An X-ray photoelectron and absorption spectroscopic investigation of the electronic structure of cubanite, CuFe2S3

X-ray photoelectron and absorption spectra have been obtained for natural specimens of cubanite and compared with the corresponding spectra for chalcopyrite. Synchrotron X-ray photoelectron spectra of surfaces prepared by fracture under ultra-high vacuum revealed some clear differences for the two minerals, most notably those reflecting their different structures. In particular, the concentration of the low binding energy S species formed at cubanite fracture surfaces was approximately double that produced at chalcopyrite surfaces. However, the core electron binding energies for the two S environments in cubanite were not significantly different, and were similar to the corresponding values for the single environment in chalcopyrite. High binding energy features in the S 2p and Cu 2p spectra were not related to surface species produced either by the fracture or by oxidation, and most probably arose from energy loss due to inter-band excitation. Differences relating to the Fe electronic environments were detectable, but were smaller than expected from some of the observed physical properties and Mössbauer spectroscopic parameters for the two minerals. X-ray absorption and photoelectron spectra together with the calculated densities of states for cubanite confirmed an oxidation state of Cu^I in the mineral. It was concluded that the best formal oxidation state representation for cubanite is Cu^I(Fe₂)^VS ₃ ^?II .     

The significance of dilution in evaluating possible impacts of wastewater discharges from large cruise ships

In response to public concerns about discharges from large cruise ships, Alaska's Department of Environmental Conservation (ADEC) sampled numerous effluents in the summer of 2000. The data showed that basic marine sanitation device (MSD) technology for black water (sewage) was not performing as expected. Untreated gray water had high levels of conventional pollutants and surprisingly high levels of bacteria. Both black water and gray water discharges sometimes exceeded state water quality standards for toxicants. The state convened a Science Advisory Panel (the Panel) to evaluate impacts associated with cruise ship wastewater discharges. The effluent data received wide media coverage and increased public concerns. Consequently, legislative decisions were made at the State and Federal level, and regulations were imposed before the Panel completed its evaluation. The Panel demonstrated that following the rapid dilution from moving cruise ships, the effluent data from the Summer of 2000 would not have exceeded water quality standards, and environmental effects were not expected.     

Effect of water on the heat capacity of polymerized aluminosilicate glasses and melts

The effect of water on heat capacity has been determined for four series of hydrated synthetic aluminosilicate glasses and supercooled liquids close to albite, phonolite, trachyte, and leucogranite compositions. Heat capacities were measured at atmospheric pressure by differential scanning calorimetry for water contents between 0 and 4.9 wt % from 300 K to about 100 K above the glass transition temperature (T_g). The partial molar heat capacity of water in polymerized aluminosilicate glasses, which can be considered as independent of composition, is (J/mol K). In liquids containing at least 1 wt % H₂O, the partial molar heat capacity of water is about 85 J/mol K. From speciation data, the effects of water as hydroxyl groups and as molecular water have tentatively been estimated, with partial molar heat capacities of 153 ± 18 and 41 ± 14 J/mol K, respectively. In all cases, water strongly increases the configurational heat capacity at T_g and exerts a marked depressing effect on T_g, in close agreement with the results of viscosity experiments on the same series of glasses. Consistent with the Adam and Gibbs theory of relaxation processes, the departure of the viscosity of hydrous melts from Arrhenian variations correlates with the magnitude of configurational heat capacities.     

Silica and pyroxene in IVA irons; possible formation of the IVA magma by impact melting and reduction of L-LL-chondrite materials followed by crystallization and cooling

