Toward enhanced subsurface intervention methods using chaotic advection

Many intervention activities in the terrestrial subsurface involve the need to recover/emplace distributions of scalar quantities (e.g. dissolved phase concentrations or heat) from/in volumes of saturated porous media. These scalars can be targeted by pump-and-treat methods or by amendment technologies. Application examples include in-situ leaching for metals, recovery of dissolved contaminant plumes, or utilizing heat energy in geothermal reservoirs. While conventional pumping methods work reasonably well, costs associated with maintaining pumping schedules are high and improvements in efficiency would be welcome. In this paper we discuss how transient switching of the pressure at different wells can intimately control subsurface flow, generating a range of "programmed" flows with various beneficial characteristics. Some programs produce chaotic flows which accelerate mixing, while others create encapsulating flows which can isolate fluid zones for lengthy periods. In a simplified model of an aquifer subject to balanced pumping, chaotic flow topologies have been predicted theoretically and verified experimentally using Hele-Shaw cells. Here, a survey of the key characteristics of chaotic advection is presented. Mathematical methods are used to show how these characteristics may translate into practical situations involving regional flows and heterogeneity. The results are robust to perturbations, and withstand significant aquifer heterogeneity. It is proposed that chaotic advection may form the basis of new efficient technologies for groundwater interventions.     

Effect of topography on nitrous oxide emissions from winter wheat fields in Central France

We assessed nitrous oxide (N₂O) emissions at shoulder and foot-slope positions along three sloping sites (1.6–2.1%) to identify the factors controlling the spatial variations in emissions. The three sites received same amounts of total nitrogen (N) input at 170 kg N ha⁻¹. Results showed that landscape positions had a significant, but not consistent effect on N₂O fluxes with larger emission in the foot-slope at only one of the three sites. The effect of soil inorganic N (NH₄⁺ + NO₃⁻) contents on N₂O fluxes (r² = 0.55, p < 0.001) was influenced by water-filled pore space (WFPS). Soil N₂O fluxes were related to inorganic N at WFPS > 60% (r² = 0.81, p < 0.001), and NH₄⁺ contents at WFPS < 60% (r² = 0.40, p < 0.01), respectively. Differences in WFPS between shoulder and foot-slope correlated linearly with differences in N₂O fluxes (r² = 0.45, p < 0.001). We conclude that spatial variations in N₂O emission were regulated by the influence of hydrological processes on soil aeration intensity.     

Late 20th century mangrove encroachment in the coastal Australian monsoon tropics parallels the regional increase in woody biomass

In Kakadu National Park, a World Heritage property in the Australian monsoon tropics 250 km to the east of Darwin, a number of recent studies have shown that woody encroachment (expansion of woody communities) and densification (increased biomass in woody communities) has occurred in the last 40 years. The cause of this increase in woody biomass is poorly understood, but possibly associated with the control of invasive Asian water buffalo, trend to higher rainfall, and increased frequency of fires. Mangroves provide an important context to understand these landscape changes, given that they are unaffected by fire or feral water buffalo. We examine change in mangrove distribution in a series of coastal tropical swamps fringing Darwin, Northern Territory, Australia over a 30-year period using a series of 7 aerial photographs spanning 23 years from 1974 and a 2004 high-resolution satellite image. In late 1974, Darwin was impacted by an intense tropical cyclone. Vegetation at 3,000 randomly placed points was manually classified, and a multinomial logistic model was used to asses the impact of landscape position (coastal, intertidal, and upper-tidal) and swamp on mangrove change between 1974 and 2004. Over the study period, there was instability and slight mangrove loss at the coast, stability in the intertidal zone, and mangrove gain in the upper-tidal zone, with an overall increase in mangrove presence of 16.2% above the pre-cyclone distribution. A swamp that was impacted by drainage works for mosquito control and the construction of a sewage treatment plant showed a greater mangrove increase than the two unmodified swamps. The mangrove expansion is consistent with woody encroachment observed in nearby but ecologically distinct systems. Plausible causes for this change include changed local hydrology, changes in sea level, and elevated atmospheric CO₂ concentrations.     

