Dissecting the ecosystem service of large-scale pollutant retention: The role of wetlands and other landscape features

Various features of a landscape contribute to the regulating ecosystem service of reducing waterborne pollutant loading to downstream environments. At local scales, wetlands have been shown to be effective in retaining pollutants. Here, we investigate the landscape-scale contribution to pollutant retention provided by multiple wetlands. We develop a general analytical model which shows that the retention contribution of wetlands and other landscape features is only significant if a large fraction of the total waterborne pollutant transport passes through them. Next, by means of a statistical analysis of official data, we quantify the nutrient retention contribution of wetlands for multiple sub-catchments in two Swedish Water Management Districts. We compare this with the retention contribution of two other landscape features: the waterborne transport distance and major lakes. The landscape-scale retention contribution of wetlands is undetectable; rather, the other two landscape features account for much of the total nutrient retention.     

Solvophobic approach for predicting sorption of hydrophobic organic chemicals on synthetic sorbents and soils

The application of a solvophobic approach for predicting the sorption of hydrophobic organic compounds (HOC) was evaluated with data collected using synthetic sorbents and soils. The experimental data consisted of batch equilibrium sorption coefficients (K_D), as well as soil-TLC and reversed-phase liquid chromatographic (RPLC) retention factors (κ′). All data were collected using aqueous solutions and binary or ternary solvent mixtures of water, methanol, acetone, and acetonitrile. As predicted by the theory, the chromatographic retention factors and sorption coefficients for HOC decreased log-linearly with increasing fraction of organic cosolvent in binary solvents. Model parameters estimated from the binary solvent data could be used to predict sorption (or retention) from ternary solvents. Reasonable agreement was found between model parameters reported in the literature and those estimated using the data from batch sorption, soil-TLC, and RPLC studies.     

Chromatographic retention-activity relationships for prediction of the toxicity pH-dependence of phenols

An investigation of the use of the chromatographic retention (log k) as an in vitro approach for modeling the pH-dependence of the toxicity to Guppy of phenols is developed. A data set of 19 phenols with available experimental toxicity-pH data was used. The importance of the mechanism of toxic action (MOA) of phenols was studied. log k data at three pH values were used for the phenols classification and two groups or 'MODEs' were identified. For one 'MODE' a quantitative retention-activity relationship (QRAR) model was calculated. Finally, the model was used to assess the toxicity to Guppy of phenols at different pH values. The results of this investigation suggest that chromatographic retention data allows fish toxicity modeling, in the 5.5-8 pH range of interest.     

A new method of predicting of gas chromatographic retention indices for polychlorinated dibenzofurans (PCDFs)

A new method has been developed to describe the quantitative relationship between molecular structures of PCDFs and their gas chromatographic retention indices on a 30-m fused silica column coated with DB-5 stationary phase. The regression equation is derived with a multiple correlation coefficient greater than 0.9995. The highest residual is 20 index units. The standard deviation is less than 7 index units. Using this regression equation, the retention indices of PCDFs for which data is not available have also been predicted.     

The impact of wet flue gas desulfurization scrubbing on mercury emissions from coal-fired power stations

This article introduces a predictive capability for Hg retention in any Ca-based wet flue gas desulfurization (FGD) scrubber, given mercury (Hg) speciation at the FGD inlet, the flue gas composition, and the sulphur dioxide (SO2) capture efficiency. A preliminary statistical analysis of data from 17 full-scale wet FGDs connects flue gas compositions, the extents of Hg oxidation at FGD inlets, and Hg retention efficiencies. These connections clearly signal that solution chemistry within the FGD determines Hg retention. A more thorough analysis based on thermochemical equilibrium yields highly accurate predictions for total Hg retention with no parameter adjustments. For the most reliable data, the predictions were within measurement uncertainties for both limestone and Mg/lime systems operating in both forced and natural oxidation mode. With the U.S. Environmental Protection Agency's (EPA) Information Collection Request (ICR) database, the quantitative performance was almost as good for the most modern FGDs, which probably conform to the very high SO2 absorption efficiencies assumed in the calculations. The large discrepancies for older FGDs are tentatively attributed to the unspecified SO2 capture efficiencies and operating temperatures and to the possible elimination of HCl in prescrubbers. The equilibrium calculations suggest that Hg retention is most sensitive to inlet HCl and O2 levels and the FGD temperature; weakly dependent on SO2 capture efficiency; and insensitive to HgCl2, NO, CA:S ratio, slurry dilution level in limestone FGDs, and MgSO3 levels in Mg/lime systems. Consequently, systems with prescrubbers to eliminate HCl probably retain less Hg than fully integrated FGDs. The analysis also predicts re-emission of Hg(O) but only for inlet O2 levels that are much lower than those in full-scale FGDs.     

