Reactivity of ammonium chloride/mercuric chloride mixtures with monel containers. The new compounds (NH4)(2)(NH3)(x)[Ni(NH3)(2)Cl-4] and (NH4)(5)Cl-2[CuCl2][CuCl4]

Ammonium chloride/mercuric chloride mixtures (molar ratio 2: 1) react at 350degreesC with Monel (Cu68Ni32) to yield (NH4)NiCl3 and mercury and copper amalgam, respectively. With larger amounts of (NH4)Cl in the reaction mixture, dark green (NH4)(2)(NH3)(x)[Ni(NH3)(2)Cl-4] (x approximate to 0.77) (1) is also formed as a main product. Light blue crystals of the mixed-valent copper(I,II) chloride (NH4)(5)Cl-5[CuCl2][CuCl4] (2) were obtained as a minor byproduct from a 4:1 reaction mixture. The crystal structures were determined from single crystal X-ray data; (1): tetragonal, I4/mmm, a = 770.9(1), e = 794.2(2) pm, 190 reflections, R-1 = 0.0263; (2): tetragonal, I4/mcm, a = 874.8(1), c = 2329.2(3) pm, 451 reflections, R-1 = 0.0736. In (1) Ni2+ resides in trans-[Ni(NH3)(2)Cl-4](2-) octahedra, and in (2) copper(l) is linearly two-coordinated in ECUC121- and copper(II) resides in a flattened tetrahedron [CuCl4](2-) with a tetrahedricity of 89%. (C) 2001 Elsevier Science.

Thermophysical properties of ammonium-based bis{(trifluoromethyl)sulfonyl} imide ionic liquids: Volumetric and transport properties

Density, rheological properties, and conductivity of a homologous series of ammonium-based ionic liquids N-alkyl-triethylammonium bis{(trifluoromethyl) sulfonyl}imide were studied at atmospheric pressure as a function of alkyl chain length on the cation, as well as of the temperature from (293.15 to 363.15) K. From these investigations, the effect of the cation structure was quantified on each studied properties, which demonstrated, as expected, a decrease of the density and conductivity, a contrario of an increase of the viscosity with the alkyl chain length on the ammonium cation. Furthermore, rheological properties were measured for both pure and water-saturated ionic liquids. The studied ionic liquids were found to be Newtonian and non-Arrhenius. Additionally, the effect of water content in the studied ionic liquids on their viscosity was investigated by adding water until they were saturated at 293.15 K. By comparing the viscosity of pure ionic liquids with the data measured in water-saturated samples, it appears that the presence of water decreases dramatically the viscosity of ionic liquids by up to three times. An analysis of involved transport properties leads us to a classification of the studied ionic liquids in terms of their ionicity using the Walden plot, from which it is evident that they can be classified as "good" ionic liquids. Finally, from measured density data, different volumetric properties, that is, molar volumes and thermal expansion coefficients were determined as a function of temperature and of cationic structure. Based on these volumetric properties, an extension of Jacquemin's group contribution model has been then established and tested for alkylammonium-based ionic liquids within a relatively good uncertainty close to 0.1 %. © 2012 American Chemical Society.

Mutual Solubilities of Ammonium-Based Ionic Liquids with Water and with Water/Methanol Mixture

Over the last two decades, ionic liquids have gained importance as alternative solvents to conventional VOCs in the field of homogeneous catalysis. This success is not only due to their ability to dissolve a large amount of metal catalysts, but it is also due to their potential to enhance yields of enantiopure products. The art of preparation of a specific enantiomer is a highly desired one and searched for in pharmaceutical industry. This work presents a study on solubility in water and in water/methanol mixture of a set of ILs composed of the bis (trifluoromethylsulfonyl) imide anion and of the N-alkyl-triethyl-ammonium cation (abbrev. [NR,222][NTf2]) with the alkyl chain R ranging from 6 to 12 carbons. Mutual solubilities between ILs and water, as well as between ILs and methanol/water mixture were investigated in detail. These solubilities were measured using two well-known and accurate experimental techniques based on a volumetric and a cloud-point methods. Both methods enabled us to measure the Tx diagrams reflecting the mutual solubilities between water (or water/methanol) and selected ILs in the temperature range from 293.15 to 338.15 K. The data were fitted by using the modified Flory-Huggins equation proposed by de Sousa and Rebelo and compared also with the prediction carried out by the Cosmo-RS methodology

