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Preliminary Survey of the Chemical Parameters of Streams Draining the Adirondack High Peaks

Author: Jeffrey R. Chiarenzelli, Department of Geology, St. Lawrence University, Canton, New York 13617 Back to Table of Contents >> From Peer Review - Volume 19 (2013) (2013)

 

Stream water chemistry in the Adirondack High Peaks is largely unknown but of concern because of chronic acidification, the limited capacity of bedrock to buffer acidity, and potential biological impacts/changes. Seventeen streams in the High Peaks were sampled over a two day period by volunteers for multi-element concentration, pH, and acid neutralizing capacity. The streams are dilute, and have a variable, but generally low, capacity to neutralize acidity. They are enriched in aluminum, and have silicon and calcium as their dominant cations. Stream chemistry is controlled by hydrolysis of plagioclase feldspar and low pH; although some streams were well buffered with near neutral pH values. Subtle differences in stream chemistry most likely reflect the presence or absence of calcium-rich minerals in xenoliths entrained within the meta-igneous bedrock. With limited soil development, short water retention times, and plagioclase-rich crystalline bedrock (anorthosite), drainage basins in the High Peaks region may serve as a harbinger of changes that will eventually affect the entire region.

Photo Credit

Rockwell Falls on the Upper Hudson by Ken Rimany

Key Words

High Peaks, Stream Chemistry, Massif Anorthosite

 Introduction and Geological Setting

The Adirondack Park is a six million acre patchwork of public and private land within what has been historically termed the Adirondack Blue Line. From a regulatory perspective the Blue Line demarks the jurisdiction of the Adirondack Park Agency; however, from a geological perspective it closely follows the domal exposure of Precambrian crystalline rocks that range in age from 1000-1350 million years old (McLelland et al., 1988). One of the first experiments in public land acquisition, the park has been often cited as an example of how the preservation of other relatively undeveloped areas of public and private land might be structured and the numerous difficulties encountered in such an arrangement (Jenkins and Keal, 2004; Schneider, 1997; Terrie, 1997). Despite its location within a day’s drive of millions of people in various urban centers, the park has extensive wilderness areas and a limited human population (Jenkins and Keal, 2004). As a consequence, major pollution threats to the park are generally considered to be external. Among these acid precipitation (Jenkins et al., 2007) and far-traveled contaminants, such as mercury, are considered to be of the most concern and perhaps linked (Brown et al., 2010).

Landmark studies on the acidification of Adirondack Lakes were initially carried out by the Adirondack Lakes Survey Corporation (ALSC) in 19841987 and monitoring of select lakes continues even today. The goals of the ALSC study included determination of how many and which lakes had been acidified and the effects on fish populations (Baker et al., 1993; Kretser et al., 1989).   Some evidence suggests that considerable progress has been made in reducing sulfur deposition (primarily via sulfur dioxide) through the nation-wide reductions in the use of high sulfur fuels (Driscoll et al., 2003). Changes in NOx deposition have been minimal at best and the deposition of acidic species remains a considerable challenge in the region (Jenkins et al., 2007). As a consequence, acidification and deleterious effects on aquatic life persists in a number of waterways in the Adirondack region. Recent work has emphasized the episodic acidity of some streams and rivers (Jenkins et al., 2007; Lawrence, 2002; Lawrence et al., 2004; 2008). Most of the acidified water bodies occur in the western part of the Adirondack region (Jenkins et al., 2007; Lawrence, 2002; Lawrence et al., 2004; 2008; Chiarenzelli et al., 2012) where air masses from mid-western sources deposit acidic compounds, among other contaminants (Chiarenzelli et al., 2006), perhaps in part enhanced by lake-effect precipitation (Chiarenzelli et al., 2002) .

The Adirondack region is a small part of an extensive area of related rocks which form the deep crustal root of a billion year old and highly eroded mountain belt. These rocks extend from Greenland, along eastern Canada primarily in Quebec and Ontario, into the Adirondacks, and then occur in a series of basement inliers in the Appalachian Mountains. Collectively, they are termed the Grenville Province (Figure 1). The Adirondack region consists of an oval NNE-trending topographic dome approximately 200 kilometers across, cored by Mesoproterozoic crystalline rocks formed between 1000-1350 million years ago (Ma). Metamorphic assemblages indicate the rocks exposed at the surface were buried by as much as 30 kilometers approximately 1000 Ma (McLelland et al., 1996).

