Rémi Freydier

Measurement of the isotopic composition of dissolved iron in the open ocean

This work demonstrates for the first time the feasibility of the measurement of the isotopic composition of dissolved iron in seawater for a typical open ocean Fe concentration range (0.1-1nM). It also presents the first data of this kind. Iron is preconcentrated using a Nitriloacetic Acid Superflow resin and purified using an AG1x4 anion exchange resin. The isotopic ratios are measured with a MC-ICPMS Neptune, coupled with a desolvator (Aridus II), using a 57Fe-58Fe double spike mass bias correction. Measurement precision (0.13‰, 2SD) allow resolving small iron isotopic composition variations within the water column, in the Atlantic sector of the Southern Ocean (from deltaFe=-0.19 to +0.32‰). Isotopically light iron found in the Upper Circumpolar Deep Water is hypothesized to result from organic matter remineralization. Shallow samples suggest that, if occurring, an iron isotopic fractionation during iron uptake by phytoplankton is characterized by a fractionation factor, such as: abs(deltaFe(plankton-seawater))< 0.48‰.

Persisting impact of historical mining activity to metal (Pb, Zn, Cd, Tl, Hg) and metalloid (As, Sb) enrichment in sediments of the Gardon River, Southern France

In this study, we assessed past and present influence of ancient mining activity on metal(loid) enrichment in sediments of a former mining watershed (Gardon River, SE France), that is now industrialized and urbanized. A sedimentary archive and current sediments were characterized combining geochemical analyses, zinc isotopic analyses and sequential extractions. The archive was used to establish local geochemical background and recorded (i) increasing enrichment factors (EFs) for Pb, Zn, Cd, Tl, Hg, As and Sb throughout the industrial era, (ii) a contamination peak in 1976 attributed to a tailings dam failure, and (iii) current levels in 2002 and 2011 similar to those of 1969, except for Sb and Hg, reflecting a persisting contamination pattern. Inter-element relationships and spatial distribution of EF values of current sediments throughout the watershed suggested that both ancient and current contamination had a common origin for Pb, Zn, Cd, Tl and As related to the exploitation of Pb/Zn mineralization while old Sb mines and coal extraction area were the main sources for Sb and Hg respectively. This prevailing mining origin was reflected for Zn by a relatively uniform isotopic composition at δ(66)Zn=0.23 ± 0.03‰, although slight decrease from 0.23‰ to 0.18‰ was recorded from upstream to downstream sites along the river course in relation with the contribution of the lighter δ(66)Zn signature (~0.08‰) of acid mine drainage impacted tributaries. Results from sequential extractions revealed that the potential mobility of the studied metal(loid)s varied in the order Sb<Tl≈As<Zn<Pb<Cd, with an increase of the mobile pool for Cd, Pb, Zn and to a lesser extent for As and Tl associated to increased enrichment. Altogether, these results tend to demonstrate that ancient mining activity still contributes to metal enrichment in the sediments of the Gardon River and that some of these metals may be mobilized toward the water compartment.

Evidence for Non-Conservative Behaviour of Chlorine in Humid Tropical Environments

The knowledge of the biogeochemical cycle of chlorine (Cl)is important since this element is used as a tracer of geochemical and hydrological processes in oceanic or continental environments. More specifically, Cl can be used to correct surface water composition from atmospheric contribution in order to calculate precise chemical weathering rates in watersheds. Beyond the problem of potential Cl sources in a given watershed, which is directly related to the lithology, vegetation, and industrial activities, the Cl normalization is based on the assumption that this element behaves conservatively during surface processes (e.g., chemical weathering, adsorption/desorption processes).The purpose of the present study is to forecast the geochemical behavior of Cl in a forested ecosystem located under humid tropical environment.For this reason, we have analyzed the Cl (and also Ca and Na) concentrations ofsurface waters (rainwater, groundwater, river water) over a two-year period in the Nsimi–Zoetele watershed (Cameroon).The Cl mass balance for the watershed appears to be equilibrated over the studied period (1995–1996) but Cl behavior in Mengong River draining the watershed suggests a non-conservative behavior. Indeed, Cl concentrationsin the Mengong River are low during dry seasons and high during wet seasons, which is the reverse tendency to what is usually observed taking into account dilution and evaporation processes. As Cl concentrations in the Mengong River are lower than those measured in all the feeding reservoirs, Cl should be adsorbed onto the soils of the watershed. However, as the Cl mass balance is equilibrated over the whole-year, Cl should be adsorbed and releasedat a seasonal scale. The results we obtained for this small watershed were not generalized for a larger studied basin (i.e., Nyong River basin). Even if these results should be followed by further investigations, this study suggests that Cl normalization should be used with caution to avoid under- or over-estimation of chemical weathering rates.

