Concentrations, sources and risks of polycyclic aromatic hydrocarbons in sediments from the Parnaiba Delta basin, Northeast Brazil.

The Parnaíba River is the main river in the Parnaíba Delta basin, the largest delta in the Americas. About 18 polycyclic aromatic hydrocarbons (PAHs) were identified and the environmental risk associated with the sediments was evaluated. The study found that PAHs levels ranged from 5.92 to 1521.17 ng g-1, which was classified as low to high pollution, and that there were multiple sources of pollution along the river, with pyrolytic sources predominating, mainly from urban activity such as trucking, although the influence of rural activity cannot be ruled out. PAHs correlated with black carbon and organic matter and showed high correlation with acenaphthylene, phenanthrene, pyrene, benzo(a)anthracene, chrysene, benzo(ghi)perylene, and ∑PAHs. The benzo(a)pyrene levels were classified as a risk to aquatic life because the threshold effect level and the probable effect level were exceeded. In addition, the sediments were classified as slightly contaminated with a benzo(a)pyrene toxicity equivalent value of 108.43 ng g-1. Thus, the priority level PAH exhibited carcinogenic and mutagenic activity that posed a potential risk to human health.

Hydrocarbon markers for assessing the influence of human activities in the tropical semi-arid region (Acaraú River, state of Ceará, Brazil).

Coastal ecosystems are facing increasing anthropogenic stressors, including rapid urbanization rates and extensive fossil fuel usage. Nevertheless, the distribution of hydrocarbons in the Brazilian semi-arid region remains relatively uncharacterized. In this study, we analyzed ten surface sediment samples (0-2 cm) along the banks of the Acaraú River to assess the chronic contributions of aliphatic and aromatic hydrocarbons. The Acaraú River is a crucial riverine-estuarine area in the semi-arid region of Northeast Brazil. Ultrasound-assisted extraction and gas chromatograph coupled to a mass spectrometer were used to identify target compounds: 45 PAHs, 27 n-alkanes (C10-C38), and two isoprenoids. At most stations, the predominant grain size was sand, and the organic carbon content was less than 1%. The total n-alkanes concentration ranged from 14.1 to 170.0 µg g-1, while individual pristane and phytane concentrations ranged from not detected (nd) to 0.4 µg g-1 and nd to 0.7 µg g-1, respectively. These concentrations resemble those found in unpolluted sediments and are lower compared to samples from urbanized coastal areas. The total USEPA PAHs concentration varied from 157.8 to 1364 ng g-1, leading to the characterization of sediment samples as moderately polluted. Based on diagnostic ratios calculated from both alkane and PAH concentrations, the sediment samples were predominantly deriving from pyrolytic sources, with some contribution from petrogenic sources. The most abundant group was 5-ring PAHs (mean: 47.3 ± 36.7%), followed by 3-ring PAHs (mean: 17.9 ± 13.7%). This predominance indicates a pyrolytic origin of hydrocarbons in the Acaraú River. The concentrations reported here were representative of the level of background hydrocarbons in the region. Regarding the sediment quality assessment, BaP TPE calculated for the Acaraú River ranged from 13.2 to 1258.4 ng g-1 (mean: 409.3 ± 409.4 ng g-1). When considering site-specific sediment quality values for the coast of the state of Ceará, half of the stations are classified as strongly contaminated, and toxic effects are expected to occur (SQGq >0.25) for the ∑16 PAHs measured in the samples, especially due to dibenz [a,h]anthracene concentrations.

Levels, source appointment, and ecological risk of petroleum hydrocarbons in tropical coastal ecosystems (northeast Brazil): Baseline for future monitoring programmes of an oil spill area.

We reviewed 20 years of levels, sources, and environmental risks related to the main petroleum hydrocarbons in the northeast region of Brazil. The aim of this study was to conduct a systematic review to serve as a comprehensive baseline for future monitoring programmes related to the oil spill disaster in 2019/2020. Most contamination levels of both PAHs and AHs were classified as low, except those in specific areas influenced by human activities, such as ports, highly urbanised mangroves, or rivers of medium-sized cities with inadequate liquid and solid waste treatment. Most hydrocarbons were linked to natural sources and burning processes, except in regions of extraction activities and petrochemical facilities as well as highly urbanised areas, where degraded petroleum and oil hydrocarbons predominated. Only 2.5% of the samples exceeded threshold effect levels for ∑16-PAHs and no samples exceeded probable effect levels. When regional threshold levels were used, however, the probable effect for the ∑16-PAHs measured was high, ranging from 5.8 to 6.1%. The few studies reporting biological responses showed that hydrocarbons from anthropogenic sources can induce adverse effects on marine organisms even at low to moderate levels. As the region has recently received a considerable quantity of crude oil, studies should be prioritised for a more precise assessment of the impact of this oil spill.

Marine debris on a tropical coastline: Abundance, predominant sources and fate in a region with multiple activities (Fortaleza, Ceará, northeastern Brazil).

The aim of the present study was to perform the first assessment of the abundance and classification of marine debris as well as determine the sources, transport and fate of this debris on an urbanized coast with multiple human activities. More than 80% of the marine debris was composed of synthetic materials. The beached marine debris was classified according to size. Meso-debris accounted for the highest portion of contamination (55%), followed by macro-debris (25.1%) and small debris (19.9%). Contamination by debris, such as cotton swabs (31%) and lollipop sticks (36.8%) accounted for the largest portion of the small debris class. Human recreational activities were the predominant source of debris, followed by navigation/fishing activities, domestic activities and industrial/port activities. The assessment of the predominance of human activities and the results of the model revealed a larger contribution of debris from recreational activities on nearby beaches on the small to larger scale and that rivers exert less of an influence due to the fact that they do not flow the entire year.

