TRENDS IN PRECIPITATION AND STREAM CHEMISTRY IN A PRISTINE OLD-GROWTH FOREST WATERSHED,OLYMPIC NATIONAL PARK,WASHINGTON1

ABSTRACT: Human induced long-term changes in precipitation and stream chemistry have been observed in eastern North America and Europe, but few long-term studies have been conducted in coastal western North America. The objectives of this research were to determine: (1) time trends in precipitation and stream chemistry in a pristine old-growth forest watershed, and (2) seasonal patterns in precipitation and stream chemistry. It was conducted in 58 ha West Twin Creek Watershed, Hoh River Valley, Olympic National Park, Washington from 1984 to 1993. Vegetation consists of old-growth forest, with western hemlock, Douglas-fir, western redcedar, Pacific silver fir, and Sitka spruce being the dominant tree species. Annual precipitation varied from 2336 to 4518 mm during the study period with the majority of the rain falling between October and May. Chemistry of precipitation was strongly dominated by oceanic influences with Na and Cl being the dominant ions. The chemistry of the stream was influenced by bedrock weathering and was dominated by Ca, HCO₃, and SO₄ and was not strongly related to precipitation chemistry. The pH of precipitation averaged 5.3 over time and ranged from 4.3 to 7.1, while the stream pH averaged 7.5 and ranged from 5.5 to 9.0. There were few long-term trends in the chemical constituents of bulk precipitation or stream water with the exception of a slight decrease in NO₃ in precipitation and an increase of SO₄ in stream water. A trend of decreasing concentrations of Ca, Mg and Na in precipitation also occurred. There were no significant seasonal patterns in precipitation although the highest SO₄ concentrations usually occurred in late spring and summer perhaps due marine algal activity. Strong seasonal trends occurred in concentrations of HCO₃, SO₄, Ca, Mg, and Na in stream water resulting from weathering and stream flow patterns, with highest ion concentrations occurring just before the onset of the rainy season. Pulses of NO₃ in the stream were observed during fall and early winter resulting from the release of NO₃ which had accumulated in soils or sediments.     

BIOGEOCIIEMISTRY OF AN OLD-GROWTH FORESTED WATERSHED,OLYMPIC NATIONAL PARK,WASHINGTON1

ABSTRACT: The biogeochemistry of a coastal old-growth forested watershed in Olympic National Park, Washington, was examined. Objectives were to determine: (1) concentrations of major cations and anions and dissolved organic C (DOC) in precipitation, throughfall, stemflow, soil solution and the stream; (2) nutrient input/output budgets; and (3) nutrient retention mechanisms in the watershed. Stemilow was more acidic (pH 4.0–4.5) than throughfall (pH 5.1) and precipitation (pH 5.3). Organic acids were important contributors to acidity in throughfall and stemflow and tree species influenced pH. Soil solution pH averaged 6.2 at 40 cm depth. Stream pH was higher (7.6). Sodium (54.0 μeq L-¹) and Cl (57.6 μeq L^?1) were the dominant ions in precipitation, reflecting the close proximity to the ocean. Throughfall and stemflow were generally enriched in cations, especially K. Cation concentrations in soil solutions were generally less than those in stemilow. Ion concentrations increased in the stream. Dominant ions were Ca (759.7 μeq L^?1), Na (174.4 μeq L^?1), HCO₃ (592.0 μeq L^?1), and SO₄ (331.5 μeq L^?1) with seasonal peaks in the fall. Bedrock weathering strongly influenced stream chemistry. Highest average NO₃ concentrations were in the stream (5.2 μeq L^?1) with seasonal peaks in the fall and lowest concentrations in the growing season. Nitrogen losses were similar to inputs; annual inputs were 4.8 kg/ha (not including fixation) and stream losses were 7.1 kg/ha. Despite the age and successional status of the forest, plant uptake is an important N retention mechanism in this watershed.     

ESTIMATION OF EPISODIC STREAM ACIDIFICATION BASED ON MONTHLY OR ANNUAL SAMPLING1

ABSTRACT: Programs of monthly or annual stream water sampling will rarely observe the episodic extremes of acidification chemistry that occur during brief, unpredictable runoff events. When viewed in the context of data from several streams, however, baseflow measurements of variables such as acid neutralizing capacity, pH and NO₃· are likely to be highly correlated with the episodic extremes of those variables from the same stream and runoff season. We illustrate these correlations for a water chemistry record, nearly two years in length, obtained from intensive sampling of 13 small Northeastern U.S. streams studied during USEPA's Episodic Response Project. For these streams, simple regression models estimate episodic extremes of acid neutralizing capacity, pH, NO₃·, Ca²⁺, SO₄^2?, and total dissolved Al with good relative accuracy from statistics of monthly or annual index samples. Model performances remain generally stable when episodic extremes in the second year of sampling are predicted from first-year models. Monthly or annual sampling designs, in conjunction with simple empirical models calibrated and maintained through intensive sampling every few years, may estimate episodic extremes of acidification chemistry with economy and reasonable accuracy. Such designs would facilitate sampling a large number of streams, thereby yielding estimates of the prevalence of episodic acidification at regional scales.     

