GGR Critical Review of Analytical Developments in 2004–2005

In 2005 Geostandards and Geoanalytical Research embarked upon a new initiative for its readers. Key researchers in various fields of geoanalytical technique development and their application were identified and invited to provide reviews pertinent to their expertise. As noted in the first of these publications "…instead of revisiting the historical context or decades of development in each analytical technique, the goal here has been to capture a snapshot of "hot topics" across a range of fields as represented in the… literature" (Hergt et al . 2005). Rather than prepare an annual review, a decision was taken earlier this year to provide a biennial summary of progress and accomplishments, in this case for the years 2004–2005. The principal techniques employed in Earth and environmental sciences are covered here, and include laser ablation and multicollector ICP-MS, ICP-AES, thermal ionisation and secondary ion mass spectrometry, as well as neutron activation analysis, X-ray fluorescence and atomic absorption spectrometry. A comprehensive review of the development of reference materials, often essential to these techniques, is also provided. The contributions assembled serve both to keep readers informed of advances they may be unfamiliar with, but also as a means of showcasing examples of the breadth and depth of work being conducted in these fields.     

Reference Materials in Geoanalytical Research -Review for 2004 and 2005

This review gives an overview of the use and development of reference materials of geochemical and environmental interest in the literature of the years 2004 and 2005. In these years the performance of existing methods has been improved and new geochemical applications using new techniques have been developed. Accordingly, there was an increasing need for new reference materials, especially for in situ microanalysis and for precise stable isotope measurements. In addition, there was a notable trend for further characterisation of existing reference materials, mainly for the platinum-group elements. This review focuses on five topics: reference materials for platinum-group elements, reference glasses for in situ microanalysis, zircon reference materials, isotopic reference materials, and the development and certification of reference materials.     

长白山锦北雨养泥炭剖面元素富集规律分析

为了揭示长白山锦北泥炭沼泽区泥炭沉积环境和重金属元素的历史变化及其对环境的指示意义,利用荷兰W ardenaar泥炭采样器采取泥炭样品并对样品进行高分辨率切割。用原子吸收分光光度计和等离子体发射光谱仪测定不同深度剖面Ca,Mg,Na,K,A l,Ti,Cu,Zn,Fe,Mn,Pb,Cr,N i和Co的浓度。研究分析了Ca,Mg,Na,K,A l,Ti,Mn,Zn,Cu,Pb,Cr,N i和Co在泥炭剖面的分布趋势并对其进行了相关分析和富集分析,得出Mn,Zn,Cu,Pb,Cr,N i和Co呈显著相关且在泥炭表层明显累积,揭示出泥炭表层重金属元素的大气沉降来源,表明近年来人类重金属消耗量及排放量的增加是大气沉降重金属元素的主要释放源,而且环境中重金属污染有加重的趋势。     

High resolution profiles of trace metals in pore waters of marine and riverine sediments assessed by DET and DGT

In polluted aquatic systems, toxic metals are often accumulated in bottom sediments. They are, however, not necessarily stored definitively because diagenetic processs can modify redox, pH and even the amount of complexing ligands, releasing the trace metals back into the pore waters and the water column. Especially the labile metal fraction in the pore waters is important since this is the bioavailable fraction determining the bio-toxicity of the sediments. The goal of our study was therefore to assess, with novel sampling techniques, this bioavailable metal fraction in the pore waters as well as the flux towards the overlying water column. High-resolution profiles of trace metals in pore waters of marine and riverine sediments were assessed by DET （diffusive equilibrium in thin films） and DGT （diffusive gradients in thin films） gel techniques. The DET technique uses a diffusive gel layer that equilibrates with the aquatic system and with this technique the concentrations of total dissolved trace metals are obtained directly. The DGT technique uses an acrylamide diffusive gel backed by a resin gel （Chelex） which binds trace metals. With the DGT technique only labile species of selected metals can be captured. According to the redox potential measurements, the marine sediments were suboxic （200 mV to -220 mV versus Ag/AgCl electrode）, while the riverine sediments were completely anoxic （-160 mV to -220 mV versus Ag/AgCl electrode）. This redox potential was apparently controlling the trace metals species in the pore waters： for example a strong correlation between Mn and Co was found in the riverine sediments （for DET and DGT sampling）, while in the marine sediments trace metals presented various behaviors.     

