Jonatan Val

Acute toxicological effects on the earthworm Eisenia fetida of 18 common pharmaceuticals in artificial soil.

Following soil applications of recycled water and biosolids, pharmaceutical residues can eventually enter the terrestrial environment. In vitro and in vivo assays have largely focused on the acute ecotoxicity of these compounds in aquatic systems. However, studies on the ecotoxicological effects of pharmaceuticals in soil biota are especially scarce. The aim of this study was to investigate the acute toxicity of 18 pharmaceuticals (4 NSAIDs, 5 blood lipid-lowering agents, 6 β-blockers and 3 antibiotics) that are usually found in the environment by using an Eisenia fetida bioassay. In addition, the presence of these pharmaceuticals in artificial soil was verified at the end of the test. Our results indicate that seven of the studied drugs cause acute adverse effects in E. fetida, in particular, the NSAIDs and the blood lipid-lowering agents. Ibuprofen (LC50=64.80 mg/kg) caused the highest acute toxicity for all tested compounds, followed by diclofenac (LC50=90.49 mg/kg) and simvastatin (LC50=92.70 mg/kg). Other tested pharmaceuticals from NSAIDs and blood lipid-lowering families have toxicity effects, from a LC50=140.87 mg/kg for gemfibrozil to 795.07 mg/kg for lovastatin. Atorvastatin, bezafibrate, β-blockers and antibiotics showed no detectable lethality in E. fetida. The four NSAIDs showed evidence of modification of their original chemical structure after 14 days so the detected toxicity may be due to the original product as well as their degradation products. The three blood lipid-lowering agents seem to be more stable in soil. From an environmental perspective, the lethal concentrations of the tested drugs are much greater than those reported in wastewater and biosolids, therefore acute toxic effects may be improbable. However, little is known about the accumulation of these substances in soils after regular applications, so accumulative and chronic effects cannot be excluded. Moreover, more studies are needed to determine the role of the degradation products of these pharmaceuticals on terrestrial toxicity.

Irrigation agriculture affects organic matter decomposition in semi-arid terrestrial and aquatic ecosystems

Many dryland areas are being converted into intensively managed irrigation crops, what can disrupt the hydrological regime, degrade soil and water quality, enhance siltation, erosion and bank instability, and affect biological communities. Still, the impacts of irrigation schemes on the functioning of terrestrial and aquatic ecosystems are poorly understood. Here we assess the effects of irrigation agriculture on breakdown of coarse organic matter in soil and water. We measured breakdown rates of alder and holm oak leaves, and of poplar sticks in terrestrial and aquatic sites following a gradient of increasing irrigation agriculture in a semi-arid Mediterranean basin transformed into irrigation agriculture in 50% of its surface. Spatial patterns of stick breakdown paralleled those of leaf breakdown. In soil, stick breakdown rates were extremely low in non-irrigated sites (0.0001-0.0003 day(-1)), and increased with the intensity of agriculture (0.0018-0.0044 day(-1)). In water, stick breakdown rates ranged from 0.0005 to 0.001 day(-1), and increased with the area of the basin subject to irrigation agriculture. Results showed that irrigation agriculture affects functioning of both terrestrial and aquatic ecosystems, accelerating decomposition of organic matter, especially in soil. These changes can have important consequences for global carbon budgets.

Impacts of agricultural irrigation on nearby freshwater ecosystems: the seasonal influence of triazine herbicides in benthic algal communities.

A small hydrological basin (Lerma, NE Spain), transformed from its natural state (steppe) to rain-fed agriculture and recently to irrigation agriculture, has been monitored across four seasons of an agricultural year. The goal of this study was to assess how and whether agricultural activities impacted the nearby freshwater ecosystems via runoff. Specifically, we assessed the toxicity of three triazine herbicides, terbuthylazine, atrazine and simazine on the photosynthetic efficiency and structure of algal benthic biofilms (i.e., phototropic periphyton) in the small creek draining the basin. It was expected that the seasonal runoff of the herbicides in the creek affected the sensitivity of the periphyton in accord with the rationale of the Pollution Induced Community Tolerance (PICT): the exposure of the community to pollutants result in the replacement of sensitive species by more tolerant ones. In this way, PICT can serve to establish causal linkages between pollutants and the observed biological impacts. The periphyton presented significantly different sensitivities against terbuthylazine through the year in accord with the seasonal application of this herbicide in the crops nowadays. The sensitivity of already banned herbicides, atrazine and simazine does not display a clear seasonality. The different sensitivities to herbicides were in agreement with the expected exposures scenarios, according to the agricultural calendar, but not with the concentrations measured in water, which altogether indicates that the use of PICT approach may serve for long-term monitoring purposes. That will provide not only causal links between the occurrence of chemicals and their impacts on natural communities, but also information about the occurrence of chemicals that may escape from traditional sampling methods (water analysis). In addition, the EC50 and EC10 of periphyton for terbuthylazine or simazine are the first to be published and can be used for impact assessments.

