Nonylphenol (NP), nonylphenol mono-and di-ethoxylate (NP1EO, NP2EO) and bisphenol A (BPA) were determined in water, suspended particulate matter (s.p.m.) and bed sediment collected from the most polluted stretch of Tiber river (Italy) in the neighbourhood of Rome. Analytes were recovered from water samples by solid-phase extraction (SPE) on Si-C 18 cartridges and analysed by HPLC with fluorescence detection. Solid samples were extracted by using an aqueous solution of the non-ionic surfactant Tween 80.Results indicated that 2-42% of NP, 9-45% of NP1EO, 11-18% of NP2EO and 4-62% of BPA respectively occurred in the suspended phase. In general, for all compounds a higher affinity for s.p.m. than for bed sediments was observed, reflecting differences in the nature of particles and in their sorption capacity for organic micro-pollutants. The partition of target compounds in river compartments was affected by differences in hydrological conditions between the two sampling campaigns. Run-off from the basin or resuspension/redissolution from sediments was an important source of nonylphenol and bisphenol A during high discharge regimes. Partition coefficients of compounds (log K oc ) between water and s.p.m. were calculated under stable flow condition. K oc values, experimentally measured in the river, were higher than those predicted by K ow , implying that specific chemical interaction could occur in the sorption mechanisms for these group of compounds.
In the present work, the oligochaete Lumbriculus variegatus was exposed for 56 d to lake sediment spiked with 4-nonylphenol (4-NP), which is a breakdown product of alkylphenol polyethoxylates, an important class of nonionic surfactants. During the exposure period, the content of 4-NP was determined in the oligochaetes, sediment, overlying water, and pore water in order to monitor the distribution of the 4-NP in the compartments of the test system. Concentration of 4-NP in L. variegatus increased linearly over the course of the test, with an uptake rate coefficient of 1.9 x 10(-2) (+/- 0.2 x 10(-2); [g carbon/(g lipid x h)]). No steady state was reached at the end of the exposure period, suggesting that the elimination of 4-NP by the organism was negligible. Ingested sediments played an important role in the accumulation of 4-NP in L. variegatus, which may achieve very high 4-NP body concentrations. The 56-d biota sediment accumulation factor (BSAF) was 24 +/- 7 g carbon/g lipid. L. variegatus also was exposed to 4-NP-contaminated field sediment, and field oligochaetes and sediments were collected for 4-NP pollution assessment in aquatic ecosystem. The 4-NP uptake with natural sediment was in accordance with that measured with spiked sediments, suggesting that the bioavailability of sediment-associated 4-NP for L. variegatus was not affected by 4-NP sediment concentration and abiotic sediment characteristics. The BSAFs measured in field oligochaetes, ranging from 39 to 55 g carbon/g lipid, was relatively higher than the bioaccumulation factor measured in laboratory tests. The results suggest that 4-NP concentration can reach high levels in benthic oligochaetes; this can be an important way of exposure for their pelagic predators.
Preparation of 2-Zincio-1,3-dithianes and Di(1,3-dithian-2-yl)zinc and Their Reaction with Highly Functionalized Halides and α,β-Unsaturated Carbonyl Compounds.-Lithiation of 1,3-dithianes (I) followed by transmetalation with zinc chloride gives 2-zincio-1,3-dithianes. They readily react with electrophiles. Transmetalation with 0.5 equivalent of zinc salt provides a di(1,3-dithian-2-yl)zinc, which effectively adds to the enone (VI). -(CERE, V.; DE ANGELIS, S.; POLLICINO, S.; RICCI, A.; REDDY, CH. K.; KNOCHEL, P.; CAHIEZ, G.; Synthesis
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