Characterization of the toxic effects of cadmium and 3.5-dichlorophenol on nitrifying activity and mortality in biologically activated sludge systems—effect of low temperature

Background, aims, and scope  Sometimes, urban wastewaters convey a more or less significant part of toxic products from industries or the craft industry. Nitrifying activity can be affected by these substances, implying higher ammonia concentrations in the outlet effluent and contributing to toxicity for the aquatic environment. Moreover, the more stringently treated wastewater standards now require a reliable treatment for nitrogen. One of the key issues is the identification of the inhibition behavior of nitrifying bacteria facing a toxic substance. This new understanding could then finally be integrated into models in order to represent and to optimize wastewater treatment plants (WWTP) operation in cases involving ‘toxic scenarios’. Materials and methods  The toxic substances studied in this work, cadmium and 3.5-dichlorophenol (3.5-DCP), are representative of chemical substances commonly found in municipal sewage and industrial effluents and symbolize two different contaminant groups. The effects of Cd and 3.5-DCP on nitrification kinetics have been investigated using respirometry techniques. Results  IC50 values determination gives concentrations of 3.1 mg/L for 3.5-DCP and 45.8 mg/L for Cd at 21 ± 1°C. The variation to low temperature seems to have no real effect on IC50 for DCP, but induces a decrease of cadmium IC50 to 27.5 mg/L at 14°C. Finally, specific respirometric tests have been carried out in order to determine the potential effect of these toxic substances on the nitrifying decay rate b _a . No significant effect has been noticed for Cd, whereas the presence of 3.5-DCP (at IC50 concentration) induced a dramatic increase of b _a at 20°C. The same behavior has been confirmed by experiments performed in winter periods with a sludge temperature around 12°C. Discussion  The target substances have different modes of action on activity and mortality, notably due to the abilities of the contaminant to be precipitated, accumulated, or even to be progressively degraded. Studies realized at low temperature confirmed this assumption, and put in evidence the effect of temperature on toxic substances capable of being biosorbed. However, the change in the sludge sample characteristics can be pointed out as a problem in the investigation of the temperature effect on nitrification inhibition, as biosorption, bioaccumulation, and predation are directly linked to the sludge characteristics (VSS concentration, temperature) and the plant operating conditions (loading rates, sludge age, etc.). Conclusions  This work brings new understandings concerning the action mode of these specific contaminants on nitrifying bacteria and, in particular, on the role of temperature. The experiments lead to the determination of the IC50 values for both toxic substances on biological nitrification. The inhibition mechanisms of Cd and 3.5-DCP on nitrifying activity have been simply represented by a non-competitive inhibition model. Recommendations and perspectives  Other experiments carried out in a continuous lab-scale pilot plant should be done with a proper control of the operating conditions and of the sludge characteristics in order to better understand the mechanisms of nitrification inhibition for each contaminant. Finally, these first results show that toxic substances can have an effect on the growth rate but also on the decay rate, depending on the characteristics of the toxic substance and the sludge. This eventual double effect would imply different strategies of WWTP operation according to the behavior of the contaminant on the bacteria.     

Sorption of polycyclic aromatic hydrocarbons (PAHs) to carbonaceous materials in a river floodplain soil

We report on sorption isotherm of phenanthrene (Phe) for river floodplain soil associated with carbonaceous materials, with particular attention being devoted to the natural loading of Phe. Our sorption experiments with original soil samples, size, and density sub-fractions showed that the light fraction had the highest sorption capacity comparable to low rank coals. In addition, the light fraction contributed most for the sorption of Phe in total soil samples. K_oc values for all fractions were in the same range, thus indicating that coal and coal-derived particles in all samples are responsible for the enhanced sorption for Phe. Sorption was strongly nonlinear and the combined partitioning and pore-filling model gave a better fit than the Freundlich sorption model. In addition, the spiked PAHs did not show the same behavior as the naturally aged ones, therefore the accessibility of indigenous background organic contaminants was reduced when coal and coal-derived particles are associated with the soils.     

Complexation-flocculation of organic contaminants by the application of oxyhumolite-based humic organic matter

Control of hazardous organic micropollutants is a challenging water quality issue. Dissolved humic organic matter (DOM) isolated from oxyhumolite coal mined in Bohemia was investigated as a complexation agent to remove polycyclic aromatic hydrocarbons (PAHs) and functionalized phenols from water by a two-stage process involving complexation and flocculation. After the formation of humic-contaminant complexes, ferric salts were added resulting in the precipitation and flocculation of the DOM and the associated pollutants. Flocculation experiments with ferric ion coagulants indicated that precipitation of oxyhumolite DOM together with the complexed contaminants occurred at lower ferric ion concentrations than with the reference DOM in acidic environments (pH approximately 3.5). The complexation-flocculation removal rates for non-reactive PAHs characterized by small localization energies of pi-electrons correlated well with the complexation constants. On the other hand, the combined complexation-flocculation removal rates for activated PAHs including trans-stilbene, anthracene and 9-methyl anthracene, as well as functionalized polar phenols, were higher than predicted from the complexation coefficients. Methodological studies revealed for the first time that the ferric ion coagulant contributed to enhanced removal rates, most probably due to ferric ion-catalyzed pollutant degradation resulting in oxidized products.     

