Fate Processes Research Articles

Experimental Validation of Hydrogen Atom Transfer Gibbs Free Energy as a Predictor of Nitroaromatic Reduction Rate Constants.

Nitroaromatic compounds (NACs) are a class of prevalent contaminants. Abiotic reduction is an important fate process that initiates NAC degradation in the environment. Many linear free energy relationship (LFER) models have been developed to predict NAC reduction rates. Almost all LFERs to date utilize experimental aqueous-phase one-electron reduction potential ( EH1) of NAC as a predictor, and thus, their utility is limited by the availability of EH1 data. A promising new approach that utilizes computed hydrogen atom transfer (HAT) Gibbs free energy instead of EH1 as a predictor was recently proposed. In this study, we evaluated the feasibility of HAT energy for predicting NAC reduction rate constants. Using dithionite-reduced quinones, we measured the second-order rate constants for the reduction of seven NACs by three hydroquinones of different protonation states. We computed the gas-phase energies for HAT and electron affinity (EA) of NACs and established HAT- and EA-based LFERs for six hydroquinone species. The results suggest that HAT energy is a reliable predictor of NAC reduction rate constants and is superior to EA. This is the first independent, experimental validation of HAT-based LFER, a new approach that enables rate prediction for a broad range of structurally diverse NACs based solely on molecular structures.

Biophysical implications of Maxwell stress in electric field stimulated cellular microenvironment on biomaterial substrates

A number of experimental studies have established the critical role of electric field stimulation on cell functionality modulation of various cell types on a wide range of biomaterial platforms in vitro. In particular, cell fate processes, morphological changes and electroporation are significantly modulated over a narrow range of electric field stimulation conditions. Although a few studies using electrical network theory, first principle simulations and electrohydrodynamic models are reported in the literature, the present study establishes a theoretical foundation to a new perspective that bioelectric stress can significantly influence cell morphological changes/electroporation and in a broader sense, the cell response to electric field on biomaterial substrates. A single cell is modelled as a spherical membrane separating the culture medium and the cytoplasm having different dielectric properties. The analytical solutions to the Laplace equation and Poisson equation for the system are adopted to quantitatively capture the potential distribution in the cellular microenvironment for different cases. These include a cell on a conducting substrate, on an insulating substrate and a cell with surface charge density, in electric field stimulated cellular microenvironment. The biophysical significance of the normal stress distribution has been discussed in terms of the variation in the cellular deformation, depending on the frequency of the electric field and substrate conductivity. A significant difference has been observed in the deformation behavior at higher frequencies (>109 Hz) compared to low frequency and DC electric fields. This theoretical study therefore unravels the significance of substrate conductivity in synergy with electric field parameters to modulate cell response. In addition, the tangential component of the Maxwell stress tensor (shear stress), a measure of the stretching force on the membrane, has been used to obtain estimates of the critical electric field required for membrane rupture. It has been predicted that a cell with surface charge density requires electric fields of the order of 10 kV/mm in order to undergo membrane rupture, which is in line with the experimental observations reported in the literature. Taken together, the presented analysis is expected to provide guidelines to develop next generation biomaterials and biomedical devices for regenerative medicine and cancer treatments.

Storm effects on nitrogen flux and longitudinal variability in a river–reservoir system

AbstractSustainable management of the nitrogen (N) cycle remains a considerable global challenge that has major implications for aquatic ecosystems. Dams play a critical yet often neglected role in addressing this challenge as they increase hydraulic residence time and denitrification potential. However, during storm events when the majority of N loading occurs, less is known about the effects dams have on N fate and transport processes. Here, we examined the flux of N species and phosphorus (P) and longitudinal profiles of nitrate (NO3−) along a sixth‐order river–reservoir system at baseflow and across the falling limb of a multiday, 1‐year storm hydrograph. During the storm event, the reservoir reduced total NO3− flux by 19.1% and P flux by 12.7%. On the contrary, ammonium (NH4+) fluxes were 200% higher downstream of the dam in comparison with fluxes into the reservoir, indicating that there was a substantial net export of NH4+ from the reservoir during the storm event. Longitudinally along the river to reservoir transition, a breakpoint of statistical significance was identified, highlighting the sharp contrast between NO3− concentrations within the river and reservoir. Results suggest that frequent storm events such as the one presented here can greatly alter N removal processes in river–reservoir systems. Overall, this study highlights the need to better understand the role that storm events play in river–reservoir N cycling dynamics.

