The effects of scale and spatial heterogeneities on diffusion in volcanic breccias and basalts: Amchitka Island, Alaska

Knowledge of the factors that influence the diffusion of contaminants, such as the diffusivity and the connected porosity, is crucial to modeling the long-term fate and transport of contaminants in subsurface systems with small or negligible advective flow, such as in fractured crystalline rock. Fractured rock is naturally heterogeneous, and hence, understanding the diffusivity of a molecule through this material (or the formation factor of the medium) becomes a complex problem, with critical concerns about the scale of laboratory measurements and about the spatial variability of these measurements relative to the scale needed for fate and transport modeling. This study employed both electrical and tracer-based laboratory methods to investigate the effects of scale and pore system connectivity on the diffusivity for volcanic matrix rock derived from the study site, a former underground nuclear test site at Amchitka Island, Alaska. The results of these investigations indicate a relatively well-connected pore system with scale effects generally limited to approximately 6 cm lengths and well-correlated to observed heterogeneous features. An important conclusion resulting from this study, however, is that there is a potential for the estimated diffusivity to be misrepresented by an order of magnitude if multiple samples or longer sample lengths are not used. Given the relatively large number of measurements resulting from these investigations, an analysis of the probability density function (PDF) of the diffusivity was possible. The PDF of the diffusivity was shown to generally follow a normal distribution for individual geologic layers. However, when all of the geologic layers are considered together, the distribution of the subsurface as a whole was shown to follow a lognormal distribution due to the order of magnitude differences amongst the layers. An understanding of these distributions is essential for future stochastic modeling efforts.     

A detailed field-based evaluation of naphthenic acid mobility in groundwater

An anaerobic plume of process-affected groundwater was characterized in a shallow sand aquifer adjacent to an oil sands tailings impoundment. Based on biological oxygen demand measurements, the reductive capacity of the plume is considered minimal. Major dissolved components associated with the plume include HCO₃, Na, Cl, SO₄, and naphthenic acids (NAs). Quantitative and qualitative NA analyses were performed on groundwater samples to investigate NA fate and transport in the subsurface. Despite subsurface residence times exceeding 20 years, significant attenuation of NAs by biodegradation was not observed based on screening techniques developed at the time of the investigation. Relative to conservative tracers (i.e., Cl), overall NA attenuation in the subsurface is limited, which is consistent with batch sorption and microcosm studies performed by other authors. Insignificant biological oxygen demand and low concentrations of dissolved As (< 10 µg L^− 1) in the plume suggest that the potential for secondary trace metal release, specifically As, via reductive dissolution reactions driven by ingress of process-affected water is minimal. It is also possible that readily leachable As is not present in significant quantities within the sediments of the study area. Thus, for similar plumes of process-affected groundwater in shallow sand aquifers which may occur as oil sands mining expands, a reasonable expectation is for NA persistence, but minimal trace metal mobilization.     

Influence of temporally variable groundwater flow conditions on point measurements and contaminant mass flux estimations

Monitoring of contaminant concentrations, e.g., for the estimation of mass discharge or contaminant degradation rates, often is based on point measurements at observation wells. In addition to the problem, that point measurements may not be spatially representative, a further complication may arise due to the temporal dynamics of groundwater flow, which may cause a concentration measurement to be not temporally representative. This paper presents results from a numerical modeling study focusing on temporal variations of the groundwater flow direction. “Measurements” are obtained from point information representing observation wells installed along control planes using different well frequencies and configurations. Results of the scenario simulations show that temporally variable flow conditions can lead to significant temporal fluctuations of the concentration and thus are a substantial source of uncertainty for point measurements. Temporal variation of point concentration measurements may be as high as the average concentration determined, especially near the plume fringe, even when assuming a homogeneous distribution of the hydraulic conductivity. If a heterogeneous hydraulic conductivity field is present, the concentration variability due to a fluctuating groundwater flow direction varies significantly within the control plane and between the different realizations. Determination of contaminant mass fluxes is also influenced by the temporal variability of the concentration measurement, especially for large spacings of the observation wells. Passive dosimeter sampling is found to be appropriate for evaluating the stationarity of contaminant plumes as well as for estimating average concentrations over time when the plume has fully developed. Representative sampling has to be performed over several periods of groundwater flow fluctuation. For the determination of mass fluxes at heterogeneous sites, however, local fluxes, which may vary considerably along a control plane, have to be accounted for. Here, dosimeter sampling in combination with time integrated local water flux measurements can improve mass flux estimates under dynamic flow conditions.     

