulation of organic matter as the supply of electron acceptors with water renewal is limited. In this context it is expected that nitrogen recycling prevails over nitrogen dissipation. To test this hypothesis, denitrification rates, fluxes of dissolved oxygen (SOD), inorganic carbon (DIC) and nitrogen and sediment features were measured in winter and summer 2007 on 22 shallow riverine wetlands in the Po River Plain (Northern Italy). Fluxes were determined from incubations of intact cores by measurement of concentration changes or isotope pairing in the case of denitrification. Sampled sites were eutrophic to hypertrophic; 10 were connected and 12 were isolated from the adjacent rivers, resulting in large differences in nitrate concentrations in the water column (from <5 to 1,133 μM). Benthic metabolism and denitrification rates were investigated by two overarching factors: season and hydrological connectivity. SOD and DIC fluxes resulted in respiratory quotients greater than one at most sampling sites. Sediment respiration was coupled to both ammonium efflux, which increased from winter to summer, and nitrate consumption, with higher rates in river-connected wetlands. Denitrification rates measured in river-connected wetlands (35–1,888 μmol N m^?2 h^?1) were up to two orders of magnitude higher than rates measured in isolated wetlands (2–231 μmol N m^?2 h^?1), suggesting a strong regulation of the process by nitrate availability. These rates were also significantly higher in summer (9–1,888 μmol N m^?2 h^?1) than in winter (2–365 μmol N m^?2 h^?1). Denitrification supported by water column nitrate (D_W) accounted for 60–100% of total denitrification (Dtot); denitrification coupled to nitrification (D_N) was probably controlled by limited oxygen availability within sediments. Denitrification efficiency, calculated as the ratio between N removal via denitrification and N regeneration, and the relative role of denitrification for organic matter oxidation, were high in connected wetlands but not in isolated sites. This study confirms the importance of restoring hydraulic connectivity of riverine wetlands for the maintenance of important biogeochemical functions such as nitrogen removal via denitrification.     

Three-dimensional spatial patterns of trace gas concentrations in baseflow-dominated agricultural streams: implications for surface–ground water interactions and biogeochemistry

Small streams that drain agricultural landscapes have come under close scrutiny as potentially significant indirect sources of greenhouse gases (GHGs) to the atmosphere. By exploring the stream-ground water connection in three dimensional space (horizontally and vertically beneath the stream channel, and longitudinally along the stream corridor) our results show (1) ground water can be a significant source of greenhouse gases to streams draining agricultural watersheds with concentrations in excess of atmospheric equilibrium by 221?μmol?C?L^?1 carbon dioxide, 0.64?μmol?C?L^?1 methane, and 0.65?μmol?N?L^?1 nitrous oxide (N₂O); (2) changes in the stream-ground water connection can create seemingly erratic patterns in GHG concentrations over short longitudinal distances (order of meters); (3) soil-stream interfaces are hotspots for denitrification and methanogenesis; however, no significant N₂O production was observed at such an interface under a riparian forest; and (4) nitrate (NO₃ ^?) and N₂O can be preserved as electron acceptors in oxic ground waters draining agriculture landscapes; hence, soil nitrification was the major source of N₂O to stream water, with a legacy in ground water dating back to the 1960s; N₂O tracked the seepage of NO₃ ^? into surface waters. In this study, we demonstrate the utility of detailed measurements of multiple trace gases towards revealing spatial and temporal patterns of surface–ground water interactions and biogeochemistry across several small baseflow-dominated stream ecosystems in central Wisconsin, USA.     

Reduction of nitrate in clayey subsoils controlled by geochemical and microbial barriers

