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.

     

Occurrence and treatment trials of endocrine disrupting chemicals (EDCs) in wastewaters

This study demonstrates that both synthetic and natural endocrine disrupting chemicals (EDCs) (e.g., bisphenol A, estrone and 17beta-estradiol) were found in the crude wastewaters from two wastewater treatment works (WwTWs). Conventional biological processes can lower EDCs concentrations to several tens to hundreds ngl(-1). Since natural EDCs (e.g., estrone and 17beta-estradiol) have biological activity and adverse impact on the environment at extremely low concentrations (several tens of ngl(-1)), further treatment after conventional biological processes is required. Preliminary trials with ferrate(VI) and electrochemical oxidation process demonstrated that both processes can effectively reduce EDCs to very low levels, ranging between 10 and 100ngl(-1), but the former is more effective than the latter to reduce COD concentration in wastewater for given studying conditions.     

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.     

Mechanisms of lead, copper, and zinc retention by phosphate rock

The solid-liquid interface reaction between phosphate rock (PR) and metals (Pb, Cu, and Zn) was studied. Phosphate rock has the highest affinity for Pb, followed by Cu and Zn, with sorption capacities of 138, 114, and 83.2 mmol/kg PR, respectively. In the Pb-Cu-Zn ternary system, competitive metal sorption occurred with sorption capacity reduction of 15.2%, 48.3%, and 75.6% for Pb, Cu, and Zn, respectively compared to the mono-metal systems. A fractional factorial design showed the interfering effect in the order of Pb>Cu>Zn. Desorption of Cu and Zn was sensitive to pH change, increasing with pH decline, whereas Pb desorption was decreased with a strongly acidic TCLP extracting solution (pH = 2.93). The greatest stability of Pb retention by PR can be attributed to the formation of insoluble fluoropyromorphite [Pb(10)(PO(4))(6)F(2)], which was primarily responsible for Pb immobilization (up to 78.3%), with less contribution from the surface adsorption or complexation (21.7%), compared to 74.5% for Cu and 95.7% for Zn. Solution pH reduction during metal retention and flow calorimetry analysis both supported the hypothesis of retention of Pb, Cu, and Zn by surface adsorption or complexation. Flow calorimetry indicated that Pb and Cu adsorption onto PR was exothermic, while Zn sorption was endothermic. Our research demonstrated that PR can effectively remove Pb from solutions, even in the presence of other heavy metals (e.g. Cu, Zn).     

Application of a constructed wetland for industrial wastewater treatment: a pilot-scale study

The main objective of this study was to examine the efficacy and capacity of using constructed wetlands on industrial pollutant removal. Four parallel pilot-scale modified free water surface (FWS) constructed wetland systems [dimension for each system: 4-m (L)x1-m (W)x1-m (D)] were installed inside an industrial park for conducting the proposed treatability study. The averaged influent contains approximately 170 mg l(-1) chemical oxygen demand (COD), 80 mg l(-1) biochemical oxygen demand (BOD), 90 mg l(-1) suspend solid (SS), and 32 mg l(-1) NH(3)-N. In the plant-selection study, four different wetland plant species including floating plants [Pistia stratiotes L. (P. stratiotes) and Ipomoea aquatica (I. aquatica)] and emergent plants [Phragmites communis L. (P. communis) and Typha orientalis Presl. (T. orientalis)] were evaluated. Results show that only the emergent plant (P. communis) could survive and reproduce with a continuous feed of 0.4m(3)d(-1) of the raw wastewater. Thus, P. communis was used in the subsequent treatment study. Two different control parameters including hydraulic retention time (HRT) (3, 5, and 7d) and media [vesicles ceramic bioballs and small gravels, 1cm in diameter] were examined in the treatment study. Results indicate that the system with a 5-d HRT (feed rate of 0.4m(3)d(-1)) and vesicles ceramic bioballs as the media had the acceptable and optimal pollutant removal efficiency. If operated under conditions of the above parameters, the pilot-plant wetland system can achieve removal of 61% COD, 89% BOD, 81% SS, 35% TP, and 56% NH(3)-N. The treated wastewater meets the current industrial wastewater discharge standards in Taiwan.