Hydrochemical behaviour of dissolved nitrogen and carbon in a headwater stream of the Canadian Shield: relevance of antecedent soil moisture conditions

This paper examines the impact of contrasting antecedent soil moisture conditions on the hydrochemical response, here the changes in dissolved nitrogen (NO₃^?, NH₄⁺ and dissolved organic nitrogen (DON)) and dissolved organic carbon (DOC) concentrations, of a first‐order stream during hydrological events. The study was performed in the Hermine, a 5 ha forested watershed of the Canadian Shield. It focused on a series of eight precipitation events (spring, summer and fall) sampled every 2 or 3 h and showing contrasted antecedent moisture conditions. The partition of the eight events between two groups (dry or wet) of antecedent moisture conditions was conducted using a principal component analysis (PCA). The partition was controlled (first axis explained 86% of the variability) by the antecedent streamflow, the streamflow to precipitation ratio Q/P and by the antecedent groundwater depth. The mean H⁺, NO₃^?, NH₄⁺, total dissolved nitrogen and DOC concentrations and electrical conductivity values in the stream were significantly higher following dry antecedent conditions than after wetter conditions had prevailed in the Hermine, although the temporal variability was high (17 to 138%). At the event scale, a significantly higher proportion of the changes in DON, NO₃^?, and DOC concentrations in the stream was explained by temporal variations in discharge compared with the seasonal and annual scales. Two of the key hydrochemical features of the dry events were the synchronous changes in DOC and flow and the frequent negative relationships between discharge and NO₃^?. The DON concentrations were much less responsive than DOC to changes in discharge, whereas NH was not in phase with streamflow. During wet events, the synchronicity between streamflow and DON or NO₃^? was higher than during dry events and discharge and NO₃^? were generally positively linked. Based on these observations, the hydrological behaviour of the Hermine is conceptually compatible with a two‐component model of shallow (DON and DOC rich; variable NO₃^?) and deep (DON and DOC poor; variable NO₃^?) subsurface flow. The high NO₃^? and DOC levels measured at the early stages of dry events reflected the contribution from NO₃^?‐rich groundwaters. The contribution of rapid surface flow on water‐repellent soil materials located close to the stream channel is hypothesized to explain the DOC levels. An understanding of the complex interactions between antecedent soil moisture conditions, the presence of soil nutrients available for leaching and the dynamics of soil water flow paths during storms is essential to explain the fluxes of dissolved nitrogen and carbon in streams of forested watersheds. Copyright © 2007 John Wiley & Sons, Ltd.     

太湖西北湖区浮游植物和无机、有机氮的时空分布特征

以太湖重度蓝藻水华发生的西北湖区为研究对象,从河口至湖心区设置5个采样点,于2012年10月至2013年10月逐月采集表层水体样品,测定了水温、溶解氧和浮游细菌丰度,并分析了浮游植物群落结构的组成、溶解性无机氮(DIN)和有机氮(DON)浓度以及氮磷比.研究结果表明,太湖西北湖区浮游植物主要由蓝藻、硅藻、绿藻和隐藻组成.可能由于风、浪等混合作用使太湖西北湖区不同采样点之间蓝藻细胞密度没有显著差异.蓝藻生物量在浮游植物中所占比例最高为34%±15%,春季部分点位隐藻生物量高于50%,表明隐藻与蓝藻的相互竞争趋势显著.CCA排序图结果表明,DIN、DON浓度以及总氮∶总磷比(TN∶TP比)是影响西北湖区浮游植物优势属分布的重要环境因子.5个采样点铵态氮(NH_4~+-N)与DIN浓度具有显著差异,与DON浓度没有显著差异.夏季蓝藻水华暴发期间,可能由于蓝藻的吸收利用引起NH_4~+-N和硝态氮(NO_3~--N)浓度迅速降低.此外,由于NH_4~+-N浓度还可能受到沉积物NH_4~+-N释放的影响,因此,蓝藻细胞密度与NO_3~--N的相关系数和显著水平均高于NH_4~+-N.夏季TN∶TP比和DIN∶TP比降至最低,表明该湖区浮游植物,尤其是蓝藻的生长可能受到氮限制.蓝藻细胞密度与DON浓度呈显著负相关,表明在氮限制条件下,DON可能是蓝藻氮素利用的重要补充.     