Application of different RP-HPLC methods for the determination of the octanol/water partition coefficient of selected tetrachlorobenzyltoluenes.

Reversed-phase high-performance liquid chromatography (RP-HPLC) in both, isocratic and gradient elution mode (stationary phase: LiChrospher 100 RP-18; mobile phase: water/methanol or water/acetonitrile) was used for a renewed determination of octanol/water partition coefficients (Kow) of selected tetrachlorobenzyltoluene (TCBT) isomers. Reported Kow values identify this substance class as very hydrophobic but the data are relatively inconsistent. Based on a series of calibration runs with hydrophobic reference substances of different chemical structure at various eluent compositions we tested different approaches for the evaluation of isocratic retention factors (logk) and found substantial differences between the direct calibration procedure at special methanol volume fractions in the mobile phase (0.95-0.80) and the use of retention factors extrapolated to pure water as eluent (logkw). The logKow values obtained for the TCBTs with the latter approach are around 0.5 units higher and closer to literature data. The gradient elution experiments yield slightly better results compared to the isocratic direct calibration procedure, but not as good as the calibration with log kw. In addition, the use of the RP-HPLC retention factors for estimating sorption coefficients (Koc) of TCBT isomers is discussed.     

Application of an empirical transport model to simulate retention of nanocrystalline titanium dioxide in sand columns

Nanocrystalline titanium dioxide was injected into sand columns to simulate subsurface injection for creation of a permeable treatment barrier. Past usage of this material as an ex situ pilot scale treatment filter has shown that it has a high adsorption capacity for a number of heavy metals and therefore would be a good candidate for injection technology. Three suspension concentrations (50, 75 and 100 mg l(-1)) were pumped through packed sand columns at different flow velocities (3.0, 6.8 and 14.1 cm min(-1)). Little to no particles was detected in the effluent. Most of the nanoparticles remained in the sand columns, with an increasing then decreasing retained solids pattern. Application of a one-dimensional advection-dispersion flow model, that included two empirical kinetic terms to account for particle retention in the porous media, produced data fits that followed the general trend of the data, but did not truly capture the concentration maxima in the data sets. Discussion of these results highlights the limited ability of existing models to aid in predicting particle retention of non-ideal materials for engineering purposes.     

Functional models for colloid retention in porous media at the triple line

Spectral confocal microscope visualizations of microsphere movement in unsaturated porous media showed that attachment at the Air Water Solid (AWS) interface was an important retention mechanism. These visualizations can aid in resolving the functional form of retention rates of colloids at the AWS interface. In this study, soil adsorption isotherm equations were adapted by replacing the chemical concentration in the water as independent variable by the cumulative colloids passing by. In order of increasing number of fitted parameters, the functions tested were the Langmuir adsorption isotherm, the Logistic distribution, and the Weibull distribution. The functions were fitted against colloid concentrations obtained from time series of images acquired with a spectral confocal microscope for three experiments performed where either plain or carboxylated polystyrene latex microspheres were pulsed in a small flow chamber filled with cleaned quartz sand. Both moving and retained colloids were quantified over time. In fitting the models to the data, the agreement improved with increasing number of model parameters. The Weibull distribution gave overall the best fit. The logistic distribution did not fit the initial retention of microspheres well but otherwise the fit was good. The Langmuir isotherm only fitted the longest time series well. The results can be explained that initially when colloids are first introduced the rate of retention is low. Once colloids are at the AWS interface they act as anchor point for other colloids to attach and thereby increasing the retention rate as clusters form. Once the available attachment sites diminish, the retention rate decreases.     

