The impact of chronic and acute problems on sea turtles: The consequences of the oil spill and ingestion of anthropogenic debris on the tropical semi-arid coast of Ceará, Brazil.

Sea turtle mortality is often related to materials that reach the coast from different anthropic activities worldwide. This study aimed to investigate whether sea turtle mortality was related to older marine problems, such as solid waste, or one of the largest oil spill accidents on the Brazilian coast, that occurred in 2019. We posed three questions: 1) Are there solid residues in the digestive tract samples, and which typology is the most abundant? 2) Can meso­ and macro-waste marine pollutants cause mortality? 3) Is the dark material found really oil? A total of 25 gastrointestinal content (GC) samples were obtained, of which 22 ingested waste of anthropogenic origin and 18 were necropsied. These 22 samples were obtained during or after the 2019 oil spill, of which 17 specimens were affected, making it possible to suggest oil ingestion with the cause of death in the animals that could be necropsied. Macroscopic data showed that the most abundant solid waste was plastic (76.05 %), followed by fabrics (12.18 %) and oil-like materials. However, chemical data confirmed only three specimens with oil levels ranging from remnants to high. It was possible to infer possible causes of death in 16 of the total 18 necropsied cases: Most deaths were due to respiratory arrest (62.5 %), followed by pulmonary edema (12.5 %), cachexia syndrome (12.5 %), circulatory shock (6.25 %), and head trauma (6.25 %), which may have been caused by contact with solid waste, oil, or both. The study showed that not all dark material found in the GCs of turtles killed in oiled areas is truly oil, and in this sense, a chemical analysis step to prove the evidence of oil must be added to international protocols.

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.

Tarballs on the Brazilian coast in late 2022 sustain Lepas anatifera Linnaeus, 1758 (Crustacea: Cirripedia): Occurrence and risk of petroleum hydrocarbon ingestion.

Since the 2019 oil spill on the northeastern coast of Brazil, oil materials have washed up on the beaches. A characteristic of the recent oil spill that began in late August was that some of the oiled material, such as tarballs, contained the goose barnacle species Lepas anatifera (Cirripedia, Lepadomorpha), which is well-known for its cosmopolitan distribution and wide occurrence in the oceans. The findings of this study provide information on the occurrence and contamination of petroleum hydrocarbons in animals adhered to the surfaces of tarballs sampled from beaches in the Brazilian states of Ceará and Rio Grande do Norte, between September and November 2022. The size of the barnacles varied from 0.122 to 2.20 cm, suggesting that the tarballs had been floating in the ocean for at least a month. All groups of L. anatifera collected from the tarballs had polycyclic aromatic hydrocarbons (PAHs) present (∑21PAHs from 476.33 to 3816.53 ng g-1). In comparison to high-molecular-weight PAHs, which are primarily from pyrolytic sources, low-molecular-weight PAHs, such as naphthalene and phenanthrene, which are mostly related to petrogenic sources, were shown to be more abundant. In addition, dibenzothiophene, which is exclusive of petrogenic origin, was found in all samples (30.74-537.76 ng g-1). The aliphatic hydrocarbons (AHs): n-alkanes, pristane, and phytane were also found and displayed petroleum characteristics. These results highlight the danger of increasing the absorption of petrogenic PAHs and AHs by organisms that use tarballs as substrates. L. anatifera is a crucial component of the food chain because many animals such as crabs, starfish, and gastropods consume it.

Is there a similarity between the 2019 and 2022 oil spills that occurred on the coast of Ceará (Northeast Brazil)? An analysis based on forensic environmental geochemistry.

The main objective of this study was to investigate the 2019 and 2022 oil spill events that occurred off the coast of the State of Ceará, Northeastern Brazil. To further assess these mysterious oil spills, we investigated whether the oils stranded on the beaches of Ceará in 2019 and 2022 had the same origin, whether their compositional differences were due to weathering processes, and whether the materials from both were natural or industrially processed. We collected oil samples in October 2019 and January 2022, soon after their appearance on the beaches. We applied a forensic environmental geochemistry approach using both one-dimensional and two-dimensional gas chromatography to assess chemical composition. The collected material had characteristics of crude oil and not refined oils. In addition, the 2022 oil samples collected over 130 km of the east coast of Ceará had a similar chemical profile and were thus considered to originate from the same source. However, these oils had distinct biomarker profiles compared to those of the 2019 oils, including resistant terpanes and triaromatic steranes, thus excluding the hypothesis that the oil that reached the coast of Ceará in January 2022 is related to the tragedy that occurred in 2019. From a geochemical perspective, the oil released in 2019 is more thermally mature than that released in 2022, with both having source rocks with distinct types of organic matter and depositional environments. As the coast of Ceará has vast ecological diversity and Marine Protected Areas, the possibility of occasional oil spills in the area causing severe environmental pollution should be investigated from multiple perspectives, including forensic environmental geochemistry.

