Secondary Ion Mass Spectrometry Bias on Isotope Ratios in Dolomite–Ankerite,Part II: δ13C Matrix Effects

This study is Part II of a series that documents the development of a suite of calibration reference materials for in situ SIMS analysis of stable isotope ratios in Ca‐Mg‐Fe carbonates. Part I explored the effects of Fe²⁺ substitution on SIMS δ¹⁸O bias measured from the dolomite–ankerite solid solution series [CaMg(CO₃)₂–CaFe(CO₃)₂], whereas this complementary work explores the compositional dependence of SIMS δ¹³C bias (calibrated range: Fe# = 0.004–0.789, where Fe# = molar Fe/(Mg+Fe)). Under routine operating conditions for carbonate δ¹³C analysis at WiscSIMS (CAMECA IMS 1280), the magnitude of instrumental bias increased exponentially by 2.5–5.5‰ (session‐specific) with increasing Fe‐content in the dolomite structure, but appeared insensitive to minor Mn substitution [< 2.6 mole % Mn/(Ca+Mg+Fe+Mn)]. The compositional dependence of bias (i.e., the matrix effect) was expressed using the Hill equation, yielding calibration residual values ≤ 0.3‰ relative to CRM NBS‐19 for eleven carbonate reference materials (6‐μm‐diameter spot size measurements). Based on the spot‐to‐spot repeatability of a drift monitor material that ‘bracketed’ each set of ten sample‐spot analyses, the analytical precision was ± 0.6–1.2‰ (2s, standard deviations). The analytical uncertainty for individual sample analyses was approximated by combining the precision and calibration residual values (propagated in quadrature), suggesting an uncertainty of ± 1.0–1.5‰ (2s).     

Precise and Accurate Doping of Nanoporous Silica Gel for the Synthesis of Trace Element Microanalytical Reference Materials

This study presents an experimental procedure to fabricate high‐purity silica glass containing a selected element at a specified mass fraction. The procedure was used to prepare glasses doped with trace‐level mass fractions of Ti with the goal of improving analytical confidence when measuring trace elements in quartz. Systematic tests were performed to determine the ideal conditions and procedures for doping nanoporous silica gel with the highest efficiency of dopant recovery. Silica gel was cleaned in concentrated HCl, immersed in a non‐polar doping medium at a controlled pH and doped with precise quantities of ICP‐MS standard solution. Using liquids composed of longer chain molecules as the doping medium diminishes recovery, suggesting that large molecules could obstruct nanopores to inhibit capillary uptake of the dopant. A control experiment using crystalline quartz reinforced the effectiveness of nanoporous silica gel for doping with trace‐level precision. Layered aggregates of silica gel doped with different Ti mass fractions were hot‐pressed to create multi‐layered reference materials that were analysed with multiple techniques at a variety of spatial scales. Analyses at the intra‐grain scale (cathodoluminescence scanning electron microscopy, electron probe microanalysis), at the single grain scale (SIMS), at the sample layer scale (EPMA, laser ablation‐ICP‐MS) and at the bulk scale (ICP‐OES) demonstrated acceptable homogeneity at sample volumes characteristic of most microanalysis techniques and show that nanoporous silica gel holds promise as a highly retentive doping substrate for preparing reference materials for laser‐, electron‐ and ion‐beam microanalysis.     

Appropriate Sampling for Optimised Measurement (ASOM), rather than the Theory of Sampling (TOS) Approach,to Ensure Suitable Measurement Quality: A Refutation of Esbensen and Wagner (2014)

The ‘Appropriate Sampling for Optimised Measurement’ (ASOM) approach considers measurement to be the focus of the sampling process, and sampling to be only the first part of the measurement process. To achieve ASOM, the uncertainty of measurements, including its contribution from sampling, needs to be estimated and optimised in order to achieve fitness‐for‐purpose. Such samples are then ‘sufficiently’ representative. The ‘Theory of Sampling’ (TOS) focuses on the processes of primary sampling and sample preparation and assumes that samples are ‘representative’ if they are correctly prepared by nominally ‘correct’ protocols. It defines around ten sampling ‘errors’, which are either modelled or minimised to improve sampling quality. It is argued that the ASOM approach is more effective in achieving appropriate measurement quality than in applying TOS to just the first part of the measurement process. The comparison is made less effective by the different objectives, scopes, terminology and assumptions of the two approaches. ASOM can be applied to in situ materials that are too variable to be modelled accurately, or where sources of uncertainty are unsuspected. The proposed integration of ASOM with TOS (Esbensen and Wagner 2014, Trends in Analytical Chemistry, 57, 93–106) is therefore effectively impossible. However, some TOS procedures can be useful within the ASOM approach.     

