Inorganic ion composition in Tardigrada: cryptobionts contain a large fraction of unidentified organic solutes.

PubMed

Halberg, Kenneth Agerlin; Larsen, Kristine Wulff; Jørgensen, Aslak; Ramløv, Hans; Møbjerg, Nadja

2013-04-01

Many species of tardigrades are known to tolerate extreme environmental stress, yet detailed knowledge of the mechanisms underlying the remarkable adaptations of tardigrades is still lacking, as are answers to many questions regarding their basic biology. Here, we present data on the inorganic ion composition and total osmotic concentration of five different species of tardigrades (Echiniscus testudo, Milnesium tardigradum, Richtersius coronifer, Macrobiotus cf. hufelandi and Halobiotus crispae) using high-performance liquid chromatography and nanoliter osmometry. Quantification of the ionic content indicates that Na(+) and Cl(-) are the principal inorganic ions in tardigrade fluids, albeit other ions, i.e. K(+), NH4(+), Ca(2+), Mg(2+), F(-), SO4(2-) and PO4(3-) were also detected. In limno-terrestrial tardigrades, the respective ions are concentrated by a large factor compared with that of the external medium (Na(+), ×70-800; K(+), ×20-90; Ca(2+) and Mg(2+), ×30-200; F(-), ×160-1040, Cl(-), ×20-50; PO4(3-), ×700-2800; SO4(2-), ×30-150). In contrast, in the marine species H. crispae, Na(+), Cl(-) and SO4(2-) are almost in ionic equilibrium with (brackish) salt water, while K(+), Ca(2+), Mg(2+) and F(-) are only slightly concentrated (×2-10). An anion deficit of ~120 mEq l(-1) in M. tardigradum and H. crispae indicates the presence of unidentified ionic components in these species. Body fluid osmolality ranges from 361±49 mOsm kg(-1) in R. coronifer to 961±43 mOsm kg(-1) in H. crispae. Concentrations of most inorganic ions are largely identical between active and dehydrated groups of R. coronifer, suggesting that this tardigrade does not lose large quantities of inorganic ions during dehydration. The large osmotic and ionic gradients maintained by both limno-terrestrial and marine species are indicative of a powerful ion-retentive mechanism in Tardigrada. Moreover, our data indicate that cryptobiotic tardigrades contain a large fraction of unidentified organic osmolytes, the identification of which is expected to provide increased insight into the phenomenon of cryptobiosis.

A re-assessment of aerosol size distributions from Masaya volcano (Nicaragua)

NASA Astrophysics Data System (ADS)

Martin, R. S.; Ilyinskaya, E.; Sawyer, G. M.; Tsanev, V. I.; Oppenheimer, C.

2011-01-01

Cascade impactors were used to sample volcanic aerosol from Masaya (Nicaragua) in 2007, 2009 and 2010. Differences were found in the size distributions of volcanic aerosol between these recent campaigns and with a campaign in 2001: (1) SO 42- showed modes in both the fine (<1 μm; with low Na +/K +) and coarse (>1 μm; with high Na +/K +) fractions in all of the recent campaigns despite being unimodal in 2001 (<1 μm); (2) The modal diameters for SO 42- roughly doubled in 2009, compared to 2007 or 2010; (3) total Cl - was depleted in volcanic aerosol compared to background aerosol in all the more recent campaigns but was enriched in 2001. Other aspects of the volcanic aerosol appear to be persistent, such as a fine SO 42--H +-Na +-K + mode, which was the most abundant mode in all campaigns, and a coarse Cl --F --Mg 2+-Ca 2+ mode of lower abundance. Water uptake and speciation in the aerosol were investigated using the equilibrium model, ISORROPIA II. Results show that the coarse SO 42--rich mode deliquesces at lower relative humidity (40% RH) than the fine SO 42--rich mode (50% RH) due to increased Na +/K + in the former. The aerosol was predicted to be dry at ambient relative humidity in 2009 and dominated by NaHSO 4, KHSO 4, CaSO 4 and MgSO 4. In contrast, model results predict a liquid aerosol at ambient relative humidity in 2010. These results indicate that aerosol emissions from a volcano can vary in ionic composition and even more so in physical speciation (i.e., salts or solutions). These observations are set against a near-constant magmatic gas composition at Masaya, which highlights the significance of atmospheric and dynamic factors in the formation of volcanic aerosols.

Silver(I) complexes of the weakly coordinating solvents SO(2) and CH(2)Cl(2): crystal structures, bonding, and energetics of [Ag(OSO)][Al{OC(CF(3))(3)}(4)], [Ag(OSO)(2/2)][SbF(6)], and [Ag(CH(2)Cl(2))(2)][SbF(6)].

PubMed

Decken, Andreas; Knapp, Carsten; Nikiforov, Grigori B; Passmore, Jack; Rautiainen, J Mikko; Wang, Xinping; Zeng, Xiaoqing

2009-06-22

Pushing the limits of coordination chemistry: The most weakly coordinated silver complexes of the very weakly coordinating solvents dichloromethane and liquid sulfur dioxide were prepared. Special techniques at low temperatures and the use of weakly coordinating anions allowed structural characterization of [Ag(OSO)][Al{OC(CF(3))(3)}(4)], [Ag(OSO)(2/2)][SbF(6)], and [Ag(Cl(2)CH(2))(2)][SbF(6)] (see figure). An investigation of the bonding shows that these complexes are mainly stabilized by electrostatic monopole-dipole interactions.The synthetically useful solvent-free silver(I) salt Ag[Al(pftb)(4)] (pftb=--OC(CF(3))(3)) was prepared by metathesis reaction of Li[Al(pftb)(4)] with Ag[SbF(6)] in liquid SO(2). The solvated complexes [Ag(OSO)][Al(pftb)(4)], [Ag(OSO)(2/2)][SbF(6)], and [Ag(CH(2)Cl(2))(2)][SbF(6)] were prepared and isolated by special techniques at low temperatures and structurally characterized by single-crystal X-ray diffraction. The SO(2) complexes provide the first examples of coordination of the very weak Lewis base SO(2) to silver(I). The SO(2) molecule in [Ag(OSO)][Al(pftb)(4)] is eta(1)-O coordinated to Ag(+), while the SO(2) ligands in [Ag(OSO)(2/2)][SbF(6)] bridge two Ag(+) ions in an eta(2)-O,O' (trans,trans) manner. [Ag(CH(2)Cl(2))(2)][SbF(6)] contains [Ag(CH(2)Cl(2))(2)](+) ions linked through [SbF(6)](-) ions to give a polymeric structure. The solid-state silver(I) ion affinities (SIA) of SO(2) and CH(2)Cl(2), based on bond lengths and corresponding valence units in the corresponding complexes and tensimetric titrations of Ag[Al(pftb)(4)] and Ag[SbF(6)] with SO(2) vapor, show that SO(2) is a weaker ligand to Ag(+) than the commonly used weakly coordinating solvent CH(2)Cl(2) and indicated that binding strength of SO(2) to silver(I) in the silver(I) salts increases with increasing size of the corresponding counteranion ([Al(pftb)(4)](-)>[SbF(6)](-)). The experimental findings are in good agreement with theoretical gas-phase ligand-binding energies of [Ag(L)(n)](+) (L=SO(2), CH(2)Cl(2); n=1, 2) and solid-state enthalpies obtained from Born-Fajans-Haber cycles by using the volume-based thermodynamics (VBT) approach. Bonding analysis (VB, NBO, MO) of [Ag(L)(n)](+) suggests that these complexes are almost completely stabilized by electrostatic interaction, that is, monopole-dipole interaction, with almost no covalent contribution by electron donation from the ligand orbitals into the vacant 5s orbital of Ag(+). All experimental findings and theoretical considerations demonstrate that SO(2) is less covalently bound to Ag(+) than CH(2)Cl(2) and support the thesis that SO(2) is a polar but non-coordinating solvent towards Ag(+).

The formation of supercooled brines, viscous liquids, and low-temperature perchlorate glasses in aqueous solutions relevant to Mars

NASA Astrophysics Data System (ADS)

Toner, J. D.; Catling, D. C.; Light, B.

2014-05-01

Salt solutions on Mars can stabilize liquid water at low temperatures by lowering the freezing point of water. The maximum equilibrium freezing-point depression possible, known as the eutectic temperature, suggests a lower temperature limit for liquid water on Mars; however, salt solutions can supercool below their eutectic before crystallization occurs. To investigate the magnitude of supercooling and its variation with salt composition and concentration, we performed slow cooling and warming experiments on pure salt solutions and saturated soil-solutions of MgSO4, MgCl2, NaCl, NaClO4, Mg(ClO4)2, and Ca(ClO4)2. By monitoring solution temperatures, we identified exothermic crystallization events and determined the composition of precipitated phases from the eutectic melting temperature. Our results indicate that supercooling is pervasive. In general, supercooling is greater in more concentrated solutions and with salts of Ca and Mg. Slowly cooled MgSO4, MgCl2, NaCl, and NaClO4 solutions investigated in this study typically supercool 5-15 °C below their eutectic temperature before crystallizing. The addition of soil to these salt solutions has a variable effect on supercooling. Relative to the pure salt solutions, supercooling decreases in MgSO4 soil-solutions, increases in MgCl2 soil-solutions, and is similar in NaCl and NaClO4 soil-solutions. Supercooling in MgSO4, MgCl2, NaCl, and NaClO4 solutions could marginally extend the duration of liquid water during relatively warm daytime temperatures in the martian summer. In contrast, we find that Mg(ClO4)2 and Ca(ClO4)2 solutions do not crystallize during slow cooling, but remain in a supercooled, liquid state until forming an amorphous glass near -120 °C. Even if soil is added to the solutions, a glass still forms during cooling. The large supercooling effect in Mg(ClO4)2 and Ca(ClO4)2 solutions has the potential to prevent water from freezing over diurnal and possibly annual cycles on Mars. Glasses are also potentially important for astrobiology because of their ability to preserve pristine cellular structures intact compared to solutions that crystallize.

Natural contamination with arsenic and other trace elements in groundwater of the Central-West region of Chaco, Argentina.

PubMed

Blanes, Patricia S; Buchhamer, Edgar E; Giménez, María C

2011-01-01

This study covered the central agricultural region of the Chaco province, which lacks a permanent river networks. However, during the rainy period there is localized groundwater recharge. About 84 groundwater samples were taken during the period April-December 2007. These groundwater samples were collected from two different depths: 62 samples from shallow wells (4 to 20 m) and 24 samples from deep wells (20 to 100 m). Chemical variables were determined: pH, specific conductance, total dissolved solid, hardness, alkalinity, HCO(3)-, CO(3)(2-), SO(4)(2-), Cl-, NO(3)-, NO(2) -, NH(4)+, F-, As((tot)), Na+, K+, Ca2+, Mg2+, Fe, Cu, Ni, Pb and Zn. The chemical composition of groundwater in the study area is dominantly sodium bicarbonate and sodium chloride bicarbonate, comprising more than 60% (52/86) of shallow and deep groundwater samples. Of the 86 analyzed groundwater samples, 88% exceeded the WHO (World Health Organization) and CAA (Código Alimentario Argentino) standards (10 μg/L) for As (arsenic) and 9% exceeded the WHO standard (1.5 mg/L) for F(-).Groundwater highly contaminated with As (max. 1,073 μg/L) and F- (max. 4.2 mg/L) was found in shallow aquifer. The contaminated groundwater is characterized by high pH (max. 8.9), alkalinity (max. HCO(3)- 1,932 mg/L), SO(4)(2-) (max. 11,862 mg/L), Na(+) (max. 3,158 mg/L), Cl(-) (max. 10,493 mg/L) and electric conductivity greater than 33.3 μS/cm. Other associated elements (Ni, Pb, Cu and Zn) are present in low concentrations, except for Fe that in 32% of samples exceeded the guideline value of 0.3 mg/L suggested by the CAA.

Chemical characteristics of ambient aerosols contributed by cooking process at Noorpur village near New Delhi

NASA Astrophysics Data System (ADS)

Singh, Sudha

Generally, industrial and transport sectors are considered as major contributors of air pollution but recently, biomass burning is also reported as a major source of atmospheric aerosols (1, 2) especially in the developing world where solid fuels such as dung cake, wood and crop residues are used in traditional cooking which are responsible for poor air quality, respiratory problems and radiative forcing etc .In India, most of the research has been focused on emission estimates from biomass burning and cooking. No effort has been made to understand the chemistry and sources of fine aerosols in rural areas during cooking hours. This study fills this knowledge gap and strengthens our understanding about abundance of various chemical constituents of atmospheric aerosols emitted during cooking hours.Aerosol samples were collected from village called Noorpur (28.470 N, 77.030 E) which lies near Delhi city. Sampling was carried out during August 2011-May 2012 by using handy sampler (Envirotech model APM 821) installed at the terrace of a building (~6m). The aerosol samples were collected on 8 hourly basis at a flow rate of 1 LPM. Water extracts of these filters were analyzed for major anions (F-, Cl-, NO3-, SO42-) and major cations (Na+, NH4+, K+, Ca2+ Mg2+) by ion chromatography (Metrohm 883 Basic IC Plus). During cooking period, the concentration of the major ions followed the order of Ca2+> SO42-> NO3-> Cl-> K+> NH4+> Mg2+> Na2+> F-. Among anion SO42 (5 µg/m3) showed highest value and in case of cations Ca2+ (7.32µg/m3) has highest value.

Major impact of volcanic gases on the chemical composition of precipitation in Iceland during the 2014-2015 Holuhraun eruption

NASA Astrophysics Data System (ADS)

Stefánsson, Andri; Stefánsson, Gerdur; Keller, Nicole S.; Barsotti, Sara; Sigurdsson, Árni; Thorláksdóttir, Svava Björk; Pfeffer, Melissa Anne; Eiríksdóttir, Eydís. S.; Jónasdóttir, Elín. Björk; von Löwis, Sibylle; Gíslason, Sigurdur R.

2017-02-01

The Holuhraun eruption in 2014-2015 was the largest in Iceland for more than 200 years. It resulted in emissions of large quantities of volcanic gases into the atmosphere (11 megaton (Mt) SO2, 0.1 Mt HCl, and 0.05 Mt HF). During the eruption the volcanic gases had major effects on F, SO4 and to a lesser extent Cl concentrations in precipitaxtion throughout Iceland, effects not observed in recent decades. The concentrations of F, Cl, and SO4 (n = 705) reached values of 444 µm 12,270 µm, and 17,324 µm during the eruption and were on average 20 times higher for F and SO4 and much lower for Cl compared to preeruption times. The concentrations of major cations (Si, Na, K, Ca, Mg, Al, and Fe) (n = 151) in the precipitation were taken as having originated from seawater spray and dissolution of rock dust and aerosol. Based on the mixing model developed here, it is demonstrated that the source of the enrichment of F and SO4 was indeed the volcanic gas emissions with >60-100 mol % of SO4 and F in the precipitation originated from volcanic gas, whereas the Cl originated mostly from seawater spray, making the volcanic gas input of Cl relatively less important than for F and SO4. The results showed that large volcanic eruptions can have major effects on atmospheric chemistry and impact the composition of precipitation.

Preparation and characterization of [H2-DABCO][ClO4]2 as a new member of DABCO-based ionic liquids for the synthesis of pyrimido[4,5-b]-quinoline and pyrimido[4,5-d]pyrimidine derivatives

NASA Astrophysics Data System (ADS)

Shirini, Farhad; Langarudi, Mohaddeseh Safarpoor Nikoo; Daneshvar, Nader; Jamasbi, Negar; Irankhah-Khanghah, Mahsa

2018-06-01

[H2-DABCO][ClO4]2, as a novel DABCO-based ionic liquid, has been synthesized, characterized, and used as an affordable and recyclable catalyst in the synthesis of pyrimido [4,5-b]-quinoline and pyrimido [4,5-d]pyrimidine derivatives. The procedure shows several advantages over the previous methods such as simplicity, high yields, short reaction times, easy work-up, and use of a non-metal catalyst. Moreover, this paper virtually debates the impact of anions and cations on moisture-resistant property and catalytic activity in DABCO-based ionic liquids through the comparison of [DABCO](SO3H)2(Cl)2, [DABCO](SO3H)2(HSO4)2, [H2-DABCO][H2PO4]2, [H2-DABCO][HSO4]2, and [H2-DABCO][ClO4]2.

Evolution of aerosol chemistry in Xi'an, inland China, during the dust storm period of 2013 - Part 1: Sources, chemical forms and formation mechanisms of nitrate and sulfate

NASA Astrophysics Data System (ADS)

Wang, G. H.; Cheng, C. L.; Huang, Y.; Tao, J.; Ren, Y. Q.; Wu, F.; Meng, J. J.; Li, J. J.; Cheng, Y. T.; Cao, J. J.; Liu, S. X.; Zhang, T.; Zhang, R.; Chen, Y. B.

2014-11-01

A total suspended particulate (TSP) sample was collected hourly in Xi'an, an inland megacity of China near the Loess Plateau, during a dust storm event of 2013 (9 March 18:00-12 March 10:00 LT), along with a size-resolved aerosol sampling and an online measurement of PM2.5. The TSP and size-resolved samples were determined for elemental carbon (EC), organic carbon (OC), water-soluble organic carbon (WSOC) and nitrogen (WSON), inorganic ions and elements to investigate chemistry evolution of dust particles. Hourly concentrations of Cl-, NO3-, SO42-, Na+ and Ca2+ in the TSP samples reached up to 34, 12, 180, 72 and 28 μg m-3, respectively, when dust peak arrived over Xi'an. Chemical compositions of the TSP samples showed that during the whole observation period NH4+ and NO3- were linearly correlated with each other (r2=0.76) with a molar ratio of 1 : 1, while SO42- and Cl- were well correlated with Na+, Ca2+, Mg2+ and K+ (r2 > 0.85). Size distributions of NH4+ and NO3- presented a same pattern, which dominated in the coarse mode (> 2.1 μm) during the event and predominated in the fine mode (< 2.1 μm) during the non-event. SO42- and Cl- also dominated in the coarse mode during the event hours, but both exhibited two equivalent peaks in both the fine and the coarse modes during the non-event, due to the fine-mode accumulations of secondarily produced SO42- and biomass-burning-emitted Cl- and the coarse-mode enrichments of urban soil-derived SO42- and Cl-. Linear fit regression analysis further indicated that SO42- and Cl- in the dust samples possibly exist as Na2SO4, CaSO4 and NaCl, which directly originated from Gobi desert surface soil, while NH4+ and NO3- in the dust samples exist as NH4NO3. We propose a mechanism to explain these observations in which aqueous phase of dust particle surface is formed via uptake of water vapor by hygroscopic salts such as Na2SO4 and NaCl, followed by heterogeneous formation of nitrate on the liquid phase and subsequent absorption of ammonia. Our data indicate that 54 ± 20% and 60 ± 23% of NH4+ and NO3- during the dust period were secondarily produced via this pathway, with the remaining derived from the Gobi desert and Loess Plateau, while SO42- in the event almost entirely originated from the desert regions. Such cases are different from those in the East Asian continental outflow region, where during Asia dust storm events SO42- is secondarily produced and concentrates in sub-micrometer particles as (NH4)2SO4 and/or NH4HSO4. To the best of our knowledge, the current work for the first time revealed an infant state of the East Asian dust ageing process in the regions near the source, which is helpful for researchers to understand the panorama of East Asian dust ageing process from the desert area to the downwind region.

Aerosol composition, chemistry, and source characterization during the 2008 VOCALS Experiment

DOE Office of Scientific and Technical Information (OSTI.GOV)

Lee, Y.; Springston, S.; Jayne, J.

2010-03-15

Chemical composition of fine aerosol particles over the northern Chilean coastal waters was determined onboard the U.S. DOE G-1 aircraft during the VOCALS (VAMOS Ocean-Cloud-Atmosphere-Land Study) field campaign between October 16 and November 15, 2008. SO42-, NO3-, NH4+, and total organics (Org) were determined using an Aerodyne Aerosol Mass Spectrometer, and SO42-, NO3-, NH4+, Na+, Cl-, CH3SO3-, Mg2+, Ca2+, and K+ were determined using a particle-into-liquid sampler-ion chromatography technique. The results show the marine boundary layer (MBL) aerosol mass was dominated by non- sea-salt SO42- followed by Na+, Cl-, Org, NO3-, and NH4+, in decreasing importance; CH3SO3-, Ca2+, and K+more » rarely exceeded their respective limits of detection. The SO42- aerosols were strongly acidic as the equivalent NH4+ to SO42- ratio was only {approx}0.25 on average. NaCl particles, presumably of sea-salt origin, showed chloride deficits but retained Cl- typically more than half the equivalency of Na+, and are externally mixed with the acidic sulfate aerosols. Nitrate was observed only on sea-salt particles, consistent with adsorption of HNO3 on sea-salt aerosols, responsible for the Cl- deficit. Dust particles appeared to play a minor role, judging from the small volume differences between that derived from the observed mass concentrations and that calculated based on particle size distributions. Because SO42- concentrations were substantial ({approx}0.5 - {approx}3 {micro}g/m3) with a strong gradient (highest near the shore), and the ocean-emitted dimethylsulfide and its unique oxidation product, CH3SO3-, were very low (i.e., {le} 40 parts per trillion and <0.05 {micro}g/m3, respectively), the observed SO42- aerosols are believed to be primarily of terrestrial origin. Back trajectory calculations indicate sulfur emissions from smelters and power plants along coastal regions of Peru and Chile are the main sources of these SO4- aerosols. However, compared to observations, model calculations appeared to underestimate sulfate concentrations based on an existing emission inventory. The agreement between observations and model predictions of CO as well as total sulfur is reexamined in this work with a new emission inventory made available recently.« less

Kinetics of heterogeneous reactions of HO2 radical at ambient concentration levels with (NH4)2SO4 and NaCl aerosol particles.

PubMed

Taketani, Fumikazu; Kanaya, Yugo; Akimoto, Hajime

2008-03-20

The HO2 uptake coefficient (gamma) for inorganic submicrometer wet and dry aerosol particles ((NH4)2SO4 and NaCl) under ambient conditions (760 Torr and 296 +/- 2 K) was measured using an aerosol flow tube (AFT) coupled with a chemical conversion/laser-induced fluorescence (CC/LIF) technique. The CC/LIF technique enabled experiments to be performed at almost the same HO2 radical concentration as that in the atmosphere. HO2 radicals were injected into the AFT through a vertically movable Pyrex tube. Injector position-dependent profiles of LIF intensity were measured as a function of aerosol concentration. Measured gamma values for dry aerosols of (NH4)2SO4 were 0.04 +/- 0.02 and 0.05 +/- 0.02 at 20% and 45% relative humidity (RH), respectively, while those of NaCl were <0.01 and 0.02 +/- 0.01 at 20% and 53% RH, respectively. For wet (NH4)2SO4 aerosols, measured gamma values were 0.11 +/- 0.03, 0.15 +/- 0.03, 0.17 +/- 0.04, and 0.19 +/- 0.04, at 45%, 55%, 65%, and 75% RH, respectively, whereas for wet NaCl aerosols the values were 0.11 +/- 0.03, 0.09 +/- 0.02, and 0.10 +/- 0.02 for 53%, 63%, and 75% RH, respectively. Wet (NH4)2SO4 and NaCl aerosols doped with CuSO4 showed gamma values of 0.53 +/- 0.12 and 0.65 +/- 0.17, respectively. These results suggest that compositions, RH, and phase for aerosol particles are significant to HO2 uptake. Potential HO2 loss processes and their atmospheric contributions are discussed.

Responses of hydrochemical inorganic ions in the rainfall-runoff processes of the experimental catchments and its significance for tracing

USGS Publications Warehouse

Gu, W.-Z.; Lu, J.-J.; Zhao, X.; Peters, N.E.

2007-01-01

Aimed at the rainfall-runoff tracing using inorganic ions, the experimental study is conducted in the Chuzhou Hydrology Laboratory with special designed experimental catchments, lysimeters, etc. The various runoff components including the surface runoff, interflow from the unsaturated zone and the groundwater flow from saturated zone were monitored hydrometrically. Hydrochemical inorganic ions including Na+, K+, Ca2+, Mg2+, Cl-, SO42-, HCO3- + CO32-, NO3-, F-, NH4-, PO42-, SiO2 and, pH, EC, 18O were measured within a one month period for all processes of rainfall, various runoff components and groundwater within the catchment from 17 boreholes distributed in the Hydrohill Catchment, few soil water samples were also included. The results show that: (a) all the runoff components are distinctly identifiable from both the relationships of Ca2+ versus Cl-/SO42-, EC versus Na+/(Na+ + Ca2+) and, from most inorganic ions individually; (b) the variation of inorganic ions in surface runoff is the biggest than that in other flow components; (c) most ions has its lowermost concentration in rainfall process but it increases as the generation depths of runoff components increased; (d) quantitatively, ion processes of rainfall and groundwater flow display as two end members of that of other runoff components; and (e) the 18O processes of rainfall and runoff components show some correlation with that of inorganic ions. The results also show that the rainfall input is not always the main source of inorganic ions of various runoff outputs due to the process of infiltration and dissolution resulted from the pre-event processes. The amount and sources of Cl- of runoff components with various generation mechanisms challenge the current method of groundwater recharge estimation using Cl-.

Stoichiometry of water-soluble ions in PM2.5: Application in source apportionment for a typical industrial city in semi-arid region, Northwest China

NASA Astrophysics Data System (ADS)

Zhou, Haijun; Lü, Changwei; He, Jiang; Gao, Manshu; Zhao, Boyi; Ren, Limin; Zhang, Lijun; Fan, Qingyun; Liu, Tao; He, Zhongxiang; Dudagula; Zhou, Bin; Liu, Hualin; Zhang, Yu

2018-05-01

Water-soluble ions (WSIs) are major components of PM2.5 and it is valuable for understanding physical and chemical characteristics, sources, behaviors and formation mechanism of WSIs. Baotou is a traditionally industrial city in semi-arid region and frequently subjected to dust storms from March to May. In recent years, air pollution has been listed as one of the most important environmental problems in Baotou. To investigate the seasonal variations and sources of WSIs in PM2.5, the WSIs including SO42-, NO3-, Cl-, F-, NH4+, K+, Na+, Ca2+ and Mg2+ were monitored at six urban sites in Baotou. The results showed that high concentrations of Ca2+ and Na+ were found responding to dust storm events, while high concentrations of SO42-, NO3-, NH4+, K+ and Cl- were observed during haze days. The correlations analysis indicated that excess sulfuric and nitric acid was likely neutralized by carbonate minerals such as calcite, aragonite and dolomite in normal days and cations were fully neutralized during all the sampling periods, while cations were excessive in dust storm days. The concentrations of [NH4+ + SO42- + NO3-], [Na+ + Ca2+ + Mg2+] and [Cl- + K+ + F-] indicated the northwest and southeast region of Baotou presented comparatively high contributions of secondary aerosol and crustal dust, respectively, which were mainly related to the industrial distribution and urbanization process. The cluster analysis, ternary diagram and principal component analysis have a good agreement in source apportionment, where crustal dust sources, secondary aerosol source and the mixture of coal combustion, biomass burning and industrial pollution sources were the main sources of WSIs in PM2.5. The seasonal pattern of sulfur oxidation ratio (SOR) was September > April > November > January, while the nitrogen oxidation ratio (NOR) April > January > November > September in Baotou. This work evaluated the seasonal variation, distribution and source of WSIs on the basis of its stoichiometry in PM2.5, which help to explore the potential sources of these inorganic aerosols and provide scientific suggestion for air quality improvement in Baotou.

The origin of high sulfate concentrations in a coastal plain aquifer, Long Island, New York

USGS Publications Warehouse

Brown, C.J.; Schoonen, M.A.A.

2004-01-01

Ion-exchange batch experiments were run on Cretaceous (Magothy aquifer) clay cores from a nearshore borehole and an inland borehole on Long Island, NY, to determine the origin of high SO42- concentrations in ground water. Desorption batch tests indicate that the amounts of SO 42- released from the core samples are much greater (980-4700 ??g/g of sediment) than the concentrations in ground-water samples. The locally high SO42- concentrations in pore water extracted from cores are consistent with the overall increase in SO 42- concentrations in ground water along Magothy flow paths. Results of the sorption batch tests indicate that SO42- sorption onto clay is small but significant (40-120 ??g/g of sediment) in the low-pH (<5) pore water of clays, and a significant part of the SO42- in Magothy pore water may result from the oxidation of FeS2 by dissolved Fe(III). The acidic conditions that result from FeS2 oxidation in acidic pore water should result in greater sorption of SO42- and other anions onto protonated surfaces than in neutral-pH pore water. Comparison of the amounts of Cl- released from a clay core sample in desorption batch tests (4 ??g/g of sediment) with the amounts of Cl- sorbed to the same clay in sorption tests (3.7-5 ??g/g) indicates that the high concentrations of Cl- in pore water did not originate from connate seawater but were desorbed from sediment that was previously in contact with seawater. Furthermore, a hypothetical seawater transgression in the past is consistent with the observed pattern of sorbed cation complexes in the Magothy cores and could be a significant source of high SO42- concentrations in Magothy ground water.

A simple and efficient method for preparing partially purified phosvitin from egg yolk using ethanol and salts.

PubMed

Ko, K Y; Nam, K C; Jo, C; Lee, E J; Ahn, D U

2011-05-01

The objective of this study was to develop a new protocol that could be used for large-scale separation of phosvitin from egg yolk using ethanol and salts. Yolk granules, which contain phosvitin, were precipitated after diluting egg yolk with 9 volumes of distilled water. The pH of the yolk solution was adjusted to pH 4.0 to 8.0 using 6 N HCl or NaOH, and then yolk granules containing phosvitin was separated by centrifugation at 3,220 × g for 30 min. Lipids and phospholipids were removed from the insoluble yolk granules using 85% ethanol. The optimal volumes and concentration of ethanol in removing lipids from the precipitants were determined. After centrifugation, the lipid-free precipitants were homogenized with 9 volumes of ammonium sulfate [(NH(4))(2)SO(4)] or NaCl to extract phosvitin. The optimal pH and concentration of (NH(4))(2)SO(4) or NaCl for the highest recovery rate and purity for phosvitin in final solution were determined. At pH 6.0, all the phosvitin in diluted egg yolk solution was precipitated. Among the (NH(4))(2)SO(4) and NaCl conditions tested, 10% (NH(4))(2)SO(4) or 10% NaCl at pH 4.0 yielded the greatest phosvitin extraction from the lipid-free precipitants. The recovery rates of phosvitin using (NH(4))(2)SO(4) and NaCl were 72 and 97%, respectively, and their purity was approximately 85%. Salt was removed from the extract using ultrafiltration. The salt-free phosvitin solution was concentrated using ultrafiltration, the impurities were removed by centrifugation, and the resulting solution was freeze-dried. The partially purified phosvitin was suitable for human use because ethanol was the only solvent used to remove lipids, (NH(4))(2)SO(4) or NaCl was used to extract phosvitin, and ultrafiltration was used to remove salt and concentrate the extract. The developed method was simple and suitable for a large-scale preparation of partially purified phosvitin.

Size-resolved chemical composition of aerosol emitted by Erebus volcano, Antarctica

NASA Astrophysics Data System (ADS)

Ilyinskaya, E.; Oppenheimer, C.; Mather, T. A.; Martin, R. S.; Kyle, P. R.

2010-03-01

Persistent, open-vent degassing of Erebus volcano, Antarctica, is a significant point source of gases and aerosol to the austral polar troposphere. We report here on the chemical composition and size distribution of the Erebus aerosol, focusing on the water-soluble fraction. The aerosol was sampled at the rim of the active crater using a cascade impactor, which collected and sized particles in 14 size bins from >10 to 0.01 μm. The soluble fraction of the Erebus aerosol is distinct from other volcanic sources in several respects. It is dominated by chloride-bearing particles (over 30% of total mass) and has an unusually high Cl-/SO42- molar ratio of 3.5. Coarse particles contribute little to the total mass of the soluble fraction. Elevated concentrations of F-, Cl-, Br-, and SO42- are found in a narrow particle size fraction of 0.1-0.25 μm. The detection of particulate Br- reinforces our understanding of the potential for quiescent volcanic emissions to deplete tropospheric ozone. The small aerosol size reflects the low atmospheric temperature and humidity, which inhibit particle growth. Halide-alkali metal salts (Na, K)(Cl, F) appear to be the most abundant species in the aerosol. The concentration of Pb is high compared to other volcanoes; its exsolution may be promoted by the high abundance of halogens in Erebus magma. Despite the previously reported high NOx content in the plume, we did not detect significant quantities of nitrate in the near-vent aerosol. Our findings emphasize the potential regional significance of emissions from Erebus for understanding the Antarctic atmospheric composition and glaciochemical records.

Raman Spectroscopic Observations of the Ion Association between Mg(2+) and SO4(2-) in MgSO4-Saturated Droplets at Temperatures of ≤380 °C.

PubMed

Wan, Ye; Wang, Xiaolin; Hu, Wenxuan; Chou, I-Ming

2015-08-27

Liquid–liquid phase separation was observed in aqueous MgSO4 solutions with excess H2SO4 at elevated temperatures; the aqueous MgSO4/H2SO4 solutions separated into MgSO4-rich droplets (fluid F1) and a MgSO4-poor phase (fluid F2) during heating. The phase separation temperature increases with SO4(2–)/Mg2+ ratio at a constant MgSO4 concentration. At a MgSO4/H2SO4 ratio of 5, the liquid–liquid phase separation temperature decreases with an increase in MgSO4 concentration up to ∼1.0 mol/kg and then increases at higher concentrations, showing a typical macroscale property of polymer solutions with a lower critical solution temperature (LCST) of ∼271.4 °C. In situ Raman spectroscopic analyses show that the MgSO4 concentration in fluid F1 increases with an increase in temperature, whereas that in fluid F2 decreases with an increase in temperature. In addition, HSO4(–), which does not readily form complexes with Mg(2+), tends to accumulate in fluid F2. Analyses of the v1(SO4(2–)) bands confirmed the presence of four-sulfate species of unassociated SO4(2–) (∼980 cm(–1)), contact ion pairs (CIPs; ∼995 cm(–1)), and triple ion pairs (TIPs; ∼1005 cm(–1)) in aqueous solution, and more complex ion pair chain structure (∼1020 cm(–1)) in fluid F1. Comparison of the sulfate species in fluids F1 and F2 at 280 °C suggests that SO4(2–) in fluid F2 is less associated with Mg(2+). On the basis of in situ visual and Raman spectroscopic observations, we suggest that the formation of the complex Mg(2+)–SO4(2–) ion association might be responsible for the liquid–liquid phase separation. In addition, Raman spectroscopic analyses of the OH stretching bands indicate that the hydrogen bonding in fluid F1 is stronger than that in fluid F2, which might be ascribed to the increasing probability of collision of H2O with Mg(2+) and SO4(2–) in fluid F1.

Tetrahalide complexes of the [U(NR)2]2+ ion: synthesis, theory, and chlorine K-edge X-ray absorption spectroscopy.

PubMed

Spencer, Liam P; Yang, Ping; Minasian, Stefan G; Jilek, Robert E; Batista, Enrique R; Boland, Kevin S; Boncella, James M; Conradson, Steven D; Clark, David L; Hayton, Trevor W; Kozimor, Stosh A; Martin, Richard L; MacInnes, Molly M; Olson, Angela C; Scott, Brian L; Shuh, David K; Wilkerson, Marianne P

2013-02-13

Synthetic routes to salts containing uranium bis-imido tetrahalide anions [U(NR)(2)X(4)](2-) (X = Cl(-), Br(-)) and non-coordinating NEt(4)(+) and PPh(4)(+) countercations are reported. In general, these compounds can be prepared from U(NR)(2)I(2)(THF)(x) (x = 2 and R = (t)Bu, Ph; x = 3 and R = Me) upon addition of excess halide. In addition to providing stable coordination complexes with Cl(-), the [U(NMe)(2)](2+) cation also reacts with Br(-) to form stable [NEt(4)](2)[U(NMe)(2)Br(4)] complexes. These materials were used as a platform to compare electronic structure and bonding in [U(NR)(2)](2+) with [UO(2)](2+). Specifically, Cl K-edge X-ray absorption spectroscopy (XAS) and both ground-state and time-dependent hybrid density functional theory (DFT and TDDFT) were used to probe U-Cl bonding interactions in [PPh(4)](2)[U(N(t)Bu)(2)Cl(4)] and [PPh(4)](2)[UO(2)Cl(4)]. The DFT and XAS results show the total amount of Cl 3p character mixed with the U 5f orbitals was roughly 7-10% per U-Cl bond for both compounds, which shows that moving from oxo to imido has little effect on orbital mixing between the U 5f and equatorial Cl 3p orbitals. The results are presented in the context of recent Cl K-edge XAS and DFT studies on other hexavalent uranium chloride systems with fewer oxo or imido ligands.

Chemical characteristics of ambient aerosols contributed by cooking process at Noorpur village near Delhi (India)

NASA Astrophysics Data System (ADS)

Singh, Sudha; Kumar, Bablu; Gupta, Gyan Prakash; Kulshrestha, U. C.

2013-05-01

Combustion of fuels such as wood, crop residue and dung cakes etc. is one of the major sources of air pollution in developing countries. These fuels are still used commonly for cooking purpose in rural India. This study investigates the chemical composition of the ambient aerosols during cooking hours at a village called Noorpur (28.470 N, 77.030 E) which lies near Delhi city. Aerosol sampling was carried out during August 2011-May 2012 by using handy sampler (Envirotech model APM 821) installed at the terrace of a building (˜6m). The samples were collected on 8 hourly basis using Teflon filters. The water extract of these filters was analyzed for major anions (F-, Cl-, NO3-, SO42-) and major cations (Na+, NH4+, K+, Ca2+ Mg2+) by ion chromatography (Metrohm 883 Basic IC Plus). Results highlighted that cooking process contributed significant amount of SO42- and K+ṡ. Biomass burning is considered as a potential source of K+ in air. The high concentration of SO42- might be due to oxidation of SO2 contributed by the combustion of dung cakes. Further, the detailed results will be discussed during the conference.

Interactions of aerosols (ammonium sulfate, ammonium nitrate and ammonium chloride) and of gases (HCl, HNO 3) with fogwater

NASA Astrophysics Data System (ADS)

Ruprecht, Heidi; Sigg, Laura

The concentrations of aerosols (NH 4NO 3, (NH 4) 2SO 4 and NH 4Cl) and of gases (HCl (g), HNO 3(g), NH 3(g) were determined by denuder methods under different conditions (in the absence of fog, before, during and after fog events). At this site situated in an urban region, high concentrations of the gaseous strong acids HCl (g) and HNO 3(g) are observed. NH 4Cl and NH 4NO 3 aerosols represent a major fraction of the Cl - and NO 3- aerosols (<2.4 μm)collected by denuders. During a fog event, very high concentrations of SO 42- were found in small aerosols, which are attributed to the aqueous phase oxidation of SO 2 under the influence of high pH due to the presence of NH 3. Differences in SO 42- concentrations measured in aerosols (<2.4 μm) and in fog droplets were probably due to mass-transport limitations of the SO 2 oxidation. Ammonium sulfate aerosols represent in some cases a significant fraction of the total S present (SO 2(g) + SO 42-. Soluble aerosols and gases contribute to the composition of fogwater and are released again after fog dissipation.

Growth of sodium chlorate crystals in the presence of potassium sulphate

NASA Astrophysics Data System (ADS)

Kim, E. L.; Tsyganova, A. A.; Vorontsov, D. A.; Ovsetsina, T. I.; Katkova, M. R.; Lykov, V. A.; Portnov, V. N.

2015-09-01

In this work, we investigated the morphology and growth rates of NaClO3 crystals in solutions with K2SO4 additives. NaClO3 crystals were grown using the temperature gradient technique under concentration convection. We found that the crystal habitus changed from cubic to tetrahedral, and the growth of the cubic {100}, tetrahedral {111} and rhomb-dodecahedral {110} faces decelerated with an increase in the concentration of SO42- ions. The {110} face was the most and the {100} face was the least inhibited by sulphate ions. The mechanism of SO42- ions action is their adsorption on the crystal surface, which impedes attachment of the crystal's building units. We conclude that different atomic structure and charge state of various crystal faces determine their sensitivity to the action of the SO42- ions.

Sulfur, Chlorine and Fluorine Degassing and Atmospheric Loading by the Roza eruption, Columbia River Basalt Group, Washington

NASA Technical Reports Server (NTRS)

Thordarson, Th.; Self, S

1996-01-01

In this study we attempt to quantify the amount of S, Cl and F released by the 1300 cu km Roza member (approximately 14.7 Ma) of the Columbia River Basalt Group, which was produced by a moderate-size flood basalt eruption in the mid-Miocene. Our results are the first indication of the potential atmospheric SO2 yield from a flood basalt eruption, and indicate the mechanism by which flood basalt eruptions may have seriously affected the environment. Glass inclusions in phenocrysts and quenched glass in products from various stages of the eruption were analyzed for concentrations of S, Cl and F and major elements. Glass inclusions contain 1965 +/- 110 ppm S, 295 +/- 65 ppm Cl and 1310 +/- 110 ppm F. Groundmass glass of Roza dike selvages contains considerably lower concentrations: 1110 +/- 90 ppm S, 245 +/- 30 ppm Cl and 1020 +/- 25 ppm F. Scoria clasts from near vent deposits contain 665 +/- 75 ppm S, 175 +/- 5 ppm Cl and 950 +/- 20 ppm F, and the groundmass glass of lava selvages contains 520 +/- 30 ppm S, 190 +/- 30 ppm Cl and 890 +/- 55 ppm F. In crystalline lava, the concentrations are 195 ppm S, 100 ppm Cl and 830 ppm F. Volatile element concentrations in these samples represent the progress of degassing through the eruption and can be used to estimate the potential amount of the volatiles S, Cl and F released by the magma into the atmosphere, as well as to evaluate the amount liberated by various phases of the eruption. The total amount of volatiles released by the Roza eruption is estimated to have been approximately 12,420 MtSO2, approximately 710 MtHCI and approximately 1780 MtHF. The Roza magma liberated approximately 9620 MtSO, (77% of the total volatile mass released), approximately 400 MtHCI (56%) and approximately 1450 MtHF (81%) at the vents and lofted by the eruption columns to altitudes of 7-13 km. Degassing of the lava is estimated to have released an additional approximately 2810 MtSO2, approximately 310 MtHCI and approximately 330 MtHF. The Roza eruption is likely to have lasted for approximately 10 years, indicating an annual H2SO4-mass loading of approximately 1800 Mt. Thus, the atmospheric perturbations associated with the Roza eruption may have been of the magnitude predicted for a severe "nuclear" or "volcanic" winter, but lasting up to a decade or more.

A kinetic study of the interaction between atomic oxygen and aerosols

NASA Technical Reports Server (NTRS)

Akers, F. I.; Wightman, J. P.

1976-01-01

This study was concerned with the effects of NH4Cl and (NH4)2SO4 aerosols on the kinetics of disappearance of atomic oxygen. Atomic oxygen was generated by a 2.45-GHz microwave discharge and the kinetics of disappearance measured in a fast flow system using NO2 titration. Values of the recombination coefficient for heterogeneous wall recombination were determined for clean, H2SO4-coated, and (NH4)2SO4-coated Pyrex to be 0.000050, 0.000020, and 0.000019, respectively. A rapid exothermic chemical reaction was found to occur between atomic oxygen and an NH4Cl wall coating; the products were NH3, NO, H2O, and HCl. The NH4Cl aerosol was generated by gas phase reaction of NH3 with HCl. The aerosol particles were approximately spherical and nearly monodisperse with a mean diameter of 1.6 plus or minus 0.2 micron. The rate constant for the disappearance of atomic oxygen in the presence of NH4Cl aerosol was measured. No significant decrease was observed in the rate of disappearance of atomic oxygen in the presence of an (NH4)2SO4 aerosol at a concentration of 285 mg per cu m.

The State of Ambient Air Quality of Jeddah, Saudi Arabia

NASA Astrophysics Data System (ADS)

Hussain, M. M.; Aburizaiza, O. S.; Khwaja, H. A.; Siddique, A.; Nayebare, S. R.; Zeb, J.; Blake, D. R.

2014-12-01

Ambient air pollution in major cities of Saudi Arabia is a substantial environmental and health concern. A study was undertaken to assess the air quality of Jeddah, Saudi Arabia by the analysis of respirable particulate matter (PM2.5), black carbon (BC), trace metals (Na, Mg, Al, Si, S, Cl, K, Ca, Ti, V, Cr, Mn, Fe, Ni, Cu, Zn, Br, Sr, Cd, Sb, and Pb), and water-soluble ions (F-, Cl-, NO3-, SO42-, C2O42-, and NH42+). Sulfur and BC mass concentration ranged 0.99 - 7.39 μg/m3 and 0.70 - 3.09 μg/m3, respectively, while the PM2.5 mass concentration ranged 23 - 186 μg/m3. Maximum BC contribution to PM2.5 was 5.6%. Atmospheric PM2.5 concentrations were well above the 24 h WHO guideline of 20 μg/m3. Air Quality Index (AQI) indicates that there were 8% days of moderate air quality, 28% days of unhealthy air quality for sensitive groups, 55% days of unhealthy air quality, and 9% days of very unhealthy air quality during the study period. Sulfate SO42- dominated the identifiable components. The major contributors to PM2.5 were soil and crustal material; vehicle emissions (black carbon factor); and fuel oil combustion in industries (sulfur factor), according to the Positive Matrix Factorization (PMF). This study highlights the importance of focusing control strategies not only on reducing PM concentration, but also on the reduction of toxic components of the PM, to most effectively protect human health and the environment.

Testing a High-Sensitivity ATR FTIR Water Monitor for Ionic CWA Breakdown Products

DTIC Science & Technology

2003-12-31

for ClO4− (perchlorate) 37 The Limits of Detection for ClO3− (chlorate) 41 The Limits of Detection for PFOS− ( perfluorooctanesulfonate ) 44 The... perfluorooctanesulfonate (PFOS−), C8F17SO3−, perfluorobutanesulfonate (PFBS−), C4F9SO3−, trifluoromethanesulfonate, CF3SO3−, permanganate, MnO4−, perrhenate, ReO4...become a significant environmental concern in many western states.3 Perfluorooctanesulfonate was, for decades a key ingredient in aqueous film

Multivariate statistics as means of tracking atmospheric pollution trends in Western Poland.

PubMed

Astel, Aleksander M; Walna, Barbara; Simeonov, Vasil; Kurzyca, Iwona

2008-02-15

This study was carried out over a period of 4 years (2002-2005) at 2 sites located in western Poland differing as regards to human impact by analysis of chemical composition of bulk precipitation. The aim of the study was to determine the sources of pollutions and assess their quantitative contribution to the bulk precipitation composition and to analyse long term-changes in the chemical quality of precipitation. Based on this information the possible transboundary impacts of pollution were also determined. The samples were characterized by determining the values of pH, electrolytic conductivity and concentration levels of Cl(-), F(-), SO(4)(2-), NO(3)(-), Na(+), K(+), Mg(2+), Ca(2+) and NH(4)(+). Analytical measurements were connected with application of principal component regression (PCR) and time series analysis (TS). Based on PCR results three major sources of pollutants in central part of Poland have been identified and quantitatively assessed as follows: "combined" (Poznań - 31%, WNP - 32%), "soil-particulates" (Poznań - 2%, WNP - 26%), "anthropogenic-fossil fuels" (Poznań - 43%, WNP - 23%). Time series analysis enabled discovering 12-month time cycle for NO(3)(-), NH(4)(+), Cl(-), F(-) and SO(4)(2-) in average monthly concentration values in bulk precipitation collected in Wielkopolski National Park. Seasonal variation in the emission of precursors of NO(3)(-) and NH(4)(+) was caused by changes in intensity of fertilizer application in agriculture and automobile exhaust emissions. Decreasing trend was visible for sulphates, nitrates, chlorides and fluorides which is an important indication of the acid rain reduction in the ecologically protected area and in Poznań.

Theoretical studies of the nucleophilic substitution of halides and amine at a sulfonyl center.

PubMed

Sung, Dae Dong; Kim, Tae Joon; Lee, Ikchoon

2009-06-25

Gas-phase nucleophilic substitution reactions, F(-) + CH(3)SO(2)F, Cl(-) + CH(3)SO(2)Cl, Cl(-) + CH(3)SO(2)F, and NH(3) + CH(3)SO(2)Cl, have been investigated at the B3LYP/6-311+G** and MP2/6-31+G* levels of theory. A very shallow well for the reaction intermediate in a triple-well potential energy surface (PES) was observed for the identity fluoride exchange, but double well PESs were obtained for the other three reactions with three different PES profiles. NBO analyses of the transition states showed substantial charge transfer interactions in all cases which provided a much larger amount of stabilization energy compared with the corresponding species at the carbon center of methyl halides. This difference is primarily caused by the strong electropositive nature of the sulfur center. The F-S-F axial linkage in the distorted TBP type intermediate in the identity fluoride exchange reaction exhibited a weak three-center, four-electron omega-bonding, which is considered to provide stability of the intermediate. All the reactant (RC) and product complexes (PC) have Cs symmetry. The symmetry plane bisects angles HCH (of methyl group), OSO (of sulfonyl group), and HNH (of ammonia). Vicinal charge transfer interactions between the two out-of-plane C-H, S-O, and N-H bonds provide extra stabilization to the ion-dipole complexes together with H-bond formation of in-plane H atom with the nucleophile and/or leaving group.

The major-ion composition of Carboniferous seawater

NASA Astrophysics Data System (ADS)

Holt, Nora M.; García-Veigas, Javier; Lowenstein, Tim K.; Giles, Peter S.; Williams-Stroud, Sherilyn

2014-06-01

The major-ion chemistry (Na+, Mg2+, Ca2+, K+, SO42-, and Cl-) of Carboniferous seawater was determined from chemical analyses of fluid inclusions in marine halites, using the cryo scanning electron microscopy (Cryo-SEM) X-ray energy-dispersive spectrometry (EDS) technique. Fluid inclusions in halite from the Mississippian Windsor and Mabou Groups, Shubenacadie Basin, Nova Scotia, Canada (Asbian and Pendleian Substages, 335.5-330 Ma), and from the Pennsylvanian Paradox Formation, Utah, USA, (Desmoinesian Stage 309-305 Ma) contain Na+-Mg2+-K+-Ca2+-Cl- brines, with no measurable SO42-, which shows that the Carboniferous ocean was a “CaCl2 sea”, relatively enriched in Ca2+ and low in SO42- with equivalents Ca2+ > SO42- + HCO3-. δ34S values from anhydrite in the Mississippian Shubenacadie Basin (13.2-14.0 ‰) and the Pennsylvanian Paradox Formation (11.2-12.6 ‰) support seawater sources. Br in halite from the Shubenacadie Basin (53-111 ppm) and the Paradox Basin (68-147 ppm) also indicate seawater parentages. Carboniferous seawater, modeled from fluid inclusions, contained ∼22 mmol Ca2+/kg H2O (Mississippian) and ∼24 mmol Ca2+/kg H2O (Pennsylvanian). Estimated sulfate concentrations are ∼14 mmol SO42-/kg H2O (Mississippian), and ∼12 mmol SO42-/kg H2O (Pennsylvanian). Calculated Mg2+/Ca2+ ratios are 2.5 (Mississippian) and 2.3 (Pennsylvanian), with an estimated range of 2.0-3.2. The fluid inclusion record of seawater chemistry shows a long period of CaCl2 seas in the Paleozoic, from the Early Cambrian through the Carboniferous, when seawater was enriched in Ca2+ and relatively depleted in SO42-. During this ∼200 Myr interval, Ca2+ decreased and SO42- increased, but did not cross the Ca2+-SO42- chemical divide to become a MgSO4 sea (when SO42- in seawater became greater than Ca2+) until the latest Pennsylvanian or earliest Permian (∼309-295 Ma). Seawater remained a MgSO4 sea during the Permian and Triassic, for ∼100 Myr. Fluid inclusions also record a long interval, from the Early Cambrian to the Middle Devonian, when seawater had low Mg2+/Ca2+ ratios (<2) that coincide with calcite seas. The Mg2+/Ca2+ ratio of seawater rose from 0.9 in the Middle Devonian, to 2.5 in the Middle/Late Mississippian, 2.3 in the Middle Pennsylvanian, and 3.5 in the Early Permian. The transition from calcite seas to aragonite seas, established from the mineralogy of oölites and early marine cements, occurred in the Late Mississippian. Fluid inclusions show that seawater Mg2+/Ca2+ ratios rose above 2 by the Middle to Late Mississippian coinciding exactly with the shift to aragonite seas. Aragonite seas existed for ∼100 Myr, from the Late Mississippian until the Late Triassic/Early Jurassic.

Measuring and modeling the salting-out effect in ammonium sulfate solutions.

PubMed

Wang, Chen; Lei, Ying Duan; Endo, Satoshi; Wania, Frank

2014-11-18

The presence of inorganic salts significantly influences the partitioning behavior of organic compounds between environmentally relevant aqueous phases, such as seawater or aqueous aerosol, and other, nonaqueous phases (gas phase, organic phase, etc.). In this study, salting-out coefficients (or Setschenow constants) (KS [M(-1)]) for 38 diverse neutral compounds in ammonium sulfate ((NH4)2SO4) solutions were measured using a shared headspace passive dosing method and a negligible depletion solid phase microextraction technique. The measured KS were all positive, varied from 0.216 to 0.729, and had standard errors in the range of 0.006-0.060. Compared to KS for sodium chloride (NaCl) in the literature, KS values for (NH4)2SO4 are always higher for the same compound, suggesting a higher salting-out effect of (NH4)2SO4. A polyparameter linear free energy relationship (pp-LFER) for predicting KS in (NH4)2SO4 solutions was generated using the experimental data for calibration. pp-LFER predicted KS agreed well with measured KS reported in the literature. KS for (NH4)2SO4 was also predicted using the quantum-chemical COSMOtherm software and the thermodynamic model AIOMFAC. While COSMOtherm generally overpredicted the experimental KS, predicted and experimental values were correlated. Therefore, a fitting factor needs to be applied when using the current version of COSMOtherm to predict KS. AIOMFAC tends to underpredict the measured KS((NH4)2SO4) but always overpredicts KS(NaCl). The prediction error is generally larger for KS(NaCl) than for KS((NH4)2SO4). AIOMFAC also predicted a dependence of KS on the salt concentrations, which is not observed in the experimental data. In order to demonstrate that the models developed and calibrated in this study can be applied to estimate Setschenow coefficients for atmospherically relevant compounds involved in secondary organic aerosol formation based on chemical structure alone, we predicted and compared KS for selected α-pinene oxidation products.

Metastable Solution Thermodynamic Properties and Crystal Growth Kinetics

NASA Technical Reports Server (NTRS)

Kim, Soojin; Myerson, Allan S.

1996-01-01

The crystal growth rates of NH4H2PO4, KH2PO4, (NH4)2SO4, KAl(SO4)2 central dot 12H2O, NaCl, and glycine and the nucleation rates of KBr, KCl, NaBr central dot 2H2O, (NH4)2Cl, and (NH4)2SO4 were expressed in terms of the fundamental driving force of crystallization calculated from the activity of supersaturated solutions. The kinetic parameters were compared with those from the commonly used kinetic expression based on the concentration difference. From the viewpoint of thermodynamics, rate expressions based on the chemical potential difference provide accurate kinetic representation over a broad range of supersaturation. The rates estimated using the expression based on the concentration difference coincide with the true rates of crystallization only in the concentration range of low supersaturation and deviate from the true kinetics as the supersaturation increases.

Comparisons of plutonium, thorium, and cerium tellurite sulfates.

PubMed

Lin, Jian; Cross, Justin N; Diwu, Juan; Meredith, Nathan A; Albrecht-Schmitt, Thomas E

2013-04-15

The hydrothermal reaction of PuCl3 or CeCl3 with TeO2 in the presence of sulfuric acid under the comparable conditions results in the crystallization of Pu(TeO3)(SO4) or Ce2(Te2O5)(SO4)2, respectively. Pu(TeO3)(SO4) and its isotypic compound Th(TeO3)(SO4) are characterized by a neutral layer structure with no interlamellar charge-balancing ions. However, Ce2(Te2O5)(SO4)2 possesses a completely different dense three-dimensional framework. Bond valence calculation and UV-vis-NIR spectra indicate that the Ce compound is trivalent whereas the Pu and Th compounds are tetravalent leading to the formation of significantly different compounds. Pu(TeO3)(SO4), Th(TeO3)(SO4), and Ce2(Te2O5)(SO4)2 represent the first plutonium/thorium/cerium tellurite sulfate compounds. Our study strongly suggests that the chemistries of Pu and Ce are not the same, and this is another example of the failure of Ce as a surrogate.

Leachability and phytoavailability of nitrogen, phosphorus, and potassium from different bio-composts under chloride- and sulfate-dominated irrigation water.

PubMed

Ahmad, Zahoor; Yamamoto, Sadahiro; Honna, Toshimasa

2008-01-01

Concerns over increased phosphorus (P) application with nitrogen (N)-based compost application have shifted the trend to P-based composed application, but focusing on one or two nutritional elements does not serve the goals of sustainable agriculture. The need to understand the nutrient release and uptake from different composts has been further aggravated by the use of saline irrigation water in the recent scenario of fresh water shortage. Therefore, we evaluated the leachability and phytoavailability of P, N, and K from a sandy loam soil amended with animal, poultry, and sludge composts when applied on a total P-equivalent basis (200 kg ha(-1)) under Cl(-) (NaCl)- and SO4(2-) (Na2SO4)-dominated irrigation water. Our results showed that the concentration of dissolved reactive P (DRP) was higher in leachates under SO(4)(2-) than Cl(-) treatments. Compost amendments differed for DRP leaching in the following pattern: sludge > animal > poultry > control. Maize (Zea mays L.) growth and P uptake were severely suppressed under Cl(-) irrigation compared with SO4(2-) and non-saline treatments. All composts were applied on a total P-equivalent basis, but maximum plant (shoot + root) P uptake was observed under sludge compost amendment (73.4 mg DW(-1)), followed by poultry (39.3 mg DW(-1)), animal (15.0 mg DW(-1)), and control (1.2 mg DW(-1)) treatment. Results of this study reveal that irrigation water dominated by SO4(2-) has greater ability to replace/leach P, other anions (NO3(-)), and cations (K+). Variability in P release from different bio-composts applied on a total P-equivalent basis suggested that P availability is highly dependent on compost source.

Optical sensing of hydrogen sulphate using rhodamine 6G hydrazide from aqueous medium

NASA Astrophysics Data System (ADS)

Upadhyay, Yachana; Bothra, Shilpa; Kumar, Rajender; Choi, Heung-Jin; Sahoo, Suban K.

2017-06-01

This communication reports the application of rhodamine 6G hydrazide (L) for the selective colorimetric and turn-on fluorescent sensing of hydrogen sulphate ions from aqueous medium. The ring opening of the colourless spirocyclic form of L was selectively triggered in the presence of HSO4- among the other tested anions (F-, Cl-, Br-, I-, AcO-, H2PO4-, NO3-, ClO4-, CN-, HO-, AsO33 - and SO42 -), which gives rise to a pink colour and strong fluorescence in the visible region. Sensor L showed a detection limit down to micromolar range without any interference from the other tested competitive anions. Sensor L was applied for the construction of two inputs (HO- and HSO4-) INHIBIT type molecular logic gate and naked-eye detection of HSO4- using test paper strips.

Hydrogeochemical characterization of fluoride rich groundwater of Wailpalli watershed, Nalgonda District, Andhra Pradesh, India.

PubMed

Reddy, A G S; Reddy, D V; Rao, P N; Prasad, K Maruthy

2010-12-01

The groundwater of Nalgonda district is well known for its very high fluoride content for the past five decades. Many researchers have contributed their scientific knowledge to unravel causes for fluoride enrichment of groundwater. In the present paper, an attempt has been made to relate the high fluoride content in the groundwater to hydrogeochemical characterization of the water in a fracture hard rock terrain--the Wailpally watershed. Groundwater samples collected from all the major geomorphic units in pre- and post-monsoon seasons were analyzed for its major ion constituents such as Ca(2+), Mg(2+), Na(+), K(+), CO3-, HCO3-, Cl(-), SO4(-2), NO3-, and F(-). The groundwaters in the watershed have the average fluoride content of 2.79 mg/l in pre-monsoon and 2.83 mg/l in post-monsoon. Fluoride concentration in groundwater does not show perceptible change neither with time nor in space. The ionic dominance pattern is in the order of Na(+) > Ca(2+) > Mg(2+) > K(-) among cations and HCO3- Cl(-) > SO4(-2) NO3- F(-) among anions in pre-monsoon. In post-monsoon, Mg replaces Ca(2+) and NO3- takes the place of SO4(-2). The Modified Piper diagram reflect that the water belong to Ca(+2)-Mg(+2)-HCO3- to Na(+)-HCO3- facies. Negative chloralkali indices in both the seasons prove that ion exchange between Na(+) and K(+) in aquatic solution took place with Ca(+2) and Mg(+2) of host rock. The interpretation of plots for different major ions and molar ratios suggest that weathering of silicate rocks and water-rock interaction is responsible for major ion chemistry of groundwater in Wailpally watershed. Chemical characteristics and evolution of this fluoride-contaminated groundwater is akin to normal waters of other hard rock terrain; hence, it can be concluded that aquifer material play an important role in the contribution of fluoride in to the accompanying water. High fluoride content in groundwater can be attributed to the continuous water-rock interaction during the process of percolation with fluoride-bearing country rocks under arid, low precipitation, and high evapotranspiration conditions.

Microwave Spectroscopic Investigations of the C-H\\cdotsπ Containing Complexes CH_2F_2\\cdotsPROPYNE and CH_2ClF\\cdotsPROPYNE

NASA Astrophysics Data System (ADS)

Peebles, Rebecca A.; Peebles, Sean A.; Christenholz, Cori L.; Ernst, Anthony A.; Dhahir, Yasser J.

2013-06-01

The spectra of the CH_2F_2\\cdotspropyne and CH_2ClF\\cdotspropyne complexes have been studied by chirped-pulse and resonant cavity Fourier-transform microwave spectroscopy and by ab initio calculations at the MP2/6-311++G(2d,2p) level. Both complexes contain C-H\\cdotsπ contacts, with the halogen atoms angled towards the methyl group end of the propyne. While CH_2F_2\\cdotspropyne has C_s symmetry, CH_2ClF\\cdotspropyne has C_1 symmetry, with the fluorine and chlorine atoms straddling the propyne. Investigation of four single ^{13}C and the DC≡CCH_3 isotopologues in CH_2F_2\\cdotspropyne has allowed a detailed structural determination, while only the ^{35}Cl and ^{37}Cl isotopologues have so far been assigned for CH_2ClF\\cdotspropyne. Experimental data will be compared with ab initio results and with the analogous acetylene complexes, both of which have C_s symmetry structures, with double C-H\\cdotsπ interactions.

Specificity of pyrometamorphic minerals of the ellestadite group

NASA Astrophysics Data System (ADS)

Zateeva, S. N.; Sokol, E. V.; Sharygin, V. V.

2007-12-01

Numerous rare and new mineral species are synthesized during the process of pyrometamorphism (Gross, 1977; Chesnokov et al., 1987; Chesnokov and Shcherbakova, 1991; Chesnokov, 1999), including silicooxides, chloride-, fluoride, and sulfate-silicates, carbonate-sulfides, chloride-oxides, etc. Having made sense of numerous findings of compounds of this type, Chesnokov (1999) set forth the concept of the crystallochemical transition at extreme temperatures attaining 1200-1450°C in pyrogenic systems. First of all, intertype transitions (oxygen-bearing-oxygen-free) and interclass transitions (chloride-silicate, carbonate-sulfide, chlorideoxide) are realized. The specificity of pyrometamorphic mineral assemblages consists in the abundance of silicates with additional anions (F-, Cl-, (CO3)2-) (Sokol et al., 2005). Minerals of the ellestadite group Ca10(SiO4)3 - x (SO4)3 - x (PO4)2 x (OH,F,Cl)2 are a spectacular example of these features. In the general case, they are silicate-sulfate-phosphate-hydroxide-chlorides-fluorides. The detailed description of these minerals based on the study of the original collection of pyrometamorphic minerals is presented in this paper.

Permanent electric dipole moments of PtX (X = H, F, Cl, Br, and I) by the composite approach

NASA Astrophysics Data System (ADS)

Deng, Dan; Lian, Yongqin; Zou, Wenli

2017-11-01

Using the FPD composite approach of Peterson et. al. we calculate the permanent electric dipole moments of PtX (X = H, F, Cl, Br, and I) at the equilibrium geometries of their ground states. The dipole moment of PtF is estimated to be 3.421 Debye, being very close to the experimental value of 3.42(6) Debye. This research also suggests the ordering of dipole moments of PtX being proportional to the electronegativity of X.

A new method of calculating electrical conductivity with applications to natural waters

USGS Publications Warehouse

McCleskey, R. Blaine; Nordstrom, D. Kirk; Ryan, Joseph N.; Ball, James W.

2012-01-01

A new method is presented for calculating the electrical conductivity of natural waters that is accurate over a large range of effective ionic strength (0.0004–0.7 mol kg-1), temperature (0–95 °C), pH (1–10), and conductivity (30–70,000 μS cm-1). The method incorporates a reliable set of equations to calculate the ionic molal conductivities of cations and anions (H+, Li+, Na+, K+, Cs+, NH4+, Mg2+, Ca2+, Sr2+, Ba2+, F-, Cl-, Br-, SO42-, HCO3-, CO32-, NO3-, and OH-), environmentally important trace metals (Al3+, Cu2+, Fe2+, Fe3+, Mn2+, and Zn2+), and ion pairs (HSO4-, NaSO4-, NaCO3-, and KSO4-). These equations are based on new electrical conductivity measurements for electrolytes found in a wide range of natural waters. In addition, the method is coupled to a geochemical speciation model that is used to calculate the speciated concentrations required for accurate conductivity calculations. The method was thoroughly tested by calculating the conductivities of 1593 natural water samples and the mean difference between the calculated and measured conductivities was -0.7 ± 5%. Many of the samples tested were selected to determine the limits of the method and include acid mine waters, geothermal waters, seawater, dilute mountain waters, and river water impacted by municipal waste water. Transport numbers were calculated and H+, Na+, Ca2+, Mg2+, NH4+, K+, Cl-, SO42-, HCO3-, CO32-, F-, Al3+, Fe2+, NO3-, and HSO4- substantially contributed (>10%) to the conductivity of at least one of the samples. Conductivity imbalance in conjunction with charge imbalance can be used to identify whether a cation or an anion measurement is likely in error, thereby providing an additional quality assurance/quality control constraint on water analyses.

A new method of calculating electrical conductivity with applications to natural waters

NASA Astrophysics Data System (ADS)

McCleskey, R. Blaine; Nordstrom, D. Kirk; Ryan, Joseph N.; Ball, James W.

2012-01-01

A new method is presented for calculating the electrical conductivity of natural waters that is accurate over a large range of effective ionic strength (0.0004-0.7 mol kg-1), temperature (0-95 °C), pH (1-10), and conductivity (30-70,000 μS cm-1). The method incorporates a reliable set of equations to calculate the ionic molal conductivities of cations and anions (H+, Li+, Na+, K+, Cs+, NH4+, Mg2+, Ca2+, Sr2+, Ba2+, F-, Cl-, Br-, SO42-, HCO3-, CO32-, NO3-, and OH-), environmentally important trace metals (Al3+, Cu2+, Fe2+, Fe3+, Mn2+, and Zn2+), and ion pairs (HSO4-, NaSO4-, NaCO3-, and KSO4-). These equations are based on new electrical conductivity measurements for electrolytes found in a wide range of natural waters. In addition, the method is coupled to a geochemical speciation model that is used to calculate the speciated concentrations required for accurate conductivity calculations. The method was thoroughly tested by calculating the conductivities of 1593 natural water samples and the mean difference between the calculated and measured conductivities was -0.7 ± 5%. Many of the samples tested were selected to determine the limits of the method and include acid mine waters, geothermal waters, seawater, dilute mountain waters, and river water impacted by municipal waste water. Transport numbers were calculated and H+, Na+, Ca2+, Mg2+, NH4+, K+, Cl-, SO42-, HCO3-, CO32-, F-, Al3+, Fe2+, NO3-, and HSO4-substantially contributed (>10%) to the conductivity of at least one of the samples. Conductivity imbalance in conjunction with charge imbalance can be used to identify whether a cation or an anion measurement is likely in error, thereby providing an additional quality assurance/quality control constraint on water analyses.

Coupling between sulfur recycling and syndepositional carbonate dissolution: evidence from oxygen and sulfur isotope composition of pore water sulfate, South Florida Platform, U.S.A.

NASA Astrophysics Data System (ADS)

Ku, T. C. W.; Walter, L. M.; Coleman, M. L.; Blake, R. E.; Martini, A. M.

1999-10-01

Sulfur cycling in Fe-poor, organic-rich shelf carbonates, known to have rapid rates of SO4-2 reduction, remains poorly studied despite the volumetric significance of shelf deposits in modern and ancient carbon budgets. We investigated sulfur cycling in modern carbonates of the Florida Platform from end-member depositional environments (muddy sands from the Atlantic reef tract and finer-grained mudbank and island flank deposits from Florida Bay). Relations between pore water chemistry (SO4-2, ΣCO2, Ca-2/Cl-) and oxygen and sulfur stable isotope compositions of SO4-2 require direct coupling between sulfur redox cycling and syndepositional carbonate dissolution. Oxygen isotope compositions of pore water sulfate were remarkably shifted away from the established value for marine SO4-2 (+9.5‰), despite near normal SO4-2/Cl- ratios. Chemical evolution was least in reef tract pore waters and greatest in Florida Bay. Relative to overlying seawater, mudbank sediments exhibited sulfate depletion, with δ18OSO4 and δ34SSO4 values both increasing by about 7‰. More bioturbated island flank sediments, colonized by Thalassia grass, had a 5‰ increase in δ18OSO4, variable δ34SSO4 values (+17.7 to +23.3‰) and exceptionally high Ca+2/Cl- ratios. The large excess of Ca+2 (up to 1.7 mM) requires a much larger acid source than the amounts derived from utilization of dissolved O2 (∼0.3 mM) and small degrees of net SO4-2 reduction (<0.5 mM reduced). A conceptual model was constructed using chemical and isotopic data on natural pore waters and on sulfate isotope fractionation factors obtained from sediment incubation experiments. The model outputs show that pore water compositions can be explained by a redox cycle where microbial SO4-2 reduction is followed by very efficient H2S oxidation, thus maintaining virtually invariant SO4-2/Cl- ratios. The enhanced O2 transport may be driven by associated marine grass rhizome systems and microbial communities established in bioturbated sediments. The net result of the cycle is that the rate of sulfide oxidation, which is largely balanced by the rate of microbial sulfate reduction, is stoichiometrically related to the rate of carbonate dissolution. This is consistent with previously reported rates of carbonate dissolution (∼400 μmol/cm2-yr) and average rates of sulfate reduction (∼200 μmol/cm2-yr) from the Florida Platform and a 2:1 stoichiometry.

Reaction of Chlorosulfonyl Isocyanate (CSI) with Fluorosubstituted Alkenes: Evidence of a Concerted Pathway for Reaction of CSI with Fluorosubstituted Alkenes (Preprint)

DTIC Science & Technology

2010-06-01

ABSTRACT Concerted reactions are indicated for the electrophilic addition of chlorosulfonyl isocyanate with monofluoroalkenes. A vinyl fluorine atom on...SO2Cl R F O ‡ N SO2Cl F R O Abstract: Concerted reactions are indicated for the electrophilic addition of chlorosulfonyl isocyanate with...monofluoroalkenes. A vinyl fluorine atom on an alkene raises the energy of a step-wise transition state more than the energy of the competing concerted

Application of ion chromatography to the determination of water-soluble inorganic and organic ions in atmospheric aerosols.

PubMed

Yu, Xue-Chun; He, Ke-Bin; Ma, Yong-Liang; Yang, Fu-Mo; Duan, Feng-Kui; Zheng, Ai-Hua; Zhao, Cheng-Yi

2004-01-01

A simple, sensitive and convenient ion chromatography(IC) method was established for the simultaneous determination of twelve water-soluble inorganic anions(F- , Cl- , NO2(-), NO3(-), SO3(2-), SO4(2-) , PO4(3-)), and fifteen water-soluble organic ions(formate, acetate, MSA, oxalate, malonate, succinate, phthalates, etc.) in atmospheric aerosols. The linear concentrations ranged from 0.005 microg/m3 to 500 microg/m3 ( r = 0.999-0.9999). The relative standard deviation (RSD) were 0.43%-2.00% and the detection limits were from 2.7 ng/m3 to 88 ng/m3. The proposed method was successfully applied to the simultaneous determination of those inorganic ions and organic ions in PM2.5 of Beijing.

Sulfur(VI) fluoride exchange (SuFEx): another good reaction for click chemistry.

PubMed

Dong, Jiajia; Krasnova, Larissa; Finn, M G; Sharpless, K Barry

2014-09-01

Aryl sulfonyl chlorides (e.g. Ts-Cl) are beloved of organic chemists as the most commonly used S(VI) electrophiles, and the parent sulfuryl chloride, O2 S(VI) Cl2 , has also been relied on to create sulfates and sulfamides. However, the desired halide substitution event is often defeated by destruction of the sulfur electrophile because the S(VI) Cl bond is exceedingly sensitive to reductive collapse yielding S(IV) species and Cl(-) . Fortunately, the use of sulfur(VI) fluorides (e.g., R-SO2 -F and SO2 F2 ) leaves only the substitution pathway open. As with most of click chemistry, many essential features of sulfur(VI) fluoride reactivity were discovered long ago in Germany.6a Surprisingly, this extraordinary work faded from view rather abruptly in the mid-20th century. Here we seek to revive it, along with John Hyatt's unnoticed 1979 full paper exposition on CH2 CH-SO2 -F, the most perfect Michael acceptor ever found.98 To this history we add several new observations, including that the otherwise very stable gas SO2 F2 has excellent reactivity under the right circumstances. We also show that proton or silicon centers can activate the exchange of SF bonds for SO bonds to make functional products, and that the sulfate connector is surprisingly stable toward hydrolysis. Applications of this controllable ligation chemistry to small molecules, polymers, and biomolecules are discussed. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

On the intermolecular vibrational coupling, hydrogen bonding, and librational freedom of water in the hydration shell of mono- and bivalent anions.

PubMed

Ahmed, Mohammed; Namboodiri, V; Singh, Ajay K; Mondal, Jahur A

2014-10-28

The hydration energy of an ion largely resides within the first few layers of water molecules in its hydration shell. Hence, it is important to understand the transformation of water properties, such as hydrogen-bonding, intermolecular vibrational coupling, and librational freedom in the hydration shell of ions. We investigated these properties in the hydration shell of mono- (Cl(-) and I(-)) and bivalent (SO4(2-) and CO3(2-)) anions by using Raman multivariate curve resolution (Raman-MCR) spectroscopy in the OH stretch, HOH bend, and [bend+librational] combination bands of water. Raman-MCR of aqueous Na-salt (NaCl, NaI, Na2SO4, and Na2CO3) solutions provides ion-correlated spectra (IC-spectrum) which predominantly bear the vibrational characteristics of water in the hydration shell of respective anions. Comparison of these IC-spectra with the Raman spectrum of bulk water in different spectral regions reveals that the water is vibrationally decoupled with its neighbors in the hydration shell. Hydrogen-bond strength and librational freedom also vary with the nature of anion: hydrogen-bond strength, for example, decreases as CO3(2-) > SO4(2-) > bulk water ≈ Cl(-) > I(-); and the librational freedom increases as CO3(2-) ≈ SO4(2-) < bulk water < Cl(-) < I(-). It is believed that these structural perturbations influence the dynamics of coherent energy transfer and librational reorientation of water in the hydration shell of anions.

A slow calcium-dependent component of charge movement in Rana temporaria cut twitch fibres.

PubMed

Hui, C S

1998-06-15

1. Charge movement was studied in highly stretched frog cut twitch fibres in a double Vaseline-gap voltage-clamp chamber, with the internal solution containing either 0.1 mM EGTA or 20 mM EGTA plus 1. 8 mM total Ca2+. 2. Fibres were stimulated with TEST pulses lasting 100-400 ms. Replacement of the external Cl- with an 'impermeant' anion, such as SO42-, CH3SO3-, gluconate or glutamate, greatly reduced the calcium-dependent Cl- current in the ON segment and generated a slowly decaying inward OFF current in charge movement traces. 3. Application of 20 mM EGTA to the internal solution abolished the slow inward OFF current, implying that the activation of the current depended on the presence of Ca2+ in the myoplasm. The possibility that the slow inward OFF current was carried by cations flowing inwards or anions flowing outwards was studied and determined to be unlikely. 4. During a long (2000 ms) TEST pulse, a slowly decaying ON current was also observed. When the slow ON and OFF currents were included as parts of the total charge movement, ON-OFF charge equality was preserved. This slow capacitive current is named Idelta. 5. When Cl- was the major anion in the external solution, the OFF Idelta was mostly cancelled by a slow outward current carried by the inflow of Cl-. 6. The OFF Idelta component showed a rising phase. The average values of the rising time constants in CH3SO3- and SO42- were similar and about half of that in gluconate. 7. The OFF Idelta component in CH3SO3- had a larger magnitude and longer time course than that in SO42-. The maximum amount of Qdelta in CH3SO3- was about three times as much as that in SO42-, whereas the voltage dependence of Qdelta was similar in the two solutions. 8. Since the existence of Qdelta depends on the presence of Ca2+ in the myoplasm, it is speculated that Qdelta could be a function of intracellular calcium release.

Relationship between anode material, supporting electrolyte and current density during electrochemical degradation of organic compounds in water.

PubMed

Guzmán-Duque, Fernando L; Palma-Goyes, Ricardo E; González, Ignacio; Peñuela, Gustavo; Torres-Palma, Ricardo A

2014-08-15

Taking crystal violet (CV) dye as pollutant model, the electrode, electrolyte and current density (i) relationship for electro-degrading organic molecules is discussed. Boron-doped diamond (BDD) or Iridium dioxide (IrO2) used as anode materials were tested with Na2SO4 or NaCl as electrolytes. CV degradation and generated oxidants showed that degradation pathways and efficiency are strongly linked to the current density-electrode-electrolyte interaction. With BDD, the degradation pathway depends on i: If ii(lim), generated oxidants play a major role in the CV elimination. When IrO2 was used, CV removal was not dependent on i, but on the electrolyte. Pollutant degradation in Na2SO4 on IrO2 seems to occur via IrO3; however, in the presence of NaCl, degradation was dependent on the chlorinated oxidative species generated. In terms of efficiency, the Na2SO4 electrolyte showed better results than NaCl when BDD anodes were employed. On the contrary, NaCl was superior when combined with IrO2. Thus, the IrO2/Cl(-) and BDD/SO4(2-) systems were better at removing the pollutant, being the former the most effective. On the other hand, pollutant degradation with the BDD/SO4(2-) and IrO2/Cl(-) systems is favored at low and high current densities, respectively. Copyright © 2014 Elsevier B.V. All rights reserved.

AB Initio Study of the Structure and Spectroscopic Properties of Halogenated Thioperoxy Radicals

NASA Technical Reports Server (NTRS)

Munoz, Luis A.; Binning, R. C., Jr.; Weiner, Brad R.; Ishikawa, Yasuyuki

1997-01-01

Thioperoxy (XSO or XOS) radicals exist in a variety of chemical environments, and they have as a consequence drawn some interest. HSO, an important species in the chemistry of the troposphere, has been examined both experimentally. The halogenated (X = F, Cl or Br) peroxy species and isovalent thioperoxy species have been studied less, but they too are potentially interesting because oxidized sulfur species and halogen sources are present in the atmosphere. Learning the fate of XSO and XOS radicals is important to understanding the atmospheric oxidation chemistry of sulfur compounds. Of these, FSO and ClSO are particularly interesting because they have been directly detected spectroscopically. Recent studies in our laboratory on the photochemistry of thionyl halides (X2SO; where X = F or Cl) have suggested new ways to generate XSO species. The laser-induced photodissociation of thionyl fluoride, F2SO, at 193 nm and thionyl chloride, ClSO, at 248 nm is characterized by a radical mechanism, X2SO -> XSO + X. The structure of FSO has been characterized experimentally by Endo et cd. employing microwave spectroscopy. Using the unrestricted Hartree-Fock (UHF) self-consistent field (SCF) method, Sakai and Morokuma computed the electronic structure of the ground (sup 2)A" and the first excited (sup 2)A' states of FSO. Electron correlation was not taken into account in their study. In a laser photodissociation experiment, Huber et al. identified ClSO mass spectromctrically. ClSO has also been detected in low temperature matrices by EPR and in the gas phase by far IR laser magnetic resonance. Although the structure of FSO is known in detail, the only study, experimental or theoretical, of CISO has been an ab initio HFSCF study by Hinchliffe. Electron correlation corrections were also excluded from this study. In order to better understand the isomerization and dissociation dynamics of the radical species, we have performed ab initio correlated studies of the potential energy surfaces (PES) of ClSO and its isomer ClOS at the QCISD(T)/6-31 G* level of theory. For FSO and FOS, more extensive QCISD/6-31 1G(2df) calculations have been possible, and the results are summarized here.

[Water-soluble anions of atmosphere on Tianwan nuclear power station].

PubMed

Zhao, Heng-Qiang; He, Ying; Zheng, Xiao-Ling; Chen, Fa-Rong; Pang, Shi-Ping; Wang, Cai-Xia; Wang, Xiao-Ru

2010-11-01

Three major water-soluble anions (Cl-, SO4(2-) and NO3-) in the atmosphere of the Tianwan nuclear power station in Lianyungang were determined by ion chromatography from June 2005 to May 2006. The results showed that the annual average concentration of Cl-, SO4(2-) and NO3- in the atmosphere of Tianwan nuclear power station was (33.12 +/- 53.63) microg x m(-3), (53.34 +/- 30.34) microg x m(-3) and (8.34 +/- 4.47) microg x m(-3), respectively. The concentrations of the three water-soluble anions showed evident trend of seasonal variation. The concentrations of Cl-, SO4(2-) reached the highest level in summer and the lowest level in winter, while the concentration of NO3- in autumn and winter was higher than those in summer and spring. Meteorological parameters such as wind direction, wind speed, temperature and relative humidity were studied and showed definite influence to the anions concentration of the atmosphere. This is the first simultaneous monitoring of corrosive anions in the atmosphere of Chinese coastal nuclear power plant, and it will provide basis for the prevention of marine atmospheric corrosion, which will ensure the safely operating of our nuclear power industry.

[Changes in bio-availability of immobilized Cu and Zn bound to phosphate in contaminated soils with different nutrient addition].

PubMed

Xu, Ming-Gang; Zhang, Qian; Sun, Nan; Shen, Hua-Ping; Zhang, Wen-Ju

2009-07-15

Bio-availability of Cu and Zn fixed by phosphate in contaminated soils with application of nutrients were measured by pot experiment. It was simulated for the third national standardization of copper and zinc polluted soils by adding copper and zinc nitrate into red and paddy soils, respectively and together. Phosphate amendment was added to the soils to fix Cu and Zn, then added KCl and NH4Cl or K2SO4 and (NH4)2SO4 fertilizers following to plant Ryegrass, which was harvested after 40 d. Available Cu/Zn content in soils and biomass, Cu/Zn content in the shoot of Ryegrass were determined. Results showed that, compared with no nutrient application, adding KCl and NH4 Cl/K2SO4 and (NH4)2SO4 to polluted red and paddy soils increased the available Cu and Zn content in red soil significantly. The increasing order was KCl and NH4 Cl > K2SO4 and (NH4)2SO4. Especially in single Zn polluted red soil, the available Zn content increased by 133.4% in maximum. Although adding K2SO4 and (NH4)2SO4 could promote the growth of Ryegrass on red soil, and the largest increasing was up to 22.2%, it increased Cu and Zn content in the shoot of Ryegrass for 21.5%-112.6% remarkably. These nutrient effects on available Cu and Zn were not significantly in paddy soil. It was suggested that application of nitrogen and potassium fertilizers to soils could change the bioavailability of Cu/Zn. So it is necessary to take full account of the nutrient influence to the heavy metal stability which fixed by phosphate in contaminated soils when consider contaminated soils remediation by fertilization.

Fog water chemistry in Shanghai

NASA Astrophysics Data System (ADS)

Li, Pengfei; Li, Xiang; Yang, Chenyu; Wang, Xinjun; Chen, Jianmin; Collett, Jeffrey L., Jr.

2011-08-01

With the aim of understanding the fog chemistry in a Chinese megacity, twenty-six fog water samples were collected in urban Shanghai from March 2009 to March 2010. The following parameters were measured: pH, electrical conductivity (EC), ten inorganic major ions ( SO42-, NO3-, NO2-, F -, Cl -, Na +, K +, Ca 2+, Mg 2+, NH4+) and four major organic acids (CH 3COO -, HCOO -, CO42-, MSA). The total ionic concentration (TIC) and EC of fog samples were one or two orders of magnitude higher than those often found in Europe, North America and other Asian countries. Pollutants were expected to be mainly from local sources, including factories, motor vehicle emissions and civil construction. Non-local sources such as moderate- and long-range transport of sea salt also contributed to pollution levels in fog events as indicated by back trajectory analysis. The pH of the fog water collected during the monitoring period varied from 4.68 to 6.58; acidic fogs represented about 30.8% of the total fog events during this period. The fog water was characterized by high concentrations of SO42- (20.0% of measured TIC), NO3- (17.1%), NH4+ (28.3%) and Ca 2+ (14.4%). SO42- and NO3-, the main precursors of fog acidity, were related to burning fossil fuels and vehicle emissions, respectively. NH4+, originating from the scavenging of gaseous ammonia and particulate ammonium nitrate and ammonium sulfate, and Ca 2+, originating from the scavenging of coarse particles, acted as acid neutralizers and were the main cause for the relatively high pH of fogs in Shanghai. The ratio of ( SO42- + NO3-)/( NH4+ + Ca 2+) was lower than 1, indicating the alkaline nature of the fog water. A high ratio of NO3-/ SO42- and low ratio of HCOO -/CH 3COO - were consistent with large contributions from vehicular emissions that produce severe air pollution in megacities.

Oxidation of bisphenol F (BPF) by manganese dioxide.

PubMed

Lu, Zhijiang; Lin, Kunde; Gan, Jay

2011-10-01

Bisphenol F (BPF), an environmental estrogen, is used as a monomer in plastic industry and its environmental fate and decontamination are emerging concern. This study focused on the kinetics, influencing factors and pathways of its oxidation by MnO(2). At pH 5.5, about 90% of BPF was oxidized in 20 min in a solution containing 100 μM MnO(2) and 4.4 μM BPF. The reaction was pH-dependent, following an order of pH 4.5 > pH 5.5 > pH 8.6 > pH 7.5 > pH 6.5 > pH 9.6. Humic acids inhibited the reaction at low (≤ pH 5.5) and high pH (≥ pH 8.6) at high concentrations. In addition, metal ions and anions also suppressed the reaction, following the order Mn(2+) > Ca(2+) > Mg(2+) > Na(+) and HPO(4)(2-) > Cl(-) > NO(3)(-) ≈ SO(4)(2-), respectively. A total of 5 products were identified, from which a tentative pathway was proposed. Copyright © 2011 Elsevier Ltd. All rights reserved.

Identification of anthropogenic and natural inputs of sulfate and chloride into the karstic ground water of Guiyang, SW China: combined delta37Cl and delta34S approach.

PubMed

Liu, Cong-Qiang; Lang, Yun-Chao; Satake, Hiroshi; Wu, Jiahong; Li, Si-Liang

2008-08-01

Because of active exchange between surface and groundwater of a karstic hydrological system, the groundwater of Guiyang, the capital city of Guizhou Province, southwest China, has been seriously polluted by anthropogenic inputs of NO3-, SO4(2-), Cl-, and Na+. In this work, delta37Cl of chloride and delta34S variations of sulfate in the karstic surface/groundwater system were studied, with a main focus to identify contaminant sources, including their origins. The surface, ground, rain, and sewage water studied showed variable delta37Cl and delta34S values, in the range of -4.1 to +2.0 per thousand, and -20.4 to +20.9 per thousand for delta37Cl and delta34S (SO4(2-)), respectively. The rainwater samples yielded the lowest delta37Cl values among those observed to date for aerosols and rainwater. Chloride in the Guiyang area rain waters emanated from anthropogenic sources rather than being of marine origin, probably derived from HCl (g) emitted by coal combustion. By plotting 1/SO4(2-) vs delta34S and 1/Cl- vs delta37Cl, respectively, we were able to identify some clusters of data, which were assigned as atmospheric deposition (acid rain component), discharge from municipal sewage, paleo-brine components in clastic sedimentary rocks, dissolution of gypsum mainly in dolomite, oxidation of sulfide minerals in coal-containing clastic rocks, and possibly degradation of chlorine-containing organic matter. We conclude that human activities give a significant input of sulfate and chloride ions, as well as other contaminants, into the studied groundwater system through enhanced atmospheric deposition and municipal sewage, and that multiple isotopic tracers constitute a powerful tool to ascertain geochemical characteristics and origin of complex contaminants in groundwater.

Remedial Investigation Report, Presidio Main Installation, Presidio of San Francisco. Volume 6: Appendices A-F

DTIC Science & Technology

1997-01-01

Version 1 .0 )9-/77 Background data analysis Az. CdB . C t_ I eF2 G S21.4 Cal-Ba Method• detection limit Mediki czi.ii- 23.6 Cl-B O.. 13.9ol DATA15 Ca...E F G H T2 4124 CoI-Cr TTL5 i.2 305 0-0 Ca=Lonomllmen97.534 Create ineprt 41.1 Cal-Cr ENTER DATA 7 J42,8251 Histogram 41.2 Wa-0 IT 42.1 Cdct Ditibto

On the oxidation of the three-dimensional aromatics [B(12)X(12)](2-) (X=F, Cl, Br, I).

PubMed

Boeré, René T; Derendorf, Janis; Jenne, Carsten; Kacprzak, Sylwia; Kessler, Mathias; Riebau, Rainer; Riedel, Sebastian; Roemmele, Tracey L; Rühle, Monika; Scherer, Harald; Vent-Schmidt, Thomas; Warneke, Jonas; Weber, Stefan

2014-04-07

The perhalogenated closo-dodecaborate dianions [B12 X12 ](2-) (X=H, F, Cl, Br, I) are three-dimensional counterparts to the two-dimensional aromatics C6 X6 (X=H, F, Cl, Br, I). Whereas oxidation of the parent compounds [B12 H12 ](2-) and benzene does not lead to isolable radicals, the perhalogenated analogues can be oxidized by chemical or electrochemical methods to give stable radicals. The chemical oxidation of the closo-dodecaborate dianions [B12 X12 ](2-) with the strong oxidizer AsF5 in liquid sulfur dioxide (lSO2 ) yielded the corresponding radical anions [B12 X12 ](⋅-) (X=F, Cl, Br). The presence of radical ions was proven by EPR and UV/Vis spectroscopy and supported by quantum chemical calculations. Use of an excess amount of the oxidizing agent allowed the synthesis of the neutral perhalogenated hypercloso-boranes B12 X12 (X=Cl, Br). These compounds were characterized by single-crystal X-ray diffraction of dark blue B12 Cl12 and [Na(SO2 )6 ][B12 Br12 ]⋅B12 Br12 . Sublimation of the crude reaction products that contained B12 X12 (X=Cl, Br) resulted in pure dark blue B12 Cl12 or decomposition to red B9 Br9 , respectively. The energetics of the oxidation processes in the gas phase were calculated by DFT methods at the PBE0/def2-TZVPP level of theory. They revealed the trend of increasing ionization potentials of the [B12 X12 ](2-) dianions by going from fluorine to bromine as halogen substituent. The oxidation of all [B12 X12 ](2-) dianions was also studied in the gas phase by mass spectrometry in an ion trap. The electrochemical oxidation of the closo-dodecaborate dianions [B12 X12 ](2-) (X=F, Cl, Br, I) by cyclic and Osteryoung square-wave voltammetry in liquid sulfur dioxide or acetonitrile showed very good agreement with quantum chemical calculations in the gas phase. For [B12 X12 ](2-) (X=F, Cl, Br) the first and second oxidation processes are detected. Whereas the first process is quasi-reversible (with oxidation potentials in the range between +1.68 and +2.29 V (lSO2 , versus ferrocene/ferrocenium (Fc(0/+) ))), the second process is irreversible (with oxidation potentials ranging from +2.63 to +2.71 V (lSO2 , versus Fc(0/+) )). [B12 I12 ](2-) showed a complex oxidation behavior in cyclic voltammetry experiments, presumably owing to decomposition of the cluster anion under release of iodide, which also explains the failure to isolate the respective radical by chemical oxidation. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

42 CFR Appendix - Tables to Subpart L of Part 84

Code of Federal Regulations, 2010 CFR

2010-10-01

... respiratory protection against more than one gas of a type, as for use in chlorine and sulfur dioxide, the... Ammonia Equilibrated NH3 1000 32 4 50 50 Chlorine As received Cl2 500 64 3 5 35 Chlorine Equilibrated Cl2... Sulfur dioxide As received SO2 500 64 3 5 30 Sulfur dioxide Equilibrated SO2 500 32 4 5 30 1 Minimum life...

Fast O2 Binding at Dicopper Complexes Containing Schiff-Base Dinucleating Ligands

PubMed Central

Company, Anna; Gómez, Laura; Mas-Ballesté, Rubén; Korendovych, Ivan V.; Ribas, Xavi; Poater, Albert; Parella, Teodor; Fontrodona, Xavier; Benet-Buchholz, Jordi; Solà, Miquel; Que, Lawrence; Rybak-Akimova, Elena; Costas, Miquel

2008-01-01

A new family of dicopper(I) complexes [CuI2RL](X)2, (R = H, 1X, R = tBu, 2X and R = NO2, 3X, X = CF3SO3, ClO4, SbF6 or BArF, BArF = [B{3,5-(CF3)2-C6H3}4]−), where RL is a Schiff-base ligand containing two tridentate binding sites linked by a xylyl spacer have been prepared, characterized, and their reaction with O2 studied. The complexes were designed with the aim of reproducing structural aspects of the active site of type 3 dicopper proteins; they contain two three-coordinate copper sites and a rather flexible podand ligand backbone. The solid state structures of 1ClO4, 2CF3SO3, 2ClO4 and 3BArF·CH3CN have been established by single crystal X-ray diffraction analysis. 1ClO4 adopts a polymeric structure in solution while 2CF3SO3, 2ClO4 and 3BArF·CH3CN are monomeric. The complexes have been studied in solution by means of 1H and 19F NMR spectroscopy, which put forward the presence of dynamic processes in solution. 1-3BArF and 1-3CF3SO3 in acetone react rapidly with O2 to generate metaestable [CuIII2(μ-O)2(RL)]2+ 1-3(O2) and [CuIII2(μ-O)2(CF3SO3)(RL)]+ 1-3(O2)(CF3SO3) species, respectively that have been characterized by UV-vis spectroscopy and resonance Raman analysis. Instead, reaction of 1-3BArF with O2 in CH2Cl2 results in intermolecular O2 binding. DFT methods have been used to study the chemical identities and structural parameters of the O2 adducts, and the relative stability of the CuIII2(μ-O)2 form with respect to the CuII2(μ-η2: η2-peroxo) isomer. The reaction of 1X, X = CF3SO3 and BArF with O2 in acetone has been studied by stopped-flow exhibiting an unexpected very fast reaction rate (k = 3.82(4) × 103 M−1s−1, ΔH‡ = 4.9 ± 0.5 kJ·mol−1, ΔS‡ = −148 ± 5 J·K−1·mol−1), nearly three orders of magnitude faster than in the parent [CuI2(m-XYLMeAN)]2+. Thermal decomposition of 1-3(O2) does not result in aromatic hydroxylation. The mechanism and kinetics of O2 binding to 1X (X = CF3SO3 and BArF) is discussed and compared with those associated to selected examples of reported models of O2-processing copper proteins. A synergistic role of the copper ions in O2 binding and activation is clearly established from this analysis. PMID:17500512

Investigating the Weak to Evaluate the Strong: An Experimental Determination of the Electron Binding Energy of Carborane Anions and the Gas phase Acidity of Carborane Acids

DOE Office of Scientific and Technical Information (OSTI.GOV)

Meyer, Matthew M; Wang, Xue B; Reed, Christopher A

2009-12-23

Five CHB 11X 6Y 5 - carborane anions from the series X = Br, Cl, I and Y = H, Cl, CH 3 were generated by electrospray ionization, and their reactivity with a series of Brønsted acids and electron transfer reagents were examined in the gas phase. The undecachlorocarborane acid, H(CHB 11Cl 11), was found to be far more acidic than the former record holder, (1-C 4F 9SO 2) 2NH (i.e., ΔH° acid = 241 ± 29 vs 291.1 ± 2.2 kcal mol -1) and bridges the gas-phase acidity and basicity scales for the first time. Its conjugate base, CHBmore » 11Cl 11 -, was found by photoelectron spectroscopy to have a remarkably large electron binding energy (6.35 ± 0.02 eV) but the value for the (1-C 4F 9SO 2) 2N - anion is even larger (6.5 ± 0.1 eV). Consequently, it is the weak H-(CHB 11Cl 11) BDE (70.0 kcal mol -1, G3(MP2)) compared to the strong BDE of (1-C 4F 9SO 2) 2N-H (127.4 ± 3.2 kcal mol -1) that accounts for the greater acidity of carborane acids.« less

A naphthalene exciplex based Al3+ selective on-type fluorescent probe for living cells at the physiological pH range: experimental and computational studies.

PubMed

Banerjee, Arnab; Sahana, Animesh; Das, Sudipta; Lohar, Sisir; Guha, Subarna; Sarkar, Bidisha; Mukhopadhyay, Subhra Kanti; Mukherjee, Asok K; Das, Debasis

2012-05-07

2-((Naphthalen-6-yl)methylthio)ethanol (HL) was prepared by one pot synthesis using 2-mercaptoethanol and 2-bromomethylnaphthalene. It was found to be a highly selective fluorescent sensor for Al(3+) in the physiological pH (pH 7.0-8.0). It could sense Al(3+) bound to cells through fluorescence microscopy. Metal ions like Mn(2+), Fe(3+), Co(2+), Ni(2+), Cu(2+), Zn(2+), Ag(+), Cd(2+), Hg(2+), Cr(3+) and Pb(2+) did not interfere. No interference was also observed with anions like Cl(-), Br(-), F(-), SO(4)(2-), NO(3)(-), CO(3)(2-), HPO(4)(2-) and SCN(-). Experimentally observed structural and spectroscopic features of HL and its Al(3+) complex have been substantiated by computational calculations using density functional theory (DFT) and time dependent density functional theory (TDDFT).

Chemical profile of size-fractionated soils collected in a semiarid industrial area of Argentina

NASA Astrophysics Data System (ADS)

Morales Del Mastro, Anabella; Pereyra, Marcelo; Londonio, Agustín; Pereyra, Victoria; Rebagliati, Raúl Jiménez; Dawidowski, Laura; Gómez, Darío; Smichowski, Patricia

2014-12-01

A study was undertaken to assess the chemical profile of soil collected in Bahía Blanca (Argentina). In this industrial city, semiarid soils are affected by different industrial and agricultural activities, the presence of a saltpeter extraction facility, traffic and increasing urbanization. Sixteen soil samples (superficial and sub-superficial) were collected. Samples were sieved in two fractions (A < 37 μm, and 37 < B < 50 μm) before elemental analysis. Major, minor and trace elements namely, Al, As, Ba, Ca, Cd, Cr, Cu, Fe, Mg, Mn, Mo, Ni, Pb, Sb, Ti, V and Zn were determined by inductively coupled plasma optical emission spectrometry (ICP OES). Anions (Cl-, F-, SO42-) and cations (K+, Na+ and NH4+) were determined by high performance liquid chromatography (HPLC) after an aqueous extraction. As expected, crustal elements namely, Al, Ca, Fe, Mg and Ti exhibited the highest concentrations. Mean elemental concentration ranged from <0.3 μg g-1 (Sb) to 14.6 ± 0.6% (Ca). Ions concentrations in the soluble fraction measured at mg g-1 levels were in the order Cl- > Na+ ≅ SO42- > K+ > NO3-. Three indicators, namely, (i) coefficient of variation, (ii) coefficient of divergence and (iii) ratio of elemental concentration with respect to Ca were used to assess chemical, spatial and inter-profile variability. Chloride > Ca > Na+ > Mo > SO42-, dominated the variability indicating that these are key chemical markers for future assessment of crustal contribution to airborne particles in the area. The ratios Xi/Ca allowed discriminating the soil of the semi-arid region surrounding Bahía Blanca. The chemical profiles obtained in this study, particularly those of topsoil, will be a key input to characterize soil resuspension and its contribution to airborne particulate matter in a forthcoming receptor model analysis.

Recharge processes drive sulfate reduction in an alluvial aquifer contaminated with landfill leachate

USGS Publications Warehouse

Scholl, M.A.; Cozzarelli, I.M.; Christenson, S.C.

