Seasonal connections between meteoric water and streamflow generation along a mountain headwater stream

In snowmelt-driven mountain watersheds, the hydrologic connectivity between meteoric waters and stream flow generation varies strongly with the season, reflecting variable connection to soil and groundwater storage within the watershed. This variable connectivity regulates how streamflow generation mechanisms transform the seasonal and elevational variation in oxygen and hydrogen isotopic composition (δ¹⁸O and δD) of meteoric precipitation. Thus, water isotopes in stream flow can signal immediate connectivity or more prolonged mixing, especially in high-relief mountainous catchments. We characterized δ¹⁸O and δD values in stream water along an elevational gradient in a mountain headwater catchment in southwestern Montana. Stream water isotopic compositions related most strongly to elevation between February and March, exhibiting higher δ¹⁸O and δD values with decreasing elevation. These elevational isotopic lapse rates likely reflect increased connection between stream flow and proximal snow-derived water sources heavily subject to elevational isotopic effects. These patterns disappeared during summer sampling, when consistently lower δ¹⁸O and δD values of stream water reflected contributions from snowmelt or colder rainfall, despite much higher δ¹⁸O and δD values expected in warmer seasonal rainfall. The consistently low isotopic values and absence of a trend with elevation during summer suggest lower connectivity between summer precipitation and stream flow generation as a consequence of drier soils and greater transpiration. As further evidence of intermittent seasonal connectivity between the stream and adjacent groundwaters, we observed a late-winter flush of nitrate into the stream at higher elevations, consistent with increased connection to accumulating mineralized nitrogen in riparian wetlands. This pattern was distinct from mid-summer patterns of nitrate loading at lower elevations that suggested heightened human recreational activity along the stream corridor. These observations provide insights linking stream flow generation and seasonal water storage in high elevation mountainous watersheds. Greater understanding of the connections between surface water, soil water and groundwater in these environments will help predict how the quality and quantity of mountain runoff will respond to changing climate and allow better informed water management decisions.     

40Ar-39Ar dating of the H3 chondrite Sainte Rose

Abstract— A whole rock sample from the H3 chondrite Sainte Rose, which was discovered in 1983, was dated with the ⁴⁰Ar-³⁹Ar technique. From the K/Ca spectrum and from an analysis of the ³⁹Ar recoil effect we conclude that this meteorite has at least two distinguishable K-carriers: a low temperature, high-K/Ca, fine-grained carrier with a typical grain size of about 2 μm and a high temperature, low-K/Ca, more coarse-grained carrier. The K-Ar clocks of both were started 4.40 ± 0.01 Ga ago.     

Effects of natural attenuation processes on groundwater contamination caused by abandoned waste sites in Berlin

The aim of this research project is to identify, characterize and quantify natural attenuation (NA) processes in groundwater affected by emissions of abandoned waste disposal sites in Berlin-Kladow/Gatow, Germany. It is part of the funding priority called KORA established by the Federal Ministry for Education and Research (BMBF) to explore the extent to which NA can be used for remedial purposes for varied forms of soil and groundwater contamination. Information on the emission behaviour of individual parameters is generated on the basis of hydrogeochemical comparison of 20 years old and new data. Using groundwater-modelling and CFC-analysis, information on the transport and retention of pollutants in groundwater is compiled. The microbial colonization of contaminated aquifers is characterized by molecular biological methods [polymerase chain reaction (PCR) and denaturing gradient gel electrophoresis (DGGE)] to differentiate between contaminated and not contaminated zones.     

Application of precise 142Nd/144Nd analysis of small samples to inclusions in diamonds (Finsch,South Africa) and Hadean Zircons (Jack Hills,Western Australia)