Controls on surface water chemistry in two lake‐watersheds in the Adirondack region of New York: differences in nitrogen solute sources and sinks

The southwestern Adirondack region of New York receives among the highest rates of atmospheric nitrogen (N) deposition in the USA. Atmospheric N deposition to sensitive ecosystems, like the Adirondacks, may increase the acidification of soils through losses of exchangeable nutrient cations, and the acidification of surface waters associated with enhanced mobility of nitrate (NO₃^?). However, watershed attributes, including surficial terrestrial characteristics, in‐lake processing, and geological settings, have been found to complicate the relationships between atmospheric N deposition and N drainage losses. We studied two lake‐watersheds in the southwestern Adirondacks, Grass Pond and Constable Pond, which are located in close proximity (～26 km) and receive similarly high N deposition, but have contrasting watershed attributes (e.g. wetland area, geological settings). Since the difference in the influence of N deposition was minimal, we were able to examine both within‐ and between‐watershed influences of land cover, the contribution of glacial till groundwater inputs, and in‐lake processes on surface water chemistry with particular emphasis on N solutes and dissolved organic carbon (DOC). Monthly samples at seven inlets and one outlet of each lake were collected from May to October in 1999 and 2000. The concentrations of NO₃^? were high at the Grass Pond inlets, especially at two inlets, and NO₃^? was the major N solute at the Grass Pond inlets. The concentrations of likely weathering products (i.e. dissolved Si, Ca²⁺, Mg²⁺, Na⁺) as well as acid neutralizing capacity and pH values, were also particularly high at those two Grass Pond inlets, suggesting a large contribution of groundwater inputs. Dissolved organic N (DON) was the major N solute at the Constable Pond inlets. The higher concentrations of DON and DOC at the Constable Pond inlets were attributed to a large wetland area in the watershed. The DOC/DON ratios were also higher at the Constable Pond inlets, possibly due to a larger proportion of coniferous forest area. Although DON and DOC were strongly related, the stronger relationship of the proportion of wetland area with DOC suggests that additional factors regulate DON. The aggregated representation of watershed physical features (i.e. elevation, watershed area, mean topographic index, hypsometric‐analysis index) was not clearly related to the lake N and DOC chemistry. Despite distinctive differences in inlet N chemistry, NO₃^? and DON concentrations at the outlets of the two lakes were similar. The lower DOC/DON ratios at the lake outlets and at the inlets having upstream ponds suggest the importance of N processing and organic N sources within the lakes. Although an inverse relationship between NO₃^? and DOC/DON has been suggested to be indicative of a N deposition gradient, the existence of this relationship for sites that receive similar atmospheric N deposition suggest that the relationship between NO₃^? and the DOC/DON ratio is derived from environmental and physical factors. Our results suggest that, despite similar wet N deposition at the two watershed sites, N solutes entering lakes were strongly affected by hydrology associated with groundwater contribution and the presence of wetlands, whereas N solutes leaving lakes were strongly influenced by in‐lake processing. Copyright © 2006 John Wiley & Sons, Ltd.     

Factors controlling nitrogen and dissolved organic carbon exports across timescales in two watersheds with different land uses

