Estimating contaminant mass discharge: a field comparison of the multilevel point measurement and the integral pumping investigation approaches and their uncertainties

In this field study, two approaches to assess contaminant mass discharge were compared: the sampling of multilevel wells (MLS) and the integral groundwater investigation (or integral pumping test, IPT) that makes use of the concentration-time series obtained from pumping wells. The MLS approached used concentrations, hydraulic conductivity and gradient rather than direct chemical flux measurements, while the IPT made use of a simplified analytical inversion. The two approaches were applied at a control plane located approximately 40m downgradient of a gasoline source at Canadian Forces Base Borden, Ontario, Canada. The methods yielded similar estimates of the mass discharging across the control plane. The sources of uncertainties in the mass discharge in each approach were evaluated, including the uncertainties inherent in the underlying assumptions and procedures. The maximum uncertainty of the MLS method was about 67%, and about 28% for the IPT method in this specific field situation. For the MLS method, the largest relative uncertainty (62%) was attributed to the limited sampling density (0.63 points/m(2)), through a novel comparison with a denser sampling grid nearby. A five-fold increase of the sampling grid density would have been required to reduce the overall relative uncertainty for the MLS method to about the same level as that for the IPT method. Uncertainty in the complete coverage of the control plane provided the largest relative uncertainty (37%) in the IPT method. While MLS or IPT methods to assess contaminant mass discharge are attractive assessment tools, the large relative uncertainty in either method found for this reasonable well monitored and simple aquifer suggests that results in more complex plumes in more heterogeneous aquifers should be viewed with caution.     

Hydrogen peroxide stabilization in one-dimensional flow columns

Rapid hydrogen peroxide decomposition is the primary limitation of catalyzed H(2)O(2) propagations in situ chemical oxidation (CHP ISCO) remediation of the subsurface. Two stabilizers of hydrogen peroxide, citrate and phytate, were investigated for their effectiveness in one-dimensional columns of iron oxide-coated and manganese oxide-coated sand. Hydrogen peroxide (5%) with and without 25 mM citrate or phytate was applied to the columns and samples were collected at 8 ports spaced 13 cm apart. Citrate was not an effective stabilizer for hydrogen peroxide in iron-coated sand; however, phytate was highly effective, increasing hydrogen peroxide residuals two orders of magnitude over unstabilized hydrogen peroxide. Both citrate and phytate were effective stabilizers for manganese-coated sand, increasing hydrogen peroxide residuals by four-fold over unstabilized hydrogen peroxide. Phytate and citrate did not degrade and were not retarded in the sand columns; furthermore, the addition of the stabilizers increased column flow rates relative to unstabilized columns. These results demonstrate that citrate and phytate are effective stabilizers of hydrogen peroxide under the dynamic conditions of one-dimensional columns, and suggest that citrate and phytate can be added to hydrogen peroxide before injection to the subsurface as an effective means for increasing the radius of influence of CHP ISCO.     

Partitioning of metals in a degraded acid sulfate soil landscape: influence of tidal re-inundation

The oxidation and acidification of sulfidic soil materials results in the re-partitioning of metals, generally to more mobile forms. In this study, we examine the partitioning of Fe, Cr, Cu, Mn, Ni and Zn in the acidified surface soil (0-0.1 m) and the unoxidised sub-soil materials (1.3-1.5 m) of an acid sulfate soil landscape. Metal partitioning at this acidic site was then compared to an adjacent site that was previously acidified, but has since been remediated by tidal re-inundation. Differences in metal partitioning were determined using an optimised six-step sequential extraction procedure which targets the “labile”, “acid-soluble”, “organic”, “crystalline oxide”, “pyritic” and “residual” fractions. The surficial soil materials of the acidic site had experienced considerable losses of Cr, Cu, Mn and Ni compared to the underlying parent material due to oxidation and acidification, yet only minor losses of Fe and Zn. In general, the metals most depleted from the acidified surface soil materials exhibited the greatest sequestration in the surface soil materials of the tidally remediated site. An exception to this was iron, which accumulated to highly elevated concentrations in the surficial soil materials of the tidally remediated site. The “acid-soluble”, “organic” and “pyritic” fractions displayed the greatest increase in metals following tidal remediation. This study demonstrates that prolonged tidal re-inundation of severely acidified acid sulfate soil landscapes leads to the immobilisation of trace metals through the surficial accumulation of iron oxides, organic material and pyrite.     

