A PCE groundwater plume discharging to a river: influence of the streambed and near-river zone on contaminant distributions

An investigation of a tetrachloroethene (PCE) groundwater plume originating at a dry cleaning facility on a sand aquifer and discharging to a river showed that the near-river zone strongly modified the distribution, concentration, and composition of the plume prior to discharging into the surface water. The plume, streambed concentration, and hydrogeology were extensively characterized using the Waterloo profiler, mini-profiler, conventional and driveable multilevel samplers (MLS), Ground Penetrating Radar (GPR) surveys, streambed temperature mapping (to identify discharge zones), drivepoint piezometers, and soil coring and testing. The plume observed in the shallow streambed deposits was significantly different from what would have been predicted based on the characteristics of the upgradient plume. Spatial and temporal variations in the plume entering the near-river zone contributed to the complex contaminant distribution observed in the streambed where concentrations varied by factors of 100 to 5000 over lateral distances of less than 1 to 3.5 m. Low hydraulic conductivity semi-confining deposits and geological heterogeneities at depth below the streambed controlled the pattern of groundwater discharge through the streambed and influenced where the plume discharged into the river (even causing the plume to spread out over the full width of the streambed at some locations). The most important effect of the near-river zone on the plume was the extensive anaerobic biodegradation that occurred in the top 2.5 m of the streambed, even though essentially no biodegradation of the PCE plume was observed in the upgradient aquifer. Approximately 54% of the area of the plume in the streambed consisted solely of PCE transformation products, primarily cis-1,2-dichloroethene (cDCE) and vinyl chloride (VC). High concentrations in the interstitial water of the streambed did not correspond to high groundwater-discharge zones, but instead occurred in low discharge zones and are likely sorbed or retarded remnants of past high-concentration plume discharges. The high-concentration areas (up to 5529 microg/l of total volatile organics) in the streambed are of ecological concern and represent potential adverse exposure locations for benthic and hyporheic zone aquatic life, but the effect of these exposures on the overall health of the river has yet to be determined. Even if the upgradient source of PCE is remediated and additional PCE is prevented from reaching the streambed, the high-concentration deposits in the streambed will likely take decades to hundreds of years to flush completely clean under natural conditions because these areas have low vertical groundwater flow velocities and high retardation factors. Despite high concentrations of contaminants in the streambed, PCE was detected in the surface water only rarely due to rapid dilution in the river and no cDCE or VC was detected. Neither the sampling of surface water nor the sampling of the groundwater from the aquifer immediately adjacent to the river gave an accurate indication of the high concentrations of PCE biodegradation products present in the streambed. Sampling of the interstitial water of the shallow streambed deposits is necessary to accurately characterize the nature of plumes discharging to rivers.     

Effects of bis(tributyltin)oxide on antipredator behavior in threespine stickleback Gasterosteus aculeatus L.

Antipredator behavior was used as a parameter to detect effects caused by exposure to the organotin compound bis(tributyltin)oxide (TBTO). Three groups of threespine sticklebacks (Gasterosteus aculeatus L.) were exposed to 3, 9 and 27 ppb TBTO, respectively. A fourth control group was given the same treatment as the other three groups, but no TBTO. Antipredator behavior of the fish was evoked using a dummy heron (Ardea cinerea) bill. TBTO exposure caused significant changes in the spatial position of the fish in the aquarium (P(Loc)), their response to predator attack (P(Res)), recovery time (P(Rec)) and latency time (P(Lat)). Some of the effects were, however, reversible after the exposure was terminated. We suggest that behavior as an indicator of pollution may be used as an ecologically relevant integrative biomarker.     

Framing the Long-Term <Emphasis Type="Italic">In Situ</Emphasis> Liability Issue for Geologic Carbon Storage in the United States

This paper examines how legal standards of liability may apply to geologic carbon storage. The liability regime governing geologic carbon storage will shape the technology's cost-effectiveness and overall attractiveness. We classify potential sources of liability into operational, in situ, and climate liability. As a first step, we explore in situ liability in the United States. After summarizing legal standards of liability including negligence, breach of implied warranty, strict liability, and product liability, we discuss how liability may be addressed at the level of the federal government, state government, industry, and the firm. Finally, we address the implications of judicial treatment of liability for carbon storage, including the apportionment of liability and the adequacy of current regulations.     

