Atmospheric PAHs in rural, urban, industrial and beach locations in Buenos Aires Province, Argentina: sources and health risk assessment.

The first atmospheric PAHs levels and associated inhalation cancer risk were assessed over southwest Buenos Aires region by deploying PUF disk PAS samplers. Eight sampling location included coastal zones, touristic beaches, and rural inland areas were considered. PUF disks were fortified with surrogate standards and extracted by automated Soxhlet prior to GC-MS analysis. Σ16 PAHs ranged from 1.13 to 44.5 ng m-3 (10.3 ± 9.8), while urban locations showed up to 10 times higher PAH levels than rural or beach locations. Direct sources of PAHs, such as intensive vehicle traffic, heating, and general combustion activities, were identified. PAHs with four to six rings (46.62%) were predominantly Flt, Pyr, BbF, and BkF, and carcinogenic risk was expressed by BaP (0.10 ± 0.07 ng m-3) and BaPTEQs (0.26 ± 0.22 ng m-3). Inhalation ECR (2.23E-5, WHO) presented the lowest risk at beach locations. Molecular ratios and PCA showed a strong dominance in pyrolytic sources, such as biomass and coal combustion, with a particular signature in fires at inland locations. Overall, this study demonstrated that PUF disk passive air sampling provided a sound and simple approach for tracking air PAHs, their sources and public health risks, bringing a cost-effective tool for pollution control measures, even at small and remote towns. This is particularly relevant in extensive countries with medium or low income, such as Argentina.

Distribution of Butyltin Compounds in the Coastal Environment of the Bahía Blanca Estuary, Argentina.

This study evaluates for the first time the distribution and accumulation of butyltin compounds (BTs) in different compartments such as seawater, sediments, suspended particulate matter (SPM), and mussels (Brachidontes rodriguezii) in the Bahía Blanca estuary. The samples were collected from six sampling sites with different anthropogenic impacts. A better visualization and interpretation of data was achieved using chemometric tools (Tucker4 model), which made it possible to reveal the main relationships among the variables. This analysis showed the presence of BTs in all the estuarine environmental compartments, even in sites with low human intervention. The relationships found among BTs levels, seasons, and environmental matrices show the importance of biological processes such as phytoplankton blooms and remobilization of sediments (by tidal dynamics and/or periodic dredging) in BTs distribution and degradation. In addition, partition coefficients showed that mussels mainly bioaccumulate tributyltin from sediment, water and, to a lesser extent, SPM.

Adenocarcinoma de células basales / Basal cell adenocarcinoma

El adenocarcinoma de células basales, también conocido como carcinoma salival basaloide, adenoma maligno de células basales, es una neoplasia epitelial de bajo grado, infiltrante, localmente destructivo y con tendencia a ser recidivante. Su aparición es entre la 5ª y 6ª década de vida, sin predilección por sexo. Clínicamente se manifiesta con un edema o un aumento repentino de tamaño en la zona, de consistencia firme, crecimiento lento e indoloro. El diagnóstico de certeza es a través de la histopatología; su tratamiento quirúrgico, y tiene buen pronóstico en sus estadios iniciales (AU)

Basal cells adenocarcinoma also known as salivary basaloide carcinoma basal cells malignant adenoma is a low degree, infiltrating, locally destructive and prone to be relapsing, epithelial neoplasia. It occurs between the 5th and 6th decade of life, with no predilection for sex. Clinically it manifests with an edema or sudden increased size in the area, of firm consistency, slow growth and pain-less. Its treatment is surgical and the diagnosis of certainty is histopathological with a good prognosis. The purpose of this presentation is to show the case of a 57- years-old male patient with clinical and anatomopathological diagnosis of adenocarcinoma of basal cells located in the yugal mucosa (AU)

Spatiotemporal distribution of organotin compounds in the coastal water of the Bahía Blanca estuary (Argentina).

