Molecular characterization of dissolved organic matter (DOM) along a river to ocean transect of the lower Chesapeake Bay by ultrahigh resolution electrospray ionization Fourier transform ion cyclotron resonance mass spectrometry

In this study, electrospray ionization coupled to Fourier transform ion cyclotron resonance mass spectrometry (ESI-FTICR-MS) is utilized to molecularly characterize DOM as it is transported along a river to estuary to ocean transect of the lower Chesapeake Bay system. The ultrahigh resolving power (greater than 500,000) and mass accuracy of FTICR-MS allow for the resolution of the thousands of components in a single DOM sample, and can therefore elucidate the molecular-level changes that occur during DOM transformation from a terrestrial location to the marine environment. An important feature of FTICR-MS is that its sensitivity allows for direct analysis of low salinity samples without employing the traditional concentration approaches involving C₁₈ extraction or ultrafiltration. To evaluate the advantages of using direct analysis, a C₁₈ extract of riverine water is compared to its whole, unfractionated water, and it was determined that the C₁₈ extraction is selective in that it eliminates two major series of compounds. One group is aliphatic amines/amides that are not adsorbed to the C₁₈ disk because they exist as positive ions prior to extraction. The second group is tannin-like compounds with higher oxygen contents and a more polar quality that also allow them not to be adsorbed to the C₁₈ disk. This direct approach could not be used for brackish/saline waters, so the C₁₈ method is resorted to for those samples. Along the subject transect, a significant difference is observed in the molecular composition of DOM, as determined from assigned molecular formulas. The DOM tends to become more aliphatic and contain lower abundances of oxygen-rich molecules as one progresses from inshore to the offshore. A considerable amount of molecular formula overlap does exist between samples from sites along the transect. This can be explained as either the presence of refractory material that persists throughout the transect, due to its resistance to degradation, or that the assigned molecular formulas are the same but the chemical structures are different. ESI-FTICR-MS is a powerful technique for the investigation of DOM and has the ability to detect compositional variations along the river to ocean transect. Visualization tools such as two dimensional and three dimensional van Krevelen diagrams greatly assist in highlighting the shift from the more aromatic, terrestrial DOM to the more aliphatic, marine DOM.     

Uneven urban metabolisms: toward an integrative (ex)urban political ecology of sustainability in and around the city

ABSTRACT

Expanding cities present a sustainability challenge, as the uneven proliferation of hybrid landscape types becomes a major feature of 21st century urbanization. To fully address this challenge, scholars must consider the broad range of land uses that being produced beyond the urban core and how land use patterns in one location may be tied to patterns in other locations. Diverse threads within political ecology provide useful insights into the dynamics that produce uneven urbanization. Specifically, urban political ecology (UPE) details how economic power influences the development decision-making that proliferate urban forms, patterns of uneven access, and modes of decision-making, frequently viewing resource extraction and development through the urban metabolism lens. The political ecology of exurbia, or, perhaps, an exurban political ecology (ExPE), examines the symbolic role nature and the rural have played in conservation and development efforts that produce social, economic, and environmental conflicts. While UPE approaches tend to privilege macroscale dynamics, ExPE emphasizes the role of landowners, managers, and other actors in struggles over the production of exurban space, including through decision-making institutions and within the context of broader political economic forces. Three case studies illustrate the strengths and weaknesses of these approaches, demonstrating the benefits for and giving suggestions on how to integrate their insights into urban sustainability research. Integrated political ecology approaches demonstrate how political-economic processes at a variety of scales produce diverse local sustainability responses.     

Assessment of chemical and physical treatments to selectively kill non-indigenous freshwater zooplankton species

Non-indigenous zooplankton species pose a biosecurity threat to New Zealand’s freshwater native taxa. Nine species are known to have established in New Zealand lakes to date. The spread of some zooplankton taxa is linked to the translocation of farmed fish, principally grass carp (Ctenopharyngodon idella), and recreational vessel movements. The aims of this study were to assess the effectiveness of a range of chemical and physical treatments for transport water and associated equipment to kill freshwater cladoceran, copepod, and rotifer zooplankton species, and their risk to non-target fish. Sodium chloride was the most effective and applicable chemical treatment tested at length in the cladoceran and, combined with physical treatment via mechanical filtration of water or hot water immersion of equipment (to also manage the risk of diapausing eggs), represents an effective option for the control of non-indigenous zooplankton, with limited impact on stenohaline fish.     

