Non-reactive solute diffusion in unconfined and confined specimens of a compacted soil

The effect of specimen confinement on the determination of the effective diffusion coefficients, D*, for chloride, a non-reactive (non-adsorbing) solute, diffusing in a compacted soil was evaluated. The diffusion tests were performed by placing an acetic acid/sodium acetate buffer solution containing ZnCl2 (pH approximately 4.8) in a reservoir in contact with unconfined and confined specimens of a compacted sand-clay mixture for test durations of 7 or 14 d. The concentrations of chloride in the reservoir were measured as a function of time during the test, as well as a function of depth within the specimen at the end of the test. The resulting concentration distributions were analyzed using two models to Fick's second law for non-reactive solute diffusion in porous media, viz., (1) an analytical model assuming the porosity distribution could be represented by a single, weighted mean porosity and (2) a commercially available model, POLLUTE, that directly accounted for the measured porosity distribution. The D* for unconfined specimens based on the analytical model tended to be overestimated by a factor ranging from 1.13 to 1.59 relative to the D* using POLLUTE, whereas the D* values based on both methods for confined specimens typically were more consistent. In addition, the D* for unconfined specimens was greater than the D* for confined specimens when soil concentrations were used for the analysis, presumably due to the higher porosity for the unconfined specimens relative to the confined specimens. Analyses based on reservoir concentrations were inconsistent and contradictory in some cases, suggesting that the D* values based on soil concentrations were more reliable.     

Evaluation of simplified mass transfer models to simulate the impacts of source zone architecture on nonaqueous phase liquid dissolution in heterogeneous porous media

Nonaqueous phase liquid (NAPL) dissolution was studied in three-dimensional (3D) heterogeneous experimental aquifers (25.5 cm x 9 cm x 8.5 cm) with two different longitudinal correlation lengths (2.1 cm and 1.1 cm) and initial spill volumes (22.5 ml and 10.5 ml). Spatial and temporal distributions of NAPL during dissolution were measured using magnetic resonance imaging (MRI). At high NAPL spill volume, average effluent concentrations initially increased during dissolution, as NAPL pools transitioned to NAPL ganglia, and then decreased as the total NAPL-water interfacial area decreased over time. Experimental results were used to test six dissolution models: (i and ii) a one-dimensional (1D) model using either specific NAPL-water interfacial area values estimated from MR images at each time step (i.e., 1D quasi-steady state model), or an empirical mass transfer (Sh') correlation (i.e., 1D transient model), (iii and iv) a multiple analytical source superposition technique (MASST) using either the NAPL distribution determined from MR images at each time step (i.e., MASST steady state model), or the NAPL distribution determined from mass balance calculations (i.e., MASST transient model), (v) an equilibrium streamtube model, and (vi) a 3D grid-scale pool dissolution model (PDM) with a dispersive mass flux term. The 1D quasi-steady state model and 3D PDM captured effluent concentration values most closely, including some concentration fluctuations due to changes in the extent of flow reduction. The 1D transient, MASST steady state and transient, and streamtube models all showed a monotonic decrease in effluent concentration values over time, and the streamtube model was the most computationally efficient. Changes during dissolution of the effective NAPL-water interfacial area estimated from imaging data are similar to changes in effluent concentration values. The 1D steady state model incorporates estimates of the effective NAPL-water interfacial area directly at each time point; the 3D PDM does so indirectly through mass balance and a relative permeability function, which causes reduced water flow through high saturation NAPL regions. Hence, when model accuracy is required, the results indicate that a surrogate of this effective interfacial area is required. Approaches to include this surrogate in the MASST and streamtube models are recommended.     

Using trace element concentrations in Corbicula fluminea to identify potential sources of contamination in an urban river

We used the biomonitor, Corbicula fluminea, to investigate the contributions of trace elements associated with different point sources and land uses in a large river. Trace elements were analyzed in tissues of clams collected from 15 tributary streams draining five land use or point source types: agriculture, forest, urban, coal-fired power plant (CFPP), and wastewater (WWTP). Clams from forested catchments had elevated Hg concentrations, and concentrations of arsenic and selenium were highest (5.0+/-0.2 and 13.6+/-0.9 microg g(-1) dry mass (DM), respectively) in clams from CFPP sites. Cadmium concentrations were significantly higher in clams from urban and CFPP sites (4.1+/-0.2 and 3.6+/-0.9 microg g(-1) DM, respectively). Non-metric multidimensional scaling (NMS) of tissue concentrations in clams clustered at CFPP and forest/agriculture sites at opposite ends of the ordination space, and the distribution of sites was driven by Cu, Zn, Cd, and Hg.     

