Automated cleaning and uncertainty attribution of archival bathymetry based on a priori knowledge

Hydrographic offices hold large valuable historic bathymetric data sets, many of which were collected using older generation survey systems that contain little or no metadata and/or uncertainty estimates. These bathymetric data sets generally contain large outlier (errant) data points to clean, yet standard practice does not include rigorous automated procedures for systematic cleaning of these historical data sets and their subsequent conversion into reusable data formats. In this paper, we propose an automated method for this task. We utilize statistically diverse threshold tests, including a robust least trimmed squared method, to clean the data. We use LOESS weighted regression residuals together with a Student-t distribution to attribute uncertainty for each retained sounding; the resulting uncertainty values compare favorably with native estimates of uncertainty from co-located data sets which we use to estimate a point-wise goodness-of-fit measure. Storing a cleansed validated data set augmented with uncertainty in a re-usable format provides the details of this analysis for subsequent users. Our test results indicate that the method significantly improves the quality of the data set while concurrently providing confidence interval estimates and point-wise goodness-of-fit estimates as referenced to current hydrographic practices.     

Suffocation of pilchards (Sardinops sagax) by a green microalgal bloom in Wellington Harbour,New Zealand

A bloom of the green microalga Tetraselmis sp. in a small lagoon in Wellington Harbour, New Zealand, is considered to have caused a fish kill of pilchards (Sardinops sagax). The fish deaths are attributed to anoxia brought about by a combination of reduced dissolved oxygen levels and the microalgae sticking to and clogging the secondary gill lamellae of the fish.     

Mechanism and kinetics of pseudomorphic mineral replacement reactions: A case study of the replacement of pentlandite by violarite

Although pseudomorphic mineral replacement reactions are common in all geological environments, and have long been considered important to many geological processes such as metamorphism, metasomatism, diagenesis, and chemical weathering, their mechanisms are still not well known. We present a combined textural and kinetic study of the replacement of pentlandite, (Fe,Ni)₉S₈, by violarite (NiFe)₃S₄, and describe the mechanisms and kinetic behavior of this reaction by considering the role of the fluid phase, the causes of coupling between pentlandite dissolution and violarite precipitation, the rate-limiting steps controlling the kinetic behavior, and the origin of the length scale of the features preserved during pseudomorphism.The experiments were conducted under mild hydrothermal conditions (80-210 °C, vapor saturated pressures). Reaction kinetics shows a complex behavior depending on various physical and chemical parameters including temperature, pH, concentrations of various reaction species, solid-weight-to-fluid-volume-ratio and specific surface area. The rate of replacement (i) increases with temperature from 80 to 125 °C, then decreases as temperature further increases to 210 °C, (ii) first increases then decreases with decreasing pH from pH 6 to 1, (iii) increases with increasing concentration of oxidants such as O_2(aq), H₂O₂, and KMnO₄, but decreases with increasing concentration of Ni²⁺ and Fe³⁺, and with increasing solid-weight-to-fluid-volume ratio, (iv) increases linearly with the specific surface area. This kinetic behavior as well as the resulting textures revealed a coupled dissolution-reprecipitation reaction mechanism.Nanometer-scale pseudomorphic replacement, through which the crystallographic orientation of pentlandite is inherited by violarite, occurs only between 1 < pH < 6, and spatial coupling between dissolution and reprecipitation is controlled by the local solution chemistry as well as by epitaxial nucleation mediated by the pentlandite substrate. The kinetic results show that pentlandite dissolution is rate-limiting under mild acidic to neutral conditions (1 < pH < 6), while violarite precipitation is rate-limiting under strong acidic conditions (pH 1). The difference in rate-limiting steps influences the coupling mechanism and causes the different degrees of preservation (length scale of pseudomorphism) and different morphologies observed at high and low pHs: pentlandite dissolution being rate-limiting results in nanoscale coupling between dissolution and precipitation and thus nanoscale pseudomorphism (length scale <20 nm), in which the replacement precisely preserves the morphology and internal details, resembling remarkably the natural pentlandite/violarite assemblages. In contrast, violarite precipitation being rate-limiting results in microscale pseudomorphism (length scale ∼10 μm): the morphology of the pentlandite grains is only roughly preserved and internal details are not preserved.This case study illustrates some general principles of replacement reactions proceeding via the coupled dissolution-reprecipitation mechanism: (i) primary mineral dissolution needs to be rate-limiting compared to the secondary mineral precipitation in order to achieve a high degree pseudomorphic replacement; (ii) the effects of solution composition on reaction kinetics can be qualitatively rationalized by considering the rate-limiting step reaction.     

