Tracking Colloid Transport in Porous Media Using Discrete Flow Fields and Sensitivity of Simulated Colloid Deposition to Space Discretization

Advances in pore structure characterization and lattice−Boltzmann (LB) simulations of flow fields in pore spaces are making mechanistic simulations of colloid transport in real porous media a realistic goal. The primary challenge to reach this goal may be the computational demand of LB flow simulations in discretized porous medium domains at an assemblage scale. In this work, flow fields in simple cubic and dense packing systems were simulated at different discretization resolutions using the LB method. The simulated flow fields were incorporated into to a three-dimensional particle tracking model to simulate colloid transport in the two systems. The simulated colloid deposition tended to become asymptotic at a critical discretization resolution (voxel−grain size ratio = 0.01) at groundwater flow regimes for colloids down to submicrometer level under favorable conditions and down to around 1 μm under unfavorable conditions. The average simulated fluid velocities near grain surfaces were extracted to explain the sensitivities of simulated depositions to space discretization under both conditions. At the critical discretization resolution, current computation capacity would allow flow simulations and particle tracking in assemblage porous medium domains. In addition, particle tracking simulations revealed that colloids may be retained in flow vortices under conditions both favorable and unfavorable for deposition. Colloid retention in flow vortices has been proposed only very recently. Here we provide a mechanistic confirmation to this novel retention process

Role of Low Flow and Backward Flow Zones on Colloid Transport in Pore Structures Derived from Real Porous Media

To examine the relevance of low flow zones and flow vortices to colloid transport in real porous media, lattice-Boltzmann (LB) simulations were combined with X-ray microtomography (XMT) to simulate flow fields in glass beads and quartz sand. Backward flow zones were demonstrated to be widely present in both porous media, with a greater volume fraction in the former relative to the latter porous media. Glass beads in the XMT images were approximated as spheres and their coordinates and radii were extracted to allow reconstruction of pore structures. LB simulations were again performed and the simulated flow fields in the reconstructed pore structures were coupled to a three-dimensional particle tracking algorithm. Particle tracking simulations demonstrated that significant amounts of colloids stayed in the simulated domains for long periods (up to 50 pore volumes). The percentages of colloids with long residence time increased as the depth of the secondary energy minimum increased. The majority of the colloids with long residence time were translated to low flow zones while being associated with grain surfaces via secondary minima. A small fraction of colloids entered low flow zones without being associated with the grains surfaces. Backward flow zones were also found to trap a small fraction of colloids for significantly long time (up to 10 pore volumes). In overall, however, backward flow zones trapped fewer colloids for shorter durations than low flow zones. In summary, this work demonstrates the importance of temporary trapping of colloids by the low flow and backward flow zones in real porous media. This trapping process can explain a number of intriguing experimental observations

Colloid Retention in Porous Media: Mechanistic Confirmation of Wedging and Retention in Zones of Flow Stagnation

A three-dimensional particle tracking model for colloid transport in porous media was developed that predicts colloid retention in porous media in the presence of an energy barrier via two mechanisms:  (1) wedging of colloids within grain to grain contacts; (2) retention of colloids (without attachment) in flow stagnation zones. The model integrates forces experienced by colloids during transport in porous media, i.e., fluid drag, gravity, diffusion, and colloid−surface Derjaguin−Landau−Verwey−Overbeek interac tions. The model was implemented for a fluid flow field that explicitly represented grain to grain contacts. The model utilized a variable time stepping routine to allow finer time steps in zones of rapid change in fluid velocity and colloid−surface interaction forces. Wedging was favored by colloid:collector ratios greater than about 0.005, with this threshold ratio increasing with decreasing fluid velocity. Retention in flow stagnation zones was demonstrated for colloid:collector ratios less than about 0.005, with this threshold decreasing with increasing fluid velocity. Both wedging and retention in flow stagnation zones were sensitive to colloid−surface interaction forces (energy barrier height and secondary energy minimum depth). The model provides a mechanistic basis for colloid retention in the presence of an energy barrier via processes that were recently hypothesized to explain experimental observations

Lack of Enantioselective Microbial Degradation of Chlordane in Long Island Sound Sediment

Numerous studies have examined the enantiomeric compositions of trans- and cis-chlordane in soils (agricultural, background, and house foundation soils) and in the atmosphere. In contrast, little is known about the enantiomeric compositions of chlordane in sediment. In this work, surficial sediments and sediment cores were collected at various sites in Long Island Sound (LIS) previously surveyed by the National Oceanic and Atmospheric Administration's (NOAA) National Status and Trends (NS&T) Program. Archived surficial sediments at selected sites were acquired from the NS&T Specimen Bank. The chlordanes were racemic or nearly racemic in most archived and recently collected sediments, indicating that the enantiomeric compositions of the sources of chlordane to LIS sediment did not change in the past two decades, and that house foundation soils are likely the major source of chlordanes to LIS. Invariant enantiomeric compositions temporally in surficial sediments and at different depths in sediment cores clearly indicate the lack of enantioselective biodegradation in LIS sediment, in striking contrast to the widely observed enantioselective biodegradation of chlordanes in soils

