Lichens as bio-monitors of polycyclic aromatic hydrocarbons: Measuring the impact of features and traffic patterns.

The role of road characteristics, including gradient and speed control devices, in influencing emission dynamics remains to be fully elucidated. Most studies have focused on fuel consumption as an indirect indicator of sector emissions instead of directly quantifying specific pollutants, like polycyclic aromatic hydrocarbons (PAHs). This research approach is often due to the complexities involved in capturing these pollutants and their subsequent analysis. Bio-monitors, such as lichens, offer an economically viable method. Their wide distribution across various habitats enables the comparison of PAH levels in diverse environments. Against this background, The present work analyses the ability of tropical lichens to indicate the effect that traffic patterns and geometric design features of roads (traffic activity, road gradient, traffic control devices, and vehicular speed) have on the emission of PAH concentration. Results showed that PAHs in lichens strongly correlated with the road gradient (Spearman correlation, p<0.005 with R=0.98). Each 1% increase in road gradient implies a rise of 24 ngPAH/gLichen in National Road. Additionally, a trend coherent of PAH concentration with the vehicle speed profile was observed on Panamericana Road. Speed control devices were associated with higher concentrations of PAHs due to acceleration and braking actions that increment fuel consumption. Finally, the results evidenced that lichens helped determine the source of aromatics and their carcinogenic potential using the diagnostic ratio of PAHs and the carcinogenic equivalence sum, respectively.

Osmoregulatory responses in the neotropical fish species Astyanax lacustris, exposed to single and combined microplastics, polycyclic aromatic hydrocarbons, and their mixture.

Microplastic (MP) pollution poses a significant environmental threat. These MPs can adsorb toxic compounds such as polycyclic aromatic hydrocarbons (PAH), which are highly lipophilic and carcinogenic. To assess the potential effects of virgin MP, PAH, and MP+PAH in association with osmoregulation and energetic substrate, we conducted experiments with the tetra cardinal Astyanax lacustris. The environmentally relevant concentration of MP (10 mg L-1) and 20 % of the LC50-96 h of crude oil for A. lacustris (2.28 µg L-1) were used during the 96-h exposure. Fish were exposed to virgin MP, PAH, MPC (MP loaded with PAH), PAH+MP (PAH and MP in association), and the control without (CT) and with handling (CH). After 96 h, blood was collected for osmoregulatory parameters (plasma osmolality; Na+, K+, Cl-, Mg2+; glycose and lactate); gills for osmoregulatory enzyme activities (Na+, K+ ATPase, H+ ATPase, and carbonic anhydrase); and white muscle samples were used to determine glycogen as an energetic substrate. The low molecular weight PAH was not detected in PAH-loaded MP (MPC) and PAH in combination with MP (PAH+MP). The PAH concentration of the MPC and PAH+MP was similar and low compared to other works. Virgin MP, PAH, MPC, and PAH+MP were able to cause muscle glycogen depletion. The activity of v-type H+ ATPase and plasma Na+ concentrations were lower in PAH with MP (MPC). However, the hydromineral balance (K+, Mg2+, Cl-, and osmolality) was not affected by any treatment. In this sense, we can conclude that the MPC caused osmoregulatory disturbances not seen in the MP associated with PAH (MP+PAH). However, this seems unrelated to the PAH leaking from the MPC or the PAH absorption to the virgin MP once the PAH concentrations from the MPC and PAH+MP were similar.

Aromatic hydrocarbons extracted by headspace and microextraction methods in water-soluble fractions from crude oil, fuels and lubricants.

Two extraction protocols were developed for the determination of mono- and poly-aromatic hydrocarbons in water-soluble fractions from gasoline, diesel, crude, mineral insulating, and lubricant oils. Development of the procedures was based on clean miniaturized strategies, such as headspace extraction and vortex-assisted dispersive liquid micro-extraction, together with quantification by gas chromatography-mass spectrometry. The mono-aromatic hydrocarbons were extracted using the headspace extraction method. The linear range obtained was 10-500 µg L-1, with r2 > 0.99. Based on the parameters of the analytical curves, detection and quantification limits of 2.56-3.20 and 7.76-9.71 µg L-1 were estimated. In addition, the method showed adequate recoveries of 69.4-83.5%, with a satisfactory precision of 4.7-17.1% (n = 5). Micro-extraction was applied for the poly-aromatics and the most favorable variables were sample volume (5.00 mL) in sodium chloride medium (1%, w/v), trichloromethane as extractor solvent (75 µL), acetone as disperser (925 µL) and vortexing for 1 min. Under these conditions, analytical curves of 0.15-4.00 µg L-1 were obtained and limits of determination and quantification were 0.03-0.15 and 0.09-0.46 µg L-1, respectively. Recovery values of 87.6-124.5% and a maximum relative standard deviation of 18.9% (n = 5) verify satisfactory accuracy and precision. This led to the achievement of enrichment factors for poly-aromatic hydrocarbons of 41-89 times. Finally, the methods were employed in samples of water-soluble fractions for the determination of analytes. The values followed the order: gasoline > diesel > crude > lubricant > mineral insulating oil. These results indicate an increase in lighter fractions, followed by poly-aromatics in more refined products.

