Effect of Reduced Winter Precipitation and Increased Temperature on Watershed Solute Flux, 1988–2002, Northern Michigan

Since 1987 we have studied weekly change in winter (December–April) precipitation, snowpack, snowmelt, soil water, and stream water solute flux in a small (176-ha) Northern Michigan watershed vegetated by 65–85 year-old northern hardwoods. Our primary study objective was to quantify the effect of change in winter temperature and precipitation on watershed hydrology and solute flux. During the study winter runoff was correlated with precipitation, and forest soils beneath the snowpack remained unfrozen. Winter air temperature and soil temperature beneath the snowpack increased while precipitation and snowmelt declined. Atmospheric inputs declined for H⁺, NO₃⁻, NH₄⁺, dissolved inorganic nitrogen (DIN), and SO₄²⁻. Replicated plot-level results, which could not be directly extrapolated to the watershed scale, showed 90% of atmospheric DIN input was retained in surface shallow (<15 cm deep) soils while SO₄²⁻ flux increased 70% and dissolved organic carbon (DOC) 30-fold. Most stream water base cation (C_B), HCO₃⁻, and Cl⁻ concentrations declined with increased stream water discharge, K⁺, NO₃⁻, and SO₄²⁻ remained unchanged, and DOC and dissolved organic nitrogen (DON) increased. Winter stream water solute outputs declined or were unchanged with time except for NO₃⁻ and DOC which increased. DOC and DIN outputs were correlated with the percentage of winter runoff and stream discharge that occurred when subsurface flow at the plot-level was shallow (<25 cm beneath Oi). Study results suggest that the percentage of annual runoff occurring as shallow lateral subsurface flow may be a major factor regulating solute outputs and concentrations in snowmelt-dominated ecosystems.     

Contrasting nutrient exports from a forested and an agricultural catchment in south-eastern Australia

Dissolved organic carbon (DOC) and total and inorganic nitrogen and phosphorus concentrations were determined over 3 years in headwater streams draining two adjacent catchments. The catchments are currently under different land use; pasture/grazing vs plantation forestry. The objectives of the work were to quantify C and nutrient export from these landuses and elucidate the factors regulating export. In both catchments, stream water dissolved inorganic nutrient concentrations exhibited strong seasonal variations. Concentrations were highest during runoff events in late summer and autumn and rapidly declined as discharge increased during winter and spring. The annual variation of stream water N and P concentrations indicated that these nutrients accumulated in the catchments during dry summer periods and were flushed to the streams during autumn storm events. By contrast, stream water DOC concentrations did not exhibit seasonal variation. Higher DOC and NO₃ ⁻ concentrations were observed in the stream of the forest catchment, reflecting greater input and subsequent breakdown of leaf-litter in the forest catchment. Annual export of DOC was lower from the forested catchment due to the reduced discharge from this catchment. In contrast however, annual export of nitrate was higher from the forest catchment suggesting that there was an additional NO₃ ⁻ source or reduction of a NO₃ ⁻ sink. We hypothesize that the denitrification capacity of the forested catchment has been significantly reduced as a consequence of increased evapotranspiration and subsequent decrease in streamflow and associated reduction in the near stream saturated area.     

Dissolved Nitrogen, Phosphorus, and Sulfur forms in the Ecosystem Fluxes of a Montane Forest in Ecuador

The N, P, and S cycles in pristine forests are assumed to differ from those of anthropogenically impacted areas, but there are only a few studies to support this. Our objective was therefore to assess the controls of N, P, and S release, immobilization, and transport in a remote tropical montane forest. The study forest is located on steep slopes of the northern Andes in Ecuador. We determined the concentrations of NO₃-N, NH₄-N, dissolved organic N (DON), PO₄-P, dissolved organic P (DOP), SO₄-S, dissolved organic S (DOS), and dissolved organic C (DOC) in rainfall, throughfall, stemflow, lateral flow (in the organic layer), litter leachate, mineral soil solution, and stream water of three 8–13 ha catchments (1900–2200 m a.s.l.). The organic forms of N, P, and S contributed, on average, 55, 66, and 63% to the total N, P, and S concentrations in all ecosystem fluxes, respectively. The organic layer was the largest source of all N, P, and S species except for inorganic P and S. Most PO₄ was released in the canopy by leaching and most SO₄ in the mineral soil by weathering. The mineral soil was a sink for all studied compounds except for SO₄. Consequently, concentrations of dissolved inorganic and organic N and P were as low in stream water (TDN: 0.34–0.39 mg N l⁻¹, P not detectable) as in rainfall (TDN: 0.39–0.48 mg N l⁻¹, P not detectable), whereas total S concentrations were elevated (stream water: 0.04–0.15, rainfall: 0.01–0.07 mg S l⁻¹). Dissolved N, P, and S forms were positively correlated with pH at the scale of soil peda except inorganic S. Soil drying and rewetting promoted the release of dissolved inorganic N. High discharge levels following heavy rainstorms were associated with increased DOC, DON, NO₃-N and partly also NH₄-N concentrations in stream water. Nitrate-N concentrations in the stream water were positively correlated with stream discharge during the wetter period of the year. Our results demonstrate that the sources and sinks of N, P, and S were element-specific. More than half of the cycling N, P, and S was organic. Soil pH and moisture were important controls of N, P, and S solubility at the scale of individual soil peda whereas the flow regime influenced the export with stream water.     

