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XVII Биогеохимические чтения памяти В.В. Ковальского

Журнальные статьи

Alvira, F. C.; Rozzi, F. Ramirez; Bilmes, G. M. Laser-Induced Breakdown Spectroscopy Microanalysis of Trace Elements in Homo sapiens Teeth //APPLIED SPECTROSCOPY Volume: 64 Issue: 3 Pages: 313-319 Published: MAR 2010

Two of the main items from which to retrieve data in anthropology are teeth and bones. Identification or trace elements in their composition allows valuable information to be obtained about alimentary habits and community life conditions of groups and individuals. Conventional methods used to determine the presence of trace elements require sample preparation, with partial or total destruction of the pieces, which in most cases are unique. In this work we show the possibilities of laser-induced breakdown spectroscopy (LIES) as a nearly nondestructive tool in anthropology and paleontology for the measurement of the presence and distribution of trace elements in teeth. We applied LIBS to the determination of strontium and magnesium in dentin and enamel or Neolithic, middle age, and modern Homo sapiens teeth. Mg/Ca and Sr/Ca distribution maps of dentin and enamel in modern teeth were created using the data obtained. Ablation threshold fluences of dentin and enamel were also measured using the photoacoustic signal induced by laser ablation. Significant variations were found in the Mg/Ca and Sr/Ca ratios in the tooth dental tissue and between the teeth of the groups and individuals studied. These results can be useful for evolutionary anthropology studies as they can provide information regarding early nutrition, seasonality, and residential mobility

Anderson, Rika E.; Beltran, Monica Torres; Hallam, Steven J.; et al. Microbial community structure across fluid gradients in the Juan de Fuca Ridge hydrothermal system // FEMS MICROBIOLOGY ECOLOGY Volume: 83 Issue: 2 Pages: 324-339 Published: FEB 2013

Physical and chemical gradients are dominant factors in shaping hydrothermal vent microbial ecology, where archaeal and bacterial habitats encompass a range between hot, reduced hydrothermal fluid and cold, oxidized seawater. To determine the impact of these fluid gradients on microbial communities inhabiting these systems, we surveyed bacterial and archaeal community structure among and between hydrothermal plumes, diffuse flow fluids, and background seawater in several hydrothermal vent sites on the Juan de Fuca Ridge using 16S rRNA gene diversity screening (clone libraries and terminal restriction length polymorphisms) and quantitative polymerase chain reaction methods. Community structure was similar between hydrothermal plumes and background seawater, where a number of taxa usually associated with low-oxygen zones were observed, whereas high-temperature diffuse fluids exhibited a distinct phylogenetic profile. SUP05 and Arctic96BD-19 sulfur-oxidizing bacteria were prevalent in all three mixing regimes where they exhibited overlapping but not identical abundance patterns. Taken together, these results indicate conserved patterns of redox-driven niche partitioning between hydrothermal mixing regimes and microbial communities associated with sinking particles and oxygen-deficient waters. Moreover, the prevalence of SUP05 and Arctic96BD-19 in plume and diffuse flow fluids indicates a more cosmopolitan role for these groups in the ecology and biogeochemistry of the dark ocean.

Batista, Bruno Lemos; Rodrigues, Jairo Lisboa; Nunes, Juliana Andrade Exploiting dynamic reaction cell inductively coupled plasma mass spectrometry (DRC-ICP-MS) for sequential determination of trace elements in blood using a dilute-and-shoot procedure //ANALYTICA CHIMICA ACTA Volume: 639 Issue: 1-2 Pages: 13-18

Inductively coupled plasma mass spectrometry with quadrupole (q-ICP-MS) and dynamic reaction cell (DRC-ICP-MS) were evaluated for sequential determination of As, Cd, Co, Cr, Cu, Mn, Pb, Se, Tl, V and Zn in blood. The method requires as little as 100 mu L of blood. Prior to analysis, samples (100 mu L) were diluted 1:50 in a solution containing 0.01% (v/v) Triton (R) X-100 and 0.5% (v/v) nitric acid. The use of the DRC was only mandatory for Cr, Cu, V and Zn. For the other elements the equipment may be operated in a standard mode (q-ICP-MS). Ammonia was used as reaction gas. Selection of best flow rate of ammonium gas and optimization of the quadrupole dynamic band-pass tuning parameter (RPq) were carried out, using a ovine base blood for Cr and V and a synthetic matrix solution (SMS) for Zn and Cu diluted 1:50 and spiked to contain 1 mu g L(-1) of each element. Method detection limits (3 s) for (75)As, (114)Cd, (59)Co, (51)Cr, (63)Cu (55)Mn, (208)Pb, (82)Se, (205)Tl, (51)V, and (64)Zn were 14.0, 3.0, 11.0, 7.0, 280, 9.0, 3.0, 264, 0.7, 6.0 and 800 ng L(-1), respectively. Method validation was accomplished by the analysis of blood Reference Materials produced


Crystals of gem-quality andradite (variety "demantoid") from Val Malenco, Italy, have been analyzed for major, rare-earth and other trace elements (Sc, Ti, V, Cr, Co, Ni, Zn, Sr, Y, Zr), together with samples from Aosta Valley, Italy, and from the classic deposits of the world (Russia, Iran, Pakistan, Namibia, Madagascar). They are all of gem quality and vary from bright green to yellow-green in color. The samples are homogeneous within the limit of the analytical error and cover a restricted range of composition from almost pure andradite (Adr >= 98 mol.%) to members of andradite-uvarovite (Adr(81-96)Uv(3-18)) or andradite-grossular (Adr(92-94)Grs(6-8)) solid solution, with the sole exception of the sample from Namibia, showing a composition varying from pure andradite to almost pure grossular (Adr(11)Grs(89)). All the samples have a low abundance of most trace elements, except for Cr, which ranges from a few ppm to more than 5 wt% Cr(2)O(3). The substitution of Fe(3+) and Cr(3+) for Al at the [Y] site significantly controls the geometry of the structural sites and the incorporation of the REE. In particular, (i) the samples showing a composition close to pure andradite exhibit LREE-enriched and HREE-depleted patterns with a strong positive Eu anomaly, whereas (ii) the uvarovite-enriched samples show flatter patterns with a small positive Eu anomaly, and (iii) grossular-rich samples are LREE-depleted with no Eu anomaly or a negative one. However, such a compositional variation may also arise from differences in the bulk composition of the host rocks and from changes in the physicochemical conditions during growth

Brazelton, William J.; Morrill, Penny L.; Szponar, Natalie; et al. Bacterial Communities Associated with Subsurface Geochemical Processes in Continental Serpentinite Springs //APPLIED AND ENVIRONMENTAL MICROBIOLOGY Volume: 79 Issue: 13 Pages: 3906-3916 Published: JUL 2013

Reactions associated with the geochemical process of serpentinization can generate copious quantities of hydrogen and low-molecular-weight organic carbon compounds, which may provide energy and nutrients to sustain subsurface microbial communities independently of the photosynthetically supported surface biosphere. Previous microbial ecology studies have tested this hypothesis in deep sea hydrothermal vents, such as the Lost City hydrothermal field. This study applied similar methods, including molecular fingerprinting and tag sequencing of the 16S rRNA gene, to ultrabasic continental springs emanating from serpentinizing ultramafic rocks. These molecular surveys were linked with geochemical measurements of the fluids in an interdisciplinary approach designed to distinguish potential subsurface organisms from those derived from surface habitats. The betaproteobacterial genus Hydrogenophaga was identified as a likely inhabitant of transition zones where hydrogen-enriched subsurface fluids mix with oxygenated surface water. The Firmicutes genus Erysipelothrix was most strongly correlated with geochemical factors indicative of subsurface fluids and was identified as the most likely inhabitant of a serpentinization-powered subsurface biosphere. Both of these taxa have been identified in multiple hydrogen-enriched subsurface habitats worldwide, and the results of this study contribute to an emerging biogeographic pattern in which Betaproteobacteria occur in near-surface mixing zones and Firmicutes are present in deeper, anoxic subsurface habitats


In temperate forest ecosystems, management is one of the most relevant factors that can drive the temporal pattern of species. As species in an ecosystem show susceptibility to stress and disturbance, it is useful to take into account the plant community "compositional dimension", which derives from species behaviour and ecological attributes and provides information on the mechanisms underlying species assemblages. Taking into account the influence of environmental factors on species diversity and composition, in order to determine the most suitable ecological behaviour type of each species, the research aim was to generate a model for Ostrya carpinifolia coppiced woods (central Italy) that describes forest ecosystem regeneration after coppicing by the assessment of change in the composition of ecological behaviour types. Vascular species cover percentage, field data, soil data, light intensity at the undergrowth, dominant tree layer cover and time since last logging were recorded for 63 plots covering 400 m(2) each (20 x 20 m), randomly selected within a set of homogeneous macro-environmental conditions. Low species richness is related to stressing factors (acid soil, high soil skeleton percentage), while high species richness is linked to high light intensity at the undergrowth level due to scarce canopy cover soon after coppicing. The driving forces affecting floristic composition, highlighted through multi-response permutation procedures (MRPP) were light intensity at the undergrowth, regenerative phase, dominant tree layer cover, acidity, presence/absence of outcropping rock or rock fragments and total nitrogen content. Six species groups, each one characterized by homogeneous ecological behaviour, were defined by indicator species analysis (ISA) and tested using bioindication values analysis. Floristic successional change, related to time since last coppicing, turned out to follow an ecological cycling process characterized by cyclical occurrence/disappearance of species belonging to the six groups.