2006-01-01

Natural attenuation of contaminants in groundwater depends on an adequate supply of electron acceptors to stimulate biodegradation. In an alluvial aquifer contaminated with leachate from an unlined municipal landfill, the mechanism of recharge infiltration was investigated as a source of electron acceptors. Water samples were collected monthly at closely spaced intervals in the top 2 m of the saturated zone from a leachate-contaminated well and an uncontaminated well, and analyzed for ??18O, ??2H, non-volatile dissolved organic carbon (NVDOC), SO42-, NO3- and Cl-. Monthly recharge amounts were quantified using the offset of the ??18O or ??2H from the local meteoric water line as a parameter to distinguish water types, as evaporation and methanogenesis caused isotopic enrichment in waters from different sources. Presence of dissolved SO42- in the top 1 to 2??m of the saturated zone was associated with recharge; SO42- averaged 2.2??mM, with maximum concentrations of 15??mM. Nitrate was observed near the water table at the contaminated site at concentrations up to 4.6??mM. Temporal monitoring of ??2H and SO42- showed that vertical transport of recharge carried SO42- to depths up to 1.75??m below the water table, supplying an additional electron acceptor to the predominantly methanogenic leachate plume. Measurements of ??34S in SO42- indicated both SO42- reduction and sulfide oxidation were occurring in the aquifer. Depth-integrated net SO42- reduction rates, calculated using the natural Cl- gradient as a conservative tracer, ranged from 7.5 ?? 10- 3 to 0.61??mM??d- 1 (over various depth intervals from 0.45 to 1.75??m). Sulfate reduction occurred at both the contaminated and uncontaminated sites; however, median SO42- reduction rates were higher at the contaminated site. Although estimated SO42- reduction rates are relatively high, significant decreases in NVDOC were not observed at the contaminated site. Organic compounds more labile than the leachate NVDOC may be present in the root zone, and SO42- reduction may be coupled to methane oxidation. The results show that sulfur (and possibly nitrogen) redox processes within the top 2??m of the aquifer are directly related to recharge timing and seasonal water level changes in the aquifer. The results suggest that SO42- reduction associated with the infiltration of recharge may be a significant factor affecting natural attenuation of contaminants in alluvial aquifers. ?? 2006 Elsevier B.V. All rights reserved.

Effects of hardness and alkalinity in culture and test waters on reproduction of Ceriodaphnia dubia

USGS Publications Warehouse

Lasier, P.J.; Winger, P.V.; Hardin, I.R.

2006-01-01

Ceriodaphnia dubia were cultured in four reconstituted water formulations with hardness and alkalinity concentrations ranging from soft to the moderately hard water that is required by whole-effluent toxicity (WET) testing methods for culturing test organisms. The effects of these culture formulations alone and in combination with two levels of Cl-, SO42, and HCO3- on reproduction of C. dubia were evaluated with the standard three-brood test. Reproduction was significantly reduced when test waters had lower hardness than culture waters. However, reproduction was not significantly different when animals cultured in low-hardness waters were exposed to moderately hard waters. The hardness of the culture water did not significantly affect the sensitivity of C. dubia to the three anions. Conversely, increased hardness in test waters significantly reduced the toxicities of Cl- and SO42-, with HCO3- toxicity following the same pattern. Alkalinity exhibited no consistent effect on Cl- and SO42- toxicity. The physiological stress of placing animals cultured in moderately hard water into softer test waters might contribute to marginal failures of otherwise nontoxic effluents. The standard WET protocol should be revised to allow the culture of C. dubia under lower hardness conditions to better represent local surface water chemistries.

Catalytical Photocyclization of Arylamines with a-Olefins in the Synthesis of 2-Alkylquinoline

ERIC Educational Resources Information Center

Makhmutov, Aynur; Usmanov, Salavat; Mustafin, Ahat

2016-01-01

The article deals with the results of investigation of the process of catalytical photocyclization of aniline and aniline hydrochloride with a-olefins (hexene-1, heptene-1 and octene-1). The following compounds of d- and f-metals are tested as probable catalysts: CuSO4•5H2O, EuCl3•6H2O, PrCl3•6H2O, TbCl3•6H2O, La2O3, MnO2, NiSO4•6H2O, NiCl2•6H2O,…

A Highly Reactive Dicationic Iridium(III) Catalyst for Polarized Nazarov Cyclization

PubMed Central

Vaidya, Tulaza; Atesin, Abdurrahman C.; Herrick, Ildiko R.; Frontier, Alison J.; Eisenberg, Richard

2010-01-01

Pushing the Nazarov Envelope A new electrophilic complex [IrBr(CO)(diethylisopropylidene malonate)((R)-(+)-BINAP)](SbF6)2 (2) exhibits unusual activity in the catalysis of polarized Nazarov cyclization. Aryl vinyl ketones that show poor reactivity with well-known catalysts such as [Ir(CH3)(CO)(1,2-diiodobenzene)(dppe)](B(Arf)4−)2 (1), Sc(OTf)3 + LiClO4 and Cu(ClO4)2, can be cyclized with 2 + AgSbF6 (1:1) under mild conditions with concurrent AgBr precipitation. PMID:20358570

Investigation of efflorescence of inorganic aerosols using fluorescence spectroscopy.

PubMed

Choi, Man Yee; Chan, Chak K

2005-02-17

The phase transition is one of the most fundamental phenomena affecting the physical and chemical properties of atmospheric aerosols. Efflorescence, in particular, is not well understood, partly because the molecular interactions between the solute and water molecules of saturated or supersaturated solution droplets have not been well characterized. Recently, we developed a technique that combines the use of an electrodynamic balance and a fluorescence dye, 8-hydroxyl-1,3,6-pyrenetrisulfonate (pyranine), to study the distributions of solvated and free water in aqueous droplets (Choi, M. Y.; Chan, C. K.; Zhang, Y. H. J. Phys. Chem. A 2004, 108, 1133). We found that the equality of the amounts of solvated and free water is a necessary but not sufficient condition for efflorescence. For efflorescing compounds such as Na2SO4, (NH4)2SO4, and a mixture of NaCl and Na2SO4, the amount of free water decreases, while that of solvated water is roughly constant in bulk measurements and decreases less dramatically than that of free water in single-particle measurements as the relative humidity (RH) decreases. Efflorescence of the supersaturated droplets of these solutions occurs when the amounts of free and solvated water are equal, which is consistent with our previous observation for NaCl. For nonefflorescing compounds in single-particle levitation experiments such as MgSO4 and Mg(NO3)2, the amounts of free and solvated water are equal at a water-to-solute molar ratio of about 6, at which spectral changes due to the formation of contact ion pairs between magnesium and the anions occur as shown by Raman spectroscopy. Fluorescence imaging shows that the droplets of diluted Mg(NO3)2 (at 80% RH) and MgSO4 are homogeneous but those of NaCl, Na2SO4, (NH4)2SO4, and supersaturated Mg(NO3)2 (at 10% RH) are heterogeneous in terms of the solvated-to-free water distribution. The solvated-to-free water ratios in NaCl, Na2SO4, and (NH4)2SO4 droplets are higher in the outer regions by about half a radius deep than at the center of the droplets.

Salinization owing to evaporation from bare-soil surfaces and its influences on the evaporation

NASA Astrophysics Data System (ADS)

Shimojimaa, Eiichi; Yoshioka, Ryuma; Tamagawa, Ichiro

1996-04-01

To investigate the relationship between evaporation and salinization, the surfaces of three columns of uniform porous materials, desert dune sand, silica sand and glass beads, respectively, were exposed to a temperature-, humidity- and/or wind-speed-controlled ambient atmosphere. For the dune sand, chemicals such as Na +, Ca 2+, Cl - and SO 42-, dissolved mainly from CaSO 4, Na 2SO 4, CaCO 3 and NaC1 in the sand particles, caused marked salinization near the top surface. Slow dissolution of Na 2SO 4 and CaSO 4 influenced the development of concentration profiles for SO 42- and Na + markedly for months after the beginning of the experiment, while the profile of Cl - was not affected directly, because dissolution of NaCl was rapid. Concentration profiles of Cl - for the glass beads and for the silica sand columns filled with a high concentration of NaCI solution of (10 4 mg1 -1 for Cl -), were analysed similarly. Experimental results suggested that the vapour flux in a dry soil became larger because of the increase in the gradient of the vapour density caused by greater chemical enrichment near the top surface compared with that at the evaporation surface. The vapour flux also became smaller as the gradient of the vapour density decreased, owing to the markedly enriched evaporation surface. In the experiment with glass beads, filled with the NaCl solution, solute crystallization (4-10 mm thick) was observed. For the dune sand, only when a turbulent airflow was applied did a crust (a few millimetres in thickness) form entirely on the top surface. Such deposition led to a reduction in the flux of water vapour as the permeable cross-sectional area decreased. The resistance to transfer increased three to ten times for the glass beads but only by 30% for the dune sand. The lower increase for the dune sand may be due to penetration of the applied airflow into cracks in the crust.

[Effects of different salt and alkali stresses on ion distribution in Red globe/Beta grapevines].

PubMed

Du, Yuan-peng; Jin, Xue-juan; Guo, Shu-hua; Fu, Qing-qing; Zhai, Heng

2015-06-01

The potted Red globe/Beta grapevines were selected to irrigated with NaCl, Na2SO4, NaHCO3, NH4Cl, (NH4)2SO4. Hence, the ions which induced leaf etiolation were screened and the impacts of different salt and alkali on ion distribution in different organs of grapevines were investigated. It was found that NaHCO3 exerted the greatest effects on grapevines, leaf etiolation at 14 days after treatment. By contrast, NaCl and NH4Cl treatments induced leaf etiolation at 28 days after treatment. The Na+ content in all the detected organs were significantly increased under NaHCO3 and NaCl treatment, and Na+ content in root under NaHCO3 treatment was 6.4 times as that in control root. NaHCO3 and NaCl treatments significantly decreased K+ content in the organs with the exception of leaf. NaHCO3 treatment significantly decreased K/Na in different organs, which declined to 0.1 in root. By contrast, NaCl treatment significantly decreased K/Na in the detected organs with exception of stem. Besides, the transport of Ca2+, Mg2+, Fe2+ to aboveground organs was significantly decreased by NaHCO3 and NaCl treatments. K/Na ratio in the detected organs were decreased under NH4Cl, (NH4) 2SO4 and Na2SO4 treatments, especially under NH4 Cl treatment. Taken together, NaHCO3 was the primary factor resulting in leaf etiolation, followed by NaCl and NH4Cl, while (NH4) 2SO4 and Na2SO4 produced impacts.

A salting out system for improving the efficiency of the headspace solid-phase microextraction of short and medium chain free fatty acids.

PubMed

Fiorini, Dennis; Pacetti, Deborah; Gabbianelli, Rosita; Gabrielli, Serena; Ballini, Roberto

2015-08-28

Given the importance of short and medium chain free fatty acids (FFAs) in several fields, this study sought to improve the extraction efficiency of the solid-phase microextraction (SPME) of FFAs by evaluating salting out agents that appear promising for this application. The salts ammonium sulfate ((NH4)2SO4) and sodium dihydrogen phosphate (NaH2PO4) were tried on their own and in combination (3.7/1), in four different total amounts, as salting out agents in the headspace-SPME-gas chromatographic (HS-SPME-GC) analysis of the FFAs from acetic acid (C2) to decanoic acid (C10). Their performance in a model system of an aqueous standard mixture of FFAs at a pH of 3.5 was compared to that of the more commonly used sodium chloride (NaCl) and sodium sulfate (Na2SO4). All of the salts and salt systems evaluated, in proper amount, gave improved results compared to NaCl (saturated), which instead gave interesting results only for the least volatile FFAs C8 and C10. For C2-C6, the salt system that gave the best results compared to NaCl was (NH4)2SO4/NaH2PO4, in the highest of the four amounts evaluated, with factor increases between 1.2 and 4.1-fold, and NaH2PO4, between 1.0 and 4.3-fold. The SPME extraction efficiency given by the mixture (NH4)2SO4/NaH2PO4 was also assessed on biological and food samples, confirming that overall it performed better than NaCl. Copyright © 2015 Elsevier B.V. All rights reserved.

Archeological Excavations at Two Prehistoric Campsites Near Keystone Dam, El Paso, Texas.

DTIC Science & Technology

1985-07-19

LA Cl) en n en eneM 260 E-a~ 4) V I-II 1-44- 060 0 C.L 0 0. 0. U . 0 0 c 4-. 4-1 b ) 4- 0 0)b Z- c. Vd c*1. ) 1- . - -c*1 -* -4 *d d-,I -bo~ -I . as4...2 17n33w 4 1 2311 flk 3 17n33w 0 2 2017 f1k 2 17n33w 5 5 2326 fUk 3 10sl4w 5 2 2017 f1k 3 17n33w 5 4 2328 fUk 2 10sl4w 7 2 2018 flk 3 17n33w 6 1

Behaviour of complexes of f-elements in the environment - An experimental and theoretical analysis

NASA Astrophysics Data System (ADS)

Ivanova, Bojidarka; Spiteller, Michael

2017-01-01

The paper provides a comprehensive study of lanthanide and actinide complexes to a matter of key area in the field of the chemistry, i.e. environmental analytical chemistry. The content has involved: (i) solution and sorption behaviour of lanthanides (Lnn+, Ln = Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Py, Ho, Er, Tm, Yb and Lu) onto Y(O)O(H) minerals (Y = Fe, Mn or Si); (ii) ligand exchange processes with participation of inorganic OH-, F-, Cl-, Br-, SO42-, SO32-, IO3-, NO32-, CO32- and/or HCO3- ligands as well as mixed ligand complexes, including solvent molecules such as {[LnOR]2+}, {[Ln(OR)2]+} (R = CH3OH, CH3CH2CH2OH) and {[Ln(CH3CN)x(H2O)z]3+} (x = 6-8, z = 0-4); (iii) the actinide speciation has involved different oxidation states (+4)-(+6) and ions {[UOH]3+}, {[UX]3+} (X = F or Cl), {[UFx]y+/-} (x = 2-6, y = 0-2), {[U(CO3)x]y-} (x = 4 or 5, y = 4 or 6), {[U(SO4)]2+], {[U(NO3)]3+}, {[U(NO3)2]2+}, [[UO2(CO3)3]5-}, {[(UO2)x(OH)z]y+/-} (x = 1-4, y = 1 or 2, z = 1-7), {[UO2Fx]y+/-} (x = 1-4, y = 1 or 2), {[UO2(CO3)x]y-} (x = 2, or 3, y = 2, or 4), {[(UO2)2(CO3)(OH)3]-}, {[(UO2)3O(OH)2(HCO3)]+}, {[(UO2)11(CO3)6(OH)12]2-}, {[UO2(SO4)x]y-}, (x = 2 or 3, y = 2 or 4), {[UO2SiO(OH)3]+}, {[AnCx]y+/-} (x,y = 1 and 2), {[CAnH]+/-}, {[CxAny]0} (x,y = 2 and 3), {[AnHx]y+} (x = 1-3, y = 0-5), {[AnXn]m+/-} (n = 1-6, m = 1-4, X = F-, Br-, I-), {[AnOxFz]y+/-} (x, z = 1 or 2, y = 0, 1 and 2), {[AnNx]y+} (x = 1 and 2), {[AnxOz(OH)n]y+/-} (x = 1-3, z = 1-4, y = 0, 1 or 2, n = 0 or 1) and Ann+ (n = 0-6) at An = Th, Pa, U, Np, Pu, Am, Cm, Bk, Cf, Es, Fm, Md, No and Lr, respectively. Correlation analysis between thermodynamic parameters, accounting for different surface interactions of adsorbed species and experimental mass spectrometric data, including liquid, semi-liquid and solid-state measurements in a large set of experimental conditions such as pH = 2-13, low and intermediate ionic strength, solvent type, ε = 0-78.0, variety of solvent proton accepting and donating numbers and T = 25-400 °C has carried out.

The inorganic speciation of tin(II) in aqueous solution

NASA Astrophysics Data System (ADS)

Cigala, Rosalia Maria; Crea, Francesco; De Stefano, Concetta; Lando, Gabriele; Milea, Demetrio; Sammartano, Silvio

2012-06-01

This paper reports new voltammetric measurements on the interactions between tin(II) and the most important natural inorganic ligands, OH-, Cl-, F-, CO32-, SO42- and PO43-. For a better understanding of tin(II) speciation, an analysis is also given of prior data on the same systems from the literature. The formation constants were determined at t = 25 °C in different ionic media and at different ionic strengths, specifically the following: Sn(OH)q (0.1 ⩽ I/mol L-1 ⩽ 1.0 in NaNO3), SnClr and Sn(OH)Cl (0.1 ⩽ I/mol L-1 ⩽ 2.3 in Na(NO3, Cl)), Sn(SO4)r (0.1 ⩽ I/mol L-1 ⩽ 1.6 in Na(NO3, SO4)), SnHqCO3 and SnHqPO4 (0.15 ⩽ I/mol L-1 ⩽ 1.0 in NaNO3), where the subscripts r and q represent the stoichiometric coefficients. Concerning the SnFr species, reliable literature values were considered (0.15 ⩽ I/mol L-1 ⩽ 1.0 in NaClO4). Fifteen voltammetric measurements were performed in synthetic seawater; the total seawater binding ability was evaluated by a model in which synthetic seawater is expressed as a single salt, BA. The formation of species between tin(II) and the anion of the marine salt (A) was also proposed, and the corresponding stability constants at different salinities (5 ⩽ S ⩽ 50) were reported. In addition, studies on the solubility of Sn(OH)2(s) were carried out using voltammetry and light scattering measurements. The "extra-stability" of the mixed species with respect to the parent species was evaluated, in particular for Sn(OH)Cl and the corresponding species involving the anion of the marine salt (A). The dependence of the formation constants on ionic strength was analysed using extended Debye-Hückel and Specific ion Interaction Theory (SIT) type equations. Tin(II) speciation was also evaluated in different natural fluid conditions, where, in all cases, carbonate complexation was predominant, hampering the formation of hydrolytic species throughout the investigated pH range. Moreover, some formation enthalpy changes were calculated for the Sn(OH)+, Sn(OH)2(aq), Sn(OH)2(s), Sn(OH)3-, Sn(OH)22+, Sn(OH)42+, Sn(OH)Cl, SnCl+, SnCl2 and SnCl3- species on the basis of the available literature stability constant values at different temperatures and using the empirical relationships reported in the literature. The ΔH values at t = 25 °C were positive in all cases except for the Sn(OH)2(s) and Sn(OH)3- species, indicating an increase in the stability constant values with increasing temperature. This work represents an advance in the knowledge, understanding and modelling of the inorganic speciation of tin(II) in natural fluids, particularly for solutions containing chloride, fluoride, sulphate, carbonate and phosphate anions.

Characterization and source analysis of water-soluble inorganic ionic species in PM2.5 in Taiyuan city, China

NASA Astrophysics Data System (ADS)

He, Qiusheng; Yan, Yulong; Guo, Lili; Zhang, Yanli; Zhang, Guixiang; Wang, Xinming

2017-02-01

PM2.5 samples were collected in urban area in Taiyuan for four seasons from August 2009 to April 2010. The Water-soluble inorganic ions (WSI, including F-, Cl-, NO3-, SO42 -, Na+, NH4+, K+, Mg2 +, and Ca2 +) were analyzed by ion chromatography. The daily PM2.5 levels in the field samples varied from 49.90 to 477.93 μg/m3 with the mean of 209.54 μg/m3, which all largely exceeded the PM2.5 24-hour limitation value of 35 μg/m3 in Environmental Protection Administration of United States and 75 μg/m3 in Ministry of Environmental Protection of China. The WSI average concentration was 68.86 μg/m3 and accounted for about 32.86% of PM2.5. As the most abundant anion and cation, SO42 - and NH4+ were 43.53 and 14.78 percent of WSI, respectively. PM2.5 in Taiyuan was acidic by the micro-equivalents concentration methods but nearly neutral in autumn, and the chemical forms of WSI were mainly NH4HSO4, (NH4)2SO4 and NH4NO3. PM2.5 and WSI levels showed obvious seasonal variation and were the highest in winter in all samples. PM2.5, SO42 -, and some coal-related ions such as NH4+ and Cl- were higher in winter than other seasons, which mainly attributed to more coal combustion for power and indoor heating supply. The ratio analysis showed that Mg2 + and Ca2 + were not only from soil dust, but also from coal combustion and industry emission. Biomass burning such as the cornstalk and tree branches led to the highest K+ emission in autumn and summer. Wind had a regular influence on the PM2.5 and WSI, and would transport the soil dust mainly from the northwest and also lead to re-suspension of dust in the air when the wind speed was high. Furthermore, the dustpan topography easily helped the pollutants to concentrate in Taiyuan city, and some coal coking industries might contribute to high PM2.5 and WSI in Taiyuan.

AN EXPERIMENTAL STUDY ON ARTIFICIAL CONDENSATION NUCLEI,

DTIC Science & Technology

NH4Cl, CaCl2, P205, NH4NO3, (NH4)2SO4, etc.) and suspensoids such as camphor , silicon minerals, kaolin, lamp black, and calcium lime (CaO). The...findings reveal that the above mentioned soluble nuclei and camphor powder are active artificial hygroscopic condensation nuclei and that lamp black

Electrodeposition of platinum on highly oriented pyrolytic graphite. Part I: electrochemical characterization.

PubMed

Lu, Guojin; Zangari, Giovanni

2005-04-28

The electrochemical deposition of Pt on highly oriented pyrolytic graphite (HOPG) from H2PtCl6 solutions was investigated by cyclic voltammetry and chronoamperometry. The effects of deposition overpotential, H2PtCl6 concentration, supporting electrolyte, and anion additions on the deposition process were evaluated. Addition of chloride inhibits Pt deposition due to adsorption on the substrate and blocking of reduction sites, while SO4(2-) and ClO4- slightly promote Pt reduction. By comparing potentiostatic current-time transients with the Scharifker-Hills model, a transition from progressive to instantaneous nucleation was observed when increasing the deposition overpotential. Following addition of chloride anions the fit of experimental transients with the instantaneous nucleation mode improves, while the addition of SO4(2-) induces only small changes. Chloride anions strongly inhibit the reduction process, which is shifted in the cathodic direction. The above results indicate that the most appropriate conditions for growing Pt nanoparticles on HOPG with narrow size distribution are to use an H2PtCl6 solution with HCl as supporting electrolyte and to apply a high cathodic overpotential.

The chemistry of the severe acidic precipitation in Shanghai, China

NASA Astrophysics Data System (ADS)

Huang, Kan; Zhuang, Guoshun; Xu, Chang; Wang, Ying; Tang, Aohan

2008-07-01

Seventy-six rain samples from forty-seven rain events and TSP aerosol samples throughout the entire year of 2005 were collected in Shanghai, China. The annual mean pH in rain was 4.49 with the lowest pH of 2.95, and the frequency of acid rain was 71% in 2005. The acidity of rain increased more than 15 times in the past 8 years compared to 1997. The volume-weighted mean ionic concentrations of the acidic ions, SO 42- and NO 3- in rainwater were 199.59 and 49.80 μeq/L with maximum of 832.67 and 236.59 μeq/L, respectively. The concentration of SO 42- was higher than the most polluted cities abroad, indicating Shanghai has been a severe polluted city over the world. The high coal/fuel consumption from urbanization and the rapid increase of vehicles resulted in the high emission of SO 2 and NO x, the precursor of the high concentration of acidic ions, SO 42- and NO 3-, which were the main reason of the severe acid rain in Shanghai. The major ions showed clear temporal variations with higher concentrations of SO 42-, NO 3-, NH 4+, and Ca 2+ in spring/winter, of Na +, Cl -, K +, and Mg 2+ in autumn, and the lowest of all the ions in summer. SO 42- and NO 3- were mainly in the form of CaSO 4 and Ca(NO 3) 2, which showed the dominant neutralization effect of Ca 2+ over NH 4+. Source identification indicated that SO 42-, NO 3-, NH 4+ and most Ca 2+ derived from anthropogenic sources, K +, Mg 2+ and partial Ca 2+ originated from mineral, and almost all the Cl - and Na + from the sea. The chemistry of precipitation in Shanghai was under the influence of local pollution sources and the long- and moderate-range transport through back trajectory analysis.

Arene-mercury complexes stabilized by gallium chloride: relative rates of H/D and arene exchange.

PubMed

Branch, Catherine S; Barron, Andrew R

2002-11-27

We have previously proposed that the Hg(arene)(2)(GaCl(4))(2) catalyzed H/D exchange reaction of C(6)D(6) with arenes occurs via an electrophilic aromatic substitution reaction in which the coordinated arene protonates the C(6)D(6). To investigate this mechanism, the kinetics of the Hg(C(6)H(5)Me)(2)(GaCl(4))(2) catalyzed H/D exchange reaction of C(6)D(6) with naphthalene has been studied. Separate second-order rate constants were determined for the 1- and 2-positions on naphthalene; that is, the initial rate of H/D exchange = k(1i)[Hg][C-H(1)] + k(2i)[Hg][C-H(2)]. The ratio of k(1i)/k(2i) ranges from 11 to 2.5 over the temperature range studied, commensurate with the proposed electrophilic aromatic substitution reaction. Observation of the reactions over an extended time period shows that the rates change with time, until they again reach a new and constant second-order kinetics regime. The overall form of the rate equation is unchanged: final rate = k(1f)[Hg][C-H(1)] + k(2f)[Hg][C-H(2)]. This change in the H/D exchange is accompanied by ligand exchange between Hg(C(6)D(6))(2)(GaCl(4))(2) and naphthalene to give Hg(C(10)H(8))(2)(GaCl(4))(2,) that has been characterized by (13)C CPMAS NMR and UV-visible spectroscopy. The activation parameters for the ligand exchange may be determined and are indicative of a dissociative reaction and are consistent with our previously calculated bond dissociation for Hg(C(6)H(6))(2)(AlCl(4))(2). The initial Hg(arene)(2)(GaCl(4))(2) catalyzed reaction of naphthalene with C(6)D(6) involves the deuteration of naphthalene by coordinated C(6)D(6); however, as ligand exchange progresses, the pathway for H/D exchange changes to where the protonation of C(6)D(6) by coordinated naphthalene dominates. The site selectivity for the H/D exchange is initially due to the electrophilic aromatic substitution of naphthalene. As ligand exchange occurs, this selectivity is controlled by the activation of the naphthalene C-H bonds by mercury.

Visible light-induced degradation of acetone over SO42-/MoOx/MgF2 catalysts.

PubMed

He, Yiming; Sheng, Tianlu; Wu, Ying; Chen, Jianshan; Fu, Ruibiao; Hu, Shengming; Wu, Xintao

2009-08-30

A visible light active photodegration catalyst was prepared by doping MoO(3) into MgF(2) matrix. The addition of SO(4)(2-) into MoO(x)/MgF(2) could improve the catalytic activity greatly and an acetone conversion of 96.1% under visible light was obtained on the SO(4)(2-)/5%MoO(x)/MgF(2) (SMM) catalyst. By BET, XRD, Raman, FT-IR, XPS, UV-vis technology the specific area, structure and photoadsorption ability of the catalysts were characterized. The high photocatlaytic activity of the SMM catalyst is attributed to its large specific area, the high dispersal of MoO(3) domains in MgF(2) and the inhibiting effect of MgF(2) matrix on the electron-hole pair recombination.

Chemical composition of precipitation in a Mexican Maya region

NASA Astrophysics Data System (ADS)

Bravo, H. A.; Saavedra, M. I. R.; Sánchez, P. A.; Torres, R. J.; Granada, L. M. M.

The chemical characteristics of wet precipitation in Puerto Morelos, Quintana Roo State, Mexico, were measured from April 1994 to December 1995. Puerto Morelos is located in the Caribbean Mayan coastal region of the Peninsula of Yucatan, and is normally exposed to winds from the Caribbean region. Wetfall was analyzed for pH, conductivity and Cl -, NO 3-, SO 42-, Na +, NH 4+, K +, Mg 2+ and Ca 2+ ion concentrations. Volume-weighted mean pH for the whole sampling period was 5.35, although values as low as 4.6 were measured in several rain samples. Concentrations of all species correlated negatively with rain volume. Sea-salt aerosols contributed with most of the Na +, Cl -, Mg 2+, K + and SO 42- found in wet precipitation. The mean [SO 42-excess] was 9.7 μEq l -1, which agrees with the background hemispheric values of ≈10 μEq l -1 reported elsewhere. The mean [NO 3-] was 11.4 μEq l -1, almost four times higher than the background hemispheric value of ≈2.5 μEq l -1 reported elsewhere. However, a major component causing the slight acidity character of rain in Puerto Morelos seems to be H 2SO 4.

NMR shielding calculations across the periodic table: diamagnetic uranium compounds. 2. Ligand and metal NMR.

PubMed

Schreckenbach, Georg

2002-12-16

In this and a previous article (J. Phys. Chem. A 2000, 104, 8244), the range of application for relativistic density functional theory (DFT) is extended to the calculation of nuclear magnetic resonance (NMR) shieldings and chemical shifts in diamagnetic actinide compounds. Two relativistic DFT methods are used, ZORA ("zeroth-order regular approximation") and the quasirelativistic (QR) method. In the given second paper, NMR shieldings and chemical shifts are calculated and discussed for a wide range of compounds. The molecules studied comprise uranyl complexes, [UO(2)L(n)](+/-)(q); UF(6); inorganic UF(6) derivatives, UF(6-n)Cl(n), n = 0-6; and organometallic UF(6) derivatives, UF(6-n)(OCH(3))(n), n = 0-5. Uranyl complexes include [UO(2)F(4)](2-), [UO(2)Cl(4)](2-), [UO(2)(OH)(4)](2-), [UO(2)(CO(3))(3)](4-), and [UO(2)(H(2)O)(5)](2+). For the ligand NMR, moderate (e.g., (19)F NMR chemical shifts in UF(6-n)Cl(n)) to excellent agreement [e.g., (19)F chemical shift tensor in UF(6) or (1)H NMR in UF(6-n)(OCH(3))(n)] has been found between theory and experiment. The methods have been used to calculate the experimentally unknown (235)U NMR chemical shifts. A large chemical shift range of at least 21,000 ppm has been predicted for the (235)U nucleus. ZORA spin-orbit appears to be the most accurate method for predicting actinide metal chemical shifts. Trends in the (235)U NMR chemical shifts of UF(6-n)L(n) molecules are analyzed and explained in terms of the calculated electronic structure. It is argued that the energy separation and interaction between occupied and virtual orbitals with f-character are the determining factors.

Observed and predicted reproduction of Ceriodaphnia dubia exposed to chloride, sulfate, and bicarbonate

USGS Publications Warehouse

Lasier, Peter J.; Hardin, Ian R.

2010-01-01

Chronic toxicities of Cl-, SO42-, and HCO3- to Ceriodaphnia dubia were evaluated in low- and moderate-hardness waters using a three-brood reproduction test method. Toxicity tests of anion mixtures were used to determine interaction effects and to produce models predicting C. dubia reproduction. Effluents diluted with low- and moderate-hardness waters were tested with animals acclimated to low- and moderate-hardness conditions to evaluate the models and to assess the effects of hardness and acclimation. Sulfate was significantly less toxic than Cl- and HCO3- in both types of water. Chloride and HCO3- toxicities were similar in low-hardness water, but HCO3- was the most toxic in moderate-hardness water. Low acute-to-chronic ratios indicate that toxicities of these anions will decrease quickly with dilution. Hardness significantly reduced Cl- and SO42- toxicity but had little effect on HCO3-. Chloride toxicity decreased with an increase in Na+ concentration, and CO3- toxicity may have been reduced by the dissolved organic carbon in effluent. Multivariate models using measured anion concentrations in effluents with low to moderate hardness levels provided fairly accurate predictions of reproduction. Determinations of toxicity for several effluents differed significantly depending on the hardness of the dilution water and the hardness of the water used to culture test animals. These results can be used to predict the contribution of elevated anion concentrations to the chronic toxicity of effluents; to identify effluents that are toxic due to contaminants other than Cl-, SO42-, and HCO3-; and to provide a basis for chemical substitutions in manufacturing processes.

Study of the reaction of atomic oxygen with aerosols

NASA Technical Reports Server (NTRS)

Akers, F. I.; Wightman, J. P.

1975-01-01

The rate of disappearance of atomic oxygen was measured at several pressures in a fast flow pyrex reactor system with its walls treated with (NH4)2SO4 (s), H2SO4 (l), and NH4CL (s). Atomic oxygen, P-3 was generated by dissociation of pure, low pressure oxygen in a microwave discharge. Concentrations of atomic oxygen were measured at several stations in the reactor system using chemiluminescent titration with NO2. Recombination efficiencies calculated from experimentally determined wall recombination rate constants are in good agreement with reported values for clean Pyrex and an H2SO4 coated wall. The recombination efficiency for (NH4)2SO4, results in a slightly lower value than for H2S04. A rapid exothermic reaction between atomic oxygen and the NH4Cl wall coating prevented recombination efficiency determination for this coating. The results show that the technique is highly useful for wall recombination measurements and as a means of extrapolating to the case of free stream aerosol-gas interactions.

Work function tunability of borophene via doping: A first principle study

NASA Astrophysics Data System (ADS)

Katoch, Neha; Sharma, Munish; Thakur, Rajesh; Ahluwalia, P. K.

2018-04-01

A first principle study of structural properties, work function and electronic properties of pristine and substitutional doped borophene atomic layer with X atoms (X = F, Cl, H, Li, Na) have been carried out within the framework of density functional theory (DFT). Studied adsorption energies are high for all dopants indicating adsorption to be chemisorption type. The reduction in work function of pristine borophene has been found with n-type (Li, Na) dopants is of the order of 0.42 eV which is higher than that of the reduction in work function of borophene with p-type (F, Cl) dopants. For H dopants there is no reduction in work function of borophene. Quantum ballistic conductance has been found to modulate with doping. The quantum ballistic conductance is decreasing for doped borophene in the order Li > Cl ˜ H ˜ Na > F as compared to pristine borophene.

Simulation of the Interaction Between Airdrop Platforms and Aircraft Rollers

DTIC Science & Technology

1982-04-01

0? y coordinates 1 36 138 1 40 42 Ask 46 89.0 7879 80 8’W82 83 84 495211 2 I 5 2 60.0 -& - --------- 59 6006 26 Eg I 20.0 10.0 ~1 ;94:2 57 %- A 63 5...o5: cc0 C’)L cl Cl 0- 0.0 CRC X 00 1%0. z -J .1L vi co 02.~j_____ I- i __________ _ Il ) co V~fC M T 0 O) C)0 f - CW - N - - ciOc’o 0) - 0) - Ws 8 M

[Size distributions and source apportionment of soluble ions in aerosol in Nanjing].

PubMed

Xue, Guo-Qiang; Zhu, Bin; Wang, Hong-Lei

2014-05-01

To explore the seasonal variation and source apportionment of soluble ions in PM10, PM2.1 and PM1.1, the aerosol mass. concentration and soluble ion concentration were investigated during a one-year observation in the urban-district and north suburb. As the results showed, (1)The concentrations of PM10, PM2.1, PM1.1 were in the order of winter > spring > autumn > summer. In spring, summer and autumn, the concentrations of PM10, PM2.1, PM1.1 in the north suburb were higher than in the urban, while the situation, was opposite in winter. (2) SO(2-)(4), NO(-)(3), Ca2+, NH(+)(4), Cl-, K+, Na+, F-, NO;, Mg2+ were measured, and their total concentration in PM10 was 46 microg.m -3 in urban sites and 39.6 microg m in north suburbs. Mass fraction percentage o f water soluble ion in PM2.1-10, PM1 1-2.1, PM1.1 in the urban district increased from 20.4% to 49.5% and 56% , and the value in the north suburb increased from 18.3% to 37. 9% and 42.5%. (3) Major ions, SO(2-)(4), NO(-)(3) , NH(+)(4) , second components and Ca2+ , had significant seasonal variation. In the urban district, the highest concentrations were observed in winter, and the lowest in summer, while in the. north suburb, the highest concentrations were observed in spring, and the lowest in summer. The seasonal changing climate in Nanjing and different anthropogenic influences with land surface in urban-suburb may be the major factors for the ions' seasonal variation. (4) NH(+)(4) , SO(2-)(4) , NO(-)(3) came from secondary chemical reactions of NH3, SO2, NO,, and these precursors mostly came from automobile exhaust in Summer while equally came from automobile exhaust and fossil fuel in winter. Cl- came from biomass burning in Winter . while transported from sea salt with Na+ in Summer. Ca2+ and Mg2+ came from ground dust and construction dust. K+, F- , NO(-)(2) may come from biomass burning and industrial emissions.

Impact of urban development on the chemical composition of ground water in a fen-wetland complex

USGS Publications Warehouse

Panno, S.V.; Nuzzo, V.A.; Cartwright, K.; Hensel, B.R.; Krapac, I.G.

1999-01-01

A 15-month-long hydrogeologic investigation of a fen-wetland complex in northeastern Illinois, USA indicated the encroachment of ground-water-borne anthropogenic contaminants into two of three high quality fens. Ground-water flow directions and chemical evidence indicated that plumes of ground water with anomalously large concentrations of Na+ and Cl- originated from a private septic system and from rock salt spread on an adjacent road. The contamination, in turn, had an adverse effect on fen vegetation; within the plumes, diverse vegetation was replaced by the more salt-tolerant narrow-leaf cattail (Typha angustifolia). Ground water of the third fen contained large concentrations of SO42- as high as 516 mg/L. The SO42- anomaly was observed on a transient and/or seasonal basis in the fen ground water and in an adjacent marsh and pond. Isotopically light ??34S values in these waters indicated that the addition of SO42- resulted from the oxidation of pyrite within underlying peat and/or pyritic gravel. However, the large SO42- concentrations had no discernible effect on fen vegetation. The results of this investigation indicate how easily construction of houses with private septic systems and deicing agents from roadway maintenance can contaminate fen ground water with relatively large concentrations of Na+ and Cl-, resulting in a significant loss of biodiversity in fens.

The variation of characteristics and formation mechanisms of aerosols in dust, haze, and clear days in Beijing

NASA Astrophysics Data System (ADS)

Wang, Ying; Zhuang, Guoshun; Sun, Yele; An, Zhisheng

A 4-year campaign from 2001 to 2004 monitoring PM 2.5 and TSP in the spring season in urban Beijing, China was performed to study the variation of characteristics and the different formation mechanisms of aerosols in dust, haze, and clear days. A total of 315 aerosol samples were collected and used in this study. The aerosols were more basic in dust days and more acidic in haze days. The ions presented in the order of SO42->Ca 2+≫ NO3->Cl -> NH4+>Na + in dust days, and of SO42-> NO3-> NH4+≫Cl ->Ca 2+>K + in haze days. Ions has been classified into three groups, "Na +, Mg 2+, Ca 2+", "K +, SO42-, Cl -", and " NO3-, NH4+", representing crust, pollution-crust, and pollution species, respectively. Crust and pollution ions were the main ion fractions in dust and haze days, respectively. The variation of Ca 2+/Al showed that the increase of dust in dust and haze days was from soil and construction, respectively. "CaCO 3, CaSO 4, and (NH 4) 2SO 4" and "(NH 4) 2SO 4, NH 4NO 3, and Ca(NO 3) 2" were the major species in dust and haze days, respectively. The formation of CaSO 4 on airborne soil particles and the formation of (NH 4) 2SO 4 and NH 4NO 3 were the predominant pathways of sulfate and nitrate formations in dust and haze days, respectively. Sulfate might be mainly formed through heterogeneous reactions in the aqueous surface layer on the pre-existing particles, while nitrate mainly through homogeneous gas-phase reactions in the spring season in Beijing. The formation of sulfate and nitrate was accelerated in dust and haze days.

The effect of sea-water intrusion due to the large scale construction in a coastal region

NASA Astrophysics Data System (ADS)

Hyun, S.; Jin, S.; Woo, N. C.; Lee, J.; Lee, H.; Kim, Y.

2010-12-01

This study was carried out for estimating the seawater intrusion at the disturbed aquifer by a large scale construction when building a power plant in a coastal region, located in southeastern part of the Korean peninsula. Groundwater sampling and vertical profiling of electrical conductivity(EC) for 8 monitoring wells were carried. EC profiling results shows that maximum EC for PW-5, 6 and 7 is over 40 mS/cm, for PZ-1, 3, 4 and 8 is 18.76, 4.46, 26.16, 21.42 mS/cm and for PZ-2 is 0.79 mS/cm,respectively. Chemical composition of water samples shows that water types of Na-Cl for PZ-5, 6, and 7 (excavated and backfilled area), Na-Cl-SO4 for PZ-4 and PZ-8, Na-Ca-Mg-Cl for PZ-1, Ca-Na-SO4-Cl for PZ-2, and Mg-Ca-Na-SO4 for PZ-3. In addition, the bivariate plot of SO4/Cl(meq ratios) and SO4(mmol/L) indicates that PZ-4, 5, 6, 7 and 8 appear to be seawater, PZ-1 is located at mixing zone between freshwater and seawater, and PZ-2 is freshwater. However, based on the high SO42- level and (HCO3-/Sum anions} ratio less than 0.8, groundwater at PZ-3 seems to show the gypsum dissolution. The gypsum dissolution was attributed to the effect of sea-water intrusion on ageing of lean concrete that was used for backfill around the PZ-3. Key words : large scale construction, EC profiling, hydrochemistry, sea-water intrusion, concrete ageing Acknowledgement This study has been carried out under the Nuclear R&D Program [No. 2010-0001070] supported by the Ministry of Education, Science and Technology, Republic of Korea.

Toxic fluoride and arsenic contaminated groundwater in the Lahore and Kasur districts, Punjab, Pakistan and possible contaminant sources.

PubMed

Farooqi, Abida; Masuda, Harue; Firdous, Nousheen

2007-02-01

The present study is the first attempt to put forward possible sources of As, F- and SO4(2-) contaminated groundwater in the Kalalanwala area, Punjab, Pakistan. Five rainwater and 24 groundwater samples from three different depths were analyzed. Shallow groundwater from 24 to 27 m depth contained high F- (2.47-21.1mg/L), while the groundwater samples from the deeper depth were free from fluoride contamination. All groundwater samples contained high As (32-1900 microg/L), in excess of WHO drinking water standards. The SO4(2-) ranges from 110 to 1550 mg/L. Delta34S data indicate three sources for SO4(2-) air pollutants (5.5-5.7 per thousand), fertilizers (4.8 per thousand), and household waste (7.0 per thousand). Our important finding is the presence of SO4(2-), As and F- in rainwater, indicating the contribution of these elements from air pollution. We propose that pollutants originate, in part, from coal combusted at brick factories and were mobilized promotionally by the alkaline nature of the local groundwater.

Donnan membrane technique (DMT) for anion measurement.

PubMed

Vega, Flora Alonso; Weng, Liping; Temminghoff, Erwin J M; Van Riemsdijk, Willem H

2010-04-01

Donnan membrane technique (DMT) is developed and tested for determination of free anion concentrations. Time needed to reach the Donnan membrane equilibrium depends on type of ions and the background. The Donnan membrane equilibrium is reached in 1 day for Cl(-), 1-2 days for NO(3)(-), 1-4 days for SO(4)(2-) and SeO(4)(2-), and 1-14 days for H(2)PO(4)(-) in a background of 2-200 mM KCl or K(2)SO(4). The strongest effect of ionic strength on equilibrium time is found for H(2)PO(4)(-), followed by SO(4)(2-) and SeO(4)(2-), and then by Cl(-) and NO(3)(-). The negatively charged organic particles of fulvic and humic acids do not pass the membrane. Two approaches for the measurement of different anion species of the same element, such as SeO(4)(2-) and HSeO(3)(-), using DMT are proposed and tested. These two approaches are based on transport kinetics or response to ionic strength difference. A transport model that was developed previously for cation DMT is applied in this work to analyze the rate-limiting step in the anion DMT. In the absence of mobile/labile complexes, transport tends to be controlled by diffusion in solution at a low ionic strength, whereas at a higher ionic strength, diffusion in the membrane starts to control the transport.

Haloacyl complexes of boron, [(CF3)3BC(O)Hal]- (Hal=F, Cl, Br, I).

PubMed

Finze, Maik; Bernhardt, Eduard; Willner, Helge; Lehmann, Christian W

2005-11-04

The haloacyltris(trifluoromethyl)borate anions [(CF3)3BC(O)Hal]- (Hal=F, Cl, Br, I) have been synthesized by reacting (CF3)3BCO with either MHal (M=K, Cs; Hal=F) in SO2 or MHal (M=[nBu4N]+, [Et4N]+, [Ph4P]+; Hal=Cl, Br, I) in dichloromethane. Metathesis reactions of the fluoroacyl complex with Me3SiHal (Hal=Cl, Br, I) led to the formation of its higher homologues. The thermal stabilities of the haloacyltris(trifluoromethyl)borates decrease from the fluorine to the iodine derivative. The chemical reactivities decrease in the same order as demonstrated by a series of selected reactions. The new [(CF3)3BC(O)Hal]- (Hal=F, Cl, Br) salts are used as starting materials in the syntheses of novel compounds that contain the (CF3)3B-C fragment. All borate anions [(CF3)3BC(O)Hal]- (Hal=F, Cl, Br, I) have been characterized by multinuclear NMR spectroscopy (11B, 13C, 17O, 19F) and vibrational spectroscopy. [PPh4][(CF3)3BC(O)Br] crystallizes in the monoclinic space group P2/c (no. 13) and the bond parameters are compared with those of (CF3)3BCO and K[(CF3)3BC(O)F]. The interpretation of the spectroscopic and structural data are supported by DFT calculations [B3LYP/6-311+G(d)].

Ion composition of coarse and fine particles in Iasi, north-eastern Romania: Implications for aerosols chemistry in the area

NASA Astrophysics Data System (ADS)

Arsene, Cecilia; Olariu, Romeo Iulian; Zarmpas, Pavlos; Kanakidou, Maria; Mihalopoulos, Nikolaos

2011-02-01

Atmospheric loadings of the aerosols coarse (particles of AED > 1.5 μm) and fine fractions (particles of AED < 1.5 μm) were determined in Iasi, north-eastern Romania from January 2007 to March 2008. Concentrations of water soluble ions (SO 42-, NO 3-, Cl -, C 2O 42-, NH 4+, K +, Na +, Ca 2+ and Mg 2+) were measured using ion chromatography (IC). In the coarse particles, calcium and carbonate are the main ionic constituents (˜65%), whereas in the fine particles SO 42-, NO 3-, Cl - and NH 4+ are the most abundant. Temperature and relative humidity (RH) associated with increased concentrations of specific ions might be the main factors controlling the aerosol chemistry at the investigated site. From August 2007 to March 2008 high RH (as high as 80% for about 82% of the investigated period) was prevailing in Iasi and the collected particles were expected to have deliquesced and form an internal mixture. We found that in fine particles ammonium nitrate (NH 4NO 3) is important especially under conditions of NH 4+/SO 42- ratio higher than 1.5 and high RH (RH above deliquescence of NH 4Cl, NH 4NO 3 and (NH 4) 2SO 4). At the investigated site large ammonium artifacts may occur due to inter-particle interaction especially under favorable meteorological conditions. A methodology for estimating the artifact free ambient ammonium concentration is proposed for filter pack sampling data of deliquesced particles. Nitrate and sulfate ions in coarse particles are probably formed via reactions of nitric and sulfuric acid with calcium carbonate and sodium chloride which during specific seasons are abundant at the investigated site. In the fine mode sulfate concentration maximized during summer (due to enhanced photochemistry) and winter (due to high concentration of SO 2 emitted from coal burning). Natural contributions, dust or sea-salt related, prevail mainly in the coarse particles. From May 2007 to August 2007, when air masses originated mainly from Black Sea, in the coarse particles an nss-Cl/Na ratio of 1.11 was measured. Elevated levels of chloride in fine particles have been attributed to waste burning in the proximity of the investigated site or to NaCl salt widely spread on roads during winter. Considering the importance of atmospheric aerosols, this study may constitute a reference point for Eastern Europe.

Contribution of an ancient evaporitic-type reservoir to lake vostok chemistry

NASA Astrophysics Data System (ADS)

de Angelis, M.; Thiemens, M. H.; Savarino, J.; Petit, J. R.

2003-04-01

Accretion ice 1 (3538 to 3608 m) contents visible sediment inclusions likely incorporated into ice in a shallow bay upstream Vostok where glacier moves against a relief rise. Ion chromatography measurements indicate that elemental concentrations are linked to inclusions abundances. More than 80% of SO_42- is present as CaSO_4 or MgSO_4. While SO_42- concentrations and the relative proportion of CaSO_4 and MgSO_4 varies in a wide range in accreted ice, concentration profiles of Na and Cl, present as NaCl, are much more regular even along individual crystals. Question rises about the presence of such salts in lake water: The 17O anomaly of sulphate in one samples taken at 3570 m suggests that less than 10% of total sulphate comes from DMS oxidation, ruling out any significant contribution of glacer melt water. Fe concentrations are low (10 ppb) excluding sulphate production from the pyrite oxidation by biogenic in-situ activity. This conclusion is supported by the isotopic signature of 34S. Taken all together, these observations strongly suggest the contribution of an evaporitic-type basin to the lake salinity. Assuming that sediments accumulated in an isolated reservoir prior the lake formation, seismotectonic activated hydrothermal circulation may pulse NaCl rich water with sulphate salts through faults up to their vents in a shallow bay upstream Vostok, where they could be incorporated in the accreted ice and also contribute to lake salinity.

Seasonal variations in the major chemical species of snow at the South East Dome in Greenland

NASA Astrophysics Data System (ADS)

Oyabu, Ikumi; Matoba, Sumito; Yamasaki, Tetsuhide; Kadota, Moe; Iizuka, Yoshinori

2016-03-01

We analyze snow-pit samples collected in May 2015 at the South East Dome (SE Dome) on the Greenland ice sheet. The analysis includes high-resolution records of δD and δ18O, as well as the major ions, CH3SO3-, Cl-, NO3-, SO42-, Na+, NH4+, K+, Ma2+, and Ca2+. We find that the 3.55-m snow pit recorded temperature and aerosol proxies back to summer or autumn of 2014. This indicates a higher accumulation rate than those at other major drilling sites in Greenland. Due to this high accumulation rate, ion concentrations except Na+ are lower than those typical of the central Greenland ice sheet. Concerning seasonal variability, the Na+, Cl-, Ca2+, Mg2+, and NO3- vary similarly to other sites in Greenland, with the Na+ and Cl- peaking in winter to early spring, Ca2+ peaking in spring, Mg2+ peaking in winter to spring, and NO3- towards a peak in summer while showing smaller peaks in winter to spring. The NH4+ increased in spring, and SO42- increased in autumn to winter at SE Dome. On the other hand, the seasonal trend in the Cl-/Na+ ratio differs from those in the inland region. As we did not fully recover one seasonal cycle, some seasonal peaks may have been missed.

Hemolysis area: A new parameter of erythrocyte osmotic fragility for screening of thalassemia trait

PubMed Central

Tatu, Thanusak; Sweatman, Denis

2018-01-01

BACKGROUND: One-tube osmotic fragility test (OFT) is widely used for screening thalassemia traits. Interobserver variation may occur with 0.36% NaCl-based OFT due to the naked eye result reading style. PURPOSE: The purpose of this study was to establish and evaluate the novel numerical OFT-based parameter, so-called hemolysis area (HA), in screening thalassemia traits. MATERIALS AND METHODS: The portable spectrophotometer was invented capable of calculating the HA values. The HA values were then compared among 69, 156, and 19 blood samples having positive, negative, and suspicious 0.36% NaCl-based OFT results, respectively; 109 and 135 blood samples having mean corpuscular volume (MCV) ≤80 fL and >80 fL, respectively; and 138 and 106 blood samples having mean corpuscular hemoglobin (MCH) ≤27 pg and >27 pg, respectively. In addition, the HA values were compared in 166 blood samples having different globin gene genotypes. Finally, the HA cutoff value was determined by receiver operation curve (ROC) analysis. RESULTS: The HA values in samples having positive, suspicious, and negative 0.36% NaCl-based OFT were 33.3 ± 14.4, 42.9 ± 10.5, and 65.3 ± 13.4, respectively; in sample having MCV ≤80 fL and >80 fL were 43.1 ± 19.6 and 63.8 ± 14.5, respectively; and in samples having MCH ≤27 pg and >27 pg were 46.7 ± 20.1 and 64.8 ± 14.2, respectively. The HA values in normal, hemoglobin E, SEA-α thalassemia 1, and β-thalassemia traits were 67.1 ± 12.6, 36.4 ± 13.9, 20.2 ± 4.8, and 18.6 ± 1.1, respectively. All were significantly different. ROC analysis established 52.4 as the HA cutoff that had comparable effectiveness to the conventional screening tests. CONCLUSION: The new HA value was effective and could be an alternative choice for screening thalassemia traits. PMID:29692590

The impacts of anthropogenic emissions on the precipitation chemistry at an elevated site in North-eastern China

NASA Astrophysics Data System (ADS)

Wang, Yan; Wai, Ka Ming; Gao, Jian; Liu, Xiaohuan; Wang, Tao; Wang, Wenxing

Ninety precipitation samples were collected from 2004 to 2006 at the summit of the Mt. Tai in order to detect the impacts of regional sources of pollution on precipitation chemistry in the highly polluted North China Plains. The annual volume-weighted pH of the precipitation was found to be 4.7, in contrast to the less-acidic nature (pH>5.6) of precipitation in northern China reported in many past studies. Non-sea-salt (nss)-SO 42- (131.5 μeq L -1), NH 4+ (82.2 μeq L -1) and Ca 2+ (61.4 μeq L -1) were the most abundant species in precipitation. The wide range of the Cl -/Na + ratios (0.2-5.4) in precipitation implied the co-existence of Cl - enrichment and depletion. The nss-SO 42-, NO 3-, NH 4+, Ca 2+ and K + concentrations peaked in spring, but with the lowest acidity. The very strong correlations of Ca 2+ with nss-SO 42- and NO 3- suggested a significant uptake of nss-SO 42- and NO 3- on dust aerosol during spring. Samples with the lowest pH value (4.5) are associated with the stagnant air conditions. The nss-SO 42- and NH 4+ concentrations at Mt. Tai were the highest compared with those at the EANET, NADP and EMEP sites of similar elevations. With relatively high rainfall amount measured at our site, the high wet deposition of the major acidic/alkaline species exerted large loadings to the ecosystem. The associated impacts on agriculture, soil and aquatic systems should be investigated.

Excimer laser debridement of necrotic erosions of skin without collateral damage

NASA Astrophysics Data System (ADS)

Wynne, James J.; Felsenstein, Jerome M.; Trzcinski, Robert; Zupanski-Nielsen, Donna; Connors, Daniel P.

2011-07-01

Pulsed ArF excimer laser radiation at 6.4 eV, at fluence exceeding the ablation threshold, will debride burn eschar and other dry necrotic erosions of the skin. Debridement will cease when sufficiently moist viable tissue is exposed, due to absorption by aqueous chloride ions (Cl-) through the non-thermal process of electron photodetachment, thereby inhibiting collateral damage to the viable tissue. ArF excimer laser radiation debrides/ablates ~1 micron of tissue with each pulse. While this provides great precision in controlling the depth of debridement, the process is relatively time-consuming. In contrast, XeCl excimer laser radiation debrides ~8 microns of tissue with each pulse. However the 4.0 eV photon energy of the XeCl excimer laser is insufficient to photodetach an electron from a Cl- ion, so blood or saline will not inhibit debridement. Consequently, a practical laser debridement system should incorporate both lasers, used in sequence. First, the XeCl excimer laser would be used for accelerated debridement. When the necrotic tissue is thinned to a predetermined thickness, the ArF excimer laser would be used for very precise and well-controlled debridement, removing ultra-thin layers of material with each pulse. Clearly, the use of the ArF laser is very desirable when debriding very close to the interface between necrotic tissue and viable tissue, where the overall speed of debridement need not be so rapid and collateral damage to viable tissue is undesirable. Such tissue will be sterile and ready for further treatment, such as a wound dressing and/or a skin graft.

Chemical characterization and source apportionment of size-resolved particles in Hong Kong sub-urban area

NASA Astrophysics Data System (ADS)

Gao, Yuan; Lee, Shun-Cheng; Huang, Yu; Chow, Judith C.; Watson, John G.

2016-03-01

Size-resolved particulate matter (PM) samples were collected with a 10-stage Micro-Orifice Uniform Deposit Impactor (MOUDI) at a sub-urban site (Tung Chung) in Hong Kong for four non-consecutive months representing four seasons from 2011 to 2012. Major chemical components were water-soluble anions (i.e., Cl-, NO3-, and SO42 -), cations (i.e., NH4+, Na+, K+, and Ca2 +), organic and elemental carbon and elements. Both chemical mass closure and positive matrix factorization (PMF) were employed to understand the chemical composition, resolve particle size modes, and evaluate the PM sources. Tri-modal size distributions were found for PM mass and major chemical components (e.g., SO42 -, NH4+, and OC). Mass median aerodynamic diameters (MMADs) with similar standard deviations (1.32 < σ < 1.42) were 0.4, 0.7 and 3.8 μm, consistent with condensation, droplet and coarse modes. A bi-modal distribution peaking at condensation and droplet modes was found for EC, with a single mode peaking at 3.8 μm for Cl-. Besides secondary SO42 -, carbonaceous aerosol dominated the condensation mode with 27% by engine exhaust and 18-19% each by residual oil combustion (shipping) and coal/biomass burning. Secondary SO42 - is also the most dominant component in the droplet mode, accounting for 23% of PM mass, followed by an industrial source (19%). Engine exhaust, secondary NO3-, and sea salt each accounted for 13-15% of PM mass. Sea salt and soil are the dominated sources in the coarse mode, accounting for 80% of coarse mass.

Origin of rainwater acidity near the Los Azufres geothermal field, Mexico

USGS Publications Warehouse

Verma, M.P.; Quijano, J.L.; Johnson, Chad; Gerardo, J.Y.; Arellano, V.

2000-01-01

The chemical and isotopic compositions of rainwater were monitored at Los Azufres geothermal field (88 MWe) and its surroundings during May - September 1995, which is the rainy season. Samples were collected from eight sites: three within the field, three in its surroundings and two sufficiently far from the field such that they have no geothermal input. The concentrations of Cl-, SO42- and NO3- were measured in about 350 samples and found to be generally <5 ppm. Chloride concentrations remained constant with time, but sulfate and nitrate concentrations decreased, which suggests a nearby industrial source for the sulfate and nitrate. A mixing model for Cl-, SO42- and ??34S also suggests an industrial source for the rainwater sulfur. The determination of pH was found to be necessary, but is not sufficient to characterize rainwater acidity. The Gran titration method was used to determine alkalinity with respect to equivalence point of H2CO3(*). Values of alkalinity were found to range from 10-4 to 10-6 eq/L, and were negative only for some samples from Vivero and Guadalajara. Thus, SO42- and NO3- are in general not in acidic form (i.e. balanced by Na+, Ca2+, etc. rather than H+). Sulfate ??34S values were about -1.5??? in Los Azufres and its surroundings, and in Morelia, but differed from the value of -0.2??? for Guadalajara. The ??34S values for H2S from the Los Azufres geothermal wells are in the range -3.4 to 0.0???. The ??34S ranges for the natural and anthropogenic sources for environmental sulfur overlap, making it difficult to differentiate between the contribution of different sources. However, a similarity of values of ??34S at Los Azufres and Morelia (85 km distant) suggest a regional source of sulfate that is not associated with geothermal emissions from Los Azufres. (C) 2000 Published by Elsevier Science Ltd on behalf of CNR.The chemical compositions of rainwater were analyzed at Los Azufres geothermal field in Spain from May-September 1995. The concentrations of Cl-, SO42- and NO3- were measured and found to be generally <5 ppm. Chloride concentrations remained constant with time, but sulfate and nitrate concentrations decreased, suggesting a nearby industrial source. A mixing model for Cl-, SO42-, and ??34S also suggested an industrial source for the rainwater sulfur.

[Isolation and purification of alpha-glycerophosphate oxidase in a polyethylene glycol/(NH4 )2SO4 aqueous two-phase system].

PubMed

Meng, Yao; Jin, Jiagui; Liu, Shuangfeng; Yang, Min; Zhang, Qinglian; Wan, Li; Tang, Kun

2014-02-01

Alpha-glycerophosphate oxidase (alpha-GPO) from Enterococcus casseli flavus was successfully isolated and purified by using polyethylene glycol (PEG)/(NH4)2SO4 aqueous two-phase system (ATPS). The results showed that the chosen PEG/(NH4)2SO4 ATPS could be affected by PEG molecular weight, pH, concentration of PEG and (NH4)2SO4, and inorganic salt as well as additional amount of crude enzyme. After evaluating these influencing factors, the final optimum purification strategy was formed by 16.5% (m/m) PEG2000, 13.2% (m/m) (NH4)2SO4, pH 7.5 and 30% (m/m) additive crude enzyme, respectively. The NaCl was a negative influencing factor which would lead to lower purification fold and activity recovery. These conditions eventually resulted in the activity recovery of 89% (m/m), distribution coefficient of 1.2 and purification fold of 7.0.

Decolorization and mineralization of Allura Red AC aqueous solutions by electrochemical advanced oxidation processes.

PubMed

Thiam, Abdoulaye; Sirés, Ignasi; Garrido, José A; Rodríguez, Rosa M; Brillas, Enric

2015-06-15

The decolorization and mineralization of solutions containing 230 mg L(-1) of the food azo dye Allura Red AC at pH 3.0 have been studied upon treatment by electrochemical oxidation with electrogenerated H2O2 (EO-H2O2), electro-Fenton (EF) and photoelectro-Fenton (PEF). Experiments were performed with a stirred tank reactor containing a boron-doped diamond (BDD) or Pt anode and an air-diffusion cathode to generate H2O2. The main oxidants were hydroxyl radicals formed at the anode surface from water oxidation and in the bulk from Fenton's reaction between H2O2 and added Fe(2+). The oxidation ability increased in the sequence EO-H2O2 < EF < PEF and faster degradation was always obtained using BDD. PEF process with BDD yielded almost total mineralization following similar trends in SO4(2-), ClO4(-) and NO3(-) media, whereas in Cl(-) medium, mineralization was inhibited by the formation of recalcitrant chloroderivatives. GC-MS analysis confirmed the cleavage of the −N=N− bond with formation of two main aromatics in SO4(2-) medium and three chloroaromatics in Cl(-) solutions. The effective oxidation of final oxalic and oxamic acids by BDD along with the photolysis of Fe(III)-oxalate species by UVA light accounted for the superiority of PEF with BDD. NH4(+), NO3(-) and SO4(2-) ions were released during the mineralization. Copyright © 2015 Elsevier B.V. All rights reserved.

Aggregation and charge behavior of metallic and nonmetallic nanoparticles in the presence of competing similarly-charged inorganic ions.

PubMed

Mukherjee, Biplab; Weaver, James W

2010-05-01

The influence of competing, similarly charged, inorganic ions on the size and charge behavior of suspended titanium-dioxide (nTiO(2)), silver (nAg) and fullerene (nC(60)) nanoparticles (NPs) was investigated. Under pH and ionic conditions similar to natural water bodies, Ca(2+) induced aggregation of nTiO(2) and nAg NPs more strongly than K(+) and Na(+). Although K(+) and Na(+) had a similar effect on aggregation, K(+) provided better screening of the particle surface charge presumably because of its small hydrated radius. These effects were decidedly more prominent for TiO(2) than Ag. Anions (co-ions), SO(4)(2-) and Cl(-), affected the surface charge behavior of nTiO(2) but not of nAg NPs. The zeta potential (ZP) of nTiO(2) NPs was more negative at higher SO(4)(2-)/Cl(-) ratios than lower. When Mg(2+) was the counterion, charge inversion and rapid aggregation of nC(60) NPs occurred under alkaline conditions, with a more pronounced effect for Cl(-) than SO(4)(2-). Response dissimilarities suggest fundamental differences in the interfacial-interaction characteristics of these NPs in the aquatic environment with corresponding differences in transport of these particles. Our study also shows the important role played by the iso-electric point pH (pH(iep)) of the NPs in determining their aggregation kinetics in the environment.

Glyoxal and Methylglyoxal Setschenow Salting Constants in Sulfate, Nitrate, and Chloride Solutions: Measurements and Gibbs Energies.

PubMed

Waxman, Eleanor M; Elm, Jonas; Kurtén, Theo; Mikkelsen, Kurt V; Ziemann, Paul J; Volkamer, Rainer

2015-10-06

Knowledge about Setschenow salting constants, KS, the exponential dependence of Henry's Law coefficients on salt concentration, is of particular importance to predict secondary organic aerosol (SOA) formation from soluble species in atmospheric waters with high salt concentrations, such as aerosols. We have measured KS of glyoxal and methylglyoxal for the atmospherically relevant salts (NH4)2SO4, NH4NO3, NaNO3, and NaCl and find that glyoxal consistently "salts-in" (KS of -0.16, -0.06, -0.065, -0.1 molality(-1), respectively) while methylglyoxal "salts-out" (KS of +0.16, +0.075, +0.02, +0.06 molality(-1)). We show that KS values for different salts are additive and present an equation for use in atmospheric models. Additionally, we have performed a series of quantum chemical calculations to determine the interactions between glyoxal/methylglyoxal monohydrate with Cl(-), NO3(-), SO4(2-), Na(+), and NH4(+) and find Gibbs free energies of water displacement of -10.9, -22.0, -22.9, 2.09, and 1.2 kJ/mol for glyoxal monohydrate and -3.1, -10.3, -7.91, 6.11, and 1.6 kJ/mol for methylglyoxal monohydrate with uncertainties of 8 kJ/mol. The quantum chemical calculations support that SO4(2-), NO3(-), and Cl(-) modify partitioning, while cations do not. Other factors such as ion charge or partitioning volume effects likely need to be considered to fully explain salting effects.

Indoor/outdoor of PM10 relationships and its water-soluble ions composition in selected primary schools in Malaysia

NASA Astrophysics Data System (ADS)

Mohamad, Noorlin; Latif, Mohd Talib

2013-11-01

Measurements of PM10 and water-soluble ions were carried out on indoor and outdoor PM10 (particles > 10 μm in aerodynamic diameter) aerosols sampled at selected primary schools of Kuala Lumpur (S1) and Putrajaya (S2), respectively. Samples were collected using a low volume sampler on Teflon filters. The water-soluble ions chloride (Cl-), nitrate (NO3-), sulfate (SO42-), calcium (Ca2+), magnesium (Mg2+), sodium (Na+), potassium (K+) and ammonium (NH4+) was analyzed using ion chromatography. The results showed that the indoor PM10 mass concentrations in S1 and S2 were 96.6 and 69.5 μg/m3, while the outdoor PM10 mass concentrations were 80.1 and 85.2 μg/m3, respectively. This indicated that NO3- were the most dominant ions, followed by SO42-, Ca2+, K+ and Na+, while Cl-, Mg2+ and Na+ were present at low concentrations. Pearson's correlation test applied to all the data showed high correlation between SO42- and NO3-, indicating a common anthropogenic origin. In addition, the correlations between Na+ and Ca2+ indicated crustal origins that significantly contributed to human exposure.

Atmospheric dry deposition on pines in the Eastern Brook Lake Watershed, Sierra Nevada, California

NASA Astrophysics Data System (ADS)

Bytnerowicz, Andrzej; Dawson, P. J.; Morrison, C. L.; Poe, M. P.

Atmospheric dry deposition to branches of Pinus contorta and P. albicaulis was measured during summer 1987 in a sub-alpine zone at Eastern Brook Lake Watershed (EBLW), eastern Sierra Nevada, California. Results are presented as deposition fluxes of NO 3-, SO 42-, PO 43-, Cl -, F -, NH 4+, Ca 2+, Mg 2+, Na +, K +, Zn 2+, Fe 3+, Mn 2+, Pb 2+ and H +, and compared with other locations in California and elsewhere. Deposition fluxes of anions and cations to the pine branches were low, several times lower than the values determined near the Emerald Lake Watershed (ELW), another sub-alpine location in the western Sierra Nevada. The sums of deposition fluxes of the measured cations and anions to pine surfaces were similar, in contrast to the ELW location where the sums of cation fluxes were much higher than the sums of anion fluxes. A strong positive correlation between depositions of NO 3- and NH 4+, as well as SO 42- and Ca 2+, suggested that large portions of these ions might have originated from particulate NH 4NO 3 and CaSO 4 deposited on pine surfaces. An estimated total N dry deposition (surface deposition of NO 3- and NH 4+ and internal uptake of NO 2 and HNO 3) to the forested area of the EBLW was 29.54 eq ha -1 yr - (about 414 g H ha -1 yr -1).

Origin of soluble chemical species in bulk precipitation collected in Tokyo, Japan: Statistical evaluation of source materials

NASA Astrophysics Data System (ADS)

Tsurumi, Makoto; Takahashi, Akira; Ichikuni, Masami

An iterative least-squares method with a receptor model was applied to the analytical data of the precipitation samples collected at 23 points in the suburban area of Tokyo, and the number and composition of the source materials were determined. Thirty-nine monthly bulk precipitation samples were collected in the spring and summer of 1987 from the hilly and mountainous area of Tokyo and analyzed for Na +, K +, NH 4+, Mg 2+, Ca 2+, F -, Cl -, Br -, NO 3- and SO 42- by atomic absorption spectrometry and ion chromatography. The pH of the samples was also measured. A multivariate ion balance approach (Tsurumi, 1982, Anal. Chim. Acta138, 177-182) showed that the solutes in the precipitation were derived from just three major sources; sea salt, acid substance (a mixture of 53% HNO 3, 39% H 2SO 4 and 8% HCl in equivalent) and CaSO 4. The contributions of each source to the precipitation were calculated for every sampling site. Variations of the contributions with the distance from the coast were also discussed.

Multiple regression equations modelling of groundwater of Ajmer-Pushkar railway line region, Rajasthan (India).

PubMed

Mathur, Praveen; Sharma, Sarita; Soni, Bhupendra

2010-01-01

In the present work, an attempt is made to formulate multiple regression equations using all possible regressions method for groundwater quality assessment of Ajmer-Pushkar railway line region in pre- and post-monsoon seasons. Correlation studies revealed the existence of linear relationships (r 0.7) for electrical conductivity (EC), total hardness (TH) and total dissolved solids (TDS) with other water quality parameters. The highest correlation was found between EC and TDS (r = 0.973). EC showed highly significant positive correlation with Na, K, Cl, TDS and total solids (TS). TH showed highest correlation with Ca and Mg. TDS showed significant correlation with Na, K, SO4, PO4 and Cl. The study indicated that most of the contamination present was water soluble or ionic in nature. Mg was present as MgCl2; K mainly as KCl and K2SO4, and Na was present as the salts of Cl, SO4 and PO4. On the other hand, F and NO3 showed no significant correlations. The r2 values and F values (at 95% confidence limit, alpha = 0.05) for the modelled equations indicated high degree of linearity among independent and dependent variables. Also the error % between calculated and experimental values was contained within +/- 15% limit.

A two force-constant model for complexes B⋯M-X (B is a Lewis base and MX is any diatomic molecule): Intermolecular stretching force constants from centrifugal distortion constants D(J) or Δ(J).

PubMed

Bittner, Dror M; Walker, Nicholas R; Legon, Anthony C

2016-02-21

A two force-constant model is proposed for complexes of the type B⋯MX, in which B is a simple Lewis base of at least C2v symmetry and MX is any diatomic molecule lying along a Cn axis (n ≥ 2) of B. The model assumes a rigid subunit B and that force constants beyond quadratic are negligible. It leads to expressions that allow, in principle, the determination of three quadratic force constants F11, F12, and F22 associated with the r(B⋯M) = r2 and r(M-X) = r1 internal coordinates from the equilibrium centrifugal distortion constants DJ (e) or ΔJ (e), the equilibrium principal axis coordinates a1 and a2, and equilibrium principal moments of inertia. The model can be applied generally to complexes containing different types of intermolecular bond. For example, the intermolecular bond of B⋯MX can be a hydrogen bond if MX is a hydrogen halide, a halogen-bond if MX is a dihalogen molecule, or a stronger, coinage-metal bond if MX is a coinage metal halide. The equations were tested for BrCN, for which accurate equilibrium spectroscopic constants and a complete force field are available. In practice, equilibrium values of DJ (e) or ΔJ (e) for B⋯MX are not available and zero-point quantities must be used instead. The effect of doing so has been tested for BrCN. The zero-point centrifugal distortion constants DJ (0) or ΔJ (0) for all B⋯MX investigated so far are of insufficient accuracy to allow F11 and F22 to be determined simultaneously, even under the assumption F12 = 0 which is shown to be reasonable for BrCN. The calculation of F22 at a series of fixed values of F11 reveals, however, that in cases for which F11 is sufficiently larger than F22, a good approximation to F22 is obtained. Plots of F22 versus F11 have been provided for Kr⋯CuCl, Xe⋯CuCl, OC⋯CuCl, and C2H2⋯AgCl as examples. Even in cases where F22 ∼ F11 (e.g., OC⋯CuCl), such plots will yield either F22 or F11 if the other becomes available.

A two force-constant model for complexes B⋯M-X (B is a Lewis base and MX is any diatomic molecule): Intermolecular stretching force constants from centrifugal distortion constants DJ or ΔJ

NASA Astrophysics Data System (ADS)

Bittner, Dror M.; Walker, Nicholas R.; Legon, Anthony C.

2016-02-01

A two force-constant model is proposed for complexes of the type B⋯MX, in which B is a simple Lewis base of at least C2v symmetry and MX is any diatomic molecule lying along a Cn axis (n ≥ 2) of B. The model assumes a rigid subunit B and that force constants beyond quadratic are negligible. It leads to expressions that allow, in principle, the determination of three quadratic force constants F11, F12, and F22 associated with the r(B⋯M) = r2 and r(M-X) = r1 internal coordinates from the equilibrium centrifugal distortion constants DJ e or ΔJ e , the equilibrium principal axis coordinates a1 and a2, and equilibrium principal moments of inertia. The model can be applied generally to complexes containing different types of intermolecular bond. For example, the intermolecular bond of B⋯MX can be a hydrogen bond if MX is a hydrogen halide, a halogen-bond if MX is a dihalogen molecule, or a stronger, coinage-metal bond if MX is a coinage metal halide. The equations were tested for BrCN, for which accurate equilibrium spectroscopic constants and a complete force field are available. In practice, equilibrium values of DJ e or ΔJ e for B⋯MX are not available and zero-point quantities must be used instead. The effect of doing so has been tested for BrCN. The zero-point centrifugal distortion constants DJ 0 or ΔJ 0 for all B⋯MX investigated so far are of insufficient accuracy to allow F11 and F22 to be determined simultaneously, even under the assumption F12 = 0 which is shown to be reasonable for BrCN. The calculation of F22 at a series of fixed values of F11 reveals, however, that in cases for which F11 is sufficiently larger than F22, a good approximation to F22 is obtained. Plots of F22 versus F11 have been provided for Kr⋯CuCl, Xe⋯CuCl, OC⋯CuCl, and C2H2⋯AgCl as examples. Even in cases where F22 ˜ F11 (e.g., OC⋯CuCl), such plots will yield either F22 or F11 if the other becomes available.

Ion chemistry and source identification of coarse and fine aerosols in an urban area of eastern central India

NASA Astrophysics Data System (ADS)

Verma, Santosh K.; Deb, Manas K.; Suzuki, Yukio; Tsai, Ying I.

2010-01-01

This work focuses on size segregated atmospheric aerosol mass concentrations and water soluble inorganic components in Chhattisgarh, the eastern central India. Investigation on the monitoring of ambient air levels of atmospheric particulates were done around a large source of primary anthropogenic particulate emissions: the industrial area and coal based power plants. Chemical characterization was carried out for aerosol samples collected in urban area, Raipur, (21°14'N, 81°38'E) of Chhattisgarh region over a period of one year, using cascade impactor. Annual mean of mass concentration for coarse (PM 2.5-10) and fine (PM 2.5) aerosols were monitored to be 238.1 ± 89.9 and 167.0 ± 75.3 µg m - 3 respectively This work deals with the seasonal variation and meteorological influences of inorganic components of the aerosols viz. NO 3-, Cl - and SO 42-, Mg 2+, Na +, K +, Ca 2+ and NH 4+. The annual mean concentration of the inorganic components were monitored to be 3.8 ± 2.5, 8.9 ± 2.7, 10.2 ± 1.5, 2.6 ± 0.6, 8.7 ± 7.2, 4.6 ± 1.8, 16.4 ± 6.9 and 0.4 ± 0.5 µg m - 3 respectively in coarse particles and 8.2 ± 7.1, 6.8 ± 3.6, 46.5 ± 32.8, 1.7 ± 0.6, 7.4 ± 3.6, 5.9 ± 3.4, 10.2 ± 2.9, and 8.8 ± 7.7 µg m - 3 respectively in fine particles, for the above ions. The average distribution of nitrate and sulphate in PM 2.5-10 were found to be 1.6 and 4.2% and in PM 2.5 were 4.9 and 27.9% respectively indicating the dominance of sulphate in both PM 2.5-10 and PM 2.5 particles. Here, industrial emission plays important role for contribution of PM 2.5 particle loading in the atmosphere. The cation-anion rational analysis indicated that the PM 2.5-10 particles were mostly neutralized and PM 2.5 particle were acidic. The major ions were mainly in the form of NaCl > CaSO 4 > K 2SO 4 > MgSO 4 > KCl > NH 4Cl > Ca(NO 3) 2 > KNO 3 > MgCl 2 > Mg(NO 3) 2 > NH 4NO 3 > (NH 4) 2SO 4 in coarse aerosol particles and (NH 4) 2SO 4 > K 2SO 4 > CaSO 4 > NaCl > NH 4NO 3 > CaCl 2 > KNO 3 > MgCl 2 > Ca(NO 3) 2 > KCl > NH 4Cl in fine particles.

One-pot fabrication of FRET-based fluorescent probe for detecting copper ion and sulfide anion in 100% aqueous media

NASA Astrophysics Data System (ADS)

Lv, Kun; Chen, Jian; Wang, Hong; Zhang, Peisheng; Yu, Maolin; Long, Yunfei; Yi, Pinggui

2017-04-01

The design of effective tools for detecting copper ion (Cu2 +) and sulfide anion (S2 -) is of great importance due to the abnormal level of Cu2 + and S2 - has been associated with an increase in risk of many diseases. Herein, we report on the fabrication of fluorescence resonance energy transfer (FRET) based fluorescent probe PF (PEI-FITC) for detecting Cu2 + and S2 - in 100% aqueous media via a facile one-pot method by covalent linking fluorescein isothiocyanate (FITC) with branched-polyethylenimine (b-PEI). PF could selectively coordinate with Cu2 + among 10 metal ions to form PF-Cu2 + complex, resulting in fluorescence quenching through FRET mechanism. Furthermore, the in situ generated PF-Cu2 + complex can be used to selectively detect S2 - based on the displacement approach, resulting in an off-on type sensing. There is no obvious interference from other anions, such as Cl-, NO3-, ClO4-, SO42 -, HCO3-, CO32 -, Br-, HPO42 -, F- and S2O32 -. In addition, PF was successfully used to determine Cu2 + and S2 - in human serum and tap water samples. Therefore, the FRET-based probe PF may provide a new method for selective detection of multifarious analysts in biological and environmental applications, and even hold promise for application in more complicated systems.

Sensitivity of Tropospheric Chemical Composition to Halogen-Radical Chemistry Using a Fully Coupled Size-Resolved Multiphase Chemistry-Global Climate System: Halogen Distributions, Aerosol Composition, and Sensitivity of Climate-Relevant Gases

DOE Office of Scientific and Technical Information (OSTI.GOV)

Long, M.; Keene, W. C.; Easter, Richard C.

Observations and model studies suggest a significant but highly non-linear role for halogens, primarily Cl and Br, in multiphase atmospheric processes relevant to tropospheric chemistry and composition, aerosol evolution, radiative transfer, weather, and climate. The sensitivity of global atmospheric chemistry to the production of marine aerosol and the associated activation and cycling of inorganic Cl and Br was tested using a size-resolved multiphase coupled chemistry/global climate model (National Center for Atmospheric Research’s Community Atmosphere Model (CAM); v3.6.33). Simulation results showed strong meridional and vertical gradients in Cl and Br species. The simulation reproduced most available observations with reasonable confidence permittingmore » the formulation of potential mechanisms for several previously unexplained halogen phenomena including the enrichment of Br- in submicron aerosol, and the presence of a BrO maximum in the polar free troposphere. However, simulated total volatile Br mixing ratios were generally high in the troposphere. Br in the stratosphere was lower than observed due to the lack of long-lived organobromine species in the simulation. Comparing simulations using chemical mechanisms with and without reactive Cl and Br species demonstrated a significant temporal and spatial sensitivity of primary atmospheric oxidants (O3, HOx, NOx), CH4, and non-methane hydrocarbons (NMHC’s) to halogen cycling. Simulated O3 and NOx were globally lower (65% and 35%, respectively, less in the planetary boundary layer based on median values) in simulations that included halogens. Globally, little impact was seen in SO2 and non-sea-salt SO42- processing due to halogens. Significant regional differences were evident: The lifetime of nss-SO42- was extended downwind of large sources of SO2. The burden and lifetime of DMS (and its oxidation products) were lower by a factor of 5 in simulations that included halogens, versus those without, leading to a 20% reduction in nss-SO42- in the southern hemisphere planetary boundary layer based on median values.« less

Ce-Fe-modified zeolite-rich tuff to remove Ba(2+)-like (226)Ra(2+) in presence of As(V) and F(-) from aqueous media as pollutants of drinking water.

PubMed

Olguín, María Teresa; Deng, Shuguang

2016-01-25

The sorption behavior of the Ba(2+)-like (226)Ra(2+) in the presence of H2AsO4(-)/HAsO4(2-) and F(-) from aqueous media using Ce-Fe-modified zeolite-rich tuff was investigated in this work. The Na-modified zeolite-rich tuff was also considered for comparison purposes. The zeolite-rich tuff collected from Wyoming (US) was in contact with NaCl and CeCl3-FeCl3 solutions to obtain the Na- and Ce-Fe-modified zeolite-rich tuffs (ZUSNa and ZUSCeFe). These zeolites were characterized by scanning electron microscopy and X-ray diffraction. The BET-specific surface and the points of zero charge were determined as well as the content of Na, Ce and Fe by neutron activation analysis. The textural characteristics and the point of zero charge were changed by the presence of Ce and Fe species in the zeolitic network. A linear model described the Ba(2+)-like (226)Ra(2+) sorption isotherms and the distribution coefficients (Kd) varied with respect to the metallic species present in the zeolitic material. The As(V) oxianionic chemical species and F(-) affected this parameter when the Ba(2+)-like (226)Ra(2+)-As(V)-F(-) solutions were in contact with ZUSCeFe. The H2AsO4(-)/HAsO4(2-) and F(-) were adsorbed by ZUSCeFe in the same amount, independent of the concentration of Ba(2+)-like (226)Ra(2+) in the initial solution. Copyright © 2015 Elsevier B.V. All rights reserved.

Development of N(2) Sensor for Determination of PN(2) in Body Tissues.

DTIC Science & Technology

1986-08-01

NK3)4C1 2 ]Cl Acid -140 -340 Acid -120 -280 +500 . + Zn Amalgam +700 +900 2 cis-Ru(N( 3 )4C1 2 C1 Buffer -130 -305 (major) ,450 + Zn Amalgam -210...increase under N 2 -400 mV under N 2 cis- [1u (en) 2C12 )C1 Buffer -125 -350 Buffer + Zn - so -400 .475 Amalgam +780 cis-(Ru(en)2Br 2 ] r Acid -120...375 Acid + Zn - 0 -280 plateau Amalgam 600-8SO cis- ([ (bipyr)C12 1Cl Buffer .455 +320 Buffer + Zn +575 +380 Nme Amalgam 1Acid = 0.1M H2SO42Buffer

Topics in Optical Materials and Device Research - II. Volume I.

DTIC Science & Technology

1982-01-01

Reflectometry Nicolet Optical Waveguide Computer Wavelength Multiplexing Silicon C it --l Pulse Generator CDSilicon Nitride 8 rystal-Growth Mechanism...expression for the power lost due to transition radiation will be given by SPTZ t) LA- L E- F, Q (18) -- 42 . c ; os )a -, - )(a+L - ~ O ~ o ~/-/3)CL - C /(d...IKe r1 ) J y 0 aJ., - C ,,-- O --) f2¢.,+-,) .T,,.,,() ,.(;,_, - LJ i (_1,,,, J _f-a.) - ao ,."T, (,) ,, ~Ca-)] (Al) / " 00,2 (fvid. = - L .z , ) (-1

Kinetic and thermodynamic factors controlling the distribution of SO32- and Na+ in calcites and selected aragonites

USGS Publications Warehouse

Busenberg, E.; Plummer, Niel

1985-01-01

Significant amounts of SO42-, Na+, and OH- are incorporated in marine biogenic calcites. Biogenic high Mg-calcites average about 1 mole percent SO42-. Aragonites and most biogenic low Mg-calcites contain significant amounts of Na+, but very low concentrations of SO42-. The SO42- content of non-biogenic calcites and aragonites investigated was below 100 ppm. The presence of Na+ and SO42- increases the unit cell size of calcites. The solid-solutions show a solubility minimum at about 0.5 mole percent SO42- beyond which the solubility rapidly increases. The solubility product of calcites containing 3 mole percent SO42- is the same as that of aragonite. Na+ appears to have very little effect on the solubility product of calcites. The amounts of Na+ and SO42- incorporated in calcites vary as a function of the rate of crystal growth. The variation of the distribution coefficient (D) of SO42- in calcite at 25.0??C and 0.50 molal NaCl is described by the equation D = k0 + k1R where k0 and k1 are constants equal to 6.16 ?? 10-6 and 3.941 ?? 10-6, respectively, and R is the rate of crystal growth of calcite in mg??min-1??g-1 of seed. The data on Na+ are consistent with the hypothesis that a significant amount of Na+ occupies interstitial positions in the calcite structure. The distribution of Na+ follows a Freundlich isotherm and not the Berthelot-Nernst distribution law. The numerical value of the Na+ distribution coefficient in calcite is probably dependent on the number of defects in the calcite structure. The Na+ contents of calcites are not very accurate indicators of environmental salinities. ?? 1985.

Synthetic, Infrared, 1H and 13C NMR Spectral Studies on N-(2-/3-Substituted Phenyl)-4-Substituted Benzenesulphonamides, 4-X'C6H4SO2NH(2-/3-XC6H4), where X' = H, CH3, C2H5, F, Cl or Br, and X = CH3 or Cl

NASA Astrophysics Data System (ADS)

Gowda, B. Thimme; Shetty, Mahesha; Jayalakshmi, K. L.

2005-02-01

Twenty three N-(2-/3-substituted phenyl)-4-substituted benzenesulphonamides of the general formula, 4-X'C6H4SO2NH(2-/3-XC6H4), where X' = H, CH3, C2H5, F, Cl or Br and X = CH3 or Cl have been prepared and characterized, and their infrared spectra in the solid state, 1H and 13C NMR spectra in solution were studied. The N-H stretching vibrations, νN-H, absorb in the range 3285 - 3199 cm-1, while the asymmetric and symmetric SO2 vibrations vary in the ranges 1376 - 1309 cm-1 and 1177 - 1148 cm-1, respectively. The S-N and C-N stretching vibrations absorb in the ranges 945 - 893 cm-1 and 1304 - 1168 cm-1, respectively. The compounds do not exhibit particular trends in the variation of these frequencies on substitution either at ortho or meta positions with either a methyl group or Cl. The observed 1H and 13C chemical shifts of are assigned to protons and carbons of the two benzene rings. Incremental shifts of the ring protons and carbons due to -SO2NH(2-/3-XC6H4) groups in C6H5SO2NH(2-/3-XC6H4), and 4- X'C6H4SO2- and 4-X'C6H4SO2NH- groups in 4-X'C6H4SO2NH(C6H5) are computed and employed to calculate the chemical shifts of the ring protons and carbons in the substituted compounds, 4-X'C6H4SO2NH(2-/3-XC6H4). The computed values agree well with the observed chemical shifts.

Performance of an alkalophilic and halotolerant laccase from gamma-proteobacterium JB in the presence of industrial pollutants.

PubMed

Singh, Gursharan; Sharma, Prince; Capalash, Neena

2009-08-01

An alkalophilic and halotolerant laccase from gamma-proteobacterium JB catalyzed in high concentrations of organic solvents and various salts. The enzyme retained 80-100% activity in 10% concentration of dimethylsulfoxide (DMSO), ethanol, acetone or methanol; 100, 85 and 50% activity in 20 mM MgCl(2), 5.0 mM MnCl(2) and 0.1 mM CuCl(2); 140, 120 and 110% activity in 5.0 mM MnSO(4), 10 mM MgSO(4) and 1mM CaSO(4), respectively. Sodium halides inhibited the enzyme in the order: F(-)> Br(-)> I(-)> Cl(-). In 0.5 M NaCl, pH 6.0, laccase was approximately 60% active. Decolorization of indigo carmine by laccase at pH 9.0 was not inhibited even in the presence of 0.5 M NaCl. Release of chromophoric, reducing and hydrophobic compounds during biobleaching of straw rich-soda pulp by laccase was not inhibited when the enzyme was applied in the presence of 1 M NaCl at pH 8.0. Laccase retained 50% residual activity even when incubated with 5% calcium hypochlorite for 30 min.

Water-soluble ions and trace elements in surface snow and their potential source regions across northeastern China

NASA Astrophysics Data System (ADS)

Wang, Xin; Pu, Wei; Zhang, Xueying; Ren, Yong; Huang, Jianping

2015-08-01

We collected 92 snow samples from 13 sites across northeastern China from January 7 to February 15, 2014. The surface snow samples were analyzed for the major water-soluble ions (SO42-, NO3-, F-, Cl-, Na+, K+, Ca2+, Mg2+, and NH4+) and trace element (Al, As, Mn, V, Cd, Cu, Pb, Zn, Fe, Cr, and Ni). The results indicated that the higher concentrations of NO3- and SO42- and the trace elements Zn, Pb, Cd, Ni, and Cu were likely attributable to enhanced local industrial emissions in East Asia especially in China. In addition, snow samples characterized by higher enrichment factors of trace elements (Cu, Cd, As, Zn, Pb) were indicative of an anthropogenic source. Emissions from fossil fuel combustion and biomass burning were likely important contributors to the chemical elements in seasonal snow with long-range transport. On the other hand, the large attribution of K+ appeared in the higher latitude demonstrated that biomass burning was a dominated factor of the chemical species in seasonal snow in the higher latitude of China than that in the lower latitude. Finally, an interannual comparison with the 2010 China snow survey also confirmed the source attributions of chemical speciation in seasonal snow in these regions.

Synthesis and spectroscopic studies of binuclear metal complexes of a tetradentate N2O2 Schiff base ligand derived from 4,6-diacetylresorcinol and benzylamine.

PubMed

Shebl, Magdy

2008-09-01

A tetradentate N2O2 donor Schiff base ligand, H2L, was synthesized by the condensation of 4,6-diacetylresorcinol with benzylamine. The structure of the ligand was elucidated by elemental analyses, IR, 1H NMR, electronic and mass spectra. Reaction of the Schiff base ligand with nickel(II), cobalt(II), iron(III), cerium(III), vanadyl(IV) and uranyl(VI) ions in 1:2 molar ratio afforded binuclear metal complexes. Also, reaction of the ligand with several copper(II) salts, including Cl-, NO3-, AcO-, ClO4- and SO42- afforded different metal complexes that reflect the non-coordinating or weakly coordinating power of the ClO(4)(-) anion as compared to the strongly coordinating power of SO42- and Cl- anions. Characterization and structure elucidation of the prepared complexes were achieved by elemental and thermal analyses, IR, 1H NMR, electronic, mass and ESR spectra as well as magnetic susceptibility measurements. The metal complexes exhibited different geometrical arrangements such as square planar, octahedral, square pyramidal and pentagonal bipyramidal arrangements. The variety in the geometrical arrangements depends on the nature of both the anion and the metal ion.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Willow, Soohaeng Yoo; Xantheas, Sotiris S.

The effect of the Hofmeister anion series on the structure and stability of proteins is often discussed using simple systems such as a water-vapor interface with the assumption that the vapor region mimics the hydrophobic surface. Microscopic theories suggest that the Hofmeister anion series is highly correlated with the different contributions of the various ions to the surface tension of such a water-vapor interface. Proteins, however, have both hydrophobic and hydrophilic regions rather than just a pure hydrophobic one. Using a solvated parallel β -sheet layer consisting of both hydrophobic and positively charged hydrophilic surfaces as a more realistic modelmore » to represent a protein surface, we investigated the interaction of such a system with hydrophilic-like (SO42-) and hydrophobic-like (ClO4-) anions via Born-Oppenheimer Molecular Dynamics (BOMD) simulations. We found that both the SO42- and ClO4- anions prefer to reside on the hydrophilic rather than on the hydrophobic surface of the parallel β -sheet layer. In addition, our simulations suggest that the ClO4- ions not only penetrate towards the peptide groups through the hydrophilic residues, but also allow water molecules to penetrate as well to form water-peptide hydrogen bonds, while the SO42- ions stabilize the interface of the water-hydrophilic surface. Our results render a plausible explanation of why hydrophobic-like Hofmeister anions act as protein denaturants. This work was supported by the US Department of Energy, Office of Science, Office of Basic Energy Sciences, Division of Chemical Sciences, Geosciences and Biosciences. Pacific Northwest National Laboratory (PNNL) is a multiprogram national laboratory operated for DOE by Battelle.« less

The effects of fuel composition and ammonium sulfate addition on PCDD, PCDF, PCN and PCB concentrations during the combustion of biomass and paper production residuals.

PubMed

Lundin, Lisa; Jansson, Stina

2014-01-01

The use of waste wood as an energy carrier has increased during the last decade. However, the higher levels of alkali metals and chlorine in waste wood compared to virgin biomass can promote the formation of deposits and organic pollutants. Here, the effect of fuel composition and the inhibitory effects of ammonium sulfate, (NH4)2SO4, on the concentrations of persistent organic pollutants (POPs) in the flue gas of a lab-scale combustor was investigated. Ammonium sulfate is often used as a corrosion-preventing additive and may also inhibit formation of polychlorinated dibenzo-p-dioxins (PCDDs) and dibenzofurans (PCDFs). In addition to PCDDs and PCDFs, polychlorinated naphthalenes (PCN) and biphenyls (PCB) were also analyzed. It was found that the flue gas composition changed dramatically when (NH4)2SO4 was added: CO, SO2, and NH3 levels increased, while those of HCl decreased to almost zero. However, the additive's effects on POP formation were less pronounced. When (NH4)2SO4 was added to give an S:Cl ratio of 3, only the PCDF concentration was reduced, indicating that this ratio was not sufficient to achieve a general reduction in POP emissions. Conversely, at an S:Cl ratio of 6, significant reductions in the WHO-TEQ value and the PCDD and PCDF contents of the flue gas were observed. The effect on the PCDF concentration was especially pronounced. PCN formation seemed to be promoted by the elevated CO concentrations caused by adding (NH4)2SO4. Copyright © 2013. Published by Elsevier Ltd.

Exploring the background features of acidic and basic air pollutants around an industrial complex using data mining approach.

PubMed

Chen, Ho-Wen; Tsai, Ching-Tsan; She, Chin-Wen; Lin, Yo-Chen; Chiang, Chow-Feng

2010-11-01

Air pollution data around a monitored site are normally difficult to analyze due to highly inter-related meteorological and topographical factors on top of many complicated atmospheric chemical interactions occurred in local and regional wind fields. The challenge prompts this study to develop a comprehensive data-mining algorithm of cluster analysis followed by meteorological and interspecies correlations to mitigate the inherent data complexity and dissimilarity. This study investigated the background features of acidic and basic air pollutants around a high-tech industrial park in Taiwan. Monthly samplings were taken at 10 sites around the park in a year. The temporal distribution plots show a baseline with two characteristic groups of high and low peaks. Hierarchical cluster analysis confirms that high peaks were primarily associated with low speed south wind in summer for all the chemical species, except for F(-), Cl(-), NH(3) and HF. Crosschecking with the topographical map identifies several major external sources in south and southwest. Further meteorological correlation suggests that HCl is highly positively associated with humidity, while Cl(-) is highly negatively associated with temperature, both for most stations. Interestingly, HNO(3) is highly negatively associated with wind speed for most stations and the hotspot was found in summer and around the foothill of Da-Tu Mountain in the northwest, a stagnant pocket on the study site. However, F(-) is highly positively associated with wind speed at downwind stations to the prevailing north wind in winter, indicating an internal source from the north. The presence of NH(4)(+) stimulates the formation of NO(3)(-), SO(4)(-2) (R=0.7), and HNO(3), H(2)SO(4), NH(3) (R=0.3-0.4). As H(2)SO(4) could be elevated to a level as high as 40% of the regulated standard, species interactions may be a dominate mechanism responsible for the substantial increase in summer from external sources. Copyright © 2010 Elsevier Ltd. All rights reserved.

Spatially resolved micro-Raman observation on the phase separation of effloresced sea salt droplets.

PubMed

Xiao, Han-Shuang; Dong, Jin-Ling; Wang, Liang-Yu; Zhao, Li-Jun; Wang, Feng; Zhang, Yun-Hong

2008-12-01

We report on the investigation of the phase separation of individual seawater droplets in the efflorescence processes with the spatially resolved Raman system. Upon decreasing the relative humidity (RH), CaSO4.0.5H2O separated out foremost fromthe droplet atan unexpectedly high RH of approcimately 90%. Occasionally, CaSO4.2H2O substituted for CaSO4.O.5H2O crystallizing first at approximately 78% RH. Relatively large NaCI solids followed to crystallize at approximately 55% RH and led to the great loss of the solution. Then, the KMgCl3.6H2O crystallites separated out from the residual solutions, adjacentto NaCl at approximately 44% RH. Moreover, a shell structure of dried sea salt particle was found to form at low RHs, with the NaCl crystals in the core and minor supersaturated solutions covered with MgSO4 gel coating on the surface. Ultimately, the shielded solution partly effloresced into MgSO4 hydrates at very dry state (<5% RH).

Chemical Composition of Atmospheric Aerosols From High and Low Altitude Sites in Northern and Western India

NASA Astrophysics Data System (ADS)

Rastogi, N.; Athiyarath, S.; Sarin, M.; R, R.

2006-12-01

The chemical composition of ambient aerosols, collected during wintertime from four designated sites: Ahmedabad (23.0oN, 72.6oE, 49 m asl), Mt Abu (24.6oN, 72.7oE, 1680 m asl), Hisar (29.2oN, 75.7oE, 216m asl) and Nainital (29.4oN, 79.5oE, 1940 m asl), has been studied to understand the potential role of regional emission sources as well as the long-range transport of chemical constituents through free troposphere. The two high altitude sites, Mt Abu and Nainital, exhibit free tropospheric characteristics during wintertime; whereas the urban sites (Ahmedabad and Hisar) are within boundary layer. The ratios of major ionic species, measured in water extracts of aerosols, are considered to be advantageous in order to remove the effect of aerosol mass loading on the atmospheric concentrations of species at different sites. At low-altitude-urban sites (Ahmedabad and Hisar), geometric mean of Ca2+/Na+ ratios (4.3 and 4.5) and HCO3-/ Ca2+ ratios (1.7 and 1.5) are comparable; whereas significant differences are observed in Cl-/Na+ (1.1 and 0.6), SO42-/Ca2+ (1.5 and 3.5) and SO42-/NO3- (2.1 and 1.0). These differences are attributed to relative dominance of anthropogenic emissions over the northern site (Hisar). In contrast, major differences arise over Mt Abu and Nainital with respect to Cl-/Na+ (1.0 and 0.2), Ca2+/Na+ (9.0 and 4.4) and HCO3-/ Ca2+ (1.8 and 0.9) ratios; whereas SO42-/Ca2+ (2.3 and 3.1) and SO42-/NO3- (5.3 and 5.9) ratios are comparable. Such regional differences for a high altitude site could arise due to semi-arid climate and high abundance of mineral dust at Mt Abu. Higher SO42-/NO3- ratios over high altitude sites than those over low altitude sites are attributed to the relative difference in the size distribution of SO42- (fine mode) and NO3- (coarse mode) aerosols.

Partitioning of mercury in aqueous biphasic systems and on ABEC resins.

PubMed

Rogers, R D; Griffin, S T

1998-06-26

Poly(ethylene glycol)-based aqueous biphasic systems (PEG-ABS) can be utilized to separate and recover metal ions in environmental and hydrometallurgical applications. A concurrent study was conducted comparing the partitioning of mercury between aqueous layers in an ABS [Me-PEG-5000/(NH4)2SO4] and partitioning of mercury from aqueous solutions to aqueous biphasic extraction chromatographic (ABEC-5000) resins. In ammonium sulfate solutions, mercury partitions to the salt-rich phase in ABS, but by using halide ion extractants, mercury will partition to the PEG-rich phase after formation of a chloro, bromo or iodo complex. The efficacy of the extractant increases in the order Cl-

[Characteristics of aerosol water-soluble inorganic ions in three types air-pollution incidents of Nanjing City].

