Multi-Elemental Analysis of ATHO-G Rhyolitic Glass (MPI-DING Reference Material) by Femtosecond and Nanosecond LA-ICP-MS: Evidence for Significant Heterogeneity of B,V, Zn,Mo, Sn,Sb, Cs,W, Pt and Pb at the Millimetre Scale

This paper reports on the application of variants of LA-ICP-MS – including infrared femtosecond laser ablation (fs-LA) inductively coupled plasma-quadrupole mass spectrometry (ICP-QMS) and nanosecond laser ablation (ns-LA) coupled with single-collector sector-field (SF-) ICP-MS – to the in situ determination of trace elements in different splits of the reference material (RM) ATHO-G (MPI-DING). Analyses of the materials performed by fs- and ns-LA-ICP-MS demonstrated the efficiency of the techniques with typical accuracy at a level of ≤ ± 20%. One ‘anomalous’ split, however, displayed a significant discrepancy from the reference concentrations for B, V, Zn, Mo, Sn, Sb, Cs, W and Pb. Three- to six-fold enrichment of V, Mo, Cs and Pt relative to the reference contents in this split is likely to have been due to direct contact of the silicate melt with Pt crucible walls and ceramics. Boron, Zn, Sn, Sb, W and Pb depletion relative to the reference concentrations is probably due to siderophile element adsorption by the Pt walls and/or related to the formation of volatile-depleted compositional cords during the preparation process. Our results imply that additional precautions should be taken against volatile/siderophile element heterogeneity in marginal/surface layers (≤ 10 mm) during the preparation of RMs by the fusion technique.     

Reconstitution de données climatiques pour l’Algérie du Nord : application des réseaux neuronaux

In the present context of climate change and preservation of biodiversity, the appreciation of the vulnerability of the natural ecosystems and their capacity of adaptation appears among the main preoccupations to the world level (GIEC, 2007). This assessment of the ecosystems requires the availability of climatic data, what is often made difficult by the weak density or even the absence of meteorological stations notably, to the level of the mountains zones. In order to study the climate–vegetation relationship in North Algeria, we use an automatic interpolation method, the neural network method, for the reconstitution of climatic data of the sampled sites, (1035 phytoecological samples), from the existing meteorological network (269 stations). This method is characterized by a great suppleness of non-linearity and by its capacity for reconstituting information from partial and not well-defined indications such as the case of data provided from meteorological networks. In order to reconstitution of climatic data, we use the explicate variables, longitude, latitude and altitude, the variables to explain being the rainfall and temperatures. To define the best approach, the network calibration has been activated on climatic parameters taken globally or solely, for the whole of study zone, and by geographical sector. The results of the interpolation are expressed through a climatic parameter cartography, released automatically by the MapInfo software. The reliability results obtained by this method can be appreciated by elaboration of errors maps comparing to reference data.     

New Approach to Geochemical Measurement: Estimation of Measurement Uncertainty from Sampling,rather than an Assumption of Representative Sampling

It is argued that the current division between field sampling and chemical analysis is counterproductive in terms of ensuring that geochemical measurement results are fit for their intended purpose. An integrated approach to the whole measurement process has many advantages including no dependence on the two assumptions that either the samples are necessarily representative if taken with a correct protocol, or that the measurement results can be assumed to be true values of chemical concentration. The measurement results then require values of measurement uncertainty, including that from sampling as well as from chemical analysis. This enables the user of the measurement results, rather than the producer, to judge their fitness for a specific purpose. Case studies are used to illustrate the practicality and benefits of this new approach, including the use of measurement results with optimal, but relatively high, levels of uncertainty to make reliable decisions. This contrasts with the traditional assumption that pursuit of the lowest possible measurement uncertainty is the best approach.     

Palaeoecological constraints on late Glacial and Holocene ice retreat in the Southern Andes (53°S)

