Evaluation of adsorption capacities of humic acids extracted from Algerian soil on polyaniline for application to remove pollutants such as Cd(Ⅱ), Zn(Ⅱ) and Ni(Ⅱ) and characterization with cavity microelectrode

The adsorption capacities of new humic acids isolated from Yakouren forest (YHA) and Sahara (Tamenrasset: THA) soils (Algeria) and commercial humic acid (PFHA) on polyaniline emeraldine base (PEB) were studied at pH 6.6. Also the adsorption of heavy metals such as Cd2+, Zn2+ and Ni2+ on humic acid-polyaniline systems (HA-PEB) was investigated at the same conditions. HA-PEB compounds were characterized by scanning electron microscopy (SEM), infrared spectrometry and cavity microelectrode. In addition, batch adsorption and cavity microelectrode were used in the adsorption study of Cd2+, Zn2+ and Ni2+ on HA-PEB. To develop biocaptors of polluting metals using a cavity microelectrode modified by HA-PEB systems, the adsorption kinetic and adsorption capacity were investigated. The SEM analysis showed that the presence of humic acid affected the PEB surface and caused the formation of a granular morphology. The maximum adsorption capacities (qmax) of PFHA, THA and YHA determined by adsorption isotherms were 91.31, 132.1 and 151.0 mg/g, respectively. Batch adsorption results showed that qmax of Cd2+, Zn2+ and Ni2+ on HA-PEB followed the order: THA-PEB > YHA-PEB > PFHA-PEB. The voltammograms obtained with HA-PEB modified cavity microelectrode showed the appearance of new redox couples reflecting the adsorption of HA on PEB. Metal-humic acid-polyaniline voltammograms were characterized by appearance of oxidation-reduction couples or reduction wave corresponding to metal. Finally, the result may be exploited to develop a biocaptor based on the cavity microelectrode amended by THA-PEB and YHA-PEB.     

Surface charge and adsorption from water onto quartz sand of humic acid

The surface charge of humic acid under different conditions of ionic strength, pH, and the presence of various cationic ions (Cu(2+), Zn(2+), Ba(2+), and Ca(2+)) was determined by a titration method using a cationic polyelectrolyte as titrant. Adsorption isotherms in batch experiments of the polymer from water onto quartz sand were determined at 20 degrees C, 40 degrees C, and 60 degrees C and under different conditions of ionic strength, pH, and the presence of various cationic ions (Cu(2+), Zn(2+), Ba(2+), and Ca(2+)). The data indicate significant decrease of humic acid surface charge by decreasing the pH value from 10.0 to 4.1. Similar decrease of humic acid surface charge was observed by increasing either the ionic strength or the affinity of the divalent cation toward the humic acid. At ambient temperature the adsorption of humic acid on the quartz sand seems to be controlled mainly by electrical interaction between the organic particle and the solid substrate. A correlation is found between the surface charge and the adsorbed amount of the polymer, the adsorbed amount increases when the surface charge of humic acid decreases. The increase of the adsorbed amount with the temperature suggests that adsorption process is endothermic.     

Characterization of fulvic acids during olive mill waste composting (Elemental,Thermal and fluorescence analyses)

Elemental analysis, fluorescence spectroscopy and differential scanning calorimetry (DSC) were applied to the study of fulvic acids isolated from different stages during olive mill waste composting. The fulvic extracted acids are characterized by a high nitrogen content and O/C ratio values that may result from the high degree of humification and the synthesis of more condensed humic complexes. This was confirmed by fluorescence spectroscopy in the synchronous-scan mode by the decrease of shoulder intensities at intermediate wavelengths indicating the increase of polycondensation and conjugation of unsaturated structures and the greater uniformity of fluorophores. Fluorescence spectra in the emission, excitation and synchronous modes became simpler with compost maturation. This was confirmed by DSC results which proved the high degree of polycondensation of aromatic nuclei of fulvic acid molecules during olive mill waste composting.     