Several areas within the Bahía Blanca estuary (BBE), with different maritime traffic intensity, were studied in order to confirm the presence and assess the distribution of tributyltin (TBT), dibutyltin (DBT), and monobutyltin (MBT) in the water column. The organotin compounds (OTCs) were determined in the water samples-taken in summer, autumn, winter, and spring of 2014-by gas chromatography coupled to mass spectrometry after liquid-liquid extraction with hexane. The incidence of TBT throughout the whole sampling period indicated a continuous presence of this compound to the study area. However, in accordance with the butyltin degradation index (BDI), TBT was not recently introduced in the BBE. Furthermore, the average TBT levels exceeded the international guideline established by the Oslo-Paris commission (0.62 ng Sn L-1). As a result, certain biological effects could be expected to occur in sensitive species such as mussels. While DBT were below the detection limit in the 75% of the samples analyzed, MBT was detected in all the samples and no significant differences were found among the concentrations measured in the different seasons (Kruskal-Wallis test, p > 0.05). In addition, no correlations were found among the OTCs levels and the evaluated physiochemical parameters (Spearman coefficient, p > 0.05).

Fast and Feasible Ultrasound-Assisted Pretreatment for the Determination of Organotin Compounds in Environmental Samples.

The goal of this study was to improve an already established reference method, such as the one devoted to organotin compounds determination (Reference Method for Marine Pollution Studies, No. 59, UNEP). The proposed upgrade consists of replacing the mechanical shaking by ultrasound energy and applying low temperature throughout the whole procedure. The optimization of the new operational conditions was performed by using a factorial design. Quality control was performed using a certified sediment reference material (PACS-2) for sediments (82.5-97% of recovery) and recoveries on spiked samples for suspended particulate matter (SPM) and mussels (94-100%). The proposed procedure was applied to surface sediment samples, SPM, and native bivalve mollusks (Brachidontes rodriguezii) collected in Bahia Blanca estuary, a very industrialized zone. The relative standard deviation (RSD %) of the environmental samples were less than 7.9%. It is important to note that the proposed procedure reduced the sample pretreatment time about seven times.

Organotin compounds in Brachidontes rodriguezii mussels from the Bahía Blanca Estuary, Argentina.

Levels of tributyltin and its breakdown compounds, including the first record of monobutyltin (MBT) in history for Latin America, were determined in native mussels (Brachidontes rodriguezii) by means of CG-MS, after extraction/derivatization assisted by ultrasound. The samples were collected in 2013 in Bahía Blanca Estuary (Argentina) at 6 sites, which reflect different levels of maritime activities. Total butyltins (TBts = TBT+ DBT+ MBT) levels ranged from 19.64 to 180.57ng Sn g-1 dry weight. According to the Oslo-Paris commission, the results indicated that 73.9% of mussels could be under biological effects risks associated with TBT pollution. In accordance with the calculated bioaccumulation factors, approximately 56% of samples appeared to have accumulated TBT through the sediments. All sampling sites were shown to be impacted by organotin compounds (OTCs) showing variable levels through seasons, which could be related with the variation of the water temperature. Degradation index analyses suggested aged inputs of TBT possibly under a general degradation process at the area of study. In addition, the occurrence of DBT and MBT could not be uniquely attributed to the degradation pathway of the TBT; in fact, results outlined the possible contribution of some punctual and diffuse sources at the area such as proximity to plastic industries, industrial effluents, sewage outlets and domestic wastewaters.

Ionic liquid mediated extraction, assisted by ultrasound energy, of available/mobilizable metals from sediment samples.

A new extraction method for metals from sediment samples was developed. In this procedure, the chelating agent EDTA was combined with a minimal amount of the ionic liquid 1-butyl-3-methylimidazolium tetrafluoroborate (Bmim[BF4]), assisted by ultrasound energy. The available analytes -Cd, Cr, Cu, Ni, Pb and Zn- were extracted under optimal conditions for a 12.5 ratio (extractant volume/sample mass) with 0.005molL-1 EDTA solution, 0.1molL-1 NaHCO3, 5.0mmolL-1 Bmim[BF4] and 7.0min of sonication time, using an ultrasonic bath (output power of 160W). The best extractions were obtained with 100W (power dissipated in the liquid). These conditions were obtained applying the univariate method. It is important to highlight that the conventional method (extraction with 0.05molL-1 EDTA solution only) consumes 6h to extract available metals from sediment samples selectively, and with the proposed procedure the extraction time is noticeable reduced to 7.0min. Extractable metal concentrations obtained were measured by flame atomic absorption spectrometry. The results showed good agreement with those obtained by the conventional method using a Student's paired t-test.

