Peter S. Murdoch

Regional nitrogen budgets and riverine N & P fluxes for the drainages to the North Atlantic Ocean: Natural and human influences

We present estimates of total nitrogen and total phosphorus fluxes in rivers to the North Atlantic Ocean from 14 regions in North America, South America, Europe, and Africa which collectively comprise the drainage basins to the North Atlantic. The Amazon basin dominates the overall phosphorus flux and has the highest phosphorus flux per area. The total nitrogen flux from the Amazon is also large, contributing 3.3 Tg yr-1 out of a total for the entire North Atlantic region of 13.1 Tg yr-1. On a per area basis, however, the largest nitrogen fluxes are found in the highly disturbed watersheds around the North Sea, in northwestern Europe, and in the northeastern U.S., all of which have riverine nitrogen fluxes greater than 1,000 kg N km-2 yr-1.

Regional trends in aquatic recovery from acidification in North America and Europe

Rates of acidic deposition from the atmosphere (‘acid rain’) have decreased throughout the 1980s and 1990s across large portions of North America and Europe. Many recent studies have attributed observed reversals in surface-water acidification at national and regional scales to the declining deposition. To test whether emissions regulations have led to widespread recovery in surface-water chemistry, we analysed regional trends between 1980 and 1995 in indicators of acidification (sulphate, nitrate and base-cation concentrations, and measured (Gran) alkalinity) for 205 lakes and streams in eight regions of North America and Europe. Dramatic differences in trend direction and strength for the two decades are apparent. In concordance with general temporal trends in acidic deposition, lake and stream sulphate concentrations decreased in all regions with the exception of Great Britain; all but one of these regions exhibited stronger downward trends in the 1990s than in the 1980s. In contrast, regional declines in lake and stream nitrate concentrations were rare and, when detected, were very small. Recovery in alkalinity, expected wherever strong regional declines in sulphate concentrations have occurred, was observed in all regions of Europe, especially in the 1990s, but in only one region (of five) in North America. We attribute the lack of recovery in three regions (south/central Ontario, the Adirondack/Catskill mountains and midwestern North America) to strong regional declines in base-cation concentrations that exceed the decreases in sulphate concentrations.

The role of nitrate in the acidification of streams in the Catskill Mountains of New York

Research on the effects of acidic deposition in the United States has focused largely on the role of sulfur deposition in the acidification of surface waters. Results from both long-term (up to 70 years) and recent monitoring of stream chemistry in the Catskill Mountains of New York indicate, however, that nitric acid has a significant and increasing role in surface water acidification that, during high-flow periods, rivals the role of sulfuric acid. Nitrate increases with increased stream flow throughout the year except during the late summer, when biological activity and its attendant nitrogen uptake are greatest; peak concentrations as high as 128 micrograms/l have been recorded during spring snowmelt. In contrast, sulfate concentrations decrease with increased flow.

Effect of groundwater springs on NO3− concentrations during summer in Catskill Mountain streams

Groundwater and stream water data collected at three headwater catchments in the Neversink River watershed indicate that base flow is sustained by groundwater from two sources: a shallow flow system within the till and soil and a deep flow system within bedrock fractures and bedding planes that discharges as perennial springs. Data from eight wells finished near the till/bedrock interface indicate that saturated conditions are not maintained in the shallow flow system during most summers. In contrast, the discharge of a perennial spring remained constant during two summer rainstorms, providing evidence that the deep flow system is disconnected from the shallow flow system in summer. Discharge from perennial springs was the principal source of streamflow in a headwater reach during low flow. Mean NO3− concentrations were 20–25 μmol L−1 in five perennial springs during the summer but only 5–10 μmol L−1 in shallow groundwater. Thus the deep flow system does not reflect typical NO3− concentrations in the soil during summer. A hydrologic budget at a headwater drainage reveals that March and late fall are the principal groundwater recharge periods. Residence time modeling based on analyses of 18O and 35S indicates that groundwater in the deep flow system is 6–22 months old. These data indicate that summer base flow largely originates from previous dormant seasons when available soil NO3− is greater. In these Catskill watersheds, high base flow concentrations of NO3− during summer do not provide sufficient evidence that the atmospheric N deposition rate exceeds the demand of terrestrial vegetation.

