The Dynamics of Per- and Polyfluoroalkyl Substances (PFAS) at Interfaces in Porous Media: A Computational Roadmap from Nanoscale Molecular Dynamics Simulation to Macroscale Modeling.

Managing and remediating perfluoroalkyl and polyfluoroalkyl substance (PFAS) contaminated sites remains challenging. The major reasons are the complexity of geological media, partly unknown dynamics of the PFAS in different phases and at fluid-fluid and fluid-solid interfaces, and the presence of cocontaminants such as nonaqueous phase liquids (NAPLs). Critical knowledge gaps exist in understanding the behavior and fate of PFAS in vadose and saturated zones and in other porous media such as concrete and asphalt. The complexity of PFAS-surface interactions warrants the use of advanced characterization and computational tools to understand and quantify nanoscale behavior of the molecules. This can then be upscaled to the microscale to develop a constitutive relationship, in particular to distinguish between surface and bulk diffusion. The dominance of surface diffusion compared to bulk diffusion results in the solutocapillary Marangoni effect, which has not been considered while investigating the fate of PFAS. Without a deep understanding of these phenomena, derivation of constitutive relationships is challenging. The current Darcy scale mass-transfer models use constitutive relationships derived from either experiments or field measurements, which makes their applicability potentially limited. Here we review current efforts and propose a roadmap for developing Darcy scale transport equations for PFAS. We find that this needs to be based on systematic upscaling of both experimental and computational studies from nano- to microscales. We highlight recent efforts to undertake molecular dynamics simulations on problems with similar levels of complexity and explore the feasibility of conducting nanoscale simulations on PFAS dynamics at the interface of fluid pairs.

Toward a Spatiotemporal Understanding of Dolomite Dissolution in Sandstone by CO2-Enriched Brine Circulation.

In this study, we introduce a stochastic method to delineate the mineral effective surface area (ESA) evolution during a recycling reactive flow-through transport experiment on a sandstone under geologic reservoir conditions, with a focus on the dissolution of its dolomite cement, Ca1.05Mg0.75Fe0.2(CO3)2. CO2-enriched brine was circulated through this sandstone specimen for 137 cycles (∼270 h) to examine the evolution of in situ hydraulic properties and CO2-enriched brine-dolomite geochemical reactions. The bulk permeability of the sandstone specimen decreased from 356 mD before the reaction to 139 mD after the reaction, while porosity increased from 21.9 to 23.2% due to a solid volume loss of 0.25 mL. Chemical analyses on experimental effluents during the first cycle yielded a dolomite reactivity of ∼2.45 mmol m-3 s-1, a corresponding sample-averaged ESA of ∼8.86 × 10-4 m2/g, and an ESA coefficient of 1.36 × 10-2, indicating limited participation of the physically exposed mineral surface area. As the dissolution reaction progressed, the ESA is observed to first increase and then decrease. This change in ESA can be qualitatively reproduced employing scanning electron microscopy-image-based stochastic analyses on dolomite dissolution. These results provide a new approach to analyze and upscale the ESA during geochemical reactions, which are involved in a wide range of geoengineering operations.

Tomographic Reservoir Imaging with DNA-Labeled Silica Nanotracers: The First Field Validation.

This study presents the first field validation of using DNA-labeled silica nanoparticles as tracers to image subsurface reservoirs by travel time based tomography. During a field campaign in Switzerland, we performed short-pulse tracer tests under a forced hydraulic head gradient to conduct a multisource-multireceiver tracer test and tomographic inversion, determining the two-dimensional hydraulic conductivity field between two vertical wells. Together with three traditional solute dye tracers, we injected spherical silica nanotracers, encoded with synthetic DNA molecules, which are protected by a silica layer against damage due to chemicals, microorganisms, and enzymes. Temporal moment analyses of the recorded tracer concentration breakthrough curves (BTCs) indicate higher mass recovery, less mean residence time, and smaller dispersion of the DNA-labeled nanotracers, compared to solute dye tracers. Importantly, travel time based tomography, using nanotracer BTCs, yields a satisfactory hydraulic conductivity tomogram, validated by the dye tracer results and previous field investigations. These advantages of DNA-labeled nanotracers, in comparison to traditional solute dye tracers, make them well-suited for tomographic reservoir characterizations in fields such as hydrogeology, petroleum engineering, and geothermal energy, particularly with respect to resolving preferential flow paths or the heterogeneity of contact surfaces or by enabling source zone characterizations of dense nonaqueous phase liquids.

Experimental observation of permeability changes in dolomite at CO2 sequestration conditions.

Injection of cool CO2 into geothermally warm carbonate reservoirs for storage or geothermal energy production may lower near-well temperature and lead to mass transfer along flow paths leading away from the well. To investigate this process, a dolomite core was subjected to a 650 h, high pressure, CO2 saturated, flow-through experiment. Permeability increased from 10(-15.9) to 10(-15.2) m(2) over the initial 216 h at 21 °C, decreased to 10(-16.2) m(2) over 289 h at 50 °C, largely due to thermally driven CO2 exsolution, and reached a final value of 10(-16.4) m(2) after 145 h at 100 °C due to continued exsolution and the onset of dolomite precipitation. Theoretical calculations show that CO2 exsolution results in a maximum pore space CO2 saturation of 0.5, and steady state relative permeabilities of CO2 and water on the order of 0.0065 and 0.1, respectively. Post-experiment imagery reveals matrix dissolution at low temperatures, and subsequent filling-in of flow passages at elevated temperature. Geochemical calculations indicate that reservoir fluids subjected to a thermal gradient may exsolve and precipitate up to 200 cm(3) CO2 and 1.5 cm(3) dolomite per kg of water, respectively, resulting in substantial porosity and permeability redistribution.

