The effect of chlorine and chlorine dioxide on pathogenic free‐living amoebae (PFLA) in simulated natural conditions: The presence of bacteria and organic matter

Bacteria and bovine faecal matter were introduced into cultures of pathogenic free‐living amoebae, with chlorine or chlorine dioxide. The bacteria and faeces were to simulate natural conditions for a more exacting test of disinfectant demand when compared to axenic conditions. Both chlorine and chlorine dioxide were effective disinfectants under all conditions tested. Axenically and monoxenically cultured amoebae were used, the latter exerted a greater disinfectant demand.     

The crystal structure of Ca5(PO4)2SiO4 (Silico-Carnotite)

Summary The crystal structure of Ca₅(PO₄)₂SiO₄ (silico-carnotite) has been determined from 3358 x-ray diffraction data collected by a counter method and has been refined toR _w =0.038,R=0.045, in space group Pnma. The unit cell parameters area=6.737 (1) Å,b=15.508 (2) Å andc=10.132 (1) Å at 24°C;Z=4. The observed density is 3.06 and the calculated density is 3.03 g · cm^–3. The crystal contains about 2.5% V₂O₅ as an impurity. The bond lengths within the tetrahedral anions suggest that substitution or disorder of PO₄ ^3–, SiO₄ ^4– and possibly VO₄ ^3– occurs among the anion sites. The structure has some relationship to that of Ca₅(PO₄)₃OH, the predominant inorganic phase in the human body, but suggests that the Ca₅(PO₄)₃OH type structure may not be stable without some of the OH positions being filled. Ca₅(PO₄)₂SiO₄ is more closely related to K₃Na(SO₄)₂ (glaserite) if it is considered that there are systematic cation vacancies in Ca₅(PO₄)₂SiO₄.This type of structure is consistent with the view that cation vacancies in the glaserite-type structure account for solid solutions between Ca₂SiO₄ and Ca₃(PO₄)₂ and between Ca₃(PO₄)₂ and CaNaPO₄.

---

Die Kristallstruktur vonCa ₅(PO ₄)₂ SiO ₄ (Silicocarnotit)

Zusammenfassung Die Kristallstruktur von Ca₅(PO₄)₂SiO₄ (Silicocarnotit) wurde aus 3358 Röntgendiffraktometer-Daten bestimmt und in Raumgruppe Pnma aufR _w =0,038,R=0,045 verfeinert. Die Gitterkonstanten (bei 24° C) sind:a=6,737 (1) Å,b=15,508 (2) Å undc=10,132 (1) Å,Z=4; D_obs.=3,06 g · cm^–3, D_exp.=3,03 g · cm^–3. Der Kristall enthält etwa 2,5% V₂O₅ als Verunreinigung. Die Bindungslängen in den tetraedrischen Anionen legen nahe, daß unter den Anionenplätzen gegenseitige Vertretung oder Unordnung von PO₄ ^3–, SiO₄ ^4– und möglicherweise VO₄ ^3– auftritt. Die Struktur zeigt einige Verwandtschaft zu der von Ca₅(PO₄)₃OH, der wichtigsten anorganischen Substanz im menschlichen Körper, weist aber darauf hin, daß eine Struktur vom Ca₅(PO₄)₃OH-Typ ohne Besetzung eines Teiles der OH-Position nicht stabil ist. Ca₅(PO₄)₂SiO₄ zeigt engere Beziehungen zu K₃Na(SO₄)₂ (Glaserit), wenn man berücksichtigt, daß in Ca₅(PO₄)₃SiO₄ systematische Kationen-Leerstellen sind. Dieser Strukturtyp ist mit derAuffassung in Übereinstimmung, daß Kationenleerstellen für die festen Lösungen zwischen Ca₂SiO₄ und Ca₃(PO₄)₂ und zwischen Ca₃(PO₄)₂ und CaNaPO₄ verantwortlich sind.

