Measuring and modeling atmospheric particles and particle bound mercury Hg(p) at five characteristic-sampling sites

The main purpose of this study was to monitor ambient air particles and particulate-bound mercury Hg(p) in total suspended particulates (TSP) concentration, dry deposition at five characteristic-sampling sites. In addition, the calculated/measured dry deposition flux ratios of ambient air particles and particulate-bound mercury Hg(p) using three dry deposition models during the years of 2009–2010 were also studied. The results showed that the order of seasonal variations for mean particulate-bound mercury Hg(p) concentrations in TSP at Bei-shi (suburban/coastal), Chang-hua (downtown) and He-mei (residential) were all shown as spring > fall, winter > summer, respectively. However, the order of seasonal variations mean particulate-bound mercury Hg(p) concentrations in TSP that occurred at Gao-mei (wetland) were shown as spring > fall > winter > summer, respectively. Finally, the results of this study also indicated that using the Noll and Fang model exhibited batten prediction results for ambient air particles and particulate-bound mercury Hg(p) dry deposition when compared with the other depositions models at any of the characteristic-sampling sites for this study.     

Monitoring and modeling concentration and dry deposition of ambient air particulates and metallic elements Mn, Fe, Zn, Cr and Cu in central Taiwan

Experiments were carried out between September 2009 and August 2010 at Bei-shi and Gao-mei in Taichung, and at Quan-xing, Chang-Hua and He-mei in Changhua. Dry-deposition flux models of metallic elements Mn, Fe, Zn, Cu and Cr bound to air particulates at five characteristic sampling sites were developed. Results concerning metallic elements Mn, Zn, Cr and Cu, revealed that Zhang’s model yielded the best results concerning the dry-deposition flux of particles of size 10 μm at Bei-shi, Chang-Hua, He-mei, Quan-xing and Gao-mei sampling sites. For the metallic element Cr, the model of Noll and Fang exhibited the best dry-deposition flux results for particles of size 10 μm at Bei-shi, He-mei and Gao-mei sampling sites. For metallic element Fe, the model of Noll and Fang yielded the best results for the dry-deposition flux of particles of size 5.6 μm at Bei-shi, Chang-Hua, He-mei and Quan-xing sampling sites. For metallic element Fe, Zhang’s model yielded the best dry-deposition flux results for particles of size 5.6 μm at the Gao-mei sampling site. For ambient air particles, Zhang’s model yielded the best average calculated/modeled ratios for particles of size 3 μm, and the model of Noll and Fang yielded the best average calculated/modeled for particles of size 10 μm. Finally, the models of both Zhang and Noll and Fang yielded more accurate predictions of the dry-deposition of metallic elements in ambient air when the particles were larger than 5.6 μm.     

Facies, dissolution seams and stable isotope compositions of the Rohtas Limestone (Vindhyan Supergroup) in the Son valley area, central India

The early Mesoproterozoic Rohtas Limestone in the Son valley area of central India represents an overall shallowing-upward carbonate succession. Detailed facies analysis of the limestone reveals outer- to inner-shelf deposition in an open marine setting. Wave-ripples, hummocky cross stratifications and edgewise conglomerates argue against a deep marine depositional model for the Rohtas Limestone proposed earlier. Stable isotope analysis of the limestone shows that δ¹³C and δ¹⁸O values are compatible with the early Mesoproterozoic open seawater composition. The ribbon limestone facies in the Rohtas Limestone is characterized by micritic beds, each decoupled in a lower band enriched and an upper band depleted in dissolution seams. Band-wise isotopic analysis reveals systematic short-term variations. Comparative enrichment of the heavier isotopes in the upper bands is attributed to early cementation from sea water and water derived from the lower band undergoing dissolution because of lowering of pH at depth. The short-term positive shifts in isotopic compositions in almost every upward gradational transition from a seamed band to a non-seamed band support the contention that dissolution seams here are of early diagenetic origin, although their formation was accentuated under overburden pressure.     

