Mechanisms of lead, copper, and zinc retention by phosphate rock

The solid-liquid interface reaction between phosphate rock (PR) and metals (Pb, Cu, and Zn) was studied. Phosphate rock has the highest affinity for Pb, followed by Cu and Zn, with sorption capacities of 138, 114, and 83.2 mmol/kg PR, respectively. In the Pb-Cu-Zn ternary system, competitive metal sorption occurred with sorption capacity reduction of 15.2%, 48.3%, and 75.6% for Pb, Cu, and Zn, respectively compared to the mono-metal systems. A fractional factorial design showed the interfering effect in the order of Pb>Cu>Zn. Desorption of Cu and Zn was sensitive to pH change, increasing with pH decline, whereas Pb desorption was decreased with a strongly acidic TCLP extracting solution (pH = 2.93). The greatest stability of Pb retention by PR can be attributed to the formation of insoluble fluoropyromorphite [Pb(10)(PO(4))(6)F(2)], which was primarily responsible for Pb immobilization (up to 78.3%), with less contribution from the surface adsorption or complexation (21.7%), compared to 74.5% for Cu and 95.7% for Zn. Solution pH reduction during metal retention and flow calorimetry analysis both supported the hypothesis of retention of Pb, Cu, and Zn by surface adsorption or complexation. Flow calorimetry indicated that Pb and Cu adsorption onto PR was exothermic, while Zn sorption was endothermic. Our research demonstrated that PR can effectively remove Pb from solutions, even in the presence of other heavy metals (e.g. Cu, Zn).     

Co-injection of air and steam for the prevention of the downward migration of DNAPLs during steam enhanced extraction: an experimental evaluation of optimum injection ratio predictions

When steam is injected into soil containing a dense volatile non-aqueous phase liquid contaminant, the DNAPL vaporized within the heated soil region condenses and accumulates ahead of the steam condensation front. If enough DNAPL accumulates, gravitational forces can overcome trapping forces allowing the liquid contaminant to flow downward. By injecting air with steam, a portion of the DNAPL vapor remains suspended in equilibrium with the air, decreasing liquid contaminant accumulation ahead of the steam condensation front, and thus reducing the possibility of downward migration. In a previous work, a theoretical model was developed to predict the optimum injection ratio of air to steam that would eliminate accumulation of DNAPL ahead of the temperature front and thus minimize the potential for downward migration. In this work, the theoretical model is summarized, and an experiment is presented in order to evaluate the optimum injection ratio prediction. In the experiment, a two-dimensional water saturated sand pack is contaminated with a known mass of TCE (DNAPL). The system is then remediated by co-injecting air and steam at the predicted optimum injection ratio, calculated based on the average contaminant soil concentration in the sand pack. Results for the co-injection of air and steam are compared to results for the injection of pure steam or pure air. Injection at the predicted optimum injection ratio for a volumetric average NAPL saturation, reduced accumulation of the contaminant ahead of the condensation front by over 90%, as compared to steam injection alone. This indicates that the optimum injection ratio prediction is a valuable tool for limiting the spreading of DNAPL during steam-enhanced extraction. Injection at the optimum injection ratio resulted in earlier recovery of contaminant than for steam injection alone. Co-injection of steam and air is also shown to result in much higher recovery rates than air injection alone.     

Effect of surfactants at low concentrations on the sorption of atrazine by natural sediment.

A series of experiments were carried out to determine the effect of surfactants at low concentrations on the sorption of atrazine by natural sediments. With surfactant concentrations ranging from 0 to 20 mg/ L, anionic and cationic surfactants appreciably reduce the adsorption of atrazine, while nonionic surfactant decreases the adsorption of atrazine at concentrations equal to or less than 1 mg/L and increases adsorption at higher concentrations. Desorption of atrazine in the presence of different sodium dodecylbenzene sulfonate (SDBS) concentrations shows that a portion of the bound pesticide resists desorption in the SDBS free system. However, the addition of SDBS accelerates the desorption of atrazine. Furthermore, the nature of sediment and the contacting sequence of SDBS, at 10 mg/L, with the sediment, also influence the adsorption of atrazine. The conclusions in this study could be explained partially by the effect of the type and concentration of surfactants and the characteristics of sediments.     

Comparative study of extraction methods for the determination of PAHs from contaminated soils and sediments

The following four methods were compared on the extraction efficiency of 16 EPA (US Environmental Protection Agency) polycyclic aromatic hydrocarbons (PAHs): German method of the Verband Deutscher Landwirtschaftlicher Untersuchungs und Forschungsanstalten (VDLUFA), two methods of the International Organization for Standardization using shaking (ISO A) and Soxhlet extraction (ISO B) and an ultrasonic method. Recovery rates of 16 PAHs were determined in two soils. Extraction efficiency was evaluated in five soils and three sediments. Effect of drying soils and sediments on extraction efficiency was tested using the VDLUFA and the ultrasonic methods. Our study shows that the number of aromatic rings, rather than extraction procedures, significantly influenced recovery rates of individual PAHs. No significant differences in extraction efficiency of the four methods were observed for less polluted samples. For highly polluted soils, extraction efficiency decreased in the following order: VDLUFA method > ISO A > ultrasonic method > ISO B. Influence of soil moisture on extraction efficiency depended to some extent on both solvent used and content of PAHs in samples. A mixture of dichloromethane/acetone (5:1) is recommended for PAH extraction from moist samples when the ultrasonic method is used.     