¹⁴⁶Sm–¹⁴²Nd and ¹⁴⁷Sm–¹⁴³Nd systematics were investigated in garnet inclusions in diamonds from Finsch (S. Africa) and Hadean zircons from Jack Hills (W. Australia) to assess the potential of these systems as recorders of early Earth evolution. The study of Finsch inclusions was conducted on a composite sample of 50 peridotitic pyropes with a Nd model age of 3.3 Ga. Analysis of the Jack Hills zircons was performed on 790 grains with ion microprobe ²⁰⁷Pb/²⁰⁶Pb spot ages from 3.95 to 4.19 Ga. Finsch pyropes yield 100 × ?¹⁴²Nd = ? 6 ± 12 ppm, ?¹⁴³Nd = ? 32.5, and ¹⁴⁷Sm/¹⁴⁴Nd = 0.1150. These results do not confirm previous claims for a 30 ppm ¹⁴²Nd excess in South African cratonic mantle. The lack of a ¹⁴²Nd anomaly in these inclusions suggests that isotopic heterogeneities created by early mantle differentiation were remixed at a very fine scale prior to isolation of the South African lithosphere. Alternatively, this result may indicate that only a fraction of the mantle experienced depletion during the first 400 Myr of its history. Analysis of the Jack Hills zircon composite yielded 100 × ?¹⁴²Nd = 8 ± 10 ppm, ?¹⁴³Nd = 45 ± 1, and ¹⁴⁷Sm/¹⁴⁴Nd = 0.5891. Back-calculation of this present-day ?¹⁴³Nd yields an unrealistic estimate for the initial ?¹⁴³Nd of ? 160 ?-units, clearly indicating post-crystallization disturbance of the ¹⁴⁷Sm–¹⁴³Nd system. Examination of ^146,147Sm–^142,143Nd data reveals that the Nd budget of the Jack Hills sample is dominated by non-radiogenic Nd, possibly contained in recrystallized zircon rims or secondary subsurface minerals. This secondary material is characterized by highly discordant U–Pb ages. Although the mass fraction of altered zircon is unlikely to exceed 5–10% of total sample, its high LREE content precludes a reliable evaluation of ¹⁴⁶Sm–¹⁴²Nd systematics in Jack Hills zircons.     

Coupled redox transformations of catechol and cerium at the surface of a cerium(III) phosphate mineral

Highly insoluble Ce-bearing phosphate minerals form by weathering of apatite [Ca₅(PO₄)₃.(OH,F,Cl)], and are important phosphorous repositories in soils. Although these phases can be dissolved via biologically-mediated pathways, the dissolution mechanisms are poorly understood. In this paper we report spectroscopic evidence to support coupling of redox transformations of organic carbon and cerium during the reaction of rhabdophane (CePO₄·H₂O) and catechol, a ubiquitous biogenic compound, at pH 5. Results show that the oxic–anoxic conditions influence the mineral dissolution behavior. Under anoxic conditions, the release of P and Ce occurs stoichiometrically. In contrast, under oxic conditions, the mineral dissolution behavior is incongruent, with dissolving Ce³⁺ ions oxidizing to CeO₂. Reaction product analysis shows the formation of CO₂, polymeric C, and oxalate and malate. The presence of more complex forms of organic carbon was also confirmed. Near edge X-ray absorption fine structure spectroscopy measurements at Ce-M_4,5 and C-K absorption edges on reacted CePO₄·H₂O samples in the absence or presence of catechol and dissolved oxygen confirm that (1) the mineral surface converts to the oxide during this reaction, while full oxidation is limited to the near-surface region only; (2) the Ce valence remains unchanged when the reaction between CePO₄·H₂O and O₂ but in the absence of catechol. Carbon K-edge spectra acquired from rhabdophane reacted with catechol under oxic conditions show spectral features before and after reaction that are considerably different from catechol, indicating the formation of more complex organic molecules. Decreases in intensity of characteristic catechol peaks are accompanied by the appearance of new π^* resonances due to carbon in carboxyl (ca. 288.5 eV) and carbonyl (ca. 289.3 eV) groups, and the development of broad structure in the σ^* region characteristic of aliphatic carbon. Evolution of the C K-edge spectra is consistent with aromatic-ring cleavage and polymerization. These results further substantiate that the presence of catechol, O₂ (aq) causes both the oxidation of structural Ce³⁺ and the transformation of catechol to more complex organic molecules. Scanning Transmission X-Ray Microscopy measurements at the C K and Ce M_4,5 edges indicate three dominant organic species, varying in complexity and association with the inorganic phase. Untransformed catechol is loosely associated with CeO₂, whereas more complex organic molecules that exhibit lower aromaticity and stronger CO π^* resonances of carboxyl-C and carbonyl-C groups are only found in association with the grains. These results further serve as basis to postulate that, in the presence of O₂, CeO₂ can mediate the oxidative polymerization of catechol to form higher molecular weight polymers. The present work provides evidence for a pathway of biologically-induced, non-enzymatic oxidation of cerium and formation of small CeO₂ particles at room temperature. These findings may have implications for carbon cycling in natural and cerium-contaminated soils and aqueous environments.     