Evaluating air-water and NAPL-water interfacial adsorption and retention of Perfluorocarboxylic acids within the Vadose zone

The release and transport of linear perfluorocarboxylic acids (PFCA) within the vadose-zone beneath per- and polyfluoroalkyl substance (PFAS)- and non-aqueous phase liquid (NAPL)-contaminated source areas is influenced by multi-phase interfacial retention phenomena. Conceptually, interfacial adsorption results in retardation of PFCA velocities in subsurface multiphase systems. However, site hydrochemical factors influencing interfacial adsorption are not yet fully elucidated. Herein, air-water and NAPL-water interfacial tension isotherms were prepared for six homologous PFCAs of environmental significance for deionized water and five synthetic groundwaters of increasing ionic strength. The isotherms were successfully modeled by the Langmuir-Szyskowski equation and parameters used to fit the measured data are provided. Concentration-dependent interfacial adsorption coefficients and retardation factors are also provided for each PFCA and ionic strength condition and are evaluated to assess their significance. Simplifying relationships for predicting interfacial adsorption based on PFCA chain length were found to be less appropriate for natural groundwaters that contain a mixture of dissolved divalent and monovalent ions. Air-water interfacial (AWI) adsorption increased in a threshold manner with ionic strength from 0 to 6 mM, whereafter further adsorption was marginal. PFCA retention within water-unsaturated porous media is shown to depend on a number of inter-related factors and conditions that complicate the use of retardation factors within analytical models typically used for predicting transport rates under field conditions. Numerical simulation is thus necessary to model fundamental fate and transport processes. Mathematical relationships for incorporating interfacial adsorption in future and existing unsaturated flow and transport models are described.

Fate, eco-toxicological characteristics, and treatment processes applied to water polluted with glyphosate: A critical review

Glyphosate is the most widely used active ingredient of Glyphosate Based Herbicides (GBHs), and which has environmental mobility towards water by its physicochemical characteristics. These properties determine its low availability in living organisms (log Kow < 0), which is increased by the presence of co-adjuvant activators in GBHs and its biodegradation (metabolites). Eco-toxicological studies have determined that glyphosate affects to several aquatic trophic-levels (freshwater/marine environments), being more toxics GBHs. Therefore, its potential environmental risk has promoted the development of conventional (biological and physicochemical) and non-conventional (Advanced-Oxidation-Processes or AOPs, combined processes) treatment strategies. Biological processes will generate incomplete degradation (metabolites generation), and variable removal efficiencies (25–99%). Physicochemical processes will be efficient (approx. 90%) but transferring the glyphosate from water to the adsorbent material (dangerous waste generation). Currently, AOPs will arise as a rapid (minutes) and effective alternative for glyphosate removal (>90%), depending on operational conditions, and without generation of intermediate metabolites. Moreover, new strategies (electrochemical) will avoid the hazardous waste production. Other combined processes (biological + physicochemical) will also reach glyphosate efficiencies removal above 90% but needing large spaces. However, their physical characteristics would make them feasible to be applied in agricultural areas.

A Diffusion-Reaction Model for Predicting Enzyme-Mediated Dynamic Hydrogel Stiffening.

