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Considerations of uncertainty in setting critical loads of acidity of soils: the role of weathering rate determination.

The concept of critical loads has been generally accepted throughout Europe, and increasingly in Asian countries and the rest of the world, as providing the data which forms the basis for international negotiations on abatement strategies for emissions of acidifying pollutants. Central to the determination of quantitative critical loads of acidity for forests (and other ecosystems) is the rate at which the minerals in the soil weather or dissolve. Seven methods for determining these rates on a regional basis for the production of critical load maps have been suggested by the official bodies which are responsible for co-ordinating the European critical load mapping efforts. These methods are largely correlations which require a knowledge of the soil parent material and/or the soil mineralogy. The purpose of this paper is to review these weathering rate calculation methods and to assess whether it is currently possible to calculate numerically accurate critical loads for the production of regional critical load maps. A consideration of the data used to generate these methods and comparisons of the weathering rates calculated using various methods leads to the conclusion that at present it is not. Further work is needed to develop and maintain the initial credibility of critical loads both scientifically and as an aid to policy decisions.

Journal Article↗

Development of combinatorial chemistry methods for coatings: high-throughput weathering evaluation and scale-up of combinatorial leads.

Combinatorial screening of materials formulations followed by the scale-up of combinatorial leads has been applied for the development of high-performance coating materials for automotive applications. We replaced labor-intensive coating formulation, testing, and measurement with a "combinatorial factory" that includes robotic formulation of coatings, their deposition as 48 coatings on a 9x12-cm plastic substrate, accelerated performance testing, and automated spectroscopic and image analysis of resulting performance. This high-throughput (HT) performance testing and measurement of the resulting properties provided a powerful set of tools for the 10-fold accelerated discovery of these coating materials. Performance of coatings is evaluated with respect to their weathering, because this parameter is one of the primary considerations in end-use automotive applications. Our HT screening strategy provides previously unavailable capabilities of (1) high speed and reproducibility of testing by using robotic automation and (2) improved quantification by using optical spectroscopic analysis of discoloration of coating-substrate structure and automatic imaging of the integrity loss of coatings. Upon testing, the coatings undergo changes that are impossible to quantitatively predict using existing knowledge. Using our HT methodology, we have developed several cost-competitive coatings leads that match the performance of more costly coatings. These HT screening results for the best coating compositions have been validated on the traditional scales of coating formulation and weathering testing. These validation results have confirmed the improved weathering performance of combinatorially developed coatings over conventional coatings on the traditional scale.

Coated Materials, Biocompatible↗

Cl K-edge X-ray spectroscopic investigation of enzymatic formation of organochlorines in weathering plant material.

The contribution of halocarbons from plant weathering to the total organohalogen budget of terrestrial systems is gaining recognition. To evaluate the formation of such halocarbons, speciation of chlorine in Sequoia sempervirens (redwood) needles was examined in the presence of an external chloroperoxidase (CPO) enzyme using Cl K-edge X-ray absorption spectroscopy. The Cl forms in fresh and naturally weathered needles and in model laboratory reactions were compared. To provide a straightforward analogue to the enzymatic chlorination in plants, chlorination reactions were conducted for phenol, a common moiety of plant macromolecules. Plant material chlorination was also examined in the presence of hypochlorite in an ancillary mechanistic investigation. The dominant form of Cl in fresh, unreacted plant material was found to be inorganic Cl-, which was partially converted to organochlorine in the presence of CPO. Chlorination is affected by the nature of reactant (CPO, H2O2) addition, reaction time, and temperature. The organochlorines produced in these laboratory investigations closely resemble those produced during the natural weathering of redwood needles. A striking consistency in chlorine speciation observed among the various sample types suggests that (i) CPO produced by terrestrial organisms could play a vital role in the generation of organochlorines associated with the degradation of plant material and (ii) initial targets of enzymatic chlorination might include lignin-like macromolecules rich in aromatic character and hydroxyl groups. These findings lend further credibility to a significant biogenic contribution to the global organohalogen burden by elucidating a probable route of enzymatic chlorination of natural organic matter in terrestrial systems.

Chloride Peroxidase↗

Change of mechanical properties during short-term natural weathering of MSWI bottom ash.

