Revealing the environmental pollution of two estuaries through histopathological biomarkers in five fishes from different trophic guilds of northeastern Brazil.

Estuaries in Brazil are mostly anthropically affected due to the discharge of industrial and domestic effluents. In two of them, the Santa Cruz Channel Estuary (ITAP) and Sirinhaém River Estuary (SIR), historically affected by mercury pollution and sugarcane industry in Northeast Brazil, we assessed environmental pollution using liver and gill histopathological biomarkers in fish from different trophic levels. Liver samples exhibited serious damages such as hepatic steatosis, necrosis, and infiltration. The gills showed moderate to severe changes, such as lifting of epithelial cells, lamellar aneurysm, and rupture of lamellar epithelium. Most of the changes in the liver and gills were reported for species Centropomus undecimalis and the Gobionellus stomatus, which were considered as good sentinels of pollution. The combination of biomarker methodologies was efficient in diagnosing the serious damage to the species, reinforcing the need for monitoring the health of the ecosystems evaluated.

In Situ Photochemical Transformation of Hg Species and Associated Isotopic Fractionation in the Water Column of High-Altitude Lakes from the Bolivian Altiplano.

Photochemical reactions are major pathways for the removal of Hg species from aquatic ecosystems, lowering the concentration of monomethylmercury (MMHg) and its bioaccumulation in foodwebs. Here, we investigated the rates and environmental drivers of MMHg photodegradation and inorganic Hg (IHg) photoreduction in waters of two high-altitude lakes from the Bolivian Altiplano representing meso- to eutrophic conditions. We incubated three contrasting waters in situ at two depths after adding Hg-enriched isotopic species to derive rate constants. We found that transformations mostly occurred in subsurface waters exposed to UV radiation and were mainly modulated by the dissolved organic matter (DOM) level. In parallel, we incubated the same waters after the addition of low concentrations of natural MMHg and followed the stable isotope composition of the remaining Hg species by compound-specific isotope analysis allowing the determination of enrichment factors and mass-independent fractionation (MIF) slopes (Δ199Hg/Δ201Hg) during in situ MMHg photodegradation in natural waters. We found that MIF enrichment factors potentially range from -11 to -19‰ and average -14.3 ± 0.6‰ (1 SE). The MIF slope diverged depending on the DOM level, ranging from 1.24 ± 0.03 to 1.34 ± 0.02 for the low and high DOM waters, respectively, and matched the MMHg MIF slope recorded in fish from the same lake. Our in situ results thus reveal (i) a relatively similar extent of Hg isotopic fractionation during MMHg photodegradation among contrasted natural waters and compared to previous laboratory experiments and (ii) that the MMHg MIF recorded in fish is characteristic for the MMHg bonding environment. They will enable a better assessment of the extent and conditions conducive to MMHg photodegradation in aquatic ecosystems.

ENSO Climate Forcing of the Marine Mercury Cycle in the Peruvian Upwelling Zone Does Not Affect Methylmercury Levels of Marine Avian Top Predators.

Climate change is expected to affect marine mercury (Hg) biogeochemistry and biomagnification. Recent modeling work suggested that ocean warming increases methylmercury (MeHg) levels in fish. Here, we studied the influence of El Niño Southern Oscillations (ENSO) on Hg concentrations and stable isotopes in time series of seabird blood from the Peruvian upwelling and oxygen minimum zone. Between 2009 and 2016, La Niña (2011) and El Niño conditions (2015-2016) were accompanied by sea surface temperature anomalies up to 3 °C, oxycline depth change (20-100 m), and strong primary production gradients. Seabird Hg levels were stable and did not co-vary significantly with oceanographic parameters, nor with anchovy biomass, the primary dietary source to seabirds (90%). In contrast, seabird Δ199Hg, proxy for marine photochemical MeHg breakdown, and δ15N showed strong interannual variability (up to 0.8 and 3‰, respectively) and sharply decreased during El Niño. We suggest that lower Δ199Hg during El Niño represents reduced MeHg photodegradation due to the deepening of the oxycline. This process was balanced by equally reduced Hg methylation due to reduced productivity, carbon export, and remineralization. The non-dependence of seabird MeHg levels on strong ENSO variability suggests that marine predator MeHg levels may not be as sensitive to climate change as is currently thought.