Hydrogels with spatiotemporally tunable mechanical properties have been increasingly employed for studying the impact of tissue mechanics on cell fate processes. These dynamic hydrogels are particularly suitable for recapitulating the temporal stiffening of a tumor microenvironment. To this end, we have reported an enzyme-mediated stiffening hydrogel system where tyrosinase (Tyrase) was used to stiffen orthogonally crosslinked cell-laden hydrogels. Herein, a mathematical model was proposed to describe enzyme diffusion and reaction within a highly swollen gel network, and to elucidate the critical factors affecting the degree of gel stiffening. Briefly, Fick’s second law of diffusion was used to predict enzyme diffusion in a swollen poly(ethylene glycol) (PEG)-peptide hydrogel, whereas the Michaelis–Menten model was employed for estimating the extent of enzyme-mediated secondary crosslinking. To experimentally validate model predictions, we designed a hydrogel system composed of 8-arm PEG-norbornene (PEG8NB) and bis-cysteine containing peptide crosslinker. Hydrogel was crosslinked in a channel slide that permitted one-dimensional diffusion of Tyrase. Model predictions and experimental results suggested that an increasing network crosslinking during stiffening process did not significantly affect enzyme diffusion. Rather, diffusion path length and the time of enzyme incubation were more critical in determining the distribution of Tyrase and the formation of additional crosslinks in the hydrogel network. Finally, we demonstrated that the enzyme-stiffened hydrogels exhibited elastic properties similar to other chemically crosslinked hydrogels. This study provides a better mechanistic understanding regarding the process of enzyme-mediated dynamic stiffening of hydrogels.

The fate and behaviour of gunshot residue: recreational shooter distribution

ABSTRACTDespite continued improvements in gunshot residue (GSR) detection and analysis, there are still challenges in the interpretation of GSR evidence. The level and distribution of GSR present on an individual can be influenced by many factors, dependent upon the context of any given case. Due and diligent attention must therefore be placed upon fate and behaviour processes in relation to GSR when assessing and interpreting any case findings. The distribution of GSR upon the body of a recreational shooter was assessed. Samples were taken from 17 positions across a shooter’s body immediately after the discharge of one round of ammunition. The shooting hand prevailed as the most GSR-contaminated area, with as many as 351 characteristic GSR particles identified. The face and supporting hand also exhibited high levels of GSR contamination. This level of contamination raises questions concerning the fate and behaviour of GSR particles within the general environment, specifically with regard to transfer processes.

Multi-objective multi-pollutant waste load allocation model for rivers using coupled archived simulated annealing algorithm with QUAL2Kw

Abstract A simulation-optimization approach is a suitable tool in waste load allocation problems when considering competing objectives and complex pollutant fate and transport processes in water bodies. Here, an archived multi-objective simulated annealing (AMOSA) algorithm is developed to determine various decision variables related to multi-pollutant waste load allocation (MPWLA) problems. The developed AMOSA algorithm has been coupled to QUAL2Kw in order to derive optimal MPWLA programs in Gheshlagh River, Kordestan, Iran. Minimizing wastewater treatment plant (WWTP) costs, improving the EquityMeasure, and enhancing water quality index (WQI) of the river have been considered as objective functions of MPWLA problems. The applied WQI integrates various water quality parameters (biochemical oxygen demand (BOD), dissolved oxygen (DO), NH4-N, NO3-N, PO4-P, total suspended solids (TSS), and Coliform) in monitoring stations along the river. Results show in the scenario with the best EquityMeasure, higher pollutant removal rates have been allocated to Sanandaj WWTP effluent and pollutant point source No. 7 (creek of landfill leachate) due to their greater contributions to Gheshlagh River contamination. Owing to high pollutant load effluents and unsuitable background conditions in Gheshlagh River, more specific studies show that the water quality index may not be improved over 0.22, no matter how much cost is incurred or equity is sacrificed.

Environmental Fate of RNA Interference Pesticides: Adsorption and Degradation of Double-Stranded RNA Molecules in Agricultural Soils.

Double-stranded RNA (dsRNA) pesticides are a new generation of crop protectants that interfere with protein expression in targeted pest insects by a cellular mechanism called RNA interference (RNAi). The ecological risk assessment of these emerging pesticides necessitates an understanding of the fate of dsRNA molecules in receiving environments, among which agricultural soils are most important. We herein present an experimental approach using phosphorus-32 (32P)-radiolabeled dsRNA that allows studying key fate processes of dsRNA in soils with unprecedented sensitivity. This approach resolves previous analytical challenges in quantifying unlabeled dsRNA and its degradation products in soils. We demonstrate that 32P-dsRNA and its degradation products are quantifiable at concentrations as low as a few nanograms of dsRNA per gram of soil by both Cerenkov counting (to quantify total 32P-activity) and by polyacrylamide gel electrophoresis followed by phosphorimaging (to detect intact 32P-dsRNA and its 32P-containing degradation products). We show that dsRNA molecules added to soil suspensions undergo adsorption to soil particle surfaces, degradation in solution, and potential uptake by soil microorganisms. The results of this work on dsRNA adsorption and degradation advance a process-based understanding of the fate of dsRNA in soils and will inform ecological risk assessments of emerging dsRNA pesticides.

Advancements in Life Cycle Human Exposure and Toxicity Characterization.

Background:The Life Cycle Initiative, hosted at the United Nations Environment Programme, selected human toxicity impacts from exposure to chemical substances as an impact category that requires global guidance to overcome current assessment challenges. The initiative leadership established the Human Toxicity Task Force to develop guidance on assessing human exposure and toxicity impacts. Based on input gathered at three workshops addressing the main current scientific challenges and questions, the task force built a roadmap for advancing human toxicity characterization, primarily for use in life cycle impact assessment (LCIA).Objectives:The present paper aims at reporting on the outcomes of the task force workshops along with interpretation of how these outcomes will impact the practice and reliability of toxicity characterization. The task force thereby focuses on two major issues that emerged from the workshops, namely considering near-field exposures and improving dose–response modeling.Discussion:The task force recommended approaches to improve the assessment of human exposure, including capturing missing exposure settings and human receptor pathways by coupling additional fate and exposure processes in consumer and occupational environments (near field) with existing processes in outdoor environments (far field). To quantify overall aggregate exposure, the task force suggested that environments be coupled using a consistent set of quantified chemical mass fractions transferred among environmental compartments. With respect to dose–response, the task force was concerned about the way LCIA currently characterizes human toxicity effects, and discussed several potential solutions. A specific concern is the use of a (linear) dose–response extrapolation to zero. Another concern addresses the challenge of identifying a metric for human toxicity impacts that is aligned with the spatiotemporal resolution of present LCIA methodology, yet is adequate to indicate health impact potential.Conclusions:Further research efforts are required based on our proposed set of recommendations for improving the characterization of human exposure and toxicity impacts in LCIA and other comparative assessment frameworks. https://doi.org/10.1289/EHP3871

Dynamic control of hydrogel crosslinking via sortase-mediated reversible transpeptidation