The present work describes the change of mechanical properties during the natural weathering of freshly quenched processed bottom ash. An unconfined uniaxial compression to failure test of the unbound material was used to determine compressive strength and modulus of elasticity. Three main stages of mechanical behavior were determined. In the first stage, during a period lower than 30 days, mechanical properties suddenly increase, with a compressive strength and elastic modulus 7 times greater than the initial parameters. During the second stage, compressive strength and modulus of elasticity lightly increase until approximately 90 days of curing time. Starting from this period both mechanical properties remain steady and independent of the curing time. The neoformed phases, the elevated water content, and the improvement of particle contact after compaction act as a binder layer among particles, increasing the mechanical parameters during the short-term natural weathering process. Because of this, the freshly compacted bottom ash progresses from behaving as an unbound material into a bound pavement material. These mechanical properties obtained from freshly quenched bottom ash are 6-7 times greater than those obtained from previously weathered bottom ash. The bottom ash expansion and leaching of metals were also evaluated.

Construction Materials↗

Alteration processes in volcanic soils and identification of exobiologically important weathering products on Mars using remote sensing.

Determining the mineralogy of the Martian surface material provides information about the past and present environments on Mars which are an integral aspect of whether or not Mars was suitable for the origin of life. Mineral identification on Mars will most likely be achieved through visible-infrared remote sensing in combination with other analyses on landed missions. Therefore, understanding the visible and infrared spectral properties of terrestrial samples formed via processes similar to those thought to have occurred on Mars is essential to this effort and will facilitate site selection for future exobiology missions to Mars. Visible to infrared reflectance spectra are presented here for the fine-grained fractions of altered tephra/lava from the Haleakala summit basin on Maui, the Tarawera volcanic complex on the northern island of New Zealand, and the Greek Santorini island group. These samples exhibit a range of chemical and mineralogical compositions, where the primary minerals typically include plagioclase, pyroxene, hematite, and magnetite. The kind and abundance of weathering products varied substantially for these three sites due, in part, to the climate and weathering environment. The moist environments at Santorini and Tarawera are more consistent with postulated past environments on Mars, while the dry climate at the top of Haleakala is more consistent with the current Martian environment. Weathering of these tephra is evaluated by assessing changes in the leachable and immobile elements, and through detection of phyllosilicates and iron oxide/oxyhydroxide minerals. Identifying regions on Mars where phyllosilicates and many kinds of iron oxides/oxyhydroxides are present would imply the presence of water during alteration of the surface material. Tephra samples altered in the vicinity of cinder cones and steam vents contain higher abundances of phyllosilicates, iron oxides, and sulfates and may be interesting sites for exobiology.

Evolution, Planetary↗

Spectral evidence for weathered basalt as an alternative to andesite in the northern lowlands of Mars.

Mineral abundances derived from the analysis of remotely sensed thermal emission data from Mars have been interpreted to indicate that the surface is composed of basalt (Surface Type 1) and andesite (Surface Type 2). The global distribution of these rock types is divided roughly along the planetary dichotomy which separates ancient, heavily cratered crust in the southern hemisphere (basalt) from younger lowland plains in the north (andesite). But the existence of such a large volume of andesite is difficult to reconcile with our present understanding of the geological evolution of Mars. Here we reinterpret martian surface rock lithologies using mineral abundances from previous work and new mineralogies derived from a spectral end-member set representing minerals common in unaltered and low-temperature aqueously altered basalts. Our results continue to indicate the dominance of unaltered basalt in the southern highlands, but reveal that the northern lowlands can be interpreted as weathered basalt as an alternative to andesite. The coincidence between locations of such altered basalt and a suggested northern ocean basin implies that lowland plains material may be composed of basalts weathered under submarine conditions or weathered basaltic sediments transported into this depocentre.

Journal Article↗

Space weathering on airless planetary bodies: clues from the lunar mineral hapkeite.

Physical and chemical reactions occurring as a result of the high-velocity impacts of meteorites and micrometeorites and of cosmic rays and solar-wind particles are major causes of space weathering on airless planetary bodies, such as the Moon, Mercury, and asteroids. These weathering processes are responsible for the formation of their regolith and soil. We report here the natural occurrence of the mineral hapkeite, a Fe2Si phase, and other associated Fe-Si phases (iron-silicides) in a regolith breccia clast of a lunar highland meteorite. These Fe-Si phases are considered to be a direct product of impact-induced, vapor-phase deposition in the lunar soil, all part of space weathering. We have used an in situ synchrotron energy-dispersive, single-crystal x-ray diffraction technique to confirm the crystal structure of hapkeite as similar to the structure of synthetic Fe2Si. This mineral, hapkeite, is named after Bruce Hapke of the University of Pittsburgh, who predicted the presence and importance of vapor-deposited coatings on lunar soil grains some 30 years ago. We propose that this mineral and other Fe-Si phases are probably more common in the lunar regolith than previously thought and are directly related to the formation of vapor-deposited, nanophase elemental iron in the lunar soils.

