Activity–composition relations for phases in petrological calculations: an asymmetric multicomponent formulation

For petrological calculations, including geothermobarometry and the calculation of phase diagrams (for example, P–T petrogenetic grids and pseudosections), it is necessary to be able to express the activity–composition (a–x) relations of minerals, melt and fluid in multicomponent systems. Although the symmetric formalism—a macroscopic regular model approach to a–x relations—is an easy-to-formulate, general way of doing this, the energetic relationships are a symmetric function of composition. We allow asymmetric energetics to be accommodated via a simple extension to the symmetric formalism which turns it into a macroscopic van Laar formulation. We term this the asymmetric formalism (ASF). In the symmetric formalism, the a–x relations are specified by an interaction energy for each of the constituent binaries amongst the independent set of end members used to represent the phase. In the asymmetric formalism, there is additionally a "size parameter" for each of the end members in the independent set, with size parameter differences between end members accounting for asymmetry. In the case of fluid mixtures, for example, H₂O–CO₂, the volumes of the end members as a function of pressure and temperature serve as the size parameters, providing an excellent fit to the a–x relations. In the case of minerals and silicate liquid, the size parameters are empirical parameters to be determined along with the interaction energies as part of the calibration of the a–x relations. In this way, we determine the a–x relations for feldspars in the systems KAlSi₃O₈–NaAlSi₃O₈ and KAlSi₃O₈–NaAlSi₃O₈–CaAl₂Si₂O₈, for carbonates in the system CaCO₃–MgCO₃, for melt in the melting relationships involving forsterite, protoenstatite and cristobalite in the system Mg₂SiO₄–SiO₂, as well as for fluids in the system H₂O–CO₂. In each case the a–x relations allow the corresponding, experimentally determined phase diagrams to be reproduced faithfully. The asymmetric formalism provides a powerful and flexible way of handling a–x relations of complex phases in multicomponent systems for petrological calculations.     

Surface complexation modeling for predicting solid phase arsenic concentrations in the sediments of the Mississippi River Valley alluvial aquifer, Arkansas, USA

The potential health impact of As in drinking water supply systems in the Mississippi River Valley alluvial aquifer in the state of Arkansas, USA is significant. In this context it is important to understand the occurrence, distribution and mobilization of As in the Mississippi River Valley alluvial aquifer. Application of surface complexation models (SCMs) to predict the sorption behavior of As and hydrous Fe oxides (HFO) in the laboratory has increased in the last decade. However, the application of SCMs to predict the sorption of As in natural sediments has not often been reported, and such applications are greatly constrained by the lack of site-specific model parameters. Attempts have been made to use SCMs considering a component additivity (CA) approach which accounts for relative abundances of pure phases in natural sediments, followed by the addition of SCM parameters individually for each phase. Although few reliable and internally consistent sorption databases related to HFO exist, the use of SCMs using laboratory-derived sorption databases to predict the mobility of As in natural sediments has increased. This study is an attempt to evaluate the ability of the SCMs using the geochemical code PHREEQC to predict solid phase As in the sediments of the Mississippi River Valley alluvial aquifer in Arkansas. The SCM option of the double-layer model (DLM) was simulated using ferrihydrite and goethite as sorbents quantified from chemical extractions, calculated surface-site densities, published surface properties, and published laboratory-derived sorption constants for the sorbents. The model results are satisfactory for shallow wells (10.6 m below ground surface), where the redox condition is relatively oxic or mildly suboxic. However, for the deep alluvial aquifer (21-36.6 m below ground surface) where the redox condition is suboxic to anoxic, the model results are unsatisfactory.     

Trace metals and radionuclides reveal sediment sources and accumulation rates in Jordan Cove, Connecticut

