SVM application in hazard assessment: Self-heating for sulfurized rust

In order to assess the oxidation self-heating hazard of sulfurized rust, for particular ambient conditions in crude oil tanks, the support vector machine (SVM) technique is applied to predict the maximum temperature (T_max) of oxidation self-heating process. Five governing parameters are selected, i.e. the water content, mass of sulfurized rust, operating temperature, air flow rate and oxygen concentration in the respiratory/safety valve. The efficiency and validity of the SVM predictions are investigated in the case of two sets of data: more than 85 experiments performed in academic lab (China) and almost 17 additional results collected from existing literature. Two main steps are also discussed: the training process (on selected subsets of data) and prediction process (for the remaining subsets of data). It can be concluded that for both datasets the maximum temperature (T_max) values calculated by SVM technique were in good accordance with the experimental results, with relative errors smaller than 15% except for a few cases.The SVM technique seems therefore to be relevant and very helpful for complex implicit processes such as chemical reactions, as it is the case of the oxidation of sulfurized rust in oil tanks. Furthermore, such predictive methods can be continuously be improved through additional experiments feedback (larger databases) and can then be of crucial help for monitoring and early warning of hazardous reactions.     

C2–C8 NMHCs over the Eastern Mediterranean: Seasonal variation and impact on regional oxidation chemistry

More than 2500 measurements of C₂–C₈ non-methane hydrocarbons (NMHCs) have been conducted at Finokalia sampling station on the island of Crete over a thirty-month period (September 2003–February 2006), to investigate the factors controlling NMHC levels and estimate their role in the oxidizing capacity of the Eastern Mediterranean atmosphere. Atmospheric concentrations of NMHCs range from below the detection limit (5 pptv) to a few ppbv and present a hydroxyl radical (OH) driven seasonal pattern with lower values during summer. The diel variability was also influenced by the reaction of the NMHC with the OH radical, exhibiting a nighttime maximum and a midday or early afternoon minimum. Long-lived compounds demonstrate higher concentrations under the influence of the northern sector (European continent), indicating that besides chemistry, transport significantly contributes to NMHCs levels in the area. Based on the observed NMHCs diurnal cycles, mean OH radical levels of 3.5 × 10⁶ molecules cm⁻³ have been derived for May–October period.     

Identification of new ozonation disinfection byproducts of 17β-estradiol and estrone in water

Estrogens are a class of micro-pollutants found in water at low concentrations (in the ng L⁻¹ range), but often sufficient to exert estrogenic effects due to their high estrogenic potency. Disinfection of waters containing estrogens through oxidative processes has been shown to lead to the formation of disinfection byproducts, which may also be estrogenic. The present work investigates the formation of disinfection byproducts of 17β-estradiol (E2) and estrone (E1) in the treatment of water with ozone. Experiments have been carried out at two different concentrations of the estrogens in ground water (100 ng L⁻¹ and 100 μg L⁻¹) and at varying ozone dosages (0-30 mg L⁻¹). Detection of the estrogens and their disinfection byproducts in the water samples has been performed by means of ultra performance liquid chromatography-tandem mass spectrometry (UPLC-MS/MS) with a triple quadrupole (QqQ) and a quadrupole-time of flight (QqTOF) instrument. Both E2 and E1 have been found to form two main byproducts, with molecular mass (MM) 288 and 278 in the case of E2, and 286 and 276 in the case of E1, following presumably the same reaction pathways. The E2 byproduct with MM 288 has been identified as 10epsilon-17beta-dihydroxy-1,4-estradieno-3-one (DEO), in agreement with previously published results. The molecular structures and the formation pathways of the other three newly identified byproducts have been suggested. These byproducts have been found to be formed at both high and low concentrations of the estrogens and to be persistent even after application of high ozone dosages.     

Copper mobilization affected by weather conditions in a stormwater detention system receiving runoff waters from vineyard soils (Champagne, France)

Copper, a priority substance on the EU-Water Framework Directive list, is widely used to protect grapevines against fungus diseases. Many vineyards being located on steep slopes, large amounts of Cu could be discharged in downstream systems by runoff water. The efficiency of stormwater detention basins to retain copper in a vineyard catchment was estimated. Suspended solids, dissolved (Cu_diss) and total Cu (Cu_tot) concentrations were monitored in runoff water, upstream, into and downstream from a detention pond. Mean Cu_tot concentrations in entering water was 53.6 μg/L whereas it never exceeded 2.4 μg/L in seepage. Cu_tot concentrations in basin water (>100 μg/L in 24% of the samples) exceeded LC₅₀ values for several aquatic animals. Copper was principally sequestered by reduced compounds in the basin sediments (2/3 of Cu_tot). Metal sequestration was reversible since sediment resuspension resulted in Cu remobilization. Wind velocity controlled resuspension, explained 70% of Cu_diss variability and could help predicting Cu mobilization.     

Lactate oxidation in pyrite suspension: a Fenton-like process in situ generating H2O2

Pyrite is a common mineral at many mining sites. In this study, the mineral pyrite was studied as a Fenton-like reagent for environmental concerns. We selected lactate as a model target molecule to evaluate the Fenton-like catalytic efficiency of pyrite upon organic oxidation. A complete set of control experiments in both aerobic and anaerobic atmospheres unequivocally established that the pyrite in aqueous solution could spontaneously in situ generate OH and H₂O₂, serving as a Fenton-like reagent to catalyze the oxidation of lactate to pyruvate with no need for additional H₂O₂. We called it the pyrite-only Fenton-like (PF) reagent. Monitoring concentration changes of lactate and pyruvate with the time indicated that the pyrite mediated the favorable pyruvate formation at pH 4.5, 60 °C, under air atmosphere. The PF reaction could be stimulated by visible light illumination. Under the optimum conditions, up to 50% of lactate was degraded within 10 d. The results suggest that pyrite and its Fenton-like processes may be potentially practical in wastewater treatment.     