Cell-laden hydrogels whose crosslinking density can be dynamically and reversibly tuned are highly sought-after for studying pathophysiological cellular fate processes, including embryogenesis, fibrosis, and tumorigenesis. Special efforts have focused on controlling network crosslinking in poly(ethylene glycol) (PEG) based hydrogels to evaluate the impact of matrix mechanics on cell proliferation, morphogenesis, and differentiation. In this study, we sought to design dynamic PEG-peptide hydrogels that permit cyclic/reversible stiffening and softening. This was achieved by utilizing reversible enzymatic reactions that afford specificity, biorthogonality, and predictable reaction kinetics. To that end, we prepared PEG-peptide conjugates to enable sortase A (SrtA) induced tunable hydrogel crosslinking independent of macromer contents. Uniquely, these hydrogels can be completely degraded by the same enzymatic reactions and the degradation rate can be tuned from hours to days. We further synthesized SrtA-sensitive peptide linker (i.e., KCLPRTGCK) for crosslinking with 8-arm PEG-norbornene (PEG8NB) via thiol-norbornene photocrosslinking. These hydrogels afford diverse softening paradigms through control of network structures during crosslinking or by adjusting enzymatic parameters during on-demand softening. Importantly, user-controlled hydrogel softening promoted spreading of human mesenchymal stem cells (hMSCs) in 3D. Finally, we designed a bis-cysteine-bearing linear peptide flanked with SrtA substrates at the peptide’s N- and C-termini (i.e., NH2-GGGCKGGGKCLPRTG-CONH2) to enable cyclic/reversible hydrogel stiffening/softening. We show that matrix stiffening and softening play a crucial role in growth and chemoresistance in pancreatic cancer cells. These results represent the first dynamic hydrogel platform that affords cyclic gel stiffening/softening based on reversible enzymatic reactions. More importantly, the chemical motifs that affords such reversible crosslinking were built-in on the linear peptide crosslinker without any post-synthesis modification. Statement of SignificanceCell-laden ‘dynamic’ hydrogels are typically designed to enable externally stimulated stiffening or softening of the hydrogel network. However, no enzymatic reaction has been used to reversibly control matrix crosslinking. The application of SrtA-mediated transpeptidation in crosslinking and post-gelation modification of biomimetic hydrogels is innovative because of the specificity of the reaction and reversible tunability of crosslinking kinetics. While SrtA has been previously used to crosslink and fully degrade hydrogels, matrix softening and reversible stiffening of cell-laden hydrogels has not been reported. By designing simple peptide substrates, this unique enzymatic reaction can be employed to form a primary network, to gradually soften hydrogels, or to reversibly stiffen hydrogels. As a result, this dynamic hydrogel platform can be used to answer important matrix-related biological questions that are otherwise difficult to address.

Maxent estimation of aquatic Escherichia coli stream impairment.

BackgroundThe leading cause of surface water impairment in United States’ rivers and streams is pathogen contamination. Although use of fecal indicators has reduced human health risk, current approaches to identify and reduce exposure can be improved. One important knowledge gap within exposure assessment is characterization of complex fate and transport processes of fecal pollution. Novel modeling processes can inform watershed decision-making to improve exposure assessment.MethodsWe used the ecological model, Maxent, and the fecal indicator bacterium Escherichia coli to identify environmental factors associated with surface water impairment. Samples were collected August, November, February, and May for 8 years on Sinking Creek in Northeast Tennessee and analyzed for 10 water quality parameters and E. coli concentrations. Univariate and multivariate models estimated probability of impairment given the water quality parameters. Model performance was assessed using area under the receiving operating characteristic (AUC) and prediction accuracy, defined as the model’s ability to predict both true positives (impairment) and true negatives (compliance). Univariate models generated action values, or environmental thresholds, to indicate potential E. coli impairment based on a single parameter. Multivariate models predicted probability of impairment given a suite of environmental variables, and jack-knife sensitivity analysis removed unresponsive variables to elicit a set of the most responsive parameters.ResultsWater temperature univariate models performed best as indicated by AUC, but alkalinity models were the most accurate at correctly classifying impairment. Sensitivity analysis revealed that models were most sensitive to removal of specific conductance. Other sensitive variables included water temperature, dissolved oxygen, discharge, and NO3. The removal of dissolved oxygen improved model performance based on testing AUC, justifying development of two optimized multivariate models; a 5-variable model including all sensitive parameters, and a 4-variable model that excluded dissolved oxygen.DiscussionResults suggest that E. coli impairment in Sinking Creek is influenced by seasonality and agricultural run-off, stressing the need for multi-month sampling along a stream continuum. Although discharge was not predictive of E. coli impairment alone, its interactive effect stresses the importance of both flow dependent and independent processes associated with E. coli impairment. This research also highlights the interactions between nutrient and fecal pollution, a key consideration for watersheds with multiple synergistic impairments. Although one indicator cannot mimic theplethora of existing pathogens in water, incorporating modeling can fine tune an indicator’s utility, providing information concerning fate, transport, and source of fecal pollution while prioritizing resources and increasing confidence in decision making.

