Copper Isotopic Analysis in Geological and Biological Reference Materials by MC‐ICP‐MS

The characterisation of relative copper isotope amount ratios (δ⁶⁵Cu) helps constrain a variety of geochemical processes occurring in the geosphere, biosphere and hydrosphere. The accurate and precise determination of δ⁶⁵Cu in matrix reference materials is crucial in the effort to validate measurement methods. With the goal of expanding the number and variety of available geological and biological materials, we have characterised the δ⁶⁵Cu values of ten reference materials by MC‐ICP‐MS using C‐SSBIN model for mass bias correction. SGR‐1b (Green River shale), DOLT‐5 (dogfish liver), DORM‐4 (fish protein), TORT‐3 (lobster hepatopancreas), MESS‐4 (marine sediment) and PACS‐3 (marine sediment) have for the first time been characterised for δ⁶⁵Cu. Additionally, four reference materials (with published δ⁶⁵Cu values) have been characterised: BHVO‐1 (Hawaiian basalt), BIR‐1 (Icelandic basalt), W‐2a (diabase) and Seronorm? Trace Elements Serum L‐1 (human serum). The reference materials measured in this study possess complex and varied matrices with copper mass fractions ranging from 1.2 µg g^?1 to 497 µg g^?1 and δ⁶⁵Cu values ranging from ?0.20‰ to 0.52‰ with a mean expanded uncertainty of ± 0.07‰ (U, k = 2), covering much of the natural copper isotope variability observed in the environment.     

High‐ to ultrahigh‐temperature metamorphism in the lower crust: An example resulting from Hikurangi Plateau collision and slab rollback in New Zealand

Lower crustal xenoliths erupted from an intraplate diatreme reveal that a portion of the New Zealand Gondwana margin experienced high‐temperature (HT) to ultrahigh‐temperature (UHT) granulite facies metamorphism just after flat slab subduction ceased at c. 110–105 Ma. P–T calculations for garnet–orthopyroxene‐bearing felsic granulite xenoliths indicate equilibration at ~815 to 910°C and 0.7 to 0.8 GPa, with garnet‐bearing mafic granulite xenoliths yielding at least 900°C. Supporting evidence for the attainment of HT and UHT conditions in felsic granulite comes from re‐integration of exsolution in feldspar (~900–950°C at 0.8 GPa), Ti‐in‐zircon thermometry on Y‐depleted overgrowths on detrital zircon grains (932°C ± 24°C at aTiO₂ = 0.8 ± 0.2), and correlation of observed assemblages and mineral compositions with thermodynamic modelling results (≥850°C at 0.7 to 0.8 GPa). The thin zircon overgrowths, which were mainly targeted by drilling through the cores of grains, yield a U–Pb pooled age of 91.7 ± 2.0 Ma. The cause of Late Cretaceous HT‐UHT metamorphism on the Zealandia Gondwana margin is attributed to collision and partial subduction of the buoyant oceanic Hikurangi Plateau in the Early Cretaceous. The halt of subduction caused the fore‐running shallowly dipping slab to rollback towards the trench position and permitted the upper mantle to rapidly increase the geothermal gradient through the base of the extending (former) accretionary prism. This sequence of events provides a mechanism for achieving regional HT–UHT conditions in the lower crust with little or no sign of this event at the surface.     

Petrology of the 1979 eruption of Soufriere volcano,St. Vincent,Lesser Antilles

Major element, trace element, and Sr isotope data are used to study the temporal variation in the chemistry of the ejecta from the 1979 eruption of Soufriere volcano, St. Vincent, and to compare the compositions of the 1979 and 1971/2 magmas. Both the 1971/2 and 1979 products were basaltic andesites almost identical in petrography. A small temporal variation in chemistry is apparent in the 1979 samples but these cannot be related to the 1971/2 lava by fractional crystallisation of phenocryst phases, and the two eruptions may therefore have sampled different batches of magma. ⁸⁷Sr/⁸⁶Sr ratios of the two magmas were identical within analytical error.Microprobe analyses of phenocryst phases and glasses from the 1979 ejecta are presented. Clinopyroxene phenocryst cores with very high Mg/Fe ratios indicate that the basaltic andesites are products of fractionation of magnesian parents. Such magmas are represented by lavas on St. Vincent similar to the microphyric alkali picrites found to the south in Grenada. A common origin for the basaltic andesites of both islands by fractional crystallisation of picritic magmas is suggested. Dacitic glass is abundant in the groundmass of scoria blocks from the eruption. It does not represent the liquid originally in equilibrium with the phenocryst phases, but rather this liquid modified by quench crystallisation. Published interpretations suggesting that dacitic glass compositions in tephra from eruptions of the Soufriere are evidence of mixed-magma eruptions are therefore rejected.     

