Toward Improved Bioremediation Strategies: Response of BAM-Degradation Activity to Concentration and Flow Changes in an Inoculated Bench-Scale Sediment Tank.

Compound-specific isotope analysis (CSIA) can reveal mass-transfer limitations during biodegradation of organic pollutants by enabling the detection of masked isotope fractionation. Here, we applied CSIA to monitor the adaptive response of bacterial degradation in inoculated sediment to low contaminant concentrations over time. We characterized Aminobacter sp. MSH1 activity in a flow-through sediment tank in response to a transient supply of elevated 2,6-dichlorobenzamide (BAM) concentrations as a priming strategy and took advantage of an inadvertent intermittence to investigate the effect of short-term flow fluctuations. Priming and flow fluctuations yielded improved biodegradation performance and increased biodegradation capacity, as evaluated from bacterial activity and residual concentration time series. However, changes in isotope ratios in space and over time evidenced that mass transfer became increasingly limiting for degradation of BAM at low concentrations under such stimulated conditions, and that activity decreased further due to bacterial adaptation at low BAM (µg/L) levels. Isotope ratios, in conjunction with residual substrate concentrations, therefore helped identifying underlying limitations of biodegradation in such a stimulated system, offering important insight for future optimization of remediation schemes.

Magnitude of Diffusion- and Transverse Dispersion-Induced Isotope Fractionation of Organic Compounds in Aqueous Systems.

Determining whether aqueous diffusion and dispersion lead to significant isotope fractionation is important for interpreting the isotope ratios of organic contaminants in groundwater. We performed diffusion experiments with modified Stokes diaphragm cells and transverse-dispersion experiments in quasi-two-dimensional flow-through sediment tank systems to explore isotope fractionation for benzene, toluene, ethylbenzene, 2,6-dichlorobenzamide, and metolachlor at natural isotopic abundance. We observed very small to negligible diffusion- and transverse-dispersion-induced isotope enrichment factors (ε < -0.4 ‰), with changes in carbon and nitrogen isotope values within ±0.5‰ and ±1‰, respectively. Isotope effects of diffusion did not show a clear correlation with isotopologue mass with calculated power-law exponents ß close to zero (0.007 < ß < 0.1). In comparison to ions, noble gases, and labeled compounds, three aspects stand out. (i) If a mass dependence is derived from collision theory, then isotopologue masses of polyatomic molecules would be affected by isotopes of multiple elements resulting in very small expected effects. (ii) However, collisions do not necessarily lead to translational movement but can excite molecular vibrations or rotations minimizing the mass dependence. (iii) Solute-solvent interactions like H-bonds can further minimize the effect of collisions. Modeling scenarios showed that an inadequate model choice, or erroneous choice of ß, can greatly overestimate the isotope fractionation by diffusion and, consequently, transverse dispersion. In contrast, available data for chlorinated solvent and gasoline contaminants at natural isotopic abundance suggest that in field scenarios, a potential additional uncertainty from aqueous diffusion or dispersion would add to current instrumental uncertainties on carbon or nitrogen isotope values (±1‰) with an additional ±1‰ at most.

Mass-Transfer-Limited Biodegradation at Low Concentrations-Evidence from Reactive Transport Modeling of Isotope Profiles in a Bench-Scale Aquifer.

Organic contaminant degradation by suspended bacteria in chemostats has shown that isotope fractionation decreases dramatically when pollutant concentrations fall below the (half-saturation) Monod constant. This masked isotope fractionation implies that membrane transfer is slow relative to the enzyme turnover at µg L-1 substrate levels. Analogous evidence of mass transfer as a bottleneck for biodegradation in aquifer settings, where microbes are attached to the sediment, is lacking. A quasi-two-dimensional flow-through sediment microcosm/tank system enabled us to study the aerobic degradation of 2,6-dichlorobenzamide (BAM), while collecting sufficient samples at the outlet for compound-specific isotope analysis. By feeding an anoxic BAM solution through the center inlet port and dissolved oxygen (DO) above and below, strong transverse concentration cross-gradients of BAM and DO yielded zones of low (µg L-1) steady-state concentrations. We were able to simulate the profiles of concentrations and isotope ratios of the contaminant plume using a reactive transport model that accounted for a mass-transfer limitation into bacterial cells, where apparent isotope enrichment factors *ε decreased strongly below concentrations around 600 µg/L BAM. For the biodegradation of organic micropollutants, mass transfer into the cell emerges as a bottleneck, specifically at low (µg L-1) concentrations. Neglecting this effect when interpreting isotope ratios at field sites may lead to a significant underestimation of biodegradation.

