David Toczydlowski

Stream chemistry and hydrologic pathways during snowmelt in a small watershed adjacent Lake Superior

In regions with airborne contaminants and large snowpacks, there is concern over the impact that snowmelt chemical “pulses” — periods of sharp increase in meltwater solute concentration — could have on aquatic resources during spring runoff. A major variable in determining such an effect is the flow path of snowmelt solutes to the stream or lake. From December 1988, to late April 1989, the quality and quantity of precipitation, snowmelt, soil solution and streamwater were measured in a 176-ha gauged watershed on the south shore of Lake Superior. The main objectives were to (1) examine the change in flow path meltwaters take to the stream during distinct winter and spring hydrologic periods, (2) quantify ecosystem-level ion budgets prior to, during, and following snowmelt, and (3) examine if streamwater chemistry might be a sensitive indicator of change in ecosystem flow paths. Prior to peak snowmelt, groundwater made up 80% of stream discharge. During peak snowmelt, the groundwater level rose to the soil surface resulting in lateral water movement through near-surface macropores and as overland flow. Near the end of snowmelt, melt-waters exerted a piston action on deeper soil solution again increasing its relative contribution to streamwater discharge. Net groundwater drawdown during the study resulted in streamwater discharge about equal to precipitation inputs. Unfrozen soils and brief mid-winter thaws resulted in steady snowmelt throughout early and mid-winter. The snowpack lost > 50% of most ions prior to the period of major snowmelt and high stream discharge in late March and early April. Snowmelt and streamwater NO3− and NH4 pulses occurred before the period of overland flow and peak streamwater discharge (April 4–24). During overland flow, stream discharge of total N, P, DOC, and AI peaked. Nutrient budgets computed for distinct hydrologic periods were much more helpful in explaining ecosystem pathways and processes than were changes in solute concentration. For the study period, watershed base cation (CB) discharge was 23 times input and SO42− discharge exceeded input by 42%. H+ was the most strongly conserved ion with output < 0.2% of input. Also conserved were NH4+ with only 1.4% of input leaving the ecosystem and NO3− with output equal to 9.4% of input.

Seasonal change in precipitation, snowpack, snowmelt, soil water and streamwater chemistry, northern Michigan

We have studied weekly precipitation, snowpack, snowmelt, soil water and streamwater chemistry throughout winter for over a decade in a small (176 ha) northern Michigan watershed with high snowfall and vegetated by 60 to 80 year-old northern hardwoods. In this paper, we examine physical, chemical, and biological processes responsible for observed seasonal change in streamwater chemistry based upon intensive study during winter 1996-1997. The objective was to define the contributions made to winter and spring streamwater chemical concentration and flux by processes as snowmelt, over-winter forest floor and surface soil mineralization. immobilization, and exchange, and subsurface flowpath. The forest floor and soils were unfrozen beneath the snowpack which permitted most snowmelt to enter. Over-winter soil mineralization and other biological processes maintain shallow subsurface ion and dissolved organic carbon (DOC) reservoirs. Small, but steady, snowmelt throughout winter removed readily mobilized soil NO 3 - which resulted in high over-winter streamwater concentrations but little flux. Winter soil water levels and flowpaths were generally deep which increased soil water and streamwater base cation (C B ), HCO 3 - , and Si concentrations. Spring snowmelt increased soil water levels and removal of ions and DOC from the biologically active forest floor and shallow soils. The snowpack solute content was a minor component in determining streamwater ion concentration or flux during and following peak snowmelt. Exchangeable ions, weakly adsorbed anions, and DOC in the forest floor and surface soils dominated the chemical concentration and flux in soil water and streamwater. Following peak snowmelt, soil microbial immobilization and rapidly increased plant uptake of limiting nutrients removed nearly all available nitrogen from soil water and streamwater. During the growing season high evapotranspiration increased subsurface flowpath depth which in turn removed weathering products, especially C B , HCO 3 - , and Si, from deeper soils. Soil water was a major component in the hydrologic and chemical budgets.