Coimbra, Rute; Oloriz, Federico Contrast comparison of differential diagenetic pathways of Lower Tithonian carbonate materials from the Betic Cordillera (S. Spain): Evidence for physico-chemical paleo-seawater properties //PALAEOGEOGRAPHY PALAEOCLIMATOLOGY PALAEOECOLOGY Volume: 321 Pages: 65-79 Published: MAR 1 2012

The reconstruction of paleoenvironmental conditions is based on the study of ancient rock materials. For this purpose, skeletal materials are often assumed to have higher preservation potential, sometimes favored over the use of matrix micrite. However, factors such as ecology, depositional setting, mineralogy and diagenetic processes may obscure original geochemical signals, and care must be taken when reading such an intricate record. This work provides a thorough comparison between geochemical signatures of different carbonate materials, interpreted in the light of their paleoenvironmental significance. Burial and diagenetic processes are taken into account, contextualized by ammonite and belemnite ecology. Two sections deposited in epioceanic Tethyan areas and corresponding to the same Lower Tithonian ammonite biozone are under scope: a condensed pelagic and cephalopod-rich limestone (the Alamedilla sector) intercalated in thick mafic rocks piles, and a typical Ammonitico Rosso facies (the Cardador section). In contrast to depositional and taphonomic histories typical for a Tethyan top-swell site (i.e., rather calcareous Ammonitico Rosso), events of carbonate-mud deposition, rapid burial and early lithification, synsedimentary sliding and over imposition of firmground horizons characterize pelagic cephalopod-rich limestones. Differential taphonomy of carbonate skeletals agrees with differential preservation, favoring inner-cast preservation in Ammonitico Rosso and shell preservation (neomorphic calcite) in pelagic cephalopod-rich limestones


On the basis of a synthesis of recent progress in belowground ecology, we advance and discuss a hypothesis that relates root trait evolution to the increased dominance of angiosperms into dry upland habitats and the decline of atmospheric CO2 concentration that began in the Cretaceous. Our hypothesis is built from examining patterns of fine root adaptations during the Cretaceous, when angiosperms dramatically diversified in association with arbuscular and ectomycorrhizal root-fungal symbionts. We then explore the potential effects of root adaptations and mycorrhizas on the geochemical carbon cycle. On the basis of phylogenetic analyses of root traits among extant plant species, we suggest that angiosperm taxa, which diversified since the early Cretaceous, evolved thinner roots with greater root length per unit of biomass invested (i.e., specific root length [SRL]) than earlier diverging taxa. We suggest that these changes in root morphology were facilitated by a decline in atmospheric CO2, which likely caused water to become more limiting and nutrients more bound to organic matter. Under these conditions, we suggest that thin roots with long SRL would have allowed plants to more efficiently forage for soil water and nutrients. This assertion is supported by the observation that SRL correlates with greater root length density in soil and increased root capacity to take up water. Simulations indicate that the evolution of angiosperm root systems with greater SRL and ectomycorrhizas during the Cretaceous and Cenozoic substantially increased mineral weathering rates, with a fourfold increase in SRL, equivalent to a quadrupling of atmospheric CO2 concentration. The hypothesis presented here raises the possibility that plant hydraulic status and nutrient balance together shaped whole-plant growth strategies, with important consequences for the evolution of the biosphere.

Cowen, James P.; Copson, David A.; Jolly, James; et al. Advanced instrument system for real-time and time-series microbial geochemical sampling of the deep (basaltic) crustal biosphere // DEEP-SEA RESEARCH PART I-OCEANOGRAPHIC RESEARCH PAPERS Volume: 61 Pages: 43-56 Published: MAR 2012

Integrated Ocean Drilling Program borehole CORK (Circulation Obviation Retrofit Kit) observatories provide long-term access to hydrothermal fluids circulating within the basaltic crust (basement), providing invaluable opportunities to study the deep biosphere. We describe the design and application parameters of the GeoMICROBE instrumented sled, an autonomous sensor and fluid sampling system. The GeoMICROBE system couples with CORK fluid delivery lines to draw large volumes of fluids from crustal aquifers to the seafloor. These fluids pass a series of in-line sensors and an in situ filtration and collection system. GeoMICROBE's major components include a primary valve manifold system, a positive displacement primary pump, sensors (e.g., fluid flow rate, temperature, dissolved O-2, electrochemistry-voltammetry analyzer), a 48-port in situ filtration and fluid collection system, computerized controller, seven 24 V-40 A batteries and wet-mateable (ODI) communications with submersibles. This constantly evolving system has been successfully connected to IODP Hole 1301A on the eastern flank of the Juan de Fuca Ridge. Also described here is a mobile pumping system (MPS), which possesses many of the same components as the GeoMICROBE (e.g., pump, sensors, controller), but is directly powered and controlled in real time via submersible operations; the MPS has been employed repeatedly to collect pristine basement fluids for a variety of geochemical and microbial studies. (C) 2011 Elsevier Ltd. All rights reserved

Donovan, John J.; Lowers, Heather A.; Rusk Brian G Improved electron probe microanalysis of trace elements in quartz //American Mineralogist(USA). 2011 г., т. 96, N 2,274-282

Quartz occurs in a wide range of geologic environments throughout the Earth's crust. The concentration and distribution of trace elements in quartz provide information such as temperature and other physical conditions of formation. Trace element analyses with modern electron-probe microanalysis (EPMA) instruments can achieve 99% confidence detection of similar to 100 ppm with fairly minimal effort for many elements in samples of low to moderate average atomic number such as many common oxides and silicates. However, trace element measurements below 100 ppm in many materials are limited, not only by the precision of the background measurement, but also by the accuracy with which background levels are determined. A new "blank" correction algorithm has been developed and tested on both Cameca and JEOL instruments, which applies a quantitative correction to the emitted X-ray intensities during the iteration of the sample matrix correction based on a zero level (or known trace) abundance calibration standard. This iterated blank correction, when combined with improved background fit models, and an "aggregate" intensity calculation utilizing multiple spectrometer intensities in software for greater geometric efficiency, yields a detection limit of 2 to 3 ppm for Ti and 6 to 7 ppm for Al in quartz at 99% t-test confidence with similar levels for absolute accurac

Donovan, John J.; Lowers, Heather A.; Rusk Brian G Improved electron probe microanalysis of trace elements in quartz //American Mineralogist(USA). 2011 г., т. 96, N 2,274-282

Quartz occurs in a wide range of geologic environments throughout the Earth's crust. The concentration and distribution of trace elements in quartz provide information such as temperature and other physical conditions of formation. Trace element analyses with modern electron-probe microanalysis (EPMA) instruments can achieve 99% confidence detection of similar to 100 ppm with fairly minimal effort for many elements in samples of low to moderate average atomic number such as many common oxides and silicates. However, trace element measurements below 100 ppm in many materials are limited, not only by the precision of the background measurement, but also by the accuracy with which background levels are determined. A new "blank" correction algorithm has been developed and tested on both Cameca and JEOL instruments, which applies a quantitative correction to the emitted X-ray intensities during the iteration of the sample matrix correction based on a zero level (or known trace) abundance calibration standard. This iterated blank correction, when combined with improved background fit models, and an "aggregate" intensity calculation utilizing multiple spectrometer intensities in software for greater geometric efficiency, yields a detection limit of 2 to 3 ppm for Ti and 6 to 7 ppm for Al in quartz at 99% t-test confidence with similar levels for absolute accurac


Garnet-pyroxene-wollastonite zoned skarns in the Hirao limestone, Fukuoka, Japan, were formed during metamorphic activity associated with the emplacement of the Hirao granodiorite. In this area, rocks along the contact between a marble unit and a metamorphosed basic dike (MB) were replaced by clinopyroxene, garnet, wollastonite, and vesuvianite during infiltration metasomatism involving H2O-rich fluids. Whole-rock analysis of skarn-, marble-, and MB-hosted mineral zone samples indicates that the garnet zone skarn rocks are enriched in rare earth elements (REE). Marble trace element systematics indicate that Ce, alkali elements, Th, Pr, Zr, and Nb were all added during metamorphic activity. The majority of these elements were derived from metamorphic fluids, although some originated from the MB. Micro-scale mineral analysis was performed using laser ablationinductively coupled plasma-mass spectrometry (LA-ICP-MS), revealing that vesuvianite preferentially hosts the REE within the garnet zone rocks, even though it is only present in small amounts (3% modal abundance). The vesuvianite commonly co-exists with a Ca-rich garnet and both minerals can contain significant concentrations of REE. The results suggest that the distribution of the REE in garnet and vesuvianite may be a function of fluid composition, with REE-enriched vesuvianite forming during interaction with light rare earth element (LREE)-enriched but heavy rare earth element (HREE)-unenriched fluids. The correlation of REE concentrations and Eu anomalies in vesuvianite indicates that the fluid was REE-enriched but Eu-depleted

