Geology topics

M.J. Mitchell

Publications and source records attributed to M.J. Mitchell.

10 recordsLinked to original sources

USGS2010

Identifying sources of stream water sulfate after a summer drought in the Sleepers River watershed (Vermont, USA) using hydrological, chemical, and isotopic techniques

In many forested headwater catchments, peak SO 4 2 - concentrations in stream water occur in the late summer or fall following drought potentially resulting in episodic stream acidification. The sources of highly elevated stream water SO 4 2 - concentrations were investigated in a first order stream at the Sleepers River watershed (Vermont, USA) after the particularly dry summer of 2001 using a combination of hydrological, chemical and isotopic approaches. Throughout the summer of 2001 SO 4 2 - concentrations in stream water doubled from ???130 to 270 ??eq/L while flows decreased. Simultaneously increasing Na + and Ca 2+ concentrations and ?? 34 S values increasing from +7??? towards those of bedrock S (???+10.5???) indicated that chemical weathering involving hydrolysis of silicates and oxidation of sulfide minerals in schists and phyllites was the cause for the initial increase in SO 4 2 - concentrations. During re-wetting of the watershed in late September and early October of 2001, increasing stream flows were accompanied by decreasing Na + and Ca 2+ concentrations, but SO 4 2 - concentrations continued to increase up to 568 ??eq/L, indicating that a major source of SO 4 2 - in addition to bedrock weathering contributed to peak SO 4 2 - concentrations. The further increase in SO 4 2 - concentrations coincided with an abrupt decrease of ?? 34 S values in stream water SO 4 2 - from maximum values near +10??? to minimum values near -3???. Soil investigations revealed that some C-horizons in the Spodsols of the watershed contained secondary sulfide minerals with ?? 34 S values near -22???. The shift to negative ?? 34 S values of stream water SO 4 2 - indicates that secondary sulfides in C-horizons were oxidized to SO 4 2 - during the particularly dry summer of 2001. The newly formed SO 4 2 - was transported to the streams during re-wetting of the watershed contributing ???60% of the SO 4 2 - during peak concentrations in the stream water. Thereafter, the contribution of SO 4 2 - from oxidation of secondary sulfides in C-horizons decreased rapidly and pedogenic SO 4 2 - reemerged as a dominant SO 4 2 - source in concert with decreasing SO 4 2 - concentrations in spring of 2002. The study provides evidence that a quantitative assessment of the sources of stream water SO 4 2 - in forested watersheds is possible by combining hydrological, chemical and isotopic techniques, provided that the isotopic compositions of all potential SO 4 2 - sources are distinctly different. ?? 2010 Elsevier Ltd.

Applied Geochemistry↗

USGS2008

Influences of calcium availability and tree species on Ca isotope fractionation in soil and vegetation

The calcium (Ca) isotope system is potentially of great use for understanding biogeochemical processes at multiple scales in forest ecosystems, yet remains largely unexplored for this purpose. In order to further our understanding of Ca behavior in forests, we examined two nearly adjacent hardwood-dominated catchments with differing soil Ca concentrations, developed from crystalline bedrock, to determine the variability of 44Ca/ 40Ca ratios (expressed as ??44Ca) within soil and vegetation pools. For both sugar maple and American beech, the Ca isotope compositions of the measured roots and calculated bulk trees were considerably lighter than those of soil pools at these sites, suggesting that the trees were able to preferentially take up light Ca at the root-soil interface. The Ca isotope compositions of three of four root samples were among the lightest values yet reported for terrestrial materials (??44Ca ???-3.95???). Our results further indicate that Ca isotopes were fractionated along the transpiration streams of both tree species with roots having the least ??44Ca values and leaf litter the greatest. An approximately 2??? difference in ??44Ca values between roots and leaf litter of both tree species suggests a persistent fractionation mechanism along the transpiration stream, likely related to Ca binding in wood tissue coupled with internal ion exchange. Finally, our data indicate that differing tree species demand for Ca and soil Ca concentrations together may influence Ca isotope distribution within the trees. Inter-catchment differences in Ca isotope distributions in soils and trees were minor, indicating that the results of our study may have broad transferability to studies of forest ecosystems in catchments developed on crystalline substrates elsewhere. ?? 2008 Springer Science+Business Media B.V.

