Early-indicator signals of groundwater contamination: the case of seawater encroachment

 An early indication of groundwater contamination occurs when pollutant concentrations start to fluctuate and exceed background values of ambient fresh groundwater. An analysis of a characteristic situation of this type uses data from Israel's coastal phreatic granular aquifer. The pollutant is generally seawater, and the contamination process involves replacement of freshwater by encroaching sea- or other saltwater, a process augmented by human activity. The contamination process involves three stages: (1) groundwater composition remains relatively stable with small salinity content; (2) small salinity changes are perceptible with reversible fluctuations; and (3) salinity concentration increases at a sharply higher rate. The second stage is a useful early-indicator signal of contamination. Early-indicator signals of groundwater pollutant concentrations involve "minor" fluctuations in water chemistry at the advent of the contamination process. The intensity and magnitude of such a salinization/pollution process at any given location depends upon lithologic matrix, aquifer heterogeneity, and resultant flow domain characteristics, as well as contaminant properties. If such "signs" are detected at a sufficiently early stage, appropriate management steps may be taken to rectify further seawater and/or saltwater encroachment. Received: 23 July 1996 · Accepted: 25 June 1997     

Lead and its isotopes in the sediment of three sites on the Lebanese coast: Identification of contamination sources and mobility

Lead concentrations and isotopic composition of sediment samples collected from three sites within the Lebanese coastal zones were measured: at Akkar, Dora and Selaata. Akkar is located far from any direct source of contamination, while Dora and Selaata receive urban and industrial wastes, respectively. Low Pb concentrations (6–16 μg g⁻¹) were detected in the Akkar sediments, and high concentrations of Pb (70–101 μg g⁻¹) were detected in the Dora sediments. Measuring stable isotope ratios of Pb makes it possible to identify the principal sources of Pb in the Akkar sediments as Pb emitted from gasoline combustion and Pb originating from natural sources. On the other hand, Pb stable isotopic ratios in Dora sediments indicate that they are more highly influenced by anthropogenic sources. Isotopic Pb ratios in the Selaata deposits, where Pb concentrations range between 5 and 35 μg g⁻¹, have an exceptional radiogenic signature for marine sediments 1.25 < ²⁰⁶Pb/²⁰⁷Pb < 1.6 and 0.5 < ²⁰⁶Pb/²⁰⁸Pb < 0.67, which shows the impact of the phosphogypsum discharged by Selaata’s chemical plant. Isotopic Pb analysis applied to EDTA extracts, to test the mobility of Pb, shows that that this mobility is high (>60%) after 24 h of extraction, and that the extracted Pb is less radiogenic than the residual Pb.     

Pathways and regulation of carbon, sulfur and energy transfer in marine sediments overlying methane gas hydrates on the Opouawe Bank (New Zealand)

This study combines sediment geochemical analysis, in situ benthic lander deployments and numerical modeling to quantify the biogeochemical cycles of carbon and sulfur and the associated rates of Gibbs energy production at a novel methane seep. The benthic ecosystem is dominated by a dense population of tube-building ampharetid polychaetes and conspicuous microbial mats were unusually absent. A 1D numerical reaction-transport model, which allows for the explicit growth of sulfide and methane oxidizing microorganisms, was tuned to the geochemical data using a fluid advection velocity of 14 cm yr⁻¹. The fluids provide a deep source of dissolved hydrogen sulfide and methane to the sediment with fluxes equal to 4.1 and 18.2 mmol m⁻² d⁻¹, respectively. Chemosynthetic biomass production in the subsurface sediment is estimated to be 2.8 mmol m⁻² d⁻¹ of C biomass. However, carbon and oxygen budgets indicate that chemosynthetic organisms living directly above or on the surface sediment have the potential to produce 12.3 mmol m⁻² d⁻¹ of C biomass. This autochthonous carbon source meets the ampharetid respiratory carbon demand of 23.2 mmol m⁻² d⁻¹ to within a factor of 2. By contrast, the contribution of photosynthetically-fixed carbon sources to ampharetid nutrition is minor (3.3 mmol m⁻² d⁻¹ of C). The data strongly suggest that mixing of labile autochthonous microbial detritus below the oxic layer sustains high measured rates of sulfate reduction in the uppermost 2 cm of the sulfidic sediment (100-200 nmol cm⁻³ d⁻¹). Similar rates have been reported in the literature for other seeps, from which we conclude that autochthonous organic matter is an important substrate for sulfate reducing bacteria in these sediment layers. A system-scale energy budget based on the chemosynthetic reaction pathways reveals that up to 8.3 kJ m⁻² d⁻¹ or 96 mW m⁻² of catabolic (Gibbs) energy is dissipated at the seep through oxidation reactions. The microorganisms mediating sulfide oxidation and anaerobic oxidation of methane (AOM) produce 95% and 2% of this energy flux, respectively. The low power output by AOM is due to strong bioenergetic constraints imposed on the reaction rate by the composition of the chemical environment. These constraints provide a high potential for dissolved methane efflux from the sediment (12.0 mmol m⁻² d⁻¹) and indicates a much lower efficiency of (dissolved) methane sequestration by AOM at seeps than considered previously. Nonetheless, AOM is able to consume a third of the ascending methane flux (5.9 mmol m⁻² d⁻¹ of CH₄) with a high efficiency of energy expenditure (35 mmol CH₄ kJ⁻¹). It is further proposed that bioenergetic limitation of AOM provides an explanation for the non-zero sulfate concentrations below the AOM zone observed here and in other active and passive margin sediments.     

