Mercury levels in selected bycatch fish species from industrial shrimp-trawl fishery in the SE Gulf of California

Baseline Hg concentration in bycatch fish from the SE Gulf of California were determined in muscle and liver of 19 species. Levels of Hg in muscle were compared with legal limits of this element in national and international legislation. Considering all fish species, mean concentrations in liver (2.458 ± 1.997 μg g⁻¹) were significantly higher (p < 0.05) than in muscle (0.993 ± 0.670 μg g⁻¹). The sequence of averaged Hg concentrations in most ichthyofauna was liver > muscle. Highest level of Hg in muscle (2.556 μg g⁻¹) and liver (7.515 μg g⁻¹) corresponded to Diapterus peruvianus and Ophioscion strabo, respectively. Considering muscle samples, none of the species had levels of Hg above the limit (1.0 μg g⁻¹ wet weight) in the Mexican legislation; with respect to the Japanese (0.4 μg g⁻¹ wet weight) and British (0.3 μg g⁻¹ wet weight) legislations, 26.3% and 31.6% of the species respectively, were above the corresponding limits.     

Baseline concentrations of faecal sterols and assessment of sewage input into different inlets of Admiralty Bay,King George Island,Antarctica

The Antarctic region is one of the best preserved environments in the world. However, human activities such as the input of sewage result in the alteration of this pristine site. We report baseline values of faecal sterols in Admiralty Bay, Antarctica. Four sediment cores were collected during the 2006/2007 austral summer at the Ezcurra (THP and BAR), Mackelar (REF) and Martel (BTP) inlets. Concentrations of faecal sterols (coprostanol + epicoprostanol) were <0.16 μg g⁻¹, suggesting no sewage contamination and probable “biogenic” contributions for these compounds. Baseline values, calculated using the mean concentration of faecal sterols in core layers for THP, BAR, REF and BTP, were 0.04 ± 0.02, 0.03 ± 0.01, 0.07 ± 0.01 and 0.04 ± 0.02 μg g⁻¹, respectively. These results established as natural contributions of faecal sterols, suggesting that these markers can be useful indicators of human-derived faecal input and contributing to monitoring programs to prevent anthropogenic impacts.     

Phosphorus retention and release by sediments in the eutrophic Mai Po Marshes,Hong Kong

This study examined the phosphorus retention and release characteristics of sediments in the eutrophic Mai Po Marshes in Hong Kong. Results of chemical fractionation show that the sum of inorganic P pools exceeded 50% of the total sediment P content, with the redox-sensitive iron-bound P (Fe(OOH) ≈ P) being the dominant P fraction. Given the considerable average Fe(OOH) ≈ P concentration of 912 μg g⁻¹, Mai Po sediments demonstrated a great potential to release bioavailable P under low sediment redox potentials. This was further supported by the high mean anaerobic P flux of 31.8 mg m⁻² d⁻¹ recorded in Mai Po sediment cores, indicating the role of bottom sediments as a net P source. Although sediments in Mai Po had appreciable Langmuir adsorption maxima (1642–3582 mg kg⁻¹), the high zero equilibrium P concentrations (0.02–0.51 mg L⁻¹) obtained suggest that sediment sorption processes would contribute to sustaining the eutrophic conditions in overlying water column even with a further reduction in external P load. Concerted efforts should be made to reduce internal loading of P, especially under reducing conditions, to complement the implementation of zero discharge policy for Deep Bay for effective eutrophication abatement and long-term water quality improvement in the Mai Po Marshes.     

High cyst concentrations of the potentially toxic dinoflagellate Alexandrium tamarense species complex in Bedford Basin,Halifax, Nova Scotia,Canada

We report a large cyst bed of the potentially toxic and bloom-forming dinoflagellate Alexandrium tamarense species complex in bottom sediments from the port of Halifax, Nova Scotia, Canada. The average cyst concentrations of that species ranged from 4033 ± 2647 to 220 872 ± 148 086 cysts g^?1 of dry sediments and the highest concentrations were found near ship terminals in Bedford Basin. Although this species is endemic to this region, our work strongly suggests that some of the cysts of A. tamarense species complex found in the port of Halifax were introduced through discharged ballast water and sediments.     