Re-Os and Mo isotope systematics of black shales from the Middle Proterozoic Velkerri and Wollogorang Formations, McArthur Basin, northern Australia

Joint application of the Mo isotope paleoredox proxy and Re-Os deposition-age geochronometer to euxinic black shales has potential for tracing the evolution of ocean redox chemistry over geological time. Here, we report new Re-Os and Mo isotope data for the Mesoproterozoic Velkerri Formation (Roper Group) and Paleoproterozoic Wollogorang Formation (Tawallah Group), McArthur Basin, northern Australia. New Re-Os ages of 1361 ± 21 Ma (2σ, n = 14, mean square of weighted deviates [MSWD] = 1.3, Model 1) and 1417 ± 29 Ma (2σ, n = 12, MSWD = 1.3, Model 1) constrain the depositional age of the Velkerri Formation and its contained biomarkers, as well as acritarchs and microfossils from the Roper Group. Black shales from the upper Velkerri Formation have high Mo abundances (105-119 ppm) and degree of pyritization [DOP] values (0.90-0.92) implying quantitative conversion of molybdate (MoO₄²⁻) to thiomolybdate (MoS₄²⁻) in overlying bottom waters. The average δ^97/95Mo (0.72 ± 0.10‰, 2σ, n = 6) of these shales is consistent with previous data, but represents a significantly more precise determination for global seawater δ^97/95Mo at 1.4 Ga. This value is lighter than present-day seawater by ∼0.85‰ and reflects expanded strongly euxinic deep ocean conditions ([H₂S]_aq > 11 μM) relative to oxic, suboxic, and weakly/intermittently euxinic ([H₂S]_aq < 11 μM) marine deposition in the 1.4 Ga oceans. Mass-balance modelling suggests Mo removal into strongly euxinic and oxic sediments may have comprised 30-70% and less than 15%, respectively, of the oceanic Mo sink at 1.4 Ga as opposed to 5% and 35% today, respectively.The Re-Os radioisotope system in organic-rich shales serves as a test for post-depositional alteration that could affect the usefulness of paleoredox tracers such as Mo stable isotopes. Re-Os isotope data for the Wollogorang Formation black shales are scattered and yield a highly imprecise date of 1359 ± 150 Ma (2σ, n = 21, MSWD = 85, Model 3). This age is younger than U-Pb zircon ages from interbedded tuffs that constrain the age of deposition at ca. 1730 Ma. In conjunction with previous petrological, geochemical, and paleomagnetic data, the Re-Os isotope data suggest hydrothermal fluid flow through the Wollogorang Formation, possibly associated with formation of the ca. 1640 Ma McArthur River Pb-Zn-Ag sedimentary exhalative deposit, resulted in post-depositional mobilization of Re and Os. Based on the degree of deviation of the Re-Os data from a 1730 Ma reference line, open-system behavior of Re and Os was greatest near the base of the black shale unit. Wollogorang Formation black shales are enriched in Mo (41-58 ppm), but are characterized by variable δ^97/95Mo (0.3-0.8‰) and DOP (0.57-0.92). The lightest δ^97/95Mo values occur near the base of the black shale unit. Based on the Re-Os systematics, hydrothermal fluids have probably overprinted the authigenic δ^97/95Mo signature in those shales. However, the heaviest δ^97/95Mo values in the Wollogorang Formation come from stratigraphically higher shales, and are similar to those observed for the Velkerri Formation, and thus may reflect seawater δ^97/95Mo at 1.73 Ga.     

Re-evaluating Nd/Nd in lunar mare basalts with implications for the early evolution and bulk Sm/Nd of the Moon