Attenuation of aqueous metal transport at two natural acid rock drainage occurrences in the Yukon Territory, Canada

Naturally acidic drainage associated with pyritic black shale has been observed in many locations in the Yukon Territory. While not necessarily linked to known mineral deposits, most of these natural acid rock drainage occurrences show elevated dissolved concentrations of trace elements, especially zinc, nickel, copper, cadmium and arsenic. Based on field observations, microbial investigation, chemical analyses and geochemical modeling, the fate and transport of potentially deleterious elements at two natural acid drainage occurrences with slightly different settings are examined. The Macintosh Creek is a small, acidic stream （pH 2.98-3.40）, 2 km long, located in the Macmillan Pass area of east-central Yukon amidst known sedimentary exhalative massive sulfide mineralization but remains undisturbed by exploration activities. Its trace metal content is apparently derived from groundwater discharges, which gave as much as 5.0, 2.5, 0.7, 0.13 and 0.03 mg/L ofZn, Ni, Cu and As, respectively. Interaction and sorption reactions with algal mats, biofilms and iron oxyhydroxides appear to be the dominant mechanisms attenuating aqueous contaminant transport along the stream. Cryogenic precipitation further consolidates the ferricrete formation and reduces the mobility of the sorbed metals. The tributaries of the Engineering Creek along the Dempster Highway in northern Yukon drain through a series of dolomite, phyllite, argillite, limestone, black shale, sandstone and conglomerate with no known concentration of mineralization. In this area, the water chemistry fully reflects the local geology with acidic streams invariably associated with black shale occurrences. Groundwater seeps in the headwaters area of the km-180 Creek completely enclosed in black shale gave pH 3.0 and as much as 148, 39, 2.9 and 9.1 mg/L of Zn, Ni, Cu and As, respectively. Sorption with iron oxyhydroxide and organic matter appear to dominate the attenuation of contaminant transport along the stream. However, once entered into carbonate-dominated terrains, secondary carbonate minerals exercise additional geochemical control on the local water chemistry as a result of neutralization.     

Influence of humic acid on bioavailability of heavy metals in sediments

The mimetic ocean environment and chemical method were used to research the bioavailability effect of humic acid on five heavy metals in sediment, including Cd, Cu, Zn, Pb and Ni. The sediment was separated into four containers with artificial seawater, and each of them had different concentrations of humic acid. The values of concentrations covered the whole range found in natural sediment （0.1%-10%）. According to the 48 hours LC50 of clam and distribution coefficient, metals were added in artificial seawater, and their speciation was determined at first and then after two days＇ incubation. It was found the bioavailability of heavy metals was reduced in the presence of humic acid. The obvious negative effect on Zn was observed, but the influence on Cd was not remarkable. In addition, the contents of Pb and Ni increased obviously in organic phase, and they are correlative with the concentrations of humic acid.     

The distribution of radiogenic heat production as a function of depth in the Sierra Nevada Batholith, California

Geochemical analyses and geobarometric determinations have been combined to create a depth vs. radiogenic heat production database for the Sierra Nevada batholith, California. This database shows that mean heat production values first increase, then decrease, with increasing depth. Heat production is 2 μW/m³ within the 3-km-thick volcanic pile at the top of the batholith, below which it increases to an average value of 3.5 μW/m³ at 5.5 km depth, then decreases to 0.5–1 μW/m³ at 15 km depth and remains at these values through the entire crust below 15 km. Below the crust, from depths of 40–125 km, the batholith's root and mantle wedge that coevolved beneath the batholith appears to have an average radiogenic heat production rate of 0.14 μW/m³. This is higher than the rates from most published xenolith studies, but reasonable given the presence of crustal components in the arc root assemblages. The pattern of radiogenic heat production interpreted from the depth vs. heat production database is not consistent with the downward-decreasing exponential distribution predicted from modeling of surface heat flow data. The interpreted distribution predicts a reasonable range of geothermal gradients and shows that essentially all of the present day surface heat flow from the Sierra Nevada could be generated within the 35 km thick crust. This requires a very low heat flux from the mantle, which is consistent with a model of cessation of Sierran magmatism during Laramide flat-slab subduction, followed by conductive cooling of the upper mantle for 70 m.y. The heat production variation with depth is principally due to large variations in uranium and thorium concentration; potassium is less variable in concentration within the Sierran crust, and produces relatively little of the heat in high heat production rocks. Because silica content is relatively constant through the upper 30 km of the Sierran batholith, while U, Th, and K concentrations are highly variable, radiogenic heat production does not vary directly with silica content.     