In situ cosmogenic 10Be production-rate calibration from the Southern Alps,New Zealand

We present a ¹⁰Be production-rate calibration derived from an early Holocene debris-flow deposit at about 1000 m above sea level in the central Southern Alps, New Zealand, in the mid-latitude Southern Hemisphere. Ten radiocarbon ages on macrofossils from a soil horizon buried by the deposit date the deposit to 9690 ± 50 calendar years before AD2008. Surface ¹⁰Be concentrations of seven large boulders partially embedded in the stable surface of the deposit are tightly distributed, yielding a standard deviation of ～2%. Conversion of the ¹⁰Be measurements to sea level/high-latitude values using each of five standard scaling methods indicates ¹⁰Be production rates of 3.84 ± 0.08, 3.87 ± 0.08, 3.83 ± 0.08, 4.15 ± 0.09, and 3.74 ± 0.08 atoms g^?1 a^?1, relative to the ‘07KNSTD’ ¹⁰Be AMS standard, and including only the local time-integrated production-rate uncertainties. When including a sea level high-latitude scaling uncertainty the overall error is ～2.5% (1σ) for each rate. To test the regional applicability of this production-rate calibration, we measured ¹⁰Be concentrations in a set of nearby moraines deposited before 18 060 ± 200 years before AD2008. The ¹⁰Be ages are only consistent with minimum-limiting ¹⁴C age data when calculated using the new production rates. This also suggests that terrestrial in situ cosmogenic-nuclide production did not change significantly from Last Glacial Maximum to Holocene time in New Zealand. Our production rates agree well with those of a recent calibration study from northeastern North America, but are 12–14% lower than other commonly adopted values. The production-rate values presented here can be used elsewhere in New Zealand for rock surfaces exposed during or since the last glacial period.     

Determination of selected persistent organic pollutants in wastewater from landfill leachates,using an amperometric biosensor

Landfill leachates that contain persistent organic pollutants (POPs) are a big threat to groundwater systems and are projected to have hazardous effects in the long term if proper management strategies of the landfills are not put in place by those responsible. Monitoring the levels of POPs in landfill leachates is very crucial. This work presents an amperometric biosensor for determination of selected POPs in landfill leachates. The biosensor is based on kinetic inhibition of horseradish peroxidase (HRP). The enzyme was immobilised by electrostatic attachment on a polyaniline-modified Pt electrode surface. Selected POPs inhibited HRP enzyme activity and the decrease in the enzyme activity was used to determine these environmental pollutants. Selected polybrominated diphenyl ethers (PBDEs), polybrominated biphenyls (PBBs) and polychlorinated biphenyls (PCBs) were the analytes of choice because they are commonly found in South Africa water systems. Limits of detection for the amperometric biosensor were established as 0.014, 0.018, 0.022, 0.016 and 0.019 μg l⁻¹ for BDE-100, PBB-1, PCB-1, PCB-28 and PCB-101, respectively. The HRP biosensor system gave different linear ranges for; BDE-100 (0.424–25.8 μg l⁻¹), PBB-1 (0.862–13.4 μg l⁻¹), PCB-1 (0.930–18.1 μg l⁻¹), PCB-28 (0.730–15.7 μg l⁻¹) and PCB-101 (0.930–27.1 μg l⁻¹). Inhibition studies on HRP biosensor response toward the reduction of H₂O₂ in the absence and presence of the selected POPs were carried out to investigate the inhibition kinetics and its mechanism. The results obtained indicated that the inhibition mechanism was competitive for PBDEs and non-competitive for biphenyls (PCBs and PBBs). The application of the biosensor was tested on wastewater samples obtained from landfill leachate for determination of selected POPs. The leachate samples were found to contain PCB-28 (0.28 ± 0.03 μg l⁻¹) and PCB-101 (0.31 ± 0.02 μg l⁻¹). The samples were also analysed by GC–MS as a cross-check method and the two sets of results were in close agreement.     