Weighted road density: A simple way of assigning traffic-related air pollution exposure

BackgroundExisting traffic variables used for predicting NO₂ in epidemiological studies are either difficult to acquire or explain only a small proportion of the variance. The purpose of this study was to develop and validate a new predictor, weighted road density, which combines the maximum amount of information related to traffic into a single variable without the requirement of obtaining traffic counts for a given area.MethodTwo week NO₂ samples were collected using the readings of up to 32 passive samplers on 3 separate rounds between September and December 2006 and again in 2007. Several types of traffic related explanatory variables based on traffic counts, distance to main road and the proposed weighted road density were constructed using GIS software, and tested for association with the NO₂ samplers. Assessment of the best model was based on R² values, as well as leave-one-out cross validation.ResultsThe weighted road density variable and the density variable based on traffic counts resulted in a similar R² (0.59) for predicting NO₂, although weighted road density was much easier to construct and outperformed other variables such as distance to main road.ConclusionAs well as being a powerful predictor for use in a land use regression model, weighted road density can be used as a proxy for exposure to traffic-related pollution, for use in circumstances where direct measurements of pollutant levels are not feasible or are not required.     

Commercial bumblebee hives to assess an anthropogenic environment for pollinator support: a case study in the region of Ghent (Belgium)

Anthropogenic changes of the environment influence the distribution and abundance of pollinators such as bumblebees and have been proposed as one of the main causes in their worldwide decline. In order to evaluate the impact of expanding anthropogenic landscapes on supporting pollinator potential, reliable tools are needed. Bombus terrestris is one of the most abundant bumblebee species in Europe, and these bumblebees are known as generalist pollinators of not only wild flowers in nature but also of crops in agriculture. For more than two decades, these bumblebees have been commercially mass reared for biological pollination in greenhouses. In this project, we placed commercial hives of the bumblebee B. terrestris containing one queen and 40 workers, in three different locations in the region of Ghent (Belgium), and the performance of these hives was followed during a 4-week period in spring 2012. In parallel, we determined the floral richness and diversity index in the chosen study sites. The sites consisted of a rich urban environment with patchy green areas opposed to an urban environment with poor landscape metrics; a third rural study site showed average positive landscape metrics. The results demonstrated that the hive biomass and numbers of workers increased significantly in the rich compared to the poor environment, providing a mechanism to discriminate between study sites. In addition, the bumblebee-collected pollen showed that the flowering plants Salix spp. and Rosaceae/Prunus spp. are dominant food sources in all anthropogenic environments during early spring. Finally, the results are discussed in relation to the optimization of the experimental setup and to the use of commercial bumblebee hives in assessing local pollinator support within any given environment.     

Dietary exposure to dioxin-like compounds in three age groups: results from the Flemish environment and health study

Lipophilic contaminants are present in the environment and bioaccumulate in the food chain. Therefore, their intake via animal fat of various sources was assessed for three age groups of the Flemish population, participating in a large biomonitoring program of the Flemish government. In total, 1636 adolescents (14-15 years), 1186 mothers (18-44 years), and 1586 adults (50-65 years) participated in the study and completed a semi quantitative food frequency questionnaire. Individual consumption data were combined, via a so-called simple distribution approach, with recent data on polychlorinated dibenzo-p-dioxins/furans and dioxin-like polychlorinated biphenyls, measured via the chemical-activated luciferase gene expression (CALUX) bio-assay in food items available on the Flemish market. The median (95th percentile) estimated intakes of dioxin-like contaminants were 2.24 (4.61), 2.09 (4.26), and 1.74 (3.53) pg CALUX-TEQ kg(-1) bw d(-1) for, respectively adolescents, mothers and adults. These data are in the same range as those found in other European studies. The CALUX-TEQ results of respectively 59.8%, 53.7% and 36.2% of the adolescent, mother and adult population exceed the tolerable weekly intake (TWI) of 14 pg WHO-TEQ kg(-1) bw w(-1), as derived by the Scientific Committee on Food [Scientific Committee on Food, 2001. Opinion of the Scientific Committee on Food on the Risk Assessment of Dioxins and Dioxin-like PCBs in Food, CS/CNTM/DIOXIN/20 final Brussels, Belgium]. The main contributors of dioxin-like substances are fish and seafood (25-43% of the total intake), added fats (22-25% of the total intake) and dairy products (17-20% of the total intake).     