The Effects of Air Pollution on Exposed Cotton Fabrics

This report covers the results of one-year exposure studies of cotton fabrics exposed at different environmental sites in the metropolitan St. Louis, Mo., and Chicago, III. areas. The 12 sites range from heavy industrial to essentially rural. The data presented definitely establish a relationship between air pollution and accelerated degradation of cotton fabrics. The data include strength retention of several cotton fabrics and air pollution data, as determined by periodic measurement of dustfall, suspended particulate matter, sulfation, and sulfur dioxide.     

Three-fluid retention in porous media involving water, PCE and air

A classical way to obtain three-fluid retention curves in porous media from measured two-fluid retention curves is based on the Leverett concept, which states that the total volumetric liquid content in a water-wet porous medium, containing water, a nonaqueous-phase liquid (NAPL) and air, is a function of the capillary pressure across the interface between the continuous NAPL and air. This functional relationship results from the assumed condition that in a three-fluid porous medium, the intermediate wetting fluid spreads over the water-air interface. Application of Leverett's concept may not be valid, however, for nonspreading NAPLs like perchloroethylene (PCE). This paper discusses measurements of both PCE-air and water-PCE-air retention curves using a long vertical column in conjunction with a dual-energy gamma radiation system. The data indicate that the Leverett concept was applicable only until a critical PCE saturation had been reached.     

Relative retention times of chlorinated monoterpenes

GC retention times for 67 chlorinated monoterpenes, belonging to the technical pesticide Toxaphene have been measured under the same conditions and relative retention times have been determined. They consisted of 45 chlorinated bornanes, 13 chlorinated bornenes, 8 chlorinated dihydrocamphenes and 1 chlorinated camphene. Useful correlations between structure and retention time were found. Similar changes in structure for different compounds lead to similar changes in retention times. These correlations allow to predict retention times for yet unknown Toxaphene congeners.     

The use of environmental metabolomics to determine glyphosate level of exposure in rapeseed (Brassica napus L.) seedlings

Metabolic profiling in plants can be used to differentiate between treatments and to search for biomarkers for exposure. A methodology for processing Ultra-High-Performance Liquid Chromatography-Diode-Array-Detection data is devised. This methodology includes a scheme for selecting informative wavelengths, baseline removal, retention time alignment, selection of relevant retention times, and principal component analysis (PCA). Plant crude extracts from rapeseed seedling exposed to sublethal concentrations of glyphosate are used as a study case. Through this approach, plants exposed to concentrations down to 5 μM could be distinguished from the controls. The compounds responsible for this differentiation were partially identified and were different from those specific for high exposure samples, which suggests that two different responses to glyphosate are elicited in rapeseed depending on the level of exposure. The PCA loadings indicate that a combination of other metabolites could be more sensitive than the response of shikimate to detect glyphosate exposure.     

水力停留时间对曝气生物滤池处理效能及运行特性的影响

通过实验室模型试验研究了曝气生物滤池处理模拟生活污水的效能,分析了水力停留时间(HRT)变化对曝气生物滤池处理效果及运行特性的影响规律。研究发现,当HRT大于0.6h时,曝气生物滤池具有良好的有机物和浊度的去除效果,而当HRT为0．4h时,处理效果则显著下降;反应器的硝化反硝化脱氮能力受HRT的影响比较明显,缩短HRT将使氨氮和总氮去除率迅速下降,当HRT为1.25h时,氨氮和总氮去除率分别达到70%和40％以上;缩短HRT会在一定程度上促进亚硝酸盐积累现象的发生。而反应器的过滤周期则与HRT呈明显的线性关系。     

The utility of distributed air volume sets when sampling ambient air using solid adsorbents

Use of solid adsorbents for air sampling always raises questions of adequate retention, blank corrections and artifact formation. Universally valid answers to these questions are unavailable. Collection of a small set of data by sampling over a large range of air volume can provide situation-specific indications of data quality not possible with the more usual tandem bed approach. Further, it does so in a direct simple way that is especially useful in monitoring applications. The distributed air volume sampling approach is illustrated using Tenax as the adsorbent.     

