Stability of massive ground ice bodies in University Valley,McMurdo Dry Valleys of Antarctica: Using stable O–H isotope as tracers of sublimation in hyper-arid regions

To date, studies of the stability of subsurface ice in the McMurdo Dry Valleys of Antarctica have been mainly based on climate-based vapor diffusion models. In University Valley (1800 m), a small glacier is found at the base of the head of the valley, and adjacent to the glacier, a buried body of massive ice was uncovered beneath 20–40 cm of loose cryotic sediments and sandstone boulders. This study assesses the origin and stability of the buried body of massive ice by measuring the geochemistry and stable O–H isotope composition of the ice and applies a sublimation and molecular diffusion model that accounts for the observed trends. The results indicate that the buried massive ice body represents an extension of the adjacent glacier that was buried by a rock avalanche during a cold climate period. The contrasting δ¹⁸O profiles and regression slope values between the uppermost 6 cm of the buried massive ice (upward convex δ¹⁸O profile and S_D-18O = 5.1) and that below it (progressive increase in δ¹⁸O and S_D-18O = 6.4) suggest independent post-depositional processes affected the isotope composition of the ice. The upward convex δ¹⁸O profile in the uppermost 6 cm is consistent with the ice undergoing sublimation. Using a sublimation and molecular diffusion model, and assuming that diffusion occurred through solid ice, the sublimation rate needed to fit the measured δ¹⁸O profile is 0.2 ? 10^? 3 mm yr^? 1, a value that is more similar to net ice removal rates derived from ³He data from cobbles in Beacon Valley till (7.0 ? 10^? 3 mm yr^? 1) than sublimation rates computed based on current climate (0.1–0.2 mm yr^?1). We suggest that the climate-based sublimation rates are offset due to potential ice recharge mechanisms or to missing parameters, particularly the nature and thermo-physical properties of the overlying sediments (i.e., temperature, humidity, pore structure and ice content, grain size).     

Modeling of diffusion behavior of humic acid and Nd in the presence of humic acid in compacted bentonite

The diffusion behavior of HA and Nd in the presence of HA in compacted bentonite was investigated experimentally by means of the through-diffusion method. Breakthrough of HA is observed in 1 and 0.1 mol dm⁻³ NaCl solution and is more significant with a lower dry density such as 1.2 Mg m⁻³. The one dimensional diffusion model taking parallel complexation equilibrium into account was fitted to the experimentally obtained breakthrough curves and concentration profiles, and the diffusion parameters, such as effective diffusivity and rock capacity factor, were evaluated. The obtained effective diffusivity, around 10⁻¹¹ m² s⁻¹, for HA and Nd–HA is comparable to the previously reported value. Using these parameters, predictive calculations were performed to evaluate the effect of HA concentration and sorption distribution coefficient. It is indicated that the effect of sorption distribution coefficient is significant only for a short period and that relatively low HA concentrations might bring higher diffused mass depending on the diffusion behavior of dominant species.     

Subduction erosion of forearc mantle wedge implicated in the genesis of the South Sandwich Island (SSI) arc: Evidence from boron isotope systematics

The South Sandwich volcanic arc is sited on a young oceanic crust, erupts low-K tholeiitic rocks, is characterized by unexotic pelagic and volcanogenic sediments on the down-going slab, and simple tectonic setting, and is ideal for assessing element transport through subduction zones. As a means of quantifying processes attending transfer of subduction-related fluids from the slab to the mantle wedge, boron concentrations and isotopic compositions were determined for representative lavas from along the arc. The samples show variable fluid-mobile/fluid-immobile element ratios and high enrichments of B/Nb (2.7 to 55) and B/Zr (0.12 to 0.57), similar to those observed in western Pacific arcs. δ¹¹B values are among the highest so far reported for mantle-derived lavas; these are highest in the central part of the arc (+ 15 to + 18‰) and decrease toward the southern and northern ends (+ 12 to + 14‰). δ¹¹B is roughly positively correlated with B concentrations and with ⁸⁷Sr/⁸⁶Sr ratios, but poorly coupled with other fluid-mobile elements such as Rb, Ba, Sr and U. Peridotites dredged from the forearc trench also have high δ¹¹B (ca. + 10‰) and elevated B contents (38–140 ppm). Incoming pelagic sediments sampled at ODP Site 701 display a wide range in δ¹¹B (+ 5 to ? 13‰; average = ? 4.1‰), with negative values most common. The unusually high δ¹¹B values inferred for the South Sandwich mantle wedge cannot easily be attributed to direct incorporation of subducting slab materials or fluids derived directly therefrom. Rather, the heavy B isotopic signature of the magma sources is more plausibly explained by ingress of fluids derived from subduction erosion of altered frontal arc mantle wedge materials similar to those in the Marianas forearc. We propose that multi-stage recycling of high-δ¹¹B and high-B serpentinite (possibly embellished by arc crust and volcaniclastic sediments) can produce extremely ¹¹B-rich fluids at slab depths beneath the volcanic arc. Infiltration of such fluids into the mantle wedge likely accounts for the unusual magma sources inferred for this arc.     

