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Creators/Authors contains: "Richard, A"

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  1. Free, publicly-accessible full text available October 14, 2026
  2. This dataset provides comprehensive measurements of nutrient concentrations and fluxes in foliage, fine roots, wood, litterfall, and throughfall in hardwood and conifer stands across temperate forest stands at three long-term ecological research sites in the northeastern United States: Cone Pond, NH, Hubbard Brook, NH, and Sleepers River, VT. These sites vary in bedrock composition, parent material, and soil chemistry, but share similar climatic characteristics. Tissue nutrient concentrations were determined in leaves, fine roots, wood, and branches using site- and tissue-specific methods, with additional quality control through certified standards and duplicate sampling. Nutrient fluxes via litterfall and throughfall were measured over multiple years. Nutrient fluxes in roots were estimated from minirhizotron-based turnover rates and fine root biomass. Annual nutrient accumulation and uptake were calculated by integrating biomass production and nutrient concentrations. This dataset supports cross-site comparisons of forest biogeochemistry and provides a basis for evaluating nutrient limitations, cycling processes, and ecosystem responses to environmental gradients in northeastern temperate forests. 
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  3. In the northeastern United States, both hardwood and conifer forests have developed on sites with contrasting soils, allowing an examination of the effect of site and forest type on ecosystem nutrient cycling. We measured biomass production and nutrient fluxes in northern hardwood and conifer stands at three sites differing in soil fertility. We found that leaf, root, and wood concentrations of calcium (Ca), magnesium (Mg), and potassium reflected differences in soil base cation availability, while concentrations of nitrogen (N) and phosphorus (P) were more consistent across sites. Nutrient uptake was calculated as the sum of litterfall, net throughfall (throughfall minus precipitation), root turnover, and accumulation in perennial tissues (wood). We propose a novel metric of nutrient cycling, the nutrient retention fraction (NRF), defined as the proportion of annual nutrient uptake retained in biomass accretion. Because the NRF is unitless, it can be compared across nutrients; Ca and Mg had the highest NRF and P the lowest ( p = 0.05). Across sites and elements, NRFs were lower for conifers (5.0 ± 0.6%) than for hardwoods (7.2 ± 0.5%), associated with their lower productivity. Nutrient-use efficiency (biomass production divided by nutrient uptake) tended to be high where foliar concentrations indicated low availability of that nutrient. Nutrient retention of N and P was higher where availability of the other element was high, which could be a mechanism contributing to N and P co-limitation. 
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    Free, publicly-accessible full text available January 12, 2027
  4. This article considers the problem of modeling a class of nonstationary time series using piecewise autoregressive (AR) processes in the presence of outliers. The number and locations of the piecewise AR segments, as well as the orders of the respective AR processes, are assumed to be unknown. In addition, each piece may contain an unknown number of innovational and/or additive outliers. The minimum description length (MDL) principle is applied to compare various segmented AR fits to the data. The goal is to find the “best” combination of the number of segments, the lengths of the segments, the orders of the piecewise AR processes, and the number and type of outliers. Such a “best” combination is implicitly defined as the optimizer of an MDL criterion. Since the optimization is carried over a large number of configurations of segments and positions of outliers, a genetic algorithm is used to find optimal or near‐optimal solutions. Numerical results from simulation experiments and real data analyses show that the procedure enjoys excellent empirical properties. 
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    Free, publicly-accessible full text available July 24, 2026
  5. Free, publicly-accessible full text available June 30, 2026
  6. Prior studies of halobenzene−ammonia complexes have shown that the nature of the cationic intermediate (i.e., Wheland-type vs ion-radical) may play a key role in determining the reaction products. To probe this link, we report here the reaction dynamics of the chlorobenzene-ammonia 1:1 complex (PhCl···NH3) using product ion imaging following two-color resonant two-photon ionization. A threshold value of 8.863 ± 0.008 eV was determined for the appearance of protonated aniline, which accompanies Cl atom loss and is the dominant product channel at energies near threshold. Scanning down to energies close to threshold, we find no evidence for a roaming halogen radical mechanism leading to HCl products, which was evidenced in the related bromobenzene−ammonia complex, and proceeded through an ion-radical intermediate structure. Here, supporting calculations indicate that both types of intermediates are present, but the Wheland-type structure is significantly more stable. Addressing a key question of earlier work, analysis of the PhCl···NH3 potential energy surface (PES) in the reactant region establishes a complicated entrance channel pathway linking the in-plane σ-type complex to the Wheland intermediate (iWH) on the [PhCl···NH3]+• cationic surface. This pathway involves stepwise transition of the weakly bound ammonia from the initial in-plane σ-type complex to an ortho Wheland intermediate, followed by rearrangement to the ipso position. Finally, given that fluorine has been shown to stabilize aromatic ions, we hypothesized that fluorine substitution might alter the structure of the intermediate, favoring the ion-radical intermediate. To test this hypothesis, as an illustrative example the PES of the meta-PhClF-NH3 system on the cationic surface was computed. Confirming our hypothesis, these calculations show an inversion in stability for the Wheland-type and ion−radical complex intermediates, with the latter preferred energetically at the examined level of theory. 