Group IVA is a large magmatic group of iron meteorites. The mean Δ¹⁷O (=δ¹⁷O − 0.52·δ¹⁸O) of the silicates is ∼+1.2‰, similar to the highest values in L chondrites and the lowest values in LL chondrites; δ¹⁸O values are also in the L/LL range. This strongly suggests that IVA irons formed by melting L-LL parental material, but the mean Ni content of IVA irons (83 mg/g) is much lower than that of a presumed L-LL parent (∼170 mg/g) and the low-Ca pyroxene present in two IVA meteorites is Fs13, much lower than the Fs20-29 values in L and LL chondrites. Thus, formation from L-LL precursors requires extensive addition of metallic Fe, probably produced by reduction of FeS and FeO. Group IVA also has S/Ni, Ga/Ni, and Ge/Ni ratios that are much lower than those in L-LL chondrites or any chondrite group that preserves nebular compositions, implying loss of these volatile elements during asteroidal processing. We suggest that these reduction and loss processes occurred near the surface of the asteroid during impact heating, and resulted partly from reduction by C, and partly from the thermal dissociation of FeS and FeO with loss of O and S. The hot (∼1770 K) low-viscosity melt quickly moved through channels in the porous asteroid to form a core. Two members of the IVA group, São João Nepomuceno (hereafter, SJN) and Steinbach, contain moderate amounts of orthopyroxene and silica, and minor amounts of low-Ca clinopyroxene. Even though SJN formed after ∼26% crystallization and Steinbach formed after ∼77% crystallization of the IVA core, both could have originated within several tens of meters of the core-mantle interface if 99% of the crystallization occurred from the center outwards. Two other members of the group (Gibeon and Bishop Canyon) contain tabular tridymite, which we infer to have initially formed as veins deposited from a cooling SiO-rich vapor. The silicates were clearly introduced into IVA irons after the initial magma crystallized. Because the γ-iron crystals in SJN are typically about 5 cm across, an order of magnitude smaller than in IVA irons that do not contain massive silicates, we infer that the metal was in the γ-iron field when the silicates were injected. The SJN and Steinbach silicate compositions are near the low-Ca-pyroxene/silica eutectic compositions. We suggest that a tectonic event produced a eutectic-like liquid and injected it together with unmelted pyroxene grains into fissures in the solid metal core. Published estimates of IVA metallographic cooling rates range from 20 to 3000 K/Ma, leading to a hypothesized breakup of the core during a major impact followed by scrambling of the core and mantle debris [Haack, H., Scott, E.R.D., Love, S.G., Brearley, A. 1996. Thermal histories of IVA stony-iron and iron meteorites: evidence for asteroid fragmentation and reaccretion. Geochim. Cosmochim. Acta60, 3103-3113]. This scrambling model is physically implausible and cannot explain the strong correlation of estimated cooling rates with metal composition. Previous workers concluded that the low-Ca clinopyroxene in SJN and Steinbach formed from protopyroxene by quenching at a cooling rate of 10¹² K/Ma, and suggested that this also supported an impact-scrambling model. This implausible spike in cooling rate by a factor of 10¹⁰ can be avoided if the low-Ca clinopyroxene were formed by a late shock event that converted orthopyroxene to clinopyroxene followed by minimal growth in the clinopyroxene field, probably because melt was also produced. We suggest that metallographic cooling-rate estimates (e.g., based on island taenite) giving similar values throughout the metal compositional range are more plausible, and that the IVA parent asteroid can be modeled by monotonic cooling followed by a high-temperature impact event that introduced silicates into the metal and a low-temperature impact event that partially converted orthopyroxene into low-Ca clinopyroxene.     

Size‐based differences in isotopic niche width (δ13C and δ15N) of green turtles (Chelonia mydas) nesting on Príncipe Island,Gulf of Guinea

Within the same population, nesting green turtles (Chelonia mydas) might exploit different niches by exhibiting polymorphic foraging strategies and/or inhabiting geographically distinct foraging areas. This is crucial information for the conservation of this species. Here, we used stable carbon and nitrogen isotope ratios (δ¹³C and δ¹⁵N) to test for differences in a population of green turtles nesting on Príncipe Island (1°37′N; 7°24?′E), Central Africa. A total of 60 nesting females were sampled on the two main nesting beaches of the island in December 2012. Minimum curved carapace length (CCL) was recorded, and δ¹³C and δ¹⁵N values were measured in the epidermis of each individual. Overall, CCL varied from 87.0 to 108.0 cm (mean ± SD =100.0 ± 5.1), δ¹³C values from ?19.4 to ?8.6‰ (?17.3 ± 1.8) and δ¹⁵N values from 7.9 to 17.3‰ (13.6 ± 1.5). Despite the large variation in both isotopic ratios, their distributions were unimodal, showing an absence of polymorphic foraging strategies and isotopically distinct foraging areas. However, smaller females (< median, 100.8 cm) occupied a much larger isotopic niche (i.e., four times greater) than larger females. These results suggest that nesting green turtles may forage opportunistically on the resources available in each of their foraging home ranges, with smaller females venturing to more isotopic‐diversified areas and/or exhibiting broader foraging strategies than larger females. In addition, and in accordance with other studies, findings suggest that the foraging grounds used by the Príncipe green turtle nesting females are distributed mainly throughout the Gulf of Guinea.     

