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At least 1,135 records · Page 63Linked to original sources

Vector analysis of chemical variation in the lavas of Parícutin volcano, Mexico

Compositional variations in the lavas of Parícutin volcano, Mexico, have been examined by an extended method of Q-mode factor analysis. Each sample composition is treated as a vector projected from an original eight-dimensional space into a vector system of three dimensions. The compositions represented by the vectors after projection are closely similar to the original compositions except for Na2O and Fe2O3. The vectors in the three-dimensional system cluster about three different planes that represent three stages of compositional change in the Parícutin lavas. Because chemical data on the compositions of the minerals in the lavas are presently lacking, interpretations of the mineral phases that may have been involved in fractional crystallization are based on CIPW norm calculations. Changes during the first stage are attributed largely to the fractional crystallization of plagioclase and olivine. Changes during the second stage can be explained by the separation of plagioclase and pyroxene. Changes during the final stage may have resulted mostly from the assimilation of a granitic material, as previously proposed by R. E. Wilcox.

Journal of the International Association for Mathe↗

Effects of a legal drain clean-out on wetlands and waterbirds: a recent case history

Repairs to legal drains in the United States may be regulated to protect adjacent wetlands under Section 404 of the Federal Water Pollution Control Act, commonly known as the Clean Water Act (CWA). However, few studies have examined effects of legal drain clean-outs on adjacent wetlands and associated migratory waterbird populations. I compare water regimes, cover-to-open water ratios, and waterbird use on Bruns, Big, Meszaros, and Kraft sloughs (BBMK) in Sargent County, North Dakota before and after the clean-out of Crete-Cogswell Drain No. 11, and relate wetland habitat loss to observed disease-related mortality among staging waterfowl in fall 1990 and spring 1991. Water regimes of BBMK were exceptionally stable, with few records of drawdowns before 1984 when the clean-out began. After the clean-out (1987-90), BBM were dry by mid-summer in all years and open area declined by 96% by 1990, whereas Kraft Slough (a control area) had water throughout all years and percent open area did not change. Numerous species of waterbirds nested in BBMK before the clean-out, and mean ranks of waterbird density were similar. After the clean-out, waterbirds failed to breed successfully in all years at BBM, and use as major waterfowl staging areas and for waterfowl hunting also ended. At Kraft Slough, use by breeding and staging waterbirds continued in all years, as did waterfowl hunting. Reduced access to fresh water after the Drain No. 11 clean-out may have contributed to a dieoff of 487 lesser snow geese (Chen caerulescens) from necrotic enteritis in Kraft Slough in November 1990. Loss of three major staging areas in Sargent County as a result of the drain clean-out has further concentrated migrant waterfowl, particularly during drought periods, increasing the magnitude of risk when epizootics occur in southeastern North Dakota. Ducks and geese banded in Sargent County have been recovered from 34 and 14 states, 7 and 6 provinces of Canada, and 13 and 1 other countries, respectively, indicating waterfowl populations from a wide area are potentially vulnerable to epizootics when crowded into limited roosting habitat. Despite causing the loss of wetland habitat for thousands of midcontinent waterfowl and other waterbirds, a Federal Court in North Dakota ruled that the clean-out of Drain No. 11 met the criteria necessary to be considered maintenance under Section 404 clause (f)(1)(c) and was not recaptured under clause (f)(2). This outcome suggests current law does not protect wetland functions needed to support migratory waterbird populations or associated recreational values when sites have become naturally restored through lack of maintenance of legal drains.

Wetlands↗

Extreme variation of sulfur isotopic compositions in pyrite from the Qiuling sediment-hosted gold deposit, West Qinling orogen, central China: An in situ SIMS study with implications for the source of sulfur

