Analytical model for site-specific isotope fractionation in 13C during sorption: determination by isotopic 13C NMR spectrometry with vanillin as model compound

The aim of this study was to conceive a reactive transport model capable of providing quantitative site-specific enrichment factors for fractionation in ¹³C isotopic content during sorption. As test compound the model treats vanillin, for which the ¹³C isotopic content at natural abundance at each of the 8 carbon positions can be measured by quantitative ¹³C nuclear magnetic resonance spectrometry. This technique determines the isotope ratios with a resolution better than ±1‰ (0.1%) at each carbon position. Site-specific isotope fractionations were recorded in chromatography column experiments with silica RP-18 as stationary phase. The one dimensional reactive transport model accounted for the sorption/desorption behavior of 8 individual ¹³C-isotopomers and one ¹²C-isotopomer of vanillin and reproduced satisfactorily the bulk (average over the whole compound) fractionation observed during elution. After model calibration, the enrichment factors were fitted for each carbon site where a significant fractionation was recorded. To show the interest of such a transport model for environmental studies, the model, extended to three dimensions, was exploited to simulate reactive transport in an aquifer. These results show that significant ¹³C isotope fractionation is expected for 4 out of 8 ¹³C-isotopomers in vanillin, and illustrate that bulk isotope ratios measured by conventional compound specific isotope analysis and mass spectrometry would hardly document significant isotope fractionations in vanillin. It is concluded that modeling of site-specific isotope ratios in molecules is a priori feasible and may help to quantify unknown processes in the environment.     

Hexavalent chromium removal by a novel Serratia proteamaculans isolated from the bank of Sebou River (Morocco)

The novel Serratia proteamaculans isolated from a chromium-contaminated site was tolerant to a concentration of 500 mg Cr(VI)/l. The optimum pH and temperature for reduction of Cr(VI) by S. proteamaculans were found to be 7.0 and 30 °C, respectively. The Cr(VI) reduction rate decreased with the increase in Cr(VI) concentration from 100 to 400 mg/l, suggesting the enzymatic chromium reduction. Resting and permeabilised cell assays provided the better evidence that chromate reduction in S. proteamaculans is enzymatic. Reduction by cell-free filtrate shows no extracellular chromate-reducing activity, revealing that this activity may be associated to membrane fraction and/or cytosolic fraction. Assays conducted with cytosolic and particulate fraction of S. proteamaculans confirmed the role of membrane-bound proteins in Cr(VI) reduction. Furthermore, chromium reduced by heat-treated cells suggests that membrane-associated chromate reductase activity of S. proteamaculans is preceded by its adsorption on the cell surface.     

Microwave treatment and struvite recovery potential of dairy manure

Microwave digestion of liquid dairy manure was tested for the release of nutrients, such as orthophosphates, ammonia-nitrogen, magnesium, calcium and potassium, both with and without the aid of an oxidizing agent (hydrogen peroxide). The orthophosphate to total phosphorus ratio of the manure increased from 21% to greater than 80% with 5 minutes of microwave treatment. More than 36% of total chemical oxygen demand (t-COD) of the manure was reduced when microwave digestion was assisted with peroxide addition. In addition, the volatile fatty acids (VFAs) distribution shifted to simpler chain acids (acetic acid in particular) with an increase in operating temperature. In the second part of the study, digested manure with increased soluble phosphate was tested for the recovery of struvite (magnesium ammonium phosphate) at different pH. It was found that up to 90% of orthophosphate can be removed from the solution. Overall, it was concluded that the oxidizing agent-assisted microwave digestion process can be used upstream of anaerobic digestion, following which the anaerobically digested manure can be used for struvite recovery. Thus, this microwave digestion process presents the potential for enhanced efficiencies in both manure digestion and struvite recovery.     

