Atrazine distribution measured in soil and leachate following infiltration conditions

Atrazine transport through packed 10 cm soil columns representative of the 0-10 cm soil horizon was observed by measuring the atrazine recovery in the total leachate volume, and upper and lower soil layers following infiltration of 7.5 cm water using a mechanical vacuum extractor (MVE). Measured recoveries were analyzed to understand the influence of infiltration rate and delay time on atrazine transport and distribution in the column. Four time periods (0.28, 0.8, 1.8, and 5.5 h) representing very high to moderate infiltration rates (26.8, 9.4, 4.2, and 1.4 cm/h) were used. Replicate soil columns were tested immediately and following a 2-d delay after atrazine application. Results indicate atrazine recovery in leachate was independent of infiltration rate, but significantly lower for infiltration following a 2-d delay. Atrazine distribution in the 0-1 and 9-10 cm soil layers was affected by both infiltration rate and delay. These results are in contrast with previous field and laboratory studies that suggest that atrazine recovery in the leachate increases with increasing infiltration rate. It appears that the difference in atrazine recovery measured using the MVE and other leaching experiments using intact soil cores from this field site and the rain simulation equipment probably illustrates the effect of infiltrating water interacting with the atrazine present on the soil surface. This work suggests that atrazine mobilization from the soil surface is also dependent on interactions of the infiltrating water with the soil surface, in addition to the rate of infiltration through the surface soil.     

Using polymer solutions to enhance recovery of mobile coal tar and creosote DNAPLs

Direct pumping and enhanced recovery of coal tar and creosote dense, non-aqueous phase liquids (DNAPLs) from the subsurface have had mixed results because these DNAPLs are viscous fluids that can potentially alter aquifer wettability. To improve the inefficiencies associated with waterflooding, the research presented here considered the use of a polymer solution that can be added to the injected flood solution to increase the viscosity and decrease the velocity of the flooding solution. Results from one-dimensional, vertically oriented laboratory column experiments that evaluate the recovery of coal-derived DNAPL with both water and polymer flooding solutions are presented. The final DNAPL saturation remaining in the column was assessed in water and oil-wet systems for three viscous DNAPLs. Adding polymer to increase the aqueous solution viscosity did not have a significant impact in water-wet systems. A final DNAPL saturation of approximately 19% was achieved for both water and polymer floods. In contrast, the addition of polymer significantly improved recovery in oil-wet systems. The final saturation was over 40% in oil-wet systems after waterflooding, but approximately 19% with a polymer flushing solution. Although the final saturation produced with polymer flooding was similar between the oil- and water-wet systems, differences in the relative permeability and distribution of DNAPL in the porous matrix caused the DNAPL recovery to be much slower in the oil-wet system.     

Effects of temperature on mineralisation of petroleum in contaminated Antarctic terrestrial sediments

Although petroleum contamination has been identified at many Antarctic research stations, and is recognized as posing a significant threat to the Antarctic environment, full-scale in situ remediation has not yet been used in Antarctica. This is partly because it has been assumed that temperatures are too low for effective biodegradation. To test this, the effects of temperature on the hydrocarbon mineralisation rate in Antarctic terrestrial sediments were quantified. 14C-labelled octadecane was added to nutrient amended microcosms that were incubated over a range of temperatures between -2 and 42 degrees C. We found a positive correlation between temperature and mineralisation rate, with the fastest rates occurring in samples incubated at the highest temperatures. At temperatures below or near the freezing point of water there was a virtual absence of mineralisation. High temperatures (37 and 42 degrees C) and the temperatures just above the freezing point of water (4 degrees C) showed an initial mineralisation lag period, then a sharp increase in the mineralisation rate before a protracted plateau phase. Mineralisation at temperatures between 10 and 28 degrees C had no initial lag phase. The high rate of mineralisation at 37 and 42 degrees C was surprising, as most continental Antarctic microorganisms described thus far have an optimal temperature for growth of between 20 and 30 degrees C and a maximal growth temperature <37 degrees C. The main implications for bioremediation in Antarctica from this study are that a high-temperature treatment would yield the most rapid biodegradation of the contaminant. However, in situ biodegradation using nutrients and other amendments is still possible at soil temperatures that occur naturally in summer at the Antarctic site we studies (Casey Station 66 degrees 17(') S, 110 degrees 32(') E), although treatment times could be excessively long.     

