Effect of liming on polycyclic aromatic hydrocarbons leaching from hydrocarbon-contaminated tectogenic industriosol.

Soil stabilization/solidification is commonly employed remediation method for contaminated soils. Until now, limited attention has been given to the application of quicklime in polycyclic aromatic hydrocarbons (PAHs) contaminated soil. We treated a tectogenic industriosol spiked with 50 mg kg-1 of four PAHs (12.5 mg kg-1 each of fluorene (FLU), phenanthrene (PHE), fluoranthene (FLT) and pyrene (PYR)) using three different liming agents at 1% (w:w): quicklime (CaO), hydrated lime (Ca(OH)2) and carbonate calcium (CaCO3). All treated samples were leached in water at a solid-liquid ratio of 10, with subsequent analysis of leached soil and leachates for PAHs content. Results revealed that the addition of liming agents led to a reduction in FLU and PHE concentrations in treated soil by 6.81 ± 2.47% and 28.88 ± 4.18%, respectively, compared to a not-treated sol. However, no significant impact was observed on the 4-cycles PAHs (FLT and PYR). The addition of liming agents also significantly decreased the amount of PAHs in the leachate, by 100% for FLU and PHE, and by 74.9 ± 17.5% and 72.3 ± 34.8%, for FLT and PYR, respectively, compared to not limed soil. Among the liming agents, quicklime was the most effective in reducing the amount of 4 cycles PAHs in the leachate. Various mechanisms, such as encapsulation, volatilization and oxidation could contribute to this observed reduction. Quicklime treatment at a concentration of 1% w:w in PAHs-contaminated soil emerges as a promising technique to effectively reduce PAHs concentration in soils and mitigate PAHs mobility through leaching. This study also sheds light on the possibility to limit CO2 emissions and resources exploitation to assure the remediation process, thereby enhancing its overall environmental sustainability.

Epilithic biofilms, POCIS, and water samples as complementary sources of information for a more comprehensive view of aquatic contamination by pesticides and pharmaceuticals in southern Brazil.

Spatial-temporal monitoring of the presence of pesticides and pharmaceuticals in water requires rigor in the choice of matrix to be analyzed. The use of matrices, isolated or combined, may better represent the real state of contamination. In this sense, the present work contrasted the effectiveness of using epilithic biofilms with active water sampling and with a passive sampler-POCIS. A watershed representative of South American agriculture was monitored. Nine sites with different rural anthropic pressures (natural forest, intensive use of pesticides, and animal waste), and urban areas without sewage treatment, were monitored. Water and epilithic biofilms were collected during periods of intensive pesticide and animal waste application. After the harvest of the spring/summer crop, a period of low agrochemical input, the presence of pesticides and pharmaceuticals was monitored using the POCIS and epilithic biofilms. The spot water sampling leads to underestimation of the level of contamination of water resources as it does not allow discrimination of different anthropic pressures in rural areas. The use of endogenous epilithic biofilms as a matrix for the analysis of pesticides and pharmaceuticals is a viable and highly recommended alternative to diagnose the health of water sources, especially if associated with the use of POCIS.

Presence of pharmaceuticals and bacterial resistance genes in river epilithic biofilms exposed to intense agricultural and urban pressure.

The continuous discharge of pharmaceutical compounds into the aquatic environment has raised concerns over the contamination of water resources. Urban activities and intensive animal breeding are important sources of contamination. The accumulation of antibiotics may lead to the transfer or alternatively maintain the presence of resistance genes in natural microbial communities existing in epilithic biofilms. The objective of this study was to evaluate the pharmaceutical contamination levels and the presence of resistance genes in biofilms from a South Brazilian watershed. The Guaporé watershed exhibits a high diversity of land use, including agricultural and urban areas with differing levels of anthropogenic pressure. Seventeen sites along the Guaporé watershed were monitored. Biofilm samples were collected in two seasons (winter and summer), and the pharmaceutical concentration and quantity of resistance genes were analyzed. All monitored sites were contaminated with pharmaceuticals. Agricultural activities contribute through transferring pharmaceuticals derived from the application of animal waste to agricultural fields. The most contaminated site (pharmaceuticals and bacterial resistance genes) was located in an urban area exposed to high pressure. Decreases in the contamination of biofilms were also observed, exemplifying processes of natural attenuation in the watershed. The quality of the biofilms sampled throughout the watershed served as a useful tool to understand and monitor environmental pollution.

Extraction of extracellular polymeric substances from dam lake fresh sediments derived from crystalline bedrock.

