Biodegradation study of PDLA/cellulose microfibres biocomposites by Pseudomonas aeruginosa.

Aerobic biodegradation of biocomposites has been studied in both solid and liquid media. The research was concentrated on the biodegradation under aerobic and mesophilic conditions using poly-d-lactic acid (PDLA) and PDLA/cellulose microfibres (CMFs) samples as the sole carbon source. To determine the efficiency of the biodegradation, quantitative (mass variations, optical density (OD)) and qualitative (FTIR, NMR and SEM) analyses have been used to follow the polymer changes after degradation. The weight loss and OD of the biocomposites samples PDLA/CMFs were slower than that of pristine PDLA. The PDLA displayed the most important loss of weight (7.09%, 8.95%) compared to its initial weight and the lowest weight loss was detected in PDLA/CMF300 (1.04%, 2.19%) in solid and liquid mediums respectively. Also, the OD value of PDLA was increased from the seven days (0.381) to the last day (0.969). It appears that the major rate-determining factor affecting material degradation was its crystallinity without or with minimal assistance from abiotic factor because crystalline phases inhibit the diffusion of small water molecules. Otherwise, the Pseudomonas aeruginosa was isolated from Mediterranean soil has been found to be a novel candidate to biodegrade PDLA under mesophilic conditions.

Environmental quality assessment of the fish farms' impact in the Monastir Bay (eastern of Tunisia, Central Mediterranean): a benthic foraminiferal perspective.

Offshore fish farms have been active inside the Monastir Bay, Hammemet Gulf for over 10 years, but their environmental impact is still unknown. This study focuses on the evaluation of the fish farming activity impact in the Monastir Bay as revealed by geochemical and benthic foraminiferal data. Samples were collected around three fish cages at different water depths. Total organic carbon (TOC) and total phosphate (TP) in the sediment show higher values beneath the fish cages and decrease proportionally with distance from the cages. Living foraminiferal assemblages around fish farms are dominated by stress-tolerant species with higher abundances of Ammonia tepida, Rosalina bradyi, Elphidium crispum, and Peneroplis planatus. On the basis of our results, A. tepida and Quinqueloculina seminula are confirmed to be tolerant to elevated nutriment content, while Ammonia parkinsoniana seems to be more sensitive to organic enrichment. We also test the Foram-AMBI that is revealed to be a very promising tool by which evaluating the ecological quality status of marine sediment. The results of the present study confirm the suitability of living benthic foraminifera as bioindicators of organic enrichment induced by aquaculture activities.

Testing the impact of contaminated sediments from the southeast marine coast of Tunisia on biota: a multibiomarker approach using the flatfish Solea senegalensis.

Coastal marine areas are highly vulnerable to the exposure to various types of stressors and impact of chemical pollution resulting from increasing anthropogenic activities, namely pollution by metals and polycyclic aromatic hydrocarbons (PAHs). To assess ecosystem quality and functions, biomarkers can provide information about the presence and adverse effects of pollutants. Accordingly, the present study was conducted to evaluate the chronic (28 days) biologic effects of putatively contaminated sediments from the Zarzis area, located in the south of the Gulf of Gabes on the Southern Tunisian coast, on the marine flatfish Solea senegalensis. Sediments were collected at three sampling sites, impacted by wastewater discharges, aquaculture activities, and industrial contamination, and then surveyed for metals (Cd, Cu, Cr, Hg, Zn, and Pb) and organic contaminants (polycyclic aromatic hydrocarbons). The quantified biomarkers involved the determination of oxidative stress, phase II metabolism, and the extent of lipid peroxidation (catalase, CAT; glutathione peroxidase activity: total and selenium-dependent, T-GPx and Se-GPx; activities of glutathione-S-transferases, GSTs; levels of lipid peroxidation, by means of the thiobarbituric acid reactive substances assay, TBARS) and neurotoxicity (activity of acetylcholinesterase, AChE). S. senegalensis exposed to potentially contaminated sediments, collected near the aquaculture facility, presented the highest values for the generality of biomarkers tested, and a significant inhibition of AChE activity. A few lesions have been also recorded in the gills and liver tissues of S. senegalensis following chronic exposure. However, the observed lesions in gills (e.g., epithelial lifting, lamellar fusion, gills hyperplasia and hypertrophy, and leukocyte infiltration) and liver (cytoplasmic vacuolation, enlargement of sinusoids, foci of necrosis, and eosinophilic bodies) were of minimal pathological importance and/or low prevalence that did not significantly affect the weighted histopathological indices. Finally, the biological responses evidenced by this flatfish can be potentially caused by metal and PAH pollution occurring in specific areas in the southeast of Tunisia. The type and extent of the observed biochemical alterations strongly suggest that the contaminated sediments from the surveyed areas could cause early adverse biological effects on exposed biota.

