The contribution of L. C. Gray to the economic theory of exhaustible natural resources and its roots in the history of economic thought

The paper opens with an assessment of natural resources economics up to 1913–14 when Gray published his two pioneering articles in natural resources economics (Part I). An in-depth study of Gray, weighing his contribution to the microeconomic theory of the mine and the macroeconomic theory of conservation against current literature, constitutes the main body of the paper (Part II). Gray and Hotelling's contributions to the theory of the mine are compared (Part III). The paper concludes with a comparison drawn between the author's findings and the scant attention previously paid to Gray's contributions to natural resources economics.“So far as I know, this is the first attempt to apply economic theory to this particular problem of conservation.” (H. C. Taylor, unpublished letter to C. R. Van Hise, May 23, 1913, a reference to Gray's “Economic Possibilities of Conservation”).     

Reduction of silver solubility by humic acid and thiol ligands during acanthite (beta-Ag2S) dissolution

Precipitation of highly insoluble metal sulfide minerals like acanthite (beta-Ag2S) or red cinnabar (HgS) is in principle an effective means to reduce metal availability and toxicity in contaminated soils. Unfortunately, experiments have shown that red cinnabar may be solubilized in the presence of dissolved organic matter or thiol ligands. To determine whether the same applies to acanthite, a laboratory synthesized beta-Ag2S mineral was incubated for up to 3 weeks in the presence of KNO3, dissolved humic acids, cysteine, methionine and thiosulfate. XPS analysis identified Ag2O (52%), Ag2SO4 (8%) and Ag2S (40%) on the particle surfaces. Ag was released into solution in the presence of KNO3 and methionine, presumably from mixed-oxidation surface layers. Contrary to earlier results with cinnabar, however, humic acids reduced Ag concentrations in solution by about 75%, and cysteine and thiosulfate, each containing a free -SH functional group, almost completely suppressed Ag release into solution.     

Contribution of Pendant Ester Group Hydrolysis to the Erosion of Acrylic Polymers in Binders Aimed at Organotin-Free Antifouling Paints

Specific polymeric material applications as bioactive molecules delivery systems involve a strictly controlled degradation of polymer matrixes. One possibility to obtain a zero-order kinetic for small molecules release consists in a simple hydrolysis of ester groups contained in the macromolecular structure. The chemical degradation can lead to the continuous surface erosion of the formulated resins without loss of their mechanical properties and to a permanent activity of the delivery systems. Hydrolysis is a very well-known reaction in the case of organic molecules containing ester groups. The mechanism seems to be more complicated when ester groups are located in macromolecular structures. With the aim of antifouling applications, acrylic acid polymers bearing lateral ester groups of different chemical structures (hydrophilic, hydrophobic, hydrolyzable) have been prepared, characterized, and immersed in water, at pH 8, and their hydrolysis has been studied. Experimental data display two parameters, at least, which must be taken into account: the reactivity of the ester groups toward hydrolysis and the hydrophilic/hydrophobic balance of the polymer. The susceptibility of the acrylic polymers to hydrolysis has been compared to the erosion characteristics of the corresponding films. The results confirm that hydrolysis is necessary to obtain a regular degradation of the films without loss of mechanical properties. A relationship has been observed between the characteristics of hydrolysis and erosion for each studied polymer.     

Cement/clay interactions-- a review: experiments, natural analogues, and modeling

The concept of storing radioactive waste in geological formations calls for large quantities of concrete that will be in contact with the clay material of the engineered barriers as well as with the geological formation. France, Switzerland and Belgium are studying the option of clayey geological formations. The clay and cement media have very contrasted chemistries that will interact and lead to a degradation of both types of material. The purpose of this review is to establish an exhaustive list of laboratory experiments so as to identify the reaction sequences in the evolution of both the clay minerals and accessory minerals during their alteration in an alkaline environment. We review the data on clay dissolution kinetics in this environment, and include an invaluable study of natural analogues that allow one to correlate the phenomena in time. The available data and experiments make it possible to construct predictive numerical models. However, as the quality of the data is inhomogeneous, we recommend a continuation of the thermodynamic and kinetic data acquisition. It is obvious that the numerical modeling of the alkaline disturbance will be more relevant if it can combine the advantages of the different detailed models: mineralogical completeness, combined modeling of the clay and cement media, evolution of the porosity, consideration of the pCO2 and all the surface reactions.     