Riparian control on NO3 −, DOC, and dissolved Fe concentrations in mountainous streams, northern Japan

We evaluated (1) the longitudinal pattern of stream chemistry and (2) the effects of the riparian zone on this longitudinal pattern for nitrate (NO₃ ⁻), dissolved organic carbon (DOC), and total dissolved iron (Fe). We selected two small watersheds; the “southern watershed” had an extending riparian wetland and the “northern watershed” had a narrow riparian area. Stream NO₃ ⁻ concentrations decreased from the spring to outlet of both watersheds. In the southern watershed, stream DOC concentration decreased from the spring to midstream and then increased to the outlet. Stream Fe concentration in the southern watershed longitudinally increased. On the other hand, the northern watershed exhibited no longitudinal pattern for DOC and Fe concentrations. In both watersheds, while NO₃ ⁻ concentrations in the soil and ground water were lower than those in the stream waters, DOC and Fe concentrations exhibited the opposite patterns. The longitudinal decreases of NO₃ ⁻ concentrations in both streams and increase of stream Fe in the southern watershed mainly resulted from the inflow of the soil and ground water to the stream. The decrease in stream DOC from the spring to midstream in the southern watershed was due to the deep groundwater having low DOC, while the subsequent increase to the surrounding soil and ground water. Moreover, considerations of stream solute flow with soil and ground water chemistry suggested other mechanisms adding NO₃ ⁻ and removing/diluting DOC and Fe, especially for the northern watershed; coexistence of oxidizing and reducing conditions in the riparian zone might control the longitudinal concentration change in the stream water chemistry.     

Solute Sources in Stream Water during Consecutive Fall Storms in a Northern Hardwood Forest Watershed: A Combined Hydrological, Chemical and Isotopic Approach

Understanding the effects of climate change including precipitation patterns has important implications for evaluating the biogeochemical responses of watersheds. We focused on four storms in late summer and early fall that occurred after an exceptionally dry period in 2002. We analyzed not only the influence of these storms on episodic chemistry and the role of different water sources in affecting surface water chemistry, but also the relative contributions of these storms to annual biogeochemical mass balances. The study site was a well studied 135-ha watershed in the Adirondack Park of New York State (USA). Our analyses integrated measurements on hydrology, solute chemistry and the isotopic composition of NO₃⁻(δ¹⁵N and δ¹⁸O) and SO₄²⁻(δ³⁴S and δ¹⁸O) to evaluate how these storms affected surface water chemistry. Precipitation amounts varied among the storms (Storm 1: Sept. 14–18, 18.5 mm; Storm 2: Sept. 21–24, 33 mm; Storm 3: Sept. 27–29, 42.9 mm; Storm 4: Oct. 16–21, 67.6 mm). Among the four storms, there was an increase in water yields from 2 to 14%. These water yields were much less than in studies of storms in previous years at this same watershed when antecedent moisture conditions were higher. In the current study, early storms resulted in relatively small changes in water chemistry. With progressive storms the changes in water chemistry became more marked with particularly major changes in C_b (sum of base cations), Si, NO₃⁻, and SO₄²⁻, DOC and pH. Analyses of the relationships between Si, DOC, discharge and water table height clearly indicated that there was a decrease in ground water contributions (i.e., lower Si concentrations and higher DOC concentrations) as the watershed wetness increased with storm succession. The marked changes in chemistry were also reflected in changes in the isotopic composition of SO₄²⁻ and NO₃⁻. There was a strong inverse relationship between SO₄²⁻ concentrations and δ³⁴S values suggesting the importance of S biogeochemical redox processes in contributing to SO₄²⁻ export. The isotopic composition of NO₃⁻ in stream water indicated that this N had been microbially processed. Linkages between SO₄²⁻ and DOC concentrations suggest that wetlands were major sources of these solutes to drainage waters while the chemical and isotopic response of NO₃⁻ suggested that upland sources were more important. Although these late summer and fall storms did not play a major role in the overall annual mass balances of solutes for this watershed, these events had distinctive chemistry including depressed pH and therefore have important consequences to watershed processes such as episodic acidification, and the linkage of these processes to climate change.     