High spatial resolution textural (scanning electron microscope (SEM)), chemical (electron microprobe (EMP)) and laser ablation-inductively coupled plasma-mass spec- trometry (LA-ICP-MS)), and sulfur isotopic (secondary ion mass spectrometry (SIMS)) analyses of pyrite from the Qiuling sediment-hosted gold deposit (232±4 Ma) in the West Qinling orogen, central China were conducted to distinguish pyrite types and gain insights into the source and evolution of sulfur in hydrothermal fluids. The results reveal an enormous variation (−27.1 to +69.6‰) in sulfur isotopic composition of pyrite deposited during three paragenetic stages. Pre-ore framboidal pyrite, which is characterized by low concentra- tions of As, Au, Cu, Co, and Ni, has negative δ34S values of −27.1 to −7.6‰ that are interpreted in terms of bacterial re- duction of marine sulfate during sedimentation and diagenesis of the Paleozoic carbonate and clastic sequences, the predom- inant lithologies in the deposit area, and the most important hosts of many sediment-hosted gold deposits throughout the West Qinling orogen. The ore-stage hydrothermal pyrite con- tains high concentrations of Au, As, Cu, Sb, Tl, and Bi and hasa relatively narrow range of positive δ34S values ranging from +8.1 to +15.2‰. The sulfur isotope data are comparable to those of ore pyrite from many Triassic orogenic gold deposits and Paleozoic sedimentary exhalative (SEDEX) Pb-Zn de- posits in the West Qinling orogen, both being hosted mainly in the Devonian sequence. This similarity indicates that sulfur, responsible for the auriferous pyrite at Qiuling, was largely derived from the metamorphic devolatization of Paleozoic marine sedimentary rocks. Post-ore-stage pyrite, which is sig- nificantly enriched in Co and Ni but depleted in Au and As, has unusually high δ34S values ranging from +37.4 to +69.6 ‰, that are interpreted to result from thermochemical reduc- tion of evaporite sulfates in underlying Cambrian sedimentary rocks with very high δ34S values. The variations in Au content and sulfur isotopic compositions across a single ore-stage py- rite grain may reflect displacement of indigenous groundwater with low δ34S values by auriferous metamorphic fluids with high δ34S values. The very low-grade metamorphism of the host rocks and the metamorphic derivation of sulfur for the ore pyrite indicate that the Qiuling sediment-hosted gold deposit is an epizonal manifestation of an orogenic gold system in the West Qinling orogen.

Mineralium Deposita↗

Dramatic fluctuations in liver mass and metal content of eared grebes ( Podiceps nigricollis ) during autumnal migration

Adult eared grebes exhibit threefold fluctuation in body mass and up to a fivefold variation in liver weight during the course of their annual breeding and migratory cycle. Concentrations of 20 metals or metalloids were quantified in the liver from eared grebes obtained at three phases of their annual cycle: newly arrived migrants (July-August-September), staging (October-November), and immediate post-migration (December-January). Values for twelve elements (Al, B, Cd, Cr, Cu, Fe, Hg, Mg, Mn, Ni, Se, and Zn) that were detected in more than one-half of the samples were low. Hepatic concentrations of elements known to be toxic to free-ranging birds (e.g., Cd, Hg, Pb, Se) were well below known effect thresholds. No differences in metal concentrations were observed between newly arrived migrants and staging birds despite the large increases in body and liver mass. However, in the immediate post-migration period after body and liver mass have rapidly declined, Al values decreased, whereas Se and Zn concentrations actually increased. Total liver burdens of elements tended to be greatest in staging grebes compared to other collection periods, and paralleled changes in body and liver mass. The need for temporally- and physiologically-matched reference birds, and at least knowledge of circannual organ mass fluctuations, appears to be a requirement for ecotoxicological exposure assessments in species such as the eared grebe. Generation of additional avian toxicity data from controlled dosing studies during potentially vulnerable phases of their annual cycle (e.g., molt, post-migration) seems warranted. Although it is commonly accepted that hepatic metal concentrations are principally affected by contaminant exposure, we have shown differential alterations related to the stage of the annual cycle. Our findings may be of broad significance, as well as of immediate importance in resolving the cause of the die-off of approximately 150,000 eared grebes (perhaps 7% of the North American population) at the Salton Sea in 1991-1992.