Biogeochemistry↗

USGS2007

Sulfur species behavior in soil organic matter during decomposition

Soil organic matter (SOM) is a primary re??servoir of terrestrial sulfur (S), but its role in the global S cycle remains poorly understood. We examine S speciation by X-ray absorption near-edge structure (XANES) spectroscopy to describe S species behavior during SOM decomposition. Sulfur species in SOM were best represented by organic sulfide, sulfoxide, sulfonate, and sulfate. The highest fraction of S in litter was organic sulfide, but as decomposition progressed, relative fractions of sulfonate and sulfate generally increased. Over 6-month laboratory incubations, organic sulfide was most reactive, suggesting that a fraction of this species was associated with a highly labile pool of SOM. During humification, relative concentrations of sulfoxide consistently decreased, demonstrating the importance of sulfoxide as a reactive S phase in soil. Sulfonate fractional abundance increased during humification irrespective of litter type, illustrating its relative stability in soils. The proportion of S species did not differ systematically by litter type, but organic sulfide became less abundant in conifer SOM during decomposition, while sulfate fractional abundance increased. Conversely, deciduous SOM exhibited lesser or nonexistent shifts in organic sulfide and sulfate fractions during decomposition, possibly suggesting that S reactivity in deciduous litter is coupled to rapid C mineralization and independent of S speciation. All trends were consistent in soils across study sites. We conclude that S reactivity is related to spqciation in SOM, particularly in conifer forests, and S species fractions in SOM change, during decomposition. Our data highlight the importance of intermediate valence species (sulfoxide and sulfonate) in the pedochemical cycling of organic bound S. Copyright 2007 by the American Geophysical Union.

Journal of Geophysical Research G: Biogeosciences↗

USGS2007

Factors controlling nitrogen release from two forested catchments with contrasting hydrochemical responses

Quantifying biogeochemical cycles of nitrogen (N) and the associated fluxes to surface waters remains challenging, given the need to deal with spatial and temporal variability and to characterize complex and heterogeneous landscapes. We focused our study on catchments S14 and S15 located in the Adirondack Mountains of New York, USA, which have similar topographic and hydrologic characteristics but contrasting stream nitrate ($\hbox{NO}_{3}^{-}$) concentrations. We characterized the mechanisms by which $\hbox{NO}_{3}^{-}$ reaches the streams during hydrological events in these catchments, aiming to reconcile our field data with our conceptual model of factors that regulate nutrient exports from forested catchments. Combined hydrometric, chemical and isotopic (δ$\hbox{NO}_{3}^{-}$) data showed that the relative contributions of both soil and ground water sources were similar between the two catchments. Temporal patterns of stream chemistry were markedly different between S14 and S15, however, because the water sources in the two catchments have different solute concentrations. During late summer/fall, the largest source of $\hbox{NO}_{3}^{-}$ in S14 was till groundwater, whereas shallow soil was the largest $\hbox{NO}_{3}^{-}$ source in S15. $\hbox{NO}_{3}^{-}$ concentrations in surface water decreased in S14, whereas they increased in S15 because an increasing proportion of stream flow was derived from shallow soil sources. During snowmelt, the largest sources of $\hbox{NO}_{3}^{-}$were in the near‐surface soil in both catchments. Concentrations of $\hbox{NO}_{3}^{-}$ increased as stream discharge increased and usually peaked before peak discharge, when shallow soil water sources made the largest contribution to stream discharge. The timing of peaks in stream $\hbox{NO}_{3}^{-}$concentrations was affected by antecedent moisture conditions. By elucidating the factors that affect sources and transport of N, including differences in the soil nutrient cycling and hydrological characteristics of S14 and S15, this study contributes to the overall conceptualization of $\hbox{NO}_{3}^{-}$ release from temperate forested catchments.

Hydrological Processes↗

USGS2006

Solute sources in stream water during consecutive fall storms in a northern hardwood forest watershed: A combined hydrological, chemical and isotopic approach

