Cation sorption on the muscovite (0 0 1) surface in chloride solutions using high-resolution X-ray reflectivity

The structure and mechanism of cation sorption at the (0 0 1) muscovite-water interface were investigated in 0.01 and 0.5 m KCl, CsCl, and CaCl₂ and 0.01 m BaCl₂ solutions at slightly acidic pH by high-resolution X-ray reflectivity. Structural relaxations of atom positions in the 2M₁ muscovite were small (?0.07 Å) and occurred over a distance of 30 to 40 Å perpendicular to the interface. Cations in all solutions were sorbed dominantly in the first and second solution layers adjacent to the mineral surface. The derived heights of the first solution layer in KCl and CsCl solutions, 1.67(6)-1.77(7) and 2.15(9)-2.16(2) Å, respectively, differ in magnitude by the approximate difference in crystallographic radii between K and Cs, and correspond closely to the interlayer cation positions in bulk K- and Cs-mica structures. The first solution layer heights in CaCl₂ and BaCl₂ solutions, 2.46(5)-2.56(11) and 2.02(5) Å, respectively, differ in a sense opposite to that expected based on crystallographic or hydrated radii of the divalent cations. The derived ion heights in all solutions imply that there is no intercalated water layer between the first solution layer and the muscovite surface. Molecular compositions were assigned to the first two solution layers in the electron density profiles using models that constrain the number density of sorbed cations, water molecules, and anions by considering the permanent negative charge of the muscovite and average solution density. The models result in partial charge balance (at least 50%) by cations sorbed in the first two layers in the 0.01 m solutions and approximately full charge balance in the 0.5 m solutions. Damped oscillations of model water density away from the first two solution layers agree with previous X-ray reflectivity results on the muscovite (0 0 1) surface in pure water.     

Do medical marijuana centers behave like locally undesirable land uses? Implications for the geography of health and environmental justice

As of 2013, medical marijuana is legal in 20 US States and the District of Columbia, but few studies have investigated the impact of the retail centers that sell the drug. We draw upon the social construction literature to frame our research and help us determine whether medical marijuana centers in Denver, Colorado, are considered locally undesirable land uses (LULUs). The geography of health and environmental justice frameworks lead us to hypothesize that marijuana centers are more likely to be opened in Hispanic, Black, and poor neighborhoods than in non-Hispanic White and affluent neighborhoods. We also hypothesize that marijuana centers will tend to increase the minority composition and poverty of the neighborhoods in which they are located. Contrary to expectations, we find no empirical support for these two hypotheses. Instead, results suggest that marijuana centers are likely to be situated in neighborhoods with higher crime rates and more retail employment. Thus, despite the view by many planners and law enforcement officials that these centers are problematic, they do not take on LULU characteristics in siting and demographic changes. This finding, while limited to Denver, has important implications for policymakers who are considering similar marijuana policies.     

The Burrum River estuary: identifying reference sites for Australian sub-tropical estuarine systems using paleolimnological methods

There is a pressing need to obtain historical information on estuaries so that levels of natural variability and ecosystem thresholds can be identified. Once these factors are known, estuaries that exhibit high conservation value and minimal impact from anthropogenic activity can be acknowledged and protected. In order to understand and quantify the level of change that may have occurred due to human impact, near pristine estuaries that have the potential to act as reference sites need to be identified. However, this is often difficult due to a lack of documented knowledge of estuary variability. This paper retrospectively assesses environmental conditions in the Burrum River, a sub-tropical east Australian estuary on the coast of Queensland, using diatom and stable isotope analyses. These techniques were combined with AMS ¹⁴C dating methods to determine if this system has undergone any natural or anthropogenically induced change. Diatom assemblages have shown very little variation over the past 5,000 years, indicating minimal changes to water quality. Upper and lower limits for δ¹³C and δ¹⁵N stable isotope results also infer that the sources of carbon and nitrogen to the Burrum River estuary have remained constant over this time period. Carbon inputs have been dominated by marine autotrophic production, whilst nitrogen inputs are indicative of terrestrial sources. Hence, the Burrum River has not been altered by anthropogenic activities and is a suitable reference site for benchmarking impacted sub-tropical estuaries. This paper demonstrates that paleolimnological techniques can be applied successfully to identify estuaries that are suitable as reference sites.     

Water quality changes in Lake McKenzie,Fraser Island,Australia: a Palaeolimnological approach

Surface water resources are highly valued for their ecological services and functions. However, their quality is under threat from anthropogenic activities and climate change. A detailed understanding of natural aquatic conditions and variability is rare. This is particularly the case in Australia where the variable climate produces significant ecological changes within natural thresholds and few long-term environmental data sets exist. Palaeoecology represents a means to identify natural fluctuations of aquatic ecosystems and provide long-term data for effective environmental management. This study uses a palaeoecological approach to identify biological and sediment changes in Lake McKenzie, Fraser Island, Australia. A sediment core was extracted from the lake and the fossil diatom assemblage and sediment particle size analysed. Inferred environmental changes were detected throughout the core that pre-date European impacts. The likely causes of these changes are climatic oscillations. Further dating is required to establish a detailed chronological record and identify the timing of detected environmental change at Lake McKenzie.     