Bulletin of Environmental Contamination and Toxico↗

Factors affecting the toxicity of methylmercury injected into eggs

We developed a standardized protocol for comparing the sensitivities of the embryos of different bird species to methylmercury when methylmercury was injected into their eggs. During the course of developing this protocol, we investigated the effects of various factors on the toxicity of the injected methylmercury. Most of our experiments were done with chicken ( Gallus domesticus ), mallard ( Anas platyrhynchos ), and ring-necked pheasant ( Phasianus colchicus ) eggs, all of which were purchased in large numbers from game farms. A smaller amount of work was done with double-crested cormorant ( Phalacrocorax auritus ) eggs collected from the wild. Several solvents were tested, and corn oil at a rate of 1 μl/g egg contents was selected for the final standardized protocol because it had minimal toxicity to embryos and because methylmercury dissolved in corn oil yielded a dose–response curve in a range of egg concentrations that was similar to the range that causes reproductive impairment when the mother deposits methylmercury into her own eggs. The embryonic stage at which eggs were injected with corn oil altered mercury toxicity; at early stages, the corn oil itself was toxic. Therefore, in the final protocol we standardized the time of injection to occur when each species reached the morphologic equivalent of a 3-day-old chicken embryo. Although solvents can be injected directly into the albumen of an egg, high embryo mortality can occur in the solvent controls because of the formation of air bubbles in the albumen. Our final protocol used corn oil injections into the air cell, which are easier and safer than albumen injections. Most of the methylmercury, when dissolved in corn oil, injected into the air cell passes through the inner shell membrane and into the egg albumen. Most commercial incubators incubate eggs in trays with the air cell end of the egg pointing upward, but we discovered that mercury-induced mortality was too great when eggs were held in this orientation. In addition, some species of bird eggs require incubation on their sides with the eggs being rolled 180° for them to develop normally. Therefore, we adopted a procedure of incubating the eggs of all species on their sides and rolling them 180° every hour. Little has been published about the conditions of temperature, humidity, and the movements to which eggs of wild birds need to be subjected for them to hatch optimally under artificial incubation. Not unexpectedly, hatching success in an artificial incubator is generally less than what natural incubation by the parents can achieve. However, the survival of control embryos of most wild bird species was good (generally ≥ 80%) up to within 1 or 2 days of hatching when we incubated the eggs at 37.5°C (or 37.6°C for gallinaceous species) at a relative humidity that resulted in an approximate 15% to 16% loss in egg weight by the end of incubation and by incubating the eggs on their sides and rolling them 180°/h. To improve statistical comparisons, we used survival through 90% of incubation as our measurement to compare survival of controls with survival of eggs injected with graded concentrations of mercury.

Archives of Environmental Contamination and Toxico↗

Plagioclase zonation styles in hornblende gabbro inclusions from Little Glass Mountain, Medicine Lake volcano, California: Implications for fractionation mechanisms and the formation of composition gaps

The rhyolite of Little Glass Mountain (73–74% SiO 2 ) is a single eruptive unit that contains inclusions of quenched andesite liquid (54–61% SiO 2 ) and partially crystalline cumulate hornblende gabbro (53–55% SiO 2 ). Based on previous studies, the quenched andesite inclusions and host rhyolite lava are related to one another through fractional crystallization and represent an example of a fractionation-generated composition gap. The hornblende gabbros represent the cumulate residue associated with the rhyolite-producing and composition gap-forming fractionation event. This study combines textural (Nomarski Differential Interference Contrast, NDIC, imaging), major element (An content) and trace element (Mg, Fe, Sr, K, Ti, Ba) data on the style of zonation of plagioclase crystals from representative andesite and gabbro inclusions, to assess the physical environment in which the fractionation event and composition gap formation took place. The andesite inclusions (54–61% SiO 2 ) are sparsely phyric with phenocrysts of plagioclase, augite and Fe-oxide±olivine, +/–orthopyroxene, +/–hornblende set within a glassy to crystalline matrix. The gabbro cumulates (53–55% SiO 2 ) consist of an interconnected framework of plagioclase, augite, olivine, orthopyroxene, hornblende and Fe-oxide along with highly vesicular interstitial glass (70–74% SiO 2 ). The gabbros record a two-stage crystallization history of plagioclase+olivine+augite (Stage I) followed by plagioclase+orthopyroxene+ hornblende+Fe-oxide (Stage II). Texturally, the plagioclase crystals in the andesite inclusions are characterized by complex, fine-scale oscillatory zonation and abundant dissolution surfaces. Compositionally (An content) the crystals are essentially unzoned from core-to-rim. These features indicate growth within a dynamic (convecting?), reservoir of andesite magma. In contrast, the plagioclase crystals in the gabbros are texturally smooth and featureless with strong normal zonation from An 74 at the core to around An 30 . K, and Ba abundances increase and Mg abundances decrease steadily towards the rim. Ti, Fe, and Sr abundances increase and then decrease towards the rim. The trace element variations are fully consistent with the two-stage crystallization sequence inferred from the gabbro mineralogy. These results indicate progressive closed-system in situ crystallization in a quiescent magmatic boundary layer environment located along the margins of the andesite magma body. The fractional crystallization that generated the host rhyolite lava is one of inward solidification of a crystallizing boundary layer followed by melt extraction and accumulation of highly evolved interstitial liquid. This mechanism explains the formation of the composition gap between parental andesite and rhyolite magma compositions.

