Sherry L. Schiff

The significance of storms for the concentration and export of dissolved organic carbon from two Precambrian Shield catchments

Dissolved organic carbon (DOC) concentrations and DOC export arestudied during storms to examine the relationship between DOCconcentration and stream discharge and to assess the importance of stormson DOC export. Storms were monitored in seven subcatchments within twosmall watersheds (Harp 4--21 and Harp 3A) on the Precambrian Shield inCentral Ontario, Canada. Stream DOC concentrations increase during stormsby as much as 100% and 410% in Harp3A and Harp 4--21 respectively. The seasonal regression between DOC andstream discharge is significant in subcatchments without wetlands(r2 > 0.7) but is not significant in thetwo subcatchments with small wetland areas (r2 <0.06). On average, regressions based on weekly data yield accurate estimatesof DOC export but the variation in regressions among individual storms andthe small number of high DOC samples result in uncertainties of more than30% in DOC export. The period-weighted calculation ofDOC export from weekly data underestimates export by 14%and 22% in Harp 3A and Harp 4--21 respectively. Stormswere responsible for 57% to 68% of theDOC export in the autumn and 29% to 40%of the DOC export in the spring. A single large storm accounted for31% of the autumn DOC export in Harp 3A. The importanceof individual storms for DOC export and the variation in the relationshipbetween DOC and stream discharge among storms make it difficult to predictthe effects of climate change on DOC export and DOC concentrations.

Sources and flowpaths of dissolved organic carbon during storms in two forested watersheds of the Precambrian Shield

Dissolved organic carbon (DOC) concentrations and export were studied in two small catchments in central Ontario to examine DOC sources and to assess the hypothesis that organic matter adjacent to the stream is a significant contributor of DOC during storms. Different DOC dynamics and exports were observed according to the depth of the riparian water table. In Harp 4-21, riparian flowpaths were predominantly through A and upper B soil horizons and riparian soils contributed between 73 and 84% of the stream DOC export during an autumn storm. In Harp 3A, riparian flowpaths were predominantly through lower B horizons. Consequently, riparian soils were less important and hillslopes contributed more than 50% of the stream DOC export in subcatchments without wetlands during storms. Wetlands and adjacent soils contributed significantly to DOC export in Harp 3A; 8% of the total catchment area exported 32 to 46% of the storm runoff DOC. DOC export dynamics in wetlands and riparian soils were distinctly different. In wetlands, transport was affected by leaching and flushing of DOC at the wetland surface leading to lower DOC concentrations with successive storms. In riparian soils, groundwater flowpaths were more important and stronger positive relationships between discharge and DOC concentration were observed. Precipitation, throughfall and stemflow were minor sources of stream DOC during storms and contributed less than 20% of the total export.

Export of DOC from forested catchments on the Precambrian Shield of Central Ontario: Clues from 13C and 14C

Export of dissolved organic carbon (DOC) from forested catchmentsis governed by competing processes of production, decomposition, sorptionand flushing. To examine the sources of DOC, carbon isotopes (14Cand 13C) were analyzed in DOC from surface waters, groundwatersand soils in a small forested catchment on the Canadian Shield in centralOntario. A significant fraction (greater than 50%) of DOCin major inflows to the lake is composed of carbon incorporated into organicmatter, solubilized and flushed into the stream within the last 40 years. Incontrast, 14C in groundwater DOC was old indicating extensiverecycling of forest floor derived organic carbon in the soil column beforeelution to groundwater in the lower B and C soil horizons. A small uplandbasin had a wide range in 14C from old groundwater values atbaseflow under dry basin conditions to relatively modern values during highflow or wetter antecedent conditions. Wetlands export mainly recently fixedcarbon with little seasonal range. DOC in streams entering the small lakemay be composed of two pools; an older recalcitrant pool delivered bygroundwater and a young labile pool derived from recent organic matter.The relative proportion of these two pools changes seasonally due thechanges in the water flowpaths and organic carbon dynamics. Althoughchanges in local climate (temperature and/or precipitation) may alterthe relative proportions of the old and young pools, the older pool islikely to be more refractory to sedimentation and decomposition in thelake setting. Delivery of older pool DOC from the catchment andsusceptibility of this older pool to photochemical decomposition mayconsequently be important in governing the minimum DOC concentrationlimit in lakes.