High temperature thermal stability investigations of ammonium sulphide passivated InGaAs and interface formation with Al2O3 studied by synchrotron radiation based photoemission

High resolution synchrotron radiation core level photoemission measurements have been used to undertake a comparative study ofthe high temperature thermal stability ofthe ammonium sulphide passivated InGaAs surface and the same surface following the atomic layer deposition (ALD) of an ultrathin (∼1 nm) Al2O3 layer. The solution based ex situ sulphur passivation was found to be effective at removing a significant amount of the native oxides and protecting the surface against re-oxidation upon air exposure. The residual interfacial oxides which form between sulphur passivated InGaAs and the ultrathin Al2O3 layer can be substantially removed at high temperature (up to 700 ◦C) without impacting on the InGaAs stoichiometry while significant loss of indium was recorded at this temperature on the uncovered sulphur passivated InGaAs surface.

Development of a modified flyash as a permeable reactive barrier media for a former manufactured gas plant site Northern Ireland

A sequential biological permeable reactive barrier (PRB) was determined to be the best option for remediating groundwater that has become contaminated with a wide range of organic contaminants (i.e., benzene, toluene, ethylbenzene, xylene and polyaromatic hydrocarbons), heavy metals (i.e., lead and arsenic), and cyanide at a former manufactured gas plant after 150 years of operation in Portadown, Northern Ireland. The objective of this study was to develop a modified flyash that could be used in the initial cell within a sequential biological PRB to filter complex contaminated groundwater containing ammonium. Flyash modified with lime (CaOH) and alum was subjected to a series of batch tests which investigated the modified cation exchange capacity (CEC) and rate of removal of anions and cations from the solution. These tests showed that a high flyash composition medium (80%) could remove 8.65 mol of ammonium contaminant for every kilogram of medium. The modified CEC procedure ruled out the possibility of cation exchange as the major removal mechanism. The medium could also adsorb anions as well as cations (i.e., Pb and Cr), but not with the same capacity. The initial mechanism for Pb and Cr removal is probably precipitation. This is followed by sorption, which is possibly the only mechanism for the removal of dichromate anions. Scanning electron microscopic analysis revealed very small (

Elucidation of the electrochemical oxidation pathway of ammonia in dimethylformamide and the room temperature ionic liquid, 1-ethyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide

The direct electrochemical oxidation of ammonia has been examined in both the organic solvent dimethylformamide (DMF) and the room temperature ionic liquid 1-ethyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide [EMIM][N(Tf)(2)]. The corresponding voltammetric responses have been shown to be similar in each solvent with a broad oxidative wave occurring upon the introduction of ammonia to the solution and the appearance of a new reductive wave following the oxidation. The oxidative reaction process has been examined and a suitable reaction pathway has been deduced, corresponding to the formation of ammonium cations after oxidation of the ammonia. A linear response of limiting current against vol% ammonia was observed in both DMF and [EMIM][N(Tf)(2)], suggesting potential application for analytical methods.

Fixed Bed Study of Ammonia Removal from Aqueous Solutions Using Natural Zeolite

Purpose
– The purpose of this paper is to investigate the performance of natural Jordanian zeolite tuff to remove ammonia from aqueous solutions using a laboratory batch method and fixed-bed column apparatus. Equilibrium data were fitted to Langmuir and Freundlich models.

Design/methodology/approach
– Column experiments were conducted in packed bed column. The used apparatus consisted of a bench-mounted glass column of 2.5 cm inside diameter and 100 cm height (column volume = 490 cm3). The column was packed with a certain amount of zeolite to give the desired bed height. The feeding solution was supplied from a 30 liter plastic container at the beginning of each experiment and fed to the column down-flow through a glass flow meter having a working range of 10-280ml/min.

Findings
– Ammonium ion exchange by natural Jordanian zeolite data were fitted by Langmuir and Freundlich isotherms. Continuous sorption of ammonium ions by natural Jordanian zeolite tuff has proven to be effective in decreasing concentrations ranging from 15-50 mg NH4-N/L down to levels below 1 mg/l. Breakthrough time increased by increasing the bed depth as well as decreasing zeolite particle size, solution flow-rate, initial NH4+ concentration and pH. Sorption of ammonium by the zeolite under the tested conditions gave the sorption capacity of 28 mg NH4-N/L at 20°C, and 32 mg NH4-N/L at 30°C.

