Heather Handley

Amphibole “sponge” in arc crust?

Pressure-temperature-time paths followed by arc magmas ascending through the lithosphere dictate the phase assemblage that crystallizes, and hence the compositions of liquid fractionates. Here we use La/Yb and Dy/Yb versus SiO 2 relationships from selected volcanoes to show that amphibole is an important mineral during differentiation of arc magma. Production of intermediate and silicic arc magmas occurs as magmas stall and cool in the mid-lower crust, where amphibole is stable. Because amphibole is rarely a phenocryst phase, we term this “cryptic amphibole fractionation.” If this process is as widespread as our investigation suggests, then (1) amphibole cumulates may act as an effective filter for water dissolved in mantle-derived magmas; (2) amphibole cumulates may act as a fertile source of intracrustal melts and fluids; and (3) recycling of amphibole cumulates has the potential to return incompatible trace elements and water to the mantle.

Mantle flow, volatiles, slab-surface temperatures and melting dynamics in the north Tonga arc―Lau back-arc basin

The Fonualei Spreading Center affords an excellent opportunity to evaluate geochemical changes with increasing depth to the slab in the Lau back-arc basin. We present H2O and CO2concentrations and Sr, Nd, Pb, Hf and U-Th-Ra isotope data for selected glasses as well as new Hf isotope data from boninites and seamounts to the north of the Tonga arc. The Pb and Hf isotope data are used to show that mantle flow is oriented to the southwest and that the tear in the northern end of the slab may not extend east as far as the boninite locality. Along the Fonualei Spreading Center, key geochemical parameters change smoothly with increasing distance from the arc front and increasing slab surface temperatures. The latter may range from 720 to 866°C, based on decreasing H2O/Ce ratios. Consistent with experimental data, the geochemical trends are interpreted to reflect changes in the amount and composition of wet pelite melts or super-critical fluids and aqueous fluids derived from the slab. With one exception, all of the lavas preserve both238U excesses and 226Ra excesses. We suggest that lavas from the Fonualei Spreading Center and Valu Fa Ridge are dominated by fluid-fluxed melting whereas those from the East and Central Lau Spreading Centers, where slab surface temperatures exceed ∼850–900°C, are largely derived through decompression. A similar observation is found for the Manus and East Scotia back-arc basins and may reflect the expiry of a key phase such as lawsonite in the subducted basaltic crust.

Insights into the Galápagos plume from uranium‐series isotopes of recently erupted basalts

Uranium-series isotopes (238U-230Th-226Ra-210Pb), major element, trace element, and Sr-Nd isotopic data are presented for recent (<60 years old) Galapagos archipelago basalts. Volcanic rocks from all centers studied (Fernandina, Cerro Azul, Sierra Negra, and Wolf Volcano) display 230Th excesses (4%–15%) and steep rare earth element (REE) patterns indicative of residual garnet during partial melting of their mantle source. Rare earth element modeling suggests that only a few percent of garnet is involved. Correlations between (238U/232Th), radiogenic isotopes and Nb/Zr ratio suggest that the U/Th ratio of these Galapagos volcanic rocks is primarily controlled by geochemical source variations and not fractionation during partial melting. The lowest (230Th/238U) ratio is not observed at Fernandina (the supposed center of the plume) but at the more geochemically “depleted” Wolf Volcano, further to the north. Small radium excesses are observed for all samples with (226Ra/230Th) ranging from 1.107 to 1.614. The 226Ra-230Th disequilibria do not correlate with other uranium-series parent-daughter nuclide pairs or geochemical data, suggesting modification at shallow levels on timescales relevant to the half-life of 226Ra (1600 years). The combination of 226Ra and 210Pb excesses is inconsistent with interaction of magma with cumulate material unless decoupling of 210Pb (or an intermediate daughter, such as 222Rn) occurs prior to modification of Ra-Th disequilibria. An intriguing correlation of (210Pb/226Ra)0 with Nb/Zr and radiogenic isotopes requires further investigation but suggests possible control via magmatic degassing and accumulation that may somehow be related to source heterogeneities.

Widespread copper and lead contamination of household drinking water, New South Wales, Australia

This study examines arsenic, copper, lead and manganese drinking water contamination at the domestic consumers kitchen tap in homes of New South Wales, Australia. Analysis of 212 first draw drinking water samples shows that almost 100% and 56% of samples contain detectable concentrations of copper and lead, respectively. Of these detectable concentrations, copper exceeds Australian Drinking Water Guidelines (ADWG) in 5% of samples and lead in 8%. By contrast, no samples contained arsenic and manganese water concentrations in excess of the ADWG. Analysis of household plumbing fittings (taps and connecting pipework) show that these are a significant source of drinking water lead contamination. Water lead concentrations derived for plumbing components range from 108µg/L to 1440µg/L (n=28, mean - 328µg/L, median - 225µg/L). Analysis of kitchen tap fittings demonstrates these are a primary source of drinking water lead contamination (n=9, mean - 63.4µg/L, median - 59.0µg/L). The results of this study demonstrate that along with other potential sources of contamination in households, plumbing products that contain detectable lead up to 2.84% are contributing to contamination of household drinking water. Given that both copper and lead are known to cause significant health detriments, products for use in contact with drinking water should be manufactured free from copper and lead.