Effect of housing geometry on the performance of Chemcatcher passive sampler for the monitoring of hydrophobic organic pollutants in water

Passive sampling of pollutants in water has been gaining acceptance for environmental monitoring. Previously, an integrative passive sampler (the Chemcatcher) was developed and calibrated for the measurement of time weighted average concentrations of hydrophobic pollutants in water. Effects of physicochemical properties and environmental variables (water temperature and turbulence) on kinetic and thermodynamic parameters characterising the exchange of analytes between the sampler and water have been published. In this study, the effect of modification in sampler housing geometry on these calibration parameters was studied. The results obtained for polycyclic aromatic hydrocarbons show that reducing the depth of the cavity in the sampler body geometry increased the exchange kinetics by approximately twofold, whilst having no effect on the correlation between the uptake and offload kinetics of analytes. The use of performance reference compounds thus avoids the need for extensive re-calibration when the sampler body geometry is modified.     

Variation of MCPA, metribuzine, methyltriazine-amine and glyphosate degradation, sorption, mineralization and leaching in different soil horizons

Pesticide mineralization and sorption were determined in 75 soil samples from 15 individually drilled holes through the vadose zone along a 28 km long transect of the Danish outwash plain. Mineralization of the phenoxyacetic acid herbicide MCPA was high both in topsoils and in most subsoils, while metribuzine and methyltriazine-amine was always low. Organic matter and soil pH was shown to be responsible for sorption of MCPA and metribuzine in the topsoils. The sorption of methyltriazine-amine in topsoil was positively correlated with clay and negatively correlated with the pH of the soil. Sorption of glyphosate was tested also high in the subsoils. One-dimensional MACRO modeling of the concentration of MCPA, metribuzine and methyltriazine-amine at 2 m depth calculated that the average concentration of MCPA and methyltriazine-amine in the groundwater was below the administrative limit of 0.1 μg/l in all tested profiles while metribuzine always exceeded the 0.1 μg/l threshold value.     

Regio- and stereoselective isomerization of hexabromocyclododecanes (HBCDs): kinetics and mechanism of gamma- to alpha-HBCD isomerization

Hexabromocyclododecanes (HBCDs) are high production volume chemicals (>20000 ty(-1)) used as flame retardants for plastics and textiles. Lately, we reported on the stereoselective isomerization of beta-HBCDs. Herein we present insights into the mechanism and kinetics of (+)gamma- to (+)alpha- and of (-)gamma- to (-)alpha-HBCD isomerization. Only two of the six bromine atoms migrated, indicating that rearrangements of gamma- to alpha-HBCDs are regio- and stereoselective as well. The apparent first-order isomerization rate constants increased from 0.0013 to 0.0031 to 0.0070 min(-1) at 120, 130, and 140 degrees C, respectively, corresponding to half-lives of 540, 230, and 99 min. Thus, a thermal treatment of materials containing gamma-HBCDs at temperatures >100 degrees C may induce the formation of alpha-HBCDs and, hence, may alter the diastereomeric ratio of a HBCD mixture. The inversion of vicinal dibromides in like-configurations (RR/SS) prevailed, whereas unlike-configurations (RS/SR) were not affected. An intramolecular, stereoselective migration of neighboring bromine atoms via a four-center transition state would explain the observed stereoisomer pattern and first-order kinetics. Despite the fact that vicinal dibromides in HBCDs prefer synclinal (gauche) conformations, antiperiplanar (staggered) conformations are assumed to facilitate concerted 1.2-shifts of both bromine atoms. A conformation analysis revealed that under kinetic control, only those bromine atoms in the more flexible part of the molecules are migrating, whereas those in the conserved triple-turn motive were not affected. Thus, this structural motive, common to all alpha-, beta-, and gamma-HBCDs, is more rigid and less reactive than the flexible part, containing the reacting dibromides in like-configurations.     