Occurrence and Transformation of Ephedrine/Pseudoephedrine and Methcathinone in Wastewater in China

Previous wastewater-based epidemiology studies on methcathinone (MC), a controlled substance in many countries, attributed its occurrence in wastewater to its misuse. However, such attribution did not consider the possibility that MC may also come from the transformation of ephedrine (EPH) and pseudo-ephedrine (PEPH). In this work, EPH/PEPH and MC in wastewater of six major Chinese cities were systematically examined. EPH/PEPH concentrations in all the cities showed clear seasonal variations, with maximum and minimum concentrations observed in winter and summer, respectively. In contrast, MC concentrations were the lowest in winter, leading to minimum concentration ratios between MC and EPH/PEPH in winter. Lack of MC seizure in the cities suggests that MC abuse could not account for the ubiquitous detection of the substance in the wastewater of these cities. Batch experiments confirmed EPH/PEPH transformation into MC in wastewater. The significantly lower transformation rate at a lower temperature was consistent with low MC concentrations in winter. These results indicate that when monitoring MC through wastewater, EPH/PEPH concentrations must be determined simultaneously to avoid false identification of MC abuse. The observed ratios of MC to EPH/PEPH concentrations in this work may be used to determine MC abuse. Alternatively, other biomarkers (e.g., cathinone) may be considered to avoid interference from EPH/PEPH transformation

Accumulation Dynamics of Chlordanes and Their Enantiomers in Cockerels (<i>Gallus gallus</i>) after Oral Exposure

After a single oral exposure of technical chlordane, levels of cis-chlordane (CC), trans-chlordane (TC), heptachlor (HEP), heptachlorepoxide (HEPX), and oxychlordane (OXY) were determined in gastrointestinal residues, droppings, and various tissues of cockerels at times of 60, 120, 160, 200, 300, 500, 1000, and 2000 min. Over 98% of CC and TC were found to be bioaccessible; only 1.1% of CC and TC were directly excreted through droppings without further biotransformation. According to the single-compartment toxicokinetic modeling, CC and TC shared similar absorption rates in the whole body while TC showed a slightly more rapid elimination rate, with a half-life of 13.4 h for CC and 12.5 h for TC. The metabolites HEPX and OXY appeared quickly in tissues 60 min after exposure and were mainly accumulated in fat and liver tissues. Concentrations of CC, TC, and HEP in cockerel tissues roughly followed the order as fat > intestine > skin > liver> brain > muscle > blood. Levels of CC, TC, and HEP in various tissues showed significant correlation with the lipid contents of the tissues (p < 0.05) for samples beginning 500 min after exposure. A multicompartment toxicokinetic model was developed to characterize the accumulation dynamics of CC and TC in the various tissues. All tissues of cockerels enantioselectively accumulated (−)-CC and (+)-TC, and fat, skin, and liver tissues showed a relatively stronger capacity of enantioenrichment. The enantiomer fractions (EFs) of droppings remained nearly racemic at first but gradually decreased to less than 0.5 for CC and increased to more than 0.5 for TC, which could rule out enantioselective absorption and excretion of CC and TC in cockerels. The one-compartment toxicokinetic model was applied to the individual enantiomers of CC and TC. Different elimination rates but similar absorption rates were observed between the enantiomers for both CC and TC

Persistent Chlordane Concentrations in Long Island Sound Sediment: Implications from Chlordane, ²¹⁰Pb, and ¹³⁷Cs Profiles

Concentrations of chlordane, a banned termiticide and pesticide, were examined in recently collected surficial sediment (10 sites) and sediment cores (4 sites) in Long Island Sound (LIS).The highest chlordane concentrations were observed in western LIS, near highly urbanized areas. Chlordane concentrations did not decrease significantly in the past decade when compared to the data collected in 1996, consistent with the observation of near-constant chlordane levels in blue mussel tissues collected during the same time period. Chlordane concentrations in many of the sites exceeded levels above which harmful effects on sediment-dwelling organisms are expected to frequently occur. Chlordane concentrations in two of the four sediment cores showed a peak below the sediment surface, suggesting reduced chlordane inputs in recent years. The lack of a chlordane concentration maximum below the sediment surface in the other two cores, coupled with the lack of a well-defined 137Cs peak, indicated significant sediment mixing. Simulations of 137Cs and 210Pb profiles in sediment cores with a simple sediment-mixing model were used to constrain both the deposition rate and the bioturbation rate of the sediment. Simulations of the chlordane profiles indicated continued chlordane input to LIS long after chlordane was phased out in the U.S. Continued chlordane input and significant sediment mixing may have contributed to the persistent chlordane concentrations in surficial sediment, which poses long-term threats to benthic organisms in LIS

