Biosorption of Cr(III) from aqueous solution by freeze-dried activated sludge: Equilibrium,kinetic and thermodynamic studies

Batch biosorption experiments were conducted to remove Cr(III) from aqueous solutions using activated sludge from a sewage treatment plant. An investigation was conducted on the effects of the initial pH, contact time, temperature, and initial Cr(III) concentration in the biosorption process. The results revealed that the activated sludge exhibited the highest Cr(III) uptake capacity (120 mg·g⁻¹) at 45°C, initial pH of 4, and initial Cr(III) concentration of 100 mg·L⁻¹. The biosorption results obtained at various temperatures showed that the biosorption pattern accurately followed the Langmuir model. The calculated thermodynamic parameters, ΔG^o (−0.8– −4.58 kJ·mol⁻¹), ΔH^o (15.6–44.4 kJ·mol⁻¹), and ΔS^o (0.06–0.15 kJ·mol⁻¹·K⁻¹) clearly indicated that the biosorption process was feasible, spontaneous, endothermic, and physical. The pseudo first-order and second-order kinetic models were adopted to describe the experimental data, which revealed that the Cr(III) biosorption process conformed to the second-order rate expression and the biosorption rate constants decreased with increasing Cr(III) concentration. The analysis of the values of biosorption activation energy (E_a = −7 kJ·mol⁻¹) and the intra-particle diffusion model demonstrated that Cr(III) biosorption was film-diffusion-controlled.     

Impact of solids on biphasic biodegradation of phenanthrene in the presence of hydroxypropyl-<Emphasis Type="Italic">β</Emphasis>-cyclodextrin (HPCD)

The consequence of polycyclic aromatic hydrocarbons (PAHs) in the environment is of great concern. The hydrophobic properties of PAHs significantly impact phase distribution causing limited bioavailability. Enhanced biodegradation has been extensively carried out by surfactants and the redeployment effect was recognized. However, the quantitative relationship concerning the impact of solids was rarely reported. A batch of biphasic tests were carried out by introducing Mycobacterium vanbaalenii PYR-1 and hydroxypropyl-β-cyclodextrin (HPCD) into a mixture of phenanthrene solution and various glass beads (GB37-63, GB105-125, and GB350-500). The comparative results demonstrated that HPCD had little effect on microbial growth and was not degradable by bacterium. A model was proposed to describe the biodegradation process. The regression results indicated that the partition coefficient k _d (1.234, 0.726 and 0.448 L·g^?1) and the degradation rate k (0 mmol·L^?1: 0.055, 0.094, and 0.112; 20 mmol·L^?1: 0.126, 0.141, and 0.156; 40 mmol·L^?1: 0.141, 0.156 and 0.184 d^?1) were positively and negatively correlated with the calculated total surface area (TSA) of solids, respectively. Degradation enhanced in the presence of HPCD, and the enhancing factor f was calculated (20 mmol·L^?1: 15.16, 40.01, and 145.5; 40 mmol·L^?1: 13.29, 37.97, and 138.4), indicating that the impact of solids was significant for the enhancement of biodegradation.     

Development of pretreatment protocol for DNA extraction from biofilm attached to biologic activated carbon (BAC) granules

The biologic activated carbon (BAC) process is widely used in drinking water treatments. A comprehensive molecular analysis of the microbial community structure provides very helpful data to improve the reactor performance. However, the bottleneck of deoxyribonucleic acid (DNA) extraction from BAC attached biofilm has to be solved since the conventional procedure was unsuccessful due to firm biomass attachment and adsorption capacity of the BAC granules. In this study, five pretreatments were compared, and adding skim milk followed by ultrasonic vibration was proven to be the optimal choice. This protocol was further tested using the vertical BAC samples from the full-scale biofilter of Pinghu Water Plant. The results showed the DNA yielded a range of 40 μg·g^-1 BAC (dry weight) to over 100 μg·g^-1 BAC (dry weight), which were consistent with the biomass distribution. All results suggested that the final protocol could produce qualified genomic DNA as a template from the BAC filter for downstream molecular biology researches.     

Sorption of tetracycline to sediments and soils: assessing the roles of pH,the presence of cadmium and properties of sediments and soils

Batch sorption experiments were conducted to evaluate the sorption behavior of tetracycline (TC, H₃L) on sediments and soils in the presence and absence of cadmium (Cd), as affected by pH and properties of sediments and soils. The results indicated stronger nonlinearity and higher capacity of TC sorption on sediments than on soils. Sorption of TC also strongly depended on environmental factors and sediment/soil properties. Lower pH facilitated TC sorption through a cation exchange mechanism, which also took place at pH values above 5.5, where TC existed as a zwitterion (H₂L⁰) or anions (HL^- and L^2-). When pH was above 7, however, ligand-promoted dissolution of TC might occur due to TC weakening the Al-O bond of aluminum oxide and the Fe-O bond of iron oxide. Natural organic matter (NOM) plays a more important role in TC sorption than cation exchange capacity (CEC) and clay contents. The presence of Cd (II) increased TC sorption on both sediments and soils, which resulted from the decrease of equilibrium solution pH caused by Cd²⁺ exchange with H⁺ ions of sediment/soil surfaces. The increase of TC sorption was also related to the formation of TC-Cd complexes, where Cd²⁺ acted as a bridge between the sediment/soil and TC.     