Evaluation of synchrotron X-ray computerized microtomography for the visualization of transport processes in low-porosity materials

Synchrotron-source X-ray computerized microtomography (CMT) is evaluated as a method to visualize transport processes. We conclude that CMT is adequate for visualization of transport experiments if the right conditions exist. Namely, 1) not much more than one-order-of-magnitude range in concentration data is needed for the study, 2) the pore space in the samples are greater than approximately 2--50 mum, depending on the sample size and system setup; 3) the sample is fine-grained enough so that a representative elemental volume (REV) can be contained by a 2--10 mm diameter sample, and 4) the transport process is slow enough that significant changes do not occur within the 25--50 min (and possibly less in the future) needed to collect data for one three-dimensional image. Absorption edge difference imaging (AEDI) in association with CMT is introduced as a method to enhance pore-space visualization. We successfully imaged the pore space in a low-porosity granodiorite, diorite and fine-grained granite cores and a higher-porosity soil aggregate sample. We found that the pore space important to transport in the core samples was smaller than what we were able to visualize with CMT. We also made rudimentary associations of minerals with pore-space location.     

Efficacy of in-situ for the remediation of PAH contaminated soils

Polycyclic aromatic hydrocarbons (PAHs) are of environmental concern because many PAHs are either carcinogens or potential carcinogens. Petroleum products are a major source of PAHs. The occurrence of PAH contamination is widespread and novel treatment technologies for the remediation of contaminated soils are necessary.Ozone has been found to be extremely useful for the degradation of PAHs in soils. For these compounds, the reaction with molecular ozone appears to be the more important degradation pathway. Greater than 95% removal of phenanthrene was achieved with an ozonation time of 2.3 h at an ozone flux of 250 mg h⁻¹. After 4.0 h of treatment at an ozone flux of 600 mg h⁻¹, 91 % of the pyrene was removed. We have also found that the more hydrophobic PAHs (e.g. chrysene) react more slowly than would be expected on the basis of their reactivity with ozone, suggesting that partitioning of the contaminant into soil organic matter may reduce the reactivity of the compound. Even so, after 4 h of exposure to ozone, the chrysene concentration in a contaminated Metea soil was reduced from 100 to 50 mg kg⁻¹ .Ozone has been found to be readily transported through columns packed with a number of geological materials, including Ottawa sand, Metea soil, Borden aquifer material and Wurtsmith aquifer material. All of these geological materials exerted a limited (finite) ozone demand, i.e. the rate of ozone degradation in soil columns is very slow after the ozone demand is met. Moisture content was found to increase the ozone demand, most likely owing to the dissolution of gaseous ozone into the pore water. As once the initial ozone demand is met, little degradation of ozone is observed, it should be possible to achieve ozone penetration to a considerable distance away from the injection well, suggesting that in-situ ozonation is a feasible means of treating uncontaminated unsaturated soils. This is substantiated by two field studies where in-situ ozonation was apparently successful at remediating the sites.     

Spring bloom sedimentation in a subarctic ecosystem

A 5-yr study (1985 to 1989) of spring bloom sedimentation in Auke Bay, Alaska, indicates that the sinking response of diatoms to ambient nutrients influences both species succession during the spring bloom and the subsequent sedimentation of new production. Diatoms from the genera Thalassiosira, Chaetoceros and Skeletonema formed the bulk of the spring bloom each year. Growth of Thalassiosira spp. consistently initiated the primary bloom, while Skeletonema costatum tended to grow later in, or after, the primary bloom. We postulate that this successional pattern is driven by interspecific nutrient competition. Overall, sedimentation flux of the dominant species of bloom diatoms was correlated with surface concentrations of cells integrated over the bloom period. In fact, different linear relationships existed when Thalassiosira and Chaetoceros spp. were considered separately, but not for Skeletonema sp., indicating that marked differences exist between the sedimentation tendencies of these genera. The observed inter-generic differences are explicable by the different overall sinking rates, as well as different nutrient-sensitivities of the sinking rates of each genus. Thalassiosira spp., the fastestsinking and most nutrient-sensitive species, contributed up to 10 x more carbon to the benthos in all years of the study, reaching a maximum of 11.1 gCm^-2 over a single spring bloom event in 1988. This study indicates that the tendency to sink to the benthos during and/or after a bloom is highly dependent on species-specific cell physiology, and supports the idea that it is the fast-sinking, nutrient-sensitive diatoms, such as Thalassiosira species, that constitute the major source of vertical carbon flux in this embayment and other such coastal ecosystems during the spring bloom.     

