Insights into the organic matter composition of soda lakes in the Pantanal, Brazil, through fatty acids analysis in sediments.

We conducted a geochemical analysis on three sediment cores collected from soda and freshwater lakes in the Pantanal region, in Brazil. Our objective was to identify the primary sources of organic matter associated with the Pleistocene-Holocene transition, as previously documented in that area. The Nhecolandia region, located in the Pantanal, encompasses over 10,000 lakes, with approximately 10% of them exhibiting alkaline characteristics. Soda lakes became highly saline and alkaline after ~ 910 cal yr BP, which influences biogeochemistry and aquatic ecology. They have high electrical conductivity and pH can reach 10.5. In contrast to freshwater, soda lakes are absent of surrounding vegetation. Literature suggests a strong influence by the Last Glacial Maximum on the region. We hypothesized that periods of aridity and increased precipitation influenced the composition of organic matter present in sediments and preserved within these cores. Our analysis focused on examining the presence and distribution of fatty acids, organic carbon content, and total nitrogen. In general, the cores exhibited two distinct parts in terms of organic matter sources: the upper sections of the cores were primarily composed by terrestrial sources, identified by the presence of long-chain fatty acids, while the deeper sections were dominated by aquatic sources, therefore short-chain fatty acids. We did not find significant difference among fatty acid profile that could distinguish freshwater from soda lakes, the only remarkable difference was the occurrence of saturated fatty acids, which is lower in freshwater lake. These findings suggest the occurrence of humid and arid periods in the region. The C/N ratio displayed a similar trend to the fatty acid's profiles, exhibiting an abrupt change that was likely induced by climate variations. Although diagenesis can alter the composition of organic matter and, subsequently, the C/N values, it is noteworthy that the abrupt change observed in the Salina da Ponta (soda lake) core corresponds to 3,200 years BP. This coincides with documented climate changes that occurred during the Holocene. Our study revealed the influence of past climatic conditions on the sources and variations of organic matter in sediment cores from the Pantanal's soda and freshwater lakes. Consideration of diagenesis and climate variations is crucial for interpreting sedimentary records.

Use of fatty acids as tracer of organic matter input associated with level of land urbanization.

Suspended sediments (SSs) were examined regarding the content of fatty acids (FAs) to associate them with sources of soil entry into the river. The source of organic matter was traced through fatty acid distribution, as well as erosion. Also, TOC, TN, and TOC/NT were used to support the results of FAs. For this, a tropical river was chosen to understand the main source of input considering the level of land occupation along the river. The Barigui river, in southern Brazil, was segmented in four distinct areas regarding the soil occupation (P1, P2, P3, and P4). Nine sampling campaigns were conducted from Nov/2014 to Nov/2015 using a time-integrated sampler. Site P1 has the lowest level of urbanization and showed the lowest concentration of FAs (16.35 µg-1). In contrast, site P4, the most urbanized, showed the highest content of fatty acids, including those associated with erosion, 378.53 µg g-1, specifically those with long chains. The mean concentrations of the saturated fatty acids (FAs) was 283.40 µg g-1, monounsaturated fatty acids (MUFAs) was 79.46 µg g-1, and polyunsaturated fatty acids (PUFAs) was 15.66 µg g-1. Twenty-seven fatty acids were examined, nevertheless C15:0, C16:0, C18:0, and C18:1ω9 prevailed in all samples. Generally, those acids indicate sewage inputs. Statics analyses were used to find the relation between the source of organic matter (autochthonous, allochthones, and anthropogenic) and FAs. Finally, the input of organic matter is associated with land occupation, which can be distinguished by FA distribution.

PAHs in Water, Sediment and Biota in an Area with Port Activities.

The study reports concentration of 16 PAHs in sediment, water, plankton and in muscle and liver of sampled fishes from Paranagua Bay in Southern Brazil. According to the range of PAHs concentration found in sediments (ΣPAHs 15.33-133.61 µg g-1) and water (ΣPAHs 51.20-162.37 µg L-1), the area was characterized as slightly polluted. In contrast, significant concentration of PAHs was found in fish and plankton, ranging from 26.52 to 2055.00 µg g-1 and 175.41 to 2096.10 µg g-1, respectively. The concentrations were 15 times more than in sediments. Even though the concentration of PAHs in water and sediments are low, the concentration in fish tissues are alarmingly. The hypothesis of bioaccumulation is not discharged. Accumulation levels of PAHs in the biota were used to calculate biota-sediment accumulation factor (BSAF) and bioaccumulation factor (BAF). For example, fish sampled from site 11 had a BAF of 49 and BSAF of 2.3, whereas for plankton the BAF was 16.3 and BSAF 0.7. Mean values of BAF and BSAF were higher in plankton samples. It is known that PAHs are enzymatically metabolized by organisms, thus the lower BSAF in fish might have resulted from biochemical transformation. Statistical analysis indicates no significant correlation between total PAHs concentration in fish tissues and total lipid content in fishes (p > 0.1).Accumulation in tissues is controlled by lipid content, although factors, such as spatial distribution of compounds, trophic level, and behavior of each species in the environment, must be considered. Besides, size and nutritional conditions can affect both absorption as well as metabolic process and excretion. A positive and significant correlation was found between total PAHs and trophic positions obtained from FishBase data (r2 = 0.784; p < 0.05). Thus, it seems that the area, with great influence of urban and industrial activities, and the bioaccumulation compounds, such as PAHs, depend on others factors, as well as resuspension of sediments and releasing of compounds for biota.

