Using the precision of the mean to estimate suitable sample sizes for monitoring total phosphorus in Australian catchments

The effect of the sample size on prediction quality is well understood. Recently, studies have assessed this relationship using near‐continuous water quality samples. However, this is rarely possible because of financial constraints, and therefore, many studies have relied on simulation‐based methods utilizing more affordable surrogates. A limitation of simulation‐based methods is the requirement of a good relationship, which is often not present. Therefore, catchment managers require a direct method to estimate the effect of sample size on the mean using historical water quality data. One measure of prediction quality is the precision with which a mean is estimated; this is the focus of this work. By characterizing the effect of sample size on the precision of the mean, it is possible for catchment managers to adjust the sample size in relation to both the cost and the precision. Historical data are often sparse and generally collected using several different sampling schemes, all without inclusion probabilities. This means that an approach is needed to obtain unbiased estimates of the variance of the mean using a model‐based approach. With the use of total phosphorus data from 17 sub‐catchments in southeastern Australia, the ability of a model‐based approach to estimate the effect of sample size on the precision of event and base‐flow mean concentrations. The results showed that for estimating annual base‐flow mean concentration, little gain in precision was achieved above 12 observations per year. Sample sizes greater than 12 samples per event improved event‐based estimates; however, the inclusion of more than 12 samples per event did not greatly reduce the event mean concentration uncertainties. The precision of the base‐flow estimates was most correlated to percentage urban cover, whereas the precision of the event mean estimates was most correlated with catchment size. The method proposed in this work could be readily applied to other water quality variables and other monitoring sites. Copyright © 2014 John Wiley & Sons, Ltd.     

Vadose CO2 gas drives dissolution at water tables in eogenetic karst aquifers more than mixing dissolution

Most models of cave formation in limestone that remains near its depositional environment and has not been deeply buried (i.e. eogenetic limestone) invoke dissolution from mixing of waters that have different ionic strengths or have equilibrated with calcite at different _pCO₂ values. In eogenetic karst aquifers lacking saline water, mixing of vadose and phreatic waters is thought to form caves. We show here calcite dissolution in a cave in eogenetic limestone occurred due to increases in vadose CO₂ gas concentrations and subsequent dissolution of CO₂ into groundwater, not by mixing dissolution. We collected high‐resolution time series measurements (1 year) of specific conductivity (SpC), temperature, meteorological data, and synoptic water chemical composition from a water table cave in central Florida (Briar Cave). We found SpC, _pCO₂ and calcite undersaturation increased through late summer, when Briar Cave experienced little ventilation by outside air, and decreased through winter, when increased ventilation lowered cave CO_2(g) concentrations. We hypothesize dissolution occurred when water flowed from aquifer regions with low _pCO₂ into the cave, which had elevated _pCO₂. Elevated _pCO₂ would be promoted by fractures connecting the soil to the water table. Simple geochemical models demonstrate that changes in _pCO₂ of less than 1% along flow paths are an order of magnitude more efficient at dissolving limestone than mixing of vadose and phreatic water. We conclude that spatially or temporally variable vadose CO_2(g) concentrations are responsible for cave formation because mixing is too slow to generate observed cave sizes in the time available for formation. While this study emphasized dissolution, gas exchange between the atmosphere and karst aquifer vadose zones that is facilitated by conduits likely exerts important controls on other geochemical processes in limestone critical zones by transporting oxygen deep into vadose zones, creating redox boundaries that would not exist in the absence of caves. Copyright © 2014 John Wiley & Sons, Ltd.     

