Legacy pollutants in fractured aquifers: Analytical approximations for back diffusion to predict atrazine concentrations under uncertainty.

We present novel analytical approximations for the estimation of travel distance and relative height of solute concentration peaks within a single fracture system for pollutants that have been temporarily applied at a constant rate in the past. These approximations are used to investigate the spatiotemporal evolution of the concentration of atrazine, as an example for many other so-called legacy compounds that are still found in the groundwater of fractured rock aquifers even decades after their application has stopped. This is done in a stochastic framework to account for the uncertainty in relevant parameters, focusing on probabilities of exceeding the given legal concentration limit and the expected length of the recovery period. We specifically consider the properties of the Muschelkalk limestone aquifer in the Ammer river catchment in SW Germany, and the three major types of carbonate rock facies: Shoal, Tempestite, and Basinal limestones. Atrazine sorption parameters have been determined in laboratory experiments. The simulations confirm that diffusion-limited sorption and desorption may cause considerable atrazine levels long after application stop. For the properties of the considered rock facies types, and corresponding parameter ranges, atrazine concentration above the legal limit is supposed to be limited to locations referring to only a few years of travel time. If the concentration exceeds the legal limit by the year 2022, it will take decades to centuries until recovery.

Comprehensive Multi-compartment Sampling for Quantification of Long-Term Accumulation of PAHs in Soils.

Long-term accumulation in the soils of ubiquitous organic pollutants such as many polycyclic aromatic hydrocarbons (PAHs) depends on deposition from the atmosphere, revolatilization, leaching, and degradation processes such as photolysis and biodegradation. Quantifying the phase distribution and fluxes of these compounds across environmental compartments is thus crucial to understand the long-term contaminant fate. The gas-phase exchange between soil and atmosphere follows chemical fugacity gradients that can be approximated by gas-phase concentrations, yet which are difficult to measure directly. Thus, passive sampling, measured sorption isotherms, or empirical relationships to estimate sorption distribution have been combined in this study to determine aqueous (or gas) phase concentrations from measured bulk concentrations in soil solids. All these methods have their strengths and weaknesses but agree within 1 order of magnitude except for ex situ passive samplers employed in soil slurries, which estimated much lower concentrations in soil water and gas likely due to experimental artifacts. In field measurements, PAH concentrations determined in the atmosphere show a pronounced seasonality with some revolatilization during summer and gaseous deposition during winter, but overall dry deposition dominates annual mean fluxes. The characteristic patterns of PAHs in the different phases (gas phase, atmospheric passive samplers, bulk deposition, and soil solids) confirm the expected compound-specific distribution pattern and behavior. Since revolatilization fluxes in summer are only minor and wet and dry deposition is ongoing, our results clearly show that the PAH loads in topsoils will continue to increase.