A Three-Dimensional View on Soil Biogeochemistry: A Dataset for a Forested Headwater Catchment.

Current understanding of the variability in soil properties and their relationship to processes and spatial patterns in forested landscapes is limited due to the scarcity of datasets providing such information. Here we present a spatially highly resolved dataset () that provides detailed information on the three-dimensional variability of biogeochemical properties in the Wüstebach catchment (western Germany), a long-term environmental observation site of the TERENO (Terrestrial Environmental Observatories) project. High-resolution soil sampling was conducted, and physical and biogeochemical soil parameters were recorded per horizon. The dataset is helpful in the analysis of the spatial heterogeneity in biogeochemical properties within soil horizons and with depth through the soil profile. In addition, it shows links between hydrological and biogeochemical properties and processes within the system. Overall, the dataset provides a high-resolution view into (re)cycling, leaching, and storage of nutrients on the catchment scale in a forested headwater catchment.

A Dataset for Three-Dimensional Distribution of 39 Elements Including Plant Nutrients and Other Metals and Metalloids in the Soils of a Forested Headwater Catchment.

Quantification and evaluation of elemental distribution in forested ecosystems are key requirements to understand element fluxes and their relationship with hydrological and biogeochemical processes in the system. However, datasets supporting such a study on the catchment scale are still limited. Here we provide a dataset comprising spatially highly resolved distributions of 39 elements in soil profiles of a small forested headwater catchment in western Germany () to gain a holistic picture of the state and fluxes of elements in the catchment. The elements include both plant nutrients and other metals and metalloids that were predominately derived from lithospheric or anthropogenic inputs, thereby allowing us to not only capture the nutrient status of the catchment but to also estimate the functional development of the ecosystem. Soil samples were collected at high lateral resolution (≤60 m), and element concentrations were determined vertically for four soil horizons (L/Of, Oh, A, B). From this, a three-dimensional view of the distribution of these elements could be established with high spatial resolution on the catchment scale in a temperate natural forested ecosystem. The dataset can be combined with other datasets and studies of the TERENO (Terrestrial Environmental Observatories) Data Discovery Portal () to reveal elemental fluxes, establish relations between elements and other soil properties, and/or as input for modeling elemental cycling in temperate forested ecosystems.

Do lab-derived distribution coefficient values of pesticides match distribution coefficient values determined from column and field-scale experiments? A critical analysis of relevant literature.

In this study, we analyzed sorption parameters for pesticides that were derived from batch and column or batch and field experiments. The batch experiments analyzed in this study were run with the same pesticide and soil as in the column and field experiments. We analyzed the relationship between the pore water velocity of the column and field experiments, solute residence times, and sorption parameters, such as the organic carbon normalized distribution coefficient ( ) and the mass exchange coefficient in kinetic models, as well as the predictability of sorption parameters from basic soil properties. The batch/column analysis included 38 studies with a total of 139 observations. The batch/field analysis included five studies, resulting in a dataset of 24 observations. For the batch/column data, power law relationships between pore water velocity, residence time, and sorption constants were derived. The unexplained variability in these equations was reduced, taking into account the saturation status and the packing status (disturbed-undisturbed) of the soil sample. A new regression equation was derived that allows estimating the values derived from column experiments using organic matter and bulk density with an value of 0.56. Regression analysis of the batch/column data showed that the relationship between batch- and column-derived values depends on the saturation status and packing of the soil column. Analysis of the batch/field data showed that as the batch-derived value becomes larger, field-derived values tend to be lower than the corresponding batch-derived values, and vice versa. The present dataset also showed that the variability in the ratio of batch- to column-derived value increases with increasing pore water velocity, with a maximum value approaching 3.5.

Fate of two herbicides in zero-tension lysimeters and in field soil.