Influence of global change-related impacts on the mercury toxicity of freshwater algal communities

The climatic-change related increase of temperatures, are expected to alter the distribution and survival of freshwater species, ecosystem functions, and also the effects of toxicants to aquatic biota. This study has thus assessed, as a first time, the modulating effect of climate-change drivers on the mercury (Hg) toxicity of freshwater algal photosynthesis. Natural benthic algal communities (periphyton) have been exposed to Hg under present and future temperature scenarios (rise of 5 °C). The modulating effect of other factors (also altered by global change), as the quality and amount of suspended and dissolved materials in the rivers, has been also assessed, exposing algae to Hg in natural river water or a synthetic medium. The EC50 values ranged from the 0.15-0.74 ppm for the most sensitive communities, to the 24-40 ppm for the most tolerant. The higher tolerance shown by communities exposed to higher Hg concentrations, as Jabarrella was in agreement with the Pollution Induced Community Tolerance concept. In other cases, the dominance of the invasive diatom Didymosphenia geminata explained the tolerance or sensitivity of the community to the Hg toxicity. Results shown that while increases in the suspended solids reduced Hg bioavailability, changes in the dissolved materials - such as organic carbon - may increase it and thus its toxic effects on biota. The impacts of the increase of temperatures on the toxicological behaviour of periphyton (combining both changes at species composition and physiological acclimation) would be certainly modulated by other effects at the land level (i.e., alterations in the amount and quality of dissolved and particulate substances arriving to the rivers).

Effects of 18 pharmaceuticals on the physiological diversity of edaphic microorganisms

Pharmaceutical residues can enter the terrestrial environment through the application of recycled water and contaminated biosolids to agricultural soils, were edaphic microfauna can would be threatened. This study thus assessed the effect of 18 widely consumed pharmaceuticals, belonging to four groups: antibiotics, non-steroidal anti-inflammatory drugs (NSAIDs), blood lipid-lowering agents (BLLA) and β-blockers, on the physiology of soil microbial communities from a ecological crop field. Biolog EcoPlates, containing 31 of the most common carbon sources found in forest and crop soils, were used to calculate both the averaged well colour development (AWCD), as an indicator of the entire capacity of degrading carbon sources, and the diversity of carbon source utilization, as an indicator of the physiological diversity. The results show that pharmaceuticals impact microbial communities by changing the ability of microbes to metabolize different carbon sources, thus affecting the metabolic diversity of the soil community. The toxicity of the pharmaceuticals was inversely related to the log Kow; indeed, NSAIDs were the least toxic and antibiotics were the most toxic, while BLLA and β-blockers presented intermediate toxicity. The antibiotic sulfamethoxazole imposed the greatest impact on microbial communities at concentrations from 100 mg/L, followed by the other two antibiotics (trimethoprim and tetracycline) and the β-blocker nadolol. Other chemical parameters (i.e. melting point, molecular weight, pKa or solubility) had little influence on toxicity. Microbial communities exposed to pharmaceuticals having similar physicochemical characteristics presented similar physiological diversity patterns of carbon substrate utilization. These results suggest that the repeated amendment of agricultural soils with biosolids or sludges containing pharmaceutical residuals may result in soil concentrations of concern regarding key ecological functions (i.e. the carbon cycle).

Global change impacts on river ecosystems: A high-resolution watershed study of Ebro river metabolism.