Hyland, Ethan; Sheldon, Nathan D.; Fan, Majie Terrestrial paleoenvironmental reconstructions indicate transient peak warming during the early Eocene climatic optimum// GEOLOGICAL SOCIETY OF AMERICA BULLETIN Volume: 125 Issue: 7-8 Pages: 1338-1348 Published: JUL-AUG 2013

Major changes in climate and ecology occurred during the early Eocene climatic optimum, sometime between 52 and 50 Ma. Recent work suggests that the timing and duration of the event are characterized by different responses in the marine and terrestrial realms, and that traditional causal mechanisms may not adequately explain such differences. We applied high-resolution paleopedology, geochemical analysis, and phytolith biostratigraphy techniques to paleosol suites within the well-described Wind River Formation of western Wyoming, USA. This multiproxy record indicates a short (<1 m.y.) peak period of carbon isotopic enrichment (up to 2% higher) and elevated pCO(2), high temperatures (up to 8 degrees C higher), increased precipitation (up to 500 mm yr(-1) higher), and shifts in floral composition (up to 10%). Terrestrial climatic and ecological changes of this kind during the early Eocene climatic optimum are consistent with changes in contemporaneous records that have been ascribed to high atmospheric pCO(2), but a transient peak interval suggests that the cause of high atmospheric pCO(2) during the early Eocene was likely not increased volcanism or decreased silicate weathering, which operate on longer timescales. Instead, terrestrial records from across western North America agree that early Eocene climatic optimum changes may have been caused by other sources, such as a combination of increased ventilation of oceanic carbon and increased petroleum generation in sedimentary basins. The climatic and environmental changes exhibited by this and other North American terrestrial records also define a pattern of regional response that is relevant for understanding the impacts of global climate change events.

Jackson, Robert B.; Vengosh, Avner; Darrah, Thomas H.; et al. Increased stray gas abundance in a subset of drinking water wells near Marcellus shale gas extraction // PROCEEDINGS OF THE NATIONAL ACADEMY OF SCIENCES OF THE UNITED STATES OF AMERICA Volume: 110 Issue: 28 Pages: 11250-11255 Published: JUL 9 2013

Horizontal drilling and hydraulic fracturing are transforming energy production, but their potential environmental effects remain controversial. We analyzed 141 drinking water wells across the Appalachian Plateaus physiographic province of northeastern Pennsylvania, examining natural gas concentrations and isotopic signatures with proximity to shale gas wells. Methane was detected in 82% of drinking water samples, with average concentrations six times higher for homes <1 km from natural gas wells (P = 0.0006). Ethane was 23 times higher in homes <1 km from gas wells (P = 0.0013); propane was detected in 10 water wells, all within approximately 1 km distance (P = 0.01). Of three factors previously proposed to influence gas concentrations in shallow groundwater (distances to gas wells, valley bottoms, and the Appalachian Structural Front, a proxy for tectonic deformation), distance to gas wells was highly significant for methane concentrations (P = 0.007; multiple regression), whereas distances to valley bottoms and the Appalachian Structural Front were not significant (P = 0.27 and P = 0.11, respectively). Distance to gas wells was also the most significant factor for Pearson and Spearman correlation analyses (P < 0.01). For ethane concentrations, distance to gas wells was the only statistically significant factor (P < 0.005). Isotopic signatures (delta C-13-CH4, delta C-13-C2H6, and delta H-2-CH4), hydrocarbon ratios (methane to ethane and propane), and the ratio of the noble gas He-4 to CH4 in groundwater were characteristic of a thermally postmature Marcellus-like source in some cases. Overall, our data suggest that some homeowners living < 1 km from gas wells have drinking water contaminated with stray gases.

Jackson, W. Andrew; Davila, Alfonso F.; Estrada, Nubia; et al. Perchlorate and chlorate biogeochemistry in ice-covered lakes of the McMurdo Dry Valleys, Antarctica // GEOCHIMICA ET COSMOCHIMICA ACTA Volume: 98 Pages: 19-30 Published: DEC 1 2012

We measured chlorate (ClO3-) and perchlorate (ClO4-) concentrations in ice covered lakes of the McMurdo Dry Valleys (MDVs) of Antarctica, to evaluate their role in the ecology and geochemical evolution of the lakes. ClO3- and ClO4- are present throughout the MDV Lakes, streams, and other surface water bodies. ClO3- and ClO4- originate in the atmosphere and are transported to the lakes by surface inflow of glacier melt that has been differentially impacted by interaction with soils and aeolian matter. Concentrations of ClO3- and ClO4- in the lakes and between lakes vary based on both total evaporative concentration, as well as biological activity within each lake. All of the lakes except the East lobe of Lake Bonney support biological reduction of ClO3- and ClO4- either in the anoxic bottom waters or sediment. The younger less saline lakes (Miers and Hoare), have surface ClO3- and ClO4- concentrations, and ratios of ClO3-/Cl- and ClO4-/Cl-, similar to source streams, while Lake Fryxell has concentrations similar to input streams but much lower ClO3-/Cl- and ClO4-/Cl- ratios, reflecting the influence of a large Cl- source in bottom sediments. ClO3- and ClO4- in Lake Bonney are the highest of all the lakes reflecting the lake's greater age and higher concentration of Cl-. ClO4- appears to be stable in the East Lobe and its concentration is highly correlated with Cl- concentration suggesting that some ClO4- at depth is a remnant of the initial seawater that formed Lake Bonney. ClO3- and ClO4- concentrations provide a simple and sensitive means to evaluate microbial activity in these lakes due to their relatively low concentrations and lack of biological sources, unlike NO3-, NO2-, and SO42-. (C) 2012 Elsevier Ltd. All rights reserved.

Jin, Yuxi; Noble, Paula J.; Poulson, Simon R. Paleoenvironmental and paleoecological implications of Permian (Guadalupian) radiolarian and geochemical variations in the Lamar Limestone, Delaware Basin, West Texas (USA) // PALAEOGEOGRAPHY PALAEOCLIMATOLOGY PALAEOECOLOGY Volume: 346 Pages: 37-53 Published: AUG 15 2012

Geochemical proxies integrated with well-preserved radiolarian data from the Lamar Limestone and lower part of the Reef Trail Member of the Bell Canyon Formation provide insights into paleoceanographically and climatically driven controls on radiolarian distribution in the northern part of the Delaware Basin of west Texas, during late Guadalupian time. Data from a section of the Lamar Limestone (similar to 8.9 m; similar to 500 kyr interval), indicate that major variations between sphaerellarian-dominated and Follicucullus-dominated faunas appear to be controlled by fluctuations in nutrient supply and salinity. Geochemical parameters of bulk carbonate carbon and oxygen isotopes (delta C-13(carb) and delta O-18(carb)), organic carbon isotope (delta C-13(org)), and total organic carbon (TOC) were analyzed and show variations on two scales. On a fine-scale, sphaerellarian-dominated beds are associated with a relatively siltier lithology, higher TOC, and higher radiolarian richness but lower diversity, and are interpreted as the result of a rise in productivity stimulated from increased terrestrial input. The radiolarian variations and geochemical evidence imply that the Permian spongiose spumellarians are more opportunistic than Follicucullus (albaillellids) in response to eutrophication. On a broad-scale, delta O-18(carb) variations in limestone samples are interpreted mainly as a proxy for paleosalinity in response to changes in basin circulation. Mg/Ca ratios from the carbonate fraction co-vary with delta O-18(carb) and are used as an additional paleosalinity proxy in this basin. The limestone beds in the middle part of the section have lighter delta O-18(carb), values compared to limestone beds above and below, and likely represent the interval when the Delaware Basin was less restricted and had relatively normal marine salinity. Impacts of diagenesis are mild but are likely the cause for systematically light delta O-18(carb) values in silty limestone beds in the middle interval. The Mg/Ca ratios and delta O-18(carb) values in the limestone samples both increase from the middle to the top of the section, implying a gradually enhanced evaporitic environment coupled with increased salinity towards the top section. Collectively, these data paint a picture of intermittent restriction in the Delaware Basin, prior to the change to a dominantly evaporative regime in the late Permian, and on a finer scale, show pronounced and frequent ecological fluctuations that appear to be driven by fluxes in terrestrial input and, to some extent, paleoproductivity. (C) 2012 Elsevier B.V. All rights reserved.