Major and trace elements of selected pedons in the USA

Few studies of soil geochemistry over large geographic areas exist, especially studies encompassing data from major pedogenic horizons that evaluate both native concentrations of elements and anthropogenically contaminated soils. In this study, pedons (n = 486) were analyzed for trace (Cd, Co, Cr, Cu, Hg, Mn, Ni, Pb, Zn) and major (Al, Ca, Fe, K, Mg, Na, P, Si, Ti, Zr) elements, as well as other soil properties. The objectives were to (i) determine the concentration range of selected elements in a variety of U.S. soils with and without known anthropogenic additions, (ii) illustrate the association of elemental source and content by assessing trace elemental content for several selected pedons, and (iii) evaluate relationships among and between elements and other soil properties. Trace element concentrations in the non-anthropogenic dataset (NAD) were in the order Mn > (Zn, Cr, Ni, Cu) > (Pb, Co) > (Cd, Hg), with greatest mean total concentrations for the Andisol order. Geometric means by horizon indicate that trace elements are concentrated in surface and/or B horizons over C horizons. Median values for trace elements are significantly higher in surface horizons of the anthropogenic dataset (AD) over the NAD. Total Al, Fe, cation exchange capacity (CEC), organic C, pH, and clay exhibit significant correlations (0.56, 0.74, 0.50, 0.31, 0.16, and 0.30, respectively) with total trace element concentrations of all horizons of the NAD. Manganese shows the best inter-element correlation (0.33) with these associated total concentrations. Total Fe has one of the strongest relationships, explaining 55 and 30% of the variation in total trace element concentrations for all horizons in the NAD and AD, respectively.     

Estimation of odor emission rate from landfill areas using the sniffing team method

The monitoring of the odor annoyance generated by a landfill area is difficult, since it is a multi-area-sources problem, with a discontinuous odor emission. This paper proposes an adaptation of the method of sniffing team campaigns to the particular case of fresh waste odors. The method is based on the field determination of odor perception points, followed by data processing with a bi-Gaussian-type model, adapted to handle the odors. In a first step, field observers delineate the region in which odor impact is experienced and then the emission rate is manipulated in a dispersion model until the predicted size of the impact zone matches that observed in the field. In a second step the adjusted emission rate is entered into the model to calculate the percentiles corresponding to the average annoyance zone. The originality of the proposed method is the introduction of all observation points and of all recorded meteorological data into the model. The paper discusses the method limitations and the errors induced on the results, i.e. the odor emission rate and the percentile lines (or iso-concentration lines) which are used to describe the odor concentrations on a map of the surroundings of the plant. The proposed method proves to be reliable for diffuse sources, such as landfill areas. The obtained results are coherent with other results found in the literature with other techniques.     

An environmental threshold for degree of phosphorus saturation in sandy soils

There is critical need for a practical indicator to assess the potential for phosphorus (P) movement from a given site to surface waters, either via surface runoff or subsurface drainage. The degree of phosphorus saturation (DPS), which relates a measure of P already adsorbed by a soil to its P adsorption capacity, could be a good indicator of that soil's P release capability. Our primary objective was to find a suitable analytical protocol for determining DPS and to examine the possibility of defining a threshold DPS value for Florida's sandy soils. Four farmer-owned dairy sprayfields were selected within the Suwannee River basin and soil profiles were randomly obtained from each site, as well as from adjacent unimpacted sites. The soil samples were divided either by horizon or depth, and DPS was determined for each soil sample using ammonium-oxalate (DPS(Ox)), Mehlich-1 (DPS(M1)), and Mehlich-3 (DPS(M3)) extracts. All methods of DPS calculations were linearly related to one another (r2 > 0.94). Relationships between water-soluble P and DPS indicate that the respective change points are: DPS(Ox) = 20%, DPS(M1) = 20%, and DPS(M3) = 16%. These relationships include samples from Ap, E, and Bt horizons, and various combinations thereof, suggesting that DPS values can be used as predictors of P loss from a soil irrespective of the depth of the soil within a profile. Taking into consideration the change points, confidence intervals, agronomic soil test values, and DPS values from other studies, we suggest replacing Mehlich-1 P values in the Florida P Index with the three DPS categories (DPS(M1) = <30, 30-60, and >60%) to assign different P loss ratings in the P Index.     