Global change is transforming freshwater ecosystems, mainly through changes in basin flow dynamics. This study assessed how the combination of climate change and human management of river flow impacts metabolism of the Ebro River (the largest river basin in Spain, 86,100km(2)), assessed as gross primary production-GPP-and ecosystem respiration-ER. In order to investigate the influence of global change on freshwater ecosystems, an analysis of trends and frequencies from 25 sampling sites of the Ebro river basin was conducted. For this purpose, we examined the effect of anthropogenic flow control on river metabolism with a Granger causality study; simultaneously, took into account the effects of climate change, a period of extraordinary drought (largest in past 140years). We identified periods of sudden flow changes resulting from both human management and global climate effects. From 1998 to 2012, the Ebro River basin was trending toward a more autotrophic condition indicated by P/R ratio. Particularly, the results show that floods that occurred after long periods of low flows had a dramatic impact on the respiration (i.e., mineralization) capacity of the river. This approach allowed for a detailed characterization of the relationships between river metabolism and drought impacts at the watershed level. These findings may allow for a better understanding of the ecological impacts provoked by flow management, thus contributing to maintain the health of freshwater communities and ecosystem services that rely on their integrity.

Addressing the local aspects of global change impacts on stream metabolism using frequency analysis tools

Global change, as a combination of climate change, human activities on watersheds and the river flow regulation, causes intense changes in hydrological cycles and, consequently, threatens the good ecological status of freshwater biological communities. This study addresses how and whether the combination of climatic drivers and local human impacts may alter the metabolism of freshwater communities. We identified a few factors modulating the natural water flow and quality in 25 point spread within the Ebro river Basin: waste water spills, industrial spills, reservoir discharges, water withdrawals, agricultural use, and the presence of riparian forests. We assessed their impacts on the freshwater metabolism as changes in the annual cycle of both gross primary production-GPP - and ecosystem respiration-ER -. For this purpose, daily data series were analyzed by continuous wavelet transformation, allowing for the assessment of the metabolic ecosystem Frequency Spectrum Patterns (FSPs). Changes in the behavior of ecosystem metabolism were strongly associated with local characteristics at each sampling point, however in 20 out of 25 studied points, changes in metabolic ecosystem FSP were related to climatic change events (the driest period of the last 140years). The changes in FSP indicate that severe impacts on how biological communities use carbon sources occur as a result of the human water management - too much focus on human needs - during intense climatic events. Results show that local factors, and specially the flow regulation, may modulate the impact of global change. As example those points exposed to a more intense anthropization showed a clear disruption - and even disappearance - of the annual FSP. This information may help managers to understand the action mechanisms of non-climatic factors at ecosystem level, leading to better management policies based on the promotion of ecosystem resilience. The method here presented may help on improving the calculation of ecological flows to maintain the river metabolic annual cycles as close as possible to the natural ones.

Development of a new methodology for the creation of water temperature scenarios using frequency analysis tool

Thermal quality in river ecosystems is a fundamental property for the development of biological processes and many of the human activities linked to the aquatic environment. In the future, this property is going to be threatened due to global change impacts, and basin managers will need useful tools to evaluate these impacts. Currently, future projections in temperature modelling are based on the historical data for air and water temperatures, and the relationship with past temperature scenarios; however, this represents a problem when evaluating future scenarios with new thermal impacts. Here, we analysed the thermal impacts produced by several human activities, and linked them with the decoupling degree of the thermal transfer mechanism from natural systems measured with frequency analysis tools (wavelet coherence). Once this relationship has been established we develop a new methodology for simulating different thermal impacts scenarios in order to project them into future. Finally, we validate this methodology using a site that changed its thermal quality during the studied period due to human impacts. Results showed a high correlation (r2=0.84) between the decoupling degree of the thermal transfer mechanisms and the quantified human impacts, obtaining 3 thermal impact scenarios. Furthermore, the graphic representation of these thermal scenarios with its wavelet coherence spectrums showed the impacts of an extreme drought period and the agricultural management. The inter-conversion between the scenarios gave high morphological similarities in the obtained wavelet coherence spectrums, and the validation process clearly showed high efficiency of the developed model against old methodologies when comparing with Nash-Stucliffe criterion. Although there is need for further investigation with different climatic and anthropic management conditions, the developed frequency models could be useful in decision-making processes by managers when faced with future global change impacts.