Dynamics of dissolved major (Na,K, Ca,Mg, and Si) and trace (Al,Fe, Mn,Zn, Cu,and Cr) elements along the lower Orinoco River

This study addresses the changes in dissolved major and trace element concentrations along the Orinoco River, including the mixing zone between the Orinoco and Apure Rivers. Water samples from the Apure and Orinoco Rivers were collected monthly in four sectors over a period of 15 months. Auxiliary parameters (pH, dissolved oxygen, conductivity, and temperature), total suspended sediments, dissolved organic carbon (DOC), and major (Na, K, Ca, Mg, and Si) and trace (Al, Fe, Mn, Zn, Cu, and Cr) element concentrations were measured in all sectors. The relative contribution of both rivers after the Apure–Orinoco confluence was determined using Ca as a tracer. Moreover, a mixing model was developed to determine whether dissolved species exhibit a conservative behavior during mixing. The results indicate that DOC is removed from waters during the Apure–Orinoco mixing, probably due to absorption of DOC on mineral phases supplied by the Apure River. Dissolved Na, Ca, and Mg behave conservatively during the mixing processes, and their concentrations are controlled by a dilution process. The anomaly in the temporal pattern of K in the Orinoco is caused by the input of biogenic K originating from the Apure River during the high‐water stage. The loss of dissolved Si during the low‐water stage can be explained by the uptake of Si by diatoms. Dissolved Mn, Zn, Al, and Fe showed a non‐conservative behavior during the Apure–Orinoco mixing. The removal of Mn and Zn from the dissolved phase can be explained by the formation of Mn‐oxyhydroxides and the scavenging of Zn onto Mn oxides. Dissolved Fe is controlled by redox processes, although the removals of Fe and Al due to the preferential adsorption of large organometallic complexes by mineral surfaces after the Apure–Orinoco confluence can affect the mobility of both elements during transport. The conservative behavior shown by Cu and Cr can be related to the tendency of both elements to be complexed with small organic colloids, which are not preferentially adsorbed by clays.     

Monazite as a monitor for melt‐rock interaction during cooling and exhumation

Granulite facies cordierite–garnet–biotite gneisses from the southeastern Reynolds Range, central Australia, contain both orthopyroxene‐bearing and orthopyroxene‐free quartzofeldspathic leucosomes. Mineral reaction microstructures at the interface of gneiss and leucosome observed in outcrop and petrographically, reflect melt‐rock interaction during crystallization. Accessory monazite, susceptible to fluid alteration, dissolution and recrystallization at high temperature, is tested for its applicability to constrain the chemical and P–T–time evolution of melt‐rock reactions during crystallization upon cooling. Bulk rock geochemistry and phase equilibria modelling constrain peak pressure and temperature conditions to 6.5–7.5 kbar and ~850°C, and U–Pb geochronology constrains the timing of monazite crystallization to 1.55 Ga, coeval with the Chewings Orogeny. Modelling predicts the presence of up to 15 vol.% melt at peak metamorphic conditions. Upon cooling below 800°C, melt extraction and in situ crystallization of melt decrease the melt volume to less than 7%, at which time it becomes entrapped and melt pockets induce replacement reactions in the adjacent host rock. Replacement reactions of garnet, orthopyroxene and K‐feldspar liberate Y, REE, Eu and U in addition to Mg, Fe, Al, Si and K. We demonstrate that distinguishing between monazite varieties solely on the basis of U–Pb ages cannot solve the chronological order of events in this study, nor does it tie monazite to the evolution of melt or stability of rock‐forming minerals. Rather, we argue that analyses of various internal monazite textures, their composition and overprinting relations allow us to identify the chronology of events following the metamorphic peak. We infer that retrograde reactions involving garnet, orthopyroxene and K‐feldspar can be attributed to melt‐rock interaction subsequent to partial melting, which is reflected in the development of compositionally distinct monazite textural domains. Internal monazite textures and their composition are consistent with dissolution and precipitation reactions induced by a high‐T melt. Monazite rims enriched in Y, HREE, Eu and U indicate an increased availability of these elements, consistent with the breakdown of orthopyroxene, garnet and K‐feldspar observed petrographically. Our study indicates that compositional and textural analysis of monazite in relation to major rock‐forming minerals can be used to infer the post‐peak chemical evolution of partial melts during high‐ to ultrahigh‐temperature metamorphism.     