Johnston, D. T.; Poulton, S. W.; Goldberg, T.; et al. Late Ediacaran redox stability and metazoan evolution // EARTH AND PLANETARY SCIENCE LETTERS Volume: 335 Pages: 25-35 Published: JUN 15 2012

The Neoproterozoic arrival of animals fundamentally changed Earth's biological and geochemical trajectory. Since the early description of Ediacaran and Cambrian animal fossils, a vigorous debate has emerged about the drivers underpinning their seemingly rapid radiation. Some argue for predation and ecology as central to diversification, whereas others point to a changing chemical environment as the trigger. In both cases, questions of timing and feedbacks remain unresolved. Through these debates, the last fifty years of work has largely converged on the concept that a change in atmospheric oxygen levels, perhaps manifested indirectly as an oxygenation of the deep ocean, was causally linked to the initial diversification of large animals. What has largely been absent, but is provided in this study, is a multi-proxy stratigraphic test of this hypothesis. Here, we describe a coupled geochemical and paleontological investigation of Neoproterozoic sedimentary rocks from northern Russia. In detail, we provide iron speciation data, carbon and sulfur isotope compositions, and major element abundances from a predominantly siliciclastic succession (spanning > 1000 m) sampled by the Kel'tminskaya-1 drillcore. Our interpretation of these data is consistent with the hypothesis that the pO(2) threshold required for diversification of animals with high metabolic oxygen demands was crossed prior to or during the Ediacaran Period. Redox stabilization of shallow marine environments was, however, also critical and only occurred about 560 million years ago (Ma), when large motile bilaterians first enter the regional stratigraphic record. In contrast, neither fossils nor geochemistry lend support to the hypothesis that ecological interactions altered the course of evolution in the absence of environmental change. Together, the geochemical and paleontological records suggest a coordinated transition from low oxygen oceans sometime before the Marinoan (similar to 635 Ma) ice age, through better oxygenated but still redox-unstable shelves of the early Ediacaran Period, to the fully and persistently oxygenated marine environments characteristic of later Ediacaran successions that preserve the first bilaterian macrofossils and trace fossils. (C) 2012 Elsevier B.V. All rights reserved.


Pulsatilla patens has a circumpolar distribution from Eurasia to North America. This species occurs in the central and central-eastern parts of Europe, where is a rare and threatened species. In Poland, the largest number of sites is found in the north-east. A study on populations of P patens was carried out in 2009-2010, at two wildlife refuges of the NATURA 2000 (N2000) network situated in North-Eastern Poland. Local names are following: the "Sejnenskie Lake District" (SLD) and the "Grasslands in the Military Training Grounds in Orzysz" (GMO). The current population structure of P. patens was estimated including the number, density and structure of different life cycle stages. Seventy-nine research plots of 2 m x 2 m were established at sites: dry heath, xeric sand calcareous grassland and pine forest. In each plot, all individuals were recorded and classified into life cycle stages: juvenile, vegetative and flowering individuals. The studies were carried out twice a year - in spring, during the full bloom of Easter pasque flower and in summer, in time of its fructification. The bioindication method was applied in order to determine the climatic and soil conditions of the habitats. Relationships were estimated between these population characteristics and habitat-related features such as the cover of phanerogams, cryptogams, litter, and bare soil. The population found on the GMO, was composed of 316 individuals which gives the density 6.4 ind. per plot while the one in SLD consisted of 202 individuals which gives the density 6.7 ind. per plot. The age structure of the populations proved that these were stable populations. This was evidenced by a large share of vegetative individuals - in both populations they prevailed (ca 64%). The highest share of juvenile individuals was noticed at the sites characterized by a moderate cover of cryptogams (21-35%). The analysis of correlations showed that on the non-forest habitats - dry heath and xeric sand calcareous grassland, the total number of individuals and number of vegetative individuals were negatively correlated with the cover of phanerogams and the cover of cryptogams. It was recorded negative impact of dense moss layer on the number of juvenile individuals. Moreover, the cover of litter had negative influence on the total number of individuals, number of juvenile and vegetative individuals. In contrast, the total number of individuals and number of juvenile individuals at that sites was positively affected by the cover of bare soil. A positive correlation was found between the number of vegetative individuals and phanerogams, and also between the number of juvenile individuals and the cover of bare soil at forest habitats.

Kaasalainen, Hanna; Stefansson, Andri The chemistry of trace elements in surface geothermal waters and steam, Iceland //CHEMICAL GEOLOGY Volume: 330 Pages: 60-85 Published: NOV 10 2012

The geochemistry of trace elements in surface geothermal fluids in Iceland was studied. The sampled fluids included hot springs, mud pots, steam vents and soil solutions with temperatures ranging from 4 to 100 degrees C, pH between 2.01 and 9.10 and total dissolved solids between 86 and 4375 ppm. The surface geothermal waters may be categorized into three groups based on their chemical composition, namely NaCl waters, steam-heated acid-sulfate waters and mixed waters. NaCl waters with pH >8 are considered to represent aquifer geothermal fluids that have undergone boiling in the upflow. They contained only low concentrations of most metals, <0.1 ppb of Cd and Co, <1 ppb of Ni, Pb, Cr and Cu and <10 ppb of Zr, V and Zn, whereas somewhat higher concentrations of Ba (0.06-15 ppb), Sr (1.2-107 ppb), Cs (0.08-19 ppb), Rb (7.1-163 ppb), Li (18-380 ppb), As (<0.2-252 ppb), Sb (0.05-40 ppb). Mo (0.16-50 ppb), W (2.4-88 ppb), Mn (0.1-163 ppb), Fe (1.8-157 ppb) and Al (21-1510 ppb) were found. Steam-heated acid-sulfate waters typically had a pH <4. They form by condensation and mixing of steam in shallow non-thermal water. Compared to NaCl waters, steam-heated acid-sulfate waters typically had high concentrations of Al (0.02-267 ppm), Fe (0.66-360 ppm), Mn (44-4231 ppb), V (1.1-1120 ppb), Cr (0.15-660 ppb), Zn (3.1-633 ppb), Ni (0.20-192 ppb), Cu (0.09-121 ppb), Co (0.02-90 ppb), Ba (1.0-60 ppb) and Sr (2.8-316 ppb), whereas concentrations of Li (<0.03-57 ppb), Cs (<0.01-0.77 ppb), Rb (0.12-24 ppb), As (<0.1-61 ppb), Mo (<0.01-14 ppb), Sb (<0.01-25 ppb) and W (<0.01-6.9 ppb) were lower. Mixed waters are mixtures between NaCl waters, steam-heated acid-sulfate waters and non-thermal water, and showed chemical characteristics of these end-member waters. The steam discharged by the steam vents was found to carry trace elements including B, As, Cu and Cd in the ppt to ppb concentration range. The geochemistry of Li, Cs, Rb, As, Mo, Sb and Win surface geothermal waters was dominated by rock leaching, together with mixing of condensed steam and non-thermal surface waters at a low pH and with incorporation into secondary minerals including aluminum silicates and sulfides under alkaline conditions. In contrast, aqueous Ba and Sr concentrations were largely influenced by the formation of secondary minerals including sulfates, carbonates and Ca-minerals in all water types. At a low pH, the behavior of Al, Fe, Mn, Co. Ni, Zn, Cd, Cu, Pb, Cr and V was generally dominated by rock leaching, though occasionally by mineral precipitation in the case of Fe, Al, Cu, Co and Zr. With increasing pH, these metals became immobile due to their incorporation into secondary sulfide (Fe, Co, Ni, Zn, Cd, Cu, Pb), (hydr)oxide (Al, Fe, Cr, V. Zr) and aluminum

Keller, Katy; Blum, Joel D.; Kling, George W. Stream geochemistry as an indicator of increasing permafrost thaw depth in an arctic watershed //CHEMICAL GEOLOGY Volume: 273 Issue: 1-2 Pages: 76-81 Published: APR 30 2010

The presence of permafrost has a strong influence on arctic hydrology, ecology, and engineering. Therefore, understanding the response of permafrost to arctic warming is critical to predicting the regional effects of global climate change. Recent research suggests that thaw depth may be increasing in response to warming, but physical thaw depth surveys in the Alaskan arctic are often not sensitive enough to detect incremental increases and cannot measure increases in the permafrost thaw bulbs beneath lakes and streams. Here we assess the use of geochemical tracers in stream water to identify changes in thaw depth in an arctic watershed. Based on marked differences in geochemistry with depth in soils and permafrost on the Alaskan North Slope, we used Sr-87/Sr-86 and elemental ratios in an arctic stream as tracers of increases in the maximum depth of soil water flow and therefore the integrated thaw depth in the watershed. From 1994 to 2004, stream water Sr-87/Sr-86, Ca/Na, and Ca/Ba at base flow showed significant trends with time, consistent with increasing depth of soil water flowpaths. Although long time series will be necessary to identify long-term trends, stream geochemistry may be useful as a qualitative indicator of changes in thaw depth in other areas where permafrost and active layer soil geochemistry differs. (C) 2010 Elsevier BM. All rights reserved.