California↗

Investing in a nest egg: Intraspecific variation in the timing of egg laying across a latitudinal gradient

Avian reproductive strategies vary widely, and many studies of life-history variation have focused on the incubation and hatching stages of nesting. Birds make proximate decisions regarding reproductive investment during the laying stage, and these decisions likely constrain and tradeoff with other traits and subsequent behaviors. However, we know relatively little about egg-laying stage behaviors given the difficulty of locating and monitoring nest sites from the onset of laying. We used non-invasive continuous video recording to quantify variation in the egg-laying behaviors of burrowing owls ( Athene cunicularia) along a 1400-km latitudinal gradient in western North America. Burrowing owls laid eggs disproportionately in the morning hours, and that tendency was strongest among first eggs in a clutch. However, selection appeared to act more strongly on laying intervals (the time between laying of consecutive eggs) than on the diel time of laying, and laying intervals varied widely among and within clutches. Laying intervals declined seasonally and with increasing clutch size but increased with increasing burrow temperature and as a function of laying stage nest attentiveness, which may be a strategy to preserve egg viability. Laying interval was positively correlated with the duration of hatching intervals, suggesting that laying interval duration is one mechanism (along with timing of incubation onset) that generates variation in hatching asynchrony. Our results lend support to two general hypotheses to explain laying schedules; selection favors laying eggs in the morning, but other selective pressures may override that pattern. These conclusions indicate that allocation decisions during laying are an important part of avian life-history strategies which are subject to energetic constraints and tradeoffs with other traits.

Oecologia↗

Total grain size distribution of an intense Hawaiian fountaining event: Case study of the1959 Kīlauea Iki eruption

The 1959 eruption of Kīlauea Iki on the Island of Hawai’i is a principal example of powerful Hawaiian fountaining. Over 36 days (including repose periods), 16 fountaining episodes created a small cone, a downwind tephra blanket of approximately 0.003 km 3 and a lava lake of about 0.04 km 3 volume. During the explosive activity, the maximum fountain heights reached 600 m. Based on a dataset of more than 450 tephra grain size samples, we present both a total grain size distribution (TGSD) of the entire downwind tephra deposit, and also TGSDs for two eruptive subunits (the opening and the closing stages). The opening stage was characterized by persistent fountaining over a period of 8 days with fountain heights averaging ∼ 100 m; in contrast, the closing stage was characterized by two short (hours-long) but powerful fountaining episodes (up to 600 m). The significantly different fountaining intensities are reflected in the characteristics of the TGSDs. For the closing stages, we link bimodality of TGSDs to periods of simultaneous deposition of ballistics and fallout from the convective cloud, both of which are a function of the maximum fountain height. The 1959 Kīlauea Iki case study presents a well-constrained set of TGSD data linked with Hawaiian-style fountaining of two contrasting intensities and can be used as a valuable reference point for eruption source parameters in future modeling of pyroclast dispersal during Hawaiian fountaining eruptions.

