Changes in dissolved organic matter (DOM) amount and composition along nested headwater stream locations during baseflow and stormflow

Amount and composition of dissolved organic matter (DOM) were evaluated for multiple, nested stream locations in a forested watershed to investigate the role of hydrologic flow paths, wetlands and drainage scale. Sampling was performed over a 4‐year period (2008–2011) for five locations with drainage areas of 0.62, 3.5, 4.5, 12 and 79 ha. Hydrologic flow paths were characterized using an end‐member mixing model. DOM composition was determined using a suite of spectrofluorometric indices and a site‐specific parallel factor analysis model. Dissolved organic carbon (DOC), humic‐like DOM and fluorescence index were most sensitive to changes with drainage scale, whereas dissolved organic nitrogen, specific UV absorbance, Sr and protein‐like DOM were least sensitive. DOM concentrations and humic‐like DOM constituents were highest during both baseflow and stormflow for a 3.5‐ha catchment with a wetland near the catchment outlet. Whereas storm‐event concentrations of DOC and humic DOM constituents declined, the mass exports of DOC increased with increasing catchment scale. A pronounced dilution in storm‐event DOC concentration was observed at peak stream discharge for the 12‐ha drainage location, which was not as apparent at the 79‐ha scale, suggesting key differences in supply and transport of DOM. Our observations indicate that hydrologic flow paths, especially during storms, and the location and extent of wetlands in the catchment are key determinants of DOM concentration and composition. This study furthers our understanding of changes in DOM with drainage scale and the controls on DOM in headwater, forested catchments. Copyright © 2014 John Wiley & Sons, Ltd.     

Controls on surface water chemistry in two lake‐watersheds in the Adirondack region of New York: differences in nitrogen solute sources and sinks

The southwestern Adirondack region of New York receives among the highest rates of atmospheric nitrogen (N) deposition in the USA. Atmospheric N deposition to sensitive ecosystems, like the Adirondacks, may increase the acidification of soils through losses of exchangeable nutrient cations, and the acidification of surface waters associated with enhanced mobility of nitrate (NO₃^?). However, watershed attributes, including surficial terrestrial characteristics, in‐lake processing, and geological settings, have been found to complicate the relationships between atmospheric N deposition and N drainage losses. We studied two lake‐watersheds in the southwestern Adirondacks, Grass Pond and Constable Pond, which are located in close proximity (～26 km) and receive similarly high N deposition, but have contrasting watershed attributes (e.g. wetland area, geological settings). Since the difference in the influence of N deposition was minimal, we were able to examine both within‐ and between‐watershed influences of land cover, the contribution of glacial till groundwater inputs, and in‐lake processes on surface water chemistry with particular emphasis on N solutes and dissolved organic carbon (DOC). Monthly samples at seven inlets and one outlet of each lake were collected from May to October in 1999 and 2000. The concentrations of NO₃^? were high at the Grass Pond inlets, especially at two inlets, and NO₃^? was the major N solute at the Grass Pond inlets. The concentrations of likely weathering products (i.e. dissolved Si, Ca²⁺, Mg²⁺, Na⁺) as well as acid neutralizing capacity and pH values, were also particularly high at those two Grass Pond inlets, suggesting a large contribution of groundwater inputs. Dissolved organic N (DON) was the major N solute at the Constable Pond inlets. The higher concentrations of DON and DOC at the Constable Pond inlets were attributed to a large wetland area in the watershed. The DOC/DON ratios were also higher at the Constable Pond inlets, possibly due to a larger proportion of coniferous forest area. Although DON and DOC were strongly related, the stronger relationship of the proportion of wetland area with DOC suggests that additional factors regulate DON. The aggregated representation of watershed physical features (i.e. elevation, watershed area, mean topographic index, hypsometric‐analysis index) was not clearly related to the lake N and DOC chemistry. Despite distinctive differences in inlet N chemistry, NO₃^? and DON concentrations at the outlets of the two lakes were similar. The lower DOC/DON ratios at the lake outlets and at the inlets having upstream ponds suggest the importance of N processing and organic N sources within the lakes. Although an inverse relationship between NO₃^? and DOC/DON has been suggested to be indicative of a N deposition gradient, the existence of this relationship for sites that receive similar atmospheric N deposition suggest that the relationship between NO₃^? and the DOC/DON ratio is derived from environmental and physical factors. Our results suggest that, despite similar wet N deposition at the two watershed sites, N solutes entering lakes were strongly affected by hydrology associated with groundwater contribution and the presence of wetlands, whereas N solutes leaving lakes were strongly influenced by in‐lake processing. Copyright © 2006 John Wiley & Sons, Ltd.     