Petrogenetic links between lepidolite-subtype aplite-pegmatite,aplite veins and associated granites at Segura (central Portugal)

In the Segura area, Variscan S-type granites, aplite veins and lepidolite-subtype granitic aplite-pegmatite veins intruded the Cambrian schist-metagraywacke complex. The granites are syn D3. Aplite veins also intruded the granites. Two-mica granite and muscovite granite have similar ages of 311.0 ± 0.5 Ma and 312.9 ± 2.0 Ma but are not genetically related, as indicated by their geochemical characteristics and (⁸⁷Sr/⁸⁶Sr)₃₁₁ values. They correspond to distinct pulses of magma derived by partial melting of heterogeneous metapelitic rocks. Major and trace elements suggest fractionation trends for: (a) muscovite granite and aplite veins; (b) two-mica granite and lepidolite-subtype aplite-pegmatite veins, but with a gap in most of these trends. Least square analysis for major elements, and modeling of trace elements, indicate that the aplite veins were derived from the muscovite granite magma by fractional crystallization of quartz, plagioclase, K-feldspar and ilmenite. This is supported by the similar (⁸⁷Sr/⁸⁶Sr)₃₁₁ and δ¹⁸O values and the behavior of P₂O₅ in K-feldspar and albite. The decrease in (⁸⁷Sr/⁸⁶Sr)₃₁₁ and strong increase (1.6‰) in δ¹⁸O from two-mica granite to lepidolite-subtype aplite-pegmatite veins, and the behaviors of Ca, Mn and F of hydroxylapatite indicate that these veins are not related to the two-mica granite.     

Background concentrations of heavy metals in aquatic bryophytes used for biomonitoring in basaltic areas (a case study from central France)

 Studies were made of the aquatic bryophytes Fontinalis antipyretica Hedw., Platyhypnidium rusciforme (Neck.)Fleisch and Chiloscyphus sp. (Hoffm.)Dum. from streams embedded in basaltic rocks (Le Puy, central France). Water from these streams possessed elevated levels of Cu, Zn, Sr, V, Ba, Ni and Co, reflecting the geochemistry of the basalts, a basic type of igneous rocks containing elevated levels of these elements. The concentration of elements in bryophytes is correlated to the chemical composition of water of their sampling sites. Contents of trace elements in plants were higher than background values. The elevated levels of these elements possibly caused disturbances in the ionic equilibrium within the bryophytes. The molar ratio between contents of Ca and Mg in water (from 0.44 to 1) was different from that typical for natural water. Received: 16 September 1998 · Accepted: 17 December 1998     

Natural attenuation of TCE, As, Hg linked to the heterogeneous oxidation of Fe(II): an AFM study

Hydrous ferric oxide (HFO) colloids formed, in strictly anoxic conditions upon oxidation of Fe²⁺ ions adsorbed on mineral surface, were investigated under in situ conditions by contact mode atomic force microscopy (AFM). Freshly cleaved and acid-etched large single crystals of near endmember phlogopite were pre-equilibrated with dissolved Fe(II) and then reacted with Hg(II), As(V) and trichlorethene (TCE)-bearing solutions at 25 °C and 1 atm. HFO structures are found to be of nanometer scale. The As(V)–Fe(II) and Hg(II)–Fe(II) reaction products are round (25 nm) microcrystallites located predominantly on the layer edges and are indicative of an accelerated Fe(II) oxidation rate upon formation of Fe(II) inner sphere surface complexes with the phyllosilicate edge surface sites. On the other hand, TCE–Fe(II)–phlogopite reaction products are needle-shaped (45 nm long) particles located on the basal plane along the Periodic Bond Chains (PCBs) directions. Experiments with additions of sodium chloride confirm the importance of the Fe(II) adsorption step in the control of the overall heterogeneous Fe(II)–TCE electron transfer reaction.

Kinetic measurements at the nanomolar level of Hg° formed upon reduction of Hg(II) by Fe(II) in presence of phlogopite particles provide further convincing evidence for reduction of Hg(II)_aq coupled to the oxidation of Fe(II) adsorbed at the phlogopite–fluid interface, and indicate that sorption of Fe(II) to mineral surfaces enhances the reduction rate of Hg(II) species. The Hg(II) reduction reaction follows a first-order kinetic law. Under our experimental conditions, which were representative of many natural systems, 80% of the mercury is transferred to the atmosphere as Hg° in less than 2 h.

