Ecotoxicology and geostatistical techniques employed in subtropical reservoirs sediments after decades of copper sulfate application.

Spatial distribution linked to geostatistical techniques contributes to sum up information into an easier-to-comprehend knowledge. This study compares copper spatial distribution in surface sediments and subsequent categorization according to its toxicological potential in two reservoirs, Rio Grande (RG) and Itupararanga (ITU) (São Paulo-Brazil), where copper sulfate is applied and not applied, respectively. Sediments from 47 sites in RG and 52 sites in ITU were collected, and then, copper concentrations were interpolated using geostatistical techniques (kriging). The resulting sediment distributions were classified in categories based on sediment quality guides: threshold effect level and probable effect level; regional reference values (RRVs) and enrichment factor (EF). Copper presented a heterogenic distribution and higher concentrations in RG (2283.00 ± 1308.75 mg/kg) especially on the upstream downstream, associated with algicide application as well as the sediment grain size, contrary to ITU (21.81 ± 8.28 mg/kg) where a no-clear pattern of distribution was observed. Sediments in RG are predominantly categorized as "Very Bad", whereas sediments in ITU are mainly categorized as "Good", showing values higher than RRV. The classification is supported by the EF categorization, which in RG is primarily categorized as "Very High" contrasting to ITU classified as "Absent/Very Low". Copper total stock in superficial sediment estimated for RG is 4515.35 Ton of Cu and for ITU is 27.45 Ton of Cu.

Spatial distribution, bioavailability, and toxicity of metals in surface sediments of tropical reservoirs, Brazil.

Depending on the environmental conditions, surface sediments can retain all the contaminants present and provide a record of the anthropic activities affecting the aquatic environment. In order to analyze the impacts on reservoirs, surface sediments were collected in three characteristic regions (riverine, transitional, and limnetic zones) of seven reservoirs in São Paulo State, Brazil. Analyses were made of grain size, organic matter (OM), total phosphorus (TP), and total nitrogen (TN). Inductively coupled plasma-atomic emission spectroscopy (ICP-AES) was used to determine pseudo-total and bioavailable metals (Cu, Cd, Cr, Ni, Pb, Zn, Mn, Fe, and Al). A Horiba probe was used to measure dissolved oxygen (DO), pH, redox potential (ORP), and temperature (Temp) in the bottom water. The data were analyzed using multivariate statistics. Enrichment factors (EF), pollution load index values (PLI), and background values (BG) were also determined in order to evaluate the potential toxicity. Intra-reservoir and inter-reservoir spatial heterogeneity (p < 0.05) were observed using two-way analysis of similarities. Principal component analysis indicated greater influence of metals in the Barra Bonita, Salto Grande, and Rio Grande reservoirs, corroborating the PLI, EF, and BG data. Bioavailable Cu was found in the Rio Grande reservoir, possibly associated with copper sulfate used to control algal blooms, while bioavailable Ni in the Barra Bonita reservoir was attributed to the presence of industrial wastes and natural geology. The bottom water conditions indicated that the metals remained in insoluble forms.

Metals and limnological variables in an urban reservoir: compartmentalization and identification of potential impacted areas.

Reservoirs in urban areas are used for different purposes and are liable to different types of pressures that can cause the loss of chemical and biological quality, hence diminishing their ecological, economic, and cultural benefits. Here, a study of surface water heterogeneity was undertaken at the Guarapiranga urban reservoir (São Paulo, Brazil) in order to improve understanding of the structure and functioning of these ecosystems. Sampling was performed during the dry and rainy seasons at 33 sites. Limnological variables and total contents of the metals cadmium, nickel, lead, and zinc were analyzed. The risks associated with the metals were evaluated based on the toxicity unit approach. A principal component analysis enabled differentiation of the reservoir into six different areas. Some of the most powerful discriminatory variables (nutrients and metals) showed the existence of anthropogenic impacts on the system. The most strongly affected compartments were located in the following: (1) upstream area, under the influence of the Parelheiros stream, with the highest total phosphorus levels (318 mg L-1) and (2) dam area, with high values for total nitrogen, suspended organic matter, total solids, and pH. The results for the dam compartment were a consequence of substantial urbanization and a longer residence time. Despite high levels of cadmium during the rainy season, no significant potential risk for zooplankton was observed. The data indicated the need to control unauthorized land occupation and to implement adequate sanitation in the Guarapiranga watershed. This research provides information that should assist water resource agencies in the sustainable management of urban reservoirs.

Metals in sediments: bioavailability and toxicity in a tropical reservoir used for public water supply.

Sediments may be a repository of contaminants in freshwater ecosystems. One way to assess the quality of this compartment, in terms of potentially bioavailable metals, is by the analysis of acid-volatile sulfide (AVS) and simultaneously extracted metals (SEM). In order to investigate the bioavailability, toxicity, and compartmentalization of different metals (Cd, Cr, Cu, Ni, Pb, Zn), sampling of surface sediments was performed at nine stations along the Paiva Castro reservoir (São Paulo, Brazil). The metals were analyzed using atomic absorption spectroscopy. Sediment organic matter (OM), organic carbon (OC), and grain size were also measured. The parameters pH, EH, temperature, and dissolved oxygen were determined at the sediment-water interface. Chronic and acute toxicological tests were performed with sediments from the area where water was extracted for the public water supply. Low levels of OM, associated with loss of stratification in the water column, explained the relatively low AVS values. The molar ratio ∑[SEM]-[AVS]/fOC was less than 130 mmol/kg(-1) for all the sampling stations, indicating that the metals were not bioavailable. With the exception of Cd, metal levels were in accordance with background concentrations and the threshold effect level (TEL) established by the Canadian Council of Ministers of the Environment. The ecotoxicological tests confirmed the absence of toxic effects to biota. Application of principal component analysis indicated the presence of four compartments along the reservoir: (1) a riverine zone, potentially threatened by contamination with Cd; (2) an intermediate zone; (3) a limnic area; and (4) the area where water was taken for the public water supply.

Zooplankton functional diversity in subtropical reservoirs of distinct trophic states (São Paulo state, Brazil).

Studies on functional traits of aquatic communities are useful for understanding the ecosystem dynamics as well as the diversity of ecological niches. Here, we characterize zooplankton functional groups and which limnological factors are responsible to changes in traits. Water samples were collected to evaluate limnological parameters and vertical hauls with plankton net (68 µm) were performed to characterize the community in seven reservoirs (Itupararanga, Atibainha, Salto Grande, Rio Grande, Igaratá, Barra Bonita, and Broa, São Paulo state, Brazil). Each species identified was classified according to a trophic group, reproduction mode, body length, habitat, and feeding habitats. Our results showed a predominance of pelagic suspensory herbivores with cilia (31%) followed by pelagic herbivore suspension filter feeders (17%) and raptorial omnivores (15.38%). The other individuals were categorized as pelagic herbivore suspension with oral device (12.3%), littoral herbivores suspensive with cilia (12.3%), pelagic-sucking herbivores (9.2%), and littoral grazing herbivores (3%). The dominance of herbivores may be influenced by the availability of nutrients, influencing their food sources. The abundance of omnivores engaged in predatory behavior can be attributed to disponible prey, thereby exerting significant repercussions on the organization of biological communities.

Past environmental changes: using sedimentary photosynthetic pigments to enhance subtropical reservoir management.

The historical impacts of eutrophication processes were investigated in six subtropical reservoirs (São Paulo, Brazil) using a paleolimnological approach. We questioned whether the levels of pigment indicators of algal biomass could provide information about trophic increase and whether carotenoid pigments could offer additional insights. The following proxies were employed: organic matter, total phosphorus, total nitrogen, photosynthetic pigments (by high-performance liquid chromatography), sedimentation rates, and geochronology (by 210 Pb technique). Principal component analysis indicated a gradient of eutrophication. In eutrophic reservoirs (e.g., Rio Grande and Salto Grande), levels of lutein and zeaxanthin increased over time, suggesting growth of Chlorophyta and Cyanobacteria. These pigments were significantly associated with algal biomass, reflecting their participation in phytoplankton composition. In mesotrophic reservoirs, Broa and Itupararanga, increases and significative linear correlations (r > 0.70) between pigments and nutrients are mainly linked to agricultural and urban activities. In the oligotrophic reservoir Igaratá, lower pigment and nutrient levels reflected lesser human impact and good water quality. This study underscores eutrophication's complexity across subtropical reservoirs. Photosynthetic pigments associated with specific algal groups were informative, especially when correlated with nutrient data. The trophic increase, notably in the 1990s, may have been influenced by neoliberal policies. Integrated pigment and geochemical analysis offers a more precise understanding of eutrophication changes and their ties to human factors. Such research can aid environmental monitoring and sustainable policy development.

Reconstructing 90 years of anthropogenic activities in a subtropical reservoir: a chemometric and paleolimnological perspective.

Environmental reference conditions (RC) and historical trends are crucial for assessing the degree of freshwater impact and formulating restoration measures. This is particularly relevant for freshwater systems used as potable water sources. Using sediments from the Carlos Maggiolo reservoir (Minas, Uruguay), located in a watershed with a mining history, this study aimed to (1) establish metal (As, Cr, Cu, Ni, Pb, and Zn) RC using a predicted interval (PI) chemometric technique; (2) evaluate metal enrichment and toxicity over time and space; and (3) assess environmental changes examining geochemical proxies. Surface sediments from 29 stations were used to establish RC and a core from the dam area was sampled to infer past conditions. The sediments were submitted to partial digestion and analyzed by inductively coupled plasma optical emission spectrometry- ICP-OES. Enrichment factor (EF) calculated using both PI and bottom core values did not show significant differences over time. Over space and time, most metals primarily originated from natural sources (EF < 2). The PI in mg/kg was Cr: 23.74-37.32; Cu: 25.75-48.99; Ni: 16.29-25.55; Pb: 7.63-13.75; and Zn: 94.34-174.80. A stratigraphically constrained cluster analysis corroborated by a permutational multivariate analysis of variance categorized the reservoir into two zones: Zone I, before reservoir operation to ~ 1996, and Zone II from ~ 1997 to 2017. The average concentrations of the main metals of toxicological interest in zones I and II, respectively, were as follows: Cr 37.60 ± 1.59, 34.54 ± 1.49 mg/kg; Cu 49.76 ± 2.84, 44.55 ± 2.70 mg/kg; Ni 24.11 ± 0.67, 22.53 ± 1.22 mg/kg; Pb 12.40 ± 0.63, 13.52 ± 0.82 mg/kg; Zn 99.25 ± 3.12, 93.86 ± 4.42 mg/kg; Mn 1160.56 ± 68.88, 1441.61 ± 83.55 mg/kg; and P 1243.21 ± 271.56, 1128.42 ± 183.10 mg/kg. According to a principal component analysis, the period preceding reservoir operation until ~ 1985 was linked to mining activities and application of Cu2SO4, and the period from 1985s to 2000 was influenced by C and P concentrations due to increasing agricultural and afforestation activities in the watershed that consume P fertilizers. The most recent period, from 2000 to ~ 2017, was characterized by an increase in sedimentation rates mainly associated with erosion, particularly in the agricultural areas. This subsequent soil loss in the watershed could compromise the reservoir's useful life. This study contributes to a better understanding of metal geochemistry in subtropical reservoirs and aids in formulating effective recovery and restoration measures.

Chronostratigraphy elucidates environmental changes in lacustrine sedimentation rates and metal accumulation.

All changes taking place in a watershed have repercussions on lacustrine environments, being these, the sink of all activities occurring in the basin. Lake Titicaca, the world's highest and navigable lake, is not unfamiliar with these phenomena that can alter the sedimentation dynamics and metal accumulation. This study aimed to identify temporal trends of sedimentation rates by employing a geochronological analysis (210Pb, 137Cs) and to propose metal background values in Puno Bay, as well as to identify metal concentrations (As, Ba, Ca, Cr, Cu, K, Mg, Mo, Ni, Pb, Zn) in the projected timeline to propose, for the first time, background values in Puno Bay. Two sediment cores were collected from the outer and inner bays. Sediment rate (SR) was calculated through the excess of 210Pb (210Pbxs) applying the Constant Flux Constant Sedimentation (CFCS) model. Results show that SR in the outer bay was 0.48 ± 0.08 cm a-1 and for the inner bay was 0.64 ± 0.07 cm a-1. Sediment quality guidelines (SQGs) did not indicate toxicity was likely to occur, except for As. However, enrichment factors (EFs) indicated that all metal accumulation is geogenic. Climatic factors had a marked influence on sedimentation rates for the outer bay, and in the case of the inner bay, it was a sum of climatic and human-based factors.

Spatial distribution of arsenic and metals suggest a high ecotoxicological potential in Puno Bay, Lake Titicaca, Peru.

Spatial distribution and interpolation methods provide a summarized overview about the pollution dispersion, concerning the environment's quality. A high-altitude lake was taken as a model to assess the metalloid As and metals Cr, Cu, Ni, Pb, Zn distribution in superficial sediment and classify them according to their ecotoxicological potential in the aquatic environment. Surface sediments were collected from 11 sites along Puno Bay located at the western area of Lake Titicaca, Peru, and analyzed for pseudo total-metals. Sediment concentration data and quality were plotted using the Inverse Distance Weighting (IDW) as an interpolation method. High concentrations of As were found especially in the outer bay (81.73 mg.kg-1). Spatial heterogeneity was evidenced for metal by the coefficient of variation, although no significative differences were observed between the two bays applying a Kruskall Wallis test (p < 0.05, df = 1). Sediment quality classification showed that most metal values were below TEL and toxicity was unlikely to occur, only As exceeded threefold PEL values, which categorized sediment as "Very Bad", indicating a rather high ecotoxicological potential to the aquatic environment. In conclusion, spatial analysis connected to interpolation methods demonstrated the superficial sediment heterogeneity in Puno Bay.

Geochemistry and sedimentary photopigments as proxies to reconstruct past environmental changes in a subtropical reservoir.

Sediment cores were used to establish past environmental impacts associated with eutrophication, erosion and metal contamination in the subtropical Atibainha reservoir (São Paulo State, Brazil). We hypothesize that: (1) the levels of nutrients, determined by a spectrophotometric method, reflect the contributions of these elements over time and (2) changes in sedimentation rates, determined by 210Pb geochronology, and metal flows, determined by ICP-AEOS, are related to anthropic activities. Stratigraphic changes in the analysed variables were used to divide the sediment cores into three intervals, according to PCA and cluster analysis (Euclidian distances, Ward's method). Interval I, composed by the period prior to operation of the reservoir, was influenced by organic matter levels. Interval II, between 1967 and 1993 (PC2: 14.94% of the total variability), a period of minor impacts, was mainly influenced by Mn (eigenvalue of 0.71) and Zn (0.74). Interval III, which included sediment deposited between 1993 and 2015 (PC1: 60.28% of the total variability), was influenced by the highest levels of the pigments lutein (0.86), zeaxanthin (0.90) and fucoxanthin (0.65), together with total nitrogen (0.78) and sedimentation rate (0.91), suggesting changes in the phytoplankton community composition probably associated to the intensification of eutrophication and erosion processes. Despite the limitations of applying paleolimnological techniques in reservoirs and the use of pigments as proxies in regions with higher temperatures, it was observed that the anoxic conditions and the aphotic environment in the hypolimnion acted to preserve pigments associated with the groups Chlorophyta (lutein), Cyanobacteria (zeaxanthin) and Bacillariophyta (fucoxanthin). The isolated analysis of nutrients was not sufficient to make conclusive inferences regarding the eutrophication history, since the levels of TP tended to decrease over time, in contrast to an increase in the levels of TN. Despite intensification of eutrophication and erosion, associated to anthropic activities, no signs of metal contamination were recorded.

Connections among Land Use, Water Quality, Biodiversity of Aquatic Invertebrates, and Fish Behavior in Amazon Rivers.

Rivers in the Amazon have among the greatest biodiversity in the world. The Xingu River, one of the tributaries of the Amazon River, has a length of 1640 km, draining 510,000 km2 in one of the most protected regions on the planet. The Middle Xingu region in Brazil has been highly impacted by mining and livestock farming, leading to habitat fragmentation due to altered water quality. Therefore, comparing two rivers (the preserved Xingu River and the impacted Fresco River) and their confluence, the aims of the present study were to (1) assess the land uses in the hydrographic basin; (2) determine the water quality by measurements of turbidity, total solids, and metals (Cd, Cu, Fe, Mn, Pb, Zn, and Hg); (3) compare the zooplankton biodiversity; and (4) to evaluate the avoidance behavior of fish (Astyanax bimaculatus) when exposed to waters from the Xingu and Fresco Rivers. Zooplankton were grouped and counted down to the family level. For the analysis of fish avoidance, a multi-compartment system was used. The forest class predominated at the study locations, accounting for 57.6%, 60.8%, and 63.9% of the total area at P1XR, P2FR, and P3XFR, respectively, although since 1985, at the same points, the forest had been reduced by 31.3%, 25.7%, and 27.9%. The Xingu River presented almost 300% more invertebrate families than the Fresco River, and the fish population preferred its waters (>50%). The inputs from the Fresco River impacted the water quality of the Xingu River, leading to reductions in local invertebrate biodiversity and potential habitats for fish in a typical case of habitat fragmentation due to anthropic factors.

