240Pu/239Pu signatures allow refining the chronology of radionuclide fallout in South America.

Atmospheric nuclear tests (1945-1980) have led to radioactive fallout across the globe. French tests in Polynesia (1966-1974) may influence the signature of fallout in South America in addition to those conducted by USA and former USSR until 1963 in the Northern hemisphere. Here, we compiled the 240Pu/239Pu atom ratios reported for soils of South America and conducted additional measurements to examine their latitudinal distributions across this continent. Significantly lower ratio values were found in the 20-45° latitudinal band (0.04 to 0.13) compared to the rest of the continent (up to 0.20) and attributed to the contribution of the French atmospheric tests to the ultra-trace plutonium levels found in these soils. Based on sediment cores collected in lakes of Chile and Uruguay, we show the added value of measuring 240Pu/239Pu atom ratios to refine the age models of environmental archives in this region of the world.

Phytoremediation of metals by colonizing plants developed in point bars in the channeled bed of the Dilúvio Stream, Southern Brazil.

Urban rivers are intensely impacted by pollution with metals resulting from anthropogenic activities, and these elements present in water and sediments can be ecofriendly phytoremediated. This study aimed to evaluate the levels of metals in the sediments and colonizing plants growing in point bars in the channeled bed of the Dilúvio Stream, Southern Brazil. Sediment and plants were sampled at five-point bars with consolidated vegetation. These point bars are formed mainly by sand, with increasing concentrations of clay plus silt, carbon, nitrogen, and metals (Zn, Cu, Cr, Ni, Pb, and Cd) downstream. The concentration of Zn (338 µg/g) and Cu (219 µg/g) in sediments were 1.6 and 1.11 above the probable effect level at the most downstream site. The translocation factor was low in all sites and for all potentially toxic metals evaluated (ranging from 0.01 to 0.63). However, bioaccumulation factor exhibited high values, especially for Cd (average of 2.51), Ni (1.62), Zn (1.49), and Cr (1.25), suggesting that the colonizing plants have more potential for phytostabilization and phytoaccumulation than phytoextraction. These plants can be considered as natural filtering reducing the environmental contamination and the flow of these contaminants in the drainage network. Statement of novelty: Colonizing plants growing in point bars of urban rivers are common around the world; however, their phytoremediation potential is poorly studied. Colonizing plants may be useful for phytoremediation of water, effluents, and sediments of the Dilúvio Stream (Southern Brazil), polluted by potentially toxic metals that originated from the urbanization.

Mobilization and transport of pesticides with runoff and suspended sediment during flooding events in an agricultural catchment of Southern Brazil.

Brazil is one of the largest consumers of pesticides in the world, and these chemicals present a high contamination risk for the country's water bodies. The mechanisms of mobilization and transport of pesticides from cropland to river systems are controlled by runoff and erosion processes occurring at the catchment scale. In addition to the excessive use of pesticides, the transport processes of these substances are also accelerated by inadequate soil management and the absence of soil conservation measures at the catchment scale. The current research relied on hydrological monitoring to investigate the transport and persistence of pesticides in response to hydrological dynamics. The study was conducted in the Conceição River watershed where runoff and suspended sediment fluxes are continuously monitored at the outlet. This study area is representative of the grain production system in southern Brazil including the application of large amounts of pesticides combined with extensive runoff and erosion problems. Sample collection in the river for pesticide analysis included the analysis of both water and suspended sediment. The sediment deposit analysis was performed in a single location at 4 depths. Results demonstrate the occurrence of pesticides including simazine, 2,4-D, carbendazim, imidacloprid, tebuconazole, propiconazole, tetraconazole, and trifloxystrobin in water, while glyphosate and AMPA were detected in suspended sediments, and AMPA and carbendazim were found in sediment deposits. The study demonstrated the strong dependence of the mechanisms of pesticide mobilization and transport in the catchment with the intra- and interevent variability of hydro-sedimentary processes. Pesticide detections can be related to several factors, including the magnitude of the rainfall event, the period of pesticide application, or the transport of suspended sediment. All these factors are correlated, and the mechanisms of transportation play an important role in the connections between sink and sources. The results suggest that pesticide monitoring should take into account the runoff and erosion pathways in each particular catchment, and it should especially include the monitoring of major rainfall events for identifying and quantifying the occurrence of pesticides in the environment. The transport of pesticides indicates to be potentiated by intensive pesticide use, the magnitude of rainfall-runoff events, and the absence of runoff control measures (e.g., terracing). These results demonstrate that water and soil conservation techniques should be planned and coordinated at the watershed scale to reduce the connectivity of water and sediment flows from agricultural areas to river systems with the implementation of effective runoff control practices. This will control the mobilization agents (runoff), as well as limit the connection between the sources and the water bodies.