Comparative study of humic acids of the mound of a wood-feeding termite and of the litter directly below in the Amazon river delta

In order to determine the role of termites in the recycling of organic matter and in humification processes, organic matter from the mound of a wood-feeding termite (Nasutitermes sp.) and from the litter directly below has been studied in secondary forest on the campus of Belem University, in Brazil. The carbon content was slightly lower in the litter (just beneath the mound) than in the mound, but nitrogen was much more abundant in the mound. As a consequence, the C/N ratio of fragmented litter total organic matter is very high, which shows that the humification process is not complete. Therefore, plant debris seemed to be more degraded in the mound than in the litter, indicating a humification gradient from mound to litter. Humic acid extracted from the mound and from the litter was compared by using elemental, E4/E6 ratio, spectroscopic (FTIR) analyses, and Sephadex gel chromatography. First, humic acids were more abundant in the mound than in the litter, showing that humification processes were more advanced in the mound than in the litter. Gel-permeation chromatography showed that the humic acids of the mound contained more low-molecular-weight fractions than those of the litter. In addition, the results of infrared spectra, E4/E6 ratio and elemental composition can confirm the fulvic character of mound material and the humic character of litter material. Therefore, the plant debris seems to follow two different humification pathways in the two environments, as long as the mound is alive.     

Life-Cycle Impact Assessment of oil drilling mud system in Algerian arid area

The objective of this work is to assess the environmental impacts of the drilling mud system in Algeria's arid region. Water-based mud (WBM) and oil-based mud (OBM) are used during well drilling in Hassi Messaoud petroleum field, and have a considerable pollution potential particularly on the aquifer system which constitutes the single resource of drinking water in the Sahara. The Life-Cycle Assessment (LCA) approach is applied to evaluate the impacts of several drilling mud systems across all stages of their life cycle, e.g. use, treatment and disposal. Environmental impacts of five treatments scenarios corresponding to the drilling waste management applied in Hassi Messaoud are compared: reserve pit without treatment (burial option), secondary high centrifugation (vertical cuttings dryer), stabilisation/solidification online, stabilisation/solidification off line and thermal desorption. The impact assessment is carried on using the LCIA models of Impact 2002+ method in SIMAPRO7 software. This assessment identifies human toxicity and terrestrial eco-toxicity as the major impact categories in this specific arid context and quantifies the emissions contributions. The local environmental impact is the most important of the drilling mud life cycle and is mainly linked to emissions from reserve pits, treated cuttings, and drilling phase 16″ through the Turonian and Albian aquifer. The main contributing substances are aromatic hydrocarbons fraction and metals in particular barium, zinc, antimony, arsenic, and aluminium. Concerning the comparison of the treatment scenarios, it appears that stabilisation/solidification online is the best one; it has the lowest impact score in the two dominating categories because of the waste minimisation: mud storage avoided in the reserve pit. The second best scenario is the thermal desorption which obtains the lowest impact score in carcinogen effects due to hydrocarbons reduction (<1%) and avoided impacts of recovered oil. The toxic substances fate modeling will be improved by taking into account their site-specific impact.     

Chemically degraded soil rehabilitation process using medicinal and aromatic plants: review

In recent decades, the increasing number of degraded lands worldwide makes their rehabilitation essential and crucial. Various techniques have emerged to fulfill these needs but most of them are expensive and difficult to be applied. Revegetation is a cost effective, environmental friendly, and aesthetically pleasing approach suitable for degraded areas. However, the use of edible crops, especially for areas with heavy metals (HM) contamination, is not ecologically suitable because the HM may enter the food chain. Alternatively, non-edible, fast-growing, deep-rooting, and metal-stabilizing plants with high biomass, which can produce high-value products hold a great potential and have been regarded as potential candidates of edible crops. This current review presents the benefits of using aromatic and medicinal plants (AMPs) and their associated microorganisms for revegetation of degraded sites as they are high-value economic crops. We discussed the effect of various stress on productivity of secondary metabolites in AMPs in addition to the potential health risk with human consumption of these plants and their products. A focus was also given to the effect of HM stress on the essential oil (EO) content of certain AMPs. Reported data showed that AMPs growing on HM-contaminated soils are safe products to use as they are not significantly contaminated themselves by HM.

     

Characterization of fulvic acids during olive mill waste composting (Elemental, Thermal and fluorescence analyses)

Elemental analysis, fluorescence spectroscopy and differential scanning calorimetry (DSC) were applied to the study of fulvic acids isolated from different stages during olive mill waste composting. The fulvic extracted acids are characterized by a high nitrogen content and O/C ratio values that may result from the high degree of humification and the synthesis of more condensed humic complexes. This was confirmed by fluorescence spectroscopy in the synchronous-scan mode by the decrease of shoulder intensities at intermediate wavelengths indicating the increase of polycondensation and conjugation of unsaturated structures and the greater uniformity of fluorophores. Fluorescence spectra in the emission, excitation and synchronous modes became simpler with compost maturation. This was confirmed by DSC results which proved the high degree of polycondensation of aromatic nuclei of fulvic acid molecules during olive mill waste composting.     

Closely associated theropod trackways from the Jurassic of Zimbabwe

Eighty-eight tracks of large theropod dinosaurs were found in the mid-Jurassic of Zimbabwe. Among the tracks, at least five adjacent trackways are recorded. The adjacent tracks were probably made by animals traveling as a group, given that they are in relatively close succession; that there are three overlapping tracks (among just 23) suggesting reasonably close associations of the animals; that all the tracks are apparently of the same ichnotaxon; that the preservational types of the tracks are similar; and that the tracks are all of animals traveling in one general direction closely associated in time (there are no returning tracks of the same animals or of those of other species; presence of such tracks would be highly probable if the tracks were made over a period of time of even several hours). Nearby, recently discovered giant sauropod tracks, the first in sub-Saharan Africa, indicate a realistic potential of predator/prey interactions between the two groups of dinosaurs.     

Behavior of As,Cd, Co,Cr, Cu,Pb, Ni,and Zn at the soil/plant interface around an uncontrolled landfill (Casablanca,Morocco)

The present work undertaken in the environmental context aims to study the distribution of heavy metals in plants that grow naturally around uncontrolled landfills. The study's goal was to identify plants that can be used to remediate contaminated soils. For this purpose, 14 plants species and their rhizospheric soil samples were collected and analyzed for arsenic, cadmium, cobalt, chromium, copper, lead, nickel, and zinc by inductively coupled plasma‐atomic emission spectrometry. The results showed the presence of elevated metal concentrations in soil, many exceeding the regulatory values, and that many species exhibited an ability to accumulate multiple metals in their shoots and roots without sustaining toxicity. This was confirmed by bioconcentration and translocation factors generally higher than 1.     

Validation of diffusive mini-samplers for aldehyde and VOC and its feasibility for measuring the exposure levels of elementary school children

Exposure to various chemicals can cause adverse effects to health, such as asthma and allergies, especially in children. Data on personal exposure levels in children are scarce, thus small lightweight diffusive mini-samplers for aldehydes and volatile organic compounds (VOCs) were designed to measure the exposure level of children to these chemicals. The aim of the study was to validate and examine the applicability of these mini-samplers for measuring daily chemical exposure. The diffusive mini-samplers are 20 mm in length, 11 mm in diameter, and 1.67 g in weight. The devices are cylindrically shaped with polytetrafluoroethylene membrane filters placed at each end. To measure aldehydes and acetone, 20 mg of 2,4-dinitrophenylhydrazine was used as an absorbent. To measure VOCs, a carbon molecular sieve was used. The sampling rate for each chemical was determined by parallel sampling with active samplers in a closed exposure bag. The blank levels of the chemicals and the storage stability of the device were tested. The mini-samplers were compared to commercially available diffusive samplers. To examine the applicability of the samplers, 65 elementary school children carried them for 24 h. The sampling rates for formaldehyde, acetaldehyde, and acetone were 20.9, 22.9, and 19.7 mL min(-1), respectively. The limits of quantification (LOQ) for the 24-hour sampling by high-performance liquid chromatography/ultraviolet (HPLC/UV) analysis were 8.3, 7.6, and 8.8 μg m(-3) for formaldehyde, acetaldehyde, and acetone, respectively. The sampling rates for the 11 VOCs were determined and ranged from 3.3 mL min(-1) for styrene and 2-ethyl-1-hexanol to 11.7 mL min(-1) for benzene. The LOQ for the 24-hour sampling by gas chromatography-mass spectrometry (GC-MS) analysis ranged from 5.9-105.2 μg m(-3), 1.1-24.7 parts per billion. The storage stability after 5 days ranged from 94.8 to 118.2%. Formaldehyde, acetone, benzene, and toluene were detected above the LOQ in more than 90% of the children, and the median concentrations were 21.7, 20.9, 10.1, and 21.5 μg m(-3), respectively. This study shows that the diffusive samplers developed were suitable for children to carry and were capable of measuring the children's daily chemical exposure.