Calculated physical properties of polychlorinated dibenzo-p-dioxins and dibenzofurans

The modified neglect of diatomic overlap (MNDO) method, a semi-empirical molecular orbital calculation, has been used to calculate the heats of formation, ionization potentials, dipole moments, and LUMOs (lowest unoccupied molecular orbitals) for all of the tetra, penta, hexa, hepta, and octa-chlorinated dibenzo-p-dioxins and dibenzofurans. These data have been used to predict gas chromatographic retention indexes.     

Multivariate characterization of polycyclic aromatic hydrocarbons using semi-empirical molecule orbital calculations and physical data

Multivariate characterization of 60 polycyclic aromatic hydrocarbons (PAHs) was performed using data from literature and semi-empirical molecular orbital calculations. This dataset was analyzed by principal component analysis and projections to latent structures by means of partial least square. The PAHs were found to distribute in the chemical domain in several groups mainly governed by the number of aromatic rings and the number of five-membered rings. The multivariate model and training set was used to predict GC retention times on a non-polar column (DB-5). Using a 2(4) experimental design on the principal components of the chemical characterization model, a test set of PAHs was selected dependent on the distribution in the chemical domain of the PAHs. Such a test set is expected to improve selection of PAHs for future testing and modeling of both biological and chemical responses. Although the model of GC retention times was good, the precision was however not good enough for practical use.     

As(V) retention on soils and forest by-products and other waste materials

As(V) retention capacity is determined by means of adsorption/desorption trials performed for coarse and fine ground mussel shell, forest and vineyard soils with or without fine shell, pine wood ash, oak wood ash, pine sawdust and slate-processing fines. Pine ash shows the highest arsenic retention potential (with >97 % adsorption and ≤1 % desorption), followed by shell-amended forest soil (adsorption between 96 and 92 %), by un-amended forest soil (adsorption between 98 and 86 %) and by the amended vineyard soil (adsorption between 92 and 75 %). Sawdust is the material with the lowest arsenic retention capacity in most cases, with un-amended vineyard soil also showing poor results. In the case of oak ash, As(V) percentage adsorption becomes higher with increasing added arsenic concentrations, while this increase in added arsenic causes lower percentage adsorption in the case of slate fines. Regarding adsorption ability, As(V) adsorption data were fitted to Freundlich and Langmuir models, showing good fitting, with pine ash and shell-amended forest soil having the highest K _F values. In view of that, mussel shell amendment would be useful to increase arsenic retention on forest and vineyard soils, while pine ash could be used to retain arsenic even from wastewaters.     

废旧镍镉电池的生物沥滤处理——沥滤停留时间的影响研究

用污泥加硫酸化液沥滤镍镉电池中的重金属是一种全新的工艺,该工艺主要由生物酸化反应器和金属沥滤反应器两个反应器组成.生物酸化反应器中产生的酸液就是沥滤电池中重金属的反应液.研究表明,酸化液在沥滤反应池的停留时间对沥滤的效果有显著影响.在1、4、7、12 d 4个停留时间中,4 d的效果是最好的,对金属Cd和Ni都用40 d左右基本实现了全部滤除;1d略微慢一些,Cd用了40 d,Ni用了45 d;7 d和12 d的沥滤时间都长于50 d.4 d产生的金属废液量是1 d的1/4,考虑到后续处理金属沥滤废液的工作量,选择4d的停留时间要优于1d.