The Moon likely accreted from melt and vapor ejected during a cataclysmic collision between Proto-Earth and a Mars-sized impactor very early in solar system history. The identical W, O, K, and Cr isotope compositions between materials from the Earth and Moon require that the material from the two bodies were well-homogenized during the collision process. As such, the ancient isotopic signatures preserved in lunar samples provide constraints on the bulk composition of the Earth. Two recent studies to obtain high-precision ¹⁴²Nd/¹⁴⁴Nd ratios of lunar mare basalts yielded contrasting results. In one study, after correction of neutron fluence effects imparted to the Nd isotope compositions of the samples, the coupled ¹⁴²Nd-¹⁴³Nd systematics were interpreted to be consistent with a bulk Moon having a chondritic Sm/Nd ratio [Rankenburg K., Brandon A. D. and Neal C. R. (2006) Neodymium isotope evidence for a chondritic composition of the Moon. Science312, 1369-1372]. The other study found that their data on the same and similar lunar mare basalts were consistent with a bulk Moon having a superchondritic Sm/Nd ratio [Boyet M. and Carlson R. W. (2007) A highly depleted Moon or a non-magma origin for the lunar crust? Earth Planet. Sci. Lett.262, 505-516]. Delineating between these two potential scenarios has key ramifications for a comprehensive understanding of the formation and early evolution of the Moon and for constraining the types of materials available for accretion into large terrestrial planets such as Earth.To further examine this issue, the same six lunar mare basalt samples measured in Rankenburg et al. [Rankenburg K., Brandon A. D. and Neal C. R. (2006) Neodymium isotope evidence for a chondritic composition of the Moon. Science312, 1369-1372] were re-measured for high-precision Nd isotopes using a multidynamic routine with reproducible internal and external precisions to better than ±3 ppm (2σ) for ¹⁴²Nd/¹⁴⁴Nd ratios. The measurements were repeated in a distinct second analytical campaign to further test their reproducibility. Evaluation of accuracy and neutron fluence corrections indicates that the multidynamic Nd isotope measurements in this study and the 3 in Boyet and Carlson [Boyet M. and Carlson R. W. (2007) A highly depleted Moon or a non-magma origin for the lunar crust? Earth Planet. Sci. Lett.262, 505-516] are reproducible, while static measurements in the previous two studies show analytical artifacts and cannot be used at the resolution of 10 ppm to determine a bulk Moon with either chondritic or superchondritic Sm/Nd ratios. The multidynamic data are best explained by a bulk Moon with a superchondritic Sm/Nd ratio that is similar to the present-day average for depleted MORB. Hafnium isotope data were collected on the same aliquots measured for their ¹⁴²Nd/¹⁴⁴Nd isotope ratios in order to assess if the correlation line for ¹⁴²Nd-¹⁴³Nd systematics reflect mixing processes or times at which lunar mantle sources formed. Based on the combined ¹⁴²Nd-¹⁴³Nd-¹⁷⁶Hf obtained we conclude that the ¹⁴²Nd-¹⁴³Nd correlation line measured in this study is best interpreted as an isochron with an age of 229⁺²⁴₋₂₀Ma after the onset of nebular condensation. The uncertainties in the data permit the sources of these samples to have formed over a 44 Ma time interval. These new results for lunar mare basalts are thus consistent with a later Sm-Nd isotope closure time of their source regions than some recent studies have postulated, and a superchondritic bulk Sm/Nd ratio of the Moon and Earth. The superchondritic Sm/Nd signature was inherited from the materials that accreted to make up the Earth-Moon system. Although collisional erosion of crust from planetesimals is favored here to remove subchondritic Sm/Nd portions and drive the bulk of these bodies to superchondritic in composition, removal of explosive basalt material via gravitational escape from such bodies, or chondrule sorting in the inner solar system, may also explain the compositional features that deviate from average chondrites that make up the Earth-Moon system. This inferred superchondritic nature for the Earth similar to the modern convecting mantle means that there is no reason to invoke a missing, subchondritic reservoir to mass balance the Earth back to chondritic for Sm/Nd ratios. However, to account for the subchondritic Sm/Nd ratios of continental crust, a second superchondritic Sm/Nd mantle reservoir is required.     

Superposed lateral ramps in the Pell City thrust sheet, Appalachian thrust belt, Alabama

In the Appalachian thrust belt in Alabama, thrust sheets of Paleozoic strata generally strike northeastward and are imbricated northwestward; four transverse zones cross the regional strike of the thrust belt. The large-scale Pell City thrust sheet ends southwestward at an oblique lateral ramp within the Harpersville transverse zone, where the leading edge of the thrust sheet (the Pell City fault) curves abruptly 55° counterclockwise. The northwest-striking segment of the Pell City fault conforms to the geometry of an oblique lateral ramp in the footwall. Furthermore, the Pell City fault cuts up section in the hanging wall southwestward toward the transverse zone, indicating a hanging-wall lateral ramp emplaced over the footwall oblique lateral ramp.In the hanging wall adjacent to the northwest-trending segment of the Pell City fault, a pervasive train of upright, isoclinal folds (with 50% apparent shortening) trends N15°W, oblique to the regional translation direction. The fold train is limited to the southwestern part of the Pell City thrust sheet; farther northeast, the regional northeasterly strike prevails. The isoclinal folds in the hanging wall indicate contractional crowding perpendicular to the footwall oblique lateral ramp.     