Seasonal variation of heavy metals in ambient air and precipitation at a single site in Washington, DC

Atmospheric samples of precipitation and ambient air were collected at a single site in Washington, DC, for 7 months (for ambient air samples) and 1 year (for wet deposition samples) and analyzed for arsenic, cadmium, chromium and lead. The ranges of heavy metal concentrations for 6-day wet deposition samples collected over the 1-year period were 0.20-1.3 microg/l, 0.060-5.1 microg/l, 0.062-4.6 microg/l and 0.11-3.2 microg/l for arsenic, cadmium, chromium and lead, respectively, with a precision better than 5% for more than 95% of the measurements. The ranges of heavy metal concentrations for the 6-day ambient air samples were 0.800-15.7 ng/m(3), 1.50-30.0 ng/m(3), 16.8-112 ng/m(3), and 2.90-137 ng/m(3) for arsenic, cadmium, chromium and lead, respectively, with a precision better than 10%. The spread in the heavy metal concentration over the observation period suggests a high seasonal variability for heavy metal content in both ambient air and wet deposition samples.     

Reduced mercury deposition in New Hampshire from 1996 to 2002 due to changes in local sources

Changes in deposition of gaseous divalent mercury (Hg(II)) and particulate mercury (Hg(p)) in New Hampshire due to changes in local sources from 1996 to 2002 were assessed using the Industrial Source Complex Short Term (ISCST3) model (regional and global sources and Hg atmospheric reactions were not considered). Mercury (Hg) emissions in New Hampshire and adjacent areas decreased significantly (from 1540 to 880 kg yr⁻¹) during this period, and the average annual modeled deposition of total Hg also declined from 17 to 7.0 μg m⁻² yr⁻¹ for the same period. In 2002, the maximum amount of Hg deposition was modeled to be in southern New Hampshire, while for 1996 the maximum deposition occurred farther north and east. The ISCST3 was also used to evaluate two future scenarios. The average percent difference in deposition across all cells was 5% for the 50% reduction scenario and 9% for the 90% reduction scenario.     

Spatial and temporal variability of outdoor coarse particulate matter mass concentrations measured with a new coarse particle sampler during the Detroit Exposure and Aerosol Research Study

The Detroit Exposure and Aerosol Research Study (DEARS) provided data to compare outdoor residential coarse particulate matter (PM_10–2.5) concentrations in six different areas of Detroit with data from a central monitoring site. Daily and seasonal influences on the spatial distribution of PM_10–2.5 during Summer 2006 and Winter 2007 were investigated using data collected with the newly developed coarse particle exposure monitor (CPEM). These data allowed the representativeness of the community monitoring site to be assessed for the greater Detroit metro area. Multiple CPEMs collocated with a dichotomous sampler determined the precision and accuracy of the CPEM PM_10–2.5 and PM_2.5 data.CPEM PM_2.5 concentrations agreed well with the dichotomous sampler data. The slope was 0.97 and the R² was 0.91. CPEM concentrations had an average 23% negative bias and R² of 0.81. The directional nature of the CPEM sampling efficiency due to bluff body effects probably caused the negative CPEM concentration bias.PM_10–2.5 was observed to vary spatially and temporally across Detroit, reflecting the seasonal impact of local sources. Summer PM_10–2.5 was 5 μg m^?3 higher in the two industrial areas near downtown than the average concentrations in other areas of Detroit. An area impacted by vehicular traffic had concentrations 8 μg m^?3 higher than the average concentrations in other parts of Detroit in the winter due to the suspected suspension of road salt. PM_10–2.5 Pearson Correlation Coefficients between monitoring locations varied from 0.03 to 0.76. All summer PM_10–2.5 correlations were greater than 0.28 and statistically significant (p-value < 0.05). Winter PM_10–2.5 correlations greater than 0.33 were statistically significant (p-value < 0.05). The PM_10–2.5 correlations found to be insignificant were associated with the area impacted by mobile sources during the winter. The suspected suspension of road salt from the Southfield Freeway, combined with a very stable atmosphere, caused concentrations to be greater in this area compared to other areas of Detroit. These findings indicated that PM_10–2.5, although correlated in some instances, varies sufficiently across a complex urban airshed that that a central monitoring site may not adequately represent the population's exposure to PM_10–2.5.     

Columnar optical properties of tropospheric aerosol by combined lidar and sunphotometer measurements at Taipei,Taiwan

Vertical extinction profiles and columnar optical properties (optical depth, Angstrom exponent, lidar ratio, and particle depolarization) of aerosols were obtained by simultaneous measurements with a depolarization lidar and a sunphotometer at Taipei, Taiwan from February 2004 to January 2006. Columnar optical depths are high in Feb–Apr (0.61–0.75) by sunphotometer measurements. Lidar measurements show the contribution of aerosols in the free atmosphere on columnar optical depths are about 44–50% in Feb–Apr and about 26–37% in other months. Back-trajectory analyses and depolarization measurements show almost all of non-spherical aerosols originated from Northwest China which indicate Asian dusts frequently transported to Taipei from dust source regions in the free atmosphere. Aerosols with depolarization lower than 5% are found mostly originated from South China or Southeast Asia. Good correlations between columnar lidar ratio, particle depolarization, and Angstrom exponent are found for cases that columnar water vapor less than 1.5 cm. The effect of water vapor on particle depolarization is briefly discussed.     