Minimal pesticide-primed soil inoculum density to secure maximum pesticide degradation efficiency in on-farm biopurification systems

Addition of pesticide-primed soil containing adapted pesticide degrading bacteria to the biofilter matrix of on farm biopurification systems (BPS) which treat pesticide contaminated wastewater, has been recommended, in order to ensure rapid establishment of a pesticide degrading microbial community in BPS. However, uncertainties exist about the minimal soil inoculum density needed for successful bioaugmentation of BPS. Therefore, in this study, BPS microcosm experiments were initiated with different linuron primed soil inoculum densities ranging from 0.5 to 50 vol.% and the evolution of the linuron mineralization capacity in the microcosms was monitored during feeding with linuron. Successful establishment of a linuron mineralization community in the BPS microcosms was achieved with all inoculum densities including the 0.5 vol.% density with only minor differences in the time needed to acquire maximum degradation capacity. Moreover, once established, the robustness of the linuron degrading microbial community towards expected stress situations proved to be independent of the initial inoculum density. This study shows that pesticide-primed soil inoculum densities as low as 0.5 vol.% can be used for bioaugmentation of a BPS matrix and further supports the use of BPS for treatment of pesticide-contaminated wastewater at farmyards.     

Characterization of silver release from commercially available functional (nano)textiles

Silver, both in the nano as well as in other forms, is used in many applications including antimicrobial textiles. Washing of such textiles has already been identified as an important process that results in the release of silver into wastewater. This study thus investigated the release of silver from eight different commercially available silver-textiles during a washing and rinsing cycle. The silver released was size-fractionated and characterized using electron microscopy. In addition, the antimicrobial functionality of the textiles was tested before and after washing. Three of the textiles contained nanosized silver (labeled or confirmed by manufacturers’ information), another used a metallic silver wire and four contained silver in undeclared form. The initial silver content of the textiles was between 1.5 and 2925 mg Ag/kg. Only four of the investigated textiles leached detectable amounts of silver, of which 34-80% was in the form of particles larger than 450 nm. Microscopic analysis of the particles released in the washing solutions identified Ti/Si-AgCl nanocomposites, AgCl nanoparticles, large AgCl particles, nanosilver sulfide and metallic nano-Ag, respectively. The nanoparticles were mainly found in highly agglomerated form. The identified nanotextiles showed the highest antimicrobial activity, whereas some of the other textiles, e.g. the one with a silver wire and the one with the lowest silver content, did not reduce the growth of bacteria at all. The results show that different silver textiles release different forms of silver during washing and that among the textiles investigated AgCl was the most frequently observed chemical form in the washwater.     

Pesticide residue dynamics in passion fruits: Comparing field trial and modelling results

We evaluated the exposure to pesticides from the consumption of passion fruits and subsequent human health risks by combining several methods: (i) experimental field studies including the determination of pesticide residues in/on passion fruits, (ii) dynamic plant uptake modelling, and (iii) human health risk assessment concepts. Eight commonly used pesticides were applied onto passion fruits cultivated in Colombia. Pesticide concentrations were measured periodically (between application and harvest) in whole fruits and fruit pulp. Measured concentrations were compared with predicted residues calculated with a dynamic and crop-specific pesticide uptake model, namely dynamiCROP. The model accounts for the time between pesticide application and harvest, the time between harvest and consumption, the amount of spray deposition on plant surfaces, uptake processes, dilution due to crop growth, degradation in plant components, and reduction due to food processing (peeling). Measured and modelled residues correspond well (r² = 0.88-0.99), with all predictions falling within the 90% confidence interval of the measured values. A mean error of 43% over all studied pesticides was observed between model estimates and measurements. The fraction of pesticide applied during cultivation that is eventually ingested by humans is on average 10⁻⁴-10⁻⁶, depending on the time period between application and ingestion and the processing step considered. Model calculations and intake fractions via fruit consumption based on experimental data corresponded well for all pesticides with a deviation of less than a factor of 2. Pesticide residues in fruits measured at recommended harvest dates were all below European Maximum Residue Limits (MRLs) and therefore do not indicate any violation of international regulatory thresholds.     

Nonideal transport of contaminants in heterogeneous porous media: 10. Impact of co-solutes on sorption by porous media with low organic-carbon contents

The impact of co-solutes on sorption of tetrachloroethene (PCE) by two porous media with low organic-carbon contents was examined by conducting batch experiments. The two media (Borden and Eustis) have similar physical properties, but significantly different organic-carbon (OC) contents. Sorption of PCE was nonlinear for both media, and well-described by the Freundlich equation. For the Borden aquifer material (OC = 0.03%), the isotherms measured with a suite of co-solutes present (1,2-dichlorobenzene, bromoform, carbon tetrachloride, and hexachloroethane) were identical to the isotherms measured for PCE alone. These results indicate that there was no measurable impact of the co-solutes on PCE sorption for this system. In contrast to the Borden results, there was a measurable reduction in sorption of PCE by the Eustis soil (OC = 0.38%) in the presence of the co-solutes. The organic-carbon fractions of both media contain hard-carbon components, which have been associated with the manifestation of nonideal sorption phenomena. The disparity in results observed for the two media may relate to relative differences in the magnitude and geochemical nature of these hard-carbon components.     