Removal of high concentrations of polycyclic aromatic hydrocarbons from contaminated soil by biodiesel

Solubilizing experiments were carried out to evaluate the ability of biodiesel to remove polycyclic aromatic hydrocarbons (PAHs) from highly contaminated manufactured gas plant (MGP) and PAHs spiked soils with hydroxypropyl-β-cyclodextrin (HPCD) and tween 80 as comparisons. Biodiesel displayed the highest solubilities of phenanthrene (420.7 mg·L^-1), pyrene (541.0 mg·L^-1), and benzo(a)pyrene (436.3 mg·L^-1). These corresponded to several fold increases relative to 10% HPCD and tween 80. Biodiesel showed a good efficiency for PAH removal from the spiked and MGP soils for both low molecular weight and high molecular weight PAHs at high concentrations. Biodiesel was the best agent for PAH removal from the spiked soils as compared with HPCD and tween 80; as over 77.9% of individual PAH were removed by biodiesel. Tween 80 also showed comparable capability with biodiesel for PAH solubilization at a concentration of 10% for the spiked soils. Biodiesel solubilized a wider range of PAHs as compared to HPCD and tween 80 for the MPG soils. At PAH concentrations of 229.6 and 996.9 mg·kg^-1, biodiesel showed obvious advantage over the 10% HPCD and tween 80, because it removed higher than 80% of total PAH. In this study, a significant difference between PAH removals from the spiked and field MGP soils was observed; PAH removals from the MGP soil by HPCD and tween 80 were much lower than those from the spiked soil. These results demonstrate that the potential for utilizing biodiesel for remediation of highly PAH-contaminated soil has been established.     

Beurteilung des Ozonrisikos für die Waldregionen Bayerns am Beispiel des Jahres 2002 und des Extremtrockenjahres 2003 auf der Basis der externen Ozonexposition und der internen Ozonaufnahme

Background, aim, and scope Increasing background concentrations of ground-level tropospheric ozone and more frequent and prolonged summer drought incidences due to climate change are supposed to increase the stress on Bavarian forests. For such scenarios growth reduction and yield losses are predicted. Sustainable forest management in Bavaria aims to significantly increase the proportion of beech (Fagus sylvatica L.) because of its broad ecological amplitude. In our regional study different approaches for calculating ozone impact were used to estimate the risks for Bavarian forests in the average climatic, rather moist year 2002 and the extremely dry year 2003.Materials and methods Measurements were conducted for eleven forest ecosystem sites and two forest research sites representing typical Bavarian forest stands under different climatic conditions and situated in different altitudes. For risk assessment currently used approaches were applied either based on the calculation of the cumulative ozone exposure (external dose; MPOC maximal permitted ozone concentration; critical level AOT40_phen? accumulated ozone exposure over a threshold of 40 nl [O₃] l^–1, for the effective phenolgy of beech) or based on the calculation of the phytomedically relevant ozone flux into the stomata (internal dose, critical level AF_st>1,6, accumulated stomatal flux above a flux threshold of 1.6 nmol O₃?m^–2 PLA; PLA = projected leaf area). For calculations continuously recorded ozone concentrations and meteorological and phenological data from nearby rural open field background measuring stations from the national air pollution control and from forested sites were used. Additionally ozone induced leaf symptoms were assessed.Results The exposure-based indices AOT40_phen and MPOC as well as the flux-based index AF_st>1.6suggest that Bavarian forests are at risk from O₃ during a rather moist average year concerning climate conditions (2002) as well as in an extreme dry year (2003). Thus, growth reductions of 5?% are predicted when thresholds are exceeded. Threshold exceedance occurred in both years at all plots, mostly already at the beginning of the growing season and often even many times over. Ozone induced leaf symptoms could be detected only on a few plots in a very slight occurrence.Discussion The results for the applied critical level indices differed depending on climatic conditions during the growing seasons: Regarding exposure-based indices, the highest degree of threshold exceedance occurred in the dry year of 2003 at all plots; the flux-based approach indicated the highest stomatal ozone uptake and thus an increased risk at moist sites or during humid years, whereas the risk was decreasing at dry sites with prolonged water limitation. Hence, soil and accordingly plant water availability was the decisive factor for the flux-modelled internal ozone uptake via stomata. Drought and increased ozone impact can generate synergistic, but also antagonistic effects for forest trees. At water limited rather dry forest sites restricted transpiration and thus production, but concurrently lower ozone uptake and reduced risk for damage can be expected.Conclusions, recommendations, and perspectives For realistic site-specific risk assessment in forest stands the determination of the internal ozone dose via modeling flux based internal stomatal ozone uptake is more appropriate than the calculation of the external ozone dose. The predicted 5?% growth reductions are in discrepancy with the frequently observed increment increase during the last decades in forest stands. Comprehensive and significant statistical verification for ozone induced forest growth reduction as well as the systematic validation of thresholds for ozone in the field is still lacking. However, a multiplicity of different specific new and retrospective growth analysis data should allow closing the gap. Moreover, the determination of canopy transpiration with sap flow measurements is a novel approach to provide cause-effect related, site specific results for the effective internal ozone dose as well as for canopy water supply and consecutively for regional risk estimation. A further future objective is the refinement of O₃ flux modelling by further consideration of soil/water budget characteristics and the above mentioned improved estimations of crown and canopy transpiration. Further, the introduction of threshold ranges for forest trees in view of their specific regional climatic conditions and their validation in real forest stands is necessary for developing meaningful ozone risk predictions for forests.     