Toxicity Assessment of Impacted Sediments from Southeast Coast of Tunisia Using a Biomarker Approach with the Polychaete Hediste diversicolor.

Toxicity caused by exposure to pollutants from marine sediments is a consequence of the interaction between biota and xenobiotics most frequently released by anthropogenic activities. The present work intended to characterize the toxicity of natural sediments putatively impacted by distinct human activities, collected at several sites located in the south of the Gulf of Gabes, Zarzis area, Tunisia. The selected toxicity criteria were analysed following ecologically relevant test conditions. Organisms of the polychaete species Hediste diversicolor were chronically exposed (28 days) to the mentioned sediments. Toxicity endpoints were biomarkers involved in the toxic response to common anthropogenic chemicals, namely neurotoxic (acetylcholinesterase), anti-oxidant (catalase, glutathione peroxidase), metabolic (glutathione S-transferases) enzymatic activities, and oxidative damage (lipid peroxidation, TBARS assay). The chemical characterization of sediments showed that the samples collected from the site near an aquaculture facility were highly contaminated by heavy metals (Cd, Cu, Cr, Hg, Pb, and Zn) and polycyclic aromatic hydrocarbons (fluorene, phenanthrene, anthracene, fluoranthene and pyrene). H. diversicolor individuals exposed to the sediments from this specific site showed the highest values among all tested biomarkers, suggesting that these organisms were possibly under a pro-oxidative stress condition potentially promoted by anthropogenic pollution. Moreover, it was possible to conclude that individuals of the polychaete species H. diversicolor responded to the chronic exposure to potentially contaminated sediments from the southeast coast of Tunisia, eliciting adaptive responses of significant biological meaning.

Biodegradation of oxytetracycline and enrofloxacin by autochthonous microbial communities from estuarine sediments.

This work investigated the potential of microbial communities native to an estuarine environment to biodegrade enrofloxacin (ENR) and oxytetracycline (OXY). Sediments collected from two sites in the Douro river estuary (Porto, Portugal) were used as inocula for the biodegradation experiments. Experiments were carried out for one month, during which ENR and OXY (1 mg L-1) were supplemented individually or in mixture to the cultures at 10-day intervals. Acetate (400 mg L-1) was added to the cultures every 3 days to support microbial growth. A series of experimental controls were established in parallel to determine the influence of abiotic breakdown and adsorption in the removal of the antibiotics. Removal of antibiotics was followed by measuring their concentration in the culture medium. Additionally, next-generation sequencing of the 16S rRNA gene amplicon was employed to understand how microbial communities responded to the presence of the antibiotics. At the end of the biodegradation experiments, microbial cultures derived from the two estuarine sediments were able to remove up to 98% of ENR and over 95% of OXY. The mixture of antibiotics did not affect their removal. ENR was removed mainly by biodegradation, while abiotic mechanisms were found to have a higher influence in the removal of OXY. Both antibiotics adsorbed at different extents to the estuarine sediments used as inocula but exhibited a higher affinity to the sediment with finer texture and higher organic matter content. The presence of ENR and OXY in the culture media influenced the dynamics of the microbial communities, resulting in a lower microbial diversity and richness and in the predominance of bacterial species belonging to the phylum Proteobacteria. Therefore, microbial communities native from estuarine environments have potential to respond to the contamination caused by antibiotics and may be considered for the recovering of impacted environments through bioremediation.

Ultrasonic power improvement of flumequine degradation effectiveness in aqueous solution via direct and indirect action of mechanical acoustic wave.