Late Glacial to Holocene ice retreat was investigated along a 120 km long fjord system, reaching from Gran Campo Nevado (GCN) to Seno Skyring in the southernmost Andes (53°S). The aim was to improve the knowledge on regional and global control on glacier recession with special emphasis on latitudinal shifting of the westerlies. The timing of ice retreat was derived from peat and sediment cores, using mineralogical and chemical characteristics, and pollen as proxies. Stratigraphy was based on ¹⁴C-AMS ages and tephrochronology. The ice retreat of the Seno Skyring Glacier lobe is marked by an ice rafted debris layer which was formed around 18,300 to 17,500 cal. yr B.P. Subsequently, fast glacier retreat occurred until around 15,000 to 14,000 cal. yr B.P. during which around 84% of Skyring Glacier were lost. This fast recession was probably also triggered by an increase of the Equilibrium Line Altitude (ELA) from 200 to 300 m. Subsequently, the ice surface was lowered below the ELA in an area that previously made up more than 50% of the accumulation area. Much slower retreat and glacier fluctuations of limited extent in the fjord channel system northeast of GCN occurred between around 14,000 to 11,000 cal. yr B.P. during both the Antarctic Cold Reversal and the Younger Dryas. This slow down of retreat indicates a decline in the general warming trend and/or increased precipitation, due to a southward migration of the westerlies. After around 11,000 cal. yr B.P. pollen distribution shows evolved Magellanic Rainforest and similar climate as at present, which lasted throughout most of the Holocene. Only Late Neoglacial moraine systems were formed in the period 1220–1460 AD, and subsequently in the 1620s AD, and between 1870 and 1910 AD. The results indicate that the Gran Campo Nevado ice cap has reacted more sensitive and partly distinct to climate change, compared to the Patagonian Ice Field.     

Declining Oxygen on the British Columbia Continental Shelf

The first thorough examination of oxygen concentrations in Canadian waters of the Pacific Ocean reveals several patterns in space and time. Sub-surface concentrations of oxygen tend to be lower in shelf waters than in deep-sea waters on the same isopycnal and lower in southern waters of the continental shelf than farther north. The lowest near-bottom concentration was 0.7 ml L^?1 (31 μmol kg^?1) in mid-shelf waters in summer off southwest Vancouver Island in the Juan de Fuca Eddy region. Oxygen concentration there declined at a rate of 0.019 ml L^?1 y^?1 (0.83 μmol kg^?1 y^?1) from 1979 to 2011. This decline is attributed mainly to changes in oxygen concentrations on the same density surfaces, rather than to changes in the depth of constant-density surfaces. A numerical simulation of ocean currents and nutrient concentrations in and surrounding the Juan de Fuca Eddy in summer reveals persistent upwelling into the centre of this eddy and slow bottom currents within the eddy. Upwelled water at bottom of the Juan de Fuca Eddy has water properties associated with the California Undercurrent on the 26.6 sigma-t surface at 200 m depth, where oxygen concentration is typically 2.0 ml L^?1 (87 μmol kg^?1) and declined at a rate of 0.025 ml L^?1 y^?1 (1.1 μmol kg^?1 y^?1) from 1981 to 2011, mainly as a result of changes on constant-density surfaces rather than to uplifting isopycnals. We propose that upwelling advects deep, oxygen-poor water onto the continental shelf bottom, and the slow bottom currents allow time for oxidation of organic material in bottom waters to further reduce the oxygen concentration.

RÉSUMÉ?[Traduit par la rédaction] Le premier examen approfondi des concentrations d'oxygène dans les eaux canadiennes de l'océan Pacifique révèle plusieurs configurations dans le temps et dans l'espace. Les concentrations d'oxygène sous la surface ont tendance à être plus faibles dans les eaux de la plate-forme continentale que dans les eaux de l'océan profond sur la même isopycne et plus faibles dans les eaux du sud de la plate-forme que plus loin au nord. La concentration la plus faible près du fond était de 0.7 ml L^?1 (31 μmol kg^?1) dans les eaux du milieu de la plate-forme en été au large du sud-ouest de l’île de Vancouver dans la région du remous de Juan de Fuca. Les concentrations en oxygène à cet endroit ont diminué au rythme de 0.019 ml L^?1 a^?1 (0.83 μmol kg^?1 a^?1) entre 1979 et 2011. Cette diminution est principalement attribuée aux changements dans les concentrations d'oxygène sur les surfaces d’égale densité plutôt qu'aux changements dans la profondeur des surfaces de densité constante. Une simulation numérique des courants océaniques et des concentrations de nutrients dans le remous de Juan de Fuca et dans les régions avoisinantes en été révèle des remontées d'eau froide persistantes vers le centre de ce remous et des courants de fond lents à l'intérieur du remous. L'eau qui a remonté au fond du remous de Juan de Fuca a des propriétés liées au sous-courant de Californie sur la surface sigma–t 26.6 à une profondeur de 200 m, où la concentration en oxygène est normalement de 2.0 ml L^?1 (87 μmol kg^?1), et a diminué au taux de 0.025 ml L^?1 a^?1 (1.1 μmol kg^?1 a^?1) de 1981 à 2011, principalement à cause des changements sur les surfaces de densité constante plutôt que du soulèvement des isopycnes. Nous pausons l'hypothèse que les remontées d'eau advectent des eaux profondes pauvres en oxygène au bas de la plate-forme continentale et que les lents courants de fond donnent le temps à l'oxydation de la matière organique dans les eaux de fond, ce qui réduit davantage la concentration de l'oxygène.     

