Production and detection of carbon dioxide on Iapetus

Cassini VIMS detected carbon dioxide on the surface of Iapetus during its insertion orbit. We evaluated the CO₂ distribution on Iapetus and determined that it is concentrated almost exclusively on Iapetus’ dark material. VIMS spectra show a 4.27-μm feature with an absorption depth of 24%, which, if it were in the form of free ice, requires a layer 31 nm thick. Extrapolating for all dark material on Iapetus, the total observable CO₂ would be 2.3 × 10⁸ kg.Previous studies note that free CO₂ is unstable at 10 AU over geologic timescales. Carbon dioxide could, however, be stable if trapped or complexed, such as in inclusions or clathrates. While complexed CO₂ has a lower thermal volatility, loss due to photodissociation by UV radiation and gravitational escape would occur at a rate of 2.6 × 10⁷ kg year⁻¹. Thus, Iapetus’ entire inventory of surface CO₂ could be lost within a few decades.The high loss/destruction rate of CO₂ requires an active source. We conducted experiments that generated CO₂ by UV radiation of simulated icy regolith under Iapetus-like conditions. The simulated regolith was created by flash-freezing degassed water, crushing it into sub-millimeter sized particles, and then mixing it with isotopically labeled amorphous carbon (¹³C) dust. These samples were placed in a vacuum chamber and cooled to temperatures between 50 K and 160 K. The samples were irradiated with UV light, and the products were measured using a mass spectrometer, from which we measured ¹³CO₂ production at a rate of 2.0 × 10¹² mol s⁻¹. Extrapolating to Iapetus and adjusting for the solar UV intensity and Iapetus’ surface area, we calculated that CO₂ production for the entire surface would be 1.1 × 10⁷ kg year⁻¹, which is only a factor of two less than the loss rate. As such, UV photochemical generation of CO₂ is a plausible source of the detected CO₂.     

Book review

Offshore Soil Mechanics edited by Philip George and David Wood. Cambridge University Engineering Department and Lloyd's Register of Shipping, London, 1976. 468 pp. £7.50 + shipping.

Beach Processes and Sedimentation by Paul D. Komar. Prentice‐Hall, Inc. Englewood Cliffs, New Jersey, 1976. 429 pp., $26.95.     

High‐frequency water quality monitoring in an urban catchment: hydrochemical dynamics,primary production and implications for the Water Framework Directive

This paper describes the hydrochemistry of a lowland, urbanised river‐system, The Cut in England, using in situ sub‐daily sampling. The Cut receives effluent discharges from four major sewage treatment works serving around 190 000 people. These discharges consist largely of treated water, originally abstracted from the River Thames and returned via the water supply network, substantially increasing the natural flow. The hourly water quality data were supplemented by weekly manual sampling with laboratory analysis to check the hourly data and measure further determinands. Mean phosphorus and nitrate concentrations were very high, breaching standards set by EU legislation. Although 56% of the catchment area is agricultural, the hydrochemical dynamics were significantly impacted by effluent discharges which accounted for approximately 50% of the annual P catchment input loads and, on average, 59% of river flow at the monitoring point. Diurnal dissolved oxygen data demonstrated high in‐stream productivity. From a comparison of high frequency and conventional monitoring data, it is inferred that much of the primary production was dominated by benthic algae, largely diatoms. Despite the high productivity and nutrient concentrations, the river water did not become anoxic, and major phytoplankton blooms were not observed. The strong diurnal and annual variation observed showed that assessments of water quality made under the Water Framework Directive (WFD) are sensitive to the time and season of sampling. It is recommended that specific sampling time windows be specified for each determinand, and that WFD targets should be applied in combination to help identify periods of greatest ecological risk. © 2015 The Authors. Hydrological Processes published by John Wiley & Sons Ltd.     

Non‐uniqueness with refraction inversion – a syncline model study

Non‐uniqueness occurs with the 1D parametrization of refraction traveltime graphs in the vertical dimension and with the 2D lateral resolution of individual layers in the horizontal dimension. The most common source of non‐uniqueness is the inversion algorithm used to generate the starting model. This study applies 1D, 1.5D and 2D inversion algorithms to traveltime data for a syncline (2D) model, in order to generate starting models for wave path eikonal traveltime tomography. The 1D tau‐p algorithm produced a tomogram with an anticline rather than a syncline and an artefact with a high seismic velocity. The 2D generalized reciprocal method generated tomograms that accurately reproduced the syncline, together with narrow regions at the thalweg with seismic velocities that are less than and greater than the true seismic velocities as well as the true values. It is concluded that 2D inversion algorithms, which explicitly identify forward and reverse traveltime data, are required to generate useful starting models in the near‐surface where irregular refractors are common. The most likely tomogram can be selected as either the simplest model or with a priori information, such as head wave amplitudes. The determination of vertical velocity functions within individual layers is also subject to non‐uniqueness. Depths computed with vertical velocity gradients, which are the default with many tomography programs, are generally 50% greater than those computed with constant velocities for the same traveltime data. The average vertical velocity provides a more accurate measure of depth estimates, where it can be derived. Non‐uniqueness is a fundamental reality with the inversion of all near‐surface seismic refraction data. Unless specific measures are taken to explicitly address non‐uniqueness, then the production of a single refraction tomogram, which fits the traveltime data to sufficient accuracy, does not necessarily demonstrate that the result is either ‘correct’ or the most probable.     

