Domoic acid at trace levels in lagoon waters: assessment of a method using internal standard quantification.

Domoic acid (DA) is a neurotoxin produced by different algae, including pennate diatoms, principally from the genus Pseudo-nitzschia, and it is the main cause of amnesic shellfish poisoning. Determination of this toxin in seawater samples is fundamental to define the real contamination risks for aquatic species. We have developed two very sensitive instrumental methods using hydrophilic interaction liquid chromatography coupled using tandem mass spectrometry in positive and negative polarity modes. Instrumental detection limits were 9 pg mL(-1) for positive and 19 pg mL(-1) for negative ionisation. A procedural method based on solid-phase extraction for the determination of dissolved DA present in seawater has been developed, and an extraction procedure was employed for the determination of the toxin in the particulate fraction. DA quantification was performed using the internal standard method to account for signals fluctuations and random errors during sample treatment. To our knowledge, this is the first study to use this quantification method for DA determination. Trueness, extraction yield, matrix effects, repeatability and procedural detection limits were evaluated during method validation. Procedural detection limits of 0.3 pg mL(-1) (positive mode) and 0.6 pg mL(-1) (negative mode) were found for the dissolved fraction, and absolute limits of 0.4 pg (positive mode) and 6.0 pg (negative mode) for particulate samples were obtained. The most sensitive method in positive mode was applied to define DA occurrence in the Venice Lagoon. Trace concentrations of domoic acid ranging from 1.5 to 16.2 pg mL(-1) were found for the first time in the Venetian environment.

Sources of high PM2.5 concentrations in Milan, Northern Italy: molecular marker data and CMB modelling.

In Milan (MI), the largest city in Northern Italy, the annually average PM2.5 concentration is above 25 µg m(-3), the value that the EU established as a target for 2010, and the upper limit from 2015 onwards (2008/30/CE). Over a three-year period (2006-2009) PM concentrations and chemical compositions were measured in an urban site (MI), a rural site (OB) and a remote site (ASC) in Northern Italy. Chemical characterization (EC/OC, inorganic ions, elements, C20-C32 n-alkanes, C2-C5 mono and dicarboxylic acids, levoglucosan and PAHs) was carried out on PM2.5 samples from the three sites, and PM10 from MI. Molecular markers were used in Chemical Mass Balance (CMB) modelling to estimate the contributions of primary sources to OC, and then PM mass from each source was reconstructed in MI, OB and ASC for different seasons. Estimates of the traffic (TR) source contribution to PM2.5 mass ranged from 4.1 (± 2.0) µg m(-3) during the summer, to 13.3 (± 6.7) µg m(-3) during the winter in MI. TR was the main primary source for PM2.5 concentrations in MI (17-24%). Its contribution was lower at the OB site (7-9%) and at the remote ASC site (3-4%). TR is a local source, while biomass burning (BB) is a diffuse regional source in Northern Italy: during fall and winter, BB was 25-30% and 27-31% of PM2.5 at MI and OB respectively. Other primary sources accounted for a small amount of the PM2.5, i.e. natural gas combustion (0-1%), plant debris (0-4%), road dust (RD=0-4%; but 15% at ASC during winter and 10% of PM10 at MI during summer) and sea salt (0-1%). Secondary inorganic+organic aerosol constituted the major part of the PM2.5 mass during spring and summer (50-65%) at the three sites.

Polychlorinated biphenyls in sediments of the Tam Giang-Cau Hai Lagoon, Central Vietnam.

The Tam Giang-Cau Hai Lagoon, the largest in south east Asia, suffers from a great anthropogenic pressure and appears subject to a process of progressive environmental deterioration. To establish causes, history and trends of lagoon contamination, sediment samples representing three major parts of the systems were sampled and analysed for porosity, organic carbon, total nitrogen, delta(13)C, grain size, radiotracers and PCBs. PCB surficial concentrations range from 10.2 to 24.5 microg kg(-1), and maximum values are close to NOAA ERL guidelines. The downcore distribution of PCBs shows two well defined peaks in the core from Tam Giang (25.5 and 16.2 microg kg(-1)), whereas the sediment from Cau Hai is characterised by a maximum at the surface. Therefore, present trends indicate that contamination is still increasing or slightly decreasing. The prevailing congeners are 3-CB and 4-CB, hence recent PCBs appear to be mostly originated by Aroclor 1016- and 1242-like mixtures, with some samples influenced also by Aroclor 1248. Present sources seem to be similar everywhere and probably they are widespread all over the territory of the Thua Thien-Hue province.