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.

Indiscriminate use of glyphosate impregnates river epilithic biofilms in southern Brazil.

Epilithic biofilms are communities of microorganisms composed mainly of microbial cells, extracellular polymeric substances from the metabolism of microorganisms, and inorganic materials. Biofilms are a useful tool to assess the impact of anthropic action on aquatic environments including the presence of pesticide residues such as glyphosate. The present work seeks to monitor the occurrence of glyphosate and AMPA residues in epilithic biofilms occurring in a watershed. For this, epilithic biofilm samples were collected in the Guaporé River watershed in the fall and spring seasons of 2016 at eight points. Physicochemical properties of the water and biofilms were determined. The determination of glyphosate and AMPA was performed using an ultra-high performance liquid chromatograph coupled to a tandem mass spectrometer. The concentrations of glyphosate and AMPA detected in epilithic biofilms vary with the season (from 90 to 305 µg kg-1 for glyphosate and from 50 to 240 µg kg-1 for AMPA, in fall and spring, respectively) and are strongly influenced by the amount of herbicide applications. Protected locations and those with poor access not demonstrate the presence of these contaminants. In the other seven points of the Guaporé River watershed, glyphosate was detected in concentrations ranging from 10 to 305 µg kg-1, and concentrations of AMPA ranged from 50 to 670 µg kg-1. An overview of the contamination in the Guaporé watershed shows that the most affected areas are located in the Marau sub-watershed, which are strongly influenced by the presence of the city of Marau. This confirms the indiscriminate use of glyphosate in the urban area (weed control, domestic gardens and horticulture) and constitutes a problem for human and animal health. The results showed that biofilms can accumulate glyphosate resulting from the contamination of water courses and are sensitive to the sources of pollution and pesticides present in rivers.

Phosphorus seasonal sorption-desorption kinetics in suspended sediment in response to land use and management in the Guaporé catchment, Southern Brazil.

Phosphate sorption-desorption parameters like maximum phosphorus (P) adsorption capacity (P max), equilibrium phosphorus concentration (EPC), water desorbable P (α), potentially bioavailable P (ß), and mobility index (α/ß ratio) were determined in order to understand the sediment source-sink nature in Guaporé catchment in southern Brazil during summer and winter 2013 and 2014. The result showed a significant (p = 0.05) variation across sediment site or seasons and revealed the most sorption-desorption parameters (P max, α, ß) with the increments following the order urban sediments > intensive agriculture under CT > intensive agriculture under NT > low agriculture sub-catchments (sub1 and sub2) > native forest. In the main river points, these parameters decreased along the river (P1 to P5). The results were more obvious in winter than the summer season. In contrast, the low values of λ and α/ß ratio in the sediment from native forest and relatively less polluted catchment (sub1) during summer season show the quick P desorption when compared to specific Fe and Al oxides bound to stable P in intensive agriculture sediments. These findings clearly indicated that agricultural practices, sediment characteristics, and hydrological factors have a major impact on seasonal sediment P bioavailability and mobility. The urban untreated discharges may be a single major P source and, if it is not wisely managed, proves a major threat to water quality. These results have serious implications for the river ecosystem and will be of great importance to improve the environmental and economic performance of agricultural practices aiming to reduce soil-based P legacy to surface waters.

Copper and zinc accumulation and fractionation in a clayey Hapludox soil subject to long-term pig slurry application.

Pig slurry (PS) recycling as fertilizer is commonly practiced as an option for minimizing livestock waste. Successive PS applications on the soil can lead to crop toxicity and environmental risk. Despite extensive investigation of macronutrient behavior, the fate of trace metals remains uncertain and only a few long-term field studies have been reported to date. This study was designed to assess the impact of 11-year continuous PS spreading on Cu and Zn accumulation and fractionation in a Brazilian clayey Hapludox soil. Three different PS application rates--50, 100 and 200m3 ha(-1)year(-1)--were monitored at six soil depths in comparison to a non-amended control soil. The modified Geological Survey of Canada sequential extraction protocol was applied. A statistically significant increase in Cu and Zn total concentration (assessed by the sum of fractions) was noted only within the 0-5 cm soil layer for the 50 and 100 m3 ha(-1) year(-1) (PS50 and PS100) treatments, and up to 10-15 cm for the 200 m3 ha(-1)year(-1) (PS200) treatment. The mass balance, determined for the 22 PS amendments over the period, confirmed the overall exogenous Cu and Zn accumulation within the surface layers. More than 70% of the natural heavy metal content was originally in the residual fraction. However, this was the only fraction not influenced by the PS amendments. After PS input, the exogenous Cu was mainly detected in the fraction bound to organic matter (66.4%) within the PS200 0-5 cm soil layer. Exogenous Zn was mainly distributed between the adsorbed fraction (36.7%) and the organic matter fraction (32.0%) within the PS200 0-5 cm layer.