Increased toxicity of benzo(a)pyrene-7,8-dihydrodiol in the presence of polychlorobiphenylols

Benzo(a)pyrene (BaP) and polychlorinated biphenyls (PCBs) often co-exist in contaminated environments. Polychlorobiphenylols (OH-PCBs), formed by CYP-dependent monooxygenation of PCBs, are potent inhibitors of the glucuronidation of hydroxylated BaP metabolites. We hypothesized that OH-PCBs could drive the biotransformation of (−)BaP-7,8-dihydrodiol (BaP-7, 8-D) away from detoxication and towards formation of the reactive metabolite. A mixture of five OH-PCBs with 4–6 Cl atoms was infused into isolated, perfused, biliary intact livers (n=3 fish) removed from 3-methylcholanthrene-induced channel catfish. Controls (n=3) were infused with vehicle. Subsequently, [³H]-BaP-7, 8-D was infused into each liver and bile was collected for 1 h. The livers were taken for analysis of metabolites and DNA adducts. Induction status was confirmed by EROD assay. Bile was analyzed for metabolites. It was found that preinfusion of the mixture of OH-PCBs reduced the extent of glucuronidation of BaP-7, 8-D and increased the formation of DNA adducts 5-fold over controls. GSH conjugates, tetrols and triols were increased in the OH-PCB-infused fish, providing further support for our hypothesis that if the glucuronidation were inhibited, CYP-dependent activation would increase. These studies suggest a mechanism for synergy of toxicity of PAH and PCBs.     

Improved Monte Carlo inversion of surface wave data

Inversion of surface wave data suffers from solution non‐uniqueness and is hence strongly biased by the initial model. The Monte Carlo approach can handle this non‐uniqueness by evidencing the local minima but it is inefficient for high dimensionality problems and makes use of subjective criteria, such as misfit thresholds, to interpret the results. If a smart sampling of the model parameter space, which exploits scale properties of the modal curves, is introduced the method becomes more efficient and with respect to traditional global search methods it avoids the subjective use of control parameters that are barely related to the physical problem. The results are interpreted drawing inference by means of a statistical test that selects an ensemble of feasible shear wave velocity models according to data quality and model parameterization. Tests on synthetic data demonstrate that the application of scale properties concentrates the sampling of model parameter space in high probability density zones and makes it poorly sensitive to the initial boundary of the model parameters. Tests on synthetic and field data, where boreholes are available, prove that the statistical test selects final results that are consistent with the true model and which are sensitive to data quality. The implemented strategies make the Monte Carlo inversion efficient for practical applications and able to effectively retrieve subsoil models even in complex and challenging situations such as velocity inversions.     

Remineralization and accumulation of organic carbon and nitrogen in marine sediments of eutrophic bays: the case of the Bay of Concepcion, Chile

The Bay of Concepcion (36°40′S; 73°02′W) is a semi-enclosed and shallow embayment in which biogeochemical processes are seasonally coupled to coastal upwelling during the austral spring and summer. The nutrient cycle in the bay is complex due to the combined effects of a pronounced O₂ minimum layer and high nutrient concentrations both originating from subsurface equatorial water during coastal upwelling and a rapid rate of sediment nutrient recycling. The sediments are characterized by a high content of organic matter mainly due to the extremely high rates of phytoplankton production and deposition. During the upwelling period, a black flocculent layer frequently covers the sediment–water interface in the inner part of the bay where an extensive mat of Beggiatoa spp. develops. Three approaches are used to analyse the extent to which the benthic system recycles or retains nutrients at two stations, located at the centre (station C, St. C) and mouth (station B, St. B) of the bay for a 1-year period (March 1996–1997): (1) estimation of C and N remineralization rates based on SO₄²⁻ reduction measurements, (2) calculation of C and N turnover rates using a diagenetic model applied to total organic carbon and total nitrogen vertical distributions and, (3) construction of C and N budgets from direct measurements of sedimentation (from a sediment trap) and estimates of the C and N burial rates. Depth-integrated SO₄²⁻ reduction rates varied between 3.4 (winter) and 25.5 (summer) mmol m⁻² d⁻¹. Estimated C and N oxidation rates ranged between 7.9 and 87.8 mol C m⁻² yr⁻¹ and between 0.9 and 6.9 mol N m⁻² yr⁻¹, respectively. Each approach yielded minor differences in the C and N remineralization rates (and also minor differences between both studied stations), except when the kinetic model was applied to C and N distribution without including the presence of the flocculent layer. The rates of carbon oxidation and sulphate reduction were considerably higher than in other coastal sediments with similar depositional regime. The C and N burial rates were 2.23 and 0.21 (St. C) and 1.30 and 0.09 (St. B) mol m⁻² yr⁻¹, respectively. The C/N ratio of the buried fraction was ca. 10.6 at St. C and 14.4 at St. B. Because the observed differences in burial rates could not be ascribed to distinctive depositional (both stations have similar sediment accumulation rates) and oceanographic (similar O₂ concentration and hydrography) conditions, differences may be due to in part spatial heterogeneity in the supply of organic matter. The degree of preservation of organic matter as plankton detritus and nitrogen accumulating bacterial biomass associated with Beggiatoa spp. at St. C may also be involved.     

