Modelling the property of compounds from structure: statistical methods for models validation

This study discusses some statistical methods used in quantitative structure–property relationships model’s validation and comparison. The paper also introduces a series of online tools for model’s validation. The implemented diagnostic tool that incorporated analytical approaches are exemplified on a series of models which estimate and predict the boiling points of a sample of 73 alkanes. The used parameters and methods are presented, and some reference values are provided.     

Desulfurization of coke oven gas from the coking of coking coal blended with a sorbent and waste plastic

A new way to implement the simultaneous reutilization of solid waste, the desulfurization of coke oven gas (COG), and even the desulfurization of coke by the co-coking of coking coal (CC) and waste plastic (WP) blended with a sorbent is proposed; the evolution of H₂S and the removal efficiency of H₂S from COG during the co-coking process were investigated in a lab-scale cylindrical reactor. The experimental results indicated that for the coking of CC blended with ZnO, Fe₂O₃, or blast furnace dust (BFD) as a sorbent, the instantaneous concentration of H₂S in COG was lower than 500 mg/m³ (which meets the technical specification requirement of the Chinese Cleaner Production Standard–Coking Industry, HJ/T 126-2003) when the molar ratio between the key component of the sorbent and the volatile S in CC or the CC/WP blend, n _Zn+Fe/n _S, was about 1.2 for ZnO and Fe₂O₃, but not for BFD under the same conditions, suggesting that ZnO and Fe₂O₃ are promising sorbents, but that BFD must be treated chemical or thermally before being used as a sorbent because of the size and complicated nature of the influence of its phase/chemical composition on its desulfurization ability. However, for the co-coking of CC and WP blended with ZnO as a sorbent, n _Zn+Fe/n _S must increase to 1.4 and 1.7 for 100/2 and 100/5 blends of CC/WP, respectively, to ensure a satisfactory efficiency for H₂S removal from COG. Part of this paper was presented at the International Symposium on EcoTopia Science 2005 (ISET05), Aug 8–9, 2005, Chikusa-ku, Nagoya, Japan     

Distribution-free two-sample comparisons in the case of heterogeneous variances

Behavioral ecologists are often faced with a situation where they need to compare the central tendencies of two samples. The standard tools of the t test and Mann–Whitney U test (equivalent to the Wilcoxon rank-sum test) are unreliable when the variances of the groups are different. The problem is particularly severe when sample sizes are different between groups. The unequal-variance t test (Welch test) may not be suitable for nonnormal data. Here, we propose the use of Brunner and Munzel’s generalized Wilcoxon test followed by randomization to allow for small sample sizes. This tests whether the probability of an individual from one population being bigger than an individual from the other deviates from random expectation. This probability may sometimes be a more clear and informative measure of difference between the groups than a difference in more commonly used measures of central tendency (such as the mean). We provide a recipe for carrying out a statistical test of the null hypothesis that this probability is 50% and demonstrate the effectiveness of this technique for sample sizes typical in behavioral ecology. Although the test is not available in any commercial software package, it is relatively straightforward to implement for anyone with some programming ability. Furthermore, implementations in R and SAS are freely available on the internet.     

Coastal erosion and shore protection: A brief historical analysis

Since the Neolithic, humans have gathered along coastal plains, where they had to face sea level rise and subsidence without the technology to oppose these processes. When sea level stabilized, approx. 6.000 yr. B.P., coastal colonization was allowed, but where mountain deforestation was carried out river sediment input increased tremendously: settlements were disconnected from the shore and harbour siltation occurred. Shore erosion was a limited process at the time and local solutions were adopted: clay dikes, wood piles, fascinates and rock revetments. Along the Mediterranean, in China and Japan the construction of more complex structures has been documented since the Middle Ages. Further human development, with river bed quarrying, wetland reclamation, dam construction and mountain re-afforestation, favoured a coastal erosion that nowadays threatens most world coasts. From the Venetian “Murazzi” to the recent 114-km-long concrete element defence at the Yellow river delta, shore protection structures evolved following the different needs (protect coastal communication routes, urban and industrial settlements, tourist resorts). Beach nourishment, previously performed with inland quarried materials, is now intensively carried out with marine aggregates. The vernacular solution, left to undeveloped countries, has been recently revaluated by “green engineering”. However, with Sea Level Rise, the debate of whether to defend, accommodate or retreat is open.     

Characteristic volume fractions of different grains in porous media for anomalous dispersion

Anomalous solute transport in porous media is an important issue in groundwater research. In this paper, we explore the relationship between the anomalous solute transport and the volume fractions of different grains in the porous media. Via simulation, we find that there is a maximum and a minimum in the degree of anomalous transport when changing the volume fractions of different grains. Moreover, the characteristic volume fractions corresponding to the anomalous transport maximum and minimum vary little with the flow field and diffusion coefficient of the solute. We also find that the volume fraction corresponding to the most anomalous dispersion is close to the threshold of the site percolation for simple-cubic networks.     