Extracellular polymeric substances (EPS) produced by microorganisms have a key role in the sedimentary compartment, e.g. promoting aggregation and biostabilisation of sediment particles and increasing chemical reactivity at the water/sediment interface. Therefore, proper extraction methods are needed to study this EPS matrix. In this work, nine extraction methods based on physical (centrifugation, sonication), chemical (sodium hydroxide, sodium pyrophosphate, sodium tetraborate), and both chemical and physical (cation exchange resins, i.e. CER) treatments and their combinations, as well as the solid:liquid ratio used for extraction, were compared based on the quantity and compositions of extracted EPS. The organic carbon extracted was quantified and the nature of biochemical macromolecules (proteins, polysaccharides, and humic-like compounds) was evaluated using colorimetric methods. The amount of ATP was used as an indicator of cell lysis and showed contamination with intracellular materials in EPS extracted with chemical methods. Moreover, chemical extraction presented a large quantity of impurities due to non-removal of reactant salts by ultracentrifugation. For the nine methods tested, humic-like substances represented the main fraction of the extracted EPS, but for chemical extraction, the presence of humic materials from the sediment organic fraction was due to non-specific extraction of the EPS fraction. Therefore, chemicals methods are not recommended to extract EPS from sediment. Despite their low extraction efficiency, physical methods and CER, i.e. 'soft' extraction methods, are preferred using a solid:liquid ratio 1:40.

The use of epilithic biofilms as bioaccumulators of pesticides and pharmaceuticals in aquatic environments.

Biofilms are a consortium of communities of organisms that live in syntrophic relationships and present a higher organization level than that of individual cells. Biofilms dominate microbial life in streams and rivers, enable crucial ecosystem processes, contribute to global biogeochemical flows and represent the main active bacterial life form. Epilithic biofilms are the main biomass found in rivers; their exposure to contaminants can lead to changes in their structure and composition. The composition of these communities is influenced by physicochemical factors, temperature, light and prior exposure to pollutants, among other factors, and it can be used for water quality monitoring purposes. The heterogenous composition of biofilms enables them to accumulate compounds in an integrative manner. Moreover, the availability of several sorption sites and their likely saturation can contribute to bioaccumulation. In aquatic environments, biofilms are also susceptible to the acquisition of antibiotic resistance genes and participate in their dissemination. Anthropic pressure intensification processes continuously expose water resources and, consequently, biofilm communities to different contamination sources. Therefore, the use of biofilms to indicate environmental pollution is reinforced by the progress of studies on the subject. Biofilm communities' response to pollutants in aquatic environments can be mainly influenced by the presence of different organisms, which may change due to community development or age. The current research aims to review studies about biofilm contamination and highlight the importance of biofilm use to better evaluate and maintain the quality of water bodies.

"Modern agriculture" transfers many pesticides to watercourses: a case study of a representative rural catchment of southern Brazil.

The total cultivated area in Brazil reached to 62 million ha in 2018, with the predominance of genetically modified soybean and corn (36 and 17 million ha, respectively) in no-tillage systems. In 2018, 5.3 × 105 Mg of active ingredient of pesticides was applied in cropfields, representing about 7.3 L of commercial product by habitant. However, the monitoring of water courses contamination by pesticides remains scarce and is based on traditional grab sampling systems. In this study, we used the grab (water) and passive sampling (Polar Organic Chemical Integrative Sampler-POCIS) to monitor pesticide contamination in the river network of a representative agricultural catchment of southern Brazil. We selected 18 sampling sites located in tributaries and in the main course of the Guaporé River, in Rio Grande do Sul State, with different land use predominance including forest, urban, and agricultural areas. Altogether, 79 and 23 pesticides were, respectively, analyzed in water and POCIS samples. The water of Guaporé River and its tributaries were highly contaminated by many pesticides, especially by four herbicides (2,4-D, atrazine, deethyl-atrazine, and simazine), three fungicides (carbendazim, tebuconazole, and epoxiconazole), and one insecticide (imidacloprid). The amount, type, and concentration of pesticides detected were completely different depending on the sampling technic used. POCIS was effective to discriminate the contamination according to the main land use of each sampling site. The monitored areas with the predominance of soybean cultivation under no-tillage tended to have higher concentrations of fungicide, while in the more diversified region, the herbicides showed higher values. The presence of five herbicides used in corn and grassland forage production was correlated with areas of integrated crop-livestock systems, in contrast to higher contamination by 2,4-D in areas of intensive production of soybean and winter cereals.

Sorption of selected pharmaceuticals by a river sediment: role and mechanisms of sediment or Aldrich humic substances.

Sorption of pharmaceuticals onto sediments is frequently related to organic matter content. Thus, the present work aimed to compare the effect of humic substances (HS) extracted from a river sediment versus Aldrich (HS) on the sorption of selected pharmaceuticals onto this river sediment. The results exhibited no "unique" effect of the presence of HS from the same origin. Thus, the sediment HS increased the sorption of sulfamethoxazole (SMX), diclofenac (DCF), and trimethoprim (TMP), but reduced the sorption of atenolol (ATN). The presence of Aldrich HS increased the sorption of TMP and ATN and decreased the sorption of SMX and DCF. Fluorescence quenching measurements revealed that these effects cannot be explained only by the presence of pharmaceutical HS associations. The use of several sorption models suggested that the sorption of SMX, DCF, and ATN involves multilayer mechanisms. Furthermore, it was pointed out that the presence of HS does not change the sorption mechanisms although it was observed interaction between HS and the sediment. Indeed, the sediment HS sorbs onto the sediment whereas the Aldrich HS tends to mobilize organic compounds from the sediment to the solution.