Ongoing increases in dissolved organic carbon are sustained by decreases in ionic strength rather than decreased acidity in waters recovering from acidic deposition.

Dissolved organic carbon (DOC) has received considerable attention in freshwater research, particularly since the early 2000s when increasing trends became apparent. However, remaining questions need to be resolved to address future effects of DOC on surface waters. This study was undertaken to determine (1) the relative importance of acidity and ionic strength in driving DOC increases in waters recovering from acidification and (2) the role played by long-term acid rain effects on soil. Data obtained from temporal and spatial monitoring of 142 headwater streams throughout the Adirondack region of New York (USA) were used to evaluate chemical relationships involving DOC. Year-round monitoring of three streams of differing acidification status were combined with intermittent stream surveys during spring snowmelt throughout this 24,243 km2 region that is recovering from acidification of soils and surface waters. Despite acidic deposition decreases reaching levels estimated for the early 1900s, DOC concentrations exhibited linear increases from the early 2000s through 2019. Ionic strength or conductivity showed consistent inverse relationships with DOC in all data comparisons from 2004-05 to 2018-19. In contrast, relationships between pH and DOC did not support increasing pH as an important factor in DOC increases. Inconsistent relationships between pH and DOC were due to strongly acidic organic acids that remain unprotonated throughout the pH range of these waters and limited weak-acid deprotonation below pH 6.2. Decreasing ionic strength increases DOC solubility by expanding the diffuse double layer, which fosters disaggregation of organic matter and dispersion of colloids. This affect controlled DOC solubilization below a pH of approximately 6.2. Distinguishing between ionic strength and pH effects is important because further large reductions in acidic deposition are not expected but continued soil-water dilution is likely from soil-Ca2+ depletion and the decreasing rate of Ca2+ leaching by SO42- and NO3-, which are still being released from soil organic matter.

Long-term dataset on aquatic responses to concurrent climate change and recovery from acidification.

Concurrent regional and global environmental changes are affecting freshwater ecosystems. Decadal-scale data on lake ecosystems that can describe processes affected by these changes are important as multiple stressors often interact to alter the trajectory of key ecological phenomena in complex ways. Due to the practical challenges associated with long-term data collections, the majority of existing long-term data sets focus on only a small number of lakes or few response variables. Here we present physical, chemical, and biological data from 28 lakes in the Adirondack Mountains of northern New York State. These data span the period from 1994-2012 and harmonize multiple open and as-yet unpublished data sources. The dataset creation is reproducible and transparent; R code and all original files used to create the dataset are provided in an appendix. This dataset will be useful for examining ecological change in lakes undergoing multiple stressors.

Patterns of nutrient dynamics in Adirondack lakes recovering from acid deposition.

With decreases in acid deposition, nitrogen : phosphorus (N:P) ratios in lakes are anticipated to decline, decreasing P limitation of phytoplankton and potentially changing current food web dynamics. This effect could be particularly pronounced in the Adirondack Mountains of New York State, a historic hotspot for effects of acid deposition. In this study, we evaluate spatial patterns of nutrient dynamics in Adirondack lakes and use these to infer potential future temporal trends. We calculated Mann-Kendall tau correlations among total phosphorus (TP), chlorophyll a, dissolved organic carbon (DOC), acid neutralizing capacity (ANC), and nitrate (NO3- ) concentrations in 52 Adirondack Long Term Monitoring (ALTM) program lakes using samples collected monthly during 2008-2012. We evaluated the hypothesis that decreased atmospheric N and S deposition will decrease P limitation in freshwater ecosystems historically impacted by acidification. We also compared these patterns among lake watershed characteristics (i.e., seepage or lacking a surface outlet, chain drainage, headwater drainage, thin glacial till, medium glacial till). We found that correlations (P < 0.05) were highly dependent upon the different hydrologic flowpaths of seepage vs. drainage lakes. Differentiations among watershed till depth were also important in determining correlations due to water interaction with surficial geology. Additionally, we found low NO3- :TP (N:P mass) values in seepage lakes (2.0 in winter, 1.9 in summer) compared to chain drainage lakes (169.4 in winter, 49.5 in summer) and headwater drainage lakes (97.0 in winter, 10.9 in summer), implying a high likelihood of future shifts in limitation patterns for seepage lakes. With increasing DOC and decreasing NO3- concentrations coinciding with decreases in acid deposition, there is reason to expect changes in nutrient dynamics in Adirondack lakes. Seepage lakes may become N-limited, while drainage lakes may become less P-limited, both resulting in increased productivity. Long-term measurements of TP and chlorophyll a from the Adirondacks are needed to inform how future decreases in atmospheric N and S deposition will influence the trophic status of lake ecosystems throughout the region.

