Marcelo R. Alexandre

Radiocarbon dating of individual lignin phenols: A new approach for establishing chronology of late quaternary lake sediments

The reliability of chronology is a prerequisite for meaningful paleoclimate reconstructions from sedimentary archives. The conventional approach of radiocarbon dating bulk organic carbon in lake sediments is often hampered by the old carbon effect, i.e., the assimilation of ancient dissolved inorganic carbon (DIC) derived from carbonate bedrocks or other sources. Therefore, radiocarbon dating is ideally performed on organic compounds derived from land plants that use atmospheric CO(2) and rapidly delivered to sediments. We demonstrate that lignin phenols isolated from lake sediments using reversed phase high performance liquid chromatography (HPLC) can serve as effective (14)C dating materials for establishing chronology during the late Quaternary. We developed a procedure to purify lignin phenols, building upon a published method. By isolating lignin from standard wood reference substances, we show that our method yields pure lignin phenols and consistent ages as the consensus ages and that our procedure does not introduce radiocarbon contamination. We further demonstrate that lignin phenol ages are compatible with varve counted and macrofossil dated sediment horizons in Steel Lake and Fayetteville Green Lake. Applying the new method to lake sediment cores from Lake Qinghai demonstrates that lignin phenol ages in Lake Qinghai are consistently younger than bulk total organic carbon (TOC) ages which are contaminated by old carbon effect. We also show that the age offset between lignin and bulk organic carbon differs at different Lake Qinghai sedimentary horizons, suggesting a variable hard water effect at different times and that a uniform age correction throughout the core is inappropriate.

Coordination polymer adsorbent for matrix solid-phase dispersion extraction of pesticides during analysis of dehydrated Hyptis pectinata medicinal plant by GC/MS.

The coordination polymer [Zn(BDC)(H(2)O)(2)](n) was tested for extraction of pyrimethanil, ametryn, dichlofluanid, tetraconazole, flumetralin, kresoxim-methyl and tebuconazole from the medicinal plant Hyptis pectinata, with analysis using gas chromatography-mass spectrometry in selected ion monitoring mode (GC/MS, SIM). Experiments carried out at different fortification levels (0.1, 0.5 and 1.0 μg g(-1)) resulted in recoveries in the range 73-97%, and RSD values were between 5 and 12% for the [Zn(BDC)(H(2)O)(2)](n) sorbent. Detection and quantification limits ranged from 0.02 to 0.07 μg g(-1) and from 0.05 to 0.1 μg g(-1), respectively, for the different pesticides studied. The method developed was linear over the range tested (0.04-14.0 μg g(-1)), with correlation coefficients ranging from 0.9987 to 0.9998. Comparison between [Zn(BDC)(H(2)O)(2)](n) and the commercial phase C(18)-bonded silica showed good performance of the [Zn(BDC)(H(2)O)(2)](n) polymeric sorbent for the pesticides tested.

Distribution and sources of aliphatic hydrocarbons in surface sediments of Sergipe River estuarine system

The assessment of aliphatic hydrocarbons was performed in the Sergipe River estuarine system, northeastern Brazil. Aliphatic hydrocarbons concentration ranged from 9.9 ug g⁻¹ up to 30.8 ug g⁻¹ of dry sediment. The carbon preference index (CPI, based on nC₂₄ to nC₃₄ range), indicated predominance of petrogenic input in two of the sites analyzed (P4 and P5). The unresolved complex mixture (UCM) was found to be present in seven of the nine sites sampled (except for P4 and P5). Overall, the results of this work suggest that there is a mix of organic matter sources to the sediment. Although the coast of Sergipe has an intense off shore petroleum exploration and the Sergipe River crosses the entire city of Aracaju, the capital city of Sergipe, non-significant anthropogenic fingerprint was assessed.

Assessment of anthropogenic contamination with sterol markers in surface sediments of a tropical estuary (Itajaí-Açu, Brazil).

The Itajaí-Açu estuarine region is one of the most important estuarine systems of south Brazil, due to the location of the Itajaí Harbor, which is the major route of international trading of the state and the largest national fishing pole landing. In addition, industries as well as urban and tourism activities are potential sources of pollution in this area. In the present study, sediment samples from 12 stations along the estuarine system were collected and extracted followed by ultra-high performance liquid chromatography tandem mass spectrometry (UHPLC-MS/MS) analysis. Eight sterols were identified and quantified, indicating natural and anthropogenic sources. Coprostanol concentrations ranged from <4 up to 8930 ng g(-1) of dry weight sediment with higher values being observed in the area next to the Itajaí Harbor and under influence of Itajaí-Mirim River flow, which receives wastewater from several cities. Concentrations and selected sterol ratios were useful tools used to distinguish anthropogenic and biogenic organic matter (OM) sources in the studied area, where coprostanol concentrations higher than 500 ng g(-1) were observed in 42% of the stations analyzed, indicating strong sewage contamination. Factor analysis with principal component analysis (FA/PCA) has distinguished two different groups of samples, with high and low total sterol concentrations. FA/PCA results revealed that the stations located in the estuary were separated by PC1 because they are clearly contaminated by sewage, also pointed by coprostanol/(coprostanol+cholestanol) and coprostanol/cholesterol ratios and by the higher concentrations of fecal sterols.