By ~500 Ma the region was worn down to sea level and lower Paleozoic rocks of marine affinity blanketed the region. The roots of this mountain belt were once again exposed by doming and uplift which began nearly 160 million years ago (Roden-Tice, 2005) stripping back the Lower Paleozoic section which unconformably overlies the Precambrian basement rocks along the edge of the dome. This uplift may be related to thermal effects of movement of the continent over the Great Meteor hotspot (Taylor and Fitzgerald, 2011). The region’s seismicity, radial drainage, and past re-leveling surveys indicate uplift continues to this day (Isachsen, 1975; 1981).

The High Peaks region underlies the center of the dome and is in turn underlain primarily by an exceptionally coarse, monominerallic (>90% plagioclase feldspar), crystalline rock known as massif anorthosite (Figure 1; Buddington, 1939; Isachsen and Fisher, 1970). Massif anorthosite is enigmatic in that it is found almost exclusively in the Grenville Province and thus has a relatively limited spatial and temporal occurrence. Because it has been metamorphosed at high temperatures and pressures, deep within the roots of a mountain belt, it is technically considered a metamorphosed anorthosite or meta-anorthosite. However, original igneous textures are often well preserved and often the only indication of this high-grade metamorphic event is a small amount of garnet grown during metamorphism. This has led many researchers to drop the “meta-“ prefix and this usage will be followed here.

Massif anorthosite, composed nearly completely of plagioclase feldspar of andesine composition, is spatially associated with a suite of metamorphosed igneous rocks collectively known as the anorthosite-mangerite-charnockite- granite (AMCG) suite, as well as, gabbroic variants into which anorthosite grades upon increasing mafic mineral content (Buddington, 1939). Massif anorthosite is believed to have formed by the crystallization and separation of plagioclase from mafic magmas ponded at the base of the crust (McLelland et al., 2010; Regan et al., 2010). These magmas are believed to have been generated by decompressional melting of the mantle following a mountain building event known as the Shawinigan Orogeny (Regan et al., 2010). Because of the high temperature of mantle melts, the lower crust in contact with the mafic magmas also melted to yield the felsic igneous rocks (MCG) found in and around the Marcy Massif. Often these rocks show mutual cross-cutting relations indicating they formed contemporaneously, whereas, their composition and isotopic systematics indicate they are not comagmatic, requiring at least two distinct magma sources (McLelland et al., 1996; 2010; Regan et al., 2010); one mantle, and one crustal, derived.

Our goal in this study was to capitalize on a fairly unique sampling opportunity to take a “snapshot” of water chemistry in the High Peaks during a single weekend in the early Fall. Specifically, we hoped to document the chemistry of streams draining the High Peaks region and determine their capacity to buffer acidity. Since the High Peaks region is underlain almost exclusively by anorthosite and related rocks with limited buffering capacity, has only sporadic glacial cover and soil development, and is upstream of practically all local human influence, it was anticipated that the water chemistry would largely reflect the influence of precipitation over other factors. As it turns out, the data indicate other factors including the nature of the bedrock also have a strong influence on water chemistry.

Our preliminary data should serve as a baseline for any future work designed to investigate changes in stream water chemistry due to external factors such as environmental regulations, reductions in emissions, changes in energy policies/use, global climate change, changes in atmospheric composition, changes in precipitation amounts, changes in population, and/or input from emerging or enhanced anthropogenic activities (e.g. Chiarenzelli, 2008; Driscoll et al., 2003; Jenkins et al., 2007; McKibben, 2002; Stager and Martin, 2002). It is also one of the few studies to address acidification of streams, aside from work in the western Adirondacks (Lawrence, 2002; Lawrence et al., 2004; 2008), and the only to do so in the High Peaks region.

Methodology

Samples were collected on the weekend of October 4 and 5th, 2008 by groups of volunteers in association with St. Lawrence University’s Outing Club’s Peak Weekend. The goal of the decades old activity is to put St. Lawrence students, alumni, and staff on all of the 46 High Peaks (those greater than 4000’) during the course of the weekend (Figure 2). The sampling event was organized and coordinated primarily by geology majors Johanna Palmer and Thomas Wright.  Using routes selected for peak ascent, specific stream crossing sites (Table 1) were chosen to provide a reasonable geographic coverage of the region’s streams and assigned to participants leading the ascents by the various routes.

