Gaseous mercury emissions from urban surfaces: Controls and spatiotemporal trends

The spatial and temporal variability of Hg emissions from urban paved surfaces was assessed through repeated measurements under varying environmental conditions at six sample sites in Toronto, Ontario, Canada. The results show significant spatial variability of the Hg emissions with median values ranging from below detection limit to 5.2 ng/m²/h. Two of the sites consistently had higher Hg emissions (on several occasions >20 ng/m²/h) than the other 4, which were equivalently low (maximum emission: 2.1 ng/m²/h). A surrogate measure of the pavement Hg concentrations was obtained during each day of sampling through the collection of street dust. The median street dust concentration also showed significant spatial variability (ranging from 9.6 to 44.5 ng/g). Regression analysis showed that the spatial variability of the Hg emissions was significantly related to the street dust concentrations. Controlled experiments using Hg amended street dust confirmed the relationship between Hg surface concentration and emission magnitude. Within a given sample site, Hg emissions varied temporally and multiple regression analysis showed that within-site variability was significantly influenced by changes in solar radiation with only a minor effect from surface temperature. Controlled experiments using shade cloths confirmed that solar radiation can have a large influence on the magnitude of Hg emissions within a given site. The emissions measured in Toronto were contextualized through comparison sampling in Austin, Texas. The Hg emissions measured in Austin were within the range detected in Toronto and also showed significant correlation with Hg street dust concentrations between sites. To provide a holistic assessment of Hg emissions from urban environments, samples were also collected from other common urban surfaces (soil, roofs, and windows). Soils consistently had higher emissions than all the other surfaces (7.3 ng/m²/h, n = 39).     

Recent progress on combining geomorphological and geochronological data with ice sheet modelling,demonstrated using the last British–Irish Ice Sheet

Palaeo-ice sheets are important analogues for understanding contemporary ice sheets, offering a record of ice sheet behaviour that spans millennia. There are two main approaches to reconstructing palaeo-ice sheets. Empirical reconstructions use the available glacial geological and chronological evidence to estimate ice sheet extent and dynamics but lack direct consideration of ice physics. In contrast, numerically modelled simulations implement ice physics, but often lack direct quantitative comparison with empirical evidence. Despite being long identified as a fruitful scientific endeavour, few ice sheet reconstructions attempt to reconcile the empirical and model-based approaches. To achieve this goal, model-data comparison procedures are required. Here, we compare three numerically modelled simulations of the former British–Irish Ice Sheet with the following lines of evidence: (a) position and shape of former margin positions, recorded by moraines; (b) former ice-flow direction and flow-switching, recorded by flowsets of subglacial bedforms; and (c) the timing of ice-free conditions, recorded by geochronological data. These model–data comparisons provide a useful framework for quantifying the degree of fit between numerical model simulations and empirical constraints. Such tools are vital for reconciling numerical modelling and empirical evidence, the combination of which will lead to more robust palaeo-ice sheet reconstructions with greater explicative and ultimately predictive power.     

Multi‐scale stratigraphic forward modelling of the Surat Basin for geological storage of CO2

Underground geological storage of CO₂ (GSC) requires a high level of subsurface understanding that is often hindered by a lack of data. This study demonstrates the use of stratigraphic forward modelling (SFM) in generating and characterising a static reservoir model using limited well data, with multiple potential applications within the GSC workflow. Sedsim SFM software was used to create a static model of the Surat Basin, including a high‐resolution nested model of the EPQ‐7 GSC tenement within the basin. Deposition and burial of the Jurassic Precipice Sandstone, Evergreen Formation and Hutton Sandstone were simulated. Modelling results show a close match with gamma‐ray well logs in the tenement area, and the model can be considered a credible model of the subsurface. The Sedsim‐predicted formation thicknesses and porosity and permeability distributions meet criteria set for GSC, suggesting that the EPQ‐7 tenement may be a prospective GSC location.     

Ca isotope cycling in a forested ecosystem

Reports of large Ca isotope fractionations between trees and soils prompted this study of a Boreal forest ecosystem near La Ronge, Saskatchewan, to improve understanding of this phenomenon. The results on five tree species (black spruce, trembling aspen, white spruce, jack pine, balsam poplar) confirm that nutrient Ca uptake by plants favors the light isotopes, thus driving residual Ca in plant available soil pools towards enrichment in the heavy isotopes. Substantial within-tree fraction occurs in tissues formed along the transpiration stream, with low δ⁴⁴Ca values in fine roots (2 mm), intermediate values in stemwood, and high values in foliage. Separation factors between different plant tissues are similar between species, but the initial fractionation step in the tips of the fine roots is species specific, and/or sensitive to the local soil environment. Soil water δ⁴⁴Ca values appear to increase with depth to at least 35 cm below the top of the forest floor, which is close to the deepest level of fine roots. The heavy plant fractionated signature of Ca in the finely rooted upper soils filters downward where it is retained on ion exchange sites, leached into groundwater, and discharged into surface waters.The relationship between Ca uptake by tree fine roots and the pattern of δ⁴⁴Ca enrichment with soil depth was modeled for two Ca pools: the forest floor (litter) and the underlying (upper B) mineral soil. Six study plots were investigated along two hillside toposequences trending upwards from a first order stream. We used allometric equations describing the Ca distribution in boreal tree species to calculate weighted average δ⁴⁴Ca values for the stands in each plot and estimate Ca uptake rates. The δ⁴⁴Ca value of precipitation was measured, and soil weathering signatures deduced, by acid leaching of lower B mineral soils. Steady state equations were used to derive a set of model Ca fluxes and fractionation factors for each plot. The model reproduces the increase in δ⁴⁴Ca with depth found in forest floor and upper B soil waters. Transient model runs show that the forest Ca cycle is sensitive to changes in plant Ca uptake rate, such as would occur during ontogeny or disturbance. Accordingly, secular records of δ⁴⁴Ca in tree ring cellulose have the potential to monitor changes in the forest Ca cycle through time, thus providing a new tool for evaluating natural and anthropogenic impacts on forest health. Another model run shows that by changing the size of the isotope fractionation factor and adjusting for differences in forest productivity, that the range in Ca isotope fractionation in forested ecosystems reported in the literature, thus far, is reproduced. As a quantitative tool, the Ca cycling model produces a reasonable set of relative Ca fluxes for the La Ronge site, consistent with Environment Canada’s measurements for wet deposition in the region and simulated Ca release from soil mineral weathering using the PROFILE model. But the sensitivity of the model is limited by the small range of fractionation observed in this boreal shield setting of ∼1‰, which limits accuracy. If the model were applied to a site with a greater range in δ⁴⁴Ca values among the principal Ca fluxes, it is capable of producing robust and reliable estimations of Ca fluxes that are otherwise difficult to measure in forested ecosystems.     