Canonical Variable Selection for Ecological Modeling of Fecal Indicators.

More than 270,000 km of rivers and streams are impaired due to fecal pathogens, creating an economic and public health burden. Fecal indicator organisms such as are used to determine if surface waters are pathogen impaired, but they fail to identify human health risks, provide source information, or have unique fate and transport processes. Statistical and machine learning models can be used to overcome some of these weaknesses, including identifying ecological mechanisms influencing fecal pollution. In this study, canonical correlation analysis (CCorA) was performed to select parameters for the machine learning model, Maxent, to identify how chemical and microbial parameters can predict impairment and F-somatic bacteriophage detections. Models were validated using a bootstrapping cross-validation. Three suites of models were developed; initial models using all parameters, models using parameters identified in CCorA, and optimized models after further sensitivity analysis. Canonical correlation analysis reduced the number of parameters needed to achieve the same degree of accuracy in the initial model (84.7%), and sensitivity analysis improved accuracy to 86.1%. Bacteriophage model accuracies were 79.2, 70.8, and 69.4% for the initial, CCorA, and optimized models, respectively; this suggests complex ecological interactions of bacteriophages are not captured by CCorA. Results indicate distinct ecological drivers of impairment depending on the fecal indicator organism used. impairment is driven by increased hardness and microbial activity, whereas bacteriophage detection is inhibited by high levels of coliforms in sediment. Both indicators were influenced by organic pollution and phosphorus limitation.

Designer hydrogels: Shedding light on the physical chemistry of the pancreatic cancer microenvironment

Pancreatic ductal adenocarcinoma (PDAC) is currently the third leading cause of cancer mortality in the United States, with a 5-year survival of ∼8%. PDAC is characterized by a dense and hypo-vascularized stroma consisting of proliferating cancer cells, cancer-associated fibroblasts, macrophages and immune cells, as well as excess matrices including collagens, fibronectin, and hyaluronic acid. In addition, PDAC has increased interstitial pressures and a hypoxic/acidic tumor microenvironment (TME) that impedes drug delivery and blocks cancer-directed immune mechanisms. In spite of increasing options in targeted therapy, PDAC has mostly remained treatment recalcitrant. Owing to its critical roles on governing PDAC progression and treatment outcome, TME and its interplay with the cancer cells are increasingly studied. In particular, three-dimensional (3D) hydrogels derived from or inspired by components in the TME are progressively developed. When properly designed, these hydrogels (e.g., Matrigel, collagen gel, hyaluronic acid-based, and semi-synthetic hydrogels) can provide pathophysiologically relevant compositions, conditions, and contexts for supporting PDAC cell fate processes. This review summarizes recent efforts in using 3D hydrogels for fundamental studies on cell-matrix or cell-cell interactions in PDAC.

Linking watershed modeling and bacterial source tracking to better assess E. coli sources

Terrestrial fate and transport processes of E. coli can be complicated by human activities like urbanization or livestock grazing. There is a critical need to address contributing sources of bacterial contamination, properly assess the management of critical sources, and ultimately reduce E. coli concentrations in impaired water bodies. In particular, characterization of wildlife animal contributions and other “background” input sources of microbial pollution are highly uncertain and data are scarce. This study attempts to identify critical sources of E. coli and the efficacy of conservation practices for mitigating E. coli concentrations in the Arroyo Colorado watershed, Texas, using a process-based hydrologic and water quality model. We propose to incorporate a bacterial source tracking assessment into the modeling framework to fill the gap in data on wildlife and human contribution. In addition, other sources identified through a GIS survey, national census, and local expert knowledge were incorporated into the model as E. coli sources. Results suggest that simulated distribution of E. coli sources significantly improved after incorporating this enhanced data on E. coli sources into the model (R2 = 0.90) compared to the SWAT result without BST (R2 = 0.59). Scenario assessments indicate that wildlife contributions may remain significant despite land use change and urbanization, expected to mostly occur in agricultural and range lands. A combination of nonpoint source management measures, voluntary implementation of advanced treatment by wastewater plants where possible, and installation of aerators in the zone of impairment were demonstrated to be effective measures for restoring the recreation and aquatic life uses of the Arroyo Colorado.