Porewater Stoichiometry of Terminal Metabolic Products, Sulfate, and Dissolved Organic Carbon and Nitrogen in Estuarine Intertidal Creek-bank Sediments

Porewater equilibration samplers were used to obtain porewater inventories of inorganic nutrients (NH₄⁺, NO_x, PO₄³⁻), dissolved organic carbon (DOC) and nitrogen (DON), sulfate (SO₄²⁻), dissolved inorganic carbon (DIC), hydrogen sulfide (H₂S), chloride (Cl⁻), methane (CH₄) and reduced iron (Fe²⁺) in intertidal creek-bank sediments at eight sites in three estuarine systems over a range of salinities and seasons. Sulfate reduction (SR) rates and sediment particulate organic carbon (POC) and nitrogen (PON) were also determined at several of the sites. Four sites in the Okatee River estuary in South Carolina, two sites on Sapelo Island, Georgia and one site in White Oak Creek, Georgia appeared to be relatively pristine. The eighth site in Umbrella Creek, Georgia was directly adjacent to a small residential development employing septic systems to handle household waste. The large data set (>700 porewater profiles) offers an opportunity to assess system-scale patterns of porewater biogeochemical dynamics with an emphasis on DOC and DON distributions. SO₄²⁻ depletion (SO₄²⁻)_Dep was used as a proxy for SR, and (SO₄²⁻)_Dep patterns agreed with measured (³⁵S) patterns of SR. There were significant system-scale correlations between the inorganic products of terminal metabolism (DIC, NH₄⁺ and PO₄³⁻) and (SO₄²⁻)_Dep, and SR appeared to be the dominant terminal carbon oxidation pathway in these sediments. Porewater inventories of DIC and (SO₄²⁻)_Dep indicate a 2:1 stoichiometry across sites, and the C:N ratio of the organic matter undergoing mineralization was between 7.5 and 10. The data suggest that septic-derived dissolved organic matter with a C:N ratio below 6 fueled microbial metabolism and SR at a site with development in the upland. Seasonality was observed in the porewater inventories, but temperature alone did not adequately describe the patterns of (SO₄²⁻)_Dep, terminal metabolic products (DIC, NH₄⁺, PO₄³⁻), DOC and DON, and SR observed in this study. It appears that production and consumption of labile DOC are tightly coupled in these sediments, and that bulk DOC is likely a recalcitrant pool. Preferential hydrolysis of PON relative to POC when overall organic matter mineralization rates were high appears to drive the observed patterns in POC:PON, DOC:DON and DIC:DIN ratios. These data, along with the weak seasonal patterns of SR and organic and inorganic porewater inventories, suggest that the rate of hydrolysis limits organic matter mineralization in these intertidal creek-bank sediments.     

Seasonal Variations of Dissolved Nitrogen and DOC:DON Ratios in an Intermittent Mediterranean Stream

Seasonal variations of dissolved inorganic nitrogen (DIN) (NO₃–N and NH₄–N) and dissolved organic nitrogen (DON) were determined in Fuirosos, an intermittent stream draining an unpolluted Mediterranean forested catchment (10.5 km²) in Catalonia (Spain). The influence of flow on streamwater concentrations and seasonal differences in quality and origin of dissolved organic matter, inferred from dissolved organic carbon to nitrogen ratios (DOC:DON ratios), were examined. During baseflow conditions, nitrate and ammonium had opposite behaviour, probably controlled by biological processes such as vegetation uptake and mineralization activity. DON concentrations did not have a seasonal trend. During storms, nitrate and DON increased by several times but discharge was not a good predictor of nutrient concentrations. DOC:DON ratios in streamwater were around 26, except during the months following drought when DOC:DON ratios ranged between 42 and 20 during baseflow and stormflow conditions, respectively. Annual N export during 2000–2001 was 70 kg km⁻¹ year⁻¹, of which 75% was delivered during stormflow. The relative contribution of nitrogen forms to the total annual export was 57, 35 and 8% as NO₃–N, DON and NH₄–N, respectively.     