Testing the fidelity of thermometers at ultrahigh temperatures

A highly residual granulite facies rock (sample RG07‐21) from Lunnyj Island in the Rauer Group, East Antarctica, presents an opportunity to compare different approaches to constraining peak temperature in high‐grade metamorphic rocks. Sample RG07‐21 is a coarse‐grained pelitic migmatite composed of abundant garnet and orthopyroxene along with quartz, biotite, cordierite, and plagioclase with accessory rutile, ilmenite, zircon, and monazite. The inferred sequence of mineral growth is consistent with a clockwise pressure–temperature (P–T) evolution when compared with a forward model (P–T pseudosection) for the whole‐rock chemical composition. Peak metamorphic conditions are estimated at 9 ± 0.5 kbar and 910 ± 50°C based on conventional Al‐in‐orthopyroxene thermobarometry, Zr‐in‐rutile thermometry, and calculated compositional isopleths. U–Pb ages from zircon rims and neocrystallized monazite grains yield ages of c. 514 Ma, suggesting that crystallization of both minerals occurred towards the end of the youngest pervasive metamorphic episode in the region known as the Prydz Tectonic Event. The rare earth element compositions of zircon and garnet are consistent with equilibrium growth of these minerals in the presence of melt. When comparing the thermometry methods used in this study, it is apparent that the Al‐in‐orthopyroxene thermobarometer provides the most reliable estimate of peak conditions. There is a strong textural correlation between the temperatures obtained using the Zr‐in‐rutile thermometer––maximum temperatures are recorded by a single rutile grain included within orthopyroxene, whereas other grains included in garnet, orthopyroxene, quartz, and biotite yield a range of temperatures down to 820°C. Ti‐in‐zircon thermometry returns significantly lower temperature estimates of 678–841°C. Estimates at the upper end of this range are consistent with growth of zircon from crystallizing melt at temperatures close to the elevated (H₂O undersaturated) solidus. Those estimates, significantly lower than the calculated temperature of this residual solidus, may reflect isolation of rutile from the effective equilibration volume leading to an activity of TiO₂ that is lower than the assumed value of unity.     

Titanite dates crystallization: Slow Pb diffusion during super‐solidus re‐equilibration

Titanite can be found in rocks of wide compositional range, is reactive, growing or regrowing during metamorphic and hydrothermal events, and is generally amenable to U–Pb geochronology. Experimental evidence suggest that titanite has a closure temperature for Pb ranging from 550 to 650°C, and thus titanite dates are commonly interpreted as cooling ages. However, this view has been challenged in recent years by evidence from natural titanite which suggests the closure temperature may be significantly higher (up to 800°C). Here, we investigate titanite in an enclave of migmatitic gneiss included within a granite intrusion. The titanite crystals exhibit textural features characteristic of fluid‐mediated mass transfer processes on length scales of <100 µm. These textural features are associated with variation in both Pb concentrations and distinct U–Pb isotopic compositions. Zr‐in‐titanite thermometry indicates that modification of the titanite occurred at temperatures in excess of 840°C, in the presence of a high‐T silicate melt. The Pb concentration gradients preserved in these titanite crystals are used to determine the diffusivity of Pb in titanite under high‐T conditions. We estimate diffusivities ranging from 2 × 10^?22 to 5 × 10^?25 m²/s. These results are significantly lower than experimental data predict yet are consistent with other empirical data on natural titanites, suggesting that Pb diffusivity is similar to that of Sr. Thus our data challenge the wide‐held assumption that U–Pb titanite dates only reflect cooling ages.     

Automated AF-demagnetization on the 2G-Enterprises through-bore,cryogenic magnetometer

Since the early sixties, alternating field demagnetization (AFD) has been a standard laboratory technique for demagnetizing rocks to expose the multicomponent structure of their natural remanent magnetization (NRM). In the majority of AFD implementations, however, the procedure remains as labour-intensive as ever. The implementation that we have developed at the Australian Geological Survey Organisation, automates the procedure for AFD based on the static method, and results in significant productivity and efficiency gains without compromising data quality. A properly formulated procedure for static AFD may be the only method of retrieving higher-coercivity components of natural remanence in samples prone to developing gyroremanence at higher alternating fields (AFs). Our AFD environment comprises: a 2G-Enterprises through-bore, cryogenic magnetometer; 2G AF-coils and control equipment; and personal computer software, developed by us, to control all procedural aspects for a complete AFD of a sample including, importantly, a counteracting procedure to neutralize the effects of gyroremanence build-up at higher AFs. With our system, AFD of 8 samples/day, each of 20+ steps, requires only 20 min of user attention compared with a full day for conventional systems.