The reduction of a heavy metal (Hg), a toxic oxyanion (arsenate ion) and a chlorinated solvent (TCE) thus appear to be driven by the high reactivity of adsorbed Fe(II). This is of environmental relevance since these three priority pollutants are that way reductively transformed to a volatile, an immobilizable and a biodegradable species, respectively. Such kinetic data and reaction pathways are important in the evaluation of natural evaluation scenarios, in the optimization of Fe(II)/mineral mixtures as reductants in technical systems, and in general, in predicting the fate and transport of pollutants in natural systems.     

Contamination by heavy metals (Cd, Zn, Cu, and Hg) of eight fish species in the Gironde estuary (France)

The Gironde estuary, one of the largest in Europe, is considerated as a reference ecological system, with all the western European diadromous fish species present. The national biomonitoring program on the coastal marine environment has revealed since 1979 severe metal pollution (mostly cadmium [Cd]) in oysters collected from the estuary. No data are available on metal contamination levels in fish, despite their ecological and economic importance. We present the results from a detailed study based on 4 metals (Cd, zinc [Zn], copper [Cu], and mercury [Hg]) measured in 4 organs (gills, dorsal skeletal muscle, liver, and kidneys) from 8 fish species illustrating several ecological combinations: European eel (Anguilla anguilla), twaite shad (Alosa fallax), bass (Dicentrarchus labrax), meagre (Argyrosomus regius), flounder (Platichthys flesus),, thin-lippid grey mullet (Liza ramada), sole (Solea vulgaris), and Canary drum (Umbrina canariensis). The results show very marked differences between species and organs, as well as very significant variations between the 4 metals. Although metal concentrations measured in fish muscle are low, except in the case of Hg for theA. fallax, high levels of Cu and Cd were observed in the kidneys and livers ofL. ramada andA. anguilla. A multifactorial analysis based on rank ordered metal concentrations for the 8 fish species clearly shows 4 clusters of species assigned to the different degrees of metal contamination, from the lowest contaminated (A. regius, D. labrax, S. vulgaris, andU. canariensis), to the most contaminated group (L. ramada). The most contaminated species (L. ramada, A. angailla, andP. flesus) are characterized by long residence times in the estuary, between 3.5 and 14 yr. ForL. ramada, biofilms with high metal storage capacities would be the principal uptake route; the two other species are benthic with a carnivorous regime. Comparisons between our data and four estuaries (Seine, France; Mersey, U.K.; La Plata, Argentina; Guadalquivir, Spain), on a limited number of common species, metals and fish organs, clearly reveal higher Cd bioaccumulation levels in the Gironde estuary.     

X-ray absorption fine structure study of As(V) and Se(IV) sorption complexes on hydrous Mn oxides

X-ray absorption fine structure (XAFS) spectroscopic analysis at the As, Se, and Mn K-edges was used to study arsenate [As(V)O₄³⁻] and selenite [Se(IV)O₃²⁻] sorption complexes on the synthetic hydrous manganese oxides (HMOs) vernadite (δ-MnO₂) and K-birnessite (nominal composition: K₄Mn₁₄O₂₇ · 9H₂O). No significant changes were observed in sorption complex structure as a function of sorbent, pH (5 to 8), surface coverage (0.04 to 0.73 μmol/m²), or reaction time (5 to 22 h) in the arsenate or selenite systems. In the arsenate/HMO system, extended XAFS parameters indicate an average second-neighbor As(V) coordination of 2.0 ± 0.4 Mn at an average distance of 3.16 ± 0.01 Å, which is consistent with formation of As(V)O₄ sorption complexes sharing corners with two adjacent Mn(IV)O₆ surface species (i.e., bidentate, binuclear). In the selenite/HMO system, selenite surface complexes are surrounded by two shells of Mn atoms, which could represent two different adsorption complexes or a precipitate. The first shell consists of 1.6 ± 0.4 Mn at 3.07 ± 0.01 Å, which is consistent with the selenite anion forming bidentate (mononuclear) edge-sharing complexes with Mn(II)O₆ or Mn(III)O₆ octahedra. The second shell consists of 1.4 ± 0.4 Mn at 3.49 ± 0.03 Å, consistent with selenite forming monodentate, corner-sharing complexes with Mn(II)O₆ or Mn(III)O₆ octahedra. Pauling bond valence analysis that uses the extended XAFS-derived bond lengths for As(V)-O, Se(IV)-O, and Mn-O bonds indicates that the proposed surface complexes of selenite and arsenate on HMOs should be stable. Although a nearly identical Se(IV) coordination environment is found in a crystalline Mn(II)-Se(IV) precipitate (which has a structure similar to that of MnSeO₃ · H₂O), there are significant differences in the X-ray absorption near-edge structure and extended XAFS spectra of this precipitate and the selenite/HMO sorption samples. These differences coupled with transmission electron microscopy results suggest that if a precipitate is present it lacks long-range order characteristic of crystalline MnSeO₃ · H₂O.     