Evaluation of infrared femtosecond laser ablation for the analysis of geomaterials by ICP-MS

The capabilities of an infrared (IR) Ti:sapphire femtosecond laser (≈800 nm) to ablate and analyze geomaterials such as monazite, zircon and synthetic glass reference materials is evaluated, with emphasis on U/Pb ratio determinations useful for dating accessory minerals in rocks. We particularly discuss the influence of pulse duration (respectively 60, 200, 350, 500, 670, 830, 2000 and 3000 fs) on the internal precision (2 min ablation), reproducibility over two weeks and accuracy of quadrupole ICP-MS measurements. The best results for all these criteria are obtained when using the shortest pulse duration (60 fs). It was found that internal precision and reproducibility were improved by a factor of 3 and 4, respectively, from picosecond to 60 fs pulsewidths. Reproducibility at this pulse duration for U/Pb ratio determinations is of 2% RSD or better, depending on the material analyzed, and this ratio is accurate within this uncertainty. Lead isotopic ratios also benefit from the shortest pulsewidth. They are measured at 60 fs with a precision (<0.5% RSD) approaching the limitations of quadrupole ICP-MS. Preliminary data were also obtained using the 3rd harmonic (≈266 nm) of the Ti:sapphire fundamental wavelength and they are compared with the infrared mode. There seems to be no obvious analytical benefit to switch from IR to UV in the femtosecond laser ablation regime. Analyses of zircon 91500 with IR pulses led to better repeatability, around 0.9% (10 values, 1σ), compared to 3% for the UV pulses. The accuracy appears to be comparable for the two wavelengths.

Amorphous Materials: Properties, Structure, and Durability{dagger} Arsenic enrichment in hydrous peraluminous melts: Insights from femtosecond laser ablation-inductively coupled plasma-quadrupole mass spectrometry, and in situ X-ray absorption fine structure spectroscopy

Abstract Despite the ubiquity of arsenic in hydrothermal-magmatic environments, its abundance, distribution, and chemical and structural status in natural silicate melts and glasses remain poorly known. Here we report the first in situ measurements of the redox state and molecular structure of As, using X-ray absorption fine structure (XAFS) spectroscopy, in a rhyolitic peraluminous glass from Macusani (SE Peru) that is representative of anatectic melts derived from metasedimentary crustal protoliths. Arsenic abundances as well as the concentrations of other trace elements were measured in the glass using a femtosecond laser ablation-inductively coupled plasma-quadrupole mass spectrometry (LA-ICP-QMS). The glass shows enrichments, by factors of 10 to 100, in comparison with the mean continental crust values, for As and other incompatible trace elements (e.g., Be, B, Rb, Sn, Sb, and Ta), and by factors of 100 to 200 for Li, Cd, and Cs. Arsenic is present in the peraluminous glass in trivalent state in the form of oxy-hydroxide complexes like AsO(OH)2- and/or As(OH)3, similar to those dominant in the aqueous fluid vapor phases at hydrothermal-magmatic conditions. The similar As chemical speciation between the fluid and the melt is consistent with As fluid/melt partitioning coefficients close to one, as observed in experiments on rhyolite-water systems. The depolymerized melt structure caused by elevated H2O, F, and P contents is likely to allow accomodation of high concentrations of metalloid hydroxide/hydrated complexes. Consequently, hydrous silicate melts may be important transporting media in shallow magmatic-hydrothermal settings for As and similar elements like B and Sb due to their high affinity to water and hydroxide ligands

High-precision determination of the isotopic composition of dissolved iron in iron depleted seawater by double spike multicollector-ICPMS.

This work demonstrates the feasibility of the measurement of the isotopic composition of dissolved iron in seawater for an iron concentration range, 0.05-1 nmol L(-1), allowing measurements in most oceanic waters, including Fe depleted waters of high nutrient low chlorophyll areas. It presents a detailed description of our previously published protocol, with significant improvements on detection limit and blank contribution. Iron is preconcentrated using a nitriloacetic acid superflow resin and purified using an AG 1-x4 anion exchange resin. The isotopic ratios are measured with a multicollector-inductively coupled plasma mass spectrometer (MC-ICPMS) Neptune, coupled with a desolvator (Aridus II or Apex-Q), using a (57)Fe-(58)Fe double spike mass bias correction. A Monte Carlo test shows that optimum precision is obtained for a double spike composed of approximately 50% (57)Fe and 50% (58)Fe and a sample to double spike quantity ratio of approximately 1. Total procedural yield is 91 +/- 25% (2SD, n = 55) for sample sizes from 20 to 2 L. The procedural blank ranges from 1.4 to 1.1 ng, for sample sizes ranging from 20 to 2 L, respectively, which, converted into Fe concentrations, corresponds to blank contributions of 0.001 and 0.010 nmol L(-1), respectively. Measurement precision determined from replicate measurements of seawater samples and standard solutions is 0.08 per thousand (delta(56)Fe, 2SD). The precision is sufficient to clearly detect and quantify isotopic variations in the oceans, which so far have been observed to span 2.5 per thousand and thus opens new perspectives to elucidate the oceanic iron cycle.