Hawaii↗

Bayesian analysis of the impact of rainfall data product on simulated slope failure for North Carolina locations

In the past decades, many different approaches have been developed in the literature to quantify the load-carrying capacity and geotechnical stability (or the Factor of Safety, F_s) of variably saturated hillslopes. Much of this work has focused on a deterministic characterization of hillslope stability. Yet, simulated F_s values are subject to considerable uncertainty due to our inability to characterize accurately the soil mantle’s properties (hydraulic, geotechnical and geomorphologic) and spatiotemporal variability of the moisture content of the hillslope interior. This is particularly true at larger spatial scales. Thus, uncertainty-incorporating analyses of physically based models of rain-induced landslides are rare in the literature. Such landslide modeling is typically conducted at the hillslope scale using gauge-based rainfall forcing data with rather poor spatiotemporal coverage. For regional landslide modeling, the specific advantages and/or disadvantages of gauge-only, radar-merged and satellite-based rainfall products are not clearly established. Here, we compare and evaluate the performance of the Transient Rainfall Infiltration and Grid-based Regional Slope-stability analysis (TRIGRS) model for three different rainfall products using 112 observed landslides in the period between 2004 and 2011 from the North Carolina Geological Survey database. Our study includes the Tropical Rainfall Measuring Mission (TRMM) Multi-satellite Precipitation Analysis Version 7 (TMPA V7), the North American Land Data Assimilation System Phase 2 (NLDAS-2) analysis, and the reference ‘truth’ Stage IV precipitation. TRIGRS model performance was rather inferior with the use of literature values of the geotechnical parameters and soil hydraulic properties from ROSETTA using soil textural and bulk density data from SSURGO (Soil Survey Geographic database). The performance of TRIGRS improved considerably after Bayesian estimation of the parameters with the DiffeRential Evolution Adaptive Metropolis (DREAM) algorithm using Stage IV precipitation data. Hereto, we use a likelihood function that combines binary slope failure information from landslide event and ‘null’ periods using multivariate frequency distribution-based metrics such as the False Discovery and False Omission Rates. Our results demonstrate that the Stage IV-inferred TRIGRS parameter distributions generalize well to TMPA and NLDAS-2 precipitation data, particularly at sites with considerably larger TMPA and NLDAS-2 rainfall amounts during landslide events than null periods. TRIGRS model performance is then rather similar for all three rainfall products. At higher elevations, however, the TMPA and NLDAS-2 precipitation volumes are insufficient and their performance with the Stage IV-derived parameter distributions indicate their inability to accurately characterize hillslope stability.

North Carolina↗

Isotopic evidence for the source of sulfur in the Upper Freeport coal bed (west-central Pennsylvania, U.S.A.)

Sulfur isotopic variations were used to determine the sources of sulfur in a medium-sulfur coal (???2 wt%S) that lacked marine influence, which is often cited as a major source of sulfur in coal. Variations in the amount and isotopic composition of the organic and pyritic sulfur among the coal-bed facies of the Upper Freeport coal bed (Middle Pennsylvanian) are attributed to differential incorporation of syngenetic and epigenetic sulfur. These variations reflect varying environmental conditions during paleopeat formation, porosity and permeability, and the availability of sulfate and iron. A large increase in the abundance and sulfur isotopic value of pyritic sulfur in the upper facies of the coal bed, in proximity to the overlying lacustrine shale, corresponds to an increase in massive and irregular forms of pyrite. This relationship is attributed to at least two stages of epigenetic pyrite incorporation. An early stage of epigenetic pyrite, moderately enriched in 34S, apparently formed during the fluvial-lacustrine period immediately following peat accumulation. A late stage of epigenetic pyrite, highly enriched in 34S, formed after compaction of the original peat as cleat- and fracture-filling pyrite; this sulfur was probably derived from bacterial reduction of dissolved sulfate in groundwater. Isotopic mass-balance calculations indicate that this late-stage epigenetic pyrite may account for up to ???50% of the pyritic sulfur in some upper facies of the coal bed. These results suggest that most of the pyritic sulfur in the Upper Freeport coal bed may be epigenetic, incorporated either soon after peat accumulation or later during coalification. ?? 1994.