A training session was held to insure each assigned sample collector knew where to sample and how to complete the sampling event. Each group was assigned two pre-cleaned, metals-certified, plastic 150 mL Wheaton Clean-pak® containers which were filled directly from the stream at a depth of ~5 centimeters. Samples were sealed and placed in backpacks without preservation or filtration of any type. Modified chain-of-custody forms where utilized and each sample container had a unique six number sample identifier and bar code to insure samples were not misidentified or mislocated. One container was designated for ICP-MS analysis at ACME Analytical Laboratories in Vancouver, British Columbia; the other for pH measurement and acid neutralization capacity (ANC) at the Department of Geology, St. Lawrence University. Samples were collected on the evening of the 5th at a designated drop off point and those for multi-element analysis shipped on the following Monday afternoon. Those collected for pH and ANC measurement were refrigerated in the dark and analyzed within a week of collection.

Once received, multi-element ICP-MS data for 72 elements was evaluated through the use of an Excel® spreadsheet. Mean, standard deviation, number of detectable measurements, high, and low values were calculated using built-in functions. The total dissolved solids (TDS) were calculated by summation of the detected concentrations of each element. Correlation coefficients between each element were evaluated by using the built-in function of Excel®. Quality assurance and quality control samples included analytical standards, duplicates, and blanks prepared and analyzed along with the actual samples. These data were compared to, and consistent with, the results of over ten years’ quality assurance data from similar geochemical studies reported elsewhere (e.g. Chiarenzelli et al., 2012).

Results

Table 1 gives sample locations and Table 2 summarizes the data set. In regards to quality control, the data were found to be accurate (comparison with actual standard values) and precise (comparison of replicate analyses). In general, the relative percent difference (RPD) of standard values and replicate measurements varied systematically with concentration but was generally less than 10%. Iron was an exception with an RPD of 31.0% and was detected in only 7 of 17 samples. Elements with the greater concentrations and found well above their respective detection limits tended to have the higher accuracy and precision.

A detailed summary of quality assurance procedures and results have been published elsewhere (Chiarenzelli et al., 2012) and are not repeated here in the interest of brevity. Table 2 provides detection limits, RPD between replicate samples, and summarizes the dataset. For example, calcium had a mean concentration and standard deviation of 2076±923 parts per billion (ppb), had a RPD of 2.27% between replicate samples, and was found above detection limit (50 ppb) in all samples. Calcium concentrations in stream samples ranged from 1061-4098 ppb. In general, the dataset indicated a high degree of similarity in the chemical composition of all streams sampled and was dominated by Si and Ca.

The pH of the streams varied from 4.90-6.42 units with a mean value of 5.74. Most chemical variation appeared to be a function of pH. For example, Al concentrations in stream waters have an inverse relationship with pH, while Ca has a positive correlation (Table 3). Total dissolved solids (TDS) varied between 6.22-16.1 ppm with a mean of 8.9. However, since anions were not measured, actual TDS values are likely significantly larger. Subsequent studies in the Raquette River drainage basin, that included both all major cations and anions, suggests TDS values are likely twice the reported mean value of 8.9 ppm. Total dissolved solids where also highly correlated to pH (r2 = 0.78).

Acid neutralizing capacity measures the amount of resistance of natural waters to acidification with a strong acid (Jenkins et al., 2007).   The ANC values measured by Gran titration ranged between 25-95 ?eq/L with a mean value of 41.8 and also varied systematically with pH (r2 = 0.84) and TDS (r2 = 0.88). A mean value of 41.8 ?eq/L indicates an acidic pH and susceptibility for severe “event” acidification because of minimal amounts of strong bases in the water, primarily Ca and Mg.

While the precise meteorological and hydrological conditions at each sample location cannot be determined, estimates of the general conditions prior to, and during, the sampling events are available from archival weather reports from local airports and United States Geological Survey gauging stations, respectively. Here weather conditions from the Saranac Lake Airport (ele. 507 m), a few tens of kilometers northwest of the sampling sites, are utilized. During the period one week prior to sampling on October 4th and 5th the mean daily temperature ranged from 16.7 to 5.6oC. Little to no precipitation occurred until the 1st of October when 1.42 cm of rain was recorded at the Saranac Lake airport. This was followed by 0.38 and 0.20 cm on the 2nd and 3rd of October, respectively. The hydrograph for the United States Geological Survey gauging station Ausable River at Ausable Forks (#04275500) located a few tens of kilometers northeast of the sampling sites, and draining most of the streams sampled in the eastern part of the study area, shows a rise in discharge above long term mean values, presumably related to rainfall over the High Peaks region with peaks on the 2nd and 4th of October (Figure 3). Given that sampling occurred on the 4th  and 5th of October and discharge was ~33% greater than long-term averages for those dates, enhanced discharge is believed to have been caused by runoff from precipitation events.

