Experimental and modeling study of de novo formation of PCDD/PCDF on MSW fly ash

The effect of sulfur dioxide （SO2） on the formation of polychlorinated dibenzo-p-dioxins （PCDDs） and polychlorinated dibenzofurans （PCDFs） has been studied in an entrained-flow reactor （EFR） under simulated waste combustion conditions. A chlorination model based on conditional probability was employed to evaluate the homologue patterns of PCDDs and PCDFs. Results revealed that the presence of SO2 did not alter the formation pathway although SO2 suppressed PCDD/F formation. The prediction model of PCDF showed good agreement with the experimental data （R--0.95）, whereas the prediction for PCDDs did not correlate well with the experimental data. This may be explained because potential chlorination pathways play a significant role in PCDF formation, whereas PCDDs are mainly formed through condensation reactions. Furthermore, the result indicated that the steric hindrance during formation has more effects on PCDD than on PCDF due to the symmetric molecular structures of PCDDs.     

Long-Term Impacts of Land-Use Change on Non-Point Source Pollutant Loads for the St. Louis Metropolitan Area, USA

A land-use-change simulation model (LEAM) and a non-point-source (NPS) water quality model (L-THIA) were closely coupled as LEAMwq in order to determine the long-term implications of various degree of urbanization on NPS total nitrogen (TN), total suspended particles (TSP), and total phosphorus (TP) loads. A future land-use projection in the St. Louis metropolitan area from 2005 to 2030 using three economic growth scenarios (base, low, and high) and a long-term precipitation dataset were used to predict the mean annual surface runoff and mean annual NPS pollutant loads in the region. Results show mean annual TN increases of 0.21%, 0.13%, and 0.14% by 2030 compared to 2000 under the base, high, and low scenarios, respectively. TSP and TP showed similar trends with different magnitudes. Corresponding changes in annual mean surface runoff were shown to be lower than expected, which might be attributed to the small-scale conversion pattern of land uses. In the most dramatic change (high growth) scenario, the runoff would increase across time but at varying rates, and temporal pollutant loads would result in a more complicated pattern than in the other scenarios. This is attributed to the complex interactions between event mean concentrations of pollutants and the magnitude of changes in land-use acreages. By integrating L-THIA with LEAM, LEAMwq was found to be a useful planning tool to illustrate in a quick and simple manner how future water quality is connected to decision-making on future land-use change.     

A passive air sampler for characterizing the vertical concentration profile of gaseous phase polycyclic aromatic hydrocarbons in near soil surface air

Air-soil exchange is an important process governing the fate of polycyclic aromatic hydrocarbons (PAHs). A novel passive air sampler was designed and tested for measuring the vertical concentration profile of 4 low molecular weight PAHs in gaseous phase (PAH_LMW4) in near soil surface air. Air at various heights from 5 to 520 mm above the ground was sampled by polyurethane foam disks held in down-faced cartridges. The samplers were tested at three sites: A: an extremely contaminated site, B: a site near A, and C: a background site on a university campus. Vertical concentration gradients were revealed for PAH_LMW4 within a thin layer close to soil surface at the three sites. PAH concentrations either decreased (Site A) or increased (Sites B and C) with height, suggesting either deposition to or evaporation from soils. The sampler is a useful tool for investigating air-soil exchange of gaseous phase semi-volatile organic chemicals.     

A Method for Assessing Hydrologic Alteration within Ecosystems

Hydrologic regimes play a major role in determining the biotic composition, structure, and function of aquatic, wetland, and riparian ecosystems. But human land and water uses are substantially altering hydrologic regimes around the world. Improved quantitative evaluations of human-induced hydrologic changes are needed to advance research on the biotic implications of hydrologic alteration and to support ecosystem management and restoration plans. We propose a method for assessing the degree of hydrologic alteration attributable to human influence within an ecosystem. This method, referred to as the "Indicators of Hydrologic Alteration," is based upon an analysis of hydrologic data available either from existing measurement points within an ecosystem (such as at stream gauges or wells) or model-generated data. We use 32 parameters, organized into five groups, to statistically characterize hydrologic variation within each year. These 32 parameters provide information on ecologically significant features of surface and ground water regimes influencing aquatic, wetland, and riparian ecosystems. We then assess the hydrologic perturbations associated with activities such as dam operations, flow diversion, groundwater pumping, or intensive land-use conversion by comparing measures of central tendency and dispersion for each parameter between user-defined "pre-impact" and "post-impact" time frames, generating 64 Indicators of Hydrologic Alteration. This method is intended for use with other ecosystem metrics in inventories of ecosystem integrity, in planning ecosystem management activities, and in setting and measuring progress toward conservation or restoration goals.     