Precambrian Shield Wetlands: Hydrologic Control of the Sources and Export of Dissolved Organic Matter

Most Precambrian Shield forested catchments have some wetland component. Even small riparian wetlands are important modifiers of stream chemistry. Dissolved organic matter (DOM) is one of the most important products exported by wetlands in streams. Stratigraphic control of hydraulic conductivity generally leads to decreasing conductivity with depth. Thus important flowpaths occur in the uppermost organic rich layers and are reflected in chemical profiles of dissolved organic carbon (DOC). Accumulation of DOC in peat porewaters is the net effect of production, consumption and transport. DOC profiles vary with degree of interaction with the surrounding upland catchment and distance from the edge of the wetland as well as internal processes within the wetland. In wetlands, DOM production is offset by flushing resulting in decreasing DOC concentrations with increasing flows. Despite old carbon (2,000 to 3,000 years) at relatively shallow depths, 14C activity in DOC exported from wetlands is mostly modern (recent carbon), consistent with shallow flowpaths and export of DOM from shallow organic rich horizons. In contrast, the source area for DOM in upland catchments with developed B horizon soils increases with antecedent soil moisture conditions resulting in increasing DOC concentrations with higher stream flows. Activity of 14C in stream DOC from upland catchments span a range from low activities (older carbon) similar to B horizon soil water during dry moisture conditions to values slightly less than modern (more recent carbon) during high moisture conditions. The more modern carbon activities reflect the increased contribution of the organic rich litter and A horizon soil layers in the area immediately bordering the stream under wet antecedent moisture conditions. Reduced hydrologic export or loss of wetlands under drier climatic conditions may result in in larger fluctuations in stream DOC concentrations and reduced DOM loads to lakes.

Chemical Characteristics of Particulate, Colloidal, and Dissolved Organic Material in Loch Vale Watershed, Rocky Mountain National Park

The chemical relationships among particulate and colloidal organicmaterial and dissolved fulvic acid were examined in an alpine andsubalpine lake and two streams in Loch Vale Watershed, Rocky MountainNational Park. The alpine lake, Sky Pond, had the lowest dissolved organiccarbon (DOC) (0.37 mgC/L), the highest particulate carbon (POC) (0.13mgC/L), and high algal biomass. The watershed of Sky Pond is primarilytalus slope, and DOC and POC may be autochthonous. Both Andrews Creekand Icy Brook gain DOC as they flow through wet sedge meadows. Thesubalpine lake, The Loch, receives additional organic material from thesurrounding forest and had a higher DOC (0.66 mgC/L). Elemental analysis,stable carbon isotopic compositon, and 13C-NMR characterizationshowed that: 1) particulate material had relatively high inorganic contentsand was heterogeneous in compositon, 2) colloidal material was primarilycarbohydrate material with a low inorganic content at all sites; and 3)dissolved fulvic acid varied in compositon among sites. The lowconcentration and carbohydrate-rich character of the colloidal materialsuggests that this fraction is labile to microbial degradation and may beturning over more rapidly than particulate fractions or dissolved fulvic acid.Fulvic acid from Andrews Creek had the lowest N content and aromaticity,whereas Sky Pond fulvic acid had a higher N content and lower aromaticitythan fulvic acid from The Loch. The UV-visible spectra of the fulvic acidsdemonstrate that variation in characteristics with sources of organic carboncan explain to some extent the observed non-linear relationship betweenUV-B extinction coefficients and DOC concentrations in lakes.