An integrated assessment to reconstruct the history of changes influenced by multiple anthropogenic activities (City of Fortaleza, Ceará, Brazil).

In this study, the multi-marker approach was used for the first time with a highly urbanized lake located in the city of Fortaleza, Brazil, to provide a comprehensive view of temporal trends in sources of pollutants and evaluate the relation between the influence of anthropogenic activities and socioeconomic development. Total concentrations of the markers analyzed ranged from 21.0 to 103.8 ng g-1, 450.2 to 2390.2 ng g-1, and 233.8 to 9827.3 ng g-1 for ∑PAHs, ∑n-alk, and ∑sterols, respectively. Concentrations and patterns of PAH, AH, and sterol ratio distribution changed over time and may be associated with different episodes in the history of the city of Fortaleza. The marker ratio distribution in the sediment core revealed an overlap of natural and anthropogenic sources, with degraded oil, biogenic inputs, pyrogenic processes, and fecal contamination from humans and animals in the past changing to petroleum fossil inputs and high contamination from sewage in the present day. The distribution of markers and the chronological history of Fortaleza revealed two distinct periods related to human activities during the development of the city. In the first period (prior to the 1950s), the main human activities were animal breeding and the use of biomass for domestic activities, public and cargo transportation, and commercial activities, especially food production. In the second period (after the 1950s), expansion of the city occurred due to the so-called Brazilian economic miracle and the main human activities were industrialization and urbanization processes, involving deforestation, paving, sewage discharge, and petroleum combustion.

Dealing with complex contamination scenarios: using a multi-geochemical approach to assess environmental quality and identify pollution sources in a semi-arid estuary from Brazil.

The Jundiaí-Potengi Estuary (EJP) is located on the semi-arid coast of northeastern Brazil and is influenced by multiple sources of contamination. The sediment quality of EJP was assessed by using a multi-geochemical approach during the dry and wet seasons. Sediments were analyzed for concentrations of nutrients, metals, polycyclic aromatic hydrocarbons (PAHs), pesticides, hormones (natural and synthetic), and sterols. The results were integrated by multivariate methods. The sediment was altered by the presence of contaminants from anthropogenic and natural sources. The middle and lower estuarine areas were considered more degraded in both seasons. In these regions, metals, hormones, sterols, and PAHs were found, indicating that these regions are severely affected by industrial, sanitary and aquaculture effluents, combustion of fossil fuels, and oil spills. The upstream region was contaminated by pesticides. The contamination pattern along the EJP shows the prevalence of local sources which continuously release the chemicals into the estuary. Worse conditions occurred during the rainy season, when the runoff from urban and rural areas is more intense and carries a greater load of contaminants to the EJP.

Tracking the historical urban and rural sources of fecal pollution in a South American tropical semi-arid region using sterols and endocrine-disrupting chemicals.

Sterols and endocrine-disrupting chemicals were analyzed in two dated sediment cores collected in the Jaguaribe river to determine the recent decades' influence of urbanization and agropastoral activities on the inputs of fecal pollution in a semi-arid region of Brazil. Stigmasterol and sitosterol were the most abundant of the 6 sterols examined in both cores, indicating an important contribution of organic matter from mangrove forests to the study region. Coprostanol presented a continuous increase in concentrations from the 1930s to the 2000s in one core, however, showing higher concentrations (>100 ng g-1) in the upper layers of both cores. The sterols diagnostic ratios indicated fecal pollution through both cores, especially from the 1940s to 1970s. The coprostanol levels followed the variations in population growth in the state of Ceará. Estriol and estrone were the most abundant estrogenic hormones found in both cores. These compounds are probably related to the intense livestock activities in the Ceará state, especially after the 1970s. The baseline levels of fecal sterols and estrogen hormones found in this study possibly represent a previous unimpacted scenario and may be used for future evaluations of fecal pollution from urbanization and livestock activities.

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.

A better understanding of air quality resulting from the effects of the 2020 pandemic in a city in the equatorial region (Fortaleza, Brazil).