Evaluating sulfur dynamics during storm events for three watersheds in the northeastern USA: a combined hydrological,chemical and isotopic approach

Concerns related to climate change have resulted in an increasing interest in the importance of hydrological events such as droughts in affecting biogeochemical responses of watersheds. The effects of an unusually dry summer in 2002 had a marked impact on the biogeochemistry of three watersheds in the north‐eastern USA. Chemical, isotopic and hydrological responses with particular emphasis on S dynamics were evaluated for Archer Creek (New York), Sleepers River (Vermont) and Cone Pond (New Hampshire) watersheds. From 1 August to 14 September 2002, all three watersheds had very low precipitation (48 to 69 mm) resulting in either very low or no discharge (mean 0·015, 0·15 and 0·000 mm day^?1 for Archer Creek, Sleepers River and Cone Pond, respectively). From 15 September to 31 October 2002, there was a substantial increase in precipitation totals (212, 246 and 198 mm, respectively) with increased discharge. Archer Creek was characterized by a large range of SO₄^2? concentrations (152 to 389 µeq L^?1, mean = 273 µeq L^?1) and also exhibited the greatest range in δ³⁴S values of SO₄^2? (?1·4 to 8·8 ‰ ). Sleepers River's SO₄^2? concentrations ranged from 136 to 243 µeq L^?1 (mean = 167 µeq L^?1) and δ³⁴S values of SO₄^2? ranged from 4·0 to 9·0 ‰ . Cone Pond's SO₄^2? concentrations (126–187 µeq L^?1, mean = 154 µeq L^?1) and δ³⁴S values (2·4 to 4·3 ‰ ) had the smallest ranges of the three watersheds. The range and mean of δ¹⁸O‐SO₄^2? values for Archer Creek and Cone Pond were similar (3·0 to 8·9 ‰ , mean = 4·5 ‰ ; 3·9 to 6·3 ‰ , mean = 4·9 ‰ ; respectively) while δ¹⁸O‐SO₄^2? values for Sleepers River covered a larger range with a lower mean (1·2 to 10·0 ‰ , mean = 2·5). The difference in Sleepers River chemical and isotopic responses was attributed to weathering reactions contributing SO₄^2?. For Archer Creek wetland areas containing previously reduced S compounds that were reoxidized to SO₄^2? probably provided a substantial source of S. Cone Pond had limited internal S sources and less chemical or isotopic response to storms. Differences among the three watersheds in S biogeochemical responses during these storm events were attributed to differences in S mineral weathering contributions, hydrological pathways and landscape features. Further evaluations of differences and similarities in biogeochemical and hydrological responses among watersheds are needed to predict the impacts of climate change. Copyright © 2008 John Wiley & Sons, Ltd.     

Obituary Robert W. Pennak

Obituary

Obituary Robert W. Pennak     

Relationship of topography to surface water chemistry with particular focus on nitrogen and organic carbon solutes within a forested watershed in Hokkaido,Japan

We studied the relationships between streamwater chemistry and the topography of subcatchments in the Dorokawa watershed in Hokkaido Island, northern Japan, to examine the use of topography as a predictor of streamwater chemistry in a watershed with relatively moderate terrain compared with other regions of Japan. Topographic characteristics of the Dorokawa watershed and its subcatchments were expressed as topographic index (TI) values, which ranged from 4·5 to 20·4 for individual grid cells (50 × 50 m²), but averaged from 6·4 to 7·4 for the 20 subcatchments. Streamwater samples for chemical analyses were collected four times between June and October 2002 from 20 locations in the watershed. The pH of water that passed through the watershed increased from ～5·0 to 7·0, with major increases in Na⁺ and Ca²⁺ and marked decreases in NO₃^? and SO . Distinctive spatial patterns were observed for dissolved organic carbon (DOC), dissolved organic nitrogen (DON), and NO₃^? concentrations of streamwater across the watershed. Statistical analyses indicated significant linear relationships between the average TI values of subcatchments and DOC, DON, and NO₃^? concentrations. Furthermore, the proportion of DOC in streamwaters in the wet season increased with TI values relative to other nitrogen species, whereas NO₃^? concentrations decreased with TI. The gradients of soil wetness and the presence of wetlands explained many of the observed spatial and temporal patterns of DOC, DON, and NO₃^? concentrations in the surface waters of the Dorokawa watershed. Our results suggest that the TI is especially useful for predicting the spatial distribution of DOC, DON and NO₃^? in the surface waters of Hokkaido, where topographical relief is moderate and wetlands more common than in other regions of Japan. Copyright © 2006 John Wiley & Sons, Ltd.     

