Phosphate Lu–Hf geochronology

Igneous, metamorphic and biogenic apatite contains Lu and Hf in proportions that make this mineral suitable for dating by the ¹⁷⁶Lu–¹⁷⁶Hf method. We present a new method for separation of Lu and Hf from apatite that involves a single extraction column step for Hf and a second exchange column step for Lu. This procedure allows rapid sample processing prior to analysis by MC-ICP-MS. Results from the igneous Gardiner, Skaergaard and Khibina Intrusions indicate that the closure temperature for the Lu–Hf isotopic system in apatite is relatively high. The Lu–Hf isochron age of 60 Ma for the Skaergaard Intrusion, East Greenland, is older than the generally accepted emplacement age, but does not appear to be a product of mixing. A centimeter-sized apatite from the Otter Lake area, Grenvillian Province, yields high and variable ¹⁷⁶Lu/¹⁷⁷Hf ratios showing that metamorphic apatite may, in some cases, allow for mono-mineral dating. The most important application of the method is undoubtedly its potential use for dating sedimentary formations. Although we find biogenic apatite in porous matrix highly susceptible to post-depositional resetting of the Lu–Hf isotopic system, the preservation of a near-depositional age for a shark tooth from the impermeable London Clay and recent work on crystalline authigenic phosphorites [Earth Planet. Sci. Lett. 201 (2002) 203] show the Lu–Hf system to be a promising tool for direct dating of sedimentary formations.     

Identifying Critical Locations in a Spatial Network with Graph Theory

Effective management of infrastructural networks in the case of a crisis requires a prior analysis of the vulnerability of spatial networks and identification of critical locations where an interdiction would cause damage and disruption. This article presents a mathematical method for modelling the vulnerability risk of network elements which can be used for identification of critical locations in a spatial network. The method combines dual graph modelling with connectivity analysis and topological measures and has been tested on the street network of the Helsinki Metropolitan Area in Finland. Based on the results of this test the vulnerability risk of the network elements was experimentally defined. Further developments are currently under consideration for eventually developing a risk model not only for one but for a group of co‐located spatial networks.     

Complexation of Gold(III)-Chloride at the Surface of Hematite

The acid/base properties of the hematite/water interface and surfacecomplexation with gold has been studied by potentiometric titrations in thefour component system H⁺ – FeOH –AuCl ₄ ^- – Cl^-. Equilibrium measurementswere performed in NaCl media at 298.2 K. In the evaluation of equilibriummodel from experimental data the constant capacitance model was applied. Theacid/base properties were investigated in 0.1 M NaCl in the range 2.6 pH 7.4. The resulting intrinsic constants for protonation anddeprotonation of hydroxyl groups at the surface were log _1,1,0,0(int) ^s = 7.10 ± 0.06 andlog _{-1,1,0,0(int)} ^s = - 7.80 ±0.06. The density of proton active surface sites was 2.85nm^-2 and the specific capacitance 2.5 C V^-1 m^-2. In the investigation of surface complexation of gold, thepotentiometric titrations were performed in the range 2.0 pH 10.2.Titration data was supplemented with analysis of Au in the aqueous phase byatomic absorbance spectrometry. The equilibrium model proposed consists ofthe following monodentate surface complexes: FeOHAuCl₃(log _0,1,1,-1 ^s = 1.45 ± 0.03),FeOHAuCl₂OH (log _-1,1,1,-2 ^s = -3.89 ± 0.02), FeOHAu(OH)₃ (log _-3,1,1,-4 ^s = -21.94 ± 0.05). Aslightly better fit could be obtained by assuming formation of a bidentatecomplex with the composition(FeO)₂Au(OH)H₂O. However, based onstructural arguments this complex was rejected.     