Structural evolution and the partitioning of deformation during basin growth and inversion: A case study from the Mizen Basin Celtic Sea,offshore Ireland

The Celtic Sea basins lie on the continental shelf between Ireland and northwest France and consist of a series of ENE–WSW trending elongate basins that extend from St George’s Channel Basin in the east to the Fastnet Basin in the west. The basins, which contain Triassic to Neogene stratigraphic sequences, evolved through a complex geological history that includes multiple Mesozoic rift stages and later Cenozoic inversion. The Mizen Basin represents the NW termination of the Celtic Sea basins and consists of two NE–SW-trending half-grabens developed as a result of the reactivation of Palaeozoic (Caledonian, Lower Carboniferous and Variscan) faults. The faults bounding the Mizen Basin were active as normal faults from Early Triassic to Late Cretaceous times. Most of the fault displacement took place during Berriasian to Hauterivian (Early Cretaceous) times, with a NW–SE direction of extension. A later phase of Aptian to Cenomanian (Early to Late Cretaceous) N–S-oriented extension gave rise to E–W-striking minor normal faults and reactivation of the pre-existing basin bounding faults that propagated upwards as left-stepping arrays of segmented normal faults. In common with most of the Celtic Sea basins, the Mizen Basin experienced a period of major erosion, attributed to tectonic uplift, during the Paleocene. Approximately N–S Alpine regional compression-causing basin inversion is dated as Middle Eocene to Miocene by a well-preserved syn-inversion stratigraphy. Reverse reactivation of the basin bounding faults was broadly synchronous with the formation of a set of near-orthogonal NW–SE dextral strike-slip faults so that compression was partitioned onto two fault sets, the geometrical configuration of which is partly inherited from Palaeozoic basement structure. The segmented character of the fault forming the southern boundary of the Mizen Basin was preserved during Alpine inversion so that Cenozoic reverse displacement distribution on syn-inversion horizons mirrors the earlier extensional displacements. Segmentation of normal faults therefore controls the geometry and location of inversion structures, including inversion anticlines and the back rotation of earlier relay ramps.     

Cumulative spatial impact layers: A novel multivariate spatio‐temporal analytical summarization tool

Scientific inquiry often requires analysis of multiple spatio‐temporal datasets, ranging in type and size, using complex multi‐step processes demanding an understanding of GIS theory and software. Cumulative spatial impact layers (CSIL) is a GIS‐based tool that summarizes spatio‐temporal datasets based on overlapping features and attributes. Leveraging a recursive quadtree method, and applying multiple additive frameworks, the CSIL tool allows users to analyze raster and vector datasets by calculating data, record, or attribute density. Providing an efficient and robust method for summarizing disparate, multi‐format, multi‐source geospatial data, CSIL addresses the need for a new integration approach and resulting geospatial product. The built‐in flexibility of the CSIL tool allows users to answer a range of spatially driven questions. Example applications are provided in this article to illustrate the versatility and variety of uses for this CSIL tool and method. Use cases include addressing regulatory decision‐making needs, economic modeling, and resource management. Performance reviews for each use case are also presented, demonstrating how CSIL provides a more efficient and robust approach to assess a range of multivariate spatial data for a variety of uses.     

The oxygen isotope compositions of olivine in main group (MG) pallasites: New measurements by adopting an improved laser fluorination approach

Oxygen isotope measurements of olivine in main group (MG) pallasites by traditional laser fluorination method are associated with some uncertainties including terrestrial weathering, incomplete olivine reaction, and sample state. We improved our laser fluorination approach by pretreating olivine grains with acid to remove terrestrial weathering products and by modifying the sample holder for an efficient and complete laser reaction. Our experiments on Brahin olivine demonstrate that acid-washing successfully removes the terrestrial weathering with <0.1‰ variation in δ¹⁸O value and, at the same time, improving the ∆¹⁷O value significantly. We also achieved a complete olivine fluorination by employing a custom-designed sample holder with “V”-shaped profile having rounded bottom because incomplete/partial reaction of olivine gives comparatively lighter δ¹⁸O values. Using these new techniques, we present precise triple oxygen isotope data (N = 72) of 25 olivine samples separated from main group pallasites. The data are, on average, ~0.5‰ heavier in δ¹⁸O relative to the values published in the literature for the same samples. Critically, the ∆¹⁷O values of MG pallasites and to some extent their Fo-contents suggest that there are at least two populations of olivine. Based on our improved data set, we propose that MG pallasites potentially have high-∆¹⁷O- and low-∆¹⁷O-bearing subgroups that are statistically distinct. The subgroups present average ∆¹⁷O values of −0.166 ± 0.003 (2SE; N = 16) and −0.220 ± 0.003 (2SE; N = 9), respectively. Furthermore, the high-∆¹⁷O-bearing subgroup samples trend toward lower Fo-contents compared to the other subgroup. Taken together, our data provide evidence that argues against a single parent body origin for MG pallasites.     