A late Pleistocene record of aeolian sedimentation in Blanche Cave, Naracoorte, South Australia

We provide geochemical analyses and grain size data for a clearly layered, 80 cm thick sedimentary deposit close to a roof collapse in Blanche Cave near Naracoorte in SE South Australia. This deposit contains aeolian material deposited between 40 ka and 14 ka cal BP and which yields airborne sediments spanning the Last Glacial Maximum, a period of time with little information for the Australian continent. The deposit also contains abundant vertebrate fossil material derived from owl pellets, accumulation and pitfall entrapment. Below the studied profile, large vertebrate remains are found but are not discussed here. No Holocene sedimentation occurred at the site examined in the cave, and the top of the sequence is capped with a layer that has been anthropologically disturbed and contains exotic Pinus pollen. Chronologies of the deposit were obtained using two dating techniques: single stage accelerator mass spectrometer (SSAMS) ¹⁴C analysis of 23 charcoal samples and optically stimulated luminescence (OSL) dating of quartz from 6 sediment samples. The ¹⁴C chronology is preferred to describe the history of the deposits since the OSL chronology, which consistently overestimates the associated radiocarbon dates, may be inaccurate due to complexities in calculating dose rates, and may in addition represent the timing of sediment deposition through the cave opening rather than sediment transport to the deposit site. Morphological analysis of single quartz grains and grain size analysis indicate different provenance that is confirmed through the geochemical analyses of bulk sediment. Major elements were measured by X-ray Fluorescence (XRF), trace and rare earth elements by Laser Ablation Inductively Coupled Plasma Mass Spectrometry (LA ICP-MS), and Neodymium isotopic ratios were obtained using a Thermal Ionisation Mass Spectrometer (TIMS).Our results indicate that the aeolian material deposited in Blanche Cave over the 40–14 ka cal BP period originated from different sources across South Australia, although Nd isotopes clearly indicate a close association with sediments of the Kanmantoo Group outcropping along the eastern portion of the Mount Lofty Ranges and the Padthaway Ridge further south, both being located to the NW and NNW of the cave. During the latter part of Marine Isotope Stage 3, conditions were wetter and windblown sediment came from the coastal region just north and south of the Coorong Lagoon, with winds originating from the north-northwest. At that time, woody taxa appear to have vegetated the landscape. During the drier phases, especially the Last Glacial Maximum, sediment came from further inland, thus suggesting a different predominant wind direction, more from the northwest. The deglaciation saw material originating from a more northerly direction.     

Urbanization and Rainfall–Runoff Relationships in the Milwaukee River Basin

To understand the changing rainfall–runoff relationship, this study examined climate and streamflow data in the Milwaukee River Basin in southeastern Wisconsin, of which four catchments with different degrees of urbanization were selected for analysis. This study analyzed temperature, precipitation, and streamflow data with a range of statistical methods, including the Mann–Kendall test, double-mass technique, and quantile regression. Runoff ratios and extreme flow indexes were higher in more urbanized catchments. Catchments with long-term data (>forty years) showed significantly increasing runoff ratios and slopes in double-mass curves. Overall, there are signs of changes in the rainfall–runoff relationship, but how much they can be attributed to land use changes is uncertain.     

Comparison of CO2 Dynamics and Air–Sea Gas Exchange in Differing Tropical Reef Environments

An array of MAPCO₂ buoys, CRIMP-2, Ala Wai, and Kilo Nalu, deployed in the coastal waters of Hawaii, have produced multi-year high temporal resolution CO₂ records in three different coral reef environments off the island of Oahu, Hawaii. This study, which includes data from June 2008 to December 2011, is part of an integrated effort to understand the factors that influence the dynamics of CO₂–carbonic acid system parameters in waters surrounding Pacific high-island coral reef ecosystems and subject to differing natural and anthropogenic stresses. The MAPCO₂ buoys are located on the Kaneohe Bay backreef, and fringing reef sites on the south shore of Oahu, Hawaii. The buoys measure CO₂ and O₂ in seawater and in the atmosphere at 3-h intervals, as well as other physical and biogeochemical parameters (conductivity, temperature, depth, chlorophyll-a, and turbidity). The buoy records, combined with data from synoptic spatial sampling, have allowed us to examine the interplay between biological cycles of productivity/respiration and calcification/dissolution and biogeochemical and physical forcings on hourly to inter-annual time scales. Air–sea CO₂ gas exchange was also calculated to determine whether the locations were sources or sinks of CO₂ over seasonal, annual, and interannual time periods. Net annualized fluxes for CRIMP-2, Ala Wai, and Kilo Nalu over the entire study period were 1.15, 0.045, and ?0.0056 mol C m^?2 year^?1, respectively, where positive values indicate a source or a CO₂ flux from the water to the atmosphere, and negative values indicate a sink or flux of CO₂ from the atmosphere into the water. These values are of similar magnitude to previous estimates in Kaneohe Bay as well as those reported from other tropical reef environments. Total alkalinity (A_T) was measured in conjunction with pCO₂, and the carbonic acid system was calculated to compare with other reef systems and open ocean values around Hawaii. These findings emphasize the need for high-resolution data of multiple parameters when attempting to characterize the carbonic acid system in locations of highly variable physical, chemical, and biological parameters (e.g., coastal systems and reefs).