Trace elements in the sediments of a large Mediterranean marina (Port Camargue, France): Levels and contamination history

The study of trace elements (Cu, Zn, Pb, As, Hg) and butyltin concentrations in the sediments of Port Camargue enabled assessment of the levels and history of the contamination of the largest European marina linked with the use of antifouling paints. Surface sediments near the boat maintenance area were heavily contaminated with up to 1497 μg g(-1) of Cu, 475 μg g(-1) of Zn, 0.82 μg g(-1) of Hg, 94 μg g(-1) of Pb and over 10,000 ngSn g(-1) of tributyltin (TBT). High concentrations of Hg and TBT indicate ongoing sources of these elements despite the ban on their use as biocides in paints. Sediment cores provided records of contamination since 1969. The peak concentrations of As, Hg, Pb and TBT in the sediment profile reflect their presence on boat hulls when the marina was built at the end of the 1960s. Degradation of TBT in the sediments near the boat maintenance area is slow compared to other less contaminated area of the marina.

Near Infra Red femtosecond Laser Ablation: the influence of energy and pulse width on the LA-ICP-MS analysis of monazite

We studied the influence of pulse energy (E0) and pulse width (τ) of Near Infra Red femtosecond Laser Ablation coupled to Inductively Coupled Plasma Mass Spectrometry (LA-ICP-MS). A particular emphasis was put on the 206Pb/238U and 208Pb/232Th repeatability from Moacyr monazite (Itambe, Brazil). Synthetic glass (Standard Reference Material) NIST610 was used as a reference material, as well as a monazite from Manangotry (Madagascar). Pulse energy was investigated in the range E0 = 0.03 to 0.8 mJ/pulse (τ = 60 fs) while pulse width has been studied from τ = 60 fs to 300 fs (E0 = 0.1 mJ/pulse). Data suggest that pulse width has no detectable influence on the accuracy and repeatability of measured elemental ratios in the range of 60–300 fs. Observed measurements repeatabilities are 2.5%RSD and 1.8%RSD for 206Pb/238U and 208Pb/232Th, respectively. At 60 fs, the 0.03–0.8 mJ/pulse energy range studied does not induce any detectable change in data accuracy and repeatability. Uncertainties of 1.1–2.8%RSD were obtained for 206Pb/238U. In the range of E0 = 0.1–0.8 mJ/pulse, matrix matched calibration using Manangotry monazite gives a similar good repeatability of 2.4%RSD for 206Pb/238U. No clear matrix effect could be highlighted.

Trace elements biomonitoring in a historical mining district (les Malines, France)

The aim of this study is to investigate the trace elements (TE) contents of potential biomonitors in a historical Zn-Pb mining district: apiary products (honey, royal-jelly and beeswax) lichen and moss were sampled and analysed. In spite of high TE concentrations in mining waste and soil, apiary products are free of TE contamination originating from historical mining. Lichen/moss show high TE levels, which suggest atmospheric input of local dust. Pb isotopes analysis proved the origin of TE found in lichen/moss to be mainly mining waste. These results help discuss the choice of relevant organisms for monitoring TE in the environment and bring additional data on the potential impacts of brownfields left after mining, especially on food products from apiaries.

Child neurodevelopment in a Bolivian mining city

This study evaluates the neurodevelopment of children living near contaminated mining industries during their first year of life. Participants from the city of Oruro (Bolivia) were prospectively recruited during pregnancy. Follow-up occurred between May 2007 and November 2009. Information about the socioeconomic status and medical history of the pregnant women were collected using questionnaires. Neurodevelopment was evaluated for 246 children using the Bayley Scales of Infant Development (BSID) at 10.5-12.5 months of age. Exposure to trace elements (Pb, As, Cd, Sb, Cs, Zn, Fe, Cu, Se, Rb, and Sr) during prenatal life was evaluated by testing maternal blood concentrations before delivery. Almost all measured levels were lower than the control limits. The blood lead concentration of pregnant women was low, considering the contaminated environmental context. The geometric mean was 1.76 μg/dL (95% CI: 1.68-1.84), a level comparable with those observed in non-contaminated areas. The only element found to be relatively elevated was antimony, with a geometric mean of 1.03 μg/dL (95% CI: 0.96-1.11). Our results suggest that women from this mining area were not highly exposed. The Bayley Scales of Infant Development (BSID) did not reveal mental or psychomotor abnormalities. Surprisingly, at the observed low levels, lead was positively associated with the childrens BSID performance.