Emerging and traditional organic markers: Baseline study showing the influence of untraditional anthropogenic activities on coastal zones with multiple activities (Ceará coast, Northeast Brazil).

Molecular markers are useful tools to characterize natural and anthropogenic impacts on coastal zones. Distribution of n-alkanes showed that the Pacoti River was predominantly influenced by terrigenous input. Distribution of polycyclic aromatic hydrocarbon (PAH) indices showed a mix of natural sources, especially pyrogenic influences. Sterol and hormone levels showed sewage discharge. Integrated geographic assessment showed that pyrogenic process and sewage discharge are predominant along the river because of natural and different anthropogenic activities. The upstream region is influenced by rural activities such as livestock and discharge from the sewage treatment plant, whereas the estuarine region is influenced by urban and industrial activities, predominantly the discharge of treated or untreated sewage, vehicle traffic, and manufacture of red ceramics. On the other hand, on the river mouth, there is the predominance of aquaculture activities. Traditional anthropogenic markers are not sufficient for producing a comprehensive assessment of anthropogenic impacts in areas with multiple activities.

Emerging and Traditional Organic Markers in Areas with Multiple Anthropogenic Activities: Development of an Analytical Protocol and Its Application in Environmental Assessment Studies.

This work describes the development of an analytical protocol combining cleanup by liquid-solid extraction and GC-MS for the determination of emerging and traditional multi-molecular markers. The procedure was used for the environmental assessment of a coastal region with multiple human activities. Global recovery rates ranged from 45.49% to 119.4% for the 46 substances analyzed: pesticides (73.7%-97.7%), PAHs (52.5%-93.7%), sterols (66.7%-119.4%) and natural and synthetic hormones (45.5%-119.1%) and the rates were compared to those reported in studies on both individual classes and multi-classes of contaminants. The analytical protocol demonstrated satisfactory efficiency and could be used successfully in environmental assessments and source assignment studies. The environmental assessment study revealed that the Acaraú River in northeastern Brazil is influenced by the combination of urban and rural activities. The sources of PAHs are vehicular traffic and the burning of biomass; pesticides stem from pest control in agribusiness and public health campaigns; sterols and hormones stem from a combination of natural inputs, human sewage (treated and raw) and animal husbandry activities.

The legacy of organochlorine pesticide usage in a tropical semi-arid region (Jaguaribe River, Ceará, Brazil): Implications of the influence of sediment parameters on occurrence, distribution and fate.

Between the 1940s and 1990s, immeasurable amounts of organochlorine pesticides (OCPs) were used in endemic disease control campaigns and agriculture in the tropical semi-arid regions of Brazil. The present study evaluated the legacy of banned OCP usage, considering the levels, ecological risk and dependence on sediment physicochemical properties for the fate and distribution in the Jaguaribe River. The sum concentration of OCPs (ΣOCPs) ranged from 5.09 to 154.43 ng·g(-1), comparable to the levels found in other tropical and subtropical regions that have traditionally used OCPs. The environmental and geographical distribution pattern of p,p-DDT, p,p-DDD and p,p-DDE shows that the estuarine zone contained more than 3.5 times the levels observed in the fluvial region, indicating that the estuary of the Jaguaribe River is a sink. The temporal pattern indicates application of dichloro-diphenyl-trichloroethanes (DDTs) in the past; however, there is evidence of recent input of these pesticides. High ecological risk was observed for levels of γ-hexachlorocyclohexanes (γ-HCH) and heptachlor, and moderate ecological risk was observed for levels of DDTs in sediments from the Jaguaribe River. The heptachlor, γ-HCH and hexachlorobenzene (HCB) concentrations depend on the organic and inorganic fractions of sediment from the Jaguaribe River, whereas the p,p-DDE, p,p-DDD, p,p-DDT and α-endosulfan concentrations depend solely on the organic fraction of the sediment.

Relation factor: a new strategy for quality control in the determination of pesticides in environmental aqueous matrices.

The effects promoted by environmental aqueous matrices on pesticide determinations have been assessed, and for the first time, a simple, low-cost and efficient strategy for the correction of analytical results has been determined. This method can be useful as a parameter of quality control in a quality assurance programs. Evaluation of the matrix effect showed that environmental aqueous matrices, e.g., estuarine water, promote a distinctive and significant effect on the determination of pesticides. The picloram, atrazine and methyl parathion pesticides suffered the smallest effects promoted by the estuarine matrix, whereas chlorpyrifos and cypermethrin suffer a significant effect. For picloram, the matrix effect was a function of its physiochemical properties. However, for atrazine, methyl parathion, chlorpyrifos and cypermethrin, the matrix effect was promoted by environmental matrix components. As strategy for analytical quality control, it has been determined that there are relation factors (RFs) between pesticides and the selected surrogates standards. These RFs are not altered by the complexities and compositions of simple and complex aqueous matrices. Predetermined RFs was applied to the picloram, atrazine and methyl parathion assessment in a real sample from the estuary of the Jaguaribe River, and the results showed that when no quality control was applied, the concentration levels would be underestimated, leading to incorrect results and inaccurate conclusions.