The Oligocene Lund Tuff, Great Basin, USA: a very large volume monotonous intermediate

Unusual monotonous intermediate ignimbrites consist of phenocryst-rich dacite that occurs as very large volume (>1000 km³) deposits that lack systematic compositional zonation, comagmatic rhyolite precursors, and underlying plinian beds. They are distinct from countless, usually smaller volume, zoned rhyolite–dacite–andesite deposits that are conventionally believed to have erupted from magma chambers in which thermal and compositional gradients were established because of sidewall crystallization and associated convective fractionation. Despite their great volume, or because of it, monotonous intermediates have received little attention. Documentation of the stratigraphy, composition, and geologic setting of the Lund Tuff – one of four monotonous intermediate tuffs in the middle-Tertiary Great Basin ignimbrite province – provides insight into its unusual origin and, by implication, the origin of other similar monotonous intermediates.The Lund Tuff is a single cooling unit with normal magnetic polarity whose volume likely exceeded 3000 km³. It was emplaced 29.02±0.04 Ma in and around the coeval White Rock caldera which has an unextended north–south diameter of about 50 km. The tuff is monotonous in that its phenocryst assemblage is virtually uniform throughout the deposit: plagioclase>quartz≈hornblende>biotite>Fe–Ti oxides≈sanidine>titanite, zircon, and apatite. However, ratios of phenocrysts vary by as much as an order of magnitude in a manner consistent with progressive crystallization in the pre-eruption chamber. A significant range in whole-rock chemical composition (e.g., 63–71 wt% SiO₂) is poorly correlated with phenocryst abundance.These compositional attributes cannot have been caused wholly by winnowing of glass from phenocrysts during eruption, as has been suggested for the monotonous intermediate Fish Canyon Tuff. Pumice fragments are also crystal-rich, and chemically and mineralogically indistinguishable from bulk tuff. We postulate that convective mixing in a sill-like magma chamber precluded development of a zoned chamber with a rhyolitic top or of a zoned pyroclastic deposit. Chemical variations in the Lund Tuff are consistent with equilibrium crystallization of a parental dacitic magma followed by eruptive mixing of compositionally diverse crystals and high-silica rhyolite vitroclasts during evacuation and emplacement. This model contrasts with the more systematic withdrawal from a bottle-shaped chamber in which sidewall crystallization creates a marked vertical compositional gradient and a substantial volume of capping-evolved rhyolite magma. Eruption at exceptionally high discharge rates precluded development of an underlying plinian deposit.The generation of the monotonous intermediate Lund magma and others like it in the middle Tertiary of the western USA reflects an unusually high flux of mantle-derived mafic magma into unusually thick and warm crust above a subducting slab of oceanic lithosphere.     

Scaling and Demographic Issues in Global Change Research: The Great Plains, 1880-1990

This paper is about the scales at which demographic data are available, and demographic research is conducted, and their implications for understanding the relationship between population and environment. It describes a multi-disciplinary project designed to study the long-term relationship between population, land use, and environment in the U.S. Great Plains. The paper begins with a discussion of the scales at which data are readily available for demographic, agricultural land use, and environmental data for the United States. Some of these data can be obtained at relatively high resolutions, but the lowest common denominator for many of the long term data is the county, a fairly large unit. I then discuss the advantages and disadvantages of the different scales available. The third section of the paper uses county net migration as an example of research that can be done, and the scale at which it is effective. The example shows that the county is an effective unit for the study of migration, and that the research results are significant. The conclusion suggests that the study of population processes in an environmental and economic context is appropriate at the county level for some questions, but that scaling the results to larger units may be difficult because of the need to be certain about the contexts in which those processes take place. We probably should not study net migration at the national or continental scale, but aggregating county-level or regional studies to a larger scale may be successful.     

Paleolimnology of McNearney lake: an acidic lake in northern Michigan

McNearney Lake is an acidic (pH=4.4) lake in the Upper Peninsula of Michigan with low acid neutralizing capacity (ANC=-38 eq L^-1) and high SO _inf4 ^sup2- and aluminium concentrations. Oligotrophy is indicated by high Secchi transparency and by low chlorophyll a, total phosphorus, and total nitrogen concentrations. The lake water is currently acidic because base cations are supplied to the lake water at a low rate and because SO _inf4 ^sup2- from atmospheric deposition was not appreciably retained by the lake sediments or watershed and was present in the water column.This interdisciplinary paleolimnological study indicates that McNearney Lake is naturally acidic and has been so since at least 4000 years B.P., as determined from inferred-pH techniques based on contemporary diatom-pH relationships. Predicted pH values ranged from 4.7 to 5.0 over the 4000-year stratigraphy. Considerable shifts in species composition and abundance were observed in diatom stratigraphy, but present-day distributions indicate that all abundant taxa most frequently occur under acidic conditions, suggesting that factors other than pH are responsible for the shifts. The diatom-inferred pH technique as applied to McNearney Lake has too large an uncertainly and is not sensitive enough to determine the subtle recent changes in lakewater pH expected from changes in atmospheric deposition because: (1) McNearney Lake has the lowest pH in the contemporary diatom data set in the region and confidence intervals for pH predictions increase at the extremes of regressions; (2) other factors in addition to pH may be responsible for the diatom species distribution in the lake and in the entire northern Great Lakes region; (3) McNearney Lake has a well-buffered pH as a consequence of its low pH and high aluminium concentrations and is not expected to exhibit a large pH change as a result of changes in atmospheric deposition; and (4) atmospheric deposition in the region is modest and would not cause a pH shift large enough to be discernable in McNearney Lake.Elevated atmospheric deposition is indicated in recent sediments by Pb, V, and polycyclic aromatic hydrocarbon accumulation rates and to a lesser extent by those of Cu and Zn; however, these accumulation rates are substantially lower than those observed for acidified lakes in the northeastern United States. Although atmospheric loadings of materials associated with fossil fuel combustion have recently increased to McNearney Lake and apparently are continuing, the present study of the diatom subfossil record does not indicate a distinct, recent acidification (pH decrease).Order of the first two authors is alphabetical     

Chaos in the solar system

We have accumulated thousands of orbits of test particles in the Solar System from the asteroid belt to beyond the orbit of Neptune. We find that the time for an orbit to make a close encounter with a perturbing planet, T _c ,is a function of the Lyapunov time, T _ty .The relation is log (T _c /T _o )= a + b log (T _ly T _o )where T _o is a fiducial period which we have taken as the period of the principal perturber or the period of the asteroid. There are exceptions to this rule interior to the 2/3 resonance with Jupiter. There, at least in the restricted problem, for sufficiently small Jupiter mass, orbits may have a positive Lyapunov exponent and still be blocked from having a close approach to Jupiter by a zero velocity curve. Of more serious concern is whether the relation holds for purely secular resonances, and if it does, how to choose T _o .This is the case of interest for the planets in the solar system.     

Numerical modelling of multiphase flow in porous media

The simultaneous flow of immiscible fluids in porous media occurs in a wide variety of applications. The equations governing these flows are inherently nonlinear, and the geometries and material properties characterizing many problems in petroleum and groundwater engineering can be quite irregular. As a result, numerical simulation often offers the only viable approach to the mathematical modelling of multiphase flows. This paper provides an overview of the types of models that are used in this field and highlights some of the numerical techniques that have appeared recently. The exposition includes discussions of multiphase, multispecies flows in which chemical transport and interphase mass transfers play important roles. The paper also examines some of the outstanding physical and mathematical problems in multiphase flow simulation. The scope of the paper is limited to isothermal flows in natural porous media; however, many of the special techniques and difficulties discussed also arise in artificial porous media and multiphase flows with thermal effects.