Discussion

Source of Dissolved Solids in High Peaks Streams

Using the weight ratios of common cations and anions Gibbs (1970) found that the composition of natural waters worldwide were dominated by three factors including precipitation (lower right hand corner on Figure 4), rock weathering (middle left hand edge), and vaporation/crystallization (upper right hand corner). When total dissolved solids for High Peaks streams are plotted versus the weight ratio of Na/(Ca+Na) on Figure 4 they plot in the lower left hand corner outside of the boomerang-shaped region which encompasses the bulk of natural waters determined by Gibbs (1970). This is true even if the TDS values, which average 8.9 ppm, are doubled or tripled to account for anionic contributions. Moreover, they fall within the region noted by Eilers et al. (1992) for dilute lake waters in areas dominated by crystalline bedrock (e.g. Sierra Nevada, Maine, Minnesota, Norway). This suggests that the High Peaks stream samples generally have lower TDS values than waters considered dominated by rock weathering and have lower Na/(Ca+Na) weight ratios than waters dominated by precipitation. Further, the High Peaks waters form a tight cluster with the exception of sample JT-20 from Johns Brook which has the highest TDS values and Ca concentration of any of the samples measured and plots to the right of the main cluster of data.

The fact that the samples cluster on the left hand side of Figure 4 indicates that they are relatively enriched in Ca compared to Na; however, Na is more prevalent in precipitation. This enrichment in Ca observed in the High Peaks stream water samples is likely a clear indicator of the influence of rock weathering. However, TDS concentrations fall below those generally associated with rivers dominated by rock weathering and, in fact, fall within and slightly above the upper range of those reported for precipitation (Eby, 2004; Gibbs, 1970), indicating High Peaks waters are dilute. In contrast to most other regional studies this one was carried out in drainage basins which are underlain by a single lithology (coarsely crystalline massif anorthosite) devoid of minerals that readily dissolve (Eby, 2004). In addition, the streams sampled are small and of limited length in their headwater region. Hence their position on Figure 4 is a consequence of the characteristics of their drainage basin and dominated by the limited susceptibility of a single, albeit somewhat variable, rock type to weathering.

The lack of data for anionic compounds (not measured) precludes the use of the full complement of Piper Diagrams (Piper, 1953) which are often used to evaluate the mixing of water sources. Cation data were used to construct the cation Piper plot, which uses a triangular diagram with the normalized concentrations of Ca, Mg, and Na. On such a plot all of the High Peaks stream samples form a relatively tight, but linear cluster (Figure 5a) with very consistent proportions of Mg. If this linearity represents a mixing line it is between sources with various proportions of Ca to Na but with similar amounts of Mg. Variability in Ca, Na, and K is not uncommon among andesine feldspars in the High Peaks region (Figure 1 of Casey et al., 1991) and the trend could conceivably be a function of variable feldspar composition within various drainage basins.

Alternatively, this linearity on Figure 5a may indicate a difference in the amount of runoff to groundwater in each stream at the time of sampling. Groundwater has more time to interact with rock and should be more reflective of rock chemistry. Precipitation, which feeds overland flow, generally is enriched in Na over Ca (Gibbs, 1970). Greater proportions of precipitation in the streams would elongate the cluster towards the Na corner of the diagram, generating a linear pattern.  Stream flow during the sampling event is considered to reflect precipitation events as shown by the hydrograph discussed above (Figure 3).

One additional factor to be considered is the possible influence of a soluble carbonate phase on water chemistry. As noted above, Johns Brook has the highest TDS, ANC, and Ca, Sr, and Mg concentrations and drains an area known to contain large marble and calc-silicate xenoliths (Isachsen and Fisher, 1970).   The influence of highly soluble calcite would result in elongation of the cluster towards Ca. Review of Figure 4 indicates that most of the samples are enriched in calcium over sodium. Given andesine’s composition of greater amounts of Na than Ca (specifically An30-An50), the influence of marble or calc-silicate xenoliths seems plausible to drive the stream water composition to the left (Ca-end). This is in general agreement with the higher pH values measured in Ca-rich waters which serves as a strong buffering agent of acidity. In addition, dissolution of calcite in xenoliths could explain other water chemistry parameters such as high TDS, ANC, and Sr concentrations.