Chemometric approach to visualize and easily interpret data from sequential extraction procedures applied to sediment samples.

The aim of this study was to assess metal mobility/availability in coastal surface (oxic) sediment samples from the Bahía Blanca estuary. Particularly, two sequential extraction procedures able to discriminate metals associated to amorphous Fe and Mn oxides and those associated with crystalline oxides of Fe were applied. Sequential procedures differ in the number of steps, type of reagents used, and in the order in which metals associated to organic matter are extracted. The studied metals were Cd, Cr, Cu, Pb, Ni and Zn because of their hazardous potential and relative abundance in the estuary. Tucker4 model with three factors describes appropriately the data sets (explained variance of 64.05%). This model made it possible to visualize and explain the information underlying in the data set. From the multivariate analysis, it was possible to evaluate the metal behaviour and their availability. In this way, Cd and Zn are associated to the more available fractions whereas Ni, Cr, Cu and Pb are mainly associated to the unavailable fractions. On the other hand, Zn and Cu are associated to organic matter fraction. Despite the fact that the two-fractionation schemes are quite different, the results obtained with both schemes are comparable.

Performance evaluation of two chelating ion-exchange sorbents for the fractionation of labile and inert metal species from aquatic media.

The performance of two iminodiacetate chelating resins, applied in an element fractionation scheme, was investigated for the characterization of marine and stream water samples collected in potentially contaminated harbor and industrial zones. The comparison involved an evaluation of the sorption/desorption behavior of Cd, Cu, Pb and Zn on Chelex-100, a sorbent extensively employed for metal speciation studies, and on Lewatit TP-207, a material with similar chelating characteristics for which no applications for fractionation studies are reported. A characterization of the latter resin in terms of the influence of sample pH on the uptake of metals from aqueous solutions and their subsequent acid elution was carried out. Fractionation studies were performed on natural water samples and model solutions resembling their composition, spiked with micromolar concentrations of the metals. The operationally defined fractionation scheme is based on dynamic adsorption of the resin-labile fractions of metals on microcolumns made of the sorbents. This stage is followed by a batch procedure in which the eluent from the column is contacted with fresh resin to discriminate between the relatively stable species unable to react with the resin during the column interaction time, and the strongly complexed metals that do not interact with the sorbent even for periods of several hours. Results were obtained from coarsely filtered sub-samples and from specimens passed through membrane filters of pore size 0.45 and 0.22 microm. The method was also assessed with model solutions of the metals containing variable concentrations (in the 10(-3)-10(-7) molar range) of complex forming agents such as nitrilotriacetic acid and trans-1,2-diaminocyclohexane-N,N,N',N'-tetraacetic acid. An additional batch method, in which a fixed amount of resin was contacted with sample solution for increasing periods of time and the amount of metal remaining in solution measured as a function of the elapsed time, was used to obtain information on the kinetics of dissociation of species formed in the presence of added complexants. The behavior of both resins was similar, demonstrating that the discrimination of species derived from experiments with Chelex-100 may be properly validated by independent fractionation tests carried out with Lewatit TP-207. The behavior of the sorbents is also discussed in terms of the possible influence of particulate or colloidal materials and of kinetic effects related to the presence of complexing agents.

Evaluation of sorption and desorption characteristics of cadmium, lead and zinc on Amberlite IRC-718 iminodiacetate chelating ion exchanger.

A chelating type ion exchange resin (Amberlite IRC-718), containing iminodiacetate groups as active sites, has been characterized regarding the sorption and subsequent elution of Cd, Zn and Pb, aiming to metal preconcentration from solution samples of different origins. The methodology developed is based on off-line operation employing mini columns made of the sorbent. The eluted metals were determined by flame atomic absorption spectrometry. The effect of column conditioning, influent pH and flow rate during the sorption step, and the nature of the acid medium employed for desorption of the retained metals were investigated. Working (breakthrough) and total capacities were measured under dynamic operating conditions and the results compared with those obtained with Chelex-100, a resin extensively employed for analytical preconcentration. Structural information on the complexation of metals by the chelating groups was obtained by Fourier Transform infrared spectrometry. The analytical response of the Amberlite sorbent was assessed for the analysis of water samples and digestates of marine sediments.