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.     

Nicholas Crisp's “Porcellien”: A petrological comparison of sherds from the Vauxhall (London; ca. 1751–1764) and Indeo Pottery (Bovey Tracey,Devonshire; ca. 1767–1774) factory sites

The character of porcelain wares made by Nicholas Crisp early and late in his career was assessed using microchemical and petrographic data for sherds excavated from the sites of the factories he operated at Vauxhall and Bovey Tracey. The results indicate that, over time, Crisp increasingly made use of diverse types of pastes as he struggled to produce a commercially viable line of porcelain. Based on the analysis of a limited number of samples, he appears to have largely restricted himself at Vauxhall to using soapstone (Mg‐rich)‐ and flint‐glass (Pb‐rich) frit‐bearing pastes that varied in the amount of calcite they contained. He also experimented with Mg+Pb‐rich pastes at Bovey Tracey, but included a novel ingredient (barite) and varied the proportion of other minor constituents (e.g., bone ash), apparently in an effort to resolve some of the firing problems that plagued him at Vauxhall. In addition, Crisp appears to have produced bone ash (phosphatic) porcelain at Bovey Tracey, and, in collaboration with William Cookworthy, the proprietor of the Plymouth factory, fired a range of true porcelain (Si+Al‐rich) pastes. Bulk compositional data indicate that Crisp's diopside‐bearing Mg+Pb‐rich wares were derived from pastes containing talc and calcite rather than dolomite. The mineralogy of these and some contemporary magnesian/plombian porcelains are interpreted using the SiO₂‐CaO‐MgO phase diagram. This diagram shows that these wares can form and preserve diopside (Ca‐Mg silicate) given suitable bulk CaO contents and kiln‐firing temperatures. Phosphatic sherds from Bovey Tracey are compositionally distinct (lower SiO₂ and higher Al₂O₃ and bone‐ash components) from a single bone‐ash sample from Vauxhall, indicating that Crisp experimented with novel bone‐ash pastes, and was not positively influenced by the Vauxhall phosphatic recipe, if indeed one existed. True porcelains from Bovey Tracey have more extreme SiO₂/Al₂O₃ ratios (= 2.0 [two sherds]; 4.5 [one sherd]) than their Plymouth/Bristol counterparts (SiO₂/Al₂O₃ = 2.3–3.0). Collectively, the analytical data underscore the experimental—and ultimately unsuccessful—character of the diverse wares produced by Nicholas Crisp. © 2000 John Wiley & Sons, Inc.     

The need for and use of socio-economic scenarios for climate change analysis: A new approach based on shared socio-economic pathways

Socio-economic scenarios constitute an important tool for exploring the long-term consequences of anthropogenic climate change and available response options. A more consistent use of socio-economic scenarios that would allow an integrated perspective on mitigation, adaptation and residual climate impacts remains a major challenge. We assert that the identification of a set of global narratives and socio-economic pathways offering scalability to different regional contexts, a reasonable coverage of key socio-economic dimensions and relevant futures, and a sophisticated approach to separating climate policy from counter-factual “no policy” scenarios would be an important step toward meeting this challenge. To this end, we introduce the concept of “shared socio-economic (reference) pathways”. Sufficient coverage of the relevant socio-economic dimensions may be achieved by locating the pathways along the dimensions of challenges to mitigation and to adaptation. The pathways should be specified in an iterative manner and with close collaboration between integrated assessment modelers and impact, adaptation and vulnerability researchers to assure coverage of key dimensions, sufficient scalability and widespread adoption. They can be used not only as inputs to analyses, but also to collect the results of different climate change analyses in a matrix defined by two dimensions: climate exposure as characterized by a radiative forcing or temperature level and socio-economic development as classified by the pathways. For some applications, socio-economic pathways may have to be augmented by “shared climate policy assumptions” capturing global components of climate policies that some studies may require as inputs. We conclude that the development of shared socio-economic (reference) pathways, and integrated socio-economic scenarios more broadly, is a useful focal point for collaborative efforts between integrated assessment and impact, adaptation and vulnerability researchers.     

