Humic Ion-Binding Model VI: An Improved Description of the Interactions of Protons and Metal Ions with Humic Substances

Humic Ion-Binding Model VI, a discrete site/electrostatic model of the interactions of protons and metals with fulvic and humic acids, is applied to 19 sets of published data for proton binding, and 110 sets for metal binding. Proton binding is described with a site density, two median intrinsic equilibrium constants, two parameters defining the spread of equilibrium constants around the medians, and an electrostatic constant. Intrinsic equilibrium constants for metal binding are defined by two median constants, log K_MA and log K_MB, which refer to carboxyl and weaker-acid sites respectively, together with a parameter, LK₁, defining the spreads of values around the medians. A further parameter, LK₂, takes account of small numbers of strong binding sites. By considering results from many data sets, a universal average value of LK₁ is obtained, and a correlation established between log K_MB and log K_MA. In addition, a relation between LK₂ and the equilibrium constant for metal-NH₃ complexation is tentatively suggested. As a result, metal-binding data can be fitted by the adjustment of a single parameter, log K_MA. Values of log K_MA are derived for 22 metal species. Model VI accounts for competition and ionic strength effects, and for proton-metal exchange.     

Noble gases in the Allende and Abee meteorites and a gas-rich mineral fraction: investigation by stepwise heating

Noble gases in three meteoritic samples were examined by stepwise heating, in an attempt to relate peaks in the outgassing curves to specific minerals: NeKrXe in Allende (C3V) and an Allende residue insoluble in HF-HCl, and Xe in Abee (E4). In Allende, chromite and carbon contain most of the trapped Ne (²⁰Ne/²²Ne ≈ 8.7) and anomalous Xe enriched in light and heavy isotopes, and release it at ~850°C (bulk meteorite) or 1000°C (residue). Mineral Q, containing most of the trapped Ar, Kr, Xe as well as some Ne (²⁰Ne/²²Ne ≈ 10.4), releases its gases mainly between 1200 and 1600°C, well above the release temperatures of organic polymers (300–500°) or amorphous carbon (800–1000°). The high noble-gas release temperature, ready solubility in oxidizing acids, and correlation with acid-soluble Fe and Cr all point to an inorganic rather than carbonaceous nature of Q.All the radiogenic ¹²⁹Xe is contained in HCl, HF-soluble minerals, and is distributed as follows over the peaks in the release curve: Attend 1000° (75%), 1300° (25%); Abee (data of Hohenberg and Reynolds, 1969) ~850° (15%), 1100° (60%), 1300° (25%). No conclusive identifications of host phases can yet be given; possible candidates are troilite and silicates for Allende, and djerfisherite, troilite and silicates for Abee.Mineral Q strongly absorbs air xenon, and releases some of it only at 800–1000°C. Dilution by air Xe from Q and other minerals may explain why temperature fractions from bulk meteorites often contain less ^124–130Xe for a given enrichment in heavy isotopes than does xenon from etched chromitecarbon samples, although chromite-carbon is the source of the anomalous xenon in either case. Air xenon contamination thus is an important source of error in the derivation of fission xenon spectra.     

Chemical fractionations in meteorites—X. Ureilites

Four ureilites (Dyalpur, Goalpara, Haverö, and Novo Urei) were analyzed by radiochemical neutron activation analysis for Ag, Au, Bi, Br, Cd, Cs, Ge, In, Ir, Ni, Rb, Re, Sb, Se, Te, Tl, and U. An attempt has been made to resolve the data into contributions from the parent ultramafic rock and the injected, carbon- and gas-rich vein material. Interelement correlations, supported by analyses of separated vein material (WANKE et al, 1972), suggest that the vein material is enriched about 10-fold in refractory Ir and Re over moderately volatile Ni and Au, and is low in volatiles except Ge, C, and noble gases. It appears to be a refractory-rich nebular condensate that precipitated carbon by surface catalytic reactions at ˜500K and trapped noble gases but few other volatiles. The closest known analogue is a Cr- and C-rich fraction from the Allende meteorite, highly enriched in heavy noble gases and noble metals. By analogy with Allende, the gas-bearing phase in ureilites may have been an Fe, Cr-sulfide.