Hillslope Nutrient Dynamics Following Upland Riparian Vegetation Disturbance

We investigated the effects of removing near-stream Rhododendron and of the natural blowdown of canopy trees on nutrient export to streams in the southern Appalachians. Transects were instrumented on adjacent hillslopes in a first-order watershed at the Coweeta Hydrologic Laboratory (35°03′N, 83°25′W). Dissolved organic carbon (DOC), K⁺, Na⁺, Ca²⁺, Mg²⁺, NO₃ ⁻-N, NH₄ ⁺-N, PO₄ ³⁻-P, and SO₄ ²⁻ were measured for 2 years prior to disturbance. In August 1995, riparian Rhododendron on one hillslope was cut, removing 30% of total woody biomass. In October 1995, Hurricane Opal uprooted nine canopy trees on the other hillslope, downing 81% of the total woody biomass. Over the 3 years following the disturbance, soilwater concentrations of NO₃ ⁻-N tripled on the cut hillslope. There were also small changes in soilwater DOC, SO₄ ²⁻, Ca²⁺, and Mg²⁺. However, no significant changes occurred in groundwater nutrient concentrations following Rhododendron removal. In contrast, soilwater NO₃ ⁻-N on the storm-affected hillslope showed persistent 500-fold increases, groundwater NO₃ ⁻-N increased four fold, and streamwater NO₃ ⁻-N doubled. Significant changes also occurred in soilwater pH, DOC, SO₄ ²⁻, Ca²⁺, and Mg²⁺. There were no significant changes in microbial immobilization of soil nutrients or water outflow on the storm-affected hillslope. Our results suggest that Rhododendron thickets play a relatively minor role in controlling nutrient export to headwater streams. They further suggest that nutrient uptake by canopy trees is a key control on NO₃ ⁻-N export in upland riparian zones, and that disruption of the root–soil connection in canopy trees via uprooting promotes significant nutrient loss to streams. Received 30 January 2001; accepted 25 July 2002.     

Landscape Controls on Organic and Inorganic Nitrogen Leaching across an Alpine/Subalpine Ecotone,Green Lakes Valley,Colorado Front Range

Here we report measurements of organic and inorganic nitrogen (N) fluxes from the high-elevation Green Lakes Valley catchment in the Colorado Front Range for two snowmelt seasons (1998 and 1999). Surface water and soil samples were collected along an elevational gradient extending from the lightly vegetated alpine to the forested subalpine to assess how changes in land cover and basin area affect yields and concentrations of ammonium-N (NH₄-N), nitrate-N (NO₃-N), dissolved organic N (DON), and particulate organic N (PON). Streamwater yields of NO₃-N decreased downstream from 4.3 kg ha⁻¹ in the alpine to 0.75 kg ha⁻¹ at treeline, while yields of DON were much less variable (0.40–0.34 kg ha⁻¹). Yields of NH₄-N and PON were low and showed little variation with basin area. NO₃-N accounted for 40%–90% of total N along the sample transect and was the dominant form of N at all but the lowest elevation site. Concentrations of DON ranged from approximately 10% of total N in the alpine to 45% in the subalpine. For all sites, volume-weighted mean concentrations of total dissolved nitrogen (TDN) were significantly related to the DIN:DON ratio (R ² = 0.81, P < 0.001) Concentrations of NO₃-N were significantly higher at forested sites that received streamflow from the lightly vegetated alpine reaches of the catchment than in a control catchment that was entirely subalpine forest, suggesting that the alpine may subsidize downstream forested systems with inorganic N. KCl-extractable inorganic N and microbial biomass N showed no relationship to changes in soil properties and vegetative cover moving downstream in catchment. In contrast, soil carbon–nitrogen (C:N) ratios increased with increasing vegetative cover in catchment and were significantly higher in the subalpine compared to the alpine (P < 0.0001) Soil C:N ratios along the sample transect explained 78% of the variation in dissolved organic carbon (DOC) concentrations and 70% of the variation in DON concentrations. These findings suggest that DON is an important vector for N loss in high-elevation ecosystems and that streamwater losses of DON are at least partially dependent on catchment soil organic matter stoichiometry. Received 26 July 2001; accepted 6 May 2002.     

