In situ laboratory X-ray powder diffraction study of wollastonite carbonation using a high-pressure stage

A high-pressure gas stage, recently developed for in-situ X-ray powder diffraction studies of polymer crystallization under CO_2, has been used to observe the carbonation of wollastonite under various temperature/pressure conditions despite the fact that the stage was not designed for use with moisture-containing samples. The rate of carbonation of wollastonite at 60 °C was found to be pressure-independent. Additional experiments at 34.5 bar between 43 and 73 °C enabled an activation energy of 53 kJ mol⁻¹ to be determined for the rate-limiting step. This value agrees very well with a published value for the leaching of Ca from wollastonite in acidic conditions and suggests that Ca leaching is the rate-limiting step in wollastonite carbonation at these temperatures.     

Effects of changing solution chemistry on Fe/Fe isotope fractionation in aqueous Fe-Cl solutions

The range in ⁵⁶Fe/⁵⁴Fe isotopic compositions measured in naturally occurring iron-bearing species is greater than 5‰. Both theoretical modeling and experimental studies of equilibrium isotopic fractionation among iron-bearing species have shown that significant fractionations can be caused by differences in oxidation state (i.e., redox effects in the environment) as well as by bond partner and coordination number (i.e., nonredox effects due to speciation).To test the relative effects of redox vs. nonredox attributes on total Fe equilibrium isotopic fractionation, we measured changes, both experimentally and theoretically, in the isotopic composition of an Fe²⁺-Fe³⁺-Cl-H₂O solution as the chlorinity was varied. We made use of the unique solubility of FeCl₄⁻ in immiscible diethyl ether to create a separate spectator phase against which changes in the aqueous phase could be quantified. Our experiments showed a reduction in the redox isotopic fractionation between Fe²⁺- and Fe³⁺-bearing species from 3.4‰ at [Cl⁻] = 1.5 M to 2.4‰ at [Cl⁻] = 5.0 M, due to changes in speciation in the Fe-Cl solution. This experimental design was also used to demonstrate the attainment of isotopic equilibrium between the two phases, using a ⁵⁴Fe spike.To better understand speciation effects on redox fractionation, we created four new sets of ab initio models of the ferrous chloride complexes used in the experiments. These were combined with corresponding ab initio models for the ferric chloride complexes from previous work. At 20 °C, 1000 ln β (β = ⁵⁶Fe/⁵⁴Fe reduced partition function ratio relative to a dissociated Fe atom) values range from 6.39‰ to 5.42‰ for Fe(H₂O)₆²⁺, 5.98‰ to 5.34‰ for FeCl(H₂O)₅⁺, and 5.91‰ to 4.86‰ for FeCl₂(H₂O)₄, depending on the model. The theoretical models predict ferric-ferrous fractionation about half as large (depending on model) as the experimental results.Our results show (1) oxidation state is likely to be the dominant factor controlling equilibrium Fe isotope fractionation in solution and (2) nonredox attributes (such as ligands present in the aqueous solution, speciation and relative abundances, and ionic strength of the solution) can also have significant effects. Changes in the isotopic composition of an Fe-bearing solution will influence the resultant Fe isotopic signature of any precipitates.     

Wide‐area estimates of evapotranspiration by red gum (Eucalyptus camaldulensis) and associated vegetation in the Murray–Darling River Basin,Australia