The ultramafic rock contains siderophiles and chalcophiles (Ni, Au, Ge, S, Se) at ˜0.05 of Cl chondrite level, and highly volatile elements (Rb, Cs, Bi, Tl, Br, Te, In, Cd) at ˜0.01 Cl level. It probably represents the residue from partial melting of a C3V-like chondrite body, under conditions where phase separation was incomplete so that some liquid was retained. The vein material was injected into this rock at some later time.     

Greatlakean Substage: A replacement for Valderan Substage in the Lake Michigan basin

New evidence from recent field and seismic investigations in the Lake Michigan basin and in the type areas of the Valders, Two Creeks and Two Rivers deposits necessitates revision of late-glacial ice-front positions, rock- and time-stratigraphic nomenclature and climatic interpretations and deglaciation patterns for the period ca. 14,000–7,000 radiocarbon years B.P. The previously reported and long accepted pattern of deglaciation for the Lake Michigan basin started with a regular retreat from the Lake Border Morainic System, with a minor oscillation marked by the Port Huron moraine(s) and then an extensive Twocreekan deglaciation followed by a major (320 km) post-Twocreekan advance (Valders). However, we now record a major retreat between the times of the Lake Border and Port Huron moraines, followed by a gradual retreat from the Port Huron limit and interrupted by a minor standstill (deposition of Manitowoc Till), a retreat (Twocreekan) and a readvance (Two Rivers Till). No Woodfordian or younger readvance was as extensive as had been the preceding one. This sequence argues for a normal, climatically controlled, progressive deglaciation rather than one interrupted by a major post-Twocreekan (formerly Valderan) surge. This revision appears finally to harmonize the geologic evidence and the palynological record for the Great Lakes region. Our investigations show that Valders Till from which the Valderan Substage was named is late-Woodfordian in age. We propose the term “Greatlakean” as a replacement for the now misleading time-stratigraphic term “Valderan”. The type section and the definition of the upper and lower boundaries of the Greatlakean Substage remain the same as those originally proposed for the Valderan Substage but the name is changed.     

A service-based framework for the OAIS model for earth science data management

The Consultative Committee for Space Data Systems (CCSDS), in 2002, released their first version of a Reference Model for an Open Archival Information System (OAIS). In 2003, the model was adopted by the International Standards Organization (ISO) as ISO 14721:2003. The CCSDS document was updated in 2012 with additional focus on verifying the authenticity of data and developing concepts of access rights and a security model. The OAIS model is the basis of research data management systems across institutions and disciplines around the world. The Organization for the Advancement of Structured Information Standards (OASIS), in 2006, released their first version of a Reference Model for Service Oriented Architecture (SOA). OASIS defines the SOA as “a paradigm for organizing and utilizing distributed capabilities that may be under the control of different ownership domains.” Systems designed around the SOA model benefit from improved scalability, flexibility, and agility. This paper applies the SOA model to the OAIS repository to describe how repositories can be implemented and extended through the use of services that may be internal or external to the host institution, including the consumption of network- or cloud-based services and resources. We use the Service Oriented Architecture (SOA) design paradigm to describe a set of potential extensions to OAIS Reference Model: purpose and justification for each extension, where and how each extension connects to the model, and an example of a specific service that meets the purpose.     

The Rock of Gibraltar re‐visited

Gibraltar, a 6km² peninsula jutting south from Spain at the western entrance to the Mediterranean Sea, is dominated by its 424 m‐high Rock: famous as a landmark to seafarers since ancient times. Twenty‐five years ago, an article in Geology Today (1991, v.7, pp.95–101) interpreted the Rock as a partly overturned mass of Early Jurassic dolomitic limestone, thrust into position during continent–continent collision about 15–20 million years before present and shaped finally by shoreline processes active during Quaternary tectonic uplift. Later articles featured the complex of tunnels and chambers excavated between 1782 and 1968 by British military engineers within its 2.6 km‐long main ridge (1992, v.8, pp.92–98), and the Neanderthals known to have used some of its caves (1997, v.13, pp.179–184). Significant aspects of the Rock's geological history have clarified since then.     

