Equilibrium and structural studies of silicon(iv) and aluminium(iii) in aqueous solution. V. Acidity constants of silicic acid and the ionic product of water in the medium range 0.05–2.0 M Na(CI) at 25°C

The apparent ionization constants for silicic acid, k₁ and k₂, and the ionic product of water, k_w, have been determined in 0.05, 0.1, 0.2, 0.4 and 2.0 M Na(CI) media at 25°C. The medium dependence of these constants was found to fit equations of the form

$\text{log}\text{k}{}_{\mathrm{i}}\text{=}\text{log}\text{K}{}_{\mathrm{i}}\text{+a}{}_{\mathrm{i}}\text{I}{}^{\mathrm{<mtext>1</mtext><mtext>2</mtext>}}\text{(1+I}{}^{\mathrm{<mtext>1</mtext><mtext>2</mtext>}}\text{)+b}{}_{\mathrm{i}}\text{I}$

where K₁ is the ionization constant in pure water, α_i and b_i are parameters of which b_i has been adjusted to present data. The following results were obtained (α_i, b_i): pK₁ = 9.84, (1.022, ?0.11); pK₂ = 13.43, (2.044, ?0.20); and pK_w = 14.01 (1.022, ?0.22). k_i values are collected in Tables I and II. Attempts have been made to explain the medium dependence of k₁ and k₂ with weak sodium silicate complexing according to the equilibria

$\text{Na}{}^{\mathrm{+}}\text{+}\text{SiO(OH)}{}^{\mathrm{?}}{}_3\text{?}\text{NaSiO(OH)}{}_3\text{;k}{}_{11}$

$\text{Na}{}^{\mathrm{+}}\text{+}\text{SiO}{}_2\text{(OH)}{}^2{}_2\text{?}\text{NaSiO}{}_2\text{(HO)}{}^{\mathrm{?}}{}_2\text{; k}{}_{21}$

giving k₁₁ = 0.37M^?1 and k₂₁= 3.0M^?1. However, these weak interactions cannot be interpreted unambiguously from potentiometric data at different 1-levels. Probably the medium dependence could equally well be expressed by variations in the activity coefficients.The measurements were performed as potentiometric titrations using a hydrogen electrode. The average number of OH^- reacted per Si(OH)₄, Z, has been varied within the limits 0 ? Z ? 1.1 and B₁, the total concentration of Si(OH)₄, between 0.001 M and 0.008 M. k₁ was evaluated from experimental data with B ? 0.003 M, and k₂ with B ? 0.008 M and Z ? 0.95.     

The impact of oestrogenic and androgenic contamination on marine organisms in the United Kingdom--summary of the EDMAR programme. Endocrine Disruption in the Marine Environment

This paper summarises results of the EDMAR programme which is investigating oestrogenic and androgenic endocrine disruption in UK coastal waters. Most of the data concern fish. Four species (flounder, viviparous blenny and two sand gobies) are experiencing feminisation in industrialised estuaries. In males this includes vitellogenin (VTG) synthesis, ovotestis induction and/or feminised sexual characteristics. Although reproductive success may be impaired in some cases, implications for fish populations are still unclear. Suspected causative contaminants include natural oestrogenic substances and synthetic oestrogen mimics. The majority of the oestrogenic activity is adsorbed to sediments, and routes of exposure may include benthic food chain transfer. Some natural androgenic substances are also being discharged to estuaries, but their activity appears low.     

The P–T–t evolution of the exhumed Himalayan metamorphic core in the Likhu Khola region,East Central Nepal

The recent identification of multiple strike‐parallel discontinuities within the exhumed Himalayan metamorphic core has helped revise the understanding of convergence accommodation processes within the former mid‐crust exposed in the Himalaya. Whilst the significance of these discontinuities to the overall development of the mountain belt is still being investigated, their identification and characterization has become important for potential correlations across regions, and for constraining the kinematic framework of the mid‐crust. The result of new phase equilibria modelling, trace element analysis and high‐precision Lu–Hf garnet dating of the metapelites from the Likhu Khola region in east central Nepal, combined with the previously published monazite petrochronology data confirms the presence of one of such cryptic thrust‐sense tectonometamorphic discontinuities within the lower portion of the exhumed metamorphic core and provides new constraints on the P–T estimates for that region. The location of the discontinuity is marked by an abrupt change in the nature of P–T–t paths of the rocks across it. The rocks in the footwall are characterized by a prograde burial P–T path with peak metamorphic conditions of ~660°C and ~9.5 kbar likely in the mid‐to‐late Miocene, which are overlain by the hanging wall rocks, that preserve retrograde P–T paths with P–T conditions of >700°C and ~7 kbar in the early Miocene. The occurrence of this thrust‐sense structure that separates rock units with unique metamorphic histories is compatible with orogenic models that identify a spatial and temporal transition from early midcrustal deformation and metamorphism in the deeper hinterland to later deformation and metamorphism towards the shallower foreland of the orogen. Moreover, these observations are comparable with those made across other discontinuities at similar structural levels along the Himalaya, confirming their importance as important orogen‐scale structures.     