About half the water samples have pH values higher than natural, non-anthropogenic impacted, rainwater (~5.7) and some approach neutral pH. Because acid precipitation (pH < 5.7) occurs in the Adirondack region (Jenkins et al., 2007), this indicates that considerable buffering of acidity is taking place in some drainage basins in the High Peaks. This result was not anticipated because of the uniform rock type and limited buffering capacity of massif anorthosite. Note that a linear trend also occurs between Si and Ca on Figure 5b indicating possible mixing of waters enriched in Si (silicate minerals) and Ca (carbonate minerals) or minerals that contain both, such as andesine. A clear distinction between the Johns Brook sample and the rest is shown in Figure 5b as well as Figure 5a. Calcium dominates the dissolved species in the water from this stream. Clearly, knowledge of the detailed geology and geomorphology of individual drainage basins is needed to understand the effects of acidic precipitation in detail even in an area of relatively simple geology.

Figure 6 shows the normalized proportions of the mean water chemistry of Adirondack High Peaks streams matched against the average chemical composition of anorthosite from Buddington (1939), the rock type that underlies the region.   There is, in general, excellent agreement between the two. However, variation in the solubility of major cations is considerable and results in notable differences as well. Although Al2O3 makes up approximately 25.61% of the Marcy anorthosite it is much less abundant in High Peaks stream water, making up only 4.3% of the total dissolved solids on the average. This is a function of the low solubility of aluminum, even at acidic pH values, which is typically incorporated into aluminum-rich, residual weathering products or relatively insoluble hydroxide phases. Calcium, Mg, and Na are 2-4 times as abundant in stream waters as in anorthosite, indicating their greater solubility and relatively rapid release during hydrolysis (Casey et al., 1991). As plagioclase feldspar weathers by incongruent dissolution it loses Ca, Na, Si (in the form of H4SiO4), and alters to hydrous, aluminous phyllosilicate mineral phases such as kaolinite or gibbsite.

The difference in the behavior of trivalent, insoluble cations (i.e. Al, Fe, Mn) and soluble mono- and divalent cations (i.e. Na, K, Ca, Mg) during weathering are evident when concentrations are plotted against one another on scatterplots. Plotting aluminum versus calcium yields a negative correlation (Figure 7) and a power correlation gives the best fit (r2 = 0.82). Aluminum is positively correlated with Zn and Fe concentrations and negatively correlated with Mg, Si, and Sr (in addition to Ca). Calcium on the other hand is positive correlated with Mg, Sr, Si, Na, and K concentrations, and is negatively correlated with Fe, Zn, and Mn (in addition to Al; Table 3). These trends are consistent with weathering of anorthositic rocks, primarily andesine via hydrolysis releasing mono- and divalent cations and silicic acid. Aluminum and trivalent cations like ferric iron form residual phases and rapidly increase in concentration in acidic waters; although their concentration is relatively small when compared to other more soluble components. Most Fe is likely derived from the weathering of ferrous iron in mafic silicates like olivine, pyroxene, and hornblende; Al and Si are key components of feldspar. Potassium was found above the detection limit of 50 ppb in only 11 of 17 samples and its relatively low concentrations indicate the much greater abundance of plagioclase relative to potassium feldspar within the region. Where potassium is detected, it likely indicates the local concentrations of ubiquitous intrusive granitic and charnockitic sheets, enriched in potassium feldspar, noted throughout the High Peaks region (Buddington, 1939).

In general, the water chemistry in the region is largely controlled by at least two major processes: 1) the hydrolysis of andesine feldspar; 2) the response of the system to enhanced acidity facilitating the solubility of aluminum, normally nearly insoluble at near neutral pH. In addition, the presence or absence of soluble xenoliths appears to be important as well (Figure 4a) in terms of elevating Ca concentrations, TDS, and ANC. However, it should be stressed that the chemical differences among the High Peaks streams are fairly subtle and when normalized for TDS a limited range in chemistry is observed (Figure 8). Study of geomorphological parameters such as basin area, relief, slope, stream order, among others may help further refine the preliminary interpretations presented here. However, the relatively limited variation observed emphases the dominant role of the underlying anorthositic bedrock, in determining stream chemistry.

Implications of the Data Collected and Future Study

At the onset of this project it was suspected that the stream chemistry of water in the High Peaks region would be most strongly influenced by precipitation. The reasons for this are numerous and include limited soil development and minor amounts of unconsolidated sediment blanketing bedrock, short and fast overland flow paths down steep terrain, minimized weathering due to harsh climatic conditions and limited forest development, the resistance of coarse-grained, nearly monomineralic, metaigneous rock to weathering (limited porosity and permeability), and relatively high amounts of precipitation. A highly dominant precipitation source may well be true for some of the anionic species not measured in this study including SO2 and NOx or for mercury and other contaminants with limited sources within the Adirondack region. However, it is clear that the bedrock in the Adirondack High Peak region has a strong influence on the multi-element chemistry, pH, and ANC of streams in the region.

