A simple procedure to harmonize class boundaries of assessment systems at the pan-European scale

A procedure for a large scale harmonization of assessment systems is delineated. The data collected for the two E.U. co-funded projects STAR and AQEM have been used as a benchmark dataset against which a test dataset derived from Italian standard monitoring programs was compared. A central step in the procedure adopted is the calculation of Intercalibration Common Metrics (STAR_ICMs). For both the benchmark and test datasets, six metrics were calculated, normalized and averaged to obtain an ICM index. The median values obtained for this index within each of the High and Good status classes, as defined within the STAR/AQEM dataset, were compared to the classes defined by the National method applied in Italy before WFD approval. The process of harmonization involved the re-positioning of the boundaries between Italian method quality classes until no more differences were found with the values observed in the STAR/AQEM samples. The re-setting of the Italian assessment boundaries by a step-by-step procedure lead to comparable STAR_ICM index values in the two datasets. Within this example, small refinements of the boundaries between high/good and good/moderate status were sufficient to harmonize the Italian assessment quality classes to the benchmark classification. Once a benchmark dataset is agreed among different countries, the procedure outlined can be easily applied to compare and harmonize assessment systems within and outside Europe. The main scientific and practical advantages of the procedure are listed and commented, especially facing the next steps of the Water Framework Directive Intercalibration process.     

Kinetic and chemical assessment of the UV/H2O2 treatment of antiepileptic drug carbamazepine

The UV/H2O2-induced degradation of carbamazepine, a worldwide used antiepileptic drug, recently found as contaminant in many municipal sewage treatment plant (STP) effluents and other aquatic environments, is investigated. The oxidation treatment caused an effective removal of the drug. At complete abatement of the substrate after 4 min treatment, a 35% value of removed total organic carbon (TOC) was obtained. A kinetic constant of (2.05+/-0.14) x 10(9) lmol(-1)s(-1) was determined for OH radical attack to carbamazepine in the UV/H2O2 process. Preparative TLC of the reaction mixture led to the isolation of acridine-9-carboxaldehyde as a reaction intermediate. HPLC and GC/MS analysis indicated formation of small amounts of acridine, salicylic acid, catechol and anthranilic acid among the reaction products. Under the same reaction conditions, synthetically prepared 10,11-epoxycarbamazepine was easily degraded to acridine as main product, suggesting that this epoxide is a likely intermediate in the oxidative conversion of carbamazepine to acridine. Under sunlight irradiation, carbamazepine in water underwent slow degradation to afford likewise acridine as main product. In view of the mutagenic properties of acridine, these results would raise important issues concerning the possible environmental impact of carbamazepine release through domestic wastewaters and support the importance of prolonged oxidation treatments to ensure complete degradation of aromatic intermediates.     

Effects of sensitizers on the photodegradation of the systemic fungicide triadimenol

The photochemical behaviour of triadimenol (1) under various conditions has been examined. Significant degradation is obtained only in the presence of electron-acceptor sensitizers as 9,10-dicyanoanthracene or 2,4,6-triphenylpyrylium tetrafluoroborate, and long irradiation times are required. 1H-1,2,4-Triazole (2), 4-chlorophenyl formate (3), 4-chlorophenol (4), 1-(4-chlorophenoxy)-3,3-dimethyl-1-(1H-1,2,4-triazol-1-yl)butan-2-one (5), 4-chlorophenyl 2,2-dimethylpropanoate (6) and 4-chlorobenzoic acid (7) were identified as photoproducts by NMR and GC-MS.     

Stream water chemistry in the arsenic-contaminated Baccu Locci mine watershed (Sardinia, Italy) after remediation

The abandoned Pb–As Baccu Locci mine represents the first and only case of mine site remediation in Sardinia, Italy. Arsenic is the most relevant environmental concern in the Baccu Locci stream watershed, with concentrations in surface waters up to and sometimes over 1 mg/L. The main remediation action consisted in creation of a “storage site”, for the collection of contaminated materials from different waste-rock dumps and most of tailings piles occurring along the Baccu Locci stream. This paper reports preliminary results on the level of contamination in the Baccu Locci stream after the completion of remediation measures. Post-remediation stream water chemistry has not substantially changed compared to the pre-remediation situation. In particular, dissolved As maintains an increasing trend along the Baccu Locci stream, with a concentration of about 400 μg/L measured at a distance of 7 km from the storage site. Future monitoring will provide fundamental information on the effectiveness of remediation actions conducted and their applicability to other mine sites in Sardinia. At the stage of mine site characterisation of future remediation plans, it is recommended to pay more attention to the understanding of mineralogical and geochemical processes responsible for pollution. Moreover, mixing of materials with different composition and reactivity in a storage site should require careful consideration and long-term leaching tests.     