Preliminary investigations of 18O/16O and D/H compositions in rhyo-ignimbrites in the In Hihaou (In Zize) Magmatic Center,central Ahaggar,Algeria

The 620 M.y.-old in Hihaou (In Zize) magmatic complex located at the north-western boundary of the Archaean In Ouzzal block (western Ahaggar), is composed of massive alkaline rhyo-ignimbrites and rhyolitic domes, which are intruded by a granophyric and granitic body. The whole is preserved in a cauldron structure. Extrusive rocks are strongly ¹⁸O-depleted, with -values as low as –1.5/SMOW, while granophyres are less depleted (minimum -¹⁸O value=+2.0/SMOW. The granite has values around + 6/SMOW. D/H compositions are rather low, with D–90 to –110/SMOW. Isotopic zoning of quartz phenocrysts, ¹⁸O/¹⁶O fractionation among coexisting phases, and heterogeneity of the whole-rock -¹⁸O values, suggest that the volcanic rocks have interacted with meteoric water after the eruption. Several mechanisms of isotopic alteration are discussed. The hydrothermal alteration does not seem to have been controlled by the granitic intrusion, but rather seems to have followed the deposition of thick pyroclastic deposits on permeable arkosic sandstones and fluvio-glacial conglomerates. Pervasive circulation of water through the cooling volcanic deposits could have produced the observed ¹⁸O depletion.     

Geochemical and statistical approach to evaluate background concentrations of Cd,Cu, Pb and Zn (case study: Eastern Poland)

An attempt was made to evaluate background concentrations of Cd, Cu, Pb and Zn by means of geochemical and statistical approach. As many as 753 samples taken from 51 profiles located in Eastern Poland were analysed. For the estimation of geochemical background values, direct geochemical methods and a statistical analysis for the whole population of samples were applied. Average values of heavy metal concentration in loess sediments (bedrock) as well as in profiles not affected by human activity were measured. The iterative 2σ technique and calculated distribution function were chosen as statistical methods. The resulting values (background concentrations range) were as follows: Cd 0.5–0.9 mg kg⁻¹, Cu 5–16 mg kg⁻¹, Pb 12–26 mg kg⁻¹ and Zn 31–47 mg kg⁻¹. All the methods applied gave similar results. The highest deviation of the background was noted for Cu and the lowest for Zn. The lowest values of background were obtained for loess sediments and the highest in the case of the multiple 2σ method.     

Quantum-mechanical Hartree-Fock study of calcite (CaCO3) at variable pressure,and comparison with magnesite (MgCO3)

The static crystal energy of calcite and its structure configuration as functions of pressure were determined by ab initio all-electron periodic Hartree-Fock calculations (CRYSTAL code). Ca, O and C atoms were represented by 22, 18 and 14 atomic orbitals, respectively, in form of contracted Gaussian-type functions. Comparison between theoretical and experimental data was performed for binding energy, equilibrium unit-cell and bond lengths, bulk modulus and C ₃₃ and C ₁₁ + C ₁₂ elastic constants, and vibrational frequency of the symmetrical C-O stretching mode. The agreement is generally satisfactory. A larger compressibility is observed for structural parameters of calcite than for those of magnesite coming from a similar calculation. The Ca-O and C-O chemical bonding was characterized by electron density maps and by Mulliken atomic charges; these are discussed and compared to values determined by empirical fitting of Born-type interatomic potentials.     