PubMed

Zhang, Qiu-Chen; Zhu, Bin; Su, Ji-Feng; Wang, Hong-Lei

2012-06-01

In order to compare aerosol water-soluble inorganic species in different air-pollution periods, samples of PM10, PM2.1, PM1.1 and the main water-soluble ions (NH4+, Mg2+, Ca2+, Na+, K+, NO2(-), F(-), NO3(-), Cl(-), SO4(2-)) were measured, which were from 3 air-pollution incidents (continued pollution in October 16-30 of 2009, sandstorm pollution in April 27-30 of 2010, and crop burning pollution in June 14 of 2010. The results show that aerosol pollution of 3 periods is serious. The lowest PM2.1/PM10 is only 0.27, which is from sandstorm pollution period, while the largest is 0. 7 from crop burning pollution period. In continued pollution periods, NO3(-) and SO4(2-) are the dominant ions, and the total anions account for an average of 18.62%, 32.92% and 33.53% of PM10, PM2.1 and PM1.1. Total water-soluble ions only account for 13.36%, 23.72% and 28.54% of PM10, PM2.1 and PM1.1 due to the insoluble species is increased in sandstorm pollution period. The mass concentration of Ca2+ in sandstorm pollution period is higher than the other two pollution periods, and which is mainly in coarse particles with diameter larger than 1 microm. All the ten water-soluble ions are much higher in crop burning pollution especially K+ which is the tracer from crop burning. The peak mass concentrations of NO3(-), SO4(2-) and NH4+ are in 0.43-0.65 microm.

Characterization, expression patterns and functional analysis of the MAPK and MAPKK genes in watermelon (Citrullus lanatus).

PubMed

Song, Qiuming; Li, Dayong; Dai, Yi; Liu, Shixia; Huang, Lei; Hong, Yongbo; Zhang, Huijuan; Song, Fengming

2015-12-23

Mitogen-activated protein kinase (MAPK) cascades, which consist of three functionally associated protein kinases, namely MEKKs, MKKs and MPKs, are universal signaling modules in all eukaryotes and have been shown to play critical roles in many physiological and biochemical processes in plants. However, little or nothing is known about the MPK and MKK families in watermelon. In the present study, we performed a systematic characterization of the ClMPK and ClMKK families including the identification and nomenclature, chromosomal localization, phylogenetic relationships, ClMPK-ClMKK interactions, expression patterns in different tissues and in response to abiotic and biotic stress and transient expression-based functional analysis for their roles in disease resistance. Genome-wide survey identified fifteen ClMPK and six ClMKK genes in watermelon genome and phylogenetic analysis revealed that both of the ClMPK and ClMKK families can be classified into four distinct groups. Yeast two-hybrid assays demonstrated significant interactions between members of the ClMPK and ClMKK families, defining putative ClMKK2-1/ClMKK6-ClMPK4-1/ClMPK4-2/ClMPK13 and ClMKK5-ClMPK6 cascades. Most of the members in the ClMPK and ClMKK families showed differential expression patterns in different tissues and in response to abiotic (e.g. drought, salt, cold and heat treatments) and biotic (e.g. infection of Fusarium oxysporum f. sp. niveum) stresses. Transient expression of ClMPK1, ClMPK4-2 and ClMPK7 in Nicotiana benthamiana resulted in enhanced resistance to Botrytis cinerea and upregulated expression of defense genes while transient expression of ClMPK6 and ClMKK2-2 led to increased susceptibility to B. cinerea. Furthermore, transient expression of ClMPK7 also led to hypersensitive response (HR)-like cell death and significant accumulation of H2O2 in N. benthamiana. We identified fifteen ClMPK and six ClMKK genes from watermelon and analyzed their phylogenetic relationships, expression patterns and protein-protein interactions and functions in disease resistance. Our results demonstrate that ClMPK1, ClMPK4-2 and ClMPK7 positively but ClMPK6 and ClMKK2-2 negatively regulate the resistance to B. cinerea when transiently expressed in N. benthamiana and that ClMPK7 functions as a regulator of HR-like cell death through modulating the generation of H2O2.

Aqueous extracts of a Mars analogue regolith that mimics the Phoenix landing site do not inhibit spore germination or growth of model spacecraft contaminants Bacillus subtilis 168 and Bacillus pumilus SAFR-032

NASA Astrophysics Data System (ADS)

Nicholson, Wayne L.; McCoy, Lashelle E.; Kerney, Krystal R.; Ming, Douglas W.; Golden, D. C.; Schuerger, Andrew C.

2012-08-01

Because Mars is a primary target for life detection and habitability assessment missions, its exploration is also by necessity a Planetary Protection issue. The recent finding of significant levels of perchlorate (ClO4-) in regolith sampled from the Phoenix landing site raises the question of its potential biotoxicity to putative indigenous martian life, microbial forward contaminants from Earth, or future human visitors. To address this issue, an analogue regolith was constructed based on regolith chemistry data from the Phoenix landing site. A Mars Aqueous Regolith Extract (MARE) was prepared from the Phoenix analogue regolith and analyzed by ion chromatography. The MARE contained (mg/L) the cations Na+ (1411 ± 181), Mg2+ (1051 ± 160), Ca2+ (832 ± 125), and K+ (261 ± 29), and the anions SO42-(5911±993), ClO4-(5316±1767), Cl(171±25) and F- (2.0 ± 0.4). Nitrogen-containing species NO3-(773±113) and NO2-(6.9±2.3) were also present as a result of regolith preparation procedures, but their relevance to Mars is at present unknown. The MARE was tested for potential toxic effects on two model spacecraft contaminants, the spore-forming bacteria Bacillus subtilis strain 168 and Bacillus pumilus strain SAFR-032. In B. subtilis, spore germination and initial vegetative growth (up to ˜5 h) was not inhibited in a rich complex medium prepared with the MARE, but growth after 5 h was significantly suppressed in medium prepared using the MARE. Both B. subtilis and B. pumilus exhibited significantly higher rates of spore germination and growth in the MARE vs. DW with no additions (likely due to endogenous spore nutrients), but germination and growth was further stimulated by addition of glucose and a combination of buffered inorganic salts (K2HPO4, KH2PO4, (NH4)2SO4, and MgSO4). The data indicate that the aqueous environment in the regolith from the Phoenix landing site containing high levels of perchlorate does not pose a significant barrier to growth of putative forward contaminants such as B. subtilis and B. pumilus under Earth laboratory conditions.

Assessment of chemical quality of groundwater in coastal volcano-sedimentary aquifer of Djibouti, Horn of Africa

NASA Astrophysics Data System (ADS)

Ahmed, Abdoulkader Houssein; Rayaleh, Waiss Elmi; Zghibi, Adel; Ouddane, Baghdad

2017-07-01

This research is conducted to evaluate the current status of hydrogeochemical contaminants and their sources in groundwater in the volcano-sedimentary aquifer of Djibouti. Groundwater samples were mostly collected from the volcanic and inferoflux aquifers and then were analyzed for quality on physicochemical parameters (EC, pH, Temperature, Cl-, SO42-, HCO3-, NO3-, Na+, Ca2+, Mg2+, K+, Br-, F-), minor and trace elements (Li, Ba, B, Sr, Si, Al, Cr, Fe, Mn, Mo, Pb, Co, Cu, Ni, Zn, Ti, V, As, Se). The interpretations of hydrochemical data are shown numerically and graphically through the Piper diagram such as the multivariate statistical analysis, binary diagram, the calculation of the saturation indexes, the index of base exchanges and ratio of Na+/Cl-, SO42-/Cl-, HCO3-/Cl-. The seawater ratio and ionic deviation in the groundwater were calculated using the chloride concentration. These processes can be used as indicators of seawater intrusion progress. This study reveals three groundwater quality groups and how the quality of water supply has been deteriorated through the process of seawater intrusion. The seawater intrusion extends into the Gulf basalts aquifer that covers nearly 12% of the whole area according to some observations. Some toxic elements present in drinking water (As and Se) have already exceeded the maximum permissible in almost the entire of the Gulf basalts aquifer affected by seawater intrusion. Indeed, some correlations were found between As, Se, with electrical conductivity and among other minor and trace elements such as Br, B, Sr, Co and Cr. It indicates that all these elements are mainly controlled by naturel/geogenic processes. The Principal component Analysis and the Hierarchical Cluster Analysis have led to the confirmation of the hypotheses developed in the previous hydrochemical study in which two factors explain the major hydrochemical processes in the aquifer. These factors reveal first the existence of an intensive intrusion of seawater and second the mechanisms of contamination through the recharge processes of groundwater. Consequently, the assessment of water quality and the determination of the risk of water contamination by pollution seems to be very useful for an effective management of groundwater resources, and also for preventing salinization and minimizing the phenomena of seawater intrusion.

Effects of strong hydrogen bonds and weak intermolecular interactions on supramolecular assemblies of 4-fluorobenzylamine

NASA Astrophysics Data System (ADS)

Wang, Shi; Ding, Xue-Hua; Li, Yong-Hua; Huang, Wei

2015-07-01

A series of supramolecular salts have been obtained by the self-assembly of 4-fluorobenzylamine and halide ions or metal chloride with 18-crown-6 as the host in the hydrochloric acid medium, i.e. (C7H9FN)+ṡX- (X = Cl-, 1; Br-, 2), [(C7H9FN)2ṡ(18-crown-6)2]2+ṡ(MCl4)2- (M = Mn, 3; Co, 5; Zn, 7; Cd, 8), [(C7H9FN)ṡ(18-crown-6)]+ṡ(FeCl4)- (4) and [(C7H9FN)ṡ(18-crown-6)]+ṡ1/2(CuCl4)2- (6). Structural analyses indicate that 1-2 crystallize in the triclinic space group P-1, 4 in orthorhombic space group Pnma and 3, 5, 6-8 in the monoclinic space group P21/c or C2/c. In these compounds, extensive intermolecular interactions have been utilized for the self-assembly of diverse supramolecular architectures, ranging from strong N-H⋯X (X = O, Cl, Br) hydrogen bonds to weak C-H⋯Y (Y = F, Cl, π) interactions. N-H⋯Cl/Br hydrogen bonds offer the major driving force in the crystal packing of salts 1-2 while N-H⋯O hydrogen bonds are found in salts 3-8.

EXAFS study of mercury(II) sorption to Fe- and Al-(hydr)oxides - II. Effects of chloride and sulfate

USGS Publications Warehouse

Kim, C.S.; Rytuba, J.J.; Brown, Gordon E.

2004-01-01

Common complexing ligands such as chloride and sulfate can significantly impact the sorption of Hg(II) to particle surfaces in aqueous environmental systems. To examine the effects of these ligands on Hg(II) sorption to mineral sorbents, macroscopic Hg(II) uptake measurements were conducted at pH 6 and [Hg]i=0.5 mM on goethite (??-FeOOH), ??-alumina (??-Al2O3), and bayerite (??-Al(OH)3) in the presence of chloride or sulfate, and the sorption products were characterized by extended X-ray absorption fine structure (EXAFS) spectroscopy. The presence of chloride resulted in reduced uptake of Hg(II) on all three substrates over the Cl- concentration ([Cl-]) range 10-5 to 10-2 M, lowering Hg surface coverages on goethite, ??-alumina, and bayerite from 0.42 to 0.07 ??mol/m2, 0.06 to 0.006 ??mol/m2, and 0.55 to 0.39 ??mol/m2 ([Cl -]=10-5 to 10-3 M only), respectively. This reduction in Hg(II) uptake is primarily a result of the formation of stable, nonsorbing aqueous HgCl2 complexes in solution, limiting the amount of free Hg(II) available to sorb. At higher [Cl-] beam reduction of Hg(II) to Hg(I) was observed, resulting in the possible formation of aqueous Hg2Cl2 species and the precipitation of calomel, Hg 2Cl2(s). The presence of sulfate caused enhanced Hg(II) uptake over the sulfate concentration ([SO42-]) range 10-5 to 0.9 M, increasing Hg surface coverages on goethite, ??-alumina, and bayerite from 0.39 to 0.45 ??mol/m2, 0.11 to 0.38 ??mol/m2, and 0.36 to 3.33 ??mol/m2, respectively. This effect is likely due to the direct sorption or accumulation of sulfate ions at the substrate interface, effectively reducing the positive surface charge that electrostatically inhibits Hg(II) sorption. Spectroscopic evidence for ternary surface complexation was observed in isolated cases, specifically in the Hg-goethite-sulfate system at high [SO42-] and in the Hg-goethite-chloride system. ?? 2003 Elsevier Inc. All rights reserved.

Synthesis and characterization of prospective polyanionic electrode materials for high performance energy storage applications

NASA Astrophysics Data System (ADS)

Jayachandran, M.; Durai, G.; Vijayakumar, T.

2018-04-01

In the present study, Polyanionic compound (SO4)-group based on Li2Ni(SO4)2 (Lithium Nickel Sulphate) composite electrodes materials were prepared by a ball-milling method and solid-state reaction route. X-ray diffraction analysis confirmed the formation of a polycrystalline orthorhombic phase of composite Li2Ni(SO4)2 with an average crystallite size of about 50.16 nm. Field Emission Scanning electron microscopy investigation reveals the spherical shape particles with the particle size of around 200–500 nm. Raman and FTIR analysis confirms the structural and functional groups of the synthesized materials and also the formation of Li2Ni(SO4)2. The electrochemical measurements using cyclic voltammetry (CV) and galvanostatic charging-discharging (GCD) techniques were carried out to study the electrochemical supercapacitive performance of the composite Li2Ni (SO4)2 electrodes. From the CV investigations, an areal capacitance of 508 mF cm‑2 was obtained at 10 mV s‑1. The galvanostatic charge-discharge (GCD) measurements exhibited the areal capacitance of 101 mF cm‑2 at a constant current density of 2 mA cm‑2 in 2 M KOH. These GCD profiles were linear and also symmetric in nature with the maximum columbic efficiency of about 85%. The electrochemical performance of the composite Li2Ni(SO4)2 electrode material shows excellent performance for supercapacitor applications.

Uranyl coordination in ionic liquids: the competition between ionic liquid anions, uranyl counterions, and Cl- anions investigated by extended X-ray absorption fine structure and UV-visible spectroscopies and molecular dynamics simulations.

PubMed

Gaillard, C; Chaumont, A; Billard, I; Hennig, C; Ouadi, A; Wipff, G

2007-06-11

The first coordination sphere of the uranyl cation in room-temperature ionic liquids (ILs) results from the competition between its initially bound counterions, the IL anions, and other anions (e.g., present as impurities or added to the solution). We present a joined spectroscopic (UV-visible and extended X-ray absorption fine structure)-simulation study of the coordination of uranyl initially introduced either as UO2X2 salts (X-=nitrate NO3-, triflate TfO-, perchlorate ClO4-) or as UO2(SO4) in a series of imidazolium-based ILs (C4mimA, A-=PF6-, Tf2N-, BF4- and C4mim=1-methyl-3-butyl-imidazolium) as well as in the Me3NBuTf2N IL. The solubility and dissociation of the uranyl salts are found to depend on the nature of X- and A-. The addition of Cl- anions promotes the solubilization of the nitrate and triflate salts in the C4mimPF6 and the C4mimBF4 ILs via the formation of chloro complexes, also formed with other salts. The first coordination sphere of uranyl is further investigated by molecular dynamics (MD) simulations on associated versus dissociated forms of UO2X2 salts in C4mimA ILs as a function of A- and X- anions. Furthermore, the comparison of UO2Cl(4)2-, 2 X- complexes with dissociated X- anions, to the UO2X2, 4 Cl- complexes with dissociated chlorides, shows that the former is more stable. The case of fluoro complexes is also considered, as a possible result of fluorinated IL anion's degradation, showing that UO2F42- should be most stable in solution. In all cases, uranyl is found to be solvated as formally anionic UO2XnAmClp2-n-m-p complexes, embedded in a cage of stabilizing IL imidazolium or ammonium cations.

Electron Collision Shift of the Lyman-Alpha Line in H and He+

DTIC Science & Technology

1988-09-09

K ’ O iA ONA ’F’ )E i CE ’ O...ViDshing ton, DC 20375-5000 ’,.- K ..r, ’ 5 SO/I Ni, Sr. O (c), S VBO 9 ""Cl( ’/ N S’$ , N’ Dr. (A -i N VhF ()R(,A l ,’A 0ON (if apph(able) Office of...defined by c ~n C k CL SI~p ppkpppp, a n e k C L S p p pkp p p p S kp ( k ) momentum of the colliding electron before (after) the collision, L S =

Synthesis and characterization of novel Na15 (SO4 )5 F4 Cl:Ce3+ halosulfate phosphors.

PubMed

Bhake, A M; Nair, Govind B; Zade, G D; Dhoble, S J

2016-12-01

A series of Na 15 (SO 4 ) 5 F 4 Cl phosphors doped with Ce 3+ ions was prepared using the wet chemical method. X-Ray diffraction studies were used to determine their phase formation and purity. Fourier transform infrared spectroscopy effectively identified the chemical bonds present in the molecule. The photoluminescence properties of the as-prepared phosphors were investigated and the Ce 3+ ions in these hosts were found to give broadband emission in the UV range. For the thermoluminescence study, phosphors were irradiated with a 5 Gy dose of γ-rays from a 60 Co source. Chen's half-width method was employed to calculate the trapping parameters from the thermoluminescence glow curve. Copyright © 2016 John Wiley & Sons, Ltd. Copyright © 2016 John Wiley & Sons, Ltd.

A search for non-standard model W helicity in top quark decays

NASA Astrophysics Data System (ADS)

Kilminster, Benjamin John

The structure of the tbW vertex is probed by measuring the polarization of the W in t → W + b → l + v + b. The invariant mass of the lepton and b quark measures the W decay angle which in turn allows a comparison with polarizations expected from different possible models for the spin properties of the tbW interaction. We measure the fraction by rate of Ws produced with a V + A coupling in lieu of the Standard Model V-A to be fV + A = -0.21+0.42-0.24 (stat) +/- 0.21 (sys). We assign a limit of fV + A < 0.80 95% Confidence Level (CL). By combining this result with a complementary observable in the same data, we assign a limit of fV + A < 0.61 95% CL. We find no evidence for a non-Standard Model tbW vertex.

Major hydrogeochemical processes in the two reservoirs of the Yangbajing geothermal field, Tibet, China

NASA Astrophysics Data System (ADS)

Guo, Qinghai; Wang, Yanxin; Liu, Wei

2007-10-01

The Yangbajing geothermal field with the highest reservoir temperature in China is located about 90 km northwest to Lhasa City, capital of Tibet, where high temperature geothermal fluids occur both in shallow and deep reservoirs. The geophysical survey by the INDEPTH (International Deep Profiling of Tibet and the Himalayas) project group proved the existence of magmatic heat source at Yangbajing. In the study area, the hydrochemistry of cold surface waters and groundwaters and that of thermal groundwaters from both reservoirs are distinctively different. However, analysis of the relationship between enthalpy values and Cl concentrations of cold groundwaters and geothermal fluids indicates that the geothermal fluids from the shallow reservoir were formed as a result of mixing of cold groundwaters with geothermal fluids from the deep reservoir. In other words, the geothermal fluids from the deep reservoir flowed upwards into the shallow reservoir where it was diluted by the shallow cold groundwaters to form the shallow geothermal fluids with much lower temperature. A binary mixing model with two endmembers (the cold groundwaters and the deep geothermal fluids) was proposed and the mixing ratios for the geothermal fluid from each shallow well were estimated. Using the mixing ratios, the concentrations of some constituents in shallow geothermal fluids, such as As, B, SiO 2, SO 42- and F, were calculated and their differences with the actual concentrations were estimated. The results show that the differences between estimated and actual concentrations of As and B are small (the average absolute values being only 1.9% and 7.9%, respectively), whereas those of SiO 2, SO 42- and F are much bigger, indicating that other hydrogeochemical processes are responsible for the concentrations of these constituents. It is postulated that SiO 2 precipitation due to water temperature decrease, H 2S oxidation and ion exchange between OH - in geothermal waters and exchangeable F - in fluoride bearing silicate minerals during the geothermal fluid upflow might be the causes for the observed concentration differences.

Hydrogeochemistry and environmental impact of geothermal waters from Yangyi of Tibet, China

NASA Astrophysics Data System (ADS)

Guo, Qinghai; Wang, Yanxin; Liu, Wei

2009-02-01

The Yangyi geothermal field, located 72 km northwest to Lhasa City, capital of Tibet, has a high reservoir temperature up to at least 207.2 °C. The geothermal waters from both geothermal wells and hot springs belong to the HCO 3 (+CO 3)-Na type. Factor analysis of all the chemical constituents shows that they can be divided into two factors: F 1 factor receives the contributions of SO 42-, Cl -, SiO 2, As, B, Na +, K +, and Li +; whereas F 2 factor is explained by HCO 3-, F -, CO 32-, Ca 2+, and Sr 2+. The F 1 factor can be regarded as an indicator of the reservoir temperature distribution at Yangyi, but its variable correlation with the results of different geothermometers (Na-K, quartz and K-Mg) does not allow one to draw further inferences. Different from F 1, the F 2 factor is an indicator of a group of hydrogeochemical processes resulting from the CO 2 pressure decrease in geothermal water during its ascent from the deep underground, including transformation of HCO 3- to CO 32-, precipitation of Ca 2+ and Sr 2+, and release of F - from some fluoride-bearing minerals of reservoir rocks. The plot of enthalpy vs. chloride, prepared on the basis of Na-K equilibrium temperatures, suggests that a parent geothermal liquid (PGL) with Cl - concentration of 185 mg/L (that of sample YYT-8) and enthalpy of 1020 J/g (corresponding to a temperature of 236-237 °C, i.e., somewhat higher than that of sample YYT-6) is present in the geothermal reservoir of the Yangyi area, below both the Qialagai valley and the Bujiemu valley, although the samples less affected by mixing and cooling (YYT-6 and YYT-7) come from the second site. The discharge of geothermal waters with high contents of toxic elements such as B, As and F into the Luolang River, the only drinking water source for local residents, has caused slight pollution of the river water. Great care should therefore be taken in the geothermal water resource management at Yangyi.

Rain water chemistry in Ankara, Turkey

NASA Astrophysics Data System (ADS)

Tuncel, Semra G.; Ungör, Sevgi

Samples of rain water were collected in Ankara for the period between September 1989 and May 1990, by using wet-only sampler. Concentrations of major cations (H +, Na + K + Ca 2+ and NH 4+) and major anions (Cl -, NO 3- and SO 42-) were determined for the first time in Turkey. The rain water was not acidic owing to high concentrations of alkaline soil particles in the atmosphere. However, the concentrations of acid forming ions, such as SO 4- and N03, were higher than the concentrations expected in a typical urban atmosphere. Most of the SO 4- in rain water was in the form of CaSO 4. Rain-aerosol coupling were examined by simultaneous sampling of aerosols with rain. The ions most efficiently scavenged from the atmosphere were found to be SO 42- and Ca 2+.

Effects of Simulated Nitrogen Deposition on Soil Net Nitrogen Mineralization in the Meadow Steppe of Inner Mongolia, China

PubMed Central

Liu, Xing-ren; Ren, Jian-qiang; Li, Sheng-gong; Zhang, Qing-wen

2015-01-01

Effects of simulated nitrogen (N) deposition on soil net nitrogen mineralization (NNM) were examined in situ during two growing seasons, using the resin-core technique in the semiarid meadow steppe in Inner Mongolia, China. The aim of this study is to clarify the effect of N levels (0, 10, and 20 kg N ha−1yr−1) and forms (NH4 + and NO3 -) on soil mineral N and NNM. Our results showed that N levels had no significant differences on soil mineral N and NNM. In the first year, three N treatments ((NH4)2SO4, NH4Cl and KNO3) increased soil NH4 + concentrations but had no significant effects on soil NO3 - concentrations. In the second year, (NH4)2SO4 treatment increased soil NO3 - concentrations, NH4Cl and KNO3 treatments decreased them. Three N treatments significantly decreased soil NH4 + concentrations in the later stages of the second year. As for the soil NNM, three N treatments had no significant effects on the rates of soil NNM (R m) and net nitrification (R n) in the first year, but significantly decreased them in the second year. The contribution of N addition to Rm was higher from (NH4)2SO4 than from NH4Cl and KNO3. However, Soil R m was mainly affected by soil water content (SWC), accumulated temperature (Ta), and soil total N (TN). These results suggest that the short-term atmospheric N deposition may inhibit soil NNM in the meadow steppe of Inner Mongolia. PMID:26218275

Seasonal variations and size distributions of water-soluble ions of atmospheric particulate matter at Shigatse, Tibetan Plateau.

PubMed

Yang, Yongjie; Zhou, Rui; Yan, Yan; Yu, Yue; Liu, Junqing; Di, Yi'an; Du, Zhenyu; Wu, Dan

2016-02-01

Size-segregated atmospheric particulate matter (PM) samples were collected from July 2012 to September 2013 at Shigatse, high-altitude (3836 m above sea level) site on the south Tibetan Plateau (TP); objectives were to determine the characteristics and size distribution of water-soluble ions (WSIs). Eight major WSIs (Na(+), K(+), Mg(2+), Ca(2+), NH4(+), Cl(-), SO4(2-), and NO3(-)) were detected by ion chromatography. The total concentrations of WSIs were 6370 ± 1916 ng m(-3) in dry season (October - December, January - April), and 5261 ± 769 ng/m(3) during wet phase (May - September). The contribution of K(+) (130 ng m(-3)), Cl(-) (2035 ng m(-3)), SO4(2-) (1176 ng m(-3)), and NO3(-) (706 ng m(-3))(-)were significantly enhanced in dry season, and that of Na(+) (455 ng m(-3)), Mg(2+)(65.4 ng m(-3)), Ca(2+)(1034 ng m(-3)), and NH4(+) (1948 ng m(-3)) were significantly enhanced during wet phase. Mg(2+) and Ca(2+) were concentrated in the coarse mode, and the other ions concentrated in fine mode and coarse mode during two seasons. The correlation coefficients between K(+) and NH4(+), Cl(-), SO4(2-) and NO3(-) were 0.58 (P < 0.01), 0.40 (P < 0.05), 0.82 (P < 0.01) and 0.69 (P < 0.01), indicating their dominant contribution from biomass burning in dry season. The significant correlation between NH4(+) and HCO3(-) which were calculated by ion balance (r = 0.89, P < 0.01), suggesting the source from nitrogen fertilizers during wet phase. Copyright © 2015 Elsevier Ltd. All rights reserved.

Atomic contributions from spin-orbit coupling to 29Si NMR chemical shifts in metallasilatrane complexes.

PubMed

Autschbach, Jochen; Sutter, Kiplangat; Truflandier, Lionel A; Brendler, Erica; Wagler, Jörg

2012-10-01

New members of a novel class of metallasilatrane complexes [X-Si-(μ-mt)(4)-M-Y], with M=Ni, Pd, Pt, X=F, Cl, Y=Cl, Br, I, and mt=2-mercapto-1-methylimidazolide, have been synthesized and characterized structurally by X-ray diffraction and by (29)Si solid-state NMR. Spin-orbit (SO) effects on the (29)Si chemical shifts induced by the metal, by the sulfur atoms in the ligand, and by heavy halide ligands Y=Cl, Br, I were investigated with the help of relativistic density functional calculations. Operators used in the calculations were constructed such that SO coupling can selectively be switched off for certain atoms. The unexpectedly large SO effects on the (29)Si shielding in the Ni complex with X=Y=Cl reported recently originate directly from the Ni atom, not from other moderately heavy atoms in the complex. With respect to Pd, SO effects are amplified for Ni owing to its smaller ligand-field splitting, despite the smaller nuclear charge. In the X=Cl, Y=Cl, Br, I series of complexes the Y ligand strongly modulates the (29)Si shift by amplifying or suppressing the metal SO effects. The pronounced delocalization of the partially covalent M←Y bond plays an important role in modulating the (29)Si shielding. We also demonstrate an influence from the X ligand on the (29)Si SO shielding contributions originating at Y. The NMR spectra for [X-Si-(μ-mt)(4)-M-Y] must be interpreted mainly based on electronic and relativistic effects, rather than structural differences between the complexes. The results highlight the sometimes unintuitive role of SO coupling in NMR spectra of complexes containing heavy atoms. Copyright © 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Ash leachates from some recent eruptions of Mount Etna (Italy) and Popocatépetl (Mexico) volcanoes and their impact on amphibian living freshwater organisms

NASA Astrophysics Data System (ADS)

D'Addabbo, M.; Sulpizio, R.; Guidi, M.; Capitani, G.; Mantecca, P.; Zanchetta, G.

2015-12-01

Leaching experiments were carried out on fresh ash samples from Popocatépetl 2012, Etna 2011, and Etna 2012 eruptions, in order to investigate the release of compounds in both double-deionized and lake (Lake Ohrid, FYR of Macedonia) waters. The experiments were carried out using different grain sizes and variable stirring times (from 30 min to 7 days). Results were discussed in the light of changing pH and release of compounds for the different leachates. In particular, Etna samples induced alkalinization, and Popocatépetl samples induced acidification of the corresponding leachates. The release of different elements does not show correlation with the stirring time, with the measured maximum concentrations reached in the first hours of washing. General inverse correlation with grain size was observed only for Na+, K+, Cl-, Ca2+, Mg2+, SO42-, and Mn2+, while the other analysed elements show a complex, scattering relationship with grain size. Geochemical modelling highlights leachates' saturation only for F and Si, with Popocatépetl samples sometimes showing saturation in Fe. The analysed leachates are classified as undrinkable for humans on the basis of European laws, due to excess in F-, Mn2+, Fe, and SO42- (the latter only for Popocatépetl samples). Finally, the Etna 2012 and Popocatépetl leachates were used for toxicity experiments on living biota (Xenopus laevis). They are mildly toxic, and no significant differences exist between the toxic profiles of the two leachates. In particular, no significant embryo mortality was observed; while even at high dilutions, the leachates produced more than 20 % of malformed larvae.

Atmospheric fate of hydrofluoroolefins, CxF2x+1CHCH2 (x = 1,2,3,4 and 6): Kinetics with Cl atoms and products.

PubMed

Ballesteros, Bernabé; Jiménez, Elena; Moreno, Alberto; Soto, Amparo; Antiñolo, María; Albaladejo, José

2017-01-01

Rate coefficients for the gas-phase reactions of C x F 2x+1 CHCH 2 (x = 1, 2, 3, 4 and 6) with Cl atoms were determined at (298 ± 2) K and (710 ± 5) Torr of air using a relative rate technique. Two experimental setups with simulation chambers were employed with Fourier Transform Infrared (FTIR) spectroscopy and Gas Chromatography coupled to Mass Spectrometry (GC-MS) as detection techniques. The Cl-rate coefficients obtained were (in 10 -10  cm 3  molecule -1  s -1 ): (0.85 ± 0.11) for CF 3 CHCH 2 , (1.11 ± 0.08) for C 2 F 5 CHCH 2 , (1.12 ± 0.18) for C 3 F 7 CHCH 2 , (0.97 ± 0.09) for C 4 F 9 CHCH 2 , and (0.99 ± 0.08) for C 6 F 13 CHCH 2 . Additionally, the gas-phase products were identified and quantified, when possible, by FTIR spectroscopy or GC-MS. The main reaction product was reported to be C x F 2x+1 C(O)CH 2 Cl. The fluorinated species, C x F 2x+1 CHO and C x F 2x+1 C(O)CH 2 Cl, were identified. CF 3 C(O)CH 2 Cl and CF 3 CHO were found to be formed with molar yield of (69 ± 5)% and (9 ± 1)%, respectively. The global lifetime of the investigated C x F 2x+1 CHCH 2 due to their Cl-reaction is more than 100 days so this route does not compete with the removal by OH radicals. This lifetime is long enough for C x F 2x+1 CHCH 2 to be transported to remote areas where they can be degraded. However, at a local scale, in marine regions at dawn the removal of C x F 2x+1 CHCH 2 is expected to occur in ca. 1 day. The atmospheric degradation of these hydrofluoroolefins by Cl atoms is not expected to be a source of bioaccumulative perfluorinated carboxylic acids, C x F 2x+1 C(O)OH. Additionally, the UV absorption cross sections of CF 3 C(O)CH 2 Cl were determined together with the rate coefficient of the OH reaction by an absolute kinetic method at room temperature. Copyright © 2016 Elsevier Ltd. All rights reserved.

Fetal fibronectin, cervical length, and the risk of preterm birth in patients with an ultrasound or physical exam indicated cervical cerclage.

PubMed

Kim, Renita S; Gupta, Simi; Lam-Rachlin, Jennifer; Saltzman, Daniel H; Rebarber, Andrei; Fox, Nathan S

2016-11-01

The objective of this study is to estimate the risk of preterm birth in patients with an ultrasound or physical exam indicated cervical cerclage based on the results of fetal fibronectin (fFN) and cervical length (CL) screening. Retrospective cohort of patients with a singleton pregnancy and an ultrasound or physical exam indicated Shirodkar cerclage placed by one maternal-fetal medicine practice from November 2005 to January 2015. Patients routinely underwent serial CL and fFN testing from 22 to 32 weeks. Based on ROC curve analysis, a short CL was defined as ≤15 mm. All fFN and CL results included are from after the cerclage placement. One hundred and four patients were included. Seventy eight (75%) patients had an ultrasound-indicated cerclage and 26 (25%) patients had a physical exam-indicated cerclage. A positive fFN was associate with preterm birth <32 weeks (15.6% versus 4.2%, p = 0.043),  <35 weeks (37.5% versus 11.1%, p = 0.002),  <37 weeks (65.6% versus 20.8%, p < 0.001), and earlier gestational ages at delivery (35.2 ± 3.9 versus 37.4 ± 2.9, p = 0.001). A short CL was also associated with preterm birth <35 weeks (50.0% versus 11.9%, p < 0.01), preterm birth <37 weeks (55.0% versus 29.8%, p = 0.033), and earlier gestational ages at delivery (34.8 ± 4.1 versus 37.2 ± 3.0, p = 0.004). The risk of preterm birth <32,  <35, and <37 weeks increased significantly with the number of abnormal markers. In patients with an ultrasound or physical exam indicated cerclage, a positive fFN and a short CL are both associated with preterm birth. The risk of preterm birth increases with the number of abnormal biomarkers.

[Influencing factors and mechanism of arsenic removal during the aluminum coagulation process].

PubMed

Chen, Gui-Xia; Hu, Cheng-Zhi; Zhu, Ling-Feng; Tong, Hua-Qing

2013-04-01

Aluminum coagulants are widely used in arsenic (As) removal during the drinking water treatment process. Aluminium chloride (AlCl3) and polyaluminium chloride (PACl) which contains high content of Al13 were used as coagulants. The effects of aluminum species, pH, humic acid (HA) and coexisting anions on arsenic removal were investigated. Results showed that AlCl3 and PACl were almost ineffective in As(II) removal while the As(V) removal efficiency reached almost 100%. pH was an important influencing factor on the arsenic removal efficiency, because pH influenced the distribution of aluminum species during the coagulation process. The efficiency of arsenic removal by aluminum coagulants was positively correlated with the content of Al13 species. HA and some coexisting anions showed negative impact on arsenic removal because of the competitive adsorption. The negative influence of HA was more pronounced at low coagulant dosages. PO4(3-) and F(-) showed marked influence during arsenic removal, but there was no obvious influence when SiO3(2-), CO3(2-) and SO4(2-) coexisted. The present study would be helpful to direct arsenic removal by enhanced coagulation during the drinking water treatment.

Copper and Gold Partitioning Between Brine and Vapor as a Function of Reduced Sulfur

NASA Astrophysics Data System (ADS)

Ehlich, J. J.; Frank, M. R.; Bodnar, R. J.

2017-12-01

This study examined Cu and Au partitioning between sulfur-rich vapors (v) and brines (b) at conditions representative of porphyry ore deposits. Experiments were conducted at 700 °C and 100 MPa, with oxygen fugacity, f(O2), buffered by either Ni-NiO or MnO-Mn3O4. Sulfur fugacity, f(S2), was buffered by pyrrhotite + chalcopyrite or bornite + pyrrhotite + chalcopyrite mineral assemblages between log -5.6 and log 0.6. The fugacities of H2S and SO2 were calculated using the known values of fO2 and fS2. In each experiment, a gold capsule was loaded with a sulfide assemblage, a quartz core to trap fluid inclusions, and a 5 wt.% NaCl-equivalent aqueous solution containing NaCl, KCl and HCl with molar NaCl:KCl and NaCl:HCl ratios of 1 and 100, respectively. Coexisting low salinity (v) and high salinity (b) inclusions were trapped in the quartz and their salinities were estimated using microthermometry, and verified against expected salinities from the NaCl-H2O system. Na, K, Fe, Cu, and Au concentrations from 73 b and 39 v fluid inclusions were determined using laser ablation inductively coupled plasma mass spectrometry (LA-ICP-MS). Nernst-style partition coefficients between b and v for a given element (Dxb/v) were determined as a function of O2, S2, H2S, and SO2 fugacities. DCub/v ranged from 2.8 to 6.6 and increased with increasing f(O2), decreased with increasing f(S2), and decreased with increasing f(H2S). Gold partition coefficients ranged from 4.6 to 8.5, with DAub/v increasing with increasing f(O2), decreasing with increasing f(S2), and decreasing with increasing f(H2S). The absolute concentrations of Cu and Au increased in both the b and v phases with increasing f(H2S), but the increase was proportionally greater in v than b. Cu and Au partitioned into b relative to v at all conditions, but Dxb/v decreased slightly with decreasing O2 or increasing S2 fugacity. Dxb/v for Cu and Au appear most strongly linked to H2S, consistently decreasing with increasing f(H2S), but our data suggest that Cu and Au prefer chloride-complexes in porphyry systems (Dxb/v always >1). Reduced sulfur species may become increasingly important ligands in the porphyry-epithermal transition, in particularly high f(H2S) systems, or in systems dominated by a low salinity supercritical fluid or vapor.

The measurement of sulfate mineral solubilities in the Na-K-Ca-Cl-SO 4-H 2O system at temperatures of 100, 150 and 200°C

NASA Astrophysics Data System (ADS)

Freyer, Daniela; Voigt, Wolfgang

2004-01-01

At T > 100°C development of thermodynamic models suffers from missing experimental data, particularly for solubilities of sulfate minerals in mixed solutions. Solubilities in Na +-K +-Ca 2+-Cl --SO 42-/H 2O subsystems were investigated at 150, 200°C and at selected compositions at 100°C. The apparatus used to examine solid-liquid phase equilibria under hydrothermal conditions has been described. In the system NaCl-CaSO 4-H 2O the missing anhydrite (CaSO 4) solubilities at high NaCl concentrations up to halite saturation have been determined. In the system Na 2SO 4-CaSO 4-H 2O the observed glauberite (Na 2SO 4 · CaSO 4) solubility is higher than that predicted by the high temperature model of Greenberg and Møller (1989), especially at 200°C. At high salt concentrations, solubilities of both anhydrite and glauberite increase with increasing temperature. Stability fields of the minerals syngenite (K 2SO 4 · CaSO 4 · H 2O) and goergeyite (K 2SO 4 · 5 CaSO 4 · H 2O) were determined, and a new phase was found at 200°C in the K 2SO 4-CaSO 4-H 2O system. Chemical and single crystal structure analysis give the formula K 2SO 4 · CaSO 4. The structure is isostructural with palmierite (K 2SO 4 · PbSO 4). The glaserite ("3 K 2SO 4 · Na 2SO 4") appears as solid solution in the system Na 2SO 4-K 2SO 4-H 2O. Its solubility and stoichiometry was determined as a function of solution composition.

Soil salination indicators

USDA-ARS?s Scientific Manuscript database

Salts are naturally present in soils, and many salt elements are essential nutrients for plants. The most common soluble salts in soil include major cations of sodium (Na+), magnesium (Mg2+), calcium (Ca2+), potassium (K+), and anions of chloride (Cl-), sulfate (SO42-), bicarbonate (HCO3-) and carbo...

Assessment of Groundwater quality in Krishnagiri and Vellore Districts in Tamil Nadu, India

NASA Astrophysics Data System (ADS)

Shanmugasundharam, A.; Kalpana, G.; Mahapatra, S. R.; Sudharson, E. R.; Jayaprakash, M.

2017-07-01

Groundwater quality is important as it is the main factor determining its suitability for drinking, domestic, agricultural and industrial purposes. The suitability of groundwater for drinking and irrigation has been assessed in north and eastern part of Krishnagiri district, South-western part of Vellore district and contiguous with Andhra Pradesh states, India. A total of 31 groundwater samples were collected in the study area. The groundwater quality assessment has been carried out by evaluating the physicochemical parameters such as pH, EC, TDS, {HCO}3^{ - }, Cl-, {SO}4^{2 - }, Ca2+, Mg2+, Na+ and K+. The dominant cations are in the order of Na+ > K+ > Ca2+ > Mg2+ while the dominant anions have the trends of Cl- > {HCO}3^{ - } > {SO}4^{2 - } > CO3. The quality of the water is evaluated using Wilcox diagram and the results reveals that most of the samples are found to be suitable for irrigation. Based on these parameters, groundwater has been assessed in favor of its suitability for drinking and irrigation purpose.

Comparison of forest edge effects on throughfall deposition in different forest types.

PubMed

Wuyts, Karen; De Schrijver, An; Staelens, Jeroen; Gielis, Leen; Vandenbruwane, Jeroen; Verheyen, Kris

2008-12-01

This study examined the influence of distance to the forest edge, forest type, and time on Cl-, SO4(2-), NO3(-), and NH4+ throughfall deposition in forest edges. The forests were dominated by pedunculate oak, silver birch, or Corsican/Austrian pine, and were situated in two regions of Flanders (Belgium). Along transects, throughfall deposition was monitored at distances of 0-128 m from the forest edge. A repeated-measures analysis demonstrated that time, forest type, and distance to the forest edge significantly influenced throughfall deposition of the ions studied. The effect of distance to the forest edge depended significantly on forest type in the deposition of Cl-, SO4(2-), and NO3(-): the edge effect was significantly greater in pine stands than in deciduous birch and oak stands. This finding supports the possibility of converting pine plantations into oak or birch forests in order to mitigate the input of nitrogen and potentially acidifying deposition.

Preparation of Zn(BH4)2 and diborane and hydrogen release properties of Zn(BH4)2+xMgH2 (x=1, 5, 10, and 15)

NASA Astrophysics Data System (ADS)

Kwak, Young Jun; Kwon, Sung Nam; Song, Myoung Youp

2015-09-01

Zn(BH4)2 was prepared by milling ZnCl2 and NaBH4 in a planetary ball mill under Ar atmosphere, and Zn(BH4)2+xMgH2 (x=1, 5, 10, and 15) samples were prepared. Diborane (B2H6) and hydrogen release characteristics of the Zn(BH4)2 and Zn(BH4)2+xMgH2 samples were studied. The samples synthesized by milling ZnCl2 and NaBH4 contained Zn(BH4)2 and NaCl, together with small amounts of ZnCl2 and NaBH4. We designated these samples as Zn(BH4)2(+NaCl). The weight loss up to 400 °C of the Zn(BH4)2(+NaCl) sample synthesized by milling 4 h was 11.2 wt%. FT-IR analysis showed that Zn(BH4)2 was formed in the Zn(BH4)2(+NaCl) samples. MgH2 was also milled in a planetary ball mill, and mixed with the Zn(BH4)2(+NaCl) synthesized by milling for 4 h in a mortar and pestle. The weight loss up to 400 °C of Zn(BH4)2(+NaCl)+MgH2 was 8.2 wt%, corresponding to the weight % of diborane and hydrogen released from the Zn(BH4)2(+NaCl)+MgH2 sample, with respect to the sample weight. DTA results of Zn(BH4)2(+NaCl)+xMgH2 showed that the decomposition peak of Zn(BH4)2 was at about 61 °C, and that of MgH2 was at about 370-389 °C.

Groundwater chemistry and occurrence of arsenic in the Meghna floodplain aquifer, southeastern Bangladesh

USGS Publications Warehouse

Zahid, A.; Hassan, M.Q.; Balke, K.-D.; Flegr, M.; Clark, D.W.

2008-01-01

Dissolved major ions and important heavy metals including total arsenic and iron were measured in groundwater from shallow (25-33 m) and deep (191-318 m) tube-wells in southeastern Bangladesh. These analyses are intended to help describe geochemical processes active in the aquifers and the source and release mechanism of arsenic in sediments for the Meghna Floodplain aquifer. The elevated Cl- and higher proportions of Na+ relative to Ca2+, Mg2+, and K+ in groundwater suggest the influence by a source of Na+ and Cl-. Use of chemical fertilizers may cause higher concentrations of NH 4+ and PO 43- in shallow well samples. In general, most ions are positively correlated with Cl-, with Na+ showing an especially strong correlation with Cl-, indicating that these ions are derived from the same source of saline waters. The relationship between Cl-/HCO 3- ratios and Cl- also shows mixing of fresh groundwater and seawater. Concentrations of dissolved HCO 3- reflect the degree of water-rock interaction in groundwater systems and integrated microbial degradation of organic matter. Mn and Fe-oxyhydroxides are prominent in the clayey subsurface sediment and well known to be strong adsorbents of heavy metals including arsenic. All five shallow well samples had high arsenic concentration that exceeded WHO recommended limit for drinking water. Very low concentrations of SO 42- and NO 3- and high concentrations of dissolved Fe and PO 43- and NH 4+ ions support the reducing condition of subsurface aquifer. Arsenic concentrations demonstrate negative co-relation with the concentrations of SO 42- and NO 3- but correlate weakly with Mo, Fe concentrations and positively with those of P, PO 43- and NH 4+ ions. ?? 2007 Springer-Verlag.

Perchlorate in pleistocene and holocene groundwater in North-Central New Mexico

USGS Publications Warehouse

Plummer, Niel; Böhlke, J.K.; Doughten, M.W.

2006-01-01

Groundwater from remote parts of the Middle Rio Grande Basin in north-central New Mexico has perchlorate (ClO4-) concentrations of 0.12-1.8 ??g/L Because the water samples are mostly preanthropogenic in age (0-28 000 years) and there are no industrial sources in the study area, a natural source of the ClO4- is likely. Most of the samples have Br-, Cl-, and SO42- concentrations that are similar to those of modern bulk atmospheric deposition with evapotranspiration (ET) factors of about 7-40. Most of the ET values for Pleistocene recharge were nearly twice that for Holocene recharge. The NO3-/Cl- and ClO4-/Cl- ratios are more variable than those of Br -/Cl- or SO42-/Cl-. Samples thought to have recharged under the most arid conditions in the Holocene have relatively high NO3-/Cl- ratios and low ??15N values (+1 per mil (???)) similar to those of modern bulk atmospheric N deposition. The ??18O values of the NO 3- (-4 to 0 ???) indicate that atmospheric N0 3- was not transmitted directly to the groundwater but may have been cycled in the soils before infiltrating. Samples with nearly atmospheric NO3-/Cl- ratios have relatively high ClO4- concentrations (1.0-1.8 ??g/L) with a nearly constant ClO4-/Cl- mole ratio of (1.4 ?? 0.1) ?? 10-4, which would be consistent with an average ClO 4- concentration of 0.093 ?? 0.005 ??g/L in bulk atmospheric deposition during the late Holocene in north-central NM. Samples thought to have recharged underwetter conditions have higher ??15N values (+3 to +8 ???), lower N03-/Cl- ratios, and lower ClO4-/Cl- ratios than the ones most likely to preserve an atmospheric signal. Processes in the soils that may have depleted atmospherically derived NO3- also may have depleted ClO4- to varying degrees prior to recharge. If these interpretations are correct, then ClO4- concentrations of atmospheric origin as high as 4 ??g/L are possible in preanthropogenic groundwater in parts of the Southwest where ET approaches a factor of 40. Higher ClO4- concentrations in uncontaminated groundwater could occur in recharge beneath arid areas where ET is greater than 40, where long-term accumulations of atmospheric salts are leached suddenly from dry soils, or where other (nonatmospheric) natural sources of ClO/4- exist.

Chemical composition of rainwater in a tropical urban area of northern India

NASA Astrophysics Data System (ADS)

Jawad Al Obaidy, Abdul Hameed M.; Joshi, Himanshu

Rainwater samples during the monsoon of 2001 and 2002 were collected from Roorkee urban area, a medium sized "town group" situated on the right bank of Solani River, a tributary of the Ganga River, near the Himalayan foothills and analyzed for EC, pH, TSS, TDS and major ions. The median value of pH was 7.05, well above 5.6, which is the reference pH. The ratios of SO 42-+NO 3- and Ca 2++Mg 2+ (TA/TC) have been considered for acidity. In this study, ratio of TA/TC is quite below 1.0, indicating alkaline nature of rainwater. The concentration of ions in rain water have been observed to follow the pattern Ca 2+>HCO 3->Cl ->NO 3->Na +>Mg 2+>SO 42->K +. In order to estimate the marine and non-marine contribution, sea salt fraction has been calculated taking Na + as reference. All ionic ratios have been found to be higher than the recommended sea water ratios in all three types of land use, viz. residential, commercial and industrial, suggesting a significant contribution of non-marine origin for these components. A comparison with the data of the other Indian sites validates the inverse relation of Cl - and Na + with distance from the sea and highlights higher Ca 2+ concentration and lower SO 42- concentration.

Changes in Aerosol Chemistry in the Plume of Kilauea Volcano Caused by the 2008 Summit Eruption

NASA Astrophysics Data System (ADS)

Ilyinskaya, E.; Oppenheimer, C.

2009-05-01

In March 2008 an eruption began in Halema'uma'u summit crater of Kilauea volcano; this was the first summit eruption since 1982. Prior to the new active phase, degassing in the crater was predominantly from several small fumaroles emitting a weak translucent plume. The 2003-2007 average SO2 emission rate was 140 tonnes per day and increased drastically to over 2000 tonnes per day in March 2008. The plume emitted from the crater during the eruption was concentrated and opaque, containing both ash and aerosol particles. Aerosol particles were sampled in the plume from Halema'uma'u before the start of the new eruptive phase (August 2007) and during it (May 2008). Particles emitted from Pu'u'O'o crater were collected at the rim and 8- 10km downwind. Sampling was done with a cascade impactor which collects and segregates PM10 (particle matter <10 μm) into 14 size fractions. There is a significant increase in PM sulphate concentration during the eruptive phase, or from 0.11 up to 6.3 μg per m3 of sampled air. Cl- concentration increased from 0.097 to 0.338 μgm-3, while F- was not detected either before or during the eruption. The SO42-/Cl- ratio increased from 0.15 to 18.8. The concentration peak of SO42- shifts to a coarser PM size fraction during the active phase, or from 0.18-0.32 to 0.32-0.56 μm. It is possible that higher water vapour content during the eruption favours more rapid particle growth. PM collected at Pu'u'O'o rim shows a noteworthy bimodal SO42- concentration distribution with a finer peak between 0.32-0.56 μm and a coarser peak between 1.0-1.4 μm. The coarser PM is efficiently removed from the plume and is not detected when sampled 8km downwind of the source. Near-vent nitrate was not detected in pre-eruptive samples but was found in concentrations between 0.17-0.58 μgm-3 in syn-eruptive PM; these are much lower than the concentrations seen at Pu'u'O'o (up to 3.0 μgm-3). Work in progress is analysis of metal content in the pre- and syn-eruptive PM which will be correlated with the size-resolved chemistry of anions. Further field sampling will be made in April 2009 now that the eruptive activity is significantly diminished and potentially coming to an end.

Biotic and abiotic processes controlling water chemistry during snowmelt at rabbit ears pass, Rocky Mountains, Colorado, U.S.A.

USGS Publications Warehouse

Peters, N.E.; Leavesley, G.H.

1995-01-01

The chemical composition of snowmelt, groundwater, and streamwater was monitored during the spring of 1991 and 1992 in a 200-ha subalpine catchment on the western flank of the Rocky Mountains near Steamboat Springs, Colorado. Most of the snowmelt occurred during a one-month period annually that began in mid-May 1991 and mid-April 1992. The average water quality characteristics of individual sampling sites (meltwater, streamwater, and groundwater) were similar in 1991 and 1992. The major ions in meltwater were differentially eluted from the snowpack, and meltwater was dominated by Ca2+, SO4/2-, and NO3/-. Groundwater and streamwater were dominated by weathering products, including Ca2+, HCO3/- (measured as alkalinity), and SiO2, and their concentrations decreased as snowmelt progressed. One well had extremely high NO3/- concentrations, which were balanced by Ca2+ concentrations. For this well, hydrogen ion was hypothesized to be generated from nitrification in overlying soils, and subsequently exchanged with other cations, particularly Ca2+. Solute concentrations in streamwater also decreased as snowmelt progressed. Variations in groundwater levels and solute concentrations indicate thai most of the meltwater traveled through the surficial materials. A mass balance for 1992 indicated that the watershed retained H+, NH4/+, NO3/-, SO4/2- and Cl- and was the primary source of base cations and other weathering products. Proportionally more SO4/2- was deposited with the unusually high summer rainfall in 1992 compared to that released from snowmelt, whereas NO3/- was higher in snowmelt and Cl- was the same. The sum of snowmelt and rainfall could account for greater than 90% of the H+ and NH4/+ retained by the watershed and greater than 50% of the NO3/-.The chemical composition of snowmelt, groundwater, and streamwater was monitored during the spring of 1991 and 1992 in a 200-ha subalpine catchment on the western flank of the Rocky Mountains near Steamboat Springs, Colorado. The major ions in meltwater were differentially eluted from the snowpack, and meltwater was dominated by Ca2+, SO42-, and NO3-. Groundwater and streamwater were dominated by weathering products and their concentrations decreased as snowmelt progressed. Solute concentrations in streamwater also decreased as snowmelt progressed. A mass balance for 1992 showed that the watershed retained H+, NH4+, NO3-, SO42- and Cl- and was the primary source of base cations and other weathering products.

Amino Compounds as Inhibitors of De Novo Synthesis of Chlorobenzenes

NASA Astrophysics Data System (ADS)

Wang, Si-Jia; He, Pin-Jing; Lu, Wen-Tao; Shao, Li-Ming; Zhang, Hua

2016-04-01

The inhibitory effects of four amino compounds on the formation of chlorobenzenes (CBzs) - dioxin precursors and indicators, and the inhibitory mechanisms were explored. The results show NH4H2PO4 can decrease the total yields of CBzs (1,2di-CBz, 1,3di-CBz, 1,4di-CBz, penta-CBz and hexa-CBz) by 98.1%±1.6% and 96.1%±0.7% under air and nitrogen flow. The inhibitory effects indicated by the total yields of CBzs follow the order NH4H2PO4 > NH4HF2 > (NH4)2SO4 > NH4Br under air flow and NH4H2PO4 ≈ (NH4)2SO4 ≈ NH4HF2 >NH4Br under nitrogen flow. The inhibition mechanism revealed by thermal analysis that CuCl2 was converted to CuPO3 by reacting with NH4H2PO4 below 200 °C, which can block the transfer of chlorine and formation of C-Cl bonds at 350 °C. The effects of the other three inhibitors were weaker because their reactions with CuCl2, which form other copper compounds, and the reaction of CuCl2 with carbon, which forms C-Cl bonds, were almost simultaneous and competitive. Oxygen influenced the yield of CBzs obviously, and the total yield of five CBzs sharply increased with oxygen. Because of their high efficiency, low environmental impact, low cost, and availability, amino compounds - especially NH4H2PO4 - can be utilized as inhibitors of CBzs during incineration.

Spin-orbit coupling calculations with the two-component normalized elimination of the small component method

NASA Astrophysics Data System (ADS)

Filatov, Michael; Zou, Wenli; Cremer, Dieter

2013-07-01

A new algorithm for the two-component Normalized Elimination of the Small Component (2cNESC) method is presented and tested in the calculation of spin-orbit (SO) splittings for a series of heavy atoms and their molecules. The 2cNESC is a Dirac-exact method that employs the exact two-component one-electron Hamiltonian and thus leads to exact Dirac SO splittings for one-electron atoms. For many-electron atoms and molecules, the effect of the two-electron SO interaction is modeled by a screened nucleus potential using effective nuclear charges as proposed by Boettger [Phys. Rev. B 62, 7809 (2000), 10.1103/PhysRevB.62.7809]. The use of the screened nucleus potential for the two-electron SO interaction leads to accurate spinor energy splittings, for which the deviations from the accurate Dirac Fock-Coulomb values are on the average far below the deviations observed for other effective one-electron SO operators. For hydrogen halides HX (X = F, Cl, Br, I, At, and Uus) and mercury dihalides HgX2 (X = F, Cl, Br, I) trends in spinor energies and SO splittings as obtained with the 2cNESC method are analyzed and discussed on the basis of coupling schemes and the electronegativity of X.

The contribution of residential coal combustion to atmospheric PM2. 5 in northern China during winter

NASA Astrophysics Data System (ADS)

Liu, Pengfei; Zhang, Chenglong; Xue, Chaoyang; Mu, Yujing; Liu, Junfeng; Zhang, Yuanyuan; Tian, Di; Ye, Can; Zhang, Hongxing; Guan, Jian

2017-09-01

A vast area in northern China, especially during wintertime, is currently suffering from severe haze events due to the high levels of atmospheric PM2. 5. To recognize the reasons for the high levels of PM2. 5, daily samples of PM2. 5 were simultaneously collected at the four sampling sites of Beijing city (BJ), Baoding city (BD), Wangdu county (WD) and Dongbaituo (DBT) during the winter and spring of 2014-2015. The concentrations of the typical water-soluble ions (WSIs, such as Cl-, NO3-, SO42- and NH4+) at DBT were found to be remarkably higher than those at BJ in the two winters, but almost the same as those at BJ in the two springs. The evidently greater concentrations of OC, EC and secondary inorganic ions (NO3-, SO42-, NH4+ and Cl-) at DBT than at WD, BD and BJ during the winter of 2015 indicated that the pollutants in the rural area were not due to transportation from neighbouring cities but dominated by local emissions. As the distinct source of atmospheric OC and EC in the rural area, the residential coal combustion also made a contribution to secondary inorganic ions through the emissions of their precursors (NOx, SO2, NH3 and HCl) as well as heterogeneous or multiphase reactions on the surface of OC and EC. The average mass proportions of OC, EC, NO3- and SO42- at BD and WD were found to be very close to those at DBT, but were evidently different from those at BJ, implying that the pollutants in the cities of WD and BD, which are fully surrounded by the countryside, were strongly affected by the residential coal combustion. The OC / EC ratios at the four sampling sites were almost the same value (4.8) when the concentrations of PM2. 5 were greater than 150 µg m-3, suggesting that the residential coal combustion could also make a dominant contribution to atmospheric PM2. 5 at BJ during the severe pollution period when the air parcels were usually from southwest-south regions, where a high density of farmers reside. The evident increase in the number of the species involved in significant correlations (p < 0. 05) from the countryside to the cities further confirmed that residential coal combustion was the dominant source of key species in the rural area. However, the complex sources including local emissions and regional transportation were responsible for the atmospheric species in the cities. Strong correlations among OC, EC, Cl-, NO3- and NH4+ were found at the four sampling sites but only a strong correlation was found between OC (or EC) and SO42- at BJ, implying that the formation rate of SO42- via heterogeneous or multiphase reactions might be relatively slower than those of NO3-, NH4+ and Cl-. Based on the chemical mass closure (CMC) method, the contributions of the primary particle emission from residential coal combustion to atmospheric PM2. 5 at BJ, BD, WD and DBT were estimated to be 32, 49, 43 and 58 %, respectively.

Superelectrophilic tetrakis(carbonyl)palladium(II)- and -platinum(II) undecafluorodiantimonate(V), [Pd(CO)4][Sb(2)F(11)]2 and [Pt(CO)4][Sb(2)F(11)]2: syntheses, physical and spectroscopic properties, their crystal, molecular, and extended structures, and density functional calculations: an experimental, computational, and comparative study .

PubMed

Willner, H; Bodenbinder, M; Bröchler, R; Hwang, G; Rettig, S J; Trotter, J; von Ahsen, B; Westphal, U; Jonas, V; Thiel, W; Aubke, F

2001-01-31

The salts [M(CO)(4)][Sb(2)F(11)](2), M = Pd, Pt, are prepared by reductive carbonylation of Pd[Pd(SO(3)F)(6)], Pt(SO(3)F)(4) or PtF(6) in liquid SbF(5), or HF-SbF(5). The resulting moisture-sensitive, colorless solids are thermally stable up to 140 degrees C (M = Pd) or 200 degrees C (M = Pt). Their thermal decompositions are studied by differential scanning calorimetry (DSC). Single crystals of both salts are suitable for an X-ray diffraction study at 180 K. Both isostructural salts crystallize in the monoclinic space group P2(1)/c (No. 14). The unit cell volume of [Pt(CO)(4)][Sb(2)F(11)](2) is smaller than that of [Pd(CO)(4)][Sb(2)F(11)](2) by about 0.4%. The cations [M(CO)(4)](2+), M = Pd, Pt, are square planar with only very slight angular and out-of-plane deviations from D(4)(h)() symmetry. The interatomic distances and bond angles for both cations are essentially identical. The [Sb(2)F(11)](-) anions in [M(CO)(4)][Sb(2)F(11)](2,) M = Pd, Pt, are not symmetry-related, and both pairs differ in their Sb-F-Sb bridge angles and their dihedral angles. There are in each salt four to five secondary interionic C- -F contacts per CO group. Of these, two contacts per CO group are significantly shorter than the sum of the van der Waals radii by 0.58 - 0.37 A. In addition, structural, and spectroscopic details of recently synthesized [Rh(CO)(4)][Al(2)Cl(7)] are reported. The cations [Rh(CO)(4)](+) and [M(CO)(4)](2+), M = Pd, Pt, are characterized by IR and Raman spectroscopy. Of the 16 vibrational modes (13 observable, 3 inactive) 10 (Pd, Pt) or 9 (Rh), respectively, are found experimentally. The vibrational assignments are supported by DFT calculations, which provide in addition to band positions also intensities of IR bands and Raman signals as well as internal force constants for the cations. (13)C NMR measurements complete the characterization of the square planar metal carbonyl cations. The extensive characterization of [M(CO)(4)][Sb(2)F(11)](2), M = Pd, Pt, reported here, allows a comparison to linear and octahedral [M(CO)(n)()][Sb(2)F(11)](2) salts [M = Hg (n = 2); Fe, Ru, Os (n = 6)] and their derivatives, which permit a deeper understanding of M-CO bonding in the solid state for superelectrophilic cations with [Sb(2)F(11)](-) or [SbF(6)](-) as anions.

Utilization of GIS modeling in geoenvironmental studies of Qaroun Lake, El Fayoum Depression, Egypt

NASA Astrophysics Data System (ADS)

Attia, Abdelaal H.; El-Sayed, Salah Abdelwahab; El-Sabagh, Moustafa E.

2018-02-01

Qaroun Lake, the study area, is a natural protectorate located at the northern part of El Fayoum Depression, Egypt. An integrated approach including hydrochemistry, mineralogy of sediments and GIS analysis and modeling was conducted in order to determine the different geoenvironmental parameters affecting the lake environmental system. Forty two environmental water and sediment samples were collected from the lake and relevant drains in 2013. The water samples were analyzed for major ions and trace elements and the sediment ones were analyzed for clay and non-clay minerals. This study showed that the saline water of the lake (31490 < TDS < 45100 mg/l) typically is Na-Cl-SO4 water possessing primary salinity properties dominated by alkalies and strong acids. The order of ionic dominance was Na+ > Mg2+ > Ca2+ > K+ - Cl- > SO42- > HCO3- > CO32-. The water salt assemblages were KCl - NaCl - Na2SO4 - MgSO4 - CaSO4 - Ca(HCO3)2 reflecting a mixed water type. The contents of NaCl, Na2SO4 and MgSO4 salts were found to be fully controlled with the lake depths. The hydrogeochemical investigations revealed that the evaporation concentration is the primary process of the lake water evolution. The presence of trace elements in the lake water is essentially of allochtonous origin. The GIS-based maps indicated that the concentrations of Zn, Co, Mo, Pb, F and Cd elements in water had increased in the eastern part of the lake; meanwhile, the contents of NO3- ions had increased in the southwestern part indicating that these parts were the most vulnerable to the potential pollution with such elements. The XRD analysis revealed the existence of different mineral assemblages (quartz, kaolinite, goethite, calcite, halite, hematite, feldspar, gypsum, dolomite and saponite) in bottom sediments. The mineral concentrations varied greatly from place to another place along the lake and their distributions were asymmetric. The dominant minerals were the quartz and calcite. The mineralogical compositions of sediments were highly affected by the natural and man-mad activities. The most effective processes were the type of the water and solid materials coming from the northern geologic formations (by the northern winds) and from the eastern and southern drains. The land coverage change detection maps indicated the positive and negative changes in the lake area and its surroundings during the period of 1987-2000. The positive change in the area of the lake was about 12.63 km2 along the northern part of the lake, while the negative one was about 4.56 km2 in the southern parts. Based on the obtained results, some recommendations were presented to avoid the detrimental effects originated from the natural and human activities.

NOAA PMEL Station Chemistry Data

DOE Data Explorer

Quinn, Patricia

2008-04-04

Submicron and supermicron samples are analyzed by ion chromatography for Cl-, NO3-, SO4-2, Na+, NH4+, K+, Mg2+, and Ca+2. The analysis of MSA-, Br-, and oxalate has been added to some stations. Samples also are analyzed for total mass by gravimetric analysis at 55 +/- 5% RH.

Theoretical calculations of high-pressure phases of NiF2: An ab initio constant-pressure study

NASA Astrophysics Data System (ADS)

Kürkçü, Cihan; Merdan, Ziya; Öztürk, Hülya

2016-12-01

We have studied the structural properties of the antiferromagnetic NiF2 tetragonal structure with P42/ mnm symmetry using density functional theory (DFT) under rapid hydrostatic pressure up to 400 GPa. For the exchange correlation energy we used the local density approximation (LDA) of Ceperley and Alder (CA). Two phase transformations are successfully observed through the simulations. The structures of XF2-type compounds crystallize in rutile-type structure. NiF2 undergoes phase transformations from the tetragonal rutile-type structure with space group P42/ mnm to orthorhombic CaCl2-type structure with space group Pnnm and from this orthorhombic phase to monoclinic structure with space group C2/ m at 152 GPa and 360 GPa, respectively. These phase changes are also studied by total energy and enthalpy calculations. According to these calculations, we perdict these phase transformations at about 1.85 and 30 GPa.

Geochemical Composition of Surface Water in the Mineralized Lom Basin, East Cameroon: Natural and Anthropogenic Sources.

NASA Astrophysics Data System (ADS)

Mimba, M. E.; Ohba, T.; Nguemhe Fils, S. C.; Wirmvem, M. J.

2016-12-01

Thousands of people in East Cameroon depend on surface water for consumption and domestic purposes. The Lom basin, north of the region, is heavily mineralized especially in gold owing to its regional geological setting. Although research has been done regarding the rock type, age, formation history and reconnaissance gold surveys, surface water investigation in the area has received limited attention. Thus, this study appraises the first regional hydrogeochemical program for environmental assessment of the mineralized Lom basin. Fifty-two representative stream water samples were collected under base flow conditions and analysed for major cations (Ca2+, Mg2+, Na+, K+ ), major anions (HCO3-, F-, Cl-, NO2-, NO3-, Br-, PO43-, SO42- ) and stable isotopes (δD and δ18O). Calcium and HCO3- were the dominant ions. The chemical facies were CaHCO3 and NaHCO3 indicating surface water draining igneous/metamorphic rocks in hot and humid equatorial climate, resulting in the discordant dissolution of primary silicate minerals. From the isotopic evaluation, the stream water is of meteoric origin, shows negligible evaporation effect and has a common recharge source. The major ion geochemistry demonstrated the potential to discriminate between natural and anthropogenic origins. Distribution trends of Ca2+, Mg2+, Na+, K+, HCO3- and SO42- showed a correlation with the lithology and the occurrence of sulphide minerals associated with hydrothermal gold mineralization in the area. The distribution patterns of NO3- and Cl- reflect pollution from settlement. Overall, the chemistry of stream water in the Lom basin is mainly controlled by rock weathering compared to anthropogenic influence. Surface water quality is easily influenced by anthropogenic activities, and stream sediment collects effectively trace metals resulting from such activities. Hence, geochemical mapping incorporating stream water and stream sediment is of considerable value in future investigations within the Lom basin.

Chemical characterization of ambient aerosol collected during the southwest monsoon and intermonsoon seasons over the Arabian Sea: Anions and cations

NASA Astrophysics Data System (ADS)

Johansen, Anne M.; Siefert, Ronald L.; Hoffmann, Michael R.

1999-11-01

Ambient aerosol samples were collected over the northern Indian Ocean during two 1 month-long research cruises (German R/V Meteor) that took place during the intermonsoon (May) and SW monsoon (July/August) of 1995. A high volume and two small volume collectors were used to collect samples, which were subsequently analyzed for ferrous iron, 32 elements, and anions and cations. The present paper focuses on the bulk aerosol material, the ions, while utilizing some of the trace metal data that were presented in more detail in our previous paper [Siefert et al., 1999]. Data are analyzed and interpreted with the aid of principal component and multiple linear regression analyses. Intermonsoon samples were strongly influenced by continental material, both of crustal and anthropogenic origin. The crustal component (24.5±13% of the total suspended particulate mass (TSP), 6.0±4.4 μg m-3) contained 3.2% gypsum (CaSO4). While more than half of the TSP (21.2±9.6 μg m-3) during the SW monsoon was sea-salt-derived due to the strong winds prevailing during this season, only 1.7±1.1% (0.7±0.4 μg m-3) was found to be of crustal origin. Sulfate (SO42-) sources were determined and quantified with linear regression analyses utilizing specific tracers for the independent variables. Lead (Pb) was found to be a more reliable surrogate for anthropogenic SO42- compared to nitrate (NO3-) during the relatively polluted intermonsoon. Soluble calcium (Ca2+) served as the tracer for gypsum, and methane sulfonate (MSA) served as the tracer for biogenically derived SO42- during both seasons. On the basis of this analysis, 75% of the non-sea-salt sulfate (NSS-SO42-) (0.8±0.2 μg m-3, representing ˜2.4% of TSP) was found to be of biogenic origin during the SW monsoon with the remaining 25% of anthropogenic origin. During the intermonsoon, NSS-SO42- accounted for 2.1±1.2 μg m-3 (˜9.2% of TSP) and had a composition that was 65% anthropogenic, 21% biogenic, and 14% gypsum-derived. Linear regression analyses revealed that the bio-SO42-/MSA weight ratios appear to be consistent with the temperature dependence proposed by Hynes et al. [1986]. In this case the yield of SO42- increased relative to MSA with an increase in temperature. Three samples during the SW monsoon, near the coast of Oman, showed lower temperatures, due to coastal upwelling, than the rest of the samples; at 24°C the bio-SO42-/MSA weight ratio was 6.8±0.5. The remainder of the SW monsoon samples were collected at an average temperature of 27.2°C, for which the bio-SO42-/MSA weight ratio was 13.5±4.4. At an average temperature of 28.9°C during the intermonsoon, sampling gave a ratio of 17.7±4.8. These observations indicate a temperature dependence factor between 24° and 29°C of 2.2 (i.e., a 2.2 increase in the ratio of bio-SO42-/MSA with every degree temperature increase). Cl- deficits determined during both seasons appear to indicate that different mechanisms may govern the observed depletion of Cl- in each season.

42 CFR 84.207 - Bench tests; gas and vapor tests; minimum requirements; general.

Code of Federal Regulations, 2010 CFR

2010-10-01

... 64 3 50 50 Ammonia Equilibrated NH3 1000 32 4 50 50 Chlorine As received Cl2 500 64 3 5 35 Chlorine... 4 5 50 Sulfur dioxide As received SO2 500 64 3 5 30 Sulfur dioxide Equilibrated SO2 500 32 4 5 30 1... respiratory protection against more than one type of gas or vapor, as for use in ammonia and in chlorine, the...

42 CFR 84.207 - Bench tests; gas and vapor tests; minimum requirements; general.

Code of Federal Regulations, 2011 CFR

2011-10-01

... 64 3 50 50 Ammonia Equilibrated NH3 1000 32 4 50 50 Chlorine As received Cl2 500 64 3 5 35 Chlorine... 4 5 50 Sulfur dioxide As received SO2 500 64 3 5 30 Sulfur dioxide Equilibrated SO2 500 32 4 5 30 1... respiratory protection against more than one type of gas or vapor, as for use in ammonia and in chlorine, the...

Winter measurements of trace gas and aerosol composition at a rural site in southern ontario

NASA Astrophysics Data System (ADS)

Daum, P. H.; Kelly, T. J.; Tanner, R. L.; Tang, X.; Anlauf, K.; Bottenheim, J.; Brice, K. A.; Wiebe, H. A.

This paper reports the results of continuous measurements of concentrations of trace gas and aerosol species at Powassan, Ontario, a rural location in southern Ontario, from 20 January to 24 February 1984. The measurements included aerosol H + , NH 4+, Na +, Ca 2+ , NO 3-, SO 42- and Cl -, gaseous SO 2, NO, NO' y; ( = NO + NO2 + PAN + HNO3), HNO 3, PAN, and O 3. Average values of concentrations for key species during the project were: SO 2, 7.3 ppb; NO y, 7.5 ppb; HNO 3, 0.85 ppb; O 3, 33 ppb; NH 4+ 1.5 ppb; NO 3-, 0.4 ppb; and SO 42-, 0.9 ppb. Concentrations of primary pollutants (e.g. SO 2) were typically much higher, and concentrations of secondary species (e.g. SO 42-) typically lower, than observed at this location in summer. However, clear-air t- NO 3-/SO 42- ratios averaged 5-10 times higher in winter than in summer which suggests that HNO 3 is a more important source of atmospheric acidity, relative to SO 42- aerosol, in winter than in summer. Pollutant concentrations were highly variable; back trajectory calculations indicate that periods of high concentrations of both primary and secondary species were typically associated with air-mass back trajectories from the southern sectors while periods of low concentrations of secondary species were associated with back trajectories from the north. Comparison of these measurements with those at other locations suggests that concentrations at Powassan were characteristic of those prevailing over a much larger, possibly regional, area.

[The corrosion of pure iron in five different mediums].

PubMed

Xu, Li; Zhu, Shengfa; Huang, Nan; Li, Xinchang; Zhang, Yu

2009-08-01

The sectional test was adopted in this study to investigate the corrosion of pure iron in 0.15 mol/L NaCl solution, Ringer solution, PBS(-) solution, SBF solution and M199 cell culture medium at three different times. The result shows that different mediums have different corrosion effects on pure iron. The arrangement according to the medium's corrosion ability from the strongest to weakest is 0.15 mol/L NaCl solution (Ringer solution), PBS(-) solution, SBF solution and M199 cell culture medium. The results of scanning electron microscopy and energy dispersive X-ray spectrum analyses show that the addition of HPO4(2-), H2POC4-, Ca2+, Mg2+, SO4(2-) and the organic component can inhibit the corrosion to some degree.

Single particle characterization using a light scattering module coupled to a time-of-flight aerosol mass spectrometer

NASA Astrophysics Data System (ADS)

Cross, E. S.; Onasch, T. B.; Canagaratna, M.; Jayne, J. T.; Kimmel, J.; Yu, X.-Y.; Alexander, M. L.; Worsnop, D. R.; Davidovits, P.

2008-12-01

We present the first single particle results obtained using an Aerodyne time-of-flight aerosol mass spectrometer coupled with a light scattering module (LS-ToF-AMS). The instrument was deployed at the T1 ground site approximately 40 km northeast of the Mexico City Metropolitan Area (MCMA) as part of the MILAGRO field study in March of 2006. The instrument was operated as a standard AMS from 12-30 March, acquiring average chemical composition and size distributions for the ambient aerosol, and in single particle mode from 27-30 March. Over a 75-h sampling period, 12 853 single particle mass spectra were optically triggered, saved, and analyzed. The correlated optical and chemical detection allowed detailed examination of single particle collection and quantification within the LS-ToF-AMS. The single particle data enabled the mixing states of the ambient aerosol to be characterized within the context of the size-resolved ensemble chemical information. The particulate mixing states were examined as a function of sampling time and most of the particles were found to be internal mixtures containing many of the organic and inorganic species identified in the ensemble analysis. The single particle mass spectra were deconvolved, using techniques developed for ensemble AMS data analysis, into HOA, OOA, NH4NO3, (NH4)2SO4, and NH4Cl fractions. Average single particle mass and chemistry measurements are shown to be in agreement with ensemble MS and PTOF measurements. While a significant fraction of ambient particles were internal mixtures of varying degrees, single particle measurements of chemical composition allowed the identification of time periods during which the ambient ensemble was externally mixed. In some cases the chemical composition of the particles suggested a likely source. Throughout the full sampling period, the ambient ensemble was an external mixture of combustion-generated HOA particles from local sources (e.g. traffic), with number concentrations peaking during morning rush hour (04:00-08:00 LT) each day, and more processed particles of mixed composition from nonspecific sources. From 09:00-12:00 LT all particles within the ambient ensemble, including the locally produced HOA particles, became coated with NH4NO3 due to photochemical production of HNO3. The number concentration of externally mixed HOA particles remained low during daylight hours. Throughout the afternoon the OOA component dominated the organic fraction of the single particles, likely due to secondary organic aerosol formation and condensation. Single particle mass fractions of (NH4)2SO4 were lowest during the day and highest during the night. In one instance, gas-to-particle condensation of (NH4)2SO4 was observed on all measured particles within a strong SO2 plume arriving at T1 from the northwest. Particles with high NH4Cl mass fractions were identified during early morning periods. A limited number of particles (~5% of the total number) with mass spectral features characteristic of biomass burning were also identified.

Hydrothermal syntheses and anion-induced structural transformation of three Cadmium phosphonates

NASA Astrophysics Data System (ADS)

Hu, Han; Zhai, Fupeng; Liu, Xiaofeng; Ling, Yun; Chen, Zhenxia; Zhou, Yaming

2018-05-01

Three cadmium phosphonate coordinated polymers, namely as [Cd5(ptz)3(SO4)2(5H2O)]·6H2O (Cdptz-1), [Cd3(ptz)2(Cl)2(4H2O)]·2H2O (Cdptz-2) and [Cd4(ptz)2(SO4)(Cl)(OH)H2O]·H2O (Cdptz-3) have been hydrothermally synthesized using 4-(1,2,4-triazol-4-yl)phenylphosphonic acid (H2ptz) as ligand. Single crystal X-ray analyses revealed Cdptz-2 as layered structure and Cdptz-1,3 as pillar-layered structures with Cl- or SO42- as bridging anions. Due to the weak bonding between metal and anions, Cdptz-1 and 2 can reversibly convert into each other by simple immersing in the corresponding solution at room temperature. While the transformations between Cdptz-1,2 and Cdptz-3 can only happen under hydrothermal condition. The causes for the transformation involve the metal-ligand bond breaking/formation, replacement of anions and enhancement/decrement of the network dimensionality.

A thermodynamic model for the prediction of phase equilibria and speciation in the H 2O-CO 2-NaCl-CaCO 3-CaSO 4 system from 0 to 250 °C, 1 to 1000 bar with NaCl concentrations up to halite saturation

NASA Astrophysics Data System (ADS)

Li, Jun; Duan, Zhenhao

2011-08-01

A thermodynamic model is developed for the calculation of both phase and speciation equilibrium in the H 2O-CO 2-NaCl-CaCO 3-CaSO 4 system from 0 to 250 °C, and from 1 to 1000 bar with NaCl concentrations up to the saturation of halite. The vapor-liquid-solid (calcite, gypsum, anhydrite and halite) equilibrium together with the chemical equilibrium of H+,Na+,Ca, CaHCO3+,Ca(OH)+,OH-,Cl-, HCO3-,HSO4-,SO42-, CO32-,CO,CaCO and CaSO 4(aq) in the aqueous liquid phase as a function of temperature, pressure and salt concentrations can be calculated with accuracy close to the experimental results. Based on this model validated from experimental data, it can be seen that temperature, pressure and salinity all have significant effects on pH, alkalinity and speciations of aqueous solutions and on the solubility of calcite, halite, anhydrite and gypsum. The solubility of anhydrite and gypsum will decrease as temperature increases (e.g. the solubility will decrease by 90% from 360 K to 460 K). The increase of pressure may increase the solubility of sulphate minerals (e.g. gypsum solubility increases by about 20-40% from vapor pressure to 600 bar). Addition of NaCl to the solution may increase mineral solubility up to about 3 molality of NaCl, adding more NaCl beyond that may slightly decrease its solubility. Dissolved CO 2 in solution may decrease the solubility of minerals. The influence of dissolved calcite on the solubility of gypsum and anhydrite can be ignored, but dissolved gypsum or anhydrite has a big influence on the calcite solubility. Online calculation is made available on www.geochem-model.org/model.

Testing V-A in Top Decay at CDF at √s = 1.8 TeV

NASA Astrophysics Data System (ADS)

Kilminster, Ben

2004-02-01

The structure of the tbW vertex can be probed by measuring the polarization of the W in t → W + b → l + ν + b. The invariant mass of the the lepton and b quark measures the W decay angle which in turn allows a comparison with polarizations expected from a V-A and V+A tbW vertex. We measure the fraction by rate of Ws produced with a V+A coupling in lieu of the Standard Model V-A to be fV+A = -0.21-0.24+0.42 (stat) ± 0.21 (sys). We assign a limit of fV+A < 0.80 @ 95% CL. By combining this result with a complementary observable in the same data, we assign a limit of fV+A < 0.61 @ 95% CL. From this CDF Run I preliminary result, we find no evidence for a non-standard Model tbW vertex.

Solute and geothermal flux monitoring using electrical conductivity in the Madison, Firehole, and Gibbon Rivers, Yellowstone National Park

USGS Publications Warehouse

McCleskey, R. Blaine; Clor, Laura; Lowenstern, Jacob B.; Evans, William C.; Nordstrom, D. Kirk; Heasler, Henry; Huebner, Mark

2012-01-01

The thermal output from the Yellowstone magma chamber can be estimated from the Cl flux in the major rivers in Yellowstone National Park; and by utilizing continuous discharge and electrical conductivity measurements the Cl flux can be calculated. The relationship between electrical conductivity and concentrations of Cl and other geothermal solutes (Na, SO4, F, HCO3, SiO2, K, Li, B, and As) was quantified at monitoring sites along the Madison, Gibbon, and Firehole Rivers, which receive discharge from some of the largest and most active geothermal areas in Yellowstone. Except for some trace elements, most solutes behave conservatively and the ratios between geothermal solute concentrations are constant in the Madison, Gibbon, and Firehole Rivers. Hence, dissolved concentrations of Cl, Na, SO4, F, HCO3, SiO2, K, Li, Ca, B and As correlate well with conductivity (R2 > 0.9 for most solutes) and most exhibit linear trends. The 2011 flux for Cl, SO4, F and HCO3 determined using automated conductivity sensors and discharge data from nearby USGS gaging stations is in good agreement with those of previous years (1983–1994 and 1997–2008) at each of the monitoring sites. Continuous conductivity monitoring provides a cost- and labor-effective alternative to existing protocols whereby flux is estimated through manual collection of numerous water samples and subsequent chemical analysis. Electrical conductivity data also yield insights into a variety of topics of research interest at Yellowstone and elsewhere: (1) Geyser eruptions are easily identified and the solute flux quantified with conductivity data. (2) Short-term heavy rain events can produce conductivity anomalies due to dissolution of efflorescent salts that are temporarily trapped in and around geyser basins during low-flow periods. During a major rain event in October 2010, 180,000 kg of additional solute was measured in the Madison River. (3) The output of thermal water from the Gibbon River appears to have increased by about 0.2%/a in recent years, while the output of thermal water for the Firehole River shows a decrease of about 10% from 1983 to 2011. Confirmation of these trends will require continuing Cl flux monitoring over the coming decades.

[Composition and source of atmosphere aerosol water soluble ions over the East China Sea in winter].

PubMed

He, Yu-Hui; Yang, Gui-Peng; Zhang, Hong-Hai

2011-08-01

With the ion chromatographic method, the water-soluble ion concentrations of Cl(-), NO3(-), SO4(2-) , CH3SO3(-) (MSA), Na+, K+, NH4+, Mg2+ and Ca2+ in the atmospheric aerosol over the East China Sea in winter 2009 was determined and the sources of these ions was investigated through correlation analysis by SPSS (statistical package for social sciences) software. The results indicated that the concentrations of secondary ions in aerosol were the highest (non-sea-salt sulfates nss-SO4(2-), NO3(-), NH4+), accounting for 78.4% of total determining ions. The calculation results of equivalent concentration of anions and cations showed that the acid ions of aerosol were neutralized inadequately. The stoichiometry of NH4+ in different compounds showed that NH4HSO4 was the main binding form of NH4+ and SO4(2-) in the aerosol. The concentration of methanesulfonic acid (MSA) was low, and the average value was (0.0088 +/- 0.0037) microg x m(-3). According to calculation, the contribution of sea-salt sulfates was 4.5% to total sulfates, and that of biogenous sulfates was 1.4% to non-sea-salt sulfate (nss-SO4(2-)), showing that human input was the main source of sulfates in aerosol over the East China Sea. In addition, nss-SO4(2-)/NO3(-) in the aerosol was 1.08, reflecting that China's energy structure adjustment played an important role in recent years.

Ionic association and solvation in solutions of magnesium and nickel perchlorates in acetonitrile

NASA Astrophysics Data System (ADS)

Kalugin, O. N.; Agieienko, V. N.; Otroshko, N. A.; Moroz, V. V.

2009-02-01

The paper presents the conductometric data on solutions of Mg(ClO4)2 and Ni(ClO4)2 in acetonitrile over the temperature ranges 5-55°C for Mg(ClO4)2 and 25-75°C for Ni(ClO4)2. The extended Lee-Wheaton equation for unsymmetrical electrolytes was used to determine the limiting equivalent conductivities of the Mg2+, Ni2+, and ClO{4/-} ions and first-step ionic association constants with the formation of [KtClO4]+ ion pairs. Lower ionic association constants for Ni(ClO4)2 compared with Mg(ClO4)2 were a consequence of stronger non-Coulomb repulsion in the formation of [KtClO4]+ ion pairs because of the formation of a firmer solvation shell by the nickel compared with magnesium cation. The structure-dynamic parameter of ionic solvation was estimated. It was found that spatial-time correlations in the nearest environment of ions increased in the series ClO{4/-} > Mg2+ > Ni2+.

Iron(II) complexes of new hexadentate 1,1,1-tris-(iminomethyl)ethane podands, and their 7-methyl-1,3,5-triazaadamantane rearrangement products.

PubMed

Diener, Sara A; Santoro, Amedeo; Kilner, Colin A; Loughrey, Jonathan J; Halcrow, Malcolm A

2012-04-07

New iron(II) podand complexes have been prepared, by condensation of 2-(aminomethyl)-2-methyl-1,3-diaminopropane with 3 equiv of a heterocyclic aldehyde in the presence of hydrated Fe[BF(4)](2) or Fe[ClO(4)](2) as templates. The 2-(aminomethyl)-2-methyl-1,3-diaminopropane is prepared in situ by deprotonation of its trihydrochloride salt. The chloride must be removed from these reactions by precipitation with silver, to avoid the formation of the alternative 2,4,6-trisubstituted-7-methyl-1,3,5-triazaadamantane condensation products, or their FeCl(2) adducts. The crystal structures of two 2,4,6-tri(pyridyl)-7-methyl-1,3,5-triazaadamantane-containing species are presented, and contain two different geometric isomers of this tricyclic ring with three equatorial, or two equatorial and one axial, pyridyl substituents. Both structures feature strong C-HX (X = Cl or F) hydrogen bonding from the aminal C-H groups in the triazaadamantane ring. Five iron(II) podand complexes were successfully obtained, all of which contain low-spin iron centres.

Character of Mg(ClO4)2 Brines Under Mars Regolith Conditions

NASA Technical Reports Server (NTRS)

Zent, A. P.; Sizemore, H. G.; Rempel, A. W.

2013-01-01

Elsewhere, we report on our investigation of the initiation and growth of ice lenses under Mars like conditions. In that work, we assume that the soil-water-ice system is gas and solute free. We conclude that initiation of lens initiation - the unloading of particle-particle contacts by thermomolecular forces at a given soil horizon - may be a common process in the shallow Martian regolith, and that the dominant property controlling the rate of lens growth is the freezing point depression (Delta-T(sub f)) associated with the interfacial forces of the soil. Lens growth is thus favored in clay-sized soils over silt soils due to the greater Delta-T(sub f), but segregated ice was observed at the Phoenix site, where soils were predominantly siltsized.. Perchlorate salts were also observed at the Phoenix site, and will strongly affect some of the properties associated with potential ice lens growth, over and above increases to Delta-T(sub f),. Here, we investigate the nature of Mg(ClO4)2 brines under Mars-like conditions, with particular emphasis on those aspects that might influence the in situ segregation of residual liquids during phase change, potentially leading to the formation of subsurface excess ice. We also discuss cyclic variations in the water activity (a(sub w)) that might affect the habitability of solutions in the shallow regolith.

Sex Differences in Lopinavir (LPV) and Ritonavir (RTV) Pharmacokinetics (PKs) Among HIV-infected Females and Males

PubMed Central

Umeh, OC; Currier, JS; Park, JG; Cramer, Y; Hermes, AE; Fletcher, CV

2012-01-01

Objectives We compared the pharmacokinetics of lopinavir (LPV) and ritonavir (RTV) between female and males. Methods This two-step, multicenter, pharmacokinetic study enrolled HIV-infected adults on lopinavir/ritonavir (LPV/r) capsules (400/100mg BID) plus 1 or more NRTIs. All subjects underwent 12 hour pharmacokinetic sampling. The PK sampling was repeated in subjects receiving the LPV/r tablet formulation. Results Step 1 enrolled 37 women and 40 men; step 2 included 42 subjects from step 1 plus 35 new participants (39 women and 38 men). LPV pharmacokinetics in females and males were not significantly different with either formulation. Females had significantly higher median RTV AUC0–12h with both the soft gel capsule and tablet formulations (SGC:5395 vs. 4119 ng*hr/ml, p=0.026; tablet 5310 vs. 3941 ng*hr/ml, p=0.012), higher median Cmax (SGC:802 vs. 635 ng/mL, p=0.032; tablet: 773 vs. 570 ng/ml, p=0.006)) and lower median CL/F (SGC:18.54 vs. 24.31 L/hour, p=0.026; tablet: 18.83 vs. 25.37 L/hour, p=0.012). RTV CL/F was slower in females after weight adjustment with both formulations. Conclusion The pharmacokinetics of LPV in the SGC and tablet formulations are comparable in HIV infected subjects. Females had higher RTV AUC0–12h and lower CL/F with both formulations. The mechanism of the sex difference in RTV CL/F warrants elucidation. PMID:21233301

1,5-Diamido-9,10-anthraquinone, a Centrosymmetric Redox-Active Bridge with Two Coupled β-Ketiminato Chelate Functions: Symmetric and Asymmetric Diruthenium Complexes.

PubMed

Ansari, Mohd Asif; Mandal, Abhishek; Paretzki, Alexa; Beyer, Katharina; Fiedler, Jan; Kaim, Wolfgang; Lahiri, Goutam Kumar

2016-06-06

The dinuclear complexes {(μ-H2L)[Ru(bpy)2]2}(ClO4)2 ([3](ClO4)2), {(μ-H2L)[Ru(pap)2]2}(ClO4)2 ([4](ClO4)2), and the asymmetric [(bpy)2Ru(μ-H2L)Ru(pap)2](ClO4)2 ([5](ClO4)2) were synthesized via the mononuclear species [Ru(H3L)(bpy)2]ClO4 ([1]ClO4) and [Ru(H3L)(pap)2]ClO4 ([2]ClO4), where H4L is the centrosymmetric 1,5-diamino-9,10-anthraquinone, bpy is 2,2'-bipyridine, and pap is 2-phenylazopyridine. Electrochemistry of the structurally characterized [1]ClO4, [2]ClO4, [3](ClO4)2, [4](ClO4)2, and [5](ClO4)2 reveals multistep oxidation and reduction processes, which were analyzed by electron paramagnetic resonance (EPR) of paramagnetic intermediates and by UV-vis-NIR spectro-electrochemistry. With support by time-dependent density functional theory (DFT) calculations the redox processes could be assigned. Significant results include the dimetal/bridging ligand mixed spin distribution in 3(3+) versus largely bridge-centered spin in 4(3+)-a result of the presence of Ru(II)-stabilizig pap coligands. In addition to the metal/ligand alternative for electron transfer and spin location, the dinuclear systems allow for the observation of ligand/ligand and metal/metal site differentiation within the multistep redox series. DFT-supported EPR and NIR absorption spectroscopy of the latter case revealed class II mixed-valence behavior of the oxidized asymmetric system 5(3+) with about equal contributions from a radical bridge formulation. In comparison to the analogues with the deprotonated 1,4-diaminoanthraquinone isomer the centrosymmetric H2L(2-) bridge shows anodically shifted redox potentials and weaker electronic coupling between the chelate sites.

The Acute Toxicity of Major Ion Salts to Ceriodaphnia Dubia. Ii. Empirical Relationships in Binary Salt Mixtures

EPA Science Inventory

Many human activities increase concentrations of major geochemical ions (Na+, K+, Ca+2, Mg+2, Cl, SO42, and HCO3/CO32) in fresh water systems, and can thereby adversely affect aquatic life. Such effects involve several toxicants, multiple mechanisms of toxicity, various ion inte...

Chemical characterisation of meltwater draining from Gangotri Glacier, Garhwal Himalaya, India

NASA Astrophysics Data System (ADS)

Singh, Virendra Bahadur; Ramanathan, Al; Pottakkal, Jose George; Sharma, Parmanand; Linda, Anurag; Azam, Mohd Farooq; Chatterjee, C.

2012-06-01

A detailed analytical study of major cations (Ca2 + , Mg2 + , Na + , K + ) and anions (SO4^{2-}, HCO3-, Cl - , NO3-) of meltwater draining from Gangotri Glacier was carried out to understand major ion chemistry and to get an insight into geochemical weathering processes controlling hydrochemistry of the glacier. In the meltwater, the abundance order of cations and anions varied as follows: Ca2 + > Mg2 + > K + > Na + and SO4^{2-} > HCO3- > Cl - > NO3-, respectively. Calcium and magnesium are dominant cations while sulphate and bicarbonate are dominant anions. Weathering of rocks is the dominant mechanism controlling the hydrochemistry of drainage basin. The relative high contribution of (Ca+Mg) to the total cations (TZ + ), high (Ca+Mg)/(Na+K) ratio (2.63) and low (Na+K)/TZ + ratio (0.29) indicate the dominance of carbonate weathering as a major source for dissolved ions in the glacier meltwater. Sulphide oxidation and carbonation are the main proton supplying geochemical reactions controlling the rock weathering in the study area. Statistical analysis was done to identify various factors controlling the dissolved ionic strength of Gangotri Glacier meltwater.

Determination of mercury and inorganic ions in rainwater collected in two different regions of Queretaro, Mexico from 2009 to 2014

NASA Astrophysics Data System (ADS)

Garcia, R.; Peralta, O.; Alvarez, H.; Carrasco, M.

2016-12-01

The objective of this study was to evaluate the concentration of mercury (Hg) and inorganic ions in rainwater collected in Juriquilla and San Joaquin during the rainy seasons from 2009 to 2014. A total of 380 rainwater samples were collected and analyzed for pH, conductivity, the ions NO3-, SO42-, Cl-, Ca2+, Mg2+, Na+, K+, NH4+ and Hg. The ions were measured by Ion Chromatography (IC) and Hg was measured by Hydride Vapor Generator system coupled to an Atomic Absorption Spectrometer (HVG-AAS). Ammonium presented the higher volume-weighted-mean-concentration (VWMC), followed by SO42-, NO3-, Ca2+, Cl-, Na+, Mg2+ and K+. Sulfate showed a significant increasing trend emission in San Joaquin due to the burning cinnabar (HgS) for the extraction of mercury in artisanal ovens. The authors emphasized that the associations between Hg concentrations and local meteorological conditions, such as wind's speed and direction, play an important role in the study of the chemical of precipitation.

The Measurement of Sulfur Oxidation Products and Their Role in Homogeneous Nucleation

NASA Technical Reports Server (NTRS)

Eisele, F. L.

1997-01-01

The loss rate of H2SO4 vapor onto submicron particles was measured for three different particle substrates. The experimental technique involved direct flow tube measurements of H2SO4 decay rates onto a polydisperse aerosol using chemical ionization mass spectroscopic detection. The aerosols of this study were partially hydrated crystalline salts with diameters in the size range of 20 to 400 nm. The mass accommodation coefficients, a, were calculated from the first-order rate constants for H2SO4 loss to be 0.73 + 0.21 and 0.79 + 0.23 for loss onto (NH4)2SO4 and NaCl, respectively. Measurements of the loss rate of H2SO4 onto a NaCl aerosol coated with stearic acid resulted in lower mass accommodation coefficients with values of 0.31 and 0.19 for aerosol with high and low stearic acid coverage, respectively. The observed decrease in a on an aerosol with a hydrocarbon coating suggests that aerosol composition is a key factor in H2SO4 adsorption on to a particle surface.

Growth responses and ion accumulation in the halophytic legume Prosopis strombulifera are determined by Na2SO4 and NaCl.

PubMed

Reginato, M; Sosa, L; Llanes, A; Hampp, E; Vettorazzi, N; Reinoso, H; Luna, V

2014-01-01

Halophytes are potential gene sources for genetic manipulation of economically important crop species. This study addresses the physiological responses of a widespread halophyte, Prosopis strombulifera (Lam.) Benth to salinity. We hypothesised that increasing concentrations of the two major salts present in soils of central Argentina (Na2SO4, NaCl, or their iso-osmotic mixture) would produce distinct physiological responses. We used hydroponically grown P. strombulifera to test this hypothesis, analysing growth parameters, water relations, photosynthetic pigments, cations and anions. These plants showed a halophytic response to NaCl, but strong general inhibition of growth in response to iso-osmotic solutions containing Na2SO4. The explanation for the adaptive success of P. strombulifera in high NaCl conditions seems to be related to a delicate balance between Na(+) accumulation (and its use for osmotic adjustment) and efficient compartmentalisation in vacuoles, the ability of the whole plant to ensure sufficient K(+) supply by maintaining high K(+)/Na(+) discrimination, and maintenance of normal Ca(2+) levels in leaves. The three salt treatments had different effects on the accumulation of ions. Findings in bi-saline-treated plants were of particular interest, where most of the physiological parameters studied showed partial alleviation of SO4(2-)-induced toxicity by Cl(-). Thus, discussions on physiological responses to salinity could be further expanded in a way that more closely mimics natural salt environments. © 2013 German Botanical Society and The Royal Botanical Society of the Netherlands.

Synthetic and Spectroscopic Studies on N-(i,j-Disubstituted Phenyl)-4- Substituted Benzenesulphonamides, 4-X'C6H4SO2NH(i,j-X2C6H3), where X' = H, CH3, C2H5, F, Cl or Br; i, j = 2, 3; 2, 4; 2, 5; 2, 6 or 3, 4; and X = CH3 or Cl

NASA Astrophysics Data System (ADS)

Shetty, Mahesha; Gowda, B. Thimme

2005-02-01

Fifty four N-(i,j-disubstituted phenyl)-4-substituted benzenesulphonamides of the general formula 4-X'C6H4SO2NH(i,j-X2C6H3), where X' = H, CH3, C2H5, F, Cl or Br; i,j = 2,3; 2,4; 2,5; 2,6 or 3, 4; and X = CH3 or Cl, are prepared and characterized and their infrared, 1H and 13C NMR spectra in solution are studied. The N-H stretching vibrations νN-H absorb in the range 3305 - 3205 cm-1, while the asymmetric and symmetric SO2 vibrations vary in the ranges 1377 - 1307 cm-1 and 1184 - 1128 cm-1, respectively. The N-(i,j-disubstituted phenyl)-4-substituted benzenesulphonamides show C-S, S-N and C-N stretching vibrations in the ranges 844 - 800 cm-1, 945 - 891 cm-1 and 1309 - 1170 cm-1, respectively. The compounds do not exhibit particular trends in the variation of these frequencies on substitution either at ortho or meta positions with either a methyl group or Cl. The observed 1H and 13C chemical shifts of are assigned to protons and carbon atoms of the two benzene rings. Incremental shifts of the ring protons and carbon atoms due to -SO2NH(i,j-X2C6H3) groups in C6H5SO2NH(i,j-X2C6H3) and 4-X'C6H4SO2NH- groups in 4-X'C6H4SO2NH(C6H*) are computed and employed to calculate the chemical shifts of the ring protons and carbon atoms in the substituted compounds 4-X'C6H4SO2NH(i,j-X2C6H3). The different methods of calculation lead to almost the same values in most cases and agree well with the observed chemical shifts, indicating the validity of the principle of additivity of the substituent effects with chemical shifts in these compounds.