AQDS and Redox-Active NOM Enables Microbial Fe(III)-Mineral Reduction at cm-Scales.

Redox-active organic molecules such as anthraquinone-2,6-disulfonate (AQDS) and natural organic matter (NOM) can act as electron shuttles thus facilitating electron transfer from Fe(III)-reducing bacteria (FeRB) to terminal electron acceptors such as Fe(III) minerals. In this research, we examined the length scale over which this electron shuttling can occur. We present results from agar-solidified experimental incubations, containing either AQDS or NOM, where FeRB were physically separated from ferrihydrite or goethite by 2 cm. Iron speciation and concentration measurements coupled to a diffusion-reaction model highlighted clearly Fe(III) reduction in the presence of electron shuttles, independent of the type of FeRB. Based on our fitted model, the rate of ferrihydrite reduction increased from 0.07 to 0.19 µmol d-1 with a 10-fold increase in the AQDS concentration, highlighting a dependence of the reduction rate on the electron-shuttle concentration. To capture the kinetics of Fe(II) production, the effective AQDS diffusion coefficient had to be increased by a factor of 9.4. Thus, we postulate that the 2 cm electron transfer was enabled by a combination of AQDS molecular diffusion and an electron hopping contribution from reduced to oxidized AQDS molecules. Our results demonstrate that AQDS and NOM can drive microbial Fe(III) reduction across 2 cm distances and shed light on the electron transfer process in natural anoxic environments.

Modeling of Contaminant Biodegradation and Compound-Specific Isotope Fractionation in Chemostats at Low Dilution Rates.

We present a framework to model microbial transformations in chemostats and retentostats under transient or quasi-steady state conditions. The model accounts for transformation-induced isotope fractionation and mass-transfer across the cell membrane. It also verifies that the isotope fractionation ϵ can be evaluated as the difference of substrate-specific isotope ratios between inflow and outflow. We explicitly considered that the dropwise feeding of substrate into the reactor at very low dilution rates leads to transient behavior of concentrations and transformation rates and use this information to validate conditions under which a quasi-steady state treatment is justified. We demonstrate the practicality of the code by modeling a chemostat experiment of atrazine degradation at low dilution/growth rates by the strain Arthrobacter aurescens TC1. Our results shed light on the interplay of processes that control biodegradation and isotope fractionation of contaminants at low (µg/L) concentration levels. With the help of the model, an estimate of the mass-transfer coefficient of atrazine through the cell membrane was achieved (0.0025 s-1).

Mass Transfer Limitation during Slow Anaerobic Biodegradation of 2-Methylnaphthalene.

While they are theoretically conceptualized to restrict biodegradation of organic contaminants, bioavailability limitations are challenging to observe directly. Here we explore the onset of mass transfer limitations during slow biodegradation of the polycyclic aromatic hydrocarbon 2-methylnaphthalene (2-MN) by the anaerobic, sulfate-reducing strain NaphS2. Carbon and hydrogen compound specific isotope fractionation was pronounced at high aqueous 2-MN concentrations (60 µM) (εcarbon = -2.1 ± 0.1‰/εhydrogen = -40 ± 7‰) in the absence of an oil phase but became significantly smaller (εcarbon = -0.9 ± 0.3‰/εhydrogen = -6 ± 3‰) or nondetectable when low aqueous concentrations (4 µM versus 0.5 µM) were in equilibrium with 80 or 10 mM 2-MN in hexadecane, respectively. This masking of isotope fractionation directly evidenced mass transfer limitations at (sub)micromolar substrate concentrations. Remarkably, oil-water mass transfer coefficients were 60-90 times greater in biotic experiments than in the absence of bacteria (korg-aq2-MN = 0.01 ± 0.003 cm h-1). The ability of isotope fractionation to identify mass transfer limitations may help study how microorganisms adapt and navigate at the brink of bioavailability at low concentrations. For field surveys our results imply that, at trace concentrations, the absence of isotope fractionation does not necessarily indicate the absence of biodegradation.