Role of Dectin-1 in immune response of macrophages induced by <i>Fonsecaea monophora</i> wild strain and melanin-deficient mutant strain

Chromoblastomycosis is a chronic granulomatous subcutaneous fungal disease caused mainly by Fonsecaea monophora in southern China. Melanin is an important virulence factor in wild strain (Mel+), and the strains lack of the polyketide synthase gene is a melanin-deficient mutant strain (Mel-). We investigated the effect of melanin in F. monophora on Dectin-1 receptor-mediated immune responses in macrophages. Conidia and tiny hyphae of Mel+ and Mel- were co-cultured with THP-1 macrophages expressing normal or low levels of Dectin-1. Compare the killing rate, phagocytosis rate, and expression levels of the inflammatory cytokines tumour necrosis factor-α, interleukin-1β, interleukin-6, and nitric oxide in each group. The results showed that the killing rate, phagocytosis rate, and pro-inflammatory factor levels of Mel+ infected macrophages with normal expression of Dectin-1 were lower than those of Mel-. And the knockdown of Dectin-1 inhibited the phagocytic rate, killing rate, and proinflammatory factor expression in macrophages infected with Mel+ and Mel-. And there was no significant difference in the above indexes between Mel+ and Mel- groups in Dectin-1 knockdown macrophages. In summary, the study reveals that melanin of F. monophora inhibits the immune response effect of the host by hindering its binding to Dectin-1 on the surface of macrophage, which may lead to persistent fungal infections.</p

Enantioselective Behavior of α-HCH in Mouse and Quail Tissues

α-HCH (hexachlorocyclohexane) is chiral and can still be detected in almost all environmental media. In this study, the enantioselective behavior of α-HCH in mice (CD1) and quail (Coturnix japonica) was investigated and compared after a single dose of exposure. The primary nerve cell culture was conducted to evaluate the enantioselective metabolic capacity of nerve cells of mouse and quail for α-HCH. In various tissues of the mice and quail, the α-HCH concentrations showed a typical pattern of first-order dynamics after exposure. The enantiomeric fractions (EFs) in nonbrain tissues of mice decreased substantially, indicating continuous depletion of (+)-α-HCH in mice. Tissue-specific EF trends in quail and enantioselective degradation of (−)-α-HCH in quail liver were observed. These observations indicated that the dynamic changes of EFs in mice and quail were independent of concentration changes in the same tissues. In brain tissues, the enantioenrichment of (+)-enantiomer was totally independent of their concentrations in blood. The in vitro metabolism of α-HCH in the primary nerve cells were negligible, and the slight EF changes in primary nerve cells demonstrated that metabolism, uptake, and excretion in the brain cells would not lead to the observed dramatic enantioenrichment of (+)-α-HCH in the brain tissues of the two animals. The enantioselective transport across the blood−brain barrier was the primary cause for the enantioenrichment of (+)-α-HCH in the brain tissues

Accumulation Dynamics of Chlordanes and Their Enantiomers in Cockerels (<i>Gallus gallus</i>) after Oral Exposure

After a single oral exposure of technical chlordane, levels of cis-chlordane (CC), trans-chlordane (TC), heptachlor (HEP), heptachlorepoxide (HEPX), and oxychlordane (OXY) were determined in gastrointestinal residues, droppings, and various tissues of cockerels at times of 60, 120, 160, 200, 300, 500, 1000, and 2000 min. Over 98% of CC and TC were found to be bioaccessible; only 1.1% of CC and TC were directly excreted through droppings without further biotransformation. According to the single-compartment toxicokinetic modeling, CC and TC shared similar absorption rates in the whole body while TC showed a slightly more rapid elimination rate, with a half-life of 13.4 h for CC and 12.5 h for TC. The metabolites HEPX and OXY appeared quickly in tissues 60 min after exposure and were mainly accumulated in fat and liver tissues. Concentrations of CC, TC, and HEP in cockerel tissues roughly followed the order as fat > intestine > skin > liver> brain > muscle > blood. Levels of CC, TC, and HEP in various tissues showed significant correlation with the lipid contents of the tissues (p < 0.05) for samples beginning 500 min after exposure. A multicompartment toxicokinetic model was developed to characterize the accumulation dynamics of CC and TC in the various tissues. All tissues of cockerels enantioselectively accumulated (−)-CC and (+)-TC, and fat, skin, and liver tissues showed a relatively stronger capacity of enantioenrichment. The enantiomer fractions (EFs) of droppings remained nearly racemic at first but gradually decreased to less than 0.5 for CC and increased to more than 0.5 for TC, which could rule out enantioselective absorption and excretion of CC and TC in cockerels. The one-compartment toxicokinetic model was applied to the individual enantiomers of CC and TC. Different elimination rates but similar absorption rates were observed between the enantiomers for both CC and TC