Occurrence of phthalic acid esters (PAEs) and active pharmaceutical ingredients (APIs) in key species of anthozoans in Mediterranean Sea.

The Mediterranean Sea's biodiversity is declining due to climate change and human activities, with plastics and emerging contaminants (ECs) posing significant threats. This study assessed phthalic acid esters (PAEs) and active pharmaceutical ingredients (APIs) occurrence in four anthozoan species (Cladocora caespitosa, Eunicella cavolini, Madracis pharensis, Parazoanthus axinellae) using solid phase microextraction (SPME) and liquid chromatography coupled to tandem mass spectrometry (LC-MS/MS). All specimens were contaminated with at least one contaminant, reaching maximum values of 57.3 ng/g for the ∑PAEs and 64.2 ng/g (wet weight) for ∑APIs, with dibutyl phthalate and Ketoprofen being the most abundant. P. axinellae was the most contaminated species, indicating higher susceptibility to bioaccumulation, while the other three species showed two-fold lower concentrations. Moreover, the potential adverse effects of these contaminants on anthozoans have been discussed. Investigating the impact of PAEs and APIs on these species is crucial, given their key role in the Mediterranean benthic communities.

Hotspots of microplastic accumulation at the land-sea transition and their spatial heterogeneity: The Po River prodelta (Adriatic Sea).

Deltas are the locus of river-borne sediment accumulation, however, their role in sequestering plastic pollutants is still overlooked. By combining geomorphological, sedimentological, and geochemical analyses, which include time-lapse multibeam bathymetry, sediment provenance, and µFT-IR analyses, we investigate the fate of plastic particles after a river flood event providing an unprecedented documentation of the spatial distribution of sediment as well as of microplastics (MPs), including particles fibers, and phthalates (PAEs) abundances in the subaqueous delta. Overall sediments are characterized by an average of 139.7 ± 80 MPs/kg d.w., but display spatial heterogeneity of sediment and MPs accumulation: MPs are absent within the active sandy delta lobe, reflecting dilution by clastic sediment (ca. 1.3 Mm3) and sediment bypass. The highest MP concentration (625 MPs/kg d.w.) occurs in the distal reaches of the active lobe where flow energy dissipates. In addition to MPs, cellulosic fibers are relevant (of up to 3800 fibers/kg d.w.) in all the analyzed sediment samples, and dominate (94 %) with respect to synthetic polymers. Statistically significant differences in the relative concentration of fiber fragments ≤0.5 mm in size were highlighted between the active delta lobe and the migrating bedforms in the prodelta. Fibers were found to slightly follow a power law size distribution coherent with a one-dimensional fragmentation model and thus indicating the absence of a size dependent selection mechanism during burial. Multivariate statistical analysis suggests traveling distance and bottom-transport regime as the most relevant factors controlling particle distribution. Our findings suggest that subaqueous prodelta should be considered hot spots for the accumulation of MPs and associated pollutants, albeit the strong lateral heterogeneity in their abundances reflects changes in the relative influence of fluvial and marine processes.

Correction to: Biodegradation of naphthenic acids: identification of Rhodococcus opacus R7 genes as molecular markers for environmental monitoring and their application in slurry microcosms.

The published online version contains mistake in the author list for the author "M. Cappelletti" was incorrectly presented.

Biodegradation of naphthenic acids: identification of Rhodococcus opacus R7 genes as molecular markers for environmental monitoring and their application in slurry microcosms.

Nowadays, the increase of the unconventional oil deposit exploitation and the amount of oil sands process-affected waters (OSPW) in tailing ponds emerges the importance of developing bio-monitoring strategies for the restoration of these habitats. The major constituents of such deposits are naphthenic acids (NAs), emerging contaminant mixtures with toxic and recalcitrant properties. With the aim of developing bio-monitoring strategies based on culture-independent approach, we identified genes coding for enzymes involved in NA degradation from Rhodococcus opacus R7 genome, after the evaluation of its ability to mineralize model NAs. R. opacus R7 whole-genome analysis unveiled the presence of pobA and chcpca gene clusters putatively involved in NAs degradation. Gene expression analysis demonstrated the specific induction of R7 aliA1 gene, encoding for a long-chain-fatty-acid-CoA ligase, in the presence of cyclohexanecarboxylic acid (CHCA) and hexanoic acid (HA), selected as representative compounds for alicyclic and linear NAs, respectively. Therefore, aliA1 gene was selected as a molecular marker to monitor the biodegradative potential of slurry-phase sand microcosms in different conditions: spiked with CHCA, in the presence of R. opacus R7, the autochthonous microbial community, and combining these factors. Results revealed that the aliA1-targeting culture-independent approach could be a useful method for bio-monitoring of NA degradation in a model laboratory system.