In Germany, zero-tension lysimeters are used as part of the registration requirements in case pesticides pose a potential threat to contaminate the groundwater. However, the water regime and the method of pesticide sampling differ between the lysimeters and the field. We monitored the transport of the two herbicides ethidimuron [1-(5- ethylsulfonyl-1,3,4-thiadiazol-2-yl)-1,3-dimethylurea] (ETD) and methabenzthiazuron [1-benzothiazol-2-yl-1,3-dimethyl-urea] (MBT) and their main metabolite, accompanied with bromide as conservative tracer, in zero-tension lysimeters filled with undisturbed soil and in the field. The herbicides were applied as a short pulse to the bare soil surface. Herbicide concentrations were analyzed in the drainage water of the 1.2-m-deep lysimeters and from soil cores taken from the field during six campaigns. Soil coring in the field emphasized matrix flow and allowed us to estimate the field-based dissipation and sorption parameters. Based on mass recovery calculations, the field fate half-life was 870 d for ETD compared with 389 d for its main metabolite. The initially fast field-based dissipation of MBT with a half-life value of approximately 1 mo was followed by a much slower dissipation. The retardation factor was estimated from the concentration profiles by inversely solving the convection-dispersion equation and yielded 18.2 +/- 1.3 for ETD and 36.9 +/- 17.5 for MBT. For the lysimeters, a leaching period of 2 1/2 yr was too short to monitor bulk herbicide mass through the soil matrix. Only 1.7% of the applied EDT and 1.4% of the applied MBT were sampled in the drainage water at 1.2 m depth. Despite contrasting sorption and dissipation properties, both herbicides appeared fast and at the same time in the drainage water, hinting at preferential flow phenomena. Compared with field fate of herbicides measured by soil coring, zero-potential lysimeters emphasize the transport of small amounts of herbicides triggered by preferential flow events.

Transport of sulfadiazine in undisturbed soil columns: effects of flow rate, input concentration and pulse duration.

Antibiotics reach soils via spreading of manure or sewage sludge. Knowledge on the transport behavior of antibiotics in soils is needed to assess their environmental fate. The effect of flow rate and applied mass, i.e., input concentration and pulse duration, on the transport of 14C-sulfadiazine (SDZ; 4-aminoN-pyrimidin-2-yl-benzenesulfonamide) was investigated with soil column experiments and numerical studies. Sulfadiazine was applied in pulses (6.8, 68 or 306 h) under steady-state (0.051 and 0.21 cm h(-1)) and intermittent flow conditions and at two input concentrations (0.57 and 5.7 mg L(-1)). Breakthrough curves (BTCs) of 14C were measured and for one experiment concentrations of SDZ, and its transformation products 4-(2-iminopyrimidin-1(2H)-yl)aniline (An-SDZ) and N(1)-2-(4-hydroxypyrimidinyl)benzenesulfanilamide (4-OH-SDZ) were determined. After finalizing the leaching experiments, 14C was quantified in different slices of the columns. A lower flow rate led to remarkably lower eluted masses compared with the higher flow rates. All BTCs could be described well using a three-site attachment-detachment model for which a common set of parameters was determined. However, the BTC obtained with the high input concentration was slightly better described with a two-site isotherm-based model. The prediction of the concentration profiles was good with both model concepts. The fitted sorption capacities decreased in the order SDZ > 4-OH-SDZ > An-SDZ. Overall, the experiments reveal the presence of similar mechanisms characterizing SDZ transport. The dependence of model performance on concentration implies that although the three-site attachment-detachment model is appropriate to predict the transport of SDZ in soil columns, not all relevant processes are adequately captured.

Transport and transformation of sulfadiazine in soil columns packed with a silty loam and a loamy sand.

Concerning the transport of the veterinary antibiotic sulfadiazine (SDZ) little is known about its possible degradation during transport. Also its sorption behaviour is not yet completely understood. We investigated the transport of SDZ in soil columns with a special emphasis on the detection of transformation products in the outflow of the soil columns and on modelling of the concentration distribution in the soil columns afterwards. We used disturbed soil columns near saturation, packed with a loamy sand and a silty loam. SDZ was applied as a 0.57 mg L(-1) solution at a constant flow rate of 0.25 cm h(-1) for 68 h. Breakthrough curves (BTC) of SDZ and its transformation products 4-(2-iminopyrimidin-1(2H)-yl)aniline and 4-hydroxy-SDZ were measured for both soils. For the silty loam we additionally measured a BTC for an unknown transformation product which we only detected in the outflow samples of this soil. After the leaching experiments the (14)C-concentration was quantified in different layers of the soil columns. The transformation rates were low with mean SDZ mass fractions in the outflow samples of 95% for the loamy sand compared to 97% for the silty loam. The formation of 4-(2-iminopyrimidin-1(2H)-yl)aniline appears to be light dependent and did probably not occur in the soils, but afterwards. In the soil columns most of the (14)C was found near the soil surface. The BTCs in both soils were described well by a model with one reversible (kinetic) and one irreversible sorption site. Sorption kinetics played a more prominent role than sorption capacity. The prediction of the (14)C -concentration profiles was improved by applying two empirical models other than first order to predict irreversible sorption, but also these models were not able to describe the (14)C concentration profiles correctly. Irreversible sorption of sulfadiazine still is not well understood.