Many small estuaries are influenced by flow restrictions resulting from transportation rights-of-way and other causes. The biogeochemical functioning and history of such systems can be evaluated through study of their sediments. Ten long and six short cores were collected from the length of Jordan Cove, Connecticut, a Long Island Sound subestuary, and analyzed for stratigraphy, radionuclides (¹⁴C, ²¹⁰Pb, ²²⁶Ra, ¹³⁷Cs, and ⁶⁰Co), and metals (Ag, Cd, Cu, Pb, Zn, Fe, and Al). For at least 3,800 yr, rising sea level has gradually inundated Jordan Cove, filling it with mud similar to that currently being deposited there. Long-term sediment accumulation in the cove averaged close to 0.1 cm yr⁻¹ over the last three millennia. Recent sediment accumulation rates decrease inland from 0.84 cm yr⁻¹ to 0.40 cm yr⁻¹, and are slightly faster than relative sea-level rise at this site (0.3 cm yr⁻¹). Similarity of depth distributions of trace metals was used to confirm relative sediment accumulation rates. ⁶⁰Co and Ag are derived from sources outside the cove and its watershed, presumably the Millstone nuclear power plant and regional contaminated sediments, respectively. The combined data suggest that Long Island Sound is an important source of sediment to the cove; a minor part of total sediment is supplied from the local watershed. Trace metal levels are strongly correlated with Fe but not with either organic matter or Al. Sediment quality has declined in the cove over the past 60 yr, but only slightly. Cu, Pb, and Zn data correlate strongly with Fe but not with either organic matter or aluminum. Ratios of Ag to Fe and to trace metals suggest that Ag in the cove is derived almost entirely from Long Island Sound. This result supports the notion that Fenormalized Ag can serve as a better tracer of some kinds of contamination than more common and abundant metals, like Cu, Pb, and Zn. *** DIRECT SUPPORT *** A01BY085 00008     

Seasonal and Sub-Seasonal Circulation Anomalies Associated with Persistent Rainy Days in 2018/2019 Winter in Shanghai,China

Shanghai experienced the longest rainy days in 2018/2019 winter since 1988. The physical cause of such an unusual climate condition was investigated through the diagnosis of observational data. From a seasonal perspective, a long persistent rainy winter was often associated with an El Niño condition in the equatorial Pacific. This abnormal oceanic condition induces a remote teleconnection pattern with pronounced low-level southerly anomalies over East China. The wind anomalies transported moisture from tropical oceans and caused persistent rainfall in East Asia. Meanwhile, the local rainfall time series exhibited a strong quasi-biweekly oscillation (QBWO). Three persistent rainy events were identified in the 2018/2019 winter and they all occurred during the active phase of the QBWO. The first two events were associated with a low pressure anomaly west of Shanghai. Southerly anomalies associated with the low pressure system advected high mean moisture into central eastern China, leading to the persistent rainfall there. The third event was associated with a high pressure anomaly in lower troposphere to the east of Shanghai, which induced anomalous southerlies to its west, favoring the occurrence of rainfall in Shanghai. The result suggests the importance of high-frequency variability in affecting seasonal rainfall anomalies.     

Calculated mineral equilibria in the greenschist-blueschist-eclogite facies in Na2O−FeO−MgO−Al2O3−SiO2−H2O

The new, greatly expanded internally-consistent dataset of Holland and Powell includes thermodynamic data for a wide range of mineral end-members in common rock-forming minerals, in particular, including FeMg_-1 substitutions in glaucophane, garnet, chloritoid and carpholite, and FeMg_-1 and MgSiAl_-1Al_-1 substitutions in talc and chlorite. Moreover, we have the uncertainties and correlations for these data. With the data, we have calculated the full pressure-temperature phase diagram for the system Na₂O–FeO–MgO–Al₂O₃–SiO₂–H₂O (NFMASH) for quartz (or coesite) and H₂O in excess, in the range 300°–800°C and 5–50 kbars. By solving the set of non-linear equations formed by the equilibrium relationships for an independent set of equations between the end-members in an assemblage in NFMASH, the compositions of the minerals (and PT) can be calculated. Thus the changes in MgSiAl_-1Al_-1 along NMASH reactions, and FeSiAl_-1Al_-1 along NFASH reactions, are calculated, and the changes in FeMg_-1 and MgSiAl_-1Al_-1 along NFMASH reactions are calculated. From this information it is straightforward to generate PT diagrams for specific rock compositions. Mineral assemblages and mineral compositional changes in the phase diagram are discussed in relation to greenschist, blueschist and eclogite facies assemblages in metapelitic rocks. It is found that the correspondence between the predictions of the phase diagrams and the observations on rocks is remarkably good. When semiquantitative extensions of the phase diagram to include Ca(MgFe)_-1, NaSiCa_-1Al_-1, Fe³⁺Al_-1 and KNa_-1 substitutions are taken into account the agreement is essentially complete.     