Critical aggregates concentration of fatty esters present in biodiesel determined by turbidity and fluorescence.

Biodiesel for combustible engine is available as mixture of fossil diesel and fatty esters obtained by transesterification of vegetable oils. The use of biodiesel reduces the amount of SOx, mainly. However, it was already observed that biodiesel has a different behavior in environment in cases of accidental spill and groundwater contamination. It was noticed that the biodegradation of hydrocarbons (cyclic and aliphatic) in the presence of biodiesel are speeded, although the mechanism is still unclear. Considering the chemical structure of fatty esters, it was investigated the formation of aggregates in water solution by fatty esters present in commercial biodiesel. In Brazil, biodiesel is composed by 95% of fossil diesel and 5% of fatty esters mixture. In this work, fatty esters were treated as neutral surfactant, i.e., it was treated as a molecule with polar and non-polar part. Turbidity and fluorescence were used to determine the critical aggregates concentration (CAC). Water solutions containing fatty esters were examined exploiting changes in turbidity and fluorescence intensity of pyrene. Abrupt changes were attributed to aggregates formation, following the same behavior of traditional amphiphilic compounds. It was determined the CAC for ethyl palmitate, ethyl stearate, ethyl oleate, and ethyl linoleate. The values of CAC for fatty esters varied from 1.91 to 4.27 µmol/L, while CAC for the mixture of esters (biodiesel) was 2.01 for methyl esters and 1.19 for ethyl esters, both prepared using soybean oil. The aggregates formation was also determined by fluorescence measurements considering the changes in intensity of peaks I and III of pyrene. Pyrene senses the changes in environment polarity. The values found of CAC by fluorescence for individual ethyl esters varied from 1.85 to 3.21 µmol/L, while mixtures of ethyl esters was 2.23 and 2.07 µmol/L for mixture of methyl esters. The results clearly showed that fatty esters form aggregates and might be responsible for speed degradation of compounds by accommodation of them in inner part of aggregates.

Assessment of historical fecal contamination in Curitiba, Brazil, in the last 400 years using fecal sterols.

A 400-year sedimentary record of the Barigui River was investigated using fecal biomarkers and nutrient distribution. The temporal variability in cholesterol, cholestanol, coprostanol, epicoprostanol, stigmastanol, stigmasterol, stigmastenol, sitosterol, and campesterol between 1600 and 2011 was assessed. Anthropogenic influences, such as deforestation and fecal contamination from humans and livestock, were observed from 1840. The sterol ratios exhibit evidence of hens, horses, cows, and an unknown herbivore, which may be a capybara (Hydrochoerus hydrochaeris), from 1820 and has been observed more markedly from 1970 onward. Human fecal contamination was detected from 1840 and was observed more markedly from 1930 due to population growth. Thus, the sanitation conditions and demographic growth of Curitiba seemed to be the main factors of human sewage pollution, as the coprostanol concentration over time was strongly correlated with the population growth (r=0.71, p<0.001) although diagenetic processes have also been observed.(1.)

Evaluation of potential sewage contamination by fecal sterol biomarkers adsorbed in natural biofilms.

The use of biofilms for adsorption of sterols was investigated for the first time to evaluate sewage contamination in the Barigüi River, Curitiba (Brazil). The characteristics of a biofilm that favor its use in monitoring include the relatively rapid development of biofilms and their capacity to sorb hydrophobic compounds. Some fecal sterols considered to be biomarkers for human and animal feces have relatively high octanol-water partitioning coefficients (log KOW); thus, sterols were expected to be readily sorbed in the biofilms. The biofilms were developed on glass plates (0.48 m(2)) previously coated with a fine layer of stearic acid and supported by a PVC tube that was submersed in the river 20 cm above the river bottom. After a certain period of incubation time, the biofilm growth was scraped from the plates and analyzed for the following fecal steroids: coprostanol (5ß-cholestan-3ß-ol), epicoprostanol (5ß-cholestan-3α-ol), cholesterol (5,6-cholesten-3ß-ol), cholestanol (5α-cholestan-3ß-ol), stigmastanol (24ß-ethyl-5α-cholestan-3ß-ol) and coprostanone (5ß-cholestan-3-one). Six samples were collected between March 2012 and June 2012. All analyzed compounds were detected, and in general, cholesterol was present in high amounts (23 160-41.9 ng g(-1) dry biofilm). Variation among campaigns was observed in the distribution of sterols, with cholestanol showing the least variation among the samples. Sterol ratios that are commonly used for evaluating sewage contamination were calculated; these ratios indicated some periods of potential sewage influence. However, these sterol ratios are intended to be applied primarily for sediments and not for biological compartments; thus, the results must be carefully interpreted. Biofilms developed under natural conditions can be a tool for monitoring some important sterols that are used as biomarkers of fecal pollution.