NITROGEN AND PHOSPHORUS CONCENTRATIONS IN FOREST STREAMS OF THE UNITED STATES1

ABSTRACT: Seventy to eighty percent of the water flowing in rivers in the United States originates as precipitation in forests. This project developed a synoptic picture of the patterns in water chemistry for over 300 streams in small, forested watersheds across the United States. Nitrate (NO₃^?) concentrations averaged 0.31 mg N/L, with some streams averaging ten times this level. Nitrate concentrations tended to be higher in the northeastern United States in watersheds dominated by hardwood forests (especially hardwoods other than oaks) and in recently harvested watersheds. Concentrations of dissolved organic N (mean 0.32 mg N/L) were similar to those of NO₃～, whereas ammonium (NH₄⁺) concentrations were much lower (mean 0.05 mg N/L). Nitrate dominated the N loads of streams draining hardwood forests, whereas dissolved organic N dominated the streams in coniferous forests. Concentrations of inorganic phosphate were typically much lower (mean 12 mg P/L) than dissolved organic phosphate (mean 84 mg P/L). The frequencies of chemical concentrations in streams in small, forested watersheds showed more streams with higher NO₃^? concentrations than the streams used in national monitoring programs of larger, mostly forested watersheds. At a local scale, no trend in nitrate concentration with stream order or basin size was consistent across studies.     

EFFECTS OF FOREST HERBICIDE APPLICATIONS ON STREAMWATER CHEMISTRY IN SOUTHWESTERN BRITISH COLUMBIA1

ABSTRACT: The herbicide glyphosate was applied to portions of two watersheds in southwestern British Columbia to kill vegetation that was competing with Pseudotsuga menziesii (Douglas-fir) plantations. This application had little significant effect on streamwater chemistry (K⁺, Na²⁺, Mg²⁺, Ca²⁺, Cl^-, NOs₃^-, NH₄⁺, PO4^3-, SO₄⁼, and SiO₂ concentrations, electrical conductivity, and pH) when vegetation cover in a watershed was reduced by 4%, but had significant (P>0.05) effects, which lasted for at least five years, when cover was reduced by 43%. In this case, most parameters increased in value following the application, with K⁺ and Mg²⁺ concentrations and pH values exhibiting the most prolonged increases and NO₃^- concentrations exhibiting the greatest percentage increases. Sulphate and dissolved SiO₂ concentrations decreased following the application. Streamwater chemical fluxes showed similar trends to concentrations except that changes in fluxes were less significant and no decreases were observed. Forest management induced losses of NO₃-N in streamwater during the first five post-treatment years in the study area decreased in the order: herbicide application (approximately 40 kg/ha) < clearcutting and slashburning (approximately 20 kg/ha) < clearcutting (approximately 10 kg/ha). In watersheds similar to those of the study area, herbicide application is likely to have a greater impact on streamwater chemistry, in general, than would clearcutting or clearcutting followed by slashburning.     

Hydrobiogeochemical Controls on Riparian Nutrient and Greenhouse Gas Dynamics: 10 Years Post‐Restoration

Little is known about the impact of agricultural legacy on subsurface biogeochemical processes in the years following restoration of riparian wetlands (WLs). More knowledge is also needed on the relative importance of seasons, precipitation events, and inputs of water and nutrients driving nitrogen (N), phosphorus (P), sulfur (S), and greenhouse gas (GHG) (N₂O, CO₂, CH₄) dynamics in these systems. This investigation of a riparian zone comprising a restored WL area and a nonrestored well‐drained alluvium (AL) area in the United States Midwest revealed that despite successful hydrological restoration a decade earlier, biogeochemical conditions in the WL area remained less anoxic than in natural WLs, and not significantly different from those in the AL area. No significant differences in N, P, S, and C compound concentrations or fluxes were observed between the AL and WL areas. Over the duration of the study, nitrate (NO₃^?) and soluble reactive phosphorus appeared to be primarily driven by hillslope contributions. Ammonium (NH₄⁺), sulfate (SO₄^2?), and CO₂ responded strongly to seasonal changes in biogeochemical conditions in the riparian zone, while N₂O and CH₄ fluxes were most influenced by large rewetting events. Overall, our results challenge overly simplistic assumptions derived from direct interpretation of redox thermodynamics, and show complex patterns of solutes and GHGs at the riparian zone scale.     