Experimental analysis of arsenic precipitation during microbial sulfate and iron reduction in model aquifer sediment reactors

Microbial SO₄²⁻ reduction limits accumulation of aqueous As in reducing aquifers where the sulfide that is produced forms minerals that sequester As. We examined the potential for As partitioning into As- and Fe-sulfide minerals in anaerobic, semi-continuous flow bioreactors inoculated with 0.5% (g mL⁻¹) fine-grained alluvial aquifer sediment. A fluid residence time of three weeks was maintained over a ca. 300-d incubation period by replacing one-third of the aqueous phase volume of the reactors with fresh medium every seven days. The medium had a composition comparable to natural As-contaminated groundwater with slightly basic pH (7.3) and 7.5 μM aqueous As(V) and also contained 0.8 mM acetate to stimulate microbial activity. Medium was delivered to a reactor system with and without 10 mmol L⁻¹ synthetic goethite (α-FeOOH). In both reactors, influent As(V) was almost completely reduced to As(III). Pure As-sulfide minerals did not form in the Fe-limited reactor. Realgar (As₄S₄) and As₂S₃(am) were undersaturated throughout the experiment. Orpiment (As₂S₃) was saturated while sulfide content was low (∼50 to 150 μM), but precipitation was likely limited by slow kinetics. Reaction-path modeling suggests that, even if these minerals had formed, the dissolved As content of the reactor would have remained at hazardous levels. Mackinawite (Fe_1 + xS; x ? 0.07) formed readily in the Fe-bearing reactor and held dissolved sulfide at levels below saturation for orpiment and realgar. The mackinawite sequestered little As (<0.1 wt.%), however, and aqueous As accumulated to levels above the influent concentration as microbial Fe(III) reduction consumed goethite and mobilized adsorbed As. A relatively small amount of pyrite (FeS₂) and greigite (Fe₃S₄) formed in the Fe-bearing reactor when we injected a polysulfide solution (Na₂S₄) to a final concentration of 0.5 mM after 216, 230, 279, and 286 days. The pyrite, and to a lesser extent the greigite, that formed did sequester As from solution, containing 0.84 and 0.23 wt.% As on average, respectively. Our results suggest that As precipitation during Fe-sulfide formation in nature occurs mainly in conjunction with pyrite formation. Our findings imply that the effectiveness of stimulating microbial SO₄²⁻ reduction to remediate As contamination may be limited by the rate and extent of pyrite formation and the solubility of As-sulfides.     

A geochemical investigation of hydrologically derived threats to rare biota: the Drummond Nature Reserve, Western Australia

The Drummond Nature Reserve (DNR), a high-value conservation area 100?km northeast of Perth, Western Australia, contains two rare freshwater claypans and a diverse range of rare and threatened vascular plants. Groundwater/surface-water interactions were investigated via isotopic (??¹⁸O and ??D) and major ion analysis. The groundwater chemical and isotope analyses combined with nutrient data allowed for the assessment of potential hydrologically derived threats to the claypans and their associated conservation values. Groundwater composition is typically Na?CCl to Na?CMg?CCl; whereas the claypan??s ephemeral fresh surface water is Na?CCl?CHCO₃. Distinct ??¹⁸O and ??D isotopic signatures for the claypan surface waters and adjoining groundwaters indicate that there currently is minimal connection between these two hydrological systems. Hence the current threat to the freshwater claypans and associated biota from rising saline and acidic groundwater is minimal. Elevated nutrient (N) levels identified in groundwaters along the reserve??s western boundary may be linked to fertiliser regimes employed in adjoining agricultural lands. The ecosystem associated with the southwest claypan is particularly vulnerable to N and P inputs via surface-water flows, which could cause algal blooms, vegetation degradation and weed infestation.     

Rare earth elements (REE) and yttrium in stream waters, stream sediments, and Fe-Mn oxyhydroxides: Fractionation, speciation, and controls over REE + Y patterns in the surface environment