Cartilage chondroprotection and repair with pulsed electromagnetic fields: I-ONE therapy

Articular cartilage is a complex tissue characterised by chondrocytes that are embedded within an organised dense extracellular matrix of collagen and proteoglycan. Under physiologic condition, articular metabolism is slow, but under pathological condition turnover can increase and the matrix undergoes faster mechanical failure and deterioration, resulting in cartilage degeneration. Moreover, modest damage of the articular cartilage, resulting from trauma or less invasive surgical procedure, produces an inflammatory reaction of the joint cartilage, which can cause irreversible degeneration through the increase in catabolic cytokines synthesis and the decrease in anabolic activity of chondrocytes. Pro-inflammatory cytokines increase the synthesis of matrix-degrading enzymes and limit the production of proteoglycans. It is known that physical stimuli modulate cartilage metabolism. In particular, pulsed electromagnetic fields (I-ONE therapy, Igea, Carpi, Italy) allow to treat homogenously the whole cartilage surface and thickness and the underlying subchondral bone. In vitro I-ONE therapy increases the binding between adenosine and A_2A adenosine receptor on human neutrophils cell membrane, on bovine chondrocytes and on fibroblast-like synoviocytes. It has been shown that drugs with A_2A adenosine receptor agonist activity prevent articular cartilage degeneration in animals. We hypothesised that the adenosine agonist effect of I-ONE therapy can also prevent cartilage degeneration. In a recent study, De Mattei et al. demonstrated how I-ONE therapy can strongly inhibit the release of PGE₂ in bovine synovial fibroblasts exerting an anti-apoptotic effect on cells. Ex vitro, in bovine full thickness articular cartilage explants, I-ONE therapy induces the largest increase in proteoglycan synthesis and in IGF-1 synthesis, when cartilage is exposed to specific parameters of pulsed electromagnetic fields. These effective parameters were subsequently used in in vivo experiments. The effect of I-ONE therapy was investigated on Dunkin Hartley osteoarthritic knee by Mankin score and by histomorphometric and densitometric analysis; I-ONE therapy prevented cartilage degeneration and subchondral bone sclerosis. Osteochondral grafts were performed in the knees of sheep; I-ONE therapy favoured osteochondral grafts integration and prevented cyst-like resorption area formation, which can compromise the stability of graft and the success of the technique. To support the in vitro results, biochemical analyses of the synovial fluid were also performed in this animal model. The amount of inflammatory catabolic cytokines (IL-1β and TNF-α) in the synovial fluid of I-ONE treated animals was significantly lower than in control animals. On the contrary, TGF-β1 was significantly higher in stimulated animals than it was in controls. These results demonstrate not only the capability of I-ONE therapy to control the inflammatory reaction but also its capability to favour cartilage anabolic activity. These results provide the rational to design clinical studies to demonstrate the possibility to transfer the treatment to humans. Two randomised, prospective, double-blind clinical studies (Level I), one conducted to patients treated by arthroscopy with condroabrasion and/or perforations at the knee and the other after anterior cruciate ligament reconstruction, demonstrated that biophysical stimulation with I-ONE therapy leads to complete patient’s recovery in a significantly shorter time (P < 0.005). Moreover, a significant number of treated patients made lower use of anti-inflammatory drugs than the patients in the placebo group. We did not observe negative side effects, patient’s compliance was good and treatment was well accepted. I-ONE therapy significantly reduces patients’ recovery time, joint swelling and has a chondroprotective effect over articular cartilage. I-ONE treatment is a new therapy for the joint preservation.     

Evaluation of ABC efflux transporters genes expression in kidney of rainbow trout (Oncorhynchus mykiss) fed with melamine and cyanuric acid diets

Gene expression experiments were targeted in order to monitor the ABC efflux transporters, which is potentially involved in cellular detoxification/defense. Changes in expression levels of different ABC genes in kidney of Oncorhynchus mykiss fed with melamine and melamine + cyanuric acid enriched diets were recorded in both treated groups by mRNA ΔΔ_CT relative quantification method. Expression profiles of eight different ABC genes basically showed low alterations in melamine group and more consistent changes in melamine + cyanuric acid treated fish, compared with own control. In the last group ABCC2 gene over expression was the more evident alteration. These results suggest that ABC efflux system could be involved in mobilization of hydrophilic molecules in the forcing condition of chronic exposure.     

Hormetic effect(s) of tetracyclines as environmental contaminant on Zea mays

Animal wastes from intensive pig farming as fertilizers may expose crops to antimicrobials. Zea mays cultivations were carried out on a virgin field, subjected to dressing with pig slurries contaminated at 15 mg L⁻¹ of Oxy- and 5 mg L⁻¹ of Chlor-tetracycline, and at 8 mg L⁻¹ of Oxy and 3 mg L⁻¹ of Chlor, respectively. Pot cultivation was performed outdoor (Oxy in the range 62.5-1000 ng g⁻¹ dry soil) and plants harvested after 45 days. Tetracyclines analyses on soils and on field plants (roots, stalks, and leaves) did not determine the appreciable presence of tetracyclines. Residues were found in the 45-day pot corn only, in the range of 1-50 ng g⁻¹ for Oxy in roots, accounting for a 5% carry-over rate, on average. Although no detectable residues in plants from on land cultivations, both experimental batches showed the same biphasic growth form corresponding to a dose/response hormetic curve.