Humans are contaminated by mercury in different forms from different sources. In practice, contamination by methylmercury from fish consumption is assessed by measuring hair mercury concentration, whereas exposure to elemental and inorganic mercury from other sources is tested by analysis of blood or urine. Here, we show that diverse sources of hair mercury at concentrations as low as 0.5 ppm can be individually identified by specific coordination to C, N, and S ligands with high energy-resolution X-ray absorption spectroscopy. Methylmercury from seafood, ethylmercury used as a bactericide, inorganic mercury from dental amalgams, and exogenously derived atmospheric mercury bind in distinctive intermolecular configurations to hair proteins, as supported by molecular modeling. A mercury spike located by X-ray nanofluorescence on one hair strand could even be dated to removal of a single dental amalgam. Chemical forms of other known or putative toxic metals in human tissues could be identified by this approach with potential broader applications to forensic, energy, and materials science.

The freshwater cyprinid Tanichthys albonubes was used to assess the bioavailability of divalent mercury (Hg­(II)) complexed in dissolved organic matter (DOM) to fish. The fish acquired 0.3 to 2.2 μg Hg/g dry weight after 8 weeks in aquaria containing DOM from a Carex peat with complexed mercury at initial concentrations of 14 nM to 724 nM. Changes in the relative proportions of dithiolate Hg­(SR)2 and nanoparticulate β-HgS in the DOM, as quantified by high energy-resolution XANES (HR-XANES) spectroscopy, indicate that Hg­(SR)2 complexes either produced by microbially induced dissolution of nanoparticulate β-HgS in the DOM or present in the original DOM were the forms of mercury that entered the fish. In the fish with 2.2 μg Hg/g, 84 ± 8% of Hg­(II) was bonded to two axial thiolate ligands and one or two equatorial N/O electron donors (Hg­[(SR)2+(N/O)1–2] coordination), and 16% had a Hg­(SR)4 coordination, as determined by HR-XANES. For comparison, fish exposed to Hg2+ from 40 nM HgCl2 contained 10.4 μg Hg/g in the forms of dithiolate (20 ± 10%) and tetrathiolate (23 ± 10%) complexes, and also Hg x S y clusters (57 ± 15%) having a β-HgS-type local structure and a dimension that exceeded the size of metallothionein clusters. There was no evidence of methylmercury in the fish or DOM within the 10% uncertainty of the HR-XANES. Together, the results indicate that inorganic Hg­(II) bound to DOM is a source of mercury to biota with dithiolate Hg­(SR)2 complexes as the immediate species bioavailable to fish, and that these complexes transform in response to cellular processes.

Of all divalent metals, mercury (Hg II ) has the highest affinity for metallothioneins. Hg II is considered to be enclosed in the α and β domains as tetrahedral α‐type Hg 4 Cys 11‐12 and β‐type Hg 3 Cys 9 clusters similar to Cd II and Zn II . However, neither the four‐fold coordination of Hg nor the existence of Hg–Hg atomic pairs have ever been demonstrated, and the Hg II partitioning among the two protein domains is unknown. Using high energy‐resolution XANES spectroscopy, MP2 geometry optimization, and biochemical analysis, evidence for the coexistence of two‐coordinate Hg‐thiolate complex and four‐coordinate Hg‐thiolate cluster with a metacinnabar‐type (β‐HgS) structure in the α domain of separate metallothionein molecules from blue mussel under in vivo exposure is provided. The findings suggest that the CXXC claw setting of thiolate donors, which only exists in the α domain, acts as a nucleation center for the polynuclear complex and that the five CXC motifs from this domain serve as the cluster‐forming motifs. Oligomerization is driven by metallophilic Hg⋅⋅⋅Hg interactions. Our results provide clues as to why Hg has higher affinity for the α than the β domain. More generally, this work provides a foundation for understanding how metallothioneins mediate mercury detoxification in the cell under in vivo conditions.

Fluoxetine (FLX) the active pharmaceutical ingredient (API) in Prozac(®) is a widely prescribed psychoactive drug which ubiquitous occurrence in the aquatic environment is associated to a poor removal rate in waste-water treatment plant (WWTP) systems. This API acts as a selective serotonin reuptake inhibitor (SSRI) frequently reported to cause disrupting effects in non-target species. The objective of this study includes a multibiomarker response evaluation on mussel Mytilus galloprovincialis during two weeks exposure to 75 ng L(-1) FLX assessing antioxidant enzymes activities--superoxide dismutase (SOD), catalase (CAT) and glutathione-S-transferase (GST); lipid peroxidation (LPO), acetylcholinesterase (AChE) neurotoxic response and endocrine disruption through alkali-labile phosphates (ALP) indirect measurement of vitellogenin-like proteins. Results show transient tissue-specific enzymatic responses and damage affecting mostly mussel gills. However, the clear ALP levels inhibition throughout time in both sex-differentiated gonads gives evidence to FLX reinforced action as an endocrine disruptor rather than an oxidative or neurotoxic inducer.

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