Empirical likelihood confidence intervals for adaptive cluster sampling

Adaptive cluster sampling (ACS) is an efficient sampling design for estimating parameters of rare and clustered populations. It is widely used in ecological research. The modified Hansen-Hurwitz (HH) and Horvitz-Thompson (HT) estimators based on small samples under ACS have often highly skewed distributions. In such situations, confidence intervals based on traditional normal approximation can lead to unsatisfactory results, with poor coverage properties. Christman and Pontius (Biometrics 56:503–510, 2000) showed that bootstrap percentile methods are appropriate for constructing confidence intervals from the HH estimator. But Perez and Pontius (J Stat Comput Simul 76:755–764, 2006) showed that bootstrap confidence intervals from the HT estimator are even worse than the normal approximation confidence intervals. In this article, we consider two pseudo empirical likelihood functions under the ACS design. One leads to the HH estimator and the other leads to a HT type estimator known as the Hájek estimator. Based on these two empirical likelihood functions, we derive confidence intervals for the population mean. Using a simulation study, we show that the confidence intervals obtained from the first EL function perform as good as the bootstrap confidence intervals from the HH estimator but the confidence intervals obtained from the second EL function perform much better than the bootstrap confidence intervals from the HT estimator, in terms of coverage rate.     

Green technology for sustainable surface protection of steel from corrosion: a review

Plants contain substances that inhibit corrosion. Here we review biomass-based corrosion inhibitors from plant leaves, nuts, and fruit peels, after treatment with acids, bases or saline solutions. The mechanism of corrosion inhibition involves a monolayer coverage, according to isotherm and Langmuir models. Plant extract-based corrosion inhibitors contain heteroatoms whose electrons pair in the p-electron level in multiple bonds and the vacant d-orbitals of iron. Corrosion inhibition under marine conditions involves various chemical interactions between metals and dissolved ionic components.

     

Nano-structured dynamic Schiff base cues as robust self-healing polymers for biomedical and tissue engineering applications: a review

Polymer materials are vulnerable to damages, failures, and degradations, making them economically unreliable. Self-healing polymers, on the other hand, are multifunctional materials with superior properties of autonomic recovery from physical damages. These materials are suitable for biomedical and tissue engineering in terms of cost and durability. Schiff base linkages-based polymer materials are one of the robust techniques owing to their simple self-healing mechanism. These are dynamic reversible covalent bonds, easy to fabricate at mild conditions, and can self-reintegrate after network disruption at physiological conditions making them distinguished. Here we review self-healing polymer materials based on Schiff base bonds. We discuss the Schiff base bond formation between polymeric networks, which explains the self-healing phenomenon. These bonds have induced 100% recovery in optimal cases.

     

Metal contamination and solid phase partitioning of metals in urban roadside sediments

This study was undertaken to assess the anthropogenic impact on metal concentrations of urban roadside sediments (N = 633) in Seoul city, Korea and to estimate the potential mobility of selected metals (Zn, Cu, Pb, Cr, Ni, and Cd) using sequential extraction. Comparison of metal concentrations in roadside sediments with mean background values in sediments collected from first- or second-order streams in Korea shows that Zn, Cu and Pb are most affected by anthropogenic inputs. The 206Pb/207Pb ratios of roadside sediments (range = 1.1419-1.1681; mean 1.1576 +/- 0.0068) suggest that Pb is mainly derived from industrial sources rather than from leaded gasoline. A five-step sequential extraction of roadside sediments showed that Zn, Cd and to a lesser degree Ni occur predominantly in the carbonate bound fraction, while Pb is highest in the reducible fraction, Cu in the organic fraction, and Cr in the residual fraction. It was found that the concentrations in the readily available exchangeable fraction were generally low for most metals examined, except for Ni whose exchangeable fraction was appreciable (average 15.2%). Considering the proportion of metals bound to the exchangeable and carbonate fractions, the comparative mobility of metals probably decreases in the order of Zn > Ni > Cd > Pb > Cu > Cr. As potential changes of redox state and pH may remobilize the metals bound to carbonates, reducible, and/or organic matter, and may release and flush them through drain networks into streams, careful monitoring of environmental conditions appears to be very important. With respect to ecotoxicity, it is apparent the Zn and Cu pollution is of particular concern in Seoul city.     