Role of organic acids in enhancing the desorption and uptake of weathered p,p'-DDE by Cucurbita pepo

Experiments were conducted to assess the effect of seven organic acids [succinic, tartaric, malic, malonic, oxalic, citric, ethylene-diaminetetraacetic (EDTA)] over a concentration range of two orders of magnitude (0.001-0.10 M) on the abiotic desorption of weathered p,p'-DDE and the extraction of polyvalent inorganic ions from soil. At 0.05 M all organic acids significantly increased contaminant desorption by 19-80%. Organic acids also increased the aqueous concentration of eight inorganic constituents extracted from soil, with at least a six-fold increase in the release of Al, Fe, Mn, and P at 0.001 M. Zucchini seedlings grown for 28 d in soil containing weathered p,p'-DDE (300 ng/g, dry weight) were periodically amended with distilled water, citric or oxalic acids (0.01 M). Plants receiving water removed 1.7% of the p,p'-DDE from the soil. Seedlings amended with citric or oxalic acids removed 2.1 and 1.9% of the contaminant, respectively, and contained up to 66% more contaminant in the shoot system than unamended vegetation. A second crop of untreated (distilled water) zucchini in the same soil removed more contaminant than the first crop (2.5%), although the addition of organic acids did not further enhance contaminant uptake. The data indicate that the addition of low molecular weight organic acids causes the partial dissolution of the soil structure through the chelation of inorganic structural ions, potentially enhancing bioavailability and having implications for the phytoremediation of persistent organic pollutants in soil.     

Iron‐mediated abiotic degradation of RDX in a contaminated aquifer

The influence of aqueous‐ and mineral‐phase iron on royal demolition explosive (RDX) destruction has been previously investigated in theoretical settings and bench‐scale tests by various practitioners. The feasible use of in situ redox manipulation to create reactive Fe(II) is contingent upon the aquifer containing enough iron oxides and iron‐bearing clay minerals for the treated zone to remain effective. The following is a summary of a bench‐scale assessment of this relationship using aquifer material from an ongoing groundwater remediation effort at the Iowa Army Ammunition Plant (IAAP). A bench‐scale study was designed to determine the relative contributions of the biotic and iron‐mediated abiotic degradation processes to the net decrease in RDX observed at the site using saturated aquifer samples collected from within the RDX plume. Sterilized samples with a sufficient stoichiometric excess of both soluble and mineral‐phase iron reduced concentrations of RDX in both the soil and water fractions to the same extent as the samples containing native biota. These results indicate that in situ, abiotic degradation of RDX is feasible in areas unsuitable to biotic degradation processes, yielding an additional alternative for in situ RDX remediation. © 2012 Wiley Periodicals, Inc.     

Longitudinal data analysis in support of functional stability concepts for leachate management at closed municipal landfills

Landfill functional stability provides a target that supports no environmental threat at the relevant point of exposure in the absence of active control systems. With respect to leachate management, this study investigates “gateway” indicators for functional stability in terms of the predictability of leachate characteristics, and thus potential threat to water quality posed by leachate emissions. Historical studies conducted on changes in municipal solid waste (MSW) leachate concentrations over time (longitudinal analysis) have concentrated on indicator compounds, primarily chemical oxygen demand (COD) and biochemical oxygen demand (BOD). However, validation of these studies using an expanded database and larger constituent sets has not been performed. This study evaluated leachate data using a mixed-effects regression model to determine the extent to which leachate constituent degradation can be predicted based on waste age or operational practices. The final dataset analyzed consisted of a total of 1402 samples from 101 MSW landfills. Results from the study indicated that all leachate constituents exhibit a decreasing trend with time in the post-closure period, with 16 of the 25 target analytes and aggregate classes exhibiting a statistically significant trend consistent with well-studied indicators such as BOD. Decreasing trends in BOD concentration after landfill closure can thus be considered representative of trends for many leachate constituents of concern.     

A risk index methodology for potentially polluting marine sites

Attempting to assess the risk of a release from a potentially polluting marine site (PPMS) can be a very subjective process. The Marine Site Risk Index (MaSiRI) is designed to provide a more objective approach to this process by adopting a table-based evaluation scheme, while still allowing for the inevitable unknown conditions by including a subjective ‘expert correction’ in a suitably controlled manner. Building on a geographic database of PPMS records, the MaSiRI algorithm applies data filters to remove PPMS records for which it is not applicable and then estimates a basic risk index based on core data that almost all sites would contain. It can then refine the results for those sites that have auxiliary data, varying the assessed risk as appropriate, according to standard rule-sets. A risk level of confidence is computed and adjusted to express dynamic confidence in the risk value (e.g., due to reliance on estimates rather than measured values), and where appropriate an upper and lower bound of risk can be used to assess the range of values associated with an estimated parameter. This information can be visualized by a composite quality symbol proposed here. MaSiRI is demonstrated on three illustrative shipwrecks and then compared against the DEvelopment of European guidelines for Potentially Polluting (DEEPP) project database from the Pelagos Sanctuary in the western Mediterranean. The aggregate results of the comparison are broadly similar to DEEPP, within the limits of the comparison, but provide a more detailed analysis in the case of estimated pollutant volume and ubiquitous assessment of levels of confidence.