Relatively little detailed study has occurred on the acidification of streams in the Adirondack region with the exception of the western Adirondacks (Lawrence, 2002, Lawrence et al., 2004; 2008). There both chronic and episodic acidification has been recognized as problematic. Little or no work has occurred in the High Peaks region but the limited number of geological variables makes it an ideal area to study subtle differences in headwater drainage basins and their response to acidification. In addition, because of the limited potential for storage of acidic species in shallow soils and the rapid flow-through of water, these drainage basins should respond quickly to any changes in wet and/or dry deposition of contaminants and thus represent a potential opportunity to preview changes that will eventually affect the entire region.

Clearly more monitoring and study of the High Peaks region is needed. Additional species such as anions and mercury should be added to the analyte list. Studies involving seasonal or event sampling are of high importance, as are the establishment of permanent monitoring sites. Our study underscores the need for detailed understanding of the bedrock geology and its relation to water chemistry. Seasonal differences should also be investigated to provide a more complete picture of the potential for episodic acidification events. And finally, incorporation of geomorphological parameters will allow a more detailed understanding of the stream water chemistry than this preliminary survey allows. An intriguing research question is how rapidly downstream changes in pH, chemical makeup, and contaminant levels occur.

Summary

A unique sampling opportunity allowed the near simultaneous collection of 17 stream samples in the Adirondack High Peaks region on October 4th and 5th of 2008 assisted by students, staff, and alumni of St. Lawrence University. The samples were analyzed for pH, ANC, and 72 elements by inductively coupled plasma – mass spectrometry (ICP-MS). Samples were dilute (low total dissolved solids 6.22 -16.1 ppm), acidic (4.90 – 6.42), with relatively high aluminum (54-562 ppb), but dominated by silicon and calcium. Aluminum concentrations are correlated with low pH, low TDS, low ANC, and higher iron and zinc concentrations. Calcium concentrations are correlated with higher pH, higher TDS, higher ANC, and elevated concentrations of soluble mono- and divalent cations. The elemental proportions in each stream sample are highly similar but with subtle differences. The data suggests the weathering of massif anorthosite, which underlies the entire High Peaks region, contributes the bulk of the chemical constituents to the stream water. Samples with the greatest TDS, pH, ANC, and Ca concentrations drain watersheds known to have soluble carbonate derived from xenoliths of marble and calc-silicate gneisses entrained in the anorthosite. This data can be compared with future sampling events to monitor the effects of possible future changes on water chemistry in the High Peaks region. Because of limited soil cover and limited retention times, the drainage basins of this area may well serve as a harbinger of changes that will eventually affect the entire region.

 

Acknowledgments

I would like to gratefully acknowledge the help of the St. Lawrence University Outing Club with organizing and carry out the sampling event. Specifically, geology majors Johanna Palmer and Thomas Wright were instrumental in coordinating much of the study. I would also like to thank the students, alumni, and staff of St. Lawrence University for their generous support of, and assistance with, this project.

 

Figure Captions

Figure 1. Simplified geological map of the Adirondack region showing the Marcy anorthosite massif. Small inset shows location of the Adirondacks with respect to the greater contiguous Grenville Province. The study area is shown in the red rectangle and is blown up in Figure 2.

Figure 2. Location diagram showing the sampling sites utilized in this study, geological contacts, drainages and lakes, and select peaks.

Figure 3. Hydrograph showing the discharge recorded at the Ausable Forks USGS gauging station (#04275500) on the Ausable River for the period September 28 to October 5th, 2008.

Figure 4. Diagram after Gibbs (1970) plotting the total dissolved solids (TDS) versus the ratio of Na/(Na+Ca) for High Peaks streams sampled during this study. The black line outlines the field of natural waters noted by Gibbs. The red star indicates the sample from Johns Brook.

Figure 5. Ternary diagram plotting the normalized concentrations of for High Peak streams sampled in this study: a) Ca, Mg, and Na b) Ca, Si, and Na. Red stars indicate the sample from Johns Brook.

Figure 6. Scatter plot of aluminum versus calcium concentrations for High Peaks streams sampled in this study. Note that the trend line is for a power regression.