Analysis of earth dams affected by the 2001 Bhuj Earthquake

An earthquake of magnitude of 7.6 (M_w 7.6) occurred in Bhuj, India on January 26, 2001. This event inflicted damages of varying extents to a large number of small to moderate size multi-zone earth dams in the vicinity of the epicenter. Some of the distress was due to the liquefaction of saturated alluvium in foundation. Liquefaction was relatively localized for the majority of these dams because the earthquake struck in the middle of a prolonged dry season when the reservoirs behind these dams were nearly empty and shallow alluvium soils underneath the downstream portions of the dams were partly dry. Otherwise, liquefaction of foundation soils would have been more extensive and damage to these dams more significant. Six such dams have been examined in this paper. Four of these facilities, Chang, Shivlakha, Suvi, and Tapar were within the 50 km of epicenter region. These dams underwent free-field ground motion with peak ground accelerations between 0.28g to 0.52g. Of these Chang Dam underwent severe slumping, whereas Shivlakha, Suvi, and Tapar Dams were affected severely especially over the upstream sections. Fatehgadh Dam and Kaswati Dam were affected relatively less severely. Foundation conditions underneath these dams were first examined for assessing liquefaction potential. A limited amount of subsurface information available from investigations undertaken prior to the earthquake indicates that, although the foundation soils within the top 2.0 to 2.5 m underneath these dams were susceptible to liquefaction, Bhuj Earthquake did not trigger liquefaction because of lack of saturation of these layers underneath the downstream portions of these dams. These dams were then analyzed using a simple sliding block procedure using appropriate estimates of undrained soil strength parameters. The results of this analysis for these structures were found to be in general agreement with the observed deformation patterns.     

Plagioclase buoyancy in basaltic liquids as determined with a centrifuge furnace

Plagioclase buoyancy experiments have been carried out in a high-temperature centrifuge furnace using seventeen basaltic liquids and plagioclase crystals of three compositions: An₈₉, An⁷⁶ and An₅₅. The results show that the floating tendency of plagioclase in basaltic liquids is at least 0.03 g/cm³ greater than indicated by the calculations. If this correction factor is applied to calculations of plagioclase buoyancy in the Skaergaard Intrusion, it is found that the plagioclase crystals in the lower and middle zones were less dense than the coexisting liquids.Other phenomena relevant to crystal transport in basaltic liquids were observed in the centrifuge experiments. These included crystal flotation by rising bubbles, plagioclase sinking because of the formation of plagioclase-magnetite composite grains, graded bedding of olivine and magnetite, and more than 60% intercumulus basaltic liquid between settled olivine crystals.     