The current research work aimed to describe the roles of ultrasonic power under sono-Fenton process in the degradation of flumequine (FLU) in water. For this purpose, the effects of some parameters including temperature, ferrous ion concentration, chemical oxidant concentration (S2O82- and Cl-) and the initial pH value of the reaction kinetics were investigated. Results showed that the degradation of FLU antibiotic was accelerated by ultrasonic irradiation and the presence of an inorganic oxidant. The sono-generation of active species such as hydroxyl radicals (HO and HOO) and sulfate radicals (SO4-) as strong oxidizing agents improved the FLU degradation. In fact, the peroxydisulfate anion (S2O82-) has been identified as among parameters that enhanced the degradation process. Under optimal conditions, 98% of the flumequine removal was carried out within 80 min at 60 °C.

Spatial distribution and contamination assessment of heavy metals in marine sediments of the southern coast of Sfax, Gabes Gulf, Tunisia.

In order to investigate the current distribution of metal concentrations in surface marine sediments of the southern coast of Sfax (Tunisia), thirty-nine samples were collected in the vicinity of a mixed industrial and domestic wastewater effluent discharge. In comparison with the threshold effect level and probable effect level, the majority of metals had high ecological and biological risks. Enrichment factor and geoaccumulation Index showed that the majority of sediments are unpolluted by As, Ni and Pb, moderately polluted by Cr and Cu and moderately to strongly polluted by P, Y, Zn. Besides, all sites are extremely polluted by Cd. Principal component analysis indicates that As, Cu and Ni were mainly from lithogenic sources, whereas Cd, Cr, F, P, Pb, Y and Zn were mainly derived from anthropogenic source. Findings of this research can be used as suitable reference for future studies and environmental management plans in the region.

Risk assessment of occupational exposure to heavy metal mixtures: a study protocol.

BACKGROUND: Sfax is a very industrialized city located in the southern region of Tunisia where heavy metals (HMs) pollution is now an established matter of fact. The health of its residents mainly those engaged in industrial metals-based activities is under threat. Indeed, such workers are being exposed to a variety of HMs mixtures, and this exposure has cumulative properties. Whereas current HMs exposure assessment is mainly carried out using direct air monitoring approaches, the present study aims to assess health risks associated with chronic occupational exposure to HMs in industry, using a modeling approach that will be validated later on. METHODS: To this end, two questionnaires were used. The first was an identification/descriptive questionnaire aimed at identifying, for each company: the specific activities, materials used, manufactured products and number of employees exposed. The second related to the job-task of the exposed persons, workplace characteristics (dimensions, ventilation, etc.), type of metals and emission configuration in space and time. Indoor air HMs concentrations were predicted, based on the mathematical models generally used to estimate occupational exposure to volatile substances (such as solvents). Later on, and in order to validate the adopted model, air monitoring will be carried out, as well as some biological monitoring aimed at assessing HMs excretion in the urine of workers volunteering to participate. Lastly, an interaction-based hazard index HIint and a decision support tool will be used to predict the cumulative risk assessment for HMs mixtures. DISCUSSION: One hundred sixty-one persons working in the 5 participating companies have been identified. Of these, 110 are directly engaged with HMs in the course of the manufacturing process. This model-based prediction of occupational exposure represents an alternative tool that is both time-saving and cost-effective in comparison with direct air monitoring approaches. Following validation of the different models according to job processes, via comparison with direct measurements and exploration of correlations with biological monitoring, these estimates will allow a cumulative risk characterization.

Natural and anthropogenic particulate-bound aliphatic and polycyclic aromatic hydrocarbons in surface waters of the Gulf of Gabès (Tunisia, southern Mediterranean Sea).

Particulate-bound aliphatic and polycyclic aromatic hydrocarbons (AHs and PAHs) were investigated in the surface waters of the Gulf of Gabès (Tunisia, southern Mediterranean Sea). Samples were collected off the Sfax and Gabès-Ghannouch coasts. Concentrations in total resolved n-alkanes ranged from 0.03 to 3.2 µg L-1, and concentrations in total parents + alkylated PAHs ranged from bdl to 108.6 ng L-1. The highest concentrations were recorded in the southern Sfax. AHs were mainly of biogenic origin with odd n-alkane predominance, although an anthropogenic contribution was also detected. The PAH molecular patterns revealed a mixed origin with the presence of low molecular weight and alkylated compounds, characteristic of uncombusted oil-derived products, and the presence of high molecular weight compounds, typical of combustion residues. Rainfall events induced an increase in PAH concentrations by a factor 1.5-23.5. The particle-water partition coefficients (Koc) suggest that the partitioning of PAHs between the particulate and dissolved phases is driven by hydrophobicity and organic matter composition.