Originality/value
– This research investigates the performance of natural Jordanian zeolite tuff to remove ammonia from aqueous solutions using a laboratory batch method and fixed-bed column apparatus. The equilibrium data of the sorption of Ammonia were plotted by using the Langmuir and Freundlich isotherms, then the experimental data were compared to the predictions of the above equilibrium isotherm models. It is clear that the NH4+ ion exchange data fitted better with Langmuir isotherm than with Freundlich model and gave an adequate correlation coefficient value.

Interannual and (multi-)decadal variability in the sedimentary BIT index of Lake Challa, East Africa, over the past 2200 years: assessment of the precipitation proxy

The branched vs. isoprenoid tetraether (BIT) index is based on the relative abundance of branched tetraether lipids (brGDGTs) and the isoprenoidal GDGT crenarchaeol. In Lake Challa sediments the BIT index has been applied as a proxy for local monsoon precipitation on the assumption that the primary source of brGDGTs is soil washed in from the lake's catchment. Since then, microbial production within the water column has been identified as the primary source of brGDGTs in Lake Challa sediments, meaning that either an alternative mechanism links BIT index variation with rainfall or that the proxy's application must be reconsidered. We investigated GDGT concentrations and BIT index variation in Lake Challa sediments at a decadal resolution over the past 2200 years, in combination with GDGT time-series data from 45 monthly sediment-trap samples and a chronosequence of profundal surface sediments.

Our 2200-year geochemical record reveals high-frequency variability in GDGT concentrations, and therefore in the BIT index, superimposed on distinct lower-frequency fluctuations at multi-decadal to century timescales. These changes in BIT index are correlated with changes in the concentration of crenarchaeol but not with those of the brGDGTs. A clue for understanding the indirect link between rainfall and crenarchaeol concentration (and thus thaumarchaeotal abundance) was provided by the observation that surface sediments collected in January 2010 show a distinct shift in GDGT composition relative to sediments collected in August 2007. This shift is associated with increased bulk flux of settling mineral particles with high Ti / Al ratios during March–April 2008, reflecting an event of unusually high detrital input to Lake Challa concurrent with intense precipitation at the onset of the principal rain season that year. Although brGDGT distributions in the settling material are initially unaffected, this soil-erosion event is succeeded by a massive dry-season diatom bloom in July–September 2008 and a concurrent increase in the flux of GDGT-0. Complete absence of crenarchaeol in settling particles during the austral summer following this bloom indicates that no Thaumarchaeota bloom developed at that time. We suggest that increased nutrient availability, derived from the eroded soil washed into the lake, caused the massive bloom of diatoms and that the higher concentrations of ammonium (formed from breakdown of this algal matter) resulted in a replacement of nitrifying Thaumarchaeota, which in typical years prosper during the austral summer, by nitrifying bacteria. The decomposing dead diatoms passing through the suboxic zone of the water column probably also formed a substrate for GDGT-0-producing archaea. Hence, through a cascade of events, intensive rainfall affects thaumarchaeotal abundance, resulting in high BIT index values.

Decade-scale BIT index fluctuations in Lake Challa sediments exactly match the timing of three known episodes of prolonged regional drought within the past 250 years. Additionally, the principal trends of inferred rainfall variability over the past two millennia are consistent with the hydroclimatic history of equatorial East Africa, as has been documented from other (but less well dated) regional lake records. We therefore propose that variation in GDGT production originating from the episodic recurrence of strong soil-erosion events, when integrated over (multi-)decadal and longer timescales, generates a stable positive relationship between the sedimentary BIT index and monsoon rainfall at Lake Challa. Application of this paleoprecipitation proxy at other sites requires ascertaining the local processes which affect the productivity of crenarchaeol by Thaumarchaeota and brGDGTs.