Floodplain red gum forests (Eucalyptus camaldulensis plus associated grasses, reeds and sedges) are sites of high biodiversity in otherwise arid regions of southeastern Australia. They depend on periodic floods from rivers, but dams and diversions have reduced flood frequencies and volumes, leading to deterioration of trees and associated biota. There is a need to determine their water requirements so environmental flows can be administered to maintain or restore the forests. Their water requirements include the frequency and extent of overbank flooding, which recharges the floodplain soils with water, as well as the actual amount of water consumed in evapotranspiration (ET). We estimated the flooding requirements and ET for a 38 134 ha area of red gum forest fed by the Murrumbidgee River in Yanga National Park, New South Wales. ET was estimated by three methods: sap flux sensors placed in individual trees; a remote sensing method based on the Enhanced Vegetation Index from MODIS satellite imagery and a water balance method based on differences between river flows into and out of the forest. The methods gave comparable estimates yet covered different spatial and temporal scales. We estimated flood frequency and volume requirements by comparing Normalized Difference Vegetation Index values from Landsat images with flood history from 1995 to 2014, which included both wet periods and dry periods. ET during wet years is about 50% of potential ET but is much less in dry years because of the trees' ability to control stomatal conductance. Based on our analyses plus other studies, red gum trees at this location require environmental flows of 2000 GL yr^?1 every other year, with peak flows of 20 000 ML d^?1, to produce flooding sufficient to keep them in good condition. However, only about 120–200 GL yr^?1 of river water is consumed in ET, with the remainder flowing out of the forest where it enters the Murray River system. Copyright © 2015 John Wiley & Sons, Ltd.     

Hydrologic processes on tree islands in the Everglades (Florida, USA): tracking the effects of tree establishment and growth

The hydrodynamics of tree islands during the growth of newly planted trees has been found to be influenced by both vegetation biomass and geologic conditions. From July 2007 through June 2009, groundwater and surface-water levels were monitored on eight recently planted tree islands at the Loxahatchee Impoundment Landscape Assessment (LILA) facility in Boynton Beach, Florida, USA. Over the 2-year study, stand development coincided with the development of a water-table depression in the center of each of the islands that was bounded by a hydraulic divide along the edges. The water-table depression was greater in islands composed of limestone as compared to those composed of peat. The findings of this study suggest that groundwater evapotranspiration by trees on tree islands creates complex hydrologic interactions between the shallow groundwater in tree islands and the surrounding surface water and groundwater bodies.     

Multi-method assessment of connectivity between surface water and shallow groundwater: the case of Limarí River basin,north-central Chile

A study that tests the applicability and consistency of independent but complementary approaches in the assessment of interactions between surface water and shallow groundwater within a water-stressed basin is described. The mostly agricultural Limarí basin in arid north-central Chile was chosen as a suitable case study. The analyses involved: (1) a connectivity index method, (2) hydrochemistry, and (3) water isotopic geochemistry. Chemical and isotopic data were obtained from two sampling campaigns conducted in April (fall) and December (summer) of 2011 in 22 sampling locations, which included surface water and groundwater. The results obtained by each of the methodologies were mutually consistent and indicate high connectivity conditions. Additionally, the relative contribution by different sources was assessed through end-member mixing analysis, and for reaches of the river that showed gaining conditions, the contribution of groundwater inflow to stream discharge was estimated. It is suggested that this multi-method approach is useful for the characterization of surface-water–groundwater interactions, since it at least represents a suitable starting point for obtaining basic information on these relationships. Thus, it may become the base for further studies in arid and semi-arid basins facing water management challenges.     

Vegetation-groundwater dynamics at a former uranium mill site following invasion of a biocontrol agent: A time series analysis of Landsat normalized difference vegetation index data

Because groundwater recharge in dry regions is generally low, arid and semiarid environments have been considered well-suited for long-term isolation of hazardous materials (e.g., radioactive waste). In these dry regions, water lost (transpired) by plants and evaporated from the soil surface, collectively termed evapotranspiration (ET), is usually the primary discharge component in the water balance. Therefore, vegetation can potentially affect groundwater flow and contaminant transport at waste disposal sites. We studied vegetation health and ET dynamics at a Uranium Mill Tailings Radiation Control Act (UMTRCA) disposal site in Shiprock, New Mexico, where a floodplain alluvial aquifer was contaminated by mill effluent. Vegetation on the floodplain was predominantly deep-rooted, non-native tamarisk shrubs (Tamarix sp.). After the introduction of the tamarisk beetle (Diorhabda sp.) as a biocontrol agent, the health of the invasive tamarisk on the Shiprock floodplain declined. We used Landsat normalized difference vegetation index (NDVI) data to measure greenness and a remote sensing algorithm to estimate landscape-scale ET along the floodplain of the UMTRCA site in Shiprock prior to (2000–2009) and after (2010–2018) beetle establishment. Using groundwater level data collected from 2011 to 2014, we also assessed the role of ET in explaining seasonal variations in depth to water of the floodplain. Growing season scaled NDVI decreased 30% (p < .001), while ET decreased 26% from the pre- to post-beetle period and seasonal ET estimates were significantly correlated with groundwater levels from 2011 to 2014 (r² = .71; p = .009). Tamarisk greenness (a proxy for health) was significantly affected by Diorhabda but has partially recovered since 2012. Despite this, increased ET demand in the summer/fall period might reduce contaminant transport to the San Juan River during this period.     