Investigating factors controlling the temporal patterns of nitrogen (N) and dissolved organic carbon (DOC) exports on the basis of a comparative study of different land uses is beneficial for managing water resources, especially in agricultural watersheds. We focused our research on an agricultural watershed (AW) and a forested watershed (FW) located in the Shibetsu watershed of eastern Hokkaido, Japan, to investigate the temporal patterns of N and DOC exports and factors controlling those patterns at different timescales (inter‐annual, seasonal, and hydrological event scales). Results showed that the annual patterns of N and DOC exports significantly varied over time and were probably controlled by climate. Higher discharge volumes in 2003, a wet year, showed higher N and DOC loadings in both watersheds. However, this process was also regulated by land use associated with N inputs. Higher concentrations and loadings were shown in the agricultural watershed. At the seasonal scale, N and DOC exports in the AW and the FW were more likely controlled by sources associated with land use. The Total N (TN) and Nitrate‐N (NO₃^?‐N) had higher concentrations during snowmelt season in the AW, which may be attributed to manure application in late autumn or early winter in the agricultural watershed. Concentrations of TN, NO₃^?‐N, dissolved organic nitrogen (DON), and DOC showed higher values during the summer rainy season in the FW, related to higher litter decomposition during summer and autumn and the fertilizer application in the agricultural area during summer. Higher DOC concentrations and loadings were observed during the rainy season in the AW, which is probably attributed to higher DOC production related to temperature and microbial activity during summer and autumn in grasslands. Correlations between discharge and concentrations differed during different periods or in different watersheds, suggesting that weather discharge can adequately represent the fact that N export depends on N concentrations, discharge level, and other factors. The differing correlations between N/DOC concentrations and the Si concentration indicated that the N/DOC exports might occur along different flow paths during different periods. During baseflow, the high NO₃^?‐N exports were probably derived from deep groundwater and might have percolated from uplands during hydrological events. During hydrological events, NO₃^?‐N exports may occur along near‐surface flow paths and in deep groundwater, whereas DOC exports could be related to near‐surface flow paths. At the event scale, the relationships between discharge and concentrations of N and DOC were regulated by antecedent soil moisture (shallow groundwater condition) in each watershed. These results indicated that factors controlling N and DOC exports varied at different timescales in the Shibetsu area and that better management of manure application during winter in agricultural lands is urgently needed to control water pollution in streams. Copyright © 2013 John Wiley & Sons, Ltd.     

Wetland nitrogen dynamics in an Adirondack forested watershed

Wetlands often form the transition zone between upland soils and watershed streams, however, stream–wetland interactions and hydrobiogeochemical processes are poorly understood. We measured changes in stream nitrogen (N) through one riparian wetland and one beaver meadow in the Archer Creek watershed in the Adirondack Mountains of New York State, USA from 1 March to 31 July 1996. In the riparian wetland we also measured changes in groundwater N. Groundwater N changed significantly from tension lysimeters at the edge of the peatland to piezometer nests within the peatland. Mean N concentrations at the peatland perimeter were 1·5, 0·5 and 18·6 µmol L^?1 for NH₄⁺, NO₃^? and DON (dissolved organic nitrogen), respectively, whereas peatland groundwater N concentration was 56·9, 1·5 and 31·6 µmol L^?1 for NH₄⁺, NO₃^? and DON, respectively. The mean concentrations of stream water N species at the inlet to the wetlands were 1·5, 10·1 and 16·9 µmol L^?1 for NH₄⁺, NO₃^? and DON, respectively and 1·6, 28·1 and 8·4 µmol L^?1 at the wetland outlet. Although groundwater total dissolved N (TDN) concentrations changed more than stream water TDN through the wetlands, hydrological cross‐sections for the peatland showed that wetland groundwater contributed minimally to stream flow during the study period. Therefore, surface water N chemistry was affected more by in‐stream N transformations than by groundwater N transformations because the in‐stream changes, although small, affected a much greater volume of water. Stream water N input–output budgets indicated that the riparian peatland retained 0·16 mol N ha^?1 day^?1 of total dissolved N and the beaver meadow retained 0·26 mol N ha^?1 day^?1 during the study period. Nitrate dominated surface water TDN flux from the wetlands during the spring whereas DON dominated during the summer. This study demonstrates that although groundwater N changed significantly in the riparian peatland, those changes were not reflected in the stream. Consequently, although in‐stream changes of N concentrations were less marked than those in groundwater, they had a greater effect on stream water chemistry—because wetland groundwater contributed minimally to stream flow. Copyright © 2004 John Wiley & Sons, Ltd.     