---

---

With 9 Figures     

Use of in situ-produced Be in carbonate-rich environments: A first attempt

We have determined the production rate of in situ-produced ¹⁰Be in calcite through measurements of ¹⁰Be and ³⁶Cl concentrations in the same calcite samples and of ¹⁰Be concentrations in depth profiles of flint from the same erosional surface. This yields a ¹⁰Be production rate in calcite of 37.9 ± 6.0 at/g/yr at sea level and high latitude, approximately sixfold higher than production in the coexisting flint. We propose that this higher rate of production may be due to high production cross sections for C spallation by cosmic rays with energies below 50 MeV. These results also open the possibility of dating burial events in carbonate-rich environments by differential radioactive decay of ¹⁰Be and ³⁶Cl.     

Mineralogical and Geochemical Constraints on the Sediment Sources of Late Stone Age Pottery from the Birimi Site,Northern Ghana

The mineralogy and bulk chemical compositions of 15 Kintampo (Late Stone Age) potsherds from the Birimi site on the Gambaga Escarpment and eight samples of local sediment were determined with the intent of characterizing these wares and identifying the material used in their manufacture. Sediment from clay pits still used by potters north of the escarpment contains iron‐rich laterite clasts (100 × XFeO_t = 100 × FeO_t/[FeO_t + Al₂O₃ + SiO₂] ≥10). Sedimentary clasts in stream sediments are relatively siliceous and iron‐poor (100 × XFeO_t < 10). Bulk geochemical data together with the compositions of lithic clasts (laterite, siltstone/sandstone) link the pottery to sediment sources, including escarpment sediments not presently used by Ghanaian potters. Fresh granite clasts found in some of the sherds were not found in the analyzed sediment samples, although some of their distinctive mineralogical constituents (e.g., variably barian alkali feldspar) are present. The analytical data suggest that pots found at Birimi were made locally by mixing escarpment sediment with clay and stream sediment brought in from below the escarpment. This contrasts with present‐day practice, whereby the pots themselves are imported. The place where Birimi pottery was made and the outcrop source of aluminous sediment (mudstone with an “escarpment” trace element signature) used in these wares, however, remain unidentified. © 2013 Wiley Periodicals, Inc.     

Paleoclimatic implications of glacial and postglacial refugia for Pinus pumila in western Beringia

Palynological results from Julietta Lake currently provide the most direct evidence to support the existence of a glacial refugium for Pinus pumila in mountains of southwestern Beringia. Both percentages and accumulation rates indicate the evergreen shrub survived until at least ∼ 19,000 ¹⁴C yr BP in the Upper Kolyma region. Percentage data suggest numbers dwindled into the late glaciation, whereas pollen accumulation rates point towards a more rapid demise shortly after ∼ 19,000 ¹⁴C yr BP. Pinus pumila did not re-establish in any great numbers until ∼ 8100 ¹⁴C yr BP, despite the local presence ∼ 9800 ¹⁴C yr BP of Larixdahurica, which shares similar summer temperature requirements. The postglacial thermal maximum (in Beringia ∼ 11,000-9000 ¹⁴C yr BP) provided Pinus pumila shrubs with equally harsh albeit different conditions for survival than those present during the LGM. Regional records indicate that in this time of maximum warmth Pinus pumila likely sheltered in a second, lower-elevation refugium. Paleoclimatic models and modern ecology suggest that shifts in the nature of seasonal transitions and not only seasonal extremes have played important roles in the history of Pinus pumila over the last ∼ 21,000 ¹⁴C yr BP.     