Nitrogen deposition to lakes in national parks of the western Great Lakes region: Isotopic signatures, watershed retention, and algal shifts

Atmospheric deposition is a primary source of reactive nitrogen (Nr) to undisturbed watersheds of the Great Lakes region of the U.S., raising concerns over whether enhanced delivery over recent decades has affected lake ecosystems. The National Atmospheric Deposition Program (NADP) has been measuring Nr deposition in this region for over 35 years. Here we explore the relationships among NADP-measured Nr deposition, nitrogen stable isotopes (δ15N) in lake sediments, and the response of algal communities in 28 lakes situated in national parks of the western Great Lakes region of the U.S. We find that 36% of the lakes preserve a sediment δ15N record that is statistically correlated with some form of Nr deposition (total dissolved inorganic N, nitrate, or ammonium). Furthermore, measured long-term (since 1982) nitrogen biogeochemistry and inferred critical nitrogen loads suggest that watershed nitrogen retention and climate strongly affect whether sediment δ15N is related to Nr deposition in lake sediment records. Measurements of algal change over the last ~ 150 years suggest that Nr deposition, in-lake nutrient cycling, and watershed inputs are important factors affecting diatom community composition, in addition to direct climatic effects on lake physical limnology. The findings suggest that bulk sediment δ15N does reflect Nr deposition in some instances. In addition, this study highlights the interactive effects of Nr deposition and climate variability.

Temporal patterns of dissolved organic matter biodegradability are similar across three rivers of varying size

Dissolved organic matter (DOM) composition may be an important determinant of its fate in freshwaters, but little is known about temporal variability in DOM composition and the biodegradability of DOM in northern temperate watersheds. We measured biodegradable dissolved organic carbon (BDOC) via incubation assays and DOM composition using optical indices on 11 dates in three Lake Superior tributaries. Percent BDOC (%BDOC) and BDOC concentrations were seasonally synchronous across these watersheds, despite that they vary in size by orders of magnitude (1.7 to 3400 km2). Relative to %BDOC, BDOC concentrations were more tightly constrained among sites on any given date. BDOC also varied within seasons; for example, %BDOC on two different dates in winter were among the highest (29% and 54%) and lowest (0%) values observed for each site (overall %BDOC range: 0 to 72%). DOM composition varied the most among tributaries during a summer storm event when BDOC (both as percent and concentration) was elevated but was remarkably similar among tributaries during fall, spring, and winter. Multivariate models identified humic-like and tryptophan-like fluorophores as predictors of %BDOC, but DOM composition only described 21% of the overall variation in %BDOC. Collectively, these three rivers exported ~18 Gg C yr−1 as DOC and ~2 Gg C yr−1 as BDOC, which corresponded to 9 to 17% of annual DOC exported in biodegradable form. Our results suggest much of the C exported from these northern temperate watersheds may be biodegradable within 28 days and that large pulses of labile DOM can be exported during storm events and spring snowmelt.

Of Small Streams and Great Lakes: Integrating Tributaries to Understand the Ecology and Biogeochemistry of Lake Superior

Lake Superior receives inputs from approximately 2,800 tributaries that provide nutrients and dissolved organic matter (DOM) to the nearshore zone of this oligotrophic lake. Here, we review the magnitude and timing of tributary export and plume formation in Lake Superior, how these patterns and interactions may shift with global change, and how emerging technologies can be used to better characterize tributary–lake linkages. Peak tributary export occurs during snowmelt-driven spring freshets, with additional pulses during raindriven storms. Instream processing and transformation of nitrogen, phosphorus, and dissolved organic carbon (DOC) can be rapid but varies seasonally in magnitude. Tributary plumes with elevated DOC concentration, higher turbidity, and distinct DOM character can be detected in the nearshore during times of high runoff, but plumes can be quickly transported and diluted by in-lake currents and mixing. Understanding the variability in size and load of these tributary plumes, how they are transported within the lake, and how long they persist may be best addressed with environmental sensors and remote sensing using autonomous and unmanned vehicles. The connections between Lake Superior and its tributaries are vulnerable to climate change, and understanding and predicting future changes to these valuable freshwater resources will require a nuanced and detailed consideration of tributary inputs and interactions in time and space.