Development of a New Method of Extraction of Interstitial Water from Low‐Porosity Consolidated Sediments Recovered During Super‐Deep Drilling Projects

During the Integrated Ocean Drilling Program (IODP) Expedition 338, several methods were tested for the extraction of interstitial water in consolidated, low‐porosity deep‐sea sediments from Site C0002 in the Kumano Basin. On the basis of those tests, we propose a modified ground rock interstitial normative determination (GRIND) method of extraction of interstitial water. In separate runs of the new method, sediment samples were ground in a ball mill with either ultrapure water or a solution of HNO₃. The interstitial water was then extracted with a conventional squeezer. Sufficient solution was extracted by this method to analyse most major and a few minor components of interstitial water that were comparable to those previously reported for samples extracted by the conventional squeezing method. The new method requires much smaller amounts of sediment than that of the conventional method and will be useful for analysis of samples recovered during super‐deep drilling programmes.     

Evaluating the Effects of Autofluorescence during Raman Hyperspectral Imaging

Raman hyperspectral imaging is becoming a popular technique to analyse geological materials. Autofluorescence can affect the quality of the spectra that comprise hyperspectral data sets. Few studies have addressed potential misinterpretation of Raman images from hyperspectral data sets affected by autofluorescence. Additionally, little work has been done to develop methods for identifying the spatial distribution of spectra affected by autofluorescence. This study illustrates how autofluorescence may lead to misinterpretation of the distribution of materials based on intensity at a point images. A method is proposed utilising signal to axis analysis to create images that identify regions affected by autofluorescence. Post‐processing baseline correction is often used to address autofluorescence, and most software programs utilise a form of partial least squares regression modelling based on a subjective choice of polynomial order. This study shows that an inappropriate choice of polynomial order can introduce error, which may lead to misinterpretation of Raman images. A signal to axis analysis method is proposed to statistically compare seemingly ‘appropriate’ baseline correction trials. Although post‐processing of hyperspectral data sets and creating Raman images seem simple, data quality issues such as autofluorescence must be considered. If baseline correction is deemed necessary, it should be addressed as an experiment involving statistical comparison.     

The Orosirian-Statherian banded iron formation-bearing sequences of the southern border of the Espinhaço Range,Southeast Brazil

The Serra da Serpentina and the Serra de São José groups are two distinct banded iron formation-bearing metasedimentary sequences along the eastern border of the southern Espinhaço Range that were deposited on the boundary between the Orosirian and Statherian periods.The Serra da Serpentina Group (SSG) has an Orosirian maximum depositional age (youngest detrital zircon grain age = 1990 ± 16 Ma) and consists of fine clastic metasediments at the base and chemical sediments, including banded iron formations (BIFs), on the top, corresponding to the Meloso and Serra do Sapo formations, respectively, and correlating with the pre-Espinhaço Costa Sena Group. The SSG represents sedimentary deposition on an epicontinental-epeiric, slow downwarping sag basin with little tectonic activity.The younger Serra de São José Group (SJG) is separated from the older SSG by an erosional unconformity and was deposited in a tectonically active continental rift-basin in the early stages of the opening of the Espinhaço Trough. The Serra do São José sediments stretch along the north-south axis of the rift and comprise a complete cycle of transgressive sedimentary deposits, which were subdivided, from base to top, into the Lapão, Itapanhoacanga, Jacém and Canjica formations. The Itapanhoacanga Formation has a maximum depositional age of 1666 ± 32 Ma (Statherian), which coincides with the maximum depositional age (i.e., 1683 ± 11 Ma) of the São João da Chapada Formation, one of the Espinhaço Supergroup's basal units. The Serra de São José Rift and the Espinhaço Rift likely represent the same system, with basal units that are facies variations of the same sequence.The supracrustal rocks have undergone two stages of deformation during the west-verging Brasiliano orogeny that affected the eastern margin of the São Francisco Craton and generated a regional-scale, foreland N–S trending fold-thrust belt, which partially involved the crystalline basement. Thrust faults have segmented the terrain into a large number of tectonic blocks, where the stratigraphic sequence was nevertheless well preserved.     