Effects of decreased atmospheric deposition on the sulfur budgets of two Dutch moorland pools

The chemical composition of surface waters of two Dutch moorland pools and of incident precipitation, was monitored from 1982 to 1990. For this period, sulfur and water budgets were calculated using a hydrochemical model developed for well-mixed non-stratifying lakes. Total atmospheric deposition of S decreased significantly after 1986 at both locations. A model describing the sulfur budget in terms of input, output and reduction/oxidation processes predicted a fast decrease of pool water SO₄ ²⁻ concentrations after a decrease of atmospheric input. However, SO₄ ²⁻ concentrations in the surface water was lowered only slightly or remained constant. Apparently a source within the lake caused the unexpectedly high SO₄ ²⁻ concentrations. The possible supply of SO₄ ²⁻ from the sediment through regulation by (K-)Al-SO₄ containing minerals or desorption of SO₄ ²⁻ from positively charged surfaces in the sediment was evaluated. Solubility calculations of pore water with respect to alunite, basaluminite and jurbanite indicated that SO₄ ²⁻ concentration was not regulated by these minerals. It is suggested here (1) that desorption of SO₄ ²⁻ from peaty sediments may account for the estimated SO₄ ²⁻ supply provided that the adsorption complex is periodically recharged by partial oxidation of the upper bottom sediments and (2) that because of exposure of a part of the pool bottom to the atmosphere during dry summers and subsequent oxidation of reduced S, the amount of SO₄ ²⁻ may be provided which complements the decreasing depositional SO₄ ²⁻ input. In future research these two mechanisms need to be investigated.     

DOC and DIC in Flowpaths of Amazonian Headwater Catchments with Hydrologically Contrasting Soils

Organic and inorganic carbon (C) fluxes transported by water were evaluated for dominant hydrologic flowpaths on two adjacent headwater catchments in the Brazilian Amazon with distinct soils and hydrologic responses from September 2003 through April 2005. The Ultisol-dominated catchment produced 30% greater volume of storm-related quickflow (overland flow and shallow subsurface flow) compared to the Oxisol-dominated catchment. Quickflow fluxes were equivalent to 3.2 ± 0.2% of event precipitation for the Ultisol catchment, compared to 2.5 ± 0.3% for the Oxisol-dominated watershed (mean response ±1 SE, n = 27 storms for each watershed). Hydrologic responses were also faster on the Ultisol watershed, with time to peak flow occurring 10 min earlier on average as compared to the runoff response on the Oxisol watershed. These different hydrologic responses are attributed primarily to large differences in saturated hydraulic conductivity (K _s). Overland flow was found to be an important feature on both watersheds. This was evidenced by the response rates of overland flow detectors (OFDs) during the rainy season, with overland flow intercepted by 54 ± 0.5% and 65 ± 0.5% of OFDs for the Oxisol and Ultisol watersheds respectively during biweekly periods. Small volumes of quickflow correspond to large fluxes of dissolved organic C (DOC); DOC concentrations of the hydrologic flowpaths that comprise quickflow are an order of magnitude higher than groundwater flowpaths fueling base flow (19.6 ± 1.7 mg l⁻¹ DOC for overland flow and 8.8 ± 0.7 mg l⁻¹ DOC for shallow subsurface flow versus 0.50 ± 0.04,mg l⁻¹ DOC in emergent groundwater). Concentrations of dissolved inorganic C (DIC, as dissolved CO₂–C plus HCO₃⁻–C) in groundwater were found to be an order of magnitude greater than quickflow DIC concentrations (21.5 mg l⁻¹ DIC in emergent groundwater versus 1.1 mg l⁻¹ DIC in overland flow). The importance of deeper flowpaths in the transport of inorganic C to streams is indicated by the 40:1 ratio of DIC:DOC for emergent groundwater. Dissolved CO₂–C represented 92% of DIC in emergent groundwater. Results from this study illustrate a highly dynamic and tightly coupled linkage between the C cycle and the hydrologic cycle for both Ultisol and Oxisol landscapes: organic C fluxes strongly tied to flowpaths associated with quickflow, and inorganic C (particularly dissolved CO₂) transported via deeper flowpaths.     

Influence of drought-induced acidification on the mobility of dissolved organic carbon in peat soils

