Constraints on clinopyroxene/melt partitioning of REE, Rb, Sr, Ti, Cr, Zr, and Nb during mantle melting: First insights from direct peridotite melting experiments at 1.0 GPa

Earlier piston-cylinder experiments in our laboratory produced a collection of mantle melting run products at 1.0 GPa that have now been analyzed by ion probe for selected REE, Ti, Cr, Rb, Sr, Y, Zr, and Nb. Natural starting materials were used and experiments were run in graphite-lined Pt capsules with the melt separated from the residual minerals into a layer of vitreous carbon spheres (VCS) to circumvent quench modification. The glass phase in 18 run products, representing melt percentages of ∼2-20 wt%, yielded excellent data that were inverted to yield the first estimates ever of clinopyroxene/melt distribution coefficients, Ds, derived from direct peridotite partial melting experiments. Uncertainties were estimated with a Monte Carlo method.For the REE and Y, these Ds were then compared to Ds calculated with the widely-used model of Wood and Blundy (1997) and the two sets overlap at the ±2σ level in 123 of 128 cases (∼96%). This indicates to us that: 1) the experiments analyzed here are well equilibrated with respect to major and trace element distributions, thus supporting the efficacy of the VCS technique and its variation involving diamond (e.g., Baker and Stolper, “Determining the composition of high-pressure mantle melts using diamond aggregates” [1994], Geochim. Cosmochim. Acta58, 2811-2827); 2) the model of Wood and Blundy (1997), calibrated largely on the basis of large melt fraction, inverse- or sandwich-type experiments, describes REE and Y partitioning during peridotite melting well, even very near the solidus; and it suggests that the cpx/melt Ds derived here for other elements, not modeled by the Wood and Blundy formulation, are probably also correct for peridotite melting to within their ±2σ uncertainties. D^sp/liq and D^cpx/liq values for Cr calculated directly from electron microprobe data decrease by about a factor of five with increasing temperature and melt percentage.The degree to which our experiments appear to have equilibrated seems at odds with recent measurements of the diffusivities of REE in diopside which suggest that relatively small percentages of our starting mineral grains should have equilibrated diffusively. Instead, we suggest that equilibration occurs much more rapidly through the processes of recrystallization and grain coarsening, accomplished through dissolution and reprecipitation. This suggestion is supported by the observation that our final grain sizes are typically 5-10 times larger than the ∼10 μm starting sizes, indicating that substantial mass transfer occurred in our experiments, probably mediated by the melt phase in which diffusion is faster.     

Domoic acid excretion in dungeness crabs, razor clams and mussels

Domoic acid (DA) is a neurotoxic amino acid produced by several marine algal species of the Pseudo-nitzschia (PN) genus. We studied the elimination of DA from hemolymph after intravascular (IV) injection in razor clams (Siliqua patula), mussels (Mytilus edulis) and Dungeness crabs (Cancer magister). Crabs were also injected with two other organic acids, dichloroacetic acid (DCAA) and kainic acid (KA). For IV dosing, hemolymph was repetitively sampled and DA concentrations measured by HPLC-UV. Toxicokinetic analysis of DA in crabs suggested most of the injected dose remained within hemolymph compartment with little extravascular distribution. This observation is in sharp contrast to results obtained from clams and mussels which exhibited similarly large apparent volumes of distribution despite large differences in overall clearance. These findings suggest fundamentally different storage and elimination processes are occurring for DA between bivalves and crabs.     

Solubility of hydrous ferric oxide and iron speciation in seawater

Iron solubility equilibria were investigated in seawater at 36.22‰ salinity and 25°C using several filtration and dialysis techniques. In simple filtration experiments with 0.05 μm filters and Millipore ultra-filters, ferric chlorides fluorides, sulfates, and FeOH²⁺ species were found to be insignificant relative to Fe(OH)₂⁺ at p[H⁺] = ?log [H⁺] greater than 6.0. Hydrous ferric oxide freshly precipitated from seawater yielded a solubility product of ${}^1\text{K}{}_{\mathrm{<mtext>so</mtext>}}\text{=}\text{[Fe}{}^{\mathrm{3+}}\text{][H}{}^{\mathrm{+}}\text{]}{}^{\mathrm{?3}}\text{= 4.7 · 10}{}^5$. Solubility studies based on the rates of dialysis of various seawater solutions and on the filtration of acidified seawater solutions indicated the existence of the Fe(OH)₃⁰ species. The formation constant for this species can be calculated as ${}^1\text{β}{}_3\text{=}\text{[Fe(OH)}{}_3{}^0\text{] [H}{}^{\mathrm{+}}\text{]}{}^3\text{/[Fe}{}^{\mathrm{3+}}\text{] = 2.4 · 10}{}^{\mathrm{?14}}$. The Fe(OH)₄^? species is present at concentrations which are negligible compared to Fe(OH)₂⁺ and Fe(OH)₃⁰ in the normal pH range of seawater. However, there is at least one other significant ferric complex in seawater above p[H⁺] = 8.0 (possibly with bicarbonate, carbonate, or borate ions) in addition to the Fe(OH)₂⁺ and Fe(OH)₃⁰ species.     