Species phylogenetic relatedness, priority effects, and ecosystem functioning

Species immigration history can structure ecological communities through priority effects, which are often mediated by competition. As competition tends to be stronger between species with more similar niches, we hypothesize that species phylogenetic relatedness, under niche conservatism, may be a reasonable surrogate of niche similarity between species, and thus influence the strength of priority effects. We tested this hypothesis using a laboratory microcosm experiment in which we established bacterial species pools with different levels of phylogenetic relatedness and manipulated the immigration history of species from each pool into microcosms. Our results showed that strong priority effects, and hence multiple community states, only emerged for the species pool with the greatest phylogenetic relatedness. Community assembly also resulted in a significant positive relationship between bacterial phylogenetic diversity and ecosystem functions. Interestingly, these results emerged despite a lack of phylogenetic conservatism for most of the bacterial functional traits considered. Our results highlight the utility of phylogenetic information for understanding the structure and functioning of ecological communities, even when phylogenetically conserved functional traits are not identified or measured.     

Effects of a diesel oxidation catalyst on gaseous pollutants and fine particles from an engine operating on diesel and biodiesel

The effects of a diesel oxidation catalytic (DOC) converter on diesel engine emissions were investigated on a diesel bench at various loads for two steady-state speeds using diesel fuel and B20. The DOC was very effective in hydrocarbon (HC) and CO oxidation. Approximately 90%–95% reduction in CO and 36%–70% reduction in HC were realized using the DOC. Special attention was focused on the effects of the DOC on elemental carbon (EC) and organic carbon (OC) fractions in fine particles (PM_2.5) emitted from the diesel engine. The carbonaceous compositions of PM_2.5 were analyzed by the method of thermal/optical reflectance (TOR). The results showed that total carbon (TC), OC and EC emissions for PM_2.5 from diesel fuel were generally reduced by the DOC. For diesel fuel, TC emissions decreased 22%–32% after the DOC depending on operating modes. The decrease in TC was attributed to 35%–97% decrease in OC and 3%–65% decrease in EC emissions. At low load, a significant increase in the OC/EC ratio of PM_2.5 was observed after the DOC. The effect of the DOC on the carbonaceous compositions in PM_2.5 from B20 showed different trends compared to diesel fuel. At low load, a slight increase in EC emissions and a significant decrease in OC/EC ratio of PM_2.5 after DOC were observed for B20.     

Environmental impact of historical harbour city Zadar (Croatia) on the composition of marine sediments and soils

Sediment samples and soils along the coast line of the Adriatic Sea were sampled along a transect near the coast line at Zadar/Croatia, ranging from north-western suburbs via the historical centre and the industrial area to south-east suburbs. The sediments were dominated by carbonates and clay minerals, and contaminations with Cd–Cu–Pb–Zn–TOC (total organic carbon) at the historical centre and the industrial site were detected, as well as P and Mo input at the mouth of a small creek, probably from agriculture. No trends between the composition of surface and subsurface sea sediments were seen. At the historic harbour site, total element concentrations versus grain size showed a minimum in the fine silt fraction for most of the elements analysed. The soil samples behind the shoreline were not carbonaceous, but dominated by Fe–Al– oxides, some contained high levels of Be–Cd–Cu–Sn–Zn. Surprisingly, high TOC values within the soils might be assigned to human impacts, not to humus. Contrary to data from street dust samples from Seoul city/Korea, which were measured within our laboratory at the same time, Pt–Ir–Au were at ambient levels due to the limited use of catalysts in cars in the Zadar area at the time of sampling.     

The role of black carbon as a catalyst for environmental redox transformation

Black carbon (BC) is an important class of geosorbents that control the fate and transport of organic pollutants in soil and sediment. We previously demonstrated a new role of BC as an electron transfer mediator in the abiotic reduction of nitroaromatic and nitramine compounds by Oh and Chiu (Environ Sci Technol 43:6983–6988, 2009). We proposed that BC can catalyze the reduction of nitro compounds because it contains microscopic graphitic (graphene) domains, which facilitate both sorption and electron transfer. In this study, we assessed the ability of different types of BC—graphite, activated carbon, and diesel soot—to mediate the reduction of 2,4-dinitrotoluene (DNT) and 2,4-dibromophenol (DBP) by H₂S. All three types of BC enhanced DNT and DBP reduction. H₂S supported BC-mediated reduction, as was observed previously with a thiol reductant. The results suggest that BC may influence the fate of organic pollutants in reducing subsurface environments through redox transformation in addition to sorption.