Chlorellestadite, Ca5(SiO4)1.5(SO4)1.5Cl, a new ellestadite- group mineral from the Shadil-Khokh volcano, South Ossetia

NASA Astrophysics Data System (ADS)

Środek, Dorota; Galuskina, Irina O.; Galuskin, Evgeny; Dulski, Mateusz; Książek, Maria; Kusz, Joachim; Gazeev, Viktor

2018-05-01

Chlorellestadite (IMA2017-013), ideally Ca5(SiO4)1.5(SO4)1.5Cl, the Cl-end member of the ellestadite group was discovered in a calcium-silicate xenolith in rhyodacite lava from the Shadil Khokh volcano, Greater Caucasus, South Ossetia. Chlorellestadite forms white, tinged with blue or green, elongate crystals up to 0.2-0.3 mm in length. Associated minerals include spurrite, larnite, chlormayenite, rondorfite, srebrodolskite, jasmundite and oldhamite. The empirical crystal chemical formula of the holotype specimen is Ca4.99Na0.01(SiO4)1.51(SO4)1.46(PO4)0.03(Cl0.61OH0.21F0.11)Σ0.93. Unit-cell parameters of chlorellestadite are: P63/m, a = 9.6002(2), c = 6.8692(2) Å, V = 548.27(3)Å3, Z = 2. Chlorellestadite has a Mohs hardness of 4-4.5 and a calculated density of 3.091 g/cm3. The cleavage is indistinct, and the mineral shows irregular fracture. The Raman spectrum of chlorellestadite is similar to the spectra of other ellestadite group minerals, with main bands located at 267 cm-1 (Ca-O vibrations), and between 471 and 630 cm-1 (SiO4 4- and SO4 2- bending vibrations) and 850-1150 cm-1 (SiO4 4- and SO4 2- stretching modes). Chlorellestadite forms in xenoliths of calcium-silicate composition when they are exposed to Cl-bearing volcanic exhalations at about 1000 °C under low pressure conditions.

The occurrence and hydrochemistry of fluoride and boron in carbonate aquifer system, central and western Estonia.

PubMed

Karro, Enn; Uppin, Marge

2013-05-01

Silurian-Ordovician (S-O) aquifer system is an important drinking water source of central and western Estonia. The fluoride and boron contents of groundwater in aquifer system vary considerably. The fluoride concentration in 60 collected groundwater samples ranged from 0.1 to 6.1 mg/l with a mean of 1.95 mg/l in the study area. Boron content in groundwater varied from 0.05 mg/l to 2.1 mg/l with a mean value of 0.66 mg/l. Considering the requirements of EU Directive 98/83/EC and the Estonian requirements for drinking water quality, the limit value for fluoride (1.5 mg/l) and for boron (1.0 mg/l) is exceeded in 47 and 28 % of wells, respectively. Groundwater with high fluoride and boron concentrations is found mainly in western Estonia and deeper portion of aquifer system, where groundwater chemical type is HCO3-Cl-Na-Mg-Ca, water is alkaline, and its Ca(2+) content is low. Groundwater of the study area is undersaturated with respect to fluorite and near to equilibrium phase with respect to calcite. The comparison of TDS versus Na/(Na + Ca) and Cl/(Cl + HCO3) points to the dominance of rock weathering as the main process, which promotes the availability of fluoride and boron in the groundwater. The geological sources of B in S-O aquifer system have not been studied so far, but the dissolution of fluorides from carbonate rocks (F = 100-400 mg/kg) and K-bentonites (F = 2,800-4,500 mg/kg) contributes to the formation of F-rich groundwater.

Assessment of groundwater quality in Kashipur Block, Purulia district, West Bengal

NASA Astrophysics Data System (ADS)

Kundu, Anindita; Nag, S. K.

2018-03-01

Hydrogeochemical investigation of groundwater resources of Kashipur Block, Purulia district, West Bengal has been carried out to assess the water quality for domestic and irrigation uses. Twenty groundwater samples were collected and analyzed for pH, electrical conductivity, total dissolved solids, hardness, major anions (CO3 2-, HCO3 -, Cl-, SO4 2-, F-) and cations (Ca2+, Mg2+, Fe2+, Na+, K+). Study results reveal that the groundwater of the area is mostly acidic in nature. The trend amongst average ionic concentrations of cations and anions is Mg2+ > Ca2+ > Na+ > Fe2+ > K+ and Cl- > HCO3 - > CO3 2- > SO4 2- > F- respectively during the post monsoon whereas the trend for cations and anions are Mg2+ > Ca2+> Na+ > K+ > Fe and Cl- > HCO3 - > SO4 2- > F- > CO3 - in pre monsoon session, respectively. To explore the ionic toxicity of the study area, the derived parameters like sodium adsorption ratio, soluble sodium percentage, residual sodium carbonate, magnesium adsorption ratio, Kelly's ratio and permeability index were calculated. The hydro geochemical data suggest that weathering of rock forming minerals along with secondary contributions from agricultural and anthropogenic sources are mainly controlling the groundwater composition of Kashipur Block, Purulia District. According to piper diagram, water samples of most of the area of the block are fresh water and in some areas sulphate rich throughout the year. All samples are distributed to central rock dominance category. Groundwater chemistry of this block is mainly controlled by the interaction existing between the litho units and the percolating water into the subsurface domain. However, the groundwater quality and suitability of this study area can be termed as good to moderate with a few exceptions which have been encountered on a local scale.

Impact of environmental conditions on aggregation kinetics of hematite and goethite nanoparticles

NASA Astrophysics Data System (ADS)

Xu, Chen-yang; Deng, Kai-ying; Li, Jiu-yu; Xu, Ren-kou

2015-10-01

Hematite and goethite nanoparticles were used as model minerals to investigate their aggregation kinetics under soil environmental conditions in the present study. The hydrodynamic diameters of hematite and goethite nanoparticles were 34.4 and 66.3 nm, respectively. The positive surface charges and zeta potential values for goethite were higher than for hematite. The effective diameter for goethite was much larger than for hematite due to anisotropic sticking of needle-shaped goethite during aggregation. Moreover, the critical coagulation concentration (CCC) values of nanoparticles in solutions of NaNO3, NaCl, NaF, and Na2SO4 were 79.2, 75.0, 7.8, and 0.5 mM for hematite and they were 54.7, 62.6, 5.5, and 0.2 mM for goethite, respectively. The disparity of anions in inducing hematite or goethite aggregation lay in the differences in interfacial interactions. NO3 - and Cl- could decrease the zeta potential and enhance aggregation mainly through increasing ionic strength and compressing electric double layers of hematite and goethite nanoparticles. F- and SO4 2- highly destabilized the suspensions of nanoparticles mainly through specific adsorption and then neutralizing the positive surface charges of nanoparticles. Specific adsorption of cations could increase positive surface charges and stabilize hematite and goethite nanoparticles. The Hamaker constants of hematite and goethite nanoparticles were calculated to be 2.87 × 10-20 and 2.29 × 10-20 J-1, respectively. The predicted CCC values based on DLVO theory were consistent well with the experimentally determined CCC values in NaNO3, NaCl, NaF, and Na2SO4 systems, which demonstrated that DLVO theory could successfully predict the aggregation kinetics even when specific adsorption of ions occurred.

Rotational spectrum of the nitrogen trifluoride-chlorine monofluoride complex and the inductive effect of groups R=CH 3, H, F on R 3N/ClF interactions

NASA Astrophysics Data System (ADS)

Waclawik, E. R.; Legon, A. C.; Holloway, J. H.

1998-10-01

Rotational constants B0, centrifugal distortion constants DJ and DJK, and nuclear quadrupole coupling constants χ aa( 14N) and χaa(Cl) were determined by pulsed-nozzle, Fourier transform microwave spectroscopy for the isotopomers F314N⋯ 35ClF and F314N⋯ 37ClF of a complex formed by nitrogen trifluoride and chlorine monofluoride. The distance r(N⋯Cl) and the intermolecular stretching force constant kσ for this symmetric-top species are compared with those of several axially symmetric complexes B⋯ClF in which a nitrogen atom of the base B interacts with ClF. In particular, it is shown that r(N⋯Cl) decreases along the series R 3N⋯ClF, where R=F, H or CH 3, while kσ increases dramatically.

A field study to evaluate runoff quality from green roofs.

PubMed

Vijayaraghavan, K; Joshi, U M; Balasubramanian, R

2012-03-15

Green (vegetated) roofs are emerging as practical strategies to improve the environmental quality of cities. However, the impact of green roofs on the storm water quality remains a topic of concern to city planners and environmental policy makers. This study investigated whether green roofs act as a source or a sink of various metals (Na, K, Ca, Mg, Al, Fe, Cu, Cd, Pb, Zn, Mn, Cr, Ni, Li and Co), inorganic anions (NO3-, NO2-, PO4(3-), SO4(2-), Cl-, F- and Br-) and cation (NH4+). A series of green roof assemblies were constructed. Four different real rain events and several artificial rain events were considered for the study. Results showed that concentrations of most of the chemical components in runoff were highest during the beginning of rain events and subsided in the subsequent rain events. Some of the important components present in the runoff include Na, K, Ca, Mg, Li, Fe, Al, Cu, NO3-, PO4(3-) and SO4(2-). However, the concentration of these chemical components in the roof runoff strongly depends on the nature of substrates used in the green roof and the volume of rain. Based on the USEPA standards for freshwater quality, we conclude that the green roof used in this study is reasonably effective except that the runoff contains significant amounts of NO3- and PO4(3-). Copyright © 2011 Elsevier Ltd. All rights reserved.

Characterization of brines and evaporites of Lake Katwe, Uganda

NASA Astrophysics Data System (ADS)

Kasedde, Hillary; Kirabira, John Baptist; Bäbler, Matthäus U.; Tilliander, Anders; Jonsson, Stefan

2014-03-01

Lake Katwe brines and evaporites were investigated to determine their chemical, mineralogical and morphological composition. 30 brine samples and 3 solid salt samples (evaporites) were collected from different locations of the lake deposit. Several analytical techniques were used to determine the chemical composition of the samples including Inductively Coupled Plasma-Atomic Emission Spectrometry (ICP-AES), Inductively Coupled Plasma-Sector Field Mass Spectrometry (ICP-SFMS), ion chromatography, and potentiometric titration. The mineralogical composition and morphology of the evaporites was determined using X-ray diffraction (XRD) and scanning electron microscopy (SEM), respectively. Physical parameters of the lake brines such as density, electrical conductivity, pH, and salinity were also studied. The results show that the lake brines are highly alkaline and rich in Na+, Cl-, CO32-, SO42-, and HCO3- with lesser amounts of K+, Mg2+, Ca2+, Br-, and F- ions. The brines show an intermediate transition between Na-Cl and Na-HCO3 water types. Among the trace metals, the lake brines were found to be enriched in B, I, Sr, Fe, Mo, Ba, and Mn. The solid salts are composed of halite mixed with other salts such as hanksite, burkeite and trona. It was also observed that the composition of the salts varies considerably even within the same grades.

Influence of hydrogen bond accepting ability of anions on the adsorption performance of ionic liquid surface molecularly imprinted polymers.

PubMed

Zhu, Guifen; Gao, Xia; Wang, Xiaolong; Wang, Jianji; Fan, Jing

2018-01-12

To illuminate the influence mechanism of anionic structure of ionic liquids (ILs) on the adsorption performance of surface molecularly imprinted polymers (MIPs), in this work, six newly designed MIPs were prepared on the surface of amino-poly(styrene-divinylbenzene) particles by using imidazolium ILs with the same cation [C 4 mim] + but different anions (Cl, CH 3 SO 3 , PF 6 , BF 4 , C 4 F 7 O 2 , C 4 F 9 SO 3 ) as template molecules, methacrylic acid as functional monomer, and ethylene dimethacrylate as cross-linker. The resulting MIP materials were characterized by IR and SEM, and the influence of hydrogen bond accepting ability of anions on the adsorption performance of the MIPs for the ILs was investigated in acetonitrile. It was found that adsorption capacity of the MIPs towards the ILs decreased in the order MIP [C4mim][Cl]  > MIP [C4mim][C4F7O2]  ≥ MIP [C4mim][BF4] and MIP [C4mim][CH3SO3]  > MIP [C4mim][C4F9SO3]  > MIP [C4mim][PF6] , which is in good agreement with the ability of anions of the ILs to form hydrogen bonds. Ultraviolet, 1 H-NMR and 35 Cl-NMR spectroscopy was then used to study the interactions of anions of the ILs with the functional monomer. It was found that the hydrogen bond interaction between anions of the ILs and acidic proton of the functional monomer was the main driving force for the high adsorption selectivity of the imprinted polymers, and the stronger hydrogen bond interaction indicates higher binding capacity and higher selectivity of the polymers towards the ILs. It was also verified that the ILs with stronger hydrogen bond accepting ability of anions could be selectively extracted by the corresponding IL-MIPs. These results may provide new insight into the recognition mechanism of MIPs for ILs, and are also useful for the rational design of this new class of imprinting materials. Copyright © 2017 Elsevier B.V. All rights reserved.

Episodic acidification of a coastal plain stream in Virginia

USGS Publications Warehouse

O'Brien, A. K.; Eshleman, K.N.

1996-01-01

This study investigates the episodic acidification of Reedy Creek, a wetland-influenced coastal plain stream near Richmond, Virginia. Primary objectives of the study were to quantify the episodic variability of acid- base chemistry in Reedy Creek, to examine the seasonal variability in episodic response and to explain the hydrological and geochemical factors that contribute to episodic acidification. Chemical response was similar in each of the seven storms examined, however, the ranges in concentrations observed were commonly greater in summer/fall storms than in winter/spring storms. An increase in SO4/2- concentration with discharge was observed during all storms and peak concentration occurred at or near peak flow. Small increases in Mg2+, Ca2+, K+ concentrations and dissolved organic carbon (DOC) were observed during most storms. At the same time, ANC, Na+ and Cl- concentrations usually decreased with increasing discharge. In summer/fall storms, the absolute increase in SO4/2- concentration was one-third to 15 times the increase observed in winter/spring storms; the decrease in ANC during summer/fall storms was usually within the range of the decrease observed in winter/spring storms. In contrast, the decrease in Na+ and Cl- concentrations during winter/spring storms was much greater than that observed during summer/fall storms. Data show that while base flow anion deficit was higher in summer/fall than in winter/spring, anion deficit decreased during most summer/fall storms. In contrast, base flow anion deficit was lower in spring and winter, but increased during winter/spring storms. Increased SO4/2- concentration was the main cause of episodic acidification during storms at Reedy Creek, but increased anion deficit indicates organic acids may contribute to episodic acidification during winter/spring storms. Changes in SO4/2- concentration coincident with the hydrograph rise indicate quick routing of water through the watershed. Saturation overland flow appears to be the likely mechanism by which solutes are transported to the stream during storm flow.

Geochemical and hydrological constraints on the deep subsurface terrestrial ecosystems

NASA Astrophysics Data System (ADS)

Silver, B.; Onstott, T.; Hinton, S.; King, H.; Sherwood Lollar, B.; Lippmann-Pipke, J.

2008-12-01

Pore water and fluid inclusion compositions were determined on pristine rock cores from the Ventersdorp and Witwatersrand Supergroup by leaching experiments in order to constrain the origin of the chemical nutrients in the fracture water of the Witwatersrand basin. Subsequent chemical extractions including fusion analyses of the rock cores constrained the redox relevant mineral abundances of these strata. The resulting data set was used in mixing models with meteoric water from the overlying Transvaal dolomitic aquifer. The model also incorporated dissolved gas concentrations, radiogenic and radiolytic reactions, mineral dissolution and oxidation reactions, mineral equilibria and microbial redox reactions at rates that were varied over the course of one million years. Results revealed pore water and fluid inclusion leachates rich in Na, Ca, Si, Cl, acetate, SO42- and formate, with the resulting inferred fluid inclusion concentrations exceeding pore water concentrations, which in turn exceeded fracture water concentrations in nearly all observed elements. The model successfully simulated dissolved He and Cl concentrations with a mixing rate of 1e-5 L/year, corresponding to a fracture water velocity of 1 mm/year. Upon examining the viability of Fe reduction, SO42- reduction, acetogenesis, methanogenesis, NO3- reduction, anaerobic NH3 oxidation and HS- oxidation, model results indicate that SO42-reduction is the dominant metabolic process at high and low salinities and can be sustained at rates of 1.2e-12 M SO42- s-1 for biomasses of 2e8 cells/mL water. Final electron acceptor and donor concentrations and Free Energy Flux (FEF) calculations suggest that acetogenesis is not the source of acetate, nor is the syntrophic degradation of light hydrocarbons the source of the observed carboxylic acids. Ambient concentrations are instead likely the result of production via the thermally activated step-wise decarboxylation of abiogenic hydrocarbons and consumption by carboxylic acid utilizing metabolic reactions consistent with phylogenetic data showing few acetogens, no hydrocarbon oxidizers and a significant abundance of acetoclastic methanogens.

Appraisal of long term groundwater quality of peninsular India using water quality index and fractal dimension

NASA Astrophysics Data System (ADS)

Rawat, Kishan Singh; Singh, Sudhir Kumar; Jacintha, T. German Amali; Nemčić-Jurec, Jasna; Tripathi, Vinod Kumar

2017-12-01

A review has been made to understand the hydrogeochemical behaviour of groundwater through statistical analysis of long term water quality data (year 2005-2013). Water Quality Index ( WQI), descriptive statistics, Hurst exponent, fractal dimension and predictability index were estimated for each water parameter. WQI results showed that majority of samples fall in moderate category during 2005-2013, but monitoring site four falls under severe category (water unfit for domestic use). Brownian time series behaviour (a true random walk nature) exists between calcium (Ca^{2+}) and electric conductivity (EC); magnesium (Mg^{2+}) with EC; sodium (Na+) with EC; sulphate (SO4^{2-}) with EC; total dissolved solids (TDS) with chloride (Cl-) during pre- (2005-2013) and post- (2006-2013) monsoon season. These parameters have a closer value of Hurst exponent ( H) with Brownian time series behaviour condition (H=0.5). The result of times series analysis of water quality data shows a persistent behaviour (a positive autocorrelation) that has played a role between Cl- and Mg^{2+}, Cl- and Ca^{2+}, TDS and Na+, TDS and SO4^{2-}, TDS and Ca^{2+} in pre- and post-monsoon time series because of the higher value of H (>1). Whereas an anti-persistent behaviour (or negative autocorrelation) was found between Cl- and EC, TDS and EC during pre- and post-monsoon due to low value of H. The work outline shows that the groundwater of few areas needs treatment before direct consumption, and it also needs to be protected from contamination.

Studies on the movements of ionic selectivity, compatible solutes, and intracellular ions caused in the leaves of spinach (Spinacia oleracea L.) plants cultured in a nutrient solution with seawater.

PubMed

Sun, Jin; Jia, Yongxia; Guo, Shirong; Chen, Lifang

2010-01-01

Analyses of ionic selectivity, compatible solutes, and intracellular ions in the leaves of spinach (Spinacia oleracea L.) plants cultured in the Hoagland's nutrient solution with or.without seawater (40%) were carried out using two cultivars--the Helan No.3 (seawater tolerant) and the Yuanye (seawater sensitive). When both cultivars were subjected to seawater stress, the leaves of the Helan No. 3 spinach preferred potassium (K+), calcium (Ca2+), magnesium (Mg2+), and sulfate (SO4(2-)) over sodium (Na+) and chlorine (Cl-) to keep high ratios of K/Na, Mg/Na, Ca/Na, and SO4(2-)/Cl- compared with the Yanye spinach. Moreover, those of the Helan No. 3 spinach under the seawater stress showed high efficiency of accumulation of compatible solutes (sugars and proline), low degradation of proteins, and suppression of free amino acids. However, the activities of plasma membrane H+ -ATPase and tonoplast H+ -ATPase in the leaves of spinach with the stress were enhanced. Taken together, the Helan No. 3 spinach under the seawater stress seems to acquire a high tolerance to the seawater salinity by inducing a high ion uptake, low concentration of Na+ and Cl-, efficient accumulation of compatible solutes, low decomposition of proteins, and suppression of free amino acids in the leaves.

Suppression of chlorinated aromatics by nitrogen and sulphur inhibitors in iron ore sintering.

PubMed

Zhang, Yadi; Buekens, Alfons; Liu, Lina; Zhang, Yibo; Zeng, Xiaolan; Sun, Yifei

2016-07-01

Dioxins generated by iron and steel industry account for the majority of industrial dioxins emissions. This study compares the performance of different additives (including calcium sulphate dehydrate CaSO4·2H2O; calcium polysulphide CaSx; ammonium sulphate (NH4)2SO4; 4-methylthiosemicarbazide H3C-SC(NH)2NH2 and thiourea H2NCSNH2) as suppressant of chlorinated aromatics in iron ore sintering. The formation of chlorobenzenes (CBz) and polychlorinated biphenyls (PCBs), used as surrogates for dioxins, was suppressed significantly in the present of various inhibitors (1 wt%) except for CaSO4·2H2O. Moreover, a larger molar ratio of (S + N)/Cl leads to a higher suppression efficiency, so that the inhibition capacity of (NH4)2SO4 on both CBz and PCBs was weaker than H2NCSNH2. The generation of dioxin-like PCBs (Co- or dl-PCB) was also analysed. Copyright © 2016 Elsevier Ltd. All rights reserved.

One year online measurements of water-soluble ions at the industrially polluted town of Nanjing, China: Sources, seasonal and diurnal variations.

PubMed

Wang, Honglei; An, Junlin; Cheng, Mengtian; Shen, Lijuan; Zhu, Bin; Li, Yi; Wang, Yuesi; Duan, Qing; Sullivan, Amy; Xia, Li

2016-04-01

Half-hourly mass concentrations water-soluble ions (WSIs) and PM2.5 were measured online a Rapid Collector of Fine Particles and Ion Chromatography system (RCFP-IC) and FH62C14 Continuous Particulate Monitor in Nanjing from October 18, 2013 to November 17, 2014. The WSIs concentration ranged from 7.07 to 333.42 μg m(-3) with an annual mean of 76.32 μg m(-3). The WSIs ranked in the order of SO4(2-) > NH4(+) > NO3(-) > Cl(-) > NO2(-) > K(+) > Ca(2+) > Na(+) > Mg(2+). The PM2.5 concentration ranged from 4.00 to 400 μg m(-3) with an annual mean of 83.58 μg m(-3). The concentrations of WSIs varied in the order of winter (115.77 μg m(-3)) > spring (76.10 μg m(-3)) > autumn (63.72 μg m(-3)) > summer (59.75 μg m(-3)), with the highest level in January (123.99 μg m(-3)) and lowest level in August (43.73 μg m(-3)). Different WSIs had distinct diurnal variations. The source analysis of the WSIs in the PCA/APCS mode illustrated that the sources consisted of secondary aerosol, coal combustion, mineral dust, biomass burning, traffic emissions and sea salt. In addition, there were seasonal variations amongst the various sources. The haze formation mechanism was different in summer and winter. The winter was dominated by NH4NO3 (18.56%), (NH4)2SO4 (28.63%), NH4(+) (11.27%), SO4(2-) (18.35%) and NO3(-) (13.13%), and by NH3 (25.93%), (NH4)2SO4 (13.37%), SO4(2-) (15.74%) and NO3(-) (9.97%) in summer. Consequently, the proportions of HCl, HNO3, NH4(+), SO4(2-) and NO3(-) were much larger during haze episodes in winter, while it was dominated by NH4NO3, NH4(+), (NH4)2SO4, SO4(2-) and NO3(-) during summer haze episodes. Copyright © 2016 Elsevier Ltd. All rights reserved.

Time-related variation of volatile contents of Western Ghats volcanic formations, Deccan, India

NASA Astrophysics Data System (ADS)

Marzoli, Andrea; Callegaro, Sara; Baker, Don R.; De Min, Angelo; Renne, Paul R.

2016-04-01

Deccan volcanism in India covered more than 1 million square km and reached a maximum thickness of about 3 km, as presently preserved in the Western Ghats volcanic lava piles. Volcanic activity started at about 66.4 Ma (Jawhar formation) and ended at about 65.5 Ma (Mahabaleshwar unit; Renne et al., 2015). Deccan volcanism straddled the Cretaceous-Paleogene boundary (ca. 66.0 Ma) and possibly contributed to the end-Cretaceous mass extinction event through emission of gases such as SO2, CO2, Cl, F that may have triggered global climate changes. Severe pollution by volcanic gases is supported by the high S and Cl contents (up to 1400 and up to 900 ppm, respectively; Self et al., 2008) measured in a few olivine- and plagioclase-hosted melt inclusions from the Jawhar, Neral, and Thakurvadi Formations (early lava flows, ca. 66.3-66.4 ± 0.1 Ma; Renne et al., 2015) and by magmatic S contents (up to 1800 ppm; Callegaro et al., 2014) calculated from S measurements in clinopyroxenes from the Mahabaleshwar unit (ca. 65.5 ± 0.1; Schoene et al., 2015). Here, we present new analyses of S, Cl, and F, obtained by ion-probe and synchrotron light micro-fluorescence analyses on clinopyroxenes and plagioclase phenocrysts from ?al? lava flow units of the Western Ghats. The volatile contents of the host magmas have been calculated from recently published clinopyroxene/basalt partition coefficients. These new data will describe the time-related variation of volatile elements hosted and eventually emitted by Deccan lavas and shed light on their environmental impact. References: Callegaro S. et al. (2014). Geology 42, 895-898. Renne P.R. et al. (2015). Science 350, 76-78. Schoene B. et al. (2015). Science 347, 192-184. Self S. et al. (2008). Science 319, 1654-1657.

Prime Contract Awards Alphabetically by Contractor, by State or Country, and Place. Part 16. (Robert E. Rivera Const. Co.-Singapore Aircraft Industries)

DTIC Science & Technology

1989-01-01

E 0 , f- ~ - el 2.0 >f ~~.- 0 V?0 ) *-’Q) Q: Z 10 1Z o Oc 4V cc o S7 - L E) o 0 0 a) .97 -L ) U c c r_ In CL M) E2 -4 CL W) > V a) C. L- L. - C V...4 -140)(m0)) 00000000000000000 ))))))))))))))) 11 a)1 W-4N,41 I N -IN m Go00 0000* 400000000000000000000000O0000000 II El W-40 1102 42 02222Z...34 :: mmmmmmimmcl3mmmmmmmm m commmmm U-4 zzzzzzzzzzzzzzzzz z zzzzzz M-4c,)O:: in m in m m o 0 0 In In In In In In In on In In U") In In en CY) U) In W W) 9) U"I M-4" " C14

The acute toxicity of major ion salts to Ceriodaphnia dubia: I. Influence of background water chemistry

EPA Science Inventory

The ions Na+, K+, Ca2+, Mg2+, Cl-, SO42-, and HCO3-/CO32- (referred to as “major ions”) are present in all fresh waters and are physiologically required by aquatic organisms, but can be increased to harmful levels by a variety of anthropogenic activities that speed ge...

40 CFR Appendix A to Subpart A of... - Class I Controlled Substances

Code of Federal Regulations, 2010 CFR

2010-07-01

...) 1.0 C2 F3 Cl3-Trichlorotrifluoroethane (CFC-113) 0.8 C2 F4 Cl2-Dichlorotetrafluoroethane (CFC-114) 1... F4 Br2-Dibromotetrafluoroethane (Halon-2402) 6.0 All isomers of the above chemicals C. Group III: CF3...) 1.0 C3 F2 Cl6-(CFC-212) 1.0 C3 F3 Cl5-(CFC-213) 1.0 C3 F4 Cl4-(CFC-214) 1.0 C3 F5 Cl3-(CFC-215) 1.0...

Field measurements of dry deposition to spruce foliage and petri dishes in the Black Forest, F.R.G.

USGS Publications Warehouse

Shanley, J.B.

1989-01-01

Dry deposition fluxes Ca2+, Mg2+, K+, Mn2+, Pb2+ and SO42- to spruce foliage and petri dishes were measured in two high-elevation sites (>900 m) in the southern Black Forest, F.R.G., during 12 periods (2-7 days, each) from mid-September to mid-November, 1983, In situ extraction of deposited material from small spruce branches allowed repeated use of the same foliar collecting surfaces for a direct comparison of deposition between periods. Fluxes were corrected for leaching of internally cycled constituents using factors determined from serial extraction experiments. The ratio of flux to petri dishes vs foliage (P/F) was >1.0 for Ca2+, Pb2+ and SO42-, and somewhat 900 m) in the southern Black Forest, F.R.G., during 12 periods (2-7 days, each) from mid-September to mid-November, 1983. The ratio of flux to petri dishes vs foliage (P/F) was >1.0 for Ca2+, Pb2+, and SO42-, and somewhat <1.0 but more constant for Mg2+. Temporal variations in dry deposition fluxes at an exposed site near the industrialized Rhine Valley correlated with variations in total air particulate concentrations at a nearby air quality station. Deposition rates were comparable in magnitude but different in temporal pattern at a remote site in the Black Forest interior. Fluxes at each site reached a minimum during the period of 4-9 November when a regional air inversion confined pollutants to the Rhine Valley below the study sites. High fluxes accompanied the inversion break-up.

Heavy haze episodes in Beijing during January 2013: Inorganic ion chemistry and source analysis using highly time-resolved measurements from an urban site.

PubMed

Han, Bin; Zhang, Rui; Yang, Wen; Bai, Zhipeng; Ma, Zhiqiang; Zhang, Wenjie

2016-02-15

The heavy air pollution that occurred in Beijing in January of 2013 attracted intense attention around the world. During this period, we conducted highly time-resolved measurements of inorganic ions associated with PM2.5 at an urban site of Beijing, and investigated ion chemistry and potential sources. Hourly concentrations of Cl(-), NO3(-), SO4(2-), Na(+), NH4(+), K(+), Mg(2+), and Ca(2+) were measured. Peak concentrations of SO4(2-) and NO3(-) were observed on the 10th-15th, 21st-24th, and the 26th-30th during this monitoring campaign. The percentages of SO4(2-) and NH4(+) in total ion concentration increased with the enhancement of PM2.5 concentrations, indicating that high concentrations of SO4(2-) and NH4(+) may play important roles in the formation of haze episodes. The ratio of [NO3(-)]/[SO4(2-)] was calculated, revealing that the sources of SO4(2-) would contribute more to the formation of PM2.5 than mobile sources. Diurnal variations of SO4(2-), NO3(-), NH4(+) (SNA) exhibited a similar pattern, with high concentrations at night and low levels during the day, revealing that meteorological conditions, such as mixing layer height, relative humidity, were likely to be responsible for high levels of SNA at night. The roles of meteorological conditions were further discussed in the formation of secondary inorganic ions. Relative humidity and temperature played key roles and exhibited positive correlations with secondary inorganic ions. An aerosol inorganics simulation model showed that SNA existed mainly in the aqueous phase during the sampling period. Furthermore, potential sources were identified by applying positive matrix factorization model. Secondary nitrate, secondary sulfate, coal combustion and biomass burning, as well as fugitive dust, were considered to be major contributors to total ions. Copyright © 2015. Published by Elsevier B.V.

Sulfate reduction and other sedimentary biogeochemistry in a northern New England salt marsh

NASA Technical Reports Server (NTRS)

Hines, Mark E.; Knollmeyer, Stephen L.; Tugel, Joyce B.

1992-01-01

Sulfate reduction rates, dissolved iron and sulfide concentrations, and titration alkalinity were measured in salt marsh soils along a transect that included areas inhabited by both the tall and short forms of Spartina alterniflora and by Spartina patens. Pore waters were collected with in situ 'sippers' to acquire temporal data from the same location without disturbing plant roots. During 1984, data collected at weekly intervals showed rapid temporal changes in belowground biogeochemical processes that coincided with changes in S. alterniflora physiology. Rates of SO4(-2) reduction increased fivefold (to greater than 2.5 micromol ml(sup -1)d(sup -1)) when plants began elongating aboveground yet decreased fourfold upon plant flowering. This rapid increase in rates of SO4(-2) reduction must have been fueled by dissolved organic matter released from roots only during active growth. Once plants flowered, the supply of oxidants to the soil decreased and sulfide and alkalinity concentrations increased despite decreases in SO4(-2) reduction and increases in SO4(-2):Cl(-) ratios. Sulfide concentrations were highest in soils inhabited by tallest plants. During 1985, S. alterniflora became infested with fly larvae (Chaetopsis apicalis John) and aboveground growth ceased in late June. This cessation was accompanied by decreased rates of SO4(-2) reduction similar to those noted during the previous year when flowering occurred. After the fly infestation, the pore-water chemical profiles of these soils resembled profiles of soils inhabited by the short form of S. alterniflora. The SO4(-2) reduction rates in S. patens soils are the first reported. Rates were similar to those in S. alterniflora except that they did not increase greatly when S. patens was elongating. Tidal and rainfall events produced desiccation-saturation cycles that altered redox conditions in the S. patens soils, resulting in rapid changes in the dissolution and precipitation of iron and in the magnitude and spatial distribution of SO4(-2) reduction.

Densities and apparent molar volumes of atmospherically important electrolyte solutions. 1. The solutes H2SO4, HNO3, HCl, Na2SO4, NaNO3, NaCl, (NH4)2SO4, NH4NO3, and NH4Cl from 0 to 50 °C, including extrapolations to very low temperature and to the pure liquid state, and NaHSO4, NaOH, and NH3 at 25 °C.

PubMed

Clegg, S L; Wexler, A S

2011-04-21

Calculations of the size and density of atmospheric aerosols are complicated by the fact that they can exist at concentrations highly supersaturated with respect to dissolved salts and supercooled with respect to ice. Densities and apparent molar volumes of solutes in aqueous solutions containing the solutes H(2)SO(4), HNO(3), HCl, Na(2)SO(4), NaNO(3), NaCl, (NH(4))(2)SO(4), NH(4)NO(3), and NH(4)Cl have been critically evaluated and represented using fitted equations from 0 to 50 °C or greater and from infinite dilution to concentrations saturated or supersaturated with respect to the dissolved salts. Using extrapolated densities of high-temperature solutions and melts, the relationship between density and concentration is extended to the hypothetical pure liquid solutes. Above a given reference concentration of a few mol kg(-1), it is observed that density increases almost linearly with decreasing temperature, and comparisons with available data below 0 °C suggest that the fitted equations for density can be extrapolated to very low temperatures. As concentration is decreased below the reference concentration, the variation of density with temperature tends to that of water (which decreases as temperature is reduced below 3.98 °C). In this region below the reference concentration, and below 0 °C, densities are calculated using extrapolated apparent molar volumes which are constrained to agree at the reference concentrations with an equation for the directly fitted density. Calculated volume properties agree well with available data at low temperatures, for both concentrated and dilute solutions. Comparisons are made with literature data for temperatures of maximum density. Apparent molar volumes at infinite dilution are consistent, on a single ion basis, to better than ±0.1 cm(3) mol(-1) from 0 to 50 °C. Volume properties of aqueous NaHSO(4), NaOH, and NH(3) have also been evaluated, at 25 °C only. In part 2 of this work (ref 1 ) an ion interaction (Pitzer) model has been used to calculate apparent molar volumes of H(2)SO(4) in 0-3 mol kg(-1) aqueous solutions of the pure acid and to represent directly the effect of the HSO(4)(-) ↔ H(+) + SO(4)(2-) reaction. The results are incorporated into the treatment of aqueous H(2)SO(4) density described here. Densities and apparent molar volumes from -20 to 50 °C, and from 0 to 100 wt % of solute, are tabulated for the electrolytes listed in the title and have also been incorporated into the extended aerosol inorganics model (E-AIM, http://www.aim.env.uea.ac.uk/aim/aim.php) together with densities of the solid salts and hydrates.

Water-soluble part of the aerosol in the dust storm season—evidence of the mixing between mineral and pollution aerosols

NASA Astrophysics Data System (ADS)

Wang, Ying; Zhuang, Guoshun; Sun, Yele; An, Zhisheng

Six dust episodes were observed in Beijing in 2002. Both TSP (Total Suspended Particulate, particle size smaller than 100 μm) and PM 2.5 (particle size smaller than 2.5 μm) aerosol samples in these episodes were collected and their characteristics of water-soluble part were elaborated in demonstrating the mixing of mineral aerosol with pollution aerosol in the long-range transport of Asia aerosols with various sources and different paths. The dust storm peaked on 20 March, in which the highest concentrations of TSP and PM 2.5 were 10.9 and 1.4 mg m -3, respectively. The mass fraction of water-soluble part generally decreased with the increase of dust intensity. SO 42- contributed 38-70% to the total anions and Ca 2+ contributed 37-80% to the total cations, indicating that SO 42- and Ca 2+ were the most abundant anion and cation, respectively. The major ions of the water-soluble parts could be classified into three groups, i.e., the crust ions (Ca 2+, Na +, and Mg 2+), the pollution-crust ions (SO 42-, Cl -, and K +), and the pollution ions (NO 3-, NH 4+, NO 2-, and F -). Crust ions and pollution ions were the main ion fractions in super dust and non-dust days, respectively, whereas the pollution-crust ions were the main ion fractions in both dust days of various dust intensity and non-dust days, which demonstrated clearly that the mixing between mineral and pollution aerosols was ubiquitous during the dust seasons (even in the super dust storm days) although it was more obvious in those normal and weak dust episodes. The main chemical species of the water-soluble part of the aerosols were CaCO 3 in the super dust storm, CaSO 4 in the normal and the weak dust events, and NH 4NO 3 in the non-dust event days. The secondary transformation of sulfate and nitrate occurred on dust particles both during and after dust days provided the strong evidence of the mixing between mineral and pollution aerosols during the long-range transport of dust.

Chemical characteristics, deposition fluxes and source apportionment of precipitation components in the Jiaozhou Bay, North China

NASA Astrophysics Data System (ADS)

Xing, Jianwei; Song, Jinming; Yuan, Huamao; Li, Xuegang; Li, Ning; Duan, Liqin; Qu, Baoxiao; Wang, Qidong; Kang, Xuming

2017-07-01

To systematically illustrate the chemical characteristics, deposition fluxes and potential sources of the major components in precipitation, 49 rainwater and snow water samples were collected in the Jiaozhou Bay from June 2015 to May 2016. We determined the pH, electric conductivity (EC) and the concentrations of main ions (Na+, K+, Ca2 +, Mg2 +, NH4+, SO42 -, NO3-, Cl- and F-) as well as analyzed their source contributions and atmospheric transport. The results showed that the precipitation samples were severely acidified with an annual volume-weighted mean (VWM) pH of 4.77. The frequency of acid precipitation (pH < 5.6) reached up to 71.4%, and the mean EC value was relatively higher at 64.9 μS cm- 1, all of which suggested a higher atmospheric pollution level over the Jiaozhou Bay. Surprisingly, NH4+ (40.4%), which is higher than Ca2 + (29.3%), is the dominant species of cations, which is different from that in most areas of China. SO42 - was the most abundant anions, and accounted for 41.6% of the total anions. The wet deposition fluxes of sulfur (S) was 12.98 kg ha- 1 yr- 1. Rainfall, emission intensity and long-range transport of natural and anthropogenic pollutants together control the concentrations and wet deposition fluxes of chemical components in the precipitation. Non-sea-salt SO42 - and NO3- were the primary acid components while NH4+ and non-sea-salt Ca2 + were the dominating neutralizing constituents. The comparatively lower rainwater concentration of Ca2 + in the Jiaozhou Bay than that in other regions in Northern China likely to be a cause for the strong acidity of precipitation. Based on the combined enrichment factor and correlation analysis, the integrated contributions of sea-salt, crustal and anthropogenic sources to the total ions of precipitation were estimated to be 28.7%, 14.5% and 56.8%, respectively. However, the marine source fraction of SO42 - may be underestimated as the contribution from marine phytoplankton was neglected. Therefore, the precipitation components in the Jiaozhou Bay present complex chemical characteristics under the combined effects of natural changes and anthropogenic activities.

Effect of Halide Flux on Physicochemical Properties of MgCl2-Based Molten Salts for Accelerating Zirconium Production: Thermodynamic Assessment

NASA Astrophysics Data System (ADS)

Shin, Jae Hong; Park, Joo Hyun

2016-09-01

The effective halide flux additive for increasing the density of MgCl2 mixture and for decreasing the activity of MgCl2 was investigated in order to improve the reaction efficiency between gaseous ZrCl4 and fresh Mg melt to produce zirconium sponge. Thermochemical computation using FactSageTM software was primarily carried out, followed by the experimental confirmation. The addition of CaCl2, BaCl2, MgF2, and CaF2 to the molten MgCl2 increases the density of the melts, indicating that these halide additives can be a candidate to increase the density of the MgCl2-based molten salts. Among them, BaCl2, MgF2, and CaF2 are the useful additives. The activity of MgCl2 can be reduced by the addition of BaCl2, KCl, NaCl, MgF2, and CaF2, among which the CaF2 is the most effective additive to reduce the activity of MgCl2 with the strongest negative deviation from an ideality. Thus, the addition of CaF2 to the MgCl2, forming the MgCl2-CaF2 binary melt, is the most effective way not only to increase the density of the melt but also to decrease the activity of MgCl2, which was experimentally confirmed. Consequently, the production rate of zirconium sponge by magnesiothermic reduction process can be accelerated by the addition of CaF2.

Soil fluoride fractions and their bioavailability to tea plants (Camellia sinensis L.).

PubMed

Yi, Xiaoyun; Qiao, Sha; Ma, Lifeng; Wang, Jie; Ruan, Jianyun

2017-10-01

Drinking teas containing high fluoride (F) imposes fluorosis risk. The soil F bioavailability is an important factor influencing its uptake and contents in teas. The present work was conducted to investigate F fractions in soil and their bioavailability to tea plants. Tea seedlings were cultivated on 6 typical soils treated with a mixture consisting of dolomite, lime, peat and KCl at variable rates in the pot experiment. Soils and young shoots were collected in pairs from 63 sites of 21 plantations in a field experiment. Soil fluoride was sequentially separated into hot water soluble [Formula: see text], exchangeable [Formula: see text] (by 1 mol L -1 MgCl 2 , pH = 7.0), F bound to Mn and Fe hydroxides [F (oxides,s) ], and organic matter [F (OM,s) ] or extracted independently by water [Formula: see text] or 0.01 mol L -1 CaCl 2 solution [Formula: see text]. Averaged [Formula: see text], [Formula: see text], F (oxides,s) and F (OM,s) accounted for 51, 14, 5 and 30 % of the total sequential extracts, respectively. There were significant correlations among [Formula: see text], [Formula: see text] and F (OM,s) . Fluoride contents in leaves correlated with [Formula: see text] (r = 0.71, p < 0.001), [Formula: see text] (r = 0.93, p < 0.001) and F (OM,s) (r = 0.69, p < 0.01) but not other fractions in the pot experiment and with [Formula: see text] (r = 0.43-0.57, p < 0.001) and [Formula: see text] (r = 0.42-0.79, p < 0.001) in the field experiment. It was concluded that 0.01 M CaCl 2 extractable fluoride can be a good indicator of soil F bioavailability to tea plants. The significant correlations among some of the F fractions suggested that F in solution, AlF complexes (AlF 2 + , AlF 2+ ) and those bound to organic matter likely represent the available pools to tea plants.

A quality-assurance assessment for constituents reported by the national atmospheric deposition program and the national trends network

NASA Astrophysics Data System (ADS)

See, Randolph B.; Schroder, LeRoy J.; Willoughby, Timothy C.

A continuing quality-assurance program has been operated by the U.S. Geological Survey to evaluate any bias introduced by routine handling, shipping, and laboratory analyses of wet-deposition samples collected in the National Atmospheric Deposition Program (NADP) and National Trends Network (NTN). Blind-audit samples having a variety of constituent concentrations and values were selected. Only blind-audit samples with constituent concentrations and values less than the 95th-percentile concentration for natural wet-deposition samples were included in the analysis. Of the major ions, there was a significant increase of Ca 2+, Mg 2+, Na 2+, K +, SO 42- and Cl -1 in samples handled according to standard protocols and shipped in NADP/NTN sample-collection buckets. For 1979-1987, graphs of smoothed data showing the estimated contamination in blind-audit samples indicate a decrease in the median concentration and ranges of Ca 2+, Mg 2+ and SO 42- contamination of blind-audit samples shipped in sample-collection buckets. Part of the contamination detected in blind-audit samples can be attributed to contact with the sample-collection bucket and lid; however, additional sources also seem to contaminate the blind-audit sample. Apparent decreases in the magnitude and range of sample contamination may be caused by differences in sample-collection bucket- and lid-washing procedures by the NADP/NTN Central Analytical Laboratory. Although the degree of bias is minimal for most constituents, summaries of the NADP/NTN data base may contain overestimates of Ca 2+, Mg 2+, Na -, K + and SO 42- and Cl - concentrations, and underestimates of H + concentrations.

A quality-assurance assessment for constituents reported by the National Atmospheric Deposition Program and the National Trends Network

USGS Publications Warehouse

See, R.B.; Schroder, L.J.; Willoughby, T.C.

1989-01-01

A continuing quality-assurance program has been operated by the U.S. Geographical Survey to evaluate any bias introduced by routine handling, shipping, and laboratory analyses of wet-deposition samples collected in the National Atmospheric Deposition Program (NADP) and National Trends Network (NTN). Blind-audit samples having a variety of constituent concentrations and values were selected. Only blind-audit samples with constituent concentrations and values less than the 95th-percentile concentration for natural wet-deposition samples were included in the analysis. Of the major ions, there was a significant increase of Ca2+, Mg2+, K+ SO42+ and Cl- in samples handled according to standard protocols and shipped in NADP/NTN sample-collection buckets. For 1979-1987, graphs of smoothed data showing the estimated contaminations in blind-audit samples indicate a decrease in the median concentration and ranges of Ca2+, Mg2+ and SO42- contamination of blind-audit samples shipped in sample-collection buckets. Part of the contamination detected in blind-audit samples can be attributed to contact with the sample-collection bucket and lid; however, additional sources also seem to contaminate the blind-audit sample. Apparent decreases in the magnitude and range of sample contamination may be caused by differences in sample-collection bucket- and lid-washing procedures by the NADP/NTN Central Analytical Laboratory. Although the degree of bias is minimal for most constituents, summaries of the NADP/NTN data base may contain overestimates of Ca2+, Mg2+, Na-, K+, SO42- and Cl- concentrations, and underestimates of H+ concentrations.

Hydrochemistry of the Mahomet Bedrock Valley Aquifer, East-Central Illinois: indicators of recharge and ground-water flow

USGS Publications Warehouse

Panno, S.V.; Hackley, Keith C.; Cartwright, K.; Liu, Chao-Li

1994-01-01

A conceptual model of the ground-water flow and recharge to the Mahomet Bedrock Valley Aquifer (MVA), east-central Illinois, was developed using major ion chemistry and isotope geochemistry. The MVA is a 'basal' fill in the east-west trending buried bedrock valley composed of clean, permeable sand and gravel to thicknesses of up to 61 m. It is covered by a thick sequence of glacial till containing thinner bodies of interbedded sand and gravel. Ground water from the MVA was found to be characterized by clearly defined geochemical regions with three distinct ground-water types. A fourth ground-water type was found at the confluence of the MVA and the Mackinaw Bedrock Valley Aquifer (MAK) to the west. Ground water in the Onarga Valley, a northeastern tributary of the MVA, is of two types, a mixed cation-SO42- type and a mixed cation-HCO3- type. The ground water is enriched in Na+, Ca2+, Mg2+, and SO42- which appears to be the result of an upward hydraulic gradient and interaction of deeper ground water with oxidized pyritic coals and shale. We suggest that recharge to the Onarga Valley and overlying aquifers is 100% from bedrock (leakage) and lateral flow from the MVA to the south. The central MVA (south of the Onarga Valley) is composed of relatively dilute ground water of a mixed cation-HCO3- type, with low total dissolved solids, and very low concentrations of Cl- and SO42-. Stratigraphic relationships of overlying aquifers and ground-water chemistry of these and the MVA suggest recharge to this region of the MVA (predominantly in Champaign County) is relatively rapid and primarily from the surface. Midway along the westerly flow path of the MVA (western MVA), ground water is a mixed cation-HCO3- type with relatively high Cl-, where Cl- increases abruptly by one to ??? two orders of magnitude. Data suggest that the increase in Cl- is the result of leakage of saline ground water from bedrock into the MVA. Mass-balance calculations indicate that approximately 9.5% of recharge in this area is from bedrock. Concentrations of Na+, HCO3-, As, and TDS also increase in the western MVA. Ground water in the MAK is of a Ca2+-HCO3- type. Mass-balance calculations, using Cl- as a natural, conservative tracer, indicate that approximately 17% of the ground water flowing from the confluence area is derived from the MVA.

Diazo dye Congo Red degradation using a Boron-doped diamond anode: An experimental study on the effect of supporting electrolytes.

PubMed

Jalife-Jacobo, H; Feria-Reyes, R; Serrano-Torres, O; Gutiérrez-Granados, S; Peralta-Hernández, Juan M

2016-12-05

Diazo dye Congo Red (CR) solutions at 100mg/L, were degraded using different supporting electrolytes in an electrochemical advanced oxidation process (EAOPs), like the anodic oxidation (AOx/BDD). All experiments were carried out in a 3L flow reactor with a Boron-doped diamond (BDD) anode and stainless steel cathode (AISI 304), at 7.5, 15, 30 and 50mA/cm(2) current densities (j). Furthermore, each experiment was carried out under a flow rate of 7L/min. Additionally, HClO4, NaCl, Na2SO4, and H2SO4 were tested as supporting electrolytes at a 50mM concentration. The degradation process was at all times considerably faster in NaCl medium. Solutions containing SO4(2-) or ClO4(-) ions were less prompted to degradation due to the low oxidation power of these species into the bulk. Dissolved organic carbon (DOC) analysis, was carried out to evaluate the mineralization of CR. The degradation of CR, was evaluated with the HPLC analysis of the treated solutions. Copyright © 2016 Elsevier B.V. All rights reserved.

Water activities of NaClO4, Ca(ClO4)2, and Mg(ClO4)2 brines from experimental heat capacities: Water activity >0.6 below 200 K

NASA Astrophysics Data System (ADS)

Toner, J. D.; Catling, D. C.

2016-05-01

Perchlorate salts found on Mars are extremely hygroscopic and form low eutectic temperature aqueous solutions, which could allow liquid water to exist on Mars despite cold and dry conditions. The formation, dynamics, and potential habitability of perchlorate salt solutions can be broadly understood in terms of water activity. Water activity controls condensation and evaporation of water vapor in brines, deliquescence and efflorescence of crystalline salts, and ice formation during freezing. Furthermore, water activity is a basic parameter defining the habitability of aqueous solutions. Despite the importance of water activity, its value in perchlorate solutions has only been measured at 298.15 K and at the freezing point of water. To address this lack of data, we have determined water activities in NaClO4, Ca(ClO4)2, and Mg(ClO4)2 solutions using experimental heat capacities measured by Differential Scanning Calorimetry. Our results include concentrations up to near-saturation and temperatures ranging from 298.15 to 178 K. We find that water activities in NaClO4 solutions increase with decreasing temperature, by as much as 0.25 aw from 298.15 to 178 K. Consequently, aw reaches ∼0.6-0.7 even for concentrations up to 15 molal NaClO4 below 200 K. In contrast, water activities in Ca(ClO4)2 and Mg(ClO4)2 solutions generally decrease with decreasing temperature. The temperature dependence of water activity indicates that low-temperature NaClO4 solutions will evaporate and deliquesce at higher relative humidity, crystallize ice at higher temperature, and potentially be more habitable for life (at least in terms of water activity) compared to solutions at 298.15 K. The opposite effects occur in Ca(ClO4)2 and Mg(ClO4)2 solutions.

Monsoonal variations in atmospheric surfactants at different coastal areas of the Malaysian Peninsula.

PubMed

Jaafar, Shoffian Amin; Latif, Mohd Talib; Razak, Intan Suraya; Shaharudin, Muhammad Zulhilmi; Khan, Md Firoz; Wahid, Nurul Bahiyah Abd; Suratman, Suhaimi

2016-08-15

This study determined the effect of monsoonal changes on the composition of atmospheric surfactants in coastal areas. The composition of anions (SO4(2-), NO3(-), Cl(-), F(-)) and the major elements (Ca, K, Mg, Na) in aerosols were used to determine the possible sources of surfactants. Surfactant compositions were determined using a colorimetric method as methylene blue active substances (MBAS) and disulphine blue active substances (DBAS). The anion and major element compositions of the aerosol samples were determined by ion chromatography (IC) and inductively coupled plasma mass spectrometry (ICP-MS), respectively. The results indicated that the concentrations of surfactant in aerosols were dominated by MBAS (34-326pmolm(-3)). Monsoonal changes were found to significantly affect the concentration of surfactants. Using principal component analysis-multiple linear regressions (PCA-MLR), major possible sources for surfactants in the aerosols were motor vehicle emissions, secondary aerosol and the combustion of biomass along with marine aerosol. Copyright © 2016 Elsevier Ltd. All rights reserved.

Anomalous chemical changes in well waters and possible relation to earthquakes.

USGS Publications Warehouse

Chi-Yu, King; Evans, William C.; Presser, T.; Husk, R.H.

1981-01-01

Water level, temperature, salinity, electric conductivity, and pH have been measured periodically for several years at three water wells located along a 17km segment of the San Andreas fault between San Juan Bautista and Cienega Winery in central California. Water samples were collected at the same time for subsequent chemical analyses in the laboratory. Some sudden large changes in salinity and conductivity were recorded in early March 1980 at the two wells near San Juan Bautista. These changes coincided approximately with the beginning of an episode of increased local seismicity, including a magnitude 4.8 earthquake on April 13. Analyses of water samples revealed corresponding changes in ion concentrations, especially of Na+, Ca2+, Mg2+, 035SO42-, 046HCO3-, F-, and Cl-. The observed changes may be the result of mixing of waters from different aquifers through cracks developed in the water barriers by a possible crustal strain episode that may have occurred in the study area.-Authors

Multivariate statistical techniques for the evaluation of groundwater quality of Amaravathi River Basin: South India

NASA Astrophysics Data System (ADS)

Loganathan, K.; Ahamed, A. Jafar

2017-12-01

The study of groundwater in Amaravathi River basin of Karur District resulted in large geochemical data set. A total of 24 water samples were collected and analyzed for physico-chemical parameters, and the abundance of cation and anion concentrations was in the following order: Na+ > Ca2+ > Mg2+ > K+ = Cl- > HCO3 - > SO4 2-. Correlation matrix shows that the basic ionic chemistry is influenced by Na+, Ca2+, Mg2+, and Cl-, and also suggests that the samples contain Na+-Cl-, Ca2+-Cl- an,d mixed Ca2+-Mg2+-Cl- types of water. HCO3 -, SO4 2-, and F- association is less than that of other parameters due to poor or less available of bearing minerals. PCA extracted six components, which are accountable for the data composition explaining 81% of the total variance of the data set and allowed to set the selected parameters according to regular features as well as to evaluate the frequency of each group on the overall variation in water quality. Cluster analysis results show that groundwater quality does not vary extensively as a function of seasons, but shows two main clusters.

The major-ion composition of Cenozoic seawater: the past 36 million years from fluid inclusions in marine halite

USGS Publications Warehouse

Brennan, Sean T.; Lowenstein, Tim K.; Cendon, Dioni I.

2013-01-01

Fluid inclusions from ten Cenozoic (Eocene-Miocene) marine halites are used to quantify the major-ion composition (Mg2+, Ca2+, K+, Na+, SO42−, and Cl−) of seawater over the past 36 My. Criteria used to determine a seawater origin of the halites include: (1) stratigraphic, sedimentologic, and paleontologic observations; (2) Br− in halite; (3) δ34S of sulfate minerals; (4) 87Sr/86Sr of carbonates and sulfates; and (5) fluid inclusion brine compositions and evaporation paths, which must overlap from geographically separated basins of the same age to confirm a “global” seawater chemical signal. Changes in the major-ion chemistry of Cenozoic seawater record the end of a systematic, long term (>150 My) shift from the Ca2+-rich, Mg2+- and SO42−-poor seawater of the Mesozoic (“CaCl2 seas”) to the “MgSO4 seas” (with higher Mg2+ and SO42−>Ca2+) of the Cenozoic. The major ion composition of Cenozoic seawater is calculated for the Eocene-Oligocene (36-34 Ma), Serravallian-Tortonian (13.5-11.8 Ma) and the Messinian (6-5 Ma), assuming chlorinity (565 mmolal), salinity, and the K+ concentration (11 mmolal) are constant and the same as in modern seawater. Fluid inclusions from Cenozoic marine halites show that the concentrations of Mg2+and SO42− have increased in seawater over the past 36 My and the concentration of Ca2+ has decreased. Mg2+ concentrations increased from 36 mmolal in Eocene-Oligocene seawater (36-34 Ma) to 55 mmolal in modern seawater. The Mg2+/Ca2+ ratio of seawater has risen from ∼2.3 at the end of the Eocene, to 3.4 and 4.0, respectively, at 13.5 to 11.8 Ma and 6 to 5 Ma, and to 5 in modern seawater. Eocene-Oligocene seawater (36-34 Ma) has estimated ranges of SO42− = 14–23 mmolal and Ca2+ = 11–20 mmolal. If the (Ca2+)(SO42−) product is assumed to be the same as in modern seawater (∼300 mmolal2), Eocene-Oligocene seawater had Ca2+ ∼16 mmolal and SO42− ∼19 mmolal. The same estimates of Ca2+ and SO42− for Serravallian-Tortonian seawater (13.5-11.8 Ma) are SO42− = 19–27 mmolal and Ca2+ = 8–16 mmolal and SO42− ∼24 mmolal and Ca2+ ∼ 13 mmolal if the (Ca2+)(SO42−) product is equal to that in modern seawater. Messinian seawater has an estimated range of SO42− ∼21–29 mmolal and Ca2+ ∼7–15 mmolal with SO42− ∼26 mmolal and Ca2+ ∼12 mmolal assuming the (Ca2+)(SO42−) product is equal to that in modern seawater. Regardless of the estimation procedure, SO42− shows progressively increasing concentrations from 36 Ma to the present values, which are the highest of the Cenozoic.

Protein adsorption to poly(ethylenimine)-modified Sepharose FF: V. Complicated effects of counterions.

PubMed

Liu, Na; Yu, Linling; Sun, Yan

2015-07-24

In the previous studies on protein adsorption to poly(ethylenimine) (PEI)-grafted Sepharose FF resins, a critical ionic capacity (600mmol/L) of PEI-Sepharose resins was found for the adsorption of bovine serum albumin (BSA), above which both protein capacity and uptake rate increased drastically. In this work, the influence of counterions on the PEI-Sepharose resin with an ionic capacity of 683mmol/L (FF-PEI-L680) was investigated with sodium salts of SCN(-), Cl(-), HPO4(2-) and SO4(2-). Linear gradient elution, batch adsorption and breakthrough experiments showed that counterion preference, effective pore diffusion coefficient (De) and dynamic binding capacity (DBC) values increased in the order of SCN(-), Cl(-), HPO4(2-) and SO4(2-), while static adsorption capacity decreased in this order. It is considered that higher counterion preference of the ion exchange groups resulted in lower protein binding strength and adsorption capacity, while the De value increased due to the enhanced "chain delivery" effect (a kind of surface diffusion). Besides, the DBC value was mainly dependent on De value. In particular, SO4(2-) was the most favorable counterion for the PEI-Sepharose resin, which gave rise to the highest De value (De/D0=1.17, D0 is protein diffusivity in free solution) and DBC value (118mg/mL at a residence time of 2min). Moreover, the effects of counterions on BSA adsorption to DEAE Sepharose FF and Q Sepharose FF, which were non-grafted resins, were also studied for comparisons. It was found that the counterion preferences of the two non-grafted resins were different from each other and also different from that of FF-PEI-L680. The different counterion preferences were attributed to the differences in the ion-exchange ligand chemistries. In addition, the De values for DEAE Sepharose FF and Q Sepharose FF kept unchanged. The low counterion sensitivity of De values could be interpreted as the lack of "chain delivery" effect for the non-grafted resins. The results indicate that protein adsorption and chromatographic performance with PEI-Sepharose can be improved by proper counterions. For the four counterions tested, SO4(2-) was the most favorable for providing the best adsorption and elution outcomes with FF-PEI-L680. Copyright © 2015 Elsevier B.V. All rights reserved.

The promotion effect of coexisting hygroscopic composition on the reaction between oxalic acid and calcite during humidifying process

NASA Astrophysics Data System (ADS)

Ma, Q.; He, H.

2012-12-01

Internally mixed oxalic acid with mineral dust has been frequently detected in field measurements (Sullivan and Prather, 2007; Wang et al., 2012; Yang et al., 2009). Meanwhile, Furukawa and Takahashi (Furukawa and Takahashi, 2011) found that most of the oxalic acid in mineral mixture is present as metal oxalate complexes in the aerosols, however, the formation mechanism of these complexes is not well known. It was reported that cloud process of H2C2O4/CaCO3 mixture could lead to the formation of calcium oxalate (Gierlus et al., 2012). Recently, we used Raman spectroscopy to investigate the hygroscopic behavior of H2C2O4/CaCO3 mixture below saturation condition as well as the effect of coexisting hygroscopic compositions, e.g. Ca(NO3)2, NaCl, NH4NO3, and (NH4)2SO4. It was found that there was no interaction between H2C2O4 and calcite without third component during humidifying process under ambient condition. In contrast, the presence of coexisting Ca(NO)3, NaCl, or NH4NO3 could promote the reaction between H2C2O4 and calcite by providing an aqueous circumstance after deliquescence, resulting in the formation of calcium oxalate hydrates. Moreover, substitution of strong acid (HNO3) by medium acid (H2C2O4) occurred when water vapor was absorbed in Ca(NO3)2/H2C2O4 mixture (Ma and He, 2012). As for (NH4)2SO4, there existed a competition effect between (NH4)2SO4 and H2C2O4 for the reaction with CaCO3. CaCO3 was preferentially reacted with (NH4)2SO4 to form gypsum in the solution, while the residual NH4+ and C2O42- ions were bonded to (NH4)2C2O4 after efflorescence. These results implies a potential formation pathway of metal oxalate complexes in the atmosphere and also suggests that synergistic effect between different constituents in humidifying process of mixed particles should be considered in future hygroscopic behavior studies.

An Electronic Tongue Designed to Detect Ammonium Nitrate in Aqueous Solutions

PubMed Central

Campos, Inmaculada; Pascual, Lluis; Soto, Juan; Gil-Sánchez, Luis; Martínez-Máñez, Ramón

2013-01-01

An electronic tongue has been developed to monitor the presence of ammonium nitrate in water. It is based on pulse voltammetry and consists of an array of eight working electrodes (Au; Pt; Rh; Ir; Cu; Co; Ag and Ni) encapsulated in a stainless steel cylinder. In a first step the electrochemical response of the different electrodes was studied in the presence of ammonium nitrate in water in order to further design the wave form used in the voltammetric tongue. The response of the electronic tongue was then tested in the presence of a set of 15 common inorganic salts; i.e.; NH4NO3; MgSO4; NH4Cl; NaCl; Na2CO3; (NH4)2SO4; MgCl2; Na3PO4; K2SO4; K2CO3; CaCl2; NaH2PO4; KCl; NaNO3; K2HPO4. A PCA plot showed a fairly good discrimination between ammonium nitrate and the remaining salts studied. In addition Fuzzy Art map analyses determined that the best classification was obtained using the Pt; Co; Cu and Ni electrodes. Moreover; PLS regression allowed the creation of a model to correlate the voltammetric response of the electrodes with concentrations of ammonium nitrate in the presence of potential interferents such as ammonium chloride and sodium nitrate. PMID:24145916

Transformations of snow chemistry in the boreal forest: Accumulation and volatilization

USGS Publications Warehouse

Pomeroy, J.W.; Davies, T.D.; Jones, H.G.; Marsh, P.; Peters, N.E.; Tranter, M.

1999-01-01

This paper examines the processes and dynamics of ecologically-important inorganic chemical (primarily NO3-N) accumulation and loss in boreal forest snow during the cold winter period at a northern and southern location in the boreal forest of western Canada. Field observations from Inuvik, Northwest Territories and Waskesiu, Saskatchewan, Canada were used to link chemical transformations and physical processes in boreal forest snow. Data on the disposition and overwinter transformation of snow water equivalent, NO3-, SO42- and other major ions were examined. No evidence of enhanced dry deposition of chemical species to intercepted snow was found at either site except where high atmospheric aerosol concentrations prevailed. At Inuvik, concentrations of SO42- and Cl- were five to six times higher in intercepted snow than in surface snow away from the trees. SO4-S and Cl loads at Inuvik were correspondingly enhanced three-fold within the nearest 0.5 m to individual tree stems. Measurements of snow affected by canopy interception without rapid sublimation provided no evidence of ion volatilization from intercepted snow. Where intercepted snow sublimation rates were significant, ion loads in sub-canopy snow suggested that NO3- volatized with an efficiency of about 62% per snow mass sublimated. Extrapolating this measurement from Waskesiu to sublimation losses observed in other southern boreal environments suggests that 19-25% of snow inputs of NO3- can be lost during intercepted snow sublimation. The amount of N lost during sublimation may be large in high-snowfall, high N load southern boreal forests (Quebec) where 0.42 kg NO3-N ha-1 is estimated as a possible seasonal NO3- volatilization. The sensitivity of the N fluxes to climate and forest canopy variation and implications of the winter N losses for N budgets in the boreal forest are discussed.This paper examines the processes and dynamics of ecologically-important inorganic chemical (primarily NO3-N) accumulation and loss in boreal forest snow during the cold winter period at a northern and southern location in the boreal forest of western Canada. Field observations from Inuvik. Northwest Territories and Waskesiu, Saskatchewan, Canada were used to link chemical transformations and physical processes in boreal forest snow. Data on the disposition and overwinter transformation of snow water equivalent, NO3-, SO42- and other major ions were examined. No evidence of enhanced dry deposition of chemical species to intercepted snow was found at either site except where high atmospheric aerosol concentrations prevailed. At Inuvik, concentrations of SO42- and Cl- were five to six times higher in intercepted snow than in surface snow away from the trees. SO4-S and Cl loads at Inuvik were correspondingly enhanced three-fold within the nearest 0.5 m to individual tree stems. Measurements of snow affected by canopy interception without rapid sublimation provided no evidence of ion volatilization from intercepted snow. Where intercepted snow sublimation rates were significant, ion loads in sub-canopy snow suggested that NO3- volatized with an efficiency of about 62% per snow mass sublimated. Extrapolating this measurement from Waskesiu to sublimation losses observed in other southern boreal environments suggests that 19-25% of snow inputs of NO3- can be lost during intercepted snow sublimation. The amount of N lost during sublimation may be large in high-snowfall, high N load southern boreal forests (Quebec) where 0.42 kg NO3-N ha-1 is estimated as a possible seasonal NO3- volatilization. The sensitivity of the N fluxes to climate and forest canopy variation and implications of the winter N losses for N budgets in the boreal forest are discussed.

18F-Fluorosulfate for PET Imaging of the Sodium-Iodide Symporter: Synthesis and Biologic Evaluation In Vitro and In Vivo.

PubMed

Khoshnevisan, Alex; Chuamsaamarkkee, Krisanat; Boudjemeline, Mehdi; Jackson, Alex; Smith, Gareth E; Gee, Antony D; Fruhwirth, Gilbert O; Blower, Philip J

2017-01-01

Anion transport by the human sodium-iodide symporter (hNIS) is an established target for molecular imaging and radionuclide therapy. Current radiotracers for PET of hNIS expression are limited to 124 I - and 18 F-BF 4 - We sought new 18 F-labeled hNIS substrates offering higher specific activity, higher affinity, and simpler radiochemical synthesis than 18 F-BF 4 - METHODS: The ability of a range of anions, some containing fluorine, to block 99m TcO 4 - uptake in hNIS-expressing cells was measured. SO 3 F - emerged as a promising candidate. 18 F-SO 3 F - was synthesized by reaction of 18 F - with SO 3 -pyridine complex in MeCN and purified using alumina and quaternary methyl ammonium solid-phase extraction cartridges. Chemical and radiochemical purity and serum stability were determined by radiochromatography. Radiotracer uptake and efflux in hNIS-transduced HCT116-C19 cells and the hNIS-negative parent cell line were evaluated in vitro in the presence and absence of a known competitive inhibitor (NaClO 4 ). PET/CT imaging and ex vivo biodistribution measurement were conducted on BALB/c mice, with and without NaClO 4 inhibition. Fluorosulfate was identified as a potent inhibitor of 99m TcO 4 - uptake via hNIS in vitro (half-maximal inhibitory concentration, 0.55-0.56 μM (in comparison with 0.29-4.5 μM for BF 4 - , 0.07 μM for TcO 4 - , and 2.7-4.7 μM for I - ). Radiolabeling to produce 18 F-SO 3 F - was simple and afforded high radiochemical purity suitable for biologic evaluation (radiochemical purity > 95%, decay-corrected radiochemical yield = 31.6%, specific activity ≥ 48.5 GBq/μmol). Specific, blockable hNIS-mediated uptake in HCT116-C19 cells was observed in vitro, and PET/CT imaging of normal mice showed uptake in thyroid, salivary glands (percentage injected dose/g at 30 min, 563 ± 140 and 32 ± 9, respectively), and stomach (percentage injected dose/g at 90 min, 68 ± 21). Fluorosulfate is a high-affinity hNIS substrate. 18 F-SO 3 F - is easily synthesized in high yield and very high specific activity and is a promising candidate for preclinical and clinical PET imaging of hNIS expression and thyroid-related disease; it is the first example of in vivo PET imaging with a tracer containing an S- 18 F bond. © 2017 by the Society of Nuclear Medicine and Molecular Imaging.

Cognitive benefits of lithium chloride in APP/PS1 mice are associated with enhanced brain clearance of β-amyloid.

PubMed

Pan, Yijun; Short, Jennifer L; Newman, Stephanie A; Choy, Kwok H C; Tiwari, Durgesh; Yap, Christopher; Senyschyn, Danielle; Banks, William A; Nicolazzo, Joseph A

2018-05-01

Epidemiological evidence suggests that people with bipolar disorder prescribed lithium exhibit a lower risk of Alzheimer's disease (AD) relative to those prescribed other mood-stabilizing medicines. Lithium chloride (LiCl) reduces brain β-amyloid (Aβ) levels, and the brain clearance of Aβ is reduced in AD. Therefore, the purpose of this study was to assess whether the cognitive benefits of LiCl are associated with enhanced brain clearance of exogenously-administered Aβ. The brain clearance of intracerebroventricularly (icv) administered 125 I-Aβ 42 was assessed in male Swiss outbred mice administered daily oral NaCl or LiCl (300 mg/kg for 21 days). LiCl exhibited a 31% increase in the brain clearance of 125 I-Aβ 42 over 10 min, which was associated with a 1.6-fold increase in brain microvascular expression of the blood-brain barrier efflux transporter low density lipoprotein receptor-related protein 1 (LRP1) and increased cerebrospinal fluid (CSF) bulk-flow. 8-month-old female wild type (WT) and APP/PS1 mice were also administered daily NaCl or LiCl for 21 days, which was followed by cognitive assessment by novel object recognition and water maze, and measurement of soluble Aβ 42 , plaque-associated Aβ 42 , and brain efflux of 125 I-Aβ 42 . LiCl treatment restored the long-term spatial memory deficit observed in APP/PS1 mice as assessed by the water maze (back to similar levels of escape latency as WT mice), but the short-term memory deficit remained unaffected by LiCl treatment. While LiCl did not affect plaque-associated Aβ 42 , soluble Aβ 42 levels were reduced by 49.9% in APP/PS1 mice receiving LiCl. The brain clearance of 125 I-Aβ 42 decreased by 27.8% in APP/PS1 mice, relative to WT mice, however, LiCl treatment restored brain 125 I-Aβ 42 clearance in APP/PS1 mice to a rate similar to that observed in WT mice. These findings suggest that the cognitive benefits and brain Aβ 42 lowering effects of LiCl are associated with enhanced brain clearance of Aβ 42 , possibly via brain microvascular LRP1 upregulation and increased CSF bulk-flow, identifying a novel mechanism of protection by LiCl for the treatment of AD. Crown Copyright © 2018. Published by Elsevier Inc. All rights reserved.

Enrichment of fluoride in groundwater under the impact of saline water intrusion at the salt lake area of Yuncheng basin, northern China

NASA Astrophysics Data System (ADS)

Gao, Xubo; Wang, Yanxin; Li, Yilian; Guo, Qinghai

2007-12-01

Long-term intake of high-fluoride groundwater causes endemic fluorosis. This study, for the first time, discovered that the salt lake water intrusion into neighboring shallow aquifers might result in elevation of fluoride content of the groundwater. Two cross-sections along the groundwater flow paths were selected to study the geochemical processes controlling fluoride concentration in Yuncheng basin, northern China. There are two major reasons for the observed elevation of fluoride content: one is the direct contribution of the saline water; the other is the undersaturation of the groundwater with respect to fluorite due to salt water intrusion, which appears to be more important reason. The processes of the fluorine activity reduction and the change of Na/Ca ratio in groundwater induced by the intrusion of saline water favor further dissolution of fluorine-bearing mineral, and it was modeled using PHREEQC. With the increase in Na concentration (by adding NaCl or Na2SO4 as Na source, calcium content kept invariable), the increase of NaF concentration was rapid at first and then became slower; and the concentrations of HF, HF{2/-}, CaF+, and MgF+ were continuously decreasing. The geochemical conditions in the study area are advantageous to the complexation of F- with Na+ and the decline of saturation index of CaF2, regardless of the water type (Cl-Na or SO4-Na type water).

The acute toxicity of major ion salts to Ceriodaphnia dubia: III. Mathematical models for mixture toxicity

EPA Science Inventory

Based on previous research on the acute toxicity of major ions (Na+, K+, Ca2+, Mg2+, Cl, SO42, and HCO3/CO32) to C. dubia, two mathematical models were developed for predicting the LC50 for any ion mixture, excluding those dominated by K toxicity. One model addresses a mechanism...

Atmospheric dry deposition in the vicinity of the Salton Sea, California - II: Measurement and effects of an enhanced evaporation system

USGS Publications Warehouse

Alonso, R.; Bytnerowicz, A.; Yee, J.L.; Boarman, W.I.

2005-01-01

A study was conducted to determine the effects of salt spray drift from pilot technologies employed by the US Bureau of Reclamation on deposition rates of various air-born ions. An enhanced evaporation system (EES) was tested in the field at the Salton Sea, California. Dry deposition of NO3-, NH4+, SO42-, Cl-, Ca2+, Na+, K+ and Se was assessed by using nylon filters and branches of natural vegetation exposed for one-week long periods. The simultaneous exposure of both lyophilized branches and branches of live plants offered important information highlighting the dynamics of deposited ions on vegetation. The EES significantly increased the deposition rates of Cl-, SO42- and Na+ in an area of about 639-1062 m surrounding the sprayers. Similarly, higher deposition of Ca 2+ and K+ caused by the EES was detected only when deposition was assessed using nylon filters or lyophilized branches. Deposition fluxes of NO3-, NH4+ and Se were not affected by the spraying system. Techniques for measuring dry deposition and calculating landscape-level depositional loads in non-forested systems need further development. ?? 2005 Elsevier Ltd. All rights reserved.

Molecules in high spin states III: The millimeter/submillimeter-wave spectrum of the MnCl radical (X 7Σ+)

NASA Astrophysics Data System (ADS)

Halfen, D. T.; Ziurys, L. M.

2005-02-01

The pure rotational spectrum of the MnCl radical (X 7Σ+) has been recorded in the range 141-535 GHz using millimeter-submillimeter direct absorption spectroscopy. This work is the first time the molecule has been studied with rotational resolution in its ground electronic state. MnCl was synthesized by the reaction of manganese vapor, produced in a Broida-type oven, with Cl2. Transitions of both chlorine isotopomers were measured, as well as lines originating in several vibrationally excited states. The presence of several spin components and manganese hyperfine interactions resulted in quite complex spectra, consisting of multiple blended features. Because 42 rotational transitions were measured for Mn35Cl over a wide range of frequencies with high signal-to-noise, a very accurate set of rotational, fine structure, and hyperfine constants could be determined with the aid of spectral simulations. Spectroscopic constants were also determined for Mn37Cl and several vibrationally excited states. The values of the spin-rotation and spin-spin parameters were found to be relatively small (γ=11.2658 MHz and λ=1113.10 MHz for Mn35Cl); in the case of λ, excited electronic states contributing to the second-order spin-orbit interaction may be canceling each other. The Fermi contact hyperfine term was found to be large in manganese chloride with bF(Mn35Cl)=397.71 MHz, a result of the manganese 4s character mixing into the 12σ orbital. This orbital is spσ hybridized, and contains some Mn 4pσ character, as well. Hence, it also contributes to the dipolar constant c, which is small and positive for this radical (c=32.35 MHz for Mn35Cl). The hyperfine parameters in MnCl are similar to those of MnH and MnF, suggesting that the bonding in these three molecules is comparable.

Molecules in high spin states III: the millimeter/submillimeter-wave spectrum of the MnCl radical (X (7)Sigma(+)).

PubMed

Halfen, D T; Ziurys, L M

2005-02-01

The pure rotational spectrum of the MnCl radical (X (7)Sigma(+)) has been recorded in the range 141-535 GHz using millimeter-submillimeter direct absorption spectroscopy. This work is the first time the molecule has been studied with rotational resolution in its ground electronic state. MnCl was synthesized by the reaction of manganese vapor, produced in a Broida-type oven, with Cl(2). Transitions of both chlorine isotopomers were measured, as well as lines originating in several vibrationally excited states. The presence of several spin components and manganese hyperfine interactions resulted in quite complex spectra, consisting of multiple blended features. Because 42 rotational transitions were measured for Mn(35)Cl over a wide range of frequencies with high signal-to-noise, a very accurate set of rotational, fine structure, and hyperfine constants could be determined with the aid of spectral simulations. Spectroscopic constants were also determined for Mn(37)Cl and several vibrationally excited states. The values of the spin-rotation and spin-spin parameters were found to be relatively small (gamma=11.2658 MHz and lambda=1113.10 MHz for Mn(35)Cl); in the case of lambda, excited electronic states contributing to the second-order spin-orbit interaction may be canceling each other. The Fermi contact hyperfine term was found to be large in manganese chloride with b(F)(Mn(35)Cl)=397.71 MHz, a result of the manganese 4s character mixing into the 12sigma orbital. This orbital is spsigma hybridized, and contains some Mn 4psigma character, as well. Hence, it also contributes to the dipolar constant c, which is small and positive for this radical (c=32.35 MHz for Mn(35)Cl). The hyperfine parameters in MnCl are similar to those of MnH and MnF, suggesting that the bonding in these three molecules is comparable.

Electrodeposition of platinum nanoparticles in a room-temperature ionic liquid.

PubMed

Zhang, Da; Chang, Wan Cheng; Okajima, Takeyoshi; Ohsaka, Takeo

2011-12-06

The electrochemistry of the [PtCl(6)](2-)-[PtCl(4)](2-)-Pt redox system on a glassy carbon (GC) electrode in a room-temperature ionic liquid (RTIL) [i.e., N,N-diethyl-N-methyl-N-(2-methoxyethyl)ammonium tetrafluoroborate (DEMEBF(4))] has been examined. The two-step four-electron reduction of [PtCl(6)](2-) to Pt, i.e., reduction of [PtCl(6)](2-) to [PtCl(4)](2-) and further reduction of [PtCl(4)](2-) to Pt, occurs separately in this RTIL in contrast to the one-step four-electron reduction of [PtCl(6)](2-) to Pt in aqueous media. The cathodic and anodic peaks corresponding to the [PtCl(6)](2-)/[PtCl(4)](2-) redox couple were observed at ca. -1.1 and 0.6 V vs a Pt wire quasi-reference electrode, respectively, while those observed at -2.8 and -0.5 V were found to correspond to the [PtCl(4)](2-)/Pt redox couple. The disproportionation reaction of the two-electron reduction product of [PtCl(6)](2-) (i.e., [PtCl(4)](2-)) to [PtCl(6)](2-) and Pt metal was also found to occur significantly. The electrodeposition of Pt nanoparticles could be carried out on a GC electrode in DEMEBF(4) containing [PtCl(6)](2-) by holding the potential at -3.5 or -2.0 V. At -3.5 V, the four-electron reduction of [PtCl(6)](2-) to Pt can take place, while at -2.0 V the two-electron reduction of [PtCl(6)](2-) to [PtCl(4)](2-) occurs. The results obtained demonstrate that the electrodeposition of Pt at -3.5 V may occur via a series of reductions of [PtCl(6)](2-) to [PtCl(4)](2-) and further [PtCl(4)](2-) to Pt and at -2.0 V via a disproportionation reaction of [PtCl(4)](2-) to [PtCl(6)](2-) and Pt. Furthermore, the deposition potential of Pt nanoparticles was found to largely influence their size and morphology as well as the relative ratio of Pt(110) and Pt(100) crystalline orientation domains. The sizes of the Pt nanoparticles prepared by holding the electrode potential at -2.0 and -3.5 V are almost the same, in the range of ca. 1-2 nm. These small nanoparticles are "grown" to form bigger particles with different morphologies: In the case of the deposition at -2.0 V, the GC electrode surface is totally, relatively compactly covered with Pt particles of relatively uniform size of ca. 10-50 nm. On the other hand, in the case of the electrodeposition at -3.5 V, small particles of ca. 50-100 nm and the grown-up particles of ca. 100-200 nm cover the GC surface irregularly and coarsely. Interestingly, the Pt nanoparticles prepared by holding the potential at -2.0 and -3.5 V are relatively enriched in Pt(100) and Pt(110) facets, respectively. © 2011 American Chemical Society

Considerations in Physiological Metric Selection for Online Detection of Operator State: A Case Study

DTIC Science & Technology

2016-07-17

e.g., we omit functional magnetic resonance imaging; fMRI ). Researchers have investigated fatigue and related constructs using several different...integration and links to underlying memory systems. Personality and So- cial Psychology Review, 4(2), 108–131. 26. Prinzel, L. J., Freeman, F. G

A revised Pitzer model for low-temperature soluble salt assemblages at the Phoenix site, Mars

NASA Astrophysics Data System (ADS)

Toner, J. D.; Catling, D. C.; Light, B.

2015-10-01

The Wet Chemistry Laboratory (WCL) on the Mars Phoenix Lander measured ions in a soil-water extraction and found Na+, K+, H+ (pH), Ca2+, Mg2+, SO42-, ClO4-, and Cl-. Equilibrium models offer insights into salt phases that were originally present in the Phoenix soil, which dissolved to form the measured WCL solution; however, there are few experimental datasets for single cation perchlorates (ClO4-), and none for mixed perchlorates, at low temperatures, which are needed to build models. In this study, we measure ice and salt solubilities in binary and ternary solutions in the Na-Ca-Mg-ClO4 system, and then use this data, along with existing data, to construct a low-temperature Pitzer model for perchlorate brines. We then apply our model to a nominal WCL solution. Previous studies have modeled either freezing of a WCL solution or evaporation at a single temperature. For the first time, we model evaporation at subzero temperatures, which is relevant for dehydration conditions that might occur at the Phoenix site. Our model indicates that a freezing WCL solution will form ice, KClO4, hydromagnesite (3MgCO3·Mg(OH)2·3H2O), calcite (CaCO3), meridianiite (MgSO4·11H2O), MgCl2·12H2O, NaClO4·2H2O, and Mg(ClO4)2·6H2O at the eutectic (209 K). The total water held in hydrated salt phases at the eutectic is ∼1.2 wt.%, which is much greater than hydrated water contents when evaporation is modeled at 298.15 K (∼0.3 wt.%). Evaporation of WCL solutions at lower temperatures (down to 210 K) results in lower water activities and the formation of more dehydrated minerals, e.g. kieserite (MgSO4·H2O) instead of meridianiite. Potentially habitable brines, with water activity aw > 0.6, can occur when soil temperatures are above 220 K and when the soil liquid water content is greater than 0.4 wt.% (100 ×gH2O gsoil-1). In general, modeling indicates that mineral assemblages derived from WCL-type solutions are characteristic of the soil temperature, water content, and water activity conditions under which they formed, and are useful indicators of past environmental conditions.

Infrared Spectroscopic and Electronic Structure Investigations of Beryllium Halide Molecules, Cations, and Anions in Noble Gas Matrices.

PubMed

Yu, Wenjie; Andrews, Lester; Wang, Xuefeng

2017-11-22

Laser-ablated Be atoms, cations, and electrons were reacted with F 2 , ClF, Cl 2 , NF 3 , CCl 4 , CF 2 Cl 2 , HCl, DCl, and SiCl 4 diluted in noble gases. The major products were the dihalides BeF 2 , BeClF, BeCl 2 , and the hydride chloride HBeCl, whose identities were confirmed by comparison with previous evaporative work, deuterium substitution, and vibrational frequency calculations. The matrix-isolated fundamental frequency of the BeF molecule is higher, and the frequency of BeCl is lower, than that determined for the gas-phase molecules. The BeF + and BeCl + cations formed strong dipole-induced dipole complexes in solid Ne, Ar, Kr, and Xe with stepwise increase in computed noble gas dissociation energies. Going down the family NgBeF + and NgBeCl + series (Ng = Ne, Ar, Kr, Xe) the Mulliken charges q(Be) decrease, while q(Ng) increases, and the dipole moments decrease, which suggests covalent bonding in the xenon species. We find that the largest intramatrix shift is Ne to Ar which follows the largest factor increase for the Ng atomic polarizabilities. Extra electrons produce Cl - , which reacts with HCl to form the stable HCl 2 - anion and possibly with BeCl 2 to give BeCl 3 - . A weak band observed in neon experiments with F 2 is probably due to BeF 3 - .

Bismuth heterocycles based on a diphenyl sulfone scaffold: synthesis and substituent effect on the antifungal activity against Saccharomyces cerevisiae.

PubMed

Murafuji, Toshihiro; Fujiwara, Yudai; Yoshimatsu, Daisuke; Miyakawa, Isamu; Migita, Kouto; Mikata, Yuji

2011-02-01

A series of heterocyclic organobismuth(III) compounds 2 [ClBi(5-R-C6H(3)-2-SO2C6H(4)-1'-): R=Me, Ph, MeO, Cl, H, t-Bu, CF3, F, Me2N] was synthesized in order to study the relative importance of structure and specific substitutions in relation to their lipophilicity and antifungal activity against the yeast Saccharomyces cerevisiae. A clear structure-activity relationship between the size of the inhibition zone and the value of ClogP was found for 2. These results suggest that the higher the lipophilicity, the lower the antifungal activity. Thus, 2e (R=H) and 2h (R=F), which had ClogP values of 1.18 and 1.45, respectively, were most active. In contrast, 2b (R=Ph) and 2f (R=t-Bu) had ClogP values of 3.06 and 3.00, respectively, and exhibited no antifungal activity. Compound 6b ClBi[5-(OH)C6H(3)-2-SO(2)-5'-(OH)C6H(3)-1'-] had an estimated ClogP value of 0.81 but exhibited only low activity in spite of its low ClogP value, suggesting that such a considerable decrease in lipophilicity lowers inhibition activity. Bismuth carboxylate 7b derived from p-nitrobenzoic acid and 2e exhibited inhibition activity comparable to those of 2e and 2h despite its higher lipophilicity (ClogP=2.68). Copyright © 2010 Elsevier Masson SAS. All rights reserved.

Synthesis, characterisation and antibacterial activity of [(p-cym)RuX(L)](+/2+) (X = Cl, H2O; L = bpmo, bpms) complexes.

PubMed

Tripathy, Suman Kumar; Taviti, Ashoka Chary; Dehury, Niranjan; Sahoo, Anupam; Pal, Satyanaryan; Beuria, Tushar Kant; Patra, Srikanta

2015-03-21

Mononuclear half-sandwiched complexes [(p-cym)RuCl(bpmo)](ClO4) {[1](ClO4)} and [(p-cym)RuCl(bpms)](PF6) {[2](PF6)} have been prepared by reacting heteroscorpionate ligands bpmo = 2-methoxyphenyl-bis(3,5-dimethylpyrazol-1-yl)methane and bpms = 2-methylthiophenyl-bis(3,5-dimethylpyrazol-1-yl)methane, respectively, with a dimeric precursor complex [(p-cym)RuCl(μ-Cl)]2 (p-cym = 1-isopropyl-4-methylbenzene) in methanol. The corresponding aqua derivatives [(p-cym)Ru(H2O)(bpmo)](ClO4)2 {[3](ClO4)2} and [(p-cym)Ru(H2O)(bpms)](PF6)2 {[4](PF6)2} are obtained from {[1](ClO4)} and {[2](PF6)}, respectively, via Cl(-)/H2O exchange process in the presence of appropriate equivalents of AgClO4/AgNO3 + KPF6 in a methanol-water mixture. The molecular structures of the complexes {[1]Cl, [3](ClO4)2 and [4](PF6)(NO3)} are authenticated by their single crystal X-ray structures. The complexes show the expected piano-stool geometry with p-cym in the η(6) binding mode. The aqua complexes [3](ClO4)2 and [4](PF6)2 show significantly good antibacterial activity towards E. coli (gram negative) and B. subtilis (gram positive) strains, while chloro derivatives ({[1](ClO4)} and {[2](PF6)} are found to be virtually inactive. The order of antibacterial activity of the complexes according to their MIC values is [1](ClO4) (both 1000 μg mL(-1)) < [2](PF6) (580 μg mL(-1) and 750 μg mL(-1)) < [3](ClO4)2 (both 100 μg mL(-1)) < [4](PF6)2 (30 μg mL(-1) and 60 μg mL(-1)) for E. coli and B. subtilis strains, respectively. Further, the aqua complexes [3](ClO4)2 and [4](PF6)2 show clear zones of inhibition against kanamycin, ampicillin and chloramphenicol resistant E. coli strains. The detailed mechanistic aspects of the aforesaid active aqua complexes [3](ClO4)2 and [4](PF6)2 have been explored, and it reveals that both the complexes inhibit the number of nucleoids per cell in vivo and bind to DNA in vitro. The results indeed demonstrate that both [3](ClO4)2 and [4](PF6)2 facilitate the inhibition of bacterial growth by binding to DNA.

Solubility of gold in oxidized, sulfur-bearing fluids at 500-850 °C and 200-230 MPa: A synthetic fluid inclusion study

NASA Astrophysics Data System (ADS)

Guo, Haihao; Audétat, Andreas; Dolejš, David

2018-02-01

Although Au solubility in magmatic-hydrothermal fluids has been investigated by numerous previous studies, there is a dearth of data on oxidized (log fO2 > FMQ+2.5; FMQ - fayalite-magnetite-quartz buffer), sulfur-bearing fluids such as those that formed porphyry Cu-Au (-Mo) deposits. We performed experiments to constrain the effects of fluid salinity, HCl content, sulfur content, fO2 and temperature on Au solubility in such oxidized, sulfur-bearing fluids. For this purpose, small aliquots of fluids equilibrated with Au metal were trapped at high pressure and temperature in the form of synthetic fluid inclusions in quartz and were subsequently analyzed by LA-ICP-MS. Additionally, Raman spectra were collected from quartz-hosted fluid inclusions at up to 600 °C to help to identify the nature of dissolved gold and sulfur species. Gold solubility was found to be affected most strongly by the HCl content of the fluid, followed by fO2, fluid salinity and temperature. Compared to these factors the sulfur content of the fluid has relatively little influence. At 600 °C and 100 MPa, fluids with geologically realistic HCl contents (∼1.1 wt%) and salinities (7-50 wt% NaClequiv) dissolve ∼1000-3000 ppm Au at oxygen fugacities controlled by the magnetite-hematite buffer. At even more oxidized conditions (three log units above the hematite-magnetite fO2 buffer), HCl-, NaCl- and H2SO4-rich fluids can dissolve up to 5 wt% Au at 800 °C and 200 MPa. The observed Au solubility trends are controlled by HCl0 species in the Na-H-Cl-SO4 fluid and are quantitatively reproduced by existing thermodynamic data for Au-Cl complexes. In all experiments, AuCl0 and AuCl2- species are predicted to occur in comparable although variable concentrations, and account for more than 95% of Au solutes. Natural, high-temperature (>500 °C) brine inclusions from porphyry Cu-Au (-Mo) deposits contain significantly less Au than gold-saturated brines that were synthesized experimentally, implying that the natural brines were Au-undersaturated. Consequently, gold grades in Au-rich porphyries were not controlled by the precipitation of native Au, but rather by factors that caused the precipitation of Au-bearing hydrothermal sulfides such as bornite.

Composition of Simulated Martian Brines and Implications for the Origin of Martian Salts

NASA Technical Reports Server (NTRS)

Bullock, M. A.; Moore, J. M.; Mellon, M. T.

2004-01-01

We report on laboratory experiments that have produced dilute brines under controlled conditions meant to simulate past and present Mars. We allowed an SNC-derived mineral mix to react with pure water under a simulated present-Mars atmosphere for seven months. We then subjected the same mineral mix to a similar aqueous environment for one year, but with a simulated Mars atmosphere that contained the added gases SO2, HCl and NO2. The addition of acidic gases was designed to mimic the effects of volcanic gases that may have been present in the martian atmosphere during periods of increased volcanic activity. The experiments were performed at one bar and at two different temperatures in order to simulate subsurface conditions where liquid water and rock are likely to interact on Mars. The dominant cations dissolved in the solutions we produced were Ca(2+), Mg(2+), Al(3+) and Na(+), while the major anions are dissolved C, F(-), SO4(2-) and Cl(-). Typical solution pH was 4.2 to 6.0 for experiments run with a Mars analog atmosphere, and 3.6-5.0 for experiments with acidic gases added. Abundance patterns of elements in the synthetic sulfate-chloride brines produced under acidic conditions were distinctly unlike those of terrestrial ocean water, terrestrial continental waters, and those measured in the martian fines at the Mars Pathfinder and Viking 1 and 2 landing sites. In particular, the S/Cl ratio in these experiments was about 200, compared with an average value of approx. 5 in martian fines. In contrast, abundance patterns of elements in the brines produced under a present day Mars analog atmosphere were quite similar to those measured in the martian fines at the Mars Pathfinder and Viking 1 and 2 landing sites. This suggests that salts present in the martian regolith may have formed over time as a result of the interaction of surface or subsurface liquid water with basalts in the presence of a martian atmosphere similar in composition to that of today, rather than in an atmosphere higher in acidic volatiles.

Spin-Orbit Effect on the Molecular Properties of TeXn (X = F, Cl, Br, and I; n = 1, 2, and 4): A Density Functional Theory and Ab Initio Study.

PubMed

Moon, Jiwon; Kim, Joonghan

2016-09-29

Density functional theory (DFT) and ab initio calculations, including spin-orbit coupling (SOC), were performed to investigate the spin-orbit (SO) effect on the molecular properties of tellurium halides, TeXn (X = F, Cl, Br, and I; n = 1, 2, and 4). SOC elongates the Te-X bond and slightly reduces the vibrational frequencies. Consideration of SOC leads to better agreement with experimental values. Møller-Plesset second-order perturbation theory (MP2) seriously underestimates the Te-X bond lengths. In contrast, B3LYP significantly overestimates them. SO-PBE0 and multireference configuration interactions with the Davidson correction (MRCI+Q), which include SOC via a state-interaction approach, give the Te-I bond length of TeI2 that matches the experimental value. On the basis of the calculated thermochemical energy and optimized molecular structure, TeI4 is unlikely to be stable. The use of PBE0 including SOC is strongly recommended for predicting the molecular properties of Te-containing compounds.

Equatorially connected diruthenium(II,III) units toward paramagnetic supramolecular structures with singular magnetic properties.

PubMed

Barral, M Carmen; Gallo, Teresa; Herrero, Santiago; Jiménez-Aparicio, Reyes; Torres, M Rosario; Urbanos, Francisco A

2006-05-01

The reaction of Ru2Cl(O2CMe)(DPhF)3 (DPhF = N,N'-diphenylformamidinate) with mono- and polycarboxylic acids gives a clean substitution of the acetate ligand, leading to the formation of complexes Ru2Cl(O2CC6H5)(DPhF)3 (1), Ru2Cl(O2CC6H4-p-CN)(DPhF)3 (2), [Ru2Cl(DPhF)3(H2O)]2(O2C)2 (3), [Ru2Cl(DPhF)3]2[C6H4-p-(CO2)2] (4), and [Ru2Cl(DPhF)3]3[C6H3-1,3,5-(CO2)3] (5). The preparation of [Ru2(NCS)(DPhF)3]3[C6H3-1,3,5-(CO2)3] (6) and {[Ru2(DPhF)3(H2O)]3[C6H3-1,3,5-(CO2)3]}(SO3CF3)3 (7) from 5 is also described. All complexes are characterized by elemental analysis, IR and electronic spectroscopy, mass spectrometry, cyclic voltammetry, and variable-temperature magnetic measurements. The crystal structure determinations of complexes 2.0.5THF and 3.THF.4H2O (THF = tetrahydrofuran) are reported. The reactions carried out demonstrate the high chemical stability of the fragment [Ru2(DPhF)3]2+, which is preserved in all tested experimental conditions. The stability of this fragment is also corroborated by the mass spectra. Electrochemical measurements reveal in all complexes one redox process due to the equilibrium Ru2(5+) <--> Ru2(6+). In the polynuclear complex 7, some additional oxidation processes are also observed that have been ascribed to the presence of two types of dimetallic units rather than two consecutive reversible oxidations. The magnetic behavior toward temperature for complexes 1-7 from 300 to 2 K is analyzed. Complexes 1-7 show low values of antiferromagnetic coupling in accordance with the molecular nature in 1 and 2 and the absence of important antiferromagnetic interaction through the carboxylate bridging ligands in 3-7, respectively. In addition, the magnetic properties of complex 7 do not correspond to any magnetic behavior described for diruthenium(II,III) complexes. The experimental data of compound 7 are simulated considering a physical mixture of S = 1/2 and 3/2 spin states. This magnetic study demonstrates the high sensitivity of the electronic configuration of the unit [Ru2(DPhF)3]2+ to small changes in the nature of the axial ligands. Finally, the energy gap between the pi and delta orbitals in these types of compounds allows the tentative assignment of the transition pi --> delta.

Advances in Constraining Solubilities of H-O-C-S-Cl-bearing Fluids in Silicate Melts

NASA Astrophysics Data System (ADS)

Webster, J. D.

2009-12-01

Magmatic-hydrothermal fluids that are variably enriched in the volatile components H2O, CO2/CH4, H2S/SO2, Cl, F, ± B alter rock; dissolve, transport, and deposit ore metals, and drive volcanism. The efficacy of these processes varies directly with the compositions and quantities, and in particular, with the molar volumes of the fluids involved. Although natural hydrothermal fluids are geochemically diverse, experimental constraints on volatile solubilities in silicate melts are largely limited to two volatiles. Recent experimental research, however, has begun to address mutual solubility relationships of three and four volatiles in felsic to intermediate aluminosilicate melts at shallow crustal pressures. Following well-established correlations demonstrating that as little as a few hundred to thousand ppm CO2 or Cl reduce H2O solubility in melts, and hence enhance the tendency for magma to exsolve one or two fluid phases, recent work shows fundamentally important solubility relationships involving H2O, S, and Cl. Research on rhyodacitic (Botcharnikov et al., 2004) and phonolitic melts at 200 MPa reveals that hundreds to thousands of ppm S will reduce Cl solubility in these melts. Thus, S reduces Cl solubility, which in turn reduces H2O solubility in melts. Other investigations have determined that CaSO4 solubility in oxidizing hydrothermal fluids varies directly with the concentrations of NaCl ± KCl in these fluids (Newton and Manning, 2005; Webster et al., 2009). The CaSO4 contents in the most alkali chloride-enriched fluids exceed 60 wt.%. It follows that some mineralizing saline magmatic fluids are strongly enriched in Ca, Na, K, Cl, SO4, and reduced S species. Research on H2O-, CO2-, and Cl-bearing melts at 200 MPa also highlights critical reciprocal volatile solubility behavior. Work at 1200°C on andesitic melts saturated in two fluids determines that the presence of CO2 enlarges the immiscibility gap for vapor plus brine and increases the activities of H2O and Cl (Botcharnikov et al. 2007). Conversely, other work involving Cl-enriched phonolitic melts plus two fluids at 900°C observes that the presence of Cl strongly reduces CO2 solubility in the melt. In fact, for runs containing as much as 80 mole percent CO2 in the fluid, the CO2/CO3 contents of the melts were reduced to values below the limit of detection for FTIR (< ca. 30-40 ppm). Thus, Cl works to reduce CO2 solubility, which in turn reduces H2O solubility in phonolitic melts. Current work on the solubility of H-O-C-S in haplogranitic melts at 200 MPa demonstrates that the addition of C reduces the (fluid/melt) partition coefficient for S. In addition, these experimentally determined partition coefficients decrease in the order CO2 > S > H2O, and their ranges are virtually identical to and thus confirm modeled values computed (Scaillet and Pichavant, 2003) for pre-eruptive magmatic fluids based on volatile fugacities of volcanic gases of arc-related magmas. Botcharnikov R et al (2004) Chem. Geol. 213, 207-225. Botcharnikov R, Holtz F, Behrens H (2007) Eur. J. Mineral. 19, 671-680. Newton R, Manning C (2005) J. Petrol. 46, 701-716. Scaillet B, Pichavant M (2003) Volcanic Degassing, Geol. Soc. Spec. Pub. 213, 23-52. Webster J, Sintoni M, De Vivo B (2009) Chem. Geol. 263, 19-36.

Precipitation chemistry in and ionic loading to an Alpine Basin, Sierra Nevada

NASA Astrophysics Data System (ADS)

Williams, Mark W.; Melack, John M.