Hydrogeochemical modelling of an active system of uranium fixation by organic soils and sediments (Needle's Eye,Scotland)

Uranium accumulation in organic-rich sediments can be closely modelled by assuming that the dominant effect of the uranium-organic matter interaction is the direct or indirect reduction of uranyl compounds to form U(IV) minerals, especially uraninite-pitchblende. Application of this model to the Needle's Eye (Scotland) site where uranium is actively accumulating in Quaternary sediments demonstrates that uranium accumulation is both effective and rapid in environments involving shallow, organic-rich, reducing horizons. The period of uranium deposit formation at Needle's Eye is estimated to be as short as 5000 years. The transport of uranium to the site of deposition by oxidizing groundwaters and the channelling of these oxidizing uraniferous groundwaters are identified as important factors involved in the rapid accumulation of uranium. The regional hydrogeological model indicates that a fault in the area appears to act as a hydraulic screen for the uraniferous groundwaters. On one side of the fault the Quaternary sediments are well drained whilst on the other the flow of groundwater seeps out creating a major flux just at the bottom of the organic-rich layers. The local hydrogeological model shows that the groundwater flow is vertical in this area. A third significant factor in the development of these uranium accumulations is the presence of a significant nearby source of leachable primary uranium. In the case of the Needle's Eye site this is in the form of some thirty 185 ±20 Ma, pitchblende-bearing veins.     

Nature and composition of shore-zone sediments between Jeddah and Yanbu, eastern Red Sea

The shore-zone sediments between Jeddah and Yanbu, west coast of Saudi Arabia, are composed mostly of skeletal carbonate sands. The nearshore sediments containing benthic foraminifera, algal fragments and molluscs are multimodal, the mean grain size varying between 0.76 and 2.35 ø. The beach sediments, except samples dominated by cerithid gastropods in some localities, are relatively finer than the nearshore sediments. Although the beaches to a great extent comprise sand-sized material, fine lime muds and coarse clastic gravels occur in certain areas. The dune sediments comprising mostly algal grains and ooids are very fine with 50 percent of the material in the 0.25–0.18 mm size grade. Except a general northward decrease in mean grain size, regional trends in the textural parameters of the sediments between Jeddah and Yanbu are not quite apparent. Lateral variations in the textural characteristics suggest a landward migration of the sediments in the shore zone under the influence of northerly and northwesterly winds. The carbon and oxygen (δ ¹³C + 4.80 to 4.84‰ PDB) (δ ¹³O − 0.04 to + 0.53‰ PDB) isotopic ratios of the lime muds occurring in certain shallow margins in the shore-zone, which are much higher than those of the green algae, indicate that the fine carbonates are at least in part inorganic in origin.

Like the shallow-water carbonates in tropical seas, aragonite and high Mg-calcite are the dominant carbonate minerals in the shore-zone sediments. There is a landward increase in aragonite contents caused by the landward migration of fine material from the nearshore. The dominant clay mineral in the nearshore sediments is kaolinite with subordinate swelling chlorite and little illite. Kaolinite is contributed by the coastal regions under the sub-tropical humid climate. Swelling chlorite is considered to have been formed in the nearshore by mechanical mixture of chlorite and montmorillonite derived from the metamorphic and igneous terrains of the Tertiary mountains bordering the coastal plain.     

Weibull statistical analysis of granite bending strength

Summary  This paper describes and discusses the adequacy of Weibull statistical analysis to analyse the bending strength of granite. The experimental results show that strength variability is related with a specific origin of failure. This conclusion is based on analysing the influence of the surface condition (extrinsic defects) on the bending strength results treated by the Weibull statistics. The conclusions drawn from this study have been validated by analysing the results of the critical flaw dimension estimated by applying the linear elastic fracture mechanics (LEFM) formulae. Results obtained from fractographic examination also have been used to describe the location of the origin of the fracture and understand the distribution of defects; i.e., there is a unimodal distribution of defects (intrinsic defects), despite the fact that some outlier values are normally observed in the fractured surfaces. Correspndence: P. M. Amaral, Department of Materials Engineering, Instituto Superior Técnico, Technical University of Lisbon, Av. Rovisco Pais, 1049-001 Lisboa, Portugal     

Heat capacity, entropy, and magnetic properties of jarosite-group compounds

Jarosite phases are common minerals in acidic, sulfate-rich environments. Here, we report heat capacities (C _p) and standard entropies (S°) for a number of jarosite samples. Most samples are close to the nominal composition AFe₃(SO₄)₂(OH)₆, where A = K, Na, Rb, and NH₄. One of the samples has a significant number of defects on the Fe sites and is called the defect jarosite; others are referred to as A-jarosite. The samples, their compositions, and the entropies at T = 298.15 K are: