Recent and historical deposition of mercury (Hg) was examined over a broad geographic area from southwestern Northwest Territories to Labrador and from the U.S. Northeast to northern Ellesmere Island using dated sediment cores from 50 lakes (18 in midlatitudes (41-50 degrees N), 14 subarctic (51-64 degrees N) and 18 in the Arctic (65-83 degrees N)). Distinct increases of Hg overtime were observed in 76% of Arctic, 86% of subarctic and 100% of midlatitude cores. Subsurface maxima in Hg depositional fluxes (microg m(-2) y(-1)) were observed in only 28% of midlatitude lakes and 18% of arctic lakes, indicating little recent reduction of inputs. Anthropogenic Hg fluxes adjusted for sediment focusing and changes in sedimentation rates (deltaF(adj,F)) ranged from -22.9 to 61 microg m(-2) y(-1) and were negatively correlated (r = -0.57, P < 0.001) with latitude. Hg flux ratios (FRs; post-1990)/pre-1850) ranged from 0.5 to 7.7. The latitudinal trend for Hg deltaF(adj,F) values showed excellent agreement with predictions of the global mercury model, GRAHM for the geographic location of each lake (r = 0.933, P < 0.001). The results are consistent with a scenario of slow atmospheric oxidation of mercury, and slow deposition of reactive mercury emissions, declining with increasing latitude away from emission sources in the midlatitudes, and support the view that there are significant anthropogenic Hg inputs in the Arctic.
A survey was conducted of water and sediment from across Canada in 1993-94 to assess the effectiveness of the 1989 regulation of antifouling uses of tributyltin (TBT) under the Canadian Pest Control Products Act. The survey was also designed to assess concentrations of 13 other organotin species in water and sediment, and in sewage treatment plant influents, effluents and sludges. The main conclusion is that the 1989 regulation has only been partially effective. It has had some effect in the reduction of TBT concentrations in fresh water, but not in sea water. It has had less effect in the reduction of TBT concentrations in sediment, probably because of the longer persistence of TBT in sediment than in water. In many locations the TBT concentration was high enough to cause acute and chronic toxicity to aquatic and benthic organisms. In some areas there may be potential for recycling TBT from contaminated sediments back into the water column. In addition, it appears that large harbours that handle ships legally painted with TBT-containing antifouling paints continued to experience ecotoxicologically significant TBT contamination. Other organotin species found appear to pose no acute or chronic hazards to fresh water or marine organisms, but nothing is known of their hazards to benthic organisms. The presence of monooctyltin and dioctyltin in sediments and sewage treatment plant influents, effluents and sludges is reported for the first time, and tripropyltin is quantified in sediments for the first time.
Three metal–organic frameworks (MOFs), MIL-100(Fe, Cr) and NH2-MIL-101(Al), were prepared, and their adsorption equilibria for phenol and p-nitrophenol (PNP) from water were investigated. All three MOFs show similar and limited adsorption capacities for phenol, but NH2-MIL-101(Al) reveals exceptional adsorption capacity for PNP, greatly exceeding those of MIL-100(Fe, Cr). MIL-100(Fe, Cr) possess similar adsorption affinity for phenol and PNP, which suggests that the effect of metal ions and the coordinatively unsaturated sites in MOFs show negligible effect for phenol and PNP adsorption from water. NH2-MIL-101(Al) exhibits superior adsorption capacity for PNP and uniquely higher adsorption selectivity for PNP over phenol than a benchmark activated carbon. The remarkable adsorption affinity is attributed to the hydrogen bonding between PNP and the amino groups in NH2-MIL-101(Al). Phenol and PNP displayed a fast adsorption kinetics on NH2-MIL-101(Al) and followed a pseudo-second-order kinetic model. This work highlights that introducing functional groups into MOFs through an organic linker is a promising way to tailor MOFs for aqueous adsorption and separation.
Mechanical stimuli can modify the energy landscape of chemical reactions and enable reaction pathways, offering a synthetic strategy that complements conventional chemistry. These mechanochemical mechanisms have been studied extensively in one-dimensional polymers under tensile stress using ring-opening and reorganization, polymer unzipping and disulfide reduction as model reactions. In these systems, the pulling force stretches chemical bonds, initiating the reaction. Additionally, it has been shown that forces orthogonal to the chemical bonds can alter the rate of bond dissociation. However, these bond activation mechanisms have not been possible under isotropic, compressive stress (that is, hydrostatic pressure). Here we show that mechanochemistry through isotropic compression is possible by molecularly engineering structures that can translate macroscopic isotropic stress into molecular-level anisotropic strain. We engineer molecules with mechanically heterogeneous components-a compressible ('soft') mechanophore and incompressible ('hard') ligands. In these 'molecular anvils', isotropic stress leads to relative motions of the rigid ligands, anisotropically deforming the compressible mechanophore and activating bonds. Conversely, rigid ligands in steric contact impede relative motion, blocking reactivity. We combine experiments and computations to demonstrate hydrostatic-pressure-driven redox reactions in metal-organic chalcogenides that incorporate molecular elements that have heterogeneous compressibility, in which bending of bond angles or shearing of adjacent chains activates the metal-chalcogen bonds, leading to the formation of the elemental metal. These results reveal an unexplored reaction mechanism and suggest possible strategies for high-specificity mechanosynthesis.
Two new three-dimensional isostructural lanthanide metal-organic frameworks (Ln(III)-MOFs), [LnL(HO)]·3HO·0.75DMF (1-Ln; Ln = Dy(III) and Eu(III) ions, HL = biphenyl-3'-nitro-3,4',5-tricarboxylic acid, DMF = N,N'-dimethylformamide), were synthesized and characterized. The appearance of temperature-dependent out-of-phase (χ″) signal reveals that complex 1-Dy displays slow magnetic relaxation behavior with the energy barrier (ΔU) of 57 K and a pre-exponential factor (τ) of 3.89 × 10 s at 1200 Oe direct current field. The luminescence explorations demonstrated that 1-Eu exhibits high quenching efficiency and low detection limit for sensing nitrobenzene and CrO. Meanwhile, the fluorescence intensity of the quenched 1-Eu samples will be resumed after washing with DMF or water, indicating that 1-Eu may be used as a highly selective and recyclable luminescence sensing material for sensing nitrobenzene and CrO anion.
The impact of inherited genetic variation on gene expression in humans is well-established. The majority of known expression quantitative trait loci (eQTLs) impact expression of local genes (cis-eQTLs). More research is needed to identify effects of genetic variation on distant genes (trans-eQTLs) and understand their biological mechanisms. One common trans-eQTLs mechanism is “mediation” by a local (cis) transcript. Thus, mediation analysis can be applied to genome-wide SNP and expression data in order to identify transcripts that are “cis-mediators” of trans-eQTLs, including those “cis-hubs” involved in regulation of many trans-genes. Identifying such mediators helps us understand regulatory networks and suggests biological mechanisms underlying trans-eQTLs, both of which are relevant for understanding susceptibility to complex diseases. The multitissue expression data from the Genotype-Tissue Expression (GTEx) program provides a unique opportunity to study cis-mediation across human tissue types. However, the presence of complex hidden confounding effects in biological systems can make mediation analyses challenging and prone to confounding bias, particularly when conducted among diverse samples. To address this problem, we propose a new method: Genomic Mediation analysis with Adaptive Confounding adjustment (GMAC). It enables the search of a very large pool of variables, and adaptively selects potential confounding variables for each mediation test. Analyses of simulated data and GTEx data demonstrate that the adaptive selection of confounders by GMAC improves the power and precision of mediation analysis. Application of GMAC to GTEx data provides new insights into the observed patterns of cis-hubs and trans-eQTL regulation across tissue types.
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