Permeability reduction produced by grain reorganization and accumulation of exsolved CO2 during geologic carbon sequestration: a new CO2 trapping mechanism.

Carbon sequestration experiments were conducted on uncemented sediment and lithified rock from the Eau Claire Formation, which consisted primarily of K-feldspar and quartz. Cores were heated to accentuate reactivity between fluid and mineral grains and to force CO(2) exsolution. Measured permeability of one sediment core ultimately reduced by 4 orders of magnitude as it was incrementally heated from 21 to 150 °C. Water-rock interaction produced some alteration, yielding sub-µm clay precipitation on K-feldspar grains in the core's upstream end. Experimental results also revealed abundant newly formed pore space in regions of the core, and in some cases pores that were several times larger than the average grain size of the sediment. These large pores likely formed from elevated localized pressure caused by rapid CO(2) exsolution within the core and/or an accumulating CO(2) phase capable of pushing out surrounding sediment. CO(2) filled the pores and blocked flow pathways. Comparison with a similar experiment using a solid arkose core indicates that CO(2) accumulation and grain reorganization mainly contributed to permeability reduction during the heated sediment core experiment. This suggests that CO(2) injection into sediments may store more CO(2) and cause additional permeability reduction than is possible in lithified rock due to grain reorganization.

[Discussing the safety application of Chinese materia medics in patients with cardiovascular diseases].

Along with the development of Chinese medicine and pharmacy (CMP), Chinese materia medica (CMM) has been used more and more widely at home and abroad. But we have to confront worsening problems such as lack of safety evidence, immature self -formulation technologies, lack of knowledge about their toxicities, and public misunderstanding, especially for patients with cardiovascular disease (CVD). Therefore, we cardiovascular physicians are requested improve knowledge for CMM preparations and their effects and side effects, supervise and identify the interactions between CMM and Westem medicine. Meanwhile, the researchers are also requested to assess the safety and efficacy of CMM through rigorous experimental designs, further improve the quality, safety, and efficacy of CMM, strictly formulate the specification of CMM products, guide the rational use of CMM by clinicians and the general public.

Determination of organotins in aquatic food by gas chromatography with pulsed flame photometric detection.

A method based on gas chromatography (GC)-pulsed flame photometric detection (PFPD) was developed to determine the levels of organotins in aquatic food. After being purified by gel-permeation chromatography in ethyl actate-tetrahydrofuran, the organotin compounds were derivatized by pentylmagnesium bromide. The derivative products were injected into the GC system and detected by PFPD (sulfur mode). The method was validated by analysis of the certified reference material and spiked samples. Recoveries of organotins ranged from 84.1 to 116.6% with relative standard deviation between 1.3 and 16.0% when spiked at levels of 2, 10, and 40 microg/kg. The limits of detection varied from 0.1 to 1.2 microg/kg for shellfish and 0.1 to 0.5 microg/kg for fish. The proposed method was suitable for determining organotins in aquatic foods.

Friction and relative energy dissipation in sheared granular materials.

The oscillating cylinder of a low-frequency inverted torsion pendulum is immersed into layers of noncohesive granular materials, including fine sand and glass beads. The relative energy dissipation and relative modulus of the granular system versus the amplitude and immersed depth of the oscillating cylinder are measured. A rheological model based on a mesoscopic picture is presented. The experimental results and rheological model indicate that small slides in the inhomogeneous force chains are responsible for the energy dissipation of the system, and the friction of the grains plays two different roles in the mechanical response of sheared granular material: damping the energy and enhancing the elasticity.

Study on the contamination level and intake of organotins of Chinese dietary / 中华预防医学杂志

<p><b>OBJECTIVE</b>To obtain the baseline data of organotins' pollution of Chinese meal in order to carry on primary danger analysis of the exposure.</p><p><b>METHODS</b>The samples of the third Chinese total diet study were determined by gas-chromatography pulsed flame photometric detector to estimate dietary intake of organotins. The dietary intake of organotins was estimated according to the contamination level of organotins and food consumption.</p><p><b>RESULTS</b>Only several kinds of organotin were founded in several foods and no organotins was found in fruit, sugar and alcoholic beverages. Dimethyltin (DMT) were detected in some samples from Southern 1 area, the content ranged from 1.5 microg/kg to 4.1 microg/kg. Butyltin compounds existed in seafoods from Southern 1 area, the contents of tributyltin (TBT), dibutyltin (DBT) and monobutyltin (MTB) being 0.9 microg/kg, 1.1 microg/kg, 1.4 microg/kg respectively. The lower limit and upper limit of exposure to tributyltin were from 0.003 microg x kg(-1) x d(-1) to 0.006 microg x kg(-1) x d(-1) and from 0.004 microg x kg(-1) x d(-1) to 0.019 microg x kg(-1) x d(-1) respectively. Comparing to ADI of tributyltin (WHO), the Chinese dietary intake of tributyltin only accounted for 2.5% and that of butyltin only accounted for 3.5%. To identify the contamination source of organotins in Southern 1 area, the individual samples of aquatic food from individual province were analyzed, revealing that Fujian province and Shanghai City were the main contributors of organotins pollution in this area. The belt fish and yellow croaker were typical pollution samples. Higher levels of DMT were detected in seafood samples from Shanghai.</p><p><b>CONCLUSION</b>The exposure level of Chinese dietary was relative low, however the sources of organotin pollution needs further investigation.</p>