Sediment source fingerprinting: benchmarking recent outputs, remaining challenges and emerging themes.

PURPOSE: This review of sediment source fingerprinting assesses the current state-of-the-art, remaining challenges and emerging themes. It combines inputs from international scientists either with track records in the approach or with expertise relevant to progressing the science. METHODS: Web of Science and Google Scholar were used to review published papers spanning the period 2013-2019, inclusive, to confirm publication trends in quantities of papers by study area country and the types of tracers used. The most recent (2018-2019, inclusive) papers were also benchmarked using a methodological decision-tree published in 2017. SCOPE: Areas requiring further research and international consensus on methodological detail are reviewed, and these comprise spatial variability in tracers and corresponding sampling implications for end-members, temporal variability in tracers and sampling implications for end-members and target sediment, tracer conservation and knowledge-based pre-selection, the physico-chemical basis for source discrimination and dissemination of fingerprinting results to stakeholders. Emerging themes are also discussed: novel tracers, concentration-dependence for biomarkers, combining sediment fingerprinting and age-dating, applications to sediment-bound pollutants, incorporation of supportive spatial information to augment discrimination and modelling, aeolian sediment source fingerprinting, integration with process-based models and development of open-access software tools for data processing. CONCLUSIONS: The popularity of sediment source fingerprinting continues on an upward trend globally, but with this growth comes issues surrounding lack of standardisation and procedural diversity. Nonetheless, the last 2 years have also evidenced growing uptake of critical requirements for robust applications and this review is intended to signpost investigators, both old and new, towards these benchmarks and remaining research challenges for, and emerging options for different applications of, the fingerprinting approach.

Investigating the relationships between chemical element concentrations and discharge to improve our understanding of their transport patterns in rural catchments under subtropical climate conditions.

Solute and particulate elemental concentrations (C) exhibit different responses to changes in discharge (Q), and those relationships are not well understood in subtropical agricultural environments. The objective is to describe the transport processes of different chemical elements during a set of contrasted rainfall events (2011-2015) that occurred in a small rural catchment under subtropical climate. The study was carried out in the Lajeado Ferreira Creek catchment (1.23 km2), southern Brazil. To this end, the concentrations in dissolved organic carbon (DOC), Cl-, NO3-, SO4-, ten chemical elements (in either dissolved or particulate forms) and suspended sediment concentrations (SSC) were determined. Metric indices were then calculated to characterize their transport patterns: (i) the best fit slope between log-C and log-Q (ß), (ii) the coefficient of variation of C and Q, (iii) shape of the hysteresis loop and hysteresis index, and (iv) the flushing index. All particulate elements along with the dissolved inorganic phosphorus (PO4-3) were shown to be controlled by the sediment dynamics. Geogenic elements (Fe2+, Zn2+, Cu2+, Mn2+, Si4+) showed a dilution effect with increasing Q values, likely because they were mainly transported with subsurface and base flow. Dissolved elements that are mainly supplied with fertilizers (Na+ and Cl-) as well as DOC showed a dilution effect, although they were mainly transported by surface runoff. Finally, a chemostatic behavior was found for those chemical elements (Mg2+, K+, Ca2+, NO3- and SO42-) that are supplied by more than one flow pathways. The results demonstrate that under subtropical climate conditions, the transport of essential nutrients including PO4-3 and metals (in particulate form), are mainly transported with surface runoff. Accordingly, runoff control on cultivated hillslopes should be improved to reduce the potential contaminant supply to the river and to reduce the potentially deleterious impacts that they may cause in downstream regions.

