We evaluated long-term surface water nitrate and atmospheric nitrogen (N) deposition trends for a group of nine predominantly forested Appalachian Mountain watersheds during a recent multidecadal period (1986-2009) in which regional NOx emissions have been progressively reduced. Statistical analysis showed unexpected linear declines in both annual surface water nitrate-N concentrations (mean =46.4%) and yields (mean =47.7%) among the watersheds corresponding to comparable declines in annual wet N deposition (mean =34.4%) resulting from U.S. NOx emission control programs during the same time period. Nitrate-N concentration trends were robust across a large geographical region and appeared insensitive to watershed size across several orders of magnitude-suggesting that the improvements in water quality are probably propagated to surface and estuarine waters downstream. Surface waters are thus responding to declining atmospheric N deposition in much the same way they responded to declining sulfur deposition-although only one watershed showed a 1:1 relationship. Application of a kinetic N saturation model indicated that all nine forested watersheds are exhibiting signs of N saturation as evidenced by a limited, but variable, efficiency of demand for N. Further reductions in N deposition would be expected to produce additional reductions in streamwater N loads.

Stream conductivity reflects both landscape and anthropogenic interactions, although increasing chloride inputs from road salt in eastern North America is also important. Employing a spatially extensive database derived from the Maryland Biological Stream Survey (MBSS), we examined relationships of stream conductivity to landscape attributes and determined relationships between stream MBSS fish metrics, abundance, and biomass as well as fish assemblages by means of conductivity (as a chloride surrogate) to estimate potential effects. Background stream conductivity for the MBSS strata and Maryland L3 ecoregions ranged from 51 to 150 μS/cm, with the Piedmont having the highest background conductivity (145–160 μS/cm). For MBSS sites there were strong relationships of stream conductivity and chloride with both impervious surface and road density, and 0.26% of the MBSS sites exceeded the U.S. Environmental Protection Agency's acute chloride criterion and 1.5% the chronic chloride criterion. For the Maryland Piedmont species assemblage, observed conductivity values between 230 and 540 μS/cm caused important alterations in the biotic community as measured by the series of fish metrics, and thus affected fish species assemblages associated with chloride concentrations between 33 and 108 mg/L. Maryland coastal, coldwater, and highland species assemblages displayed variable responses of conductivity to fish metrics, abundance, and biomass. If regional conductivity and chloride levels continue to increase or remain high from road deicing owing to an increase in urbanization in a watershed or climatic changes, differences in stream fish assemblages and therefore fish diversity may become more apparent. Because of the linkage between salt usage and impervious road surfaces resulting from urbanization, it is important to manage effectively the use of road salt to protect biotic resources. Received January 24, 2012; accepted June 5, 2012

Using a spatially extensive urban database constructed from the Maryland Biological Stream Survey (MBSS), we describe the relationships of nutrients in small-order streams to eight defined categories of percent catchment urbanization, correlations between chloride and conductivity in urban streams, and relationships between nutrients and chloride with two Maryland-specific indices of biotic integrity for benthic macroinvertebrates and fish assemblages. Stream nutrients become elevated with increasing percent catchment urbanization, followed by increases in all four measured nitrogen species and total phosphorus at catchment urbanization levels greater than 10%. There was a strong collinear relationship (r 2 =0.90) between chloride and conductivity (trimeans) across all eight urbanization classes, where Cl (mg/L)=−0.397+0.188*conductivity (μS/cm). Critical values for all water quality parameters with the two Maryland biological indices were derived using quantile regression, with significant regressions developed for 11 of 16 water quality parameters and the two biotic indices. For nitrate (NO 3 -N), the critical thresholds between fair and poor stream quality for the two Maryland biological indices were 0.83 mg/L (benthic macroinvertebrate assemblages) and 0.86 mg/L (fish assemblages). Increasing stream nutrient and chloride levels, associated with widespread catchment urbanization intensity, now affect many small streams in Maryland, with implications for decreasing water quality in major tributaries and the Chesapeake Bay.

In this study we report on changes in the magnitude and mechanisms of episodic acidification of a small acid-sensitive stream in western Maryland (U.S.) during the 1990s, a period in which wet sulfate deposition declined by 10-25% due to implementation of the Clean Air Act Amendments (CAAA) of 1990. We observed a relatively minor trend in the magnitude of episodic acidification over this period, as measured bytransient changes in acid neutralizing capacity (deltaANC) and minimum values of ANC (ANC(min)) during 22 events sampled prior to and following CAAA implementation. Any relationship to changes in atmospheric deposition appears to be confounded by large hydroclimatological variability between the two sampling periods. Nonetheless, results obtained prior to implementation of the CAAA indicated that the mechanism of episodic acidification was mostly attributable to flushing of accumulated sulfate from the watershed, whereas results obtained post-CAAA indicated domination by base cation dilution. This shift in the mechanism of episodic acidification is qualitatively consistent with hydrochemical theory, as well as with empirical results from surface waters in other regions where dramatic declines in sulfate deposition have taken place.

Recovery of streamwater acid neutralizing capacity (ANC) resulting from declines in regional acid deposition was examined using contemporary (1990-2005) data from two long-term monitoring stations located on the Appalachian Plateau in western Maryland, U.S. Two computational methods were used to estimate daily, monthly, and annual fluxes and discharge-weighted concentrations of ANC, sulfate, nitrate, and base cations over the period of record, and two statistical methods were used to evaluate long-term trends in fluxes and concentrations. The methods used to estimate concentrations, as well as the statistical techniques, produced very similar results, underlining the robustness of the identified trends. We found clear evidence that streamwater sulfate concentrations have declined at an average rate of about 3 microeq L(-1) yr(-1) at the two sites due to a 34% reduction in wet atmospheric sulfur deposition. Trends in nitrate concentrations appear to be related to other watershed factors, especially forest disturbance. The best evidence of recovery is based on a doubling of ANC (from 21 to 42 microeq L(-1)) at the more acid-sensitive site over the 16-year period. A slowing, or possible reversal, in the sulfate, nitrate, and SBC trends is evident in our data and may portend a decline in the rate of--or end to--further recovery.