Persistent memory of diffusing particles.

The variance of the advection-diffusion processes with variable coefficients is exactly decomposed as a sum of dispersion terms and memory terms consisting of correlations between velocity and initial positions. For random initial conditions, the memory terms quantify the departure of the preasymptotic variance from the time-linear diffusive behavior. For deterministic initial conditions, the memory terms account for the memory of the initial positions of the diffusing particles. Numerical simulations based on a global random walk algorithm show that the influence of the initial distribution of the cloud of particles is felt over hundreds of dimensionless times. In case of diffusion in random velocity fields with finite correlation range the particles forget the initial positions in the long-time limit and the variance is self-averaging, with clear tendency toward normal diffusion.

Characterization of subsoil heterogeneity, estimation of grain size distribution and hydraulic conductivity at the Krauthausen test site using Cone Penetration Test.

A Cone Penetration Test (CPT) survey with a high spatial resolution was performed in order to investigate the stratigraphy as well as the spatial variability of various soil properties of the Krauthausen test site. Analyses of the CPT measurements showed the subsurface to be dominated by a planar layered structure. Variogram analysis of the various CPT parameters disclosed that within each layer the soil properties have an anisotropic spatial correlation structure. A correlation analysis of the measured CPT data and co-located grain size distributions from soil samples was performed. Since the correlation coefficients were greater equal to 0.7, a reliable empirical relationship between the data sets could be developed. Based on this empirical relationship grain size distributions were estimated at CPT locations. The statistical processing of estimated and measured grain size distributions with respect to their spatial correlation structure disclosed good agreement between the data sets. The estimated grain size distributions from CPT data were used to estimate the hydraulic conductivity in the aquifer. The results provide detailed information of the spatial heterogeneity of the hydraulic conductivity at Krauthausen test site. The validation of these results, using a prior investigation of hydraulic conductivity statistics, suggests the CPT a fast and inexpensive tool for the estimation of three dimensional hydraulic conductivity fields with sufficient accuracy.

Transport and deposition of metabolically active and stationary phase Deinococcus radiodurans in unsaturated porous media.

Bioremediation is a cost-efficient cleanup technique that involves the use of metabolically active bacteria to degrade recalcitrant pollutants. To further develop this technique it is important to understand the migration and deposition behavior of metabolically active bacteria in unsaturated soils. Unsaturated transport experiments were therefore performed using Deinococcus radiodurans cells that were harvested during the log phase and continuously supplied with nutrients during the experiments. Additional experiments were conducted using this bacterium in the stationary phase. Different water saturations were considered in these studies, namely 100 (only stationary phase), 80, and 40%. Results from this study clearly indicated thatthe physiological state of the bacteria influenced its transport and deposition in sands. Metabolically active bacteria were more hydrophobic and exhibited greater deposition than bacteria in the stationary phase, especially at a water saturation of 40%. The breakthrough curves for active bacteria also had low concentration tailing as a result of cell growth of retained bacteria that were released into the liquid phase. Collected breakthrough curves and deposition profiles were described using a model that simultaneously considers both chemical attachment and physical straining. New concepts and hypotheses were formulated in this model to include biological aspects associated with bacteria growth inside the porous media.

Bacteria transport and deposition under unsaturated conditions: the role of the matrix grain size and the bacteria surface protein.

Unsaturated (80% water saturated) packed column experiments were conducted to investigate the influence of grain size distribution and bacteria surface macromolecules on bacteria (Rhodococcus rhodochrous) transport and deposition mechanisms. Three sizes of silica sands were used in these transport experiments, and their median grain sizes were 607, 567, and 330 microm. The amount of retained bacteria increased with decreasing sand size, and most of the deposited bacteria were found adjacent to the column inlet. The deposition profiles were not consistent with predictions based on classical filtration theory. The experimental data could be accurately characterized using a mathematical model that accounted for first-order attachment, detachment, and time and depth-dependent straining processes. Visual observations of the bacteria deposition as well as mathematical modelling indicated that straining was the dominant mechanism of deposition in these sands (78-99.6% of the deposited bacteria), which may have been enhanced due to the tendency of this bacterium to form aggregates. An additional unsaturated experiment was conducted to better deduce the role of bacteria surface macromolecules on attachment and straining processes. In this case, the bacteria surface was treated using a proteolitic enzyme. This technique was assessed by examining the Fourier-transform infrared spectrum and hydrophobicity of untreated and enzyme treated cells. Both of these analytical procedures demonstrated that this enzymatic treatment removed the surface proteins and/or associated macromolecules. Transport and modelling studies conducted with the enzyme treated bacteria, revealed a decrease in attachment, but that straining was not significantly affected by this treatment.