Why did some larger benthic foraminifera become so large and flat?

Biostromes and low-relief bioherms, some of which are characterized by exceptionally large, flat specimens of larger benthic foraminifera, are common in Palaeogene and Miocene carbonates, most notably those deposited along the Neotethys Seaway and tropical Pacific islands. By incorporating insights from palaeoceanographic research and the biology of living larger benthic foraminifera, a scenario is proposed that can account for palaeontological and sedimentological features while augmenting previous interpretations. Sexual reproduction by gamete broadcasting is common in foraminiferal taxa, including extant Nummulitidae and Amphisteginidae. Resultant zygotes can develop into tiny, resistant, easily dispersed propagules that recruit in suitable benthic-environmental conditions. The role of algal symbiosis in the biology of larger benthic foraminifera is well-documented. Palaeoceanographically, such taxa proliferated during times of reduced thermal stratification of the oceans. In regions with exceptionally clear, nutrient-depleted waters, ‘twilight-zone’ light penetration was sufficient, at least intermittently, to support some photosynthesis. On outer-shelf or promontory sites at depths of ca 100 to 200 m, the tiny propagules of larger benthic foraminiferal species, incorporating algal symbionts with the lowest light requirements, could have settled and recruited, growing very slowly, nourished by feeding on bacteria and the limited photosynthate produced by their algal symbionts. Under such conditions, thin microspheric individuals of one or two larger benthic foraminiferal taxa could have survived and grown slowly over several years to very large shell diameters, seldom reproducing asexually. Resulting carbonate accumulation rates would have been very slow, such that even rare disturbances by currents, major storms or internal waves could have produced evidence of winnowing and sedimentary structures. The fossil evidence of such habitats should include biostromes or possibly low-relief bioherms of low diversity assemblages characterized by abundant, exceptionally large, flat, microspheric larger benthic foraminifera.     

Exploring the Effects of Shoreline Development on Fringing Salt Marshes Using Nekton,Benthic Invertebrate,and Vegetation Metrics

Fringing marshes are important but often overlooked components of estuarine systems. Due to their relatively small size and large edge to area ratio, they are particularly vulnerable to impacts from adjacent upland development. Because current shoreland zoning policies aim to limit activities in upland buffer zones directly next to coastal habitats, we tested for relationships between the extent of development in a 100-m buffer adjacent to fringing salt marshes and the structure of marsh plants, benthic invertebrates, and nekton communities. We also wanted to determine useful metrics for monitoring fringing marshes that are exposed to shoreline development. We sampled 18 fringing salt marshes in two estuaries along the coast of southern Maine. The percent of shoreline developed in 100-m buffers around each site ranged from 0 to 91 %. Several variables correlated with the percent of shoreline developed, including one plant diversity metric (Evenness), two nekton metrics (Fundulus heteroclitus %biomass and Carcinus maenas %biomass), and several benthic invertebrate metrics (nematode and insect/dipteran larvae densities in the high marsh zone) (p?<?0.05). Carcinus maenas, a recent invader to the area, comprised 30–97 % of the nekton biomass collected at the 18 sites and was inversely correlated with Fundulus %biomass. None of these biotic metrics correlated with the other abiotic marsh attributes we measured, including porewater salinity, marsh site width, and distance of the site to the mouth of the river. In all, between 25 and 48 % of the variance in the individual metrics we identified was accounted for by the extent of development in the 100-m buffer zone. Results from this study add to our understanding of fringing salt marshes and the impacts of shoreline development to these habitats and point to metrics that may be useful in monitoring these impacts.     