Radiocarbon dating of small terrestrial gastropod shells in North America

Fossil shells of small terrestrial gastropods are commonly preserved in wetland, alluvial, loess, and glacial deposits, as well as in sediments at many archeological sites. These shells are composed largely of aragonite (CaCO₃) and potentially could be used for radiocarbon dating, but they must meet two criteria before their ¹⁴C ages can be considered to be reliable: (1) when gastropods are alive, the ¹⁴C activity of their shells must be in equilibrium with the ¹⁴C activity of the atmosphere, and (2) after burial, their shells must behave as closed systems with respect to carbon. To evaluate the first criterion, we conducted a comprehensive examination of the ¹⁴C content of the most common small terrestrial gastropods in North America, including 247 AMS measurements of modern shell material (3749 individual shells) from 46 different species. The modern gastropods that we analyzed were all collected from habitats on carbonate terrain and, therefore, the data presented here represent worst-case scenarios. In sum, ～78% of the shell aliquots that we analyzed did not contain dead carbon from limestone or other carbonate rocks even though it was readily available at all sites, 12% of the aliquots contained between 5 and 10% dead carbon, and a few (3% of the total) contained more than 10%. These results are significantly lower than the 20–30% dead carbon that has been reported previously for larger taxa living in carbonate terrain. For the second criterion, we report a case study from the American Midwest in which we analyzed fossil shells of small terrestrial gastropods (7 taxa; 18 AMS measurements; 173 individual shells) recovered from late-Pleistocene sediments. The fossil shells yielded ¹⁴C ages that were statistically indistinguishable from ¹⁴C ages of well-preserved plant macrofossils from the same stratum. Although just one site, these results suggest that small terrestrial gastropod shells may behave as closed systems with respect to carbon over geologic timescales. More work on this subject is needed, but if our case study site is representative of other sites, then fossil shells of some small terrestrial gastropods, including at least five common genera, Catinella, Columella, Discus, Gastrocopta, and Succinea, should yield reliable ¹⁴C ages, regardless of the local geologic substrate.     

Health, sexuality and place: the different geographies of HIV-positive gay men in Auckland, New Zealand

This paper employs interview narratives alongside participant-led photography and caption writing to examine the different daily geographies of 15 HIV-positive gay men in Auckland, New Zealand. Difference for these men is rooted in both their HIV status and their sexuality, and this difference has implications for their engagement with the world at a range of spatial and temporal scales. Giving voice to such experiences begins to answer calls for geographers to consider more deeply the connections between health, sexuality and place.     

Isotope measurements of single ostracod valves and gastropod shells for climate reconstruction: evaluation of within-sample variability and determination of optimum sample size

Sediment cores from Lakes Punta Laguna, Chichancanab, and Petén Itzá on the Yucatan Peninsula were used to (1) investigate “within-horizon” stable isotope variability (δ¹⁸O and δ¹³C) measured on multiple, single ostracod valves and gastropod shells, (2) determine the optimum number of individuals required to infer low-frequency climate changes, and (3) evaluate the potential for using intra-sample δ¹⁸O variability in ostracod and gastropod shells as a proxy measure for high-frequency climate variability. Calculated optimum sample numbers (“n”) for δ¹⁸O and δ¹³C in the ostracod Cytheridella ilosvayi and the gastropod Pyrgophorus coronatus vary appreciably throughout the cores in all three lakes. Variability and optimum “n” values were, in most cases, larger for C. ilosvayi than for P. coronatus for δ¹⁸O measurements, whereas there was no significant difference for δ¹³C measurements. This finding may be explained by differences in the ecology and life history of the two taxa as well as contrasting modes of calcification. Individual δ¹⁸O measurements on C. ilosvayi in sediments from Lake Punta Laguna show that samples from core depths that have high mean δ¹⁸O values, indicative of low effective moisture, display lower variability, whereas samples with low mean δ¹⁸O values, reflecting times of higher effective moisture, display higher variability. Relatively dry periods were thus consistently dry, whereas relatively wet periods had both wet and dry years. This interpretation of data from the cores applies to two important periods of the late Holocene, the Maya Terminal Classic period and the Little Ice Age. δ¹⁸O variability during the ancient Maya Terminal Classic Period (ca. 910–990 AD) indicates not only the driest mean conditions in the last 3,000 years, but consistently dry climate. Variability of δ¹³C measurements in single stratigraphic layers displayed no relationship with climate conditions inferred from δ¹⁸O measurements.     

A ∼33,000 year record of environmental change from Arolik Lake, Ahklun Mountains, Alaska, USA

A continuous record of lacustrine sedimentation capturing the entire full-glacial period was obtained from Arolik Lake in the Ahklun Mountains, southwestern Alaska. Fluctuations in magnetic susceptibility (MS), grain size, organic-matter (OM) content, C/N ratios, ¹³C, and biogenic silica (BSi) record marked environmental changes within the lake and its watershed during the last 33 cal ka. Age control is provided by 31 ¹⁴C ages on plant macrofossils in four cores between 5.2 and 8.6 m long. Major stratigraphic units are traceable throughout the lake subbottom in acoustical profiles, and provisional ages are derived for six prominent tephra beds, which are correlated among the cores. During the interstadial interval between 33 and 30 cal ka, OM and BSi contents are relatively high with values similar to those of the Pleistocene–Holocene transition, suggesting a similar level of aquatic productivity. During the glacial interval that followed (30–15 cal ka), OM and BSi decrease in parallel with declining summer insolation. OM and BSi values remain relatively uniform compared with the higher variability before and after this interval, and they show no major shifts that might correlate with climate fluctuations evidenced by the local moraine record, nor with other global climate changes. The glacial interval includes a clay-rich unit with a depauperate diatom assemblage that records the meltwater spillover of an ice-dammed lake. The meltwater pulse, and therefore the maximum extent of ice attained by a major outlet glacier of the Ahklun Mountain ice cap, lasted from 24 to 22 cal ka. The Pleistocene–Holocene transition (15–11 cal ka) exhibits the most prominent shifts in OM and BSi, but rapid and dramatic fluctuations in OM and BSi continue throughout the Holocene, indicating pronounced paleoenvrionmental changes.     