A microbial fuel cell in contaminated ground delineated by electrical self-potential and normalized induced polarization data

There is a growing interest in the use of geophysical methods to aid investigation and monitoring of complex biogeochemical environments, for example delineation of contaminants and microbial activity related to land contamination. We combined geophysical monitoring with chemical and microbiological analysis to create a conceptual biogeochemical model of processes around a contaminant plume within a manufactured gas plant site. Self-potential, induced polarization and electrical resistivity techniques were used to monitor the plume. We propose that an exceptionally strong (>800 mV peak to peak) dipolar SP anomaly represents a microbial fuel cell operating in the subsurface. The electromagnetic and electrical geophysical data delineated a shallow aerobic perched water body containing conductive gasworks waste which acts as the abiotic cathode of microbial fuel cell. This is separated from the plume below by a thin clay layer across the site. Microbiological evidence suggests that degradation of organic contaminants in the plume is dominated by the presence of ammonium and its subsequent degradation. We propose that the degradation of contaminants by microbial communities at the edge of the plume provides a source of electrons and acts as the anode of the fuel cell. We hypothesize that ions and electrons are transferred through the clay layer that was punctured during the trial pitting phase of the investigation. This is inferred to act as an electronic conductor connecting the biologically mediated anode to the abiotic cathode. Integrated electrical geophysical techniques appear well suited to act as rapid, low cost sustainable tools to monitor biodegradation.

Perturbed frequency-selective surfaces fabricated on large thin polymer membranes for multiband infrared applications

The design, fabrication, and characterization of single-screen perturbed frequency-selective surfaces (FSS) at infrared frequencies for single and multiband applications are reported. Single-band FSS based on parallel strips have been perturbed by decreasing the length of every second strip within the array in order to achieve dual band-stop responses. The same principle has been extended to design FSS exhibiting tri- and quadreflection bands. In addition, strip FSSs have been perturbed by replacing every second strip for a metallic ring, resulting in dual-band filters with different polarization responses of the bands. These designs have been fabricated on large thin polyimide membranes using sacrificial silicon wafers. An oxide interlayer between the sacrificial silicon wafer and the polyimide membrane is employed to stop the silicon etching and is wet etched subsequently by a solution of ammonium fluoride and acetic acid that does not attack either the polyimide membrane or the aluminium FSS elements. Fourier transform infrared spectroscopy measurements are presented to validate the predicted responses of the fabricated prototypes.

ZnO nanofluids: Green synthesis, characterization, and antibacterial activity

Zinc oxide nanoparticles have been synthesized by microwave decomposition of zinc acetate precursor using an ionic liquid, 1-butyl-3-methylimidazolium bis(trifluoromethylsulfonyl) imide, [bmim][NTf2] as a green solvent. The structure and morphology of ZnO nanoparticles have been characterized using X-ray diffraction and transmission electron microscopy. The ZnO nanofluids have been prepared by dispersing ZnO nanoparticles in glycerol as a base fluid in the presence of ammonium citrate as a dispersant. The antibacterial activity of suspensions of ZnO nanofluids against (E. coli) has been evaluated by estimating the reduction ratio of the bacteria treated with ZnO. Survival ratio of bacteria decreases with increasing the concentrations of ZnO nanofluids and time. The results show that an increase in the concentrations of ZnO nanofluids produces strong antibacterial activity toward E. coli. (C) 2010 Elsevier B.V. All rights reserved.

Distinct patterns of nitrate reductase activity in brown algae: Light and ammonium sensitivity in Laminaria digitata is absent in Fucus species

Fucus and Laminaria species, dominant seaweeds in the intertidal and subtidal zones of the temperate North Atlantic, experience tidal cycles that are not synchronized with light:dark (L:D) cycles. To investigate how nutrient assimilation is affected by light cycles, the activity of nitrate reductase (NR) was examined in thalli incubated in outdoor tanks with flowing seawater and natural L:D cycles. NR activity in Laminaria digitata (Huds.) Lamour. showed strong diel patterns with low activities in darkness and peak activities near midday. This diel pattern was controlled by light but not by a circadian rhythm. In contrast, there was no diel variation in NR activity in Fucus serratus L., F. vesiculosus (L.) Lamour., and F. spiralis L. either collected directly from the shore or maintained in the outdoor tanks. In laboratory cultures, transfer to continuous darkness suppressed NR activity in L. digitata, but not in F. vesiculosus; continuous light increased NR activity in L. digitata but decreased activity in F. vesiculosus. Furthermore, 4 d enrichment with ammonium (50 mu mol . L-1 pulses), resulted in NR activity declining by > 80% in L. digitata, but no significant changes in F. serratus. Seasonal differences in maximum NR activity were present in both genera with activities highest in late winter and lowest in summer. This is the first report of NR activity in any alga that is not strongly regulated by light and ammonium. Because light and tidal emersion do not always coincide, Fucus species may have lost the regulation of NR by light that has been observed in other algae and higher plants.