Groundwater flushing of solutes at wetland and hillslope positions during storm events in a small glaciated catchment in western New York,USA

While the role of groundwater in flushing of solutes has long been recognized, few studies have explicitly studied the within‐event changes in groundwater chemistry. We compared the changes in groundwater chemistry during storm events for a wetland and hillslope position in a small (1·5 ha) glaciated, forested catchment in western New York. Flushing responses for dissolved organic carbon (DOC) and nitrogen (DON), nitrate (NO₃) and sulfate (SO₄) in wetland and hillslope groundwaters were also compared against the corresponding responses in stream water. Eight storm events with varying intensity, amount, and antecedent moisture conditions were evaluated. Solute flushing patterns for wetland and hillslope groundwaters differed dramatically. While DOC concentrations in wetland groundwater followed a dilution trend, corresponding values for hillslope groundwater showed a slight increase. Concentrations for NO₃ in wetland groundwater were below detection limits, but hillslope groundwaters displayed high NO₃ concentrations with a pronounced increase during storm events. Flushing responses at all positions were also influenced by the size of the event and the time between events. We attributed the differences in flushing to the differences in hydrologic flow paths and biogeochemical conditions. Flushing of the wetland did appear to influence storm‐event stream chemistry but the same could not be said for hillslope groundwaters. This suggests that while a variety of flushing responses may be observed in a catchment, only a subset of these responses affect the discharge chemistry at the catchment outlet. Copyright © 2009 John Wiley & Sons, Ltd.     

Relationship of topography to surface water chemistry with particular focus on nitrogen and organic carbon solutes within a forested watershed in Hokkaido,Japan

We studied the relationships between streamwater chemistry and the topography of subcatchments in the Dorokawa watershed in Hokkaido Island, northern Japan, to examine the use of topography as a predictor of streamwater chemistry in a watershed with relatively moderate terrain compared with other regions of Japan. Topographic characteristics of the Dorokawa watershed and its subcatchments were expressed as topographic index (TI) values, which ranged from 4·5 to 20·4 for individual grid cells (50 × 50 m²), but averaged from 6·4 to 7·4 for the 20 subcatchments. Streamwater samples for chemical analyses were collected four times between June and October 2002 from 20 locations in the watershed. The pH of water that passed through the watershed increased from ～5·0 to 7·0, with major increases in Na⁺ and Ca²⁺ and marked decreases in NO₃^? and SO . Distinctive spatial patterns were observed for dissolved organic carbon (DOC), dissolved organic nitrogen (DON), and NO₃^? concentrations of streamwater across the watershed. Statistical analyses indicated significant linear relationships between the average TI values of subcatchments and DOC, DON, and NO₃^? concentrations. Furthermore, the proportion of DOC in streamwaters in the wet season increased with TI values relative to other nitrogen species, whereas NO₃^? concentrations decreased with TI. The gradients of soil wetness and the presence of wetlands explained many of the observed spatial and temporal patterns of DOC, DON, and NO₃^? concentrations in the surface waters of the Dorokawa watershed. Our results suggest that the TI is especially useful for predicting the spatial distribution of DOC, DON and NO₃^? in the surface waters of Hokkaido, where topographical relief is moderate and wetlands more common than in other regions of Japan. Copyright © 2006 John Wiley & Sons, Ltd.     

Effects of permafrost degradation on thermokarst lake hydrochemistry in the Qinghai-Tibet Plateau,China

Thermokarst lakes play a key role in the hydrological and biogeochemical cycles of permafrost regions. Current knowledge regarding the changes caused by permafrost degradation to the hydrochemistry of lakes in the Qinghai-Tibet Plateau (QTP) is limited. To address this gap, a systematic investigation of thermokarst lake water, suprapermafrost water, ground ice, and precipitation was conducted in the hinterland of the QTP. The thermokarst lake water in the QTP was identified to be of the Na-HCO₃-Cl type. The mean concentrations of HCO₃⁻ and Na⁺ were 281.8 mg L⁻¹ (146.0–546.2 mg L⁻¹) and 73.3 mg L⁻¹ (9.2–345.8 mg L⁻¹), respectively. The concentrations of Li⁺, NH₄⁺, K⁺, F⁻, NO₂⁻, and NO₃⁻ were relatively low. Freeze-out fractionation concentrated the dissolved solids within the lake water during winter, which was deeply deepened on lake depth and lake ice thickness. Owing to solute enrichment, the ground ice was characterized by high salinity. Conversely, repeated replenishment via precipitation led to lower solute concentrations in the ground ice near the permafrost table compared to that within the permafrost. Although lower solute concentration existed in precipitation, the soil leaching and saline ground ice melting processes enhanced the solute load in suprapermafrost water, which is considered an important water and solute resource in thermokarst lakes. The influencing mechanism of permafrost degradation on thermokarst lake hydrochemistry is presumably linked to: (1) the liberation of soluble materials sequestered in ground ice; (2) the increase of solutes in suprapermafrost water and soil pore water; and (3) the changes in lake morphometry. These results have major implications on the understanding of the effects of ground ice melting on ecosystem functions, biogeochemical processes, and energy balance in a rapidly changing climate.     