Effect of major ion variations in the marine environment on the specific gravity-conductivity-chlorinity-salinity relationship

Partial equivalent conductances and partial equivalent volumes of the major constituents in seawater were used to evaluate the specific gravity-conductivity-chlorinity-salinity relationships in the marine environment. For example, in the open ocean, the relationships between Cl‰ and both S‰ and specific gravity are valid to within 0.014‰ and 0.014 σ_t, respectively. The relationships between conductivity and S‰ and specific gravity are valid to within 0.006‰ and 0.007 σ_t. In river diluted nearshore areas specific gravity anomalies inferred from Cl‰, can be as great as 0.06 σ_t and 0.04 σ_t when inferred from a conductivity ratio measurement.     

Constraints from Moho geometry and crustal thickness on the geodynamic origin of the Vrancea Seismogenic Zone (Romania)

Reprocessing of industry deep seismic reflection data (Ramnicu Sarat and Braila profiles) from the SE Carpathian foreland of Romania provides important new constraints on geodynamic models for the origin of the intermediate depth Vrancea Seismogenic Zone (VSZ). Mantle (70–200 km) earthquakes of the VSZ are characterized by high magnitudes (greater than 6.5), frequent occurrence rates (approximately 25 years), and confinement in a very narrow (30 × 70 × 200 km³) near vertical zone atypical for a Wadati–Benioff plane, located in front of the orogen. These two deep (20 s) seismic reflection profiles (70 km length across the foreland) reveal (1) a high-amplitude, gently east-dipping reflection across most of the section from what we interpret to be the Moho at  15 s (40–42 km) on the Ramnicu Sarat line to  16 s (47–48 km) on the Braila line, (2) a thick sedimentary cover increasing in thickness from east (1 s;  800 m) to west (7.5 s; 14 km), (3) an eastward increase in crustal thickness from 38 km (near VSZ) to  45 km, (4) seismic and topographic evidence for a newly imaged, possibly seismically active basement fault with a surface offset of 30 m observed on the Ramnicu Sarat line, (5) a lack of notable west-dipping structures in the crust and across the Moho, and (6) variable displacements on Peceneaga–Camena Fault of  5 km at Moho and  200 m at the basement–sedimentary cover contact.These observations appear to argue against recent models for west-dipping subduction of oceanic lithosphere at or in the vicinity of the Vrancea Seismogenic Zone given the lack of west-dipping fabrics in the lower crust and across the crust–mantle boundary. Consequently, one possible explanation for the geodynamic origin of VSZ could be partial delamination of the continental lithosphere in an intra-plate setting along a sub-horizontal lithospheric interface in the Carpathian hinterland that likely involves remnant lithospheric coupling between the crust and uppermost mantle in the foreland.     

Numerical solution of micro-physical equations in a model of a convective cloud

Summary The procedure for computation and the numerical results of the first testing of the so-called Mi-operation, which is a construction unit of the model of a convective cloud[1] and represents the formulation of microphysical phenomena occurring in a convective cloud, are described. In this paper the Mi-operation is applied to the case of the liquid stage, restricted to condensation and drop evaporation. The solution of the corresponding system of kinetic equations serves the purpose of an initial test of the applicability of the integration method to the type of equations mentioned.     

Isoseismals of the strongest Friuli aftershocks of September 1976

Summary Isoseismal maps of the three strongest Friuli aftershocks of September 1976 were compiled using the contributions from European countries within the shaken area. The characteristic features of the macroseismic fields are discussed.     

Comparison of surface and borehole locations of induced seismicity

Monitoring of induced microseismic events has become an important tool in hydraulic fracture diagnostics and understanding fractured reservoirs in general. We compare microseismic event and their uncertainties using data sets obtained with surface and downhole arrays of receivers. We first model the uncertainties to understand the effect of different acquisition geometries on location accuracy. For a vertical array of receivers in a single monitoring borehole, we find that the largest part of the final location uncertainty is related to estimation of the backazimuth. This is followed by uncertainty in the vertical position and radial distance from the receivers. For surface monitoring, the largest uncertainty lies in the vertical position due to the use of only a single phase (usually P‐wave) in the estimation of the event location. In surface monitoring results, lateral positions are estimated robustly and are not sensitive to the velocity model. In this case study, we compare event location solutions from two catalogues of microseismic events; one from a downhole array and the second from a surface array of 1C geophone. Our results show that origin time can be reliably used to find matching events between the downhole and surface catalogues. The locations of the corresponding events display a systematic shift consistent with a poorly calibrated velocity model for downhole dataset. For this case study, locations derived from surface monitoring have less scatter in both vertical and horizontal directions.     