1991-07-01

Wet deposition of solutes to an alpine catchment in the southern Sierra Nevada was measured from October 1984 through March 1988. Rainfall had a volume-weighted pH of 4.9, and snowfall had a volume-weighted pH of 5.3. Acetic and formic acids were important components of all wet deposition, contributing 25-30% of the measured anions in snowfall and, through analysis of charge balance deficits, the same percentage in rainfall. The NO3- to SO42- equivalent ratio for all wet deposition was 1.16. Ammonium concentration was tenfold greater than H+ in rainfall; ammonium nitrate and ammonium sulfate appear to be the principal nitrate and sulfate containing aerosols in wet deposition. Snowmelt runoff (1985 and 1986) or snowpack runoff plus rainfall during the period of snowpack runoff (1987) supplied 90% of the annual solute flux from wet deposition to the catchment. The amount of snow water equivalence (mm m-2) and H+, SO42-, and Cl- (eq m-2) in cumulative snowfall measured on snowboards was similar to the accumulated deposition of these parameters measured in snowpils at midwinter and during maximum snow accumulation periods, while about 20% of the NO3- in snowfall was not stored in the winter snowpack. Dry deposition was therefore not an important contributor of H+, NO3-, and SO42- to the winter snowpack. The source of the ions in snowfall was air masses that originated over the Pacific Ocean, while low Cl- and Na+ relative to NO3- and NH4+ in rainfall indicate that local urban and agricultural areas were the major source of the ions in rainfall.

[Effect of developing tourism on chemical characteristic of precipitation: taking Lijiang for example].

PubMed

Zhang, Ning-Ning; He, Yuan-Qing; Wang, Chun-Feng; Pang, Hong-Xi; He, Xian-Zhong

2011-02-01

1090 precipitation samples were collected from 1989 to 2006 at Lijiang City. The analyzed results indicate that the average pH value is 6.08 at study period, which is higher than the average pH value (5.0) during 1987 to 1989, and the annual pH value show an increasing trend, suggesting there are more alkaline mass input to air after 1989. the concentrations of major ions Cl-, SO4(2-), NO3-, Na+, Ca2+, Mg2+ and NH4+ are 11.56, 32.64, 3.63, 2.54, 50.19, 7.73 and 11.36 microeq x L(-1), respectively. By computed the correlation coefficients and sources contribution among major ions, it find that Ca2+ and Mg2+ are from soil-derived sources, and about 57.2% of SO4(2-) also come from soil-derived sources; 95.4% of total NO3- and 41.9% of SO4(2-) come from anthropogenic sources, and only Na+ and 25.7% of Cl- come from sea source, meaning that the chemical composition of precipitation at Lijiang region is main influenced by regional sources. According to the variation of tour scale at Lijiang city, it can be divided into 3 periods of 1987-1989, 1989-1996 and 1997-2006. The percent of soil-derived ions at different periods is 40%, 53% and 72%, respectively, showing a significant increase trend; but the percent of anthropology-derived ions at different periods is 39%, 36% and 15%, respectively, showing a decrease trend. It explains that more dust input to the air by expending city scale, changing the land form and overusing water resources. But in order to develop tourism, the pollutants related to industries are controlled well.

Biogeochemical cycles at the sulfate-methane transition zone (SMTZ) and geochemical characteristics of the pore fluids offshore southwestern Taiwan

NASA Astrophysics Data System (ADS)

Hu, Ching-Yi; Frank Yang, Tsanyao; Burr, George S.; Chuang, Pei-Chuan; Chen, Hsuan-Wen; Walia, Monika; Chen, Nai-Chen; Huang, Yu-Chun; Lin, Saulwood; Wang, Yunshuen; Chung, San-Hsiung; Huang, Chin-Da; Chen, Cheng-Hong

2017-11-01

In this study, we used pore water dissolved inorganic carbon (DIC), SO42-, Ca2+ and Mg2+ gradients at the sulfate-methane transition zone (SMTZ) to estimate biogeochemical fluxes for cored sediments collected offshore SW Taiwan. Net DIC flux changes (ΔDIC-Prod) were applied to determine the proportion of sulfate consumption by organic matter oxidation (heterotrophic sulfate reduction) and anaerobic oxidation of methane (AOM), and to determine reliable CH4 fluxes at the SMTZ. Our results show that SO42- profiles are mainly controlled by AOM rather than heterotrophic sulfate reduction. Refinement of CH4 flux estimates enhance our understanding of methane abundance from deep carbon reservoirs to the SMTZ. Concentrations of chloride (Cl-), bromide (Br-) and iodide (I-) dissolved in pore water were used to identify potential sources that control fluid compositions and the behavior of dissolved ions. Constant Cl- concentrations throughout ∼30 m sediment suggest no influence of gas hydrates for the compositions within the core. Bromide (Br-) and Iodine (I-) concentrations increase with sediment depth. The I-/Br- ratio appears to reflect organic matter degradation. SO42- concentrations decrease with sediment depth at a constant rate, and sediment depth profiles of Br- and I- concentrations suggests diffusion as the main transport mechanism. Therefore diffusive flux calculations are reasonable. Coring sites with high CH4 fluxes are more common in the accretionary wedge, amongst thrust faults and fractures, than in the passive continental margin offshore southwestern Taiwan. AOM reactions are a major sink for CH4 passing upward through the SMTZ and prevent high methane fluxes in the water column and to the atmosphere.

Population pharmacokinetics of levamisole in children with steroid-sensitive nephrotic syndrome

PubMed Central

Kreeftmeijer-Vegter, A R; Dorlo, T P C; Gruppen, M P; de Boer, A; de Vries, P J

2015-01-01

Aim The aim was to investigate the population pharmacokinetics of levamisole in children with steroid-sensitive nephrotic syndrome. Methods Non-linear mixed effects modelling was performed on samples collected during a randomized controlled trial. Samples were collected from children who were receiving 2.5 mg kg–1 levamisole (or placebo) orally once every other day. One hundred and thirty-six plasma samples were collected from 38 children from India and Europe and included in the analysis. A one compartment model described the data well. Results The apparent clearance rate (CL/F) and distribution volume (V/F) were 44 l h–1 70 kg–1 and 236 l 70 kg–1, respectively; estimated interindividual variability was 32–42%. In addition to allometric scaling of CL/F and V/F to body weight, we identified a significant proportional effect of age on CL/F (–10.1% per year). The pharmacokinetics parameters were not affected by gender, tablet strength or study centre. The median (interquartile range) maximum plasma concentration of levamisole was 438.3 (316.5–621.8) ng ml–1, and the median area under the concentration–time curve was 2847 (2267–3761) ng ml–1 h. Median tmax and t½ values were 1.65 (1.32–2.0) h and 2.60 (2.06–3.65) h, respectively. Conclusions Here, we present the first pharmacokinetic data regarding levamisole in children with steroid-sensitive nephrotic syndrome. The pharmacokinetic profile of levamisole in children was similar to findings reported in adults, although the elimination rate was slightly higher in children. PMID:25677380

Chemical characteristics of size-resolved atmospheric aerosols in Iasi, north-eastern Romania: nitrogen-containing inorganic compounds control aerosol chemistry in the area

NASA Astrophysics Data System (ADS)

Giorgiana Galon-Negru, Alina; Iulian Olariu, Romeo; Arsene, Cecilia

2018-04-01

This study assesses the effects of particle size and season on the content of the major inorganic and organic aerosol ionic components in the Iasi urban area, north-eastern Romania. Continuous measurements were carried out over 2016 using a cascade Dekati low-pressure impactor (DLPI) performing aerosol size classification in 13 specific fractions over the 0.0276-9.94 µm size range. Fine-particulate Cl-, NO3-, NH4+, and K+ exhibited clear minima during the warm season and clear maxima over the cold season, mainly due to trends in emission sources, changes in the mixing layer depth and specific meteorological conditions. Fine-particulate SO42- did not show much variation with respect to seasons. Particulate NH4+ and NO3- ions were identified as critical parameters controlling aerosol chemistry in the area, and their measured concentrations in fine-mode (PM2.5) aerosols were found to be in reasonable good agreement with modelled values for winter but not for summer. The likely reason is that NH4NO3 aerosols are lost due to volatility over the warm season. We found that NH4+ in PM2.5 is primarily associated with SO42- and NO3- but not with Cl-. Actually, indirect ISORROPIA-II estimations showed that the atmosphere in the Iasi area might be ammonia rich during both the cold and warm seasons, enabling enough NH3 to be present to neutralize H2SO4, HNO3, and HCl acidic components and to generate fine-particulate ammonium salts, in the form of (NH4)2SO4, NH4NO3, and NH4Cl. ISORROPIA-II runs allowed us to estimate that over the warm season ˜ 35 % of the total analysed samples had very strongly acidic pH (0-3), a fraction that rose to ˜ 43 % over the cold season. Moreover, while in the cold season the acidity is mainly accounted for by inorganic acids, in the warm ones there is an important contribution by other compounds, possibly organic. Indeed, changes in aerosol acidity would most likely impact the gas-particle partitioning of semi-volatile organic acids. Overall, we estimate that within the aerosol mass concentration the ionic mass brings a contribution as high as 40.6 %, with the rest still being unaccounted for.

Chemical characteristics of atmospheric PM2.5 loads during air pollution episodes in Giza, Egypt

NASA Astrophysics Data System (ADS)

Hassan, Salwa K.; Khoder, Mamdouh I.

2017-02-01

Several types of pollution episodes, including dust storm (DSs), haze dust (HDs), straw rice combustions (SRCs) are common phenomena and represent severe environmental hazard in Egypt. This study provides the first comprehensive analysis of the chemical characteristics of aerosol during air pollution episodes at an urban area in Giza, Egypt. PM2.5 samples during various PM episodes during 2013-2014 were collected and analyzed. Results indicate that the highest PM2.5 mass concentrations were found during DSs (250 μg/m3), followed by HDs (130 μg/m3) and SRCs (103 μg/m3). Average PM2.5 mass concentrations were 1.91, 3.68 and 1.68 times higher than on normal days (NDs) during HDs, DSs and SRCs, respectively. The highest total water-soluble ions concentration was 61.1 μg/m3 during HDs, followed by SRCs (41.9 μg/m3) and DSs (35.2 μg/m3). SO42- is the most abundant chemical components on the three PM episodes. Secondary inorganic ions (NO3-, SO42-, and NH4+) were enriched during HDs. The total secondary inorganic ions concentrations were 3.17, 1.39 and 1.75 times higher than NDs during HDs days, DSs days and SRCs days, respectively. PM from SRCs showed high K+ and Cl-. SO42-/K+, NO3-/SO42- and Cl-/K+ ratios proved effective as indicators for different pollution episodes. A Ca2+/Al ratio indicates that soil dust was dominant during DSs. Ion balance calculations indicated that PM2.5 from HDs was acidic, while the DSs and SRCs particles were alkaline and the NDs particle's was nearly neutral. The total crustal and anthropogenic metals concentrations were higher in DSs than other PM episodes and normal days. The enrichment factors values in PM episodes and normal days indicate that Fe and Mn in NDs, HDs, DSs and SRCs as well as Cr and Ni in DSs come mainly from crustal sources, whereas Cr, Ni, Co, Cu, Zn, Pb and Cd in PM episodes and NDs are anthropogenic.

Halocarbons in the stratosphere

NASA Astrophysics Data System (ADS)

Fabian, P.; Borchers, R.

1981-12-01

The possible impact of chlorine compounds on the Earth's ozone layer has caused concern. Profiles of the anthropogenic halocarbons F-11 (CFC13) and F-12 (CF2Cl2) have already been measured in the stratosphere1-4. Measurements of the vertical distribution of methyl chloride (CH3Cl), the most important natural chlorine-bearing species confirm that chlorine of anthropogenic origin now predominates the stratosphere5,6. More halogen radicals are added through decomposition of various other halocarbons, most of them released by man. We report here the first measurements of vertical profiles of F-13 (CF3Cl), F-14 (CF4), F-113 (C2F3Cl3), F-114 (C2F4Cl2), F-115 (C2F5Cl), F-116 (C2F6), and F-13 B(CF3Br) resulting from gas chromatography-mass spectrometer (GC-MS) analysis of air samples collected cryogenically between 10 and 33 km, at 44° N. Some data for F-22 (CHF2C1), methyl bromide (CH3Br) and methyl chloroform (CH3CC13) also presented are subject to confirmation.

Fabrication and characterization of Antheraea pernyi silk fibroin-blended P(LLA-CL) nanofibrous scaffolds for peripheral nerve tissue engineering

NASA Astrophysics Data System (ADS)

Wang, Juan; Sun, Binbin; Bhutto, Muhammad Aqeel; Zhu, Tonghe; Yu, Kui; Bao, Jiayu; Morsi, Yosry; El-Hamshary, Hany; El-Newehy, Mohamed; Mo, Xiumei

2017-03-01

Electrospun nanofibers have gained widespreading interest for tissue engineering application. In the present study, ApF/P(LLA-CL) nanofibrous scaffolds were fabricated via electrospinning. The feasibility of the material as tissue engineering nerve scaffold was investigated in vitro. The average diameter increased with decreasing the blend ratio of ApF to P(LLA-CL). Characterization of 13C NMR and FTIR clarified that there is no obvious chemical bond reaction between ApF and P(LLA-CL). The tensile strength and elongation at break increased with the content increase of P(LLA-CL). The surface hydrophilic property of nanofibrous scaffolds enhanced with the increased content of ApF. Cell viability studies with Schwann cells demonstrated that ApF/P(LLA-CL) blended nanofibrous scaffolds significantly promoted cell growth as compare to P(LLA-CL), especially when the weight ratio of ApF to P(LLA-CL) was 25:75. The present work provides a basis for further studies of this novel nanofibrous material (ApF/P(LLA-CL)) in peripheral nerve tissue repair or regeneration.

Stable isotope analyses of oxygen (18O:17O:16O) and chlorine (37Cl:35Cl) in perchlorate: reference materials, calibrations, methods, and interferences

USGS Publications Warehouse

Böhlke, John Karl; Mroczkowski, Stanley J.; Sturchio, Neil C.; Heraty, Linnea J.; Richman, Kent W.; Sullivan, Donald B.; Griffith, Kris N.; Gu, Baohua; Hatzinger, Paul B.

2017-01-01

RationalePerchlorate (ClO4−) is a common trace constituent of water, soils, and plants; it has both natural and synthetic sources and is subject to biodegradation. The stable isotope ratios of Cl and O provide three independent quantities for ClO4− source attribution and natural attenuation studies: δ37Cl, δ18O, and δ17O (or Δ17O or 17Δ) values. Documented reference materials, calibration schemes, methods, and interferences will improve the reliability of such studies.MethodsThree large batches of KClO4 with contrasting isotopic compositions were synthesized and analyzed against VSMOW-SLAP, atmospheric O2, and international nitrate and chloride reference materials. Three analytical methods were tested for O isotopes: conversion of ClO4− to CO for continuous-flow IRMS (CO-CFIRMS), decomposition to O2 for dual-inlet IRMS (O2-DIIRMS), and decomposition to O2 with molecular-sieve trap (O2-DIIRMS+T). For Cl isotopes, KCl produced by thermal decomposition of KClO4 was reprecipitated as AgCl and converted into CH3Cl for DIIRMS.ResultsKClO4 isotopic reference materials (USGS37, USGS38, USGS39) represent a wide range of Cl and O isotopic compositions, including non-mass-dependent O isotopic variation. Isotopic fractionation and exchange can affect O isotope analyses of ClO4− depending on the decomposition method. Routine analyses can be adjusted for such effects by normalization, using reference materials prepared and analyzed as samples. Analytical errors caused by SO42−, NO3−, ReO42−, and C-bearing contaminants include isotope mixing and fractionation effects on CO and O2, plus direct interference from CO2 in the mass spectrometer. The results highlight the importance of effective purification of ClO4− from environmental samples.ConclusionsKClO4 reference materials are available for testing methods and calibrating isotopic data for ClO4− and other substances with widely varying Cl or O isotopic compositions. Current ClO4−extraction, purification, and analysis techniques provide relative isotope-ratio measurements with uncertainties much smaller than the range of values in environmental ClO4−, permitting isotopic evaluation of environmental ClO4− sources and natural attenuation.

A versatile tripodal amide receptor for the encapsulation of anions or hydrated anions via formation of dimeric capsules.

PubMed

Arunachalam, M; Ghosh, Pradyut

2010-02-01

A bowl-shaped tripodal receptor with an appropriately positioned amide functionality on the benzene platform and electron-withdrawing p-nitrophenyl terminals (L(1)) has been designed, synthesized, and studied for the anion binding properties. The single-crystal X-ray crystallographic analysis on crystals of L(1) with tetrabutylammonium salts of nitrate (1), acetate (2), fluoride (3), and chloride (4) obtained in moist dioxane medium showed encapsulation of two NO(3)(-), [(AcO)(2)(H(2)O)(4)](2-), [F(2)(H(2)O)(6)](2-), and [Cl(2)(H(2)O)(4)](2-) respectively as the anionic guests inside the staggered dimeric capsular assembly of L(1). The p-nitro substitution in the aryl terminals assisted the formation of dimeric capsular assembly of L(1) exclusively upon binding/encapsulating above different guests. Though L(1) demonstrates capsule formation upon anion or hydrated anion complexation for all of the anions studied here, its positional isomer with the o-nitro-substituted tripodal triamide receptor L(2) selectively formed the dimeric capsular assembly upon encapsulation of [F(2)(H(2)O)(6)](2-) and noncapsular aggregates in the cases of other anions such as Cl(-), NO(3)(-), and AcO(-). Interestingly, structural investigations upon anion exchange of the complexes revealed that both isomers have selectivity toward the formation of a [F(2)(H(2)O)(6)](2-) encapsulated dimeric capsule. In contrast, solution-state (1)H NMR titration studies of L(1) and L(2) in DMSO-d(6) with AcO(-) indicated 1:3 (host:guest) binding.

Impact of Climate Variability on the Hydrogeochemistry of Ecologically Important Prairie Wetlands and Lakes

NASA Astrophysics Data System (ADS)

Goldhaber, M. B.; Mills, C. T.; Mushet, D. M.; Stricker, C. A.; Rover, J.

2015-12-01

The Prairie Pothole region encompasses 715,000 km2 of the north central US and south central Canada and contains millions of small wetlands and lakes. It sustains large populations of shore birds and migratory waterfowl. PPR ecology is influenced by wetland geochemistry, which can range dramatically over short distances (≤ 200m) from dilute Ca2+-HCO3- to saline Na+-Mg2+-SO42- compositions. These compositional differences result, in part, from long-term critical zone processes in upland areas coupled to groundwater inflow, but they are also influenced by climate. Climate impacts on the geochemistry of 167 wetlands/lakes from a 9700 km2 area of North Dakota (USA) were studied. The chemical composition of these wetlands was determined in the early 1970's during slightly dry climatic conditions and again in 2012-2013, a period of exceptional precipitation. Dilution dominated wetland geochemical trends. Concentrations of Cl-, Na+, K+, and Mg2+ generally decreased in 2012-2013 compared to earlier data. In contrast Ca2+ increased, and SO42- change was variable. The processes driving these modifications were evaluated using inverse (mass balance based) geochemical modeling. The decrease in the largely inert ion, Na+ by rainwater addition was used to approximate the net dilution factor of the wetlands which ranged to >9. This volume increase was associated with large expansions of wetland area determined from time-series Landsat data. Introducing dissolution of authigenic CaCO3, a known constituent of wetland sediments, matched the observed Ca2+ increase. Addition of SO42--enriched groundwater (composition determined from well analyses) was required to model wetlands with increased SO42-. Those wetlands with increased SO42- had more negative δ34SSO4 values, a result consistent with a previously established isotopically light marine pyrite source for groundwater SO42-. Understanding the evolution of wetland chemistry may aid in assessing future climatic impacts to the PPR.

Evaluation of shallow sediment methane cycling in a pockmark field on the Chatham Rise, New Zealand

NASA Astrophysics Data System (ADS)

Coffin, R. B.; Rose, P. S.; Klaucke, I.; Bialas, J.; Pecher, I. A.; Gorman, A. R.

2014-12-01

Seismic studies have identified an extensive field (>20,000 km2) of seafloor depressions, or pockmarks, on the southwestern flank of the Chatham Rise, New Zealand. It has been suggested that these pockmarks result from gas hydrate dissociation linked to sea-level changes during glacial-interglacial cycles. Gas hydrates are predominately composed of methane (CH4), a potent greenhouse gas. Surface sediment cores (~ 8 m) were collected from the pockmark field on the Chatham Rise during a research cruise in February 2013 to evaluate the association of the features with CH4 releases. A suite of geochemical parameters are interpreted to determine the methane contribution to solid phase sediment and pore water. The upward flux of CH4 in sediments is often quantified using pore water sulfate (SO42-) profiles, assuming steady-state consumption of SO42- and CH4 by anaerobic oxidation of methane (AOM): CH4 + SO42- → HCO3- + HS- + H2O. This reaction is one of the primary controls on CH4 distributions in sediments. This work will present pore water SO42-, sulfide (HS-) and chloride (Cl-) depth profiles in sediment collected from the pockmark field. Theoretical SO42- distributions in the absence of AOM are compared to observed SO42- profiles as a preliminary assessment of the influence of CH4 on sediment geochemistry in and around the seafloor depressions. In addition isotopically-light CH4 is incorporated into sediment carbon pools via AOM and subsequent CO2 fixation. Stable carbon isotope distributions in the organic and inorganic carbon pools are presented to determine the influence of CH4 in sediments in the vicinty of the pockmarks. Collectively, the geochemical data are used to assess the role of gas hydate dissociation in pockmark formation on the Chatham Rise. Despite sesimic data interpretation in this region there is no modern day contribution of CH4 to shallow sediment carbon cycling and data are presented to assess paleogeochemical methane cycling.

Field performance of a semi-continuous monitor for ambient PM2.5 water-soluble inorganic ions and gases at a suburban site

NASA Astrophysics Data System (ADS)

Young, Li-Hao; Li, Chiao-Hsin; Lin, Ming-Yeng; Hwang, Bing-Fang; Hsu, Hui-Tsung; Chen, Yu-Cheng; Jung, Chau-Ren; Chen, Kuan-Chi; Cheng, Dung-Hung; Wang, Ven-Shing; Chiang, Hung-Che; Tsai, Perng-Jy

2016-11-01

To reduce sampling artifacts and to improve time-resolved measurements of inorganic aerosol system, a recently commercialized semi-continuous In-situ Gas and Aerosol Composition (IGAC) monitoring system was evaluated against a reference annular denuder system (ADS; denuder/two-stage filter pack) at a suburban site over a year, during which the average PM2.5 was 37.0 ± 24.8 μg/m3. A suite of eight ions SO42-, NO3-, Cl-, NH4+, Na+, K+, Ca2+ and Mg2+ and two gases SO2 and NH3 were the target species. In comparison to the reference ADS method, the IGAC performed well in measuring the major ions SO42-, NO3- and NH4+, and the SO2. For those species, the linear slopes, intercepts and R2 values between the two methods all passed the performance evaluation criteria outlined by earlier similar studies. The performance of IGAC on Cl-, Na+, K+ and NH3 was marginally acceptable, whereas Ca2+ and Mg2+ could not be properly evaluated due to the low concentrations (<0.2 μg/m3) and hence inadequate amount of sample size. The ionic balance of the hourly IGAC samples averaged very close to unity, as did the daily ADS samples, though the former was considerably more variable than the latter. The overall performance of the IGAC has been shown to be comparable to other similar monitors and its improvements are discussed.

Properties of fluorosulfate-based ionic liquids and geometries of (FO2SOH)OSO2F- and (FO2SOH)2O2SOF-.

PubMed

Enomoto, Takeshi; Matsumoto, Kazuhiko; Hagiwara, Rika

2011-12-14

A room temperature ionic liquid (IL) based on the fluorosulfate anion (SO(3)F(-)) has been synthesized by the reaction of 1-ethyl-3-methylimidazolium (EMIm(+)) chloride and fluorosulfuric acid (HOSO(2)F). The viscosity, ionic conductivity, and electrochemical window of EMImSO(3)F at 25 °C are 46.6 mPa s, 10.8 mS cm(-1), and 4.3 V, respectively. According to a solvatochromic measurement using ILs, there is a trend in the donor ability of fluoro- and oxofluoroanions, PF(6)(-) < BF(4)(-) < N(SO(2)CF(3))(2)(-) < SO(3)CF(3)(-) < SO(3)F(-) < PO(2)F(2)(-), which is explained by the atomic charges obtained from quantum mechanical calculations. The 1 : 2 and 1 : 3 stoichiometric reactions of EMImCl and HOSO(2)F give EMIm(FO(2)SOH)OSO(2)F and EMIm(FO(2)SOH)(2)O(2)SOF, respectively. Both the salts are liquid at room temperature without a HOSO(2)F dissociation pressure (< 1 Pa) and have low viscosity and high ionic conductivity (9.2 mPa s and 30.8 mS cm(-1) for EMIm(FO(2)SOH)OSO(2)F and 5.1 mPa s and 43.2 mS cm(-1) for EMIm(FO(2)SOH)(2)O(2)SOF). The vibrational modes and bonding properties of these anionic species are discussed with the aid of quantum mechanical calculations. The (FO(2)SOH)OSO(2)F(-) anion in EMIm(FO(2)SOH)OSO(2)F does not have an inversion centre, which stands in contrast to the one with an inversion centre (e.g. observed in solid Cs(FO(2)SOH)OSO(2)F). The (FO(2)SOH)(2)O(2)SOF(-) anion in EMIm(FO(2)SOH)(2)O(2)SOF is characterized by vibrational spectroscopy under C(s) symmetry.

Weekday/weekend differences in ambient aerosol level and chemical characteristics of water-soluble components in the city centre

NASA Astrophysics Data System (ADS)

Khoder, M. I.; Hassan, S. K.

Weekday and weekend ambient aerosol samples were collected from the city centre of Cairo, namely "Ramsis" during the summer season of the year 2006, and have been analyzed for water-soluble ionic species. The average concentrations of the total suspended particulate matter (TSP) and their water-soluble components were higher during weekdays than on weekends, indicating that the decreased traffic density on weekends leads to a decrease in the levels of the TSP and their water-soluble ionic species. The average concentrations of the TSP were 454 μg m -3 on weekdays and 298 μg m -3 on weekends. The weekday/weekend concentration ratios were 1.52 for TSP, 1.27 for SO 42-, 1.64 for Cl -, 1.54 for NO 3-, 1.17 for NH 4+, 1.67 for Ca 2+, 1.83 for Na +, 1.75 for K + and 1.73 for Mg 2+. City centre of Cairo has high levels of the TSP and their water-soluble ionic species compared with many polluted cities in the world. Among all of the measured water-soluble components, SO 42- was the most abundant species followed by Ca 2+ on weekdays and weekends. The average mass ratios of NO 3-/SO 42- in the TSP were 0.41 on weekdays and 0.34 on weekends, suggesting that the stationary source emissions were more predominant. The NH 4+/SO 42- molar ratios and its relation with the concentrations of TSP and Ca 2+ during the weekdays and weekends indicate that the chemical form of sulfate and ammonium in aerosol particles varies with TSP and Ca 2+ levels. At high TSP and Ca 2+ levels, and NH 4+/SO 42- molar ratios less than one, SO 42- in aerosol particles may be present as CaSO 4 and (NH 4) 2SO 4·CaSO 4·2H 2O, whereas it is expected to be present as (NH 4) 2SO 4, (NH 4) 2SO 4·CaSO 4·2H 2O and CaSO 4 at low levels of TSP and Ca 2+, and NH 4+/SO 42- molar ratios between 1 and 2. The mean pH values of the TSP were 7.65 on weekdays and 6.97 on weekends, indicating that aerosol particles brought a large amount of crustal species, and might alleviate the tendency of acidification. The relationships between the concentrations of acidic components (NO 3- and SO 42-) and basic components (NH 4+, Ca 2+ and Mg 2+) on weekdays and weekends indicate that the acidity of aerosol particles is neutralized. Ca 2+ and NH 4+ are the most dominant neutralization substances in Cairo atmosphere.

Crystal structure, quantum mechanical investigation, IR and NMR spectroscopy of two new organic salts: (C8H12NO)·[NO3] (I) and (C8H14N4)·[ClO4]2 (II)

NASA Astrophysics Data System (ADS)

Bayar, I.; Khedhiri, L.; Soudani, S.; Lefebvre, F.; Pereira da Silva, P. S.; Ben Nasr, C.

2018-06-01

Two new organic-inorganic hybrid materials, 4-methoxybenzylammonium nitrate, (C8H12NO)·[NO3] (I), and 2-(1-piperazinyl)pyrimidinium bis(perchlorate), (C8H14N4)·[ClO4]2(II), have been synthesized by an acid/base reaction at room temperature, their structures were determined by single crystal X-ray diffraction. Compound (I) crystallizes in the orthorhombic system and Pnma space group with a = 15.7908 (7), b = 6.8032 (3), c = 8.7091 (4) Å, V = 935.60 (7) Å3 with Z = 4. Full-matrix least-squares refinement converged at R = 0.038 and wR(F2) = 0.115. Compound (II) belongs to the monoclinic system, space group P21/c with the following parameters: a = 10.798(2), b = 7.330(1), c = 21.186(2) Å, β = 120.641 (4)°, V = 1442.7 (3) Å3and Z = 4. The structure was refined to R = 0.044, wR(F2) = 0.132. In the structures of (I) and (II), the anionic and cationic entities are interconnected by hydrogen bonding contacts forming three-dimensional networks. Intermolecular interactions were investigated by Hirshfeld surfaces and the contacts of the four different chloride atoms in (II) were compared. The Molecular Electrostatic Potential (MEP) maps and the HOMO and LUMO energy gaps of both compounds were computed. The vibrational absorption bands were identified by infrared spectroscopy. These compounds were also investigated by solid-state 13C, 35Cl and 15N NMR spectroscopy. DFT calculations allowed the attribution of the IR and NMR bands.

Improved process for generating ClF/sub 3/ from ClF and F/sub 2/

DOEpatents

Reiner, R.H.; Pashley, J.H.; Barber, E.J.

The invention is an improvement in the process for producing gaseous ClF/sub 3/ by reacting ClF and F/sub 2/ at elevated temperature. The improved process comprises conducting the reaction in the presence of NiF/sub 2/, which preferably is in the form of particles or in the form of a film or layer on a particulate substrate. The nickel fluoride acts as a reaction catalyst, significantly increasing the reaction rate and thus permitting valuable reductions in process temperature, pressure, and/or reactor volume.

Solid polymer electrolytes

DOEpatents

Abraham, Kuzhikalail M.; Alamgir, Mohamed; Choe, Hyoun S.

1995-01-01

This invention relates to Li ion (Li.sup.+) conductive solid polymer electrolytes composed of poly(vinyl sulfone) and lithium salts, and their use in all-solid-state rechargeable lithium ion batteries. The lithium salts comprise low lattice energy lithium salts such as LiN(CF.sub.3 SO.sub.2).sub.2, LiAsF.sub.6, and LiClO.sub.4.

Tularosa Basin Play Fairway Analysis: Water Chemistry

DOE Data Explorer

Adam Brandt

2015-12-15

This shapefile contains 409 well data points on Tularosa Basin Water Chemistry, each of which have a location (UTM), temperature, quartz and Potassium/Magnesium geothermometer; as well as concentrations of chemicals like Mn, Fe, Ba, Sr, Cs, Rb, As, NH4, HCO3, SO4, F, Cl, B, SiO2, Mg, Ca, K, Na, and Li.

Downstream composition changes of acidic volcanic waters discharged into the Banyupahit stream, Ijen caldera, Indonesia

NASA Astrophysics Data System (ADS)

Delmelle, P.; Bernard, A.

2000-04-01

The crater lake of Kawah Ijen volcano contains extremely low pH (<0.4) waters with high SO4 (∼70000 mg/kg), Cl (∼21000 mg/kg), F (∼1500 mg/kg), Al (∼5000 mg/kg), Fe (∼2000 mg/kg) and trace metal (Cu ∼0.5, Zn ∼4, Pb ∼3 mg/kg) contents. These brines seep outward through the western crater rim and reappear on the other side as streamlets, which form the headwaters of the Banyupahit stream. The Banyupahit first mixes with fresh rivers and thermal springs in the Ijen caldera and then irrigates a coastal agricultural plain which is 30 km from the summit crater. We discuss the downstream composition changes affecting the Banyupahit waters by using stable isotope, chemical and mineralogical data collected from sites along the stream length. The saturation of the stream waters with respect to minerals was evaluated with SOLVEQ and WATEQ4F and compared with the geochemical observations. An aluminous mineralogy (alunogen, pickeringite, tamarugite and kalinite) develops in the upper part of the Banyupahit due to concentration of the headwaters by evaporation. Downstream attenuation of dissolved element concentrations results principally from dilution and from mineral precipitation. The stream pH changes from ∼0 at the source to >4 close to the mouth. The δD and δ18O values and the relative SO4-Cl-F contents of the Banyupahit waters indicate that the tributaries are mostly meteoric. Dissolved SO4 in the acidic stream come only from the crater lake seepages and are not involved later in microbially mediated reactions, as shown by their δ34S and δ18O values. Re-equilibration of the stream SO4 oxygen-isotope composition with H2O from tributaries does not occur. Calcium, SiO2, Al, Fe, K and SO4 behave non-conservatively in the stream waters. Gypsum, silica (amorphous or poorly ordered), a basic aluminum hydroxysulfate (basaluminite?), K-jarosite and amorphous ferric hydroxide may exert a solubility control on these elements along the entire stream length, or in certain stream sections, consistent with the thermochemical model results. Downstream concentration trends and mineral saturation levels suggest that precipitation of Sr-, Pb-rich barite and celestite consume Ba, Sr and Pb, whereas dissolved Cu, Pb and Zn may adsorb onto solid particles, especially after the junctions of the acidic stream with non-acidic rivers. We calculated that significant fluxes of SO4, F, Cl, Al, SiO2, Ti, Mn and Cu may reach the irrigation system, possibly causing serious environmental impacts such as soil acidification and induration.

Selective detection of pyrophosphate anion by a simple Cd(II) based terpyridine complex

NASA Astrophysics Data System (ADS)

Purohit, Aditya Kumar; Ghosh, Biswa Nath; Kar, Pravin Kumar

2018-01-01

A simple ratiometric terpyridine-Cd(ll) complex was synthesized by the treatment of CdCl2 with terpyridine ligand 4‧-(4-N,N‧-dimethylaminophenyl)-2,2‧:6‧,2″-terpyridine. The synthesized complex was found to act as a selective fluorescent chemosensor for pyrophosphate P2O74 - (PPi) over other anions like F-, Cl-, Br-, CO32 -, SO32 -, AcO-, NO2-, and H2PO4-. Furthermore, the receptor probe was also successfully employed in HeLa cell for PPi detection, which indicates this can be used as a chemosensor for cells.

Physicochemical quality evaluation of groundwater and development of drinking water quality index for Araniar River Basin, Tamil Nadu, India.

PubMed

Jasmin, I; Mallikarjuna, P

2014-02-01

Groundwater is the most important natural resource which cannot be optimally used and sustained unless its quality is properly assessed. In the present study, the spatial and temporal variations in physicochemical quality parameters of groundwater of Araniar River Basin, India were analyzed to determine its suitability for drinking purpose through development of drinking water quality index (DWQI) maps of the post- and pre-monsoon periods. The suitability for drinking purpose was evaluated by comparing the physicochemical parameters of groundwater in the study area with drinking water standards prescribed by the World Health Organization (WHO) and Bureau of Indian Standards (BIS). Interpretation of physicochemical data revealed that groundwater in the basin was slightly alkaline. The cations such as sodium (Na(+)) and potassium (K(+)) and anions such as bicarbonate (HCO3 (-)) and chloride (Cl(-)) exceeded the permissible limits of drinking water standards (WHO and BIS) in certain pockets in the northeastern part of the basin during the pre-monsoon period. The higher total dissolved solids (TDS) concentration was observed in the northeastern part of the basin, and the parameters such as calcium (Ca(2+)), magnesium (Mg(2+)), sulfate (SO4 (2-)), nitrate (NO3 (-)), and fluoride (F(-)) were within the limits in both the seasons. The hydrogeochemical evaluation of groundwater of the basin demonstrated with the Piper trilinear diagram indicated that the groundwater samples of the area were of Ca(2+)-Mg(2+)-Cl(-)-SO4 (2-), Ca(2+)-Mg(2+)-HCO3 (-) and Na(+)-K(+)-Cl(-)-SO4 (2-) types during the post-monsoon period and Ca(2+)-Mg(2+)-Cl(-)-SO4 (2-), Na(+)-K(+)-Cl(-)-SO4 (2-) and Ca(2+)-Mg(2+)-HCO3 (-) types during the pre-monsoon period. The DWQI maps for the basin revealed that 90.24 and 73.46% of the basin area possess good quality drinking water during the post- and pre-monsoon seasons, respectively.

Towards a better prediction of peak concentration, volume of distribution and half-life after oral drug administration in man, using allometry.

PubMed

Sinha, Vikash K; Vaarties, Karin; De Buck, Stefan S; Fenu, Luca A; Nijsen, Marjoleen; Gilissen, Ron A H J; Sanderson, Wendy; Van Uytsel, Kelly; Hoeben, Eva; Van Peer, Achiel; Mackie, Claire E; Smit, Johan W

2011-05-01

It is imperative that new drugs demonstrate adequate pharmacokinetic properties, allowing an optimal safety margin and convenient dosing regimens in clinical practice, which then lead to better patient compliance. Such pharmacokinetic properties include suitable peak (maximum) plasma drug concentration (C(max)), area under the plasma concentration-time curve (AUC) and a suitable half-life (t(½)). The C(max) and t(½) following oral drug administration are functions of the oral clearance (CL/F) and apparent volume of distribution during the terminal phase by the oral route (V(z)/F), each of which may be predicted and combined to estimate C(max) and t(½). Allometric scaling is a widely used methodology in the pharmaceutical industry to predict human pharmacokinetic parameters such as clearance and volume of distribution. In our previous published work, we have evaluated the use of allometry for prediction of CL/F and AUC. In this paper we describe the evaluation of different allometric scaling approaches for the prediction of C(max), V(z)/F and t(½) after oral drug administration in man. Twenty-nine compounds developed at Janssen Research and Development (a division of Janssen Pharmaceutica NV), covering a wide range of physicochemical and pharmacokinetic properties, were selected. The C(max) following oral dosing of a compound was predicted using (i) simple allometry alone; (ii) simple allometry along with correction factors such as plasma protein binding (PPB), maximum life-span potential or brain weight (reverse rule of exponents, unbound C(max) approach); and (iii) an indirect approach using allometrically predicted CL/F and V(z)/F and absorption rate constant (k(a)). The k(a) was estimated from (i) in vivo pharmacokinetic experiments in preclinical species; and (ii) predicted effective permeability in man (P(eff)), using a Caco-2 permeability assay. The V(z)/F was predicted using allometric scaling with or without PPB correction. The t(½) was estimated from the allometrically predicted parameters CL/F and V(z)/F. Predictions were deemed adequate when errors were within a 2-fold range. C(max) and t(½) could be predicted within a 2-fold error range for 59% and 66% of the tested compounds, respectively, using allometrically predicted CL/F and V(z)/F. The best predictions for C(max) were obtained when k(a) values were calculated from the Caco-2 permeability assay. The V(z)/F was predicted within a 2-fold error range for 72% of compounds when PPB correction was applied as the correction factor for scaling. We conclude that (i) C(max) and t(½) are best predicted by indirect scaling approaches (using allometrically predicted CL/F and V(z)/F and accounting for k(a) derived from permeability assay); and (ii) the PPB is an important correction factor for the prediction of V(z)/F by using allometric scaling. Furthermore, additional work is warranted to understand the mechanisms governing the processes underlying determination of C(max) so that the empirical approaches can be fine-tuned further.

Mimicking the cell membrane: bio-inspired simultaneous functions with monovalent anion selectivity and antifouling properties of anion exchange membrane

NASA Astrophysics Data System (ADS)

Zhao, Yan; Liu, Huimin; Tang, Kaini; Jin, Yali; Pan, Jiefeng; der Bruggen, Bart Van; Shen, Jiangnan; Gao, Congjie

2016-11-01

A new bio-inspired method was applied in this study to simultaneously improve the monovalent anion selectivity and antifouling properties of anion exchange membranes (AEMs). Three-layer architecture was developed by deposition of polydopamine (PDA) and electro-deposition of N-O-sulfonic acid benzyl chitosan (NSBC). The innermost and outermost layers were PDA with different deposition time. The middle layer was prepared by NSBC. Fourier transform infrared spectroscopy and scanning electron microscopy confirmed that PDA and NSBC were successfully modified on the surfaces of AEMs. The contact angle of the membranes indicated an improved hydrophilicity of the modified membranes. A series of electrodialysis experiments in which Cl-/SO42- separation was studied, demonstrating the monovalent anion selectivity of the samples. The Cl-/SO42- permselectivity of the modified membranes can reach up to 2.20, higher than that of the commercial membrane (only 0.78) during 90 minutes in electrodialysis (ED). The increase value of the resistance of the membranes was also measured to evaluate the antifouling properties. Sodium dodecyl benzene sulfonate (SDBS) was used as the fouling material in the ED process and the membrane area resistance of modified membrane increase value of was only 0.08 Ωcm2 30 minutes later.

The influence of continental air masses on the aerosols and nutrients deposition over the western North Pacific

NASA Astrophysics Data System (ADS)

Fu, Jiangping; Wang, Bo; Chen, Ying; Ma, Qingwei

2018-01-01

The air masses transported from East Asia have a strong impact on the aerosol properties and deposition in the marine boundary layer of the western North Pacific (WNP) during winter and spring. We joined a cruise between 17 Mar. and 22 Apr. 2014 and investigated the changes of aerosol composition and size distribution over the remote WNP and marginal seas. Although the secondary aerosol species (SO42-, NO3- and NH4+) in remote WNP were influenced significantly by the continental transport, NH4+ concentrations were lower than 2.7 μg m-3 in most sampling days and not correlated with non-sea-salt (nss)-SO42- suggesting that the ocean could be a primary source of NH4+. Moderate Cl- depletion (23%) was observed in remote WNP, and the inverse relationship between Cl- depletion percentages and nss-K+ in aerosols suggested that the transport of biomass burning smoke from East Asia might be a vital extra source of Cl-. Both Asian dust and haze events were encountered during the cruise. Asian dust carried large amounts of crustal elements such as Al and Ti to the WNP, and the dusty Fe deposition may double its background concentration in seawater. Differently, a dramatic increase of dry deposition flux of dissolved particulate inorganic nitrogen was observed during the haze event. Our study reveals that the transport of different continental air masses may have distinct biogeochemical impacts on the WNP by increasing the fluxes of different nutrient elements and potentially changing the nutrient stoichiometry.

Fluorine and chlorine in mantle minerals and the halogen budget of the Earth's mantle

NASA Astrophysics Data System (ADS)

Urann, B. M.; Le Roux, V.; Hammond, K.; Marschall, H. R.; Lee, C.-T. A.; Monteleone, B. D.

2017-07-01

The fluorine (F) and chlorine (Cl) contents of arc magmas have been used to track the composition of subducted components, and the F and Cl contents of MORB have been used to estimate the halogen content of depleted MORB mantle (DMM). Yet, the F and Cl budget of the Earth's upper mantle and their distribution in peridotite minerals remain to be constrained. Here, we developed a method to measure low concentrations of halogens (≥0.4 µg/g F and ≥0.3 µg/g Cl) in minerals by secondary ion mass spectroscopy. We present a comprehensive study of F and Cl in co-existing natural olivine, orthopyroxene, clinopyroxene, and amphibole in seventeen samples from different tectonic settings. We support the hypothesis that F in olivine is controlled by melt polymerization, and that F in pyroxene is controlled by their Na and Al contents, with some effect of melt polymerization. We infer that Cl compatibility ranks as follows: amphibole > clinopyroxene > olivine orthopyroxene, while F compatibility ranks as follows: amphibole > clinopyroxene > orthopyroxene ≥ olivine, depending on the tectonic context. In addition, we show that F, Cl, Be and B are correlated in pyroxenes and amphibole. F and Cl variations suggest that interaction with slab melts and fluids can significantly alter the halogen content of mantle minerals. In particular, F in oceanic peridotites is mostly hosted in pyroxenes, and proportionally increases in olivine in subduction-related peridotites. The mantle wedge is likely enriched in F compared to un-metasomatized mantle, while Cl is always low (<1 µg/g) in all tectonic settings studied here. The bulk anhydrous peridotite mantle contains 1.4-31 µg/g F and 0.14-0.38 µg/g Cl. The bulk F content of oceanic-like peridotites (2.1-9.4 µg/g) is lower than DMM estimates, consistent with F-rich eclogite in the source of MORB. Furthermore, the bulk Cl budget of all anhydrous peridotites studied here is lower than previous DMM estimates. Our results indicate that nearly all MORB may be somewhat contaminated by seawater-rich material and that the Cl content of DMM could be overestimated. With this study, we demonstrate that the halogen contents of natural peridotite minerals are a unique tool to understand the cycling of halogens, from ridge settings to subduction zones.

High-level expression of a novel chromoplast phosphate transporter ClPHT4;2 is required for flesh color development in watermelon.

PubMed

Zhang, Jie; Guo, Shaogui; Ren, Yi; Zhang, Haiying; Gong, Guoyi; Zhou, Ming; Wang, Guizhang; Zong, Mei; He, Hongju; Liu, Fan; Xu, Yong

2017-02-01

Chromoplast development plays a crucial role in controlling carotenoid content in watermelon flesh. Modern cultivated watermelons with colorful flesh are believed to originate from pale-colored and no-sweet progenitors. But the molecular basis of flesh color formation and regulation is poorly understood. More chromoplasts and released carotenoid globules were observed in the red-fleshed fruit of the 97103 cultivar than in the pale-colored fruits of the PI296341-FR line. Transcriptome profiles of these two materials identified Cla017962, predicted as ClPHT4;2, was dramatically up-regulated during flesh color formation. High ClPHT4;2 expression levels were closely correlated with increased flesh carotenoid contents among 198 representative watermelon accessions. Down-regulation of ClPHT4;2 expression in transgenic watermelons reduced the fruit carotenoid accumulation. ClPHT4;2 as a function of chromoplast-localized phosophate transporter was tested by heterologous expression into a yeast phosphate-uptake-defective mutant, western blotting, subcellular localization, and immunogold electron microscopy analysis. Two transcription factors, ClbZIP1 and ClbZIP2, were identified, which responded to ABA and sugar signaling to regulate ClPHT4;2 transcription only in cultivated watermelon species. Our findings suggest that elevated ClPHT4;2 gene expression is necessary for carotenoid accumulation, and may help to characterize the co-development of flesh color and sweetness during watermelon development and domestication. © 2016 The Authors. New Phytologist © 2016 New Phytologist Trust.

Activation barriers for series of exothermic homologous reactions. V. Boron group diatomic species reactions

NASA Astrophysics Data System (ADS)

Blue, Alan S.; Belyung, David P.; Fontijn, Arthur

1997-09-01

Semiempirical configuration interaction (SECI) theory is used to predict activation barriers E, as defined by k(T)=ATn exp(-E/RT). Previously SECI has been applied to homologous series of oxidation reactions of s1, s2, and s2p1 metal atoms. Here it is extended to oxidation reactions of diatomic molecules containing one s2p1 atom. E values are calculated for the reactions of BH, BF, BCl, AlF, AlCl, AlBr, GaF, GaI, InCl, InBr, InI, TlF, TlCl, TlBr, and TlI with O2, CO2, SO2, or N2O. These values correlate with the sums of the ionization potentials and Σ-Π promotion energies of the former minus the electron affinities of the latter. In the earlier work n was chosen somewhat arbitrarily, which affected the absolute values of E. Here it is shown that examination of available experimental and theoretical results allows determination of the best values of n. Using this approach yields n=1.9 for the present series. For the seven reactions which have been studied experimentally, the average deviation of the SECI activation barrier prediction from experiment is 4.0 kJ mol-1. Energy barriers are calculated for another 52 reactions.

Prevalence of liver fluke infection in Irish horses and assessment of a serological test for diagnosis of equine fasciolosis.

PubMed

Quigley, A; Sekiya, M; Egan, S; Wolfe, A; Negredo, C; Mulcahy, G

2017-03-01

There is little information on the prevalence of Fasciola hepatica infection in the horse population in Ireland or the potential impact of fluke infection on animal health. To investigate F. hepatica infection in the Irish horse population and to assess the diagnostic potential of an indirect enzyme-linked immunosorbent assay (ELISA) based on the F. hepatica recombinant cathepsin L1 (CL1) antigen. Cross-sectional abattoir survey of horses for liver fluke status. Animals (n = 200) were examined at an abattoir between May 2013 and April 2014. Horses were graded ante mortem for body condition score. Blood and faeces were collected and livers were examined post mortem by gross morphology. A cohort (n = 35) of livers were also examined histologically. Haematology and blood biochemistry, including serum liver enzyme activities, were measured and faeces were sedimented for egg counts. Serum was assayed by indirect ELISA using a recombinant CL1. The prevalence of liver fluke infection was 9.5%. There was no correlation between liver fluke status and time of year, breed classification, age group, sex, body condition score, ante mortem assessment, strongyle infection status, serum liver enzyme activities or CL1 concentration. A comparison of the CL1 ELISA in horse sera compared with a reference standard diagnosis showed high specificity of 95.6% (95% confidence interval [CI] 91.5-98.0%), but low sensitivity of 42.1% (95% CI 20.2-66.5%). This study is limited by its nature as an abattoir study, the relatively small number of animals examined (n = 200), and the absence of a known negative group of horses. Blood biomarkers are not good indicators of liver fluke infection and the CL1 ELISA is not a sensitive tool for diagnosis of fluke infection in the horse. The prevalence of F. hepatica in horses indicates that further research is required to assess the potential impact of liver fluke on equine liver health. © 2016 EVJ Ltd.

Assessment of groundwater quality from Bankura I and II Blocks, Bankura District, West Bengal, India

NASA Astrophysics Data System (ADS)

Nag, S. K.; Das, Shreya

2017-10-01

Hydrochemical evaluation of groundwater has been conducted in Bankura I and II Blocks to analyze and determining groundwater quality in the area. Thirty-six groundwater samples were analyzed for their physical and chemical properties using standard laboratory methods. The constituents have the following ranges in the water: pH 6.4-8.6, electrical conductivity 80-1900 μS/cm, total hardness 30-730 mg/l, TDS 48-1001 mg/l, Ca2+ 4.2-222.6 mg/l, Na+ 2.33-103.33 mg/l, Mg2+ 1.56-115.36 mg/l, K+ 0.67-14 mg/l and Fe BDL-2.53 mg/l, {HCO}3^{ - } 48.8-1000.4 mg/l, Cl- 5.6-459.86 mg/l and {SO}4^{ = } BDL-99.03 mg/l. Results also show that bicarbonate ions ( {HCO}3^{ - } ) dominate the other anions (Cl- and {SO}4^{2 - } ). Sodium adsorption ratio (SAR), soluble sodium percentage (SSP), residual sodium carbonate (RSC), magnesium adsorption ratio (MAR), total hardness (TH), and permeability index (PI) were calculated as derived parameters, to investigate the ionic toxicity. Concerned chemical parameters when plotted in the U.S. Salinity diagram indicate that waters are of C1-S1, C2-S1 and C3-S1 types, i.e., low salinity and low sodium which is good for irrigation. The values of Sodium Adsorption Ratio indicate that the groundwater of the area falls under the category of low sodium hazard. So, there is neither salinity nor toxicity problem of irrigation water, and hence the ground water can safely be used for long-term irrigation. The chemical parameters when plotted in Piper's trilinear diagram are found to concentrate in the central and west central part of the diamond-shaped field. Based on the analytical results, groundwater in the area is found to be generally fresh and hard to very hard. The abundance of the major ions is as follows: HCO3 > Cl > SO4 and Ca > Na > Mg > K > Fe. Results also show that bicarbonate ions ( {HCO}3^{ - } ) dominate the other anions (Cl- and {SO}4^{2 - } ). According to Gibbs diagrams samples fall in the rock dominance field and the chemical quality of groundwater is related to the lithology of the area. The alkaline earth elements (Ca and Mg) occur in greater abundance than alkaline elements (Na and K). A comparative study of our analytical results with the WHO standards of drinking water indicate that the present waters are also good for drinking purposes.

A Neutral Silicon/Phosphorus Frustrated Lewis Pair.

PubMed

Waerder, Benedikt; Pieper, Martin; Körte, Leif A; Kinder, Timo A; Mix, Andreas; Neumann, Beate; Stammler, Hans-Georg; Mitzel, Norbert W

2015-11-02

Frustrated Lewis pairs (FLPs) have a great potential for activation of small molecules. Most known FLP systems are based on boron or aluminum atoms as acid functions, few on zinc, and only two on boron-isoelectronic silicenium cation systems. The first FLP system based on a neutral silane, (C2F5)3SiCH2P(tBu)2 (1), was prepared from (C2F5)3SiCl with C2F5 groups of very high electronegativity and LiCH2P(tBu)2. 1 is capable of cleaving hydrogen, and adds CO2 and SO2. Hydrogen splitting was confirmed by H/D scrambling reactions. The structures of 1, its CO2 and SO2 adducts, and a decomposition product with CO2 were elucidated by X-ray diffraction. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Melt inclusion constraints on volatile systematics and degassing history of the 2014-2015 Holuhraun eruption, Iceland

NASA Astrophysics Data System (ADS)

Bali, E.; Hartley, M. E.; Halldórsson, S. A.; Gudfinnsson, G. H.; Jakobsson, S.

2018-02-01

The mass of volatiles emitted during volcanic eruptions is often estimated by comparing the volatile contents of undegassed melt inclusions, trapped in crystals at an early stage of magmatic evolution, with that of the degassed matrix glass. Here we present detailed characterisation of magmatic volatiles (H2O, CO2, S, Fl and Cl) of crystal-hosted melt and fluid inclusions from the 2014-2015 Holuhraun eruption of the Bárðarbunga volcanic system, Iceland. Based on the ratios of magmatic volatiles to similarly incompatible trace elements, the undegassed primary volatile contents of the Holuhraun parental melt are estimated at 1500-1700 ppm CO2, 0.13-0.16 wt% H2O, 60-80 ppm Cl, 130-240 ppm F and 500-800 ppm S. High-density fluid inclusions indicate onset of crystallisation at pressures ≥ 0.4 GPa ( 12 km depth) promoting deep degassing of CO2. Prior to the onset of degassing, the melt CO2 content may have reached 3000-4000 ppm, with the total magmatic CO2 budget estimated at 23-55 Mt. SO2 release commenced at 0.12 GPa ( 3.6 km depth), eventually leading to entrapment of SO2 vapour in low-density fluid inclusions. We calculate the syn-eruptive volatile release as 22.2 Mt of magmatic H2O, 5.9-7.7 Mt CO2, and 11.3 Mt of SO2 over the course of the eruption; F and Cl release were insignificant. Melt inclusion constraints on syn-eruptive volatile release are similar to estimates made during in situ field monitoring, with the exception of H2O, where field measurements may be heavily biased by the incorporation of meteoric water.

[Pollution Characteristics and Light Extinction Effects of Water-soluble Ions in PM2.5 During Winter Hazy Days at North Suburban Nanjing].

PubMed

Zhou, Yao-yao; Ma, Yan; Zheng, Jun; Cui, Fen-ping; Wang, Li

2015-06-01

To investigate the characteristics of water-soluble ions in PM2.5 and their contribution to light extinction in haze days, on-line monitoring of PM2.5. was conducted at North Suburban Nanjing from 25 January through 3 February, 2013. Water-soluble components were collected with a particle-into-liquid sampler (PILS), and analyzed by ion chromatography (IC) for the contents of SO4(2-), NO3-, NH4+, Cl-, Na+, K+, Mg2+ and Ca2+ Simultaneously particle size distributions were measured using scanning mobility particle sizer (SMPS) and Aerodynamic Particle Sizer (APS). The absorption and scattering coefficients were measured by three-wavelength photoacoustic soot spectrometer (PASS-3). Trace gases (SO2, NO2 etc.) were also monitored. The results showed that the average concentrations of total water-soluble ions were 70.3 and 22.9 microg x m(-3) in haze and normal days, respectively. Secondary hygroscopic components including SO4(2-), NO3- and NH4+ were the major ionic pollutants. Hazy days favored the conversion of SO2 and NOx, to SO4(2-) and NO3-, respectively, and in particular the oxidation of NOx. Using multiple linear regression statistical method, the empirical relationship between the dry aerosol extinction coefficient and the chemical composition was established. NH4NO3 was found to be the largest contributor to aerosol extinction in winter in Nanjing, followed by (NH4)2SO4, OC and EC. In two heavy pollution events, the increase of ion concentrations was influenced by the increase of primary emissions and secondary transformation.

Chlorine and fluorine partition coefficients and abundances in sub-arc mantle xenoliths (Kamchatka, Russia): Implications for melt generation and volatile recycling processes in subduction zones

NASA Astrophysics Data System (ADS)

Bénard, A.; Koga, K. T.; Shimizu, N.; Kendrick, M. A.; Ionov, D. A.; Nebel, O.; Arculus, R. J.

2017-02-01

We report chlorine (Cl) and fluorine (F) abundances in minerals, interstitial glasses, and melt inclusions in 12 andesite-hosted, spinel harzburgite xenoliths and crosscutting pyroxenite veins exhumed from the sub-arc lithospheric mantle beneath Avacha volcano in the Kamchatka Arc (NE Russia). The data are used to calculate equilibrium mineral-melt partition coefficients (D mineral / melt) for Cl and F relevant to subduction-zone processes and unravel the history of volatile depletion and enrichment mechanisms in an arc setting. Chlorine is ∼100 times more incompatible in pyroxenes (DClmineral/melt = 0.005-0.008 [±0.002-0.003]) than F (DFmineral/melt = 0.50-0.57 [±0.21-0.24]), which indicates that partial melting of mantle sources leads to strong depletions in Cl relative to F in the residues. The data set in this study suggests a strong control of melt composition on DCl,Fpyroxene/melt, in particular H2O contents and Al/(Al + Si), which is in line with recent experiments. Fluorine is compatible in Ca-amphibole in the 'wet' sub-arc mantle (DFamphibole/melt = 3.5-3.7 [±1.5]) but not Cl (DClamphibole/melt = 0.03-0.05 [±0.01-0.03]), indicating that amphibole may fractionate F from Cl in the mantle wedge. The inter-mineral partition coefficients for Cl and F in this study are consistent amongst different harzburgite samples, whether they contain glass or not. In particular, disseminated amphibole hosts much of the Cl and F bulk rock budgets of spinel harzburgites (DClamphibole/pyroxene up to 14 and DFamphibole/pyroxene up to 40). Chlorine and fluorine are variably enriched (up to 1500 ppm Cl and 750 ppm F) in the parental arc picrite and boninite melts of primitive pyroxenite veins (and related melt inclusions) crosscutting spinel harzburgites. Based on the data in this study, the main inferences on the behaviour of Cl and F during melting and metasomatic processes in the sub-arc mantle are as follow: (i) Melting models show that most depleted mantle protoliths of intra-oceanic arc sources can have extremely low Cl/F (0.002-0.007) before being overprinted by subduction-derived components. (ii) Chlorine has a higher percolation distance in the mantle than F. Even for small fluid or melt volumes, Cl and F signatures of partial melting are overprinted by those of pervasive percolation, which increases Cl/F in percolating agents and bulk peridotites during chromatographic interaction and/or amphibole-forming metasomatic reactions. These processes ultimately control the bulk Cl and F compositions of the residual mantle lithosphere beneath arcs, and likely in other tectonic settings. (iii) Fluxed melting models suggest that Cl enrichment in arc picrite and boninite melts in this study, and in many arc melt inclusions reported in the literature, could be related to the infiltration of high Cl/F fluids derived from subducted serpentinite or altered crust in mantle wedge sources. However, these high Cl/F signatures should be re-evaluated with new models in light of the possible overprint of pervasive percolation effects in the mantle. The breakdown of amphibole (and/or mica) in the deep metasomatised mantle at higher pressure and temperature conditions than in the slab may explain, at least in part, the positive correlations between F abundances and Cl/F in primitive arc melt inclusions and slab depth.

Sulfur cycling in wetland peat of the New Jersey Pinelands and its effect on stream water chemistry

NASA Astrophysics Data System (ADS)

Mandernack, Kevin W.; Lynch, L.; Krouse, H. R.; Morgan, M. D.

2000-12-01

The dynamics of sulfur cycling in wetland peat along an elevational transect at high, intermediate, and low locations (MS, NW, and LB sites, respectively) was investigated in the watershed of McDonalds Branch within the New Jersey Pinelands, by utilizing both soil incubation experiments (with 35SO 42- as a radiotracer) and stable isotope (δ 34S and δ 18O) analyses of soil, rain, and streamwater. The results indicate that sulfur cycling can vary greatly among different portions of the watershed and this can have large effects on streamwater chemistry and δ 34S values over distances as short as 1 km. Laboratory incubations of peat samples collected in July 1993 revealed the co-occurrence of dissimilatory sulfate reduction (DSR; rates ranging from 0.2 to 22.1 nmol/wet g/day) and net generation of sulfate (NaH 2PO 4 extractable) in the porewater. Generation of sulfate, which was most pronounced at the LB site, may involve oxidation of reduced sulfur in the peat and/or hydrolysis of ester sulfates (ES). Seasonal changes in streamwater SO 42-/Cl - molar ratios were similar at LB and NW, being low during the summer and high in the winter, probably a result of higher rates of DSR within the peat during the summer. Consistent with this, higher δ 34S values of sulfate in streamwater at NW during the summer are attributable to kinetic isotope effects associated with DSR. In contrast to NW, δ 34S values of streamwater sulfate at LB were consistently lower, fluctuated little throughout the year, and were most negative during the summer (as much as 9‰ lower than streamwater at NW 1 km upstream). In comparison to NW, SO 42-/Cl - ratios were lower in streamwater at LB throughout most of the year except for reversals during the summer, which coincided with the lowest δ 34S values. In addition, there was a marked difference in the relationship of δ 18O vs. δ 34S of sulfate in LB and NW streamwater, further suggesting that sulfur cycling varies greatly over relatively short distances within this watershed. In order to explain some of these site-specific differences in streamwater SO 42-/Cl - ratios, δ 34S, and δ 18O values, we hypothesize that the ES pool at LB may, by means of hydrolysis or isotopic exchange with streamwater sulfate, serve as an additional source of isotopically light sulfate to streamwater throughout most of the year. During the summer, drier conditions lower the water table at LB and enhance oxidation of reduced sulfur which releases a pulse of even isotopically lighter sulfate to the stream.

Rotational spectrum of CH3CN⋯ClF and evidence for the +I effect of a CH3 group on the ‘chlorine’ bond N⋯ClF

NASA Astrophysics Data System (ADS)

Page, M. D.; Waclawik, E. R.; Holloway, J. H.; Legon, A. C.

1999-10-01

The ground-state rotational spectra of the isotopomers CH 3C 14N⋯ 35ClF, CH 3C 14N⋯ 37ClF, CD 3C 14N⋯ 35ClF and CH 3C 15N⋯ 35ClF of a symmetric-rotor complex formed by methyl cyanide and chlorine monofluoride have been observed and analysed to give the spectroscopic constants B0, DJ, DJK, χaa( 14N), χaa(Cl) and Mbb. Interpretations of these quantities on the basis of simple models enabled the geometry and strength of binding of the complex to be determined. It is found that the atoms C-CN⋯ClF lie on the C 3 axis of this complex of C 3v symmetry and that the distance r(N⋯Cl)=2.561(2) Å. The quadratic force constants associated with the intermolecular stretching mode and with the bending motion of the CH 3CN subunit pivoted at its mass centre were determined from the centrifugal distortion constants DJ and 2 DJ+ DJK. Their values were k σ=13.9(3) N m -1 and k α=3.0(1)×10 -20 J rad -2, respectively. A comparison of r(N⋯Cl) values and of k σ values establishes that the +I effect of the CH 3 group when it replaces H in HCN leads to a similar shortening of r(N⋯Cl) and to a similar increase in k σ in the two series RCN⋯ClF and RCN⋯HCl (R=H or CH 3).

The stability of Cl-CO3-scapolite relative to plagioclase + CaCO3 + CaSO4 in the presence of NaCl brines as a function of P-T-XNaCl

NASA Astrophysics Data System (ADS)

Harlov, D. E.; Budzyn, B.

2008-12-01

Cl-CO3-scapolite [(Na,Ca)4[Al3 (Al,Si) 3 Si3 O24](Cl, CO3 , SO4 )] occurs as a common partial to total alteration of plagioclase in deep-crustal xenoliths, skarns, marbles, gabbros, metabasites, calc-silicate gneisses, as well as in quartzofeldspathic granulite-facies rocks in general (Moecher and Essene, 1990, J Petrol 31, 997). Alteration of plagioclase to Cl-CO3-scapolite is presumed due to metasomatism by CO2-NaCl-H2O fluids (Satish-Kumar and Santosh, 1998, Geol Mag 135, 27). Previous experimental work on CO3-scapolite has focused on reversing the equilibrium 3 CaAl2 Si2 O8 + CaCO3 = Ca4 Al6 Si6 O24 CO3 in either pure CO2 (Goldschmidt and Newton, 1977, Am Mineral 62, 1063) or in CO2-H2O (Huckenholz and Seiberl, 1989 Abs IGC 28, 2.79). These experiments have determined that the anorthite- calcite-scapolite equilibrium is nearly pressure-invariant in P-T space (200 to 1500 MPa) occurring at approximately 790 to 820 °C (Huckenholz and Seiberl, 1989). In this study, a series of experiments, involving the equilibrium 3 Plagioclase(An60) + 0.5 CaCO3 + 0.5 CaSO4 = [(Na,Ca)4[Al3 (Al,Si)3 Si3 O24](Cl, CO3, SO4 )] plus an NaCl brine (10/90, 20/80, 30/70, and 50/50 molar NaCl/H2O) have been done at 500, 1000, and 1500 MPa and 600 to 900 °C. Natural plagioclase and scapolite, along with synthetic calcite and anhydrite, were lightly ground together in equi-molar amounts in ethanol. The mineral mix (10 mg) + NaCl brine (5 mg), or pure H2O (1.5 mg), were loaded into 3 mm diameter/1.3 mm long Pt capsules which were arc-welded shut, folded, and placed horizontally in a CaF2 setup (with graphite oven), such that the thermocouple tip touched the Pt capsule, or placed in a hydrothermal autoclave (600 and 700 °C; 500 MPa) with an internal thermocouple. A series of duplicate experiments for the same mineral mix, at the same P-T conditions, were done utilizing pure H2O as the flux. The H2O-only experiments duplicated the P-T reversals of Huckenholz and Seiberl (1989). In contrast, the NaCl/H2 O experiments indicate that the stability field of Cl-CO3-scapolite (SiO2 =52.1, Al2O3=24.9, CaO=11.9, Na2O=7.60, Cl=1.86, CO3=2.00, SO4=0.45), relative to plagioclase, greatly expands in the presence of NaCl brines at NaCl concentrations above 10 percent NaCl such that Cl-CO2-scapolite is stable over 600 to 900 °C and 500 to 1500 MPa. This result further strengthens the proposition that NaCl brines, coupled with CO2-bearing fluids, can be and probably are involved during high-grade scapolitization of plagioclase-bearing rocks in the mid to lower crust and upper mantle.

Water-soluble main ions in precipitation over the southeastern Adriatic region: chemical composition and long-range transport.

PubMed

Dorđević, Dragana S; Tosić, Ivana; Unkasević, Miroslava; Durasković, Pavle

2010-11-01

Precipitation samples collected from 1995 to 2000 at meteorological station in the eastern outskirts of Herceg Novi (Montenegro) were analysed on Na(+), K(+), Mg(2+), Ca(2+), Cl(-), SO(4) (2-), NO(3)(-) and NH(4)(+). Four-day backward trajectory simulations were conducted during the precipitation period to investigate the regional transport of main ions and their deposition in the region of the southeastern Adriatic Sea. The air mass trajectories were classified into six trajectory categories by the origin and direction of their approach to Herceg Novi. A bottle and funnel with a small net between them was used for sampling at a height of 1.5 m above the ground. The concentrations of Cl(-), NO(3)(-), NH(4)(+) and SO(4)(2-) were determined spectrophotometrically, the concentrations of Na(+) and K(+) were determined by the FAES method and the concentrations of Mg(2+) and Ca(2+) by the FAAS method. The factor analysis technique (PCA analysis) based on the calculation of the factors was employed to differentiate the contribution of emission sources to the content of the main ions in the precipitation. The obtained data sets were processed using the SPSS 11.5 statistical program. The Hybrid Single-Particle Lagrangian Integrated Trajectory model was used to study the air origin for the city of Herceg Novi (42°27'N, 18°33'E), Montenegro. The following origins of the air masses were considered: northern Europe (NE), eastern Europe-northeastern Europe (EE-NE); eastern Mediterranean-southeastern Europe (EM-SE); Africa-Central Mediterranean (A-CM); western Mediterranean (WM); western Europe-Central Europe (WE-CE) and undefined. The heights and frequencies of precipitation coming by air masses from northern Europe and eastern-northeastern Europe are the lowest. On the contrary, the heights and frequencies of precipitation coming by air masses from the western Mediterranean (36.6%) and Africa and the Central Mediterranean (30.6%) are the highest. The sea salt components (Na(+), Cl(-), Mg(2+)) are significantly correlated, except for air masses originating from the northern and eastern European regions. Significant correlations between SO(4)(2-) and NO(3)(-) are found in air masses coming from the western Europe and North Africa, over the Mediterranean. The highest volume-weighted mean (VWM) of: SO(4)(2-), NH(4)(+) and Mg(2+) are for precipitation from EE-NE while the highest values of VWM of Cl(-) are from WM and of K(+) are from WE-CE. Long-range transport of Sahara dust is confirmed. For better estimation of origins of water-soluble ions in precipitation expanding list of analysis on anions of organic acids, such as HCOO(-), CH(3)COO(-), and C(2)H(2)COO(-), could be indicative of volatile organic compounds emitted by vegetation but also traffic. The chemical composition of precipitation together with a study of air backward trajectories is the proper tool for tracking the long-range transport of water-soluble ions and estimating transboundary pollution.

NHC→SiCl4 : an ambivalent carbene-transfer reagent.

PubMed

Böttcher, Tobias; Steinhauer, Simon; Lewis-Alleyne, Lesley C; Neumann, Beate; Stammler, Hans-Georg; Bassil, Bassem S; Röschenthaler, Gerd-Volker; Hoge, Berthold

2015-01-07

The addition of BCl3 to the carbene-transfer reagent NHC→SiCl4 (NHC=1,3-dimethylimidazolidin-2-ylidene) gave the tetra- and pentacoordinate trichlorosilicon(IV) cations [(NHC)SiCl3 ](+) and [(NHC)2 SiCl3 ](+) with tetrachloroborate as counterion. This is in contrast to previous reactions, in which NHC→SiCl4 served as a transfer reagent for the NHC ligand. The addition of BF3 ⋅OEt2 , on the other hand, gave NHC→BF3 as the product of NHC transfer. In addition, the highly Lewis acidic bis(pentafluoroethyl)silane (C2 F5 )2 SiCl2 was treated with NHC→SiCl4 . In acetonitrile, the cationic silicon(IV) complexes [(NHC)SiCl3 ](+) and [(NHC)2 SiCl3 ](+) were detected with [(C2 F5 )SiCl3 ](-) as counterion. A similar result was already reported for the reaction of NHC→SiCl4 with (C2 F5 )2 SiH2 , which gave [(NHC)2 SiCl2 H][(C2 F5 )SiCl3 ]. If the reaction medium was changed to dichloromethane, the products of carbene transfer, NHC→Si(C2 F5 )2 Cl2 and NHC→Si(C2 F5 )2 ClH, respectively, were obtained instead. The formation of the latter species is a result of chloride/hydride metathesis. These compounds may serve as valuable precursors for electron-poor silylenes. Furthermore, the reactivity of NHC→SiCl4 towards phosphines is discussed. The carbene complex NHC→PCl3 shows similar reactivity to NHC→SiCl4 , and may even serve as a carbene-transfer reagent as well. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Pre-eruptive volatile and erupted gas phase characterization of the 2014 basalt of Bárðarbunga volcanic system, Iceland.

NASA Astrophysics Data System (ADS)

Haddadi, Baptiste; Moune, Séverine; Sigmarsson, Olgeir; Gauthier, Pierre-Jean; Gouhier, Mathieu

2015-04-01

The 2014 Holuhraun eruption on the Bárðarbunga Volcanic System is the largest fissure eruption in Iceland since the 1783 Laki eruption. The eruption started end of August 2014 and has been characterized by large emission of SO2 into the atmosphere. It provides a rare opportunity to study in details magmatic and degassing processes during a large-volume fissure eruption. In order to characterize the pre-eruptive magmatic composition and to assess the plume chemistry at the eruption site, lava and tephra were sampled together with the eruption plume. The basalt composition is olivine tholeiite with MgO close to 7 wt%. It is phenocryst-poor with plagioclase as the dominant mineral phase but olivine and clinopyroxene are also present together with sulphide globules composed principally of pyrite and chalcopyrite. The volatile (S, Cl and F) and major element concentrations were measured by the electron microprobe in melt inclusions (MIs) trapped in plagioclase and clinopyroxene and groundmass glass. The MIs composition ranges from fairly primitive basaltic compositions (MgO: 9.03 wt%) down to evolved qz-tholeiites (MgO: 5.57 wt%), with estimated pre-eruptive S concentrations of 1500 ppm. Tephra groundmass glass contains 400 ppm S, whereas Cl and F concentrations are respectively slightly lower and indistinguishable from those in the MIs. This implies limited exsolution of halogens but 75% of the initial sulphur content. Relatively to their total iron content, MIs are sulphur saturated, and their oxygen fugacity close to the FMQ buffer. The difference between the estimated initial volatile concentrations measured in the MIs and in the tephra groundmass (i.e. the so-called petrological method) yields 7.2 Mt SO2, limited HCl and no HF atmospheric mass loading from the Holuhraun 2014 eruption. The SO2/HCl molar ratio of the gas phase, calculated from the MIs, is 13 and 14, respectively, using average and estimated pre-eruptive S and Cl concentrations in the MIs. Filter-pack sampling of the gas plume was performed 2 October 2014 few hundred meters to the W of the active crater row. Filter packs were composed of three filters in series: one PTFE filter to collect particulate phases, followed by two impregnated filters to trap major gaseous species (SO2, HF and HCl). Sulphate (SO4) and halide (Cl- and F-) ion concentrations were determined by ion chromatography. The SO2/HCl molar ratio in the erupted gas phase at the eruption site is 29-46, only slightly higher than that estimated from the MIs. Trace element volatility and fluxes are discussed elsewhere (Gauthier et al., 2015) but the average SO2 flux calculated from lava volume estimate end of November as 1.2 km3 (Gouhier et al., 2015) is close to 1100 kg/sec. This is the highest SO2 flux ever estimated from gas plume measurements. References: Gauthier et al. (2015) Trace element degassing patterns and volcanic fluxes to the atmosphere during the 2014 Holuhraun eruption, Iceland. EGU General Assembly 2015. Gouhier et al. (2015) Retrieval of lava and SO2 long-lived emissions using MSG-SEVIRI data during the 2014 Holuhraun eruption. EGU General Assembly 2015.

Chemical vs. Physical Acceleration of Cement Hydration

PubMed Central

Bentz, Dale P.; Zunino, Franco; Lootens, Didier

2016-01-01

Cold weather concreting often requires the use of chemical accelerators to speed up the hydration reactions of the cement, so that setting and early-age strength development will occur in a timely manner. While calcium chloride (dihydrate – CaCl2·2H2O) is the most commonly used chemical accelerator, recent research using fine limestone powders has indicated their high proficiency for physically accelerating early-age hydration and reducing setting times. This paper presents a comparative study of the efficiency of these two approaches in accelerating hydration (as assessed via isothermal calorimetry), reducing setting times (Vicat needle), and increasing early-age mortar cube strength (1 d and 7 d). Both the CaCl2 and the fine limestone powder are used to replace a portion of the finest sand in the mortar mixtures, while keeping both the water-to-cement ratio and volume fractions of water and cement constant. Studies are conducted at 73.4 °F (23°C) and 50 °F (10 °C), so that activation energies can be estimated for the hydration and setting processes. Because the mechanisms of acceleration of the CaCl2 and limestone powder are different, a hybrid mixture with 1 % CaCl2 and 20 % limestone powder (by mass of cement) is also investigated. Both technologies are found to be viable options for reducing setting times and increasing early-age strengths, and it is hoped that concrete producers and contractors will consider the addition of fine limestone powder to their toolbox of techniques for assuring performance in cold weather and other concreting conditions where acceleration may be needed. PMID:28077884

Variations in trace metal and halogen ratios in magmatic gases through an eruptive cycle of the Pu'u O'o vent, Kilauea, Hawaii: July-August 1985

DOE Office of Scientific and Technical Information (OSTI.GOV)

Miller, T.L.; Zoller, W.H.; Crowe, B.M.

1990-08-10

Particle and gas samples were obtained before and after eruptive episode 35 in July and August 1985 at the fuming Pu'u O'o vent, Kilauea volcano, Hawaii. The sampling system employed consisted of a particle filter followed by four {sup 7}LiOH treated filters to collect acidic gases. The filters were analyzed using instrumental neutron activation analysis (INAA). The results indicate that Br/Cl and Re/Cl ratios do not fluctuate through an eruption cycle but the F/Cl, F/Br and metal/Cl ratios (In and Cd) do change through the cycle. An inverse relationship between F/Cl and metal/Cl was observed. The changes are probably duemore » to influxes of relatively undegassed magma during the repose period releasing fume with lower F/Cl, F/BR and higher metal/Cl ratios. As the magma in the Pu'u O'o conduit gradually degasses either before or several days after an eruptive episode, F/Cl and F/Br ratios increase and the metal/Cl ratios decrease. One sample collected on July 24, two days before eruptive episode 35, did not follow this general trend. This can be explained by a gas pulse from a deeper, less degassed portion of magma making its way to the top of the conduit.« less

"Variations in trace metal and halogen ratios in magmatic gases through an eruptive. Cycle of the Pu'u O'o Vent, Kilauea, Hawaii: July-August 1985""

NASA Astrophysics Data System (ADS)

Miller, Theresa L.; Zoller, William H.; Crowe, Bruce M.; Finnegan, David L.

1990-08-01

Particle and gas samples were obtained before and after eruptive episode 35 in July and August 1985 at the fuming Pu'u O'o vent, Kilauea volcano, Hawaii. The sampling system employed consisted of a particle filter followed by four 7LiOH treated filters to collect acidic gases. The filters were analyzed using instrumental neutron activation analysis (INAA). The results indicate that Br/Cl and Re/Cl ratios do not fluctuate through an eruption cycle but the F/Cl, F/Br and metal/Cl ratios (In and Cd) do change through the cycle. An inverse relationship between F/Cl and metal/Cl was observed. The changes are probably due to influxes of relatively undegassed magma during the repose period releasing fume with lower F/Cl, F/Br and higher metal/Cl ratios. As the magma in the Pu'u O'o conduit gradually degasses either before or several days after an eruptive episode, F/Cl and F/Br ratios increase and the metal/Cl ratios decrease. One sample collected on July 24, two days before eruptive episode 35, did not follow this general trend. This can be explained by a gas pulse from a deeper, less degassed portion of magma making its way to the top of the conduit.

Inverted cucurbit[6]uril supramolecular assemblies formed in the presence of tetrachlorozincate anions

NASA Astrophysics Data System (ADS)

Chen, Kai; Xu, Jing; Qiu, Sheng-Chao; Wang, Yuan; Chen, Min-Dong; Zhang, Yun-Qian; Xiao, Xin; Tao, Zhu

2017-10-01

We investigated the interactions in an inverted cucurbit[6]uril (iQ[6]) with a series of 1,ω-alkyldimins and their supramolecular assemblies in the presence of the tetrachlorozincate anion ([ZnCl4]2-) structure directing agent. iQ[6] forms an outer surface interaction with [ZnCl4]2- to form different iQ[6]/[ZnCl4]2--based supramolecular assemblies with different length 1,ω-alkyldimins. Interestingly, most 1,ω-alkyldimins were not visible in crystals structures in the presence of concentrated HCl. The porous iQ[6]/[ZnCl4]2--based supramolecular assemblies could be used as materials for adsorbing volatile compounds.

Structural and energetic properties of acetonitrile-Group IV (A & B) halide complexes.

PubMed

Helminiak, Heather M; Knauf, Robin R; Danforth, Samuel J; Phillips, James A

2014-06-19

We have conducted an extensive computational study of the structural and energetic properties of select acetonitrile-Group IV (A & B) tetrahalide complexes, both CH3CN-MX4 and (CH3CN)2-MX4 (M = Si, Ge, Ti; X = F, Cl). We have also examined the reactivity of CH3CN with SiF4, SiCl4, GeCl4, and TiCl4, and measured low-temperature IR spectra of thin films containing CH3CN with SiF4, GeCl4, or TiCl4. The six 1:1 complexes fall into two general structural classes. CH3CN-TiCl4, CH3CN-TiF4, and CH3CN-GeF4, exhibit relatively short M-N bonds (~2.3 Å), an intermediate degree of distortion in the MX4 subunit, and binding energies ranging from 11.0 to 13.0 kcal/mol. Conversely, CH3CN-GeCl4, CH3CN-SiF4, and CH3CN-SiCl4, are weakly bonded systems, with long M-N distances (>3.0 Å), little distortion in the MX4 subunit, and binding energies ranging from 3.0 to 4.4 kcal/mol. The structural features of analogous 2:1 systems resemble those of their 1:1 counterparts, whereas the binding energies (relative to three isolated fragments) are roughly twice as large. Calculated M-N potential curves in the gas phase and bulk, dielectric media are reported for all 1:1 complexes, and for two systems, CH3CN-GeF4 and CH3CN-SiF4, these data predict significant condensed-phase structural changes. The effect on the CH3CN-SiF4 potential is extreme; the curve becomes quite flat over a broad range in dielectric media, and at higher ε values, the global minimum shifts inward by about 1.0 Å. In bulk reactivity experiments, no reaction was observed between CH3CN and SiF4, SiCl4, or GeCl4, whereas CH3CN and TiCl4 were found to react immediately upon contact. Also, thin-film IR spectra indicate a strong interaction between CH3CN and TiCl4, yet only weak interactions between CH3CN and GeCl4 or SiF4 in the solid state.

Unimolecular HCl and HF elimination reactions of 1,2-dichloroethane, 1,2-difluoroethane, and 1,2-chlorofluoroethane: assignment of threshold energies.

PubMed

Duncan, Juliana R; Solaka, Sarah A; Setser, D W; Holmes, Bert E

2010-01-21

The recombination of CH(2)Cl and CH(2)F radicals generates vibrationally excited CH(2)ClCH(2)Cl, CH(2)FCH(2)F, and CH(2)ClCH(2)F molecules with about 90 kcal mol(-1) of energy in a room temperature bath gas. New experimental data for CH(2)ClCH(2)F have been obtained that are combined with previously published studies for C(2)H(4)Cl(2) and C(2)H(4)F(2) to define reliable rate constants of 3.0 x 10(8) (C(2)H(4)F(2)), 2.4 x 10(8) (C(2)H(4)Cl(2)), and 1.9 x 10(8) (CH(2)ClCH(2)F) s(-1) for HCl and HF elimination. The product branching ratio for CH(2)ClCH(2)F is approximately 1. These experimental rate constants are compared to calculated statistical rate constants (RRKM) to assign threshold energies for HF and HCl elimination. The calculated rate constants are based on transition-state models obtained from calculations of electronic structures; the energy levels of the asymmetric, hindered, internal rotation were directly included in the state counting to obtain a more realistic measure for the density of internal states for the molecules. The assigned threshold energies for C(2)H(4)F(2) and C(2)H(4)Cl(2) are both 63 +/- 2 kcal mol(-1). The threshold energies for CH(2)ClCH(2)F are 65 +/- 2 (HCl) and 63 +/- 2 (HF) kcal mol(-1). These threshold energies are 5-7 kcal mol(-1) higher than the corresponding values for C(2)H(5)Cl or C(2)H(5)F, and beta-substitution of F or Cl atoms raises threshold energies for HF or HCl elimination reactions. The treatment presented here for obtaining the densities of states and the entropy of activation from models with asymmetric internal rotations with high barriers can be used to judge the validity of using a symmetric internal-rotor approximation for other cases. Finally, threshold energies for the 1,2-fluorochloroethanes are compared to those of the 1,1-fluorochloroethanes to illustrate substituent effects on the relative energies of the isomeric transition states.

Experimental Acquisition, Development, and Transmission of Leishmania tropica by Phlebotomus duboscqi

DTIC Science & Technology

2012-09-10

repeatedly isolated from the rock hyrax (Procavia capensis) in Israel and Kenya, and from domestic dogs in Morocco (Dereure et al., 1991; Sang et al., 1994...1991. Leishmania tropica in Morocco: infection in dogs . Transactions of the Royal Society ofTropical Medicine and Hygiene 85, 595. 42 H.A. Hanafi et al...flies is enhanced by regurgitation of fPPG. Nature 430,463-467. Sacks, D.L., Kenney, R.T., Kreutzer, R.D., Jaffe, C.L., Sharma, M.C., Sinha, S.P., Neva

Experimental Acquisition, Development, and Transmission of Leishmania tropica by Phlebotomus duboscqi

DTIC Science & Technology

2013-01-01

repeatedly isolated from the rock hyrax (Procavia capensis) in Israel and Kenya, and from domestic dogs in Morocco (Dereure et al., 1991; Sang et al., 1994...Leishmania tropica in Morocco: infection in dogs . Transactions of the Royal Society of Tropical Medicine and Hygiene 85, 595. 42 H.A. Hanafi et al...cutaneous leishmaniasis by sand flies is enhanced by regurgitation of fPPG. Nature 430, 463–467. Sacks, D.L., Kenney, R.T., Kreutzer, R.D., Jaffe, C.L

Effect of shift in growth temperature on tolerance of psychrotrophic and mesophilic strains of Bacillus cereus to heat and sodium chloride.

PubMed

Mahakarnchanakul, W; Beuchat, L R

1999-01-01

A shift in growth temperature of a psychrotrophic (F3802A/84) strain and a mesophilic strain (B4ac-1) of Bacillus cereus grown at 30 degrees C for 10 h, then at 37 degrees C or 40 degrees C for 14 h, enhanced thermotolerance. Sodium chloride, at concentrations of 2.0 and 4.0% in brain heart infusion (BHI) broth, had no effect on thermotolerance of strain B4ac-1 heated at 50 degrees C, whereas the same concentrations of NaCl caused a decrease in thermotolerance of strain F3802A/84 heated at 48 degrees C. A downshift in growth temperature from 30 degrees C to 10 degrees C followed by incubation for 3 to 9 days increased thermotolerance of strain F3802A/84 but not strain B4ac-1 heated in BHI broth containing 2.0 or 4.0% NaCl compared to thermotolerance in BHI broth containing 0.5% NaCl. Protein analysis using one-dimensional gel electrophoresis revealed an increase in proteins with molecular weights of 54, 50, 44, and 42 kDa in cells of strain F3802A/84 and 83 and 69 kDa in cells of strain B4ac-1 subjected to an upshift in growth temperature from 30 degrees C to 37 degrees C or 40 degrees C, respectively. A downshift in growth temperature from 30 degrees C to 10 degrees C resulted in substantial amounts of proteins with molecular weights of 63, 40, and 29 kDa produced by strain F3802A/84 and 63 kDa to be produced by strain B4ac-1. Proteins produced in response to upshift or downshift in growth temperature are suspected to play an important role in heat resistance of the psychrotrophic and mesophilic strains of B. cereus examined in this study. Changes in resistance to heat or refrigeration temperatures, as well as tolerance to NaCl, as affected by previous exposure of cells to temperature shifts may influence the ability of B. cereus to grow in minimally processed foods during distribution and storage.

Solid polymer electrolytes

DOEpatents

Abraham, K.M.; Alamgir, M.; Choe, H.S.

1995-12-12

This invention relates to Li ion (Li{sup +}) conductive solid polymer electrolytes composed of poly(vinyl sulfone) and lithium salts, and their use in all-solid-state rechargeable lithium ion batteries. The lithium salts comprise low lattice energy lithium salts such as LiN(CF{sub 3}SO{sub 2}){sub 2}, LiAsF{sub 6}, and LiClO{sub 4}. 2 figs.

Source identification of particulate matter in a semi-urban area of Malaysia using multivariate techniques.

PubMed

Wahid, N B A; Latif, M T; Suan, L S; Dominick, D; Sahani, M; Jaafar, S A; Mohd Tahir, N

2014-03-01

This study aims to determine the composition and sources of particulate matter with an aerodynamic diameter of 10 μm or less (PM10) in a semi-urban area. PM10 samples were collected using a high volume sampler. Heavy metals (Fe, Zn, Pb, Mn, Cu, Cd and Ni) and cations (Na(+), K(+), Ca(2+) and Mg(2+)) were detected using inductively coupled plasma mass spectrometry, while anions (SO4 (2-), NO3 (-), Cl(-) and F(-)) were analysed using Ion Chromatography. Principle component analysis and multiple linear regressions were used to identify the source apportionment of PM10. Results showed the average concentration of PM10 was 29.5 ± 5.1 μg/m(3). The heavy metals found were dominated by Fe, followed by Zn, Pb, Cu, Mn, Cd and Ni. Na(+) was the dominant cation, followed by Ca(2+), K(+) and Mg(2+), whereas SO4 (2-) was the dominant anion, followed by NO3 (-), Cl(-) and F(-). The main sources of PM10 were the Earth's crust/road dust, followed by vehicle emissions, industrial emissions/road activity, and construction/biomass burning.

Likelihood of atom-atom contacts in crystal structures of halogenated organic compounds.

PubMed

Jelsch, Christian; Soudani, Sarra; Ben Nasr, Cherif

2015-05-01

The likelihood of occurrence of intermolecular contacts in crystals of halogenated organic compounds has been analysed statistically using tools based on the Hirshfeld surface. Several families of small halogenated molecules (containing organic F, Cl, Br or I atoms) were analysed, based on chemical composition and aromatic or aliphatic character. The behaviour of crystal contacts was also probed for molecules containing O or N. So-called halogen bonding (a halogen making short interactions with O or N, or a π interaction with C) is generally disfavoured, except when H is scarce on the molecular surface. Similarly, halogen⋯halogen contacts are more rare than expected, except for molecules that are poor in H. In general, the H atom is found to be the preferred partner of organic halogen atoms in crystal structures. On the other hand, C⋯C interactions in parallel π-stacking have a high propensity to occur in halogenated aromatic molecules. The behaviour of the four different halogen species (F, Cl, Br, I) is compared in several chemical composition contexts. The analysis tool can be refined by distinguishing several types for a given chemical species, such as H atoms bound to O or C. Such distinction shows, for instance, that C-H⋯Cl and O-H⋯O are the preferred interactions in compounds containing both O and Cl.

On the Ground Electronic States of TiF and TiCl

NASA Astrophysics Data System (ADS)

Boldyrev, Alexander I.; Simons, Jack

1998-04-01

The low-lying electronic states of TiF and TiCl have been studied using high levelab initiotechniques. Both are found to have two low-lying excited electronic states,4Σ-(0.080 eV (TiF) and 0.236 eV (TiCl)) and2Δ (0.266 eV (TiF) and 0.348 eV (TiCl)), and4Φ ground states at the highest CCSD(T)/6-311++G(2d,2f) level of theory. Our theoretical predictions of4Φ ground electronic states for TiF and TiCl support recent experimental findings by Ram and Bernath, and our calculated bond lengths and vibrational frequencies are in reasonable agreement with their experimental data.

Placebo effects of a sham opioid solution: a randomized controlled study in patients with chronic low back pain.

PubMed

Klinger, Regine; Kothe, Ralph; Schmitz, Julia; Kamping, Sandra; Flor, Herta

2017-10-01

This study tested the experimental placebo effect in a group of chronic pain patients. Forty-eight patients having chronic back pain participated in a randomized clinical trial that tested the efficacy of a sham opioid solution (NaCl) compared with an alleged neutral, completely inactive solution (NaCl). We shaped the placebo effect by 2 interventions: verbal instruction and conditioning. The patients were either told that the "solution reduces pain and improves physical capacity" or the "solution is neutral, a placebo." Half of each group was additionally conditioned (coupling solution with reduced experimental pain), yielding 4 subgroups with 12 participants each. Outcome measures were as follows: the patients' clinical back pain ratings and acute pain ratings (both examined by numerical rating scale 0-10) and self-rated functional capacity (0%-100%; time required for the exercise). Expected pain relief before and after solution intake was also assessed. The inactive solution (NaCl), when presented as an effective treatment (sham "opioid" solution), induced placebo analgesia as evident in lower ratings of the patients' clinical back pain (F(3.12,144.21) = 25.05, P < 0.001), acute pain ratings (F(1.99,87.40) = 18.12, P < 0.01), and time needed to complete a series of daily activities exercises (F(1,44) = 8.51, P < 0.01) as well as increased functional capacity (F(1,44.00) = 19.42, P < 0.001). The 2 manipulations (instruction and conditioning) changed pain expectations, and they were maintained in both sham opioid groups. The results suggest that it may be clinically useful to explicitly integrate placebo analgesia responses into pain management.

An Inhibitor of the δPKC Interaction with the d Subunit of F1Fo ATP Synthase Reduces Cardiac Troponin I Release from Ischemic Rat Hearts: Utility of a Novel Ammonium Sulfate Precipitation Technique

PubMed Central

Ogbi, Mourad; Obi, Ijeoma; Johnson, John A.

2013-01-01

We have previously reported protection against hypoxic injury by a cell-permeable, mitochondrially-targeted δPKC-d subunit of F1Fo ATPase (dF1Fo) interaction inhibitor [NH2-YGRKKRRQRRRMLA TRALSLIGKRAISTSVCAGRKLALKTIDWVSFDYKDDDDK-COOH] in neonatal cardiac myo-cytes. In the present work we demonstrate the partitioning of this peptide to the inner membrane and matrix of mitochondria when it is perfused into isolated rat hearts. We also used ammonium sulfate ((NH4)2SO4) and chloroform/methanol precipitation of heart effluents to demonstrate reduced card-iac troponin I (cTnI) release from ischemic rat hearts perfused with this inhibitor. 50% (NH4)2SO4 saturation of perfusates collected from Langendorff rat heart preparations optimally precipitated cTnI, allowing its detection in Western blots. In hearts receiving 20 min of ischemia followed by 30, or 60 min of reperfusion, the Mean±S.E. (n = 5) percentage of maximal cTnI release was 30±7 and 60±17, respectively, with additional cTnI release occurring after 150 min of reperfusion. Perfusion of hearts with the δPKC-dF1Fo interaction inhibitor, prior to 20 min of ischemia and 60–150 min of reperfusion, reduced cTnI release by 80%. Additionally, we found that when soybean trypsin inhibitor (SBTI), was added to rat heart effluents, it could also be precipitated using (NH4)2SO4 and detected in western blots. This provided a convenient method for normalizing protein recoveries between groups. Our results support the further development of the δPKC-dF1Fo inhibitor as a potential therapeutic for combating cardiac ischemic injury. In addition, we have developed an improved method for the detection of cTnI release from perfused rat hearts. PMID:23936451

Surface tensions of inorganic multicomponent aqueous electrolyte solutions and melts.

PubMed

Dutcher, Cari S; Wexler, Anthony S; Clegg, Simon L

2010-11-25

A semiempirical model is presented that predicts surface tensions (σ) of aqueous electrolyte solutions and their mixtures, for concentrations ranging from infinitely dilute solution to molten salt. The model requires, at most, only two temperature-dependent terms to represent surface tensions of either pure aqueous solutions, or aqueous or molten mixtures, over the entire composition range. A relationship was found for the coefficients of the equation σ = c(1) + c(2)T (where T (K) is temperature) for molten salts in terms of ion valency and radius, melting temperature, and salt molar volume. Hypothetical liquid surface tensions can thus be estimated for electrolytes for which there are no data, or which do not exist in molten form. Surface tensions of molten (single) salts, when extrapolated to normal temperatures, were found to be consistent with data for aqueous solutions. This allowed surface tensions of very concentrated, supersaturated, aqueous solutions to be estimated. The model has been applied to the following single electrolytes over the entire concentration range, using data for aqueous solutions over the temperature range 233-523 K, and extrapolated surface tensions of molten salts and pure liquid electrolytes: HCl, HNO(3), H(2)SO(4), NaCl, NaNO(3), Na(2)SO(4), NaHSO(4), Na(2)CO(3), NaHCO(3), NaOH, NH(4)Cl, NH(4)NO(3), (NH(4))(2)SO(4), NH(4)HCO(3), NH(4)OH, KCl, KNO(3), K(2)SO(4), K(2)CO(3), KHCO(3), KOH, CaCl(2), Ca(NO(3))(2), MgCl(2), Mg(NO(3))(2), and MgSO(4). The average absolute percentage error between calculated and experimental surface tensions is 0.80% (for 2389 data points). The model extrapolates smoothly to temperatures as low as 150 K. Also, the model successfully predicts surface tensions of ternary aqueous mixtures; the effect of salt-salt interactions in these calculations was explored.

Corrosion of Continuous Fiber Reinforced Aluminum Metal Matrix Composites (CF-AMCs)

NASA Astrophysics Data System (ADS)

Tiwari, Shruti

The first objective of this research is to study the atmospheric corrosion behavior of continuous reinforced aluminum matrix composites (CF-AMCs). The materials used for this research were alumina (Al2O3) and nickel (Ni) coated carbon (C) fibers reinforced AMCs. The major focus is to identify the correlation between atmospheric parameters and the corrosion rates of CF-AMCs in the multitude of microclimates and environments in Hawai'i. The micro-structures of CF-AMCs were obtained to correlate the microstructures with their corrosion performances. Also electrochemical polarization experiments were conducted in the laboratory to explain the corrosion mechanism of CF-AMCs. In addition, CF-AMCs were exposed to seven different test sites for three exposure periods. The various climatic conditions like temperature (T), relative humidity (RH), rainfall (RF), time of wetness (TOW), chloride (Cl- ) and sulfate (SO42-) deposition rate, and pH were monitored for three exposure period. Likewise, mass losses of CF-AMCs at each test site for three exposure periods were determined. The microstructure of the CF-AMCS showed that Al/C/50f MMCs contained a Ni-rich phase in the matrix, indicating that the Ni coating on the C fiber dissolved in the matrix. The intermetallic phases obtained in Al-2wt% Cu/Al 2O3/50f-T6 MMC and Al-2wt%-T6 monolith were rich in Cu and Fe. The intermetallic phases obtained in Al 7075/Al2O3/50f-T6 MMC and Al 7075-T6 monolith also contained traces of Mg, Zn, Ni, and Si. Electrochemical polarization experiment indicated that the Al/Al 2O3/50f Al-2wt% Cu/Al2O3/50f-T6 and Al 7075/Al2O3/50f-T6 MMC showed similar corrosion trends as their respective monoliths pure Al, Al-2wt%-T6 and Al 7075-T6 in both aerated and deaerated condition. Al2O3 fiber, being an insulator, did not have a great effect on the polarization behavior of the composites. Al/C/50f MMCs corroded at a much faster rate as compared to pure Al monolith due to the galvanic effect between C and Al. According to the mass loss data of Al/C/50f MMCs, corrosion rate was high at marine environments (high Cl-) when compared to a tropical rainforest microclimate and low in a test site with a high SO2 and acid rain. Due to presence of conductive C fiber, the galvanic corrosion was a dominating corrosion mechanism. Due to high volume fraction of C, the corrosion phenomenon was cathodically controlled. The galvanic corrosion between C fiber and Al matrix showed a strong positive correlation with Cl - deposition rate. Lower corrosion rate at volcanic test site was attributed to dissolution of Ni rich phase, a potential cathodic site that promotes corrosion of Al/C/50f MMCs. Based on the mass loss data of Al2O3 based CF-AMCs and the monoliths showed maximum corrosion at volcanic test site when compared to any other test site. Due to the small volume fraction of intermetallic phases, the corrosion was anodically controlled. And hence the maximum anodic dissolution was found at volcanic test site (high SO2 and acid rain). The second objective of this thesis is to study the effect localized deformation on the corrosion of CF-AMCs. Corrosion initiation on Al (2 wt% Cu)/Al2O3/60f (60% fiber), Al 6061/Al2O 3/60f, and Al/Al2O3/60f CF-AMCs was studied in an aqueous environment The CF-AMCs and their monolithic alloys were deformed locally using a 1/16" diameter silicon nitride ball and 15-60 Kg load in a Rockwell hardness testing machine. Corrosion initiated at the deformed sites, and after longer exposures, spread over the entire region. Localized mechanical deformation resulted in micro-crevice formations at the fiber matrix interface. When deformed material is exposed to a corrosive solution, the crevices at the fiber matrix interface likely increased the hydrogen ion concentration lowering the pH at those regions, a process that leads to premature corrosion. The copper (Cu) rich CF-AMCs in aqueous solution resulted in dissolution of Cu rich phase and their subsequent deposition and redistribution as Cu over the deformed CF-AMCs surface. The corrosion rates of deformed CF-AMCs were higher than the non-deformed CF-AMCs.

Assessing the potential roles of silicon and germanium phthalocyanines in planar heterojunction organic photovoltaic devices and how pentafluoro phenoxylation can enhance π-π interactions and device performance.