Paleoenvironment,prehistory, and accelerated slope erosion along the central Israeli coastal plain (Palmahim): A geoarchaeological case study

The late Quaternary history and systematics of slope erosion along a segment of the Central Israeli Coastal Plain is examined in conjunction with a series of terminal Paleolithic occupations. Three sites situated along the slope afford site-specific and intersite data that enable reconstructions of local geological and archaeological sequences and correlations. The earliest (Kebaran) component is located on the midslope while the later (Geometric Kebaran) is situated along the footslope. Paleotopographic relations and sediment analyses indicate that the later Geometric Kebaran deposits were derived from the paleosol developed on the midslope. Paleoenvironmental contexts at the sites reveal that the rich Kebaran soil is diagnostic of an ancient swamp and attendant moist interval. Concentrations of cultural debris along these fragile midslopes imply a density of occupation and impact that may have increased rates of degradation. Extensive as well as intensive utilization of the midslope is suggested. The occupation contrasts markedly with the later Geometric Kebaran sites which display minimal sedimentation and a broader range of site distribution. The site-specific evidence and regional distribution patterns argue for more varied settlement, proportionately reduced site sizes, and consequently, reduced slope utilization towards the close of the Paleolithic.     

The impact of sewage-contaminated river water on groundwater ammonium and arsenic concentrations at a riverbank filtration site in central Delhi,India

The groundwater abstracted at a well field near the Yamuna River in Central Delhi, India, has elevated ammonium (NH₄ ⁺) concentrations up to 35 mg/L and arsenic (As) concentrations up to 0.146 mg/L, constituting a problem with the provision of safe drinking and irrigation water. Infiltrating sewage-contaminated river water is the primary source of the NH₄ ⁺ contamination in the aquifer, leading to reducing conditions which probably trigger the release of geogenic As. These conclusions are based on the evaluation of six 8–27-m deep drillings, and 13 surface-water and 69 groundwater samples collected during seven field campaigns (2012–2013). Results indicate that losing stream conditions prevail and the river water infiltrates into the shallow floodplain aquifer (up to 16 m thickness), which consists of a 1–2-m thick layer of calcareous nodules (locally known as kankar) overlain by medium sand. Because of its higher hydraulic conductivity (3.7 × 10^?3 m/s, as opposed to 3.5 × 10^?4 m/s in the sand), the kankar layer serves as the main pathway for the infiltrating water. However, the NH₄ ⁺ plume front advances more rapidly in the sand layer because of its significantly lower cation exchange capacity. Elevated As concentrations were only observed within the NH₄ ⁺ plume indicating a causal connection with the infiltrating reducing river water.     

Recent terrestrial and satellite observations to model deformations at Colli Albani volcano (central Italy)

The Colli Albani volcanic complex (Rome, Italy) has been dominated by episodic eruptions commencing around 561?ka and ending with the most recent activity of the Albano maar phase (<70?ka). Earthquakes of moderate intensity, gas emissions and significant ground deformations are the recent evidences of a residual activity. Former geodetic data from leveling surveys, GPS stations and InSAR observations tracked ongoing significant uplift of the order of few mm/year near the Colli Albani western flank. Different uplift rates were detected by each technique in different time spans, suggesting also the possibility of sporadic recharge of the hydrothermal system. The renewed high precision leveling data from IGMI survey carried out in 1997/1999 and the last leveling survey carried out in 2006 show that the uplift along the route is currently significant at an average rate of ~3?mm/year. Radar interferograms from ALOS satellite show uplift rate of ~6?mm/year, southwest of the central sector of the leveling route. We have undertaken a joint inversion of the various geodetic data (vertical rates from leveling surveys, GPS site velocities and InSAR observations acquired by ALOS satellite) using a nonlinear inversion technique to estimate the parameters of a point-pressure source, possibly capable of explaining the ongoing deformation at Colli Albani volcano.     

Hydrogeology and hydrogeochemistry at a site of strategic importance: the Pareja Limno-reservoir drainage basin (Guadalajara,central Spain)

