A New Reference Material for Tritium Organic Molecules in Sediment: Results of an International Intercomparison Exercise

Solid matrix ³H reference materials are challenging to prepare given the volatile nature of ³H and are often unrepresentative of the range of ³H forms that may be encountered during routine analysis. As a result, few ³H reference materials are currently available, undermining verification of analytical techniques for environmental ³H measurement. To address this, an International Working Group on Organically‐Bound Tritium Analysis determined to produce a tritium natural matrix reference material (NMRM). The reference material comprises marine sediment blended with sewage sludge contaminated with ³H‐organic species arising from authorised discharges from a radiopharmaceutical manufacturing site. Previous studies have demonstrated that the ³H species have persisted in the environment over three decades providing valuable supporting data to underpin the characterisation of the NMRM. The preparation and characterisation of the NMRM are described along with the subsequent application of the reference material in an international intercomparison exercise involving nineteen laboratories from nine countries. A reference value of 168 ± 22 Bq kg^?1 was derived from the data arising from the proficiency test.     

The synergistic effect of calcium on organic carbon sequestration to ferrihydrite

Sequestration of organic carbon (OC) in environmental systems is critical to mitigating climate change. Organo-mineral associations, especially those with iron (Fe) oxides, drive the chemistry of OC sequestration and stability in soils. Short-range-ordered Fe oxides, such as ferrihydrite, demonstrate a high affinity for OC in binary systems. Calcium commonly co-associates with OC and Fe oxides in soils, though the bonding mechanism (e.g., cation bridging) and implications of the co-association for OC sequestration remain unresolved. We explored the effect of calcium (Ca²⁺) on the sorption of dissolved OC to 2-line ferrihydrite. Sorption experiments were conducted between leaf litter-extractable OC and ferrihydrite at pH 4 to 9 with different initial C/Fe molar ratios and Ca²⁺ concentrations. The extent of OC sorption to ferrihydrite in the presence of Ca²⁺ increased across all tested pH values, especially at pH ≥ 7. Sorbed OC concentration at pH 9 increased from 8.72 ± 0.16 to 13.3 ± 0.20 mmol OC g^?1 ferrihydrite between treatments of no added Ca²⁺ and 30 mM Ca²⁺ addition. Batch experiments were paired with spectroscopic studies to probe the speciation of sorbed OC and elucidate the sorption mechanism. ATR-FTIR spectroscopy analysis revealed that carboxylic functional moieties were the primary sorbed OC species that were preferentially bound to ferrihydrite and suggested an increase in Fe-carboxylate ligand exchange in the presence of Ca at pH 9. Results from batch to spectroscopic experiments provide significant evidence for the enhancement of dissolved OC sequestration to 2-line ferrihydrite and suggest the formation of Fe–Ca-OC ternary complexes. Findings of this research will inform modeling of environmental C cycling and have the potential to influence strategies for managing land to minimize OM stabilization.     

Modeling of the swelling–shrinkage behavior of expansive clays during wetting–drying cycles

Acta Geotechnica - This paper presents a constitutive model for simulating the swelling–shrinkage volume change of expansive soils during wetting–drying cycles. Based on the concept of...     

Diagenesis impact on a deeply buried sandstone reservoir (Es1 Member) of the Shahejie Formation,Nanpu Sag,Bohai Bay Basin,East China

Diagenesis has a significant impact on reservoir quality in deeply buried formations. Sandstone units of the Shahejie Formation (Es₁ Member) of Nanpu Sag, Bohai Bay Basin, East China is a typical deeply buried sandstone with large hydrocarbon accumulations. The methodology includes core observations and thin section studies, using fluorescence, scanning electron microscope (SEM), cathodoluminescence (CL), fluid inclusion and isotope and electron probing analysis as well as the numerical determination of reservoir characteristics. The sandstones consist of medium to coarse-grained, slight to moderate sorted lithic arkose and feldspathic litharenite. Porosity and permeability values range from 0.5 to 30% and 0.006 to 7000 mD, respectively. The diagenetic history reveals mixed episodes of diagenesis and deep burial followed by uplift. The main diagenetic events include compaction, cementation alteration, dissolution of unstable minerals and grain fracturing. Compaction resulted in densification and significantly reduced the primary porosity. Quartz, calcite and clay are the dominant pore-occluding cement and occur as euhedral to subhedral crystals. Alteration and dissolution of volcanic lithic fragments and pressure solution of feldspar grains were the key sources of quartz cement whereas carbonate cement is derived from an external source. Clay minerals resulted from the alteration of feldspar and volcanic lithic fragments. Porosity and permeability data predict a good inverse relationship with cementation whereas leaching of metastable grains, dissolution of cement and in some places formation of pore-lining chlorite enhanced the reservoir quality. The best reservoir is thicker sandstone bodies that are medium to coarse-grained, well-sorted sandstone with low primary ductile grains with a minor amount of calcite cement. The present study shows several diagenetic stages in the Es₁ Member, but the overall reservoir quality is preserved.     