PubMed

Lessard, Benoît H; White, Robin T; Al-Amar, Mohammad; Plint, Trevor; Castrucci, Jeffrey S; Josey, David S; Lu, Zheng-Hong; Bender, Timothy P

2015-03-11

In this study, we have assessed the potential application of dichloro silicon phthalocyanine (Cl2-SiPc) and dichloro germanium phthalocyanine (Cl2-GePc) in modern planar heterojunction organic photovoltaic (PHJ OPV) devices. We have determined that Cl2-SiPc can act as an electron donating material when paired with C60 and that Cl2-SiPc or Cl2-GePc can also act as an electron acceptor material when paired with pentacene. These two materials enabled the harvesting of triplet energy resulting from the singlet fission process in pentacene. However, contributions to the generation of photocurrent were observed for Cl2-SiPc with no evidence of photocurrent contribution from Cl2-GePc. The result of our initial assessment established the potential for the application of SiPc and GePc in PHJ OPV devices. Thereafter, bis(pentafluoro phenoxy) silicon phthalocyanine (F10-SiPc) and bis(pentafluoro phenoxy) germanium phthalocyanine (F10-GePc) were synthesized and characterized. During thermal processing, it was discovered that F10-SiPc and F10-GePc underwent a reaction forming small amounts of difluoro SiPc (F2-SiPc) and difluoro GePc (F2-GePc). This undesirable reaction could be circumvented for F10-SiPc but not for F10-GePc. Using single crystal X-ray diffraction, it was determined that F10-SiPc has significantly enhanced π-π interactions compared with that of Cl2-SiPc, which had little to none. Unoptimized PHJ OPV devices based on F10-SiPc were fabricated and directly compared to those constructed from Cl2-SiPc, and in all cases, PHJ OPV devices based on F10-SiPc had significantly improved device characteristics compared to Cl2-SiPc.

New molten salt systems for high-temperature molten salt batteries: LiF-LiCl-LiBr-based quaternary systems

NASA Astrophysics Data System (ADS)

Fujiwara, Syozo; Inaba, Minoru; Tasaka, Akimasa

To develop novel multi-component molten salt systems more effectively, we developed a simulative technique using the CALPHAD (Calculation of Phase Diagram and Thermodynamics) method to estimate the ionic conductivity and the melting point. The validity of this new simulative technique was confirmed by comparing the simulated ionic conductivities and melting points of typical high-temperature molten salts, such as LiF-LiCl-LiBr, LiF-LiBr-KBr, LiCl-LiBr-KBr, and LiCl-LiBr-LiI, with those reported data in the literature or experimentally obtained. This simulative technique was used to develop new quaternary molten salt systems for use as electrolytes in high-temperature molten salt batteries (called thermal batteries). The targets of the ionic conductivity and the melting point were set at 2.0 S cm -1 and higher at 500 °C, and in the range of 350-430 °C, respectively, to replace the LiCl-KCl system (1.85 S cm -1 at 500 °C) within the conventional design of the heat generation system for thermal batteries. Using the simulative method, six kinds of novel quaternary systems, LiF-LiCl-LiBr-MX (M = Na and K; X = F, Cl, and Br), which contain neither environmentally instable anions such as iodides nor expensive cations such as Rb + and Cs +, were proposed. Experimental results showed that the LiF-LiCl-LiBr-0.10NaX (X = Cl and Br) and LiF-LiCl-LiBr-0.10KX (X = F, Cl, and Br) systems meet our targets of both the ionic conductivity and the melting point.

Structural variety in copper(II) complexes of 3-formylchromone: Synthesis, spectral, thermal, molecular modeling and biological studies

NASA Astrophysics Data System (ADS)

Shebl, Magdy; Adly, Omima M. I.; Taha, A.; Elabd, N. N.

2017-11-01

The compound in the title (L) was synthesized and reacted with Cu(II) metal ion with different anions (OAc-, NO3-, SO42-, ClO4-, Cl- and Br-) in absence and presence of auxiliary ligands (L‧); N,O-donor; or N,N-donor; to form binary and ternary Cu(II)-chelates. The metal complexes were fully characterized by analytical and spectral techniques in addition to thermal, conductivity and magnetic susceptibility measurements. The obtained results showed that the ligand behaves as a neutral bidentate, forming chelates with molar ratios: 1:1, 1:2 and 1:3; M:L for binary and 1:2:1 and 1:1:1; M:L:L‧ for ternary complexes, which can be formulated as: [LmCuXn(H2O)y]·zH2O, m = 1 or 2, n = 0, 1 or 2, X = OAc-, SO42-, Cl- or Br-, y = 0 or 2, z = 0 or 0.5; [LmCu(H2O)n]X2·zMeOH, m = 2 or 3, n = 0 or 2, X = ClO4- or NO3-, z = 0 or 1 and [Lm L'Cu(H2O)n](NO3)x·yS, m = 1 or 2, n = 0 or 2, X = 1 or 2, y = 0.5 or 4, S = H2O or MeOH. The ESR spin Hamiltonian parameters of some complexes were calculated. Kinetic parameters (Ea, A, ΔH, ΔS and ΔG) of the thermal decomposition stages have been evaluated using Coats-Redfern equations. The structural parameters of the ligand and its metal complexes have been calculated and correlated with the experimental data. The metal complexes exhibited octahedral and square planar geometrical arrangements according to the nature of the anion. The ligand and its metal complexes showed antibacterial activity towards Gram-positive bacteria, Gram-negative bacteria, yeast and fungus.

Integrated Population Pharmacokinetic Analysis of Rivaroxaban Across Multiple Patient Populations

PubMed Central

Zhang, Liping; Frede, Matthias; Kubitza, Dagmar; Mueck, Wolfgang; Schmidt, Stephan; Solms, Alexander; Yan, Xiaoyu; Garmann, Dirk

2018-01-01

The population pharmacokinetics (PK) of rivaroxaban have been evaluated in several population‐specific models. We developed an integrated population PK model using pooled data from 4,918 patients in 7 clinical trials across all approved indications. Effects of gender, age, and weight on apparent clearance (CL/F) and apparent volume of distribution (V/F), renal function, and comedication on CL/F, and relative bioavailability as a function of dose (F) were analyzed. Virtual subpopulations for exposure simulations were defined by age, creatinine clearance (CrCL) and body mass index (BMI). Rivaroxaban PK were adequately described by a one‐compartment disposition model with a first‐order absorption rate constant. Significant effects of CrCL, use of comedications, and study population on CL/F, age, weight, and gender on V/F, and dose on F were identified. CrCL had a modest influence on exposure, whereas age and BMI had a minor influence. The model was suitable to predict rivaroxaban exposure in patient subgroups of special interest. PMID:29660785

Synthesis, characterization, and application of two Al(OR(F))3 Lewis superacids.

PubMed

Kraft, Anne; Trapp, Nils; Himmel, Daniel; Böhrer, Hannes; Schlüter, Peter; Scherer, Harald; Krossing, Ingo

2012-07-23

We report herein the synthesis and full characterization of the donor-free Lewis superacids Al(OR(F))(3) with OR(F) = OC(CF(3))(3) (1) and OC(C(5)F(10))C(6)F(5) (2), the stabilization of 1 as adducts with the very weak Lewis bases PhF, 1,2-F(2)C(6)H(4), and SO(2), as well as the internal C-F activation pathway of 1 leading to Al(2)(F)(OR(F))(5) (4) and trimeric [FAl(OR(F))(2)](3) (5, OR(F) = OC(CF(3))(3)). Insights have been gained from NMR studies, single-crystal structure determinations, and DFT calculations. The usefulness of these Lewis acids for halide abstractions has been demonstrated by reactions with trityl chloride (NMR; crystal structures). The trityl salts allow the introduction of new, heteroleptic weakly coordinating [Cl-Al(OR(F))(3)](-) anions, for example, by hydride or alkyl abstraction reactions. Copyright © 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Zincobotryogen, ZnFe3+(SO4)2(OH)ṡ7H2O: validation as a mineral species and new data

NASA Astrophysics Data System (ADS)

Yang, Zhuming; Giester, Gerald; Mao, Qian; Ma, Yuguang; Zhang, Di; Li, He

2017-06-01

Zincobotryogen occurs in the oxidation zone of the Xitieshan lead-zinc deposit, Qinghai, China. The mineral is associated with jarosite, copiapite, zincocopiapite, and quartz. The mineral forms prismatic crystals, 0.05 to 2 mm in size. It is optically positive (2Vcalc = 54.1°), with Z ‖ b and X ∧ c = 10°. The elongation is negative. The refractive indices are n α = 1.542(5), n β = 1.551(5), n γ = 1.587(5). The pleochroism scheme is X = colorless, Y = light yellow, Z = yellow. Microprobe analysis gave (in wt%): SO3 = 38.04, Al2O3 = 0.04, Fe2O3 = 18.46, ZnO = 13.75, MgO = 1.52, MnO = 1.23, H2O = 31.06 (by calculation), Total = 104.10. The simplified formula is (Zn,Mg)Fe3+(SO4)2(OH)ṡ7H2O. The mineral is monoclinic, P121/ n1, a = 10.504(2), b = 17.801(4), c = 7.1263(14) Å, and β = 100.08(3)°, V = 1311.9(5) Å3, Z = 4. The strongest lines in the powder X-ray diffraction pattern d(I)( hkl) are: 8.92 (100)(110), 6.32 (77)(-101), 5.56 (23)(021), 4.08 (22)(-221),3.21 (31)(231), 3.03 (34)(032), 2.77 (22)(042). The crystal structure was refined using 2816 unique reflections to R1( F) = 0.0355 and wR2( F 2) = 0.0651. The refined formula is (Zn0.84Mg0.16)Fe3+(SO4)2(OH)ṡ7H2O. The atomic arrangement is characterized by chains with composition [Fe3+(SO4)2(OH)(H2O)]2- and 7 Å repeat distance running parallel to the c-axis. The chain links to a [ MO(H2O)5] octahedron ( M = Zn, Mg) and an unshared H2O molecule, and forms a larger chain building module with composition [ M 2+Fe3+(SO4)2(OH)(H2O)6(H2O)]. The inter-chain module linkage involves only hydrogen bonding.

Seasonal variation of fine- and coarse-mode nitrates and related aerosols over East Asia: synergetic observations and chemical transport model analysis

NASA Astrophysics Data System (ADS)

Uno, Itsushi; Osada, Kazuo; Yumimoto, Keiya; Wang, Zhe; Itahashi, Syuichi; Pan, Xiaole; Hara, Yukari; Kanaya, Yugo; Yamamoto, Shigekazu; Fairlie, Thomas Duncan

2017-11-01

We analyzed long-term fine- and coarse-mode synergetic observations of nitrate and related aerosols (SO42-, NO3-, NH4+, Na+, Ca2+) at Fukuoka (33.52° N, 130.47° E) from August 2014 to October 2015. A Goddard Earth Observing System chemical transport model (GEOS-Chem) including dust and sea salt acid uptake processes was used to assess the observed seasonal variation and the impact of long-range transport (LRT) from the Asian continent. For fine aerosols (fSO42-, fNO3-, and fNH4+), numerical results explained the seasonal changes, and a sensitivity analysis excluding Japanese domestic emissions clarified the LRT fraction at Fukuoka (85 % for fSO42-, 47 % for fNO3-, 73 % for fNH4+). Observational data confirmed that coarse NO3- (cNO3-) made up the largest proportion (i.e., 40-55 %) of the total nitrate (defined as the sum of fNO3-, cNO3-, and HNO3) during the winter, while HNO3 gas constituted approximately 40 % of the total nitrate in summer and fNO3- peaked during the winter. Large-scale dust-nitrate (mainly cNO3-) outflow from China to Fukuoka was confirmed during all dust events that occurred between January and June. The modeled cNO3- was in good agreement with observations between July and November (mainly coming from sea salt NO3-). During the winter, however, the model underestimated cNO3- levels compared to the observed levels. The reason for this underestimation was examined statistically using multiple regression analysis (MRA). We used cNa+, nss-cCa2+, and cNH4+ as independent variables to describe the observed cNO3- levels; these variables were considered representative of sea salt cNO3-, dust cNO3-, and cNO3- accompanied by cNH4+), respectively. The MRA results explained the observed seasonal changes in dust cNO3- and indicated that the dust-acid uptake scheme reproduced the observed dust-nitrate levels even in winter. The annual average contributions of each component were 43 % (sea salt cNO3-), 19 % (dust cNO3-), and 38 % (cNH4+ term). The MRA dust-cNO3- component had a high value during the dust season, and the sea salt component made a large contribution throughout the year. During the winter, cNH4+ term made a large contribution. The model did not include aerosol microphysical processes (such as condensation and coagulation between the fine anthropogenic aerosols NO3- and SO42- and coarse particles), and our results suggest that inclusion of aerosol microphysical processes is critical when studying observed cNO3- formation, especially in winter.

Physiologically Based Pharmacokinetic Modeling in Lead Optimization. 1. Evaluation and Adaptation of GastroPlus To Predict Bioavailability of Medchem Series.

PubMed

Daga, Pankaj R; Bolger, Michael B; Haworth, Ian S; Clark, Robert D; Martin, Eric J

2018-03-05

When medicinal chemists need to improve bioavailability (%F) within a chemical series during lead optimization, they synthesize new series members with systematically modified properties mainly by following experience and general rules of thumb. More quantitative models that predict %F of proposed compounds from chemical structure alone have proven elusive. Global empirical %F quantitative structure-property (QSPR) models perform poorly, and projects have too little data to train local %F QSPR models. Mechanistic oral absorption and physiologically based pharmacokinetic (PBPK) models simulate the dissolution, absorption, systemic distribution, and clearance of a drug in preclinical species and humans. Attempts to build global PBPK models based purely on calculated inputs have not achieved the <2-fold average error needed to guide lead optimization. In this work, local GastroPlus PBPK models are instead customized for individual medchem series. The key innovation was building a local QSPR for a numerically fitted effective intrinsic clearance (CL loc ). All inputs are subsequently computed from structure alone, so the models can be applied in advance of synthesis. Training CL loc on the first 15-18 rat %F measurements gave adequate predictions, with clear improvements up to about 30 measurements, and incremental improvements beyond that.

On the Ground Electronic States of TiF and TiCl

PubMed

Boldyrev; Simons

1998-04-01

The low-lying electronic states of TiF and TiCl have been studied using high level ab initio techniques. Both are found to have two low-lying excited electronic states, 4Sigma- (0.080 eV (TiF) and 0.236 eV (TiCl)) and 2Delta (0.266 eV (TiF) and 0.348 eV (TiCl)), and 4Phi ground states at the highest CCSD(T)/6-311++G(2d,2f) level of theory. Our theoretical predictions of 4Phi ground electronic states for TiF and TiCl support recent experimental findings by Ram and Bernath, and our calculated bond lengths and vibrational frequencies are in reasonable agreement with their experimental data. Copyright 1998 Academic Press.

Trace element and major ion composition of wet and dry depositon in Ankara, Turkey

NASA Astrophysics Data System (ADS)

Kaya, Güven; Tuncel, Gürdal

Daily, wet-only precipitation samples collected over a two year period were analyzed for SO 42-, NO 3-, Cl -, NH 4+, H +, Ca, Mg, K, Na, Al, Cu, Cd, Cr, Zn, V and Ni. Weekly dry-deposition samples collected on petri-dishes over the same period were analyzed only for major ions. Concentrations of ions and elements in Ankara precipitation are comparable with concentrations reported in literature for other urban areas. However, the wet deposition fluxes are the lowest among literature values, owing to small annual precipitation in the region. Although, annual average pH in precipitation is 4.7, episodic rain events with fairly low pH's were observed. Approximately half of the acidity in Ankara precipitation is neutralized in the winter season, while the acidity is completely neutralized by airborne soil particles that are rich in CaCO 3 in the summer precipitation. The SO 42- and NO 3- contributes approximately equally on the free acidity in winter. Main forms of SO 42- and NO 3- in precipitation are CaSO 4 and Ca(NO 3) 2, respectively. Crustal elements and ions have higher concentrations during summer season, while anthropogenic ions and elements did not show well-defined seasonal cycles. The lack of industrial activity in Ankara has profound influence on the temporal behavior of elements and ions.

Why are SiX5(-) and GeX5(-) (X = F, Cl) stable but not CF5(-) and CCl5(-)?

PubMed

Marchaj, Marzena; Freza, Sylwia; Skurski, Piotr

2012-03-01

The possible existence of the CF(5)(-), CCl(5)(-), SiF(5)(-), SiCl(5)(-), GeF(5)(-), and GeCl(5)(-) anions has been investigated using ab initio methods. The species containing Si and Ge as central atoms were found to adopt the D(3h)-symmetry trigonal bipyramidal equilibrium structures whose thermodynamic stabilities were confirmed by examining the most probable fragmentation channels. The ab initio re-examination of the electronic stabilities of the SiF(5)(-), SiCl(5)(-), GeF(5)(-), and GeCl(5)(-) anions [using the OVGF(full) method with the 6-311+G(3df) basis set] led to the very large vertical electron detachment (VDE) energies of 9.316 eV (SiF(5)(-)) and 9.742 eV (GeF(5)(-)), whereas smaller VDEs of 6.196 and 6.452 eV were predicted for the SiCl(5)(-) and GeCl(5)(-) species, respectively. By contrast, the high-symmetry and structurally compact anionic CF(5)(-) and CCl(5)(-) systems cannot exist due to the strongly repulsive potential predicted for the X(-) (F(-) or Cl(-)) approaching the CX(4) (CF(4) or CCl(4)). The formation of weakly bound CX(4)···X(-) (CF(4)···F(-) and CCl(4)···Cl(-)) anionic complexes (consisting of pseudotetrahedral neutral CX(4) with the weakly tethered X(-)) might be expected at low temperatures (approaching 0 K), whereas neither CX(5)(-) (CF(5)(-), CCl(5)(-)) systems nor CX(4)···X(-) (CF(4)···F(-) and CCl(4)···Cl(-)) complexes can exist in the elevated temperatures (above 0K) due to their susceptibility to the fragmentation (leading to the X(-) loss). © 2012 American Chemical Society

Cl-rich hydrous mafic mineral assemblages in the Highiș massif, Apuseni Mountains, Romania

NASA Astrophysics Data System (ADS)

Bonin, Bernard; Tatu, Mihai

2016-08-01

The Guadalupian (Mid-Permian) Highiș massif (Apuseni Mountains, Romania) displays a bimodal igneous suite of mafic (gabbro, diorite) and A-type felsic (alkali feldspar granite, albite granite, and hybrid granodiorite) rocks. Amphibole is widespread throughout the suite, and yields markedly high chlorine contents. Three groups are identified: Cl-rich potassic hastingsite (2.60-3.40 wt% Cl) within A-type felsic rocks and diorite, mildly Cl-rich pargasite to hornblende (0.80-1.90 wt% Cl) within gabbro, and low F-Cl hornblende within gabbro and hybrid granodiorite. Coexisting biotite is either Cl-rich within diorite, or F-Cl-poor to F-rich within A-type felsic rocks. Chlorine and fluorine are distributed in both mafic phases, according to the F-Fe and Cl-Mg avoidance rules. The low-Ti contents suggest subsolidus compositions. Cl-rich amphibole within diorite and A-type felsic rocks yields a restricted temperature range - from 575 °C down to 400 °C, whereas mildly Cl-rich amphibole within gabbro displays the highest range - from 675 to 360 °C. Temperatures recorded by Cl-rich biotite within diorite range from 590 to 410 °C. Biotite within A-type felsic rocks yields higher temperatures than amphibole: the highest values- from 640 to 540 °C - are recorded in low-F-Cl varieties, whereas the lowest values- from 535 to 500 °C - are displayed by F-rich varieties. All data point to halogen-rich hydrothermal fluids at upper greenschist facies conditions percolating through fractures and shear zones and pervasively permeating the whole Highiș massif, with F precipitating as interstitial fluorite and Cl incorporating into amphibole, during one, or possibly several, hydrothermal episodes that would have occurred during a ~ 150 My-long period of time extending from the Guadalupian (Mid-Permian) to the Albian (Mid-Cretaceous).

Effect of industrial dust on precipitation chemistry in the Czech Republic (Central Europe) from 1850 to 2013.

PubMed

Kopáček, Jiří; Hejzlar, Josef; Krám, Pavel; Oulehle, Filip; Posch, Maximilian

2016-10-15

Using statistical relationships between the composition of precipitation at eight long-term monitoring stations and emission rates of sulphur (S) and nitrogen (N) compounds, as well as industrial dust in the Czech Republic and Slovakia (Central Europe), we modelled historic pH and concentrations of sulphate (SO4(2-)), nitrate (NO3(-)), ammonium (NH4(+)), chloride (Cl(-)), base cations (BC), and bicarbonate (HCO3(-)) in bulk precipitation from 1850 to 2013. Our model suggests that concentrations of SO4(2-), NO3(-), and HCO3(-) were similar (11-16 μeq l(-1)) in 1850. Cations were dominated by NH4(+) and BC (24-27 μeq l(-1)) and precipitation pH was >5.6. The carbonate buffering system was depleted around 1920 and precipitation further acidified at an exponential rate until the 1980s, when concentrations of SO4(2-), NO3(-), Cl(-), NH4(+) and BC reached maxima of 126, 55, 16, 76, and 57 μeq l(-1), respectively, and pH decreased to 4.2. Dust emissions from industrial sources were an important source of BC. Without their contribution, pH would have decreased to 4.0 in the 1980s, and the carbonate buffering system would have been depleted already in the 1870s. Since the late 1980s, concentrations of strong acid anions and BC have decreased by 46-81% (i.e. more than in Europe on average) due to a 53-93% reduction in regional emissions of S and N compounds and dust from industrial and agricultural sources. The present composition of precipitation is similar to the late 19th century, except for NO3(-) concentrations, which are similar to those during 1926-1950. Precipitation pH now exceeds 5.0, the carbonate buffering system has been re-established, and HCO3(-) has again become (after almost a century) a significant component of precipitation chemistry. Copyright © 2016 Elsevier Ltd. All rights reserved.

Density of high-spin states in38Ar and42Ca

NASA Astrophysics Data System (ADS)

Kern, Th.; Betz, P.; Bitterwolf, E.; Glatz, F.; Röpke, H.

1980-03-01

The γ-decay modes of38Ar levels with E x ≦11,630keV and of42Ca levels with E x ≦10,036keV have been studied using the35Cl( α, pγ) reaction at 16MeV and the39K( α, pγ) reaction at 15.14 MeV, respectively. In both nuclei the number of states with J≧6 exceeds fifty. Weak coupling calculations of the Bansal and French type reproduce the density of high-spin states. The success of the model implies that the excitations of up to four particles from the d 3/2 into the f 7/2 shell play a role in both nuclei. The structure of deformed states was found to be predominantly 4 p/s 6 h in38Ar and 4 p/s 2 h in42Ca, respectively.

Modeling and observational constraints on the sulfur cycle in the marine troposphere: a focus on reactive halogens and multiphase chemistry

NASA Astrophysics Data System (ADS)

Chen, Q.; Breider, T.; Schmidt, J.; Sherwen, T.; Evans, M. J.; Xie, Z.; Quinn, P.; Bates, T. S.; Alexander, B.

2017-12-01

The radiative forcing from marine boundary layer clouds is still highly uncertain, which partly stems from our poor understanding of cloud condensation nuclei (CCN) formation. The oxidation of dimethyl sulfide (DMS) and subsequent chemical evolution of its products (e.g. DMSO) are key processes in CCN formation, but are generally very simplified in large-scale models. Recent research has pointed out the importance of reactive halogens (e.g. BrO and Cl) and multiphase chemistry in the tropospheric sulfur cycle. In this study, we implement a series of sulfur oxidation mechanisms into the GEOS-Chem global chemical transport model, involving both gas-phase and multiphase oxidation of DMS, DMSO, MSIA and MSA, to improve our understanding of the sulfur cycle in the marine troposphere. DMS observations from six locations around the globe and MSA/nssSO42- ratio observations from two ship cruises covering a wide range of latitudes and longitudes are used to assess the model. Preliminary results reveal the important role of BrO for DMS oxidation at high latitudes (up to 50% over Southern Ocean). Oxidation of DMS by Cl radicals is small in the model (within 10% in the marine troposphere), probably due to an underrepresentation of Cl sources. Multiphase chemistry (e.g. oxidation by OH and O3 in cloud droplets) is not important for DMS oxidation but is critical for DMSO oxidation and MSA production and removal. In our model, about half of the DMSO is oxidized in clouds, leading to the formation of MSIA, which is further oxidized to form MSA. Overall, with the addition of reactive halogens and multiphase chemistry, the model is able to better reproduce observations of seasonal variations of DMS and MSA/nssSO42- ratios.

Speciation of the major inorganic salts in atmospheric aerosols of Beijing, China: Measurements and comparison with model

NASA Astrophysics Data System (ADS)

Tang, Xiong; Zhang, Xiaoshan; Ci, Zhijia; Guo, Jia; Wang, Jiaqi

2016-05-01

In the winter and summer of 2013-2014, we used a sampling system, which consists of annular denuder, back-up filter and thermal desorption set-up, to measure the speciation of major inorganic salts in aerosols and the associated trace gases in Beijing. This sampling system can separate volatile ammonium salts (NH4NO3 and NH4Cl) from non-volatile ammonium salts ((NH4)2SO4), as well as the non-volatile nitrate and chloride. The measurement data was used as input of a thermodynamic equilibrium model (ISORROPIA II) to investigate the gas-aerosol equilibrium characteristics. Results show that (NH4)2SO4, NH4NO3 and NH4Cl were the major inorganic salts in aerosols and mainly existed in the fine particles. The sulfate, nitrate and chloride associated with crustal ions were also important in Beijing where mineral dust concentrations were high. About 19% of sulfate in winter and 11% of sulfate in summer were associated with crustal ions and originated from heterogeneous reactions or direct emissions. The non-volatile nitrate contributed about 33% and 15% of nitrate in winter and summer, respectively. Theoretical thermodynamic equilibrium calculations for NH4NO3 and NH4Cl suggest that the gaseous precursors were sufficient to form stable volatile ammonium salts in winter, whereas the internal mixing with sulfate and crustal species were important for the formation of volatile ammonium salts in summer. The results of the thermodynamic equilibrium model reasonably agreed with the measurements of aerosols and gases, but large discrepancy existed in predicting the speciation of inorganic ammonium salts. This indicates that the assumption on crustal species in the model was important for obtaining better understanding on gas-aerosol partitioning and improving the model prediction.

Evaluation of groundwater quality in rural-areas of northern Malawi: Case of Zombwe Extension Planning Area in Mzimba

NASA Astrophysics Data System (ADS)

Chidya, Russel C. G.; Matamula, Swithern; Nakoma, Oliver; Chawinga, Charles B. J.

2016-06-01

Many people in in the Sub-Saharan region rely on groundwater for drinking and other household uses. Despite this significance, information on the chemical composition of the water in the boreholes and emperical data on groundwater quality is limited in some rural areas of Malawi. This study was conducted to evaluate the physico-chemical quality of water from boreholes (n = 20) in Zombwe Extension Planning Area (EPA), Mzimba in Northern Malawi to ascertain their safety. Desktop studies and participatory approaches were employed to assess the socio-economic activities and water supply regime in the study areas. The water samples were analysed for pH, conductivity (EC), turbidity, water temperature, nitrate (NO3-), magnesium (Mg), calcium (Ca), zinc (Zn), fluoride (F-), and sulphate (SO42-). In-situ and laboratory analyses were carried out using portable meters and standard procedures. The results were compared with national (Malawi Bureau of Standards - MBS) and international standards (World Health Organization - WHO) for drinking water. The following ranges were obtained: pH (6.00-7.80), EC (437-3128 μS/cm), turbidity (0.10-5.80 NTU), water temperature (27.0-30.60 °C), NO3- (0.30-30.00 mg/L), F- (0.10-8.10 mg/L), Mg (31.00-91.00 mg/L), Ca (20.00-197.10 mg/L), SO42- (10.20-190 mg/L), Fe (0.10-3.60 mg/L) and Zn (0.00-5.10 mg/L). Generally, some parameters tested at several sites (>80%, n = 20) complied with both MBS and WHO limits. No significant differences (p > 0.05) was observed for most parameters (>65%, n = 11). Groundwater contamination was not significant in the area despite some parameters like F-, Ca and SO42- showing higher levels at other sites. Some sites registered very hard water (244.60-757.80 mg/L CaCO3) probably due to mineralization influenced by underground rock material. Further studies are needed to ascertain the groundwater quality of other parameters (like F-, and SO42-) which registered higher levels at some sites. Routine monitoring of the groundwater in the study area and entire Malawi is needed for spatio-temporal variation assessment and to ensure good public health.

New molten salt systems for high temperature molten salt batteries: Ternary and quaternary molten salt systems based on LiF-LiCl, LiF-LiBr, and LiCl-LiBr

NASA Astrophysics Data System (ADS)

Fujiwara, Syozo; Inaba, Minoru; Tasaka, Akimasa

Using a new simulative technique developed by us, we systematically investigated new ternary or quaternary molten salt systems, which are based on LiF-LiCl, LiF-LiBr, and LiCl-LiBr binary systems, for use as electrolytes in thermal batteries, and evaluated their ionic conductivities and melting points experimentally. It was confirmed experimentally that LiF-LiBr-KF (melting point: 425 °C, ionic conductivity at 500 °C: 2.52 S cm -1), LiCl-LiBr-KF (405 °C, 2.56 S cm -1), LiCl-LiBr-NaF-KF (425 °C, 3.11 S cm -1), LiCl-LiBr-NaCl-KCl (420 °C, 2.73 S cm -1), and LiCl-LiBr-NaBr-KBr (420 °C, 2.76 S cm -1) meet our targets for both melting point (350-430 °C) and ionic conductivity (2.0 S cm -1 and higher at 500 °C). A single cell using the newly developed LiCl-LiBr-NaCl-KCl molten salt as an electrolyte was prepared, and the DC-IR of the cell decreased by 20% than that of a single cell using the conventional LiCl-KCl molten salt. It was therefore concluded that the use of new quaternary molten salt systems can improve the discharge rate-capability in practical battery applications because of their high ionic conductivities.

Remedial Investigation/Feasibility Study (RI/FS) Report, Davis Global Communications Site. Volume 3

DTIC Science & Technology

1994-02-23

ESCP! PrO ~f, Hard, light Olive brown to Oliv Drown (2 a~ , t, sil dry. grosses and rootlets presert r ~Hard. dark bofwn (lOYR 4/3) cjoyey SiT, cry F... CON ,1NUOUS CORING PROJECT NO.: 409717 CUENT: HAZWRAP LOCATION: McCLELLAN AIR FORCE BASE L!J - DAVIS, CA | BORING NO. SBB-23 ’• F/ • j- - - o L Fm G...FFT§,77.,...".. . ...P ?E. ATIE :bEt; IT,ý IR1L_’T < • nOR CONS !STENCY. SO)L STRUtCTURE. i-" ..LL 6" -6" -6" ’ -T S S = ; ’•: .. . . Cl- X - L- N

Computation provides chemical insight into the diverse hydride NMR chemical shifts of [Ru(NHC)4(L)H]0/+ species (NHC = N-heterocyclic carbene; L = vacant, H2, N2, CO, MeCN, O2, P4, SO2, H-, F- and Cl-) and their [Ru(R2PCH2CH2PR2)2(L)H]+ congeners.

PubMed

Häller, L Jonas L; Mas-Marzá, Elena; Cybulski, Mateusz K; Sanguramath, Rajashekharayya A; Macgregor, Stuart A; Mahon, Mary F; Raynaud, Christophe; Russell, Christopher A; Whittlesey, Michael K

2017-02-28

Relativistic density functional theory calculations, both with and without the effects of spin-orbit coupling, have been employed to model hydride NMR chemical shifts for a series of [Ru(NHC) 4 (L)H] 0/+ species (NHC = N-heterocyclic carbene; L = vacant, H 2 , N 2 , CO, MeCN, O 2 , P 4 , SO 2 , H - , F - and Cl - ), as well as selected phosphine analogues [Ru(R 2 PCH 2 CH 2 PR 2 ) 2 (L)H] + (R = i Pr, Cy; L = vacant, O 2 ). Inclusion of spin-orbit coupling provides good agreement with the experimental data. For the NHC systems large variations in hydride chemical shift are shown to arise from the paramagnetic term, with high net shielding (L = vacant, Cl - , F - ) being reinforced by the contribution from spin-orbit coupling. Natural chemical shift analysis highlights the major orbital contributions to the paramagnetic term and rationalizes trends via changes in the energies of the occupied Ru d π orbitals and the unoccupied σ* Ru-H orbital. In [Ru(NHC) 4 (η 2 -O 2 )H] + a δ-interaction with the O 2 ligand results in a low-lying LUMO of d π character. As a result this orbital can no longer contribute to the paramagnetic shielding, but instead provides additional deshielding via overlap with the remaining (occupied) d π orbital under the L z angular momentum operator. These two effects account for the unusual hydride chemical shift of +4.8 ppm observed experimentally for this species. Calculations reproduce hydride chemical shift data observed for [Ru( i Pr 2 PCH 2 CH 2 P i Pr 2 ) 2 (η 2 -O 2 )H] + (δ = -6.2 ppm) and [Ru(R 2 PCH 2 CH 2 PR 2 ) 2 H] + (ca. -32 ppm, R = i Pr, Cy). For the latter, the presence of a weak agostic interaction trans to the hydride ligand is significant, as in its absence (R = Me) calculations predict a chemical shift of -41 ppm, similar to the [Ru(NHC) 4 H] + analogues. Depending on the strength of the agostic interaction a variation of up to 18 ppm in hydride chemical shift is possible and this factor (that is not necessarily readily detected experimentally) can aid in the interpretation of hydride chemical shift data for nominally unsaturated hydride-containing species. The synthesis and crystallographic characterization of the BAr F 4 - salts of [Ru(IMe 4 ) 4 (L)H] + (IMe 4 = 1,3,4,5-tetramethylimidazol-2-ylidene; L = P 4 , SO 2 ; Ar F = 3,5-(CF 3 ) 2 C 6 H 3 ) and [Ru(IMe 4 ) 4 (Cl)H] are also reported.

The effect of hydrochloric acid addition to increase carbon nanotubes dispersibility as drug delivery system by covalent functionalization

NASA Astrophysics Data System (ADS)

Wulan, P. P. D. K.; Ulwani, S. H.; Wulandari, H.; Purwanto, W. W.; Mulia, K.

2018-03-01

This study is to obtain the effect of adding hydrochloric acid (HCl) to the mixture of sulfuric acid (H2SO4) and HNO3 in CNT covalent functionalization. HCl expected to increase the dispersibility of functionalized CNT by improving the dispersion time period done with H2SO4 or HNO3. Functionalization used mixture of H2SO4 and HNO3 with volume ratio of 3:1. Covalent functionalization used 0.5 grams of MWCNT ultra sonicated in 50mL HNO3 with and mixture of H2SO4 and HNO3. Additions of 200 mL HCl used variation of molarity from 1M, 2M, 3M, 4M, 5M to 6M. CNT were oxidized to form carboxylic and hydroxyl bonds on the surface that increase dispersibility of CNT. FTIR spectrums showed the existences of carboxyl and hydroxyl group on spectra of 2600-3700 cm-1 and 900-1400 cm-1. Dispersion tests, which showed functionalized CNT (f-CNT) dispersion capabilities, were done by dissolving f-CNT in water. The study resulted that 6M f-CNT (NSC6) gave the best dispersion with zeta potential value of -37.1mV. NSC6 gave the longest dispersion time which was 20 days until f-CNT settle again. SEM-EDS micrographs showed the surface structure of 6M f-CNT without significant damage and no longer contain impurities of Fe, Ni, and Cl.

Atmospheric dry deposition in the vicinity of the Salton Sea, California - I: Air pollution and deposition in a desert environment

USGS Publications Warehouse

Alonso, R.; Bytnerowicz, A.; Boarman, W.I.

2005-01-01

Air pollutant concentrations and atmospheric dry deposition were monitored seasonally at the Salton Sea, southern California. Measurements of ozone (O 3), nitric acid vapor (HNO3), ammonia (NH3), nitric oxide (NO), nitrogen dioxide (NO2) and sulfur dioxide (SO 2) were performed using passive samplers. Deposition rates of NO 3-, NH4+, Cl-, SO 42-, Na+, K+ and Ca2+ to creosote bush branches and nylon filters as surrogate surfaces were determined for one-week long exposure periods. Maximum O3 values were recorded in spring with 24-h average values of 108.8 ??g m-3. Concentrations of NO and NO2 were low and within ranges of the non-urban areas in California (0.4-5.6 and 3.3-16.2 ??g m-3 ranges, respectively). Concentrations of HNO3 (2.0-6.7 ??g m-3) and NH 3 (6.4-15.7 ??g m-3) were elevated and above the levels typical for remote locations in California. Deposition rates of Cl-, SO42-, Na+, K+ and Ca2+ were related to the influence of sea spray or to suspended soil particles, and no strong enrichments caused by ions originated by human activities were detected. Dry deposition rates of NO3- and NH4+ were similar to values registered in areas where symptoms of nitrogen saturation and changes in species composition have been described. Deposition of nitrogenous compounds might be contributing to eutrophication processes at the Salton Sea. ?? 2005 Elsevier Ltd. All rights reserved.

Partitioning of F and Cl Between Apatite and a Synthetic Shergottite Liquid (QUE 94201) at 4 Gpa from 1300 TO 1500 C

NASA Technical Reports Server (NTRS)

McCubbin, F. M.; Barnes, J. J.; Vander Kaaden, K. E.; Boyce, J. W.

2017-01-01

Apatite [Ca5(PO4)3(F,Cl,OH)] is present in a wide range of planetary materials. Due to the presence of volatiles within its crystal structure (Xsite), many recent studies have attempted to use apatite to constrain the volatile contents of planetary magmas and mantle sources. In order to use the volatile contents of apatite to accurately determine the abundances of volatiles in coexisting silicate melt or fluids, thermodynamic models for the apatite solid solution and for the apatite components in multicomponent silicate melts and fluids are required. Although some thermodynamic models for apatite have been developed, they are incomplete. Furthermore, no mixing model is available for all of the apatite components in silicate melts or fluids, especially for F and Cl components. Several experimental studies have investigated the apatite-melt and apatite-fluid partitioning behavior of F, Cl, and OH in terrestrial and planetary systems, which have determined that apatite-melt partitioning of volatiles are best described as exchange equilibria similar to Fe-Mg partitioning between olivine and silicate melt. However, McCubbin et al., recently reported that the exchange coefficients vary in portions of apatite compositional space where F, Cl, and OH do not mix ideally in apatite. In particular, solution calorimetry data of apatite compositions along the F-Cl join exhibit substantial excess enthalpies of mixing, and McCubbin et al. reported substantial deviations in the Cl-F exchange Kd along the F-Cl apatite join that could be explained by the preferential incorporation of F into apatite. In the present study, we assess the effect of apatite crystal chemistry on F-Cl exchange equilibria between apatite and melt at 4 GPa over the temperature range of 1300-1500 C. The goal of these experiments is to assess the variation in the Ap-melt Cl-F exchange Kd over a broad range of F:Cl ratios in apatite. The results of these experiments could be used to understand at what composition apatite shifts from a hexagonal unit cell with space group P63/m to a unit cell with monoclinic symmetry within space group P21/b. We anticipate that this transition occurs at >70% chlorapatite based on solution calorimetry data.

Pyrosequencing analysis yields comprehensive assessment of microbial communities in pilot-scale two-stage membrane biofilm reactors.

PubMed

Ontiveros-Valencia, Aura; Tang, Youneng; Zhao, He-Ping; Friese, David; Overstreet, Ryan; Smith, Jennifer; Evans, Patrick; Rittmann, Bruce E; Krajmalnik-Brown, Rosa

2014-07-01

We studied the microbial community structure of pilot two-stage membrane biofilm reactors (MBfRs) designed to reduce nitrate (NO3(-)) and perchlorate (ClO4(-)) in contaminated groundwater. The groundwater also contained oxygen (O2) and sulfate (SO4(2-)), which became important electron sinks that affected the NO3(-) and ClO4(-) removal rates. Using pyrosequencing, we elucidated how important phylotypes of each "primary" microbial group, i.e., denitrifying bacteria (DB), perchlorate-reducing bacteria (PRB), and sulfate-reducing bacteria (SRB), responded to changes in electron-acceptor loading. UniFrac, principal coordinate analysis (PCoA), and diversity analyses documented that the microbial community of biofilms sampled when the MBfRs had a high acceptor loading were phylogenetically distant from and less diverse than the microbial community of biofilm samples with lower acceptor loadings. Diminished acceptor loading led to SO4(2-) reduction in the lag MBfR, which allowed Desulfovibrionales (an SRB) and Thiothrichales (sulfur-oxidizers) to thrive through S cycling. As a result of this cooperative relationship, they competed effectively with DB/PRB phylotypes such as Xanthomonadales and Rhodobacterales. Thus, pyrosequencing illustrated that while DB, PRB, and SRB responded predictably to changes in acceptor loading, a decrease in total acceptor loading led to important shifts within the "primary" groups, the onset of other members (e.g., Thiothrichales), and overall greater diversity.

Secondary effects of anion exchange on chloride, sulfate, and lead release: systems approach to corrosion control.

PubMed

Willison, Hillary; Boyer, Treavor H

2012-05-01

Water treatment processes can cause secondary changes in water chemistry that alter finished water quality including chloride, sulfate, natural organic matter (NOM), and metal release. Hence, the goal of this research was to provide an improved understanding of the chloride-to-sulfate mass ratio (CSMR) with regards to chloride and sulfate variations at full-scale water treatment plants and corrosion potential under simulated premise plumbing conditions. Laboratory corrosion studies were conducted using Pb-Sn solder/Cu tubing galvanic cells exposed to model waters with low (approx. 5 mg/L Cl(-) and 10 mg/L SO(4)(2-)) and high (approx. 50 mg/L Cl(-) and 100 mg/L SO(4)(2-)) concentrations of chloride and sulfate at a constant CSMR of ≈ 0.5. The role of NOM during corrosion was also evaluated by changing the type of organic material. In addition, full-scale sampling was conducted to quantify the raw water variability of chloride, sulfate, and NOM concentrations and the changes to these parameters from magnetic ion exchange treatment. Test conditions with higher concentrations of chloride and sulfate released significantly more lead than the lower chloride and sulfate test waters. In addition, the source of NOM was a key factor in the amount of lead released with the model organic compounds yielding significantly less lead release than aquatic NOM. Copyright © 2012 Elsevier Ltd. All rights reserved.

Influence of marine, terrestrial and anthropogenic sources on ionic and metallic composition of rainwater at a suburban site (northwest coast of Spain)

NASA Astrophysics Data System (ADS)

Moreda-Piñeiro, Jorge; Alonso-Rodríguez, Elia; Moscoso-Pérez, Carmen; Blanco-Heras, Gustavo; Turnes-Carou, Isabel; López-Mahía, Purificación; Muniategui-Lorenzo, Soledad; Prada-Rodríguez, Darío

2014-05-01

In the present research, the rainwater chemistry of soluble (SF) and non-soluble (NSF) fractions is studied over a one a half year period (from March 2011 to August 2012) at a suburban site (Oleiros, A Coruña, Spain). The monthly rainfall in this region during the studied period ranged from 10 to 137 mm, while the NSF ranged from 0.9 to 54 mg L-1. More rainfall occurs within October-January. Eighteen samples, which provide information pertaining to the monthly variation in chemistry, were analyzed. Trace metals (Al, As, Ba, Co, Cu, Cr, Fe, Mn, Ni, Pb, Sr, V, Zn) were enclosed in the study of both fractions of the rainwater. Major inorganic ions (Cl-, NO3-, SO42-, Na+, K+, Ca2+, Mg2+ and NH4+) were also enclosed in the study of the SF of the rainwater. After partition coefficients analysis, univariate and principal components analysis (PCA) and air mass back trajectories analysis, three sources were found for the ionic and metal composition of the SF of rainwater; terrestrial (Ca2+, non sea salt SO42-, Al and Fe), marine (Mg2+, Na+, Cl-) and anthropogenic (K+, NH4+, NO3-, Fe, Mn, Pb, Sr, V and Zn). Results also suggest ubiquitous sources for Ba, Co, Cu, Cr and Ni. One source (terrestrial) was found for NSF of rainwater.

Assessment of hydrogeochemistry and environmental isotopes of surface and groundwaters in the Kütahya Plain, Turkey

NASA Astrophysics Data System (ADS)

Abadi Berhe, Berihu; Erdem Dokuz, Uğur; Çelik, Mehmet

2017-10-01

The aim of the present work is to determine the geochemical processes that control the nature of the groundwater and assess the quality of water for drinking and public health purposes. Surface and groundwater samples of Kütahya plain were analyzed for their physio-chemical and environmental isotope properties. The relative concentrations of the water ions were found to occur in the order of Ca2+>Mg2+>(K+ + Na+) and HCO3->SO42->Cl-. Piper diagram shows that Ca-Mg/Mg-Ca-HCO3 was the dominant water types. Waters in the area were super-saturated with respect to carbonates. However, they were under-saturated with respect to sulphate minerals. The groundwaters had a mean isotopic composition of -67.32 δ2H and -9.72 δ18O and were comparatively lower than surface waters -64.64 δ2H and -9.25 δ18O. Tritium activities in groundwater from the wells ranged from 1.00 to 8.38 TU with a mean value of 4.37 TU. The impact of agricultural practices and poor sanitation conditions is indicated by the positive correlation between K+ - NO3-, K+- NO2- and HCO3- - Cl- ions as well as Na+ and Mg2+ ions with SO42-ion. The groundwater quality of Kütahya plain is influenced by various natural and anthropogenic factors.

Selective inclusion of PO4(3-) within persistent dimeric capsules of a tris(thiourea) receptor and evidence of cation/solvent sealed unimolecular capsules.

PubMed

Dey, Sandeep Kumar; Das, Gopal

2012-08-07

A tren-based tris(thiourea) receptor, L with electron-withdrawing p-nitrophenyl terminals has been established as a competent hydrogen-bonding scaffold that can selectively encapsulate PO(4)(3-) within persistent and rigid dimeric capsules, assembled by aromatic π-stacking interactions between the receptor side-arms. A quaternary ammonium salt of PO(4)(3-) capsules (complexes 1 and 1b, 2:1 host-guest) can reproducibly be obtained in quantitative yields by a solution-state deprotonation of [HL](+) moieties and a bound HPO(4)(2-) anion of complex 1a (HPO(4)(2-) complex of protonated L, 2:1 host-guest), induced by the presence of a large excess of anions such as HCO(3)(-), CH(3)CO(2)(-), and F(-). Qualitative as well as quantitative (1)H and (31)P NMR experiments (DMSO-d(6)) have been carried out in detail to demonstrate the selective and preferential inclusion of PO(4)(3-) by L in solution-states. Competitive crystallization experiments performed in the presence of an excess of anions such as HCO(3)(-), HSO(4)(-), CH(3)CO(2)(-), NO(3)(-) and halides (F(-) and Cl(-)) further establish the phenomenon of selective PO(4)(3-) encapsulation as confirmed by (1)H NMR, (31)P NMR, FT-IR and powder X-ray diffraction patterns of the isolated crystals. X-ray structural analyses and (31)P NMR studies of the isolated crystals of phosphate complexes (1, 1a and 1b) provide evidence of the binding discrepancy of inorganic phosphates with protonated and neutral form of L. Furthermore, extensive studies have been carried out with other anions of different sizes and dimensions in solid- and solution-states (complexes 2a, 3, 4 and 5). Crystal structure elucidation revealed the formation of a solvent (DMSO) sealed unimolecular capsule in the F(-) encapsulated complex, 2a (1:1 host-guest), a CO(3)(2-) encapsulated centrosymmetric molecular capsule in 3 (2:1 host-guest) and a cation (tetrabutylammonium) sealed SO(4)(2-) encapsulated unimolecular capsule in 4 (1:1 host-guest). 2D-NOESY NMR experiments carried out on these capsule complexes further confirm the relevant binding stoichiometry of complexes (2a-4) except for the PO(4)(3-)-encapsulated complex (1b) which showed a 1:1 host-guest stoichiometry in solution.

Ab initio study of the structural, electronic, elastic and thermal conductivity properties of SrClF with pressure effects

NASA Astrophysics Data System (ADS)

Lv, Zhen-Long; Cui, Hong-Ling; Wang, Hui; Li, Xiao-Hong; Ji, Guang-Fu

2017-04-01

SrClF is an important optical crystal and can be used as pressure gauge in diamond anvil cell at high pressure. In this work, we performed a systematic study on the structural, electronic and elastic properties of SrClF under pressure, as well as its thermal conductivity, by first-principles calculation. Different exchange-correlation functionals were tested and PBESOL was finally chosen to study these properties of SrClF. Studies reveal that SrClF has a bulk modulus of about 56.2 GPa (by fitting equation of states) or 54.3 GPa (derived from elastic constants), which agree well with the experimental result. SrClF is mechanically and dynamically stable up to 50 GPa. Its elastic constants increase with the applied pressure, but its mechanical anisotropy deteriorates as the pressure increases. Investigation of its electronic properties reveals that SrClF is a direct band-gap insulator with a gap value of 5.73 eV at 0 GPa, which decreases with the increasing pressure and the reason is found by analysing the partial density of states. Based on the calculated phonon dispersion curves, thermal conductivity of SrClF is predicated. At ambient conditions, the predicted thermal conductivity is about 3.74 Wm-1 K-1, while that obtained using the simplified Slack model give a slightly larger value of 4.62 Wm-1 K-1.

The Role of Intercalated Cell Nedd4-2 in BP Regulation, Ion Transport, and Transporter Expression.

PubMed

Nanami, Masayoshi; Pham, Truyen D; Kim, Young Hee; Yang, Baoli; Sutliff, Roy L; Staub, Olivier; Klein, Janet D; Lopez-Cayuqueo, Karen I; Chambrey, Regine; Park, Annie Y; Wang, Xiaonan; Pech, Vladimir; Verlander, Jill W; Wall, Susan M

2018-06-01

Background Nedd4-2 is an E3 ubiquitin-protein ligase that associates with transport proteins, causing their ubiquitylation, and then internalization and degradation. Previous research has suggested a correlation between Nedd4-2 and BP. In this study, we explored the effect of intercalated cell (IC) Nedd4-2 gene ablation on IC transporter abundance and function and on BP. Methods We generated IC Nedd4-2 knockout mice using Cre-lox technology and produced global pendrin/ Nedd4-2 null mice by breeding global Nedd4-2 null ( Nedd4-2 -/- ) mice with global pendrin null ( Slc26a4 -/- ) mice. Mice ate a diet with 1%-4% NaCl; BP was measured by tail cuff and radiotelemetry. We measured transepithelial transport of Cl - and total CO 2 and transepithelial voltage in cortical collecting ducts perfused in vitro Transporter abundance was detected with immunoblots, immunohistochemistry, and immunogold cytochemistry. Results IC Nedd4-2 gene ablation markedly increased electroneutral Cl - /HCO 3 - exchange in the cortical collecting duct, although benzamil-, thiazide-, and bafilomycin-sensitive ion flux changed very little. IC Nedd4-2 gene ablation did not increase the abundance of type B IC transporters, such as AE4 ( Slc4a9 ), H + -ATPase, barttin, or the Na + -dependent Cl - /HCO 3 - exchanger ( Slc4a8 ). However, IC Nedd4-2 gene ablation increased CIC-5 total protein abundance, apical plasma membrane pendrin abundance, and the ratio of pendrin expression on the apical membrane to the cytoplasm. IC Nedd4-2 gene ablation increased BP by approximately 10 mm Hg. Moreover, pendrin gene ablation eliminated the increase in BP observed in global Nedd4-2 knockout mice. Conclusions IC Nedd4-2 regulates Cl - /HCO 3 - exchange in ICs., Nedd4-2 gene ablation increases BP in part through its action in these cells. Copyright © 2018 by the American Society of Nephrology.

Contingent use of fetal fibronectin testing and cervical length measurement in women with preterm labour.

PubMed

Audibert, François; Fortin, Suzanne; Delvin, Edgard; Djemli, Anissa; Brunet, Suzanne; Dubé, Johanne; Fraser, William D

2010-04-01

To evaluate the contingent use of fetal fibronectin (fFN) testing and cervical length (CL) measurement to predict preterm delivery, and to validate the use of phosphorylated IGFBP-1 as a predictor of preterm delivery. We recruited 71 women with a clinical diagnosis of preterm labour between 24 and 34 weeks, and tested for the presence of fFN and IGFBP-1 in the cervicovaginal secretions of all women immediately before CL measurement. Among the 66 women with complete outcome, four were excluded from the final analysis as two had assessment for fFN but no CL measurement, and another two had CL measured but no screening for fFN. Among 62 women with complete results, the mean gestational age at recruitment was 29.4 +/- 2.5 weeks. Six women (9.6%) delivered within two weeks of assessment, and 14 (22.5%) delivered before 34 weeks. A positive fFN test resulted in a sensitivity of 83%, a specificity of 84%, a positive predictive value of 36%, and a negative predictive value of 98% for delivery within two weeks; for CL < 25 mm, these figures were 50%, 52%, 10%, and 91%, respectively, and for a positive IGFBP-1, they were 17%, 93%, 20%, and 91%, respectively. A policy of contingent use of fFN (in which the test was assumed to be positive if CL < or = 15 mm, and fFN was only measured if the CL was between 16 and 30 mm) gave sensitivity, specificity, positive and negative predictive values of 80%, 61%, 17%, and 97%, respectively for delivery within two weeks. Using this contingent use protocol, only one third of women needed fFN screening after CL measurement. In this study, IGFBP-1 screening did not predict preterm delivery and fFN screening provided the best predictive capacity. A policy of contingent use of testing for fFN after CL measurement, or contingent use of CL measurement after fFN screening (depending on available resources) is a promising approach to limit use of resources.

Measurement and modeling of CO₂ solubility in natural and synthetic formation brines for CO₂ sequestration.

PubMed

Zhao, Haining; Dilmore, Robert; Allen, Douglas E; Hedges, Sheila W; Soong, Yee; Lvov, Serguei N

2015-02-03

CO2 solubility data in the natural formation brine, synthetic formation brine, and synthetic NaCl+CaCl2 brine were collected at the pressures from 100 to 200 bar, temperatures from 323 to 423 K. Experimental results demonstrate that the CO2 solubility in the synthetic formation brines can be reliably represented by that in the synthetic NaCl+CaCl2 brines. We extended our previously developed model (PSUCO2) to calculate CO2 solubility in aqueous mixed-salt solution by using the additivity rule of the Setschenow coefficients of the individual ions (Na(+), Ca(2+), Mg(2+), K(+), Cl(-), and SO4(2-)). Comparisons with previously published models against the experimental data reveal a clear improvement of the proposed PSUCO2 model. Additionally, the path of the maximum gradient of the CO2 solubility contours divides the P-T diagram into two distinct regions: in Region I, the CO2 solubility in the aqueous phase decreases monotonically in response to increased temperature; in region II, the behavior of the CO2 solubility is the opposite of that in Region I as the temperature increases.

Diketonylpyridinium Cations as a Support of New Ionic Liquid Crystals and Ion-Conductive Materials: Analysis of Counter-Ion Effects

PubMed Central

Pastor, María Jesús; Cuerva, Cristián; Campo, José A.; Schmidt, Rainer; Torres, María Rosario; Cano, Mercedes

2016-01-01

Ionic liquid crystals (ILCs) allow the combination of the high ionic conductivity of ionic liquids (ILs) with the supramolecular organization of liquid crystals (LCs). ILCs salts were obtained by the assembly of long-chained diketonylpyridinium cations of the type [HOOR(n)pyH]+ and BF4−, ReO4−, NO3−, CF3SO3−, CuCl42− counter-ions. We have studied the thermal behavior of five series of compounds by differential scanning calorimetry (DSC) and hot stage polarized light optical microscopy (POM). All materials show thermotropic mesomorphism as well as crystalline polymorphism. X-ray diffraction of the [HOOR(12)pyH][ReO4] crystal reveals a layered structure with alternating polar and apolar sublayers. The mesophases also exhibit a lamellar arrangement detected by variable temperature powder X-ray diffraction. The CuCl42− salts exhibit the best LC properties followed by the ReO4− ones due to low melting temperature and wide range of existence. The conductivity was probed for the mesophases in one species each from the ReO4−, and CuCl42− families, and for the solid phase in one of the non-mesomorphic Cl− salts. The highest ionic conductivity was found for the smectic mesophase of the ReO4− containing salt, whereas the solid phases of all salts were dominated by electronic contributions. The ionic conductivity may be favored by the mesophase lamellar structure. PMID:28773485

Ion balance and acidity of size-segregated particles during haze episodes in urban Beijing

NASA Astrophysics Data System (ADS)

Tian, Shili; Pan, Yuepeng; Wang, Yuesi

2018-03-01

In this study, we investigated how the ion balance causes variations in size segregated aerosol acidity and atmospheric processing on clean versus hazy days using a 9-stage sampler. We calculated the ratios (in charge equivalents, RC/A) between measured cations (Na+, NH4+, K+, Mg2 +, and Ca2 +) and anions (SO42 -, NO3- and Cl-) for different aerosol size fractions. The ratios were typically close to unity in the accumulation mode (0.65-2.1 μm), and increased significantly when the particle size increased or decreased. In the coarse size range (aerodynamic diameter > 2.1 μm), high RC/A values were most likely caused by the undetermined CO32- and HCO3- content of the mineral dust. In contrast, the high RC/A values for submicron aerosols (< 1.1 μm) were likely caused by the presence of water-soluble organic anions. The RC/A values for all size fractions were lower on hazy days than clean days, indicating that aerosol acidity was enhanced on polluted days. Simiar temporal trend between RC/A and in-situ pH indicated that RC/A was a good indicator of aerosol acidity in fine mode aerosol. The SO42 - and NO3- contents in fine particles were completely neutralized as the RC/A values for PM2.1 approached unity, and mean values of RC/A were 1.34 and 1.16 during the transition and polluted periods, respectively. The lowest RC/A values were observed in the size fraction with the highest concentrations of SO42 -, NO3- and NH4+ (SNA) and concentrations of SNA increased with the increasing aerosol acidity. Significant correlations between [NO3-]/[SO42 -] and [NH4+]/[SO42 -] during NH4+-rich conditions in fine size fractions indicated fine mode NO3- in Beijing was mainly formed by gas-phase homogeneous reaction between the ambient NH3 and HNO3.

Determination of folates by HPLC-chemiluminescence using a ruthenium(II)-cerium(IV) system, and its application to pharmaceutical preparations and supplements.

PubMed

Ikeda, Rie; Ichiyama, Kosuke; Tabuchi, Naoto; Wada, Mitsuhiro; Kuroda, Naotaka; Nakashima, Kenichiro

2014-11-01

A chemiluminescence (CL) reaction of folic acid (FA) with ruthenium (II) and cerium (IV) was applied to quantify FA-related compounds such as FA, dihydrofolic acid, tetrahydrofolic acid, 5-methyltetrahydrofolic acid, 5-formyltetrahydrofolic acid and methotrexate (MTX). Among the FAs, 5-methyltetrahydrofolic acid provided the highest CL intensity. HPLC-CL detection of FA was applied to quantify FA in pharmaceutical preparations and supplements. Analytical samples were separated on a semi-micro ODS column with a mixture of 20 mM phosphate buffer (pH 5.7) and acetonitrile (94 : 6, v/v %). The separated samples were mixed with a post-column CL reagent consisting of 1.5 mM Ru(bipy)3 (2+) and 1.0 mM Ce(SO4)2 , then the generated CL was monitored. The calibration range for FA was 10-100 μM and the limit of detection was 1.34 μM (signal-to-noise ratio of 3). Repeatabilities were 4.2, 4.6 and 5.0 RSD% (10, 25, 50 μM), and the recoveries for FA supplement, vitamin B complex supplement and FA-containing medication (tablet) were 102.4 ± 10.5, 103.3 ± 13.3 and 100.3 ± 8.5%, respectively. The described method is robust against changes in the chromatographic parameters of ± 3.3 or ± 1.5%. The measured FA content corresponded well to the labeled content of FA-containing products (100.6-104.9%), demonstrating the precision and accuracy of this method for the evaluation of FA pharmaceutical preparations. Copyright © 2014 John Wiley & Sons, Ltd.

Development of polyethersulfone (PES)/silver nanoparticles (AgNPs)/polyethylene glycol (PEG) nanofiltration membrane

NASA Astrophysics Data System (ADS)

Johary, Fasihah; Jamaluddin, Nur Adibah; Rohani, Rosiah; Hassan, Abdul Rahman; Sharifuddin, Syazrin Syima; Isa, Mohd Hafez Mohd

2018-06-01

Nanofiltration is a membrane-based separation process that has been used widely in the separation and purification fields for various applications such as dye desalting, applications of water softening, pharmaceuticals and wastewater treatment. In this research, polyethersulfone (PES), polyethylene glycol (PEG), Pluronic F108 and silver nanoparticles (AgNPs) nanofiltration membrane was prepared using casting solution technique with N-methyl-2-pyrrolidone (NMP) was used as a solvent. The effects of Pluronic F108 and silver nanoparticles (AgNPs) concentrations in the casting solutions on the membrane performance/properties were also studied. The membrane pure water permeation (PWP) and salt rejection tests were carried out for membrane performance analysis. Scanning electron microscopy (SEM) was used for the membrane morphology characterization. Fourier transform infrared spectroscopy was utilized to identify functional groups in the membrane. Membrane with 2.0 wt.% of Pluronic F108 and 0.05 wt.% of AgNPs showed the best performances for both PWP (40.89 L/m2h) as well as permeation flux of salts solution of NaCl (43.95 L/m2h), Na2SO4 (21.16 L/m2h), MgCl2 (26.46 L/m2h) and MgSO4 (20.41 L/m2h). All fabricated membranes with different formulation of dope composition obtained high salts rejection in the range of 79% to 91%. SEM images showed addition of AgNPs has improved fabricated membrane morphology with higher pore density and larger macro-void structure.

Monsoon rain chemistry and source apportionment using receptor modeling in and around National Capital Region (NCR) of Delhi, India

NASA Astrophysics Data System (ADS)

Tiwari, Suresh; Kulshrestha, U. C.; Padmanabhamurty, B.

Studies on monsoon precipitation chemistry were carried out to understand the nature of rainwater and sources of pollution at eight different locations in and around the National Capital Region (NCR) of Delhi during southwest monsoon in the years 2003-2005. These sites were Bulandshahr (BUL), Garhmuktesar (GAR), Muradnagar (MUR), Sardhana (SAR), Panipat (PAN), Charkhi Dadri (CHA), Hodal (HOD) and Bahror (BAH). The rainwater samples, collected at these locations, were analyzed for major anions, cations and pH. The data were assessed for its quality. In general, the order of concentrations of major ions was observed to be: Ca 2+>SO 42->HCO 3->NH 4+>Cl ->NO 3->Na +>Mg 2+>K +>F -. The average pH of rainwater at these stations was observed to be 6.39, ranging from 5.77 to 6.62, indicating alkaline nature. However, a few rain events, 31% at Panipat, 12% at Muradnagar and 29% at Sardhana, were observed to be acidic (pH<5.6). Acidity observed at Panipat and Muradnagar is attributed to industrial influence but at Sardhana to weak organic acids contributed by surrounding vegetation. No definite trends are found for most of the components at all the sites. However, concentrations of Cl - at Bulandshahr; NO 3- at Muradnagar and Hodal; F - at Panipat and Bahror; Na + at Bulandshahr; K + at Bahror and Bulandshahr; Ca 2+ at Bulandshahr, Muradnagar, Charkhi Dadri and Sardhana; Mg 2+ at Panipat, Bahror, Bulandshahr, Hodal and Sardhana have increased from 2003 to 2005. For source identification, principal component analysis (PCA) was made, which showed that in general, at all the sites; suspended soil-dust and sea salts which are natural sources, were identified as the most dominating. Sources like agriculture including cattle, brick kilns and industries were reflected in third or fourth PC indicating moderate influence of anthropogenic activities in this region.

Synergistic effects of sodium hypochlorite and ultraviolet radiation in reducing the levels of selected foodborne pathogenic bacteria.

PubMed

Ha, Ji-Hyoung; Ha, Sang-Do

2011-05-01

The purpose of this study was to determine whether combined treatment would produce synergistic effects to facilitate the sterilization of food products during production relative to single treatment. To assess this hypothesis, we investigated the bactericidal effects of ultraviolet (UV) irradiation and a commercial chemical disinfectant, sodium hypochlorite (NaClO), on Bacillus cereus F4810/72, Cronobacter sakazakii KCTC 2949, Staphylococcus aureus ATCC 35556, Escherichia coli ATCC 10536, and Salmonella Typhimurium novobiocin/nalidixic acid in vitro. Various concentrations of NaClO (20, 60, 100, and 200 ppm NaClO) were tested along with exposure to UV radiation at various doses (6, 96, 216, 360, and 504 mW s/cm(2)). The combined NaClO/UV treatments resulted in greater reductions in bacterial counts than either treatment alone. The synergy values against B. cereus, C. sakazakii, S. aureus, Salmonella Typhimurium, and E. coli were 0.25-1.17, 0.33-1.97, 0.42-1.72, 0.02-1.44, and 0.01-0.85 log(10) CFU/mL, respectively. The results of this study suggest that a significant synergistic benefit results from combined NaClO/UV processing against food-borne pathogenic bacteria in vitro.

Letter Report on Relative Aerial Combat of the F-84E Versus the F-86A capability

DTIC Science & Technology

1951-01-30

o_ 600 ssoo > 4 o _ _ _ 6dLi 00 CL L-L 40000 0 S0 1 iso gure 2- 6 - z oo .. 600 s_.O ••• J oo:0 O:S 0:0 0:qs O:0 0:I 1 Ld.ELFRTO "WME 4• s. . 5P.84...LEGEND F-86A ------ F-84E. 0 ALTIrlUDE , 5• 5I--- I ,OH ATT DE. 0J𔃾 A I ISO zoo ?50 300 350 400 4S0 IAS - MPI- SECRET inclosure Figu.re 4...242, AFMC 01-275, & AFMC 02-005). 2. Please direct further questions to Lezora U. Nobles, AFMC CSO/SCOC, DSN 787- 8583 . L E RA LU. N OB LE S AFMC STINFO

The air pollution caused by the burning of fireworks during the lantern festival in Beijing

NASA Astrophysics Data System (ADS)

Wang, Ying; Zhuang, Guoshun; Xu, Chang; An, Zhisheng

The effects of the burning of fireworks on air quality in Beijing was firstly assessed from the ambient concentrations of various air pollutants (SO 2, NO 2, PM 2.5, PM 10 and chemical components in the particles) during the lantern festival in 2006. Eighteen ions, 20 elements, and black carbon were measured in PM 2.5 and PM 10, and the levels of organic carbon could be well estimated from the concentrations of dicarboxylic acids. Primary components of Ba, K, Sr, Cl -, Pb, Mg and secondary components of C 5H 6O 42-, C 3H 2O 42-, C 2O 42-, C 4H 4O 42-, SO 42-, NO 3- were over five times higher in the lantern days than in the normal days. The firework particles were acidic and of inorganic matter mostly with less amounts of secondary components. Primary aerosols from the burning of fireworks were mainly in the fine mode, while secondary formation of acidic anions mainly took place on the coarse particles. Nitrate was mainly formed through homogeneous gas-phase reactions of NO 2, while sulfate was largely from heterogeneous catalytic transformations of SO 2. Fe could catalyze the formation of nitrate through the reaction of α-Fe 2O 3 with HNO 3, while in the formation of sulfate, Fe is not only the catalyst, but also the oxidant. A simple method using the concentration of potassium and a modified method using the ratio of Mg/Al have been developed to quantify the source contribution of fireworks. It was found that over 90% of the total mineral aerosol and 98% of Pb, 43% of total carbon, 28% of Zn, 8% of NO 3-, and 3% of SO 42- in PM 2.5 were from the emissions of fireworks on the lantern night.

Crystal growth and crystal structures of six novel phases in the Mn/As/O/Cl(Br) system, as well as magnetic properties of α-Mn3(AsO4)2

NASA Astrophysics Data System (ADS)

Weil, Matthias; Kremer, Reinhard K.

2017-01-01

Chemical vapour transport reactions (900 °C → 820 °C, Cl2 or Br2 as transport agent) of in situ formed Mn3(AsO4)2 yielded the orthoarsenates(V) α-Mn3(AsO4)2 and β-Mn3(AsO4)2 as well as the oxoarsenate(V) halide compounds Mn7(AsO4)4Cl2, Mn11(AsO4)7Cl, Mn11(AsO4)7Br and Mn5(AsO4)3Cl. The crystal structures of all six phases were determined from single crystal X-ray diffraction data. The crystal structures of α-and β-Mn3(AsO4)2 are isotypic with the corresponding phosphate phases γ- and α-Mn3(PO4)2, respectively, and are reported here for the first time. A comparative discussion with other structures of general composition M3(AsO4)2 (M = Mg; divalent first-row transition metal) is given. The unique crystal structures of Mn7(AsO4)4Cl2 and that of the two isotypic Mn11(AsO4)7X (X = Cl, Br) structures are composed of two [MnO5] polyhedra, two [MnO4Cl2] polyhedra (one with site symmetry 1 bar), two AsO4 tetrahedra, and one [MnO5] polyhedron, three [MnO6] octahedra (one with site symmetry.m.), one [MnO4X], one [MnO5X] polyhedron and four AsO4 tetrahedra, respectively. The various polyhedra of the three arsenate(V) halides are condensed into three-dimensional framework structures by corner- and edge-sharing. Mn5(AsO4)3Cl adopts the chloroapatite structure. The magnetic and thermal properties of pure polycrystalline samples of a-Mn3(AsO4)2 were investigated in more detail. The magnetic susceptibility proves all Mn atoms to be in the oxidation state +2 yielding an effective magnetic moment per Mn atom of 5.9 μB. Long-range antiferromagnetic ordering is observed below 8.2 K consistent with the negative Curie-Weiss temperature of -50 K derived from the high temperature susceptibility data.

Halo-substituted thiosemicarbazones and their copper(II), nickel(II) complexes: Detailed spectroscopic characterization and study of antitumour activity against HepG2 human hepatoblastoma cells

NASA Astrophysics Data System (ADS)

Jagadeesh, M.; Kalangi, Suresh K.; Sivarama Krishna, L.; Reddy, A. Varada

2014-01-01

Copper(II) and nickel(II) complexes of two different halogen substituted thiosemicarbazone ligands were synthesized. The ligands 3,4-difluoroacetophenone thiosemicarbazone (1) and 2-bromo-4'-chloroacetophenone thiosemicarbazone (2) were characterized and confirmed spectroscopically by FT-IR, FT-Raman, UV-vis and fluorescence spectral analysis, while the respective copper(II) complexes [Cu(C9H9N3F2S)2Cl2] (1a), [Cu(C9H9N3ClBrS)2Cl2] (2a) and nickel(II) complexes [Ni(C9H9N3F2S)2] (1b), [Ni(C9H9N3ClBrS)2] (2b) were characterized by FT-IR, UV-vis and electron paramagnetic spectroscopy (EPR). The EPR spectra of the Cu(II) complexes provided the rhombic octahedral and axial symmetry of the complexes 1a and 2a respectively. For the complex 1a, the g values calculated as g1 = 2.1228, g2 = 2.0706 and g3 = 2.001 between 2900 and 3300 G. While for the complex 2a, a set of two resonance absorptions were observed. The synthesized compounds were tested for antitumor activity and showed that the ability to kill liver cancer cells significantly. Out of all the synthesized compounds, copper(II) complexes 1a and 2a showed high cytotoxic effect on liver cancer cells with 67.51% and 42.77% of cytotoxicity respectively at 100 μM.

Geothermal solute flux monitoring and the source and fate of solutes in the Snake River, Yellowstone National Park, WY

USGS Publications Warehouse

McCleskey, R. Blaine; Lowenstern, Jacob B.; Schaper, Jonas; Nordstrom, D. Kirk; Heasler, Henry P.; Mahony, Dan

2016-01-01

The combined geothermal discharge from over 10,000 features in Yellowstone National Park (YNP) can be can be estimated from the Cl flux in the Madison, Yellowstone, Falls, and Snake Rivers. Over the last 30 years, the Cl flux in YNP Rivers has been calculated using discharge measurements and Cl concentrations determined in discrete water samples and it has been determined that approximately 12% of the Cl flux exiting YNP is from the Snake River. The relationship between electrical conductivity and concentrations of Cl and other geothermal solutes was quantified at a monitoring site located downstream from the thermal inputs in the Snake River. Beginning in 2012, continuous (15 min) electrical conductivity measurements have been made at the monitoring site. Combining continuous electrical conductivity and discharge data, the Cl and other geothermal solute fluxes were determined. The 2013–2015 Cl fluxes (5.3–5.8 kt/yr) determined using electrical conductivity are comparable to historical data. In addition, synoptic water samples and discharge data were obtained from sites along the Snake River under low-flow conditions of September 2014. The synoptic water study extended 17 km upstream from the monitoring site. Surface inflows were sampled to identify sources and to quantify solute loading. The Lewis River was the primary source of Cl, Na, K, Cl, SiO2, Rb, and As loads (50–80%) in the Snake River. The largest source of SO4 was from the upper Snake River (50%). Most of the Ca and Mg (50–55%) originate from the Snake Hot Springs. Chloride, Ca, Mg, Na, K, SiO2, F, HCO3, SO4, B, Li, Rb, and As behave conservatively in the Snake River, and therefore correlate well with conductivity (R2 ≥ 0.97).

Dakar Senegal Limited Surface Observations Climatic Summary (LISOCS). Parts A, C-F.

DTIC Science & Technology

1985-09-01

REING S O NOWO IS N-OUS TOR A D OR RAIN & R A D/OR HAIL 08 WITH FOG AND OR SLOWI G AND OR WITH EST NO OFLO T 5ST-AD TO O DRIZZLE DRIZZ SLEET E . HAZE 0...7.259 7. OURS TOTAL OBS .44 3419 35? 347 371 2 67 371 b3 S 6 3589 333 529 42 USAF ETAC ’om’ 0-69-5 (OL A)oCT 7 o¢1" .. CL ] IA I C L2 N T MEANS AND

A novel dual-ratiometric-response fluorescent probe for SO2/ClO- detection in cells and in vivo and its application in exploring the dichotomous role of SO2 under the ClO- induced oxidative stress.

PubMed

Dou, Kun; Fu, Qiang; Chen, Guang; Yu, Fabiao; Liu, Yuxia; Cao, Ziping; Li, Guoliang; Zhao, Xianen; Xia, Lian; Chen, Lingxin; Wang, Hua; You, Jinmao

2017-07-01

Intracellular reactive sulfur species and reactive oxygen species play vital roles in immunologic mechanism. As an emerging signal transmitter, SO 2 can be generated as the anti-oxidant, while SO 2 is also a potential oxidative stress-inducer in organism. Aiming to elucidate in-depth the dichotomous role of SO 2 under oxidative stress, we designed a dual-response fluorescent probe that enabled the respective or successive detection of SO 2 and ClO - . The probe itself emits the red fluorescence (625 nm) which can largely switch to blue (410 nm) and green fluorescence (500 nm) respectively in response to SO 2 and ClO - , allowing the highly selective and accurate ratiometric quantification for both SO 2 and ClO - in cells. Moreover the ultrafast (SO 2 : <60 s; ClO - : within sec) and highly sensitive (detection limits: SO 2 : 3.5 nM; ClO - : 12.5 nM) detection were achieved. With the robust applicability, the developed probe was successfully used to quantify SO 2 and endogenous ClO - in respectively the HeLa cells and the RAW 264.7 cells, as well as to visualize the dynamic of SO 2 /ClO - in zebrafish. The fluorescent imaging studies and flow cytometry analysis confirmed the burst-and-depletion and meanwhile the oxidative-and-antioxidative effects of intracellular SO 2 under the NaClO induced oxidative stress. Copyright © 2017 Elsevier Ltd. All rights reserved.

Absolute infrared intensities for F-113 and F-114 and an assessment of their greenhouse warming potential relative to other chlorofluorocarbons

NASA Astrophysics Data System (ADS)

Rogers, Jerry D.; Stephens, Robert D.

1988-03-01

The literature concerning the "greenhouse" warming potentials of Chlorofluorocarbons F-11, F-12, F-22, F-113, F-114, F-134a, and F-142b is reviewed. Additionally, infrared intensities are reported for each of the fundamental absorption bands of F-113 (CF2ClCFCl2) and F-114 (CF2ClCF2Cl) in the region between 8 and 20 μm. The measurements were made with a Fourier transform infrared spectrometer operated at 0.04 cm-1 apodized resolution. The total intensities measured for this region were 4905 cm-2 atm-1 for F-113 and 6064 cm-2 atm-1 for F-114, compared to a total intensity of 3404 cm-2 atm-1 for F-12 (CF2Cl2) in the same region. On the basis of these infrared intensities and the atmospheric lifetimes of F-113 and of F-114 relative to F-12, and on a per unit mass basis, F-113 and F-114 are about 0.8 and 1.9 times as effective, respectively, as F-12 in the "greenhouse" warming of the Earth.

Evaluation of the Giggenbach bottle method using artificial fumarolic gases

NASA Astrophysics Data System (ADS)

Lee, S.; Jeong, H. Y.

2013-12-01

Volcanic eruption is one of the most dangerous natural disasters. Mt. Baekdu, located on the border between North Korea and China, has been recently showing multiple signs of its eruption. The magmatic activity of a volcano strongly affects the composition of volcanic gases, which can provide a useful tool for predicting the eruption. Among various volcanic gas monitoring methods, the Giggenbach bottle method involves the on-site sampling of volcanic gases and the subsequent laboratory analysis, thus making it possible to detect a range of volcanic gases at low levels. In this study, we aim to evaluate the effectiveness of the Giggenbach bottle method and develop the associated analytical tools using artificial fumarolic gases with known compositions. The artificial fumarolic gases are generated by mixing CO2, CO, H2S, SO2, Ar, and H2 gas streams with a N2 stream sparged through an acidic medium containing HCl and HF. The target compositions of the fumarolic gases are selected to cover those reported for various volcanoes under different tectonic environments as follows: CO2 (2-12 mol %), CO (0.3-1 mol %), H2S (0.7-2 mol %), SO2 (0.6-4 mol %), Ar (0.3-0.7 mol %), H2 (0.3-0.7 mol %), HCl (0.2-1 mol %), and HF (< 0.015 mol %). The artificial fumarolic gases are collected into an evacuated bottle partially filled with 4 M NaOH solution containing 0.5 mM Cd(CH3COO)2. While non-condensable components such as CO, Ar, H2, and N2 accumulate in the headspace of the bottle, acidic components including CO2, SO2, HCl, and HF dissolve into the alkaline solution. In case of H2S, it reacts with dissolved Cd2+ to precipitate as CdS(s). The gas accumulated in the headspace can be analyzed for CO, Ar, H2, and N2 on a gas chromatography. The alkaline solution is first separated from yellowish CdS precipitates by filtration, and then pretreated with hydrogen peroxide to oxidize dissolved SO2 (H2SO3) to SO42-. The resultant solution can be analyzed for SO2 as SO42-, HCl as Cl-, and HF as F- on an ion chromatography and CO2 on an ionic carbon analyzer. Also, the amount of H2S can be determined by measuring the remaining dissolved Cd2+ on an inductively coupled plasma-mass spectrometry.

Eu(2+)-Activated Alkaline-Earth Halophosphates, M5(PO4)3X:Eu(2+) (M = Ca, Sr, Ba; X = F, Cl, Br) for NUV-LEDs: Site-Selective Crystal Field Effect.

PubMed

Kim, Donghyeon; Kim, Sung-Chul; Bae, Jong-Seong; Kim, Sungyun; Kim, Seung-Joo; Park, Jung-Chul

2016-09-06

Eu(2+)-activated M5(PO4)3X (M = Ca, Sr, Ba; X = F, Cl, Br) compounds providing different alkaline-earth metal and halide ions were successfully synthesized and characterized. The emission peak maxima of the M5(PO4)3Cl:Eu(2+) (M = Ca, Sr, Ba) compounds were blue-shifted from Ca to Ba (454 nm for Ca, 444 nm for Sr, and 434 nm for Ba), and those of the Sr5(PO4)3X:Eu(2+) (X = F, Cl, Br) compounds were red-shifted along the series of halides, F → Cl → Br (437 nm for F, 444 nm for Cl, and 448 nm for Br). The site selectivity and occupancy of the activator ions (Eu(2+)) in the M5(PO4)3X:Eu(2+) (M = Ca, Sr, Ba; X = F, Cl, Br) crystal lattices were estimated based on theoretical calculation of the 5d → 4f transition energies of Eu(2+) using LCAO. In combination with the photoluminescence measurements and theoretical calculation, it was elucidated that the Eu(2+) ions preferably enter the fully oxygen-coordinated sites in the M5(PO4)3X:Eu(2+) (M = Ca, Sr, Ba; X = F, Cl, Br) compounds. This trend can be well explained by "Pauling's rules". These compounds may provide a platform for modeling a new phosphor and application in the solid-state lighting field.

Effect of TCE concentration and dissolved groundwater solutes on NZVI-promoted TCE dechlorination and H2 evolution.

PubMed

Liu, Yueqiang; Phenrat, Tanapon; Lowry, Gregory V

2007-11-15

Nanoscale zero-valent iron (NZVI) is used to remediate contaminated groundwater plumes and contaminant source zones. The target contaminant concentration and groundwater solutes (NO3-, Cl-, HCO3-, SO4(2-), and HPO4(2-)) should affect the NZVI longevity and reactivity with target contaminants, but these effects are not well understood. This study evaluates the effect of trichloroethylene (TCE) concentration and common dissolved groundwater solutes on the rates of NZVI-promoted TCE dechlorination and H2 evolution in batch reactors. Both model systems and real groundwater are evaluated. The TCE reaction rate constant was unaffected by TCE concentration for [TCE] < or = 0.46 mM and decreased by less than a factor of 2 for further increases in TCE concentration up to water saturation (8.4 mM). For [TCE] > or = 0.46 mM, acetylene formation increased, and the total amount of H2 evolved at the end of the particle reactive lifetime decreased with increasing [TCE], indicating a higher Fe0 utilization efficiency for TCE dechlorination. Common groundwater anions (5mN) had a minor effect on H2 evolution but inhibited TCE reduction up to 7-fold in increasing order of Cl- < SO4(2-) < HCO3- < HPO4(2). This order is consistent with their affinity to form complexes with iron oxide. Nitrate, a NZVI-reducible groundwater solute, present at 0.2 and 1 mN did not affect the rate of TCE reduction but increased acetylene production and decreased H2 evolution. NO3- present at > 3 mM slowed TCE dechlorination due to surface passivation. NO3- present at 5 mM stopped TCE dechlorination and H2 evolution after 3 days. Dissolved solutes accounted for the observed decrease of NZVI reactivity for TCE dechlorination in natural groundwater when the total organic content was small (< 1 mg/L).

Atmospheric occurrence, homologue patterns and source apportionment of short- and medium-chain chlorinated paraffins in Shanghai, China: Biomonitoring with Masson pine (Pinus massoniana L.) needles.

PubMed

Wang, Xue-Tong; Zhou, Jun; Lei, Bing-Li; Zhou, Jing-Ming; Xu, Si-Yue; Hu, Bao-Ping; Wang, De-Qing; Zhang, Dong-Ping; Wu, Ming-Hong

2016-08-01

A comprehensive survey was conducted to Masson pine (Pinus massoniana L.) needles widely distributed in Shanghai in order to investigate the levels and homologue group patterns of short- and medium-chain chlorinated paraffins (SCCPs and MCCPs), to identify and quantitatively assess source contributions to the total CPs in pine needle samples. The concentration ranged from not detected (ND) to 13,600ngg(-1) with a geometric mean (GM) value of 63.7ngg(-1) for ΣSCCPs, from 12.4 to 33,500ngg(-1) with a GM value of 677ngg(-1) for ΣMCCPs, and from 14.0 to 45,700ngg(-1) with a GM value of 768ngg(-1) for total CPs. For different sampling units, the pollution levels both for SCCPs and MCCPs in pine needles were in the same orders: Pudong>suburbs>Puxi>Chongming. These significant differences in SCCPs and MCCPs among four sampling units could be associated with difference in industrial activities and to some extent also in population density. All pine needle samples (n=131) were divided into 2 groups by hierarchical cluster analysis (HCA) for SCCPs and MCCPs, the most abundant homologue groups in the bulk of pine needle samples were C11Cl5-7 and C13Cl5-7 for SCCPs, and C14Cl7-8 and C15Cl7-8 for MCCPs. Correlation analysis suggested that SCCPs and MCCPs in pine needles in the studied area may be derived from different sources. Four sources for pine needles were identified by the FA-MLR model; their relative contributions to the total CP burden in pine needles were 18.0% for F1 (attributed to commercial SCCP mixture), 42.2% for F2 (attributed to commercial MCCP mixture), 29.3% for F3 (attributed to LRAT), and 10.5% for F4 (unknown source). CP contamination of atmospheric air by point sources and long-range atmospheric transport in Shanghai should receive more attention by local government. Copyright © 2016 Elsevier B.V. All rights reserved.

The absorption, fluorescence and phosphorescence spectra of α and β-F, Cl, Br-naphthalenes in crystalline matrixes at 77 K

NASA Astrophysics Data System (ADS)

Iliescu, T.; Milea, I.; Abdolrahman, P. M.

1984-03-01

The paper studies the absorption, fluorescence and phosphorescence spectra of α and β-F, Cl, Br-naphtalenes (α, β-F, Cl,BrN) in different matrixes at 77 K and different concentrations. From these spectra one obtaines the vibrational frequences.

Environmental and health risks of chlorine trifluoride (ClF3), an alternative to potent greenhouse gases in the semiconductor industry.

PubMed

Tsai, Wen-Tien

2011-06-15

The first accident involving chlorine trifluoride (ClF(3)) in the history of semiconductor fabrication processes occurred on 28 July 2006 at Hsinchu (Taiwan), resulting in a large release of the highly reactive material and causing the chemical burn to several workers. ClF(3) is used primarily as an in situ cleaning gas in the manufacture of semiconductor silicon-wafer devices in replacement of perfluorocompounds (PFCs) because they have the high potential to contribute significantly to the global warming. This article aimed at reviewing ClF(3) in the physicochemical properties, the industrial uses, and the environmental implications on the basis of its toxicity, reactivity, health hazards and exposure limits. The health hazards of probable decomposition/hydrolysis products from ClF(3) were also evaluated based on their basic physicochemical properties and occupational exposure limits. The occupational exposure assessment was further discussed to understand potentially hazardous risks caused by hydrogen fluoride and fluorides from the decomposition/hydrolysis products of ClF(3). Copyright © 2010 Elsevier B.V. All rights reserved.

Atmospheric aerosol monitoring and characterization: An emission control strategy to protect tropical forests

NASA Astrophysics Data System (ADS)

Mateus, V. L.; do Valles, T. V.; de Oliveira, T. B.; de Almeida, A. C.; Maia, L. F. P. G.; Saint'Pierre, T. D.; Gioda, A.

2013-12-01

Human activity represents one of the most harmful activities for biodiversity. Population growth has caused increasing interferences in natural areas suffering agriculture or urbanization. As a consequence, tropical forests are at risk, since they shelter more than half of the global biodiversity. In this context, protected areas are indeed important to preserve natural populations as well as threatened habitats. Aerosol samples were collected in two protected areas in Rio de Janeiro, Brazil, in order to quantify water-soluble species and evaluate anthropogenic influences considering secondary aerosol formation and organic compounds. Samplings were conducted at the National Park of Serra dos Orgãos (Parnaso) and the National Forest Mario Xavier (Flonamax) during 24 h every six days using a high-volume sampler from July 2010 to June 2012 (PM10) and from July 2011 to August 2012 (TSP), respectively. The aerosol mass was determined by Gravimetry. The water-soluble ionic composition (WSIC) was obtained by Ion Chromatography in order to determine the major anions (Br-, Cl-, F-, NO2-, NO3-, PO43-, SO42-) and cations (Li+, Ca2+, K+, Mg2+, Na+, NH4+); total water-soluble carbon (TWSC), water-soluble organic carbon (WSOC) were determined by a TOC analyzer and the elements were determined by Inductively Coupled Plasma Optical Emission Spectrometry. PM10 average concentrations ranged from 11.1 to 67.6 μg m-3 and TSP from 5.7 to 242.6 μg m-3. Regarding the ions, the highest cation concentration was measured for Na+ at both Parnaso and Flonamax sites, respectively, 2.9 and 6.1 μg m-3. Both sites are near to the coast, justifying these results. On the other hand, SO42- was the predominant anion measured at both sites with average concentrations ranged from 2.3 to 2.7 μg m-3. Around 50% of sulphate had a non-marine origin in the former site, while in the latter the percentage was of circa 40%. The correlation between NO3- and nss-SO42- was much stronger at Parnaso (r = 0.87) than at Flonamax (r = 0.46), suggesting a marked anthropogenic influence in the former. WSOC and nss-SO42- showed a moderate correlation ( r = 0.3-0.5) at both sites suggesting secondary aerosol formation. The dissimilarity between the areas regarding to water-soluble species are probably due to the particle size. However, both sites are influenced by highways, which, at first glance, is the highest anthropogenic input. In the conference, we will provide more data related to chemical characterization as well as the enrichment factor (EF) and principal component analysis (PCA), to better understand the source apportionment.

Inhibition of EBV-mediated membrane fusion by anti-gHgL antibodies

DOE Office of Scientific and Technical Information (OSTI.GOV)

Sathiyamoorthy, Karthik; Jiang, Jiansen; Mohl, Britta S.

Herpesvirus entry into cells requires the coordinated action of multiple virus envelope glycoproteins, including gH, gL, and gB. For EBV, the gp42 protein assembles into complexes with gHgL heterodimers and binds HLA class II to activate gB-mediated membrane fusion with B cells. EBV tropism is dictated by gp42 levels in the virion, as it inhibits entry into epithelial cells while promoting entry into B cells. The gHgL and gB proteins are targets of neutralizing antibodies and potential candidates for subunit vaccine development, but our understanding of their neutralizing epitopes and the mechanisms of inhibition remain relatively unexplored. Here we studiedmore » the structures and mechanisms of two anti-gHgL antibodies, CL40 and CL59, that block membrane fusion with both B cells and epithelial cells. We determined the structures of the CL40 and CL59 complexes with gHgL using X-ray crystallography and EM to identify their epitope locations. CL59 binds to the C-terminal domain IV of gH, while CL40 binds to a site occupied by the gp42 receptor binding domain. CL40 binding to gHgL/gp42 complexes is not blocked by gp42 and does not interfere with gp42 binding to HLA class II, indicating that its ability to block membrane fusion with B cells represents a defect in gB activation. Furthermore, these data indicate that anti-gHgL neutralizing antibodies can block gHgL-mediated activation of gB through different surface epitopes and mechanisms.« less

Inhibition of EBV-mediated membrane fusion by anti-gHgL antibodies

DOE Office of Scientific and Technical Information (OSTI.GOV)

Sathiyamoorthy, Karthik; Jiang, Jiansen; Möhl, Britta S.

Herpesvirus entry into cells requires the coordinated action of multiple virus envelope glycoproteins, including gH, gL, and gB. For EBV, the gp42 protein assembles into complexes with gHgL heterodimers and binds HLA class II to activate gB-mediated membrane fusion with B cells. EBV tropism is dictated by gp42 levels in the virion, as it inhibits entry into epithelial cells while promoting entry into B cells. The gHgL and gB proteins are targets of neutralizing antibodies and potential candidates for subunit vaccine development, but our understanding of their neutralizing epitopes and the mechanisms of inhibition remain relatively unexplored. Here we studiedmore » the structures and mechanisms of two anti-gHgL antibodies, CL40 and CL59, that block membrane fusion with both B cells and epithelial cells. We determined the structures of the CL40 and CL59 complexes with gHgL using X-ray crystallography and EM to identify their epitope locations. CL59 binds to the C-terminal domain IV of gH, while CL40 binds to a site occupied by the gp42 receptor binding domain. CL40 binding to gHgL/gp42 complexes is not blocked by gp42 and does not interfere with gp42 binding to HLA class II, indicating that its ability to block membrane fusion with B cells represents a defect in gB activation. These data indicate that anti-gHgL neutralizing antibodies can block gHgL-mediated activation of gB through different surface epitopes and mechanisms.« less

Inhibition of EBV-mediated membrane fusion by anti-gHgL antibodies

DOE PAGES

Sathiyamoorthy, Karthik; Jiang, Jiansen; Mohl, Britta S.; ...

2017-09-22

Herpesvirus entry into cells requires the coordinated action of multiple virus envelope glycoproteins, including gH, gL, and gB. For EBV, the gp42 protein assembles into complexes with gHgL heterodimers and binds HLA class II to activate gB-mediated membrane fusion with B cells. EBV tropism is dictated by gp42 levels in the virion, as it inhibits entry into epithelial cells while promoting entry into B cells. The gHgL and gB proteins are targets of neutralizing antibodies and potential candidates for subunit vaccine development, but our understanding of their neutralizing epitopes and the mechanisms of inhibition remain relatively unexplored. Here we studiedmore » the structures and mechanisms of two anti-gHgL antibodies, CL40 and CL59, that block membrane fusion with both B cells and epithelial cells. We determined the structures of the CL40 and CL59 complexes with gHgL using X-ray crystallography and EM to identify their epitope locations. CL59 binds to the C-terminal domain IV of gH, while CL40 binds to a site occupied by the gp42 receptor binding domain. CL40 binding to gHgL/gp42 complexes is not blocked by gp42 and does not interfere with gp42 binding to HLA class II, indicating that its ability to block membrane fusion with B cells represents a defect in gB activation. Furthermore, these data indicate that anti-gHgL neutralizing antibodies can block gHgL-mediated activation of gB through different surface epitopes and mechanisms.« less

Line Lists for LiF and LiCl in the X 1Σ+ Ground State

NASA Astrophysics Data System (ADS)

Bittner, Dror M.; Bernath, Peter F.

2018-03-01

Vibration–rotation line lists for 6LiF, 7LiF, 6Li35Cl, 6Li37Cl, 7Li35Cl, and 7Li37Cl in the X 1Σ+ ground states have been prepared. The rovibrational energy levels have been calculated using potential energy surfaces determined by direct potential-fitting employing the rotational and rovibrational transition frequencies of all isotopologues, and required the inclusion of Born–Oppenheimer breakdown terms. Dipole moment functions calculated ab initio at the MRCI/aug-cc-pwCV5Z level have been used for line strength calculations. Partition functions for temperatures up to 5000 K have been calculated. LiF and LiCl are predicted to be present in the atmospheres of hot rocky exoplanets, brown dwarfs, and cool stars.

Apatite-Melt Partitioning at 1 Bar: An Assessment of Apatite-Melt Exchange Equilibria Resulting from Non-Ideal Mixing of F and Cl in Apatite

NASA Technical Reports Server (NTRS)

McCubbin, F. M.; Ustunisik, G.; Vander Kaaden, K. E.

2016-01-01

The mineral apatite [Ca5(PO4)3(F,Cl,OH)] is present in a wide range of planetary materials. Due to the presence of volatiles within its crystal structure (X-site), many recent studies have attempted to use apatite to constrain the volatile contents of planetary magmas and mantle sources. In order to use the volatile contents of apatite to precisely determine the abundances of volatiles in coexisting silicate melt or fluids, thermodynamic models for the apatite solid solution and for the apatite components in multi-component silicate melts and fluids are required. Although some thermodynamic models for apatite have been developed, they are incomplete. Furthermore, no mixing model is available for all of the apatite components in silicate melts or fluids, especially for F and Cl components. Several experimental studies have investigated the apatite-melt and apatite-fluid partitioning behavior of F, Cl, and OH in terrestrial and planetary systems, which have determined that apatite-melt partitioning of volatiles are best described as exchange equilibria similar to Fe-Mg partitioning between olivine and silicate melt. However, McCubbin et al. recently reported that the exchange coefficients may vary in portions of apatite compositional space where F, Cl, and OH do not mix ideally in apatite. In particular, solution calorimetry data of apatite compositions along the F-Cl join exhibit substantial excess enthalpies of mixing. In the present study, we conducted apatite-melt partitioning experiments in evacuated, sealed silica-glass tubes at approximately 1 bar and 950-1050 degrees Centigrade on a synthetic Martian basalt composition equivalent to the basaltic shergottite Queen Alexandria Range (QUE) 94201. These experiments were conducted dry, at low pressure, to assess the effects of temperature and apatite composition on the partitioning behavior of F and Cl between apatite and basaltic melt along the F-Cl apatite binary join, where there is non-ideal mixing of F and Cl in apatite.

Characterization of groundwater resources in the Trinity and Woodbine aquifers in Texas.

PubMed

Chaudhuri, Sriroop; Ale, Srinivasulu

2013-05-01

A vast region in north-central Texas, centering on Dallas-Fort Worth metroplex, suffers from intense groundwater drawdown and water quality degradation, which led to inclusion of 18 counties of this region into Priority Groundwater Management Areas. We combined aquifer-based and county-based hydrologic analyses to (1) assess spatio-temporal changes in groundwater level and quality between 1960 and 2010 in the Trinity and Woodbine aquifers underlying the study region, (2) delve into major hydrochemical facies with reference to aquifer hydrostratigraphy, and (3) identify county-based spatial zones to aid in future groundwater management initiatives. Water-level and quality data was obtained from the Texas Water Development Board (TWDB) and analyzed on a decadal scale. Progressive water-level decline was the major concern in the Trinity aquifer with >50% of observations occurring at depths >100 m since the 1980s, an observation becoming apparent only in the 2000s in the Woodbine aquifer. Water quality degradation was the major issue in the Woodbine aquifer with substantially higher percentage of observations exceeding the secondary maximum contaminant levels (SMCL; a non-enforceable threshold set by the United State Environmental Protection Agency (USEPA)) and/or maximum contaminant level (MCL, a legally enforceable drinking water standard set by the USEPA) for sulfate (SO4(2-)), chloride (Cl(-)), and fluoride (F(-)) in each decade. In both aquifers, however, >70% of observations exceeded the SMCL for total dissolved solids indicating high groundwater salinization. Water-level changes in Trinity aquifer also had significant negative impact on water quality. Hydrochemical facies in this region sequentially evolved from Ca-Mg-HCO3 and Ca-HCO3 in the fluvial sediments of the west to Na-SO4-Cl in the deltaic sediments to the east. Sequentially evolving hydrogeochemical facies and increasing salinization closely resembled regional groundwater flow pattern. Distinct spatial zones based on homogenous hydrologic characteristics have become increasingly apparent over time indicating necessity of zone-specific groundwater management strategies. Copyright © 2013 Elsevier B.V. All rights reserved.

[Effect of simulated inorganic anion leaching solution of electroplating sludge on the bioactivity of Acidithiobacillus ferrooxidans].

PubMed

Chen, Yan; Huang, Fang; Xie, Xin-Yuan

2014-04-01

An Acidithiobacillus ferrooxidans strain WZ-1 (GenBank sequence number: JQ968461) was used as the research object. The effects of Cl-, NO3-, F- and 4 kinds of simulated inorganic anions leaching solutions of electroplating sludge on the bioactivity of Fe2+ oxidation and apparent respiratory rate of WZ-1 were investigated. The results showed that Cl-, NO3(-)- didn't have any influence on the bioactivity of WZ-1 at concentrations of 5.0 g x L(-1), 1.0 g x L(-1), respectively. WZ-1 showed tolerance to high levels of Cl- and NO3- (about 10.0 g x L(-1), 5.0 g x L(-1), respectively), but it had lower tolerance to F- (25 mg x L(-1)). Different kinds of simulated inorganic anions leaching solutions of electroplating sludge had significant differences in terms of their effects on bioactivity of WZ-1 with a sequence of Cl-/NO3(-)/F(-) > or = NO3(-)/F(-) > Cl-/F(-) > Cl(-)/NO3(-).

Feed component inhibition in ethanolic fermentation by Saccharomyces cerevisiae.

PubMed

Maiorella, B L; Blanch, H W; Wilke, C R

1984-10-01

Inhibition by secondary feed components can limit productivity and restrict process options for the production of ethanol by fermentation. New fermentation processes (such as vacuum or extractive fermentation), while selectively removing ethanol, can concentrate nonmetabolized feed components in the remaining broth. Stillage recycle to reduce stillage waste treatment results in the buildup of nonmetabolized feed components. Continuous culture experiments are presented establishing an inhibition order: CaCl(2), (NH(4))(2)xSO(4) > NaCl, NH(4)Cl > KH(2)PO(4) > xylose, MgCl(2) > MgSO(4) > KCl. Reduction of the water activity alone is not an adequate predictor of the variation in inhibitory concentration among the different components tested. As a general trend, specific ethanol productivity increases and cell production decreases as inhibitors are added at higher concentration. We postulate that these results can be interpreted in terms of an increase in energy requirements for cell maintenance under hypertonic (stressed) conditions. Ion and carbohydrate transport and specific toxic effects are reviewed as they relate to the postulated inhibition mechanism. Glycerol production increases under hypertonic conditions and glycerol is postulated to function as a nontoxic osmoregulator. Calcium was the most inhibitory component tested, causing an 80%decline in cell mass production at 0.23 mol Ca(2+)/L and calcium is present at substantial concentration in many carbohydrate sources. For a typical final cane molasses feed, stillage recycle must be limited to less than onethird of the feed rate; otherwise inhibitory effects will be observed.