A drought outlook study in Korea

Abstract

Techniques are proposed for developing a monthly and weekly drought outlook and the drought outlook components are evaluated. A drought index, the surface water supply index (SWSI) was modified and used for the drought outlook. A water balance model (abcd) was successfully calibrated using a regional regression, including monthly and weekly factors, and was used to convert meteorology to hydrology. For the monthly drought outlook, an ensemble technique was applied, both with and without monthly industrial meteorology information (MIMI). For the weekly drought outlook, a deterministic forecasting technique was applied employing the Global Data Assimilation and Prediction System (GDAPS). The methodologies were applied to the Geum River basin in Korea. While only the weekly outlook using the GDAPS has sufficient forecasting capability to suggest it might be useful, the accuracy of the monthly drought outlook is expected to improve as the climate forecast accuracy increases.

Editor Z.W. Kundzewicz; Associate editor D. Hughes

Citation Kim, Y.-O., Lee, J.-K., and Palmer, R.N., 2012. A drought outlook study in Korea. Hydrological Sciences Journal, 57 (6), 1141–1153.     

Short-term residence and movement patterns of the annular seabream Diplodus annularis in a temperate marine reserve

The short-term movements of a small temperate fish, the annular seabream Diplodus annularis (Linnaeus 1758), were examined using standard tag-recapture and passive acoustic telemetry in Palma Bay (NW Mediterranean), a marine protected area (MPA). The study aimed to provide valuable information for assessing the recreational fishery and its results suggest that MPAs can be used to protect the adult stock of D. annularis. All the fish tagged with standard tags were recaptured near the release locations, with a maximum distance of ∼300 m. The maximum time between release and recapture was 185 d. Two different arrays of acoustic receivers were deployed, one in 2008 and another in 2009, within the MPA. Twenty adults were surgically tagged with acoustic transmitters. Fish monitored in 2008 (n = 12) were translocated from the point of capture to analyse the movement behaviour after artificial displacement. Upon release at displaced locations, 67% of the fish moved towards the original capture location using a time of return that ranged from 0.75 to 15.25 h. Fish monitored in 2009 (n = 8) were released at the point of capture. They showed high site fidelity with a maximum period of 27 d between the first time and the last time they were detected.     

Reconstruction of New Zealand Temperatures Back to AD 1720 Using Libocedrus bidwillii Tree-Rings

The longest chronology from New Zealand so faris from Libocedrus bidwillii Hook. f. (i.e.,from AD 1992 back to AD 1140, a span of 853 years). A subset of 11 chronologies was selected from anetwork of 23 sites to reconstruct past temperaturesbased on the similarity of significant responsefunctions. A comparison of climate data overdifferent seasons with these 11 chronologies wascarried out using a bootstrap transfer function. Average late-summer (February–March) temperature wasselected for reconstruction based on independentverification results. The reconstructed temperaturewas then presented for the period back to AD 1720. The chronologies reconstructed years experiencing hotsummers better than cold summers. The power spectrumof the reconstructed temperatures showed periodicitiessimilar to those of the observed temperatures. Reconstructed temperatures were significantlycorrelated with other proxy climate reconstructionsderived from tree rings in New Zealand. However,unlike the other tree ring-based reconstructions, theLibocedrus bidwillii series reconstructed boththe 1950s and 1970s warming periods. The resultsalso compared very favourably with other palaeoclimateevidence.     

Tourmaline in Proterozoic Massive Sulfide Deposits from Rajasthan, India

We have analyzed the chemical composition and boron isotope composition of tourmaline from tourmalinites, granite and a quartz-tourmaline vein from the Deri ore zone and from a pegmatitic band in the Rampura-Agucha ore body. These two Proterozoic massive sulfide deposits occur in the Aravalli-Delhi orogenic belt, Rajasthan, northwest India. Tourmaline from stratiform tourmalinites closely associated with the massive sulfides in the Deri deposit have preserved their original chemical compositions despite regional and thermal metamorphism in the area. These tourmalines have low Fe/(Fe + Mg) ratios (0.19–0.30; mean 0.26) that suggest formation close to the sediment-sea water interface. The δ¹¹B values (−15.5 and −16.4‰) are compatible with boron derived from leaching of argillaceous sediments and/or felsic volcanics underlying the original massive sulfide deposit during its formation. Boron isotope compositions measured in tourmaline from a post-ore granite and quartz-tourmaline vein in the Deri deposit indicate that boron in these tourmalines was derived from the tourmalinites produced during ore formation. The boron isotope systematics of a coarse brown tourmaline crystal from a pegmatitic band on the hanging wall contact of the Rampura-Agucha deposit indicate that 45 ± 25% of the boron within the original tourmaline was lost during upper amphibolite facies regional metamorphism. Received: 3 April 1996 / Accepted: 11 April 1996     

