RESUMEN

Long-term data are required to quantify the impacts of historic industrial pollution and subsequent remedial action on the nearshore benthic community in the St. Lawrence River Area of Concern at Cornwall, Ontario. Specifically, high-quality temporal records are needed to understand changes in benthic invertebrate assemblages in response to multiple possible drivers including industrial pollution, environmental heterogeneity, and climate warming. We compare long-term records of subfossil chironomid assemblages and geochemical variables among sediment cores from two Cornwall sites with differing pollution histories and a minimally disturbed downstream reference site. Chironomids were functionally absent from the Cornwall sediment cores when mercury and zinc concentrations were elevated. As metal concentrations decreased in more recent sediment intervals, chironomid abundance and the relative abundance of pollution-sensitive taxa increased. Recently deposited sediment in all three sediment cores display increased relative abundance of warm-water, macrophyte-associated taxa. We conclude that these temporal changes in chironomid assemblages provide evidence for ecological recovery for both of the impacted sites, consistent with the objectives of the current management strategy. These findings advance our understanding of industrial impacts on fluvial chironomid ecology, directly inform local management strategies, and further develop the application of chironomids as bioindicators for contaminated sediments.

Asunto(s)

Chironomidae , Animales , Ontario , Clima , Biomarcadores Ambientales , Contaminación Ambiental

RESUMEN

Four bis[2-{pyrazol-1-yl}-6-{pyrazol-3-yl}pyridine] ligands have been synthesized, with butane-1,4-diyl (L1 ), pyrid-2,6-diyl (L2 ), benzene-1,2-dimethylenyl (L3 ) and propane-1,3-diyl (L4 ) linkers between the tridentate metal-binding domains. L1 and L2 form [Fe2 (µ-L)2 ]X4 (X- =BF4 - or ClO4 - ) helicate complexes when treated with the appropriate iron(II) precursor. Solvate crystals of [Fe2 (µ-L1 )2 ][BF4 ]4 exhibit three different helicate conformations, which differ in the torsions of their butanediyl linker groups. The solvates exhibit gradual thermal spin-crossover, with examples of stepwise switching and partial spin-crossover to a low-temperature mixed-spin form. Salts of [Fe2 (µ-L2 )2 ]4+ are high-spin, which reflects their highly twisted iron coordination geometry. The composition and dynamics of assembly structures formed by iron(II) with L1 -L3 vary with the ligand linker group, by mass spectrometry and 1 H NMR spectroscopy. Gas-phase DFT calculations imply the butanediyl linker conformation in [Fe2 (µ-L1 )2 ]4+ influences its spin state properties, but show anomalies attributed to intramolecular electrostatic repulsion between the iron atoms.