Rapid quantification of humic and fulvic acids by HPLC in natural waters

A simple method based on high-performance size-exclusion chromatography (HPSEC) has been developed for rapid quantification of humic and fulvic acids (HA and FA) in stream waters. A Tsk-gel column was used to separate natural dissolved organic matter (DOM) into two components: peak A and B. In terms of HPSEC chromatograms and fluorescence patterns, peak A and B were similar to the corresponding XAD-extracted HA and FA, respectively. It is suggested that peak A fraction mainly consisted of HA, and peak B fraction FA. The similar separation of HA and FA using HPSEC and a conventional XAD method suggests the consistency of molecular size distribution and physical–chemical properties of DOM. HPSEC offers a simple and rapid method for the quantification of HA and FA instead of tedious extractions of humic substances. Analyses of natural water samples show that the calculation of HA/FA based on UV absorbance was under- or over-estimated, the calibration using the extracted HS allows a more accurate quantification. The fast screening of HA and FA provides useful quantitative and qualitative information that can be used in environmental or monitoring studies.     

Influence of alcohols on the extraction of cerium(IV) by Aliquat-336 in kerosene

Tricaprylmethylammonium chloride (Aliquat-336) diluted with kerosene was used to extract cerium(IV) from nitric acid medium. Various alcohols were used as modifiers to overcome the third phase problem. The different parameters affecting the extraction process including nitric, nitrate, hydrogen ion, extractant and metal concentrations as well as the temperature were separately investigated. The effect of the investigated alcohols on the extraction process was also studied in detail at two different concentrations and correlated to their physical constants. Based on the obtained results, the extraction equilibrium was deduced and the optimum conditions for the extraction of cerium(IV) were proposed. The method was tested and applied to the separation of cerium from the hydrous oxide cake resulting from monazite sand.     

Petrological and geochronological constraints on the origin of the Palimé–Amlamé granitoids (South Togo, West Africa): A segment of the West African Craton Paleoproterozoic margin reactivated during the Pan-African collision

The Palimé–Amlamé Pluton (PAP) in southern Togo, consists of silica-rich to intermediate granitoids including enclaves of mafic igneous rocks and of gneisses. They are commonly called the “anatectic complex of Palimé–Amlamé” and without any convincing data, they were interpreted either as synkinematic Pan-African granitoids or as reworked pre Pan-African plutons. New field and petrological observations, mineral and whole-rock chemical analyses together with U–Pb zircon dating, have been performed to evaluate the geodynamic significance of the PAP within the Pan-African orogenic belt. With regard to these new data, the granitoids and related enclaves probably result from mixing and mingling processes between mafic and silicic magmas from respectively mantle and lower crust sources. They display Mg–calc-alkaline chemical features and present some similarities with Late Archaean granites such as transitional (K-rich) TTGs and sanukitoids.

The 2127 ± 2 Ma age obtained from a precise U/Pb concordia on zircon, points out a Paleoproterozoic age for the magma crystallization and a lower intercept at 625 ± 29 Ma interpreted as rejuvenation during Pan-African tectonics and metamorphism. Based on these results, a Pan-African syn to late orogenic setting for the PAP, i.e. the so-called “anatectic complex of Palimé–Amlamé”, can be definitively ruled out. Moreover according to its location within the nappe pile and its relationships with the suture zone, the PAP probably represents a fragment of the West African Craton reactivated during the Pan-African collision.     

Residual strength of slip zones of large landslides in the Three Gorges area, China

Slip zones of the large landslides in the Three Gorges area are commonly composed of fine-grained soils with substantial amount of coarse-grained particles, particularly gravel-sized particles. In this study, residual strength of the soils from slip zones of these landslides were examined in relation to their index properties based on a survey of 170 landslides. It was found that laboratory-determined residual friction angle using gravel-free fraction of the disturbed soils from the slip zones was closely related to clay content, liquid limit and plasticity index. On the other hand, in-situ residual friction angle of these soils (i.e. including gravel fraction) showed very weak correlations with clay content and Atterberg limits, but was largely dependent on gravel and fines (clays + silts) contents, increasing with gravels and decreasing with fines, and displayed strong linear correlation with the ratio of gravel to fines contents. These observations indicate that among the index properties, clay content and Atterberg limits can be used to estimate residual strength of the soils finer than 2 mm, but they are not appropriate evaluate the residual strength of the soils containing considerable amount of gravel-sized particles. For the latter, particle size distribution (particularly the ratio of gravel to fines contents) appears to be a useful index. Additionally, it was found that there was no identifiable correlation between relative abundance of individual major clay minerals and residual friction angles of both gravel-free fraction of disturbed and in-situ soils, suggesting that influence of clay minerals on residual strength of these soils can not be simply evaluated based on their abundance.     