Determination of polycyclic aromatic hydrocarbons extracted from lichens by gas chromatography-mass spectrometry.

Lichens are well-known biomonitors for semi-volatile pollutants, due to their ability to absorb and retain different chemical compounds such as Polycyclic Aromatic Hydrocarbons (PAHs), directly linked to levels in the atmosphere. Based on that, this paper proposes an analytical method capable of quantifying 16 EPA-PAHs from lichens found in an intertropical zone, as a natural alternative to typical capture methods, with the aim of monitoring atmospheres polluted by toxic compounds. An analytical protocol, including sample pre-treatment, followed by ultrasound extraction, clean-up in a chromatographic column, concentration and quantification by Gas Chromatography-Mass Spectrometry (GC-MS) using Selective Ion Monitoring has been developed. Additionally, a set of guidelines on lichen collection and sample handling is given, in order to achieve representative samples.•Limits of quantification (LOQ) and detection (LOD) varied from 2.0 to 16 µg/L and 1.0 to 5.0 µg/L, respectively. Calibration curves had correlation coefficients higher than 0.99 in all cases.•Validation of the method for determining PAHs concentration associated to 30 lichen samples collected along two roads, with high and low traffic volumes was carried out.•The method showed good performance according to the sources of PAHs, traffic patterns and gradient in roads.

Impact of polycyclic aromatic hydrocarbons in mangroves from the Colombian pacific coast: Evaluation in sediments and bivalves.

Bivalves and sediments were sampled from mangroves in the Pacific Coast of Colombia to evaluate the concentrations of the 16 polycyclic aromatic hydrocarbons (PAHs) prioritized by U.S.EPA. Mangroves are highly vulnerable to anthropogenic activities, such as oil spills, which affect sediments and the organisms that depend on that ecosystem. Twelve samples of mangrove and non-mangrove (sandy) sediments and 20 samples of Anadara tuberculosa from mangrove were collected in marine and estuarine areas. In sediments and A. tuberculosa, the highest concentration of Æ©16PAHs was found in estuarine mangroves close to the Rosario River mouth, ranging from 171.4 to 564.0 ng g-1 and 31.0 to 169.0 ng g-1, respectively. For the bivalve, the concentrations showed less variability than sediment, with 25% and 20% of bivalve samples exceeding the limits established by the European Regulatory Commission and Ministry of Health and Social Protection of Colombia, respectively, which can cause effects on people's health. The PAHs isomeric ratios determined in sediments indicated that these compounds were originated mainly from petrogenic sources. The PAHs profile reveals the dominance of 3 and 4 rings PAHs in sediments and dominance of 4 rings PAHs in bivalves.

Genotoxic, metabolic, and biological responses of Chironomus sancticaroli Strixino & Strixino, 1981 (Diptera: Chironomidae) after exposure to BBP.

Benzyl butyl phthalate (BBP), which is widely used in industrial production, reaches the aquatic environment, mainly owing to improper disposal of plastic products. In the water, it remains adsorbed to sedimentary particles causing toxic effects in aquatic invertebrates such as Chironomidae, which are important in maintaining ecosystem dynamics and are an important link in the food chain. However, the effects of BBP on Chironomidae are still poorly known. Thus, the toxic effects of BBP on Chironomus sancticaroli at acute (48 h), subchronic (8 d), and chronic (25 d) exposures of concentrations between 0.1 and 2000 µg·L-1 were determined. Genotoxicity effects, changes in the oxidative stress pathway, and development and emergence of organisms were evaluated. Biochemical markers showed a reduction in cholinesterase (ChE) activity, indicating a neurotoxic effect on acute exposure (1-1000 µg·L-1). The antioxidant pathway, glutathione S-transferase (GST) activity showed reduction on acute (0.1; 1-2000 µg·L-1) and subchronic (1-2000 µg·L-1) exposures and reduction in superoxide dismutase (SOD) activity at all evaluated concentrations, suggesting oxidative stress. In contrast, lipid peroxidation was not observed. DNA damage occurred on acute (10 µg·L-1) and subchronic (10-2000 µg·L-1) exposures, indicating genotoxic effects. At concentrations above 10 µg·L-1, no emergence of adults occurred, while lower concentrations (0.1 and 1 µg·L-1) showed a reduction in the number of adults, mainly males. The observed effects indicate that BBP is genotoxic and causes biochemical alterations presenting high toxicity at the population level.

Acute exposure to the water-soluble fraction of gasoline (WSFG) affects oxygen consumption, nitrogenous-waste and Mg excretion, and activates anaerobic metabolism in the goldfish Carassius auratus.