Contaminants of food

A scheme has been developed to rank 70 industrial organic chemicals in order of their priority for further study as potential contaminants of food. Numerical scales were developed for the following seven key criteria concerning environmental issues, food and toxicity:

-Production volume

-Pattern of usage

-Possible fate in the environment

-Likelihood of chemical entering the food chain

-Mechanism of entry into the food chain

-Persistence and accumulation in the food chain

-Toxicity.

Each chemical was assigned a score for the above criteria, which were combined to give an overall ranking for the chemicals. This scheme has been endorsed by the MAFF Steering Group on Chemical Aspects of Food Surveillance. It will be used in the assessment of relative priorities for further non-statutory surveillance for these contaminants in the UK food supply.     

TNT particle size distributions from detonated 155-mm howitzer rounds

To achieve sustainable range management and avoid or minimize environmental contamination, the Army needs to know the amount of explosives deposited on ranges from different munitions and how these are degraded and transported under different geological and climatic conditions. The physical form of the deposited explosives has a bearing on this problem, yet the shapes and size distributions of the explosive particles remaining after detonations are not known. We collected residues from 8 high-order and 6 low-order non-tactical detonations of TNT-filled 155-mm rounds. We found significant variation in the amount of TNT scattered from the high-order detonations, ranging from 0.00001 to 2% of the TNT in the original shell. All low-order detonations scattered percent-level amounts of TNT. We imaged thousands of TNT particles and determined the size, mass and surface-area distributions of particles collected from one high-order and one low-order detonation. For the high-order detonation, particles smaller than 1 mm contribute most of the mass and surface area of the TNT scattered. For the low-order detonation, most of the scattered TNT mass was in the form of un-heated, centimeter-sized pieces whereas most of the surface area was again from particles smaller than 1 mm. We also observed that the large pieces of TNT disintegrate readily, giving rise to many smaller particles that can quickly dissolve. We suggest picking up the large pieces of TNT before they disintegrate to become point sources of contamination.     

Odours from pulp mill effluent treatment ponds: the origin of significant levels of geosmin and 2-methylisoborneol (MIB)

Pulp and paper mills are well known for their sharp, sulphurous stack emissions, but the secondary treatment units also can be significant contributors to local odour. This study investigated the source(s) of earthy/musty emissions from a mixed hardwood pulp mill in response to a high local odour. Samples from five sites in the mill over five months were analyzed for earthy/musty volatile organic compounds (VOCs), examined microscopically, and plated for bacteria and moulds. In all cases, activated sludge showed substantial geosmin levels and to a lesser extent 2-methylisoborneol (MIB) at 2000-9000 times their odour threshold concentrations (OTCs). These VOCs were lower or absent upstream and downstream, suggesting that they were produced within the bioreactor. Geosmin and MIB were highest in late summer and declined over winter, and correlated with different operating parameters. Geosmin was most closely coupled with temperature and MIB with nitrogen uptake. Cyanobacteria were present in all sludge samples, but actinomycetes were not found. Gram-negative bacteria and one fungal species isolated from the bioreactor and secondary outfall tested negative for geosmin or MIB. We conclude: (i) geosmin and MIB contribute significantly to airborne odours from this mill, but are diluted below OTC levels at the river; (ii) these VOCs are generated by biota in the activated sludge; and (iii) cyanobacteria are likely primary source(s). The growth of cyanobacteria in activated sludge represents a loss of energy to the heterotrophic population; thus earthy/musty odours may represent a diagnostic for less than optimal conditions.     

Estimation of the net air-sea flux of ammonia over the southern bight of the North Sea

Measurements of airborne gaseous ammonia and total dissolved ammonium in sea water determined on cruises on the North Sea have been used to calculate net fluxes of ammonia between air and sea. The system is finely balanced with the majority of net fluxes from air to sea, but some periods occur when the sea becomes a net source of ammonia in air. Examination of the field data suggests that the main factor determining the direction of flux is the airborne ammonia concentration, which when elevated causes ammonia deposition to the sea. It is calculated that ammonia deposition to the southern bight of the North Sea (below 56°N) amounts to 7.6 x 103 tonnes N per year, about one-half of an earlier upper limit estimate. Comparison with studies from the Pacific Ocean, in which the sea acts as a source of atmospheric ammonia, reveals that the major differences arise from much higher concentrations of airborne ammonia in the North Sea atmosphere caused by advection from adjacent land.