Vertical distribution of redox zones, concentrations of redox‐sensitive constituents, numbers of aerobic heterotrophic bacteria, and potential denitrification activity were studied in 1‐m cores taken at the transition between the oxidized and reduced layers in two Danish clayey subsoils. Based on the matrix soil colors, a redox sequence of oxidized, suboxic, and reduced zones was identified at both sites. The geochemical composition of the oxidized brown colored zone (to depths of 2.6 and 3.2 m) was characterized by high concentrations of NO₃ ^? and low amounts of total organic carbon, exchangeable forms of NH₄ ⁺, Fe²⁺, and Mn²⁺, and structural Fe(II) in the clay minerals. In the underlying 20‐ to 30‐cm‐deep suboxic zone, decreasing NO₃ ^? concentrations were observed together with increasing amount of exchangeable forms of Fe²⁺ and Mn²⁺, and structural Fe(II). Finally, in the reduced grey zone, NO₃ ^? was no longer present and maximum concentrations of other redox sensitive constituents occurred. Throughout the subsoils, the distribution of exchangeable Fe²⁺ corresponded most closely to changes in the colors of redox zones. The low‐organic Havrebjerg site displayed geochemical profiles indicating that NO₃ ^? was chemically reduced by structural Fe(II) in the clay minerals of the suboxic zone, and that the Fe(II) formed a geochemical barrier for the downward progression of NO₃ ^?. Aerobic heterotrophic bacteria occurred only in low numbers at this site and potential denitrification activity was very low. In contrast, the Sparresholm site had a significant population of bacteria in the suboxic zone, which also contained a heterogeneous distribution of potential denitrification activity. Specific microsites with facilitated transport of soluble organic substrates are proposed to support the denitrification activity in a heterogeneous distribution, constituting a microbial barrier for downward progression of NO₃ ^? in this subsoil.     

Nitrate reduction in marine sediment: Pathways and interactions with iron and sulfur cycling

Abstract

In coastal marine sediments, the interactions between NO₃ ^? reduction and transformations of Fe and S compounds often occur in a strong gradient of electron activity ("redoxcline"). Denitrification activity is observed throughout the NC₃ ^?‐containing surface zone, although the reduction step from N₂O to N₂ can be inhibited by H₂S in the “redoxcline.”; Survival of denitrifiers is generally poor in NO₃ ^?‐free, reduced sediment; such populations are likely to employ Fe³⁺ reduction in their energy metabolism. At depth, the sediments often contain a larger capacity for “nitrate ammonification”; (dissimilatory NO₃ ^? reduction to NH₄ ⁺) than for denitrification. The “nitrate ammonification”; is found commonly among fermenting bacteria, although SO₄ ^2? reducers may also be involved. In situ activities observed in whole sediment cores indicate that “nitrate ammonification”; may account for as much as one‐third of the carbon oxidation in organic‐rich sediments. The control of partitioning between denitrification and “nitrate ammonification”; at low NO₃ ^? concentrations is poorly investigated, but the larger metabolic capacity of fermenting and S O₄ ^2?‐reducing baceria in relatively reduced sediment could be important. In addition to bacterial reduction, chemical NO₃ ^? reduction is possible where significant amounts of Fe²⁺ (or H₂S) accumulate in the “redoxcline.”;     

Ground water flow paths in relation to nitrogen chemistry in the near-stream zone

Interactions between ground water flow paths and water chemistry were studied in the riparian zone of a small headwater catchment near Toronto, Ontario. Significant variations in oxygen — 18 and chloride indicated the presence of distinct sources of water in the ground water flow system entering the near-stream zone. Shallow ground water at the upland perimeter of the riparian zone had nitrate-N, chloride and dissolved oxygen concentrations which ranged between 100–180 µg L^–1, 1.2–1.8 mg L^–1 and 4.6–9.1 mg L^–1 respectively. Concentrations of nitrate — N in deep ground water flowing upward beneath the riparian wetland were < 10 µg L^–1, whereas chloride and dissolved oxygen ranged between 0.6–0.9 mg L^–1 and 0.4–2.2 mg L^–1 respectively. Ammonium — N concentrations (20–60 µg L^–1) were similar in shallow and deep ground water. Ground water was transported through the wetland to the stream by three hydrologic pathways. 1) Shallow ground water emerged as springs near the base of the hillslope producing surface rivulets which crossed the riparian zone to the stream. 2) Deep ground water flowed upward through organic soils and entered the rivulets within the wetland. 3) Deep ground water reached the stream as bed and bank seepage. Springs were higher in nitrate and chloride than rivulets entering the stream, whereas bank seeps had lower concentrations of nitrate and chloride and considerably higher ammonium concentrations than the rivulets. These contrasts in nitrate and chloride concentrations were related to initial differences in the ion chemistry of shallow and deep ground water rather than to element transformations within the riparian wetland. Differences in ammonium concentration between seeps and rivulets were caused by immobilization of ammonium in the substrates of aerobic rivulets, whereas little ammonium depletion probably occurred in deep ground water flowing upward through reduced subsurface organic soils around the stream perimeter.     