Seasonal distribution of aliphatic hydrocarbons in the Vaza Barris Estuarine System, Sergipe, Brazil

The seasonal assessment of anthropogenic activities in the Vaza Barris estuarine river system, located in the Sergipe state, northeastern Brazil, was performed using the aliphatic hydrocarbon distribution. The aliphatic hydrocarbon and isoprenoid (Pristane and Phytane) concentrations ranged between 0.19 μg g(-1) and 8.5 μg g(-1) of dry weight. Data were analyzed using Kruskal-Wallis test, with significance level set at p<0.05, and no seasonality distribution change was observed. The Carbon Preference Index (CPI), associated with n-alkanes/n-C16, Low Molecular Weight/High Molecular Weight ratio (LMW/HMW) and Terrigenous to Aquatic Ratio (TAR) suggested biogenic input of aliphatic hydrocarbons for most samples, with significant contribution of higher plants.

Multiclass MSPD method for pesticide determination in dehydrated Hyptis pectinata (sambacaitá) medicinal plant by GC-MS

A method was developed using matrix solid-phase dispersion (MSPD), together with gas chromatography coupled to mass spectrometry (GC-MS) for determination of ametryn, tetraconazole, flumetralin, tebuconazole, pyrimethanil, dichlofluanid and kresoxim-methyl in dehydrated Hyptis pectinata (sambacaita) medicinal plant material. The evaluated parameters included the type and amount of sorbent (C18, neutral alumina, silica gel and Florisil) and the nature of the eluent (dichloromethane, ethyl acetate and dichloromethane:ethyl acetate (1:1, v/v)). The best results were obtained using 0.5 g of plant material, 0.5 g of C18 as sorbent and dichloromethane (20 mL) as the eluting solvent. The method was validated using plant samples spiked with pesticides at different concentration levels (0.05-1.0 µg g-1). Average recoveries (using four replicates) ranged from 83 to 127%, with relative standard deviations between 4 and 15%. Limits of detection (LOD) and quantification (LOQ) were in the ranges 0.02-0.07 µg g-1 and 0.05-0.1 µg g-1, respectively.

Evaluation of anthropogenic contamination using sterol markers in a tropical estuarine system of northeast Brazil.

The São Francisco River estuarine system, located in the Northeast coast of Brazil, has great economic, tourist and social importance. Its waters are used for activities such as agriculture, aquaculture, navigation and fishery, which supplies the surrounding communities. In this study, sterols markers were determined in twenty-eight sediment samples from São Francisco River estuary by gas chromatography - mass spectrometry (GC-MS). Sterol analysis was useful to distinguish between anthropogenic and biogenic organic matter (OM) sources in the studied area. Six sterols were quantified, suggesting different sources. Concentrations of fecal sterol (coprostanol) were lower than 500ngg(-1), suggesting no indicative of severe sewage contamination.However, two stations showed concentrations around 100ngg(-1) and the values for the coprostanol/(coprostanol+cholestanol) and coprostanol/cholesterol ratios indicates sewage contamination. The results in this study may be considered as baseline concentrations to be used as future reference for monitoring programs to prevent anthropogenic impacts.

Concentration, distribution and source apportionment of polycyclic aromatic hydrocarbons (PAH) in Poxim River sediments, Brazil

The individual concentrations, total amount and sources of 16 priority polycyclic aromatic hydrocarbons (PAH) in sediments collected along of the Poxim River, Aracaju, Brazil, were for the first time determined. The ΣPAH ranged between 2.2±1.5ngg-1 and 28.4±6.9ngg-1, with a mean value of 14.4±9.3ngg-1. The Pearson correlation test and Principal component analysis (PCA) were used to assess the correlation between the PAH, organic matter and grain size; and to differentiate the sampling stations. Diagnostic ratios presented predominance of pyrogenic sources. Therefore, the PAH quantified showed the influence of anthropogenic activities near of the Poxim River.

Polycyclic aromatic hydrocarbons (PAH) in superficial water from a tropical estuarine system: Distribution, seasonal variations, sources and ecological risk assessment

This study aimed to evaluate the PAH distribution, sources, seasonal variations and ecological risk assessment in superficial water from the Japaratuba River, Brazil. PAH concentrations ranged from 4 to 119ngL-1. It was observed that the PAH total concentrations and profiles showed significant differences when comparing the dry season (summer) with the rainy season (winter). Furthermore, most of the PAH originated from pyrogenic sources in the winter, whereas a mixture of sources was observed in the summer. PAH concentration levels found in this study were considered lower than those obtained in other estuarine systems. Ecological risk assessment was determined for individual PAH, based on the risk quotient (RQ) to evaluate the risk of aquatic biotas exposure to PAH. Results suggested that the Japaratuba River has achieved a moderate degree of ecological risk for high molecular weight, showing the importance of identifying these carcinogenic and mutagenic compounds in aquatic systems.

An Astrobiological Experiment to Explore the Habitability of Tidally Locked M-Dwarf Planets

We present a summary of a three-year academic research proposal drafted during the Sao Paulo Advanced School of Astrobiology (SPASA) to prepare for upcoming observations of tidally locked planets orbiting M-dwarf stars. The primary experimental goal of the suggested research is to expose extremophiles from analogue environments to a modified space simulation chamber reproducing the environmental parameters of a tidally locked planet in the habitable zone of a late-type star. Here we focus on a description of the astronomical analysis used to define the parameters for this climate simulation.