An abiotic typology and reference conditions for nutrients and chlorophyll-a in subtropical reservoirs (São Paulo State, Brazil).

The establishment of reference conditions and typology are two important steps in water resources management. The reference conditions enable the determination of how impacted an ecosystem is, while the typology facilitates the implementation of management procedures. A study of subtropical reservoirs in São Paulo State (Brazil) was performed to obtain (1) an abiotic typology, using principal component analysis (PCA) and cluster analysis (Ward's method with Euclidean distances), and (2) reference conditions for total phosphorus (TP), total nitrogen (TN), and chlorophyll-a (Chl-a) in the dry and rainy seasons for one of the established typologies. Two main statistical techniques were used: the lake population distribution approach and the trisection method. PCA identified an environmental gradient in the east-west direction, with reservoirs at higher latitudes and with larger dimensions in the west, and smaller reservoirs in eastern areas with higher altitude and higher average annual rainfall. The PCA and cluster analysis indicated that there were four main types of reservoirs. The nutrient criteria techniques, obtained for 13 type I rainy-east reservoirs, were not significantly different (t test, p < 0.05). Although the methods resulted in similar reference conditions, one-way ANOVA indicated significant differences between the seasons for Chl-a, which levels were slightly higher in the rainy season. As far as we know, this is the first study to simultaneously provide an abiotic typology and reference conditions for chlorophyll-a and nutrients in different seasons, considering subtropical reservoirs in South America. This investigation makes an important contribution to the monitoring and management of subtropical reservoirs, and the promotion of dialog between the scientific community and managers, aiming at ensuring the sustainability of water bodies.

Predicting zebrafish spatial avoidance triggered by discharges of dairy wastewater: An experimental approach based on self-purification in a model river.

Wastewater discharges from dairy industries can cause a range of harmful effects in aquatic ecosystems, including a decline in biodiversity due to species evasion. Therefore, it is important to know the purification potential of rivers for the removal of pollutants released in dairy wastewater (DWW). The hypothesis adopted in this work was that the release of DWW into stretches of the Ribeirão dos Pombos River (São Paulo State, Brazil) might trigger an avoidance response, resulting in fish migrating to other regions, with the response being greater when the self-cleaning potential of the river is smaller. Therefore, the goals of the present study were to: (i) investigate how land use and seasonality of the rainfall regime influence the quality of the water in different areas of the river (P1: river source; P2: urban region; P3: rural region); (ii) assess the potential of the river to purify DWW; and (iii) evaluate the potential toxicity and repellency of DWW to the freshwater fish Danio rerio, using acute toxicity (mortality) and non-forced avoidance tests, respectively. P1 was shown to be the most preserved area. The chemical composition of the river varied seasonally, with higher concentrations of Cl- and SO42- at P3 during the rainy period. The river purification potential for DWW was higher at P2, due to greater microbiological activity (associated with higher BOD). The DWW was more acutely toxic in water from P2. The avoidance response was strongly determined by the concentration of DWW, especially for water from P2. The high capacity for self-cleaning at P2 did not seem sufficient to maintain the stability of the ecosystem. Finally, the non-forced exposure system proved to be a suitable approach that can assist in predicting how contaminants may affect the spatial distributions of organisms.

Factors that control the spatial and temporal distributions of phosphorus, nitrogen, and carbon in the sediments of a tropical reservoir.