Antimony distribution and environmental mobility at an historic antimony smelter site, New Zealand

A historic antimony smelter site at Endeavour Inlet, New Zealand has smelter residues with up to 17 wt.% antimony. Residues include coarse tailings (cm scale particles, poorly sorted), sand tailings (well sorted) and smelter slag (blocks up to 30 cm across). All of this material has oxidised to some degree over the ca. 100 years since the site was abandoned. Oxidation has resulted in acidification of the residues down to pH 2-5. Smelter slag contains pyrrhotite (FeS) and metallic antimony, and oxidation is restricted to surfaces only. The coarse tailings are the most oxidised, and few sulfide grains persist. Unoxidised sand tailings contain 10-20 vol.% stibnite (Sb2S3) containing up to 5% As, with subordinate arsenopyrite (FeAsS), and minor pyrite (FeS2). The sand tailings are variably oxidised on a scale of 2-10 cm, but original depositional layering is preserved during oxidation and formation of senarmontite (Sb2O3). Oxidation of sand tailings has resulted in localised mobility of both Sb and As on the cm scale, resulting in redistribution of these metalloids with iron oxyhydroxide around sand grain boundaries. Experiments demonstrate that Sb mobility decreases with time on a scale of days. Attenuation of both As and Sb occurs due to adsorption on to iron oxyhydroxides which are formed during oxidation of the smelter residues. There is no detectable loss of Sb or As from the smelter site into the adjacent river, <50 m away, which has elevated Sb (ca. 20 microg/l) and As (ca. 7 microg/l) from mineralised rocks upstream. Despite the high concentrations of Sb and As in the smelter residues, these metalloids are not being released into the environment.     

Modelling episodic acidification of surface waters: the state of science

Field studies of chemical changes in surface waters associated with rainfall and snowmelt events have provided evidence of episodic acidification of lakes and streams in Europe and North America. Modelling these chemical changes is particularly challenging because of the variability associated with hydrological transport and chemical transformation processes in catchments. This paper provides a review of mathematical models that have been applied to the problem of episodic acidification. Several empirical approaches, including regression models, mixing models and time series models, support a strong hydrological interpretation of episodic acidification. Regional application of several models has suggested that acidic episodes (in which the acid neutralizing capacity becomes negative) are relatively common in surface waters in several regions of the US that receive acid deposition. Results from physically based models have suggested a lack of understanding of hydrological flowpaths, hydraulic residence times and biogeochemical reactions, particularly those involving aluminum. The ability to better predict episodic chemical responses of surface waters is thus dependent upon elucidation of these and other physical and chemical processes.     

The global re-cycling of persistent organic pollutants is strongly retarded by soils

'Persistent organic pollutants' (POPs) are semi-volatile, mobile in the environment and bioaccumulate. Their toxicity and propensity for long-range atmospheric transport (LRAT) has led to international bans/restrictions on their use/release. LRAT of POPs may occur by a 'single hop' or repeated temperature-driven air-surface exchange. It has been hypothesised that this will result in global fractionation and distillation-with condensation and accumulation in polar regions. Polychlorinated biphenyls (PCBs)--industrial chemicals banned/restricted in the 1970s--provide a classic illustration of POP behaviour. A latitudinally-segmented global PCB inventory has been produced, which shows that approximately 86% of the 1.3 x 10(6) tonnes produced was used in the temperate industrial zone of the northern hemisphere. A global survey of background surface soils gives evidence for 'fractionation' of PCBs. More significantly, however, very little of the total inventory has 'made the journey' via primary emission and/or air-surface exchange and LRAT out of the heavily populated source regions, in the 70 years since PCBs were first produced. Soils generally occlude PCBs, especially soils with dynamic turnover of C/bioturbation/burial mechanisms. This limits the fraction of PCBs available for repeated air-soil exchange. The forested soils of the northern hemisphere, and other C-rich soils, appear to be playing an important role in 'protecting' the Arctic from the advective supply of POPs. Whilst investigations on POPs in remote environments are important, it is imperative that researchers also seek to better understand their release from sources, persistence in source regions, and the significant loss mechanisms/global sinks of these compounds, if they wish to predict future trends.