Standard and Non-Standard Solar Models

We summarize the physical input and assumptions commonly adopted in modern standard solar models that also produce good agreement with solar oscillation frequencies. We discuss two motivations for considering non-standard models: the solar neutrino problem and surface lithium abundance problem. We begin to explore the potential for mixed core models to solve the neutrino problem, and compare the structure, neutrino flux, and oscillation frequency predictions for several models in which the inner 25% of the radius is homogenized, taking into account the effects of non-local equilibrium abundances of ³He. The results for the neutrino flux and helioseismic predictions are far from satisfactory, but such models have the potential to reduce the predicted ⁷Be/⁸B neutrino flux ratio, and further studies are warranted. Finally, we discuss how much the neutrino problem can be alleviated in the framework of the standard solar model by using reaction rates, abundances and neutrino capture cross-sections at the limits of their uncertainties, while still satisfying the constraints of helioseismology.     

Ultraviolet irradiation of naphthalene in H2O ice: Implications for meteorites and biogenesis

Abstract— The polycyclic aromatic hydrocarbon (PAH) naphthalene was exposed to ultraviolet radiation in H₂O ice under astrophysical conditions, and the products were analyzed using infrared spectroscopy and high‐performance liquid chromatography. As we found in our earlier studies on the photoprocessing of coronene in H₂O ice, aromatic alcohols and ketones (quinones) were formed. The regiochemistry of the reactions is described and leads to specific predictions of the relative abundances of various oxidized naphthalenes that should exist in meteorites if interstellar ice photochemistry influenced their aromatic inventory. Since oxidized PAHs are present in carbon‐rich meteorites and interplanetary dust particles (IDPs), and ubiquitous in and fundamental to biochemistry, the delivery of such extraterrestrial molecules to the early Earth may have played a role in the origin and evolution of life.     

A Simplified Kinetic Element Formulation for the Rotation of a Perturbed Mass-Asymmetric Rigid Body

Euler's equations, describing the rotation of an arbitrarily torqued mass asymmetric rigid body, are scaled using linear transformations that lead to a simplified set of first order ordinary differential equations without the explicit appearance of the principal moments of inertia. These scaled differential equations provide trivial access to an analytical solution and two constants of integration for the case of torque-free motion. Two additional representations for the third constant of integration are chosen to complete two new kinetic element sets that describe an osculating solution using the variation of parameters. The elements' physical representations are amplitudes and either angular displacement or initial time constant in the torque-free solution. These new kinetic elements lead to a considerably simplified variation of parameters solution to Euler's equations. The resulting variational equations are quite compact. To investigate error propagation behaviour of these new variational formulations in computer simulations, they are compared to the unmodified equations without kinematic coupling but under the influence of simulated gravity-gradient torques.     

Protostellar evolution during time-dependent anisotropic collapse

The formation and collapse of a protostar involves the simultaneous infall and outflow of material in the presence of magnetic fields, self-gravity and rotation. We use self-similar techniques to self-consistently model the anisotropic collapse and outflow by using a set of angle-separated self-similar equations. The outflow is quite strong in our model, with the velocity increasing in proportion to radius, and material formally escaping to infinity in the finite time is required for the central singularity to develop.
Analytically tractable collapse models have been limited mainly to spherically symmetric collapse, with neither magnetic field nor rotation. Other analyses usually employ extensive numerical simulations, or either perturbative or quasistatic techniques. Our model is unique as an exact solution to the non-stationary equations of self-gravitating magnetohydrodynamics (MHD), which features co-existing regions of infall and outflow.
The velocity and magnetic topology of our model is quadrupolar, although dipolar solutions may also exist. We provide a qualitative model for the origin and subsequent evolution of such a state. However, a central singularity forms at late times, and we expect the late-time behaviour to be dominated by the singularity, rather than depend on the details of its initial state. Our solution may, therefore, have the character of an attractor among a much more general class of self-similarity.