Episodic Acidification of Small Streams in the Northeastern United States: Ionic Controls of Episodes

As part of the Episodic Response Project (ERP), we intensively monitored discharge and stream chemistry of 13 streams located in the Northern Appalachian region of Pennsylvania and in the Catskill and Adirondack Mountains of New York from fall 1988 to spring 1990. The ERP clearly documented the occurrence of acidic episodes with minimum episodic pH ≤ 5 and inorganic monomeric Al (Alim) concentrations > 150 μg/L in at least two study streams in each region. Several streams consistently experienced episodes with maximum Alim concentrations >350 μg/L. Acid neutralizing capacity (ANC) depressions resulted from complex interactions of multiple ions. Base cation decreases often made the most important contributions to ANC depressions during episodes. Organic acid pulses were also important contributors to ANC depressions in the Adirondack streams, and to a lesser extent, in the Catskill and Pennsylvania streams. Nitrate concentrations were low in the Pennsylvania streams, whereas the Catskill and Adirondack study streams had high NO3- concentrations and large episodic pulses (≤ 54 μ eq/L). Most of the Pennsylvania study streams also frequently experienced episodic pulses of SO42- (≤ 78 μ eq/L), whereas the Adirondack and Catskill streams did not. High baseline concentrations of SO42- (all three study areas) and NO3- (Adirondacks and Catskills) reduced episodic minimum ANC, even when these ions did not change during episodes. The ion changes that controlled the most severe episodes (lowest minimum episodic ANC) differed from the ion changes most important to smaller, more frequent episodes. Pulses of NO3- (Catskills and Adirondacks), SO42- (Pennsylvania), or organic acids became more important during major episodes. Overall, the behavior of streamwater SO42- and NO3- is an indicator that acidic deposition has contributed to the severity of episodes in the study streams.

POTENTIAL EFFECTS OF CLIMATE CHANGE ON FRESHWATER ECOSYSTEMS OF THE NEW ENGLAND/MID‐ATLANTIC REGION

Numerous freshwater ecosystems, dense concentrations of humans along the eastern seaboard, extensive forests and a history of intensive land use distinguish the New England/Mid-Atlantic Region. Human population densities are forecast to increase in portions of the region at the same time that climate is expected to be changing. Consequently, the effects of humans and climatic change are likely to affect freshwater ecosystems within the region interactively. The general climate, at present, is humid continental, and the region receives abundant precipitation. Climatic projections for a 2 x CO1 atmosphere, however, suggest warmer and drier conditions for much of this region. Annual temperature increases ranging from 3-5°C are projected, with the greatest increases occurring in autumn or winter. According to a water balance mode!, the projected increase in temperature will result in greater rates of evaporation and evapotranspiration. This could cause a 21 and 31% reduction in annual stream flow in the southern and northern sections of the region, respectively, with greatest reductions occurring in autumn and winter. The amount and duration of snow cover is also projected to decrease across the region, and summer convective thunderstorms are likely to decrease in frequency but increase in intensity. The dual effects of climate change and direct anthropogenic stress will most likely alter hydrological and biogeochemica! processes, and, hence, the flora! and fauna! communities of the region’s freshwater ecosystems. For example, the projected increase in evapotranspiration and evaporation could eliminate most bog ecosystems, and increases in water temperature may increase bioaccumulation, and possibly biomagnification, of organic and inorganic contaminants. Not a!! change may be adverse. For example, a decrease in runoff may reduce the intensity of ongoing estuarine eutrophication, and acidification of aquatic habitats during the spring snowmelt period may be ameliorated. Recommendations for future monitoring efforts include: (1) extending and improving data on the distribution, abundance and effect of anthropogenic stressors (non-point pollution) within the region; and (2) improving scientific knowledge regarding the contemporary distribution and abundance of aquatic species. Research recommendations include: (1) establishing a research centre(s) where field studies designed to understand interactions between freshwater ecosystems and climate change can be conducted; (2) projecting the future distribution, activities and direct effects of humans within the region; (3) developing mathematical analyses, experimental designs and aquatic indicators that distinguish between climatic and anthropogenic effects on aquatic systems; (4) developing and refining projections of climate variability such that the magnitude, frequency and seasonal timing of extreme events can be forecast; and (5) describing quantitatively the flux of materials (sediments, nutrients, metals) from watersheds characterized by a mosaic of land uses. 0 1997 by John Wiley & Sons, Ltd.