Compositional variability on the surface of 1 Ceres revealed through GRaND measurements of high‐energy gamma rays

High‐energy gamma rays (HEGRs) from Ceres’s surface were measured using Dawn's Gamma Ray and Neutron Detector (GRaND). Models of cosmic‐ray‐initiated gamma ray production predict that the HEGR flux will inversely vary with single‐layer hydrogen concentrations for Ceres‐like compositions. The measured data confirm this prediction. The hydrogen‐induced variations in HEGR rates were decoupled from the measurements by detrending the HEGR data with Ceres single‐layer hydrogen concentrations determined by GRaND neutron measurements. Models indicate that hydrogen‐detrended HEGR counting rates correlate with water‐free average atomic mass, which is denoted as <A>*. HEGR variations across Ceres’s surface are consistent with <A>* variations of ±0.5 atomic mass units. Chemical variations in the CM and CI chondrites, our closest analogs to Ceres’s surface, suggest that <A>* variations on Ceres are primarily driven by variations in the concentration of Fe, although other elements such as Mg and S could contribute. Dawn observations have shown that Ceres’s interior structure and surface composition have been modified by some combination of physical (i.e., ice‐rock fractionation) and/or chemical (i.e., alteration) processes that has led to variations in bulk surface chemistry. Locations of the highest inferred <A>* values, and thus possibly the highest Fe and least altered materials, tend to be younger, less cratered surfaces that are broadly associated with the impact ejecta of Ceres’s largest craters.     

Metamorphic carbonate–mafic amphibolite interactions from Arinteiro,northwest Spain

Some contacts between interlayered marbles and amphibolites at the Arinteiro copper mine are associated with zoned metasomatic calc-silicate assemblages. Textures indicate that formation of the calc-silicate zones involved mass transfer over distances up to 15 cm and that pore fluid solution (infiltration) may have been a significant reaction mechanism. The sequence of minerals is very similar to previously described products of metasomatic interactions between marbles and pelites. Similar metasomatic processes involving primary concentrations of carbonates can be invoked to explain the common occurrence of zoned calc-silicate patches and folia in metaigneous amphibolites both near Arinteiro and in other terrains.     

On the role of spatial resolution on snow estimates using a process‐based snow model across a range of climatology and elevation

Hydrological processes in mountainous settings depend on snow distribution, whose prediction accuracy is a function of model spatial scale. Although model accuracy is expected to improve with finer spatial resolution, an increase in resolution comes with modelling costs related to increased computational time and greater input data and parameter information. This computational and data collection expense is still a limiting factor for many large watersheds. Thus, this work's main objective is to question which physical processes lead to loss in model accuracy with regard to input spatial resolution under different climatic conditions and elevation ranges. To address this objective, a spatially distributed snow model, iSnobal, was run with inputs distributed at 50‐m—our benchmark for comparison—and 100‐m resolutions and with aggregated (averaged from the fine to the large resolution) inputs from the 50‐m model to 100‐, 250‐, 500‐, and 750‐m resolution for wet, average, and dry years over the Upper Boise River Basin (6,963 km²), which spans four elevation bands: rain dominated, rain–snow transition, and snow dominated below treeline and above treeline. Residuals, defined as differences between values quantified with high resolution (>50 m) models minus the benchmark model (50 m), of simulated snow‐covered area (SCA) and snow water equivalent (SWE) were generally slight in the aggregated scenarios. This was due to transferring the effects of topography on meteorological variables from the 50‐m model to the coarser scales through aggregation. Residuals in SCA and SWE in the distributed 100‐m simulation were greater than those of the aggregated 750 m. Topographic features such as slope and aspect were simplified, and their gradient was reduced due to coarsening the topography from the 50‐ to 100‐m resolution. Therefore, solar radiation was overestimated, and snow drifting was modified and caused substantial SCA and SWE underestimation in the distributed 100‐m model relative to the 50‐m model. Large residuals were observed in the wet year and at the highest elevation band when and where snow mass was large. These results support that model accuracy is substantially reduced with model scales coarser than 50 m.