Origin,toxicological and narcotic potential of sedimentary PAHs and remarkable even/odd n-alkane predominance in Bushehr Peninsula,the Persian Gulf

Surface sediments (n = 17) were collected from 6 sites located in the coasts of the Bushehr Peninsula. ∑₁₆PAH concentrations were in the range of 285.9–1288 ng g^? 1 dw and the sediments were moderately polluted. Py, Ph, B(a)A and Flu showed > 70% of the detected values in order of the mentioned rank. 4-ring PAHs were the dominant compounds and the molecular ratios presented the dominant pyrolytic source. The toxicity of PAHs for sediment dwelling life was averagely equivalent to occurrence of 0.08 ng g^? 1 of Dioxin in dw of the examined sediments. The evaluated narcotic potential (confidence level of 99%) was 0.027–3.04 and upper part of the Bushehr Peninsula, where the human population is more concentrated, showed more narcotic potential. ∑ n-alkane concentrations (n-C₁₅ ? n-C₃₂) were in the range of 3.10–35.6 μg g^? 1 dw. The dominant distribution of even carbon number n-alkanes was traced back to a possibly autochthonous source.     

Sewage organic markers in surface sediments around the Brazilian Antarctic station: Results from the 2009/10 austral summer and historical tendencies

The discharge of sewage into the Antarctic marine environments by scientific stations has resulted in local changes in these pristine sites. To assess the distribution and concentration of sewage indicators from the Brazilian Antarctic station, sediments were sampled during the 2009/10 austral summer at four points (water depth of 20 and 60 m). Concentrations of faecal sterols and linear alkylbenzenes (LABs) ranged from <0.01 to 0.17 μg g⁻¹ and <1.0 to 46.5 ng g⁻¹ dry weight, respectively. Maximum concentration of faecal sterols was similar to the value previously calculated as the background level for this area (0.19 μg g⁻¹), and it is lower than the concentration observed in previous studies (1997–2008), whereas the LABs concentrations remained practically constant (35 ng g⁻¹). Despite the low concentrations of sewage markers, the permanent human activities in the region require monitoring programs to determine continuing trends and prevent the increase of anthropogenic impacts.     

Sources and distribution of organic matter in northern Patagonia fjords,Chile (∼44–47°S): A multi-tracer approach for carbon cycling assessment

We investigated the provenance of organic matter in the inner fjord area of northern Patagonia, Chile (～44–47°S), by studying the elemental (organic carbon, total nitrogen), isotopic (δ¹³C, δ¹⁵N), and biomarker (n-alkanoic acids from vascular plant waxes) composition of surface sediments as well as local marine and terrestrial organic matter. Average end-member values of N/C, δ¹³C, and δ¹⁵N from organic matter were 0.127±0.010, ?19.8±0.3‰, and 9.9±0.5‰ for autochthonous (marine) sources and 0.040±0.018, ?29.3±2.1‰, and 0.2±3.0‰ for allochthonous (terrestrial) sources. Using a mixing equation based on these two end-members, we calculated the relative contribution of marine and terrestrial organic carbon from the open ocean to the heads of fjords close to river outlets. The input of marine-derived organic carbon varied widely and accounted for 13–96% (average 61%) of the organic carbon pool of surface sediments. Integrated regional calculations for the inner fjord system of northern Patagonia covered in this study, which encompasses an area of ～4280 km², suggest that carbon accumulation may account for between 2.3 and 7.8×10⁴ ton C yr^?1. This represents a storage capacity of marine-derived carbon between 1.8 and 6.2×10⁴ ton yr^?1, which corresponds to an assimilation rate of CO₂ by marine photosynthesis between 0.06 and 0.23×10⁶ ton yr^?1. This rate suggests that the entire fjord system of Patagonia, which covers an area of ～240,000 km², may represent a potentially important region for the global burial of marine organic matter and the sequestration of atmospheric CO₂.     