Application of Experimental Polystyrene Partition Constants and Diffusion Coefficients to Predict the Sorption of Neutral Organic Chemicals to Multiwell Plates in in Vivo and in Vitro Bioassays.

Sorption to the polystyrene (PS) of multiwell plates can affect the exposure to organic chemicals over time in in vitro and in vivo bioassays. Experimentally determined diffusion coefficients in PS ( DPS) were in a narrow range of 1.25 to 8.0 · 10-16 m2 s-1 and PS-water partition constants ( KPS/w) ranged from 0.04 to 5.10 log-units for 22 neutral organic chemicals. A kinetic model, which explicitly accounts for diffusion in the plastic, was applied to predict the depletion of neutral organic chemicals from different bioassay media by sorption to various multiwell plate formats. For chemicals with log Kow > 3, the medium concentrations decreased rapidly and considerably in the fish embryo toxicity assay but medium concentrations remained relatively constant in the cell-based bioassays with medium containing 10% fetal bovine serum (FBS), emphasizing the ability of the protein- and lipid-rich medium to compensate for losses by multiwell plate sorption. The PS sorption data may serve not only for exposure assessment in bioassays but also to model the contaminant uptake by and release from plastic packaging material and the chemical transport by PS particles in the environment.

Contaminant concentration versus flow velocity: drivers of biodegradation and microbial growth in groundwater model systems.

Aromatic hydrocarbons belong to the most abundant contaminants in groundwater systems. They can serve as carbon and energy source for a multitude of indigenous microorganisms. Predictions of contaminant biodegradation and microbial growth in contaminated aquifers are often vague because the parameters of microbial activity in the mathematical models used for predictions are typically derived from batch experiments, which don't represent conditions in the field. In order to improve our understanding of key drivers of natural attenuation and the accuracy of predictive models, we conducted comparative experiments in batch and sediment flow-through systems with varying concentrations of contaminant in the inflow and flow velocities applying the aerobic Pseudomonas putida strain F1 and the denitrifying Aromatoleum aromaticum strain EbN1. We followed toluene degradation and bacterial growth by measuring toluene and oxygen concentrations and by direct cell counts. In the sediment columns, the total amount of toluene degraded by P. putida F1 increased with increasing source concentration and flow velocity, while toluene removal efficiency gradually decreased. Results point at mass transfer limitation being an important process controlling toluene biodegradation that cannot be assessed with batch experiments. We also observed a decrease in the maximum specific growth rate with increasing source concentration and flow velocity. At low toluene concentrations, the efficiencies in carbon assimilation within the flow-through systems exceeded those in the batch systems. In all column experiments the number of attached cells plateaued after an initial growth phase indicating a specific "carrying capacity" depending on contaminant concentration and flow velocity. Moreover, in all cases, cells attached to the sediment dominated over those in suspension, and toluene degradation was performed practically by attached cells only. The observed effects of varying contaminant inflow concentration and flow velocity on biodegradation could be captured by a reactive-transport model. By monitoring both attached and suspended cells we could quantify the release of new-grown cells from the sediments to the mobile aqueous phase. Studying flow velocity and contaminant concentrations as key drivers of contaminant transformation in sediment flow-through microcosms improves our system understanding and eventually the prediction of microbial biodegradation at contaminated sites.

Shift in Mass Transfer of Wastewater Contaminants from Microplastics in the Presence of Dissolved Substances.