Dissolution/precipitation kinetics of boehmite and gibbsite: Application of a pH-relaxation technique to study near-equilibrium rates

The dissolution and precipitation rates of boehmite, AlOOH, at 100.3 °C and limited precipitation kinetics of gibbsite, Al(OH)₃, at 50.0 °C were measured in neutral to basic solutions at 0.1 molal ionic strength (NaCl + NaOH + NaAl(OH)₄) near-equilibrium using a pH-jump technique with a hydrogen-electrode concentration cell. This approach allowed relatively rapid reactions to be studied from under- and over-saturation by continuous in situ pH monitoring after addition of basic or acidic titrant, respectively, to a pre-equilibrated, well-stirred suspension of the solid powder. The magnitude of each perturbation was kept small to maintain near-equilibrium conditions. For the case of boehmite, multiple pH-jumps at different starting pHs from over- and under-saturated solutions gave the same observed, first order rate constant consistent with the simple or elementary reaction: .

This relaxation technique allowed us to apply a steady-state approximation to the change in aluminum concentration within the overall principle of detailed balancing and gave a resulting mean rate constant, (2.2 ± 0.3) × 10⁻⁵ kg m⁻² s⁻¹, corresponding to a 1σ uncertainty of 15%, in good agreement with those obtained from the traditional approach of considering the rate of reaction as a function of saturation index. Using the more traditional treatment, all dissolution and precipitation data for boehmite at 100.3 °C were found to follow closely the simple rate expression:

R_net,boehmite=10^-5.485{m_OH^-}{1-exp(ΔG_r/RT)}, with R_net in units of mol m⁻² s⁻¹. This is consistent with Transition State Theory for a reversible elementary reaction that is first order in OH⁻ concentration involving a single critical activated complex. The relationship applies over the experimental ΔG_r range of 0.4–5.5 kJ mol⁻¹ for precipitation and −0.1 to −1.9 kJ mol⁻¹ for dissolution, and the pH_m ≡ −log(mH⁺) range of 6–9.6. The gibbsite precipitation data at 50 °C could also be treated adequately with the same model:R_net,gibbsite=10^-5.86{m_OH^-}{1-exp(ΔG_r/RT)}, over a more limited experimental range of ΔG_r (0.7–3.7 kJ mol⁻¹) and pH_m (8.2–9.7).     

Tourmaline mineralization in the Barberton greenstone belt,South Africa: early Archean metasomatism by evaporite-derived boron

Tourmaline-rich rocks are common in the lowgrade, interior portions of the Barberton greenstone belt of South Africa, where shallow-marine sediments and underlying altered basaltic and komatiitic lavas contain up to 50% tourmaline. The presence of tourmaline-bearing rip-up clasts, intraformational tourmalinite pebbles, and tourmaline-coated grains indicates that boron mineralization was a low-temperature, surficial process. The association of these lithologies with stromatolites, evaporites, and shallow-water sedimentary structures and the virtual absence of tourmaline in correlative deep-water facies rocks in the greenstone bels strengthens this model.Five tourmaline-bearing lithologic groups (basalts, komatiites, evaporite-bearing sediments, stromatolitic sediments, and quartz veins) are distinguished based on field, petrographic, and geochemical criteria. Individual tourmaline crystals within these lithologies show internal chemical and textural variations that reflect continued growth through intervals of change in bulk-rock and fluid composition accompanying one or more metasomatic events. Large single-crystal variations exist in Fe/Mg, Al/Fe, and alkali-site vacancies. A wide range in tourmaline composition exists in rocks altered from similar protoliths, but tourmalines in sediments and lavas have similar compositional variations. Boron-isotope analysis of the tourmalines suggest that the boron enrichment in these rocks has a major marine evaporitic component. Sediments with gypsum pseudomorphs and lavas altered at low temperatures by shallow-level brines have the highest ¹¹B values (+2.2 to-1.9); lower ¹¹B values of late quartz veins (-3.7 to-5.7) reflect intermediate temperature, hydrothermal remobilization of evaporitic boron. The ¹¹B values of tourmaline-rich stromatolitic sediments (-9.8 and-10.5) are consistent with two-stage boron enrichment, in which earlier marine evaporitic boron was hydrothermally remobilized and vented in shallow-marine or subaerial sites, mineralizing algal stromatolites. The stromatolite-forming algae preferentially may have lived near the sites of hydrothermal discharge in Archean times.