Use of a food web model to evaluate the factors responsible for high PCB fish concentrations in Lake Ellasjøen, a high Arctic Lake

Background, aim, and scope

Lake Ellasjøen, located in the Norwegian high arctic, contains the highest concentrations of polychlorinated biphenyls (PCBs) ever recorded in fish and sediment from high arctic lakes, and concentrations are more than 10 times greater than in nearby Lake Øyangen. These elevated concentrations in Ellasjøen have been previously attributed, in part, to contaminant loadings from seabirds that use Ellasjøen, but not Øyangen, as a resting area. However, other factors, such as food web structure, organism growth rate, weight, lipid content, lake morphology, and nutrient inputs from the seabird guano, also differ between the two systems. The aim of this study is to evaluate the relative influence of these factors as explanatory variables for the higher PCB fish concentrations in Ellasjøen compared with Øyangen, using both a food web model and empirical data.

Methods

The model is based on previously developed models but parameterized for Lakes Ellasjøen and Øyangen using measured data wherever possible. The model was applied to five representative PCB congeners (PCB 105, 118, 138, 153, and 180) using measured sediment and water concentrations as input data and evaluated with previously collected food web data.

Results

Modeled concentrations are within a factor of two of measured concentrations in 60% and 40% of the cases in Lakes Ellasjøen and Øyangen, respectively, and within a factor of 10 in 100% of the cases in both lakes. In many cases, this is comparable to the variability associated with the data as well as the efficacy of the predictions of other food web model applications.

Discussion

We next used the model to quantify the relative importance of five major differences between Ellasjøen and Øyangen by replacing variables representing each of these factors in the Ellasjøen model with those from Øyangen, in separate simulations. The model predicts that the elevated PCB concentrations in Ellasjøen water and sediment account for 49%–58% of differences in modeled fish PCB concentrations between lakes. These elevated sediment and, to a lesser extent, water concentrations in Ellasjøen are due to PCB loadings from seabird guano. However, sediment–water fugacity ratios of PCBs are consistently greater in Ellasjøen compared with Øyangen, which suggests that internal lake processes also contribute to differences in sediment and water concentrations. We hypothesize that the nutrients associated with guano influence sediment–water fugacity ratios of PCBs by increasing the stock of pelagic algae. As both these algae and the guano settle, their organic carbon content is degraded faster than PCBs, which causes an extra magnification step in Ellasjøen before these detrital particles are consumed by benthic organisms, which are in turn consumed by fish. The model predicts that the remaining ～50% of the differences in PCB concentrations observed between the fish of these lakes are due to other subtle differences in their food web structures.

Conclusions

In conclusion, based on the results of a food web model, we found that the most dominant factors influencing the higher PCB fish concentrations in Lake Ellasjøen compared with Øyangen are the higher sediment and water concentrations in Ellasjøen, caused by seabird guano. Together, sediment and water are predicted to account for 49%–58% of differences in fish concentrations between lakes. Although seabird guano provides a source of nutrients to the lake, in addition to contaminants, empirical data and indirect model results suggest that nutrients are not leading to decreased bioaccumulation, in contrast to what has been observed in temperate, pelagic food webs.

Recommendations and perspectives

The results of this study emphasize the importance of considering even small differences in food web structure when comparing bioaccumulation in two lakes; although the food web structures of Ellasjøen and Øyangen differ only slightly, the model predicts that these differences account for most of the remaining ～50% of the differences in PCB fish concentrations between the two lakes. This study further demonstrates the utility of food web models as we were able to predict and tease apart the influence of various factors responsible for the elevated concentrations in the fish from Lake Ellasjøen, which would have been difficult using the field data alone.     

Acid generation upon thermal concentration of natural water: The critical water content and the effects of ionic composition

Thermal evaporation of a variety of simulated pore waters from the region of Yucca Mountain, Nevada, produced acidic liquids and gases during the final stages of evaporation. Several simulated pore waters were prepared and then thermally distilled in order to collect and analyze fractions of the evolved vapor. In some cases, distillates collected towards the end of the distillation were highly acidic; in other cases the pH of the distillate remained comparatively unchanged during the course of the distillation. The results suggest that the pH values of the later fractions are determined by the initial composition of the water. Acid production stems from the hydrolysis of magnesium ions, especially at near dryness. Near the end of the distillation, magnesium nitrate and magnesium chloride begin to lose water of hydration, greatly accelerating their thermal decomposition to form acid. Acid formation is promoted further when precipitated calcium carbonate is removed. Specifically, calcium chloride-rich pore waters containing moderate (10–20 ppm) levels of magnesium and nitrate and low levels of bicarbonate produced mixtures of nitric and hydrochloric acid, resulting in a precipitous drop in pH to values of 1 or lower after about 95% of the original volume was distilled. Waters with either low or moderate magnesium content coupled with high levels of bicarbonate produced slightly basic fractions (pH 7–9). If calcium was present in excess of bicarbonate, waters containing moderate levels of magnesium produced acid even in the presence of bicarbonate, due to the precipitation of calcium carbonate. Other salts such as halite and anhydrite promote the segregation of acidic vapors from residual basic solids. The concomitant release of wet acid gas has implications for the integrity of the alloys under consideration for containers at the Yucca Mountain nuclear waste repository. Condensed acid gases at very low pH, especially mixtures of nitric and hydrochloric acid, are capable of corroding even alloys, such as nickel-based Alloy 22, which are considered to be corrosion-resistant under milder conditions.