Flood effects on invertebrates, sediments and particulate organic matter in the hyporheic zone of a gravel-bed stream

1. We investigated the effects of a flood on the fauna and physical habitat of the hyporheic zone of the Kye Burn, a fourth order gravel‐bed stream in New Zealand. 2. Freeze core hyporheic samples (to 50 cm depth) and benthic samples (to 10 cm) were taken, along with measurements of vertical hydrological gradient, before, 2 days after and 1 month after the flood (estimated return period: 1.5 years, estimated Q_max = 10.4 m³ s^?1). 3. The composition of the hyporheos differed over the three sampling occasions with fewer taxa collected immediately postflood than preflood. The equitability of the community was higher on both postflood occasions, consistent with the reduced densities of two abundant taxa (Leptophlebiidae and Copepoda). 4. Total invertebrate abundance was lower on the postflood occasions than preflood in both benthic (0–10 cm) and hyporheic (10–50 cm) sediments. Several taxa, including asellotan isopods and amphipods, recovered within 1 month of the event. Hyporheic densities of larval Hydora and nematodes did not differ among the three sampling occasions, but the water mite Pseudotryssaturus was more abundant 1 month after the flood than preflood. There was no evidence of vertical movements (to 50 cm) by any taxa in response to the flood. 5. The proportion of fine sediments (<1 mm) in the subsurface sediments (10–50 cm) increased over the three sampling occasions and median particle size declined, but sediment porosity did not change. More particulate organic matter was found in the sediments after the flood. 6. Our study provides little evidence that the hyporheic zone (to 50 cm) acted as a significant refuge during the flood event, although movements to or recolonisation from sediments deeper than 50 cm could explain the recovery of many crustacean and mite taxa within 1 month.     

Relationships between DOC bioavailability and nitrate removal in an upland stream: An experimental approach

The Catskill Mountains of southeastern New York State have among thehighest rates of atmospheric nitrogen deposition in the United States. Somestreams draining Catskill catchments have shown dramatic increases in nitrateconcentrations while others have maintained low nitrate concentrations. Streamsin which exchange occurs between surface and subsurface (i.e. hyporheic) watersare thought to be conducive to nitrate removal via microbial assimilationand/ordenitrification. Hyporheic exchange was documented in the Neversink River inthesouthern Catskill Mountains, but dissolved organic carbon (DOC) and nitrate(NO₃ ^–) losses along hyporheic flowpaths werenegligible. In this study, Neversink River water was amended with natural,bioavailable dissolved organic carbon (BDOC) (leaf leachate) in a series ofexperimental mesocosms that simulated hyporheic flowpaths. DOC and N dynamicswere examined before and throughout a three week BDOC amendment. In addition,bacterial production, dissolved oxygen demand, denitrification, and sixextracellular enzyme activities were measured to arrive at a mechanisticunderstanding of potential DOC and NO₃ ^– removalalong hyporheic flowpaths. There were marked declines in DOC and completeremoval of nitrate in the BDOC amended mesocosms. Independent approaches wereused to partition NO₃ ^– loss into two fractions:denitrification and assimilation. Microbial assimilation appears to be thepredominant process explaining N loss. These results suggest that variabilityinBDOC may contribute to temporal differences in NO₃ ^–export from streams in the Catskill Mountains.     

Mass spectrometric monitoring of gases (CO2, CH4, O2) in a mesotrophic peat core from Kopparås Mire, Sweden

Membrane inlet mass spectrometry was used to monitor dissolved gas concentrations (CO₂, CH₄ and O₂) in a mesotrophic peat core from Kopparås, Sweden. 1 A comparison of depth profiles (down to 22 cm) with an ombrotrophic peat core (Ellergower, SW Scotland) investigated previously, revealed major differences in gas concentrations. Thus methane reached concentrations more than twice as high (800 μM) at depths greater than 12 cm in the Kopparås core. As shown previously, the primary determinant of the depth of the oxic zone is the level of the water table. Whereas in the Scottish cores, mass spectrometric detectability of O₂ was confined to the first 3 cm below this level, in the Swedish core penetration of O₂ was greater (7 cm). CO₂ profiles were similar in cores from both locations. 2 A thick layer of Sphagnum mosses dominated the plant cover of the Swedish peat core. A poorly developed deep root system, as distinct from that of the vascular plant cover in Scottish cores, diminished gas exchange rates, and presumably aerobic methane oxidation at depth around roots. These characteristics may contribute to the development of discontinuities in gas profiles at depths greater 15 cm as upward gas transport is established predominantly by diffusion and/or ebullition in the Swedish core. 3 Monitoring gas concentrations at the peat surface and at 2 cm depth after changing water tables showed a delayed response of approximately 4 days as a result of the high water content and moisture‐regulating capacity of mosses. 4 Recovery processes at 2 cm depth after raising the water table revealed final production rates of dissolved CO₂ and CH₄ in the peat pore water between 0.8 and 4.4 μmol h^?1 L^?1 and between 0.1 and 1.7 μmol h^?1 L^?1, respectively. Higher production rates were found during the day, indicating a diurnal rhythm due to plant photosynthetic activity even at the low values of photosynthetically active radiation (PAR: 110 μmol s^?1 m^?2) used in the experimental set‐up. 5 In the water‐logged mesotrophic Kopparås core changes of dissolved gas concentrations (DGC) at 3 and 14 cm depth were surface temperature‐dependent rather than light dependent. This suggests that changes of air temperature alters the covering vegetation to increase the conductivity for dissolved gases through vascular plants and to facilitate gas transport by diffusion and/or ebullition.     