Chemical Geology↗

Silicate melt inclusions and glasses in lunar soil fragments from the Luna 16 core sample

More than 2000 fragments were studied microscopically, and electron microprobe analyses were made of 39 selected areas, from a few square mm of polished surface, through 75- to 425-μm fragments of lunar soil from two samples of the Luna 16 core. The silicate melt inclusions and glasses differ in important details from those observed earlier in the Apollo samples. Melt inclusions in olivine contain epitaxially oriented daughter crystals, but also show a similar epitaxy around the outside of the crystals not observed in previous lunar samples. Melt inclusions in ilmenite suggest trapping at successive stages in a differentiation sequence. There is abundant evidence for late-stage silicate liquid immiscibility, with melt compositions similar but not identical to those from Apollo 11 and 12. A comparison of the alkali ratio of any given bulk rock analysis with that of its late-stage, high-silica melt shows gross differences for different rocks. This is pertinent to understanding late-stage differentiation processes. Glass fragments and spherules exhibit a wide range of crystallization textures, reflecting their wide range of compositions and cooling histories. No significant differences were found between the two portions of core examined (Zones A and D).

Earth and Planetary Science Letters↗

Evaluation of the efficiency of streamflow data collection strategies for alluvial rivers

Streamflow discharge is usually determined indirectly from measurements of the river stage at gaging stations and through the use of stage-discharge relationships (rating curves). However, in alluvial streams, stage-discharge relationships change continually and, sometimes, quite markedly. Such changes may be caused by major floods, seasonal variations, or long-term secular trends associated with changes in the river channel. Consequently, reliable estimates of discharge using rating curves are not possible unless frequent direct measurements of discharge are made. Such measurements involve appreciable costs, and it is important to evaluate their contribution in increasing the accuracy of estimation of quantities of interest such as mean daily, monthly or annual flow. A methodology for the evaluation of the efficiency of data-collection strategies for alluvial rivers is developed and applied to stations on the Missouri River, U.S.A. A flexible and expedient model describing the variability of discharges and shifts in the stage-discharge relationship is developed. Procedures for the estimation of parameters and the validation of the model using actual data are presented. The calibrated and validated model is then employed in simulations to evaluate the effect of sampling strategies (such as frequency and accuracy of discharge measurements) on the accuracy of estimated mean daily, monthly and annual flow. Curves relating the cost of sampling to the achieved accuracy can be generated, and the optimization of sampling strategies given accuracy or budget objectives or constraints can be achieved.

Journal of Hydrology↗

The geology, botany and chemistry of selected peat-forming environments from temperate and tropical latitudes

Peat has been studied in several geologic settings: (1) glaciated terrain in cold temperate Maine and Minnesota, U.S.A.; (2) an island in the Atlantic Ocean off the coast of Maine, where sea level is rising; (3) the warm temperate U.S. Atlantic and Gulf Coastal Plains, where sea level has changed often; and (4) the tropical coast of Sarawak, Malaysia, and the tropical delta of the Batang Hari River, Sumatra, Indonesia. Most of these deposits are domed (ombrotrophic or partly ombrotrophic) bogs in which peat accumulation continued above the surface of the surrounding soil. However, the bogs of the U.S. Atlantic and Gulf Coastal Plains are comparatively not as domed, and many have almost level surfaces. In some bogs, aquatic or semi-aquatic plant materials accumulated, replaced water in the depressions, and formed a surface on which marsh or swamp vegetation could subsequently live, die, and accumulate. In others, the plant materials accumulated initially on level silt or sand surfaces supporting marshes or swamps. As the peat dome formed, plants growing on it changed from luxuriant ones near the base of the dome, where nutrients were brought into the bog by surface and ground water, to stunted ones at the top of the dome, where the raised bogs are fed by nutrient-poor precipitation. The physical and chemical changes that take place in the sequence of environments from the pond stage of deposit development, through the grassy marsh stage, through the forested swamp stage, and finally through the heath dome stage can be measured in terms of acidity and ash, volatile matter, carbon, hydrogen, nitrogen, sulfur and oxygen contents, as well as in the kind and distribution of trace elements. The organic and inorganic contents of the deposits relate to geomorphology, and geomorphology relates to their settings. As models of coal formation, some domed peat deposits may help in solving problems of distribution and character of ancient coal beds. But clearly not all peat deposits are precursors of coal. Most Holocene peat deposits are subject to destruction by erosion, fire and decomposition through microbial and chemical oxidation before burial. The best environments for coal precursors have biomass accumulation, a continuously rising water table within the mass, and minimum influx of clay and silt until preservation by burial. The most suitable settings for future economic coal deposits are domed bogs that accumulate thick, widespread peat having low ash and low sulfur contents. The ombrotrophic peat deposits of tropical Sarawak and Sumatra are thick and extensive, contain low-ash and low-sulfur peat, and have high heating values. They are considered to be the best tropical coal analogs because of their extent and chances of preservation; the base of the peat is below adjacent river levels, and chemical and structural conditions are favorable for accumulation.