Analysis of Electrical Analogue of a Biological Cell and Its Response to External Electric Field

Abstract: The use of electric field stimulation to elicit a desired cell/tissue response has become a versatile strategy in regenerative medicine. Using an array of cell types and biomaterial substrates, our group has experimentally investigated the influence of external electric field parameters on the modulation of cellular functionality in vitro. However, the mechanism of action of electric field is not clearly understood, especially in cases where cell fate processes such as differentiation and proliferation are significantly enhanced due to electric field stimulation. In order to understand these important phenomena, it is necessary to first examine the response on a single cell. In this direction, we analyze the response of an electrical analogue of a single biological cell, wherein an electrical equivalent resistor-capacitor (R-C) network has been constructed by considering membranes as capacitive and surrounding biological media (cytoplasm and nucleoplasm) as resistive components. The response of this electrical analogue of a biological cell to external electric field (E-field) is determined using analytical techniques and SPICE-based simulations. The solutions for the network provide a time constant of â�� 30 I¼s, which is higher compared to the case when membranes were considered to be purely capacitive. The above model formulation has been further extended to determine the steady-state current response under various input signals, like sinusoidal, square, and triangular pulses using SPICE simulation package. In the context of regenerative engineering, the results of the present work are perceived to be important to design electric field-based stimulation strategies to obtain desired responses of electroactive tissues. Lay Summary: The importance of the effect of electric field on cells and tissues has become evident over the last two decades. Prior studies indicate that based on the electric field parameters, it is possible to get various cellular responses. The current study is an attempt to investigate why this is the case by approximating a single cell into an equivalent electrical network with resistors and capacitors. The network response is studied using simulation tools to get current waveforms and analytical techniques to obtain time constants, which provide vital insights into the observed cell behaviors reported in the literature. © 2018, The Regenerative Engineering Society.

Improving the SoilPlusVeg model to evaluate rhizoremediation and PCB fate in contaminated soils

Tools to predict environmental fate processes during remediation of persistent organic pollutants (POPs) in soil are desperately needed since they can elucidate the overall behavior of the chemical and help to improve the remediation process. A dynamic multimedia fate model (SoilPlusVeg) was further developed and improved to account for rhizoremediation processes. The resulting model was used to predict Polychlorinated Biphenyl (PCB) fate in a highly contaminated agricultural field (1089 ng/g d.w.) treated with tall fescue (Festuca arundinacea), a promising plant species for the remediation of contaminated soils. The model simulations allowed to calculate the rhizoremediation time (about 90 years), given the available rhizoremediation half-lives and the levels and fingerprints of the PCB congeners, to reach the legal threshold, to show the relevance of the loss processes from soil (in order of importance: degradation, infiltration, volatilization, etc.) and their dependence on meteorological and environmental dynamics (temperature, rainfall, DOC concentrations). The simulations showed that the effective persistence of PCBs in soil is deeply influenced by the seasonal variability. The model also allowed to evaluate the role of DOC as a possible enhancer of PCB degradation as a microorganism “spoon feeder” of PCBs in the soil solution. Additionally, we preliminary predicted how the contribution of PCB metabolites could modify the PCB fingerprint and their final total concentrations. This shows that the SoilPlusVeg model could be used in selecting the best choices for a sustainable rhizoremediation of a POP contaminated site.

Toxicological and chemical studies of wastewater from hydraulic fracture and conventional shale gas wells.