Analysis of the long-term behavior of solute transport with nonlinear equilibrium sorption using breakthrough curves and temporal moments.

We analyzed the long-term behavior of breakthrough curves (BTCs) and temporal moments of a solute subjected to Freundlich equilibrium sorption (s = kc(n)). For one-dimensional transport in a homogeneous porous medium, we derived a power-law relation between travel time, tau, and solute displacement, chi, with the exponent being equal to the Freundlich n exponent. The mean solute velocity, derived from the first time moment, was found to change as tau(n-1). For n values larger than 0.66, the second time moment could be related to c chi(2/n), where c is a constant. An approach based on the use of a critical concentration was developed to estimate the presence of the asymptotic regime in the tail of the BTC. This approach was tested successfully using numerical case studies. One-dimensional numerical simulations with varying values of k, n and initial mass were run to verify the closed form analytical expressions for the large time behavior of temporal moments and the tailing part of breakthrough curves. Good agreement between the slope of the tailing part of log-log transformed BTCs and the predicted slope using asymptotic theory was found. Asymptotic theory in general underestimated the magnitude of the concentration in the tail. The quality of the estimated concentrations in the tail improved for small values of the dispersivity. Experimental BTCs of uranin and benazolin were analyzed in combination with sorption/desorption batch experiments using asymptotic theory. A good agreement between the value of n parameter derived from desorption experiment with benazolin and the value of the n parameter derived from the tail of the BTC was found.

Three-dimensional nickel ion transport through porous media using magnetic resonance imaging.

The transport of Ni2+ ions in a column, filled with porous media, was observed in three dimensions and time by magnetic resonance imaging (MRI) in a clinical scanner. For porous media we used glass beads or quartz sand in a saturated continuous flow mode. The magnetic moment of Ni2+ decreased the T1 relaxation time of 1H in aqueous solution. This concentration-dependent effect was used by a fast low angle shot (FLASH) MRI sequence for imaging the concentration of the dissolved ions. Since Ni2+ behaves as a conservative tracer under the chosen conditions, the tracer motion was representative for the water flow in the porous medium. Currently, we can achieve an isotropic spatial resolution of 1.5 mm and a temporal resolution of 170 s. The transport observation gives direct access to hydraulic flow properties of the porous media. The fluid flow velocity field was calculated by a fronttracking method and the statistical properties of the velocities were investigated. We also compared the experimental data with the three-dimensional particle tracking model PARTRACE, which uses the experimental flow field as input.

Analyses of locally measured bromide breakthrough curves from a natural gradient tracer experiment at Krauthausen.

Solute travel time distributions were derived from breakthrough curves (BTCs) of bromide concentrations, which were measured during a large-scale tracer experiment in a quaternary fluviatile aquifer at Krauthausen. Travel time distributions to a specific point in the aquifer were derived from locally measured BTCs, using averaged absolute concentrations cabs(x1,t), normalized concentrations cnorm(x1,t), and velocity-weighted normalized concentrations cvw(x1,t). The travel time distributions were characterized in terms of equivalent convective-dispersive transport parameters: the equivalent solute velocity and equivalent dispersivity. Parameters were derived from BTCs using moment analyses and least-squares fits of the 1-D convection-dispersion equation (CDE). Both local and averaged BTCs showed pronounced tailing which was not well described by the 1-D CDE and which indicates the presence of macroscopic regions with low velocities in the aquifer. Therefore, dispersivities derived from CDE fits were significantly smaller than those derived from time moments. The BTCs of cabs(x1,t) were dominated by only a few local BTCs with high concentrations and were less representative for the travel time distribution than BTCs of averaged normalized concentrations. Dispersivities derived from cnorm(x1,t) and cvw(x1,t) were very similar. Finally, estimates of dispersivities and vertical correlation length of lnK, gamma 3, from BTCs were in agreement with a first-order estimate of the dispersivity and gamma 3 based on grain size data and flow meter measurements.