Monazite behaviour and age significance in poly-metamorphic high-grade terrains: A case study from the western Musgrave Block, central Australia

Integrated, in situ textural, chemical and electron microprobe age analysis of monazite grains in a migmatitic metapelitic gneiss from the western Musgrave Block, central Australia has identified evidence for multiple events of growth and recrystallisation during poly-metamorphism in the Mesoproterozoic. Garnet + sillimanite-bearing metapelite underwent partial melting and segregation to palaeosome and leucosome during metamorphism between 1330 and 1296 Ma, with monazite grains in leucosome recording crystallisation at 1300 Ma. Monazite breakdown during melting is inferred to have occurred in the palaeosome. During a subsequent granulite facies event at 1200 Ma, deformation and metamorphism of leucosome and palaeosome resulted in partial disturbance of ages and potential minor growth on 1300 Ma monazite in leucosome. Growth of new, high-Y (+HREE) monazite in palaeosome domains occurred during garnet breakdown in the presence of sillimanite to cordierite and spinel, as a result of post-peak isothermal decompression. Diffusive enrichment of resorbed garnet rims in Y + HREE suggests garnet breakdown occurred slower than volume diffusion of REE. Monazite in both palaeosome and leucosome were subsequently partially to penetratively recrystallised during a retrogression event that is suggested to have occurred at 1150–1130 Ma. The intensity of recrystallisation and disturbance of ages appears linked to proximity to retrogressed garnet porphyroblasts and their occurrence in the relatively reactive or ‘fertile’ local environments provided by the palaeosome/mesosome volumes, which caused localised changes in retrogressive fluids towards compositions more aggressive to monazite. Like reaction textures, it is apparent that domainal equilibrium and reaction may control or at least strongly influence monazite REE and U–Th–Pb chemistry and hence ages.     

Biological and Geochemical Record of Anthropogenic Impacts in Recent Sediments from Lake Pupuke, Auckland City, New Zealand

Frozen sediment cores from Lake Pupuke in Auckland City, New Zealand, contain a high resolution decadal to annual scale record of changing lake paleoenvironments and geochemistry that reflects changing landuse and hydrology in the catchment over the past c. 190 years. A reliable chronology is available from AMS ¹⁴C and ²¹⁰Pb dating of the sediments, with the timing of the older part of the record supported by the first appearance of pollen of introduced Pinus and Plantago lanceolata associated with European settlement of Auckland in the early 1840s. Diatom stratigraphy, sediment elemental and carbon isotope geochemistry reflect changes in sediment sources and lake conditions commensurate with European development of the Lake Pupuke catchment, in particular enhanced algal productivity controlled by the influx of nutrients after c. 1920 AD. Attempts to prevent nuisance algal blooms in 1933, 1934 and 1939 using CuSO₄ addition produced Cu spikes in the sediment that allowed confirmation of the accuracy of the ²¹⁰Pb chronology. Hence, the elemental and isotopic composition of the Lake Pupuke sediments reflect the timing of significant anthropogenic activities, rather than climatic variations, that have occurred within the watershed over the past c. 190 years. The comparison of records of land use change in the catchment with the multi-proxy record of changes in the sediments usually allowed unambiguous identification of the signatures of change and their causes.