Determining groundwater degradation from irrigation in desert-marginal northern China

Groundwater degradation from irrigated agriculture is of concern in semi-arid northern China. Data-scarcity often means the causes and extent of problems are not fully understood. An irrigated area in Inner Mongolia was studied, where abstraction from an unconfined Quaternary aquifer has increased threefold over 20 years to 20 million m³/year; groundwater levels are falling at up to 0.5 m/year; and groundwater is increasingly mineralised (TDS increase from 400 to 700–1,900 mg/L), with nitrate concentrations up to 137 mg/L N. Residence-time (chlorofluorocarbons), stable-isotope and hydrogeochemical indicators helped develop a conceptual model of groundwater system evolution, demonstrating a direct relationship between modern water proportion and the degree of groundwater mineralisation, indicating that irrigation-water recycling is reducing groundwater quality. The investigations suggest that before irrigation development, active recharge to the aquifer from wadis significantly exceeded groundwater inflow from nearby mountains, previously held to be the main groundwater input. Away from active wadis, groundwater is older with a probable pre-Holocene component. Proof-of-concept groundwater modelling supports geochemical evidence, indicating the importance of wadi recharge and irrigation return flows. Engineering works protecting the irrigated area from flooding have reduced good quality recharge; active recharge is now dominated by irrigation returns, which are degrading the aquifer.     

Are 3C 120 and Other Active Galactic Nuclei Overweight Microquasars?

The appearance of superluminal radio knots follows drops in the X-ray flux in the FR1 radio galaxy 3C 120 and possibly the FR2 source 3C 111. This corresponds in a very general way to the behavior of the X-ray binary GRS 1915 + 105, but the light curves of the microquasar are much richer in detail. Starting in 2003.7, the character of the radio and X-ray light curves of 3C 120 changed, perhaps signaling a new stage of activity. I discuss here what one might expect when a microquasar is scaled up to AGN dimensions, and compare this with what we see in 3C 120. There is a mismatch between expectations and observations.     

Tolerance of ciliated protozoan Paramecium bursaria （Protozoa,Ciliophora） to ammonia and nitrites

The tolerance to ammonia and nitrites in freshwater ciliate Paramecium bursaria was measured in a conventional open system. The ciliate was exposed to different concentrations of ammonia and nitrites for 2h and 12h in order to determine the lethal concentrations. Linear regression analysis revealed that the 2h-LC50 value for ammonia was 95.94 mg/L and for nitrite 27.35 mg/L using probit scale method (with 95% confidence intervals). There was a linear correlation between the mortality probit scale and logarithmic concentration of ammonia which fit by a regression equation y=7.32x-9.51 (R^2=0.98; y, mortality probit scale; x, logarithmic concentration of ammonia), by which 2 h-LC50 value for ammonia was found to be 95.50 mg/L. A linear correlation between mortality probit scales and logarithmic concentration of nitrite is also followed the regression equation y=2.86x 0.89 (R^2=0.95; y, mortality probit scale; x, logarithmic concentration of nitrite). The regression analysis of toxicity curves showed that the linear correlation between exposed time of ammonia-N LC50 valueand ammonia-N LC50 value followed the regression equation y=2 862.85e-0.08x (R^2=0.95; y, duration of exposure to LC50 value; x, LC50 value), and that between exposed time of nitrite-N LC50 value and nitrite-N LC50 value followed the regression equation y = 127.15e-0.13x (R^2=0.91; y, exposed time of LC50 value; x, LC50 value). The results demonstrate that the tolerance to ammonia in P. bursaria is considerably higher than that of the larvae or juveniles of some metozoa, e.g. cultured prawns and oysters. In addition, ciliates, as bacterial predators, are likely to play a positive role in maintaining and improving water quality in aquatic environments with high-level ammonium, such as sewage treatment systems.