Mercury in the ecosystem of Admiralty Bay,King George Island,Antarctica: Occurrence and trophic distribution

Mercury (Hg) can reach the environment through natural and human-related sources, threatening ecosystems all over the planet due to its well known deleterious effects. Therefore, Antarctic trophic webs, despite being relatively isolated, are not exempt of its influence. To evaluate Hg concentrations in an Antarctic ecosystem, different tissues from 2 species of invertebrates, 2 of fish, 8 of birds, 4 of pinnipeds and at least 5 of vegetation were investigated (n = 176). For animals, values ranged from 0.018 to 48.7 μg g^? 1 dw (whole Antarctic krill and Antarctic Fur Seal liver). They were generally correlated to trophic position (assessed by δ¹⁵N and δ¹³C) but also to cephalopods and myctophids consumption. For vegetation, values ranged from 0.014 to 0.227 μg g^? 1 dw (Colobanthus quitensis and an unidentified lichen), with lichens presenting significantly higher values than mosses, likely due to year-round exposure and absorption of animal derived organic matter, as hypothesized by literature.     

Evidence for a hypogene paleohydrogeological event at the prospective nuclear waste disposal site Yucca Mountain,Nevada, USA,revealed by the isotope composition of fluid-inclusion water

Secondary calcite residing in open cavities in the unsaturated zone of Yucca Mountain has long been interpreted as the result of downward infiltration of meteoric water through open fractures. In order to obtain information on the isotopic composition (δD and δ¹⁸O) of the mineral-forming water we studied fluid inclusions from this calcite. Water was extracted from inclusions by heated crushing and the δD values were measured using a continuous-flow isotope-ratio mass spectrometry method. The δ¹⁸O values were calculated from the δ¹⁸O values of the host calcite assuming isotopic equilibrium at the temperature of formation determined by fluid-inclusion microthermometry.The δD values measured in all samples range between ? 110 and ? 90‰, similar to Holocene meteoric water. Coupled δ¹⁸O–δD values plot significantly, 2 to 8‰, to the right of the meteoric water line. Among the various processes operating at the topographic surface and/or in the unsaturated zone only two processes, evaporation and water–rock exchange, could alter the isotope composition of percolating water. Our analysis indicates, however, that none of these processes could produce the observed large positive δ¹⁸O-shifts. The latter require isotopic interaction between mineral-forming fluid and host rock at elevated temperature (>100 °C), which is only possible in the deep-seated hydrothermal environment. The stable isotope data are difficult to reconcile with a meteoric origin of the water from which the secondary minerals at Yucca Mountain precipitated; instead they point to the deep-seated provenance of the mineral-forming waters and their introduction into the unsaturated zone from below, i.e. a hypogene origin.     

Cooling-induced fractionation of mantle Li isotopes from the ultraslow-spreading Gakkel Ridge