A strong relationship between dissolved organic carbon (DOC) and sulphate (SO₄^2?) dynamics under drought conditions has been revealed from analysis of a 10‐year time series (1993–2002). Soil solution from a blanket peat at 10 cm depth and stream water were collected at biweekly and weekly intervals, respectively, by the Environmental Change Network at Moor House‐Upper Teesdale National Nature Reserve in the North Pennine uplands of Britain. DOC concentrations in soil solution and stream water were closely coupled, displaying a strong seasonal cycle with lowest concentrations in early spring and highest in late summer/early autumn. Soil solution DOC correlated strongly with seasonal variations in soil temperature at the same depth 4‐weeks prior to sampling. Deviation from this relationship was seen, however, in years with significant water table drawdown (>?25 cm), such that DOC concentrations were up to 60% lower than expected. Periods of drought also resulted in the release of SO₄^2?, because of the oxidation of inorganic/organic sulphur stored in the peat, which was accompanied by a decrease in pH and increase in ionic strength. As both pH and ionic strength are known to control the solubility of DOC, inclusion of a function to account for DOC suppression because of drought‐induced acidification accounted for more of the variability of DOC in soil solution (R²=0.81) than temperature alone (R²=0.58). This statistical model of peat soil solution DOC at 10 cm depth was extended to reproduce 74% of the variation in stream DOC over this period. Analysis of annual budgets showed that the soil was the main source of SO₄^2? during droughts, while atmospheric deposition was the main source in other years. Mass balance calculations also showed that most of the DOC originated from the peat. The DOC flux was also lower in the drought years of 1994 and 1995, reflecting low DOC concentrations in soil and stream water. The analysis presented in this paper suggests that lower concentrations of DOC in both soil and stream waters during drought years can be explained in terms of drought‐induced acidification. As future climate change scenarios suggest an increase in the magnitude and frequency of drought events, these results imply potential for a related increase in DOC suppression by episodic acidification.     

Nitrogen Cycling and Mass Balance for a Forested Catchment in the Italian Alps. Assessment of Nitrogen Status

During 1999–2001 the chemical composition and fluxes were measured in rainfall, throughfall, soil solution and stream water in a remote forested site in the Italian Alps. The analysis of temporal patterns revealed the differential behaviour of nitrogen and sulphur and suggested that different mechanisms controlled their flux. No important changes in sulphate concentration and fluxes emerged as the solution passed through the various components of the forest ecosystem, and temporal variations of SO₄ in the soil solution and stream were likely driven by the physical process of dilution. The availability of nitrate and ammonia, by contrast, was drastically reduced as throughfall water entered the soil and passed through the mineral layers, irrespective of season. The calculated hydrochemical budget based on throughfall and soil solution N fluxes revealed that ~80% N retention in the forest soil, corresponding to 12 kg ha⁻¹ yr⁻¹, despite a relatively high N deposition loading (15 kg ha⁻¹ yr⁻¹). Most of the leached nitrogen (90%) was in the organic form. Indicators of the N status of this ecosystem, such as C/N ratio in solid and solution phase of the soil and N foliage content as well as land use history were examined. Despite the strong N retention in the forested part of the catchment, the stream water N–NO₃ levels were consistently above 10 μg l⁻¹ suggesting that the Val Masino catchment as a whole was less efficient in processing atmospheric N inputs. This contrasting N behaviour illustrates the role of landscape features, such as the soil cover and vegetation type, that is characteristic of an alpine catchment.     

Abiotic reaction of nitrite with dissolved organic carbon? Testing the Ferrous Wheel Hypothesis

The Ferrous Wheel Hypothesis (Davidson et al. 2003) postulates the abiotic formation of dissolved organic N (DON) in forest floors, by the fast reaction of NO₂ ⁻ with dissolved organic C (DOC). We investigated the abiotic reaction of NO₂ ⁻ with dissolved organic matter extracted from six different forest floors under oxic conditions. Solutions differed in DOC concentrations (15–60 mg L⁻¹), NO₂ ⁻ concentrations (0, 2, 20 mg NO₂ ⁻-N L⁻¹) and DOC/DON ratio (13.4–25.4). Concentrations of added NO₂ ⁻ never decreased within 60 min, therefore, no DON formation from added NO₂ ⁻ took place in any of the samples. Our results suggest that the reaction of NO₂ ⁻ with natural DOC in forest floors is rather unlikely.     

Sensitivity of dissolved organic carbon exchange and sediment bacteria to water quality in mangrove forests

Poor water quality affects the biogeochemistry functions and the biological community structure of coastal ecosystems. In this study we investigated the effect of water quality on: (a) The exchange of dissolved organic carbon (DOC) between floodwater and mangrove forests, (b) the abundance of sediment bacteria, (c) the microbial community composition, and (d) the microbial catabolic activity. We selected six mangrove forests that were flooded by creeks with differing water qualities to test for thresholds of nutrient concentrations associated with changes in DOC dynamics and the microbial community. Our results show that in sites flooded by water high in soluble reactive phosphorus (SRP) (>20 μg l⁻¹) and NH₄ ⁺ (>30 μg l⁻¹) the DOC concentrations in the floodwater were higher than in ebb water, suggesting DOC import by the mangroves. In contrast, in sites flooded by water low in SRP (<20 μg l⁻¹) and NH₄ ⁺ (<30 μg l⁻¹), DOC concentrations in the floodwater were lower than in the ebb water, suggesting DOC export by the mangroves. Bacterial abundance was higher in sediments with low bulk density, high organic carbon and when flooded by water with low N:P (1–2), but the microbial composition and total catabolic activity assessed using Biolog Ecoplates™ did not differ among sites. The relationship between water quality, microbial communities and DOC exchange suggests that, at least during some periods of the year, poor water quality increases bacterial abundance and modifies DOC exchange of mangrove forests with floodwater and thus, their role in supporting near-shore productivity.     