Examining the contributions of glacial till water to storm runoff using two‐ and three‐component hydrograph separations

Two- and three-component hydrograph separations based on 18O and dissolved silica are used to investigate the contributions of glacial till water to the storm runoff of a headwater stream on the Canadian Shield. Two-component isotopic hydrograph separations based on 18O indicate that the volume and flux of event water could be accounted for by direct precipitation onto saturated areas. Three-component hydrograph separations distinguish between event water, preevent soil water, and preevent till water. These results show that groundwater flow through coarse-textured glacial tills can make a significant contribution to stream discharge during runoff events (29 and 62% in this study) despite the lower hydraulic conductivities of the tills compared to the overlying soils. The three-component hydrograph separations also demonstrate that the relative contributions of preevent soil water and preevent till water changed during one runoff event such that the average water chemistry of the preevent component varied during the event. Two-component hydrograph separations using dissolved silica indicate that seasonal changes in the till water contributions also occur and are related to groundwater levels. Measurements of vertical hydraulic gradients during runoff events indicate that the increase in flow from the tills to the soils is minimal and cannot account for the large and rapid increase in till water flow into the stream. Till water that has discharged to the soils prior to the event is probably being flushed from the soils into the stream during events.

A validation of the 3H/3He method for determining groundwater recharge

Tritium and He isotopes have been measured at a site where groundwater flow is nearly vertical for a travel time of 100 years and where recharge rates are spatially variable. Because the mid-1960s 3H peak (arising from aboveground testing of thermonuclear devices) is well-defined, the vertical groundwater velocity is known with unusual accuracy at this site. Utilizing 3H and its stable daughter 3He to determine groundwater ages, we compute a recharge rate of 0.16 m/yr, which agrees to within about 5% of the value based on the depth of the 3H peak (measured both in 1986 and 1991) and two-dimensional modeling in an area of high recharge. Zero 3H/3He age occurs at a depth that is approximately equal to the average depth of the annual low water table, even though the capillary fringe extends to land surface during most of the year at the study site. In an area of low recharge (0.05 m/yr) where the 3H peak (and hence the vertical velocity) is also well-defined, the 3H/3He results could not be used to compute recharge because samples were not collected sufficiently far above the 3H peak; however, modeling indicates that the 3H/3He age gradient near the water table is an accurate measure of vertical velocities in the low-recharge area. Because 3H and 3He have different diffusion coefficients, and because the amount of mechanical mixing is different in the area of high recharge than in the low-recharge area, we have separated the dispersive effects of mechanical mixing from molecular diffusion. We estimate a longitudinal dispersivity of 0.07 m and effective diffusion coefficients for 3H (3HHO) and 3He of 2.4×10−5 and 1.3×10−4 m2/day, respectively. Although the 3H/3He age gradient is an excellent indicator of vertical groundwater velocities above the mid-1960s 3H peak, dispersive mixing and diffusive loss of 3He perturb the age gradient near and below the 3H peak.

Tritium and helium: 3 as groundwater age tracers in the Borden Aquifer

Vertical profiles of 3H and He isotope ratios have been measured in groundwater from the well-characterized Borden aquifer, Ontario. The sum of 3H and tritiogenic 3He (3He*) is used as an equivalent nondecaying tracer, while the ratio of 3He* to 3H is used to compute groundwater ages. The mid-1960s 3H peak is not always apparent using the 3H data because both dispersion and radioactive decay have significantly reduced the magnitude of the 3H bomb peak. However, the sum of 3H and 3He* clearly defines the bomb peak at several locations. The accuracy of the 3H/3He dating method depends on the ability of the saturated zone to retain 3He* against diffusive loss at the water table and on the amount of dispersive mixing that occurs within the saturated zone of shallow unconfined aquifers. Helium 3 confinement is strong while dispersive mixing is weak in the Borden aquifer, resulting in an excellent delineation of groundwater travel times. Computed 3H/3He age profiles are compared with travel times predicted using a previously calibrated flow model. Although the 3H/3He age profiles are vertically offset from the modeled travel times, the travel time and 3H/3He age gradients compare exceptionally well. Recharge rates have been computed using the 3H/3He age gradients and vary from 62 cm yr−1 beneath the Borden landfill to 14 cm yr−1 north of the landfill. The 3H/3He-computed recharge agrees well with the recharge function used in previous flow modeling.