Understanding the effects of climate change including precipitation patterns has important implications for evaluating the biogeochemical responses of watersheds. We focused on four storms in late summer and early fall that occurred after an exceptionally dry period in 2002. We analyzed not only the influence of these storms on episodic chemistry and the role of different water sources in affecting surface water chemistry, but also the relative contributions of these storms to annual biogeochemical mass balances. The study site was a well studied 135-ha watershed in the Adirondack Park of New York State (USA). Our analyses integrated measurements on hydrology, solute chemistry and the isotopic composition of NO 3 − (δ 15 N and δ 18 O) and SO 4 2− (δ 34 S and δ 18 O) to evaluate how these storms affected surface water chemistry. Precipitation amounts varied among the storms (Storm 1: Sept. 14–18, 18.5 mm; Storm 2: Sept. 21–24, 33 mm; Storm 3: Sept. 27–29, 42.9 mm; Storm 4: Oct. 16–21, 67.6 mm). Among the four storms, there was an increase in water yields from 2 to 14%. These water yields were much less than in studies of storms in previous years at this same watershed when antecedent moisture conditions were higher. In the current study, early storms resulted in relatively small changes in water chemistry. With progressive storms the changes in water chemistry became more marked with particularly major changes in C b (sum of base cations), Si, NO 3 − , and SO 4 2− , DOC and pH. Analyses of the relationships between Si, DOC, discharge and water table height clearly indicated that there was a decrease in ground water contributions (i.e., lower Si concentrations and higher DOC concentrations) as the watershed wetness increased with storm succession. The marked changes in chemistry were also reflected in changes in the isotopic composition of SO 4 2− and NO 3 − . There was a strong inverse relationship between SO 4 2− concentrations and δ 34 S values suggesting the importance of S biogeochemical redox processes in contributing to SO 4 2− export. The isotopic composition of NO 3 − in stream water indicated that this N had been microbially processed. Linkages between SO 4 2− and DOC concentrations suggest that wetlands were major sources of these solutes to drainage waters while the chemical and isotopic response of NO 3 − suggested that upland sources were more important. Although these late summer and fall storms did not play a major role in the overall annual mass balances of solutes for this watershed, these events had distinctive chemistry including depressed pH and therefore have important consequences to watershed processes such as episodic acidification, and the linkage of these processes to climate change.

Biogeochemistry↗

USGS2005

Tracing sources of streamwater sulfate during snowmelt using S and O isotope ratios of sulfate and 35S activity

The biogeochemical cycling of sulfur (S) was studied during the 2000 snowmelt at Sleepers River Research Watershed in northeastern Vermont, USA using a hydrochemical and multi-isotope approach. The snowpack and 10 streams of varying size and land use were sampled for analysis of anions, dissolved organic carbon (DOC), 35 S activity, and δ 34 S and δ 18 O values of sulfate. At one of the streams, δ 18 O values of water also were measured. Apportionment of sulfur derived from atmospheric and mineral sources based on their distinct δ 34 S values was possible for 7 of the 10 streams. Although mineral S generally dominated, atmospheric-derived S contributions exceeded 50% in several of the streams at peak snowmelt and averaged 41% overall. However, most of this atmospheric sulfur was not from the melting snowpack; the direct contribution of atmospheric sulfate to streamwater sulfate was constrained by 35 S mass balance to a maximum of 7%. Rather, the main source of atmospheric sulfur in streamwater was atmospheric sulfate deposited months to years earlier that had microbially cycled through the soil organic sulfur pool. This atmospheric/pedospheric sulfate (pedogenic sulfate formed from atmospheric sulfate) source is revealed by δ 18 O values of streamwater sulfate that remained constant and significantly lower than those of atmospheric sulfate throughout the melt period, as well as streamwater 35 S ages of hundreds of days. Our results indicate that the response of streamwater sulfate to changes in atmospheric deposition will be mediated by sulfate retention in the soil.

Vermont↗

USGS2005

Sources of nitrate in snowmelt discharge: Evidence from water chemistry and stable isotopes of nitrate

To determine whether NO 3 − concentration pulses in surface water in early spring snowmelt discharge are due to atmospheric NO 3 − , we analyzed stream δ 15 N-NO 3 − and δ 18 O-NO 3 − values between February and June of 2001 and 2002 and compared them to those of throughfall, bulk precipitation, snow, and groundwater. Stream total Al, DOC and Si concentrations were used to indicate preferential water flow through the forest floor, mineral soil, and ground water. The study was conducted in a 135-ha subcatchment of the Arbutus Watershed in the Huntington Wildlife Forest in the Adirondack Region of New York State, U.S.A. Stream discharge in 2001 increased from 0.6 before to 32.4 mm day −1 during snowmelt, and element concentrations increased from 33 to 71 μmol L −1 for NO 3 − , 3 to 9 μmol L −1 for total Al, and 330 to 570 μmol L −1 for DOC. Discharge in 2002 was variable, with a maximum of 30 mm day −1 during snowmelt. The highest NO 3 − , Al, and DOC concentrations were 52, 10, and 630 μmol L −1 , respectively, and dissolved Si decreased from 148 μmol L −1 before to 96 μmol L −1 during snowmelt. Values of δ 15 N and δ 18 O of NO 3 − in stream water were similar in both years. Stream water, atmospherically-derived solutions, and groundwaters had overlapping δ 15 N-NO 3 − values. In stream and ground water, δ 18 O-NO 3 − values ranged from +5.9 to +12.9‰ and were significantly lower than the +58.3 to +78.7‰ values in atmospheric solutions. Values of δ 18 O-NO 3 − indicating nitrification, increase in Al and DOC, and decrease in dissolved Si concentrations indicating water flow through the soil suggested a dilution of groundwater NO 3 − by increasing contributions of forest floor and mineral soil NO 3 − during snowmelt.