Copepod assemblages in a highly complex hydrographic region

Community structure and diversity patterns of planktonic copepods were investigated for the Southwestern Atlantic Ocean between 34 and 41°S. Our objectives were (1) to define copepod assemblages, (2) to accurately identify their association to different water masses/hydrodynamic regimes, (3) to characterize the assemblages in terms of their community structure, and (4) to test if frontal boundaries between water masses separate copepod assemblages. Biogeographic patterns were investigated using multivariate analysis (cluster and ANOSIM analyses). Biodiversity patterns were examined using different univariate indexes (point species richness and taxonomic distinctness). Five regions of similar copepod assemblages were defined for our study area each one corresponding to different environments (freshwater, estuarine, continental shelf, Malvinas and Brazil current assemblages). These assemblages have major community structure differences. In spite of the complex oceanographic scenario of our study area, that can lead us to expect a pattern of copepod communities with diffuse boundaries, we found a strong spatial correspondence between these limits and the presence of permanent frontal structures.     

Morphology of the Blanco Transform Fault Zone-NE Pacific: Implications for its tectonic evolution

The right-lateral Blanco Transform Fault Zone (BTFZ) offsets the Gorda and the Juan de Fuca Ridges along a 350 km long complex zone of ridges and right-stepping depressions. The overall geometry of the BTFZ is similar to several other oceanic transform fault zones located along the East Pacific Rise (e.g., Siquieros) and to divergent wrench faults on continents; i.e., long strike-slip master faults offset by extensional basins. These depressions have formed over the past 5 Ma as the result of continual reorientation of the BTFZ in response to changes in plate motion. The central depression (Cascadia Depression) is flanked by symmetrically distributed, inward-facing back-tilted fault blocks. It is probably a short seafloor spreading center that has been operating since about 5 Ma, when a southward propagating rift failed to kill the last remnant of a ridge segment. The Gorda Depression on the eastern end of the BTFZ may have initially formed as the result of a similar occurrence involving a northward propagating rift on the Gorda ridge system. Several of the smaller basins (East Blanco, Surveyor and Gorda) morphologically appear to be oceanic analogues of continental pull-apart basins. This would imply diffuse extension rather than the discrete neovolcanic zone associated with a typical seafloor spreading center. The basins along the western half of the BTFZ have probably formed within the last few hundred thousands years, possibly as the result of a minor change in the Juan de Fuca/Pacific relative motion.     

三峡库区坡耕地退耕与粮食安全的空间分异

坡耕地退耕还林还草作为生态环境建设的一项重要措施，已在全国逐步开展。坡耕地退耕使耕地数量减少，并影响到退耕地区粮食产量减少，尤其在坡耕地分布集中、交通不便地区的尤为突出。本文利用GIS技术对三峡库区坡耕地空间分布进行了分析，探讨了三峡库区坡耕地退耕后粮食安全隐患产生的原因，初步揭示了粮食供需矛盾的空间差异，并结合交通便利状况，划分粮食安全区、警戒区，危机区等三种不同类型的区域。     

Direct Determination of Lead Isotope Ratios by Laser Ablation-Inductively Coupled Plasma-Quadrupole Mass Spectrometry in Lake Sediment Samples

A direct method for the determination of lead isotopic ratios by laser ablation-inductively coupled plasma-quadrupole mass spectrometry (LA-ICP-QMS) is presented. Samples of lake sediments were ground and pressed as pellets before being analysed. Mass bias was corrected by analysing an external calibration sample manufactured with pure silica doped with NIST SRM 981 solution. The efficiency of the mass bias correction was checked by comparing the ICP-MS data with lead isotopic ratios determined by thermal ionisation mass spectrometry (TIMS). The average long term reproducibilities were 0.40%, 0.40%, 0.20% and 0.30% (RSD) respectively for the ²⁰⁶Pb/²⁰⁴Pb, ²⁰⁷Pb/²⁰⁴Pb, ²⁰⁶Pb/²⁰⁷Pb and ²⁰⁸Pb/²⁰⁶Pb ratios. The method was applied to the study of lake sediment samples, in order to determine the amount and origin of historical contamination by lead.