The impacts of anthropic activities have had profound effects on the nitrogen (N) and phosphorus (P) cycles in many aquatic ecosystems. We investigated the spatial and temporal distributions of carbon (C), N, and P in the sediments of a tropical Paiva Castro Reservoir (São Paulo, Brazil), as well as their release and retention in the system. In 2010, surface sediments were collected at nine sites in the reservoir, and a core was obtained in the limnetic zone, in 2010. The core was dated using the 210Pb technique. The organic C content was estimated from organic matter concentration, which was measured by the loss-on-ignition method, and the concentrations of P and N were determined by spectrophotometry. Marked spatial heterogeneity in the Paiva Castro sediments associated with both natural variations in the water body and variations induced by human impacts was observed. Heterogeneity was evidenced by a decrease in the allochthonous contribution of organic matter (C/N) in the upstream-downstream direction and increases of N and P, mainly associated with water flows in the different compartments of the reservoir. In the core, C and N concentrations display significant positive correlations with increases in population and agricultural activities in the drainage basin through time. The C/P molar ratios in surface sediments are indicative of human impacts in the region, as C:P ratios in the sediment are low (7.8:1) compared to the Redfield ratio (C:P = 108:1). Predominance of oxic conditions at the sediment surface and particles sizes < 63 µm provided favorable conditions for P retention in the sediments, which helps prevent eutrophication. Approaches used in this research should be extended to other locations, especially in mesotrophic and oligotrophic reservoirs, to provide information on historical impacts in such aquatic ecosystems.

Influence of interspecific interactions on avoidance response to contamination.

An increasing number of studies have shown the ability of organisms to escape from toxic effects due to contamination, by moving spatially towards less contaminated habitats. However, this issue has been investigated in monospecific scenarios, without considering possible interactions between species during the contamination avoidance process. It is widely known that the spatial distribution of one species can be affected by another one, in different ways. Therefore, the main question addressed in the present study was as follows: Might interspecific interaction between the freshwater fish Danio rerio (zebrafish) and Poecilia reticulata (guppy) change their behavior patterns in terms of avoidance in the presence of a copper gradient? Zebrafish and guppies exposed to a copper gradient were tested for avoidance responses in a free-choice, non-forced, static, multi-compartmented exposure system, using two distinct approaches: (1) monospecific tests, in which only one species was exposed to the copper gradient, at two different population densities; and (2) multispecific tests, in which both species were tested simultaneously. In the control (with no copper) monospecific tests, both species were randomly distributed; however, in the control multispecific test, P. reticulata tended to aggregate. In the monospecific tests with a copper gradient, both species avoided copper in a similar way, with AC50 (concentration triggering avoidance in 50% of the exposed population) values between 15 and 18 µg·L-1, irrespective of the population density. However, in the multispecific tests, P. reticulata displaced D. rerio to previously avoided copper levels, consequently increasing the AC50 of D. rerio to 75 µg·L-1. This study shows the importance of understanding the interactions among species in contaminated areas, and the way that one species can prevent the avoidance behavior of another.

Ecological and toxicological responses in a multistressor scenario: Are monitoring programs showing the stressors or just showing stress? A case study in Brazil.

The Metropolitan Region of São Paulo (MRSP) is located in the Brazilian State of São Paulo and reservoirs in this region are vital for water supply and energy production. Changes in economic, social, and demographic trends produced pollution of water bodies, decreasing water quality for human uses and affecting freshwater populations. The presence of emerging pollutants, classical priority substances, nutrient excess and the interaction with tropical-climate conditions require periodic reviews of water policies and monitoring programs in order to detect and manage these threats in a global change scenario. The objective of this work is to determine whether the monitoring program of the São Paulo's Environmental Agency, is sufficient to explain the toxicological and biological responses observed in organisms in reservoirs of the MRSP, and whether it can identify the possible agents causing these responses. For that, we used publicly available data on water quality compiled by this agency in their routine monitoring program. A general overview of these data and a chemometric approach to analyze the responses of biotic indexes and toxicological bioassays, as a function of the physical and chemical parameters monitored, were performed. Data compiled showed temporal and geographical information gaps on variables measured. Toxicological responses have been observed in the reservoirs of the MRSP, together with a high incidence of impairments of the zooplankton community. This demonstrates the presence of stressors that affect the viability of organisms and populations. The statistical approach showed that the data compiled by the environmental agency are insufficient to identify and explain the factors causing the observed ecotoxicological responses and impairments in the zooplankton community, and are therefore insufficient to identify clear cause-effect relationships. Stressors different from those analyzed could be responsible for the observed responses.