Slurry phase bioremediation of PAHs in industrial landfill samples at laboratory scale.

The effect of Tween 80 and selected bacteria additions on the bioremediation of PAH contaminated landfill soil (70.38mgkg(-1)) was evaluated in a slurry phase bioreactor. A phenanthrene-degrading consortium was selected by enrichment cultures and used as autochthonous inoculum. The Tween 80 addition increased the aqueous concentration of both high and low molecular weight PAHs. In the experiment with Tween 80 and inoculum addition, added microorganisms improved (>90%) the biodegradation of two- and three-ring PAHs as well as of the four-ring PAHs pyrene and fluoranthene. Biodegradation of the higher molecular weight PAHs was about 30% in experiments with Tween 80 addition, with and without inoculum addition.

Selection of surfactants for enhancing diesel hydrocarbons-contaminated media bioremediation.

The use of surfactants represents a valuable method to enhance the access of the microorganisms to low-soluble and recalcitrant compounds in bioremediation techniques. The choice of surfactants is the first step of feasibility studies for this application. So far, no defined procedures are present in literature to select the most suitable surfactant for the treatment of a specific contaminated site. Furthermore, the characterisation of physico-chemical parameters is important to understand the reason of successes and failures. In this paper a step procedure to select and characterise a commercial surfactant to be used in bioremediation enhancement of hydrocarbon-contaminated media was developed. Among the commercial surfactants, the procedure was applied to alkyl polyethoxylates (Brij family) and sorbitan derivates (Tween family). The selection resulted in the application of Brij 56 and Tween 80 as biodegradation-enhancer in different lab scale systems for remediation of diesel contamination. In liquid systems, Tween 80 greatly increased biodegradation of highly branched and high-molecular weight hydrocarbons, while Brij 56 enhanced degradation of highly branched hydrocarbons. Based on these results, the potential applications and the limitations of these surfactants at full scale level were estimated.

Dioxygenation of naphthalene by Pseudomonas fluorescens N3 dioxygenase: optimization of the process parameters.

The bioconversion of naphthalene to the 1,2-dihydro-1,2-dihydroxy derivative was performed in good yield using an Escherichia coli recombinant strain carrying Pseudomonas fluorescens N3 dioxygenase. However, the efficiency of such transformation is affected by many process parameters, and their optimization is essential to the scaling up of the process. The following process parameters were considered for optimization: cell concentration together with the corresponding glucose concentration (DCW/L); pH of medium; temperature; stirring speed; air flow; substrate concentration; Fe(2+) concentration; microelements concentration; reaction volume. We used a two-step multivariate experimental design to select important variables and assign them optimal values. The most significant parameters were selected by adopting a Plackett-Burman design, and were then correlated, using a full factorial design, with the experimental results. The experimental results illustrate that the optimized process of recombinant whole cell biotransformation in two-liquid phase systems enhances the naphthalene dihydrodiol yield threefold. This biotransformation opens the way to future experiments involving different substrates.

Bioremediation of diethylhexyl phthalate contaminated soil: a feasibility study in slurry- and solid-phase reactors.

The aim of the research was to verify the possibility of applying bioremediation as a treatment strategy on a poly(vinyl chloride) (PVC) manufacturing site in the north of Italy contaminated by diethylhexyl phthalate (DEHP) at a concentration of 5.51 mg/g of dry soil. Biodegradation kinetic experiments with DEHP contaminated soil samples were performed in both slurry- and solid-phase systems. The slurry-phase results showed that the cultural conditions, such as N and P concentrations and the addition of a selected DEHP degrading strain, increased the natural DEHP degradation rate. On the basis of these data, experiments to simulate bioventing on contaminated soil columns were performed. The DEHP concentration reached 0.63 mg/g of dry soil in 76 days (89% of degradation). A kinetic equation was developed to fit the experimental data and to predict the concentration of contaminant after treatment. The data obtained are encouraging for a future in situ application of the bioventing technology.

Naphthalene biodegradation kinetics in an aerobic slurry-phase bioreactor.

The research was focused on the slurry-phase biodegradation of naphthalene in soil. Among ex situ techniques, the slurry phase offers the advantage of increased availability of contaminants to bacteria. From naphthalene contaminated soil, a Pseudomonas putida M8 strain capable to degrade naphthalene was selected. Experiments were performed in a stirred and oxygenated reactor. In this study, the influence of air flow rate and agitation rate on volatilisation and biodegradation of naphthalene was investigated. The hydrocarbon disappearance, the carbon dioxide production, and the ratio of total heterotrophic and naphthalene-degrading bacteria was monitored. The results obtained confirm that the selected bioremediation technology is successful in the treatment of contaminated soils.