Effects of acid deposition on watershed ecosystems of national parks in the great lakes basin

Legally protected national parks provide an appropriate substrate for essential long-term study of ecosystem structure and function, and for detecting trends in natural and human-induced stress. The absence of unplanned site manipulation in such areas is especially valuable for such research. Our present research has two major components. The first is the long-term ecosystem-level study of the effects of atmospheric contaminants on ecosystem processes. The overall objective is to evaluate ecosystem aquatic/terrestrial linkages and their role in establishing aquatic ecosystem sensitivity to anthropic atmospheric inputs. Four watershed/lake ecosystems, representative of much of the regions diversity, are under study. Two mature boreal sites on Isle Royale are characterized by first-order perennial surface stream input and lake outflow. Two additional mainland northern hardwood sites, one with shallow soils and one with soils derived from glacial till, are characterized by sensitive aquatic systems. One site is in a private reserve and the other in Pictured Rocks National Lakeshore. Surface outflow is gaged by Parshall flume and stage height recorder. Meteorological stations record variables for estimating evapotranspiration. One-tenth ha plots have been established in all watersheds and three sites have had intensive study of precipitation modification by canopy and forest soil. Five-year mean maximum and minimum lake pH varies from 6.85 to 4.94, Ca2+ from 1070 to 54 μ eq l-1, K+ from 5.42 to 8.35 μ eq l-1, NH4+from 10.12 to 3.23 μ eq l-1, HCO3sup-from 635 to 24 μ eq l-1, NO3sup-from 3.27 to 1.54 μ eq l-1, and SO4sup2-from 110 to 52.7 μ eq l-1. The relatively high NO3sup-values observed in one lake are the result of stream drainage from a watershed dominated by Alnus rugosa, and another has high seasonal NO3sup-inputs during spring runoff. However, owing to periodic winter thaws, significant snowpack release of nutrients generally precedes maximum spring stream runoff. Water chemistry in both sensitive and non-sensitive lakes appears to be primarily reflecting how the conterminous terrestrial system is retaining atmospheric inputs more than the quality of direct lake atmospheric input. This is especially evident for H+, NO3sup-and SO4sup2-.The second component is the assessment of watershed acidification, SO4sup2-output and soil retention across an input gradient. An anthropic deposition gradient provides the opportunity for intersite time-trend analyses as to the effects of inputs. Our study objective was to see if the decreasing west to east input/output values for SO4sup2-, noted in small first-order watersheds in national parks from Minnesota to Ohio, might be related to present atmospheric inputs, potential and total soil SO4sup2-adsorption, or soil SO4sup2-desorption from earlier higher inputs. Precipitation pH ranged from 5.05 at Fernberg, Minnesota to 4.24 at Wooster, Ohio. Minimum and maximum concentrations of NH4+, NO3sup-, SO4sup2-and Cl- were also found at these stations. Stream water concentrations of NO3sup-and SO4sup2-increase in a similar but sharper gradient. Streams are well buffered. Cation, HCO3sup-, NO3sup-and especially SO4sup2-output increase west to east, but H+ output decreases. At the eastern site stream SO4sup2-concentration and output exceed HCO3sup-. Potential soil SO4sup2-adsorption capacity increases eastward, but this capacity is filled. Crystalline Fe hydrous oxides appear more effective than amorphous Fe hydrous oxides at adsorbing SO4sup2-. High anthropic anion inputs, inability of forest soil to adsorb additional inputs and perhaps SO4sup2-desorption appear responsible for the replacement of HCO3sup-by SO4sup2-in stream water. The major cation accompanying SO4sup2-is Ca2+.