Evidence for Neotethys rooted within the Vardar suture zone from the Voras Massif, northernmost Greece

Three conflicting models are currently proposed for the location and tectonic setting of the Eurasian continental margin and adjacent Tethys ocean in the Balkan region during Mesozoic–Early Tertiary time. Model 1 places the Eurasian margin within the Rhodope zone relatively close to the Moesian platform. A Tethyan oceanic basin was located to the south bordering a large “Serbo-Pelagonian” microcontinent. Model 2 correlates an integral “Serbo-Pelagonian” continental unit with the Eurasian margin and locates the Tethys further southwest. Model 3 envisages the Pelagonian zone and the Serbo-Macedonian zone as conjugate continental units separated by a Tethyan ocean that was sutured in Early Tertiary time to create the Vardar zone of northern Greece and former Yugoslavia. These published alternatives are tested in this paper based on a study of the tectono-stratigraphy of a completely exposed transect located in the Voras Mountains of northernmost Greece. The outcrop extends across the Vardar zone, from the Pelagonian zone in the west to the Serbo-Macedonian zone in the east.Within the Voras Massif, six east-dipping imbricate thrust sheets are recognised. Of these, Units 1–4 correlate with the regional Pelagonian zone in the west (and related Almopias sub-zone). By contrast, Units 5–6 show a contrasting tectono-stratigraphy and correlate with the Paikon Massif and the Serbo-Macedonian zone to the east. These units form a stack of thrust sheets, with Unit 1 at the base and Unit 6 at the top. Unstacking these thrust sheets places ophiolitic units between the Pelagonian zone and the Serbo-Macedonian zone, as in Model 3. Additional implications are, first, that the Paikon Massif cannot be seen as a window of Pelagonian basement, as in Model 1, and, secondly, Jurassic andesitic volcanics of the Paikon Massif locally preserve a gneissose continental basement, ruling out a recently suggested origin as an intra-oceanic arc.We envisage that the Almopias (Vardar) ocean rifted in Triassic time, followed by seafloor spreading. The Almopias ocean was consumed beneath the Serbo-Macedonian margin in Jurassic time, generating subduction-related arc volcanism in the Paikon Massif and related units. Ophiolites were emplaced onto the Pelagonian margin in the west and covered by Late Jurassic (pre-Kimmeridgian) conglomerates. Other ophiolitic rocks formed within the Vardar zone (Ano Garefi ophiolite, Unit 4) in latest Jurassic–Early Cretaceous time and were not deformed until Early Tertiary time. The Vardar zone finally sutured in the Early Tertiary creating the present imbricate thrust structure of the Voras Mountains.     

Biogenic nanoparticulate UO2: Synthesis, characterization, and factors affecting surface reactivity

The surface reactivity of biogenic, nanoparticulate UO₂ with respect to sorption of aqueous Zn(II) and particle annealing is different from that of bulk uraninite because of the presence of surface-associated organic matter on the biogenic UO₂. Synthesis of biogenic UO₂ was accomplished by reduction of aqueous uranyl ions, by Shewanella putrefaciens CN32, and the resulting nanoparticles were washed using one of two protocols: (1) to remove surface-associated organic matter and soluble uranyl species (NAUO2), or (2) to remove only soluble uranyl species (BIUO2). A suite of bulk and surface characterization techniques was used to examine bulk and biogenic, nanoparticulate UO₂ as a function of particle size and surface-associated organic matter. The N₂-BET surface areas of the two biogenic UO₂ samples following the washing procedures are 128.63 m² g⁻¹ (NAUO2) and 92.56 m² g⁻¹ (BIUO2), and the average particle sizes range from 5-10 nm based on TEM imaging. Electrophoretic mobility measurements indicate that the surface charge behavior of biogenic, nanoparticulate UO₂ (both NAUO2 and BIUO2) over the pH range 3-9 is the same as that of bulk. The U L_III-edge EXAFS spectra for biogenic UO₂ (both NAUO2 and BIUO2) were best fit with half the number of second-shell uranium neighbors compared to bulk uraninite, and no oxygen neighbors were detected beyond the first shell around U(IV) in the biogenic UO₂. At pH 7, sorption of Zn(II) onto both bulk uraninite and biogenic, nanoparticulate UO₂ is independent of electrolyte concentration, suggesting that Zn(II) sorption complexes are dominantly inner-sphere. The maximum surface area-normalized Zn(II) sorption loadings for the three substrates were 3.00 ± 0.20 μmol m⁻² UO₂ (bulk uraninite), 2.34 ± 0.12 μmol m⁻² UO₂ (NAUO2), and 2.57 ± 0.10 μmol m⁻² UO₂ (BIUO2). Fits of Zn K-edge EXAFS spectra for biogenic, nanoparticulate UO₂ indicate that Zn(II) sorption is dependent on the washing protocol. Zn-U pair correlations were observed at 2.8 ± 0.1 Å for NAUO2 and bulk uraninite; however, they were not observed for sample BIUO2. The derived Zn-U distance, coupled with an average Zn-O distance of 2.09 ± 0.02 Å, indicates that Zn(O,OH)₆ sorbs as bidentate, edge-sharing complexes to UO₈ polyhedra at the surface of NAUO2 nanoparticles and bulk uraninite, which is consistent with a Pauling bond-valence analysis. The absence of Zn-U pair correlations in sample BIUO2 suggests that Zn(II) binds preferentially to the organic matter coating rather than the UO₂ surface. Surface-associated organic matter on the biogenic UO₂ particles also inhibited particle annealing at 90 °C under anaerobic conditions. These results suggest that surface-associated organic matter decreases the reactivity of biogenic, nanoparticulate UO₂ surfaces relative to aqueous Zn(II) and possibly other environmental contaminants.     