In aqueous environments, hydrophobic organic contaminants are often associated with particles. Besides natural particles, microplastics have raised public concern. The release of pollutants from such particles depends on mass transfer, either in an aqueous boundary layer or by intraparticle diffusion. Which of these mechanisms controls the mass-transfer kinetics depends on partition coefficients, particle size, boundary conditions, and time. We have developed a semianalytical model accounting for both processes and performed batch experiments on the desorption kinetics of typical wastewater pollutants (phenanthrene, tonalide, and benzophenone) at different dissolved-organic-matter concentrations, which change the overall partitioning between microplastics and water. Initially, mass transfer is externally dominated, while finally, intraparticle diffusion controls release kinetics. Under boundary conditions typical for batch experiments (finite bath), desorption accelerates with increasing partition coefficients for intraparticle diffusion, while it becomes independent of partition coefficients if film diffusion prevails. On the contrary, under field conditions (infinite bath), the pollutant release controlled by intraparticle diffusion is not affected by partitioning of the compound while external mass transfer slows down with increasing sorption. Our results clearly demonstrate that sorption/desorption time scales observed in batch experiments may not be transferred to field conditions without an appropriate model accounting for both the mass-transfer mechanisms and the specific boundary conditions at hand.

Formation of N-Nitrosodimethylamine during Chloramination of Secondary and Tertiary Amines: Role of Molecular Oxygen and Radical Intermediates.

N-Nitrosodimethylamine (NDMA) is a carcinogenic disinfection byproduct from water chloramination. Despite the identification of numerous NDMA precursors, essential parts of the reaction mechanism such as the incorporation of molecular O2 are poorly understood. In laboratory model systems for the chloramination of secondary and tertiary amines, we investigated the kinetics of precursor disappearance and NDMA formation, quantified the stoichiometries of monochloramine (NH2Cl) and aqueous O2 consumption, derived 18O-kinetic isotope effects (18O-KIE) for the reactions of aqueous O2, and studied the impact of radical scavengers on NDMA formation. Although the molar NDMA yields from five N,N-dimethylamine-containing precursors varied between 1.4% and 90%, we observed the stoichiometric removal of one O2 per N,N-dimethylamine group of the precursor indicating that the oxygenation of N atoms did not determine the molar NDMA yield. Small 18O-KIEs between 1.0026 ± 0.0003 and 1.0092 ± 0.0009 found for all precursors as well as completely inhibited NDMA formation in the presence of radical scavengers (ABTS and trolox) imply that O2 reacted with radical species. Our study suggests that aminyl radicals from the oxidation of organic amines by NH2Cl and N-peroxyl radicals from the reaction of aminyl radicals with aqueous O2 are part of the NDMA formation mechanism.

Compound-Specific Stable Isotope Fractionation of Pesticides and Pharmaceuticals in a Mesoscale Aquifer Model.

Compound-specific isotope analysis (CSIA) receives increasing interest for its ability to detect natural degradation of pesticides and pharmaceuticals. Despite recent laboratory studies, CSIA investigations of such micropollutants in the environment are still rare. To explore the certainty of information obtainable by CSIA in a near-environmental setting, a pulse of the pesticide bentazone, the pesticide metabolite 2,6-dichlorobenzamide (BAM), and the pharmaceuticals diclofenac and ibuprofen was released into a mesoscale aquifer with quasi-two-dimensional flow. Concentration breakthrough curves (BTC) of BAM and ibuprofen demonstrated neither degradation nor sorption. Bentazone was transformed but did not sorb significantly, whereas diclofenac showed both degradation and sorption. Carbon and nitrogen CSIA could be accomplished in similar concentrations as for "traditional" priority pollutants (low µg/L range), however, at the cost of uncertainties (0.4-0.5‰ (carbon), 1‰ (nitrogen)). Nonetheless, invariant carbon and nitrogen isotope values confirmed that BAM was neither degraded nor sorbed, while significant enrichment of (13)C and in particular (15)N corroborated transformation of diclofenac and bentazone. Retardation of diclofenac was reflected in additional (15)N sorption isotope effects, whereas isotope fractionation of transverse dispersion could not be identified. These results provide a benchmark on the performance of CSIA to monitor the reactivity of micropollutants in aquifers and may guide future efforts to accomplish CSIA at even lower concentrations (ng/L range).