Influence of water treatment residuals on phosphorus solubility and leaching

Laboratory and greenhouse studies compared the ability of water treatment residuals (WTRs) to alter P solubility and leaching in Immokalee sandy soil (sandy, siliceous, hyperthermic Arenic Alaquod) amended with biosolids and triple superphosphate (TSP). Aluminum sulfate (Al-WTR) and ferric sulfate (Fe-WTR) coagulation residuals, a lime softening residual (Ca-WTR) produced during hardness removal, and pure hematite were examined. In equilibration studies, the ability to reduce soluble P followed the order Al-WTR > Ca-WTR = Fe-WTR > hematite. Differences in the P-fixing capacity of the sesquioxide-dominated materials (Al-WTR, Fe-WTR, hematite) were attributed to their varying reactive Fe- and Al-hydrous oxide contents as measured by oxalate extraction. Leachate P was monitored from greenhouse columns where bahiagrass (Paspalum notatum Flugge) was grown on Immokalee soil amended with biosolids or TSP at an equivalent rate of 224 kg P ha(-1) and WTRs at 2.5% (56 Mg ha(-1)). In the absence of WTRs, 21% of TSP and 11% of Largo cake biosolids total phosphorus (PT) leached over 4 mo. With co-applied WTRs, losses from TSP columns were reduced to 3.5% (Fe-WTR), 2.5% (Ca-WTR), and <1% (Al-WTR) of applied P. For the Largo biosolids treatments all WTRs retarded downward P flux such that leachate P was not statistically different than for control (soil only) columns. The phosphorus saturation index (PSI = [Pox]/ [Al(ox) + Fe(ox)], where Pox, Al, and Fe(ox) are oxalate-extractable P, Al, and Fe, respectively) based on a simple oxalate extraction of the WTR and biosolids is potentially useful for determining WTR application rates for controlled reduction of P in drainage when biosolids are applied to low P-sorbing soils.     

Concentration and chemical speciation for the determination of Cu,Zn, Ni,Pb and Cd from refuse dump soils using the optimized BCR sequential extraction procedure

The optimized BCR sequential extraction procedure (proposed by the Standards, Measurements and Testing Programme (SM&T) of the European Union) was applied to seven topsoil samples from refuse dump sites for the determination of Cu, Zn, Ni, Pb and Cd. The metals were partitioned into four operationally defined chemical fractions: acid extractable, reducible, oxidizable and residual, and analysed using flame atomic absorption spectrophotometry, FAAS. The results were compared with total metal concentrations obtained using HNO₃, HClO₄ and HF digestion procedures. Results for total metal analysis ranged from - 15.55 to 43.45 for Cu, 37.15 to 222.35 for Zn, 5.15 to 12.10 for Ni, 10.30 to 93.05 for Pb and 0.35 to 3.75 for Cd in μgg⁻¹ dry weight. The results of the partitioning study showed that zinc prevailed in the more soluble fractions and was distributed between the acid-extractable (32.4%) and the reducible (40.3%) fractions, whereas Pb was distributed mainly in the reducible fraction. Copper and nickel were predominantly associated with the reducible and residual fractions - 53.4, 33.3 and 51.1, 24.1% respectively. The ranking of the four fractions for the partitioning of cadmium was: reducible > residual > oxidizable > acid extractable. The percentage recovery for all metals when comparing total metal concentration with the fractional sum of the optimized BCR procedure, were of the order: Zn(93%) > Pb(83%) > Cu(78) > Cd > (68%) > Ni(63%).