MSWI fly ash particle analysis by scanning electron microscopy-energy dispersive X-ray spectroscopy.

Municipal solid waste incinerator (MSWI) fly ash was investigated to study metal distribution on the particle surface. A detailed investigation into the distribution of chlorine, copper, iron, and zinc was carried out by electron microscopy coupled with X-ray fluorescence spectroscopy. Compositional and leaching test data were used to identify the correlation of significant variables and to formulate a hypothesis about metals speciation. The presence of copper chloride, iron, and zinc oxides was inferred. The iron and zinc accumulation in the submicron nuclei indicates that these metals came from the condensation of volatile species. As far as concerns copper, morphological data together with the element correlation study suggest that this element accumulates on particles involved in heterogeneous condensation processes. Furthermore, during such processes, particles of small size containing copper are formed.

Supercritical fluid extraction: an innovative tool for a fly ash-like model support.

The performance of the supercritical fluid extraction (SFE) technique to obtain a new and more appropriate model support for PCDD/F formation studies was investigated. To characterize fly ash and model supports and relate their chemical-physical properties, surface area and pore size were determined. To evaluate the influence on reactivity of the different model supports with respect to raw fly ash, a kinetic study of the thermal behavior of dibenzofuran (DF) was performed. Rate constants as well as the activation and thermodynamic parameters for the different systems were also compared. The model support obtained from SFE was very similar to raw fly ash from the structural, physical-chemical, and kinetic points of view.

Thermal oxidation kinetics and mechanism of sludge from a wastewater treatment plant.

The organic fraction of a sludge from a wastewater biological treatment plant is characterized by the total organic carbon, TOC, content, cyclohexane and toluene extractions, and thermal desorptions in nitrogen and air flow at different temperatures. The inorganic fraction is characterized by water extraction, FT-IR spectroscopy, thermogravimetric analysis, and scanning electron microscopy/energy dispersion X-ray analysis. The thermal degradation rate of organic carbon is studied in batch experiments in air, in the 250-500 degrees C temperature range. The sample TOC is used to measure the decrease of reagent concentration with time. The TOC vs time data are well fitted by a generalized kinetic model, previously proposed for the MSWIs fly ash thermal degradation. The rate constants of the immediate carbon gasification, k2, and of the dissociative oxygen chemisorption, k1, followed by C(O) intermediate gasification, k3, together with activation and thermodynamic parameters are calculated. The rate determining step is the C(O) oxidation. The influence of desorbed or extracted organic compounds on kinetics and the role of the C(O) formation in explaining the reaction mechanism as well as the comparison with fly ash kinetics are discussed.

[Ozone therapy in lumbar sciatic pain]. / Ozonoterapia intradiscale nella lombosciatalgia.

INTRODUCTION: Medical ozone is a mixture of oxygen and ozone which can be used for several medical applications. Ozone was first applied clinically to the treatment of lumbar sciatic pain peridurally, while Pietrogrande was the first in Italy to report on its intradiscal administration to treat nucleus polposus herniation. On account of these considerations, we have decided to introduce this method in our Institute (I.C.O.T. Latina) as an alternative to surgery in the treatment of lumbar sciatic pain supported by an intradiscal hernia. MATERIAL AND METHODS: September, 1995, to April, 1997, we treated more than 1000 patients with intradiscal ozone infiltration. We prospectively analyzed the first 50 patients, with 6 months' follow-up at least; all of them were preliminarily submitted to clinical examination, electromyography, CT and MRI. After local anesthesia, we injected the disk, with 18-20 G needles and under CT or fluoroscopic guidance, with 12 ml of a mixture of oxygen and ozone at a concentration of 20-30 micrograms/ml. The treatment was repeated two or three more times at intervals of 3, 15 or, when necessary, 30 days. After each treatment, CT follow-ups were carried out and the final follow-up was made 3 months later. RESULTS: We divided our results into clinical and instrumental. As for clinical response, we had 68% positive results (40% excellent, 28% good) and 32% negative results (10% of patients underwent surgery and 22 are under medical and physical treatment). As for CT response, we had 82% positive results (36% excellent, 46% good), while no major changes between pre- and post-treatment CT findings in the remaining 18% of cases. CONCLUSIONS: Ozone therapy, thanks to its ease of execution and noninvasiveness, permits the successful outpatient treatment of lumbar sciatic pain. Moreover, the lack of major complications and the good results obtained compared to other methods, such as chemonucleolysis, percutaneous automated discectomy, microsurgery and conventional surgery, suggest that ozone therapy can be considered the treatment of choice for lumbar sciatic pain and a valid alternative to surgery in many cases.