Abandoned bodies and spaces of sacrifice: Pesticide drift activism and the contestation of neoliberal environmental politics in California

Recent research suggests that many key strands of California’s agrofood activism appear to accommodate, rather than confront, the neoliberalization of environmental governance, and that such accommodations might problematically constrain the transformative potential of activists’ work. In this paper, I examine the case of pesticide drift activism in California, which, as an exception to this trend, provides a provocative and useful case study for interrogating the influence of neoliberalization on social/environmental activism. I argue that California’s pesticide drift activism can be understood as a reaction to the spaces of sacrifice created and exacerbated by the failure of unionization-based pesticide reform efforts, a promising but compromised regulatory apparatus, longstanding farmworker powerlessness, neoliberal regulatory rollback, and neoliberalized pesticide politics – a mosaic of factors that have worked together to produce a regulatory structure that has always been better at registering pesticides than at reducing pollution. I show that pesticide drift activists’ reliance on confrontational practice, collective action, and strategic alliances have been crucial to the movement’s success with bringing visibility to this issue and with gaining traction in the political arena. Thus, at the same time that neoliberalization can exacerbate physical spaces of sacrifice, this case study illustrates that it can also, unexpectedly perhaps, generate new, non-neoliberal political spaces for social change.     

Defect properties of albite

Knowledge of the defect properties of Lunar and Mercurian minerals has recently become important, with the advent of models which attempt to explain the formation of the thin exosphere of these celestial bodies. Here, we have calculated the formation energies of sodium and oxygen vacancies in the mineral albite (NaAlSi₃O₈), as well as the Schottky defect energy for the removal of a Na₂O unit. We have employed both the supercell and Mott–Littleton approaches, using Kohn–Sham density functional theory and classical interatomic potential methods. As well as reporting the defect energies and structures, we comment upon the relative merits of the methods used.     

An ecosystem model with iron limitation of primary production in the equatorial Pacific at 140°W

We construct a one-dimensional ecosystem model (nitrate, ammonium, phytoplankton, zooplnakton and detritus) with simple physics and biology in order to focus on the structural relations and intrinsic properties of the food web that characterizes the biological regime in the central equatorial Pacific at 140°W. When possible, data collected during the EgPac and other cruises were used to calibrate model parameters for two simulations that differ in the limiting nutrient, i.e. nitrogen or iron. Both simulations show annual results in good agreement with the data, but phytoplankton biomass and primary production show a more pronounced annual variability when iron is used as the limiting nutrient. This more realistically reproduces the variability of biological production and illustrates the greater coupling between vertical physical processes and biological production when the limiting nutrient is iron rather than nitrogen. The iron simulation also illustrates how iron supply controls primary production variability, how grazingbalances primary production and controls phytoplankton biomass, and how both iron supply and grazingcontrol primary production. These results suggest that it is not possible to capture primary production variability in the central equatorial Pacific with biological models using nitrogen as the limiting nutrient. Other indirect results of this modeling study were: (1) partitioning of export production between dissolved and particulate matter is almost equal, suggesting that the importance of DOC export may have been previously overestimated; (2) lateral export of live biomass has to be taken into account in order to balance the nitrogen budget on the equator at 140°W; and (3) preferential uptake of ammonium (i.e. nitrate uptake inhibition by ammonium) associated with high regeneration of nitrogen (low f ratio as a consequence of the food web structure imposed by iron limitation) largely accounts for the surface build-up of upwelled nitrate.     