Distribution of high field strength elements (Y, Zr, REE, Hf, Ta, Th, U) in adjacent magnetite and chert bands and in reference standards FeR-3 and FeR-4 from the Temagami iron-formation, Canada, and the redox level of the Neoarchean ocean

Adjacent magnetite and chert bands and reference standards FeR-3 and FeR-4 from the Neoarchean Temagami iron-formation (IF) show shale-normalized rare earth and yttrium (REY) patterns with low Nd/Yb ratios and positive Eu, Gd and Y anomalies, indicating that they formed as marine chemical sediments. In contrast to previous claims, none of the samples shows any Ce anomaly, indicating the absence of oxidative Ce-REY decoupling and arguing against oxic conditions in the wider vicinity of the Neoarchean “Temagami seabasin”. The distribution of Zr, Hf and Ta yields Zr/Hf and Hf/Ta ratios that differ from those of chondrites, average upper continental crust and local shales, suggesting that the Temagami IF is the only case observed so far in which a significant fraction of these elements is non-detrital but sourced from seawater. If Neoarchean seawater was characterized by Zr/Hf and Hf/Ta ratios similar to those of modern seawater these ratios point towards preferential scavenging of Hf over Zr and Ta, as is typical of the modern ocean. Similar to the 2.9 Ga old Mozaan IF in the Pongola Supergroup, South Africa, the Temagami IF shows low Th/U ratios that differ from those of the respective local shales and from that of average upper continental crust. Decoupling of U and Th results from U⁴⁺ oxidation in the Earth's surface system and fractionated Th/U ratios in these marine chemical sediments are, therefore, at odds with the lack of Ce anomalies. This suggests a different redox-sensitivity of the two paleo-redox-proxies Th–U and Ce-REY and demonstrates that the Temagami IF and the Mozaan IF warrant further study of other paleo-redox-proxies.     

Microbial reduction of ferrous arsenate: Biogeochemical implications for arsenic mobilization

In reduced aqueous environments, the presence of As in solution is a function of both biotic and abiotic mechanisms. Recent studies have demonstrated a significant release of As(III) through the microbial reduction of dissolved and mineral-bound As(V), which raises health concerns when the greater comparative mobility and toxicity of As(III) is considered. These release mechanisms do not operate in isolation but occur in concert with a number of removal processes, including secondary mineralization and sorption to other natural substrates. Thermodynamic and applied experimental studies have shown that ferrous arsenates, such as symplesite [Fe(II)₃(As(V)O₄)₂·8H₂O], may provide a significant sink for Fe(II) and As(V). In this study, the stability of a representative ferrous arsenate phase in the presence of the arsenate-reducing bacterium Shewanella sp. strain ANA-3 is examined. The reduction of ferrous arsenate by ANA-3 results in the release of aqueous As(III) and, subsequently, the progressive nucleation of a biogenic ferrous arsenite phase proximal to the microbial cells. The valence states of secondary solid-phase products were verified using X-ray absorption spectroscopy (XAS). Electron microscopy reveals that nucleation occurs on cellular exudates which may imply a role of extracellular reduction through c-type cytochromes as investigated in recent literature. These observations provide new insights into the reduction mechanisms of ANA-3 and the biogeochemical cycling of As(III) in natural systems.     

Damage field and site effects: multidisciplinary studies of the 1964 earthquake series in Central Switzerland

Central Switzerland shows comparatively high seismic activity by Swiss standards. Many historical earthquakes are known and several of them caused damage. The last major event dates back to 1964 and has the characteristics of an earthquake swarm. Among dozens of felt shocks were two main shocks (Mw = 5 and 5.7) that moderately damaged a limited area with hundreds of buildings suffering loss. Our aim here was to reconstruct the damage field and to analyze whether it was influenced by site effects. Given the existence of a contemporary damage assessment and other historical sources, we could describe the damage field in detail. For about 95% of the affected buildings, we could reconstruct the location and extent of loss, using assessments from the European Macroseismic Scale (EMS 98). Spatial analysis of the resulting data showed that most losses were concentrated in the villages of Sarnen and Kerns. Damage to residential houses and barns was by far most frequent (90%), but expensive losses to the relatively few sacral buildings were responsible for almost 50% of the repair costs. We compared the damage data with deposit thickness and soil composition and carried out field experiments using H/V spectral ratios to measure the fundamental frequency of ground resonance at 75 sites to estimate the frequency band in which amplification occurs. Our results show that locations on both thick fluviatile sediments and large alluvial cones showed higher intensities than did other ground types. Moreover, at some sites, intensity was probably increased by a layer of weathered rock below thin deposits.