Burning through organizational boundaries? Examining inter-organizational communication networks in policy-mandated collaborative bushfire planning groups

Collaboration can enhance cooperation across geographic and organizational scales, effectively “burning through” those boundaries. Using structured social network analysis (SNA) and qualitative in-depth interviews, this study examined three collaborative bushfire planning groups in New South Wales, Australia and asked: How does participation in policy-mandated collaboration affect bushfire communication networks amongst organizational representatives? Inter-organizational communication networks became more active, less centralized, and more closely connected during planning than they had been prior. However, efforts to institutionalize collaboration were intrinsically biased towards placing administrative power and influence in public agencies. Further, collaborative planning groups did not maintain “during planning” levels of network activity and structure after planning was completed. In one case, the mandated planning process had a negative impact on inter-agency communication networks. Contextual aspects such as group size, history of inter-organizational conflict and fire occurrence, and process management were important in the development of inter-organizational networks. Though communication diminished after planning was completed, participation in the collaborative planning effort may serve as an important basis for the continuation of inter-organizational relationships beyond the scope of the planning process.     

Transition from calc-alkaline to potassium-rich magmatism in subduction environments: geochemical and Sr, Nd, Pb isotopic constraints from the island of Vulcano (Aeolian arc)

The problem of mantle metasomatism vs. crustal contamination in the genesis of arc magmas with different potassium contents has been investigated using new trace element and Sr–Nd–Pb isotopic data on the island of Vulcano, Aeolian arc. The analysed rocks range in age from 120 ka to the present day, and cover a compositional range from basalt to rhyolite of the high-K calc-alkaline (HKCA) to shoshonitic (SHO) and potassic (KS) series. Older Vulcano products (>30 ka) consist of HKCA–SHO rocks with SiO₂=48–56%. They show lower contents of K₂O, Rb and of several other incompatible trace element abundances and ratios than younger rocks with comparable degree of evolution. ⁸⁷Sr/⁸⁶Sr ranges from 0.70417 to 0.70504 and increases with decreasing MgO and compatible element contents. ²⁰⁶Pb/²⁰⁴Pb ratios display significant variations (19.31 to 19.76) and are positively correlated with MgO, ¹⁴³Nd/¹⁴⁴Nd (0.512532–0.512768), ²⁰⁷Pb/²⁰⁴Pb (15.66–15.71) and ²⁰⁸Pb/²⁰⁴Pb (39.21–39.49). Overall, geochemical and isotopic data suggest that the evolution of the older series was dominated by assimilation–fractional crystallisation (AFC) with an important role for continuous mixing with mafic liquids. Magmas erupted within the last 30 ka consist mostly of SHO and KS intermediate and acid rocks, with minor mafic products. Except for a few acid rocks, they display moderate isotopic variations (e.g. ⁸⁷Sr/⁸⁶Sr=0.70457–0.70484; ²⁰⁶Pb/²⁰⁴Pb=19.28–19.55, but ²⁰⁷Pb/²⁰⁴Pb=15.66–15.82), which suggest an evolution by fractional crystallisation, or in some cases by mixing, with little interaction with crustal material. The higher Sr isotopic ratios (⁸⁷Sr/⁸⁶Sr=0.70494–0.70587) of a few, low-volume, intermediate to acid rocks support differentiation by AFC at shallow depths for some magma batches. New radiogenic isotope data on the Aeolian islands of Alicudi and Stromboli, as well as new data for lamproites from central Italy, are also reported in order to discuss along-arc compositional variations and to evaluate the role of mantle metasomatism. Geochemical and petrological data demonstrate that the younger K-rich mafic magmas from Vulcano cannot be related to the older HKCA and SHO ones by intra-crustal evolutionary processes and point to a derivation from different mantle sources. The data from Alicudi and Stromboli suggest that, even though interaction between magma and wall rocks of the Calabrian basement during shallow level magma evolution was an important process locally, a similar interpretation can be extended to the entire Aeolian arc. Received: 27 September 1999 / Accepted: 24 May 2000