Origin and distribution of hydrocarbons and organic matter in the surficial sediments of the Sfax-Kerkennah channel (Tunisia, Southern Mediterranean Sea).

We investigated the origin and distribution of aliphatic and polycyclic aromatic hydrocarbons (AHs and PAHs) and organic matter (OM) in surficial sediments of the Sfax-Kerkennah channel in the Gulf of Gabès (Tunisia, Southern Mediterranean Sea). TOC, AH and PAH concentrations ranged 2.3-11.7%, 8-174µgg-1sed.dw and 175-10,769ngg-1sed.dw, respectively. The lowest concentrations were recorded in the channel (medium sand sediment) and the highest ones in the Sfax harbor (very fine sand sediment). AHs, PAHs and TOC were not correlated for most of the stations. TOC/N and δ13C values revealed a mixed origin of OM with both marine and terrestrial sources. Hydrocarbon molecular composition highlighted the dominance of petrogenic AHs and the presence of both petrogenic and pyrogenic PAHs, associated with petroleum products and combustion processes. This work underscores the complex distribution patterns and the multiple sources of OM and hydrocarbons in this highly anthropogenized coastal environment.

Removal of bisphenol A and some heavy metal ions by polydivinylbenzene magnetic latex particles.

In this study, magnetic polydivinylbenzene latex particles MPDVB with a core-shell structure were tested for the removal of bisphenol A (BPA), copper Cu(II), lead Pb(II), and zinc Zn(II) from aqueous solutions by a batch-adsorption technique. The effect of different parameters, such as initial concentration of pollutant, contact time, adsorbent dose, and initial pH solution on the adsorption of the different adsorbates considered was investigated. The adsorption of BPA, Cu(II), Pb(II), and Zn(II) was found to be fast, and the equilibrium was achieved within 30 min. The pH 5-5.5 was found to be the most suitable pH for metal removal. The presence of electrolytes and their increasing concentration reduced the metal adsorption capacity of the adsorbent. Whereas, the optimal pH for BPA adsorption was found 7, both hydrogen bonds and π-π interaction were thought responsible for the adsorption of BPA on MPDVB. The adsorption kinetics of BPA, Cu(II), Pb(II), and Zn(II) were found to follow a pseudo-second-order kinetic model. Equilibrium data for BPA, Cu(II), Pb(II), and Zn(II) adsorption were fitted well by the Langmuir isotherm model. Furthermore, the desorption and regeneration studies have proven that MPDVB can be employed repeatedly without impacting its adsorption capacity.

Electrochemical treatment of olive mill wastewater: treatment extent and effluent phenolic compounds monitoring using some uncommon analytical tools.

Problems related with industrials effluents can be divided in two parts: (1) their toxicity associated to their chemical content which should be removed before discharging the wastewater into the receptor media; (2) and the second part is linked to the difficulties of pollution characterisation and monitoring caused by the complexity of these matrixes. This investigation deals with these two aspects, an electrochemical treatment method of an olive mill wastewater (OMW) under platinized expanded titanium electrodes using a modified Grignard reactor for toxicity removal as well as the exploration of the use of some specific analytical tools to monitor effluent phenolic compounds elimination. The results showed that electrochemical oxidation is able to remove/mitigate the OMW pollution. Indeed, 87% of OMW color was removed and all aromatic compounds were disappeared from the solution by anodic oxidation. Moreover, 55% of the chemical oxygen demand (COD) and the total organic carbon (TOC) were reduced. On the other hand, UV-Visible spectrophotometry, Gaz chromatography/mass spectrometry, cyclic voltammetry and 13C Nuclear Magnetic Resonance (NMR) showed that the used treatment seems efficaciously to eliminate phenolic compounds from OMW. It was concluded that electrochemical oxidation in a modified Grignard reactor is a promising process for the destruction of all phenolic compounds present in OMW. Among the monitoring analytical tools applied, cyclic voltammetry and 13C NMR a re among th e techniques that are introduced for thefirst time to control the advancement of the OMW treatment and gave a close insight on polyphenols disappearance.

Benthic foraminiferal assemblages as pollution proxies in the northern coast of Gabes Gulf, Tunisia.