Preparation of solar-enhanced AlZnO@carbon nano-substrates for remediation of textile wastewaters

Photoactive aluminum doped ZnO(AlZnO) was synthesized by sol-gel method.After that,AlZnO photocatalyst was deposited on five carbon-based materials(CBMs) using ultrasonic route followed by solid-state mixing using ball mill.The CBMs used were poly aniline(PANI),carbon nitride(CN),carbon nanotubes(CNT),graphene(G),and carbon nanofibers(CNF).The crystal phases,elemental compositions,morphological,and optical properties of the AlZnO@CBMs composites were investigated.Experimental results revealed that two of AlZnO@CBMs composites exhibited superior bleaching efficiency(100% removal) and photocatalytic stability(three cycles) for 50 μmol/L Methylene Blue(MB) contaminated water after 60 min irradiation in visible light at pH 6.5,0.7% H_2O_2,and 5 g/L inorganic salts.Under optimum conditions,AlZnO@CBMs nanocomposites were employed for the treatment of mixed dyestuffs composed of MB,Methyl Orange(MO),Astrazone Blue FRR(BB 69),and Rhodamine B(RhB) dyes under dark,ultraviolet,visible,and direct sunlight.For mixed dyestuffs,the AlZnO@G achieved the highest dye sorption capacity(60.91 μmol dye stuffs/g) with kinetic rate 8.22 × 10~(-3) min~(-1) in 90 min via multi-layer physisorption(Freundlich isotherm) on graphene sheet.In additions,AlZnO@CN offered the highest photo-kinetic rate(K_(photo)) of～54.1 × 10~(-3) min~(-1)(93.8% after 60 min) under direct sunlight.Furthermore,the selective radical trapping experiment confirmed that the holes and oxidative superoxide radicals are crucial on dyes photodegradation pathway.Owing to their superior performance,AlZnO@G and AlZnO@CN nanocomposites can offer an effective in-situ solar-assisted adsorption/photocatalytic remediation of textile wastewater effluents.     

Oxidative co-treatment using hydrogen peroxide with anaerobic digestion of excess municipal sludge.

The effect of an oxidative co-treatment on anaerobic digestion of a mixture of primary and waste activated sludge was investigated. The oxidant used in this study was hydrogen peroxide (H2O2). A maximum improvement in solid destruction of 15.2% was achieved in the overall process, with a dosage of 2.0 g H2O2/g influent volatile suspended solids (VSS(influent)). All configurations operated at this dosage also showed statistically significant increases in solids removal. A statistically significant enhancement in overall solids destruction was observed for the lower oxidant dosage (0.5 H2O2/g VSS(influent)). Surprisingly, for 1.0 g H2O2/g VSS(influent), only one of the three configurations involving oxidative co-treatment showed significant increases in solids destruction. Special attention was paid to the performance of this process relative to fecal coliforms destruction. Class A biosolids were obtained for all the different hydrogen peroxide dosages used when oxidative co-treatment is combined with a two-stage anaerobic digestion process.     