Global travertine deposition modulated by oscillations in climate

Travertine deposits are important records of past fluid flow in the Earth's crust, and document fluid migration through both tectonic activity and changes in climate. While many studies hint at possible relationships between travertine formation and global climate, none have investigated these connections on a global scale. Here we compile 1649 published travertine ages from six continents to test the hypothesis that global and/or regional changes in climate regulate travertine deposition. Peaks in bedded travertine ages occur with main frequencies that correspond to 100‐kyr changes in global climate, where most peaks occur during glacial terminations or interglacial periods, including a large peak that coincides with the Early Holocene climatic optimum. Time–series analysis also suggests a possible connection with 41‐kyr obliquity cycles. At regional scales, many peaks also correspond with local times of high precipitation or wet conditions. This can be attributed to higher groundwater recharge rates, providing the necessary water to form travertine. Many bedded travertine‐depositing systems may therefore be water‐limiting and sufficient CO₂ may be present even during times of no travertine deposition. Exceptions to this conclusion are banded vein travertine deposits, which typically form during times of dry climate when water tables are low. Copyright © 2019 John Wiley & Sons, Ltd.     

Deep‐water dunes on drowned isolated carbonate terraces (Mozambique Channel,south‐west Indian Ocean)

Subaqueous sand dunes are common bedforms on continental shelves dominated by tidal and geostrophic currents. However, much less is known about sand dunes in deep‐marine settings that are affected by strong bottom currents. In this study, dune fields were identified on drowned isolated carbonate platforms in the Mozambique Channel (south‐west Indian Ocean). The acquired data include multibeam bathymetry, multi‐channel high‐resolution seismic reflection data, sea floor imagery, a sediment sample and current measurements from a moored current meter and hull‐mounted acoustic Doppler current profiler. The dunes are located at water depths ranging from 200 to 600 m on the slope terraces of a modern atoll (Bassas da India Atoll) and within small depressions formed during tectonic deformation of drowned carbonate platforms (Sakalaves Seamount and Jaguar Bank). Dunes are composed of bioclastic medium size sand, and are large to very large, with wavelengths of 40 to 350 m and heights of 0·9 to 9·0 m. Dune migration seems to be unidirectional in each dune field, suggesting a continuous import and export of bioclastic sand, with little sand being recycled. Oceanic currents are very intense in the Mozambique Channel and may be able to erode submerged carbonates, generating carbonate sand at great depths. A mooring located at 463 m water depth on the Hall Bank (30 km west of the Jaguar Bank) showed vigorous bottom currents, with mean speeds of 14 cm sec^?1 and maximum speeds of 57 cm sec^?1, compatible with sand dune formation. The intensity of currents is highly variable and is related to tidal processes (high‐frequency variability) and to anticyclonic eddies near the seamounts (low‐frequency variability). This study contributes to a better understanding of the formation of dunes in deep‐marine settings and provides valuable information about carbonate preservation after drowning, and the impact of bottom currents on sediment distribution and sea floor morphology.     