The year 2020 was atypical due to the pandemic caused by the SARS-CoV-2 virus (COVID-19), providing a unique opportunity to understand changes in air quality due to the reduction in urban activity. Therefore, the aim of the present study was to perform an integrated evaluation on the influence of the effects of the 2020 pandemic on air quality in the city of Fortaleza, investigating levels of PM2.5, PM10, NO2, NO, SO2, CO, and O3, corresponding health risks, as well as the influence of meteorological variables and urban activity. In all phases analyzed, significant reductions were found in NOx, NO, NO2, and CO. A considerable reduction in PM2.5 and PM10 was found in the early phases, with an increase in the later phases. These findings are explained by the nearly 50% reduction in vehicular traffic and the consequent reduction in fossil fuel emissions, mainly in the partial lockdown and total lockdown periods, as well as reductions in commercial (stores/shops) and industrial activities. The variation in O3 was initially non-significant, followed by a considerable increase in the last three phases analyzed; this increase was influenced by changes in temperature and the incidence of sunlight. SO2 concentrations increased in the period studied, demonstrating that the vehicular fleet, local commerce, and other activities are not the predominant sources of this compound. Estimated health risks were reduced by half during the lockdown period, especially for non-smokers, followed by a drastic increase in the last three phases. The planetary boundary layer was positively correlated with O3 and PM10 and negatively correlated with NOx, NO2, and NO, indicating its influence on the distribution of pollutants in the lower atmosphere and, consequently, air quality.

Influence of the seasonality and of urban variables in the BTEX and PM2.5 atmospheric levels and risks to human health in a tropical coastal city (Fortaleza, CE, Brazil).

The International Agency for Research on Cancer (IARC) classifies benzene in group 1 (carcinogenic to humans). Particulate matter (PM) has recently also been classified in this category. This was an advance toward prioritizing the monitoring of particles in urban areas. The aim of the present study was to assess levels of PM2.5 and BTEX (benzene, toluene, ethylbenzene, and xylene), the influence of meteorological variables, the planetary boundary layer (PBL), and urban variables as well as risks to human health in the city of Fortaleza, Brazil, in the wet and dry periods. BTEX compounds were sampled using the 1501 method of NIOSH and determined by GC-HS-PID/FID. PM2.5 was monitored using an air sampling pump with a filter holder and determined by the gravimetric method. Average concentrations of BTEX ranged from 1.6 to 45.5 µg m-3, with higher values in the wet period, which may be explained by the fact that annual distribution is influenced by meteorological variables and the PBL. PM2.5 levels ranged from 4.12 to 33.0 µg m-3 and 4.18 to 86.58 µg m-3 in the dry and wet periods, respectively. No seasonal pattern was found for PM2.5, probably due to the influence of meteorological variables, the PBL, and urban variables. Cancer risk ranged from 2.46E-04 to 4.71E-03 and 1.72E-04 to 2.01E-03 for benzene and from 3.07E-06 to 7.04E-05 and 3.08E-06 to 2.85E-05 for PM2.5 in the wet and dry periods, respectively. Cancer risk values for benzene were above the acceptable limit established by the international regulatory agency in both the dry and wet periods. The results obtained of the noncarcinogenic risks for the compounds toluene, ethylbenzene, and xylene were within the limits of acceptability. The findings also showed that the risk related to PM is always greater among smokers than nonsmokers.

Evaluation of OSPM against air quality measurements in Brazil - the case study of Fortaleza, Ceará.

The contribution of vehicle emissions to air pollution is considered a large environmental and health problem in big Brazilian cities caused, among other factors, by slow renewal of the old vehicle fleet. Brazilian studies usually only consider traffic-related issues in transportation analysis, with minor assessments of emissions and close to non-existent assessment of air quality. On this background, this research aimed to calibrate and evaluate the Operational Street Pollution Model (OSPM®) to Brazilian conditions by implementing Brazilian emission factors. The urban background concentrations were modeled with the Urban Background Model (UBM) as part of the air quality system (THOR-AirPAS). In this case, we used meteorological data from a ground meteorological station outside Fortaleza processed by meteorological pre-processor and regional background concentrations from the Integrated Forecast System (IFS) as input to UBM. New air quality measurements were collected in busy streets of the city of Fortaleza during the year of 2017. The study collected samples of daily NO2 and PM10 concentrations to evaluate OSPM daily estimations. In addition, a transportation travel demand model (TRANUS) has been calibrated to the case study area with observed traffic data collected, in order to provide Annual Average Daily Traffic (AADT) as inputs to OSPM®. Two sets of emission factors were evaluated. Official Brazilian emission factors were applied to OSPM®, as well as adjusted emission factors derived in the project based on calibration that were higher than the official emission factors. Data showed that concentrations are significantly influenced by meteorological factors (such as temperature, wind speeds, wind directions), and especially precipitation for PM10 concentrations. OSPM® simulated results showed concentration levels and patterns close to air quality measurements with default emission factors and calibrated emission for UBM but large underestimations if official emissions were used for both UBM and OSPM. Implications: Busy urban streets in Brazilian cities with intense flow of diesel vehicles (such as buses and trucks) can significantly increase air pollution, especially for NO2 and PM10. With OSPM calibrated and evaluated to Brazilian conditions, the model system can be used by authorities to assess the impact of policy measures, such as vehicle access restrictions in Low Emission Zones, in order to consider not only traffic related issues, but also air pollution due to mobile sources with outdated emission technologies.