Disentangling late quaternary fluvial and climatic drivers of palaeohydrological change in the Najaf Sea basin,Western Iraq

The water resource provided by lake basins in the western desert of Iraq is important for human occupation of areas outside the Tigris-Euphrates floodplain, both in the past and into the future. This paper presents the first geomorphological and geochronological study of the date of formation of the Najaf Sea and the only such study of any lake basin to the west of Mesopotamia. Geomorphological shoreline features and a palaeochannel linking to the Euphrates were studied and dated using optically stimulated luminescence (OSL) and radiocarbon dating. Provenance was determined using heavy mineral analysis. Past environments in the Najaf Sea were reconstructed by molluscan analysis. The earliest OSL ages date from c. 30 000 and 22 000 years ago and seem to predate lake formation. Younger OSL ages date the highest lake level at c. 19 m asl to between 1620–1760 AD (base) to 1906–1974 AD (near surface). The radiocarbon ages are affected by a freshwater reservoir effect, but the maximum ages recorded for either of the c. 15 m and c. 17 m asl shorelines are c. 800 cal. BC. This predates the first archaeological sites in the Najaf basin and is similar to maximum ages of c. 850 and c. 1100 cal. BC from the associated palaeochannel. This timing does not seem to be linked to a humid climate event. We therefore conclude that the establishment of the Najaf Sea in the Najaf basin occurred as a result of an avulsion event within the Euphrates system that diverted flow to the basin. The trigger for this avulsion event likely related to rapid sediment accumulation and may have been either autogenic or driven by human activity. This study therefore suggests that Najaf Sea formation facilitated human expansion beyond the Tigris- Euphrates floodplain and occurred due to avulsion of the Euphrates.     

Effects of forest land management on erosion and revegetation after the eruption of Mount St. Helens

The 1980 eruption of Mount St. Helens covered soils with a tephra blanket and killed the forest tree cover in a 550 km² area. After the eruption, rates of sheetwash and rill erosion, and plant cover were measured on tephra-covered hillslopes which had been subject to three land-management practices: grass seeding; scarification, and salvage logging. On rapidly-eroding hillslopes subject to grass seeding, limited plant covers were established only after erosion had declined sharply. Logging of trees downed by the eruption and scarification of previously logged surfaces slowed erosion, although the effect was small because erosion rates had already slowed substantially by the time these two practices were implemented. The factors controlling erosion, revegetation, and their relative timing at Mount St. Helens are similar to those following explosive volcanic eruptions elsewhere, suggesting that grass seeding is not likely to be effective at slowing erosion following most tephra eruptions, and that early mechanical disturbance could be an effective erosion-control measure. The results also indicate that even without deliberate conservation measures, processes which mechanically disturb a surface layer of low hydraulic conductivity (such as frost-action or trampling) can radically reduce runoff and erosion before revegetation has an important effect.     

Particle dislodgement from a flat sand bed by wind

The rate, with respect to area and time, at which grains are dislodged from a sand bed for given wind conditions is an important factor in determining the grain transport rate and the intensity of grain activity in each of the transport modes. The literature of the subject contains little direct information about particle dislodgement. The paper describes a series of experiments in which dyed sand grains, spread on the surface of quartz dune sand in a wind-tunnel, were photographed at five second intervals while the sand was exposed to wind. The data on rate of loss of coloured grains was used, for two of three chosen size fractions, to deduce the dislodgement rate for each size fraction. The variation of this dislodgement rate with shear velocity is shown graphically for values of u_* between 24 cm s^?1 and 50 cm s^?1. Because of the artificial method of distribution of the coloured sand grains, the results should be applied with caution to natural conditions. The interpretation of the observations of dyed grain loss involved the numerical simulation of the process which comprises removal of coloured grains, slightly offset by replenishment as upwind coloured grains settle briefly in the observed zone. An estimation of grain excursion length has to be incorporated in the simulation. This estimation was made by trial, but general corroboration was found from earlier work. Comparisons are made between dislodgement rates obtained thus and rates estimated by Anderson (1986) and by Jensen and Sorensen (1986). Reasonable agreement with the latter is found in the u_* range 30 cm s^?1.     