Linking Microbial Activities and Low-Molecular-Weight Thiols to Hg Methylation in Biofilms and Periphyton from High-Altitude Tropical Lakes in the Bolivian Altiplano.

The sources and factors controlling concentrations of monomethylmercury (MMHg) in aquatic ecosystems need to be better understood. Here, we investigated Hg transformations in sediments, periphyton associated with green algae's or aquatic plants, and benthic biofilms from the Lake Titicaca hydrosystem and compared them to the occurrence of active methylating microorganisms and extracellular Hg ligands. Intense Hg methylation was found in benthic biofilms and green algae's periphyton, while it remained low in sediments and aquatic plants' periphyton. Demethylation varied between compartments but remained overall in the same range. Hg methylation was mainly carried out by sulfate reducers, although methanogens also played a role. Its variability between compartments was first explained by the presence or absence of the hgcAB genes. Next, both benthic biofilm and green algae's periphyton exhibited a great diversity of extracellular low-molecular-weight (LMW) thiols (13 or 14 compounds) present at a range of a few nmol L-1 or µmol L-1 but clearly dominated by cysteine and 3-mercaptopropionic acid. Hg methylation was overall positively correlated to the total thiol concentrations, albeit to different extents according to the compartment and conditions. This work is the first examining the interplay between active methylating bacterial communities and extracellular ligands in heterotrophic biofilms and supports the involvement of LMW thiols in Hg methylation in real aquatic systems.

Association of a Specific Algal Group with Methylmercury Accumulation in Periphyton of a Tropical High-Altitude Andean Lake.

Periphyton relevance for methylmercury (MeHg) production and accumulation are now well known in aquatic ecosystems. Sulfate-reducing bacteria and other microbial groups were identified as the main MeHg producers, but the effect of periphyton algae on the accumulation and transfer of MeHg to the food web remains little studied. Here we investigated the role of specific groups of algae on MeHg accumulation in the periphyton of Schoenoplectus californicus ssp. (Totora) and Myriophyllum sp. in Uru Uru, a tropical high-altitude Bolivian lake with substantial fishing and mining activities accruing around it. MeHg concentrations were most strongly related to the cell abundance of the Chlorophyte genus Oedogonium (r 2 = 0.783, p = 0.0126) and to no other specific genus despite the presence of other 34 genera identified. MeHg was also related to total chlorophyll-a (total algae) (r 2 = 0.675, p = 0.0459), but relations were more significant with chlorophyte cell numbers, chlorophyll-b (chlorophytes), and chlorophyll-c (diatoms and dinoflagellates) (r 2 = 0.72, p = 0.028, r 2 = 0.744, p = 0.0214, and r 2 = 0.766, p = 0.0161 respectively). However, Oedogonium explains most variability of chlorophytes and chlorophyll-c (r 2 = 0.856, p = < 0.001 and r 2 = 0.619, p = 0.002, respectively), suggesting it is the most influential group for MeHg accumulation and periphyton algae composition at this particular location and given time.

Metal concentration and bioaccessibility in different particle sizes of dust and aerosols to refine metal exposure assessment.