Long‐term streamflow trends in Hawai'i and implications for native stream fauna

Climate change has fundamentally altered the water cycle in tropical islands, which is a critical driver of freshwater ecosystems. To examine how changes in streamflow regime have impacted habitat quality for native migratory aquatic species, we present a 50‐year (1967–2016) analysis of hydrologic records in 23 unregulated streams across the five largest Hawaiian Islands. For each stream, flow was separated into direct run‐off and baseflow and high‐ and low‐flow statistics (i.e., Q10 and Q90) with ecologically important hydrologic indices (e.g., frequency of flooding and low flow duration) derived. Using Mann–Kendall tests with a running trend analysis, we determined the persistence of streamflow trends through time. We analysed native stream fauna from ~400 sites, sampled from 1992 to 2007, to assess species richness among islands and streams. Declines in streamflow metrics indicated a general drying across the islands. In particular, significant declines in low flow conditions (baseflows), were experienced in 57% of streams, compared with a significant decline in storm flow conditions for 22% of streams. The running trend analysis indicated that many of the significant downward trends were not persistent through time but were only significant if recent decades (1987–2016) were included, with an average decline in baseflow and run‐off of 10.90% and 8.28% per decade, respectively. Streams that supported higher native species diversity were associated with moderate discharge and baseflow index, short duration of low flows, and negligible downward trends in flow. A significant decline in dry season flows (May–October) has led to an increase in the number of no‐flow days in drier areas, indicating that more streams may become intermittent, which has important implications for mauka to makai (mountain to ocean) hydrological connectivity and management of Hawai'i's native migratory freshwater fauna.     

Thermodynamic stability studies of the basic copper carbonate mineral,malachite

Natural malachite is a well defined solid demonstrating reproducible solubility behavior over a wide range of pH. The following equilibrium constants associated with the malachite dissolution equilibrium at 25°C, 1 atm were determined:

(infinite dilution)

$\text{K}{}^1{}_{\mathrm{sp}}\text{=}\text{[Cu}{}^{\mathrm{2+}}\text{]}{}^2\text{[CO}{}^{\mathrm{2?}}{}_3\text{]K}{}^2{}_{\mathrm{w}}\text{a}{}^2{}_{\mathrm{H+}}\text{= 10. ± 0.2 × 10}{}^{\mathrm{?32}}$

(0.72 ionic strength)

(36.9‰ salinity seawater). The temperature dependence of a “mixed” equilibrium constant, K_sp⁺, of the form:

has been measured at I = 0.72, yielding the relationship:

$\text{log K}{}^2{}_{\mathrm{sp}}\text{= (? 9.8 ± 0.03) × 10}{}^4\text{(}\text{1}\text{T°K}\text{) + (1.52 ± 0.09)}$

within a 5–25°C temperature range. The effect of pressure on the solubility of malachite in water and seawater was estimated from partial molar volume and compressibility data. For 25 °C at infinite dilution $\text{K'}{}_{\mathrm{sp}}\text{(1000 bar)}\text{K'}{}_{\mathrm{sp}}\text{(0)}\text{= 240}$ and in seawater $\text{K′}{}_{\mathrm{sp}}\text{(1000)}\text{K'}{}_{\mathrm{sp}}\text{(0)}\text{= 44}$.Comparison of stoichiometric and apparent malachite equilibrium constants has been used to estimate the extent of copper(II) ion interaction at the ionic strength of seawater. In dilute carbonate medium (total alkalinity, TA = 2.4 meq/kg H₂O, pH 8.3), 2.9% of total dissolved copper exists as the free copper(II) ion and in seawater (S = 36.9%., TA = 2.3 meq/kg H₂O, pH = 8.1), $\text{[Cu}{}^{\mathrm{2+}}\text{]}\text{T(Cu)}$ is 3.1%.Total dissolved copper levels of approximately 450–750 nMol/Kg are necessary to attain malachite saturation conditions in the open ocean. Observations of malachite particles suspended in seawater must be explained by precipitation or solid phase substitution reactions from localized environments rather than by direct precipitation from bulk seawater.