New evidence of sea‐level lowstands and paleoenvironment during MIS 6 and 4 in the Cantabrian coastal karst: the Cobiheru cave (North Iberia)

The geomorphological evolution of the Cobiheru Cave shows the influence of the non‐carbonate coastal mountain ranges on coastal karst evolution, as well as the temporal distribution of the cold‐adapted fauna sites in the Cantabrian Coast. Geomorphological observation and uranium/thorium (U/Th) dating lead to the construction of an evolution model. The model comprises two episodes of cave deposition occurring at c. 60–70 and 130–150 ka, linked to cold climate conditions, global sea‐level lowstands and the erosion of alluvial fans that covered the karst. Moreover, the comparison between the Cobiheru record and some raised beaches identified in previous studies sets the beginning of the sea‐level lowering in the Cantabrian Sea during the marine isotope stages (MIS) 5–4 transition. Two palaeoenvironments are inferred based on finding Equus ferus and Elona quimperiana. A wet deciduous forest would have developed on the emerged marine terrace of the Cobiheru Cave since at least the Middle Pleistocene, and an open landscape with scarce vegetation would have been present at c. 65 ka. The erosional event identified in the Cobiheru Cave helps to understand the temporal distribution of cold‐adapted mammals located in the Asturias region. The probable sites of cold‐adapted fauna developed in caves and alluvial fans would have disappeared after 65 ka. Therefore, palaeontological and palaeoclimate research based on cold‐adapted mammals suggests the occurrence of an hiatus in the palaeontological record prior to 50 ka. Copyright © 2017 John Wiley & Sons, Ltd.     

Behaviour of Fe<Subscript>4</Subscript>O<Subscript>5</Subscript>–Mg<Subscript>2</Subscript>Fe<Subscript>2</Subscript>O<Subscript>5</Subscript> solid solutions and their relation to coexisting Mg–Fe silicates and oxide phases

Experiments at high pressures and temperatures were carried out (1) to investigate the crystal-chemical behaviour of Fe₄O₅–Mg₂Fe₂O₅ solid solutions and (2) to explore the phase relations involving (Mg,Fe)₂Fe₂O₅ (denoted as O₅-phase) and Mg–Fe silicates. Multi-anvil experiments were performed at 11–20 GPa and 1100–1600 °C using different starting compositions including two that were Si-bearing. In Si-free experiments the O₅-phase coexists with Fe₂O₃, hp-(Mg,Fe)Fe₂O₄, (Mg,Fe)₃Fe₄O₉ or an unquenchable phase of different stoichiometry. Si-bearing experiments yielded phase assemblages consisting of the O₅-phase together with olivine, wadsleyite or ringwoodite, majoritic garnet or Fe³⁺-bearing phase B. However, (Mg,Fe)₂Fe₂O₅ does not incorporate Si. Electron microprobe analyses revealed that phase B incorporates significant amounts of Fe²⁺ and Fe³⁺ (at least ~?1.0 cations Fe per formula unit). Fe-L_2,3-edge energy-loss near-edge structure spectra confirm the presence of ferric iron [Fe³⁺/Fe_tot?=?~?0.41(4)] and indicate substitution according to the following charge-balanced exchange: [4]Si⁴⁺?+?[6]Mg²⁺?=?2Fe³⁺. The ability to accommodate Fe²⁺ and Fe³⁺ makes this potential “water-storing” mineral interesting since such substitutions should enlarge its stability field. The thermodynamic properties of Mg₂Fe₂O₅ have been refined, yielding H°_1bar,298?=???1981.5 kJ mol^??1. Solid solution is complete across the Fe₄O₅–Mg₂Fe₂O₅ binary. Molar volume decreases essentially linearly with increasing Mg content, consistent with ideal mixing behaviour. The partitioning of Mg and Fe²⁺ with silicates indicates that (Mg,Fe)₂Fe₂O₅ has a strong preference for Fe²⁺. Modelling of partitioning with olivine is consistent with the O₅-phase exhibiting ideal mixing behaviour. Mg–Fe²⁺ partitioning between (Mg,Fe)₂Fe₂O₅ and ringwoodite or wadsleyite is influenced by the presence of Fe³⁺ and OH incorporation in the silicate phases.     

Patterns of water, heat, and solute flux through streambeds around small dams

Hyporheic exchange, enhanced by complex stream channel morphology, can influence biogeochemical processing in the streambed. These processes chemically alter water passing temporarily through the streambed, which eventually returns to the stream channel and can potentially affect surface water quality. To assess the degree of biogeochemical cycling induced by complex streambed morphology, we instrumented two 20-m reaches of Red Canyon Creek, Wyoming, each containing a small log dam, with in-stream minipiezometers and temperature data loggers. We simultaneously observed pore water geochemistry and streambed temperature dynamics in several bedforms located upstream or downstream of the dams. We modeled seepage flux into the streambed using heat transport modeling.
Upstream of the dams, low-permeability sediments have settled out in low-velocity pools, and enhanced anaerobic biogeochemical cycling occurred in the streambed. Rapid flux into the streambed occurred in glides immediately above the dams, where streambed temperature dynamics and geochemistry were nearly identical to the stream. In riffle sequences downstream of the dams, the streambed was oxygen rich, showed evidence of nitrification, and temperature dynamics indicated high connectivity between the streambed and the stream. Further downstream, streambed pore water geochemistry indicated ground water discharge occurring at the pool-riffle transition. Assessing streambed biogeochemical cycling may be facilitated by coupling streambed temperature measurements with pore water geochemistry and can aid in understanding how hyporheic exchange contributes to overall stream biogeochemistry.