Experimental Evidence of Helical Flow in Porous Media.

Helical flow leads to deformation of solute plumes and enhances transverse mixing in porous media. We present experiments in which macroscopic helical flow is created by arranging different materials to obtain an anisotropic macroscopic permeability tensor with spatially variable orientation. The resulting helical flow entails twisting streamlines which cause a significant increase in lateral mass exchange and thus a large enhancement of plume dilution (up to 235%) compared to transport in homogenous media. The setup may be used to effectively mix solutes in parallel streams similarly to static mixers, but in porous media.

Dynamics of suspended and attached aerobic toluene degraders in small-scale flow-through sediment systems under growth and starvation conditions.

The microbially mediated reactions, that are responsible for field-scale natural attenuation of organic pollutants, are governed by the concurrent presence of a degrading microbial community, suitable energy and carbon sources, electron acceptors, as well as nutrients. The temporal lack of one of these essential components for microbial activity, arising from transient environmental conditions, might potentially impair in situ biodegradation. This study presents results of small scale flow-through experiments aimed at ascertaining the effects of substrate-starvation periods on the aerobic degradation of toluene by Pseudomonas putida F1. During the course of the experiments, concentrations of attached and mobile bacteria, as well as toluene and oxygen were monitored. Results from a fitted reactive-transport model, along with the observed profiles, show the ability of attached cells to survive substrate-starvation periods of up to four months and suggest a highly dynamic exchange between attached and mobile cells under growth conditions and negligible cell detachment under substrate-starvation conditions. Upon reinstatement of toluene, it was readily degraded without a significant lag period, even after a starvation period of 130 days. Our experimental and modeling results strongly suggest that aerobic biodegradation of BTEX-hydrocarbons at contaminated field sites is not hampered by intermittent starvation periods of up to four months.

Particle-facilitated transport of lindane in water-saturated tropical lateritic porous media.

The persistent insecticide lindane [(1α,2α,3ß,4α,5α,6ß)-1,2,3,4,5,6-hexachlorocyclohexane] is still in use in many tropical countries and remains a threat to soil and water quality. We studied the sorption and transport of lindane onto and through lateritic soils in both the absence and presence of lignite particles, onto which lindane may preferably sorb. We determined a linear distribution coefficient of lindane onto the soil matrix of 3.38 ± 0.16 L kg. Soil particles were not released from the porous medium on changing ionic strength, and also transport of lindane was not affected by changes in ionic strength. We fitted coupled transport models for lindane and the particles to the data, revealing that: (i) sorption kinetics of lindane onto the matrix is described best by intraparticle diffusion; (ii) 20% of the total porosity of the lateritic sample is intraparticle porosity; and (iii) only lignite particles with a median diameter <0.45 µm were not retained in the porous medium and thus facilitated the transport of lindane. We conclude that although lindane and similar pollutants may sorb on tropical lateritic porous media, their transport may be facilitated by particles with high organic-C content or dissolved organic C (DOC). This may be of relevance in farmlands and swamp groundwater systems where DOC, produced by leaching or slow biodegradation of surface organic matter, could cause rapid groundwater contamination by sorbing pollutants. Moreover, the results of this study can help to understand nanoparticle behavior in lateritic soils as the size of particles that facilitate lindane transport approaches the nanoparticle size range.

Model complexity needed for quantitative analysis of high resolution isotope and concentration data from a toluene-pulse experiment.