Air↗

On the role of the weather in the deaths of R. F. Scott and his companions.

Robert Falcon Scott and his companions reached the South Pole in January of 1912, only to die on their return journey at a remote site on the Ross Ice Shelf, about 170 miles from their base camp on the coast. Numerous contributing causes for their deaths have been proposed, but it has been assumed that the cold temperatures they reported encountering on the Ross Ice Shelf, near 82-80 degrees S during their northward trek toward safety, were not unusual. The weather in the region where they perished on their unassisted trek by foot from the Pole remained undocumented for more than half a century, but it has now been monitored by multiple automated weather stations for more than a decade. The data recorded by Scott and his men from late February to March 19, 1912, display daily temperature minima that were on average 10 to 20 degrees F below those obtained in the same region and season since routine modern observations began in 1985. Only 1 year in the available 15 years of measurements from the location where Scott and his men perished displays persistent cold temperatures at this time of year close to those reported in 1912. These remarkably cold temperatures likely contributed substantially to the exhaustion and frostbite Scott and his companions endured, and their deaths were therefore due, at least in part, to the unusual weather conditions they endured during their cold march across the Ross Ice Shelf of Antarctica.

Journal Article↗

Influence of citric acid amendments on the availability of weathered PCBs to plant and earthworm species.

A series of small and large pot trials were conducted to assess the phytoextraction potential of several plant species for weathered polychlorinated biphenyls (PCBs) in soil (105 microg/g Arochlor 1268). In addition, the effect of citric acid on PCB bioavailability to both plants and earthworms was assessed. Under small pot conditions (one plant, 400 g soil), three cucurbits (Cucurbita pepo ssp pepo [zucchini] and ssp ovifera [nonzucchini summer squash], Cucumis sativus, cucumber) accumulated up to 270 microg PCB/g in the roots and 14 microg/g in the stems, resulting in 0.10% contaminant removal from soil. Periodic 1 mM subsurface amendments of citric acid increased the stem and leaf PCB concentration by 330 and 600%, respectively, and resulted in up to a 65% increase in the total amount of contaminant removed from soil. Although citric acid at 10 mM more than doubled the amount of PCB desorbed in abiotic batch slurries, contaminant accumulation by two earthworm species (Eisenia foetida and Lumbricus terrestris) was unaffected by citric acid at 1 and 10 mM and ranged from 11-15 microg/g. Two large pot trials were conducted in which cucurbits (C. pepo ssp pepo and ssp ovifera, C. sativus) and white lupin (Lupinus albus) were grown in 70 kg of PCB-contaminated soil White lupin was the poorest accumulator of PCBs, with approximately 20 microg/g in the roots and 1 microg/g in the stems. Both C. pepo ssp ovifera (summer squash) and C. sativus (cucumber) accumulated approximately 65-100 microg/g in the roots and 6-10 microg/g in the stems. C. pepo ssp pepo (zucchini) accumulated significantly greater levels of PCB than all other species, with 430 microg/g in the roots and 22 microg/g in the stems. The mechanism by which C. pepo spp pepo extracts and translocates weathered PCBs is unknown, but confirms earlier findings on the phytoextraction of other weathered persistent organic pollutants such as chlordane, p,p'-DDE, and polycyclic aromatic hydrocarbons.

Animals↗

Major Element, REE, and Other Trace Element Behavior in Amphibolite Weathering under Semiarid Conditions in Southern India.

A body of komatiitic amphibolite, an enclave within the Archean high-grade orthogneisses in southern India, shows mild chemical weathering under semiarid conditions. Along fractures, chemical weathering has advanced (Chemical Index of Alteration &sqbl0;CIA&sqbr0;=53; CIA of fresh rock approximately 26) to the extent that secondary Mg-Fe-Al clay minerals have formed and the rock has turned brownish red, soft, and fine grained. The weathering process has resulted in the mobilization and redistribution of the so-called immobile elements Fe, Al, Ti, and REE effected by the nature of secondary mineral formation (talc vs. aluminous clay minerals) and also possibly by soil microbes. In the initial stages of secondary mineral formation, there is a small loss of Fe, Al, and REE (noticeably Eu). However, in the fracture zone as well as in the incipiently altered zone, there is significant REE enrichment, probably affected by a different precipitation mechanism. Mobilized REE may have come from a minor alteration of clinopyroxene.