"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.

Effects of Rhizophagus clarus and P availability in the tolerance and physiological response of Mucuna cinereum to copper.

Arbuscular mycorrhizal fungi (AMF) improve plant ability to uptake P and tolerate heavy metals. This study aimed to evaluate the effect of available P and the inoculation of Rhizophagus clarus in a Cu-contaminated soil (i) on the activity of acid phosphatases (soil and plant), the presence of glomalin, and (ii) in the biochemical and physiological status of Mucuna cinereum. A Typic Hapludalf soil artificially contaminated by adding 60 mg kg-1 Cu was used in a 3 × 2 factorial design with three replicates. Treatments consisted of three P levels: 0, 40, and 100 mg kg-1 P. Each P treatment level was inoculated (+AMF)/non-inoculated (-AMF) with 200 spores of R. clarus per pot, and plants grown for 45 days. The addition of at least 40 mg kg-1 P and the inoculation of plants with R. clarus proved to be efficient to reduce Cu phytotoxicity and increase dry matter yield. Mycorrhization and phosphate fertilization reduced the activity of enzymes regulating oxidative stress (SOD and POD), and altered the chlorophyll a fluorescence parameters, due to the lower stress caused by available Cu. These results suggest a synergism between the application of P and the inoculation with R. clarus, favoring the growth of M. cinereum in a Cu-contaminated soil. This study shows that AMF inoculation represents an interesting alternative to P fertilization to improve plant development when exposed to excess Cu.

Sediment pollution in margins of the Lake Guaíba, Southern Brazil.

Sediments are formed by deposition of organic and inorganic particles on depth of water bodies, being an important role in aquatic ecosystems, including destination and potential source of essential nutrients and heavy metals, which may be toxic for living organisms. The Lake Guaíba supplies water for approximately two million people and it is located in the metropolitan region of Porto Alegre, Rio Grande do Sul State, Brazil. Thus, the aim of this study was to evaluate the sediment pollution in the margins of Lake Guaíba in the vicinity of Porto Alegre city. Surface sediment was sampled in 12 sites to assess the concentration of several elements (C, N, P, Fe, Al, Ca, Mg, Na, K, Mn, Ba, Zn, V, Pb, Cu, Cr, Ni, Cd, Mo, and Se) and the mineralogical composition. Sediment in margins of Lake Guaíba presented predominantly (> 95%) sandy fraction in all samples, but with significant differences between evaluated sites. Sediments in the margins of Lake Guaíba showed indications of punctual water pollution with Pb, Cu, Cr, Ni, TOC, TKN, and P, mainly derived from urban streams that flow into the lake. In order to solve these environmental liabilities, public actions should not focus only on Guaíba, but also in the streams that flow into the lake.

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.

Physiological and nutritional status of black oat (Avena strigosa Schreb.) grown in soil with interaction of high doses of copper and zinc.

Vineyard sandy acid soils from South Brazil have experienced heavy metal contamination due to replacement of copper (Cu)-based by zinc (Zn)-based products to control foliar diseases. Thus, we evaluate physiological and nutritional status of black oat (Avena strigosa Schreb.), a common interrow crop in vineyards from this region. Soil was collected in a natural field from Santana do Livramento, in Rio Grande do Sul, the southernmost state of Brazil. Black oat was cultivated for 30 days in a greenhouse with application of 0, 30, and 60 mg Cu kg(-1) combined with 0, 15, 30, 60, 120, and 180 mg Zn kg(-1). After the trial period, dry matter accumulation of roots and shoots, Cu and Zn contents in roots and shoots, chlorophyll a fluorescence, photosynthetic pigments and catalase (CAT, EC 1.11.1.6) and peroxidase (POD, EC 1.11.1.7) activity were determined. Cu and Zn toxicity was evidenced by the decrease in plant growth of black oat as well as by the decrease of photochemical efficiency associated with the decrease in photosynthetic pigment content, especially with the highest doses of Cu and Zn. Furthermore, the activity of antioxidant enzymes (CAT and POD) was increased in intermediate doses of Zn, indicating the activation of the antioxidant system, but the stress condition in treatments with high levels of Cu and Zn was not reversed.