Hydrogen-facilitated corrosion and stress corrosion cracking of austenitic stainless steel of type 310

DOE Office of Scientific and Technical Information (OSTI.GOV)

Qiao Lijie; Chu Wuyang; Miao Huijun

1993-04-01

The effects of hydrogen precharge and stress on anodic dissolution for Type 310 austenitic stainless steel (ASS) have been investigated. An experiment determining the effect of hydrogen on stress corrosion cracking (SCC) was carried out in a boiling 42% MgCl[sub 2] solution and in a 2.5 mol/l H[sub 2]SO[sub 4] + 1 mol/l HCl solution. The results showed that both hydrogen and stress would increase the dissolution rate, and the effects of hydrogen and stress on the dissolution rate were synergistic rather than simply additive. Hydrogen lowered the threshold stress and the shortened fracture time of SCC in a boilingmore » MgCl[sub 2] solution by a factor of 1/5 and 10, respectively.« less

Authenticity screening of seized whiskey samples using electrophoresis microchips coupled with contactless conductivity detection.

PubMed

Rezende, Kariolanda C A; Moreira, Roger Cardoso; Logrado, Lucio Paulo Lima; Talhavini, Márcio; Coltro, Wendell K T

2016-10-01

This report describes for the first time the use of microchip electrophoresis (ME) devices integrated with capacitively coupled contactless conductivity detection (C 4 D) to investigate the authenticity of seized whiskey samples, which were probably adulterated by simple dilution with tap water. The proposed microfluidic platform was explored for the monitoring of anionic species (Cl - and F - ) in both original and tampered samples. The best separations were achieved within 70 s using a running buffer composed of lactic acid and histidine (pH = 5.9). ME-C 4 D devices were used to analyze samples from three different brands (five samples each). Based on the presence of inorganic anions like Cl - , F - , SO 4 2- and NO 2 - in different amounts, the authenticity of seized whiskeys was compared to original samples. According to the reported data, the proposed microfluidic platform can be useful to help regulatory authorities in the investigation and monitoring of authenticity of commercialized whiskey beverages. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Platinum and palladium incorporation into phosphate/viologen-phosphonates of zirconium and hafnium: synthesis and characterization

NASA Astrophysics Data System (ADS)

Dokoutchaev, Alexandre; Krishnan, Venkatesan V.; Thompson, Mark E.; Balasubramanian, Mahalingam

1998-10-01

We have continued previous efforts to synthesize and characterize a microporous metal phosphate/viologen-phosphonate compound, [(ZrF) 2(PO 4)(O 3PCH 2CH 2-4,4'-bipyridinium-CH 2CH 2PO 3)] ṡF·2H 2O, ZrPO PV. A derivative of this material has been shown to be an efficient catalyst for the production of hydrogen peroxide from hydrogen and oxygen. This paper has two objectives—one is to optimize the synthetic routes leading to the preparation of MPO PV (M=zirconium or hafnium) and the second is to characterize MPO PV and the derivatives formed by Pt or Pd incorporation by transmission electron microscopy (TEM), scanning electron microscopy (SEM), X-ray powder diffraction (XRD), inductively coupled plasma-mass spectrometry (ICP-MS) and X-ray absorption fine structure analysis (XAFS). Powder XRD data have shown much higher crystallinity in MPO PV samples prepared by hydrothermal methods than those prepared by reflux methods. In the hydrothermal synthesis, the amount of mineralizer (HF) present controlled the crystallite size (as determined from TEM micrographs). The larger the quantity of HF in the bomb, the larger the size of the crystals but the lower the yield of the MPO PV material. Crystal sizes of about 2.5 μm in length and 0.15 μm in diameter have been made with very large quantities of HF as mineralizer (10 times the required stoichiometric amount). Ion exchange of the material by PdCl 42- has resulted in the incorporation of the PdCl 42- ions in place of X - in the material. This has been confirmed by XAFS studies that demonstrate the oxidation state of Pd is 2+ and show four Cl atoms bound to Pd. Upon reduction it has been confirmed (by XAFS) that the palladium exists as metal with oxidation state of zero. Ion exchange by PdCl 42- and PtCl 42- and subsequent reduction of the material suspension by hydrogen result in the formation of separate Pt and Pd colloids in the close vicinity of the crystallites. TEM micrographs show clearly that the Pt metal obtained after reduction forms much smaller particles in comparison to Pd. These exchanged and reduced materials have also been investigated as catalysts for production of hydrogen peroxide in mixed acetone/water medium. The production of hydrogen peroxide is enhanced by increasing amounts of Pd in the catalyst. Hydrogen peroxide yields are the highest for catalysts containing only Pd as opposed to a mixture of Pt and Pd.

Highly efficient photodynamic therapy colloidal system based on chloroaluminum phthalocyanine/pluronic micelles.

PubMed

Py-Daniel, Karen R; Namban, Joy S; de Andrade, Laise R; de Souza, Paulo E N; Paterno, Leonardo G; Azevedo, Ricardo B; Soler, Maria A G

2016-06-01

Phthalocyanine derivatives comprise the second generation of photosensitizer molecules employed in photodynamic therapy (PDT) and have attracted much attention due to their outstanding photosensitizing performance. Most phthalocyanines are hydrophobic compounds that require association to drug delivery systems for clinical use. In this study, formulations of Pluronic F127 micelles incorporated with chloroaluminum phthalocyanine, or else F127/AlClPc, were produced at optimized conditions aiming at efficient and biocompatible PDT colloidal systems. Absorption/emission spectroscopies, as well as dynamic light scattering were performed to evaluate the optimum conditions for the F127 micelle formation and AlClPc incorporation. The micelles formation was attained with F127 concentrations ranging from 50 to 150mgmL(-1). At these conditions, AlClPc photosensitizer molecules were encapsulated into the hydrophobic micelle core and, therefore, readily solubilized in physiological medium (PBS pH 7.2). Encapsulation efficiency of about 90% resulted from different AlClPc concentrations. Identification of singlet oxygen production by irradiated F127/AlClPc formulations indicated good applicability for PDT. In vitro tests conducted with A549 human lung carcinoma cell line incubated with the F127/AlClPc formulations, at different AlClPc loadings, followed by only 18min of light irradiation (660nm LED, fluence of 25.3J/cm(2)), showed a cellular damage as high as 90% for rather low dosages of AlClPc (0.1-5.0μgmL(-1)). Further, no cytotoxicity occurred on non-irradiated cells. These findings suggest those F127/AlClPc formulations are highly promising for PDT applications, since they are easily prepared and the incubation and irradiation times are significantly shortened. Copyright © 2016 Elsevier B.V. All rights reserved.

Growth Performance, Carcass Characteristics and Plasma Mineral Chemistry as Affected by Dietary Chloride and Chloride Salts Fed to Broiler Chickens Reared under Phase Feeding System

PubMed Central

Mushtaq, M. M. H.; Pasha, T. N.; Akram, M.; Mushtaq, T.; Parvin, R.; Choi, H. C.; Hwangbo, J.; Kim, J. H.

2013-01-01

Requirements of dietary chloride (dCl) and chloride salts were determined by using 4×2 factorial arrangement under four phase feeding program. Four levels (0.31, 0.45, 0.59 and 0.73%) and two sources (NH4Cl and CaCl2) of the dCl were allocated to 1,472 chicks in eight dietary treatments in which each treatment was replicated four times with 46 birds per replicate. The four phase feeding program was comprised of four dietary phases: Prestarter (d 1 to 10), Starter (d 11 to 20), Grower (d 21 to 33) and Finisher (d 34 to 42); and diets were separately prepared for each phase. The cations, anions, pH, dissolved oxygen (DO), temperature, electrical conductivity (EC), total dissolved solids (TDS) and salinity were analyzed in drinking water and were not affected by dietary treatments. BW gain (BWG; p≤0.009) and feed:gain (FG; p≤0.03) were improved in CaCl2 supplemented diets during d 1 to 10. The maximum response of BWG and FG was observed at 0.38% and 0.42% dCl, respectively, for d 34 to 42. However, the level of dCl for BWG during d 21 to 33 (p≤0.04) and d 34 to 42 (p≤0.009) was optimized at 0.60% and 0.42%, respectively. The level of dCl for optimized feed intake (FI; p≤0.006), FG (p≤0.007) and litter moisture (LM; p≤0.001) was observed at 0.60%, 0.38% and 0.73%, respectively, for d 1 to 42. Water intake (DWI) was not affected by increasing dCl supplementation (p>0.05); however, the ratio between DWI and FI (DWI:FI) was found highest at 0.73% dCl during d 1 to 10 (p≤0.05) and d 21 to 33 (p≤0.009). Except for d 34 to 42 (p≤0.006), the increasing level of dCl did not result in a significant difference in mortality during any phase. Blood pH and glucose, and breast and thigh weights (percentage of dressed weight) were improved while dressing percentage (DP) and gastrointestinal health were exacerbated with NH4Cl as compared to CaCl2 supplemented diets (p≤0.001). Higher plasma Na+ and HCO3− and lower Cl− and Ca++ were observed in NH4Cl supplemented diets (p≤0.001). Increasing supplementation of dCl increased plasma Cl− (p≤0.04; quadratically) and linearly reduced plasma K+ (p≤0.001), Ca++ (p≤0.003), HCO3− (p≤0.001), and Na+ (p≤0.001; quadratically). Consequently, higher requirements of dietary chloride are suggested for feed intake; nevertheless, lower levels of dietary chloride are sufficient to support optimal BWG and FG with increasing age. The NH4Cl supplemented diets ameliorate breast and thigh meat yield along with overall energy balance (glucose). PMID:25049859

Gas phase acid, ammonia and aerosol ionic and trace element concentrations at Cape Verde during the Reactive Halogens in the Marine Boundary Layer (RHaMBLe) 2007 intensive sampling period

NASA Astrophysics Data System (ADS)

Sander, R.; Pszenny, A. A. P.; Keene, W. C.; Crete, E.; Deegan, B.; Long, M. S.; Maben, J. R.; Young, A. H.

2013-07-01

We report mixing ratios of soluble reactive trace gases sampled with mist chambers and the chemical composition of bulk aerosol and volatile inorganic bromine (Brg) sampled with filter packs during the Reactive Halogens in the Marine Boundary Layer (RHaMBLe) field campaign at the Cape Verde Atmospheric Observatory (CVAO) on São Vicente island in the tropical North Atlantic in May and June 2007. The gas-phase data include HCl, HNO3, HONO, HCOOH, CH3COOH, NH3, and volatile reactive chlorine other than HCl (Cl*). Aerosol samples were analyzed by neutron activation (Na, Al, Cl, V, Mn, and Br) and ion chromatography (SO42-, Cl-, Br-, NH4+, Na+, K+, Mg2+, and Ca2+). Content and quality of the data, which are available under doi:10.5281/zenodo.6956, are presented and discussed.

Gas phase acid, ammonia and aerosol ionic and trace element concentrations at Cape Verde during the Reactive Halogens in the Marine Boundary Layer (RHaMBLe) 2007 intensive sampling period

NASA Astrophysics Data System (ADS)

Sander, R.; Pszenny, A. A. P.; Keene, W. C.; Crete, E.; Deegan, B.; Long, M. S.; Maben, J. R.; Young, A. H.

2013-12-01

We report mixing ratios of soluble reactive trace gases sampled with mist chambers and the chemical composition of bulk aerosol and volatile inorganic bromine (Brg) sampled with filter packs during the Reactive Halogens in the Marine Boundary Layer (RHaMBLe) field campaign at the Cape Verde Atmospheric Observatory (CVAO) on São Vicente island in the tropical North Atlantic in May and June 2007. The gas-phase data include HCl, HNO3, HONO, HCOOH, CH3COOH, NH3, and volatile reactive chlorine other than HCl (Cl*). Aerosol samples were analyzed by neutron activation (Na, Al, Cl, V, Mn, and Br) and ion chromatography (SO42-, Cl-, Br-, NH4+, Na+, K+, Mg2+, and Ca2+). Content and quality of the data, which are available under doi:10.5281/zenodo.6956, are presented and discussed.

Atmospheric chemistry of CF3CF═CH2 and (Z)-CF3CF═CHF: Cl and NO3 rate coefficients, Cl reaction product yields, and thermochemical calculations.

PubMed

Papadimitriou, Vassileios C; Lazarou, Yannis G; Talukdar, Ranajit K; Burkholder, James B

2011-01-20

Rate coefficients, k, for the gas-phase reactions of Cl atoms and NO(3) radicals with 2,3,3,3-tetrafluoropropene, CF(3)CF═CH(2) (HFO-1234yf), and 1,2,3,3,3-pentafluoropropene, (Z)-CF(3)CF═CHF (HFO-1225ye), are reported. Cl-atom rate coefficients were measured in the fall-off region as a function of temperature (220-380 K) and pressure (50-630 Torr; N(2), O(2), and synthetic air) using a relative rate method. The measured rate coefficients are well represented by the fall-off parameters k(0)(T) = 6.5 × 10(-28) (T/300)(-6.9) cm(6) molecule(-2) s(-1) and k(∞)(T) = 7.7 × 10(-11) (T/300)(-0.65) cm(3) molecule(-1) s(-1) for CF(3)CF═CH(2) and k(0)(T) = 3 × 10(-27) (T/300)(-6.5) cm(6) molecule(-2) s(-1) and k(∞)(T) = 4.15 × 10(-11) (T/300)(-0.5) cm(3) molecule(-1) s(-1) for (Z)-CF(3)C═CHF with F(c) = 0.6. Reaction product yields were measured in the presence of O(2) to be (98 ± 7)% for CF(3)C(O)F and (61 ± 4)% for HC(O)Cl in the CF(3)CF═CH(2) reaction and (108 ± 8)% for CF(3)C(O)F and (112 ± 8)% for HC(O)F in the (Z)-CF(3)CF═CHF reaction, where the quoted uncertainties are 2σ (95% confidence level) and include estimated systematic errors. NO(3) reaction rate coefficients were determined using absolute and relative rate methods. Absolute measurements yielded upper limits for both reactions between 233 and 353 K, while the relative rate measurements yielded k(3)(295 K) = (2.6 ± 0.25) × 10(-17) cm(3) molecule(-1) s(-1) and k(4)(295 K) = (4.2 ± 0.5) × 10(-18) cm(3) molecule(-1) s(-1) for CF(3)CF═CH(2) and (Z)-CF(3)CF═CHF, respectively. The Cl-atom reaction with CF(3)CF═CH(2) and (Z)-CF(3)CF═CHF leads to decreases in their atmospheric lifetimes and global warming potentials and formation of a chlorine-containing product, HC(O)Cl, for CF(3)CF═CH(2). The NO(3) reaction has been shown to have a negligible impact on the atmospheric lifetimes of CF(3)CF═CH(2) and (Z)-CF(3)CF═CHF. The energetics for the reaction of Cl, NO(3), and OH with CF(3)CF═CH(2) and (Z)-CF(3)CF═CHF in the presence of O(2) were investigated using density functional theory (DFT).

Wet-dry seasonal and vertical geochemical variations in soil water and their driving forces under different land covers in southwest China karst

NASA Astrophysics Data System (ADS)

Wang, Peng; Hu, Bill X.; Wu, Chuanhao; Xu, Kai

2017-04-01

Karst aquifers supply drinking water for 25% of the world's population, and they are, however, vulnerable to climate change. Bimonthly hydrochemical data in karst soil water samples from July 2010 to July 2011 were obtained to reveal the seasonal and vertical geochemical variations in soil water under five vegetation types in Qingmuguan, a small karst catchment in southwest China. Soil water chemistry was dominated by Ca2+, HCO3-, and SO42- because of the dissolution of limestone, dolomite, and gypsum minerals in the strata. The predominant hydrochemical types in soil water were Ca2+-HCO3-, Ca2+-SO42-, and mixed Ca2+-HCO3-SO42-. Ca2+ and HCO3- concentrations ranked in the following order: shrub land > dry land > afforestation farmland > bamboo land > grassland. In warm and wet seasons, the main ion concentrations in soil water from grasslands were low. Na+, K+, Ca2+, Mg2+, HCO3-, SO42-, and Cl- concentrations in soil water from other lands were high. An opposite trend was observed in cold and dry seasons. Marked seasonal variations were observed in Ca2+, HCO3-, and NO3- in soil water from dry land. The main ion concentrations in soil water from bamboo lands decreased as soil depth increased. By contrast, the chemistry of soil water from other lands increased as soil depth increased. Their ions were accumulated in depth. A consistent high and low variation between the main ions in soil water and the contents of carbonate and CO2 was found in the soil. Hydrochemical changes in soil water were regulated by the effects of dilution and soil CO2.

Synthetic, Infrared, 1Hand 13CNMR Spectral Studies on N-(p-Substituted Phenyl)-p-Substituted Benzenesulphonamides, p-X'C6H4SO2NH- (p-XC6H4), where X' or X = H, CH3, C2H5, F, Cl or Br

NASA Astrophysics Data System (ADS)

Gowda, B. Thimme; Jayalakshmi, K. L.; Shetty, Mahesha

2004-05-01

Thirty N-(p-substituted phenyl)-p-substituted benzenesulphonamides of the general formula, p-X'C6H4SO2NH(p-XC6H4), where X' or X = H, CH3, C2H5, F, Cl or Br, are synthesised and their infrared spectra in the solid state and 1H and 13C NMR spectra in solution are measured. The N-H stretching vibrational frequencies, νN-H vary in the range 3334 - 3219 cm-1, while the asymmetric and symmetric SO2 vibrations appear in the ranges 1377 - 1311 cm-1 and 1182 - 1151 cm-1, respectively. The compounds exhibit S-N and C-N stretching vibrational absorptions in the ranges 937 - 898 cm-1 and 1310 - 1180 cm-1, respectively. There are no particular trends in the variation of these frequencies on substitution with either electron withdrawing or electron donating groups. The 1H and 13C chemical shifts of N-(p-substituted phenyl)-p-substituted benzenesulphonamides, are assigned to various protons and carbons of the two benzene rings. Further, incremental shifts of the ring protons and carbons due to -SO2NH(p-XC6H4) groups in the compounds of the formula, C6H5SO2NH(p-XC6H4), and p-X'C6H4SO2- and p-X'C6H4SO2NH- groups in the compounds of the formula, p-X'C6H4SO2NH(C6H5) are computed and used to calculate the 1H and 13C chemical shifts of the parallely substituted compounds of the general formula p-X'C6H4SO2NH(p-XC6H4). The computed values agree well with the observed chemical shifts. The above incremental shifts are found to correlate with the Hammett substituent parameters.

Kinetic studies of the reaction of the SO radical with NO2 and ClO from 210 to 363 K

NASA Technical Reports Server (NTRS)

Brunning, J.; Stief, L. J.

1986-01-01

The rates of the reactions of the SO radical with NO2 and ClO (significant in the upper atmosphere of earth and Venus) were determined in a discharge flow system near 1 torr pressure with detection of radical and molecular species using collision-free sampling mass spectrometry. The rate constants were obtained from the decay of SO radicals in the presence of an excess of NO2 and ClO. The NO2 reaction was examined between 210 and 363 K and found to be temperature invariant: SO + NO2 yields SO2 + NO; k1 = (1.37 + or - 0.10) x 10 to the -11th cu cm/s. In addition, the ClO reaction was observed to be independent of temperature between 248 and 363 K: SO + ClO yields SO2 + Cl; k2 = (3.22 + or - 0.48) x 10 to the -11th cu cm/s. A comparison was made with previous investigations of these reactions at room temperature and with other radical-radical reactions involving SO or ClO.

Formation of light absorbing organo-nitrogen species from evaporation of droplets containing glyoxal and ammonium sulfate.

PubMed

Lee, Alex K Y; Zhao, Ran; Li, Richard; Liggio, John; Li, Shao-Meng; Abbatt, Jonathan P D

2013-11-19

In the atmosphere, volatile organic compounds such as glyoxal can partition into aqueous droplets containing significant levels of inorganic salts. Upon droplet evaporation, both the organics and inorganic ions become highly concentrated, accelerating reactions between them. To demonstrate this process, we investigated the formation of organo-nitrogen and light absorbing materials in evaporating droplets containing glyoxal and different ammonium salts including (NH4)2SO4, NH4NO3, and NH4Cl. Our results demonstrate that evaporating glyoxal-(NH4)2SO4 droplets produce light absorbing species on a time scale of seconds, which is orders of magnitude faster than observed in bulk solutions. Using aerosol mass spectrometry, we show that particle-phase organics with high N:C ratios were formed when ammonium salts were used, and that the presence of sulfate ions promoted this chemistry. Since sulfate can also significantly enhance the Henry's law partitioning of glyoxal, our results highlight the atmospheric importance of such inorganic-organic interactions in aqueous phase aerosol chemistry.

The ground state of metallic nano-structures in heavily irradiated NaCl-KBF4

NASA Astrophysics Data System (ADS)

Cherkasov, F. G.; L'Vov, S. G.; Tikhonov, D. A.; den Hartog, H. W.; Vainshtein, D. I.

ESR, NMR and static magnetic susceptibility measurements of heavily irradiated NaCl-K and NaCl-KBF4 are reported. Up to 10% of the NaCl-molecules are transformed into metallic Na nanoparticles and Cl-2 precipitates. In addition, there are paramagnetic F- and F-aggregates, which are coupled by exchange interactions to the conduction electrons in the nanoparticles. Above 160 K the NMR and ESR signals of NaCl-K and NaCl-KBF4 show Pauli paramagnetism and the properties of the Na nanoparticles are similar to bulk sodium. A single ESR line is observed revealing exchange interaction between conduction electrons in the nano-particles and F-aggregates. The observed decrease of the ESR susceptibility with decreasing temperature is due to a metal-insulator transition. The conduction electrons are localized below 40 K and the above mentioned F-aggregate centers contribute significantly to the overall ESR signal. For NaCl-KBF4 we observed that with decreasing temperature the ESR line shifts towards lower fields due to antiferromagnetic ordering and internal magnetic fields.

Chemical Properties of Dialkyl Halonium Ions (R2Hal+) and Their Neutral Analogues, Methyl Carboranes, CH3-(CHB11Hal11), Where Hal = F, Cl.

PubMed

Stoyanov, Evgenii S

2017-04-20

Chloronium cations in their salts (C n H 2n+1 ) 2 Cl + {CHB 11 Cl 11 - }, with n = 1 to 3 and exceptionally stable carborane anions, are stable at ambient and elevated temperatures. The temperature at which they decompose to carbocations with HCl elimination (below 150 °C) decreases with the increasing n from 1 to 3 because of increasing ionicity of C-Cl bonds in the C-Cl + -C bridge. At room temperature, the salts of cations with n ≥ 4 [starting from t-Bu 2 Cl + or (cyclo-C 5 H 11 ) 2 Cl + ] are unstable and decompose. With decreasing chloronium ion stability, their ability to interact with chloroalkanes to form oligomeric cations increases. It was shown indirectly that unstable salt of fluoronium ions (CH 3 ) 2 F + (CHB 11 F 11 - ) must exist at low temperatures. The proposed (CH 3 ) 2 F + cation is much more reactive than the corresponding chloronium, showing at room temperature chemical properties expected of (CH 3 ) 2 Cl + at elevated temperatures.

Particulate emissions from a mid-latitude prescribed chaparral fire

NASA Technical Reports Server (NTRS)

Cofer, Wesley R., III; Levine, Joel S.; Sebacher, Daniel I.; Winstead, Edward L.; Riggin, Philip J.; Brass, James A.; Ambrosia, Vincent G.

1988-01-01

Particulate emission from a 400-acre prescribed chaparral fire in the San Dimas Experimental Forest was investigated by collecting smoke aerosol on Teflon and glass-fiber filters from a helicopter, and using SEM and EDAX to study the features of the particles. Aerosol particles ranged in size from about 0.1 to 100 microns, with carbon, oxygen, magnesium, aluminum, silicon, calcium, and iron as the primary elements. The results of ion chromatographic analysis of aerosol-particle extracts (in water-methanol) revealed the presence of significant levels of NO2(-), NO3(-), SO4(2-), Cl(-), PO4(3-), C2O4(2-), Na(+), NH4(+), and K(+). The soluble ionic portion of the aerosol was estimated to be about 2 percent by weight.

Deposition measurement of particulate matter in connection with corrosion studies.

PubMed

Ferm, Martin; Watt, John; O'Hanlon, Samantha; De Santis, Franco; Varotsos, Costas

2006-03-01

A new passive particle collector (inert surrogate surface) that collects particles from all directions has been developed. It was used to measure particle deposition at 35 test sites as part of a project that examined corrosion of materials in order that variation in particulate material could be used in development of dose-response functions in a modern multi-pollutant environment. The project, MULTI-ASSESS, was funded by the EU to examine the effects of air pollution on cultural heritage. Passive samplers were mounted rain-protected, and both in wind-protected and wind-exposed positions, to match the exposure of the samples for corrosion studies. The particle mass and its chemical content (nitrate, ammonium, sulfate, calcium, sodium, chloride, magnesium and potassium) were analysed. The loss of light reflectance on the surrogate surface was also measured. Very little ammonium and potassium was found, and one or more anions are missing in the ion balance. There were many strong correlations between the analysed species. The mass of analysed water-soluble ions was fairly constant at 24% of the total mass. The particle mass deposited to the samplers in the wind-protected position was about 25% of the particles deposited to an openly exposed sampler. The Cl-/Na+ ratios indicate a reaction between HNO(3) and NaCl. The deposited nitrate flux corresponds to the missing chloride. The Ca2+ deposition equals the SO4(2-) deposition and the anion deficiency. The SO4(2-) deposition most likely originates from SO2 that has reacted with basic calcium-containing particles either before or after they were deposited. The particle depositions at the urban sites were much higher than in nearby rural sites. The deposited mass correlated surprisingly well with the PM(10) concentration, except at sites very close to traffic.

A novel dichromate-sensitive fluorescent nano-chemosensor using new functionalized SBA-15.

PubMed

Hosseini, Morteza; Gupta, Vinod Kumar; Ganjali, Mohammad Reza; Rafiei-Sarmazdeh, Zahra; Faridbod, Farnoush; Goldooz, Hassan; Badiei, Ali Reza; Norouzi, Parviz

2012-02-17

A novel fluorescence nano-chemosensor for Cr(2)O(7)(2-) anion has been developed by assembly of fluorescent aluminum complex of 8-hydroxyquinoline (AlQ(x)) within the channels of modified SBA-15. SBA-SPS-AlQ(x) shows a fluorescence emission at 486 nm. The observed remarkable fluorescence of SBA-SPS-AlQ(x) quenches in presence of Cr(2)O(7)(2-) anion. The results showed that this fluorescent nano-material can be a useful chemo-sensor for determination of dichromate anions in aqueous solutions. The linear detecting range of fluorescent nano-chemosensor for Cr(2)O(7)(2-) anion was 0.16-2.9 μmol L(-1). The lowest limit of detection (LDL) was also found to be 0.2 ng mL(-1) in aqueous solutions. SBA-SPS-AlQ(x) showed selectively and sensitively fluorescent quenching response toward Cr(2)O(7)(2-) ion in comparison with I(3)(-), NO(3)(-), CN(-), CO(3)(2-), Br(-), Cl(-), F(-), H(2)PO(4)(-) and SO(4)(2-) ions, which was because of the higher stability of its inorganic complex with dichromate ion. Copyright © 2011 Elsevier B.V. All rights reserved.

Cellulose Derived Graphenic Fibers for Capacitive Desalination of Brackish Water.

PubMed

Pugazhenthiran, Nalenthiran; Sen Gupta, Soujit; Prabhath, Anupama; Manikandan, Muthu; Swathy, Jakka Ravindran; Raman, V Kalyan; Pradeep, Thalappil

2015-09-16

We describe a simple and inexpensive cellulose-derived and layer-by-layer stacked carbon fiber network electrode for capacitive deionization (CDI) of brackish water. The microstructure and chemical composition were characterized using spectroscopic and microscopic techniques; electrochemical/electrical performance was evaluated by cyclic voltammetry and 4-probe electrical conductivity and surface area by Brunauer-Emmett-Teller analysis, respectively. The desalination performance was investigated using a laboratory batch model CDI unit, under fixed applied voltage and varying salt concentrations. Electro-adsorption of NaCl on the graphite reinforced-cellulose (GrC) electrode reached equilibrium quickly (within 90 min) and the adsorbed salts were released swiftly (in 40 min) back into the solution, during reversal of applied potential. X-ray photoelectron spectroscopic studies clearly illustrate that sodium and chloride ions were physisorbed on the negative and positive electrodes, respectively during electro-adsorption. This GrC electrode showed an electro-adsorption capacity of 13.1 mg/g of the electrode at a cell potential of 1.2 V, with excellent recyclability and complete regeneration. The electrode has a high tendency for removal of specific anions, such as fluoride, nitrate, chloride, and sulfate from water in the following order: Cl->NO3->F->SO4(2-). GrC electrodes also showed resistance to biofouling with negligible biofilm formation even after 5 days of incubation in Pseudomonas putida bacterial culture. Our unique cost-effective methodology of layer-by-layer stacking of carbon nanofibers and concurrent reinforcement using graphite provides uniform conductivity throughout the electrode with fast electro-adsorption, rapid desorption, and extended reuse, making the electrode affordable for capacitive desalination of brackish water.

The indoor-outdoor characteristics of water-soluble ion in PM2.5 in Tianjin wintertime.

PubMed

Wang, Baoqing; Niu, Honghong; Liu, Bowei; Hu, Xinxin; Ren, Zihui

2018-05-15

The indoor and outdoor PM 2.5 mass concentration, water-soluble ion by filter sampler was analyzed on December 3-21, 2015 during wintertime in Tianjin, China. The results indicate that high humidity conditions result in the accumulation of atmospheric pollutants and reduce atmosphere visibility. The I/O ratio for PM 2.5 concentration in dormitory and lab are less than 1 in haze days. Indoor PM 2.5 concentration increases rapidly with outdoor PM 2.5 concentration increasing in haze days. The filtration factors of the dormitory and lab indicate nearly half of the outdoor PM 2.5 enters indoor environment. The human activities in dormitory could cause more the formation of PM 2.5 than those in lab. The concentration of SO 4 2- is the highest ion in water-soluble ion for outdoor PM 2.5 . The SO 4 2- , NO 3 - , NH 4 + , and Cl - are generated mainly by outdoor sources; however, the Na + , Ca 2+ , and Mg 2+ are generated mainly by indoor sources. The NH 4 NO 3 , (NH 4 ) 2 SO 4 , and NH 4 Cl accounts for 20.2~41.8%, 32.0~51.4%, and 6.4~10.6% of the total water-soluble ion in different indoor-outdoor environment. The total secondary aerosols including NH 4 NO 3 , (NH 4 ) 2 SO 4 , and NH 4 Cl in PM 2.5 are 28.3, 42.1, 28.2, 31.0, and 33.9% in outdoor environment for haze days, outdoor environment for non-haze days, dormitory for haze days, dormitory for non-haze days, and lab for haze days, respectively.

Excimer laser beam delivery systems for medical applications

NASA Astrophysics Data System (ADS)

Kubo, Uichi; Hashishin, Yuichi; Okada, Kazuyuki; Tanaka, Hiroyuki

1993-05-01

We have been doing the basic experiments of UV laser beams and biotissue interaction with both KrF and XeCl lasers. However, the conventional optical fiber can not be available for power UV beams. So we have been investigating about UV power beam delivery systems. These experiments carry on with the same elements doped quartz fibers and the hollow tube. The doped elements are OH ion, chlorine and fluorine. In our latest work, we have tried ArF excimer laser and biotissue interactions, and the beam delivery experiments. From our experimental results, we found that the ArF laser beam has high incision ability for hard biotissue. For example, in the case of the cow's bone incision, the incision depth by ArF laser was ca.15 times of KrF laser. Therefore, ArF laser would be expected to harden biotissue therapy as non-thermal method. However, its beam delivery is difficult to work in this time. We will develop ArF laser beam delivery systems.

Spectroscopy and heats of formation of CXI (X = Br, Cl, F) iodocarbenes: quantum chemical characterisation of the ?, ? and ? states

NASA Astrophysics Data System (ADS)

Bacskay, George B.

2015-07-01

The equilibrium energies of the iodocarbenes CXI (X = Br, Cl, F) in their ?, ? and ? states and their atomisation and dissociation energies in the complete basis limit were determined by extrapolating valence correlated (R/U)CCSD(T) and Davidson corrected multi-reference configuration interaction (MRCI) energies calculated with the aug-cc-pVxZ (x = T,Q,5) basis sets and the ECP28MDF pseudopotential of iodine plus corrections for core and core-valence correlation, scalar relativity, spin-orbit coupling and zero-point energies. Spin-orbit energies were computed in a large basis of configurations chosen so as to accurately describe dissociation to the 3P and 2P states of C and of the halogens X and I, respectively. The computed singlet-triplet splittings are 13.6, 14.4 and 27.3 kcal mol-1 for X = Br, Cl and F, respectively. The enthalpies of formation at 0 K are predicted to be 97.4, 82.6 and 38.1 kcal mol-1 with estimated errors of ±1.0 kcal mol-1. The ? excitation energies (T00) in CBrI and CClI are calculated to be 41.1 and 41.7 kcal mol-1, respectively. The Renner-Teller intersections in both molecules are predicted to be substantially higher than the dissociation barriers on the ? surfaces. By contrast, in CFI the ? state is found to be unbound with respect to dissociation.

Crystal structures of Ca(ClO4)2·4H2O and Ca(ClO4)2·6H2O

PubMed Central

Hennings, Erik; Schmidt, Horst; Voigt, Wolfgang

2014-01-01

The title compounds, calcium perchlorate tetra­hydrate and calcium perchlorate hexa­hydrate, were crystallized at low temperatures according to the solid–liquid phase diagram. The structure of the tetra­hydrate consists of one Ca2+ cation eightfold coordinated in a square-anti­prismatic fashion by four water mol­ecules and four O atoms of four perchlorate tetra­hedra, forming chains parallel to [01-1] by sharing corners of the ClO4 tetra­hedra. The structure of the hexa­hydrate contains two different Ca2+ cations, each coordinated by six water mol­ecules and two O atoms of two perchlorate tetra­hedra, forming [Ca(H2O)6(ClO4)]2 dimers by sharing two ClO4 tetra­hedra. The dimers are arranged in sheets parallel (001) and alternate with layers of non-coordinating ClO4 tetra­hedra. O—H⋯O hydrogen bonds between the water mol­ecules as donor and ClO4 tetra­hedra and water mol­ecules as acceptor groups lead to the formation of a three-dimensional network in the two structures. Ca(ClO4)2·6H2O was refined as a two-component inversion twin, with an approximate twin component ratio of 1:1 in each of the two structures. PMID:25552974

Experimental Constraints on the Partitioning Behavior of F, Cl, and OH Between Apatite and Basaltic Melt

NASA Technical Reports Server (NTRS)

McCubbin, Francis M.; Barnes, Jessica J.; Vander Kaaden, Kathleen E.; Boyce, Jeremy W.; Ustunisik, Gokce; Whitson, Eric S.

2017-01-01

The mineral apatite is present in a wide range of planetary materials. The presence of volatiles (F, Cl, and OH) within its crystal structure (X-site) have motivated numerous studies to investigate the partitioning behavior of F, Cl, and OH between apatite and silicate melt with the end goal of using apatite to constrain the volatile contents of planetary magmas and mantle sources. A number of recent experimental studies have investigated the apatite-melt partitioning behavior of F, Cl, and OH in magmatic systems. Apatite-melt partitioning of volatiles are best described as exchange equilibria similar to Fe-Mg partitioning between olivine and silicate melt. However, the partitioning behavior is likely to change as a function of temperature, pressure, oxygen fugacity, apatite composition, and melt composition. In the present study, we have conducted experiments to assess the partitioning behavior of F, Cl, and OH between apatite and silicate melt over a pressure range of 0-6 gigapascals, a temperature range of 950-1500 degrees Centigrade, and a wide range of apatite ternary compositions. All of the experiments were conducted between iron-wustite oxidation potentials IW minus 1 and IW plus 2 in a basaltic melt composition. The experimental run products were analyzed by a combination of electron probe microanalysis and secondary ion mass spectrometry (NanoSIMS). Temperature, apatite crystal chemistry, and pressure all play important roles in the partitioning behavior of F, Cl, and OH between apatite and silicate melt. In portions of apatite ternary space that undergo ideal mixing of F, Cl, and OH, exchange coefficients remain constant at constant temperature and pressure. However, exchange coefficients vary at constant temperature (T) and pressure (P) in portions of apatite compositional space where F, Cl, and OH do not mix ideally in apatite. The variation in exchange coefficients exhibited by apatite that does not undergo ideal mixing far exceeds the variations induced by changes in temperature (T) or pressure (P) . In regions where apatite undergoes ideal mixing of F, Cl, and OH, temperature has a stronger effect than pressure on the partitioning behavior, but both are important. Furthermore, fluorine becomes less compatible in apatite with increasing pressure and temperature. We are still in the process of analyzing our experimental run products, but we plan to quantify the effects of P and T on apatite-melt partitioning of F, Cl, and OH.

Tropical land-cover change alters biogeochemical inputs to ecosystems in a Mexican montane landscape.

PubMed

Ponette-González, A G; Weathers, K C; Curran, L M

2010-10-01

In tropical regions, the effects of land-cover change on nutrient and pollutant inputs to ecosystems remain poorly documented and may be pronounced, especially in montane areas exposed to elevated atmospheric deposition. We examined atmospheric deposition and canopy interactions of sulfate-sulfur (SO4(2-)-S), chloride (Cl-), and nitrate-nitrogen (NO(3-)-N) in three extensive tropical montane land-cover types: clearings, forest, and coffee agroforest. Bulk and fog deposition to clearings was measured as well as throughfall (water that falls through plant canopies) ion fluxes in seven forest and five coffee sites. Sampling was conducted from 2005 to 2008 across two regions in the Sierra Madre Oriental, Veracruz, Mexico. Annual throughfall fluxes to forest and coffee sites ranged over 6-27 kg SO4(2-)-S/ha, 12-69 kg Cl-/ha, and 2-6 kg NO(3-)-N/ha. Sulfate-S in forest and coffee throughfall was higher or similar to bulk S deposition measured in clearings. Throughfall Cl- inputs, however, were consistently higher than Cl- amounts deposited to cleared areas, with net Cl- fluxes enhanced in evergreen coffee relative to semi-deciduous forest plots. Compared to bulk nitrate-N deposition, forest and coffee canopies retained 1-4 kg NO(3-)-N/ha annually, reducing NO(3-)-N inputs to soils. Overall, throughfall fluxes were similar to values reported for Neotropical sites influenced by anthropogenic emissions, while bulk S and N deposition were nine- and eightfold greater, respectively, than background wet deposition rates for remote tropical areas. Our results demonstrate that land-cover type significantly alters the magnitude and spatial distribution of atmospheric inputs to tropical ecosystems, primarily through canopy-induced changes in fog and dry deposition. However, we found that land cover interacts with topography and climate in significant ways to produce spatially heterogeneous patterns of anion fluxes, and that these factors can converge to create deposition hotspots. For land managers, this finding suggests that there is potential to identify species and ecosystems at risk of excess and increasing deposition in montane watersheds undergoing rapid transformation. Our data further indicate that montane ecosystems are vulnerable to air pollution impacts in this and similar tropical regions downwind of urban, industrial, and agricultural emission sources.

Pseudomonas aeruginosa Reduces VX-809 Stimulated F508del-CFTR Chloride Secretion by Airway Epithelial Cells

PubMed Central

Stanton, Bruce A.; Coutermarsh, Bonita; Barnaby, Roxanna; Hogan, Deborah

2015-01-01

Background P. aeruginosa is an opportunistic pathogen that chronically infects the lungs of 85% of adult patients with Cystic Fibrosis (CF). Previously, we demonstrated that P. aeruginosa reduced wt-CFTR Cl secretion by airway epithelial cells. Recently, a new investigational drug VX-809 has been shown to increase F508del-CFTR Cl secretion in human bronchial epithelial (HBE) cells, and, in combination with VX-770, to increase FEV1 (forced expiratory volume in 1 second) by an average of 3-5% in CF patients homozygous for the F508del-CFTR mutation. We propose that P. aeruginosa infection of CF lungs reduces VX-809 + VX-770- stimulated F508del-CFTR Cl secretion, and thereby reduces the clinical efficacy of VX-809 + VX-770. Methods and Results F508del-CFBE cells and primary cultures of CF-HBE cells (F508del/F508del) were exposed to VX-809 alone or a combination of VX-809 + VX-770 for 48 hours and the effect of P. aeruginosa on F508del-CFTR Cl secretion was measured in Ussing chambers. The effect of VX-809 on F508del-CFTR abundance was measured by cell surface biotinylation and western blot analysis. PAO1, PA14, PAK and 6 clinical isolates of P. aeruginosa (3 mucoid and 3 non-mucoid) significantly reduced drug stimulated F508del-CFTR Cl secretion, and plasma membrane F508del-CFTR. Conclusion The observation that P. aeruginosa reduces VX-809 and VX-809 + VX-770 stimulated F508del CFTR Cl secretion may explain, in part, why VX-809 + VX-770 has modest efficacy in clinical trials. PMID:26018799

Pseudomonas aeruginosa Reduces VX-809 Stimulated F508del-CFTR Chloride Secretion by Airway Epithelial Cells.

PubMed

Stanton, Bruce A; Coutermarsh, Bonita; Barnaby, Roxanna; Hogan, Deborah

2015-01-01

P. aeruginosa is an opportunistic pathogen that chronically infects the lungs of 85% of adult patients with Cystic Fibrosis (CF). Previously, we demonstrated that P. aeruginosa reduced wt-CFTR Cl secretion by airway epithelial cells. Recently, a new investigational drug VX-809 has been shown to increase F508del-CFTR Cl secretion in human bronchial epithelial (HBE) cells, and, in combination with VX-770, to increase FEV1 (forced expiratory volume in 1 second) by an average of 3-5% in CF patients homozygous for the F508del-CFTR mutation. We propose that P. aeruginosa infection of CF lungs reduces VX-809 + VX-770- stimulated F508del-CFTR Cl secretion, and thereby reduces the clinical efficacy of VX-809 + VX-770. F508del-CFBE cells and primary cultures of CF-HBE cells (F508del/F508del) were exposed to VX-809 alone or a combination of VX-809 + VX-770 for 48 hours and the effect of P. aeruginosa on F508del-CFTR Cl secretion was measured in Ussing chambers. The effect of VX-809 on F508del-CFTR abundance was measured by cell surface biotinylation and western blot analysis. PAO1, PA14, PAK and 6 clinical isolates of P. aeruginosa (3 mucoid and 3 non-mucoid) significantly reduced drug stimulated F508del-CFTR Cl secretion, and plasma membrane F508del-CFTR. The observation that P. aeruginosa reduces VX-809 and VX-809 + VX-770 stimulated F508del CFTR Cl secretion may explain, in part, why VX-809 + VX-770 has modest efficacy in clinical trials.

Reactions occurring during the sulfation of sodium chloride deposited on alumina substrates

NASA Technical Reports Server (NTRS)

Wu, C. S.; Birks, N.

1986-01-01

The reaction between solid NaCl and air containing 1 pct SO2 has been studied between 500 and 700 C. The reaction product, Na2SO4, forms not only on the surface of the NaCl but also on surrounding areas of the substrate due to the volatility of the NaCl at these temperatures. At the higher temperatures, the vapor pressure of NaCl is so high that the majority of the reaction product is distributed on the substrate. Above 625 C, the reaction product is a liquid solution of NaCl and Na2SO4 that exists only so long as NaCl is supplied from the original crystal source. Eventually, the liquid solidifies by constitutional solidification as the NaCl is converted to Na2SO4. While it exists, the liquid NaCl-Na2SO4 solution is shown to be highly corrosive to Al2O3 and, on a scale of Al2O3 growing on alloy HOS 875, particularly attacks the grain boundaries of the scale at preferred sites where chromium and iron oxides and sulfides rapidly develop. This is proposed as one mechanism by which NaCl deposition contributes to the initiation of low temperature hot corrosion.

Process optimisation for anion exchange monolithic chromatography of 4.2kbp plasmid vaccine (pcDNA3F).

PubMed

Ongkudon, Clarence M; Danquah, Michael K

2010-10-15

Anion exchange monolithic chromatography is increasingly becoming a prominent tool for plasmid DNA purification but no generic protocol is available to purify all types of plasmid DNA. In this work, we established a simple framework and used it to specifically purify a plasmid DNA model from a clarified alkaline-lysed plasmid-containing cell lysate. The framework involved optimising ligand functionalisation temperature (30-80°C), mobile phase flow rate (0.1-1.8mL/min), monolith pore size (done by changing the porogen content in the polymerisation reaction by 50-80%), buffer pH (6-10), ionic strength of binding buffer (0.3-0.7M) and buffer gradient elution slope (1-10% buffer B/min). We concluded that preferential pcDNA3F adsorption and optimum resolution could be achieved within the tested conditions by loading the clarified cell lysate into 400nm pore size of monolith in 0.7M NaCl (pH 6) of binding buffer followed by increasing the NaCl concentration to 1.0M at 3%B/min. Copyright © 2010 Elsevier B.V. All rights reserved.

Quantitative fetal fibronectin testing in combination with cervical length measurement in the prediction of spontaneous preterm delivery in symptomatic women.

PubMed

Bruijn, Mmc; Vis, J Y; Wilms, F F; Oudijk, M A; Kwee, A; Porath, M M; Oei, G; Scheepers, Hcj; Spaanderman, Mea; Bloemenkamp, Kwm; Haak, M C; Bolte, A C; Vandenbussche, Fpha; Woiski, M D; Bax, C J; Cornette, Jmj; Duvekot, J J; Nij Bijvanck, Bwa; van Eyck, J; Franssen, Mtm; Sollie, K M; van der Post, Jam; Bossuyt, Pmm; Opmeer, B C; Kok, M; Mol, Bwj; van Baaren, G-J

2016-11-01

To evaluate whether in symptomatic women, the combination of quantitative fetal fibronectin (fFN) testing and cervical length (CL) improves the prediction of preterm delivery (PTD) within 7 days compared with qualitative fFN and CL. Post hoc analysis of frozen fFN samples of a nationwide cohort study. Ten perinatal centres in the Netherlands. Symptomatic women between 24 and 34 weeks of gestation. The risk of PTD <7 days was estimated in predefined CL and fFN strata. We used logistic regression to develop a model including quantitative fFN and CL, and one including qualitative fFN (threshold 50 ng/ml) and CL. We compared the models' capacity to identify women at low risk (<5%) for delivery within 7 days using a reclassification table. Spontaneous delivery within 7 days after study entry. We studied 350 women, of whom 69 (20%) delivered within 7 days. The risk of PTD in <7 days ranged from 2% in the lowest fFN group (<10 ng/ml) to 71% in the highest group (>500 ng/ml). Multivariable logistic regression showed an increasing risk of PTD in <7 days with rising fFN concentration [10-49 ng/ml: odds ratio (OR) 1.3, 95% confidence interval (95% CI) 0.23-7.0; 50-199 ng/ml: OR 3.2, 95% CI 0.79-13; 200-499 ng/ml: OR 9.0, 95% CI 2.3-35; >500 ng/ml: OR 39, 95% CI 9.4-164] and shortening of the CL (OR 0.86 per mm, 95% CI 0.82-0.90). Use of quantitative fFN instead of qualitative fFN resulted in reclassification of 18 (5%) women from high to low risk, of whom one (6%) woman delivered within 7 days. In symptomatic women, quantitative fFN testing does not improve the prediction of PTD within 7 days compared with qualitative fFN testing in combination with CL measurement in terms of reclassification from high to low (<5%) risk, but it adds value across the risk range. Quantitative fFN testing adds value to qualitative fFN testing with CL measurement in the prediction of PTD. © 2015 Royal College of Obstetricians and Gynaecologists.

Effects of inorganic seeds on secondary organic aerosol formation from photochemical oxidation of acetone in a chamber

NASA Astrophysics Data System (ADS)

Ge, Shuangshuang; Xu, Yongfu; Jia, Long

2017-12-01

Photochemical oxidations of acetone were studied under different inorganic seed (NaCl, (NH4)2SO4 and NaNO3) conditions in a self-made chamber. The results show that no secondary organic aerosol (SOA) can be formed in the experiments either in the absence of artificially added seed particles or in the presence of solid status of the added particles. Liquid water content is the key factor for the formation of SOA in the experiments with seeds. The amount of SOA was only about 4-7 μg m-3 in the experiments with the initial acetone of ∼15 ppm under different seed conditions. The analysis of SOA compositions by Exactive-Orbitrap mass spectrometer equipped with electro-spray interface (ESI-MS) shows that chlorine-containing and sulfur-containing compounds were detected in SOA formed from the experiments with NaCl and (NH4)2SO4 seeds, respectively, which were not identified in SOA from those with NaNO3. The compositions of SOA were mainly esters, organonitrates, hydroperoxides, etc. It is concluded that inorganic seed particles participated into the formation of SOA. Acetone SOA was mainly formed in the aqueous phase in which dissolved SOA precursors underwent further oxidation reactions, esterification reactions and/or radical-radical reactions. Our experiments further demonstrate that low-molecular-weight VOCs, such as acetone, can form SOA under certain conditions in the atmosphere, although their contributions to SOA may not be large.

[Hydrochemical Characteristics and Influencing Factors in Different Geological Background: A Case Study in Darongjiang and Lingqu Basin, Guangxi, China].

PubMed

Sun, Ping-an; Yu, Shi; Mo, Fu-zhen; He, Shi-yi; Lu, Ju-fang; Yuan, Ya-qiong

2016-01-15

The observation and sampling were carried out in May 2013 to April 2014 in a hydrological year for two river basins with different geological background in upstream of Li river basin. The seasonal variations of river water chemistry and its main influencing factors were discussed in this paper. The results showed that the hydrochemistry types of both Darongjiang basin with 9% of carbonates and Lingqu basin with nearly 50% of carbonates in area belonged to Ca-HCO3 type. Ca2+ and HCO3- were the main cations and anions. The main ion concentrations were higher in winter and lower in summer, affected by the change of the flow. Ca2+, Mg2+, HCO3- were mainly sourced from the weathering of carbonates by carbonic acid. The weathering of carbonates by sulfuric acid and the weathering of silicate rocks also had contribution to the river water chemistry. In addition, comparing to the Lingqu basin, the contribution of the weathering of carbonates was much more than the percent of carbonates area, because the carbonate rocks were eroded by the allogenic water. On the other hand, K+, Na+, Cl-, NO3-, SO4(2-) were mainly affected by the atmospheric precipitation and human activities. Comparing to the Darongjiang Basin, the effects of human activities on the changes of K+, Na+, Cl-, NO3-, SO4(2-) were more significant in Lingqu Basin.

Discovery of C5-C17 poly- and perfluoroalkyl substances in water by in-line SPE-HPLC-Orbitrap with in-source fragmentation flagging.

PubMed

Liu, Yanna; Pereira, Alberto Dos Santos; Martin, Jonathan W

2015-04-21

The presence of unknown organofluorine compounds in environmental samples has prompted the development of nontargeted analytical methods capable of detecting new perfluoroalkyl and polyfluoroalkyl substances (PFASs). By combining high volume injection with high performance liquid chromatography (HPLC) and ultrahigh resolution Orbitrap mass spectrometry, a sensitive (0.003-0.2 ng F/mL for model mass-labeled PFASs) untargeted workflow was developed for discovery and characterization of novel PFASs in water. In the first step, up to 5 mL of water is injected to in-line solid phase extraction, chromatographed by HPLC, and detected by electrospray ionization with mass spectral acquisition in parallel modes cycling back and forth: (i) full scan with ultrahigh resolving power (RP = 120,000, mass accuracy ≤3 ppm), and (ii) in-source fragmentation flagging scans designed to yield marker fragment ions including [C2F5](-) (m/z 118.992), [C3F7](-) (m/z 168.988), [SO4H](-) (m/z 96.959), and [Cl](-) (m/z 34.9). For flagged PFASs, plausible empirical formulas were generated from accurate masses, isotopic patterns, and fragment ions. In the second step, another injection is made to collect high resolution MS/MS spectra of suspect PFAS ions, allowing further confirmation of empirical formulas while also enabling preliminary structural characterization. The method was validated by applying it to an industrial wastewater, and 36 new PFASs were discovered. Of these, 26 were confidently assigned to 3 new PFAS classes that have not previously been reported in the environment: polyfluorinated sulfates (CnFn+3Hn-2SO4(-); n = 5, 7, 9, 11, 13, and 15), chlorine substituted perfluorocarboxylates (ClCnF2nCO2(-); n = 4-11), and hydro substituted perfluorocarboxylates (HCnF2nCO2(-); n = 5-16). Application of the technique to environmental water samples is now warranted.

Elimination characteristics of post-operative isoflurane levels in alveolar exhaled breath via PTR-MS analysis.

PubMed

Fernández Del Río, R; O'Hara, M E; Pemberton, P; Whitehouse, T; Mayhew, C A

2016-10-12

Isoflurane (1-chloro-2,2,2-trifluoroethyl difluoromethyl ether), C 3 H 2 ClF 5 O, is a commonly used inhalation anaesthetic. Using a proton transfer reaction mass spectrometer (PTR-MS) we have detected isoflurane in the breath of patients several weeks following major surgery. That isoflurane is detected in the breath of patients so long after being anaesthetised raises questions about when cognitive function has fully returned to a patient. Temporal profiles of isoflurane concentrations in breath are presented for five patients (F/M 3/2, mean age 50 years, min-max 36-58 years) who had undergone liver transplant surgery. In addition, results from a headspace analysis of isoflurane are presented so that the product ions resulting from the reactions of H 3 O + with isoflurane in PTR-MS could be easily identified in the absence of the complex chemical environment of breath. Six product ions were identified. In order of increasing m/z (using the 35 Cl isotope where appropriate) these are [Formula: see text] (m/z 51), CHFCl + (m/z 67), CF 3 CHCl + (m/z 117), C 3 F 4 OCl + (m/z 163), C 3 H 2 F 4 OCl + (m/z 165), and C 3 F 4 OCl + H 2 O (m/z 183). No protonated parent was detected. For the headspace study both clean air and CO 2 enriched clean air (4% CO 2 ) were used as buffer gases in the drift tube of the PTR-MS. The CO 2 enriched air was used to determine if exhaled breath would affect the product ion branching ratios. Importantly no significant differences were observed, and therefore for isoflurane the product ion distributions determined in a normal air mixture can be used for breath analysis. Given that PTR-MS can be operated under different reduced electric fields (E/N), the dependence of the product ion branching percentages for isoflurane on E/N (96-138 Td) are reported.

Degradation of ciprofloxacin antibiotic by Homogeneous Fenton oxidation: Hybrid AHP-PROMETHEE method, optimization, biodegradability improvement and identification of oxidized by-products.

PubMed

Salari, Marjan; Rakhshandehroo, Gholam Reza; Nikoo, Mohammad Reza

2018-09-01

The main purpose of this experimental study was to optimize Homogeneous Fenton oxidation (HFO) and identification of oxidized by-products from degradation of Ciprofloxacin (CIP) using hybrid AHP-PROMETHEE, Response Surface Methodology (RSM) and High Performance Liquid Chromatography coupled with Mass Spectrometry (HPLC-MS). At the first step, an assessment was made for performances of two catalysts (FeSO 4 ·7H 2 O and FeCl 2 ·4H 2 O) based on hybrid AHP-PROMETHEE decision making method. Then, RSM was utilized to examine and optimize the influence of different variables including initial CIP concentration, Fe 2+ concentration, [H 2 O 2 ]/[ Fe 2+ ] mole ratio and initial pH as independent variables on CIP removal, COD removal, and sludge to iron (SIR) as the response functions in a reaction time of 25 min. Weights of the mentioned responses as well as cost criteria were determined by AHP model based on pairwise comparison and then used as inputs to PROMETHEE method to develop hybrid AHP-PROMETHEE. Based on net flow results of this hybrid model, FeCl 2 ·4H 2 O was more efficient because of its less environmental stability as well as lower SIR production. Then, optimization of experiments using Central Composite Design (CCD) under RSM was performed with the FeCl 2 ·4H 2 O catalyst. Biodegradability of wastewater was determined in terms of BOD 5 /COD ratio, showing that HFO process is able to improve wastewater biodegradability from zero to 0.42. Finally, the main intermediaries of degradation and degradation pathways of CIP were investigated with (HPLC-MS). Major degradation pathways from hydroxylation of both piperazine and quinolonic rings, oxidation and cleavage of the piperazine ring, and defluorination (OH/F substitution) were suggested. Copyright © 2018 Elsevier Ltd. All rights reserved.

Exposures to conditioned flavours with different hedonic values induce contrasted behavioural and brain responses in pigs.

PubMed

Clouard, Caroline; Jouhanneau, Mélanie; Meunier-Salaün, Marie-Christine; Malbert, Charles-Henri; Val-Laillet, David

2012-01-01

This study investigated the behavioural and brain responses towards conditioned flavours with different hedonic values in juvenile pigs. Twelve 30-kg pigs were given four three-day conditioning sessions: they received three different flavoured meals paired with intraduodenal (i.d.) infusions of 15% glucose (F(Glu)), lithium chloride (F(LiCl)), or saline (control treatment, F(NaCl)). One and five weeks later, the animals were subjected to three two-choice feeding tests without reinforcement to check the acquisition of a conditioned flavour preference or aversion. In between, the anaesthetised pigs were subjected to three (18)FDG PET brain imaging coupled with an olfactogustatory stimulation with the conditioned flavours. During conditioning, the pigs spent more time lying inactive, and investigated their environment less after the F(LiCl) than the F(NaCl) or F(Glu) meals. During the two-choice tests performed one and five weeks later, the F(NaCl) and F(Glu) foods were significantly preferred over the F(LICl) food even in the absence of i.d. infusions. Surprisingly, the F(NaCl) food was also preferred over the F(Glu) food during the first test only, suggesting that, while LiCl i.d. infusions led to a strong flavour aversion, glucose infusions failed to induce flavour preference. As for brain imaging results, exposure to aversive or less preferred flavours triggered global deactivation of the prefrontal cortex, specific activation of the posterior cingulate cortex, as well as asymmetric brain responses in the basal nuclei and the temporal gyrus. In conclusion, postingestive visceral stimuli can modulate the flavour/food hedonism and further feeding choices. Exposure to flavours with different hedonic values induced metabolism differences in neural circuits known to be involved in humans in the characterization of food palatability, feeding motivation, reward expectation, and more generally in the regulation of food intake.

Volcán Popocatépetl, Mexico. Petrology, magma mixing, and immediate sources of volatiles for the 1994- Present eruption

USGS Publications Warehouse

Witter, J.B.; Kress, V.C.; Newhall, C.G.

2005-01-01

Volcán Popocatépetl has been the site of voluminous degassing accompanied by minor eruptive activity from late 1994 until the time of writing (August 2002). This contribution presents petrological investigations of magma erupted in 1997 and 1998, including major-element and volatile (S, Cl, F, and H2O) data from glass inclusions and matrix glasses. Magma erupted from Popocatépetl is a mixture of dacite (65 wt % SiO2, two-pyroxenes + plagioclase + Fe–Ti oxides + apatite, ∼3 wt % H2O, P = 1·5 kbar, fO2 = ΔNNO + 0·5 log units) and basaltic andesite (53 wt % SiO2, olivine + two-pyroxenes, ∼3 wt % H2O, P = 1–4 kbar). Magma mixed at 4–6 km depth in proportions between 45:55 and 85:15 wt % silicic:mafic magma. The pre-eruptive volatile content of the basaltic andesite is 1980 ppm S, 1060 ppm Cl, 950 ppm F, and 3·3 wt % H2O. The pre-eruptive volatile content of the dacite is 130 ± 50 ppm S, 880 ± 70 ppm Cl, 570 ± 100 ppm F, and 2·9 ± 0·2 wt % H2O. Degassing from 0·031 km3 of erupted magma accounts for only 0·7 wt % of the observed SO2 emission. Circulation of magma in the volcanic conduit in the presence of a modest bubble phase is a possible mechanism to explain the high rates of degassing and limited magma production at Popocatépetl.

Frequency of Application of AmF/NaF/SnCl2 Solution and Its Potential in Inhibiting the Progression of Erosion in Human Dental Enamel - An In Vitro Study.

PubMed

da Silva, Camilla Vieira; Nazello, Jessica Laporta; de Freitas, Patricia Moreira

To evaluate whether increasing the frequency of its use can enhance the protective effect of AmF/NaF/SnCl2 solution against dental erosion. Sixty human enamel samples were obtained from sound human third molars, and after the formation of incipient erosive lesions (1% citric acid, pH 4.0, for 3 min), they were divided into five treatment groups (n = 12): G1 - deionised water (negative control); G2 - NaF solution (positive control) once a day; G3 - NaF solution (positive control) twice a day; G4 - AmF/NaF/SnCl2 solution once a day; G5 - AmF/NaF/SnCl2 solution twice a day. The samples were then subjected to 5 days of erosive cycling through 6 daily immersions (2 min each) in citric acid solution (0.05 M, pH 2.6). At the end of erosive cycling, surface wear was determined by means of optical profilometry. One-way ANOVA showed that the surface wear was affected by surface treatments (p < 0.001). Tukey's test showed no difference between the groups in which NaF was applied once or twice, but they showed limited reduction in wear compared to the deionised water group (G1). In the groups treated with the AmF/NaF/SnCl2 solution, there was a statistically significant difference between one and two application times (p < 0.001). Although both demonstrated statistically significantly reduced tissue loss, increasing the frequency increased its anti-erosive potential. The AmF/NaF/SnCl2 solution proved to be effective in reducing dental enamel surface loss and its use twice a day potentiated its anti-erosive effect.

Precipitation composition and wet deposition temporal pattern in Central Serbia for the period from 1998 to 2004.

PubMed

Golobocanin, D; Zujić, A; Milenković, A; Miljević, N

2008-07-01

Bulk samples collected on a daily basis at three principal meteorological stations in central Serbia were analyzed on chloride (Cl(-)), nitrate (NO(3)(-)), sulfate (SO(4)(2-)), sodium (Na(+)), ammonium (NH(4)(+)), potassium (K(+)), calcium (Ca(2+)), and magnesium (Mg(2+)) in addition to precipitation amount, pH and conductivity measurements over the period 1998-2004. The data were subjected to variety of analyses (linear regression, principal component analysis, time series analysis) to characterize precipitation chemistry in the study area. The most abundant ion was SO(2-)(4) with annual volume weighted mean concentration of 242 microeq L(-1). Neutralization of precipitation acidity occurs both as a result of the dissolution of alkaline compounds containing Ca(2+), Mg(2+), and K(+) as well as the absorption of ammonia. The ratio of SO(4)(2-)/NO(3)(-) was above 5, which indicated that the combustion process of low-grade domestic lignite for electricity generation from coal-fired thermal power plants was the main source of pollution in the investigated area. A considerable mean annual bulk wet deposition of SO(4)-S determined by precipitation amount and concentrations of sulfate in the precipitation was calculated to be 12-35 kg ha(-1).

Water-soluble ions measured in fine particulate matter next to cement works

NASA Astrophysics Data System (ADS)

Galindo, N.; Yubero, E.; Nicolás, J. F.; Crespo, J.; Pastor, C.; Carratalá, A.; Santacatalina, M.

2011-04-01

PM2.5 samples were collected for one year in a suburban area close to an industrial complex formed by two cement factories and some quarries in southeastern Spain. Samples were analyzed by ion chromatography to determine the concentrations of major inorganic ions: Cl -, NO 3-, SO 42-, Na +, NH 4+, K +, Mg 2+ and Ca 2+. The average PM2.5 concentration (17.6 μg m -3) was within the interval reported for other Mediterranean suburban environments. Concentration peaks were registered during both winter and summer, concurrently with maxima levels of nitrate and sulfate, due to stagnation conditions and African dust episodes, respectively. Sulfate was found to be a main contributor to PM2.5 aerosol mass (4.2 μg m -3, 24%), followed by nitrate and ammonium (1.5 μg m -3, 9% each one). Correlation analyses demonstrated that fine sulfate was present as (NH 4) 2SO 4, CaSO 4 and Na 2SO 4 since ammonium concentrations were not high enough to neutralize both anions. The mean concentration of calcium (1.0 μg m -3), an element commonly found in the coarse fraction, was higher than those found in other locations of the Mediterranean basin. Additionally, the lowest levels were registered during summer, in contrast with previous findings. This was attributed to resuspension and transport of mineral dust from the neighboring quarries and cement plants during fall and winter, which was supported by the results of the CPF analysis. Atmospheric levels of potassium and chloride (0.28 and 0.51 μg m -3 annual average, respectively) also seemed to be affected by cement works, as suggested by correlation and CPF analyses. In the case of Cl -, a marked seasonality was observed, with mean winter concentrations considerably higher than summer ones, indicating a clear prevalence of anthropogenic sources over sea spray emissions.

The effects of phenoseason and storm characteristics on throughfall solute washoff and leaching dynamics from a temperate deciduous forest canopy.

PubMed

Van Stan, John T; Levia, Delphis F; Inamdar, Shreeram P; Lepori-Bui, Michelle; Mitchell, Myron J

2012-07-15

Seasonal variations in the washoff and leaching dynamics of throughfall ionic fluxes represent a significant process affecting the biogeochemical cycling of forested ecosystems-particularly for temperate deciduous forests with distinct phenological seasons (or "phenoseasons"). Most studies on temperate deciduous forests aggregate seasonal throughfall fluxes to the leafed (growing) and leafless (dormant) periods, yet the phenological conditions controlling seasonality demand finer-scale demarcations that include the transitional phenoseasons (leaf senescence and emergence). To fill these gaps our study examines the washoff and leaching dynamics of Na(+), Mg(2+), K(+), Ca(2+), Cl(-), SO(4)(2-), and NO(3)(-) throughfall derived from bulk and sequentially sampled rain events across leafed, leafless and both transitional phenoseasons over a 3-year period (2008-2010). As throughfall washoff and leached solute fluxes are also closely-coupled to rainfall conditions, we further examine the effects of storm characteristics on phenoseasonal washoff-dominated (Na(+) and Cl(-)) and leaching-dominated (K(+), Ca(2+), Mg(2+)) fluxes through intrastorm event comparison plots and factorial MANOVA. Highly significant differences in leached and washoff solute fluxes were found across meteorological conditions (p<0.001) nested within phenoseasonal divisions (p<0.00001). Phenoseasonal washoff Na(+) and Cl(-) fluxes seemed to be more closely related to leaf area; whereas, leaching flux and canopy exchange of all solutes to correspond more with major phenological changes (when the canopies tend to be most metabolically active). The greatest differences in leached Mg(2+), K(+), Ca(2+), and SO(4)(2-) fluxes were not between the full leafed and leafless phenoseasons (33-80% difference), but between the transitional periods (80 to 200 fold greater during leaf senescence than leaf emergence). Intrastorm average canopy NO(3)(-) leaching, however, ranged from low losses (1 μmol(c)m(-2)h(-1)) to canopy uptake (-2 μmol(c)m(-2)h(-1)) during both transitional phenoseasons. K(+), Ca(2+), Mg(2+) were all markedly more exchangeable during senescence, with Ca(2+) and Mg(2+) being more tightly held by the canopy. Leaching rates and fluxes for all measured solutes were negligible to negative during emergence, except for K(+) and SO(4)(2-). Our results indicate that much of the variance in timing and magnitude of throughfall solute fluxes to forest soils within temperate deciduous ecosystems may be ascribed to phenologically-delineated seasons and storm conditions. Copyright © 2012 Elsevier B.V. All rights reserved.

Artificial sweeteners as waste water markers in a shallow unconfined aquifer

NASA Astrophysics Data System (ADS)

Bichler, Andrea; Muellegger, Christian; Hofmann, Thilo

2013-04-01

One key factor in groundwater quality management is the knowledge of flow paths and recharge. In coupled ground- and surface water systems the understanding of infiltration processes is therefore of paramount importance. Recent studies show that artificial sweeteners - which are used as sugar substitutes in food and beverages - are suitable tracers for domestic wastewater in the aquatic environment. As most rivers receive sewage discharges, artificial sweeteners might be used for tracking surface waters in groundwater. In this study artificial sweeteners are used in combination with conventional tracers (inert anions Cl-, SO42-, stable water isotopes δ18O, δ2H) to identify river water infiltration and the influence of waste water on a shallow unconfined aquifer used for drinking water production. The investigation area is situated in a mesoscale alpine head water catchment. The alluvial aquifer consists of quaternary gravel deposits and is characterized by high hydraulic permeability (kfmax 5 x 10-2 ms-1), high flow velocities (vmax 250 md-1) and a considerable productivity (2,5 m3s-1). A losing stream follows the aquifer in close proximity and is susceptible to infiltrate substantial volumes of water into the alluvial sediments. Water sampling campaigns in March and July 2012 confirmed the occurrence of artificial sweeteners (Acesulfam ACE, Sucralose SUC, Saccharin SAC and Cyclamat CYC) at the investigated site. The local sewage treatment plant was identified as point source of artificial sweeteners in the river water, with ACE concentrations up to 0,6 μgL-1. ACE concentrations in groundwater where approximately of one order of magnitude lower: ACE was present in 33 out of 40 sampled groundwater wells with concentrations up to 0,07 μgL-1, thus indicating considerable influence of sewage water loaded surface water throughout the aquifer. Elevated concentrations of ACE and SAC in single observation wells denote other sources of locally limited contamination. Also, the temporal variability of sweeteners in surface water and the drinking water production well is compared with other tracers. ACE, Cl-and SO42- exhibit similar patterns in the river water. However, this behaviour cannot be observed in the production well, where ACE concentrations are varying compared to Cl- and SO42-.This suggests that the production well does receive groundwater being infiltrated prior to the sewage water treatment plant. Time series analysis of 18O, δ2H will give more insight in travel times and the location of infiltration zones.

Emergency Destruction of Information Storing Media. Appendix 2. Destruct Technology Compendium

DTIC Science & Technology

1987-12-01

L C U) 00 r. C 0 Z EC 0 00 CD CD 00 C4 C ) .0 -F 0 j o ) .0...0 cmc ,go~ S.- .) cm X.3 .1 . 1 1 1 1 1V ,a Ic 00 ON .t CM CI CmcyI CI W! W! U c t!.- CCJ .C-c v4 N OD V t 40 -z -- a- -~ LL A to) N ot SQ0 U. L CL...Y LL CL No LA ILP- LDl a .49 zII ii a A C.0 Am to- • ! t -.- t - - - - lin -sea hi ~ ~~~ CM .-. 2 2 Ll L . C C4 00 L h a so 0~ UP ,nDa gus 0. 1~2’ - - L

Evaluation of Rehabilitation Efficiency of Clogged wells drilled in fractured bedrock and alluvium

NASA Astrophysics Data System (ADS)

Lee, C.; Hamm, S.; Lee, J.; Ok, S.; Han, S.; Choo, C.; Kim, M.

2011-12-01

In Korea, more than one million of groundwater wells have been developed since 1990s. However, the groundwater wells have not been properly managed. Moreover, the importance of well maintenance and well rehabilitation has not been well recognized. In this circumstance, groundwater wells are usually terminated in 20-year operation due to well clogging, groundwater pollution, land use change, etc. which are originated from physical, chemical, biological, and artificial changes of and around the wells. The clogged state of the wells with diminished amount down to 80-85% can be ameliorated by various rehabilitation techniques as increasing discharge amount as well as extending the durability of the wells. In European countries and the USA, rehabilitation techniques of the clogged wells have been developed with understanding the cause and prevention of well bore clogging since 1990s. In recent years, the Korean Ministry of Environment (KME) recognized the importance of well rehabilitation. Under the support of the KME, this study evaluated the efficieny of rehabilitation using air surging, high-pressure water injection, brush & air surging, and explosive charge methods as applying to seven wells installed in fractured granite of Mt. Geumjeong and one well drilled in alluvial deposit of the Jeungsan-Ri area, Gyeongnam Province in the southeastern part of Korea. Hydraulic conductivity was estimated by using slug and pumping tests before and after well rehabilitation in order to assess physical, chemical, and biological changes of the wells. Hydraulic conductivity and pumping capacity of fractured bedrock are closely related to fracture characteristics such as fracture aperture, frequency, length, orientation, dip angle, interconnectivity, plane features, and filling materials. The evolution of clogging and filling of materials on and around the well makes decrease hydraulic conductivity and pumping capacity of the well. In this study, in addition of hydraulic conductivity estimation, optical televiewer (RG HI-OPTV type) and acoustic televiewer (RG HIRAT type) logs were used to quantitatively detect clogging and filling of the wells. Explosive charge method proved about 166% increase of specific capacity after rehabilitation than before. Water quality change occurred as showing the increase of EC, turbidity, and Ca2+, Mg2+, K+, Mn2+, Zn2+, SO42-, Cl-, F-, NO3-, and SiO2 concentrations, and the decrease of temperature, pH, Eh, DO, and Na+, Fe2+, and HCO3- concentrations. On the other hand, brushing method increased about 184% of specific capacity after rehabilitation than before. Water quality change showed the increase of Eh, DO, and Fe2+, HCO3-, F-, and SiO2 concentrations, and the decrease of temperature, turbidity, pH, EC, and Ca2+, Na+, Mg2+, K+, Mn2+, Zn2+, SO42-, Cl-, and NO3- concentrations. Keywords: slug test, optical and acoustic televiewers, hydraulic conductivity, rehabilitation, clogging. Acknowledgement This work was financially supported by the Korea Ministry of Environment as "The GAIA Project".

Synthesis, luminescence, and energy-transfer properties of β-Na2Ca4(PO4)2(SiO4):A (A = Eu(2+), Dy(3+), Ce(3+)/Tb(3+)) phosphors.

PubMed

Li, Kai; Shang, Mengmeng; Geng, Dongling; Lian, Hongzhou; Zhang, Yang; Fan, Jian; Lin, Jun

2014-07-07

A series of β-Na2Ca4(PO4)2(SiO4) (β-NCPS):A (A = Eu(2+), Dy(3+), Ce(3+)/Tb(3+)) phosphors were prepared via a high-temperature solid-state reaction route. The X-ray diffraction, Fourier transform infrared, photoluminescence (PL), cathodoluminescence (CL) properties, fluorescent lifetimes, and absolute quantum yield were exploited to characterize the samples. Under UV radiation, the β-NCPS:Eu(2+) phosphors present bright green emissions, and the β-NCPS:Ce(3+) phosphors show strong blue emissions, which are attributed to their 4f(6)5d(1) → 4f(7) and 5d-4f allowed transitions, respectively. The β-NCPS:Ce(3+), Tb(3+) phosphors display intense tunable color from blue to green and high absolute quantum yields (81% for β-NCPS:0.12Ce(3+) and 83% for β-NCPS:0.12Ce(3+), 0.08Tb(3+)) when excited at 365 nm. Simultaneously, the energy transfer from Ce(3+) to Tb(3+) ions is deduced from the spectral overlap between Ce(3+) emission and Tb(3+) excitation spectra and demonstrated by the change of emission spectra and decay lifetimes. Moreover, the energy-transfer mechanism from Ce(3+) to Tb(3+) ions is confirmed to be exchange interaction according to the discussion of expression from Dexter and Reisfeld. Under a low-voltage electron-beam excitation, the β-NCPS:A (A = Eu(2+), Dy(3+), Ce(3+)/Tb(3+)) phosphors exhibit their characteristic emissions, and the emission profiles of β-NCPS:Ce(3+),Tb(3+) phosphors are obviously different from those of the PL spectra; this difference might be ascribed to their different luminescence mechanisms. These results in PL and CL properties suggest that β-NCPS:A (A = Eu(2+), Dy(3+), Ce(3+)/Tb(3+)) phosphors are potential candidates for solid-state lighting and field-emission displays.

Electron paramagnetic resonance g-tensors from state interaction spin-orbit coupling density matrix renormalization group

NASA Astrophysics Data System (ADS)

Sayfutyarova, Elvira R.; Chan, Garnet Kin-Lic

2018-05-01

We present a state interaction spin-orbit coupling method to calculate electron paramagnetic resonance g-tensors from density matrix renormalization group wavefunctions. We apply the technique to compute g-tensors for the TiF3 and CuCl42 - complexes, a [2Fe-2S] model of the active center of ferredoxins, and a Mn4CaO5 model of the S2 state of the oxygen evolving complex. These calculations raise the prospects of determining g-tensors in multireference calculations with a large number of open shells.

Risk stratification with cervical length and fetal fibronectin in women with threatened preterm labor before 34 weeks and not delivering within 7 days.

PubMed

Hermans, Frederik J R; Bruijn, Merel M C; Vis, Jolande Y; Wilms, Femke F; Oudijk, Martijn A; Porath, Martina M; Scheepers, Hubertina C J; Bloemenkamp, Kitty W M; Bax, Caroline J; Cornette, Jérôme M J; Nij Bijvanck, Bas W A; Franssen, Maureen T M; Vandenbussche, Frank P H A; Kok, Marjolein; Grobman, William A; Van Der Post, Joris A M; Bossuyt, Patrick M M; Opmeer, Brent C; Mol, Ben Willem J; Schuit, Ewoud; Van Baaren, Gert-Jan

2015-07-01

To stratify the risk of spontaneous preterm delivery using cervical length (CL) and fetal fibronectin (fFN) in women with threatened preterm labor who remained pregnant after 7 days. Prospective observational study. Nationwide cohort of women with threatened preterm labor from the Netherlands. Women with threatened preterm labor between 24 and 34 weeks with a valid CL and fFN measurement and remaining pregnant 7 days after admission. Kaplan-Meier and Cox proportional hazards models were used to estimate cumulative percentages and hazard ratios (HR) for spontaneous delivery. Spontaneous delivery between 7 and 14 days after initial presentation and spontaneous preterm delivery before 34 weeks. The risk of delivery between 7 and 14 days was significantly increased for women with a CL < 15 mm or a CL ≥15 to <30 mm and a positive fFN, compared with women with a CL ≥30 mm: HR 22.3 [95% confidence interval (CI) 2.6-191] and 14 (95% CI 1.8-118), respectively. For spontaneous preterm delivery before 34 weeks the risk was increased for women with a CL < 15 mm [HR 6.3 (95% CI 2.6-15)] or with a CL ≥15 to <30 mm with either positive fFN [HR 3.6 (95% CI 1.5-8.7)] or negative fFN [HR 3.0 (95% CI 1.2-7.1)] compared with women with a CL ≥ 30 mm. In women remaining pregnant 7 days after threatened preterm labor, CL and fFN results can be used in risk stratification for spontaneous delivery. © 2015 Nordic Federation of Societies of Obstetrics and Gynecology.

Effect of iron salt counter ion in dose-response curves for inactivation of Fusarium solani in water through solar driven Fenton-like processes

NASA Astrophysics Data System (ADS)

Aurioles-López, Verónica; Polo-López, M. Inmaculada; Fernández-Ibáñez, Pilar; López-Malo, Aurelio; Bandala, Erick R.

2016-02-01

The inactivation of Fusarium solani in water was assessed by solar driven Fenton-like processes using three different iron salts: ferric acetylacetonate (Fe(acac)3), ferric chloride (FeCl3) and ferrous sulfate (FeSO4). The experimental conditions tested were [Fe] ≈ 5 mg L-1, [H2O2] ≈ 10 mg L-1 and [Fe] ≈ 10 mg L-1; [H2O2] ≈ 20 mg L-1 mild and high, respectively, and pH 3.0 and 5.0, under solar radiation. The highest inactivation rates were observed at high reaction conditions for the three iron salts tested at pH 5.0 with less than 3.0 kJ L-1 of accumulate energy (QUV) to achieve over 99.9% of F. solani inactivation. Fe(acac)3 was the best iron salt to accomplishing F. solani inactivation. The modified Fermi equation was used to fix the experimental inactivation, data showed it was helpful for modeling the process, adequately describing dose-response curves. Inactivation process using FeSO4 at pH 3.0 was modeled fairly with r2 = 0.98 and 0.99 (mild and high concentration, respectively). Fe(acac)3, FeCl3 and FeSO4 at high concentration (i.e. [Fe] ≈ 10 mg L-1; [H2O2] ≈ 20 mg L-1) and pH 5.0 showed the highest fitting values (r2 = 0.99). Iron salt type showed a remarkable influence on the Fenton-like inactivation process.

Leaching characteristics of ash from the May 18, 1980, eruption of Mount St. Helens Volcano, Washington

USGS Publications Warehouse

Smith, David Burl; Zielinski, Robert A.; Taylor, Howard E.

1982-01-01

Leaching of freshly erupted air-fall ash, unaffected by rain, from the May 18, 1.980,eruption of Mount St. Helens volcano, Washington, shows that Ca 2+, Na+, Mg+, SO4 2-, and Cl- are the predominant chemical species released on first exposure of the ash to water. Extremely high correlation of Ca with SO4 and Na with Cl in water leachates suggests the presence of CaSO4 and NaCl salts on the ash. The amount of water soluble material on ash increases with distance from source and with the weight fraction of small (less than 63 micrometers) ash particles of high-surface area. This suggests that surface reactions such as adsorption are responsible for concentrating the soluble material. CaSO4, NaCl, and other salts are probably formed as microscopic crystals in the high-temperature core of the eruption column and are then adsorbed by silicate ash particles. The environmentally important elements Zn, Cu, Cd, F, Pb, and Ba are released by a water leach in concentrations which could pose short-term hazards to some forms of aquatic life. However, calculated concentrations are based on a water-to-ash ratio of 4:1 or less, which is probably an underestimation of the regionally operative ratio. A subsequent leach of ash by warm alkaline solution shows dramatic increases in the amount of dissolved SiO2, U, and V, which are probably caused by increased dissolution of the glassy component of ash. Glass dissolution by alkaline ground water is a mechanism for providing these three elements to sedimentary traps where they may co-accumulate as uraniferous silica or U-V minerals. Leaching characteristics of ash from Mount St. Helens are comparable to characteristics of ash of similar composition from volcanoes in Guatemala. Ashes from each locality show similar ions predominating for a given leachate and similar fractions of a particular element in the ash removed on contact with the leach solution.

Incomplete turgor adjustment in Cladophora rupestrisunder fluctuating salinity regimes

NASA Astrophysics Data System (ADS)

Wiencke, Christian; Gorham, John; Tomos, Deri; Davenport, John

1992-04-01

Turgor pressure fluctuates strongly in Cladophora rupestrissubjected to low salinities and shows only a small tendency to readjust to the normal value in full seawater (incomplete turgor adjustment). This was revealed by direct turgor pressure measurements and by chemical analyses of osmotic solutes after exposure of upper and lower shore Cladophorato the different salinity regimes occurring in the intertidal zone or representing steady state osmotic acclimation. The main internal osmotic solutes were K +, Cl -, amino acids, NO 3-and glycine betaine. Na +, SO 42-and PO 43-were of less importance. The sum of the charges on the cations was similar to that for the anions. K +, Cl -and, to a lesser extent, amino acids were responsible for limited turgor pressure adjustment which did occur. The concentrations of the major osmotic solutes were influenced not only by salinity but also by light: those of amino acids and NO 3-were increased while those of K +and Cl -were decreased under illumination. Cladophorapopulations from the upper and lower shore differed in their ability to restore internal K +and Cl -levels on transfer to full seawater after long term exposure to low salinity. This may indicate ecotypic variation.

Conductive diamond electrochemical oxidation of caffeine-intensified biologically treated urban wastewater.

PubMed

Martín de Vidales, María J; Millán, María; Sáez, Cristina; Pérez, José F; Rodrigo, Manuel A; Cañizares, Pablo

2015-10-01

In this work, the usefulness of Conductive Diamond Electrochemical Oxidation (CDEO) to degrade caffeine in real urban wastewater matrixes was assessed. The oxidation of actual wastewater intensified with caffeine (from 1 to 100 mg L(-1)) was studied, paying particular attention to the influence of the initial load of caffeine and the differences observed during the treatment of caffeine in synthetic wastewater. The results showed that CDEO is a technology that is capable of efficiently degrading this compound even at very low concentrations and that it can even be completely depleted. Profiles of the ionic species of S (SO4(2-)), N (NH4(+), NO3(-)) and Cl (ClO(-), ClO3(-) and ClO4(-)) were monitored and explained for plausible oxidation mechanisms. It was observed that the efficiency achieved is higher in the treatment of real wastewater than in the oxidation of synthetic wastewater because of the contribution of electrogenerated oxidant species such as hypochlorite. The formation of chlorate and perchlorate during electrochemical processes was observed, and a combined strategy to prevent this important drawback was successfully tested based on the application of low current densities with the simultaneous dosing of hydrogen peroxide. Copyright © 2015 Elsevier Ltd. All rights reserved.

The acute toxicity of major ion salts to Ceriodaphnia dubia: I. ...

EPA Pesticide Factsheets

The ions Na+, K+, Ca2+, Mg2+, Cl-, SO42-, and HCO3-/CO32- (referred to as “major ions”) are present in all fresh waters and are physiologically required by aquatic organisms, but can be increased to harmful levels by a variety of anthropogenic activities that speed geochemical weathering or otherwise introduce or concentrate ions. While toxicity of these ions to aquatic organisms has been previously shown, it is also known that their toxicity can vary depending on the concentrations of other co-occurring anions, and understanding these relationships is key to predicting toxicity and establishing appropriate environmental limits. In this paper we conduct a series of experiments with Ceriodaphnia dubia to evaluate the acute toxicity of all twelve major ionsalts (pairing one of the cations with one of the anions) and to determine how toxicity of these salts varies as a function of background water chemistry. All salts except CaSO4 and CaCO3 were acutely toxic to C. dubia below saturation, with the lowest LC50s found for K salts. Of the remaining salts, all but CaCl2 showed some degree of decreased toxicity as the ionic content of the background water increased. Experiments that independently varied Ca:Mg ratio, Na:K ratio, Cl:SO4 ratio, and alkalinity/pH were used to show that Ca concentration was the primary factor influencing the toxicities of Na and Mg salts. In contrast, the toxicities of K salts were primarily influenced by the concentration of Na. Th

The 1985 chlorine and fluorine inventories in the stratosphere based on ATMOS observations at 30 deg North latitude

NASA Technical Reports Server (NTRS)

Zander, R.; Gunson, M. R.; Farmer, C. B.; Rinsland, C. P.; Irion, F. W.; Mahieu, E.

1992-01-01

Results are presented of an investigation of the Cl and F inventories derived from the concentrations of eleven Cl- and F-bearing organic and inorganic species throughout the atmosphere, based on observations with the Atmospheric Trace Molecule Spectroscopy instrument aboard the Space Shuttle during the Spacelab 3 mission of April 29 to May 6, 1985. It was found that, in April-May 1985, near 30 deg N, the mean total stratospheric concentrations of Cl and F were 2.58 +/-0.10 ppbv and 1.15 +/-0.12 ppbv, respectively. Partitioning among the source, sink, and reservoir species was consistent with the conservation of the F and Cl budgets throughout the stratosphere. It is shown that the budgets of Cl and F above about 45 km altitude can be determined accurately by measuring only HCl, HF, and CF4 and provide a straightforward timely reference point for future inventories and trends evaluations.

F-Cl-OH partitioning between biotite and apatite

NASA Astrophysics Data System (ADS)

Zhu, Chen; Sverjensky, Dimitri A.

1992-09-01

An assessment of F-C1-OH partitioning between natural apatite and biotite in a variety of rocks was used to evaluate reciprocal (Mg, Fe 2+, Al VI) (F, Cl, OH) mixing properties for biotite according to the reciprocal salt solution model of WOOD and NICHOLLS (1978). Ideal mixing of F-C1-OH and Fe-Mg-Al VI in the hydroxyl and octahedral sites is assumed for biotites with dilute Cl concentrations. The reciprocal interaction parameters, in terms of Gibbs free energies, for the reactions KMg3[ AlSi3O10]( OH) 2 + KFe3[ AlSi3O10]( F) 2 = KMg3[ AlSi3O10]( F) 2 + KFe3[ AlSi3O10]( OH) 2 Phl Fann Fphl Ann and KMg3[ AlSi3O10]( Cl) 2 + KFe3[ AlSi3O10]( OH) 2 = KMg3[ AlSi3O10]( OH) 2 + KFe3[ AlSi3O10] ( Cl) 2 Clphl Ann Phl Clann are about -10 kcal/mol and -4.5 kcal/mol, respectively. These mixing properties are consistent with standard state thermodynamic properties for F and Cl endmember phases from ZHU and SVERJENSKY (1991). The approach of studying F-C1-OH partitioning between biotite and apatite permits distinguishing the reciprocal effects from the effects of temperature, pressure, and fluid composition. The resultant mixing properties are consistent with observations both in hydrothermal experiments and in natural mineral assemblages. The mixing properties presented in this study enable us now to predict F and Cl concentrations of hydrothermal fluids from the measured F and Cl concentrations in biotite with variable Fe-Mg-Al VI proportions. A case study of the Santa Rita porphyry copper deposits, New Mexico, shows that hydrothermal fluids responsible for the phyllic alteration had a salinity about 3 molal Cl -, in agreement with fluid inclusion studies. Our internally consistent standard thermodynamic properties and solid solution models also lead to recalibration of the apatite-biotite geothermometer. The revised geothermometer predicts temperatures that agree with those estimated from other independent geothermometers. The large reciprocal effects in biotite also point out the need to revise other geothermometers using biotite and to revise the ideal mixing model for biotite in petrologic studies.

Oxygen isotope activities and concentrations in aqueous salt solutions at elevated temperatures: Consequences for isotope geochemistry

USGS Publications Warehouse

Truesdell, A.H.

1974-01-01

Studies of the effect of dissolved salts on the oxygen isotope activity ratio of water have been extended to 275??C. Dehydrated salts were added to water of known isotope composition and the solutions were equilibrated with CO2 which was sampled for analysis. For comparison similar studies were made using pure water. Results on water nearly coincide with earlier calculations. Salt effects diminish with increasing temperature only for solutions of MgCl2 and LiCl. Other salt solutions show complex behavior due to the temperature-dependent formation of ion pairs of changing character. Equilibrium fractionations (103 ln ??) between 1 molal solutions and pure water at 25, 100, and 275??C are: NaCl 0.0, -1.5, +1.0; KCl 0.0, -1.0, +2.0; LiCl -1.0, -0.6, -0.5; CaCl2 -0.4, -1.8, +0.8; MgCl2 -1.1, -0.7, -0.3; MgSO4 -1.1, +0.1, -; NaF (0.8 m) 0.0, -1.5, -0.3; and NH4Cl (0.55 m) 0.0, -1.2, -1.3. These effects are significant in the isotope study of hot saline fluids responsible for ore deposition and of fluids found in certain geothermal systems. Minor modification of published isotope geothermometers may be required. ?? 1974.

Energetic Diagrams and Structural Properties of Monohaloacetylenes HC≡CX (X = F, Cl, Br).

PubMed

Khiri, D; Hochlaf, M; Chambaud, G

2016-08-04

Highly correlated electronic wave functions within the Multi Reference Configuration Interaction (MRCI) approach are used to study the stability and the formation processes of the monohaloacetylenes HCCX and monohalovinylidenes C2HX (X = F, Cl, Br) in their electronic ground state. These tetra-atomics can be formed through the reaction of triatomic fragments C2F, C2Cl, and C2Br with a hydrogen atom or of C2H with halogen atoms via barrierless reactions, whereas the reactions between the diatomics [C2 + HX] need to overcome barriers of 1.70, 0.89, and 0.58 eV for X = F, Cl, and Br. It is found that the linear HCCX isomers, in singlet symmetry, are more stable than the singlet C2HX iso-forms by 1.995, 2.083, and 1.958 eV for X = F, Cl, and Br. The very small isomerization barriers from iso to linear forms are calculated 0.067, 0.044, and 0.100 eV for F, Cl, and Br systems. The dissociation energies of the HCCX systems (without ZPE corrections), resulting from the breaking of the CX bond, are calculated to be 5.647, 4.691, and 4.129 eV for X = F, Cl, Br, respectively. At the equilibrium geometry of the X(1)Σ(+) state of HCCX, the vertical excitation energies in singlet and triplet symmetries are all larger than the respective dissociation energies. Stable excited states are found only as (3)A', (3)A″, and (1)A″ monohalovinylidene structures.

Installation and Implementation of a Comprehensive Groundwater Monitoring Program for the Indian Wells Valley, California

DTIC Science & Technology

2010-04-01

isotopes. Laboratory analysis for general chemistry included Na, Ca, Mg, K, Fe, Cl, HCO3, CO3 , SO4, F, B, NO3, arsenic (As), hardness, alkalinity...used for interpretations within the project. Prior to this effort, a single -location repository for isotopic data related to IWV investigations...canyons of importance to this study (Indian Wells Canyon, Freeman Canyon, and the upgradient canyons of Cow Haven, Sage, and Horse). Single samples

Synthesis, characterization, X-ray crystal structure and conductometry studying of a number of new Schiff base complexes; a new example of binuclear square pyramidal geometry of Cu(II) complex bridged with an oxo group

NASA Astrophysics Data System (ADS)

Golbedaghi, Reza; Alavipour, Ehsan

2015-11-01

Three new binuclear Cu(II), Mn(II), Co(II) complexes [Cu2(L) (ClO4)](ClO4)2 (1), [Mn2(L) (ClO4)](ClO4)2 (2), and [Co2(L) (ClO4)](ClO4)2 (3), {L = 1,3-bis(2-((Z)-(2-aminopropylimino)methyl)phenoxy)propan-2-ol} have been synthesized. Single crystal X-ray structure analysis of complex 1 showed that the complex is binuclear and all nitrogen and oxygen atoms of ligand (N4O3) are coordinated to two Cu(II) center ions. In addition, the crystal structure studying shows, a perchlorate ion has been bridged to the Cu(II) metal centers. However, two distorted square pyramidal Cu(II) ions are bridged asymmetrically by a perchlorate ion and oxygen of hydroxyl group of Schiff base ligand. In addition, the conductometry behaviors of all complexes were studied in acetonitrile solution.

Enhanced phosphate selectivity from wastewater using copper-loaded chelating resin functionalized with polyethylenimine.

PubMed

An, Byungryul; Nam, Juhee; Choi, Jae-Woo; Hong, Seok-Won; Lee, Sang-Hyup

2013-11-01

In water and wastewater, phosphate is considered a critical contaminant due to cause algae blooms and eutrophication. To meet the stringent regulation of phosphate in water, a new commercial chelating resin functionalized with polyethylenimine was tested for phosphate removal by loading Cu(2+) and Fe(2+)/Fe(3+) to enhance selectivity for phosphate. Batch and column experiments showed that CR20-Cu exhibited high selectivity for phosphate over other strong anions such as sulfate. The average binary phosphate/nitrate and phosphate/sulfate factors for CR20-Cu were calculated to be 7.3 and 4.8, respectively, which were more than 0.97 and 0.22 for a commercial anion exchanger (AMP16). The optimal pH for the phosphate removal efficiency was determined to be 7. According to the fixed-bed column test, the breakthrough sequence for multiple ions was HPO4(2-)>SO4(2-)>NO3(-)>Cl(-). Saturated CR20-Cu can be regenerated using 4% NaCl at pH 7. More than 95% of the phosphate from CR20-Cu was recovered, and the phosphate uptake capacity for CR20-Cu was not reduced after 7 regeneration cycles. Copyright © 2013 Elsevier Inc. All rights reserved.

Boiler Control Systems Oxygen Trim Systems Manual.

DTIC Science & Technology

1983-02-01

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Effect of deforestation on stream water chemistry in the Skrzyczne massif (the Beskid Śląski Mountains in southern Poland).

PubMed

Kosmowska, Amanda; Żelazny, Mirosław; Małek, Stanisław; Siwek, Joanna Paulina; Jelonkiewicz, Łukasz

2016-10-15

The purpose of the study was to identify the factors affecting stream water chemistry in the small mountain catchments deforested to varying degrees, from 98.7 to 14.1%, due to long-term acid deposition. Water samples were collected monthly in 2013 and 2014 from 17 streams flowing across three distinct elevation zones in the Skrzyczne massif (Poland): Upper, Middle and Lower Forest Zone. Chemical and physical analyses, including the pH, electrical conductivity (EC), total mineral content (Mt), water temperature, and the concentrations of Ca(2+), Mg(2+), Na(+), K(+), HCO3(-), SO4(2-), Cl(-), and NO3(-), were conducted. Based on Principal Component Analysis (PCA), the most important factor affecting water chemistry was human impact associated with changes in pH, SO4(2-) concentration, and the concentration of most of the main ions. The substantial acidity of the studied environment contributed to the exclusion of natural factors, associated with changes in discharge, from the list of major factors revealed by PCA. All of the streams were characterized by very low EC, Mt, and low concentrations of the main ions such as Ca(2+) and HCO3(-). This is the effect of continuous leaching of solutes from the soils by acidic precipitation. The lowest parameter values were measured for the streams situated in the Upper Forest Zone, which is associated with greater acid deposition at the higher elevations. In the streams located in the Upper Forest Zone, a higher percentage of SO4(2-) occurred than in the streams situated in the Middle and Lower Forest Zones. However, the largest share of SO4(2-) was measured in the most deforested catchment. The saturation of the studied deforested catchment with sulfur compounds is reflected by a positive correlation between SO4(2-) and discharge. Hence, a forest acts as a natural buffer that limits the level of acidity in the natural environment caused by acidic atmospheric deposition. Copyright © 2016 Elsevier B.V. All rights reserved.

Growth and scintillation properties of Eu doped BaCl2/LiF eutectic scintillator

NASA Astrophysics Data System (ADS)

Kamada, Kei; Hishinuma, Kosuke; Kurosawa, Shunsuke; Yamaji, Akihiro; Shoji, Yasuhiro; Pejchal, Jan; Yokota, Yuui; Ohashi, Yuji; Yoshikawa, Akira

2015-12-01

Eu doped BaCl2/LiF eutectics were grown by the micro-pulling down method and their directionally solidified eutectic (DSE) system has been investigated. The grown eutectic showed main phases of cubic LiF and orthorhombic BaCl2. In these eutectics, the 399 nm emission of Eu2+ 4f5d was obtained. It shows the intrinsic decay time of about 410 ns. The light yield of the 1-mm-thick eutectic showed 7000 ph/5.5 MeV alpha-ray.

Accurate multireference calculations of the electronic structure of TiF 2 and TiCl 2

NASA Astrophysics Data System (ADS)

Vogel, M.; Wenzel, W.

2005-09-01

We report a systematic study of the electronic structure of two members of the transition metal dihalide family, TiF 2 and TiCl 2. Using the configuration interaction method in large basis sets we investigated the lowest 15 states of TiF 2 and TiCl 2. We report bond lengths, frequencies and dissociation energies of both molecules. For TiF 2 we found a near degeneracy of the ground and the first excited state with a possible breakdown of the Born-Oppenheimer approximation.

Phase Behavior of Complex Superprotonic Solid Acids

NASA Astrophysics Data System (ADS)

Panithipongwut, Chatr

Superprotonic phase transitions and thermal behaviors of three complex solid acid systems are presented, namely Rb3H(SO4) 2-RbHSO4 system, Rb3H(SeO4)2-Cs 3H(SeO4)2 solid solution system, and Cs6 (H2SO4)3(H1.5PO4) 4. These material systems present a rich set of phase transition characteristics that set them apart from other, simpler solid acids. A.C. impedance spectroscopy, high-temperature X-ray powder diffraction, and thermal analysis, as well as other characterization techniques, were employed to investigate the phase behavior of these systems. Rb3H(SO4)2 is an atypical member of the M3H(XO4)2 class of compounds (M = alkali metal or NH4+ and X = S or Se) in that a transition to a high-conductivity state involves disproportionation into two phases rather than a simple polymorphic transition [1]. In the present work, investigations of the Rb3H(SO4)2-RbHSO4 system have revealed the disproportionation products to be Rb2SO 4 and the previously unknown compound Rb5H3(SO 4)4. The new compound becomes stable at a temperature between 25 and 140 °C and is isostructural to a recently reported trigonal phase with space group P3m of Cs5H 3(SO4)4 [2]. At 185 °C the compound undergoes an apparently polymorphic transformation with a heat of transition of 23.8 kJ/mol and a slight additional increase in conductivity. The compounds Rb3H(SeO4)2 and Cs 3H(SeO4)2, though not isomorphous at ambient temperatures, are quintessential examples of superprotonic materials. Both adopt monoclinic structures at ambient temperatures and ultimately transform to a trigonal (R3m) superprotonic structure at slightly elevated temperatures, 178 and 183 °C, respectively. The compounds are completely miscible above the superprotonic transition and show extensive solubility below it. Beyond a careful determination of the phase boundaries, we find a remarkable 40-fold increase in the superprotonic conductivity in intermediate compositions rich in Rb as compared to either end-member. The compound Cs6(H2SO4)3(H 1.5PO4)4 is unusual amongst solid acid compounds in that it has a complex cubic structure at ambient temperature and apparently transforms to a simpler cubic structure of the CsCl-type (isostructural with CsH2PO4) at its transition temperature of 100-120 °C [3]. Here it is found that, depending on the level of humidification, the superprotonic transition of this material is superimposed with a decomposition reaction, which involves both exsolution of (liquid) acid and loss of H2O. This reaction can be suppressed by application of sufficiently high humidity, in which case Cs6(H2SO4)3(H 1.5PO4)4 undergoes a true superprotonic transition. It is proposed that, under conditions of low humidity, the decomposition/dehydration reaction transforms the compound to Cs6(H2-0.5xSO 4)3(H1.5PO4)4-x, also of the CsCl structure type at the temperatures of interest, but with a smaller unit cell. With increasing temperature, the decomposition/dehydration proceeds to greater and greater extent and unit cell of the solid phase decreases. This is identified to be the source of the apparent negative thermal expansion behavior. References: [1] L.A. Cowan, R.M. Morcos, N. Hatada, A. Navrotsky, S.M. Haile, Solid State Ionics 179 (2008) (9-10) 305. [2] M. Sakashita, H. Fujihisa, K.I. Suzuki, S. Hayashi, K. Honda, Solid State Ionics 178 (2007) (21-22) 1262. [3] C.R.I. Chisholm, Superprotonic Phase Transitions in Solid Acids: Parameters affecting the presence and stability of superprotonic transitions in the MHnXO4 family of compounds (X=S, Se, P, As; M=Li, Na, K, NH4, Rb, Cs), Materials Science, California Institute of Technology, Pasadena, California (2003).

