Feasibility study of preparation and certification of reference materials for nitrogen dioxide and sulfur dioxide in diffusive samplers

This paper presents the results of a feasability study for the preparation and certification of reference materials (RMs) for nitrogen dioxide (NO(2)) and sulfur dioxide (SO(2)) in diffusive samplers. RMs for NO(2) were prepared by exposure to gas mixtures in a chamber while the RMs for SO(2) were prepared by liquid spiking. Certification of RMs for NO(2) was found feasible with a certified uncertainty of 5.8% and a proposed shelf life of 5 years. The uncertainty was calculated with contribution from the homogeneity of preparation, stability and transport of the CRMs and from an external verification of the certified value. To reach 5.8% of uncertainty, the contribution of the differences between the results of analysis by ion chromatography and colorimetry must be eliminated. It is proposed to solve this by pre-extracting the samplers with water before analysis. The results of this study indicate that the samplers are stable for at least two years before and after exposure when stored in a refrigerator. By contrast, the certification of RMs for SO(2) was found to not be feasible due to instability problems. This instability was attributed to reaction of sulfate on the walls of the samplers. Alternatively, the preparation of RMs by simultaneous exposure to SO(2) and NO(2) has been tested. Satisfying homogeneities has been reached both for NO(2) and SO(2).     

Trace Element Analyses in an Epiphytic Lichen and its Bark Substrate to Assess Suitability for Air Biomonitoring

Total concentrations of Cd, Cr, Fe, Ni, Pb and Zn were compared from October 1996 to April 1998 in Physcia biziana (Massal.) Zhalbr. v. leptophylla Vezda and in the bark of Quercus ilex L. sampled from the same trees at an urban park. Trace metal concentrations were also measured in the bark covered by the lichen thalli. The lichens showed significantly higher Cr, Fe, Ni and Zn concentrations than both uncovered and covered barks. By contrast, both types of barks had higher concentrations of Cd and Pb than lichens. Trace elements showed a wide temporal variation of concentrations both in the lichens and barks. No relationship was found between the analysed matrices as regards the time course of trace element concentrations.     

A Tool for Classification and Regression Using Random Forest Methodology: Applications to Landslide Susceptibility Mapping and Soil Thickness Modeling

Classification and regression problems are a central issue in geosciences. In this paper, we present Classification and Regression Treebagger (ClaReT), a tool for classification and regression based on the random forest (RF) technique. ClaReT is developed in Matlab and has a simple graphic user interface (GUI) that simplifies the model implementation process, allows the standardization of the method, and makes the classification and regression process reproducible. This tool performs automatically the feature selection based on a quantitative criterion and allows testing a large number of explanatory variables. First, it ranks and displays the parameter importance; then, it selects the optimal configuration of explanatory variables; finally, it performs the classification or regression for an entire dataset. It can also provide an evaluation of the results in terms of misclassification error or root mean squared error. We tested the applicability of ClaReT in two case studies. In the first one, we used ClaReT in classification mode to identify the better subset of landslide conditioning variables (LCVs) and to obtain a landslide susceptibility map (LSM) of the Arno river basin (Italy). In the second case study, we used ClaReT in regression mode to produce a soil thickness map of the Terzona catchment, a small sub-basin of the Arno river basin. In both cases, we performed a validation of the results and a comparison with other state-of-the-art techniques. We found that ClaReT produced better results, with a more straightforward and easy application and could be used as a valuable tool to assess the importance of the variables involved in the modeling.     

Identification and field bioassays of the sex pheromone of the yellow-legged clearwing Synanthedon vespiformis (Lepidoptera: Sesiidae)

The yellow-legged clearwing (YLC) Synanthedon vespiformis (Lepidoptera: Sesiidae) occurs in the Mediterranean and central Europe. It is polyphagous, boring into the woody parts of broadleaf species including forest trees as well as various Rosaceae species. S. vespiformis has been reported as an economically important pest causing severe injury to stone fruit plantations. Many attractants for sesiid species were discovered by random field screening using 2,13- and 3,13-octadecadienyl alcohols, acetates and aldehydes, including one for S. vespiformis; and about 20 sex pheromones of sesiids have been identified so far. In the present study we identified the natural composition of the sex pheromone of YLC laboratory reared females as a blend of E3,Z13- and Z3,Z13-octadecadienyl acetates, at a ratio of 4:1. We developed an efficient lure for monitoring the pest. Pheromone funnel traps with rubber septa, impregnated with 1 mg pheromone blend, efficiently captured males for 10 weeks. Suspension of Shin-Etsu^? ropes containing a 2:1 blend of E3,Z13-18:Ac and Z3,Z13-18:Ac at 13.74 mg/ha/h, resulted in shutdown of trap catches in the treated plots and closely situated neighboring plots indicating that mating disruption is feasible.     

