Metals and metalloids in freshwater fish from the floodplain of Tablas de Daimiel National Park, Spain.

The Tablas de Daimiel National Park (TDNP) is a floodplain ecosystem in central Spain with a potential risk of heavy metal and metalloid pollution. The objective of this study was to know the accumulation of arsenic (As), cadmium (Cd), mercury (Hg), lead (Pb), and selenium (Se) in muscle of six species of freshwater fish from the floodplain of TDNP. We obtained muscle samples of Cyprinus carpio (n = 89); Squalius pyrenaicus (n = 16); Ameiurus melas (n = 9); Lepomis gibbosus (n = 8); Micropterus salmoides (n = 6) and Carassius auratus (n = 5). A. melas, which is a predatory species, had significantly higher Hg concentrations than omnivorous or herbivorous species (i.e. C. carpio). On the contrary, A. melas showed lower concentrations of As, Pb and Se than omnivorous species (i.e. S. pyrenaicus and L. gibbosus ). The concentration of Hg was positively associated with fish size in C. carpio and A. melas. Some individuals of C. carpio (5.7%) and S. pyrenaicus (12.5%) showed Pb muscle concentrations above the maximum residue levels established by the European legislation for human consumers. The observed muscle Se concentrations can be associated with adverse effects on fish such as blood changes, reduced growth, mortality of juveniles and reproductive failure. The accumulation of Se in this floodplain located in a seleniferous area and the contamination produced by spent Pb shot pellets used for hunting in the past are discussed as potential sources of the elevated levels of these two elements in fish from this floodplain wetland.

Nutrient enrichment and trace element accumulation in sediments caused by waterbird colonies at a Mediterranean semiarid floodplain.

Waterfowl are vectors of nutrients, metals, and other pollutants (i.e. PCBs and microorganisms) on wetlands and other water bodies, especially when bird population density is high, e.g., in nesting, roosting or breeding periods. This work reports the effects caused by the increase in breeding pairs of herons and cormorants between 2010 and 2014 on sediments in an eutrophic Mediterranean wetland belonging to La Mancha Húmeda Biosphere Reserve. Nutrients, metals, metalloids, and isotopic composition (δ15N and δ13C) were analysed in sediments and faeces at several points in the Tablas de Daimiel National Park (TDNP), as well as in the nearby Navaseca wetland, which receives inputs from a wastewater treatment plant (WWTP). Sediments from Navaseca and from one site that is affected by heron colonies (Garcera) in the TDNP showed higher concentrations of organic matter, total organic carbon, total nitrogen, total phosphorus, Al, Co, Cu, Cr, Fe, Ni and Zn than the rest of the sampling sites. Significant correlations between these variables were found, probably suggesting that they have a common organic source. The highest δ15N values in sediments of the TDNP were registered in Guadiana, a site where there is no impact from colonies; these values might therefore be due to anthropogenic activities. Metal and metalloid content in sediments was lower than the regional reference values in soils, except for Se in the TDNP, and Zn and Cu in Navaseca. High Se level in TDNP sediment may be caused by seleniferous soils located upstream. Results showed a low impact of bird droppings compared to other sources of nutrients in the annual input in the TDNP.

Marchiafava-Bignami Disease Associated with Spinal Involvement.

Marchiafava-Bignami disease (MBD) is a rare disorder of unknown etiology, strongly associated with alcoholism and malnutrition. MBD causes primary involvement of the corpus callosum, leading to confusion, dysarthria, seizures, and frequent death. We report the case of a 54-year-old male without a history of alcoholism or known malabsorption disease, who presented with altered consciousness and neurologic impairment. Complex B deficiency was addressed. Magnetic resonance imaging (MRI) showed typical corpus callosum lesions. The clinical features and radiologic images suggested spinal cord involvement. Brain histopathologic findings were consistent with MBD. Despite vitamin replacement therapy, he had a poor outcome.

Wax esters of uropygial gland secretion as biomarkers of endocrine disruption in birds exposed to treated sewage water.

The chemical composition of the uropygial gland secretion of birds shows seasonal, sex and age-related variations following sex hormones fluctuations. We explore the use of the composition of the uropygial gland secretion as a non-invasive biomarker of endocrine disruption in 137 common moorhens (Gallinula chloropus) from Navaseca Pond, which receives the effluent of a wastewater treatment plant, and from the more pristine Tablas de Daimiel National Park in Spain. Wax ester and fatty acid compositions were measured by means gas chromatography - mass spectrometry (GC-MS) in the uropygial gland secretion of moorhens from both wetlands. Organochlorine compounds (p,p'-DDE and PCBs) were measured in blood and uropygial gland secretion of moorhens as indicators of anthropogenic pollutants, and this information was interpreted together with previous results of the accumulation of metals and metalloids in blood and feathers of these moorhens and a wide range of endocrine disrupting chemicals (EDCs) measured in water from both study sites. PCBs and p,p'-DDE were found in 32% of the blood and 51% of uropygial gland secretion samples, being at highest levels in Navaseca. Wax composition was dominated by monoesters of 35-38 carbons and displayed a clear seasonal variation, in which long-chain wax esters were more abundant in spring-summer than in autumn-winter. This seasonal change was less evident in birds from Navaseca, where the presence of shorter wax esters was associated with the higher concentration of PCBs in uropygial gland secretion. The observed effect may not be associated with this specific type of pollutants because moorhens in Navaseca are also exposed to a wide diversity endocrine disruptors as shown in a previous study. Uropygial gland secretion can be a useful non-invasive sample for integrating chemical monitoring of pollutants and their effects as endocrine disruptors in birds.

Urbanization and cattle density are determinants in the exposure to anticoagulant rodenticides of non-target wildlife.

The persistence and toxicity of second generation anticoagulant rodenticides (SGARs) in animal tissues make these compounds dangerous by biomagnification in predatory species. Here we studied the levels of SGARs in non-target species of wildlife and the environmental factors that influence such exposure. Liver samples of terrestrial vertebrates (n = 244) found dead between 2007 and 2016 in the region of Aragón (NE Spain) were analysed. The presence of SGARs was statistically analysed with binary or ordinal logistic models to study the effect of habitat characteristics including human population density, percentage of urban surface, livestock densities and surface of different types of crops. SGARs residues were detected in 83 (34%) of the animals and levels >200 ng/g were found in common raven (67%), red fox (50%), red kite (38%), Eurasian eagle-owl (25%), stone marten (23%), Eurasian buzzard (17%), northern marsh harrier (17%), and Eurasian badger (14%). The spatial analysis revealed that the presence of SGARs residues in wildlife was more associated with the use of these products as biocides in urban areas and cattle farms rather than as plant protection products in agricultural fields. This information permits to identify potential habitats where SGARs may pose a risk for predatory birds and mammals.

Metals and metalloids in blood and feathers of common moorhens (Gallinula chloropus) from wetlands that receive treated wastewater.

We addressed the hypothesis that birds in eutrophic wetlands receiving wastewater treatment plant (WWTP) effluents are exposed to high levels of metals and metalloids and this may drive an ecological trap in some species attracted to these highly productive ecosystems. Levels of metals and metalloids were determined in sediment and in blood and feathers of common moorhens (Gallinula chloropus) from two wetlands in Central Spain: Navaseca Pond, which receives directly the effluent of a WWTP; and Tablas de Daimiel National Park, which is a floodplain less affected by urban discharges. Sediment concentrations of Cr, Mn, Fe, Co, Ni, Cu, Zn, Cd and Pb were higher in Navaseca Pond than in Tablas de Daimiel; only Se was higher in Tablas de Daimiel than in Navaseca. Blood levels of Hg and Se were higher in moorhens from Tablas de Daimiel than those from Navaseca. In the case of Hg these levels were below the threshold of adverse effect, but Se levels in 24% of moorhens from Tablas de Daimiel were above the threshold value associated with Se toxicity in birds (1000 ng/mL). In feathers, Hg, Se, Mn, Cu and As levels were higher in Tablas de Daimiel than in Navaseca. Body condition of moorhens was negatively associated with blood Se levels in the moorhens from Tablas de Daimiel. We can reject the hypothesis of a higher accumulation of metals and metalloids in birds associated with the WWTP effluent, but Se levels may need further research considering the nature of the floodplain of Tablas de Daimiel National Park.

A negative association between bromadiolone exposure and nestling body condition in common kestrels: management implications for vole outbreaks.

BACKGROUND: Vole outbreaks have been extensively described, along with their impacts on humans, particularly in agricultural areas. The use of rodenticides is a common legal practice to minimise crop damage induced by high vole density for biocidal use. However, rodenticides can have negative direct and indirect impacts on non-target species that feed on voles. We studied whether the use of a second-generation anticoagulant rodenticide (SGAR), bromadiolone, can be detected in the blood of fledglings of wild common kestrels Falco tinnunculus in two areas of central Spain, exploring its possible indirect effects. RESULTS: We found that 16.9% of fledglings had a detectable concentration of bromadiolone in their blood, with an average concentration of 0.248 ± 0.023 ng mL-1 . Fledglings with bromadiolone in their blood, regardless of the concentration, had 6.7% lower body mass than those without detectable bromadiolone. CONCLUSION: The use of bromadiolone was detectable in the blood of alive non-target species. Detected bromadiolone in blood may reduce the body condition of nestlings, potentially reducing their fitness. The source of bromadiolone found in nestlings needs to be determined in future studies to derive accurate management advice. However, we urge the discontinuation of official SGAR distribution to farmers and their use in agrarian lands to minimise damage of voles on crops, particularly where common kestrels breed, and encourage the use of alternative effective practices. © 2016 Society of Chemical Industry.