Cobalt-induced oxidative stress in brain, liver and kidney of goldfish Carassius auratus

Cobalt is an essential element, but at high concentrations it is toxic. In addition to its well-known function as an integral part of cobalamin (vitamin B₁₂), cobalt has recently been shown to be a mimetic of hypoxia and a stimulator of the production of reactive oxygen species. The present study investigated the responses of goldfish, Carassius auratus, to 96 h exposure to 50, 100 or 150 mg L⁻¹ Co²⁺ in aquarium water (administered as CoCl₂). The concentrations of cobalt in aquaria did not change during fish exposure. Exposure to cobalt resulted in increased levels of lipid peroxides in brain (a 111% increase after exposure to 150 mg L⁻¹ Co²⁺) and liver (30-66% increases after exposure to 50-150 mg L⁻¹ Co²⁺), whereas the content of protein carbonyls rose only in kidney (by 112%) after exposure to 150 mg L⁻¹ cobalt. Low molecular mass thiols were depleted by 24-41% in brain in response to cobalt treatment. The activities of primary antioxidant enzymes, superoxide dismutase (SOD) and catalase, were substantially suppressed in brain and liver as a result of Co²⁺ exposure, whereas in kidney catalase activity was unchanged and SOD activity increased. The activities of glutathione-related enzymes, glutathione peroxidase and glutathione-S-transferase, did not change as a result of cobalt exposure, but glutathione reductase activity increased by ∼40% and ∼70% in brain and kidney, respectively. Taken together, these data show that exposure of fish to Co²⁺ ions results in the development of oxidative stress and the activation of defense systems in different goldfish tissues.     

Ecotoxicity evaluation of selected sulfonamides

Sulfonamides (SAs) are a group of antibiotic drugs widely used in veterinary medicine. The contamination of the environment by these pharmaceuticals has raised concern in recent years. However, knowledge of their (eco)toxicity is still very basic and is restricted to just a few of these substances. Even though their toxicological analysis has been thoroughly performed and ecotoxicological data are available in the literature, a systematic analysis of their ecotoxicological potential has yet to be carried out. To fill this gap, 12 different SAs were chosen for detailed analysis with the focus on different bacteria as well as non-target organisms (algae and plants). A flexible (eco)toxicological test battery was used, including enzymes (acetylcholinesterase and glutathione reductase), luminescent marine bacteria (Vibrio fischeri), soil bacteria (Arthrobacter globiformis), limnic unicellular green algae (Scenedesmus vacuolatus) and duckweed (Lemna minor), in order to take into account both the aquatic and terrestrial compartments of the environment, as well as different trophic levels. It was found that SAs are not only toxic towards green algae (EC₅₀ = 1.54-32.25 mg L⁻¹) but have even stronger adverse effect on duckweed (EC₅₀ = 0.02-4.89 mg L⁻¹) than atrazine - herbicide (EC₅₀ = 2.59 mg L⁻¹).     

Determination of 2,4- and 2,6-dinitrotoluene biodegradation limits

This study was carried out to explore the lowest achievable dinitrotoluene (DNT) isomer concentrations that would support sustained growth of DNT degrading microorganisms under an aerobic condition. Studies were conducted using suspended (chemostat) and attached growth (column) systems. The biodegradation limits for 2,4-dinitrotoluene chemostat and column system were 0.054 ± 0.005 and 0.057 ± 0.008 μM, respectively, and for 2,6-dinitrotoluene, the limits for chemostat and column system were 0.039 ± 0.005 and 0.026 ± 0.013 μM, respectively. The biodegradation limits determined in this study are much lower than the regulatory requirements, inferring that bacterial ability to metabolize DNT does not preclude applications of bioremediation (including natural attenuation) for DNT contaminated media.     