Treatment of a clinical analysis laboratory wastewater from a hospital by photo-Fenton process at four radiation settings and toxicity response

Environmental Science and Pollution Research - The photo-Fenton process was performed with four radiation settings to treat clinical analysis laboratory wastewater (CALWW) from a hospital, with the...     

Towards a rational design of materials for the removal of environmentally relevant cations: polymer inclusion membranes (PIMs) and surface-modified PIMs for Sn2+ sequestration in aqueous solution

Environmental Science and Pollution Research - This work is focused on the design and preparation of polymer inclusion membranes (PIMs) for potential applications for stannous cation sequestration...     

Chemical and spectroscopic characterization of organic matter during the anaerobic digestion and successive composting of pig slurry

In this work, anaerobic digestion of pig slurry and successive composting of the digestate after centrifugation were studied by means of chemical analysis, FTIR and fluorescence spectroscopy as excitation–emission matrix (EEM). Chemical analysis highlighted the organic matter transformation occurring during the processes. A decrease of volatile solids and total organic carbon were observed in the digestate with respect to the fresh pig slurry as a consequence of the consumption of sugars, proteins, amino acids and fatty acids used by microorganisms as a C source. Water Extractable Organic Matter (WEOM) was obtained for all samples and fractionated into a hydrophilic and a hydrophobic fraction. The highest WEOM value was found in the pig slurry indicating a high content of labile organic C. The digestate centrifuged and the digestate composted showed lower hydrophilic and higher hydrophobic contents because of the decrease of labile C. Total phenolic content was lower in the digestate with respect to fresh pig slurry sample (36.7%) as a consequence of phenolic compounds degradation. The strong decrease of total reducing sugars in the digestate (76.6%) as compared to pig slurry confirmed that anaerobic process proceed mainly through consumption of sugars which represent a readily available energy source for microbial activity. FTIR spectra of pig slurry showed bands indicative of proteins and carbohydrates. A drop of aliphatic structures and a decrease of polysaccharides was observed after the anaerobic process along with the increase of the peak in the aromatic region. The composted substrate showed an increase of aromatic and a relative decrease of polysaccharides. EEM spectra provided tryptophan:fulvic-like fluorescence ratios which increased from fresh substrate to digestate because of the OM decompostion. Composted substrate presented the lowest ratio due to the humification process.     

Removal of heavy metal ions from wastewaters using dendrimer-functionalized multi-walled carbon nanotubes

Dendrimer-functionalized multi-walled carbon nanotubes (MWCNT) for heavy metal ion removal from wastewaters were developed. Triazole dendrimers (TD) were built directly onto the carbon nanotube surface by successive click chemistry reactions affording the zero- and first-generation dendrimer-functionalized MWCNT (MWCNT-TD1 and MWCNT-TD2). The Moedritzer-Irani reaction carried out on the amino groups present on the MWCNT-TD2 sample gave the corresponding α-aminophosphonate nanosystem MWCNT-TD2P. Both MWCNT-TD2 and MWCNT-TD2P nanosystems have been characterized by physical, chemical, and morphological analyses. Their chelating abilities towards the toxic metal ions Pb²⁺, Hg²⁺, and Ni²⁺ and the harmless Ca²⁺ ion have been experimentally evaluated in the two different sets of experiments and at the salt concentrations of 1 mg/mL or 1 μg/mL by inductively coupled plasma mass spectrometry (ICP-MS). The results of these studies pointed out the interesting chelating behavior for the phosphonated nanosystem towards the Hg²⁺ ion. The complexation mode of the best chelating system MWCNT-TD2P with mercury was investigated through density functional theory (DFT) calculations, suggesting a chelation mechanism involving the two oxygen atoms of the phosphate group. The synthesized dendrimers, supported on the multi-walled carbon nanotubes, have shown the potential to be used for the selective toxic metal ion removal and recovery.