秘鲁航磁特征及铁矿类型

为了解秘鲁国铁矿分布规律,对秘鲁22.5万km2的航磁资料进行了化极、延拓、求导等各种处理工作,通过分析已知铁矿的航磁异常,结合秘鲁区域地质构造以及秘鲁各地质年代地层及岩性特征,归纳得出与不同铁矿类型有关的磁异常类型。它们主要有:陆相火山喷溢型的铁矿异常;受断裂构造控制的与第三纪早、中期的火山喷发物质有关的磁异常区;第三纪早、中期的火山喷发物质掩盖区的磁异常;分布于海岸带内的正磁异常带;位于闪长岩体的岩浆期后热液脉状铁矿异常;矽卡岩型铁矿异常。这对认识安第斯山大地构造以及圈定有利的铁矿成矿靶区有一定的意义。     

Accurate and High‐Precision Determination of Boron Isotopic Ratios at Low Concentration by MC‐ICP‐MS (Neptune)

We report an approach for the accurate and reproducible measurement of boron isotope ratios in natural waters using an MC‐ICP‐MS (Neptune) after wet chemistry sample purification. The sample matrix can induce a drastic shift in the isotopic ratio by changing the mass bias. It is shown that, if no purification is carried out, the direct measurement of a seawater diluted one hundred times will induce an offset of ?7‰ in the isotopic ratio, and that, for the same concentration, the greater the atomic mass of the matrix element, the greater the bias induced. Whatever the sample, it is thus necessary to remove the matrix. We propose a method adapted to water samples allowing purification of 100 ng of boron with a direct recovery of boron in 2 ml of 3% v/v HNO₃, which was our working solution. Boron from the International Atomic Energy Agency IAEA‐B1 seawater reference material and from the two groundwater reference materials IAEA‐B2 and IAEA‐B3, was chemically purified, as well as boron from the certified reference material NIST SRM 951 as a test. The reproducibility of the whole procedure (wet chemistry and MC‐ICP‐MS measurement) was ± 0.4‰ (2s). Accuracy was verified by comparison with positive‐TIMS values and with recommended values. Seawater, being homogeneous for boron isotope ratios, is presently the only natural water material that is commonly analysed for testing accuracy worldwide. We propose that the three IAEA natural waters could be used as reference samples for boron isotopes, allowing a better knowledge of their isotopic ratios, thus contributing to the certification of methods and improving the quality of the boron isotopic ratio measurements for all laboratories.     

Microzooplankton feeding impact in a coastal upwelling system on the NW Iberian margin: The Ría de Vigo

The dilution technique, combined with identification and enumeration of pico-, nano- and micro-plankton by microscopy, was used to estimate microzooplankton impact on the microbial community in surface waters of a coastal embayment on the NW Iberian upwelling system. Microzooplankton were important consumers of autotrophic and heterotrophic plankton in this system, feeding up to 93% of standing stock and more than 100% of production of several groups. Heterotrophic bacteria and heterotrophic picoflagellates experienced the highest and constant impact, with 75–84% of their standing stocks and 85–102% of their production being channelled through the microbial food web. Pico- and nano-phytoplankton were also consumed, although maximum grazing occurred on diatoms during upwelling events, coinciding with highest primary production. Predation on pico-nano-heterotrophs was especially relevant under downwelling conditions, when consumption of total carbon and particularly autotrophic carbon was considerably lower than during upwelling. The results suggest that the existence of a multivorous food web, extending from the microbial loop to the herbivorous food web, could be a major feature in this coastal upwelling system. The microbial loop, which occurs as a permanent background in the system, would contribute to sustain the microbial food web during downwelling, whereas the herbivorous food web could coexist with a microbial food web based on large diatoms during upwelling. The multivorous food web would partially divert diatoms from sinking and hence favour the retention of organic matter in the water column. This could enhance the energy transfer to higher pelagic trophic levels in coastal upwelling systems.     

Lichenometry in the Cordillera Blanca, Peru: “Little Ice Age” moraine chronology

This paper is a comparison and compilation of lichenometric and geomorphic studies performed by two independent teams in the Cordillera Blanca, Peru, in 1996 and 2002 on 66 “Little Ice Age” moraines of 14 glaciers. Using eleven new control points, we recalibrated the initial rapid growth phase of the previously established Rhizocarpon subgenus Rhizocarpon growth curve. This curve was then used to estimate the age of “Little Ice Age” moraines. The time of deposition of the most prominent and numerous terminal and lateral moraines on the Pacific-facing side of the Cordillera Blanca (between AD 1590 and AD 1720) corresponds to the coldest and wettest phase in the tropical Andes as revealed by ice-core data. Less prominent advances occurred between AD 1780 and 1880.