SOIL CALCIUM STATUS AND THE RESPONSE OF STREAM CHEMISTRY TO CHANGING ACIDIC DEPOSITION RATES

Despite a decreasing trend in acidic deposition rates over the past two to three decades, acidified surface waters in the northeastern United States have shown minimal changes. Depletion of soil Ca pools has been suggested as a cause, although changes in soil Ca pools have not been directly related to long-term records of stream chemistry. To investigate this problem, a comprehensive watershed study was conducted in the Neversink River Basin, in the Catskill Mountains of New York, during 1991–1996. Spatial variations of atmospheric deposition, soil chemistry, and stream chemistry were evaluated over an elevation range of 817–1234 m to determine whether these factors exhibited elevational patterns. An increase in atmospheric deposition of SO4 with increasing elevation corresponded with upslope decreases of exchangeable soil base concentrations and acid-neutralizing capacity of stream water. Exchangeable base concentrations in homogeneous soil incubated within the soil profile for one year also decreased wi...

CHEMICAL CHARACTERISTICS AND TEMPORAL TRENDS IN EIGHT STREAMS OF THE CATSKILL MOUNTAINS, NEW YORK

Discharge to concentration relationships for eight streams studied by the U.S. Geological Survey (USGS) as part of the U.S. Environmental Protection Agencys (U.S. EPA) Long-Term Monitoring Project (1983–89) indicate acidification of some streams by H2SO4 and HNO3 in atmospheric deposition and by organic acids in soils. Concentrations of major ions in precipitation were similar to those reported at other sites in the northeastern United States. Average concentrations of SO42− and NO3− were similar among streams, but base cation concentrations differed widely, and these differences paralleled the differences in acid neutralizing capacity (ANC). Baseflow ANC is not a reliable predictor of stream acidity at high flow; some streams with high baseflow ANC (>150 Μeq L−1) declined to near zero ANC at high flow, and one stream with low baseflow ANC (<50 Μeq L−1) did not approach zero ANC as flow increased. Episodic decreases in ANC and pH during peak flows were associated with increased concentrations of NO3− and dissolved organic carbon (DOC). Aluminum concentrations exceeding 300 Μg L−1 were observed during peak flows in headwater streams of the Neversink River and Rondout Creek. Seasonal Kendall Tau tests for temporal trends indicate that SO42− concentrations in streamwater generally decreased and NO3− concentrations increased during the period 1983–1989. Combined acid anion concentrations (SO42− + NO3−) were generally unchanged throughout the period of record, indicating both that the status of these streams with respect to acidic deposition is unchanged, and that NO3− is gradually replacing SO42− as the dominant acid anion in the Catskill streams.

Episodic Acidification of Small Streams in the Northeastern United States: Episodic Response Project

The Episodic Response Project (ERP) was an interdisciplinary study de- signed to address uncertainties about the occurrence, nature, and biological effects of ep- isodic acidification of streams in the northeastern United States. The ERP research consisted of intensive studies of the chemistry and biological effects of episodes in 13 streams draining forested watersheds in the three study regions: the Northern Appalachian region of Penn- sylvania and the Catskill and Adirondack Mountains of New York. Wet deposition was measured in each of the three study regions. Using automated instruments and samplers, discharge and chemistry of each stream was monitored intensively from fall 1988 through spring 1990. Biological studies focused on brook trout and native forage fish. Experimental approaches included in situ bioassays, radio transmitter studies of fish movement, and fish population studies. This paper provides an overview of the ERP, describes the methodology used in hydrologic and water chemistry components of the study, and summarizes the characteristics of the study sites, including the climatic and deposition conditions during the ERP and the general chemical characteristics of the study streams.

Hydrogeologic comparison of an acidic-lake basin with a neutral-lake basin in the West-Central Adirondack Mountains, New York

Two small headwater lake basins that receive similar amounts of acidic atmospheric deposition have significantly different lake outflow pH values; pH at Panther Lake (neutral) ranges from about 4.7 to 7; that at Woods Lake (acidic) ranges from about 4.3 to 5. A hydrologic analysis, which included monthly water budgets, hydrograph analysis, examination of flow duration and runoff recession curves, calculation of ground-water storage, and an analysis of lateral flow capacity of the soil, indicates that differences in lakewater pH can be attributed to differences in the ground-water contribution to the lakes. A larger percentage of the water discharged from the neutral lake is derived from ground water than that from the acidic lake. Ground water has a higher pH resulting from a sufficiently long residence time for neutralizing chemical reactions to occur with the till. The difference in ground-water contribution is attributed to a more extensive distribution of thick till (<3 m) in the neutral-lake basin than in the acidic-lake basin; average thickness of till in the neutral-lake basin is 24 m whereas that in the other is 2.3 m. During the snowmelt period, as much as three months of accumulated precipitation may be released within two weeks causing the lateral flow capacity of the deeper mineral soil to be exceeded in the neutral-lake basin. This excess water moves over and through the shallow acidic soil horizons and causes the lakewater pH to decrease during snowmelt