Assessing seasonal and spatial trends of persistent organic pollutants (POPs) in Indian agricultural regions using PUF disk passive air samplers

The first survey of persistent organic pollutant (POP) concentrations in air across several Indian agricultural regions was conducted in 2006-2007. Passive samplers comprising polyurethane foam (PUF) disks were deployed on a quarterly basis at seven stations in agricultural regions, one urban site and one background site. The project was conducted as a sub-project of the Global Atmospheric Passive Sampling (GAPS) Network. In addition to revealing new information on air concentrations of several organochlorine pesticides (OCPs) and polychlorinated biphenyls (PCBs), the study has demonstrated the feasibility of conducting regional-scale monitoring for POPs in India using PUF disk samplers. The following analytes were detected with relatively high concentrations in air (mean for 2006 and 2007, pg/m³): α- and γ-hexachlorocyclohexane (HCH) (292 and 812, respectively); endosulfan I and II (2770 and 902, respectively); p,p′-DDE and p,p′-DDT (247 and 931, respectively); and for the sum of 48 PCBs, 12,100 (including a site with extremely high air concentrations in 2007) and 972 (when excluding data for this site).     

Cocaine and other illicit drugs in airborne particulates in urban environments: a reflection of social conduct and population size

Levels of cocaine and other psychoactive substances in atmospheric particulate matter (PM) were determined in urban environments representing distinct social behaviours with regard to drug abuse: night-life, university and residential areas. Three cities (with population >1 million and <0.3 million inhabitants) were selected. Mean daily levels of drugs in PM were 11-336 pg/m³ for cocaine, 23-34 pg/m³ for cannabinoids, and 5-90 pg/m³ for heroin. The highest levels were recorded on weekends, with factors with respect to weekdays of 1-3 for cocaine, 1-2 for cannabinoids and 1.1-1.7 for heroin. Higher levels were detected in the night-life areas, pointing towards consumption and trafficking as major emission sources, and possibly ruling out drug manufacture. The similarities in temporal trends at all sites suggested a city-scale transport of psychoactive substances. Correlations were detected between cocaine and amphetamine consumption (r² = 0.98), and between heroin and cannabinoids (r²>0.82).     

Reproduction and biochemical responses in Enchytraeus albidus (Oligochaeta) to zinc or cadmium exposures

To better understand chemical modes of action, emphasis has been given to stress responses at lower levels of biological organization. Cholinesterases and antioxidant defenses are among the most used biomarkers due to their crucial role in the neurocholinergic transmission and in cell homeostasis preventing DNA damage, enzymatic inactivation and lipid peroxidation. The main goal of this study was to investigate the effects of zinc and cadmium on survival and reproduction of E. albidus and to assess metals oxidative stress potential and neurotoxic effects at concentrations that affected reproduction. Both metals affected the enchytraeids’ survival and reproduction and induced significant changes in the antioxidant defenses as well as increased lipid peroxidation, indicating oxidative damage. This study demonstrates that determining effects at different levels of biological organization can give better information on the physiological responses of enchytraeids in metal contamination events and further unravel the mechanistic processes dealing with metal stress.     

Growth of soybean at future tropospheric ozone concentrations decreases canopy evapotranspiration and soil water depletion

Tropospheric ozone is increasing in many agricultural regions resulting in decreased stomatal conductance and overall biomass of sensitive crop species. These physiological effects of ozone forecast changes in evapotranspiration and thus in the terrestrial hydrological cycle, particularly in intercontinental interiors. Soybean plots were fumigated with ozone to achieve concentrations above ambient levels over five growing seasons in open-air field conditions. Mean season increases in ozone concentrations ([O₃]) varied between growing seasons from 22 to 37% above background concentrations. The objective of this experiment was to examine the effects of future [O₃] on crop ecosystem energy fluxes and water use. Elevated [O₃] caused decreases in canopy evapotranspiration resulting in decreased water use by as much as 15% in high ozone years and decreased soil water removal. In addition, ozone treatment resulted in increased sensible heat flux in all years indicative of day-time increase in canopy temperature of up to 0.7 °C.