Multiple P–T–d–t paths reveal the evolution of the final Nuna assembly in northeast Australia

The final assembly of the Mesoproterozoic supercontinent Nuna was marked by the collision of Laurentia and Australia at 1.60 Ga, which is recorded in the Georgetown Inlier of NE Australia. Here, we decipher the metamorphic evolution of this final Nuna collisional event using petrostructural analysis, major and trace element compositions of key minerals, thermodynamic modelling, and multi-method geochronology. The Georgetown Inlier is characterised by deformed and metamorphosed 1.70–1.62 Ga sedimentary and mafic rocks, which were intruded by c. 1.56 Ga old S-type granites. Garnet Lu–Hf and monazite U–Pb isotopic analyses distinguish two major metamorphic events (M1 at c. 1.60 Ga and M2 at c. 1.55 Ga), which allows at least two composite fabrics to be identified at the regional scale—c. 1.60 Ga S1 (consisting in fabrics S1a and S1b) and c. 1.55 Ga S2 (including fabrics S2a and S2b). Also, three tectono-metamorphic domains are distinguished: (a) the western domain, with S1 defined by low-P (LP) greenschist facies assemblages; (b) the central domain, where S1 fabric is preserved as medium-P (MP) amphibolite facies relicts, and locally as inclusion trails in garnet wrapped by the regionally dominant low-P amphibolite facies S2 fabric; and (c) the eastern domain dominated by upper amphibolite to granulite facies S2 foliation. In the central domain, 1.60 Ga MP–medium-T (MT) metamorphism (M1) developed within the staurolite–garnet stability field, with conditions ranging from 530–550°C at 6–7 kbar (garnet cores) to 620–650°C at 8–9 kbar (garnet rims), and it is associated with S1 fabric. The onset of 1.55 Ga LP–high-T (HT) metamorphism (M2) is marked by replacement of staurolite by andalusite (M2a/D2a), which was subsequently pseudomorphed by sillimanite (M2b/D2b) where granite and migmatite are abundant. P–T conditions ranged from 600 to 680°C and 4–6 kbar for the M2b sillimanite stage. 1.60 Ga garnet relicts within the S2 foliation highlight the progressive obliteration of the S1 fabric by regional S2 in the central zone during peak M2 metamorphism. In the eastern migmatitic complex, partial melting of paragneiss and amphibolite occurred syn- to post- S2, at 730–770°C and 6–8 kbar, and at 750–790°C and 6 kbar, respectively. The pressure–temperature–deformation–time paths reconstructed for the Georgetown Inlier suggest a c. 1.60 Ga M1/D1 event recorded under greenschist facies conditions in the western domain and under medium-P and medium-T conditions in the central domain. This event was followed by the regional 1.56–1.54 Ga low-P and high-T phase (M2/D2), extensively recorded in the central and eastern domains. Decompression between these two metamorphic events is ascribed to an episode of exhumation. The two-stage evolution supports the previous hypothesis that the Georgetown Inlier preserves continental collisional and subsequent thermal perturbation associated with granite emplacement.     

Re-Os isotopic composition of peridotitic sulphide inclusions in diamonds from Ellendale, Australia: Age constraints on Kimberley cratonic lithosphere

Sulphide-bearing diamonds recovered from the ∼20 Ma Ellendale 4 and 9 lamproite pipes in north-western Australia were investigated to determine the nitrogen aggregation state of the diamonds and Re-Os isotope geochemistry of the sulphide inclusions. The majority of diamond studies have been based on diamonds formed in the sub-continental lithospheric mantle (SCLM) below stable cratons, whereas the Ellendale lamproites intrude the King Leopold Orogen, south of the Kimberley craton. The sulphide inclusions consist of pyrrhotite-pentlandite-chalcopyrite assemblages, and can be divided into peridotitic and eclogitic parageneses on the basis of their Ni and Os contents. A lherzolitic paragenesis for the high-Ni sulphide inclusions is suggested from their Re and Os concentrations. Regression analysis of the Re-Os isotope data for the lherzolitic sulphides yields an age of 1426 ± 130 Ma, with an initial ¹⁸⁷Os/¹⁸⁸Os ratio of 0.1042 ± 0.0034. The upper limit of the uncertainty on the ¹⁸⁷Os/¹⁸⁸Os initial ratio gives a Re depletion age of 2.96 Ga, indicating the presence of SCLM beneath Ellendale since at least the Mesoarchaean, with the lherzolitic diamond-forming event much younger and unrelated to the craton keel stabilisation. The nitrogen aggregation state of the diamonds and calculated mantle residence temperatures suggest an origin and storage of the Ellendale diamonds in a stable cratonic SCLM, consistent with the King Leopold Orogen being cratonised by about 1.8 Ga. The diamonds do not show evidence for pervasive deformation or platelet degradation, which suggests that the diamonds had a relatively undisturbed 1.4 billion year mantle storage history.     