Li isotopic compositions of magmatic rocks have gained considerable attention recently as probes of mantle-scale processes. However, the concentrations and isotopic composition of Li in mantle minerals from mid-ocean ridges remain relatively unconstrained. This is largely because of the general presence of seawater alteration in abyssal peridotites. Lithium elemental and isotopic compositions for mineral separates of coexisting olivine, clinopyroxene, orthopyroxene and bulk rocks of serpentine-free Gakkel Ridge peridotites were investigated. Bulk rocks have Li contents of 1.6 to 2.7 ppm and δ⁷Li values of 3 to 5‰, which fall within the range of reported normal pristine “MORB mantle” values. Lithium concentrations vary in the order cpx (2.1–4.7 ppm) > opx (0.9–1.7 ppm) ≥ olivine (0.4–0.9 ppm), the opposite found in “equilibrated” mantle peridotite xenoliths (Seitz and Woodland, 2000). The Li isotopic compositions indicate a systematic mineral variation with δ⁷Li_olivine (7.14‰–15.09‰) > δ⁷Li_opx (1.81‰–3.66‰) > δ⁷Li_cpx (?2.43‰ ? ?0.39‰). The δ⁷Li values of cpx are negatively correlated with their Li concentrations with the lightest value for the most enriched cpx grains. There is a first order negative linear correlation between Δ_{olivine–cpx} (δ⁷Li_olivine ? δ⁷Li_cpx) and ^ol/cpxD (Li_olivine/Li_cpx).Numerical simulations indicate that the observed systematic inter-mineral variations of Li concentrations and isotopic compositions could be explained by a cooling driven diffusive redistribution between minerals in a closed system if there is a temperature dependent partitioning of Li between olivine and clinopyroxene. The studied Gakkel Ridge abyssal peridotites may alternatively have cooled under a variable cooling rate with a rapid cooling before the Li system was closed, which is less likely given the tectonic setting. Our calculations confirm that Li systematics in minerals, especially in coexisting mineral phases could potentially be used as a mantle geospeedometer, even for slowly cooled mantle rocks.     

A lithium isotopic study of sub-greenschist to greenschist facies metamorphism in an accretionary prism,New Zealand

To investigate the behavior of Li during low-grade metamorphism and fluid flux in an accretionary prism we measured the Li concentrations ([Li]) and isotopic compositions (δ⁷Li) of sub-greenschist and greenschist-facies Otago Schist composites, as well as cross-cutting quartz veins, which are interpreted to have precipitated from slab-derived fluids. The average [Li] of sub-greenschist facies composites (41 ± 13 μg/g, 2σ) is statistically distinct (97% confidence level, student t test) to that of greenschist facies composites (34 ± 9 μg/g, 2σ), which have experienced mass addition of silica in the form of quartz veins having [Li] between 0.4–2.3 μg/g. A linear regression of the correlation between [Li] and calculated mass additions suggests that the depletion of [Li] in greenschist facies composites is due to both dilution from the addition of the quartz veins, as well as metamorphic dehydration. The [Li] of both groups of composites correlates with their CIA (Chemical Index of Alteration) values (50–58), which are low, consistent with the inferred graywacke protolith of the Otago Schist. The δ⁷Li of sub-greenschist and greenschist facies composites are remarkably constant, with an average δ⁷Li of 0.2 ± 1.7 (2σ) and ?0.5 ± 1.9 (2σ), respectively, and comparable to that of the average upper continental crust. Thus, metamorphism has had no discernable effect on δ⁷Li in these samples. The Li isotopic signature of the schists is similar to that seen in pelitic sedimentary rocks and likely reflects the δ⁷Li of the protoliths. The surprisingly light δ⁷Li of the quartz veins (?2.8 to ?1.4) likely records kinetic fractionation associated with Li ingress into the veins from surrounding wallrock.An isotopic equilibrium fluid flow model indicates that: 1) if the [Li] of slab-derived fluids is less than a few μg/g, the δ⁷Li of the overlying lithologies (i.e., the schists) is not significantly influenced by the fluid flux, regardless of the δ⁷Li of the fluids, 2) the slab-derived fluids will have heavy δ⁷Li of > + 10 after reacting with the prism sediments during their ascent, and 3) the [Li] of the slab-derived fluids is likely in the range of 0 < [Li] ≤ 41(μg/g). Thus, isotopically heavy slab-derived fluids that traverse sediments in accretionary prisms may leave little trace in the rocks and their surface compositional characteristics will reflect the net result of their interaction with the sediments of the prism.     

Vertical distribution of HTO and 125I− transport parameters in Boom Clay in the Essen-1 borehole (Mol,Belgium)

In the frame of the R&D activities performed on the Boom Clay for assessing the suitability of deep clayey formations for radioactive waste disposal, the transferability of the scientific results obtained on the Boom Clay in Mol to the whole Campine Basin is investigated. Boreholes were drilled at different locations (e.g. Mol, Doel, Essen) and cores were sampled over the entire thickness of the Boom Clay formation on which the migration parameters for iodide and tritiated water (HTO) are determined.At Essen, the transport parameters in the Boom Clay can be considered as homogeneous in the range from 159 m to 241 m Below Drilling Table. The average hydraulic conductivity is (5.4 ± 1.7) × 10⁻¹² m/s. The average ηR value for iodide is 0.25 ± 0.03 and 0.42 ± 0.05 for HTO. For HTO, this high value is mainly due to a higher value in the Putte Member (0.46 ± 0.03) compared to the other members (0.39 ± 0.02). The apparent diffusion coefficient is (1.3 ± 0.1) × 10⁻¹⁰ m²/s for HTO and (1.1 ± 0.2) × 10⁻¹⁰ m²/s for iodide. The expected effect of ionic strength (increasing with depth) on the ηR value of iodide is of the same size as the measurement error, what might explain why it was not observed.On a lateral (horizontal) level, the hydraulic conductivity at the Essen-1 borehole (5.4 × 10⁻¹² m/s) lies between that of Boom Clay in Mol-1 (2.5 × 10⁻¹² m/s) and that of Boom Clay in Doel-2b (1.4 × 10⁻¹¹ m/s). For iodide, the higher ηR value in Essen-1 and Doel-2b (ηR ≈ 0.25) than in Mol-1 (ηR ≈ 0.16) can partly be explained by a higher ionic strength of the pore water. Apart from the Putte Member at Essen-1, the HTO porosities of the Terhagen Member and the Transition zone in Essen are in the range of the average porosities observed in Mol and Doel (ηR ≈ 0.37–0.39). For both iodide and HTO, the value of the apparent diffusion coefficient D_app is similar in Mol-1 and in Doel-2b, with a clearly higher value for HTO than for iodide. In Essen-1, the apparent diffusion coefficients for iodide and HTO are nearly equal, and slightly smaller than the iodide value in Mol-1/Doel-2b. Accordingly, the HTO apparent diffusion coefficient is considerably smaller in Essen-1 than in Mol-1/Doel-2b.     

Balancing the global oceanic neodymium budget: Evaluating the role of groundwater

The distinctly different, ε_Nd(0) values of the Atlantic, Indian, and Pacific Oceans requires that the residence time of Nd in the ocean (i.e., τ_Nd) be on the order of, or less than, the ocean mixing time of ∼ 500–1500 yr. However, estimates of τ_Nd, based on river influxes, range from 4000 to 15,000 yr, thus exceeding the ocean mixing time. In order to reconcile the oceanic Nd budget and lower the residence time by roughly a factor of 10, an additional, as yet unidentified, and hence “missing Nd flux” to the ocean is necessary. Dissolution of materials deposited on continental margins has previously been proposed as a source of the missing flux. In this contribution, submarine groundwater discharge (SGD) is examined as a possible source of the missing Nd flux. Neodymium concentrations (n = 730) and ε_Nd(0) values (n = 58) for groundwaters were obtained from the literature in order to establish representative groundwater values. Mean groundwater Nd concentrations and ε_Nd(0) values were used along with recent estimates of the terrestrial (freshwater) component of SGD (6% of river discharge on a global basis) to test whether groundwater discharge to the coastal oceans could account for the missing flux. Employing mean Nd concentrations of the compiled data base (i.e., 31.8 nmol/kg for all 730 analyses and 11.3 nmol/kg for 141 groundwater samples from a coastal aquifer), the global, terrestrial-derived SGD flux of Nd is estimated to range between 2.9 × 10⁷ and 8.1 × 10⁷ mol/yr. These estimates are of the same order of magnitude, and within a factor of 2, of the missing Nd flux (i.e., 5.4 × 10⁷ mol/yr). Applying the SGD Nd flux estimates, the global average ε_Nd(0) of SGD is predicted to be − 9.1, which is similar to our estimate for the missing Nd flux (− 9.2), and in agreement with the mean (± S.D.) ε_Nd(0) measured in groundwaters (i.e., ε_Nd(0) = −8.9 ± 4.2). The similarities in the estimated SGD Nd flux and corresponding ε_Nd(0) values to the magnitude and isotope composition of the missing Nd flux are compelling, and suggest that discharge of groundwater to the oceans could account for the missing Nd flux. Future investigations should focus on quantifying the Nd concentrations and isotope compositions of groundwater from coastal aquifers from a variety of coastal settings, as well as the important geochemical reactions that effect Nd concentrations in subterranean estuaries in order to better constrain contributions of SGD to the oceanic Nd budget.     