Trends in mercury concentrations in New York State fish.

Atmospheric emissions of mercury in the US are being reduced, but worldwide mercury emissions remain high. Mercury is also being removed from many consumer items. Changes over time in mercury concentrations in fish remain important to resource managers and the general public. There is hope that mercury concentrations in fish will decline, and the number of fish consumption advisories due to mercury will decrease. We compared mercury concentrations in yellow perch (Perca flavescens) from a group of Adirondack lakes with data collected 12-17 years earlier and found variable responses among lakes. We observed an average decline of 14% in yellow perch mercury concentrations over the past 15 years.

Chronic and episodic acidification of Adirondack streams from acid rain in 2003-2005.

Limited information is available on streams in the Adirondack region of New York, although streams are more prone to acidification than the more studied Adirondack lakes. A stream assessment was therefore undertaken in the Oswegatchie and Black River drainages; an area of 4585 km(2) in the western part of the Adirondack region. Acidification was evaluated with the newly developed base-cation surplus (BCS) and the conventional acid-neutralizing capacity by Gran titration (ANC(G)). During the survey when stream water was most acidic (March 2004), 105 of 188 streams (56%) were acidified based on the criterion of BCS < 0 microeq L(-1), whereas 29% were acidified based on an ANC(G) value < 0 microeq L(-1). During the survey when stream water was least acidic (August 2003), 15 of 129 streams (12%) were acidified based on the criterion of BCS < 0 microeq L(-1), whereas 5% were acidified based on ANC(G) value < 0 microeq L(-1). The contribution of acidic deposition to stream acidification was greater than that of strongly acidic organic acids in each of the surveys by factors ranging from approximately 2 to 5, but was greatest during spring snowmelt and least during elevated base flow in August. During snowmelt, the percentage attributable to acidic deposition was 81%, whereas during the October 2003 survey, when dissolved organic carbon (DOC) concentrations were highest, this percentage was 66%. The total length of stream reaches estimated to be prone to acidification was 718 km out of a total of 1237 km of stream reaches that were assessed.

Lake variability: key factors controlling mercury concentrations in New York State fish.

A 4year study surveyed 131 lakes across New York State beginning in 2003 to improve our understanding of mercury and gather information from previously untested waters. Our study focused on largemouth and smallmouth bass, walleye and yellow perch, common piscivorous fish shown to accumulate high mercury concentrations and species important to local fisheries. Fish from Adirondack and Catskill Forest Preserve lakes generally had higher mercury concentrations than those from lakes in other areas of the state. Variability between nearby individual lakes was observed, and could be due to differences in water chemistry, lake productivity or the abundance of wetlands in the watershed. We found the following factors impact mercury bioaccumulation: fish length, lake pH, specific conductivity, chlorophyll a, mercury concentration in the water, presence of an outlet dam and amount of contiguous wetlands.

Factors affecting acid neutralizing capacity in the Adirondack region of New York: a solute mass balance approach.