A methodology for making initial estimates of groundwater recharge from groundwater vulnerability mapping

Recharge to an aquifer can be estimated by first calculating the effective rainfall using a soil moisture budgeting technique, and then by applying a recharge coefficient to indicate the proportion of this effective rainfall that contributes to groundwater recharge. In the Republic of Ireland, the recharge coefficient is determined mainly by the permeability and thickness of the superficial deposits (subsoils) that overlie the country’s aquifers. The properties of these subsoils also influence groundwater vulnerability, and a methodology has been developed for determining the recharge coefficient using the groundwater vulnerability classification. The results of four case studies have been used to develop a quantified link between subsoil permeability, aquifer vulnerability, recharge and runoff. Recharge and runoff coefficients are each classed into three groupings: high, intermediate and low. A high recharge coefficient equates to a low runoff coefficient, and vice versa. A GIS-based tool enables preliminary estimates of recharge to be made using these recharge coefficient groupings. Potential recharge is calculated as the product of effective rainfall and recharge coefficient. The actual recharge is then calculated taking account of the ability of the aquifer to accept the available recharge. The methodology could be applied to other temperate climate zones where the main aquifers have a substantial covering of superficial deposits.     

The use of solar faculae in studies of the sunspot cycle

Comparison of the long-term variation of photospheric faculae areas with that of sunspots shows that studies of faculae provide both complementary and supplementary information on the behaviour of the solar cycle. Detailed studies of the development of sunspots with respect to faculae show that there is a high degree of order over much of a given cycle, but marked differences from cycle to cycle. Within a cycle the relationship between spot and faculae areas appears to be similar for the N and S solar hemispheres, and over the early stages of a cycle it is directly related to the magnitude of the maximum sunspot number subsequently attained in that cycle.This result may well have predictive applications, and formulae are given relating the peak sunspot number to simple parameters derived from this early developmental stage. Full application to the current cycle 21 is denied due to the cessation of the Greenwich daily photoheliographic measurements, but use of the cruder weekly data suggests a maximum smoothed sunspot number of 150 ± 22.The effects of the incompatibility of the spot and faculae data, in that faculae are unobservable over a large fraction of the solar disc and also do not always develop associated spots, have been examined in a detailed study of two cycles and shown not to vitiate the results.Now at NOAA, Environmental Data Service, NGSTDC, Boulder, Colo. 80302, U.S.A.