Photoadaptation of carboxylating enzymes and photosynthesis during a spring bloom

Properties of the light saturation curve of photosynthesis and ribulose-1,5-bisphosphate carboxylase (RuBPC) activity are shown to change qualitatively in a natural population of marine phytoplankton during a spring bloom. Evidence is presented to show that these changes constitute photoadapative responses to increasing irradiance. As irradiance increased during the bloom, both the level of light-saturated photosynthesis (P_m) and the initial slope of the light saturation curve (α = photosynthetic efficiency) increased whether those parameters were normalized to chlorophyll a concentration (P_m^b, α^b) or to cell numbers (P_m^c, α^c). The magnitudes of these changes were such that I_k (= P_m/α, the photoadaptation parameter) did not change, but I_m, the light intensity at which photosynthesis becomes saturated, increased. RuBPC activity, both chlorophyll a (RuBPC^b) and cell number normalized (RuBPC^c), also increased during the bloom. We suggest that these adaptations were achieved by simultaneously increasing the number of photosynthetic units, proportionately decreasing the photosynthetic unit size, and increasing both the concentrations of the enzymes of the dark reactions and possibly also of photosynthetic electron transport components.We also observed diminished levels of photoinhibition in the high light adapted cells late in the bloom and have suggested that this was a consequence of the same suite of physiological changes.In situ carbon fixation per cell increased during the bloom whereas no change occurred in this parameter when normalized to chlorophyll a concentration. Although these photoadaptive responses thus permitted carbon to be fixed in situ more rapidly per cell, at a constant efficiency with respect to investment of energy in the photosynthetic apparatus, they did not result in a change in growth rate. Based on consideratios of the role of time scale in physiological adaptation, however, it is suggested that the observed alterations in photosynthesis with increasing irradiance might permit a cell to more rapidly fill an energy quota for division, possibly an advantage in a mixing environment in which energy is patchily distributed, both spatially and temporalyy.Phosphoenolpyruvate carboxylase activity when normalized to chlorophyll a (PEPC^b) did not change during the bloom while chlorophyll a normalized dark carbon fixation decreased sharply and was quantitatively small compared to PEPC^b. On this basis and considering that RuBPC^b increased during the bloom, it is suggested that, although PEPC may be involved in dark carbon fixation, its most important quantitative role is probably an indirect one in light dependent photosynthesis.We have also considered the relevance of laboratory results on photoadaptation to interpretations of field studies and have suggested that batch culture studies must be treated with caution but that turbidistat and semi-continuous methods provide reasonable simulations of natural conditions.     

Sediment-starved sand ridges on a mixed carbonate/siliciclastic inner shelf off west-central Florida

High-resolution side-scan mosaics, sediment analyses, and physical process data have revealed that the mixed carbonate/siliciclastic, inner shelf of west-central Florida supports a highly complex field of active sand ridges mantled by a hierarchy of bedforms. The sand ridges, mostly oriented obliquely to the shoreline trend, extend from 2 km to over 25 km offshore. They show many similarities to their well-known counterparts situated along the US Atlantic margin in that both increase in relief with increasing water depth, both are oriented obliquely to the coast, and both respond to modern shelf dynamics. There are significant differences in that the sand ridges on the west-central Florida shelf are smaller in all dimensions, have a relatively high carbonate content, and are separated by exposed rock surfaces. They are also shoreface-detached and are sediment-starved, thus stunting their development. Morphological details are highly distinctive and apparent in side-scan imagery due to the high acoustic contrast. The seafloor is active and not a relict system as indicated by: (1) relatively young AMS ¹⁴C dates (<1600 yr BP) from forams in the shallow subsurface (1.6 meters below seafloor), (2) apparent shifts in sharply distinctive grayscale boundaries seen in time-series side-scan mosaics, (3) maintenance of these sharp acoustic boundaries and development of small bedforms in an area of constant and extensive bioturbation, (4) sediment textural asymmetry indicative of selective transport across bedform topography, (5) morphological asymmetry of sand ridges and 2D dunes, and (6) current-meter data indicating that the critical threshold velocity for sediment transport is frequently exceeded. Although larger sand ridges are found along other portions of the west-central Florida inner shelf, these smaller sand ridges are best developed seaward of a major coastal headland, suggesting some genetic relationship. The headland may focus and accelerate the N–S reversing currents. An elevated rock terrace extending from the headland supports these ridges in a shallower water environment than the surrounding shelf, allowing them to be more easily influenced by currents and surface gravity waves. Tidal currents, storm-generated flows, and seasonally developed flows are shore-parallel and oriented obliquely to the NW–SE trending ridges, indicating that they have developed as described by the Huthnance model. Although inner shelf sand ridges have been extensively examined elsewhere, this study is the first to describe them in a low-energy, sediment-starved, dominantly mixed siliciclastic/carbonate sedimentary environment situated on a former limestone platform.