Acidification recovery in a changing climate: Observations from thirty-five years of stream chemistry monitoring in forested headwater catchments at the Turkey Lakes watershed,Ontario

Long-term ecosystem studies are valuable for understanding integrated ecosystem response to global changes in atmospheric deposition and climate. We examined trends for a 35-year period (1982/83–2017/18) in concentrations of a range of solutes in precipitation and stream water from nine headwater catchments spanning elevation and surficial geology gradients at the Turkey Lakes watershed (TLW) in northeastern Ontario, Canada. Average annual water year (WY, October to September) concentrations in precipitation significantly declined over the period for sulphate (SO₄²⁻), nitrate (NO₃⁻) and chloride (Cl⁻), while calcium (Ca²⁺) and potassium (K⁺) concentrations increased, resulting in a significant pH increase from 4.2 to 5.7. Trends in stream chemistry through time are generally consistent with expectations associated with acidification recovery. Concentration of many stream water solutes (SO₄²⁻, Cl⁻, calcium [Ca²⁺], magnesium [Mg²⁺] and NH₄⁺ generally decreased, while others (silica [SiO₂] and dissolved organic carbon [DOC]) generally increased. Increases were also observed for alkalinity (six of nine catchments), acid neutralizing capacity ([ANC]; six of nine catchments) and pH (eight of nine catchments), while conductivity declined (six of nine catchments). Variability in trends among catchments are associated with differences in surficial geology and wetland cover. While absolute solute concentrations were generally lower at bedrock dominated high-elevation catchments compared to till dominated lower elevation catchments, the rate of change of concentration was often greater for high elevation catchments. This study confirms continued, but non-linear stream chemistry recovery from acidification, particularly at the less buffered high and moderate elevation sites. The heterogeneity of responses among catchments highlights our incomplete understanding of the relative importance of different mechanisms influencing stream chemistry and the consequences for downstream ecosystems.     

Assessing DOC export from a Sphagnum‐dominated peatland using δ13C and δ18O–H2O stable isotopes

Dissolved organic carbon (DOC) originating in peatlands can be mineralized to carbon dioxide (CO₂) and methane (CH₄), two potent greenhouse gases. Knowledge of the dynamics of DOC export via run‐off is needed for a more robust quantification of C cycling in peatland ecosystems, a prerequisite for realistic predictions of future climate change. We studied dispersion pathways of DOC in a mountain‐top peat bog in the Czech Republic (Central Europe), using a dual isotope approach. Although δ¹³C_DOC values made it possible to link exported DOC with its within‐bog source, δ¹⁸O_H2O values of precipitation and run‐off helped to understand run‐off generation. Our 2‐year DOC–H₂O isotope monitoring was complemented by a laboratory peat incubation study generating an experimental time series of δ¹³C_DOC values. DOC concentrations in run‐off during high‐flow periods were 20–30 mg L^?1. The top 2 cm of the peat profile, composed of decaying green moss, contained isotopically lighter C than deeper peat, and this isotopically light C was present in run‐off in high‐flow periods. In contrast, baseflow contained only 2–10 mg DOC L^?1, and its more variable C isotope composition intermittently fingerprinted deeper peat. DOC in run‐off occasionally contained isotopically extremely light C whose source in solid peat substrate was not identified. Pre‐event water made up on average 60% of the water run‐off flux, whereas direct precipitation contributed 40%. Run‐off response to precipitation was relatively fast. A highly leached horizon was identified in shallow catotelm. This peat layer was likely affected by a lateral influx of precipitation. Within 36 days of laboratory incubation, isotopically heavy DOC that had been initially released from the peat was replaced by isotopically lighter DOC, whose δ¹³C values converged to the solid substrate and natural run‐off. We suggest that δ¹³C systematics can be useful in identification of vertically stratified within‐bog DOC sources for peatland run‐off.     