Controls on δ34S and δ18O of dissolved sulfate in aquifers of the Murray Basin, Australia and their use as indicators of flow processes

The usefulness of stable isotopes of dissolved SO4 (δ34S and δ18O) to study recharge processes and to identify areas of significant inter-aquifer mixing was evaluated in a large, semi-arid groundwater basin in south-eastern Australia (the Murray Basin). The distinct isotopic signatures in the oxidizing unconfined Murray Group Aquifer and the deeper reducing Renmark Group confined aquifer may be more sensitive than conventional chemical tracers in establishing aquifer connections. δ34S values in the unconfined Murray Group Aquifer in the south and central part of the study area decrease along the hydraulic gradient from 20.8 to 0.3‰. The concomitant increasing SO4/Cl ratios, as well as relatively low δ18OSO4 values, suggest that vertical input of biogenically derived SO4 via diffuse recharge is the predominant source of dissolved SO4 to the aquifer. Further along the hydraulic gradient towards the discharge area near the River Murray, δ34S values in the unconfined Murray Group Aquifer increase, and SO4/Cl ratios decrease, due to upward leakage of waters from the confined Renmark Group Aquifer which has a distinctly low SO4/Cl and high δ34S (14.9–56.4‰). Relatively positive δ34S and δ18OSO4 values, and low SO4/Cl in the Renmark Group Aquifer is typical of SO4 removal by bacterial reduction. The S isotope fractionation between SO4 and HS− of ∼24‰ estimated for the confined aquifer is similar to the experimentally determined chemical fractionation factor for the reduction process but much lower than the equilibrium fractionation (∼70‰) even though the confined groundwater residence time is >300 Ka years. Mapping the spatial distribution of δ34S and SO4/Cl of the unconfined Murray Group Aquifer provides an indicative tool for identifying the approximate extent of mixing, however the poorly defined end-member isotopic signatures precludes quantitative estimates of mixing fractions.

Tracing the Sources of Exported Nitrate in the Turkey Lakes Watershed Using 15N/14N and 18O/16O isotopic ratios

Nitrate produced by bacterially mediated nitrification in soils is isotopically distinct from atmospheric nitrate in precipitation. 15N/14N and 18O/16O isotopic ratios of nitrate can therefore be used to distinguish between these two sources of nitrate in surface waters and groundwaters. Two forested catchments in the Turkey Lakes Watershed (TLW) near Sault Ste. Marie, Ontario, Canada were studied to determine the relative contributions of atmospheric and microbial nitrate to nitrate export. The TLW is reasonably undisturbed and receives a moderate amount of inorganic nitrogen bulk deposition (8.7 kg N · ha−1· yr−1) yet it exhibits unusually low inorganic nitrogen retention (average = 65% of deposition). The measured isotopic ratios for nitrate in precipitation ranged from +35 to +59‰ (VSMOW) for δ18O and −4 to +0.8‰ (AIR) for δ15N. Nitrate produced from nitrification at the TLW is expected to have an average isotope value of approximately −1.0‰ for δ18O and a value of about 0 to +6‰ for δ15N, thus, the isotopic separation between atmospheric and soil sources of nitrate is substantial. Nitrate produced by nitrification of ammonium appears to be the dominant source of the nitrate exported in both catchments, even during the snowmelt period. These whole catchment results are consistent with the results of small but intensive plot scale studies that have shown that the majority of the nitrate leached from these catchments is microbial in origin. The isotopic composition of stream nitrate provides information about N-cycling in the forested upland and riparian zones on a whole catchment basis.