Mercury species accumulation and trophic transfer in biological systems using the Almadén mining district (Ciudad Real,Spain) as a case of study

The impact of mercury (Hg) pollution in the terrestrial environments and the terrestrial food chains including the impact on human food consumption is still greatly under-investigated. In particular, studies including Hg speciation and detoxification strategies in terrestrial animals are almost non-existing, but these are key information with important implications for human beings. Therefore, in this work, we report on Hg species (inorganic mercury, iHg, and monomethylmercury, MeHg) distribution among terrestrial animal tissues obtained from a real-world Hg exposure scenario (Almadén mining district, Spain). Thus, we studied Hg species (iHg and MeHg) and total selenium (Se) content in liver and kidney of red deer (Cervus elaphus; n?=?41) and wild boar (Sus scrofa; n?=?16). Similar mercury species distribution was found for both red deer and wild boar. Major differences were found between tissues; thus, in kidney, iHg was clearly the predominant species (more than 81 %), while in liver, the species distribution was less homogeneous with a percentage of MeHg up to 46 % in some cases. Therefore, Hg accumulation and MeHg transfer were evident in terrestrial ecosystems. The interaction between total Se and Hg species has been evaluated by tissue and by animal species. Similar relationships were found in kidney for both Hg species in red deer and wild boar. However, in liver, there were differences between animals. The possible underlying mechanisms are discussed.     

Benthic ecosystem functioning in the severely contaminated Mar Piccolo of Taranto (Ionian Sea,Italy): focus on heterotrophic pathways

The benthic ecosystem functioning is a rarely applied holistic approach that integrates the main chemical and biological features of the benthic domain with the key processes responsible for the flux of energy and C through the system. For the first time, such conceptual model, with an emphasis on the heterotrophic pathways, has been applied to the sediments at four stations within one of the most polluted coastal areas in Italy: the Mar Piccolo of Taranto. The functioning of the benthic ecosystem was different according to the investigated site. Nearby the military arsenal, i.e., the main source of organic contaminants and heavy metals, the system seemed inhibited at all the investigated structural and functional levels. Slow microbial processes of C reworking together with very limited densities of benthic fauna suggested a modest transfer of C both into a solid microbial loop and to the higher trophic levels. On the other hand, the ingression of marine water through the “Navigabile” channel seemed to stimulate the organic matter degradation and, consequently, the proliferation of meiofauna and macrofauna. In the innermost part of the basin, the system functioning, to some extent, is less impacted by contaminants and more influenced by mussel farms. The organic matter produced by these bivalves fueled faster C reworking by benthic prokaryotes and enhanced the proliferation of filter feeders.     

Proteomic changes in <Emphasis Type="Italic">Corbicula fluminea</Emphasis> exposed to wastewater from a psychiatric hospital

The increase use of pharmaceutical compounds in veterinary practice and human population results in the ubiquitous presence of these compounds in aquatic ecosystems. Because pharmaceuticals are highly bioactive, there is concern about their toxicological effects in aquatic organisms. Therefore, the aim of this study was to assess the effects of an effluent from a psychiatric hospital (containing a complex mixture of 25 pharmaceutical compounds from eleven therapeutic classes) on the freshwater clam Corbicula fluminea using a proteomic approach. The exposure of C. fluminea to this complex effluent containing anxiolytics, analgesics, lipid regulators, beta blockers, antidepressants, antiepileptics, antihistamines, antihypertensives, antiplatelets and antiarrhythmics induced protein changes after 1 day of exposure in clam gills and digestive gland more evident in the digestive gland. These changes included increase in the abundance of proteins associated with structural (actin and tubulin), cellular functions (calreticulin, proliferating cell nuclear antigen (PCNA), T complex protein 1 (TCP1)) and metabolism (aldehyde dehydrogenase (ALDH), alcohol dehydrogenase, 6 phosphogluconate dehydrogenase). Results from this study indicate that calreticulin, PCNA, ALDH and alcohol dehydrogenase in the digestive gland and T complex protein 1 (TCP1)) and 6 phosphogluconate dehydrogenase in the gills represent useful biomarkers for the ecotoxicological characterization of psychiatric hospital effluents in this species.     

Impact of temperature on the dynamics of organic matter and on the soil-to-plant transfer of Cd,Zn and Pb in a contaminated agricultural soil

Predicting the soil-to-plant transfer of metals in the context of global warming has become a major issue for food safety. It requires a better understanding of how the temperature alters the bioavailability of metals in cultivated soils. This study focuses on one agricultural soil contaminated by Cd, Zn and Pb. DGT measurements were performed at 10, 20 and 30 °C to assess how the bioavailability of metals was affected by a rise in soil temperature. A lettuce crop was cultivated in the same conditions to determine if the soil-to-plant transfer of metals increased with a rise in soil temperature. A gradual decline in Cd and Zn bioavailability was observed from 10 to 30 °C, which was attributed to more intense complexation of metals in the pore water at higher temperatures. Together with its aromaticity, the affinity of dissolved organic matter (DOM) for metals was indeed suspected to increase with soil temperature. One main output of the present work is a model which satisfactorily explains the thermal-induced changes in the characteristics of DOM reported in Cornu et al. (Geoderma 162:65–70, 2011) by assuming that the mineralization of initial aliphatic compounds followed a first-order reaction, increased with soil temperature according to the Arrhenius law, and due to a priming effect, led to the appearance of aromatic molecules. The soil-to-plant transfer of Cd and Zn was promoted at higher soil temperatures despite a parallel decrease in Cd and Zn bioavailability. This suggests that plant processes affect the soil-to-plant transfer of Cd and Zn the most when the soil temperature rises.     

Release of PCBs from Silvretta glacier (Switzerland) investigated in lake sediments and meltwater

This study is part of our investigations about the release of persistent organic pollutants from melting Alpine glaciers and the relevance of the glaciers as secondary sources of legacy pollutants. Here, we studied the melt-related release of polychlorinated biphenyls (PCBs) in proglacial lakes and glacier streams of the catchment of the Silvretta glacier, located in the Swiss Alps. To explore a spatial and temporal distribution of chemicals in glacier melt, we combined two approaches: (1) analysing a sediment record as an archive of past remobilization and (2) passive water sampling to capture the current release of PCBs during melt period. In addition, we determined PCBs in a non-glacier-fed stream as a reference for the background pollutant level in the area. The PCBs in the sediment core from the Silvretta lake generally complied with trends of PCB emissions into the environment. Elevated concentrations during the most recent ten years, comparable in level with times of the highest atmospheric input, were attributed to accelerated melting of the glacier. This interpretation is supported by the detected PCB fractionation pattern towards heavier, less volatile congeners, and by increased activity concentrations of the radioactive tracer ¹³⁷Cs in this part of the sediment core. In contrast, PCB concentrations were not elevated in the stream water, since no significant difference between pollutant concentrations in the glacier-fed and the non-glacier-fed streams was detected. In stream water, no current decrease of the PCBs with distance from the glacier was observed. Thus, according to our data, an influence of PCBs release due to accelerated glacier melt was only detected in the proglacial lake, but not in the other compartments of the Silvretta catchment.     

Fluoride in weathered rock aquifers of southern India: Managed Aquifer Recharge for mitigation

Climatic condition, geology, and geochemical processes in an area play a major role on groundwater quality. Impact of these on the fluoride content of groundwater was studied in three regions—part of Nalgonda district in Telangana, Pambar River basin, and Vaniyar River basin in Tamil Nadu, southern India, which experience semi-arid climate and are predominantly made of Precambrian rocks. High concentration of fluoride in groundwater above 4 mg/l was recorded. Human exposure dose for fluoride through groundwater was higher in Nalgonda than the other areas. With evaporation and rainfall being one of the major contributors for high fluoride apart from the weathering of fluoride rich minerals from rocks, the effect of increase in groundwater level on fluoride concentration was studied. This study reveals that groundwater in shallow environment of all three regions shows dilution effect due to rainfall recharge. Suitable managed aquifer recharge (MAR) methods can be adopted to dilute the fluoride rich groundwater in such regions which is explained with two case studies. However, in deep groundwater, increase in fluoride concentration with increase in groundwater level due to leaching of fluoride rich salts from the unsaturated zone was observed. Occurrence of fluoride above 1.5 mg/l was more in areas with deeper groundwater environment. Hence, practicing MAR in these regions will increase the fluoride content in groundwater and so physical or chemical treatment has to be adopted. This study brought out the fact that MAR cannot be practiced in all regions for dilution of ions in groundwater and that it is essential to analyze the fluctuation in groundwater level and the fluoride content before suggesting it as a suitable solution. Also, this study emphasizes that long-term monitoring of these factors is an important criterion for choosing the recharge areas.     

Suitability of passive sampling for the monitoring of pharmaceuticals in Finnish surface waters

The occurrence of five pharmaceuticals, consisting of four anti-inflammatory and one antiepileptic drug, was studied by passive sampling and grab sampling in northern Lake Päijänne and River Vantaa. The passive sampling was performed by using Chemcatcher® sampler with a SDB-RPS Empore disk as a receiving phase. In Lake Päijänne, the sampling was conducted during summer 2013 at four locations near the discharge point of a wastewater treatment plant and in the years 2013 and 2015 at four locations along River Vantaa. The samples were analyzed by liquid chromatography coupled to tandem mass spectrometry (LC-MS/MS) in the multiple reaction monitoring mode. The concentrations of carbamazepine, diclofenac, ibuprofen, ketoprofen, and naproxen in Lake Päijänne determined by passive sampling ranged between 1.4–2.9 ng L^?1, 15–35 ng L^?1, 13–31 ng L^?1, 16–27 ng L^?1, and 3.3–32 ng L^?1, respectively. Similarly, the results in River Vantaa ranged between 1.2–40 ng L^?1, 15–65 ng L^?1, 13–33 ng L^?1, 16–31 ng L^?1, and 3.3–6.4 ng L^?1. The results suggest that the Chemcatcher passive samplers are suitable for detecting pharmaceuticals in lake and river waters.     

Biodegradability of the anticancer drug etoposide and identification of the transformation products

Etoposide susceptibility to microbiological breakdown was studied in a batch biotransformation system, in the presence or absence of artificial wastewater containing nutrients, salts and activated sludge at two concentration levels. The primary focus of the present study was to study etoposide transformation products by ultra-high performance liquid chromatography coupled to high-resolution hybrid quadrupole-Orbitrap tandem mass spectrometry (MS/MS). Data-dependent experiments combining full-scan MS data with product ion spectra were acquired to identify the molecular ions of etoposide transformation products, to propose the molecular formulae and to elucidate their chemical structures. Due to the complexity of the matrix, visual inspection of the chromatograms showed no clear differences between the controls and the treated samples. Therefore, the software package MZmine was used to facilitate the identification of the transformation products and speed up the data analysis. In total, we propose five transformation products; among them, four are described as etoposide transformation products for the first time. Even though the chemical structures of these new compounds cannot be confirmed due to the lack of standards, their molecular formulae can be used to target them in monitoring studies.     

Integrated spatial health assessment of yellow perch (<Emphasis Type="Italic">Perca flavescens</Emphasis>) populations from the St. Lawrence River,Quebec, Canada) part A: physiological parameters and pathogen assessment

A multi-disciplinary approach was used to evaluate the health of yellow perch (Perca flavescens) in the St. Lawrence River (Quebec, Canada), which is experiencing a severe population decline in the downstream portion of the river. Physiological parameters, liver alterations, trace metal concentrations, parasite prevalence and abundance, stable isotope composition, and the presence/absence of the viral hemorragic septicemia virus (VHSV) were evaluated in perch collected at six sites along the river: Lake St. François, Lake St. Louis (north and south), Beauregard Island, and Lake St. Pierre (north and south). Trace metal concentrations in surface water were higher in Lake St. Louis and downstream of a major urban wastewater treatment plant discharge, indicating that this effluent was a significant source of Cu, As, Ag, Zn, and Cd. Levels of Pb in surface water exceeded thresholds for the protection of aquatic life in Lake St. Louis and were negatively correlated with body condition index in this lake. In Lake St. Pierre, Cu, Ag, and Cd bioaccumulated significantly in perch liver and lower body condition index and greater liver damage were observed compared to upstream sites. Parasite analyses indicated a higher abundance of metacercariae of the trematodes Apophallus brevis and Diplostomum spp. in Lake St. Louis, and VHSV was not detected in the liver of yellow perch for all studied sites. Overall, results suggested that the global health of yellow perch from Lake St. Pierre is lower compared to upstream studied sites, which could contribute to the documented population collapse at this site.     

Linking landscape development intensity within watersheds to methyl-mercury accumulation in river sediments

An indicator of the disturbance of natural systems, the landscape development intensity (LDI) index, was used to assess the potential for land-use within watersheds to influence the production/accumulation of methyl-mercury (MeHg) in river sediments. Sediment samples were collected from locations impacted by well-identified land-use types within the Mobile-Alabama River Basin in Southeastern USA. The samples were analyzed for total-Hg (THg) and MeHg concentrations and the obtained values correlated to the calculated LDI indexes of the sampled watersheds to assess the impact of prevalent land use/land cover on MeHg accumulation in sediments. The results show that unlike THg, levels of MeHg found in sediments are impacted by the LDI indexes. Overall, certain combinations of land-use types within a given watershed appear to be more conducive to MeHg accumulation than others, therefore, pointing to the possibility of targeting land-use practices as potential means for reducing MeHg accumulation in sediments, and ultimately, fish contamination.