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

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

Dissolved organic carbon export from a cutover and restored peatland

High demand for horticultural peat has increased peatland drainage and peat extraction in Canada. The hydrology and carbon cycling of these cutover peatlands is greatly altered, necessitating active restoration efforts to permit the regeneration of Sphagnum mosses and the re‐establishment of natural peatland function. The effect of peatland extraction and restoration on the export of dissolved organic carbon (DOC) was examined for three successive seasons (May to October, 1999 to 2001) at two different sites (cutover and restored) in eastern Québec. A shift towards higher DOC concentrations was observed following peatland extraction (maximum: 182·6 mg L^?1) and concentrations remained high post‐restoration (maximum: 191·0 mg L^?1). The cutover site exported more DOC than the restored site in all three study seasons. The highest exports occurred during the wettest year (1999), with cutover and restored site export of 10·3 and 4·8 g m^?2, respectively. In 2000, 8·5 g C m^?2 was released from the cutover site, while the restored site released less than half that amount (3·4 g C m^?2). In 2001, the restored site released about the same amount of DOC as in the previous year (3·5 g C m^?2), while the cutover site load dropped to 6·2 g C m^?2. Both sites were net exporters of DOC in all years. Copyright © 2007 John Wiley & Sons, Ltd.     

Total waterborne carbon export and DOC composition from ten nested subarctic peatland catchments—importance of peatland cover,groundwater influence,and inter‐annual variability of precipitation patterns

Waterborne carbon (C) export from terrestrial ecosystems is a potentially important flux for the net catchment C balance and links the biogeochemical C cycling of terrestrial ecosystems to their downstream aquatic ecosystems. We have monitored hydrology and stream chemistry over 3 years in ten nested catchments (0.6–15.1 km²) with variable peatland cover (0%–22%) and groundwater influence in subarctic Sweden. Total waterborne C export, including dissolved and particulate organic carbon (DOC and POC) and dissolved inorganic carbon (DIC), ranged between 2.8 and 7.3 g m^–2 year^–1, representing ~10%–30% of catchment net ecosystem exchange of CO₂. Several characteristics of catchment waterborne C export were affected by interacting effects of peatland cover and groundwater influence, including magnitude and timing, partitioning into DOC, POC, and DIC and chemical composition of the exported DOC. Waterborne C export was greater during the wetter years, equivalent to an average change in export of ~2 g m^–2 year^–1 per 100 mm of precipitation. Wetter years led to a greater relative increase in DIC export than DOC export due to an inferred relative shift in dominance from shallow organic flow pathways to groundwater sources. Indices of DOC composition (SUVA₂₅₄ and a₂₅₀/a₃₆₅) indicated that DOC aromaticity and average molecular weight increased with catchment peatland cover and decreased with increased groundwater influence. Our results provide examples on how waterborne C export and DOC composition might be affected by climate change. Copyright © 2012 John Wiley & Sons, Ltd.     

Temporal and spatial variations in the discharge and dissolved organic carbon of drip waters in Beijing Shihua Cave,China

To detect the causal relationship between cave drip waters and stalagmite laminae, which have been used as a climate change proxy, three drip sites in Beijing Shihua Cave were monitored for discharge and dissolved organic carbon (DOC). Drip discharges and DOC were determined at 0 to 14‐day intervals over the period 2004–2006. Drip discharges show two types of response to surface precipitation variations: (1) a rapid response; and (2) a time‐lagged response. Intra‐annual variability in drip discharge is significantly higher than inter‐annual variability. The content of DOC in all drip waters varies inter‐ and intra‐annually and has good correlation with drip water discharge at the rapid response sites. High DOC was observed in July and August in the three years observed. The flushing of soil organic matter is dependent upon the intensity of rain events. The DOC content of drip water increases sharply above a threshold rainfall intensity (>50 mm d^?1) and shows several pulses corresponding with intense rain events (>25 mm d^?1). The DOC content was lower and less variable during the dry period than during the rainy period. The shape of DOC peak also varies from year to year as it is influenced by the intensity and frequency of rainfall. The different drip sites show marked differences in DOC response, which are dominated by hydrological behaviour linked to the recharge of the soil and karst micro‐fissure/porosity network. The results explain why not all stalagmite laminae are consistent with climate changes and suggest that the structure of the rainy season events could be preserved in speleothems. Copyright © 2008 John Wiley & Sons, Ltd.     