Effects of zinc addition to a copper-contaminated vineyard soil on sorption of Zn by soil and plant physiological responses.

The occurrence of high levels of Cu in vineyard soils is often the result of intensive use of fungicides for the preventive control of foliar diseases and can cause toxicity to plants. Nowadays many grape growers in Southern Brazil have replaced Cu-based with Zn-based products. The aim of the study was to evaluate whether the increase in Zn concentration in a soil with high Cu contents can interfere with the dynamics of these elements, and if this increase in Zn may cause toxicity to maize (Zea mays L.). Soil samples were collected in two areas, one in a vineyard with more than 30 years of cultivation and high concentration of Cu and the other on a natural grassland area adjacent to the vineyard. Different doses of Cu and Zn were added to the soil, and the adsorption isotherms were built following the Langmuir's model. In a second experiment, the vineyard soil was spiked with different Zn concentrations (0, 30, 60, 90, 180, and 270mg Zn kg(-1)) in 3kg pots where maize was grown in a greenhouse for 35 days. When Cu and Zn were added together, there was a reduction in the quantities adsorbed, especially for Zn. Zn addition decreased the total plant dry matter and specific leaf mass. Furthermore, with the increase in the activity of catalase, an activation of the antioxidant system was observed. However, the system was not sufficiently effective to reverse the stress levels imposed on soil, especially in plants grown in the highest doses of Zn. At doses higher than 90Znmgkg(-1) in the Cu-contaminated vineyard soil, maize plants were no longer able to activate the protection mechanism and suffered from metal stress, resulting in suppressed dry matter yields due to impaired functioning of the photosynthetic apparatus and changes in the enzymatic activity of plants. Replacement of Cu- by Zn-based fungicides to avoid Cu toxicity has resulted in soil vineyards contaminated with these metals and damaging of plant photosynthetic apparatus and enzyme activity.

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.

Transferência de nitrogênio e fósforo para águas superficiais em uma bacia hidrográfica com agricultura e produção pecuária intensiva no Sul do Brasil / Transfer of nitrogen and phosphorus to surface water in a watershed with agriculture and intensive livestock production in Southern Brazil

Neste trabalho, foram avaliadas as concentrações de fósforo (P) solúvel e nitrato nas águas dos canais de drenagem de uma bacia hidrográfica, com agricultura e produção pecuária intensiva do Sul do Brasil, a fim de avaliar os impactos das atividades agropecuárias no ecossistema aquático. Amostras de água foram coletadas em 11 pontos nos canais de drenagem em três períodos distintos. Coletas diárias, por um período de 30 dias, foram efetuadas no médio curso e no exutório da bacia hidrográfica. As concentrações de nitrato e P solúvel foram maiores nas áreas mais antropizadas e com granjas de suínos próximas a cursos d'água. Nas coletas diárias, observou-se que as concentrações de P mudaram consideravelmente nos dias de chuva, mas a concentração de nitrato manteve certa regularidade durante os períodos com e sem chuva. As altas concentrações de P solúvel e nitrato encontradas foram atribuídas ao manejo inadequado das atividades agropecuárias desenvolvidas na bacia hidrográfica.

In order to evaluate the impact of agricultural activities on aquatic ecosystem, the concentration of nitrate and soluble phosphorus (P) in the stream water were assessed in a rural watershed under intensive agriculture and livestock production in southern Brazil. Water samples were collected at 11 points along the drainage system in three different periods. Additionally, daily collections were made during 30 days in the middle and at the outlet of the watershed. Nitrate and soluble P concentrations were higher in the points closer to the more anthropized areas and pig farms. The soluble P concentration changed substantially according to the rainfall events, while nitrate concentration show little change with rainfall regime. The high nitrate and soluble P concentrations were attributed to poor management of the intensive livestock activities undertaken in the watershed.