Osmium isotope and highly siderophile element systematics of the lunar crust

Coupled ¹⁸⁷Os/¹⁸⁸Os and highly siderophile element (HSE: Os, Ir, Ru, Pt, Pd, and Re) abundance data are reported for pristine lunar crustal rocks 60025, 62255, 65315 (ferroan anorthosites, FAN) and 76535, 78235, 77215 and a norite clast in 15455 (magnesian-suite rocks, MGS). Osmium isotopes permit more refined discrimination than previously possible of samples that have been contaminated by meteoritic additions and the new results show that some rocks, previously identified as pristine, contain meteorite-derived HSE. Low HSE abundances in FAN and MGS rocks are consistent with derivation from a strongly HSE-depleted lunar mantle. At the time of formation, the lunar floatation crust, represented by FAN, had 1.4 ± 0.3 pg g^? 1 Os, 1.5 ± 0.6 pg g^? 1 Ir, 6.8 ± 2.7 pg g^? 1 Ru, 16 ± 15 pg g^? 1 Pt, 33 ± 30 pg g^? 1 Pd and 0.29 ± 0.10 pg g^? 1 Re (～ 0.00002 × CI) and Re/Os ratios that were modestly elevated (¹⁸⁷Re/¹⁸⁸Os = 0.6 to 1.7) relative to CI chondrites. MGS samples are, on average, characterised by more elevated HSE abundances (～ 0.00007 × CI) compared with FAN. This either reflects contrasting mantle-source HSE characteristics of FAN and MGS rocks, or different mantle–crust HSE fractionation behaviour during production of these lithologies. Previous studies of lunar impact-melt rocks have identified possible elevated Ru and Pd in lunar crustal target rocks. The new results provide no supporting evidence for such enrichments.If maximum estimates for HSE in the lunar mantle are compared with FAN and MGS averages, crust–mantle concentration ratios (D-values) must be ≤ 0.3. Such D-values are broadly similar to those estimated for partitioning between the terrestrial crust and upper mantle, with the notable exception of Re. Given the presumably completely different mode of origin for the primary lunar floatation crust and tertiary terrestrial continental crust, the potential similarities in crust–mantle HSE partitioning for the Earth and Moon are somewhat surprising. Low HSE abundances in the lunar crust, coupled with estimates of HSE concentrations in the lunar mantle implies there may be a ‘missing component’ of late-accreted materials (as much as 95%) to the Moon if the Earth/Moon mass-flux estimates are correct and terrestrial mantle HSE abundances were established by late accretion.     

Nature of decadal-scale sediment accumulation on the western shelf of the Mississippi River delta