Combining visible-based-color parameters and geochemical tracers to improve sediment source discrimination and apportionment.

Parameter selection in fingerprinting studies are often time-consuming and costly because successful fingerprint properties are generally highly site-specific. Recently, spectroscopy has been applied to trace sediment origin as a rapid, less expensive, non-destructive and straightforward alternative. We show in this study the first attempt to combine both geochemical tracers and color parameters derived from the visible (VIS) spectrum in a single estimate of sediment source contribution. Moreover, we compared the discrimination power and source apportionment using VIS-based-color parameters and using the whole ultra-violet-visible (UV-VIS) spectrum in partial last square regression (PLSR) models. This study was carried out in a small (1.19 km(2)) rural catchment from southern Brazil. The sediment sources evaluated were crop fields, unpaved roads, and stream channels. Color parameters were only able to discriminate unpaved roads from the other sources, disabling its use to fingerprint sediment sources itself. Nonetheless, there was a great improvement in source discrimination combining geochemical tracers and color parameters. Unlike VIS-based-color parameters, the distances between sediment sources were always significantly different using the whole UV-VIS-spectrum. It indicates a loss of information and, consequently, loss of discriminating power when using VIS-based-color parameters instead of the whole UV-VIS spectrum. Overall, there was good agreement in source ascription obtained with geochemical tracers alone, geochemical tracers coupled with color parameters, and UV-VIS-PLSR models, and all of them indicate clearly that the main sediment source was the crop fields, corresponding to 57 ± 14, 48 ± 13, and 62 ± 18%, respectively. Prediction errors for UV-VIS-PLSR models (6.6 ± 1.1%) were very similar to those generated in a mixed linear model using geochemical tracers alone (6.4 ± 3.6%), but the combination of color parameters and geochemical tracers decreases the prediction error (5.4 ± 2.0%). Therefore, the use of VIS-based-color parameters combined to geochemical tracers can be a rapid and inexpensive way to improve source discrimination and precision of sediment source apportionment.

Modeling field-scale vertical movement of zinc and copper in a pig slurry-amended soil in Brazil.

Organic amendments often represent a source of trace metals (TMs) in soils, which may partly leach into the groundwater. The objectives of this study were (1) to validate Hydrus-2D for modeling the transport of Zn and Cu in an Alfisol amended with pig slurry (PS) by comparing numerical simulations and experimental field data, and (2) to model the next 50 years of TM movements under scenarios of suspended or continued PS amendments. First, between 2000 and 2008, we collected detailed Zn and Cu data from a soil profile in Santa Maria, Brazil. Two hypotheses about Zn and Cu reactivity with the solid phase were tested, considering physical, hydraulic, and chemical characteristics of six soil layers. Using a two-site sorption model with a sorption kinetic rate adjusted based on laboratory EDTA extractions, Hydrus simulations of the vertical TM transport were found to satisfactorily describe the soil Zn and Cu concentration profiles. Second, the long-term fate of Zn and Cu in the soil was assessed using the validated parameterized model. Numerical simulations showed that Zn and Cu did not present risks for groundwater pollution. However, future Cu accumulation in the surface soil layer would exceed the Brazilian threshold for agricultural soils.

Using a two site-reactive model for simulating one century changes of Zn and Pb concentration profiles in soils affected by metallurgical fallout.

Predicting the transfer of contaminants in soils is often hampered by lacking validation of mathematical models. Here, we applied Hydrus-2D software to three agricultural soils for simulating the 1900-2005 changes of zinc and lead concentration profiles derived from industrial atmospheric deposition, to validate the tested models with plausible assumptions on past metal inputs to reach the 2005 situation. The models were set with data from previous studies on the geochemical background, estimated temporal metal deposition, and the 2005 metal distributions. Different hypotheses of chemical reactions of metals with the soil solution were examined: 100% equilibrium or partial equilibrium, parameterized following kinetic chemical extractions. Finally, a two-site model with kinetic constant values adjusted at 1% of EDTA extraction parameters satisfactory predicted changes in metal concentration profiles for two arable soils. For a grassland soil however, this model showed limited applicability by ignoring the role of earthworm activity in metal incorporation.