Millennium scale environment changes of the Okhotsk Sea during last 80 kyr and their phase relationship with global climate changes

The paper presents the records of several paleoproductivity proxies (PP) (biogenic opal and Ba (Si_bio, Ba_bio), organic carbon (C_org) and carbonate Ca_carb, chlorin and benthic foraminifera abundance (BFA)) in sediments of the Okhotsk Sea for the last 80 kyr with a resolution of ∼100–300 years. The sediment age model was based on the AMS ¹⁴C data, records of benthic foraminifera δ¹⁸O, paleointensity of the Earth’s geomagnetic field and magnetic susceptibility. PP values demonstrate series of severe prolonged productivity drops in the Okhotsk Sea followed by a sharp increase during the last glaciation. On the basis of quantitative estimations of the paleoproductivity in the Okhotsk Sea during the cold MIS 2 and warm Holocene (Gorbarenko and Goldberg, 2005), it is suggested that the millennium scale relationship in productivity-climate changes of this basin was similar: an increase in the sea’s productivity was related with regional climate warming and vice-versa. The PP records of productivity/climate oscillations in the Okhotsk Sea during MIS 2–4 occurred contemporaneously with the North Atlantic cold Heinrich events (HE) and Greenland Dansgaard-Oyeshger interstadial (DOI). Observed successions of prolonged climate cooling events followed by rapid, abrupt warming are similar to climate and environmental oscillations in the N. Atlantic and Greenland, that confirms the millennium-scale climate changes synchronicities in the Northern Hemisphere including the far NW Pacific, the hydrology and climate conditions of which are close to those of the Okhotsk Sea. Synchronism of the N. Hemisphere severe cooling (including the Okhotsk Sea) with the Antarctic warming suggests that mechanisms of the “seesaw” effect (Blunier and Brook, 2001) in the low latitude heat redistribution between high latitudes of both hemispheres were more complicated than direct NADW formation forcing and encompasses the global atmospheric reorganization. Within the PP used a closer connection in the Okhotsk Sea millennium oscillations was observed for the C_org, BFA and chlorin; Ba_bio increases more closely to DOI. Si_bio variability does not show any evident correlation with productivity changes.     

Subcellular Distribution of Heavy Metals in Organs of BivalveModiolus Modiolus Living Along a Metal Contamination Gradient

Concentration and distribution of Fe, Zn, Cu, Cd, Mn, Pb, Ni among subcellular fractions (cellular membrane structures and cytosol) and Zn, Cu, Cd among cytoplasmic proteins in the kidney and digestive gland of musselModiolus modiolus living along a polymetallic concentration gradient were studied. It was found in the kidney ofM. modiolus from contaminated sites that the Fe percent increased in the “membrane” fraction, whereas Zn, Pb, Ni and Mn percent increased in the cytosol compared to the kidney of the control mussel. Note kidney cytosol ofM. modiolus from clean and contaminated sites sequestered major parts of Cu and Cd. In the digestive gland ofM. modiolus from contaminated sites Fe, Zn, Cd, Mn, Ni percent increased in the “membrane” fraction, whereas Cu, Pb percent increased in the cytosol compared to digestive gland of control mussel. Gel-filtration chromatography shows kidney ofM. modiolus contains increased metallothionein-like protein levels irrespective of ambient dissolved metal concentrations. It was shown that the metal detoxification system in the kidney and digestive gland ofM. modiolus was efficient under extremely high ambient metal levels. However, under complex environmental contamination in the kidney ofM. modiolus, the metal detoxification capacity of metallothionein-like proteins was damaged.     

Community Structure of Free-living Marine Nematodes in the Area of Agar-Producing Alga Ahnfeltia To b u c h i e n s i s Field (Starka Strait,Peter the Great Bay,East Sea)

The structure of the nematodes communities has been studied in the sediments on two sites located outside and under the layer ofAhnfeltia tobuchiensis (Kanno and Matsubara 1932; Makijenko 1970). Bottom sediments at the stations were represented by sands with a different degree of silting. Specific structure of nematodes at the stations was significantly different under the similar environmental conditions (water depth, dissolved oxygen saturation, salinity, temperature of the bottom layer and organic carbon content inside of the sediment). Nematodes dominated (75.7 %) in meiobenthos community under the layer of A.tobuchiensis where concentration of silt particles was 12 %. Representatives of the family Comesomatidae were dominant. Low index of species diversity and high Simpson domination index were detected in this community. Under a layer ofA. tobuchiensis with the thickness of 30 cm concentration of the silt particles was 5.39 %; nematodes density was low and made 32.1 % of the general density of meiobenthos. Species of the families Xyalidae and Monoposthiidae were dominant. Outside of A.tobuchiensis, field percentage of silt particles was minimal (3.1 %) and representatives of families Cyatholaimidae and Axonolaimidae dominated. The specific structure of nematodes in this type of the ground is characterized by high index of species diversity and low level of domination.     