Journal Article↗

Airway cooling and mucosal injury during cold weather exercise.

In human subjects that exercise strenuously in cold weather, there is evidence that hyperventilation with cold air leads to peripheral airway cooling, desiccation and mucosal injury. Our hypothesis was that hyperventilation with cold air can result in penetration of unconditioned air (air that is not completely warmed and humidified) into the peripheral airways of exercising horses, resulting in peripheral airway mucosal injury. To test this hypothesis, a thermister-tipped catheter was inserted through the midcervical trachea and advanced into a sublobar bronchus in three horses that cantered on a treadmill at 6.6 m/s while breathing cold (5 degrees C) air. The mean (+/- s.e.) intra-airway temperature during cantering was 33.3 +/- 0.4 degrees C, a value comparable to the bronchial lumen temperatures measured in man during maximal exercise while breathing subfreezing dry air. In a second experiment, 6 fit Thoroughbred racehorses with satisfactory performance were used to determine whether strenuous exercise in cold conditions can produce airway injury. Horses were assigned to Exercise (E) or Control (C) groups in a random crossover design. Samples of bronchoalveolar lavage fluid (BALF) in the E treatment were recovered within 30 min of galloping exercise in 4 degrees C, 100% relative humidity (E), while in C BALF samples were obtained when the horses had not performed any exercise for at least 48 h prior. Ciliated epithelial cells in BALF were higher in E than in the C treatment. Similar results have been found in human athletes and laboratory animal models of cold weather exercise. These results support the hypothesis that, similar to man, horses that exercise in cold weather experience peripheral airway mucosal injury due to the penetration of unconditioned air. Furthermore, these results suggest that airway cooling and desiccation may be a factor in airway inflammation commonly found in equine athletes.

Air↗

Atmospheric science. Weather forecasting with ensemble methods.

Traditional weather forecasting has been built on a foundation of deterministic modeling--start with initial conditions, put them into a supercomputer model, and end up with a prediction about future weather. But as Gneiting and Raftery discuss in their Perspective, a new approach--ensemble forecasting--was introduced in the early 1990s. In this method, up to 100 different computer runs, each with slightly different starting conditions or model assumptions, are combined into a weather forecast. In concert with statistical techniques, ensembles can provide accurate statements about the uncertainty in daily and seasonal forecasting. The challenge now is to improve the modeling, statistical analysis, and visualization technologies for disseminating the ensemble results.

Journal Article↗

Stormy weather in galaxy clusters

Recent x-ray, optical, and radio observations coupled with particle and gas dynamics numerical simulations reveal an unexpectedly complex environment within clusters of galaxies, driven by ongoing accretion of matter from large-scale supercluster filaments. Mergers between clusters and continuous infall of dark matter and baryons from the cluster periphery produce long-lived "stormy weather" within the gaseous cluster atmosphere-shocks, turbulence, and winds of more than 1000 kilometers per second. This weather may be responsible for shaping a rich variety of extended radio sources, which in turn act as "barometers" and "anemometers" of cluster weather.

Journal Article↗

Resistance of weathered cotton cellulose to cellulase action.

Increased resistance of weathered cotton cellulose to microbial breakdown has been shown to be the result of development of resistance to the action of fungal cellulases. Photochemical activity during weathering exposure transforms the cellulose into an altered substrate that prevents access of the enzymes to susceptible sites of the cellulose molecule. It is postulated that the altered substrate consists of cellulose molecules of low degrees of polymerization, with some ring openings and altered chain ends. Weathered cellulose fails to adsorb cellulases.

Journal Article↗

Contrasting patterns of mortality and hospital admissions during hot weather and heat waves in Greater London, UK.

BACKGROUND: Epidemiological research has shown that mortality increases during hot weather and heat waves, but little is known about the effect on non-fatal outcomes in the UK. AIMS AND METHODS: The effects of hot weather and heat waves on emergency hospital admissions were investigated in Greater London, UK, for a range of causes and age groups. Time series analyses were conducted of daily emergency hospital admissions, 1 April 1994 to 31 March 2000, using autoregressive Poisson models with adjustment for long term trend, season, day of week, public holidays, the Christmas period, influenza, relative humidity, air pollution (ozone, PM10), and overdispersion. The effects of heat were modelled using the average of the daily mean temperature over the index and previous two days. RESULTS: There was no clear evidence of a relation between total emergency hospital admissions and high ambient temperatures, although there was evidence for heat related increases in emergency admissions for respiratory and renal disease, in children under 5, and for respiratory disease in the 75+ age group. During the heat wave of 29 July to 3 August 1995, hospital admissions showed a small non-significant increase: 2.6% (95% CI -2.2 to 7.6), while daily mortality rose by 10.8% (95% CI 2.8 to 19.3) after adjusting for time varying confounders. CONCLUSIONS: The impact of hot weather on mortality is not paralleled by similar magnitude increases in hospital admissions in the UK, which supports the hypothesis that many heat related deaths occur in people before they come to medical attention. This has evident implications for public health, and merits further enquiry.