The effect of current reversal on coated titanium electrodes

NASA Astrophysics Data System (ADS)

Elnathan, Francis

Coated titanium electrodes have applications in the electrochemical industry, including water treatment and swimming pool chlorination. Current/polarity reverse electrolysis is a technique used for "self-cleaning" of the coated titanium anodes employed in water disinfection and treatment. However, the literature holds very little information about the effects of polarity reversal on these anodes. The present work appears to be the first to investigate coated titanium anodes in polarity reversal in a systematic method. Two commercial titanium electrodes (RuTi and IrTa) were studied. Polarity reversal was the main electrochemical technique employing a current density of 1200 A/m 2, except when current density was studied. The effects of NO 3-, SO42-, ClO4 -, HPO42-, CO32-, Mg2+ and Ca2+ on electrode lifetime were examined. Analysis of the electrochemical results showed that plateau time (tau p), for gas evolution, is highly important to the lifetime of the coated titanium anodes. The effects of three electrolysis variables on the coated titanium anode life were examined. Current density was observed to have an inverse relationship with anode life while reversal cycle time had a direct relation with lifetime. NaCl concentration had no discernible effect. In general, the RuTi electrode exhibited longer lifetimes than IrTa except for a few specific conditions. The influence of the concentration of five anions (NO3-, SO42-, ClO 4-, HPO42-, and CO3 2-) was determined. Changing the composition and concentration of anions affected the lifetimes of the two electrodes, especially nitrate, hydrogen phosphate and carbonate. The lifetime of IrTa was highest in nitrate, and increased as a function of nitrate concentration. The service life of RuTi was highest in hydrogen phosphate, and increased with increasing hydrogen phosphate concentration. Lifetime of both anodes decreased with increasing carbonate ions. The effects of Mg2+ and Ca2+ on electrode lifetime were examined with three anions (NO3-, HPO42-, ClO4-) electrolytes. While there were numerous effects and interactions between Mg2+ or Ca2+ and anions on lifetime, these effects were found to mainly affect the amount of time the electrodes spent in the charging and discharging reactions. The times related to gas evolution (which is the plateau time, tau p) were found to be strikingly similar. The charging times (tau C) which are related to adsorption and desorption of species were not also any significantly different. Coating dissolution, substrate and/or coating passivation mechanisms were identified as being responsible for coated titanium anode failure in current reverse and hard water electrolysis. IrTa is believed to have failed predominantly by the dissolution mechanism in nitrate, hydrogen phosphate and perchlorate. RuTi failed predominantly by substrate and/or coating passivation in hydrogen phosphate, nitrate and carbonate. Anode failure is believed to be the result of plateau (taup) and charging (tauC)reactions occurring at the coating/electrolyte and/or substrate/coating interface. The tau p and tauC are useful determinants for the process of anode failure.

Capturing temporal and spatial variability in the chemistry of shallow permafrost ponds

NASA Astrophysics Data System (ADS)

Morison, Matthew Q.; Macrae, Merrin L.; Petrone, Richard M.; Fishback, LeeAnn

2017-12-01

Across the circumpolar north, the fate of small freshwater ponds and lakes (< 1 km2) has been the subject of scientific interest due to their ubiquity in the landscape, capacity to exchange carbon and energy with the atmosphere, and their potential to inform researchers about past climates through sediment records. A changing climate has implications for the capacity of ponds and lakes to support organisms and store carbon, which in turn has important feedbacks to climate change. Thus, an improved understanding of pond biogeochemistry is needed. To characterize spatial and temporal patterns in water column chemistry, a suite of tundra ponds were examined to answer the following research questions: (1) does temporal variability exceed spatial variability? (2) If temporal variability exists, do all ponds (or groups of ponds) behave in a similar temporal pattern, linked to seasonal hydrologic drivers or precipitation events? Six shallow ponds located in the Hudson Bay Lowlands region were monitored between May and October 2015 (inclusive, spanning the entire open-water period). The ponds span a range of biophysical conditions including pond area, perimeter, depth, and shoreline development. Water samples were collected regularly, both bimonthly over the ice-free season and intensively during and following a large summer storm event. Samples were analysed for nitrogen speciation (NO3-, NH4+, dissolved organic nitrogen) and major ions (Cl-, SO42-, K+, Ca2+, Mg2+, Na+). Across all ponds, temporal variability (across the season and within a single rain event) exceeded spatial variability (variation among ponds) in concentrations of several major species (Cl-, SO42-, K+, Ca2+, Na+). Evapoconcentration and dilution of pond water with precipitation and runoff inputs were the dominant processes influencing a set of chemical species which are hydrologically driven (Cl-, Na+, K+, Mg2+, dissolved organic nitrogen), whereas the dissolved inorganic nitrogen species were likely mediated by processes within ponds. This work demonstrates the importance of understanding hydrologically driven chemodynamics in permafrost ponds on multiple scales (seasonal and event scale).

Electrocoagulation mechanism of perfluorooctanoate (PFOA) on a zinc anode: Influence of cathodes and anions.

PubMed

Wang, Yujuan; Lin, Hui; Jin, Fangyuan; Niu, Junfeng; Zhao, Jinbo; Bi, Ying; Li, Ying

2016-07-01

Batch experiments were conducted to investigate the effects of cathode materials and anions (Cl(-), SO4(2-), NO3(-), and CO3(2-)/HCO3(-)) on perfluorooctanoate (PFOA) removal in electrocoagulation process using zinc anode. The results indicated that the hydroxide flocs generated in-situ in the electrocoagulation process using the stainless steel rod as cathode were more effective than those using aluminum rod as cathode for the removal of PFOA after 20min of electrocoagulation at a current density of 0.5mAcm(-2). Hydroxide flocs generated in-situ in the electrocoagulation in the presence of Cl(-)/NO3(-) could effectively remove PFOA from aqueous solution with the removal ratios of 99.7%/98.1% and 98.9%/97.3% using stainless steel rod and aluminum rod as cathode, respectively. However, the PFOA removal ratios were 96.2%/4.1% and 7.4%/4.6% using stainless steel rod and aluminum rod as cathode, respectively, in the presence of SO4(2-) and CO3(2-)/HCO3(-). The different removal ratios of PFOA during the electrocoagulation process were primarily due to the fact that the hydroxide flocs generated in-situ were different in the presence of diverse cathodes and anions. We firstly demonstrated that Zn0.70Al0.30(OH)2(CO3)0.15·xH2O and ZnO generated in-situ in the electrocoagulation process (except for CO3(2-)/HCO3(-)) using zinc anode and aluminum/stainless steel rod cathode governed the sorption of PFOA. The adsorbent hydroxide flocs in-situ generated in the presence of Cl(-) could effectively remove PFOA from aqueous solution containing CO3(2-)/HCO3(-) anion at the initial hydroxide flocs concentration of 2000mgL(-1). These results provided an effective and alternative method to remove PFOA from aqueous solution containing CO3(2-)/HCO3(-) anion. Copyright © 2016 Elsevier B.V. All rights reserved.

An improved model for the calculation of CO2 solubility in aqueous solutions containing Na+, K+, Ca2+, Mg2+, Cl-, and SO42-

USGS Publications Warehouse

Duan, Zhenhao; Sun, R.; Zhu, Chen; Chou, I.-Ming

2006-01-01

An improved model is presented for the calculation of the solubility of carbon dioxide in aqueous solutions containing Na+, K+, Ca2+, Mg2+, Cl-, and SO42- in a wide temperature-pressure-ionic strength range (from 273 to 533 K, from 0 to 2000 bar, and from 0 to 4.5 molality of salts) with experimental accuracy. The improvements over the previous model [Duan, Z. and Sun, R., 2003. An improved model calculating CO2 solubility in pure water and aqueous NaCl solutions from 273 to 533K and from 0 to 2000 bar. Chemical Geology, 193: 257-271] include: (1) By developing a non-iterative equation to replace the original equation of state in the calculation of CO 2 fugacity coefficients, the new model is at least twenty times computationally faster and can be easily adapted to numerical reaction-flow simulator for such applications as CO2 sequestration and (2) By fitting to the new solubility data, the new model improved the accuracy below 288 K from 6% to about 3% of uncertainty but still retains the high accuracy of the original model above 288 K. We comprehensively evaluate all experimental CO2 solubility data. Compared with these data, this model not only reproduces all the reliable data used for the parameterization but also predicts the data that were not used in the parameterization. In order to facilitate the application to CO2 sequestration, we also predicted CO2 solubility in seawater at two-phase coexistence (vapor-liquid or liquid-liquid) and at three-phase coexistence (CO2 hydrate-liquid water-vapor CO2 [or liquid CO2]). The improved model is programmed and can be downloaded from the website http://www.geochem-model.org/programs.htm. ?? 2005 Elsevier B.V. All rights reserved.

Hydrogeochemistry of the Overland Flow in Soil at Agroecosystems in Eastern Amazon

NASA Astrophysics Data System (ADS)

Costa, C. F. G. D.; Figueiredo, R. O.; Oliveira, F. D. A.

2014-12-01

In the watershed of the Timboteua and Buiuna streams, northeast of Pará state, Amazon, it was characterized the overland flow dissolved material by some hydrogeochemical variables: electrical conductivity (EC), pH, chloride (Cl-), nitrate (NO3-), phosphate (PO43-), and sulfate (SO42-). In two small holder properties three overland flow experimental plots (1m2) were placed in each of the six evaluated ecosystems under similar biophysical conditions, totaling 18 plots. There was also installed three rainwater collectors and two rain gauges in a nearby area. In the rainy season were collected 234 samples of rainwater and overland flow. The evaluation of the measured variables promote the hydrogeochemical characterization of the overland flow at soil under chop-and-mulch and slash-and-burn practices in the different ecosystems found in the familiar agriculture of this watershed, in which it was identified some distinct hydrogeochemical characteristics of the overland flow. The lowest losses of NO3- (variation range = 0.07 to 2.57 μM) was found in agroecosystem - chop-and-mulch, this nutrient obtained higher values in agroecosystem - slash-and-burn (RQ). In agroecosystem (RQ) initially, there was a high value of PO43- (8.87 μM); EC (121 μS cm-1) and a subsequent sharp decline. Secondary successional forest (CP) of 20 years presented in overland flow pH 4.8 and EC 25 μS cm-1 (average 6 months), low loss of NO3- (0.2 μM) and PO43- (0.05 μM), and large range of variation of SO42- (0.7 to 21.5 μM). While Cl- and SO42- overland flow concentrations were affect by the rainfall variation, the increase of NO3- and PO43-concentrations were more related to the ecosystem management, with the first element responding to the presence of nitrogen-fixing species and the second responding to the burning practices. In summary: This study was efficient to characterize the hydrogeochemical of the overland flow and its relation to the altered ecosystems by Amazonian family farming.

Biogenic emissions and biomass burning influences on the chemistry of the fogwater and stratiform precipitations in the African equatorial forest

NASA Astrophysics Data System (ADS)

Lacaux, J. P.; Loemba-Ndembi, J.; Lefeivre, B.; Cros, B.; Delmas, R.

An automatic wet-only precipitation collector and a fogwater collector were operated in the coastal forest of equatorial Congo (Dimonika), for a complete seasonal cycle (November 1986-September 1987). Inorganic (Na +, K +, NH 4+, Ca 2+, NO 3-, Cl -, SO 42-) and organic (HCOO -, CH 3COO -) ions were determined in 33 stratiform rain events and nine fog events. With the raindrop size distributions, measured over a 1 year period (June 1988-June 1989) at the site of Enyelé in the Equatorial forest of Congo, were established the relationship between the liquid water content ( LWC in gm -3) and the rate of rainfall ( R in mm h -1) for the stratiform rains: LWC = 0.055 × R0.871 with a correlation coefficient of 0.98. Taking into account the dilution effect due to LWC, ionic concentrations of fogwater and stratiform precipitation are enriched during the dry season. In particular, K +, NO 3-, SO 42- and Ca 2+ are considerably enriched indicating the seasonal influence of the biomass burning due to savanna fires and terrigenous source from deserts of the Southern Hemisphere. Comparison of the chemical contents of fogwater—which mainly represents the local emission of the forest—and stratiform precipitation—which represent the air chemical content of the planetary boundary layer—during the dry season enabled us to show the following. Fog and rain with comparable chemical contents in mineral elements indicate a generalized contamination of the boundary layer by marine (Na +, Cl -), terrigenous (Ca 2+) and above all by biomass burning (K +, NO 3-, SO 42-) sources. The organic content (HCOO -, CH 3COO -) higher for the fogs than for rains, unexplainable by the dilution effect, has its source at a local level in the forest ecosystem. The estimation, from the organic content of fog and rain, of the gaseous concentrations of formic and acetic acids confirm the production of carboxylic acids measured in Amazonia during ABLE (for HCOOH : 510 ppt at canopy level and 170 ppt in free troposphere and for CH 3COOH : 410 ppt and 210 ppt, respectively).

Sahara dust, ocean spray, volcanoes, biomass burning: pathways of nutrients into Andean rainforests

NASA Astrophysics Data System (ADS)

Fabian, P.; Rollenbeck, R.; Spichtinger, N.; Brothers, L.; Dominguez, G.; Thiemens, M.

2009-10-01

Regular rain and fogwater sampling in the Podocarpus National Park, on the humid eastern slopes of the Ecuadorian Andes, along an altitude profile between 1960 and 3180 m, has been carried out since 2002. The samples, accumulated over about 1-week intervals, were analysed for pH, conductivity and major ions (K+, Na+, NH4+, Ca2+, Mg2+, Cl-, SO42-, NO3-, PO43-). About 35% of the weekly samples had very low ion contents, with pH mostly above 5 and conductivity below 10 μS/cm. 10-days back trajectories (FLEXTRA) showed that respective air masses originated in pristine continental areas, with little or no obvious pollution sources. About 65%, however, were significantly loaded with cations and anions, with pH as low as 3.5 to 4.0 and conductivity up to 50 μS/cm. The corresponding back trajectories clearly showed that air masses had passed over areas of intense biomass burning, active volcanoes, and the ocean, with episodic Sahara and/or Namib desert dust interference. Enhanced SO42- and NO3+ were identified, by combining satellite-based fire pixel observations with back trajectories, as predominantly resulting from biomass burning. Analyses of oxygen isotopes 16O, 17O, and 18O in nitrate show that nitrate in the samples is indeed a product of atmospheric conversion of precursors. Some SO42-, about 10% of the total input, could be identified to originate from active volcanoes, whose plumes were encountered by about 10% of all trajectories. Enhanced Na+, K+, and Cl- were found to originate from ocean spray sources. They were associated with winds providing Atlantic air masses to the receptor site within less than 5 days. Episodes of enhanced Ca2+ and Mg2+ were found to be associated with air masses from African deserts. Satellite aerosol data confirm desert sources both on the Northern (Sahara) as on the Southern Hemisphere (Namib), depending on the season. A few significant PO43- peaks are related with air masses originating from North African phosphate mining fields.

A new pullulan-producing yeast and medium optimization for its exopolysaccharide production

NASA Astrophysics Data System (ADS)

Zhao, Shuangzhi; Chi, Zhenming

2003-04-01

Yeast strain Y68 producing high level of pullulan was isolated from the phyton collected in Toulouse, France. This strain was identified to be Rhodotorula bacarum by BIOLOG analysis. This is the first report that pullulan was produced by Rhodotorula bacarum. The optimal medium (g L-1) for pullulan production by this strain was 80 glucose, 20 soybean cake hydrolysate, 5 K2HPO4, 1 NaCl, 0.2 MgSO4·7H2O, 0.6 (NH4)2SO4, pH 7.0. Under this condition, 54 gL-1 pullulan was produced within 60 h at 30°C. Pullulan is a better starting material for producing marine prodrugs.

Towards the establishment of a general rate law for gypsum nucleation

NASA Astrophysics Data System (ADS)

Reznik, Itay J.; Ganor, Jiwchar; Gruber, Chen; Gavrieli, Ittai

2012-05-01

Gypsum nucleation kinetics from a wide range of chemical compositions (1.45 < Ca2+/SO42- < 115), ionic strengths (I = 2.5-10 m) and saturation state with respect to gypsum (Ωgyp = 1.07-8.4) were examined in batch experiments containing mixtures of Ca2+-rich Dead Sea brine and SO42-rich seawater with or without addition of extra Na2SO4 and CaCl2·2H2O. The induction times attained in the present study were compiled together with literature values from experiments carried out under significantly different conditions (synthetic NaCl solutions; I = 0.09-6.3 m; Ca2+/SO42- = 1; Ωgyp:1.59-7.76). Despite the variability in the experimental solutions, a single rate law based on classic nucleation theory was formulated to describe the induction times from more than 80 experiments: logT=log{1}/{3.17·Cs·exp{-}7.08ln2Ω}+0.072·Cs·exp-{1.426}/{ln2Ω} where Tind is the induction time, Cs is the solubility of gypsum and Ω is the saturation state with respect to gypsum. The rate law provides Tind for gypsum precipitation from aqueous solutions at 25 °C, containing no synthetic antiscalants or catalysts, within a 95% confidence interval within a factor of 5. Based on this rate law, we show that at present most of the precipitation of gypsum from the Dead Sea brine occurs following significant evaporation in the industrial evaporation ponds and not in the Dead Sea itself. Whereas Tind in Dead Sea brines is very long (on the order of 3 years), the evaporation of brine in the industrial ponds leads to increased Ω values, and thus to short Tind in the order of a few days. However, if seawater or reject brine from seawater desalinization will be introduced to the Dead Sea to restore its declining level, Tind will be significantly reduced and gypsum nucleation and precipitation will occur. For evaporated seawater, the proposed rate law predicts that even though saturation is obtained when seawater is evaporated by a factor of 2.8, gypsum will nucleate at reasonable times (few years) only when seawater are evaporated by a factor of ˜3.3.

Near-thermal reactions of Au(+)(1S,3D) with CH3X (X = F,Cl).

PubMed

Taylor, William S; Matthews, Cullen C; Hicks, Ashley J; Fancher, Kendall G; Chen, Li Chen

2012-01-26

Reactions of Au(+)((1)S) and Au(+)((3)D) with CH(3)F and CH(3)Cl have been carried out in a drift cell in He at a pressure of 3.5 Torr at both room temperature and reduced temperatures in order to explore the influence of the electronic state of the metal on reaction outcomes. State-specific product channels and overall two-body rate constants were identified using electronic state chromatography. These results indicate that Au(+)((1)S) reacts to yield an association product in addition to AuCH(2)(+) in parallel steps with both neutrals. Product distributions for association vs HX elimination were determined to be 79% association/21% HX elimination for X = F and 50% association/50% HX elimination when X = Cl. Reaction of Au(+)((3)D) with CH(3)F also results in HF elimination, which in this case is thought to produce (3)AuCH(2)(+). With CH(3)Cl, Au(+)((3)D) reacts to form AuCH(3)(+) and CH(3)Cl(+) in parallel steps. An additional product channel initiated by Au(+)((3)D) is also observed with both methyl halides, which yields CH(2)X(+) as a higher-order product. Kinetic measurements indicate that the reaction efficiency for both Au(+) states is significantly greater with CH(3)Cl than with CH(3)F. The observed two-body rate constant for depletion of Au(+)((1)S) by CH(3)F represents less than 5% of the limiting rate constant predicted by the average dipole orientation model (ADO) at room temperature and 226 K, whereas CH(3)Cl reacts with Au(+)((1)S) at the ADO limit at both room temperature and 218 K. Rate constants for depletion of Au(+)((3)D) by CH(3)F and CH(3)Cl were measured at 226 and 218 K respectively, and indicate that Au(+)((3)D) is consumed at approximately 2% of the ADO limit by CH(3)F and 69% of the ADO limit by CH(3)Cl. Product formation and overall efficiency for all four reactions are consistent with previous experimental results and available theoretical models.

Structures of M2(SO2)6B12F12 (M = Ag or K) and Ag2(H2O)4B12F12: Comparison of the Coordination of SO2 versus H2O and of B12F122- versus Other Weakly Coordinating Anions to Metal Ions in the Solid State.

PubMed

Malischewski, Moritz; Peryshkov, Dmitry V; Bukovsky, Eric V; Seppelt, Konrad; Strauss, Steven H

2016-12-05

The structures of three solvated monovalent cation salts of the superweak anion B 12 F 12 2- (Y 2- ), K 2 (SO 2 ) 6 Y, Ag 2 (SO 2 ) 6 Y, and Ag 2 (H 2 O) 4 Y, are reported and discussed with respect to previously reported structures of Ag + and K + with other weakly coordinating anions. The structures of K 2 (SO 2 ) 6 Y and Ag 2 (SO 2 ) 6 Y are isomorphous and are based on expanded cubic close-packed arrays of Y 2- anions with M(OSO) 6 + complexes centered in the trigonal holes of one expanded close-packed layer of B 12 centroids (⊙). The K + and Ag + ions have virtually identical bicapped trigonal prism MO 6 F 2 coordination spheres, with M-O distances of 2.735(1)-3.032(2) Å for the potassium salt and 2.526(5)-2.790(5) Å for the silver salt. Each M(OSO) 6 + complex is connected to three other cationic complexes through their six μ-SO 2 -κ 1 O,κ 2 O' ligands. The structure of Ag 2 (H 2 O) 4 Y is unique [different from that of K 2 (H 2 O) 4 Y]. Planes of close-packed arrays of anions are offset from neighboring planes along only one of the linear ⊙···⊙···⊙ directions of the close-packed arrays, with [Ag(μ-H 2 O) 2 Ag(μ-H 2 O) 2 )] ∞ infinite chains between the planes of anions. There are two nearly identical AgO 4 F 2 coordination spheres, with Ag-O distances of 2.371(5)-2.524(5) Å and Ag-F distances of 2.734(4)-2.751(4) Å. This is only the second structurally characterized compound with four H 2 O molecules coordinated to a Ag + ion in the solid state. Comparisons with crystalline H 2 O and SO 2 solvates of other Ag + and K + salts of weakly coordinating anions show that (i) N[(SO 2 ) 2 (1,2-C 6 H 4 )] - , BF 4 - , SbF 6 - , and Al(OC(CF 3 ) 3 ) 4 - coordinate much more strongly to Ag + than does Y 2- , (ii) SnF 6 2- coordinates somewhat more strongly to K + than does Y 2- , and (iii) B 12 Cl 12 2- coordinates to K + about the same as, if not slightly weaker than, Y 2- .

Stable Isotope Analysis of Chlorate

NASA Astrophysics Data System (ADS)

Brundrett, M.; Jackson, W. A.; Sturchio, N. C.; Bohlke, J. K.; Hatzinger, P.

2016-12-01

Studies have confirmed the presence of chlorate (ClO3-) throughout terrestrial and extraterrestrial systems generally in excess of perchlorate (ClO4-) [1, 2]. ClO3- occurrence, production, and post depositional transformation has significant implications to our understanding of atmospheric Cl cycling and potential biogeochemical reactions on Earth and Mars. The isotopic composition of oxyanions can be used to evaluate their production mechanisms and post-depositional alteration [3, 4]. However, no information is available on the natural isotopic composition of ClO3-. The objective of this study was to develop a method to measure the stable isotope composition (δ18O, δ17O and δ37Cl) of ClO3- and to determine the isotopic composition of ClO3- in natural desert salt accumulations that have been studied previously for NO3- and ClO4- isotopic composition. The process of ClO3- purification and analysis of δ18O, δ 17O and δ37Cl is problematic but has recently been resolved by adapting previously published methods for ClO4-. Competitive anions (e.g. NO3-, Cl-, ClO4-, and SO4-2) are removed through a series of processes including biological reduction, solid phase extraction, and anion or cation exchange. Initial results for control samples treated with the above method have a maximum variation of ± 2 ‰. These methods are being applied to representative samples to determine if various sources of natural and synthetic ClO3- have distinctive isotopic compositions, as reported previously for ClO4- [3, 4]. Establishing the range of isotopic composition of natural ClO3- also could provide information about atmospheric ClO3- production mechanisms and post-depositional processing, with implications for the atmospheric chemistry of oxychlorine compounds and the global biogeochemical cycling of Cl. [1] Jackson et al. (2015) EPSL 430, 470-476. [2] Rao et al. (2010) ES&T 44, 8429-8434. [3] Jackson et al. (2010) ES&T 44, 4869-4876. [4] Bao and Gu (2004) ES&T 38, 5073-5077.

A dosing algorithm for metformin based on the relationships between exposure and renal clearance of metformin in patients with varying degrees of kidney function.

PubMed

Duong, Janna K; Kroonen, M Y A M; Kumar, S S; Heerspink, H L; Kirkpatrick, C M; Graham, G G; Williams, K M; Day, R O

2017-08-01

The aims of this study were to investigate the relationship between metformin exposure, renal clearance (CL R ), and apparent non-renal clearance of metformin (CL NR /F) in patients with varying degrees of kidney function and to develop dosing recommendations. Plasma and urine samples were collected from three studies consisting of patients with varying degrees of kidney function (creatinine clearance, CL CR ; range, 14-112 mL/min). A population pharmacokinetic model was built (NONMEM) in which the oral availability (F) was fixed to 0.55 with an estimated inter-individual variability (IIV). Simulations were performed to estimate AUC 0-τ , CL R , and CL NR /F. The data (66 patients, 327 observations) were best described by a two-compartment model, and CL CR was a covariate for CL R . Mean CL R was 17 L/h (CV 22%) and mean CL NR /F was 1.6 L/h (69%).The median recovery of metformin in urine was 49% (range 19-75%) over a dosage interval. When CL R increased due to improved renal function, AUC 0-τ decreased proportionally, while CL NR /F did not change with kidney function. Target doses (mg/day) of metformin can be reached using CL CR /3 × 100 to obtain median AUC 0-12 of 18-26 mg/L/h for metformin IR and AUC 0-24 of 38-51 mg/L/h for metformin XR, with C max  < 5 mg/L. The proposed dosing algorithm can be used to dose metformin in patients with various degrees of kidney function to maintain consistent drug exposure. However, there is still marked IIV and therapeutic drug monitoring of metformin plasma concentrations is recommended.

Spermatozoa from the maned wolf (Chrysocyon brachyurus) display typical canid hyper-sensitivity to osmotic and freezing-induced injury, but respond favorably to dimethyl sulfoxide.

PubMed

Johnson, Amy E M; Freeman, Elizabeth W; Wildt, David E; Songsasen, Nucharin

2014-06-01

We assessed the influences of medium osmolality, cryoprotectant and cooling and warming rate on maned wolf (Chrysocyon brachyurus) spermatozoa. Ejaculates were exposed to Ham's F10 medium (isotonic control) or to this medium plus NaCl (350-1000mOsm), sucrose (369 and 479mOsm), 1M glycerol (1086mOsm) or dimethyl sulfoxide (Me2SO, 1151mOsm) for 10 min. Each sample then was diluted back into Ham's medium and assessed for sperm motility and plasma membrane integrity. Although glycerol and Me2SO had no influence (P>0.05), NaCl and sucrose solutions affected sperm motility (P<0.05), but not membrane integrity. Motility of sperm exposed to <600mOsm NaCl or sucrose was less (P<0.05) than fresh ejaculate, but comparable (P>0.05) to the control. As osmolality of the NaCl solution increased, motility decreased to <5%. In a separate study, ejaculates were diluted in Test Yolk Buffer containing 1M glycerol or Me2SO and cooled from 5°C to -120°C at -57.8°C, -124.2°C or -67.0°C/min, frozen in LN2, thawed in a water bath for 30s at 37°C or 10s at 50°C, and then assessed for motility, plasma- and acrosomal membrane integrity. Cryopreservation markedly (P<0.05) reduced sperm motility by 70% compared to fresh samples. Higher (P<0.05) post-thaw motility (20.0±1.9% versus 13.5±2.1%) and membrane integrity (51.2±1.7% versus 41.5±2.2%) were observed in samples cryopreserved in Me2SO than in glycerol. Cooling rates influenced survival of sperm cryopreserved in glycerol with -57.8°C/min being advantageous (P<0.05). The findings demonstrate that although maned wolf spermatozoa are similar to domestic dog sperm in their sensitivity to osmotic-induced motility damage, the plasma membranes tolerate dehydration, and the cells respond favorably to Me2SO as a cryoprotectant. Published by Elsevier Inc.

Pollution from the 2014-15 Bárðarbunga eruption monitored by snow cores from the Vatnajökull glacier, Iceland

NASA Astrophysics Data System (ADS)

Galeczka, Iwona; Eiriksdottir, Eydis Salome; Pálsson, Finnur; Oelkers, Eric; Lutz, Stefanie; Benning, Liane G.; Stefánsson, Andri; Kjartansdóttir, Ríkey; Gunnarsson-Robin, Jóhann; Ono, Shuhei; Ólafsdóttir, Rósa; Jónasdóttir, Elín Björk; Gislason, Sigurdur R.

2017-11-01

The chemical composition of Icelandic rain and snow is dominated by marine aerosols, however human and volcanic activity can also affect these compositions. The six month long 2014-15 Bárðarbunga volcanic eruption was the largest in Iceland for more than 200 years and it released into the atmosphere an average of 60 kt/day SO2, 30 kt/day CO2, 500 t/day HCl and 280 t/day HF. To study the effect of this eruption on the winter precipitation, snow cores were collected from the Vatnajökull glacier and the highlands northeast of the glacier. In addition to 29 bulk snow cores from that precipitated from September 2014 until March 2015, two cores were sampled in 21 and 44 increments to quantify the spatial and time evolution of the chemical composition of the snow. The pH and chemical compositions of melted snow samples indicate that snow has been affected by the volcanic gases emitted during the Bárðarbunga eruption. The pH of the melted bulk snow cores ranged from 4.41 to 5.64 with an average value of 5.01. This is four times greater H+ activity than pure water saturated with the atmospheric CO2. The highest concentrations of volatiles in the snow cores were found close to the eruption site as predicted from CALPUFF SO2 gas dispersion quality model. The anion concentrations (SO4, Cl, and F) were higher and the pH was lower compared to equivalent snow samples collected during 1997-2006 from the unpolluted Icelandic Langjökull glacier. Higher SO4 and Cl concentrations in the snow compared with the unpolluted rainwater of marine origin confirm the addition of a non-seawater SO4 and Cl. The δ34S isotopic composition confirms that the sulphur addition is of volcanic aerosol origin. The chemical evolution of the snow with depth reflects changes in the lava effusion and gas emission rates. Those rates were the highest at the early stage of the eruption. Snow that fell during that time, represented by samples from the deepest part of the snow cores, had the lowest pH and highest concentrations of SO4, F, Cl and metals, compared with snow that fell later in the winter. Also the Al concentration, did exceed World Health Organisation drinking water standard of 3.7 μmol/kg in the lower part of the snow core closest to the eruption site. Collected snow represents the precipitation that fell during the eruption period. Nevertheless, only minor environmental impacts are evident in the snow due to its interaction with the volcanic aerosol gases. In addition, the microbial communities identified in the snow that fell during the eruption were similar to those found in snow from other parts of the Arctic, confirming an insignificant impact of this eruption on the snow microecology.

SO2 absorption in EmimCl-TEG deep eutectic solvents.

PubMed

Yang, Dezhong; Zhang, Shaoze; Jiang, De-En; Dai, Sheng

2018-06-06

Deep eutectic solvents (DESs) based on 1-ethyl-3-methylimidazolium chloride (EmimCl) and triethylene glycol (TEG) with different molar ratios (from 6 : 1 to 1 : 1) were prepared. FTIR and theoretical calculation indicated that the C2-H on the imidazolium ring form hydrogen bonds with the hydroxyl group rather than the ether O atom of the TEG. The EmimCl-TEG DESs can efficiently capture SO2; in particular, EmimCl-TEG (6 : 1) can capture 0.54 g SO2 per gram of solvent at 0.10 atm and 20 °C, the highest absorption amount for DESs under the same conditions. Theoretical calculation showed that the high SO2 absorption capacity was mainly due to the strong charge-transfer interaction between SO2 and the anion Cl-. Moreover, SO2 desorption in the DESs can be controlled by tuning the interaction between EmimCl and TEG, and the DESs can be cycled many times.

Fluid-Evaporation Records Preserved in Meridiani Rocks

NASA Technical Reports Server (NTRS)

Rao, M. N.; Nyquist, Laurence E.; Sutton, S. R.

2009-01-01

We have shown earlier that the high SO3/Cl ratios found in secondary mineral assemblages in shergottite GRIM glasses (Gas-Rich Impact-Melt) likely resulted from interactions of regolith materials with sulfate-rich (and Cl-poor) solutions. The low SO3/Cl ratios determined in secondary salts in nakhalite fracture-fillings presumably formed by rock interactions with chloride-rich (and SO4-poor) solutions near Mars surface. The SO3 and Cl abundances determined by APXS in abraded rocks (RAT) from Endurance, Fram and Eagle craters indicate that these salt assemblages likely formed by evaporative concentration of brine fluids at Meridiani. The SO3/Cl ratios in the abraded rocks are examined here, instead of their absolute abundances, because the abundance ratios might provide better guide-lines for tracking the evolution of evaporating fluids at Meridiani. The SO3/Cl ratios in these samples, in turn, might provide clues for the mobile element ratios of the altering fluids that infiltrated into the Meridiani rocks.

Fluids on differentiated asteroids: Evidence from phosphates in differentiated meteorites GRA 06128 and GRA 06129

NASA Astrophysics Data System (ADS)

Shearer, Charles K.; Burger, Paul V.; Papike, James J.; Sharp, Zachary D.; McKeegan, Kevin D.

2011-09-01

Abstract- Paired meteorites Graves Nunatak 06128 and 06129 (GRA) represent an ancient cumulate lithology (4565.9 Ma ± 0.3) containing high abundances of sodic plagioclase. Textures and stable isotope compositions of GRA indicate that superimposed on the igneous lithology is a complex history of subsolidus reequilibration and low-temperature alteration that may have extended over a period of 150 Myr. In GRA, apatite is halogen-rich with Cl between 4.5 and 5.5 wt% and F between 0.3 and 0.9 wt%. The Cl/(Cl+F+OH) ratio of the apatite is between 0.65 and 0.82. The Cl and F are negatively correlated and are heterogeneously distributed in the apatite. Merrillite is low in halogens with substantial Na in the 6-fold coordinated Na-site (≈2.5%) and Mg in the smaller octahedral site. The merrillite has a negative Eu anomaly, whereas the apatite has a positive Eu anomaly. The chlorine isotope composition of the bulk GRA leachate is +1.2‰ relative to standard mean ocean chloride (SMOC). Ion microprobe chlorine isotope analyses of the apatite range between -0.5 and +1.2‰. Textural relationships between the merrillite and apatite, and the high-Cl content of the apatite, suggest that the merrillite is magmatic in origin, whereas the apatite is a product of the interaction between merrillite and a Cl-rich fluid. If the replacement of merrillite by apatite occurred at approximately 800 °C, the fluid composition is f(HCl)/f(H2O) = 0.0383 and a HCl molality of 2.13 and f(HCl)/f(HF) = 50-100. It is anticipated that the calculated f(HCl)/f(H2O) and a HCl molality are minimum values due to assumptions made on the OH component in apatite and basing the calculations on the apatite with the lowest XCl. The bulk δ37Cl of GRA is a >2σ outlier from chondritic meteorites and suggests that parent body processes resulted in fractionation of the Cl isotopes.

Origin, speciation, and fluxes of trace-element gases at Augustine volcano, Alaska: Insights into magma degassing and fumarolic processes

NASA Astrophysics Data System (ADS)

Symonds, Robert B.; Reed, Mark H.; Rose, William I.

1992-02-01

Thermochemical modeling predicts that trace elements in the Augustine gas are transported from near-surface magma as simple chloride (NaCl, KCl, FeCl 2, ZnCl 2, PbCl 2, CuCl, SbCl 3, LiCl, MnCl 2, NiCl 2, BiCl, SrCl 2), oxychloride (MoO 2Cl 2), sulfide (AsS), and elemental (Cd) gas species. However, Si, Ca, Al, Mg, Ti, V, and Cr are actually more concentrated in solids, beta-quartz (SiO 2), wollastonite (CaSiO 3), anorthite (CaAl 2Si 2O 8), diopside (CaMgSi 2O 6), sphene (CaTiSiO 5), V 2O 3(c), and Cr 2O 3(c), respectively, than in their most abundant gaseous species, SiF 4, CaCl 2, AlF 2O, MgCl 2 TiCl 4, VOCl 3, and CrO 2Cl 2. These computed solids are not degassing products, but reflect contaminants in our gas condensates or possible problems with our modeling due to "missing" gas species in the thermochemical data base. Using the calculated distribution of gas species and the COSPEC SO 2 fluxes, we have estimated the emission rates for many species (e.g., COS, NaCl, KCl, HBr, AsS, CuCl). Such forecasts could be useful to evaluate the effects of these trace species on atmospheric chemistry. Because of the high volatility of metal chlorides (e.g., FeCl 2, NaCl, KCl, MnCl 2, CuCl), the extremely HCl-rich Augustine volcanic gases are favorable for transporting metals from magma. Thermochemical modeling shows that equilibrium degassing of magma near 870°C can account for the concentrations of Fe, Na, K, Mn, Cu, Ni and part of the Mg in the gases escaping from the dome fumaroles on the 1986 lava dome. These calculations also explain why gases escaping from the lower temperature but highly oxidized moat vents on the 1976 lava dome should transport less Fe, Na, K, Mn and Ni, but more Cu; oxidation may also account for the larger concentrations of Zn and Mo in the moat gases. Nonvolatile elements (e.g., Al, Ca, Ti, Si) in the gas condensates came from eroded rock particles that dissolved in our samples or, for Si, from contamination from the silica sampling tube. Only a very small amount of rock contamination occurred (water/rock ratios between 10 4 and 10 6). Erosion is more prevalent in the pyroclastic flow fumaroles than in the summit vents, reflecting physical differences in the fumarole walls: ash vs. lava. Trace element contents of volcanic gases show enormous variability because of differences in the intensive parameters of degassing magma and variable amounts of wall rock erosion in volcanic fumaroles.

Hypotonic activation of short ClC3 isoform is modulated by direct interaction between its cytosolic C-terminal tail and subcortical actin filaments.

PubMed

McCloskey, Diana T; Doherty, Lynda; Dai, Yan-Ping; Miller, Lisa; Hume, Joseph R; Yamboliev, Ilia A

2007-06-08

Short ClC3 isoform (sClC3) functions as a volume-sensitive outwardly rectifying anion channel (VSOAC) in some cell types. In previous studies, we have shown that the hypotonic activation of sClC3 is linked to cell swelling-mediated remodeling of the actin cytoskeleton. In the present study, we have tested the hypothesis that the cytosolic tails of sClC3 bind to actin directly and that binding modulates the hypotonic activation of the channel. Co-sedimentation assays in vitro demonstrated a strong binding between the glutathione S-transferase-fused cytosolic C terminus of sClC3 (GST-sClC3-CT) to filamentous actin (F-actin) but not to globular monomeric actin (G-actin). The GST-fused N terminus (GST-sClC3-NT) exhibited low binding affinity to both G- and F-actin. Co-sedimentation experiments with progressively truncated GST-sClC3-CT indicated that the F-actin binding region is located between amino acids 690 and 760 of sClC3. Two synthetic peptides mapping basic clusters of the cytosolic sClC3-CT (CTP2, isoleucine 716 to leucine 734; and CTP3, proline 688 to proline 709) prevented binding of GST-sClC3-CT to F-actin in vitro. Dialysis into NIH/3T3 cells of these two peptides (but not of synthetic peptide CTP1 (isoleucine 737 to glutamine 748)) reduced the maximal current density by 60 and 38%, respectively. Based on these results, we have concluded that, by direct interaction with subcortical actin filaments, sClC3 contributes to the hypotonic stress-induced VSOACs in NIH/3T3 cells.

The Electrochemical Co-reduction of Mg-Al-Y Alloys in the LiCl-NaCl-MgCl2-AlF3-YCl3 Melts

NASA Astrophysics Data System (ADS)

Li, Mei; Liu, Yaochen; Han, Wei; Wang, Shanshan; Zhang, Milin; Yan, Yongde; Shi, Weiqun

2015-04-01

The electrochemical formation of Mg-Al-Y alloys was studied in the LiCl-NaCl-MgCl2 melts by the addition of AlF3 and YCl3 on a molybdenum electrode at 973 K (700 °C). In order to reduce the volatilization of salt solvent in the electrolysis process, the volatile loss of LiCl-NaCl-MgCl2 and LiCl-KCl-MgCl2 melts was first measured in the temperature range from 873 K to 1023 K (600 °C to 750 °C). Then, the electrochemical behaviors of Mg(II), Al(III), Y(III) ions and alloy formation processes were investigated by cyclic voltammetry, chronopotentiometry, and open circuit chronopotentiometry. The cyclic voltammograms indicate that the under-potential deposition of magnesium and yttrium on pre-deposited Al leads to formation of Mg-Al and Al-Y intermetallic compounds. The Mg-Al-Y alloys were prepared by galvanostatic electrolysis in the LiCl-NaCl-MgCl2-AlF3-YCl3 melts and characterized by X-ray diffraction and scanning electron microscopy with energy dispersive spectrometry. Composition of the alloys was analyzed by inductively coupled plasma-atomic emission spectrometer, and current efficiency was also determined by the alloy composition.

An alkaline tin(II) halide compound Na{sub 3}Sn{sub 2}F{sub 6}Cl: Synthesis, structure, and characterization

DOE Office of Scientific and Technical Information (OSTI.GOV)

Gong, Pifu; University of the Chinese Academy of Sciences, Beijing 100049; Luo, Siyang

A new alkali tin(II) halide compound, Na{sub 3}Sn{sub 2}F{sub 6}Cl, is synthesized by hydrothermal method. This compound crystallizes trigonally in space group of R-3c (167), and processes a zero-dimensional (0D) structure consisted of Na{sup +} cations, Cl{sup −} anions and the isolated [SnF{sub 3}]{sup -} trigonal pyramids in which the stereochemically active 5s{sup 2} lone pair electrons are attached to the Sn{sup 2+} cations. Interestingly, the [SnF{sub 3}]{sup −} trigonal pyramids are parallel arranged in the a-b plane, while oppositely arranged in line with rotation along the c- axis. Moreover, the energy bandgap, thermal stability and electronic structure of Na{submore » 3}Sn{sub 2}F{sub 6}Cl are characterized and the results reveal that this compound has and indirect bandgap of 3.88 eV and is stable under 270 °C. - Graphical abstract: A zero-dimensional alkaline tin halide compound, Na{sub 3}Sn{sub 2}F{sub 6}Cl, is synthesized by hydrothermal method. Interestingly, both the anions and cations coordinating polyhedra exhibit order arranged with the [SnF{sub 3}]{sup -} trigonal pyramids rotating along the c- axis.« less

Excess heat capacity and entropy of mixing along the chlorapatite-fluorapatite binary join

NASA Astrophysics Data System (ADS)

Dachs, Edgar; Harlov, Daniel; Benisek, Artur

2010-10-01

The heat capacity at constant pressure, C p, of chlorapatite [Ca5(PO4)3Cl - ClAp], and fluorapatite [Ca5(PO4)3F - FAp], as well as of 12 compositions along the chlorapatite-fluorapatite join have been measured using relaxation calorimetry [heat capacity option of the physical properties measurement system (PPMS)] and differential scanning calorimetry (DSC) in the temperature range 5-764 K. The chlor-fluorapatites were synthesized at 1,375-1,220°C from Ca3(PO4)2 using the CaF2-CaCl2 flux method. Most of the chlor-fluorapatite compositions could be measured directly as single crystals using the PPMS such that they were attached to the sample platform of the calorimeter by a crystal face. However, the crystals were too small for the crystal face to be polished. In such cases, where the sample coupling was not optimal, an empirical procedure was developed to smoothly connect the PPMS to the DSC heat capacities around ambient T. The heat capacity of the end-members above 298 K can be represented by the polynomials: C {p/ClAp} = 613.21 - 2,313.90 T -0.5 - 1.87964 × 107 T -2 + 2.79925 × 109 T -3 and C {p/FAp} = 681.24 - 4,621.73 × T -0.5 - 6.38134 × 106 T -2 + 7.38088 × 108 T -3 (units, J mol-1 K-1). Their standard third-law entropy, derived from the low-temperature heat capacity measurements, is S° = 400.6 ± 1.6 J mol-1 K-1 for chlorapatite and S° = 383.2 ± 1.5 J mol-1 K-1 for fluorapatite. Positive excess heat capacities of mixing, Δ C {p/ex}, occur in the chlorapatite-fluorapatite solid solution around 80 K (and to a lesser degree at 200 K) and are asymmetrically distributed over the join reaching a maximum of 1.3 ± 0.3 J mol-1 K-1 for F-rich compositions. They are significant at these conditions exceeding the 2 σ-uncertainty of the data. The excess entropy of mixing, Δ S ex, at 298 K reaches positive values of 3-4 J mol-1 K-1 in the F-rich portion of the binary, is, however, not significantly different from zero across the join within its 2 σ-uncertainty.

The speciation and transport of palladium in hydrothermal fluids: Experimental modeling and thermodynamic constraints

NASA Astrophysics Data System (ADS)

Tagirov, Boris R.; Baranova, Nina N.; Zotov, Alexandr V.; Akinfiev, Nikolay N.; Polotnyanko, Natalya A.; Shikina, Nadezhda D.; Koroleva, Lyudmila A.; Shvarov, Yuri V.; Bastrakov, Evgeniy N.

2013-09-01

The solubility of PdO(cr) was measured in NaOH (to 0.1m, mol/kg H2O) solutions at 400 °C, 1 kbar, and the solubility of Pd(cr) was determined at 400-500 °C, 1 kbar in acidic chloride solutions (to 1.5m NaCl) buffered with respect to hydrogen. The Pd electrode potential Eo(PdCl42-)/Pd for the reaction PdCl42- + 2e- = Pd(cr) + 4 Cl- was determined at 50 and 70 °C in 1m chloride solutions. These data, together with reliable literature values, were used for calculation of the standard thermodynamic properties and the formation constants for Pd-OH, Pd-Cl, and Pd-S-HS complexes within the framework of the revised Helgeson-Kirkham-Flowers model. It was found that PdCl3- and PdCl42- become the most important Pd complexes in high temperature (t > 300 °C), chloride-rich fluids, and PdCl42- predominates at m(Cl) > 0.1. The stability of Pd-Cl complexes increases sharply with increase in temperature. The near-neutral chloride-sulfide solutions (1m NaCl, <0.1m Stot) can transport Pd at ppm concentration levels at t ⩾ 600 °C, whereas decrease in temperature and increase in pH can lead to effective deposition of Pd minerals. The stability of Pd-S-HS complexes (Pd(°, Pd(HS)3- and PdS(HS)2-) decreases with increase in temperature. Therefore, the role of these complexes in hydrothermal transport of palladium is restricted to the low temperature solutions (t < 100 °C) and sulfur can be considered an efficient depositing agent for Pd. The calculated HKF Equation of State parameters were used to predict thermodynamic properties of Pd2+, Pd-OH, Pd-Cl, and Pd-S-HS complexes to 700 °C, 2 kbar. These parameters are incorporated into the FreeGs web-enabled database (http://www-b.ga.gov.au/minerals/research/methodology/geofluids/thermo/calculator/search.jsp) that can be used for geochemical application of thermodynamic data obtained in the present study.

Site selectivity on chalcogen atoms in superconducting La(O,F)BiSSe

DOE Office of Scientific and Technical Information (OSTI.GOV)

Tanaka, Masashi, E-mail: Tanaka.Masashi@nims.go.jp; Matsushita, Yoshitaka; Fujioka, Masaya

2015-03-16

Single crystals of La(O,F)BiSSe were grown by using a CsCl flux method. Single crystal X-ray structural analysis reveals that the crystal structure is isostructural to the BiS{sub 2}- or BiSe{sub 2}-based compounds crystallizing with space group P4/nmm (lattice parameters a = 4.1110(2) Å, c = 13.6010(7) Å). However, the S atoms are selectively occupied at the apical site of the Bi-SSe pyramids in the superconducting layer. The single crystals show a superconducting transition at around 4.2 K in the magnetic susceptibility and resistivity measurements. The superconducting anisotropic parameter is determined to be 34–35 from its upper critical magnetic field. The anisotropy is in the same range withmore » that of other members of the La(O,F)BiCh{sub 2} (Ch = S, Se) family under ambient pressure.« less

Impact of urbanization on the ecology of Mukuvisi River, Harare, Zimbabwe

NASA Astrophysics Data System (ADS)

Moyo, N. A. G.; Rapatsa, M. M.

2016-04-01

The main objective in this study was to compare the physico-chemical characteristics and biota of a river (Mukuvisi) passing through an urban area to that of a non-urbanised river (Gwebi). Five sites in the Mukuvisi River and five sites in the Gwebi River were sampled for water physico-chemical parameters (pH, conductivity, DO, BOD, TDS, ammonia, Cl, SO42-, PO42-, NO33-, F-, Pb, Cu, Fe, Mn, Zn and Cr) once every month between August, 2012-August, 2013. Cluster analysis based on the physico-chemical parameters grouped the sites into two groups. Mukuvisi River sites formed their own grouping except for one site which was grouped with Gwebi River sites. Principal Component Analysis (PCA) was used to extract the physico-chemical parameters that account for most variations in water quality in the Mukuvisi and Gwebi Rivers. PCA identified sulphate, chloride, fluoride, iron, manganese and zinc as the major factors contributing to the variability of Mukuvisi River water quality. In the Gwebi river, sulphate, nitrate, fluoride and copper accounted for most of the variation in water quality. Canonical Correspondence Analysis (CCA) was used to explore the relationship between physico-chemical parameters and macroinvertebrate communities. CCA plots in both Mukuvisi and Gwebi Rivers showed significant relationships between macroinvertebrate communities and water quality variables. Phosphate, ammonia and nitrates were correlated with Chironomidae and Simulidae. Gwebi River had higher (P < 0.05, ANOVA) macroinvertebrates and fish diversity than Mukuvisi River. Clarias gariepinus from the Mukuvisi River had high liver histological lesions and low AChE activity and this led to lower growth rates in this river.

Functional anion concept: effect of fluorine anion on hydrogen storage of sodium alanate.

PubMed

Yin, Li-Chang; Wang, Ping; Kang, Xiang-Dong; Sun, Cheng-Hua; Cheng, Hui-Ming

2007-03-28

Doping NaAlH(4) with Ti-catalyst has produced a promising hydrogen storage system that can be reversibly operated at moderate temperature conditions. Of the various dopant precursors, TiCl(3) was well recognized due to its pronounced catalytic effect on the reversible dehydrogenation processes of sodium aluminium hydrides. Quite recently we experimentally found that TiF(3) was even better than TiCl(3) in terms of the critical hydrogen storage properties of the doped hydrides, in particular the dehydriding performance at Na(3)AlH(6)/NaH + Al step at moderate temperature. We present here the DFT calculation results of the TiF(3) or TiCl(3) doped Na(3)AlH(6). Our computational studies have demonstrated that F(-) and Cl(-) anions differ substantially from each other with regard to the state and function in the doped sodium aluminium hydride. In great contrast to the case of chloride doping where Cl(-) anion constitutes the "dead weight" NaCl, the fluoride doping results in a substitution of H(-) by F(-) anion in the hydride lattice and accordingly, a favorable thermodynamics adjustment. These results well explain the observed dehydriding performance associated with TiF(3)/TiCl(3)-doping. More significantly, the coupled computational and experimental efforts allow us to put forward a "functional anion" concept. This renews the current mechanism understanding in the catalytically enhanced sodium alanate.

Passivation effect of Cl, F and H atoms on CuIn0.75Ga0.25Se2 (1 1 2) surface

NASA Astrophysics Data System (ADS)

Qi, Rong-fei; Wang, Zhao-hui; Tang, Fu-ling; Agbonkina, Itohan C.; Xue, Hong-tao; Si, Feng-juan; Ma, Sheng-ling; Wang, Xiao-ka

2018-06-01

Using the first-principles calculations within the density functional-theory (DFT) framework, we theoretically investigated the surface reconstruction, surface states near the Fermi level and their passivation on CuIn0.75Ga0.25Se2 (1 1 2) (CIGS) surface by chlorine, fluorine and hydrogen. Surface reconstruction appears on CIG-terminated CIGS (1 1 2) surface and it is a self-passivation. For the locations of Cl, F and H atoms adsorbing on Se-terminated CIGS (1 1 2) surface, four high symmetry adsorption sites: top sites, bridge sites, hexagonal close-packed (hcp) sites and faced centered cubic (fcc) sites were studied respectively. With the coverage of 0.5 monolayer (ML), Cl, F and H adatoms energetically occupy the top sites on the CIGS (112) surface. The corresponding adsorption energies were -2.20 eV, -3.29 eV, -2.60 eV, respectively. The bond length and electronic properties were analyzed. We found that the surface state density near the Fermi level was markedly diminished for 0.5 ML Cl, F and H adsorption on Se-terminated CIGS (1 1 2) surface at top sites. It was also found that H can more efficiently passivate the surface state density than Cl and F atoms, and the effect of adsorption of Cl atoms is better than that of F.

REE speciation in low-temperature acidic waters and the competitive effects of aluminum

USGS Publications Warehouse

Gimeno, Serrano M.J.; Auque, Sanz L.F.; Nordstrom, D. Kirk

2000-01-01

The effect of simultaneous competitive speciation of dissolved rare earth elements (REEs) in acidic waters (pH 3.3 to 5.2) has been evaluated by applying the PHREEQE code to the speciation of water analyses from Spain, Brazil, USA, and Canada. The main ions that might affect REE are Al3+, F-, SO42-, and PO43-. Fluoride, normally a significant complexer of REEs, is strongly associated with Al3+ in acid waters and consequently has little influence on REEs. The inclusion of aluminum concentrations in speciation calculations for acidic waters is essential for reliable speciation of REEs. Phosphate concentrations are too low (10-4 to 10-7 m) to affect REE speciation. Consequently, SO42- is the only important complexing ligand for REEs under these conditions. According to Millero [Millero, F.J., 1992. Stability constants for the formation of rare earth inorganic complexes as a function of ionic strength. Geochim. Cosmochim. Acta, 56, 3123-3132], the lanthanide sulfate stability constants are nearly constant with increasing atomic number so that no REE fractionation would be anticipated from aqueous complexation in acidic waters. Hence, REE enrichments or depletions must arise from mass transfer reactions. (C) 2000 Elsevier Science B.V. All rights reserved.

Modification of the Selectivity Properties of Tubular Ceramic Membranes after Alkaline Treatment

PubMed Central

Dutournié, Patrick; Limousy, Lionel; Anquetil, Jérôme

2017-01-01

This work focuses on the selectivity modification of ceramic membranes after a mild alkaline treatment. Filtration of pure salt-water solutions was carried out with commercial titania membranes before and after the treatment. After treatment, the rejection of NaF significantly decreased, while the rejection of NaCl and NaBr increased. Additionally, NaI and Na2SO4 remained close to zero. Pore size and electrical charge being almost unchanged, only significant modifications in the dielectric effects can explain this modification of selectivity. Therefore, the surface chemistry and the interaction (nature and magnitude) with the solvent and with the species present in the solution appear to be modified by the alkaline treatment. This trend is also illustrated by discussing the electric and the dielectric properties that were numerically identified before and after treatment. The alkaline treatment significantly decreased the apparent dielectric constant of NaCl-water solution in the pore, highlighting the rejection of sodium chloride. Contrariwise, the modification of the surface chemistry increased the apparent dielectric constant of NaF-water solution by promoting fluoride transmission. PMID:29160802

Quantitative fetal fibronectin and cervical length in symptomatic women: results from a prospective blinded cohort study.

PubMed

Levine, Lisa D; Downes, Katheryne L; Romero, Julie A; Pappas, Hope; Elovitz, Michal A

2018-05-15

Our objectives were to determine whether quantitative fetal fibronectin (fFN) and cervical length (CL) screening can be used alone or in combination as prognostic tests to identify symptomatic women at the highest or lowest risk for spontaneous preterm birth (sPTB). A prospective, blinded cohort study of women presenting with a singleton gestation to our triage unit between 22-33w6d with preterm labor symptoms was performed. Women with ruptured membranes, moderate/severe bleeding, and dilation >2 cm were excluded. The primary outcome was sPTB <37 weeks. We evaluated test characteristics of quantitative fFN and CL assessment, both separately and in combination, considering traditionally reported cut-points (fFN ≥50 and CL <25), as well as cut-points above and below these measures. We found interactions between fFN >50 and CL <25 and sPTB by parity and obstetric history (p < .05) and therefore stratified results. Test characteristics are presented with positive predictive value (PPV) and negative predictive value (NPV). Five hundred eighty women were enrolled and 537 women were available for analysis. Overall sPTB rate was 11.1%. Among nulliparous women, increasing levels of fFN were associated with increasing risk of sPTB, with PPV going from 26.5% at ≥20 ng/mL to 44.4% at ≥200 ng/mL. A cut-point of 20 ng/mL had higher sensitivity (69.2%) and higher NPV (96.8%) and therefore identified a "low-risk" group. fFN was not informative for multiparous women regardless of prior obstetrical history or quantitative level chosen. For all women, a shorter CL was associated with an increased sPTB risk. Among nulliparas and multiparas without a prior sPTB, a CL <20 mm optimized test characteristics (PPV 25 and 20%, NPV 95.5, and 92.7%, respectively). For multiparas with a prior sPTB, CL <25 mm was more useful. Using fFN and CL in combination for nulliparas did not improve test characteristics over using the individual fFN (p = .74) and CL (p = .31) components separately. This study identifies the importance of stratifying by parity and obstetrical history when using screening modalities for risk assessment in symptomatic women. For nulliparous women, either quantitative fFN or cervical length assessment can be utilized, depending on resources available, but a lower cut-point of 20 ng/mL should be used for quantitative fFN. For multiparous women, fFN is not useful and cervical length assessment should be the main screening tool utilized when there is clinical uncertainty. Regardless of parity, the PPV of fFN and CL is low and therefore the greatest clinical utility remains in its NPV.

Two Small Molecules Restore Stability to a Subpopulation of the Cystic Fibrosis Transmembrane Conductance Regulator with the Predominant Disease-causing Mutation.

PubMed

Meng, Xin; Wang, Yiting; Wang, Xiaomeng; Wrennall, Joe A; Rimington, Tracy L; Li, Hongyu; Cai, Zhiwei; Ford, Robert C; Sheppard, David N

2017-03-03

Cystic fibrosis (CF) is caused by mutations that disrupt the plasma membrane expression, stability, and function of the cystic fibrosis transmembrane conductance regulator (CFTR) Cl - channel. Two small molecules, the CFTR corrector lumacaftor and the potentiator ivacaftor, are now used clinically to treat CF, although some studies suggest that they have counteracting effects on CFTR stability. Here, we investigated the impact of these compounds on the instability of F508del-CFTR, the most common CF mutation. To study individual CFTR Cl - channels, we performed single-channel recording, whereas to assess entire CFTR populations, we used purified CFTR proteins and macroscopic CFTR Cl - currents. At 37 °C, low temperature-rescued F508del-CFTR more rapidly lost function in cell-free membrane patches and showed altered channel gating and current flow through open channels. Compared with purified wild-type CFTR, the full-length F508del-CFTR was about 10 °C less thermostable. Lumacaftor partially stabilized purified full-length F508del-CFTR and slightly delayed deactivation of individual F508del-CFTR Cl - channels. By contrast, ivacaftor further destabilized full-length F508del-CFTR and accelerated channel deactivation. Chronic (prolonged) co-incubation of F508del-CFTR-expressing cells with lumacaftor and ivacaftor deactivated macroscopic F508del-CFTR Cl - currents. However, at the single-channel level, chronic co-incubation greatly increased F508del-CFTR channel activity and temporal stability in most, but not all, cell-free membrane patches. We conclude that chronic lumacaftor and ivacaftor co-treatment restores stability in a small subpopulation of F508del-CFTR Cl - channels but that the majority remain destabilized. A fuller understanding of these effects and the characterization of the small F508del-CFTR subpopulation might be crucial for CF therapy development. © 2017 by The American Society for Biochemistry and Molecular Biology, Inc.

A multimodal histamine ligand for chromatographic purification of plasmid DNA.

PubMed

Černigoj, Urh; Vidic, Urška; Barut, Miloš; Podgornik, Aleš; Peterka, Matjaž; Štrancar, Aleš

2013-03-15

To exploit different chromatographic modes for efficient plasmid DNA (pDNA) purification a novel monolithic chromatographic support bearing multimodal histamine (HISA) groups was developed and characterized. Electrostatic charge of HISA groups depends on the pH of the mobile phase, being neutral above pH 7 and becoming positively charged below. As a consequence, HISA groups exhibit predominantly ion-exchange character at low pH values, which decreases with titration of the HISA groups resulting in increased hydrophobicity. This feature enabled separation of supercoiled (sc) pDNA from other plasmid isoforms (and other process related impurities) by adjusting salt or pH gradient. The dynamic binding capacity (DBC) for a 5.1kbp large plasmid at pH 5 was 4.0 mg/ml under low salt binding conditions, remaining relatively high (3.0 mg/ml) even in the presence of 1.0 M NaCl due to the multimodal nature of HISA ligand. Only slightly lower DBC (2.7 mg/ml) was determined under preferentially hydrophobic conditions in 3.0 M (NH(4))(2)SO(4), pH 7.4. Open circular and sc pDNA isoforms were baseline separated in descending (NH(4))(2)SO(4) gradient. Furthermore, an efficient plasmid DNA separation was possible both on analytical as well as on preparative scale by applying the descending pH gradient at a constant concentration (above 3.0 M) of (NH(4))(2)SO(4). Copyright © 2013 Elsevier B.V. All rights reserved.

Pentacoordinate silicon(IV): cationic, anionic and neutral complexes derived from the reaction of NHC→SiCl4 with highly Lewis acidic (C2F5)2SiH2.

PubMed

Böttcher, T; Steinhauer, S; Neumann, B; Stammler, H-G; Röschenthaler, G-V; Hoge, B

2014-06-14

Addition of NHC→SiCl4 to the highly Lewis acidic bis(pentafluoroethyl)silane ((C2F5)2SiH2) afforded the salt [(NHC)2SiCl2H][(C2F5)2SiCl3] with pentacoordinate silicon in the cation and the anion. The anion represents the first example of a chlorosilicate structurally characterized in the solid state. In this reaction, the long sought pentacoordinate NHC-adduct of silicochloroform was identified as an intermediate and its crystal structure is presented.

Isotope characterisation of deep aquifers in the Gwda catchment, northern Poland

NASA Astrophysics Data System (ADS)

Kotowski, Tomasz; Satora, Stefan

2016-06-01

We present the results of isotope measurements (δ18O, δ D, δ13CDIC and 14C) and chemical analyses (TDS, TOC, HCO3-, SO42-, Cl-, NO3-, NH4+, Ca2+, Mg2+ Na+ and K+) conducted on groundwater samples collected from deep Cenozoic aquifers. These aquifers are the basic source of drinking water at numerous localities within the study area in northern Poland. Most of the δ18O determinations are characterised by low variability (i.e., > 70 per cent of δ18O are between -9.5‰ and -9.2‰). In most cases tritium activity was not detected or its content slightly exceeded the uncertainty of measurement (from ±0.3 T.U. to ± 0.5 T.U.). On average, 14C activity is twice higher than that under similar conditions and in hydrogeological systems. The δ13CDIC values fall within the -13.6‰ to -12.8‰ range. A slight variability is observed when considering all isotope and chemical data within the study area and under these hydrogeological conditions. In general, the results of isotope and chemical analyses seem to be homogeneous, indicating the presence of closely similar groundwaters in the system, irrespective of geological formation. It is likely that there is a significant hydraulic connection between shallow and deep aquifers in the Gwda catchment, which indicates the potential for seepage of pollutants from shallow Pleistocene to deep Miocene aquifers. This can endanger the latter by e.g., high concentrations of NO3-, SO42- and Cl- ions from shallow aquifers within the Gwda catchment.

Changing fluxes of carbon and other solutes from the Mekong River.

PubMed

Li, Siyue; Bush, Richard T

2015-11-02

Rivers are an important aquatic conduit that connects terrestrial sources of dissolved inorganic carbon (DIC) and other elements with oceanic reservoirs. The Mekong River, one of the world's largest rivers, is firstly examined to explore inter-annual fluxes of dissolved and particulate constituents during 1923-2011 and their associated natural or anthropogenic controls. Over this period, inter-annual fluxes of dissolved and particulate constituents decrease, while anthropogenic activities have doubled the relative abundance of SO4(2-), Cl(-) and Na(+). The estimated fluxes of solutes from the Mekong decrease as follows (Mt/y): TDS (40.4) > HCO3(-) (23.4) > Ca(2+) (6.4) > SO4(2-) (3.8) > Cl(-) (1.74)~Na(+) (1.7) ~ Si (1.67) > Mg(2+) (1.2) > K(+ 0.5). The runoff, land cover and lithological composition significantly contribute to dissolved and particulate yields globally. HCO3(-) and TDS yields are readily predicted by runoff and percent of carbonate, while TSS yield by runoff and population density. The Himalayan Rivers, including the Mekong, are a disproportionally high contributor to global riverine carbon and other solute budgets, and are of course underlined. The estimated global riverine HCO3(-) flux (Himalayan Rivers included) is 34,014 × 10(9) mol/y (0.41 Pg C/y), 3915 Mt/y for solute load, including HCO3(-), and 13,553 Mt/y for TSS. Thereby this study illustrates the importance of riverine solute delivery in global carbon cycling.

Water-soluble ions in atmospheric aerosols measured in five sites in the Yangtze River Delta, China: Size-fractionated, seasonal variations and sources

NASA Astrophysics Data System (ADS)

Wang, Honglei; Zhu, Bin; Shen, Lijuan; Xu, Honghui; An, Junlin; Xue, Guoqiang; Cao, Jinfei

2015-12-01

In order to investigate the regional variations of water-soluble ions (WSIs), size-resolved measurement of aerosol particles and WSIs was conducted by using Anderson Sampler and Ion Chromatography at five sites (Nanjing, Suzhou, Lin'an, Hangzhou and Ningbo) in the Yangtze River Delta (YRD) region, China in the Autumn of 2012 and Winter, Spring and Summer of 2013. WSIs exhibited obvious seasonal variations due to the monsoon conversion, with the highest level in winter and lowest level in summer. The aerosol mass concentrations and WSIs in different size segments varied with four seasons. The dominant ions concentrations in PM2.1 ranked in the order of SO42- > NO3- > NH4+ > Cl- > K+ > Ca2+, and the dominant ions concentrations in PM2.1-10 ranked in the order of Ca2+ > NO3- > SO42- > Cl- > NH4+ > Na+. The size spectra of mass and WSIs concentration peaked mostly at 0.43-0.65 μm in four seasons. The concentration discrepancies of WSIs in different cities were caused by the geographic locations and emission source. It's belonged to ammonium-rich distribution in PM2.1 and ammonium-poor distribution in PM2.1-10 in the YRD region. The impact of temperature on mass concentrations of NO3- and NH4+ in PM2.1 were stronger than those in PM2.1-10. PCA analysis shows that the sources of WSIs dominant by anthropogenic sources, soil particles or falling dust, sea salt and burning process.

Chemical and Sr isotopic characteristics of rainwater on the Alxa Desert Plateau, North China: Implication for air quality and ion sources

NASA Astrophysics Data System (ADS)

Rao, Wenbo; Han, Guilin; Tan, Hongbing; Jin, Ke; Wang, Shuai; Chen, Tangqing

2017-09-01

The major ions and Sr isotopes in rainwater have been studied during 2013-2015 on the Alxa Desert Plateau in order to identify the source of rainwater chemistry and to assess air quality in the desert area of northern China. The pH and EC values of rainwater vary from 6.7 to 8.1 and from 35 to 1237 μS cm- 1, respectively, at the two meteorological stations (AYQ and YBL) in the Alxa Desert Plateau. Ca2 +, SO42 -, Na+ and Cl- are the dominant ions in rainwater, possessing > 85% of total ions. The mean daily wet deposition fluxes of soluble ions are 8709 μeq/m2/d at YBL and 5459 μeq/m2/d at AYQ, approaching the values at Xi'an, Beijing, Guangzhou, and Chengdu. Statistical analysis shows that SO42 - and NO3- in rainwater were mainly from anthropogenic sources while Ca2 + and K+ originated from terrestrial sources. Cl- was mainly from seawater sources, and Na+ was partly from mineral weathering. Major ions are well correlated with each other in rainwater, revealing that substances of various origins were synchronously carried into the atmosphere by wind. By using Sr isotope techniques, three main end-members controlling base cations of rainwater are identified: silicates, carbonates and seawater. Based on the analyses of acid-soluble fractions of desert soils, local soil dust could be the most important source of base cations in rainwater whereas the effect of the anthropogenic sources could be neglected.

Semiconducting perovskites (2-XC6H4C2H4NH3)2SnI4 (X = F, Cl, Br): steric interaction between the organic and inorganic layers.

PubMed

Xu, Zhengtao; Mitzi, David B; Dimitrakopoulos, Christos D; Maxcy, Karen R

2003-03-24

Two new semiconducting hybrid perovskites based on 2-substituted phenethylammonium cations, (2-XC(6)H(4)C(2)H(4)NH(3))(2)SnI(4) (X = Br, Cl), are characterized and compared with the previously reported X = F compound, with a focus on the steric interaction between the organic and inorganic components. The crystal structure of (2-ClC(6)H(4)C(2)H(4)NH(3))(2)SnI(4) is solved in a disordered subcell [C2/m, a = 33.781(7) A, b = 6.178(1) A, c = 6.190(1) A, beta = 90.42(3)(o), and Z = 2]. The structure is similar to the known (2-FC(6)H(4)C(2)H(4)NH(3))(2)SnI(4) structure with regard to both the conformation of the organic cations and the bonding features of the inorganic sheet. The (2-BrC(6)H(4)C(2)H(4)NH(3))(2)SnI(4) system adopts a fully ordered monoclinic cell [P2(1)/c, a = 18.540(2) A, b = 8.3443(7) A, c = 8.7795(7) A, beta = 93.039(1)(o), and Z = 2]. The organic cation adopts the anti conformation, instead of the gauche conformation observed in the X = F and Cl compounds, apparently because of the need to accommodate the additional volume of the bromo group. The steric effect of the bromo group also impacts the perovskite sheet, causing notable distortions, such as a compressed Sn-I-Sn bond angle (148.7(o), as compared with the average values of 153.3 and 154.8(o) for the fluoro and chloro compounds, respectively). The optical absorption features a substantial blue shift (lowest exciton peak: 557 nm, 2.23 eV) relative to the spectra of the fluoro and chloro compounds (588 and 586 nm, respectively). Also presented are transport properties for thin-film field-effect transistors (TFTs) based on spin-coated films of the two hybrid semiconductors.

Degradation of Alzheimer's amyloid fibrils by microglia requires delivery of ClC-7 to lysosomes

PubMed Central

Majumdar, Amitabha; Capetillo-Zarate, Estibaliz; Cruz, Dana; Gouras, Gunnar K.; Maxfield, Frederick R.

2011-01-01

Incomplete lysosomal acidification in microglia inhibits the degradation of fibrillar forms of Alzheimer's amyloid β peptide (fAβ). Here we show that in primary microglia a chloride transporter, ClC-7, is not delivered efficiently to lysosomes, causing incomplete lysosomal acidification. ClC-7 protein is synthesized by microglia but it is mistargeted and appears to be degraded by an endoplasmic reticulum–associated degradation pathway. Activation of microglia with macrophage colony-stimulating factor induces trafficking of ClC-7 to lysosomes, leading to lysosomal acidification and increased fAβ degradation. ClC-7 associates with another protein, Ostm1, which plays an important role in its correct lysosomal targeting. Expression of both ClC-7 and Ostm1 is increased in activated microglia, which can account for the increased delivery of ClC-7 to lysosomes. Our findings suggest a novel mechanism of lysosomal pH regulation in activated microglia that is required for fAβ degradation. PMID:21441306

Chlorinated hydrocarbon contaminants and metabolites in polar bears (Ursus maritimus) from Alaska, Canada, East Greenland, and Svalbard: 1996-2002.

PubMed

Verreault, Jonathan; Muir, Derek C G; Norstrom, Ross J; Stirling, Ian; Fisk, Aaron T; Gabrielsen, Geir W; Derocher, Andrew E; Evans, Thomas J; Dietz, Rune; Sonne, Christian; Sandala, Gregory M; Gebbink, Wouter; Riget, Frank F; Born, Erik W; Taylor, Mitch K; Nagy, John; Letcher, Robert J

2005-12-01

A suite of chlorinated hydrocarbon contaminants (CHCs) including organochlorine pesticides (OCPs) and by-products, polychlorinated biphenyls (PCBs), and methyl sulfone (MeSO2) PCB and p,p'-dichlorodiphenyldichloroethylene (p,p'-DDE) metabolites were determined in adipose tissue of 107 adult and sub-adult polar bears, almost exclusively females, sampled between 1996 and 2002 from populations spanning Arctic and Subarctic regions of Alaska, Canada, East Greenland, and Svalbard. The East Greenland and Svalbard populations of polar bears were distinguished by higher proportions of dichlorodiphenyldichloroethane (DDT)-related compounds, nonachlors, oxychlordane, and higher-chlorinated and persistent PCB congeners (hepta- to nona-chlorinated). Conversely, Alaska, the westernmost population of the North American Arctic, was characterized by higher proportions of relatively volatile compounds such as hexachlorocyclohexanes (HCHs) and pentachlorobenzene (PnCBz), lower-chlorinated PCB congeners (tri- to penta-chlorinated), and lower proportions of oxychlordane. Geometric mean (GM) with 95% confidence limits (CL) SigmaHCH concentrations were highest in Alaska male polar bear fat samples (GM 593; CL 363-909 ng g-1 lipid weight), SigmaDDT concentration were highest in East Greenland female samples (GM 309; CL 249-490 ng g-1 l.w.), and Sigma42PCB (GM 5972; CL 4637-9129 ng g-1 l.w.) and SigmaMeSO2-PCB (GM 198; CL 162-279 ng g-1 l.w.) concentrations were highest in female samples collected from Svalbard. The distribution of Sigma-chlordane-related compounds (SigmaCHL), SigmaCBz, mirex, and dieldrin was relatively uniform among the populations of polar bears investigated. The present 1996-2002 data of female polar bear fat samples was compared to spatial assessments of female polar bear fat samples collected between 1989 and 1993 from comparable populations. The two-point temporal comparisons showed a general decrease for age-adjusted mean concentrations of SigmaCHL, p,p'-DDE, Sigma42PCB, SigmaMeSO2-PCB and 3-MeSO2-p,p'-DDE over a period of approximately 10 years. However, concentrations of dieldrin were comparatively unchanged. Comparisons of present 2001-2002 concentrations in fat of female polar bears from Western Hudson Bay showed great consistency with temporal trends (1991-1999) previously reported for the same region, i.e. the apparent non-decreasing trend of SigmaCHL, beta-HCH, SigmaHCH and dieldrin, and the apparent declining trend for SigmaPCB. However, present concentrations of alpha-HCH and SigmaCBz were elevated, and SigmaDDT was notably lower in Western Hudson Bay samples compared to the last measurements in fat samples collected in 1999, which was not in accord with reported temporal trends for this region. As a result of their relatively high degree of contamination, East Greenland and Svalbard polar bears are at higher health risk of contaminant exposure among Arctic and Subarctic populations. In addition to continued biomonitoring, further research on health and population status is needed to evaluate the impact from chronic exposure of polar bear populations to CHCs and their metabolites.

Stereochemical Alignment in Triphospha[3]ferrocenophanes

PubMed Central

Borucki, Stefan; Kelemen, Zsolt; Maurer, Martin; Bruhn, Clemens

2017-01-01

Abstract A series of triphospha[3]ferrocenophanes of the type Fe(C5H4‐PtBu)2PX with X=H, F, Cl, Br, I, NEt2, tBu has been prepared and characterized by heteronuclear NMR spectroscopy and X‐ray crystallography. Despite having three stereogenic centers, the selective formation of a reduced number of diastereomers (either one or two) has been observed for these ferrocenophanes. Theoretical calculations revealed that the inversion of the central stereogenic center inverts the frontier orbital sequence leading to either an iron or a phosphorus centered HOMO depending on the respective diastereomer. CV measurements supported these results. For the all‐tert‐butyl substituted [3]ferrocenophane Fe(C5H4)2(PtBu)3 a chiral staggered conformation has been found in the solid state which differs substantially from the only other all‐organo substituted [3]ferrocenophane, Fe(C5H4)2(PPh)3. PMID:28557205

Geology, mineralization, and fluid inclusion study of the Kuru-Tegerek Au-Cu-Mo skarn deposit in the Middle Tien Shan, Kyrgyzstan

NASA Astrophysics Data System (ADS)

Soloviev, Serguei G.; Kryazhev, Sergey; Dvurechenskaya, Svetlana

2018-02-01

The Kuru-Tegerek Cu-Au-Mo deposit is situated in a system of Late Carboniferous subduction-related magmatic arcs of the Middle Tien Shan, which together constitute a metallogenic belt of Cu-Au-Mo (±W) porphyry, with local skarns, deposits. The deposit is related to magnetite-series gabbro-diorite to tonalite intrusion. It contains prograde magnesian and calcic skarns with abundant magnetite, associated with gabbro-diorite, and retrograde skarn with Cu mineralization, formed after intrusion of tonalite. Subsequent propylitic alteration introduced abundant chalcopyrite and pyrrhotite, and native Au culminating in zones overprinting magnetite and garnet skarn. Later quartz-muscovite-carbonate veins, formed after intrusion of late mafic quartz monzogabbro dikes, contain chalcopyrite, pyrite, arsenopyrite and other sulfides and sulfosalts, tellurides, and native Au. The earliest retrograde skarn garnet contains gaseous low-salinity (1.7-3.4 wt.% NaCl eq.) fluid inclusions homogenizing at 460-500 °C into vapor, indicating that the early fluid released from crystallizing magma was a low-density vapor. It was followed by more saline (4.0-5.0 wt.% NaCl eq.), high-temperature (400-440 °C) aqueous fluid, as fluid release from the magma progressed. Boiling of this fluid at temperatures of 420 to 370 °C and a pressure of 350-300 bar produced a low-salinity (0.6-1.2 wt.% NaCl eq.), essentially gaseous, and high-salinity (from 39 to 31 wt.% NaCl eq.) brine, with possible metal (including Cu) partitioning into both gaseous and aqueous-saline phases. Boiling was coeval with sulfide deposition in the retrograde skarn. The latest episode of the retrograde skarn stage included direct separation of saline ( 40-42 wt.% NaCl eq.) fluid from crystallizing magma. The separation of saline ( 40 to 14 wt.% NaCl eq.) fluids from a crystallizing magmatic melt continued during the propylitic stage, when fluid cooling from 370 to 320 °C, together with decreasing fO2, caused Cu and especially Au precipitation. A new influx of possibly magma-derived, low-salinity (4.5-6.7 wt.% NaCl eq.) aqueous, and then NaCl-CO2-H2O fluids, corresponds to the phyllic (quartz-muscovite-carbonate-sulfide) stage. These fluids may have a deeper source, associated with the late mafic quartz monzogabbro dikes. Fluid cooling (from 340 to 255 °C) and boiling of the NaCl-CO2-H2O fluid, together with increased fS2, increased the Au endowment.

Crown Ether Complexes of Alkali-Metal Chlorides from SO2.

PubMed

Reuter, Kirsten; Rudel, Stefan S; Buchner, Magnus R; Kraus, Florian; von Hänisch, Carsten

2017-07-18

The structures of alkali-metal chloride SO 2 solvates (Li-Cs) in conjunction with 12-crown-4 or 1,2-disila-12-crown-4 show strong discrepancies, despite the structural similarity of the ligands. Both types of crown ethers form 1:1 complexes with LiCl to give [Li(1,2-disila-12-crown-4)(SO 2 Cl)] (1) and [Li(12-crown-4)Cl]⋅4 SO 2 (2). However, 1,2-disila-12-crown-4 proved unable to coordinate cations too large for the cavity diameter, for example, by the formation of sandwich-type complexes. As a result, 12-crown-4 reacts exclusively with the heavier alkali-metal chlorides NaCl, KCl and RbCl. Compounds [Na(12-crown-4) 2 ]Cl⋅4 SO 2 (3) and [M(12-crown-4) 2 (SO 2 )]Cl⋅4 SO 2 (4: M=K; 5: M=Rb) all showed S-coordination to the chloride ions through four SO 2 molecules. Compounds 4 and 5 additionally exhibit the first crystallographically confirmed non-bridging O,O'-coordination mode of SO 2 . Unexpectedly, the disila-crown ether supports the dissolution of RbCl and CsCl in the solvent and gives the homoleptic SO 2 -solvated alkali-metal chlorides [MCl⋅3 SO 2 ] (6: M=Rb; 7: M=Cs), which incorporate bridging μ-O,O'-coordinating moieties and the unprecedented side-on O,O'-coordination mode. All compounds were characterised by single-crystal X-ray diffraction. The crown ether complexes were additionally studied by using NMR spectroscopy, and the presence of SO 2 at ambient temperature was revealed by IR spectroscopy of the neat compounds. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Comparison of the solubilizing efficiencies of some pH lowering (sulphur and (NH4)2SO4) amendments on Cd and Zn mobility in soils.

PubMed

Amoakwah, Emmanuel; Van Slycken, Stijn; Essumang, David K

2014-08-01

The use of conventional methods to clean up the soil is very expensive and destructive to the ecosystem. The concept of phytoextraction has been introduced to safely manage soils contaminated with heavy metals. However, using plants to remediate polluted soils is a lengthy process. This has necessitated the use of amendments to potentially enhance solubilization of metals in order to increase their bioavailability in the soil solution. A pot experiment was conducted to study the effect of some selected pH lowering amendments [elemental sulphur and (NH4)2SO4] on the solubility and availability of Cd and Zn. The application of these amendments resulted in a decrease in the pH of the soil. The decrease in pH significantly enhanced the solubilization and the mobility of Cd and Zn into the soil solution. The CaCl2 extraction protocol was employed to study the effects of the various amendments on the mobility of Cd and Zn.

Importance of chlorine speciation on de novo formation of polychlorinated dibenzo-p-dioxins and polychlorinated dibenzofurans.

PubMed

Wikström, Evalena; Ryan, Shawn; Touati, Abderrahmane; Telfer, Marnie; Tabor, Dennis; Gullett, Brian K

2003-03-15

The role of chlorine speciation on de novo formation of polychlorinated dibenzo-p-dioxins and polychlorinated dibenzofurans (PCDDs/Fs) has been studied thoroughly in an entrained flow reactor during simulated waste combustion. The effects of gas-phase chlorine species such as chlorine (Cl2), hydrogen chloride (HCl), and chlorine radicals (Cl*), as well as ash-bound chlorine, on PCDD/F de novo formation were isolated for investigation. The ash-bound chlorine alone was observed to be a sufficient chlorine source for PCDD/F formation. The addition of HCl to the system did not influence the yields of the PCDDs/Fs nor the degree of chlorination due to its poor chlorinating ability. Addition of 200 ppm of Cl2 to the ash-feed system resulted in increased PCDD/F yields, especially for the octa- and hepta-chlorinated congeners. Altering the reaction temperature to enable the presence of only Cl2 to the system did not change the yields of PCDD/F compared to those when both Cl2/Cl* were present. However, comparison between ash-bound and gas-phase chlorine, the latter at a concentration typical of a realistic combustion process, revealed ash-bound chlorine to be the more important chlorine source for de novo formation of PCDD/F in a full-scale incinerator.

Critical Manifolds, Travelling Waves and an Example from Population Genetics.

DTIC Science & Technology

1980-11-01

sko ). in fact, If e seo0 k E [ zk 0 , k1 ] and u c N(k), then whenever Izj = k, z l < 0 and whenever Iwj = k, Iw 1 0. -6- Proof. The last sentence...s .k Let cI be aboundfor JZJ and JWJ forall u E N(k’l) and e :s F0 . Choose k 0 so that ko (2 + cl) is a lower bound for the quadratic forms -Z (x...7- Now since k E [sk0 , kl] - ko k+ s50. Also, because k I /cok O , - ko + kc 0 :_ 0. Furthermore at least one of these terms is negative, so (Z < 0. If

Distinct structural changes detected by X-ray fiber diffraction in stabilization of F-actin by lowering pH and increasing ionic strength.

PubMed

Oda, T; Makino, K; Yamashita, I; Namba, K; Maéda, Y

2001-02-01

Lowering pH or raising salt concentration stabilizes the F-actin structure by increasing the free energy change associated with its polymerization. To understand the F-actin stabilization mechanism, we studied the effect of pH, salt concentration, and cation species on the F-actin structure. X-ray fiber diffraction patterns recorded from highly ordered F-actin sols at high density enabled us to detect minute changes of diffraction intensities and to precisely determine the helical parameters. F-actin in a solution containing 30 mM NaCl at pH 8 was taken as the control. F-actin at pH 8, 30 to 90 mM NaCl or 30 mM KCl showed a helical symmetry of 2.161 subunits per turn of the 1-start helix (12.968 subunits/6 turns). Lowering pH from 8 to 6 or replacing NaCl by LiCl altered the helical symmetry to 2.159 subunits per turn (12.952/6). The diffraction intensity associated with the 27-A meridional layer-line increased as the pH decreased but decreased as the NaCl concentration increased. None of the solvent conditions tested gave rise to significant changes in the pitch of the left-handed 1-start helix (approximately 59.8 A). The present results indicate that the two factors that stabilize F-actin, relatively low pH and high salt concentration, have distinct effects on the F-actin structure. Possible mechanisms will be discussed to understand how F-actin is stabilized under these conditions.

The Perils of Electron Microprobe Analysis of Apatite

NASA Astrophysics Data System (ADS)

Henderson, C. E.; Essene, E. J.; Wang, K. L.; Zhang, Y.

2010-12-01

Accurate electron microprobe analysis of apatite is problematic, especially for F and Cl, whose concentrations are essential in calculating a non-analyzable OH component. The issues include beam-induced sample damage and temporal variation of F and Cl X-rays; both effects are mainly dependent on beam current, beam spot size and apatite orientation [1]. To establish a rigorous analytical procedure, several oriented apatite samples, including the well-known Durango and Wilberforce fluorapatites, were analyzed for a large suite of elements, including oxygen. Careful X-ray spectroscopy was performed, including selection of appropriate analytical standards, background measurement positions and comparison of area peak factors. Polarized infrared spectra on oriented apatite samples were also collected for complementary information. The results show that when apatite samples are oriented with the c-axis parallel to the electron beam, there is significant nonlinear variation (an increase or decrease, depending on measurement conditions) of F and Cl X-ray intensities during analyses, and systematically higher-than-expected F apparent concentrations, despite the careful selection of electron beam conditions from a series of X-ray time scans and zero-time count rate extrapolation. On the other hand, when the electron beam is oriented perpendicular to the c-axis, with a ≤ 15 nA beam current and a ≥ 5 µm diameter defocused beam, F and Cl X-ray intensities do not vary or vary slowly and predictably with time, yielding quantitative analysis results for the Durango and Wilberforce apatites (both containing little OH) which are in good agreement with published wet chemical analyses. Furthermore, the OH and CO2 contents inferred for three other analyzed apatite samples are roughly consistent with infrared analyses. For example, for an apatite from Silver Crater Mine in Ontario, significant deficiency in the P site, as well as extra F, was inferred from microprobe analyses. Infrared spectra show a strong band of (CO3)2- for this apatite, which indicates a possible substitution of (CO3)2-(F)- for (PO4)3-. Other techniques to mitigate temporal variation of F and Cl, including alternative metal coatings, concurrent stage movement, and cryogenic sample-cooling were attempted, but did not eliminate the disparity in measured F concentrations between the two sample orientations. Thus, we believe that F measurements on F-rich apatite samples of unknown orientation are immediately suspect and should be regarded as upper limits of true F concentration. X-ray mapping, CL imaging and subsequent quantitative analyses show compositional variations in Na, S, Si, and REE in the Durango and Wilberforce fluorapatite samples used in this study. Problems of electron beam sensitivity, X-ray intensity anisotropy due to sample orientation, and compositional heterogeneity call into question their continued use as routine microanalysis reference materials. Microanalysts are encouraged to use more robust calibration standards, such as Cl-rich or other F-poor apatites for Ca, P, O and Cl, and MgF2 for F measurements. [1] Stormer, J.C., Pierson, M.L, and Tacker, R.C. (1993) Variation of F and Cl X-ray intensity due to anisotropic diffusion in apatite during electron microprobe analysis. Am. Min., 78, 641-648.

Halogen degassing during ascent and eruption of water-poor basaltic magma

USGS Publications Warehouse

Edmonds, M.; Gerlach, T.M.; Herd, Richard A.

2009-01-01

A study of volcanic gas composition and matrix glass volatile concentrations has allowed a model for halogen degassing to be formulated for K??lauea Volcano, Hawai'i. Volcanic gases emitted during 2004-2005 were characterised by a molar SO2/HCl of 10-64, with a mean of 33; and a molar HF/HCl of 0-5, with a mean of 1.0 (from approximately 2500 measurements). The HF/HCl ratio was more variable than the SO2/HCl ratio, and the two correlate weakly. Variations in ratio took place over rapid timescales (seconds). Matrix glasses of Pele's tears erupted in 2006 have a mean S, Cl and F content of 67, 85 and 173??ppm respectively, but are associated with a large range in S/F. A model is developed that describes the open system degassing of halogens from parental magmas, using the glass data from this study, previously published results and parameterisation of sulphur degassing from previous work. The results illustrate that halogen degassing takes place at pressures of < 1??MPa, equivalent to < ~ 35??m in the conduit. Fluid-melt partition coefficients for Cl and F are low (< 1.5); F only degasses appreciably at < 0.1??MPa above atmospheric pressure, virtually at the top of the magma column. This model reproduces the volcanic gas data and other observations of volcanic activity well and is consistent with other studies of halogen degassing from basaltic magmas. The model suggests that variation in volcanic gas halogen ratios is caused by exsolution and gas-melt separation at low pressures in the conduit. There is no evidence that either diffusive fractionation or near-vent chemical reactions involving halogens is important in the system, although these processes cannot be ruled out. The fluxes of HCl and HF from K??lauea during 2004-5 were ~ 25 and 12??t/d respectively. ?? 2008 Elsevier B.V.

Metal organic framework Cu9Cl2(cpa)6 as tunable molecular magnet

NASA Astrophysics Data System (ADS)

Hamilton, Heather S. C.; Farmer, William M.; Skinner, Samuel F.; ter Haar, Leonard W.

2018-05-01

Chemical modifications of the magnetic metal organic framework (MOF) Cu9X2(cpa)6.42H2O (X = F, Cl, Br; cpa = anion of 2-carboxypentonicacid) have been investigated as a means of modifying, in a tunable manner, the magnetism of this 2-D material best described as a triangles-in-triangles (TIT) or triangulated-Kagomé-latttice (TKL). Since numerous theoretical studies have already attempted to describe the enigmatic ground state of this Heisenberg lattice, tunable chemical modifications should provide an excellent opportunity to expand this class of materials for studies concerning fundamental physics of frustrated spins, and applications such as adiabatic demagnetization refrigeration (ADR) that depend on the magnetocaloric effect (MCE). The chemical modification investigated is the intercalation of d- and f-orbital ions into the voids of the framework (channels of nearly 20 Å diameter). Magnetic measurements in the temperature range 1.8 - 300 K confirm signature features of TKL magnetism in intercalated samples persist, specifically: i) large negative Weiss constant (θCW); ii) absence of a phase transition down to 1.8 K; iii) minimum in χMT; iv) low temperature χMT values increasingly divergent at low fields indicating net ferromagnetic correlations; and, v) increasing field dependence of magnetization at low temperatures suggestive of intermediate plateaus, or ferrimagnetism, not saturation.

Evaluation of the effects of the solution used for electrochemical dissolution of nickel-titanium endodontic files on dentine structure, microhardness and cell viability.

PubMed

Amaral, C C F; Ormiga, F; Boldrini, L C; Miranda, P G; Mendonça, T A; Granjeiro, J M; Gomes, J A C P

2018-05-15

To evaluate the effects of the [NaF 12 g/L + NaCl 1 g/L] solution used in the electrochemical dissolution process of fractured endodontic files, as well as its NiTi-containing product, on dentine hardness, topography and human fibroblast viability. Sixty single-rooted human teeth were evaluated for dentine microhardness using the Vickers hardness test and the area and number of dentinal tubules by scanning electron microscopy. The samples were divided according to the dentine surface treatment: distilled water; 17% EDTA; [NaF 12 g/L + NaCl 1 g/L]; and 17% EDTA + [NaF 12 g/L + NaCl 1 g/L]. Thirty-six single-rooted human teeth were divided according to the irrigation protocol: Dulbecco's Modified Eagle's Medium + 10% fetal bovine serum; 5.25% NaOCl; [NaF 12 g/L + NaCl 1 g/L]; and [NaF 12 g/L + NaCl 1 g/L+NiTi]. The extracts in contact with the apical foramen were used in the MTT assay to evaluate human fibroblast viability, with dilutions of 100, 50, 25 and 12.5%. Statistical tests used were paired t-tests, one-way ANOVA, Tukey's test, Kruskal-Wallis test and Dunn's post-test. The [NaF 12 g/L + NaCl 1 g/L] solution did not modify the dentine microhardness or the average dentinal tubule area. However, the EDTA induced changes in the dentine structure and microhardness (p<0.05). The [NaF 12 g/L + NaCl 1 g/L] solution and its NiTi-containing product had lower cytotoxicity than NaOCl at dilutions of 25% and 50% (p<0.01). The [NaF 12 g/L + NaCl 1 g/L] solution did not alter dentine microhardness or damage the dentine structure. It also demonstrated lower cytotoxicity than NaOCl. This article is protected by copyright. All rights reserved. This article is protected by copyright. All rights reserved.

Rapid increase in red blood cell density driven by K:Cl cotransport in a subset of sickle cell anemia reticulocytes and discocytes.

PubMed

Fabry, M E; Romero, J R; Buchanan, I D; Suzuka, S M; Stamatoyannopoulos, G; Nagel, R L; Canessa, M

1991-07-01

We have previously demonstrated that young normal (AA) and sickle cell anemia (SS) red blood cells are capable of a volume regulatory decrease response (VRD) driven by a K:Cl cotransporter that is activated by low pH or hypotonic conditions. We now report on the characteristics of young SS cells (SS2, discocytes) capable of rapid increase in density in response to swelling. We have isolated cells with high VRD response (H-VRD) and low VRD response (L-VRD) cells by incubation and density-gradient centrifugation under hypotonic conditions. Comparison of these cells in patients homozygous for hemoglobin (Hb)S indicated that H-VRD cells have 91% more reticulocytes (P less than 9 x 10(-9) than L-VRD cells, 25% less HbF (P less than 5.5 x 10(-5), 106% more NEM (N-methylmaleimide)-stimulated K:Cl cotransport activity (P less than 2 x 10(-4), and 86% more volume-stimulated K:Cl cotransport activity (P less than 1.8 x 10(-3). H-VRD and L-VRD cells have similar G-6-PD and Na+/H+ antiport activity. In agreement with the reduced percent HbF in H-VRD cells, F cells (red blood cells that contain fetal Hb) are depleted from the H-VRD population; however, F reticulocytes are enriched in the H-VRD population to the same extent as non-F reticulocytes, which suggests that both F and non-F reticulocytes have a similar initial distribution of volume-sensitive K:Cl cotransport activity but that it may be more rapidly inactivated in F than in S reticulocytes. We find that H-VRD cells consist of 20% reticulocytes (or 79% of all reticulocytes in SS2) and 80% more mature cells. This study demonstrates the role of K:Cl cotransport in determining red blood cell density, the heterogeneity of K:Cl cotransport activity in reticulocytes, and the capacity for rapid change in the density of reticulocytes with high K:Cl cotransport activity. We speculate that the H-VRD population may be more susceptible to generation of dense and irreversibly sickled cells.

Direct solar-pumped iodine laser amplifier

NASA Technical Reports Server (NTRS)

Han, Kwang S.; Hwang, In H.; Stock, Larry V.

1988-01-01

A XeCl laser which was developed earlier for an iodine laser oscillator was modified in order to increase the output pulse energy of XeCl laser so that the iodine laser output energy could be increased. The electrical circuit of the XeCl laser was changed from a simple capacitor discharge circuit of the XeCl laser to a Marx system. Because of this improvement the output energy from the XeCl laser was increased from 60 mj to 80 mj. Subsequently, iodine laser output energy was increased from 100 mj to 3 mj. On the other hand, the energy storage capability and amplification characteristics of the Vortek solar simulator-pumped amplifier was calculated expecting the calculated amplification factor is about 2 and the energy extraction efficiency is 26 percent due to the very low input energy density to the amplifier. As a result of an improved kinetic modeling for the iodine solar simulator pumped power amplifier, it is found that the I-2 along the axis of the tube affects seriously the gain profile. For the gas i-C3F7I at the higher pressures, the gain will decrease due to the I-2 as the pumping intensity increases, and at these higher pressures an increase in flow velocity will increase the gain.

Two-Dimensional Large Gap Topological Insulators with Tunable Rashba Spin-Orbit Coupling in Group-IV films

PubMed Central

Zhang, Shou-juan; Ji, Wei-xiao; Zhang, Chang-wen; Li, Ping; Wang, Pei-ji

2017-01-01

The coexistence of nontrivial topology and giant Rashba splitting, however, has rare been observed in two-dimensional (2D) films, limiting severely its potential applications at room temperature. Here, we through first-principles calculations to propose a series of inversion-asymmetric group-IV films, ABZ2 (A ≠ B = Si, Ge, Sn, Pb; Z = F, Cl, Br), whose stability are confirmed by phonon spectrum calculations. The analyses of electronic structures reveal that they are intrinsic 2D TIs with a bulk gap as large as 0.74 eV, except for GeSiF2, SnSiCl2, GeSiCl2 and GeSiBr2 monolayers which can transform from normal to topological phases under appropriate tensile strain of 4, 4, 5, and 4%, respectively. The nontrivial topology is identified by Z2 topological invariant together with helical edge states, as well as the berry curvature of these systems. Another prominent intriguing feature is the giant Rashba spin splitting with a magnitude reaching 0.15 eV, the largest value reported in 2D films so far. The tunability of Rashba SOC and band topology can be realized through achievable compressive/tensile strains (−4 ~ 6%). Also, the BaTe semiconductor is an ideal substrate for growing ABZ2 films without destroying their nontrivial topology. PMID:28368035

Crystal structures of Sr(ClO4)2·3H2O, Sr(ClO4)2·4H2O and Sr(ClO4)2·9H2O

PubMed Central

Hennings, Erik; Schmidt, Horst; Voigt, Wolfgang

2014-01-01

The title compounds, strontium perchlorate trihydrate {di-μ-aqua-aquadi-μ-perchlorato-strontium, [Sr(ClO4)2(H2O)3]n}, strontium perchlorate tetra­hydrate {di-μ-aqua-bis­(tri­aqua­diperchloratostrontium), [Sr2(ClO4)4(H2O)8]} and strontium perchlorate nona­hydrate {hepta­aqua­diperchloratostrontium dihydrate, [Sr(ClO4)2(H2O)7]·2H2O}, were crystallized at low temperatures according to the solid–liquid phase diagram. The structures of the tri- and tetra­hydrate consist of Sr2+ cations coordinated by five water mol­ecules and four O atoms of four perchlorate tetra­hedra in a distorted tricapped trigonal–prismatic coordination mode. The asymmetric unit of the trihydrate contains two formula units. Two [SrO9] polyhedra in the trihydrate are connected by sharing water mol­ecules and thus forming chains parallel to [100]. In the tetra­hydrate, dimers of two [SrO9] polyhedra connected by two sharing water mol­ecules are formed. The structure of the nona­hydrate contains one Sr2+ cation coordinated by seven water mol­ecules and by two O atoms of two perchlorate tetra­hedra (point group symmetry ..m), forming a tricapped trigonal prism (point group symmetry m2m). The structure contains additional non-coordinating water mol­ecules, which are located on twofold rotation axes. O—H⋯O hydrogen bonds between the water mol­ecules as donor and ClO4 tetra­hedra and water mol­ecules as acceptor groups lead to the formation of a three-dimensional network in each of the three structures. PMID:25552979