A combined glass dissolution/diffusion experiment in Boom Clay at 30 °C

At the appropriate times, silica diffusion in clay is possibly the rate determining process for the dissolution of vitrified waste disposed of in a clay layer. For testing this hypothesis, combined glass dissolution/silica diffusion experiment are performed. SON68 glass coupons doped with the radioactive tracer ³²Si are sandwiched between two cores of humid Boom Clay, heated to 30 °C. Due to glass dissolution, ³²Si is released and diffuses into the clay. At the end of an experiment, the mass loss of the glass coupon is measured and the clay core is sliced to determine the diffusion profile of the ³²Si released from the glass in the clay.Both mass loss and the ³²Si diffusion profile in the clay are described well by a model combining glass dissolution according to a linear rate law with silica diffusion in the clay. Fitting the experiments to this model leads to an apparent silica diffusion coefficient in the clay between 7 × 10⁻¹³ m²/s and 1.2 × 10⁻¹² m²/s. Previously determined values from diffusion experiments at 25 °C are around 6 × 10⁻¹³ m²/s (In-Diffusion experiments) and 2 × 10⁻¹³ m²/s (percolation experiments). The maximal glass dissolution rate for glass next to clay is around 1.6 × 10⁻⁷ g glass/m² s (i.e. 0.014 g glass/m² day). In undisturbed clay, the measured silica concentration is around 5 mg/L. Combining these values with the previously measured (In-Diffusion experiments) product of accessible porosity and retardation factor, leads in two ways to a silica glass saturation concentration in clay between 8 and 10 mg Si/L.Another candidate for the rate determining process of the dissolution of vitrified waste disposed in a clay layer is silica precipitation. Although silica precipitation due to glass dissolution has been shown experimentally at 90 °C, extending the model with silica precipitation does not lead to much better fits, nor could meaningful values of a possible precipitation rate be obtained.     

Spatial and temporal distribution of zooplankton related to the environmental conditions in the coral reef lagoon of New Caledonia,Southwest Pacific

The distribution of zooplanktonic prey of fish larvae was examined in three bays and two lagoonal stations in the Southwest lagoon of New Caledonia. Water column conditions were characterized by increasing chlorophyll a and particulate organic matter (POM) concentrations from the lagoon to the estuarine bay. The mean zooplankton settled volume and total density were significantly higher in the estuarine bay, reaching 35.1 mL m⁻³ and 3.5 × 10⁵ individuals m⁻³, respectively. The total zooplankton density also progressively increased along the sampling period. The composition of assemblages differed between the lagoon and the bays, and was similar in the three bays. Wind speed, surface temperature, chlorophyll a and POM explained these variations, as revealed by a co-inertia analysis (COIA). The prey preferred by fish larvae, i.e. small crustaceans and small copepods, were more abundant in bays. Sheltered bays, most influenced by terrigenous inputs, are likely to provide the best feeding conditions.     

Development of the sediment and water quality management strategies for the Salt-water River,Taiwan

The Salt-water River watershed is one of the major river watersheds in the Kaohsiung City, Taiwan. Water quality and sediment investigation results show that the river water contained high concentrations of organics and ammonia–nitrogen, and sediments contained high concentrations of heavy metals and organic contaminants. The main pollution sources were municipal and industrial wastewaters. Results from the enrichment factor (EF) and geo-accumulation index (I_geo) analyses imply that the sediments can be characterized as heavily polluted in regard to Cd, Cr, Pb, Zn, and Cu. The water quality analysis simulation program (WASP) model was applied for water quality evaluation and carrying capacity calculation. Modeling results show that the daily pollutant inputs were much higher than the calculated carrying capacity (1050 kg day⁻¹ for biochemical oxygen demand and 420 kg day⁻¹ for ammonia–nitrogen). The proposed watershed management strategies included river water dilution, intercepting sewer system construction and sediment dredging.     