Hydrogeological study of an anti-tank range

The Arnhem Anti-Tank Range (Canadian Forces Base [CFB] Valcartier, Canada, in operation since the 1970s) has been characterized, including the drilling, installation, and characterization of 25 wells and a ground-penetrating radar survey. The observed particular features of this site include highly variable flow velocities (from < 3 to 1200 m/yr) and transient flow regime in the regional aquifer below the contaminant source zone of the impact area, sharp flow direction shifts, discontinuous stratigraphy and a local perched aquifer. A transient ground water flow model permitted us to understand how the complex hydrogeological setting shapes contaminant transport in the regional aquifer. The model explains the highly variable energetic material (EM) concentrations measured in the plume with peaks associated to spring and to a lesser extent to fall recharge events. As a conclusion from this work, the authors suggest that the characterization of contaminant sources on slopes should extend over all seasons to be sure to detect potential transient flow conditions and variable contaminant concentrations.     

Formation of halogenated acetaldehydes, and occurrence in Canadian drinking water

Controlled laboratory chlorination of acetaldehyde (ACD) under typical drinking water conditions (pH 6.7, 7.6 and 8.8, and temperature 4 degrees C and 21 degrees C) revealed that the formation of chloral hydrate (CH), the most common halogenated acetaldehyde (HAs), increased with contact time (0-10 days). However, at increased pH and temperature, CH reached maximum levels and subsequently broke down partially to chloroform and other unidentified compounds. After 10 days contact time, a maximum of 63% (molar) of the initial ACD consumed were converted into CH or chloroform (TCM). Various surveys of drinking water systems indicated that ACD is not the only precursor of CH. A suite of aldehydes (including ACD), and chlorinated disinfection by-products (including TCM and CH) were found in most distribution systems. The levels of bromide in source water impacted speciation of HAs. In addition to CH, brominated and other mixed (Cl/Br) acetaldehydes were detected in most samples; the speciation of HAs and THMs followed comparable trends. Similar to chloroform for trihalomethanes, CH contributed from as low as 5% to up to 60% of the total HAs. The bromine incorporation factors (BIF) in THMs and HAs were shown to increase with increasing bromide ion concentrations in the source water. Brominated THMs are more readily formed than their HA analogues; in fact, BIF values for THMs were 2-3 times higher than for the HAs. It was found that HAs may be as high as THMs in some drinking waters. As a result, the determination of the other target HAs, in addition to CH, is necessary for a better assessment of the pool of disinfection by-products in drinking water.     

Thermogravimetric desorption and de novo tests I: method development and validation

Thermogravimetric analysis (TGA) has been combined with evolved gas analysis (EGA) with the purpose of simulating the thermal behaviour of filter dust samples under inert (desorption) and de novo test oxidising conditions. Emphasis is on studying de novo formation of dioxins, surrogates and precursors arising from filter dust derived from thermal processes, such as municipal solid waste incineration and metallurgy. A new method is tested for sampling and analysing dioxin surrogates and precursors in the TGA effluent, which are collected on sampling tubes; the adsorbed compounds are eventually desorbed and quantified by TD-GC-MS. The major sources of error and losses are considered, including potential sorbent artefacts, possible breakthrough of volatiles through sampling tubes, or eventual losses of semi-volatiles due to their incomplete desorption or re-condensation inside the TG Analyser. The method is optimised and validated for di- to hexa-chlorinated benzenes in a range of 10-1000ppb with average recovery exceeding 85%. The results are compared with data obtained in similar studies, performed by other research groups. As a result, the method provides the means for simulating de novo synthesis of dioxins in fly-ash and facilitates reliable and easy estimation of de novo activity, comparable with results of other studies, in combination with wide flexibility of testing conditions.     

Surface functionalization of natural hydroxyapatite by polymerization of β-cyclodextrin: application as electrode material for the electrochemical detection of Pb(II)

Environmental Science and Pollution Research - A composite material prepared by polymerization of β-cyclodextrin (β-CD) on the surface of natural hydroxyapatite using citric acid as cross...