Assessment of a sequential phase extraction procedure for uranium-series isotope analysis of soils and sediments

The study of uranium-series (U-series) isotopes in soil and sediment materials has been proposed to quantify rates and timescales of soil production and sediment transport. Previous works have studied bulk soil or sediment material, which is a complex assemblage of primary and secondary minerals and organic compounds. However, the approach relies on the fractionation between U-series isotopes in primary minerals since they were liberated from the parent rock via weathering. In addition, secondary minerals and organic compounds have their own isotopic compositions such that the composition of the bulk material may not reflect that of primary minerals. Hence, there is a need for a sample preparation procedure that allows the isolation of primary minerals in soil or fluvial sediment samples. In this study, a sequential extraction procedure to separate primary minerals from soils and sediments was assessed. The procedure was applied to standard rock sample powders (TML-3 and BCR-2) to test whether it introduced any artefactual radioactive disequilibrium. A new step was introduced to remove the clay-sized fraction (<2 µm). Significant amounts (5-14%) of U and Th were removed from the rock standards during the procedure. No significant alteration in ((234)U/(238)U) and ((230)Th/(238)U) activity ratios of the rock standards occurred during the procedure. Aliquots of soil sample were subjected to the sequential extraction process to test how each step modifies the uranium-series activity ratios and mineralogy. Although no secondary minerals were detected in the unleached soil aliquots, the sequential leaching process removed up to 17% of U and Th and modified their activity ratios by up to 3%. The modification of the activity ratios poses a demand for careful means to avoid redistribution of isotopes back to the residual phase during phase extraction.

Australian atmospheric lead deposition reconstructed using lead concentrations and isotopic compositions of archival lichen and fungi.

Lead concentrations and their isotopic compositions were measured in lichen genera Cladonia and Usnea and fungi genus Trametes from the Greater Sydney region (New South Wales, Australia) that had been collected and archived over the past 120 years. The median lead contents were elevated in lichens and fungi prior to the introduction of leaded petrol (Cladonia 12.5 mg/kg; Usnea 15.6 mg/kg; Trametes 1.85 mg/kg) corresponding to early industrial development. During the use of leaded petrol for automobiles in Australia from 1932 to 2002, total median lead concentrations rose: Cladonia 18.8 mg/kg; Usnea 21.5 mg/kg; Trametes 4.3 mg/kg. Following the cessation of leaded petrol use, median total lead concentrations decreased sharply in the 2000s: Cladonia 4.8 mg/kg; Usnea 1.7 mg/kg. The lichen and fungi isotopic compositions reveal a significant decrease in (206)Pb/(207)Pb values from the end of 19th century to the 1970s. The following decades were characterised by lower allowable levels of lead additive in fuel and the introduction of unleaded petrol in 1985. The environmental response to these regulatory changes was that lichen and fungi (206)Pb/(207)Pb values increased, particularly from 1995 onwards. Although the lead isotope ratios of lichens continued to increase in the 2000s they do not return to pre-leaded petrol values. This demonstrates that historic leaded petrol emissions, inter alia other sources, remain a persistent source of anthropogenic contamination in the Greater Sydney region.

Geochemical sources, forms and phases of soil contamination in an industrial city

This study examines current soil contamination in an Australian industrial city, Newcastle. Public (roadside verges and parks) and private (homes) surface soils (n=170) contained metal(loid)s elevated above their respective Australian Health Investigation Levels (HIL). Lead (Pb), the most common contaminant in the city, exceeds the HIL for residential soils (HIL-A, 300mg/kg) in 88% of private soils (median: 1140mg/kg). In-vitro Pb bio-accessibility analysis of selected soils (n=11) using simulated gastric fluid showed a high affinity for Pb solubilisation (maximum Pb concentration: 5190mg/kg, equating to 45% Pb bio-accessibility). Highly soluble Pb-laden Fe- and Mn-oxides likely contribute to the bio-accessibility of the Pb. Public and private space surface soils contain substantially less radiogenic Pb (range: 208Pb/207Pb: 2.345-2.411, 206Pb/207Pb: 1.068-1.312) than local background soil (208Pb/207Pb: 2.489, 206Pb/207Pb: 1.198), indicating anthropogenic contamination from the less radiogenic Broken Hill type Pb ores (208Pb/207Pb: 2.319, 206Pb/207Pb: 1.044). Source apportionment using Pb isotopic ratio quantification and soil mineralogy indicate the citys historic copper and steel industries contributed the majority of the soil contaminants through atmospheric deposition and use of slag waste as fill material. High-temperature silicates and oxides combined with rounded particles in the soil are characteristic of smelter dust emissions. Additionally, a preliminary investigation of polycyclic aromatic hydrocarbons in soils, sometimes associated with ferrous metal smelting, coal processing or burning of fossil fuels, shows that these too pose a health exposure risk (calculated in comparison to benzo(a)pyrene: n=12, max: 13.5mg/kg, HIL: 3mg/kg).