International Journal of Coal Geology↗

Rates of zinc and trace metal release from dissolving sphalerite at pH 2.0-4.0

High-Fe and low-Fe sphalerite samples were reacted under controlled pH conditions to determine nonoxidative rates of release of Zn and trace metals from the solid-phase. The release (solubilization) of trace metals from dissolving sphalerite to the aqueous phase can be characterized by a kinetic distribution coefficient, (Dtr), which is defined as [(Rtr/X(tr)Sph)/(RZn/X(Zn) Sph)], where R is the trace metal or Zn release rate, and X is the mole fraction of the trace metal or Zn in sphalerite. This coefficient describes the relationship of the sphalerite dissolution rate to the trace metal mole fraction in the solid and its aqueous concentration. The distribution was used to determine some controls on metal release during the dissolution of sphalerite. Departures from the ideal Dtr of 1.0 suggest that some trace metals may be released via different pathways or that other processes (e.g., adsorption, solubility of trace minerals such as galena) affect the observed concentration of metals. Nonoxidative sphalerite dissolution (mediated by H+) is characterized by a "fast" stage in the first 24-30 h, followed by a "slow" stage for the remainder of the reaction. Over the pH range 2.0-4.0, and for similar extent of reaction (reaction time), sphalerite composition, and surface area, the rates of release of Zn, Fe, Cd, Cu, Mn and Pb from sphalerite generally increase with lower pH. Zinc and Fe exhibit the fastest rates of release, Mn and Pb have intermediate rates of release, and Cd and Cu show the slowest rates of release. The largest variations in metal release rates occur at pH 2.0. At pH 3.0 and 4.0, release rates show less variation and appear less dependent on the metal abundance in the solid. For the same extent of reaction (100 h), rates of Zn release range from 1.53 ?? 10-11 to 5.72 ?? 10-10 mol/m2/s; for Fe, the range is from 4.59 ?? 10-13 to 1.99 ?? 10-10 mol/m2/s. Trace metal release rates are generally 1-5 orders of magnitude slower than the Zn or Fe rates. Results indicate that the distributions of Fe and Cd are directly related to the rate of sphalerite dissolution throughout the reaction at pH 3.0 and 4.0 because these two elements substitute readily into sphalerite. These two metals are likely to be more amenable to usage in predictive acid dissolution models because of this behavior. The Pb distribution shows no strong relation to sphalerite dissolution and appears to be controlled by pH-dependent solubility, most likely related to trace amounts of galena. The distribution of Cu is similar to that of Fe but is the most-dependent of all metals on its mole fraction ratio (Zn:Cu) in sphalerite. The Mn distributions suggest an increase in the rate of Mn release relative to sphalerite dissolution occurs in low Mn samples as pH increases. The Mn distribution in high Mn samples is nearly independent of pH and sphalerite dissolution at pH 2.0 but shows a dependence on these two parameters at higher pH (3.0-4.0).

Applied Geochemistry↗

Relationships between water and gas chemistry in mature coalbed methane reservoirs of the Black Warrior Basin