Nutrient release from fish silage using microwave-enhanced advanced oxidation process

The microwave-enhanced advanced oxidation process was used to treat fish silage for nutrient release and solids reduction prior to its use as a fertilizer for greenhouse operations. Fifteen sets of experiments with varying hydrogen peroxide dosages and treatment temperatures were conducted to evaluate the effectiveness of the process on the solubilization of fertilizer constituents. It was found that up to 26% of total Kjeldahl nitrogen could be released as ammonia with 6% hydrogen peroxide dosage at 170°C. An increase of nitrate/nitrite concentration was observed with higher hydrogen peroxide dosage and higher microwave temperature; the highest concentration of 10.2 mg L^{? 1} nitrates/nitrites was achieved at at 170°C and 6% H₂O₂ dosage. Up to 20 ± 9.5% of total chemical oxygen demand was reduced at temperatures between 120 and 170°C. Large quantities of volatile fatty acids were generated at lower temperatures, corresponding to an increase in soluble chemical oxygen demand, but not at higher temperatures. The treatment of fish silage using the microwave-enhanced advanced oxidation process appears to be promising.     

Ultrafiltration tests for the reutilization of greenhouse wastewater

Abstract

A lab‐scale experiment was performed using two different pore‐size ultrafiltration membranes to investigate the removal efficiency of Tomato Mosaic Virus (ToMV), retainability of pollutant and nutrients, and flow characteristics. From the experiment, it may be concluded that ultrafiltration can be used effectively to eliminate ToMV. Tests with a 30K pore‐size ultrafiltration membrane achieved 99% virus removal efficiency and a 5K membrane practically removed 100% of the virus in greenhouse wastewater. Nutrient analysis indicated that all the essential nutrients could be retained and re‐utilized.     

Assessment of nitrogen oxides and ground-level ozone behavior in a dense air quality station network: Case study in the Lesser Antilles Arc

ABSTRACT

This paper presents a study on ground-level ozone (O₃), nitrogen oxides (NO_x = NO + NO₂) concentrations, and their variabilities in the ambient air of three sites of a tropical archipelago that is moderately urbanized. Statistical analysis was performed on a quite complete (>80%) set of 5 years of measurements (2008–2012). There are few studies on those pollutants and their seasonal behavior in the Caribbean area, where pollution level and cities configuration are different from megacities. Analyses are focused on pollutant variations at the scale of the day, the week, and the seasons, using hourly data. The observations show that NO_x concentrations are more elevated during the wet season, whereas O₃ concentrations are higher in the dry season. Amplitudes of ozone cycles are strongly influenced by meteorological conditions (temperature, global radiation, and wind speed) and prevailing levels of NO_x. An ozone weekend effect is detected with the highest amplitude in the city, where anthropogenic activity is the lowest during the weekend. Due to the nature and the origin of pollutants, NO_x shows higher variability than O₃ in the time series. Our results evince the need for continuous measurements of volatile organic compounds (VOCs) in order to better quantify their contribution in O₃ formation in an insular context where numerous natural sources have been identified.

Implications: Statistical analyses of observed NO_x and O₃ concentrations for 5 years for a typical low industrialized site of the Caribbean area have been done. Air quality for those components is correct based on the standards of the World Health Orgaization, pollutant source spatial distributions, and level of industrialization. Observations show the same patterns as in megacities but also a strong impact of weather conditions and road traffic. Behaviors of O₃ cannot be fully explained without VOCs monitoring. Localization and type of AQS should be reconsidered to improve the accuracy of concentrations of the pollutant and better understand their behaviors.     

Pyrolysis Kinetics and Residue Characteristics of Petrochemical Industrial Sludge

ABSTRACT

This study investigated the pyrolysis characteristics of sludge from wastewater treatment plants in the petrochemical industry and focused on the pyrolysis kinetics, elemental composition of residue, and volatile organic compounds (VOCs) of exhaust gas. As pyrolysis temperature increased to 773 K, the increasing rate of crude oil production tended to a stable condition. The result indicated that the optimal temperature of crude oil and water mixed production was 773 K. When pyrolysis temperature increased from 673 to 973 K, carbon, oxygen, nitrogen, and hydrogen concentrations of residue decreased and the sulfur concentration of residue increased. The concentrations of benzene, toluene, ethylbenzene, and styrene increased by the increasing pyrolysis temperature. We found that the reaction order of sludge pyrolysis was 2.5 and the activation energy of the reaction was 11.06 kJ/mol. We believe that our pyrolysis system is transitional between devolatilization and combustion.