A geochemical approach to distinguishing competing tectono-magmatic processes preserved in small eruptive centres

Small eruptive centres (SECs) representing short-lived, isolated eruptions are effective samples of mantle heterogeneity over a given area, as they are generally of basaltic composition and show evidence of little magmatic processing. This is particularly powerful in volcanic arcs where the original melting process generating stratovolcanoes is often obscured by additions from the down-going slab (fluids and sediments) and the overlying crust. The Pucón area of southern Chile contains active and dormant stratovolcanoes, Holocene, basaltic SECs and an arc-scale strike-slip fault (the Liquiñe Ofqui Fault System: LOFS). The SECs show unexpected compositional heterogeneity considering their spatial proximity. We present a detailed study of these SECs combining whole rock major and trace element concentrations, U-Th isotopes and olivine-hosted melt inclusion major element and volatile contents to highlight the complex inter-relations in this small but active area. We show that heterogeneity preserved at individual SECs relates to different processes: some start in the melting region with the input of slab-derived fluids, whilst others occur later in a centre’s magmatic history with the influence of crustal contamination prior to olivine crystallisation. These signals are deduced through the combination of the different geochemical tools used in this study. We show that there is no correlation between composition and distance from the arc front, whilst the local tectonic regime has an effect on melt composition: SECs aligned along the LOFS have either equilibrium U-Th ratios or small Th-excesses instead of the large—fluid influenced—U-excesses displayed by SECs situated away from this feature. One of the SECs is modelled as being generated from fluid-enriched depleted mantle, a source which it may share with the stratovolcano Villarrica, whilst another SEC with abundant evidence of crustal contamination may share its plumbing system with its neighbouring stratovolcano Quetrupillán, showing that polygenetic–monogenetic connections are unpredictable. Such marked preservation of individual magmatic histories highlights the isolation of individual melting events even in complex and highly volcanically active areas.

210Pb-226Ra disequilibria in young gas-laden magmas

We present new 238U-230Th-226Ra-210Pb and supporting data for young lavas from southwest Pacific island arcs, Eyjafjallajökull, Iceland, and Terceira, Azores. The arc lavas have significant 238U and 226Ra excesses, whereas those from the ocean islands have moderate 230Th and 226Ra excesses, reflecting mantle melting in the presence of a water-rich fluid in the former and mantle melting by decompression in the latter. Differentiation to erupted compositions in both settings appears to have taken no longer than a few millennia. Variations in the (210Pb/226Ra)0 values in all settings largely result from degassing processes rather than mineral-melt partitioning. Like most other ocean island basalts, the Terceira basalt has a 210Pb deficit, which we attribute to ~8.5 years of steady 222Rn loss to a CO2-rich volatile phase while it traversed the crust. Lavas erupted from water-laden magma systems, including those investigated here, commonly have near equilibrium (210Pb/226Ra)0 values. Maintaining these equilibrium values requires minimal persistent loss or accumulation of 222Rn in a gas phase. We infer that degassing during decompression of water-saturated magmas either causes these magmas to crystallize and stall in reservoirs where they reside under conditions of near stasis, or to quickly rise towards the surface and erupt.

Remobilisation of industrial lead depositions in ash during Australian wildfires

This study examined the recycling of lead (Pb) in ash from wildfires, its source and potential contribution to environmental contamination. Ash from wildfires was collected from four Australian sites following uncontrolled fires during 2012 to 2013 close to major urban populations in Sydney (New South Wales), Hobart (Tasmania) and Adelaide (South Australia). The samples were analysed for their total Pb concentration and Pb isotopic composition to determine the sources of Pb and the extent, if any, of industrial contamination and its recycling into the ecosystem. Median ash concentrations (23mg/kg) released from a wildfire close to Australias largest city, Sydney, exceeded the median ash Pb concentrations from wildfires from the less populated locations of Hobart, Adelaide and NSW Central Coast. Lead isotopic compositions of Duffys Forest wildfire ash demonstrate that anthropogenic inputs from legacy leaded petrol depositions were the predominant source of contamination. Despite the cessation of leaded petrol use in Australia in 2002, historic petrol Pb deposits continue to be a substantial source of contamination in ash: petrol Pb contributed 35% of the Pb in the Woy Woy ash, 73% in Duffys Forest ash, 39% in Forcett ash and 5% in Cherryville ash. The remobilisation of legacy industrial Pb depositions by wildfires in ash results in it being a persistent and problematic contaminant in contemporary environmental systems because of its known toxicity.