Leggett, R. W. A Physiological Systems Model for Iodine for Use in Radiation Protection // RADIATION RESEARCH Volume: 174 Issue: 4 Pages: 496-516 Published: OCT 2010

This paper summarizes the biokinetic database for iodine in the human body and proposes a biokinetic model for systemic iodine for use in dose assessments for internally deposited radioiodine. The model consolidates and extends existing physiological systems models describing three subsystems of the iodine cycle in the body: circulating inorganic iodide, thyroidal iodine (trapping and organic binding of iodide and synthesis, storage and secretion of thyroid hormones), and extrathyroidal organic iodine. Thyroidal uptake of inorganic iodide is described as a function of stable iodine intake (Y, mu g day(-1)) and thyroidal secretion of hormonal iodine (S, mu g day(-1)). Baseline parameter values are developed for reference adults with typical iodine intake. Compared with the current systemic biokinetic model of the International Commission on Radiological Protection (ICRP) for occupational intake of radioiodine, the proposed model predicts higher absorbed doses to the thyroid per unit uptake to blood for very short-lived iodine isotopes, similar absorbed doses to thyroid for iodine isotopes with half-life of at least a few hours, and substantially higher estimates of absorbed dose to stomach wall, salivary gland and kidneys for most iodine isotopes. Absorbed dose estimates for intravenous administration of radioiodine-labeled thyroid hormones based on the proposed model differ substantially in some cases from current ICRP values. (C) 2010 by Radiation Research Society

Liu Rui; Zhou HanWen; Zhang Li; et al. Paleoproterozoic reworking of ancient crust in the Cathaysia Block, South China: Evidence from zircon trace elements, U-Pb and Lu-Hf isotopes //CHINESE SCIENCE BULLETIN Volume: 54 Issue: 9 Pages: 1543-1554 Published: MAY 2009

A combined study of zircon LA-ICP-MS U-Pb dating, trace elements and Hf isotope was carried out for gneissic granite from the Sanzhishu area in Jingning, SW Zhejiang Province. Nearly all the zircons separated from the granite exhibited oscillatory zoning and high Th/U ratios (> 0.1). The REE profile showed a pronounced positive Ce anomaly, negative Eu anomaly and an enrichment of HREE, which are typical characteristics of magmatic zircon. Thirteen concordant or nearly concordant analytical data yielded a weighted mean (207)Pb/(206)Pb age of 1860 +/- 13 Ma (MSWD=0.084), representing the formation age of the granite. The magmatic zircons had negative epsilon Hf(t) values of -15.6 to -10.0 and two-stage Hf model ages of 3.1 to 3.4 Ga, indicating that the granites were formed by reworking of ancient crust. The major- and trace-element data indicate that the gneissic granites are metaluminous high-K calc-alkaline rocks and exhibit the same geochemical characteristics as aluminous A-type granites, implying the emplacement of the granite in a post-orogenic extensional tectonic setting. We conclude that the Paleoproterozoic crustal reworking event in the Cathaysia Block of South China marked the transition from assembly to break-up of the Columbia supercontinent

Malavolta, Marco; Piacenza, Francesco; Basso, Andrea; et al. Speciation of trace elements in human serum by micro anion exchange chromatography coupled with inductively coupled plasma mass spectrometry //ANALYTICAL BIOCHEMISTRY Volume: 421 Issue: 1 Pages: 16-25

Speciation analysis of essential trace elements in human serum provides important information on nutritional status and homeostatic mechanisms regulating transport processes, acute phase reactions, and protection against oxidative damage. Anion exchange high-performance liquid chromatography (HPLC) combined with inductively coupled plasma mass spectrometry (ICP-MS) has proved to be a useful tool in speciation. Here we describe a fast method that can be applied to carry out the speciation of Fe, Cu, Zn, and Se in as little as 1 ml of serum. The method employs monolithic anion exchange micro columns installed on a tandem HPLC system coupled on-line with an ICP-MS detector. The chromatographic separation is similar to those reported previously but with considerable gain in terms of time and sample requirement. Reproducibility is acceptable for most species. Using our method, we were able to find species-specific differences between different commercially available trace element reference materials. Because the method chosen to collect blood might interfere with speciation, the proposed methodology was used to compare heparinized plasma, ethylenediaminetetraacetic acid (EDTA) plasma, and serum from adult healthy volunteers. As expected, EDTA strongly affects speciation analysis (especially for Fe and Zn), whereas changes due to the use of lithium-heparin (Li-He) as anticoagulant appear to be minimized. (C) 2011 Elsevier Inc. All rights reserved.

Martin, R. S.; Witt, M. L. I.; Sawyer, G. M.; et al. Bioindication of volcanic mercury (Hg) deposition around Mt. Etna (Sicily)// CHEMICAL GEOLOGY Volume: 310 Pages: 12-22 Published: JUN 5 2012

Mt. Etna is a major natural source of Hg to the Mediterranean region. Total mercury concentrations, [Hg](tot), in Castanea sativa (sweet chestnut) leaves sampled 7-13 km from Etna's vents (during six campaigns in 2005-2011) were determined using atomic absorption spectroscopy. [H-g](tot), in C. sativa was greatest on Etna's SE flank reflecting Hg deposition from the typically overhead volcanic plume. [Hg](tot) also showed Hg accumulation over the growing season, increasing with leaf age and recent eruptive activity. [Hg](tot) in C. sativa was not controlled by [Hg](tot) in soils, which instead was greatest on Etna's NW flank, and was correlated with the proportion of organic matter in the soil (% Org). An elevated [Hg](tot)/% Org ratio in soils on Etna's SE flank is indicative of increased Hg deposition. This ratio was also found to decrease with local soil pH, suggesting that Hg deposited to the low pH and organic-poor soils on Etna's SE flank may not be retained but will instead be released to groundwater or re-emitted to the atmosphere. These results show that the deposition of volcanic Hg has clear impacts and confirm that Etna is an important source of Hg to the local environment. (C) 2012 Elsevier B.V. All rights reserved.

Melton, G. L.; McNeill, J.; Stachel, T.; et al. Trace elements in gem diamond from Akwatia, Ghana and DeBeers Pool, South Africa //CHEMICAL GEOLOGY Volume: 314 Pages: 1-8 Published: JUL 7 2012

Monocrystalline gem-quality diamonds from Akwatia, Ghana and De Beers Pool, South Africa were analyzed for their trace element content using an ultra-sensitive 'off-line' LA-ICP-MS method. Concentrations of 27 elements analyzed range from ppt to ppm level but mostly are below the LOQ. Ce-N/Eu-N (1-6; N = chondrite normalized) and Ce-N/Ti-N (0.6 to 12) indicate mildly elevated LREEN/MREEN and variable LREEN/Ti-N. One diamond from Ghana is distinct (G103) by having a much steeper LREEN/MREEN slope than the other samples and overall matches the trace element pattern of low-Mg carbonatitic melt inclusions in fibrous diamonds from Kankan, Guinea (Weiss et al., 2009). Syngenetic garnet inclusions indicate that the diamond growth medium must have been highly enriched in LREE, with Ce-N/Eu-N and Ce-N/Ti-N from 9 to 370 and 10 to 3400, respectively. This extreme discrepancy in trace element ratios between these gem diamonds and inclusion-based melt compositions is inconsistent with the commonly made interpretation that trace impurities in gem diamond represent trapped inclusions of the diamond forming fluid/melt. Mixtures of submicroscopic inclusions of common peridotitic and metasomatic phases in equilibrium with a basaltic melt mimic the relative Ce, Eu and Ti abundances of the studied diamonds. But models are dominated by orthopyroxene and hence, do not correspond to modal relationships expected for peridotitic sources. The models also require at least 0.5% of the sample volume be occupied by inclusions, which would affect diamond transparency. Incorporation of exotic minerals that are normally rare or as yet undiscovered in peridotite (e.g. crichtonite group minerals and REE phosphates) could significantly lower the required inclusion abundance to an extent that preserves the transparent nature of gem diamonds. The principal finding of our study is that, with one exception, the trace element patterns of these gem diamonds do not yield a faithful representation of the diamond growth medium and hence caution is required when extrapolating gem quality diamond trace element measurements into "fluid" compositions. (C) 2012 Elsevier B.V. All rights reserved

Norris, Pauline; Chen, Chien-Wei; Pan, Wei-Ping A technique for sequential leaching of coal and fly ash resulting in good recovery of trace elements //ANALYTICA CHIMICA ACTA Volume: 663 Issue: 1 Pages: 39-42