We have collected ∼500 stream waters and associated bed-load sediments over an ∼400 km² region of Eastern Canada and analyzed these samples for Fe, Mn, and the rare earth elements (REE + Y). In addition to analyzing the stream sediments by total digestion (multi-acid dissolution with metaborate fusion), we also leached the sediments with 0.25 M hydroxylamine hydrochloride (in 0.05 M HCl), to determine the REE + Y associated with amorphous Fe- and Mn-oxyhydroxide phases. We are thus able to partition the REE into “dissolved” (<0.45 μm), labile (hydroxylamine) and detrital sediment fractions to investigate REE fractionation, and in particular, with respect to the development of Ce and Eu anomalies in oxygenated surface environments. Surface waters are typically LREE depleted ([La/Sm]_NASC ranges from 0.16 to 5.84, average = 0.604, n = 410; where the REE are normalized to the North America Shale Composite), have strongly negative Ce anomalies ([Ce/Ce^∗]_NASC ranges from 0.02 to 1.25, average = 0.277, n = 354), and commonly have positive Eu anomalies ([Eu/Eu^∗]_NASC ranges from 0.295 to 1.77, average = 0.764, n = 84). In contrast, the total sediment have flatter REE + Y patterns relative to NASC ([La/Sm]_NASC ranges from 0.352 to 1.12, average = 0.778, n = 451) and are slightly middle REE enriched ([Gd/Yb]_NASC ranges from 0.55 to 3.75, average = 1.42). Most total sediments have negative Ce and Eu anomalies ([Ce/Ce^∗]_NASC ranges from 0.097 to 2.12, average = 0.799 and [Eu/Eu^∗]_NASC ranges from 0.39 to 1.43, average = 0.802). The partial extraction sediments are commonly less LREE depleted than the total sediments ([La/Sm]_NASC ranges from 0.24 to 3.31, average = 0.901, n = 4537), more MREE enriched ([Gd/Yb]_NASC ranges from 0.765 to 6.28, average = 1.97) and Ce and Eu anomalies (negative and positive) are more pronounced.The partial extraction recovered, on average ∼20% of the Fe in the total sediment, ∼80% of the Mn, and 21-29% of the REEs (Ce = 19% and Y = 32%). Comparison between REEs in water, partial extraction and total sediment analyses indicates that REEs + Y in the stream sediments have two primary sources, the host lithologies (i.e., mechanical dispersion) and hydromorphically transported (the labile fraction). Furthermore, Eu appears to be more mobile than the other REE, whereas Ce is preferentially removed from solution and accumulates in the stream sediments in a less labile form than the other REEs + Y. Despite poor statistical correlations between the REEs + Y and Mn in either the total sediment or partial extractions, based on apparent distribution coefficients and the pH of the stream waters, we suggest that either sediment organic matter and/or possibly δ-MnO₂/FeOOH are likely the predominant sinks for Ce, and to a lesser extent the other REE, in the stream sediments.     

Impact of artificial subsurface drainage on groundwater travel times and baseflow discharge in an agricultural watershed,Iowa (USA)

Pollutant delivery through artificial subsurface drainage networks to streams is an important transport mechanism, yet the impact of drainage tiles on groundwater hydrology at the watershed scale has not been well documented. In this study, we developed a two‐dimensional, steady‐state groundwater flow model for a representative Iowa agricultural watershed to simulate the impact of tile drainage density and incision depth on groundwater travel times and proportion of baseflow contributed by tile drains. Varying tile drainage density from 0 to 0.0038 m^?1, while maintaining a constant tile incision depth at 1.2 m, resulted in the mean groundwater travel time to decrease exponentially from 40 years to 19 years and increased the tile contribution to baseflow from 0% to an upper bound of 37%. In contrast, varying tile depths from 0.3 to 2.7 m, while maintaining a constant tile drainage density of 0.0038 m^?1, caused mean travel times to decrease linearly from 22 to 18 years and increased the tile contribution to baseflow from 30% to 54% in a near‐linear manner. The decrease in the mean travel time was attributed to decrease in the saturated thickness of the aquifer with increasing drainage density and incision depth. Study results indicate that tile drainage affects fundamental watershed characteristics and should be taken into consideration when evaluating water and nitrate export from agricultural regions. Copyright © 2011 John Wiley & Sons, Ltd.     

Hillslopes in humid-tropical climates aren't always wet: Implications for hydrologic response and landslide initiation in Puerto Rico

The devastating impacts of the widespread flooding and landsliding in Puerto Rico following the September 2017 landfall of Hurricane Maria highlight the increasingly extreme atmospheric disturbances and enhanced hazard potential in mountainous humid-tropical climate zones. Long-standing conceptual models for hydrologically driven hazards in Puerto Rico posit that hillslope soils remain wet throughout the year, and therefore, that antecedent soil wetness imposes a negligible effect on hazard potential. Our post-Maria in situ hillslope hydrologic observations, however, indicate that while some slopes remain wet throughout the year, others exhibit appreciable seasonal and intra-storm subsurface drainage. Therefore, we evaluated the performance of hydro-meteorological (soil wetness and rainfall) versus intensity-duration (rainfall only) hillslope hydrologic response thresholds that identify the onset of positive pore-water pressure, a predisposing factor for widespread slope instability in this region. Our analyses also consider the role of soil-water storage and infiltration rates on runoff generation, which are relevant factors for flooding hazards. We found that the hydro-meteorological thresholds outperformed intensity-duration thresholds for a seasonally wet, coarse-grained soil, although they did not outperform intensity-duration thresholds for a perennially wet, fine-grained soil. These end-member soils types may also produce radically different stormflow responses, with subsurface flow being more common for the coarse-grained soils underlain by intrusive rocks versus infiltration excess and/or saturation excess for the fine-grained soils underlain by volcaniclastic rocks. We conclude that variability in soil-hydraulic properties, as opposed to climate zone, is the dominant factor that controls runoff generation mechanisms and modulates the relative importance of antecedent soil wetness for our hillslope hydrologic response thresholds.