Australian ‘gayborhoods’ and ‘lesborhoods’: a new method for estimating the number and prevalence of adult gay men and lesbian women living in each Australian postcode

ABSTRACT

Gay men and lesbian women often demonstrate unique settlement patterns, forming what have been referred to as ‘gayborhoods’. This study sought to provide the first postcode-level estimates of population size and prevalence of gay and lesbian people in Australia. Data on same-gender-partnered households from the Australian Census were combined with information from six different surveys conducted from 2011 to 2017. We estimated that in 2016 there were 132,203 gay men (1.5% of adult males; 95% CI: 1.4–1.6) and 79,931 lesbian women (0.9% of adult females; 95% CI: 0.8–1.0) in Australia. While many postcodes were sparsely populated by gay and lesbian people (40.1% had prevalences of <0.1%), 24.6% were moderately populated (prevalences in the 50-95th percentile) and 2.7% were highly populated (95th percentile). By jurisdiction, the Australian Capital Territory had the highest prevalences of gay men (2.1%; 95% CI: 2.0–2.2) and lesbian women (1.5%; 95% CI: 1.4–1.6). Although the majority of highly populated postcodes were found in major cities (83.7%), some were also found in regional and remote area (16.3%). This method can be applied in other countries to enhance populate estimates. The accompanying dataset can be used to guide service delivery, conduct geographically contextualised research and develop policies relevant to gay men and lesbian women in Australia.     

Detrital record of Mesozoic shortening in the Yanshan belt, NE China: testing structural interpretations with basin analysis

The Yanshan fold‐thrust belt is an exposed portion of a major Mesozoic orogenic system that lies north of Beijing in northeast China. Structures and strata within the Yanshan record a complex history of thrust faulting characterized by multiple deformational events. Initially, Triassic thrusting led to the erosion of a thick sequence of Proterozoic and Palaeozoic sedimentary strata from northern reaches of the thrust belt; Triassic–Lower Jurassic strata that record this episode are deposited in a thin belt south of this zone of erosion. This was followed by postulated Late Jurassic emplacement of a major allochthon (the Chengde thrust plate), which is thought to have overridden structures and strata associated with the Triassic event and is cut by two younger thrusts (the Gubeikou and Chengde County thrusts). The Chengde allochthon is now expressed as a major east–west trending, thrust‐bounded synform (the Chengde synform), which has been interpreted as a folded klippe 20 km wide underlain by a single, north‐vergent thrust fault. Two sedimentary basins, defined on the basis of provenance, geochronology and palaeodispersal trends, developed within the Yanshan belt during Late Jurassic–Early Cretaceous time and are closely associated with the Chengde thrust and allied structures. Shouwangfen basin developed in the footwall of the Gubeikou thrust and records syntectonic unroofing of the hanging wall of that fault. Chengde basin developed in part atop Proterozoic strata interpreted as the upper plate of the Chengde allochthon and records unroofing of the adjacent Chengde County thrust. Both the Chengde County thrust and the Gubeikou thrust are younger than emplacement of the postulated Chengde allochthon, and structurally underlie it, yet neither Shouwangfen basin nor Chengde basin contain a detrital record of the erosion of this overlying structure. In addition, facies, palaeodispersal patterns and geochronology of Upper Jurassic strata that are cut by the Chengde thrust suggest only limited (ca. 5 km) displacement along this fault. We suggest that the units forming the Chengde synform are autochthonous, and that the synform is bounded by two limited‐displacement faults of opposing north and south vergence, rather than a single large north‐directed thrust. This conclusion implies that the Yanshan belt experienced far less Late Jurassic shortening than was previously thought, and has major implications for the Mesozoic evolution of the region. Specifically, we argue that the bulk of shortening and uplift in the Yanshan belt was accomplished during Triassic–Early Jurassic time, and that Late Jurassic structures modified and locally ponded sediments from a well‐developed southward drainage system developed atop this older orogen. Although Upper Jurassic strata are widespread throughout the Yanshan belt, it is clear that these strata developed within several discrete intermontane basins that are not correlable across the belt as a single entity. Thus, the Yanshan has no obvious associated foreland basin, and determining where the Mesozoic erosional products of this orogen ultimately lie is one of the more intriguing unresolved questions surrounding the palaeogeography of North China.     

Another Year of Record Heat for the Oceans

Changes in ocean heat content(OHC), salinity, and stratification provide critical indicators for changes in Earth’s energy and water cycles. These cycles have been profoundly altered due to the emission of greenhouse gasses and other anthropogenic substances by human activities, driving pervasive changes in Earth’s climate system. In 2022, the world’s oceans, as given by OHC, were again the hottest in the historical record and exceeded the previous 2021 record maximum.According to IAP/CAS data, ...