Coal and fly ash contain many elements. These elements exist in different forms which may change throughout the coal combustion process. There are several processes, including X-ray techniques and leaching techniques by which studies have attempted to assess the form of a particular element in a sample. This work focuses oil determining the leachability of selected elements sequentially leached in four extraction solutions: water, 1 M ammonium acetate, 3 M hydrochloric acid and 50% hydrofluoric acid. The emphasis is oil evaluating the steps involved in the leaching process with the mass recovery for each element being the basis for evaluation, The total amount of each element that will leach Out under the given extraction condition is presented as a fraction of the total present in the material. The materials evaluated were NIST coal and fly ash standards. The elements measured in this study include aluminum, barium, beryllium, Calcium, chromium, cobalt, iron. magnesium, manganese, nickel. potassium, sodium. Strontium, vanadium and zinc. (C) 2010 Elsevier B.V. All rights reserved

Pedrini-Martha, Veronika; Sager, Manfred; Werner, Richard; et al Patterns of Urban Mercury Contamination Detected by Bioindication With Terrestrial Isopods//ARCHIVES OF ENVIRONMENTAL CONTAMINATION AND TOXICOLOGY Volume: 63 Issue: 2 Pages: 209-219 Published: AUG 2012

Mercury (Hg) is a trace element with high toxicological impact on potential receptors, including human beings. Global Hg emissions are predicted to increase significantly during the next 40 years. After emission, the metal is transported by air currents and precipitations, leading to increasing depositions even in areas far from emission sources. In the terrestrial environment, Hg is subjected to redistribution and transformation into different inorganic and metal-organic species that are taken up by vegetation and soil organisms. In the present study, the woodlouse (Porcellio scaber) was used as a biological indicator of total Hg pollution in the city of Dornbirn (province of Vorarlberg), Austria. Woodlice were collected from 30 sampling points scattered over the city area, 25 of them situated within a rectangular transect crossing the city area from west-northwest to east-southeast, starting near the Rheintal motorway and ending at the slopes of the Bregenzer Wald hills. In addition to woodlice, soil substrate samples were collected at nine of the selected sampling points. Total Hg concentrations were measured in isopod tissues and soil substrate samples by means of an Hg analyzer. Total Hg concentrations in isopod tissues were significantly correlated with Hg soil contents (P < 0.05). Moreover, a gradient of increasing Hg concentrations was observed in isopod samples along the transect across Dornbirn, with the lowest concentrations detected in woodlouse samples near the Rheintal motorway and the highest levels toward the ascending slopes of the Bregenzer Wald hills. This gradient of increasing Hg concentrations across the city matches a concomitant increase in wet precipitations along the same direction, indicating that deposition by wet precipitation may be an important source for Hg contamination in the city of Dornbirn. Overall, the degree of Hg contamination across the study area can be regarded as rather low, i.e., comparable with concentrations observed in other, unpolluted terrestrial habitats. It is concluded that bioindication by total Hg analysis in woodlice can be applied to distinguish between different levels and sources of contamination in urban areas

Re, A.; Angelici, D.; Lo Giudice,A New markers to identify the provenance of lapis lazuli: trace elements in pyrite by means of micro-PIXE//APPLIED PHYSICS A-MATERIALS SCIENCE & PROCESSING Volume: 111 Issue: 1 Pages: 69-74 Published: APR 2013

Lapis lazuli has been used for glyptics and carving since the fifth millennium BC to produce jewels, amulets, seals, inlays, etc; the identification of the origin of the stone used for carving artworks may be valuable for reconstructing old trade routes. Since ancient lapis lazuli art objects are precious, only non-destructive techniques can be used to identify their provenance, and ion beam analysis (IBA) techniques allow us to characterise this stone in a fully non-invasive way. In addition, by using an ion microprobe, we have been able to focus the analysis on single crystals, as their typical dimensions may range from a few microns to hundreds of microns. Provenance markers, identified in previous IBA studies and already presented elsewhere, were based on the presence/absence of mineral phases, on the presence/quantity of trace elements inside a phase and on characteristic features of the luminescence spectra. In this work, a systematic study on pyrite crystals, a common accessory mineral in lapis lazuli, was carried out, following a multi-technique approach: optical microscopy and SEM-EDX to select crystals for successive trace element micro-PIXE measurements at two Italian facilities, the INFN Laboratori Nazionali di Legnaro and the INFN LABEC laboratory in Firenze. The results of this work allowed us to obtain new markers for lapis lazuli provenance identification

Reed, Daniel C.; Algar, Christopher K.; Huber, Julie A.; et al. Gene-centric approach to integrating environmental genomics and biogeochemical models// PROCEEDINGS OF THE NATIONAL ACADEMY OF SCIENCES OF THE UNITED STATES OF AMERICA Volume: 111 Issue: 5 Pages: 1879-1884 Published: FEB 4 2014

Rapid advances in molecular microbial ecology have yielded an unprecedented amount of data about the evolutionary relationships and functional traits of microbial communities that regulate global geochemical cycles. Biogeochemical models, however, are trailing in the wake of the environmental genomics revolution, and such models rarely incorporate explicit representations of bacteria and archaea, nor are they compatible with nucleic acid or protein sequence data. Here, we present a functional gene-based framework for describing microbial communities in biogeochemical models by incorporating genomics data to provide predictions that are readily testable. To demonstrate the approach in practice, nitrogen cycling in the Arabian Sea oxygen minimum zone (OMZ) was modeled to examine key questions about cryptic sulfur cycling and dinitrogen production pathways in OMZs. Simulations support previous assertions that denitrification dominates over anammox in the central Arabian Sea, which has important implications for the loss of fixed nitrogen from the oceans. Furthermore, cryptic sulfur cycling was shown to attenuate the secondary nitrite maximum often observed in OMZs owing to changes in the composition of the chemolithoautotrophic community and dominant metabolic pathways. Results underscore the need to explicitly integrate microbes into biogeochemical models rather than just the metabolisms they mediate. By directly linking geochemical dynamics to the genetic composition of microbial communities, the method provides a framework for achieving mechanistic insights into patterns and biogeochemical consequences of marine microbes. Such an approach is critical for informing our understanding of the key role microbes play in modulating Earth's biogeochemistry.

Saenger, Casey; Affek, Hagit P.; Felis, Thomas; et al. Carbonate clumped isotope variability in shallow water corals: Temperature dependence and growth-related vital effects // GEOCHIMICA ET COSMOCHIMICA ACTA Volume: 99 Pages: 224-242 Published: DEC 15 2012

Geochemical variations in shallow water corals provide a valuable archive of paleoclimatic information. However, biological effects can complicate the interpretation of these proxies, forcing their application to rely on empirical calibrations. Carbonate clumped isotope thermometry (Delta(47)) is a novel paleotemperature proxy based on the temperature dependent "clumping" of C-13-O-18 bonds. Similar Delta(47)-temperature relationships in inorganically precipitated calcite and a suite of biogenic carbonates provide evidence that carbonate clumped isotope variability may record absolute temperature without a biological influence. However, large departures from expected values in the winter growth of a hermatypic coral provided early evidence for possible Delta(47) vital effects. Here, we present the first systematic survey of Delta(47) in shallow water corals. Sub-annual Red Sea Delta(47) in two Porites corals shows a temperature dependence similar to inorganic precipitation experiments, but with a systematic offset toward higher Delta(47) values that consistently underestimate temperature by similar to 8 degrees C. Additional analyses of Porites, Siderastrea, Astrangia and Caryophyllia corals argue against a number of potential mechanisms as the leading cause for this apparent Delta(47) vital effect including: salinity, organic matter contamination, alteration during sampling, the presence or absence of symbionts, and interlaboratory differences in analytical protocols. However, intra-and inter-coral comparisons suggest that the deviation from expected Delta(47) increases with calcification rate. Theoretical calculations suggest this apparent link with calcification rate is inconsistent with pH-dependent changes in dissolved inorganic carbon speciation and with kinetic effects associated with CO2 diffusion into the calcifying space. However, the link with calcification rate may be related to fractionation during the hydration/hydroxylation of CO2 within the calcifying space. Although the vital effects we describe will complicate the interpretation of Delta(47) as a paleothermometer in shallow water corals, it may still be a valuable paleoclimate proxy, particularly when applied as part of a multi-proxy approach. (C) 2012 Elsevier Ltd. All rights reserved.