Redox-active ligands in artificial photosynthesis: a review

Environmental Chemistry Letters - Given the rising socioeconomic issues of fossil fuels, efficient artificial photosynthesis would be an important milestone toward a sustainable world. A key step...     

Biodegradation of phthalate esters by two bacteria strains

In this study two aerobic phthalic acid ester (PAE) degrading bacteria strains, DK4 and O18, were isolated from river sediment and petrochemical sludge, respectively. The two strains were found to rapidly degrade PAE with shorter alkyl-chains such diethyl phthalate (DEP), dipropyl phthalate (DPrP), di-n-butyl phthalate (DBP), benzylbutyl phthalate (BBP) and diphenyl phthalate (DPP) are very easily biodegraded, while PAE with longer alkyl-chains such as dicyclohexyl phthalate (DCP) and dihexyl phthalate (DHP) and di-(2-ethylhexyl) phthalate (DEHP) are poorly degraded. The degradation rates of the eight PAEs were higher for strain DK4 than for strain O18. In the simultaneous presence of strains DK4 and O18, the degradation rates of the eight PAEs examined were enhanced. When the eight PAEs were present simultaneously, degradation rates were also enhanced. We also found that PAE degradation was delayed by the addition of nonylphenol or selected polycyclic aromatic hydrocarbons (PAHs) at a concentration of 1 microg/g in the sediment. The bacteria strains isolated, DK4 and O18, were identified as Sphigomonas sp. and Corynebacterium sp., respectively.     

Isotopic characterisation of lead in contaminated soils from the vicinity of a non-ferrous metal smelter near Plovdiv, Bulgaria

Soil samples from the vicinity of a non-ferrous metal smelter near Plovdiv, Bulgaria contained very high concentrations of cadmium, lead and zinc (up to 140, 4900 and 5900 mg kg(-1), respectively). A roadside soil in a relatively uncontaminated area also contained high concentrations of the same metals (24, 1550 and 1870 mg kg(-1), respectively) indicating that the transport of ores could be a source of contamination. Even though the lead isotope ratios in all the samples fell within a very narrow range (for example, 1.186-1.195 for (206)Pb/(207)Pb), the samples could be differentiated into three distinct groups: ores ((206)Pb/(207)Pb and (208)Pb/(207)Pb ratios of 1.1874-1.1884 and 2.4755-2.4807, respectively), current deposition (1.1864 and 2.4704-2.4711, respectively) and local background (1.1927-1.1951 and 2.4772-2.4809, respectively). Although most of the current deposition has its origin in the ores used at the smelter, up to 12% could be from other sources such as petrol lead.     

Toxicity of acid-sulphate soil leachate and aluminium to the embryos and larvae of Australian bass (Macquaria novemaculeata) in estuarine water

The toxicity of leachate water from acid-sulphate soil to the early life stages of Australian bass, Macquaria novemaculeata, incubated in seawater was evaluated. Acid-sulphate soil leachate water (pH> or =6.8) delayed the hatching of fertilised eggs, but after 48 h the per cent hatching was normal. In comparison, acidic saline water (25 per thousand salinity) at pH 4.0 or less prevented embryos from hatching. The survival of yolk-sac larvae exposed to acid-sulphate soil leachate water at a concentration of 32% in seawater and an initial pH of 7.2, was significantly different to controls after 96 hours. In corresponding tests with only acidified saline water (20 per thousand salinity), pH levels equal to or below 5.0 killed yolk-sac larvae after 96 h exposure. Aluminum showed a pH dependent toxicity to yolk-sac larvae, with added aluminium as low as 200 microg litre(-1) having a significant effect on larval survival at pH 5.5, and concentrations of 600-800 microg litre(-1) having a significant effect on larval survival at an initial pH range of 6.0 < pH < 6.8. It was concluded that significant mortality of the early life stages of Australian bass would occur if they are exposed to acid-sulphate soil leachate that results in a pH in the receiving estuarine water below 5.5, or when the pH is below 6.8 and aluminium is present at a total concentration of 800 microg litre(-1) or greater.     

On-road motor vehicle emissions and fuel consumption in urban driving conditions

This paper reports on the analysis of on-road vehicle speed, emission, and fuel consumption data collected by four instrumented vehicles. Time-, distance-, and fuel-based average fuel consumption, as well as CO, HC, NOx, and soot emission factors, were derived. The influences of instantaneous vehicle speed on emissions and fuel consumption were studied. It was found that the fuel-based emission factors varied much less than the time- and distance-based emission factors as instantaneous speed changed. The trends are similar to the results obtained from laboratory tests. The low driving speed contributed to a significant portion of the total emissions over a trip. Furthermore, the on-road data were analyzed using the modal approach. The four standard driving modes are acceleration, cruising, deceleration, and idling. It was found that the transient driving modes (i.e., acceleration and deceleration) were more polluting than the steady-speed driving modes (i.e., cruising and idling) in terms of g/km and g/sec. These results indicated that the on-road emission measurement is feasible in deriving vehicle emissions and fuel consumption factors in urban driving conditions.