[CT-guided percutaneous treatment of osteoid osteoma]. / Trattamento percutaneo dell'osteoma osteoide sotto guida con Tomografia Computerizzata.

CT was used to localize and guide the percutaneous ablation of osteoid osteomas in 11 patients whose age ranged 5 to 63 years. The treatment was performed directly in the CT room ensuring maximum asepsis. General anesthesia was used in children and in vertebral and sacroiliac localizations, while the peripheral block was used in peripheral localizations. In the latter cases, an ischemic band was used to reduce bleeding. A dedicated drill resection system guided by a Kirschner guide wire was used for removal. The treatment was curative in the short period in all the patients, with complete symptom remission. Only one patient required retreatment after 6 months. In our series of patients no major complications, e.g., bleeding or infections, were observed. In 8 cases the resection yielded enough material for histology. To conclude, this technique can be considered a valuable alternative to surgery in the treatment of osteoid osteomas.

[Echography, magnetic resonance and double-contrast arthrography of the rotator cuff. A prospective study in 30 patients]. / L'ecografia, la risonanza magnetica e l'artrografia con doppio mezzo di contrasto della cuffia dei rotatori. Studio prospettico in 30 pazienti.

Shoulder pain is a common clinical problem with different etiologies. Without a specific diagnosis, treatment could be ineffective, causing functional limitation, chronic pain and atrophy. US and MRI allow in many cases to correctly define the different etiologies causing shoulder pain, often due to rotator cuff conditions. From June to September 1992, thirty patients with clinically suspected acute or chronic rotator cuff lesion were studied with US, MRI and double contrast arthrography. US and MRI findings were evaluated and compared using arthrography and surgery as the gold standard. The overall accuracy of MRI was 93%: the method yielded accurate information about size and number of rotator cuff tears, and about bursal, bone and muscle involvement. US accuracy was 83% in the diagnosis of large tears, 63% in the diagnosis of small and partial tears and only 11% in the diagnosis of tendinitis. Both MRI and arthrography exhibited high accuracy (respectively 91 and 100%) in the detection of rotator cuff tears when their results were compared with surgical findings. A flow chart to be used in the patients with acute or chronic shoulder pain was drawn from the critical analysis of the above results.

[Magnetic resonance and arthroscopy of the knee. A double-blind study in 40 patients]. / Risonanza magnetica e artroscopia del ginocchio. Studio a doppio cieco in 40 pazienti.

To evaluate the capabilities of ultra-low-field MR for the high-resolution imaging of the knee with a short acquisition time, a prospective double-blind study was carried out on 40 consecutive patients with acute or chronic articular conditions who were examined with both MR imaging and arthroscopy. Three-dimensional gradient-echo MR sequences were employed which allow many thin high-resolution slices to be obtained in a relatively short time. To evaluate the results arthroscopy, performed the day after MR imaging, was considered the gold standard. MR imaging and arthroscopy were in agreement in 84.6% of meniscal tears with 91.6% sensitivity and 80% specificity, in 82% of anterior cruciate ligament lesions with 100% sensitivity and 80% specificity and in 81% of cartilage lesions with 100% sensitivity and 61% specificity. On the whole, MR imaging and arthroscopy were in agreement in 82.5% of cases with 97.2% sensitivity and 75.3% specificity. MR imaging gave more information about collateral ligament, muscle and bone involvement. These results confirm the capabilities of ultra-low-field MR imaging in the study of the knee: the technique allows diagnostic studies to be performed in a short time, at a low cost, and with similar results to those obtained with higher field strengths.

[Normal anatomy and findings in traumatic pathology of the popliteal system. A MR study]. / Anatomia normale e rilievi nella patologia traumatica del sistema popliteo. Analisi mediante RM.

To date, the lesions of the popliteal system, which are responsible for the so-called postero-lateral knee instability, are still an imperfectly known chapter of knee conditions. We retrospectively analyzed 215 consecutive MR examinations performed May-August 1991 to evaluate MR capabilities in correctly depicting both the normal anatomy and the pathologic conditions of the popliteal system. Using our standard protocols for knee study and two different magnets (0.064 and 0.5 T), we identified 23 lesions of the popliteus and of its meniscal and peritoneal insertions, and 17 lesions involving also other capsular and ligamentous structures of the knee. Coronal T1-weighted images were the best ones to correctly identify normal knee anatomy, whereas sagittal T2-weighted images were more sensitive in detecting popliteal lesions. Our results had clinical or surgical confirmation in all cases.