Shi Zhongli; Cao Junling; Chen Jinghong; et al Butenolide induced cytotoxicity by disturbing the prooxidant-antioxidant balance, and antioxidants partly quench in human chondrocytes //TOXICOLOGY IN VITRO Volume: 23 Issue: 1 Pages: 99-104 Published: FEB 2009

Butenolide (BUT), a mycotoxin produced by Fusarium species, was detected often in corns or grains from endemic Kashin-Beck disease (KBD) areas in China. In this Study, we evaluated the cytotoxicity of BUT on chondrocytes and the possible toxic mechanism with the aim Of understanding the pathogenesis and of directing future therapeutic interventions for KBD. Exposure of human chondrocytes and engineered cartilage to high concentration of BUT (>1 mu g/ml) resulted in significant cytotoxicity, manifested by losses in cell viability and changes in cell morphology. BUT with high concentration (>1 mu g/ml) also induced significant oxidative damage to chondrocytes in vitro evidenced by increasing both lipid peroxidation and endogenous antioxidants. Furthermore, free radical scavenging agents, such as selenium (Se), vitamin C (VC) and vitamin E (VE), partly blocked BUT-induced oxidative damage. In conclusion, this finding indicates that BUT induces cytotoxicity to human chondrocytes, and the disturbance of prooxidant-antioxidant balance may play a pivotal role in BUT-induced injuries in chondrocytes. Moreover, Se, VC or VE can quench the toxic effects of BUT to a certain extent, which will possibly direct future therapeutic interventions against KBD. (C) 2008 Elsevier Ltd. All rights reserved,

Sturtz, Timothy M.; Adar, Sara D.; Gould, Timothy; et alConstrained source apportionment of coarse particulate matter and selected trace elements in three cities from the multi-ethnic study of atherosclerosis//ATMOSPHERIC ENVIRONMENT Volume: 84 Pages: 65-77 Published: FEB 2014

PM10-2.5 mass and trace element concentrations were measured in Winston-Salem, Chicago, and St. Paul at up to 60 sites per city during two different seasons in 2010. Positive Matrix Factorization (PMF) was used to explore the underlying sources of variability. Information on previously reported PM10-25 tire and brake wear profiles was used to constrain these features in PMF by prior specification of selected species ratios. We also modified PMF to allow for combining the measurements from all three cities into a single model while preserving city-specific soil features. Relatively minor differences were observed between model predictions with and without the prior ratio constraints, increasing confidence in our ability to identify separate brake wear and tire wear features. Brake wear, tire wear, fertilized soil, and resuspended soil were found to be important sources of copper, zinc, phosphorus, and silicon, respectively, across all three urban areas. (C) 2013 Published by Elsevier Ltd

Taseska, M.; Jacimovic, R.; Stibilj, V.; et al.Determination of trace elements in some copper minerals by k(0)-neutron activation analysis //APPLIED RADIATION AND ISOTOPES Volume: 70 Issue: 1 Pages: 35-39 Published: JAN 2012

Trace element contents in two copper minerals [brochantite [Cu4SO4(OH)(6)] and native Cu] using k(0)-NAA were determined before and after quantitative removal of copper. The distribution of 44 elements in the studied minerals was investigated. An important advantage of the proposed method is the possibility to determine the content of several elements (Al, Dy, Mg, Mn and V) via their short-lived nuclides after the electrolytic removal of Cu due to the elimination of matrix interferences. (C) 2011 Elsevier Ltd. All rights reserved

Taseska, M.; Jacimovic, R.; Stibilj, V.; et al.Determination of trace elements in some copper minerals by k(0)-neutron activation analysis //APPLIED RADIATION AND ISOTOPES Volume: 70 Issue: 1 Pages: 35-39 Published: JAN 2012

Trace element contents in two copper minerals [brochantite [Cu4SO4(OH)(6)] and native Cu] using k(0)-NAA were determined before and after quantitative removal of copper. The distribution of 44 elements in the studied minerals was investigated. An important advantage of the proposed method is the possibility to determine the content of several elements (Al, Dy, Mg, Mn and V) via their short-lived nuclides after the electrolytic removal of Cu due to the elimination of matrix interferences. (C) 2011 Elsevier Ltd. All rights reserved

Taylor, H. E.; Antweiler, R. C.; Roth, D. A.; et al. Selected Trace Elements in the Sacramento River, California: Occurrence and Distribution//ARCHIVES OF ENVIRONMENTAL CONTAMINATION AND TOXICOLOGY Volume: 62 Issue: 4 Pages: 557-569 Published: MAY 2012

The impact of trace elements from the Iron Mountain Superfund site on the Sacramento River and selected tributaries is examined. The concentration and distribution of many trace elements-including aluminum, arsenic, boron, barium, beryllium, bismuth, cadmium, cerium, cobalt, chromium, cesium, copper, dysprosium, erbium, europium, iron, gadolinium, holmium, potassium, lanthanum, lithium, lutetium, manganese, molybdenum, neodymium, nickel, lead, praseodymium, rubidium, rhenium, antimony, selenium, samarium, strontium, terbium, thallium, thulium, uranium, vanadium, tungsten, yttrium, ytterbium, zinc, and zirconium-were measured using a combination of inductively coupled plasma-mass spectrometry and inductively coupled plasma-atomic emission spectrometry. Samples were collected using ultraclean techniques at selected sites in tributaries and the Sacramento River from below Shasta Dam to Freeport, California, at six separate time periods from mid-1996 to mid-1997. Trace-element concentrations in dissolved (ultrafiltered [0.005-mu m pore size]) and colloidal material, isolated at each site from large volume samples, are reported. For example, dissolved Zn ranged from 900 mu g/L at Spring Creek (Iron Mountain acid mine drainage into Keswick Reservoir) to 0.65 mu g/L at the Freeport site on the Sacramento River. Zn associated with colloidal material ranged from 4.3 mu g/L (colloid-equivalent concentration) in Spring Creek to 21.8 mu g/L at the Colusa site on the Sacramento River. Virtually all of the trace elements exist in Spring Creek in the dissolved form. On entering Keswick Reservoir, the metals are at least partially converted by precipitation or adsorption to the particulate phase. Despite this observation, few of the elements are removed by settling; instead the majority is transported, associated with colloids, downriver, at least to the Bend Bridge site, which is 67 km from Keswick Dam. Most trace elements are strongly associated with the colloid phase going downriver under both low- and high-flow conditions

Taylor, H. E.; Antweiler, R. C.; Roth, D. Trace elements and metal pollution in aerosols at an alpine site, New Zealand: Sources, concentrations and implications//ATMOSPHERIC ENVIRONMENT Volume: 82 Pages: 206-217 Published: JAN 2014

Atmospheric aerosol samples were collected at a remote site in New Zealand's Southern Alps. Collected samples were found to be a mixture of New Zealand and Australian sourced sediment, using their trace element signatures. Aerosol concentrations and the relative contribution of different sources was found to be a function of specific air-mass trajectories influencing the study site, dust entrainment rates in source areas and rainfall. Results show that Australian dust is a major source of particulate matter in New Zealand, particularly in remote alpine locations; however, locally derived dust is also important. Metal pollutants, including Pb, Cu and Sn, were enriched in the samples by approximately 15 times and up to >100 times expected natural concentrations, confirming that metal pollution is a ubiquitous component of the atmosphere, even in relatively remote locations. Moreover, pollutants were highly enriched in otherwise clean air, i.e. during and following rainfall. Additionally, high concentrations of elements naturally enriched in sea water, e.g. Sr, Ba and Rb, were deposited alongside mineral dust, reflecting the oceanic origin of air influencing the site and the role of sea spray in contributing aerosol to the atmosphere. These elements experienced the greatest enrichment during rainfall, implying sea spray and pollution become relatively important during otherwise clean air conditions. (C) 2013 Elsevier Ltd. All rights reserved.

Ulloa, Osvaldo; Canfield, Donald E.; DeLong, Edward F.; et al. Microbial oceanography of anoxic oxygen minimum zones //PROCEEDINGS OF THE NATIONAL ACADEMY OF SCIENCES OF THE UNITED STATES OF AMERICA Volume: 109 Issue: 40 Pages: 15996-16003 Published: OCT 2 2012

Vast expanses of oxygen-deficient and nitrite-rich water define the major oxygen minimum zones (OMZs) of the global ocean. They support diverse microbial communities that influence the nitrogen economy of the oceans, contributing to major losses of fixed nitrogen as dinitrogen (N-2) and nitrous oxide (N2O) gases. Anaerobic microbial processes, including the two pathways of N-2 production, denitrification and anaerobic ammonium oxidation, are oxygen-sensitive, with some occurring only under strictly anoxic conditions. The detection limit of the usual method (Winkler titrations) for measuring dissolved oxygen in seawater, however, is much too high to distinguish low oxygen conditions from true anoxia. However, new analytical technologies are revealing vanishingly low oxygen concentrations in nitrite-rich OMZs, indicating that these OMZs are essentially anoxic marine zones (AMZs). Autonomous monitoring platforms also reveal previously unrecognized episodic intrusions of oxygen into the AMZ core, which could periodically support aerobic metabolisms in a typically anoxic environment. Although nitrogen cycling is considered to dominate the microbial ecology and biogeochemistry of AMZs, recent environmental genomics and geochemical studies show the presence of other relevant processes, particularly those associated with the sulfur and carbon cycles. AMZs correspond to an intermediate state between two "end points" represented by fully oxic systems and fully sulfidic systems. Modern and ancient AMZs and sulfidic basins are chemically and functionally related. Global change is affecting the magnitude of biogeochemical fluxes and ocean chemical inventories, leading to shifts in AMZ chemistry and biology that are likely to continue well into the future.