A study of chemical and sedimentological parameters integrated with benthic foraminifera investigation was conducted along the northern coast of Gabes Gulf. Thirty-two samples were studied and a total of 68 benthic foraminiferal species were identified. Heavy metals enrichment factors and total hydrocarbon concentrations showed both metal and petrogenic pollution related mainly to phosphogypsum, sewage, and fishing activities. Statistical analysis (bivariate correlation and hierarchical cluster analysis) show a possible control of these pollutants on density, diversity, as well as the taxonomic composition of the benthic foraminiferal assemblages. The extent to which the population was found less dense and less diversified corresponded to the degree to which the sediment was contaminated. In these contaminated sites, an increase in relative abundance of opportunistic species such Ammonia tepida and Haynesina germanica was found. Far from pollution, foraminiferal assemblages are dominated by species characteristic of Mediterranean shallow water (Ammonia beccarii, Ammonia parkinsoniana, Elphidium crispum, Elphidium williamsoni, Elphidium advenum, Peneroplis planatus, Peneroplis pertesus).

A case study on co-exposure to a mixture of organic solvents in a Tunisian adhesive-producing company.

OBJECTIVES: to assess environmental and biological monitoring of exposure to organic solvents in a glue-manufacturing company in Sfax, Tunisia. METHODS: Exposure of volunteer workers, in the solvented glue-work-stations, in the control laboratory and in the storage rooms of the finished products, was assessed through indoor-air and urine measurements. Informed consent of the workers was obtained. RESULTS AND DISCUSSION: The exposure indexes were found with high values in the solvented workshop as well as in the control laboratory and were respectively, 8.40 and 3.12. These indexes were also correlated with hexane and toluene indoor air concentrations. As to urine, the obtained results for the 2,5-hexandione and hippuric acid, metabolites of hexane and toluene, respectively, were in accord with the indoor-air measurements, with an average of 0.46 mg/l and 1240 mg/g of creatinine. CONCLUSION: This study assessed for the first time biological exposure to organic solvents used in Tunisian adhesive industries. Although values are likely to underestimate true exposure levels, some figures exceed European and American occupational exposure guidelines.

Effect of chronic and subchronic organic solvents exposure on balance control of workers in plant manufacturing adhesive materials.

High-level occupational exposure to volatile organic solvents may elicit neurotoxic effects, especially on central and peripheral structures involved in balance ability. Studies on balance control in relation with exposure levels close to the threshold limit values are scarce. This study aimed to assess the neurotoxic effects of chronic and subchronic exposure to organic solvents among workers in plant manufacturing adhesive materials. Balance control was evaluated in 18 subjects, mainly exposed to n-hexane and toluene, with current median exposure levels of 222 and 102 mg/m(3), respectively, and a median exposure duration of 21 years, and in 32 nonexposed controls, using posturography tests with and without sensory conflicting situations. Tests were undergone at the beginning of the work shift (chronic exposure) following a week end, and after 72 h (subchronic exposure). Balance control performance was lower in chronically exposed workers compared to controls, and got worse after subchronic exposure, particularly during situations, where vestibular information was important. Our study suggests that a low-level and prolonged exposure to volatile organic solvents, mainly n-hexane and toluene, in the workplace is associated with deleterious central effects involved in postural regulation. This neurotoxicity is characterized by difficulties to use the most relevant information to control balance, leading to altered management of sensory conflicting situations.

Olive mill wastewater degradation by Fenton oxidation with zero-valent iron and hydrogen peroxide.

The degradation of olive mill wastewater (OMW) with hydroxyl radicals generated from zero-valent iron and hydrogen peroxide has been investigated by means of chemical oxygen demand (COD) and phenolic compounds analyses. The effects of the H2O2 dose, the pH and the organic matter concentration have been studied. The optimal experimental conditions were found to have continuous presence of iron metal, acid pH (2.0-4.0), and relatively concentrated hydrogen peroxide (9.5M). Coloration of OMW disappeared and phenolic compound decreased to 50% of initial concentration after 3h reaction time. The application of zero-valent Fe/H2O2 procedure permitted high removal efficiencies of pollutants from olive mill wastewater. The results show that zero-valent Fe/H2O2 could be considered as an effective alternative solution for the treatment of OMW or may be combined with a classical biological process to achieve high quality of effluent water.