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    Free, publicly-accessible full text available September 4, 2026
  7. This paper introduces new algorithms for conducting and improving watershed analysis, implemented with the particular goal of improving the ability to measure the shapes of mineral grains to be subsequently be analyzed by mass spectrometry. This application requires a high degree of accuracy and fidelity in terms of both separating all touching grains and preserving their shapes. The algorithms are designed to take advantage of a vector-based programming environment. A new implementation of the Euclidean distance transform utilizes the fact that the distance from any adjacent pair of voxels to the nearest boundary must be within one voxel of each other. In practice, however, this algorithm is outperformed by a smoothed approximate distance transform that is faster to compute and results in less irregular watershed boundaries. A one-pass rainfall-based watershed algorithm is introduced that runs in linear time with the number of segmented voxels, and requires no priority queue. Unlike marker-based watershed algorithms based on the basin-filling approach, the rainfall approach finds watersheds associated with all local maxima in the distance map, even if a marking algorithm is used. A post-watershed smoothing algorithm improves watershed boundaries and eliminates small spurious watersheds. The one-pass watershed and post-watershed smoothing algorithms run in times superior or comparable to basin-fill watershed algorithms implemented in other environments, and offers excellent ability to separate touching objects efficiently while placing watershed boundaries that maximize the preservation of details of particle shape. Further time improvement could come from implementing them in a vector-based environment that allows explicit multi-threading. 
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    Free, publicly-accessible full text available March 1, 2026
  8. Abstract Most work on how estuarine dynamics impact dissolved oxygen (DO) distributions has focused on tides, but in shallow estuaries with large fetch or small tides, wind can be the primary mixing agent and also drives advection. To investigate how these processes affect DO distributions, an observational study was conducted in the shallow, microtidal Neuse Estuary. Salinity, DO, and velocity profiles were measured at multiple positions along and across the estuary over a 6‐month period. A one‐dimensional model (General Ocean Turbulence Model) provided additional insight into the response of salinity and DO to wind. Salinity and oxygen conservation equation terms were calculated from observations and simulations. Cross‐estuary wind drove lateral circulation and tilted the isohalines, reducing stratification; lateral advection and enhanced mixing reduced vertical gradients and increased the bottom DO. Down‐estuary wind tended to increase the exchange flow and stratification, but concurrently the surface wind‐mixed layer deepened over time. The balance of these processes determined if the water column became fully mixed or remained stratified, and the depth of the pycnocline and oxycline. An expression for steady state surface layer thickness was derived by considering the competition between the horizontal and vertical buoyancy flux, and the predictions agreed well with observations and simulations. Up‐estuary wind inhibited the exchange flow and the combination of advection and mixing homogenized the water column. While these patterns generally held for purely across‐ or along‐channel wind, the response was often more complex as the wind vector varied in orientation and with time. 
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    Free, publicly-accessible full text available June 1, 2026
  9. Metallosphaera sedulais a thermoacidophilic archaeon that obtains all of its energy for growth from aerobic respiration and oxidative phosphorylation at the expense of selected organic and inorganic sources of electrons. Initial velocities for the oxidation of soluble ferrous ions by intact cells at 60 °C and pH 1.5 were determined using an integrating cavity absorption meter that permitted accurate absorbance measurements to quantify the increase in soluble ferric iron in the presence of turbid suspensions of the live organisms.M. sedulathat was cultured on yeast extract either in the absence or the presence of 20 mM soluble ferrous iron exhibited turnover numbers for soluble iron oxidation of 304 ± 26 and 333 ± 31 attamoles/cell/min, respectively. These functional data were consistent with the transcriptomic evidence presented by others, that the proteins presumably responsible for aerobic respiration on soluble iron are expressed constitutively inM. sedula. Intact cells ofM. sedulawere characterized by electrical impedance, laser light diffraction, and transmission electron microscopic measurements. All three types of measurements were consistent with the surprising observation that cells cultured on yeast extract in the presence of soluble iron bifurcated into approximately equal numbers of coccoidal cells of two sizes, smaller cells with an average diameter of 0.6 μm and larger cells with an average diameter of 1.35 μm. Cells cultured on the same concentration of yeast extract but in the absence of soluble iron comprised a single cell size with an intermediate average diameter of 1.06 μm. This unexpected bifurcation of a clonal cell population into two demonstrably different sizes when the extracellular nutrient environment changes has not previously been reported forM. sedula, or any other single-celled archaeon or eubacterium. 
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    Free, publicly-accessible full text available May 9, 2026
  10. Free, publicly-accessible full text available May 1, 2026