Investigation of surfactant-enhanced mass removal and flux reduction in 3D correlated permeability fields using magnetic resonance imaging

Magnetic resonance imaging (MRI) was used to visualize the NAPL source zone architecture before and after surfactant-enhanced NAPL dissolution in three-dimensional (3D) heterogeneously packed flowcells characterized by different longitudinal correlation lengths: 2.1 cm (aquifer 1) and 1.1 cm (aquifer 2). Surfactant flowpaths were determined by imaging the breakthrough of a paramagnetic tracer (MnCl(2)) analyzed by the method of moments. In both experimental aquifers, preferential flow occurred in high permeability materials with low NAPL saturations, and NAPL was preferentially removed from the top of the aquifers with low saturation. Alternate flushing with water and two surfactant pulses (5-6 pore volumes each) resulted in approximately 63% of NAPL mass removal from both aquifers. However, overall reduction in mass flux (Mass Flux 1) exiting the flowcell was lower in aquifer 2 (68%) than in aquifer 1 (81%), and local effluent concentrations were found to increase by as high as 120 times at local sampling ports from aquifer 2 after surfactant flushing. 3D MRI images of NAPL revealed that NAPL migrated downward and created additional NAPL source zones in previously uncontaminated areas at the bottom of the aquifers. The additional NAPL source zones were created in the direction transverse to flow in aquifer 2, which explains the higher mass flux relative to aquifer 1. Analysis using a total trapping number indicates that mobilization of NAPL trapped in the two coarsest sand fractions is possible when saturation is below 0.5 and 0.4, respectively. Results from this study highlight the potential impacts of porous media heterogeneity and NAPL source zone architecture on advanced in-situ flushing technologies.     

Recovery of mercury-contaminated fisheries

In this paper, we synthesize available information on the links between changes in ecosystem loading of inorganic mercury (Hg) and levels of methylmercury (MeHg) in fish. Although it is widely hypothesized that increased Hg load to aquatic ecosystems leads to increases in MeHg in fish, there is limited quantitative data to test this hypothesis. Here we examine the available evidence from a range of sources: studies of ecosystems contaminated by industrial discharges, observations of fish MeHg responses to changes in atmospheric load, studies over space and environmental gradients, and experimental manipulations. A summary of the current understanding of the main processes involved in the transport and transformation from Hg load to MeHg in fish is provided. The role of Hg loading is discussed in context with other factors affecting Hg cycling and bioaccumulation in relation to timing and magnitude of response in fish MeHg. The main conclusion drawn is that changes in Hg loading (increase or decrease) will yield a response in fish MeHg but that the timing and magnitude of the response will vary depending of ecosystem-specific variables and the form of the Hg loaded.     

Variation of stabilised,microbial and biologically active carbon and nitrogen in soil under contrasting land use and agricultural management practices

Land use and agricultural practices modify both the amounts and properties of C and N in soil organic matter. In order to evaluate land use and management-dependent modifications of stable and labile C and N soil pools, (i). organic C and total N content, (ii). microbial (C(mic)) and N (N(mic)) content and (iii). C and N mineralisation rates, termed biologically active C and N, were estimated in arable, grassland and forest soils from northern and southern Germany. The C/N-ratios were calculated for the three levels (i)-(iii) and linked to the eco-physiological quotients of biotic-fixed C and N (C(mic)/C(org), N(mic)/N(t)) and biomass-specific C and N mineralisation rate (qCO(2), qN(min)). Correlations could mainly be determined between organic C, total N, C(mic), N(mic) and C mineralisation for the broader data set of the land use systems. Generally, the mineralisation activity rate at 22 degrees C was highly variable and ranged between 0.11 and 17.67 microg CO(2)-C g(-1) soil h(-1) and -0.12 and 3.81 microg (deltaNH(4)(+)+deltaNO(3)(-))-N g(-1) soil h(-1). Negative N data may be derived from both N immobilisation and N volatilisation during the experiments. The ratio between C and N mineralisation rate differed significantly between the soils ranging from 5 to 37, and was not correlated to the soil C/N ratio and C(mic)/N(mic) ratio. The C/N ratio in the 'biologically active' pool was significantly smaller in soils under conventional farming than those under organic farming systems. In a beech forest, it increased from the L, Of to the Ah horizon. The biologically active C and N pools refer to the current microbial eco-physiology and are related to the need for being C and N use efficient as indicated by metabolic qCO(2) and qN(min) quotients.