Kinetics and mechanism of nitrite oxidation by hypochlorous acid in the aqueous phase

The rate coefficient for the reaction of nitrite with hypochlorite and hypochlorous acid has been studied using spectrophotometric measurements. The reaction rate has been determined in a wide range of H(+) concentration (5< or =-log[H(+)]< or =11). The kinetics were carried out as a function of NO(2)(-), H(+) and total hypochlorite ([HOCl](total)=[HOCl]+[ClO(-)]+[ClNO(2)]) concentrations. The observed overall rate law is described by: -d[HClO](T)dt=[a[NO(2)(-)](2)+b[NO(2)(-)]][H(+)](2)c+d[H(+)]+e[NO(2)(-)][H(+)](2)[HOCl](total)At T=298 K and in Na(2)SO(4) at an ionic strength (I=1.00 M), we obtained using a nonlinear fitting procedure: a=(1.83+/-0.36)x10(7) s(-1), b=(1.14+/-0.23)x10(5) Ms(-1), c=(1.12+/-0.17)x10(-13) M, d=(1.43+/-0.29)x10(-6) M(2) and e=(1.41+/-0.28)x10(3) M where the errors represent 2sigma. According to the overall rate law, a/b=k(1)/k(3), b/e=k(3), c=K(w), d/c=K(a), d=K(a)K(w) and e=K(1)K(a). In Na(2)SO(4) at an ionic strength (I=1.00 M), the values of K(1) and K(a) are (1.1+/-0.1)x10(-4) and 1.28x10(7) M(-1), respectively. A mechanism is proposed for the NO(2)(-) oxidation which involves the reversible initial step: NO(2)(-)+HOCl left harpoon over right harpoon ClNO(2)+OH(-) (K(1)), while ClNO(2) undergoes the two parallel reactions: attack by NO(2)(-) (k(1)) and hydrolysis (k(3)). ClNO(2) and N(2)O(4) are proposed as important intermediates as they control the mechanism. The rate coefficients k(1) and k(3) have been determined at different ionic strengths in NaCl and Na(2)SO(4). The influence of the ionic strength and ionic environment has been studied in this work.     

Diuron mobility through vineyard soils contaminated with copper

The herbicide diuron is frequently applied to vineyard soils in Burgundy, along with repeated treatments with Bordeaux mixture (a blend of copper sulfate and calcium hydroxide) that result in elevated copper concentrations. Cu could in principle affect the fate and transport of diuron or its metabolites in the soil either directly by complexation or indirectly by altering the populations or activity of microbes involved in their degradation. To assess the effect of high Cu concentrations on diuron transport, an experiment was designed with ten undisturbed columns of calcareous and acidic soils contaminated with 17--509 mg kg(-1) total Cu (field-applied). Grass was planted on three columns. Diuron was applied to the soils in early May and in-ground lysimeters were exposed to outdoor conditions until November. Less than 1.2% of the diuron applied was found in the leachates as diuron or its metabolites. Higher concentrations were found in the effluents from the grass-covered columns (0.1--0.45%) than from the bare-soil columns (0.02--0.14%), and they were correlated with increases in dissolved organic carbon. The highest amounts of herbicide were measured in acidic-soil column leachates (0.98--1.14%) due to the low clay and organic matter contents of these soils. Cu also leached more readily through the acidic soils (32.8--1042 microg) than in the calcareous soils (9.5--63.4 microg). Unlike in the leachates, the amount of diuron remaining in the soils at the end of the experiment was weakly related to the Cu concentrations in the soils.     

Biological Air Quality Monitoring: a Review

Air quality monitoring is currently ensured by captors measuring few physicochemical parameters, then they cannot evaluate unforeseen compounds and the interaction effects of pollutants. On the contrary, the use of bioindicators can answer these problems. Among them, plants are used in two ways:1) Passive bioindicators: trees, lichens and mosses are used to determine the distribution and even the contaminants long-term effects on vast zones and, possibly, the concentrations of pollutants to which they were exposed.2) Active bioindicators: tobacco and mosses make available the defective zones in plants and enable determination of deposition fluxes.Moreover, techniques based on biomarkers identification should increase the answer's sensitivity. However, the plants present the disadvantage of being unable to provide a response in a time lapse comparable with that of the on-line analysers. Lastly, the development of tools using animal cells should allow, in the near future, to measure the total polluting load under conditions close to those of the routine techniques. Then, the real impact of the contaminant on public health could be approached.