Decomposition and oxidation of sodium 3,5,6-trichloropyridin-2-ol in sub- and supercritical water

Sodium 3,5,6-trichloropyridin-2-ol (STCP) is a necessary precursor compound for the production of chlorpyrifos and triclopyr, which are extensively used as pesticide and herbicide, respectively. In the process of STCP production, however, large amount of wastewater containing STCP is discharged, which causes increasingly environmental concerns. Therefore, it is of great significance to develop a rapid and effective method for the disposal of containing STCP contaminants. In this work, the thermal decomposition of STCP in sub- and supercritical water was investigated using a continuous tubular reactor. While STCP was stable below 280 °C, it could be effectively decomposed at elevated temperature. FT-IR spectra of the decomposition products indicated that the pyridine ring structure in the STCP molecule was stable even at temperatures up to 400 °C. The decomposition reaction was mainly caused by the substitution of Cl groups in the STCP molecule with OH groups, resulting in polyhydroxylated pyridines as the major decomposition product. Moreover, high pressure favored the substitution reaction. To completely decompose STCP into non-toxic or low toxic compounds, supercritical water oxidation (SCWO) was employed to evaluate the oxidation of STCP using H₂O₂ as an oxidant. It was found that STCP could be completely oxidized to H₂O, CO₂ and corresponding inorganic ammonium salts with an oxidation rate of 99%.     

Field-scale operation of methane biofiltration systems to mitigate point source methane emissions

Methane biofiltration (MBF) is a novel low-cost technique for reducing low volume point source emissions of methane (CH₄). MBF uses a granular medium, such as soil or compost, to support the growth of methanotrophic bacteria responsible for converting CH₄ to carbon dioxide (CO₂) and water (H₂O). A field research program was undertaken to evaluate the potential to treat low volume point source engineered CH₄ emissions using an MBF at a natural gas monitoring station. A new comprehensive three-dimensional numerical model was developed incorporating advection-diffusive flow of gas, biological reactions and heat and moisture flow. The one-dimensional version of this model was used as a guiding tool for designing and operating the MBF. The long-term monitoring results of the field MBF are also presented. The field MBF operated with no control of precipitation, evaporation, and temperature, provided more than 80% of CH₄ oxidation throughout spring, summer, and fall seasons. The numerical model was able to predict the CH₄ oxidation behavior of the field MBF with high accuracy. The numerical model simulations are presented for estimating CH₄ oxidation efficiencies under various operating conditions, including different filter bed depths and CH₄ flux rates. The field observations as well as numerical model simulations indicated that the long-term performance of MBFs is strongly dependent on environmental factors, such as ambient temperature and precipitation.     

Experimental investigation on oxidation of sulfurized rust in oil tank

Oxidation of sulfurized rust in oil tank is complicated, and it is influenced by numerous factors such as water content, air humidity, operating temperature etc. The paper focuses on the oxidation process of sulfurized rust in the wild. Firstly, samples collected from a petrochemical company were put into the sulfurization & oxidation experimental apparatus to gain wet and dry sulfurized rusts. Their chemical compositions and phase were analyzed by Energy Dispersive X-ray Spectrometer (EDS) -scanning electron microscope (SEM) technique. The results showed that both wet and dry sulfurized rusts had S, Fe₂O₃, Fe₃S₄ and FeS₂, whereas FeS only existed in wet sulfurized rust. The two kinds of rusts gave a short length of side, diamond appearance and a large pore size in structure. Then oxidation of wet sulfurized rust was investigated, which included electrochemical reaction stage, electrochemical & chemical reaction coexisting stage and chemical reaction stage. The final oxidation product of wet sulfurized was determined to be Fe₂O₃. On the basis of this study, an indicator for monitoring and early-warning was proposed to prevent plants in vicinity of the accidental vessel or tank from fire and explosion.     

Isolation,identification and desulfurization mechanism of a sulfur-oxidizing bacterium with salt tolerance北大核心CSCD

Micro-organism with efficient desulfurization performance is a key factor in the biological desulfurization technology. This study aimed to seek such a sulfur-oxidizing strain and understand its desulfurization mechanism. Wastewater in a sewage station of natural gas purification plant was used to screen the sulfide-oxidizing strain, and to identify it based on sequence similarity analysis of 16S rDNA and the morphological characteristics. Thiosulfate was used as substrate for investigating the sulfur oxidation performance and salinity tolerance; the OD600, content change of thiosulfate, sulfate, sulfur, pH and total alkalinity in the cultural system were also investigated. The strain DS-B was found to share the highest sequence similarity with Thioalkalivibrio thiocyanoxidans ARh2, therefore determined as Thioalkalivibrio. At the optimum temperature of 35 °C for growth and degradation, the removal efficiency of thiosulfate could reach 98.7% after 7 days. Strain DS-B had strong resistance to thiosulfate, and the optimal concentration of S2O32- was 2 × 104 mg/L. The analysis for sulfur oxides showed that it could oxidize thiosulfate by the pathway of S2O32-→SO42- / S2O32- → S → SO42-. Therefore the strain DS-B is a sulfur-oxidizing bacterium with great application prospect for its strong salt tolerance and conspicuous removal capability for thiosulfate.