Water, Air, & Soil Pollution↗

USGS2004

The application of an integrated biogeochemical model (PnET-BGC) to five forested watersheds in the Adirondack and Catskill regions of New York

PnET-BGC is an integrated biogeochemical model formulated to simulate the response of soil and surface waters in northern forest ecosystems to changes in atmospheric deposition and land disturbances. In this study, the model was applied to five intensive study sites in the Adirondack and Catskill regions of New York. Four were in the Adirondacks: Constable Pond, an acid-sensitive watershed; Arbutus Pond, a relatively insensitive watershed; West Pond, an acid-sensitive watershed with extensive wetland coverage; and Willy's Pond, an acid-sensitive watershed with a mature forest. The fifth was Catskills: Biscuit Brook, an acid-sensitive watershed. Results indicated model-simulated surface water chemistry generally agreed with the measured data at all five sites. Model-simulated internal fluxes of major elements at the Arbutus watershed compared well with previously published measured values. In addition, based on the simulated fluxes, element and acid neutralizing capacity (ANC) budgets were developed for each site. Sulphur budgets at each site indicated little retention of inputs of sulphur. The sites also showed considerable variability in retention of NO3-. Land-disturbance history and in-lake processes were found to be important in regulating the output of NO3- via surface waters. Deposition inputs of base cations were generally similar at these sites. Various rates of base cation outputs reflected differences in rates of base cation supply at these sites. Atmospheric deposition was found to be the largest source of acidity, and cation exchange, mineral weathering and in-lake processes served as sources of ANC. ?? 2004 John Wiley and Sons, Ltd.

Hydrological Processes↗

USGS2000

Nitrogen solutes in an Adirondack forested watershed: Importance of dissolved organic nitrogen

Nitrogen (N) dynamics were evaluated from 1 June 1995 through 31 May 1996 within the Arbutus Lake watershed in the Adirondack Mountains of New York State, U.S.A. At the Arbutus Lake outlet dissolved organic nitrogen (DON), NO3/- and NH4/+ contributed 61%, 33%, and 6% respectively, to the total dissolved nitrogen (TDN) flux (259 mol ha-1 yr-1). At the lake inlet DON, NO3/-, and NH4/+ constituted 36%, 61%, and 3% respectively, of TDN flux (349 mol ha-1 yr-1). Differences between the factors that control DON, NO3/-, and NH4+ stream water concentrations were evaluated using two methods for estimating annual N flux at the lake inlet. Using biweekly sampling NO3/- and NH4/+ flux was 10 and 4 mol ha-1 yr-1 respectively, less than flux estimates using biweekly plus storm and snowmelt sampling. DON flux was 18 mol ha-1 yr-1 greater using only biweekly sampling. These differences are probably not of ecological significance relative to the total flux of N from the watershed (349 mol ha-1 yr-1). Dissolved organic N concentrations were positively related to discharge during both the dormant (R2 = 0.31; P<0.01) and growing season (R2= 0.09; P<0.01). There was no significant relationship between NO3/- concentration and discharge during the dormant season, but a significant negative relationship was found during the growing season (R2 = 0.29; P<0.01). Biotic controls in the growing season appeared to have had a larger impact on stream water NO3- concentrations than on DON concentrations. Arbutus Lake had a major impact on stream water N concentrations of the four landscape positions sampled, suggesting the need to quantify within lake processes to interpret N solute losses and patterns in watershed-lake systems.

Biogeochemistry↗

USGS1996

Climatic control of nitrate loss from forested watersheds in the northeast United States

Increased losses of nitrate from watersheds may accelerate the depletion of nutrient cations and affect the acidification and trophic status of surface waters. Patterns of nitrate concentrations and losses were evaluated in four forested watersheds (East Bear Brook Watershed, Lead Mountain, ME; Watershed 6, Hubbard Brook Experimental Forest, White Mountains, NH; Arbutus Watershed, Huntington Forest, Adirondack Mountains, NY; Biscuit Brook, Catskill Mountains, NY) located across the northeastern United States. A synchronous pattern was observed in nitrate concentrations of drainage waters from these four sites from 1983 through 1993. Most notably, high concentrations and high drainage water losses followed an anomalous cold period (mean daily temperature -11.4 to -16 ??C in December 1989) for all four sites. After high nitrate losses during the snowmelt of 1990, nitrate concentrations and fluxes decreased at all sites. These results suggest that climatic variation can have a major effect on nitrogen flux and cycling and may influence temporal patterns of nitrate loss in a region.

Environmental Science & Technology↗