To assess the concern over declining base cation levels in forest soils caused by acid deposition, input-output budgets (1990s average) for sulphate (SO(4)), inorganic nitrogen (NO(3)-N; NH(4)-N), calcium (Ca), magnesium (Mg) and potassium (K) were synthesised for 21 forested catchments from 17 regions in Canada, the United States and Europe. Trend analysis was conducted on monthly ion concentrations in deposition and runoff when more than 9 years of data were available (14 regions, 17 sites). Annual average SO(4) deposition during the 1990s ranged between 7.3 and 28.4 kg ha(-1) per year, and inorganic nitrogen (N) deposition was between 2.8 and 13.8 kg ha(-1) per year, of which 41-67% was nitrate (NO(3)-N). Over the period of record, SO(4) concentration in deposition decreased in 13/14 (13 out of 14 total) regions and SO(4) in runoff decreased at 14/17 catchments. In contrast, NO(3)-N concentrations in deposition decreased in only 1/14 regions, while NH(4)-N concentration patterns varied; increasing at 3/14 regions and decreasing at 2/14 regions. Nitrate concentrations in runoff decreased at 4/17 catchments and increased at only 1 site, whereas runoff levels of NH(4)-N increased at 5/17 catchments. Decreasing trends in deposition were also recorded for Ca, Mg, and K at many of the catchments and on an equivalent basis, accounted for up to 131% (median 22%) of the decrease in acid anion deposition. Base cation concentrations in streams generally declined over time, with significant decreases in Ca, Mg and K occurring at 8, 9 and 7 of 17 sites respectively, which accounted for up to 133% (median 48%) of the decrease in acid anion concentration. Sulphate export exceeded input at 18/21 catchments, likely due to dry deposition and/or internal sources. The majority of N in deposition (31-100%; median 94%) was retained in the catchments, although there was a tendency for greater NO(3)-N leaching at sites receiving higher (<7 kg ha(-1) per year) bulk inorganic N deposition. Mass balance calculations show that export of Ca and Mg in runoff exceeds input at all 21 catchments, but K export only exceeds input at 16/21 sites. Estimates of base cation weathering were available for 18 sites. When included in the mass balance calculation, Ca, Mg and K exports exceeded inputs at 14, 10 and 2 sites respectively. Annual Ca and Mg losses represent appreciable proportions of the current exchangeable soil Ca and Mg pools, although losses at some of the sites likely occur from weathering reactions beneath the rooting zone and there is considerable uncertainty associated with mineral weathering estimates. Critical loads for sulphur (S) and N, using a critical base cation to aluminium ratio of 10 in soil solution, are currently exceeded at 7 of the 18 sites with base cation weathering estimates. Despite reductions in SO(4) and H(+) deposition, mass balance estimates indicate that acid deposition continues to acidify soils in many regions with losses of Ca and Mg of primary concern.
Dissolved organic carbon (DOC) fluxes at eight headwater basins in south-central Ontario were strongly related to seasonal streamflow, and extreme events contributed to both interannual and intercatchment variability. Six catchments with high stream DOC and greater peatland coverage exhibited a different seasonal pattern of DOC concentration compared with two catchments with low DOC and less wetland influence. In wetland-dominated catchments, DOC concentrations decreased during fall wet-up and spring melt, and because of the dominance of the spring melt period in annual budgets, variations in spring flow explained 39%–48% of the intervariability in DOC concentration. Significant increases in average DOC concentration between 1980 and 2001 at all six wetland-dominated catchments were driven by relatively high DOC concentrations in the latter years of record, consistent with low spring flow in these years, and were not translated into greater DOC export to downstream lakes. Localized rainstorms in summer and fall resulted in differences in DOC export among adjacent catchments, and a single fall storm in September 1998 was only detected at one of six catchments draining into Harp Lake but accounted for one-quarter of the annual tributary DOC load to the lake.
Dissolved organic carbon (DOC) plays an important role in surface water chemistry and ecology and trends in DOC concentration have been also associated with shifts in terrestrial carbon pools. Numerous studies have reported long-term trends in DOC concentration; however, some studies consider changes in average measured DOC whereas other compute discharge weighted concentrations. Because of differences in reporting methods and variable record lengths it is difficult to compare results among studies and make regional generalizations. Furthermore, changes in stream discharge may impact longterm trends in DOC concentration and the potentially subtle effect of shifts in stream flow may be missed if only measured DOC concentrations are considered. In this study we compare trends in volume-weighted vs. average measured DOC concentration between 1980 and 2001 at seven headwater streams in southcentral Ontario, Canada that vary in wetland coverage and DOC (22-year mean vol. wt.) from 3.4 to 10.6 mg l -1 . On average, annual measured DOC concentrations were 13-34% higher than volumeweighted values, but differences of up to 290% occurred in certain years. Estimates of DOC flux were correspondingly higher using measured concentration values. Both measured and volume-weighted DOC concentrations increased significantly between 1980 and 2001, but slopes were larger in measured data (0.04-0.35 mg l -1 year -1 compared with 0.05-0.15 mg l -1 year -1 ) and proportional increases at the most wetland-influenced sites ranged from 32 to 43% in volume-weighted DOC and from 52 to 75% in measured DOC. In contrast, DOC flux did not change with time when estimated using either method, because of the predominant influence of stream flow on DOC export. Our results indicate that changes in stream flow have an important impact on trends in DOC concentration, and extrapolation of trend results from one region to another should be made cautiously and consider methodological and reporting differences among sites.
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