EXPORTS OF ORGANIC CARBON IN BRITISH RIVERS

This study provides the first detailed estimate of riverine organic carbon fluxes in British rivers, as well as highlighting major gaps in organic carbon data in national archives. Existing data on organic carbon and suspended solids concentrations collected between 1989 and 1993, during routine monitoring by the River Purification Boards (RPBs) in Scotland and the National River Authorities (NRAs) in England and Wales, were used with annual mean flows to estimate fluxes of dissolved and particulate organic carbon (DOC and POC) in British rivers. Riverine DOC exports during 1993 varied from 7·7–103·5 kg ha⁻¹ year⁻¹, with a median flux of 31·9 kg ha⁻¹ year⁻¹ in the 85 rivers for which data were available. There was a trend for DOC fluxes to increase from the south and east to the north and west. A predictive model based on mean soil carbon storage in 17 catchments, together with regional precipitation totals, explained 94% of the variation in the riverine DOC exports in 1993. This model was used to predict riverine DOC fluxes in regions where no organic carbon data were available. Calculated and predicted fluxes were combined to produce an estimate for exports of DOC to tidal waters in British rivers during 1993 of 0·68±0·07 Mt. Of this total, rivers in Scotland accounted for 53%, England 38% and Wales 9%. Scottish blanket peats would appear to be the largest single source of DOC exports in British rivers. An additional 0·20 Mt of organic carbon were estimated to have been exported in particulate form in 1993, approximately two–thirds of which was contributed by English rivers. It is suggested that riverine losses of organic carbon have the potential to affect the long-term dynamics of terrestrial organic carbon pools in Britain and that rivers may regulate increases in soil carbon pools brought about by climate change. © 1997 by John Wiley & Sons, Ltd.     

Nutrient budget of a montane evergreen broad‐leaved forest at Ailao Mountain National Nature Reserve,Yunnan, southwest China

Hydrological fluxes and associated nutrient budget were studied during a 2 year period (1998–99) in a montane moist evergreen broad‐leaved forest at Ailao Mountain, Yunnan. Water samples of rainfall, throughfall, and stemflow, and of surface runoff, soil water, and stream flow were collected bimonthly to determine the concentration and fluxes of nutrients. Soil budgets were determined from the difference between precipitation input (including nutrient leaching from canopy) and output via runoff and drainage. The forest was characterized by low canopy interception and surface runoff, and high percolation and stream flow. Concentrations of nutrients were increased in throughfall and stemflow compared with precipitation. Surface runoff and drainage water had higher nutrient concentrations than precipitation and stream water. Total nitrogen and NH₄⁺‐N concentrations were higher in soil water than stream water, whereas K⁺, Ca²⁺, and Mg²⁺ concentrations were lower in the former than the latter. Annual nutrient fluxes decreased with soil depth following the pattern of water flux. Annual losses of most nutrient elements via stream flow were less than the corresponding inputs via throughfall and stemflow, except for calcium, for which solute loss was greater than the inputs via precipitation. Leaching losses of that element may be compensated by weathering. Losses of nitrogen, phosphorus, potassium, magnesium, sodium, and sulphur could be replaced through atmospheric inputs. Copyright © 2002 John Wiley & Sons, Ltd.     

Hydrological and catchment controls on event-scale dissolved organic carbon dynamics in boreal headwater streams

Hydrological events transport large proportions of annual or seasonal dissolved organic carbon (DOC) loads from catchments to streams. The timing, magnitude and intensity of these events are very sensitive to changes in temperature and precipitation patterns, particularly across the boreal region where snowpacks are declining and summer droughts are increasing. It is important to understand how landscape characteristics modulate event-scale DOC dynamics in order to scale up predictions from sites across regions, and to understand how climatic changes will influence DOC dynamics across the boreal forest. The goal of this study was to assess variability in DOC concentrations in boreal headwater streams across catchments with varying physiographic characteristics (e.g., size, proportion of wetland) during a range of hydrological events (e.g., spring snowmelt, summer/fall storm events). From 2016 to 2017, continuous discharge and sub-daily chemistry grab samples were collected from three adjacent study catchments located at the International Institute for Sustainable Development-Experimental Lakes Area in northwestern Ontario, Canada. Catchment differences were more apparent in summer and fall events and less apparent during early spring melt events. Hysteresis analysis suggested that DOC sources were proximal to the stream for all events at a catchment dominated by a large wetland near the outlet, but distal from the stream at the catchments that lacked significant wetland coverage during the summer and fall. Wetland coverage also influenced responses of DOC export to antecedent moisture; at the wetland-dominated catchment, there were consistent negative relationships between DOC concentrations and antecedent moisture, while at the catchments without large wetlands, the relationships were positive or not significant. These results emphasize the utility of sub-daily sampling for inferring catchment DOC transport processes, and the importance of considering catchment-specific factors when predicting event-scale DOC behaviour.     