CUMULATIVE IMPACTS OF LANDUSE ON WATER QUALITY IN A SOUTHERN APPALACHIAN WATERSHED1

ABSTRACT: Water quality variables were sampled over 109 weeks along Coweeta Creek, a fifth-order stream located in the Appalachian mountains of western North Carolina. The purpose of this study was to observe any changes in water quality, over a range of flow conditions, with concomitant downstream changes in the mix of landuses. Variables sampled include pH, HCO₃^2?, conductivity, NO₃^?_?-N, NH₄⁺-N, PO₄^3?-P, C1^?-, Na, K, Ca²⁺, Mg²⁺, SO₄^2?, 5iO₂, turbidity, temperature, dissolved oxygen, total and fecal coliform, and focal streptococcus. Landcover/landuse was interpreted from 1:20,000 aerial photographs and entered in a GIS, along with information on total and paved road length, building location and density, catchment boundaries, hydrography, and slope. Linear regressions were performed to relate basin and near-stream landscape variables to water quality. Consistent, cumulative, downstream changes in water quality variables were observed along Coweeta Creek, concomitant with downstream, human-caused changes in landuse. Furthermore, larger downstream changes in water quality variables were observed during stormflow when compared to baseflow, suggesting cumulative impacts due to landscape alteration under study conditions were much greater during storm events. Although most water quality regulations, legislation, and sampling are promulgated for baseflow conditions, this work indicates they should also consider the cumulative impacts of physical, chemical, and biological water quality during stormflow.     

Two‐Stage Ditch Floodplains Enhance N‐Removal Capacity and Reduce Turbidity and Dissolved P in Agricultural Streams

Two‐stage ditches represent an emerging management strategy in artificially drained agricultural landscapes that mimics natural floodplains and has the potential to improve water quality. We assessed the potential for the two‐stage ditch to reduce sediment and nutrient export by measuring water column turbidity, nitrate (NO₃^?), ammonium (NH₄⁺), and soluble reactive phosphorus (SRP) concentrations, and denitrification rates. During 2009‐2010, we compared reaches with two‐stage floodplains to upstream reaches with conventional trapezoid design in six agricultural streams. At base flow, these short two‐stage reaches (<600 m) reduced SRP concentrations by 3‐53%, but did not significantly reduce NO₃^? concentrations due to very high NO₃^? loads. The two‐stage also decreased turbidity by 15‐82%, suggesting reduced suspended sediment export during floodplain inundation. Reach‐scale N‐removal increased 3‐24 fold during inundation due to increased bioreactive surface area with high floodplain denitrification rates. Inundation frequency varied with bench height, with lower benches being flooded more frequently, resulting in higher annual N‐removal. We also found both soil organic matter and denitrification rates were higher on older floodplains. Finally, influence of the two‐stage varied among streams and years due to variation in stream discharge, nutrient loads, and denitrification rates, which should be considered during implementation to optimize potential water quality benefits.     

Impact of an Invasive Exotic Species on Stream Nitrogen Levels in Southern Illinois1

Abstract: Autumn‐olive (Elaeagnus umbellata Thunb.) is an invasive, exotic shrub that has become naturalized in the eastern United States. Autumn‐olive fixes nitrogen (N) via a symbiotic relationship with the actinomycete Frankia. At the plot scale, the presence of autumn‐olive has been related to elevated soil water nitrate‐N (NO₃^?‐N) concentrations. This study examined the relationship between autumn‐olive cover in a watershed and stream water quality. Stream water nitrate‐N (NO₃^?‐N) and ammonium‐N (NH₄⁺‐N) concentrations were measured in 12 first order ephemeral streams draining watersheds with mixed forest cover and a range of 0‐35% autumn‐olive cover. Percent autumn‐olive cover was positively correlated with mean stream NO₃^?‐N concentrations, but was not correlated with mean stream NH₄⁺‐N concentrations. While other studies have demonstrated a significant relationship between native N‐fixers and stream NO₃^?‐N, this is the first study to document a relationship for an invasive, exotic N‐fixing species. Results suggest that this exotic species can be an additional source of NO₃^? in local and regional water bodies and demonstrates an additional negative ecosystem consequence of invasion beyond losses in biodiversity.     

Effects of NO,NO<Subscript>2</Subscript>, CO and SO<Subscript>2</Subscript> on NO oxidation over Pt/TiO<Subscript>2</Subscript> for hybrid fast SCR process

The selective catalytic reduction (SCR) rate of NO with N-containing reducing agents can be enhanced considerably by converting part of NO into NO₂. The enhanced reaction rate is more pronounced even at lower temperatures by using an equimolar mixture of NO and NO₂ (fast SCR reaction). The oxidation characteristics of NO over catalyst Pt/TiO₂ have been determined in a fixed bed reactor (8 mm-ID) with different concentrations of oxygen, nitric oxide and nitrogen dioxide in the presence of 8% water. The conversion of NO to NO₂ increases with increasing oxygen (O₂) concentration from 3 to 12%, but it levels off at higher O₂ concentrations. The NO conversion to NO₂ decreases with increasing NO concentration and it also decreases by an addition of NO₂ in the feed stream. Therefore, the oxidation of NO over Pt/TiO₂ catalyst could be auto-inhibited by the reaction product of NO₂. The effects of CO and SO₂ on NO oxidation characteristics have also been determined. In fact, the presence of SO₂ significantly suppresses oxidation of NO but due to the less stability of sulfate on anatase structure in TiO₂, it becomes less significant. On the other hand, the presence of CO increases NO oxidation significantly due to the auto-inhibition effect by CO. Moreover, the effect of SO₂/CO on NO oxidation has also been determined and it was observed that NO oxidation decreases with the increase in SO₂/CO ratio.