Vulnerability and adaptation in a dryland community of the Elqui Valley, Chile

Livelihoods in drylands are already challenged by the demands of climate variability, and climate change is expected to have further implications for water resource availability in these regions. This paper characterizes the vulnerability of an irrigation-dependent agricultural community located in the Elqui River Basin of Northern Chile to water and climate-related conditions in light of climate change. The paper documents the exposures and sensitivities faced by the community in light of current water shortages, and identifies their ability to manage these exposures under a changing climate. The IPCC identifies potentially increased aridity in this region with climate change; furthermore, the Elqui River is fed by snowmelt and glaciers, and its flows will be affected by a warming climate. Community vulnerability occurs within a broader physical, economic, political and social context, and vulnerability in the community varies amongst occupations, resource uses and accessibility to water resources, making some more susceptible to changing conditions in the future. This case study highlights the need for adaptation to current land and water management practices to maintain livelihoods in the face of changes many people are not expecting.     

Impacts of changes in the flue-cured tobacco sector on farmers in Ontario, Canada

Impacts of the forces and processes of agricultural restructuring are described in this paper through an analysis of farmers’ ‘lived experience’ in the tobacco sector of Ontario, Canada. The paper argues that the political and economic changes in the 1980s fundamentally altered tobacco farming and the broader rural community. The analysis is based upon a survey of farmers and former farmers, and includes examples of individual case histories. The results show the ways in which farmers’ well-being was affected and provides insights into coping mechanisms.     

Bed-material transport estimated from channel surveys: Vedder River,British Columbia

This study investigates the possibility to estimate bed-material transfer in gravel-bed rivers by analysis of morphological changes along Vedder River, British Columbia. Data from repeated cross-section surveys are used to estimate volume changes along the length of an 8 km reach. Gravel budgets are based on a continuity approach. An error analysis is performed to evaluate the uncertainty in the best estimate of transport rates. The mean annual gravel transport into the reach over a 9 year period was estimated to be 36600 ± 5600 m³ yr^?1. The sediment transport regime along the length of the river is evaluated and examined in relation to peak flood flows. Significant spatial and temporal variability in transport rates is demonstrated, making dubious the generalization of transport estimates from hydraulic calculations, or from sample measurements at a single cross-section. The assumptions, procedures and limitations of the ‘morphological approach’ to sediment transport analysis are discussed. It is concluded that this approach provides information of quality comparable or superior to that of direct measurements of transport, yet requires less field effort. It also provides additional information about river morphological changes, making it a preferred method for geomorphlogical investigations and for many river management concerns.     

Intercomparison campaign of vertical ozone profiles including electrochemical sondes of ECC and Brewer-Mast type and a ground based UV-differential absorption lidar

An intercomparison campaign was conducted at the Observatoire de Haute Provence (OHP) in Southern France in September 1989 in order to compare the three instruments used for vertical tropospheric ozone profiling in the European TOR (Tropospheric Ozone Research Project) network: balloon borne ECC and Brewer-Mast sondes and a ground based UV-DIAL (DifferentialAbsorptionLidar). Additionally, a stratospheric lidar system and the Dobson spectrophotometer of the OHP were operated. Seven simultaneously measured vertical ozone profiles gave evidence for systematic differences of 15% between both types of electrochemical sondes in the troposphere, the Brewer-Mast sondes reading the smaller ozone values. These differences might be explained on the one hand by a possible contamination of the ozone sensor with reducing substances, causing a negative bias mainly for Brewer-Mast sondes and, on the other hand, by the evolution of the sonde background current during the flight, causing a positive bias for ECC sondes and a negative bias for Brewer-Mast sondes. The tropospheric lidar system, measuring the vertical ozone distribution between 6 and 12–15 km, showed ozone concentrations intermediate between the sonde results. This is in good agreement with its estimated systematic error of better than 7% in the upper troposphere. In the stratosphere, the differences between electrochemical sondes and the lidar are between 5 and 10% before the normalisation with the total ozone values measured by the Dobson spectrophotometer, and always below 5% after. While the Dobson normalisation thus corrects rather well the stratospheric part of the sonde profile, it only partially reduces errors occurring in the troposphere.