Calibration of paired watersheds: Utility of moving sums in presence of externalities

Historically, paired watershed studies have been used to quantify the hydrological effects of land use and management practices by concurrently monitoring 2 similar watersheds during calibration (pretreatment) and post‐treatment periods. This study characterizes seasonal water table and flow response to rainfall during the calibration period and tests a change detection technique of moving sums of recursive residuals (MOSUM) to select calibration periods for each control–treatment watershed pair when the regression coefficients for daily water table elevation were most stable to minimize regression model uncertainty. The control and treatment watersheds were 1 watershed of 3–4‐year‐old intensely managed loblolly pine (Pinus taeda L.) with natural understory, 1 watershed of 3–4‐year‐old loblolly pine intercropped with switchgrass (Panicum virgatum), 1 watershed of 14–15‐year‐old thinned loblolly pine with natural understory (control), and 1 watershed of switchgrass only. The study period spanned from 2009 to 2012. Silvicultural operational practices during this period acted as external factors, potentially shifting hydrologic calibration relationships between control and treatment watersheds. MOSUM results indicated significant changes in regression parameters due to silvicultural operations and were used to identify stable relationships for water table elevation. None of the calibration relationships developed using this method were significantly different from the classical calibration relationship based on published historical data. We attribute that to the similarity of historical and 2010–2012 leaf area index on control and treatment watersheds as moderated by the emergent vegetation. Although the MOSUM approach does not eliminate the need for true calibration data or replace the classic paired watershed approach, our results show that it may be an effective alternative approach when true data are unavailable, as it minimizes the impacts of external disturbances other than the treatment of interest.     

Stock Origins of Subadult and Adult Atlantic Sturgeon, Acipenser oxyrinchus, in a Non-natal Estuary, Long Island Sound

The anadromous acipenserid Atlantic sturgeon Acipenser oxyrinchus was listed in 2012 under the U.S. Endangered Species Act as having four endangered and one threatened distinct population segment (DPS) in American waters. Anthropogenic activities outside of natal estuaries, particularly bycatch, may hinder the abilities of some populations to rebuild. Most Atlantic sturgeon are residential for their first 2–6 years within their natal estuaries, whereas older subadults and adults may migrate to non-natal estuaries and coastal locations. Previous studies demonstrated that subadults and adults aggregate during summer at locations in Long Island Sound (LIS) and its tributary, the Connecticut River; however, the population origin of these fish is unknown. Because of its geographic proximity and relatively robust population, we hypothesized that the LIS and Connecticut River aggregations were almost solely derived from the Hudson River. We used microsatellite nuclear DNA analysis at 11 loci and mitochondrial DNA control region sequence analyses to estimate the relative contributions of nine Atlantic sturgeon populations and the five DPS to these aggregations using individual-based assignment tests and mixed-stock analysis. From 64 to 73 % of specimens from LIS were estimated to be of Hudson origin. Similarly, 66–76 % of specimens from the Connecticut River were of Hudson origin. However, moderate numbers of specimens were detected from distant spawning populations in the southeastern DPS and from two populations once thought to be extirpated or nearly so, the James River (6–7.3 %), and the Delaware River (7.6–12 %). Additionally, specimens were detected from all five DPS in both the LIS and Connecticut River collections. These results highlight the difficulty of evaluating the status of individual Atlantic sturgeon populations because of the propensity of subadults and adults to migrate for extended duration to distant sites where they may be vulnerable to anthropogenic disturbances.     

Activity–composition relations for phases in petrological calculations: an asymmetric multicomponent formulation

For petrological calculations, including geothermobarometry and the calculation of phase diagrams (for example, P–T petrogenetic grids and pseudosections), it is necessary to be able to express the activity–composition (a–x) relations of minerals, melt and fluid in multicomponent systems. Although the symmetric formalism—a macroscopic regular model approach to a–x relations—is an easy-to-formulate, general way of doing this, the energetic relationships are a symmetric function of composition. We allow asymmetric energetics to be accommodated via a simple extension to the symmetric formalism which turns it into a macroscopic van Laar formulation. We term this the asymmetric formalism (ASF). In the symmetric formalism, the a–x relations are specified by an interaction energy for each of the constituent binaries amongst the independent set of end members used to represent the phase. In the asymmetric formalism, there is additionally a "size parameter" for each of the end members in the independent set, with size parameter differences between end members accounting for asymmetry. In the case of fluid mixtures, for example, H₂O–CO₂, the volumes of the end members as a function of pressure and temperature serve as the size parameters, providing an excellent fit to the a–x relations. In the case of minerals and silicate liquid, the size parameters are empirical parameters to be determined along with the interaction energies as part of the calibration of the a–x relations. In this way, we determine the a–x relations for feldspars in the systems KAlSi₃O₈–NaAlSi₃O₈ and KAlSi₃O₈–NaAlSi₃O₈–CaAl₂Si₂O₈, for carbonates in the system CaCO₃–MgCO₃, for melt in the melting relationships involving forsterite, protoenstatite and cristobalite in the system Mg₂SiO₄–SiO₂, as well as for fluids in the system H₂O–CO₂. In each case the a–x relations allow the corresponding, experimentally determined phase diagrams to be reproduced faithfully. The asymmetric formalism provides a powerful and flexible way of handling a–x relations of complex phases in multicomponent systems for petrological calculations.     

Trace metals and radionuclides reveal sediment sources and accumulation rates in Jordan Cove, Connecticut

Many small estuaries are influenced by flow restrictions resulting from transportation rights-of-way and other causes. The biogeochemical functioning and history of such systems can be evaluated through study of their sediments. Ten long and six short cores were collected from the length of Jordan Cove, Connecticut, a Long Island Sound subestuary, and analyzed for stratigraphy, radionuclides (¹⁴C, ²¹⁰Pb, ²²⁶Ra, ¹³⁷Cs, and ⁶⁰Co), and metals (Ag, Cd, Cu, Pb, Zn, Fe, and Al). For at least 3,800 yr, rising sea level has gradually inundated Jordan Cove, filling it with mud similar to that currently being deposited there. Long-term sediment accumulation in the cove averaged close to 0.1 cm yr⁻¹ over the last three millennia. Recent sediment accumulation rates decrease inland from 0.84 cm yr⁻¹ to 0.40 cm yr⁻¹, and are slightly faster than relative sea-level rise at this site (0.3 cm yr⁻¹). Similarity of depth distributions of trace metals was used to confirm relative sediment accumulation rates. ⁶⁰Co and Ag are derived from sources outside the cove and its watershed, presumably the Millstone nuclear power plant and regional contaminated sediments, respectively. The combined data suggest that Long Island Sound is an important source of sediment to the cove; a minor part of total sediment is supplied from the local watershed. Trace metal levels are strongly correlated with Fe but not with either organic matter or Al. Sediment quality has declined in the cove over the past 60 yr, but only slightly. Cu, Pb, and Zn data correlate strongly with Fe but not with either organic matter or aluminum. Ratios of Ag to Fe and to trace metals suggest that Ag in the cove is derived almost entirely from Long Island Sound. This result supports the notion that Fenormalized Ag can serve as a better tracer of some kinds of contamination than more common and abundant metals, like Cu, Pb, and Zn. *** DIRECT SUPPORT *** A01BY085 00008     

Alluvial gold in Kalimantan, Indonesia: A colloidal origin?

Extensive placer gold deposits occur in Quaternary palaeochannels in the Ampalit and Cempaga Buang drainage basins near Kasongan, Central Kalimantan, Indonesia. Broad interfluvial Pleistocene terraces surrounding the drainages also contain significant amounts of placer gold. The “channel” and “terrace” gold deposits together cover an area in excess of 180 km².Exploration for gold at Ampalit followed traditional alluvial methods, and assumed that mechanical and gravitational factors were the principal mechanisms affecting gold accumulation and concentration. Gold was considered to be physically reworked from terraces and redeposited in the present drainage channels or underlying, laterally displaced, palaeochannels. However, a comparison of gold grains from the Ampalit drainage channel and adjacent terraces indicates that gold grains in the drainage channels are possibly of colloidal origin and not mechanically transported to their present domain.The morphology of gold grains from the Ampalit drainage is compared with grains from adjacent terraces, using scanning electron microscopy and atomic force microscopy. The latter procedure allows for nondestructive analysis to give true three dimensional surface topography down to nanometre resolution. Evidence from force microscopy supports a colloidal origin for gold aggregates.The average purity of gold produced from the Ampalit dredging operation is 970 fine (970/1000) and the majority of examined gold grains extracted from beneath the drainage channel have a purity of 998 fine. This unusually high degree of purity suggests a selective dissolution/aggregation mechanism. We propose that gold is transported downward and laterally in groundwater percolating through the terrace sands and gravels to the current drainage as a humic acid-stabilised colloid. As the pregnant groundwater migrates toward the present drainage channels, it encounters a sleep chemical gradient and the colloid aggregates. The aggregation process occurs near clay zones within palaeochannel sands and gravels beneath the present river sediments. Here the colloidal aggregates form small grains (usually <1 mm) of extremely high purity.Today, the inherently unstable gold deposits at Ampalit are in a state of both aggregation and dissolution. Identification of low energy zones, location of point bar lags in palaeo and recent drainage channels, and the extrapolation of areas of low energy are not solely valid as exploration guides for gold accumulation in this environment. Exploration methods that also recognise ground water migration and composition, and the geochemical controls of dissolution and aggregation, will improve the ability to identify ore accumulations, thus contributing to improved economics of mining these deposits.     

Determining Paleosol Topography Using Seismic Refraction

The seismic refraction reversed profiling technique has been used to investigate the topography of the last interglacial soil (paleosol S1) within the central Chinese Loess Plateau near Xifeng. The results suggest an essentially flat-lying soil at a depth which varies by only a few meters over an area of more than 10 km². In addition, the results indicate a high-velocity layer at 50-60 m depth which is thought to coincide with a layer of carbonate concretions at the base of paleosol S5. The results agree well with the local loess-paleosol stratigraphy for this area and indicate that the seismic refraction method is a rapid technique for investigating paleotopography.     

Precise/ Small Sample Size Determinations of Lithium Isotopic Compositions of Geological Reference Materials and Modern Seawater by MC-ICP-MS

The Li isotope ratios of four international rock reference materials, USGS BHVO-2, GSJ JB-2, JG-2, JA-1 and modern seawater (Mediterranean, Pacific and North Atlantic) were determined using multi-collector inductively coupled plasma-mass spectrometry (MC-ICP-MS). These reference materials of natural samples were chosen to span a considerable range in Li isotope ratios and cover several different matrices in order to provide a useful benchmark for future studies. Our new analytical technique achieves significantly higher precision and reproducibility (< ± O.3%o 2s) than previous methods, with the additional advantage of requiring very low sample masses of ca . 2 ng of Li.     

Adsorption kinetics of CO2, CH4, and their equimolar mixture on coal from the Black Warrior Basin,West-Central Alabama

Laboratory experiments were conducted to investigate the adsorption kinetic behavior of pure and mixed gases (CO_2, CH₄, approximately equimolar CO₂ + CH₄ mixtures, and He) on a coal sample obtained from the Black Warrior Basin at the Littleton Mine (Twin Pine Coal Company), Jefferson County, west-central Alabama. The sample was from the Mary Lee coal zone of the Pottsville Formation (Lower Pennsylvanian). Experiments with three size fractions (45–150 µm, 1–2 mm, and 5–10 mm) of crushed coal were performed at 40 °C and 35 °C over a pressure range of 1.4–6.9 MPa to simulate coalbed methane reservoir conditions in the Black Warrior Basin and provide data relevant for enhanced coalbed methane recovery operations. The following key observations were made: (1) CO₂ adsorption on both dry and water-saturated coal is much more rapid than CH₄ adsorption; (2) water saturation decreases the rates of CO₂ and CH₄ adsorption on coal surfaces, but it appears to have minimal effects on the final magnitude of CO₂ or CH₄ adsorption if the coal is not previously exposed to CO₂; (3) retention of adsorbed CO₂ on coal surfaces is significant even with extreme pressure cycling; and (4) adsorption is significantly faster for the 45–150 μm size fraction compared to the two coarser fractions.     

Distribution and mode of occurrence of zinc and lead in glacial soils

The distribution and mode of occurrence of zinc and lead have been examined in glacial soils developed over a complex Precambrian marble-paragneiss terrain in the Adirondack Mountains of New York. Based on distribution within the soil profiles, zinc is enriched in the B₁ horizon of soils sampled over marble and lead is generally enriched in the A horizon, particularly in soils developed over paragneiss. Contrast is calculated using

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, where is the mean of n_A anomalous and n_B background samples, and S_p is the pooled standard deviation) for zinc, lead and cold-extractable heavy metals in soils sampled over marble and paragneiss. The t-values indicate that the B₁, soil horizon is the most suitable for sampling on a regular basis, even though lead is most concentrated in the A horizon.The distribution of zinc and lead among exchangeable, organic, iron-manganese oxide, clay, silt and sand fractions of B₁ horizons from two anomalous and one background soil indicates that both zinc and lead are tied up principally in iron and manganese oxides. The anomalous samples exhibit zinc enrichment in the Fe-oxide digestion and high Mn/Fe ratios for the Mn-oxide digestion (as well as the total analysis). In terms of total contribution to the sample, significant proportions of zinc in the clastic fraction can be attributed to zinc substitution into clays plus the ineffective removal of Fe-oxides by the ammonium oxalate extraction procedure. Lead, on the other hand, occurs in significant concentrations in clay, silt and sand as well as Fe- and Mn-oxides, probably as a trace constituent in feldspars or adsorbed onto clay surfaces.