High rates of acidic deposition in the Adirondack region of New York have accelerated acidification of soils and surface waters. Annual input-output budgets for major solutes and acid-neutralizing capacity (ANC) were estimated for 43 drainage lake-watersheds in the Adirondacks from 1998 to 2000. Sulfate was the predominant anion on an equivalent basis in both precipitation and drainage export. Calcium ion had the largest cation drainage export, followed by Mg2+. While these watersheds showed net nitrogen (N) retention, the drainage losses of SO4(2-), Cl-, base cations, and ANC exceeded their respective inputs from precipitation. Land cover (forest type and wetlands) affected the export of SO4(2-), N solutes, and dissolved organic carbon (DOC). The relationships of solute export with elevation (negative for base cations and Cl-, positive for NO3- and H+) suggest the importance of the concomitant changes of biotic and abiotic watershed characteristics associated with elevational gradients. The surface water ANC increased with the sum of base cations and was greatest in the lakes with watersheds characterized by thick deposits of glacial till. The surface water ANC was also higher in the lake-watersheds with lower DOC export. Some variation in lake ANC was associated with variability in acidic deposition. Using a classification system previously developed for Adirondack lakes on the basis primarily of surficial geology, lake-watersheds were grouped into five classes. The calculated ANC fluxes based on the major sinks and sources of ANC were comparable with measured ANC for the thick-till (I) and the medium-till lake-watersheds with low DOC (II). The calculated ANC was overestimated for the medium-till with high DOC (III) and the thin-till with high DOC (V) lake-watersheds, suggesting the importance of naturally occurring organic acids as an ANC sink, which was not included in the calculations. The lower calculated estimates than the measured ANC for the thin-till lake-watersheds with low DOC (IV) were probably due to the mobilization of Al as an ANC source in these watersheds that were highly sensitive to strong acid inputs. Our analysis of various drainage lakes across the Adirondacks on the basis of solute mass balances, coupled with the use of a lake classification system and GIS data, demonstrates that the lake-watersheds characterized by shallow deposits of glacial till are highly sensitive to acidic deposition not only in the southwestern Adirondack region where previous field-based studies were intensively conducted but also across the entire Adirondack region. Moreover, the supply of organic acids and Al mobilization substantially modify the acid-base status of surface waters.

Use of stream chemistry for monitoring acidic deposition effects in the Adirondack region of New York.

Acid-neutralizing capacity (ANC) and pH were measured weekly from October 1991 through September 2001 in three streams in the western Adirondack Mountain region of New York to identify trends in stream chemistry that might be related to changes in acidic deposition. A decreasing trend in atmospheric deposition of SO4/2- was observed within the region over the 10-yr period, although most of the decrease occurred between 1991 and 1995. Both ANC and pH were inversely related to flow in all streams; therefore, a trend analysis was conducted on (i) the measured values of ANC and pH and (ii) the residuals of the concentration-discharge relations. In Buck Creek, ANC increased significantly (p < 0.05) over the 10 yr, but the residuals of ANC showed no trend (p > 0.10). In Bald Mountain Brook, ANC and residuals of ANC increased significantly (p < 0.01), although the trend was diatonic-a distinct decrease from 1991 to 1996 was followed by a distinct increase from 1996 to 2001. In Fly Pond outlet, ANC and residuals of ANC increased over the study period (p < 0.01), although the trend of the residuals resulted largely from an abrupt increase in 1997. In general, the trends observed in the three streams are similar to results presented for Adirondack lakes in a previous study, and are consistent with the declining trend in atmospheric deposition for this region, although the observed trends in ANC and pH in streams could not be directly attributed to the trends in acidic deposition.

Chemical response of lakes in the Adirondack Region of New York to declines in acidic deposition.

Long-term changes in the chemistry of wet deposition and lake water were investigated in the Adirondack Region of New York. Marked decreases in concentrations of SO4(2-) and H+ in wet deposition have occurred at two sites since the late 1970s. These decreases are consistent with long-term declines in emissions of sulfur dioxide (SO2) in the eastern United States. Changes in wet NO3- deposition and nitrogen oxides (NOx) emissions have been minor over the same interval. Virtually all Adirondack Lakes have shown marked decreases in concentrations of SO4(2-), which coincide with decreases in atmospheric S deposition. Concentrations of NO3- have also decreased in several Adirondack lakes. As atmospheric N deposition has not changed over this period, the mechanism contributing to this apparent increase in lake/watershed N retention is not evident. Decreases in concentrations of SO4(2-) + NO3- have resulted in increases in acid-neutralizing capacity (ANC) and pH and resulted in a shift in the speciation of monomeric Al from toxic inorganic species toward less toxic organic forms in some lakes. Nevertheless, many lakes continue to exhibit pH values and concentrations of inorganic monomeric Al that are critical to aquatic biota. Extrapolation of rates of ANC increase suggests that the time frame of chemical recovery of Adirondack Lakes will be several decades if current decreases in acidic deposition are maintained.