Petrological, organic geochemical and geochemical characteristics of coal from the Soko mine, Serbia

A petrological, organic geochemical and geochemical study was performed on coal samples from the Soko Mine, Soko Banja basin, Serbia. Ten coal and two carbonaceous clay samples were collected from fresh, working faces in the underground brown coal mine from different parts of the main coal seam. The Lower Miocene, low-rank coal of the Soko Mine is a typical humic coal with huminite concentrations of up to 76.2 vol.%, liptinite less than 14 vol.% and inertinite less than 11 vol.%. Ulminite is the most abundant maceral with variable amounts of densinite and clay minerals. Sporinite and resinite are the most common macerals of the liptinite group. Inertodetrinite is the most abundant maceral of the inertinite group. The mineral-bituminous groundmass identified in some coal samples, and carbonaceous marly clay, indicate sub-aquatic origin and strong bacterial decomposition. The mean random huminite reflectance (ulminite B) for the main coal seam is 0.40 ± 0.05% Rr, which is typical for an immature to early mature stage of organic matter.The extract yields from the coal of the Soko Banja basin ranges from 9413 to 14,096 ppm, in which alkanes constituted 1.0–20.1%, aromatics 1.3–14.7%, asphaltenes 28.1–76.2% and resins 20.2–43.5%. The saturated hydrocarbon fractions included n-C₁₅ to n-C₃₂, with an odd carbon number that predominate in almost all the samples. The contents of n-C₂₇ and n-C₂₉ alkanes are extremely high in some samples, as a contribution of epicuticular waxes from higher plants. Acyclic isoprenoid hydrocarbons are minor constituents in the aliphatic fraction, and the pristane/phytane (Pr/Ph) ratio varies between 0.56 and 3.13, which implies anaerobic to oxic conditions during sedimentation. The most abundant diterpanes were abietane, dehydroabietane and 16α(H)-phyllocladane. In samples from the upper part of the coal seam, diterpanes are the dominant constituents of the alkane fraction. Polycyclic alkanes of the triterpane type are important constituents of alkane fractions. The occurrence of ββ- and αβ-type hopanes from C₂₇ to C₃₁, but without C₂₈, is typical for the Soko Banja coals.The major and trace elements in the coal were analysed using X-ray fluorescence (XRF), and inductively coupled plasma-mass spectrometry (ICP-MS). In comparison with world lignites, using the geometric mean value, the coal from the Soko Banja Basin has a high content of strontium (306.953 mg/kg). Higher values than the world lignites were obtained for Mo (3.614 mg/kg), Ni (8.119 mg/kg), Se (0.884 mg/kg), U (2.642 mg/kg) and W (0.148 mg/kg). Correlation analysis shows inorganic affinity for almost all the major and trace elements, except for S, which has an organic affinity.     

MODIS-NDVI-based mapping of the length of the growing season in northern Fennoscandia

Northern Fennoscandia is an ecologically heterogeneous region in the arctic/alpine-boreal transition area. Phenology data on birch from 13 stations and 16-day MODIS-NDVI composite satellite data with 250 m resolution for the period 2000 to 2006 were used to map the growing season. A new combined pixel-specific NDVI threshold and decision rule-based mapping method was developed to determine the onset and end of the growing season. A moderately high correlation was found between NDVI data and birch phenology data. The earliest onset of the growing season is found in the narrow strip of lowland between the mountains and the sea along the coast of northern Norway. The onset follows a clear gradient from lowland to mountain corresponding to the decreasing temperature gradient. In autumn, the yellowing of the vegetation shows a more heterogeneous pattern. The length of the growing season is between 100 and 130 days in 55% of the study area.