Nutrient inputs from submarine groundwater discharge on the Santiago reef flat,Bolinao, Northwestern Philippines

Submarine groundwater discharge (SGD) on the reef flat of Bolinao, Pangasinan (Philippines) was mapped using electrical resistivity, ²²²Rn, and nutrient concentration measurements. Nitrate levels as high as 126 μM, or 1–2 orders of magnitude higher than ambient concentrations, were measured in some areas of the reef flat. Nutrient fluxes were higher during the wet season (May–October) than the dry season (November–April). Dissolved inorganic nitrogen (DIN = NO₃ + NO₂ + NH₄) and soluble reactive phosphorus (SRP) fluxes during the wet season were 4.4 and 0.2 mmoles m⁻² d⁻¹, respectively. With the increase population size and anthropogenic activities in Bolinao, an enhancement of SGD-derived nitrogen levels is likely. This could lead to eutrophic conditions in the otherwise oligotrophic waters surrounding the Santiago reef flat.     

Pliocene climate change of the Southwest Pacific and the impact of ocean gateways

The transition from the early Pliocene “Warmhouse” towards the present “Icehouse” climate and the role of Gateway dynamics are intensively debated. Both, the constrictions of the Central American Seaway and the Indonesian Gateway affected ocean circulation and climate during the Pliocene epoch. Here, we use combined δ¹⁸O and Mg/Ca ratios of planktonic foraminifera (marine protozoa) from surface and subsurface levels to reconstruct the thermal structure and changes in salinities from the Southwest Pacific Deep Sea Drilling Project (DSDP) Site 590B from 6.5 to 2.5 Ma. Our data suggest a gradual cooling of ~ 2 °C and freshening of the sea surface during ~ 4.6–4 Ma with an increased meridional temperature gradient between the West Pacific Warm Pool and the Southwest Pacific when the closing of the Central American Seaway reached a critical threshold. After ~ 3.5 Ma, the restricted Indonesian Gateway might have amplified the East Australian Current, allowing enhanced heat transport towards the Southwest Pacific with reduced meridional temperature gradients when the global climate gradually cooled. At the same time our data suggest a cooling and freshening of Subantarctic Mode Water (SAMW) or/and an increased northward flow of SAMW towards Site 590B, possibly a first step towards the present Antarctic Frontal System.     

Characteristics and role of groundwater dissolved organic matter on arsenic mobilization and poisoning in Bangladesh

The fluorescence and molecular weight characteristics of dissolved organic matter (DOM) in groundwater of Bangladesh were investigated to evaluate its multiple roles on arsenic (As) mobilization and poisoning. Fluorescence properties of DOM were measured in groundwater samples collected from two As contaminated areas of Bangladesh (Faridpur at the Ganges floodplain and Sonargaon at the Meghna floodplain) from different locations and depths. The three dimensional excitation–emission matrix (3DEEM) fluorescence spectra of groundwater samples showed two characteristic peaks around Ex/Em = 335–365 nm/435–480 nm for fulvic-like peaks and peak at around Ex/Em = 275–290 nm/310–335 nm for the protein-like materials. The similarity of fluorescence spectra of groundwater and surface water of both the study areas with high intensity of fluorescence and its strong correlation with DOC reflect the in situ generation of fluorescent DOM from sedimentary organic matter (SOM) and recent recharge of terrestrial labile organic carbon into shallow aquifer. High performance size-exclusion chromatography (HPSEC) analysis of DOM shows positive correlations between fluorescence intensities (FI) of small molecular fractions (0.65 kDa) and As concentrations, with the signatures of protein-like peaks of DOM in groundwater. This result provides new evidence that small molecular weight fraction of DOM in groundwater of Bangladesh can play an important role on As mobilization and toxicity. In addition, high concentration of fluorescence materials in DOM of As contaminated groundwater of Bangladesh may pose a threat to public health.     