Factors influencing the release of dissolved organic carbon and dissolved forms of nitrogen from a small upland headwater during autumn runoff events

We identify and assess the relative importance of the principal factors influencing the release of dissolved organic carbon (DOC) and dissolved forms of nitrogen (N) from a small upland headwater dominated by podzolic soils during a sequence of autumn runoff events. We achieve this by subjecting high‐resolution hydrometeorological and hydrochemical data to an R‐mode principal component factor analysis and a stepwise multivariate regression analysis. We find that the release of DOC and N is influenced by four principal factors, namely event magnitude, soil water flow through the Bs horizon, the length of time since the soil profile was last flushed, and rewetting of the H horizon. The release of DOC and dissolved organic nitrogen (DON) is most strongly influenced by the combination of event magnitude and soil water flow through the Bs horizon, and to a lesser extent by the length of time since the soil profile was last flushed. Rewetting of the H horizon also influences the release of DOC, but this is not the case for DON. The release of nitrate (NO₃‐N) is most strongly influenced by the combination of the length of time since the soil profile was last flushed and rewetting of the H horizon, and to a lesser extent by event magnitude. Soil water flow through the Bs horizon does not influence the release of NO₃‐N. We argue that the mechanisms by which the above factors influence the release of DOC and N are probably strongly associated with moisture‐dependent biological activity, which governs the turnover of organic matter in the soil and limits the availability of NO₃‐N in the soil for leaching. We conclude that the release of DOC and N from upland headwaters dominated by podzolic soils is largely controlled by the variable interaction of hydrometeorological factors and moisture‐dependent biological processes, and that a shift in climate towards drier summers and wetter winters may result in the release of DOC and N becoming increasingly variable and more episodic in the future. Copyright © 2006 John Wiley & Sons, Ltd.     

The influence of fire and permafrost on sub‐arctic stream chemistry during storms

Permafrost and fire are important regulators of hydrochemistry and landscape structure in the discontinuous permafrost region of interior Alaska. We examined the influence of permafrost and a prescribed burn on concentrations of dissolved organic carbon (DOC), dissolved organic nitrogen (DON) and other solutes ( , Ca²⁺, K⁺, Mg²⁺, Na⁺) in streams of an experimentally burned watershed and two reference watersheds with varying extents of permafrost in the Caribou–Poker Creeks Research Watershed in interior Alaska. The low‐permafrost watershed has limited permafrost (3%), the high‐permafrost watershed has extensive permafrost (53%), and the burn watershed has intermediate permafrost coverage (18%). A three end‐member mixing model revealed fundamental hydrologic and chemical differences between watersheds due to the presence of permafrost. Stormflow in the low‐permafrost watershed was dominated by precipitation and overland flow, whereas the high‐permafrost watershed was dominated by flow through the active layer. In all watersheds, organic and groundwater flow paths controlled stream chemistry: DOC and DON increased with discharge (organic source) and base cations and (from weathering processes) decreased. Thawing of the active layer increased soil water storage in the high‐permafrost watershed from July to September, and attenuated the hydrologic response and solute flux to the stream. The FROSTFIRE prescribed burn, initiated on 8 July 1999, elevated nitrate concentrations for a short period after the first post‐fire storm on 25 July, but there was no increase after a second storm in September. During the July storm, nitrate export lagged behind the storm discharge peak, indicating a flushing of soluble nitrate that likely originated from burned soils. Copyright © 2006 John Wiley & Sons, Ltd.