Determination of Bromine and Iodine in Twenty-three Geochemical Reference Materials by ICP-MS

Trace amounts (from nanogram to microgram levels) of bromine and iodine were determined by inductively coupled plasma-mass spectrometry (ICP-MS) in twenty-three geochemical reference materials issued by the GSJ, USGS, IAEA etc. The pyrohydrolysis technique was used to separate bromine and iodine from samples analysed in the form of powder. The accuracy and precision of the experimental values were assessed by the comparative analysis of well established reference materials such as USGS AGV-1, BCR-1 and IGGE GBW07312. The measured values agreed well with reported values within a 10% error range. We also report reliable new data for these elements in these geochemical reference materials.     

On the origin of oriented rutile needles in garnet from UHP eclogites

Although oriented rutile needles in garnet have been reported from several ultrahigh‐pressure (UHP) rocks and considered to be important UHP indicators, their crystallographic features including growth habit and lattice correspondences with garnet host have never been properly characterized. This paper presents a detailed analytical electron microscopic (AEM) study on evenly distributed oriented rutile needles in garnet of two eclogitic rocks from Sulu. Some garnet in one UHP diamondiferous quartzofeldspathic rock from the Saxonian Erzgebirge, and in one high‐pressure (HP) felsic granulite from Bohemia also contain a few unevenly distributed oriented rutile needles. They have also been studied for the purpose of comparison. Despite different distribution patterns, AEM revealed that all rutile needles are oriented along the 〈111〉 directions of garnet with their lateral sides surrounded by the {110} planes of garnet, and that the growth directions of most needles are close to the normal of the {101} planes of rutile. No other specific crystallographic orientation relationships between rutile and garnet host were observed, and there is no pyroxene associated with rutile, as necessitated by the precipitation reaction of rutile in garnet as previously proposed. A simple solid‐state precipitation scenario for the formation of the rutile needles in garnet in these two eclogitic rocks is not justified. Three alternative mechanisms are considered for the formation of oriented rutile needles: (i) the rutile needles may be inherited from precursor minerals; (ii) the rutile needles may be formed by a dissolution–reprecipitation mechanism; and (iii) the rutile needles may be formed by cleaving and healing of garnet with rutile deposition. None of these mechanisms can fully explain the observations, although the first one is less likely and the third one is preferred. This study presents an example where the presence of oriented/aligned inclusions in minerals does not necessarily imply a precipitation origin.     

Eclogite and carpholite-bearing metasedimentary rocks in the North Qilian suture zone, NW China: implications for Early Palaeozoic cold oceanic subduction and water transport into mantle

Low‐temperature eclogite and eclogite facies metapelite together with serpentinite and marble occur as blocks within foliated blueschist that was originated from greywacke matrix; they formed a high‐pressure low‐temperature (HPLT) subduction complex (mélange) in the North Qilian oceanic‐type suture zone, NW China. Phengite–eclogite (type I) and epidote–eclogite (type II) were recognized on the basis of mineral assemblage. Relic lawsonite and lawsonite pseudomorphs occur as inclusions in garnet from both types of eclogite. Garnet–omphacite–phengite geothermobarometry yields metamorphic conditions of 460–510 °C and 2.20–2.60 GPa for weakly deformed eclogite, and 475–500 °C and 1.75–1.95 GPa for strongly foliated eclogite. Eclogite facies metasediments include garnet–omphacite–phengite–glaucophane schist and various chloritoid‐bearing schists. Mg‐carpholite was identified in some high‐Mg chloritoid schists. P–T estimates yield 2.60–2.15 GPa and 495–540 °C for Grt–Omp–Phn–Gln schist, and 2.45–2.50 GPa and 525–530 °C for the Mg‐carpholite schist. Mineral assemblages and P–T estimates, together with isotopic ages, suggest that the oceanic lithosphere as well as pelagic to semi‐pelagic sediments have been subducted to the mantle depths (≥75 km) before 460 Ma. Blueschist facies retrogression occurred at c. 454–446 Ma and led to eclogite deformation and dehydration of lawsonite during exhumation. The peak P–Tconditions for eclogite and metapelite in the North Qilian suture zone demonstrate the existence of cold subduction‐zone gradients (6–7 °C km^?1), and this cold subduction brought a large amount of H₂O to the deep mantle in the Early Palaeozoic times.     

Ultrahigh-pressure eclogite transformed from mafic granulite in the Dabie orogen, east-central China