Integrated environmental risk assessment of chemical pollution in a Mediterranean floodplain by combining chemical and biological methods.

The Tablas de Daimiel National Park (TDNP) is a unique floodplain ecosystem in central Spain, serving as permanent resting and breeding areas for many waterbird species. In the last decades, this biodiversity hotspot has been severely endangered by poorly treated wastewater discharges from upstream urban communities arriving through its two major contributors, the Cigüela and Guadiana rivers. In this work, we analysed the potential risk of this constant input of micropollutants (estrogens, dioxin-like compounds and other endocrine disruptors) for the resident wildlife. We sampled 12 locations in TDNP and in the nearby Navaseca Pond during 2013, and performed a series of in-vivo and in-vitro bioassays, including Daphnia magna post-exposure feeding inhibition and recombinant yeast-based assays for dioxin-like and estrogenic activities. These results were then compared with the chemical composition of the samples, analysed by GC-MS/MS and LC-MS/MS, and evaluated according to their toxic potential as toxic equivalents or TEQ. The Navaseca Pond, heavily impacted by wastewater from the town of Daimiel, showed the highest levels of toxic compounds, estrogenic activity, and Daphnia toxicity. Conversely, the less impacted TDNP sites showed low residue levels of contaminants, low estrogenicity and dioxin-like activity and negligible toxicity. The results indicates that the current good chemical status of TDNP is menaced by both the inflow of wastewater treatment plants effluents from Guadiana and Cigüela rivers into TDNP tributaries and, as it occurs in the Navaseca Pond, by direct sewage discharges.

Effects of invasive fish and quality of water and sediment on macrophytes biomass, and their consequences for the waterbird community of a Mediterranean floodplain.

Floodplains are among the most threatened ecosystems world-wide because of multiple stressors, i.e., invasive species, pollution and aquifer overexploitation; the Tablas de Daimiel National Park (Spain) is a clear example of these kinds of impact. This work aims to test whether invasive fish and/or the water and sediment quality are significant drivers of the decline of stonewort (Chara spp.) meadows in the Tablas de Daimiel, investigating how this could explain changes observed in the waterbird community. Bird surveys performed monthly between June 2010 and April 2014 have shown that herbivorous species like the red-crested pochard (Netta rufina) reached historical records between September 2010 and June 2011, but have decreased since then. Piscivorous waterbirds like the great cormorant (Phalacrocorax carbo) and herons increased in population after 2011, however. These changes may be due to the decline of Chara spp. meadows, connected to overexploitation by herbivores, or to changes in water and sediment quality. To test this hypothesis, we studied the growth of Chara spp. biomass in ten sites of the Tablas de Daimiel, where experimental exclosures were set up to exclude herbivory by birds, and bioturbation and herbivory by fish. Our results have shown that the absence of Chara spp. in the Tablas de Daimiel is mostly explained by presence of invasive fish (i.e. common carp). Moreover, the physicochemical characteristics of the water (lower values of conductivity and higher values of inorganic carbon and organic nitrogen), as well as of the sediment (lower values of inorganic and organic phosphorus), favour the increase of Chara spp., in the absence of the fish effect. These results led the National Park managers to begin the control of invasive fish as an urgent measure to assure the ecological conservation of this Mediterranean wetland.

Interspecific and geographical differences in anticoagulant rodenticide residues of predatory wildlife from the Mediterranean region of Spain.

We studied the prevalence of anticoagulant rodenticides (ARs) in the liver of 344 individuals representing 11 species of predatory wildlife that were found dead in the Mediterranean region of Spain (Catalonia and Majorca Island). Six different ARs (brodifacoum, bromadiolone, difenacoum, flocoumafen, difethialone, warfarin) were found in the liver of 216 (62.8%) animals and >1 AR co-occurred in 119 individuals (34.6%). The occurrence of ARs was positively correlated with the human population density. Catalonia and Majorca showed similar prevalence of AR detection (64.4 and 60.4%, respectively), but a higher prevalence was found in the resident population of Eurasian scops owl (Otus scops) from Majorca (57.7%) compared to the migratory population from Catalonia (14.3%). Birds of prey had lower levels of bromadiolone than hedgehogs, whereas no difference was found for other ARs. The risk of SGAR poisoning in wild predators in NE Spain is believed to be elevated, because 23.3% of the individuals exhibited hepatic concentration of ARs exceeding 200 ng/g.