Sediment delivered to coastal systems by rivers (15×10⁹ tons) plays a key role in the global carbon and nutrient cycles, as deltas and continental shelves are considered to be the main repositories of organic matter in marine sediments. The Mississippi River, delivering more than 60% of the total dissolved and suspended materials from the conterminous US, dominates coastal and margin processes in the northern Gulf of Mexico. Draining approximately 41% of the conterminous US, the Mississippi and Atchafalaya river system deliver approximately 2×10⁸ tons of suspended matter to the northern Gulf shelf each year. Unlike previous work, this study provides a comprehensive evaluation of sediment accumulation covering majority of the shelf (<150 m water depth) west of the Mississippi Delta from 92 cores collected throughout the last 15 years. This provides a unique and invaluable data set of the spatial and modern temporal variations of the sediment accumulation in this dynamic coastal environment.Three types of ²¹⁰Pb profiles were observed from short cores (15–45 cm) collected on the shelf. Proximal to Southwest Pass in 30–100 m water depths, non-steady-state profiles were observed indicating rapid accumulation. Sediment accumulation rates in this area are typically >2.5 cm yr⁻¹ (>1.8 g cm⁻² yr⁻¹). Kasten cores (∼200 cm in length) collected near Southwest Pass also indicate rapid deposition (>4 cm yr⁻¹; >3 g cm⁻² yr⁻¹) on a longer timescale than that captured in the box cores. Near shore (<20 m), profiles are dominated by sediments reworked by waves and currents with no accumulation (the exception is an area just south of Barataria Bay where accumulation occurs). The remainder of the shelf (distal of Southwest Pass) is dominated by steady-state accumulation beneath a ∼10-cm thick mixed layer. Sediment accumulation rates for the distal shelf are typically <0.7 cm yr⁻¹ (<0.5 g cm⁻² yr⁻¹). A preliminary sediment budget based on the distribution of ²¹⁰Pb accumulation rates indicates that 40–50% of the sediment delivered by the river is transported out of the study region. Sediment is moved to distal regions of the shelf/slope through two different mechanisms. Along-isobath sediment movement occurs by normal resuspension processes west of the delta, whereas delivery of sediments south and southwest of the delta may be also be influenced by mass movement events on varying timescales.     

Mercury in the ecosystem of Admiralty Bay,King George Island,Antarctica: Occurrence and trophic distribution

Mercury (Hg) can reach the environment through natural and human-related sources, threatening ecosystems all over the planet due to its well known deleterious effects. Therefore, Antarctic trophic webs, despite being relatively isolated, are not exempt of its influence. To evaluate Hg concentrations in an Antarctic ecosystem, different tissues from 2 species of invertebrates, 2 of fish, 8 of birds, 4 of pinnipeds and at least 5 of vegetation were investigated (n = 176). For animals, values ranged from 0.018 to 48.7 μg g^? 1 dw (whole Antarctic krill and Antarctic Fur Seal liver). They were generally correlated to trophic position (assessed by δ¹⁵N and δ¹³C) but also to cephalopods and myctophids consumption. For vegetation, values ranged from 0.014 to 0.227 μg g^? 1 dw (Colobanthus quitensis and an unidentified lichen), with lichens presenting significantly higher values than mosses, likely due to year-round exposure and absorption of animal derived organic matter, as hypothesized by literature.     

Distribution and sources of polycyclic aromatic hydrocarbons in surface sediments of the Hormuz strait,Persian Gulf

The concentrations of 16 polycyclic aromatic hydrocarbons (PAHs) were determined in the sediment from the Hormuz strait, Persian Gulf. The sum of 16 PAHs (ΣPAH) concentrations varied from 72.17 to 277.77 ng g⁻¹ dry weight, with an average value of 131.20 ± 59.29 ng g⁻¹ dry weight. An ecological risk assessment of PAHs, indicated that adverse biological effects caused by acenaphthene and acenaphthylene occasionally may take place in the sediment of Hormuz strait. PAH source identification showed that the PAHs in the sediments come from pyrogenic and mixed origin. Based on classification of pollution levels, sediments from Hormuz strait could be considered as low to moderately polluted with PAHs.     

PAHs contamination and bacterial communities in mangrove surface sediments of the Jiulong River Estuary,China