Influence of the crystal field effect on chemical transport in Earth's mantle: Cr3+ and Ga3+ diffusion in periclase

Experiments were performed to determine concentration-dependent diffusion coefficients of Cr³⁺ and Ga³⁺ in periclase at temperatures of 1563–2273 K. Diffusion profiles measured in the quenched samples are consistent with a theoretical model in which the mobile species is a bound M³⁺-vacancy pair, and each profile was fitted to determine the binding energy and diffusion coefficient of the pair. Trivalent chromium-vacancy pairs diffuse more slowly than Ga³⁺-vacancy pairs, and with higher migration energy, 237 kJ/mol vs. 190 kJ/mol. Cation vacancies also bind less tightly to Cr³⁺ than to Ga³⁺, with average binding free energies of ?22 and ?83 kJ/mol, respectively. At all concentrations and temperatures, Cr³⁺ diffuses much more slowly than Ga³⁺, by up to two orders of magnitude. The differences between Cr³⁺ and Ga³⁺ cannot be explained by differences in ionic radius or dipole polarizability, but are consistent with the influence of the crystal field on the partially occupied 3d orbitals of Cr³⁺. The crystal field splitting stabilizes Cr³⁺ on the octahedral cation site, increasing the energy required for Cr³⁺ to exchange positions with an adjacent vacancy. It also makes Cr³⁺-vacancy pairs less favorable, with the presence of a nearest-neighbor vacancy disrupting the symmetry of the octahedral site, thus diminishing the crystal field stabilization. Trends in the diffusion of first-row divalent transition metals in periclase can also be explained by the crystal field effect. High-spin to low-spin transitions in Fe²⁺, Co²⁺ or Mn²⁺ would significantly enhance their crystal field stabilization in periclase, and if such spin transitions occur in the deep mantle, they would be expected to slow the diffusivity of these ions significantly, perhaps by several orders of magnitude.     

Investigating Bermuda's pollution history through stable isotope analyses of modern and museum-held gorgonian corals

For centuries, Bermuda has been challenged with wastewater management for the protection of human and environmental health. By quantifying the δ¹⁵N of the common sea fan Gorgonia ventalina sampled from 30 sites throughout Bermuda we show that sewage-derived nitrogen is detectable on nearshore coral reefs and declines across the lagoon to the outer rim. We also sampled gorgonians from two museum collections representing a 50y time-series (1958–2008). These samples revealed an increase in δ¹⁵N of > 4.0‰ until the mid-1970s, after which δ¹⁵N values slowly declined by ~ 2.0‰. A δ¹⁵N chronology from a gorgonian skeleton exhibited a similar decline over the last 30–40 years of approximately 0.6‰. We conclude that policies have been effective in reducing sewage impacts to Bermudian reefs. However, significant sources of sewage pollution persist and are likely have a strong impact on harbor and nearshore coral communities and human health.     

Estimating groundwater recharge from water isotope (δ2H, δ18O) depth profiles in the Densu River basin,Ghana

Abstract

Accurate estimation of groundwater recharge is essential for the proper management of aquifers. A study of water isotope (δ²H, δ¹⁸O) depth profiles was carried out to estimate groundwater recharge in the Densu River basin in Ghana, at three chosen observation sites that differ in their altitude, geology, climate and vegetation. Water isotopes and water contents were analysed with depth to determine water flow in the unsaturated zone. The measured data showed isotope enrichment in the pore water near the soil surface due to evaporation. Seasonal variations in the isotope signal of the pore water were also observed to a depth of 2.75 m. Below that depth, the seasonal variation of the isotope signal was attenuated due to diffusion/dispersion and low water flow velocities. Groundwater recharge rates were determined by numerical modelling of the unsaturated water flow and water isotope transport. Different groundwater recharge rates were computed at the three observation sites and were found to vary between 94 and 182 mm/year (± max. 7%). Further, the approximate peak-shift method was applied to give information about groundwater recharge rates. Although this simple method neglects variations in flow conditions and only considers advective transport, it yielded mean groundwater recharge rates of 110–250 mm/year (± max. 30%), which were in the same order of magnitude as computed numerical modelling values. Integrating these site-specific groundwater recharge rates to the whole catchment indicates that more water is potentially renewed than consumed nowadays. With increases in population and irrigation, more clean water is required, and knowledge about groundwater recharge rates – essential for improving the groundwater management in the Densu River basin – can be easily obtained by measuring water isotope depth profiles and applying a simple peak-shift approach.