The kinetics of denitrification in permeable sediments

Permeable sediments comprise the majority of shelf sediments, yet the rates of denitrification remain highly uncertain in these environments. Computational models are increasingly being used to understand the dynamics of denitrification in permeable sediments, which are complex environments to study experimentally. The realistic implementation of such models requires reliable experimentally derived data on the kinetics of denitrification. Here we undertook measurements of denitrification kinetics as a function of nitrate concentration in carefully controlled flow through reactor experiments on sediments taken from six shallow coastal sites in Port Phillip Bay, Victoria, Australia. The results showed that denitrification commenced rapidly (within 30 min) after the onset of anoxia and the kinetics could be well described by Michaelis–Menten kinetics with half saturation constants (apparent K_m) ranging between 1.5 and 19.8 μM, and maximum denitrification rate (V_max) were in the range of 0.9–7.5 nmol mL^?1 h^?1. The production of N₂ through anaerobic ammonium oxidation (anammox) was generally found to be less than 10 % of denitrification. V_max were in the same range as previously reported in cohesive sediments despite organic carbon contents one order of magnitude lower for the sediments studied here. The ratio of sediment O₂ consumption to V_max was in the range of 0.02–0.09, and was on average much lower than the theoretical ratio of 0.8. As a consequence, models implemented with the theoretical ratio of 0.8 are likely to overestimate denitrification by a factor of ~3. The most likely explanation for this is that the microbial community is not able to instantaneously shift or optimally use a particular electron acceptor in the highly dynamic redox environment experienced in permeable sediments. In contrast to previous studies, we did not observe any significant rates of oxic denitrification.     

Residue incorporation depth is a controlling factor of earthworm‐induced nitrous oxide emissions

Earthworms can increase nitrous oxide (N₂O) emissions, particularly in no‐tillage systems where earthworms are abundant. Here, we study the effect of residue incorporation depth on earthworm‐induced N₂O emissions. We hypothesized that cumulative N₂O emissions decrease with residue incorporation depth, because (i) increased water filled pore space (WFPS) in deeper soil layers leads to higher denitrification rates as well as more complete denitrification; and (ii) the longer upward diffusion path increases N₂O reduction to N₂. Two 84‐day laboratory mesocosm experiments were conducted. First, we manually incorporated maize (Zea mays L.) residue at different soil depths (incorporation experiment). Second, ¹³C‐enriched maize residue was applied to the soil surface and anecic species Lumbricus terrestris (L.) and epigeic species Lumbricus rubellus (Hoffmeister) were confined to different soil depths (earthworm experiment). Residue incorporation depth affected cumulative N₂O emissions in both experiments (P < 0.001). In the incorporation experiment, N₂O emissions decreased from 4.91 mg N₂O–N kg^?1 soil (surface application) to 2.71 mg N₂O–N kg^?1 soil (40–50 cm incorporation). In the earthworm experiment, N₂O emissions from L. terrestris decreased from 3.87 mg N₂O–N kg^?1 soil (confined to 0–10 cm) to 2.01 mg N₂O–N kg^?1 soil (confined to 0–30 cm). Both experimental setups resulted in dissimilar WFPS profiles that affected N₂O dynamics. We also found significant differences in residue C recovery in soil organic matter between L. terrestris (28–41%) and L. rubellus (56%). We conclude that (i) N₂O emissions decrease with residue incorporation depth, although this effect was complicated by dissimilar WFPS profiles; and (ii) larger residue C incorporation by L. rubellus than L. terrestris indicates that earthworm species differ in their C stabilization potential. Our findings underline the importance of studying earthworm diversity in the context of greenhouse gas emissions from agro‐ecosystems.