Refined exposure assessments were realized for children, 7-9yrs, in the mining/smelting city of Oruro, Bolivia. Aerosols (PM>2.5, PM1-2.5, PM0.4-1 and PM0.5) and dust (separated in different particle size fractions: 2000-200µm, 200-50µm, 50-20µm, 20-2µm and <2µm) were sampled on football fields highly frequented by children in both the mining and smelting areas. Trace element concentrations (Ag, As, Cd, Cu, Pb, Sb, Sn and Zn) in each size fraction of dust and aerosols, lung bioaccessibility of metals in aerosols, and gastric bioaccessibility of metals in dust were measured. Exposure was assessed considering actual external exposure (i.e. exposure pathways: metals inhaled and ingested) and simulated internal exposure (i.e., complex estimation using gastric and lung bioaccessibility, deposition and clearance of particles in lungs). Significant differences between external and simulated internal exposure were attributed to dissemblances in gastric and lung bioaccessibilities, as well as metal distribution within particle size range, revealing the importance of both parameters in exposure assessment.

Geographical origin of Amazonian freshwater fishes fingerprinted by 87Sr/86Sr ratios on fish otoliths and scales.

Calcified structures such as otoliths and scales grow continuously throughout the lifetime of fishes. The geochemical variations present in these biogenic structures are particularly relevant for studying fish migration and origin. In order to investigate the potential of the (87)Sr/(86)Sr ratio as a precise biogeochemical tag in Amazonian fishes, we compared this ratio between the water and fish otoliths and scales of two commercial fish species, Hoplias malabaricus and Schizodon fasciatus, from three major drainage basins of the Amazon: the Madeira, Solimões, and Tapajós rivers, displaying contrasted (87)Sr/(86)Sr ratios. A comparison of the (87)Sr/(86)Sr ratios between the otoliths and scales of the same individuals revealed similar values and were very close to the Sr isotopic composition of the local river where they were captured. This indicates, first, the absence of Sr isotopic fractionation during biological uptake and incorporation into calcified structures and, second, that scales may represent an interesting nonlethal alternative for (87)Sr/(86)Sr ratio measurements in comparison to otoliths. Considering the wide range of (87)Sr/(86)Sr variations that exist across Amazonian rivers, we used variations of (87)Sr/(86)Sr to discriminate fish origin at the basin level, as well as at the sub-basin level between the river and savannah lakes of the Beni River (Madeira basin).

Influence of source distribution and geochemical composition of aerosols on children exposure in the large polymetallic mining region of the Bolivian Altiplano.

The Bolivian Altiplano (Highlands) region is subject to intense mining, tailing and smelting activities since centuries because of the presence of large and unique polymetallic ore deposits (Ag, Au, Cu, Pb, Sn, Sb, Zn). A large scale PM(10), PM(2.5) aerosol monitoring survey was conducted during the dry season in one of the largest mining cities of this region (Oruro, 200,000 inhabitants). Aerosol fractions, source distribution and transport were investigated for 23 elements at approximately 1 km(2) scale resolution, and compared to children exposure data obtained within the same geographical space. As, Cd, Pb, Sb, W and Zn in aerosols are present at relatively high concentrations when compared to studies from other mining regions. Arsenic exceeds the European council PM(10) guide value (6 ng/m(3)) for 90% of the samples, topping 200 ng/m(3). Ag, As, Cd, Cu, Pb and Sb are present at significantly higher levels in the district located in the vicinity of the smelter zone. At the city level, principal component analysis combined with the mapping of factor scores allowed the identification and deconvolution of four individual sources: i) a natural magmatic source (Co, Cs, Fe, K, Mn, Na, Rb and U) originating from soil dust, resuspended by the traffic activity; ii) a natural sedimentary source (Mg, Ca, Sr, Ba and Th) resulting from the suspension of evaporative salt deposits located South; iii) an anthropogenic source specifically enriched in mined elements (As, Cd, Cu, Pb, Sb and Zn) mainly in the smelting district of the city; and iv) a Ni-Cr source homogenously distributed between the different city districts. Enrichment factors for As, Cd and Sb clearly show the impact of smelting activities, particularly in the finest PM(2.5) fraction. Comparison to children's hair metal contents collected in five schools from different districts shows a direct exposure to smelting activity fingerprinted by a unique trace elements pattern (Ag, As, Cu, Pb, Sb).