Synthesis of hydrogarnet from molten slag and its hydrogen chloride fixation performance at high temperature

Hydrogarnet was synthesized hydrothermally below 200°C using molten slag obtained from municipal solid waste. For comparison, it was also synthesized using pure-phase CaO–Al₂O₃–SiO₂–H₂O, as reported previously. The structural and textural properties of this material were investigated using various analytical and spectroscopic techniques such as X-ray diffraction, X-ray fluorescence spectrometry, atomic absorption spectrometry (AAS), thermogravimetry/differential thermal analysis, Fourier transform infrared spectroscopy, and scanning electron microscopy. The Cl⁻ fixation ability of hydrogarnet was investigated in the temperature range 500–800°C in a fixed-bed flow reactor using a HCl concentration (1000 p.p.m.v.) similar to that of incinerator exhaust gas. Under these experimental conditions, the hydrogarnet was capable of reducing the HCl gas level to less than 1 p.p.m.v. Analysis of the spent catalyst revealed that the hydrogarnet was being transformed into wadalite and CaCl₂ at high temperatures. The elution test for chromium ions in hydrogarnet obtained from slag was also used, and it was found that chromium ions were not eluted from hydrogarnet. Received: January 27, 2001 / Accepted: October 11, 2001     

Photodegradation of tetraphenyltin contained in polychlorinated biphenyl-based transformer oil simulants in alkaline 2-propanol solution

The photodegradation of tetraphenyltin (TePT) contained in polychlorinated biphenyl (PCB)-based transformer oil simulants by ultraviolet (UV) irradiation in alkaline 2-propanol solutions was examined. In the absence of PCBs, the TePT level fell to below 1% of the initial concentration within 30 min. In the absence of both PCBs and an alkali, the concentrations of tri-, di-, and monophenyltins initially increased to a few milligrams per liter, and then reduced to below the detection limits within 90 min. The addition of an alkali to the reaction solution slightly accelerated the photodecomposition of TePT. The decomposition of other phenyltins (PTs) was also accelerated. When PCBs with concentrations of approximately 80 times the initial TePT concentration were added, only a small fraction of the TePT decomposed within 100 min. Moreover, the levels of PTs did not change during irradiation. TePT and other PTs did decompose when the level of PCBs was reduced to the same concentration as that of TePT; however, the decomposition rates were slower than those in the absence of PCBs. In the actual treatment process, TePT and other PTs in PCB-based transformer oil are decomposed by catalytic reduction, which is used after UV irradiation. Therefore, in the actual treatment of PCB-based transformer oil wastes, pollution due to PTs can be prevented.     

Mobility of heavy metals from polluted sediments of a semi-enclosed basin: in situ benthic chamber experiments in Taranto’s Mar Piccolo (Ionian Sea,Southern Italy)

In situ benthic flux experiments were conducted at two stations in the Mar Piccolo of Taranto (Italy), one of the most industrialised and contaminated coastal areas of the Mediterranean. Sediments of the two stations are notably different in their trace metal content, with a station closer to a Navy harbour showing higher mean concentrations of almost all investigated metals (Al, As, Cd, Cr, Cu, Fe, Hg, Mn, Ni, Pb, V and Zn). Conversely, both stations are characterised by significant Hg contamination, compared to the local baseline. Results of a sequential extraction scheme on surface sediments suggest a relatively scarce mobility of the examined metals (Zn > Ni > Cr > As > Cu > Pb). A Hg-specific extraction procedure showed that most of the element (93.1 %) occurs in a fraction comprising Hg bound to Fe/Mn oxi-hydroxides. Reduction of these oxides may affect Hg remobilisation and redistribution. Porewater profiles of dissolved trace metals were quite similar in the two sites, although significant differences could be observed for Al, Cu, Fe and Hg. The highest diffusive fluxes were observed for As, Fe and Mn. Mobility rates of several trace elements (Al, As, Cd, Cr, Cu, Fe, Hg, Mn, Ni, Pb, V and Zn) were directly measured at the sediment–water interface. Results from benthic in situ incubation experiments showed increasing dissolved metal concentrations with time, resulting in higher fluxes for Cu, Fe, Hg, V and Zn in the most contaminated site. Conversely, fluxes of Mn, Ni and Pb were comparable between the two stations. The estimated flux of Hg (97 μg m^?2 day^?1) was the highest observed among similar experiments conducted in other highly contaminated Mediterranean coastal environments. Benthic fluxes could be partially explained by considering rates of organic matter remineralisation, dissolution of Fe/Mn oxy-hydroxides and metal speciation in sediments. Seasonal and spatial variation of biogeochemical parameters can influence metal remobilisation in the Mar Piccolo area. In particular, metals could be promptly remobilised as a consequence of oxygen depletion, posing a serious concern for the widespread fishing and mussel farming activities in the area.     

Design of water quality monitoring networks with two information scenarios in tropical Andean basins

Design and redesign of water quality monitoring networks were evaluated for two similarly sized watersheds in the tropical Andes via optimization techniques using geographic information system technology (GIS) and a matter-element analysis of 5-day biological oxygen demand (BOD₅) and total suspended solids (TSS). This resulted in a flexible, objectively based design for a 1128-km² watershed without prior water quality data (La Miel River), and a network redesign of a 1052-km² watershed with historical water quality monitoring (Chinchiná River). Monitoring design for the undocumented basin incorporated mathematical expressions for physical, anthropological, and historical factors—and was based on clear objectives for diagnosis and intervention of water pollution. Network redesign identified network redundancy, which resulted in a 64% reduction in the number of water quality monitoring stations along the channel, and a 78% reduction of stations throughout the basin. Most tropical drainage basins throughout the world have little to no prior water quality data. But even in well-studied drainage basins like the Chinchiná River, which is among the most thoroughly studied basins in Colombia, redesign of historical and existing monitoring networks will become a standard tool to advance the restoration of polluted surface waters, not only in Colombia, but also throughout the world.