Sixteen sediment samples collected from eight transects in a mangrove swamp of the Jiulong River Estuary, Fujian, China were investigated for their content of polycyclic aromatic hydrocarbons (PAHs) and the biodegradation potential of the indigenous microorganisms. The bacterial community structures in the mangrove sediments and in enrichment cultures were also investigated. The results showed that the total PAHs concentration of mangrove sediments ranged from 280 to 1074 ng g⁻¹ dry weight, that the PAHs composition pattern in the mangrove sediments was dominated by high molecular weight PAH components (4–6 rings), and that Benzo[ghi]perylene and Indeno[1,2,3-cd]pyrene were the most dominant at different stations. Abundant PAH-degrading bacteria were found in all the stations, the values of phenanthrene-degrading bacteria ranged from 5.85 × 10⁴ to 7.80 × 10⁵ CFU g⁻¹ dry weight, fluoranthene-degrading bacteria ranged from 5.25 × 10⁴ to 5.79 × 10⁵ CFU g⁻¹ dry weight, pyrene-degrading bacteria ranged from 3.10 × 10⁴ to 6.97 × 10⁵ CFU g⁻¹ dry weight and the benzo(a)pyrene-degrading bacteria ranged from 5.25 × 10⁴ to 7.26 × 10⁵ CFU g⁻¹ dry weight. DGGE analysis of PCR-amplified 16S rDNA gene fragments confirmed that there was a remarkable shift in the composition of the bacterial community due to the addition of the different model PAH compound phenanthrene (three ring PAH), fluoranthene(four ring PAH), pyrene(four ring PAH) and benzo(a)pyrene(five ring PAH) during enrichment batch culture. Eleven strains were obtained with different morphology and different degradation ability. The presence of common bands for microbial species in the cultures and in the native mangrove sediment DNA indicated that these strains could be potential in situ PAH-degraders.     

Content and distribution of trace metals in surface sediments from the northern Bering Sea,Chukchi Sea and adjacent Arctic areas

Concentrations of trace metals (Zn, Cr, Cu, V, Cd and Pb), total organic carbon (TOC), black carbon (BC) and their granulometry were examined in 25 surface sediment samples from the northern Bering Sea, Chukchi Sea and adjacent areas. Trace metal concentrations in the sediments varied from 21.06–168.21 mg kg⁻¹ for Zn, 8.91–46.94 mg kg⁻¹ for Cr, 2.69–49.39 mg kg⁻¹ for Cu, 32.46–185.54 mg kg⁻¹ for V, 0.09–0.92 mg kg⁻¹ for Cd, and 0.95–15.25 mg kg⁻¹ for Pb. The geoaccumulation index (I_geo) indicated that trace metal contamination (Zn and Cd) existed in some stations of the study area. The distribution of grain size plays an important role in influencing the distribution of trace metals (Zn, Cr, Cu, V, and Pb) in sediments from the Chukchi Sea and adjacent areas.     

Embryotoxic and genotoxic effects of heavy metals and pesticides on early life stages of Pacific oyster (Crassostrea gigas)

This study evaluated embryotoxicity and genotoxicity of two dissolved metals copper and cadmium (Cu and Cd) and two pesticides (metolachlor and irgarol) occurring in Arcachon Bay (SW France) in Pacific oyster (Crassostrea gigas) larvae and investigated the relationship between those two endpoints. Embryotoxicity was measured by calculating the percentage of abnormal D-shaped larvae and genotoxicity was evaluated with DNA strand breaks using the comet assay. After 24 h exposure, significant increases of the percentage of abnormal D-larvae and the DNA strand breaks were observed from 0.1 μg L⁻¹ for Cu, 10 μg L⁻¹ for Cd and 0.01 μg L⁻¹ for both irgarol and metolachlor in comparison with the controls. A strong positive relationship between embryotoxicity and genotoxicity was recorded for Cu, Cd and metolachlor. The current study suggests that copper, irgarol and metolachlor can induce larval abnormalities and DNA damage in a population of exposed oysters at environmentally relevant concentrations.     