Separating microbial- and physical-induced effects on the isotope signals of contaminants has been identified as a challenge in interpreting compound-specific isotope data. In contrast to simple analytical tools, such as the Rayleigh equation, reactive-transport models can account for complex interactions of different fractionating processes. The question arises how complex such models must be to reproduce the data while the model parameters remain identifiable. In this study, we reanalyze the high-resolution data set of toluene concentration and toluene-specific δ(13)C from the toluene-pulse experiment performed by Qiu et al. (this issue). We apply five reactive-transport models, differing in their degree of complexity. We uniquely quantify degradation and sorption properties of the system for each model, estimate the contributions of biodegradation-induced, sorption-induced, and transverse-dispersion-induced isotope fractionation to the overall isotope signal, and investigate the error introduced in the interpretation of the data when individual processes are neglected. Our results show that highly resolved data of both concentration and isotope ratios are needed for unique process identification facilitating reliable model calibration. Combined analysis of these highly resolved data demands reactive transport models accounting for nonlinear degradation kinetics and isotope fractionation by both reactive and physical processes such as sorption and transverse dispersion.

Direct experimental evidence of non-first order degradation kinetics and sorption-induced isotopic fractionation in a mesoscale aquifer: 13C/12C analysis of a transient toluene pulse.

The injection of a mixed toluene and D2O (conservative tracer) pulse into a pristine mesoscale aquifer enabled a first direct experimental comparison of contaminant-specific isotopic fractionation from sorption versus biodegradation and transverse dispersion on a relevant scale. Water samples were taken from two vertically resolved sampling ports at 4.2 m distance. Analysis of deuterium and toluene concentrations allowed quantifying the extent of sorption (R = 1.25) and biodegradation (37% and 44% of initial toluene at the two sampling ports). Sorption and biodegradation were found to directly affect toluene (13)C/(12)C breakthrough curves. In particular, isotope trends demonstrated that biodegradation underwent Michaelis-Menten kinetics rather than first-order kinetics. Carbon isotope enrichment factors obtained from an optimized reactive transport model (Eckert et al., this issue) including a possible isotope fractionation of transverse dispersion were ε(equ)(sorption) = -0.31 ‰, ε(kin)(transverse-dispersion) = -0.82 ‰, and ε(kin)(biodegradation) = -2.15 ‰. Extrapolation of our results to the scenario of a continuous injection predicted that (i) the bias in isotope fractionation from sorption, but not transverse dispersion, may be avoided when the plume reaches steady-state; and (ii) the relevance from both processes is expected to decrease at longer flow distances when isotope fractionation of degradation increasingly dominates.

Cell-sorting at the A/P boundary in the Drosophila wing primordium: a computational model to consolidate observed non-local effects of Hh signaling.

Non-intermingling, adjacent populations of cells define compartment boundaries; such boundaries are often essential for the positioning and the maintenance of tissue-organizers during growth. In the developing wing primordium of Drosophila melanogaster, signaling by the secreted protein Hedgehog (Hh) is required for compartment boundary maintenance. However, the precise mechanism of Hh input remains poorly understood. Here, we combine experimental observations of perturbed Hh signaling with computer simulations of cellular behavior, and connect physical properties of cells to their Hh signaling status. We find that experimental disruption of Hh signaling has observable effects on cell sorting surprisingly far from the compartment boundary, which is in contrast to a previous model that confines Hh influence to the compartment boundary itself. We have recapitulated our experimental observations by simulations of Hh diffusion and transduction coupled to mechanical tension along cell-to-cell contact surfaces. Intriguingly, the best results were obtained under the assumption that Hh signaling cannot alter the overall tension force of the cell, but will merely re-distribute it locally inside the cell, relative to the signaling status of neighboring cells. Our results suggest a scenario in which homotypic interactions of a putative Hh target molecule at the cell surface are converted into a mechanical force. Such a scenario could explain why the mechanical output of Hh signaling appears to be confined to the compartment boundary, despite the longer range of the Hh molecule itself. Our study is the first to couple a cellular vertex model describing mechanical properties of cells in a growing tissue, to an explicit model of an entire signaling pathway, including a freely diffusible component. We discuss potential applications and challenges of such an approach.