Although ultrahigh‐pressure (UHP) metamorphic rocks are present in many collisional orogenic belts, almost all exposed UHP metamorphic rocks are subducted upper or felsic lower continental crust with minor mafic boudins. Eclogites formed by subduction of mafic lower continental crust have not been identified yet. Here an eclogite occurrence that formed during subduction of the mafic lower continental crust in the Dabie orogen, east‐central China is reported. At least four generations of metamorphic mineral assemblages can be discerned: (i) hypersthene + plagioclase ± garnet; (ii) omphacite + garnet + rutile + quartz; (iii) symplectite stage of garnet + diopside + hypersthene + ilmenite + plagioclase; (iv) amphibole + plagioclase + magnetite, which correspond to four metamorphic stages: (a) an early granulite facies, (b) eclogite facies, (c) retrograde metamorphism of high‐pressure granulite facies and (d) retrograde metamorphism of amphibolite facies. Mineral inclusion assemblages and cathodoluminescence images show that zircon is characterized by distinctive domains of core and a thin overgrowth rim. The zircon core domains are classified into two types: the first is igneous with clear oscillatory zonation ± apatite and quartz inclusions; and the second is metamorphic containing a granulite facies mineral assemblage of garnet, hypersthene and plagioclase (andesine). The zircon rims contain garnet, omphacite and rutile inclusions, indicating a metamorphic overgrowth at eclogite facies. The almost identical ages of the two types of core domains (magmatic = 791 ± 9 Ma and granulite facies metamorphic zircon = 794 ± 10 Ma), and the Triassic age (212 ± 10 Ma) of eclogitic facies metamorphic overgrowth zircon rim are interpreted as indicating that the protolith of the eclogite is mafic granulite that originated from underplating of mantle‐derived magma onto the base of continental crust during the Neoproterozoic (c. 800 Ma) and then subducted during the Triassic, experiencing UHP eclogite facies metamorphism at mantle depths. The new finding has two‐fold significance: (i) voluminous mafic lower continental crust can increase the average density of subducted continental lithosphere, thus promoting its deep subduction; (ii) because of the current absence of mafic lower continental crust in the Dabie orogen, delamination or recycling of subducted mafic lower continental crust can be inferred as the geochemical cause for the mantle heterogeneity and the unusually evolved crustal composition.     

Characteristics and implication of clay minerals in the northern and southern parts of the Chelung-pu fault, Taiwan

In this study, we report the characteristics of clay minerals present in the Chelung-pu fault in Taiwan. In the 1999 Chi-Chi earthquake, different slip motions were recorded along the Chelung-pu fault in the northern and southern parts of the fault. The characteristics of clay minerals present in the fault zones can be attributed to the differences in motion. We analyzed the shallow drill core samples obtained from the northern and southern sites penetrating the fault. The clay minerals identified in most of the samples from both the sites are smectite, illite, and chlorite. There are illite–smectite mixed layers with a high illite content and no chlorite–smectite mixed layer. In some samples, no smectite is detected. We also examined the iron content and symmetry of iron and magnesium in the silicate and hydroxide layers in chlorite. At the northern site, the total iron content in chlorite of gouge is larger than that of the host rocks. On the other hand, at the southern site, the total iron content varies widely. It is hypothesized that the smectite consumption and differences in the characteristics of chlorite may be controlled by the differences in the lithology, fluid chemistry, fluid temperature, or fault activities (heating or breakage) between the northern and southern sites.     

Trace elements in the Goze Delchev coal deposit, Bulgaria

The geochemistry of trace elements in the underground and open-pit mine of the Goze Delchev subbituminous coal deposit have been studied. The coals in both mines are highly enriched in W, Ge and Be, and at less extent in As, Mn and Y as compared with the world-wide Clarkes for subbituminous coals. Ni and Ti are also enhanced in the underground coals, and Zr, Cr and Mo in the open-pit mine coals.Characteristic for the trace element contents in the deposit is a regular variation with depth. The following patterns were distinguished for profile I: a — the element content decreases from the bottom to the top of the bed paralleling ash distribution (Fe, Co, As, Sb, V, Y, Mo, Cs, REE, Hf, Ta, Th, P and Au); b — Ge and W are enriched in the near-bottom and near-top coals; c — in the middle part of the bed the content of K and Rb is maximal, while that of U is slightly enriched; d — Ba content decreases from the top to the bottom of the bed. In profile II, W and Be contents decrease from the bottom to the top. The near-bottom, and especially the near-roof samples of profile IV are highly enriched in Ge, while for W the highest is the content of the near-bottom sample.Ge, Be, As, Mn, Cl and Br are mainly organically associated. The organic affiliation is still strong for Co, B, Sr, Ba, Sb, U, Th, Mo, La, Ce, Sm, Tb and Yb in the underground coals, and Fe, Co, Na, W, Sr, Y and Ag in the coals from the open-pit mine. K, Rb, Ti, Zr, Hf and Ta are of dominant inorganic affinity. The chalcophile and siderophile elements correlate positively with Fe and each other and may be bound partly with pyrite or other sulphides and iron containing minerals.Compared statistically by the t-criteria, the elements Na, Li, Cu, Zn, Pb, Cr, Ni, Co, Mo, Fe and Be are of higher content in the open-pit mine. Tungsten is the only element of higher concentration in the underground mine. The contents of Ge, As, Sr, V, Mn, Y, Zr and P are not statistically different in both mines.It was supposed that there were multiple sources of the trace elements in the deposit. The source of the highly enriched elements (W, Ge, Be, and As) most probably were the thermal waters in the source area. The contemporary mineral springs are of high content of these elements. Another source were the hosting Mesta volcanic rocks, which are enriched in Sb, Mo, Hf, U, Th, As, Li and Rb. Some of the volcanics were hydrothermally altered and enriched or depleted of many elements. Thus, the hydrothermal solutions were also suppliers of elements for the coals. It is obvious that the contents, distribution and paragenesis, of the trace elements in both Goze Delchev coals reflect the geochemical specialization of the source area, including rocks, paleo- and contemporary thermal waters.