Figure 7. Pie chart showing the normalized abundance of the major cationic components of anorthosite (Buddington, 1939) and High Peaks Stream water composition (this study). Note that rock chemistry is given in oxide percentages and water chemistry in normalized elemental concentrations.

Figure 7. Plot of major element concentrations normalized to 100% for each of the High Peaks streams sampled in this study. Filled circle indicates mean percentage of total for each element and upper and lower bars indicate standard deviation of entire dataset. This diagram shows the limited range in stream composition when differences in TDS are normalized.

Tables

Table 1. Sampling locations utilized in this study.

Table 2. Summary of stream water chemistry results collected for this study.

Table 3. Correlation coefficient matrix for major components of stream water in the High Peaks region.

 

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McLelland, J., Daly, S., and McLelland, J.M., 1996, The Grenville Orogenic Cycle (ca. 1350–1000 Ma): An Adirondack perspective: Tectonophysics, v. 265, p. 1–28.

McLelland, J., Chiarenzelli, J., Whitney, P., and Isachsen, Y., 1988. U-Pb zircon geochronology of the Adirondack Mountains and implications for their geologic evolution. Geology, v. 16, p. 920-924.

Piper, A.M. (1953). A Graphic Procedure in the Geochemical Interpretation of Water Analysis. Washington D.C.: United States Geological Survey.

 

Regan, S. P., Chiarenzelli, J. R., McLelland, J. M., and Cousens, B. L., 2011. Evidence for an enriched asthenospheric source for coronitic metagabbros in the Adirondack Highlands: Geosphere, v. 7, p. 694-709.

 

Roden-Tice, M. K. and Tice, S. J., 2005. Regional Scale Mid-Jurassic to Late Cretaceous

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Terrie, Phillip G., Contested Terrain; A New History of Nature and People in the Adirondacks, Syracuse: Adirondack Museum/Syracuse University Press, 1997. ISBN 978-0-8156-0904-9.

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Figure 5

 

Figure 6

 

Figure 7

 

Figure 8

 

Table 1. Stream sample locations and physicochemical parameters.
Sample Stream Elevation Latitude Longitude TDS ANC pH
(m) (decimal degrees) (ppm) (?eq/L) (units)
JT-7 East Inlet 685 44.069638 73.810711 8.73 31 6.26
JT-8 Slide Brook 850 44.047759 73.795070 11.35 69 6.30
JT-9 Big Sally Brook 683 44.037474 73.807165 11.49 69 6.19
JT-10 Indian Pass Brook 711 44.186389 74.002552 9.36 57 6.18
JT-12 Santanoni Brook 1077 44.076903 74.087143 7.19 25 5.10
JT-13 Santanoni Brook 594 44.095187 74.125432 7.10 30 5.44
JT-14 East Branch Ausable 551 44.133144 73.811785 8.35 44 5.78
JT-15 Trib. To Arnold Lake 1046 44.136316 73.938717 6.22 36 5.26
JT-16 Slide Brook 586 44.169550 73.840476 8.43 57 6.09
JT-17 Porter Brook 578 44.151136 73.751923 12.97 95 6.42
JT-18 Gill Creek 525 44.128530 73.807795 7.85 23 5.77
JT-19 Gill Creek 990 44.098157 73.824349 7.25 9 4.90
JT-20 Johns Brook 609 44.173937 73.838505 16.06 83 6.30
JT-21 Opalescent Creek 993 44.110127 73.960400 6.64 17 5.29
JT-22 Marcy Brook 719 44.156908 73.953898 6.47 16 5.25
JT-23 Ward Brook 648 44.175669 74.169506 8.08 30 5.75
JT-24 Trib. To Ward Brook 626 44.186065 74.201331 7.45 20 5.34

 