Adolescent↗

Weather conditions and sudden sensorineural hearing loss.

BACKGROUND: Climatic or meteorological condition changes have been implicated in the pathogenesis of Idiopathic Sudden Sensorineural Hearing Loss (ISSHL). We investigated the seasonal distribution of ISSHL and evaluated the influence of meteorological parameters (such as temperature, humidity, and atmospheric pressure), their variation and covariation on the incidence of the disease. METHODS: A total of 82 cases of ISSHL, admitted to our department over a five-year period, were enrolled in the study. Seasonal distribution of the disease was investigated by dividing the year in four seasons. Meteorological data included daily values of 13 distinct parameters recorded at the meteorological station of the University of Ioannina during this period. A relationship between each meteorological variable and the incidence of ISSHL was investigated by applying (chi2) test on data from 13 contingency tables as well as by using logistic regression and t-test approaches. In addition, the influence of different weather types on the incidence of ISSHL was investigated using Cluster Analysis in order to create eight clusters (weather types) characteristic for the prefecture of Ioannina. RESULTS: The results of the study could not indicate any seasonal distribution of the disease. The incidence of ISSHL could not be significantly correlated either to any distinct meteorological parameter or to any specific weather type. CONCLUSIONS: Meteorological conditions, such as those dominating in the Northwestern Greece, and/or their changes, have no proven effect on the incidence of ISSHL.

Journal Article↗

Aryl hydrocarbon receptor-independent toxicity of weathered crude oil during fish development.

Polycyclic aromatic hydrocarbons (PAHs), derived largely from fossil fuels and their combustion, are pervasive contaminants in rivers, lakes, and nearshore marine habitats. Studies after the Exxon Valdez oil spill demonstrated that fish embryos exposed to low levels of PAHs in weathered crude oil develop a syndrome of edema and craniofacial and body axis defects. Although mechanisms leading to these defects are poorly understood, it is widely held that PAH toxicity is linked to aryl hydrocarbon receptor (AhR) binding and cytochrome P450 1A (CYP1A) induction. Using zebrafish embryos, we show that the weathered crude oil syndrome is distinct from the well-characterized AhR-dependent effects of dioxin toxicity. Blockade of AhR pathway components with antisense morpholino oligonucleotides demonstrated that the key developmental defects induced by weathered crude oil exposure are mediated by low-molecular-weight tricyclic PAHs through AhR-independent disruption of cardiovascular function and morphogenesis. These findings have multiple implications for the assessment of PAH impacts on coastal habitats.

Abnormalities, Multiple↗

Bronchoconstriction due to cold weather in COPD. The roles of direct airway effects and cutaneous reflex mechanisms.

To clarify how cold weather may induce bronchoconstriction in patients with COPD, a series of challenges were performed in 20 patients with COPD in stable condition as well as in 13 healthy subjects. A whole-body exposure to -17 degrees C during resting nasal breathing was performed to study the reflex effects of facial cooling on lung function. In addition, a near-maximal hyperventilation of cold air was performed in a warm room to study the direct airway effects of cold air. The whole-body exposure to cold air induced statistically significant bronchoconstriction in both groups, the maximal decrements in FEV1 being 9.4 +/- 1.4% in the patients with COPD and 10.3 +/- 0.8% in the healthy subjects (p = NS). The whole-body exposure to cold air also increased the resting ventilation. The hyperventilation challenge induced bronchoconstriction only in the patients with COPD, the maximal decrements in FEV1 being 8.0 +/- 1.3% and 1.5 +/- 1.0%, respectively (p < 0.01). These results suggest that cooling of the facial skin is predominantly responsible for the bronchoconstriction due to cold weather both in patients with COPD and in healthy subjects. At high ventilation level, as during heavy exercise, the direct airway effects of cold air may also contribute to the bronchoconstriction in patients with COPD. Some patients with severe COPD might benefit from wearing protective clothing over their face in cold weather.

Adult↗