Water and gas chemistry in coalbed methane reservoirs of the Black Warrior Basin reflects a complex interplay among burial processes, basin hydrodynamics, thermogenesis, and late-stage microbial methanogenesis. These factors are all important considerations for developing production and water management strategies. Produced water ranges from nearly potable sodium-bicarbonate water to hypersaline sodium-chloride brine. The hydrodynamic framework of the basin is dominated by structurally controlled fresh-water plumes that formed by meteoric recharge along the southeastern margin of the basin. The produced water contains significant quantities of hydrocarbons and nitrogen compounds, and the produced gas appears to be of mixed thermogenic-biogenic origin. Late-stage microbial methanogenesis began following unroofing of the basin, and stable isotopes in the produced gas and in mineral cements indicate that late-stage methanogenesis occurred along a CO 2 -reduction metabolic pathway. Hydrocarbons, as well as small amounts of nitrate in the formation water, probably helped nourish the microbial consortia, which were apparently active in fresh to hypersaline water. The produced water contains NH 4 + and NH 3 , which correlate strongly with brine concentration and are interpreted to be derived from silicate minerals. Denitrification reactions may have generated some N 2 , which is the only major impurity in the coalbed gas. Carbon dioxide is a minor component of the produced gas, but significant quantities are dissolved in the formation water. Degradation of organic compounds, augmented by deionization of NH 4 + , may have been the principal sources of hydrogen facilitating late-stage CO 2 reduction.

Alabama↗

Contrasting demographic responses under future climate for two populations of a montane amphibian

For species with complex life histories, climate change can have contrasting effects for different life stages within locally adapted populations and may result in responses counter to general climate change predictions. Using data from two, 14-year demographic studies for a North American montane amphibian, Cascades frog ( Rana cascadae ), we quantified how aspects of current climate influenced annual survival of larvae and adult stages and modeled the stochastic population growth rate (λ s ) of each population for current (1980–2006) and future periods (2080s). Climate drivers of survival for the populations were similar for larvae (i.e., decreases in precipitation lead to pond drying and mortality), but diverged for terrestrial stages where decreases in winter length and summer precipitation had opposite effects. By the 2080s, we predict one population will be in sharp decline (λ s = 0.90), while the other population will remain nearly stable (λ s = 0.99) in the absence of other stressors, such as mortality due to disease. Our case study demonstrates a result counter to many climate envelope predictions in that stage-specific responses to local climate and hydrology result in a higher extinction risk for the more northern population.

California, Oregon, Washington↗

Effects of Phos-Chek® G75-F and Silv-Ex® on red-winged blackbird ( Agelaius phoeniceus ) embryos

Effects of field application levels of wildfire control chemicals, Phos-Chek ® G75-F (PC) and Silv-Ex ® (SE), were examined on red-winged blackbird ( Agelaius phoeniceus ) embryos. Embryos were more sensitive to PC and SE when eggs were immersed for 10 s at an early developmental stage (days 3–5 of incubation) than at a later stage (days 6–9 of incubation). The LC 50 (concentration causing 50% mortality) for early stage embryos exposed to PC was 213.3 g/L (slope = 1.6; 95% confidence interval [CI] = 129.1–326.1). The no observed effect concentration (NOEC) was below 135 g PC/L, which caused a significant increase in embryonic mortality and represents the lowest field coverage level of 1 gal/100 feet 2 . The LC 50 for early stage embryos exposed to SE was 19.8 g/L (slope = 1.5; 95% CI = 11.7–52.2). Significant mortality was observed at 10 g SE/L and marginal at 7.5 g SE/L with an apparent NOEC around 5 g SE/L. Neither chemical resulted in apparent developmental malformations.

Environmental Pollution↗

Near-term spatial hydrologic forecasting in Everglades, USA for landscape planning and ecological forecasting

Operational ecological forecasting is an emerging field that leverages ecological models in a new, cross-disciplinary way – using a real-time or nearly real-time climate forecast to project near-term ecosystem states. These applications give decision-makers lead time to anticipate and manage state changes that degrade ecosystem functions or directly impact humans. The Everglades Forecasting model (EverForecast) is an operational forecast model designed specifically for conservation management purposes including water management. It provides up to six-month forecasts of daily projected, spatially continuous stage values across the Everglades. We validated EverForecast quarterly to measured historical values at 207 gages (1 Jan 2000 – 31 Dec 2019). EverForecast hindcasted water stage accurately captured measured stage variation, with a low percentage of measured stage exceeding hindcasted values. Over the whole spatial extent, the mean RMSE is 20.98 cm, the mean MAE is 14.42 cm, and the mean MBE is 0.91 cm.

Florida↗