Vukovic, Gordana; Urosevic, Mira Anicic; Razumenic, Ivana; et al. Air quality in urban parking garages (PM10, major and trace elements, PAHs): Instrumental measurements vs. active moss biomonitoring//ATMOSPHERIC ENVIRONMENT Volume: 85 Pages: 31-40 Published: MAR 2014

This study was performed in four parking garages in downtown of Belgrade with the aim to provide multi-pollutant assessment. Concentrations of 16 US EPA priority PAHs and Al, Ba, Ca, Cd, Co, Cr, Cu, Fe, K, Mg, Mn, Na, Ni, Pb, Sr and Zn were determined in PM10 samples. The carcinogenic health risk of employees' occupational exposure to heavy metals (Cd, Cr, Ni and Pb) and PAHs (B[a]A, Cry, B[b]F, B[k]F, B[a]P and DB[ah]A) was estimated. A possibility of using Sphagnum girgensohnii moss bags for monitoring of trace element air pollution in semi-enclosed spaces was evaluated as well. The results showed that concentrations of PM10, Cd, Ni and B[a]P exceeded the EU Directive target values. Concentration of Zn, Ba and Cu were two orders of magnitude higher than those measured at different urban sites in European cities. Cumulative cancer risk obtained for heavy metals and PAHs was 4.51 x 10(-5) and 3.75 x 10(-5) in M and PP, respectively; upper limit of the acceptable US EPA range is 10(-4). In the moss, higher post-exposure than pre-exposure (background) element concentrations was observed. In comparison with instrumental monitoring data, similar order of abundances of the most elements in PM10 and moss samples was found.

Wang, Juanjuan; Vollrath, Susann; Behrends, Thilo; et al Distribution and Diversity of Gallionella-Like Neutrophilic Iron Oxidizers in a Tidal Freshwater Marsh//APPLIED AND ENVIRONMENTAL MICROBIOLOGY Volume: 77 Issue: 7 Pages: 2337-2344 Published: APR 2011

Microbial iron oxidation is an integral part of the iron redox cycle in wetlands. Nonetheless, relatively little is known about the composition and ecology of iron-oxidizing communities in the soils and sediments of wetlands. In this study, sediment cores were collected across a freshwater tidal marsh in order to characterize the iron-oxidizing bacteria (FeOB) and to link their distributions to the geochemical properties of the sediments. We applied recently designed 16S rRNA primers targeting Gallionella-related FeOB by using a nested PCR-denaturing gradient gel electrophoresis (DGGE) approach combined with a novel quantitative PCR (qPCR) assay. Gallionella-related FeOB were detected in most of the samples. The diversity and abundance of the putative FeOB were generally higher in the upper 5 to 12 cm of sediment than in deeper sediment and higher in samples collected in April than in those collected in July and October. Oxygen supply by macrofauna appears to be a major force in controlling the spatial and temporal variations in FeOB communities. The higher abundance of Gallionella-related FeOB in April coincided with elevated concentrations of extractable Fe(III) in the sediments.

Zaichick, Sofia; Zaichick, Vladimir Trace elements of normal, benign hypertrophic and cancerous tissues of the Human prostate gland investigated by neutron activation analysis //APPLIED RADIATION AND ISOTOPES Volume: 70 Issue: 1 Pages: 81-87 Published: JAN 2012

The Ag, Co, Cr, Fe, Hg, Rb, Sb, Sc, Se, and Zn contents in normal (n=37), benign hypertrophic (n=43), and cancerous tissues (n=60) of the human prostate gland were investigated by neutron activation analysis. Mean values (M +/- SEM) for content (mg/kg, dry weight basis) of trace elements in the normal tissue were: Ag-0.048 +/- 0.009, Co-0.045 +/- 0.004, Cr-0.53 +/- 0.08, Fe-111 +/- 9, Hg-0.056 +/- 0.011, Rb-12.7 +/- 0.9, Sb-0.045 +/- 0.007, Sc-0.029 +/- 0.005, Se-0.70 +/- 0.04, and Zn-1000 +/- 110, respectively. It was observed that in benign hypertrophic tissues the contents of Co, Cr, Hg, Sb, and Se were higher than in normal tissues, with statistically significant differences. The contents of Co, Rb, Sc, and Zn were significantly lower and those of Ag, Cr, Fe, Hg, and Sb were significantly higher in cancerous tissues than in normal tissues. (C) 2011 Published by Elsevier Ltd.

Zaichick, Sofia; Zaichick, Vladimir Trace elements of normal, benign hypertrophic and cancerous tissues of the Human prostate gland investigated by neutron activation analysis //APPLIED RADIATION AND ISOTOPES Volume: 70 Issue: 1 Pages: 81-87 Published: JAN 2012

The Ag, Co, Cr, Fe, Hg, Rb, Sb, Sc, Se, and Zn contents in normal (n=37), benign hypertrophic (n=43), and cancerous tissues (n=60) of the human prostate gland were investigated by neutron activation analysis. Mean values (M +/- SEM) for content (mg/kg, dry weight basis) of trace elements in the normal tissue were: Ag-0.048 +/- 0.009, Co-0.045 +/- 0.004, Cr-0.53 +/- 0.08, Fe-111 +/- 9, Hg-0.056 +/- 0.011, Rb-12.7 +/- 0.9, Sb-0.045 +/- 0.007, Sc-0.029 +/- 0.005, Se-0.70 +/- 0.04, and Zn-1000 +/- 110, respectively. It was observed that in benign hypertrophic tissues the contents of Co, Cr, Hg, Sb, and Se were higher than in normal tissues, with statistically significant differences. The contents of Co, Rb, Sc, and Zn were significantly lower and those of Ag, Cr, Fe, Hg, and Sb were significantly higher in cancerous tissues than in normal tissues. (C) 2011 Published by Elsevier Ltd.

Zhang Da-Cheng; Ma Xin-Wen; Wen Wei-Qiang; et al. Influence of Laser Wavelength on Laser-induced Breakdown Spectroscopy Applied to Semi-Quantitative Analysis of Trace-Elements in a Plant Sample //CHINESE PHYSICS LETTERS Volume: 27 Issue: 6 Article Number: 063202 Published: JUN 2010

Laser-induced breakdown spectroscopy (LIBS) as a powerful analytical technique is applied to analyze trace-elements in fresh plant samples. We investigate the LIBS spectra of fresh holly leaves and observe more than 430 lines emitted from 25 elements and molecules in the region 230-438 nm. The influence of laser wavelength on LIBS applied to semi-quantitative analysis of trace-element contents in plant samples is studied. The results show that the UV laser has lower relative standard deviations and better repeatability for semi-quantitative analysis of trace-element contents in plant samples. This work may be helpful for improving the quantitative analysis power of LIBS applied to plant samples

Zhang, Yan; Gladyshev, Vadim N. Comparative Genomics of Trace Elements: Emerging Dynamic View //Chemical Reviews(USA). 2009 г., т. 109, N 10, 4828-4861


Zhelev, Zhivko M.; Popgeorgiev, Georgi S.; Angelov, Mladen V. Investigating the Changes in the Morphological Content of the Blood of Pelophylax ridibundus (Amphibia: Ranidae) as a Result of Anthropogenic Pollution and Its Use as an Environmental Bioindicator// Acta Zoologica Bulgarica(BGR). 2013 г., т. 65, N 2,187-196

The current research examines some of the basic morphological hematological indicators (erythrocyte count, leukocyte count, hemoglobin, differential blood formula) in adult, fertile species within a population of the marsh frog Pelophylax ridibundus, inhabiting two heavily polluted rivers in Bulgaria. One of the two rivers is Sazliika River, which is polluted with nitrates, phosphates, biological oxygen demand in five days and insoluble substances, and the other one is Topolnica River, polluted with heavy metals. The paper explores the use of these indicators as biological markers for the quality of the environment in the two rivers. Statistically significant differences were found between the examined parameters in the two rivers and the control group. The living in toxic conditions resulted in a single type change in the blood toxicology (increased erythrocyte count and amount of hemoglobin). The changes in the differential blood formula differ considerably - the samples from Sazliika exhibit adaptive characteristics (neutrophilia, monocytosis and lymphopenia in general leukocytosis), whereas the samples from Topolnica showed lymphopenia accompanied with neutropenia and monocytosisin general leukocytosis. This is an evidence of the degenerative effects of toxicity

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