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.

Influence of sediment parameters on the distribution and fate of PAHs in an estuarine tropical region located in the Brazilian semi-arid (Jaguaribe River, Ceará coast).

18 polycyclic aromatic hydrocarbons (PAHs) were evaluated in the Jaguaribe River to explore the influence of grain size, organic carbon, humic and fulvic acids and black carbon on their adsorption onto sediment. The ∑PAHs concentrations variated from 0.6 to 3752.0 ng g-1 with highest concentrations in the estuarine zone. The PAHs predominant source along the river was from mixed sources, mainly related to biomass combustion, small oil spills related to recreational nautical activities and runoff from cities. Organic and inorganic parameters presented influence on PAHs distribution along the river, with humic acid as a determinant factor. These research findings are of importance to an assessment of the fate and transport of PAHs in estuarine systems.

Influence of anthropogenic activities and risk assessment on protected mangrove forest using traditional and emerging molecular markers (Ceará coast, northeastern Brazil).

Anthropogenic molecular markers were used to assess chemicals inputs and ecological risks associated from multiple sources to sediments in one of the largest tropical mangrove forests of South America, with a particular focus on lesser studied compounds resulting from rural activities. Total concentrations ranged from 23.4 to 228.2 ng g-1 for polycyclic aromatic hydrocarbons (∑PAHs), 750.4 to 5912.5 ng g-1 for aliphatic hydrocarbons (∑AHs), 32.4 to 696.6 ng g-1 for pesticides (∑pesticides), 23.1 to 2109.7 ng g-1 for coprostanol and sterols (∑sterols), 139.3 to 580.2 ng g-1 for naturals hormones (∑natural hormones) and 334.1 to 823.4 ng g-1 for synthetics hormones (∑synthetic hormones). The PAHs and AHs used as traditional anthropogenic markers showed a mixture between natural and anthropogenic sources, related mainly to inputs from higher plants, phytoplankton and both, biomass and petroleum combustion. Rural activities linked to agricultural pest control are the predominant source of pesticides, although minor inputs from pesticides used in urban public health campaigns and household activities were also detected. Synthetic hormones levels are two to three orders of magnitude greater than natural hormones levels and no correlations were observed between the main sewage markers and synthetic hormone concentrations, rural activities such as animal husbandry, which use drugs in management, may be the predominant anthropogenic sources of these compounds in the region. Traditional markers failed to detect ecological risks in rural areas, where synthetic substances (e.g. pesticides and hormones) are widely used and introduced in the environment.

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.

Estimated Levels of Environmental Contamination and Health Risk Assessment for Herbicides and Insecticides in Surface Water of Ceará, Brazil.

Methodology using solid phase extraction and high performance liquid chromatography (SPE-C18/HPLC-DAD) was applied to pesticide determinations in ten water reservoirs in the semidarid region of northeastern Brazil. The validated method was suitable for determination of herbicides and insecticide in surface water. The recovery efficiency of atrazine, methyl-parathion and simazine was approximately 70%. The method also showed good linearity and selectivity with correlation coefficients (R) greater than 0.99. The limits of detection were below the maximum residue limits (MRLs) established by government agencies. Studied reservoirs showed presence of atrazine at mean levels from 7.0 to 15.0 µg/L. Simazine and methyl parathion were not detected during the period. The atrazine levels measured from this semiarid region are of the same magnitude as those found in regions with moderate to high agricultural activity. According to detected atrazine concentrations, the annual health risk to humans was insignificant. However, the control of herbicides is important to maintain the quality of water in the reservoirs of Ceará, Brazil.

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.

4-hydroxy-2,5-dimethylphenyl-benzophenone: conformational stability, FT-IR and Raman investigation.

In this paper we have studied the 4-hydroxyl-2,5 dimethylphenyl-benzophenone. Also, it was analyzed the vibrational assignment (FT-IR and Raman) in conjunction with computational results. The conformational analysis showed three barrier heights where two are due to the dihedral rotation and the other one is attributed to hydroxyl rotation. While the high dihedral rotational barrier (TS1) is 6.06-7.22 kcal mol(-1), the lower one (TS2) is almost three times smaller. The variations with the change of basis set is 5-8% to TS1, and 3-15% in the values predicted to TS2. In the case of OH rotational barrier, the values range from 3.70 to 4.86 kcal mol(-1), and it is also observed that this transition state is less sensitive to the change of basis set and to the method. Two isomers was detected due to the changes in the OH rotation with the gap energy lower than 0.7 kcal mol(-1), and at this point is seen that semi-empirical methods fail into describe the most stable conformation which may be due to the small energy gap. The enthalpy formation at 0 K and 298 K was 111.71 and 102.20 kcal mol(-1), respectively.