Monitoring of water quality inflow and outflow of a farm in Italian Padana plain for rice cultivation: a case study of two years

Environmental Science and Pollution Research - Rice cultivation requires a large use of pesticides and nutrients to control weed proliferation and improve production. The water quality of four...     

Preliminary toxicological assessment of phthalate esters from drinking water consumed in Portugal

This paper reports, for the first time, the concentrations of selected phthalates in drinking water consumed in Portugal. The use of bottled water in Portugal has increased in recent years. The main material for bottles is polyethylene terephthalate (PET). Its plasticizer components can contaminate water by leaching, and several scientific studies have evidenced potential health risks of phthalates to humans of all ages. With water being one of the most essential elements to human health and because it is consumed by ingestion, the evaluation of drinking water quality, with respect to phthalate contents, is important. This study tested seven commercial brands of bottled water consumed in Portugal, six PET and one glass (the most consumed) bottled water. Furthermore, tap water from Lisbon and three small neighbor cities was analyzed. Phthalates (di-n-butyl phthalate ester (DnBP), bis(2-ethylhexyl) phthalate ester (DEHP), and di-i-butyl phthalate ester (DIBP)) in water samples were quantified (PET and glass) by means of direct immersion solid-phase microextraction and ionic liquid gas chromatography associated with flame ionization detection or mass spectrometry due to their high boiling points and water solubility. The method utilized in this study showed a linear range for target phthalates between 0.02 and 6.5 μg L^?1, good precision and low limits of detection that were between 0.01 and 0.06 μg L^?1, and quantitation between 0.04 and 0.19 μg L^?1. Only three phthalates were detected in Portuguese drinking waters: dibutyl (DnBP), diisobutyl (DIBP), and di(ethylhexyl) phthalate (DEHP). Concentrations ranged between 0.06 and 6.5 μg L^?1 for DnBP, between 0.02 and 0.16 μg L^?1 for DEHP, and between 0.1 and 1.89 μg L^?1 for DIBP. The concentration of DEHP was found to be up to five times higher in PET than in glass bottled water. Surprisingly, all the three phthalates were detected in glass bottled water with the amount of DnBP being higher (6.5 μg L^?1) than in PET bottled water. These concentrations do not represent direct risk to human health. Regarding potable tap water, only DIBP and DEHP were detected. Two of the cities showed concentration of all three phthalates in their water below the limits of detection of the method. All the samples showed phthalate concentrations below 6 μg L^?1, the maximum admissible concentration in water established by the US Environmental Protection Agency. The concentrations measured in Portuguese bottled waters do not represent any risk for adult's health.     

Study on the photodegradation of amidosulfuron in aqueous solutions by LC-MS/MS

Sulfonylurea herbicides are extensively widespread for the protection of a variety of crops and vegetables because of their low application rates, high selectivity and low persistency in the environment; unfortunately, their low persistence does not always correspond to a lower toxicity, since new species potentially more toxic and stable than the precursor herbicides can form, owing to natural degradation processes. Here, the photodegradation of amidosulfuron in aqueous solutions was studied by high-performance liquid chromatography with diode array detection and tandem mass spectrometry to identify the degradation products in order to outline the environmental fate of the molecules generating from the simulation of one of the natural processes that can occur, i.e., photoinduced degradation. The photodegradation process results in a first order kinetic reaction with a t _1/2 value of 276 h (11.5 days) and a kinetic constant of 0.0027 h^?1, and three possible degradation products were identified. The results obtained are then compared to those obtained in previous works carried out in comparable experimental conditions about nicosulfuron and tribenuron-methyl, two sulfonylurea herbicides belonging to different classes, and to literature data: hypotheses on the existence of preferential degradation pathways are then drawn, in consequence of the molecular structure of the sulfonylurea pesticide. In particular, the use of organic solvents to obtain complete solubilization of the sample plays a fundamental role and deeply influences the degradation processes that, therefore, not always fully adhere to the actual natural photodegradation pathways. Moreover, considerations about toxicity were driven since the complete mineralisation of the sample is not reached: even when the parent pesticides are totally degraded, they are, however, transformed into other organic compounds showing, if subject to ecotoxicological tests, at least the same toxicity of the precursor herbicides. The evidence here presented suggests that, at least for the class of sulfonylurea pesticides, their professed low persistence actually does not produce any real advantage.     

Photodegradation of the pure and formulated alpha-cypermethrin insecticide gives different products

Alpha-cypermethrin is a broad-spectrum insecticide widely used in the treatment of rice crops, mainly commercialized as a CONTEST^® formulation. The photodegradation of alpha-cypermethrin and of the commercial formulation has not yet been systematically investigated in paddy water under natural conditions. Here, paddy water solutions of alpha-cypermethrin and CONTEST^® formulation at 5.0 mg L^?1 were irradiated under simulated sunlight for 10 days. Hydrolysis experiments were carried out on the same solutions preserved in the dark. Analysis by ultra-high-performance liquid chromatography–tandem mass spectrometry was developed for the identification of photodegradation products. Results show that degradation of pure alpha-cypermethrin and the formulation counterpart produces both common and different photodegradation products. Five out eleven photodegradation products were identified for the first time, in particular three in the alpha-cypermethrin paddy water solution and four in the formulation. Our findings underline the importance of carrying out photodegradation experiments directly on the commercial formulation, since degradation products could be different from the pure insecticide.     

Genetic divergence among three sympatric species of Mediterranean Patella (Archaeogastropoda)

Patella caerulea L., P. aspera Lam. (=P. ulyssiponensis Gmelin). P. rustica L. (=P. lusitanica Gmelin) are coexisting Mediterranean species of the genus Patella. P. caerulea and P. rustica have a haploid complement of n=9 with seven metacentric and two telocentric chromosomes, while P. aspera has a haploid complement of n=8 without telocentric chromosomes. To better define the phylogenetic relationships among these three species, an electrophoretic analysis of 12 enzyme coding loci was performed on samples of the three species collected from Laigueglia (Liguria, Italy) in 1989. On the whole, genotypic frequencies were in agreement with Hardy-Weinberg expectations and no significant differences were observed among the populations of the three species as far as their genetic structure is concerned. Nearly 50% of the sampled loci were diagnostic. Nei's genetic distance was 0.82 between P. caerulea and P. aspera, 0.97 between P. aspera and P. rustica and 0.94 between P. caerulea and P. rustica. By greatly separating P. rustica from the other two species, results of the electrophoretic analysis are consistent with the traditional view, which regards P. aspera and P. caerulea as more closely related than P. rustica on the basis of radular teeth morphology. Using genetic distances and the assumptions of the molecular clock, lineages leading to P. aspera and to P. caerulea may have diverged from the stem common to P. rustica ca. 18 million years ago.