A small calcareous basin in central Spain was studied to establish the role of groundwater in the Pareja Limno-reservoir. Limno-reservoirs aim to preserve a constant water level in the riverine zone of large reservoirs to mitigate the impacts arising from their construction. Groundwater flow contribution (mean 60 %) was derived by recharge estimation. In situ measurements (spring discharge, electrical conductivity and sulfate) were undertaken and spring discharge was compared with a drought index. Twenty-eight springs were monitored and three hydrogeological units (HGUs) were defined: a carbonate plateau (HGU1), the underlying aquitard (HGU2), and the gypsum-enriched HGU3. HGU1 is the main aquifer and may play a role in the preservation of the limno-reservoir water level. Hydrogeochemical sampling was conducted and the code PHREEQC used to describe the main geochemical processes. Weathering and dissolution of calcite and gypsum seem to control the hydrogeochemical processes in the basin. Water progresses from Ca²⁺–HCO₃ ^– in the upper basin to Ca²⁺–SO₄ ^2– in the lower basin, where HGU3 outcrops. A clear temporal pattern was observed in the limno-reservoir, with salinity decreasing in winter and increasing in summer. This variation was wider at the river outlet, but the mixing of the river discharge with limno-reservoir water buffered it.     

Malacological records from the Upper Pleistocene at Portelet (Jersey, Channel Islands): comparisons with western and central Europe

New sampling of Mollusca from Portelet, Jersey, Channel Islands, has allowed characterization of local conditions during deposition of the pre-Kesselt Weichselian loess. The Portelet fauna also allows a reassessment of the distribution of the Columella fauna in western Europe. Comparison of the Portelet fauna with those of eastern France and central Europe shows a decrease of the number of species present in this far-western locality which appears to be either a result of the operation of a typical 'peninsula' effect comparable to that seen in other zoological groups or a consequence of their occurrence in a marginal part of the European loess belt.     

Rapid, oxygen-dependent microbial Mn(II) oxidation kinetics at sub-micromolar oxygen concentrations in the Black Sea suboxic zone

Microbial Mn(II) oxidation kinetics in response to oxygen concentration were assessed in suboxic zone water at six sites throughout the Black Sea. Mn(II) oxidation rates increased asymptotically with increasing oxygen concentration, consistent with Michaelis-Menten enzyme kinetics. The environmental half-saturation constant, K_E, of Mn(II) removal (oxidation) varied from 0.30 to 10.5 μM dissolved oxygen while the maximal environmental rate, V_E−max, ranged from 4 to 50 nM h⁻¹. These parameters varied spatially and temporally, consistent with a diverse population of enzymes catalyzing Mn oxide production in the Black Sea. Coastally-influenced sites produced lower K_E and higher V_E−max constants relative to the Western and Eastern Gyre sites. In the Bosporus Region, the Mn(II) residence time calculated using our K_E and V_E−max values with 0.1 μM oxygen was 4 days, 25-fold less than previous estimates. Our results (i) indicate that rapid Mn(II) oxidation to solid phase Mn oxides in the Black Sea’s suboxic zone is stimulated by oxygen concentrations well below the 3-5 μM concentration reliably detected by current oceanographic methods, (ii) suggest the existence of multiple, diverse Mn(II)-oxidizing enzymes, (iii) are consistent with shorter residence times than previously calculated for Mn(II) in the suboxic zone and (iv) cast further doubt on the existence of proposed reactions coupling solid phase Mn oxide production to electron acceptors other than oxygen.     

Hydrogeological study of the intensely exploited aquifer of the Santa Croce leather-producing district, Tuscany (central Italy)

A hydrogeological study was undertaken to define the groundwater circulation in the Santa Croce area (Tuscany, central Italy) where the existing multilayered aquifer has long been intensively exploited. Investigations carried out on about 150 wells revealed the existence of a deep piezometric depression (to 20?m below sea level) which drains groundwater from the entire surrounding area. Samples from about 70 water points, collected twice in 2007, were analysed for major elements and stable isotope composition. Three major groups of waters, which mix in the study area, have been distinguished: (1) waters of the Ca?CMg?CHCO₃ type mainly flowing along the Arno River Plain; (2) waters of the Na?CK?CCl/Ca?CMg?CHCO₃?CSO_4, type with SO₄ content up to 275?mg/L, inflowing from the Pisane Hills; (3) relatively high-salinity waters mainly of the Na?CHCO₃ type which, with Cl concentrations up to 750?mg/L, likely arise from a normal fault located at the foot of the northern hills. The characteristics of the different components are greatly affected by significant modifying processes such as cation exchange and sulfate reduction. The achieved conceptual model suggests the southern hills as the main recharging area of the aquifer system from which water circulation, characterized by pathways of different length and depth, develops.