New technology has enabled recovery of inaccessible natural gas shale deposits; however, the potential impacts to human health from the migration of brines into drinking water or surface spills are unknown. To provide information that can inform these potential impacts, chemical characterization and in vitro toxicologic testing were conducted using pre- and postinjection waters from conventional and unconventional oil and gas wells. Wastewater concentrations may be diluted or reduced by fate and transport processes when released into the environment by unknown amounts, and laboratory studies only imply potential effects. In acute cytotoxicity and wound healing assays, there was dose-dependent toxicity in human and rat cells with growth promotion at low concentrations. Lethality was measured in time studies up to 10 d postinjection. Produced water samples from both well types were equally toxic to human cells and were corrosive at high concentrations. Measurement of protein and gene expression identified metabolic pathways responding to both well types as NADPH quinone oxidoreductase oxidative stress-responsive enzyme and tight junction protein genes. A KCl sample of matched ionic strength showed a different toxicity profile from produced waters, indicating that salts alone were not the cause of toxicity. Organic chemicals and branched alkanes were present in hydraulic fracture wells, and mainly branched alkanes were present in conventional wells. One organic substance was still present after 240 d. The known properties of these chemicals include potential toxicity to multiple human organs, sensitization, irritation, developmental effects, and tumor promotion, depending on the concentrations and synergistic effects of chemicals during exposure. Environ Toxicol Chem 2018;37:2098-2111. © 2018 SETAC.

Multiphoton 3D Microprinting of Protein Micropatterns with Spatially Controlled Heterogeneity – A Platform for Single Cell Matrix Niche Studies

AbstractReconstituting the biomimetic cell niche in vitro is important as it allows to determine how niche factors may affect cellular fate processes. Many biofabrication and micropatterning technologies are developed to achieve this goal. However, the critical outstanding challenges are the capabilities to spatially control the micropatterns and to decouple the different niche factors. Multiphoton microfabrication is an emerging technology with unique advantages. A multiphoton 3D microprinting platform has been previously established to create protein microstructures and micropatterns with sub‐micrometer resolution and its ability to control the topological features, porosity, and mechanical properties of microprinted protein cell niche has been demonstrated. Here, it is demonstrated that the multiphoton microprinting technology is able to precisely control the local density of the matrix niche factor, and more importantly, spatially control and decouple the mechanical and matrix niche factors. The results show that 1) the micropatterned matrix niche retains its bioactivities; 2) mesenchymal stem cells (MSCs) are able to sense the elastic modulus of the cell niche when the mechanical and matrix niche factors are decoupled; and 3) MSCs prefer to bind to and spread on fibronectin among other matrix proteins. These results path the way to future development of a “programmable” cell niche platform.

Atmospheric degradation of HCFO-1233zd(E) initiated by OH radical, Cl atom and O3 molecule: Kinetics, reaction mechanisms and implications

A degradation of trans-CF3CH=CHCl (HCFO-1233zd(E)) by reaction with OH radical, Cl atom and O3 molecule over the temperature range 200–1000 K has been studied employing the density functional theory. The potential energy surfaces accompnying the degradation have further been characterized in terms of single point energies derived from the coupled cluster CCSD(T) theory. Different possible pathways including H-abstraction, addition, isomerisation, dissociation and secondary reactions in absence and presence of O2/NOx are considered to elucidate the underlying mechanisms of the titled reactions. It has been shown that the initiation of degradation proceeds predominantly via addition to olefinic carbon with contributions from the direct H-abstraction channels being negligible as a result of the higher energy barrier. Calculated rate coefficients for the reaction of HCFO-1233zd(E) with OH was estimated to be 3.2 × 10−13 cm3 molecule‒1 sec‒1 whereas those for the reactions with Cl and O3 are predicted to be 3.7 × 10‒11 cm3 molecule‒1 sec‒1 and 50.0 × 10‒21 cm3 molecule‒1 sec‒1, respectively, which compare well with those from the earlier experiments. The present endeavor describes the atmospheric fate and oxidation processes of titled molecule and provides comprehensive data on the product branching ratios, atmospheric lifetimes and global warming potentials.