Hydraulic Conductivity Measurements in the Unsaturated Zone Using Improved Well Analyses

The flow of ponded water into and through the unsaturated zone depends on both the saturated and unsaturated components of the hydraulic conductivity. Recent studies indicate that the ratio of the saturated (K_fs) to the unsaturated (φ_m) components (K_fs/φ_m=α*) of flow lies within prescribed bounds for most field soils, i.e., 1m⁻¹≤α*≤ 100 m⁻¹. In addition, the fact that the calculation of K_fs and φ_m is not strongly dependent on the choice of α*, suggests that a site estimation of α* leads to reasonable "best estimates" of K_fs and φ_m when using the constant head well permeameter technique. As a consequence, measurement of the steady flow rate using only one ponded head may be all that is necessary for many practical applications. Multiple head measurements or independent measurements of α* or φ_m can be used, however, to give more accurate estimates of K_fs if required.     

Sulphur isotope equilibrium during sulphur hydrolysis at high temperatures

Studies of the sulphur hydrolysis reaction, 4S + 4H₂O /ag 3H₂S + HSO₄^? + H⁺, were conducted between 200 and 320°C in sealed silica glass tubes. The isotope exchange reaction: H₂¹⁸O + HS¹⁶O₄^? /ag H₂¹⁶O + HS¹⁸O₄^? is so rapid at the low pH (1.5–3) as to be unquenchable. However, the sulphur isotope exchange reaction: H₂³⁴S+ H³²SO₄^? /ag H₂³²S + H³⁴SO₄^? gave t12 values of 0.1, 0.3 and 1.7 days at 320, 260 and 200°C respectively and equilibrium H₂S - HSO₄^? sulphur isotope fractionation values of 20.9, 22.4, 24.8, 26.7 and 29.3‰ at 320, 290, 260, 230 and 200°C respectively. This latter data is represented by: 1000lnα_(HSO4^??H2S) = 5.07 (10⁶T^?2) + 6.33, and has valuable applications in geothermal and ore deposit studies.     

Rivers in Australia

As a continent, Australia is unusual. It has a long history of habitation by a relatively small population of Aboriginals with a low technology culture. Just over 200 years ago, in 1788, it was invaded by a technological society from the UK, and the settlers brought with them an understanding of rivers and the landscapes in which they were situated which was quite at odds with the reality of the Australian continent. Australia is a piece of old continental crust derived from the break-up of Gondwana that, unlike other Gondwana continents, has experienced little tectonic modification since the break-up. It is a low relief continent dominated by arid and semi arid climates. Australian river systems have poor slope-channel coupling and poor hydrological connectivity and are characterized by low rates of sediment delivery. The flow of Australian rivers has high interannual variability, two to three times that of comparable rivers elsewhere, and highly variable flood behavior. In this paper, examples are given of particular Australian rivers to illustrate the manner in which the morphological and climatic characteristics of the continent combine to produce some distinctive river systems.     

Closed-loop reservoir management on the Brugge test case

This paper proposes an augmented Lagrangian method for production optimization in which the cost function to be maximized is defined as an augmented Lagrangian function consisting of the net present value (NPV) and all the equality and inequality constraints except the bound constraints. The bound constraints are dealt with using a trust-region gradient projection method. The paper also presents a way to eliminate the need to convert the inequality constraints to equality constraints with slack variables in the augmented Lagrangian function, which greatly reduces the size of the optimization problem when the number of inequality constraints is large. The proposed method is tested in the context of closed-loop reservoir management benchmark problem based on the Brugge reservoir setup by TNO. In the test, we used the ensemble Kalman filter (EnKF) with covariance localization for data assimilation. Production optimization is done on the updated ensemble mean model from EnKF. The production optimization resulted in a substantial increase in the NPV for the expected reservoir life compared to the base case with reactive control.