Total and labile metals in surface sediments of the tropical river-estuary system of Marabasco (Pacific coast of Mexico): Influence of an iron mine

Marabasco is a tropical river-estuary system comprising the Marabasco river and the Barra de Navidad Lagoon. The river is impacted by the Peña Colorada iron mine, which produces 3.5 million tons of pellets per year. Thirteen surface sediment samples were collected in May 2005 (dry season) in order to establish background levels of Al, Cd, Co, Cu, Fe, Ni, Pb, and Zn in the system and to ascertain the potential mobility of metals in the sediments. Analyses were carried out in the fraction finer than 63 μm, and labile metals extracted according the BCR procedure. Certified reference materials were used for validation of methods.Total concentrations of Cd, Co, Cu, Ni, Pb, and Zn were in the range of 0.05–0.34, 6–95, 0.7–31, 9–26, 2–18, and 53–179 mg kg⁻¹, respectively; Al and Fe ranges of 24–127, and 26–69 mg g⁻¹ correspondingly. Cadmium was found to be significantly labile in the sediments (20–100%), followed by Co (0–35%), Ni (3–16%) and Zn (0–25%), whereas the labile fraction for Cu, Fe and Pb was almost negligible (<4%).According with the total metal concentrations, background levels and normalised enrichment factors (NEF) of the metals studied, the impact of the Peña Colorada iron mine on the Marabasco system is lower than expected when compared with other similar World systems influenced by mining activities.     

Mercury emissions and stable isotopic compositions at Vulcano Island (Italy)

Sampling and analyses methods for determining the stable isotopic compositions of Hg in an active volcanic system were tested and optimized at the volcanic complex of Vulcano (Aeolian Islands, Italy). Condensed gaseous fumarole Hg_(fum)^T, plume gaseous elemental Hg_(g)⁰ and plume particulate Hg_(p)^II were obtained at fumaroles F0, F5, F11, and FA. The average total Hg emissions, based on Hg^T/SO₂ in condensed fumarolic gases and plumes, range from 2.5 to 10.1 kg y^? 1, in agreement with published values [Ferrara, R., Mazzolai, B., Lanzillotta, E., Nucaro, E., Pirrone, N., 2000. Volcanoes as emission sources of atmospheric mercury in the Mediterranean Basin. Sci. Total Environ. 259(1–3), 115–121; Aiuppa, A., Bagnato, E., Witt, M.L.I., Mather, T.A., Parello, F., Pyle, D.M., Martin, R.S., 2007. Real-time simultaneous detection of volcanic Hg and SO₂ at La Fossa Crater, Vulcano (Aeolian Islands, Sicily). Geophys. Res. Lett. 34(L21307).]. Plume Hg_(p)^II increases with distance from the fumarole vent, at the expense of Hg_(g)⁰ and indicates significant in-plume oxidation and condensation of fumarole Hg_(fum)^T.Relative to the NIST SRM 3133 Hg standard, the stable isotopic compositions of Hg are δ²⁰²Hg_(fum)^T = ? 0.74‰ ± 0.18 (2SD, n = 4) for condensed gaseous fumarole Hg_(fum)^T, δ²⁰²Hg_(g)⁰ = ? 1.74‰ ± 0.36 (2SD, n = 1) for plume gaseous elemental Hg_(g)⁰ at the F0 fumarole, and δ²⁰²Hg_(p)^II = ? 0.11‰ ± 0.18 (2SD, n = 4) for plume particulate Hg_(p)^II. The enrichment of Hg_(p)^II in the heavy isotopes and Hg_(g)⁰ in the light isotopes relative to the total condensed fumarolic Hg_(fum)^T gas complements the speciation data and demonstrates a gas-particle fractionation occurring after the gas expulsion in ambient T° atmosphere. A first order Rayleigh equilibrium condensation isotope fractionation model yields a fractionation factor α_cond-gas of 1.00135 ± 0.00058.     