Does It Pay Off to Explicitly Link Functional Gene Expression to Denitrification Rates in Reaction Models?

Environmental omics and molecular-biological data have been proposed to yield improved quantitative predictions of biogeochemical processes. The abundances of functional genes and transcripts relate to the number of cells and activity of microorganisms. However, whether molecular-biological data can be quantitatively linked to reaction rates remains an open question. We present an enzyme-based denitrification model that simulates concentrations of transcription factors, functional-gene transcripts, enzymes, and solutes. We calibrated the model using experimental data from a well-controlled batch experiment with the denitrifier Paracoccous denitrificans. The model accurately predicts denitrification rates and measured transcript dynamics. The relationship between simulated transcript concentrations and reaction rates exhibits strong non-linearity and hysteresis related to the faster dynamics of gene transcription and substrate consumption, relative to enzyme production and decay. Hence, assuming a unique relationship between transcript-to-gene ratios and reaction rates, as frequently suggested, may be an erroneous simplification. Comparing model results of our enzyme-based model to those of a classical Monod-type model reveals that both formulations perform equally well with respect to nitrogen species, indicating only a low benefit of integrating molecular-biological data for estimating denitrification rates. Nonetheless, the enzyme-based model is a valuable tool to improve our mechanistic understanding of the relationship between biomolecular quantities and reaction rates. Furthermore, our results highlight that both enzyme kinetics (i.e., substrate limitation and inhibition) and gene expression or enzyme dynamics are important controls on denitrification rates.

Unraveling biogeochemical complexity through better integration of experiments and modeling.

The evolution of groundwater quality in natural and contaminated aquifers is affected by complex interactions between physical transport and biogeochemical reactions. Identifying and quantifying the processes that control the overall system behavior is the key driver for experimentation and monitoring. However, we argue that, in contrast to other disciplines in earth sciences, process-based computer models are currently vastly underutilized in the quest for understanding subsurface biogeochemistry. Such models provide an essential avenue for quantitatively testing hypothetical combinations of interacting, complex physical and chemical processes. If a particular conceptual model, and its numerical counterpart, cannot adequately reproduce observed experimental data, its underlying hypothesis must be rejected. This quantitative process of hypothesis testing and falsification is central to scientific discovery. We provide a perspective on how closer interactions between experimentalists and numerical modelers would enhance this scientific process, and discuss the potential limitations that are currently holding us back. We also propose a data-model nexus involving a greater use of numerical process-based models for a more rigorous analysis of experimental observations while also generating the basis for a systematic improvement in the design of future experiments.

Chromium (VI) removal kinetics by magnetite-coated sand: Small-scale flow-through column experiments.

Magnetite nanoparticles are promising materials for treating toxic Cr(VI), but safe handling is challenging due to their small size. We prepared flow-through columns containing 10% or 100% (v/v) magnetite-coated sand. Cr(VI) removal efficiency was determined for different Cr(VI) concentrations (0.1 or 1.0 mM), neutral or alkaline pH, and oxic/anoxic conditions. We formulated a reactive-transport model that accurately predicted total Cr removal, accounting for reversible and irreversible (chemi)sorption reactions. Our results show that the material removes and irreversibly sequesters Cr(VI). For the concentration range used 10% and 100% (v/v) -packed columns removed > 99% and 72% of influent Cr(VI), respectively. Two distinct parameter sets were necessary to fit the identical model formulation to the 10 or 100% (v/v) columns (e.g., maximum sorption capacities (qmax) of 1.37 µmol Cr/g sand and 2.48 µmol Cr/g, respectively), which we attributed to abrasion-driven magnetite micro-particle detachment during packing yielding an increase in reactive surface area. Furthermore, experiments under oxic conditions showed that, even when handled in the presence of O2, the magnetite-coated sand maintained a high removal capacity (47%). Our coupled experimental and modelling analyses indicates that magnetite-coated sand is a promising and suitable medium for treating Cr(VI)-contaminated water in fixed-bed reactors or permeable reactive barriers.