Table 2. Summary of analytical results
DL Count Mean Std. Dev. High Low RPD
?g/L ?g/L ?g/L ?g/L ?g/L %
Ag <.05 0 nd nd nd nd
Al <1 18 261.1 166.9 562.0 54.0 6.81
As <.5 0 nd nd nd nd
Au <.05 0 nd nd nd nd
B 5 1 5.00 #DIV/0! 5.00 5.00
Ba <0.05 18 3.26 0.88 4.60 1.73 0.69
Be <.05 0 nd nd nd nd
Bi <.05 0 nd nd nd nd
Br <5 0 nd nd nd nd
Ca <50 18 2076.9 922.8 4098.0 1061.0 9.09
Cd <.05 7 0.07 0.01 0.08 0.06 0.00
Ce <0.01 18 0.09 0.04 0.16 0.03 0.00
Cl <1000 1 3000.0 #DIV/0! 3000.0 3000.0
Co <0.02 13 0.14 0.09 0.33 0.02 5.71
Cr <.5 6 0.75 0.23 1.10 0.50
Cs <.01 2 0.01 0.00 0.01 0.01
Cu <.1 3 0.33 0.40 0.80 0.10
Dy <.01 15 0.01 0.00 0.02 0.01 0.00
Er <.01 9 0.01 0.00 0.01 0.01
Eu <.01 7 0.01 0.00 0.01 0.01 0.00
Fe <10 7 24.57 11.39 41.00 10.00 30.99
Ga <.05 0 nd nd nd nd
Gd <.05 18 0.01 0.01 0.03 0.01 0.00
Ge <.05 0 nd nd nd nd
Hf <.02 0 nd nd nd nd
Hg <.1 5 0.10 0.00 0.10 0.10
Ho <.01 0 nd nd nd nd
In <.01 0 nd nd nd nd
Ir <.05 0 nd nd nd nd
K <50 11 122.0 70.3 233.0 50.0
La <0.01 18 0.04 0.02 0.09 0.02 0.00
Li <.1 5 0.10 0.00 0.10 0.10
Lu <.01 0 nd nd nd nd
Mg <50 18 304.3 174.5 701.0 123.0 9.30
Mn <.05 13 7.71 4.57 12.75 0.06 3.27
Mo <.1 0 nd nd nd nd
Na <50 18 768.9 597.7 3024.0 372.0 8.99
Nb <.01 0 nd nd nd nd
Nd <0.01 18 0.07 0.03 0.16 0.03 0.00
Ni <.2 0 nd nd nd nd
Os <.05 0 nd nd nd nd
P <20 0 nd nd nd nd
Pb <.1 0 nd nd nd nd
Pd <.2 0 nd nd nd nd
Pr <0.01 18 0.01 0.01 0.03 0.01 0.00
Pt <.01 0 nd nd nd nd
Rb <0.01 18 0.19 0.13 0.57 0.05 0.00
Re <.01 0 nd nd nd nd
Rh <.01 0 nd nd nd nd
Ru <.05 0 nd nd nd nd
S <1000 18 1333.3 485.1 2000.0 1000.0 0.00
Sb <.05 4 0.07 0.00 0.07 0.07 0.00
Sc <1 18 1.00 0.00 1.00 1.00 0.00
Se <.5 0 nd nd nd nd
Si <40 18 3711.6 677.1 5236.0 2755.0 6.67
Sm <.02 4 0.02 0.00 0.03 0.02
Sn <.05 0 nd nd nd nd
Sr <0.01 18 12.13 4.12 20.71 7.28 5.22
Ta <.02 0 nd nd nd nd
Tb <.01 0 nd nd nd nd
Te <.05 0 nd nd nd nd
Th <.05 0 nd nd nd nd
Ti <10 0 nd nd nd nd
Tl <.01 8 0.01 0.00 0.01 0.01 0.00
Tm <.01 0 nd nd nd nd
U <.02 0 nd nd nd nd
V <.2 3 0.20 0.00 0.20 0.20 0.00
W <.02 0 nd nd nd nd
Y <0.01 18 0.06 0.02 0.11 0.02 0.00
Yb <.01 12 0.01 0.00 0.01 0.01
Zn <.5 17 4.15 2.56 9.30 0.70 9.03
Zr <.02 13 0.02 0.01 0.04 0.02 0.00
TDS 18 8734.1 2645.8 16061.4 6217.2
ANC 17 41.82 25.46 95.00 9.00
pH 17 5.74 0.49 6.42 4.90

 

 

Table 3.   Correlation coefficients for select elements in Adirondack High Peaks streams.
r2 Al Ca Fe K Mg Mn Na Rb Si Sr Zn
Al -0.82 0.80 -0.51 -0.76 0.39 -0.50 -0.41 -0.86 -0.9 0.95
Ca -0.66 0.67 0.91 -0.59 0.74 0.60 0.84 0.88 -0.7
Fe 0.05 -0.59 0.89 -0.27 -0.51 -0.8 -0.6 0.79
K 0.77 0.37 0.45 0.88 0.60 0.50 -0.36
Mg -0.60 0.75 0.56 0.78 0.69 -0.75
Mn -0.48 0.11 -0.67 -0.23 0.43
Na 0.35 0.36 0.62 0.42
Rb 0.53 0.45 -0.26
Si 0.78 -0.85
Sr -0.80
Zn

 

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