Cosmogenic 3He and 21Ne dating of biotite and hornblende

Stable cosmogenic isotopes such as ³He and ²¹Ne are useful for dating of diverse lithologies, quantifying erosion rates and ages of ancient surfaces and sediments, and for assessing complex burial histories. Although many minerals are potentially suitable targets for ³He and ²¹Ne dating, complex production systematics require calibration of each mineral–isotope pair. We present new results from a drill core in a high-elevation ignimbrite surface, which demonstrates that cosmogenic ³He and ²¹Ne can be readily measured in biotite and hornblende. ²¹Ne production rates in hornblende and biotite are similar, and are higher than that in quartz due to production from light elements such as Mg and Al. We measure ²¹Ne_hbl/²¹Ne_qtz = 1.35 ± 0.03 and ²¹Ne_bio/²¹Ne_qtz = 1.3 ± 0.02, which yield production rates of 25.6 ± 3.0 and 24.7 ± 2.9 at g^? 1 yr^? 1 relative to a ²¹Ne_qtz production rate of 19.0 ± 1.8 at g^? 1 yr^? 1. We show that nucleogenic ²¹Ne concentrations produced via the reaction ¹⁸O(α,n)²¹Ne are manageably small in this setting, and we present a new approach to deconvolve nucleogenic ²¹Ne by comparison to nucleogenic ²²Ne produced from the reaction ¹⁹F(α,n)²²Ne in F-rich phases such as biotite. Our results show that hornblende is a suitable target phase for cosmogenic ³He dating, but that ³He is lost from biotite at Earth surface temperatures. Comparison of ³He concentrations in hornblende with previously measured mineral phases such as apatite and zircon provides unambiguous evidence for ³He production via the reaction ⁶Li(n,α)³H → ³He. Due to the atypically high Li content in the hornblende (~ 160 ppm) we estimate that Li-produced ³He represents ~ 40% of total ³He production in our samples, and must be considered on a sample-specific basis if ³He dating in hornblende is to be widely implemented.     

A lithium isotopic study of sub-greenschist to greenschist facies metamorphism in an accretionary prism,New Zealand

To investigate the behavior of Li during low-grade metamorphism and fluid flux in an accretionary prism we measured the Li concentrations ([Li]) and isotopic compositions (δ⁷Li) of sub-greenschist and greenschist-facies Otago Schist composites, as well as cross-cutting quartz veins, which are interpreted to have precipitated from slab-derived fluids. The average [Li] of sub-greenschist facies composites (41 ± 13 μg/g, 2σ) is statistically distinct (97% confidence level, student t test) to that of greenschist facies composites (34 ± 9 μg/g, 2σ), which have experienced mass addition of silica in the form of quartz veins having [Li] between 0.4–2.3 μg/g. A linear regression of the correlation between [Li] and calculated mass additions suggests that the depletion of [Li] in greenschist facies composites is due to both dilution from the addition of the quartz veins, as well as metamorphic dehydration. The [Li] of both groups of composites correlates with their CIA (Chemical Index of Alteration) values (50–58), which are low, consistent with the inferred graywacke protolith of the Otago Schist. The δ⁷Li of sub-greenschist and greenschist facies composites are remarkably constant, with an average δ⁷Li of 0.2 ± 1.7 (2σ) and ?0.5 ± 1.9 (2σ), respectively, and comparable to that of the average upper continental crust. Thus, metamorphism has had no discernable effect on δ⁷Li in these samples. The Li isotopic signature of the schists is similar to that seen in pelitic sedimentary rocks and likely reflects the δ⁷Li of the protoliths. The surprisingly light δ⁷Li of the quartz veins (?2.8 to ?1.4) likely records kinetic fractionation associated with Li ingress into the veins from surrounding wallrock.An isotopic equilibrium fluid flow model indicates that: 1) if the [Li] of slab-derived fluids is less than a few μg/g, the δ⁷Li of the overlying lithologies (i.e., the schists) is not significantly influenced by the fluid flux, regardless of the δ⁷Li of the fluids, 2) the slab-derived fluids will have heavy δ⁷Li of > + 10 after reacting with the prism sediments during their ascent, and 3) the [Li] of the slab-derived fluids is likely in the range of 0 < [Li] ≤ 41(μg/g). Thus, isotopically heavy slab-derived fluids that traverse sediments in accretionary prisms may leave little trace in the rocks and their surface compositional characteristics will reflect the net result of their interaction with the sediments of the prism.