Permeability/performance reference compounds (PRCs) are analytically noninterfering organic compounds with moderate to high fugacity from semipermeable membrane devices (SPMDs) that are added to the lipid prior to membrane enclosure. Assuming that isotropic exchange kinetics (IEK) apply and that SPMD-water partition coefficients are known, measurement of PRC dissipation rate constants during SPMD field exposures and laboratory calibration studies permits the calculation of an exposure adjustment factor (EAF). In theory, PRC-derived EAF ratios reflect changes in SPMD sampling rates (relative to laboratory data) due to differences in exposure temperature, membrane biofouling, and flow velocity-turbulence at the membrane surface. Thus, the PRC approach should allow for more accurate estimates of target solute/vapor concentrations in an exposure medium. Undersome exposure conditions, the impact of environmental variables on SPMD sampling rates may approach an order of magnitude. The results of this study suggest that most of the effects of temperature, facial velocity-turbulence, and biofouling on the uptake rates of analytes with a wide range of hydrophobicities can be deduced from PRCs with a much narrower range of hydrophobicities. Finally, our findings indicate that the use of PRCs permits prediction of in situ SPMD sampling rates within 2-fold of directly measured values.

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The history of the Amazon River is a much-discussed subject, and the timing of the development of a transcontinental system in particular is a matter of some controversy, with estimations varying between the Early Miocene and the Pliocene or even the Pleistocene. To shed further light on this, we studied the sediment provenance of an Oligocene to Late Pleistocene marine sedimentary section from the Ceará Rise (ODP Site 925), a topographic high in the central Atlantic Ocean, using major element concentrations and Nd isotopic composition in 85 samples. In addition, the carbon isotopic composition of bulk organic matter and changes in the distribution of glycerol dialkyl glycerol tetraethers (GDGTs) were used to identify periods of increased river outflow. On the basis of these results, we suggest that the history of the development of the Amazon River is characterized by specific steps. During the late Oligocene/Early Miocene (30-18.3 Ma), the terrigenous mass accumulation rates (TARs) were high, and sediment and GDGT compositions suggest that a large river system existed, which at times received weathering products from a younger and probably Andean sediment source. A shift to a younger Andean sediment provenance after 8.7 Ma indicates that the Amazon River became permanently connected with the Andes. Between 18.3 and 4.5 Ma, TARs were generally low, and GDGTs were derived for the most part from in situ production in marine waters. Around 4.5 Ma, the river expanded, probably due to ongoing tectonic activity, and uplift in the Andes increased Andean rock erosion. This led to a strong increase in terrigenous sediment deposition and enhanced organic matter preservation on the Ceará Rise, and the delivery of terrestrial (both soil and riverine) branched GDGTs to the Ceará Rise.

Este é o primeiro trabalho que relata a ocorrência de resíduos de cocaína (COC) e benzoilecgonina (BE) em amostras coletadas em seis estações de esgoto diferentes (ETE) instaladas no Distrito Federal (DF) do Brasil. As concentrações de BE nos afluentes de esgoto foram utilizadas para calcular o consumo de cocaína (kg ano -1 por 1000 habitantes) em cada uma das regiões atendidas pelas ETE, em duas campanhas de amostragem (março e junho de 2010). Dentre as ETE estudadas, amostras provenientes de Samambaia apresentaram as maiores concentrações (de 3866 a 2477 ng L -1 de BE e 805 a 579 ng L -1 de COC) e doses por habitante (mais de 13 doses habitante -1 por ano). A extrapolação para toda a população do DF indica um consumo anual alcançando 1,0 tonelada de cocaína base livre, ou 1,1 tonelada de cloridrato de cocaína. Este trabalho também aborda a influência da forma de apresentação da cocaína (base livre ou sal cloridrato) e a integração com resultados de perfil químico na busca de estimativas mais realistas, principalmente no que se refere aos pontos de vista da criminalística e da segurança pública. This is the first report on the occurrence of cocaine (COC) and benzoylecgonine (BE) residues in six samples collected from different wastewater treatment plants (WTP) located in the Brazilian Federal District (FD). Concentrations of BE in the influent sewage were used to calculate cocaine consumption (kg year -1 per 1000 inhabitants) for each region attended by the WTP from two sampling campaigns (March and June, 2010). Among the WTP studied, samples from Samambaia showed higher concentrations (from 3866 to 2477 ng L -1 of BE and 805 to 579 ng L -1 of COC) and doses per inhabitants (more than 13 doses inhabitant -1 per year). The extrapolation to the whole FD population points out to an annual consumption reaching 1.0 ton of free base cocaine, or 1.1 tons of cocaine hydrochloride. The work also addresses the influence of the cocaine presentation form (free base or hydrochloride) and the integration with chemical profiling results in a more realistic estimate, mainly concerning the viewpoints of forensics and law enforcement.

Rasgão Reservoir, located close to the Metropolitan region of São Paulo, Brazil, has been analyzed previously, and its sediment was found to be highly toxic, with high levels of metals and polycyclic aromatic hydrocarbons and a complete absence of benthic life. Polychlorinated biphenyls also were present, as was mutagenic activity, detected with the Salmonella/microsome assay. Because of the extremely complex mixture of contaminants in these sediments, a toxicity identification evaluation was performed on the pore water and elutriate using Ceriodaphnia dubia and Vibrio fischeri. Toxicity characterization, identification, and confirmation procedures were performed in one representative sample of the reservoir, and the results indicated that ammonia was the main cause of the toxicity detected with C. dubia in both sediment pore water and elutriate. Chemical analysis corroborated this observation by revealing un-ionized ammonia concentrations as high as 5.14 mg/L in pore water and 2.06 mg/L in elutriate. These high ammonia levels masked possible toxicity caused by other classes of compounds. The toxicity detected with V. fischeri decreased with the time of sample storage and was related to the organic fraction of the pore water and the elutriate, in which compounds such as benzothiazole and nonylphenol were detected.

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