Interaction between lateral sorting in river bends and vertical sorting in dunes

Sediment is sorted in river bends under the influence of gravity that pulls the heavier grains downslope and secondary flow that drags the finer grains upslope. Furthermore, when dunes are present, sediment is also sorted vertically at the dune lee side. However, sorting functions are poorly defined, since the relation to transverse bed slope and the interaction between lateral and vertical sorting is not yet understood for lack of data under controlled conditions. The objective of this study is to describe lateral sorting as a function of transverse bed slope and to gain an understanding of the interaction between lateral and vertical sorting in river bends. To this end, experiments were conducted with a poorly sorted sediment mixture in a rotating annular flume in which secondary flow intensity can be controlled separately from the main flow velocity, and therefore transverse bed slope towards the inner bend and dune dimensions can be systematically varied. Sediment samples were taken along cross-sections at the surface of dune troughs and dune crests, and over the entire depth at the location of dune crests (bulk samples), which enabled comparison of the relative contribution of vertical sorting by dunes to lateral sorting by the transverse bed slope. The data show that lateral sorting is always the dominant sorting mechanism in bends, and bulk samples showed minor effects of vertical sorting by dunes as long as all grain-size fractions are mobile. An empirical bend sorting model was fitted that redistributes the available sediment fractions over the cross-section as a function of transverse bed slope. Comparison with field data showed that the model accurately reproduces spatially-averaged trends in sorting at the bend apex in single-thread channels. The bend sorting model therefore provides a better definition of bend sorting with conservation of mass by size fraction and adds to current understanding of bend sorting. The implication for numerical modelling is that bend sorting mechanisms can be modelled independently of dunes, allowing the application of the active layer concept.     

Thermodynamics of arsenates, selenites, and sulfates in the oxidation zone of sulfide ores: VI. Solubility of synthetic analogs of ahlfeldite and cobaltomenite at 25°C

The understanding of the mechanisms of the selenium behavior under near-surface conditions is an urgent problem of modern mineralogy and geochemistry, and is very important for solving environmental problems. The objective of this study is to synthesize analogs of ahlfeldite and cobaltomenite and to estimate their solubility in water. These analogs have been synthesized by mixing aqueous solutions of cobalt and nickel nitrates, respectively, and sodium selenite acidified with a solution of nitric acid. The obtained samples have been identified by X-ray diffraction and IR spectroscopy. The solubility has been determined by the isothermal saturation method in ampoules at 25°C, while the solubility products have been calculated using the Geochemist’s Workbench (GMB 7.0) software package. The solubility products of ahlfeldite and cobaltomenite are 10^?9.20 and 10^?9.44, respectively. The Eh-pH diagrams were calculated and plotted with the GMB 7.0 software package. The Eh-pH diagrams of the Ni-Se-H₂O and Co-Se-H₂O systems have been calculated for the average contents of these elements in underground water and their contents in acidic water of the oxidation zone of sulfide deposits. The formation of ahlfeldite and cobaltomenite under near-surface conditions is discussed.     

MinIdent: An application to the identification and classification of amphiboles

Summary Amphibole data in the MinIdent database (Smith andLeibovitz, 1986) were initially entered using species names quoted in the original source. The database has been updated by reclassifying these early data using the program AMPHTAB supplied by N. M. S. Rock and by adding supplemental data from the more recent literature, with the species names again checked using AMPHTAB. Associated MinIdent mineral identification software was utilized to determine which minerals in the database most closely resemble a series of unknown specimens chemically, as expressed in the Chemical Matching Index, CM, a relative figure-of-merit. Chemical data fromMogessie and Tessadri (1982) and Hawthorne (1983) were used to check the agreement between MinIdent and AMPHTAB for the classification of 221 unknown amphiboles.With 450 amphibole analyses entered and compiled in MinIdent, the name assigned by AMPHTAB showed the highest value of CM in MinIdent for 127 of the 221 unknown amphiboles (57.5°/x) and the second highest value for another 32 (14.5%). A chemically adjacent amphibole field had the highest value of CM for 59 of the 221 unknowns (26.7%), where chemically adjacent refers to a change in one chemical parameter. The greatest discrepancy between the two programs occurred in the hornblendes, with an agreement of just 20%, although for 58% of the unknowns the species with the highest CM in MinIdent was in a chemical field adjacent to the species name assigned by AMPHTAB. In many cases the disagreement between MinIdent and AMPHTAB could be ascribed to a lack of data in MinIdent.A comparison of the two programs suggests that the assignment of a single name to an unknown amphibole by AMPHTAB with no direct indication of its reliability may be; misleading. Standard analytical errors are frequently sufficient to overlap the arbitrary boundaries between amphibole species fields. In such cases it may be preferable to use a program such as MinIdent which, rather than assigning an arbitrary amphibole name, presents a list of 20 amphiboles with the degree of similarity between them and the unknown amphibole indicated. MinIdent offers the additional benefit of allowing input of other than chemical data and bases the match between unknown and standard data upon all input data. This will become more of an advantage as instruments such as automated refractometers become available for routine use.