Contribution of Sediment Respiration to Summer CO2 Emission from Low Productive Boreal and Subarctic Lakes

We measured sediment production of carbon dioxide (CO₂) and methane (CH₄) and the net flux of CO₂ across the surfaces of 15 boreal and subarctic lakes of different humic contents. Sediment respiration measurements were made in situ under ambient light conditions. The flux of CO₂ between sediment and water varied between an uptake of 53 and an efflux of 182 mg C m⁻² day⁻¹ from the sediments. The mean respiration rate for sediments in contact with the upper mixed layer (SedR) was positively correlated to dissolved organic carbon (DOC) concentration in the water (r² = 0.61). The net flux of CO₂ across the lake surface [net ecosystem exchange (NEE)] was also closely correlated to DOC concentration in the upper mixed layer (r² = 0.73). The respiration in the water column was generally 10-fold higher per unit lake area compared to sediment respiration. Lakes with DOC concentrations <5.6 mg L⁻¹ had net consumption of CO₂ in the sediments, which we ascribe to benthic primary production. Only lakes with very low DOC concentrations were net autotrophic (<2.6 mg L⁻¹) due to the dominance of dissolved allochthonous organic carbon in the water as an energy source for aquatic organisms. In addition to previous findings of allochthonous organic matter as an important driver of heterotrophic metabolism in the water column of lakes, this study suggests that sediment metabolism is also highly dependent on allochthonous carbon sources.     

Role of SO4 adsorption and desorption in the long-term S budget of a coniferous catchment on the Canadian Shield

The hypothesis that SO₄ desorption can explain apparent long term net SO₄-S losses (5 kg·ha^–1·yr^–1 on average) at the Lake Laflamme catchment from 1982 to 1991 is examined. Field observations show that SO₄ concentrations in the soil solution are strongly buffered during percolation through the Bf horizon. In the Bf horizon, SO₄ exchange reactions between the adsorbed and aqueous compartments are rapid (hours). Most (60%) of the adsorbed SO₄ may be readily desorbed with deionized water. These observations and the presence of an important adsorbed SO₄-S reservoir in the Bf horizon (113 kg·ha^–1) as compared with annual wet SO₄-S deposition (7 kg·ha^–1), suggest that on the short-term, adsorption and desorption reactions can control dissolved SO₄ concentration in the Bf horizon. To examine whether SO₄ adsorption/desorption could explain long-term SO₄-S losses by the catchment, an aggregated Langmuir isotherm for the Bf horizon was used to calculate the catchment's resilience to changing SO₄-S loads. The results indicate that the soil should adjust rapidly (within 4 years) to changing SO₄-S loads and that SO₄ desorption alone cannot explain long-term net SO₄-S losses. Other possibilities, such as an underestimation of dry deposition or the weathering of S-bearing minerals also appear unlikely. Our results suggest a net release of SO₄-S from the soil organic S reservoirs (1230 kg·ha^–1) present in the catchment.     