Concentration of heavy metals in various children's herbal tea types and their correlations

This investigation was undertaken to determine the concentrations of cadmium, lead, mercury, zinc, copper and magnesium in six tea types used as children's tea. Six types of tea of different herbal composition used for children's consumption (T1, T2, T3, T4, T5 and T6) were analyzed in three subsequent collections. The analysis of cadmium showed that the concentration was very similar in all types of children's tea, ranging from 0.233 to 0.369 mg/kg. Lead concentrations were in the range of 0.340-1.564 mg/kg without any significant differences. The analysis of mercury detected very low concentration of this metal in all samples (0.002-0.004 mg/kg). In zinc, the values ranged from 36.633 to 71.711 mg/kg, with significant differences (p < 0.001) according to tea type. Copper concentration was 10.089-30.178 mg/kg with the highest value in T4. The concentration of magnesium was significantly higher in tea T1 and T2 (102.311 and 129.422 mg/kg) in comparison with other tea types where the level was 19.811-37.411 mg/kg. The maximum tolerable limit determined by Codex Alimentarius was not exceeded in any sample. In general, correlation analysis detected high positive correlation between cadmium and lead (r = 0.89), cadmium and mercury (r = 0.92) and between lead and mercury (r = 0.77).     

Field scale characterization and modeling of contaminant release from a coal tar source zone

A coal tar contaminated site was characterized using traditional and innovative investigation methods. A careful interpretation of hydrogeological and hydrogeochemical data allowed for the conceptualization of the heterogeneous coal tar distribution in the subsurface. Past and future contaminant release from the source zone was calculated using a modeling framework consisting of a three-dimensional steady-state groundwater flow model (MODFLOW) and two hydrogeochemical models (MIN3P). Computational time of long-term simulations was reduced by simplifying the coal tar composition using 3 composite and 2 individual constituents and sequential application of a 2D centerline model (for calibration and predictions) and a 3D model (only for predictions). Predictions were carried out for a period of 1000 years. The results reveal that contaminant mass flux is governed by the geometry of zones containing residual coal tar, amount of coal tar, its composition and the physicochemical properties of the constituents. The long-term predictions made using the 2D model show that even after 1000 years, source depletion will be small with respect to phenanthrene, 89% of initial mass will be still available, and for the moderately and sparingly soluble composite constituents, 60% and 98%, respectively.     

Accelerated seeded precipitation pre-treatment of municipal wastewater to reduce scaling

Membrane based treatment processes are very effective in removing salt from wastewater, but are hindered by calcium scale deposit formation. This study investigates the feasibility of removing calcium from treated sewage wastewater using accelerated seeded precipitation. The rate of calcium removal was measured during bench scale batch mode seeded precipitation experiments at pH 9.5 using various quantities of calcium carbonate as seed material. The results indicate that accelerated seeded precipitation may be a feasible option for the decrease of calcium in reverse osmosis concentrate streams during the desalination of treated sewage wastewater for irrigation purposes, promising decreased incidence of scaling and the option to control the sodium adsorption ratio and nutritional properties of the desalted water. It was found that accelerated seeded precipitation of calcium from treated sewage wastewater was largely ineffective if carried out without pre-treatment of the wastewater. Evidence was presented that suggests that phosphate may be a major interfering substance for the seeded precipitation of calcium from this type of wastewater. A pH adjustment to 9.5 followed by a 1-h equilibration period was found to be an effective pre-treatment for the removal of interferences. Calcium carbonate seed addition at 10 g l⁻¹ to wastewater that had been pre-treated in this way was found to result in calcium precipitation from supersaturated level at 60 mg l⁻¹ to saturated level at 5 mg l⁻¹. Approximately 90% reduction of the calcium level occurred 5 min after seed addition. A further 10% reduction was achieved 30 min after seed addition.     

Minimizing opportunity costs to aquatic connectivity restoration while controlling an invasive species

Controlling invasive species is critical for conservation but can have unintended consequences for native species and divert resources away from other efforts. This dilemma occurs on a grand scale in the North American Great Lakes, where dams and culverts block tributary access to habitat of desirable fish species and are a lynchpin of long‐standing efforts to limit ecological damage inflicted by the invasive, parasitic sea lamprey (Petromyzon marinus). Habitat restoration and sea‐lamprey control create conflicting goals for managing aging infrastructure. We used optimization to minimize opportunity costs of habitat gains for 37 desirable migratory fishes that arose from restricting sea lamprey access (0–25% increase) when selecting barriers for removal under a limited budget (US$1–105 million). Imposing limits on sea lamprey habitat reduced gains in tributary access for desirable species by 15–50% relative to an unconstrained scenario. Additional investment to offset the effect of limiting sea‐lamprey access resulted in high opportunity costs for 30 of 37 species (e.g., an additional US$20–80 million for lake sturgeon [Acipenser fulvescens]) and often required ≥5% increase in sea‐lamprey access to identify barrier‐removal solutions adhering to the budget and limiting access. Narrowly distributed species exhibited the highest opportunity costs but benefited more at less cost when small increases in sea‐lamprey access were allowed. Our results illustrate the value of optimization in limiting opportunity costs when balancing invasion control against restoration benefits for diverse desirable species. Such trade‐off analyses are essential to the restoration of connectivity within fragmented rivers without unleashing invaders.