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Zusammenfassung Ausgangspunkt war das Amphibol-Datenmaterial (Smith und Leibovitz, 1986) mit den dort verwendeten Artnamen. Diese Basisdaten wurden vervollständigt und erneuert durch Reklassifizierung mittels des AMPHTAB Programms, ergänzt durch N. M. S. Rock, und durch Hinzufügung weiterer Daten aus der neuesten Literatur, deren Speciesnamen wiederum mit AMPHTAB überprüft wurden. Außerdem wurde eine MinIdent Mineralidentifizierungs-Software verwendet, um die Minerale zu bestimmen, die in ihrem Chemismus am ehesten einer Serie von unbekannten Amphibol-Species entsprechen, wie sie im Chemical Matching Index (CM) aufscheinen. Zur Klassifikation von 221 unbekannten Amphibolen wurden chemische Daten von Mogessie und Tessadri (1982) verwendet um die Übereinstimmung zwischen MinIdent und AMPHTAB zu überprüfen.Unter den 450 in MinIdent zusammengestellten und eingegebenen Amphibolanalysen zeigen die bei AMPHTAB angegebenen die höchsten CM Werte, nämlich 127 von 221 unbekannten Amphibolen (57,5%) und weitere 32 (14,5%) die zweithöchsten Werte. Innerhalb eines chemisch benachbarten Amphibolfeldes hatten 59 der 221 unbekannten Amphibole (26,7%) die höchsten CM Werte, wobei unter achemisch benachbart die Änderung eines chemischen Parameters zu verstehen ist. Die größten Unterschiede zwischen den beiden Programmen traten bei den Hornblenden auf. Die Übereinstimmung lag bei nur 20%, obwohl bei 58% der unbekannten Amphibole die Species mit dem höchsten CM Wert in MinIdent in ein chemisches Feld zu liegen kamen, welches zu den bei AMPHTAB angegebenen Speciesnamen eine benachbarte Position einnimmt. Die Unterschiede zwischen MinIdent und AMPHTAB könnten in vielen Fällen auf ein Fehlen von Daten in MinIdent zurükzuführen sein.Ein Vergleich beider Programme deutet an, daß die Angabe eines Einzelnamens für ein unbekanntes Amphibol im AMPHTAB Programm ohne Angaben über die Zuverlässigkeit zu Mißverständnissen führen kann. Normale analytische Fehler können bereits dazu führen, daß die Grenzen zweier willkürlicher Amphibolfelder überlappen. In derartigen Fällen emphiehlt sich die Anwendung des MinIdent Programmes, welches eben nicht einen willkürlichen Amphibolnamen angibt, sondern eine Liste von 20 Amphibolen mit dem Grad ihrer Ähnlichkeit, und einem Hinweis auf den unbekannten Amphibol. MinIdent bietet den zusätzlichen Vorteil, daß man außer chemischen auch andere Daten eingeben kann, und stellt dann sämtliche Daten des unbekannten Amphibols den Standard Daten gegenüber. Dieser Klassifizierungsvorgang wird mit der zunehmenden Routineanwendung von automatischen Refraktometern verstärkte Anwendung finden.

     

An occurrence of grandidierite,kornerupine, and tourmaline in southeastern Ontario,Canada

Grandidierite, kornerupine, and tourmaline occur in high-grade pelitic gneisses from southeastern Ontario, Canada. The kornerupine occurs in quartz-bearing layers associated with biotite, cordierite, garnet, ilmenite, K-feldspar, magnetite, quartz, and, less commonly, sillimanite. Grandidierite is found in quartz-poor, cordierite+sillimanite segregations in contact with biotite, cordierite, ilmenite, K-feldspar, magnetite, sillimanite, and, more rarely, garnet. Tourmaline is sporadically distributed in all compositional layers, but is not in contact with the other borosilicates. There is no textural evidence for a reactive relationship among the three borosilicates. Neither chemical or textural equilibrium has been achieved on the scale of a thin section.It is proposed that the granite, K-feldspar-rich leucosomes, and different borosilicate assemblages in adjacent compositional layers evolved along a path of decreasing pressure and increasing temperature. The P-T path intersected a series of dehydration and melting reactions. This P-T path indicates that uplift had occurred before cooling had started and before the maximum temperature was reached. Corona and symplectite textures developed at various times during uplift both before and after cooling had started.