Biogeochemical processes in the groundwater discharge zone of urban streams

The influence of biogeochemical processes on nitrogen and organic matter transformation and transport was investigated for two urban streams receiving groundwater discharge during the dry summer baseflow period. A multiple lines of evidence approach involving catchment-, and stream reach-scale investigations were undertaken to describe the factors that influence pore water biogeochemical processes. At the catchment-scale gaining stream reaches were identified from water table mapping and groundwater discharge estimated to be between 0.1 and 0.8 m³ m^?2 d^?1 from baseflow analysis. Sediment temperature profiles also suggested that the high groundwater discharge limited stream water infiltration into the sediments. At the stream reach-scale, dissolved organic carbon (DOC) and dissolved organic nitrogen (DON) concentrations were higher in stream water than in groundwater. However, DOC and DON concentrations were greatest in sediment pore water. This suggests that biodegradation of sediment organic matter contributes dissolved organic matter (DOM) to the streams along with that delivered with groundwater flow. Pore water ammonium (NH₄ ⁺) was closely associated with areas of high pore water DOM concentrations and evidence of sulfate (SO₄ ^2?) reduction (low concentration and SO₄:Cl ratio). This indicates that anoxic DOM mineralization was occurring associated with SO₄ ^2? reduction. However the distribution of anoxic mineralization was limited to the center of the streambed, and was not constrained by the distribution of sediment organic matter which was higher along the banks. Lower sediment temperatures measured along the banks compared to the center suggests, at least qualitatively, that groundwater discharge is higher along the banks. Based on this evidence anoxic mineralization is influenced by groundwater residence time, and is only measurable along the center of the stream where groundwater flux rates are lower. This study therefore shows that the distribution of biogeochemical processes in stream sediments, such as anoxic mineralization, is strongly influenced by both the biogeochemical conditions and pore water residence time.     

Environmental chemistry of rivers and lakes, part v: a comparative study of the chemical and physicochemical characteristics of organic carbon dissolved in river and lake waters

To determine the chemical and physicochemical characteristics of dissolved organic carbon in the Ado River and the Yasu River, the main rivers flowing into Lake Biwa, the adsorption behavior onto hydrous iron oxide (HIO) and the reactivity to KMnO₄ oxidant were investigated in parallel with measurement of the distribution profiles of dissolved organic carbon (DOC) along the rivers. In one year of observation at the mouths of the two rivers, DOC concentrations were found to vary in the Ado over the range 0.28–1.21 mg C l⁻¹ and in the Yasu over the range 1.01–2.68 mg C l⁻¹. Act-DOC, one of the fractions separated from the total DOC by its adsorption-active character onto HIO at pH 4, was thought primarily to control the variation of total DOC, as in Lake Biwa. The int-DOC, another fraction separated by its adsorption-inert or -inactive character onto HIO, remained at almost a steady value around 0.18 ± 0.07 mg C l⁻¹ in the Ado, which was lower than that (0.35 ± 0.05 mg C l⁻¹) in Lake Biwa. The act-DOC in river waters was reactive to KMnO₄ oxidant, showing a linear relation with the amount of permanganate consumed for the reaction (chemical oxygen demand: COD). In river waters, the relation can be approximated by a straight line expressed as COD (mg O₂ l⁻¹) = 0.64 × act-DOC (mg C l⁻¹) − 0.02. In contrast, in the lake water the relation was COD (mg O₂ l⁻¹) = 0.97 × act-DOC (mg C l⁻¹) − 0.50. Received: March 3, 1999 / Accepted: December 2, 1999     

The organic carbon dynamics of a moorland catchment in N. W. England

The carbon cycle was quantified in the catchment of Doe House Gill, which drains high-relief moorland, with thin organic-rich soils (leptosols and podzols) 10–25 cm deep, in northern England. The soil C pool of 8,300 g m^-2 is due mainly to humic acid and older humin. If steady state is assumed, and a single soil C pool, the average ¹⁴C content of the whole soil (93% modern) yields a mean carbon residence time of 800 years, although this varied from 300 to 1,600 years in the four samples studied. Stream water fluxes of dissolved and particulate organic carbon (DOC, POC) were 2.5 and 0.4 g m⁻² a⁻¹ respectively in 2002–2003, lower than values for some other upland streams in the UK. The C pool, flux, and isotope data were used, with the assumption of steady state, to calibrate DyDOC, a model that simulates the soil carbon cycle, including the generation and transport of DOC. According to DyDOC, the litter pool (ca. 100 gC m⁻²) turns over quickly, and most (>90%) of the litter carbon is rapidly mineralised. The soil is calculated to gain only 16 gC m⁻² a⁻¹, and to lose the same amount, about 80% as CO₂ and 20% as DOC. From the DO¹⁴C content of 107.5% modern (due to “bomb carbon”) the model could be calibrated by assuming all DOC to come directly from litter, but DOC is more likely a mixture, derived from more than one soil C pool. The seasonal variability exhibited by stream water DOC concentration (maximum in September, minimum in January) is attributed mainly to variations in rainfall and evapotranspiration, rather than in the metabolic production rate of “potential DOC”. The model predicts that, for a Q ₁₀ of 2, the total soil organic C pool would decrease by about 5% if subjected to warming over 200 years. DyDOC predicts higher DOC fluxes in response to increased litter inputs or warming, and can simulate changes in DOC flux due to variations in sorption to soil solids, that might occur due to acidification and its reversal.