Contamination of aquatic environments by petroleum and its products (e.g. gasoline) is a hazard for aquatic organisms as a result of the potential toxicity of monocyclic aromatic hydrocarbons (BTEX) and polycyclic aromatic hydrocarbons (PAH). Our goal was to evaluate the acute effects of the water-soluble fraction of gasoline (WSFG) on nitrogen excretion, osmoregulation, and metabolism of goldfish Carassius auratus. We first chemically characterized the WSFG and then tested its effects on these physiological aspects of C. auratus, in several different exposure scenarios (0, 0.25, 5, 10 and 25% of WSFG). The WSFG contained high concentrations BTEX (toluene 70% and benzene 17%) relative to PAH (<1%), and low levels of several metals (Al, Fe, Zn, Sr). Routine O2 uptake rate (MO2) of goldfish was inhibited by exposure to 5% WSFG, and during post-exposure recovery, MO2 increased in a dose-dependent fashion. Ammonia excretion was not affected by exposure to WSFG, but urea-N excretion increased progressively with the WSFG concentration. The same pattern of dose/response was observed for net Mg2+ loss rates and steadily increasing plasma lactate concentrations. Loss rates of Na+, Ca2+, K+ and Cl-, and plasma concentrations of Mg2+ and urea-N were not significantly altered. We propose that acute exposure to WSFG inhibits aerobic metabolism and activates anaerobic metabolism, breaking down ATP such that bound Mg2+ is liberated and the purine ring component is metabolized to urea-N, both of which are subsequently excreted.

Cytotoxicity and enzymatic biomarkers as early indicators of benthic responses to the soluble-fraction of diesel oil.

Xenobiotics from oil tanker leaks and industrial discharges are amongst the main human impacts to confined coastal areas. We assessed the genotoxic responses to the water-soluble fraction of diesel oil in the polychaete Laeonereis culveri and the bivalve Anomalocardia flexuosa, two widespread benthic species in subtropical estuaries from the Southwestern Atlantic. We hypothesized that the highest responsiveness would be expressed by significantly different biomarkers responses between control and oil-impacted treatments. Responsiveness to diesel oil was investigated using an experimental design with two fixed factors (contaminant percentages and times of exposure). After exposure, we monitored the responses of the oxidative stress enzymes and performed micronuclei tests. Results were congruent for both species. Antioxidant defense of glutathione S-transferase and the induction of micronuclei and nuclear buds, the latter just for the bivalve, were significantly affected by polycyclic aromatic hydrocarbons, with significant increases on the seventh day of exposure and in the higher concentrations, compared to controls groups. We assessed the benefits and drawbacks of using each biomarker in laboratory experiments. Both species are indicators of early, and rapid responses to genotoxic contaminants in subtropical estuarine habitats. We suggest that the micronuclei frequency in A. flexuosa is a simple, fast and cheap test for genotoxicity in oil-impacted areas. Such early biomarkers are needed to develop better protocols for impact assessment and monitoring under real field conditions.

Preconcentration of polar phenolic compounds from water samples and soil extract by liquid-phase microextraction and determination via liquid chromatography with ultraviolet detection.

This work proposes a liquid-phase microextraction (LPME) method to extract the highly polar compounds phenol (Ph), o-cresol (o-Cr), m-cresol (m-Cr), p-cresol (p-Cr), and 2,4-dimethylphenol (2,4-DMP) from aqueous matrices. The first extraction step of the LPME method employed a common volumetric flask and n-octanol, and the second extraction step used NaOH as the acceptor phase. The optimized extraction conditions were 900 µL of n-octanol as the extraction solvent, NaOH at 0.60 mol L(-1) as the acceptor phase, an extraction time of 5.0 min, HCl at 0.01 mol L(-1) and NaCl at 20.0% as the donor phase, and an extraction temperature of 20.0°C. The analysis of 50.0 mL of aqueous sample, pretreated under the optimized LPME conditions, afforded a limit of detection (LOD) between 0.3 and 3.5 µg L(-1), a limit of quantification (LOQ) between 1.2 and 11.6 µg L(-1), and a linear range from 2.50 to 50.0 µg L(-1) for Ph, o-Cr, m-Cr and p-Cr and from 12.5 to 250 µg L(-1) for 2,4-DMP. The proposed LPME method was a successful sample preparation strategy, and allowed for precise and accurate quantification of polar phenolic compounds in aqueous matrices such as tap water, river water, groundwater, and seawater, and also in a soil extract. The recovery values ranged from 72.5% to 126.0%, and the relative standard deviation was between 0.3 and 11.5%.

Interaction of phenol, o-cresol, and p-cresol with a clay-rich soil sample.

The present paper describes an interaction study of phenol, o-cresol, and p-cresol with a rich-clay soil sample (clay content of 62.3%). Experiments performed using long contact times, in concentrations of 50.0 mg L(-1) showed practically no signal of phenol, o-cresol, and p-cresol after 48, 72, and 120 h, respectively, suggesting a sorption process. Sorption experiments in the period of 24 h were carried out with the phenolic compounds in concentrations between 5.00 and 500.0 mg L(-1), and negligible interaction between the phenolic species and the soil was observed. Additional experiments were carried out using HgCl(2) or NaN(3) solution as biodegradation inhibitors. After 10 days of contact time in the presence of inhibitors, no alterations in the concentrations of the three compounds studied were observed, and the results suggest no sorption process, with the compounds being almost entirely biodegraded by the soil sample, or possibly the formation of nonextractable residues could occur.