Citation Adomako, D., Maloszewski, P., Stumpp, C., Osae, S. & Akiti, T. T. (2010) Estimating groundwater recharge from water isotope (δ²H, δ¹⁸O) depth profiles in the Densu River basin, Ghana. Hydrol. Sci. J. 55(8), 1405–1416.     

Modeling of the river ecological status with macrophytes using artificial neural networks

Biomonitoring methods based on macrophytes have been used mandatorily in the assessment of freshwaters since the implementation of the Water Framework Directive (WFD). The Macrophyte Index for Rivers (MIR) was developed in Poland for the monitoring of running waters under the WFD requirements. This index shows the degree of river degradation under the influence of water pollutants, especially nutrients. The aim of the present study was to determine the relationship between the MIR and various hydrochemical parameters using artificial neural networks (ANNs). Physico-chemical parameters of water (monthly results for the whole year), which were derived from 147 lowland river survey sites, all located in Poland, were applied to model the MIR values. Water quality variables were determined over three timeframes: the annual average; the average for the vegetation period; and the average for the summer period. Quality of the networks was assessed using coefficient of determination (R²), Nash-Sutcliffe efficiency (NSE) and root mean square error (RMSE). The best modeling quality was obtained for yearly average values of water quality parameters. The quality statistics were: R² = 0.722, NSE = 0.721 and RMSE = 0.056 (training dataset); R² = 0.555, NSE = 0.533 and RMSE = 0.101 (validation dataset); R² = 0.650. NSE = 0.600 and RMSE = 0.089 (testing dataset). This indicates that macrophytes reflect the whole year impact of pollution, whereas summer.     

The effect of Hurricane Lili on the distribution of organic matter along the inner Louisiana shelf (Gulf of Mexico,USA)

On October 3, 2002 Hurricane Lili made landfall on a previously studied region of the inner Louisiana shelf as a Category 2 storm with winds over 160 km/h. A week after the hurricane, major impacts of the storm were not evident in the water column except for the lower than expected inshore salinities (∼12 psu) for this time of year, which was characterized by low river discharge. Turbidity profiles were typical of those measured during previous investigations with suspended sediment concentrations >75 mg/L at inshore stations and <50 mg/L in surface waters and offshore. The implication is that the sediments resuspended during the hurricane settled soon after the storm passage. Water column particulate organic carbon (POC) concentrations ranged from 0.1 to over 2.0 mg/L, with the highest concentrations measured near the seabed and in the inshore portions of the study area. Suspended particles were characterized by low organic matter content (%POC of 0.5–2 wt%), low chlorophyll:POC ratios (Chl:POC<4 mg/g) and moderately elevated POC:particulate nitrogen ratios (POC:PN of 10–14 mol/mol), all suggesting their source was locally resuspended seabed sediment rather than from algal biomass or land-derived vascular plant detritus.Post hurricane sediment deposition throughout the study area resulted in a storm layer that ranged from <0.5 to 20 cm in thickness. In most locations sediment accumulation ranged from 3 to 10 cm. The storm deposits were generally composed of silty clays with a coarser, somewhat sandy 1–2 cm basal layer. Surface sediments from the storm layer were characterized by relatively high mineral surface areas (SA of 30–50 m²/g) and elevated OC contents (%OC of 1.0–2.0%). The dispersal of fine sediments following the hurricane resulted in marked changes in the SA and %OC values of surface sediments from offshore locations, which prior to the storm contained coarser, organic-poor particles (SA of 5–15 m²/g and %OC of 0.2–0.6%). The OC:SA and OC:N ratios of storm layer sediments ranged from 0.4 to 0.6 mg OC/m² and from 10 to 12 mol/mol, respectively, and were comparable to those measured in surface sediments prior to the hurricane. Such similarities in the composition of the organic matter reinforce the idea that the source of the storm deposits was the finer fraction of resuspended seabed sediments, with little evidence for inputs from local land-derived sources or autochthonous algal production. Overall, the magnitude of sediment and organic matter deposition on the seabed after the storm greatly exceeded the annual inputs from the Atchafalaya River and coastal primary production. The combined effects of hurricane-driven erosion and post-storm deposition represent a major perturbation to the benthic community of the region, which is already subject to these types of disturbances due to the combined effects of peaks in river discharge and the passage of storm fronts.