具有经济性前景的粗岩屑堆天然冷能集聚分析

The coarse-detrital deposits have the properties of cold accumulation and maintenance of cold for a long time. Now, at some place where the mean annual temperature of air is positive, one even can get the permafrost by artificial formation of the burial mound. According to these properties, some lowenergy storehouses are built for various purposes.     

Sorption of noble gases by solids,with reference to meteorites. III. Sulfides,spinels, and other substances; on the origin of planetary gases

To simulate trapping of noble gases by meteorites, we reacted 15 FeCr or FeCrNi alloy samples with CO, H₂O or H₂S at 350–720 K, in the presence of noble gases. The reaction products, including (Fe,Cr)₂O₃, FeCr₂S₄, FeS, C, and Fe₃C, were analyzed by mass spectrometry, usually after chemical separation by selective solvents. Three carbon samples were prepared by catalytic decomposition of CO or by dehydration of carbohydrates with H₂SO₄.The spinel and carbon samples were similar to those of earlier studies (Yang et al., 1982 and Yang and Anders, 1982), with only minor effects attributable to the presence of Ni. All samples sorted substantial amounts of noble gases, with distribution coefficients of 10^?1–10^?2 cm³ STP/g atm for Xe. On the basis of release temperature three gas components were distinguished: a generally dominant physisorbed component (20–80% of total), and two more strongly bound, chemisorbed and trapped components. Judging from the elemental pattern, the adsorbed components were acquired at the highest noble gas partial pressure encountered by the sample—atmosphere or synthesis vessel.Sulfides, particularly daubréelite, showed three distinctive trends relative to chromite or magnetite: the high-T component was larger, 30–70% of the total; $\text{Ne}\text{Xe}$ ratios were higher, by up to 10², possibly due to preferential diffusion of Ne during synthesis. In one synthesis, at relatively high P, the gases were sorbed with only minimal elemental fractionation, presumably by occlusion.Most of the features of primordial noble gases can be explained in terms of the data and concepts presented in the three papers of this series. The elemental fractionation pattern of Ar, Kr, Xe in meteorites, terrestrial rocks, and planets resembles the adsorption pattern on the solids studied: carbon, spinels, Sulfides, etc. The variation in $\text{Ne}\text{Ar}$ ratio may be explained by preferential diffusion of Ne. The high release temperature of meteoritic noble gases may be explained by transformation of physisorbed to chemisorbed gas, as observed in some experiments. The ready loss of meteoritic heavy gases on surficial oxidation (“Phase Q”) is consistent with adsorption, as is the high abundance. Extrapolation of the limited laboratory data suggests that the observed amounts of noble gases could have been adsorbed from a solar gas at 160–170 K and 10^?6–10^?5 atm, i.e. in the early contraction stages of the solar nebula. The principal unsolved problem is the origin of isotopically anomalous, apparently mass-fractionated noble gases in the Earth's atmosphere and in meteoritic carbon and chromite.     

Amino-acid racemizarion in Quaternary shell deposits at Willapa Bay,Washington

Extents of racemization ($\text{d}\text{l}$ ratios) of amino acids in fossil Saxidomus giganteus (Deshayes) and Ostrea lurida Carpenter were measured on shell deposits exposed at 21 sites on the east side of Willapa Bay, Washington. Amino acids from Saxidomus show less variability in $\text{d}\text{Spl}$ ratios and, therefore, are of greater use in correlation and age estimation than are amino acids from Ostrea. Shells of two different ages, about 120,000 ± 40,000 yr old and about 190,000 ± 40,000 yr old, are present. These ages correspond to Stages 5 and 7 of the marine isotope record defined by Shackleton and Opdyke in 1973 and hence the shell deposits likely formed during two different high stands of sea level. The stratigraphic record at Willapa Bay is consistent with this interpretation.